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Publication numberUS3729416 A
Publication typeGrant
Publication dateApr 24, 1973
Filing dateMay 24, 1971
Priority dateMay 27, 1970
Also published asDE2025945A1
Publication numberUS 3729416 A, US 3729416A, US-A-3729416, US3729416 A, US3729416A
InventorsBruening J, Eckert H, Heins A
Original AssigneeHenkel & Cie Gmbh
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Liquid softening rinsing agent compositions
US 3729416 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent O 3,729,416 LIQUID SOFTENING RINSING AGENT COMPOSITIONS Jiirgen Briining, Luchtringen, Hans-Werner Eckert, Dusseldorf, and Arnold Heins, Hilden, Germany, assignors to Henkel & Cie GmbH, Dusseldorf-Holthausen, Germany No Drawing. Filed May 24, 1971, Ser. No. 146,515 Claims priority, application Germany, May 27, 1970, P 20 25 945.4 Int. Cl. D06m 13/46 US. Cl. 252-83 4 Claims ABSTRACT OF THE DISCLOSURE Liquid softening rinsing agent compositions for Washed textiles containing, in the rinse liquid, from 0.1 to 2.0 gm./l. of an unsaturated carboxylic acid ester f the formula wherein R and R are selected from the group consisting of alkyl and alkenyl having from 10 to 24 carbon atoms, R is alkyl having 1 to 4 carbon atoms, A is selected from the group consisting of alkenyl and alkenylene having from 2 to 5 carbon atoms, X is an anion selected from the group consisting of halide and the anion of an organic, non-surface-active acid and n is an integer of 1 or 2. Liquid compositions containing from 1 to 25% by wegiht of said carboxylic acid esters and the process of softening washed textiles are also disclosed.

THE PRIOR ART After the drying of washed textiles, particularly those of cotton or similar cellulose fibers, a distinct hardening or harshening of the handle or hand can be observed. This phenomenon is particularly exhibited if the textiles have been washed in drum-washing machines with a strong mechanical agitation. This undesirable hardening of the textile goods can be avoided, as is well known, when a softening rinsing agent is added to the last rinsing liquor of the washing process, that conventionally contains cationic compounds with at least two longer-chain alkyl radicals in the molecule. There are liquid softening rinsing agents for laundry on the market which contain as active ingredient difattyalkyldimethylammonium salts, generally in the form of halides, in an aqueous dispersion. It is known, however, that such cationic softening rinsing agents, even in a strict adherence to the application directions, effect adversely the absorptivity of the treated laundry.

OBJECTS OF THE INVENTION L in wherein R and R are selected from the group consisting of alkyl and alkenyl having from to 24 carbon atoms, R is alkyl having 1 to 4 carbon atoms, A is selected 3,729,416 Patented Apr. 24:, 1973 from the group consisting of alkenyl and alkenylene having from 2 to 5 carbon atoms, X is an anion selected from the group consisting of halide and the anion of an organic, non-surface-active acid and n is an integer of 1 or 2.

A further object of the present invention is the obtention of liquid softening rinsing agent compositions consisting essentially of (A) From 1% to 25% by weight of an unsaturated carboxylic acid ester of the formula wherein R and R are selected from the group consisting of alkyl and alkenyl having from 10 to 24 carbon atoms, R is alkyl having 1 to 4 carbon atoms, A is selected from the group consisting of alkenyl and alkenylene having from 2 to 5 carbon atoms, X is an anion selected from the group consisting of halide and the anion of an organic, non-surface-active acid and n is an integer of 1 or 2.

(B) From 0.2% to 8% by weight of at least one nonionic surface-active dispersing agent,

(C) From 0.2% to 30% by weight of at least one water-soluble organic solvent, and

(D) The remainder to by weight of water.

A yet further object of the invention is the development of a process for the softening of washed textiles which consists of rinsing said washed textiles with a rinse liquid containing from 0.1 to 2.0 gm./l. of an unsaturated carboxylic acid ester of the formula wherein R and R are selected from the group consisting of alkyl and alkenyl having from 10 to 24 carbon atoms, R is alkyl having 1 to 4 carbon atoms, A is selected from the group consisting of alkenyl and alkenylene having from 2 to 5 carbon atoms, X is an anion selected from the group consisting of halide and the anion of an organic, non-surface-active acid and n is an integer of 1 or 2, drying said textiles and recovering said softened, washed textiles.

