NL8800397A - PHOSPHATE-FREE TISSUE-SOFTENING DETERGENT COMPOSITION. - Google Patents

Description

* fc VO 1047

Phosphate-free fabric softening detergent composition.

The invention relates to a phosphate-free laundry softening detergent composition based on a clay softening agent and a cationic diammonium softening agent. The invention relates in particular to a solid phosphate-free detergent, containing surfactant detergent, clay softener and a diammonium salt as softener, to a method of preparing the detergent and to its use in the washing of textile materials.

Powdered detergent compositions containing a surfactant detergent (anionic, nonionic, etc.) with a clay softening agent and a cationic softening agent and / or antistatic agent such as a quaternary ammonium compound, quaternary di-ammonium compound and the like are known. Representative patent literature in this field are U.S. Patents 3,862,058, 3,886,075, 3,915,882, 3,948,790, 4,203,851, and U.K. patent-15 application GB 2,141,152A. Other patent literature relating to clay-containing fabric treatment compositions are U.S. Pat. Nos. 3,594,212 and 4,062,647. The use of bentonites for fabric softening is known from British Pat. Nos. 401,413 and 461,221.

Although satisfactory cleaning and softening compositions have been achieved with the known clay as softener-containing detergent compositions, it is desirable to reduce the amount of clay softener needed without adversely affecting the softening and cleaning performance of the compositions.

Furthermore, the undesirably high phosphate content of surface water is attributed to the polyphosphate content of detergents. It has been found that an increased phosphate content in surface water contributes to stronger algae growth with the result that the biological balance of the water can be adversely altered.

Recent legislation aims to reduce the amount of polyphosphates in detergents and in some areas in which polyphosphates cause a problem or prohibit the use of polyphosphate builder salts in detergents.

An object of the invention is to provide a phosphate-free, clay softener-containing detergent composition containing a diammonium compound as a softener.

Another object of the invention is to provide a phosphate-free detergent in the form of spray-dried beads, in which the spray-dried beads are mixed with a diammonium compound as an emollient and a mineral clay as a fabric softener, as well as a method of preparing the composition .

A further object of the invention is to provide a polyphosphate-free built-up clay softener-containing powder detergent composition with a reduced clay softener content, without adversely affecting the cleaning, whitening or softening action of the composition.

Yet another object of the invention is to provide a polyphosphate-free clay softener-containing powder detergent composition, in which the diammonium salt as a cationic softener and the clay softener can be added later to the spray dried beads or granules.

These and other objects of the invention are accomplished by use as a cationic softening compound of a diammonium salt of formula I-healed formula, wherein R 1 represents an aliphatic hydrocarbon group having 12 to 30 carbon atoms, each of groups> R 4, R ^ and independently of each other are aliphatic hydrocarbon radicals having 1-22 carbon atoms, it being understood that the total number of carbon atoms in all aliphatic hydrocarbon radicals - R ^ is not greater than 75 and that no more than two of the radicals R '- Rc are greater than 12 carbon atoms, R 30 represents -C 1 C 1 -C 3 or -C 1 C 1 C 1 Cl 2 - and X is an anion which forms a water-soluble salt.

The diammonium compounds of formula 1 can be dispersed in an aqueous or organic carrier and sprayed onto the detergent granules or beads. The diammonium compounds can also be heated to a temperature above their melting temperatures and then sprayed onto the detergent granules or beads. Another possibility is that the diammonium compounds as an aqueous dispersion, organic solution or melt are added to the clay softener and then mixed with the detergent granules or beads. desired level of softening performance is achieved with lower levels of the clay softener and without adversely affecting other detergent properties, including cleaning performance and whitening performance. Another advantage of the composition is that it forms little foam.

The diammonium compounds are soluble in conventional organic solvents and / or form stable dispersions in water.

The diammonium compounds are generally insoluble in water.

Since the diammonium salts of formula 1 are available or can be prepared in organic solutions or aqueous dispersions, they can be easily and safely handled in powder processors and easily sprayed or otherwise mixed with the built-up granular or powdered laundry detergent compositions.

In a preferred embodiment of the invention, the diammonium softener and clay softener 20 are premixed and then included as the later added ingredient in the spray dried granules or powdered laundry detergent composition.

A typical build up spray dried beaded composition containing the emollient of formula 1 and a clay emollient may contain the following ingredients: 25 _ _ _ ______ Amount __ (wt%)

Components Total Spray Dried Composition Pearls Surfactant Compound 1-95 10-60 Organic and Inorganic Detergent-30 Builders Salts 2-80 15-90 Clay Softener 1-50 0 Softener of Formula I 0.2-5 0 Fillers 0-25 0-10 Bleaches and bleach additives 0-25 0-5 35 optical brighteners, pigments, dyes 0-10 0.8 * 8 8 C 0 o ΐ / J »4

F

Quantity (wt%)

Components Total Spray Dried Composition _ Pearls Anti-foaming agents; suds suppressors, 5 etc. 0-10 0-8 enzymes 0-5 0 pH regulators, buffers, etc. 0-10 0-8 anti-redeposition agents, perfume, etc. 0-5 0-3 water __ remainder 10 In a preferred method for To prepare the built-up granular or powder softener detergent composition, the pH-insensitive, heat-stable detergent ingredients are mixed in a crank mixer and spray dried to form spray dried beads, which are evenly mixed or sprayed with the diammonium compound of Formula 1 and the mineral clay softener and with the components of the mixture which are pH sensitive and / or heat sensitive or may otherwise react with the anionic surfactant or other component of the spray dried beads or granules. As examples of ingredients to be added later, which can be mixed with the spray-dried beads, mention is made, for example, of the bleaching agent, the enzymes, the perfume, nonionic surfactant and the like. The diammonium compound of formula 1, as mentioned, can be previously mixed with the clay softener and then mixed with the spray dried beads or granules. Mixing procedures are well known in this art and those skilled in the art can easily determine the optimal mixing conditions.

