US3886079A

US3886079A - Detergent compositions and detergent adjuvant combinations thereof, and processes for forming the same

Info

Publication number: US3886079A
Application number: US184059A
Authority: US
Inventors: Jr Oliver W Burke
Original assignee: BURKE OLIVER W JUN
Current assignee: BURKE OLIVER W JUN
Priority date: 1971-09-27
Filing date: 1971-09-27
Publication date: 1975-05-27
Anticipated expiration: 1992-05-27

Abstract

Detergent compositions and detergent adjuvant combinations thereof and processes for forming the same are provided, the adjuvant combination comprising an alkaline hydrated silica pigment precipitate and electrolyte, the electrolyte being selected in a controlled proportion from the class of alkali metal carbonates and/or bicarbonates, and the adjuvant being combined with soap and/or other anionic and/or non-ionic detergents and/or polymeric emulsifiers in the composition. The silica pigment precipitate may be formed in the presence of the detergent, and detergent may be added to or be formed in the presence of the adjuvant combination. The products may be dried to form concentrated liquid, paste, bar, and powdered detergent compositions, the latter preferably being spray dried.

Description

United States Patent 1191 1111 3,886,079 Burke, Jr. May 27, 1975 [54] DETERGENT COMPOSITIONS AND 3,630,919 12/1971 Sheaffer 252/88 DETERGENT ADJUVANT COMBINATIONS 3,630,929 12/1971 Van Dljk 252/136 3,708,428 l/ 1973 MacDonald 252/109 THEREOF, AND PROCESSES FOR FORMING THE SAME OTHER PUBLICATIONS Synthetic Detergents, by A. Davidsohn et al., Leonard Hill, London 1967, pp. 37, 38 & 53.

Primary ExaminerP. E. Willis, Jr. Attorney, Agent, or Firml-Iall & Houghton [5 7] ABSTRACT Detergentco mpositions and detergent adjuvant combinations thereof and processes for forming the same are provided, the adjuvant combination comprising an alkaline hydrated silica pigment precipitate and electrolyte, the electrolyte being selected in a controlled proportion from the class of alkali metal carbonates and/or bicarbonates, and the adjuvant being combined with soap and/or other anionic and/or non-ionic detergents and/or polymeric emulsifiers in the composition. The silica pigment precipitate may be formed in the presence of the detergent, and detergent may be added to or be formed in the presence of the adjuvant combination. The products may be dried to form concentrated liquid, paste, bar, and powdered detergent compositions, the latter preferably being spray dried.

21 Claims, 1 Drawing Figure PRSMRATIOH 01 12mm ADJUVAIVI COMMITIOIB of Sodium Carbonate and/or Bicarbonate and weed Alkaline Silica Pigments ,2 REGION "A" 3 h-eferrod.

3 Ranges 0 e l 1.5 l l g \4- Precipitation Region l 4- moctrolyte tarmng Region 1011. 00 per r1101. x6 0 or an emic/ PATENTEmiz-wzv ms 3.886; 079

HEPARATION OF DETERGENT ADJ'U'VANI' COMPOSITIONS of Sodium Carbonate and/ or Bicarbonate and Hydrated Alkaline Silica Pigments REGION "B" Most Preferred Ranges 3.0 b

A: REGION "A" 3 Preferred 3 Ranges 3 n a u z 1.5 o \4- Hecipitation 2 Region Electrolyte forming Region Male. co per mol Na o of Na O(SiO NVENTOR (f ir-7,- fa m/1. R

ATTORNEY 1 DETERGENT COMPOSITIONS AND DETERGENT ADJUVANT COMBINATIONS THEREOF, AND PROCESSES FOR FORMING THE SAME BACKGROUND OF THE INVENTION 1. Field of the Invention The field of this invention pertains to detergent compositions (class 252-89) and detergent adjuvants thereof and processes for forming the same.

2. Description of the Prior Art The phosphates commonly employed in detergent compositions have caused environmental pollution and it has for some time been desired to obtain detergent compositions and detergent adjuvants having reduced or no phosphate content, at reasonable costs, and the present invention aims to satisfy this want.

OBJECTS AND SUMMARY OF THE INVENTION A first object of the present invention is to provide a detergent adjuvant consisting essentially of alkaline hydrated silica pigment precipitate prepared with the aid of carbon dioxide and/or an alkali metal bicarbonate and having a bound alkali content and a free alkali electrolyte content, and the latter comprising alkali metal carbonate and/or bicarbonate, such adjuvant being combined with or suitable for combination with detergents from the class consisting of soaps, synthetic anionic detergents, non-ionic detergents, polymeric anionic and non-ionic dispersants or emulsifying agents, and combinations of the same, for assisting the detergent action thereof.

A second object of the invention is to provide improved detergent compositions by combining such detergent adjuvant in never dried form with detergent material selected from the class consisting of soaps, synthetic anionic detergents, non-ionic detergents, polymeric anionic emulsifying agents and combinations of the same.

A third object of the invention is to prepare such detergent adjuvant by reacting alkali metal silicate solutions with carbon dioxide and/or alkali metal bicarbonates in the presence of an aqueous solution of detergent selected from the class consisting of soaps, synthetic anionic detergents, non-ionic detergents, polymeric emulsifying agents and combinations of the same.

In its process aspect the invention comprises a process for preparing a detergent adjuvant combination which comprises:

a. forming an aqueous solution of water soluble alkali metal silicate,

b. adding to said solution sufficient reactant selected from the class consisting of carbon dioxide and alkali metal bicarbonate to form thereof a solution of electrolyte selected from the alkali metal carbonates and bicarbonates and having a precipitate of alkaline silica pigment therein, and

c. recovering said alkaline silica pigment and at least 25% dry basis, by weight, of the electrolyte resulting from step (b), in combination, as a detergent adjuvant combination.

' Silica pigment containing bound alkali.

In such three step process, step (b) may be conducted to provide said solution with electrolyte containing predetermined significant proportions of alkali metal bicarbonate, e.g. in the range of at least 2 mol percent to at least 90 mol percent thereof; the quantity of water of the solution may be reduced after the formation of the precipitate in step (b); in step (c) the recovery may include spray drying; in step (c) substantially all of the electrolyte of the solution may be recovered as part of said detergent adjuvant combination; and in step (c) the detergent adjuvant combination may be mixed with detergent material selected from the class consisting essentially of the water soluble members of the following groups: Group (I) soaps; Group (ll) synthetic anionic detergents; Group (lll) anionic polymeric emulsifiers; Group (IV) non-ionic detergents: Group (V) non-ionic polymeric emulsifiers; and combinations of two or more of said members; in a ratio in the range of 5:95 to :5 parts dry basis, by weight, based on the silica content as SiO and the product recovered may be a detergent composition incorporating the detergent adjuvant combination. Furthermore, in step (c) the detergent adjuvant combination, without having been dried following step (b), may be mixed with an aqueous dispersion of the detergent material selected from the class consisting essentially of the water soluble members of said groups and combinations of said members; in a ratio in the range of 5:95 to 95:5 parts dry basis, by weight, based on the silica content as SiO and dried therewith to form the product which may be spray dried when a powdered product is desired. In preparing the composition in step (c) detergent material selected from the sub-class consisting of the members of Groups (I), (ll) and (ll!) may be formed in the presence of the silica pigment by reaction of the corresponding free acid with alkalinity of the combination resulting from step (i); and detergent materialcomprising a soap may be formed in the presence of the silica pigment by saponification of a fatty acid glyceride with the aid of alkalinity of the combination resulting from step (b). In further embodiments of the invention in step (a) the aqueous solution of water soluble alkali metal silicate may contain detergent material selected from the class consisting essentially of the water soluble members of the following groups: Group (I) soaps; Group (ll) synthetic anionic detergents; Group (lll) anionic polymeric emulsifiers; Group (IV) non-ionic detergents; Group (V) non-ionic polymeric emulsifiers; and combinations of two or more of said members; in a ratio 5:95 to 95:5 parts, dry basis, by weight, based on the silica content of the solution as SiO and the product recovered may be a detergent composition incorporating the same with the detergent adjuvant combination; and in this embodiment in step (a) less than the maximum ratio of detergent to silica may be employed, and in step (c) the detergent adjuvant combination may be mixed with further detergent, material selected from the members of said class and combinations thereof, in an amount which combined with that included in step (0) lies in the aforesaid ratio range.

