EP0071481B1 - Suds control agents and detergent compositions containing them - Google Patents
Suds control agents and detergent compositions containing them Download PDFInfo
- Publication number
- EP0071481B1 EP0071481B1 EP82304013A EP82304013A EP0071481B1 EP 0071481 B1 EP0071481 B1 EP 0071481B1 EP 82304013 A EP82304013 A EP 82304013A EP 82304013 A EP82304013 A EP 82304013A EP 0071481 B1 EP0071481 B1 EP 0071481B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- suds
- gelatinised starch
- detergent composition
- control agent
- silicone oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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
- C11D3/0026—Low foaming or foam regulating compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/18—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
-
- 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
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
Definitions
- This invention relates to detergent compositions containing suds control agents and to a process for their manufacture.
- Detergent compositions particularly fabric washing detergent powders, which produce only a relatively small amount of suds in washing machines are gaining an increasing share of the European market as automatic (drum-type) washing machines become more widespread.
- existing products generally use a mixture of soaps for controlling suds produced by anionic surfactants, or by mixtures of anionic and nonionic surfactants, it is now generally accepted in the industry that such products are not ideal, since the soap tends to have adverse effects, for example, on powder properties. Consequently, there are now a large number of proposals in the literature for alternative suds-control agents which do not contain soap.
- One example of such a proposal is that in British Patent No. 1,492,939 which discloses, amongst other things a silicone-based suds control agent.
- This suds-control agent involves the use of an adsorbent carrier, and as examples of such carriers, sodium carbonate, sodium tripolyphosphate, sodium silicate, clay, starch, Kieselguhr and Fuller's Earth are listed.
- gelatinised starch is a useful material for forming the basis of a silicone-based suds control agent in that it has an optimum combination of sorbency and solubility characteristics.
- the present invention provides a detergent composition
- a detergent composition comprising an anionic surfactant and a silicone-based suds-control agent, characterised in that the suds-control agent comprises a core of gelatinised starch having a mixture of a silicone oil and hydrophobic silica adsorbed thereon.
- the suds-control agent is coated with a layer of wax, preferably paraffin wax, since we have discovered that the storage characteristics of such coated agents are superior to those of uncoated ones.
- the invention provides a process for making a detergent composition characterised by the steps of
- gelatinised starch for the adsorbent core of the suds-control agent.
- Gelatinised starch is essentially a partially hydrolysed starch which can be obtained by suspending granules of starch, such as maize starch, in water and drying the suspension in steam heated drums.
- gelatinised starches sold under the Registered Trade Mark "Amigel” by Socidt6 des Produits du Mais of Clamart, France, but we believe that other gelatinised starches will be just as effective.
- the suds-control effect of a mixture of silicone oil and hydrophobic silica is quite easily deactivated and two factors in the characteristics of the gelatinised starch which have been found to be important though not essential to its effectiveness are its ionic character and its pH.
- the gelatinised starch should be nonionic in character and also that the pH should be in the range 5.5 to 9.
- the gelatinised starch Further important characteristics of the gelatinised starch are its particle size and its particle size distribution. Small particle size, that is to say a weight average particle size of from 50 to 500 pm is important from the viewpoint of maximising the surface area of the gelatinised starch, so that it can adsorb as much of a mixture of a silicone oil and hydrophobic silica as possible.
- the particle size distribution is preferred to be narrow so that if it is decided to granulate the gelatinised starch, then the resultant granules are relatively uniform in size and shape. The subsequent coating with a layer of wax is then more likely to be of uniform thickness and to be coherent than if particles of a widely different particle size are used to form the granule.
- silicone oils used in the mixture of silicone oil and hydrophobic silica of the invention are generally from the chemical class of alkyl polysiloxanes. These materials are well known to industrial chemists and are available in a wide range of molecular weights, the higher molecular weight materials, as is usually the case with polymers, tending to be more viscous. Silicone oils are available from various suppliers, and Dow Corning Corporation of Illinois, USA, and Rhone-Poulenc Chemie, supply mixtures of silicone oils and silicas of various types, including hydrophobic silicas, which we have found very satisfactory for use as mixtures of silicone oil and hydrophobic silica in this invention.
- the process of this invention involves a granulation or agglomeration step.
- Granulation and agglomeration are well-known techniques in which liquid is added to particles of a solid, with agitation, and in which large particles are formed.