The detergent compositions may contain one or more surfactants selected from anionic, nonionic, ampholytic and sitionic detergents. The synthetic organic detergents to be used according to the invention can be selected from a wide variety of such compounds, which are well known and described in detail in "Surface Active Agents and Detergents", Part II, by Schwartz, Perry and Berch, published in 1958 by Interscience Publishers. The total amount of the one or more surfactant detergent compounds may be up to 95% by weight of the total detergent composition, although more preferred amounts are between about 1 and 70% by weight, in particular between 5 and 50% by weight, most preferably between 5 and 30% by weight, of the total detergent composition.

The detergent compositions of the invention preferably contain one or more anionic detergent compounds as the primary surfactants. The anionic detergent can be supplemented, if desired, with another type of surfactant, preferably a nonionic detergent, especially when used in combination with a detergent builder salt.

Among the anionic surfactants which can be used according to the invention are the surfactants containing an organic hydrophobic group having 8-26 carbon atoms, preferably 10-18 carbon atoms in their molecular structure and at least one water solubilizing group, selected from sulfonate, sulfate, carboxylate, phosphonate and phosphate to form a water-soluble detergent.

Examples of suitable anionic detergents are soaps, such as the water-soluble salts (e.g. sodium, potassium, ammonium and alkanolammonium salts) of higher fatty acids or resin salts, containing 2-20 carbon atoms, preferably 10-16 carbon atoms.

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

The anionic class of detergents also includes the water-soluble sulfated and sulfonated detergents having an aliphatic group, preferably an alkyl group containing from 8 to 26 carbon atoms and preferably from 12 to 22 carbon atoms (the term "alkyl" includes the alkyl moiety of the higher acyl groups). Examples of the sulfonated anionic detergents are the higher alkyl mononuclear aromatic sulfonates, such as the higher alkyl benzene sulfonates having 10 to 16 carbon atoms in the higher linear or branched chain alkyl group, for example the sodium, potassium and ammonium salts of the higher alkyl benzene sulfonates, higher alkyl toluene sulfonates and higher alkyl phenol sulfonates. Other suitable anionic detergents are the olefin sulfonates, including long chain olefin sulfonates, long chain hydroxyalkane 88835356 sulfonates, or mixtures of olefin sulfonates and hydroxy alkane sulfonates. The olefin sulfonate detergents can be conventionally prepared by reacting sulfur trioxide (SO 2) with long chain olefins containing 8-25 carbon atoms, preferably 12-21 carbon atoms, such as olefins of the formula RCH = CHR, wherein R represents an alkyl group of 6-23 carbon atoms and R represents an alkyl group of 1-17 carbon atoms or hydrogen to form a mixture of sultones and olefin sulfonic acids, which is then treated to convert the sultones to sulfonates. Other examples of sulfate or sulfonate detergents are paraffin sulfonates containing 10 -20 carbon atoms and preferably 15-20 carbon atoms. The primary paraffin sulfonates are prepared by the reaction of long chain alpha olefins and bisulfites. Paraffin sulfonates, in which the sulfonate group is distributed along the paraffin chain, are described in U.S. Pat. Nos. 2,503,280, 2,507,088, 3,260,741, 3,372,188 and German Patent 735,096.

Other suitable anionic detergents are sulfated ethoxylated higher fatty alcohols of the formula RO ^ H ^ O) SO ^ M, wherein R represents a fatty alkyl group having 10-18 carbon atoms and m has a value of 2-6 (preferably a value of about 1/5 to 1/2 of the number of carbon atoms in the group R) and M is a solubilizing salt-forming cation, such as an alkali metal, ammonium, low alkyl amino or low alkanol amino cation, or higher alkyl benzene sulfonate wherein the higher alkyl group contains 10-15 carbon atoms. The amount of ethylene oxide in the polyethoxylated higher alkanol sulfate is preferably 2-5 moles of ethylene oxide groups per mole of anionic detergent, with 3 moles being most preferred, especially when the higher alkanol contains 11-15 carbon atoms. In order to maintain the desired hydrophilic-lipophilic balance, when the carbon content of the alkyl-30 chain is in the lower portion of the range of 10-18 carbon atoms, the ethylene oxide content of the detergent can be reduced to about 2 moles per mole, while the number of ethylene oxide groups, if the higher alkanol contains 16-18 carbon atoms, can be increased to 4-5 and in some cases even 8-9. Also, the salt-forming cation can be modified to obtain the best solubility. It can be any suitable solubilizing metal or radical, but .8 SO0307 will usually be an alkali metal, for example sodium, or ammonium. When lower alkylamine or alkanolamine groups are used, the alkyl groups and alkanols usually contain 1-4 carbon atoms and the amines and alkanolamines can be mono-, di- and tri-substituted, such as in monoethanolamine, diisopropanolamine and trimethylamine. A preferred polyethoxylated alcohol sulfate detergent is available under the trade name Neodol 25-3S (Shell Chemical Company).

The highly preferred water-soluble anionic detergent compounds are the ammonium and substituted ammonium-10 (such as mono-, di- and triethanolamine), alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and magnesium) salts of the higher alkylbenzene sulfonates , olefin sulfonates and higher alkyl sulfates. Among the above-mentioned anionic materials, the most preferred are the sodium linear alkyl benzene sulfonates, especially those in which the alkyl group is a straight chain alkyl group having 12 or 13 carbon atoms.

The anionic surfactant generally constitutes the predominant detergent component and may be 30-100% of the total amount of surfactants. Preferably, the anionic material forms at least 50%, especially at least 60%, and most preferably at least 70%, and preferably up to 99%, especially up to 90%, and most preferably up to 80%, of the total amount of surfactant detergent ingredients. .

The anionic surfactant is usually included and preferably as a component of the spray dried material and will be added to the crank mixture as an aqueous solution or dispersion, especially as a highly concentrated aqueous suspension.

The next most preferred class of surfactant-active detergent ingredients are the nonionic synthetic organic detergent compounds. The nonionic synthetic organic detergents are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically prepared by condensation of an organic aromatic or alkyl aromatic hydrophobic compound with ethylene oxide (which is hydrophilic in nature). Practically any hydrophobic compound with a carbon 8800 x 8 xyl, hydroxy, amido or amino group with a free hydrogen bonded to the nitrogen can be condensed with ethylene oxide or with its polyhydration product, polyethylene glycol, to form a non- ionic detergent. The length of the hydrophilic or poly-oxyethylene chain can be easily adjusted to achieve the desired balance between the hydrophobic and hydrophilic groups.