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

DESCRIPTION OF THE INVENTION It has now been found that these disadvantages of the prior art may be avoided and the objects of the invention achieved if the washed laundry, particularly in the last rinsing liquor, is treated with an aqueous solution or dispersion of an ester of an unsaturated carboxylic ester of the Formula I wherein Preferably the concentration of these textile softening agents in the aqueous rinse liquor lies in the range of 0.1

to 2.0, particularly 0.2 to 1.0, gm./l. In addition, other substances may be present in the rinsing bath, which substances are usable for the after-treatment of washed laundry, such as optical brighteners, anti-microbial active agents, souring agents, sequestering agents, perfumes and dyes, etc. At least part of these substances should be acidic, and the amount of the acidic substances, particularly of the souring and sequestering agents is selected so that the rinsing bath has a neutral to weakly acidic pH range.

In the Formula I, the alkyl radicals R and R may be straight-chain or branched, and can be, for instance, lauryl, myristyl, cetyl, oleyl, stearyl, arachidyl, behenyl, lignoceryl, etc. Preferred are alkyl radicals R and R which are derived from natural fatty acids, particularly from hardened tallow fatty acids or coconut fatty acids.

Where A is an alkenyl, it can be, for instance, vinyl, allyl, isopropenyl, l-propenyl, Z-butenyl, 1,3-butadienyl, etc. Where A is an alkenylene, it can be, for instance, vinylene, methylvinylene, 1,4 butz.dienylene-( 1,3), etc. The radical A may be present both in the cis and in the trans form.

The particularly preferred compounds of the Formula I are the esters of acrylic, methacrylic and crotonic acids, 3-butene carboxylic acid and 3-methyl-3-butene carboxylic acid, as well as of maleic, fumaric, itaconic, mesaconic, methylenemalonic, citraconic, muconic acids, etc.

The active softening ingredients of Formula I, used according to the invention, can be prepared in a known, not claimed herein, manner. The compounds of Formula I may be obtained by the reaction of the alkali salts of the unsaturated carboxylic acids with 3-chloro-2-hydroxypropyltrialkyl-ammonium halide or by the reaction of the unsaturated carboxylic acid with glycidyl-trialkylammonium halide. In addition, the compounds may be obtained from the unsaturated carboxylic acid, an epihalohydrin, for instance, epichlorohydrin, and a tertiary amine by reaction in an inert solvent.

As indicated, the object of the invention is a liquid softening rinsing agent for laundry consisting of dispersions or solutions of esters of unsaturated carboxylic acids of the above-defined Formula I and, optionally, of other conventional ingredients of softening rinsing agents for laundry in water and/or water soluble organic solvents. Preferably, the compositions are liquid softening rinsing agent compositions consistin essentially of (A) From 1% to 25% by weight of an unsaturated carboxylic acid ester of the formula wherein R and R are selected from the group consisting of alkyl and alkenyl having from 10 to 24 carbon atoms, R is alkyl having 1 to 4 carbon atoms, A is selected from the group consisting of alkenyl and alkenylene having from 2 to 5 carbon atoms, X is an anion selected from the group consisting of halide and the anion of an organic, non-surface-active acid and n is an integer of l or 2,

(B) From 0.2% to 8% by weight of at least one nonionic surface-active dispersing agent,

(C) From 0.2% to 30% by weight of at least one water-soluble organic solvent, and

(D) The remainder to 100% by weight of water.

As other conventional ingredients of softening rinsing agents for laundry are, for instance, considered optical brighteners, antimicrobial active ingredients, souring and sequestering agents, perfumes and dyes, etc.

The carboxylic esters of the Formula I, to be used according to the invention, are mostly present as oily, pasty or waxy substances. Their consistency depends widely upon the length and degree of saturation of the radicals R and R also whether the radicals R and R possess a homogenous chain length or if they are present as technical mixtures of homologs.

Such liquid softening rinsing agents for laundry contain the carboxylic acid esters, serving as textile softeners, of the Formula I in amounts of from 1-25% by weight. If the liquid agents contain additionally nonionic dispersing agents, the latter are present in amounts of up to 8.0% by weight, preferably in amounts of from 0.2-6.0% by weight; water soluble organic solvents may be present in amounts up to 30.0% by weight, preferably in amounts of from 02-30% by weight. Water represents the balance of the compositions.

The composition of particularly interesting liquid softening rinsing agents for laundry, according to the invention, can lie within the following recipe:

Residue: water.

As other conventional ingredients of softening rinsing agents for laundry at least one of the following components may be present in the stated amount, based on the total agent composition:

0.2% to 3.0% by weight of antimicrobial active material,

0.1% to 3.0% by weight of souring and sequestering agents,

0.01% to 0.5 by weight of cotton brighteners,

0.01 to 0.5% by weight of polyamide brighteners,

0.01% to 0.5 by weight of perfumes,

0.00001 to 0.05% by Weight of dyes.

