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Publication numberUS3563905 A
Publication typeGrant
Publication dateFeb 16, 1971
Filing dateNov 17, 1967
Priority dateNov 18, 1966
Also published asDE1617120A1, DE1617120B2, DE1617120C3
Publication numberUS 3563905 A, US 3563905A, US-A-3563905, US3563905 A, US3563905A
InventorsKling Walter, Schmadel Edmund
Original AssigneeHenkel & Cie Gmbh
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Detergents and cleansers
US 3563905 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

XR 3563905 EX US. Cl. 252-152 3 Claims ABSTRACT OF THE DISCLOSURE Novel detergent and cleansing agents are disclosed characterized by their ability to inhibit the graying of textile articles which takes place in laundering. In particular the novel detergent and cleaning agents are effective to prevent the graying of textile articles prepared at least in part with synthetic fibers.

The detergent and cleaning agents of the invention are characterized by a content of 0.1 to 20 wt. percent referred to the total composition of at least one water solub le salt of a polyester, the acid radicals of which are derived from a dicarboxylic acid and the alcohol component of which is derived from a dialkanolamine or an 'N-substituted derivative thereof and which has been made water-soluble by the introduction of sulfonic acid or alkylsulfonic acid groups into the molecule. In addition to the aforesaid polyester salts the detergent and cleaning agents contain the conventional surface active materials and the usual additives such as optical brighteners, bleaching agents, sudsers, anti-foamers, etc.

This invention relates to detergent and cleaning agents characterized by their ability to inhibit the graying of textile articles in laundering.

More particularly this invention relates to detergent and cleaning agents containing water-soluble salts or polyesters the acid component of which is derived from a dicarboxylic acid and the alcohol component of which is derived from a dialkanolamine or an N-substituted derivative thereof and which has been made water soluble by the introduction of sulfonic acid or alkylsulfonic acid groups into the molecule.

It is known in the prior art to add to detergents and cleansers containing surface active compounds, substances which improve the dirt carrying and retaining ability of the washing solutions. Such substances, which are referred to hereinafter as graying inhibitors, prevent a resorption of the dissolved dirt onto the cleaned surfaces. These substances are usually polyanionic polymers which are manufactured from natural substances such as cellulose, gelatins or glue, or are prepared by the polymerization of vinyl compounds, such as acrylic acid, methacrylic acid, maleic acid and mixtures thereof with copolymerizable olefins. Further, the polysulfonates of vinyl polymers have already been proposed as useful gray'inhibiting additives for detergent and cleanser preparations. Of all of the proposed compounds, however only carboxymethylcellulose has achieved any great technical importance, inasmuch as its gray-inhibiting action excels that of any synthetic polymers that have become known. However, carboxymethylcellulose as well as the above-named synthetic polymers have the disadvantage that their gray-inhibiting action is limited to cellulose fibers, whereas they are practically inetfectual in the washing of synthetic fiber material, particularly materials prepared from polyamides, polyesters and polyolefins. This disadvantage is particularly noticeable in connection with white textiles made of synthetic fibers or mixed fabrics made of synthetic and cellulose fibers, i.e., polyester-cotton mixture, which turn irreversibly gray in use despite repeated washing and thus become unattractive and must be discarded.

It is therefore a primary object of this invention to provide new and improved detergent composiitons having increased gray inhibiting efficiency over previously known detergent compositions.

Another object is to provide improved detergent compositions containing as the gray inhibiting agent, a watersoluble salt of a polyester the acid component of which is derived from a dicarboxylic acid and the alcohol component'of which is derived from a dialkanolamine or an N-substituted derivative thereof and which has been made water soluble by the introduction of sulfonic acid or alkylsulfonic acid groups into the molecule.

A yet further object is to provide improved gray inhibiting detergent compositions which are surprisingly etfective in laundering textile articles prapared at least in part with synthetic fibers.

Still further objects and the entire scope of applicability of the present invention will become apparent from the detailed description given hereinafter.

It has now surprisingly been found that water soluble salts of polyesters the acid component of which is derived from a dicarboxylic acid and the alcohol component of which is derived from a dialltanolamine or an N- substituted derivative thereof and which has been made water soluble by the introduction of sulfonic acid or alkylsulfonic acid groups into the molecule, possess gray inhibiting properties to an exceptional degree.

