CA1208855A - Fabric conditioning agents and compositions - Google Patents

Abstract

ABSTRACT

Through-the-wash fabric conditioning compositions are disclosed especially for use with machine dryers that minimize adverse reactions taking place in the wash that otherwise ad-versely affect the performance of the separate detergent and fabric conditioning ingredients. This is accomplished by utilizing salts of certain tertiary amines and carboxylic acids in the form of 0.05 to 2 mm. nodules that pass virtually unchanged through the wash and rinse; become entangled in the fabrics when spun or wrung out; and then melt, spread, and condition the fabrics when heated in a dryer.

Description

~2~8~55 ~.
s E~RIC CONDITIONING AGENTS AND COMPOSITIONS
.,~
1-, Nabil George Kardouche ~. Philip Joseph Vincent Giardina , TECHNICAL FIELD

~i 5 Thisinvention relates to novel fabric conditioning ayents and compositions which are especialiy useful in a laundry process that involves washing followed by drying in a machine dryer at elevated temperatures. Fabric cleaning and/or stain ', removal is provided in the washer; and fabric conditioning, i.e.l0 softening and destaticization, is provided principally in the d ryer .
.,, ~ BACKGROUND ART
, , .
There have been a great many disclosures of compo-sitions which, when used separately, provide detergency, stain , 15 rernovai and fabric conditioning benefits. By fabric conditioning:- is meant improving softness, i . e. making its "handle" or texture ; more smooth, pliable and fluffy to the touch; and also reducing static "cling" in the fabrics, i.e. destaticizing. Perhaps the most ~; common fabric conditioners known in the art are cationic com-,~~ 20 pounds, especially quaternary ammonium and imidazolinium salts.
These compounds are ~widely r,1arketed for home use in the form of liquid emulsions. They must be added to the home laundry in the rinse cycle, not the wash, because cationic fabric conditioners : interact with anionic substances present in the wash, such as -` 25 anionic surfactants and builder saits, thereby rendering both ~' relatively ineffective. A commercial ~abric conciitioner of this type is DOWNY (~) The Procter ~ Gamble Company.
. Another type of compound known for this purpose comprises certain tertiary amines, as disclosed in Kenyon, Cana-30 dian Patent no. 1,087,352 issued October 14, 1980. Clay as a fabric ,conditioning ingredient is disclosed in Storm et al, U.S.
Patent No. 4,062,647 issued [)ecember 13, 1977.

, t ~2~3!35~ - -.
-Certain compositions are already known th3t provide ~ ......................................................... .
fabrics with a detergency treatment in a washer combined with a degree of fabric conditioning treatment in a subsequent machine dryer. Compositions of this kind are known in the art as :5 îhrough-the-wash fabric comditioners, and are convenient to use in that they do not require the use of a second product in the rinse cycle or in the dryer to accomplish the fabric conditioning objective. Baskerville, Jr. and Schiro, disclose in U.S. patent 3,936,537 issued on February 7~ 10 3, 1976 a composition of this type wherein the fabric conditioning agents are quaternary ammonium compounds.
The compositions of Baskerville et al comprise a r!~ixture of two components: one component is granular and consists of surfactant, cletergency builder, and other conventional detergent :-15 adjuncts; while the other component consists of particles ranging in size from 10 to 500 microns which comprise an intimate mixture of a quaternary ammonium compound and a dispersion inhibitor in the form of a solid organic r aterial which can be a paraffin wax, alcohol, aliphatic carboxylic acid, or an estcr or polyethoxylate ~o thereof which has a solubility in water of 50 ppm. max. at 25GC, :~ancl has a softening point in the range of 100 to 200F (about 38 to 93 C.).
A cornmercial cleaning/conditioning product which has utilked the teachings of Baskerville, Jr. et al is BOLD-3 (~) The 25 Procter ~ Gamble Company.
Through-the-wash compositions utilizing a mixture of tertiary amines and clay as fabric conditioner are disclosed in Crisp et al , European Patent Publication no. 0 ,û1 1,340 published May 28, 1980.
6attrell, in U.5. Patent no. 4,292,035 issued September 29, 1981, prepared through-the-wash compositions whercin fabric softening was accomplished by a complex of clay with ccrtain nitrogen containing organic compounds defined as primary, secon-s~ dary and tertiary ar;lines and their water soluble or water dis-35 pers;ble salts and organic quaternary ammoniur~, phosphonium and sulfonium compounds. The water soluble or water dispersable :"

.--J ' l1~

~2~

saits that were eY~emplified ~Nere those hzving, as their anion, ' ~ hydroxide, chloride, bromide, sulfate or methosulfate. An -~ example of salts of this kind was primary tallow amine hydro--' chloride.
. 5 Another means of providing fabric conditioning was ;C disclosed in Gaiser, U.S. Patent no. 3,442,692 issued May 6, 1969, as an article of man-Jfacture comprising a fabric c,onditioning .~ composition in conjunction with a clispensing means for use in a rnachine dryer. Preferred articles had the fabric conditioning 10 composition releasably affixed to an absorbent substrate, such as a nonwoven tissue, in the form of an impregnate or coating of q cationic fabric conditioning agent. The use of ccrtain polyols, ,~ especially sorbitan csters, as auxiliary fabric conditioning agents ~ in products of this kind is disclosed in Zaki et al, U . 5 . Patent . . .
,~ 15 4, 022, 938 issued 1~,2y 1 O, 1977 . A commercial product that has o utilized the teachings of Gaiser ana Z21ci et al is BOUNCE (~
The Procter ~ Gamble Company.
.~ Fabric conditioning articles of the Gaiser type whereinthe fabric conditioning composition was comprised of certain amine salts are disclosed by l~ardouche in U.~. P3tent 4,2~7,155 issued ,,Y, December 2, 1980, This patent ; alluded to the possibility of adding these amine salts to the wash , cycle or to the rinse cycle of a typical washing operation, and apparently envisaged~a softening process taking place during the one or the other of those tv o processes, respectively.
Clear distinctions between arnines, amides, amine salts, quaternary ammonium salts, and other classes of nitrogen-con-- taining chemical compounds appear in every textbook of organic cheraistry. Fieser and Fieser in Organic Chemistry, 2nd Ed., Heath, Boston U.S.A. 11~50) point out a number of such distinc-tions in chapter 10 beginning at page 220. Amine salts are characterized as typically odorless, nonvolatile solids, even though the amines from which they are derived are odoriferous gases or liquids. The salts are ionic in nature in the solid state.
35 and possess characteristically sharp melting points which are .~ higher than those of the corresponding amines. Low molecular ..
!

~2~85S

.,, 3 . weight amine salts are readily soluble in water and exist in the ; solution in ionized condition.

SUMMARIZED DlSCLOSlJRE OF THE I~VEi~lTlON

One embodiment of this invention is a salt of a tertiary 5 amine and a carboxylic acid in the novel form of discrcte nodules.
These nodules have been found suitable for marketing as a fabric ; conditioning agent to be added to a laundry wash liquor at the beginning of the cycle, along with a conventional detergent product. The particle size of these amine salt nodules is from 10 about O . 05 to about 2 mm ., and the melting point is preferably from about 35 to about 115 C.
-- The tertiary amine used to prepare the amine salt of this invention has the formula ' P'2 wherein R1, R2 and R are each, Independently, saturated or -~ unsaturated and wherein R1 is a long chain aliphatic group hav-ing from 12 to 22 carbon atoms and R2 and R3 are the same or - different from each other and are selected from the group con-20 sisting of aliphatic groups containing from 1 to 22 carbon atoms, ,i hydroxyalkyl groups of the formula -R40H wherein R4 is an alkylene group having from 1 'to 3 carbon atoms, and alkyl ether groups having the formula R5o(cnH2no)m- wherein R5 is hydro-gen or an alkyl or alkenyl group having from 1 to 20 carbon 25 atoms, n is 2 or 3, and rn is from 1 to 20.
The carboxylic acid used to prepare the amine salt of this invention has the formula R6 ~ C - OH

30 wherein R6 is hydrogen, or an alkyl, alkenyl, aryl, alkaryl or aralkyl group having 1 to 22 carbon atoms, or a substituted .,, i:~