- the "Eirich" pan (Registered Trade Mark) is an apparatus which is well-known in the food and detergents industry which was developed especially for granulation processes.
- fluidised bed apparatus such as the "Anhydro" fluidised bed (Registered Trade Mark) for granulation or, more preferably a Schugi (Registered Trade Mark) mixer.
- This type of mixer consists essentially of a closed cylinder provided with a set of mixer blades rotatable about its major axis. The blades are of variable pitch and are arranged so that they can impart a spiral mixing motion to particles in the mixer.
- the side-walls of the cylinder are provided with spray nozzles for the introduction of liquid.
- the process also involves a coating step and this can be a spraying step in which a solution of a wax in an organic solvent is sprayed onto the granules produced in the previous step. The solvent is then evaporated to leave a coherent coating of the wax on the granules.
- a molten wax can be used in the coating step.
- the type of wax used is not critical since, as it is present in only a relative thin layer, it will dissolve off the granules or agglomerates in the warm, detergent-rich environment of the wash liquor.
- the softening point of the wax should be below the temperature at which washing generally takes place, that is to say below about 80°C.
- wash temperatures it is becoming increasingly common for wash temperatures to be specified at as low as 60°C or even 40°C. We prefer to use paraffin wax of these softening points, but there is no reason why other waxes, should not be used.
- the relative proportions of the essential components in the preferred suds-control agents of the invention can vary quite widely, although since the gelatinised starch is intended to be present as an adsorbent it will normally be present in an amount greater than the silicone oil which it is intended to adsorb. Preferred relative proportions are: the percentages being based on the total weight of the suds-control agent.
- the suds-control agent will normally be present in detergent compositions in accordance with the invention in amounts of from 0.1 to 2%, preferably 0.1 to 1%.
- this invention is concerned with a suds-control agent and consequently no attempt has been made in this specification to describe all possible detergent compositions to which the component could be added. It is self-evident that the usual detergent composition components are appropriate provided that they have no adverse reaction with the components of the suds-control agent.
- anionic surfactants such as alkylbenzene sulphonates, primary and secondary alkyl sulphates, secondary alkane sulphonates, soaps and olefine sulphonates can be used.
- Nonionic surfactants either alone or in combination with anionic surfactants can also be used, the preferred nonionic surfactants being C, to C 24 primary or secondary alcohols ethoxylated with from 1 to 25 moles of ethylene oxide per mole of alcohol. Typical amounts of surfactant are from 3 to 25% by weight when only one species is present, and from 1 to 16% by weight when more than one is present.
- Builders may be present in amounts of from 5 to 50% by weight.
- Typical of the inorganic builders are sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate, sodium carbonate and the crystalline and amorphous forms of aluminosilicates.
- Organic builders such as sodium nitrilotriacetate, sodium citrate, sodium carboxymethyloxysuccinate, and the host of other materials have been suggested as phosphate replacers are also appropriate.
- sodium silicate as a corrosion inhibitor and powder structurant
- oxygen bleaches such as sodium perborate and sodium percarbonate
- bleach precursors such as tetraacetylethylene diamine, fluorescers, antiredeposition agents and antiashing agents
- suds- suppressing agents other than the silicone granules of the invention and moisture.
- a fabric washing powder having the following formulation was prepared by conventional spray-drying and dry-dosing techniques:
- the suds assessment test is performed by washing a standard load of clean washing in a Brandt 433 (registered trade mark) washing machine.
- the washing machine was specially modified to provide a window and the window had an arbitrary scale on it from which suds height could be read.
- the reservoir holding the wash liquor is fitted with a thermometer.
- Example 2 A similar experiment to that in Example 1 was performed, but in this example the suds-control granules were prepared from 46 parts of the gelatinised starch and 46 parts of the mixture of a silicone oil and hydrophobic silica.
- the granules were combined with the remaining components of the fabric washing powder, and the suds control performance of the powder was assessed as described above except that the powder formulation contained 1% of sodium hardened rape seed oil soap and a correspondingly reduced amount of water.
- the results of the suds control assessment are shown in Table 2.
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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)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Abstract
Description
- This invention relates to detergent compositions containing suds control agents and to a process for their manufacture.
