NO168950B - Particle-shaped detergent and plasticizer mixture - Google Patents

Description

The present invention relates to particulate mixtures of detergent and fabric softener1 which are capable of providing improved properties with regard to softness, cleaning effects, counteracting the redeposition of dirt and counteracting the effect of static electricity in substances treated with the mixtures, and in particular when washing clothes in machine.

Mixtures for simultaneous achievement of washing effect and

a reasonable degree of softness when machine washing fabrics, and thus suitable for use in the washing cycle, are well known and are readily available commercially. The reaction between anionic surfactants, perhaps the most commonly used of the available types of surfactants, and cationic softeners, particularly those of the di-lower-di-higher-alkyl quaternary

close to the ammonium type and which makes the products unstable, is likewise well known from the patent literature. Such a reaction often results in the formation of invisible deposits which are trapped in or otherwise deposited on the fabric being washed. Discoloration or other aesthetically unpleasant effects are

for the most part inevitable. The net result is often a dilution of the effective amount of anionic surfactant available for useful purposes as the loss of anionic surfactant is the main consequence of this reaction.

Although the most effective types of cationic quaternary ammonium softeners, such as the above-mentioned di-higher-alkyl types of quaternary compounds, such as distearyldimethylammonium chloride, can act in the wash cycle in the presence of anionic surfactants, builders, etc., the amount needed to achieve effective softening usually borders on the amounts that give an undesirable reaction between cationic compounds and anionic compounds. As a general rule, at least approx. 2 times as much cationic surfactant for softening as for antistatic action. Representative prior art addressing this problem is discussed below.

In US Patent No. 3,325,414, which primarily deals with detergents with controlled foaming ability, the problem with cationic and anionic surfactants and the accompanying harmful effects is discussed in more detail. The patent document also emphasizes that certain quaternary ammonium compounds within the class of cationic agents are generally unstable when heated and when they come into contact with alkaline builders, the instability being manifested by the development of strong amine odors and undesirable color. The mixtures according to this patent document are limited to the use of quaternary ammonium halides with only one higher alkyl group, and where the specified structural formula for the cationic substance is correspondingly limited. Cationic compounds of this type are clearly inferior to the di-higher-alkyl types, at least in terms of fabric softening effect.

The problem of cationic incompatibility in anionic detergents is also recognized in US Patent Nos. 3,936,537 and 4,141,841, and it is there proposed to use an organic dispersion inhibitor as an essential component together with the cationic substance. An important characteristic of such inhibitors is a maximum water solubility at 25°C of 50 ppm. Similar descriptions can also be found in US patent documents

Nos. 4,113,630, 4,196,104 and 4,272,386. In US Patent No. 4,230,590, extra powerful detergents are described which comprise conventional builders, mainly anionic surfactants, cationic softeners and a mixture of fatty acid soap and cellulose ether. The mixture of soap and cellulose ether exists in the form of threads, flakes or other form, and is present in the mixture as mainly homogeneously dispersed, separated particles.

US Patent No. 4,298,480 describes extra powerful detergents with similar compositions to that described in the section above, with the exception that cellulose ether is not included.

US Patent No. 4,329,237 describes extra powerful detergents which are also similar to those described in the two paragraphs above, except that the soap particles contain a non-ionic surface-active agent.

According to GB Patent Application No. 2 133 813A, published

1 August 1984, further improvements have been made in relation to the above-mentioned patents, which result in less greasy staining (spot staining), e.g. due to the cationic softener, in that, in addition to and homogeneously dispersed in the anionic surfactant and detergent builder, separate particles (e.g. "prills") of a mixture of the cationic amine softener and the nonionic organic surfactants.