i~

~iLZ~ 55 alkyl, alkenyl, aryl, aikaryl, or aralkyl group having from 1 to : 22 carbon aton s wherein the substituents are selected from the group consisting of halogen, carboxyl, or hydroxyl.
The amine salt is formed by reacting the amine and the 5 carboxylic acid together to form a melt, which is then chilled in a manner that produces discrete nodules. SLJitable nodulizing processes are prilling, flalcing on a chill roll, and cooling in a scraped wall heat exchanger followed by extruding.
A second embodiment of this invention is a fabric 10 conditioning/stain removal composition which comprises a blend of the amine salt nodules described supra with nodules of enzyme, I ~
~~ pero>(y bleach or porphine bleach prepared in a conventional ' manner.
A third er~bodiment of this invention is a through-the-15 wash fabric cleaningifabric conditioning composition which com-prises a blend of the amine salt nodules described supra with , detergent granules containing a detergency builder and an ani-onic, nonionic, arnphoteric or zwitterionic surfactant.
' In its processing embodiment, this invention provides a 20 process for conditioning fabrics which comprises the steps of (a) contacting the fabrics with an effective amount of the amine salt defined above in nodule form, and (b) subjecting the fabrics to a temperature within the range from about 40 C. to about 95 C.
The nodules are preferably applied to the fabrics from an aqueous 25 bath, more preferably a laundry wash or rinse liquor; and the fabrics are preferably caused to tumble in relative rlotion to each ,XA~' other while being subjected to the heat.
;'. This invention recognizes that a fabric conditioning - agent for through-the-wash applications should be present in a 30 form that can be added to the wash; survives the wash and rinse processes virtually unscathed; and is entrapped within the fabrics when they are wrung out or spun before drying. Furthermore, the chemical entity of which the fabric conditioning agent is comprised should distribute well on and through the fabrics in a 35 mechanical drying process, and should be intrinsically a compound that eFfectively softens and effectively destaticizes fabrics. The ' 8~Sr;~
~, ~h . .~
t,~ amine salt nodules herein described meet each and every one of ,r, . ~ .
i` these varied criteria exceptionally well.
The amine salts utilized in this invention effectively perform fabric softening and destaticizing functions. It is not 5 represented that amine salts are superior to conventional fabric ; conditioners when used conventionally in the laundry rinse. What ~~~ has not been taught or suggested ;n the prior art is that amine salts, when in the form of discrete nodules, constitute a through-;~ the-wash fabric conditioning ayent that accomplishes results never 10 before achieved. These nodules, when added at the beginning of the wash cycle, pass through the wash and the rinse cycles virtually unaffected by other rlaterials that are present, and in turn do not themselves affect those other materials. This occurs ~ whether the nodules are added, together with a conventional - 15 detergent composition, in the forrn of a separate fabric condi-tioning agent, or as part of a fabric conditioning/stain removal composition; or whether the nodules are added as part of a fabric cleaning/conditioning product which constitutes the sole functional composition in the laundry bath. Accordingly, this invention 20 makes possible for the first time the economic formulation of a , multi-purpose product that cleans as well as comparable single-purpose detergent compositions and conditions fabrics as well as comparable single purpose fabric conditioniny agents. Compro-mises are no longer necessary.
All compositional erhbodiments of this invention are through-the-wash products. They all utilize amine salt nodule technology which provides superior performance to such products than compositions disclosed heretoFore.
The several embodiments of this invention are improve-30 ments over the prior art in a number of different dimensions.
Amine salt nodules, when used as a single purpose product, make possible the convenience of addiny an effective fabric conditioner to the laundry at the same tirne as a conventionai detergent product is added, thereby eliminating the neecl to add anythiny to ;~ 35 the laundry at a different time, e.g. in the rinse or in the dryer .
. ~ ~

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., ~L%~38S5 . . ~

The fabric conditioning/stain removal product of this - invention is a multi-purpose laundry additive that also can be put ''7 into the laundry tub along with the regular laundry detergent product. Laundry additives containing enzyrnes and/or bleach are . 5 widely sold to boost the effectiveness of ordinary detergent `;`-~ products, for example B I Z ~) The Procter ~ Gamble Company .
This invention makes possible an improved laundry additive that , also effectively conditions the fabrics.
A fabric cleaning/conditioning product makes possible a 10 single laundry product that effectively combines the two func-i tions, cleaning and conditioning. It is simple and convenient to A~ use, and does not require adding anything to the laundry at a different time.
Conventional cationic fabric conditioners suffer from a 15 serious disaavantage in through-the-wash products: they are partially soluble under washing conditions. They interact with the anionic substances present in -the laundry liquor, especially thc anionic surfactants often used. This interaction negates the effectiveness of whatever materials are involved therewith. The - ~ 20 result is less effective softening, less effective destaticization, ~- and less effective detergency than would otherwise be obtained.
Previous attempts to protect these materials from contact with the laundry liquor, as disclosed for example in ~askerville et al cited : hereinbefore, have resulted in particles having melting points so 25 low that they are not assured of surviving unscathed through the wash cycle, especially when hot water is used.
~r, In contrast therewith, the amine salts of this invention exist in the form of ion pairs within discrete nodules. Their high and sharp melting points cause them to neither appreciably melt - 30 nor dissolve in the laundry baths at the mildly elevated temper-atures and at the pH's encountered in the wash and in the rinse, respectively. Accordingly, the functions of the fabric condi-tioner, the surfactant, the builder and indeed all other ingredi-ents are accomplished just as though the products were utilized 35 independently.

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, ' DETAILED DESCRIPTION OF THE INVENTIO~J
, r~;
The components of this invention in its several embodi-: ments are described individually as follows:

- The Essential Fabric Conditioning Compounds .
5 The fabric conclitioning compounds essential to this i~ invention are carboxylic acid salts of a tertiary amine which has ;~ at least one long aliphatic chain containing from about 12 to about 22 carbon atoms.
The tertiary ar ine salts are 2 direct procluct of the reaction between a tertiary amine and a carboxylic acid.
The tertiary amines utilized in the present invention - have the formula ~1 ~ N - R3 15 wherein R1~ Rz and R3 are each, independently, saturated or unsaturated and wherein R1 is a long chain aliphatic group having from 12 to 22 carbon atoms and R2 and R3 are the same or different from each other and are selected from the CJrOUp con-sisting of aliphatic groups containing from 1 to 22 carbon atoms, 20 hydroxyalkyl groups of the formula -R40H wherein ~4 is an alkylene group having 1 to 3 carbon atoms, and alkyl ether groups having the formula R50(CnH2nO)m- wherein R5 is l~ydro--~5 gen or an alkyl or alkenyl group having from 1 to 20 carbon atoms, n is 2 or 3, and m is from 1 to 20. Preferred amines are : 25 those wherein P~1 is an aliphatic alkyl chain having from 12 to 22 carbon atoms, R2 iS an aliphatic alkyl chain having from 12 to 22 carbon atoms, and R3 is an aliphatic alkyl chain llaving from 1 to 3 carbon atoms. Especially preferred amines are those wherein R1 and R2 are each, independently, a satura-ted linear alkyl chain 30 having from 16 to 18 carbon atoms, and R3 is methyl.
Examples of specific tertiary amines arc: lauryldimethyl-amine, myristyldiethylamine, stearyldimethylamine, tallowdimethyl-amine, coconutdimethylamine, dilaurylrnethylamine, distearyl-, .. . . . . .

s~
;, _ 9 _ .~ .
methylamine~ ditallowmethylamine, oleyldimethylamine, ~ioleyl-~ propylamine, lauryldi(3-hydroxypropyi)amine, stearyldi(2-hy-^~ droxyethyl)amine, trilaurylamine, laurylethylmethylamine, and ~(OC2H4)1 00H

(C2H4) 1 oOH

:~ The carboxylic acids utilized in the present invention have the formula : O
.. ,~ I I
i~ 10 R6 - C - OH
~ ., wherein R6 iS hydrogen, or an alkyl, alkenyl, arvl, alkaryl or aralkyl ~roup having 1 to 22 carbon atoms, or a substituted - alkyl, alkenyl, aryl, alkaryl, or aralkyl group having of from 1 to 22 carbon atoms wherein the substituents are selected from the group consisting of halo~3en, carboxyl, or hydroxyl. Preferred fatty acids are those wherein F'`6 iS a long chain, unsubstituted -. alkyl or alkenyl group l-aving from 11 to 21 carbon atoms; more preferably a saturatecl linear alkyl group having from 15 to 17 carbon atoms.
Examples of specific carboxylic acids are: formic acid, ; acetic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, oxalic acid, adipic acid, 12-hydroxy stearic acid, , benzoic acid, 4-hydroxybenzoic acid, 3-chloro benzoic acid, 4-nitro benzoic acid, 4-ethyl benzoic acid, 4-(2-chloroethyl~-- 25 benzoic acid, phenylacetic acid, (4-chlorophenyl)acetic acid, (4-hydroxyphenyl)acetic acid, and phthalic acid.
Preferred carboxylic acids are lauric, myristic, palmitic, stearic, oleic and mixtures thereof.
The amine salt is formed by a simple addition reaction, 30 well known in the art, whereby the tertiary amine is dissolved in a solverlt such as methanol, ethanol, propanol, etc., and the acid is added to the amine solution. Alternativeiy, the amine and acid can simply be mixed and melted together with stirring to form the ~2~855 salt. The molten arnine salt can then be solidified by cooling to room temperature. If the acid used to form the amine salt is a polybasic acid (e.g., oxalic acid), the salt can be monobasic or poiybasic, i.e., either one or more of the acid groups can be - 5 utilized to neutralize the amine.
The formation of amine salts proceeds according to the `~ following reaction:
O R~ O
- R -C-O-t-l + R1-N-R3 - ~ R -IC-O (3 (3 1 2 If the reaction is carried out in a lower alcohol solvent ï~i medium, the salt precipitates from solution, and can be recovered. either by filtration and/or evaporation of the solvent. Preferably the amine and acid pair used in preparing amine salts of the 15 present invention should be chosen so as to produce amine salts having a melting point somewhere within the range of from about 35 C. to 115 ~C. lmore preferably 35 C. -to 85 C.; most pref-erably 55-65 C. ) . Such salts will be solid at room temperature but will melt at typical machine dryer operating temperatures.
- 2û Amine salts having melting points higher than this range can be used in the present invention by formulating them into composi-tions which contain other materials as disclosed hereinafter so - that the formulated composition has a melting point within the desired range.
, 25 A molar ratio of amine to fatty acid of about 1:1 results in the formation of the purest amine salt and the sharpest melting point. If ratios higher or lower than this are used, the end product of this reaction will contain the amine salt plus unreacted amine or unreacted carboxylic acid, respectively. These unre-- 30 acted compounds affect the nodules in a simi lar manner as do the organic substances discussed in the section hereinafter which is entitlecl "Auxiliary Fabric Conditioning Agents and Additives".
Accordingly the considerations involved in changing the molar ratio of amine to fatty acid are dealt with therein.
Preferred amine salts for use herein are those wherein the amine moiety is a C1 2 to C22 alkyl or alkenyl dimethyl amine -~ 8~55 . ~t~ r 1 1 ~

