CA1057618A - Particulate hydroxyalkyl iminodicarboxylate detergent compositions - Google Patents

Abstract

Abstract A non-phosphate particulate heavy duty laundry detergent includes:
a mixture of a synthetic organic anionic detergent, such as sodium linear tridecyl benzene sulfonate a nonionic surface active agent, such as a higher alkyl lower alkoxylated lower alkanol; sodium silicate; sodium carbonate; an organic gum anti-redeposition agent, such as sodium carboxymethyl cellulose;
built with a hydroxyalkyl iminodicarboxylate builder salt, such as disodium 2-hydroxyethyl iminodiacetate; and preferably contains a higher alkyl poly-lower alkoxylate sulfate salt. Such compositions have detersive actions equivalent to those of phosphate detergents.

Description

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This invention reI~tes to particulate heavy duty detergent composi-tions and more particularly to detergent compositions devoid of inorganic phosphate builder salts. It is especia~ly concerned with detergent composi-tions built with hydroxyalkyl iminodicarboxylate salts and such compositions have a detersive action equivalent to that of phosphate-built detergents.
Synthetic organic detergent compositions based on anionic and non-ionic organic detergents or surface active agents usually include a builder salt to improve detergency Various phosphates, boron compounds, carbonates ~ ;
and silicates have been found to have building properties and of these the phosphates3 especially p0ntasodium tripolyphosphate, was acknowledged to be far superior. However, due to opinions tha~ phosphates in detergents contri-bu~e to eutrophication of inland waters, causing excessive algae growth, and because of go~ernment regulations, efforts have been made to produce non-phos-phate detergents including other builders than pentasodium tripolyphosphate.
One such substitute, trisodium nitrilotriacetate (NTA) is not being used in ., ~ ,- :
the United States because of an indication that it could, under certain cir-~i~ cumstances, be carcinogenic.
~, When iminodicarboxylate salts are tested as builders for organic I anionic and nonionic detergent compositions relatively few of the formulations -3 20 have detersive actions equivalent to that of phosphate-built detergents.
i Several such formulations, equi~alent in detersive action to phosphate-built .i . ~
~ detergents, are disclosed in my patent application, filed concurrently with : ~ . . . .
the present application, entitled Particulate Silicate-Hydroxyalkyl Iminodiace- ~
tate Built Detergent Compositions of Improved Properties, which relates to ~ -:. ~ , -1 detergent compositions in which the hydroxyalkyl iminodicarboxylate is incor-porated as a solid hydrate.
,...
` In accordance with the present invention a particulate heavy duty ,. . . .
- laundry detergent equi~alent in detersive action to a phosphate-built deter-~ gent comprises about 5 to 30 parts of a synthetic organic anionic detergent, ''',, ~ '.'''' .,,. : ,::
,-., :-: ., .. . - ' ., .. , " , .. , : .. ' ~ , , , .. ' , . . - ., . , .. : :

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about 1~5 to 7.5 ~arts ~ a syn~hetic org~nic nonionic detergent, about 5 to 30 parts o~ an alkali metal silicate in which the ratio of alkali metal uxide, M20 to silica is from 1:1.6 to 1:3, about 4 to 20 parts of an alkali metal carbonate, about 9 to 30 parts of a hydroxyalkyl iminodicarboxylate builder salt of the following formula Rl ~ C _ COOM
HO --~R~-- N
Rl ~ C - COOM

wherein R is a 2 to 4 carbon alkyl group, Rl and R2 are hydrogen or Cl to C3 alkyl with the carbons of Rl + R3 no more than 3, and M is 3 alkali metal, ammonium or substituted ammonium, and about 0.25 to 3 parts of an organic gum anti-redeposition agent, with ~he sum of ~he parts being from about 35 to 100 and with the proviso that when the amount of synthetic organic nonionic ~-detergent present in the composition is less than about 2.5 parts there is `
present at least about 20, preferably at least about 23, parts of the builder salt and/or there is present about 2 to 10 parts of a higher alkyl poly-lower alkoxy lower alkanol sulfate surface active agent.
Preferably, the detergent composition of the invention also contains about S to 50 parts of alkali metal sulfate and/or alkali metal chlo-ride filler salt and about 2 to 6 parts of moisture with the sum of the parts then being from about 42 to 150.
The detergent composition of the invention preferably is about 5 :- ..
l or 7 to 30%, especially about 8 to 15%, of the anionic detergent, about 1.5 to ~-3 ~
7.5% of the nonionic detergent, about 5 to 30%, especially about 12 to 20%, of the alkali metal silicate, about 4 to 20%, especially about 8 to 15%~ of -' the alkali metal carbonate, about 9 to 27% of the builder salt, about O.25 to 3%, especially about 0.3 to 2%, of the gum anti-redeposition agent, about 5 - to 50%, especially about 30 to 50%, of filler salt and about 2 to 6% of . . .
moisture, wi~h the pToviso that when the concentration of the nonionic surface ~D

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active agent is less than about 2.5% there is present at least about 20% of the builder salt and/or there i5 present about 2 OT 3 to 10% of the alkali metal higher alkyl poly-lower alkoxy lower alkanol sulfate and with the further proviso that the total amount of adjuvant materials, that is materials other than those constituents recited above, is limited to about 20%.
The detergent compositions of the invention are advantageously prepared by spray dryi~g into air ae elevated temperature an aqueous mixture :" '.

