US3897348A - Surface treating compositions containing surface active ammonioamidate compounds - Google Patents

Surface treating compositions containing surface active ammonioamidate compounds Download PDF

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US3897348A
US3897348A US37414873A US3897348A US 3897348 A US3897348 A US 3897348A US 37414873 A US37414873 A US 37414873A US 3897348 A US3897348 A US 3897348A
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Ronald Edward Atkinson
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Procter and Gamble Co
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS, OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402Amides imides, sulfamic acids
    • D06M13/422Hydrazides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K8/00Cosmetics or similar toilet preparations
    • A61K8/18Cosmetics or similar toilet preparations characterised by the composition
    • A61K8/30Cosmetics or similar toilet preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toilet preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41Amines
    • A61K8/416Quaternary ammonium compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILET PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/02Preparations for cleaning the hair
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88Ampholytes; Electroneutral compounds
    • C11D1/883Aminimide (= ammonioamidates)
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS, OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen

Abstract

Surface-treating compositions containing ammonioamidate surfaceactive compounds able to exist in either cationic or zwitterionic form are disclosed. The compositions which contain a buffering agent to control pH and the cationic or zwitterionic character of the ammonioamidates are effective in the treatment of fabric or hard surfaces. Hair treating compositions and processes are disclosed. Methods of treating fabric and hard surfaces to provide fabric softening and soil-release properties are also disclosed.

Description

United States Patent [191 Atkinson July 29, 1975 SURFACE TREATING COMPOSITIONS CONTAINING SURFACE ACTIVE AMMONIOAMIDATE COMPOUNDS [75] Inventor: Ronald Edward Atkinson, Northumberland, England [73] Assignee: The Procter & Gamble Company, Cincinnati, Ohio [22] Filed: June 27, 1973 [21] Appl. No.: 374,148

Related U.S. Application Data [63] Continuation-in-part of Ser. No. 243,089, April 11,

1972, abandoned.

[52] U.S. Cl. 252/8.75; 252/8.8; 252/525; 252/529; 252/544; 252/548; 252/DIG. 7;

252/D1G. 13; 260/404.5; 260/561 H;

[51] Int. CI. D06M 13/40; CllD 1/88 [58] Field of Search 252/8.75, 8.8, 544, 547, 252/525, DIG. 7, 529, 548;

260/561 H, 562 H, 404.5; 117/1395 CQ [56] References Cited UNITED STATES PATENTS 3,410,880 11/1968 Brocklehurst 260/561 X 3,485,806 12/1969 Bloomquist et al 260/561 X 3,546,115 12/1970 Gill ct al. 3,649,569 3/1972 McCarty 2512/88 FOREIGN PATENTS OR APPLICATIONS 1,003,926 6/1963 United Kingdom OTHER PUBLICATIONS Anderson, Ampholytic Detergents, Article in American Perfumer and Aromatics. Documentary Edition, 260, 1 19- 162 and 163.

Primary ExaminerHerbert B. Guynn Attorney, Agent, or Firm-Richard C. Witte; Julius P. Filcik; Forrest L. Collins [57] ABSTRACT 11 Claims, No Drawings SURFACE TREATING COMPOSITIONS CONTAINING SURFACE ACTIVE AMMONIOAMIDATE COMPOUNDS CROSS-REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of the application of Ronald Edward Atkinson having Ser. No. 243,089, filed Apr. 11, 1972 now abandoned.

BACKGROUND OF THE INVENTION This invention relates to surface-treating compositions comprising certain nitrogen ylides, ammonioamidates,, which are surface-active agents and are able to exist in zwitterionic (ylide) form or in cationic form.

Quaternary ammonium compounds having at least one long chain (about C upwards) hydrophobic radical in the molecule have long been known. They are useful as cationic surface-active agents (so called invert soaps), as textile softening agents and as bactericides. When intended for use as surface-active agents, the long chain group usually has from about 12 to about carbon atoms. When intended for use as textile softeners, long-chained compounds, for instance having about 16 to 22 or more carbon atoms, are preferred, especially compounds possessing two long chain groups. Typical examples include: octadecyldimethyl benzyl ammonium chloride, octadecyltrimethyl ammonium chloride, distearyl dimethyl ammonium chloride, the corresponding bromides, and many others of similar structure.

These compounds, particularly distearyl dimethyl ammonium chloride, have been used commercially in textile softening compositions intended to be added to the last rinse water after a conventional washing process, and attempts have been made to use them in detergent compositions intended to be combined washing and textile softening agents.

Being cationic, these substances ordinarily react with anionic detergents to form insoluble substances, and so their use in the presence of anionic detergents is not normally practicable. Furthermore, they have a strong affinity for fabrics, especially cotton and wools, a fact which plays an important part in their effectiveness as textile softeners and bactericides, but also has the effect that they are generally not completely washed out of the fabric in a succeeding wash. They therefore tend to build up on repeatedly washed fabrics, and may thus impair the rewetting properties of the fabrics, tend to cause discoloration, fiber snagging and even cause undesirable odors.

Other quaternary ammonium compounds constitute the known zwitterionic surface-active compounds, for example, the long-chain carboxylic betaines, sulphobetaines, sulphatoand sulphito betaines. These compounds are valuable wetting agents and detergents. They are internal salts and, therefore, do not react with the metal ions present in hard water, especially calcium ions, and thus are almost unaffected by water hardness. For the same reason, they are compatible with anionic, cationic and nonionic detergents. Their affinity for and wetting effect upon certain highly hydrophobic fibers, such as polyamine and polyester fibers, renders them particularly valuable for removing certain types of soils, especially greasy soils, from these materials. They are also remarkably effective in cleaning cotton fabrics soiled with dirt which contains clay particles. However,

LII

they are not strongly substantive to fabrics-and are not very effective textile softening agents. These known betaine and betaine -like compounds exist in zwitterionic. formover a 'wide range ofpHfln relatively strongly acid conditions they do become cationic, but the necessary acidity is outside the practical rangefor washing fabrics or human'beings.

