CA1061673A - Free flowing particulate detergent compositions containing a normally tacky detergent - Google Patents
Free flowing particulate detergent compositions containing a normally tacky detergentInfo
- Publication number
- CA1061673A CA1061673A CA234,799A CA234799A CA1061673A CA 1061673 A CA1061673 A CA 1061673A CA 234799 A CA234799 A CA 234799A CA 1061673 A CA1061673 A CA 1061673A
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- Canada
- Prior art keywords
- zeolite
- molecular sieve
- surfactant
- detergent
- detergent composition
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
ABSTRACT
Compositions containing an insoluble particulate molecular sieve zeolite and a normally tacky water-soluble organic surface active agent, usually a deter-gent, are free flowing non-tacky easily handled powders.
These compositions may be admixed with conventional detergent additives to produce laundry washing composi-tions having excellent anti-redeposition characteristics and detergency, even with the use of wash waters of high calcium hardnesses.
Compositions containing an insoluble particulate molecular sieve zeolite and a normally tacky water-soluble organic surface active agent, usually a deter-gent, are free flowing non-tacky easily handled powders.
These compositions may be admixed with conventional detergent additives to produce laundry washing composi-tions having excellent anti-redeposition characteristics and detergency, even with the use of wash waters of high calcium hardnesses.
Description
6~3 FR~E FLOWING PARTICULATE D~T~RGENT COMPOSITIONS
_CONTAINING A NORM~LLY TACKY DETERGENT
This invention ~elates to particulate detergent mixtures or compositions and more particularly, to such compositions con-taining water soluble organic surface active agents, such asdetergents. More particularly, it relates to free 10wing non-tacky par iculate detergents containing normally tacky synthetic organic detergents.
The use of many organic surface active agents (hereafter referred to as surfactants) in solid detergent products, such as laundry washing powders, has been impeded because those detergent compounds have heretofore been available only as tacky or sticky pastes or solids, at room temperature, which are difficult to handle or to admix with other ingredients of conventional detergent formulations, e.g., builder salts. The tacky character of suçh detergents may be attributed in some cases to the presence therein of minor proportions, such as about 0.1 to 30%
of water, oi~l or of products of the manufacture of the materials.
In other instances, particularly, in the case of anionic detergents or surfactants of the paraffin sulfonate type, the tacky consistency appears to be an inherent-disadvantageous property of the pure detergent.
The aforementioned disadvantages of the prior art, normally tacky, organic surfactants are overcome by the present invention, which is of a free flowing pulverulent detergent mixture comprising a particulate molecular sieve zeolite and a -normally tacky water sbluble organic surfactant, usually in a ' . ' V~i~6~7~
weight ratio of about 20:1 to about 0.5:1. The invention also includes a process for converting a normally tacky water soluble organic surfactant to a free flowing or more freely flowing powder or particulate product which comprises intimately mixing the surfactant and the zeolite molecular sieve in the above-stated proportions.
Thus, according to one aspect, the invention provides a free flow-ing particulate detergent composition in the form of particles consisting essentially of a substantially homogeneous mixture of a finely divided water- '.
insoluble crystalline aluminosilicate zeolite having an A12O3SiO2 mole ratio of 1:2 to 1:5, a moisture content of from 1% to 36%, a ne$work of substantial-ly uniformly sized pores in the range of about 3 to lO Angstroms, a particle size of 5 to 9 microns, calcium ion sequestering properties and a cation .~
which is selected from the group consisting of sodium potassium, lithium, :
ammonium and hydrogen; and a normally tacky water-soluble organic surfactant .
selected from the group consisting of anionic, nonionic, cationic and ampho- :. - .
teric surfactants in a weight ratio of zeolite to surfactant of 20:1 to about :.~ ~.
0.5:1. . ~,~
According to a further aspect, the invention provides a process ~ ~ .
for converting a normally tacky water-soluble organic surfactant selected from the group consisting of anionic, nonionic, cationic and amphoteric sur- .~ .
factants to a free-flowing non-tacky powder which comprises intimately mixing for 1 to 20 minutes at a temperature in the range of 5 to 90C. a finely di- . : :
vided, water-insoluble, crystalline aluminosilicate zeolite having an A1203 ~ . .
to SiO2 mole ratio of 1:2 to 1:5, a moisture content of from 1% to 36%, par-ticle size of 5 to 9 microns, calcium ion sequestering properties and a cation :~ ~
which is selected from the group consisting of sodium, potassium, lithium, . ~ .
ammonium and hydrogen and a network of substantially uniformly sized pores in ~
the range of 3 to about 10 Angstroms, with said surfactant, employing about ~ ;
0.5 to 20 parts of a molecular si.eve zeolite per part of the surfactant to . ~ .
form a homogeneous pulverulent product. . ;
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The free flowing pulverulent mixture of zeolite molecular sieve and normally tacky surfactant is obtained by mixing together the components thereof, as by stirring, shaking or otherwise agitating together the mole-cular sieve zeolite and the surfactant for a short period, normally about 1 to 20 minutes, advantageously 5 to 15 minutes. Usually mixing of the zeolite and surfactant will be carried out at about room temperature, e.g., about 20 to 35C., but if desired, mixing can be effected at temperatures in the range of about 10 to ~0C. and even at 5 to 90C. Other temperatures may be used providing that the materials mixed are stable thereat. Generally, the zeolite and surfactant can be mixed in any suitable vessel, for example, a tumbling drum, barrel, or jar, or the shipping container used for shipping the normally tacky organic surfactant. They may be mixed in size-reducing and blending apparatuses, too. Agitation of the molecular sieve zeolite organic surfactant may be fast, slow or medium and can be supplied by any suitable stirring, shaking or size-reducing apparatus, such as a blender (preferably of the twin-shell type), shaker, vibrator, micro-pulverizer, ~ -grinding mill or rollers for rotating the mixing vessel or container. The sticky surfactant and molecular sleve ~ ~' ;;, '.
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zeolite can also be mixed in a conventional agitated soap or detergent mixing vessel, such as a soap or detergent crutcher.
The resulting intimate mixture of molecular sieve zeolite and organic surfactant is a free flowing pulverulent mass of excellent stability. It does not separate or become sticky or tacky even on storage. The free flowing pulverulent surfactant composition of the invention can thus be handled, transported and dry mixed with conventional solid composition component detergents and adj u vants,such as builder salts, fillers, anti-redeposition agents, colorants, foaming and anti-foaming agents, etc., with far greater ease than is the case with the original tacky, sticky organic surfactant. Even in those cases where an insufficient quantity of molecular sieve zeolite is used, so that completely satisfactory flow properties 15- are not obtained, such properties are substantially improved.
The aforementioned ease of mixing the present molecular sleve zeolite-surfactant compositions with other detergent additives avoids the tedious necessity of mixing the surfactant and other de~ergent adjuvants in aqueous media and thereafter drying the aqueous mixture in order to prepare particulate solid laundry detergent formulations. However if it is desired, to obtain the final particulate laundry detergent formulation in a particular form or shape, e.g., hollow beads or granules, the molecular zeolite-surfactant mixture and the detergent adjuvants can be mixed in an aqueous medium and the aqueous dispersion or solution resulting can thereafter be dried at elevated temperature, as in a spray drier, preferably ~.~63..~
cour~ercurrentlywith hot air according to spray drying techniques which are conventional in the detergent art.
The molecular sieves utilized in the invention are water insoluble crystalline, aluminosilicate zeolites of natural or synthetic origin which are characterized by having a network of similarly or substantially uniformly sized pores in the range of about 3 to 10 Angstroms, which size is uniquely determined by the unit structure of the zeolite crystal. Of course,zeolite molecular sieves containing two or more such networks of different siæed pores can also be employed.
The molecular sieve zeolite should also be a univalent cation exchanging zeolite, i.e., it should ba an aluminosilicate of a univalent cation such as sodium, potassium, lithium (in suitable cases) or other alkali metal, ammonium or hydrogen.
Preferably, such univalent cation is an alkali metal cation, especially sodium or potassium.
Preferred crystalline types of zeolites utilized as - molecular sieves in the invention are zeolites of the following ~.
crystal structure: A, X, Y, L, mordenite, chabazite and erionite and other molecular sieve zeolites disclosed in Table 9.6 of the Breck text, m~ntioned below. Generally preferred are the molecular sieve zeolites with A12O3:SiO2 molar ratios of 1:2 to 1:4. Mixtures of these and equivalent molecular sieve zeolites can a1so be used. These preferred crystalline struc-- 25 ture types of zeolites are well known in the ion exchange art and are more particularly described in the text, "Zeolite Molecular S_ ves", by Donald W. Breck, published by John Wiley & Sons in 1974. Most preferably the molecular sieve zeolite ,~ _ .
used is a synthetic molecular sieve type A crystalline zeolite, which is more particularly described on page 133 of the afore-mentioned Breck reference. Best results are generally obtained using a Type 4A molecular sieve zeolite wherein the univalent ~
cation of the zeolite is sodium and the pore size of the zeolite is about 4 A (nominal). These especially preferred zeolite molecular sieves are described in U.S. patent 2!882,243 which refers to them as zeolite A.
Molecular sieve zeolites can be prepared in either a dehydrated, calcined form which contains up to about 3~ of moisture, e.g., 1 to 3~, or in a hydrated, i.e., water loaded form which contains additional adsorbed water in an amount up to about 36%, e.g., 4 to 30~,depending on the type of zeolite used.
Preferably the dehydrated form of the molecular sieve is employed, usually containing about 2% of water. The manufacture of such crystals is wall known in the art and they may be obtained commercially from various manufacturers, including Henkel & Cie.
and Union Carbide Corporation. In the preparation of zeolite A, referred to abo~e, the hydrated zeolite crystals that are formed in the crystallization medium (such as a hydrous amorphous sodium aluminosilicate gel) are dehydrated or calcined, accord-ing to the normal practice in preparing crystals for use as catalysts, e,g., cracking catalysts. The hydrated form of zeolite, either completely hydrated or partially hydrated, can be recovered byfilte~ing off the crystals from the crystallization medium and drying them in air at ambient temperature, without ... : , .. . .