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lC3S~8 comprising the anionic detergent, the nonionic detergent, the alkali metal silicate, the hydroxyalkyl iminodicarboxylate builder salt, the alkali metal carbonate, and the organic gum anti-redeposition agent. Under the elevated temperature conditions of spray drying, preferably effected countercurrently, less than about 2 to 2.5% of the nonionic detergent is usually retained in the dried product, any additional nonionic detergent or surface active agent ori-ginally present in the aqueous mixture usually being lost by overhead carry off, that is by pl~ning~ in the spray drying step. The resultant dried pro-duct, containing less than about 2.S% nonionic surface active agent, is often o of insufficient or unsatisfactory detersive action. To overcome this loss additional nonionic detergent or surfactant, which is usually a near liquid, paste or wa~y material at room temperature, may be sprayed onto the spray dried particulate product to provide a detergent composition of the desired nonionic detergent content and detersive action. Alternatively, a greater amount of the hydroxyalkyl iminodicarboxylate builder salt can be charged to the aqueous mixture prior to spray drying~ said greater amount being suffi-cient to provide a concentration of builder salt in the dried product of at least about 20%, frequently being 23 to 27%. As an alternative or in addition to employing the aforementioned greater concentration of builder salt, an , .
alkali metal higher alkyl poly-lower alkoxy lower alkanol sulfate can be charged to the aqueous mixture prior to spray drying, said sulfate being in an amount providing a concentration of about 3 to 10%, preferably about 3.5 to 4.5%, in the spongy dried product. Detergent compositions of the inven-.; ~ .
tion including the alkali metal higher alkyl pol7-lower alko~y lower alkanol sulfate without the use of the higher concentration of builder salt, that is, `~ utilizing a concentration of about 9 to 23% and especially about 9 to 17% of .
the hydroxyalkyl iminodicarboxylate builder salt, are especially resistant to caking on storage and hence are especially preferred.
; The detergent compositions of the present invention include as a . . .

''` :' iO57G113 primary detersive constituent a mixture ot` an anionic synthetic organic det-ergent selected from the group consisting of organic sulfonates and sulfates, and a nonionic detergent (or surface active agent), the detersive action of ; which mixture is supplemented in certain above-described embodiments of the invention by an alkali metal poly-lower aIkoxy lower alkanol sulfate. Suit-able organic sulfonate and sulfate detergents are described in McCutcheon's Deter ents and Emulsifiers 1969 Annual wherein such compounds are listed by g _ chemical formulas and trade names. Additional suitable such compounds are also described in the text Surface Active Agents and Deter~ents,Vol. II, by Schwartx, Perry and Berch (Interscience P~lblishers, 1958~ In short, such materials include hydrophilic and lipophilic groups, the lipophilic portions ~; whereof normally contain a higher hydrocarbyl chain~ usually of 10 to 20 car-bon atoms and the hgdrophilic portions of which include a salt-forming ion, `~
preferab~y an alkali metal cation. Among such useful detergents the organic sulfonates are preferred, according to the invention, but corresponding sul-fates and sometimes, phosphates and phosphonates, are useful, also. Suitable '9' ~ a~ionic detergents include, for example, the linear higher alkyl benzene su1-fonates, the branched chain higher alkyl ben~ene sulfonates (these are not usually sufficientl~ biodegradable to be accepted in modern detergent formula-tions), the higher olefin sulfonates, the higher alkyl sulfonates, paraffin ;
. ~
i sulfonates and higher alcohol sulfates. The corresponding phosphates and ~ phosphonates may also be useful, at least in part. The hydrocarbyl alkyl and