The present invention is concerned with a class of surface-active agents which are cationic under neutral or weakly acid conditions, and are zwitterionic under weakly alkaline conditions. Thus, if present atthe ordinary pH of a rinsing operation in an aqueous solution (which need not, of course, necessarily in fact constitute the rinse after a wash) they are largely in cationic form and are effective as textile softening agents substantive-to fabrics. Under the ordinarily alkaline conditions of a subsequent conventional washing operation, they convert to a zwitterionic form, and thus are removed from the fabrics. When so removed, they are compatible with the detergent composition and may even enhance its effectiveness.

SUMMARY OF THE INVENTION R, CO N N R R R or a cationic adduct thereof having the formula:

R 00 NH N R R R., x

where X is an anion; R is an aliphatic (e.g., alkyl), aromatic (e.g., phenyl) or alkaryl (e.g., alkylphenyl) group having from 1 to 25 carbon atoms; each of R and R is a methyl, ethyl, hydroxyethyl or cyanoethyl group; and R is either;

CH --CH CHR wherein R is hydrogen or alkyl of from 1 to 18 carbon atoms and R is'hydrogen or an aliphatic group (e.g.,-

alkyl) having 1 to 4 carbon atoms; at least one of R and R having an alkyl chain of at least 6 carbon atoms; and a pH buffering compound.

, The surface-treating compositions are suitable for treating textile surfaces such as those of fibers and fabrics, and also hard surfaces, such as those of ceramics, metals and the like.

In its process or method aspect, the present invention provides a method of treating fabric materials whereby the fabrics are improved in softness without undesirable build-up with succeeding washing treatments which comprise the steps of treating the fabrics with a solution of a predominantly cationic and fabricsubstantive compound described hereinbefore thereby to improve softness and, thereafter, washing the fabrics under alkaline conditions to remove the softener in a predominantly zwitterionic form. Also provided is a method of treating hard surfaces whereby the predominantly cationic and substantive form is applied to hard surfaces, said surfaces are subjected to soiling effects and the cationic form is substantially removed by altering the pH of the treated surface to effect conversion to a predominantly zwitterionic form.

In another process aspect, the ammonioamidate is applied to hair, either in a shampoo or in a rinse or lotion, after washing with a conventional shampoo, leav ing the hair glossy, easy to comb when wet or dry and acceptably free from static electricity charges which cause so-called hair fly".

DETAILED DESCRIPTION OF THE INVENTION The ammonioamidate compounds of the compositions of the invention can be conveniently prepared. For example, they can be prepared by alkylation of an acyl hydrazide of formula:

R, CO N H N R R,

by heating it together with either a benzyl halide of the formula cn R or an allyl halide of the formula Y CH CH =CH R wherein Y is a chlorine, bromine or iodine atom and the remaining symbols are as defined above. The hydrazide can be prepared, for instance, by reacting an unsymmetrical 'dialkyl hydrazine with an acyl chloride R COCl. The amidates of the invention can suitably be prepared in zwitterionic form by treating the products obtained by the above defined process with an alkali.

Acyl hydrazides can be alkylated by means of alkyl halides as is disclosed in British Pat. No. 1,003,926 but an alkyl iodide must be used to achieve practical yields of the quaternary compound, and the iodides are costly. It is an important advantage of the present inanion of a buffering agent with which the amidate is associated in a composition, as described hereinafter.

The group R, can be an alkyl group of from 1 to 25 carbon atoms. Preferably, the alkyl is either a shortchain alkyl of from 1 to 4 carbon atoms or is a hydrophobic group such as an alkyl of from 9 to 21 carbon atoms. Additionally, R, can be an alkaryl group such as an alkylbenzene group where the alkyl has from 8 to 15 carbon atoms. The alkyl benzene group can be derived from detergent alkyl benzenes known in the art. Said alkyl groups can be straight-or branch-chained. Preferably, each of the groups R and R is a methyl or an ethyl group.

The group R is preferably hydrogen, a shortchained alkyl of from 1 to 4 carbon atoms or is a hydrophobic alkyl group having 8 to 15 carbon atoms. In the latter case, again the alkyl benzyl radical constituting R, can be derived from a typical detergent alkyl benzene.

The group R is either hydrogen or a lower alkyl group having 1 to 4 carbon atoms, preferably a methyl group. In order that the compounds should be surfaceactive, at least one of the groups R, and R must have at least 6 carbon atoms in the alkyl chain, preferably at least 8, and, particularly when intended for use as textile softeners or hair conditioners, preferably at least 15 carbon atoms.

Compounds of the above formulae deserving special mention are those wherein R, is an alkyl group having 10 to 20 carbon atoms and R if present, is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R; if present is a hydrogen atom; also, those wherein R, is an alkyl group having 1 to 4 carbon atoms or an alkyl group having 9 to 21 carbon atoms or an alkyl benzene group having 8 to 15 carbon atoms in the alkyl group and R if present is an alkyl group having 8 to l5 carbon atoms, and R if present, is an alkyl group having 1 to 4 carbon atoms.

As suitable compounds, there may be mentioned particularly the compounds having the following formulae, in zwitterionic (ylide) form:

Preferred compounds according to the invention have a pKa value in the range from 5 to 7. The pKa value is the pH at which the compounds are present 50 molar percent in zwitterionic (ylide) form and 50 percent in cationic form. At a pH below the pKa value the compounds are predominantly in cationic form, and at a pH above the pKa value they are predominantly in zwitterionic form. At pH values near the pKa value both forms are present to a considerable extent.

