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Publication numberUS3154489 A
Publication typeGrant
Publication dateOct 27, 1964
Filing dateMay 28, 1962
Priority dateJul 18, 1960
Publication numberUS 3154489 A, US 3154489A, US-A-3154489, US3154489 A, US3154489A
InventorsBrandiff John S, Du Brow Paul L
Original AssigneeArmour & Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Surface active compositions
US 3154489 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 3,154,489 SURFACE ACTIVE C(BMPUSTTIONS Paul L. Du Brow, Chicago, lit, and John S. Brandiff, Baitimore, Md, assignors to Armour and (Iompany, (Ihicago, lllh, a corporation of Delaware No Drawing. Filed May 28, 1962, Ser. No. 197,896 6 Claims. (Cl. 252-8375) This invention relates generally to surface active agents, and more particularly to quaternary ammonium salts.

The present application is a continuation-in-part of our copending application Serial No. 787,335, filed January 19, 1959, now abandoned.

The quaternary ammonium salts, being cationic or cation-active agents, are not compatible with anion-active materials. Generally, the quaternary ammonium salts are precipitated or rendered inactive by organic anion-active materials, such as soaps, alkyl aryl sulfonates, other anionic synthetic detergents, and carboxymethyl 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 as the effective utilization of the quaternary ammonium salts for their functional benefits is restricted thereby. For example, the quaernary ammonium salts are very effective as softening agents for hair and cellulosic materials, such as textiles and tissue paper. 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. Consequently, 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 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 ammonium salt, etc.

We have found that a surface-active composition comprising a quaternary ammonium salt and a polyoxyethylene fatty amine condensation product is highly compatible with anion-active materials, while at the same time the condensation product add a quota of softening activity to that of the quaternary ammonium salt. Also, it has the additional eifect of conditioning the textile, etc. material for rewetting. Instead of being an inert or waste material as far as actively inducing softening is concerned, the ethoxylated fatty amine condensation product contributes actively to the softening function of the complete composition.

Therefore, a principal object of the present invention is to provide surface-active compositions, containing quaternary ammonium salts, which are compatible with anionactive 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 amine component. 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 amine, a polyoxyethylene-fatty amine condensation However, when the quaternaries are ice product containing 15 to moles ethylene oxide. Coloring and perfume may, if desired, be added to the aqueous dispersions. The compositions may be in the form of free flowing powders or aqueous dispersions.

The quaternary ammonium salt component of the surface active compositions of the invention has the formula wherein R represents benzyl or an alkyl group containing 1 to 3 carbon atoms, R represents benzyl, or an alkyl group containing 1 to 3 carbon atoms, or an alkyl group containing 12 to 18 carbon atoms, R represents an alkyl group containing 12 to 18 carbon atoms, and X represents an anion, such as halogen, acetate, phosphate, nitrite, and methyl sulfate radicals. The carbon chain of the alkyl group having 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 a dialkyl dimethyl ammonium chloride or an alkyl trimethyl ammonium chloride wherein the alkyl group is derived from hydrogenated tallow.

The polyoxyethylene-fatty amine condensation products that have peculiar efficacy as the other active component of the compositions of the instant invention may be either monoor di-tertiary fatty amines containing 15 to 60 moles of ethylene oxide.

The mono-tertiary fatty amines have the general formula N(oHion20) .11

(OH CH O) yH wherein R is an alkyl group having 8 to 18 carbon atoms in its carbon chain, in is an integer from 2 to 3, and the sum of x+y+z is an integer from 15 to 60.

In the preferred embodiments of the invention, the R group of the ethoxylated amine is 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 ethoxylated coco amine products 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 amomnium salt there should be 0.1 to 2.0 parts by weight of the fatty amine-polyoxyethylene condensation product. In other words, the weight ratio of quaternary ammonium salt to polyoxyethylenefatty amine condensation product is within the range of from 10:1 to 1:2. When the components are present in these ratios, the resulting 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 are so used, the presence of any of the aforementioned anionic precipitants does 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.

We have found that an excellent treating composition for softening fibers and conditioning them for rewetting is prepared by combining a quaternary ammonium salt containing substantially no moles of ethylene oxide but containing an alkyl group having 12 to 18 carbon atoms with a condensation product of a fatty amine containing an alkyl group having 8 to 18 carbon atoms with 15 to 60 moles of ethylene oxide, the weight ratio of the salt to the condensation product being from 10:1 to 1:2.

