SE449372B - LOW PHOSPHATE CONTENT COMPOSITION - Google Patents

Description

449,372 mega detergents containing a high proportion of nonionic surfactants.

The same detergent compositions, with or without phosphate or other detergency-supporting components, are also capable of removing clay dirt particles at least as well, and in some cases substantially better than conventional, granular detergent compositions having normally high detergency-assisting additives and additives. a number of different beneficial properties, as they contribute to e.g. soft treatment and regulation of the static electricity of the textiles and in addition they prevent color transition.

The compositions according to the invention thus give the consumer access to a perfect textile cleaning and textile treatment package. These results, which are extremely superior to the results previously obtained, in particular as regards the removal of greasy and oily dirt, are the result of a previously undetermined cleaning ability of certain selected cationic surfactants, when used in the presence of certain selected nonionic surfactants in accordance with the requirements of the cloud point and the reduced cation monomer concentration specified herein.

It is thus an object of the present invention to produce detergent compositions which provide extremely good removal of greasy and oily dirt as well as dirt caused by body exudates.

Another object of the invention is to provide detergent compositions which give extremely good effects in terms of removal of particulate dirt and textile conditioning, in addition to extremely good effect in terms of the removal of greasy and oily dirt and caused by body exudates. dirt, in the presence or absence of washing effect supporting components.

Furthermore, it is an object of the invention to produce detergent compositions which can be used in a large number of different physical forms, such as e.g. in the form of liquid, paste or powder or in granular or solid form, or in combination with a carrier material, such as e.g. a backing material.

A further object of the invention is to provide a method of washing textiles to remove greasy and oily soils and dirt caused by body exudates, as well as particulate soils, using cationic and nonionic surfactant-containing detergent compositions.

The present invention relates to a detergent composition which gives a pH of at least 6.5 in the aqueous washing solution and is substantially free of oily hydrocarbon materials, cationic materials having 13 or more ethylene oxide groups and phosphate material, which composition as a essential ingredient contains 10 to 95% by weight of a surfactant mixture, consisting essentially of: (a) a biodegradable nonionic surfactant of the formula R (OC 2 H 4) nOH, where R represents a primary or secondary alkyl chain having 8 to 22 carbon atoms and n represents an average , which amounts to 2 to 12, and with an HLB value of 5 to 17, and (b) a cationic surfactant, which is free of hydrazinium groups and has the formula R1mR2XYLZ, each of which has R1 with a straight or branched alkyl or alkenyl group, designated groups are an organic group, optionally substituted with up to 3 phenyl or hydroxyl groups and optionally interrupted by up to 4 structures, selected from ooo RR o || u ll | | Il, -c-o-, -o ~ c-, -c N-, -N-c-, o H H o o o n H o II I I I | 'I u' I u -cN-, -Nc-, -o-, -oco-, -ocN-, -Nco-, and mixtures thereof, each of the groups denoted by R1 containing 8 to 22 carbon atoms, and which may additionally contain up to 12 ethylene oxide groups, m is a number from 1 to 3, each of the groups denoted by R1 having 449,372 at most 14 carbon atoms, when m is 2, and at most 11 carbon atoms, when m is 3, each of the groups represented by R 2 is an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms or a benzyl group, at most one R 2 group in a molecule being benzyl, x is a number from 0 to 11, wherein any remaining bonds at the carbon atoms are hydrogen atoms, Y is selected from: (1) -N + - _ I “šè / + (2) -c \ N_.C ..

I (3) -š + - I (4) -s * - I (5) -š + - where p is 1 - 12 IH (c2n4o) p (ï2a4o) pa (6) -N * - where p 1 bath cases are 1 - 12 I (c2H40) pH I c (7) \\ c4%. \: N "I u / C" \ C / C \ | 449 372 (8) N, + Q and _ C (9) mixtures thereof, L is 1 or 2, the Y groups being separated by a grouping selected from R 1 and R 2 analogs having 1 to 22 carbon atoms and two free carbon single bonds, when L = 2, Z represents an anion in sufficient number to give electrical neutrality, the cationic surfactant being at least dispersible in water in admixture with the nonionic surfactant, the ratio of the nonionic to cationic the surfactant is in the range 5.1: 1 to 100: 1 and the surfactant mixture has a "cloud point" as below of 0 to 95 ° c.

Preferred compositions are those in which the reduced cation monomer concentration in the surfactant mixture is about 0.002 to about 0.2. Preferred cationic surfactants are water soluble and have a critical micelle concentration (CMC) above 10 ppm.

The conventional, cationic fabric softening treatment materials having two alkyl chains of about 18 carbon atoms each are substantially insoluble and cannot constitute the only cationic component in the compositions of the invention.

The compositions of the invention are formulated in such a way that they have a pH of at least 6.5 in the washing solution at conventional dosage levels to optimize the washing action on greasy and oily dirt, as washing solutions in the acidic pH range tend to reduce the effect on such dirt. Preferably, the compositions are alkaline in nature when placed in the washing solution and have a pH value above about 7.5, in particular at least about 8. Some of the cationic / nonionic systems according to the invention achieve optimal removal of greasy / oily dirt at these higher pH values. In such systems, the total washing effect can be improved by weighing the pH of the washing solution during the washing process. M The compositions are free from oil-like hydrocarbon materials, such as many solvents used in chemical washing, mineral oil, paraffin oil and kerosene, as these materials (which in themselves are oil-like in nature) load the washing liquid with excessively much oil-like material, thereby reducing the cleaning effect of the compositions according to the invention. .

The cationic component is free of hydrazinium groups due to the relatively high level of toxicity of these groups, which in turn makes them unsuitable for use in the compositions of the invention.

Preferred compositions contain nonionic surfactant: cationic surfactant ratios between 5.1: 1 and 50: 1, preferably from 6: 1 to 40: 1 and in particular from 6: 1 to 20: 1. The removal of greasy and oily dirt is increased to a large extent at ratios between about 8: 1 and about 20: 1, the improvement in the washing effect being generally easiest to observe when the amount of nonionic surfactant is increased, so that the ratio between nonionic surfactant and cationic surfactant is above 5.1 ~ 1 449 372 and approaches 8: 1.

Preferred compositions may contain mixed cationic and / or mixed nonionic surfactant systems. The cationic surfactants should all be within the above definition of the cationic surfactants, however, small amounts of other cationic materials may be tolerated. The mixed nonionic surfactant systems may contain nonionic surfactants which fall outside the above definition (e.g. eg alcohol ethoxylate having an average of more than 12 ethylene oxide groups per molecule), as long as at least one of the nonionic surfactants in the mixture falls within the given definition of the nonionic surfactants and this nonionic surfactant is included in such an amount that it falls within within the framework of the required ratio between nonionic surfactant and cationic surfactant. When the nonionic surfactant mixture contains a nonionic surfactant (or nonionic surfactants) which falls outside the definition of nonionic surfactants, the ratio between the surfactant (or surfactants) which fall within this definition and the surfactant which does not fall within the scope of this definition, preferably in the range of 1: 1 to about 5: 1.

The compositions of the present invention contain as essential ingredient 10 to 95% by weight, in particular from 20 to 90% by weight, of a mixture of the specially defined nonionic and cationic surfactants in the stated ratios. It is preferred that the detergent compositions contain at least about 1% of the cationic component, as otherwise sufficient cationic surfactant may not be present in the wash solution to provide the desired cleaning and conditioning results.

Preferred compositions further contain not more than about 10% of the cationic component with respect to cost and commercial availability.

The compositions of the invention may contain up to about 60% of an electrolyte (although low concentrations of about 1-20% are preferred), such as e.g. a detergent auxiliary component as well as other auxiliary or auxiliary components of the type commonly found in detergent compositions, as further explained below. The compositions are substantially free of phosphate material, however, low concentrations of a detergency-supporting phosphate material less than 20% by weight of the composition as a whole can be tolerated. For environmental reasons, it is preferable that the compositions are phosphate-free. To the extent that phosphate materials or other electrolytes are present in these compositions, they primarily affect the cleaning effect by modifying the temperature at the cloud point of the nonionic / cationic surfactant mixture, as described below.

The primary use of the compositions of the invention is in conventional household washing procedures. The compositions can also be used for other cleaning purposes, including the pre-treatment of greasy and oily stains and in industrial washing procedures. Processes for washing textiles with the compositions according to the invention, which provide extremely good removal of greasy and oily dirt and extremely good contributions to the textile conditioning, are also described herein. In these processes, the detergent compositions are used under such temperature conditions that the aqueous wash solution is either at, or near (ie within about 20 ° C from) the cloud point (ie, the temperature at which a nonionic surfactant phase is separated in the wash solution) for the nonionic / cationic surfactant mixture.

This can be conveniently achieved by formulating these nonionic / cationic surfactant mixtures in such a way that their cloud point falls between 0 and 9500, in particular between 10 and 70 ° C, in particular between 20 and 7000, in particular from 30 to SOOC. During the washing process, the temperature of the washing solution is kept within this temperature range and within 20 ° C of the temperature at the cloud point. The washing effect is further improved when the temperature of the aqueous washing solution is within about 15 ° C, in particular within about 10 ° C, from the cloud point temperature of the nonionic / cationic surfactant mixture. v; Nonionic component The nonionic surfactants used in the compositions of the invention are biodegradable and have the formula R (OC 2 H 4) nOH, where R represents a primary, branched or secondary alkyl chain having 8 to 22, preferably 10 to 20, carbon atoms and n is an average of to 2 to 12, in particular 2 to 9. Although primarily linear alcohol ethoxylates (eg alcohol ethoxylates, produced from organic alcohols containing about 20% 2-methyl branched isomers, commercially available from Shell Chemical Company under the trade name " Neodel ') is preferred from a washing effect point of view, it is possible to formulate compositions using secondary alcohol ethoxylates, which provide both optimal clay removal and optimal fat / oil removal at approximately the same nonionic surfactant: cationic surfactant ratio (nonionic surfactant: cationic surfactant ratio is between 5.1: 1 and 15: 1).

However, compositions utilizing these secondary alcohol ethoxylates tend to require higher dosage levels in the wash solution to achieve their best effect than is the case with compositions containing primary alcohol ethoxylate.

The nonionic surfactants have an HLB value (hydrophilic-lipophilic balance) of 5 to 17, preferably from about 6 to about 15. Optimal fat / oil removal is achieved when the nonionic surfactant has an HLB value of about 9 to about 13, in in particular between about 10 and about 12. For optimal removal of greasy / oily dirt, it is preferable in such compositions to use cationic surfactants, which are relatively soluble, such as e.g. quaternary ammonium compounds with a single long chain (eg C 10 -C 18 alkyl) or quaternary ammonium compounds containing in total not more than about 28 carbon atoms in their R 1 and R 2 groups. The HLB value is defined in detail in Nonionic Surfactants by M.J. Schick, MARCEL Dekker, Inc., 1966, p. 607 - 613, to which reference is made herein.

In preferred nonionic surfactants, n is 2 to 7, in particular from 4 to 7.