The nonionic detergent to be used is preferably a poly-layer alkoxylated higher alkanol, in which the alkanol contains from 8 to 22 carbon atoms, preferably from 10 to 18 carbon atoms and in which the number of molecules of the lower alkylene oxide (with 2 or 3 carbon atoms) men) is 3-20. Such materials are preferably used such that the higher alkanol is a higher fatty alcohol having 11-15 carbon atoms and containing 5-13 lower alkoxy groups per mole.

Preferably, the lower alkoxy group is an ethoxy group, but in some instances it may be desirably mixed with propoxy, which, when present, usually forms a minor (less than 50%) component. Examples of such compounds are those in which the alkanol contains 12-15 carbon atoms and 7 ethylene oxide groups per mole are present, such as Neodol 25-7 and Neodil 23-6.5 (Shell Chemical Company). The former material is a condensation product of a mixture of higher fatty alcohols having an average of 12-15 carbon atoms with about 7 moles of ethylene oxide, and the latter material is a corresponding mixture in which the higher fatty alcohol contains 12-13 carbon atoms and the number of ethylene oxide groups per mole averages about 25 is 6.5. The higher alcohols are primary alkanols. Other examples of such detergents are Tergitol 15-2-7 and Tergitol 15-S-9 (Union Carbide Corporation), both of which are linear secondary alcohol ethoxylates. The former material is a mixed ethoxylation product of a linear secondary alkanol with 11-15 carbon atoms with 7 moles of ethylene oxide, and the latter material is a similar product, but with 9 moles of ethylene oxide.

Highly preferred nonionic materials for use in the present compositions are the higher molecular weight nonionic detergents such as Neodol 45-11 (Shell Chemical Company) which are similar condensation products of fatty alcohols having 14-15 carbon atoms with 11 moles ethylene oxide per mole .

, S 8 0 0 7 i: 7 9

Of the total surfactant detergent components in the detergent composition, the nonionic surfactant material may be present in an amount of up to 70 wt%, preferably up to 50 wt%, especially up to 40 wt%, and most preferably up to about 15 wt% . When used, the nonionic surfactant is usually present in a. amount of at least 1 wt%, preferably at least 10 wt%, in particular at least 30 wt%, of the total weight of all surfactant detergent components. In terms of the total softener detergent composition, the nonionic surfactant compound will usually be present in an amount of 0.1 - 20 wt%, preferably 0.3 - 15 wt%, and especially 0.6 - 10 wt%.

Since the nonionic surfactants are often sparingly soluble in water or form viscous solutions or gels when added to water, they are usually made available in the form of solutions in an organic solvent, for example in ethanol or isopropanol, at themselves or together with water. When the nonionic surfactant is available in the form of a solution in an organic solvent, the solution is not included in the crutch mixture used for the formation of the spray dried granules or pearls, but later added to the already formed spray dried pearls. Even when the nonionic surfactant is used in the pure liquid form (most nonionic compounds are ambient temperatures liquid) or in the form of an aqueous solution, it is still preferred that the nonionic surfactant compound is later added to the spray dried beads.

Also useful are zwitterionic detergents such as g-betaines and sulfo-beta of formula 2, wherein R is an alkyl group of 10 having 8-18 carbon atoms, R and R independently of each other an alkyl or hydroxyalkyl group having 1-4 carbon atoms , R represents an alkylene or hydroxyalkylene group with 1-4 carbon atoms and X represents a carbon atom or a group S: 0. The alkyl group may contain one or more intermediates, such as amido, ether or polyether bonds, or nonfunctional substituents, such as hydroxyl or halogen, which do not significantly affect the group's hydrophobic character. When X represents a carbon atom, the detergent is called a betaine; X states one. 88'i! lit 7 Γ 10 group S: 0 for, then the detergent is called a sulfo-betaine or sultaine.

Ampholytic detergents can also be used for the invention. Ampholytic detergents are well known in the art and many useful detergents of this class are recognized

Schwartz, Perry and Berch mentioned in the aforementioned book "Surface Active Agents and Detergents". Examples of suitable amphoteric detergents are alkyl beta imino dipropionates, RN (H) COOM), alkyl 3-aminopropionates, RN (H) C H H COOM; and long chain imidazole derivatives of formula 3, 10 in which formulas R represent an acyclic hydrophobic group having 8-18 carbon atoms and M a cation to neutralize the charge of the anion. Examples of specific useful amphoteric detergents are the disodium salt of undecylcycloimidinum-ethoxyethionic acid-2-ethionic acid, dodecyl-3-alanine and the inner salt of 2-trimethylamino-15 lauric acid.

The amounts of the zwitterionic synthetic organic detergent and the ampholytic synthetic organic detergent when present in the compositions of the invention are not particularly critical and can be selected depending on the desired results. Generally, either or both classes of detergent components may be used to replace in whole or in part the anionic organic surfactant and / or nonionic organic surfactant within the above ranges.

As with the anionic and non-ionic surfactants, those skilled in the art can easily determine whether the zwitterionic and ampholytic surfactants should be included in the crank mixture used to form the spray dried beads or granules or later 30 were added to the spray dried beads to form the final built up laundry detergent composition. Briefly, when available as aqueous solutions, they will preferably be added to the crank mixture, and if available as organic solvent solutions, will be added later to the spray dried material.

The clay softening material can be selected from the .886039? * 11 various clay softeners known in this art to impart softness to the fabrics washed therewith. The preferred clay materials are smectite clay materials, of which such with an ion exchange capacity of at least 50 milli-5 equivalent / 100 g clay are preferred.

The smectite-type clays which can be used in accordance with the invention are three-layer clays characterized by the ability of the layer structure to be. increase the volume in the presence of water several times by swelling or expanding to form a thixotropic gelatinous substance.

There are two distinct classes of smectite-type clays: in the first class, aluminum oxide is present in the silicate crystal lattice; in the second class, magnesium oxide is present in the silicate crystal lattice. Within the crystal lattice of the smectite-15 clay materials, atomic substitution by iron, magnesium, sodium, potassium, calcium and the like can occur. It is common to distinguish between clay materials on the basis of their predominant cation. For example, a sodium clay is a clay in which the cation is predominantly sodium.

