LU86061A1 - SOFTENING DETERGENT COMPOSITIONS FOR HOT WATER WASHING CYCLE - Google Patents

Description

*% • ^ * The present invention relates to a composition and - a method for cleaning and softening fabrics during the washing cycle of a laundering operation. More particularly, the present invention relates to fabric softener compositions for use in the washing cycle of a laundering operation, in particular using hot water, the composition comprising a cationic quaternary ammonium compound insoluble in l water as a softener and a nonionic surfactant having a cloud point below the wash temperature and an amphoteric surfactant to raise the cloud point of the composition above the wash temperature.

The compositions useful for the treatment of fabrics in order to improve their flexibility and touch characteristics are known in the art.

When used in household laundering, fabric softeners are usually added to the rinse water during the rinse cycle, which lasts only about 2 to 5 minutes. Consequently, the consumer must monitor the laundering operation or take other precautions so that the fabric softener is · “· added at the correct time. This requires that the consumer returns to the washing machine either immediately before the start of the rinsing cycle of the washing operation, or at the start of this cycle, which of course is tedious for the consumer. In addition, special care should be taken to use the correct amount of fabric softener to avoid an overdose which could make garments hydrophobic by depositing a greasy film on the surface of the fabrics, as well as their imparting a certain degree of yellowing.

* As a solution to the above-mentioned problems, the use of fabric softeners is known which are compatible with common laundry detergents, so that the softeners can be combined with the detergents in a single package. use during the wash cycle of the laundering operation. Examples of such fabric softening compositions added during the wash cycle are described in U.S. Pat. 3,351,438, 3,660,286 and 3,703,480. In general, these fabric softening compositions for wash cycles contain a cationic quaternary ammonium type fabric softener and other ingredients which make the fabric softener compounds compatible with detergents of common laundering.

It is known, however, that the cationic softening compounds added to the washing cycle, either as an ingredient of a detergent-softening composition, or as a softener for the washing cycle, interfere with the brightening action of the colors as well as the cleaning power of the detergent. Thus, an attempt has been made to compensate to a certain extent for this interference of detergent-softening positions by using nonionic surfactants, higher levels of brightening compounds, carboxymethylcellulose, anti yellowing compounds, whitening agents, etc. However, only a small improvement in the softening compositions for the wash cycle has been achieved using various detergents, most of which are anionic.

However, there are a large number of descriptions in the art regarding detergent compositions containing cationic softeners, including softeners of the quaternary ammonium compound type, and nonionic surfactants. As a representative of this technique, mention may be made of the US patents. 4,264,457, 4,239,659, 4,259,217, 4,222,905, 3,951,879, 3,360,470, 3,351,483, 3,644,203, etc. ^ In addition, U.S. patents 3,537,993, 3,583,912, 3,983,079, 4,203,872 and 4,264,479, describe in particular ς 35 combinations of nonionic surfactant, cationic fabric softener and other surfactant -active · * 3 y * or ionic modifier, for example two zwitterionic surfactants, amphoteric surfactants, etc.

Although a large number of these formulations of the prior art provide satisfactory cleaning and / or softening under many different conditions, they still have the drawbacks of not providing suitable - comparable softening, for example to softeners. added to the rinse cycle - particularly under washing conditions in hot water, i.e. at a temperature of 60 ° C and above; to require the formation of complexes of the cationic compound; to use water-soluble cationic compounds of lower softening power, for example cationic compounds of the mono (higher alkyl) quaternary ammonium type; to be limited to liquid compositions, etc.

Although it is common for current laundry compositions and conventional household automatic washing machines, particularly in the United States, to be able to wash / clean soiled fabrics using cold or lukewarm wash water, in particular for delicate fabrics, fabrics that do not require ironing, fabrics with permanent creases, etc., it is nevertheless realized that a more effective cleaning (removal of dirt) requires higher wash temperatures. In addition, in Europe and other countries, domestic washing machines operate at elevated temperatures of 60 ° C or higher, which can reach the boiling temperature of the wash water. Although these high temperatures are advantageous for removing soiling, it does not have an equal advantage in terms of the softening action.

* The Applicant has discovered that the softening power of a detergent system based on a mixture of a nonionic detergent compound and a fabric softener of the cationic quaternary ammonium compound type is * * 4 * markedly improved. using a limited class of nonionic compounds, characterized by cloud points above the washing temperature. In addition, this improvement in softening power is obtained without adversely altering it, or by only slightly altering it, the washing power (that is to say cleaning power). This discovery constitutes the basis of an application filed the same day as the present application and having for title "Detergent-softener compositions for washing cycle" whose description is cited here for reference.

We have also discovered that the cloud point of nonionic surfactants having cloud points below 60 ° C can be raised to more than 60 ° C by incorporating a surfactant into the detergent composition. amphoteric. It has also been discovered that mixtures of mixed nonionic surfactants / am-photers are compatible with fabric softeners? of the water-insoluble cationic quaternary ammonium compound type, for example dimethyl-dis-tearyl ammonium chloride (CDMDSA) and improving the softening power of cationic tissue softeners to the same extent as the compounds not high cloud point ionic particles which, by themselves, have cloud points above the washing temperature. It has also been discovered now that the mixed nonionic / amphoteric surfactant system, even in the presence of cationic fabric softener, acts synergistically to provide a surprisingly superior cleaning action than that obtained by equal or greater amounts of each of the two surfactants used in the absence of the other.

A relationship between the cleaning power and the cloud point of a mixture of nonionic / cationic detergents is known from U.S. patents. 4,222,905 and 4,259,217. More particularly, as established in column 35 lines 40-61 of the aforementioned patent 4,259,217: "Methods for bleaching fabrics with the compositions of this invention are described herein. This provides an elimination of greasy and oily dirt and benefits for the maintenance of superior tissue. In these methods, the bleach detergent compositions are used under temperature conditions such as aqueous laundering solution is at or near temperature (i.e. about 20 ° C) of the cloud point (i.e. the temperature at which a phage rich in surfactant non-ionic active ingredient separates in the bleaching solution) from the mixture of nonionic / cationic surfactants. This can preferably be obtained by formulating these mixtures of nonionic / cationic surfactants so that their cloud point falls between about 0 and 95 ° C, especially between about 10 and 70 ° C, in particular between about 20 ° and 70 ° C, better still between; about 30 and about 50 ° C. During the washing operation, the temperature of the laundry solution is maintained within this temperature range! w tures and at * 20 ° C of the point temperature; corn. The yield is further improved when the temperature of the aqueous bleaching solution is * 15 ° C, more particularly about 25 + 10 ° C from the cloud point of the mixture of nonionic / cationic surfactants.

·>

Apparently the need to operate at temperatures of | washing equal to or less than the cloud point is based t | on the initial data that the cloud point of the mixture | 30 of surfactants in the wash water is the temperature at which micelles of the surfactant aggregate agglomerate to such an extent that these aggregates grow to the point that they separate from the solution and, as a result, turbidity is observed. An additional rise in temperature leads to complete separation of the phases of the water and of the nonionic surfactant, and, consequently, the detersive action exerted on the soiled fabrics and the overall cleaning ability are lost.

