CA1139505A - Detergent softener compositions - Google Patents
Detergent softener compositionsInfo
- Publication number
- CA1139505A CA1139505A CA000341521A CA341521A CA1139505A CA 1139505 A CA1139505 A CA 1139505A CA 000341521 A CA000341521 A CA 000341521A CA 341521 A CA341521 A CA 341521A CA 1139505 A CA1139505 A CA 1139505A
- Authority
- CA
- Canada
- Prior art keywords
- soap
- softener
- composition according
- composition
- spaghetti
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/143—Sulfonic acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/62—Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Abstract
DETERGENT SOFTENER COMPOSITIONS
ABSTRACT OF THE DISCLOSURE
Heavy duty detergent compositions, particularly for imparting improved softness and detersive effects to fabrics laundered therewith, said composition including in addition to conventional builder and principally anionic surfactant components, fatty acid soap, optionally, but preferably a minor quantity of cellulose ether, and cationic softener of the di-lower-di-higher alkyl quaternary ammonium and/or heterocyclic imide type, e.g., imidazolinium, the weight ratio of soap to softener being about 8:1 to 1:3 preferably 5:1 to 1:2 more preferably 3:2:2:3, e.g. about unity. The soap is preferably in the form of a spaghetti, flake, or other shape and is present in the product composition as substantially homogeneously dispersed, discrete particles. The cellulose ether may, preferably, be included in the soap component, or separately in the crutcher mixture of the surfactant, builder, and other components, or part of the cellulose ether may be in the soap and the remainder provided in the spray dried crutcher mix.
ABSTRACT OF THE DISCLOSURE
Heavy duty detergent compositions, particularly for imparting improved softness and detersive effects to fabrics laundered therewith, said composition including in addition to conventional builder and principally anionic surfactant components, fatty acid soap, optionally, but preferably a minor quantity of cellulose ether, and cationic softener of the di-lower-di-higher alkyl quaternary ammonium and/or heterocyclic imide type, e.g., imidazolinium, the weight ratio of soap to softener being about 8:1 to 1:3 preferably 5:1 to 1:2 more preferably 3:2:2:3, e.g. about unity. The soap is preferably in the form of a spaghetti, flake, or other shape and is present in the product composition as substantially homogeneously dispersed, discrete particles. The cellulose ether may, preferably, be included in the soap component, or separately in the crutcher mixture of the surfactant, builder, and other components, or part of the cellulose ether may be in the soap and the remainder provided in the spray dried crutcher mix.
Description
~3~
This invention relates to detergent compositions and in particular to detergent-softener compositions capable o~
imparting improved softness, detersive eEfects, soil antire-deposition and antistatic properties to fabrics treated therewith and particularly in a machine laundering process.
Compositions for simultaneously achieving detergency and an appreciable level of softness in the machine laundering of fabrics, and thus suitable for use in the wash cycle, are well-known and widely available commercially. The fugitive interaction between anionic surfactant, perhaps the most commonly used of the available types of surfactants, and cationic softeners, particularly those of the di-lower-di-higher alkyl quaternary ammonium type, is likewise well recognlzed in the patent literature. Such interaction often results in the formation ot` unsightly precipltates~which become en-trapped within or otherwise deposit upon the fahrlc being washed.
Discoloration or other aesthetically displeaslng effects are for the most part inevitable. The nee result is often a depletion in the effectlve amount af anionlc available for useful purposes since the loss of anionic is the primary consequence.
Remedial techniques heretofore proposed to abate the aforedescribed cationic-anionic problem though divergent as to ~ approach seem convergent as to result namely, less than satisfac-; tory. Thus, although~the most effective types of cationic quaternary ammonium softeners, as exemplified by the afore-mentioned di-higher alkyl type quats, such as di~stearyl dimethyl ammonium chloride~ can function in the wash cycle in the presence of anionic, builder, etc., the quantity needed to achleve
This invention relates to detergent compositions and in particular to detergent-softener compositions capable o~
imparting improved softness, detersive eEfects, soil antire-deposition and antistatic properties to fabrics treated therewith and particularly in a machine laundering process.
Compositions for simultaneously achieving detergency and an appreciable level of softness in the machine laundering of fabrics, and thus suitable for use in the wash cycle, are well-known and widely available commercially. The fugitive interaction between anionic surfactant, perhaps the most commonly used of the available types of surfactants, and cationic softeners, particularly those of the di-lower-di-higher alkyl quaternary ammonium type, is likewise well recognlzed in the patent literature. Such interaction often results in the formation ot` unsightly precipltates~which become en-trapped within or otherwise deposit upon the fahrlc being washed.
Discoloration or other aesthetically displeaslng effects are for the most part inevitable. The nee result is often a depletion in the effectlve amount af anionlc available for useful purposes since the loss of anionic is the primary consequence.
Remedial techniques heretofore proposed to abate the aforedescribed cationic-anionic problem though divergent as to ~ approach seem convergent as to result namely, less than satisfac-; tory. Thus, although~the most effective types of cationic quaternary ammonium softeners, as exemplified by the afore-mentioned di-higher alkyl type quats, such as di~stearyl dimethyl ammonium chloride~ can function in the wash cycle in the presence of anionic, builder, etc., the quantity needed to achleve
- 2 -.''~
~effective softening is usua]ly coterminous with amounts promotive of undeslred cationic-anionic interaction. As a gener~l rule, at least about twice as much cationic is required for softening ' as for antistat.
, In U.S. 3,325,414, dealing primarily with detergents of i controlled foam or sudsing capability, the cationic-anionic proble n ` and attendan~ detrimental effects are discussed in detail. The patent additionally points out that certain quaternary ammonium .. compounds, among the class of cationic agents, are generally unstable when heated and when in contact with alkaline builders, the instability being manufactured by the development o~ strong amine odors and undesirable color. The cornpositions of the patent ; are limited to the use of quaternary ammonium halides having but one higher alkyl group, the given s~ructural formula for the cationic being correspondingly limited. Cationics o this type - are markedly inferlor to the di-higher alkyl types at least insoa , as fabric softening activity is concerned.
!
Other prior art teachings at least tactically avoid the us~
, of cationic softeners altogether proposing the use of, ~or example ; 20` 'j anionic materials as softening agents. U.S. 3,676,338 is represen .
- 1 tative, this patent teaching the use of anionic softener referred 1 to as "branched-chain carboxylic acids", as fabric softener.~
. . .
Presumably, anionic detergent would be stable in the presence of . the anionic sotener.
l As the foregoing demonstrates, the remedies proposed . necessitate the discarding o softeners and principally those of :
the di-higher-di-lower alkyl quaternary ammonium salt and cyclic imide types, these having been determined by experience to be _ among the most effective softeners thus far developed in the ~rt.
. .
Ii `
~ -3-The present invention provides stable detergent softener composi-tions capable of providing improved softness, detergency, antistatic and soil antiredeposition properties to fabrics treated therewith in a laundering process comprising by weight from about 5 to 40% preferably 9 to ~0% and most preferably 9 to 30% of water soluble, non-soap, organic surfactant at least about 90% thereof being of the anionic type, from about 10 to 60% of water soluble, neutral to alkaline builder salt, from about 2 to 20% water soluble or dispersible fatty acid soap in spaghetti-like or other shaped, discrete form, from about 2 to 20% of cationic softener selected from ~a) aliphatic, di-(lower) Cl - C4 alkyl, di-(higher) C14 - C24 alkyl quaternary ammonium salts, (b) heterocyclic compounds, and mixtures of ~a) and (b), the weight ratio of soap to softener being from about 8:1 to 1:3 preferably 5:1 to 1:2 and more preferably 3:~ to 2:3, the per-cent concentration of anionic surfac-tant being at least about 1.5 x + 5, x representing the per-cent concentration of softener, wherein the soap is substantially homogeneously dispersed in said composition preferably as discrete particles.
Where optional, but preferred, cellulose ether is used, it may be combined with the soap phase wherein the soap constitutes at least about 50%, preferably above about 70%, more preferably above 80% and most preferably above 90% of the soap-cellulose ether mixture, whether combined with soap or added separately in the spray dried crutcher mixture or when used in both forms; the total cellulose ether content will vary from about 0.1% to about 10%, preferably 0.2% to 5%, and more preferably 0.2% to about 2%, all by weight based on the weight of the detergent composition.
In certain other aspects, the invention includes both the processes of formulating and using the aforedescribed compositions.
In particular, the invention provides a process for washing fabrics comprising contacting said fabrics in an aqueous medium at a temperature of from about 80 to 170F with sufficient of the composition defined above to provide a ratio of from 1.5 to 8.0 g of softener per 3500 g of fabric.
Of primary importance in the present invention is the conjoint use of the fa-tty acid component and the quaternary softener within the parameters given. As previously mentioned, ~3~"5(~i the obtention of truly effective fabric softening with cationic softener, an-ionic detergent-based compositions required high concentration levels of sof-tener, this being to -the detriment of detergency, i.e., cleaning or whiten-ing. Thus, increased cationic concentration though providing some improvement in softness, nevertheless leads to a visually discernible loss in fabric whit-ening due to cationic-anionic interaction, the latter being particularly acute with high softening cationic of di-higher-di-lower alkyl quaternary ammonium salt and/or heterocyclic imide types.
Surprisingly, it is found in the present invention that the use of approximately equal quantities of cationic and soap or within a 2:3 to 3:2 mutual weight ratio thereof, leads to even more significantly enhanced im-provement in fabric softening despite the use of relatively low softener con-centrations. Moreover, increase of the softener concentration well beyond the limits previously imposed due to cationic-anionic interaction has no adverse effect on cleaning and whitening and produces yet greater softening effects.
~ithout intending to be bound by theory, it appears that ~he soap significant-ly enhances the softness of low cationic concentrations, which are at least adequate for antistat, without adversely affecting cleaning and whitening.
As will be understood, the softening capabilities of individual com-ponents are not additive when combined and in fact the cumulative effect maywell be a net softness value less than that assigned for the most effective softening agent present in the combination. Thus, a plurality of poor sof-teners will most liXely provide an equally poor net softening result. Softn~ss is usually measured on a scale of 1 to 10 the higher values connoting in-creased softness.
If one were to combine equally a softener having a scale softness rating of 8, corresponding to moderate or effective softening, with a softener having a rating of 2, indicative of ~j :
inferior softening, the net combined softening effect would not be additive to give a scale rating of 10, indicative of excellent 'isoftness. More than likely, the resultant softening rating woul~
lie somewhere between the aforementioned 8 and 2 ratings indicatin , their respective softening effects to be mutually subtractive rath r than additive. In thls context, it is indeed surprising to find that the soap component herein, a material not having significant softening capabilities, actually improves, substantially, the softening effects of high softening cationics to the extent that cationic softener concentration normally considered to be effectiv for antistat purposes only, are likewise effective for producing excellent softening. In addition, the absence of any deleterious effects upon the detersive function of the anionic component with increased concentration of cationic enables the attainment of even ]5 ~,rcater soften-ing effects, most notable here being the quality of fluffiness. ~his in turn correspondingly maximizes the antistat f~ ction of the cationic softener and particularly as regards di-higher-di-lower alkyl quaternary ammonium salts.
! Further benefit enabled by the invention relates to the soil antiredeposition function of cellulose ether when used with ~ soap as a carrier for the cellulose ether. The soap appears to - improve the wettability of the cellulose ether rendering it more soluble or dispersible in the aqueous washing medium. Similar improvement characterizes any cellulose ether separately added to the composition, i.e., apart from that used in the soap carrier, for soil antiredeposition purposes. It further appears that the ; stability of the cationic softener in the presence of alkaline to ! neutral builder salts is enhanced in the presence of the soap or .soap-cellulose ether combination.
Fatty acid soaps useful herein include generally those derived from natural or synthetic fatty acids having from 10 to 30 carbons in the alkyl chain. Preferred are the alkali metals, e.g.
sodium and/or potassium soaps oE C10 - C24 saturated fatty acids, a particularly preferred class being the sodium and/or potassium s~lts of fatty acid mixtures derived from coconut oil and tallow, ' e.g. the combination of sodium coconut soap and potassium tallow soap in the mutual proportions respectively of 15/85. As is known as the molecular weight of the fatty acid is increased, the more pronounced becomes its foam inhibiting capacity. Thus, fatty acid ; selection herein can be made having reference to the foam level desired with the product composition. In general, effective resul :B
obtain wherein at least about 50% of the fatty acid soap is of the C10 - C18 variety. Other fatty acid soaps useful herein include those derived from oils of palm groundnut, hardened fish, e.g. cod liver and shark, seal, perilla, linseed, candlenut, hempseed, waln ~t, poppyseed, sunflower, maize, rapeseed, mustardseed, apricot ke~nel lS almond, cas~or and olive, etc. Other fatty acid soaps includ~
those ~erived from the following acids: oleic, linoleic, palmitvl ic, palmitic linolenic, ricinoleic, capric myristic and the like, othe useful combinations thereof including, without necessary limitatio , ~ 80/20 capric-lauric, 80/20 capric-myristic, 50/50 oleic-capric, ;90/10 capric-palmitic and the like. ~
. - Cationic sofeeners useful herein are known materials and . are of the high-softening type. Included are the NlN-di-(higher) C14- C24, NlM-di(lower) Cl - C4 alkyl quaternary ammonium salts I with water solubilizing anions such as halide, e.g. chloride, bromide and iodide; sulfate, methosulfate and the like and the heterocyclic imides such as the imidaæolinium.