In its product aspect the invention provides a composition comprising a detergent adjuvant combination consisting essentially of:

a. a silica pigment, and

b. an electrolyte,

c". said silica pigment being an alkaline hydrated silica pigment which has been prepared by the acidulation of aqueous sodium silicate solution with the aid of reactant selected from the class consisting of carbon dioxide and the alkali metal bicarbonates,

d. said electrolyte being selected from the class consisting of the alkali metal carbonates and bicarbonates.

e. said combination comprising by weight from 0.1 to

20 parts of said electrolyte per part of silica pigment, as SiO and f. said composition having been dried; and the electrolyte thereof may comprise alkali metal bicarbonate in predetermined significant proportions, e.g. in the range of at least 2 mol percent to at least 90 mol percent thereof.

Precipitated silica having bound alkali.

Furthermore the composition may be in the form of a spray dried powder with the advantages of such form; and may comprise a mixture of said detergent adjuvant combination with detergent material selected from the class consisting essentially of the water soluble members of the following groups: Group (l) soaps; Group (II) synthetic anionic detergents; Group (III) anionic polymeric emulsifiers; Group (IV) non-ionic detergents; Group (V) non-ionic polymeric emulsifiers; and combinations of two or more of said members, in a ratio in the range of 5195 to 955 parts dry basis, by weight, based on the silica content of the adjuvant combination as SiO and the product may comprise hydrated silica pigment (and at least a part of said electrolyte) which has been prepared in the presence of the detergent material.

In other embodiments the product may comprise the anionic detergent formed by reacting, in the presence of the precipitated silica pigment, the water insoluble anionic detergent free acid with alkali derived in the preparation of said pigment; and the total detergent in the product may comprise at least 5 parts per 100 dry basis by weight of detergents selected from particular anionic ones of the aforesaid groups.

BRIEF DESCRIPTION OF THE DRAWINGS In the accompanying drawing the single FIGURE is a chart illustrating the preferred and most preferred ranges of reactants for preparing detergent adjuvant combinations of the invention.

DESCRIPTION OF PREFERRED EMBODIMENTS In preparing the detergent adjuvant in accordance with this invention commercially available alkali metal silicates may be employed, i.e. sodium silicates of the weight ratio l la O/(SiO in which the ratio of sodium oxide to silicon dioxide may range from 1:0.48 to l:3.75 with the soluble glass range 111.6 to 123.75 being preferred and the most preferred range being 123.0 to l:3.5e.g. 3.22 in the 41 Be sodium silicate of commerce (see FIG. I).

Acidulation of the sodium silicate for forming detergent adjuvant of this invention is carried out in aqueous solution with the aid of carbon dioxide and/or alkali metal bicarbonate eg. sodium bicarbonate, and as hereinafter exemplified water soluble alkali metal salts may be included in the solution in the range of from O to 4 mols per mol of alkalinity of the sodium silicate as Na O. for regulating the particle size of the silica pigment product. Such salt may be recovered as part of the detergent adjuvant and when the salt so employed is alkali metal carbonate its recovery correspondingly increases the alkalinity of the adjuvant combination.

Such acidulation may be applied to alkali metal silicate solutions having concentrations of alkali metal silicate-formula M O(SiO in which M is alkali metal--in the range of about 20 grams per liter to about 200 grams per liter, and may be carried out at temperatures between the freezing point and boiling point of water, i.e. from about 5 to about C. at atmospheric pressure, or up to 200 C. or more if conducted under higher pressures, and with or without the initial or timed addition of electrolyte.

The carbon dioxide gas employed in this invention may be full strength or may be diluted with air or other inert gases, e.g. such as the dilute carbon dioxide gas produced by the combustion of hydrocarbons such as propane or butane.

The process of this invention may be conducted in a batchwise or stepwise manner, or continuously, depending on available equipment.

The FIGURE sets forth at A a region bounded by a, a, a", and a in which the detergent adjuvant of this invention is preferably produced, i.e. at the bottom of the preferred range aqueous sodium silicate solution of the composition Na O(SiO at about 5% concentration, by weight, will form electrolyte and precipitate alkaline hydrated silica pigment when said solution has been acidified with the addition of about 0.7 to 0.8 mols of carbon dioxide (point a) and, to reduce the alkalinity of the precipitated pigment and its serum, further carbon dioxide may be added and the electrolyte sodium carbonate can be converted in whole or in part to sodium bicarbonate as indicated along line a-a'. At the top of this preferred range aqueous sodium silicate solutions of the composition Na O(SiO will form sodium carbonate electrolyte and precipitate alkaline hydrated silica pigment when said solution is acidified with 0.4 to ()5 mols of carbon dioxide, as indicated at point a". Likewise for this precipitate the alkalinity may be converted in whole or in part through sodium carbonate to sodium bicarbonate depending on the extent of carbonation as indicated along line a"a"'.

The size of the silica particles may be regulated during the preparation of the alkaline silica pigment.

As shown in the drawing, when one mole of sodium silicate of the composition Na O(SiO (lying at the point of ordinate value 3.22, abscissa value 0, at the left side of the drawing) is aciduated with about 0.6 moles of carbon dioxide so that about 60% of the Na O is converted to Na CO then at ordinate value 3.22 and abscissa value 0.6 alkaline silica pigment will have precipitated at about (Na O)0,4(SiO i.e. Na O(SiO2)a.05, and the weight of bound alkali will be (Na O/Na O(Si- O )8.O5)( 100), equalling (62/545)(100) or about ll.4% by weight as Na O; and if the acidulation with carbon dioxide is carried to the point where one mole of CO has been reacted per mole of Na O and sodium bicarbonate is beginning to form in the serum, at about ordinate value 3.22 and abscissa value 1.0 which falls on the line b-b" in the drawing, then the bound alkali of the alkaline silica pigment precipitate will be about 2% by weight as Na O; and if the acidulation with carbon dioxide is continued until the sodium carbonate in the serum is converted to sesquicarbonate (ordinate value 3.22 and abscissa value l.5) then the bound alkali of the silica pigment will be in the range of 1% by weight as Na O. When the adjuvant alkaline silica pigment precipitate is prepared from sodium silicate of the formula N21 O(SiO H2 treated with CO until the precipitated silica has a bound alkali content of 2% by weight as Na O, and the resulting alkaline pigment slurry is dried without separating any of the liquor from the alkaline silica pigment" slurry, the dried detergent adjuvant combination will contain bound alkali and free alkali in thefamount of about 35 weight as sodium carbonate.

Table A shows the calculated composition (dry basis) of the preferred detergent adjuvant products depending on the ratio of Na O to SiO in the sodium silicate solution, and the degree of carbonation effected. The quantity of sodium carbonate in the product can be varied at will and a quantity of sodium bicarbonate included if it is desirable to lower the pH, as above described.