The cation-exchanging ability of a mineral clay is related to factors such as the expandability of the clay, the charge of the clay, which in turn is determined at least in part by the lattice structure, and the like. The ion exchange capacity of clay materials can vary widely from about 2 milliequivalents / 100 g for kaolinites to 150 milliequivalents / 100 g and more for certain montmorillonite variety clays. Illite clay materials have an ion exchange capacity in the lower part of the said range, namely around 26 milliequivalents / 100 g for an average illite clay.

It has been found that illite and kaolinite clay materials with their relatively low ion-exchange capacities are not or only marginally useful as clay softeners. Such illite and kaolinite clay materials are a major component of clay soil, which is removed from tissue surfaces using the compositions of the invention. Smectites, such as nontronite, with an ion exchange capacity of approximately 50 milliliters of 8 vvvv * 12 equivalent / 100 g, saponite with an ion exchange capacity of around 70 milliequivalent / 100 g, and montmorillonite with an ion exchange capacity of more than 70 milliequivalent / 100 g, however, have proved to be very useful emollients in that they are deposited on fabrics 5 to provide the desired softening. Clay minerals preferred according to the invention can therefore be characterized as expandable three-layer smectite-type clays with an ion exchange capacity of at least 50 milliequivalents / 100 g. A smectite-type clay, known as "foller 10 clay", found in a relatively thin vein above the Black Hills, also has the required ion-exchange properties characteristic of the clay materials to be used in accordance with the invention, and is therefore encompassed by the term "smectite-type clay".

The smectite clay materials to be used in the compositions are all commercially available. Examples of such clay materials are montmorillonite, volchonskoite, nontronite, hectorite, saponite, sauconite and vermiculite. These clay materials are available under various brand names, for example Thoxogel No. 1 (also "Thixo-Jel") and Gelwhite GP (Georgia Kaolin Company), Volclay BC and Volclay No. 325 20 (American Colloid Company), Black Hills Bentonite BH45Q (International Minerals and Chemicals) and Veegum Pro and Veegum F (RT Vanderbilt).

Such smectite-type minerals obtained under the aforementioned brand names may contain mixtures of the various discrete mineral units. Such mixtures are suitable for use according to the invention.

While any smectite-type clays with a cation exchange capacity of at least 50 milliequivalents / 100 g are particularly useful, certain clays are preferred. Gelwhite GP, for example, is an extremely white form of smectite clay and is therefore preferred when formulating white granular detergent compositions. Volclay BC, a smectite-type clay mineral, which contains at least 3% iron (expressed as Fe2 ° 3) in the crystal lattice and has a very high ion exchange capacity, is one of the most effective and effective clay materials for application in detergents and is preferable from the point of view of product performance.

Suitable clay minerals for use according to the invention can be selected due to the fact that the smectites have a true 14A X-ray diffraction pattern. This characteristic pattern in combination with the exchange capacity provides a basis for the selection of certain smectite-type minerals for use in the present granular detergent compositions.

In the compositions of the invention, the most preferred clay softeners are the aluminum silicates, in which sodium is the predominant cation, such as, for example, bentonite clay materials. Wyoming bentonite clays are particularly preferred.

Preferred swelling bentonites are marketed as industrial bentonites under the trade name Mineral Colloid (Benton Clay Company). These materials, which are the same as previously sold under the brand name Thixo-Jel, have been selectively recovered and 15 reprocessed bentonites, the most useful of which are available as Mineral Colloid 101 etc., corresponding to Thixo-Jel 1, 2, 3 and 4. Such materials have a pH (6% concentration in water) between 8 and 9.4, maximum free moisture contents of about 8% and specific gravities of about 2.6; of the powdery grade, at least 85% (and preferably 100%) has a particle size of at most 74 microns. Preferably, substantially all particles (i.e., at least 90% thereof, preferably more than 95%) have a particle size of at most 44 microns, and most preferably, all particles have a particle size of at most 44 microns. The swelling capacity of the bento-25 staples in water is usually 3-15 ml / g and the viscosity at a 6% concentration in water is usually about 8-30 centipoise.

Instead of the Thixo-Jel or Mineral Colloid bentonites, products such as those sold by the American Colloid Company, Industrial Division, as General Purpose Bentonite Powder can be used, of which at least 95% is finer than 44 micrometers (moist particle size) and at least 96% finer than 74 μm (dry particle size). Such an aqueous aluminum silicate mainly consists of montmorillonite (at least 90%) with smaller amounts of feldspar, biotite and selenite. A typical analysis on an anhydrous basis is 63.05% silica, 21.5% alumina, 3.3% ferric iron (as Fe2O ^), 0.4% ferrous iron (as FeO), 2.7% magnesium (as MgO), 2.6% sodium and pn '14 potassium (as Na20), and 0.7% calcium (as CaO), 5.6% crystal water (as H20) and 0.7% trace elements.

Although the western bentonites are preferred, it is also possible to use other bentonites, such as those obtained by treating Italian or similar bentonites, containing relatively small amounts of exchangeable monovalent metals (sodium and potassium) with alkaline materials, such as sodium carbonate, to enhance the cation exchange capacities of such products. The Na 2 O content of the bentonite should be at least about 0.5%, preferably at least 1% and especially at least 2%, so that the clay has satisfactory swelling properties with good softening and dispersing properties in aqueous suspension. Preferred swelling bentonites of the types described above are marketed under the brand names Laviosa and Winkelmann, for example Laviosa AGB and Winkelmann G-13.

Of course, other clay minerals capable of imparting "softness" to textile materials can also be used according to the invention.

The preferred clay materials are not palpable, i.e. they have a particle size that cannot be felt. Non-palpable clay materials have particle sizes less than about 50 microns; the clay materials to be used according to the invention have a particle size from about 5 micrometers to about 50 micrometers.

The clay softening compounds are present in the detergent compositions in amounts of 1-50 wt.%, Preferably of 2-30 wt.%, Especially of 4-20 wt.%, Based on the total composition.

