US3892669A

US3892669A - Clear fabric-softening composition

Info

Publication number: US3892669A
Application number: US301546A
Authority: US
Inventors: Anthony A Rapisarda; Kenneth F Schoene; William B Benken
Original assignee: Lever Brothers Co
Current assignee: Lever Brothers Co
Priority date: 1972-10-27
Filing date: 1972-10-27
Publication date: 1975-07-01
Anticipated expiration: 1992-07-01

Abstract

A clear, homogeneous, aqueous fabric softening composition contains a solubilized tetraalkyl quaternary ammonium salt having two short-chain alkyl groups and two long-chain alkyl groups, about 5 percent to about 25 percent of the latter having methyl and ethyl branching on the 2-carbon; the solubilizers comprising aryl sulfonates, diols, ethers, low molecular weight quaternaries, sulfobetaines, alkyl taurines, amine-, phosphine-, and sulfoxides, and nonionic surfactants, some of the foregoing having utility only as auxiliary solubilizers.

Description

"United States Patent Rapisarda et al. 1 July 1, 1975 1 1 CLEAR FABRIC-SOFTENING 3,681,241 8/1972 Rudy 252/8.8 x COMPQSYHON 3,703,480 11/1972 Grand et a1 v. 252/8.8 X

[75] Inventors: Anthony A. Rapisarda, Elmhurst,

NY; Kenneth R Schoene, Primary Examiner-Stephen J. Lechert, Jr. Maywood; William Benken, Attorney, Agent, or Firml(enneth F. Dusyn; Arnold Cliffside Park, both of NJ. Gram [73] Assignee: Lever Brothers Company, New

York, NY. [57] ABSTRACT [22] Filed: Oct. 27, 1972 A clear, homogeneous, aqueous fabric softening composition contains a solubilized tetraalkyl quaternary [2]] Appl 301546 ammonium salt having two short-chain alkyl groups and two long-chain alkyl groups, about 5 percent to [52] U.S. Cl. 252/8.75; 252/8.8; 252/545; about 25 percent of the latter having methyl and ethyl 252/547; 252/DlG. 14 branching on the 2-carbon; the solubilizers comprising [51] Int. Cl D06m 13/38 aryl sulfonates, diols, h l m le gh [58] Field of Search 252/8.6, 8.7, 875, 8.8, quaternaries, sulfobetaines, alkyl taurines, amine-, 252/547, 545, DIG. 14 phosphine-, and sulfoxides, and nonionic surfactants, some of the foregoing having utility only as auxiliary {56] References Cited solubilizers.

UNITED STATES PATENTS 6 Claims N0 Drawings 3,660,286 5/1972 Sepulveda et al 252/547 X 1 CLEAR FABRlC-SOFTENING COMPOSITION BACKGROUND OF THE INVENTION 1, Field of the Invention Traditionally, fabric softening compositions have been marketed in the form of opaque, liquid suspensions and have been prone to cause turbid, agglomerated, nondispersed clumps of active softener components upon addition to rinse water in an'automatic washing machine. Furthermore, if sufficient amounts of anionic detergent are carried over into the rinse water, an undesirable co-precipitate of detergent-softener active may be deposited on the treated fabrics. The fabric-softening compositions of the present invention are in solution, or at least in visually clear colloidal dispersion, and in concentrated form and do not cause turbidity in diluted concentrations in the rinse water even with anionic or other detergent active present, Further, when traditional fabric softener compositions which are based on dimethyl di(hardened tallow) ammonium halide or 2-heptadecyl-l-methyl-l(stearoyl amido ethyl) imidazoline methosulfate are exposed to the atmosphere in an uncapped bottle or in an open vessel such as a washing machine automatic open cup dispenser, a rubbery skin forms over the surface which is not readily dispersible in the rinse water. These skins also have a tendency to adhere to and build up on the walls of cup dispensers. In contrast, the products of the instant invention drain substantially completely from automatic dispensing assemblies, leaving at most only a slight film, forming minimal objectionable insoluble matter.

Heretofore, the quaternary ammonium halide employed in household fabric-softening compositions has been dimethyl di(hardened tallow)quaternary ammonium chloride, or a closely homologous substance, the term hardened tallow in this instance denoting alkyl groups, principally palmityl and stearyl, derived from hydrogenated tallow. This quaternary is not readily amenable to solublization, and the desire to formulate a clear fabric softening composition necessitated a substantially complete reformulation of traditional fabricsoftening compositions.

2. The Prior Art U.S. Pat. No. 3,033,704

Discloses the use of dimethyl di(hydrogenated tallow) alkyl quaternary ammonium chloride in conjunction with an organomercurial germicide for the treatment of fabrics.

U.S. Pat. No. 3,122,502

Discloses a fluid colloidal aqueous preparation comprising at least one cationic fabric softener and at least one organomercurial germicide. The germicide may be slurried with hexylene glycol in the manufacture of the product. The hexylene glycol remains in the product in small amounts but has no disclosed solubilizing action.

U.S. Pat, No. 3,154,489

Discloses that quaternary ammonium salts and anionic detergents are compatible in the presence of a polyoxyethylenefatty amine condensation product.

U.S. Pat. No. 3,216,944

Discloses that aqueous suspensions of dimethyl di (hardened tallow) alkyl quaternary ammonium salt is stablized against phase separation by the presence of 3,4,4'-trichlorocarbanilide.