Nonionic surfactants, which fall within the definition of the nonionic component, comprise a secondary 449 572 C15 alcohol polyethoxylate containing on average 5 moles of ethylene oxide, a C12 alcohol polyethoxylate having an average of 5 moles of ethylene oxide, a C10 alcohol polyethoxylate containing an average of 4 moles of ethylene oxide, a C14 alcohol polyethoxylate having an average of 4 moles of ethylene oxide. This latter surfactant is particularly useful for washing textiles in cold water. Examples of preferred nonionic surfactants useful in the compositions of the invention are a C 2 alcohol polyethoxylate containing an average of 3 moles of ethylene oxide, a C 12 -C 13 alcohol polyethoxylate containing on average 3 moles of ethylene oxide and the same product. which has been deducted by means of a so-called stripping process to remove substantially all fractions with lower ethoxylate and non-ethoxylated material, a C14-C15 alcohol polyethoxylate having an average of 7 moles of ethylene oxide, a C12-C13 alcohol polyethoxylate containing on average 6.5 moles of ethylene oxide, a C12 alcohol polyethoxylate having an average of 5 moles of ethylene oxide, a coconut alcohol polyethylethoxylate having an average of 5 moles of ethylene oxide, a C12-C13-3 alcohol polyethoxylate containing on average 9 moles of ethylene oxide, a C14-C15 alcohol polyethyl ethoxylate 3 moles of ethylene oxide, a C14-C15 alcohol polyethoxylate having an average of 4 moles of ethylene oxide and a C14-C15 alcohol polyethoxylate containing an average of 9 moles of ethylene oxide.

Specific examples of nonionic surfactant mixtures in which both components fall within the definition of the nonionic component are: a mixture of a C14-C15 alcohol polyethoxylate containing on average 3 moles of ethylene oxide ("Neodol 45-3") and a C14- C15 alcohol polyethoxylate, containing on average 7 moles of ethylene oxide ("Neodol 45-7"), in a ratio of the less ethoxylated nonionic surfactant to the more ethoxylated nonionic surfactant of about 1: 1 to about 3: 1, a mixture of a C10 alcohol polyethoxylate having on average 3 moles of ethylene oxide together with a secondary C15 alcohol polyethyl xylate containing on average 9 moles of ethylene oxide (Tergitel R 1s-s-9), in a ratio between the less ethoxylated nonionic surfactant and the more ethoxylated nonionic surfactant of about 1: 1 to about 4: 1 and a mixture of "Neodol 45-3" and Tergitol (:) 15-S-9 in a ratio of the less ethoxylated the nonionic surfactant and the higher ethoxylated nonionic surfactant of approx 1: 1 to about 3 ~ 1.

Preferred nonionic surfactant mixtures contain alkyl glyceryl ether compounds in addition to the necessary nonionic surfactant.

Particularly preferred glyceryl ethers have the formulas R-OCH 2 -cH-c 2 zone and Ro (cuznzo) nczxzacenzone where R represents an alkyl or alkenyl group having about 8 to about 18, preferably 8 to 12, carbon atoms or an alkaryl group having about 5 to 14 carbon atoms in the alkyl chain and n is 1 to about 6. These materials are used in compositions with the nonionic surfactant component of the invention in a ratio of nonionic surfactant to glyceryl ether of about 1: 1 to about 4: 1, in particular about 7: 3. .

Preferred compositions of the invention are substantially free of fatty acid polyglycol ether diester compounds, such as e.g. polyethylene glycol 600 dioleate or polyethylene glycol 800 distearate. Such additives do not give a positive effect and can possibly even entail a disadvantage with regard to the achievement of the dirt removal and the textile conditioning, which is possible according to the invention.

Other nonionic surfactants well known in the cleaning art may be used in combination with one or more of the nonionic surfactants which fall within the definition of nonionic surfactants useful in the present invention to provide useful nonionic surfactant mixtures. Examples of such surfactants are listed in U.S. Pat. Nos. 3,717,630 and 3,332,180, to which patents are referred herein. As non-limiting examples of suitable nonionic surfactants which can be used in conjunction with the required nonionic surfactants defined above, there may be mentioned the condensation products of aliphatic alcohols with ethylene oxide which differ in alkyl or ethylene oxide chain length (e.g. more than 12 ethylene oxide groups per molecule), so that they fall outside the above definition. These complementary nonionic surfactants may also be of the semipolar type, including water-soluble amine oxides containing an alkyl group having about 10 to 28 carbon atoms and two groups selected from the group consisting of alkyl groups and hydroxyalkyl groups. A preferred amine oxide is C 12 -C 14 alkyl dimethylamine oxide. In addition to their surfactant properties, these compounds can also be incorporated in amounts of about 3 to about 20% of the composition to modify the foaming properties of the detergent compositions in order to make them miscible with particular types of detergent compositions. Other semipolar surfactants include water-soluble phosphine oxides containing an alkyl group having about 10 to 28 carbon atoms and two groups selected from a group consisting of alkyl groups and hydroxyalkyl groups having about 1 to 3 carbon atoms, and water-soluble sulfoxides containing an alkyl group having about about 10 to 28 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties having 1 to 3 carbon atoms.

Cationic component The cationic surfactants used in the compositions of the invention have the formula R1mR2xYLZ, as stated above.

The particular cationic component to be included in a given system is highly dependent on the particular nonionic component to be used, and is selected in such a way that it is at least dispersible in water when mixed with the nonionic surfactant. The cationic surfactant is selected, taking into account the nonionic surfactant used in the particular case, in order to meet the requirements discussed below regarding the cloud point of the detergent composition. Mixtures of these cationic materials can also be used in the compositions of the invention. Preferred cationic surfactants are those which have critical micelle concentrations below about 500 ppm, especially below about 100 ppm.

In preferred cationic materials, L is equal to 1, p has a value from 1 to 12, preferably 1 to 10, and Y represents <1 449 372 13 t \\ N / L å _ I (? 2H 40) PH -N + "1" Ci + m, -N + -, -N + _ 1 \ N-ï- II (c2H40) pH (° 2H4 °) pH or mixtures thereof. However, L can be equal to 2, whereby cationic components containing two An cationic component is given below: z ï fi š ï fl š z 'clsaš5- * ï-cH2-cH2-cH2-ï * -CH5 CH§ CH; Other cationic materials useful in com- positions according to the invention, comprises phosphonium and sulfonium materials.

In preferred cationic materials described above, where m is equal to 1, preferably x = 3 and R 2 represents a methyl group. Preferred compositions of this type with a single long chain include those in which R 1 represents a C 10 -C 18 alkyl group. Particularly preferred components in this class include C16 (palmitylalkyl), trimethylammonium halide, tallow alkyltrimethylammonium halide and coconut alkyltrimethylammonium halide. In preferred systems, tallow alkyl trimethylammonium or coconut alkyl trimethylammonium material is combined with a nonionic surfactant selected from the condensation products of C12-C13 alcohol with 4-10 moles of ethylene oxide or the condensation product of C14-C15 alcohol with 6-10 moles of ethylene as ethylene for example the condensation product of C12 alcohol with 5 moles of ethylene oxide, the condensation product of C12-C13 alcohol with 6.5 moles of ethylene oxide, the condensation product of C14-C15 alcohol with 7 moles of ethylene oxide or mixtures thereof, in proportions between 449 372 14 in particular approx. 7: 1 to about 20: 1 and in particular about nonionic surfactant and cationic surfactant of from 5.1 - 1 to 30 - 1, 10: 1. In addition to extremely good removal of greasy and oily dirt, excellent removal of particulate dirt is obtained. when using the condensation product of C12-C13 alcohol with 2 - 4 moles of ethylene oxide or the condensation product of C14-C15 alcohol with 3 - 6 moles of ethylene oxide in nonionic surfactant / cationic surfactant ratios of 5.1: 1 to about 10: 1. These compositions may additionally contain up to about 15% alkanolamine, preferably monoethanolamine, as a base, to increase alkalinity and to increase the removal of dirt from body secretions. For example, coconut alkyltrimethylammonium chloride can be combined with the condensation product of C12 alcohol with 5 moles of ethylene oxide, the condensation product of C12-C13 alcohol with 6.5 moles of ethylene oxide or mixtures thereof in ratios of nonionic surfactant and cationic surfactant of 5.1: 1 to about 20 mol. : 1, in particular 5.1: 1 to about 9: 1. In another composition, coconut alkyltrimethylammonium chloride is combined with the condensation product of C1-C15 alcohol with 7 moles of ethylene oxide in nonionic surfactant: cationic surfactant ratios of from , 1: 1 to about 15: 1.

Another preferred composition utilizes cationic surfactants of the formula C s 1 | + 2 - “l 2 R -N -R 2, where R, R and Z are as defined above, in combination with the condensation product of C12-C13 alcohols with 5 10 moles of ethylene oxide or the condensation product of C14-C15 alcohol with 5 to 10 moles of ethylene oxide, such as the condensation product of C12 alcohol with 5 moles of ethylene oxide, the condensation product of C12-C13 alcohol with 6.5 moles of ethylene oxide, the condensation product of C14-C15 alcohol with 7 moles of ethylene oxide and mixtures thereof in the ratio of nonionic surfactant to cation tensile of from 5.1 = 1 to 15 = 1, in particular About 449 372 15 7: 1.

In cases where m = 2, it is preferable that x is equal to 2 and that R 2 represents a methyl group. In this case, the RT must not contain more than 14 carbon atoms. A preferred cationic material in this class is dicoco nut alkyl (G12-C14) -dimethylammonium halide.

Preferred compounds of this type utilize dicoconutalkyldimethylammonium halide together with the condensation product of C12-C13 alcohol with 6-10 moles of ethylene oxide or the condensation product of C14-C15 alcohol with 5-9 moles of ethylene oxide, e.g. the condensation product of C12-C13 alcohol with 6.5 moles of ethylene oxide, the condensation product of C14-C15 alcohol with 7 moles of ethylene oxide and mixtures thereof in proportions of nonionic surfactant and cationic surfactant of between 5.1: 1 and 15: 1, "in particularity from about 6: 1 to about 12: 1. Extremely good removal of particulate dirt in addition to excellent washing effect in terms of removal of greasy / oily dirt can be obtained using the condensation product of C12-C13 alcohol with 4-8 moles of ethylene oxide or the condensation product of C14-C15 alcohol with 4-8 moles of ethylene oxide in nonionic surfactant / cation surfactant ratios of 5.1: 1 to 15: 1.

In cases where materials with three long chains are used (m = 3), x is suitably equal to 1 and R 2 represents a methyl group. In these compositions, R 1 represents a C 8 - C 11 alkyl group. Examples of particularly preferred three long chain cationic materials are trioctylalkyl (C8) methylammonium halide and tridecylalkyl (C10) methylammonium halide.

Another type of preferred cationic surfactants for use in the compositions of the invention are the alkoxylated quaternary alkyl compounds. Examples of such compounds are given below: 449 572 W ÉHP, 'CH 3 - + + z RT - (C 2 H 40) pH H (oc 2 H 4) pN - (c 2 H 40) pH z R R where in both examples there is a number between 1' and 12 , preferably 1 to 10 (wherein the total number of ethylene oxide groups in a molecule does not exceed about 13), and each of the groups denoted by R is a C 10 - C 20 alkyl group. It is preferred that these compounds do not contain more than a total of about 10, preferably at most about 7, ethylene oxide groups to obtain the best removal of greasy and oily dirt.

The compounds of the present invention must be substantially free of cationic compounds containing about 13 or more ethylene oxide groups. These compounds tend to be relatively biodegradable, furthermore they do not improve the cleaning or textile conditioning effects obtained with the compositions and they can in some cases also reduce the overall washing effect achieved by the compositions. It should be noted that polyethoxylated cationic surfactants with a relatively low degree of ethoxylation, such as e.g. the ones described above, show better biodegradability and can advantageously be incorporated into the compositions according to the invention.

A particularly preferred type of cationic component has the formula: R 2 I - R 3 - (z 1) a - (R 4) n -z 2 - (cH 2) m W * -R 2 x R 2 where R 2 represents C 1 - C 4 alkyl or hydroxyalkyl, R 3 represents a straight or branched alkyl, alkenyl or alkylphenyl group having 5 to 30 carbon atoms or 17 449 572 2 2 X - R 2 - + η- (CH 2) s -, where s is 0 - 5, R 2 R 4 represents C -alkylene or -alkenylene, a is 0 or 1, close or1 and n = 1, close to 1, more1-s, 'z "and z2 each selected from a group consisting of OOOQHHOOHHOHH ll HII Il HI au -co-, -oc-, -o ,, -oco-, -cN-, -Nc-, -ocN-, -Nco-, and wherein at least one of the groups is an ester, reverse ester, amide or reverse amide and X represents an anion which the compound is at least dispersible in water, preferably selected from the group consisting of halide, methyl sulphate, sulphate and nitrate, preferably chloride, bromide, iodide, methyl sulphate and sulphate.

