CA1048888A - Anticaking of linear alkyl aryl sulfonate detergents - Google Patents
Anticaking of linear alkyl aryl sulfonate detergentsInfo
- Publication number
- CA1048888A CA1048888A CA75229374A CA229374A CA1048888A CA 1048888 A CA1048888 A CA 1048888A CA 75229374 A CA75229374 A CA 75229374A CA 229374 A CA229374 A CA 229374A CA 1048888 A CA1048888 A CA 1048888A
- Authority
- CA
- Canada
- Prior art keywords
- composition
- linear alkyl
- weight
- particulates
- alkyl aryl
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/046—Salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
-
- 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions
- C11D11/02—Preparation in the form of powder by spray drying
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Linear alkyl aryl sulfonate detergent products in the form of dried particulates show improved anti-caking with the addition of magnesium sulfate. The aforesaid addition of magnesium sulfate is particularly useful in spray dried deter-gent compositions to provide a non-caking hollow spherical beaded product.
Linear alkyl aryl sulfonate detergent products in the form of dried particulates show improved anti-caking with the addition of magnesium sulfate. The aforesaid addition of magnesium sulfate is particularly useful in spray dried deter-gent compositions to provide a non-caking hollow spherical beaded product.
Description
1~4~388 This invention relates to supression of the caking tendencies of linear alkyl aryl sulfonate detergents. More specifically this invention relates to non-caking linear alkyl aryl sulfonate detergent compositions in the form of dried particulates.
The prior art was directed to the use of biodegradable de-tergent compositions of the linear alkyl benzene sulfonate type.
Dried formulations containing substantial proportions of linear alkyl benzene sulfonates however presented caking problems which were not satisfactorily eliminated with presently knownanticaking additives such as low molecular weight sodium sulfonates and sodium silico-aluminate. Commercial spray dried products con-taining substantial amounts of linear alkyl benzene sulfonates were found to be particularly susceptible to caking.
It has now been found that by the addition of magnesium sul-fate to linear alkyl aryl sulfonates, the resultant dried par-ticulate products exhibit improved anti-caking characteristics.
It is therefore an object of this invention to provide a .;.
linear alkyl aryl sulfonate detergent composition which provides a non-caking product.
It is a further object of this invention to provide a par-ticulate product of the aforesaid detergent composition which is ~ non-caking.
:
It is a further object of this invention to provide a spray dried hollow spherical beaded product of the aforesaid detergent composition which is non-caking.
The aforesaid as well as other objects and advantages will be made apparent from a reading of the following detailed des-cription.
~6~4~888 In accordance with the present invention the detergent com-position may typicalIy have from about ~0 to 5~/0 by weight of linear alkyl aryl sulfonates,for most commercial formulations, and preferrably about 4~/0 by weight although more or less linear alkyl aryl sulfonate may be used as required.
In order to produce a linear alkyl benzene sulfonate ~S),it is one generally derived from the sulfonation and neutralization of detergent alkylate in which the hydrocarbyl or alkyl radical is derived from straight-chain or normal hydrocarbons instead of polypropylene. To make the biodegradable detergent, conventional reactions involve catalytic alkylation of benzene or some other aryl compounds, such as toluene or xylene, with either an n-alkene or an n-alkyl halide alkylating agent of the desired ' molecular weight range, i.e., corresponding to a carbon content of 8 to 18 carbon atoms. The alkylating agent can be derived from petroleum distillate cracking or petroleum wax cracking, catalytic dehydrogenation of n-paraffins, chlorination-dehydro-chlorination of n-paraffins, ethylene polymerization, and chlori-. nation of n-paraffins. In addition, the raw materials from which the straight-chain stock is to be derived may be and often is, subjected to is~normal separation processes, such as those in-volving molecular sieves and urea clathration to produce a more linear product than could otherwise be obtained.
The linear alkyl aryl sulfonates useful in this invention are preferably linear alkyl benzene sulfonates wherein the alkyl chain preferably has 8 to 18 carbon atoms and most preferably 10 -to 15 carbon atoms. An alkyl chain which is a straight chain containing 12 carbon atoms is generally very suitable.