The active substances, used according to the invention, show an excellent softening effect on fabric hardened by washing, particularly cotton terry cloth. Particularly advantageous, in comparison to known cationic softeners, is the practically insignificant effect on the absorptivity of these fabrics. The softening rinsing agents for washed textiles of the invention render, therefore, the fabric hardened by washing, particularly cotton terry cloth, again agreeably soft and nappy. Such treated fabrics possess, in comparison to the untreated washing goods, only a slightly diminished absorptivity and in comparison to the washing goods treated with known cationic softeners, a substantially improved absorptivity. In addition, by the treatment with the agents, according to the invention, an undesirable static charging of the textiles, particularly those of synthetic fibers, is largely prevented.

The compounds of the Formula I are obtained, as already mentioned, in the preparation generally as halides, particularly as chlorides and bromides. Preferably, the compounds of the Formula I are also incorporated into the agents of the invention as halides. However, in mixture with other ingredients of the agents, at least part of the halide anions may be replaced by other acid radicals which are generally admixed into the preparations of the invention as alkali metal salts and present in this form, conventional ingredients of the softening rinsing agents for washed textiles.

As carboxylic acid ester of the Formula I, for instance, the following may be used:

(1) Acrylic acid ester of [2-hydroxy-3- (di-hexadecylmethyl-ammonium)-propyl] chloride;

(2) Acrylic acid ester of [2-hydroxy-3-(dicocoalkylmethyl-ammonium)-propyl] chloride;

(3) Methacrylic acid ester of [2-hydroxy-3-(di-tetradecyl-methyl-amnronium) propyl] chloride;

(4) Crotonic acid ester of [2-hydroxy-3-(di-hexadecylmethyl-ammonium)-propyl] chloride;

(5) Crotonic acid ester of [2-hydroxy-3-(di-tallowalkylmethyl-ammonium)-propyl] chloride;

(6) Acrylic acid ester of [2-hydroxy-3-(di-tallowalkylmethyl-ammonium)-propyl] chloride;

(7) Crotonic acid ester of [2-hydroxy-3-(di-cocoalkylmethyl-ammonium)-propyl] chloride;

('8) Maleic acid bis-ester of [Z-hydroxy-B-(di-dodecylmethyl-ammonium)-propyl] dichloride;

(9) Maleic acid bisesters of [2-hydroxy-3-(di-cocoalkylmethy1-ammonium)-propyl] dichloride;

(10) Maleic acid bis-ester of [2-hydroxy-3-(di-tallowalkyl-methyl-ammonium)-propyl] dichloride;

(11) Fumaric acid bis-ester of [2-hydroxy-3-(di-dodecylethyl-ammonim)-proply] dichloride;

(12) Fumaric acid bis-ester of [2-hydroxy-3-(di-cocoalkyl-meth'yl-amrnonium)-propyl] dichloride;

(13) Itaconic acid bis-ester of [2-hydroxy-3-(di-dodecylmethyl-ammonium)propyl] dichloride;

(14) Muconic acid bis-ester of [2-hydroxy-3-(di-tetradecyl-methyl-ammonium)-propyl] dichloride.

In the following, the ingredients contained in the softening rinsing agents for washed textiles of the invention, are described more particularly by their various classes.

As nonionic dispersing agents, as they may be contained in the agents of the invention, nonionic surface-active agents are particularly suited, here designated in the following as nonionics. These are products which owe their hydrophilic properties to the presence of polyether chains, amineoxide, sulfoxide or phosphine oxide groups, alkylolamide groups as well quite generally to an excess of hydroxyl groups. Such nonionics contain in the molecule at least one hydrophobic radical of 8 to 26, preferably 10 to and particularly 12 to 18 carbon atoms and at least one nonionic water-solubilizing group. The preferably saturated hydrophobic radical is mostly of an aliphatic, optionally also alicyclic nature. It can be connected directly to the hydrophilic groups or over connecting members. As connecting member, for instance, benzene rings, carboxylic acid ester or carbonamide groups, ether-like or ester-like bound radicals of polyhydric alcohols, such as those of the ethylene glycol, the propylene glycol, the glycerine or of corresponding polyether radicals, are of interest.

Of particular practical interest are the products obtained by addition of ethylene oxide and/or glycide to fatty alcohols, alkylphenols, fatty acids, fatty amines, fatty acid or sulfonic acid amides having the above hydrophobic radicals. These nonionics may contain from 4 to 1 00, preferably 6 to 40 and particularly 8 to 20 ether groups, above all ethylene glycolether groups, per molecule. In addition, in these polyether chains or at their end, propylene or butyleneglycolether groups or polyether chains may be present.

