EP0094250B1 - Process for preparing granules containing silicone-based anti-foam - Google Patents
Process for preparing granules containing silicone-based anti-foam Download PDFInfo
- Publication number
- EP0094250B1 EP0094250B1 EP19830302643 EP83302643A EP0094250B1 EP 0094250 B1 EP0094250 B1 EP 0094250B1 EP 19830302643 EP19830302643 EP 19830302643 EP 83302643 A EP83302643 A EP 83302643A EP 0094250 B1 EP0094250 B1 EP 0094250B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- process according
- wax
- waxes
- water
- silicone
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/528—Carboxylic amides (R1-CO-NR2R3), where at least one of the chains R1, R2 or R3 is interrupted by a functional group, e.g. a -NH-, -NR-, -CO-, or -CON- group
-
- 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 granules containing a silicone-based antifoam and to a process for manufacturing them, as well as to a detergent powder containing the granules.
- Granules containing a silicone-based antifoam are known. Certain granules of this type are described in British patent No. 1492939 and others in French patent No. 2 462 184.
- Foam regulators can also be formed as described in FR-A-2 194 771 by melting silicone together with a water-soluble or water-dispersible meltable vehicle.
- Carbowax polyethylene glycol
- Water-insoluble waxes are not suggested in this role.
- European patent application No. 0 071 481 also relates to granules containing a silicone-based antifoam.
- the process which is described in the specification of that application involves granulating gelatinised starch whilst spraying on a mixture of a silicone oil and a hydrophobic silica. A solution of . paraffin wax in chloroform is then sprayed onto the granules and the solvent is evaporated.
- the present invention provides a process for the manufacture of granules containing a silicone-based anti-foam which comprises the steps of:
- the silicone comprises a mixture of a liquid or liquifiable polysiloxane with particles of a hydrophobic material
- the hydrophobic material is preferably a hydrophobed silica, a water-insoluble salt of an alkyl phosphoric acid, or a compound of one of the following general formulae: or where R' and R 3 represent aliphatic hydrocarbon residues containing 14 ⁇ 22 carbon atoms, R 2 and R represent hydrogen atoms or aliphatic hydrocarbon residues containing 1-22 carbon atoms, and R represents an aliphatic residue containing 1-9 carbon atoms.
- alkylene-bis-amides,and in particular ethylene and methylene-bis-stearimide are the preferred compounds, that is to say compounds of the general formula: where x is an integer from 5 to 25 and n is 1 or 2 and in particular compounds of the formula.
- Preferred waxes are of mineral origin, especially those derived from petroleum, including microcrystalline and oxidised microcrystalline petroleum waxes and paraffin waxes.
- synthetic waxes, or natural waxes such as Montan waxes, beeswax, candelilla or carnauba waxes may also be used as may a mixture of any of these waxes.
- Whatever wax is used it is preferred that its melting point is between 35° and 70°C so that it is readily liquifiable.
- the absorbent for use in the process of the present invention is preferably gelatinised starch, but other absorbents can also be used.
- Preferred are those materials which are conventionally employed as components of detergent powders, for example sodium tripolyphosphate, sodium sulphate, sodium carboxymethyl cellulose and sodium aluminosilicate.
- the apparatus in which the liquifiable mixture of silicone and wax is sprayed onto the absorbent can be any of the apparatus conventionally used for granulation or agglomeration. Examples are the Eirich (registered Trade Mark) pan, the Schugi (registered Trade Mark) mixer, or any one of the numerous fluidised bed apparatus which are available, such as the Anhydro (registered Trade Mark) fluidised bed.
- a typical composition of the granules formed in the process of the invention is:
- the absorbent can be present in amounts of from 20-80%, the silicone compound in amounts of from 5-40%, the paraffin wax in amounts of from 5-30% and the nonionic surfactant in amounts up to 10%, the percentages being expressed by weight.
- the granules may be incorporated into spray-dried (powdered) detergent compositions or into liquid ones.