3 higher fatty acyl groups of such compounds will generally be of 12 to 18 car-, . .
¦~ bon atoms and the salt-forming cations thereof will preferably be alkal; metal ~;
1 ;:
¦ cations, e.g., sodium, potassium, although ammonium and substituted ammonium ~ ~
, , .
cations derived from alkanolamines and alkylamines may be utilized also. The ' sodium salts tend to make harder detergent products, which are more freely flowing and ha~e less tendency to cake than those containing ammonnum, alkano-lamine, alkylamine and potassium cations.
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', , ~57~i~8 Among the preferred organic sulfonate detergents, linear higher a~cyl aromatic sulfona~es~ preferably those wherein the aromatic group is phenylic are utilized and ~inear tridecyl benzene sulfonates, usually as the sodium salt, are especially preferred. Of these materials it is highly preferred to employ the linear higher alkyl benzene sulfonates wherein the alkyl substitu-ents are of 12 to 18 carbon atoms~ especially of 12 to 15 carbon atoms, and in which the salt-forming cation is alkali metal3 especially sodium.
; The nonionic surface active agents utilized in the invention include higher alkyl polyalkoxylates, i.e., the condensation products of higher fatty alcohols with lower (2-4 carbon atoms) alkylene glycols and/or with lower alkylene oxides such as ethylene oxide or propylene oxide, as exemplified by Neodol~trademark) 45-11, Plurafac(trademark) B-26 and Alfonic(trademark) 1618-65. Such products are normally liquid or semi-solid at room temperature.
~- Also useful are the block copolymers o propylene glycol, propylene oxide and ethylene oxide, such as the Pluronics(trademark), e.g.7 Pluronic(trademark) . ~ .
'! L 44, and Pluronic(trademark) F-68, and the middle alkyl phenyl polyoxyethylene ethanols7 such as those sold as Igepals(trademarks). Preferably, the nonionic detergent that wi]l be utillzed in the invention is a higher alkyl polyethoxy-lated alcohol. The number of carbO~ atoms in the higher alkyl group averages from 10 to 18, preferably 12 to 15 or 18, especially preferably, 14 to 15, and the molar ratio of ethoxy to higher a~cyl groups is from 7 to 20, preferably 9 to 13, and especially preferably, about 11.
The higher alkyl polyalkoxy sulfate salt, charged in accordance with certain above-described embodiments of the invention to supplement the deter-sive effect of the organic anionic detergent and the nonionic detergent, is .; ~
a sulfated linear condensation product of a primary higher fatty alcohol with a lower alkylene glyco1 and/or a lower a~cylene oxide, such as ethylene oxide or pr~pylene oxide, as exemplified in Neodol 25-35. Preferably the higher alkyl polyethocy sulfa~e salt is a higher allcyl polyethoxy sulfate salt ~57~

wherein -the highcr alkyl group contains an average of L2 to l5 carbon atoms and the molar ratio of ethoxy to higher alkyl groups is about 2 to 7, especi-ally about 3. The higher alkyl ethoxy sulfate salt is preferably a~l alkali metal salt, especially sodi~ salt, but can also be an ammonium or substituted ammonium salt derived from, for example, a lower alkanolamine or lower alkyl-amine. "Lower" means of 1 to 3 carbon atoms, e.g. 7 triethanolamine, trimethyl-amine.
In a strict sense the higher alkyl polyethoxy sulfate salt is an an~
ionic surface active agent which may have detersive properties, too However~
it is not contemplated to be employed as an anionic detergent in place of the above-described anionic detergents.
` An important constituent of the detergents of the invention is the alkali metal silicate component. Such compounds are water soluble and are useful as builders for synthetic organic detergents. They exert alkalizing effects, help to counteract water hardness and have both an independent de-tersive effect and the property of improving the detersive properties of the anionic and nonionic detergents utilized in the present invention. The alkali metal silicates contemplated as constituents of the present compositions ha~e .- . . ..
i~ the formula M20:SiO2 wherei: M represents alkali metalg e.g., sodium or potas-sium, most preferably sodium, said ratio being preferably in the range of 1:1.6 `~
to 1:3, more preferably 1:2 to 1:2.4 and es~pecially about 1:2.
Another detergent builder that is desirable in the present composi- ~ `
tions is alkali metal carbonate, such as sodium or potassium carbonate. Sodium carbonate is preferred and will normally be utilized in the anhydrous form. -However, hydrates~ such as washing soda can also be employed, providing that the excess moisture is removed therefrom in a drying process~ e.g., by spray drying. Alkali metal sesquicarbonates and bicarbonates may be used as sub-stitutes for the carbonates providing that the mi~ing and drying steps or . ;~ .
~ other operations convert these to the carbonates. The sodium or other alkali ., . ~ :

