CA1102966A - Bleach activator granules - Google Patents
Bleach activator granulesInfo
- Publication number
- CA1102966A CA1102966A CA318,448A CA318448A CA1102966A CA 1102966 A CA1102966 A CA 1102966A CA 318448 A CA318448 A CA 318448A CA 1102966 A CA1102966 A CA 1102966A
- Authority
- CA
- Canada
- Prior art keywords
- bleach activator
- salt
- weight
- hydratable
- sodium
- 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3905—Bleach activators or bleach catalysts
- C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (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)
- Detergent Compositions (AREA)
Abstract
Abstract of the Invention Bleach activator granules for use in or with washing and bleaching compositions having a size of from 0.2 mm to 2.5 mm and being composed of:
55% to 90% by weight of at least one bleach activator for percompounds, having a titre in the peracid formation test of at least 1.5 ml 0.1N sodium thiosulphate; and 10% to 45% by weight of a binding material comprising essentially a mixture of at least two hydratable inorganic salts.
The first hydratable salt is either sodium triphosphate, borax or mixtures thereof, the second hydratable salt being a salt having solubility in water of more than 30 grams anhydrous salt per 100 ml at 60°C, a pH of around 7 up to about 11 for 10% solution, and no transition point below 35°C.
The bleach activator granules have satisfactory stability during storage, are of satisfactory mechanical strength and satisfactory disintegrating properties in contact with water.
55% to 90% by weight of at least one bleach activator for percompounds, having a titre in the peracid formation test of at least 1.5 ml 0.1N sodium thiosulphate; and 10% to 45% by weight of a binding material comprising essentially a mixture of at least two hydratable inorganic salts.
The first hydratable salt is either sodium triphosphate, borax or mixtures thereof, the second hydratable salt being a salt having solubility in water of more than 30 grams anhydrous salt per 100 ml at 60°C, a pH of around 7 up to about 11 for 10% solution, and no transition point below 35°C.
The bleach activator granules have satisfactory stability during storage, are of satisfactory mechanical strength and satisfactory disintegrating properties in contact with water.
Description
~2~6~
- 1 - C 558 (R) BLEACH ~CTIVATOR GRANULES
The invention relates to bleach activator granules for use in or with a detergent and/or bleach composition and the preparation of said bleach activator granules.
Detergent compositions which contain so-called organic bleach activators in addition to the usual detergent substances having a cleaning action, builders and bleaching materials, are known. A class of bleaching materials which are commonly used is that which provides hydrogen peroxide in solution. Examples of this class are sodium perborate, sodium percarbonate, sodium perphosphate, sodium persilicate and urea hydrogen peroxide. These compounds will herein- -after be reFerred to as "percompounds". The most commonly used percompound in detergent composltions is alkali metal perborate.
.
The organic bleach activators referred to herein increase the bleaching action of percompounds,e.g. sodium perborate, in that they are believed to react with the hydrogen peroxide to form peracids, a bleaching species which~ unlike sodium perborate, is active at - lower temperatures,e~g. 40-60C.
Examples of~solid organic bleach activators for percompounds known in the art are carboxylic anhydrides, for example succinic, benzoic ;~ and phthalic anhydrides, carboxylic acid esters, For example sodium acetoxybenze~ sulphonate,sodium para sulphonated phenyl benzoate and acetyl salicylic acid; N-acyl substituted amides, for example tetra-acetyl ethylene (or methylene) diamine and tetra-acetylglycoluril.
~' ' ~ - ' ., ' . :~ ' '.
. : ,, :
.
' , ' .:
.., :, - , '.
:- '- ' ' ' '::, .. . . . .
: .. ,, . ;. ., ,, .: ,. .... ....... . .
Since organic bleach activators are generally hydrolysable com-pounds which on direct incorporation in detergent com~ositions tend to hydrolyse or perhydrolyse owing to the action of ~oisture, alkaline substance and the percompound in the detergent composi-tion, and to attack oxidation-sensitive ingredients, they are generally protected from said in~luences.
The most common way oE protecting bleach activators is by provid-ing the bleach activators in the form of coarse granules as agglomerates or coated particles.
Various methods of preparation o granulated and/or coated bleach activator particles and use of said bleach activator particles in detergent compositions have been described in the literature.
In the majority of cases an organic substance or a mixture of organic substances is used as the binding or coating material, such as nonionic surfactants, fatty acids, polymeric materials and waxes (see e.g. US Patent Specification ~,003,8~1; US Patent Specification 3,975,280; British Patent Specificatio~n 1,398,785, and British Patent Specification 907,358. Use of organic sub-stances as binding or coating material has the disadvantage that it generally~gives handling problems, especially in hot seasons, due to stickiness, and also that the rate of solution is often low, due to increased granule disintegration time.
¦ British Patent Specification No. 1,360,427 descrihes coated activator particles constituting 5-50% by weight of bleach acti-vator and a ~airly hiyh proportion, i.e. 95-50~ by weight, o~
an inorganic coating material comprising sodium triphosphate.
i 30 The disadvantage of such granules is that they are insuf~iciently soluble in the wash liquor and have unsatis~actory disintegration properties.
..
¦ Any proper method of protecting the bleach activator against the environment must allow dissolution of the activator in the wash liquor. Release of the activator must be achieved at a period I well before the end of the wash cycle so as to give time or the , ., . , :
- 3 - C 558 (R) bleaching step to occur. Preferably this should occur as early as possible in the wash cycle for maximum bleaching to occur.