See also US Patent Nos. 4,339,335, 4,326,971,

4 416 811, 4 411 803, 4 450 085 and 4 414 129, all of which describe mixtures of detergent and softener in particulate or powder form. Although the above-mentioned detergent mixtures containing detergent/soap and cationic softener have desirable properties in terms of softening, anti-static effect and cleaning effect, further improvements in these properties are desirable while reducing the overall cost of the product. The present invention provides a particulate detergent and softener mixture which is capable of imparting to treated substances improved softness and washing action, antistatic and anti-dirt redeposition properties, in a washing process. The mixture is characterized in that it comprises from 5 to 40% by weight of a water-soluble, non-soap, organic, anionic, surfactant, from 10 to 60% by weight of a water-soluble, neutral to alkaline builder salt, and substantially homogeneously dispersed in the mixture as separate particles , from 2 to 20% by weight, based on the total mixture, of an intimate mixture of (i) a cationic amine plasticizer, and (ii) a water-soluble, ethoxylated, tertiary amine compound as dispersant and plasticizer, with the formula

where R is alkyl or alkenyl with from 8 to 22 carbon atoms, and x and y are such positive numbers that the sum x + y is from 2 to 15, the percentage concentration of anionic surfactant being at least 1.5 Cs + 5, where Cs is the percentage

concentration of the total amount of plasticizer (i) and (ii), and the amount of the ethoxylated, tertiary amine (ii)

is from 2 to 50% by weight of the mixture of (i) and (åi).

As described in the previously mentioned GB patent application

no. 2 133 813A, addition of the cationic material in intimate mixture with non-ionic organic surface-active agent in flakes, particles and similar form has the advantage that the stain-staining of clothes after drying is mitigated to a significant extent. As the non-ionic surfactant acts as

a dispersing agent that increases the uniform dispersion of the cationic softener and consequently again the deposition of softener on the treated substances, the non-ionic surfactant also contributes to uniform softness and to counteracting soil redeposition, especially in non-phosphate-containing mixtures.

However, the non-ionic, ethoxylated fatty alcohol dispersant does not contribute as such to increasing the degree of softness obtained with the aid of the cationic fabric softener. Although the reason why the nonionic dispersant does not provide an increased softening benefit is fully understood, it is believed that the reason may be that the nonionic dispersant is not substantial to, i.e. does not bind or attach to, the washed fabrics.

There are many known types and classes of fabric softening compounds, primarily nitrogen-containing compounds, such as the quaternary ammonium salt and imidazolinium salt compounds. Nevertheless, for a plasticizer-active compound to be a candidate for replacement of the "inactive" dispersant in the post-added plasticizer particles, e.g. "prills", according to the British patent application, satisfy several different criteria. The softening compound must thus also act as a dispersant for the finely divided particles of cationic fabric softener compound as soon as "prills" have been added to the washing bath, and must increase the solubility or breakdown of "prills" after introduction into the washing bath. The successful candidate softener/dispersant compound must of course also be compatible with, i.e. non-reactive with, the cationic fabric softener and must also

work into "prills", or other separate particulate form,

and must be compatible with the detergent, the builder and the other components in the detergent mixture. The replacement compound for the nonionic surfactant/dispersant should also contribute to, or at least not adversely affect, the antistatic properties of the overall detergent composition.

The present invention is based on that discovery

that by replacing the nonionic surfactant/dispersant with ethoxylated alcohol, with an equivalent amount of an ethoxylated tertiary amine, the total amount of the cationic plasticizer, in the form of its mixture with the ethoxylated amine, can be substantially reduced without a corresponding reduction in the softness imparted to the treated fabrics, and in some cases with an increase in softness. There is also no adverse effect on the antistatic properties of treated fabrics. While the overall cleaning performance, softness, anti-static and anti-redeposition properties are improved or not adversely affected, the ability to reduce the amount of the cationic amine plasticizer, which is usually the direct active ingredient in the composition, results in a quite significant cost savings.

Cationic plasticizers that can be used here are common known substances and are of the strongly plasticizing type. Included among these are the N,N-di-(higher) C2. A~ C 24 ' N,N-di-(lower) C 1 -C 4 -alkyl quaternary ammonium salts with water-solubilizing anions, such as halide, e.g. chloride, bromide and iodide; sulfate, methosulfate and the like, and the heterocyclic imides, such as imidazolinium compounds.

For convenience, the aliphatic quaternary ammonium salts can be structurally defined as follows:

where R and R<1> are each an alkyl group with 14 - 24, and preferably 14 - 22, carbon atoms,

2 3

R and R are each a lower alkyl group with 1-4, and preferably 1-3, carbon atoms,

X is an anion capable of providing water solubility or dispersibility, including the previously mentioned chloride, bromide, iodide, sulfate and methosulfate anions.