To the nonionics further belong the products, known under the trade name Pluronics or Tetronics. They are obtained from water-insoluble polyoxypropylene glycols or from water-insoluble propoxylated lower aliphatic alcohols, containing 1 to 8, preferably 3 to 6 carbon atoms, or from water-insoluble propoxylated alkylene diamines. These water-insoluble (that is hydrophobic) propylene oxide derivatives are transformed by ethoxylation to give water-solubility and come under the named nonionics. Finally, as nonionics, *Ucon-Fluid which are partly still water-soluble reaction products of the above-named aliphatic alcohols with propylene oxide, are useable.

In addition, the fatty acid or sulfonic acid alkylolamides which are derived, for instance, from mono or diethanolamine, from dihydroxypropylamine or other polyhydroxyalkylamines, for insance the glycamines are in the class of useable nonionics. They can be replaced by amides of higher primary or secondary alkylamines and polyhydroxy carboxylic acids.

To the surface-active amine oxides belong, for instance, the products derived from higher tertiary amines containing one hydrophobic alkyl radical and two shorter alkyl and/ or alkylol radicals with up to 4 carbon atoms.

As nonionic dispersing agents, optionally suitable are also non-surface-active, water-soluble or water-emulsifiable or dispersible compounds, such as partial fatty acid glycerides as well as such compounds which contain no hydrophobic radicals in the sense of the above-described nonionic surface-active agents, such as solid or liquid polyethylene glycols, ethylene oxide adducts of glycerine and other polyalcohols, etc.

As water-soluble organic solvents of interest are watersoluble lower alcohols, etheralcohols, glycolethers or ketones with 1 to 6 carbon atoms, such as water-soluble alkanols, for example, metanol, ethanol, propanol, isopropanol; water-soluble alkanediols and alkoxyalkanediols, for example, ethylene and diethylene glycol; and their mono or dimethyl or ethyl ethers; alkanones, such as acetone and methylethylketone, etc. Isopropanol is particularly of practical interest.

Inorganic and non-surface-active organic acids, innocuous to the fibers to be treated, with 1 to 8 carbon atoms, optionally in the form of their slightly acidic to slightly alkaline water-soluble salts are suitable as souring and sequestering agents, such as amidosulfonic acid, urea compounds of orthophosphoric acid, oxalic acid, lactic acid, glycolic acid, citric acid, tartaric acid, benzoic acid, phthalic acid, gluconic acid, acetic acid and propionic acid as well as benzene, toluene or xylene sulfonic acids, sulfoacetic acid or sulfobenzoic acids.

The usable brighteners are mostly, if not exclusively, derivatives of diaminostilbene-sulfonic acid, diarylpyrazolines and of the amino-coumarins.

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

In the formula R and R signify halogen atoms, alkoxy groups, amino groups or residues of aliphatic, aromatic or heterocyclic, primary or secondary amines, or residues of aminosulfonic acids, while aliphatic residues present in the above groups preferably contain 1 to 4 and especially to 4 carbon atoms, and in the heterocyclic ring systems, fiveor six-membered rings are usually of interest. Aniline, anthranilic acid or anilinesulfonic acid residues are preferred as the aromatic amines. Brighteners derived from diaminostilbenesulfonic acid are mostly used as cotton brighteners. The following products derived from the above Formula II in which R represents the residue -NHC H and R may represent the following residues, are at present on the market.

Some of these brighteners are to be regarded as transitional types to the cotton brighteners as regards their affinity (for the fiber, for example the brightener in which R equals -NHC H The compound 4,4'-bis(4-phenylvicinal-triazolyl-2-)-stilbenedisulfonic acid-2,2 also belongs to the cotton brighteners of the diaminostilbenesulfonic acid type.

Diarylpyrazolines of Formulas III and IV belong to the polyamide brighteners, of which again a few have a certain affinity for cotton fibers:

In Formula III, R and R represent hydrogen atoms, or alkyl or aryl residues possibly substituted by carboxyl, carbonarnide or ester groups.

R and R represent hydrogen or short-chain alkyl residues.

Ar and Ar represent aryl residues such as phenyl, diphenyl or naphthyl, which may carry further substituents such as hydroxy, alkoxy, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, carboxylic acid ester, sulfonic acid, sulfonamide and sulfone groups or halogen atoms.

Brighteners of this type found at present on the market are derived from the Formula IV, and the residue R may represent the groups C1, SO -NH SO -CH=CH and COOCH CH --O-CH while the residue R in all cases represents a chlorine atom. 9-cyano-anthracene is also on the market as a polyamide brightener.