or a di-C12 to C22 alkyl or alkenyl methyl amine, and the acid moiety is a C12 to C22 alkyl or alkenyl monocarboxylic acid. The amine and the acid, respectively, used to form the amine salt will often be of mixed chain lengths rather than single chain lengths, 5 since these materials are normally derived from natural fats and oils, or synthetic processes which produce a mixture of chain ~ri lengths. Also, it is often desirable to utilize mixtures of dif-ferent chain lengths in orcier to modify the physical or perfor-mance characteristics of the softening compositions.
An especially preferred amine salt is methylditallowamine .~ hydrotallowate, where the term tallow refers to the mixture of alkyl moieties derived from tallow and the term tallowate refers to the mixture of fatty acid moieties derived from tallow. This compound can also be referred to as methylditallowammonium .~ 15 tallowate or sometimes as rnethylditallowamine tallowate. Other preferred amine salts for use in the present invention are - stearyldimethylamine hydrostearate, stearyldimethylamine hydro-`~ palmitate, distearylmethylamine hydropalmitate, distearylr:lethyl-. amine hydrolaurate, and mixtures thereof. A particularly pre-s 20 ferred mixture is stearyldimethylamine hydrostearate and ;~ distearylmethylamine hydrnmyristate.
The fabric conditioning compounds of this invention are present in the detergent composition in the form of separate and discrete nodules. The term "nodule" is used generically herein to 25 mean any discrete physical form that has been made by chilling -i, from a mel t. One process for making such nodules is prilling, ;~, e.g. in a tower. Another process is flaking on a chill roll. Still another method is based on cooling in a scraped wall heat ex-changer and then extrudiny. Grinding or other comminuting : 30 processes can also be employed. It is also possible to produce very ~iny particles in the manner described supra, and then form the nodules of this invention by a process involving agglomer-ation, pelletizing, briquetting, or the like. All these processes are conventional and well known in the art in relation to other 35 materials.
,, 5 ~.

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~Z0~ ii5 ~ - 1 2-. , ~j It is intended that the fabric conditioning agents func-tion primarily in the dryer, and accordingly it is undesirable that they melt or dissolve to any great extent in the washer. Time, temperature and degree of agitation are not under the control of the product formulator, so nodules must be rnade that survive 5 well over the entire range encountered in the rcal world of manual and automatic washing processes, soaking and pretreating, high and low temperature.
The fabric conditionin~ nodules, whether in the form of prills, flakes, noodles, or other discrete particles, are of such a 10 size and composition that they become trapped, i.e. entangled in ~;, the clothes as discrete particles when spun or wrung out at the end of the rinse cycle. They remain with the fabrics when , transferred to a mechanical drier and then melt, spread, and condition the fabrics when heated to the worlcing temperature of a 15 mechanical dryer.
Configuration of the nodules also affects performance in the dryer. The larger nodules will ter)d to be entrapped by the outer surfaces of the fabrics, while the smaller nodules will penetrate further toward the inner fibers. Thus larger nodules , 20 tend to exert a stronger destaticizing efrect, which is a fabric ;~
surface phenomenon; while smaller nodules tend to exert a stronger softening effect, which is in part a Function of how ~, individual fibers slide upon one another. Nodule penetration into the fabrics is very much affected by the geometry of the nodule 25 as well as its size, decreasin~ in order from spheres to cylinders to plates (e.g. from prills to noodles to flakes). This provides another degree of freedom for the artisan to tailor make nodules : to suit his particular purposes in the dryer as well as in the wash and rinse.
An approximation for the purpose of this invention is that the controlling dimension is the mean distance of the shortest paths from the central points of the nodules to the surface.
Thus, ~or spheres or cylinders, this dimension i5 the radius for ellipsoids, the minor radius; for plates, half the thickness of the 5 plates. For convenience, the phrases nodule size and particle .' ',~
~s , .. . ....

....

, t.
v :; size as used herein will refer to twice this dimension; i.e. the . ~ r,~' ~- diameter of spheres or cylinders, the thickness nf plates, etc.
U:,ing this definition of nodule size, sizes from about 0.05 to about 2 mm. are satisfactory; sizes from about 0.1 to 5 about 1 mm. are preferred; and sizes from about 0.2 to about 0.7 mm. are especially preferred.

Auxiliary Fabrics Conditioning Agents and Additives -.
~5 ~$The cleaning/conditioning compositions of this invention can be formulated with the fabric conditioning compounds dis-10 cussed supra as the sole conditioning agents of the composition.
Alternatively, however, it is possible to utilize other conditioning agents as well.
Mineral substances. One class of auxiliary fabric conditioning agent is smectite clay. This mineral is disclosed in ;15 Storm et al, cited hereinbefore, as having both fabric softening ar,d destaticizing properties. Clay particles carry through the washing and rinsing cycles of a laundry process, became trapped in the fabrics, and are available to condition the fabrics after 4.;subsequent drying. Inasmuch as -the mechanisms by which fabric 20 are conditioned by amine salts and by clay are different, a skilled artisan is abie to utilize both technologies -to formulate a product to best meet his specific needs . I n general terms, amine salt is a - ~good softening agent and an especially good destaticizing agent, ,'while clay is a good softening agent. A blend of the two utili~es ;,fi25 these properties to great advantage and is a preferred compo-sition. Suitable amounts of clay are within the range f rom about 1 % to about 20 % by weight of thc composition, preferably from about 2 % to about 12 %. Clay can be added to the detergent granule portion of the compositions, or in limited proportions can 30 be part of -the amine salt nodules.
As described in Storm et al, preferred smectite clays have a cation exchange capacity of at least 60 meq. /100 gm. and can be sodium or calcium montmorillonites; lithium, sodium or magnesium saponites; or lithium, sodiun or magneshlm hectorites .

ss --l 4--3,~ Sodium montmorillonites are especially preferred, an example of ',7 which is Gelwhite GP (~1 which is marketed by Georgia Kaolin Company .
Organic substances. A second class of auxiliary fabric 5 conditioning agents includes cationic compounds such as quater-nary ammonium compounds, quaternary imidazoliniurn compounds '; and polyarlido quaternized biurets. Also included in this class are nonionic compounds such as protonated dipolyethoxy monoalkyl ~; amine; C1 0-C26 fatty acid esters of mono- or polyhydroxy alcoholsl0 containing 1-12 carbon atoms, especially glycerol esters; sorbitan -, esters, especially sorbitan mono- and di-esters of C1 2-C20 fattyacids; and tertiary amines which have an iso-electric point from 8.3 to 9.8 and the structure R1R2P~3N where R1 is an alkyl group having from 1 to 6 carbon atoms and R2 and R3 arc C1 0-C26 15 linear alkyl or alkenyl groups.
The abovementioned cationic and nonionic compounds are most effectively employed by incorporating therm into the amine salt nodules of this invention. Even within the nodules, how-ever, they should be ernployed in limited quantities, inasmuch as 20 they tend to increase the solubility, lower the melting point, and broaden the rnelting point range. Suitable quantities of com-pounds of this type, when used at all, are from about l % to about 200 % based on the weight of the nodules, preferably from about 1 % to about 40 %. A person skilled in the art will recog-25 nize that compounds' that are highly water soluble or have amelting point greatly different from the amine salts themselves will appreciably affect the properties of the nodules, and accordingly those compounds will be appropriate for use in relatively lower amounts than cornpounds that are less water soluble and have ; 30 mel ting points closer to those of the amine salts . I lowevcr, these auxiliaries can be useful because a suitable material can acJjust physical properties into the ~esired range for an amine salt nodule whose chemical fabric conclitioning properties are good but whose physical properties are not altogether satisfactory alone.
35 This tlechnique can be employed, for example, to use an amine "

-LZ~8S5 . 1 3 ~ salt that is a good softener but has too high a melting point when pure .
Another class of compounds that can be optionally ,~ added to the nodules influence the properties of the nodules but :' 5 are not themselves fabric conditioning agents. Such compounds are herein referred to as fabric condi tioning additives . Among '~' materials of this kind are ethoxylated surfactants, fatty alcohols and acids, waxes, resins and solvents. The same considerations ~ ~ apply as for the cationic and nonionic conditioning agents de--!~ 10 scribed above, and they can be used in the same proportions.
~ As discussed hereinbefore, use of a molar excess of `~ either the amine or the carboxylic acid used to synthesi~e the q, amine salts of this invention will result in unreacted amounts of whichever of these two ingre~lients is used in excess. The same - 15 general considerations apply to these unreacted ingredicnts that apply to the same ingredients when added separately, and apply to the cationic and nonionic conditioning agents and the condi-tioning additives discussed above.
, Surfactant According to one embodiment of this invention there is , , .
utilized a surfactant selected from the group consisting of anionic, nonionic, ampholytic and zwitterionic detergents and mixtures thereof.
, Preferred anionic non-soap surfactants are water soluble 25 salts of alkyl benzene sulfonate, alkyl sulfate, alkyl polyethoxy ether sulfate, paraffin sulfonate, alpha-olefin sulfonate, alpha-sulfocarboxylates and their esters, alkyl glyceryl ether sulfonate, fatty acid monoglyceride sul fates and sulfonates, alkyl phenol polyethoxy ether sulfate, 2-acyloxy-alkane-1-sulfonate, and 30 beta-alkyloxy alkane sulfonate. Soaps are also preferred anionic su rfac tants .
Especially preferred alkyl benzene sulfonates have about 9 to about 15 carbon atoms in a linear or branched alkyl chain, more especially about 11 to about 13 carbon atorns. Especiaily 35 preferred alkyl sulfate has about 8 to about 22 carbon atoms in .~

i, ~IL2~81~55 .~ . , .