- powdered detergent compositions they will be dosed into the powder after spray-drying, along with other materials which are conventionally post-dosed such as sodium perborate and fillers.
- liquids which are structured sometimes called false-body liquids
- the granules can be added to the liquid in the final step of the manufacturing process.
- structured liquids There are two basic types of structured liquids, one in which the structure is imparted by interaction between surfactants and electrolytes, and the other in which it is imparted by means of a colloid such as a clay. Both types are capable of suspending the granules of the invention.
- composition in powdered or in liquid form it will normally contain both an anionic and a nonionic surfactant but may also contain either alone or a soap as the major detergent-active species
- the powdered compositions will contain a detergency builder and the liquid ones will normally do so. but need not necessarily.
- Other components which will normally be present are corrosion inhibitors anti redeposition agents, fluorescers, stabilisers and substantial proportions of water.
- Typical anionic surfactants which may be present in amounts of from about 2 to 35% by weight o' the finished compositions are sodium alkylbenzene sulphonates, preferably the C 10 ⁇ C 14 alkyl compound sodium primary and secondary alkyl sulphates, preferably the C 10 ⁇ C 22 alkyl sulphates, sodium sulphonates, preferably the C 10 ⁇ C 18 sulphonates and sodium alkane sulphonates.
- Soaps of fatty acds may also be present, preferably the sodium and potassium salts of C 10 ⁇ C 22 fatty acids, both saturated and unsaturated.
- soap is the sole anionic surfactant it may be present in an amount up to about 65% or weight of the finished composition, down to about 1 ⁇ 2% by weight when other anionic surfactant are present.
- Typical soaps which can be used are those formed from coconut oil, tallow and natural containing high proportions of oleic acid such as sunflower oil.
- Typical nonionic surfactants are ethoxylated primary and secondary alcohols of from 8 to 25 carbon atoms containing from 3 to 25 moles of ethylene oxide per mole of alcohol. These materials may generaly be present in an amount of from 1 to 15% by weight, based on the weight of the finished composition
- Typical detergency builders which can be used are the water-soluble phosphates, carbonates percarbonates and aluminosilicates, particularly the sodium and potassium salts of these compounds
- Organic builders may also be used, examples being sodium carboxymethyloxysuccinate, sodium citrate sodium polyacrylates and sodium nitrilotriacetate. Any of these compounds, or any other bullder compound, in any suitable mixture, may be used in amounts of from 5 to 50% by weight of the finished composition.
- gelatinised starch (Amigel 30076 registered Trade Mark, manufactured and sold by Societe des Produits du Mais, of Clarmart, France) was placed in the pan of an Eirich (registered Trade Mark) pan granulator.
- the resultant liquid was then sprayed onto the gelatinised starch in the pan granulator then, 4.8 parts of nonionic surfactant (C l3 - 18 primary alcohol 8EO) where sprayed onto the granules.
- the following detergent composition was prepared by conventional spray-drying and dry-dosing techniques, the granules of Example 1 being added in the dry-dosing step.
- the powder obtained was divided into two batches. The first batch was immediately subjected to the foam assessment test described below. The other batch was stored in unlaminated, sealed cartons at 37°C and 60% relative humidity. The stored batches were then subjected to test after 2 weeks and 4 weeks of storage.
- 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.
Abstract
Description
- This invention relates to granules containing a silicone-based antifoam and to a process for manufacturing them, as well as to a detergent powder containing the granules.
- Granules containing a silicone-based antifoam are known. Certain granules of this type are described in British patent No. 1492939 and others in French patent No. 2 462 184.
- Suds-suppressing granules containing both silicone oil and wax, for use in detergent compositions, and a process for the manufacture of such granules is described in EP-A-0 040 091. In this process, an absorbent is first impregnated with silicone oil usually as a solution or dispersion in an organic solvent, and then optionally, a solution of a paraffin wax, preferably in a different solvent is sprayed on to the absorbent and the second solvent is evaporated to provide a final protective envelope to protect the silicone oil already applied to the absorbent.