However, although it is established by the U.S. patent. 4,259,217 supra that cationic / 5 nonionic mixtures may "depending on the identity and concentration of the cationic component ... provide the known advantages in the prior art with respect to these cationic compounds, for example ... 1 fabric softening effects ", it is nevertheless obvious that there is no mention of it or suggestion that the softening effects of cationic compounds can be greatly improved by the use of certain nonionic compounds having inherently high temperatures cloud point. This is tantamount to saying that, although the U.S. patents 4,222,905 and 4,259,217 mentioned above describe a relationship between the cloud point of the nonionic / cationic mixture, washing temperature and cleaning power, it has now been found that this is the relationship between the cloud point of the non-ionic compound alone (or non-ionic compound 20 and any electrolyte present in the washing water) and the washing temperature which determines the softening action of softeners of the insoluble cationic quaternary ammonium compound type. in water. Contrary to the need of the present invention to use non-ionic compounds at elevated cloud point temperature (i.e., greater than about 60 ° C, particularly greater than about 90 bC, more preferably above about 100 ° C), the aforementioned patents prefer non-ionic surfactants having relatively low cloud points. Consequently, the nonionic surfactants used in the composition described in these patents are ethoxylated fatty alcohols with a maximum - of 12 moles of ethylene oxide, preferably a maximum of 9 moles of ethylene oxide, and having a hydrophilic-lipophilic balance (HLB) of between about 5 and 17, preferably between about 6 and 15.

tmmmrrrr ·· '· · ** Μ) --- (Λ 7. Therefore, it was completely unexpected that the softening power of the cationic softener could be very improved without reduction and, in fact with improvement of the cleaning power of the tensio non-ionic active agent using a mixed system of nonionic / amphoteric surfactants which has a cloud point higher than the washing temperature.

It is on the basis of this discovery that the present invention has been developed.

Therefore, the object of the present invention is to improve the softening power of detergent compositions containing softening agents of the quaternary ammonium type and non-ionic detergent compounds without adversely affecting, to a large extent, the overall cleaning power.

The present invention further proposes to greatly enhance the softening and cleaning power of a detergent-softening composition containing water-insoluble cationic tissue softening compounds and nonionic surfactants having a cloud point temperature. below 60 ° C when used to wash soiled fabrics in water at a temperature of at least 60 ° C.

These objects of the invention as well as others which will emerge from the description which follows are achieved by providing a detergent laundry composition capable of washing soiled fabrics in an aqueous washing liquid, at a elevated temperature at least about 60 ° C and capable of reaching the boiling temperature of about 100 ° C, which comprises a nonionic surfactant having a cloud point below the elevated temperature, a cationic quaternary ammonium compound insoluble in water as a softening agent and an amphoteric surfactant in an amount effective to elevate the cloud point of the composition at a temperature above the elevated temperature. In the preferred embodiment, the detergent composition comprises at least one additional detergent additive selected from detergency builders, thickeners, anti-redeposition agents, corrosion inhibitors, bleaches, enzymes, dyes, whitening agents, optical brightening agents, perfumes, etc.

The nonionic compounds envisaged are only limited by their solubility in water and by their cloud point temperature.

Preferred nonionic surfactants are commercially available and originate from the condensation of an alkylene oxide or an equivalent reactant and a hydrophobic having reactive hydrogen. The hydrophobic organic compounds can be aliphatic, aromatic or heterocyclic, although the first two classes are preferred. The preferred types of hydrophobics are higher aliphatic alcohols and alkyl phenols, although others can be used such as carboxylic acids, carboxamides, mercapans, su! Fonamides, etc ... The condensation products of ethylene oxide and (higher alkyl) -phenols or higher fatty alcohols represent preferred classes of nonionic compounds. In general, the hydrophobic unit should contain at least about 6 carbon atoms, and preferably at least about 8 carbon atoms, and it may contain as much as about 50 carbon atoms or more, a preferred range being approximately 8 to 22 carbon atoms, better still 10 to 18 carbon atoms for the aliphatic alcohols and 12 to 20 carbon atoms for the (higher alkyl) phenols. The amount of alkylene oxide varies widely depending on the hydrophobic, but generally an amount of at least about 3 moles of alkylene oxide per mole of hydrophobic up to about 14 moles of alkylene oxide per hydrophobic mole will provide the required water solubility, cleaning power and trouble point temperatures. ble below about 60 ° C.

Consequently, the preferred nonionic surfactants can be represented by the formula: 9 * R0 (-CH2CH20) nH (I) 5 in which R is a primary or secondary alkyl chain of approximately 8 to 22 carbon atoms and na has an average of 3 to 14, preferably 4 to 12, in particular 6 to 11; or 10 R '0- (CH2CH20) mH (II) in which R' is a primary or secondary alkyl chain of 4 to 12 carbon atoms, and m is on average equal to 3 to 14, preferably 4 to 12, Ί_ mi them another 6 to 11.

I b

Preferred alcohols from which the compounds of formula I are prepared include lauryl, myristyl, cetyl, stearyl and oleyl alcohols and mixtures thereof. Particularly preferred values - 2Q for R are C1Q to C18 alkyls, C12 to and their mixtures being particularly preferred.

Preferred values of R 'are C6 to C12 alkyl groups * Cg and Cg groups, including octyl, isooctyl and nonyl groups, being particularly preferred.

Representative examples of a nonionic compound of formula (I) are lauryl alcohol condensed with 5 or 7 or Π moles of ethylene oxide. A representative example of a nonionic compound of formula II is isooctylphenol or nonylphenol condensed with 3 to 8 moles of ethylene oxide.

Other nonionic compounds which can be used include the polyoxyalkylene esters of organic acids such as higher fatty acids, rosin acids, tall oil, acids from petroleum oxidation products, etc. . These * 10 • * esters usually contain about 10 to about 22 carbon atoms in the acid moiety and about 3 to about 12 moles of ethylene oxide or its equivalent.

Other non-ionic surfactants are the condensation products of alkylene oxide with higher fatty acid amides. The fatty acid group generally contains about 8 to about 22 carbon atoms and is condensed with about 3 to about 12 moles of ethylene oxide as a preferred example. The corresponding carboxamides and sulfonamides can also be used as suitable equivalents.

The amount of the nonionic compound is generally the minimum amount which, when added to the wash water with the amphoteric surfactant, provides suitable cleaning power. In general, amounts of between about 0.5 and about 20%, preferably between about 1 and about 15%, and more preferably between about 1 and 10% by weight of the composition, can be used.

The compositions of the present invention are primarily intended for use with household and industrial laundry washing machines which operate at elevated wash temperatures, particularly at water temperatures above about 60 ° C, preferably above 80 ° C, and more preferably at boiling, i.e. at 100 ° C, or higher. Naturally, however, these compositions, although being particularly effective, when 'they are used at these high washing temperatures, can also exert their best softening power at lower temperatures, between less than 60 ° C and about 20 ° C or less.

When the compositions are formulated to be used at washing temperatures within a wide range, for example between 20 and 60 ° C, as well as at higher temperatures to exhibit their maximum utility for a wide range of fabrics including delicate natural and synthetic fibers, as well as more temperature sensitive fabrics such as cotton, etc., the nonionic amphoteric combination and ratio can be chosen to provide a cloud point temperature which exceeds the temperature of the washing water by at least about 20 eC, for example a cloud point temperature of the composition of between 80 ° and 90 ° C. However, when the formulation is intended to be used primarily at high washing temperatures of 60 ° C or higher, as is generally the case in Europe as well as when used in industrial washing machines , the composition will then have substantially higher cloud points, for example reaching about 50 ° C above the washing temperature. Thus, for a washing temperature of 60 ° C, the nonionic / amphoteric must have a cloud point of at least about 65 ° C, preferably of at least about 70 ° C and which can reach about 90 ° C, preferably in the range of about 70 to 85 ° C. For wash water temperatures of 100 ° C, the cloud point of the composition is selected from about 105 ° to about 150 ° C, preferably from 105 ° C to 120 ° vs.