For convenience, the aliphatic quaternary ammonium salts~
may be structurally defined as follows:
. ' 11 ~ . .
R I _R X~
', ~ ` ' ' , ; -7-, wherein R and Rl represent alkyl o;E 14 to 24 and preferably 14 to 22 carbon atoms; R2 and R3 represent lower alkyl of ~' 1 to 4 and preEerably I to 3 carbon atoms, X represents an anion capable of imparting water solubility or dispersibility includi.ng the aforementioned chloride, bromide, iodide, sulfate and methosulfate. Particularly preferred species of aliphatic i quats include:
distearyl dimethylammonium chloride di-hydrogenated tallow dimethyl ammonium chloride di tallow dimethyl ammonium chloride distearyl dimethyl ammonium methyl sulfate - di-hydrogenated tallow dimethyl ammonium methyl sulfate.
Heterocyclic imide softeners of the imidazolinium type may als--, for convenience,be structurally de~ined as follows:
.. , . _ +
/ \ ., X-i P'4 CH2CH2NH C R6 wherein R4 is lower alkyl of 1 to 4 and preferably 1 to 3 carbons;
R5 and R6 are each substantially linear higher alkyl groups of about 13 to 23 and preferably 13 to 19 carbons and X has the a~oredefined significance. Particularly preferred species of imidazoliniums include:
methyl-l-tallow amido ethyl-2-tallow imidazolinium methyl sulfate; available commercially from Sherex Chemical Co. under ~he trademark VarisoftR 475 as a liquid, 75% active ingredient in isopropanol solvent methyl-l-oleyl amido ethyl-2-ol~yl imidazolinium methyl sulfate; available commercially from Sherex Chemical Co. under the trademark varisoftR 3690, 75% active ingredient in isopropanol solvent.
'~:'..,,`
~L~3~
The concentration o soap and softener is from about 2 to 20% each based on the product deter~ent composition. For " ~est results, th~ weight ratio of soap-softener is from about 2:3 to 3:2 witll values approximating Ullity being particularly S preferred. Departures from the aforestated range are not recommended since loss of softener and/or detersive effects may be severe.
Tt is important in one aspect of the presentinvention whe the soap and cellulose ether are combined that the soap be used i with a minor quantity of cellulose ether i.e, no more than 45%
of the latter and preferably about 5-10% based on the total soap-cellulose ether admixture for incorporation into the final deter-gent composition, usually by post blending of both soap and catio ic with dried detergent. Cellulose ethers function, as is known, as soil antiredeposition agents preferred species for use herein including, without necessary l~mitation, hydroxy butyl methyl cellulose, hydroxy ethyl methyl cellulose, carboxymethyl cellulos~
(CMC) available technical grade usually haYing 0.7 mole of carboxymethyl group per anhydroglucose unit; sodium carboxymethyl hydroxyethyl cellulose (CMHEC); sodium carboxymethylethyl-cellulo~ e :, (CMEC) usually having 0.1 mole of carboxymethyl group and 1.0 mole of ethy~l group per anhydroglucose unit and hydroxybutyl methyl cellulose available commercially under the tradename METHOCELR as well as mixtures o~ the foregoing, The soap and cellulose ether when combined may first mixed in the desired amounts to :Eorm a substantially homogeneous mass which can be worked, according to well known technique, until it is sufficientl Y
` "doughy" or plastic to be in suitable form for, preferably, extrusion or other process e.g., pelleting, granulation, stamping and pressing. Working may be effected, for example, by roll milling, although this is not essential followed by extrusion _9 in a conventional soap plodder with the desired type of extrusion head. The latter is selected in accordance with the shape, i.e. geometric form, desired in the extrudate. In the present invention, extrusion in the form of spaghetti or noodles is particularly preferred. Other shaped forms such as flakes, tablets, pellets, ribbons, threads and the like are suitable altern-atives. Special extruders for the foregoi:ng purposes are well known in the art and include for example Elanco models EXD-60; EXDC-100; EX-130 and EXD-180~ a Buhler extruder and the like. Generally~ the spaghetti extrudate is a form-retaining mass, i.e. semi-solid and essentially non-tacky at room tem-perature requiring in most cases no further treatment such as water removal.If necessary, the latter can be effected by simple drying techniques. The spaghetti should have an average length of from about 2 to 20 mm with about 95% thereof within a tolerance of 0.5 to 20 mm and an average diameter or width of from about 0.2 to 2.0 mm with a range of 0.4 to 0.8 mm being pre-ferred. The bulk density of the spaghetti will usually, having reference to the type of fatty acid soap and cellulose ether used be from about 0.2 to 0.8 g/cc3. Flakes will measure about 4 mm in length and breadth and 0.2 mm in thickness~ pellets have a cross section of about 2.5 mm while tablets have a cross section of 2.5 mm and a thickness of 2.5 mm. Where soap is used absent the cellulose ether, the foregoing techniques and conditions are equally applicable except for the admixing of the two ingredients to form a homogeneous mass.
Water dispersibility of the shaped extrudate is excellent; where the fatty acid soap-cellulose ether combination is used the soap appears to function to increase the wettability of the cellulose ether e.g. carboxy-methyl cellulose and methyl cellulose~ materially enhancing its dispersibil-ity and/or solubility in a fabric washing medium containing the ultimate product composition with concomitant enhancement of antiredeposition effects.
Cellulose ethers, as is known, are commonly used as soil. anti-redeposition agents; in the present invention, their performance as such as optimized. Extrlls:ion methods particularly relevant to the foregoing are described, for example in U.S. 3,824,18 and British patent 1,204,123; also relevant in this regard is U.S. 3,726,813.
In accordance with pre:Eerred embodiments, the soap spaghetl i (with or without combined cellulose ether) as well as cationic 10. softener are dry blended, by post addition, with dried detergent in particulate form such as granules, beads and the like, the detergent having been prepared as is customary in the art, e.g., spray drying a crutcher mix of surfactant, builder filler, etc.
However, it is within the scope of the invention to add part or all of the soap-spaghetti to the crutcher mix since this pro-cedure likewise results in the desired dispersion of soap spaghetti as discrete particles.
In any event, it is advisable to maintain physical separat: on of the soap and cationic softener and thus inclusion of the softener in the soap spaghetti should be avoided. The afore-described post-blending expedient usually insures against any appreciable, inadvertent contacting of soap and softener since these are added as separate components to the detergent in dry form. Though the soap spaghetti be added to the crutcher, cationic softener nevertheles~s is post-added as explained, Although surfactants of conventional type can be used herein, it ` is preferred that at least about 90% and preferably at least about 95% oE the total surfactant or detergent be of the anionic type, these materials being particularly b~neficial in heavy duty detergent for fabric washing. ~nionics for use herein generally include the water soluble salts of organic reaction products ! having in their molecular structure an anionic solubilizing group such as SO4H, SO3H, COOH and PO4H and an alkyl or alkyl group having about 8 to 22 carbons in the alkyl group or moiety, iL.~ Ic~ r~ r~ iOllic ~ r~ saltY h~lvin~ lk~l substituents of 8 ~o 22 cal-bon atoms such as: water soluble sulfated and sulfonated anionic alkali metal and alkaline earth mctal detergent salts containing a hydrophobic higher alkyl moi~ty, such as s~]~s of hi~her alkyl mono-or poly-nuclear aryl sulfonates having ~rom about 8 to 18 carbon atoms ln the alkyl group which may have a straight preferred or branched chain - structure, preferred species including; wi~hout necessary limita-tion: sodium linear tridecylbenzene sulfonate, sodium linear dodecyl benzene sulfonate sodium linear decyl benzene sulfonate, lithium or ~otassium pentapropylene benzene sulfonate; alkali metal salts of sulfated condensation prod-ucts of ethylene oxide, e.~. containing 3 to 20 and preferably 3 to 10 moles of ethylene oxide, with aliphatic alcohols containing 8 to 18 carbon atoms or with alkyl phenols having alkyl groups containing 6 to 18 car,,on atoms, e.g., sodium nonyl phenol pentaethoxamer sulfate and sodi I
lauryl alcohol triethoxamer sulfate; alkali metal salts of satura~ed alcohols containing from about 8 to 18 carbon atoms, e.g. sodium lauryl sulfate and sodilum stearyl sulfate; alkali metal salts of higher fatty acid esters of low molecular weight alkylol sulfonic acid; e.g. fatty acid esters of the sodium salt of isethionic acid;
fatty ethanolamide sulfates; fatty acid amides of amino alkyl sulfonic acids, e.~. lauric acid amine o~ taurine; alkali metal salts of hydroxy alkane sulfonic acids having 8 to 18 carbon atom~
in the alkyl group, e.g., hexadecyl, alphahydro~y sodium sulfonat~.
The anionic or mixture thereof is used in the form of their alkali or alkaline earth metal salts. The anionic is preferably of the non-soap type, it being preferred that the soap component be utilized as taught herein. However, minor amou~ts of soap, e.g.
up to about 35% and preferably 20% based on total anionic can be ~
separately added, for example, to the crutcher mix. ~he concentra-tion of non-soap anionic should be selected so as to provide an excess with respect to cationic-softener according to the empirica 1 relationship % concentration ~ 1.5 x + 5 anioni c wl)el-ein x is the per cent collcelltLa~iol~ of cationic softeller.
This assures the minimum excess of anionic necessary for optimum overall de~ergency, so:Etening, e~c. performance in ~he product composition.
Minor amounts of ottler types of detergents can be included along with the anionic, their sum in any case not exceeding about 10% and preferably about 2-5~/~ of total detergent, i~e., such othe~
detergent plus non-soap anionic. Useful here are the nonionic surface active agents which contain an organic hydrophobic group and a hydrophilic group which is a reaction product of a solubili-zing group such as carboxylate, hydroxyl, amido or amino with ethylene oxide or with the polyhydration product thereof, poly~
ethylene glycol. Included are the condensation products of C8 to C30 fatty alcohols such as tridecyl alcohol with 3 to 100 moles e~hylene oxide; C16 to C18 alcohol with 11 to 50 moles ethylene oxide; ethylene oxide adducts with monoesters o~ polyhy~ric e.g.
hexahydric alcohol; condensation products o~ polypropylene glycol with 3 to 100 moles ethylene oxide; the condensation products of alkyl (C6 to C20 straight or branded chain) phenols with 3 to 100 20 ~ moles ethylene oxide and the like.
Suitable amphoteric detergents generally include those containing both an anionic group and a cationic group and a hydrophobic organic group which is preferabl.y a higher aliphatic radical of 10 to 20 carbon atoms; examples include the N-long cllain alkyl aminocarboxylic acids and the N-long chain alkyl iminodicarboxylic acids such as described in U.S. 3,824,189.
The compositions herein preEerably include water soluble alkaline to neutral builder salt in amounts of from about 10 to 60% by weight o~ total composition, Use~ul herein are the organic and inorganic builders including the alkali metal and alkaline earth metal phosphates, particularly the condensed phosphates such as the pyrophospllates or tripolyphosphates, silicates, borates, , -:~3~5 carbonates, bicarbonates and the like. Species thereof include sodium tri-polyphosphate, trisodium phosphate, tetrasodium pyrophosphate, sodium acid pyrophosphate, sodium monobasic phosphate, sodium dibasic phosphate, sodium hexametaphosphate; alkali metal silicates such as sodium metasilicate, sodium silicates: Na20/SiO2 of 1.6:1 to 3.2:1, sodium carbonate, sodium sulfate, borax ~sodium tetraborate) ethylene diamine tetraacetic acid tetrasodium salt, trisodium nitrilotriacetate and the like and mixtures of the foregoing.
Builder salt may be selected so as to provide either phosphate-containing or phosphate-free detergents. As to the latter embodiments, sodium carbonate is particularly effective. Another material found to provide good detergency effects is metakaolin which is generally produced by heating kaolinite lat-tice to drive off water producing a material which is substantially amorphous by x-ray examination but which retains some of the structural order of the kaolinite. Discussions of kaolin and metakaolin are found in United States Patent 4,075,280 columns 3 and 4 and Grimshaw, "The Chemistry of Physics of Clays and Allied Ceramic Materials", ~4th ed., Wiley-Interscience), pages 723-727. The metakaolin also appears to have softening utility. As to the latter, the most effective metakaolins appear to be those which behave best in the reaction with sodium hydroxide to form zeolite 4A as described in United States Patent 3,114,603 which refers to such materials as "reactive kaolin". As explained in the referenced sources, metakaolin is an alumino-silicate. The metakaolin and/or a zeolite is included in about the same amounts as the builder salt, and preferably supplemental thereto, e.g. zeo-lite-silicate in a ratio of 6:1. A particularly useful form of the meta-kaolin is that available commercially as Satintone No. 2.
