US3775316A

US3775316A - Softening finishes for washed laundry

Info

Publication number: US3775316A
Application number: US00230446A
Authority: US
Inventors: M Berg; W Fries; J Hartenstein; C Werner
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1969-04-30
Filing date: 1972-02-29
Publication date: 1973-11-27
Anticipated expiration: 1990-11-27
Also published as: DK138704C; FR2040418A1; NL7000520A; DE1922047C3; BE744712A; JPS4820204B1; DK138704B; DE1922047B2; FR2040418B1; DE1922047A1; CH529832A; AT298403B

Abstract

A SOFTENING FINISHING COMPOSITION FOR WASHED LAUNDRY HAVING A CONTENT OF TEXTILE SOFTENERS AND OPTIONALLY GERMICIDAL QUATERNARY AMMONIUM COMPOUNDS CONSISTING ESSENTIALLY OF: (1) FROM 92% TO 10% BY WEIGHT OF A FATTY ACID-HYDROXYALKYLPOLYAMINE CONDENSATION PRODUCT OF ONE MOL OF A HYDROXYALKYL-ALKYLPOLYAMINE HAVING AT LEAST ONE HYDROXYALKYL SELECTED FROM THE GROUP CONSISTING OF HYDROXYETHYL, HYDROXYPROPYL AND DIHYDROXYPROPYL AND AT LEAST TWO HYDROGEN ATOMS BONDED TO NITROGEN ATOMS, WITH 1 TO 4 MOLS OF A MIXTURE OF FATTY ACIDS HAVING FROM 8 TO 24 CARBON ATOMS, AT LEAST HALF OF SAID FATTY ACIDS IN SAID MIXTURE HAVING MORE THAN 15 CARBON ATOMS, AND (2) FROM 8% TO 90% WEIGHT OF A QUATERNARY AMMONIUM COMPOUND MIXTURE OF (A) FROM 0 TO 100% BY WEIGHT OF SAID MIXTURE OF TEXTILE SOFTENERS OF THE FORMULA

R1-N(+)(-R2)(-R3)-R4 A(-)

WHEREIN R1 AND R2 ARE ALKYL HAVING 14 TO 26 CARBON ATOMS, R3 AND R4 ARE ALKYL HAVING FROM 1 TO 4 CARBON ATOMS AND A IS THE ANION OF AN ACID, SAID SOFTENER BEING WATER-DISPERSIBLE, AND (B) FROM 100% TO 0 BY WEIGHT OF SAID MIXTURE OF A GERMICIDAL QUATERNARY AMMONIUM COMPOUND OF THE FORMULA

R5-N(+)(-R6)(-R7)-R8 A(-)

WHEREIN R5 IS AN ALIPHATIC HYDROCARBONYL HAVING 8 TO 18 CARBON ATOMS, R6 IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF ARYLALIPHATIC HYDROCARBONYL AND ALIPHATIC HYDROCARBONYL HAVING OLEFINIC BONDS, R7 AND R8 ARE HYDROCARBONYL HAVING FROM 1 TO 7 CARBON ATOMS, AND A IS THE ANION OF AN ACID, SAID GERMICIDAL COMPOUND BEING WATER-DISPERSIBLE, AS WELL AS AQUEOUS DISPERSIONS CONTAINING THE SAID SOFTENING FINISHING COMPOSITION.

Description

United States Patent 3,775,316 SOFTENING FINISHES FOR WASI-IED LAUNDRY Markus Berg, Dusseldorf-Holthausen, Walter Fries, Erkrath-Unterbach, Josef Hartenstein, Hilden, and Claus Werner, Haan, Germany, assignors to Henkel & Cie G.m.b.H., Dusseldorf-Holthausen, Germany No Drawing. Continuation of abandoned application Ser. No. 29,289, Apr. 16, 1970. This application Feb. 29, 1972, Ser. No. 230,446 Claims priority, application Germany, Apr. 30, 1969, P 19 22 047.4 Int. Cl. D06m 13/40 US. Cl. 252-8.8 8 Claims ABSTRACT OF THE DISCLOSURE A softening finishing composition for washed laundry having a content of textile softeners and optionally germicidal quaternary ammonium compounds consisting essentially of:

(1) from 92% to 10% by weight of a fatty acid-hydroxyalkylpolyamine condensation product of one mol of a hydroxyalkyl-alkylpolyamine having at least one hydroxyalkyl selected from the group consisting of hydroxyethyl, hydroxypropyl and dihydroxypropyl and at least two hydrogen atoms bonded to nitrogen atoms, with 1 to 4 mols of a mixture of fatty acids having from 8 to 24 carbon atoms, at least half of said fatty acids in said mixture having more than 15 carbon atoms, and

(2) from 8% to 90% by weight of a quaternary ammonium compound mixture of (a) from 0 to 100% by weight of said mixture of textile softeners of the formula wherein R and R are alkyl having 14 to 26 carbon atoms, R, and R are alkyl having from 1 to 4 carbon atoms and A is the anion of an acid, said softener being water-dispersible, and

(b) from 100% to 0 by weight of said mixture of a germicidal quaternary ammonium compound of the formula wherein R is an aliphatic hydrocarbonyl having 8 to 18 carbon atoms, R, is a member selected from the group consisting of arylaliphatic hydrocarbonyl and aliphatic hydrocarbonyl having olefinic bonds, R and R are hydrocarbonyl having from 1 to 7 carbon atoms, and A is the anion of an acid, said germicidal compound being water-dispersible, as well as aqueous dispersions containing the said softening finishing composition.