As used herein, the term "cloud point" refers to the temperature at which a graph 25 which shows the light scattering intensity of the composition as a function of the temperature of the solution, begins to increase suddenly at its maximum value under the following experimental conditions: The light scattering intensity is measured using a photogoniodiffusometer Model VM-12397, manufactured by the French Society of Control and Analysis Instruments, France (the device being designated below by (S0FICA)). The SOFICA sample cell and its cover are washed with hot acetone and left to dry. The mixture of surfactant is prepared and brought into solution with distilled water at a concentration of t 12 1000 ppm. A sample of about 15 ml of the solution is placed in the sample cell using a syringe with a 0.2 µm nucleopore filter. The syringe needle passes through the cover of the sample cell so that the interior of the cell is not exposed to atmospheric dust. The sample is left in a variable temperature bath and both the bath and the sample are subjected to constant stirring. The bath is maintained at temperature by heating using the S0FICÄ heater and is cooled by the addition of ice (heating rate = 1 ° C / minute); the temperature of the sample is determined by the temperature of the bath. The light scattering intensity (90 ° angle) of the sample is then determined at various temperatures, using a green filter and no polarizer in SOFICA.

In the present invention, the cloud point measurements are made for the two nonionic / amphoteric solutions (1% by weight) in distilled water and in water containing 10% NaCl, although this last case generally far exceeds the amount of salts and electrolytes actually encountered commonly. Therefore, if the non-ionic / amphoteric cloud point measured in a 10% NaCl solution satisfies the conditions of the cloud point of the present invention, then there is no problem for the formulation of compositions containing very high concentrations of detergency builder salts and other electrolytes, for example up to about 85% of the composition.

In this regard, it is known that the cloud point temperature for a given composition in the washing solution depends on the physical and chemical properties (e.g. CMC and solubility) of the cationic, nonionic / amphoteric and other components included in this composition. com-35 position, and will be lowered by increasing the length of the alkyl chains of the nonionic surfactant, at t> 1 3 decreasing the degree of ethoxylation of the nonionic component, or by adding electrolytes such as phosphates, polyphosphates , perborates, carbonates, sulfates, etc., especially in relatively small amounts (e.g., between about 1 and about 15% of a given composition).

Because in the present invention, water-insoluble cationic softening compounds are used, the cationic compounds will have substantially no effect whatsoever on the cloud point of total composition. In fact, since the cationic softening compounds used in the present invention are insoluble in water, the cloud point temperature of the total formulation is very difficult to measure since the mixtures are naturally quite cloudy. Consequently, the cloud point of the mixture of nonionic and nonionic / amphoteric compounds with or without addition of electrolytes, is determined in the absence of the cationic compound and this ensures a sufficiently precise measurement of the cloud point of the total composition. Including the cationic compound.

For washing temperatures between about 60 and 70 ° C, all of the nonionic surfactants described above, but which are ethoxylated with at least 15 moles of ethylene oxide, generally 15 to 30 moles o-25 ethylene oxide, provide cloud points above the wash temperature, and can provide improved softening without the ampho-surfactant.

However, for washing temperatures higher than 30 ° C. to 71 ° C. up to 100 ° C., in particular from 80 ° to 100 ° C., only the most highly ethoxylated surfactants, for example 25 to 30 moles of ethylene oxide per mol of hydro-phobe, for example the C 8 -C 8 alkylphenols ethoxylated with 25 to 30 moles, in particular 28 to 30 moles, and better still about 30 moles of oxide ethylene, have cloud points high enough to provide improved drowsiness without the amphoteric compound.

Although detergent compositions based on high cloud point nonionic surfactants can provide improved softening as described in the aforementioned patent application, these compositions often have the disadvantage of slightly deteriorating the cleaning power. In addition, the highly ethoxylated nonionic compounds are more expensive and less readily available commercially than the low cloud point nonionic compounds used in the present invention.

These drawbacks are avoided in the present invention since the addition of the amphoteric surfactant makes it possible to use less expensive non-ionic compounds which are readily available commercially, characterized by cloud points below 60 ° C. and by hydrophilic-lipophilic equilibria (HLB) of about 5 to "about 17; it requires very lower quantities of total surfactants to obtain an equivalent or higher cleaning power 7 Π; and it raises the cloud point of the composition to a value greater than the washing temperature chosen to reinforce the softening power of the cationic fabric softener.

It has now been found that for any of the nonionic compounds, the cloud point can be raised by as much as about 40 ° C, generally about 5-20 ° C by adding in the composition, an amphoteric surfactant compound, for example an amphoteric compound of the higher fatty alkyl type (for example copra) -30 carboxyethylated imidazoline, generally in a proportion of approximately 1 to 20%, preferably 1 to 15%, and better still from about 1 to 10% by weight of the composition.

Therefore, in a preferred embodiment of the invention, which is particularly useful for washing soiled fabrics, in washing water at an elevated temperature in the range of about 80 ° C to 100 ° C , v 15 the detergent composition comprises, in addition to the nonionic surfactant of formula I or of formula II and of the cationic quaternary ammonium compound insoluble in water used as fabric softener of formula III or # 5 formula IV, an amphoteric surfactant in an amount sufficient to raise the cloud point of the composition to a value greater than the temperature of 80 to 100 ° C, in particular greater than about 105 ° C.

Although it is not desired to be bound by any theory of operation, it is assumed that the amphoteric and nonionic surfactants form mixed micelles which are more soluble than the micelles formed from the nonionic compounds alone. These mixed micelles provide greater resistance to the formation of aggregates large enough to separate from the solution, so as to raise the cloud point.

Virtually all known amphoteric surfactants can be used to elevate the cloud point of the fabric softener composition for cationic and nonionic surfactants.

Examples of suitable amphoteric detergents are those in which both the anionic group and the cationic group contain a hydrophobic organic group, which is advantageously a higher aliphatic radical, for example of about 10 to 20 carbon atoms. Among these, mention may be made of long nitrogen chain alkylaminocarboxylic acids (for example of formula RR ^ NR'COOM); alkylimino-di-carboxylic acids with a long nitrogen chain (for example of formula RNÎR'COOM ^) and al kyl-betaï born with a long nitrogen chain (for example of formula RR3R ^ N + - R'COO ") where R is a long-chain alkyl group, for example of about 10 to 20 carbon atoms, R 'is a divalent radical linking the amino and carboxyl moieties of an amino acid (for example an alkylene radical of 35 1 with 4 carbon atoms), M is hydrogen or a metal forming a salt, R £ is a hydrogen or other substituent

V

16 monovalent substituent (for example methyl or other lower alkyl), and R3 and are monovalent substituents linked to nitrogen by carbon to nitrogen bonds (for example methyl or other lower alkyl substituents). Examples of particular amphoteric detergents are N-alkyl-beta-aminopropionic acids; N-alkyl-beta-imino-dipropionic acids and N-alkyl-N, N-dimethylglycine; the alkyl group may for example be that derived from coconut fatty alcohol, lauryl alcohol, myristyl alcohol (or a mixture of lauryl and myristylic alcohols), hydrogenated tallow alcohol , cetyl, stearyl or mixtures of such alcohols. The substituted amino propionic and iminodipropionic acids are often provided in the form of the sodium salt or other salts which may also be used in the practice of the present invention. Examples of other amphoteric detergents are fatty imidazolines such as those obtained by reacting a long chain fatty acid (for example from 10 to 20 car-20 bone atoms) with diethylene tri-friend and monohalo acids. geno-carboxyls of 2 to 6 carbon atoms, for example 1-copra-5-hydroxyethyl-5-carboxyethyl-imidazol ine; ** betaines containing a sulfonic group in place of a carboxylic group; concretes in which the long chain subset is linked to the carboxylic group without the intervention of a nitrogen atom, for example the internal salts of fatty acids of the 2-trimethylamino type such as 2-trimethylaminolauric acid , and compounds of any of the previously mentioned types in which the nitrogen atom is replaced by phosphorus.

