|Publication number||US3769222 A|
|Publication date||Oct 30, 1973|
|Filing date||Feb 9, 1971|
|Priority date||Feb 9, 1971|
|Also published as||CA971071A, CA971071A1, DE2204842A1, DE2204842C2, US3915878|
|Publication number||US 3769222 A, US 3769222A, US-A-3769222, US3769222 A, US3769222A|
|Inventors||Ding Cheng Bao, R Dickson, P Ramachandran, J Yurko|
|Original Assignee||Colgate Palmolive Co|
|Export Citation||BiBTeX, EndNote, RefMan|
|Referenced by (38), Classifications (14)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent 3,769,222 FREE FLOWIN G NONIONIC SURFACTANTS Joseph A. Yurko, Bayonne, Pallassana Ramachandran, Robinsville, Bao-ding Cheng, Highland Park, and Robert E. Dickson, Piscataway, N.J., assignors to Colgate-Palmolive Company, New York, NY. No Drawing. Filed Feb. 9, 1971, Ser. No. 114,073 Int. Cl. Clld 3/12, 1/72 U.S. Cl. 252-89 3 Claims ABSTRACT OF THE DISCLOSURE A method for converting liquid nonionic surfactants to dry free flowing form is disclosed. The new method includes the mixing of the liquid nonionic material with specific particulate carrier materials in amounts varying from 30 to 85 weight percent. Suitable carrier materials include compounds having functional properties in detergent formulations. The free flowing nonionc surfactantcarrier pre-mix is very suitable for post addition to spray dried detergent formulations in order to increase their content of nonionic surfactant.
BACKGROUND OF THE INVENTION The invention pertains to heavy duty particulate detergent formulations that include anionic, cationic, or nonionic surface active agents and detergent builders. More specifically the invention provides heavy duty detergents having a relatively high content of nonionic surface active agent.
The most commonly used surface active agents in heavy duty detergent formulations are anionic compounds having detersive properties. Typical of these anionic compounds are the higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates. These synthetic detergents are very effective in removing dirt from textile fabrics when utilized in conjunction with phosphate builders which function to soften the water being used and to provide detersive action. However, considerable controversy exists today as to the efficacy of utilizing phosphate compounds in detergent formulations due to their alleged causation of the eutrophication process in lakes, rivers and streams. Although the eutrophication process, wherein an excessive growth of plant life is promulgated in natural water bodies, is not completely understood, it is alleged that the phosphate compounds present in detergent containing waste water are a prime factor in promoting this phenomenon.
Although nonionic surfactants are not as effective as anionic surfactants in the presence of large amounts of phosphate builders, it has been discovered that when the phosphate content of a detergent formulation is substantially reduced, the nonionic surfactants appear to provide detergency properties that are superior to anionics in the same reduced phosphate content formulation. Apparently the detersive effectiveness of nonionic surfactants is affected much less by water hardness than that of the commonly used anionic surfactants. In the event that phosphate builders are totally or partially removed from detergents, the incorporation of greater and greater amounts of nonionic surfactants into detergent formulations will become very desirable.
At present, small amounts of nonionic surfactants are added to detergent formulations, primarily to reduce the amount of foam generated during the washing cycle. The most commonly used nonionic surfactants are long carbon chain alcohols ethoxylated with ethylene oxide. Typically, the nonionic ethoxamer used has a 12 to 18 carbon atom alkyl chain and an average of about to l9-ethylene oxide units. The range of ethylene oxide content that provides the greatest detergency in these surfactants usually results in a nonionic material that is a viscous liquid at room temperature and therefore unsuitable for direct addition to the dry detergent powder. However, it has been found that when a substantial amount, typically above about 5% by weight, of nonionic surfactant is incorporated into the detergent slurry before spray drying, at significant air pollution problem is encountered. This problem, known in the industry as pluming, is manifested as a dense black smoke being discharged from the spray tower.
