CA1232819A - Water insoluble antistatic compositions - Google Patents

Abstract

Abstract of the Disclosure Compositions which are particulate water insoluble and non dispersible salts of certain surface active sulfate or sulfonate anions and surface active quaternary ammonium cations are described. They are useful as wash cycle laundry softener-antistatic compositions.

Description

Sue This invention relates to solid particulate laundry softener-antistatic compositions formed when water solutions or dispersions of certain surface active sulfate or sulfonate salts are mixed with water solutions or dispersions of certain surface active qua ternary ammonium salts, and the resulting electrically neutral water insoluble and non dispersible undissociated organic salts are isolated in a form substantially free from other components. These come positions give surprising substantivity to fabrics when added to the laundry wash cycle, producing sub-staunchly softening and antistatic effects which are unexpected from an uncharged molecule since the prior art teaches that a net cat ionic charge is necessary to impart substantivity to softener-antistatic compost-lions.
The quality of softness of laundered fabric as used herein is well defined in the art and refers to the quality of a treated fabric whereby its texture is smooth, pliable, and fluffy. The use of modern heavy duty laundry detergents tends to leave laundered clothes with an undesirable harshness due partly to the deposition of Cay and My carbonates, phosphates, etc., on the clothes. It is an object of this invent-ion to provide a composition that will restore a soft pliable texture to laundered clothes.
Another problem encountered in laundering clothes, particularly if a mechanical dryer is used, is that of static cling, which is defined in the art as the tendency of laundered and dried fabric, especial-lye synthetic fabric such as nylon and polyester, to cling to itself and to the walls of the dryer due to the build-up of static electrical charges. When the fabric possesses static electrical charges it tends to attract lint and dust and furthermore is uncomfortable to wear. It is an object of this invention to provide 1;;:3Z8~9 a composition which will dissipate the static charge on laundered and dried fabric.
Qua ternary ammonium salts containing fatty alkyd groups have traditionally been used in household laundry softeners because they are substantive to the laundered fabric and provide both softening and control of static cling. However, they are incompatible with anionic detergents which severely restricts their use in the wash cycle. They are also incompatible with optical brighteners and proteolytic enzymes which are commonly incorporated into detergents and detergency boosters used in the wash cycle. The use of qua ternary ammonium salts in the rinse cycle necessitates an extra trip to the washing machine to add the softener at the appropriate time. It is a further object of this invention to provide a variety of products with soften-in and antistatic activity, including liquid or powdered detergents; dry bleaching products containing perorates, dry chlorine compounds, per carbonates, or peroxyacids; products for boosting detergency contain-in sodium tetraborate, surfactants, enzymes, optical brighteners, and the like; and wash cycle softener-antistatic compositions which can be added at the beginning of the wash cycle, thus eliminating the inconvenience of adding softener in the rinse cycle.
Many methods have been used to render qua ternary ammonium softener compositions compatible with detergents containing anionic surfactants in the laundry wash cycle.
US. Patent 4,184,970 discloses a wash cycle laundry softener composition in which particles or pills containing a qua ternary ammonium salt are sprayed with a solution of an 'anionic completing component , which can be an anionic synthetic sun-fact ant including water soluble salts of organic sulfuric acid reaction products. Optionally, the ~Z328~9 particles or pills and the completing component can be admixed as solids and sprayed with water. This procedure, however, only partially complexes the qua ternary ammonium salt, and the presence of the counter-ions from the two components causes the particles to disperse to an undesirable extent in the wash water. Also, since these pills are not homogeneous, their effectiveness depends on maintain-in the physical integrity of the particle throughout the wash cycle. It is a further object of this in-mention to provide a homogeneous composition which because of its homogeneity does not depend on maintaining a layered structure in the original particles to be effective.
US. Patent 3,703,480 discloses the use of aminopolyureylene resins mixed with qua ternary ammonium salts to form a detergent compatible softener. US.
Patent 3,626,891 discloses certain mixtures of qua ternary ammonium salts which are detergent compatible. Sun-fact ant sulfates and sulfonates and qua ternary ammonium salts have been combined in various ways in laundry softener compositions. US. Patent 4,184,970 has been described above. US. Patent 4,058,489 concerns softener qua ternary ammonium compounds and anionic surfactants combined in molar ratios of anionic sun-fact ant to qua ternary ammonium salt of 0.6 to 1 to 0.95 to 1 and kept dispersed with a non ionic or an amphoteric surfactant. US. Patent 3,644,203 concerns combinations of a fatty alcohol-fatty alcohol sulfate complex with softener qua ternary ammonium salts. The resulting softener compositions must be used in non-ionic detergents or in rinse cycle softeners. US.
Patent 4,000,077 concerns combination of softener qua ternary ammonium salts and fatty alcohol sulfates in weight ratios of 10 to 1 to 2 to 1, useful as rinse cycle softeners. US. Patent 4,173,539 relates to ~2819 fatty monoalkyl qua ternary ammonium salts and anionic detergents in aqueous suspension used as rinse cycle softeners. US. Patent 4,255,294 concerns "complexes"
of qua ternary ammonium salts and anionic detergents as wash cycle softeners. The molar ratio of anionic detergents to qua ternary ammonium salt is from 1.2 to 1 to 12 to 1, and a non ionic detergent is included as a dispersant. Canadian Patent 818,419 discloses the formation of an "electro-neutral complex" formed by combining a cat ionic textile softening agent with an anionic surfactant in the presence of a non ionic-cat ionic dispersing agent. The softening activity of this electro-neutral complex depends on a cat ionic environment, and thus is not operable with all deter-gent systems, especially those based on anionic sun-fact ants. Further, the "electro-neutral complex"
cannot be isolated in a form substantially free from other components which could be sold as an article of commerce, or admixed with other products to add soft-eying and antistatic activity. US. Patents 3,431,265 and 3,535,039 describe compositions formed by mixing a biologically active qua ternary ammonium compound with a surfactant sulfate or sulfonate which contains a glycerol moiety or a polyether moiety. These mixtures result in compositions which are water dispersible and possess no textile softening activity. All of these softener compositions depend for their softening and antistatic activity on their being effectively dispel-sod, either through the use of an excess of one of the charged components, i.e. the softener qua ternary ammonium salt or the anionic detergent or surfactant, or through the use of a non ionic surfactant or an amphoteric surfactant as a dispersant. Further those which are proposed as wash cycle products depend for their effectiveness as detergents on a very careful selection of detergent surfactant which will be 1~3Z~319 compatible with the dispersed softeners. An object of this invention is to provide a softener antistatic composition that remains a separate, solid phase during the wash cycle and the rinse cycle, and spreads on the clothes to provide softening and static protect-ion as the clothes are dried in a mechanical dryer.
It is a further object to provide a composition that, because it is a separate, solid phase, does not inter-act with the detergent surfactants and thus is compatible with all surfactant systems and detergent components, thus eliminating or easing most of the prior restriction on formulating products with softeners to be used in the wash cycle. It is a further object to provide a softener-antistatic composition which is a single chemical compound and is effective in a pure form without a requirement for dispersants, dispersion inhibitors, specially formulated detergents and the like.
We have discovered that by forming a solid, particulate, water insoluble organic salt of a surface active sulfate or sulfonate anion and a surface active qua ternary ammonium cation by methods herein described there results a composition which is a superior laundry softener and antistatic agent which is compatible with all detergent surfactant systems. These compositions are not complexes, nor are they mixtures of cat ionic salts and anionic surfactant salts, but are distinct chemical compounds which are neither anionic nor cat ionic in nature. They are undissociated organic salts, or "ion pairs" with no water soluble component.
They are distinguished from qua ternary ammonium halides, sulfates, phosphates, acetates, and the like in that the compounds of this invention do not dissociate at all in water. They are distinguished from the systems of the prior art in that they are preformed and is-fated as pure compounds, dried, and put into particles 1~3~8~9 of the desired size. By doing this the insoluble organic salt, which also forms in the systems of the prior art, becomes surprisingly much more effective as a softener-antistatic agent, and also becomes inert to the other components of the detergent or other laundry product with which it is used. Without being held to theory, we believe that we have modified the size, hardness, and the surface properties of the particles of the softener so that they both remain intact and undispersed in the wash liquor throughout the wash cycle and also tend to attach themselves to the fabric in the wash in a manner unaffected by the surfactants present.
This invention relates to particles of an undissociated organic salt which results when a sun-face active water soluble or dispersible sulfate or sulfonate salt is chemically combined with a surface active water soluble or dispersible qua ternary ammonium salt in exact stoichiometric ratio and under conditions of intimate mixing, preferably in a water medium, and the organic phase which forms is separated from the water phase in dry particulate form sub-staunchly free from other ingredients. Thus we have discovered that by isolating this water insoluble organic phase under conditions such that the counter-ions of the sulfate or sulfonate surfactant and the qua ternary ammonium surfactant are removed in the water phase and then purifying, drying, and grinding the insoluble phase, homogeneous water insoluble and under normal laundry conditions non dispersible come positions, which are undissociated organic salts of the sulfate or sulfonate anions and the qua ternary ammonium cations, result. Since the non dispersibility of the particles of this invention is vital to their function, we define non dispersibility in a functional way as being able to recover essentially unchanged in 7 ~2328l9 size and shape the particles of softener after the wash liquor containing detergent and softener has been agitated in a simulated wash cycle to which no fabric is added. This can be accomplished with standard sieves and examination of the isolated particles with a magnifying glass. These compositions, when added to the laundry wash cycle as small particles are effective softener antistatic agents when the clothes are subsequently dried in a mechanical dryer.
The compositions of this invention are chemical compounds in the classical sense in that they have a precise weight ratio of components. They are water insoluble and non dispersible undissociated ion pairs of a surface active qua ternary ammonium cation and a surface active sulfate or sulfonate anion of the structure:
i. R1R2R3R4N OS02(0)x 5 wherein Al is an alkyd, alkenyl, alkoxyalkyl or acylamidoalkyl group containing about 12 to 22 carbon atoms with the alkyd radical of the acylamidoalkyl being ethyl or propel, R2 is Al, hydroxyethyl, hydroxypropyl, ethyl, or methyl, R3 and R4 are methyl, ethyl, propel, hydroxy-ethyl, hydroxypropyl or bouncily R5 is an alkyd, alkenyl, alkaryl or moo-hydroxyalkyl group containing about 14 to 22 carbon atoms, and x is 0 or 1, and N +
R7 OS02(0)xR5

2 2 7 - 8 _ 1232~

wherein R6 is methyl or ethyl, R7 is alkyd or alkenyl containing about 14 to 22 carbon atoms, and R5 and x are as defined above.
The anionic portion of the ion pair is derived from surfactant sulfate or sulfonate salts included in the group consisting of wherein R is an alkyd or alkenyl group containing 14 to 22 carbon atoms, and is preferably an alkyd group containing about 14 to 20 carbon atoms, and is most preferably a straight chain alkyd group containing about 16 to 20 carbon atoms, and R'- S03 wherein R' is an alkyd, alkenyl, alkyd aureole, or hydroxyalkyl group containing about 14 to 22 carbon atoms.
Since the ion pair product no longer contains the original cation associated with the sulfate or sulfonate anion except as a minor impurity, its choice is one of convenience. It must, however, dissociate from the sulfate or sulfonate anion to a substantial extent in water. Suitable cations include No , K , H+, Ho ethanol ammonium, diethanol ammonium, triethanol ammonium, and other water soluble amine.
Less suitable are My and Cay which usually do not dissociate sufficiently.
Suitable surfactant alcohol sulfate salts include sodium stroll sulfate, sodium Seattle sulfate, sodium myristyl sulfate, sodium oilily sulfate, sodium lonelily sulfate, and sodium tallow sulfate, and the corresponding ammonium and potassium salts. These products are well known in the art and are readily available from many sources. Especially preferred alcohol sulfates are those of alcohols derived from 1232~19 g hydrogenated tallow or hydrogenated vegetable oil.
Sulfonates useful in this invention include those which result from the reaction of olefins containing 14 to 22 carbon atoms with sulfur trioxides The product of this reaction is a mixture of isomers of alkenyl sulfonates and hydroxyalkyl sulfonates of the structures RICH = CH-CH2SO3H

OH
in which R" is alkyd containing 11 to 19 carbon atoms:
which are neutralized with alkali metal hydroxides to the corresponding alkali metal sulfonate salts.
Also included are alkylaryl sulfonates resulting from the reaction of C8 to C18 alkyd benzenes and naphthalenes with sulfur trioxides of the structure R''' - Y - SUE
wherein R"' is alkyd containing 8 to 18 carbon atoms and Y is phenol or naphthyl, which are neutralized with alkali metal hydroxides to the corresponding alkali metal sulfonate salts.
Paraffin sulfonates of the structure Ho SHEA ) mCI Ho SHEA ) n SUE
wherein m and n are integers from O to 22 and m + n is 14 to 22; made by the sulfoxidation of n-paraffins are also included.
The cat ionic portion of the ion pair is derived from qua ternary ammonium salts whose cat ionic portions are of the structure i . RlR2R3R4N
wherein Al is an alkyd, alkenyl, alkoxyalkyl or acylamidoalkyl group containing about 12 to 22 carbon atoms with the alkyd radical of the acylamidoalkyl being ethyl or propel, R2 is Al, hydroxyethyl, hydroxypropyl, ethyl, or methyl, R3 and R4 are methyl, ethyl, propel, hydroxyethyl, hydroxypropyl or bouncily, and ii. R6 I

No 1l wherein R6 is methyl or ethyl, and R7 is alkyd or alkenyl containing about 14 to 22 carbon atoms.
Cations of the first structure are preferred, and are most preferred when Al and R2 are C16 to C20 alkyd and R3 and R4 are methyl or ethyl.
Since the ion pair product no longer contains the original anion associated with the qua ternary ammonium cation except as a minor impurity, its choice is one of convenience. It must, however, dissociate from the qua ternary ammonium cation to a substantial extent in water. Suitable anions include Of , By , I , methosulfate, ethosulfate, S04 , N03 , acetate and other anions which dissociate in water.
Suitable qua ternary ammonium salts include distearyl-dimethyl ammonium chloride, cetyltrimethyl ammonium chloride, disallow dim ethyl ammonium methosulfate, dicocodimethyl ammonium chloride, stearamidopropyl trim ethyl ammonium chloride, alkyd (C12 16) dimethylbenzyl ammonium chloride, tridecyloxy-propel trim ethyl ammonium chloride, stroll Dow-hydroxyethyl methyl ammonium chloride, dihydrogenatedtallow ethyl imidazolinium ethosulfate, dihydrogenated ~232~9 tallow dim ethyl ammonium chloride, tallow di-2-hydroxy-propel methyl ammonium chloride, stroll trim ethyl ammonium chloride, and distearamidoethyl dim ethyl ammonium chloride.
Another aspect of this invention is to the process for preparing a laundry softener-antistatic composition which is a water insoluble organic salt of a surface active sulfate or sulfonate anion and a surface active qua ternary ammonium cation. This pro-cuss consists essentially of - (i) intimately mixing, in any order from about 40 to 90 parts of water, preferably from about 50 to 80 parts of water with about 10 to 60 parts, prefer-ably about 20 to 50 parts of the combination of (a) a salt of the sulfate or sulfonate anion and a counter ion which is substantially ionized in water, and (b) a salt of the qua ternary ammonium cation and a counter ion which is substantially ionized in water, the molar ratio of a to b being from about 0.8 to 1 to 1.2 to 1 and prefer-ably being about 1 to 1;
(ii) allowing the mixture to stand at a sufficient temperature for a sufficient period of time such that the water insoluble organic salt of the sulfate or sulfonate anion and the qua ternary ammonium cation separates from the water phase in a form such that it is no more than about 60% water by weight, and is preferably less than about 40% water, and contains no more than about 0.25 moles of the salt of the counter-ions per mole of the ion pair of the sulfonate or sulfate anion and the qua ternary ammonium cation, and preferably contains less than about 0.1 mole of counter ion salt per mole of product organic salt;
(iii) evaporating the trapped water from the sulfate or sulfonate-quaternary ammonium organic 123~

salt until it contains less than about 25% water by weight, and preferably contains less than about 10%
water by weight, and (iv) grinding, spray congealing, or otherwise putting the composition in the form of small particles of less than about 500 microns, and preferably from about 50 to 400 microns in diameter.
Drying can be effected by any of a number of methods common in the art. Examples of suitable methods include the use of a Sandvik belt dryer and the use of a Mizzen soap dryer. Products which are non-tacky solids can be simultaneously dried and ground in a ribbon blender. A preferred method is spray-congealing, whereby the molten compounds are sprayed counter currently through air to give small, discrete particles, the size of which can be controlled.
The dried product is put into a powder form suitable for adding to the laundry wash cycle by methods known in the art. Hard, non-tacky solids are readily ground to particles less than about 500 microns, and preferably from about 50 microns to 400 microns in diameter, or they may be melted and spray-congealed into pills of this size. Preferred products have sistering points from about 35 to 120C, and more preferred products have sistering points from about 55 to 100C.
The compositions of this invention effect good static protection and softening with all types of laundry detergents in common use. They are effective in built powders based on polyphosphates, ETA, sodium carbonate, or zealots, and containing non ionic, anionic, and amphoteric surfactants. They can either be incorporated into the powder or added separately to the washing machine. They are also effective when added with built or unbolt liquid detergent containing non ionic, anionic, or amphoteric surfactants.
Since these compositions are uncharged and furthermore do not dissolve or disperse in the wash liquor, they do not interfere with the activity of proteolytic enzymes and optical brighteners, and thus can be used in detergents and detergency boosters containing these components.
It will be recognized that these compositions can be used in the rinse cycle of the laundry operation.
They can be added as powders or less preferably can be dispersed by methods standard in the art and added as dispersions or emulsions. They can also be applied in the dryer, where they have the advantage of being non-corrosive. For dryer application melting point modifiers, substrates and other modifications common in the art may be used.
It is understood that other adjutants commonly added to laundry softener compositions, such as perfumes, dyes, and the like, can be incorporated into the come positions of this invention.
Our invention is further illustrated by the following examples.
Example 1 Standard ethylene blue titrations were used to determine the equivalent weights of a 45% paste of sodium tallow alcohol sulfate (Avirol T-45, trademark of Continental Oil Companioned a 75~ alcohol dispersion of di(hydrogenated tallow) dim ethyl ammonium chloride (Adogen 442, trademark of Shrieks Chemicals). The equip valet weight per surface active sulfate group of the as is paste of Avirol T-45 was 1100; the equivalent weight per surface active ammonium group of the as is dispersion of Adogen 442 was 766.
55 g of Avirol T-45 (0.05 moles) was mixed 35 with 38.4 g of Adogen 442 (0.05 moles) and 100 g of water was added. The mixture was heated to 60C, then ... I.

stirred for 30 minutes at 60-70C. A water phase separated from an emulsion phase when agitation stopped, on standing about 2 hours at 70C the emulsion broke and the organic phase was nearly clear. The composition was cooled to room tempera-lure, at which temperature the organic phase was very hard and the water phase could be decanted readily.
The organic phase weighed 62.7 g and contained 21.5%
water by weight. It was broken into small lumps and spread in a thin layer to evaporate the remaining water. When it contained less than 5% water it was ground to a fine, non-tacky powder in a Waring Blender and screened through a 40 mesh sieve. To show that the composition of this example had neither cat ionic nor anionic character, 0.1 g of the dried powder was dissolved and 10 ml of trichloroethylene, and 5 ml of 1 N H2SO4 and 5 ml of ethylene blue indicator solution were added. The mixture was shaken vigorously and the layers were allowed to separate. The ethylene blue was the same intensity in both layers. If an excess of qua ternary ammonium salt were present the ethylene blue would have all remained in the water phase; if an excess of tallow sulfate were present, the ethylene blue would have been in the ethylene chloride only.
Therefore the composition of this example has no net cat ionic or anionic functionality.
The product was tested as a wash cycle softener-antistat by the following method: 8 lobs. of mixed soiled clothes containing about equal portions of synthetic fabric (nylon, polyester and acrylic), permanent press fabrics (cotton-polyester blends) and cotton fabrics were placed in a 20 gal capacity auto-matte washer and the washer was filled with 100 Pam hard water at 40C. 100 g of a powdered detergent containing 6.1% phosphorus and non ionic and anionic surfactants, and the stated quantity of the softener-1 ;~3281~

anti stat of this example were added as the washer started agitating. The washer completed its cycle of a 10 minute wash, spin, room temperature rinse, and final spin to about 50% moisture pickup. The clothes were dried in an electric hot air dryer using a 40 minute heat cycle plus a 5 minute cool-down cycle. Static was evaluated visually by a trained observer and was rated 0 if no static could be detected, + if static was just detectable, ++ if static was present but judged to be less than that produced by using the detergent alone, and +++ if there was no reduction from the detergent alone. A
rating of + is acceptable, a rating of 0 is of course preferred.
Hand was evaluated on a cotton terry cloth towel and was rated on a scale of 1 to 4, in which a ranking of 1 is the equivalent of using a qua ternary ammonium softener in the rinse cycle, and 4 is the equivalent of the detergent alone. A ranking of about 0 2.5 is acceptable, lower rankings being preferred.
Results from testing the composition of Example 1 are shown in Table 1. At 4.5 g per 8 lb. of laundry, static was eliminated and the hand was excellent. At 3 g per 8 lb. of laundry the static was 5 just detectable and the hand was still very good.

Table 1 Softening and antistatic activity of the composition of Example 1.
Quantity of composition of 30 Example 1 added to 8 lb. of laundry, q Static Hand 4.5 0

3 + 2 1~3Z819 Example 2 Compositions were prepared by the procedure of Example 1, except that the molar ratio of sodium tallow alcohol sulfate to dihydrogenated tallow dim ethyl ammonium chloride was varied.
Composition A: 55 g of Avirol T-45 (0.05 moles) was mixed with 28.7 g of Adogen 442 (0.0375 moles) and 100 g of water. The water phase which separated was cloudy, and contained about 4% of the added sodium tallow alcohol sulfate. The dried product was a non-tacky powder.
Composition B: 55 g of Avirol T-45 (0.05 moles) was mixed with 52.5 g of Adogen 442 (0.069 moles) and 100 g of water. A clear water phase that contained no surfactant separated. The dried product was a non-tacky powder.
Compositions A and B were tested by the method described in Example 1. The results are shown in Table 2. Composition A, with excess sodium tallow alcohol sulfate had both unacceptable static and softening at US g per 8 lb. of laundry. Composition B eliminated static but was less effective as a softener than was the mole/mole product of Example 1.
Table 2 25 Softener added to 8 lb. of laundry Static Hand

4.5 g of Composition A ++ 3 4.5 g of Composition B 0 2 Example 3 The organic salts listed below were prepared by the method of Example 1, and were tested as laundry wash cycle softeners. All were effective as softeners and all showed antistatic activity.
A. di(hydrogenated tallow) dim ethyl ammonium cetyl-stearyl sulfate ~32~19 B. di(hydrogenated tallow) dim ethyl ammonium C12 15 Al Kane sulfonate C. di(stearamidoethyl) dim ethyl ammonium C16 18 olefin sulfonate D. tallow trim ethyl ammonium C12_14 olefin sulfonate E, disallow methyl imidazolinium dodecyl Bunsen sulfonate.
Example To show that the softener-antistat obtained in a particulate form substantially free from other in-gradients is superior to a composition formed in situ in the wash liquor, the following detergents were prepared:
15 Ingredient Composition A Composition B
(parts by weight) Sodium tripolyphosphate 40 40 Soda ash 41.4 41.4 Sodium silicate pentahydrate 5 5 20 Sodium tetraborate pentahydrate Sodium carboxymethyl cellulose Linear alcohol ethoxylate 7 7 Sodium alkylbenzene sulfonate (90%) 1.5 25 Di(hydrogenated tallow) dim ethyl ammonium chloride (75%) 3 Composition of Example 1 3.6 To show the difference in the physical nature of the compositions 0.6 g of detergent was added to 300 g of tap water at 49C stirring with a slight vortex.
After 90 seconds the detergent solutions were poured through a 9 cm circle of black percale in a Buchner funnel, and particles trapped on the fabric were noted.
Composition A left very few large particles that were undissolved qua ternary ammonium salt. Composition B
left many small uniform particles. When viewed at lox 1 Z3Z8~9 magnification, they appeared to be no different in size and shape from the softener powder added to the deter-gent. The softening end antistatic activity of the two compositions was tested by the procedure of Example 1. Static produced on synthetic fabrics in the dryer was measured with an electrostatic voltmeter. The average charge from the load washed with Composition A
was 4.1 TV; that of the load washed with Composition B
was 3.7 TV. The hand of the cotton terry towels from Composition A was rated 3.7, those from Composition B
rated 3.2.
Liquid detergency boosters designed to be added with a detergent to the laundry wash cycle possess-in softening and antistatic activity can be prepared by mixing suitable surfactants, optical brighteners, enzymes, builder salts, polymers, and the particulate softener-antistatic compositions herein described.
Such compositions can contain from about 5% to 50% of one or more non ionic, anionic, or amphoteric surfactants;
from 0 to about 1% optical brighteners, from 0 to about 12% enzymes: from 0 to about 20% builder salts such as sodium tripolyphosphate, tetrapotassium pyrophosphate, sodium carbonate, sodium citrate, borax, and the like:
from 0 to about 5% of a polymeric anti redeposition agent such as carboxymethyl cellulose, sodium polyp acrylate, polyvinylpyrrolidone, and the like; and from about 2% to 35% of one or more particulate softener-antistatic agents herein described, the balance being water. In these compositions the softener-antistatic agent is present as particles.
Example 5 A product to be used with laundry detergents as a detergency booster-softener-antistat combination was prepared by mixing 15.4 g of tallowoyl isethionate 35 (67%), 5 g of a 10% solution of polyvinylpyrrolidone, 4 g of a 5.25% solution of optical brightener in 25%

1232~

ethanol, 160 g of water, and 15.8 g of the compost-lion of Example 1. The same composition was pro-pared without the softener-antistatic composition of Example 1. Both products were tested by the procedure in Example 1, using 57 g (1/4 cup) of the detergency booster product with 100 g of a powdered non-phosphate anionic detergent. Static charge in the synthetic fabrics was measured with an electrostatic voltmeter, and was found to be reduced by 1/2 by adding the softener-antistat (first composition above) from that of the compost-lion without the softener-antistat. The hand was also substantially improved by adding the softener-; anti stat. After the composition had stood for 16 months a sample was screened through a 200 mesh sieve, and particles of the added softener-antistat were still present.
Powdered detergency boosters designed to be added with a detergent to the laundry wash cycle possessing softening and antistatic activity can be prepared by mixing suitable surfactants, bleaches, enzymes, optical brighteners, builder salts, polymers, and other adjutants, and the particulate softener-antistatic compositions herein described. Such combo-sessions may contain from 0 to about 80% of one or more non ionic, anionic, or amphoteric surfactants; from 0 to about 30% of a powdered bleach such as sodium perorate, sodium per carbonate, proxy organic acids, dry chlorine containing compounds, and the like; from 0 to about 12% enzymes; from 0 to about 1% optical brighteners; from 20 to about 98% builder salts such as condensed phosphates, borax, sodium carbonate, zealots, trisodium nitrilotriacetate, and the like;
from 0 to about 5% of an anti redeposition polymer such as sodium carboxymethyl cellulose, sodium polyacrylateand other polycarboxylates, and the like, and from - 20 _ 1~32~9 about 2% to 50% of one or more of the particulate softener-antistatic compositions herein described.
Example 6 To prepare a detergency booster-softener-anti stat product in a powdered form, 12 g of dinonyl-phenol condensed with 150 moles of ethylene oxide (mop. 60C) was warmed to 65C, and 6 g of the come position of Example 1 was mixed in thoroughly. The mixture, containing particles of the softener-antistat in the molten non ionic surfactant, was allowed to cool to room temperature and was ground in a Waring blender and screened through a 20 mesh sieve. Using the same quantities of softener-antistat and non ionic surfactant another composition was prepared and heated to 95C
at which temperature the softener-antistat was also molten, so that the particles were destroyed and the product was dispersed in the non ionic surfactant. It was mixed, cooled, and ground in the same way as the previous composition. To test, 13.5 g (6 g of non-ionic and 4.5 g of softener-antistat) of the products were added with 100 g of a non-phosphate anionic powdered detergent to the wash cycle. The first come position, in which the softener particles remained intact, showed a large reduction in static from the detergent alone, and the hand effect was rated 2.5.
The second composition in which the softener was melted into the non ionic surfactant showed a marginal reduction in static and a hand effect rated 3.8. This demonstrates that to obtain softening and antistatic effects from the compositions of this invention it is necessary for the particles of softener to remain intact in the laundering process.
Example 7 The composition of Example 1 was mixed with sodium tetraborate decahydrate (borax) at a ratio of 3.5 parts of softener to 96.5 parts of borax, to - 21 ~23Z~319 prepare a detergency booster with softening and anti-static activity. It was tested by the procedure of Example 1 for ten cycles. Static was rated 0 for each of the 10 cycles. There was no yellowing of white fabrics in the load as evidenced by no change in the reflectance measured with a Gardener reflect-meter.
Example 8 The particles of this invention can be sup-penned in liquid laundry detergents to obtain detergent-- softener-antistat compositions. The following deter-gents were prepared:
Ingredient Composition A Composition B
(parts by weight) 15 Linear alcohol ethoxylate 25 25 Composition of Example 1 5 Avirol T-45 (see Example 1) 5.2 Adogen 442 (see Example 1) 3.6 Water 70 66.2 The "black cloth test" of Example 4 was used to show that the softener particles in Composition A
remained intact in the wash liquor, and that no part-ales were present in the wash liquor from Composition B. The two compositions were tested as detergent-softeners by the procedure of Example I Static generated on synthetic fabrics in the dryer was measured with an electrostatic voltmeter. The average charge in the load washed with Composition A was 2.4 TV; the average charge from Composition B was 3.8 TV.
The hand of the terry towels washed with Composition A
was rated marginally superior to that of the towels washed with Composition B. The detergency of Compost-lion A can be improved by the incorporation of a proteolytic enzyme. Since the softener particles are uncharged, and furthermore remain intact throughout the wash cycle, the softener does not interfere with the activity of the enzyme.

Jo ,

Claims (17)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A particulate chemical product that contains as the sole active component at least one water in-soluble, nondispersible organic salt having the structure:
i. R1R2R3R4N+ -OSO2(O)xR5 wherein R1 is an alkyl, alkenyl, alkoxyalkyl or acylamidoalkyl group containing about 12 to 22 carbon atoms with the alkyl radical of the acylamidoalkyl being ethyl or propyl;
R2 is R1, hydroxyethyl, hydroxypropyl, methyl, or ethyl;
R3 and R4 are methyl ethyl propyl, hydroxyethyl, hydroxypropyl or benzyl;
R5 is an alkyl, alkenyl, alkaryl or mono-hydroxyalkyl group containing about 14 to 22 carbon atoms; and x is 0 or 1, and ii.
-OSO2(O)xR5 wherein R6 is methyl or ethyl;
R7 is alkyl or alkenyl containing about 14 to 22 carbon atoms, and R5 and x are as defined above.

2. The chemical product of claim 1 which contains less than about 0.25 moles of inorganic salt per mole of said organic salt.

3. The chemical product of claim 1 which contains less than about 25% water by weight.

4. The chemical product of claim 1 in which the particles are of a size less than 500 microns.

5. The chemical product of claim 1 in which R1 and R2 are the same and they are alkyl or alkenyl containing about 16 to 22 carbon atoms.

6. The chemical product of claim 1 in which R1 and R2 are the same and they are alkyl or alkenyl containing about 16 to 22 carbon atoms; R3 and R4 are methyl: R5 is alkyl or alkenyl containing about 16 to 22 carbon atoms; and x is 1.

7. The process of preparing the chemical product of claim 1 which consists essentially of the steps of:
i. intimately mixing, in any order, from about 40 to 90 parts of water with about 10 to 60 parts of the combination of a. a salt of the sulfate or sulfonate anion and a counterion which is substantially ionized in water, and b. a salt of the quaternary ammonium cation and a counterion which is substantially ionized in water, the molar ratio of a to b being from about 0.8 to 1 to 1.2 to 1;
ii. allowing the mixture to stand at a sufficient temperature for a sufficient period of time such that the water insoluble organic salt of the sulfate or sulfonate anion and the quaternary ammonium cation separates from the water phase in a form such that it is no more than about 60% water by weight, and contains no more than about 0.25 moles of the salt of the counterions per mole of the ion pair of the sulfate or sulfonate anion and the quaternary ammonium cation;
iii. evaporating the trapped water from the sulfate or sulfonate-quaternary ammonium organic salt until it contains less than about 25% water by weight, and iv. grinding, spray congealing, or otherwise putting the composition in the form of small particles of less than about 500 microns in diameter.

8. In a fabric machine washing and drying method, a step for improving the softness and anti-static properties of the laundered fabrics which comprises contacting said fabrics with a product of claim 1 prior to drying said fabrics.

9. The method according to claim 8 in which said contacting step is preformed in the wash cycle of said method.

10. The method of claim 9 wherein said product is added to the laundry wash solution in the presence of an anionic detergent.

11. The method of claim 9 wherein said product is added to the laundry wash solution in the presence of an optical brightener.

12. The method of claim 9 wherein said product is added to the laundry wash solution in the presence of a proteolytic enzyme.

13. The method according to claim 8 in which said contacting step is preformed during a rinse cycle of said method.

14. The method according to claim 8 in which said contacting step is preformed in the drying cycle of said method while said fabrics are damp.

15. A laundry detergent composition comprising an anionic detergent and a product according to claim 1.

16. A composition according to claim 15 contain-in a proteolytic enzyme.

17. A laundry detergency booster comprising borax and a product according to claim 1.