EP0482807A1 - Releasably encapsulated active substrates - Google Patents
Releasably encapsulated active substrates Download PDFInfo
- Publication number
- EP0482807A1 EP0482807A1 EP91309432A EP91309432A EP0482807A1 EP 0482807 A1 EP0482807 A1 EP 0482807A1 EP 91309432 A EP91309432 A EP 91309432A EP 91309432 A EP91309432 A EP 91309432A EP 0482807 A1 EP0482807 A1 EP 0482807A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- active substrate
- encapsulated active
- substrate according
- encapsulated
- metal salt
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3907—Organic compounds
- C11D3/3917—Nitrogen-containing compounds
- C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames
-
- 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
Definitions
- the present invention relates to active substrates such as bleach activators releasably encapsulated in a coating thereon and methods of applying the same.
- bleaches and bleach activators in detergent formulations.
- One of the important aspects of such formulations is that they should be capable of being stored over a significantly long period both by the producers of such formulations, the retailers of the product and by the end user, e.g. the housewife, who usually buys in bulk and likes to use it in small aliquots for washing as and when necessary.
- the components of such formulations, especially the bleaches and bleach activators have an unacceptably short storage life due to their tendency to undergo undesirable physical or chemical changes, thereby resulting in deterioration of the formulation which may manifest itself as, e.g.
- the present invention relates to an encapsulated active substrate comprising a bleach activator releasably encapsulated in a coating of at least one metal salt of an inorganic acid, said salt being soluble in an aqueous medium such that upon contacting the encapsulated substrate with the aqueous medium the the active substrate is released into said medium.
- active substrate a bleach activator as such or a composite which comprises such bleach activator and one or more other components including conventional binders such as e.g. a bentonite clay; surfactants such as polyoxyalkylene sorbitan oleate esters, e.g. Tween (Registered Trade Mark) an alkali metal salt of a polycarboxylic acid, e.g. Dispex-G40 (Registered Trade Mark, ex Allied Colloids, UK); disintegrating aids such as cross-linked carboxy methyl cellulose derivatives e.g. Ac-di-sol (Registered Trade Mark) or a polyacrylate; and fillers such as the cellulosic type, e.g. Avicel (Registered Trade Mark).
- conventional binders such as e.g. a bentonite clay
- surfactants such as polyoxyalkylene sorbitan oleate esters, e.g. Tween (Registered Trade Mark) an alkali
- the bleach activator in the active substrate suitably comprises at least one compound selected from a cyclic anhydride of the structural formula (I) or a lactone of the structural formula (II) below: wherein Q is a divalent organic grouping such that Q and N together with the carbonyl and oxygen functions form one or more cyclic structures and in (I) R is H, an alkyl, aryl, halogen, a carboxylic or a carbonyl containing function, and in (II) R is a C 2 or higher alkyl, alkaryl, aryl, aralkyl, alkoxyl, haloalkyl, amino, amino alkyl, dialkyl amino, carboxylic or a carbonyl-containing function.
- Q is a divalent organic grouping such that Q and N together with the carbonyl and oxygen functions form one or more cyclic structures and in (I) R is H, an alkyl, aryl, halogen, a carboxylic or a carbonyl containing
- Bleach activators of formula (I) are claimed and described in our published EP-A-331300 and those of formula (II) are claimed and described in our published EP-A-332294 and are incorporated herein by reference.
- such compounds include bleach activators such as 2-hydrocarbyl (4H) 3,1-benzoxazin-4- ones (especially the 2-methyl and 2-aryl derivatives), the 2-N,N-dialkylamino (4H) 3,1-benzoxazin-4-ones (especially the 2-N,N-dimethyl derivative) and isatoic anhydride and its homologues and derivatives.
- bleach activators described in published EP-A-170386 N-alkoyl-6-aminoperoxycarboxylic acids and their salts
- GB-A-2832021 tetraacetyl ethylene diamine
- aqueous medium as used herein and throughout the specification is meant to include the aqueous alkaline medium encountered in a wash cycle or during a washing procedure.
- the metal salts of inorganic acids which can be used to form the encapsulating coating must be soluble in the aqueous medium although it would be advantageous if they are soluble in water.