U.S. Pat. No. 3,296,145

Discloses that amine oxides are compatible with germicidal water-soluble quaternary ammonium salts hav ing one long alkyl chain. Mixtures of at least one compound of each of these classes can be prepared in aque ous liquid form as surgical scrub.

U.S. Pat. No. 3,325,404

Teaches that anionic surfactants precipitate di-(long-chain)alkyl-dimethyl ammonium chloride and like quaternaries when mixed therewith in an aqueous medium, and that the precipitation is inhibited by the presence of a mono(long-chain)-tri(short-chain)alkyl or alkylaryl quaternary ammonium compounds.

U.S. Pat. No. 3,360,470

Discloses that sodium carboxymcthylcellulose inhibits yellowing of textile materials by quaternary ammonium fabric softeners when used in water containing colored colloidal particles.

U.S. Pat. No. 3,364,142

Discloses that quaternary ammonium fabric softeners in aqueous suspension are rendered freeze-thaw stable by the addition of a condensate of a fatty alcohol and ethylene oxide.

U.S. Pat. No. 3,395,100

Discloses that a di(isostearyl)dimethyl quaternary ammonium chloride can be prepared as a highlyy concentrated, e.g., percent, fluid product in a watermiscible solvent such as hcxylene glycol, Butyl Cellosolve, or an isopropanol-water mixture. The quaternary is readily dissolved in small amounts of solvent. The precise structure of the isostearyl radical is not accurately known.

US, Pat. Nov 3,454,494

Discloses that a condensation product of a fatty acid derivative and a polyfunctional amine (e.g., diethanolamine) has fabric-softening properties and that in admixture with a nonionic surfactant (e.g. an alcoholethylene oxide condensate) is compatible with anionic detergents in the wash cycle.

U.S. Pat. No. 3,501,335

Discloses that N,N-dimethyl-N-Lhydroxystearyl amine oxide, and related compounds have fabricsoftening properties.

SUMMARY OF THE INVENTION It has now been discovered that a visually clear aqueous fabric-softening composition can be prepared containing about 2 to about 20 percent of a dimethyldi(long chain) quaternary ammonium chloride having a long-chain mixture of particular molecular configurations, and one or more solubilizers.

It is therefore an object of the present invention to prepare a visually clear aqueous fabric-softening composition.

It is another object of the invention to prepare a physically stable aqueous fabric-softening composition.

It is a further object of the invention to prepare a clear, aqueous fabric-softening composition which forms a clear dispersion when diluted to use concentration.

In one embodiment of the invention there is produced a visually clear aqueous fabric-softening composition which remains clear after having been subjected to temperatures ranging from about OF to about F, and restored at room temperature.

The term fabric softening composition as used herein denotes a composition containing one or more components which bring about a desirable change in sensory and/or physical characteristics of cloth when the cloth is subjected to treatment by the compositions in an aqueous medium, and dried. It is an object of the fabric-softening treatment to impart a soft and pleasing feel to fabrics which would otherwise tend to be harsh and stiff.

Of particular utility are the solubilizers which do not produce foam. Accordingly in a preferred embodiment of the invention there is provided a non-foaming, clear liquid fabric softening composition.

It has been found that, unlike the (ii-(hardened tallow) quaternary customarily used, a quaternary of related structure but having from about to about percent 2-(short chain)alkyl branching on the longchain alkyl groups, and having a specified chain length distribution, can be solubilized to produce a clear aqueous fabric-softening composition.

As set forth in Example 14, a use concentration (equivalent to about 2 fluid ounces of whose composition in 17 gallons of water) of quaternary A without a solubilizer is turbid, but a use concentration of a product of the invention is visually clear. Use concentrations will vary with the user, but in general will range from about 1 to about 4 fluid ounces of the whole composition per 17 gallons of water. The product of the present invention has excellent fabric-softening characteristics, in opposition to the teachings of U.S. Pat. No. 3,501,335 wherein it is disclosed that fabric-softening agents must be only marginally soluble, that is, the solute is in colloidal dispersion, rather than being in true solution (column 2, lines 40-53).

The quaternary ammonium fabric softener referred to is a mixture having two long alkyl chains and two short alkyl chains, the long alkyl chains being a mixture of straight and branched configurations. It is described in and claimed in combination with certain amine oxides in US. application Ser. No. 788,918, now issued as US. Pat. No. 3,660,286, which is hereby incorporated by reference.

The aforementioned quaternary ammonium mixture has the following formula wherein R and R are independently selected from the group consisting of Radlcal I: CH (CH CI-I(CH and Radical ll: CH (CH and mixtures thereof, wherein m 8 through 14 inclusive,

y 11 through 17 inclusive, and

Radical l comprises between about 5 and about 25 percent by weight of the total of R and R and Radical 1] comprises between about 40 and about percent by weight of carbon chains where y is 1 1 through 14 inclusive, with the remainder being carbon chains where y is 15 through 17 inclusive,

R and R are independently selected from the group consisting of methyl, ethyl, propyl, and isopropyl radicals,

R is methyl or ethyl, and

X is an anion selected from the group consisting of chloride, bromide, iodide, methosulfate, and ethosulfate, which imparts water dispersibility to the quaternary.