As mentioned above, it has already been proposed to combine synthetic detergent compounds with various graying inhibitors to produce anti-graying detergent compositions. As far as is known, however, no one prior to this invention has discovered the particular combination of compounds and proportions described herein that offer extraordinary results in the important area of whiteness maintenance and whiteness retention.

These and other advantages are obtained according to this invention by providing detergent compositions comprising a detergent surfactant compound and as a graying inhibitor 0.1 to 20 wt. percent referred to the total detergent compositions of at least one water-soluble salt of a polyester the acid component of which is derived from a dicarboxylic acid and the alcohol component of which is derived from a dialkanolamine or an N-substituted derivative thereof, and which has been made watersoluble by the introduction of sulfonic acid or alkylsulfonic acid groups into the molecule.

The polyester salts incorporated into the new detergent compositions in accordance with the invention are manufactured by methods already known in the art. The starting materials for preparing the polyester salts can be aliphatic, cycloaliphatic or aromatic saturated or unsaturated dicarboxylic acids which canzontain 3 (malonic) and up to 20 carbon atoms. Instances of particularly suitable acids include malonic, succinic, glutaric, adipic, sebacic, maleic and fumaric acids, benzenedicarboxylic acids and their mixtures. .The dialkanolamines which are suitable for use in the reaction to form the polyesters are derived from alcohols having 1 to 6, preferably 2 to 3 carbon atoms, and may be straight-chained or.

branched, saturated or unsaturated and maybe substituted at the nitrogen atom by aliphatic, cycloaliphatic or aromatic hydrocarbon radicals containing 1 to 18 carbon atoms. Examples of suitable substituted alkanolamines are N-methyldiethanolamine, N-methyldipropanolamine, N- ethyldiethanolamine, N-propyldipropanolamine, N-propylenediethanolamine, N-butyldiethanolamine, N-dodecyldiethanolamine, N-oleyldiethanolamine, N-cyclohexyldipropanolamine and N-phenyldiethanolamine.

The esterification of the reaction components, which are used preferably in a 1:1 molar ratio, is carried out in a known manner as for example, by heating the dicarboxylic acid and dialkanolamine for several hours under normal pressure in vacuo or in the presence of a solvent with which the water of reaction can be removed azeotropically by distillation. By the addition of any of the conventional esterification catalysts and particularly the strong inorganic ororganic acids, the reaction can be accelerated. In place of the free dicarboxylic acids, their reactive derivatives such as their anhydrides and halides can be used as starting materials. Similarly, the dicarboxylic acids in the form of their dimethyl or diethyl esters can be re-esterified in the known manner with the al-kanolamines in the presence of conventional re-esterification catalysts.

The introduction of the sulfonic acid groups into the polyester molecule is similarly carried out usingknown methods. Unsaturated polyesters, such as those obtained by reaction of maleic acid and a dialkanolamine, or those in which the hydrocarbon radical on the nitrogen atom is unsaturated, can be converted into the corresponding sulfonates by adding alkalibisulfites onto the double bond. It is also possible to effect the sulfonation of the double bond with complex compounds of sulfur trioxide and an organic compound such as pyridine-, dioxane or N,N- dimethylaniline. In like manner, saturated polyesters can be sulfonated, in which the acid radical, such as the malonic acid radical, contains a reactive methylene group.

Furthermore, the unsaturated or saturated polyesters can be reacted with quaternizing agents containing 2 to 6 carbon atoms and a sulfonic acid or sultone group. Examples of such quarternizing agents are halogen alkylsulfonic acids or their salts, such as, l-bromopropane-3-sulfonic acid and l-chloroethane-Z-sulfonic acid or their alkali salts, and the alkanesultones such as propanesultone or butanesultone. Polymeric sulfobetaines or salts of N- alkylsulfonic acids form in this reaction. The sulfobetaines can be incorporated into the detergent and cleaning compositions as they are or after neutralizing the sulfonic acid group. The ratio of sulfonating or quaternizing agent to polyester is preferably so selected that, after the reaction is ended, there are from -1 to 2 sulfonic acid groups for every two dicarboxylic acid groups or two dialkanolamine groups.