In addition, aliphatic or aromatic substituted aminocoumarins belong to the polyamide brighteners, for example 4-methyl-7-dimethylaminoor 4-methyl-7-diethyl amino-coumarin. Further useful polyamide brighteners are the compounds l-(benzimidazolyl-Z)-2-(N-hydroxyethylbenzimidazolyl-Z')-ethylene and 1-N-ethy1-3-phenyl-7-diethylamino-carbostyril. Suitable brighteners for polyester and polamide fibers are the compounds 2,5-di-(benzoxazolyl-2)-thiophene and 1,2-di-(5'-methyl-benzoxazolyl- 2' -ethylene.

Anti-microbial active substances are here understood as bactericidal or bacteristatic or fungicidal or fungistatic acting compounds. These active substance should be water-soluble as such, or in the form of their salts. The anti-microbial active substances, usable according to the invention, are mostly quaternary ammonium compounds, particularly those which contain, in addition to a long chain aliphatic and two short-chain aliphatic hydrocarbon radicals, an organic radical in the molecule, either aromatic residue connected over an aliphatic carbon atom to the nitrogen atom or an aliphatic residue with double bonds. Examples for such anti-microbial quaternary ammonium compounds are the (following:

dimethyl-benzyl-dodecyl-ammonium chloride,

dimethyl-benzyl-tetradecyl-ammonium chloride,

dimethyl-(ethylbenzyl) -dodecyl-ammonium chloride,

dimethyl-benzyl-decylarnmonium bromide,

diethyl-benzyl-dodecyl-ammonium chloride,

diethyl-benzyl-octyl-ammonium chloride,

dibutyl-allyl-, methyl-ethyl-benzyl-, ethyl-cyclohexyl-allyland ethyl-crotyl-diethylaminoethyl-, dodecyl-ammonium chlorides.

Other usable antimicrobial active substances are the lower alcohols or diols, substituted both by bromine and nitro groups, with 3 to 5 carbon atoms, such as the compounds 2-bromo-2-nitro-propanediol-1,3, l-bromo-l-nitro- 3,3,3-trichloropropanol-2, 2-brorno-2-nitro-butanol-1.

As anti-microbial active substances, also suitable are phenolic compounds of the type of the halogenated phenols with 1 to 5 halo substituents, particularly chlorinated phenols; alkyl-, cycloalkyl-, aralkyland phenylphenols with 1 to 12 carbon atoms in the alkyl radical and with 1 to 4 halo substituents, particularly chlorine and bromine in the molecule; alkenyl bis-phenols, par- 8 ticularly derivatives substituted by 2 to 6 halogen atoms and optionally 'by lower alkyl or trifluoromethyl groups with an alkylene bridge consisting of 1 to 10 carbon atoms; hydroxy benzoic acids or their esters and amides, particularly anilides which may be substituted in the benzoic acid and/ or aniline radical especially by 2 or 3 halogen atoms and/or trifluoromethyl groups; o-phenoxyphenols which may be substituted by 1 to 7, preferably 2 to 5 halogen atoms and/ or the hydroxyl, cyano, carbomethoxy, and carboxyl group or by lower alkyl. A particularly preferred derivative of the class of o-phenoxyphenols is Z-hydroxy- 2,4,4'-trichlorodiphenyl ether.

EXAMPLES The following examples describe the preparation of some softening rinsing agents for laudry, according to the invention. The same, however, are not to be deemed limitative of the invention in any respect.

Example 1 7% by weight of the acrylic acid ester of [2-hydroxy-3- (di-hexadecyl-methyl-ammonium)propyl] chloride; 2% by weight of the adduct of nonylphenol with 9 to 10 mols of ethylene oxide;

0.05% by weight of a cotton optical brightener of the Formula II in col. 6 in which R represents anilino and R dihydroxyethylamino;

1.0% by weight of glycolic acid;

1.25% by weight of isopropanol;

Residue: water.

For the preparation of the softening rinsing agent, the softening agent together with the nonionic dispersing agent and the organic solvent were converted to a homogeneous melt at 50 to 60 C. At the same time the glycolic acid and the optical brightener were dissolved in water, and this aqueous solution added the above-named melt with vigorous agitation. The thus-obtained preparation is distinguished by good pourability and distributability in water. Perfumes and dyes may be added to the finished preparation.

The textile softener, the acrylic acid ester of [2-hydroxy-3-(dihexadecyl methylammonium)-propyl] chloide, used according to Example 1, can be prepared by the following procedure, according to US. Pat. 3,397,227.

480 gm. (1.0 mol) of di-hexadecyl-methylamine and gm. (1.25 mols) of acrylic acid were dissolved in 1 liter of isopropyl alcohol and 116 gm. (1.25 mols) of epichlorohydrin as Well as 0.5 gm. of 2,6-di-tert.-butyl-4- methylphenol as inhibitor were added to this solution. After heating for 24 hours at 60 to 65 C., the solvent and excess starting material were distilled off in vacuo. The obtained product may be used without further purification.

