PH26964A - Soil releasing detergent - Google Patents

Description

This invention relates to detergent compositions which are useful for washing synthetic organic polyme- ric fibrous materials, such as polyesters, and which impart soil releasing properties to such washed mate- rials. More particuly, the 4nvention relates to such compositions in particulate form which contain as the soil releasing agent therein a copolymer of polyethyl- ene terephthalate and polyoxyethylene terephthalate, a nonionic detergent, an alakaline builder which can de- crease the soil releasing effectiveness of the s0il re- : leasing material when the centact with such material during storagey and a stabilizing proportion of poly- vinyl pyrrolidone (PVF) to help to maintain the soil releasing characteristics of the soil releasing copoly- mer despite the presence of the alkaline builder.

In U.S, Patent applications S.N's 396,637 (Gior- dano & Cjallella) and 396,761 (Gsordano & Ciallella) there were described built nonionic synthetic organic detergent compositions which contain a preferred type of soil releasing copolymer of polyethylene terephtha- i 1ate and polyoxyethylene terephthalate. When polyester or polyester-cotton blend fabrics and items made from such fabrice have been washed in the described products such fabrics acquire soil releasing properties so that when they are subsequently soiled with a lipophilic ma-

: terial, such as dirty motor oil, such oil can more readily be removed during washing of the fabric, , whether such washing is with the invented detergent composition or with a conventional laundry deter-

gent product.

In U.S. patent application S.N, 396, 762 (Wixon) it is taught that the mentioned type of soil releasing polymer of polyethylene terephtha- late and polyoxyethylene terephthalate can he dissolved

} in molten nonionic detergent and the solution can then be sprayed onto absorbent spray dried nwoads of builder ’ material.

The described compositions and the method for the manufacture thereof are useful but in some cases, as when the builder is alkaline, its presence can adverse- ly affect the soil releasing capability of the soil feleas-

ing polymer in the mentioned detergent compositions, gfter storage at room temperatures and especially after storage at elevated temperatures, This appears:to be due to the sensitivity of the soil release promoting polymer to hy- drolysis.

It has now been discovered that when PVP, pre-~ ferably of a certain type (molecular weight range), is pre- sent in the detergent composition in intimate contact with the soil releasing polymer, sometimes coating it, the soil releasing capability of the detergent composition contain- ing such polymer is significantly improved after storage,

compared to a similar product in which no PVP is present,

- ho

In accordance with the present invention a parti- culate built nonionic synthetic organic detergent com- position for washing synthetic organic polymeric fibrous materials and imparting soil release properties to them comprises a detersive proportion of a nonionic synthe- tic organic detergent, a building proportion of a water soluble alkaline bnilder for such detergent, no soil re-— leasing proportion of a soil releasing polymer of poly- ra - ethylene terephthalate and polyoxyethylene terephthajate and a stabilizing proportion of polyvinyl pyrrolidone : (rvP) for stabilizing the soil releasing polymer in the presence of the alkaline builder.

Freferably, the water soluble alkaline builder salt will be sodium tripoly- phosphate (normally pentasodium tripolyphosphate); which may be accompanied by sodium silicate, a certain type of polymer of polyethylene terephthalate and polyoxyethyl- ene terephthalate will be used, the nonionic detergent will be a condensation product of higher fatty alcohol and ethylene oxide, and the PVP will be water soluble and within a given molecular weight range.

Limited proport- jons of moisture and adjuvants may also be present in the invented compositions.

Also within the invention are processes for the manufacture of the described stabilized soil releasing detergent compositions, and methods for washing materials with such compositions.

Although various nonionic detergents of satis- oo factory physical characteristics may be utilized, in- cluding condensation products of ethylene oxide and propylene oxide with each other and with hydroxyl-con- taining bases, such as nonyl phenol and oxo-type alco- hols, for best results it is highly preferred that the nonionic detergent be a condensation product of ethyl- } ene oxide and higher fatty alcohol. In such products the higher fatty alcohol is of 10 to 20 carbon atoms, preferably 12 to 15 or 16 carbon atoms, and the nonio- ) nic detergent contain from about 3 to 20 or 30 ethyl- ene oxide groups per mole, preferably from 4 to 11 or 12. Mogt preferably, the nonionic detergent will be one in which the higher fatty alcohol is of about 12 to 15 or 12 to 1" carbon atoms and which contains from 6 or 7 to 11 moles of ethylene oxide. Among auch gdeter- gents is Alfonic R 1214-60C, sold by the Conoco Divi- sion of E.I. DuPont de Nemours, Ince, and Neodols R 23- 6,6 and 25-7, available frou Shell Sherdcenl Jompanye

Among their especially attractive properties, in addi- . tion to good detergency with respect to oily and greasy soil deposits on goods to be washed, and excellent com- ’ patibility with the present polymeric release agents, is a comparatively low melting point, which is still appre- . . 25 ciably above room temperature, so that they may be sprayed onto hase beads as a liquid which solidifies quiekly after it has penetrated into the beads (m.p. usually being in 40 to 55°C. range).

Various builders and combinations thercef which are effective to complement the washing action of the nonionic synthetic organic detergent (a) and to im- prove such action include both water soluble and water } insoluble builders. Of the water soluble builders, which preferably are employed in this inventicn, and are preferably in mixture, both inorganic and organic builders may be useful. Among the preferred inorganic water soluble builders those that are best include va- rious phosphates, preferably polyphosphates, such as the tripolyphosphates and pyrophosphates, more specifi- cally the sodium tripolyphosphates and sodium pyrophos- phates, e.g., pentasodium tripolyphosphate, tetrasodium pyrophosphate; sodium carbonate, preferably as soda ashj and sodium silicate; and mixtures thereof. The sodium silicate is normally of Na,0:510, ratio within the range of 1:1,6 to 1:3, preferably 1:2.0 to 1:2.4 or 1:2.8, e.

Ces 1:2.4. Of the water soluble inorganic builder salts the phosphate will usually be employed in greater propor- tion, with a lesser proportion of sodium silicate, the carbonate may be employed will bicarbonate and often with a lesser proportion of sodium silicate, and the silicate . . _ og v 7 ' will rarely be used alone. Tnstrad of individunl poly- phosphates being utilized it will sometimes be prefer- red to employ mixtures of sodium pyrophosphate and sodium tripolyphosphate in proportions within the range of 1:10 to 10:1, preferably 1:5 to 5:1. Of course, it is recog- nized that changes in phosphate chemical structure may occur during crutching and spray drying, so that the finnl product may differ somewhat from the components charged to the crutcher.