It is thus clear that in order to produce a satisfatory bleach activator granule for use in a detergent bleach composition, the choice of a suitable binding agent is of essential importance.
One important requirement for a good binding material is good water-solubility so as to impart satisfactory disintegration properties to the granule. Other important requirements are:
- a good binding capacity, so as to form fairly strong granules with good resistance to break-down through mechanical action during handling, transport and storage,i.e. mechanical strength - formulation-compatible,e.g. suitable pHi - capable of producing granules with a high activator content, and preferably, - inexpensive and readily availabe.
Bleach activator granules hittlerto known in the art are deficient in some or other respects.
It is therefore an object of the present invention to provide improved bleach activator granules having the necessary attributes for a suitable use in or with washing and bleaching compositions.
According to the invention a bleach activator is provided in the form of granules for use in or with washing and bleaching compositions of a size of from 0.2 mm to 2.5 mm, which granules constitute from 55% by weight up to about 90% by weight of at least one bleach activator for percompounds, having a titre in the defined peracid formation test of at least 1.5 ml 0.1N sodium thiosulphate, and from 10% to 45% by weight of a binding material comprising essentially a mixture of at least two hydratable inorganic salts. The first hydratable salt is either sodium tri-phosphate or borax (Na2B407) or a mixture thereof and the second hydratable inorganic sal~ is a salt having solubility in water of :
: . ~ :: .
. .
: .
- ~ - C 558 (R) more than 30 grams anhydrous salt per 100 ml at 60C, a pH of around neutral up to about 11, for 10% solution, and no transition point below 35C.
The peracid forlnation test is a well-known test method for selecting suitable bleach activators. It has been described in US Patent Specification No. 3,177,148 and is as follows:
Peracid formation test:
.. .. , . _ . _ A test solution is prepared by dissolving the following materials in 1000 ml distilled ~ater:
sodium pyrophosphate (Na4P207.10~l20) - 2.5 g sodium perborate (NaB02.H~02.3H20) havin~
15 10.4% available oxygen - 0.615 g sodium dodecylbenzene sulphonate - 0.5 9 To this solution at 60C such an amount of activator is added that for each atom of available oxygen present one molecular equivalent of activator is introduced.
The mixture obtained by addition of the activator is vigorously stirred and maintained at 60C. After 5 minutes from the addition a 100 ml portion of the solution is withdrawn and immediately pipetted onto a mixture of 250 g. cracked ice and 15 ml glacial acetic acid. Potassium iodine (0.4 9) is then added and the liberated iodine is immediately titrated with 0.1N sodium thiosulphate with - starch as indicator until the first disappearance of the blue colour.
The amount of sodium thiosulphate solution used in ml. is the titre of the bleach activator.
Examples o~ bleach activators utilisable according to the invention may be compounds of the class of carboxylic anhydrides; carboxylic acid esters; and ~-acyl or 0-acyl substituted amides or aminesi such as sodium acetoxybenzene sulphonate (SABS)~ sodium para sulphonated phenyl benzoate, acetyl salicylic acid, tetraacetyl methylene diamine (TAMD), tetraacetylethylene diamine (TAED), and tetra-.
- ~, .
: :
,: :
.
..
.
.. . . .
- 5 - C 558 (~) acetylglycoluril (TAGU).
Preferred bleach activators are TAMD and TAED.
An essential feature of the bleach activator granule of the invention is that the binding material constitutes a mixture of at least two components,i.e. a first hydratable salt which is sodium triphosphate and/or borax and a second hydratable salt as defined above. For reasons of costs ancl practicability sodium triphosphate is preferably used as the first hydratable salt.
The presence of sodium triphosphate and/or borax is essential in that it governs the final strength of the granule, whereas the presence of the second hydratable salt is needed to govern the --stickiness and intermediate strength of the agglomerate during the preparation of the granules.
The second hydratable salt should have no transition point below 35C, preferably at least 37C. This limitation is deemed necessary for maintaining particle stability under fluctuating and/or severe storage conditions. A transition point lower than 35C would increase the risk of the granules to disintegrate and decompose during storage through loss of water of hydration.
High sollibility of the second hydratable salt is not only of importance for the release of the activator but also for providing a relatively fast disintegrating rate of the granule. The latter is of importance to reduce mechanical loss in the washing machine and to reduce the risk of "spotting" on clothes soaked therein.
"Mechanical loss" is a term used here to indicate the proportion of generally less soluble or heavy particles of the cleaning composition, sinking into the bottom of the washing machine and thereby excluded from contributing in the active washing pro oess.
The pH in solution is important since higher alkalinity would present problems in spraying and handling and would affect enzyme stability in the product as well as that of the activator itself.
.
, . . ' '' " '~
- 6 - C 558 (R) A suitable pH range is from about 6 to 11, preferably from 7 to 10, so as to have the least effect on the overall in use pH of the washing composition.
Preferably the proportion of sodium triphosphate and/or borax in the granule o-f the invention will be within the range of about 5%
to 35% by weight based on the total granule composition. Though a proportion smaller than 5% can be used,it is not advisable since it will tend to give granules of unacceptable mechanical strength. A
par-ticularly suitable proportional range of sodium triphosphate and/or borax is from about 7.5-30% by weight, based on the total granule composition.
Advantageously the second hydratable salt in the granule of the invention is present in a proportion ranging from about 5 to 30%
by weight, preferably from 5 to 15% by weight based on the total granule composition.