This is a continuation of Ser. No. 29,289, filed Apr. 16, 1970, now abandoned.

THE PRIOR ART After the drying of conventionally washed textiles particularly of cotton or similar cellulose fibers, a marked other textiles, such as, table linen where an agreeable hand is highly valued.

This undesirable harsh hand of the textiles can be avoided by adding cationic substances which contain at least two higher-molecular-weight fatty radicals in the molecule to the last rinsing bath. There are liquid softening finishes for washed laundry commercially available which contain as active component quaternary dialkyldimethyl ammonium salts with two higher alkyl radicals in the form of their aqueous dispersion. During the transport or in storing of such products, particularly in the cold season, on excessive cooling, particularly in freezing, a thickening of the dispersion takes place with gel formation which cannot be eliminated by either on reheating to room temperature, or by violent shaking.

OBJECTS OF THE INVENTION An object of the invention is the development of a softening and optionally germicidal finishing composition for use as an after-rinse agent for washed laundry which is stable when subjected to the cold.

Another object of the invention is the development of a softening finishing composition for washed laundry having a content of textile softeners and optionally germicidal quaternary ammonium compounds consisting essentially of:

(1) from 92% to 1 0% by weight of a fatty acid-hydroxyal-kylpolyamine condensation product of one mol of a hydroxyalkyl-alkylpolyamine having at least one hydroxyalkyl selected from the group consisting of hydroxyethyl, hydroxypropyl and dihydroxypropyl and at least two hydrogen atoms bonded to nitrogen atoms, with 1 to 4 mols of a mixture of fatty acids having from 8 to 24 carbon atoms, at least half of said fatty acids 'in said mixture having more than 15 carbon atoms, and

(2) from 8% to by weight of a quaternary ammonium compound mixture of (a) from 0 to by weight of said mixture of textile softeners of the formula wherein R and R are alkyl having 14 to 26 carbon atoms, R;, and R are alkyl having from 1 to 4 carbon atoms and A is the anion of an acid, said softener being water-dispersible, and (b) from 100% to =0 by weight of said mixture of a germicidal quaternary ammonium compound of the formula wherein R is an aliphatic hydrocarbonyl having 8 to 18 carbon atoms, R is a member selected from the group consisting of arylal'iphatic hydrocarbonyl and aliphatic hydrocarbonyl having olefinic bonds, R and R are hydrocarbonyl having from 1 to 7 carbon atoms, and A is the anion of an acid; said germicidal compound being water-dispersible.

A further object of the invention is the development of an aqueous softening finishing dispersion for washed laundry consisting essentially of an aqueous dispersion containing from 1% to 25% by weight of active softening substances consisting essentially of:

(1) from 92% to 10% by Weight of a fatty acidhydroxyalkylpolyamine condensation product of one mol of a hydroxyalkyl-alkylpolyamine having at least one hydroxyalkyl selected from the group consisting of hydroxyethyl, hydroxypropyl and dihydroxypropyl and at least two hydrogen atoms bonded to nitrogen atoms, with l to 4 mols of a mixture of fatty acids having from 8 to 24 carbon atoms, at least half of said fatty acids in said mixture having more than 15 carbon atoms, and (2) from 8% to 90% by weight of a quaternary ammonium compound mixture of (a) from to 100% by weight of said mixture of textile softeners of the formula wherein R and R are alkyl having 14 to 26 carbon atoms, R and R are alkyl having from 1 to 4 carbon atoms and A is the anion of an acid, said softener being water-dispersible, and

(b) from 100% to 0 by weight of said mixture of a germicidal quaternary ammonium compound of the formula wherein R is an aliphatic hydrocarbonyl having 8 to 18 carbon atoms, R is a member selected from the group consisting of arylaliphatic hydrocarbonyl and aliphatic hydrocarbonyl having olefinic bonds, R and R are hydrocarbonyl having from 1 to 7 carbon atoms, and A is the anion of an acid, said germicidal compound being water-dispersible, from 0 to 8% by weight of a non-ionic, surface-active emulsifying agent, from 0 to 10% by weight of a water-soluble organic solvent, from O to 1% by weight of textile optical brighteners, and from 0 to 1% by weight of conventional textile softening additives.

A yet further object of the invention is the development of a process of softening washed laundry which comprises rinsing washed laundry with water containing from 0.05 to 5 gm./l. of the above aqueous softening finishing dispersion.

These and other objects of the invention will become more apparent as the description thereof proceeds.

DESCRIPTION OF THE INVENTION The present invention relates to cold-stable compositions of softening finishing agents for washed laundry which are water-dispersible containing fatty acid-hydroxyalkyl-alkylpolyamine condensation products and quaternary ammonium compounds which may be germicidal as well as conventional ingredients of after-rinse agents.