-calcining, so that their water content is in the range of about 4 to 30~, e.g., 20 to 28.5% and such zeolites can be used,too.
However, it appears that the drier zeolites improve flowability of the detergent to a greater extent than the zeolites that contain more water, possibly because more pores thereof are "open".
The crystalline molecular sieve zeolitesused are usually also substantially free of adsorbed gases, such as carbon dioxide, since such gas-containing zeolites may produce undeslrable foaming on contact with water. Preferably the molecular sieve zeolite should be in finely divided condition, ~uch as crystals having mean particle diameters in the range of about 0.5 to about 12 microns, preferably 5 to 9 microns and especially about 5.9 to 8.3 microns. The sieves of 5.9 to 6.4 microns are generally better detergent builders, in addition to their anti-caking and flow promoting properties.
Water soluble organic surfactants which are normally tacky or sticky can be found in all of the principal surfactant categories, among water soluble organic surfactants of the anionic, nonionic, cationic and amphoteric types. These categories are more particularly described in McCutcheon's De~ergents and mulsifiers, 1969 Annual and by Schwartz, Perry and Berch, Surface Active Agents, Vol. II (Interscience Publishers 1958~.
The present compositions may include such tacky or poorly flowing or caking detergents which are inherently tacky or contain oil, water, wax, solvents or other liquids which tend to make them tacky. Such additional tackifying agents are usually only a minor proportion, ~.g., 0.1 to 10%, the surfactant.
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~6~ 73 Suitable anionic surfactants lnclude hlgher (10 to 20 carbon atom) alk~l benzene sulfonate salts wherein the alkyl group pre~erably contains 10 to 16 carbon atoms. The alkyl group is preferably a straight chain alkyl radical of about 11 to 13 or 14 carbon atoms. Preferably~ the alkyl benzene sul~onate has a hlgh content of 3- (or higher) phenyl is~mers and a correspondingly low content (well below 50~) of 2- (or lower) phenyl isomers; in other terminology, the benzene ring is prefer-ably attached in large part at the 3 or higher, eOg.~ 4, 5~
6 or 7 position of the alkyl group and the content of isomers in whlch the benzene ring is attached at the 2 or 1 position is correspondingly low, Typlcal alkyl benzene sulfonate surfactants are described ln the patent literature.
A1SQ typical of anionic surfactants are olefin sulfonate salts. Generally they contain long chain alkenyl sulfonates or long chain hydroxyalkane sulfonates (with the OH
being ~ carbon atom which is not directly attached to the carbon atom bearing the -S03 group). More usually, the olefin sulfonate detergent comprises a mixture o~ these two types of compoundæ in varying amounts~ often together with long chain disulfonates or sulfate-sulfonates. Such olefln sulfonates are described in many patents and in the article by Baumann et al. in ~ette-Seifen~Anstrichmittel 72~ No. 4, pp. 247 253 (1970). The above-mentioned dlsclosure ls incorporated here-in by reference. The number of carbon atoms in the olefin sulfonates is usually within the range of lO to 25~ more commonly .. . . . .. . . . . . . . .
7~ ~
12 to 0, e.g., a mlxture o~ principally Cl~, C14 and C16, having an average of about 14 carbon atoms or a mixture of p ipally C14, C16 and C18, having an average of about 16 carbon atoms.
Another class of water soluble organic anionic surfactants is that of the higher (10 to 20 carbon atom) paraffin sulfonates These may be the primary para~fin sulfonates made by reacting long chain alpha olefins and bisulfites, e.g., sodium bisulfite, or paraffin sulfonates having the sulfonate groups d1stributed along the paraffin chain, such as the products made by reacting a long chaln para~in with sulfur dioxide and oxygen under ultraviolet light, followed by neutralization with NaOH or other suitable base. The paraffin sulfonates are the preferred ~ organic detergents of the invent~on and, without treatment by the method of this invention, make the tackiest detergent products. They are more particularly described below.
Other anionic surfactants are water soluble salts of, for instance, s~uch high fatty carbo~ylic acids as lauric, myristic, stearic-, oleic, elaidlc, isostearic, palmitic~ undecylenic, tridecylenic, pentadecylenic3 2-lo~er alkyl hlgher alkanoic (such as 2-methyl trldecanolc, 2-methyl pentadecanoic or 2-methyl heptadecanoic) and other saturated or unsaturated fatty acids of 10 to 20 carbon atoms. Soaps of dlcarboxylic acids may also be used, such as the soaps of dimerized linoleic acld. Soaps of such other higher molecular weight acids such as rosin or tall _ 8 -~`6~3 ~ :~
oil acids, e.g., abietic acid, may also be employed.
Other anionic surfactants are sulfates o~ higher alcohols~ such as sodium lauryl sul~a~e, sodium tallow alcohol sulfate, sulfated oils, sulfates of mono- or diglycerides of higher ~atty acids, e.g., stearic monoglyceride monosul~ate;
higher alkyl polyethenoxy ether sul~ates, i.e., the sulfates of the condensation products o~ ethylene oxide and a higher aliphatic alcohol, e.g., lauryl a~cohol, wherein the molar proportion of alkylene oxide to alcohol is ~om 1:1 to 5:1; lauryl or other higher alkyl glyceryl ether sulfonates;
aromatlc polyethenoxy ether sulfates~ such as the sulfates of the condensation products of Pthylene oxide and nonyl phenol (usually having 1 to 20 oxyethylene groups per molecule, preferably 2-12). The ether sulfate may also be one having a lower alkoxy (of 1 to 14 carbon atoms, e.g., methoxy) sùbstltuent - on a carbon close to that carrying the sul~ate group, such as a monomethyl ether monosulfate of a long chain vicinal glycol, e.g., a mixture of viclnal alkanediols o~ 16 to 17 or 18 or 20 carbon atoms in a straight chainO
Additional water soluble anionic sur~actants include the higher acyl sarcosinates, e.g., sodium lauroyl sarcosinate;
the acyl esters, e.g., oleic acid ester o~ isethionates; and acyl N-methyl taurides, e.g., potassium N-methyl lauroyl- or oleyl tauride. Another type o~ anlonic sur~actant is a higher alkyl ~ .
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phenol sulfonate, for example, a higher alkyl phenol disulfonate.
The disul~onate may be one whose phenolic hydroxyl group is blocked, as by etheri~ication or esterification; thus the H of the phenollc OH may be replaced by an alkyl, e.g., ethyl, or hydroxy polyalkoxyalkyl, and the resulting alcoholic OH may be esterified to ~orm sulfate.
While the a~orementioned structural types of organic carboxylates, sulfate, and sulfonates are generally preferred types of anionic sur~actants, the correspondlng organic phosphates and phosphonates are also use~ul.
Generally, the water soluble anionic organic surfactants are ~lt8 0~ alkali metal cations, such as potassium, lithium, and especlally sodlum although salts of ammonium cations and substituted ammonium cations derived from lower (2 to 4 carbon atom) alkanolamides, e.g., triethanolamine, tripropanolamlne, and diethanol monopropanolamine, and from lower (l to 4 carbon atom) alkyl amines, e.g., methylamine, ethylamine, 8ec - butylamine, dimethylamine, tripropylamine and triisopropylamine, may be utilized too.
The nonionic surfactants having the most desirable detergency properties are usually lnherently unctuous pasty or tacky solids at room temperature~ such as those having melting points below about 40C. Typical nonionic detergents are polyethenoxy derivatlves that are usually prepared by the condensation of eth~lene oxide with compoùnds having a 6~7;~
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hydrophobic hydrocarbon chain and containing one or more active hydrogen atoms, such as higher alkylphenols, higher fa~ty alcohols, higher fatty acids, higher fatty mercaptans, higher fatty amides and polyols, e.g., fâtty alcohols having an 8 to 20, typically 10 to 18 carbon atom alkyl chain and alkoxylated with an average of about 3 to 20, typically 5 to 15 alkylene oxide units. Commercial-ly available nonionic suractants falling into this category are Neodol* 45-11, which is an ethoxylation product ~having an average of 11 ethylene oxide units) of a 14 to 15 carbon chain fatty alcohol (Shell Chemical Company); Neodol 25-7, a 12 to 15 carbon : ~
chain fatty alcohol ethoxylated with an average of 7 ethylene oxide units; Alfonic* 1618-65, a 16 to 18 carbon alkanol ethoxylated with an average of 10 to 11 ethylene oxide units ~Continental Oil Company); and Pluronic* B-26, a 12 to 13 carbon alcohol etherified with ethyl~e oxide and propylene oxide ~BASF ~hemical Company).
Cationic organic surfactants include quaternary amines ~ !
having a water soluble anion such as acetate, sulfate or chloride. Suitable quaternary ammonium salts may be derived from a higher fatty primary amine by condensation with a lower alkylene oxide similar to~that described above for preparation of nonionic surfactants. Typical cationic surfactants of this type include !' Ethoduomeens* T/12 and T/13" which are ~`thylene oxide condensates of N-tallow trimethylene dialnine (Armour Industrial Chemical Co.) and Ethoquad* 18/12, 18/25 and 0/12, which are polyetho~rlated ~ -c~uatema~y amm mium chlo ides (Armou~ Indumt~ial Chemical Co,~
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" :'' Cationic surfactants also include quaternary ammonium salts -de'rived from heterocyclic aromatic amines such as Emcol* E-607 which is N~lauryl colamino formyl methyl) pyridinium chloride ~Witco Chemical Corp.). Also sometimes classified as cationic surfactants are higher fatty amine oxides such as Aromox* 18/12, which is bis (2-hydroxyethyl) octadecylamine oxide ~Armour Industrial Chemical Co.).