In addition to the benefits of the other cationic surfactants described herein, this particular cationic component is desirable from an environmental point of view, as it is biodegradable, provides acceptable compounds from an environmental point of view, both in terms of its long alkyl chain and its nitrogen-containing segment. These preferred cationic components are useful in nonionic surfactant / cationic surfactant mixtures having a ratio of nonionic surfactant to cationic surfactant of from about 1: 1 to about 100: 1. However, when used in the compositions of the present invention, they are used in surfactant compositions which have ratios of nonionic surfactant to cationic surfactant of 5.1: 1 to about 100: 1, in particular from 5.1: 1 to about 50: 1, in particular from about 6: 1 to 40: 1, especially about 6: 1 to about 20: 1.

Particularly preferred cationic surfactants of this type are the choline ester derivatives of the following formula: 449 572 18 g cn3 3,, + _ R - -O-CH2CH2-q * CH3 X CH3 as well as the compounds in which the ester bond in the formula above is replaced by a reverse ester bond, amide or reverse amide bond.

Particularly preferred examples of this type of cation surfactants include quaternary stearoylcholinesterammonium halides (R 3 = C 17 alkyl), quaternary palmitoylcholine ester ammonium halides (R = C 15 alkyl), quaternary myristoylcholine ester ammonium halides and R = C alkylcholinesterammonium halides (R = C15 - C17 alkyl).

Further preferred cationic components of the cholinester type are illustrated by the structural formulas given below, in which p may be from 0 to 20.

O CH 3 n +3 _ R -oc- (cHQp-c-ø-c fi zcuz-Iïï -cH3 x cn3 f fl ß i: m3 x "cz flfi fršll-cnz-CHZ-oc- (cnz) pco-caz-cnz-lïf- ca3 x cH3 cH3 The preferred cationic choline derivatives discussed above can be prepared by direct esterification of a fatty acid of the desired chain length with dimethylaminoethanol in the presence of an acid catalyst.The reaction product is then quaternized with a methyl halide to give the desired cationic material. The choline-derived cationic materials can also be prepared by direct esterification of a long chain fatty acid of the desired chain length together with 2-haloethanol in the presence of an acid catalyst.The reaction product was then used to quaternize trimethylamine so that the desired cationic component can be formed.

Another type of new, highly preferred cationic materials has the formula: R 6, R 2, R 2 -O 3 (cH) no_7y- (z 2) a- (R 7) t -22- (cH 2) m N * -R 2 x . R 2 In the above formula, each of the groups represented by R 2 represents a C 1 -C 4 alkyl or hydroxyalkyl group, preferably a methyl group. The groups denoted by R are either hydrogen or C 1 -C 3 alkyl, preferably hydrogen. R 5 represents a straight or branched C 4 - C 30 alkyl, alkenyl or alkylbenzyl group, preferably a C 8 - C 18 alkyl group, in particular a C 12 alkyl group. R 5 represents a C 1 - C 10 alkylene or alkenylene group. n is 2 - 4, preferably 2, y is 1 - 20, preferably from about 1 to 10, in particular about 7, a may be 0 or 1 and t may be 0 or 1, but t = 1, when a is 1 and m is 1-5, preferably 2. Z 2 is selected from the group consisting of OOHHO 3 HOOH II II II II III I; T -co-, -c-, -O-, -oco-, -cN-, -Nc-, -ocN-, -N in -CO-, and Z1 are selected from the group consisting of: OOOHHOHO -Q- 0-, -Q-, -C-¿-, -¿-Q-, -¿-gO-, wherein at least one of the Z1 and Zz groups is selected from a group consisting of ester, reverse ester, amide or reverse amide. X represents an anion which makes the compound least dispersible in water and is selected from a group consisting of halides, methyl sulphate, sulphate and nitrate, in particular chloride, bromide, iodide, methyl sulphate and sulphate. Mixtures of the above structures can also be used. 444,372 These surfactants, when used in the compositions of the invention, provide excellent soil removal in terms of both particulate dirt and body and greasy and oily soils. In addition, the detergent compositions regulate the static electricity and thus give washed textiles a softer grip and also prevent the color transition in the washing solution. Furthermore, these new cation surfactants are desirable from an environmental point of view, as both their long chain alkyl segments and their nitrogen segments are biodegradable.

Preferred embodiments of this type of cationic component are esters, wherein R 2 represents a methyl group and Z 2 is an ester or reverse ester group. Below are some special examples of these compounds, where r is 0 or 1 and y is 1 - 20.

O ïH3 H 5 R -o (cH2cH2o) y- (cnz) tco-cnz-CH2-N * -CH3 x CH3 o ïH3 R5-o (cH2cH2o) yc-CH2 -? + - CH3 x 'CH3 CH3 o CH3 R5 -o (ÅHcH2o) yc-cnz-N * -CH3 x "r ca cH3 o I 3 U R5-o (cHcH2o) y- (cH2) tco-cnz-cnz-N * -ca x 3 CH3 21 449 372 oo H 5 HR -o (cH2cH2o) yc- (CH2) tco-cH2cH “ïs 2-N -CH3 X CH3 O CH3 ll | _ R5-o (cH2cH2cH2cH2o) yc-CHZ-N * -CH3 x CH3 fi CH3 + CH2O ) y- (CH2) tCO-CH2CH2-ï -CH3 X CH R5-0 (CH2cH CH 2 2 3 OH 5 UIR -o (CH2cH20) Ycc = cco-CHZ-ca 3 T fi CH -N + -CH3 X 2 CH3 The preferred derivatives described above can be prepared by reacting a long chain alkyl polyalkoxy (preferably polyethoxy) carboxylate with an alkyl chain of the desired length together with oxalyl chloride to give the corresponding acid chloride.The acid chloride is then reacted with dimethylaminoethanol to form suitable amine ester, which is then quaternized with a methyl halide to give the desired ester compound.Another route for the preparation of these compounds is by direct esterification. ring of the appropriate, long chain, ethoxylated carboxylic acid together with 2-haloethanol or dimethylaminoethanol in the presence of heat and an acid catalyst. The resulting reaction product is then quaternized with methyl halide or used to quaternize trimethylamine to give the desired ester compound. Formulation standards Using the nonionic and cationic components defined above, preferred compositions are formulated according to the invention based on the data obtained from the reduced monomer concentration (CR) of the cationic component in the washing solution. More specifically, the choice of a CR value for a given nonionic and cationic surfactant will determine the ratio in which these surfactants are to be combined. A reduced monomer concentration of a surfactant is obtained by dividing the concentration of the surfactant monomer present in the washing solution by the critical micelle concentration (CNC) of the surfactant. The critical micelle concentrations are determined, as the term is used herein, at 40.50 ° C in water with a mixed hardness of 6.70 dH, unless otherwise indicated. The cationic reduced monomer concentration of the nonionic / cationic surfactant mixture is determined by the following equations (1) up to and including (5). The preferred nonionic / cationic surfactant mixtures in connection with the invention are those having reduced monomer concentrations in the range of from about 0.002 to about 0.2, preferably from about 0.002 to about 0.15, and most preferably from about 0.002 to about 0. 08. To the extent that nonionic and cationic components of greater purity are used, the narrower CR regions become more suitable.

The concept of reduced monomer concentration in a one-component system as a quantity, which normalizes the degree of surfactant absorption on a textile surface (the critical element in the removal of greasy / oily dirt) is discussed in Tamamushi and Tamaki, Proceedings of the Second International Congress of Surface Activity, III, 449, Academic Press, Inc. (l957). The equations set forth below extend this concept of reduced monomer concentration to multicomponent systems utilizing surfactant monomer concentrations. The concept of surfactant monomer concentration is derived from the discussion found in Clint, J. Chem. Soc. Father. Trans., I, Zl, 152? (1975), referred to herein, in connection with an ideal solution and is based on the following quadratic equation (equation (ll) in C1int): + -c (cï) 2 [go - l] + cï (C-cš + cï) - aCcï = 0 l where as in the following equations: C = total analytical surfactant concentration in the solution (mol / l) = sum of the cationic concentration and the nonionic concentration = Cl + C2 (where "l" indicates nonionic surfactant and "2" indicates cationic surfactant) cï = critical micelle concentration (CNC) of the nonionic surfactant (mol / l) og = critical micellar concentration of the cationic surfactant (mol / l) a = total molar proportion of nonionic surfactant in the solution = Cl / (Cl + C2) B = a constant, which is based on the mixture heat = - 2,8 cï = nonionic monomer concentration og = cationic monomer concentration e = base in the natural logarithmic system = 2.7l828 x = molar proportion of the nonionic surfactant in the micelle at concentration C fl = nonionic activity coefficient in the mixed 2 micelle = eB (l_x) f2 = cationic activity coefficient in the mixed e 2 micelles = eßx + + A = f2 ° 2 f f1 ° 1 449 372 24 - reduced cationic monomer concentration H22 wo u I the molecular weight of the nonionic surfactant the molecular weight of the cationic surfactant? = total analytical surfactant concentration in the solution (ppm) = sum of the cationic concentration and the nonionic concentration (ppm) = W1 + W2 (where "1" indicates nonionic surfactant and "2" indicates cationic surfactant) Y = weight percentage nonionic surfactant in the composition - The above equation is solved for the nonionic monomer concentration by taking its positive square root (equation (12) in Clint). e? = {_§-c: >> in Uc- (eg-cï) Fnmowg- cp] 1/2} ß: 2 (-1 - 1) ° 1 By modifying this equation, which is based on the assumption that one has a regular rather than an ideal solution, the CR interval for optimal effect was obtained using the sequence - the equation: _ -wA) + Var-AF + LmcA _ 2A For a given cleaning test for a nonionic / cationic system, x was obtained by entering the values known from the test (ie cï, cš, a, C and B) in equation (1) and thus calculated x repeatedly, so that the error ix became less than 0.001 This procedure was repeated for a large number of such for search with varying conditions. The resulting x values were then used to calculate the cationic monomer concentrations using the following equation: X (1) og = (1-x) f2cš (2) 449 572 Next, the CR value was calculated using equation (5). m + CR = 92/02 The CR values obtained cover a large number of combinations and ratios of different nonionic and cationic surfactants at different concentrations and temperatures, which have been assessed in terms of their ability to remove greasy / oily dirt.

The examination of the values obtained showed that for a given system, the optimal cleaning of greasy / oily dirt was found to be at a CR value of about 0.002 to about 0.2.

This CR range (ie 0.002 to 0.2) can then be used to determine the range of optimal ratios of nonionic to cationic component for any combination of nonionic surfactant and cationic surfactant for the desired wash concentration within the total wash concentration range of 100 parts per 1,000,000 parts (ppm) to 10,000 ppm surfactant.