the alkyl chain, more especially from about 12 to about 18 carbon atoms. Especially preferred alkyl polyethoxy ether sulfate has about 10 to about 18 carbon atorns in the alkyl chain and has an ;- avera~e of about 1 to about 12 -CH2CH2O- groups per molecule, 5 especially about 10 to about 16 carbon atoms in the alkyl chain and an average of about 1 to about 6 -CH2CH2O- groups per ' molecule.
Especially preferred paraffin sulfonates are essentially ~,~ linear and contain from about 8 to about 24 carbon atoms, more 10 especially from about 14 to about 18 carbon atorns. Especially preferred alpha-olefin sulfonate has about 10 to about 24 carbon .~c atoms, more especially about lL~ to about 16 carbon atoms; alpha-olefin sulfonates can be made by reaction with sulfur trioxide followed by neutralization under conditions such that any sultones 15 present are hydrolyzed to the corresponding hydroxy alkane sulfonates. Especially preferred alpha-sulfocarboxylates contain `- From about 6 to about 20 carbon atoms; included herein are not only the salts of alpha-sulfonated fatty acids but also their esters made from alcohols containing about 1 to about 14 carbon atoms.
Especially preferred alkyl glyceryl ether sulfates are ethers of alcohols having about 1 û to about 18 carbon atoms, more especially those derived from coconut oil and tallow. Especially - preferred alkyl phenol polyethoxy ether sulfate has about 8 to about 12 carbon atoms in the alkyl chain and an average of about 25 1 to about 10 -C~12CH2O- grJups per molecule. Especially pre-ferred 2-acyloxy-alkane-1-sulfonates contain from about 2 to about 9 carbon atoms in the aryl group and about 9 to about 23 carbon atoms in the alkane moiety. Especially preferred beta-alkyloxy alkane sulfonate contains about 1 to about 3 carbon atoms in the 30 alkyl ~3roup and about 8 to about 20 carbon atoms in the alkyl moiety .
The alkyl chains of the foregoing non-soap anionic surfactants can be derived from natural sources such as coconut oil or tallow, or can be made synthetically as for example using 35 the ~ie~3ler or Oxo processes. Water solubility can be achieved by using alkali metal, ammonium, or alkanolammonium cations;

~L2~ 355 sodium is preferred. Ma~nesium and calcium are preferred ca-tions under circumstances described by Belgian Pat. No. ~'~3,636 , invented by Jones et al, issued December 30, 1976. r.lixtures of : anionic surfactants are contemplated by this invention; a pre-ferred mi>~ture contains alkyl benzene sulfonate having 11 to 13 carbon atoms in the alkyl group and alkyl polyethoxy alcohol sulfate having 10 to 16 carbon atoms in the alkyl ~roup and an average degree of ethoxylation of 1 to 6.
,~ Especially preferred soaps contain about 8 to about 24 carbon atoms, more especially about 12 ~o about 18 carbon atoms.
Soaps can be made by direct saponification of natural fats and ~, oils such as coconut oil, tallow and fish oil, or by the neutral-, . .
ization of free fatty acids obtained from either natural or syn-thetic sources. The soap cation can be alkali metal, ammonium or alkanolammonium; sodium is preferred.
Preferred nonionic surfactants are water soluble com-- pounds produced by the con~ensation of ethylene oxide with a hydrophobic compound such as an alcohol, alkyl phenol, poly-propoxy glycol, or polypropoxy ethylene diamine.
Especially preferred polyethoxy alcohols are the conden-sation product of 1 to 30 mols of ethylene oxide with 1 ~ol of branched or straight chain, primary or secondary aliphatic alcohol ; having fror~ about 8 to a~out 22 carbon atoms; r~ore especially 1 to 6 mols of ethylene~ oxide condensed with 1 mol of straight or ~3 25 branched chain, primary or secondary aliphatic alcohol having from about 10 to about 16 carbon àtoms; certain species of poly-~, ethoxy alcohols are commercially available from the Shell Chemical - Company under the trade name "Neodol"* Especialiy preferred polyethoxy alkyl phenols are the condensation product of about 1 to about 30 mols of ethylene oxide with 1 mol of alkyl phenol having a branched or straight chain alkyl group containing abouL
- 6 to about 12 carbon atoms; certain species of polyethoxy alkylphenols are commercially available from the GAF Corporation ,~ under the trade name " Igepal" .*
Especially preferred polyethoxy polypropoxy glycols are commercially available from E~ASF-Wyandotte under the trade name '' * l'rademark ~2~ S5 ;~
-. "Pluronic"* Especially preferreci conciensates of ethylene oxide -. with the reaction product of propylene oxicie and ethylene diamine are commercially available from BASF-Wyandotte under the trade ~ name "Tetronic".
Preferred se~T i-polar surfactants are water soluble amine oxides containing one alkyl moiety of from about 10 to 28 carbon atorns and 2 moieties selecte!d from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 ~, carbon atoms, and especially alkyl dimethyl amine oxides wherein 10 the alkyl group contains from about 11 to 16 carbon atoms; water soluble phosphine oxide detergents containing one alkyl moiety of "~ about 10 to 28 carbon atoms and 2 moieties selected from the .!.~
, group consisting of alkyl groups and hydroxyalkyl groups con-taining from about 1 to 3 carbon atoms; and water soluble sulf-15 oxicie detergents containing one alkyl r~oiety of frc-m about lO to :- 2~ carbon atoms and a moiety selected trom the group consistingof alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.
Preferred ampholytic surfactants are water soluble derivatives of aliphatic secondary and tertiary amines in which 20 the aliphatic moiety can be straight chain or branched anci : wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate, phosphate, or phos-~ . phonate.
Preferred zwitterion!ic surfactants are water soluble derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium cationic compounds in which the alipha~ic moieties can be straight chain or branched, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one 30 contains an anionic water solubilizing group, especiaily alkyl-dir;lethyl-ammonio-propane-sulfonates and alkyl-c:limethyl-ammonio-hydroxy-propane-sulfonates wherein the alkyl ~roup in both types contains from about 14 to 18 carbon atoms.
A typical listing of the classes anci species of surfac-. 35 tants useful in this invention appear in U.S. Pat. No. 3,664,96i issued to l~orris on May 23, 1972, * Trademark ~L2~ 51855 , ,: -19-: This listing, and the ~oregoing recitation of specific surfactant compounds and mixtures which can be used in `; the instant compositions, are representative o~ such rnaterials but ~~ are not intended to be limiting.

Detergency Builder ., According tn one embodiment of this invention, there is utilized a detergent builder selected from among any of the conventional inorganic and organic water-soluble builder salts as ,' well as various water-insoluble builders. These water-soluble ;~ 10 builder salts serve to maintain the pH of the laundry solution in the range of from about 7 to about 12, preferably frorn about 8 to about 11. Furthermore, these builder salts enhance the fabric cleaning performance of the overall detergent compositions while at the same time they serve to suspend particulate soil released from the surface of the fabrics and prevent its redeposition on the fabric surfaces. ~dditionally, in certain compositions that contain certain smectite clays as fabric softening agents, poly-anionic builder salts cause these clays to be readily and homogen-c eously dispersed throughout the aqueous laundering medium with 20 a minimum of agitation . The horT ogeneity of the clay dispersion is necessary for the clay to function effectively as 2 fabric softener, j~ while the ready dispersability allows granular detergent compo-~ sitions to be formulated.
-' Non-limiting examples of suitable water-soluble, inor-25 ganic alkaline detergent builder salts include alkali metal carbon-ates, borates, phosphates, polyphosphates, bicarbonates and silicates. Specific examples of such salts are sodium and potas-sium tetraborates, perborates, bicarbonates, carbonates, tripoly-phosphates, pyrophosphates, orthophosphates, and hexameta-30 phosphates.
Examples of suitable organic alkaline detergency builder salts are: (1 ) Water-soluble aminopolycarboxylates, e.g. sodium and potassium ethylenediaminetetraacetates, nitrilotriacetates and ., ~J-(2-hydroxyethyl)-nitrilodiacetates; (2) Water-soluble salts of --, ~

~2q~3SS

phytic acid, e.g., sodium and potassium phytates-see U.$. Pat.
No. 2,739,942; (3) Water-soluble polyphosphonates~ including specifically, sodium, potassium and lithium salts of ethane-l-hydroxy-l, l-diphosphonic acid; sodium, potassium and lithium salts of methylene diphosphonic acid; sodium, potassium and lithium salts of ethylene diphosphonic acid; and sodium, pot-assium and lithium salts of ethane-1,1,2-triphosphonic acid.
Other examples include the alkali metal salts of ethane-2-carboxy-l,l-diphosphonic acid, hydroxymethanediphosphonic acid, carbonyl-diphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid, ethane-2-hydroxy-1,1,2-triphosphonic acid, propane-1,1,3,3-tet-raphosphonic acid, propane-1,1,2,3-tetraphosphonic acid, and propane-1,2,2,3-tetraphosphonic acid; (4) Water-soluble salts of polycarboxylate polymers and copolymers as described in U.S. Pat.
No. 3,308,067.
In addition, other polycarboxylate builders which can be used satisifactorily include water soluble salts of mellitic acid, citric acid, pyromellitic acid, benzene pentacarboxylic acid, oxydiacetic acid, carboxymethyloxy-succinic acid and oxy-disuccinic acid.
Certain zeolites or aluminosilicates ~nchan~e the functionof the alkaline metal pyrophosphate and add building capacity in that the aluminosilicates sequester calcium hardness. One such aluminosilicate which is useful in the compositions of the in-vention is a crystalline water-insoluble hydrated compound of the formula Naz (AlO2)z.(SiO2) xH2O, wherein z and y are integers of at least 6; the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an interger from about 15 to about 264; said aluminosilicate ion exchange material having a particle size dia-meter from about 0.1 micron to about 100 microns, preferably 1-10 microns; a calcium ion exchange capacity on an anhydrous basis of at least about 200 milligrams equivalent of CaCO3 hardness per gram; and a calcium ion exchange rate on an anhydrous basis of at least about 2 grains/gallon/minute/gram. These synthetic alumin-osilicates are more fully described in British Pat.