The other active textile softening ingredients of the Formula I are obtained in an analogous manner.

Example 2 6% by weight of the acrylic acid ester of [2-hydroxy- 3-(di-tallowalkyl-methyl-ammonium)-propyl] chloride;

2% by weight of the adduct of one mol of tallow fatty alcohol (C /C -cut) with about 12 mols of ethylene oxide;

1.0% by weight of tartaric acid;

0.08% by weight of perfume;

0.0015 by Weight of dye;

Residue: water.

The textile softening agent composition was compounded as in Example 1.

Example 3 10% by weight of the acrylic acid ester of [2-hydroxy-3- (dicocoalkyl-methyl-ammonium)-propyl] chloride;

2% by weight of the adduct of 1 mol of cocoalcohol C /C -cut) with about 4 mols of ethylene oxide;

0.05% by weight of cotton brightener of the Formula II in col. 6 in which R represents anilino and R dihydroxyethylamino;

1.0% by weight of glycolic acid;

0.06% by weight of perfume;

0.001% by weight of dye;

% by weight of isopropanol;

Residue: water.

The textile softening agent composition was compounded as in Example 1.

Example 4 terry cloth were rinsed with an aqueous dispersion which contained 0.5 gm./l. or 1.0 gm./l. of active substances, compounded generally as in Example 4, in the last rinse of a drum-washing machine (duration: 5 minutes; liquor ratio 1:25). The samples were then centrifuged and dried by hanging. Subsequently, the hand was judged independently by 4 persons. The evaluation of the hand was expressed in numbers between 1 and 6,

1=full and very soft hand, and 6=very hard hand.

The average values of the evaluations were calculated that are summarized in the following Table I. The controlling values were as follows:

Fabric type A: Samples of new cotton terry cloth were treated for 240 hours in a washing machine under boiling washing conditions with 2.0 gm./l. of sodium tripolyphosphate solution. After drying, the hand number 6 was assigned to this thus pre-hardened fabric.

Fabric type B: Samples of new cotton terry cloth were treated 15 times with a commercial coarse washing agent under boiling washing conditions. After drying, such prehardened fabrics Were assigned the hand number 4. The hand number 1 was assigned to samples of new cotton terry cloth where the sizing was removed and they were treated with a solution of 0.5 gm./l. of ditallowalkyl-dimethyl-ammonium chloride. The softness of new, unlaundered cotton terry cloth corresponds generally to the hand numbers 1.5 to 2.

TABLE I Hand number at appli cation concentrations Type Number Active substance fabr'c 0.5 gmJl. 1.0 gm. [1.

1 Acrylic acid ester of [2-hydroxy'3-(di-hexadecylmethyl- A 2. 6 2. 1 ammonium) -propyl]chloride. B 1. 6 1. 3 2 Acrylic acid ester of [2-hydroxy-3-(di-tallowalkylmethyl- A 2. 6 2. 5 ammonium) -propyl]chloride. B 1. 3 1. 0 3 Methacrylic acid ester of [2-hydroxy-3-(di-tetradecylmethyl- A 2. 9 2. 6 ammonium)-propyl]chloride. B 1. 6 1. 5 4 Crotonic acid ester of [2-hydroxy-3-di-hexadecylmethyl- A 2. 9 2. 7 ammonium)propy]]chloride. B 1. 5 1. 3 5 Crotonic acid ester of [2-hydroxy-3-(di-cocoalkylmethyl- A 2. 6 2. 4 ammonium)-propyl]chloride. B 1. 5 1. 1 6 Maleic acid bis-ester of [2-hydroxy-3-(di-tallowaklylmethy1- A 2. 7 2. 6 ammonium)-propyl] dichloride. B 1. 6 1. 3 7 Maleic acid bis-ester of [2-hydroxy-3-(di-cocoalkyl-methyl- A 2. 9 2. 5 ammonium) -propyl] dichloride. B 1. 5 1. 4

Result 1% by weight of citric acid; 1% by weight of Z-bromo-2-nitro-propanediol-(1,3); 5% by weight of isopropanol;

Residue: water.

The textile softening agent composition was compounded as in Example 1.

Example 6 7% by weight of the crotonic acid ester of [2-hydroxy-3- (di-tallow-alkyl-methyl-ammonium)-propyl] chloride; 2% by weight of the adduct of oleyl/cetyl alcohol with about 10 mols of ethylene oxide;

1% by weight of citric acid;

1% by weight of N-dodecyl-N-benzyl-N,N-dimethylammonium chloride;

5% by weight of isopropanol;

Residue: water.

The textile softening agent composition was compounded as in Example 1.

