CA1100376A - Low density detergent compositions - Google Patents
Low density detergent compositionsInfo
- Publication number
- CA1100376A CA1100376A CA292,062A CA292062A CA1100376A CA 1100376 A CA1100376 A CA 1100376A CA 292062 A CA292062 A CA 292062A CA 1100376 A CA1100376 A CA 1100376A
- Authority
- CA
- Canada
- Prior art keywords
- sodium
- salt
- nonionic detergent
- water soluble
- fatty alcohol
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0034—Fixed on a solid conventional detergent ingredient
Abstract
PROCESS FOR MANUFACTURING LOW DENSITY
PARTICULAR BUILT NONIONIC DETERGENT COMPOSITIONS
ABSTRACT OF THE DISCLOSURE:
Low density, particulate, built synthetic organic detergent compositions containing detersive proportions of synthetic organic nonionic detergent are made by mixing together inorganic builder(s), such as sodium tripolyphosphate, sodium silicate and sodium carbonate, water soluble organic hydrotropic salt(s), such as sodium toluene sulfonate and sodium xylene sulfonate, and water, in a crutcher mix, spray drying the crutcher mix, whereby a low density particulate base product is obtained, suitable for absorbing liquid nonionic detergent and spraying onto the surfaces of such particles a detersive proportion of a nonionic detergent, such as a polyethoxylated higher fatty alcohol. Also disclosed are processes for the manufacture of the mentioned base particles onto which nonionic detergent is subsequently sprayed, and such low density particulate base and built synthetic organic detergent compositions.
PARTICULAR BUILT NONIONIC DETERGENT COMPOSITIONS
ABSTRACT OF THE DISCLOSURE:
Low density, particulate, built synthetic organic detergent compositions containing detersive proportions of synthetic organic nonionic detergent are made by mixing together inorganic builder(s), such as sodium tripolyphosphate, sodium silicate and sodium carbonate, water soluble organic hydrotropic salt(s), such as sodium toluene sulfonate and sodium xylene sulfonate, and water, in a crutcher mix, spray drying the crutcher mix, whereby a low density particulate base product is obtained, suitable for absorbing liquid nonionic detergent and spraying onto the surfaces of such particles a detersive proportion of a nonionic detergent, such as a polyethoxylated higher fatty alcohol. Also disclosed are processes for the manufacture of the mentioned base particles onto which nonionic detergent is subsequently sprayed, and such low density particulate base and built synthetic organic detergent compositions.
Description
03~76 This invention relates to a process for manufacturing a low density, particulate, built synthetic organic detergent com-position. More particularly, it relates to the inclusion of a small proportion of an organic hydrotropic salt in a crutcher mix before spray drying a substantially inorganic particulate base com-position onto which nonionic detergent is subsequently coated. It has been found that the presence of the hydrotrope in the crutcher mix results in production of substantially lower density base and final detergent composition particles. Also with the invention are a method for manufacturing such low density base particles, plus particulate base and built synthetic organic detergent com-positions which may be made by such methods.
Recently, built particulate synthetic organic detergents based on nonionic detergents have been found to posses various advantages over the previously conventional heavy duty, built, particulate anionic synthetic organic detergents. However, when manufacture of the built nonionic detergent compositions was under-taken by methods previously used for producing such counterparts, such as by spray drying the final composition from a crutcher mix, various problems were encountered. The most objectionable of these was the fuming of the nonionic detergent during the spray drying process, causing objectionable smoke from the spray drying plant and resulting in the loss of the detergent. In addition to being objectionable from the environmental standpoint the process is more costly and results in the production of detergent composition part-icles o widely varying active c~, 11003~76 ingredient (nonionic detergent) content, depending on spray tower conditions. Accordingly, post-addition of most or all of the nonionic detergent has been suggested and commercial products have been made by such method as disclosed in United States patents 3,838,072; 3,849,327; 3,886,098;
and 3,971,726; and German Offenlegungsschrift 2,514,677.
Although post-addition of the nonionic detergent, usually b~ spraying a melt thereof onto the surfaces of moving particles of a base composition, which is usually substantially inorganic and constituents the remainder of the detergent composition or st of the remainder thereof, results in a useful product, generally such product will be of a higher bulk density than that previously produced when anionic detergents (including soaps) were present in the crutcher mix. In some instances the higher density particles are acceptable and even desirable but in many cases it is important to produce low bulk density products, such as those to which the consumer has previously been accustomed, the bulk densities of which are usually in the 0.3 to 0.5 g./cc. range. It has been found that when a substantially inorganic crutcher mix is spray dried the beads produced thereby, after nonionic detergent addition, will be of a ~igher density than desired, such densities often being in the 0.55 to 0.75 g./cc. range. When nonionic detergent is post-sprayed or otherwise coated onto the base composition part-icles the densities thereof are increased slightly or sometimes may remain about the same. Thus, so as to be able to produce a commer-cial built heavy duty nonionic detergent product, efforts have been made to decrease the bulk density of the spray dried beads of the base composition and to make a low density particulate detergent from such base particles.
The use of soap and other anionic detergents, in small quantities, as constituents of an essentially inorganic crutcher mix has been found to lower the bulk density of the dried particles resulting from spray drying. Such effects are described in United States patent 3,971,726 and in the German Offenlegungsschrift pre-viously mentioned. However, the use of such detersive products, even in comparatively small proportions, may promote foaming, which is often undesirable for particular detergent compositions.
Furthermore, with the use of small quantities of anionic detergents, as described in the German Offenlegungsschrift, certain specific operating conditions may have to be maintained in the spray tower and in some cases only particular compositions will be capable of being produced in the desired low bulk density range. Such un-desirable properties in the product and such restrictions on the compositions and methods employed may be obviated by the present processes and satisfactory compositions may be made, utilizing them.
~i ': llU~376 In accordance with the present invention there is provided a process for manufacturing a low density, particulate, built synthetic organic detergent composition which comprises mixing together a plurality of components of a crutcher mix comprising inorganic builder salt(s) selected from the group consisting of water soluble polyphosphates, carbonates, silicates, borates, bicarbonates, and phosphates, water soluble organic hydrotropic salt(s) and water in such proportions that when subsequently dried the water soluble organic hydrotropic salt(s) present significantly reduces the density of the product, drying the mix and applying onto the surfaces of particles of the dried mix a detersive proportion of nonionic detergent.
The inorganic builder(s) may be sodium tripoly-phosphate, sodium silicate and sodium carbonate, often with inorganic filler salt~s), such as sodium sulfate. The water soluble organic hydrotropic salt(s) may be sodium toluene sulfonate and/or sodium xylene sulfonate. The water is usually present to the extent of 0.2 to 5% in the crutcher mix and preferably 1.2 to 2% in the final product. The density of the product is significantly reduced (to 0.25 or 0.3 to 0.45 or 0.5 g./cc. [0.25 to 0.45 g./cc. in the base composition particles]~. The detergent is normally applied to the surfaces of particles of the dried mix by spraying in an amount, of usually 5 to 17% and preferably 7 to 15~. Preferably the nonionic detergent is higher fatty alcohol polyethylene oxide condensate. Also, within the invention are a process for ma~ing the base Co~pofiition particles to be spray treated and preferred base and final detergent compositions.
The base detergent composition, sometimes referred to as the carrier composition, will usually be composed substantially of inorganic materials, primarily inorganic B _5_ 110(~!376 builder(s) and preferably also inorganic filler salt(s). However, it may also contain other desirable constituents of the final detergent composition, except the nonionic detergent, which are sufficiently heat stable to withstand a drying operation, such as conventional spray drying. Preferably, any anti-redeposition agent, such as sodium carboxymethyl cellulose, and any quantity of sodium silicate in excess of about 15%, preferably 10%, on a base composition basis, will be post-added, before, after or with the nonionic detergent, preferably as particulate solids. If desired, flow promoting clays such as that sold under the trademark Satintone, may also be post-added but use thereof is not normally needed for the manufacture of a sufficiently free flowing, non-tacky and non-caking product. Colorants, perfumes, fluorescent brighteners, fungicides, herbicides and other adjuvants may also be post-added and when sufficiently soluble, may be dispersed or dis-solved in the nonionic detergent and applied to the base particles with it, as by spraying.
The builder components of the present compositions are preferably water soluble polyphosphates, carbonates, silicates, borates, bicarbonates and phosphates, usually as the sodium or potassium salts, e.g., pentasodium tripolyphosphate, tetrapotassium pyrophosphate, sodium carbonate, potassium bicarbonate, sodium silicate (Na20:SiO2 = 1:2.35), borax and disodium hydrogen phos-phate, but it is contemplated that organic builder salts may also be employed, at least in X
~IU0376 partial replacement of the inorganic builders. Such replacement may also be made with water insoluble builders such as the sodium aluminosilicates preferably zeolites of Types A or X, crystalline or amorphous, various examples of which are disclosed in United States Patent 2,882,243; Belgian Patents 813,581 and 835,351; German Offenlegungsschriften 2,412,837 and
Recently, built particulate synthetic organic detergents based on nonionic detergents have been found to posses various advantages over the previously conventional heavy duty, built, particulate anionic synthetic organic detergents. However, when manufacture of the built nonionic detergent compositions was under-taken by methods previously used for producing such counterparts, such as by spray drying the final composition from a crutcher mix, various problems were encountered. The most objectionable of these was the fuming of the nonionic detergent during the spray drying process, causing objectionable smoke from the spray drying plant and resulting in the loss of the detergent. In addition to being objectionable from the environmental standpoint the process is more costly and results in the production of detergent composition part-icles o widely varying active c~, 11003~76 ingredient (nonionic detergent) content, depending on spray tower conditions. Accordingly, post-addition of most or all of the nonionic detergent has been suggested and commercial products have been made by such method as disclosed in United States patents 3,838,072; 3,849,327; 3,886,098;
and 3,971,726; and German Offenlegungsschrift 2,514,677.
Although post-addition of the nonionic detergent, usually b~ spraying a melt thereof onto the surfaces of moving particles of a base composition, which is usually substantially inorganic and constituents the remainder of the detergent composition or st of the remainder thereof, results in a useful product, generally such product will be of a higher bulk density than that previously produced when anionic detergents (including soaps) were present in the crutcher mix. In some instances the higher density particles are acceptable and even desirable but in many cases it is important to produce low bulk density products, such as those to which the consumer has previously been accustomed, the bulk densities of which are usually in the 0.3 to 0.5 g./cc. range. It has been found that when a substantially inorganic crutcher mix is spray dried the beads produced thereby, after nonionic detergent addition, will be of a ~igher density than desired, such densities often being in the 0.55 to 0.75 g./cc. range. When nonionic detergent is post-sprayed or otherwise coated onto the base composition part-icles the densities thereof are increased slightly or sometimes may remain about the same. Thus, so as to be able to produce a commer-cial built heavy duty nonionic detergent product, efforts have been made to decrease the bulk density of the spray dried beads of the base composition and to make a low density particulate detergent from such base particles.
