US3170876A - Textile treating compositions - Google Patents

Description

Uitd States Patent 3,1793)? TEXTHLE TREATENG (JQWPGSETE'QNE Robert A. Giney, Wilmington, Del, assignor to Atlas Chemical industries, lino, Wihnington, Deh, a corps ration of Delaware No Drawing. Fiied f sh. ll, 1%1, Ser. No. eeezs 9 Ciairns. (6i. 252--d.3)

This invention relates to novel compositions for treating textile fabrics and to concentrated aqueous dispersions of these novel compositions and the preparation of the dispersions. In particular the invention relates to compositions containing normally plastic or solid cationic textile softeners which compositions form concentrated aqueous dispersions possessing a high degree of freezethaw stability.

This application is a continuation-in-part of application Serial No. 4,872 filed January 27, 1960, now abandoned.

Cationic surface active agents have gained widespread acceptance as textile softeners. These cationic textile softeners posses many advantages, such as effectiveness in small amounts and resistance to washing, but they suffer from several disadvantages. Many of the cationic softeners are waxy or gummy in nature making them dir'licult to weigh or measure, to mix or disperse with other textile treating agentaand to place in a form, such as an aqueous dispersion, which maybe readily applied to textiles. For these reasons, it is desirable to have a concentrated aqueous dispersion of a cationic textile treating composition, which concentrated dispersion is fluid, easily handled and readily dispersed in water.

It is an object of this invention to provide a textile treating composition which may he admixed with water to form a concentrated aqueous dispersion, said concentrated dispersion being fluid, easily handled and readily dispersed in water.

' 1 It is also an object of this invention to'provide a concentrated aqueous dispersion of a textile treating composition which will remain stable throughout repeated freeze-thaw cycles.

Another object of this invention is to provide a concentrated aqueous dispersion of a textile treating composition which is readily dispersed. in water to form a dilute solution of a textile treating composition which 7 may be directly appliedto textile fabrics.

A further object is to provide a cationic textile softener composition whose softening capability is substantially unimpaired by other components-of the composition.

A still further object of this invention is to provide a cationic textile softener composition whose Wiscosityis easily controlled and which may be prepared as-a concentrated aqueous dispersion =chara'cterized by fluidity even at high concentrations of cationic textilesofte'ner. --Still another object of the invention is to provide a V method forv persion of the cationic textile softener.

I repairinga concentrated aqueous dispersion of a cationic'textile softener. .1

arrests Patented Feb. 23, 1965 have insufficient activity to act as a liuidizing agent for the cationic textile softeners useful in the practice of this invention or Will be so costly as to be impractical for use as a fiuidizing agent. These polyoxythylene castor oil compounds are nonionic emulsifiers, and their preparation is disclosed in the prior art.

In order to convert a plastic or gummy cationic textile softener into a concentrated aqueous dispersion in accordance with this invention, it is necessary that enough nonionic emulsifier be added to'the cationic component so that the mixture will form a fluid dispersion in water and yet not impair the cationics textile softener properties. In general, the nonionic emulsifier may be employed in a ratio of from about 1:1 to about 123 based on the cationic softener component. If less than a 1:3 ratio is used, there may not be enough nonionic emulsifier to form a stable, fluid dispersion when the textile softener composition is admixed with water, whereas a greater than 1:1 ratio may impair the textile softening properties of the cationic component. It should be noted that ratios of nonionic to cationic outside of the above recited ranges may be operative and are included within the scope of this invention, though'the 1:1 to about 1:3 ratios are generally preferred. a

The cationic textile softeners used'in accordance with this invention are useful in treating textile fabrics to give. a soft and pieasing feel to fabrics which would othere wisetend to be harsh or stiff; The cationic softeners of thein'vention are also described in the art of textile finishing as particularly suitable in imparting richness of hand to the textiles treated therewith.

' ative of the cationic textile softener compoundswhich may be used to form concentrated aqueous dispersions in accordance with this invention arefatty carbamides, fatty amino amide compounds, acid salts of complex amino organic compounds, quaternary ammonium com- Other objects and purposesjof tnis'iinvention will be obvious tothose skilled; in the artiu view'ofthe descriptionof the inv'entionwhich follows. It has been discoverd that a textile treating composition consisting essentially of a; cationic textile softener and a nonionic 'ernulsifierfselected from the "group consistingof apoly'oxyethylene ether bfcastor-oil and a polyoxyethylene ether of hydrogenated castor oil can'be dispersed in water to form. a concentrated aqueous dis- 7 The resultant concentrated aqueous dispersion .is fluid, easily handled and readily dispersed in water to form a dilute cationic treating solution which may be directly applied to textile fabrics.

pounds, alkylguanidine'and distearyl dimethyl ammonium chloride. further description of cationic softening agentsuseful-in this inventionrnay be found in British 7 Patents 465,166, 490,637 and 531,691 and'United States Patents 2,168,Z5 3,'2,185,427 and 2,195,194.

Compounds of ,the foregoing type may be found on the market undervarious trade names such as for example AhcovelA and Ahcovel Gmanufactured by A. Hoff: man, Arquad 'ZHT: manufactured by. Arnrour & (30., Soromine' CS, Soromine 'BSA; and 'Soror'nine ENS :manufactured by; Antara Chem. Co sapamine WL and Sapansine KWC manufactured byCiba Chemical Co, Avitone SR manufactured by Du Pont QOmp'any, Aliquat H226 ,which may be employed in the practice of the present manufactured by General vMills andjAdogen 44-2 manu;

factured by Archer Daniels Midland.

A particularly useful class of cationic textile-softeners invention include the reaction product of a hexitolepihalohydrin condensate containing from about about The polyoxyethylene ethers ofv castor oil and hydrofatty acid diamide of diethylene triamine. If more than 4 halohydrin radicals are present per hexitol, it appears I 4 halohydrin radicals per hexitol residue and a. C to C thatthe softening effect of the textile softening agent,

3 it markedly reduced. A number of suitable compounds are disclosed in application Serial No. 654,472 filed April 23, 1959, by John D. Zech. Compounds within the scope of the present invention are exemplified by the following: (The ratio in parenthesis following the epihalohydrin indicates the molar ratio of hexitol to the epihalohydrin.) 'lh reaction product of the condensate of sorbitol epichlorohydrin (1:2), and the tallow acids diamide of diethylene triamine, the reaction product of the condensate of mannit'ol epibromohydrin (1:4) and the stearic acid diamide of diethylene triamine, the reaction product of lauryl acid diamide of diethylene triamine and sorbitol epichlorohydrin (1:2), the reaction product of cotton seed oil acids diamide of diethylene triamine and dulcitol epichlorohydrin (1:1), the reaction product of lard fatty acids diamide of diethylene triamine and sorbitol epichlorohydrin (1:2), the reaction product of linoleic acid diamide of diethylene triamine and sorbitol epichlorohydrin (1:2), the reaction product of palmitic acid diamide of diethylene triamine and sorbitol epichlorohydrin (1:2).

The chemistry of the hexitol epihalohydrin condensation products and the amidation reaction products of dietbylene triamine and the C to C fatty triglycerides and C to C fatty acids have been well elucidated in the prior art.

The cationic textile softeners useful in the practice of the present invention as hereinabove exemplified are prepared by condensing the hexitol derivative with the C to C fatty acid diamide at relatively low temperatures, usually about 100 C. to about 150 C. for a short period of time of about /2 hour to about 4 hours. It is desirable however to employ a stoichiometric excess of the fatty acid diamide in preparing the compounds of the present invention in order to insure complete reaction of the halohydrin derivative.

The terms halohydrin and epihalohydrin as used in the specification and claims have a restricted meaning for those compounds containing only fluorine halogen are excluded. However, halohydrins containing chlorine, bromine, and/ or iodine in addition to fluorine are contemplated herein. This limitation is imposed because of the lack of reactivity of fluorine in such compounds due to the relative stability of the fluorine-carbon bond.

As a cooperative agent for improving water dispersability of the cationic softeners, there may be employed along with the polyoxyethylcne castor oil derivatives a glycol, alcohol, or polyglycol of low molecular weight, such as ethylene glycol, propylene glycol, tetraethylene glycol, iso propanol, etc., which multiplies the effect of the polyoxyethylene compound in attaining a lower and more consis- V tent viscosity. The glycol may be addedas'such to the mixture of polyoxyethylene castor oil and the cationic textile softener; it maybe added to the cationic textile softener or the polyoxyethylene castor oil alone prior to mixing; and it may be added tothe cationic textile softener during its preparation. It is to be noted, however, that the addition of the glycol or polyglycol in an amount of from about 15% to about by weight based on the cationic softener will make the cationic softener somewhat less viscous. However, the polyoxyethylene castor oil compound is the essential ingredient which permits the formation of concentrated aqueous dispersions of cationic softener. A more preferred range for the amount of glycol or polyglycol which may be added is about 20 to about 25% by weight based on the final composition.

As pointed out hereinabove, the cationic textile softener compositions especially useful in this invention are normally of a plastic or gummy nature and as such they are difficult to handle and difiicult to apply to textile materials. It is known that very dilute aqueous solutions of cationic textile softeners can be prepared but with some difficulty, for it is hard to measure the gummy cationic compound and it is not easily dispersed in water.

For these reasons, textile chemical specialty houses have found it desirable to sell a concentrated aqueous dispersion of cationic tex ile softening compositions which contains from about 15 to about 40% by weight of cationic softener nonionic emulsifier mixture, and known as a 15 to 40% active aqueous concentrate. The aqueous concentrate is fluid (pourable) and more easily handled than 100% active cationic softener composition. It is essential that a dispersing agent be used to form the aqueous concentrat for otherwise only very small amounts of cationic compound can be dispersed in water. In the absence of a dispersant, a very small amount of gummy cationic softener will form a very. viscous, nonpourable aqueous dispersion. In addition, it is essential that the dispersing agent which is used to form the aqueous concentrate not impair the softening properties of the cationic compound.

It has been found that fluid aqueous concentrates of cationic softeners can be prepared by using nonionic emulsifiers as dispersing agents as previously disclosed. The aqueous concentrate is prepared in accordance with this invention by heating the normally plastic cationic textile softener until it melts (generally about C. will be suificient), add the nonionic emulsifier to the melted cationic compound, add sufiicient water with agitation to the liquid nonionic-cationic mixture until a smooth, creamy, fluid aqueous concentrate is obtained. The resultant aqueous mixture is stirred while cooling to room temperature.

In general, the fluidity of the paste formed by preparing an aqeuous dispersion of the cationic textile softener and the nonionic emulsifier is affected by the pH of the undiluted cationic textile softener. It is preferred that the undiluted cationic textile softeners have a pH which will produce a smooth, creamy, fluid, 25% active aqueous concentrate rather than a very viscous, somewhat gelatinous composition. Depending upon the particular cationic textile softener used, the pH may vary from about 3 to about 9 and still give acceptable results with lower pH val es generally giving more fluid concentrates. 25% active aqueous concentrates having the more desirable viscosities and fluidity andretaining other desirable textile softener properties such as scorch resistance, may be prepared from cationic softeners having a pH from about 3 to about 6. In particular, when using a hexitol-epihalohydrin condensate-fatty acid diamide as the cationic softener, it is preferred that the pH range from about 3 to about 5.

It is a relatively easy matter to adjust the pH of the cationic textile softener used in accordance with this invention to the desired pH value. If the pH of the cationic softener is too great to give the 25% active concentrate thedesired viscosity, a buffering acid such as glacial acetic I acid or phosphoric acid, may be added to the cationic softener to reduce the pH and thereby achieve the desired fluid viscosity. The buffering acid may be added to the cationic softener prior to, during, or after the formation of the 25 active concentrate, and. in this manner, it is an easy matter to control the viscosity of the aqueous con: centrate. However, it should be noted that the pH value of from about 3 to about 9 applies only to the cationic softener, and a different pH value maybe necessary to obtain a fluid 25% active concentrate when adding the buffering acid to the already formed aqueous dispersion. As previously stated, the cationic textile softener may have a pH from about 3 to about 9, though it should be noted that cationic softeners having a pH outside of this range are included within the scope of this invention.

As set forth above, the fluidity of the 25 active concentrate is affected by the amount of nonionic emulsifier (polyoxyethylcne castor oil or hydrogenated castor oil) which is used, with greater amounts generally yielding greater fluidity. In general, the nonionic emulsifier may be used in a ratio of from about 1:1 to about 1:3 of the cationic textile softener, with the amount of nonionic emulsifier or fluidizing agent necessary to achieve a fluid emulsifiersis also described.

% active concentrate depending upon theparticular cationic softener being used. If a hexitol-epihalohydrin condensate-fatty acid diamide is used as the cationic softener, in order to achieve good fluidity and retain softener properties, it is preferred to use a ratio of nonionic emulsifier to cationic softener ranging from about 31:69 to about :65, with a 33:67 ratio giving a particularly good, fluid 25% active concentrate.

The following examples illustrate the preparation of a hexitol halohydrin-fatty acid diamide of diethylene tri-, amine condensation product, and the preparation of a fluid, 25 active, textile softener concentrate by mixing the aforesaid condensation product, a cationic textile softener, with a polyoxyethylene castor oil nonionic emulsifier in accordance with one embodiment of this invention. The use of other cationic textile softeners and nonionic Example I 913 grams of anhydrous sorbitol wereheated to a reaction temperature of between 105 and 115 CL, 2.0 gins. of BF etherate catalyst BF were then added.

. Thereafter, 1040 grams of epichlorohydrin (molal ratio of sorbitol to epichlorohydrin of 122.25) were added dropwise over a period of 1 hour and 10 minutes with vigorous stirring and temperature control in order to maintain the temperature within the above-specified limits. The temperature was maintained with the use of addi tional heat to insure completion of the reaction.

100 grams of diethylene triamine and 571 grams of edible tallow were heated together at 135 C. for 3 hours. The residue in the flask consisted of a 99% yield of tallow acids diamide of diethylene triamine. The nitrogen content of the mixture was 6.3% and the apparent molecular I weight was 700.

81 grams of the product of the above-prepared sorbitol epichlorohydrin and 664 grams of the above-prepared talene groups per mol of oil and 2250 grams of water with, stirring. centrate, remained fluid after a storage of one week at room temperature and for the period of one week when stored at a temperature of C. In addition, the product remained in a fluid state after 3 freeze-thaw cycles.

After evaluation of the fluidity of the concentrate and its stability to repeated freeze-thaw cycles, the 25% active fluid concentrate was dissolved in additional water to provide a 2.0% aqueous solution. The'temperature of the solution was 50 C. Swatches of different fabrics including cottonynylon, Orlon, rayon, Dacron, Dynel and Darvan were each immersed in 300 cc. of the 2.0% aqueous solution of the cationic textile softener. After 3 minutes, the fabrics were centrifuged for 30 seconds and allowed to dry. Each of the test samples exhibited a softness of hand or feel? which was not found in low diamide of diethylene triamine (molal ratio of sorbitol i Example II 250 grams of the above prepared reaction product of Example I was melted at 75 C. and to this melt was added with stirring 250' grams of polyoxyethylene ether ofhydrogenated castoroil containing 25 oxyethylene groups per mole of oil. This product was a paste concentrate which could'further, be diluted with water to pro- 7 vide a fluid textile concentrate which is readily'dispersible in water and which possessed excellent textile and softening properties. 1500 grams of Water at 75 C. was added to this paste concentrate and the resultant'paste was al-.

lowed to cool-to room temperature with stirring. The

- final product was readily dispersible in water andremained fluid and stable on storage. v

' Example I ll 250 grams of; distearyl' dimethyl ammoniurnch-loride was heated to 75 C. and-to this melted product was added 250 grams of polyoxyethyile'ne ether of hydrogenated vI castor oil containing 25 oxyethylene groups per molof oil.

1500 grams ofwater at Cpwas added-to this. mixture and the resultant concentrate was allowed to cool swatches not so treated.

In order to determine the ratio of the polyoxyethylene ether of hydrogenatedcastor oil to the cationic softener prepared in Example I necessary for obtaining the best combination of fluidity of 25% active concentrates and textile softener properties, various ratioswere evaluated. Samples with nonionic fluidizing agent to cationic textile softener ratios of 29:71, 31:69, 33:67, 35:65 and 37:63 were formulated into 25% active aqueous dispersions and were checked for fluidity and retention of textile softener properties. It was determined that samples containing 69% or more of the cationic softener tended to become slightly gellatinous and therefore are not preferred. Samples containing 65% or less of the cationic softener were very fluid but their softening activity was impaired to a certain degree. The 33:67 (nonioniczcationic) formed very good fluid, 25 active concentrates and retained excellent textile softening properties.

The textile softening compositions of the present invention may also be applied to textile fabrics by padding from a padder, quetch or mangle or a substantive application may be made by a jig, beck or package machine. If

the application is made by padding, the flat goods can be. padded at 125 F. from thepadder, mangle or quetchwith a 1% to 2% solution of the 25 active fluid concentrate using a wet pick-up of about Yarns and textile fabrics can also be effectively softened in a packagemachine using 2 to 3% of the 25% active fluid conof F.

Thus, having described the invention, it may be construed in accordance with the following claims. What is claimed is:

, 1. A fluid textile softening composition which is readily dispersible in water consisting essentially of about 1 part i by weight of a nonionic emulsifier selected from the group .consisting of polyoxyethylene others of castor oil .and polyoxyethylene 'ethers of hydrogenated castor oil, said others containing from 20 to 300'oxyethylen'e groups per mole of oil, and from about 1 to 3 parts by Weight of a the reaction product of a hexitol epihalohyd'rin condento room temperature with stirring. The final product was readily dispersible water, andremained iiuid and stable on storage.

I Example IV To the reaction product of Example l 'wasiadded with stirring 250 grams of propylene glycol. T0500 grams of thisrnixture was added, 250 grams of polyoxyethylene ether of hydrogenated castoroil containing 25 oxyethyl-z oxyethylene ethers contain from I groups-per mole ofoil. I v ,3 ."A composition-as in claim 1 wherein said. polyoxyethylfie ether is the ether of castor oil. 5 p 7 1 A composition as" in cIaimZ 'wh'erein said "poly-"f oxyethyleneether is the ether of hydrogenated castor oil) 5. A composition-as in ciaima wherein said polyoxy- 'ethyleneetheris present inanamount of from about v I sate containing from '1 to;4 halohydriri radicals per hexitol residue reacted with a stoichiorrietric excess of an acyclic- C to C fatty acid diamide ofdiethylenegtriamine.

',2. The composition of 'claimf lfljin which the poly- 31:69 to about .35 :65 of said reactionproduct. 6. A fluidtextile softening composition which is readily.

i dispersible in Water consisting essentially of about 1 part by-wight ofia polyoxyethylene ether fof hydrogenated .castor oil containing oxyethylene groups per moleof V The resultant product, a 25% active'fluid concastor oil and from about 1 to 3 parts by weight of tie reaction product of sorbitol epichlorohydrin condensate containing about 2 chlorine radicals per sorbitol residue reacted with a stoichiometric excess of an acyclic tallow acids diamide of diethylene triaminei 7. A fluid textile softening composition which is readily dispersible in water consisting essentially of about 1 part by weight of a polyoxyethylene ether of hydrogenated castor oil containing '25 oxyethylene groups per mole of castor oil, and from about 1 to 3 parts by weight of the reaction product of sorbitol epichlorohydrin condensate containing about 2 chlorine radicals per hexitol residue reacted with a stoichiometric excess of an acyclic tallow acids diamide of diethylene triamine, and from 15 to 35% propylene glycol based on the weight of the reaction product. i

8. A fluid textile softening composition which is readily dispersible in water consisting essentially of about 1 part by weight of a polyoxyethylene ether of hydrogenated castor oil containing '25 oxyethylene groups per mole of castor oil, and from about 1 to 3 parts by weight of the reaction product of sorbitol epichlorohydrin condensate containing about 2 chlorine radicals per hexitol residue reacted with a stoichiometric excess of an acyclic tallow acids diamide of diethylene triarnine, and 25% propylene glycol based on the Weight of the reaction product.

9. A fluid textile treating composition which is readily dispersible in water and possessing freeze-thaw stability consisting essentially of about 1 part by weight of a polyoxyethylene ether of hydrogenated castor oil containing 25 oxyethylene groups per mole of castor oil, and from about 1 to 3 parts by weight of the reaction product of sorbitol epichlorohydrin condensate containing about 2 chlorine radicals per hexitol residue and a stoichiometric excess of tallow acids diamide of diethylene triamine, and 25 propylene glycol based on the weight of said reaction product and suflicient Water to provide an aqueous concentrate in which the polyoxyethylene ether plus the reaction product content is about 25 by Weight.

References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Arquads, Armour and (30., Chicago, 111., pp. recd February 1950.

Claims (1)

1. A FLUID TEXTILE SOFTENING COMPOSITION WHICH IS READILY DISPERSIBLE IN WATER CONSISTING ESSENTIALLY OF ABOUT 1 PART BY WEIGHT OF A NONIONIC EMULSIFIER SELECTED FROM THE GROUP CONSISTING OF POLYOXYETHYLENE ETHERS OF CASTER OIL AND POLYOXYETHYLENE ETHERS OF HYDROGENATED CASTER OIL, SAID ETHERS CONTAINING FROM 20 TO 300 OXYETHYLENE GROUPS PER MOLE OF OIL, AND FROM ABOUT 1 TO 3 PARTS BY WEIGHT OF THE REACTION PRODUCT OF A HEXITOL EPIHALOHYDRIN CONDENSATE CONTAINING FROM 1 TO 4 HALOHYDRIN RADICALS PER HEXITOL RESIDUE REACTED WITH A STOICHIOMETRIC EXCESS OF AN ACYCLIC C12 TO C20 FATTY ACID DIAMIDE OF DIETHYLENE TRIAMINE.