- Foam regulators can also be formed as described in FR-A-2 194 771 by melting silicone together with a water-soluble or water-dispersible meltable vehicle. Carbowax (polyethylene glycol) is one such example of a meltable vehicle. Water-insoluble waxes are not suggested in this role.
- European patent application No. 0 071 481 also relates to granules containing a silicone-based antifoam. The process which is described in the specification of that application involves granulating gelatinised starch whilst spraying on a mixture of a silicone oil and a hydrophobic silica. A solution of . paraffin wax in chloroform is then sprayed onto the granules and the solvent is evaporated.
- In a factory environment the use of volatile organic solvents is undesirable, because many of them are either inflammable or toxic, and so we have developed a new process for manufacturing granules containing a silicone-based anti-foam which does not involve the use of an organic solvent.
- Accordingly, the present invention provides a process for the manufacture of granules containing a silicone-based anti-foam which comprises the steps of:
- (a) forming a liquified mixture of a silicone and a wax
- (b) forming an agitated bed of a granular absorbent and
- (c) spraying the liquified mixture onto the absorbent.
- Preferably the silicone comprises a mixture of a liquid or liquifiable polysiloxane with particles of a hydrophobic material, and the hydrophobic material is preferably a hydrophobed silica, a water-insoluble salt of an alkyl phosphoric acid, or a compound of one of the following general formulae:
- Mixtures of silicone oils and hydrophobed silicas are sold by the Dow Chemical Company under the trade mark DB100, and this is the preferred material for use in the process of the invention. Amongst the various nitrogen compounds which are specified above, alkylene-bis-amides,and in particular ethylene and methylene-bis-stearimide are the preferred compounds, that is to say compounds of the general formula:
- Preferred waxes are of mineral origin, especially those derived from petroleum, including microcrystalline and oxidised microcrystalline petroleum waxes and paraffin waxes. However synthetic waxes, or natural waxes such as Montan waxes, beeswax, candelilla or carnauba waxes may also be used as may a mixture of any of these waxes. Whatever wax is used it is preferred that its melting point is between 35° and 70°C so that it is readily liquifiable.
- The absorbent for use in the process of the present invention is preferably gelatinised starch, but other absorbents can also be used. Preferred are those materials which are conventionally employed as components of detergent powders, for example sodium tripolyphosphate, sodium sulphate, sodium carboxymethyl cellulose and sodium aluminosilicate.
- The apparatus in which the liquifiable mixture of silicone and wax is sprayed onto the absorbent can be any of the apparatus conventionally used for granulation or agglomeration. Examples are the Eirich (registered Trade Mark) pan, the Schugi (registered Trade Mark) mixer, or any one of the numerous fluidised bed apparatus which are available, such as the Anhydro (registered Trade Mark) fluidised bed.
-
- However, considerable variations can be made based on this composition, so that the absorbent can be present in amounts of from 20-80%, the silicone compound in amounts of from 5-40%, the paraffin wax in amounts of from 5-30% and the nonionic surfactant in amounts up to 10%, the percentages being expressed by weight.
- The granules may be incorporated into spray-dried (powdered) detergent compositions or into liquid ones. In the case of powdered detergent compositions they will be dosed into the powder after spray-drying, along with other materials which are conventionally post-dosed such as sodium perborate and fillers. In the case of liquids which are structured (sometimes called false-body liquids) the granules can be added to the liquid in the final step of the manufacturing process. There are two basic types of structured liquids, one in which the structure is imparted by interaction between surfactants and electrolytes, and the other in which it is imparted by means of a colloid such as a clay. Both types are capable of suspending the granules of the invention.
- Whether the composition is in powdered or in liquid form it will normally contain both an anionic and a nonionic surfactant but may also contain either alone or a soap as the major detergent-active species The powdered compositions will contain a detergency builder and the liquid ones will normally do so. but need not necessarily. Other components which will normally be present are corrosion inhibitors anti redeposition agents, fluorescers, stabilisers and substantial proportions of water.