- Detergent compositions, particularly fabric washing detergent powders, which produce only a relatively small amount of suds in washing machines are gaining an increasing share of the European market as automatic (drum-type) washing machines become more widespread. While existing products generally use a mixture of soaps for controlling suds produced by anionic surfactants, or by mixtures of anionic and nonionic surfactants, it is now generally accepted in the industry that such products are not ideal, since the soap tends to have adverse effects, for example, on powder properties. Consequently, there are now a large number of proposals in the literature for alternative suds-control agents which do not contain soap. One example of such a proposal is that in British Patent No. 1,492,939 which discloses, amongst other things a silicone-based suds control agent. This suds-control agent involves the use of an adsorbent carrier, and as examples of such carriers, sodium carbonate, sodium tripolyphosphate, sodium silicate, clay, starch, Kieselguhr and Fuller's Earth are listed.
- We have now discovered that gelatinised starch is a useful material for forming the basis of a silicone-based suds control agent in that it has an optimum combination of sorbency and solubility characteristics.
- Accordingly, in the first aspect, the present invention provides a detergent composition comprising an anionic surfactant and a silicone-based suds-control agent, characterised in that the suds-control agent comprises a core of gelatinised starch having a mixture of a silicone oil and hydrophobic silica adsorbed thereon.
- It is strongly preferred that the suds-control agent is coated with a layer of wax, preferably paraffin wax, since we have discovered that the storage characteristics of such coated agents are superior to those of uncoated ones.
- In its second aspect, the invention provides a process for making a detergent composition characterised by the steps of
- (a) granulating a gelatinised starch with a mixture of a silicone oil and hydrophobic silica to form granules having a weight average particle size of from 200 to 1000 pm and having the mixture of silicone oil and hydrophobic silica sorbed thereon;
- (b) coating the granules with a wax preferably by spraying them with a solution of wax in an organic solvent and in that case subsequently evaporating the organic solvent; and
- (c) admixing the resultant suds-control agent with the remainder of the composition.
- The essential feature of both aspects of this invention is the use of gelatinised starch for the adsorbent core of the suds-control agent. Gelatinised starch is essentially a partially hydrolysed starch which can be obtained by suspending granules of starch, such as maize starch, in water and drying the suspension in steam heated drums. In the work described in this specification we have used gelatinised starches sold under the Registered Trade Mark "Amigel" by Socidt6 des Produits du Mais of Clamart, France, but we believe that other gelatinised starches will be just as effective.
- The suds-control effect of a mixture of silicone oil and hydrophobic silica is quite easily deactivated and two factors in the characteristics of the gelatinised starch which have been found to be important though not essential to its effectiveness are its ionic character and its pH. We prefer, for the stability reason referred to, that the gelatinised starch should be nonionic in character and also that the pH should be in the range 5.5 to 9.
- Further important characteristics of the gelatinised starch are its particle size and its particle size distribution. Small particle size, that is to say a weight average particle size of from 50 to 500 pm is important from the viewpoint of maximising the surface area of the gelatinised starch, so that it can adsorb as much of a mixture of a silicone oil and hydrophobic silica as possible. The particle size distribution is preferred to be narrow so that if it is decided to granulate the gelatinised starch, then the resultant granules are relatively uniform in size and shape. The subsequent coating with a layer of wax is then more likely to be of uniform thickness and to be coherent than if particles of a widely different particle size are used to form the granule.
- The silicone oils used in the mixture of silicone oil and hydrophobic silica of the invention are generally from the chemical class of alkyl polysiloxanes. These materials are well known to industrial chemists and are available in a wide range of molecular weights, the higher molecular weight materials, as is usually the case with polymers, tending to be more viscous. Silicone oils are available from various suppliers, and Dow Corning Corporation of Illinois, USA, and Rhone-Poulenc Chemie, supply mixtures of silicone oils and silicas of various types, including hydrophobic silicas, which we have found very satisfactory for use as mixtures of silicone oil and hydrophobic silica in this invention.