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metal carbonate has the useflll et`fec-ts of increasing the pH of the aqueous mixture before spray drying and of giv:ing the detergent product desirable hi~her pH than would otherwise be the case. It also helps to improve product flow and storage properties, serving to sorb moisture without objectionable caking.
The iminodicarboxylate builder salts of this invention are water sol-uble hydroxyalkyl iminodicarboxylates wherein the carboxylates, i.e., the alkanoate residues, are of 2 to 4 carbon atoms, preferably of 2 to 3 carbon atoms and most preferably are of 2 carbon atoms ~acetate). In these compounds, 10 the alkanoate residue is attached to the imino nitrogen atom at the carbon atom which is alpha to the carboxylate group.
The hydroxyalkyl group of the hydroxyalkyl iminodicarboxylate salts is hydroxy-lower a~yl wherein the alkyl group is of 2 to 4 carbon atoms, and although the hydroxy group needs not be terminal, for best effects this positioning is favored. Preferably the hydroxyalkyl group is hydroxyethyl.
The hydroxyalkyl iminodicarboxylates, are found to be excellent builders for synthetic organic detergents and have desirable sequestering ~i effects against water hardness ions, such as calcium and magnesium, which might otherwise interfere with the washing action of the organic detergent.
The hydroxyalkyl iminodicarboxylates employed are preferably dialkali metal salts, for example, the dipotassium and especially3 the disodium salts. If ; desired, however, water soluble hydroxyalkyl iminodicarboxylate salts of other cations can be employed. For example, ammonium and the mono-, di-, and tri- -:.;~ .
~` alkanol ammonium and the mono-, di-, and tri-alkyl ammonium groups wherein the j alkanol and alkyl groups are lower, that is of 1 to 4 carbon atoms, pre~er-ably of 1 to 3 carbon atoms, and most preferably, of 2 carbon atoms, are also useful. Examples of such material include d~-(triethanolammonium)-2-hydroxy-, propyl iminodi-(alpha)-prop1~nate, di-(tributylammonium)-4-hydroxybutyl imino-diacetate; di-(monoisopropanolammonium)2-hydro~yethyl iminodiacetate, and di-_ 7 -~057~8 (trimethylammonium)2-hydroxyethyl iminodiacetate.
To improve the cleaning power of the detergent and to help maintain the particles of the product in smooth regular, globular and stable form, an -organic gum anti-redeposition agent, such as sodium carboxymethyl cellulose, polyvinyl alcohol, hydroxymethyl ethyl cellulose, poly~inyl pyrrolidone, poly-acrylamide, hydroxypropyl ethyl cellulose or mixtures thereof may be utilized.
Preferably the gum anti-redeposition agent is sodium carboxymethyl cellulose.
Filler salts for the present particulate detergent compositions in-clude sodium sulfate, sodium chloride and mixtures thereof. Preferably the 10 filler salt is sodium sulfate.
Together with the foregoing components of the present detergents there may be employed conventional detergent adjuvants, particularly perfumes, flm-; gicides or preservatives, such as a polyhalosalicylanilides, and fluorescent dyes or optical brighteners, such as the well known aminostilbene derivatives.
The less important conventional adjuvants which can be incorporated in these compositions include sanitizers~ such as trichlorocarbanilide, colorants, ;~`
e.g., dyes and pigments; foam improvers, e.g.9 lauric diethanolamide; foam ;
depressants, e.g.~ silicones; antioxidants, e.g., stannic chloride; and flow , improving agents, such as the clay product commercially sold to the detergent - 20 industry under the trademark ~'Satintone".
The total adjuvant content of the present particulate detergent com-` positions will in general not exoeed 20% and is preferably about 1 to 10%, more preferably about 2%. Conventional detergent adjuvants which are of high thermal stability Gan be charged to the present compositions prior to spray drying whereas those of lower thermal stability or those which would inter-fere with drying are advantageously admixed with the particulate spray dried product. Perfume and any nonionic surface active agent required are preferably added to the particulate product after spray drying so that the surfaces of the detergent particles contain a higher proportion of these materials than . . .

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the interiors thereof.
The constituents of the present detergent compositions can be admixed in a conventional soap crutcher or detergent mixer. PreferablyJ in order to prevent formation of silica geIs and precipitates, an aqueous solu-tion of hydroxyalkyl iminodicarboxylate saltJ at a pH above 12 is mixed with an aqueous solution of the alkali metal silicate in the crutcher, maintained at a moderately elevated temperature, e.g., about 55 to 80C. Preparation of the iminodicarboxylate and subsequent admixing may be in accordance with the technique descrlbed in my copending Canadian application Serial No.
212~256J filed concurrently with the present application, entitled Manufacture of Improved Aqueous Alkali Metal Silicate-Alkali Metal Hydroxyalkyl Iminodi-acetate Compositions.
After the above recited admixing, the other constituènts of the detergent compositlon may be added, including additional water over that already present with other components or reactants previously added, the anionic detergent, the nonionic detergent, any higher alkyl poly-lower alkoxy sulfate to be incorporated, the alkali metal car~onate, filler salts, the organic gum anti-redeposition agent ~desirably dissolved in water or in an ~; aqueous solution of another component) and any other adjuvants. After being .~i 20 agitated for a suitable period~of time, e.g., three minutes to one hour, at the aforementioned elevated temperature, the aqueous mixture is forced through restricted orifices, for example of cross-sectional areas equivalent to a -~
circular passage of 1 to 5 mm. in diameter, at a high pressure, e.g., 200 to ; ;
~ 1,000 lbs./sq. in., so as to result in production of a spray of aqueous `.1~ droplets. The droplets are allowed to fall through a spray tower, wherein they are contacted with a countercurrent flow of hot air, which dries them.
The drying air entering the spray drying tower will be of an initial temper-ature in the range of~about 200 to 500C. and at exit from ~he tower will ;
osually be at a temperature of about 110 to 200C. The drying operation will .. ~ ,j ;~
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be controlled, as by d~ying gas temperatures and tower throughput ra~es, to make detergent beads o a desired moisture content9 generally 1n the range of about 2 to 6%. It is then preferred for the spray dried particles to be screened and sized, to o'btain product particles in the 6 to 140 mesh range.
The particulate product may then be charged to a tumbling drum for addition by spraying of anyadditional nonionic detergent or other nonionic surface 'i active agent which may be added to increase detergency and other product pro~ -perties, and for the addition of adjuvants, such as perfumes and other mat-.
erials which are heat-sensiti~e, which are therefore desira'bly added after ` 10 spray drying.