The primary objective of the present invention is to provide a method for converting liquid nonionic surfactants to dry free flowing particulate form so that they may be post added to spray dried detergent formulations and thereby significantly increase the nonionic surfactant content of the final detergent product. The maximization of the nonionic surfactant content of the post addable free flowing powder and the selection of particularly suitable carriers for the nonionic materials are important further objectives of the invention.
SUMMARY OF THE INVENTION The present invention provides a method for obtaining free flowing particulate materials having a nonionic surfactant content of up to about by weight, and preferably above 30% by weight. The new materials are very suitable for post addition to spray dried detergent powders in order to substantially raise the nonionic surfactant content of the finished detergent product. In order to achieve an optimum post additive mixture for spray dried detergent formulations, it is desirable to maximize the loading of nonionic surfactant on the chosen carrier and also to choose carriers that contribute to the eflicacy of the detergent product. The invention provides specific carrier materials for nonionic surfactants that are capable of high nonionic loadings; some of which also contribute functional characteristics to the detergent formulation.
In accordance with the invention it has been found that silica substances in general, and microsized silicon dioxide particles in particular, are capable of carrying a high loading (about 85% by weight) of nonionic surfactant without losing their free flowing characteristics. Since microsized silicon dioxide is used as an anti-oaking agent in some detergent formulations, its use as a liquid nonionic carrier provides anti-caking properties as well as a higher nonionic content to the detergent formulation it is ultimately combined with. Further, the aforementioned silica substances, when added to a mixture of nonionic surfactant and other carrier, in accordance with the invention, substantially increases the maximum nonionic loading of the resulting post addable, free flowing mix.
Other desirable carriers for liquid nonionic surfactants are substances having building properties in the detergent formulations. In view of the desirability or reducing, and if possible eliminating, the phosphate content of detergent formulations, the use of other builders in conjunction with a higher concentration of nonionic surfactant is advantageous. In this regard it has been found that certain nonphosphate detergent builders are suitable carriers for liquid nonionic surfactants. Representative of these builder-carrier substances are the sodium salts of nitrilotriacetic acid (NTA), sodium carbonate and sodium citrate. Loadings of up to about 50% by weight of nonionic surfactant have been obtained with these buildercarriers either individually or in combination with each other in multi-component systems. The nonionic loading of these builder-carriers can be increased to over about 60 weight percent by adding a small amount, typically about 5- percent by weight, of a silica substance, preferably microsized silicon dioxide particles, to the blend. Although pyrogenic microsized silicon dioxide particles are preferred in the practice of the invention other microsized silicon dioxide particles such as silica gel and diatomaceous silica have given satisfactory results.
In further accordance with the invention, certain peroxygen bleaching agents have been found to be suitable carriers for nonionic surfactants while still retaining their free flowing properties. Peroxygen bleaching agents are advantageous carriers for liquid nonionic surfactants when it is also desirable to include a bleaching component in the final formulation. This is particularly so when only one post addition operation can be performed since both post additives can be added simultaneously in accordance with this aspect of the invention.
DESCRIPTION OF PREFERRED EMBODIMENTS In the following examples maximum loadings of liquid nonionic surfactant were applied to various particulate carriers. The maximum loading was determined by adding increasing amounts of nonionic to a given amount of carrier until the resulting mixture could not be solidified into a free flowing powder. In Examples 1-8 the nonionic surfactant utilized was an ethoxylated long chain alcohol having a chain of twelve to sixteen carbon atoms and ten to twelve ethylene oxide units. A suitable ethoxamer is available from the Shell Chemical Company under the trademark Neodol 45-11. Neodol 45-11, according to its manufacturer, is a fourteen to fifteen carbon chain ethoxylated fatty alcohol having an average of eleven ethylene oxide units. The silicon dioxide particulate material used is available under the trademark Cab-O-Sil, grade EI-I- from the Cabot Company, Cab-O-Sil is a submicroscopic particle size silica prepared by vapor phase hydrolysis of silicon tetrachloride at 1100 C. All experimental runs were made at room temperature and atmospheric pressure.
EXAMPLE 1 50 grams of molten nonionic surfactant was heated to slightly above room temperature until clear in appearance and then sprayed onto grams of colloidal pyrogenic silicon dioxide. The resulting mixture was a free flowing powder having a nonionic loading of 83.3% by weight. The following techniques were used.