Particularly preferred species of the aliphatic quaternary compounds include:

distearyldimethylammonium chloride,

di-hydrogenated tallow-dimethylammonium chloride, di-tallow-dimethylammonium chloride,

distearyldimethylammonium methylsulfate and di-hydrogenated tallow dimethylammonium methylsulfate.

Heterocyclic imide plasticizers of the imidazolinium type can also be used, and can be defined by the following structural formula:

where R 4 is a lower alkyl group with 1-4, and preferably 1-3, carbon atoms,

R 5 and R 6 are each essentially straight-chain higher alkyl groups with 13-23, and preferably 13-19, carbon atoms, and

X has the previously defined meaning.

Particularly preferred species of the imidazolinium compounds include: 1-methyl-1-tallow-amido-ethyl-2-tallow-imidazolinium methylsulfate; commercially available under the trademark "Varisoft 475" as a liquid, 75% active ingredient in isopropanol solvent,

1-methyl-1-oleyl-amido-ethyl-2-oleylimidazolinium methyl sulfate; commercially available under the trademark “Varisoft

3690", 75% active ingredient in isopropanol solvent.

Mixtures of these cationic fabric softeners can be used, including mixtures of quaternary ammonium salt and imidazolinium salt.

The ethoxylated amine compounds which have been found to be useful are the ethoxylated tertiary amine compounds which can be represented by the following formula:

where R is alkyl or alkenyl with from 8 to 22 carbon atoms, and

x and y are positive numbers, so that the sum x+y is from 2 to 15.

As examples of R, preference is given to alkyl or alkenyl groups having from 12 to 20 carbon atoms, as these can be straight-chained or branched (straight-chained are preferred). The sum x+y is preferably from 5 to 15. Certain examples of suitable R groups include decyl, dodecyl, stearyl, tallow, hydrogenated tallow, dodecyl, myristyl, oleyl and the like, usually derived from the corresponding higher fatty acid. In general, mixtures of alkyl chains of different lengths will be used, such as ci2~ C15' C14~C16' C16~<C>18' C18~C2 0 <o>sv* Stearyl, tallow and hydrogenated tallow compounds are commercially readily available, , such as e.g. Ethomeen<®->series, e.g. Ethomeen<®> T/25 (R = tallow,

x+y=15); Ethomeen<®> T/15 (R = tallow, x+y=5); The Ethomean<®>

18/15 (R = octadecyl (stearyl), x+y=5) and Varonic<®->

the series, e.g. Varonic<®> T-215 (R = tallow, x+y=15);

Varonic<®> T-210 (R = tallow, x+y=10); Varonic<®> U215 (R = mixed cetyl/stearyl, x+y=15); Varonic<®> U205 (R = mixed cetyl/stearyl, x+y=5), and is here preferred for use on the basis of the high levels of effectiveness and the relatively low cost.

In this invention they give ethoxylated fatty amines

a dual action as a dispersant for the cationic fabric softener, equivalent to the action of the non-ionic surfactant with ethoxylated fatty alcohol groups in the compositions according to the aforementioned GB patent application, and also as a softening active nitrogen compound in its own right. Based on this additional softening benefit,

can the total amount of cationic fabric softener that is subsequently added to the detergent mixture be reduced to the same total level of softener-active compounds (cationic softener plus ethoxylated amine), thereby obtaining approximately the same softness and antistatic effect, or the amount of post-added softener/antistatic agent in the form of grains, "prills", etc. can be maintained at the same level to give further increase in softening and antistatic action.

The mixture of cationic and non-ionic compounds is preferably produced in prilled form. "Prills" are prepared by spray cooling a liquefied mixture of the cationic agent and the ethoxylated amine. In the most preferred embodiment, a liquid ethoxylated amine is used and this is added to the molten cationic agent. A typical cationic agent is "Arosurf TA-100" (dimethyldistearylammonium chloride) and after this material is added, it forms a very fluid liquid when melted and heated to 90°C. In another preferred embodiment, the liquid mixture of cationic agent and ethoxylated amine can be cooled to room temperature or, if necessary, until solidification. Solids can then be ground up to the desired particle size and subsequently added to the other detergent ingredients.