Amphoteric organic surfactants are generally higher ;
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fatty carboxylates, phosphates, sulfates or sulfonates which contain a cationic substituent such as an amino group, which may -~
be quaternized, e.g., with a lower alkyl group, or chain extended at the amino group by àondensation with a lower alkylene oxide, e.g., ethylene oxide. In some instances the amino group may be a member of a heterocyclic ring. Re~resentative commercial water soluble amphoteric organic surfactants include Deripha ~151, which is sodium ~-coco betaamine propionate ~General Mills, Inc.) ~:
and Miranol* C2M (anhydrous acid) which is the anhydrous form of the heterocyclic diamino-dicarboxylate, sold by Miranol Chemical Co.
Preferably the normally tacky water soluble organic -surfactant which is used to prepare the free flowing detergent powder of the invention is an anionic surfactant and of these, ~.~
especially preferred are the higher paraffin sulfonates. The i-hydrocarbon substituent of the par~ffin sulfonate preferably contains 13 to 17 or 20 carbon atoms. The paraffin sulfonate will normally be a monosulfonate but, if desired, may be a,!di-~;
*Trademark - . : ,, :
tri- or higher sulfonate. Typically, a paraffin sulfonate may be employed in admixture with the corresponding monosulfonate, for example, as a mix-ture of mono- and di-sulfonates containing up to about 30% of the disulfo-nate.
The hydrocarbon substituent of the paraffin sulfonate will usually be linear but if desired branched chain paraffin sulfonates can be employed.
The paraffin sulfonate used may be terminally sulfonated or the sulfonate `
substituents may be joined to the 2-carbon or other carbon atom of the paraffin chain. Similarly, any di- or higher sulfonate employed may have the sulfonate groups distributed over different carbons of the hydrocarbon chain.
The weight ratio of molecular sieve zeolite and normally tacky organic surfactant employed to prepare the free flowing pulverulent deter-gent compositions of the invention will be in the range of about 20:1 to 0.5:1, preferably being about 1:1 to 0.9:1. ;
The free flowing pulverulent detergent composition of the inven-tion has an excellent detersive effect on most types of soils but, if desired it may be combined with detergency adjuvants, such as builder salts, optical brighteners, anti-redeposition agents and the like, which are conventional ingredients in laundry detergents and other types of solid or particulate washing agents. In such detergent formulations the proportion of zeolite-organic surfactant composition is generally about 20 to 70% and preferably is about 25 to 55% by weight. ;~
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The water insoluble molecular sieve zeolite present in the com-positions of the invention has an excellent building effect on the deter-gency of the composition. However, if desired, additional water soluble builder salt or mixtures of such salts may be added. Representative organic builder salts include the water soluble salts of nitrilotriacetatic acid, citric acid, 2-hydroxyethylene iminodicarboxylic acid, boroglucoheptanoic acid and polycarboxylic acids, e.g., polymaleates of low molecular weight ~generally below 1,000, e.g., ~00, 600 or 800~. Representative inorganic builder salts include alkali metal silicates, e.g., sodium silicates, having Na20:SiO2 molar ratios of 1:2 to 1:3.2, preferably 1:2 to 1:2.5, alkali metal polyphosphates, such as pentasodium tripolyphosphate and tetrasodium pyrophosphate; and alkali metal carbonates, such as sodium carbonate.
An especially desirable additional builder salt is sodium sili-cate, which is particularly effective in sequestering magnesi~m cation, and this is useful in overcoming magnesium hardness in the wash water. A pre-ferred suitable laundry detergent formulation which contains a water soluble anionic organic surfactant or detergent built with both molecular sieve zeo-lite and sodium silicate is described in copending Canadian Patent Applica-tion of B. Cheng, Serial No. 226,363, filed May 6, 1975, entitled "Detergent Composition".
The amount of additional builder salt(s) charged to the zeolite- -organic surfactant compositions of the invention '' - 1 'I ~ .
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may be from about 5 to 50% by weight of the final laundry detergent formulation and preferably is from about 10 to 35%.
Similar proportions of inorganic filler salt, e.g., sodium sulfate, so~ um chloride, may be employed.
The laundry~ldétergent formulations which are prepared from the invented molecular sieve zeolite-organic surfactant ; compositions may also advantageously include small amounts, e.g., 0.05 to 8%, of additional conventional detergent adjuvants, the total amount of such minor adjuvants generally not exceeding 20%, preferably not exceedin~ 10% of the product. ;
These adjuvants include inorganic pigments, e.g., ultramarine blue; organic pigments, e.g., Indanthreane Blue* RS, dyes, e.g., Color Index Direct Blue l; and especially the fluorescent dyes known as optical brighteners. Such brighteners may be coumarin, triazolyl stilbener~ stilbene cyanuric, `
acylamino stilbene or miscellaneous types shown in issued ; patents. The concentration of brightener is advantageously in the range of about 1/20% to 1%, e.g., 1/10% to 1/2%.
The minor adjuvants may also include an organic gum anti-redeposition agent, such as sodium carboxymethyl cellulose, polyvinyl alcohol, hydroxymethyl ethyl cellulose, polyvinyl pyrrolidone, polyacrylamide, hydroxypropyl ethyl cellulose or ,.
mixtures thereof. Preferably the anti-redeposition agent is sodium carboxymethyl cellulose.
Additional minor detergent adjuvants which may be included in the detergent formulation include perfumes;
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i73 fun~icides or preservatives such as polyhalosalicylanilides, for instance, tetrachlorosalicylanilide; sanitizersl such as trichlorocarbanilide; foam suppressors, such as NrN-dilauryl ~or di-coco alcohol) amine; enzymes, such as the subtilisin protease sold as Alcalase; bleaching agents, such as N-bromo and N-chloro imido compounds, for example, di- and tri-chloro (or bromo) cyanuric acid and water soluble salts thereof;
fabric softeners, such as l,2 alkane diols of 15 to 18 carbon atoms; and flow improving agents, such as the clay product, Satintone .
The detergent formulation may also contain a small amount of moisture, in addition to that which may be adsorbed in the zeolite molecular sieve, typically about 1 to S~.
The present compositions have been found to be effective detergents against a wide variety of soils,including clay and carbon soils, skin soil, natural and artificial sebum soils, particulate soils, etc., on a wide variety of fabrics, including cQtton, nylon and polyesters, such as polyethylene terephthalate and various blends, e.g., cotton-polyester.
~he present compositions are highly effective detergents even in the absence o conventional builder salts and other detergent adjuvants due to the excellent detergency building effect of the molecular sieve zeolite component. The molecular sieve zeolite components are highly efficient in sequestering calcium ion when washing in water of high calcium hardness.
Accordinglyj at a conventional laundry wash water concentration of about 0.15%, the present compositions remain effective as , t73 detergents even at calcium ion concentrations of 150 p.p.m.
(as CaCO ) or higher. On washing of fabrics with the present compositions no noticeable deposits of insolubles remain on the fabrics after rinsing and tumble drying, even in the absence of anti-redeposition agent in the formulation. It was surprising to discover this exce~le~ r.on-deposition characteristic of the present product in view of the known water insolubility of the molecular sieve zeolite component of the mixture. When tumble drying is not employed there may be a very slight deposit but it is much less than would be expected. Also, the zeolite molecular sieve is biologically safe, non-eutrophic, non-polluting and is harmless to laundry and laundry equipment. Any white fabrics washed with the present surfactant mixtures in the presence of colored fabrics are not substantially stained by dyes fugitive from the colored fabrics.
In addition to good building effects the present zeolite molecular sieves also counteract tackiness of detergents to a surprising extent, making them usefully free flowing and better able to be compounded with other detergent composition ingredients.
They are superior in this respect to ordinary clays and particulate carriers and they are useful builders, too.
The~following examples illustrate the invention but do not limit it. Unless otherwise indicated, all parts are by weight and temperatures are in C.
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~6 ' Paraffin sulfonate C15 (1~ 52.6 Molecular sieve zeolite 4A (2) 47.4 100.0 (1) A normally tacky sodium paraffin sulfonate wherein the n-alkyl substituent contains on the average 15 carbon atoms (Hoechst Chemical Corp.)
_CONTAINING A NORM~LLY TACKY DETERGENT
This invention ~elates to particulate detergent mixtures or compositions and more particularly, to such compositions con-taining water soluble organic surface active agents, such asdetergents. More particularly, it relates to free 10wing non-tacky par iculate detergents containing normally tacky synthetic organic detergents.
The use of many organic surface active agents (hereafter referred to as surfactants) in solid detergent products, such as laundry washing powders, has been impeded because those detergent compounds have heretofore been available only as tacky or sticky pastes or solids, at room temperature, which are difficult to handle or to admix with other ingredients of conventional detergent formulations, e.g., builder salts. The tacky character of suçh detergents may be attributed in some cases to the presence therein of minor proportions, such as about 0.1 to 30%
of water, oi~l or of products of the manufacture of the materials.
In other instances, particularly, in the case of anionic detergents or surfactants of the paraffin sulfonate type, the tacky consistency appears to be an inherent-disadvantageous property of the pure detergent.
The aforementioned disadvantages of the prior art, normally tacky, organic surfactants are overcome by the present invention, which is of a free flowing pulverulent detergent mixture comprising a particulate molecular sieve zeolite and a -normally tacky water sbluble organic surfactant, usually in a ' . ' V~i~6~7~
weight ratio of about 20:1 to about 0.5:1. The invention also includes a process for converting a normally tacky water soluble organic surfactant to a free flowing or more freely flowing powder or particulate product which comprises intimately mixing the surfactant and the zeolite molecular sieve in the above-stated proportions.
Thus, according to one aspect, the invention provides a free flow-ing particulate detergent composition in the form of particles consisting essentially of a substantially homogeneous mixture of a finely divided water- '.
insoluble crystalline aluminosilicate zeolite having an A12O3SiO2 mole ratio of 1:2 to 1:5, a moisture content of from 1% to 36%, a ne$work of substantial-ly uniformly sized pores in the range of about 3 to lO Angstroms, a particle size of 5 to 9 microns, calcium ion sequestering properties and a cation .~
which is selected from the group consisting of sodium potassium, lithium, :
ammonium and hydrogen; and a normally tacky water-soluble organic surfactant .
selected from the group consisting of anionic, nonionic, cationic and ampho- :. - .
teric surfactants in a weight ratio of zeolite to surfactant of 20:1 to about :.~ ~.