The use of soap and other anionic detergents, in small quantities, as constituents of an essentially inorganic crutcher mix has been found to lower the bulk density of the dried particles resulting from spray drying. Such effects are described in United States patent 3,971,726 and in the German Offenlegungsschrift pre-viously mentioned. However, the use of such detersive products, even in comparatively small proportions, may promote foaming, which is often undesirable for particular detergent compositions.
Furthermore, with the use of small quantities of anionic detergents, as described in the German Offenlegungsschrift, certain specific operating conditions may have to be maintained in the spray tower and in some cases only particular compositions will be capable of being produced in the desired low bulk density range. Such un-desirable properties in the product and such restrictions on the compositions and methods employed may be obviated by the present processes and satisfactory compositions may be made, utilizing them.
~i ': llU~376 In accordance with the present invention there is provided a process for manufacturing a low density, particulate, built synthetic organic detergent composition which comprises mixing together a plurality of components of a crutcher mix comprising inorganic builder salt(s) selected from the group consisting of water soluble polyphosphates, carbonates, silicates, borates, bicarbonates, and phosphates, water soluble organic hydrotropic salt(s) and water in such proportions that when subsequently dried the water soluble organic hydrotropic salt(s) present significantly reduces the density of the product, drying the mix and applying onto the surfaces of particles of the dried mix a detersive proportion of nonionic detergent.
The inorganic builder(s) may be sodium tripoly-phosphate, sodium silicate and sodium carbonate, often with inorganic filler salt~s), such as sodium sulfate. The water soluble organic hydrotropic salt(s) may be sodium toluene sulfonate and/or sodium xylene sulfonate. The water is usually present to the extent of 0.2 to 5% in the crutcher mix and preferably 1.2 to 2% in the final product. The density of the product is significantly reduced (to 0.25 or 0.3 to 0.45 or 0.5 g./cc. [0.25 to 0.45 g./cc. in the base composition particles]~. The detergent is normally applied to the surfaces of particles of the dried mix by spraying in an amount, of usually 5 to 17% and preferably 7 to 15~. Preferably the nonionic detergent is higher fatty alcohol polyethylene oxide condensate. Also, within the invention are a process for ma~ing the base Co~pofiition particles to be spray treated and preferred base and final detergent compositions.
The base detergent composition, sometimes referred to as the carrier composition, will usually be composed substantially of inorganic materials, primarily inorganic B _5_ 110(~!376 builder(s) and preferably also inorganic filler salt(s). However, it may also contain other desirable constituents of the final detergent composition, except the nonionic detergent, which are sufficiently heat stable to withstand a drying operation, such as conventional spray drying. Preferably, any anti-redeposition agent, such as sodium carboxymethyl cellulose, and any quantity of sodium silicate in excess of about 15%, preferably 10%, on a base composition basis, will be post-added, before, after or with the nonionic detergent, preferably as particulate solids. If desired, flow promoting clays such as that sold under the trademark Satintone, may also be post-added but use thereof is not normally needed for the manufacture of a sufficiently free flowing, non-tacky and non-caking product. Colorants, perfumes, fluorescent brighteners, fungicides, herbicides and other adjuvants may also be post-added and when sufficiently soluble, may be dispersed or dis-solved in the nonionic detergent and applied to the base particles with it, as by spraying.
The builder components of the present compositions are preferably water soluble polyphosphates, carbonates, silicates, borates, bicarbonates and phosphates, usually as the sodium or potassium salts, e.g., pentasodium tripolyphosphate, tetrapotassium pyrophosphate, sodium carbonate, potassium bicarbonate, sodium silicate (Na20:SiO2 = 1:2.35), borax and disodium hydrogen phos-phate, but it is contemplated that organic builder salts may also be employed, at least in X
~IU0376 partial replacement of the inorganic builders. Such replacement may also be made with water insoluble builders such as the sodium aluminosilicates preferably zeolites of Types A or X, crystalline or amorphous, various examples of which are disclosed in United States Patent 2,882,243; Belgian Patents 813,581 and 835,351; German Offenlegungsschriften 2,412,837 and
2,412,839; and Austrian Patent Applications A 4484/73;
A 4642/73; A 4666/73; A 4717/73; A 4750/73; A 4767/73;
A 4787/73; A 4788/73; A 4816/73; and A 4888/73. Additionally, such insoluble builders are described in the text Zeolite Molecular Sieves by Donald ~. Breck, published in 1974 by John Wiley & Sons, specifically being listed in Table 9.6 at pages 747-749 thereof. Of the builders present normally at least 50% will be ~ater soluble inorganic builder salts.
Preferably, this proportion will be at least 80%, more preferably, at least 9a% and most preferably, 100~. Although it is not necessary to incorporate a filler salt in the base beads or in the final detergent composition generally the presence of such material will be desirable. Among the best of the fillers, contributing particle strength, stability and flowability at relatively little cost, is sodium sulfate, which will u~ually be substantially all or all of the filler present, usuall~ heing over 50~ and preferably over 90% of the filler content.
However, other water soluble and non-deliquescent inorganic salts which are heat stable may also be employed, such as sodium chloride, sometimes found as an impurity in one of the product components, potassium sulfate, sodium bisulfate and potassium chloride.
The hydrotropic salt, which has been found to aid in the manufacture of the low density carrier particles of this invention, may be any such compound which has the property of promoting water solubility of only slightly soluble compounds and of aiding in the production of low density carrier and final product particles, especially when crutcher mixes of a base composition are spray dried at elevated temperatures. The preferred compounds of this type are water soluble salts of substituted or unsubstituted ben-zene sulfonic acids, such as the sodium and potassium salts thereof (the alkali metal salts), especially the sodium salts. Although alkali metal benzene sulfonates, such as sodium benzene sulfonate, are useful hydrotropes and may be employed in the processes of this invention, it is preferred to have one or more hydrogens of the benzene ring substituted, as by a lower alkyl group of 1 to 4 car-bon atoms, preferably 1 to 2 carbon atoms and most preferably one carbon atom (methyl), e.g., sodium toluene sulfonate, sodium xylene sulfonate, potassium toluene sulfonate and corresponding salts of cumene, mesitylene, ethylbenzene and .~
110(~376 pseudocumene. Usually, the sulfonates are mixtures of isomers, with para- and ortho-configurations normally and preferably dominat-ing, e.g., sodium p-methyl benzene sulfonate, sodium O,O-di-methyl sulfonate, sodium o,p-dimethyl benzene sulfonate. Also, mixtures of the various different types of hydrotropes may be used, e.g., sodium toluene sulfonate and sodium xylene sulfonate or the corres-ponding potassium salts.
The nonionic detergents employed are preferably poly-ethoxylated higher fatty alcohols such as the water soluble con-densation products of 3 to 15 mols of ethylene oxide, preferably 7 to 11 mols, and higher fatty alcohols of 10 to 18 carbon atoms, preferably 12 to 15 carbon atoms. Such nonionic detergents melt or soften sufficiently to be sprayable in droplet form at a tempera-ture below 45C. A preferred commercial product, which is the con-densation product of a higher fatty alcohol mixture of 12 to 15 carbon atoms with about 7 mols of ethylene oxide per mol of fatty alcohol, is sold under the trademark Neodo ~ 25-7, manufactured by Shell Chemical Co. Other commercial nonionic compounds of this general type which are also suitable include: Neodol 45-11, (also made by Shell Chemical Company); Alfonic~ 1618-65, which is a 16 to 18 carbon alkanol ethoxylated with an average of 10 to 11 mols of ethylene oxide per mol, manufactured by Continental Oil Company;
and Plurafac~ B-26, manufactured by BASF-Wyandotte.
110(1 376 In addition to the preferred polyethoxylated higher fatty alcohols and similar alkanols there may also be used, at least in part, e.g., up to 25 or 50%, various other nonionic detergents such as are described at length in McCutcheon's _etergents and Emulsifiers, 1973 Annual and in Surface Active Agents, Vol. II, by Schwartz, Perry and Berch (Interscience Publishers, 1958). Such nonionic detergents are usually pasty or waxy solvents at room temperature (20C.) and are either sufficiently water soluble to dissolve promptly in water, especially in the presence of the hydrotrope, or quickly melt and disperse therein at the temperature of the wash water, as when that temperature is a~ove 40 or 50C. They will normally not be fluid at room temperature because in such state they might tend to make a tacky agglomerate of the final particulate detergent, which could be poorly flowing and could lump or set on storage. Typical useful nonionic detergents which may be employed, providing that they are satisfactorily detersive in the present compositions at the concentrations utilized, e.g., Q.l to 0.2% of detergent composition in ~ash water, are the poly-lower alkenoxy derivatives that are usually prepared by the condensation of lo~er (2 to 4 carbon atoms) alkylene oxide, e.g., ethylene oxide, pr~pylene oxide (~ith enough ethylene oxide to make a water soluble productl, with a compound having a hydrophobic B -lo-~1~03!76 : ~
., ' ,:
e.g., hydrocarbon, chain containing one or more active hydrogen atoms, such as higher alkyl phenols, higher fatty acids, higher fatty mercaptans, higher fatty amines, higher fatty polyols and the ~
higher fatty alcohols previously mentioned. Generally, such com- ~ ;
pounds will be alkoxylated with an average of about 3 to 30, pre-ferably 3 to 15 and more preferably 7 to 11 alkylene oxide units.
The most preferred nonionic detergents are those represented by the formula RO(C2H4O)nH, wherein R is the residue of a linear saturated primary alcohol (an alkyl) of 12 to 15 carbon atoms and n is an integer from 7 to 11. Among additional nonionic detergents that may be employed are the Igepals~9 (GAF Co. Inc.); Pluronics~
(RASF-Wyandotte); Poly-Tergents~ (Olin Corp.); and Amidoxes~
(Stepan Chemical Co.).