A particular class of amphoteric surfactants are the fatty amido complex surfactants of general formula (V) 35 17 N / C \

K. Γ2 T

R - C -n + _r '__ 0M (V).

/ V

g OH "r2 _ COOM

in which R is a saturated or unsaturated straight or branched chain aliphatic group having 12 to 18 carbon atoms (for example lauryl, tridecyl, tetradecyl,; pentadecyl, palmityl, heptadecyl, stearyl, tallow, co- ^ prah, soybean, oleyl, linoleyl), R ^ and R2 each independently represent a divalent aliphatic hydrocarbon group of 2 to 5 carbon atoms (for example methylene, ethylene, propylene, butylene, 2-methylbutylene, pentylene, etc.), and M is hydrogen or an alkali metal (e.g. sodium, potassium, cesium and lithium). Examples of compounds of formula V which are commercially available include Λ 20 ii l "2 C11H23 -C - / N + CH2CH2-0Na OH" CH ^ COONa available under the designation Miranol CM (liquid) and Mi-25 ranol DM ( pulp) to the company Miranol Chemical Co.; Soro-mine AL and Soromine At from GAF Corporation and Deriphat compounds from General Mills.

The amphoteric compounds described in columns 3 and 4 of the U.S. patent. 4,203,872 can also be used. They include the following seven groups of compounds.

(1) Detergents of the betaine type of formula:

Rn 0

I c II

R, -N + -R.-C-0-35 1 J 4 R‘3 I »i 18

An appropriate example is

CH, 0 IJ II

(C10 ”C14) n ~ alkyl" N CH2C0 ~ CH, 5 (2) Detergents of the betafne type with an alkylene bridge of formula 0 R2 0 -H 1.

R, - CH, _ C _ N _ CH-CH, CH, __ N + _R._CO "10 1 L L L L \ 4 r3

A suitable example is 0 CH3 0

"H i J N

(C10-CH) n-alkyl-CH2- C _N —CHjCHjCHj — N + —CHjCO- ch3 (3) Imidazoline-type detergents of formula CHgCOOH 0 20 l + R ^ - C -N —R ^ -— 0 —CH2C0 N .CH, N "/"

A suitable example is 25 CH? C00H n 1 *

(C10Cu) n-alkyl - - N + - CH2CH2OCH2CCT

N / CH2 30 CH2 (4) Detergents of the alkyl iminopropionate type of formula

H

35 Ri - N _ CH2CH2C00H

• v 19 (5) Detergents of the alkyl iminodipropionate type of formula CH9CH9C00H / 2 2

3 5 R1-OCH2CH2CH2-N

^ CH2CH2C00H

(6) Detergents of the alkyl iminodipropionate type with ether bridge of formula 10

CH? CH? C00H

R ^ OCHgCHgCHg-N

^ CH? CH? C00H 15 (7) Amphoteric detergents based on copra-imida-zoline of formula H 0 - 1 "20 R.-C _ N + -CH? 0CH? CH? C0"

II

N CH, \ / ch2 Any mixtures of amphoteric detergents can also be used with each other and with the amine oxide type detergents listed above. In formulas (1) to (7) above, R | is a straight or branched, saturated or unsaturated radical containing about 7 to about 20, preferably about 8 to 18, and more preferably about 10 to 14 carbon atoms, R2 and R ^ each represent a lower alkyl group C 1 -C 4, preferably methyl or ethyl, preferably ethyl, R 4 is a divalent C 1 -C 4 alkylene group of> '20, "" · · preferably methylene or ethylene, preferably ethylene.

A particularly preferred group of amphoteric compounds are compounds of the (higher fatty alkyl) imidazoline carboxyethoxylates of formula (8) / H2 h9c ^ ν ^ -οη, οη, οοο ”2! I 22 1 g HOR4 - N —... C— Rj in which Rj is an aliphatic group with straight or branched chain, saturated or unsaturated of 7 to 20 carbon atoms, preferably of 8 to 18 carbon atoms, better still -1g re from 10 to 14 carbon atoms, and R ^ is a divalent lower alkyl group of 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms. Preferred Ri groups include copra, tallow, heptadecyl, oleyl, decyl and dodecyl, especially copra (ie, derived from coconut fatty acid). The preferred R 1 group is ethylene (-CHgCHg-). The copra-imi dazol i carbo-xyethylated compound is available under the designation Rexoteric CSF, which is a trademark for a Rexelin product, 100% active ingredient, or in the form 45% solution of active ingredient.

Another preferred class of amphoteric compound is carboxyethylated open chain (higher fatty alkyl) amine derivatives. They include the above groups (4), (5) and (6), i.e. detergents of the alkyl iminopropionate and ether-bridged alkyl iminopropionate types. The carboxyethylated octylamine which is available under the designation Rexoteric 0ASF from Rexolin is a particularly preferred element from this group.

Other classes of amphoteric surfactants such as sancosines, taurines, isothionates, etc. can also be used.

* 21

Although there is no strict rule regarding the choice of combinations of non-ionic surfactants and amphoteric surfactants or the appropriate amounts of each to obtain the necessary cloud point temperature in excess of the washing temperature to promote the softening power of the cationic fabric softener, it is generally sufficient to use the amphoteric surfactant with the quantity of nonionic surfactant mentioned above, in a proportion of approximately 1 at 20%, preferably from about 1 to about 15%, more preferably from about 1 to about 10%, based on the total weight of the composition. Suitable non-ionic: amphoteric ratios within the ranges of the above-mentioned amounts are in the range of about 1: 5 to 10: 1, preferably 1: 3 to 6: 1, more preferably 1: 2 at 4: 1.

However, some general principles and rules regarding factors affecting the cloud point such as the fact that the longer alkyl chain groups of the amphoteric generally lower the cloud point of the composition have been described above. As a result, it can be appreciated that within the above general ranges, the amount and nature of the amphoteric can vary widely, depending on the particular nature and the desired temperature of activity of the formulation. , as well as the nature and amounts of the other ingredients, in particular the nonionic surfactant and electrolytes.

Representative examples to show the effect of the amphoteric cloud point elevation can be seen from the following experimental results which are obtained by measuring the cloud point temperatures (° C) by the method described above - above for solutions containing 1% of active ingredient in distilled water or 35 in saline solution (NaCl at 10%): 22

Cloud point (° C) Surfactant (weight ratio) H2O dis- NaCl at 10% tilled _ A. Alkyl alcohol in 5 C12-C15 E017: 1 43¾ <25 B. Alkyl alcohol in CJ g ~ ^ ig E011 1: 1 85-2 59-2 A. + Rexoteric OASF (1: 2) 75-2 50-2 A. + Rexoteric OASF (4: 1) 58-2 28-2 10 A. + Rexoteric CSF (4: 1) 55-2 42¾ B. + Rexoteric OASF (1: 2)> 100 85-2 B. + Rexoteric OASF (4: 1) 95¾ 70 + -2 B. + Rexoteric CSF (4: 1)> 100 80- 2

Isooctyl-phenol E0130: l> 100 15 Nonyl-phenol EO120: 1> 100 72

Nonyl-phenol E0115: l 91 E0: Ethylene oxide.

* The above results also show, for comparison, the cloud point values of some non-ionic surfactants of the more strongly ethoxylated alkylphenol type.