When tested by standard wash tests and in practical automatic laun- ''' `~

dry tests, it is found that the present particulate products are excellent " ~

'' detergents, effectively washlng out soils of the various types normally en- ~ ' .; ..
countered, such as particulate (cl~y) soils, sebum soils, greasy and carbon-' aceous soils, from cotton and synthetic organic fibers and 'fabrics. The im-inodicarboxylate builders function better in this respect than all of the .'i .
presently acceptable builder subst~tutes for pentasodium tripolyphosphate and ~ trisodium nitrilotriacetate that have been tried. Mbreover the detersive, `~
'',: ~ ': , soil-suspending and whitening effects oE the present detergent compositions ' 20 are substantially equivalent to those obtained with phosphate-based detergent .
"1 formulations, even at much higher levels of phosphate contents (with compen-sating lower levels of synthetic organic detergent content). The present ~1~ products are compet1tive in price with other commercial detergent formulat1ons.

Additionally, they do not contain excessive quan'cities of potentially toxic ~"l or harmfu1 constituents.

The following examples illustrate the invention but do not limit it.

Unless otherwise indicated, all parts are by weight and temperatures are in . -.-.
i C.
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13XAMPL~ 1 ~- Higher alkyl poly-lower alkoxylate nonionic 6 surface active agent-detergent Linear tridecyl benzene sulfonate, sodium salt 12.2 (90% acti~e ingredient, balance mainly N 2 4) 2_Hydroxyeth~l iminodiacetic acid disodium salt 28.3 `l 153% solids content aqueous solution of a pH of 9.4) Aqueous sodium silicate solution (Na20:SiO2 = 1:2; 34.1 solids content = 44%) Sodium carboxymethyl cellulose 0.59 ~ :

` (85% active ingredient) .~ Sodium sulfate, anhydrous 36 ..
., ~
Water . 7 Neodol 45 11, a trademark for a liquid higher alkyl polyethoxylate, made : :
by Shell Ghemical Company, wherein the higher alkyl group is of an average of :: :
14 to 15 carbon atoms and the molar ratio of ethoxy to higher alkyl group is about 11.

Three parts of the sodium carbonate which are dissolved in about four parts of the water, utilizing a separate mixer, are admixed with the aqueous solution of 2-hydroxyethyl iminodiacetic acid disodium salt so as to raise the pH thereof to 12.7. The sodium silicate solution is added to a detergent composition crutcher and heated to about 6~C. The hydroxyethyl .~iminodiacetate solution at the elevated pH is admixed with the silicate sol~
:. . . ~ .
ution, by addition to the crutcher which already contains the silicate solu~
tion. Subsequently the rest of the carbonate is added, followed by the linear tridecyl benzene sulfona~e, as a 56% solids aqueous solution, with sodium : ~:

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sulfate impurity, two parts of the nonionic detergent and the sodium sulfate.
The sodium carboxymethyl cellulose, dissol~ed in the remaining water then is admixed with the rest of the crutcher mix. After mixing in the crutcher for a period of five minutes after addition of all materials, the crutcher mix, which is free of precipitates and gels, is pumped by a Triplex(trademark) pump at a pressure of 600 lbs./sq. in. through a plurality o~ spray nozzles~
each of which has an orifice of about one millimeter diameter, into the top of a countercurrent spray drying tower wherein the falling droplets of det~
, .:
; ergent composition are dried in heated drying air passing upwardl~ through the tower. The drying air has an initial temperature of about 400C. and a final temperature of about 130 C. The resultant product, having a moisture 1 , ~
content of about 4% and in the form of spray dried globules, is ~screened and :` sized so that the particles thereof pass through a No. 6 sieve, United States Standard Sieve Series but rest on a No. 140 mesh screen The particles are ;~ then charged to a tumbling drum and sprayed with the remaining two-thirds, e.g., 4 parts of the liquid nonionic detergent and with about 0.2% perfwne ., .
based on the weight of the particulate detergent composition. In addition to ~ the perfume, in some runs there are admixed with the particulate detergent - composition further conventional adjuvants, e.g., fluorescent brightener and/or a preservative. The amounts of these additives, together with the perfume, total about 2% of the detergent composition.
; In use it is found that the above composition is comparable in de-tergency with high phosphate compositions containing 11 to 25% of the afore~
mentioned anionîc detergent and 33 to 45% of pentasodium tripolyphosphate.
:,~, Yet~ the present product is non-eutrophying and does not contain any in-organic phosphates or unusual quantities of detergents~ surface ac~ive agents, ~`"7, builders or anti-redeposition agents Utilizing standard concentrations for detergents in automatio wash~ -;~ ~ng machines~ i~e.~ about 0~15% of spray dried detergent, the product is ~-, ., , t ,.