This calculation is performed as follows, where B, CR, c1, eg, ml and M2 are known for a given nonionic surfactant / cation surfactant pair: (a) for a given nonionic surfactant, cationic surfactant, and for each end of the CR region calculate x with the equation (1-x) eßX2 = CR using standard numerical methods, which are repeated to an error ix below 0,001, (b) determine the interval for Y with the equation Y (lx) x (lY) _ 1000 ~ _ M - M _ W Lx (xl) j &] l 2 with 100 ppm and 10,000 ppm as the limit values for W, for each end of the CR interval, ~ 449 372 26 (c) the interval for the nonionic surfactant / cationic surfactant ratio (NCR) for optimal effect is then within the range obtained by inserting the limit values for Y in the formula Y NCR - l_Y You can also proceed by combining steps (b) and (c) into a single equation, which can be solved directly with respect to NCR. ~ _L__ Non = _1_r_ = - (looo / mA + M2 (x-1) D1 ~ Y (looo / wj Ä + _1_ xMl The procedure described above is only relevant for washing solution concentrations above the critical micelle concentration of the nonionic surfactant / cationic surfactant mixture. ratios, which are as high as about five times the critical micelle concentration, CR is essentially independent of the concentration, which means that for conventional detergent concentrations (eg 100 ppm to 10,000 ppm and in particular from about 250 ppm to about 5,000 ppm), the CR value of most commercial cationic / nonionic surfactant mixtures (where the cationic component has a GMC below about 100 ppm, measured at 40.50 C in water with a mixed calcium and magnesium hardness of 6 , 70 dH) to be independent of the actual dosage level, so that the use of a concentration of about 1,000 ppm in the calculation above will give an acceptable approximation for the whole range. nges, therefore refers here to the CR value of 1,000 ppm.

As an example, the optimal grease / oil removal ratio for composition A in Example I and given CR value are calculated below. For this system, the following values are either known or selected as indicated: -n 27 449 372 used conditions) cï = 1,967 x 10,5 ppm cš = 2,187 x 10-5 ppm 5 = - 2,8 M1 = 406 ,? M2 = 520 CR = 0.0075 (selected to obtain optimal dirt removal effect for greasy / oily dirt, but could be any value between 0.002 and 0.2) Insertion of the values for B and CR in equation (a) : -2.8x2 (1-X) e = 0.0075 Repeated calculations of X gave the value x = 0.922.

With this value of x one found fl = 0.985 ra = o, o925 A, = <<>, <> 92s> <2.18vs X 10% - mas? x m5) = - 1.75 x 1o'5 Insertion of these values in equation (b) gives: Y (1-o, 922) _ o, 922 (1-Y) = looo 406.7 520 1ooo Y = 0.958 (o, 922) (o, 922-1) (- 1,75x1o'5) Inserting this value for Y in equation (c) gives the value of the nonionic / cationic ratio. _ O 958 _ NCR _ ïïåñššš ~ l $, l It should be noted that this ratio corresponds to the ratio actually obtained in Example I, Composition A.

Yes.

J>.

\ O CN ~ a AJ 28 In addition to these criteria for the reduced cation monomer concentration, the nonionic / cationic surfactant mixture must meet the specific requirements regarding the cloud point below. The cloud point of the nonionic / cationic mixture (and in preferred embodiments the nonionic / cationic mixture plus any optional electrolytes in the composition) falls between 0 and 950 ° C, preferably between 10 and 700 ° C, in particular between about 20 and about 650 C, especially between about 30 and about 500 C.

For washing effect in cold water, the surfactant mixture should have a cloud point between 0 and about 250 C. The fact that a composition has a cloud point within these temperature ranges ensures that the composition can be used under washing temperature conditions to achieve excellent good removal of greasy / oily dirt. If a composition does not have a cloud point within the specified temperature range, it will not result in the excellent cleaning according to the invention within this temperature range.

The compositions show their best effect in removing fat / oil, when the temperature of the washing solution in which they are used falls within about 200 ° C, preferably within about 150 ° C and in particular within about 100 ° C from the cloud point of the nonionic / cationic surfactant mixture. In other words, the wash solution temperature range within which the preferred compositions provide optimal grease / oil removal is between the temperature at the cloud point of the system in the absence of the cationic component and about 300 ° C, preferably about 250 ° C, most preferably about 250 ° C. 200 C, above this cloud point temperature.

The term "cloud point", as used herein, refers to the temperature at which a curve obtained by plotting the light scattering intensity of the composition against washing solution temperature begins to rise sharply to its maximum value and this under the following conditions: The light scattering intensity is measured by an apparatus designated "Model VM-12397 Photogoniodiffusometer", manufactured by Societe Français d'Instruments de Controle et dfAna- 29 449 572 lyses, France (hereinafter referred to as "SOFICA").

The instrument's sample cell with an associated lid is washed with hot acetone and allowed to dry. The surfactant mixture is prepared and dissolved with distilled water to a concentration of 1,000 ppm. A sample of approximately 15 ml of the solution is placed in the sample cell using a syringe with a 0.2 pore filter. / um nucleo- The injection needle is inserted through the cap of the sample cell so that the interior of the cell is not exposed to dust in the surrounding atmosphere. The sample is stored in a variable temperature bath. The bath temperature is raised by means of the instrument's heater and cooled by the addition of ice (heating rate Galo C / minute), the temperature of the sample being determined on the basis of the bath temperature. and both the bath and the sample are subjected to constant stirring.

The light scattering intensity (900 angle) of the sample is then determined at different temperatures using a green filter and without a polarizer in the SOFICA instrument. The preferred nonionic and cationic components of the present compositions are selected, combined and used on the basis of three main criteria: (1) the final composition must meet the above cloud point criteria and must be such that the surfactant mixture cloud point temperature is within about 200 ° C from normal washing solution temperatures, (2) the reduced cation monomer concentration of the surfactant mixture preferably falls within the range defined above and (5) the concentration of the detergent composition in the washing solution should be sufficient to give the desired washing effect below normal washing temperatures.

Particularly suitable for use in connection with the invention are biodegradable nonionic surfactants, which have relatively low CNC values and low cloud points (ie the temperature at which an aqueous solution of the surfactant exhibits turbidity). detergent compositions, the detergents of which are used at low temperatures. These surfactants can be used to prepare the desired cloud point for the nonionic / cationic mixture without any need for the addition of additional ingredients, such as e.g. electrolytes or anionic 449 372 50 surfactants. Such detergent compositions make it easier to meet the requirements set out here with respect to the cloud point and provide excellent good removal of greasy and oily dirt from textiles.

In formulating and utilizing the compositions of the invention, for the machine washing conditions common in the United States, it is preferred that the nonionic surfactant, cationic surfactant and any additional components be selected and used in such amounts that the temperature at which the detergent composition in the aqueous the washing solution has a cloud point as above, will be between about 50 ° C and 500 ° C, preferably at about 450 ° C. In cases where the compositions are used under different washing conditions, the compositions are formulated in such a way that at the the desired use concentration has its cloud point at a temperature which is within about 200 C from the desired washing temperature. Thus, the compositions are suitably formulated e.g. in Japan, where washing temperatures are generally lower than those used in the United States, so that their cloud point is close to about 150 ° C.

The temperature at the cloud point for a given composition in the washing solution depends on the physical and chemical properties (such as CNC and solubility) of the cationic and nonionic components as well as of the other components included in this composition and can be lowered. by increasing the alkyl chain lengths of the nonionic or cationic components, by lowering the degree of ethoxylation of the nonionic component or by adding electrolytes, such as e.g. phosphates, polyphosphonates, perborates, carbonates or sulphates, especially in relatively low amounts (eg from about 1 to about 15% of a given composition). More particularly, it is preferred that the detergent compositions of the invention, when used in the aqueous wash solution, have cloud points which fall within about 15 ° C, preferably within about 100 ° C and most preferably within about 50 ° C. from the temperature of the washing solution. It has been found that when these wash solution temperature / cloud point relationships are met, the washing solution capacity for removing greasy and oily dirt increases dramatically.

Without intending to bind the invention to any particular theory, it can be stated that there is reason to believe that when a detergent composition according to the invention is present in a washing solution with oil-contaminated textiles, the cationic component is adsorbed on the textile material, thereby neutralizing the negative charge on the textile material. This neutralization of the charge increases the adsorption of the nonionic surfactant on the textile material, which in turn causes the oily dirt to roll up. The dirt is then easily removed “by stirring. It is by formulation of cationic / nonionic surfactant mixtures that meet the requirements regarding cloud point and the preferred reduced cation monomer concentration that this mechanism and thereby the removal of greasy / oily dirt is optimized.

Fatty amide component In a particular embodiment of the invention, the nonionic / cationic surfactant mixture contains about 2 to about 25%, preferably about 2 to about 16% and most preferably from about 5% to about 10%, of a fatty amide surfactant. Any nonionic surfactant commonly used in detergent compositions can be used in these compositions, but preferred compositions contain the nonionic surfactants specified above to maximize the cleaning effect obtained.

In nonionic / cationic systems, the ratio of the total cationic and nonionic components to the constituent amide component ranges from about 5: 1 to about 50: 1, preferably about 8: 1 to about 25: 1. These compositions result in excellent washing effect. with regard to the removal of particulate dirt and also provides improved properties with regard to the prevention of dirt re-precipitation.

Amides useful in these preferred compositions include, but are not limited to, carboxylic acid amides, sulfonic acid amides, phosphonic acid amides, and boronic acid amides. Preferred amides include those of the formulas: R 24 or H 21 II / R 1 -CN and R 1 -sN \ R 2 or R 1 -C 20 -C 20 -alkyl, -alkenyl, -alkylphenyl or -alkylbenzyl, preferably C C18-alkyl, and in particular C11-alkyl, and where each of the groups designated by R is hydrogen or C1-C8-alkyl or -hydroxyalkyl, preferably hydrogen. Specific examples of these compositions include a mixture of stearoylcholine bromide (present in the wash solution at 120 ppm), coconut alcohol polyethoxylate with an average of 5 moles of ethylene oxide (included in the wash solution at about 557 ppm) and a middle fraction coconut ammonium alkylammonium. (present in the wash solution at about 50 ppm) and a mixture of stearoylcholine bromide (100 ppm), coconut alcohol polyethoxylate with an average of 5 moles of ethylene oxide (557 ppm) and lauramide (R 1 represents C 11 alkyl and R 2 hydrogen, at 45 ppm). Other components The compositions of the invention may also contain additional ingredients of the type generally found in detergent compositions at their conventional, technically established concentrations. These other components are preferably selected in such a way that the composition as a whole meets the above criteria with regard to the cloud point.

The compositions of the present invention may contain up to about 15%, preferably up to about 5% and most preferably from about 0.1% to 2%, of a defoamer component. Typical defoamers include long chain fatty acids, such as those described in U.S. Pat. No. 2,954,347, and combinations of certain nonionic materials therewith, as described in U.S. Pat. No. 2,954,548, to which both patents are incorporated herein by reference. Other defoaming components useful in the compositions of the invention include, but are not limited to, those described below. Preferred silicone foam damper additives are described in U.S. Pat. No. 5,955,672, to which reference is made; The silicone material may consist of alkylated polysiloxane materials, such as e.g. silica aerogels and xerogels and hydrophobic silicas of various types. The silicone material can be described as a siloxane of the formula: where x is a number from about 20 to about 2,000 and R and R 'each represent alkyl or aryl groups, especially methyl, ethyl, propyl, butyl and phenyl. Polydimethylsiloxanes (R and R 'represent methyl) having a molecular weight in the range of from about 200 to about 200,000 and above are all useful as suds control agents. Other suitable silicone materials, where the side chain groups R and R 'represent alkyl, aryl or mixed alkyl and aryl hydrocarbyl groups, exhibit useful foam control properties. Examples of such constituents include diethyl, dipropyl, dibutyl, methyl, ethyl, phenylmethyl polysiloxanes and the like. Other useful silicone defoamers may be a mixture of an alkylated siloxane, of the type described above, and solid silica. Such mixtures are prepared by attaching the silicone to the surface of the solid silica. A preferred foam control silicone material is a hydrophobic, silanated (especially trimethylsilanated) silica having a particle size in the range of from about 10 Dm to 20 cm and a specific surface area above about 50 m 2 / g, intimately mixed with dimethyl silicone liquid with a molecular weight in the range of about 500 to about 200,000 at a weight ratio of silicon to silanated silica of about 19: 1 to about 1: 2. The silicone defoamer is advantageously releasably incorporated in a water-soluble or dispersible, substantially non-dispersible surfactant, surfactant - impervious carrier material.