The products of the invention are characterized in that they contain an aqueous dispersible combination of active ingredients consisting of a mixture of (1) from 92% to 10% by weight, preferably from 90% to by weight of a fatty acid hydroxyalkylpolyamines condensation product of one mol of a hydroxyalkyl-alkylpolyamine having at least one hydroxyalkyl selected from the group consisting of hydroxyethyl, hydroxypropyl and dihydroxypropyl and at least two hydrogen atoms bonded to nitrogen atoms, preferably of the formula at least one of Y and Z is hydrogen, n is an integer from 1 to 3, and R is a member selected from the group consisting of hydrogen and alkyl having 1 to 4 carbon atoms, with 1 to 4, preferably 1.5 to 3 mols of a mixture of fatty acids having from 8 to 24 carbon atoms, preferably saturated fatty acids with 16 to 22 carbon atoms, at least half of said fatty acids in said mixture having more than 15 carbon atoms, and

(2) from 8% to by weight, preferably from 10% to 85% by weight of a quaternary ammonium compound mixture of (a) from 0 to by weight of said mixture of textile softeners of the Formula I said mixture of germicidal quaternary ammonium compounds of the Formula 11 wherein R is an aliphatic hydrocarbonyl having 8 to 18, preferably 10 to 14 carbon atoms, and preferably selected from the group consisting of alkyl, alkenyl and alkadienyl, R is a member selected from the group consisting of arylaliphatic hydrocarbonyl, preferably phenyl-lower-alkyl and lower alkyl-phenyllower alkyl and aliphatic hydrocarbonyl having olefinic bonds, preferably alkenyl and alkadienyl having from 3 to 18 carbon atoms, R; and R are hydrocarbonyl having from 1 to 7 carbon atoms, preferably alkyl having from 1 to 4 and particularly 1 to 2 carbon atoms, as well as cyclohexyl and di-lower alkylamino-lower alkyl, and A is the anion of an acid, said germicidal compound being water-dispersible.

The after-rinse agents, according to the invention, have an excellent stability toward the cold and their effectiveness and consistency are not impaired even by temporary very strong cooling.

In the following the above defined fatty acid-hydroxyalkylpolyamine condensation products are for reason of simplicity called fatty-acid condensation products.

The textile-softening or the germicidal quaternary ammonium compounds are mostly present as water-dispersible salts of an inorganic or non-surface active organic acid, particularly of a carboxylic or sulfonic acid. Such inorganic or organic acids are for example, the hydrohalic acids, sulfuric acid, nitric acid as well as acetic acid, glycolic acid, lactic acid, tartaric acid, malic acid, citric acid, acid methylsulfate, methane-, ethane-, propaneor butane-sulfonic acid or toluene sulfonic acid, etc. A preferred anion is the chloride anion.

The fatty-acid condensation products are preferably derived from the hydroxyalkyl derivatives of ethylene diamine or of diethylene triamine, such as, hydroxyethylethylene diamine, dihydroxyethylethylene diamine, hydroxyethyldiethylene triamine, hydroxypropyldiethylene triamine, etc. Of particular practical interest are the derivatives of the N-hydroxyethylethylene diamine.

Such fatty acid condensation products are obtained by the reaction of 1 to 4, preferably 1.5 to 3 mols of fatty acid radicals which can be utilized in the form of the free fatty acids, of the lower alkylesters, of the acid halides, or of the glycerides, particularly of the triglycerides, with one mol of the hydroxyalkylpolyamine Where, however, not more fatty acid is present as can be bound by the amine nitrogen as an amide and/ or to the hydroxyl groups as an ester. For instance, in the case of N-hydroxyethylethylene diamine, 2 to 3 mols of fatty acid radicals are reacted.

When lower alkyl esters of the fatty acids are employed, they are preferably those having 1 to 4 carbon atoms in the alkyl, such as, methyl, ethyl, propyl or butyl esters. When a fatty acid halide is used, preferably the chloride is used. When glycerides are employed, particularly triglycerides of the higher fatty acids, with 8 to 24, preferably 16 to 22, carbon atoms in the fatty acid radical are used. Insofar as the glycerides contain fatty acid radicals with 8 to 14 carbon atoms, the amount of fatty acid radicals with 16 to 22 carbon atoms in the mixed glycerides or mixtures of glycerides shall be at least 50%. The fatty acid radicals can be derived from the caprylic, pelargonic, capric, undecylic, lauric, myristic, palmitic, stearic, oleic, arachic or behenic acids for example. Preferably, however, natural fats are utilized. The fats of plants, land and sea animals, for example, coconut fat, palm oil, olive oil, linseed oil, cottonseed oil, soybean oil, peanut oil, rape seed oil, lard, tallow and particularly the completely or partly hardened products of these fats as well as hardened fish or whale oil are of interest as natural fats.