The specific quaternary mixture employed in the examples set forth hereinafter has the following analysis:

7( By Weight, Based on Chain Lengths Of Total Long-Chain Alkyl Long Chain Alkyls About 12.5 percent of the long-chain alkyl groups bear a methyl or ethyyl group on the 2-carbon, and these are confined to the C -C, alkyl groups, as described above. The remainder of the long-chain alkyl groups, about 87.5 percent, are straight chain and comprise about 40-60 percent C -C chain lengths and about 60-40 percent C -C chain lengths, these two last-named ranges being based on the total of the longchain alkyl groups having a straight-chain configuration.

Substances which serve to solubilize the quaternary used in the aqueous compositions of the invention fall within the classes of lower molecular weight alcohols, aryl sulfonates, C -C diols, water-soluble low molecular weight ethers, water-soluble quaternaries, sulfobetaines, alkyl taurines, amine oxides, phosphine oxides, sulfoxides, and nonionic surfactants. Mixtures of two or more of the aforementioned substances have been found to be advantageous.

The non-foaming solublizers comprise, for example the arylsulfonates, alkanediols, alkylene glycols having 2-6 carbon atoms, the methyl, ethyl, or butyl monoethers of diethylene glycol, and 2-methoxy, 2-ethoxy, or 2-butoxy ethanol.

More specifically among the species effective as solubilizers in the presence of water within the above-listed classes there may be mentioned the following:

LOW MOLECULAR WEIGHT ALCOHOLS methanol, ethanol, l-propanol, isopropanol, and tertbutanol DIOLS ethylene glycol, 1,3-propanediol, 1,5-heptanediol, and l,6-hexanediol WATER-SOLUBLE LOW-MOLECULAR WEIGHT ETHERS l,4-butanediol,

WATER-SOLUBLE QUATERNARY AMMONIUM COMPOUNDS dodecyl-dimethyl-benzyl ammonium chloride, dodecyldimethyl-ethylbenzyl ammonium chloride, myristyl-dimethylbenzyl ammonium chloride,

myristyl-dimethyl-ethylbenzyl ammonium chloride, dioctyl-dimethyl ammonium chloride, and didecyldimethyl ammonium chloride, and mixtures thereof SULFOBETAINES N-decyl sulfobetaine, N-dodecyl sulfobetaine, N- coco sulfobetaine wherein coco? designates mixed alkyl groups having the molecular weight distribution of coconut oil fatty acids, and mixtures thereof N-(Zhydroxyalkyllmethyl taurines N-(2-hydroxyoctyl)methyl taurine, and N-(2- hydroxy-decyl) methyl taurine, andmixtures thereof AMlNE OXIDES N,N-dimethyl-N-octyl amine oxide, N,N -dimethyl-N- decyl amine oxide, N,N-dimethyl-N-dodecyl amine oxide, N,N-dimethyl-N-tetradecyl amine oxide, N,N-dimethyl-N-hexadecyl amine oxide, N,N-bis(2- hydroxyethyl)-N-dodecyl amine oxide, N,N-bis(2- hydroxyethyl)-N-tetradecyl amine oxide, and mixtures thereof PHOSPHINE OXIDES SULFOXIDES Methyl hexyl sulfoxide, methyl heptyl sulfoxide, methyl octyl sulfoxide, methyl nonyl sulfoxide, methyl decyl sulfoxide, dodecyl-Z-hydroxyethyl sulfoxide, and mixtures thereof.

ARYLSULFONATES Sodium benzenesulfonate, sodium xylenesulfonate, sodium toluenesulfonate, sodium cumenesulfonate, and the corresponding potassium, ammonium, and substituted ammonium salts, and mixtures thereof. These compounds are not effective as sole solubilizers, but may be usedto advantage to lower the amount of other solubilizers.

uomomc SURFACTANTS Among the nonionic materials that can be employed in the fabric softening compositions of the invention are the Pluronics (trademark of the Wyandotte Chemicals Corp. formed by condensing propylene oxide with propylene glycol to a molecular weight of about 600-2500 torform abase followed by condensing ethylone oxide to this base to the extent of about to about 90percent by weight, total molecule basis. US. Pat.

Nos. 2,674,619 and 2,677,700 describe operable nonionic compounds; compounds formed by the simulta- L ene and oxyethylene groups, and having over 30 percent ethylene oxide by weight. These and related compounds are described in US. Pat. Nos. 2,979,528;

3,036,] 18; 3,022,335; 3,036,130, and 3,048,548, alkyl phenols having 6-12 carbon atoms in the alkyl portion,

(straight or branched) ethoxylated with 6-25 molar proportions of ethylene oxide, ethoxylates of fatty alcohols having 8-18 carbon atoms per mole and 5 to 30 molar proportions of oxyethylene groups.