It will be noted that the water soluble builders ’ mentioned are alkaline materials and usually the alkalini- ty resulting will be such that a 1% aqueous solution of the detergent compesition will be of a pH in the range of ’ about 8.5 to 12, e.g., 10.0. This alkalinity helps the detergent composition to remove various types of soil from laundry and to hold it in suspension but it also has a ne- gative effect; tending to cause degradation of the soil re- leasing polymer employed and thus interfering with such po- lymer imparting soil releasing properties to washed mater- : 20 ials

Because polyesters, whether employed alone or in blends with cotton, are lipophilic, they tend to attract and hold lipophilic soils, which consequently may still be present on laundry after washing, rinsing and drying .

Therefore, especially with respect to polyester fibers,

the imparting of soil release properties to the fibers : of materials being washed is important so that the lanndering thereof may be effective. Consequently, es~ pecially because in recent years many articles of cloth- ing and other washable household goods have been made from polyesters or polyester blends it is important that maximum soil release properties be imparted to such mate- rial. Tyerefore, any tendency of the soil releasing poly- mer being employed to degrade should be counteracted. Thus, the discovery that a certain material (PVP), stabilizes ; the soil releasing polymer employed in this invention is an important one.

The soil release promoting polymer which is an es- gential component of the compositions of this invention is a polymer of polyethylene terephthalate and polyoxy- ethylene terephthalate which is dispersible in water and is depositable from wash water containing ponionjc deter- gent and builder for the nonionic detergent, onto synthetic organic polymeric fibrous materials, especially polyesters and polyester blends, so as to impart soil release proper- ties to them, while maintaining them comfortable to a wear- er of clothing made from such materials and not preventing or significantly inhibiting vapor transmission through such clothing. Such polyesters have also been found to possess anti-redeposition properties and often assist in removing stains from substrates. They tend to maintain soil, espncinlly oily or greasy soil, dispersed in wash water during washing and rinsing, so thnt it is not redeposited on the laundry. Useful such products are copolymers of ethylene glycol or other suitahle source . of ethylene oxide moiety, polyoxyethylene glycol and terephthalate acid of suitable source of the terephtha- lic moiety. Tye copolymers may also be considered to be condensation products of polyethylene terephthalate, which pay cometimes be feferred to as an ethylene tere- - phthalate polymer, and polyoxyethylene terephthalate.

While the terephthalic moiety is preferred as the sole dibasic acid moiety in the polymer it is within the in- vention to utilize relatively small proportions of iso- phthalic acid and/or orthophthalic acid( and sometimes other basic acids, too) to modify the properties of the polymer. However, the proportions of such acids or sources of suph supplemental moieties charged to the reaction mix, and the corresponding proportions in the final polymer will normally be less than 10% each of the total phthalic moiet- jes present, and preferably will he leas than "0 thereof,

Th~ molecular weight of the ypeluwer wit) Ve dre the range of about 15,000 to 50,000, preferably being about re 19,000 to 43,000, more preferably being about 19,000 to 25,000, e.g., about 22,000. Such molecular weights are weight average molecular weights, as distinguished from number average molecular weights, which, in the case of the present polymers, are often lower. In the polymers utilized the polyoxyethylene will be of a molecular weight in the range of about 1,000 to 10,000, preferably about 2,500 to 5,000, more prefer. ably 3,000 to 4,000, e.g., ahout 3,400, I, such poly- mers the molar ratio of polyethylene terephthalate to } polyoxyethylene terephthalate units (considering £ ocu_cH {0 and A (CoH un) +O) 2° 2 27 2m as such units) will be within the range of 2:1 to 6:1, highly preferably 5:2 to 5:1, even more preferably 3:1 to 4:1, eug., about 3:1. The proportion of ethylene oxide

CT to phthalic moiety in the polymer will be at least 10:3 and often will be 20:1 or more, preferably being within the range of 20:1 to 30:1 and more preferably being about 22:1. Thus, it is seen that the polymer may be considered as being essentially a modified ethylene oxide polymer, with the phthalic moiety being pnly a minor component thereof, whether calculated on a molar or weight basis.

Tt is considered surprising that with such a small propor- . tion of ethylene tererhthalate or polyethylene terephthalate in the polymer the polymer is sufficiently similar to the polymer of the polyester fiber substrate ( or other polymers to which it is adherent, such as poly- amides) as to be retained thereon during the washing, rinsing and drying operations. Yet, as shown by com- parative experiments and various washing tests in which soil release is measured, the described polymer, in the present detergent compositions, if effective to deposit ) on washed synthetics, especially polyesters, mo as to make them hetter able to be washed fren of oily soil by ) a built nonionic detergent composition or other deter- gent product. It is considered that the polymer's in- creased hydrophilicity, attributable to the large pro- portion of hydrophilic ethylene oxide moieties therein, may be responsible for the excellent soil release proper- ties which it imparts to the material upon which it is de-~ posited, and such may also help it to coact with the built nonionic detergent.

Various literature articles, texts and patents dis- close methods for the manufacture of the present polym- mers, included among which are Journal of Polymer Science, } '

Vol. 3 pages 609-630 (1948); Jgqurnal of Polymer Science,

Pol. 8, pages 1-22 (1951); Fibers From Synthetic Polymers, “by Hill, published by Elsevier Publishing Gompany, New York,

New York, (1953), at pages 320-322; British patents 1,088,984 and1,119,367; and U.S. patents 3,557,039; 3,893,929; and 3,959,230 Although suitable methods for making the instant polymers are described in such references it is considered that pone of them discloses the parti- } 5 cular polymers which are utilized in the present invent- jon (put such are disclosed in the three patent appli- cations previously mentioned, and some are available com- mercially) and none discloses the present detergent com- ~ positions. Such polymers may be considered as having becn ol 10 randomly constructed from polyethylene terephthalate and polyoxyethylene terephthalate moieties, guch as may be ob- tained by reacting polyethylene terephthalate (e.g.y spin- : ning grade) and polyoxyethylene terephthalate or reacting the ethylene glycol, polyoxyethylene glycol and acid( or methyl ester) precursors thereof. Yet, it is also within . the invention to utilize more ordered copolymers, such as those made by reacting components of predetermined or known chain lengths or molecular weights, so as to produce what might pe referred to as block copolymers or non-random copo- lymers. Graft polymers may also be practicable,