The other essential ingredient in the composition of this invention is magnesium sulfate. The magnesium sulfate as an 1~:)4~8~8 anticaking agent for linear alkyl aryl sulfonate detergents may be present in amounts of from about 1 to 5.~/O by weight, and pre-ferably in an amount of about 2.~ to 3.2% by weight; the weights being on an anhydrous basis. The magnesium sulfates useful in the compositions of this invention may be any one the commercial grades of magnesium sulfate, such as by way of example, epsom salts or magnesium sulfate heptahydrate. It is of course under-stood that where the detergent product contains large percentages of linear alkyl aryl sulfonates, higher percentages of magnesium sulfate may be employed.
The products formed from the composition of the present in-vention may be produced by known commercial methods such as spray drying or drum drying. It is within the contemplation of this invention that any form of particulate product formed from the composition of this invention have good anti-caking character-istics.
In a typical spray drying method, the composition of this invention may be formed into a slurry, and the slurry then forced through spray nozzles into towers wherein the small liquid part-iculates are modified, solidified and dried as they contact a stream or vortex of heated air. The composition is produced thereby in the form of hollow, thin-walled spheres or beads ge-nerally having low apparent bulk densities and characterized by good solubility, good foaming properties, uniformity of particles and which are essentially non-caking.
The composition may contain any of the other ingredients usual in detergent compositions such as alkaline builder salts, bleaches, optical brighteners, sequestering agents, soil suspend-ing agents, colors, perfumes, bacteriocides and the like. Other 1~348888 organic detergents may be present in minor proportions provided that they do not impair the performance of the composition of the invention. In particular, ~ather stabilizers may be added;
examples are, fatty acyl ethanolamides, such as lauric mono-ethanolamide.
The invention is further illustrated by the following exam-ple which is not to be considered as limiting the scope of the invention~ All percentages reported in the example are by weight or unless otherwise indicated.
EXAMPLE
Five samples were prepared, slurried and spray dried by conventional methods to produce hollow spherical beaded products having the composition analyses as reported in Table 1 and the physical analyses as reported in Table 2.
, . .
Composition (%) Component 1 2 3 4 5 LAS 43.243.0 36.3 41.740.3 NaCl 6.8 5.5 9.7 13.612.6 water 2.0 2.0 1.0 1.00.9 Anticake2 1.8 1.8 0.0 0.00.0 Anticake 0.8 1.3 0.0 0.00.0 Anticake -- -- -- -- 0.8 MgSO45~ 0.2 0.2 0.2 3.20.5 Filler7 R8. R8~ R8~ R8~ R8 notes:
1. sodium alkyl benzene sulfonate, molecular weight 339, average alkyl is Cll 5 ~4~8~3
The prior art was directed to the use of biodegradable de-tergent compositions of the linear alkyl benzene sulfonate type.
Dried formulations containing substantial proportions of linear alkyl benzene sulfonates however presented caking problems which were not satisfactorily eliminated with presently knownanticaking additives such as low molecular weight sodium sulfonates and sodium silico-aluminate. Commercial spray dried products con-taining substantial amounts of linear alkyl benzene sulfonates were found to be particularly susceptible to caking.
It has now been found that by the addition of magnesium sul-fate to linear alkyl aryl sulfonates, the resultant dried par-ticulate products exhibit improved anti-caking characteristics.
It is therefore an object of this invention to provide a .;.
linear alkyl aryl sulfonate detergent composition which provides a non-caking product.
It is a further object of this invention to provide a par-ticulate product of the aforesaid detergent composition which is ~ non-caking.
:
It is a further object of this invention to provide a spray dried hollow spherical beaded product of the aforesaid detergent composition which is non-caking.
The aforesaid as well as other objects and advantages will be made apparent from a reading of the following detailed des-cription.
~6~4~888 In accordance with the present invention the detergent com-position may typicalIy have from about ~0 to 5~/0 by weight of linear alkyl aryl sulfonates,for most commercial formulations, and preferrably about 4~/0 by weight although more or less linear alkyl aryl sulfonate may be used as required.