- the solubility should preferably be at least 3g/100g of the aqueous medium at ambient temperatures, eg 15°C, although the greater the solubility, the better.
- examples of such compounds include the water soluble carbonates, sulphates and phosphates of the metals in Groups I-III of the Periodic Table, especially the alkali metals, some alkaline earth metals such as magnesium, zinc and Group III metals such as aluminium. Particularly preferred are the sulphates and phosphates of sodium, potassium, zinc and aluminium. Whichever metal salt is chosen, the salt should be such that it is capable of forming an encapsulating barrier coating on the active substrate.
- activators of the structure type (II) especially if the compound is a 2-aryl substituted benzoxazin-4-one, such activators cause dye damage.
- the performance of such activators can be improved by using an encapsulating coating of a zinc salt such as zinc sulphate.
- activators of the type (I) ie those having an isatoic anhydride type structure, the problems of staining and dye damage can be mitigated by using an encapsulating coating of an aluminium salt such as aluminium sulphate.
- the encapsulating coating should suitably form a minor proportion of the encapsulated product. That is, the active substrate should be at least 50% w/w of the encapsulated product, preferably greater than 65% w/w of the encapsulated product and most preferably from 65-80% w/w.
- the thickness of the coating encapsulating the active substrate is suitably such that it does not peel off or is not readily removed by attrition and is preferably at least 0.03 micrometers.
- the encapsulation should however be such that it completely covers the active substrate coated.
- the active substrate is suitably in the form of a powder or granules prior to encapsulation.
- the initial particle size of the substrate should be preferably from 50-200 micrometers for the powder and from 200-2000 micrometers for the granules.
- Substrates having particle sizes within this range can be produced from commercially available material by milling and/or grinding, granulation or preferably by the technique of extrusion and spheronisation.
- the powder or granules of the active substrate they may be in the form of a composite comprising the bleach activator, binders, dispersing aids, surfactants and fillers as described above.
- the encapsulating coating can be applied on the substrate by conventional means. It is preferable to create a fluidised bed of the substrate particles and to spray them with a solution of the metal salt. In using this technique the conditions should be controlled carefully in order to achieve satisfactory encapsulation. For instance, the fluidisation of the substrate particles should be such that they float in the fluidising medium as separate and distinct particles for a sufficiently long time in the coating environment so as to enable the spray of the metal salt to substantially completely encapsulate and hermetically seal substantially all of the particles individually. At the same time the residence time within the coating environment and the temperature within the coating environment should be such that before the encapsulated particles emerge from the environment they are substantially dry and resistant to (a) loss of coating by attrition and (b) agglomeration.
- a fluidising medium is also important in that it should be substantially inert to the encapsulating process and should not adversely affect the nature of the substrate being encapsulated or the encapsulating coating.
- An example of a suitable fluidising medium is air.
- the above components were formed into a dough in water and subjected to extrusion followed by spheronisation to obtain granules having a particle size of 500-1000 micrometers.
- the granules were then fluidised in a Strea-1 fluidiser at a spray rate of about 6g/min through two-fluid nozzle with atomising air pressure of about 0.8 bar.
- Air was used as the fluidising medium at an air volume of 10 units on Strea 1.
- the inlet air temperature was 48 °C and the outlet air temperature was 36 C.
- a solution of 150g of anhydrous sodium sulphate in 700g of water was used as the encapsulating solution.
- This sodium sulphate solution was sprayed in a direction cocurrent with the fluidising air using a Wurster column. The spraying of the solution took about 1.5 hours to encapsulate the granules. The encapsulated granules were then dried for a further 20 minutes during which time the temperature was increased to 52 ° C at the inlet and 46 ° C at the outlet to bake the encapsulating coating into a solid, dry barrier.
- the encapsulated granules so produced were mixed at a concentration of 5% w/w with a detergent powder containing 80% w/w ECE Base (ex Westlairds Limited, North Green, Datchet, Slough SL3 9JH, Berkshire, UK) and 15% w/w of a perborate bleach and stored in open packs at 37°C and 70% relative humidity.
- the resultant detergent formulation did not suffer any discolouration or substantial loss of activity after storage for 2 months.