The described materials are available from various sources, the products of one of which will be described in more detail here, Useful copolymers for the manufacture of the detergent compositions of this invention are marketed by Alkaril Chemicals, Inc., and commercial products of such company that have been gnccesrfully employed to produce sn-

satisfactory soil release promoting detergent compo-

Co sitions are those gold by them under the trademakts Al- karil CJ and Alkaril CF, formerly Quaker NJ and Qua- ker JCF. Froducts available from them in limited quangi- ties, designated hy them ns 2056-30R and 205A_11, have also been found to be acceptable. Tpe QCJ product, normally sup- plied as an aqueous dispersion, is also available as an essentinlly dry golid (0CF). ‘hen it 30 anhydrous or low ) in moisture content (preferrably less than 2% moisture), it looks like a light brown wax, and in it the molar ratio of ethylene oxide to phthalic moisty is nbout 22:1. Ip a 1AY dispersion in water the viscosity at 100%., 55 about 96 centistokes. The 205A-l1 polymer is like a hard, light brown wax and in it the hydrophile: hydrophobe ratio is about 16 to 1, with the viscosity boing nhout 265 centis- tokes. The 2056-34B polymer appears to*he a hard hrown wax, with a hydrophile# hydrophobe ratio of about 10.9:1 and its viscosity, under the same conditions as previously mentioned is about 255 centistokes. The higher the molecular weight of the polymer the lower the hygrophile: hydropheobe molar . ratio may be therein and still result is satisfactory goil release promotion by tha invented detergent compositions.

The QCJ and QCF polymers have melting points (by different jal thermal analysis) of about 50 to 60°C. (put minor pro- portions of such products will remain in solid state at tem-

peratures up to 100%), a carboxyl analysis of 5 to 30 equivalents/10° grams and a pH of 6 to 8 in distilled water at 5% concentration. Tye molecnlar weights (weight average) are in the range of 20,000 to 25,000 and the ethylene terephthalate; polyoxyethylene terephthalate units molar ratio is about 74:26. All theee of the men- tioned trademarked products are water soluble or substan- : tially water soluble in warm or hot water (at ho to 2070 ) } for at least are readily dispersable, and may he character- ized as of high molecular weights, over 15,000 generally in the range of 19,000 to 43,000, often preferably 10,000 to 25,000, e.g., about 22,000{ In the present application when proportions of the soil release polymer are given such are on the basis of the polymer, including any insolubles there- in (which can be less active 48 soil release agents). Ideal- ly, the release polymer employed will he 100% water soluble.

Normally, for "solution" application to materials or for solution addition to a detergent composition in wash water, the copolymers of this invention may be employed in aqueous dispersion. In such dispersions a surface active agent may be present to assist in maintaining the disper- sion uniform. Only small proportions of such surface active agent will be employed, if any. Normally, the concentration of the polymer in the aqueous medium will be about 5 to 25% on a composition basis, preferably 10 to 20%, e.g., 16%, and such is the concentration at which the mentioned com- mercial products are normally supplied when a liquid form is desired.

While liquid dispersions or solvent solutions of the polymer may be employed for direct ad- dition of the polymer to the medium in which the fabrics ’ are to be treated, when the polymer is to be incorporat- ed in a particulate detergent composition it will be pre- ferable for it to be in solid form, preferably as an an- hydrous particulate solid of a particle size like that of the other detergent composition components.

Alternatively, it may be finely divided and powdered onto spray dried beads of the other components.

In more preferred methods of incorporation in a detergent composition the polymer may be dissolved in nonionic detergent and sprayed onto base bends or may be prilled with carriers and mixed yith the hase beads, It yas been found that the polymer should : not be added to an aqueous crutcher mix containing anionie detergent and/or builder salt and it should not be brought into contact with water soluble builder salt in the presence of mo#sture, especially at an elevated temperature.

Agord- ingly, to make free flowing particulateproduct, nromally the polymer will be essentially dry or very low in moisture con- tent.

T, use of such a product also allows for the manu- facture of base beads at normal moisture content without the moisture content thereof being increased objectionably

’ by post-spraying of an aqueous dispersion of the poly- mer onto the beads. ‘ The PVP employed has heen found eflective in sta- bilizing the described soil releasing polymers in the : presence of alkaline builder, and is especinlly effect- jve in the presence of sodium tripolyphosphate, which may be accompanied by sodium silicate. Such PVE usual- 1y has a molecular weight in the range of about 5,000 to 200,000, preferably 10,000 to 160,000 and most prefer- ably about 10,000 to 50,000, However, in some cases PVF with a molecular weight greater than 200,000 has been found useful, although not as effective as the componnds within the ranges given. Thus, PVP with a moleculnr weight of about 360,000 exhibits some stabiliging effect but normally will be uneconomic in view of the superior results obtained with the lower molecular weights pro- ducts. A preferred source of PVE is GAF Corporation, New

York, N.Y. and the preferred commercial products of that company are marketed under the designations K-15 (MW. = 10,000), K-30 (M.W. = 140,000) and K-60(H.W,= 160,000).

Their K-90 product has a molecular weight of about 360, 000. All the described products are water soluble and additionally, are soluble in molten nonionic detergent of the type preferably employed in accordance with this invention } 25 (a condensation product of a higher fatty alcohol with ethyl-

ene oxide). While PVP is highly preferred it is consi- dered that other polylactam, such as polyvinyl oxazoli- dinone, may also ne useful in at Jenst partial replace- ment of the PVE, Polyacrylamide and related amides pos-~ sess some gtabilizing properties too, but they sre in- ferior to PVP in this respect.

Various suitable adjuvants may pe present in the invented detergent compositions, such as enzyme powder, which phelps to decompose stains And other soils so as to promote their removal, thereby coacting with the soil release aiding polymer; perfumes; fluorescentsbrighteners; . colorants (gyes and water dispersible pigments, such as ultramarine blue) bactericides; fungicides; and flow pro- moting gents. Some of these materials may be added in the ’ crutcher so that they are parts of the base beads, and some of them will be posteadded. Inorganic fillers, such as so- dium sulfate and sodium chloride, may be utilized but pre- ferably the proportions thereof will be limited, one rea- son for this being pecause it has peen found that sodium sulfate tends to react adversely with the present poly_ mers. Of the enzymes, both proteolytic and amylolytic en- zymes may be employed, such as those sold under the trade re names Alcalase, manufactured by Novo Industri, A/S, and

Maxazyme, both of which are alkaline proteases(substilisin),

In the invented detergent compositions the proportion of synthetic organic nonienic detergent will ne from about 5 to 30%, preferably 10 to 25% and more prefer- ably 15 or 18 to 22%, e.g., about 20 or 21%. Tye to- ‘ tal proportion of water soluble alkaline huilder will be from about 30 to 80%, preferably from ho to 75%, and more preferably 45 to 70%. When the builder are sodium tripolyphosphate and sodium silicate, as is preferrad, the proportions thereeof are preferably about 30 to 70% and 3 to 15%, respectively, more preferably