The compositions of the invention can comprise an amidate, as described herein, in its cationic or zwitterionic form together with suitable buffering agents, and may be intended for use in an aqueous liquor of pH less than, equal to, or not more than 2 units higher than the pKa value of the amidate. The pH buffering agent in these compositions is selected to ensure that an aqueous solution of the composition, having a concentration such that 0. 1% by weight of said amidate is present, will have a pH in said range. Preferably the pH of the solution is within 2 units, or more preferably within 1 unit, above or below the pKa value. In solution, the amidate will then be present to a considerable extent in the form of its cationic acid adduct and will be substantive to, and adsorbed upon most surfaces to be treated. In such solutions, the anion of the cationic form of the amidate is often that of the buffering agent. Any effective buffering agent can be used, which is effective at the de sired pH, for instance phosphates, polyphosphates, borates, salts of weak organic acids, such as citric, lactic, glycoli, malic, tartaric, acetic, capric, benzoic or adipic, the corresponding glycolic, and mixtures of any of these. Preferred buffering agents are the alkali metal (eg sodium and potassium) phosphates, polyphosphates, borates and citrates.

The compositions of the invention can be used to treat surfaces, especially textiles, on any occasion and, in particular they are suitable as rinse additives. Thus they can be added to the rinse liquor after a surface, such as that of a textile fabric, has been washed, to provide the beneficial effects described above. Rinse additive compositions, comprising an ammoniomamidate of the invention and a buffering agent effective to provide an aqueous solution of the composition with a pH which ensures the existence of the ammonioamidate in a predominantly cationic and fabric-substantive form, constitute preferred embodiments of the invention.

Suitable rinse additive compositions of the invention are exemplified as follows:

(e.g., Butyl Carbitol) Water Balance to 100 Balance to I Alternatively, the amidates can form at least part of the active organic detergent of a washing composition or liquor adapted to the washing of textile or other surfaces. A detergent composition, e.g. a conventional heavy-duty laundry detergent, containing an ammonioamidate of the invention will be formulated so that its pH in aqueous solution as used is above the pKa value of the amidate, preferably at least 2 units above it, so that the amidate will be predominantly in Zwitterionic form. Thus, the buffering agent should be such that the pH of a solution of the composition, having a concentration such that there is present 0.1 percent by weight of the said amidate, is at least 1 unit, and preferably at least 2 units, above its pKa value. The amidate will then play its part in the washing action of the detergent composition, and the proportion of it present in the rinse, when dilution with tap water or the like may have reduced the pH to near its pKa value will then be converted to some degree of cationic form and be substantive to the surface being treated. However, the pKa value of these amidates being usually in the range from 5 to 7, often the pH of even a second of third rinse water remains well above the pKa value, owing to the carrying over of alkaline builders from the wash liquor. Accordingly, this method of employing the amidates as detergent-compatible textile softeners and soil release agents would be expected to be less effective than the method of adding them in a rinse or like treatment.

However, it has been found to be more effective than would be expected, and, furthermore, it is often a more convenient method, especially for domestic users.

Generally it is preferred that the amidate, in cationic form, should be present in a treatment solution at a level such as to provide about 0.01 to 5 percent, for example about 0.1 percent, of said cationic form of the amidate, based on the dry weight of a fabric being treated. The concentration ofamidate in a treatment solution will depend, for example, on the cloth load, but can suitably be in the range from about 0.001 to 0.5 percent, preferably from about 0.02 to 0.2 percent, by weight of the solution. Correspondingly, the proportion employed in a surface treating composition will depend on the concentration at which it is intended to be used, so as to provide the above concentrations in the working solution. As a guide, an effective composition will contain about 5 percent by weight of the amidate.

The compositions of the invention can contain compatible components commonly included in compositions of the particular type. Thus the rinse additive type of compositions can contain inorganic or organic salts (other than those employed as pH buffers), chelating agents, emulsifiers, solvents, coupling agents and the like, provided that they do not displace the pH from the required range. As examples there may be mentioned: sodium sulphate, sodium chloride, and organic acid salts. The detergent compositions can contain watersoluble detergency builder salts such as the inorganic phosphates, polyphosphates, silicates, carbonates or borates, and the organic alkaline sequestrants such as nitrilotriacetates, or polycarboxylates, such as those described in US. Pat. No. 3,308,067 (Mar. 7, 1967) including gluconates, polyitaconates, and the like. Usually the salts are the sodium salts, but other cations may be used provided that the salts are sufficiently water soluble. Some of the salts can well function both as pH buffers and builders.

In such alkaline detergent compositions, the amidate in Zwitterionic form is compatible with all classes of organic detergent including anionic, nonionic and zwitterionic detergents. Most heavy duty built alkaline detergent compositions are based on anionic detergents, either soap or non-soap, and the amidates are compatible with these detergents. In soap compositions, they may act as lime-soap dispersing agents, and for this purpose are generally present at a level of about 10 percent to 20 percent by weight of the soap, but some effect is obtained by as little as 1 percent, and higher levels of up to at least 30 percent can be used. Suitable anionic non-soap detergents include any of those normally used in detergent compositions, such as alkyl benzene sulfonates, alkyl sulfates, alkyl ether sulfates and the like. Anionic surface active agents are preferably avoided in compositions containing the cationic form of the amidates, since they tend to react together to form insoluble substances. However, these insoluble substances if formed on or entrapped in a fabric do have softening properties, and they are soluble in the alkaline condition of a subsequent wash.