In addition to the adjuvants previously mentioned, which ~ are preferably post-added to the spray dried base particles, small I proportions of anionic and amphoteric detergents may also be pre-sent in the base beads or may be post-added. Such are not neces-sary for the production of the desired detergent particles and if employed are normally present in small proportions, e.g., 0.5 to 2%. Examples of such materials include the alkali metal, prefer-ably sodium, higher alkyl benzene sulfonates having 12 to 15 carbon atoms in their alkyl groups, which are preferably linear; higher fatty alcohol sulfates; higher alkyl sulfonates; higher olefine sulfonates; and polyethoxylated higher fatty alcohol sulfates. In such cases the higher alkyl or alkene groups 110(~376 are usually of 1 to 20 or 12 to 18 carbon atoms and polyethoxyla-tion is to the extent of 3 to 30 or 3 to 15 alkylene oxides per mol. Instead of the synthetic anionic organic detergents mentioned the ordinary fatty acid soaps, usually sodium soaps of mixed higher fatty acids of 8 to 18 carbon atoms, such as those obtained from tallow and coconut oil, may desirably be substituted in whole or in part and mixtures of the anionic detergents may be used, with the total amount being within the percentage range previously given.
Instead of the anionic detergents amphoteric surface active agents may be employed. These are usually higher fatty carboxylates, phosphates, sulfates or sulfonates which contain a cation sub-stituent such as an amino group which may be quaternized, for ex-ample, with lower alkyl groups, or may have the chain thereof ex-tended at the amino group by condensation with a lower alkylene oxide, e.g., ethylene oxide. Representative commercial water sol-uble amphoteric organic detergents include Deriphat~ 151 and Miranol~ C2M. Sometimes it may be desirable to employ small pro-portions of cationic organic surface active agents, especially as anti-static or softening materials. Typical of such compounds are thoduomeens~ T/12 and T/13, which are ethylene oxide condensates of N-tallow trimethylene diamines (Armour Industrial Chemical Company) and Ethylqua ~ 18/12, 18/25 and 0/12, which are poly-ethoxylated quaternary ammonium chlorides (Armour Industry Chemical Co.). Various other synthetic detergents and surface active agents which may be employed are disclosed in the McCutcheon and Schwartz et al. texts.
To manufacture the low density particulate built synthetic organic detergent composition and the corresponding low density base composition particles, which are usually substantially inorganic with respect to the normally solid components thereof, an aqueous solution-dispersion, commonly referred to as a crutcher mix, is prepared, containing the various heat-resistant components of the final product, except the nonionic detergent and any materials best post-added. To save energy and to increase throughput of the drying equipment the crutcher mix ~ill usually be of as high a solids content as feasible, e.g. about 50 to 80%, with the balance, about 2Q to 50%, being watex. More water may be used but th~n energy demands are increased, tower throughputs are diminished, products resulting may be tackier and poorer flo~ing and often the desired lo~ density ba$e and final detergent composition particles will not be obtained. ~hen the moisture content of the crutcher mix is about 20 to 50% the ~ater soluble, inorganic buildex salt(s~ content ~ill be about 10 to 50%, inorganic filler s~alt(s~ content will be about 5 to 50% and the water soluhle~ organic hydrotropic salt(s) content will be ahout Q.2 to 5%. ~hen no inorganic filler salt is present the inorganic builder salt content may he 110(~376 such as to be the balance of the composition, in addition to the water and hydrotrope (and any other heat stable adjuvants, etc., present). Sodium tripolyphosphate, normally charged as pentasodium tripolyphosphate, is a pre-ferred builder salt and usually constitutes at least half of the builder salt in the crutcher. Correspondingly, the preferred filler salt is sodium sul-fate and generally this is at least half of the filler salt content in the crutcher mix. Of course, the content of water in the crutcher mix will be sufficient to satisfactorily dissolve-disperse the other components present.
Although other drying methods may be employed, such as drum drying, tray drying, fluidized bed drying, film drying, etc., the most preferred method is spray drying, wherein the crutcher mix is sprayed at an elevated pressure, usually from 3 to 50 kg./sq. cm., preferably 20 to 40 kg./sq. cm., through a spray nozzle into a drying tower, through which drying air passes to dry the resulting droplets of crutcher mix to globular, low density, free flowing particles. Instead of spray nozzles, equivalent atomizers of other designs may also be used. The preferred spray tower design is counter-current, with the height of the tower usually being from 5 to 25 meters and with the entering hot air, usually the gaseous products of combustion of oil or gas, being at a temperature in the range of 200 to 400C. ar.d with the outlet air usually at a temperature in the range of 50 to 90C. Concurrent tower designs may also be employed wherein similar inlet and outlet air temperatures obtain. It has been mentioned in German Offenlegungsschrift 2,514,677 that low density beads are more readily produced utilizing con-current spray drying than result from countercurrent drying but with the method of the present invention low density products can be obtained with either type of tower. Countercurrent drying is preferred and has the bene-fits of greater efficiency of the drying operation because the thermal grad-ient for removal of the moisture in the partially dried product, near the exit of the tower, is greater.
The nozzle size for producing droplets of crutcher mix of desired 11~3~
size is chosen to produce base particles in the 6 to 160 mesh, United States Standard Sieve Series, range. Preferably, the product is substantially of particles in such range when it is removed from the spray tower but any off-size particles, such as may be from 2 to 10% by weight, as result outside such size range, may be removed by screening, may be size-reduced to the de-sired size range or may be recycled in the same or a subsequent crutcher mix.
In some cases the 6 to 160 mesh product may be further screened to a narrower size range, such as 8 to 100 mesh. Also, spray characteristics may be altered so as to obtain substantially such a product from spray drying, with-out the need for further screening or size-reduction.
After drying is complete and the particles in the desired size range are obtained the nonionic detergent is applied to the surfaces thereof, preferably by spraying molten detergent, which may be in concentrated aqueous solution but preferably is free of water, onto the surfaces of the tumbling base particles in an inclined drum, through which the particles progress from an elevated feed end to the discharge end. Instead of an inclined drum one may also use fluidized beds of various conventional designs and other commer-cial mixers, such as those of the Schugi type. The proportion of nonionic detergent, preferably polyethoxylated higher fatty alcohol, will desirably be from 4 to 15% and the beads onto which it is sprayed will contain about 3 to 16% moisture, preferably 5.6 to 13.3% and more preferably, 5.6 to 11.1% of water, so that the final product will constitute about 2.5 to 15%, 5 to 12%, or 5 to 10% of water. Of course, the moisture content of the base beads may be higher when additional moisture-free constituents are to be post-added.
The proportions of adjuvant materials will generally be held to less than 15%, preferably less than 10% and more preferably less than 5%
total of the total product and the proportions of individual adjuvants will be less than 5% each, preferably less than 2% each and more preferably less than 1% each, in most cases. Thus, the total range of ad~uvant content may be from about 0 or 1 to 15%, preferably from 1 to 5% and the individual component concentrations may be from 0 or 0.1 to 5%, preferably 0.2 to 1%.
If a bleaching agent, such as sodium perborate, usually as the tetrahydrate and activated, is to be incorporated with the detergent, greater percentages thereof, e.g., 5 to 40%, preferably 10 to 30%, may be present. Thus, sodium perborate is not considered as one of the ordinary adjuvants previously dis-cussed. If used, it should be post-added.
For superior products it has been found desirable for the propor-tion of builder salt or filler salt to be within the range of 3:1 to 1:2, preferably 2:1 to 1:1.5. The bulk density of the base beads is in the range of 0.2 to 0.45 g./cc. and that of the final product beads is in the range of 0.3 to 0.5 g./cc. Preferably the bulk densities will be from 0.2 to 0.35 and 0.3 to 0.45 g./cc., respectively.
Preferred detergent compositions of this invention comprise about 20 to 40% of sodium tripolyphosphate, 3 to 15% of sodium carbonate, 5 to 15%
of sodium silicate of Na20:SiO2 ratio in the range of 1:1.6 to 1:3, 0 to 5%
of borax 1 to 3% of sodium toluene sulfonate or sodium xylene sulfonate 20 to 50% of sodium sulfate, 4 to 15% of higher fatty alcohol polyethylene oxide condensation product nonionic detergent and 5 to 12% of water. In such pro-ducts the higher fatty alcohol ethylene oxide condensation product is one which melts or softens sufficiently to be sprayable in droplet form at a temperature below 45C. and in the process of the invention it is melted and sprayed onto the surfaces of the spray dried particles of base material at a temperature below 55C., while such particles are in motion and are at a temperature below 45 & . and greater than 10C. A highly preferable process is one wherein the moisture content of the crutcher mix is about 30 to 45%, the crutcher mix of such a composition as to result in a spray dried final detergent composition product which, when it includes about 7 to 13% of poly-ethoxylated higher fatty alcohol nonionic detergent post-added to the spray dried base beads, includes 28 to 38% of sodium tripolyphosphate, 3 to 8% of sodium carbonate, 5 to 10% of sodium silicate of ~a20:SiO2 ratio of 1:2 to 1:2.4, 1.2 to 2% of sodium toluene sulfonate (or sodium xylene sulfonate), 0.5 to 2% of borax, 30 to 42% of sodium sulfate and 5 to 10% of moisture. In such a product the nonionic detergent is preferably a condensation product of a higher fatty alcohol of 12 to 15 carbon atoms and about 7 mols of ethylene oxide per mol of fatty alcohol, which product is sold under the trademark Neodol 25-7. In such process, the crutcher mix, at a temperature of 80 to 105C., is sprayed into the spray drying tower, preferably a countercurrent tower, with the tower drying air inlet temperature being in the range of 200 to 400C., and the spraying is such as to result in droplets which dry to particles of a mixture of sizes substantially in the 6 to 160 mesh range. To produce such particles a nozzle orifice of a 0.2 to 0.8 mm. diameter may be employed. In the post-spraying operation the nonionic detergent is sprayed onto the surfaces of the tumbling particles of base beads in a rotating in-clined drum which may be at an angle of about 5 to 15 and which rotates at a speed of about 5 to 50 r.p.m., The nonionic detergent is at a temperature of 35 to 50C. when sprayed on the tumbling particles, which are at a temperature of 20 to 45C.