The fatty-acid condensation products are mixtures of varied compounds. The composition of these product mixtures depends to a large extent upon the mol ratio of the reaction components and upon the nature of the reacted fatty acid derivatives. If 2 to 3 mols of a fatty acid or its esters with lower alcohols are reacted with one mol of N-hydroxyethylethylene diamine, the reaction product has about the following composition:

% to 35% by weight of diamidoesters 30 %to 60% by weight of diamides 20% to 45% by weight of monoamides If 2 to 3 mols of fatty acid radicals in the form of the, triglyceride are reacted with 1 mol of N-hydroxyethylethylene diamine the reaction product has about the following composition:

5% to by weight of diamidoesters Fatty-acid 25% to 40% by weight of diamides condensation 15% to 30% by weight of monoamides product 10% to 30 by weight of mono or diglycerides 0 to 15 by weight of triglycerides The fatty-acid condensation products resulting from glycerides may contain as by-products, in addition to the listed amounts of mono, di, and triglycerides, other components such as glycerine, free fatty acids and free amines in amounts of together 1% to 10% by weight.

The preparation of the fatty-acid condensation product used according to the invention is done in a simple manner by reacting the hydroxyalkylpolyamine with the fatty acid or its ester, free acid, acid halide or glyceride by heating to temperatures of from 90 to 180 C., preferably 90 to 130 C. Depending upon the temperature used and the fatty-acid component used, up to 25 hours are required to reach the reaction equilibrium. However, it is not absolutely necessary to reach this reaction equilibrium. For technical uses, products are acceptable in which the fatty-acid condensation product amounts to at least 50% and preferably 60% to 90% of the reaction product.

In order to finish the reaction, the reaction product is cooled and in a known manner converted, for example, by a cooling cylinder to flakes, or by an extrusion press to granulates, or by spraying to powder. According to a variant of the preparation, the reaction product is treated in the melt with a water-soluble organic or inorganic acid, adjusted to from slightly alkaline to slightly acidic, and

6 subsequently subjected to the above named forming processes. In the above forms, the fatty-acid condensation products are particularly capable of being stored or shipped. According to another variant the product melt can also be dispersed in an aqueous phase either by stirring the melt, after being adjusted to from slightly alkaline to slightly acidic with the water-soluble organic or inorganic acid, into an aqueous phase, or by stirring the melt into an aqueous phase which contains the organic or inorganic acid dissolved therein, or by stirring the melt into the aqueous phase and subsequently adding the organic or inorganic acid. In this way, an aqueous dispersion is obtained which is particularly suitable for the preparation of liquid after-rinsing agent according to the invention.

As water-soluble organic or inorganic acids which are used for the adjustment to from slightly alkaline to slightly acidic are organic acids, such as acetic acid, oxalic acid, glycolic acid, lactic acid, citric acid and tartaric acid and inorganic acids such as hydrochloric acid, sulfuric acid or phosphoric acid. Preferably glycolic acid is utilized.

The cold-stable textile softening agents according to the invention are preferably the fatty-acid condensation products of glycerides of higher fatty acids and N-hydroxyethylethylene diamine, particularly the condensation product of 1 mol of hardened tallow (corresponding to 3 fatty acid radicals) and 1 mol of N-hydroxyethylethylene diamine. The invention is, therefore, described in the following for this product. The data given, however, are also valid for the derivatives of other hydroxyalkyl amines, particularly for the hydroxyalkyl-diethylene triamine as well as for the fatty acid derivatives of other origin or composition, particularly for fatty acid glycerides of completely or partially hardened fats, particularly the hardened triglycerides such as hardened palm oil, hardened whale oil or hardened mustard seed oil.

The germicidal quaternary ammonium compoundssometimes present in the cold-stable re-rinsing agents, according to the invention, are those of Formula H, and particularly dibutyl-allyl-dodecyl-ammonium chloride,

methyl-ethyl-benzyl-dodecyl-ammonium chloride,

ethyl-cyclohexyl-allyl-dodecyl-ammonium chloride and ethyl-crotyl-diethyl-aminoethyl-dodecyl-ammonium chloride In experiments it has been found that in using such quaternary ammonium compounds vvith germicidal effect together with known textile-softening quarternary ammonium compounds, a gel formation may occur which until now made a simultaneous application of these compounds difficult. A further advantage of the invention is that in the presence of the named fatty-acid condensation products, this undesirable effect between the two types of quaternary ammonium compounds surprisingly does not occur and thus in the after-rinsing compounds according to the invention both a textile-softening and a germicidal quaternary ammonium compound can be present. This combination, when applied to the textiles as an afterrinse, imparts to the treated textiles both a soft hand and, additionally, a very desirable germicidal protection in one operation.

Quaternary ammonium textile softeners are optional in the composition of the invention. The combination of the fatty-acid condensation product as the softening component with the germicidal elfective ammonium compound also results in a cold-stable after-rinsing agent which imparts both a soft hand and a germicidal protection to the textiles in one operation.

While the cold-stable combination of active ingredients of the after-rinsing agent without addition of the germicidal effective ingredient, composed of to 92% by weight of fatty-acid condensation prodnet, and

90% to 8% by weight of textile-softening quaternary ammonium compounds has the cold-stable combination of active ingredients of the invention, the concomitant use of the following composition with germicidal elfective quarternary ammonium compounds is preferred:

50% to 80% by weight of fatty-acid condensation prodnot,

25% to 10% by weight of textile-softening quaternary ammonium compounds,

25% to 10% by weight of germicidal quaternary ammonium compounds.