The polyesters containing sulfonic acid groups and manufactured in the above-described manner are of a resin-like nature, substantially insoluble in water and in organic solvents, but easily soluble in dilute alkali lyes. They may also contain secondary amounts of esters of low molecular weight and of unreacted starting substances which can be removed by extraction with organic solvents and thereafter recycled for further reaction. As these compounds, however, do not impair the cleaning properties of the agents, such separation is generally unnecessary.

As a result of the insolubility of the high molecular compounds in organic solvents, and because of their content of low-molecular constituents, the usual methods utilized for molecular weight determination are inoperative. Therefore, it is not possible to state the degree of polymerization and molecular weight of the polyesters with complete accuracy.

The detergents may contain the sulfonic acid polyesters according to the-invention in the form of their watersoluble salts and preferably in the form of their alkali metal and ammonium salts. The term ammonium salts is intended also to include the salts of the polyesters with organic ammonium bases. The polyesters can be added to the detergents in the form of their free acids, providing alkalinely reacting substances are present in a sufiiciently great excess for the formation of salts.

In addition to the salts of the polyesters, the new detergents and cleansing agents contain the surface active substances customarily used in such agents, such as those of the sulfate or sulfonate type, for example, the primary and secondary alkyl sulfates and the sulfates of ethoxylated or propoxylated fatty alcohols, and alkylbenzenesulfonates, primary and secondary olefin sulfonates, alkyl sulfonates and a-sulfofatty esters. Additional compounds of this class which may be used are the high molecular weight sulfatized partial ethers and partial esters of polyvalent alcohols; the sulfates of ethoxylated or propolylated fatty acid amides and alkylphenols; fatty acid taurides and fatty acid isoethionates and homologues thereof. Also suitable are the alkali soaps of fatty acids as well as the fatty acid condensation products of amino acids or degraded proteins; and ampholytes such as alkylbetaines and alkylsulfobetaines. The agents can furthermore contain non-ionic wash-active substances, such as alkyl and acyl polyglycolethers, co-condensation products of polyethylene glycol and polypropylene glycol, fatty acid sugar esters, aminoxides and fatty acid alkanolamides. Any of the foregoing compounds can also be used in the form of maxiures thereof. If the compounds have an aliphatic hydrocarbon radical, the latter is preferably to be straight-chained and have 8 to 22 carbon atoms. In compounds having araliphatic hydrocarbon radicals, the preferably unbranched alkyl chains contain an average of 6 to 16 carbon atoms.

Furthermore, depending on the purpose for which they are intended, the new detergents and cleansers can contain other conventional components such as pyrophosphates, polyphosphates and the more highly condensed phosphates, as well as silicates, in the form of their alkali salts; oxygen-yielding bleaches or bleaches containing active chlorine, such as alkali perborates, alkali percarbonates, alkali hypochlorites, chlorinated cyanuric acids and their alkali salts; as well as neutral salts such as magnesium silicate and sodium sulfate. Furthermore, se questering agents may be present, particularly alkali salts of aminopolycarboxylic acids, e.g., the sodium salts of aminotriacetic acid or of ethylenediaminotetraacetic acid and the alkali salts of hydroxyalkyldiphosphonic acids and aminopolyphosphonic acids, such a". the disodium salt of l-hydroxyethane-l,l-diphosphoic acid or the hexasodium salt of aminotri-(methylcnephosphonic acid).

Substances for the regulation of the pH can also be components of the mixture. These include sodium carbonate, sodium bicarbonate, lactic acid and citric acid and the like.

The detergents can also contain optical bn'ghteners, such as the derivatives of diaminostilbenedisulfonic acid or of diarylpyrazolinesulfonic acid. To control sudsing action the detergents may contain suds improvers, such as fatty acid amides, or anti-foaming agents, particularly trialkylmelamines.

The new detergents and cleansers may be in solid form, and preferably powder form, or in the form of solutions or pastes. Because of the excellent water solubility of the polyester salts they are particularly well suited for the manufacture of liquid detergent concentrates. Such liquid preparations may contain, in addition, to the abovenamed components, hydrotropic substances such as alkylbenzenesulfonates of low molecular weight, urea, and organic solvents.