The process for manufacture of the base or carrier beads has been described pTeviously in conjunction with the overall process for the manufac-ture of detergent composition particles. However, allowing for about 10% ofnonionic detergent being post-added to the base beads, the preferred and the most preferred contents of various components of the beads are somewhat different, being 22 to 44% of sodium tripolyphosphate, 3.3 to 16.7% of sodium carbonate, 5.6 to 16.7% of sodium silicate, 1.1 to 3.3% of sodium toluene sul-fonate or sodium xylene sulfonate, 0 to 5.6% of borax, 22 to 56% of sodium sulfate and 5.6 to 13.3% of water, with the more preferred ranges being 31.1 to 42.2%; 3.3 to 8.9%; 5.6 to 11.1%; 1.3 to 2.2%; 0.5 to 2.2%; 33 to 47%; and 5.6 to 11.1%, respectively.
The various advantages of the described processes and the composi-tions resulting have been referred to previously but will be recounted 110~376 briefly here. Principally, a built heavy duty nonionic detergent is manufac-tured which is in particulate form, of desired low density, non-tacky, non-caking and free flowing. It is made by an economical process which allows for ready variation in active detersive ingredient content of the composition.
The process is environmentally acceptable, producing no undesirable smoke or fumes from the drying means, such as a spray tower. Also, tower throughput is increased and energy consumption is decreased. Despite the comparatively high contents of nonionic detergent in the final particulate composition such detergent is readily sorbed by the hydrotrope-containing beads and compara-tively short mixing times, e.g., 1 to 5 minutes, are sufficient. The pre-sence of the hydrotrope in the product, while not interfering with the pro-perties of the nonionic detergent, does aid in solubilizing some compara-tively insoluble soiling substances often present on laundry and also aids in promoting solubility of any poorly soluble adjuvants which may be present in the detergent, thus preventing unwanted depositing thereof onto the laundry.
For example, colorants in detergents may be prevented from being deposited on laundry fabrics of the laundered items. However, the main advantage of the invention is in the production of desired low density particulate products and in this respect the present process, utilizing a hydrotropic salt of the type described, can produce a lower density product than is obtained with soap, mixtures of soap and nonionic detergent, and anionic detergents, em-ployed in similar quantities.
The reason for the desirable effects noted with the present pro-cesses is not clear. It has been theorized that the hydrotropic salt aids in the production of a more homogeneous crutcher mix and thereby avoids the pro-duction of weak points or rupture-prone locations on the droplet or bead as drying is effected. Therefore, the bead can swell to a larger size and main-tain such size as it is dried, leading to the production of a lower density product. However, even if such theory should become verified it would still be unexpected that the small proportion of hydrotropic salt utilized would be -1~-X
1101~3~76 sufficiently effective to significantly modify the characteristics of a crutcher mix or base droplet containing such a high percentage of inorganic salts.
The detergent compositions of this invention, when employed in the same manner as conventional heavy duty particulate detergents, at normal use concentrations, e.g., 0.1 to 0.2%, in cold, warm or hot wash waters, result in very satisfactory cleaning of the articles of laundry being washed. Addi- r tionally, the particulate detergent may be made into a paste with water for treatment of heavily soiled areas of the laundry and the presence of the 10hydrotrope assists in loosening such soil so that it may be more readily re-moved during washing.
The following examples illustrate but do not limit the invention.
Unless otherwise mentioned, all parts in the specification are by weight and all temperatures are in C.
A crutcher mix is made of 23.9% of sodium tripolyphosphate, 3.6% of sodium carbonate, 5.1% of sodium silicate, 1.1% of sodium toluene sulfonate, 0.7% of borax, 25.6% of sodium sulfate and 40% of water. All the components except the sodium silicate and the water are added as anhydrous powders.
Sodium silicate is added as 10.2% of a 50% aqueous solution and its Na20:SiO2 ratio is 1:2.35. The aqueous composition is mixed in a conventional heated detergent crutcher for a period of about 15 minutes (polyphosphate is added last) and is pumped by a high pressure pump (Triplex) at a pressure of 25 kg./
sq. cm. and at a temperature of 95C. into the top of a 20 m. tall spray tower through a plurality of 0.5 mm. dia. nozzles, which create a spray of droplets of sizes substantially in the 6 to 160 mesh, United States Standard Sieve Series, range, which produce beads of a similar size. The drying air, entering the bottom of the tower, is at a temperature of about 300C. and when it leaves the tower at the top it is at a temperature of about 90C.
The droplets of sprayed crutcher mix, falling through the tower, have an 1~003!76 average residence time therein of about one minute, with residence time modi-fications, depending on particular drying conditions, being variable to from 30 seconds to three minutes. The spray dried beads, comprising over 95% of particles in the desired 6 to 160 mesh range, are withdrawn from the tower at a temperature of about 45C., after some preliminary cooling at the base of the tower. The beads at this temperature are delivered to an inclined rotat-ing drum wherein there is sprayed onto the surfaces thereof a melt of Neodol 25-7 (higher fatty alcohol mixture of about 12 to 15 carbon atoms poly-ethoxylated with about 7 mols of ethylene oxide per mol) at a temperature of about 40C. The drum is inclined at an angle of about 7 and residence time of the particles therein is about 3 to 5 minutes. The spray nozzles are such that the droplets of spray are of sizes corresponding to about 100 to 200 mesh ant the sprays are directed onto the surfaces of the tumbling particles.
During the tumbling the product is cooled somewhat and after removal from the tumbling drum it is additionally cooled to a temperature in the 20 to 30C.
range, after which it is ready for packaging.
The product made is an excellent heavy duty laundry detergent, especially good for cold and warm water use, wherein it is superior to many detergents based on anionic synthetic active ingredients. Its bulk density before packaging is about 0.34 g./cc., having been increased slightly during the add-on of nonionic detergent, from about 0.29 g./cc. The moisture con-tent to which the crutcher mix content had been dried to form the base beads is 7.7%. The final detergent composition is of the following analysis: 33%
sodium tripolyphosphate; 5% sodium carbonate; 7% sodium silicate; 1.5% sodium toluene sulfonate; 1% borax; 35.5% sodium sulfate; 10% nonionic detergent;
and 7% water.
In a control experiment, when the same operational steps are re-peated with the same composition except that the sodium toluene sulfonate is omitted from the crutcher mix, the density of the spray dried base beads re-sulting is over 0.5 g./cc. and that of the finished detergent composition llOV376 particles is 0.59 g./cc., which is objectionably high for a product designedto be commercially marketed in replacement of conventional spray dried deter-gent compositions.
In modifications of the process of the invention the drying of the crutcher mix is effected by drum and tray drying and the products resulting are size reduced to the desired 6 to 160 mesh and narrower ranges. By such method a desirable lowering of the density of the product into the 0.3 to 0.5 g./cc. range is obtained whereas without the presence of the hydrotropic salt a higher density, outside such range, may result. The bulk density may be desirably lowered further by aerating the mix before drying, with the hydrotropic salt present therein. Also, further lowerings of the bulk den-sity of the drum dried and tray dried products, as well as those made by spray drying, as described above, are obtained when the particle size ranges are from 8 to 140 and 8 to 100 mesh, with particles outside such ranges being removed and subjected to size reduction or recycling treatments.
In other modifications of the described experiment, utilizing spray drying, the proportions of the various components of the crutcher mix are individually modified, +10, +20, and +30%, while still remaining in the ranges specified, with the proportions of other components remaining con-stant. In such cases the processing conditions are also changed, with thecrutcher mix temperature being modified to 85, 90 and 100C., the spray nozzle cross-sectional area being increased and decreased 10% and the drying air inlet temperature being changed to 250 and 350C. in various experi-ments. Also, in addition to utilizing the inclined drum described, the angle thereof is modified to 5 and 12 and in some cases the nonionic detergent is applied in a Schugi apparatus or is directed into a fluidized bed of the base particles. The temperature of the base beads is changed +5 C., as is that of the nonionic detergent being sprayed onto them. In some instances 0.6% of perfume is added with the nonionic (dissolved therein). In all such cases useful products of the present invention are obtained, with the properties thereof being as described and within the mentioned desirable ranges.
The procedure of Example 1 is repeated, with sodium xylene sulfon-ate being substituted for sodium toluene sulfonate, and essentially the same types of low density base and final products are obtained. When sodium ben-zene sulfonate is utilized instead, acceptable products result but the effects thereof are not considered to be as good as those with the methyl-substituted benzene sulfonates. When the potassium salts of the mentioned hydrotropes are used, including potassium toluene sulfonate, essentially the same types of detergent compositions are produced.
When the previous experiments are repeated, but with substitutions of Neodol 45-11 and Alfonic 1618-65 for the Neodol 25-7, similar results are obtained. When pentasodium tripolyphosphate is replaced by tetrasodium pyrophosphate and when, in manufacturing non-phosphate detergents, the sodium tripolyphosphate is completely replaced by a mixture of two parts of sodium carbonate and one part of sodium silicate, products within the specifications of this invention are obtainable. This is also the case when sodium sulfate is replaced by sodium chloride or is omitted entirely, with the difference being made up by increases in sodium tripolyphosphate and sodium carbonate, and when sodium silicates of Na2O:SiO2 ratios of 1:2.0 and 1:2.4 are used.
g
A 4642/73; A 4666/73; A 4717/73; A 4750/73; A 4767/73;
A 4787/73; A 4788/73; A 4816/73; and A 4888/73. Additionally, such insoluble builders are described in the text Zeolite Molecular Sieves by Donald ~. Breck, published in 1974 by John Wiley & Sons, specifically being listed in Table 9.6 at pages 747-749 thereof. Of the builders present normally at least 50% will be ~ater soluble inorganic builder salts.
Preferably, this proportion will be at least 80%, more preferably, at least 9a% and most preferably, 100~. Although it is not necessary to incorporate a filler salt in the base beads or in the final detergent composition generally the presence of such material will be desirable. Among the best of the fillers, contributing particle strength, stability and flowability at relatively little cost, is sodium sulfate, which will u~ually be substantially all or all of the filler present, usuall~ heing over 50~ and preferably over 90% of the filler content.
However, other water soluble and non-deliquescent inorganic salts which are heat stable may also be employed, such as sodium chloride, sometimes found as an impurity in one of the product components, potassium sulfate, sodium bisulfate and potassium chloride.