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tested and fo~d to be of acceptable to superior washing ability in hot and cold water, in hard and soft water and when tested against varying types of soils from clay soil to phospholipid or sebum soils, as compared to a com-mercially available phosphate-containing detergentJ
EXAMPL~ ?.
Parts by Wei~t ~' Nonionic surface active agent-detergent 2 (as in Example 1) ~'.
Higher alkyl polyethoxy sulfate, 8 anionic surface active agent Linea~ tridecyl benzene sulfonate, 12.2 sodium salt solution (as in Example 1) 2-Hydroxyethyl iminodiacetic acid, 22.6 -disodium salt (as in Example 1) ;
~ Aqueous sodium silicate 27.3 '',!~ (as in Example 1) ;
i Sodium carbonate, anhydrous 10 ., .
Sodium carboxymethyl cellulose 0.59 (as in Example lj :,~
Sodium sulfate 42 ~ `

j~ Water 7 ~
.:, .
~ Neodol 25-3S, a trademark for a higher alkyl polyethoxy sulfate~ sodium ~ ~ ;

;;~ salt, made by Shell Chemical Company, wherein the higher aIkyl group is of an ` ~
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- average of 12 to 15 carbon atoms and the molar ratio of ethoxy to higher aIkyl group is about 3, in 50% aqueous solution with 80~o active ingredient on a solids basis~ ~
'~', ',. '.
The above components are admixed, spray dried, screened and sized to a particulate detergent substantially as described in Example 1 with the exception that all of the nonionic surface active agent is charged to the ~ 13 -~.~57S1~3 `

, crutcher prior to spray drying, that is the post-spray dry:ing addition of a portion of the nonionic surface ~c~ive agent is omitted. The resultant ;~
, particulate detergent composition is substantially equivalent in detersive `
effect to the product of Example 1. Additionally the present product is more .
resistant to caking on storage than is the product of Example 1 .
EXA~PIE 3 Parts by Weight Nonionic surface active agent 2 ~ .
(as in Example 1) 10Linear tridecyl benzene sulfonate, 12~2 .
.
: sodium salt (as.. in Example 1) ~ ;

2-Hydroxyethyl iminodiacetic acid, 47.2 disodium salt solution (as in Example 1) :

Aqueous sodium silicate solution ~as in Example 1) 27.3 ~ :Sodium carbonate, anhydrous : 10 ~` Sodium carboxymethyl cellulose 0.59 ~ .-:(as:in Example 1) : Sodium sulfate, anhydrous :~ 33 ` ~-~
:;i ~., : , Water ~ 7 :: 20 The above components are admixed, spray dried, screened and sized ,i .~ : ~
~ to a particulate detergent composition ha~ing a particle si~e in the 6 to .. . . .
140 mesh range, substantially as described in Example 2.
The resultant particulate detergent composition is substantially .
equivalent in detersive effect to~the product of Examples 1 and 2. Addition-:,'1 :
ally, it is of acceptable flow and storage propertles. ~
-~ Substantially similar excellent results are obtained in the foregoing ~ :
xsmples 1-3 if a portion, e.g., 1/10, 1/2 or ~3, or all of the sodium sul- .^
fate is replaced by sodium chloride.

EXA~ U3 4 When, in the foregoing examples~ the proportions of components are varied ~ithin the ranges previously recited, e.g., to within 10% of the ex-tremes of the various ranges given, when the pH of the iminodicarboxylate is at 12.7 or 13~4 initially and when the other mentioned components are employ-ed, e~g., 2-hydroxyethyl iminodipropionate, the non-phosphate products made are good detergents of acceptable flow and non-caking properties, which are suitable replacements for the phosphate-containing previous standards of ex~
cellent detersi~e activities~ The detergents and surface active components , . .:
in such formulations are those of average alkyl and lower alkoxy carbon atoms ;;;~
cont0nts of the ranges recited. ~hen the use of phosphates is permissible their inclusion in any of the foregoing formulas in quantities equal to 2 to 20%, preferably 5 to 12% replacement of filler salt or iminodicarboxylate (preferably pentasodium tripolyphosphate is used)results in a further im-proved product. In many cases detergency is improved, as well as caking re-~ sistance.

`` A number of experiments is conducted in which formulas within the s present invention are compared for caking properties, on storage. Formulas tested include A~ 11% sodium linear tridecyl benzene sulfonate, 6% Neodol ~ -(trademark) 45-11, 15% disodium hydrox~ethyl iminodiacetate and 15% of sodium silicate~ with the balance being sodium sulfate, moisture, anti-redeposition agent and other adjuvants, as previously described, and B) an improved com- ~ -position containing 11% of the l;near tridecyl benzene sulfonate, 4% of ;` Neodol(trademark) 25-3S, 2% of Neodol(trademark) 45~ 12% of the iminodi-acetate and 12% of the silicate (Na20:SiO2 = 1:2~0). ~ ;
The products are made by spray drying, although the latter formula may also be made by post-spraying the nonionic detergent onto the surfaces of ~, the spray dried particles of the rest of the formula. After production of the ': `' ' :-, : , . ~

-~S7g;~L8 finished detergent composition, with particle sizes like those pre~iously mentioned, they are subJected to aging tests at 100 F. and 80% relative hum-idity in both barrier and barrier-less car~ons for 3 to 6 days. After the ends of the test times the carton contents are examined and it is found that of the detergents of the latter formula, wherein the proporti~ns of iminodi-acetate and nonionic detergent are diminished, exhibit lesser tendencies to caking than products of the other formulation. This is in part attributable to the presence of the ethoxylate sulfate detergent, too. However, the de-scribed improvements are noted also when, in other formulas, the iminodiace-lo tate content is increased by about 60% and the ethoxylated anionic detergent is omitted from the formulation The resul~s described are improved further ` ~ when at least 10% of sodium carbonate is present and extra improvements re-.
sult when this proportion is increased to 15%. Similar improvements in the non-tacky properties of the detergent are obtainable when post-sprayings of nonionic detergent are effected on both "experimental" and "control" products.
The~invention has been described with respect to speclfic examples ;~
l~ and illustrations thereof but is not to be limited to these because it is `;~ evldent that one of~skill m the~art, with the present specification before himg will be able to utilize equi~alents and substitutes, while still beirg within the concept and scope of the invention.