In addition, a cold-stable combination of active ingredients of the textile-softening fatty-acid condensation product and germicidal effective quaternary ammonium compounds has the following composition:

75% to 90% by weight of the fatty-acid condensation product 25% to 10% by weight of a germicidal quaternary ammonium compound.

For the preparation of the after-rinsing agents, according to the invention, the components are brought into an aqueous phase in any desired sequence and dispersed with agitation. The fatty-acid condensation products can be stirred into the aqueous phase immediately as product melt, or as a flaked, granulated or powdery product. The queous phase can be heated in order to speed up the dispersion. Known non-ionic dispersing or emulsifying agents can be added to stabilize the aqueous dispersion thus obtained, if necessary. The non-ionic tensides, here for the sake of simplicity called non-ionics, are the conventional non-ionic dispersing and emulsifying agents. These nonionics are products whose hydrophilic properties are due to the presence of polyether chains, amineoxide, sulfoxide or phosphineoxide groups, alkylolamide groups and quite generally to the presence of an accumulation of hydroxyl groups.

The non-ionic tensides contain in the molecule at least one hydrophobic radical of 8 to 26, preferably 10 to 20, and particularly 12 to 18 carbon atoms and at least one non-ionic hydrophilic, water-solubilizing group. The preferably saturated hydrophobic radical is either of aliphatic or alicyclic nature. The hydrophobic group can be directly bound to the hydrophilic groups or over connecting members. As connecting members, for example, benzene rings, carboxylic acid esters or carbamide groups, radicals of polyhydric alcohols bound to others or esters, such as, ethylene glycol, propylene glycol, glycerin or corresponding polyether radicals, are preferable.

Of particular practical interest as non-ionics are the products obtained by addition of ethylene oxide and/or of glycide to fatty alcohols, alkyl phenols, fatty acids, fatty amines, fatty acid amides or sulfonic acid amides. These non-ionics may contain per molecule 3 to 100, preferably 6 to 40, and particularly 8 to 20 ether radicals, preferably ethylene glycol ether radicals. Propylene or butylene glycol ether radicals or polyether chains can also be present in these polyether radicals or on their ends.

The water-soluble addition products of ethylene oxide to water-insoluble polypropylene glycols as well as addition products of propylene oxide to alkylene diamines or to lower aliphatic alcohols with 1 to 8 and preferably 3 to 6 carbon atoms, and at least two hydroxyl groups, known under the commercial trademarks *Pluronics, Tetronics, or Ucon Fluid, are also classified as "nonionics. These water-insoluble propylene oxide derivatives form the hydrophobic radicals.

Further usable non-ionics are fatty acid or sulfonic acid alkylol amides which are derived, for example, from mono or diethanolamine, from dihydroxypropylamine, or

from other polyhydroxyalkylamines, such as glycamines. They can be substituted by amides of higher primary or secondary alkylamines and polyhydroxy carboxylic acids.

The surface active amineoxides are products deriving from higher tertiary amines which contain a hydrophobic alkyl radical and two shorter alkyl and/ or alkylol radicals, each with up to 4 carbon atoms.

The agents according to the invention can be advantageously combined with other substances which have already been used in textile-softening rinsing agents. These substances are, for example, optical brighteners, scouring agents and acidic agents for removing rust and other fiber incrustations, perfumes, dyes, etc. The combined application of the described finishing agents with optical brighteners, particularly also with anionic optical brighteners is to be considered as a further essential development of the invention.

The brighteners utilized are mostly, although not exclusively, derivatives of diaminostilbene sulfonic acid, of diarylpyrazolines and of aminocoumarins.

Examples for brighteners from the class of the diaminostilbene sulfonic acid are compounds according to Formula III:

III:

In this formula R and R are halogen, alkoxy amino or radicals of aliphatic, aromatic or heterocyclic primary or secondary amines, as well as radicals of aminosulfonic acids. The aliphatic radicals, present in the above groups, contain preferably 1 to 4, and particularly 2 to 4 carbon atoms, while the heterocyclic ring systems are mainly 5 or 6 membered rings. As aromatic amines preferably radicals of aniline, anthranilic acid or anilino sulfonic acid are used. Brighteners derived from diaminostilbene sulfonic acid are used mainly for cotton. The following products deriving from Formula I are commercially available where R is NHC H and R is represented by the following radicals: NH NHCH morpholino, NHC H -NHC H SO H, and OCH In respect to their fiber afiinity some of these brighteners are to be regarded as transition to the polyamide brighteners, for example, the brightener with R =NH-C H The cotton brighteners of the diaminostilbene sulfonic acid type also include the compound 4,4 bis-(4-phenyl-vicinal-triazoly1-2)-stilbene disulfonic acid-2,2'.