Suitable nonionic and Zwitterionic detergents include those known in the art. As examples of the nonionics there may be mentioned: polyethylene oxide condensates of long chain fatty acids, fatty alcohols, amines, alkyl phenols and the like, polyethylenimine condensates of fatty acids, amines or amides; polyethoxypolypropoxy condensates such as the Pluronics (Trade name); and polyethoxy sorbitan esters such as the Tweens (Trade name). The zwitterionics include long chain alkyl or alkyl benzyl betaines; sulphobetaines, certain amino acids and the like. Other examples of suitable detergents are provided in U.S. Pat. No. 3,213,030, issued Oct. 19, 1965, lines 5375 of column 3 lines 1 to 75 of column 4 and lines 1 to 30 of column 5, which disclosure is incorporated herein by reference. Normally, the built detergent compositions of the invention will comprise the ammonioamidate of the invention in an amount of 1 percent to 20 percent, preferably percent to percent, and an admixture of detergent active and builder salt as described above in a ratio of detergent to builder of from about 2:1 to about 1:10 by weight.

The compositions also contain compatible minor ingredients of any of the types commonly used in detergent and softening compositions. These include, for example: perfumes, colors, bactericides, bleaching agents, enzymes, activators or stabilizers for them, foam-enhancing or -suppressing agents, tarnish and corrosion inhibitors, soil-suspending agents and the like.

The compositions of the invention are especially suited to the improvement of the feel or hand of treated textiles and in the treatment of other surfaces. Both on textile and like fibers and on other surfaces, for example hard surfaces, the adsorbed cationic and/or zwitterionic layer provides a surface which tends to repel important classes of soil (or dirt) and to promote their separation from the surface and their dispersion in a subsequent alkaline wash, when the adsorbed layer is rendered non-substantive. These substances can, thus, act as soil-release agents, which are removed to a considerable degree at each wash, and can be reapplied in a rinse or like treatment before the surface is reexposed to soiling. They also provide anti-static properties for the surfaces treated with them when in their cationic form.

The compositions of the invention have a further benefit, in that they reduce the extent of wrinkling or creasing of fabrics, for instance polyester-cotton fabrics, in the wash, and/or make such wrinkles or creases as are formed more easily removed by ironing. Furthermore, they have a lubricating effect so that there is less frictional resistance to the movement of an iron. Thus the effort of ironing garments treated with these compositions is appreciably lessened.

The compositions are also suitable for treating hard surfaces so as to facilitate cleaning them. By hard surfaces are meant principally those exposed to air-borne soiling, such as windows, whether of buildings or of vehicles, motor bodies and metal trim, paintwork, stone or brick work, domestic furniture especially sanitary ware and cookers and the like. The invention is also applicable to crockery, plate and cutlery and the like.

These surfaces often become soiled by air-borne dust, by spray and splashing, for instance on roads or by deposits from smoke and fumes or the like. These soil deposits usually contain grease, as for example, soot, deposits from motor exhaust or cooking fumes. They also often contain clay or like particles for example from wind-borne dust and road spray. Generally, they adhere quite strongly to most surfaces so that the surfaces must be rubbed, preferably in the presence of detergents or wetting agents, in order to clean them. Treatment with the compositions of the invention renders such surfaces easie to clean, so that if they are sprayed or flushed with water. the adherent soil deposits are mostly carried away without rubbing. Alternatively, surfaces which cannot conveniently be sprayed or flushed with water can be cleaned with a cloth wet with water, with a minimum of rubbing.

The compositions also render the treated surfaces to some degree antistatic, reducing the tendency for dust to adhere to them. They also render windows and like surfaces less liable to condensation of moisture and misting.

The hair treating compositions of this invention include shampoos, and compositions intended to be applied after shampooing, e.g., lotions or rinses. Any effective proportion of the ammonioamidates of this invention can be used in the hair shampooing and conditioning compositions of the invention, together with such conventional components as are desirable to make the product easy to apply and attractive. Usually, shampoo compositions and rinses are liquids intended to be applied in concentrated form to the wetted hair. In such compositions, generally from about 0.01 percent to about 5 percent or more by weight of ammonioamidate is suitable. At a concentration of over about 5 percent, aqueous solutions of the ammonioamidate in nearly neutral solutions which are appropriate for shampoos and the like, may become gelatinous and special precautions or other additives may be necessary to overcome this. As will be understood, quite different proportions would be suitable in compositions intended to be diluted before use.

In addition to the ammonioamidates, the shampoo compositions of this invention can contain organic water-soluble, non-soap, non-cationic surfactants. Cationic surfactants are generally avoided in shampoo compositions because they have little cleaning power on hair and are liable to be harmful to the eyes. The preferred detergents used are anionic detergents of any of the classes which are suitable per se for shampoos such as alkyl sulfate, alkyl ether sulfates, alkyl glyceryl ether sulfonates, sulfosuccinates, and others known in the art containing an alkyl or acyl group having from about 8 to about 18 carbon atoms. These detergents are normally used in the form of their alkali metal, e.g., sodium or potassium, ammonium and substituted ammonium, e.g., triethanolammonium, diethanolammonium and monoethanolammonium salts. The surfactants can be present in the usual concentrations, e.g., from about 5 percent to about percent by weight of the composition, generally from about 20 percent to about 40 percent by weight of the composition in liquid shampoos.

The anionic detergents can be replaced by nonionic, ampholytic, or zwitterionic detergents, or any of these may be present in addition to the anionic detergent. Examples of these detergents may be selected from types known in the art to be suitable for shampoo formulations. Suitable detergents are listed in Formulation and Function of Cosmetics, J. S. Jellinek, published by Wiley & Sons, 1970, pp. 230 240; and in U.S. Pat. Nos. 3,400,198; 3,580,853; 3,549,542; 3,549,546; 3,313,734; and 3,400,198, said patents being incorporated herein by reference.

The proportion of the ammonioamidates in liquid shampoo compositions can be within the range stated above but is preferably in the upper part of the range, e.g., from about 1 percent to about 3 percent by weight. It is believed that the ammonioamidates are strongly adsorbed on the keratin of the hair, but that some small degree of desorption may take place during the several rinses to which the hair is subjected after shampooing. The proportion of the ammonioamidate should be high enough to ensure that an effective amount remains on the hair after rinsing.

