US3904533A

US3904533A - Fabric conditioners

Info

Publication number: US3904533A
Application number: US072168A
Authority: US
Inventors: Oscar W Neiditch; Jerome Rudy
Original assignee: Lever Brothers Co
Current assignee: Lever Brothers Co
Priority date: 1963-07-16
Filing date: 1970-09-14
Publication date: 1975-09-09
Anticipated expiration: 1992-09-09

Abstract

A fabric conditioning formulation is disclosed which is an aqueous emulsion of a cationic fabric softening material. This invention discloses the use of low temperature stabilizers for such emulsions including moderate molecular weight quaternary ammonium compounds and a number of nonionic and amphoteric materials. Preferably the moderate molecular weight ammonium compound is used in combination with one or more of the nonionic, anionic, or amphoteric substances. Optical brightening agents suitable for use in fabric softening formulations are also discussed.

Description

United States Patent Neiditch et al. Sept. 9, 1975 [54] FABRIC CONDITIONERS 3,364,142 1/1968 Buck 252/8.8

[75] Inventors: Oscar W. Neiditch, Fair Lawn; FOREIGN PATENTS OR APPLICATIONS Jerome Rudy Livingsmn, both of 496,476 9/1953 Canada 260/240 NJ. OTHER PUBLICATIONS [73] Ass1gnee: Lever Brothers Company, New

York A.P.C. Application ofWendt, Ser, No. 381,856, published 5-11-43. [22] Filed: Sept. 14, 1970 Appl. N0.: 72,168

[63] Continuation-impart of Scr. No. 295,543, July 16,

[52] US. Cl. 252/8.8; 252/8.7; 252/8.75; 252/524; 252/528; 252/542; 252/547; 1 17/1995 CQ [51] Int. Cl. D06M 0/00 [58] Field of Search 252/8.8, 8.75, 8.7, 524, 252/528, 542, 547; 117/1395 C, 139.5 Q

[56] References Cited UNITED STATES PATENTS 2,340,881 2/1944 Kelley et al 252/8.8 3,033,704 5/1962 Sherrill et al. 252/106 X 3,044,962 7/1962 Brunt et al 252/152 X 3,093,591 6/1963 Freesc 252/8.8 X 3,122,502 2/l964 Waldman 252/8.8 3,216,944 ll/l965 Fredrickson..... 252/8.8 3,296,l45 1/1967 Findlan ct al 252/8.8 X

Arquads, Quaternary Ammonium Salts, Publ. By Armour Industrial Chem. C0., Div. of Armour and C0., Chicago 6, Illinois, pages 1 to 6 and 8.

Primary ExaminerMayer Weinblatt Attorney, Agent, or F irmBrumbaugh, Graves, Donohue & Raymond [5 7] ABSTRACT A fabric conditioning formulation is disclosed which is an aqueous emulsion of a cationic fabric softening material. This invention discloses the use of low temperature stabilizers for such emulsions including moderate molecular weight quaternary ammonium compounds anda number of nonionic and amphoteric materials. Preferably the moderate molecular weight ammonium compound is used'in combination with one or more of the nonionic, anionic, or amphoteric substances. Optical brightening agents suitable for use in fabric softening formulations are also discussed.

16 Claims, No Drawings FABRIC CONDITIONERS This application is a continuation in part of our copending application. Ser. No. 295,543 filed July 16, 1963, g The present invention relates to novel fabric conditioning formulations, and in particular, to fabric conditioning formulations which provide improved bright-' ric conditioning compounds apppearto be antagonistictoward the usual optical brightening compounds.

According to the present invention, certain novel combinations of fabric conditioners and optical brightene rs have been discovered which arenot subject to this disability. The novel formulations of the present invention comprise a mixture containing from 99.5 to 80 parts by weight of a fabric conditionerselected from the group consisting of:

7. diethyl amino ethanol-stearamide-ethyl sulfates;

8. the reaction product of an amine having the formula R NH and an epichlorohydrin; and

9. the reaction product of 2 moles of an acid of the formula R COOH and an alkylene diamine of the formula ln the foregoing formulas, R is an aliphatic hydrocarbon group containing from 16 to 20 carbon atoms; R is;an.alkyl group containing from 1 to 3 carbon atoms;- R, is selected .from the group consisting of R and R R, is an aliphatic hydrocarbon group containing from 15 to .19 carbon atoms; R is an alkylene group containing from l to. 2,carbon atoms; R is a hydroxyalkylgroup containing from 1 to 3 carbon atoms; R5 is an alkyl group of l to 3.carbon atoms; X is an anion selected from the group consisting of halides, sulfates, alkyl sulfates having I to 3 carbon atoms in the alkyl group,and acetates,,and y is the valency of X.

One of more of the foregoing fabric conditioners may be mixed with from 0.5 to 20 parts by weight of at least one, optical brightener selected from the group consisting of:

wherein M is'a cation selected from the group consisting of hydrogen and an alkali metal.

Surprisingly, mixtures of the foregoing type not only overcome the reduction in brighteneing normally caused by the cationic fabric conditioners, but also provide optical brightening in addition to the brightening obtained by the use of a fluorescent dye-detergent composition in the preceding washing step.

A further aspect of the present invention relates to the emulsions of the above-fabric conditioning compounds, withor without added brighteners, having improved stability when subjected to cyclic freezing and thawing conditions. It has been observed that such emulsions frequently gel irreversibly when subjected to cyclic freezing and thawing conditions. The tendency ranging from a fraction of aper 'cent to 2 to 3 percent by weight of the total formulation,stabilizethe emulsion and prevent the formation of an irreversible gel in the rnanner described above. Such stabilizers, however, have the disadvantage that they tend to reduce the fabric conditioning efficiency of the active ingredients, particularly when present in a concentration in excess of'ab out 1%. j

As statedf 'in formulating emulsions which contain both a fabricf'conditioner and an optical brightener of the type described above, it hasbeen noted that the problem of "irreversible gelation is aggravated. While the addition of larger amounts of stabilizer would overcome the stability problem, the use of sufficient stabilizer to prevent irreversible gelation of an emulsion of a fabric conditioning compound and an optical brightener would seriously interfere with the fabric conditioning properties of the formulation.

According to this further aspectof the invention, it has been discoyered that aqueous emulsions of fabric conditioners of theforegoing type can be stabilized by the addition of from about 1% to about 2% of a shortchain quaternary ammonium compound, i.e., one containing aliphatic radicals having from 10 to 14 carbon atoms. ,flhe short-chain quaternary ammonium compounds may be used as emulsion stabilizers either alone or in conjunction with other known emulsion stabiliz-;

ers. Such emulsions are superior fabric conditioners because the quaternary ammoniurncompounds do not adversely affect the fabric softening properties of the active compounds.

It has been further discovered that by using such short-chain quaternary ammonium compounds as emulsion stabilizers, it is possible to prepare stable emulsions of fabric conditioning compounds containing an optical brightener which retain superior softening and brightening properties. Because the short-chain quaternary ammonium compounds do not interfere with the fabric conditioning compounds of "the active ingredients, it is possible to use them in emulsions containing bothj brie conditioning compounds and optical brightene n amounts sufficient to prevent irreversible gelation without affecting the ultimate fabric softening properties of the emulsion. In this event, howi ever, it is generally preferred to use mixtures of shortchain quaternary :ammoniurn compounds and other emulsion stabilizers,--inasrnu ch as emulsions containing 4 high concentrationsof the short-chain quaternary ammonium compounds ten d to separate on standing.