The polyamide brighteners, of which again some have a certain afiinity for cotton fibers include diarylpyrazolines of the Formulas IV and V:

In the Formula IV, R and R represent hydrogen atoms, or alkyl or aryl radicals substituted by carboxyl,

carbamldo, or ester groups, R, and R represent hydrogen or short-chain alkyl radicals, Ar; and Ar represent aryl radlcals, such as phenyl, diphenyl, or naphthyl which may have other substituents, such as hydroxy, alkoxy, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, carboxylic ester, sulfonic acid, sulfonamido, and sulfone groups, or halogen. Commercially available brighteners of Formula V are available where the radical R represents the groups C1, --S -NH SO CH=CH and -COOCI-I --CH O--CH while the radical R reprcnts, in all cases, chlorine. Also 9-cyanoanthracene is commercially available as a polyamide brightener.

The polyamide brighteners also include aliphatic or aromatic substituted aminocoumarins, for example, 4-methyl- 7-dimethylamino-coumarin or 4-methyl-7-diethylaminocoumarin. Further usable as polyamide brighteners are the compounds l-(benzimidazolyl-Z')-2-(N-hydroxyethylbenzimidazolyl-2)-ethylene and 1-N-ethyl-3-phenyl-7-diethylaminocarbostyril. Suitable brighteners for polyester and polyamide fibers are the compounds 2,5-di-(benzoxazolyl-2-)-thiophene and 1,2-di-('-.methyl benzoxazolyl- 2')-ethylene.

When the brighteners, together with other ingredient compositions of the invention, are present as aqueous solutions or as a paste, and are thereafter converted into solids by heat-drying, it is recommended to add organic complexing agents as stabilizers for the brighteners in amounts of at least 0.1%, preferably 0.2% to 1% by weight of the solid products.

The liquid after-rinsing agents, according to the invention, have the following composition:

1,0% to 25.0% by weight of the combination of active substances according to the definition of the invention,

0.0 to 8.0% by weight of non-ionic, surface-active dispersing or emulsifying agents,

0.0 to 10.0% by weight of water-soluble organic solvents,

in an aqueous solution. The residue may contain besides water also known brighteners, perfumes and dyes. Inorganic salts can also be present as admixtures in amounts of less than 0.5% by weight.

The composition of especially interesting liquid afternnsing agents, according to the invention, fall within the following recipes:

0.2% to 3.0%, preferably 0.5% to 1.5% by weight of textile-softening quaternary ammonium compounds of Formula I;

1.0% to 15.0%, preferably 2.0% to 9.0% by weight of fatty-acid condensation products;

0.2% to 3.0%, preferably 0.5% to 2.5% by weight of germicidal quaternary ammonium compounds of Formula H;

0.0 to 6.0%, preferably 0.2% to 3.0% by weight of nonionic surface-active dispersing or emulsifying agents; 0.0 to 5.0%, preferably 0.2% to 2.5 by weight of watersoluble organic solvents, particularly isopropanol;

0.0 to 0.5%, preferably 0.01% to 0.3% by weight of cotton brighteners;

0.0 to 0.5%, preferably 0.01% to 0.3% by weight of polyamide brighteners;

0.0 to 0.5%, preferably 0.01% to 0.3% by weight of perfumes;

0.0 to 0.05%, preferably 0.0000l% to 0.03% by weight of dyes;

Remainder: Water 0.5 to 10.0%, preferably 1.5% to 7.0% by weight of textile-softening quaternary ammonium compounds of Formula I;

0.5% to 12.0%, preferably 1.0% to 8.0% by weight of faty-acid condensation products;

0.0 to 6.0%, preferably 0.2% to 3.0% by weight of nonionic surface-active dispersing or emulsifying agents; 0.0 to 5.0% preferably 0.2% to 2.5% by weight of watersoluble organic solvents, particularly isopropanol;

0.0 to 0.5 preferably 0.01% to 0.3% by weight of cotton brighteners;

10 0.0 to 0.5 preferably 0.01 to 0.3% by weight of polyamide brighteners; 0.0 to 0.5%, preferably 0.01% to 0.3% by weight of perfumes; 0.0 to 0.05%, preferably 0.0000l% to 0.03% by Weight of dyes; Remainder: Water (III) 1.5% to 18.0%, preferably 3.0% to 12.0% by weight of fatty-acid condensation products;

0.2% to 3.0%, preferably 0.5% to 2.5% by weight of germicidal quaternary ammonium compounds of Formula II;

0.0 to 6.0%, preferably 0.2% to 3.0% by weight of noniom'c surface-active dispersing or emulsifying agents; 0.0 to 5.0%, preferably 0.2% to 2.5% by weight of water-soluble organic solvents, particularly isopropanol;

0.0 to 0.5 preferably 0.01% to 0.3% by weight of cotton brighteners;

0.0 to 0.5%, preferably 0.01% to 0.3% by weight of polyamide brighteners;

0.0 to 0.5%, preferably 0.01% to 0.3% by weight of perfumes;

0.0 to 0.05 preferably 0.00001% to 0.03% by weight of dyes.

Remainder: Water In the above recipes, the water can completely or at least partially be replaced by water-soluble orgamc solvents.

The following specific embodiments are illustrative of the practice of the invention without being limitative in any respect.