- The process of this invention involves a granulation or agglomeration step. Granulation and agglomeration are well-known techniques in which liquid is added to particles of a solid, with agitation, and in which large particles are formed. The "Eirich" pan (Registered Trade Mark) is an apparatus which is well-known in the food and detergents industry which was developed especially for granulation processes. However, it is also possible to use fluidised bed apparatus such as the "Anhydro" fluidised bed (Registered Trade Mark) for granulation or, more preferably a Schugi (Registered Trade Mark) mixer. This type of mixer consists essentially of a closed cylinder provided with a set of mixer blades rotatable about its major axis. The blades are of variable pitch and are arranged so that they can impart a spiral mixing motion to particles in the mixer. The side-walls of the cylinder are provided with spray nozzles for the introduction of liquid. ,
- The process also involves a coating step and this can be a spraying step in which a solution of a wax in an organic solvent is sprayed onto the granules produced in the previous step. The solvent is then evaporated to leave a coherent coating of the wax on the granules. Alternatively a molten wax can be used in the coating step.
- The type of wax used is not critical since, as it is present in only a relative thin layer, it will dissolve off the granules or agglomerates in the warm, detergent-rich environment of the wash liquor. However, it is preferred that the softening point of the wax should be below the temperature at which washing generally takes place, that is to say below about 80°C. For compositions intended for low temperature washing, waxes of correspondingly low softening points will be appropriate. It is becoming increasingly common for wash temperatures to be specified at as low as 60°C or even 40°C. We prefer to use paraffin wax of these softening points, but there is no reason why other waxes, should not be used.
- The relative proportions of the essential components in the preferred suds-control agents of the invention can vary quite widely, although since the gelatinised starch is intended to be present as an adsorbent it will normally be present in an amount greater than the silicone oil which it is intended to adsorb. Preferred relative proportions are:
- The suds-control agent will normally be present in detergent compositions in accordance with the invention in amounts of from 0.1 to 2%, preferably 0.1 to 1%.
- It will be understood that this invention is concerned with a suds-control agent and consequently no attempt has been made in this specification to describe all possible detergent compositions to which the component could be added. It is self-evident that the usual detergent composition components are appropriate provided that they have no adverse reaction with the components of the suds-control agent. For example, anionic surfactants such as alkylbenzene sulphonates, primary and secondary alkyl sulphates, secondary alkane sulphonates, soaps and olefine sulphonates can be used. Nonionic surfactants, either alone or in combination with anionic surfactants can also be used, the preferred nonionic surfactants being C, to C24 primary or secondary alcohols ethoxylated with from 1 to 25 moles of ethylene oxide per mole of alcohol. Typical amounts of surfactant are from 3 to 25% by weight when only one species is present, and from 1 to 16% by weight when more than one is present.
- Builders may be present in amounts of from 5 to 50% by weight. Typical of the inorganic builders are sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate, sodium carbonate and the crystalline and amorphous forms of aluminosilicates. Organic builders such as sodium nitrilotriacetate, sodium citrate, sodium carboxymethyloxysuccinate, and the host of other materials have been suggested as phosphate replacers are also appropriate.
- Other components which may be present are sodium silicate as a corrosion inhibitor and powder structurant, oxygen bleaches such as sodium perborate and sodium percarbonate, bleach precursors such as tetraacetylethylene diamine, fluorescers, antiredeposition agents and antiashing agents, suds- suppressing agents other than the silicone granules of the invention, and moisture.
- The invention will be further illustrated in the following Examples.
-
- To this formulation was added 0.3% of a suds control agent in accordance with the invention which was prepared as follows:
- 54 parts of gelatinised starch (Amigel 30076) having a weight average particle size of 340 pm was granulated in an Eirich pan granulator while 38 parts of a mixture of a silicone oil and hydrophobic silica sold by Dow Corning Corporation under the trade mark Silicone oil DB100 was sprayed onto it. A solution of 7.5 parts of paraffin wax in chloroform was sprayed onto the granules, which were then weathered to evaporate the solvent which was recovered. The granules were then dusted with 0.5 parts of finely-divided silica to prevent stickiness. The washing powder produced in this way containing the gelatinised starch-based granules was then divided into two. The first portion was submitted immediately to the suds assessment test which is described below, while the second portion was stored at 37°C for 1 month before being submitted to the test.
- The suds assessment test is performed by washing a standard load of clean washing in a Brandt 433 (registered trade mark) washing machine. The washing machine was specially modified to provide a window and the window had an arbitrary scale on it from which suds height could be read. The reservoir holding the wash liquor is fitted with a thermometer.
-
- It can be seen from the above Table that although there is some deactivation of the suds-control effectiveness of the granules after storage for a month at 37°C, it is by no means severe. Considering that in the absence of any suds control agent the suds height would rise to over 60 cms almost immediately the washing process started, this relatively slight deactivation would be perfectly acceptable in commercial practice.