- solubility of the coating in the aqueous medium is unaffected is illustrated by a comparison of coated and uncoated spheres made with the above formulation where it can be seen that there is no significant difference between whole and crushed spheres:
- Granules containing 80% isatoic anhydride bleach activator were encapsulated with the inorganic salts detailed below. These coated granules (20 parts) were mixed with a phosphate-free detergent base which contained 25% sodium perborate monohydrate (80 parts). Samples from the detergent formulations thus prepared were then spread in narrow strips of ca. 2cm width onto a test cloth of white cotton (EMPA 221). This cloth had previously been placed in a tray and dampened with sufficient water to absorb into and dampen the strips of detergent formulation. After 30 minutes the cotton test cloth was thoroughly rinsed in running tap water and air dried.
- EMPA 221 white cotton
- Granules containing 82% 2-phenyl benzoxazine-4-one (2PB4) bleach activator were encapsulated with the inorganic salts detailed below. These coated granules (20 parts) were mixed with a phosphate-free detergent base which contained 25% sodium perborate monohydrate (80 parts). Samples from the detergent formulations thus prepared were then spread in narrow strips of ca. 2cm width onto a test cloth of cotton dyed with immedial black (EMPA 115). This cloth had previously been placed in a tray and dampened with sufficient water to absorb into and dampen the strips of detergent formulation. After 30 minutes the cotton test cloth was thoroughly rinsed in running tap water and air dried. The above test was repeated.
- 2PB4 2-phenyl benzoxazine-4-one
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Formation Of Insulating Films (AREA)
- Laminated Bodies (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Cosmetics (AREA)
Abstract
Description
- The present invention relates to active substrates such as bleach activators releasably encapsulated in a coating thereon and methods of applying the same.
- It is well known to use bleaches and bleach activators in detergent formulations. One of the important aspects of such formulations is that they should be capable of being stored over a significantly long period both by the producers of such formulations, the retailers of the product and by the end user, e.g. the housewife, who usually buys in bulk and likes to use it in small aliquots for washing as and when necessary. However, it is also well recognised that the components of such formulations, especially the bleaches and bleach activators, have an unacceptably short storage life due to their tendency to undergo undesirable physical or chemical changes, thereby resulting in deterioration of the formulation which may manifest itself as, e.g. loss of activity, discolouration, loss of attrition resistance, hydroscopicity and hence caking by absorption of moisture, staining the clothes washed or as malodour. It has been found that the bleaches and bleach activators in particular are prone to such undesirable changes.
- It has been known to apply protective barrier coatings on relatively unstable compounds to improve their storage stability. Catalysts used in chemical reactions are a well known example where barrier coatings have been applied. In the case of active substrates such as bleach activators there is the added problem that any coating applied should be such that:
- (a) the active species is readily released when in contact with the aqueous wash system,
- (b) it mitigates any problems of dye damage or staining by the use of a bleach activator
- (c) the barrier coating itself should not interfere with the other components in the formulation,
- (d) the barrier coating does not adversely affect the wash or the clothes being washed in terms of causing dye damage or staining, and
- (e) should be user friendly and friendly towards the environment when discarded with the wash water.
- It has now been found that the relative instability of active substrates such as bleach activators or the risk of dye damage or staining thereby can be mitigated by encapsulating the substrate in its powder or granular form in a barrier coating capable of releasing the active substrate in the aqueous wash system without adversely affecting the clothes being washed, the user or the environment.
- Accordingly, the present invention relates to an encapsulated active substrate comprising a bleach activator releasably encapsulated in a coating of at least one metal salt of an inorganic acid, said salt being soluble in an aqueous medium such that upon contacting the encapsulated substrate with the aqueous medium the the active substrate is released into said medium.
- By the term "active substrate" as used herein and throughout the specification is meant a bleach activator as such or a composite which comprises such bleach activator and one or more other components including conventional binders such as e.g. a bentonite clay; surfactants such as polyoxyalkylene sorbitan oleate esters, e.g. Tween (Registered Trade Mark) an alkali metal salt of a polycarboxylic acid, e.g. Dispex-G40 (Registered Trade Mark, ex Allied Colloids, UK); disintegrating aids such as cross-linked carboxy methyl cellulose derivatives e.g. Ac-di-sol (Registered Trade Mark) or a polyacrylate; and fillers such as the cellulosic type, e.g. Avicel (Registered Trade Mark).