Preferred optional ingredients useful herein include perfume such as Genie per~ume; optical brigh~eners and bluing a~ents which may be d~es or pigments, suitable materials in this regard including stilbene and Tinopal 5BM brighteners and particu- .
larly in combination and Direct Brilliant Sky Blue 6B, Solophenyl Violet 4BL, Cibacete Brilliant Blue RBL and Cibacete Violet B, Polar Brilliant Blue RAW and Calcocid Blue 2G bluing agents. The brightener may be included in amounts ran~ing up to about 1%
of the total composition while bluing agents may range up to abou :
.1% preferably up to about .01% of total composition. Bluing agent e.g. Polar Brilliant Blue may be included in the soap spaghetti. In either case, the amount need only be minimal to be effective.
Other ingredients of optimal significance include bleachin~
agents which may be of the oxygen or chlorine liberating type;
oxygen bleaches include sodium and potassium perborate, potassium monopersulfate and the like, while chlorine bleaches are typified by sodium hypochlorite, potassium dichloroisocyanurate trichlorn-isocyanuric acid and the like. The latter chlorine-liberating bleaches are representative of the bro~d class of water soluble, organic, dry solid bleaches known as the N-chloro imides includin~ ;
. their alkali metal salts. These cyclic imides have from about 4 to 6 member in the ring and are described in detail in U.S. Paten~
~effective softening is usua]ly coterminous with amounts promotive of undeslred cationic-anionic interaction. As a gener~l rule, at least about twice as much cationic is required for softening ' as for antistat.
, In U.S. 3,325,414, dealing primarily with detergents of i controlled foam or sudsing capability, the cationic-anionic proble n ` and attendan~ detrimental effects are discussed in detail. The patent additionally points out that certain quaternary ammonium .. compounds, among the class of cationic agents, are generally unstable when heated and when in contact with alkaline builders, the instability being manufactured by the development o~ strong amine odors and undesirable color. The cornpositions of the patent ; are limited to the use of quaternary ammonium halides having but one higher alkyl group, the given s~ructural formula for the cationic being correspondingly limited. Cationics o this type - are markedly inferlor to the di-higher alkyl types at least insoa , as fabric softening activity is concerned.
!
Other prior art teachings at least tactically avoid the us~
, of cationic softeners altogether proposing the use of, ~or example ; 20` 'j anionic materials as softening agents. U.S. 3,676,338 is represen .
- 1 tative, this patent teaching the use of anionic softener referred 1 to as "branched-chain carboxylic acids", as fabric softener.~
. . .
Presumably, anionic detergent would be stable in the presence of . the anionic sotener.
l As the foregoing demonstrates, the remedies proposed . necessitate the discarding o softeners and principally those of :
the di-higher-di-lower alkyl quaternary ammonium salt and cyclic imide types, these having been determined by experience to be _ among the most effective softeners thus far developed in the ~rt.
. .
Ii `
~ -3-The present invention provides stable detergent softener composi-tions capable of providing improved softness, detergency, antistatic and soil antiredeposition properties to fabrics treated therewith in a laundering process comprising by weight from about 5 to 40% preferably 9 to ~0% and most preferably 9 to 30% of water soluble, non-soap, organic surfactant at least about 90% thereof being of the anionic type, from about 10 to 60% of water soluble, neutral to alkaline builder salt, from about 2 to 20% water soluble or dispersible fatty acid soap in spaghetti-like or other shaped, discrete form, from about 2 to 20% of cationic softener selected from ~a) aliphatic, di-(lower) Cl - C4 alkyl, di-(higher) C14 - C24 alkyl quaternary ammonium salts, (b) heterocyclic compounds, and mixtures of ~a) and (b), the weight ratio of soap to softener being from about 8:1 to 1:3 preferably 5:1 to 1:2 and more preferably 3:~ to 2:3, the per-cent concentration of anionic surfac-tant being at least about 1.5 x + 5, x representing the per-cent concentration of softener, wherein the soap is substantially homogeneously dispersed in said composition preferably as discrete particles.
Where optional, but preferred, cellulose ether is used, it may be combined with the soap phase wherein the soap constitutes at least about 50%, preferably above about 70%, more preferably above 80% and most preferably above 90% of the soap-cellulose ether mixture, whether combined with soap or added separately in the spray dried crutcher mixture or when used in both forms; the total cellulose ether content will vary from about 0.1% to about 10%, preferably 0.2% to 5%, and more preferably 0.2% to about 2%, all by weight based on the weight of the detergent composition.
In certain other aspects, the invention includes both the processes of formulating and using the aforedescribed compositions.
In particular, the invention provides a process for washing fabrics comprising contacting said fabrics in an aqueous medium at a temperature of from about 80 to 170F with sufficient of the composition defined above to provide a ratio of from 1.5 to 8.0 g of softener per 3500 g of fabric.
Of primary importance in the present invention is the conjoint use of the fa-tty acid component and the quaternary softener within the parameters given. As previously mentioned, ~3~"5(~i the obtention of truly effective fabric softening with cationic softener, an-ionic detergent-based compositions required high concentration levels of sof-tener, this being to -the detriment of detergency, i.e., cleaning or whiten-ing. Thus, increased cationic concentration though providing some improvement in softness, nevertheless leads to a visually discernible loss in fabric whit-ening due to cationic-anionic interaction, the latter being particularly acute with high softening cationic of di-higher-di-lower alkyl quaternary ammonium salt and/or heterocyclic imide types.
Surprisingly, it is found in the present invention that the use of approximately equal quantities of cationic and soap or within a 2:3 to 3:2 mutual weight ratio thereof, leads to even more significantly enhanced im-provement in fabric softening despite the use of relatively low softener con-centrations. Moreover, increase of the softener concentration well beyond the limits previously imposed due to cationic-anionic interaction has no adverse effect on cleaning and whitening and produces yet greater softening effects.
~ithout intending to be bound by theory, it appears that ~he soap significant-ly enhances the softness of low cationic concentrations, which are at least adequate for antistat, without adversely affecting cleaning and whitening.
As will be understood, the softening capabilities of individual com-ponents are not additive when combined and in fact the cumulative effect maywell be a net softness value less than that assigned for the most effective softening agent present in the combination. Thus, a plurality of poor sof-teners will most liXely provide an equally poor net softening result. Softn~ss is usually measured on a scale of 1 to 10 the higher values connoting in-creased softness.
If one were to combine equally a softener having a scale softness rating of 8, corresponding to moderate or effective softening, with a softener having a rating of 2, indicative of ~j :
inferior softening, the net combined softening effect would not be additive to give a scale rating of 10, indicative of excellent 'isoftness. More than likely, the resultant softening rating woul~
lie somewhere between the aforementioned 8 and 2 ratings indicatin , their respective softening effects to be mutually subtractive rath r than additive. In thls context, it is indeed surprising to find that the soap component herein, a material not having significant softening capabilities, actually improves, substantially, the softening effects of high softening cationics to the extent that cationic softener concentration normally considered to be effectiv for antistat purposes only, are likewise effective for producing excellent softening. In addition, the absence of any deleterious effects upon the detersive function of the anionic component with increased concentration of cationic enables the attainment of even ]5 ~,rcater soften-ing effects, most notable here being the quality of fluffiness. ~his in turn correspondingly maximizes the antistat f~ ction of the cationic softener and particularly as regards di-higher-di-lower alkyl quaternary ammonium salts.
! Further benefit enabled by the invention relates to the soil antiredeposition function of cellulose ether when used with ~ soap as a carrier for the cellulose ether. The soap appears to - improve the wettability of the cellulose ether rendering it more soluble or dispersible in the aqueous washing medium. Similar improvement characterizes any cellulose ether separately added to the composition, i.e., apart from that used in the soap carrier, for soil antiredeposition purposes. It further appears that the ; stability of the cationic softener in the presence of alkaline to ! neutral builder salts is enhanced in the presence of the soap or .soap-cellulose ether combination.
Fatty acid soaps useful herein include generally those derived from natural or synthetic fatty acids having from 10 to 30 carbons in the alkyl chain. Preferred are the alkali metals, e.g.
sodium and/or potassium soaps oE C10 - C24 saturated fatty acids, a particularly preferred class being the sodium and/or potassium s~lts of fatty acid mixtures derived from coconut oil and tallow, ' e.g. the combination of sodium coconut soap and potassium tallow soap in the mutual proportions respectively of 15/85. As is known as the molecular weight of the fatty acid is increased, the more pronounced becomes its foam inhibiting capacity. Thus, fatty acid ; selection herein can be made having reference to the foam level desired with the product composition. In general, effective resul :B
obtain wherein at least about 50% of the fatty acid soap is of the C10 - C18 variety. Other fatty acid soaps useful herein include those derived from oils of palm groundnut, hardened fish, e.g. cod liver and shark, seal, perilla, linseed, candlenut, hempseed, waln ~t, poppyseed, sunflower, maize, rapeseed, mustardseed, apricot ke~nel lS almond, cas~or and olive, etc. Other fatty acid soaps includ~
those ~erived from the following acids: oleic, linoleic, palmitvl ic, palmitic linolenic, ricinoleic, capric myristic and the like, othe useful combinations thereof including, without necessary limitatio , ~ 80/20 capric-lauric, 80/20 capric-myristic, 50/50 oleic-capric, ;90/10 capric-palmitic and the like. ~
. - Cationic sofeeners useful herein are known materials and . are of the high-softening type. Included are the NlN-di-(higher) C14- C24, NlM-di(lower) Cl - C4 alkyl quaternary ammonium salts I with water solubilizing anions such as halide, e.g. chloride, bromide and iodide; sulfate, methosulfate and the like and the heterocyclic imides such as the imidaæolinium.
For convenience, the aliphatic quaternary ammonium salts~
may be structurally defined as follows:
. ' 11 ~ . .
R I _R X~
', ~ ` ' ' , ; -7-, wherein R and Rl represent alkyl o;E 14 to 24 and preferably 14 to 22 carbon atoms; R2 and R3 represent lower alkyl of ~' 1 to 4 and preEerably I to 3 carbon atoms, X represents an anion capable of imparting water solubility or dispersibility includi.ng the aforementioned chloride, bromide, iodide, sulfate and methosulfate. Particularly preferred species of aliphatic i quats include:
distearyl dimethylammonium chloride di-hydrogenated tallow dimethyl ammonium chloride di tallow dimethyl ammonium chloride distearyl dimethyl ammonium methyl sulfate - di-hydrogenated tallow dimethyl ammonium methyl sulfate.
Heterocyclic imide softeners of the imidazolinium type may als--, for convenience,be structurally de~ined as follows:
.. , . _ +
/ \ ., X-i P'4 CH2CH2NH C R6 wherein R4 is lower alkyl of 1 to 4 and preferably 1 to 3 carbons;
R5 and R6 are each substantially linear higher alkyl groups of about 13 to 23 and preferably 13 to 19 carbons and X has the a~oredefined significance. Particularly preferred species of imidazoliniums include:
methyl-l-tallow amido ethyl-2-tallow imidazolinium methyl sulfate; available commercially from Sherex Chemical Co. under ~he trademark VarisoftR 475 as a liquid, 75% active ingredient in isopropanol solvent methyl-l-oleyl amido ethyl-2-ol~yl imidazolinium methyl sulfate; available commercially from Sherex Chemical Co. under the trademark varisoftR 3690, 75% active ingredient in isopropanol solvent.
'~:'..,,`
~L~3~
The concentration o soap and softener is from about 2 to 20% each based on the product deter~ent composition. For " ~est results, th~ weight ratio of soap-softener is from about 2:3 to 3:2 witll values approximating Ullity being particularly S preferred. Departures from the aforestated range are not recommended since loss of softener and/or detersive effects may be severe.