Stable fabric conditioning emulsions of the present invention consist essentially of the following compounds in approximately the following proportions, wherein'the percentages are based on the weight of the total composition: l

a. An ac'tivefabr'ic'- conditioning compound selected from the group consisting of I compounds I) through (9) above, inclusive, the total amount of said 'compounds'being from about 4% to 7%;

b from about to about 2% of a low temperature stabilizing agent which is a short-chain quaternary ammonium compound having the generic formula:

wherein R5 is analiphatic hydrocarbon group 'conta in- 4 carbon atoms; no more than about l .0% of a lower aliphatic alcohol; up to about 1% of a supplemental low temperature stabilizing agent selected from the group consisting of N-lauryl-B-amino propionic acid, dimethyl coco amine oxide, the polyoxyethylene ester of tall oil having from8 to 30 ethylene oxide units, polyoxyethylene sorbitan monolaurate having 6 to 20 ethylene oxide units, dodecyl methyl sulfoxide, the condensates of straight and branched chain unsubstituted aliphatic alcohols having 8 to 20 carbon atoms with from 1 to 30 moles of ethylene oxide, and alkyl phenol=ethylene oxide condensates having 8 to 12 carbon atoms in the alkyl chain and 8 to 30 ethylene oxide units; and

-f. an amount of water sufficient to make l00%.

While the foregoing represents theformula of a sim ple emulsion which may be used as a fabric conditioning formulation, it may be desirable, as mentioned above, to include an optical brightener. in this event, the formulation consists essentially of the ingredients mentioned above in paragraphs (a) to (d) and the following additional ingredients:

g. from about 0.10% toabout 0.30% of anloptical brightener of the stilbene dye type selected from Mons it CH CH OH HOCH CH salt-selected from the group consisting of inorganic salts and salts of organic acids containing from 1 to and SO M

wherein M is a cation selected from the group consisting of hydrogen and an alkali metal;

h. from 0.20% to 1.0% of a supplemental low temperature stabilizing agent selected from the group consisting of N-lauryl-,8amino propionic acid, dimethyl coco amine oxide, the polyoxyethylene ester of tall oil having 8 to 30 ethylene oxide units, polyoxyethylene sorbitan monolaurate containing 6 to ethylene oxide units, dodecyl methyl sulfoxide, the condensates of straight and branched chain unsubstituted aliphatic alcohols having 8 to 20 carbon atoms with from 1 to moles of ethylene oxide, and alkyl phenol-ethylene oxide condensates having from 8 to 12 carbon atoms in the alkyl group and 8 to 30 ethylene oxide units;

i. an organic acid selected from the group consisting of aliphatic acids containing from 1 to 3 carbon atoms and hydroxy aliphatic acids containing from I to 4 carbon atoms in an amount sufficient to produce a pH in the final solution of not greater than about 7; and

j. an amount of water sufficient to make 100%.

By the term consisting essentially of used in defining the foregoing compositions, it is intended that the composition may contain such optical additional ingredients as are commonly included in fabric conditioning emulsions, to improve the consumer acceptance thereof, but which do not materially affect the fabric softening properties of the emulsions. Typical optional ingredients include, but are not limited to, perfumes, colorants and germicides.

The active fabric softening compounds, (1) through (9) of the foregoing formulations, are known in the art. In the preferred embodiments of the foregoing formulations, the fabric conditioning compound is a longchain quaternary ammonium compound, 1) above, or an alkylene amide compound, (9) above, or a mixture thereof. The long-chain quaternary ammonium compounds (1) which may be used in the preferred embodiment are those containing from 2 to 3 long-chain aliphatic hydrocarbon groups and 1 to 2 lower alkyl groups on the quaternary ammonium nitrogen. The long-chain aliphatic group may contain 16 to 20 carbon atoms, may be straight or branched chain, and may be.

saturated or unsaturated. For commercial convenience, such materials are commonly derived from tallow, which contains substantial amounts of C fatty acids.

As is well known in the art, the fabric conditioning properties of the quaternary ammonium compounds (1) are afiected by the length of thelong-chain aliphatic hydrocarbon radical. Thus, radicals of shorter chain length, i.e., below about 16 carbon atoms, are not preferred because they are substantially less effective as fabric conditioners. If the quaternary ammonium compound contains long chain radicals, having more than 20 carbon atoms, it tends to impart an undesirable water repellancy to the fabric. Experience has shown that compounds containing from 16 to 20 carbon atoms in the aliphatic group provide a satisfactory balance in the fabric conditioning property.

The lower alkyl group of the quaternary ammonium compound (1) should contain from 1 to 3 carbon atoms, and may be a straight or branched chain group. The most important groups are methyl, ethyl, propyl and isopropyl radicals.

The anion portion of the long chain quaternary ammonium compounds (1) may be a halide, particularly chloride, bromide, or iodide, a sulfate or an alkylsulfate such as methyl sulfate, or an acetate.

Preferred long chain quaternary ammonium compounds l for use in this invention have two long chain aliphatic and two lower alkyl groups. Typical compounds are dihexadecyl dimethyl ammonium bromide, distearyl diethyl ammonium chloride, distearyl dipropyl ammonium chloride and ditallow dimethyl ammonium methyl sulfate. Quaternary ammonium compounds containing three long chain aliphatic groups may be used, but lesser quantities may be required, as the fabric. conditioning properties are affected by the number of long chain aliphatic groups. A typical compound of this category is tristearyl monomethyl ammonium chloride.

The reaction product of a fatty amine and epichlorohydrin, compound (8), probably contains a number of chemical entities having fabric softening ability. Potential reaction products formed by these materials include on R Because of the bifunctional properties of the reactants, numerous other species are also possible and may be present.

' The fatty acid amides, compound (9), which may be used in the preferred embodiments are the products of the reaction of one mole of a long-chain fatty acid with two moles of a hydroxyalkyl alkylamine diamine. The long-chain fatty acid should contain from 16 to 20 carbon atoms as described above with respect to the longchain aliphatic hydrocarbon portions of the quaternary ammonium compounds (1). The hydroxyalkyl group may contain from 1 to 3 carbon atoms, typicalgroups being methanol, ethanol and propanol radicals. The alkylene group may be either methylene or ethylene. The preferred compounds contain about two fatty acid groups having a typical formula such as N,N- distearoyl-N-hydroxyethyl ethylene diamide. While reaction product of the fatty acid and alkanol alkylene diamine is nominally a diamide, spectral analysis shows that a number of chemical species are present in the material. A typical anaylsis indicates that the product contains about 25% cationics such as imidazoline, the balance being esters and amides.

The foregoing fabric conditioners may be used alone in the preferred formulations, if desired. It has been discovered, however, that improved fabric conditioning properties are obtained if the quaternary ammonium compounds and the diamides mentioned. above are used together in the weight ratio of about 1:4 to 4:1.

In place of the preferred compounds (1) or (9), or mixtures thereof as described above, compounds-(2) through (8) may be used alone or in combination with any of the fabric conditioners described herein. In each case, the fabric conditioning compounds are characterized by a cationic nitrogen atom carrying one or more long-chain aliphatic or carboxy hydrocarbon groups, having 16 to 20 carbon atoms. These long-chain groups are as described above with respect to the preferred compounds (1) and (9). The compounds (2) to (8) also contain various other functional groupings of lower alkyl, lower alkylene, lower hydroxyalkyl and lower acyl radicals. These lower groups generally contain from I to 3 carbon atoms, and are analogous in description to the lower alkyl, lower hydroxyalkyl and lower alkylene groups discussed above in connection with compounds (1) and (9).