Particularly useful defoamers are such self-emulsifying silicone defoamers as e.g. "DB-544", which is commercially available from Dow Corning and contains a siloxane / glycol copolymer together with solid silica and a siloxane resin.

Microcrystalline waxes having a melting point in the range of 55 - 115 ° C and a saponification temperature below ioo are further examples of a preferred suds control component for use in the present compositions and are described in detail in U.S. Pat. No. 4,056,481, which is incorporated herein by reference.

The microcrystalline waxes are substantially water-insoluble but are dispersible in water in the presence of organic surfactants.

Preferred microcrystalline waxes have a melting point between about 650 DEG C. and 1000 DEG C., a molecular weight in the range 400 to 1,000 and a permeation value of at least 6, measured at 250 DEG C. according to ASTM-D1521. Suitable examples of the waxes described above include: microcrystalline and oxidized microcrystalline vaseline waxes, Fischer-Tropsch and oxidized Fischer-Tropsch waxes, ozokerite, ceresin, montan wax, beeswax, candelilla and carnauba wax.

Alkyl phosphate esters constitute another preferred defoamer for use in connection with the invention. These preferred phosphate esters are predominantly monostearyl phosphate, which may additionally contain di- and tristearyl phosphate, and monooleyl phosphate, which may contain di- and tri-oleyl phosphate.

The alkyl phosphate esters often contain some trialkyl phosphate. Thus, a preferred phosphate ester may contain, in addition to the monoalkyl ester, e.g. monostearyl phosphate, up to 50 mol% dialkyl phosphate and up to about 5 mol% trialkyl phosphate.

The detergent compositions of the invention may also, with the limitations of phosphate discussed above, comprise about 1 to about 60%, preferably low levels of about 1 to about 15%, of electrolyte components, such as e.g. conventional detergents, in particular alkaline, polyvalent, anionic detergents. The alkaline salts serve primarily to maintain the pH of the cleaning solution in a range from about 7 to about 12, preferably between about 8 and about 11, to modify the cloud point of the detergent composition and to provide an ionic strength increasing material. However, it is important to emphasize that the compositions of the invention are capable of providing excellent cleaning even in the complete absence of such detergency-supporting materials.

Suitable detergency-assisting salts useful in the invention may be of the polyvalent inorganic or polyvalent organic type or mixtures of these types. As non-limiting examples of suitable, water-soluble, inorganic, alkaline, detergent salts can be mentioned: carbonates, borates, phosphates, polyphosphates, bicarbonates, silicates and sulphates of the alkali metals. Specific examples of such salts include tetraborate, perborate, bicarbonate, carbonate, tripolyphosphate, orthophosphate, pyrophosphate and hexametaphosphate of sodium and potassium. Examples of suitable organic, alkaline, detergent salts may be mentioned: (1) water-soluble aminopolyacetates, e.g. sodium and potassium ethylenediaminetetraacetate, nitrilotriacetate and -N- (2-hydroxyethyl) nitrilotriacetate, (2) water-soluble salts of phytic acid, e.g. sodium and potassium phytate and (5) potassium and lithium salts of ethane-1-hydroxy-1,1-diphosphonic acid, water-soluble polyphosphonates, including sodium, sodium, potassium and lithium salts of ethylenediphosphonic acid and similar materials.

Additional organic detergent salts useful herein include the polycarboxylate materials described in U.S. Patent No. 3,564,105, which are incorporated herein by reference, including the water-soluble alkali metal salts. The water-soluble salts of polycarboxylate polymers and copolymers of the type described in U.S. Pat. No. 5,508,067, which are incorporated herein by reference, are also suitable as detergency builders in connection with the invention.

Another class of detergency builders useful in the present invention are insoluble sodium aluminosilicates, particularly those described in Belgian Pat. No. 814,874, which is incorporated herein by reference. This patent describes and protects detergent compositions containing sodium aluminosilicate of the formula Naz (AlO2) Z (SiO2) y ~ XH2O where z and y are integers having a value of at least 6, the molar ratio of z to y is in the order of 1, 0: 1 to about 0.5: 1 and X is an integer from about 15 to about 264, which aluminosilicate has a calcium ion exchange capacity of at least 200 meq / g and a calcium ion exchange rate of at least about 2.40 dH / minute / g . A preferred material is Mixtures of organic and / or inorganic detergent support materials may be used in connection with the invention. Such a mixture of detergency support materials is described in Canadian Patent 755,058 and consists of a ternary mixture of sodium tripolyphosphate, trisodium nitrilotriacetate and trisodium ethane-1-hydroxy-1,1-diphosphonate.

Other preferred detergency builders which may be used in the compositions of the invention include alkali metal carboxymethyltartronate, commercially available with about 76% active substance together with about 7% ditarthronate, about 5% diglycolate, about 6% sodium carbonate and about 8%. % water, as well as anhydrous sodium carboxymethyl succinate, commercially available with about 76% active substance together with about 22.6% water and a mixture of other organic materials, such as carbonate.

In addition to the cationic and nonionic surfactants discussed above, the detergent compositions of the invention may further contain up to about 50%, preferably about 5 to about 50%, anionic surfactants, zwitterionic surfactants or mixtures of such surfactants. Surfactants of these types useful in the compositions of the invention are listed in U.S. Patent Nos. 5,717,650 and 5,552,880, both of which are incorporated herein by reference. Below is a list of specific, non-limiting examples of surfactants that are suitable for use in the compositions in question. These surfactants are selected in such a way that the composition as a whole meets the above criteria in terms of cloud point and reduced cation monomer concentration.

Water-soluble salts of the higher fatty acids, ie "soaps", are useful as an anion surfactant in connection with the invention. This class of surfactants includes common alkali metal soaps, such as sodium, potassium, ammonium and alkanolammonium salts of higher fatty acids having from about 8 to about 24 carbon atoms and preferably from about 10 to about 20 carbon atoms. Soaps can be made by direct saponification of fats and oils. The sodium and potassium salts of the mixtures are particularly useful or by neutralization of free fatty acids. of fatty acids, derived from coconut oil and tallow.

Another class of anionic surfactants includes water-soluble salts, especially the alkali metal, ammonium and alkanolammonium salts, of organic sulfur reaction products having an alkyl group containing about 8 to about 22 carbon atoms and a sulfonic acid or sulfuric acid ester group in the molecular structure.

(The term "alkyl" includes the alkyl moiety of acyl groups.) Examples of synthetic surfactants in this group which may be used in the present detergent compositions are sodium and potassium alkyl sulphates, especially those obtained by sulphating the higher alcohols. (8 to 18 carbon atoms), prepared by reducing the glycerides of tallow or coconut oil, and sodium and potassium alkyl benzene sulfonate, the alkyl group containing about 9 to about 15 carbon atoms in the straight or branched chain, e.g. those of the type described in U.S. Pat. Nos. 4,420,099 and 2,85, which are referred to herein.

Other anionic surfactant compounds useful in this context include the sodium alkyl glyceryl ether sulfonates, especially those ethers or higher alcohols derived from tallow and coconut oil, sodium coconut fatty acid monoglyceride sulfonate and sulfate and sodium or potassium oxide sulfate content of sodium or potassium oxide sulphate ethylene oxide per molecule and in which the alkyl groups contain about 8 to about 12 carbon atoms. The alkaline earth metal salts of synthetic anion surfactants are useful in connection with the invention. Particularly suitable are the magnesium salts of linear alkyl benzene sulfonates, in which the alkyl group contains 9 to about 15, in particular 11 to 15, carbon atoms.

Other useful anionic surfactants include the water-soluble salts of esters of α-sulfonated fatty acids having about 6 to 20 carbon atoms in the ester group, water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids having about 2 to 9 carbon atoms in the acyl group and about 9 to about 25 carbon atoms in the alkane moiety, alkyl ether sulfate, which contains about 10 to 20 carbon atoms in the alkyl group and about 1 to 50 moles of ethylene oxide, water-soluble salts of olefin sulfonate having about 12 to 24 carbon atoms and β-acyloxyalkane sulfonate, which contains about 5 carbon atoms in the alkyl group and about 8 - 20 carbon atoms in the alkane moiety.

Preferred water-soluble organic anion surfactants for use in the invention include linear alkyl benzene sulfonates containing about 10 to 16 carbon atoms in the alkyl group, alkyl sulfate having about 10 to 20 carbon atoms, alkyl glyceryl sulfonate, wherein the alkyl groups are derived from coconut oil, and alkyl ether sulfate. , wherein the alkyl moiety contains about 10 to 20 carbon atoms and wherein the average degree of ethoxylation varies between about 1 and 6.

Examples of specific, preferred anionic surfactants which may be used in connection with the invention are: linear sodium C 10 -C 12 alkylbenzenesulfonate, triethanolamine-GlO-59 449 572 C12-alkylbenzenesulfonate, sodium tallow alkyl sulphate, sodium coconut alkyl alkyl glyceryl ether sulfonate and sulphated condensation product of C14-C18 alcohol with about 1 to about 10 moles of ethylene oxide.

It should be noted that any of the anionic surfactants listed above may be used either singly or in mixtures.

Zwitterionic surfactants include derivatives of aliphatic, quaternary ammonium, phosphonium and sulfonium compounds, wherein the aliphatic moiety may be straight or branched and wherein one of the aliphatic substituents contains about 8 to 18 carbon atoms and one contains an anionic water solubilizing group.

Particularly preferred zwitterionic materials are the ethoxylated ammonium sulfonates and sulfates described in U.S. Patent Nos. 5,925,262 and 5,929,678. Inclusion of these surfactants in the compositions complements the excellent washing effect in terms of removal of greasy and oily dirt and thus at the same time provides exceptionally good clay dirt removal.

Particularly preferred ethoxylated zwitterionic surfactants have the formulas: CH 5 + | CH5 and CH5 + CH3 Compounds of the above type containing 8 moles of ethylene oxide are also preferred. Other preferred zwitterionic surfactants include those of the formula 449 372 40 CH; I + _ clö fi šš- N- (c2H4o) yc2Huso4 (c2H4o) xH where the sum of x + y is equal to Ca 15.

Although the compositions may advantageously contain electrolytes, anionic surfactants and zwitterionic surfactants, as described above, selected to meet the cloud point requirement, a preferred class of compositions is substantially free of interfering anions which may interact with the cationic component and thereby act as a barrier to the cleaning and textile conditioning function. Whether an anion will function as a "disturbing anion" or not depends on the nonionic and cationic components present in a detergent composition as well as on the properties of the special cation, such as structure, main mass and dissociation constant.

In these compositions, the anionic materials should be present in sufficiently small amounts that no more than about 10 mol%, preferably in excess of about 5 mol%, of the cationic surfactant in the wash solution is complexed by the anionic material. In preferred compositions, where an anionic material has a dissociation constant of at least about 1 x 10 -5 (such as sodium toluenesulfonate), it may e.g. in an amount of up to about 40% by weight of the cationic surfactant, while when the anionic material has a dissociation constant of at least about 1 x 10-5, but below about 1 x 10-5, it may be present in an amount of up to about 15% by weight of the cationic surfactant, and in cases where the anionic material has a dissociation constant below about 1 x 10 -5 (such as linear sodium C 11,8-alkylbenzene sulfonate), it may present only in amounts of up to about 10% by weight of the cationic surfactant. Particularly preferred compositions of this type are those which are substantially free of detergent-assisting phosphate anions, polyphosphate anions, silicate anions and polycarboxylate anions, carboxymethylcellulose and anionic surfactants.