Tt is important in one aspect of the presentinvention whe the soap and cellulose ether are combined that the soap be used i with a minor quantity of cellulose ether i.e, no more than 45%
of the latter and preferably about 5-10% based on the total soap-cellulose ether admixture for incorporation into the final deter-gent composition, usually by post blending of both soap and catio ic with dried detergent. Cellulose ethers function, as is known, as soil antiredeposition agents preferred species for use herein including, without necessary l~mitation, hydroxy butyl methyl cellulose, hydroxy ethyl methyl cellulose, carboxymethyl cellulos~
(CMC) available technical grade usually haYing 0.7 mole of carboxymethyl group per anhydroglucose unit; sodium carboxymethyl hydroxyethyl cellulose (CMHEC); sodium carboxymethylethyl-cellulo~ e :, (CMEC) usually having 0.1 mole of carboxymethyl group and 1.0 mole of ethy~l group per anhydroglucose unit and hydroxybutyl methyl cellulose available commercially under the tradename METHOCELR as well as mixtures o~ the foregoing, The soap and cellulose ether when combined may first mixed in the desired amounts to :Eorm a substantially homogeneous mass which can be worked, according to well known technique, until it is sufficientl Y
` "doughy" or plastic to be in suitable form for, preferably, extrusion or other process e.g., pelleting, granulation, stamping and pressing. Working may be effected, for example, by roll milling, although this is not essential followed by extrusion _9 in a conventional soap plodder with the desired type of extrusion head. The latter is selected in accordance with the shape, i.e. geometric form, desired in the extrudate. In the present invention, extrusion in the form of spaghetti or noodles is particularly preferred. Other shaped forms such as flakes, tablets, pellets, ribbons, threads and the like are suitable altern-atives. Special extruders for the foregoi:ng purposes are well known in the art and include for example Elanco models EXD-60; EXDC-100; EX-130 and EXD-180~ a Buhler extruder and the like. Generally~ the spaghetti extrudate is a form-retaining mass, i.e. semi-solid and essentially non-tacky at room tem-perature requiring in most cases no further treatment such as water removal.If necessary, the latter can be effected by simple drying techniques. The spaghetti should have an average length of from about 2 to 20 mm with about 95% thereof within a tolerance of 0.5 to 20 mm and an average diameter or width of from about 0.2 to 2.0 mm with a range of 0.4 to 0.8 mm being pre-ferred. The bulk density of the spaghetti will usually, having reference to the type of fatty acid soap and cellulose ether used be from about 0.2 to 0.8 g/cc3. Flakes will measure about 4 mm in length and breadth and 0.2 mm in thickness~ pellets have a cross section of about 2.5 mm while tablets have a cross section of 2.5 mm and a thickness of 2.5 mm. Where soap is used absent the cellulose ether, the foregoing techniques and conditions are equally applicable except for the admixing of the two ingredients to form a homogeneous mass.
Water dispersibility of the shaped extrudate is excellent; where the fatty acid soap-cellulose ether combination is used the soap appears to function to increase the wettability of the cellulose ether e.g. carboxy-methyl cellulose and methyl cellulose~ materially enhancing its dispersibil-ity and/or solubility in a fabric washing medium containing the ultimate product composition with concomitant enhancement of antiredeposition effects.
Cellulose ethers, as is known, are commonly used as soil. anti-redeposition agents; in the present invention, their performance as such as optimized. Extrlls:ion methods particularly relevant to the foregoing are described, for example in U.S. 3,824,18 and British patent 1,204,123; also relevant in this regard is U.S. 3,726,813.
In accordance with pre:Eerred embodiments, the soap spaghetl i (with or without combined cellulose ether) as well as cationic 10. softener are dry blended, by post addition, with dried detergent in particulate form such as granules, beads and the like, the detergent having been prepared as is customary in the art, e.g., spray drying a crutcher mix of surfactant, builder filler, etc.
However, it is within the scope of the invention to add part or all of the soap-spaghetti to the crutcher mix since this pro-cedure likewise results in the desired dispersion of soap spaghetti as discrete particles.
In any event, it is advisable to maintain physical separat: on of the soap and cationic softener and thus inclusion of the softener in the soap spaghetti should be avoided. The afore-described post-blending expedient usually insures against any appreciable, inadvertent contacting of soap and softener since these are added as separate components to the detergent in dry form. Though the soap spaghetti be added to the crutcher, cationic softener nevertheles~s is post-added as explained, Although surfactants of conventional type can be used herein, it ` is preferred that at least about 90% and preferably at least about 95% oE the total surfactant or detergent be of the anionic type, these materials being particularly b~neficial in heavy duty detergent for fabric washing. ~nionics for use herein generally include the water soluble salts of organic reaction products ! having in their molecular structure an anionic solubilizing group such as SO4H, SO3H, COOH and PO4H and an alkyl or alkyl group having about 8 to 22 carbons in the alkyl group or moiety, iL.~ Ic~ r~ r~ iOllic ~ r~ saltY h~lvin~ lk~l substituents of 8 ~o 22 cal-bon atoms such as: water soluble sulfated and sulfonated anionic alkali metal and alkaline earth mctal detergent salts containing a hydrophobic higher alkyl moi~ty, such as s~]~s of hi~her alkyl mono-or poly-nuclear aryl sulfonates having ~rom about 8 to 18 carbon atoms ln the alkyl group which may have a straight preferred or branched chain - structure, preferred species including; wi~hout necessary limita-tion: sodium linear tridecylbenzene sulfonate, sodium linear dodecyl benzene sulfonate sodium linear decyl benzene sulfonate, lithium or ~otassium pentapropylene benzene sulfonate; alkali metal salts of sulfated condensation prod-ucts of ethylene oxide, e.~. containing 3 to 20 and preferably 3 to 10 moles of ethylene oxide, with aliphatic alcohols containing 8 to 18 carbon atoms or with alkyl phenols having alkyl groups containing 6 to 18 car,,on atoms, e.g., sodium nonyl phenol pentaethoxamer sulfate and sodi I
lauryl alcohol triethoxamer sulfate; alkali metal salts of satura~ed alcohols containing from about 8 to 18 carbon atoms, e.g. sodium lauryl sulfate and sodilum stearyl sulfate; alkali metal salts of higher fatty acid esters of low molecular weight alkylol sulfonic acid; e.g. fatty acid esters of the sodium salt of isethionic acid;
fatty ethanolamide sulfates; fatty acid amides of amino alkyl sulfonic acids, e.~. lauric acid amine o~ taurine; alkali metal salts of hydroxy alkane sulfonic acids having 8 to 18 carbon atom~
in the alkyl group, e.g., hexadecyl, alphahydro~y sodium sulfonat~.
The anionic or mixture thereof is used in the form of their alkali or alkaline earth metal salts. The anionic is preferably of the non-soap type, it being preferred that the soap component be utilized as taught herein. However, minor amou~ts of soap, e.g.
up to about 35% and preferably 20% based on total anionic can be ~
separately added, for example, to the crutcher mix. ~he concentra-tion of non-soap anionic should be selected so as to provide an excess with respect to cationic-softener according to the empirica 1 relationship % concentration ~ 1.5 x + 5 anioni c wl)el-ein x is the per cent collcelltLa~iol~ of cationic softeller.
This assures the minimum excess of anionic necessary for optimum overall de~ergency, so:Etening, e~c. performance in ~he product composition.
Minor amounts of ottler types of detergents can be included along with the anionic, their sum in any case not exceeding about 10% and preferably about 2-5~/~ of total detergent, i~e., such othe~
detergent plus non-soap anionic. Useful here are the nonionic surface active agents which contain an organic hydrophobic group and a hydrophilic group which is a reaction product of a solubili-zing group such as carboxylate, hydroxyl, amido or amino with ethylene oxide or with the polyhydration product thereof, poly~
ethylene glycol. Included are the condensation products of C8 to C30 fatty alcohols such as tridecyl alcohol with 3 to 100 moles e~hylene oxide; C16 to C18 alcohol with 11 to 50 moles ethylene oxide; ethylene oxide adducts with monoesters o~ polyhy~ric e.g.
hexahydric alcohol; condensation products o~ polypropylene glycol with 3 to 100 moles ethylene oxide; the condensation products of alkyl (C6 to C20 straight or branded chain) phenols with 3 to 100 20 ~ moles ethylene oxide and the like.
Suitable amphoteric detergents generally include those containing both an anionic group and a cationic group and a hydrophobic organic group which is preferabl.y a higher aliphatic radical of 10 to 20 carbon atoms; examples include the N-long cllain alkyl aminocarboxylic acids and the N-long chain alkyl iminodicarboxylic acids such as described in U.S. 3,824,189.
The compositions herein preEerably include water soluble alkaline to neutral builder salt in amounts of from about 10 to 60% by weight o~ total composition, Use~ul herein are the organic and inorganic builders including the alkali metal and alkaline earth metal phosphates, particularly the condensed phosphates such as the pyrophospllates or tripolyphosphates, silicates, borates, , -:~3~5 carbonates, bicarbonates and the like. Species thereof include sodium tri-polyphosphate, trisodium phosphate, tetrasodium pyrophosphate, sodium acid pyrophosphate, sodium monobasic phosphate, sodium dibasic phosphate, sodium hexametaphosphate; alkali metal silicates such as sodium metasilicate, sodium silicates: Na20/SiO2 of 1.6:1 to 3.2:1, sodium carbonate, sodium sulfate, borax ~sodium tetraborate) ethylene diamine tetraacetic acid tetrasodium salt, trisodium nitrilotriacetate and the like and mixtures of the foregoing.
Builder salt may be selected so as to provide either phosphate-containing or phosphate-free detergents. As to the latter embodiments, sodium carbonate is particularly effective. Another material found to provide good detergency effects is metakaolin which is generally produced by heating kaolinite lat-tice to drive off water producing a material which is substantially amorphous by x-ray examination but which retains some of the structural order of the kaolinite. Discussions of kaolin and metakaolin are found in United States Patent 4,075,280 columns 3 and 4 and Grimshaw, "The Chemistry of Physics of Clays and Allied Ceramic Materials", ~4th ed., Wiley-Interscience), pages 723-727. The metakaolin also appears to have softening utility. As to the latter, the most effective metakaolins appear to be those which behave best in the reaction with sodium hydroxide to form zeolite 4A as described in United States Patent 3,114,603 which refers to such materials as "reactive kaolin". As explained in the referenced sources, metakaolin is an alumino-silicate. The metakaolin and/or a zeolite is included in about the same amounts as the builder salt, and preferably supplemental thereto, e.g. zeo-lite-silicate in a ratio of 6:1. A particularly useful form of the meta-kaolin is that available commercially as Satintone No. 2.
Preferred optional ingredients useful herein include perfume such as Genie per~ume; optical brigh~eners and bluing a~ents which may be d~es or pigments, suitable materials in this regard including stilbene and Tinopal 5BM brighteners and particu- .
larly in combination and Direct Brilliant Sky Blue 6B, Solophenyl Violet 4BL, Cibacete Brilliant Blue RBL and Cibacete Violet B, Polar Brilliant Blue RAW and Calcocid Blue 2G bluing agents. The brightener may be included in amounts ran~ing up to about 1%
of the total composition while bluing agents may range up to abou :
.1% preferably up to about .01% of total composition. Bluing agent e.g. Polar Brilliant Blue may be included in the soap spaghetti. In either case, the amount need only be minimal to be effective.
Other ingredients of optimal significance include bleachin~
agents which may be of the oxygen or chlorine liberating type;
oxygen bleaches include sodium and potassium perborate, potassium monopersulfate and the like, while chlorine bleaches are typified by sodium hypochlorite, potassium dichloroisocyanurate trichlorn-isocyanuric acid and the like. The latter chlorine-liberating bleaches are representative of the bro~d class of water soluble, organic, dry solid bleaches known as the N-chloro imides includin~ ;
. their alkali metal salts. These cyclic imides have from about 4 to 6 member in the ring and are described in detail in U.S. Paten~
3,325,414. Each of the oxygen and chlorine type bleaches discuss~d above are fully compatible with the compositions herein and have good stability in the presence of the anionic and cationic component They are generally used in proportions ranging from about 0.1 to 25% by weight of total solids or from about .05% to about 20% .
based on total detergent composltion.
, Yet additional optional ingredients include water soluble and/or dispersible hydrophobic colloidal cellulosic soil suspendir Ig agent which may be desired in addition to that which may be incluc ec * Trade Mark ~ 15_ ~ 3 ~ .5 0 ~
in the soap-cellulose ethe~ mixture. ~ethyl cellulose, e.g.
Methocel is particularly efEective. Polyvinyl alcohol is likewise e~fective and especia:Lly in the washing of cotton and synthetic fibers such as nylon, dacron and resin treated cotton.
The additional soil suspendinF agent may be included in amounts u~
to about2% based on total solids and up to about 4% based on total detergent composition. However, it must be emphasized that the cellulose ether component of the soap spaghetti supplies at least a major part of the anti-redeposition or soll suspending - ~unction, its effectiveness in this regard being significantly augmented by the soap material as previously explained.
Fillers may also be included ln addition to the aforementi~
ingredients, such as sodium sulfate, sodium chloride and the like The amount will range up to about 40% of total composition.
The detergent composition is prepared by conventional processing such as sray drying a crutcher mix of surfactant, builder, filler etc. with volatile ingredients such as perfume or ingredients otherwise adversely affected by the spray drying process such as peroxygen bleach, e.g. sodium perborate.