In addition to a main detergent active compound as referred to above and the ammonioamidate, the shampoo compositions can also contain other ingredients usual in shampoos such as one or more of the following substances: Suds boosters, such as fatty acid amides; emollients, such as lanolin and lecithin; bacteriostats; bactericides; preservatives; dandruff controlling agents such as zinc Z-pyridinethiol-l-oxide; opacifiers, e.g., polyethylene glycol distearate; viscosity controlling agents such as carboxymethylcellulose, alginates, etc.; resins, etc., to impart gloss to the hair; a liquid solvent or dispersing medium, e.g., water, lower alcohol, glycerol, etc.; hormone products; optical brighteners; perfume, colorant matter; etc. Preferred ingredients include bactericides, dandruff control agents, suds boosters and stabilizers, viscosity controllers, opacifiers, preservatives, color, and perfume.

The present invention also includes a method of treating hair which comprises applying thereto a composition as defined above.

The following Examples illustrate the invention:

EXAMPLE I Ten grams of palmitoyl-N,N-dimethyl hydrazide were heated with 4.2 g. of benzyl chloride for 2 hours at 100C on a steam bath. The mixture was cooled and the solid obtained was recrystallized from ethanolether mixture. Yield: 5.3 g., melting point lO7l08C. Analysis: C: 71%, H: 11.3%, N: 7.0. Theoretical analysis for C H ,CONHN(CH CH C H Cl is C: 70.7%, H: 10.6%, N: 6.6. The pKa value of this compound was 6.1.

EXAMPLE II Ten grams of palmitoyl-N,N-dimethylhydrazide were refluxed with 10 mls. of allyl chloride for 14 hours. The product was recrystallized from ethanol-ether. Yield: 8 g. Melting point 5658C. Elemental analysis was not carried out. The pKa value of this compound was 6.4

EXAMPLE III Soil release effect Test pieces of cotton muslin were washed in a commercial heavy-duty synthetic detergent composition, and half of them (A) were rinsed in water and the other half (B) were rinsed in a solution in water of 0.1 percent by weight of the ylide prepared as in Example I, and 0.036 percent by weight of citric acid. The pH of the latter rinse solution was about 5.5-6. The swatches were stained by immersion in hot, milkless tea, dried and aged at room temperature for 3 days. The swatches were then washed in a miniature washing machine, swatches A and B being washed together in the same vessel in each test. Washing conditions consisted of a three-minute wash in the same synthetic detergent composition as employed above, used at 0.3 percent and 0.5 percent concentration, each at 40C and 60C. The washed fabrics were rinsed in water and dried. In every case the test pieces B were clearly visibly whiter than the test pieces A.

Similar results were obtained when the test pieces were of cotton muslin soiled by clay, or polyestercotton soiled with air-filter dirt or with lanolin/carbon black.

EXAMPLE IV Textile softening effect Cotton terry towels were washed under the same conditions as those employed in Example III, and rinsed (A) in water and (B) in the same ylide-citric acid solution. They were then dried. Comparative towels were rinsed in a commercial cationic softener based on ditallowyldimethyl-ammonium chloride. After a single wash and rinse treatment, the softened cloths were similar in feel, and softer than those rinsed in water. After ten washes the cloths washed in the commercial softener had become softer than those washed in the ylide, but had become clearly visibly more yellow and had a greasy feel and had lost absorbency for moisture. The cloths treated with the ylide were softer than those rinsed in water, and remained white and retained their absorbency.

EXAMPLE V A multi wash and wear test was carried out using an upright-type washing machine (Hoovermatic De Luxe Twin tub). The steps of the test were as follows.

A typical mixed laundry load was washed in a conventional alkaline built detergent composition. The load was removed and rinsed, this load playing no further part in the test.

A second mixed laundry load was washed containing new test articles, in the same wash liquor.

Removed, spin dried 10 seconds.-

Rinsed in cold water 30 seconds.

Spin dried 10 seconds.

Divided and rinsed in treatment solutions 30 seconds.

Spin dried 10 seconds.

Dried in open air. I t v The test articles were then worn or used (as appropriate) and treated in the same way again, groups of test articles receiving the same rinse treatment at each repeat.

Main wash conditions were:

Detergent comosition used Daz (Procter &

Gamble Ltd.)

Concentration was 0.25% in 18 Hard water.

Liquor quantity 8 Imperial Gallons lbs.).

Temperature 48C.

pH of liquor 9-10.

Rinse conditions were:

Cold tap water 4 gallons 12 Hard.

Softener Active/cloth ratio 0.18/ by weight.

Product concentration 0.36% by weight (treatment (b) and (c) Rinse Compositions (a) Tap water.

Rinsing liquor pH: 7

(b) Composition comprising CH CH=CH -Continued 95% Water. Rinsing liquor pH: 7.6-8.2.

Test Articles Cotton Vests From first to 8th cycle those rinsed by (b) and (c) were significantly softer than those water rinsed as under (a), but no difference between (b) and (c) was distinguished with 95 percent confidence in the test; from the 4th cycle onwards, those rinsed by (b) were significantly whiter than those rinsed by (c).

Ratings (9 point Scheffe scale after the eighth cycle were:

whiteness Preference Softness (a) Water rinse +0.19 0.71 (h) Ylide rinse 1.14 0.08 (c) Cationic rinse 1.32 0.64 Least significant 1.80 0.70

difference (95% confidence) Polyester/cotton Shirts Those rinsed by (b) were significantly whiter than those rinsed by (c), and as white as if water rinsed.

Ratings after the eighth cycle were:

whiteness Preference (a) Water rinse +0.67 (b) Ylide rinse 0.50 (c) Cationic rinse 1.16

Least significant difference (95% confidence) Softening was not measured on these articles, being deemed to be of little practical importance on shirts of this type.