0.5:1. . ~,~
According to a further aspect, the invention provides a process ~ ~ .
for converting a normally tacky water-soluble organic surfactant selected from the group consisting of anionic, nonionic, cationic and amphoteric sur- .~ .
factants to a free-flowing non-tacky powder which comprises intimately mixing for 1 to 20 minutes at a temperature in the range of 5 to 90C. a finely di- . : :
vided, water-insoluble, crystalline aluminosilicate zeolite having an A1203 ~ . .
to SiO2 mole ratio of 1:2 to 1:5, a moisture content of from 1% to 36%, par-ticle size of 5 to 9 microns, calcium ion sequestering properties and a cation :~ ~
which is selected from the group consisting of sodium, potassium, lithium, . ~ .
ammonium and hydrogen and a network of substantially uniformly sized pores in ~
the range of 3 to about 10 Angstroms, with said surfactant, employing about ~ ;
0.5 to 20 parts of a molecular si.eve zeolite per part of the surfactant to . ~ .
form a homogeneous pulverulent product. . ;
',,~ .
~ - 2 - :
f.''''' ~'' "
The free flowing pulverulent mixture of zeolite molecular sieve and normally tacky surfactant is obtained by mixing together the components thereof, as by stirring, shaking or otherwise agitating together the mole-cular sieve zeolite and the surfactant for a short period, normally about 1 to 20 minutes, advantageously 5 to 15 minutes. Usually mixing of the zeolite and surfactant will be carried out at about room temperature, e.g., about 20 to 35C., but if desired, mixing can be effected at temperatures in the range of about 10 to ~0C. and even at 5 to 90C. Other temperatures may be used providing that the materials mixed are stable thereat. Generally, the zeolite and surfactant can be mixed in any suitable vessel, for example, a tumbling drum, barrel, or jar, or the shipping container used for shipping the normally tacky organic surfactant. They may be mixed in size-reducing and blending apparatuses, too. Agitation of the molecular sieve zeolite organic surfactant may be fast, slow or medium and can be supplied by any suitable stirring, shaking or size-reducing apparatus, such as a blender (preferably of the twin-shell type), shaker, vibrator, micro-pulverizer, ~ -grinding mill or rollers for rotating the mixing vessel or container. The sticky surfactant and molecular sleve ~ ~' ;;, '.
,.
.; .
.. .
."
- 2a -'~, .. . . .
,- ..... ,;: . . ~: :
: .
:
6'7~
zeolite can also be mixed in a conventional agitated soap or detergent mixing vessel, such as a soap or detergent crutcher.
The resulting intimate mixture of molecular sieve zeolite and organic surfactant is a free flowing pulverulent mass of excellent stability. It does not separate or become sticky or tacky even on storage. The free flowing pulverulent surfactant composition of the invention can thus be handled, transported and dry mixed with conventional solid composition component detergents and adj u vants,such as builder salts, fillers, anti-redeposition agents, colorants, foaming and anti-foaming agents, etc., with far greater ease than is the case with the original tacky, sticky organic surfactant. Even in those cases where an insufficient quantity of molecular sieve zeolite is used, so that completely satisfactory flow properties 15- are not obtained, such properties are substantially improved.
The aforementioned ease of mixing the present molecular sleve zeolite-surfactant compositions with other detergent additives avoids the tedious necessity of mixing the surfactant and other de~ergent adjuvants in aqueous media and thereafter drying the aqueous mixture in order to prepare particulate solid laundry detergent formulations. However if it is desired, to obtain the final particulate laundry detergent formulation in a particular form or shape, e.g., hollow beads or granules, the molecular zeolite-surfactant mixture and the detergent adjuvants can be mixed in an aqueous medium and the aqueous dispersion or solution resulting can thereafter be dried at elevated temperature, as in a spray drier, preferably ~.~63..~
cour~ercurrentlywith hot air according to spray drying techniques which are conventional in the detergent art.
The molecular sieves utilized in the invention are water insoluble crystalline, aluminosilicate zeolites of natural or synthetic origin which are characterized by having a network of similarly or substantially uniformly sized pores in the range of about 3 to 10 Angstroms, which size is uniquely determined by the unit structure of the zeolite crystal. Of course,zeolite molecular sieves containing two or more such networks of different siæed pores can also be employed.
The molecular sieve zeolite should also be a univalent cation exchanging zeolite, i.e., it should ba an aluminosilicate of a univalent cation such as sodium, potassium, lithium (in suitable cases) or other alkali metal, ammonium or hydrogen.
Preferably, such univalent cation is an alkali metal cation, especially sodium or potassium.
Preferred crystalline types of zeolites utilized as - molecular sieves in the invention are zeolites of the following ~.
crystal structure: A, X, Y, L, mordenite, chabazite and erionite and other molecular sieve zeolites disclosed in Table 9.6 of the Breck text, m~ntioned below. Generally preferred are the molecular sieve zeolites with A12O3:SiO2 molar ratios of 1:2 to 1:4. Mixtures of these and equivalent molecular sieve zeolites can a1so be used. These preferred crystalline struc-- 25 ture types of zeolites are well known in the ion exchange art and are more particularly described in the text, "Zeolite Molecular S_ ves", by Donald W. Breck, published by John Wiley & Sons in 1974. Most preferably the molecular sieve zeolite ,~ _ .
used is a synthetic molecular sieve type A crystalline zeolite, which is more particularly described on page 133 of the afore-mentioned Breck reference. Best results are generally obtained using a Type 4A molecular sieve zeolite wherein the univalent ~
cation of the zeolite is sodium and the pore size of the zeolite is about 4 A (nominal). These especially preferred zeolite molecular sieves are described in U.S. patent 2!882,243 which refers to them as zeolite A.
Molecular sieve zeolites can be prepared in either a dehydrated, calcined form which contains up to about 3~ of moisture, e.g., 1 to 3~, or in a hydrated, i.e., water loaded form which contains additional adsorbed water in an amount up to about 36%, e.g., 4 to 30~,depending on the type of zeolite used.
Preferably the dehydrated form of the molecular sieve is employed, usually containing about 2% of water. The manufacture of such crystals is wall known in the art and they may be obtained commercially from various manufacturers, including Henkel & Cie.
and Union Carbide Corporation. In the preparation of zeolite A, referred to abo~e, the hydrated zeolite crystals that are formed in the crystallization medium (such as a hydrous amorphous sodium aluminosilicate gel) are dehydrated or calcined, accord-ing to the normal practice in preparing crystals for use as catalysts, e,g., cracking catalysts. The hydrated form of zeolite, either completely hydrated or partially hydrated, can be recovered byfilte~ing off the crystals from the crystallization medium and drying them in air at ambient temperature, without ... : , .. . .
-calcining, so that their water content is in the range of about 4 to 30~, e.g., 20 to 28.5% and such zeolites can be used,too.
However, it appears that the drier zeolites improve flowability of the detergent to a greater extent than the zeolites that contain more water, possibly because more pores thereof are "open".
The crystalline molecular sieve zeolitesused are usually also substantially free of adsorbed gases, such as carbon dioxide, since such gas-containing zeolites may produce undeslrable foaming on contact with water. Preferably the molecular sieve zeolite should be in finely divided condition, ~uch as crystals having mean particle diameters in the range of about 0.5 to about 12 microns, preferably 5 to 9 microns and especially about 5.9 to 8.3 microns. The sieves of 5.9 to 6.4 microns are generally better detergent builders, in addition to their anti-caking and flow promoting properties.
Water soluble organic surfactants which are normally tacky or sticky can be found in all of the principal surfactant categories, among water soluble organic surfactants of the anionic, nonionic, cationic and amphoteric types. These categories are more particularly described in McCutcheon's De~ergents and mulsifiers, 1969 Annual and by Schwartz, Perry and Berch, Surface Active Agents, Vol. II (Interscience Publishers 1958~.
The present compositions may include such tacky or poorly flowing or caking detergents which are inherently tacky or contain oil, water, wax, solvents or other liquids which tend to make them tacky. Such additional tackifying agents are usually only a minor proportion, ~.g., 0.1 to 10%, the surfactant.
.
.
.
.., .
~6~ 73 Suitable anionic surfactants lnclude hlgher (10 to 20 carbon atom) alk~l benzene sulfonate salts wherein the alkyl group pre~erably contains 10 to 16 carbon atoms. The alkyl group is preferably a straight chain alkyl radical of about 11 to 13 or 14 carbon atoms. Preferably~ the alkyl benzene sul~onate has a hlgh content of 3- (or higher) phenyl is~mers and a correspondingly low content (well below 50~) of 2- (or lower) phenyl isomers; in other terminology, the benzene ring is prefer-ably attached in large part at the 3 or higher, eOg.~ 4, 5~
6 or 7 position of the alkyl group and the content of isomers in whlch the benzene ring is attached at the 2 or 1 position is correspondingly low, Typlcal alkyl benzene sulfonate surfactants are described ln the patent literature.
A1SQ typical of anionic surfactants are olefin sulfonate salts. Generally they contain long chain alkenyl sulfonates or long chain hydroxyalkane sulfonates (with the OH
being ~ carbon atom which is not directly attached to the carbon atom bearing the -S03 group). More usually, the olefin sulfonate detergent comprises a mixture o~ these two types of compoundæ in varying amounts~ often together with long chain disulfonates or sulfate-sulfonates. Such olefln sulfonates are described in many patents and in the article by Baumann et al. in ~ette-Seifen~Anstrichmittel 72~ No. 4, pp. 247 253 (1970). The above-mentioned dlsclosure ls incorporated here-in by reference. The number of carbon atoms in the olefin sulfonates is usually within the range of lO to 25~ more commonly .. . . . .. . . . . . . . .