TABLE A Sodium Silicate Composition Product Weight 70 Na O(SiO 1 mole C 2 moles CO SiO Na CQ SiO NaHCO These calculated figures are on an anhydrous basis and have not been corrected for bound alkali.

0 NaO- ('s'i-o) -si-ona.

in which n=50.6 and the weight ratio of Na O/SiO is 2/98.

The pigment in addition to the aforesaid silica and bound alkali content has about 8% bound water which is removable by heating the pigment to 1000 C.

The sodium silicate employable herein is represented by the formula Na O(SiO in which x lies in the range of 0.48 to 3.5 and when such sodium silicate is acidulated with carbon dioxide until the silica pigment forms then such pigment can have a bound alkali in range of 02-40% by weight based on the silica content of the pigment as SiO and further the pigment can have a bound water content of about 515% by weight or more based on the silica content of the pigment as SiO In the adjuvant combination of silica and sodium carbonate and/or sodium bicarbonate and in the detergent combinations of detergent and silica and sodium carbonate and/or sodium bicarbonate the bound alkali content of the silica is essential as it provides a means of removing heavy metal ions from the water of the cleansing operation. Thus the alkali metal ion, i.e. the sodium ion of the bound alkali exchanges with the heavy metal ion, thus the more hydratable and more soluble sodium ion of the silica is replaced by the less hydratable and less soluble heavy metal ion, i.e. by the calcium or magnesium ion.

In contrast a silica pigment which has been treated with acid and/or heavy metal salt and hasv no residual bound alkali no longer possesses the property of being able to remove heavy metal ions from the aqueous phase and thus cannot reduce the hardness of water as such hardness may be present in the cleansing operation.

The detergent materials with which the detergent ad- 5 juvant of the present invention may be used, and which may be combined therewith to form detergent compositions of the invention, are selected from the class consisting essentially of the water soluble members of the following groups: Group (I) soaps; Group (II) synthetic anionic detergents; Group (III) anionic polymeric emulsifiers; Group (IV) non-ionic detergents; Group (V) non-ionic polymeric emulsifiers; and combinations of two or more of said members; and may be combined with the adjuvant in a ratio in the range of 5:95 to :5 parts dry basis, by weight, based on the silica content of the adjuvant combination as SiO By the term soap is meant the alkali metal salts, amine salts, and ammonium salts of carboxylic acids (herein termed corresponding free acids) having from lto l0 carboxylic acid groups and having at least one carboxylic acid group attached to a chain of from 8 to 36 carbon atoms. Carboxylic acids meeting this definition are exemplified by the following: the fatty acids and the rosin acids and derivatives thereof, which have from 1 to 10 carboxyl groups and a chain of from 8 to 36 carbon atoms attached to at least one carboxyl group thereof, and such long-chain carboxylic acids include the individual fatty acids such as caprylic, capric, lauric, myristic, palmetic, stearic, oleic, linoleic, linolenic, abietic, hydroabietic, dehydroabietic, ricinoleic, and the like; the naphthenic acids; the mixed fatty acids derived from vegetable oils such as coconut, palm, linseed, cottonseed, soya, tung, perilla, tall, corn, oiticica, and castor oils, the mixed fatty acids derived from animal fats such as tallow fatty acids; the mixed fatty acids derived from fish oils, such as herring, menhadden, salmon and sardine oils, and the like; the dimers, trimers, and tetramers of the foregoing unsaturated fatty acids such as the dimer acids from bodied soya bean oil, the trimer acids from bodied linseed oil, and the dimers, trimers and tetramers of fish oil fatty acids; and it being understood that to employ unsaturated fatty acids set forth above to form soap usually such acids must be at least partially and preferably totally hydrogenated. The designated salt of the carboxylic acids, having from 8 to 18 carbon atoms are preferred.

By the term synthetic detergents is meant herein the anionic and/or non-ionic surface active agents or detergents. The anionic detergents include alkyl (C -C aryl sulfonates, ethoxylated alkyl aryl sulfonates, alkyl (C -C sulfates including fatty acid alcohol sulfates, alkyl (,;C,,,) sulfonates, ethoxylated alcohol sulfates, alkyl and alkenyl sulfonates including a-olefin sulfonates, the alkyl i.e. the monoor di-alkyl (Cg-C esters of sulphosuccinic acid. The compounds hereof are employed in the form of alkaline salts, i.e., the sodium, potassium, ammonium or amine salts, of the corresponding free acids and include: sodium octyl sulphate, sodium monyl sulphate, sodium decyl sulphate, sodium undecyl sulphate, sodium dodecyl sulphate, sodium tridecyl sulphate, sodium tetradecyl sulphate, sodium pentadecyl sulphate, sodium hexadecyl sulphate, sodium heptadecyl sulphate, sodium octadecyl sulphate,

sodium oleyl sulphate, sodium octyl sulphonate, so-

dium nonyl sulphonate, sodium decyl sulphonate, sodium undecyl sulphonate, sodium dodecyl sulphonate, sodium tridecyl sulphonate, sodium tetradecyl sulphonate, sodium pentadecyl sulphonate, sodium hexadecyl sulphonate, sodium -octadecyl sulphonate, sodium bleyl sulphonate, sodium salt of di-octyl sulphosuccinate. sodium octyl benzene sulphonate, sodium nonyl benzene sulphonate. sodium decyl benzene sulphonate, sodium undecyl benzene sulphonate, sodium dodecyl benzene sulphonate, sodium tridecyl benzene sulphonate, sodium tetradecyl benzene sulphonate, sodium pentadecyl benzene sulphonate, sodium hexadecyl benzene sulphonate, sodium heptadecyl benzene :sulphonate, sodium octadecyl benzene sulphonate, sodium tri (isopropyl) benzene sulphonate, sodium tri lisobutyl) benzene sulphonate, sodium tri (isopropyl) naphthalene sulphonate, sodium tri (isobutyl) naphthalene sulphonate, and combinations thereof, and the like.

The non-ionic detergents include alakanolamides, fatty amine oxides, ethylene oxide and propylene oxide condensates of long chain fatty alcohols, alkylphenols, fatty acids, mercaptans, amides, alkanolamides, amines, and more particularly the following represented by the formula RS(C l-l O),.-H wherein R is a 8 to 12 carbon alkyl radical and n is an integer from about 4 to 30.

It is most desirable that detergents be employed which are biodegradable, that is have essentially straight chain alkyl groups.

Among the non-ionics are the Phuronic detergents of the general formula Phenol ethylene oxide condensate (Type) (mols) Nonylphenol 9 Nonylphenol l2 Dinonylphenol 7 Dinonylphenol l5 Dodecylphenol 18 For further examples of alkyl and alkaryl compounds which may be condensed with alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide, and for example of these alkyl oxide condensates phosphated derivatives see for specific examples Papaloss U.S. Pat. No. 3,346,670 the examples thereof being incorporated herein by reference.

Included herein are other ethylene oxide condensate products for example dodecyl benzene sulfonamide condensed with 10 mols of ethylene oxide and decyl sulfonamide with 6 mols of ethylene oxide and the like.

Included herein are the amine oxide detergents of the general formula R R R N-O in which R is a radical having 8 to 28 carbon atoms and to 2 hydroxy groups and 0 to ether groups, R is a C to C alkyl radical and R is selected from the alkyl radicals and the hydroxylkyl radicals having 1 to 3 carbon atoms. For specific examples of the amine oxide detergents see Deans 8 U.S. Pat. No. 3,523,088 the examples thereof being incorporated herein by reference.