In order to produce a linear alkyl benzene sulfonate ~S),it is one generally derived from the sulfonation and neutralization of detergent alkylate in which the hydrocarbyl or alkyl radical is derived from straight-chain or normal hydrocarbons instead of polypropylene. To make the biodegradable detergent, conventional reactions involve catalytic alkylation of benzene or some other aryl compounds, such as toluene or xylene, with either an n-alkene or an n-alkyl halide alkylating agent of the desired ' molecular weight range, i.e., corresponding to a carbon content of 8 to 18 carbon atoms. The alkylating agent can be derived from petroleum distillate cracking or petroleum wax cracking, catalytic dehydrogenation of n-paraffins, chlorination-dehydro-chlorination of n-paraffins, ethylene polymerization, and chlori-. nation of n-paraffins. In addition, the raw materials from which the straight-chain stock is to be derived may be and often is, subjected to is~normal separation processes, such as those in-volving molecular sieves and urea clathration to produce a more linear product than could otherwise be obtained.
The linear alkyl aryl sulfonates useful in this invention are preferably linear alkyl benzene sulfonates wherein the alkyl chain preferably has 8 to 18 carbon atoms and most preferably 10 -to 15 carbon atoms. An alkyl chain which is a straight chain containing 12 carbon atoms is generally very suitable.
The other essential ingredient in the composition of this invention is magnesium sulfate. The magnesium sulfate as an 1~:)4~8~8 anticaking agent for linear alkyl aryl sulfonate detergents may be present in amounts of from about 1 to 5.~/O by weight, and pre-ferably in an amount of about 2.~ to 3.2% by weight; the weights being on an anhydrous basis. The magnesium sulfates useful in the compositions of this invention may be any one the commercial grades of magnesium sulfate, such as by way of example, epsom salts or magnesium sulfate heptahydrate. It is of course under-stood that where the detergent product contains large percentages of linear alkyl aryl sulfonates, higher percentages of magnesium sulfate may be employed.
The products formed from the composition of the present in-vention may be produced by known commercial methods such as spray drying or drum drying. It is within the contemplation of this invention that any form of particulate product formed from the composition of this invention have good anti-caking character-istics.
In a typical spray drying method, the composition of this invention may be formed into a slurry, and the slurry then forced through spray nozzles into towers wherein the small liquid part-iculates are modified, solidified and dried as they contact a stream or vortex of heated air. The composition is produced thereby in the form of hollow, thin-walled spheres or beads ge-nerally having low apparent bulk densities and characterized by good solubility, good foaming properties, uniformity of particles and which are essentially non-caking.
The composition may contain any of the other ingredients usual in detergent compositions such as alkaline builder salts, bleaches, optical brighteners, sequestering agents, soil suspend-ing agents, colors, perfumes, bacteriocides and the like. Other 1~348888 organic detergents may be present in minor proportions provided that they do not impair the performance of the composition of the invention. In particular, ~ather stabilizers may be added;
examples are, fatty acyl ethanolamides, such as lauric mono-ethanolamide.
The invention is further illustrated by the following exam-ple which is not to be considered as limiting the scope of the invention~ All percentages reported in the example are by weight or unless otherwise indicated.
EXAMPLE
Five samples were prepared, slurried and spray dried by conventional methods to produce hollow spherical beaded products having the composition analyses as reported in Table 1 and the physical analyses as reported in Table 2.
, . .