- Typical anionic surfactants, which may be present in amounts of from about 2 to 35% by weight o' the finished compositions are sodium alkylbenzene sulphonates, preferably the C10―C14 alkyl compound sodium primary and secondary alkyl sulphates, preferably the C10―C22 alkyl sulphates, sodium sulphonates, preferably the C10―C18 sulphonates and sodium alkane sulphonates. Soaps of fatty acds may also be present, preferably the sodium and potassium salts of C10―C22 fatty acids, both saturated and unsaturated. Where soap is the sole anionic surfactant it may be present in an amount up to about 65% or weight of the finished composition, down to about ½% by weight when other anionic surfactant are present. Typical soaps which can be used are those formed from coconut oil, tallow and natural containing high proportions of oleic acid such as sunflower oil.
- Typical nonionic surfactants, are ethoxylated primary and secondary alcohols of from 8 to 25 carbon atoms containing from 3 to 25 moles of ethylene oxide per mole of alcohol. These materials may generaly be present in an amount of from 1 to 15% by weight, based on the weight of the finished composition
- Typical detergency builders which can be used are the water-soluble phosphates, carbonates percarbonates and aluminosilicates, particularly the sodium and potassium salts of these compounds Organic builders may also be used, examples being sodium carboxymethyloxysuccinate, sodium citrate sodium polyacrylates and sodium nitrilotriacetate. Any of these compounds, or any other bullder compound, in any suitable mixture, may be used in amounts of from 5 to 50% by weight of the finished composition.
- The invention will be further illustrated by means of the following examples:-
- 47.6 parts by weight of gelatinised starch (Amigel 30076 registered Trade Mark, manufactured and sold by Societe des Produits du Mais, of Clarmart, France) was placed in the pan of an Eirich (registered Trade Mark) pan granulator. A mixture of 20.5 parts by weight of a silicone anti-foam (DB100 manufactured and sold by Dow Chemical Ltd.), 27.1 parts by weight of a paraffin wax having a melting point of 40°C were heated to 65°C with agitation to produce a homogeneous liquid. The resultant liquid was then sprayed onto the gelatinised starch in the pan granulator then, 4.8 parts of nonionic surfactant (Cl3-18 primary alcohol 8EO) where sprayed onto the granules.
- The anti-foam properties of the granules produced by the process described in Example 1 were tested as follows.
-
- The powder obtained was divided into two batches. The first batch was immediately subjected to the foam assessment test described below. The other batch was stored in unlaminated, sealed cartons at 37°C and 60% relative humidity. The stored batches were then subjected to test after 2 weeks and 4 weeks of storage.
- 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.
- In a series of experiments the height of suds which is developed by each powder at various temperatures is determined. The results are shown in Table 1 from which it can be seen that where there is some de-activation of foam control effectiveness on storage. Nevertheless, all granules provide satisfactory foam control in the formulation described at all temperatures.