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Claims (12)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A particulate heavy duty laundry detergent composition which comprises about 5 to 30 parts of synthetic organic anionic detergent selected from the group consisting of organic anionic sulfonate, sulfate, phosphate and phosphonate detergents, about 1.5 to 7.5 parts of a synthetic organic nonionic detergent or surface active agent, about 5 to 30 parts of an alkali metal silicate in which the ratio of alkali metal oxide, M20, to silica is from 1:1.6 to 1:3, about 4 to 20 parts of an alkali metal carbonate, about 9 to 30 parts of a hydroxyalkyl iminodicarboxylate builder salt of the following formula wherein R is a 2 to 4 carbon alkyl group, R1 and R2 are hydrogen or C1 to C3 alkyl with the carbons of R1 + R3 no more than 3, and M is 3 alkali metal, ammonium or substituted ammonium, and about 0.25 to 3 parts of an organic gum anti-redeposition agent, with the sum of the parts being from about 35 to 100 and with the proviso that when the amount of synthetic organic nonionic detergent or surface active agent present in the composition is less than about 2.5 parts there are present at least about 20 parts of the builder salt and/or there are present about 2 to 10 parts of a higher alkyl poly-lower alkoxy alkanol sulfate.

2. A detergent composition according to claim 1 which also contains about 5 to 50 parts of sulfate and about 2 to 6 parts of moisture, with the sum of the parts being from about 42 to 150.

3. A detergent composition according to claim 2 wherein the synthetic organic anionic detergent is an organic sulfonate detergent, the alkali metal silicate is a sodium silicate of Na2O:SiO2 ratio of 1:1.6 to 1:3 and the alkali metal hydroxyalkyl iminodicarboxylate builder salt is a dialkali metal hydroxy-lower alkyl iminodiacetate or dipropionate, with the total of mater-ials in the composition other than said anionic detergent, alkali metal silicate, builder salt or other material recited in claim 1 being less than 20% of the composition.

4. A detergent composition according to claim 3 which comprises about 5 to 30% of an organic sulfonate detergent, about 1.5 to 7.5% of a synthetic organic nonionic detergent, about 5 to 30% of sodium silicate of ratio of 1:16 to 1:3, about 4 to 20% of alkali metal carbonate, about 9 to 30% of dialkali metal hydroxy-lower alkyl iminodiacetate builder salt, about 0.25 to 3% of synthetic organic gum anti-redeposition agent, about 5 to 50%
of alkali metal sulfate as filler salt and about 2 to 6% of moisture with the total amount of adjutant materials in the composition being limited to about 20% and with the proviso that when the concentration of the nonionic surface active agent in the composition is less than about 2.5% there is present at least about 23% of the builder salt and/or there is present about 3 to 10%
of the higher alkyl poly-lower alkoxy alkanol sulfate salt.

5. A detergent composition according to claim 4 in which the sulfonate detergent is a linear higher alkyl benzene sulfonate, with the higher alkyl group being of 12 to 18 carbon atoms, the synthetic organic nonionic deter-gent is a higher alkyl polyethoxyethanol wherein the higher alkyl group is of 12 to 18 carbon atoms with the molar ratio of ethoxy to higher alkyl group being in the range of 7 to 20, the sodium silicate is of a Na20:SiO2 ratio of 1:2 to 1:2.4, the dialkali metal hydroxy-lower alkyl iminodiacetate is a dialkali metal hydroxyethyl iminodiacetate, the synthetic organic gum anti-redeposition agent is an alkali metal carboxymethyl cellulose, the total of any adjuvant materials in the composition is limited to 10% and the alkyl poly-lower alkoxy lower alkanol sulfate salt is an alkali metal higher alkyl polyethoxy sulfate wherein the alkyl group contains 12 to 15 carbon atoms and the molar ratio of the ethoxy to the higher alkyl groups is in the range of 2 to 7.

6. A detergent composition according to claim 5\ in which the linear higher alkyl benzene sulfonate is sodium linear alkyl benzene sulfonate where-in the higher alkyl group is of 12 to 15 carbon atoms, the synthetic organic nonionic surface active agent is a higher alkyl polyethoxy ethanol wherein the number of carbon atoms in the higher alkyl group averages from 12 to 15, and the molar ratio of ethoxy to higher alkyl group is from 9 to 13, the alkali metal carbonate is sodium carbonate, the iminodiacetate is disodium 2-hydroxyethyl iminodiacetate, the alkali metal carboxymethyl cellulose is sodium carboxymethyl cellulose, the filler salt is sodium sulfate and the alkali metal of the alkali metal higher alkyl polyethoxy sulfate is sodium.