The anionic detergents include the phosphorous containing organic detergent compounds such as the phosphate esters represented by the following Alkyl-O P-(OMe) Aryl-O-P- (OMe) Q (Aryl-O-) -P-OMe Alkyl-O 9 P-OMe Arylin which the alkyl has 8-27 carbon atoms and the aryl-0 is a phenoxy radical or a mono-, di-, or tri-alkylphenoxy radical in which the alkyl groups have 1 to 27 carbon atoms and Me is sodium, potassium, ammonium or substituted ammonium; the such detergents further include the ethylene oxide and propylene oxide modifications of said organic phosphates as represented by the following formulae;

Alkyl-O- (C H O) in which the alkyl and aryl group limits are defined as for the previous subclass of phosphoric acid esters, n and m are integers from 1 to 40 and Me is sodium or potassium.

Included hereunder are other phosphorous containing detergents such as the phosphonio carboxylates are described in U.S. Pat. No. 3,504,024 which are hereby incorporated by reference.

Also the phosphine oxide detergents having the formula R R R PO in which R is 10 to 28 carbon atoms radical with 0 to 2 hydroxyl groups and 0 to 5 ether groups and R" is a C to C alkyl groups and R is an alkyl radical or hydroxy alkyl radical with from I to 3 carbon atoms. For specific examples of the phosphine oxide detergents see Dean's U.S. Pat. No.

3,523,088 the examples thereof being incorporated herein by reference.

By the term anionic polymeric dispersants or anionic polymeric emulsifiers is meant polymers having organic acid groups as alkali metal salts and as "such are water soluble or dispersable.

By the term non-ionic polymeric dispersants or nonionic polymeric emulsifiers is'meant polymers which are watersoluble or dispersable without having organic acid and/or basic groups, the hydrophilic nature of these polymers being provided by the hydroxyl, or the like water solublizing non-ionic groups.

The term polymeric dispersants or polymeric emulsifiers as employed herein is used in a limited sense and meant to include both anionic dispersants or emulsifiers and/or non-ionic dispersants or emulsifiers, however, such term excludes cationic dispersants or emulsifiers.

lncludedamong the polymeric dispersants or emulsifiers are those produced by mass polymerization, or solution polymerization, suspension polymerization or, emulsion polymerization employing monomers yielding polymers that are water soluble or water dispersable or convertible to such form as with the aid of alkali. These polymers may be formed from hydrophilic monomers, or from mixtures of hydrophilic monomers with hydrophobic monomers, provided the quantity of hydrophobic monomer is not so high as to prevent the polymer from being, or being rendered, water soluble or dispersable. The hydrophilic monomers that may be employed alone or with other monomers, in forming polymers that are water solube of dispersable or convertible to such form may and include the yellowing: (1) anionic hydrophilic monomers such as those containing carboxylic, sulphonic acid or acid sulphate groups, or acid derivatives of phosphoric acid and (2) non-ionic hydrophilic monomers are those containing e.g. hydroxyl, ether, hydroxy-ester, and/or amide groups.

The polymeric dispersants or emulsifiers employed in the present invention may be prepared from one or more of the hydrophilic monomers, even polymerizing monomers of the anionic and/or non-ionic, types in the same hydrophilic polymer. Likewise the hydrophilic monomers may be polymerized with hydrophobic monomers provided the amount of hydrophobic monomer does not prevent the polymeric emulsifier from dissolving or dispersing in aqueous medium with or without the aid of a water solube base, including, for example, the alkali-metal hydroxides, bicarbonates and carbonates, and ammonia and its derivatives. The detergent compositions hereof include the water soluble or dispersable polymers in the presence of the alkaline silica and the electrolytes consisting of alkali metal carbonates and/or bicarbonates.

A variety of hydrophilic polymer can be employed as polymeric dispersants or emulsifiers especially watersoluble or water dispersible polyelectrolytes as for example those set forth'in Hendrick and Mowry U.S. Pat. No. 2,625,529, and in which is described a number of materials which are synthetic watersoluble polyelectrolytes having a weight average molecular weight of at least 10,000 and having a structure derived by the polymerization of at least one monoolefinic compound,

found that lower molecular weights polyelectrolytes of at least 1,000 to 2,000 and even as low as 700 can be employed as polymeric emulsifiers. The said Hendrick and Mowry patent is hereby incorporated by reference. Further, watersoluble anionic poiymeric dispersants which include salts of polycarboxylic acid polymers and copolymers are referred to as polyelectrolyte builder material consisting of water-soluble salts of aliphatic polycarboxylic acid as in the patent to Diehl U.S. Pat. No. 3,308,067 which is hereby incorporated by reference.

Useful in preparing the polymeric dispersants or emulsifiers hereof is vinylidene including vinyl monomer material of the following subclasses:

Monomers with carboxyl groups which includes monobasic organic acids such as acrylic, methacrylic cinnamic; propionic, crotonic and the like acids; dibasic acids including catonic, mesaconic, citraconic, itaconic, aconitic, furmaric, maleic and the like acids, and the half esters of the dibasic acids esterified with ethylene glycol, propylene glycol and the glycol ethers and the like;

Monomers with sulfonic groups which include styrene sulfonic acid (p-vinylbenzenesulfonic acid), toluene sulfonic acid and the like;

Monomers with hydroxyl and ester groups: the hydroxyalkal acrylates and methacrylates which include hydroxyethyl acrylate and methacrylate, hydroxypropyl acrylate and methacrylate and the like;

Monomers with amide groups which include acylamide, N-isopropylmethacrylamide, N-methylacrylamide, N,N-diethylacrylamide, N-ethylacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N,N- dimethylacrylamide, N,N-dimethylmethacrylamide and acrylamide and the like.

Polymers with hydrophylic groups:

the polyvinyl alcohols obtained by hydrolysis of polyvinyl acetate, polyvinyl alcohol copolymers, the N- alkyl-arylamide-vinyl alcohol copolymers which can be prepared by the hydrolysis of N-alkyl-acrylamide-vinyl acetate interpolymers (see U.S. Pat. No. 2,798,047 which is incorporated herein by reference).

Vinylidene monomers with N-vinyl lactam groups such as l-vinyl-2-pyrrolidone, l-vinyl-5-methyl-2- pyrrolidone, l-vinyl-3-butyl pyrrolidone, N-vinyl-S- methyl-S-ethyl pyrrolidone, N-vinyl-3,3,5-trimethyl pyrrolidone, N-vinyl-6butyl piperidone, 1-vinyl-2- piperidone, N-vinyl-coprolactom, Nvinyl-7ethylcoprolactam, N-vinyl-3,5-dimethyl caprolactam,

N-vinyl-4-isopropyl caprolactam, and the like;

Vinylidene monomers with ether groups such as vinyl methyl ether, vinyl butyl ether, methyl isopropenyl ether, and the like;

Other polytectrolytes: copolymers of ethylene and maleic anhydride, copolymers, maleic anhydride and methyl vinyl ether, copolymers of styrene and maleic anhydride, hydrolized polyacrylonitrile, hydrolized polymethacrylontrile.

It is understood that the more hydrophobic vinylidene monomers set forth herein may have to be combined with more hydrophilic monomers of those set forth herein in order to provide interpolymers which are water soluble or water dispersable.

Where the polymers including interpolymers are readily saponifiable as for example may be the case with the ester polymers then the more alkaline combinations of alkaline silica and sodium carbonate are to be minimized and the alkaline silica-sodium bicarbonate combinations are preferred.

When it is desirable to increase the hydrophobic nature of the polymers then a hydrophobic vinylidene monomer may be selected from the known vinylidene monomers and the term vinylidene monomer as used herein is meant to include vinyl monomer.