Claims (11)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT83302643T ATE21115T1 (en) | 1982-05-11 | 1983-05-10 | GRANULES CONTAINING SILICONE-BASED ANTFOAM AGENTS AND PROCESS FOR THEIR MANUFACTURE. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8213576 | 1982-05-11 | ||
GB8213576 | 1982-05-11 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0094250A1 EP0094250A1 (en) | 1983-11-16 |
EP0094250B1 true EP0094250B1 (en) | 1986-07-30 |
EP0094250B2 EP0094250B2 (en) | 1994-06-15 |
Family
ID=10530279
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP83302643A Expired - Lifetime EP0094250B2 (en) | 1982-05-11 | 1983-05-10 | Process for preparing granules containing silicone-based anti-foam |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0094250B2 (en) |
AT (1) | ATE21115T1 (en) |
DE (1) | DE3364903D1 (en) |
ZA (1) | ZA833292B (en) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
GB8627181D0 (en) * | 1986-11-13 | 1986-12-10 | Procter & Gamble | Softening detergent compositions |
DE3732947A1 (en) * | 1987-09-30 | 1989-04-13 | Henkel Kgaa | FOAM REGULATOR SUITABLE FOR USE IN WASHING AND CLEANING AGENTS |
JPH09502468A (en) * | 1993-07-12 | 1997-03-11 | ザ、プロクター、エンド、ギャンブル、カンパニー | Granular detergent composition containing surfactant and defoaming component |
GB9410677D0 (en) | 1994-05-27 | 1994-07-13 | Unilever Plc | Detergent compositions |
DE19636206A1 (en) * | 1996-09-06 | 1998-03-12 | Henkel Kgaa | Process for the production of paraffin-containing foam regulators |
US6200498B1 (en) | 1997-08-29 | 2001-03-13 | Henkel Kommanditgesellschaft Auf Aktien | Process for producing paraffin-containing foam regulators |
DE19837195A1 (en) * | 1998-08-17 | 2000-02-24 | Cognis Deutschland Gmbh | Producing defoaming granulate, for solid detergent, by spraying aqueous silicone emulsion onto pre-product mixture, while drying and granulating |
DE19953794A1 (en) * | 1999-11-09 | 2001-05-17 | Cognis Deutschland Gmbh | Shaped body with improved water solubility |
DE19953797A1 (en) * | 1999-11-09 | 2001-05-17 | Cognis Deutschland Gmbh | Defoamer granules |
DE19953796A1 (en) * | 1999-11-09 | 2001-05-17 | Cognis Deutschland Gmbh | Solid washing, rinsing and cleaning agents |
DE10108573A1 (en) * | 2001-02-22 | 2002-09-12 | Cognis Deutschland Gmbh | Solid detergent additives, their production and use |
US6656975B1 (en) | 2002-05-21 | 2003-12-02 | Dow Corning Corporation | Silicone dispersions |
EP1590427A2 (en) * | 2003-02-03 | 2005-11-02 | Ciba SC Holding AG | Washing agent and fabric softener formulations |
GB0518059D0 (en) | 2005-09-06 | 2005-10-12 | Dow Corning | Delivery system for releasing active ingredients |
EP2649172A1 (en) | 2010-12-10 | 2013-10-16 | Dow Corning Corporation | Granulated foam control composition |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1407997A (en) * | 1972-08-01 | 1975-10-01 | Procter & Gamble | Controlled sudsing detergent compositions |
GB1492939A (en) * | 1974-03-11 | 1977-11-23 | Procter & Gamble Ltd | Controlled-sudsing detergent compositions |
EP0008829A1 (en) * | 1978-09-09 | 1980-03-19 | THE PROCTER & GAMBLE COMPANY | Controlled sudsing detergent compositions |
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. |
NZ199235A (en) * | 1980-12-17 | 1985-02-28 | Unilever Plc | Controlled-sudsing detergent compositions |
EP0071481B1 (en) * | 1981-07-31 | 1986-06-11 | Unilever Plc | Suds control agents and detergent compositions containing them |
-
1983
- 1983-05-09 ZA ZA833292A patent/ZA833292B/en unknown
- 1983-05-10 AT AT83302643T patent/ATE21115T1/en not_active IP Right Cessation
- 1983-05-10 DE DE8383302643T patent/DE3364903D1/en not_active Expired
- 1983-05-10 EP EP83302643A patent/EP0094250B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
DE3364903D1 (en) | 1986-09-04 |
EP0094250B2 (en) | 1994-06-15 |
EP0094250A1 (en) | 1983-11-16 |
ATE21115T1 (en) | 1986-08-15 |
ZA833292B (en) | 1984-12-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0094250B1 (en) | Process for preparing granules containing silicone-based anti-foam | |
US4451387A (en) | Suds control agents and detergent compositions containing them | |
EP0266863B1 (en) | Antifoam ingredient | |
EP0040091B1 (en) | Suds suppressing granules for use in detergent compositions | |
US4265779A (en) | Suds suppressing compositions and detergents containing them | |
US5002695A (en) | Foam regulators suitable for use in detergents and cleaning preparations | |
EP0495345B1 (en) | Foam control agents in granular form | |
CZ225796A3 (en) | Washing and cleansing preparation with imminodisuccinates | |