Optionally, during compounding, the cationic agent and the ethoxylated amine may first be mixed in the desired amounts to form a substantially homogeneous mass which may be processed according to well-known techniques until it is sufficiently "doughy" or plastic to be suitably shaped. preferably for extrusion or other processing, e.g. pelleting, granulation, stamping or pressing. Processing can be carried out e.g. by grinding in a roller mill, although this is not essential, followed by extrusion in a normal soap machine with the desired type of extrusion head. The latter is chosen in accordance with the form, i.e.

the geometric shape desired on the extrudate. Extrusion in the form of "spaghetti" or noodles is preferred. Other forms, such as flakes, tablets, pellets, ribbons, threads and the like, are suitable alternatives. Special extrusion machines for the above-mentioned purposes are well known in the art and include e.g. Elanco model EXD-60, EXDC-100, EX-130 and EXD-180, a Buhler extruder and the like. Generally

the "spaghetti" extrudate is a form-stable mass, i.e. semi-solid and essentially non-sticky at room temperature so that in most cases it does not require further treatment, such as water removal. If necessary, the latter can be produced by simple drying techniques. The "spaghetti" should have an average length of 2 to 20 mm, with approx. 95% within a tolerance limit of 0.5 to 20 mm, and an average diameter or width of 0.2 to 2.00 mm, with a range of 0.4 to 0.8 mm being preferred. The mass density of the "spaghetti" will usually be from 0.9 to 1.3 g/cm 3. Flakes will measure approx. 4 mm in length and width, and 0.2 mm in thickness, pellets have a cross section of 2.5 mm, while tablets have a cross section of 2.5 mm and thickness of 2.5 mm.

Generally, from 1 to 20% by weight of ethoxylated amine is used based on the weight of the cationic plasticizer. Preferably, the ethoxylated amine should be used in amounts from 5 to 15%,

with 8 - 9% being particularly preferred.

In the particulate detergent and softener mixtures according to the invention, as mentioned, the surface-active agent or detergent is of the anionic type, these materials being particularly advantageous in extra powerful detergents for washing fabrics. Anionic surfactants that can be used here usually include the water-soluble salts of organic reaction products that have in their molecular structure an anionic solubilizing group, such as SO4H, SO^H, COOH and PO4H, and an alkyl or an alkyl group with 8 to 22 carbon atoms in the alkyl group or in the residue. Suitable detergents are anionic detergent salts with alkyl substituents of 8 to 22 carbon atoms, such as: water-soluble sulfated and sulfonated anionic alkali metal and alkaline earth metal salts, and detergent salts containing a hydrophobic higher alkyl residue, such as salts of higher alkyl mono- or polynuclear aryl sulfonates with from 8 to 18 carbon atoms in the alkyl group which may have a straight chain (preferred) or branched chain structure. Preferred species include, without necessary limitation: sodium salt of straight-chain tridecylbenzenesulfonate, sodium salt of straight-chain dodecylbenzenesulfonate, sodium salt of straight-chain decylbenzenesulfonate, lithium or potassium salt of pentapropylenebenzenesulfonate, alkali metal salts of sulfated condensation products of ethylene oxide, such as containing 3 to 20 and preferably 3 to 10 moles of ethylene oxide, with aliphatic alcohols containing 8 to 18 carbon atoms or with alkylphenols with alkyl groups containing 6 to 18 carbon atoms, e.g. sodium nonylphenol pentaethoxamer sulfate and sodium lauryl alcohol triethoxamer sulfate; alkali metal salts of saturated alcohols containing from 8 to 18 carbon atoms, e.g. sodium lauryl sulfate and sodium stearyl sulfate; alkali metal salts of higher fatty acid esters of low molecular weight sulphonic acids, e.g. fatty acid esters of the sodium salt of isethionic acid; fatty ethanolamide sulfates; fatty acid amides of aminoalkyl sulfonic acids, e.g. lauric acid amine of taurine; alkali metal salts of hydroxyalkanesulphonic acids with 8 to 18 carbon atoms in the alkyl group, e.g. hexadecyl-, oc-hydroxy sodium sulfonate. The anionic surfactant or mixture thereof is preferably used in the form of its alkali or io-alkali metal salts. As mentioned, the anionic surfactant is of the non-soap type. The concentration of anionic, non-soap-type surfactant is chosen as mentioned so that there is an excess in terms of cationic agent/plasticizer according to the empirical relationship:

% concentration =1.5 Cs+5

where Cs is the percentage concentration of cationic plasticizer.