Where the active fabric conditioner is used in the aqueous emulsion, described in the foregoing formulations, the concentration of the fabric conditioning compound in the formulation does not affect the fabric conditioning properties of'the emulsion. However, the preferred emulsions contain between about 4 and 7% by weight of the active ingredient. If excessively high concentrations of fabric conditioning compounds are used, the emulsion becomes a hard gel and is not desirable for household use. On the other hand, a weak solution is not preferred because of the large amounts of emulsion which would then be required to provide an effective amount of the fabric conditioning compound in the rinse water. Experience has indicated that emulsions containing from 4% to 7% of the fabric conditioning compounds are most acceptable from the consumers standpoint.

As stated, an important feature of the present invention is the use of an emulsion of the foregoing fabric conditioner in aqueous emulsions in which a shortchain quaternary ammonium compound is provided to stabi lize the emulsion against irreversible gelation at low temperatures. The shortchain quaternary ammonium compounds are particularly desirable as low temperature stabilizers because they have the property of preventing irreversible gelation during cyclic freezing and thawing. At the same time, they do not interfere with the fabric conditioning properties of the active ingredi ents. Hereinafter and in the appended claims, these compositions will be designated as low temperature stabilizing agents.

For use in conjunction with the usual commercial emulsions, containing from about 4 to 7% of a fabric conditioning compound, about M1 to about 2 of the low temperature stabilizing agent should be provided. In the preferred formulation, the amount of low temperature stabilizing agent is between A and 1%.

Amounts less than one-fourth percent of the low temperature stabilizing agent may be used, particularly if the formulation contains relatively small amounts of the fabric conditioning compounds. However, such small concentrations of the short-chain quaternary ammonium compounds have relatively little stabilizing value.

The maximum usable concentration of the low temperature stabilizing agent depends on the high temperature stability of the resulting emulsion. If amounts of short-chain quaternary ammonium compounds in excess of about 2% are used, it has been found that the resulting emulsion will tend to separate on standing at room temperature. It is preferred, that the amount of short-chain quaternary ammonium compound be less than 1% since emulsions containing more than 1% of the short-chain quaternary ammonium compound tend.

aliphatic hydrocarbon radicals containing from 10 to t 14 carbon atoms, and from 1 to 3 lower alkyl radicals containing from 1 to 3 carbon atoms. The short-chain aliphatic hydrocarbon radicals may be straightor branched chain, and may be saturated or unsaturated. For commercialconvenience, thealiphatic hydrocarbon radicals are usually derived from natural sources such as coconut oil, although synthetic sources may be used. The lower alkyl radicals may be straight or branched chain such as methyl, ethyl, propyl or isopropyl. The anion portion of the quaternary ammonium compound may be a sulfate or halide, especially bromides, chlorides or iodides.

Preferred compounds have two aliphatic radicals and two lower alkyl radicals. Illustrative compounds are didecyl diethyl ammonium chloride, and ditetradecyl dimethyl ammonium chloride. A preferred compound is dicoco dimethyl ammonium chloride. Monoand trisubstituted quaternary ammonium compounds may be used, such as monococo triethyl ammonium chloride, and tricoco monomethyl ammonium chloride. Such compounds have greater or lesser value as emulsion stabilizers depending on the number of aliphatic groups on the ammonium nitrogen. Accordingly, greater or lesser amounts of these compounds may be used.

Nonionic or amphoteric compounds also possess low temperature stabilizing properties in fabric conditioning emulsions. These are referred to as supplemental stabilizers in the emulsion of this invention, in amounts up to 1% to supplement the effectiveness of the above short chain quaternary ammonium stabilizer. Such supplemental stabilizers are especially advantageous where the emulsion may require excessive amounts of 3 of talloil having from 8 to 30 ethylene oxide units,

9: polyoxyethylene sorbitan monostearate having from 6 to 20 ethylene --oxide units, dodecyl methyl sulfoxide, ethylene oxide condensates of straight and branched chain unsubstituted aliphatic alcohols having from 8 to 20 carbon atoms and from to 30 ethylene oxide units, .An unexpected discovery (of the present invention is and alkyl phenol-ethylene oxide condensates having 8 that lower aliphatic alcohols adversely affect the low to 12 carbon atoms in the alkyl chain and 8 to 30 ethyltemperature stability of emulsions of fabric conditionene oxide units. Amounts greater than 1% of the foreing compounds. While in the normal case one would going compounds are generally not preferred as emulexpect that such alcohols as methyl alcohol, ethyl alcosion stabilizers, as large amounts of these stabilizers adhol, or isopropyl alcohol would improve the low temversely affect the fabric softening ability of the fabric perature stability of an aqueous emulsion, it has been conditioning-active ingredients which are present. discovered that in the emulsions of the instant invenln addition to providing for the presence of a stabition, the presence of excessive amounts of alcoholadlizer in the emulsion of the fabric conditioning comversely affects low temperature stability. In the prepounds, certain other limitations on the emulsion com- 15 ferred formulations, the emulsion is substantially free position must be observed in order to insure adequate of alcohol. Inasmuch as many of the commercially stability. It has been discovered that in order to obtain available raw materials used in the formulating emulsatisfactory emulsions, the amount of ionizable salts sions contain small amounts of alcohol, it is not practipresent should be between 0.005% and 0.10% and furcal in many instances to prepare alcohol-free emulther, the amount of lower aliphatic alcohols present sions. Satisfactory results are obtained, generally, proshould be less than 1.0%. vided that the amount of alkyl alcohol is below about The amount of ionizable salts present in the fabric 1%. conditioning formulations has been found to exert an e foregoing techniques for improving the physical influence on the viscosity of the emulsion. Thus, at exstability of a fabric softening emulsion are preferably tremely low concentrations, i.e., less than 0.005%, de-. used jointly, especially when an optical brightener is creasing the amount of ionizable salts increases the vispresent. It will be appreciated that any one of the forecosity of the emulsion. On the other hand, at higher going methods may be used to improve emulsion stabilconcentrations, i.e., in amounts in excess of 0.10%, inity desired. e the amount of ionizable ealts tend? to As stated, an important part of this invention relates 9 scihdlfy h emfflslon emulvslon of F fluld' to fabric conditioning formulations to which an optical 18 Obtained If thefofmulanon comams between brightener has been added. Such formulations may be 000572) 10% of prepared in either the dry state or as emulsions. While Typfcal lomzable Salts affectmg the f of the formulators of fabric conditioning compounds have reemulslon the Salts P the mmeral '9 Strong' alized the desirability of adding an optical brightener to bases- Such as. f and the a]kah a Most the compounds, it has been found that many combinacommoffly such Salts l sodlum potasslum and tions of optical brightener and fabric conditioners reammomum sulfates and hahdes phosphates and other sult in a marked reduction 'in the effectiveness of the such salts resulting as by-products 1n the manufacture brightenen of the various raw materials used in preparing fabric conditioning emulsions. If hard water is used in the 40 The reasons for this u t are not understood. The preparation f the f b i conditioning emulsions the fabric conditioners such as described above are waterionizable salts therein have also been observed to affect insoluble *compeunds, and o g y it is thought to the viscosity of the emulsions. These includethe divabe unlikely that y substantial unt of the condilent and trivalent metal salts, such as calcium chloride, ttonet' is deactivated y the fotmation of a complex barium chloride, and other alkaline earth salts, and alutween the large iohtled CatiOnS 0f the fabric Condiminium chloride and ferric chloride, as well as nitrates, tioner with large ionized anions 0f Optical sulfates, and phosphates of the aforementioned metals. f g one Possible explanation for this result m y Other. ionizable salts affecting the fluidity of the erhul- I h the meehantsm'b)" which. the fabric n itioner sions are the soluble salts of the abovementioned meoptical bt'tghtenet are bonded to the clc'th fabric tallic ions with organic acids containing from 1 to 4 carbemg treatedatoms- These include the aliphatic acids e as Whatever the explanation of this adverse interaction, formic, acetic, propionic and the substituted acids such ma'ny seemingly contradictory results have b as the hydroxy aliphatic acidslieitri acids, tartaric, served. For instance it has been observed that when a malonic and maleic acids. g mixture of aquaternary ammonium fabric conditioner In the preferred practice of this invention fabric cond an a id t f b i di i h as ditioning formulations are prepared from ingredients d 1 a d 9 described above, are admixed with selected so that they will be substantially free of salts. a stilbene dye having the structure:

NH NH C-N NC i r N i C--NH- CH CH- NH--C N 2 I C=N S0,,Na NaO,,S N=C 1 NH NH To the resulting,substantially saltfree emulsion, a controlled amount of an ionizable salt isadded. Salts of the hydroxy aliphatic acids .are particularly desired for the.

purpose.

many repeated applications are required before accept able brightening activity is obtained, although the dye, in the absence of the fabric conditionersfls known to be extremely effective. By contrast, when the fabric conditioners are mixed with a stilbene dye having the formula:

HOCH CH CH CH OH optical brightening is obtained after only one or two rinsings. A second optical brightener according to the present invention which has been found to yield such unexpected results has the formula:

In the foregoing dyes, the sodium cation attached to the sulfonate group may be replaced by hydrogen or another alkali metal.

Mixtures of the foregoing dyes and fabric conditioneirs may be used in either dry form or in aqueous emulsions as has been already mentioned. When prepared into a dry, or granulated fabric conditioning formulation, the composition should contain from 0.5 to parts by weight of the optical brightener, and from 99.5 to 80 parts of the fabric conditioner.

Satisfactory results may be obtained by a simple dry blending of the granulated solids. However, other methods-of preparation, such as co-melting the solids,

may also be used.

The relative proportions of the fabric conditioner and optical brightener employed will depend on the relative need for softening and whitening of the fabric. Where the primary objective is softening, and relatively little whitening is needed, the ratio of softener to brightener will be relatively high. Conversely, where it is desired to provide a substantial amount of whitening during the fabric conditioning step, the ratio of fabric conditioner to optical brightener will be considerably lower. The percentages of fabric conditioner and dye may be adjusted within the above-stated limits to suit the requirements of each case.

In addition, the solid granulated products may contain solid diluents. Such diluents, of course, should not be present to such an extent that unreasonable amounts of the product would be required to provide satisfactory fabric softening; however, the diluted mixture may nocn cu cH,cH,oH

as well as sulfates, borates, citrates, phosphates, urea and the like.

When mixtures of theforegoing optical brightener and fabric conditioner are used in emulsions, it has been found that the emulsion rapidly tends to become a heavy, viscous mass. One factor accounting for this result is that the commercially available sources of optical brighteners of the foregoing type contain substantial amounts of ionizable salts Thus, in one case, an optical brightener containing 68% active material, when added at a concentration of 0.2% by weight, provides almost 0.1% ionizable salts. As discussed above, such high levels of salts cause the emulsion to become undesirably viscous. This may be avoided by the selection of salt-free raw materials.

Incorporation 'of the foregoing optical brighteners, even in the salt-free form, however, gives rise to a physicalinstability problem. At temperatures below freezing.(ab0ut 30 the emulsion thickens to a gel-like consistency, and does not return to a fluid state upon su'bsequent'storage at room temperature.

To overcome this difficulty, additional amounts of low temperature stabilizer are required. For this purpose, the short chain quaternary ammonium compounds may be used, provided that the concentration of theshort chain quaternary ammonium compounds is not so high, as to adversely affect the stability of the resulting emulsion. However, in the usual case it is not possible to provide a sufficient amount of a short chain quaternary ammonium compound to completely stabilize the emulsion. Accordingly, the addition of a low level of a second, or supplementary, emulsion stabilizer is preferred.

The emulsion stabilizers are the amphoteric and nonionic compounds described above, which, as pointed out, are effective stabilizers in their own right and may be used above if desired. Compounds which may be used include: N-lauryl-B-amino propionic acid, dimethyl coco amine oxide, the polyoxyethylene ester of tall oil containing 8 to 30'ethylene oxide units, polyoxyethylene lauryl ether containing 1 to 30 ethylene oxide units, polyoxyethylene sorbitan monolaurate contain- 1 3 ing 6 to 20 ethylene oxide units, dodecyl methyl sulfoxide, ethylene oxide condensates of straight and branched chain unsubstituted aliphatic alcohols con taining l to 30 ethylene oxide units and alkylphe'nol ethylene oxide condensates having 8 to 12 carbon atoms in the alkyl chain and 8 to 30 ethylene oxide units. Examples of compounds which are not useful include the disodium salt of N-tallow, ,B-amino dipropionate and the sodium salt of N-lauryl ,B-amino dipropionate (both amphoteric compounds) and polyoxyethylene stearate, N-sorbitan monolaurate (both nonionicv effect on the fabric conditioning properties of the ac-' tive compounds and are therefore not preferred. On the other hand, a sufficient amount must be present to provide effective emulsion stabilization. It has been found that the optimum balance is obtained when the nonionic or amphoteric compounds are present in a range of about 0.20% to 1.0%.

When optical brighteners are used in conjunction with fabric conditioners it has also been observed that the pH of the emulsion affects the stability. In general, any pH below 7 provides adequate stability; however optimum is obtained between a pH range of about 3.0 to 4.5. At pH values above 7, the emulsion tends to precipitate upon standing. In general, the lower the pH,.

the more uniform is the absorption, but the rate of absorption is lower. A pH range of about 3.0 to 4.5 provides an optimum balance between stability, uniformity of absorption and rate of absorption.

Certain of the raw materials, especially the commercially available fatty acid amides, are quite alkaline because they usually contain free amines. Accordingly, it is necessary to acidulate the emulsion with an organic acid to a pH below 7, and preferably to a pH between about 3.0 and about 4.5

Acids which may be used for this purpose are the lower aliphatic acids containing from 1 to 3 carbon atoms, for example, acetic and propionic acids, and the hydroxy aliphatic acids containing from 1 to 4 carbon atoms such as citric, tartaric, malonic and maleic acids. The hydroxy aliphatic acids are preferred because they are free from objectionable odors.

In connection with the adjustment of the pH of the emulsion, it should be noted that in the absence of an optical brightener, the pH control is not necessary. Nevertheless, it may be desirable to add a small amount of an acidulating agent to the emulsion even when optical brighteners are not used to neutralize the free amines in the fatty acid amides. These amines are known to be irritating to the skin, and accordingly, sufficient acid may be added with the fatty acid amide to.

reduce skin irritation.