LO to 65% and 5 to 13%, e.g. 54% and 10%. The propor- tion of soil release promoting polymer will be from about 0.5 to 20%, preferably 1 to 10%, more preferably 1 to 5% and most preferably 2 to 5 Hy eR. %%h. The moisture content of the product will usunlly be from 1 to 20%, preferably 3 to 15% and more preferably 5 to 12%

Co fefey 9%. Individual adjuvants preferably constitute no more than 10% of the composition, more preferably being limited to 5% and often to 2 or 3%, with the total of ad- juvants desirably not exceeding 25%, preferably heing li- mited to 15% and more preferably being held to 5 or 10% of the composition. Of course, mixtures of individual compo- . nents of the invented compositions and of the adjuvants for them may often be desirably employed, and such are intend- ed to be included when a single type .f component is men- tioned. Enzyme powder, when present, will usually be at a concentration in the range of 0.5 to 3%, preferably 1 to 2%. Such enzyme powder is commercially available as a mixture of active enzyme and carrier material, e.g.,

Maxazyme 375.

Tne detergent compositions, whether previously manufactured and stored before use, or made immediately prior to use, may be employed in dilute aqueous solution (or dispersion) in wash water to wash all-gynthetic ma- terials, including polyesters; cotton.synthetic blends, including cotton-polyester blends; cottons; nylons; and mixtures of such materials. Normally the dry weight of materials being washed will be from 2 to 15 or 20% of the weight of the aqueous washing medium, and preferably 5 ’ to 10% thereof. The wash will be conducted with agita- tion over a period from 5 minutes to 1/2 hour or one . hour, often from 10 to 20 minutes, and after washing the materials will be rinsed, usually with several rinses, and will be dried, as in an automatic laundry dryer. The i was water will usually be at a temperature of 10 to 95%. , preferably 15 to 60°c, or 20 to 50°C., and more prefer- ably 40 to 50°C. , and the concentration of the detergent composition or the equivalent components (if geparately added to the wash water) will be from 0.05 to 1%, prefer- ably from 0.05 to 0.15%, e.g., 0.06% or 0.13%. The de- tergent compositions have a bulk density in the range of

0.2 or O.4 to 0.9 g./cc., preferably 0.6 to 0.9 g./cc eegey 0.65 g./cc. and sash detergents of such prefer- ed bulk desnsity are normally employed at a concentra- tion of about 1/4 cup (or about "0 grams) per wash, with the wash tub usually containing about 17 gallons (u.s.) of water for top loading machines and amhout 7 to 8 gal- lons for front loaders. When a "European" type of wash- ing machine is employed, wherein higher concentrations ys | of detergent composition are utilized, with lesser amounts of water, and which machines usually operate at higher washing temperatures, it may be preferable to lower the washing temperature for hest depositing of the polymer on the washed materials. The upper portion of the proad range of detergent compocition concentrations previous- ly given pay be considered as appropriate for European washing conditions whereas the corresponding interme- diate and lower parts are for "American " type front : loading and top loading washers and washing conditicns, often with the concentration for the front loading ma- chines heing lower than that for the top loaders.

The proportions of the individual active compo- nents of the present compositions in the wash water will normally be from 0.001 to 0.14% of nonionic deter- gent, 0.006 to 0."0% of builder, 0.0001 to 0.10% of soil releasing agent and 0.00002 to 0.5% of PVP. Preferably such proportions will be from 0.003 to 0.02%, 0.02 to

Co 0.05%, 0.0003 to 0.01%, and 0.00006 to 0.006%, res- pectively. When sodium tripolyphosphate and sodium silicate are present in the wash water the normal per- centages of the significant components of the present compositions that will be in wash water are 0.0006 to 0.040% of nonionic detergent, 0.017 to 0.12% of sodium tripolyphosphate, 0.002 to 0.023% of sodium silicate, _ 0.0008 to 0.009% of soil releasing polymer and 0.00013 to 0.004% of PVP, with more preferred panges being 0.009 to 0.013%, 0.024 to 0.039%, 0.003 to 0.008%, 0.001 to 0.00%%, and 0.0002 to 0.001%, respectively.

The base beads which may be employed in making the compositions of the invention are preferably spray dried from an aqueous crutcher mix which normally will contain from ahout 40 to about 70 or 75% of solids, preferably 50 to 65% thereof, with the balance peing water, preferably dionized water, gs previously described (but city water may also be employed). The crutcher mix is preferably made by sequentially adding various components thereof in a manner which will result in the most miscible, readily pumpable and non-getting slurry for spray drying. The or- der of addition of the materials may be varied, depending on the circumstances, but it is megt desirable when '"geBt- able" crutcher mixes are employed to add the silicate solu-

tion (4f any) last, and if not last, at least after the addition of any gel- or "freeze'!'-preveunting com-

bination of materials or processing aids, such as citric acid and magnesium sulfate, Normally it is preferable for all of almost all of the water to be added to the crutcher first, preferably at about the ' processing temperature, after which the processing aids (if present) ang other stable minor components, jnclud- ing pigment and fluorescent brightener, if present, are added, followed by most of the builder (5g), including phosphate builder, and silicate builder.

Usually during such additions each component will be mixed in thoroughly before addition of the next component but method of addi-

i tion may be varied, depending on the circumstances, so as to allow go-additions when such gre feasible, Sometimes component additions may be in two or more parts and some- times different components may be pre-mixed before addi- tion, to speed the mixing process.

Normally, mixing speed and power will be increased as the materials are added.

| The temperature of the agueous medium in the crutcher will usually be about room temperature or elevated, normally being in the 20 to 80°c, tange, preferably from 30 to 75 or 80°C., and more preferably 40 to 70 or 80°C.

Heating the crutcher medium may promote solution of the water soluble salts of the mix and thereby increase miscibility but the heating operation. When effected in the crutcher, can slow productior ,rates. Tepperatures higher than 80°c. (and sometimes those higher than 70°C.) will often be avoided because of the possibility of decomposition of one or more of possible crutcher mix components, e.g., sodium bicarbonate. Also, in some cases lower crugcher temperatures increase the upper limits of crutcher so- lids contents, probably due to insolubilizing of normal- ly gelling or setting components. Such problems are not usually encountered when the main builder present is a polyphosphate.