:
There are no specific requirements as to the ratio by weight of the first hydratable salt to the second hydratablesalt.Various ratiosare possible and the selection thereof for each particular case will be no problem to the man skilled in the art working ~ithin the invention.
A particularly suitable second hydratable salt for use in the present invention is disodium orthophosphate. Other examples of suitable compounds are potassium triphosphate and magnesium sulphate.
Inorganic salts, such as sodium carbonate, sodium silicate, sodium sulphate, sodium chloride, trisodium orthophosphate, sodium tri-phosphate and sodium pyrophosphate are deficient in one or more respects and are therefore unsuitable for use in the present invention. Sodium carbonate is unsuitable on account of its high pH in solution and its low transition point; sodium silicate and trisodium orthophosphate are unsuitable in view of their high pH
in solution; sodium chloride is unsuitable as it does not form a , ~ . , .
: .
. . .
- 7 - C 558 ~R) hydrate under normal conditions; sodium sulphate is unsuitable owing to its low transition point; sodium triphosphate and pyrophosphate are deficient in their low solubility.
Disodium orthophosphate (DSOP) has a solubility in water of over 40% as anhydrous salt at 60C; a pH for 10% solution of about 8.9 and a transition point of >35C. Furthermore this salt has a number of hydrates which give it high water-binding capacity.
It was also found that 50% solutions of the dihydrate, which are in : 10 completely solid form at ambient temperature, are fluid and sprayable at temperatures above 50C.
Magnesium sulphate has a solubility in water of about 35% as anhydrous salt at 60G; a pH for 10% solution of about 7 and no transition point below 35C.
Examples I-II
Some batchwise granulation experiments were carried out using an N,N,N',N'-tetraace-tylethylene diamine (TAED), sodium triphosphate (STP) mixture, containing about 85% by weigh-t of TAED.
First experiment 4.5 kg of said TAED/STP mixture were placed iln a 0.5 metre pan.
A solution containing 49% of disodium orthophosphate dihydrate was prepared. 1.25 kg of this solution at a temperature of 75C
was sprayed onto the TAED/STP rnixture using a WFM 504 jet at 3.5 kg/cm2. The resulting granules had a granulometry of about 90% (0.3-1.2 mm)g 0.5% (~ 1.2 mm) and 9.5% (~ 0.3 mm) and had the following composition~
TAED 66.5%
Sodium triphosphate (expressed as anhydrous salt) 11.7%
Disodium orthophosphate (expressed as anhydrous salt~ 8.5%
Water 13.3%
These granules had excellent disintegration characteristics in J~
- 8 - C 558 (R) the wash.
Second experiment 3.5 kg of the same TAED/STP mixture were placed in a 0.5 metre pan.
A solution containing 5.7% anhydrous sodium triphosphate and 37.5% disodium orthophosphate dihydrate was prepared. 0.75 kg of this solution at a temperature of 75C was sprayed onto -the TAED/STP mixture using a WFM 804 jet at 3.5 kg/cm2. The resulting granules had a granulometry of 20.5% [~ 1.2 mm); 77% (1.2-0.3 mm) and 2.5% (< 0.3 mm) and had the following composition: (Granule Type II).
TAED 70 0%
sodium triphosphate (expressed as anhydrous salt) 13.4%
15 disodium orthophosphate (expressed as anhydrous salt) 5.3%
water 11. 3%
These granules were readily dispersed in the wash and had quite satisfactory handling characteristics.
Storage trials were carried out with these granules for two and four weeks' periods, at 37C/70% RH (relative humidity) in laminated packets in a detergent base powder ~ to the following composition: (A similar composition comprising unprotected TAED
25 was used as comparison) % by weight Detergent base powder ~ 81.0 TAED granules 8.0 30 Sodium perborate tetrahydrate 10.0 Proteolytic enzyme (Alcalase; 1.5 Anson Units) 1.0 The detergent base powder lS an anionic/nonionic binary active powder based on sodium triphosphate.
The ~ollowing residual activities (%) were found:
,. ..
- 1 - C 558 (R) BLEACH ~CTIVATOR GRANULES
The invention relates to bleach activator granules for use in or with a detergent and/or bleach composition and the preparation of said bleach activator granules.
Detergent compositions which contain so-called organic bleach activators in addition to the usual detergent substances having a cleaning action, builders and bleaching materials, are known. A class of bleaching materials which are commonly used is that which provides hydrogen peroxide in solution. Examples of this class are sodium perborate, sodium percarbonate, sodium perphosphate, sodium persilicate and urea hydrogen peroxide. These compounds will herein- -after be reFerred to as "percompounds". The most commonly used percompound in detergent composltions is alkali metal perborate.
.
The organic bleach activators referred to herein increase the bleaching action of percompounds,e.g. sodium perborate, in that they are believed to react with the hydrogen peroxide to form peracids, a bleaching species which~ unlike sodium perborate, is active at - lower temperatures,e~g. 40-60C.
Examples of~solid organic bleach activators for percompounds known in the art are carboxylic anhydrides, for example succinic, benzoic ;~ and phthalic anhydrides, carboxylic acid esters, For example sodium acetoxybenze~ sulphonate,sodium para sulphonated phenyl benzoate and acetyl salicylic acid; N-acyl substituted amides, for example tetra-acetyl ethylene (or methylene) diamine and tetra-acetylglycoluril.
~' ' ~ - ' ., ' . :~ ' '.