No special methods of manufacture are required in preparing emulsions of the type described above. A

simple blending operation combined with moderate agitation will suffice for most cases.

In an illustrative process, the fabric conditioning emulsion is prepared by first co-melting fabric conditioning compounds (1) and (9) together with the short chain quaternary ammonium compound used as a low temperature stabilizer at a temperature of to F. The-optical brightener, a supplementary emulsion stabilizer, such as the ethylene oxide condensate of tridecyl alcohol is added to the hot melt in that order. The resulting mixture is then dispersed, while still in a mol-, ten condition, in water containing the supplementary salt if needed, and acidulant (eg sodium citrate and citric acid) at .170F., and the hot solution is agitated to promote a thorough dispersion. Thereafter the dispersion is cooled to room temperature, and the minor ingredients such as the colorants and perfume are added.

For a better understanding of the fabric conditioning emulsions of the present invention, reference may be had to the following examples.

EXAMPLE 1 Samples of a 5% emulsion of distearyl dimethyl ammonium chloride in the presence of 0%, 0.5% or 1% of dicoco dimethyl ammonium chloride were placed in storage at 10F. and cycled daily to room temperature. The samples were prepared from a distearyl dimethyl ammonium chloride containing 0.09% sodium chloride and 15.2% alcohol, and from a dicoco dimethyl ammonium chloride containing 0.09% sodium chloride and 15.2% alcohol. The resulting emulsions contained 0.0045% to 0.0054% sodium chloride and0.76% to 0.91% isopropyl alcohol.

After seven cycles, the physical state of the emulsion was noted.

Concentration of 0.0% Nonpourable, solid gel 0.571 Fluid and stable 1.07: Fluid and stable EXAMPLE 2 Example 1 was repeated substituting a 5.6% emulsion of N,N'distearoyl Nethanol ethylene diamide for the emulsion of distearyl dimethyl ammonium chloride of Example 1. The resulting emulsion contained 0.076% alcohol and 0.005% salt. The following observations were made after seven 24 hour cycles.

Concentration of :n)2(C ul=N*Cl Physical State 0.0% Nonpourable gel 0.57: Fluid and stable EXAMPLE 3 Example 1 was repeated using an emulsion containing 2.8% distearyl dimethyl ammonium chloride and 2.8% N,N'distearoyl Nethanol ethylene diamide in place of the emulsion of Example 1. The emulsion contained 0.54% alcohol and 0.033% sodium chloride. The following observations were made after seven 24 hour cycles.

Concentration of Nonpourablc gel Fluid and stable EXAMPLE 4 A series of formulations were prepared having the following basic composition:

Distearyl dimethyl ammonium chloride N,N'distcaroyl, N'ethanol ethylene diamide Dicoco dimethyl ammonium chloride The condensate of 1 mole of tridecyl alcohol with 10 moles of ethylene oxide Citric acid monohydratc Sodium citrate dihydrate An optical brightener of the formula N SO Na NaO S HOCH2CH2 CHQCHZOH Colorantsperfume and water, to make 100%.

retained their original viscosity. The valence of the cation of the added ionizable salt did not appear to be a significant factor.

EXAMPLE 5 Certain of the ingredients of the fabric conditioning formulation, particularly the quaternary ammonium compounds, contain minor amounts of isopropanol. Thus, the distearyl dimethyl ammonium chloride may contain up to 18% alcohol and the dicoco dimethyl ammonium chloride contain about 17% alcohol.

A series of formulations were made using the basic formula of Example 4, in which the amc-unt of alcohol accompanying the distearyl dimethyl ammonium chloride was 0%, 15% and 18%. Formulations in which the total alcohol content was 0.10%, 0.54% and 0.62% resulted. After storage at 10F. for 1 week it was observed that the formula containing the least amount of alcohol returned to the fluid state most readily.

EXAMPLES 61 1 A number of illustrative ,fabric conditionerfluorescent dye formulations in powdered form are set forth as follows. Each of the formulations was prepared by dry blending of the ingredients in the proportions set forth:

2.91% (by weight) /NH --NH--C N HOCH CH CH CH OH TABLE NO. 1

Powdered Fabric Conditioning Formulations Example No.

6 9 6 gms. distearyl dimethyl ammonium chloride 4 gms. salt-free optical brightencr TABLE NO. l-Continued Powdered Fabric Conditioning Formulations Example No.

The swatches of cotton cloth were washed in a Terg- O-Tometer using all," a commercially available nonionic detergent, which contained no brightener. After washing for 15 minutes at 120 F. and 150 oscillations/- f Formula m) above min., the swatches were rinsed twice for 3 minutes in 7 92 gms. distearloiyl ehhanol difamidc plain water at 120 F. and then rinsed for 3 minutes at 7 Jill" 'll'll") i if ll 1" S i L 100 F. in water at 120 li containing one of the above 1 gm. sodium chloride samples of a fabric conditioner emulsion of a concen- 8 8t) gms. quaternary ammonium complex I of u mndificd kmg Chain amide tration of l .1 02/16 gal. After the final rinse the swatch- 20 gms. salbfrec optical hrightener l0 es were dried for one-half hour in a commercial home of Formula above 9 25 gnu dimmyl dimuthy} ammonium drier. The above washing, rinsing and drying cycles chloride. were repeated 10 times. 1 a f s After the first, second, fifth and tenth washing cycles,

ormu ll ll OVC three of the cotton swatches were removed from the 74 gms. urea 10 hvcwdccyl iffliduzqlinc Sulfate final rinse water, tagged and separately dried and the 4 i l 9 hnghwmr of three dried swatches were ironed with an electric iron orniula ([0) above l l 96 gmsv ditallow dimethyl ammonium at the W001 setting.

methyl sulfate 4 gnu Sammy; Optical brightcncr of The fluorescence value of each of these swatches was Formula 4 l0) ahove measured in a Beckmann DU Spectrophotometer having a reflectance attachment and adapted for fluores- E l NO 12 cence measurements by use of a Wratten 2B filter. The fluorescence stimulatin wave len th was 380m The To illustrate the performance of various optical g g fluorescence values were measured on each side of brighteners when using in COIIJUIICUOII with fabric coneach cloth. The average of six readings, two sides of ditioners, four formulations of the composition set each of three cloths, is set forth in the following table. forth in Example 4 were prepared. One formulation, Sample A, contained 0.20% of the optical brightener of Bfighmcss Aficr washing Formula lo) 88 ShOWIl in Example 4. In the remaining Fabric Conditioner l cycle 2 cycles 5 cycles 10 cycles samples the optical brightener of Formula (10) was Simple A 177 208 v86 x66 omitted, and in place thereof, 0.20% of an optical Sample B 298 34,3 brightener was substituted according to the following sample C 221) Sample D [0.2 l4.() I93 24.] schedule:

Sample B:

I N- YCH=CH N SO Na Sample C:

\ NH NH /CN\ C\ N CNH@CH CH-Q-NH-C N /C=N SO;,Na Nao s N=C\ NH NH Sample D:

NH\ NH /CN\ /NC\ N\ C-NH -CH CH- -NH C /N C= =c SO Na mo s 7CN N-CH H..C CH. H C CH o ci+ H- C From these data it may be seen that effective bright ening develops much more rapidly when using optical brighteners of Formulas l) and l l l above (Sample A and Sample l3. respectively) than when using other types of brighteners.