Crutcher mixing times to obtain good slurries can vary widely, from as little as five minutes in small crutcher and for slurries of higher moisture contents, to as much as four hours. Te mixing times necded to bring all the crutcher mix components substantially homo- geneously together in one medium may be as little as ten minutes but in some cases can take up to an hour, although 30 minutes is a preferable upper limit. Counting any such initial admixing times, normally crutching periods will he from 15 minutes to two hours, e.g., 20 minutes to one hour, but the crutcher mix should be such as to be mobile, not gelled or set, for at least one hour, preferably for two hours, and more preferably for four hours or longer after . 25 completion of the making of the mix. The present mixes are ' - 2h are preferred for various reasons already mentioned, such as desirable bulk density, uniformity, flowabili- ty, strength and sorption properties, it is within the : invention to employ other equivalent or nearly equiva- lent base beads, such as those which are agrlomerate, mixes, granulates, grinds, prills or chopped filaments.

The nonionic detergent will nsually be at an elevated temperature, such as 40 to 90°c., preferably $0 to 8o°c., 55°C. to assure that, it will be liquid; yet, upon cool~ ing to room temperature it will desirably be solid, often resembling a waxy solid. FHven jf at room temperature the nonionic detergent is slightly tacky, this characteristic does not. necessarily make the final composition poorly } flowing because the detergent penetrates to pelow the bead 18 | surface ( to within the bead). However, waxy detergents are ’ preferred. The nonionic detergent is applied to the moving or tumbling base beads in known manner, as a gpray or as droplets. The enzyme preparation (herein referred to as enzyme, although it is recognized that it includes a car- rier material, too), soil releasing polymer, PVP and any . other powdered adjuvants may be dusted onto or mixed with the builder base particles, and perfume and any other 1li- quids to be post-added may be sprayed on at a suitable point before or after sddition(g) of the powder(g).

The nonionic detergent may be sprayed onto absorbent base builder beads and soil release promoting poly- mer and PVP may be post-added together, with the soil . release polymer being stabilizéd by the FVP against the degrading action of the alkaline builder nase beads.

Such stabilizing effect of the PVP is obtained when the release promoting polymer and the PVP are in contact, preferably when contact of the release polymer and the alkaline builder is also prevented or diminished. However, two par- ticular ways of incorporating the honienic detergent, soil release polymeraand FVE in the product arc highly effect- jve and are preferred, The more preferred method ise by spray drying an aqueous crutcher mix of the alkaline build- er salt to produce dried absorbent particles, dissolving the formula proportions of soil releasing rolymer and FVD in nonionic detergent in liquid state, and spraying or jipap. wise effectively distributing the nonionic detergent solu- tion of the release polymer and PVE onto the surfaces of the alkaline builder beads. In carrying out such a proce- dure it is highly desirable that the nonionic detergent he substantially or essentially anhydrous, normally contain- . ing less than 1%, preferably less than 0.5% and more pre- ferably less than 0.2% of moisture. It is preferred that 7 the nonionic detergent be at a temperature in the range . of 40 to 90°C., more preferably 50 to 80°C., at which the normally solid and waxy detergent will be molten and at which temperature the soil release promoting polymer and the PVP will dissolve in it (in the formula pro- portions}. Also, the base beads will preferably be warmed and are Kept in motion, as in a suitable mixer, such as a rotating longitudinal drum or tube which is inclined slightly, e.g., 5 to 10° from the horizontal.

The spray droplets will preferably br of a size delivered from a typical spray gun, usually being of a diameter in the range of about 0.1 to 1mm. The mentioned spraying and mixing can be effected in times as short as one or two minutes but normally from 5 to 10 minutes may be de- dirable. Surpringly, although the spraying of the lique- fied nonionic detergent onto the base beads brings the soil release polymer into close contact with such beads and the alkaline builder salts of which they are composed, oo apparently due to the presence of the PVF the soil release promoting polymer remains stable on storage, even at some- what elevated temperatures. Comparisons with anther soil release detergent compositions of similar formulas but without the PVP ghow that the experimental formulas are far superior in lasting soil release promoting characteris- tics.

Another preferred method for making a detergent com- position of this invention includes dissolving the PVP in a liquid medium, such as water, suitable alcohol, e.g.y me-

thanol, or suitable volatile chlorinated organic sol- vent, such as methylene chloride. Desirable concentra- tions of the PVP in the solvent will normally be with- in the range of 5 to 2%, with higher concentrations pre- ferred when solvent removal jis more of a problem, as when water is being used. Tye solvent solution of FVP is then applied to particulate soil release promoting poly- mer, with the rate of application being such as to apply the desired formula proportion of IVE tc the seil raleor ogo agent. Thus, for example, when it is desired that the fi- nal detergent composition contain 3% of release polymer and 0.5% of PVP, enough FVP solution will be sprayed or otherwise applied to the surfaces of the particles of the . release polymer to produce an intermediate product contain- ing about 86% of release polymer and about 14% of Y'VP. The particle sizes of the release polymer will preferably be within the same range as the desired sizes of the nonio- nic detergent-bnilder particles of the final detergent com- position But other sizes of particles may also he employed, although they will not he as advantageous and may geparate out to some extent from the deterpent-builder particles.

Such detergent-builder particles. will be made by spraying the formula proportion of molten nonionic detergent onto the absorbent builder salt pase beads in a manner like tpat pre- viously described. Next, the two types of particles are blended together and the formula is ready for use. The detergent composition resulting is one in which the re- lease promoting polymer is protected by the PVF frem the degrading action of the alkaline builder salt. Agdi- . 5 tionally, the presence of the nonionic deterrent on the builder salt, covering substantial portions of the sur- faces thereof, further helps to prevent detrimental interactions. pe In the applications of IVP to the base beads (with nonionic detergent and release polymer) and to the release . polymer particles the PVP protects the release polymer } from that alkaline builder and furthermore, improves the ” product otherwise. IVP possesses useful anti-redeposition properties and has been observed to promote stain removal from laundry. In the present compositions it aids in soil release, especially at room temperatures or thereabout, to an extent which is greater than that attributable to stabi- : lization of the soil release promoting polymer. A coating of the PVP helps to protect the detergent composition against the effects eof at atmospheric mositure. Yet, PVP is readily soluble in the wash water, leading to quick dissolving and dispersion of the detergent components. Although many other products have been tested, none has been found to give th e very desirable effects of PVP, not even other water soluble polymeric amides.

The following examples illustrate the invention but do not limit it. Unless otherwise indicated, all parts

Co are by weight and all temperatures are in °c.