Cotton terry towels From first to eighth cycle those rinsed by (b) and were significantly softer than those rinsed by water (a), but no difference between (b) and (c) was distinguished with 95 percent confidence in the test.

Ratings after the fifth cycle were Softness (a) Water rinse 1.05 (b) Ylide rinse 0.25 (c) Cationic rinse 0.81

Least significant difference (95% confidence) The towels treated by (b) were judged according to the mean ratings to be whiter than those treated by (0) but the difference was not distinguished with percent confidence above the random error of the test.

EXAMPLE VI Twelve pieces of cotton terry towelling were boiled in a 0.5 percent solution of an anionic detergent-based commercial heavy duty household washing composition for 4 minutes, rinsed in tap water, spinand then tumble-dried. The pieces were divided into three groups of four.

The first set was rinsed in 10 times their dry weight of cold tap water.

The second and third sets were each rinsed in 10 times their dry weight of cold tap water containing 0.05 percent by weight of, respectively, the compound (i) C H CO NH N(CH CH CH=CHCH Br and the compound (ii) C H CO NH N(CH Cl-lCl-l=CH Cl.

In each case the pH of the rinse solution was adjusted to 6 by addition of citric acid. 1

The test pieces were then spin-dried, and air-dried at room temperature. Their softness was evaluated by a panel of four judges using a Scheffe paired comparison technique.

Compound (ii) The i: values represent 95% confidence limits.

EXAMPLE VlI Antistatic Effect A sample of polyacrylonitrile fabric was washed in a conventional built anionic detergent composition in a washing machine, employing a 0.5% concentration by weight of detergent composition, rinsed with water and spin-dried in the machine. The sample was then divided into three parts A, B and C.

Part A was rinsed in tap water, the cloth to water ratio by weight being 1:10, at room temperature.

Part B was rinsed at the same temperature in the same amount of tap water to which had been added 0.2 percent by weight of a 5 percent by weight aqueous solution of ditallowyl dimethyl ammonium chloride.

Part C was rinsed as Part B but there was added, instead of the ditallowyl dimethyl ammonium chloride, 0.2 percent by weight of an aqueous solution of the compound C|5H31CO N N (CH CH CH=CH containing 5 percent of said compound and 5 percent of a sodium citrate/citric acid mixture, such that the pH of said rinse liquor was 6.

The test fabrics were then dried but not ironed.

The samples were then tested. Each sample was held in one hand by an operator and rubbed with a nylon rod held in the other hand. The fabric, after a given number of rubs, was contacted with a gold leaf electroscope.

Sample A gave a full scale deflection (over 5 divisions) after 5 rubs.

Sample B gave a deflection of 1-2 divisions after 20-35 rubs. I

Sample C gave nil deflection after 35 rubs.

Thus the ammonioamidate demonstrated better antistatic properties than the cationic softener, and much better antistatic properties than given by simple water rinsing.

EXAMPLE Vlll Antistatic Effect Four swatches each of Nylon Courtelle (Trade name) polyacrylonitrile fabric were washed in a hot 0.5 percent solution of an anionic detergent-based commercial heavy duty household washing composition for 4 minutes, rinsed, spin-dried and tumble-dried. The swatches were then rinsed in times their dry weight of water, for reference, or in a 0.05 percent solution of an ammonioamidate as indicated below. ln each case, the pH of the solution was adjusted by addition of citric acid to 6.0. The swatches were spin-dried and air dried at room temperature. They were then rubbed 10 times on a nylon rod, and the charge in the rod was determined by the deflection of a Gold Leaf Ele'ctroscope. Two readings were taken for each of the four cloths and the means and standard deviations calculated, and the latter converted to 95 percent confidence limits.

The following compounds were tested (written in ylide form) f The values obtained were:

Deflection of Electroscope These compounds all appeared to have an antistatic effect, though in some cases the test did not demonstrate the effect with 95 percent confidence.

EXAMPLE lX Soil Release Effect on Hard Surfaces A number of pieces of window glass were pretreated as follows:

a. Cleaned with a commercial window cleaning product.

b. Washed with a 5 percent by weight aqueous solution of the compound of formula: (Cgl-l CO NH N(CH -CH CH=CH C1 the solution being adjusted to pH=6 by addition of a suitable pH buffering compound. This compound had a pK value of 5.8.

c. Washed as in (b) but adjusted to pH=7.

The glasses were dried and then stained by impression of a greasy hand (greased by a commercial hand cream). The stain was rendered more visible by dusting it lightly with charcoal dust. I

Stained glasses from (b) and (0) were then gently sprayed with tap water adjusted, in one test to 2 pH units lower than that of the original solutionapplied in the pretreatments, and in a second test, with tap water adjusted to 2 pH units higher than the original solution applied. The glasses pretreated as in (a) were sprayed similarly.

It was found that more stain was removed from the glasses pretreated as in (b) or (c) when sprayed with the more alkaline tap water of the second test, than from these glasses when sprayed with less alkaline water of the first test, or than from glasses pretreated as in (a).

EXAMPLE X In a similar test to that described in Example 1X, pieces of glass were pretreated: (d) with aqueous solutions containing 2 /2 percent of said compound and 2% percent of dodecyl dimethyl ammonium propane sulphonate, a typical zwitterionic surfactant, and (e) with a 5 percent solution of said zwitterionic alone.

When washed as in Example [X with water adjusted to 2 pH units higher than the original solution applied, the stain was largely removed from glasses pretreated as (d), but almost unaffected on glasses pretreated as EXAMPLE Xl Lime Soap Dispersion A solution of each of the mixtures defined below was prepared, placed in a water bath to maintain its temperature at C and nitrogen was bubbled through the solution at a fixed rate. The foam produced was carried over for a set time into a vessel containing very hard water (2300 ppm as Ca CO wherein the foam was quenched. The water was filtered through a 200 mesh BSS sieve, and the flocculated lime soaps determined after drying by weighing.