- The bleach activator in the active substrate suitably comprises at least one compound selected from a cyclic anhydride of the structural formula (I) or a lactone of the structural formula (II) below:
wherein Q is a divalent organic grouping such that Q and N together with the carbonyl and oxygen functions form one or more cyclic structures and in (I) R is H, an alkyl, aryl, halogen, a carboxylic or a carbonyl containing function, and in (II) R is a C2 or higher alkyl, alkaryl, aryl, aralkyl, alkoxyl, haloalkyl, amino, amino alkyl, dialkyl amino, carboxylic or a carbonyl-containing function. - Bleach activators of formula (I) are claimed and described in our published EP-A-331300 and those of formula (II) are claimed and described in our published EP-A-332294 and are incorporated herein by reference.
- In particular, such compounds include bleach activators such as 2-hydrocarbyl (4H) 3,1-benzoxazin-4- ones (especially the 2-methyl and 2-aryl derivatives), the 2-N,N-dialkylamino (4H) 3,1-benzoxazin-4-ones (especially the 2-N,N-dimethyl derivative) and isatoic anhydride and its homologues and derivatives. Bleach activators described in published EP-A-170386 (N-alkoyl-6-aminoperoxycarboxylic acids and their salts) and in GB-A-2832021 (tetraacetyl ethylene diamine) can also be encapsulated in a coating to improve their stability and are incorporated herein by reference.
- The term "aqueous medium" as used herein and throughout the specification is meant to include the aqueous alkaline medium encountered in a wash cycle or during a washing procedure.
- The metal salts of inorganic acids which can be used to form the encapsulating coating must be soluble in the aqueous medium although it would be advantageous if they are soluble in water. The solubility should preferably be at least 3g/100g of the aqueous medium at ambient temperatures, eg 15°C, although the greater the solubility, the better. Examples of such compounds include the water soluble carbonates, sulphates and phosphates of the metals in Groups I-III of the Periodic Table, especially the alkali metals, some alkaline earth metals such as magnesium, zinc and Group III metals such as aluminium. Particularly preferred are the sulphates and phosphates of sodium, potassium, zinc and aluminium. Whichever metal salt is chosen, the salt should be such that it is capable of forming an encapsulating barrier coating on the active substrate.
- In the case of some compounds of the structure type (II), especially if the compound is a 2-aryl substituted benzoxazin-4-one, such activators cause dye damage. The performance of such activators can be improved by using an encapsulating coating of a zinc salt such as zinc sulphate. On the other hand, with activators of the type (I) ie those having an isatoic anhydride type structure, the problems of staining and dye damage can be mitigated by using an encapsulating coating of an aluminium salt such as aluminium sulphate.
- The encapsulating coating should suitably form a minor proportion of the encapsulated product. That is, the active substrate should be at least 50% w/w of the encapsulated product, preferably greater than 65% w/w of the encapsulated product and most preferably from 65-80% w/w.
- Ideally, the thickness of the coating encapsulating the active substrate is suitably such that it does not peel off or is not readily removed by attrition and is preferably at least 0.03 micrometers.
- The encapsulation should however be such that it completely covers the active substrate coated. The active substrate is suitably in the form of a powder or granules prior to encapsulation. The initial particle size of the substrate should be preferably from 50-200 micrometers for the powder and from 200-2000 micrometers for the granules. Substrates having particle sizes within this range can be produced from commercially available material by milling and/or grinding, granulation or preferably by the technique of extrusion and spheronisation. In producing the powder or granules of the active substrate they may be in the form of a composite comprising the bleach activator, binders, dispersing aids, surfactants and fillers as described above. The encapsulating coating can be applied on the substrate by conventional means. It is preferable to create a fluidised bed of the substrate particles and to spray them with a solution of the metal salt. In using this technique the conditions should be controlled carefully in order to achieve satisfactory encapsulation. For instance, the fluidisation of the substrate particles should be such that they float in the fluidising medium as separate and distinct particles for a sufficiently long time in the coating environment so as to enable the spray of the metal salt to substantially completely encapsulate and hermetically seal substantially all of the particles individually. At the same time the residence time within the coating environment and the temperature within the coating environment should be such that before the encapsulated particles emerge from the environment they are substantially dry and resistant to (a) loss of coating by attrition and (b) agglomeration. In this context the choice of a fluidising medium is also important in that it should be substantially inert to the encapsulating process and should not adversely affect the nature of the substrate being encapsulated or the encapsulating coating. An example of a suitable fluidising medium is air.