The hydrotropic salt, which has been found to aid in the manufacture of the low density carrier particles of this invention, may be any such compound which has the property of promoting water solubility of only slightly soluble compounds and of aiding in the production of low density carrier and final product particles, especially when crutcher mixes of a base composition are spray dried at elevated temperatures. The preferred compounds of this type are water soluble salts of substituted or unsubstituted ben-zene sulfonic acids, such as the sodium and potassium salts thereof (the alkali metal salts), especially the sodium salts. Although alkali metal benzene sulfonates, such as sodium benzene sulfonate, are useful hydrotropes and may be employed in the processes of this invention, it is preferred to have one or more hydrogens of the benzene ring substituted, as by a lower alkyl group of 1 to 4 car-bon atoms, preferably 1 to 2 carbon atoms and most preferably one carbon atom (methyl), e.g., sodium toluene sulfonate, sodium xylene sulfonate, potassium toluene sulfonate and corresponding salts of cumene, mesitylene, ethylbenzene and .~
110(~376 pseudocumene. Usually, the sulfonates are mixtures of isomers, with para- and ortho-configurations normally and preferably dominat-ing, e.g., sodium p-methyl benzene sulfonate, sodium O,O-di-methyl sulfonate, sodium o,p-dimethyl benzene sulfonate. Also, mixtures of the various different types of hydrotropes may be used, e.g., sodium toluene sulfonate and sodium xylene sulfonate or the corres-ponding potassium salts.
The nonionic detergents employed are preferably poly-ethoxylated higher fatty alcohols such as the water soluble con-densation products of 3 to 15 mols of ethylene oxide, preferably 7 to 11 mols, and higher fatty alcohols of 10 to 18 carbon atoms, preferably 12 to 15 carbon atoms. Such nonionic detergents melt or soften sufficiently to be sprayable in droplet form at a tempera-ture below 45C. A preferred commercial product, which is the con-densation product of a higher fatty alcohol mixture of 12 to 15 carbon atoms with about 7 mols of ethylene oxide per mol of fatty alcohol, is sold under the trademark Neodo ~ 25-7, manufactured by Shell Chemical Co. Other commercial nonionic compounds of this general type which are also suitable include: Neodol 45-11, (also made by Shell Chemical Company); Alfonic~ 1618-65, which is a 16 to 18 carbon alkanol ethoxylated with an average of 10 to 11 mols of ethylene oxide per mol, manufactured by Continental Oil Company;
and Plurafac~ B-26, manufactured by BASF-Wyandotte.
110(1 376 In addition to the preferred polyethoxylated higher fatty alcohols and similar alkanols there may also be used, at least in part, e.g., up to 25 or 50%, various other nonionic detergents such as are described at length in McCutcheon's _etergents and Emulsifiers, 1973 Annual and in Surface Active Agents, Vol. II, by Schwartz, Perry and Berch (Interscience Publishers, 1958). Such nonionic detergents are usually pasty or waxy solvents at room temperature (20C.) and are either sufficiently water soluble to dissolve promptly in water, especially in the presence of the hydrotrope, or quickly melt and disperse therein at the temperature of the wash water, as when that temperature is a~ove 40 or 50C. They will normally not be fluid at room temperature because in such state they might tend to make a tacky agglomerate of the final particulate detergent, which could be poorly flowing and could lump or set on storage. Typical useful nonionic detergents which may be employed, providing that they are satisfactorily detersive in the present compositions at the concentrations utilized, e.g., Q.l to 0.2% of detergent composition in ~ash water, are the poly-lower alkenoxy derivatives that are usually prepared by the condensation of lo~er (2 to 4 carbon atoms) alkylene oxide, e.g., ethylene oxide, pr~pylene oxide (~ith enough ethylene oxide to make a water soluble productl, with a compound having a hydrophobic B -lo-~1~03!76 : ~
., ' ,:
e.g., hydrocarbon, chain containing one or more active hydrogen atoms, such as higher alkyl phenols, higher fatty acids, higher fatty mercaptans, higher fatty amines, higher fatty polyols and the ~
higher fatty alcohols previously mentioned. Generally, such com- ~ ;
pounds will be alkoxylated with an average of about 3 to 30, pre-ferably 3 to 15 and more preferably 7 to 11 alkylene oxide units.
The most preferred nonionic detergents are those represented by the formula RO(C2H4O)nH, wherein R is the residue of a linear saturated primary alcohol (an alkyl) of 12 to 15 carbon atoms and n is an integer from 7 to 11. Among additional nonionic detergents that may be employed are the Igepals~9 (GAF Co. Inc.); Pluronics~
(RASF-Wyandotte); Poly-Tergents~ (Olin Corp.); and Amidoxes~
(Stepan Chemical Co.).
In addition to the adjuvants previously mentioned, which ~ are preferably post-added to the spray dried base particles, small I proportions of anionic and amphoteric detergents may also be pre-sent in the base beads or may be post-added. Such are not neces-sary for the production of the desired detergent particles and if employed are normally present in small proportions, e.g., 0.5 to 2%. Examples of such materials include the alkali metal, prefer-ably sodium, higher alkyl benzene sulfonates having 12 to 15 carbon atoms in their alkyl groups, which are preferably linear; higher fatty alcohol sulfates; higher alkyl sulfonates; higher olefine sulfonates; and polyethoxylated higher fatty alcohol sulfates. In such cases the higher alkyl or alkene groups 110(~376 are usually of 1 to 20 or 12 to 18 carbon atoms and polyethoxyla-tion is to the extent of 3 to 30 or 3 to 15 alkylene oxides per mol. Instead of the synthetic anionic organic detergents mentioned the ordinary fatty acid soaps, usually sodium soaps of mixed higher fatty acids of 8 to 18 carbon atoms, such as those obtained from tallow and coconut oil, may desirably be substituted in whole or in part and mixtures of the anionic detergents may be used, with the total amount being within the percentage range previously given.
Instead of the anionic detergents amphoteric surface active agents may be employed. These are usually higher fatty carboxylates, phosphates, sulfates or sulfonates which contain a cation sub-stituent such as an amino group which may be quaternized, for ex-ample, with lower alkyl groups, or may have the chain thereof ex-tended at the amino group by condensation with a lower alkylene oxide, e.g., ethylene oxide. Representative commercial water sol-uble amphoteric organic detergents include Deriphat~ 151 and Miranol~ C2M. Sometimes it may be desirable to employ small pro-portions of cationic organic surface active agents, especially as anti-static or softening materials. Typical of such compounds are thoduomeens~ T/12 and T/13, which are ethylene oxide condensates of N-tallow trimethylene diamines (Armour Industrial Chemical Company) and Ethylqua ~ 18/12, 18/25 and 0/12, which are poly-ethoxylated quaternary ammonium chlorides (Armour Industry Chemical Co.). Various other synthetic detergents and surface active agents which may be employed are disclosed in the McCutcheon and Schwartz et al. texts.
To manufacture the low density particulate built synthetic organic detergent composition and the corresponding low density base composition particles, which are usually substantially inorganic with respect to the normally solid components thereof, an aqueous solution-dispersion, commonly referred to as a crutcher mix, is prepared, containing the various heat-resistant components of the final product, except the nonionic detergent and any materials best post-added. To save energy and to increase throughput of the drying equipment the crutcher mix ~ill usually be of as high a solids content as feasible, e.g. about 50 to 80%, with the balance, about 2Q to 50%, being watex. More water may be used but th~n energy demands are increased, tower throughputs are diminished, products resulting may be tackier and poorer flo~ing and often the desired lo~ density ba$e and final detergent composition particles will not be obtained. ~hen the moisture content of the crutcher mix is about 20 to 50% the ~ater soluble, inorganic buildex salt(s~ content ~ill be about 10 to 50%, inorganic filler s~alt(s~ content will be about 5 to 50% and the water soluhle~ organic hydrotropic salt(s) content will be ahout Q.2 to 5%. ~hen no inorganic filler salt is present the inorganic builder salt content may he 110(~376 such as to be the balance of the composition, in addition to the water and hydrotrope (and any other heat stable adjuvants, etc., present). Sodium tripolyphosphate, normally charged as pentasodium tripolyphosphate, is a pre-ferred builder salt and usually constitutes at least half of the builder salt in the crutcher. Correspondingly, the preferred filler salt is sodium sul-fate and generally this is at least half of the filler salt content in the crutcher mix. Of course, the content of water in the crutcher mix will be sufficient to satisfactorily dissolve-disperse the other components present.
Although other drying methods may be employed, such as drum drying, tray drying, fluidized bed drying, film drying, etc., the most preferred method is spray drying, wherein the crutcher mix is sprayed at an elevated pressure, usually from 3 to 50 kg./sq. cm., preferably 20 to 40 kg./sq. cm., through a spray nozzle into a drying tower, through which drying air passes to dry the resulting droplets of crutcher mix to globular, low density, free flowing particles. Instead of spray nozzles, equivalent atomizers of other designs may also be used. The preferred spray tower design is counter-current, with the height of the tower usually being from 5 to 25 meters and with the entering hot air, usually the gaseous products of combustion of oil or gas, being at a temperature in the range of 200 to 400C. ar.d with the outlet air usually at a temperature in the range of 50 to 90C. Concurrent tower designs may also be employed wherein similar inlet and outlet air temperatures obtain. It has been mentioned in German Offenlegungsschrift 2,514,677 that low density beads are more readily produced utilizing con-current spray drying than result from countercurrent drying but with the method of the present invention low density products can be obtained with either type of tower. Countercurrent drying is preferred and has the bene-fits of greater efficiency of the drying operation because the thermal grad-ient for removal of the moisture in the partially dried product, near the exit of the tower, is greater.
The nozzle size for producing droplets of crutcher mix of desired 11~3~
size is chosen to produce base particles in the 6 to 160 mesh, United States Standard Sieve Series, range. Preferably, the product is substantially of particles in such range when it is removed from the spray tower but any off-size particles, such as may be from 2 to 10% by weight, as result outside such size range, may be removed by screening, may be size-reduced to the de-sired size range or may be recycled in the same or a subsequent crutcher mix.
In some cases the 6 to 160 mesh product may be further screened to a narrower size range, such as 8 to 100 mesh. Also, spray characteristics may be altered so as to obtain substantially such a product from spray drying, with-out the need for further screening or size-reduction.
After drying is complete and the particles in the desired size range are obtained the nonionic detergent is applied to the surfaces thereof, preferably by spraying molten detergent, which may be in concentrated aqueous solution but preferably is free of water, onto the surfaces of the tumbling base particles in an inclined drum, through which the particles progress from an elevated feed end to the discharge end. Instead of an inclined drum one may also use fluidized beds of various conventional designs and other commer-cial mixers, such as those of the Schugi type. The proportion of nonionic detergent, preferably polyethoxylated higher fatty alcohol, will desirably be from 4 to 15% and the beads onto which it is sprayed will contain about 3 to 16% moisture, preferably 5.6 to 13.3% and more preferably, 5.6 to 11.1% of water, so that the final product will constitute about 2.5 to 15%, 5 to 12%, or 5 to 10% of water. Of course, the moisture content of the base beads may be higher when additional moisture-free constituents are to be post-added.