EXAMPLES The fatty-acid condensation products which are utilized in the after-rinsing compounds, according to the invention, are prepared according to the following example, or by analogy to it:

Example 1 Percent Tri-tallow fatty acid-diamido-ester 5.6 Di-tallow fatty acid-diamide 1 36.8 'I allow fatty acid-monoamide 1 20.5 Tallow fatty acid-triglyceride 13.6 Tallow fatty acid-diglyceride 8.2 Tallow fatty acid-monoglyceride 5.1 Glycolic acid 4.2 Free glycerine and free fatty acid 4.7

Derivatives of N-hydroxyethyl ethylene di-amine or acid condensation product.

This product was used as such as the fatty acid condensation product in the following examples; however, other fatty acid condensation products as described previously may be substituted with comparable results.

fatty Example 2 865 gm. (about 1 mol) of hardened palm oil were heated to C. :and 110 gm. (about 1.05 mol) of N- hydroxyethylethylenediamine were stirred in over a period of 30 minutes. The melt was agitated for another 4 hours at C. Thereafter, the melt was cooled slightly and 65 gm. of a 70% aqueous glyooli-c acid solution was added. After another 30 minutes of agitation at 90 C., the mixture was allowed to solidify by cooling in a thin layer.

The product was used as such as the fatty acid condensation product.

In place ot the haddened palm oil, comparable results were obtained when operating as above, when utilizing 885 gm. (about 1 mol) of hardened whale oil and 52 gm. of a 70% aqueous glycolic acid or 200 gm. (about 0.2 mol) of hardened mustard seed oil, 690 gm. (about 0.8 mol) of hardened beef tallow and 48 gm. of a 70% aqueous glycolic acid.

For the preparation of the after-rinsing agents described in the following examples, the stated amounts of fatty-acid condensation product, quaternary ammonium compounds, and dispersing or emulsifying agents were mixed in any order and melted at 70 to 80 C. The melt was added with agitation to the aqueous phase, heated to 70 to 80 C., and containing the brightener. The finished dispersion was allowed to cool and the perfume and dye was added.

Example 3 1.0 weight percent of difatty alkyl-dimethyl-ammonium chloride (difatty alkyl contained 25% to 50% palmityl and 75% to 50% stearyl);

6.0 weight percent of the condensation product from 1 mol of hardened tallow and 1 mol of N-hydroxyethyl ethylene diamine;

1.5 weight percent dimethyl-benzyl-(dodecyl/tetradecyl)- ammonium chloride;

1.0 weight percent of the adduct of 1 mol of dodecyl/ tetradecyl alcohol with about 3 mols of ethylene oxide;

0.05 weight percent of cotton brightener of the Formula III in which R represents anilino and R represents dihydroxy-ethylamino;

0.2 weight percent of prefume 0.85 weight percent of isopropanol Remainder: Water Comparable amounts of the fatty acid condensation product of Example 2 may be employed.

Example 4 3.5 weight percent of difatty alkyl-dimethyl-ammonium chloride (difatty alkyl contained 25% to 50% palmityl and 75% to 50% stearyl);

2.5 weight percent of the condensation product from 1 mol of hardened tallow and 1 mol of N-hydroxyethyl ethylenediamine;

1.5 weight percent of an adduct from 1 mol of palmitylstearyl alcohol with about 12 mole of ethylene oxide;

0.05 weight percent of cotton brightener of the Formula III wherein R represents anilino and R represents dihydroxy-ethylarrrino;

0.08 weight percent of perfume;

0.0015 weight percent of dye;

1.25 weight percent of isopropanol;

Remainder: Water Comparable amounts of the fatty acid condensation products of Example 2 may be employed.

For the application of the after-rinsing agent, according to the invention, freshly-washed textiles were treated with a rinsing liquor which contains the agent of the examples in a concentration of from 0.05 to gm./l., preferably from 0.5 to 3 gm./l.

On the treatment with the after-rinsing agents, according to the invention and the above examples, textiles, particularly cotton and linen, acquire an agreeable soft hand. In addition, the colors of the such treated textiles are restored or their degree of whiteness is intensified. By the application of agents with a content of germicidalactive quaternary ammonium compounds (according to Recipe 1) the textiles receive besides bacteriostatic germ protection. The treated textiles receive also antistatic properties.

The preceding specific embodiments are illustrative of the practice of the invention. It is to be understood, however, that other expedients known to those skilled in the art or described herein may be employed without departing from the spirit of the invention or the scope of the appended claims.

We claim:

1. A softening composition for washed laundry having a content of textile softeners and optionaly germicidal quaternary ammonium compounds consisting essentially of:

(1) from 92% to 10% by weight of a fatty acid-hydroxyalkylpolyamine condensation product of one mol of hydroxyethylethylenediamine with about one mol of a triglyceride of a fatty acid having from 8 to 24 carbon atoms, at least half of said fatty acids in said triglyceride having more than 15 carbon atoms, and

(2) from 8% to by weight of a quarternary ammonium compound mixture of (a) from 0 to by weight of said mixture of textile softeners of the formula wherein R and R are alkyl having 14 to 26 carbon atoms, R and R are alkyl having from 1 to 4 carbon atoms and A is the anion of an acid, said softener being water-dispersible, and

(b) from 100% to 0 by weight of said mixture of a germicidal quaternary ammonium compound of the formula wherein R is an aliphatic hydrocarbon having 8 to 18 carbon atoms selected from the group consisting of alkyl, alkenyl and alkadienyl, R is a member selected from the group consisting of phenyl-lower-alkyl, lower alkyl-phcnyl-lower alkyl, alkenyl having 3 to 18 caron atoms and alkadienyl having from 3 to 18 carbon atoms, R-; and R are selected from the group consisting of alkyl having from 1 to 4 carbon atoms, cyclohexyl and di-lower alkylamino-lower alkyl, and A is the anion of an acid, said germicidal compound being water-dispersible.