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

Example I Dimethyl distearyl ammonium chloride 83.3 Dilauryl polyoxyethylene tertiary amine containing moles of ethylene oxide 16.7

Example 11 Diethyl dilauryl ammonium acetate 50.0 Dimyristyl polyoxyethylene tertiary amine containing 40 moles of ethylene oxide 50.0

Example III Dibenzyl dipalmityl ammonium chloride 33.3 Distearyl polyoxyethylene tertiary amine containing 60 moles ethylene oxide 66.7

Example IV Dipropyl distearyl ammonium phosphate 90.9 N-capryl-N,N'-polyoxyethylene ethylene diamine containing 45 moles ethylene oxide 9.1

Example V Trimethyl stearyl ammonium chloride 35.0 Dicapryl polyoxyethylene tertiary amine containing 15 moles ethylene oxide 65.0

Example VI Dimethyl distearyl ammonium methyl sulfate 50.0

Dilauryl polyoxyethylene tertiary amine containing 30 moles ethylene oxide 50.00

Example VII Trimethyl lauryl ammonium methyl sulfate 70.0 N-lauryl-N,N'-polyoxyethylene propylene diamine containing 45 moles ethylene oxide 30.0

Example VIII T rimethyl palmityl ammonium acetate 40.0 N-stearyl-N,N'-polyoxyethylene propylene diamine containing 60 moles ethylene oxide 60.0

Example IX Dimethyl henzyl stearyl ammonium nitrite 50.0 Dimyristyl polyoxyethylene tertiary amine containing 15 moles ethylene oxide 50.0

Example X Dimethyl benzyl myristyl ammonium chloride 83.3 Disoya polyoxyethylene tertiary amine containing 30 moles ethylene oxide 16.7

Example )6] Trimethyl stearyl ammonium chloride 90.9 Dicoco polyoxyethylene tertiary amine containing 35 moles ethylene oxide 9.1

Example XII Dimethyl distearyl ammonium methyl sulfate 75.0 N-soya-N,N'-p0lyoxyethylene propylene diamine containing 25 moles ethylene oxide 25.0

Example XIII Trimethyl palmityl ammonium chloride N-tallow-N,N'-polyoxyethylene propylene diamine containing 40 moles ethylene oxide 40.00

Example XIV Example XV Comparative tests were carried out to determine the effect of our surfactant composition as to softening and rewet results, using as comparisons the same quaternary compounds with non-ionic substitution materials. These tests comprise the present example and the following Examples XVI and XVII.

Three parts of Arquad ZI-IT (dimethyl dihydrogenated talloW quaternary ammonium compound) were combined with one part of Ethomeen 2C/ 25 (dicoco amine containing 15 moles of ethylene oxide). The above compositions were 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 ZHT (3 parts)Ethomeen 2C/25 (1 part) #4 Arquad rZHT (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 efiect.

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

#1 Arquad 2HT (3 parts)-Ethomeen 2C/50 (1 part) #2 Arquad ZHT (3 parts)Ethomid HT/ 15 (1 part) Ethomid HT/ 15 has the following formula:

0 (CH2CHgO)xH R N (CHzCHzO) E in which R is hydrogenated tallow and x plus y equals 5.

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

Example XVIII Insofar as compatibility is concerned, whiteness retention was measured when a detergent (Tide) was added to a final rinse containing Arquad ZHT. The numbers set out below refer to a drop in reflectance from a blank for the cloth. The additives and results are listed as follows.

Non-ionic Ethomeen 2C/ 3 8 4.0 Polyglycol 1,000 7.0 Polyglycol 20,000 10.0 Polyvinyl alcohol 6.8

Example XIX The stability of 3.5% Arquad ZHT formulation in waters of high electrolyte content (Los Angeles water) was determined. Separation occurred with the use of Arquad 2I-IT alone. However, there was good stability when Arquad ZHT (3 parts) was combined with Ethomeen 2C/25 (1 part).

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 onehalf 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 softness 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 or 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 the 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 polyoxyethylene-fatty amine 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 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 details 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.

We claim:

1. A treating composition for softening fibers and conditioning them for rewetting, comprising a quaternary ammonium salt having the formula where R is selected from the group consisting of an alkyl group containing 1 to 3 carbon atoms and benzyl, R is selected from the group consisting of an alkyl group containing 1 to 3 carbon atoms, an alkyl group containing 12 to 18 carbon atoms and benzyl, R is an alkyl group containing 12 to 18 carbon atoms, and X is an anion; and an ethoxylated amine selected from the group consisting of a tertiary amine having the formula where R is an alkyl group containing 8 to 18 carbon atoms, and n is an integer from 15 to 60, and a diarnine having the formula where R is an alkyl group containing 8 to 18 carbon atoms, in is an integer from 2 to 3, and the sum of x+y+z is an integer from 15 to 60, the weight ratio of the quaternary ammonium salt to ethoxylated amine being from 10:1 to 1:2.

2. A treating composition for softening fibers and conditioning them for rewetting, said composition consisting essentially of dimethyl distearyl ammonium chloride and dilauryl polyoxyethylene tertiary amine containing 15 to 60 moles ethylene oxide, the weight ratio of said chloride to said amine being from 10:1 to 1:2.

3. A treating composition for softening fibers and conditioning them for rewetting, said composition consisting essentially of dimethyl distearyl ammonium methyl sulfate and dilauryl polyoxyethylene tertiary amine containing 15 to 60 moles ethylene oxide, the weight ratio of said sulfate to said amine being from 10:1 to 1:2.

4. A treating composition for softening fibers and conditioning them for rewetting, said composition consisting essentiflly of trimethyl stearyl ammonium chloride and dicoco polyoxyethylene tertiary amine containing 15 to 60 moles ethylene oxide, the weight ratio of said chloride to said amine being from 10:1 to 1:2.