(1) The liquid nonionic was sprayed onto a laboratory dish containing the silicon dioxide carrier and mixed with a spatula to produce a free flowing powder.
(2) The liquid nonionic surfactant was sprayed into an air filled plastic bag in which the silicon dioxide particles were suspended by air currents.
(3) The liquid nonionic surfactant was sprayed into a twin shell rotating blender containing the silicon dioxide particles.
The solidification mechanism of the foregoing procedures is believed to involve the coating of the liquid surfactant particles by the microscopic silicon dioxide particles rather than the absorption or adsorption of the liquid by the particles.
The free flowing powder produced by the foregoing method can be post added to spray dried detergent powders or, detergent builders and other detergent ingredients can be added to the nonionic powder to produce a finished detergent formulation.
An example of the latter procedure is to first prepare a free flowing powder consisting of 250.0 grams of a liquid nonionic surfactant and 50.0 grams of silicon dioxide carrier (83.3 weight percent nonionic). To this blend 100.0 grams of sodium salts of (NTA) and 100.0 grams of sodium citrate were added and blended to produce a finished detergent formulation having the following approximate composition:
Weight percent Nonionic surfactant 50 Silicon dioxide 10 Sodium salt of NTA Sodium citrate 20 This later formula can be utilized as a detergent itself or as an additive to other detergent systems.
EXAMPLE 2 The liquid nonionic surfactant was slowly added to a laboratory mortar containing any one or a combination of the following inorganic particulate materials: sodium carbonate, clays (such as bentonite and zeolite), diatomaceous earth (Celite Filteraid available from Johns- Manville Company) or aluminum oxide. Upon blending the liquid nonionic and the inorganic particulate material with a pestle, partial solidification of the mixture occurs. Upon setting at room temperature for about one hour a free flowing powder is obtained.
Using the foregoing method, liquid nonionic loadings as high as 50% by weight can be obtained without impairing the fiowability of the resulting solid particulate material.
EXAMPLE 3 Colloidal pyrogenic silicon dioxide, in various amounts, was thoroughly mixed into the partially solidified mixture of Example 2 before final setting. Nonionic surfactant loadings of from 50 to weight percent (based on the total inorganic content) were obtained when from about 5 to 25 percent by weight pyrogenic silicon dioxide was added to the mixture. Representative free flowing compositions obtainable by this method are:
Weight percent Nonionic 58.9
SiO -3 17.6
Nonionic 60.0 Sodium carbonate 35.0 SiO 5.0
EXAMPLE 4 From 50 to 80 weight percent of the liquid nonionic surfactant was blended with a mixture of 15 to 45 weight percent of an organic nitrogenous compound chosen from the group consisting of melamine, glycine and iminodiacetic acid and from 0 to 50 percent by weight of any one or a mixture of the inorganic carriers of Example 2. Upon mixing, partial solidification occurs. The addition of at least 5 percent by weight of colloidal pyrogenic silicon dioxide and subsequent thorough blending results in solidification of the mixture. The solidified mixture can be broken up into a free flowing, non-caking powder. The following free flowing powder compositions have been obtained by the foregoing method:
Weight percent Nonionic 63.6 Melamine 18.1 SiO 18.3
Nonionic 70 Sodium salt of glycine or iminodiacetic acid 20 SiO 10 Nonionic 80 Sodium salt of glycine or iminodiacetic acid 3 Bentonite 7 SiOz 10 Nonionic 80 Sodium salt of glycine or iminodiacetic acid 10 SiO 10 5 Nonionic 80 Sodium salt of glycine or iminodiacetic acid 3 SiO 15 EXAMPLE 5 The procedures and compositions of Example 4 were followed except that a non-nitrogenous organic material chosen from the group consisting of sodium glycolate, glycolic acid, sorbitol, and potassium sodium tartrate, was substituted for the nitrogen containing organic compounds. The following free flowing powder formulations were obtained by the foregoing method:
Weight percent Nonionic 50 Bentonite 30 Sodium glycolate 10 SiO 10 Nonionic 60 Zeolite 13 Sodium glycolate 10 Nonionic 66.6
Potassium sodium tartrate 16.8