Ingredients of this type are pre~erably post blended. As previouC 1 ; mentioned, the soap spaghetti and cationic amine softener are simply dry blended with the dried detergent in particulate form by simple mechanical mixing which is more than adequate to achiev~
. a homogeneous product. As previously explained, part or all of the soap spaghetti may alternatively be added to the aqueous - crutcher mixture. A typical procedure would be as follows:
Water is added to a crutcher followed in order by anionic, sodium silicate, optional ingredients where used such as Satintone*#2 -and filler such as sodium sulfate and builder salt. The crutcher mixture is heated to about 140F before addition of builder, e.g.
sodium tripolyphospl~ate and the solids content of the crutched mixture before spray drying is about 55~65%. Spray drying may * Trade Mark :, -16-J
be carried out in conven~ional manner by pumpin~ the hot mixture fro~ the crutchcr to a spray tower wherc the mixture passes throu~h a spray nozzle into a hot evaporative atmosphere. Bleach and other materials remainin~ to be added are incorporated into the cooled, dried detergent mass by any suitable means such as simple mechanical mixing, In use, sufficient of the detergent composition is added to the wash cycle to provide a concentration of cationic softener in the wash medium of about 1,5 to 8,0g/3500g laundry with a -range of 1.8 to 6,Q,g being preferred. Washing temperature may range from about 70 to the boil (i.e. about 212F).
- Certain types of aliphatic quaternary ammonium compounds though relatively ineffective as regards softening are neverthele ;s quite effective as antis~ats in the compositions herein and particularly since they are physically comDatible with anionic surfactant in liquid environments, In general, such materials - encompass the ethoxylated andlor propoxylated quaternary ammonium compounds of the following formula:
r cl 3 l +
L~ Rn ¦ X-.
wherein ~ and Rn represent ethoxy or propoxy, m and n are intege~ s oE from 1 to 50 and may be the same or different and Rg representC
alkyl of 14 to 24 carbon. Compounds of this type include ~a) methylbis (2-hydroxy-ethyl) coco ammonium chloride a liquid 75%
active ingredient in isopropanol/water solvent and available commercially as Ethoquad c/12, ~rmak and Variquat 638, Sherex~;
Chemical Co.; (b) Ethoquad c/25 - same as in (a) but having 15 moles of ethylene oxide (each of ~ and Rn) and available as 95%
active ingredient; (c) methylbis (2-hydroxy-ethyl) octadecyl * Trade Mark -17-~1 S~ 't'~
an~nonium chloride, a liqui~, 75% active ingredient in isoprop~nl/
water solvent available co~nercially as Ethoquad 18/12, Armak all~ (d) same as (c) but having 15 moles of ethylene oxide (each of ~l and ~), a li~uid, 95% active ingredient and available commercially as Ethoquad 18/25, Armak. These materials can be use d in amounts ranging up to about 10% by weight of total composition.¦
The following examples are given for purposes of illustrat ior only and are not intended to lim:it the invention. All parts and percentages are given by weight.
A spray dried heavy duty detergent having the following composition is provided:
%
linear tridecylbenzene sulfonate 15 (LTBS) tripolyphosphate sodium 33 (NATPP) silicate 7 brightener (Stilbene*and Tinopal*5BM) 0,48 Q.s. sodium sulfate and water 44,52 loo. no To 9,5 g. o~ the above composition are added:
~r ms distearyl dimethyl ammonium 5 chloride (Arosurf TA-100 *
Sherex Chemical Co., 93%
'AI powder Soap spaghetti (4% carboxymethyl 5 cellulose, 90% tallow/coco 85/15; blue color Polar Brilliant Blue' spaghetti length = 15 mm;
and d:iameter = 0.5 mm.
to provide a hornogeneous composition by simple mechanical mixing, Washing tests with the foregoing composition are conducted as follows using General Electrlc washers, 17 gallons tap water at 120F (approximately 100 ppm hardness), tests are conducted on a * Tra de Ma rk , ..~,.. .
sin~le t~wel, Eabric softnesx evaluation being ~aken on a scale of 1 (no softnes.s) to 10 (excellent softness) whiteness (~b) rc.~ings are t~ken on a Gardner Color Difference ~eter in the usual manner, about 0.5 unit visu~lly discernible and with higher values indicating increased wl~iteness. Towels washed as indicated ~above were evaluated as to softness and whiteness.
Example 1 is repeated except that the soap (no CMC~
spaghetti is provided in the form o~ flakes having a length of about 4 m.m., a width of about 4 m.m. and a thickness of about 0.2 m.m.
Example l'is repeated except that the soap-CMC mixture is omitted.
The following softness and whiteness results are obtained.
Example No. Softness -b 1 10* 7.7 2 10* 6.1 3 8 ~.4 The use of the CMC-soap in spaghetti form (Example 1) provides excellent softness and more effective detergency than ,either of Examples 2 or 3. The as~erisk superscript to the softnes ~
value indicates the highly desirable quality of fluffiness indicati re of softness-plus. Thl~ same fluffy quality is obtained wlth the use of soap flakes (Example 2~. The absence of the CMC-soap in Example 3 leads to a market reduction in softness as the data demonstrates. It must be pointed out that the slight numerical difference in w'hiteness favoring Example 3 as compared to Example 2 is of questiona'ble significance even apart from po~sible experiment 1 crror sincc the 0.3 difference therebetwecn in whiteness is not within the range of visual discernibility, EXAMPLES ~ and 5 Examples l and 3 are repeated except that testing is carried out using 2 new towel specimens with ballast loads. Softness and brightness measurements are taken in the manner indicated on each towel.
The process of Example 1 is repeated but using commercial deter-gent compositions ~A~B) having the following proximate analyses:
%
A B
Linear alkyl benzene sulfonate 7.3 11.8 fatty alcohol sulfate ~ 11.5 4.0 ethoxylated sulfate DialXyl dimethyl ammonium chloride 4.7 4.5 IBentonite 18.0 21.7 Nonionic Z.7 2.8 Soap 0.7 0.9 High swelling Wyoming type such as Thiox-jel* No. l The above analyses were taken about 3 months apart on products cur-rent at that time which probably accounts for the difference in concentrations for each of the ingredients. The commercial formula includes about 5% quat and a relatively small amount of soap, the ratio of quat to soap being at least about 4.5 to l on the basis of these approximate data.
Softness and brightness measurements gave the following results:
Example No.Softness Towel 1 Towel 2 Towel 1 Towel 2
based on total detergent composltion.
, Yet additional optional ingredients include water soluble and/or dispersible hydrophobic colloidal cellulosic soil suspendir Ig agent which may be desired in addition to that which may be incluc ec * Trade Mark ~ 15_ ~ 3 ~ .5 0 ~
in the soap-cellulose ethe~ mixture. ~ethyl cellulose, e.g.
Methocel is particularly efEective. Polyvinyl alcohol is likewise e~fective and especia:Lly in the washing of cotton and synthetic fibers such as nylon, dacron and resin treated cotton.
The additional soil suspendinF agent may be included in amounts u~
to about2% based on total solids and up to about 4% based on total detergent composition. However, it must be emphasized that the cellulose ether component of the soap spaghetti supplies at least a major part of the anti-redeposition or soll suspending - ~unction, its effectiveness in this regard being significantly augmented by the soap material as previously explained.
Fillers may also be included ln addition to the aforementi~
ingredients, such as sodium sulfate, sodium chloride and the like The amount will range up to about 40% of total composition.
The detergent composition is prepared by conventional processing such as sray drying a crutcher mix of surfactant, builder, filler etc. with volatile ingredients such as perfume or ingredients otherwise adversely affected by the spray drying process such as peroxygen bleach, e.g. sodium perborate.
Ingredients of this type are pre~erably post blended. As previouC 1 ; mentioned, the soap spaghetti and cationic amine softener are simply dry blended with the dried detergent in particulate form by simple mechanical mixing which is more than adequate to achiev~
. a homogeneous product. As previously explained, part or all of the soap spaghetti may alternatively be added to the aqueous - crutcher mixture. A typical procedure would be as follows:
Water is added to a crutcher followed in order by anionic, sodium silicate, optional ingredients where used such as Satintone*#2 -and filler such as sodium sulfate and builder salt. The crutcher mixture is heated to about 140F before addition of builder, e.g.
sodium tripolyphospl~ate and the solids content of the crutched mixture before spray drying is about 55~65%. Spray drying may * Trade Mark :, -16-J
be carried out in conven~ional manner by pumpin~ the hot mixture fro~ the crutchcr to a spray tower wherc the mixture passes throu~h a spray nozzle into a hot evaporative atmosphere. Bleach and other materials remainin~ to be added are incorporated into the cooled, dried detergent mass by any suitable means such as simple mechanical mixing, In use, sufficient of the detergent composition is added to the wash cycle to provide a concentration of cationic softener in the wash medium of about 1,5 to 8,0g/3500g laundry with a -range of 1.8 to 6,Q,g being preferred. Washing temperature may range from about 70 to the boil (i.e. about 212F).
- Certain types of aliphatic quaternary ammonium compounds though relatively ineffective as regards softening are neverthele ;s quite effective as antis~ats in the compositions herein and particularly since they are physically comDatible with anionic surfactant in liquid environments, In general, such materials - encompass the ethoxylated andlor propoxylated quaternary ammonium compounds of the following formula:
r cl 3 l +
L~ Rn ¦ X-.
wherein ~ and Rn represent ethoxy or propoxy, m and n are intege~ s oE from 1 to 50 and may be the same or different and Rg representC
alkyl of 14 to 24 carbon. Compounds of this type include ~a) methylbis (2-hydroxy-ethyl) coco ammonium chloride a liquid 75%
active ingredient in isopropanol/water solvent and available commercially as Ethoquad c/12, ~rmak and Variquat 638, Sherex~;
Chemical Co.; (b) Ethoquad c/25 - same as in (a) but having 15 moles of ethylene oxide (each of ~ and Rn) and available as 95%
active ingredient; (c) methylbis (2-hydroxy-ethyl) octadecyl * Trade Mark -17-~1 S~ 't'~
an~nonium chloride, a liqui~, 75% active ingredient in isoprop~nl/
water solvent available co~nercially as Ethoquad 18/12, Armak all~ (d) same as (c) but having 15 moles of ethylene oxide (each of ~l and ~), a li~uid, 95% active ingredient and available commercially as Ethoquad 18/25, Armak. These materials can be use d in amounts ranging up to about 10% by weight of total composition.¦
The following examples are given for purposes of illustrat ior only and are not intended to lim:it the invention. All parts and percentages are given by weight.
A spray dried heavy duty detergent having the following composition is provided:
%
linear tridecylbenzene sulfonate 15 (LTBS) tripolyphosphate sodium 33 (NATPP) silicate 7 brightener (Stilbene*and Tinopal*5BM) 0,48 Q.s. sodium sulfate and water 44,52 loo. no To 9,5 g. o~ the above composition are added:
~r ms distearyl dimethyl ammonium 5 chloride (Arosurf TA-100 *
Sherex Chemical Co., 93%
'AI powder Soap spaghetti (4% carboxymethyl 5 cellulose, 90% tallow/coco 85/15; blue color Polar Brilliant Blue' spaghetti length = 15 mm;
and d:iameter = 0.5 mm.
to provide a hornogeneous composition by simple mechanical mixing, Washing tests with the foregoing composition are conducted as follows using General Electrlc washers, 17 gallons tap water at 120F (approximately 100 ppm hardness), tests are conducted on a * Tra de Ma rk , ..~,.. .
sin~le t~wel, Eabric softnesx evaluation being ~aken on a scale of 1 (no softnes.s) to 10 (excellent softness) whiteness (~b) rc.~ings are t~ken on a Gardner Color Difference ~eter in the usual manner, about 0.5 unit visu~lly discernible and with higher values indicating increased wl~iteness. Towels washed as indicated ~above were evaluated as to softness and whiteness.
Example 1 is repeated except that the soap (no CMC~
spaghetti is provided in the form o~ flakes having a length of about 4 m.m., a width of about 4 m.m. and a thickness of about 0.2 m.m.
Example l'is repeated except that the soap-CMC mixture is omitted.
The following softness and whiteness results are obtained.
Example No. Softness -b 1 10* 7.7 2 10* 6.1 3 8 ~.4 The use of the CMC-soap in spaghetti form (Example 1) provides excellent softness and more effective detergency than ,either of Examples 2 or 3. The as~erisk superscript to the softnes ~
value indicates the highly desirable quality of fluffiness indicati re of softness-plus. Thl~ same fluffy quality is obtained wlth the use of soap flakes (Example 2~. The absence of the CMC-soap in Example 3 leads to a market reduction in softness as the data demonstrates. It must be pointed out that the slight numerical difference in w'hiteness favoring Example 3 as compared to Example 2 is of questiona'ble significance even apart from po~sible experiment 1 crror sincc the 0.3 difference therebetwecn in whiteness is not within the range of visual discernibility, EXAMPLES ~ and 5 Examples l and 3 are repeated except that testing is carried out using 2 new towel specimens with ballast loads. Softness and brightness measurements are taken in the manner indicated on each towel.