5. A treating composition for softening fibers and conditioning them for rewetting, said composition consisting essentially of dimethyl distearyl ammonium methyl sulfate and N-soya-N,N'-polyoxyethylene ethylene diarnine containing 15 to 60 moles ethylene oxide, the weight ratio of said sulfate to said diamine being from 10:1 to 1:2.

6. A treating composition for softening fibers and conditioning them for rewetting, said composition consisting essentially of trirnethyl palmityl ammonium chloride and N-ta1loW-N,N-po1yoxyethylene propylene diamine con taining 15 to 60 moles ethylene oxide, the weight ratio of said chloride to said diamine being from 10:1 to 1:2.

References tl'ited in the file of this patent UNITED STATES PATENTS 2,577,773 Lambert Dec. 11, 1951 2,809,159 Welles et al. Oct. 8, 1957 2,857,330 Hall Oct. 21, 1958 2,950,253 Kling et al. Aug. 23, 1960

Patent Citations
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US2809159 *Nov 18, 1954Oct 8, 1957Dexter Chemical CorpAntistatic and rewetting treatment of textile material
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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3274106 *Jan 20, 1964Sep 20, 1966Archer Daniels Midland CoFreeze-thaw stabilizers for quaternary ammonium compounds
US3325404 *Sep 19, 1963Jun 13, 1967Millmaster Onyx CorpComposition for simultaneously laundering and softening fabrics
US3349033 *Aug 26, 1964Oct 24, 1967Millmaster Onyx CorpStable microbiologically active laundry softener
US3497365 *Jul 25, 1968Feb 24, 1970Armour Ind Chem CoProtective polish
US3519561 *Jun 23, 1966Jul 7, 1970Gaf CorpAlkoxylated tertiary amine antistatic composition
US3664952 *May 15, 1970May 23, 1972American Cyanamid CoAqueous textile softening composition
US3850818 *Sep 19, 1972Nov 26, 1974Kao CorpAntistatic softening composition containing a quaternary ammonium salt and a ethenoxy quaternary ammonium salt
US3979307 *Sep 10, 1973Sep 7, 1976Texaco Inc.Fabric softener composition
US4012326 *Jun 29, 1971Mar 15, 1977Lever Brothers CompanyAdditives for clothes dryers
US4064067 *Apr 26, 1976Dec 20, 1977E. I. Du Pont De Nemours And CompanyFluorosurfactant leveling agent
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US4548744 *Jul 22, 1983Oct 22, 1985Connor Daniel SEthoxylated amine oxides having clay soil removal/anti-redeposition properties useful in detergent compositions
US4551506 *Dec 23, 1982Nov 5, 1985The Procter & Gamble CompanyCationic polymers having clay soil removal/anti-redeposition properties useful in detergent compositions
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US4627927 *May 28, 1985Dec 9, 1986Lion CorporationAdditive composition for granular detergent
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US4659802 *Nov 22, 1983Apr 21, 1987The Procter & Gamble CompanyCationic compounds having clay soil removal/anti-redeposition properties useful in detergent compositions
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US4664848 *Nov 22, 1983May 12, 1987The Procter & Gamble CompanyDetergent compositions containing cationic compounds having clay soil removal/anti-redeposition properties
US4676921 *Dec 23, 1982Jun 30, 1987The Procter & Gamble CompanyDetergent compositions containing ethoxylated amine polymers having clay soil removal/anti-redeposition properties
US4741842 *Jan 27, 1986May 3, 1988Colgate-Palmolive CompanyParticulate detergent softener compositions comprising a mixture of cationic softener and ethoxylated amine
US7205269 *Jun 29, 2005Apr 17, 2007The Procter & Gamble CompanyLaundry detergent compositions with hueing dye
US8393473Nov 26, 2008Mar 12, 2013Akzo Nobel N.V.Mixture of collectors for flotation of clay minerals from potash ores
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EP0076572A1 *Sep 8, 1982Apr 13, 1983THE PROCTER & GAMBLE COMPANYFabric softening detergent additive products and use thereof in detergent compositions
EP0082456A2 *Dec 13, 1982Jun 29, 1983Hoechst AktiengesellschaftConcentrated premixes of fabric-softening agents
EP0181508A2 *Oct 12, 1985May 21, 1986Süd-Chemie AgWashing additive
WO2010060477A1 *Nov 26, 2008Jun 3, 2010Akzo Nobel N.V.Mixture of collectors for flotation of clay minerals from potash ores
Classifications
U.S. Classification424/70.19, 510/524, 510/123, 510/499, 510/521
International ClassificationD06M13/463, D06M13/00, C11D3/00, C11D1/44, C11D1/62, C11D1/38, D06M13/432
Cooperative ClassificationD06M2200/50, C11D1/44, C11D1/62, D06M13/432, D06M13/463, C11D3/001
European ClassificationC11D1/44, C11D3/00B3, D06M13/432, D06M13/463, C11D1/62