The polymerization technics for the monomers selected herein are well-known to the art as are likewise the polymerization catalysts such as, for example, the organic peroxides, e.g. benzoyl peroxide, the organic hydroperoxides, e.g. cumene hydroperoxide, the azocatalysts e.g. azo-bis-isobutyronitrile, the inorganic peroxygen compounds, e.g. potassium persulfate or the hydrogen peroxide and the like.

Anionic and/or non-ionic emulsifiers may be used to prepare the polymeric detergents hereof.

The terms dried and drying herein are employed in the sense in which they are employed in the drying of soap and detergent products, i.e. the sense of removing excess water as by evaporation, spray drying, reverse osmosis or other membrane methods, or other applicable procedures, the drying being effected sufficiently to produce a commercially useful product.

The following examples of specific embodiments of the invention are set forth to facilitate practice of the same, and are to be regarded as illustrative and not restrictive of the invention, the scope of which is more particularly pointed out and distinctly claimed hereinafter.

EXAMPLES EXAMPLE 1 This example was carried out in the following manner: to 2000 ml. of a 41 Be aqueous solution containing 4 mols sodium silicate of the composition represented by Na O(SiO was added 14 liters of water and placed in a precipitator vessel equipped with an agitator and the temperature thereof raised to 79 C. To this hot aqueous sodium silicate solution was gradually added 4 liters of an aqueous solution containing 4 mols of sodium carbonate and concurrently therewith but over a more extended period was added 4 mols of carbon dioxide. The time schedule of these additions is shown in Table 1.

12 On spray drying of the resulting slurry of wet precipitated alkaline silica pigment having bound alkali and free alkali therein, a detergent adjuvant having the fol lowing composition is obtained:

Detergent Adjuvant Composition Silica pigment (with 2% bound alkali) Sodium carbonate "Cale. anhydrous basis.

EXAMPLE 2 2(a). Example 1 is repeated in pound mols and prior to drying 875 lbs. of the sodium salt of dodecyl benzene sulphonate (DDBS) is added as an aqueous solution and after thorough mixing the composition, on spray drying, yields the following product:

Detergent Composition Wt., lbs.* Wt.,

Sodium salt DDBS 875 35.0 Silica Pigment (with 2% bound alkali as Na O) 787 31.6 Sodium carbonate 832 33.4

Calc. anhydrous basis.

2(b). Example 1 is repeated in pound mols with the CO addition, continued until the acidulation reaches 150% and 875 lbs. of the sodium salt of dodecyl benzene (DDBS) is then added as aqueous solution, together with 62 lbs. of carboxy methyl cellulose (CMC) and an optical brightening agent, 5 lbs., and the combination is spray dried yielding the following product:

To a stainless steel reactor with agitator is added 1400 lbs. of water, 32.7 lbs. of dodecyl benzene sulfonate, and 4 lbs. sodium hydroxide and the mixture raised to C. There is then added 310 lbs. equivalent to 200 mols Na O(SiO of 41 Be commerical sodium silicate solution. After thorough mixing carbon dioxide is introduced through a lead tube to the bottom of the reactor and over a period of 600 minutes 200 mols of carbon dioxide is introduced at a constant rate. On completion of the acidification with carbon dioxide the product is spray dried and has the following composition'.

Thecornbind oifo .he 'w t silica slurry and the de tergent paste onspraydr'ylng yields a product of the following composition z DetergeniComposition Wt, 1b.* Wt, /r* Detergent Composition Wt. grams* Wt. 7r*

Sodium salt Of DDBS 34.9 20.9 Silica Pigment (with 2% bound 'P smei t (with 2% 5 alkali) 1,182 37.5 boimd alkal as N320 Sodium Carbonate 1.214 38.5 Sodlum Carbonate Sodium salt dodecylbenzene 167.0 100.0 sulphonate 640 20.2 V Oleic acid diethanolamidc 45 1.4 *Calc; anhydrous basis Carboxy methyl cellulose 75 2,4 3,156 100.0

4 *Calc. anhydrous basis In this example 3000 ml. of type N sodium silicate (Na O(SiO containing 6 mols of Na O is diluted EXAMPLE 6 with 6 liters of water to which is added 636 g. (6 mols) ,of sodium carbonate dissolved in 8 liters of water at 60 A 270 gallon i f equ 1pped wlth dnveri 50 and the combination is placed in a ceramic vessel r.p.m. low shear stirring arm 18 charged with 780 liters and agitated by a 3 bladed 3" propeller driven 600 of 80 C. water, and 65 kllosof sodium soap of tallow The acidulating agent consists of fatty acids is added and permitted to dissolve, followed mols) of sodium bicarbonate dissolved in 15 liters of 20 y 144 kilos of Commercial Be Sodium Silicate waterat 0 C, The id i i agent i dd d to th taining 200 mols of the composition expressed by the dilute sodium silicate in a controlled manner according formula Na O/(SiO The mixture is thoroughly to Table 11 herein. blended with the aid of the agitator. While the solution TABLE II is held at 80 i 10 C. a submerged combustion burner supplied with propane and air is ignited and submerged Time (minutes Acidulation (mols NaHCOa below the surface of the solutlon. The submerged comu u l cumulative) bustion burner is operated at a relat1vely constant rate 0 so that after 150 minutes the acidulation had prog- 62 1.1 ressed to 34%, i.e. 68 mols of carbon dioxide had been absorbed by the sodium silicate solution. 129 3.9 165 6 0 1n the examples hereof heat can be supplied by vessel heating acket 180 or heating coils and any source of carbon dioxide may be used. 9 I The acidulation at 80 C. is continued for 510 min- 219 utes with the aid of the submerged combustion burner Initial precipitation of silica. until after a total of 660 minutes the acidulation has 1 reached 100%, i.e. 200 mols of carbon dioxide has The slurry of precipitated silica having bound alkali been absorbed by the silica slurry. Throughout the forand free alkali, 0n y g yields a Product Of the fOllOW- mation of the silica slurry the slow speed, low shear stirg JCOmYPOSItIOHI 40 rer is used, and from time to time water is added to compensate for the loss thereof due to operation of the V burner. Silica Com osltion Wt. rams* WL. 72* I i i V g The resulting product, when dried, has the followlng Silica Pigmenttwith 2% bound o iti alkali) 1.182 48.5 v

Sodiurit Carbonate 1,236 51,5

2,418 100.0 v7 Detergent Composition Wt. Ki1os* WI. 7c* Cale. anhydrous basis Silica pigment (with 2% bound alkali) 39.4 31.4 Sodium carbonate 21.1 16.8 EXAMPLE 5 Sodium tallow fatty acid soap 65.0 51,8 Example 4 is repeated, however prior to drying, the 125.5 100.0 silica slurry containing bound alkali and free alkali C I h d b there is added detergent paste formulated as follows: mus

EXAMPLE 7 DETERGENT PASTE FORMULATION I d w To a 270 gallon reactor with stirrer is charged 680 grams liters of 80 C. water and 144 kilos of commercial 41 Linear dodecylbenzene sulpho'nate 600 Be sodium silicate containing 200 mols of sodium sili- Caustic Soda 75 ,Sodium hypochlorite a Cate of formula 2 )a.az n he mixture is Oleic acid diethanolamide- 45 thoroughly blended. With the aid of a submerged comgfgzg mcthyl cellulme 2 3 bustion burner carbon dioxide is supplied to the reactor 1 at a constant rate at a temperature of 80 C. and after 660 minutes 200 mols of carbon dioxide has been reacted with the sodium silicate solution to yield alkaline silica and sodium-carbonate in the following proportions:

Detergent Adjuvant Composition Wt., Kilos* Wt. 7r" Detergent Composition e Sodium salt vinyl methyl iil za l ih (wuh 2% bound 3 4 65 5 Other maleic anhydride 30 18 5 copolymer bodium carbonate Zl 35 sodium salt of DDBS 5 11 60.5 100.0 Silica pigment (2% bound alkali) 85 52.4 Talc anhydrous ham Sodium carbonate 42 26.0 162 100.0

8 Cale. anhydrous basis.

iExam 1e 7 was re eated exce t that the 20 kilos of p p p EXAMPLE ll dodecylbenzene sulfonic acid was replaced with 20 kilos (l00% active basis) of nonyl phenol condensed In an agitated vessel is added 1400 lbs. of water, 310 i h 9 10 l h l id d h ble d th lbs. of aqueous sodium silicate containing 200 mols of oughly mixed and spray dried and has the following z z)a.2zr f P P *r?Q Composition; sodium salt of polyacrylic acid and after mixing the temperature is raised to 60 C. and 300 mols of carbon dioxide absorbed over a period of 900 minutes, then is Detergent Composition Wt. Kilos* Wt. added 17.9 lbs. of alipal 233** containing 28% of the 27 b d [k l. 39 4 48 8 sodium salt of ethoxylated nonyl phenol sulfonate and 355,1; g g g 2612 the combination blended and dried. The product had Nonyl phenol with 9-10 the following composition:

molecules of ethylene 25 oxide 20.0 25

loo-0 Detergent Composition WL, lbs.* Wt.,%*

"(Talc anhydrous basis Sodium polyacrylic acid salt 2O 12 30 Sodium alkyl phenol ethoxylate sulfonate 5 3 EXAMPLE 9 Silica pigment (1% bound alkali) 86 51 in an agitated vessel is added 1400 lbs. of water, 310 s diu carbonate i2 3 Sodium bicarbonate 33 20 lbs. of aqueous sodium silicate contain ng 200 mols of Trisodium phosphate 10 6 N8 O(SlO and 50 lbs. of poly(sodium styrene sul- 166 100 fonate) and after adequate mixing the solution temper- 35 r o 'Thtd h ht b ld'th d t'lh ht,tt mm was ralsed 75 C Acldulatlon Carbon anr3in";ri'ief fi .iZr.2"3ooi$32. 2;...3055833510325;rii riei nirff xide was carried out at a relative constant rate so that ?odium triplt osphaie and the like. The said phosphate salts may be added after ormat'on o the si ica. after 800 minutes 300 mols of carbon dioxide had been "1mm, product of General Aniline corp, absorbed. Then was added 10 lbs. of nonyl phenol con- 40 tiensed with 9.5 mols ethylene oxide and after uniform All above examples of detergent compositions may mixing the blend was spray dried. The product had th also be practiced with addition of conventional soap following composition: and/or detergent additives, usually in minor proportions, such as perfumes, disinfectants, bleaches, brighteners, abrasives, enzymes, solvents and oils, rnedicating Delergem Composition lbs? ingredients, and the like, without departing from the 5 It 1 S invention.

urn S O renc o f g y y 25 While there have been described herein what are at Alkyl phenol ethoxylate 1O 5 present considered preferred embodiments of the in- 5ilicallpiglri;ent 1% bound 86 43 5O vention, it will be obvious to those skilled in the art that i' 2] l Sodium Carbonate 21 I05 modifications and changes may be made therein with- Sodium bicarbonate 33 16.5 out departing from the essence of the invention. It is 200 100.0 therefore understood that the exemplary embodiments are illustrative and not restrictive of the invention, the

Talc scope of which is defined in the appended claims, and

that all modifications that come within the meaning EXAMPLE 10 and range of equivalents of the claims are intended to D I be included therein. in an agitated vessel is added 1400 lbs. of water, 3 l0 1 claim. lbs. of aqueous sodium silicate containing 200 mols of A process for preparing a detergent adjuvam Na O(SiO and 30 lbs. of the sodium salt of the cobination which comprises; P y of W methyl ether and malelc anhydflder a. forming an aqueous solution of water soluble alkali and after blending and the temperature raised to 80 metal ili CH 200 mols of carbon dioxide was reacted over a peb. adding to said solution sufficient reactant selected :riod of 500 minutes. Then 5 lbs. of dodecylbenzene sulfrom the class consisting of carbon dioxide and alphonic acid sodium salt was added and the blend spray dried and the product had the following composition:

kali metal bicarbonate to form therewith a solution of electrolyte selected from the alkali metal carbonates and bicarbonates and a precipitate of alkaline silica pigment therein containing from 0.2 to 40% bound alkali by weight based on the silica of I the pigment, and

' c. recovering and essentially drying together the combination of said alkaline silica pigment and at least 25% drybasis, by weight, of the electrolyte resulting from step'('b).

2. A process as claimed in claim 1, in which step (b) is conducted to provide said solution with electrolyte consisting at least 2 mol percent of alkali metal bicarbonate.

3. A process as claimed in claim 1, in which step (b) is conducted to provide said solution with electrolyte consisting at least mol percent of alkali metal bicarbonate.

4. A process as claimed in claim 1, in which step (b) is conducted to provide said solution with electrolyte consisting at least 30 mol percent of alkali metal bicarbonate.

5. A process as claimed in claim 1, in which step (b) is conducted to provide said solution with electrolyte consisting at least 50 mol percent of alkali metal bicarbonate.

6. A process as claimed in claim 1, in which step (b) is conducted to provide said solution with electrolyte consisting at least 90 mol percent of alkali metal bicarbonate.

7. A process for preparing a detergent composition which comprises:

a. forming an aqueous solution of water soluble alkali metal silicate containing water soluble material selected from the class consisting essentially of the members of the following groups: Group (I) soaps; Group (II) synthetic anionic detergents; Group (Ill) nonionic detergents; and combinations of two or more of said members; in a ratio in the range of 5:95 to 95:5 parts dry basis, by weight, based on the silica content as SiO b. adding to said solution sufficient reactant selected from the class consisting of carbon dioxide and alkali metal bicarbonate to form therewith a solution of said water soluble material and electrolyte selected from the alkali metal carbonates and bicarbonates with a precipitate of alkaline silica pigment therein containing from 0.2 to 40% bound alkali by weight based on the silica of the pigment, and

c. recovering the products of reaction (b) as a detergent composition incorporating said electrolyte and said alkaline silica pigment precipitate 8. A process as claimed in claim 7, in which in step (a) less than the maximum ratio of said water soluble material to silica is employed, and in step (c) the detergent adjuvant combination is mixed with further material selected from the members of said class and combinations thereof, in an amount which combined with that included in step (a) lies in the aforesaid ratio range.

9. A process as claimed in claim 7, in which, in step (c) the further material comprises material selected from the sub-class consisting of the members of Groups (I), and (II) which is formed in the presence of the silica pigment by reaction of the corresponding free acid with alkalinity of the combination resulting from step (b).

10. A composition consisting essentially of a mixture of the following components (I) and (II):

I. A detergent adjuvant combination consisting essentially of:

a. an alkaline hydrated silica pigment combined with b. an electrolyte,

c. said alkaline silica pigment having a surface area in the range of 25 to about 500 meters per gram and having been prepared in aqueous medium by the acidulation of an aqueous solution of alkali metal silicate, and having, prior to drying thereof, been combined with said electrolyte,

d. said electrolyte having been selected from the class consisting of the alkali metal carbonates and bicarbonates, and being present in an amount in the range of 0.1 to 20 parts of electrolyte per part of silica pigment, as SiO by weight and e. said combination of said electrolyte and pigment in aqueous medium having been dried, and

II. water soluble material selected from the class consisting essentially of the'members of the following groups: Group (I) soaps; Group (II) synthetic anionic detergents; Group (III) non-ionic detergents; and combinations of two or more of said members; in a ratio in the range of 5:95 to :5 parts dry basis, by weight, based on the silica content of the adjuvant combination as SiO 11. A composition as claimed in claim 10, said hydrated silica pigment and at least a part of said electrolyte having been prepared in the presence of the said water soluble material.