Composition (%) Component 1 2 3 4 5 LAS 43.243.0 36.3 41.740.3 NaCl 6.8 5.5 9.7 13.612.6 water 2.0 2.0 1.0 1.00.9 Anticake2 1.8 1.8 0.0 0.00.0 Anticake 0.8 1.3 0.0 0.00.0 Anticake -- -- -- -- 0.8 MgSO45~ 0.2 0.2 0.2 3.20.5 Filler7 R8. R8~ R8~ R8~ R8 notes:
1. sodium alkyl benzene sulfonate, molecular weight 339, average alkyl is Cll 5 ~4~8~3
2. 75% sodium xylene sulfonate, 250/o sodium toluene sulfon~e
3. hydrated sodium silico-aluminate
4. trisodium sulfosuccinate
5. anhydrous weight basis
6. estimated
7. sodium sulfate
8. remainder~
The spray dried hollow beaded products o~ samples 1-5 were prepared from formulations containing 40 percent by weight of the linear alkyl aryl sulfonates, and sample No. 4 contained 5 percent by weight anhydrous of MgS04 as the heptahydrate. Samples 1 and 2 were produced in a spray dry tower wherein the tower air inlet temperature was 815F. and the air outlet temperature was 210 to 225F. with a slurry pressure of 650 to 700 psig. For the formulation of sample 3, the corresponding air inlet temperature was 8250F., and the air outlet temperature was 225 to 2350F.
with a slurry pressure of 450 to 750 psig. For the formulation of sample 4, the corresponding air inlet temperature was 825 F., and the air outlet temperature was 225F., with a slurry pressure of 450 to 550 psig. For the formulation of sample 5, the air inlet temperature was 820F, and the air outlet temperature was 225F, with the slurry pressure of 450 to 500 psig.
Physical Properties pH 7.27.3 5.5 7.7 7.7 Density2 0.210.20 0.26 0.23 0.24 Clarity3 hazy hazy clear clear clear Particulate Size Distribution, % on U.S. Std. Sieve ~o. 20 0.6 2.0 0.0 0.2 0.0 ~lo. 4016.833.4 8.9 38.4 24.8 No. 6037.533.8 51.7 ~6.1 52.2 ~o. 8018.713.3 25.5 9.9 15.4 . 1008.5 5.4 6.6 ~ 3,7 No. 1206.4 3.9 3.7 1.5 2.0 pan 11.5 8.2 3.6 1.5 1.9 100.0100.01.00.0100.0100.0 notes:
1. 1% solution 2. g/cc.
3. 1% solution The spray dried beaded product of each of the five samples was evaluated to determine caking tendency as a function of water content according to the method reported by Monick (i.e. J. A .
Monick, "Measuring Tackiness of Detergent Powders", Soap & Chem., Spec. 42 (6), pp. 49-53, 107, June 1966) . This procedure involves applying pressure to a cylinder of powder contained in a mold to form a cake, removing the mold, and determining the force required to break the cake, A low breaking force is reported to correlate with a low tendency toward caking. Previous studies have shown that caking in detergent products increases with increasing moisture content in the product. To obtain a caking profile, the breaking force for each product is determined by varying water contents. The water contents, determined as volatiles at 150C, were adjusted by drying the products at 100C or by maintainingtbQ, products in a humid environment and then allowing the products to equilibrate in a closed jar overnight.
1~4~88 The results of the Monick tests are reported in Table 3.
' ,:
`, TABLE 3 Breaking force Sample No. Water (%)(lb.) .
1. 0.7 1.0 2.0 5~5 2.7 9.2 2. 0.7 0.0 2.0 3~0 2.4 8,52 3. 1.0 0.0 2.0 2'2 3.3 9'2 3~5 11.0 4. 1.0 0.0 1.9 0.0 2.7 0.0 3.8 1.5 4.6 4.0 5. 0.9 0.0 1.5 1.0 2.2 2.5 4.2 12.52 notes:
1. forming force, 141b. for two minutes at 80 F. (26.7 C) 2. partial breakup of cake observed .
As indicated in Table 3, the caking tendencies of samples 1, 2, 3 and 5 containing known anticaking agents are generally about the same with each of said samples requiring relatively high breaking forces, indicating substantial caking for water contents of about 3 percent. Sample ~o. 4, however, containing no heretofore known anticaking agent, but containing 3.2 percent magnesium sulfate, showed zero breaking force at 2.7 percent water. A zero breaking force indicates that the product is non-caking.
Although the invention has been described with reference to certain preferred embodiments, it is not the intention of the applicants to be limited thereby and certain obvious modifications are intended to be included within the broad scope of the in-vention as embodied in the following claims.
.