7. A detergent composition according to claim 6 which comprises: about 8 to 15% of sodium linear higher alkyl benzene sulfonate wherein the higher alkyl group is of 12 to 18 carbon atoms; about 2.5 to 7.5% of the higher alkyl polyethoxy ethanol wherein the higher alkyl group is of an average of 14 to 15 carbon atoms and the molar ratio of ethoxy to higher alkyl groups is from 9 to 13; about 12 to 20% of sodium silicate; about 8 to 15% of sodium carbonate;
about 10 to 20% of disodium 2-hydroxyethyl iminodiacetate; about 0.3 to 2%
of sodium carboxymethyl cellulose; and about 30 to 50% of sodium sulfate.

8. A detergent composition according to claim 7, in spray dried bead form of particle sizes in the 6 to 140 mesh range, which comprises: about 11%
of sodium linear tridecyl benzene sulfonate; about 6% of higher alkyl poly-ethoxy ethanol in which the higher alkyl group is of an average of 14 to 15 carbon atoms and the molar ratio of ethoxy to higher alkyl group is about 11; about 15% of sodium silicate of Na20:SiO2 ratio of about 1:2, about 10%
sodium carbonate; about 15% of disodium 2-hydroxyethyl iminodiacetate; about 0.6% of sodium carboxymethyl cellulose; about 36% of sodium sulfate; about 4% moisture and about 2% of adjuvant materials, with the particles being spray dried globules produced from crutcher mixes of said materials with the ex-ception that about 2/3 of the higher alkyl polyethoxy ethanol and the perfume are post sprayed onto the spray dried particles so that the surfaces of the beads contain a higher proportion of said higher alkyl polyethoxy ethanol and perfume than the interiors thereof.

9. A detergent composition according to claim 6 which comprises: about 8 to 15% of sodium linear higher alkyl benzene sulfonate wherein the higher alkyl group is of 12 to 18 carbon atoms; about 1.5 to 2.5% of the higher alkyl polyethoxy ethanol wherein the higher alkyl group is of an average of 14 to 15 carbon atoms and the molar ratio of ethoxy to higher alkyl groups is from 9 to 13; about 3.5 to 4.5% of a sodium higher alkyl polyethoxy sul-fate wherein the higher alkyl is of an average of 12 to 15 carbon atoms and the molar ratio of ethoxy to higher alkyl groups is from 2 to 7; about 8 to 20% of sodium silicate; about 8 to 15% of sodium carbonate; about 9 to 17% of disodium 2-hydroxy iminodiacetate; about 0.3 to 2% of sodium carboxymethyl cellulose; about 30 to 50% of sodium sulfate; and about 1 to 10% of adjuvant materials, including fluorescent brighteners, preservative and perfume.

10. A detergent composition according to claim 99 in spray dried bead form of particle sizes in the 6 to 140 mesh range, which comprises: about 11% of sodium linear tridecyl benzene sulfonate; about 2% of higher alkyl polyethoxyethanol in which the higher alkyl group is of an average of 14 to 15 carbon atoms and the molar ratio of ethoxy to higher alkyl groups is a-bout 11; about 4% of sodium higher alkyl polyethoxy sulfate in which the higher alkyl group is of an average of 12 to 15 carbon atoms and the molar ra-tio of ethoxy to higher alkyl groups is about 3; about 12% of sodium silicate of Na20:SiO2 ratio of about 1:2; about 10% of sodium carbonate; about 12% of disodium 2-hydroxyethyl iminodiacetate; about 0.5% of sodium carboxymethyl cellulose, about 42% of sodium sulfate; about 0.5% of moisture and about 2% of adjuvant materials.

11. A detergent composition according to claim 6 which comprises: about 8 to 15% of sodium linear higher alkyl benzene sulfonate wherein the higher alkyl group is of 12 to 18 carbon atoms; about 1.5 to 2.5% of higher alkyl polyethoxy ethanol in which the higher alkyl group is of an average of 14 to 15 carbon atoms and the molar ratio of ethoxy to higher alkyl groups is 9 to 13; about 8 to 20% of sodium silicate; about 8 to 15% of sodium carbonate;
about 20 to 30% of disodium 2-hydroxyethyl iminodiacetate; about 0.3 to 1% of sodium carboxymethyl cellulose; about 30 to 50% of sodium sulfate; and about 1 to 10% of adjuvant materials, including fluorescent brighteners preserva-tive and perfume.

12. A detergent composition according to claim 11, in spray dried bead form of particles in the 6 to 140 mesh range, which comprises: about 10% of sodium linear tridecyl benzene sulfonate; about 2% of higher alkyl polyethoxy ethanol in which the higher alkyl is of an average of 14 to 15 carbon atoms and the molar ratio of ethoxy to higher alkyl groups is about 11; about 12%
of sodium silicate of Na20:SiO2 ratio of about 1:2; about 10% of sodium carbonate; about 25% of disodium 2-hydroxyethyl iminodiacetate; about 0.5%
of sodium carboxymethyl cellulose; about 33% of sodium sulfate; and about 2%
of adjuvant materials.

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