The proportions of adjuvant materials will generally be held to less than 15%, preferably less than 10% and more preferably less than 5%
total of the total product and the proportions of individual adjuvants will be less than 5% each, preferably less than 2% each and more preferably less than 1% each, in most cases. Thus, the total range of ad~uvant content may be from about 0 or 1 to 15%, preferably from 1 to 5% and the individual component concentrations may be from 0 or 0.1 to 5%, preferably 0.2 to 1%.
If a bleaching agent, such as sodium perborate, usually as the tetrahydrate and activated, is to be incorporated with the detergent, greater percentages thereof, e.g., 5 to 40%, preferably 10 to 30%, may be present. Thus, sodium perborate is not considered as one of the ordinary adjuvants previously dis-cussed. If used, it should be post-added.
For superior products it has been found desirable for the propor-tion of builder salt or filler salt to be within the range of 3:1 to 1:2, preferably 2:1 to 1:1.5. The bulk density of the base beads is in the range of 0.2 to 0.45 g./cc. and that of the final product beads is in the range of 0.3 to 0.5 g./cc. Preferably the bulk densities will be from 0.2 to 0.35 and 0.3 to 0.45 g./cc., respectively.
Preferred detergent compositions of this invention comprise about 20 to 40% of sodium tripolyphosphate, 3 to 15% of sodium carbonate, 5 to 15%
of sodium silicate of Na20:SiO2 ratio in the range of 1:1.6 to 1:3, 0 to 5%
of borax 1 to 3% of sodium toluene sulfonate or sodium xylene sulfonate 20 to 50% of sodium sulfate, 4 to 15% of higher fatty alcohol polyethylene oxide condensation product nonionic detergent and 5 to 12% of water. In such pro-ducts the higher fatty alcohol ethylene oxide condensation product is one which melts or softens sufficiently to be sprayable in droplet form at a temperature below 45C. and in the process of the invention it is melted and sprayed onto the surfaces of the spray dried particles of base material at a temperature below 55C., while such particles are in motion and are at a temperature below 45 & . and greater than 10C. A highly preferable process is one wherein the moisture content of the crutcher mix is about 30 to 45%, the crutcher mix of such a composition as to result in a spray dried final detergent composition product which, when it includes about 7 to 13% of poly-ethoxylated higher fatty alcohol nonionic detergent post-added to the spray dried base beads, includes 28 to 38% of sodium tripolyphosphate, 3 to 8% of sodium carbonate, 5 to 10% of sodium silicate of ~a20:SiO2 ratio of 1:2 to 1:2.4, 1.2 to 2% of sodium toluene sulfonate (or sodium xylene sulfonate), 0.5 to 2% of borax, 30 to 42% of sodium sulfate and 5 to 10% of moisture. In such a product the nonionic detergent is preferably a condensation product of a higher fatty alcohol of 12 to 15 carbon atoms and about 7 mols of ethylene oxide per mol of fatty alcohol, which product is sold under the trademark Neodol 25-7. In such process, the crutcher mix, at a temperature of 80 to 105C., is sprayed into the spray drying tower, preferably a countercurrent tower, with the tower drying air inlet temperature being in the range of 200 to 400C., and the spraying is such as to result in droplets which dry to particles of a mixture of sizes substantially in the 6 to 160 mesh range. To produce such particles a nozzle orifice of a 0.2 to 0.8 mm. diameter may be employed. In the post-spraying operation the nonionic detergent is sprayed onto the surfaces of the tumbling particles of base beads in a rotating in-clined drum which may be at an angle of about 5 to 15 and which rotates at a speed of about 5 to 50 r.p.m., The nonionic detergent is at a temperature of 35 to 50C. when sprayed on the tumbling particles, which are at a temperature of 20 to 45C.
The process for manufacture of the base or carrier beads has been described pTeviously in conjunction with the overall process for the manufac-ture of detergent composition particles. However, allowing for about 10% ofnonionic detergent being post-added to the base beads, the preferred and the most preferred contents of various components of the beads are somewhat different, being 22 to 44% of sodium tripolyphosphate, 3.3 to 16.7% of sodium carbonate, 5.6 to 16.7% of sodium silicate, 1.1 to 3.3% of sodium toluene sul-fonate or sodium xylene sulfonate, 0 to 5.6% of borax, 22 to 56% of sodium sulfate and 5.6 to 13.3% of water, with the more preferred ranges being 31.1 to 42.2%; 3.3 to 8.9%; 5.6 to 11.1%; 1.3 to 2.2%; 0.5 to 2.2%; 33 to 47%; and 5.6 to 11.1%, respectively.
The various advantages of the described processes and the composi-tions resulting have been referred to previously but will be recounted 110~376 briefly here. Principally, a built heavy duty nonionic detergent is manufac-tured which is in particulate form, of desired low density, non-tacky, non-caking and free flowing. It is made by an economical process which allows for ready variation in active detersive ingredient content of the composition.
The process is environmentally acceptable, producing no undesirable smoke or fumes from the drying means, such as a spray tower. Also, tower throughput is increased and energy consumption is decreased. Despite the comparatively high contents of nonionic detergent in the final particulate composition such detergent is readily sorbed by the hydrotrope-containing beads and compara-tively short mixing times, e.g., 1 to 5 minutes, are sufficient. The pre-sence of the hydrotrope in the product, while not interfering with the pro-perties of the nonionic detergent, does aid in solubilizing some compara-tively insoluble soiling substances often present on laundry and also aids in promoting solubility of any poorly soluble adjuvants which may be present in the detergent, thus preventing unwanted depositing thereof onto the laundry.
For example, colorants in detergents may be prevented from being deposited on laundry fabrics of the laundered items. However, the main advantage of the invention is in the production of desired low density particulate products and in this respect the present process, utilizing a hydrotropic salt of the type described, can produce a lower density product than is obtained with soap, mixtures of soap and nonionic detergent, and anionic detergents, em-ployed in similar quantities.
The reason for the desirable effects noted with the present pro-cesses is not clear. It has been theorized that the hydrotropic salt aids in the production of a more homogeneous crutcher mix and thereby avoids the pro-duction of weak points or rupture-prone locations on the droplet or bead as drying is effected. Therefore, the bead can swell to a larger size and main-tain such size as it is dried, leading to the production of a lower density product. However, even if such theory should become verified it would still be unexpected that the small proportion of hydrotropic salt utilized would be -1~-X
1101~3~76 sufficiently effective to significantly modify the characteristics of a crutcher mix or base droplet containing such a high percentage of inorganic salts.
The detergent compositions of this invention, when employed in the same manner as conventional heavy duty particulate detergents, at normal use concentrations, e.g., 0.1 to 0.2%, in cold, warm or hot wash waters, result in very satisfactory cleaning of the articles of laundry being washed. Addi- r tionally, the particulate detergent may be made into a paste with water for treatment of heavily soiled areas of the laundry and the presence of the 10hydrotrope assists in loosening such soil so that it may be more readily re-moved during washing.
The following examples illustrate but do not limit the invention.
Unless otherwise mentioned, all parts in the specification are by weight and all temperatures are in C.
A crutcher mix is made of 23.9% of sodium tripolyphosphate, 3.6% of sodium carbonate, 5.1% of sodium silicate, 1.1% of sodium toluene sulfonate, 0.7% of borax, 25.6% of sodium sulfate and 40% of water. All the components except the sodium silicate and the water are added as anhydrous powders.
Sodium silicate is added as 10.2% of a 50% aqueous solution and its Na20:SiO2 ratio is 1:2.35. The aqueous composition is mixed in a conventional heated detergent crutcher for a period of about 15 minutes (polyphosphate is added last) and is pumped by a high pressure pump (Triplex) at a pressure of 25 kg./
sq. cm. and at a temperature of 95C. into the top of a 20 m. tall spray tower through a plurality of 0.5 mm. dia. nozzles, which create a spray of droplets of sizes substantially in the 6 to 160 mesh, United States Standard Sieve Series, range, which produce beads of a similar size. The drying air, entering the bottom of the tower, is at a temperature of about 300C. and when it leaves the tower at the top it is at a temperature of about 90C.
The droplets of sprayed crutcher mix, falling through the tower, have an 1~003!76 average residence time therein of about one minute, with residence time modi-fications, depending on particular drying conditions, being variable to from 30 seconds to three minutes. The spray dried beads, comprising over 95% of particles in the desired 6 to 160 mesh range, are withdrawn from the tower at a temperature of about 45C., after some preliminary cooling at the base of the tower. The beads at this temperature are delivered to an inclined rotat-ing drum wherein there is sprayed onto the surfaces thereof a melt of Neodol 25-7 (higher fatty alcohol mixture of about 12 to 15 carbon atoms poly-ethoxylated with about 7 mols of ethylene oxide per mol) at a temperature of about 40C. The drum is inclined at an angle of about 7 and residence time of the particles therein is about 3 to 5 minutes. The spray nozzles are such that the droplets of spray are of sizes corresponding to about 100 to 200 mesh ant the sprays are directed onto the surfaces of the tumbling particles.
During the tumbling the product is cooled somewhat and after removal from the tumbling drum it is additionally cooled to a temperature in the 20 to 30C.
range, after which it is ready for packaging.
The product made is an excellent heavy duty laundry detergent, especially good for cold and warm water use, wherein it is superior to many detergents based on anionic synthetic active ingredients. Its bulk density before packaging is about 0.34 g./cc., having been increased slightly during the add-on of nonionic detergent, from about 0.29 g./cc. The moisture con-tent to which the crutcher mix content had been dried to form the base beads is 7.7%. The final detergent composition is of the following analysis: 33%
sodium tripolyphosphate; 5% sodium carbonate; 7% sodium silicate; 1.5% sodium toluene sulfonate; 1% borax; 35.5% sodium sulfate; 10% nonionic detergent;
and 7% water.
In a control experiment, when the same operational steps are re-peated with the same composition except that the sodium toluene sulfonate is omitted from the crutcher mix, the density of the spray dried base beads re-sulting is over 0.5 g./cc. and that of the finished detergent composition llOV376 particles is 0.59 g./cc., which is objectionably high for a product designedto be commercially marketed in replacement of conventional spray dried deter-gent compositions.