12. A composition as claimed in claim 10, in which the water soluble material comprises at least 5 parts per 100, dry basis by weight, of non-ionic detergent from Group (III).

13. A composition as claimed in claim 10, in which the composition further comprises at least 5 parts per 100, dry basis by weight, of non-ionic polymeric emulsifier material.

14. A process for preparing a detergent adjuvant combination which comprises:

a. forming an aqueous solution of water soluble alkali metal silicate,

b. adding to said solution sufficient reactant selected from the class consisting of carbon dioxide and alkali metal bicarbonate to form therewith a solution of electrolyte selected from the alkali metal carbonates and bicarbonates and a precipitate of alkaline silica pigment therein containing from 0.2 to 40% bound alkali by weight based on the silica of the pigment, and

c. recovering and essentially drying together the combination of said alkaline silica pigment and at least 25% dry basis, by weight, of the electrolyte resulting from step (b), said recovery including spray drying.

15. A process for preparing a detergent adjuvant combination which comprises:

a. forming an aqueous solution of water soluble alkali metal silicate,

b. adding to said solution sufficient reactant selected from the class consisting of carbon dioxide and alkali metal bicarbonate to form therewith a solution of electrolyte selected from the alkali metal carbonates and bicarbonates and a precipitate of alkaline silica pigment therein containing from 0.2 to

40% bound alkali by weight based on the silica of the pigment, and

c. recovering and essentially drying together in combination said pigment and substantially all of the electrolyte resulting from step (b), as the detergent adjuvant combination.

16. A process for preparing a detergent adjuvant combination which comprises:

a. forming an aqueous solution of water soluble alkali metal silicate,

b, adding to said solution sufficient reactant selected from the class consisting of carbon dioxide and alkali metal bicarbonate to form therewith a solution of electrolyte selected from the alkali metal carbonates and bicarbonates with a precipitate of alkaline silica pigment therein containing from 0.2 to 40% bound alkali by weight based on the silica of the pigment, and recovering together said alkaline silica pigment and at least 25% dry basis, by weight, of the electrolyte resulting from step (b), in combination, as .a detergent adjuvant combination, said recovery including incorporating said adjuvant combination with detergent material selected from the class consisting essentially of the members of the following groups: Group (I) soaps; Group (II) synthetic anionic detergents; Group (III) non-ionic detergents; and combinations of two or more of said members; in a ratio in the range of 5:95 to 95:5 parts dry basis, by weight, based on the silica content as SiO thereby forming a detergent composition incorporating said detergent adjuvant combinationv 17. A process as claimed in claim 16, in which the detergent adjuvant combination, in step without having been dried following step (b), is mixed with an aqueous dispersion of said detergent material.

18. A process as claimed in claim 17, in which the recovery of the product is effected by spray-drying of the mixed adjuvant combination and aqueous dispersion.

19. A process as claimed in claim 16, in which there is also incorporated in the detergent and adjuvant combination material selected from the class consisting of the anionic polymeric emulsifiers and the non-ionic polymeric emulsifiers.

20. A process for preparing a detergent adjuvant combination which comprises:

a. forming an aqueous solution of water soluble alkali metal silicate.

b. adding to said solution sufficient reactant selected from the class consisting of carbon dioxide and alkali metal bicarbonate to form therewith a solution of electrolyte selected from the alkali metal carbonates and bicarbonates with a precipitate of alkaline silica pigment therein containing from 0.2 to 40% bound alkali by weight based on the silica of the pigment, and c. recovering and essentially drying together the combination of said alkaline silica pigment and at least 25% dry basis, by weight, of the electrolyte resulting from step (b), in combination, as a detergent adjuvant combination, said recovery including incorporating said adjuvant combination with detergent material selected from the class consisting essentially of the members of the following groups: Group (I) soaps; Group (II) synthetic anionic detergents; Group (Ill) non-ionic detergents; and combinations of two or more of said members; in a ratio in the range of 5:95 to 95:5 parts dry basis, by weight, based on the silica content as SiO thereby forming a detergent composition incorporating said detergent adjuvant combination, and

d. in which the detergent material comprises material selected from the sub-class consisting of the members of Groups (I) and (II) which is formed in the presence of the silica pigment by reaction of the corresponding free acid with alkalinity of the combination resulting from step (b).

21. A process for preparing a detergent adjuvant combination which comprises:

a. forming an aqueous solution of water soluble alkali metal silicate,

b. adding to said solution sufficient reactant selected from the class consisting of carbon dioxide and alkali metal bicarbonate to form therewith a solution of electrolyte selected from the alkali metal carbonates and bicarbonates with a precipitate of alkaline silica pigment therein containing from 0.2 to 40% bound alkali by weight based on the silica of the pigment, and

c. recovering and essentially drying together the combination of said alkaline silica pigment and at least 25% dry basis, by weight, of the electrolyte resulting from step (b), in combination, as a detergent adjuvant combination, said recovery including incorporating said adjuvant combination with detergent material selected from the class consisting essentially of the members of the following groups: Group (I) soaps; Group (II) synthetic anionic detergents; Group (III) non-ionic detergents; and combinations of two or more of said members; in a ratio in the range of 5:95 to 95:5 parts dry basis, by weight, based on the silica content as SiO thereby forming a detergent composition incorporating said detergent adjuvant combination, and

d. in which the detergent material comprises a soap formed in the presence of the silica pigment by saponification of fatty acid glyceride with the aid of alkalinity of the combination resulting from step

Claims

1. A PROCESS FOR PREPARING A DETERGENT ADJUVANT COMBINATION WHICH COMPRISES: A. FORMING AN AQUEOUS SOLUTION OF WATER SOLUBLE ALKALI METAL SILICATE, B. ADDING TO SAID SOLUTION SUFFICIENT REACTANT SELELCTED FROM THE CLASS CONSISTING OF CARBON DIOXIDE AND ALKALI METAL BICARBONATE TO FORM THEREWITH A SOLUTION OF ELECTROLYTE SELECTED FROM THE ALKALI METAL CARBONATES AND BICARBONATES AND A PRECIPITATE OF ALKALINE SILICA PIGMENT THEREIN CONTAINING FROM 0.2 TO 40% BOUND ALKALI BY WEIGHT BASED ON THE SILICA OF THE PIGMENT, AND C. RECOVERING AND ESSENTIALLY DRYING TOGETHER THE COMBINATION OF SAID ALKALINE SILICA PIGMENT AND AT LEAST 25% DRY BASIS, BY WEIGHT, OF THE ELECTROLYTE RESULTING FROM STEP B).

3. A process as claimed in claim 1, in which step (b) is conducted to provide said solution with electrolyte consisting at least 10 mol percent of alkali metal bicarbonate.

7. A process for preparing a detergent composition which comprises: a. forming an aqueous solution of water soluble alkali metal silicate containing water soluble material selected from the class consisting essentially of the members of the following groups: Group (I) soaps; Group (II) synthetic anionic detergents; Group (III) nonionic detergents; and combinations of two or more of said members; in a ratio in the range of 5:95 to 95:5 parts dry basis, by weight, based on the silica content as SiO2, b. adding to said solution sufficient reactant selected from the class consisting of carbon dioxide and alkali metal bicarbonate to form therewith a solution of said water soluble material and electrolyte selected from the alkali metal carbonates and bicarbonates with a precipitate of alkaline silica pigment therein containing from 0.2 to 40% bound alkali by weight based on the silica of the pigment, and c. recovering the products of reaction (b) as a detergent composition incorporating said electrolyte and said alkaline silica pigment precipitate.