. : ,, :
.
' , ' .:
.., :, - , '.
:- '- ' ' ' '::, .. . . . .
: .. ,, . ;. ., ,, .: ,. .... ....... . .
Since organic bleach activators are generally hydrolysable com-pounds which on direct incorporation in detergent com~ositions tend to hydrolyse or perhydrolyse owing to the action of ~oisture, alkaline substance and the percompound in the detergent composi-tion, and to attack oxidation-sensitive ingredients, they are generally protected from said in~luences.
The most common way oE protecting bleach activators is by provid-ing the bleach activators in the form of coarse granules as agglomerates or coated particles.
Various methods of preparation o granulated and/or coated bleach activator particles and use of said bleach activator particles in detergent compositions have been described in the literature.
In the majority of cases an organic substance or a mixture of organic substances is used as the binding or coating material, such as nonionic surfactants, fatty acids, polymeric materials and waxes (see e.g. US Patent Specification ~,003,8~1; US Patent Specification 3,975,280; British Patent Specificatio~n 1,398,785, and British Patent Specification 907,358. Use of organic sub-stances as binding or coating material has the disadvantage that it generally~gives handling problems, especially in hot seasons, due to stickiness, and also that the rate of solution is often low, due to increased granule disintegration time.
¦ British Patent Specification No. 1,360,427 descrihes coated activator particles constituting 5-50% by weight of bleach acti-vator and a ~airly hiyh proportion, i.e. 95-50~ by weight, o~
an inorganic coating material comprising sodium triphosphate.
i 30 The disadvantage of such granules is that they are insuf~iciently soluble in the wash liquor and have unsatis~actory disintegration properties.
..
¦ Any proper method of protecting the bleach activator against the environment must allow dissolution of the activator in the wash liquor. Release of the activator must be achieved at a period I well before the end of the wash cycle so as to give time or the , ., . , :
- 3 - C 558 (R) bleaching step to occur. Preferably this should occur as early as possible in the wash cycle for maximum bleaching to occur.
It is thus clear that in order to produce a satisfatory bleach activator granule for use in a detergent bleach composition, the choice of a suitable binding agent is of essential importance.
One important requirement for a good binding material is good water-solubility so as to impart satisfactory disintegration properties to the granule. Other important requirements are:
- a good binding capacity, so as to form fairly strong granules with good resistance to break-down through mechanical action during handling, transport and storage,i.e. mechanical strength - formulation-compatible,e.g. suitable pHi - capable of producing granules with a high activator content, and preferably, - inexpensive and readily availabe.
Bleach activator granules hittlerto known in the art are deficient in some or other respects.
It is therefore an object of the present invention to provide improved bleach activator granules having the necessary attributes for a suitable use in or with washing and bleaching compositions.
According to the invention a bleach activator is provided in the form of granules for use in or with washing and bleaching compositions of a size of from 0.2 mm to 2.5 mm, which granules constitute from 55% by weight up to about 90% by weight of at least one bleach activator for percompounds, having a titre in the defined peracid formation test of at least 1.5 ml 0.1N sodium thiosulphate, and from 10% to 45% by weight of a binding material comprising essentially a mixture of at least two hydratable inorganic salts. The first hydratable salt is either sodium tri-phosphate or borax (Na2B407) or a mixture thereof and the second hydratable inorganic sal~ is a salt having solubility in water of :
: . ~ :: .
. .
: .
- ~ - C 558 (R) more than 30 grams anhydrous salt per 100 ml at 60C, a pH of around neutral up to about 11, for 10% solution, and no transition point below 35C.
The peracid forlnation test is a well-known test method for selecting suitable bleach activators. It has been described in US Patent Specification No. 3,177,148 and is as follows:
Peracid formation test:
.. .. , . _ . _ A test solution is prepared by dissolving the following materials in 1000 ml distilled ~ater:
sodium pyrophosphate (Na4P207.10~l20) - 2.5 g sodium perborate (NaB02.H~02.3H20) havin~
15 10.4% available oxygen - 0.615 g sodium dodecylbenzene sulphonate - 0.5 9 To this solution at 60C such an amount of activator is added that for each atom of available oxygen present one molecular equivalent of activator is introduced.
The mixture obtained by addition of the activator is vigorously stirred and maintained at 60C. After 5 minutes from the addition a 100 ml portion of the solution is withdrawn and immediately pipetted onto a mixture of 250 g. cracked ice and 15 ml glacial acetic acid. Potassium iodine (0.4 9) is then added and the liberated iodine is immediately titrated with 0.1N sodium thiosulphate with - starch as indicator until the first disappearance of the blue colour.
The amount of sodium thiosulphate solution used in ml. is the titre of the bleach activator.
Examples o~ bleach activators utilisable according to the invention may be compounds of the class of carboxylic anhydrides; carboxylic acid esters; and ~-acyl or 0-acyl substituted amides or aminesi such as sodium acetoxybenzene sulphonate (SABS)~ sodium para sulphonated phenyl benzoate, acetyl salicylic acid, tetraacetyl methylene diamine (TAMD), tetraacetylethylene diamine (TAED), and tetra-.
- ~, .
: :
,: :
.
..
.
.. . . .
- 5 - C 558 (~) acetylglycoluril (TAGU).
Preferred bleach activators are TAMD and TAED.
An essential feature of the bleach activator granule of the invention is that the binding material constitutes a mixture of at least two components,i.e. a first hydratable salt which is sodium triphosphate and/or borax and a second hydratable salt as defined above. For reasons of costs ancl practicability sodium triphosphate is preferably used as the first hydratable salt.