Examples of specific nonionic compounds branchedchain branched nonyl phenol condensed with 8-14 molar proportions of ethylene oxide, a mixed c,, c,, secondary alcohol (Tergitol l5-S) condensed with 9-14 molar proportions of ethylene oxide, a mixed C -C alcohol made by the Oxo process (Neodol 45) condensed with 9-12 moles ethylene oxide, or a mixture of percent C and 35 percent C synthetic straight chain primary alcohols condensed with 9-15 molar proportions of ethylene oxide.

in accordance with the invention, it is contemplated that the solubilizers will be used in the following proportions by weight of the whole composition:

l. Arylsulfonates having the formula A-BZ-SO M wherein A is H, methyl, dimethyl, or isopropyl, B2 is a benzene nucleus, and M is Na, K, NH,,, or substituted ammonium, such as mono-, di-, or triethanolammonium, tetraethyl ammonium, morpholinium, etc., 0 to about 40 percent; 4

2. Amine oxides having the formula RR R N 0 wherein R and R are selected from the group consisting of methyl, ethyl, propyl, isopropyl and 2- hydroxyethyl, and R is selected from the group consisting of alkyl and 2-hydroxyalkyl having about 8 to about 14 carbon atoms, 0 to about 37 percent;

3. Alkanediols having 2-6 carbon atoms, 0 to about 40 percent;

4. Alkylene glycols and polyoxy alpha-omega diol having 2-6 carbon atoms, 0 to about 40 percent; 5. Low molecular weight, i.e., the 2-methoxy, 2-

ethoxy, and 2-butoxy monoethers of ethanol, and the methyl, ethyl, and butyl monoethers of diethyleneglycol;

6. Water-soluble quaternary ammonium compounds having the formula RR R R*NCI wherein R is an alkyl group having about 8 to about 14 carbon atoms, R and R are methyl, and R is benzyl or ethylbenzyl, 0 to about 30 percent;

7. N-alkyl sulfobetaines having the formula Crl wherein R is an alkyl group having 10-14 carbon atoms, 0 to about 20 percent; 8. N-2-hydroxymethyl taurines, wherein the alky group has 8 to 10 carbon atoms, 0 to about 30 percent; 9. Phosphine oxides having the formula R ,R ,R P 0 wherein R and R are methyl, and R is an alkyl radical having from about 10 to about 16 carbon atoms, 0 to about 20 percent; l0. Sulfoxides having the formula RR S 0 wherein R is a methyl, ethyl, or a 2-hydroxyethyl radical,

and R is an alkyl radical having about to about carbon atoms, 0 to about percent;

1 l. Nonionic surfactants selected from A the group consisting of (a) ethylene oxide condensates of aliphatic alcohols having about 8 to about 18 carbon atoms, and (b) of alkylphenols having straight or branched chain alkyl groups with about 6 to about 12 carbon atoms, the ethylene oxide forming oxyethylene groups to the extent of 5 to molar proportions per mole of condensate, and (c) ethylene oxide condensates with polyoxypropylene, having 30 to 90 percent ethylene oxide by weight per molecule, 0 to about 20 percent.

Mixtures of these solubilizers may be used; By the term substituted ammonium is meant N-alkyl substituted ammonium wherein said alkyl has 1-3 carbon atoms, N-alkanol, N,N-dialkanol, N,N,N-trialkanol substituted ammonium wherein said alkanol has 23 carbon atoms, morpholinium, and mixtures thereof.

Not every one of the useful solubilizers is effective when used alone. For example at a level of 6 percent quaternary fabric softening agent, clarity is not attained with up to 40 percent of a mixture of xyleneand toluenesulfonates as the sole solubilizer. Xyleneand toluenesulfonates however have utility in combination with other solubilizers. Also the phosphine oxides and nonionic surfactants cannot be used alone. The remaining solubilizers disclosed as useful in accordance with the instant invention may beused alone or in admixture, andas shown below the minimum requirements vary. Consequently the useful solubilizers will be so selected as to species and proportions to provide a visually clear liquid medium containing about 2 to about 20 percent of the quaternary ammonium fabric softener of the type described herein. Preferred proportions of softener are from about 4 to about 12 percent. A particularly useful level is about 6 percent.

The solubilizer will be present in proportions ranging from about 4 to about 43 percent, preferably about 7 to about 24 percent, whole composition basis, the balance being essentially water, which, along with small quantities of optional components described elsewhere herein, comprise a solvent system which is present to the extent of about 98 to about 80 percent of the whole composition.

The expression the balance essentially water as used herein allows for the inclusion of unspecified optional ingredients that do not materially alter the basic and novel characteristics of the composition. For example, germicides, optical brighteners, bluing, colorants, etc. may advantageously be incorporated into the product.

Suitable optional germicides are alkyl dimethyl ethylbenzyl ammoinium chloride (BTC 47l 4,2',4- trichloro-Z-hydroxy diphenyl ether (lrgasan CH 3565); 4',S-dibromosalicylanilide; 3,4,5- tribromosalicylanilide; and 2,2-methylenbis (3,4,6- trichlorophenol) (Hexachlorophene).

It is often desirable to impart a whitening and brightening effect to cloths during the softening step. For this purpose the clear products of the invention may contain fluoroescent optical brighteners and colorants. For example the sodium salt of 2-(stilbyl-4)-(naphthol',2:4,5)-1,2,3-triazole-2"-sulfonic acid, a compound disclosed in US. Pat. No. 2,784,183, and a disulfonate corresponding in molecular structure to the foregoing, also disclosed in US. Pat. No. 2,784, l 83, may be incorporated inproportions of about 0.02 to about 0.2 percent to impart optical brightening to fabrics treated with the softener.

Other suitable optical brighteners that may optionally be used are sodium 4,4-bis( 2-phenyl-amino4- morpholino-l,3,5-triazyl- (6))diaininostilbene-2,2- disulfonate; sodium 4,4'-bis (2,4-diphenylar'ninol ,3,5- triazyl (6))diaminostilbene-2,2-disulfonate; sodium 4,4-bis(Z-phenylamino-4-diethanolamin0 l',3,5-triazyl (6))diaminostilbene-2,2disulfonate (Calcofluor M2R); and sodium 4,4-bis(2-phenylamino-4-morpholino-l,3,5-triazyl (6))diaminostilbene-2,2'- disulfonate (Calcofluor White RC Conc.).