EXAMPLE I

Tercent

Pentasodium tripolyphosphnte 5h, 3

Neodol 23-6.5 (condensation product of 20.7 approximately 6,5 moles of ethyl- ene oxide and a higher fatty alcohol . averaging between 1? and 13 carbon atoms per mole)

Sodium silicate (Na,0:S4i0, = 1:2.h 9.58

Moisture 9.05

Soil release promoting polymer (a copolymer of polyethylene terephthalate and pnlyoxy- ethylene terephthalate of a molecular weight of about 22,000 wherein the polyoxyethylene is of a molecular weight of about 3,400, the molar ratio of polyethylene terephthalate to polyoxy- ethylene terephthalate units is about 3:1 and the proportion of ethylene oxide to phthalic moiety in the polymer is about 22:1, sold by Alkaril i Chemicals, I,c. as Alakaril QCF)

Proeteolgtic enzyme (Maxazyme) 1.32

Fluorescent brightener (Tinopal 5BM) 1.26

Polyvinyl pyrrolidone (GAF Corporation K-15 FVP 0.50

__Persent having a molecular weight of about 10,000)

Perfume 0.20

Dye (Bjue, Mix No. 5) 0.05%

Dye (Polar Brilliant Bjue) 0.04 100.00

A particulate built nonionic synthetic organic detergent composition of the above formula, which is useful for washing synthetic organic polymeric fibrous materiales, sucl aa those of polyrsters eve edvortore cotton blends and ingariing soil rolwepe properties to them, is made by the following method. First, base beads of the tripolyphosphate and silicate are made by dispersing the tripolyphosphate, as a finely divided powder, in water and adding to it the formula proportion (9.58%) of anhydrous silicate as a h7.5% solids solution, with the solids concentration of the crutcher mix made being about 55%. The water employed is deionized but some- times city water will be substituted, provding that its hardness is less than 300 pe.p.m. aS calcium carbonate. Fre- ferably, fluorescent prightener and any colorants, such as the blue dyes, which are sufficiently crutcher, are added to the crutcher, too. The crutcher mix is maintained at a temperature in the range of about 60 to 720%¢ and mixing is continuous. Tye mixing, including addition and dropping, which are both conducted while mixing, normally takes about

: 20 minutes to an pour but may be undertaken for longer periods, up to four hours or more, because the phos- phate-gilicate~dye-brightener dispersion-sclution does not tend to set in the crutcher.

After sufficient mixing to obtain a snhstantially uniform slurry, in which the flnorescent brightener and . dyes will often preferably be present, during which time } some moisture may be jost by evaporation, and may be re- plenished, if desired, the mix is dropped from the crutcher to a pump, which pymps it at a pressure of about 21 kg./sq. cm. into the top of a countercurrent spray tower wherein the initial drying temperature is about 130°C, and the final air temperature is about 105°¢., The base beads re- sulting are of a bulk density of about 0.5 r./cc, when ’ 15 cooled after manufacture, and nre of particle sizes in the range of no's 10 to 100, U.S. Sieve Series. Tey may be screened to such range or to a particulate product having fewer smaller particles, c.g., 10 to 60 sieve. Tne moist- ure content of the product is about 12.1%. The base beads are free flowing (generally with about an 30% flow rate), non-tacky, satisfactorily porous, yet firm on the surfaces thereof and are capable of readily absorbing significantly proportions of liquid nonionic detergent (and dissolved

QCF and PVP) without becoming objectionably tacky.

After cooling of the spray dried base beads they are screened so that substantially all over 95% and often over 98%) are within the range of No'g 10 to 100 sieve, U.S. Sieve Series, and gre sprayed with a solu- "tion of QCP and PVP in anhydrous monionic detergent,in final product formula proportion. . Thus, 0.5 part of the PVP and 3 parts of the PVP and 3 parts of the ACF are dissolved in 20.7 parts of Neodol 23-6.5, which is essentially anhydrous and which is at a temperature of about 7.%, and is sprayed onto tumbling pase builder bead surfaces, preferably while the beads are being mixed in a tumbling drum, which may be a longitudinal drum or tube inclined to the horizontal at about 80, The spray droplets are largely of particle sizes in the 0,1 to 1 mm. range and the spraying operation will be guch as to result in a throughout time in the sprayer-mixer of about 10 to 20 minutes, with the enzyme and perfume being applied in the mixer after the nonionic detergent containing PVP and (CF. Tye resulting detergent gompo-~ sition particles, when cooled, are of n hulk gensity of ahout 0.65 g./cc. Tue product is attarative and regular in appearance, and is free flowing and non-dusting.

The detergent compositions described ahove are excellent heavy duty 1aundry detergents and are agpecial- ly useful for washing household laundry in automatic wnsh- ing machines and at the same time imparting soil release - 3h characterisctics,to them. When employed at a tempera- ture of about 45° to 50°C. and a concentration of about 0.05 to 0.15%, e.g., 0.06%, in a 17 gallon capa- city washer, in the washing of normal loads of 100%

S polyester and £5%h polyester - 35% cotton fabrics in home laundry or commercial washing machines, whether of the top loading or front loading types, or at higher tempera- tures nnd concentratiens in furopean type washing machines, the compositions perform satisfactorily, ns would be ex- pected from a knowledge of thier components, with respect to usual washing effect characteristics, but additionally they significantly promote soil release from such materials.

They are also satisfactory for washing nylons, cottons, . acetates and blends of fibrous materinls and they promote soil release from such materials too, although not to the same great extent as with the polyesters. Tests of the washing and scil release actions of the compositions =a

General Rjectric Company top loading washing machine or a Terg-O=Tgometer test washer is used, the water tempera— ture is about h5°c, and the water contains a total of ’ about 200 p.p.m. hardness as CaCl, of mixed calcium and magnesium ions. The washing test times are all about ten 7 to fifteen pinutes and the laundry : water ratio is about 1:20, by weight, Items are rinsed twice automatically and then are dried in an antomatic laundry dryer or other suit-

ble drying means.

The presence of the PVP with the present soil release promoting polymer significantly stabilizes the release polymer so that with the human eye and by reflectometer readings it is evident that better soil relense on washing results vhen a detergent com- position comprising the release polymer and PVP is stored for 2 to !t weeks at elevated temperature and , is then ysed to treat polyesters nnd polyester-cotton blends, compared to the same product from which the

PVP was omitted (not incerporated in the nonionic gde- tergent with (CF) put which pas stored and used in the same manner. For hetter gtabilization of the polyeséer soil release promoter the ratio of PVF to soil release agent should be within the range of 1:15 to 1:2 or 1:1, k preferably 1:10 to 1:3, e.g., 1:5 or 3:4, Tue coil re- . lease promoting is more significantly on repeated laun- derings, usually up to five 1aunderings of the washed materials, with the present compositions (or with equi- valents wash water solutions).