For the softening rinsing of laundered textiles the latter are treated with a rinsing liquor which contains the softening rinsing agent for laundry of the invention in such an amount that the concentration of the softening agent in the bath liquor is 0.1 to 2.0, preferably 0.2 to 1.0 gm./l.

The textile softening effect of the active substances of Formula I, used according to the invention, was proven by a rinsing test. For this, samples of hardened cotton According to the values of Table I, the one treatment of the pre-hardened or hardened-by-washing cotton terry cloth of type A or B with the dispersions of the active substances of the invention leads to a full and soft hand that equals or even surpasses the hand of the new unlaundered fabric.

The influence of the textile softening agents of Formula I, used according to the invention, on the absorptivity of the cotton fabrics, treated with these active substances, was determined by the ascending method Border, Zeitschrift fur die gesamte Textilindustrie, 64, 593 (1962); ibid., 67, 22 (1965)].

A cotton test fabric, previously extracted with methanol and dichloromethane served as test material. This test fabric was agitated with a dispersion of 0.5 gm./l. of the test preparation (compounded as in Example 4) for 30 minutes, subsequently centrifuged, dried and air-conditioned. As comparison sample, a fabric treated analogously with water was used.

Cotton test strips, 20 cm. long and 2 cm. wide were suspended with their lower end into distilled water and the ascending height d of the water measured after a time t of 1, 2, 5, 10, 20 and 30 minutes. N=8 parallel measurements were carried out.

If the ascending height of water of the softening rinsed strip at the time 1' with the preparation of the invention i is designated as d the ascending height of the strip 1 l rinsed with water at the time j is designated as d for the absorptivity value 8; at the time i, that is the percentual residual absorptivity based on water 12 The absorption time is, according to the true dimension (sec./cm.), a reciprocial speed. An increase, there fore, corresponds a decrease in the absorptivity of the fabric.

is found 5 If t is designated as the absorption time of the fabric d rinsed with the preparation i and 1 the absorption ii time of the fabric rinsed with water, for the absorption d (percent) value, that is the residual absorptivity of the soft-rinsed Dd f0 th Vera e abso fivit Valu S fabric, referred to the sample treated with water=100%, a I e a g lip y e 10 the following equation is used.

1 i=30 i=30 d t H O N 32 100 Z i a=l00[ (percent) 1 f p z i q i fi dxj As comparison also the absorption time t of a test g z g g Ion o fabric rinsed with a solution of 0.5 gm./l. of N,N-dioctag f f ecy 1 {me i z decyl-N,N-dimethyl-ammonium chloride was determined e 1. fi 1mpr?vemen i and from it the percentual improvement 18 of the absorpi y g Slams l q g tivity of the preparations 1 with reference to N,N-dioctaa ecy lme y ammomum c on e decyl-N,N-dimethyl-ammonium chloride was calculated. was calculated. 20

t Aj=100 1] (percent) 13=100 f-d] (percent) 1 i=30 1 i= d In the Table III the measured absorption time t, the Al=1O0 Z absorption values a and the percentual improvement [3 1:1 1:1 for some carboxylic esters of the Formula I are given.

TABLE III 1. a B No. Active substance (sec.) (percent) (percent) 1 Methacrylic acid ester of [2-hydroxy-3-(rnethyl-ditetradecylam- 93 60.2 115 monium)-pro pyl] chloride. 2 Maleic acid bis estcr of [2-hydroxy-3-(methyl-didodecyl-ammon- 81 69.1 140 ium)-propyl] dichloride. 3 Fumaric acid bis-ester of [2-hydroxy-3-(methyl-didodecyl-ammon- 82 68.3 140 ium)-propyl] dichloride. 4 Fumaric acid bis-ester of [2-hydroxy-3-(methyl-ditetradecyl- 139 40.3 43

monium)-propyl] dichloride. Comparison, water 56 100 6-- Comparison,N,N.dioctadeeyl-N,N-dimethyl-ammoniu.mchloride. 200 28.0 0

In the following Table II the average absorptivity values S and the average percentual improvement of the absorptivity A for some selected substances of the invention are listed.

These tests demonstrate the superiority of the textile softening agent compositions of the invention.