Nonionic 50 Sorbitol 24 SiO 26 Nonionic 70 Glycolic acid SiO Nonionic 80 Sodium glycolate 8 Bentonite 2 SiO 10 Nonionic 70 Sodium glycolate 20 SiO 10 Nonionic 70 Sodium glycolate 10 Aluminum oxide 10 EXAMPLE 6 The liquid nonionic surfactant was mixed with trisodium nitrilotriacetate and sodium citrate-2H O. Partial solidification occurred on mixing. Pyrogenic silicon dioxide was then added and thoroughly mixed with the partially solidified mass. Full solidification of the mixture occurred. The resulting solid was then broken up into a free flowing, non-caking powder. The following composition has been obtained by the foregoing method:
' Weight percent Nonionic surfactant 56.6 Sodium salt of NTA 13.0 Sodium citrate 13.0 Si0 17.4
The resulting free flowing powder is very suitable for post addition to a spray dried detergent powder. Similar free flowing powder can be obtained without the addition of SiO by reducing the nonionic content to about 30 percent by weight.
6 EXAMPLE 7 The liquid nonionic surfactant was mixed with sodium carbonate and the sodium salt of NTA. Partial solidification occurs on mixing. Pyrogenic silicon dioxide was then added and thoroughly blended with the partially solidified mass. Full solidification of the mixture resulted. The resulting solid was then broken up into a free flowing nonca king powder.
The following composition has been obtained by the foregoing method:
Weight percent Nonionic surfactant 60.0 Sodium salt of NTA 15.0 Sodium carbonate 15.0
The resulting free flowing powder is very suitable for post addition to a spray dried detergent powder.
EXAMPLE 8 35 weight percent of liquid nonionic surfactant is blended together with 65 weight percent sodium perborate monohydrate. The resulting mixture is a free flowing powder suitable for post addition to spray dried detergent formulations.
Attempts to use sodium perborate tetrahydrate as a carrier for the liquid nonionic yielded a tacky non-flowable powder with a nonionic liquid content of about 20 percent by weight.
Runs similar to Examples 1-8 were made using liquid nonionic surfactants having a longer alkyl chain than Neodol 4511, i.e. 16-18 carbon atoms, and a higher ethylene oxide content, i.e. an average of 19 ethylene oxide units. A suitable liquid nonionic meeting these requirements is available from the Continental Oil Company under the trademark Alfonic 1618-78. It was found that, Alfonic 1618-78 can be solidified with less effort, i.e. in less time, than Neodol 45-11 and to approximately the same loadings.
Functional carriers that can be heavily loaded with nonionic surfactants and still remain free flowing, non-caking powders were found to include pyrogenic silicon dioxide, which functions as an anti-caking agent in the final formulation, and various detergent builders such as NTA, sodium carbonate and sodium citrate. When it is desired to incorporate a peroxygen bleach component into the detergent formulation, in addition to a nonionic surfactant component, it has been found that sodium perborate monohydrate is a surprisingly good carrier for the nonionic component since both can thereby be added in one post addition operation. Further, the addition of a small amount of pyrogenic silicon dioxide to mixtures of liquid nonionic surfactant and carrier material have been found to significantly increase the nonionic loadings of the final post addable mixture while still retaining the necessary free flowing characteristics.
Although phosphate detergent builders have also been found to be very suitable carriers for liquid nonionic surfactants, their use is not preferred at this time because of the alleged contribution of phosphates to the eutrophication process in natural bodies of water. However, in reduced phosphate content detergent formulations, all or part of the phosphate builder can be added to the formulation subsequent to spray drying as a carrier for nonionic surfactants. In this regard, it has been found that phosphate builders, such as the sodium tripolyphosphate can be loaded with up to about 30 percent by weight liquid nonionic surfactant while still retaining free flowing properties. In accordance with the invention the nonionic loading on phosphate carriers can be increased to about 50 percent by weight by adding about 5 percent by weight of a microsized silica substance to the nonionic-carrier mixture before final setting.