The third essential ingredient in the formulations of the present invention is the cationic fabric softener. Softeners are used to make fabrics or textiles flexible, and the terms "softening" and "softener" relate to the hand, touch or sensation; it is the tactile sensation offered by fabrics or textile materials on the hand or body and this constitutes an important aesthetic and commercial criterion. In general, cationic fabric softeners consist of at least one hydrophilic functional group carrying a negative charge and one hydrophobic group containing a quaternary ammonium atom which is positively charged.

23

In order to give sufficient flexibility to the treated tissues, it is essential that the cationic compound is insoluble in water. As used herein, a compound is considered insoluble in water if its solubility in water at the washing temperature is less than about 1 Z, preferably less than about 0.5 Z.

It is generally desirable for the cationic softening compound to be included in the composition in a form ensuring high dispersibility in the washing liquid and therefore maximum fixation to the treated fabric. This can be achieved by using particle sizes dispersed in the washing liquid of between about <10 and about 50 microns, preferably between about <10 and about 20 microns for the cationic softener.

Fabric softeners of the type water-insoluble quaternary ammonium compound type which are known in the trade can be represented by the following formula: .

20 p

Rl ^ „/ R3 * R2 / N-R4 X '(III> 11 25 Γ“ Ί + / η r5-X * (IV) / \ r6 r7 30 where Rj and Rg and Rg and Rg each independently represent a long chain aliphatic radical of 16 to 22 carbon atoms, R ^ and R ^ and Ry independently represent lower alkyl radicals, or Rg can be the group -RgNHCRg where Rg is a long aliphatic radical 3 5 11 0 chain having 16 to 22 carbon atoms, and Rg is a divalent alkyl group of 24 to 1 to 3 carbon atoms, and X is an anion forming a water-soluble salt, for example a halide-nure, that is to say to say chloride, bromide, iodide; a sulphate, acetate, hydroxide, methosulphate, ethosulphate or a mono- or dib'asic radiolec 5 mineral or similar organic solubilization. The carbon chain of the aliphatic radical containing 16 to 22 carbon atoms, in particular 16 to 20 carbon atoms, can be straight or branched, saturated or unsaturated. The lower alkyl radicals contain 1 to 4 carbon atoms and can contain a hydroxy radical. Preferably, the carbon chains are obtained from long chain fatty acids such as those derived from tallow and soybean oil. The terms "di-soy" and "di-tallow," etc., as used herein, refer to the source from which the long chain fatty alkyl chains originate. It is also possible to use, if desired, mixtures of the above, as well as other surface-active agents of the water-insoluble quaternary ammonium type. The preferred ammonium salt is a dialkyl dimethylammonium chloride in which the alkyl group is derived from hydrogenated tallow or stearic acid, or a di (higher alkyl) imidazolinium chloride. Particular examples of quaternary ammonium type dozing agents of formula III suitable for use in the composition of the present invention include: hydrogen sulfide-dimethylammonium chloride, dimethyl distearyl ammonium chloride, bromide dimethyl-stëaryl-cetyl-ammonia um, dimethyl-diketyl ammonium chloride, di-soy-dimethyl ammonium chloride, sul-fate, methosulphate, ethosulphate, bromide and hydroxide, etc.

Examples of quaternary ammonium softeners of formula IV include 1-methyl-1,2-diheptadecyl imidazol inium chloride (bromide, methosulfate), 1,2-dieicosylalkylamidoethyl-1-methyl chloride -imi-dazolinium (bromide, methosulfate, etc.), methyl sulfate 3 * "* '25 of 2-hexadecyl-1-methyl-1 [(2-dodecoylamido) ethyl] imidazo-linium, methyl sulfate of 2-heptadecyl- 1-methyl-1 [2-stëa-roylamido) ethyl] imidazolinium. 2-nonadecyl / henicosyl -1 - [(2-eicosoyl / docosoyl imido) ethyljimidazolinium chloride.

^ Dimethyldistearyl ammonium chloride is particularly preferred because of its superior softening power, its biodegradability, its low solubility in water, its availability and its cost.

The amount of cationic fabric softener 10 can generally be between about 1 and about 20 2, preferably between about 4 and about 16%, and more preferably between about 6 to 9% based on the weight of the composition.

The weight ratio of the nonionic surfactant to the cationic fabric softener can be between about 1:10 and 5: 1, preferably between about 1: 8 and 4.5: 1.

The detergent compositions of the present invention are preferably provided in the form of free flowing powders but may also be in liquid form.

The detergent composition of the invention can also comprise, and in general it comprises, water-soluble detergency builder salts. Water soluble mineral alkaline detergent builder salts which can be used alone with the detergent compound or in admixture with other builders are the alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. (The ammonium and substituted ammonium salts can also be used). Particular examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, hexametaphosiphate sodium, sodium sesquicarbonate, sodium mono- and di-orthophosphates and potassium bicarbonate:> 126 sium. The alkali metal silicates are useful detergency builder salts which also serve to make the composition anti-corrosive for parts of the washing machine. Sodium silicates having NagO / SiO 4 ratios of 1.6 / 1 to 1 / 3.2, especially about 1/2 to 1 / 2.8, are preferred. Potassium silicates can also be used in the same ratios.

Another class of detergency builders useful here are the water-insoluble aluminosilicates, both crystalline and amorphous. Various crystalline zeolites (i.e., aluminosilicates) are described in British Patent No. 1,504,168, the U.S. Patent. Nos. -4,409,136 and Canadian Patents Nos. 1,072,835 and No. 1,087,477 which are all cited herein for reference. An example of useful amorphous zeolites can be found in Belgian Patent No. 835,351, this patent also being incorporated herein by reference. The zeolites generally have the formula: 20 (M20 ^. (Al203) y. {Si02) z.WH20 in which x is equal to 1, y is between 0.8 and 1.2, and preferably is equal to 1 , z is between 1.5 and 3.55 or more, and preferably between 2 and 3 and -w is between 0 and 9, preferably between 2.5 and 6 and M is preferably sodium. A representative zeolite is of type A or of similar structure, type 4A being particularly preferred. The preferred .alumino-si 1 icates have calcium ion exchange powers of about 200 mil 1iequivalents per gram or more, for example 30,400.

Other materials such as clays, particularly water-insoluble types, can be useful additives in the compositions of the present invention. Bentonite is particularly interesting. This material is mainly montmori11onite which is a hydrated aluminum silicate in which about 1/6 of the 127 aluminum atoms can be replaced by magnesium atoms and with which various amounts of hydrogen, sodium, potassium, calcium, etc., can be weakly combined. Bentonite in its more pu-5ified form (i.e. free of sandstone, sand, etc.) suitable for detergents invariably contains at least 50% montmorillonite and thus its cation exchange power is d 'at least about 50 to 75 mil! i-equivalent per 100 g of bentonite. A particularly preferred bentonite is constituted by bentonites from Wyoming or from the western United States of America sold under the designations Thixo-jels 1,2,3 and 4 by Georgia Kaolin Co.

These bentonites are known to soften textile materials as described in British patents No. 15,401,413 and No. 461,221.

Examples of organic alkaline sequestering adjuvant builder salts which can be used alone with the detergent or in admixture with other organic or inorganic detergency builder are the alkali metal, ammonium or ammonium aminopolycarbo-pn substituted ammomum, for example the sodium and potassium ethylenediaminetetraacetates, the sodium tri otriacetates ΙΊ and potassium and the N- (2-hydroxyethyl) -nitri 1odiacetates of triethanolammonium. Mixed salts of these polycarboxylates are also suitable.