Other compatible auxiliary components which may be included in the compositions of the invention, in their conventional, technically established levels of use, include bleaching agents, bleaching activators, soil suspending agents, corrosion inhibitors, dyes, fillers, optical brighteners, germicides, pH adjusting agents, enzymes, enzyme stabilizers, perfumes, fabric softener components, antistatic agents and similar substances.

Buffering materials may also be added to control the pH of the compositions, with low molecular weight amino acids, in particular glycine, being preferred in cases where the composition is in the form of a clear liquid. However, due to the multiple and different advantages which the compositions according to the invention show with respect to the mode of operation, many components, e.g. detergents, antistatic agents, textile softeners and bactericides, usually not necessary. The compositions of the invention may additionally contain monoethanolamine, diethanolamine or triethanolamine components in amounts of up to about 50%, preferably between about 5 and about 20%. These components are useful as alkalizing agents and in formulating clear, homogeneous, liquid products which meet the cloud point requirements when placed in an aqueous wash solution.

The compositions according to the invention can be manufactured and used in a large number of different physical forms, e.g. in solid form, in powder form, in granular form or in the form of a paste or liquid. The compositions are particularly well suited for incorporation into substrate materials for use in household washing. These articles consist of a water-insoluble substrate which releasably encloses an effective amount, preferably about 20-80 g, of the detergent composition according to the invention.

A particularly preferred substrate article includes a bleaching component and a bleach activator on the substrate, together with the nonionic / cationic surfactant mixture.

A particularly preferred composition according to the invention is an aqueous, highly effective, liquid detergent composition containing from about 10 to about 50%, preferably from about 15 to 40%, of the nonionic surfactant, from from about 1 to about 10%. preferably about 1-6%, of the cationic surfactant and which additionally contains about 5 to about 50%, preferably about 10%, monoethanolamine, diethanolamine, triethanolamine or mixtures thereof. These compositions may also contain about 5 to about 20% of an anion surfactant, especially one of the ethoxylated or non-etocylated alkyl sulfate type. One embodiment of such a composition contains monoethanolamine, coconut alkyltrimethylammonium chloride as at least a portion of the cationic component and a mixture of the condensation product of secondary C12 alcohol with an average of 7 moles of ethylene oxide together with the condensation product of secondary C12 alcohol with an average of 5 moles of ethylene oxide in a ratio of higher ethoxylated nonionic material to lower ethoxylated nonionic material of about 5: 1 as the nonionic surfactant. In these compositions, the amounts and proportions of the components can be varied in such a way as to obtain a clear, homogeneous product which exhibits the required cloud point properties in the aqueous washing solution.

Washing processes The invention applies in its broadest aspect a process for cleaning solid surfaces which are soiled with greasy and / or oily materials, using an aqueous washing solution containing about 0.01 to about 0.5% by weight. of a mixture of a nonionic surfactant and a cationic surfactant, in which mixture the reduced monomer concentration of the cationic surfactant amounts to about 0.002 to about 0.2, preferably to about 0.002 to about 0.15 and most preferably from about 0.002 to about 0.08, and wherein the temperature of the solution is within about 200 ° C, preferably within about 150 ° C, most preferably within about 10 ° C, from the cloud point of the nonionic / cationic surfactant mixture. In general, it is at the point where the temperature of the washing solution is equal to the cloud point that a given system gives its best washing effect in terms of removal of greasy / oily dirt. Particularly preferred wash solutions are those in which the ratio of nonionic surfactant to cationic surfactant is 5.1: 1 to about 100: 1, especially 5.1: 1 to about 50: 1, most preferably from about 6: 1 to about 40: 1. , especially about ”5,449,372 6: 1 to about 20: 1.

Prior to this invention, it was totally unexpected that combinations of nonionic and cationic surfactants, even in the presence of a detergency builder, could provide cleaning from either greasy and oily soils or particulate soils comparable to commercially available ones. anion surfactant-based detergents with a high content of washing effect-supporting material. Furthermore, there was no indication that reduced cation monomer concentration and cloud point were critical factors in obtaining the removal of greasy and oily dirt. It was therefore completely unexpected that such Mmbüwthwær could be used to achieve superior good washing performance even in systems without phosphate or with low phosphate content as well as in systems which did not contain any washing effect supporting material or relatively low effective washing effect supporting materials.

Such a washing effect is obtained in cases where the newly discovered and prescribed criteria regarding cloud point and reduced cation monomer concentration are met in the washing process. The process requires that the wash solution be close to the cloud point temperature of the detergent composition, which is generally well above the CNC of the nonionic surfactant.

The concentration of the cationic surfactant should not be too low or too high above the GMC of the cationic surfactant to obtain the optimum grease / oil dirt removal effect. These criteria and the multiple other purifications that the expert's consideration may give rise to, such as ecological suitability and harmlessness, helps to define the preferred compositions described herein.

In the process according to the invention, it is also possible to achieve extremely good removal of particulate dirt, if sufficient cationic surfactant is present in the washing solution.

It may be necessary to balance the need for a relatively high concentration of cationic surfactant (eg at least about 50 ppm) against other factors and it may be noted that for very high ratios of nonionic surfactant: cationic surfactant, it may not be possible to at current application concentrations achieve the best removal of particulate dirt. However, the removal of particulate dirt and greasy / oily dirt achieved by these processes is superior to that achieved with all known, commercially available detergents and at the same time it is possible for the detergent product developer to meet current ecological and risk free requirements.

In addition to the benefits found for cleaning, the present invention provides an impressive array of secondary, but highly desirable, benefits which are almost unknown in the conventional anion surfactant-based detergents and prior art processes. It is e.g. depending on the identity and concentration of the cationic component, it is possible to produce beneficial effects, which are previously known for such cationic surfactants, e.g. antibacterial effect, antistatic effects, softening effects for textiles and a hitherto unobserved effect, namely the prevention or minimization of the transition of certain dyes from one textile material to another in connection with the washing process.

In general, the compositions of the invention are utilized in the washing process by providing an aqueous solution containing about 0.01 to 100 ppm) to 0.5% (10 to 100 ppm), preferably about 0.02 to 0. 2%, in particular from about 0.05 to about 0.15%, of the nonionic / cationic surfactant mixture, within the limits of the cloud point and the reduced monomer concentration indicated above, after which the soiled textiles are added in motion in this solution. The textiles are then rinsed and dried. When the compositions according to the invention are used in this way, they give extremely good removal of greasy and oily dirt as well as particulate dirt and also give good textile conditioning effect. When the compositions according to the invention are used in washing processes in other countries, in connection with industrial washing or in the cleaning of hard surfaces, concentrations as high as about 2% can be used. 45 449 372 All percentages, parts and ratios used herein refer to% by weight, parts by weight and weight ratios, respectively, unless otherwise specified.

The following non-limiting examples are intended to illustrate the compositions and process of the invention.

Example I Two compositions according to the invention were prepared by mixing together the components listed below in the amounts indicated. The cationic surfactants were chosen so that they were least dispersible in water when the compositions were used in the washing solution. §9 @ P9§ÉÉÉ9E_ê Äpgnent Weight:% C12-alcohol polyethoxylate, containing on average 5 moles of ethylene oxide (Cl2E5) HLB = = ll, CNC (determined experimentally under the conditions of use specified here) = 8 ppm 93.78 Palmitylalkyltrimoryl available as ammonium ammonium "Adogen 444") CNC determined experimentally under the conditions of use specified herein) = 7 ppm 6.22 Iieaeeeiäieë láoapeneni lilfb Cl ß Cl2E5 55.6 Coconut alkyltrimethylammonium chloride (commercially available as "Adogen 46l" Carbonate 55.8 0 r) D 5.8 When applying the above equations, the reduced cation monomer concentration for composition A was found to be about 0.0075 and for composition B about 0.025. The cloud point for composition A was about 450 C, while that for composition B was about 550 C. 449 572 us The washing effect of these compositions was examined in comparison with the washing effect of a granular standard detergent composition having the following composition: §ëeâë§el§e2 §9% Compound Weight% Sodium salt of sulphated tallow alcohol ethoxylated with 5 moles of ethylene oxide 5,5 Sodium tallow alkyl sulphate 5,5 Linear sodium C 11,8-alkylbenzene sulphonate 7,0 Silicate solids (2,0 r) 12,0 Sodium tripolyphosphate 24 , 4 Sodium sulphate 56.8 Polyethylene glycol 6000 0.9 Moisture and other constituents (eg bleach, perfume, etc.) left to 100 For each of these detergent compositions, three 28 cm X 28 cm patches (one made of double-knit polyester, one of a 65/55 blend of polyester / cotton and one of cotton only), which were stained with four different types of stains (dirty engine oil, lipstick, triolein and a clay-in-water emulsion). The three patches were then mixed with an average of 2.7 kg of pure blended laundry, containing cotton, polyester and cotton / polyester textiles, and the laundry was then washed in a normal sized Kenmore washing machine using one of the conditions described above. the compositions. Each composition was added to the wash solution at a use concentration of about 0.1%. Composition A had a pH value of 8 in the washing solution, and Composition B had a pH value of about 9.7. The wash water had a temperature of 40 ° C and a natural hardness of 8.70 dH.

After washing was completed, each of the patches was graded for the removal of each stain on a scale of 1 to 10, with 0 indicating complete removal and no removal at all. For each treatment, all clay removal grades were summed and likewise all five oil removal grades were added. For each treatment, the score for the clay removal could vary between 0 for complete removal and up to 50 for no removal at all, and for the grease and oil stains, the scores could vary between 0 for complete removal and up to 90 for no removal at all. The results obtained are summarized in the table below.

Detergent- Grease / oil- Clay removal- composition removal taking Comparative test l 78 l8 A 24 14 B 24 12 Using these values, one could thus demonstrate the extremely good washing effect in terms of removal of greasy and oily dirt as well as particulate dirt, which obtained by using the compositions according to the invention, even in the absence of any washing effect supporting components.

Substantially similar results were obtained when the nonionic components of compositions A and B above were replaced with a C 1-4 alcohol polyethoxylate having an average of 4 moles of ethylene oxide (HLB = 8.9), a C 1-5 alcohol polyethoxylate containing in an average of 6.5 moles of ethylene oxide, a C1-4 alcohol polyethoxylate with an average of 7 moles of ethylene oxide (HLB = 11.5), a C1-25 alcohol polyethoxylate with an average of 5 moles of ethylene oxide (HLB = 7.9) and the same product subjected to "stripping" to remove substantially all lower ethoxylate fractions and unethoxylated fractions, a secondary C55 alcohol polyethoxylate having an average of 9 moles of ethylene oxide (HLB = 12.7), a coconut alcohol polyethoxylate containing an average of 5 moles of ethylene oxide poly, a C1010 ethylene oxide , which contained on average 5 moles of ethylene oxide, a C14 alcohol polyethoxylate with an average of 6 moles of ethylene oxide, a C12 alcohol polyethoxylate with an average of 4 moles of ethylene oxide, a C1-25 alcohol polyethoxylate with an average of 9 moles of ethyl enoxide (HLB = 15.5), a C1-4 alcohol polyethoxylate with an average of 3 moles of ethylene oxide (HLB = = 8.9), a C14-15 alcohol polyethoxylate, which contained on average 9 moles of ethylene oxide (HLB = 12.8), and mixtures of des- 449 372 '48 said surfactants.

Excellent cleaning results were also obtained when the ratio of nonionic surfactant to cationic surfactant in compositions A and B above was 6: 1, 7: 1, 9: 1, 10: 1, 12: 1, 1? : 1, 20: 1 or 25: 1.