In a number of cases, especially in the washing of textile materials made of cellulose or regenerated cellulose, the cleansing action can be further improved by the addition of standard graying inhibitors, particularly carboxymethylcellulose. The amounts of carboxymethylcellulose to be used will be approximately from 0.1 to 3% of the total weight of the detergents.

The new detergents of the invention are suitable for the cleaning of articles of all kinds, but particularly for the washing of textiles which are made of synthetic fibers,

cellulose fibers, regenerated cellulose, or of mixtures of the aforesaid types of fibers. In comparison with detergents of the prior art, the new detergents make the washing process itself easier and improve the whiteness of the laundry.

The following examples are given for the purpose of illustrating the invention and are in nowise to be construed as a limitation thereof.

The gray-inhibiting action of the compounds described in the following Examples was tested by known methods and include the following:

(A) The redeposition method (also known as the re- 'wash method) involving the washing together of dirty and clean textile material.

(B) The deposition method, in which clean textiles are washed in an artificially dirtied wash water.

(A) REDEPOSITION METHOD In each test 4 cloth samples, each made of Baumwollrenforc or of synthetic fabric and weighing a total of 8.3 g. were washed up to five times for 30 minutes, together with 1.3 g. of an artificially soiled cotton yarn in the Launder-Ometer (Atlas, Chicago, USA). Thereafter, the reflectivity of the thusly washed samples was tested using a light meter (Elrepho, Carl Zeiss, equipped with a No. 6 filter).

The realistically simulated dust-sebum combination used for soiling the cotton yarn consisted of a mixture of kaolin, iron oxide black, carbon black and synthetic sebum (prepared from a mixture of Va fatty acids, Va fat and V3 hydrocarbons). The cotton yarn contained approximately 11% pigments and about 2% sebum after soiling.

The detergent which was used in the washing of these samples had the following composition:

Percent n-Dodecylbenzenesulfonate (sodium salt) 20 Coconut fatty alcohol sulfate (sodium salt) 2.5 Tallow fatty alcohol sulfate (sodium salt) 2.5 Sodium pyrophosphate 40 Graying inhibitor -10 Sodium sulfate 35-25 The concentration of detergent in the wash water amounted to grams per liter and the hardness of the tap water to dH. The cotton samples were washed at 90 C. for minutes at a goods-to-wash water ratio of 1:12 (wash water 115 ml.), and the synthetic fabric samples were washed at 60 C. for 30 minutes and at a goods-towash water ratio of 1:30 (wash water 290 ml.). The samples were then rinsed four times with distilled water, dried and ironed, and evaluated photometrically.

(B) DEPOSITION METHOD of a liquid preparation having the following composition:

' G./l. n-Dodecylbenzenesulfonate (sodium salt) 7.8 Coconut fatty alcohol sulfate (sodium salt) 1.1 Tallow fatty alcohol sulfate (sodium salt) 1.1 Sodium pyrophosphate 16.0 Sodium sulfate 14.0 Graying inhibitor 5.0

In each case, 100 mi. of this stock solution was diluted to one liter with tap water of 10 dH. The samples were washed at 60 C. for 10 minutes with the Terg-O-tometer Substrate, method B operating at rpm. The samples were then rinsed with distilled water three times, dried and photometrically evaluated.

Example 1 146 g. (1 mole) of adipic acid and 273 g. (1 mole) of Ndodecyldiethanolamine were heated with stirring, at a temperature of from 150 to C., until the formation of water of reaction had ended. The polyester which was formed thereafter was reacted in the fused state at 150 to 160 C. with 130 g. (1.06 mole) of propanesultone. A portion of the reaction product was dissolved in water with the addition of the equivalent amount of soda lye and adjusted to a content of 10 g. of ester salt per liter. The quantities of this solution which are stated in the following tables were added to the wash water solutions in each case.

Example 2 116 g. (1 mole) of maleic acid, 147 g. (1 mole) of N- propyldiethanolamine and 250 g. of xylene were heated together with 1 g. of p-toluenesulfonic acid in a distillation apparatus that had been provided with an apparatus for separating the water and feeding back the solvent. The heating was continued until no more water separated in the receiver. The xylene was decanted from the insoluble resin that was developed, and the residue was freed in vacuo of any remaining solvent. The residue was then boiled with a 10% aqueous solution of sodium bisulfite (total g. Na S O corresponding to 2 moles) until it had completely gone into solution. The solution was likewise adjusted to a content of 10 g. of ester salt per liter.