While the invention has been described in the foregoing specification with respect to particular examples and compositions, it will be recognized by those skilled in the art that many variations of the present invention are possible. Accordingly. the present invention is not to be limited save by the spirit of this disclosure and the following claims.

We claim;

I. An aqueous emulsion consisting essentially of the following components in approximately the following proportions by weight:

a. a fabric softening compound selected from the group consisting of 7, diethyl amino etham)l-stearamide-ethyl sulfates;

and

H. the reaction product of about 2 moles of an acid of the formula R (()()H and about 1 mole of an alkylene diamine having the formula:

N- can N said reaction product being a mixture of amides, esters and imidazolines wherein R is an aliphatic hydrocarbon group containing from l6 to 20 carbon atoms, R is an alkyl group containing from I to 3 carbon atoms R is selected from the group consisting of R and R. R, is an aliphatic hydrocarbon group containing from 15 to 1) carbon atoms R is an alkylene group containing from I to 2 carbon atoms, R is a hydroxyalkyl group containing from 1 to 3 carbon atoms X is an anion selected from the group consisting of halides, sulfates alkyl sulfates having 1 to 3 carbon atoms in the alkyl group and acetates, and y is the valency of X, the total amount of compounds (l) to (8) present being between 4% and 7%; Y

b. from about one-fourth /4 to about 271 of a low temperature stabilizing agent of the formula:

wherein R is an aliphatic hydrocarbon group containing from It) to l4 carbon atoms, each R is selected from the group consisting of R and R and R X and y are as hereinabove defined;

c. from about 000571 to about 0.10% of inert ionizable salts selected from the group consisting of inorganic salts and salts of organic acids containing from 1 to 4 carbon atoms;

d. not more than about 171 of a lower unsubstituted aliphatic alcohol;

e. from 0 to 1% of a supplementary emulsion stabilizer selected from the group consisting of N-laurylfi-amino propionic acid dimcthyl coco amine oxide, the polyoxyethylene ester of tall oil having 8 to 30 ethylene oxide units, polyoxyethylene sorbitan monostearate containing 6 to 20 ethylene oxide units dodecyl methyl sulfoxide the condensates of straight and branched chain unsubstituted aliphatic alcohols having from 8 to 20 carbon atoms with from i to 30 moles of ethylene oxide and alkyl phenol-ethylene oxide condensates having 8 to 12 carbon atoms in the alkyl chain and 8 to 30 ethylene oxide units;

f an amount of water sufficient to make 10071.

2. The formulation according to claim 1 wherein said low temperature stabilizing agent is present in an amount between about one-fourth "/1 and about 171.

3. An aqueous emulsion consisting essentially of the following components in approximately the following proportions by weight:

a. from about 4% to about 7% of a fabric softening compound of the formula:

wherein R is an aliphatic hydrocarbon group containing from 16 to 20 carbon atoms, R is an alkyl group containing from 1 to 3 carbon atoms, R is selected from the group consisting of R and R X is an anion selected from the group of halides, sulfates, alkyl sulfates having from 1 to 3 carbon atoms in the alkyl group, and acetates, and y is the valency of X;

b. from about one-fourth to about 2% of a low temperature stabilizing agent of the formula:

wherein R is an aliphatic hydrocarbon group containing from to 14 carbon atoms, each R is selected from the group consisting of R and R and R X and y are as hereinabove defined;

c. from about 0.005% to about 0.10% of inert ionizable salts selected from the group consisting of inorganic salts and salts of organic acids containing from 1 to 4 carbon atoms;

d. not more than about 1% of a lower unsubstituted aliphatic alcohol;

e. from 0 to 1% of a supplementary emulsion stabilizer selected from the group consisting of N-lauryl- B-amino propionic acid, dimethyl coco amine oxide, the polyoxyethylene ester of tall oil having 8 to 30 ethylene oxide units, polyoxyethylene sorbitan monostearate having 6 to 20 ethylene oxide units, dodecyl methyl sulfoxide, condensates of straight and branched chain unsubstituted aliphatic alcohols having 8 to 20 carbon atoms with from 1 to 30 moles of ethylene oxide, and alkyl phenol-ethylene oxide condensates having 8 to 12 carbon atoms in the alkyl chain and 8 to 30 ethylene oxide units;

f. an amount of water sufficient to make 100%.

4. An aqueous emulsion consisting essentially of the following components in approximately the following proportions by weight:

a. from about 4% to about 7% of a fabric softening compound which is the reaction product of about 2 moles of an organic acid of the formula R COOl-l and about 1 mole of an alkylene diamine having the formula:

said reaction product being a mixture of amides, esters and imidazolines wherein R is an aliphatic hydrocarbon radical containing from 15 to 19 carbon atoms, and R is a hydroxyalkyl group containing from l to 3 carbon atoms; b. from about A to about 2% of a low temperature stabilizing agent of the formula:

wherein R is an aliphatic hydrocarbon group containing from 10 to 14 carbon atoms, each R is selected from the group consisting of R and R and R X and y are as hereinabove defined;

c. from about 0.005% to about 0. 10% of inert ionizable saltsselected from the group consisting of inorganic salts and salts of organic acids containing from 1 to 4 carbon atoms;

d. not more than about 1% of a lower unsubstituted aliphatic alcohol;

e. from 0 to 1% of a supplemental emulsion stabilizer selected from the group consisting of N-lauryl-B- amino propionic acid, dimethyl cocoamine oxide, the polyoxyethylene ester of tall oil having 8 to 30 ethylene oxide units, polyoxyethylene sorbitan monostearate having 6 to 20 ethylene oxide units, dodecyl methyl sulfoxide, condensates of straight and branchedchain unsubstituted aliphatic alcohols having 8 to 20 carbon atoms with from 1 to 30 moles of ethylene oxide, and alkyl phenol-ethylene oxide condensates having 8 to 12 carbon atoms in thealkylychain and 8 to 30 ethylene oxide units;

f. an amount of water sufficient to make 5. A composition according to claim 4 wherein said low temperature stabilizing agent is present in an amount from A to 1%. i

6. An aqueous emulsion consisting essentially of the following components in approximately the, following proportions by weight:

a. from about 4 to about 7% of a mixture of i. a fabric softening compound of the formula and ii. a fabric softening compound which is the reaction product of about 2 moles of an acid having the formula R COOH and one mole of an hydroxyalkyl alkylene diamine and having the formula:

said compounds (i) and (ii) beingpresent in a ratio between about 1:4 and 4:1, wherein R is an aliphatic hydrocarbon group containing from 16 to 20 carbon atoms, R is an alkyl group containing from 1 to 3 carbon atoms, R is selected from the group consisting of R and R R, is analiphatic hydrocarbon group contair'iing from 15 to 19 carbon atoms, R is a hydroxyalkyl group containing from 1 to 3 carbon atoms, X is an anion selected from the group consisting of halides, sulfates, alkyl sulfates having 1 to 3 carbon atoms in the alkyl group, and acetates, and y is the valency of X;

b. from about A to about 2% of a low temperature stabilizing agent of the formula:

R, i a;

RTN -R,, x

c. from about 0.005% to about 0.10% of an inert ionizable salt selected from the group consisting of inorganic salts and salts of organic acids containing from 1 to 4 carbon atoms;

(1. not more than about 1% of a lower unsubstituted aliphatic alcohol;

e. from O to 1% of a supplementary emulsion stabilizer selected from the group consisting of N-lauryl- B-amino propionic acid, dimethyl cocoamine, oxide, the polyoxyehtylene ester of tall oil having 8 to 30 ethylene oxide units, polyoxyethylene sorbitan monostearate having 6 to ethylene oxide units, dodecyl methyl sulfoxide, condensates of straight and branched chain unsubstituted aliphatic alcohols having 8 to 20 carbon atoms with from 1 to moles of ethylene oxide, and alkyl phenol-ethylene oxide condensates having 8 to 12 carbon atoms in the alkyl chain and 8 to 30 ethylene oxide units;

f. an amount of water sufficient to make 100%.