7~ ~
12 to 0, e.g., a mlxture o~ principally Cl~, C14 and C16, having an average of about 14 carbon atoms or a mixture of p ipally C14, C16 and C18, having an average of about 16 carbon atoms.
Another class of water soluble organic anionic surfactants is that of the higher (10 to 20 carbon atom) paraffin sulfonates These may be the primary para~fin sulfonates made by reacting long chain alpha olefins and bisulfites, e.g., sodium bisulfite, or paraffin sulfonates having the sulfonate groups d1stributed along the paraffin chain, such as the products made by reacting a long chaln para~in with sulfur dioxide and oxygen under ultraviolet light, followed by neutralization with NaOH or other suitable base. The paraffin sulfonates are the preferred ~ organic detergents of the invent~on and, without treatment by the method of this invention, make the tackiest detergent products. They are more particularly described below.
Other anionic surfactants are water soluble salts of, for instance, s~uch high fatty carbo~ylic acids as lauric, myristic, stearic-, oleic, elaidlc, isostearic, palmitic~ undecylenic, tridecylenic, pentadecylenic3 2-lo~er alkyl hlgher alkanoic (such as 2-methyl trldecanolc, 2-methyl pentadecanoic or 2-methyl heptadecanoic) and other saturated or unsaturated fatty acids of 10 to 20 carbon atoms. Soaps of dlcarboxylic acids may also be used, such as the soaps of dimerized linoleic acld. Soaps of such other higher molecular weight acids such as rosin or tall _ 8 -~`6~3 ~ :~
oil acids, e.g., abietic acid, may also be employed.
Other anionic surfactants are sulfates o~ higher alcohols~ such as sodium lauryl sul~a~e, sodium tallow alcohol sulfate, sulfated oils, sulfates of mono- or diglycerides of higher ~atty acids, e.g., stearic monoglyceride monosul~ate;
higher alkyl polyethenoxy ether sul~ates, i.e., the sulfates of the condensation products o~ ethylene oxide and a higher aliphatic alcohol, e.g., lauryl a~cohol, wherein the molar proportion of alkylene oxide to alcohol is ~om 1:1 to 5:1; lauryl or other higher alkyl glyceryl ether sulfonates;
aromatlc polyethenoxy ether sulfates~ such as the sulfates of the condensation products of Pthylene oxide and nonyl phenol (usually having 1 to 20 oxyethylene groups per molecule, preferably 2-12). The ether sulfate may also be one having a lower alkoxy (of 1 to 14 carbon atoms, e.g., methoxy) sùbstltuent - on a carbon close to that carrying the sul~ate group, such as a monomethyl ether monosulfate of a long chain vicinal glycol, e.g., a mixture of viclnal alkanediols o~ 16 to 17 or 18 or 20 carbon atoms in a straight chainO
Additional water soluble anionic sur~actants include the higher acyl sarcosinates, e.g., sodium lauroyl sarcosinate;
the acyl esters, e.g., oleic acid ester o~ isethionates; and acyl N-methyl taurides, e.g., potassium N-methyl lauroyl- or oleyl tauride. Another type o~ anlonic sur~actant is a higher alkyl ~ .
_ g _ ' ~
106~
phenol sulfonate, for example, a higher alkyl phenol disulfonate.
The disul~onate may be one whose phenolic hydroxyl group is blocked, as by etheri~ication or esterification; thus the H of the phenollc OH may be replaced by an alkyl, e.g., ethyl, or hydroxy polyalkoxyalkyl, and the resulting alcoholic OH may be esterified to ~orm sulfate.
While the a~orementioned structural types of organic carboxylates, sulfate, and sulfonates are generally preferred types of anionic sur~actants, the correspondlng organic phosphates and phosphonates are also use~ul.
Generally, the water soluble anionic organic surfactants are ~lt8 0~ alkali metal cations, such as potassium, lithium, and especlally sodlum although salts of ammonium cations and substituted ammonium cations derived from lower (2 to 4 carbon atom) alkanolamides, e.g., triethanolamine, tripropanolamlne, and diethanol monopropanolamine, and from lower (l to 4 carbon atom) alkyl amines, e.g., methylamine, ethylamine, 8ec - butylamine, dimethylamine, tripropylamine and triisopropylamine, may be utilized too.
The nonionic surfactants having the most desirable detergency properties are usually lnherently unctuous pasty or tacky solids at room temperature~ such as those having melting points below about 40C. Typical nonionic detergents are polyethenoxy derivatlves that are usually prepared by the condensation of eth~lene oxide with compoùnds having a 6~7;~
.:.
hydrophobic hydrocarbon chain and containing one or more active hydrogen atoms, such as higher alkylphenols, higher fa~ty alcohols, higher fatty acids, higher fatty mercaptans, higher fatty amides and polyols, e.g., fâtty alcohols having an 8 to 20, typically 10 to 18 carbon atom alkyl chain and alkoxylated with an average of about 3 to 20, typically 5 to 15 alkylene oxide units. Commercial-ly available nonionic suractants falling into this category are Neodol* 45-11, which is an ethoxylation product ~having an average of 11 ethylene oxide units) of a 14 to 15 carbon chain fatty alcohol (Shell Chemical Company); Neodol 25-7, a 12 to 15 carbon : ~
chain fatty alcohol ethoxylated with an average of 7 ethylene oxide units; Alfonic* 1618-65, a 16 to 18 carbon alkanol ethoxylated with an average of 10 to 11 ethylene oxide units ~Continental Oil Company); and Pluronic* B-26, a 12 to 13 carbon alcohol etherified with ethyl~e oxide and propylene oxide ~BASF ~hemical Company).
Cationic organic surfactants include quaternary amines ~ !
having a water soluble anion such as acetate, sulfate or chloride. Suitable quaternary ammonium salts may be derived from a higher fatty primary amine by condensation with a lower alkylene oxide similar to~that described above for preparation of nonionic surfactants. Typical cationic surfactants of this type include !' Ethoduomeens* T/12 and T/13" which are ~`thylene oxide condensates of N-tallow trimethylene dialnine (Armour Industrial Chemical Co.) and Ethoquad* 18/12, 18/25 and 0/12, which are polyetho~rlated ~ -c~uatema~y amm mium chlo ides (Armou~ Indumt~ial Chemical Co,~
'"''.
*Trademark ~, .'~.
' ,'~
' ' ' , ~ ; , ~;
:. : , , , , . " : ; ~
6~
" :'' Cationic surfactants also include quaternary ammonium salts -de'rived from heterocyclic aromatic amines such as Emcol* E-607 which is N~lauryl colamino formyl methyl) pyridinium chloride ~Witco Chemical Corp.). Also sometimes classified as cationic surfactants are higher fatty amine oxides such as Aromox* 18/12, which is bis (2-hydroxyethyl) octadecylamine oxide ~Armour Industrial Chemical Co.).
Amphoteric organic surfactants are generally higher ;
:,., :
fatty carboxylates, phosphates, sulfates or sulfonates which contain a cationic substituent such as an amino group, which may -~
be quaternized, e.g., with a lower alkyl group, or chain extended at the amino group by àondensation with a lower alkylene oxide, e.g., ethylene oxide. In some instances the amino group may be a member of a heterocyclic ring. Re~resentative commercial water soluble amphoteric organic surfactants include Deripha ~151, which is sodium ~-coco betaamine propionate ~General Mills, Inc.) ~:
and Miranol* C2M (anhydrous acid) which is the anhydrous form of the heterocyclic diamino-dicarboxylate, sold by Miranol Chemical Co.
Preferably the normally tacky water soluble organic -surfactant which is used to prepare the free flowing detergent powder of the invention is an anionic surfactant and of these, ~.~
especially preferred are the higher paraffin sulfonates. The i-hydrocarbon substituent of the par~ffin sulfonate preferably contains 13 to 17 or 20 carbon atoms. The paraffin sulfonate will normally be a monosulfonate but, if desired, may be a,!di-~;
*Trademark - . : ,, :
tri- or higher sulfonate. Typically, a paraffin sulfonate may be employed in admixture with the corresponding monosulfonate, for example, as a mix-ture of mono- and di-sulfonates containing up to about 30% of the disulfo-nate.
The hydrocarbon substituent of the paraffin sulfonate will usually be linear but if desired branched chain paraffin sulfonates can be employed.
The paraffin sulfonate used may be terminally sulfonated or the sulfonate `
substituents may be joined to the 2-carbon or other carbon atom of the paraffin chain. Similarly, any di- or higher sulfonate employed may have the sulfonate groups distributed over different carbons of the hydrocarbon chain.
The weight ratio of molecular sieve zeolite and normally tacky organic surfactant employed to prepare the free flowing pulverulent deter-gent compositions of the invention will be in the range of about 20:1 to 0.5:1, preferably being about 1:1 to 0.9:1. ;
The free flowing pulverulent detergent composition of the inven-tion has an excellent detersive effect on most types of soils but, if desired it may be combined with detergency adjuvants, such as builder salts, optical brighteners, anti-redeposition agents and the like, which are conventional ingredients in laundry detergents and other types of solid or particulate washing agents. In such detergent formulations the proportion of zeolite-organic surfactant composition is generally about 20 to 70% and preferably is about 25 to 55% by weight. ;~
'''~ '.' ", ., :.
_ 13 -~.1 ', .. , , ~ :
.. , : ~ : , , ~ .
The water insoluble molecular sieve zeolite present in the com-positions of the invention has an excellent building effect on the deter-gency of the composition. However, if desired, additional water soluble builder salt or mixtures of such salts may be added. Representative organic builder salts include the water soluble salts of nitrilotriacetatic acid, citric acid, 2-hydroxyethylene iminodicarboxylic acid, boroglucoheptanoic acid and polycarboxylic acids, e.g., polymaleates of low molecular weight ~generally below 1,000, e.g., ~00, 600 or 800~. Representative inorganic builder salts include alkali metal silicates, e.g., sodium silicates, having Na20:SiO2 molar ratios of 1:2 to 1:3.2, preferably 1:2 to 1:2.5, alkali metal polyphosphates, such as pentasodium tripolyphosphate and tetrasodium pyrophosphate; and alkali metal carbonates, such as sodium carbonate.