The spray dried hollow beaded products o~ samples 1-5 were prepared from formulations containing 40 percent by weight of the linear alkyl aryl sulfonates, and sample No. 4 contained 5 percent by weight anhydrous of MgS04 as the heptahydrate. Samples 1 and 2 were produced in a spray dry tower wherein the tower air inlet temperature was 815F. and the air outlet temperature was 210 to 225F. with a slurry pressure of 650 to 700 psig. For the formulation of sample 3, the corresponding air inlet temperature was 8250F., and the air outlet temperature was 225 to 2350F.
with a slurry pressure of 450 to 750 psig. For the formulation of sample 4, the corresponding air inlet temperature was 825 F., and the air outlet temperature was 225F., with a slurry pressure of 450 to 550 psig. For the formulation of sample 5, the air inlet temperature was 820F, and the air outlet temperature was 225F, with the slurry pressure of 450 to 500 psig.
Physical Properties pH 7.27.3 5.5 7.7 7.7 Density2 0.210.20 0.26 0.23 0.24 Clarity3 hazy hazy clear clear clear Particulate Size Distribution, % on U.S. Std. Sieve ~o. 20 0.6 2.0 0.0 0.2 0.0 ~lo. 4016.833.4 8.9 38.4 24.8 No. 6037.533.8 51.7 ~6.1 52.2 ~o. 8018.713.3 25.5 9.9 15.4 . 1008.5 5.4 6.6 ~ 3,7 No. 1206.4 3.9 3.7 1.5 2.0 pan 11.5 8.2 3.6 1.5 1.9 100.0100.01.00.0100.0100.0 notes:
1. 1% solution 2. g/cc.
3. 1% solution The spray dried beaded product of each of the five samples was evaluated to determine caking tendency as a function of water content according to the method reported by Monick (i.e. J. A .
Monick, "Measuring Tackiness of Detergent Powders", Soap & Chem., Spec. 42 (6), pp. 49-53, 107, June 1966) . This procedure involves applying pressure to a cylinder of powder contained in a mold to form a cake, removing the mold, and determining the force required to break the cake, A low breaking force is reported to correlate with a low tendency toward caking. Previous studies have shown that caking in detergent products increases with increasing moisture content in the product. To obtain a caking profile, the breaking force for each product is determined by varying water contents. The water contents, determined as volatiles at 150C, were adjusted by drying the products at 100C or by maintainingtbQ, products in a humid environment and then allowing the products to equilibrate in a closed jar overnight.
1~4~88 The results of the Monick tests are reported in Table 3.
' ,:
`, TABLE 3 Breaking force Sample No. Water (%)(lb.) .
1. 0.7 1.0 2.0 5~5 2.7 9.2 2. 0.7 0.0 2.0 3~0 2.4 8,52 3. 1.0 0.0 2.0 2'2 3.3 9'2 3~5 11.0 4. 1.0 0.0 1.9 0.0 2.7 0.0 3.8 1.5 4.6 4.0 5. 0.9 0.0 1.5 1.0 2.2 2.5 4.2 12.52 notes:
1. forming force, 141b. for two minutes at 80 F. (26.7 C) 2. partial breakup of cake observed .
As indicated in Table 3, the caking tendencies of samples 1, 2, 3 and 5 containing known anticaking agents are generally about the same with each of said samples requiring relatively high breaking forces, indicating substantial caking for water contents of about 3 percent. Sample ~o. 4, however, containing no heretofore known anticaking agent, but containing 3.2 percent magnesium sulfate, showed zero breaking force at 2.7 percent water. A zero breaking force indicates that the product is non-caking.
Although the invention has been described with reference to certain preferred embodiments, it is not the intention of the applicants to be limited thereby and certain obvious modifications are intended to be included within the broad scope of the in-vention as embodied in the following claims.
.
Claims (14)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A detergent composition comprising from about 30 to 50% by weight of a linear alkyl aryl sulfonate, from about 1 to 5% by weight of magnesium sulfate, or an anhydrous basis, and the remainder inert filler; wherein the alkyl has from about 8 to 18 carbon atoms.