Suitable optional colarants are l,4-bis(2-ethylhexylam'ino)anthraquinone (Aviation Oil Blue); Acid Blue C 61585 (Polar Brilliant Blue RAW); Basic Violet l0, C.l. No. 45 170 (D&C Red No. 19 Rhodamine B); and CI. Pigment Green 74260, a chlorinated copper phthalocyanine (Heliogen Green W Powder).

The colarants, when used,fare desirably present at levels between about 0.003 and 0.2 percent, depending upon the depth "of tinting desired. For example, Polar Brilliant Blue RAW may be used in amounts from about 0.003 to about 0.02 percent, andgenerally at-a level of about 0.006 percent. Hastings Sky Blue OB may be present between about 0.05 and 0.01 percent, usually about 0.1 percent. F

Viscosity is considered by many to play an important role in ease of measuring a prescribed volume of a liquid to be poured into a'washing' machine. A viscosity of about 200 to about 500 centipoises is satisfactory for minimizing over-dosing when pouring, particularly when, as currently practices, the cap of the container serves as a measuring cup. The broad range-of useful viscosities is 1 to about 1000 centipoises. A preferred range is about to about 500 centipoises, in a composition contaiing 6 percent quaternary fabric softener solubilized with dimethyl coco amine oxide and isopropanol, a desirable viscosity of 200 centipoises can be obtained by including in the composition 0.25 percent of hydroxyethylcellulose (CellosizelQP 52000-high) at an amine oxide level and an isopropanol-level of about 7 percent each. The product may gel if higher proportions of hydroxyethylcellulose, or higher molecular weight amine oxides are used. Viscosity data at various levels of amine oxide and isopropanol in an aqueous composition .containing'6 percent quaternary and 0.25 percent Cellosize 'are given below. Cellosize 'is a trademark of Union Carbide Co. Cocol as ,used

herein refers .to the long-chain alkyl groups having the' mixed molecular distribution in coconut oil, i.e about 8 percent caprylic (Cg), 7percent capric (C 48 per- I cent lauric (C12), 17 percent myristic (C 9 percent palmitic (C16) 2 percent stearic (C18). 6 percent oleic (C and 3 percent linoleic (C Viscosity of Formula Plus 25% Hydroxyethylcellulo e (cps) '71 Dodecyl Dimethyl v Amine Oxide As ls 71 .lsopropanol (cps) -Continued TABLE 11 EFFECT ON VlSCOSlTY RESULTING FROM USE OF DODECYL hol Minimum 7:

DlMETHYL WITH 67! ADOGEN 432 AMINE OXlDE AND HYDROXYETHYLCELLULOSE llliflthariol t ano Viscosity of Formula f p I Pl .257 sopropano sz f Tert butanol 7.5 Dodecyl Dimethyl ethyl -P d I 2 Amine Oxide 7: lsopropanol As ls cellulose 512231 agzgt 4-6 (cps) (cps) l-hexanol about 4-6 3 14.8 70 l-heptanol 4 12.8 90 1-octanol"" m) 5 10.8 30 105 130:11am I 7 6.9 40 200 o ecano l5 ""Clnrity not obtained at any proportion of these alcohols with water.

The following Examples will lead to a more complete understanding of the present invention. These Exam- AMPLE 2 ples are for Illustrative purposes only and are not 70 An excellent clear fabric-softening Composition has tended to be construed as defining the limits of the scope of the invention.

EXAMPLE 1 TABLE 1 Alcohol Minimum '7? Methanol 39 Ethanol Propanol l 3.5 lsopropanol l6 Tert-butanol 15 An excellent clarifying mixture iscomposed of an aliphatic alcohol having l-4 carbon atoms and dimethyl coco" amine oxide wherein the long-chain alkyl group is a mixture having substantially the chain-length distri bution of coconut oil fatty acids. In the case of alcohols having complete miscibility with water, i.e., the first five alcohols listed hereinbelow in Table 11, there is a minimum critical proportion of the alcohol required to clarify an aqueous dispersion of the quaternary. Higher proportions of the alcohols may be used, up to the point at which the alcohol constitutes the entire solvent. ln the case of l-butanol and higher molecular weight alcohols having limited solubility in water, i.e., about 0.5 to 15 grams per 100 ml, clarity is achieved only within a narrow percentage range of alcohol in the presence of the aforementioned amine oxide. Examples of the aforementioned alcohol requirements for the clarification of 6 percent quaternary in the presence of 4 percent dimethyl coco amine oxide, the balance of the composition being water, are shown below.

the following formula:

Percent by Weight Quaternary 6.0 lsopropanol 2.0.0 Water 74.0

""wherein 12.5% of the long-chain alkyl groups have branching on the Z-curhun as hereinbefore described (Formula A).

The above composition has the following characteristics:

pH 5.5 Viscosity 10 cps Sp. Gr. 0.965 Cloud Point 50F Flash Point Closed Cup about F Open Cup about F Two ounces of the foregoing composition, as well as two ounces of similar compositions containing 30 and 40 percent isopropanol, in the rinse cycle of an automatic toploading washer provide a softening effect on cotton equal to that of a product containing 6 percent dimethyl-di(hardened tallow) ammonium chloride in an aqueous medium without an alcohol.