According to the invention, it is preferred that the clay softener and the diammonium compound be added later to the spray dried beads or granules. The diammonium softening compound is preferably dissolved in an organic solvent or dispersed in an aqueous liquid and mixed with the mineral clay particles. The diammonium softening compound and the mineral clay softening agent are then thoroughly and evenly mixed with the spray dried beads or granules.

, δ s Cf: - i> 15

The diammonium softening compound and the clay softening agent are present in the detergent compositions of the invention in an amount sufficient to provide the desired softening effect when the composition is used in conventional amounts for a laundry detergent composition, for example, from about 30-350 cc of detergent per wash load.

The detergent compositions of the invention may optionally, but preferably contain at least one detergent builder salt of the type commonly used in detergent compositions.

Suitable build-up salts are the conventional inorganic water-soluble build-up salts, such as, for example, water-soluble salts of silicates, carbonates, bicarbonates, borates, sulfates and the like. Organic builder salts are, for example, the water-soluble polyhydroxysulfonates, polyacetates, amino polyacetates, carboxylates, polycarboxylates, succinates, phytates and the like.

Specific examples of non-phosphorus-containing inorganic build-up salts are the water-soluble inorganic carbonate, bicarbonate and silicate salts. The alkali metal, for example, sodium and potassium carbonates, bicarbonates and silicates are particularly suitable.

The crystalline and amorphous aluminosilicate zeolites are particularly suitable detergent builder salts. The zeolites generally have the formula (Μ20) χ · (M203 V (Si ° 2 ^ 'WH20 25) where x = 1, y = 0.8 - 1.2 and preferably = 1, z = 1.5 - 3.5 or higher and preferably = 2 - 3, and w = 0 - 9, preferably = 2.5 - 6, and M preferably represents sodium A typical zeolite is type A or similar structure, particularly preferred for type 4A. The preferred aluminosilicates have calcium ion exchange capacities of about 200 milliequivalents / g or more, for example 400 milliequivalents / g ·

Various crystalline zeolites (aluminosilicates) that can be used are described in British Patent 1,504,168, U.S. Patent 4,409,136 and Canadian Patents 1,072,835 and 1,087,477. An example of suitable amorphous zeolites can be found in Belgian Patent 835,351.

.8 8 0 t c i '16

Water-soluble organic builder salts are particularly suitable. For example, the alkali metal, ammonium and substituted ammonium acetates, carboxylates, polycarboxylates and polyhydroxysulfonates are suitable builder salts for the compositions and methods of the invention. Specific examples of acetate and polycarboxylate builder salts are sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid, nitrilotriacetic acid, benzene poly (ie penta- and tetra) carboxylic acids, carboxymethoxy succinic acid and citric acid.

Further suitable organic builder salts are the polycarboxylate materials described in U.S. Pat. No. 2,264,103, including the water-soluble alkali metal salts of melelic acid. Also suitable are the water-soluble salts of polycarboxylate polymers and copolymers, as described in U.S. Pat. No. 3,308,067.

Specific organic builder salts that can be used are alkali metal salts of hydroxy acrylic acid polymer, preferably the sodium and potassium salts. Particularly preferred building materials are the α-hydroxyacrylic acid and sodium salt polymers. The hydroxyacrylic acid and salt polymer detergent builder salts which can be used contain monomer units of formula IV wherein and R 2 are the same or different and hydrogen or an alkyl group of 1-3 carbon atoms such as methyl, ethyl and propyl introduce. Preferably both substituents are R 2 and hydrogen. M represents hydrogen or an alkali metal, such as sodium or potassium, or an alkaline earth metal, such as calcium, magnesium or barium. Preferably M is sodium. The polymer end groups are not critical and can be H, OH, CH 2 or a hydrocarbon chain. The degree of polymerization, that is, the value of n, is generally determined by the limit compatible with the solubility of the polymer in water. For example, the hydroxy acrylic acid or salt polymer can have a molecular weight of 2000-20,000. Methods for preparing these polymers are described, for example, in U.S. Pat. Nos. 3,920,570 and 4,107,411.

Other suitable organic builder salts are alkali metal or ammonium salts of carboxymethyloxy succinic acid, preferably the trisodium salt. The carboxymethyloxy succinic acid salts to be used in the detergent compositions of the invention comply with the general formula 5, wherein M represents hydrogen, alkali metal or ammonium and at least one M is alkali metal or ammonium. The preferred alkali metals are sodium and potassium, the most preferred of which is sodium. The mono, di and trisodium salts can be used, of which the trisodium salt is most preferred.

Another organic build-up salt that can be used is the organic alkali metal low polycarboxylic build-up salt. This organic builder salt comprises alkali metal salts of low polycarboxylic acids, for example with 2-4 carboxyl groups. The preferred sodium and potassium salts of such low polycarboxylic acids are the salts of citric and tartaric acids. Most preferred are the sodium salts of citric acid, especially trisodium citrate.

Still other organic building materials which can be used are polymers and copolymers of polyacrylic acid and polyaloolic anhydride and their alkali metal salts. Such builders may, in particular, consist of a copolymer which is the reaction product of approximately equal molar amounts of methacrylic acid and maleic anhydride, which reaction product is completely neutralized to form the sodium salt. Such material is commercially available under the brand name Sokalan CP5. This build-up material can inhibit crusting even in small amounts when used.

Examples of organic alkaline sequestering builder salts, which can be used with the alkali metal low polycarboxylic acid builder salts or mixed with other organic and inorganic builder salts, are alkali metal, ammonium or substituted ammonium aminopolycarboxylates, eg sodium and potassium ethylenediamine tetraacetic acid (EDTA ), sodium and potassium nitrile triacetates (NTA), and triethanol ammonium N- (2-hydroxyethyl) nitrilodiacetates. Mixed salts of these aminopolycarboxylates can also be used.

Other suitable organic-type building materials are the polyacetalcarboxylates. The polyacetal carboxylates and their use in detergent compositions are described, for example, in U.S. Patents 4,144,226, 4,315,092, and 4,146,495.

Mixtures of organic and / or inorganic. 61:.