Other suitable organic type detergency builders include tartronate succinates and carboxymethyl glycolates. Polyacetal-carboxylates are of particular interest. Polyacetal carboxylates and their use in detergent compositions are described in U.S. patents. No. 4,144,226; Nos. 4,315,092 and No. 4,146,495. Other patents relating to similar detergency builders include Nos. 4,141,676; No. 4,169,934; No. 4,201,858; No. 4,204,852; # 4,224,420; No. 4,225,685; No. 4,226,960; No. 4,233,422; No. 4,233,423; No. 4,302,564 and No. 4,303,777. 1. European patent applications No. 0015024; N ° 0021491 and N ° 0063399 are also relevant.

- Various other detergency additives or adjuvants may be present in the detergent product to give it other desired properties, of a functional or aesthetic nature. Thus, minor amounts of soil suspending or anti-redeposition agents can be incorporated into the formulation, for example polyvinyl alcohol, fatty amides, sodium salt of carboxymethyl cellulose, 1 'hydroxypropylmethyl-ce! -lulose; optical brightening agents, for example cotton brightening agents, polyamides and polyesters, for example stilbene, triazole and benzidine sulfone, in particular triazinyl-sti 1 substituted sulfonated bene, naphthotriazole-sti1bene sulfonated, benzidine sulfone, etc., with combinations of stilbene and triazole being preferred.

It is also possible to use whitening agents such as ultramarine blue; enzymes, preferably proteolytic enzymes, such as subtilisin, bromelain, papain, trypsin and pepsin, as well as amylase-like enzymes; bactericides, for example tetrachlorosalicylani 1 ide, * 1 'hexachlorophene; fungicides; dyes; pigments (dispersible in water); 25 conservatives; ultraviolet absorbers; anti-yellowing agents such as the sodium salt of carboxymethyl cellulose, a C 2 -C 22 alkyl alcohol complex with a C 1 -C 6 alkyl sulfate; pH modifiers and pH buffers; bleaching agents preserving colors, perfumes, and defoaming agents or foam suppressants, for example silicon compounds.

Bleaches are roughly classified for convenience by chlorine bleaches and 35 oxygen bleaches. The chlorinated bleaching agents are represented by examples by sodium hypochlorite (NaOCl), potassium dichloroisocyanurate (59% available chlorine) and trichloroiso-cyanuric acid (85% chlorine available). Oxygenated bleaches are represented by sodium and potassium perborates and potassium monopersulfate.

Oxygen bleaches are preferred. Stabilizers and / or activators of bleaching agents such as, for example, tetraacetylethylene diamine can also be included.

The proportions of the components which may be present in the preferred total compositions, in percentages by weight (of active substances) based on the total weight of the final product are as follows: nonionic detergent - approximately 0.5% to approximately 20 %, preferably about 15% to about 15%, especially 1% to 10%; amphoteric surfactant - about 2 to 20%, preferably 1 to 15%, and in particular 1 to 10%; quaternary ammonium salt - about 1% to about 20%, preferably about 4% to about 16%, more preferably about 6 to 9%; alkali metal detergency builder salts - about 20% to about 85%, and preferably about 35% to about 80%, and in particular, preferably, about 60 to 75%, the * "" remains consisting of additives for detergents, inert fillers and moisture. Appropriate ranges of additives for 25 detergents are: enzymes - 0 to 2%, especially 0.7 to 1.3%; corrosion inhibitors - about 0 to 40%; and preferably 5 to 30%; defoaming agents and foam suppressants - 0 to 15%, preferably 0 to 5%, for example 0.1 to 3%; agents for suspension or anti-redeposition of soils and anti-yellowing agents - 0 to 10%, preferably 0.5 to 5%; dyes, perfumes, brighteners and brighteners totaling 0% to about 2%, and preferably 0% to about 1%; pH modifiers and T pH buffers - 0 to 5 2, preferably 0 to 2%; bleaching agent - 0% to about 40%, and preferably 0% to about 25%, for example 2 to 20%; stabilizers and active 3

'S

• '30 • whitening agents - 0 to about 15%, preferably 0 to 10%, for example 0.1 to 8%. With regard to the choice of adjuvants, they will be chosen so that they are compatible with the main constituents of the detergent composition.

Although nonionic and amphoteric compounds are preferably the only detergent surfactant compounds used in the compositions of the present invention, small amounts of other surfactant compounds, including other nonionic, anionic compounds, and zwitterionics can also be used, preferably in proportions reaching 20% by weight, in particular 10% by weight, and better still 5% by weight.

Examples of other nonionic compounds include all of those mentioned above but which contain, for example, more than 15 moles of alkylene oxide per mole of hydrophobic, for example 15 to 30 moles of oxide ethylene per mole of hydrophobic.

Examples of suitable anionic detergents include water-soluble salts, for example the sodium, potassium, ammonium and alkylammonium salts of higher fatty acids containing about 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms. carbon.

Suitable fatty acids can be obtained from oils and waxes of animal or vegetable origin, for example tallow, fat, coconut oil, tal-1 ο1 and mixtures thereof. Particularly useful are the sodium and potassium salts of mixtures of fatty acids derived from coconut oil and tallow, for example sodium coconut salt and potassium tallow soap.

The anionic class of detergents also includes water-soluble sulfated and sulfonated synthetic detergents having an alkyl radical of 8 to 26, and preferably about 12 to 22 carbon atoms, in their molecular structure. (The term alkyl includes the alkyl portion of the higher acyl radicals).

1 d.

31 • Examples of the sulfonated anionic detergents are the monocyclic aromatic (higher alkyl) sulfonates such as the (upper alkyl) benzene sulfonates containing 10 to 16 carbon atoms in the straight or branched chain alkyl group 5, for example the salts of sodium, potassium and ammonium of (higher alkyl) benzene sulfonates, (higher alkyl) thouene sulfonates, (upper alkyl) phenol sulfonates, and naphthalene sulfonate. A preferred sulfonate is a (linear alkyl) benzene sulfonate having a high content of substituted phenyl isomers in position 3 (or higher) and a correspondingly low content (much less than 50%) of substituted phenyl isomers in position 2 (or a lower position), i.e. in which the benzene ring is preferably largely connected to position 3 or a higher position (e.g. 4, 5, 6 or 7) of the alkyl group and the content of isomers in which the benzene ring is linked at position 2 or 1 is correspondingly low. Particularly preferred materials are indicated in the U.S. Patent. No. 3,320,174.

Other suitable anionic detergents are Ί olefin sulfonates, including long chain al cene sulfonates, long chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxyalkane sulfonates. These detergent olefin sulfonates can be prepared in a known manner by the reaction of SO 6 with long chain olefins containing 8 to 25, preferably 12 to 21 carbon atoms and having the formula RCH-30 CHR.J in which R is a higher alkyl group of 6 to 23 carbon atoms and R ^ is an alkyl group of 1 to 17 carbon atoms or hydrogen to form a mixture of sultones and alcene sulfonic acids which is? then treated to transform the sultones into sulfonates. Other examples of detergent sulfates or sulfonates are the paraffin sulfonates containing about 10 to 20, preferably about 15 to 20 carbon atoms, for example the primary paraffin sulfonates prepared by reacting alpha- long chain olefins, bisulfites and paraffin sulfonates in which the sul-5 fonate groups are distributed along the paraffinic chain as described in the US Patents 2,503,280; No. 2,507,088; No. 3,260,741; Nos. 3,372,188 and German Patent 735,096, sodium and potassium sulfates of higher alcohols containing 8 to 18 carbon atoms, for example sodium aurylsufate and sodium tallow alcohol sulfate; the sodium and potassium salts of esters of alpha-sulfonated fatty acids containing about 10 to 20 carbon atoms in the acyl group, for example methyl alpha-sulfomyristate and alpha-sulfo-tallow methyl, ammonium sulfates of mono- or diglycerides of higher fatty acids C- | QC- | g, for example stearic monoglyceride monosulfate; the sodium and alkylolammonium salts of alkyl polyethenoxy ether sulfates produced by the condensation of 1 to 5 moles of ethylene oxide with one mole of higher alcohol (Cg-Ci 8) î sodium (C1-C6-higher alkyl) sodium glyceryl ether sulfonates; and sodium or potassium alkylphenol-polyethenoxy ether-sulfates with about 1-6 oxyethylene groups per molecule and where the alkyl radicals contain from about 8 to about 12 carbon atoms.