EXAMPLE 3 isopropanol Amine Oxide EXAMPLE 4 Levels of about I to about 14 percent of the quaternary (A) can be solublized in the aqueous medium by The above data show slight alkyl distribution variation does not affect the level of quaternary necessary for clarity with 6.0 percent Adogen 432 as is found with about 3 to about 20 percent of dimethyl coco amine ox- 5 the dialkyl dimethyl quaternary compounds. Similarly, ide. In the compositions set forth below there is present no difference is noted between the benzyl and ethyl from about 0.2 to about 2.8 percent isopropanol added benzyl form. as a part of the liquid vehicle assoicated with the quaternary as supplied by the manufacturer. EXAMPLE 7 This example shows the effectiveness of certain longchain alkyl-dimethyl sulfobetaines in clarifying an 7! Qumemary A) Amine Oxide 7! lsopmpmml aqueous medium containing 6 percent quaternary.

L0 3.0"" 0.2 3.0 4.0"" 0.6 I 5 120-0 Long-chain alkyl Percent Observation 6.0 7.0"" L2 228W 2'8 stripped coco 7 clear 12' lauryl 7 turbid lauryl 8 clear coco 7 turbid ""lurhid I 70 coco 8 clear ""mimmum proportions for elanty. myristyl (CH) 12 very id stearyl (C 12 phase separation EXAMPLE 5 Lower molecular weight homologues of the quater 7 EXAMPLE 8 nary fabric softeners of this invention, re, the dimethyl-dioctyl-, and the dimethyl-didecyl homologues, are Mlxtures of dlmethyl amme OXIde f medlu m effective solubilizers, as seen from the data below. In all cham length alkyl Sulfobetames effectlve to 'f i y cases the quaternary fabric softener is present at 6 perquaternary (A) m an aqueous medlum, as exemphfled cent in an aqueous medium. All percentage figures below given are on the whole composition basis.

Sulfobetaine Stripped Alkyl gmups Mlmmum for Clarity Quaternary Amine Oxide Coco dodecyl coco dibutyl phase separation 3 l 3 dihexyl phase separation 3 3 1 dioctyl 5.27: 6 4 4 octyl decyl 4.8% 6 4 4 dldecyl 14.0% 6 4 4 di coco 10% di tallow opaque emulsion 3.5 parts di C and 4.0% 40 0.5 part di C," 3.2 parts di C. and 3.7% EXAMPLE 9 0.5 purt Ctt'cm The following example shows the criticahty of chamlength of 2-hydroxyalkylmethyltaurines for effective solubilization of a 6 percent aqueous dispersion of the EXAMPLE 6 fabric-softening quaternary. The chain length of the 2- (Long-chain alkyl)dimethyl benzyland ethylbenzyl hydroxyalkyl portion must be below C for effective ammonium chlorides, wherein the long-chain alkyl solubilization. group has 5-68 percent C,,, 30-60 percent C and 0-30 percent C chain lengths, are effective solubilizers for the fabric-softening quaternary of the present Percent BI invention in 6 percent aqueous dispersion. Representaweigh, tive solubilizers are listed below, with the minimum M th IT I IC Ob percentage, whole composition basis, of each required e y aurme posmon Sen/am to clarify. Z-Hydroxyoctyl- 7.0 slightly hazy Z-Hydroxy-octyl- 12.8 clear TABLE III 2-Hydroxy-dodecyl- 27.0 hazy Hydroxy-C -C 24.0 hazy Hydroxy-hexadecyl- MINIMUM 7r QUATERNARY REQUIRED TO CLARIFY 6% N- id 15 0 opaque ADOGEN 432 AIkoxy(C -C, )hydroxy- Percent 0 propyl- 22.0 translucent gel alkyl"" dimethyl benzyl ammonium chloride 8.0 alkyl"" dimethyl ethyl benzyl ammonium chloride 8.0 alkyl dimethyl benzyl/alkyl dimethyl ethyl 8.0 benzyl ammonium chloride, 1:] ratio EXAMPLE 10 alkyl dimethyl benzyl/alkyl dimethyl ethyl 8.0 benzyl ammonium chloride ratio 65 The N,N-dlmethyl-N-alkylamme oxides are more ef- "50% C 3091 C l771 Ge. 3% C 50% C C 307: C 5% C 68% C 32% C fective in clarifying the quaternary ammonium compound of the instant invention (structure A), as the alkyl group is made shorter, as shown in the following tabulation. The amine oxides employed are commercial products containing a minimum proportion of the stated chain length of the long-chain alkyl group as Proportions of dimethyl-C -amine oxide in the region of the minimum clarifying percentages cannot tolerate significant percentages of the C homologue, as seen in the following table:

% Amine Oxide Whole Composition Basis Observation After 1 Day 7 none clear 6 1 cloudy 2 cloudy 5 3 s1. cloudy 4.5 3 cloudy Other amine oxides are effective as clarifying agents for an aqueous 6 percent solution of the quaternary fabric softener, as shown below.