In addition to users of the present products noting the improved soil release in washing normal leads of laundry containing articles soiled with oils or greases, comparative tests wherein dirty motor oil is applied to gwatches of polyester and polyester-cotton blend materials . Los -

agter such swatches have been washed in either the in- vented compositions or contrel compositions ( which are the game as those of the invention but without PVP) ghow improved soil release prmoting for the invented products when both such and the control have been stored , at elevated temperature, e.g., four weeks at 45°C. be- fore being used to wash-treat the swatches. Ip such tests . skilled observers not the improvement in s0il removal by washing with a composition of the invention or a control, respectively, after first treating and then oil soiling, and such conclusions are gonfirmed by reflectometer checks of the wnshed materials. Similar results are obtained when the polyester test materials are washed with the experi- mental and control detergents, are soiled with dry motor oil and are then washed with a commercinl detergent, such as a phosphate built andonic detergent of the FAB type.

When variations of the above formulas are made,chang- ing the proportions of soil release polymer and PVP plus or minus 20% and plus or minus 50%, aimilar results are obtainable but with the greater proportions of PVP (and release polymer) the soil release effects are better aft- er storage due to improved stability of the QCF, Simi- . larly, when such changes are made in the builder, nonio- nic detergent (to Neodols 25-7 and 23-3) and enzyme com- ponents, keeping the formulas within the ranges previously given, useful products result, of improved soil re- lease characteristics despite storage, providing PVF as present. Also, when the PVF is changed to K-30 or . K-60 excellent stabilizing of the QCF results, but with K-90 the stability is less. The described re- sults are also obtainable when other polyethylene terephthalate-polyoxyethylene terepth alate copolymers 7 are employed provided that the molecular weights and ’ ) ratios are within the ranges recited in the specifica- tion. :

EXAMPLE 2 when the compositions of Example 1 are made by spray drying the base beads, having them absorb a spray of heated nonionic detergent (at 55°¢.), coating QCF particles in the 10 to 100 sieve range with PVF (K-15) to produce particles still in that range, and blending the two particulate intermediate compositions, in the appro- priate proportions, a stabilized soil release promoting detergent results. The PVP solution used js at a concen- tration of about 15% in methanol, water or methylene chlo- ride, and it is applied so as to deposit the formula pro- portion of PVP on the RCF. Instead of using an inclined drum mixer a fluid bed dryer (Automatic Co.) is employed for the coating of the QCF particles with PVP, and for evaporation of the solvent.

Co Although the described coating method is yse- : ful and the products resulting are of bulk density, detergency and soil release promoting chavncteristics for liphophilic soils that are comparable to those of the product of Example 1, and are of other good physical characteristics like those of Example 1, it is preferred to employ the absorption method described in . i Example 1 hecause it does not require any exlra equip- ment or any additional process steps other than a mixing tank for the dissolving of the {CF and PVE in the nonio- nic detergent. Also, solvemt recovery means are not peed- ed and vater evaporation doen not have to be effected.

EXAMPLE 3

Results like those given in Examples 1 and 2 are also obtainable by use of other compositions, the com- ponents of which may be separately added to the wash wa- ter at the normal washing temperatures and concentrations given. While it is preferred to utilize the compositions described, containing nonionic detergent, alkaline build- er salt, goil release imparting polyester and PVP or other suitable polylactam or polyamide, because the components thereof are in desired proportions and are ready to use, additions of different partial mixtures of comporamts or individual components may be made to the wash water, and excellent soil release characteristics will be acquired by the polyesters and polyester-cotton blend materials be- - Za «= ing washed ( And treated), Of course , when the JCF or similar soil release agent is separate from alkaline builder salt there will be little or no need to stabi- lize the release agent. Still, even in such cases ex- cellent imparting of soil release characteristics is obtainable, employing the same washing conditions as previously mentioned in Example 1 and 2, and the TFVFP contributes stain removal and soil dispersion proper- ties which further help to improve the washing charac- teristics of the detergent composition solution,

Instead of employing particulate detergent compo- sitions liquid may be utilized, such as more concentrat- : ed aqueous solutions, such as those of 5 to 25 parts solids, in water or in water and alcoholic solvent, and these are vertically useful for pre-treating before washing any portions in clothong items that sre likely to be host soil- ed by oily materials. Such use is to prvent subsequent hard-to-remove soiling and is particularly appropriate for ghirt ccllars and cuffs. work gloves and aprons, for example. The presence of the PVP is considered to help stabilize such liquid preparations but if they are made shortly before intended the such stabilization may not be necessary .

Many variations of the above formulas can be made utilizing other nonionic detergents, other builders and - Lo ~ builder combinations, other soil release promoting polymers and.other types of FVE, such as have been described in the specifigation. Also, the various proportions may be changed within the ranges aiven, and useful effects of the desired types will result. It is surprising that the present compositions are sO affective and of acceptable and practical stability despite storage at elevated tem- peratures because PVE jg extremely water soluble and would not he gxpreted to tinsulate' the soil release agent from atmospheric moisture, which, in the presence of water so- 1uble alkaline salt, would he expected to cause degradation . of the release agent. Also, when nonionic detergemt contain- ing dissolved release agent is deposited on base beads of . alkaline builder galt it would be expected that the wring- ing into intimate contact of the alkaline material and the

QCF (or QCF) would promote degradation of the release agent, even on the presence of PVP. Such does not happen, as p28 been reported above. Yet, because of the water solubility of the nonionic detergent and its hydrophilicity it would not be expected that it would restrict contact of the alka- 1ine puilder salt and the soil release promoter. In short the present jnvention, in which PVP stabilizers polyester soil rclease promoting material aginst alkeline hydroly- sis and degradation is unexpected and revresents an import- ant advance in the detergent arte. : I 1

The invention has been described with respect to various examples and illustrations thereof but is not to be considered as limited to these becnhuse one of skill in the art, with the present specification hefore him, will be able to utilize gubstitutes and equivalents without departing from the invention. - ho -

Claims (3)

CLAIM: } -

1. A process for manufacturing a particulate built nonionic synthetic organic detergent composition for yashing synthetic organic polymeric fibrous mate- rials and imparting soil release properties to them, which composition comprises a nonionic aynthetic orga- nic detergent, a water soluble alkaline builder for guch detergent, a soil releasing polymer of polyethylene tereph- thalate and polyoxyethylene terephthalate, and PVP for stabilizing the soil releasing polymer in the presence of the alkaline builder, which comprises the steps of spray drying an aqueous crutcher mix of the alkaline builder to produce dried particles thereof, and applying to such spray dried puilder particles the nonionic deter- . 15 gent in liquid state containing the soil releasing poly- 7 mer and the PVP, so that the nonionic detergent, soil re- leasing polymer and PVP are absorbed by the spray dried ‘ builder particles, said nonionic deterpent heing a con- densation product of ethylene oxide and a higher fatty alcohol of 10 to 20 carbon atoms, the builder nweing a salt selected from the group consisting of sodium tripolyphos- phate, sodium silicate, sodium pyrophosphate and sodium carbonate, and mixtures thereof, the soil releasing poly- mer being a polymer of polyethylene terephthalate and poly- 29 oxyethylene terephthalate of a molecular yeight in the range - hz of about 1,000 to 10,000 with the molar ratio of ethyl- ene tercphthalate to polyoxyethylene terephthalate units being in the range of about 2:1 to 6:1, and the PVF be- ing water soluble and of a molecular yeight in the range of about 5,000 to 200,000, the proportions of nonionic de- tergent, builder salt, soil releasing polymer and PVE pe- ing in the ranges of about 5 to 30%, 30 to RO%, 0.5 to - 20% and 0.1 to 10%, respectively, and the soil releasing polymer and PVP being dissolved in the nonionic detergent, which is essentially anhydrous, such solution being at a temperature in the range of 40 to 90°C., and it being sprayed onto the builder salt particles.