This ensures the minimal excess of anionic agent which

is necessary for optimal total washing, softening, etc. effect in the product mixture.

As mentioned, the mixtures include water-soluble

alkaline to neutral building salt in amounts from 10 to 60% by weight of the total mixture. Useful are the organic and inorganic builders, including the alkali metal and alkaline earth metal phosphates, especially the condensed phosphates, such as the pyrophosphates or tripolyphosphates, the silicates, the borates, the carbonates, the bicarbonates and the like. Species thereof include sodium tripolyphosphate, trisodium phosphate, tetrasodium pyrophosphate, sodium salt of acid pyrophosphate, sodium salt of monobasic phosphate, sodium salt of dibasic phosphate, sodium hexametaphosphate; alkali metal silicates, such as sodium metasilicate, sodium silicates, e.g. with Na2O/SiO2 ratio of 1.6:1 to 3.2:1, preferably 1:6 to 1:3.4, most preferably 1:2 to 1:3, such as 1:2.4, sodium carbonate, sodium sulfate, borax, (sodium tetraborate), tetrasodium salt of ethylenediaminetetraacetic acid, trisodium salt of nitrile acetate and the like, and mixtures of the aforementioned. The builder's salt can be chosen so that either phosphate-containing or phosphate-free detergents are obtained. As regards the latter embodiments, sodium carbonate is particularly effective. Another material that has been found to have detergent effects is metakaolin, which is usually prepared by heating kaolinite in crystal lattice form to expel water and produce a material that is essentially amorphous by X-ray examination, but retains some of the structure of the kaolinite. Mentions of kaolin and metakaolin can be found in US patent documents

No. 4,075,280, Columns 3 and 4, and in Grimshaw, "The Chemistry and Physics of Clays and Allied Ceramic Materials", (4th ed., Wiley-Interscience), pp. 723-727. The metakaolin seems

also to have softening benefits. As for the metakaolin,

then the most effective metakaolins seem to be those which behave best in the reaction with sodium hydroxide in terms of forming a "Zeolite 4A", as described in US Patent No. 3,114,603 which refers to such materials as "react-

tive kaolin". As explained in the aforementioned literature, is

metakaolin an aluminum silicate. The metakaolin and/or a zeolite are included in approximately the same amounts as the builder's salt, and ~preferably in addition to this, e.g. zeolite:silicate in a ratio of 6:1. A particularly useful form of the metakaolin is that available commercially as Satintone<®> No. 2.

Preferred optional ingredients which may be used herein include perfumes such as 'benie perfume; optical whiteners, and bluing agents which can be dyes or pigments, suitable materials in this respect include stilbene and Tinopal<® >5BM whiteners, and especially in mixture, and "Direct Brilliant Blue 6B", "Solophenyl Violet 4BL", Cibacete<®> , "Brilliant Blue RBL and Cibacete<®> Violet B; "Polar Brilliant Blue RAW" and "Calcocid Blue 2G" bluing agents. The whitening agent may be included in amounts varying up to 1% of the total mix-

ing, while the bluing agents may constitute up to 0.1%, preferably up to 0.01%, of the total mixture. Bleaching agents, e.g. "Polar Brilliant Blue", may be included in the cationic "prill". In all cases, the amount only needs to be minimal to be effective.

Other components of optimum importance include bleaching agents which may be of the oxygen or chlorine releasing type; oxygen bleaches include sodium and potassium perborate, potassium monopersulfate and the like, while typical chlorine bleaches are sodium hypochlorite, potassium dichloroisocyanurate, trichloroisocyanuric acid and the like. The latter chlorine-releasing bleaches are representative of the broad class of water-soluble, organic, dry solid bleaches known as the N-chloroimides, including their alkali metal salts. These annular imides have from 4 to 6 members in the ring, and are described in more detail in US patent document no. 3 32 5 414. The bleaching agents of both the oxygen and chlorine type mentioned above are completely compatible with the mixtures and have good stability in the presence of the anionic and cationic constituents. They are generally used in amounts ranging from 0.1 to 45% by weight of the total amount of solids, or from 0.05 to 40% based on the total amount of detergent mixture.