4 18 build-up salts are used. Although the alkali metal salts of said inorganic and organic polyvalent anionic builder salts are preferred for economic reasons, the water-soluble ammonium, alkanol ammonium, for example triethanol ammonium, diethanol ammonium and the like salts of said builder anions are also suitable. .

The builder salts, both the inorganic and organic detergent builder salts, are suitably added to the crank mixture to be incorporated with the anionic surfactant etc. into the spray dried beads or granules in amounts of 15-75% by weight, preferably 20-60% by weight, in particular 22-55% by weight, of building salts, based on the weight of the spray-dried pearls or granules, such that the finished composition after mixing with the ingredients added later is 2-30% by weight, 15 preferably contains from 10 to 70% by weight and in particular from 20 to 50% by weight of detergent build-up salt (s), based on the total composition.

The emollient compounds to be used according to the invention are diammonium compounds, which are characterized by their general water insolubility.

The diammonium compounds, which are used to improve the softening effect of the composition, are compounds of the general formula 1, wherein R ^ is an aliphatic hydrocarbon group of 12-30 carbon atoms, each of the groups R2, R3, R ^, Rg and Rg independently represent aliphatic hydrocarbon groups having 1-22 carbon atoms, it being understood that the total number of carbon atoms in all aliphatic hydrocarbon groups R ^ - Rg is not more than 75 and that no more than three of the groups R2 - Rg contains more than 12 carbon atoms, R 1, -CH 2 CH 2 or -C 1 C 2 CH 2 - and X represents a water-soluble salt-forming anion.

The preferred compounds of formula 1 are those containing only one or two, preferably only a single, long carbon chain group, i.e., having 12 or more carbon atoms. Preferably, therefore, in formula 1 R 1 is an aliphatic hydrocarbon group, which may be linear or branched and saturated or unsaturated (ie linear or branched alkyl, alkenyl or alkynyl) and which contains 16 to 22 carbon atoms, such as 18 to 20 carbon atoms, and R2 - Rg are independently »880C · 1/19 alkyl or alkenyl groups of 1-16 carbon atoms, preferably 1-12 carbon atoms, especially 1-6 carbon atoms, provided that the total number of carbon atoms in all aliphatic hydrocarbon groups R ^ -Rg not more than 50, preferably not more than 5, and which not more than 2, preferably not more than one, most preferably none of the groups R ^ -Rg contains more than 12 carbon atoms , R 1 -CH 1 CH 2 CH or -CH 1 CH 1 CH 2 -, preferably -CH 2 CH 1 CH 2 -, and X is a water-soluble salt-forming anion such as halide, eg bromide, chloride, or iodide, sulfate, methosulfate, ethosulfate, hydroxy-10de, acetate, propionate or other similar inorganic or organic solubilizing monovalent anion.

Examples of preferred R 1 groups are stearyl, tallow, hydrogenated tallow, eicosyl, soy and the like.

Examples of preferred alkyl and alkenyl groups for R 1 - R - are methyl, ethyl, propyl, isopropyl, n-butyl, tertiary

ΔO

butyl, n-butenyl, octyl, 1-octenyl and the like. Methyl, ethyl, propyl and isopropyl are particularly preferred. Most preferred are methyl and ethyl.

Specific examples of compounds of formula 1, 20 which are commercially available or can be readily prepared by conventional techniques are compounds of formulas 5-9 and the corresponding water-soluble ethosulfate, halide, acetate and the like salts.

The compound dimethyl-N-tallowalkyl-N1-trimethyl-propylene diammonium dichloride of formula 5 is particularly preferred. This compound is commercially available as Adogen 477 {Rewo Company). This compound can be prepared in the usual manner, for example, by reacting 1 mole of N-methyl-N-tallow-N'-methylpropylene diamine with 3 moles of methyl chloride, followed by quaternization of the obtained compound with methyl sulfate.

The diammonium softening compound can be impregnated into the beads or granules without the use of a solvent or carrier liquid. However, it is generally preferred to dissolve the diammonium softening compound in an organic solvent or disperse it in an aqueous carrier liquid. The softening diammonium compound is preferably premixed. fe C 0 9 7 20 with the mineral clay softener, after which the mixture is added to the spray-dried pearls or granules.

An aqueous solution and / or dispersion of the pH-insensitive and heat-stable ingredients such as one or more builder salts, fillers, anionic surfactant, pH adjuster, water and the like are mixed together to form the crank mixture, which is then spray-dried in the usual manner.

The spray-dried beads or granules are intimately mixed with the diammonium softening compound and the clay softening agent and the other ingredients, for example, nonionic capillary. active compound, bleach, enzymes, perfumes and other pH sensitive or heat sensitive and / or water insoluble ingredients to form the final softening detergent composition. The amounts of the spray dried beads or granules and components added later is such that the final composition contains the following amounts of the essential ingredients: ___ Amount (wt%) _

Ingredient _ Spacious___ Medium_____Preference

Detergent 1-95 5-50 5-30 20 Build-up salts 2-80 10-70 20-50

Clay softeners 1-30 2-20 4-10

Diammonium salt 0.25-10 0.5-5 1.0-2.5 (with formula 1)

Detergent additives, fillers, moisture 0-60 2-50 5-30

Clay softener / diammonium salt ratio - 10: 1 to 6: 1 to _____________________UI___________3_s 1______

If necessary, the rest of the composition consists of conventional detergent additives, fillers and moisture.

The use of an inert water-soluble filler salt is desirable in the laundry compositions of the invention. A preferred filler salt is an alkali metal sulfate, such as potassium or sodium sulfate, of which sodium sulfate is particularly preferred. The amount of filler will usually not exceed 5 wt%, such as 0.1-2 wt%, preferably 0.3-1 wt%, based on the composition.

* 8 Ê 0 £ c b / 21

Various auxiliary substances can be included in the detergent compositions according to the invention. These are generally perfumes, colorants, for example, pigments and dyes, bleaches, such as sodium perborate, bleach activators, bleach stabilizers, anti-redeposition agents or soil suspending agents, such as alkali metal salts of carboxymethyl cellulose, optical brighteners, such as anionic, cationic or nonionic brighteners, foam stabilizers, such as alkanolamides, foam promoters, germicides, anti-scaling agents, pH regulators, enzymes and the like, all of which are known for use in detergent compositions for washing fabrics. Flow promoters, commonly referred to as flow aids, can also be used to keep the particulate compositions in the form of free-flowing pearls or powders.