The presence of sodium triphosphate and/or borax is essential in that it governs the final strength of the granule, whereas the presence of the second hydratable salt is needed to govern the --stickiness and intermediate strength of the agglomerate during the preparation of the granules.
The second hydratable salt should have no transition point below 35C, preferably at least 37C. This limitation is deemed necessary for maintaining particle stability under fluctuating and/or severe storage conditions. A transition point lower than 35C would increase the risk of the granules to disintegrate and decompose during storage through loss of water of hydration.
High sollibility of the second hydratable salt is not only of importance for the release of the activator but also for providing a relatively fast disintegrating rate of the granule. The latter is of importance to reduce mechanical loss in the washing machine and to reduce the risk of "spotting" on clothes soaked therein.
"Mechanical loss" is a term used here to indicate the proportion of generally less soluble or heavy particles of the cleaning composition, sinking into the bottom of the washing machine and thereby excluded from contributing in the active washing pro oess.
The pH in solution is important since higher alkalinity would present problems in spraying and handling and would affect enzyme stability in the product as well as that of the activator itself.
.
, . . ' '' " '~
- 6 - C 558 (R) A suitable pH range is from about 6 to 11, preferably from 7 to 10, so as to have the least effect on the overall in use pH of the washing composition.
Preferably the proportion of sodium triphosphate and/or borax in the granule o-f the invention will be within the range of about 5%
to 35% by weight based on the total granule composition. Though a proportion smaller than 5% can be used,it is not advisable since it will tend to give granules of unacceptable mechanical strength. A
par-ticularly suitable proportional range of sodium triphosphate and/or borax is from about 7.5-30% by weight, based on the total granule composition.
Advantageously the second hydratable salt in the granule of the invention is present in a proportion ranging from about 5 to 30%
by weight, preferably from 5 to 15% by weight based on the total granule composition.
:
There are no specific requirements as to the ratio by weight of the first hydratable salt to the second hydratablesalt.Various ratiosare possible and the selection thereof for each particular case will be no problem to the man skilled in the art working ~ithin the invention.
A particularly suitable second hydratable salt for use in the present invention is disodium orthophosphate. Other examples of suitable compounds are potassium triphosphate and magnesium sulphate.
Inorganic salts, such as sodium carbonate, sodium silicate, sodium sulphate, sodium chloride, trisodium orthophosphate, sodium tri-phosphate and sodium pyrophosphate are deficient in one or more respects and are therefore unsuitable for use in the present invention. Sodium carbonate is unsuitable on account of its high pH in solution and its low transition point; sodium silicate and trisodium orthophosphate are unsuitable in view of their high pH
in solution; sodium chloride is unsuitable as it does not form a , ~ . , .
: .
. . .
- 7 - C 558 ~R) hydrate under normal conditions; sodium sulphate is unsuitable owing to its low transition point; sodium triphosphate and pyrophosphate are deficient in their low solubility.
Disodium orthophosphate (DSOP) has a solubility in water of over 40% as anhydrous salt at 60C; a pH for 10% solution of about 8.9 and a transition point of >35C. Furthermore this salt has a number of hydrates which give it high water-binding capacity.
It was also found that 50% solutions of the dihydrate, which are in : 10 completely solid form at ambient temperature, are fluid and sprayable at temperatures above 50C.
Magnesium sulphate has a solubility in water of about 35% as anhydrous salt at 60G; a pH for 10% solution of about 7 and no transition point below 35C.
Examples I-II
Some batchwise granulation experiments were carried out using an N,N,N',N'-tetraace-tylethylene diamine (TAED), sodium triphosphate (STP) mixture, containing about 85% by weigh-t of TAED.
First experiment 4.5 kg of said TAED/STP mixture were placed iln a 0.5 metre pan.
A solution containing 49% of disodium orthophosphate dihydrate was prepared. 1.25 kg of this solution at a temperature of 75C
was sprayed onto the TAED/STP rnixture using a WFM 504 jet at 3.5 kg/cm2. The resulting granules had a granulometry of about 90% (0.3-1.2 mm)g 0.5% (~ 1.2 mm) and 9.5% (~ 0.3 mm) and had the following composition~
TAED 66.5%
Sodium triphosphate (expressed as anhydrous salt) 11.7%
Disodium orthophosphate (expressed as anhydrous salt~ 8.5%
Water 13.3%
These granules had excellent disintegration characteristics in J~
- 8 - C 558 (R) the wash.
Second experiment 3.5 kg of the same TAED/STP mixture were placed in a 0.5 metre pan.
A solution containing 5.7% anhydrous sodium triphosphate and 37.5% disodium orthophosphate dihydrate was prepared. 0.75 kg of this solution at a temperature of 75C was sprayed onto -the TAED/STP mixture using a WFM 804 jet at 3.5 kg/cm2. The resulting granules had a granulometry of 20.5% [~ 1.2 mm); 77% (1.2-0.3 mm) and 2.5% (< 0.3 mm) and had the following composition: (Granule Type II).
TAED 70 0%
sodium triphosphate (expressed as anhydrous salt) 13.4%
15 disodium orthophosphate (expressed as anhydrous salt) 5.3%
water 11. 3%
These granules were readily dispersed in the wash and had quite satisfactory handling characteristics.