Other additional optional ingredients include water-soluble and/or dispersible hydrophobic colloidal cellulosic soil suspending agent. Methylcellulose, eg". Methocel<®> and carboxymethylcellulose (CMC) are particularly effective. Polyvinyl alcohol is likewise effective and especially when washing cotton and synthetic fibers, such as nylon and dacron, and resin-treated cotton. The additional soil-suspending agent may be included in amounts up to 2% based on the total weight of solids, and up to 4% based on the total weight of detergent mixture.

Fillers can also be included in addition to the previously mentioned ingredients, such as sodium sulphate, sodium chloride and the like. The amount will vary up to 40% of the total mixture.

The detergent mixture is prepared by means of conventional processing, such as spray drying of a mixture of surfactant, builder, filler, etc., without volatile components, such as perfume or components that are otherwise adversely affected by the spray drying process, such as peroxygen bleach, e.g. . sodium perborate. Components of this type are preferably mixed afterwards. As previously mentioned, the cationic softener/ethoxylated amine mixture is simply dry blended with the dried particulate detergent by simple mechanical mixing which is more than sufficient to give a homogeneous product. The following would be a typical procedure: water is mixed into a grinding mixture followed in order by anionic surfactant, sodium silicate, any ingredients used, such as Santitone<®> No. 2 and fillers, such as sodium sulfate and building salt. The grinding mixture is heated to approx. 60°C before adding builder, e.g. sodium tripolyphosphate, and the content of solids in the grinding mixture before spray drying is 55 - 65%. Spray drying can be carried out in a conventional manner by pumping the hot mixture from the grinding apparatus to a spray tower where the mixture passes through a spray nozzle and into a hot evaporating atmosphere. Bleach and other substances which remain to be added are incorporated into the cooled dried detergent mass by any suitable means, such as simple mechanical mixing.

In use, add enough of the detergent mixture to the wash cycle, whereby a concentration of cationic softener in the detergent is obtained of 1.5 to 8.0 g/3500 g of laundry at a range from 21°C to the boiling point (i.e. approx. 100°C) . In this context, it should be understood that "cold" washing means a washing temperature of up to 21°C, "hot" is from 21°C to boiling.

Certain types of aliphatic quaternary ammonium compounds, although relatively ineffective in terms of softening, are nevertheless very effective as antistatic agents in the mixtures, and especially as they are physically compatible with anionic surfactants in liquid environments. In general, such substances include the ethoxylated and/or propoxylated quaternary ammonium compounds with the following formula:

where R 7 and R 8 are each an ethoxy or propoxy group, m and n are integers from 1 to 50 and may be the same or different, R 9 is an alkyl group with 14-24 carbon atoms and X is as defined above. Compounds of this type include (a) methylbis-(2-hydroxy-ethyl)-coco ammonium chloride, a liquid with 75% active ingredient in isopropanol/water as solvent, and commercially available as Ethoquad<®> c/12, Armak<®> and Variquat<®> 638; (b) Ethoquad<®> c/25 - same

as under (a), but with 15 moles of ethylene oxide (both R 7 and R g , both m and n = 15) and available as 95% active ingredient; (c) methylbis-(2-hydroxy-ethyl)-octadecyl-ammonium chloride, a liquid with 75% active ingredient in isopropanol/water as solvent, commercially available

as Ethoquad<®> 8/12, Armak<®>, and (d) same as (c), but with

7 8 15 mol ethylene oxide (both R and R , both m and n = 15), a liquid with 95% active ingredient and commercially available as Ethoquad<®> 18/15, Armak<®>. These substances can be used in amounts varying up to 10% by weight of the total mixture.

The present invention can be practiced in various ways and a number of specific embodiments will be described to illustrate the invention with reference to the accompanying examples where all parts and percentages are based on weight.