2. A process according to claim 1, wherein the no- nionic detergent is a condensation product of a higher fat- ty alcohol of 12 to 16 carbon atoms with 3 to 20 moles of ethylene oxide per mole of higher fatty alcohol, the puilder is a sodium tripdlyphosphate with sodium silicate of Na, 0:540, ratio in the range of 1:2.0 to 1:2.9, the soil releasing polymer is of a molecular weight in the pange of about 19, 000 to 43,000, the polyoxyethylene of the polyoxyethylene ” terephthalate thereof is of a molecular weight in the range of about 2,500 to 5,000, the molar ratio of ethylene tereph- thalate to polyoxyethylene terephthalate units thereof is within the range of 5:2 to 5:1 and the molar ratio of ethyl- ene oxide to phthalic moiety therein is at least 20:1, and - Lh

* the PVP is of a molecular weight in the range of about 10,000 to 160,000, and which composition contains moist- ure, and the contnnts of such nonionic detergent, phos- phate silicate, soil releasing polymer, PVP and moist- ure of 10 to 25% 30 to 70%, 3 to 15%, 1 to 10%, 0.2 to 5% and 3 to 15%, respectively, the spray dried builder particles nd the composition particles are sizes within the range of Mo's 10 to 100, U.S.

Sieve series, and are of bulk densities within the range of 0.4 to 0.9 g./CCuy and the solution of soil releasing polymer and PVP in substantially anhydrous liquid atate nonionic detergent ' js at a temperature in the range of 50 to 80%, when sprayed onto and absorbed by the builder particles and such particles are being kept in motien when such spray- ] ing is being effected.

3, A process for manufac turing a particulate built nonionic synthetic organic detergent composition for wash~ ing synthetic organic polymeric fibrous materials and im- parting soil release properties to them, which composition comprises ~ nonionic synthetic organic detergént, © unter goluble alkaline builder for such detergent, a soil re- leasing polymer of polyethylene terephthalate and poly- oxyethylene terephthalate, and TVP for stabilizing the soil releasing polymer jn the presence of the alkaline builder, which comprises the steps of spray drying an - h5 = aqueous crutcher mix of the alkaline builder to pro- duce dried particles thereof, applying to such spray dried builder particles the nonionic detergent in liquid state so that it is absorbed by the spray dried builder particles, applying FVP in a liquid medium to particles of the soil releasing polymer and mixing such resulting particles with the builder particles contain- ing nonionic detergent, said nonionic detergent being a condensation product of ethylene oxide and a higher fatty alcohol of 10 to 20 carbon atoms, the builder being a salt selected from the group consisting of sodium tri- polyphosphate, sodium silicate, sodium pyrophosphate and sodium carbonate, and mixtures thereof, the soil releas- ing polymer being Aa polymer of polyethylene terephthalate and polyoxyethylene terephthalate of a molecular weight in the range of about 15,000 to 50,000 wherein the polyoxXy- ethylene of the polyoxyethylene terephthalate is of a mole- cular weight in the range of about 1,000 to 10,000 with the molar patio of ethylene terephthalate to polyoxyethylene terephthalate units being in the range of about 2:1 to 6:1, . and the PVP being water soluble and of a molecular weight in the range of about 5,000 to 200,000, the proportions of nonionic detergent, builder salt, soil releasing polymer and PVP being in the ranges of about 5 to 30%, 30 to 80%

0.5 to 20% and 0.5 to 10%, respectively, the nonionic dew - U6 ~ tergent being esmentially anhydrous and is of a tem- perature in the range of BO to 90%c. , the PVP being in solution in a solvent medium when it is applied to the particles of soil releasing polymer and such s0l-

vent is removed from the FVP treated soil peleasing }

polymer before blending of such polymer with the build- ; er particles containing absorbed nonionic detergent. te A process according to claim 3, wherein the nonionic detergent is A condensation product of a hirh-

er fatty alcohol of 12 to 16 carbon atoms with 3 to 20 moles of ethylene oxide per mole of higher fatty alcohol, the builder is sodium tripolyphosphate with godium sili- cate of Na,0:810, ratio in the range of 1:2.0 to 1:2.8, the soil releasing polymer is of a molecular weight in the range of about 19,000 to 43,000, the polyoxyethylene of the polyoxyethylene terephthalate thereof is of a mole- cular weight in the range of about 2,500 to 5,000, the molecular ratio of ethylene tetepthalate units thereof is within the range of 5:2 to 5:1 and the molar ratio of ethylene oxide to phthalic moiety therein is at jeast 20:1, and the PVP is of a molecular weight in the range of about 10,000 to 160,000, and which composition con- tains moisture, and the contents of such nonionic deter- gent, phosphate, silicate, soil releasing polymer, FVP and moisture in the composition are within the ranges of

- L4h7 -

Ce a 26964 10 to 29%, 30 to 70%, 3 to 15%, 1 to I0%, 0.2 to 5% and 3 to 15%, respectively, the spray dried builder ) particles and the detergent composition particles are of sizes within the range of No's 16 to 100, U.S. Sieve series, and are of bulk densities within the range of

0.4 to 0.9 g./cc., the nonionic detergent is at a tem : perature in the range of 50 to 80°. and is substantial- 1y anhydrous when it is applied in the liquid state to the spray builder particles, and the applications of such liquid state nonionic detergent to the builder par- ticles and of the PVP in a solvent medium in which it is dissolved to the soil releasing polymer particles are by spraying of such liquids onto the gurfaces of such par- ticles while the particles are being Kept in motion." ROBERT JOHN STELTENKAMP ¢ } LORETTA KATHLEEN CIALLELLA NICHAEL ALLAN COLLINS . Inventors : ~ hg -