Storage trials were carried out with these granules for two and four weeks' periods, at 37C/70% RH (relative humidity) in laminated packets in a detergent base powder ~ to the following composition: (A similar composition comprising unprotected TAED
25 was used as comparison) % by weight Detergent base powder ~ 81.0 TAED granules 8.0 30 Sodium perborate tetrahydrate 10.0 Proteolytic enzyme (Alcalase; 1.5 Anson Units) 1.0 The detergent base powder lS an anionic/nonionic binary active powder based on sodium triphosphate.
The ~ollowing residual activities (%) were found:
,. ..
2~66 - 9 - C 558 (R) TAED perborate enzyme 2 weeks 4 weeks 2 weeks 4 weeks 2 weeks 4 weeks Granule Type I 94 89 102 77 69 60 5 Granule Type II n/a 92 n/a 73 n/a 54 Unprotected 10 TAED n/a 44 n/a 43 n/a 16 Two principal tests were carried out to evaluate the utility of the granules:
1) Granule strengt_ This was assessed by the use of the "Wallace Inden-tation Tester".
i5 This apparatus determines the crush-load in grams which is the weight an individual granule will support. The apparatus is operated simply by loading up the contacting plunger with weights until the granule fails. An average is taken from about 15 (but not less than 10) granules. In general it can be said that a crush-load of above 20 grams is satisfactory.
':
2) Granule disintegration ~ _ _ _ _ This is estimated by placing 1 gram of the granules in 200 9 of distilled wa-ter at 25C in a beaker (diameter 7 cm). The liquid is stirred with a flat-bladed (5 x 1~ cm) stirrer - placed 4.2 cm above the base of the beaker. The stirrer speed was 75-80 rpm. ~isual observatinn was used to estimate the time taken for all granules to completely break up. A
satisfactory granule should have a maximum disintegration time of 50 seconds.
The follo~1ng test results were obtained:
Disintegration time (in seconds) Crush !oad (in grams) Granule I + 10 27 Granule II IS-20 ~ 55 ~,, - 10 - C 558 (R) Example III
4.0 kg of a TAED/STP mixture containing 3400 g TAED, were placed in a 0.5 metre granulating pan. A solution containing 47%
MgS04.7H20 was preferred. 2.2 kg of this solution, at a temperature of 65-70 C, was sprayed onto the TAED/STP mixture using a WFM 804 jet at 3.5 kg/cm2. The resulting granules had a granulometry of 2.7% (> 1.2 mm); 84.2% (1.2-0.3 mm) and 13.1% (< 0.3 mm) and had the following composition after weathering:
TAED 61.3%
Sodium triphosphate (anhydrous) 10.8%
Magnesium sulphate (anhydrous) 9.2%
Water 18.7%
The granules showed a disintegration time of 25-30 seconds and a mean crush-load of 46 grams.
The following experiment was carried out, using sodium silicate as the second hydrable salt.
4.0 kg of a TAED/STP mixture (3400 g TAED) in a granulating pan was sprayed with 700 g of a solution containing 12.6% sodium triphosphate and 19.1% sodium silicate (anhydrous) in the same way as in the above Example. The silicate used was neutral silicate (Na20 3.3 Si02)-The resulting granules had a granulometry of 8.2% (' 1.2 mm);
81.2% (1.2-0.3 mm) and 10.6 (< 0.3 mm) and had the following composition after weathering:
TAED 72.2%
Sodium triphosphate (anhydrous) 16.5%
Sodium silicate (anhydrous) 2.8%
Water 8.5%
Though the granules look all right and had a satisfactory crush-load ~ C 558 5R) oF 131 grams, they suffer from slow dissolving properties. The measured disintegration time was ~ 120 seconds, which is unsatisfactory.
Example IV
3400 grams oF pure TAED were mixed with 1000 grams of partially dried borax decahydrate (- 1110 grams Na2B407.10H20) in a granulating pan. A solution of 40% anhydrous disodium ortho-phosphate was preparecl. 1.5 kg of this solution, at a temperature oF 60~65C, was sprayed onto the TAED/borax mixture, using a WFM 804 jet at 3~5kg/cm2. The resulting granules had a granulo-metry of 0.8% ~> 1.2 mm); 78.3% (1.2-0.3 mm) and 20.9 (~ 0.3 mm), and had the following composition:
rAED 60.5%
borax (anhydrous) 10.5%
DSOP (anhydrous) 10.7%
water 18.3%
Disintegration time was 20 seconds.
Mean crush-load was 25 grams.
For comparison granules were prepared without the use of a second hydratable salt. The granules, which had the following composition:
TAED 69.0 Sodium triphosphate (anhydrous) 20.7 Water 10.3, showed the following granule characteristics:
Crush-load 143 g.
disintegration time > 60 seconds
1) Granule strengt_ This was assessed by the use of the "Wallace Inden-tation Tester".
i5 This apparatus determines the crush-load in grams which is the weight an individual granule will support. The apparatus is operated simply by loading up the contacting plunger with weights until the granule fails. An average is taken from about 15 (but not less than 10) granules. In general it can be said that a crush-load of above 20 grams is satisfactory.
':
2) Granule disintegration ~ _ _ _ _ This is estimated by placing 1 gram of the granules in 200 9 of distilled wa-ter at 25C in a beaker (diameter 7 cm). The liquid is stirred with a flat-bladed (5 x 1~ cm) stirrer - placed 4.2 cm above the base of the beaker. The stirrer speed was 75-80 rpm. ~isual observatinn was used to estimate the time taken for all granules to completely break up. A
satisfactory granule should have a maximum disintegration time of 50 seconds.