Suitable anionic detergents also include C 6 -C 6 acyl sarcosinates (e.g. sodium lauroyl sarcosinate), sodium and potassium salts of the reaction product of higher fatty acids containing 8 to 18 carbon atoms in the molecule, esterified with isethionic acid, and the sodium and potassium salts of (Cg-Cj g acyl) -N-methyl-taurides, for example sodium cocoyl-methyl-taurate J "35 and potassium stearoyl -methyl taurate.

v Examples of zwitterionic surfactants include derivatives of quaternary ammonium compounds \ 33. containing an aliphatic straight chain group of 14 to 18 carbon atoms and an anionic solubilization group of the sulphate or sulphonate type. Particular examples include 3- (N, N-dimethyl-N-hexadecyl-ammonio) -2-hy-s droxypropane-1-sulfonate, 3- (N, N-dimethyl-N-tallow) .am- monio) -2-hydroxypropane-1-sulfonate, 3- (Ν ,, Ν-dime thyl -N-tetradecyl-ammonio) -propane-1-sulfonate and 6-N, N- (di-methyl-N- hexadecyl-ammonio) hexanoate.

It has now been further discovered that the mixture of 10 non-ionic / amphoteric surfactants has surprisingly improved cleaning power compared to an equal weight of the same non-ionic surfactant alone or compared to the corresponding ethoxy-linked non-ionic surfactant with enough ethylene oxide to give the same cloud point. For example, using a carboxyethylated (higher fatty alkyl) imidazoline as an amphoteric surfactant, about 50 to 90% of the nonionic compound can be replaced by only about 10 to 40% of the amphoteric surfactant to achieve equal softening. 20 or higher (depending on the washing temperature) and a cleaner or equal or higher.

Since the amphoteric surfactant can act synergistically with the nonionic surfactant with regard to cleaning power, the total amount of nonionic and amphoteric surfactant in the detergent formula can be greatly reduced , for example at 3 to 20%, in particular 5 to 10% of 1 a -composition. The ratio of nonionic surfactant to amphoteric surfactant is not particularly fundamental, but for a given weight of nonionic surfactant, the cloud point rises as the amount of surfactant amphoteric increases. In general, ratios of the nonionic surfactant to the amphoteric surfactant of from about 1: 5 to 10: 1, preferably from 1: 3 to 6: 1, more preferably from 1: 2 to 4: 1 gives 35 will have improved cleaning and softening power (when it is necessary to raise the point 1Λ • of cloudy non-ionic surfactant above the washing temperature). Furthermore, in these ranges of quantities and ratios above, the mixture of “mixed nonionic / amphoteric” surfactants will be fully compatible with the softening compound that is cationic quaternary ammonium.

In addition to the so-called active materials of these compositions, other important constituents are the salt (s) of inert filler and humidity. A filler salt fa-10 promotes improvement of the mechanical properties of the product, generally improving the flow speed and - combating the tendency to adhesion. It can also promote rapid dissolution of the product in the washing water. Among the payload salts, the best is sodium sulfate, preferably in the anhydrous state. However, other fillers, including sodium chloride, sodium acetate and the alkali metal salts of these acids, can also be used, as can be starches, talcs, silicas and diver-20 its other charges which provide a support function.

The proportion of filler or mixture of fillers will be between 5 and 50%, preferably between 10 and 30%, and. better still, it will be around 20%, in particular when the anhydrous sodium sulfate is the feed salt. The humidity percentages will normally vary between 1 and 15%, preferably between 5 and 12% x and more preferably they will be around 8%. When these proportions are used, a granular or pulverulent product in particles is obtained, flowing well and which, by adjusting the particle size and the moisture content, can be prevented from being too powdery.

Regardless of the form of the bleaching detergent, its use in the washing process is essentially the same. The particulate composition is normally added to the wash water in an automatic washing machine so that the concentration in the wash water can be between about 0.05 and 1.5%, generally between 0.1 and 1.2%. The water to which it is added is preferably of medium or low hardness, for example of a hardness equivalent to 30 to 120 parts per 5 million in the form of calcium carbonate, but gold. can just as much use softer and harder waters.

The water temperature can be from 20 ° C to 100 ° C and is preferably from 60 ° to 100 ° C in case the textile material or the linen is able to withstand the high temperatures without deterioration or hue attenuation. When it is desired to operate a laundering at low temperature, the temperature can be maintained at 20-40 ° C and one can obtain under these conditions a correct cleaning and softening, although the product may not be as clean as when 'it is washed at higher temperatures. At the concentrations of the detergent compositions mentioned, the pH of the wash water is usually 7 to 11, preferably 8 to 10. At such pH, the composition is effective as a detergent, is not too harsh for the wash or the skin of the human body and it cleans and softens effectively. The weight ratio of the laundry to the wash water is generally about 1: 4 to 1:30 or 1:10 to 1:30.

The compositions of the present invention provide significantly improved softening power, at wash temperatures of at least 60 ° C, compared, for example, to identical formulations, with the difference that the amphoteric surfactant does not is not used to raise the cloud point above 60 ° C. This effect could not have been predicted from the prior art because there was no known correlation between the cloud point of the nonionic surfactant and the softening power.

- An example of formulation of a powdered detergent-softener composition according to the invention is given below, all the parts and all the percentages J ’.

v

B

4 36 "" being expressed by weight:

COMPOSITION A

"C-j ^ -C ^ / EO fatty alcohol 11: 1 2.0

Rexoteric OASF 4 * 5 (45% active ingredient) 8.9 5 Sodium metasilicate 8.0

Sodium tripolyphosphate 28.0

Sodium pyrophosphate. 10 H ^ O 24.0

Sodium orthophosphate 0.5

Ni triotriacetate (NTA), sodium salt 8.0

Dimethyl-distearyl ammonium chloride (93% active ingredient) 8.0

Minor and various additives (for example, perfume, optical brightening agents, humidity, etc.) the rest 15 Dirty fabrics are washed at 60 ° C in approximately 20 liters of water with a hardness corresponding to 0.12 g / liter using approximately 100 g of Composition A.

The washed fabrics are evaluated for their flexibility by a jury of 4 specialists on multiple replicas after a cumulative wash. For comparison, an identical composition is prepared with the difference that Rexoferic OASF is not used and that the quantity of fatty alcohol C 11 -C 1 / EO: 11: 1 is increased to 8% (Example Comparative), or else approximately 15% of fatty alcohol in C ^ 'Cj ^ / EO 30: 1 (Reference Example 1) or 15% of nonyl-phenol / E0 20: 1 (Reference Example 2) is used. in place of the nonionic surfactant and the amphoteric surfactant used in Composition D, and each of these compositions is evaluated in the same manner as for Composition A. Each of the compositions is scored on a scale of 1 to 10, the note "10" corresponding to the best quality and representing the same detergent composition (without cationic softener) and a softener added to the rinsing cycle (dimethyldis-35 tearyl ammonium chloride). On this scale, Composition A and Reference Examples 1 and 2, obtain a grade of s ~ - I 37 I * 5-6 and have an equal cleaning power. Composition I of the Comparative Example receives a score of 2-3 only.