The process of Example 1 is repeated but using commercial deter-gent compositions ~A~B) having the following proximate analyses:
%
A B
Linear alkyl benzene sulfonate 7.3 11.8 fatty alcohol sulfate ~ 11.5 4.0 ethoxylated sulfate DialXyl dimethyl ammonium chloride 4.7 4.5 IBentonite 18.0 21.7 Nonionic Z.7 2.8 Soap 0.7 0.9 High swelling Wyoming type such as Thiox-jel* No. l The above analyses were taken about 3 months apart on products cur-rent at that time which probably accounts for the difference in concentrations for each of the ingredients. The commercial formula includes about 5% quat and a relatively small amount of soap, the ratio of quat to soap being at least about 4.5 to l on the basis of these approximate data.
Softness and brightness measurements gave the following results:
Example No.Softness Towel 1 Towel 2 Towel 1 Towel 2
4 10 8 6.6 7.4 6 6 6.5 6.3 6A 8 5 6.5 6.6 *Trademark - 20 -~3~5~
The CMC-soap spaghetti composition (Example 4) is superior in both softness and detergency compared to -the soapless embodiment (Example 5 Aro-surf only) and the commercial formula (Example 6) whether the results be con-sidered singly or on an average basis. The commercial composition though marginally superior to the soapless composition does not produce visually discernible increase in detergency (whiteness) when compared to that composi-tion. On an average basis, the CMC-soap spaghetti composition provides a visually discernibla increase in whiteness when compared to either of Examples
The CMC-soap spaghetti composition (Example 4) is superior in both softness and detergency compared to -the soapless embodiment (Example 5 Aro-surf only) and the commercial formula (Example 6) whether the results be con-sidered singly or on an average basis. The commercial composition though marginally superior to the soapless composition does not produce visually discernible increase in detergency (whiteness) when compared to that composi-tion. On an average basis, the CMC-soap spaghetti composition provides a visually discernibla increase in whiteness when compared to either of Examples
5 and 6.
Example 1 is repeated as follows:
~a) same as Example 1 (b) the NATPP of Example 1 is replaced with the same amount of sodium carbonate.
In each case, testing is carried out on 2 towel specimens.
The results are as follows:
Softness -b Towel 1 Towel 2 Average - 2 towels ~a) 10 10 5.8 (b) 10+ 10~ 4.6 Superior softness is obtained for the non-phosphate run (b); how-ever, the phosphate run (a) yields superior whiteness. Nevertheless, run (b) is superior in both softness and detergency when compared to a control run, the same as run (b) but omitting the soap. The foregoing is understandable since the phosphate builders are recognized as having exceptional detersive activity as compared to other builder salts. The use of zeolite in the com-position has the effect of increasing detergency as the following example demonstrates.
~ ' :
395~?5 Example ~7b) is repeated but replacing the sodium carbonate with zeolite. The results are as follows:
Example Softness -b Towel 1 _owel 2 Average - 2 Towels 8 10 10 5.2 7(b) 10 10 4.6 The use of zeolite provides a visually discernible increase in whiteness; however, at the expense of fluffy quality of Example 7~b); never-theless, the softness rating of 10 is excellent.
The effects of decreasing the concentration of both the CMC-soap spaghetti and softener components in the sodium carbonate built composition of Example 7~b) but maintaining a unity weight ratio therebetween is observed from the following test runs:
%
~a) detergent composition of Example 7~b) 92 Arosurf TA-100 4 CMC-soap spaghetti 4 ~b) detergent composition of Example 7~b) 94 Arosurf TA-100 3 CMC-soap spaghetti 3 Softness and brightness results are as follows:
Softners -b Towel 1 Towel 2 Average - 2 Towels ~a) 10 10 5.8 ~b) 10 10 6.2 Softness is the same for ~a) and ~b). The non-visually discernible increase in detergency for run ~b) probably results from the presence of more detergent. It seems clear then that increasing the amount of cationic rel-ative to anionic does not - ~3~3~50~
affect detergency at least insofar as the human eye is concerned. It is pos-sible if not probable that by decreasing the proportion of anionic in run (b) to the value of run ~a) the brightness values would be about equal.
The effects of decreasing the concentration of both the CMC-soap spaghetti and softener components in the zeolite built composition of Example 8 but maintaining a unity weight ratio therebetween is observed from the fol-lowing test runs:
%
(a) detergent composition of Example 8 92 Arosurf TA-100 4 CMC-soap spaghetti 4 (b) detergent composition of Example 8 94 Arosurf TA-100 3 CMC-soap spaghetti 3 Softness and brightness results are as follows:
Softness b Towel 1 Towel 2 Average - 2 towels (a) 9 9 5.8 (b) 10 10 6.2 The difference in whiteness is explained by the discussion in con-nection with Example 9. The decrease in softness is probably accounted for by the fact that the effects of zeolite on softness seem to be somewhat in-consistent. The softness rating of 9 in run (b) is nevertheless indicative of good softness.
EXAMPLE ll Example 1 is repeated except that the amounts of CMC-soap and Arosurf TA-100 are 6% and 4% respectively. Softness ratings (2 towels) are and 10 , the average -b being 6.7. This is markedly superior to a con-trol run omitting the CMC-soap spaghetti ~ 3~
or soap spaghetti without CMC as to both sof~ness and brightness.
Embodiments of the present invention compare distinctly favorably with control runs wherein the cationic softener is ' omitted as the foregoing examples make clear. Inte~egtinRly, when the cationic softener is omittecl, the detergency of the resultant composition as determined by -b measurments are often inferior to the CMC-soap ~or soap, alone), cationic softener embodiments in accordance with the invention. In most cases, any difference in -b is not such as to be visually discernible, Softness ratings omitting the cationic softener are poor being in the order ~f scale 1Ø The test data thus cogently demonstrates the fact that the use of the CMC-soap (or soap without CMC~ system and cationic in accordance with the invention provides excellent .softness and in many cases flu~finess with no evidence o~ detrimen~al e~E~cts on detergency. 0~ further significance is the complete absence of a~verse e~fects upon the softening capacity of the cationic despite the presenceo~ the soap. As explained previously herein, it would normally be thought that the soap might detract from the softening efficacy of the cationic. In the present invention, quite the co~verse is the case as the prior examples ;demonstrate. It appears that the CMC-soap (or soap without CMC) spaghetti significantly enhances the softening activity of the cationic.
Examples 12-14 ~hich follow are illustrative of compo~itior s Z5 found to be particularly effective in accordance with the inventio~ .
The following heavy du~y compositions are prepared:
Example No, l2 13 14 ~fo L %
linear tridecyl benzene sulfonate 15 ~
linear dodecyl benzene sulfonate --- 23 19 . ~
E~ample N~
]2 13 14 % % D/
NATPP 33 ___ __-Na2C03 ___ 20 -__ Silicate 7 15 5 Borax 1 3 ---Zeolite ~~~ ~~~ 30 Nonionic -- 1 1 Soap --- 2 ---CMC ~-- 1 ---Brightener ,48 ,48 ,48 Satintone --- 1 ---Genie perfume ,15 --- ---Na2S04 & H20 q.s q.s q.s ; Stilbene and Tinopal 5B~
To 90 grams of each of the foregoing compositions are added 5 grams of CMC-soap spaghetti and 5 grams of Arosurf TA-100 as described in Example 1. Softness and brightness measurements are taken on washed towel specimens as described in Example l. ~Th~
results obtained compare favorably with those of Example l, i.~e., ;
~; excellent softness and detergency results obtain.
:~:
, .
Example 1 is repeated but replacing the cationic so~tener with the following:
Example No. Softener dihydr-ogenated tallow dimethyl ammoniu m chloride 16 ditallow dimethyl ammonlum chloride 17 distearyl dimethyl ammonium methyl ~ sulfate 18 di-hydrogenated tallow dimethyl ammonium methyl sulfate ~, L39SO~
Softness anci whiteness results are similar to those of Example 1.
~X~MPLES 19 & 20 Example 1 is repeated but replacing the cationic softener with the following imidazolinium compounds.
Example No. Softener -19 methyl-l-tallow amido ethyl-2-tallow imidazolinium methyl sulfate methyl-l-oleyl amido ethyl-2-oleyl imi.dazolinium methyl sulfate Softness and whiteness results are similar to those of Example l.
In the preceding examples, sufficient of the composition tested is added to the wash cycle to provide a concentration of cationic softener in the washing medium sufficient to yield a rati o~ cationic to laundry oF about .00057:1. i.e. 57 parts cationic per 10,000 parts laundry.
Antiredeposition and antistat effects obtained in accordanç
with the invention are excellent. The effects of the CMC componen~
of the soap spaghetti are effectively augmented by hydroxy alkyl methyl celluloses which are particularly effective in reducing dirt motor oil redeposition on synthetics; e.g., hydroxy butyl methyl cellulose available commercially as Methocel XD8861 (Dow) and hydro:
- ethyl methyl cellulose, available com~lercially as Tylose MH300 (Hoechst).
The soap-cellulose ether system of the invention is readil~
soluble in the aqueous washing medium as the following data indical :
Minutes to dissolve 70F $0F lOO~F 130F
CMC-soap spaghetti 5-6 5 2 Concentration of CMC-soap spaghe~ti in the aqueous solvent - medium = ?
The addition of bleach e,g. perborate, to the present comp .
osition within the concentration limits hereinbefore given can be made without significant adverse effects on either detergency or softness. Thus, no visually discernible reduction in detergency i! ;
noted. As to softness, about the only untoward effect noted is a slight reduction of the fluffy quality of the fabric indicated by ')G
;I rc~ c~i~n in tl~e so~Ln~ss r,lting of from lOi ~o lO i.n sever.ll test ~ .
~len Example L is repeated but adding Erom 0.5% to 2% of tl-e ethoxylatecl quat mat~ria]s descri~ed hereinbefore, e.g.
methylbis (2-hydroxyethyl) coco ammonium chloride, further enhancement of the antistat capabili~y of the present compositions obtains. Softness and detergency are not adversely affected, test runs establishing the ethoxylated quats to be fully compatibl~ , in the present compositions and particularly as regards the anioni~
surfactant.
Results similar to those described in the foregoing exampl s are obtained when their procedures are repeated but replacing, for example, the fatty acid soap and/or CMC with the equivalent materi ls enumerated hereinbefore. Within the limits given, the fatty acid can be varied widely, e.g. soaps of myristic, capric and li.neolic acids and their mixtures with essentially the same results. A
particularly effective alternative to the CMC is hydroxybutyl methyl cellulose (methocel XD).The particular cellulose ether selected when used with soap as a carrier is mainly on the basis of aniredeposition performance~ In those caseswhere the cellulose ether (or equivalent) may be somewhat inadequate to the task, other antiredeposition agents of the cellulose ether type (preferably) can be separately added (note Exampe 13) to the crutcher.
- The concentration of cationic softener and soap spaghetti in the composition can be increased up to about 20% with good ~ softening and whitening results provided anionic concentration and, of course, the softener/soap spaghetti ratio be limited as hereinbefore explained. As the concentration is thus increased, it may be advisable to maintain softener/soap spaghetti ratios _ to values approximating unity, this being a preferred embodiment.
;Softener and soap spaghetti are fully compatible with anionic a~ these increased concentrations, The highly concentrated form .. . _ . . ..
~.3~
of the composition is advantageous from several standpoints having reference to, for example, unusually severe laundering problems allowing the dispensing of smaller yet more potent amounts by the user.
Illustrative of the use of the cellulose ether in the crutcher is the following:
A composition of the following is crutched and spray dried.
%
tridecyl benzene sulfonate 15.0 TPP 33.0 Sodium silicate ~1:2.4 Na2O:SiO2) 7.0 Sodium Carbonate 5.0 Borax 1.0 CMC 0.25 Dow Methocel XD8861 0.56 Stilbene brightener 0.4 Tinopal 5BM 0.08 Sodium sulfate 26.71 Water 11.00 1 00 . 00 To 89.403 g of the above spray dried composition there are added Arosurf TA-100 5.0 g Soap spaghetti (No CMC) 5.0 g (Soap 85/15 tallow/coco) Non-Ionic 0.47 g (C12_15 linear aliphatic alcohol ~ 7 E.O.) Perfume O.lS g to give 100 g of product. The performance of the above is similar to Example 1. This illustrates the use of a pure soap spaghetti with all of the cellu-lose ether in the crutcher mix.
Example 1 is repeated as follows:
~a) same as Example 1 (b) the NATPP of Example 1 is replaced with the same amount of sodium carbonate.
In each case, testing is carried out on 2 towel specimens.