The follo~1ng test results were obtained:
Disintegration time (in seconds) Crush !oad (in grams) Granule I + 10 27 Granule II IS-20 ~ 55 ~,, - 10 - C 558 (R) Example III
4.0 kg of a TAED/STP mixture containing 3400 g TAED, were placed in a 0.5 metre granulating pan. A solution containing 47%
MgS04.7H20 was preferred. 2.2 kg of this solution, at a temperature of 65-70 C, was sprayed onto the TAED/STP mixture using a WFM 804 jet at 3.5 kg/cm2. The resulting granules had a granulometry of 2.7% (> 1.2 mm); 84.2% (1.2-0.3 mm) and 13.1% (< 0.3 mm) and had the following composition after weathering:
TAED 61.3%
Sodium triphosphate (anhydrous) 10.8%
Magnesium sulphate (anhydrous) 9.2%
Water 18.7%
The granules showed a disintegration time of 25-30 seconds and a mean crush-load of 46 grams.
The following experiment was carried out, using sodium silicate as the second hydrable salt.
4.0 kg of a TAED/STP mixture (3400 g TAED) in a granulating pan was sprayed with 700 g of a solution containing 12.6% sodium triphosphate and 19.1% sodium silicate (anhydrous) in the same way as in the above Example. The silicate used was neutral silicate (Na20 3.3 Si02)-The resulting granules had a granulometry of 8.2% (' 1.2 mm);
81.2% (1.2-0.3 mm) and 10.6 (< 0.3 mm) and had the following composition after weathering:
TAED 72.2%
Sodium triphosphate (anhydrous) 16.5%
Sodium silicate (anhydrous) 2.8%
Water 8.5%
Though the granules look all right and had a satisfactory crush-load ~ C 558 5R) oF 131 grams, they suffer from slow dissolving properties. The measured disintegration time was ~ 120 seconds, which is unsatisfactory.
Example IV
3400 grams oF pure TAED were mixed with 1000 grams of partially dried borax decahydrate (- 1110 grams Na2B407.10H20) in a granulating pan. A solution of 40% anhydrous disodium ortho-phosphate was preparecl. 1.5 kg of this solution, at a temperature oF 60~65C, was sprayed onto the TAED/borax mixture, using a WFM 804 jet at 3~5kg/cm2. The resulting granules had a granulo-metry of 0.8% ~> 1.2 mm); 78.3% (1.2-0.3 mm) and 20.9 (~ 0.3 mm), and had the following composition:
rAED 60.5%
borax (anhydrous) 10.5%
DSOP (anhydrous) 10.7%
water 18.3%
Disintegration time was 20 seconds.
Mean crush-load was 25 grams.
For comparison granules were prepared without the use of a second hydratable salt. The granules, which had the following composition:
TAED 69.0 Sodium triphosphate (anhydrous) 20.7 Water 10.3, showed the following granule characteristics:
Crush-load 143 g.
disintegration time > 60 seconds
Claims (5)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Bleach activator granules for use in or with a detergent and/or bleach composition of a size of from 0.2 mm to 2.5 mm, of which each granule is composed of:
1) from 55% to 90% by weight of at least one bleach activator for percompounds having a titre in the peracid formation test of at least 1.5 ml 0.1N sodium thiosulphate, and 2) from 10% to 45% by weight of a binding material comprising essentially a mixture of at least one first hydratable inorganic salt selected from the group consisting of sodium triphosphate, borax and mixtures thereof, and one second hydratable inorganic salt having solubility in water of more than 30 grams anhydrous salt per 100 ml at 60°C, a pH of about 6-11 for 10% solution, and no transition point below 35°C.
1) from 55% to 90% by weight of at least one bleach activator for percompounds having a titre in the peracid formation test of at least 1.5 ml 0.1N sodium thiosulphate, and 2) from 10% to 45% by weight of a binding material comprising essentially a mixture of at least one first hydratable inorganic salt selected from the group consisting of sodium triphosphate, borax and mixtures thereof, and one second hydratable inorganic salt having solubility in water of more than 30 grams anhydrous salt per 100 ml at 60°C, a pH of about 6-11 for 10% solution, and no transition point below 35°C.
2. Bleach activator granules according to claim 1, wherein the proportion of the first hydratable salt is 5-35% by weight and the proportion of the second hydratable salt is 5-30% by weight of the total granule composition.
3. Bleach activator granules according to claim 2, wherein said proportions are 7.5-30% by weight for the first hydratable salt and 5-15% by weight for the second hydratable salt.