The test solutions each contained 0.5% by weight of the compositions given below, and the weights of undispersed lime soap (flocculated) were as indicated:

D E F G is m CO N N+ l5 l0 5 (CH;;) CH CH=CH-, Sodium coconut soap 100 Floc (grams) 0.134 0.003 0.015 0.045

EXAMPLE XII Pieces of cotton terry towelling were given a 10 minute wash at 50C in solutions as indicated below in 18 hard water. They were then squeezed out, given two one-minute rinses in cold water (18 Hard), squeezed A. Conventional heavy duty detergent 0.55 percent B. The same with addition of 0.08 percent of the compound C l-I CO NN (CH CH CH=CH The pH of the wash solutions was 9.7

Least significant diffe rcnce EXAMPLE XIII Six swatches of human hair were given a standard preliminary wash in an unbuilt detergent composition based on mixed sodium alkyl benzene sulfonate and sodium alkyl ether sulfate active detergents. The treatment comprised a wash, water rinse, second wash and rinse followed by air drying. The swatches were then treated as follows:

i. Six swatches were wetted for 5 seconds in running litre/minute) 2H. water at 40C (105F).

ii. Each swatch was lathered by hand in commercial shampoo (2 ml).

iii. Each swatch was rinsed for seconds in 2H. running water (10 litre/minute) at 40C. (105F).

iv. Repeat of (ii).

v. Three of the swatches were rinsed in water as in (iii).

vi. The other three swatches were rinsed for 15 seconds in 0.02 percent solution (1 litre) of ammonioamidate, buffered with sodium citrate/citric acid to pH 6.5, the proportions of amidate, citrate and citric acid being 5:2:3 by weight).

vii. Each swatch was air-dried.

Ammonioamidate Used C allyl ylide (C H CO NH N CH CH=CHCH Cl Results The gloss and softness of the treated swatches were evaluated by a panel of ladies using a paired comparison technique. The results are given below in panel score units (psu), with confidence limits based upon the variability ofjudgements of the same comparisons.

Triethanolamine Coconut monoethanolamide 4 Water and miscellaneous EXAMPLE XIV When in the above examples the following ammonioamidates are substituted either wholly or in part, e.g., 1:1 ratios, for the specifically named ammonioamidates, being added in the zwitterionic or cationic (chloride, bromide, phosphate, citrate, etc.,) form as is appropriate, substantially equivalent results are obtained in that the surfaces are conditioned:

What is claimed is:

I. A surface-treating composition consisting essentially of:

a. a substituted ammoniamidate having the formula R CO N N R R R or a cationic adduct thereof having the formula wherein X is an anion; R is an alkyl, phenyl, or alkaryl group having 1 to 25 carbon atoms; each of R and R is a methyl, ethyl, hydroxyethyl or cyanoethyl group; and R is either wherein R is hydrogen or alkyl of from I to 18 carbon atoms and R is hydrogen or an alkyl group having 1 to 4 carbon atoms; at least one of R and R having an alkyl chain of at least 6 carbon atoms; and

b. a pH buffering compound selected from the group consisting of: i. the alkali metal salts and acid salts of phosphoric acid, the polyphosphoric acids, boric acid, and; ii. the acids and corresponding alkali metal salts of citric acid, lactic acid, glycolic acid, malic acid, tartaric acid, acetic acid, capric acid, benzoic acid, and adipic acid; or mixtures thereof in an amount sufficient to substantially maintain the pH of a solution containing component (a) at a level of from about 0.001 percent to about 0.5 percent by weight at less than, equal to or not greater than 2 pH units above the pKa of component (a).

2. The composition of claim 1 containing one or more non-cationic, nonsoap surface-active agents.

3. The composition of claim 1 wherein X is a halide or a methosulphate.

4. The composition of claim 3 wherein each R and R is methyl or ethyl.

5. The composition of claim 4 wherein R is an alkyl of from 1 to 4 carbon atoms, an alkyl of from 9 to 21 carbon atoms or an alkyl benzene group having from 8 to 15 carbon atoms in the alkyl group.

6. The composition of claim 5 wherein R is and R is hydrogen, an alkyl of from 1 to 4 carbon atoms or an alkyl of from 8 to carbon atoms.

7. The composition of claim 3 wherein R is -CH- CH=CHR and R is hydrogen or methyl.

8. The composition of claim 1 wherein the pKa value of the ammonioamidate is in the range of from 5 to 7.

9. The composition of claim 8 wherein the pH of the aqueous solution ranges from 2 units below to 2 units above the pKa value.

10. The composition of claim 9 wherein said buffering agent is a water-soluble buffering agent selected from the group consisting of citrates and borates, the corresponding acids and mixtures thereof.

11. A fabric softening composition consisting essentially of:

a. a substituted ammonioamidate having the formula R, CO N-N R R3 R4 or a cationic adduct thereof having the formula wherein X is an anion; R, is an alkyl, phenyl, or alkaryl group having 1 to 25 carbon atoms; each of R and R is a methyl, ethyl, hydroxyethyl or cyanoethyl group;

and R is either wherein R is hydrogen or alkyl of from 1 to 18 carbon atoms and R is hydrogen or an alkyl group having 1 to 4 carbon atoms; at least one of R and R having an alkyl chain of at least 6 carbon atoms, said compound having a pKa value of from about 5 to about 7; and

b. a pH buffering compound selected from the group consisting of the acids and corresponding alkali metal salts of citric acid, lactic acid, glycolic acid, malic acid, tartaric acid, acetic acid, capric acid, benzoic acid, and adipic acid; or mixtures thereof wherein the buffering compound is present in amount sufficient to maintain the pH of a solution containing component (a) at a level of from about 0.02 percent to about 0.2 percent by weight at less than, equal to, or not greater than 2 pH units above the pKa of component (a).