2. The composition of claim 1, wherein the linear alkyl aryl sulfonate is present in an amount of about 40% by weight.
3. The composition of claim 1, wherein the linear alkyl aryl sulfonate is an alkali salt thereof.
4. The composition of claim 3, wherein the alkali salt is sodium.
5. The composition of claim 1, wherein the linear alkyl aryl sulfonate is a linear alkyl benzene sulfonate.
6. The composition of claim 1, wherein the alkyl has from about 10 to 15 carbon atoms.
7. The composition of claim 1, wherein the magnesium sulfate is present in an amount of about 2.8 to 3.2% by weight.
8. The composition of claim 1, wherein the magnesium sulfate is present as magnesium sulfate heptahydrate.
9. The composition of claim 1, wherein said composition is in the form of particulates.
10. The composition of claim 9, wherein said particulates are spray dried hollow spherical beads.
11. The composition of claim 10, wherein the particulates exhibit a caking tendency breaking force of about zero with a water content of up to about 3%, by weight, as determined according to the method of Monick.
12. The composition of claim 9, wherein the particulates are in the form of drum dried particulates.
13. The composition of claim 1, wherein the composition is in the form of particulates and wherein the particulates exhibit a caking tendency breaking force of about zero with a water content of up to about 3%, by weight, as determined according to the method of Monick.
14. The composition of claim 12, wherein the particulates exhibit a caking tendency breaking force of about zero with a water content of up to about 3%, by weight, as determined according to the method of Monick.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US52058774A | 1974-11-04 | 1974-11-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1048888A true CA1048888A (en) | 1979-02-20 |
Family
ID=24073258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA75229374A Expired CA1048888A (en) | 1974-11-04 | 1975-06-16 | Anticaking of linear alkyl aryl sulfonate detergents |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5153508A (en) |
| CA (1) | CA1048888A (en) |
| DE (1) | DE2527344A1 (en) |
| FR (1) | FR2289603A1 (en) |
| GB (1) | GB1491289A (en) |
| IL (1) | IL47489A (en) |
| NL (1) | NL7507939A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0122664A3 (en) * | 1983-04-14 | 1987-05-27 | THE PROCTER & GAMBLE COMPANY | Alkali earth metal salt/alkali metal surfactant dry mix cakes for longer lasting dosing dispenser |
| US4482468A (en) * | 1983-11-28 | 1984-11-13 | Lever Brothers Company | Powdered nonionic-based detergent compositions containing magnesium sulfate |
| ES2177718T5 (en) * | 1996-03-23 | 2005-12-01 | THE PROCTER & GAMBLE COMPANY | DETERGENT DRYING COMPONENT BY SPRAYING THAT INCLUDES COMPLAINANT. |
| GB2425128B (en) * | 2005-04-11 | 2010-01-13 | Unilever Plc | Drying surfactant paste |
| EP2813220A3 (en) | 2010-04-09 | 2015-06-17 | Pacira Pharmaceuticals, Inc. | Method for formulating large diameter synthetic membrane vesicles |
-
1975
- 1975-06-16 CA CA75229374A patent/CA1048888A/en not_active Expired
- 1975-06-16 IL IL47489A patent/IL47489A/en unknown
- 1975-06-19 DE DE19752527344 patent/DE2527344A1/en active Pending
- 1975-06-27 GB GB27372/75A patent/GB1491289A/en not_active Expired
- 1975-07-02 FR FR7520787A patent/FR2289603A1/en active Granted
- 1975-07-03 NL NL7507939A patent/NL7507939A/en not_active Application Discontinuation
- 1975-07-17 JP JP50087830A patent/JPS5153508A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| NL7507939A (en) | 1976-05-06 |
| JPS5153508A (en) | 1976-05-12 |
| FR2289603A1 (en) | 1976-05-28 |
| IL47489A (en) | 1978-07-31 |
| GB1491289A (en) | 1977-11-09 |
| DE2527344A1 (en) | 1976-05-13 |
| FR2289603B3 (en) | 1979-02-23 |
| IL47489A0 (en) | 1975-08-31 |
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