~1 12~35S

~` No. 1,429,143 invcnted by Corkill et al, published Mar. 2~, 1976, , A second water-insoluble synthetic alu~inosilicate ion -exchange material useful herein is ar~orphous in nature and has -5 the formula Nax(xAlO2.5iO2), wherein x is a number from 1.0 to 1.2 and y is 1, said amorphous ma~erial being further charac-terized by a Mg exchange~ capacity of from about 50 mg eq.
CaCO3/g. to about 190 mg eq. CaCO3/g. and a particle diameter of from about 0.01 microns to about 5 microns. This ion ex-10 change builder is more fully described in British Pat. ~io.
1,470,250 invented by B. H. Gedge e~ al, published Apr. 14, 1 977, .:;
Enzyme According to one embodiment of this invention there is 15 utili~ed an enzyme selecteo fror.1 the group consisting of protease, arnylase and lipase. A disclosure of proteolytic enzymes suitable for use in stain removal compositions appears in McCarty, U.S.
Patent 3,519,570 issued Jul~ 7, 1970. One method o~ preparing enzyrne-containing nodules is also described therein.
A disclosure of amylolytic enzymes suitable for use in stain removal compositions appears in t~esforges, U . 5 . Patent 3,661,786 issued Mayj 9, 1972. ~tabilization of enzymes by the use of starch is also disclosed !by Desforges.
A disclosure nf discrete, shaped inorganic solids r25 containing proteolytic or amylolytic enzymes appears in van -Kampen et al, U.S. Patent 3,784,476 issued January 8, 1974.
The selected inorganic solids were soluble builder salts: sodium and potassium sulfate and ortho-, pyro- and tripolyphosphates;
ammonium carbonate, bicarbonate and chioride; and the like.
30 Processes mentioned were milling, pelleting, extruding, stamping, pressing, granulation, etc. to form ribbons, flakcs, threads, spheres, noodles, tablets, pellets, granules, etc, Individual particles were said to have a maxirnum dimension of not more than 15 mm . a minimum dirnension of not n~ore than 2 . 5 mm .; and 35 weigh between 0.05 and 100 mg~

, SS

Extrusions ~ or~anic sol~ds contalning a num~er of detergent adjuncts, includin~ enz~mes, are disclosed in Carter et al, Canadian Patent 832,976 is-sued 3anuary 27, 1970. Suit-able extrudable solids were said to be polyglycols; polyalkylene oxides, C12-C20 alpha-olefin sulfonates; sodium N-coconut acid-N-methyl taurate; condensa-tes between polyethylene oxide and polypropylene oxide; nonionic surfactants; condensates of alky-lene oxides with alcohols, alkyl phenols, amides, amines and acids;
soaps, starches and gelatinized starches; gelatin; and cellulose derivatives.
It will be noted that the conglutinated granules of McCarty, the shaped solids of Van Kampen et al, and the noodles of Carter et al, are all encompassed by the term nodules as used herein.
Pexoxy Bleach According to one embodiment of this invention there is utilized a peroxy bleach. ~he peroxy bleach can be inorganic or organic, and if the former can optionally contain a peroxy bleach activator.
By inorganic peroxy bleaches are meant inorganic peroxy-hydrates; examples are alkali metal salts of perborates, per-carbonates, persulfates, persilicates, perphosphates, and per-polyphosphates.
Preferred inorganic peroxy bleaches are the sodium and potassium salts of perborate monohydrate and perboxate tetra-hydrate. Sodium perborate tetrahydrate is especially preferred.
By organic peroxy bleach is meant urea peroxide CO(NH2)2.H2O2 or an organic peroxy acid or anhydride or salt thereof which has the general formula O~

%~ 55 Si ' ,~ --2 3---wherein R is an alkylene group containing from 1 to about 20 carbon atoms, preferably 7 to 16 carbon atoms, or a phenylene ~^.group and Y is hydrogen, halogen, alkyl, aryl or any group .
~,.,. which provides an anionic moiety in aqueous solution. Such Y
!~;, 5 groups can include, for example, . . -- .
O O
.~ 11 /1 -C-OM, . -C-0-01~,1 or -:-OM

wherein M is H or a water-soluble, salt-forming cation.
Tne organic peroxyacids and salts thereof operable in the instant invention can contain either one or two peroxy groups -~ and can be either aliphatic or aromatic. When the organic per-oxyacid is aliphatic, the unsubstituted acid has the general -~ formula '' 15 ~0 ~- HO-O-C-(CH2)n-Y
:, ~, where Y, for example, can be CH3, CH2CI, ~S' ', O O O
-OM, -S-OM or -~-O-OM
'`~ 20 ~

~,~, and n can be an integer from 1 to 20. Diperazelaic acid (n = 7) and diperdodecanedioic acid ~n - 10) are the preferred compounds ,~ of this type. The alkylene linkage and/or Y lif alkyl) can con-tain halogen or other noninterfering substituents.
' 25 When the organic peroxyacid is aromatic, the unsub-stituted acid has the general formula ~3 0 H~O-O-C-C6H4-Y
,- wherein Y is hydrogen, halogen, alkyl, ,, . ,:, . .. . .. . . .

i ~2~35iS

.';; O O
-C-OM , -S-OM or -C-O-OM
. O

for example. The percarboxy and Y groupings can be in any relative position around the aromatic ring. The ring and/or Y
`~ group (if alkyl) can contain any noninterfering substituents suchas halogen ~roups. Examplles of suitable aromatic peroxyacids and salts therof include monoperoxyphthalic acid, diperoxyt~re-phthalic acid, 4-chlorodiperoxyphthalic acid, the monosodium salt 10 of diperoxyterephthalic acid, m-chloroperoxybenzoic acid, p-nitro-~-3 peroxybenzoic acid, ancJ diperoxyisophthalic acid.
; Of all the above described organic peroxyacid com-,~ounds, the most preferred for use in the instant compositions are diperdodecanedioic acid and diperazelaic acid.
Bv peroxy bleach activator is meant an organic peracid precursor containing one or more acyl groups which is susceptible to perhvdrolysis. The preferred activators are those of the N-acyl or O-acyl-conmpound type containing an acyl radical R-CO-wherein R is a hydrocarbon group having from 1 to 8 carbon atoms. If the radicals R are aliphatic, they preferably contain 1 to 3 carbon atoms while, if they are aromatic, they preferably contain up to 8 carbon atoms. R may be unsubstituted Qr substi--:, tuted with C1 3 alkoxy groups, halogen atoms, nitro- or nitrilo groups. Aromatic radicals, In! particular, rnay be chloro- and/or ~: 25 nitro-subs~ituted. Examples of activators coming within this . definition are certain N-diacetylated arnines, N-alkyl-N-suifonyl carbonamides, N-acylhydantoins, cyclic N-acylhydrazides, triacyl cyanurates, benzoic and phthalic anhydrides, O,N,N-trisubsti-tuted hydroxyl amines, N,N'-diacyl-suifurlamides, 1,3-diacyl-4,5-30 dialkyloxy-imidazolidines, acyla~ed ç31ycolurils and carboxylic esters as disclosed in de Luque, IJ.S. patent 4,240,920 issued December 23~ 1980. Another useful peroxy bleach activator is C7 Cg acyl oxybenzene sulfo-nate.
:, ~ ,,"!

~2(~15 I!~SS

Special advantages of using a combination of porphine :_ and peroxy bleaches are also disclosed by de Luque. Combina-tions of enzyme and peroxy bleach are disclosed by McCarty (Il), - U.S. Patent 3,553,139 issued January 5, 19710 Halogen Bleach -.;.
According to one embodir~ent of this invention tl-ere is utilized a halogen bleach. Examples of suitable halogen bleaches ~,~ are N-chloro and N-bromo alkane sulfonamides and, more prefer-ably, trichloro isocyanuric acid and sodium and potassium dichloroisocyanurates.
Porphine Bleach ,~
. ~ According to one embodiment of this invention there is . utilized a porphine bleach. This can be a porphine or a mono-, di-, tri-, or tetra aza porphine; metal-free or metallated with Zn(ll), Ca(ll~, Cd(ll), Mg(ll), Sc(lll), Al(lll) or Sn(lV); and solubilized with one or more solubilizing groups which can be anionic, nonionic or cationic in nature. The porphine bleaches .: disclosed by Sakkab in U.S. patent no. 4,255,273 issued March ,~ 10, 1981 are suitable for use in this invention.
'~ 20 Preferred porphine bleaches are zinc or aluminum phthalocyanine sulfonate.

Optional Ingredients It is to be understood that the fabric cleaning/con-:
'-. 25 ditioning compositions of the present invention can contain other components commonly used in detergent compositions. Soil sus-pending agents such as water-soluble salts of carboxymethyl-cellulose, carboxyhydroxymethylcellulose, copolymers of maleic anhydride and vinyl ethers, polyacrylic acid and salts thereof, and polyethylene glycols having a molecular weight of about 400 to 10,000 are common components of detergent compositiOns and can be used at ievels of about o, 5 s~ to about 10 ~ by weight.

,;

12~ 35~ii ~. .
~ .