Claims (11)

1. A SURFACE-TREATING COMPOSITION CONSISTING ESSENTIALLY OF: A. A SUBSTITUTED AMMONIAMIDATE HAVING THE FORMULA
2. The composition of claim 1 containing one or more non-cationic, nonsoap surface-active agents.
3. The composition of claim 1 wherein X is a halide or a methosulphate.
4. The composition of claim 3 wherein each R2 and R3 is methyl or ethyl.
5. The composition of claim 4 wherein R1 is an alkyl of from 1 to 4 carbon atoms, an alkyl of from 9 to 21 carbon atoms or an alkyl benzene group having from 8 to 15 carbon atoms in the alkyl group.
6. The composition of claim 5 wherein R4 is
7. The composition of claim 3 wherein R5 is -CH2-CH CHR6 and R6 is hydrogen or methyl.
8. The composition of claim 1 wherein the pKa value of the ammonioamidate is in the range of from 5 to 7.
9. The composition of claim 8 wherein the pH of the aqueous solution ranges from 2 units below to 2 units above the pKa value.
10. The composition of claim 9 wherein said buffering agent is a water-soluble buffering agent selected from the group consisting of citrates and borates, the corresponding acids and mixtures thereof.
11. A fabric softening composition consisting essentially of: a. a substituted ammonioamidate having the formula R1 CO N N R2 R3 R4 (I) or a cationic adduct thereof having the formula (R1 CO NH N R2 R3 R4) X (II) wherein X is an anion; R1 is an alkyl, phenyl, or alkaryl group having 1 to 25 carbon atoms; each of R2 and R3 is a methyl, ethyl, hydroxyethyl or cyanoethyl group; and R4 is either
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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3976581A (en) * 1972-01-10 1976-08-24 The Procter & Gamble Company Surface treating compositions containing ammonioamidate compounds
US4065422A (en) * 1977-02-16 1977-12-27 General Mills Chemicals, Inc. High slip polymer composition containing a polyacrylamido sulfonic acid salt and an alcohol
US4078901A (en) * 1976-12-20 1978-03-14 Texaco Inc. Detergent fuel composition
US4602648A (en) * 1984-10-30 1986-07-29 Soft Sheen Products, Inc. Pre-shampoo normalizer for a hair straightening system
US5492636A (en) * 1994-09-23 1996-02-20 Quest International Fragrances Company Clear concentrated fabric softener
US5695876A (en) * 1995-09-15 1997-12-09 Ppg Industries, Inc. Method and composition for applying acidic interleaving material in aqueous media to glass sheets
US5919394A (en) * 1996-04-25 1999-07-06 Ice Ban Usa, Inc. Deicing composition and method
US5922240A (en) * 1995-11-09 1999-07-13 Ice Ban Usa, Inc. Deicing composition and method
US5932135A (en) * 1996-03-21 1999-08-03 George A. Janke Deicing composition and method
US5965058A (en) * 1996-01-22 1999-10-12 Ice Ban Usa, Inc. Deicing composition and method
US20060075576A1 (en) * 2000-06-22 2006-04-13 Price Kenneth N Rinse-added fabric treatment composition, kit containing such, and method of use therefor

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3410880A (en) * 1963-10-30 1968-11-12 Procter & Gamble N-trialkylammonium imides of higher fatty acids
US3485806A (en) * 1968-02-07 1969-12-23 Ashland Oil Inc Hydroxy substituted aminimides
US3546115A (en) * 1967-02-28 1970-12-08 Cargill Inc Fabric softener
US3649569A (en) * 1967-06-05 1972-03-14 Procter & Gamble Textile treating compounds compositions and processes for treating textiles

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3410880A (en) * 1963-10-30 1968-11-12 Procter & Gamble N-trialkylammonium imides of higher fatty acids
US3546115A (en) * 1967-02-28 1970-12-08 Cargill Inc Fabric softener
US3649569A (en) * 1967-06-05 1972-03-14 Procter & Gamble Textile treating compounds compositions and processes for treating textiles
US3485806A (en) * 1968-02-07 1969-12-23 Ashland Oil Inc Hydroxy substituted aminimides

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3976581A (en) * 1972-01-10 1976-08-24 The Procter & Gamble Company Surface treating compositions containing ammonioamidate compounds
US4078901A (en) * 1976-12-20 1978-03-14 Texaco Inc. Detergent fuel composition
US4065422A (en) * 1977-02-16 1977-12-27 General Mills Chemicals, Inc. High slip polymer composition containing a polyacrylamido sulfonic acid salt and an alcohol
US4602648A (en) * 1984-10-30 1986-07-29 Soft Sheen Products, Inc. Pre-shampoo normalizer for a hair straightening system
US5492636A (en) * 1994-09-23 1996-02-20 Quest International Fragrances Company Clear concentrated fabric softener
US5695876A (en) * 1995-09-15 1997-12-09 Ppg Industries, Inc. Method and composition for applying acidic interleaving material in aqueous media to glass sheets
US5922240A (en) * 1995-11-09 1999-07-13 Ice Ban Usa, Inc. Deicing composition and method
US5965058A (en) * 1996-01-22 1999-10-12 Ice Ban Usa, Inc. Deicing composition and method
US5932135A (en) * 1996-03-21 1999-08-03 George A. Janke Deicing composition and method
US5919394A (en) * 1996-04-25 1999-07-06 Ice Ban Usa, Inc. Deicing composition and method
US20060075576A1 (en) * 2000-06-22 2006-04-13 Price Kenneth N Rinse-added fabric treatment composition, kit containing such, and method of use therefor

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