7. A composition according to claim 6 wherein said supplementary emulsion stabilizer is present in an amount between about A and about 1%.

8. A fabric conditioning formulation consisting essentially of an aqueous emulsion of the following components in approximately the following proportions by weight:

7. diethyl amino ethanol-stearamide-ethyl sulfates;

8. the reaction product of about 2 moles of an acid of the formula R COOH and about 1 mole of an alkylene diamine having the formula:

said reaction product being a mixture of amides, esters and imidazolines wherein R, is an aliphatic hydrocar bon group containing from 16 to 20 carbon atoms, R is an alkyl group containing from 1 to 3 carbon atoms, R;, is selected from the group consisting of R and R R is an aliphatic hydrocarbon group containing from 15 to 19 carbon atoms, R is an alkylene group containing from 1 to 2carbon atoms, R is a hydroxyalkyl group containing from 1 to 3 carbon atoms, X is an anion selected from the group consisting of halides, sulfates, alkyl sulfates having l to 3 carbon atoms in the alkyl group, and acetates, and y is the valency of X, the total of said compounds (1) through (8) being from about 4% toabout 7%;

b. from about A; to about 2% of a low temperature stabilizing agent of the formula:

wherein R is an aliphatic hydrocarbon group containing from 10 to 14 carbon atoms each R is selected from the group consisting of R and R and R X and y are as hereinabove defined;

c. from about 0.005% to about 0.10% of an inert ionizable salt selected from the group consisting of inorganic, salts and salts of organic acids containing from 1 to 4 carbon atoms;

d. not more than about 1% of unsubstituted lower aliphatic alcohols;

e. an optical brightener selected from the group consisting of:

Hocmcn, CH- CH OH wherein M is a cation selected from the-group consist- R.,C =N 6B ing of hydrogen and an alkali metal, the total amount 1| 7 w of said optical brighteners being from about-0.10% to X about 0.30%; l, I i CH f. from 0.20% to 1% of a supplementaryemulsion stabilizer selected from the group consisting of N a y 'fi' Propionic acid, dimethyl COCO 7. diethyl amino ethanol-stearamidc-ethyl sulfates; amine Oxide the polyoxyethylene ester of Oil "8. the reaction product of about Z moles of an acid having 8 to 30 ethylene Oxide unitspolyoxyethyl- 'Or the formula R COOH and about 1 mole of an alene sorbitan monostearate containing 6 to 20 ethy n m' having the formula ylene oxide units, dodecyl methyl sulfoxide, the x t condensates of straight and branched chain unsubstituted aliphatic alcohols with from 1 to 30 moles of ethylene oxide and alkyl phenolethylene oxide i v condensates having 8 to 12 carbon atoms in the 15 alkyl chain and 8 to ethylene oxide units;

g. an organic acid selected from the group consisting H 7 of unsubstituted carboxylic acids containing from 1 to 3 carbon atoms and hydroxy carboxylic acids I containing f 1 to 4 carbon atoms in an amount said reaction product being a mixture of amides, esters sufficient to produce a pH below 7.0 in the result and imidazolines wherein 1 is an aliphatic hydrocar i l i bon group containing from 16 to 20 carbon atoms, R

h. an amount of water sufiicient to make 100%. is f y group containing from 1 t0 3 carbon atoms, 9. An aqueous fabric softening emulsion consisting R3 selct ed fi m the group consisting of B and 2 essentially ofthe following Components: 2 R is analiphatic hydrocarbon group containing from 15 to l9 carbon atoms, R is an alkylene group containing from 1 to 2 carbon atoms, R is a hydroxyalkyl group. containing from 1 to 3 carbon atoms, X is selected from the group consisting of halides, sulfates, I 3 alkyl sulfates havingl to 3 carbon atoms in the alkyl R: a; group, and acetates, and, y is the valency of X; and

I 1 ii. from about 0.5 to about 20 parts by weight of at a. binary mixture of .i

i. 80 to 99.5 parts by weight of at least one cationic fabric softening compound selected from the group consisting of l RINR; x i H i I least one optical brightener selected from the Y group consisting of:

H and HocH. .cH. cn cu ou HOCH2CH, cu cn ou R2 e9 wherein M is selected from the group consisting of hyi drogen and an alkali metal; (2) T Q X b. a vehicle consisting essentially of water in an 2 y amount sufficient to form a fluid emulsion at room i temperature; and

i 6 v c. an emulsion stabilizer selected from the group con- (3) Q x' sisting of quaternary ammonium compounds of the L- i y i I formula (N-R R R R ),,X wherein R is as defined above, R is an aliphatic hydrocarbon group conr i taining fromlO to 14 carbon atoms and each R is (4) i R,C0NHR ,l"-I- R i xt I selected from the group consisting of R and R and X and y are as hereinabove defined, N-lauroyl-B- y, L '1 i amino propionic acid, dimethyl cocoamine oxide,

i CONHR -,NR: I y I the polyoxyethylene esters of tall oil having 83O H i ethylene oxide units, polyoxyethylene sorbitan R,C 1Tl Q I monostearate having 6 to 20 ethylene oxide units,

(5) "N CH2 dodecyl methyl sulfoxide, condensates of straight i 3 CH2 y hols having 8-20 carbon atoms with from 1-30 and branched chain unsubstituted aliphatic alco-- moles of ethylene oxide, the alkyl phenol-ethylene oxide condensates having 8-1 2 carbon atoms in the alkyl chain and 830 ethylene oxide units, the amount of said emulsion stabilizer being sufficient to reduce the tendency of said emulsion to form an irreversible gel when subjected to freezing temperatures; and I d. from about 0.005% to about 0.10% of said emulsion being an inert inionizable salt. selected from the group consisting of inorganic salts and salts of organic acids containing from 1 to 4 carbon atoms; and

e. said emulsion having a pH less than about 7.

10. A composition according to claim 9 wherein not more than about 1% by weight of said emulsion is lower alkyl alcohols.

11. A composition according to claim 9 wherein said cationic fabric softening compound is di-tallow dimethyl ammonium halide.

12. Acomposition according to claim 11 wherein said optical brightener is the compound offormula in which M is hydrogen.

13. A composition according to claim 12 wherein said emulsion stabilizer is a straight or branched unsubstituted aliphatic alcohol having from 8-20 carbon atoms condensed with from 1-30 moles of ethylene oxide.

14. A composition according to claim 12 wherein said emulsion stabilizer is an alkyl phenol ethylene oxide condensate having 8-12 carbon atoms in the alkyl chain and from 830 ethylene oxide units.