I -e When in Composition A fatty alcohol in I i ^ 12 "^ 15 ^^ 11: 1.is replaced by an equal amount of II ^ nonyl-phenol / EO 4: 1 or nonyl-phenol / EO 8: 1 or a fatty alcohol I in C ^^ C-jg / EO 7: 1 or a fatty alcohol in C ^ -C-jg / EO 5: 1, I we also obtain a score of 5-6.

I We also obtain good results by replacing the dimethyl-distearyl ammonium chloride of I Composition A with hydrogenated dimethyl disulphide (I n) ammonium, diethyl disoja-ammonium chloride, I dimethyl-stearyl ketal-ammonium chloride or methyl-I 2-hexadecyl-1-methyl-1 [2-dodecoyl amido) ethyl] I imidazolinium sulfone, and their corresponding bromides, sulfates and hydroxides I 15 IJ.

I We also obtain good results by replacing Rexoteric OASF from 1 to Composition A by Rexoteric CSF, I Miranol DM, I î 20 CH, 0

I I O II

I (C10-C14) n-a1kyl-N + CH2C0 ', I CH, I 3

I * OR

IH "I 25 n-alkyl (C12-C18-C-N + -CH20CH2CH2C0 'I \ / cH2 · I" 2 I 30 I The detergent-softening compositions of the present invention have the particular advantage that, because they can provide better cleaning power with lower total amounts of surfactants, more highly concentrated formulations can be prepared and packaged for use by the consumer.

I 1 IS »« 38

The methods of making the compositions described herein are generally well known in the art, and reference is made in particular to the U.S. Patent.

No. 4,269,722 in which relatively high den ionic powders of den-5 loaded with a detergency builder are produced from spray dried base beads which are spray coated with nonionic detergent ( which may contain other minor conventional additives such as colorants, perfumes, brighteners, bleaches, etc.) This patent is cited for reference.

»·»

Claims (10)

1. Detergent laundry composition, capable; washing and softening soiled fabrics in an aqueous washing liquid * at a high temperature of at least 60 ° C, ^ 5 said composition being characterized in that it comprises (a) a non-surface active agent water-soluble ionic having a cloud point below the elevated temperature; (B) a fabric softening agent of the cationic compound type, insoluble in water, of quaternary ammonium, and chosen from the group comprising the compounds of formulas III and IV: 15 K ^ r3 "] + JX“ (III) R2 20 r5- ^ X * (IV> XL R6 r7., In which and R ^, and Rg and Rg each independently represent long chain aliphatic radicals of 16 with 22 carbon atoms, Rg and R ^, and Ry each independently represent lower alkyl radicals, or Rg may be the group -RgNHCRg in which Rg is a long chain aliphatic radical of 16-22 atoms carbon, and Rg is a divalent alkyl radical of 1 to 3 ^ carbon atoms, and X is a salt-forming anion; and y (c) an amphoteric surfactant in an amount sufficient to>> raise the point of composition disorder at a temperature above the high temperature λ I ♦ 40 2. Composition according to claim 1, characterized in that the nonionic surfactant (a) is I i? chosen from the group comprising the compounds of formulas i I and II: 3. Composition according to claim 1, characterized in that the amphoteric surfactant is chosen from the group consisting of:! (1) detergents of the betaine type of formula: I R, 0 ς 20 Rj. n + -r4-c-0- R3 I "Ί I (2) detergents of the betaine type with an alkyl bridge I of formula: 25 n SHI R1-CH2-CN-CH2CH2CH2-N + -R4-CO" h I (3) imidazoline-type detergents of formula I 30 I CHoCÛOH 0 1 + “- IR, -C _ N -R.-O-CH-.CO 'l I 4 2 \ / CH2 I> 35 CH2 h * 41 K (4 ) detergents of the alkyl iminopropionate type of formula H r1-n-ch2ch2cooh ^ (5) detergents of the iminodipropi.onate type of alkyl k of formula: CH, CH9C00H / 2 2 R] -N 10 \ CH2CH2C00H (6 ), detergents of the imi nodi propi onate type, ether-bridge alkyl of formula 15 ch2ch2cooh r1-och2ch2ch2-n ^ s' ^ CH2CH2C00H L 20 (7) amphoteric detergents based on copra- imidazoline of formula ΙΊ H 0 l + r, - c_n + -ch2och2ch2co 25 P | N CH? xch / (8) amphoteric detergents based on (higher fatty alkyl) imidazoline carboxyethylated of formula 30 HoC HN + -CH0CH9COO “i 1 2 2 hor2— rt = c-R1 35 and their mixtures, in which R- | represents an aliphati- radical * * Λ 42% ν that from 7 to 20 carbon atoms, Rg and R3 each represent an lower alkyl group - 1 lower than 1 to 4 carbon atoms, and * R4 represents a divalent lower alkyl radical "5 from 1 to 4 carbon atoms. 4. Composition according to claim 1, characterized in that it comprises, on the basis of the weight of the active ingredients relative to the total weight of the composition 10 approximately 0.5 to approximately 20% of (a) approximately 1 to approximately 20 % of (b) about 1 to about 20% of (c) and the rest (d) consisting of detergency builders, inert fillers and moisture. 5 - Composition according to claim 4, characterized in that the ratio of (a): (b) is 1:10 to 5: 1, and the ratio of (a) :( c) is 1: 5 at 10: 1. . 5 R0 (CH2CH20) nH (I) R • -flQ ^ -0 (CH2CH20) nlH (II) I in which R is a primary or secondary alkyl chain, straight or branched, from 8 to 22 carbon atoms, IR 'is a primary or secondary alkyl group of 7 to 12 I carbon atoms, and each of n and m is a number having I an average value of 4 to 14. 6. Composition according to claim 1, characterized in that it further comprises at least one detergency additive chosen from the group consisting of mineral salts with detergency builder, organic salts with detergency builder, agents soil suspension, anti-redeposition agents, fatty amides, foam suppressants, anti-foaming agents, optical brightening agents, 25 soluble dyes, pigments, brighteners, anti-aging agents, enzymes, corrosion inhibitors, pH modifiers, pH buffers, bactericides, fungicides, preservatives, bleaches, bleach stabilizers, bleach activators, perfumes and water. 7. Composition according to claim 1, characterized in that it comprises, on the basis of the weight of the active substances, i (a) approximately 0.5 to approximately 20% of the nonionic surfactant; (b) about 1 to about 20% of the cationic softener; (c) about 1 to about 20% of the surfactant am-s? photere; {(d) about 20 to about 85% detergency builder salts; (e) 0 to about 40% corrosion inhibitors; (f) 0 to about 40% bleaches and activators; (g) 0 to about 10% of soil suspending agents or anti-redeposition; (h) 0 to about 10% anti-yellowing agents; (i) 0 to about 2% of each of the following additives: optical brightening agents, colorants, brighteners, bactericides, fungicides and enzymes; (J) 0 to about 15% anti-foaming agents or foam suppressants; (k) 0 to about 5% of each of the following additives: pH modifiers and pH buffers; and • 5 · * (1) the remainder being water. 20 8 - Composition according to claim 3, characterized in that it comprises approximately 1 to 10% of Ja), approximately 6 to 9% of (b), approximately 1 to 10% of (c), and the rest ( d), consisting of detergent builders, inert fillers and moisture, the weight ratio of (a) :( b) being 1: 8 to 4.5: 1 and the ratio of (a) :( c) being 1: 2 to 4: 1. 9. A method for cleaning and softening soiled fabrics in washing water at a temperature of at least about 60 ° C, characterized in that it consists in washing the fabrics in an aqueous solution of the composition se-Ion la claim 1. 10. Method according to claim 9, characterized in that the temperature of the washing water is approximately | 100 ° C. r D