The results of the washing tests are summarized in the following tables. The graying of polyester fabrics was determined by Method A (redeposition method) after 5 washings in each case. The washing tests made with polyamide fabrics were carried out by Method B (deposition method). The abbreviation CMC designates carboxymethylcellulose (sodium salt) which was used for purposes of comparison.

The results show that the agents of the invention are clearly superior as graying inhibitors as compared to carboxymethylceliulose.

TABLES Percent remission at inhibitor concentration example oi gram/liter number 0 0. 1

Percent remission with the addition of the tollowl amounts of carbon lack gram/ liter Inhibitor Substrate, method A Polyester, Dlolen Inhibitor example number None CMC;

Poiyarnide, Perlon We claim:

1. A detergent composition consisting essentially of a detergent selected from the group consisting of anionic, ampholytic and non-ionic detergents, and mixtures thereof, and a graying inhibitor in amount in the range of 0.1 to 20 weight percent based on total weight of the composition, said graying inhibitor being selected from the group consisting of water-soluble alkali metal and ammonium salts of a resin-like sulfonated polyester, and the radicals of said polyester being derived from substantially equal molar amounts of a dicarboxylic acid and a substituted dialkanol amine, said dicarboxylic being selected from the group consisting of malonic, succinic, glutaric, adipic, sebacic, maleic, and fumaric acids, the alcohol component of said substituted dialkanolamine having in the range of 1 to 6 carbon atoms, and said substituted dialkanol amine being 3. The composition of claim 1 wherein the sulfonation N-substituted with a hydrocarbon radical containing in the of step (b) is etfected with propane sultone or sodium range of 1 to 18 carbon atoms, said sultonated polyester bisulfite. being made by:

(a) esterifying said dicarboxylic acid, or a reactive ester, anhydride or halide derivative thereof with said 5 References Cited UNITED STATES PATENTS dialkanol amine with heating and removal of the 2454546 11/1948 et a1 260 75T water of reaction to obtain a substantially water and 2489'943 11/1949 wllson et a1 260-7 xylene insoluble esterification reaction product, and 2798047 7/1957 Tony et a1 252 152 (b) sulfonating said esterification reaction product thus 10 FOREIGN PATENTS obtained within the range of 1 to 2 sulfonic acid 1077 498 7/1967 Great Britain groups for every two dicarboxylic acid groups. 2. The composition of claim 1 wherein said substituted LEON D ROSDOL, Primary Examiner alkanol mine is selected from the group consisting of N- methyldiethanol, N-methyldipropanol, N-ethyldiethanol, 15 RADY Asslstam Exammer N-propyldipropanol, N-propylenediethanol, N-butyldiethanol, N-dodecyldiethanol, N-oleydiethanol, N-cyclohexyldipropanol and N-phenyldiethanol amines. 25289, 99, 110, 117, 137, 138, 161; 26075, 78

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3873603 *Oct 13, 1971Mar 25, 1975Henkel & Cie GmbhPolyester sulfonates containing quaternary ammonium groups
US4116885 *Sep 23, 1977Sep 26, 1978The Procter & Gamble CompanyAnionic surfactant-containing detergent compositions having soil-release properties
US4735746 *Mar 23, 1987Apr 5, 1988Texaco Inc.Long lasting detergent bar containing a polyamide or polyester polymer
US5707949 *Apr 4, 1996Jan 13, 1998E. I. Du Pont De Nemours And CompanyPrevention of dye-bleeding and transfer during laundering
EP0279134A1 *Dec 18, 1987Aug 24, 1988Rhone-Poulenc ChimieAntiredeposition latex for washing textiles
Classifications
U.S. Classification510/276, 528/293, 560/151, 510/475, 528/307, 510/352, 528/291
International ClassificationC11D3/00, C11D3/37
Cooperative ClassificationC11D3/0036, C11D3/3715
European ClassificationC11D3/00B7, C11D3/37B4