By providing a commercially feasible method for post adding liquid nonionic surfactants to spray dried detergent 7 formulations, the invention represents a significant step towards the substantial reduction of phosphate builders from detergent formulations without a significant decrease in cleaning eflicacy.
Although the foregoing specific embodiments are presently preferred, they should not be considered as limiting the invention. Accordingly reference should be made to the following claims to determine the full scope of the invention.
What is claimed is:
1. In the method of preparing a heavy duty detergent which includes the step of spray drying a detergent slurry to form a dry, free-flowing powder, the improvement comprising adding to said spray dried powder a free flowing pre-mix including about 85% by weight of a liquid ethoxylated alcohol nonionic surface active agent and at least 5% by weight of microsized silica particles said pre-mix being prepared by mixing said liquid nonionic with a sufficient quantity of silica particles to fully solidify said liquid nonionic.
2. The method of claim 1, wherein silica particles comprise a silicon dioxide compound.
3. The product produced by the process of claim 1.
References Cited UNITED STATES PATENTS 3,562,171 2/1971 Guida 252 186 r 3,546,123 12/1970 Stahlheber et al. 252 527 2,257,545 9/1941 Curtis ,252 129 2,882,254 4/1959 Kloepfer et a1 26041 3,306,858 2/1967 Oberle 252 99 3,337,463 8/1967 Schmolka 252 s9 10 2,623,856 12/1952 Sanders 252 135 FOREIGN PATENTS 709,515 5/1954 Great Britain. 511,415 3/1955 Canada. F 918,499 2/1963 Great Britain. 19 807,640 1/1959 Great Britain.
1,275,702 10/1961 France.
LEON D. ROSDOL, Primary Examiner P. E. WILLIS, Assistant Examiner US. Cl. X.R.
252546, 559, Dig. 1, 11
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US3915878 *||Feb 26, 1973||Oct 28, 1975||Colgate Palmolive Co||Free flowing nonionic surfactants|
|US3951877 *||Jul 13, 1973||Apr 20, 1976||Lion Fat & Oil Co., Ltd.||Heavy-duty granular detergent composition with sodium citrate builder|
|US3996149 *||Jan 2, 1975||Dec 7, 1976||Burke Oliver W Jun||Detergent compositions and detergent adjuvant combinations thereof, and processes for forming the same|
|US4049558 *||Apr 22, 1976||Sep 20, 1977||Colgate-Palmolive Co.||Free flowing phosphate ester compositions for post addition to detergents|
|US4055505 *||Dec 15, 1975||Oct 25, 1977||Colgate-Palmolive Company||Activated percompound bleaching compositions|
|US4136051 *||Jul 8, 1977||Jan 23, 1979||Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa)||Pourable washing compositions containing a luminosilicates and non-ionics and method for their preparation|
|US4166039 *||Jun 23, 1975||Aug 28, 1979||The Proctor & Gamble Company||Detergent composition and process|
|US4174291 *||Jul 8, 1974||Nov 13, 1979||The Procter & Gamble Company||Crystallization seed-containing composition|
|US4263050 *||Dec 8, 1977||Apr 21, 1981||Kao Soap Co., Ltd.||Process for preparation of granules containing viscous substance at high concentration|
|US4397777 *||Jul 18, 1980||Aug 9, 1983||Colgate Palmolive Company||Heavy duty laundry detergent|
|US4615815 *||Aug 24, 1984||Oct 7, 1986||Lever Brothers Company||Free-flowing particulate fabric-softening adjunct for use in laundry detergent compositions and method of making same|
|US4639326 *||Jul 3, 1985||Jan 27, 1987||Lever Brothers Company||Process for the preparation of a powder detergent composition of high bulk density|
|US4661358 *||Aug 23, 1985||Apr 28, 1987||Quali Tech, Inc.||Wort-sequestered divalent metal salts|