` . Dyes, pigments, optical brighteners, and perfumes can be added in varying ar.~ounts as desired.
- Other materials such as fluorescers, antiseptics, ~ermi-cides, anti-tarnish agents, anti-corrosion agents, and anti-caking ' 5 agents such as sodium sulfosuccinate and sodium benzoate may -, also be added. Other materials used in detergent compositions that can be used herein are suds boosters, suds depressants, fillers such as sodium sulfate, pH buffers, and hydrotropes such .. as sodium toluene sulfonate and urea.
Other optional materials are related to fabric condi-tioning: finishing agents, sizing agents, and anti-wrinkling a~3ents such as corn starch which is disclosed in Belgian patent ~- no. 811,082 issued August 16, 1974 Processes of Manufacture and Use The amine salt nociules of the instant invention are prepared by the process described hereinbefore. In one embodi-ment of this invention, they are marketed in this form as a fabric conditioning a~ent without further processing. They are used by - 20 simply adding to the beginning of the wash at the same time as detergent is added; the user is then relieved of the need to adcl additional ma$erials to ~he laundry at any later stage of the ~; washing, rinsing and; mechanical drying cycleO A suitable amount of amine salt nodules in undiluted form to be added to a home 25 washer handling 8 pounds of clothes is in the range of 1 to 20 '~ g rams .
For convenience in dispensing or for other reasons it may be desired to admix some other substance in discrete nodular form to the a~ine salt nodules before packaging. A skilled 30 formulator is free to select the amount and type of diluent from among substances that are inert, cheap, convenient, safe and avai lable .
In a second embodiment of this invention, the amine sal-t nodules are blended with an enzyme, peroxy bleach, haloyen 35 bleach, and/or porphine bleach to provide a combination fabric .j *

~ ~. ...

,~ 1;;~1)8BSCi . !1 , 27 ., ~
J ~.` conditioning and stain removal product. These four types of stain removal ingredients have been defined hereinbefore.
~ The formulator of a product of this type has a wide -i range of compositions to choose from, according to his desire to .; 5 emphasize the varied propcrties contributed by these different - ingredients. In general terms, the five ranges of compositions identified in the table below are suitable, wherein all fiyures .: given are percentages based on the fabric conditioning/stain -` removal compositions. Each entry in the table includes two ran~es: the first is the broad range of operability, and the ~ second (in parentheses) is the narrower, more preferred range.
i~ With reference to composition e, it will be noted that, in addition to the nurnerical limits, the composition is required to contain one ; or more of the enzyme or bleach additives.
v;
.~ 15 a b c d e . .
, amine salt 1-99 % 1-95 ~1-99 . 5% 1-99.995~ 1-99.995 .' fabric conditioner (5-96) (5-90) (5-98) (5-99.92) (5-99.98) enzyme 1-50 0-50 -~ (4-25) ~0-25) peroxygen bleach 5-95 0-95 (10-80) (0-80) halogen bleach 0 . 5-60 0-60 i (2-40) (0-40) porphine bleach 0 . 005-12 0-12 (0.02-8) (0-8, diluent balance bal. bal. bal. bal.
Optionally, other additives may be added to this fabric conditioniny/stain removal product. These other additives in-clude, but are not limited to, surfactant or detergent builder as 30 described hereinbefore and those materials described herein in the section entitled Optional Ingredients. The term diluent as used in the table above includes not only materials that may be desired to control cost, but also to control density, improve prvcessing ., '~, -:~

. ~
12~0 ~3855 ..
'~ (e.g. flowability), or to contribute sorne type of performance functionality other than fabric conditioning or stain removal.
I t is preferred that the components of thé fa~ric con-ditioning/stain removal product are in noduiar form as broadly 5 defined hereinbefore. Nodulizing of the stain removal ingreclients ~,can be achieved by a number of methods which are wel I recog-3nized in the art. As these ingredients are intended for use in the wash, the nodules containing them should be water soluble or water dispersable. F~eferences that describe specific useful lO techniques are McCarty, U.S. Patent 3,519,570; van Kampen et al U.S. Patent 3,784,476; and especially Carter et al, Canadian Patent 832,976; all of which have been cited hereinbefore.
Particle si7e of the nodules of stain removal ingredients is preferably from about 0.05 to about 2 mm. This dimension is 15 less critical than the comparable dimension of amine salt nodules, -because the nodules of stain removai ingredients are expected only to be stable in shipping and storage and to dissolve or ., disperse in the wash, while the nodules of amine salt must sur-vive the wash and rinse and be of proper size to become trapped /20 in the fabrics and function effectively in the dryer.
-~In a third embodiment of this invention, the amine salt nodules are adrnixed by proportionation, batch or continuous, with detergent granules. This provides a through-the-wash ,~fabric cleaning/fabric conditioning composition -that accomplishes i~25 multiple functions in a single droduct.
The detergent granules can be formed by any of the -conventional techniques i.e., by slurrying the individual compo-nents in water and then atomking and spray-drying the resultant mixture, or by pan or drum granulation of the components. A
'30 preferred method of spray drying compositions in granule form is disclosed in U.S. Pat. Nos. 3,629,951 and 3,629,g55 issued to Davis et al on December 28, 1971.
The fabric cleaningl Fabric conditioning compositions of this invention contain an anionic, nonis)nic, ampholytic or zwitter-35 ionic surfactant, preferably anionic; a detergency builder; and an amine salt fabric conditioning agent in nodular form as defined .
!

s ` ~2al~5S
j" --2 9--....
'`~ herein. Preferably the surfactant is from about 1 % to about 50 %
;~............... by weight of the composition, more preferably from about 5 to-~ about 30 %, most preferably from 10 to 20 %. Preferably the '~ detergency builder is from about 5 % to about 95 % by weight of ';' 5 the composition, preferably from about 10 % to about 60 %, most preferably from 15 to 40 5l. Preferably the fabric conditioning ' agent is from about 1 to about 30 % by weight of the composition, preferably from about 3 to about 20 %, most preferably from 5 to 15 %.
!~ 10 The fabric cleaning/fabric conditioning compositions of : ~ this invention can also, optionally, contain other additives.
These other additives include, but are not limited to, the stain removal agents disclosed hereinbefore, and those materials de-'~ scribed herein in the section entitled Optional Ingredients. These 15 additives can be incorporated into the detergent granules or, ; optionally, they can be prepared in the form of separate water -, soluble or water dispersable nodules as described hereinbefore.In this event, the amine salt nodules, the additive nodules, and the detergent granules are all blended by proportionation to form ' 20 the final product.
,s, The pH of the fabric conditioning agents and the fabric conditioning/stain removal compositions of this invention have no ~, particular significance, as the former do not dissolve and the pH
of the latter is dominated by that of the detergent product that is 25 added to the wash at the same!tir;le. The pH of the cleaning/con-L~ ditioning compositions is controlled in the manner that is cus-tomary for detergent compositions and is no more critical than is usual for detergent compositions. Accordingly, the pH of 1 9~
:.- aqueous solutions of the fabric cleaning/conditioning compositions ii 30 is preferably from about 8 to about 12, with 9-11 especially preferrecl .
Each of the embodiments of the invention is intended to ..
be used in 3 laundry process comprising washing, rinsing and drying, The washing step can be by hand or in a machine, 35 manual or automatic. Soaking is optional. Rinsing can also be . . , by hand or by machine, wrung out or spun to remove excess ,j ' ~IL2V~355i `~;

. water. Although drying can be accomplished without difficulty byhanging on a line or spreading out in the sun, the fabric condi-tioning benefits of this invention are more pronounced when drying takes place in a mechanical dryer. Sometimes referred to as an automatic dryer, such a device tumbles the clothes with hot J air, usually at a temperature of from about 40 to about 95 C., most often at temperatures of 50-95 C. The amine salt nodules of this invention, which are entangled in the clothes leaving the rinsing step, thereupon soften or melt, spreading upon the fabric surfaces to destaticize them and penetrating toward the inner fibers thereof to soften them.

-" INDUSTRIAL APPLICATION
. ,,;
- Thc following examples describe the formulation of specific compositions of this invention and the benefits derived therefrom. They are illustrative of the invention and are not to be construed as limiting thereof.

Example 1.
", Flakes of hydrogenated tallow fatty acid (mol. wt. 274) in the amount of 21.95 pounds and chunks of di (hydrogenated tallow) methyl amine ~mol. wt. 520) in the amount of 38.05 pounds were separately added in equimolar amounts to a stainless steel -`~ vessel. Heat was applied and the ingredients melted; with con-tinuous agitation the amine salt formed and was held overnight at 1 80 F.
The amine salt melt was prilled by atomizing with air in a two-fluid nozzle and dropping through a cold-air tower. Nod-ules comprising predominantly spherical droplets (prills) were removed from the bottom of the tower and screened through a 10 mesh screen (openings 1.65 mm. ) to remove a few coarse frag-30 ments. The median particle size of the prills used was deter-.

,;i T 9~ Z ~ /B f B S C j ` ~ ~ji~
b 4' ', mined by sieve analysis to be 0.4 mm.; with 80 ~ of the clis-- ~, tribution between about 0.2 and 0.7 mm., and 96 % between about - 0 .1 and 0 . 9 mm.
- Detegent granules having composition A as shown in 5 Table I below were prepared by crutchins all ingredients and spray-drying in a conventional manner.
'~
Table 1.
.;
Ingredient A B
C13 linear alkyl benzene sulfonate 12.0 parts12.0 parts 10 Neodol 23 - 6.5Ta 0.5 2.0 Sodium tripolyphosphate 19 . 0 , ,~ Sodium pyrophosphate - 8 . 0 ;' Sodium aluminosilicate ~Zeolite A) - 20.0 ' ` "7 Sodium silicate (1.6 mol ratio SiO~/Na2O) 1.9 5.7 15 Sodium carbonate - 15 . 0 Sodium toluene sulfonate 0 . S 1 . 0 Polyacrylic acid (mol. wt. 60,000) 1.0 ' Sodiurn Sulfate balance balance ~,~ Minor Ingredientsb 0.5 0.3 ,~ 20 liilater ~ 6 ~ 5 ~, Total 66.6 parts 82.2 parts ,~
A fabric cleaning/co~ditioning composition was prepared by blending 13 parts of the amine salt nodules, 5.4 parts sodium tripolyphosphate, and 10.0 parts sodium carbonate with 66.6 parts 25 of detergent granules described above, to make Product I of this .,.