Example IA and Example IB

A) 88 parts of powdered "Arosurf TA" (dimethyldistearylammonium chloride) was heated to 90°C and a liquid melt occurred. To this melt was added 8 parts Ethomeen<® >T-25, 1 part calcium silicate and 3 parts water. The mixture was stirred well and then cooled to room temperature. A white solid was obtained. The solid was then ground to a powder (on US No. 8 sieve 0% through, US No. 100 sieve less than 10% through, a No. 8 sieve has apertures with a cross section of 2.38 mm, a No. 100 sieve has openings with a cross section of 14 9 pm). the product resembles the original "Arosurf" powder. B) Example IA was repeated, except that 8 parts of a nonionic dispersant with ethoxylated fatty alcohol groups was used in place of the ethoxylated amine.

Example 2

A spray-dried, extra-powerful detergent with the following composition was produced:

To 100 g of the above-mentioned mixture was added 4.1 g (4.1%) of the cationic powder according to example IA, or 4.5 g (4.5%) of the cationic powder according to

example IB, whereby mixtures 2A and 2B were obtained respectively. Each of the blends 2A and 2B were tested for softness and antistatic properties. The results are shown in Table A. Softness was determined under the following conditions: a quantity of fabric (total weight approx. 700 g) consisting of 4 terry towels, 3 x 38 cm test pieces of each of the following 7 fabric types: banlon, dacron double knit (DDK ), dacron/cotton blend (65/35), cotton percale, acetate jersey fabric (AJ), nylon tricot and dacron polyester single knit (DSK),

and 10 test pieces of each of three different soiled fabrics (spinach on 50/50 dacron/cotton; skin fat on DDK and Piscataway clay on 50/50 dacron/cotton) were washed at 38°C with 64 liters of wash water (150 ppm) in a "Mayta" washing machine using 100 g of wash mix. After one single wash cycle, the fabric was dried in a commercially available dryer for about 30 minutes and set aside to cool for about 2 hours.

Six experienced testers were used to evaluate the softness of the towels treated with each of the test compositions using one of two methods: for each test composition, each of the four towels was scored relative to each of the towels treated with each of the other test compositions (in four separate groupings), and given points in order from softest to hardest; or each of the four towels for each test mixture was scored on a scale of 1 (no softening)

to 10 (excellent softness), and an average of the four values was determined as the softness number. In the first test (softening by comparison) for each test mixture, the total number of first places (1 point), second places (2 points), third places (3 points), etc. were summed and the lowest sum corresponds to the best softening effect. In the latter test (sliding scale), the average softness number for each tester was used to calculate an average value together with the softness number assigned by the other testers to arrive at a single softness number, the higher the number, the better the softening effect. Both of these methods have been found to be a statistically significant and reliable method for evaluating softness.

Antistatic effect is determined by measuring static charge (volts) which builds up on test pieces of four different fabrics: dacron/cotton (65/35), dacron double knit (DDK), acetate jersey fabric (AJ) and banlon polyester, washed as . described above. Each of the three washed and machine-dried test pieces of each of the four different fabrics was clamped onto a holding frame. A small fabric sample of wool attached to the outer edge of a rotating circular holder was rotated in the holder in contact with the fabric samples for 5 seconds. The temperature was kept at 21 - 22°C and the relative humidity at 21%. The average of the voltage values for each fabric (three different test pieces) was calculated, and the average voltage values for the four different fabrics were calculated to obtain the figure for static electricity. The lower the figure for static electricity, the better the antistatic effect of the washing mixture. In general, figures for static electricity are considered to be less than approx. 5 kilovolts (KV), which are very good and are perceived by the consumer as the absence of a build-up of static electricity.

In a side-by-side softness comparison test, sample 2B received 11 first-place votes (35 points), while sample 2A received 13 first-place votes (37 points).

Example 3

Example IA was repeated except that the mixt

of dimethyldistearylammonium chloride, tallow adduct with 15 mol of ethylene oxide, calcium silicate and water was stirred and fed to the inlet of a soap extrusion apparatus where it was extruded in the form of "spaghetti" or noodles. When the "spaghetti" or noodles are added to the spray dried detergent shown in Example 2, similar results were obtained as for Mixture 2A.