2. The softening finishing composition of claim 1 containing from 90% to 15% by weight of said fatty acidhydroxyalkylpolyamine condensation product, and from 10% to 85% by weight of said quarternary ammonium compound mixture.

3. The softening finishing composition of claim 1 containing, in said quarternary ammonium compound mixture, from 80% to 20% by weight of said mixture of said textile softeners and from 20% to 80% by weight of said mixture of said germicidal quaternary ammonium compound.

4. The softening finishing composition of claim 1 wherein said triglyceride of component 1, is a hardened fatty acid triglyceride having from 16 to 22 carbon atoms in said hardened fatty acid.

5. An aqueous softening finishing dispersion for washed laundry consisting essentially of an aqueous dispersion containing from 1% to 25 by weight of active softening substances consisting essentially of (1) from 92% to 10% by weight of a fatty acid-hydroxyalkylpolyamine condensation product of one mol of hydroxyethylethylenediamine with about one mol of a triglyceride of a fatty acid having from 8 to 24 carbon atoms, at least half of said fatty acids in said triglyceride having more than 15 carbon atoms, and (2) from 8% to 90% by weight of a quaternary ammonium compound mixture of (a) from to 100% by weight of said mixture of textile softeners of the formula wherein R and R are alkyl haivng 14 to 26 carbon atoms, R and R are alkyl having from 1 to 4 carbon atoms and A is the anion of an acid, said softener being water-dispersi'ble, and

(b) from 100% to 0 by weight of said mixture of germicidal quaternary ammonium compound of the formula wherein R is an aliphatic hydrocarbon having 8 to 18 carbon atoms selected from the group consisting of alkyl, alkenyl and alkadienyl, R

is a member selected from the group consisting of phenyl-lower-alkyl, lower alkyl-phenyl-lower alkyl, alkenyl having 3 to 18 carbon atoms and alkadienyl having from 3 to 18 carbons atoms,

R, and R are selected from the group consisting of alkyl having from 1 to 4 carbon atoms, cyclohexyl and di-lower alkyl-amino-lower alkyl, and

A is the anion of an acid, said germicidal compound being water dispersible, from 0 to 8% by weight of a non-ionic, surface-active emulsifying agent, from 0 to by weight of isopropanol, and from 0 to 1% by weight of textile optical brighteners.

6. The aqueous softening finishing dispersion of claim 5 containing from 2% to 9% by weight of said fatty 14 acid-hydroxyalkylpolyamine condensation product, from 0.5% to 1.5% by weight of said textile softeners, from 0.5% to 2.5% by weight of said germicidal quaternary ammonium compound, from 0.2% to 3% by weight of said non-ionic, surface-active emulsifying agent, from 0.2% to 2.5 by weight of isopropanol, and from 0.01% to 0.3% by weight of a cotton optical brightener, from 0.01% to 0.3% by weight of a polyamide optical brightener, from 0.01% to 0.3% by weight of perfume and from 0.00001 to 0.03% by weight of dye.

7. The aqueous softening finishing dispersion of claim 5 containing from 1% to 8% by Weight of said fatty acidhydroxyalkylpolyamine condensation product, from 1.5% to 7% by weight of said textile softeners, from 0.2% to 3% by weight of said non-ionic, surface-active emulsifying agent, from 0.2% to 2.5% of isopropanol, and from 0.01% to 0.3% by weight of a cotton optical brightener, from 0.01% to 0.3% by weight of a polyamide optical brightener, from 0.01% to 0.3% by weight of perfume, and from 0.00001% to 0.03 by weight of dye.

8. The process of softening washed laundry which comprises rinsing washed laundry with water containing from 0.05 to 5 gm./1. of the aqeuous softening finishing dispersion of claim 5.

References Cited UNITED STATES PATENTS 3,454,494 7/1969 Clark et 'al. 252-88 3,122,504 2/ 1964 Wedell 252-8.75 2,425,393 8/1947 Robinson et al. 2528.8 X 3,033,704 5/1962 Sherrill et a1. 252106 X 3,644,204 2/ 1972 Heins et a1. 2528.8 3,364,142 1/1968 Buck 2528.8 3,325,404 6/ 1967 Cohen et a1 2528.75 3,349,033 10/ 1967 Zuccarelli 252-8.75 3,382,200 5/1968 Buell 2528.75 X 3,451,927 6/ 1969 Tune 252-8.75

HERBERT B. GWYNN, Primary Examiner US. Cl. X.R.

117139.5 C.Q., 139.5 F.