Minimum Percentage to Clarify Whole Amine Oxide Composition Basis N.N-bis(2-hydroxyethyl) decyl- 8 N,N-bis(2-hydroxyethyl) coco- 8 N-methyl. N-( 2-hydroxyethyl 2-hydroxy(C, -C amine oxide 8 (gel) N-methyl-N-( 2-hydroxyethyl Z-hydroxy-octadecyl 8 (gel) EXAMPLE 1 l The data below show the action of dialkyl sulfoxides in the production of a clear quaternary aqueous fabric softening composition. The percentage figures shown are based on the whole composition.

7: Qua- 7c temary Sulfoxide Sulfoxide Observation 6 dimethyl 50.0 hazy liquid 6 heptyl methyl 5.1 clear liquid 2 dodecyl methyl 2.0 opaque liquid 2 tetradecyl methyl 2.0 opaque liquid 3 hexadecyl methyl 3.0 opaque liquid 3 dodecyl methyl 3.0 clear aerated gel 3 dodecyl methyl 6.0 clearI aerated ge 6 dodecyl methyl 5.0 clear semiliquid gel EXAMPLE 12 The following data illustrate the effect of a nonionic surfactant in combination with dimethyl coco amine oxide on an aqueous product containing 6% of quaternary (A). The nonionic surfactant employed is an alkoxypolyoxyethylene ethanol wherein the alkoxy portion is composed of a mixture of chain lengths about 67 percent of which have 12 carbon atoms and about 33 percent of which 18 carbon atoms, and the oxyethylene groups are present to the extent of about 60 percent by weight of the molecule.

Viscosity Cloud Stability Nonionic (cps) Point lnitial 9 Months (R.T.)

30 44F clear trace sediment 0.25 30 47F clear trace sediment 0.50 30 47F clear trace sediment 2.00 40 49F clear trace sediment 5.00 40 41F clear clear 10.00 56F clear clear 20.00 61F clear clear Addition of less than 5 percent nonionic has little effect on viscosity. While the addition of 5-20 percent nonionic increases viscosity and improves room temperature stability, the increasing amounts of nonionic also increase the cloud point and result in decreased low temperature stability.

EXAMPLE 13 A typical clear fabric-softening composition has the following formula:

Percent Quaternary (A) 5 7 Dimethyl coco amine oxide 4-9 lsopropanol 3-1 5 Colorant (Polar Brilliant Blue) 0.005-0.015 Perfume 0. l-0.2 Water balance The proportions of amine oxide and isopropanol will be selected with respect to the proportion of quaternary to provide a visually clear solution.

EXAMPLE 14 A clear homogeneous liquid fabric softening composition is prepared having the following formula.

Percent By Weight Quaternary (A) 6.0 Dimethyl coco amine oxide 7.0 (a)lsopropanol 3.0 Colorant (Polar Brilliant Blue) 0.01 Perfume 0.15 Water Balance (Madded as a component associated with the quaternary and the amine oxide. which are commercial products containing respectively 15% and 30% isopropunul.

Two ml of the above-described composition are added to 2 liters of tap water (approximating use concentration) at about 1 10 ppm hardness as CaC O at a temperature of 120F. The composition completely dissolves, whereas a similar composition without the amine oxide when tested in the same manner produces a turbidity.

EXAMPLE l Desirable fabric softener compositions which are visually clear liquids are prepared having the following components in the indicated:proportions:

i. about 3 to about 7 percent of quaternary ammonium salt, H 1

ii. about 4 to about 8 percent of dimethyl alkyl amine oxide, wherein said alkyl is a mixture having the chainlength distribution of coconut oil,

iii. about 5 to about 35 percent of a low molecular weight alkylbenzenesulfonate selected from the group consisting of sodium toluenesulfonate and sodium xylenesulfonate,

iv. about 1.5 to about percent of isopropanol,

v. about 0 to about 0.5 percent of hydroxyethylcellulose, and

vi. about 39.5 to about 86.5 percent water, said percentages being by weight, whole composition basis.

Having described the invention, the Examples of which as described hereinabove are illustrative and not intended to be limiting, we hereby set forth the manner in which we desire to claim the invention, the scope of which is to be limited only by the appended claims.

What is claimed is:

l. A clear, single phase, liquid fabric softener composition comprising i. about 2 to about 20 percent of dialkyl dimethyl quaternary ammonium salt conforming to the formula wherein R and R are independently selected from the group consisting of Radical I: CH (CH CH(CH and Radical ll: CH -,(CH and-mixtures thereof, where m 8 through 14 inclusive, y ll through 17 inclusive, and Radical 1 comprises between about 5 and about 25 percent by weight of the total of R and R and Radical [1 comprises between about 40 and about 60 percentby weight of carbon chains where y is l I through 14 inclusive, with the remainder being carbon chains where y is through 17 inclusive, R and R are independently selected from the group consisting of methyl, ethyl, propyl, and isopropyl radicals, R is methyl or ethyl, and X is an anion selected from the group consisting of chloride, bromide,-iodide, methosulfate, and ethosulfate, which imparts water dispersibility to the quaternary,

ii. about 98 to about 80 percent of a solvent for said quaternary ammonium salt, said solvent compris- 5 ing a solubilizer selected from the group consisting a. arylsulfonates having the formula A-Bz-SO M wherein A is H, methyl, dimethyl, or isopropyl, B2 is a benzene nucleus, and M is Na, K, NH,, or substituted ammonium,