An especially desirable additional builder salt is sodium sili-cate, which is particularly effective in sequestering magnesi~m cation, and this is useful in overcoming magnesium hardness in the wash water. A pre-ferred suitable laundry detergent formulation which contains a water soluble anionic organic surfactant or detergent built with both molecular sieve zeo-lite and sodium silicate is described in copending Canadian Patent Applica-tion of B. Cheng, Serial No. 226,363, filed May 6, 1975, entitled "Detergent Composition".
The amount of additional builder salt(s) charged to the zeolite- -organic surfactant compositions of the invention '' - 1 'I ~ .
~, ,.
: - .. .. : :, . ., ~ . . .. . ; . . , ~t~6~G~3 .., ".. .
may be from about 5 to 50% by weight of the final laundry detergent formulation and preferably is from about 10 to 35%.
Similar proportions of inorganic filler salt, e.g., sodium sulfate, so~ um chloride, may be employed.
The laundry~ldétergent formulations which are prepared from the invented molecular sieve zeolite-organic surfactant ; compositions may also advantageously include small amounts, e.g., 0.05 to 8%, of additional conventional detergent adjuvants, the total amount of such minor adjuvants generally not exceeding 20%, preferably not exceedin~ 10% of the product. ;
These adjuvants include inorganic pigments, e.g., ultramarine blue; organic pigments, e.g., Indanthreane Blue* RS, dyes, e.g., Color Index Direct Blue l; and especially the fluorescent dyes known as optical brighteners. Such brighteners may be coumarin, triazolyl stilbener~ stilbene cyanuric, `
acylamino stilbene or miscellaneous types shown in issued ; patents. The concentration of brightener is advantageously in the range of about 1/20% to 1%, e.g., 1/10% to 1/2%.
The minor adjuvants may also include an organic gum anti-redeposition agent, such as sodium carboxymethyl cellulose, polyvinyl alcohol, hydroxymethyl ethyl cellulose, polyvinyl pyrrolidone, polyacrylamide, hydroxypropyl ethyl cellulose or ,.
mixtures thereof. Preferably the anti-redeposition agent is sodium carboxymethyl cellulose.
Additional minor detergent adjuvants which may be included in the detergent formulation include perfumes;
,, *Trademark ~, , `. ~ ' . ~ , : " :. ' . . , , :,: . , . ,, ,'' ,` .. , , . ,.. ,, ' . :, , . ,, . ., .. , .. ~
i73 fun~icides or preservatives such as polyhalosalicylanilides, for instance, tetrachlorosalicylanilide; sanitizersl such as trichlorocarbanilide; foam suppressors, such as NrN-dilauryl ~or di-coco alcohol) amine; enzymes, such as the subtilisin protease sold as Alcalase; bleaching agents, such as N-bromo and N-chloro imido compounds, for example, di- and tri-chloro (or bromo) cyanuric acid and water soluble salts thereof;
fabric softeners, such as l,2 alkane diols of 15 to 18 carbon atoms; and flow improving agents, such as the clay product, Satintone .
The detergent formulation may also contain a small amount of moisture, in addition to that which may be adsorbed in the zeolite molecular sieve, typically about 1 to S~.
The present compositions have been found to be effective detergents against a wide variety of soils,including clay and carbon soils, skin soil, natural and artificial sebum soils, particulate soils, etc., on a wide variety of fabrics, including cQtton, nylon and polyesters, such as polyethylene terephthalate and various blends, e.g., cotton-polyester.
~he present compositions are highly effective detergents even in the absence o conventional builder salts and other detergent adjuvants due to the excellent detergency building effect of the molecular sieve zeolite component. The molecular sieve zeolite components are highly efficient in sequestering calcium ion when washing in water of high calcium hardness.
Accordinglyj at a conventional laundry wash water concentration of about 0.15%, the present compositions remain effective as , t73 detergents even at calcium ion concentrations of 150 p.p.m.
(as CaCO ) or higher. On washing of fabrics with the present compositions no noticeable deposits of insolubles remain on the fabrics after rinsing and tumble drying, even in the absence of anti-redeposition agent in the formulation. It was surprising to discover this exce~le~ r.on-deposition characteristic of the present product in view of the known water insolubility of the molecular sieve zeolite component of the mixture. When tumble drying is not employed there may be a very slight deposit but it is much less than would be expected. Also, the zeolite molecular sieve is biologically safe, non-eutrophic, non-polluting and is harmless to laundry and laundry equipment. Any white fabrics washed with the present surfactant mixtures in the presence of colored fabrics are not substantially stained by dyes fugitive from the colored fabrics.
In addition to good building effects the present zeolite molecular sieves also counteract tackiness of detergents to a surprising extent, making them usefully free flowing and better able to be compounded with other detergent composition ingredients.
They are superior in this respect to ordinary clays and particulate carriers and they are useful builders, too.
The~following examples illustrate the invention but do not limit it. Unless otherwise indicated, all parts are by weight and temperatures are in C.
..~
~6 ' Paraffin sulfonate C15 (1~ 52.6 Molecular sieve zeolite 4A (2) 47.4 100.0 (1) A normally tacky sodium paraffin sulfonate wherein the n-alkyl substituent contains on the average 15 carbon atoms (Hoechst Chemical Corp.)
(2) A type 4A synthetic sodium molecular sieve ~eolite containing 2% moisture (proportions of molecular sieve zeolites given in this and followiny examples are on an anhydrous basis) having a mean particle diameter of 8.3 microns.
The paraffin sulfonate, which is a sticky, tacky, intractable, semi-solid at ambient temperature, is charged to a glass mixing vessel and the molecular sieve zeolite is added.
The vessel and its contents are agitated at ambient temperature for 15 minutes by rotation on a roll mill. On completion of ; agitatlon there is obtained a ~cmogeneous mixture which contains the molecular sieve zeolite and paraffin sulEonate in a ratio of 0.93:1 and whichis afree flowing non-tacky powder of excellent detergent properties when used to wash laundry at about 0.15%
concentration in an automatic washing machine. The free Elowing pulverulent zeolite-built surfactant retains its excellent~
homogeniety, flowability and non-tackiness,even on long storage in non-barrier containers.
In a variation of the above example substantially '' ' ' '. .
; - 18 - ~
, ,:
:. . .... . .
., . ,, . . . . ., . .: . , . . .: . . . . .. ....
6~,.6ti'3 similar excellent results are obtained when the molecular sieve zeolite is replaced by a sodium molecular sieve zeolite of crystalline type A having a mean particle diameter of 6.1 microns.
Similar excellent results are also obtained when the paraffin sulfonate is replaced by a mixture of sodium n-alkane monosulfonates of C14 and C15 chain lengths in approximately 2:1 ratio, said mixture also containing about 8~ of the corre~ponding n-alkane disulfonates~ 3% of unreacted paraffin starting material, and 5% of sodium sulfate.
.
EXAMPLE 2 ~
' % ~.
Molecular sieve z olite 4A (as in Example 1) 51 Higher fatty carboxylic acid soap (3) 49 100.0
The paraffin sulfonate, which is a sticky, tacky, intractable, semi-solid at ambient temperature, is charged to a glass mixing vessel and the molecular sieve zeolite is added.
The vessel and its contents are agitated at ambient temperature for 15 minutes by rotation on a roll mill. On completion of ; agitatlon there is obtained a ~cmogeneous mixture which contains the molecular sieve zeolite and paraffin sulEonate in a ratio of 0.93:1 and whichis afree flowing non-tacky powder of excellent detergent properties when used to wash laundry at about 0.15%
concentration in an automatic washing machine. The free Elowing pulverulent zeolite-built surfactant retains its excellent~
homogeniety, flowability and non-tackiness,even on long storage in non-barrier containers.
In a variation of the above example substantially '' ' ' '. .
; - 18 - ~
, ,:
:. . .... . .
., . ,, . . . . ., . .: . , . . .: . . . . .. ....
6~,.6ti'3 similar excellent results are obtained when the molecular sieve zeolite is replaced by a sodium molecular sieve zeolite of crystalline type A having a mean particle diameter of 6.1 microns.
Similar excellent results are also obtained when the paraffin sulfonate is replaced by a mixture of sodium n-alkane monosulfonates of C14 and C15 chain lengths in approximately 2:1 ratio, said mixture also containing about 8~ of the corre~ponding n-alkane disulfonates~ 3% of unreacted paraffin starting material, and 5% of sodium sulfate.
.
EXAMPLE 2 ~
' % ~.
Molecular sieve z olite 4A (as in Example 1) 51 Higher fatty carboxylic acid soap (3) 49 100.0
(3) The water soluble sodium soap of ~0% tallow fatty acid and 20~ coconut oil fatty acid.
The soap,which is a waxy solid at room temperature, of poor flow properties as fine particles,is agitated with the zeolite molecular sieve substantially as described in Example 1.
There is obtained a free ~lowing homogeneous powder in which the weight ratio of zeolite molecular sieve to the organic surfactant is about 0.95:1. The pulverulent product is non-sticky and has good detergent characteristics, with the molecular sieve helplng to build it.
. , :
' 6~3 EXAMPLE ~ % .
Molecular sieve zeolite 4A ~as in Example 1) 50 .