The results are as follows:
Softness -b Towel 1 Towel 2 Average - 2 towels ~a) 10 10 5.8 (b) 10+ 10~ 4.6 Superior softness is obtained for the non-phosphate run (b); how-ever, the phosphate run (a) yields superior whiteness. Nevertheless, run (b) is superior in both softness and detergency when compared to a control run, the same as run (b) but omitting the soap. The foregoing is understandable since the phosphate builders are recognized as having exceptional detersive activity as compared to other builder salts. The use of zeolite in the com-position has the effect of increasing detergency as the following example demonstrates.
~ ' :
395~?5 Example ~7b) is repeated but replacing the sodium carbonate with zeolite. The results are as follows:
Example Softness -b Towel 1 _owel 2 Average - 2 Towels 8 10 10 5.2 7(b) 10 10 4.6 The use of zeolite provides a visually discernible increase in whiteness; however, at the expense of fluffy quality of Example 7~b); never-theless, the softness rating of 10 is excellent.
The effects of decreasing the concentration of both the CMC-soap spaghetti and softener components in the sodium carbonate built composition of Example 7~b) but maintaining a unity weight ratio therebetween is observed from the following test runs:
%
~a) detergent composition of Example 7~b) 92 Arosurf TA-100 4 CMC-soap spaghetti 4 ~b) detergent composition of Example 7~b) 94 Arosurf TA-100 3 CMC-soap spaghetti 3 Softness and brightness results are as follows:
Softners -b Towel 1 Towel 2 Average - 2 Towels ~a) 10 10 5.8 ~b) 10 10 6.2 Softness is the same for ~a) and ~b). The non-visually discernible increase in detergency for run ~b) probably results from the presence of more detergent. It seems clear then that increasing the amount of cationic rel-ative to anionic does not - ~3~3~50~
affect detergency at least insofar as the human eye is concerned. It is pos-sible if not probable that by decreasing the proportion of anionic in run (b) to the value of run ~a) the brightness values would be about equal.
The effects of decreasing the concentration of both the CMC-soap spaghetti and softener components in the zeolite built composition of Example 8 but maintaining a unity weight ratio therebetween is observed from the fol-lowing test runs:
%
(a) detergent composition of Example 8 92 Arosurf TA-100 4 CMC-soap spaghetti 4 (b) detergent composition of Example 8 94 Arosurf TA-100 3 CMC-soap spaghetti 3 Softness and brightness results are as follows:
Softness b Towel 1 Towel 2 Average - 2 towels (a) 9 9 5.8 (b) 10 10 6.2 The difference in whiteness is explained by the discussion in con-nection with Example 9. The decrease in softness is probably accounted for by the fact that the effects of zeolite on softness seem to be somewhat in-consistent. The softness rating of 9 in run (b) is nevertheless indicative of good softness.
EXAMPLE ll Example 1 is repeated except that the amounts of CMC-soap and Arosurf TA-100 are 6% and 4% respectively. Softness ratings (2 towels) are and 10 , the average -b being 6.7. This is markedly superior to a con-trol run omitting the CMC-soap spaghetti ~ 3~
or soap spaghetti without CMC as to both sof~ness and brightness.
Embodiments of the present invention compare distinctly favorably with control runs wherein the cationic softener is ' omitted as the foregoing examples make clear. Inte~egtinRly, when the cationic softener is omittecl, the detergency of the resultant composition as determined by -b measurments are often inferior to the CMC-soap ~or soap, alone), cationic softener embodiments in accordance with the invention. In most cases, any difference in -b is not such as to be visually discernible, Softness ratings omitting the cationic softener are poor being in the order ~f scale 1Ø The test data thus cogently demonstrates the fact that the use of the CMC-soap (or soap without CMC~ system and cationic in accordance with the invention provides excellent .softness and in many cases flu~finess with no evidence o~ detrimen~al e~E~cts on detergency. 0~ further significance is the complete absence of a~verse e~fects upon the softening capacity of the cationic despite the presenceo~ the soap. As explained previously herein, it would normally be thought that the soap might detract from the softening efficacy of the cationic. In the present invention, quite the co~verse is the case as the prior examples ;demonstrate. It appears that the CMC-soap (or soap without CMC) spaghetti significantly enhances the softening activity of the cationic.
Examples 12-14 ~hich follow are illustrative of compo~itior s Z5 found to be particularly effective in accordance with the inventio~ .
The following heavy du~y compositions are prepared:
Example No, l2 13 14 ~fo L %
linear tridecyl benzene sulfonate 15 ~
linear dodecyl benzene sulfonate --- 23 19 . ~
E~ample N~
]2 13 14 % % D/
NATPP 33 ___ __-Na2C03 ___ 20 -__ Silicate 7 15 5 Borax 1 3 ---Zeolite ~~~ ~~~ 30 Nonionic -- 1 1 Soap --- 2 ---CMC ~-- 1 ---Brightener ,48 ,48 ,48 Satintone --- 1 ---Genie perfume ,15 --- ---Na2S04 & H20 q.s q.s q.s ; Stilbene and Tinopal 5B~
To 90 grams of each of the foregoing compositions are added 5 grams of CMC-soap spaghetti and 5 grams of Arosurf TA-100 as described in Example 1. Softness and brightness measurements are taken on washed towel specimens as described in Example l. ~Th~
results obtained compare favorably with those of Example l, i.~e., ;
~; excellent softness and detergency results obtain.
:~:
, .
Example 1 is repeated but replacing the cationic so~tener with the following:
Example No. Softener dihydr-ogenated tallow dimethyl ammoniu m chloride 16 ditallow dimethyl ammonlum chloride 17 distearyl dimethyl ammonium methyl ~ sulfate 18 di-hydrogenated tallow dimethyl ammonium methyl sulfate ~, L39SO~
Softness anci whiteness results are similar to those of Example 1.
~X~MPLES 19 & 20 Example 1 is repeated but replacing the cationic softener with the following imidazolinium compounds.
Example No. Softener -19 methyl-l-tallow amido ethyl-2-tallow imidazolinium methyl sulfate methyl-l-oleyl amido ethyl-2-oleyl imi.dazolinium methyl sulfate Softness and whiteness results are similar to those of Example l.
In the preceding examples, sufficient of the composition tested is added to the wash cycle to provide a concentration of cationic softener in the washing medium sufficient to yield a rati o~ cationic to laundry oF about .00057:1. i.e. 57 parts cationic per 10,000 parts laundry.
Antiredeposition and antistat effects obtained in accordanç
with the invention are excellent. The effects of the CMC componen~
of the soap spaghetti are effectively augmented by hydroxy alkyl methyl celluloses which are particularly effective in reducing dirt motor oil redeposition on synthetics; e.g., hydroxy butyl methyl cellulose available commercially as Methocel XD8861 (Dow) and hydro:
- ethyl methyl cellulose, available com~lercially as Tylose MH300 (Hoechst).
The soap-cellulose ether system of the invention is readil~
soluble in the aqueous washing medium as the following data indical :
Minutes to dissolve 70F $0F lOO~F 130F
CMC-soap spaghetti 5-6 5 2 Concentration of CMC-soap spaghe~ti in the aqueous solvent - medium = ?
The addition of bleach e,g. perborate, to the present comp .
osition within the concentration limits hereinbefore given can be made without significant adverse effects on either detergency or softness. Thus, no visually discernible reduction in detergency i! ;
noted. As to softness, about the only untoward effect noted is a slight reduction of the fluffy quality of the fabric indicated by ')G
;I rc~ c~i~n in tl~e so~Ln~ss r,lting of from lOi ~o lO i.n sever.ll test ~ .
~len Example L is repeated but adding Erom 0.5% to 2% of tl-e ethoxylatecl quat mat~ria]s descri~ed hereinbefore, e.g.
methylbis (2-hydroxyethyl) coco ammonium chloride, further enhancement of the antistat capabili~y of the present compositions obtains. Softness and detergency are not adversely affected, test runs establishing the ethoxylated quats to be fully compatibl~ , in the present compositions and particularly as regards the anioni~
surfactant.
Results similar to those described in the foregoing exampl s are obtained when their procedures are repeated but replacing, for example, the fatty acid soap and/or CMC with the equivalent materi ls enumerated hereinbefore. Within the limits given, the fatty acid can be varied widely, e.g. soaps of myristic, capric and li.neolic acids and their mixtures with essentially the same results. A
particularly effective alternative to the CMC is hydroxybutyl methyl cellulose (methocel XD).The particular cellulose ether selected when used with soap as a carrier is mainly on the basis of aniredeposition performance~ In those caseswhere the cellulose ether (or equivalent) may be somewhat inadequate to the task, other antiredeposition agents of the cellulose ether type (preferably) can be separately added (note Exampe 13) to the crutcher.
- The concentration of cationic softener and soap spaghetti in the composition can be increased up to about 20% with good ~ softening and whitening results provided anionic concentration and, of course, the softener/soap spaghetti ratio be limited as hereinbefore explained. As the concentration is thus increased, it may be advisable to maintain softener/soap spaghetti ratios _ to values approximating unity, this being a preferred embodiment.
;Softener and soap spaghetti are fully compatible with anionic a~ these increased concentrations, The highly concentrated form .. . _ . . ..
~.3~
of the composition is advantageous from several standpoints having reference to, for example, unusually severe laundering problems allowing the dispensing of smaller yet more potent amounts by the user.
Illustrative of the use of the cellulose ether in the crutcher is the following:
A composition of the following is crutched and spray dried.
%
tridecyl benzene sulfonate 15.0 TPP 33.0 Sodium silicate ~1:2.4 Na2O:SiO2) 7.0 Sodium Carbonate 5.0 Borax 1.0 CMC 0.25 Dow Methocel XD8861 0.56 Stilbene brightener 0.4 Tinopal 5BM 0.08 Sodium sulfate 26.71 Water 11.00 1 00 . 00 To 89.403 g of the above spray dried composition there are added Arosurf TA-100 5.0 g Soap spaghetti (No CMC) 5.0 g (Soap 85/15 tallow/coco) Non-Ionic 0.47 g (C12_15 linear aliphatic alcohol ~ 7 E.O.) Perfume O.lS g to give 100 g of product. The performance of the above is similar to Example 1. This illustrates the use of a pure soap spaghetti with all of the cellu-lose ether in the crutcher mix.
Claims (31)
1. A detergent softener composition capable of imparting improved softness, detergency, antistatic and soil antiredeposition properties to fabrics treated therewith in a laundering process comprising by weight from about 5 to 40% of water soluble non-soap, organic surfactant, at least about 90% thereof being of the anionic type, from about 10 to 60% of water soluble, neutral to alkaline builder salt, from about 2 to 20% water soluble or dis-persible fatty acid soap from 0 to about 4% cellulose ether, from about 2 to 20% of cationic amine softener selected from the group consisting of (a) aliphatic di-(lower) C1 - C4 alkyl, di-(higher) C14 - C24 alkyl quaternary ammonium salts (b) hetrocyclic compounds, and mixtures of (a) and (b), the weight ratio of soap to softener being from about 8:1 to 1:3 the per-cent concentration of anionic surfactant being at least about 1.5 x + 5. x representing the per-cent concentration of softener, wherein the soap is substantially homogeneously dispersed in said composition as discrete particles, and wherein no more than 45% of the said discrete particles comprises cellulose ether.
2. A composition according to claim 1 wherein said soap comprises an alkali metal salt C10 - C30 fatty acid, at least about 50% thereof being C10 - C18 fatty acid.
3. A composition according to claim 2 wherein said soap is a mixture of coconut oil and tallow fatty acid salts,
4. A composition according to claim 3 wherein said soap is an 85/15 tallow/coco mixture.
5. A composition according to claim 1 wherein said cellulose ether is carboxymethyl cellulose, sodium carboxymethyl hydroxyethyl cellulose, sodium carboxymethylethyl cellulose, hydroxybutyl methyl cellulose, hydroxyethyl methyl cellulose or mixture thereof.
6. A composition according to claim 1 wherein said softener is distearyl, dimethyl ammonium chloride.
7. A composition according to claim 1 wherein said softener is di-hydrogenated tallow dimethyl ammonium chloride.
8. A composition according to claim 1 wherein said softener is methyl-1-tallow amido ethyl-2-tallow-imidazolinium methyl sulfate.
9. A composition according to claim 1 wherein said softener is methyl-1-oleyl amido ethyl-2-oleyl imidazolinium methyl sulfate.