In modifications of the process of the invention the drying of the crutcher mix is effected by drum and tray drying and the products resulting are size reduced to the desired 6 to 160 mesh and narrower ranges. By such method a desirable lowering of the density of the product into the 0.3 to 0.5 g./cc. range is obtained whereas without the presence of the hydrotropic salt a higher density, outside such range, may result. The bulk density may be desirably lowered further by aerating the mix before drying, with the hydrotropic salt present therein. Also, further lowerings of the bulk den-sity of the drum dried and tray dried products, as well as those made by spray drying, as described above, are obtained when the particle size ranges are from 8 to 140 and 8 to 100 mesh, with particles outside such ranges being removed and subjected to size reduction or recycling treatments.
In other modifications of the described experiment, utilizing spray drying, the proportions of the various components of the crutcher mix are individually modified, +10, +20, and +30%, while still remaining in the ranges specified, with the proportions of other components remaining con-stant. In such cases the processing conditions are also changed, with thecrutcher mix temperature being modified to 85, 90 and 100C., the spray nozzle cross-sectional area being increased and decreased 10% and the drying air inlet temperature being changed to 250 and 350C. in various experi-ments. Also, in addition to utilizing the inclined drum described, the angle thereof is modified to 5 and 12 and in some cases the nonionic detergent is applied in a Schugi apparatus or is directed into a fluidized bed of the base particles. The temperature of the base beads is changed +5 C., as is that of the nonionic detergent being sprayed onto them. In some instances 0.6% of perfume is added with the nonionic (dissolved therein). In all such cases useful products of the present invention are obtained, with the properties thereof being as described and within the mentioned desirable ranges.
The procedure of Example 1 is repeated, with sodium xylene sulfon-ate being substituted for sodium toluene sulfonate, and essentially the same types of low density base and final products are obtained. When sodium ben-zene sulfonate is utilized instead, acceptable products result but the effects thereof are not considered to be as good as those with the methyl-substituted benzene sulfonates. When the potassium salts of the mentioned hydrotropes are used, including potassium toluene sulfonate, essentially the same types of detergent compositions are produced.
When the previous experiments are repeated, but with substitutions of Neodol 45-11 and Alfonic 1618-65 for the Neodol 25-7, similar results are obtained. When pentasodium tripolyphosphate is replaced by tetrasodium pyrophosphate and when, in manufacturing non-phosphate detergents, the sodium tripolyphosphate is completely replaced by a mixture of two parts of sodium carbonate and one part of sodium silicate, products within the specifications of this invention are obtainable. This is also the case when sodium sulfate is replaced by sodium chloride or is omitted entirely, with the difference being made up by increases in sodium tripolyphosphate and sodium carbonate, and when sodium silicates of Na2O:SiO2 ratios of 1:2.0 and 1:2.4 are used.
g
Claims (19)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for manufacturing a low density, particulate, built synthetic organic detergent composition which comprises mixing together a plurality of components of a crutcher mix comprising inorganic builder salt(s) selected from the group consisting of water soluble polyphosphates, carbonates, silicates, borates, bicarbonates, and phosphates, water soluble organic hydrotropic salt(s) and water in such proportions that when subsequently dried the water soluble organic hydrotropic salt(s) present signficantly reduces the density of the product, drying the mix and applying onto the surfaces of particles of the dried mix a detersive proportion of nonionic detergent.
2. A process according to claim 1 wherein the mix is a crutcher mix which. comprises about 20 to 50% of water, about 10 to 50% of water soluble, inorganic builder salt(s), about 5 to 50% of water soluble, inorganic filler salt(s) selected from the group consisting of alkali metal sulfates, chlorides, and bisulfates, and about 0.2 to 5% of water soluble organic hydrotropic salt(s), which is a water soluble salt of a substituted or unsubstituted benzene sulfonic acid and said crutcher mix is spray dried.
3. A process according to claim 2 wherein at least half of the builder salt is sodium tripolyphosphate, at least half of the filler salt is sodium sulfate, the hydrotrope is a water soluble salt of a lower alkyl substituted benzene sulfonic acid, the nonionic detergent is a polyethoxylated higher fatty alcohol, the proportion of such polyethoxylated higher fatty alcohol is from 5 to 25% of the product and the spray drying is effected in a countercurrent tower.
4. A process according to claim 3 wherein the builder salt comprises sodium tripolyphosphate, sodium silicate and sodium car-bonate, substantially all of the filler salt is sodium sulfate, the hydrotrope is a water soluble salt of a mono- or di-methyl sub-stituted benzene sulfonic acid, the proportion of builder salt to filler salt is within the range of 3:1 to 1:2, the crutcher mix is spray dried to a moisture content in the range of 3 to 16% and a bulk density of 0.2 to 0.45 g./cc., the polyethoxylated higher fatty alcohol is a condensation product of a higher fatty alcohol of 10 to 18 carbon atoms and 3 to 15 mols of ethylene oxide per mol of higher fatty alcohol and the bulk density of the product after spraying of the condensation product thereon is 0.3 to 0.5 g./cc.
5. A process according to claim 4 wherein the detergent com-position comprises about 20 to 40% of sodium tripolyphosphate, 3 to 15% of sodium carbonate, 5 to 15% of sodium silicate of Na20:SiO2 ratio in the range of 1:1.6 to 1:3, 1 to 3% of sodium toluene sul-fonate or sodium xylene sulfonate, 0 to 5% of borax, 20 to 50% of sodium sulfate, 4 to 15% of higher fatty alcohol polyethylene oxide condensation product nonionic detergent and S to 12% of water, and the higher fatty alcohol ethylene oxide condensation product is one which melts or softens sufficiently to be sprayable in droplet form at a temperature below 45°C. and is melted and sprayed onto the surfaces of the spray dried particles at a temperature below 55°C.
when such particles are in motion and at a temperature below 45 C.
and greater than 10°C.
when such particles are in motion and at a temperature below 45 C.
and greater than 10°C.
6. A process according to claim 5 wherein the moisture con-tent of the crutcher mix is about 30 to 45%, the crutcher mix is of such composition as to result in a spray dried product, when it contains about 7 to 13% of polyethoxylated higher fatty alcohol nonionic detergent which is post-added to the spray dried composi-tion, of 28 to 38% of sodium tripolyphosphate, 3 to 8% of sodium carbonate, 5 to 10% of sodium silicate of Na20:SiO2 ratio of 1:2 to 1:2.4, 1.2 to 2% of sodium toluene sulfonate, 0.5 to 2% of borax, 30 to 42% of sodium sulfate and 5 to 10% of moisture, the nonionic detergent is a condensation product of a higher fatty alcohol of 12 to 15 carbon atoms and about 7 mols of ethylene oxide per mol of fatty alcohol, the crutcher mix is at a temperature of 80 to 105°C.
when it is sprayed into the spray drying tower, the tower drying air inlet temperature is in the range of 200 to 400°C., the crutcher mix is sprayed into the tower and forms droplets of such size as to result in dried particles of a mixture of sizes sub-stantially in the 6 to 160 mesh, United States Standard Sieve Series, range, and the post spraying of nonionic detergent is onto the surfaces of such tumbling particles and is effected in a rotat-ing inclined drum with the nonionic detergent at a temperature of 35 to 50°C. and the tumbling particles being at a temperature of 20 to 45°C.
when it is sprayed into the spray drying tower, the tower drying air inlet temperature is in the range of 200 to 400°C., the crutcher mix is sprayed into the tower and forms droplets of such size as to result in dried particles of a mixture of sizes sub-stantially in the 6 to 160 mesh, United States Standard Sieve Series, range, and the post spraying of nonionic detergent is onto the surfaces of such tumbling particles and is effected in a rotat-ing inclined drum with the nonionic detergent at a temperature of 35 to 50°C. and the tumbling particles being at a temperature of 20 to 45°C.
7. A process for manufacturing a low density substantial-ly inorganic particulate base composition useful for conversion to a built synthetic organic detergent composition by addition of nonionic detergent thereto, which comprises mixing together a plurality of components of a crutcher mix comprising inorganic builder salt(s) selected from the group consisting of water soluble polyphosphates, carbonates, silicates, borates, bicarbonates, and phosphates, water soluble organic hydrotropic salt(s) and water in such proportions that when subsequently dried the water soluble organic hydrotropic salt(s) present significantly reduces the density of the product, and drying the mix.
8. A process according to claim 7 wherein the mix is a crutcher mix which comprises about 20 to 50% of water, about 10 to 50% of water soluble inorganic builder salt(s), about 5 to 50% of water soluble inorganic filler salt(s) selected from the group consisting of alkali metal sulfates, chlorides, and bisulfates, and about 0.2 to 5% of water soluble organic hydrotropic salt(s), which is a water soluble salt of a substituted or unsubstituted benzene sulfonic acid, and said crutcher mix is spray dried.
9. A process according to claim 8 wherein at least half of the builder salt is sodium tripolyphosphate, at least half of the filler salt is sodium sulfate, the hydrotrope is a water soluble salt of a lower alkyl substituted benzene sulfonic acid and the spray drying is effected in a countercurrent tower.
10. A process according to claim 9 wherein the builder salt comprises sodium tripolyphosphate, sodium silicate and sodium carbonate, substantially all of the filler salt is sodium sulfate, the hydrotrope is a water soluble salt of a mono- or di-methyl substituted benzene sulfonic acid, the propor-tion of builder salt to filler salt is within the range of 3:1 to 1:2, and the crutcher mix is spray dried to a moisture content in the range of 3 to 16% and a bulk density of 0.2 to 0.45 g./cc.
11. A process according to claim 10 wherein the spray dried base beads for addition of nonionic detergent thereto to produce a built detergent com-position comprise about 22 to 44% of sodium tripolyphosphate, 3.3 to 16.7% of sodium carbonate, 5.6 to 16.7% of sodium silicate, 1.1 to 3.3% of sodium toluene sulfonate or sodium xylene sulfonate, 0 to 5.6% of borax, 22 to 56%
of sodium sulfate and 5.6 to 13.3% of water.
of sodium sulfate and 5.6 to 13.3% of water.