Commercially, starch derivatives and particular clay materials are available as additives that improve the flowability of otherwise tacky or pasty particulate compositions; two such clay additives are currently marketed under the brand names "Satintone" and "Microsil". In the detergent compositions, bound and free water may also be present in minor amounts that do not adversely affect the fluidity of the granular or powdered compositions. The moisture content is normally 1 - 15%, preferably 5 - 12%, in particular 8 - 12% of the entire composition. Within these amounts, a satisfactory flowing particulate, powdery or granular product results; control of the particle size and the moisture content can prevent the product from dusting excessively.

Suitable amounts of the detergent additives are: enzymes - 0-2%, especially 0.2-1%; corrosion inhibitors -0-15% and preferably 2-8%; anti-foaming agents and suds suppressors 30 - 0-15%, preferably 0-8%, for example 0.1-5%; soil-suspending or anti-redeposition agents and anti-yellowing agents - 0-10%, preferably 0.3-3%; colorants, perfumes, brighteners and bluing agents total 0-2% and preferably 0-1%, such as 0.2-0.8%; pH modifiers and buffers - 0-5%, preferably 0-2%; bleach - 0-40%, preferably 0-25%, e.g. 2-20%; bleach stabilizers and bleach activators: 0-15%, preferably 0-10%, e.g. 0.1-8%. The choice of excipients takes into account their compatibility with the main components of the detergent composition.

Regardless of the shape of the laundry detergent, its application in the washing process is practically the same. The particulate composition 5 is usually added to the wash water in an automatic washing machine in such an amount that its concentration in the wash water is 0.05-1.5%, usually 0.1-1.2%. The water to which the composition is added is preferably of medium or low hardness, for example a hardness of 30-120 parts per million as calcium carbonate, but usually softer and harder waters can also be used. The water temperature can be 20-100 ° C and is preferably 60-100 ° C in those cases where the textile or laundry can tolerate high temperatures without decay or color fading. When washing at a low temperature is desired, the temperature can be kept at 20 - 40 ° C.

At the stated detergent composition concentrations, the pH of the wash water will usually be on the basic side and will be, for example, 7-12, preferably 8-11, especially 9-10. The weight ratio of laundry to wash water is usually between 1: 4 and 1:30, preferably between 1:10 and 1:30.

The invention is illustrated by the following examples, in which all parts and percentages are by weight.

The following composition is prepared by first forming the spray dried beads (A) and then adding the components (B) later.

. 8 8 C ü b & Ί 23 "A" (Spray dried pearls) ___________ Share___

Tap water 6/8

Hydrogenated fish oil or tallow oil fatty acids 2.8 5 NaOH (35.7%) 1.3

Tap water 11.5

Sodium Silicate (40%) (Na 2 O: SiO) 9.9 1 1 1

Anionic surfactant 16.0 2

Optical brightener 0.2 10 Sodium carboxymethyl cellulose 0.7

Zeolite inorganic detergent build-up salt 33.9

Sodium sulfate (anhydrous) 0.7 _

Subtotal: 83.8

Ingredients added later (B) __________ Parts _ 15 Sodium perborate 15.0

Blue bentonite clay aggloraate 16.0 3

Adogen 477 2.5

Enzyme 0.5

Magnesium Silicate / DTPA mixture No. 2 0.2 20 Potassium Methyl Siliconate (50%) 0.6 5

Non-ionic surfactant 3.0

Duet 787 (perfume) _______________________________________ 0_, 5 ___

Subtotal: 38.3

Spray dried beads (A) - 61.7. Total: 100.0 1. Linear dodecylbenzene sulfonate - as an aqueous suspension.

2. stilbene brightener No. 4, highly concentrated grains.

3. Adogen 477 is a compound of the formula 5 depicted on the formula sheet.

30 4. 61.7 parts after drying.

5. C 4-4 C 5 fatty alcohol ethoxylated with 11 moles ethylene oxide per mole.

The spray dried beads (A) are mixed with the ingredients (B) added later to form product 1 (invention). In product 1 (invention), the concentration of the mineral clay emollient is 16% and the concentration of the emollient 8800397 24

Ti

Adogen 477 2.5%.

For comparison, the same composition is prepared, but without the Adogen 477. The second composition, product 2 (comparison), contains 16% mineral clay softener and no Adogen 5 477.

Product 1 and Product 2 were used in three cycles to wash test fabrics at 60 ° C.

Evaluation of product 1 (invention) A + B regarding softening, cleaning and whitening showed that due to the addition of Adogen 477 there was no negative effect on performance parameters compared to product 2 A + B (without the softening agent Adogen 477).

The soil removal by product 1 (invention) was compared to that of product 2 (comparison), it being found that the products 1 and 2 were substantially equivalent.

The softness properties imparted to the test fabrics by product 1 and product 2 were compared, revealing that product 1 (invention) was superior to product 2 (comparison).

The efficacy of products 1 and 2 in whiteness and soil redeposition was compared on test fabrics of polyester / cotton, cotton and nylon washed therewith, where it was found that in all these test fabrics product 1 (invention) was superior to product 2 (comparison).

The washing liquid containing product 1 (invention) was found not to form a foam compared to product 2 (comparison) which did form foam.

Example I shows that the addition of Adogen 477 to the composition results in an approximately equivalent soil contamination ring, while providing superior softness and whiteness / redeposition properties and low foaming.

Example_II

Following the same general procedure as in Example I, the following composition is prepared:. 88G03 * "/ 35 25" A "(Spray Dried Pearls) __ Wt%

Sodium tridecylbenzene sulfonate 15.0

Zeolite inorganic detergent build-up product 39.3

Sodium silicate (Na2O: SiC> 2 = 1: 2.4) 7.0 5 Sodium sulfate 4.0

Optical brightener (Tinopal 5BM) 0.2

Na-carboxymethyl cellulose 0.25

NaOH (40%) ______ 1.75

Subtotal: 67.5 10 Ingredients added later (B) Wt%

Thixogel No. 1 clay 10.0

Adogen 477 2.5

Sodium perborate 15.0

Enzyme 0.5 15 Potassium methylsiliconate 0.6

Non-ionic surfactant 3.0

Magnesium Silicate / DTPA mixture No. 2 0.3

Duet 787 __ (perfume) ___ ____ __ __ 0.6

Subtotal: 32.5 20 Total: 100.0 1. * "i2 ** ^ 14 fatty alcohol condensed with 9 moles ethylene oxide per mole.