4. Bleach activator granules according to claim 1, wherein the second hydratable salt is disodium orthophosphate.
5. Bleach activator granules according to claim 1, wherein the bleach activator is N,N,N',N'-tetraacetyl ethylene diamine.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB5347377 | 1977-12-22 | ||
| GB53,473/77 | 1977-12-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1102966A true CA1102966A (en) | 1981-06-16 |
Family
ID=10467949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA318,448A Expired CA1102966A (en) | 1977-12-22 | 1978-12-21 | Bleach activator granules |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS6059958B2 (en) |
| BR (1) | BR7808427A (en) |
| CA (1) | CA1102966A (en) |
| CH (1) | CH639417A5 (en) |
| DE (1) | DE2855777C3 (en) |
| FR (1) | FR2412611A1 (en) |
| GB (1) | GB2015050B (en) |
| IT (1) | IT1109669B (en) |
| NL (1) | NL180122C (en) |
| NZ (1) | NZ189183A (en) |
| ZA (1) | ZA787140B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0790244A1 (en) | 1996-02-15 | 1997-08-20 | Hoechst Aktiengesellschaft | Ammonium nitriles and use thereof as bleach activators |
| US5969171A (en) * | 1997-07-01 | 1999-10-19 | Clariant Gmbh | Metal complexes as bleach activators |
| US5998645A (en) * | 1997-05-07 | 1999-12-07 | Clariant Gmbh | Bleaching-active metal complexes |
| US6365562B1 (en) | 2000-04-20 | 2002-04-02 | Clariant Gmbh | Laundry detergents and cleaners comprising bleaching-active dendrimer ligands and metal complexes thereof |
| US6545147B1 (en) | 1999-09-10 | 2003-04-08 | Clariant Gmbh | Bleaching-active metal complexes |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IE49996B1 (en) * | 1979-07-06 | 1986-01-22 | Unilever Ltd | Particulate bleach compositions |
| FI67092C (en) * | 1980-12-09 | 1985-01-10 | Unilever Nv | BLEKNINGSAKTIVATOR-KORN AVSEDDA FOER TVAETT- OCH / ELLER BLEKNINGSBLANDNINGAR |
| EP0075818B2 (en) * | 1981-09-28 | 1990-03-14 | BASF Aktiengesellschaft | Granular bleach activator |
| IT1180458B (en) * | 1984-03-22 | 1987-09-23 | Mira Lanza Spa | GRANULAR WHITENING ACTIVATOR AND ITS MANUFACTURING PROCESS |
| GB8422158D0 (en) * | 1984-09-01 | 1984-10-03 | Procter & Gamble Ltd | Bleach compositions |
| DE3639115A1 (en) * | 1986-11-15 | 1988-05-19 | Henkel Kgaa | STORAGE BLENDER MIXTURE WITH IMPROVED SOLUTION |
| DE19515233A1 (en) * | 1995-04-28 | 1996-10-31 | Henkel Kgaa | Storage-stable granules containing bleach activators and their production |
| EG23339A (en) * | 1999-12-20 | 2004-12-29 | Procter & Gamble | Bleach activators with improved solubility. |
| GB0710559D0 (en) * | 2007-06-02 | 2007-07-11 | Reckitt Benckiser Nv | Composition |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2048331A1 (en) * | 1970-10-01 | 1972-04-06 | Henkel & Cie GmbH, 4000 Dusseldorf | Solid, powdery to granular agents for the production of cold-acting bleaching liquors, in particular cold-acting bleaching liquors, and processes for the manufacture of these agents |
-
1978
- 1978-12-08 NL NLAANVRAGE7811971,A patent/NL180122C/en not_active IP Right Cessation
- 1978-12-12 BR BR7808427A patent/BR7808427A/en unknown
- 1978-12-15 NZ NZ189183A patent/NZ189183A/en unknown
- 1978-12-20 GB GB7849327A patent/GB2015050B/en not_active Expired
- 1978-12-20 ZA ZA787140A patent/ZA787140B/en unknown
- 1978-12-21 CH CH1303178A patent/CH639417A5/en not_active IP Right Cessation
- 1978-12-21 JP JP53156959A patent/JPS6059958B2/en not_active Expired
- 1978-12-21 CA CA318,448A patent/CA1102966A/en not_active Expired
- 1978-12-21 IT IT69928/78A patent/IT1109669B/en active
- 1978-12-21 FR FR7835883A patent/FR2412611A1/en active Granted
- 1978-12-22 DE DE2855777A patent/DE2855777C3/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0790244A1 (en) | 1996-02-15 | 1997-08-20 | Hoechst Aktiengesellschaft | Ammonium nitriles and use thereof as bleach activators |
| US5998645A (en) * | 1997-05-07 | 1999-12-07 | Clariant Gmbh | Bleaching-active metal complexes |
| US5969171A (en) * | 1997-07-01 | 1999-10-19 | Clariant Gmbh | Metal complexes as bleach activators |
| US6545147B1 (en) | 1999-09-10 | 2003-04-08 | Clariant Gmbh | Bleaching-active metal complexes |
| US6365562B1 (en) | 2000-04-20 | 2002-04-02 | Clariant Gmbh | Laundry detergents and cleaners comprising bleaching-active dendrimer ligands and metal complexes thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2855777A1 (en) | 1979-06-28 |
| BR7808427A (en) | 1979-08-21 |
| DE2855777C3 (en) | 1982-02-04 |
| CH639417A5 (en) | 1983-11-15 |
| FR2412611A1 (en) | 1979-07-20 |
| NL7811971A (en) | 1979-06-26 |
| GB2015050A (en) | 1979-09-05 |
| IT7869928A0 (en) | 1978-12-21 |
| NL180122C (en) | 1987-01-02 |
| GB2015050B (en) | 1982-03-17 |
| NL180122B (en) | 1986-08-01 |
| ZA787140B (en) | 1980-07-30 |
| JPS54109085A (en) | 1979-08-27 |
| FR2412611B1 (en) | 1982-11-05 |
| JPS6059958B2 (en) | 1985-12-27 |
| DE2855777B2 (en) | 1981-01-15 |
| NZ189183A (en) | 1980-12-19 |
| IT1109669B (en) | 1985-12-23 |
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