15. Acornposition according to claim 12 wherein said emulsion stabilizer is a quaternary ammonium compound of the formula N( R R R R ),,X wherein R R R y and X are as defined above.

wherein R, is an aliphatic hydrocarbon grouphaving from 16 to 20 carbon atoms, R is an alkyl group having from 1 to 3 carbon atoms, R is selected from the group consisting of R and R and X is an anion selected from the groupconsisting of halides, sulfates, alkyl sulfates having 1 to 3 atoms in the alkyl group and acetates and y is the valency of X; i V

b. from about Ato about 2% of a low temperature stabilizing agent of the formula the condensates of straight and branched chain.

unsubstituted aliphatic alcohols with from 1 to 30 moles of ethylene oxide and alkyl phenolethylene oxide condensates having 8 to 12 carbon atoms in the alkyl chain and 8 to 30 ethylene oxide units;

d. An optical brightener selected from the group consisting of:

. 16. A fabric conditioning formulation consisting essentially of an aqueous emulsion of ,the following components in approximately the following proportions by weight: l

a. from 4% to 7% by weight of a fabric softening compound having the formula HOCH CH UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION o PATENT NO. 2 3,904,533 P DATED September 9, 1975 age 1 of 5 INVENTOR( I Oscar W. Neiditch and Jerome Rudy It is certified that error appears in the above-identitied patent and that said Letters Patent are hereby corrected as shown below;

. Col. 1, Line 22, "appp ear" should read appear Col. 1,. Line 44, the "N" in formula (3) should be a part of the aromatic ring Col. 1, Lines 47-52, H e

a R -CONH-R NR x 1 R CONHR N-R y Q should read 1 R CO-NHR NR X CO Gr l R -CONH-R NR y Col. 1, Line 63, "7." should read (7) Col. 1, Line 64, "8." should read (8) Col. 1, Line 66, "9." should read (9) I q 'Col. 2, Line 57, "brighteneing" should read brightening Col. 4, Lines 8, 12, 25, 29, 31, 45 and 53, "a.", "b.", "c.",

"d. "e. "f. and "g. should read (a) (b) (c) (a) (e) (f) an (g) Col. 5, Lines 12, 25 and 32, "h.", "i.", and "j." should read and (j) Col. 5, Line 35, "optical" should read optional Col. 5, Line 42, "softening" should read conditioning Col. 6, Line 23, insert also between "may" and "be" Col. 6, Line 62, "embodiments" should read embodiment UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,904,533 age 2 of 5 DATED September 9, 1975 INVENTOR( I Oscar W. Neiditch and Jerome Rudy It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 6, Line 64, "alkylamine" should read alkylene Col. 7, Line 42, insert after "4" Col. 7, Line 57, "shortchain" should read short-chain Col. 8, Line 2, insert after "4" Col. 8, Line 3, insert after "l/4" Col. 8, Line 6, insert after "l/4" Col. 10, Line 1, "saltfree" should read salt free Col. 18, Line 19, "Beckmann" should read Beckman Col. 20, Line 1, "7. should read (7) Col. 20, Line 3, "8." should read (8) Col. 22, Line 3, insert after "l/4" Col. 22, Line 37, insert after "l/4" Col. 22, Line 41, insert after "4" Col. 22, Line 45, "X should read X" Col. 23, Line 4, insert after "l/4" Col. 23, Line 24, "polyoxyehtylene" should read polyoxyethylene Col. 23, Line 36, insert after "l/4" Col. 24, Line 16, "7. should read (7) Col. 24, Line 17, "8. should read (8) Col. 24, Line 33, "2carbon" should read 2 carbon Col. 24, Line 40, insert after "l/4" Col. 24, Line 60, the first "H" in the formula should read Col. 25, Line 14, "phenolethylene" should read phenol-ethylene r Col. 25, Line 34, "Y" of formula (1) should read y Col. 25, Line 54, N should be inserted in formula (3) within the aromatic ring Col. 26, Line 7, "7. should read (7) Col. 26, Line 8, "8." should read (8) Col. 26, Line 35, the first "H" of the formula should read UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. I 3, 904,533

DATED I September 9, 1975 |NVENT0R(5) 3 Oscar W. Neiditch and Jerome Rudy It is certified that error appears in the ab0veidentified patent and that said Letters Patent are hereby corrected as shown below:

Col. 26, second formula, there should be a bond from the third aromatic ring to 803M Col. 28, Line 8, "l/4to" should read l/4% to Page 5 of 5 Signed and Sealed this twen ty-fo urth D 3) Of February 1 976 [SEAL] A ttes t:

RUTH C. MASON C. MARSHALL DANN Arresting Officer ('mnmi'ssimur vfParents and Trudcmurkx

Claims

1. AN AQUEOUS EMULSION CONSISTING ESSENTIALLY OF THE FOLLOWING COMPONENTS IN APPROXIMATELY THE FOLLOWING PROPORTIONS BY WEIGHT: A. A FABRIC SOFTENING COMPOUND SELECTED FROM THE GROUP CONSISTING OF

2. The formulation according to claim 1 wherein said low temperature stabilizing agent is present in an amount between about one-fourth % and about 1%.

3. An aqueous emulsion consisting essentially of the following components in approximately the following proportions by weight: a. from about 4% to about 7% of a fabric softening compound of the formula:

4. An aqueous emulsion consisting essentially of the following components in approximately the following proportions by weight: a. from about 4% to about 7% of a fabric softening compound which is the reaction product of about 2 moles of an organic acid of the formula R4COOH and about 1 mole of an alkylene diamine having the formula:

5. A composition according to claim 4 wherein said low temperature stabilizing agent is present in an amount from 1/4 to 1%.

6. An aqueous emulsion consisting essentially of the following components in approximately the following proportions by weight: a. from about 4 to about 7% of a mixture of i. a fabric softening compound of the formula

7. DIETHL AMINO ETHANOL-STEARAMIDE-ETHYL SULFATES, AND

7. diethyl amino ethanol-stearamide-ethyl sulfates; and

7. A composition according to claim 6 wherein said supplementary emulsion stabilizer is present in an amount between about 1/4 and about 1%.

7. diethyl amino ethanol-stearamide-ethyl sulfates;

8. the reaction product of about 2 moles of an acid of the formula R4COOH and about 1 mole of an alkylene diamine having the formula

8. the reaction product of about 2 moles of an acid of the formula R4COOH and about 1 mole of an alkylene diamine having the formula:

8. A fabric conditioning formulation consistIng essentially of an aqueous emulsion of the following components in approximately the following proportions by weight: a. a fabric softening compound selected from the group consisting of

8. THE REACTION PRODUCT OF ABOUT 22 MOLES OF AN ACID OF THE FORMULA R4COOH AND ABOUT 1 MOLE OF AN ALKYLENE DIAMINE HAVING THE FORMULA:

9. An aqueous fabric softening emulsion consisting essentially of the following components: a. binary mixture of i. 80 to 99.5 parts by weight of at least one cationic fabric softening compound selected from the group consisting of

12. A composition according to claim 11 wherein said optical brightener is the compound of formula (10) in which M is hydrogen.

14. A composition according to claim 12 wherein said emulsion stabilizer is an alkyl phenol-ethylene oxide condensate having 8-12 carbon atoms in the alkyl chain and from 8-30 ethylene oxide units.

15. A composition according to claim 12 wherein said emulsion stabilizer is a quaternary ammonium compound of the formula N(R2R7R8R8)yX wherein R2, R7, R8, y and X are as defined above.

16. A fabric conditioning formulation consisting essentially of an aqueous emulsion of the following components in approximately the following proportions by weight: a. from 4% to 7% by weight of a fabric softening compound having the formula