EP0149264A1 (en) | Stable, free-flowing particulate adjuncts for use in detergent compositions | |
KR910004608B1 (en) | Antiform ingredient | |
EP0163352B1 (en) | Detergent with suds control | |
PL170372B1 (en) | Dry powdered fabric softening composition and method of obtaining same | |
NZ232056A (en) | Aqueous liquid detergent containing magnesium ions as enzyme stabiliser | |
US6288020B1 (en) | Compositions containing α-sulfofatty acid esters and methods of making and using the same | |
PL178741B1 (en) | Anti-foaming agent, method of obtaining same, and composition containing such agent | |
EP0071481B1 (en) | Suds control agents and detergent compositions containing them | |
EP0109247B1 (en) | Hydrocarbon anti-foam granules | |
EP0119746A1 (en) | Process for manufacturing detergent powder | |
US4363740A (en) | Process for making controlled sudsing detergent powder | |
EP0087233B1 (en) | Process for producing low-sudsing detergent compositions | |
EP0054436B1 (en) | Controlled-sudsing detergent compositions | |
CA1184468A (en) | Process for preparing low silicate detergent compositions | |
SE449372B (en) | LOW PHOSPHATE CONTENT COMPOSITION | |
EP0137533B1 (en) | Free-flowing particulate fabric-softening adjunct for use in laundry detergent compositions and method of making same |
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 |
Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
17P | Request for examination filed |
Effective date: 19840411 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Effective date: 19860730 Ref country code: AT Effective date: 19860730 |
|
REF | Corresponds to: |
Ref document number: 21115 Country of ref document: AT Date of ref document: 19860815 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 3364903 Country of ref document: DE Date of ref document: 19860904 |
|
ET | Fr: translation filed | ||
ITF | It: translation for a ep patent filed |
Owner name: JACOBACCI & PERANI S.P.A. |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
26 | Opposition filed |
Opponent name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN Effective date: 19870330 |
|
NLR1 | Nl: opposition has been filed with the epo |
Opponent name: HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN |
|
RAP4 | Party data changed (patent owner data changed or rights of a patent transferred) |
Owner name: UNILEVER N.V. Owner name: UNILEVER PLC |
|
ITTA | It: last paid annual fee | ||
PUAH | Patent maintained in amended form |
Free format text: ORIGINAL CODE: 0009272 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT MAINTAINED AS AMENDED |
|
27A | Patent maintained in amended form |
Effective date: 19940615 |
|
AK | Designated contracting states |
Kind code of ref document: B2 Designated state(s): AT BE CH DE FR GB IT LI NL SE |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: AEN |
|
ITF | It: translation for a ep patent filed |
Owner name: JACOBACCI CASETTA & PERANI S.P.A. |
|
NLR2 | Nl: decision of opposition | ||
ET3 | Fr: translation filed ** decision concerning opposition | ||
NLR3 | Nl: receipt of modified translations in the netherlands language after an opposition procedure | ||
EAL | Se: european patent in force in sweden |
Ref document number: 83302643.8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 19960430 Year of fee payment: 14 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19970425 Year of fee payment: 15 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19970526 Year of fee payment: 15 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19970531 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19970531 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19980409 Year of fee payment: 16 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19980416 Year of fee payment: 16 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19980429 Year of fee payment: 16 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19980510 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19981201 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19980510 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 19981201 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19990511 |
|
EUG | Se: european patent has lapsed |
Ref document number: 83302643.8 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20000131 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20000301 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
APAH | Appeal reference modified |
Free format text: ORIGINAL CODE: EPIDOSCREFNO |