Similar results were also obtained when the sodium carbonate and sodium silicate components of composition B above were replaced in whole or in part with other alkali metal tetraborate, perborate, bicarbonate or carbonate in comparable amounts.

Substantially similar results were also obtained when the cationic surfactants of compositions A and B were replaced in whole or in part with decylalkyltrimethylammonium chloride, decylalkyltrimethylammonium hydroxide, C barrels ("Varisoft 475") together with coconut alkyltrimethylammonium chloride ("Adogen 46l") in a ratio between "Varisoft" and "Adogen" of about 1: 1, 5: 5, 5: 1, 2: 5 or 1: Or a mixture of palmitylalkyltrimethylammonium chloride with coconut alkyltrimethylammonium chloride in a ratio of palmityl to coconutalkyl compound of about 5: 1, 2: 1, 5: 2, 1: 1, 1: 2 or 1: 5 or surfactants of the following formulas: ( get HoH4c2-N * -c2H4oH oi 'C12H25 o on 5 II I ol7H55-0-o-cH2cH2-m * -cnš CH; Br (CRC = 50 ppm) 49 449 572 OO CH5 II ll | _ Cl4H29-OC-CH2CH2 -C-O-CHECHB-ï + -CH; Cl CH; CH Ciís | 5 T: ïa Cl- CI-Iš - + N- CHZ-CHZ -O- C- (CHZ) 10-C-Û-Cl-Iz CHE-NP-CHB c-Hš ena at 01211254cnzcnzo) 7-c112-co-cn2cH2-Nïc1aš Br "no aínš 0101121-04 011201120) lO-g -CHE-Nïcfaš of ÅRE Example II Cl He prepared the following two detergent compositions according to the invention by combining the components listed below in the amounts indicated.

The cationic surfactants were selected so that they were at least dispersible in water when the compositions were used in the washing solution. 449 372 50 Composition Composition CD šeeresssë Eiëëzë YiEE:% cl2E5 95 91 Palmitylalkyltrimethylammonium chloride 5 6 Coconut alkyltrimethylammonium chloride 2 5 Composition C had a reduced cationic monomer concentration of about 0.006 and a cloud point of approx. reduced cation monomer concentration of about 0.055 and a cloud point of about 550 ° C.

The washing effect with respect to the removal of greasy / oily dirt and particulate dirt was then examined for both compositions using the method described above in connection with Example I. Both compositions were used at a product concentration of about 0.1% in the washing solution, in water with a temperature of 40 ° C. Composition C had a pH of 8 and composition D a pH of 7.9 in the washing solution. ningen. Composition C was used in water with a natural hardness of 6.70 dH, while Composition D was used in water with a natural hardness of 6.7 ° a, 15.5 ° aH and 20 ° 2, respectively.

The dirt removal effect for these compositions is summarized in the table below.

Detergent Hardness Grease / oil Clay removal composition (O dH) removal removal c 6.7 16 8 D 6.7 50 7 D 19.5 22 BD 20.2 21 12 The compositions described above gave extremely good dirt removal of grease and oil as well as particulate dirt and also provided good textile conditioning, even in the presence of increased concentrations of hardening ions in the washing solution without any need for washing effect supporting components. 51 449 372 Excellent cleaning results were also obtained when the ratio of nonionic surfactant to cationic surfactant in compositions C and D above was about 10: 1, 15: 1, 20: 1, 25: 1, 50: 1, 40: 1 or 50: l.

Example III Two compositions of the invention were prepared by combining the components listed below in the amounts and proportions given.

Both of these detergent compositions gave a cloudy solution when added to a 409 C wash solution, indicating the presence of separate phases in the wash solution.

Composition EF Component Weight% Weight ~% 61235 75 'Cl2_15 alcohol polyethoxylate with an average of 6.5 moles of ethylene oxide (? L2_lj Eögâ) - 80 Coconut alkyltrimethylammonium chloride 4.2 Distearyldimethylammonium chloride (commercially available as "Arosurf" CN = 1 ppm _ - Methyl (1) tallow alkyl amidoethyl (2) tallow alkyl imidazolinium methyl sulfate (commercially available as "Varisoft 475") CNC = 8.5 ppm 4.2 Monoethanolamine 16.6 - Cloud point (OC) 40 45 Reduced cation monomer concentration 0.0ll 0.050 449 372 'sz The washing effect of greasy / oily dirt and particulate dirt for compositions E and F was then examined in comparison with the comparative sample of Example I, applying the method described in Example I above. All washes were performed in water at 400 ° C and with a natural hardness of 6.7 ° dH. Compositions E and G were used at a use concentration of about 0.1% in the washing solution, while the comparative composition was used at a use concentration of 0.14%. Composition E had a pH of 10.2 in the washing solution. The obtained washing effect results are summarized in the table below.

Detergent- Grease / oil- Clay removal composition removal taking Comparative test l 75 14 E 20 8 F 55 7 Using these results thus demonstrated the extremely good washing effect in terms of removal of greasy / oily dirt and particulate dirt obtained by use of the detergent compositions of the invention.

Example IV A composition according to the invention was prepared by. _ combine the components listed below 1 with the specified quantity ratios.

Component a Weight% Cl2E5 H 46 Coconut alkyltrimethylammonium chloride 8_ Sodium carbonate 54.5 Sodium silicate (2.0 r) 11.5 Cloud point = 500 C Reduced cation monomer concentration = 0.05? The soil removal effect of this composition was examined in comparison with a standard granular detergent composition having a low phosphate content and otherwise with the composition set forth below using the test method described in Example I.

Comparative Root 2 Component in% by weight Linear sodium C15-alkylbenzenesulfonate 20.0 Silicate solids (2.0 r) 19.5 Sodium carbonate 20.8 Trisodium sulphosuccinate 2.0 Sodium metaphosphate - 0.4 Sodium sulphate 51.5 Moisture and other constituents (t. eg bleach, perfume, etc.) left to 100 Both compositions were dosed at use concentrations of 0.14% to the aqueous washing solution. Composition H had a pH of 9 in the washing solution. The washing solution had a temperature of 400 DEG C. and a natural hardness of 6.70 dH. The cleaning results obtained are summarized in the table below.

F15 * Detergent- Grease / oil- Clay removal- composition removal removal Comparative test 2 75 4 H 5? These results show the extremely good washing effect both in terms of greasy / oily dirt and particulate dirt, which is obtained by using the compositions according to the invention.

Example V The relationship between washing effect for greasy / oily dirt and cloud point / grease solution temperature was demonstrated as follows. The detergent composition tested consisted of a mixture of the condensation product of C12 alcohol with 5 moles of ethylene oxide and C16 alkyltrimethylammonium chloride in a nonionic surfactant: cation surfactant ratio of 19: 1. The composition was used at a concentration of 100 000 ppm in distilled water. ¿449 572 54 The washing effect of this composition on greasy / oily dirt was examined as a function of the washing water temperature using a Tergotometer with a 10-minute washing program and two 2-minute rinses. For each test, two 7.5 cm x 7.5 cm stripped polyester knit patches were weighed. The patches were then stained with 200 mg of technical grade triolein (containing 0.0085% "Oil Red-O" to make it visible) and weighed again. The patches were allowed to lie and age for about 2 hours and then washed in the Tergotometer (1,000 ml water; 1,000 ppm of the detergent composition), air dried and weighed again. The percentage removal of triolein was calculated using the following formula: 100 x [: weight (soiled) - weight (wash fi j / [weight (soiled) - vil fi (clean)].

This procedure was repeated at a series of wash water temperatures.

The light scattering intensity of the detergent composition as a function of solution temperature was determined as follows.

The light scattering intensity was measured with an instrument of the type Model NV-12597 Photogoniodiffusometer, manufactured by Societé Française d'instruments de controle et d'analyses, France (the instrument is hereinafter referred to as "SOFICA"). The instrument's sample cell with lid was washed with hot acetone and allowed to dry.

The surfactant mixture was prepared and dissolved with distilled water up to a solution having a concentration of 1,000 ppm. An approximately 15 ml sample of the solution was placed in the sample cell using a syringe with a 0.2 μm nucleopor filter.

The injection needle was inserted through the cap of the sample cell so that the interior of the cell was not exposed to any influence of dust in the surrounding atmosphere. The sample was then stored in a bath with a variable temperature, and both the bath and the sample were subjected to continuous stirring. The bath temperature was raised by means of the instrument's heating device and lowered by the addition of ice (heating rate approx. 10 c / minute). The temperature of the sample was determined on the basis of the temperature of the bath. The light scattering intensity of the sample was then determined at different temperatures using a green filter and without a polarizer in the "SOFICA" instrument. 55 449 572 The results obtained in these tests are summarized in the following table.

Temperature% triolein- $ spreading- C removal intensity 22 52 2 26 ~ 2 50 90 - 52 ~ 5 56 - 4 40 92 - '45 - 5 48 - 8 50 97 15 52 _ 16 56 - 25 58 - 55 60 70 48 62 - _60 65 - 82 65 - 100 70 58 - These values show that the optimal triole removal for this detergent composition takes place in a washing solution with a temperature of about S00 C. This is approximately the same temperature as that at which the light scattering of the solution begins to increase sharply in the direction of its maximum value (ie the cloud point of the nonion / cation surfactant mixture). The values therefore show that by using this detergent composition in a washing solution with a temperature close to (ie within about 20 ° C) the cloud point of the composition, the maximum trioline removal for this composition was achieved.

Example VI A highly efficient liquid detergent composition having the composition set forth below was prepared by mixing together the following components in the stated proportions. 449 372 56 Component Weight% Cl2 alcohol polyethoxylate with an average of 5 moles of ethylene oxide (CIQE5) 85.15 Palmitylalkyltrimethylammonium chloride 5.65 Ethanol 8.0 Water, fluorescent agent, white matter, perfume and other constituents 1.2 This product had a cloud point, was between 500 ° C and 500 ° C and when used in an automatic washing process at a concentration of about 0.05%, it had a pH of about 7.5 and gave excellent removal of both particulate and greasy / oily dirt. Example VII A product including a carrier or backing material for use in the automatic washing process was made by impregnating a 20 cm x 28 cm sheet of a backing material designated "Scott 8050 Industrial Towel" having an air permeability of about 0.54 me / min / m 2, a basis weight of about 92.8 g per mg and a thickness of 1.12 mm, with about 50 g of the composition described in Example VI above.

The sheet was then dried to remove excess moisture. With this product a convenient method was obtained for introducing the compositions according to the invention into the washing solution and they also gave extremely good washing effect, antistatic treatment, soft treatment and prevention of color transition.

A substrate material product can also be made by blowing a 28 cm x 28 sheet of blown polypropylene sheet with a thickness of about 0.74 mm, a basis weight of about 70.0 g per m2 and an air permeability of about 0, 17 rpm / m2 was coated with about 60 g of the detergent composition described in Example VI, after which an identical sheet of backing material was placed on top of the coated sheet and heat sealed the edges of the two backing materials to encapsulate the detergent composition in the product. Example VIII A solid, particulate detergent composition of the invention having the composition set forth below was prepared in the following manner.

Component Weight% C12 alcohol polyethoxylate with i through 5 moles of ethylene oxide (Cl2E5), 59 Coconut alkyltrimethylammonium chloride 5 Urea _ 25 Sodium carbonate 15 Sodium silicate (2.0 r) 15 Other constituents (defoamers, nonionic components, etc.) residue to 100 mixed together and then mixed with the solid urea while simultaneously heating. The resulting product was then mixed with the carbonate, silicate and other components. When this product was used as an automatic washing process at conventional dosage levels, it had a pH value of about 9 and gave an exceptionally good washing effect for both particulate and greasy / oily dirt.

Example IX A solid, particulate detergent composition of the invention having the composition set forth below was prepared in the manner described in Example VIII above.