8. A process as claimed in claim 7, in which in step (a) less than the maximum ratio of said water soluble material to silica is employed, and in step (c) the detergent adjuvant combination is mixed with further material selected from the members of said class and combinations thereof, in an amount which combined with that included in step (a) lies in the aforesaid ratio range.

10. A composition consisting essentially of a mixture of the following components (I) and (II): I. A detergent adjuvant combination consisting essentially of: a. an alkaline hydrated silica pigment combined with b. an electrolyte, c. said alkaline silica pigment having a surface area in the range of 25 to about 500 meters per gram and having been prepared in aqueous medium by the acidulation of an aqueous solution of alkali metal silicate, and having, prior to drying thereof, been combined with said electrolyte, d. said electrolyte having been selected from the class consisting of the alkali metal carbonates and bicarbonates, and being present in an amount in the range of 0.1 to 20 parts of electrolyte per part of silica pigment, as SiO2, by weight and e. said combination of said electrolyte and pigment in aqueous medium having been dried, and II. water soluble material selected from the class consisting essentially of the members of the following groups: Group (I) soaps; Group (II) synthetic anionic detergents; Group (III) non-ionic detergents; and combinations of two or more of said members; in a ratio in the range of 5:95 to 95:5 parts dry basis, by weight, based on the silica content of the adjuvant combination as SiO2.

11. A composition as claimed in claiM 10, said hydrated silica pigment and at least a part of said electrolyte having been prepared in the presence of the said water soluble material.

14. A process for preparing a detergent adjuvant combination which comprises: a. forming an aqueous solution of water soluble alkali metal silicate, b. adding to said solution sufficient reactant selected from the class consisting of carbon dioxide and alkali metal bicarbonate to form therewith a solution of electrolyte selected from the alkali metal carbonates and bicarbonates and a precipitate of alkaline silica pigment therein containing from 0.2 to 40% bound alkali by weight based on the silica of the pigment, and c. recovering and essentially drying together the combination of said alkaline silica pigment and at least 25% dry basis, by weight, of the electrolyte resulting from step (b), said recovery including spray drying.

15. A process for preparing a detergent adjuvant combination which comprises: a. forming an aqueous solution of water soluble alkali metal silicate, b. adding to said solution sufficient reactant selected from the class consisting of carbon dioxide and alkali metal bicarbonate to form therewith a solution of electrolyte selected from the alkali metal carbonates and bicarbonates and a precipitate of alkaline silica pigment therein containing from 0.2 to 40% bound alkali by weight based on the silica of the pigment, and c. recovering and essentially drying together in combination said pigment and substantially all of the electrolyte resulting from step (b), as the detergent adjuvant combination.

16. A process for preparing a detergent adjuvant combination which comprises: a. forming an aqueous solution of water soluble alkali metal silicate, b. adding to said solution sufficient reactant selected from the class consisting of carbon dioxide and alkali metal bicarbonate to form therewith a solution of electrolyte selected from the alkali metal carbonates and bicarbonates with a precipitate of alkaline silica pigment therein containing from 0.2 to 40% bound alkali by weight based on the silica of the pigment, and c. recovering together said alkaline silica pigment and at least 25% dry basis, by weight, of the electrolyte resulting from step (b), in combination, as a detergent adjuvant combination, said recovery including incorporating said adjuvant combination with detergent material selected from the class consisting essentially of the members of the following groups: Group (I) soaps; Group (II) synthetic anionic detergents; Group (III) non-ionic detergents; and combinations of two or more of said members; in a ratio in the range of 5:95 to 95:5 parts dry basis, by weight, based on the silica content as SiO2, thereby forming a detergent composition incorporating said detergent adjuvant combination.

17. A process as claimed in claim 16, in which the detergent adjuvant combination, in step (c), without having been dried following step (b), is mixed with an aqueous dispersion of said detergent material.

20. A PROCESS FOR PREPARING A DETERGENT ADJUVANT COMBINATION WHICH COMPRISES: A. FORMING AN AQUEOUS SOLUTION OF WATER SOLUBLE ALKALI METAL SILICATE, B. ADDING TO SAID SOLUTION OF WATER SOLUBLE ALKALI METAL THE CLASS CONSISTING OF CARBON DIOXIDE AND ALKALI METAL BICARBONATE TO FORM THEREWITH A SOLUTION OF ELECTROLYTE SELECTED FROM THE ALKALI METAL CARBONATES AND BICARBONATES WITH A PRECIPITATE OF ALKALINE SILICA PIGMENT THEREIN CONTAINING FROM 0.2 TO 40% BOUND ALKALI BY WEIGHT BASED ON THE SILICA OF THE PIGMENT, AND C. RECOVERING AND ESSENTIALLY DRYING TOGETHER THE COMBINATION OF SAID ALKALINE SILICA PIGMENT AND AT LEAST 25% DRY BASIS, BY WEIGHT, OF THE ELECTROLYTE RESULTING FROM STEP (B), IN COMBINATION, AS A DETERGENT ADJUVANT COMBINATION, SAID RECOVERY INCLUDING INCORPORATING SAID ADJUVANT COMBINATION WITH DETERGENT MATERIAL SELECTED FROM THE CLASS CONSISTING ESSENTIALLY OF THE MEMBERS OF THE FOLLOWING GROUPS: GROUP (I) SOAPS; GROUP (II) SYNTHETIC ANIONIC DETERGENTS; TWO OR MORE OF SAID MEMBERS; IN A RATIO IN THE RANGE OF 5:95 TO 95:5 PARTS DRY BASISM BY WEIGHT, BASED ON THE SILICA CONTENT AS SIO2, THEREBY FORMING A DETERGENT COMPOSITION INCORPORATING SAID DETERGENT ADJUVANT COMBINATION, AND D. IN WHICH THE DETERGENT MATERIAL COMPRISES MATERIAL SELECTED FROM THE SUB-CLASS CONSISTING OF THE MEMBERS OF GROUPS (I) AND (II) WHICH IS FORMED IN THE PRESENCE OF THE SILICA PIGMENT BY REACTION OF THE CORRESPONDING FREE ACID WITH ALKALINITY OF THE COMBINATION RESULTING FROM STEP (B).

21. A process for preparing a detergent adjuvant combination which comprises: a. forming an aqueous solution of water soluble alkali metal silicate, b. adding to said solution sufficient reactant selected from the class consisting of carbon dioxide and alkali metal bicarbonate to form therewith a solution of electrolyte selected from the alkali metal carbonates and bicarbonates with a precipitate of alkaline silica pigment therein containing from 0.2 to 40% bound alkali by weight based on the silica of the pigment, and c. recovering and essentially drying together the combination of said alkaline silica pigment and at least 25% dry basis, by weight, of the electrolyte resulting from step (b), in combination, as a detergent adjuvant combination, said recovery including incorporating said adjuvant combination with detergent material selected from the class consisting essentially of the members of the following groups: Group (I) soaps; Group (II) synthetic anionic detergents; Group (III) non-ionic detergents; and combinations of two or more of said members; in a ratio in the range of 5:95 to 95:5 parts dry basis, by weight, based on the silica content as SiO2, thereby forming a detergent composition incorporating said detergent adjuvant combination, and d. in which the detergent material comprises a soap formed in the presence of the silica pigment by saponification of fatty acid glyceride with the aid of alkalinity of the combination resulting from step (b).