10. A composition according to claim 1 wherein the ratio of soap to softener is about 1:1.
11. A composition according to claim 1 wherein said builder salt is an alkali metal phosphate and/or polyphosphate.
12. A composition according to claim 11 wherein said builder salt is sodium tripolyphosphate.
13. A composition according to claim 1 wherein said anionic detergent is linear tridecylbenzene sulfonate.
14. A composition according to claim 1 wherein said anionic detergent is linear dodoecyl benzene sulfonate.
15. A composition according to claim 1 containing from about 5 to 45% of metakaolin.
16. A composition according to claim 1 containing from about 5 to 45% of zeolite.
17. A composition according to claim 1 containing up to about 25% of water soluble fabric bleaching agent.
18. A composition according to claim 17 wherein said bleaching agent is alkali metal perborate.
19. A composition according to claim 1 wherein the concentration of each of the softener and soap is at least about 4%.
20. A detergent-softener product including about;
5% distearyl dimethyl-ammonium chloride 5% soap spaghetti consisting of 96% tallow/coco, 85/15 and 4% of carboxymethyl cellulose .15% perfume and 89.85% of the following detergent composition:
15% linear tridecylbenzene sulfonate 33% sodium tripolyphosphate 7% silicate 1% borax .48% brightener Q.S. sodium sulfate and water
5% distearyl dimethyl-ammonium chloride 5% soap spaghetti consisting of 96% tallow/coco, 85/15 and 4% of carboxymethyl cellulose .15% perfume and 89.85% of the following detergent composition:
15% linear tridecylbenzene sulfonate 33% sodium tripolyphosphate 7% silicate 1% borax .48% brightener Q.S. sodium sulfate and water
21. A detergent softener product including about 5% distearyl dimethyl ammonium chloride 5% soap spaghetti consisting of 96% tallow/coco, 85/15 and 4% of carboxymethyl cellulose .15% perfume and 89.85% of the following detergent composition:
23% linear dodecyl benzene sulfonate 20% sodium carbonate 15% silicate 3% borax 1% nonionic surfactant 2% fatty acid soap 1% carboxymethyl cellulose .48% brightener 1% satintone Q.S. sodium sulfate and water
23% linear dodecyl benzene sulfonate 20% sodium carbonate 15% silicate 3% borax 1% nonionic surfactant 2% fatty acid soap 1% carboxymethyl cellulose .48% brightener 1% satintone Q.S. sodium sulfate and water
22. A detergent softener product including about:
5% distearyl dimethyl ammonium chloride 5% soap spaghetti consisting of 96% tallow/coco, 85/15 and 4% of carboxymethyl cellulose .15% perfume and 89.85% of the following detergent composition 19% linear dodecylbenzene sulfonate 1% nonionic surfactant 30% zeolite 5% silicate ,48% brightener Q.S. sodium sulfate and water.
5% distearyl dimethyl ammonium chloride 5% soap spaghetti consisting of 96% tallow/coco, 85/15 and 4% of carboxymethyl cellulose .15% perfume and 89.85% of the following detergent composition 19% linear dodecylbenzene sulfonate 1% nonionic surfactant 30% zeolite 5% silicate ,48% brightener Q.S. sodium sulfate and water.
23. A composition according to claim 1 further containing up to about 3% fatty acid soap.
24. A process for washing fabrics comprising contacting said fabrics in an aqueous medium at a temperature of from about 80 to 170°F with sufficient of the composition of claim 1 to provide a ratio of from 1.5 to 8.0g of softener per 3500g of fabric.
25. A process for washing fabrics comprising contacting said fabrics in an aqueous medium at a temperature of from about 80 to 170°F with sufficient of the composition of claim 20 to provide a ratio of from 1.5 to 8.0g of softener per 3500g of fabric.
26. A process for washing fabrics comprising contacting said fabrics in an aqueous medium at a temperature of from about 80 to 170°F with sufficient of the composition of claim 21 to provide a ratio of from 1.5 to 8.0g of softener per 3500g of fabric.
27. A process for washing fabrics comprising contacting said fabrics in an aqueous medium at a temperature of from about 80 to 170°F with sufficient of the composition of claim 22 to provide a ratio of from 1.5 to 8.0g of softener per 3500g of fabric.
28. A composition according to claim 1 wherein at least part of any of the! cellulose ether is present in the soap, the said soap being present in spaghetti-like or other shaped form.
29. A composition according to claim 28 wherein the soap comprises at least about 50% of the soap-cellulose ether spaghetti combination.
30. A composition according to claim 29 wherein the soap comprises at least 80% of the spaghetti.
31. A composition according to claim 1 wherein the soap is present in spaghetti-like or other shaped form and none of the cellulose ether is present in the soap spaghetti.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/968,532 US4230590A (en) | 1978-12-11 | 1978-12-11 | Detergent softener compositions containing a soap-cellulose ether mixture |
| US968,532 | 1978-12-11 | ||
| US96,370 | 1979-11-21 | ||
| US06/096,370 US4298480A (en) | 1978-12-11 | 1979-11-21 | Detergent softener compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1139505A true CA1139505A (en) | 1983-01-18 |
Family
ID=26791632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000341521A Expired CA1139505A (en) | 1978-12-11 | 1979-12-10 | Detergent softener compositions |
Country Status (17)
| Country | Link |
|---|---|
| US (1) | US4298480A (en) |
| AT (1) | AT387231B (en) |
| AU (1) | AU5366779A (en) |
| CA (1) | CA1139505A (en) |
| CH (1) | CH644895A5 (en) |
| DE (1) | DE2949759A1 (en) |
| DK (1) | DK156583C (en) |
| ES (1) | ES486754A0 (en) |
| FR (1) | FR2444077A1 (en) |
| GB (1) | GB2038353B (en) |
| IE (1) | IE49232B1 (en) |
| IT (1) | IT1164084B (en) |
| NL (1) | NL7908918A (en) |
| NO (1) | NO152421C (en) |
| NZ (1) | NZ192354A (en) |
| PT (1) | PT70568A (en) |
| SE (1) | SE444689B (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4416811A (en) * | 1979-11-21 | 1983-11-22 | Colgate-Palmolive Company | Detergent softener compositions |
| ZA837830B (en) * | 1982-11-05 | 1985-06-26 | Colgate Palmolive Co | Detergent softener composition |
| US4615814A (en) * | 1984-04-02 | 1986-10-07 | Purex Corporation | Porous substrate with absorbed antistat or softener, used with detergent |
| GB8519047D0 (en) * | 1985-07-29 | 1985-09-04 | Unilever Plc | Detergent composition |
| US4654152A (en) * | 1985-10-07 | 1987-03-31 | Domtar Inc. | Base mix fabric softener |
| US4637890A (en) * | 1986-01-23 | 1987-01-20 | The Procter & Gamble Company | Detergent composition providing rinse cycle suds and turbidity control containing a soap, quaternary ammonium salt and a silicone |
| US4686060A (en) * | 1986-01-23 | 1987-08-11 | The Procter & Gamble Company | Detergent composition providing rinse cycle suds control containing a soap, a quaternary ammonium salt and a silicone |
| US4818422A (en) * | 1987-09-17 | 1989-04-04 | Colgate-Palmolive Co. | Fabric softening detersive article |
| GB8618635D0 (en) * | 1986-07-30 | 1986-09-10 | Unilever Plc | Detergent composition |
| US4954292A (en) * | 1986-10-01 | 1990-09-04 | Lever Brothers Co. | Detergent composition containing PVP and process of using same |
| US4704221A (en) * | 1986-10-22 | 1987-11-03 | The Procter & Gamble Company | Granular detergents which contain high levels of anionic surfactant that forms a middle-phase, surface treated with a water soluble cationic surfactant |
| TR23614A (en) * | 1987-01-29 | 1990-04-30 | Unilever Nv | CAMASIR OKTANLI GASOLINE PRODUCTION |
| CA1340941C (en) * | 1987-01-29 | 2000-04-04 | Francis Geoffrey Foster | Fabric conditioning composition |
| US4844822A (en) * | 1987-07-06 | 1989-07-04 | The Dial Corporation | Softener/antistat compositions |
| US4818421A (en) * | 1987-09-17 | 1989-04-04 | Colgate-Palmolive Co. | Fabric softening detergent composition and article comprising such composition |
| US5009800A (en) * | 1987-12-01 | 1991-04-23 | Lever Brothers Company, Division Of Conopco Inc. | Fabric softening additive for detergent compositions: cellulose ether and organic fabric softener |
| US4895667A (en) * | 1988-05-24 | 1990-01-23 | The Dial Corporation | Fabric treating compositions |
| MX9605097A (en) * | 1994-04-25 | 1997-08-30 | Procter & Gamble | Stable, aqueous laundry detergent composition having improved softening properties. |
| US5466394A (en) * | 1994-04-25 | 1995-11-14 | The Procter & Gamble Co. | Stable, aqueous laundry detergent composition having improved softening properties |
| CZ3898A3 (en) * | 1995-07-11 | 1998-08-12 | The Procter & Gamble Company | Concentrated stable preparations for softening fabrics containing chelating agents |
| US7244453B1 (en) | 2006-01-24 | 2007-07-17 | Lucia Mihalchick Litman | Anti-chlorine shampoo composition |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3325404A (en) * | 1963-09-19 | 1967-06-13 | Millmaster Onyx Corp | Composition for simultaneously laundering and softening fabrics |
| US3325414A (en) * | 1963-10-01 | 1967-06-13 | Colgate Palmolive Co | Heavy duty detergent composition containing a quaternary ammonium salt |
| DK129724A (en) * | 1968-04-03 | 1900-01-01 | ||
| GB1329429A (en) * | 1969-12-10 | 1973-09-05 | Gillette Co | Laundering composition |
| AU470133B2 (en) * | 1972-04-06 | 1976-03-04 | Colgate-Palmolive Company, The | Detergent compositions |
| US3852211A (en) * | 1972-08-09 | 1974-12-03 | Procter & Gamble | Detergent compositions |
| US3920563A (en) * | 1972-10-31 | 1975-11-18 | Colgate Palmolive Co | Soap-cationic combinations as rinse cycle softeners |
| US3954632A (en) * | 1973-02-16 | 1976-05-04 | The Procter & Gamble Company | Softening additive and detergent composition |
| US3920565A (en) * | 1973-02-23 | 1975-11-18 | Procter & Gamble | Fabric softener composition and method |
| US4178255A (en) * | 1978-05-15 | 1979-12-11 | Colgate-Palmolive Company | Detergent compositions |
| US4183815A (en) * | 1978-05-15 | 1980-01-15 | Colgate-Palmolive Company | Laundry detergent compositions |
-
1979
- 1979-11-21 US US06/096,370 patent/US4298480A/en not_active Expired - Lifetime
- 1979-12-08 DE DE19792949759 patent/DE2949759A1/en active Granted
- 1979-12-10 NO NO794012A patent/NO152421C/en unknown
- 1979-12-10 SE SE7910139A patent/SE444689B/en unknown
- 1979-12-10 IT IT51034/79A patent/IT1164084B/en active
- 1979-12-10 FR FR7930214A patent/FR2444077A1/en active Granted
- 1979-12-10 NZ NZ192354A patent/NZ192354A/en unknown
- 1979-12-10 PT PT70568A patent/PT70568A/en unknown
- 1979-12-10 CA CA000341521A patent/CA1139505A/en not_active Expired
- 1979-12-10 AT AT0778179A patent/AT387231B/en not_active IP Right Cessation
- 1979-12-10 DK DK524279A patent/DK156583C/en active
- 1979-12-11 IE IE2397/79A patent/IE49232B1/en unknown
- 1979-12-11 ES ES486754A patent/ES486754A0/en active Granted
- 1979-12-11 AU AU53667/79A patent/AU5366779A/en not_active Abandoned
- 1979-12-11 GB GB7942685A patent/GB2038353B/en not_active Expired
- 1979-12-11 NL NL7908918A patent/NL7908918A/en not_active Application Discontinuation
- 1979-12-11 CH CH1097179A patent/CH644895A5/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| CH644895A5 (en) | 1984-08-31 |
| DK156583C (en) | 1990-01-29 |
| IE49232B1 (en) | 1985-09-04 |
| NO152421B (en) | 1985-06-17 |
| DK156583B (en) | 1989-09-11 |
| ES8105031A1 (en) | 1981-05-16 |
| NZ192354A (en) | 1982-08-17 |
| GB2038353B (en) | 1983-05-11 |
| FR2444077B1 (en) | 1983-04-22 |
| ES486754A0 (en) | 1981-05-16 |
| GB2038353A (en) | 1980-07-23 |
| SE444689B (en) | 1986-04-28 |
| ATA778179A (en) | 1988-05-15 |
| DK524279A (en) | 1980-06-12 |
| NO152421C (en) | 1985-09-25 |
| NO794012L (en) | 1980-06-12 |
| DE2949759C2 (en) | 1989-05-11 |
| IE792397L (en) | 1980-06-11 |
| SE7910139L (en) | 1980-06-12 |
| US4298480A (en) | 1981-11-03 |
| IT1164084B (en) | 1987-04-08 |
| DE2949759A1 (en) | 1980-06-19 |
| AT387231B (en) | 1988-12-27 |
| PT70568A (en) | 1980-01-01 |
| NL7908918A (en) | 1980-06-13 |
| FR2444077A1 (en) | 1980-07-11 |
| IT7951034A0 (en) | 1979-12-10 |
| AU5366779A (en) | 1980-07-10 |
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