Neodol* 45-11, nonionic surfactant (4) 50 ~4) A water soluble nonionic detergent which is the reaction product of 11 mols of ethylene oxide and 1 mol of a mixture of C14 and C15 straight chain primary alkanols, said mixture ..
averaging about 14,5 carbon atoms in the alkyl substituent (Shell Chemical Co.) ;
The nonionic surfactant, which is a sticky, semi-solid at room temperature, is agi-tated with the zeolite molecular sieve .
substantially as described in Example 1. There is obtained a free flowing homogeneous powder in which the weight ratio of the molecular sieve zeolite to the organic surfactant is about :;~
1:1. The pulverulent product is non-sticky and has good detergent and 10w characteristics. Flow is improved further by increasing the proportion of the molecular sieve, se~uentially to 2:1, 4:1, ;:
l0:1 and 80:1, with respect to the surfactant. ;
EXAMPLE ~ %
Molecular sieve zeolite, 4A (as in Example 1) 50 Miranol* C2M (anhydrous acid) (5) 50 (5) An amphoteric water soluble surfactant containing both anionic and cationic substituents, as the anhydrous form of , the acid of the formula :
*Trademark ~:
-20- ~ . ' ,.", ~, :
. ..
~ 3 C H 3 ¦~ ¦ / CH2CH20CH2CooH
~ CH2COOH
OH
(Miranol Chemical Co., Inc.) The amphoteric surfactant, which is a tacky paste at ' , room ~emperature, is mixed with the molecular sieve zeolite substan-tially as described in Example 1. There is thus obtained a free fIowing homogeneous powder in which the weight ratio of the molecular sieve zeolite to the organic surfactant is about 1 The pulverulent product is non-tacky and has 'good detergent characteristics. Flowability is not as good at a ratio of 0.5:1 but is better than for the surfactant particles above. At 10~
and 50:1 ratios flowability is much improved. Similar results r .
are obtained when half the Miranol* C2M is replaced by either the paraffin sulfonate of Example 1 or the cationic compound, dimethyl ic~ ; ;
di-hydrogenated tallow ammonium chloride, and half the quantity of , -molecular sieve is also replaced ~y a Type X or Y sieve. `; -EXAMPLE 5 ~ ~
.... - .
.j . - .
Paraffin sulfonate C15 (as in Example 1) 10 Molecular sieve zeolite 4A (as in Example 1) 19.6 So~ium silicate (6) 15 NTA organic builder (7) 15 r : .
Neodol* 45-11 nonionic surfactant (as in Example 1) 2 ;~
~ i:;
CMC anti-redeposition agent (8) 0.5 ~
: . : ,' . : . .
Optical brightener (9) 0.3 Sodium sulfate filler 35.4 Water 2.2 100 .0 * Trademark -21 - :~
r--_ 36~67;~
(6) Na2O:SiO2 = 1:2.35 (7) Trisodium nitrilotriacetate (added as the monohydrate but proportions given are on an anhydrous basis) (8) Sodium carboxymethyi cellulose (detergent grade) S (9) 4,4'-bis(4-phenyl-2H-1,2,3-triazol-2-yl)-2,2'-stilbene dïsulfonic acid, potassium salt.
The paraffin sulfonate and half of the molecular sieve zeolite are agitated as described in Example 1 to obtain a free flowing, non-tacky, pulverulent mixture. The remaining portion of the molecular sieve zeolite and the nonionic surfactant are agi~ated as described in Exa~ple 3.
The two mixtures are mixed in the dry state by agitation in a ribbon mixer for about 5 minutes. To the resulting particulate mixture. the silicate, organic builder salt, anti-redeposition agent, optical brightener and filler salt are added. The agitation of the resultant mass is continued for 8 minutes and the resultant particulate solid laundry detergent is dropped from the mixer.
The detergent product is added to water of 150 p.p.m. CaCO3 equivalent mixed calcium and magnesium hardness (calcium ion:
magnesium ion ratio of 3:2) with about 1.5 grams of the detergent composition being charged per liter of water. The aqueous detergent is used to wash various fabrics in a conventional automatic washing machine at a washing temperature of about 50C., with the period for agitated washing before spinning, i.e., before centrifuging to remove the wash water prior to rinsing, being , \
. .
'73 about 10 minutes. In automatic washing tests the detergent composition is highly effective as a detergent,washing out a wide variety of 50ils including clay and carbon soils, skin soils, natural and artificial sebum soils and particulate soils from a variety of fabrics,including cotton, nylon and polyester, e.g., polyethylene terephthalate, and cotton-polyester blends. In these washing experiments only a very slight, almost unnoticeable insoluble residue is left on the clothes after rinsing, if they are line dried and none is noted after tumble drying. Thls excel-lent non-deposition characteristic of the detergent formulation obtains even when the anti-redeposition agent (CMC) is omitted from the detergent composition.
Fugutive dyes, which may bleed from colored fabrics into the wash water and stain white or undyed fabrics when conventional detergents are used, do not s~ain white fabrics when tbe zeolite mol~cular sieve containing detergents of the invention are employed to wash white and dyed clothes together.
In the foregoing detergent formulation and in the previous examples, whereapplicable, it will be appreciated that the silicate and/or the organic builder salt can be replaced completely or in part by other builder salts, e.g., sodium carbonate, 2-hydroxyethyl imino diacetic acid, disodium salt and/or pentasodium tripolyphosphate. SimiIarIy the sodium carboxymethyl cellulose can be replaced by other anti-redeposi-tion agents,such as polyvinyl pyrrolidone and polyvinyl alcohol, .
_ 23 \
~;.0~ 7~
and the filler salt can be replaced by another inert salt, such as sodium chloride. The zeolite molecular sieve can be replaced by other effective molecular sieve zeolites,including those of types X, Y and L or mordenite, chabazite and erionite crystal structures. Components and proportions may be varied,as described in the oregoing specification and free flowing products are obtainable. If desired, the formulations may be spray dried, spray cooled or post sprayed, but direct "dry" mixing is usually prefer-red because it saves energy, is less apt to cause pollution and is easier to effect with equipment that requires lower capital investments.
The invention has peen described with respect to working examples and illustrations thereof but is not to be limited to these because it is evident that one of skill in the art with - 15 access to the present specification will be able to employ substitutes and equivalents without departing from the spirit or scope of the inventlon.
', . ...
_ 24 . \ .
~ .
The soap,which is a waxy solid at room temperature, of poor flow properties as fine particles,is agitated with the zeolite molecular sieve substantially as described in Example 1.
There is obtained a free ~lowing homogeneous powder in which the weight ratio of zeolite molecular sieve to the organic surfactant is about 0.95:1. The pulverulent product is non-sticky and has good detergent characteristics, with the molecular sieve helplng to build it.
. , :
' 6~3 EXAMPLE ~ % .
Molecular sieve zeolite 4A ~as in Example 1) 50 .
Neodol* 45-11, nonionic surfactant (4) 50 ~4) A water soluble nonionic detergent which is the reaction product of 11 mols of ethylene oxide and 1 mol of a mixture of C14 and C15 straight chain primary alkanols, said mixture ..
averaging about 14,5 carbon atoms in the alkyl substituent (Shell Chemical Co.) ;
The nonionic surfactant, which is a sticky, semi-solid at room temperature, is agi-tated with the zeolite molecular sieve .
substantially as described in Example 1. There is obtained a free flowing homogeneous powder in which the weight ratio of the molecular sieve zeolite to the organic surfactant is about :;~
1:1. The pulverulent product is non-sticky and has good detergent and 10w characteristics. Flow is improved further by increasing the proportion of the molecular sieve, se~uentially to 2:1, 4:1, ;:
l0:1 and 80:1, with respect to the surfactant. ;
EXAMPLE ~ %
Molecular sieve zeolite, 4A (as in Example 1) 50 Miranol* C2M (anhydrous acid) (5) 50 (5) An amphoteric water soluble surfactant containing both anionic and cationic substituents, as the anhydrous form of , the acid of the formula :
*Trademark ~:
-20- ~ . ' ,.", ~, :
. ..
~ 3 C H 3 ¦~ ¦ / CH2CH20CH2CooH
~ CH2COOH
OH
(Miranol Chemical Co., Inc.) The amphoteric surfactant, which is a tacky paste at ' , room ~emperature, is mixed with the molecular sieve zeolite substan-tially as described in Example 1. There is thus obtained a free fIowing homogeneous powder in which the weight ratio of the molecular sieve zeolite to the organic surfactant is about 1 The pulverulent product is non-tacky and has 'good detergent characteristics. Flowability is not as good at a ratio of 0.5:1 but is better than for the surfactant particles above. At 10~
and 50:1 ratios flowability is much improved. Similar results r .
are obtained when half the Miranol* C2M is replaced by either the paraffin sulfonate of Example 1 or the cationic compound, dimethyl ic~ ; ;
di-hydrogenated tallow ammonium chloride, and half the quantity of , -molecular sieve is also replaced ~y a Type X or Y sieve. `; -EXAMPLE 5 ~ ~
.... - .
.j . - .
Paraffin sulfonate C15 (as in Example 1) 10 Molecular sieve zeolite 4A (as in Example 1) 19.6 So~ium silicate (6) 15 NTA organic builder (7) 15 r : .
Neodol* 45-11 nonionic surfactant (as in Example 1) 2 ;~
~ i:;
CMC anti-redeposition agent (8) 0.5 ~
: . : ,' . : . .
Optical brightener (9) 0.3 Sodium sulfate filler 35.4 Water 2.2 100 .0 * Trademark -21 - :~
r--_ 36~67;~
(6) Na2O:SiO2 = 1:2.35 (7) Trisodium nitrilotriacetate (added as the monohydrate but proportions given are on an anhydrous basis) (8) Sodium carboxymethyi cellulose (detergent grade) S (9) 4,4'-bis(4-phenyl-2H-1,2,3-triazol-2-yl)-2,2'-stilbene dïsulfonic acid, potassium salt.
The paraffin sulfonate and half of the molecular sieve zeolite are agitated as described in Example 1 to obtain a free flowing, non-tacky, pulverulent mixture. The remaining portion of the molecular sieve zeolite and the nonionic surfactant are agi~ated as described in Exa~ple 3.