In the composition of Example II, product 3 (invention) contained 10 wt% clay softener and 2.5 wt% of the softener Adogen 477. For comparison, product 4 was prepared, containing 16 wt% clay softener, but no Adogen 477.

The effectiveness of product 3 (invention) in soil removal was compared to that of product 4 (comparison), where it was found that products 3 and 4 were nearly equivalent.

Comparison of the softness properties imparted to the fabric by products 3 and 4 showed that product 3 (invention) was superior to product 4 (comparison).

The efficacy of products 3 and 4 in whiteness and soil redeposition was compared to the test fabric requirements of polyester / cotton, cotton and nylon which had been bleached. 8 8 0 C · 26 that product 3 (invention) in cotton and nylon was superior to product 4 (comparison), and that the efficiencies of products 3 and 4 in polyester / cotton were approximately equivalent.

Example 3 (invention) did not form foam compared to product 4 (comparison) which did form foam.

Example 2 shows that the addition of Adogen 477 to the composition allows for a significant reduction in the amount of clay softener required to achieve the desired softening, while still obtaining equivalent or superior effectiveness in soil removal, softness, whiteness / redeposition and foaming.

.6 S 0 CIS?

Claims (13)

2. Composition according to claim 1, characterized in that at least one detergent compound is an anionic synthetic detergent and at least one detergent build-up salt is an inorganic build-up salt or an organic build-up salt. 3. Composition according to claims 1-2, characterized in that in formula 1 Rj represents a linear or branched alkyl, alkenyl or alkynyl group with 16-22 carbon atoms, R2 - Rg independently of each other alkyl or alkenyl groups with 1-16 carbon atoms are provided that the total number of carbon atoms in the aliphatic hydrocarbon radicals R 1 -R 8 is not more than 50 and that no more than two of the groups R 1 -R 8. contain more than 12 carbon atoms. 2, o Composition according to claim 3, characterized in that R2 - Rg independently represent alkyl or alkenyl groups of 1-6 carbon atoms, with the proviso that the total number of carbon atoms in all aliphatic hydrocarbon groups R1 - Rg is not. $ ï i! ('7 P? Exceeds 35. 5. A composition according to claims 1-4, characterized by 10-60 wt% of at least one detergent compound, 15-90 wt% of at least one detergent build-up salt, 0.25-10 wt% of the softening diammonium compound of Formula 1, 1-30 wt% mineral clay softener and 0-50 wt% detergent additives, fillers and moisture. 6. Composition according to claim 5, characterized by 15-40 wt.% Of a linear high alkyl benzene sulfonate as anionic synthetic detergent, 25-65 wt.% Of an inorganic zeolite as detergent builder salt, 0.5-5 wt. % of the softening diammonium compound of formula 1, 2-20% by weight of mineral clay emollient and 5-40% by weight of pH insensitive and heat stable detergent additives, fillers and / or moisture or mixtures thereof. Composition according to claim 6, characterized in that the linear high alkyl benzene sulfonate is dodecyl benzene sulfonate, the inorganic detergent build-up salt is zeolite and the diammonium compound is the compound of formula 5. 8. Phosphate-free softening detergent composition, characterized by a clay softening agent and the softening diammonium compound, mixed with the spray dried laundry detergent composition of claim 1. 9. Phosphate-free, free-flowing powdered or granular laundry detergent and softening composition, characterized by (A) 25 1-95% by weight of at least one detergent compound selected from anionic, nonionic, amphoteric and zwitterionic synthetic detergents and mixtures thereof, (B) 2-20 wt% of a fabric softening mineral clay, (C) 2-80 wt% of at least one detergent builder salt and (D) 0.5-5 wt% of an emollient diammonium compound of formula 30 1, wherein an aliphatic hydrocarbon group having 12-30 carbon atoms represents each of the groups R2, R4, R4, Rg and Rg independently an aliphatic hydrocarbon group having 1-22 carbon atoms, with the it being understood that the total number of carbon atoms in all the aliphatic hydrocarbon groups - Rg does not exceed 75 and 35 that no more than three of the groups R2 - Rg contain more than 12 carbon atoms, R ^ -C ^ CH ^ - or -Ci ^ Cï ^ CI ^ - and X represents a water-soluble .88003 ?? is a salt-forming anion, and (E) 0-50% by weight of detergent additives, fillers and / or moisture. 10. A composition according to claim 9, characterized in that the spray-dried beads or granules contain an anionic surfactant compound, detergent build-up salt and one or more pH-insensitive and heat-stable detergent additives, fillers and mixtures thereof, which is the diammonium compound. premixed with the fabric softening clay and the premix uniformly mixed with the spray dried beads or granules. 11. Composition according to claims 9-10, characterized in that in formula 1 a linear or branched alkyl, alkenyl or alkynyl group with 16 - 22 carbon atoms represents R 1 - Rg independently of each other alkyl or alkenyl groups with 1 - 1 Are 16 carbon atoms, it being understood that the total number of carbon atoms in all the aliphatic hydrocarbon groups R-R is not more than 50 and that XO does not contain more than two of the groups R2-Rg more than 12 carbon atoms. Composition according to claim 11, characterized in that R 1 - R independently represent alkyl or alkenyl groups with 1-6 2 b 20 carbon atoms, with the proviso that the total number of carbon atoms in all aliphatic hydrocarbon groups R 1 - Rg does not more than 35. 13. A composition according to claims 9-12, characterized in that the softening diammonium compound is the compound of formula 5. The composition according to claim 13, characterized in that the composition contains about 10 wt% mineral clay softener and about 2.5 wt% softening diammonium compound. , 8 8 0 Ü 5 ST /