|US4695284 *||Jun 4, 1985||Sep 22, 1987||Lever Brothers Company||Cool water fabric washing process using a particulate detergent containing a nonionic and a fatty acid builder salt|
|US4713193 *||Jul 15, 1986||Dec 15, 1987||Lever Brothers Company||Stable, free-flowing particulate adjuncts for use in detergent compositions|
|US4719181 *||Dec 20, 1985||Jan 12, 1988||Warner-Lambert Company||Free flowing granular indicator material for peroxidase-like activity|
|US4869843 *||Jun 24, 1988||Sep 26, 1989||Kao Corporation||High-density granular detergent composition|
|US4919847 *||Jun 3, 1988||Apr 24, 1990||Colgate Palmolive Co.||Process for manufacturing particulate detergent composition directly from in situ produced anionic detergent salt|
|US4960452 *||Apr 22, 1988||Oct 2, 1990||Quali Tech, Inc.||Method of supplying nutrients to plants|
|US5300236 *||Sep 29, 1989||Apr 5, 1994||Lever Brothers Company, Division Of Conopco, Inc.||Composition for softening fabrics|
|US5354493 *||Oct 12, 1989||Oct 11, 1994||Henkel Kommanditgesellschaft Auf Aktien||Process for the production of surfactant-containing granulates|
|US5362413 *||Jan 14, 1991||Nov 8, 1994||The Clorox Company||Low-temperature-effective detergent compositions and delivery systems therefor|
|US5458799 *||Aug 3, 1993||Oct 17, 1995||Amway Corporation||Mix process for formulating detergents|
|US5496486 *||Jun 30, 1994||Mar 5, 1996||Amway Corporation||Process for increasing liquid surfactant loading in free flowing powder detergents|
|US5518649 *||Aug 11, 1995||May 21, 1996||Lever Brothers Company, Division Of Conopco, Inc.||Particulate detergent composition or component comprising zeolite MAP ASA carrier|
|US5635467 *||Oct 5, 1995||Jun 3, 1997||Amway Corporation||Powdered composition exhibiting increased liquid surfactant loading for free flowing powder detergents|
|US5714450 *||Mar 15, 1996||Feb 3, 1998||Amway Corporation||Detergent composition containing discrete whitening agent particles|
|US5714451 *||Mar 15, 1996||Feb 3, 1998||Amway Corporation||Powder detergent composition and method of making|
|US5990068 *||Mar 10, 1998||Nov 23, 1999||Amway Corporation||Powder detergent composition having improved solubility|
|US5998351 *||Mar 10, 1998||Dec 7, 1999||Amway Corporation||Discrete whitening agent particles method of making, and powder detergent containing same|
|US6008174 *||Oct 23, 1997||Dec 28, 1999||Amway Corporation||Powder detergent composition having improved solubility|
|US6080711 *||Mar 10, 1998||Jun 27, 2000||Amway Corporation||Powder detergent composition and method of making|
|US6177397||Mar 10, 1997||Jan 23, 2001||Amway Corporation||Free-flowing agglomerated nonionic surfactant detergent composition and process for making same|
|US6303558||May 26, 1998||Oct 16, 2001||Lever Brothers Co., Division Of Conopco||Detergent composition containing at least two granular components|
|EP0149264A1 *||Nov 2, 1984||Jul 24, 1985||Unilever N.V.||Stable, free-flowing particulate adjuncts for use in detergent compositions|
|EP0985014A1 †||May 11, 1998||Mar 15, 2000||Unilever N.V.||Detergent compositions|
|EP1133548A1 †||Nov 24, 1999||Sep 19, 2001||Unilever N.V.||Detergent compositions in tablet form|
|WO1987001012A1 *||Aug 18, 1986||Feb 26, 1987||Quali Tech, Inc.||Wort-sequestered divalent metal salts|
|U.S. Classification||510/349, 510/506, 510/443|
|International Classification||C11D1/66, C11D11/00, C11D3/26, C11D3/00, C11D3/12|
|Cooperative Classification||C11D11/0082, C11D1/72, C11D3/124|
|European Classification||C11D3/12G, C11D11/00D, C11D1/72|