- The present invention is further illustrated with reference to the following Example.
-
- The above components were formed into a dough in water and subjected to extrusion followed by spheronisation to obtain granules having a particle size of 500-1000 micrometers.
- The granules were then fluidised in a Strea-1 fluidiser at a spray rate of about 6g/min through two-fluid nozzle with atomising air pressure of about 0.8 bar.
- Air was used as the fluidising medium at an air volume of 10 units on Strea 1. The inlet air temperature was 48 °C and the outlet air temperature was 36 C.
- A solution of 150g of anhydrous sodium sulphate in 700g of water was used as the encapsulating solution.
- This sodium sulphate solution was sprayed in a direction cocurrent with the fluidising air using a Wurster column. The spraying of the solution took about 1.5 hours to encapsulate the granules. The encapsulated granules were then dried for a further 20 minutes during which time the temperature was increased to 52 ° C at the inlet and 46 ° C at the outlet to bake the encapsulating coating into a solid, dry barrier.
- The encapsulated granules so produced were mixed at a concentration of 5% w/w with a detergent powder containing 80% w/w ECE Base (ex Westlairds Limited, North Green, Datchet, Slough SL3 9JH, Berkshire, UK) and 15% w/w of a perborate bleach and stored in open packs at 37°C and 70% relative humidity. The resultant detergent formulation did not suffer any discolouration or substantial loss of activity after storage for 2 months.
- That the solubility of the coating in the aqueous medium is unaffected is illustrated by a comparison of coated and uncoated spheres made with the above formulation where it can be seen that there is no significant difference between whole and crushed spheres:
- Test conditions : 40 °C, 2.5% active isatoic anhydride (hereafter "IA") was used in detergent base containing sodium perborate tetrahydrate. Washes were carried out in a Terg-o-tometer over a period of 20 minutes. 5.85g of detergent base plus 0.15g of bleach activator at 100% active were used i.e. 0.3g of formulated isatoic anhydride spheres.
- Substrate Cloths: EMPA 114 Red wine stain and WPK BC-1 tea stain
- Measurements : Reflectance measurements were taken with ICS-Texicon Micromatch spectrometer. Results are expressed as percentage stain removal (%SR) calculated from the following expression:
- L(final) = final reflectance value
- L(initial) = initial reflectance value
- L(standard) = standard reflectance value
- L value is reflectance value as defined in Committee Internationale D'Eclarage LAB system (CIELAB).
-
- Granules containing 80% isatoic anhydride bleach activator were encapsulated with the inorganic salts detailed below. These coated granules (20 parts) were mixed with a phosphate-free detergent base which contained 25% sodium perborate monohydrate (80 parts). Samples from the detergent formulations thus prepared were then spread in narrow strips of ca. 2cm width onto a test cloth of white cotton (EMPA 221). This cloth had previously been placed in a tray and dampened with sufficient water to absorb into and dampen the strips of detergent formulation. After 30 minutes the cotton test cloth was thoroughly rinsed in running tap water and air dried.
- The above test was repeated a further three times. A panel of five observers was then used to compare the extent of brown staining of the cotton cloths under artificial daylight (D65) illumination in an ICS-Texicon light cabinet. Each observer was asked to score the staining underneath the detergent strips on a scale of 1 to 5 where;- cloth(s) with least staining = 1, and cloth(s) with most staining = 5.
-
- The results show that the bleach activator granules encapsulated with the zinc and aluminium salts exhibit significantly reduced tendency for staining of the test fabric than those encapsulated with a salt of an organic acid.