- A similar experiment to that in Example 1 was performed, but in this example the suds-control granules were prepared from 46 parts of the gelatinised starch and 46 parts of the mixture of a silicone oil and hydrophobic silica.
- The granules were combined with the remaining components of the fabric washing powder, and the suds control performance of the powder was assessed as described above except that the powder formulation contained 1% of sodium hardened rape seed oil soap and a correspondingly reduced amount of water. The results of the suds control assessment are shown in Table 2.
- It is again apparent that although some deactivation of the suds-control effectiveness of the granules occurs, it remains within acceptable limits. The effect of the combination of the granules with soap is apparent.
Claims (8)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT82304013T ATE20358T1 (en) | 1981-07-31 | 1982-07-29 | FOAM CONTROL AGENTS AND DETERGENT COMPOSITIONS CONTAINING THEM. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8123492 | 1981-07-31 | ||
GB8123492 | 1981-07-31 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0071481A1 EP0071481A1 (en) | 1983-02-09 |
EP0071481B1 true EP0071481B1 (en) | 1986-06-11 |
Family
ID=10523604
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP82304013A Expired EP0071481B1 (en) | 1981-07-31 | 1982-07-29 | Suds control agents and detergent compositions containing them |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0071481B1 (en) |
AT (1) | ATE20358T1 (en) |
DE (1) | DE3271649D1 (en) |
ES (1) | ES514599A0 (en) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ZA833292B (en) * | 1982-05-11 | 1984-12-24 | Unilever Plc | Granules containing silicone-based anti-foam and a process for preparing them |
ZA838239B (en) * | 1982-11-10 | 1985-06-26 | Unilever Plc | Hydrocarbon anti-foam granules |
GB8513074D0 (en) * | 1985-05-23 | 1985-06-26 | Unilever Plc | Antifoam ingredient |
US4652392A (en) * | 1985-07-30 | 1987-03-24 | The Procter & Gamble Company | Controlled sudsing detergent compositions |
GB8521956D0 (en) * | 1985-09-04 | 1985-10-09 | Unilever Plc | Antifoam ingredient |
GB9410677D0 (en) | 1994-05-27 | 1994-07-13 | Unilever Plc | Detergent compositions |
DE60017223T2 (en) | 1999-08-13 | 2005-12-08 | Dow Corning S.A. | Foam control agent based on silicone |
DE60039559D1 (en) | 1999-08-13 | 2008-09-04 | Dow Corning Sa | Silicone-containing foam control agent |
DE10108459A1 (en) * | 2001-02-22 | 2002-09-12 | Henkel Kgaa | Stability of foam-regulator granulates for use in detergents is improved by using a carrier containing alkali carbonate and a Bronsted acid |
CN102149803B (en) * | 2008-09-12 | 2012-12-12 | 荷兰联合利华有限公司 | Improvements relating to fabric conditioners |
US11697727B2 (en) * | 2019-12-16 | 2023-07-11 | The Goodyear Tire & Rubber Company | Silica coated starch |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2462184A1 (en) * | 1979-07-31 | 1981-02-13 | Eurand France | Antifoaming silicone oil compsn. for washing powders - is oil mixed with absorbent cpd. and granules coated with cpd. |
FR2481942B1 (en) * | 1980-05-12 | 1988-04-22 | Unilever Nv | ANTI-MOSS GRANULES, THEIR MANUFACTURING PROCESS AND THEIR USE IN DETERGENT COMPOSITIONS |
-
1982
- 1982-07-29 DE DE8282304013T patent/DE3271649D1/en not_active Expired
- 1982-07-29 EP EP82304013A patent/EP0071481B1/en not_active Expired
- 1982-07-29 AT AT82304013T patent/ATE20358T1/en not_active IP Right Cessation
- 1982-07-30 ES ES514599A patent/ES514599A0/en active Granted
Also Published As
Publication number | Publication date |
---|---|
ATE20358T1 (en) | 1986-06-15 |
DE3271649D1 (en) | 1986-07-17 |
ES8308354A1 (en) | 1983-08-16 |
ES514599A0 (en) | 1983-08-16 |
EP0071481A1 (en) | 1983-02-09 |
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