The preceding specific embodiments are illustrative of the practice of the invention. It is to be understood, how- TABLE II S A Number Active substance (percent) (percent) 1 Methacrylic acid ester of [2-hydroxy-3-(methyl-dltetradecyl-ammonium)- 76. 6 190 propyl] chloride. 2 Maleie acid bis-ester of [2-hydroxy-3-(methyl-didodecyl-ammonium)- 85.8 220 propyl] dichloride. 3 Fumaric acid bis-ester of [2-hydroxy-3-(methyl-didodecyl-ammonium)- 91.0 340 propyl] dichloride. 4. Fmnaric acid bis-ester of [2-hydroxy-3-(methyl-ditetradecyl-ammonium)- 68. 2 160 propyl] dichloride. Comparison, water 100, 0 6 Comparison, N,N-dioctadecyl-N,N-dimethylam1nonium chloride 26. 2 0

The influence of the textile softness of Formula I used according to the invention, on the absorptivity of cotton test fabrics, softening rinsed with these preparations, was also determined by the method of Ox and Schuster [Schuster, Textil-Rundschau, 20, 352 (1965)]. Here the spreading-out time t of water in a horizontally spread cotton test strip under exactly defined conditions with the use of an absorptivity value meter was determined. As test material, a cotton test fabric, previously extracted with methanol and dichloromethane; was used. It was agitated for minutes with a dispersion of the test preparation (conc. 0.5 gm./l.) subsequently dried and air-conditioned. A fabric analogously treated with water served as a comparison sample. The measurement was done with an absorptivity value meter, according to Oxe' and Schuster, the distance of the measuring contacts was adjusted to 5 cm. and a dropping time of 10 sec. was selected. In the normal case ten parallel measurements were carried out.

wherein R and R are selected from the group consisting of alkyl and alkenyl having from 10 to 24 carbon atoms, R is alkyl having 1 to 4 carbon atoms,

A is selected from the group consisting of alkenyl and alkenylene having from 2 to 5 carbon atoms, X is halide and n is an integer of 1 or 2,

(B) from 0.2% to 8% by weight of at least one nonionic surface-active dispersing agent selected from the group consisting of a water-soluble dispersing agent and a water-dispersible dispersing agent,

(C) from 0.2% to 30% by Weight of at least one Watersoluble organic solvent having from 1 to 6 carbon atoms selected from the group consisting of watersoluble alkanols, water-soluble alkanediols, Watersoluble alkoxyalkanediols, and water-soluble alkanones, and

(D) the remainder to 100% by weight of water.

2. The composition of claim 1 wherein component A is present in an amount of from 2% to 10% by Weight, component B is present in an amount of from 0.2% to 3% by weight and component C is present in an amount of from 0.2% to 10% by weight.

3. The composition of claim 1 containing at least one of the following ingredients in the amount specified:

from 0.2 to 3% by weight of antimicrobial active comfrom 0.01 to 0.5% by weight of perfumes, and from 0.00001% to 0.05% by weight of dyes. 4. A process for the softening of washed textiles which consists of rinsing said Washed textiles with water containing from 0.1 to 2.0 gm./1. of an unsaturated carboxylic acid ester of the formula l I nX- R2 11 References Cited UNITED STATES PATENTS Sobolev 260485 X Sobolev 260486 Eckert et a1. 2528.8 Buck 2528.8 Krause et a1 2528.8 X Carl 117139.5 Balle et al 2528.8 X

5 HERBERT B. GUYNN, Primary Examiner U.S. Cl. X.R.

11733.5 T, 139.5 CQ; 260485 G, 486 B

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3954632 *Feb 16, 1973May 4, 1976The Procter & Gamble CompanySoftening additive and detergent composition
US3993573 *Jan 28, 1976Nov 23, 1976The Procter & Gamble CompanySoftening additive and detergent composition
US4076632 *Feb 22, 1977Feb 28, 1978The Procter & Gamble CompanyFabric softener
US4137180 *Jul 1, 1977Jan 30, 1979Lever Brothers CompanyFabric treatment materials
US4157307 *Aug 7, 1978Jun 5, 1979The Procter & Gamble CompanyLiquid fabric softener
US4187184 *Nov 16, 1978Feb 5, 1980Lever Brothers CompanySoftening composition
US4233164 *Jun 5, 1979Nov 11, 1980The Proctor & Gamble CompanyLiquid fabric softener
US4326966 *Jun 12, 1980Apr 27, 1982Ceskoslovenska Akademie VedAgent for textile livening with an antistatic effect and favorable dermatologic properties
US4368127 *Jun 30, 1980Jan 11, 1983Akzona IncorporatedFabric softening compounds and method
US4395569 *Dec 17, 1979Jul 26, 1983Rohm And Haas CompanyMethod of preparing sulfonic acid salts of acyloxyalkylamines and polymers and compounds therefrom
Classifications
U.S. Classification510/525, 560/222, 510/516, 560/196
International ClassificationC11D3/00, D06M13/00, C11D1/38, D06M13/46, C11D1/62
Cooperative ClassificationC11D3/0015, C11D1/62, D06M13/46
European ClassificationD06M13/46, C11D1/62, C11D3/00B3L