- Granules containing 82% 2-phenyl benzoxazine-4-one (2PB4) bleach activator were encapsulated with the inorganic salts detailed below. These coated granules (20 parts) were mixed with a phosphate-free detergent base which contained 25% sodium perborate monohydrate (80 parts). Samples from the detergent formulations thus prepared were then spread in narrow strips of ca. 2cm width onto a test cloth of cotton dyed with immedial black (EMPA 115). This cloth had previously been placed in a tray and dampened with sufficient water to absorb into and dampen the strips of detergent formulation. After 30 minutes the cotton test cloth was thoroughly rinsed in running tap water and air dried. The above test was repeated.
- Reflectance measurements were taken with an ICS-Texicon Micromatch Spectrometer. The average results from 10 readings from underneath each test strip on each test cloth are expressed as percentage stain removal (%SR).
-
- Visual observations confirmed the marked reduction of 'pinholing' dye damage for the zinc and aluminium suphate coated granules when compared with uncoated granules.
- The results show that the bleach activator granules encapsulated with the zinc and aluminium salts exhibit significantly reduced tendency for dye damage.
Claims (12)
wherein Q is a divalent organic grouping such that Q and N together with the carbonyl and oxygen functions form one or more cyclic structures and in (I) R is H, an alkyl, aryl, halogen, a carboxylic or a carbonyl containing function, and in (II) R is a C2 or higher alkyl, alkaryl, aryl, aralkyl, alkoxyl, haloalkyl, amino, aminoalkyl, dialkyl amino, carboxylic or a carbonyl containing function.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9023000 | 1990-10-23 | ||
GB909023000A GB9023000D0 (en) | 1990-10-23 | 1990-10-23 | Barrier coatings |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0482807A1 true EP0482807A1 (en) | 1992-04-29 |
EP0482807B1 EP0482807B1 (en) | 1995-12-20 |
Family
ID=10684186
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91309432A Expired - Lifetime EP0482807B1 (en) | 1990-10-23 | 1991-10-14 | Releasably encapsulated active substrates |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0482807B1 (en) |
JP (1) | JPH04314799A (en) |
AT (1) | ATE131864T1 (en) |
CA (1) | CA2054003A1 (en) |
DE (1) | DE69115637T2 (en) |
ES (1) | ES2081441T3 (en) |
GB (1) | GB9023000D0 (en) |
Cited By (24)
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WO1993008254A1 (en) * | 1991-10-22 | 1993-04-29 | Basf Aktiengesellschaft | Granular bleach-activator composition |
WO1993016161A1 (en) * | 1992-02-05 | 1993-08-19 | Basf Aktiengesellschaft | Granular bleaching activator composition with variously shaped grains |
WO1993024604A1 (en) * | 1992-05-29 | 1993-12-09 | Warwick International Group Limited | Releasably encapsulated active substrates |
WO1998000515A1 (en) * | 1996-06-28 | 1998-01-08 | The Procter & Gamble Company | Coated particle-containing, non-aqueous liquid cleaning compositions |
WO1998026039A1 (en) | 1996-12-12 | 1998-06-18 | The Procter & Gamble Company | Process for making tabletted detergent compositions |
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WO2015148461A1 (en) | 2014-03-27 | 2015-10-01 | The Procter & Gamble Company | Printed water soluble pouch |
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BR0309861A (en) | 2002-05-02 | 2005-03-29 | Procter & Gamble | Particulate detergent composition comprising the same and method for cleaning fabrics |
US7790664B2 (en) | 2008-10-27 | 2010-09-07 | The Procter & Gamble Company | Methods for making a nil-phosphate liquid automatic dishwashing composition |
WO2011118340A1 (en) * | 2010-03-26 | 2011-09-29 | ライオン株式会社 | Bleach activator agglomerated substance and method for producing same |
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FR2229768A1 (en) * | 1973-05-16 | 1974-12-13 | Ppg Industries Inc | |