(a~ Trade Mark, Shell Chernical Company, for the nonionic ~; surfactant prepared by condensing 6.5 r~ols of ethylene oxide with a mixture of C~12 and C13 linear alcohols, and , then topping to remove low molecular weight odor bodies.
. 30 (b) Perfume, brightener.
,i~
"
, ,~
.~

;. ~LZ~85~i `., .~

~ :.
', invention. This product was tested for fabric destaticizing in comparison with commercially available products as will now be described .
~inety-nine grams of productC were added to a Sears 5 KENMOREd washing machine filled with 17 gallons of water having a hardness of 6 grams per U.S. gallon (Ca :1~4g =3:1) at 95 F.
- A wash load consisti--g of 33 items of mixed natural and synthetic fabrics weighing 5 ~ pounds was washed, rinsed in the ~P same hardness water, and spun. The fabric bundle was then lO dried for 60 minutes in a Sears KENMOREd electric machine dryer in a controlled humidity environment (air dew point = 0 C.).
The foregoing treatments were repeated for a commercial fabric cleaning/conditioning product, not of this invention, iden-~- tified herein as Product l l . The washing treatment was also lS repeated for TIDE~, a commercial detergent containing no special fabric conditioning ingredients. However when the fabrics . washed with TlDEe were dried, a sheet of BOli~CEe was adcied to the dryer along with the fabrics at the beginning of the drying ` cycle.
Static cling was deterr,lined by two rnethods. After t drying, the bundle of dried fabrics was transferred to a Faraday cage and the voltage was read. Individual fabrics were then removed from the bundlc in the Faraday cage and any fabrics -~'s which were clinging ~to one ~nother were noted; a low number 3,~ ' ! -s 25 (c) Product usage was calculated as though the product contained 100 parts, even though the figures reported above add up to only 95 parts . The remainder, 5 . 0 parts, which was omitted for experimental convenience, would have been filled in commercial practice with additional sndium sulfate which contributes virtually nothing to the performance of cleaning or fabric condi-tioning compositions.
(d~ Registered tradcmark, Sears Roebuck ~ Company (e) Registered trademarks, The Procter ~ Gamble Company .,, ~ ~Z( 181~55 i ~ r indicates better static cling. The voltage after all fabrics were - removed was rated, and the voltage difference linitial minus final) was recorded. A iow number indicates a low level of static cling.
The table below gives results for two comparative tests.
~ .
Voltage Dif~erenceFabrics Clinging Product I 33 Product l l81 9 Product 1 30 0 These results show tha~ the destaticization provided by a fabric cleaning/conditioning composition of this invention is considerably better than a currently marketed product of this type, and is nearly as good as is provided by using two sepa-rate-purpose products.
i, 15 Similar results are obtained when the amine salt is mixed for only ten minutes after melting and before prilling.
,~;
Example 2.
A fabric cleaning/conditioning composition was prepared by blending 13 parts of the amine salt nodules hereinbefore 20 described in Example 1, 82 parts of d~tergent granules A as defined in Example 1, and 5 parts sodium montmorillonite clay.
This product identified herein as Product l l l of this invention was tested for fabric softening in comparison with commercially avail-able products as will now bc described.
Eight and one-half grams of product were added to a ~- tub of miniature washer filled with one and one-half gallons of water having a hardness of 6 grams per U.S. gallon (Ca :Mg -3:1 ) at 95 F. A wash load consisting of 4 fabric swatches 15 inches square of cotton terry cloth and 2 fabric ,., r .

5~

- ~
~ZQ8~3SS

~, swatches 11 inches square each of polyamide, polyester and cotton/ polyester blend was washed for 12 minutes, rinsed in the same hardness water, and spun.
The foregoing treatments were repeated for Prcduct l l, 5 the commercial fabric cleaning/conditioning product not of this - invention . The washing treatment was repeated twice for T I DE .When one set of fabrics washed with T I DE were rinsed, 3 . 9 ml . of DOIII~NY were added to the tub.
.~ The damp fabrics from each treatment were dried sepa-~j 10 rately for 60 minutes in an electric machine dryer. Softness of - the terry cloth swatches was graded by an expert panel, result-ing in the following (data in panel score units, LSD (9596) = 0.5).

., _ TIDE plus DO\Y~iY +1.4 ?roduct l l l +1 . 3 : 15I'roduct l l O
Product I -O . 6 T I D E -2 . 1 ' Fabrics treated wilh Product l l l, which contained amine ,~ salt nodules and clay, were virtually as soft as those treated 20 separately with the single purpose products TIDE and DOWNY.
These fabrics were distinctly softer than those treated with Product l l which contained cationic softener agglomerates plus clay as taught by Baskerville! et al cited hereinbefore. Fabrics treated with Product 1, containing amine salt nodules as the sole 25 softening agent, were substantially softer than those washecl in regular detergent, but were not so soft as those washed in a - comparable through-the-wash composition containing clay.

Example 3.
Detergent granules having composition B as identified in 30 Table I above were prepared in the same manner as was used for , "

-.,.
_ -~
. ~ .i 3~Z~S5 ; tj~'~' , -35--composition A. A fabric cleaning/conditioning composition was prepared by dry blendin~3 82.2 parts of detergent granules B
with 8.7 parts of the aminle salt nodu!es hereinbefore described in :-~ Example 1. This product is herein identiFied as Product IV of ,-' 5 this invention. Another fabric cleaning/conditioning compositionwas prepared by dry blending 82.2 parts of detergent granules B
-~ with 15 . 6 parts of a fabric conditioning additive nodule comprising ~, 2.3 parts ditallowdimethylammonium chloride, 3.1 parts sodium montr~orillonite clay and 5 .1 parts inert ingredients. This lO product is herein identified as Product V which is not, however, according to this invention but is a reference composition.
Products IV and V were tested for clay soil detergency '~ ' using the following n ethod. Soiled swatches of cotton, poly-est~r/cotton blend, and polyester were prepared by staining in a L5 controlled rnanner with clav padded on from a water slurry and - dried. h;iniwash tubs were filled with one U.S. gallon of water at 95 ~C. and having, respectively, 2, 8 or 12 grains per U.S.
gallon of ilar~ness (Ca :Ais =3:1 ), and approximately six grams -, of productg were acided together with a speckle containing 0.03 ,~ 20 grams of PEG 80001~ and 0.09 grams inert ingrec~ients. Swatches were then washed in the test product and dried. Whiteness was ' deterr~ined using a Hunter Color Difference rneter, using the - equation ~-(7L2 _ 40Lb)/700. Results were as follows, where each entry in the table is a whiteness value avera~3ed over all 3 25 water hardnesses.
,, Fabric Type Product IVProduct V
cotton 27 23 polyester/cotton blend 59 55 polyester 50 45 30 ~9) Product usayes were adjusted in the manner described in footnote (c) in relation to Product 1.
(h) Polyethylene glyccl having a molecular weight of 8000.

-; ~ ~
1"$ ~2~8~5S
5 . -36-~` On every fabric type, the swatches washed in Product IV were - significantly whiter (95 ~ statistical level) than those washed in a corresponding manner in Product V.
~ Lipid soil removal was evaluated by washing swatches of 65 - - 5 polyester/35 cotton blend which had been soiled by panelists rubbiny over their faces, cheeks and necks in a controlled man-ner. The swatches were cut in half, and each half washed in the two products separately in the manner described above, except -: that speckles were not added. Grading was done by expert a; 10 graders who compared the two halves of each original swatch against each other. Results were as follows where entries in the table are differences in panel score units between Product IV and Product V (positive values mean Product IV is cleaner). Each ~: entry represents 10 panelists and 3 expert graders. The differ-ences in 2 grain and 12 grain water are significant at the 95 - level.

- Panel Score Units water hardness ( Product IV - Product V~

- 2 grain + 0. 84 20 8 grain + 0. 63 i' 12 grain + 0.96 ", .

,~, ,:

.,

Claims (19)

What is claimed is:

1. A fabric conditioning agent comprising a salt of (i) a tertiary amine having the formula wherein R1, R2 and R3 are each, independently, saturated or unsaturated and wherein R1 is a long chain aliphatic group having from 12 to 22 carbon atoms and R2 and R3 are the same or different from each other and are selected from the group consisting of aliphatic groups containing from 1 to 22 carbon atoms, hydroxyalkyl groups of the formula -R4OH wherein R4 is an alkylene group having from 1 to 3 carbon atoms, and alkyl ether groups having the formula R5O(CnH2nO)m-wherein R5 is hydrogen or an alkyl or alkenyl group having from 1 to 20 carbon atoms, n is 2 or 3, and m is from 1 to 20; and (ii) a carboxylic acid having the formula wherein R6 is hydrogen, or an alkyl, alkenyl, aryl, alkaryl or aralkyl group having 1 to 22 carbon atoms, or a substituted alkyl, alkenyl, aryl, alkaryl, or aralkyl group having from 1 to 22 carbon atoms wherein the substituents are selected from the group consisting of halogen, carboxyl, and hydroxyl;

wherein said tertiary amine/carboxylic acid salt exists in the form of discrete nodules having a particle size from about 0.05 to about 2 mm.

2. A fabric conditioning agent according to claim 1 wherein R1 is an aliphatic alkyl chain having from 12 to 22 carbon atoms, R2 is an aliphatic alkyl chain having from 12 to 22 carbon atoms, and R3 is an aliphatic alkyl chain having from 1 to 3 carbon atoms; wherein R6 is a long chain, unsubstituted alkyl or alkenyl group having from 11 to 17 carbon atoms; and wherein the melting point of said discrete nodules is from about 35 to about 115 °C

3. A fabric conditioning agent according to claim 2 wherein the particle size of said nodules is from about 0.1 to about 1 mm. and wherein the melting point of said nodules is from about 35 to about 85 °C.