b. alkanediols having 2-6 carbon atoms,

0. alkylene glycols having 2-6 carbon atoms,

d. methyl, ethyl, and butyl monoethers of diethyleneglycol,

e. 2-methoxy, 2-ethoxy, and 2-butoxy ethanol,

f. water-soluble quaternary ammonium compounds having the formula RR RR*NCl wherein R is an alkyl group having about 8 to about 14 carbon atoms, R and'R are methyl, 'and R isbenzyl or 'ethylberizyl, v

g. N-alkyl sulfobetaines having the formula R--N CH2CII2SO3 wherein R is an alkyl group having l0-l4 carbon atoms, I

h. N-Z-hydroxymethyl taurines, wherein the alkyl group has 8 to l0 carbon atoms,

i. amines oxides having the formula RR R N 0 wherein R and R are selected from the group consisting of methyl, ethyl, propyl, isopropyl and 2-hydroxyethyl, and R is selected from the group consisting of alkyl and 2-hydroxyalkyl having about 8 to 14 carbon atoms,

j. phosphine oxides having the formula R,R RP 0 wherein R and'R are methyl, and R is an alkyl radical having from 10 to about 16 carbon atoms, F v w k. sulfoxides having the formula R. R S 0 wherein R is a methyl, ethyl, or a 2-hydroxyethyl radical, and R is an alkyl radical having about 6 to about 10 carbon atoms, and

l. nonionic surfactants selected from the group consisting of (a) ethylene oxide condensates of aliphatic alcohols having about 8 to about 18 carbon atoms, and (b) of alkylphenols having straight or branched chain alkyl groups with about 6 to about 12 carbon atoms, the ethylene oxide forming oxyethylene groups to the extent of 5 to 30 molar proportions per mole of condensate, and (c) ethylene oxide condensates with polyoxypropylene, having 30 to 90 percent ethylene oxide by weight per molecule, and mixtures thereof, said solubilizer being present in propor tions ranging from about 4 to about 43 percent, whole composition basis, the balance being essentially water, the proportions of said components (a) (l) being selected to provide a visually clear solutionof said quaternary ammonium salt.

2. A clear, single-phase, liquid fabric-softening com- I position in accordance with claim 1 wherein said quaternary ammonium salt is present in the proportions of about 4 to about l2 percent.

3. A clear, single-phase, liquid fabric-softening com position in acordance with claim 1 wherein said quaternary ammonium salt is present in the proportion of about 6 percent.

4. A clear, single-phase, liquid fabric-softening composition in accordance with claim 1 wherein said solubilizer is selected from the group consisting of arylsulfonates, alkanediols having 2-6 carbon atoms, alkylene glycols having 2-6 carbon atoms, the methyl, ethyl, or butyl monoethers of diethylene glycol, and Z-methoxy, 2-ethoxy, or 2-butoxy ethanol.

5. A clear, single-phase, liquid fabric-softening composition in accordance with claim 1 wherein said quaternary ammonium salt is present in the proportions of about 7 percent, said amine oxide is dimethyl coco amine oxide in the proportions of about 4-9 percent and said isopropanol is present in the proportions of about 3-15 percent, the proportions of said dimethyl 18 coco amine oxide and isopropanol being selected to provide a visually clear solution.

6. A visually clear fabric softening composition comprising centages being by weight, whole composition basis.

Claims

1. A CLEAR, SINGLE PHASE, LIQUID FABRIC SOFTENER COMPOSITION COMPRISING I ABOUT 2 TO ABOUT 20 PERCENT OF DIALKYL DIMETHYL QUASTERNARY AMMONIUM SALT CONFORMING TO THE FORMULA

2. A clear, single-phase, liquid fabric-softening composition in accordance with claim 1 wherein said quaternary ammonium salt is present in the proportions of about 4 to about 12 percent.

3. A clear, single-phase, liquid fabric-softening composition in acordance with claim 1 wherein said quaternary ammonium salt is present in the proportion of about 6 percent.

4. A clear, single-phase, liquid fabric-softening composition in accordance with claim 1 wherein said solubilizer is selected from the group consisting of arylsulfonates, alkanediols having 2-6 carbon atoms, alkylene glycols having 2-6 carbon atoms, the methyl, ethyl, or butyl monoethers of diethylene glycol, and 2-methoxy, 2-ethoxy, or 2-butoxy ethanol.

5. A clear, single-phase, liquid fabric-softening composition in accordance with claim 1 wherein said quaternary ammonium salt is present in the proportions of about 5-7 percent, said amine oxide is dimethyl coco amine oxide in the proportions of about 4-9 percent and said isopropanol is present in the proportions of about 3-15 percent, the proportions of said dimethyl coco amine oxide and isopropanol being selected to provide a visually clear solution.

6. A visually clear fabric softening composition comprising i. about 3 to about 7 percent of a quaternary ammonium salt having a composition in accordance with claim 1, ii. about 4 to about 8 percent of dimethyl alkyl amine oxide, wherein said alkyl is a mixture having the chain-length distribution of coconut oil, iii. about 5 to about 35 percent of a low molecular weight alkylbenzenesulfonate selected from the group consisting of sodium toluenesulfonate and sodium xylenesulfonate, iv. about 1.5 to about 10 percent of isopropanol, v. about 0 to about 0.5 of hydroxyethylcellulose, and vi. about 39.5 to about 86.5 percent water, said percentages being by weight, whole composition basis.