US4105827A (en) * | 1973-04-20 | 1978-08-08 | Interox | Particulate peroxygen compounds coated with sodium sesquicarbonate or Na2 SO4 mNa2 CO3 |
EP0174132A2 (en) * | 1984-09-01 | 1986-03-12 | The Procter & Gamble Company | Bleach activator compositions manufacture and use thereof in laundry compositions |
GB2193510A (en) * | 1986-07-24 | 1988-02-10 | British Petroleum Co Plc | Bleach activators |
EP0332050A1 (en) * | 1988-03-10 | 1989-09-13 | Henkel Kommanditgesellschaft auf Aktien | Activators for inorganic per compounds |
-
1990
- 1990-10-23 GB GB909023000A patent/GB9023000D0/en active Pending
-
1991
- 1991-10-14 EP EP91309432A patent/EP0482807B1/en not_active Expired - Lifetime
- 1991-10-14 AT AT91309432T patent/ATE131864T1/en not_active IP Right Cessation
- 1991-10-14 DE DE69115637T patent/DE69115637T2/en not_active Expired - Fee Related
- 1991-10-14 ES ES91309432T patent/ES2081441T3/en not_active Expired - Lifetime
- 1991-10-22 CA CA002054003A patent/CA2054003A1/en not_active Abandoned
- 1991-10-23 JP JP3275708A patent/JPH04314799A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4105827A (en) * | 1973-04-20 | 1978-08-08 | Interox | Particulate peroxygen compounds coated with sodium sesquicarbonate or Na2 SO4 mNa2 CO3 |
FR2229768A1 (en) * | 1973-05-16 | 1974-12-13 | Ppg Industries Inc | |
EP0174132A2 (en) * | 1984-09-01 | 1986-03-12 | The Procter & Gamble Company | Bleach activator compositions manufacture and use thereof in laundry compositions |
GB2193510A (en) * | 1986-07-24 | 1988-02-10 | British Petroleum Co Plc | Bleach activators |
EP0332050A1 (en) * | 1988-03-10 | 1989-09-13 | Henkel Kommanditgesellschaft auf Aktien | Activators for inorganic per compounds |
Cited By (37)
Publication number | Priority date | Publication date | Assignee | Title |
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WO1993008254A1 (en) * | 1991-10-22 | 1993-04-29 | Basf Aktiengesellschaft | Granular bleach-activator composition |
WO1993016161A1 (en) * | 1992-02-05 | 1993-08-19 | Basf Aktiengesellschaft | Granular bleaching activator composition with variously shaped grains |
WO1993024604A1 (en) * | 1992-05-29 | 1993-12-09 | Warwick International Group Limited | Releasably encapsulated active substrates |
WO1998000515A1 (en) * | 1996-06-28 | 1998-01-08 | The Procter & Gamble Company | Coated particle-containing, non-aqueous liquid cleaning compositions |
WO1998026039A1 (en) | 1996-12-12 | 1998-06-18 | The Procter & Gamble Company | Process for making tabletted detergent compositions |
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US7858573B2 (en) | 2007-08-16 | 2010-12-28 | The Procter & Gamble Company | Process for making a detergent composition containing a sulfonic acid/carboxylic acid copolymer and a hydrophobic silica |
US8288333B2 (en) | 2007-08-16 | 2012-10-16 | The Procter & Gamble Company | Process for making a detergent composition comprising a hydrophilic silica and a copolymer containing a carboxylic acid monomer and a sulfonic acid monomer |
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EP2821474A1 (en) | 2011-01-12 | 2015-01-07 | The Procter and Gamble Company | Method for controlling the plasticization of a water soluble film |
WO2012097025A1 (en) | 2011-01-12 | 2012-07-19 | The Procter & Gamble Company | Method for controlling the plasticization of a water soluble film |
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WO2013128431A2 (en) | 2012-02-27 | 2013-09-06 | The Procter & Gamble Company | Methods for producing liquid detergent products |
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Also Published As
Publication number | Publication date |
---|---|
CA2054003A1 (en) | 1992-04-24 |
DE69115637D1 (en) | 1996-02-01 |
ATE131864T1 (en) | 1996-01-15 |
DE69115637T2 (en) | 1996-05-30 |
ES2081441T3 (en) | 1996-03-16 |
EP0482807B1 (en) | 1995-12-20 |
JPH04314799A (en) | 1992-11-05 |
GB9023000D0 (en) | 1990-12-05 |
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