4. A fabric conditioning agent according to claim 3 wherein R1 and R2 are each, independently, a saturated linear alkyl chain having from 16 to 18 carbon atoms; R3 is methyl; and R6 is a saturated linear alkyl chain having from 15 to 17 carbon atoms.

5. A fabric conditioning/stain removal composition com-prising:

(a) a fabric conditioning agent comprising a salt of (i) a tertiary amine having the formula wherein R1, R2 and R3 are each, indepen-dently, saturated or unsaturated and wherein R1 is a long chain aliphatic group having from 12 to 22 carbon atoms and R2 and R3 are the same or different from each other and are selected from the group consisting of aliphatic groups containing from 1 to 22 carbon atoms, hydroxyalkyl groups of the formula -R4OH wherein R4 is an alkylene group having from 1 to 3 carbon atoms, and alkyl ether groups having the formula R5O(CnH2nO)m- wherein R5 is hydrogen or an alkyl or alkenyl group having from 1 to 20 carbon atoms, n is 2 or 3, and m is from 1 to 20; and (ii) a carboxylic acid having the formula wherein R6 is hydrogen, or an alkyl, alkenyl, aryl, alkaryl or aralkyl group having 1 to 22 carbon atoms, or a substituted alkyl, alkenyl, aryl, alkaryl, or aralkyl group having from 1 to 22 carbon atoms wherein the substituents are selected from the group consisting of halogen, carboxyl, and hydroxyl;
wherein said tertiary amine/carboxylic acid salt exists in the form of discrete nodules having a particle size from about 0.05 to about 2 mm.; and (b) a stain removal agent selected from the group consisting of enzyme, peroxy bleach, halogen bleach, and porphine bleach.

6. A fabric conditioning/stain removal composition accord-ing to claim 5 wherein R1 is an aliphatic alkyl chain having from 12 to 22 carbon atoms, R2 is an aliphatic alkyl chain having from 12 to 22 carbon atoms, and R3 is an aliphatic alkyl chain having from 1 to 3 carbon atoms; wherein R6 is a long chain, unsubstituted alkyl or alkenyl group having from 11 to 17 carbon atoms;
wherein the melting point of said discrete amine salt nodules is from about 35 to about 115 °C.; wherein the stain removal agent is in the form of nodules having a particle size from about 0.05 to about 2 mm.; and wherein the enzyme is amylase, protease or lipase; the peroxygen bleach is an alkali metal salt of sodium perborate or sodium percarbonate or is diperoxyazelaic acid or diperoxydodecanedioic acid; the halogen bleach is sodium or potassium dichlorocyanurate or trichloro isocyanuric acid; and the porphine bleach is zinc or aluminum phthalocyanine sulfonate.

7. A fabric conditioning/stain removal composition accord-ing to claim 6 wherein the particle size of said amine salt nodules is from about 0.1 to about 1 mm. and wherein the melting point of said nodules is from about 35 to about 85 °C.; and wherein, when component (b) is enzyme, it is present at from about 1 to about 50 %
and the fabric conditioning agent is present at from about 1 % to about 99 %; when component (b) is per-oxygen bleach, it is present at from about 5 % to about 95 % and the fabric conditioning agent is present at from 1 % to about 95 %; when component (b) is halogen bleach it is present at from about 0.5 to about 60% and the fabric conditioning agent is present at from about 1 % to about 99.5 %; and when component (b) is porphine bleach, it is present at from about 0.005 % to about 12 % and the fabric conditioning agent is present at from about 1 % to about 99.995 % of the composition;
wherein all percentages are by weight of the fabric conditioning/stain removal composition.

8. A fabric conditioning/stain removal composition accord-ing to claim 6 wherein R1 and R2 are each, indepen-dently, a saturated linear alkyl chain having from 16 to 18 carbon atoms; R3 is methyl; and R6 is a saturated linear alkyl chain having from 15 to 17 carbon atoms;
wherein the enzyme is protease or amylase; and wherein the amounts of the components, expressed in weight %
based on the active ingredients of the fabric conditioning/stain removal composition, are: fabric conditioning agent from 5 to 99.995 %; enzyme from 0 to 10 %; peroxide bleach from 0 to 95 %; halogen bleach from 0 to 10 %; and porphine bleach from 0 to 1 %.

9. A fabric cleaning/conditioning composition comprising (A) an anionic, nonionic, amphoteric or zwitterionic surfactant;
(B) a detergency builder; and (C) a fabric conditioning agent comprising a salt of (i) a tertiary amine having the formula wherein R1, R2 and R3 are each, indepen-dently, saturated or unsaturated and wherein R1 is a long chain aliphatic group having from 12 to 22 carbon atoms and R2 and R3 are the same or different from each other and are selected from the group consisting of aliphatic groups containing from 1 to 22 carbon atoms, hydroxyalkyl groups of the formula -R4OH wherein R4 is an alkylene group having from 1 to 3 carbon atoms, and alkyl ether groups having the formula R5O(CnH2nO)m- wherein R5 is hydrogen or an alkyl or alkenyl group having from 1 to 20 carbon atoms, n is 2 or 3, and m is from 1 to 20; and (ii) a carboxylic acid having the formula wherein R6 is hydrogen, or an alkyl, alkenyl, aryl, alkaryl or aralkyl group having 1 to 22 carbon atoms, or a substituted alkyl, alkenyl, aryl, alkaryl, or aralkyl group having from 1 to 22 carbon atoms wherein the substituents are selected from the group consisting of halogen, carboxyl, and hydroxyl;

wherein said surfactant and said detergency builder are present in the form of detergent granules, and wherein said tertiary amine/car-boxylic acid salt is present in the form of separate discrete nodules having a particle size from about 0.05 to about 2 mm.

10. A fabric cleaning/conditioning composition according to claim 9 wherein said surfactant is present in an amount from about 1 % to about 50 % by weight of the compo-sition; said detergency builder is present in an amount from about 5 % to about 95 % by weight of the compo-sition; wherein said fabric conditioning agent is present in an amount from about 1 % to about 30 % by weight of the composition: and wherein R1 is an aliphatic alkyl chain having from 12 to 22 carbon atoms, R2 is an aliphatic alkyl chain having from 12 to 22 carbon atoms, and R3 is an aliphatic alkyl chain having from 1 to 3 carbon atoms, wherein R6 is a long chain, unsubsti-tuted alkyl or alkenyl group having from 11 to 17 carbon atoms; and wherein the melting point of said discrete nodules is from about 35 to about 115 °C.

11. A fabric cleaning/conditioning composition according to claim 10 wherein said surfactant is present in an amount from about 5 % to about 30 % by weight of the compo-sition; said detergency builder is present in an amount from about 10 % to about 60 % by weight of the compo-sition; wherein said fabric conditioning agent is present in an amount from about 3 % to about 20 % by weight of the composition; wherein the particle size of said nodules is from about 0.1 to about 1 mm. and wherein the melting point of said nodules is from about 35 to about 85 °C.

12. A fabric cleaning/conditioning composition according to claim 11 wherein said surfactant is present in an amount from about 10 % to about 20 % by weight of the compo-sition; said detergency builder is present in an amount from about 15 % to about 40 % by weight of the compo-sition; wherein said fabric conditioning agent is present in an amount from about 5 % to about 15 % by weight of the composition; and wherein R1 and R2 are each, independently, a saturated linear alkyl chain having from 16 to 18 carbon atoms; R3 is methyl; and R6 is a saturated linear alkyl chain having from 15 to 17 carbon atoms.

13. A fabric cleaning/conditioning composition according to claim 9 wherein there is also present from about 1 % to about 20 % smectite clay.

14. A fabric cleaning/conditioning composition according to either of claims 10 or 11 wherein there is also present from about 1 % to about 20 % smectite clay which has a cation exchange capacity of at least 60 meq./100 gm.
and is selected from the group consisting of sodium and calcium montmorillonites; lithium, sodium and magnesium saponites; and lithium, sodium and magnesium hector-ites.

15. A fabric cleaning/conditioning composition according to claim 12 wherein there is also present from about 2 % to about 12 % sodium montmorillonite.

16. A process for conditioning fabrics comprising the steps of:

(a) contacting the fabrics with an effective amount of a tertiary amine/carboxylic acid salt in the form of discrete nodules having a particle size from about 0.05 to about 2 mm., wherein said salt has been formed from the reaction of (i) a tertiary amine having the formula wherein R1, R2 and R3 are each, indepen-dently, saturated or unsaturated and wherein R1 is a long chain aliphatic group having from 12 to 22 carbon atoms and R2 and R3 are the same or different from each other and are selected from the group consisting of aliphatic groups containing from 1 to 22 carbon atoms, hydroxyalkyl groups of the formula -R4OH wherein R4 is an alkylene group having from 1 to 3 carbon atoms, and alkyl ether groups having the formula R5O(CnH2nO)m- wherein R5 is hydrogen or an alkyl or alkenyl group having from 1 to 20 carbon atoms, n is 2 or 3, and m is from 1 to 20; and (ii) a carboxylic acid having the formula wherein R6 is hydrogen, or an alkyl, alkenyl, aryl, alkaryl or aralkyl group having 1 to 22 carbon atoms, or a substituted alkyl, alkenyl, aryl, alkaryl, or aralkyl group having from 1 to 22 carbon atoms wherein the substituents are selected from the group consisting of halogen, carboxyl, and hydroxyl; and (b) subjecting the fabrics to a temperature within the range from about 40 °C. to about 95 °C .

17. A process according to claim 16 wherein the amine salt nodules are applied to the fabrics from an aqueous bath.

18. A process according to claim 16 wherein the fabrics are caused to tumble in relative motion to each other while being subjected to temperatures of 50-95 °C.

19. A process according to claim 18 wherein the amine salt nodules have a melting point from about 35 to about 85 °C. and wherein the nodules are applied to the fabrics from a laundry wash or rinse liquor.