12. A process according to claim 11 wherein the moisture content of the crutcher mix is about 30 to 45%, the crutcher mix is of such composition as to result in a spray dried particulate detergent base product comprising about 31.1 to 42.2% of sodium tripolyphosphate, 3.3 to 8.9% of sodium carbon-ate, 5.6 to 11.1% of sodium silicate of Na2O:SiO2 ratio of 1:2 to 1:2.4, 1.3 to 2.2% of sodium toluene sulfonate, 0.5 to 2.2% of borax, 33 to 47% of sodium sulfate and 5.6 to 11.1% of water, the crutcher mix is at a tempera-ture of 80 to 105°C. when it is sprayed into the spray drying tower, the tower drying air inlet temperature is in the range of 200 to 400°C. and the crutcher mix is sprayed into the tower and forms droplets of such size as to result in dried particles of a mixture of sizes substantially in the 6 to 160 mesh, United States Standard Sieve Series, range.
13. A particulate built nonionic detergent composition having a bulk density in the range of 0.3 to 0.5 g./cc. which comprises about 20 to 40% of sodium tripolyphosphate, 3 to 15% of sodium carbonate, 5 to 15% of sodium silicate of Na2O:SiO2 ratio in the range of 1:6 to 1:3, 1 to 3% of sodium toluene sulfonate or sodium xylene sulfonate, 0 to 5% of borax, 20 to 50% of sodium sulfate, 4 to 5% of polyethoxylated higher fatty alcohol nonionic detergent which is a condensation product of higher fatty alcohol(s) of 10 to 18 carbon atoms and 3 to 15 mols of ethylene oxide per mol of higher fatty alcohol, and 5 to 12% of water.
14. A composition according to claim 13 wherein the nonionic detergent is one which melts or softens sufficiently to be sprayable in droplet form at a temperature below 45°C. and coats base particles comprising the other named composition constituents and the particles are substantially of sizes in the 6 to 160 mesh, United States Standard Sieve Series, range.
15. A composition according to claim 14 comprising 28 to 38% of sodium tripolyphosphate, 3 to 8% of sodium carbonate, 5 to 10% of sodium silicate of Na2O:SiO2 ratio of 1:2 to 1:2.4, 1.2 to 2% of sodium toluene sulfonate, 0 to 2% of borax, 30 to 42% of sodium sulfate, 7 to 13% of polyethoxylated higher fatty alcohol nonionic detergent and 5 to 10% of moisture.
16. A composition according to claim 15 wherein the nonionic detergent is a condensation product of a higher fatty alcohol of about 12 to 15 carbon atoms and about 7 mols of ethylene oxide per mol of such higher fatty alcohol.
17. A low density substantially inorganic particulate base composition, useful for conversion to a built synthetic organic detergent composition by addition of nonionic detergent thereto, which comprises about 22 to 44% of sodium tripolyphosphate, 3.3 to 16.7% of sodium carbonate, 5.6 to 16.7% of sodium silicate of Na2O:SiO2 ratio in the range of 1:1.6 to 1:3, 1.1 to 3.3%
of sodium toluene sulfonate or sodium xylene sulfonate, 0 to 5.6% of borax, 22 to 56% of sodium sulfate and 5.6 to 13.3% of water.
of sodium toluene sulfonate or sodium xylene sulfonate, 0 to 5.6% of borax, 22 to 56% of sodium sulfate and 5.6 to 13.3% of water.
18. A composition according to claim 17, of particle sizes substant-ially in the 6 to 160 mesh, United States Standard Sieve Series, range and comprising about 31.1 to 42.2% of sodium tripolyphosphate, 3.3 to 8.9% of sodium carbonate, 5.6 to 11.1% of sodium silicate of Na2O:SiO2 ratio of 1:2 to 1:2.4, 1.3 to 2.2% of sodium toluene sulfonate, 0.5 to 2.2% of borax, 33 to 47% of sodium sulfate and 5.6 to 11.1% of water.
19. A composition according to claim 17, of particle sizes substant-ially in the 6 to 160 mesh, United States Standard Sieve Series, range and comprising about 31.1 to 42.2% of sodium tripolyphosphate, 3.3 to 8.9% of sodium carbonate, 5.6 to 11.1% of sodium silicate of Na2O:SiO2 ratio of 1:2 to 1:2.4, 1.3 to 2.2% of sodium xylene sulfonate, 0.5 to 2.2% of borax, 33 to 47% of sodium sulfate and 5.6 to 11.1% of water.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US74700176A | 1976-12-02 | 1976-12-02 | |
| US747,001 | 1976-12-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1100376A true CA1100376A (en) | 1981-05-05 |
Family
ID=25003259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA292,062A Expired CA1100376A (en) | 1976-12-02 | 1977-11-30 | Low density detergent compositions |
Country Status (12)
| Country | Link |
|---|---|
| AU (1) | AU520130B2 (en) |
| BE (1) | BE861431A (en) |
| CA (1) | CA1100376A (en) |
| CH (1) | CH633040A5 (en) |
| DE (1) | DE2752984C2 (en) |
| DK (1) | DK152380C (en) |
| FR (1) | FR2372889A1 (en) |
| GB (1) | GB1591516A (en) |
| IT (1) | IT1092163B (en) |
| MY (1) | MY8300070A (en) |
| SE (2) | SE441929B (en) |
| ZA (1) | ZA776948B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PH15690A (en) * | 1979-10-31 | 1983-03-11 | Unilever Nv | Detergent compositions and processes for manufacturing them |
| GB2222411A (en) * | 1988-09-01 | 1990-03-07 | Unilever Plc | Making particulate detergent compositions |
| US5576285A (en) * | 1995-10-04 | 1996-11-19 | The Procter & Gamble Company | Process for making a low density detergent composition by agglomeration with an inorganic double salt |
| US5665691A (en) * | 1995-10-04 | 1997-09-09 | The Procter & Gamble Company | Process for making a low density detergent composition by agglomeration with a hydrated salt |
| WO1999024544A1 (en) * | 1997-11-07 | 1999-05-20 | Fmc Foret, S.A. | Homogenous granules comprised of sodium tripolyphosphate, sodium sulphate and sodium carbonate, process for its preparation and applications to detergents and washing agents |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4001132A (en) * | 1974-06-17 | 1977-01-04 | The Procter & Gamble Company | Automatic dishwashing detergent composition |
-
1977
- 1977-11-21 ZA ZA00776948A patent/ZA776948B/en unknown
- 1977-11-22 SE SE7713168A patent/SE441929B/en not_active IP Right Cessation
- 1977-11-28 DE DE2752984A patent/DE2752984C2/en not_active Expired
- 1977-11-30 CA CA292,062A patent/CA1100376A/en not_active Expired
- 1977-11-30 AU AU31094/77A patent/AU520130B2/en not_active Expired
- 1977-12-01 IT IT52025/77A patent/IT1092163B/en active
- 1977-12-01 GB GB50120/77A patent/GB1591516A/en not_active Expired
- 1977-12-01 FR FR7736233A patent/FR2372889A1/en active Granted
- 1977-12-02 BE BE183110A patent/BE861431A/en not_active IP Right Cessation
- 1977-12-02 CH CH1477777A patent/CH633040A5/en not_active IP Right Cessation
- 1977-12-02 DK DK536977A patent/DK152380C/en active
-
1983
- 1983-03-22 SE SE8301557A patent/SE450642B/en not_active IP Right Cessation
- 1983-12-30 MY MY70/83A patent/MY8300070A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DK152380B (en) | 1988-02-22 |
| DK536977A (en) | 1978-06-03 |
| FR2372889A1 (en) | 1978-06-30 |
| BE861431A (en) | 1978-03-31 |
| FR2372889B1 (en) | 1982-07-30 |
| SE8301557L (en) | 1983-03-22 |
| GB1591516A (en) | 1981-06-24 |
| SE441929B (en) | 1985-11-18 |
| AU520130B2 (en) | 1982-01-14 |
| MY8300070A (en) | 1983-12-31 |
| SE450642B (en) | 1987-07-13 |
| AU3109477A (en) | 1979-06-07 |
| SE7713168L (en) | 1978-06-03 |
| DE2752984A1 (en) | 1978-06-08 |
| CH633040A5 (en) | 1982-11-15 |
| DK152380C (en) | 1988-07-25 |
| ZA776948B (en) | 1979-06-27 |
| SE8301557D0 (en) | 1983-03-22 |
| IT1092163B (en) | 1985-07-06 |
| DE2752984C2 (en) | 1984-08-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3849327A (en) | Manufacture of free-flowing particulate heavy duty synthetic detergent composition containing nonionic detergent and anti-redeposition agent | |
| US3838072A (en) | Manufacture of free flowing particulate detergent containing nonionic surface active compound | |
| US4828721A (en) | Particulate detergent compositions and manufacturing processes | |
| US3112274A (en) | Process for making a bleach composition | |
| AU623644B2 (en) | Process for manufacturing high bulk density particulate fabric softening synthetic anionic organic detergent compositions | |
| CA1096740A (en) | Concentrated heavy duty particulate laundry detergent | |
| US5149455A (en) | Process for increasing the density of spray dried, phosphate-reduced detergents | |
| US4006110A (en) | Manufacture of free-flowing particulate heavy duty synthetic detergent composition | |
| US4488972A (en) | Bentonite agglomerates | |
| US4411809A (en) | Concentrated heavy duty particulate laundry detergent | |
| US4636330A (en) | Perfume depositing detergents containing perfume in a particulate matrix of a cationic compound | |
| US4310431A (en) | Free flowing builder beads and detergents | |
| US4853259A (en) | Process for manufacturing particulate built nonionic synthetic organic detergent composition comprising polyacetal carboxylate and carbonate and bicarbonate builders | |
| US4394127A (en) | Method of depositing perfume and compositions therefor | |
| US4664817A (en) | Free flowing high bulk density particulate detergent-softener | |
| US4276326A (en) | Free flowing builder beads and detergents | |
| CA1100376A (en) | Low density detergent compositions | |
| US4720399A (en) | Process for manufacture of particulate built nonionic synthetic organic detergent composition comprising polyacetal carboxylate and carbonate and bicarbonate builders | |
| AU653408B2 (en) | Zeolite based spray-dried detergent compositions and process for preparing same | |
| GB1591515A (en) | Detergent-fabric softener compositions | |
| US4725455A (en) | Process for manufacturing particulate built nonionic synthetic organic detergent composition comprising polyacetal carboxylate and polyphosphate builders | |
| US4549978A (en) | Process for manufacture of detergent powder | |
| US4414129A (en) | Free-flowing builder beads and detergents | |
| JPS5843440B2 (en) | ``Hunmukansoushita'' Hiion Seihiyou Menkatsuseizai Ogan Yuusurusenjiyouzaino Seihou | |
| US4851137A (en) | Process for manufacturing bentonite agglomerates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |