Treating compositions for softening fibers

United States Patent Office

3,178,366

Patented Apr. 13, 1965

3,178,366

TREATING COMPOSITIONS FOR SOFTENING FIBERS

Paul L. Du Brow, Chicago, Ill., and John S. Brandifi, Baltimore, Md., assignors to Armour and Company, 6 Chicago, Ill., a corporation of Delaware

No Drawing. Filed May 28, 1962, Ser. No. 197,895

Claims. (CI. 252—8.8)

This invention relates to surfactant compositions, and jq more particularly to fiber-treating compositions for softening fibers and conditioning them for rewetting, etc.

The present application is a continuation-in-part of our copending application Serial No. 787,344, filed January 19, 1959, now abandoned. 15

The quaternary ammonium salts, being “cationic” or “cation-active” agents, are not compatible with anionactive materials. Generally, quaternary ammonium salts are precipitated or rendered inactive by organic anionactive materials such as soaps, alkyl aryl sulfonates, 20 other anionic synthetic detergents, and carboxy methyl cellulose. Also, the polyvalent inorganic anions, such as the phosphates and sulfates, act as precipitants of the quaternary ammonium salts.

This incompatibility is a serious problem, for the ef- 25 fective utilization of the quaternary ammonium salts for their functional benefits is restricted thereby. For example, the quaternary ammonium salts are very effective as softening agents for hair and cellulosic materials such as textiles and tissue paper. However, when the quater- 30 naries are used as the active ingredients for imparting “softness” to the treated material, traces of any of the aforementioned precipitants, which, are usually carried over with the base material from previous treatments, either precipitate or render the quaternary inactive. Con- 35 sequently, the possible benefits which, could be obtained from the ammonium salts are lost.

A second problem arises out of the fact that if a second material is added to the quaternary ammonium salt, it is found that the second material does not aid the 40 quaternary ammonium salts in their function as softening agents but constitute in effect waste material as far as such softening function is concerned, and in addition it is found that such added material does not tend to overcome the waterproofing characteristic of the quaternary ⁴⁵ammonium salt, etc.

We have discovered that a surface-active composition consisting of a quaternary ammonium salt in combination with an ethoxylated quaternary ammonium salt ₅θ meets the above-described problems in that the ethoxylated quaternary ammonium salt adds a full quota of softening activity to that of the first-mentioned quaternary ammonium salt, while at the same time conditioning the textile, etc. material for rewetting. Instead of ₅₅being an inert or waste material as far as actively inducing softening is concerned, the ethoxylated quaternary ammonium salt contributes actively to the softening function of the complete composition. Finally, the composition comprising the quaternary ammonium salt and the θθ ethoxylated quaternary ammonium salt is found to be highly compatible with anion-active materials.

Therefore, a principal object of the present invention is to provide surface-active compositions, containing quaternary ammonium salts, which are compatible with anion-active materials. A further object is to provide such compositions in which effective softening effects are produced through the added softening activity provided by the ethoxylated quaternary ammonium salt. A still further object is to provide such a composition which may be employed in the treating of textiles and other fibers for imparting softness thereto, while at the same time conditioning the material for rewetting. Other specific objects and advantages will appear as the details of the invention are set out.

The surface active compositions of the instant invention comprise a quaternary ammonium salt and an ethoxylated quaternary ammonium salt containing 15 to 60 moles of ethylene oxide. The compositions may be in the form of free flowing powders or aqueous dispersions. Coloring and perfume may, if desired, be added to the aqueous dispersions.

The quaternary ammonium salt component of the surface active compositions of the invention has the formula

<img file="US3178366A_D0001.tif" />

wherein R represents benzyl or an alkyl group containing 1 to 3 carbon atoms, R₄ represents benzyl, or an alkyl group containing 1 to 3 carbon atoms, or an alkyl group containing 12 to 18 carbon atoms, R₂ represents an alkyl group containing 12 to 18 carbon atoms, and X represents an anion, such as halogen, acetate, phosiphate, nitrite, and methyl sulfate radicals. The carbon chain of the alkyl group containing 12 to 18 carbon atoms may be straight or branched, and saturated or unsaturated. In the preferred embodiments of the invention, this group is derived from long chain fatty acids. The preferred ammonium salt is an alkyl trimethyl ammonium chloride or a dialkyl dimethyl ammonium chloride wherein the alkyl group is derived from hydrogenated tallow.

The ethoxylated quaternary ammonium salts that have peculiar efficacy as the other active component of the compositions of the instant invention are derivatives of ethoxylated tertiary amines and diamines containing 15 to 60 moles of ethylene oxide.

The ethoxylated quaternary ammonium salt derivatives of the tertiary amines have the formula

N— (OE₂CH₂O).H _R Ri

[XJwhere R represents an alkyl group containing 8 to 18 carbon atoms, Rj represents methyl, or ethyl, or benzyl radicals, n is an integer from 15 to· 60, and X represents an anion, such as halogen, acetate, phosphate, nitrite, and methyl sulfate radicals.

The ethoxylated quaternary ammonium salt derivatives of the ethoxylated diamines have the formula (CH₂CH₂O)xH (CH₂Cn₂O)_yII”I+

R—Jf—(0H₂)m—

R?\cH₂CH₂O) ,Π_

[X]Ri where R is an alkyl group containing 8 to 18 carbon atoms, Rj represents methyl, or. ethyl, or benzyl radicals, m is an integer from 2 to 3, the sum of x, y and z is an integer from 15 to 60, and X represents an anion, such as halogen, acetate, phosphate, nitrite, and methyl sulfate radicals.

3,178,366

In the preferred embodiments of the invention, the R groups of the ethoxylated quaternary ammonium salts are derived from long chain fatty acids. Also, the fatty acids can be derived from mixtures, such as are prepared from tallow, coconut oil, and soybean oil. The coco g ethoxylated quaternary ammonium salts are preferred for use in the surface-active compositions of this invention.

The effective proportions of the active ingredients of the compositions were found to be that for every part by weight of the quaternary ammonium salt, there should be jo 0.1 to 2.0 parts by weight of the ethoxylated quaternary ammonium salt. In other words, the weight ratio of the quaternary ammonium salt to ethoxylated quaternary ammonium salt is within the range of from 10:1 to 1:2. When the components are present in these ratios, the re- 15 suiting compositions are stable and may be diluted with water for ease of handling and addition to other aqueous media containing the base materials to be treated therewith. When the compositions the so used, the presence of any of the aforementioned anionic precipitants does 20 not render the quaternary ammonium salt ineffectual. As a consequence thereof, it is now possible to utilize quaternary ammonium salts under conditions that were considered heretofore adverse.

Specific tests on a comparative basis in which fabric 25 is treated with the surfactant compositions described herein and like fabrics treated with quaternary ammonium salts which are not ethoxylated and which are non-ionic, have demonstrated that the former compositions are more effective from the standpoint of softening, while at the 30 same time retaining the rewet characteristic of the treated material. It is believed that this is due to the active contribution in softening characteristics of the ethoxylated quaternary ammonium compound and to some property in the latter compound for retaining the rewet qualities 35 of the textiles, etc.

Having described in detail each of the component compounds constituting the surface-active compositions of the present invention, it therefore becomes convenient to present a number of specific and illustrative completed 40 compositions, the parts being given by weight.

Example I

Distearyl dimethyl ammonium chloride50

Dilauryl methyl polyoxyethylene ammonium chloride 45 containing 15 moles ethylene oxide50

Example II

Dilauryl diethyl ammonium acetate85 go

Dimyristyl methyl polyoxyethylene ammonium methyl sulfate containing 40 moles ethylene oxide15

Example III

Dipalmityl dibenzyl ammonium chloride 33

Distearyl benzyl polyoxyethylene ammonium chloride containing 60 moles ethylene oxide67

Example IV

GO

Distearyl dipropyl ammonium phosphate90

N-capryl, NN'-dimethyl polyoxyethylene propylene diammonium chloride containing 45 moles ethylene oxide_____________ 10

Example V

Stearyl trimethyl ammonium chloride35

Dicapryl methyl polyoxyethylene ammonium chloride containing 15 moles ethylene oxide65

Example VI

Distearyl dimethyl ammonium methyl sulfate50

Dilauryl benzyl polyoxyethlene ammonium chloride containing 30 moles ethylene oxide50 75

Example VII

Lauryl trimethyl ammonium methyl sulfate70

N-lauryl, NN'-diethyl polyoxyethylene ethylene diammonium ethyl sulfate containing 45 moles ethylene oxide30

Example VIII

Palmityl trimethyl ammonium acetate40

N-stearyl, NN'-dibenzyl polyoxyethylene propylene diammonium chloride containing 60 moles ethylene oxide60

Example IX

Stearyl dimethyl benzyl ammonium nitrite50

Dimyristyl methyl polyoxyethylene ammonium methyl sulfate containing 15 moles ethylene oxide50

Example X

Myristyl dimethyl benzyl ammonium chloride85

Disoya benzyl polyoxyethylene ammonium chloride containing 30 moles ethylene oxide 15

Example XI

Stearyl trimethyl ammonium chloride90

Dicoco ethyl polyoxyethylene ammonium chloride containing 35 moles ethylene oxide10

Example XII

Distearyl dimethyl ammonium methyl sulfate75

N-soya, NN'-dimethyl polyoxyethylene propylene diammonium methyl sulfate containing 25 moles ethylene oxide25

Example XIII

Palmityl trimethyl ammonium chloride60

N-tallow, NN'-dibenzyl polyoxyethylene propylene diammonium chloride containing 40 moles ethylene oxide40

Example XIV

Distearyl dimethyl ammonium methyl sulfate50

N-coco, NN'-dimethyl polyoxyethylene ethylene diammonium chloride containing 50 moles ethylene oxide __50

Example XV

Comparative tests were carried on to determine the effect of our surfactant composition as to softening and rewet results, using as comparisons the same quaternary compounds with and without non-ionic substitution materials. These tests comprise the present example and the following Examples XVI, XVII and XVIII.

Three parts of Arquad 2HT (dimethyl dihydrogenated tallow quaternary ammonium compound) were combined with one part of Ethoquad 2C/25 (quaternary ammonium salt derived from ethylene oxide addition product of dicocoamine containing 15 moles of ethylene oxide). The above compositions based on the weight of the material treated and were added to the final rinse in the treatment for textiles.

A similar test was made employing Arquad 2HT alone. It was found that the composition containing Arquad 2HT and Ethomeen not only provided increased softening but substantially retained the wettability property of the textiles.

Example XVI

The test was carried on as described in Example XV above except that the following compositions were compared:

#B. Arquad 2HT (3 parts)—Ethoquad 2C/25 (1 part).

#4. Arquad 2HT (5 parts)—Atlas G-1256 (1 part)— polyoxyethylene sorbital esters of fatty acid)—nonionic.

The test results showed #B to have increased softening and rewet effect.

3,178,366

Example XVII

Comparative tests were made as described in Example XV except that the following materials were compared: #1. Arquad 2HT (3 parts)—Ethoquad 2HT/25 (1 part). #2. Arquad 2HT (3 parts)—Ethoquad 2HT/25 (% part)—nonyl phenol plus 9 moles ethylene oxide (½ part) (non-ionic).

Ethoquad 2HT/25 has the following formula:

ch₃

Z—£(Ο₂Η₄Ο)ι₅Η^⁺ 01Ka in which R₂ is hydrogenated tallow.

In the above test, #1 was found to provide greater softening than composition #2, the addition of the nonionic in #2 reducing softening. The rewet qualities were about equal.

Example XVIII

Tests were carried on as described in Example XV except that the following compositions were tested:

#1. Arquad 2HT (3 parts)—Ethoquad 2C/50 (1 part). #2. Arquad 2HT (3 parts)—Ethomid HT/15 (1 part).

Ethomid HT/15 has the following formula:

O (CH₂CH_a0)xH (CH₂CH₂O)yH in which R is hydrogenated tallow and x plus y equals 5.

Ethomid is completely non-ionic. Its substitution reduced softening. #2 composition had poor softening and no rewet, while #1 composition had excellent softening and good rewet.

The surface active compositions of the instant invention are particularly useful in the manufacture of textiles and tissue paper for improving surface softness. Each of the above compositions was tested at concentrations of from 0.1% to 0.3% based on the weight of the material treated. For textiles, the surface active composition was added to the final rinse. In the manufacture of tissue paper, the compositions were dissolved in hot water and then added to the pulp in the beater with other paper ingredients. The mixture was digested for about one-half hour prior to felting. In all cases, the presence of trace precipitants, hereinbefore set forth, in the aqueous media did not affect adversely the quaternary ammonium salt. Surface smoothness was obtained with all compositions. When the same quaternary salts were used alone, the material was insufficiently treated and the desired degree of surface softness was not obtained.

Additional tests were made to determine the efficacy of the surface active compositions of the instant invention for effecting softening of hair and clothes after washing with conventional soaps and/or detergents with or without water softening agents being present during the washing and intermediate rinsing steps. The fabric or hair softener is usually added to the final rinse. However, the intermediate rinses usually do not remove all of the washing of cleaning agents or water softeners prior to the final rinse. Consequently, traces of anionic materials are usually present during the final rinse. Heretofore, the use of quaternary ammonium salts under these conditions has not been satisfactory. The cationic quaternary ammonium salts reacted with anionic materials to form insoluble products. The tests of each of the above compositions in laundry equipment showed that the presence of trace amounts of the cleaning agents with or without water softening materials, such as the polyphosphates, was not detrimental to the effectiveness of the quaternary ammonium salt. Here again, the desired degree of softness was only obtainable when the ethoxylated quaternary ammonium salt was present.

Aqueous dispersions were prepared from the compositions hereinbefore set forth so that the active components were present at a 0.15% concentration. These dispersions were used as hair rinses and found to be satisfactory 5. without precipitation of the quaternary salt which did occur when the ammonium salt was used as the sole softening agent.

While in the foregoing specification various embodiments of this invention have been set forth and many dejO tails thereof elaborated for the purpose of illustration, it will be apparent to those skilled in the art that this invention is susceptible to other embodiments and that many of these details can be varied widely without departing from the basic concept and spirit of this invention.