The two mixtures are mixed in the dry state by agitation in a ribbon mixer for about 5 minutes. To the resulting particulate mixture. the silicate, organic builder salt, anti-redeposition agent, optical brightener and filler salt are added. The agitation of the resultant mass is continued for 8 minutes and the resultant particulate solid laundry detergent is dropped from the mixer.
The detergent product is added to water of 150 p.p.m. CaCO3 equivalent mixed calcium and magnesium hardness (calcium ion:
magnesium ion ratio of 3:2) with about 1.5 grams of the detergent composition being charged per liter of water. The aqueous detergent is used to wash various fabrics in a conventional automatic washing machine at a washing temperature of about 50C., with the period for agitated washing before spinning, i.e., before centrifuging to remove the wash water prior to rinsing, being , \
. .
'73 about 10 minutes. In automatic washing tests the detergent composition is highly effective as a detergent,washing out a wide variety of 50ils including clay and carbon soils, skin soils, natural and artificial sebum soils and particulate soils from a variety of fabrics,including cotton, nylon and polyester, e.g., polyethylene terephthalate, and cotton-polyester blends. In these washing experiments only a very slight, almost unnoticeable insoluble residue is left on the clothes after rinsing, if they are line dried and none is noted after tumble drying. Thls excel-lent non-deposition characteristic of the detergent formulation obtains even when the anti-redeposition agent (CMC) is omitted from the detergent composition.
Fugutive dyes, which may bleed from colored fabrics into the wash water and stain white or undyed fabrics when conventional detergents are used, do not s~ain white fabrics when tbe zeolite mol~cular sieve containing detergents of the invention are employed to wash white and dyed clothes together.
In the foregoing detergent formulation and in the previous examples, whereapplicable, it will be appreciated that the silicate and/or the organic builder salt can be replaced completely or in part by other builder salts, e.g., sodium carbonate, 2-hydroxyethyl imino diacetic acid, disodium salt and/or pentasodium tripolyphosphate. SimiIarIy the sodium carboxymethyl cellulose can be replaced by other anti-redeposi-tion agents,such as polyvinyl pyrrolidone and polyvinyl alcohol, .
_ 23 \
~;.0~ 7~
and the filler salt can be replaced by another inert salt, such as sodium chloride. The zeolite molecular sieve can be replaced by other effective molecular sieve zeolites,including those of types X, Y and L or mordenite, chabazite and erionite crystal structures. Components and proportions may be varied,as described in the oregoing specification and free flowing products are obtainable. If desired, the formulations may be spray dried, spray cooled or post sprayed, but direct "dry" mixing is usually prefer-red because it saves energy, is less apt to cause pollution and is easier to effect with equipment that requires lower capital investments.
The invention has peen described with respect to working examples and illustrations thereof but is not to be limited to these because it is evident that one of skill in the art with - 15 access to the present specification will be able to employ substitutes and equivalents without departing from the spirit or scope of the inventlon.
', . ...
_ 24 . \ .
~ .
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A free flowing particulate detergent composition in the form of particles consisting essentially of a substantially homogeneous mixture of a finely divided water-insoluble crystalline aluminosilicate zeolite having an A12O3SiO2 mole ratio of 1:2 to 1:5, a moisture content of from 1% to 36%, a network of substantially uniformly sized pores in the range of about 3 to 10 Angstroms, a particle size of 5 to 9 microns, calcium ion sequestering properties and a cation which is selected from the group consisting of sodium potassium, lithium, ammonium and hydrogen; and a normally tacky water-soluble organic surfactant selected from the group consisting of anionic, nonionic, cationic and amphoteric surfactants in a weight ratio of zeolite to surfac-tant of 20:1 to about 0.5:1.
2. A detergent composition according to Claim 2 wherein the anionic surfactant is an alkali metal salt and the molecular sieve zeolite is selected from the group consisting of sodium and potassium type A, X and Y zeolites.
3. A detergent composition according to Claim 2 wherein the surfac-tant is a C10-C20 paraffin sulfonate salt and the molecular sieve zeolite is a type A molecular sieve.
4. A detergent composition according to Claim 4 wherein the higher paraffin sulfonate is a sodium monosulfonate and the molecular sieve zeolite is a sodium zeolite containing from 1% to 3% by weight of water.
5. A detergent composition according to Claim 4 wherein the paraffin sulfonate surfactant contains an alkyl group of 13 to 17 carbon atoms.
6. A detergent composition according to Claim 5 wherein the paraffin sulfonate contains about 15 carbon atoms to the alkyl substituent thereof and the ratio of molecular sieve zeolite to surfactant is from 1:1 to 0.9:1.
7. A detergent composition according to Claim 1 wherein the weight ratio of zeolite to surfactant is from 1:1 to 0.9:1.
8. A detergent composition according to Claim 2 wherein said water-soluble organic detergent is selected from the group consisting of C10-C20 alkyl sulfonates, C10-C20 alkanoic acids, C8-C20 alcohol ethoxylates having 3 to 20 ethylene oxide groups per mole of alcohol and amphoteric imidazolines having the following structural formula
9. A detergent composition according to Claim 2 which further includes an organic builder salt, said builder salt being present in a proportion of about 5% to 50% by weight of the composition.
10. A detergent composition according to Claim 9 wherein said organic builder salt is sodium or potassium nitrilotriacetate.
11. A process for converting a normally tacky water-soluble organic surfactant selected from the group consisting of anionic, nonionic, cationic and amphoteric surfactants to a free-flowing non-tacky powder which comprises intimately mixing for 1 to 20 minutes at a temperature in the range of 5 to 90°C. a finely divided, water-insoluble, crystalline aluminosilicate zeolite having an Al2O3 to SiO2 mole ratio of 1:2 to 1:5, a moisture content of from 1% to 36%, particle size of 5 to 9 microns, calcium ion sequestering proper-ties and a cation which is selected from the group consisting of sodium, potassium, lithium, ammonium and hydrogen and a network of substantially uni-formly sized pores in the range of 3 to about 10 Angstroms, with said surfac-tant, employing about 0.5 to 20 parts of a molecular sieve zeolite per part of the surfactant to form a homogeneous pulverulent product.
12. A method according to Claim 11 wherein said intimate mixing is achieved by milling said mixture on a roll mill.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US50373674A | 1974-09-06 | 1974-09-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1061673A true CA1061673A (en) | 1979-09-04 |
Family
ID=24003305
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA234,799A Expired CA1061673A (en) | 1974-09-06 | 1975-09-04 | Free flowing particulate detergent compositions containing a normally tacky detergent |
Country Status (3)
| Country | Link |
|---|---|
| CA (1) | CA1061673A (en) |
| DE (1) | DE2538680A1 (en) |
| FR (1) | FR2283953A1 (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA767017B (en) * | 1975-12-15 | 1978-06-28 | Colgate Palmolive Co | Method for reconditioning detergent powders |
| US4391727A (en) * | 1975-12-15 | 1983-07-05 | Colgate Palmolive Company | Non-caking bleach containing molecular sieve zeolite |
| US4427567A (en) | 1975-12-15 | 1984-01-24 | Colgate-Palmolive Company | Method for reconditioning of poorly flowing or caked detergent powders |
| US4414130A (en) * | 1976-08-17 | 1983-11-08 | Colgate Palmolive Company | Readily disintegrable agglomerates of insoluble detergent builders and detergent compositions containing them |
| US4411809A (en) * | 1976-12-02 | 1983-10-25 | Colgate Palmolive Company | Concentrated heavy duty particulate laundry detergent |
| US4248911A (en) * | 1976-12-02 | 1981-02-03 | Colgate-Palmolive Company | Concentrated heavy duty particulate laundry detergent |
| US4347152A (en) * | 1976-12-02 | 1982-08-31 | Colgate-Palmolive Company | Phosphate-free concentrated particulate heavy duty laundry detergent |
| US4666740A (en) * | 1976-12-02 | 1987-05-19 | The Colgate-Palmolive Co. | Phosphate-free concentrated particulate heavy duty laundry detergent |
| US4260651A (en) * | 1976-12-02 | 1981-04-07 | Colgate-Palmolive Company | Phosphate-free concentrated particulate heavy duty laundry detergent |
| US4663194A (en) * | 1976-12-02 | 1987-05-05 | The Colgate-Palmolive Co. | Phosphate-free concentrated particulate heavy duty laundry detergent |
| DE2714604C3 (en) * | 1977-04-01 | 1985-04-25 | Joh. A. Benckiser Gmbh, 6700 Ludwigshafen | Granulate based on polymer phosphate and ion-exchanging alkali aluminosilicate |
| US4269725A (en) * | 1977-04-21 | 1981-05-26 | Laporte Industries Limited | Washing compositions |
| DE2744773C3 (en) * | 1977-10-05 | 1986-08-21 | Joh. A. Benckiser Gmbh, 6700 Ludwigshafen | Granulate based on polymer phosphate and ion-exchanging alkali aluminosilicate |
| US4664950A (en) * | 1980-09-02 | 1987-05-12 | The Colgate Palmolive Co. | Concentrated heavy duty particulate laundry detergent |
| US4666738A (en) * | 1980-09-02 | 1987-05-19 | The Colgate-Palmolive Co. | Method for making a phosphate containing concentrated heavy duty particulate laundry detergent |
| ES8400768A1 (en) * | 1980-11-06 | 1983-11-01 | Procter & Gamble | Bleach activator compositions, preparation thereof and use in granular detergent compositions. |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3769222A (en) * | 1971-02-09 | 1973-10-30 | Colgate Palmolive Co | Free flowing nonionic surfactants |
-
1975
- 1975-08-30 DE DE19752538680 patent/DE2538680A1/en not_active Withdrawn
- 1975-09-04 CA CA234,799A patent/CA1061673A/en not_active Expired
- 1975-09-04 FR FR7527113A patent/FR2283953A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| FR2283953A1 (en) | 1976-04-02 |
| DE2538680A1 (en) | 1976-03-18 |
| FR2283953B1 (en) | 1979-03-09 |
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