Component Weight% ° 12E5 59 Coconut alkyltrimethylammonium chloride 5 Urea 50 Sodium tripolyphosphate 15 Other ingredients (defoamer, bleach, moisture, etc.) Residual to 100 When used in an automatic washing machine at conventional use concentrations, it had a pH of about 449 372 and gave excellent washing effect on both particulate and greasy / oily dirt.

Example X A highly effective liquid detergent composition having the composition set forth below was prepared by mixing together the following components in the amounts indicated. The composition, when prepared, had a cloudy appearance.

Component Weight% Linear sodium C15-alkylbenzene sulphonate _ 14.4 Cl2E5 37.4 Coconut alkyltrimethylammonium chloride 5.8 Sodium sulphate 13.5 Water and other constituents (eg defoamer, perfume, bleach) residue to 100 automatic washing process at a concentration of about 0.05%, it had a pH value of about 9.5 and gave excellent removal of both particulate and greasy / oily dirt. This product can also be used as a pre-treatment agent, rubbing greasy / oily dirt stains with the product before the washing step itself.

Example XI A highly efficient, liquid detergent composition according to the invention having the composition given below was prepared by mixing the following components in the indicated proportions.

Component Weight% clz-lïEe, 5 50 Tallow alkyltrimethylammonium chloride 5 Monoethanolamine 5.5 Ethanol 5 Sodium chloride 2 Water and other constituents left to 100 59 449 572 This product, when used in an automatic washing process at a concentration of about 0.05% , a pH value of about 9 and gave excellent removal of greasy / oily dirt, dirt originating from body exudates and particulate dirt and it also gave the fabrics washed with it an advantageous antistatic treatment and a color transition preventing effect.

Substantially similar results were also obtained when the cationic component was replaced in whole or in part with palmitylalkyltrimethylammonium chloride or hydrogenated tallow alkyltrimethylammonium chloride, and when the nonionic component was replaced in whole or in part by the condensation product of C12 alcohol with 5 moles of ethylene condensation C14-15 alcohol with 7 moles of ethylene oxide or mixtures of these surfactants.

Example XII A highly efficient liquid detergent composition having the composition given below was prepared by mixing together the following components in the indicated proportions. After preparation, the composition had a clear, homogeneous appearance.

Component Weight% Secondary C12 alcohol polyethoxylate with an average of 7 moles of ethylene oxide (commercially available as "Softanol 70" from Nippon Shokubai Kogyo KK) 50 Secondary C12 alcohol polyethoxylate with an average of 5 moles of ethylene oxide (commercially available as "Softanol 50") 10 Coconut alkyltrimethylammonium chloride 5 Monoethanolamine 15 Water and other constituents 40 This product had a cloud point at about 15 ° C and gave excellent removal of particulate and greasy / oily dirt as well as dirt emanating from body secretions, when used in conventional Japanese. usually utilizes lower water temperatures than in the United States. Example XIII A highly effective liquid detergent composition having the composition set forth below was prepared by mixing the following components in the proportions given below.

When prepared, the composition had a clear, homogeneous appearance.

Component Weight% Secondary Cl 2 alcohol polyethoxylate with an average of 7 moles of ethylene oxide (commercially available as "Softanol 70" from Nippon Shokubai Kogyo KK) 50.0 Secondary C12 alcohol polyethoxylate with an average of 5 moles of ethylene oxide (commercially available as "Softanol 50" ") 10.0 Monoethanolamine 5.0 Coconut alkyltrimethylammonium chloride 0.75 Methyl 1-tallowalkylamidoethyl-2-tallowalkylimidazolinium methylsulphate 0.75 Ethanol 2.0 Defoamer 0.5 Water, bleach, perfume residue to 100 This product gave excellent particle removal me, greasy / oily soils and soils derived from body secretions, when used under conventional Japanese washing conditions, which usually include lower water temperatures than those used in the United States.

Example XIV A highly efficient, liquid detergent composition having the composition given below was prepared by mixing the following components in the indicated proportions. When prepared, the composition had a clear, homogeneous appearance.

J 61 449 372 Component Weight% Secondary C12 alcohol polyethoxylate with an average of 7 moles of ethylene oxide (commercially available as "Softanol 70" from Nippon Shokubai Kogyo KK) 15.0 Secondary C12 alcohol polyethoxylate with an average of 5 moles of ethylene oxide (commercially available as "Softanol 50") 5.0 Monoethanolamine 8.0 Coconut alkyltrimethylammonium chloride 1,15 Ditalgalkyldimethylammonium chloride 0,57 Isopropanol 1,5 Glycine 1,5 Cl2_4-alkyldimethylamine oxide 10,0 Water and other constituents (including perfumes and dyes product had desirable foaming properties and provided excellent removal of particulate, oily / oily soils and soils derived from body exudates when used under conventional Japanese washing conditions, which generally include lower water temperatures than those used in the United States.

Example XV A highly efficient liquid detergent composition having the composition set forth below was prepared by mixing the following components in the indicated proportions. When finished, the composition had a clear, homogeneous appearance.

Component Weight% Sodium sulphate of Cl2_15 alcohol, ethoxylated with 5 moles of ethylene oxide 5.0 Cl2_15 E6.5 20.0 Coconut alkyltrimethylammonium chloride 5.5 Glycine s, o Sodium toluenesulphonate 10.0 Water and other constituents residue to 1002 This 44 product had desirable foaming properties and provided excellent removal of particulate, greasy / oily soils and soils derived from body exudates; when used under conventional Japanese washing conditions, which generally include lower water temperatures than those used in the United States.

Eëemgel XVI A highly efficient, liquid detergent composition having the composition given below was prepared by mixing together the components listed below in the proportions given.

Component Weight-ä Condensate of 01% -C15 fatty alcohol with an average of 7 moles of ethylene oxide 28.5 Triethanolamine salt of linear alkylbenzenesulphonic acid, wherein the alkyl chain has an average of 11, 9 carbon atoms 20.0 C8-18 alkyldihydroxyethylmethylammonium chloride 1.5 Ethanol 10 .0 Diethylenetriaminepentamethylenephosphonic acid 0.5 Citric acid 0.2 9: 1 mixture of dimethylpolysiloxane and aerogel silica, emulsified in strongly ethoxylated fatty acid (commercially available from Dow Corning as "DBšl") 0.5 capped fatty acid having 16 to 22 carbon atoms in alkyl chain 0.75 Proteolytic enzyme (Maxatase “15 ä pure enzyme) 0.4 Other constituents + water left to 100 The composition above was homogeneous and stable for long periods of storage. In addition, in view of previously known compositions, it gave an unexpectedly superior effect in terms of removing greasy stains. .Eye ._., n. 65 449 372 Substantially similar results were obtained when the cationic component was replaced in whole or in part by a comparable concentration of a quaternized nitrogen-containing constituent selected from the group consisting of: coconut alkyltrimethylammonium chloromethylbromochloromethonium bromomethyl chloride , benzyl dihydroxyethylmethylammonium chloride, quaternary, ethoxylated coconut alkylammonium compounds in which 2 to 8 moles of ethylene oxide are condensed on the nitrogen and mixtures thereof. l-

Claims (11)

10 15 20 25 30 35 449 372 se Patentkrav Detergent composition, which gives a pH of at least 6.5 in the aqueous washing solution and is substantially free of oily hydrocarbon materials, cationic materials having 13 or more ethylene oxide groups and phosphate material, characterized in that it contains as an essential ingredient 10 to 95% of a surfactant mixture, consisting essentially of: (a) a biodegradable nonionic surfactant of the formula R (OC2H4) nOH 'where R represents a primary or secondary alkyl chain with 8 to 22 carbon atoms and n represents an average, to 2-12, and with a Hua value of s to 17 (b) a cationic surfactant has the formula which amounts to, and, which is free from hydrazinium groups and _ 1 2 (1) RmRxYLZ where each of the groups denoted by R1 is an organic group with a straight or branched alkyl or alkenyl group, optionally substituted with up to 3 phenyl or hydroxyl groups and optionally interrupted with up to 4 structures, selected from ooo R 2 R 2 II II II II II ___ s; -, -co-, -oC-, -cN- , -N-c-, OH H0 O e? * fe u I | u II _C_N_, -N_C_, -O-, -oco-, -ocN-, -Nco-, and mixtures thereof, the R1 groups each containing 8 to 22 carbon atoms, and which may additionally contain up to 12 ethylene oxide groups, m is a number from 1 to 3, each R 1 group having at most 14 carbon atoms, when m = 2, and at most 11 carbon atoms, when m = 3, each of the groups denoted by R 2 is an alkyl or hydroxyalkyl radical. group having 1-4 carbon atoms or a benzyl group, at most one R2 group in a molecule being benzyl, x being a number from 0 to 11, any remaining bonds at the carbon atoms being hydrogen atoms, Y being selected from: 25 30 35 (1) (2) (3) (4) (5) (6) (7) (8) 65 åh J> \ QL »" N "f, where p is 1-12, (czalímpa (CZH o) H: JP "N 'I where p in both cases is 1-12, (c2H40) pH I c \ / and CC / \ Ná \ (9) mixtures thereof, L is 1 or 2, the Y groups being separated of a grouping selected from R1- and R2 analogs with 1 to 22 ß x -1 ro 10 15 20 25 30 35 Give 449 372 carbon atoms and two free co linker bonds, when L = 2, Z represents an anion in sufficient number to give the molecule electrical neutrality, the cationic surfactant being at least dispersible in water in admixture with the nonionic surfactant, the ratio of the nonionic to the cationic surfactant being within the range 5.1: 1 to 100: 1 and the mixture has a cloud point of 0 to 95 ° C. Detergent composition according to claim 1, characterized in that the surfactant mixture has a cloud point between 10 and 70 ° C. Detergent composition according to claim 1 or 2, characterized in that L is equal to 1. Detergent composition according to one or more of claims 1-3, characterized in that n in the nonionic surfactant is 2 to 9. Detergent composition according to one or more of Claims 1 to 4, characterized in that Y is selected from II (β 2 H 4 O) PH -N + -, '-N + -, -N + - (C 2 H 4 O) pH (c 1-10. Detergent composition according to claim 5, characterized in that Y represents m is 1, x = 3, R 1 represents a C 10 -C 18 alkyl group and each of the groups represented by R 2 is a methyl group. Detergent composition according to one or more of Claims 1 to 6, characterized in that the ratio of nonionic surfactant to cationic surfactant amounts to 6: 1 to 20: 1. H, 10 15 20 25 é ”449 572 Detergent composition according to one or more of claims 1-7, characterized in that it additionally contains up to about 50% of a component, selected from anionic surfactants, zwitterionic surfactants and mixtures thereof. Detergent composition according to one or more of Claims 1 to 8, characterized in that the total number of carbon atoms in the R 1 and R 2 groups in the cationic surfactant is at most 28. Detergent composition according to one or more of Claims 1 to 3, characterized in that the nonionic surfactant is selected from C12-C13 alcohols, condensed with 4-10 moles of ethylene oxide, C14-C15 alcohols, condensed with 6-10 moles of ethylene oxide, and mixtures thereof, and that the detergent composition contains the nonionic surfactant and the cationic surfactant in a ratio of 5.1: 1 to 30: 1. Detergent composition according to one or more of Claims 1 to 3, characterized in that the nonionic surfactant is selected from the condensation products of C12-C13 alcohol with 6-10 moles of ethylene oxide, the condensation products of C14-C15 alcohol with 5-9 moles. ethylene oxide and mixtures thereof, and that x = 2, m = 2 and each the R1 group represents a coconut alkyl group in the cationic surfactant and that the ratio of nonionic surfactant to cationic surfactant is between 5.1: 1 and 15 - 1.