Example 4

Example IA was repeated except that in ste'

for Ethomeen<®> T/25 the following ethoxylated tertiary amines were used:

(a) polyoxyethylene-(5)-octadecylamine

(b) polyoxyethylene-(5)-tallow amine

(c) polyoxyethylene-(10)-tallow amine

(d) polyoxyethylene-(15)-tallow amine

(e) polyoxyethylene-(5)-(hydrogenated tallow)

(f) polyoxyethylene-(15)-(hydrogenated tallow)

Example 5

For a spray-dried detergent mixture with the following approximate composition:

4% of the cationic plasticizer/ethoxylated amine plasticizer dispersant according to Example IA was added. Excellent washing effect and softening effect were achieved.

Example 6

4.5 g of the cationic softener/ethoxylated amine powder according to Example IA was subsequently added to the spray-dried detergent powder according to Example 2. Further improvements with respect to softening were provided (sliding scale softness number: 9-10).

The following examples illustrate the preparation and use of the mixture of cationic and non-ionic agent in prilled form.

Example 7

500 kg of dimethyldistearylammonium chloride which contained approx. 4% water was heated to 90°C and formed a melt. To this hot melt was added 25 kg Ethomeen<®> T/25. This amalgam was then sprayed downwards from the top

an approx. 24 m high tower with a diameter of approx. 5m). At the same time, cooling air at approx. 10°C sent upwards (i.e. countercurrent to the falling spray) at a speed of approx. 850_m per minute. The solidified product was collected at the bottom of the tower. The product particle is white in appearance, easily flowing, generally spherical and solid. It has a porous surface (cup-scarred appearance). The mass density of the "prill" is approx. 0.37 g/cm .

Example 8

To 95.5 g of the detergent according to example 2 (without example IA particles) 4.0 or 4.5 g of the "prilles" according to example 7 were added.

Example 9

Each of the above examples was again repeated, except that the cationic plasticizer in the mixture of cationic agent and ethoxylated amine was replaced by the following: (a) dimethyl-di-tallow-ammonium methosulfate; (b) dimethyl-dihydrogenated tallow ammonium chloride; (c) 1-methyl-1-tallow-amido-ethyl-2-tallow-imidazolinium methosulfate; (d) 1-methyl-1-oleylamidoethyl-2-oleyl-imidazolinium methosulfate.

Claims (14)

1. _ Particulate detergent and softener mixture capable of imparting to treated fabrics improved softness, washing performance, antistatic and anti-dirt redeposition properties, in a washing process, characterized in that it comprises from 5 to 40% by weight of water-soluble, non-soap-containing, organic , anionic surfactant, from 10 to 60% by weight water-soluble, neutral to alkaline building salt, and substantially homogeneously dispersed in the mixture as discrete particles, from 2 to 20% by weight, based on the total mixture, of an intimate mixture of ( i) a cationic amine as a plasticizer, and (ii) a water-soluble, ethoxylated, tertiary amine compound as a dispersant and plasticizer, of the formula where R is alkyl or alkenyl with from 8 to 22 carbon atoms, and x and y are such positive numbers that the sum x + y is from 2 to 15, the percentage concentration of anionic surfactant being at least 1.5 Cs + 5, where Cs is the percentage concentration of the total amount of plasticizer (i) and (ii), and the amount of the ethoxylated tertiary amine (ii) is from 2 to 50% by weight of the mixture of (i) and (ii). 2. Mixture according to claim 1, characterized in that R is C16-C18 alkyl. 3. Mixture according to claim 1, characterized in that R is stearyl, cetyl, tallow, hydrogenated tallow or mixtures thereof. 4. Mixture according to claim 1, characterized in that R is C10-C20 alkyl or alkenyl, and x + y is from 5 to 15. 5. Mixture according to claim 1, characterized in that the amount of the ethoxylated tertiary amine is from 2 to 20% by weight of the mixture of (i) and (ii), the mixture constituting from 2 to 15% of the total mixture. 6. Mixture according to claim 1, characterized in that the ethoxylated, tertiary amine comprises from 2 to 15% by weight of the mixture of the cationic amine (i) and ethoxylated, tertiary amine (ii), and that this mixture constitutes from 2 to 10% by weight of the total mixture. 7. Mixture according to claim 1, characterized in that the intimate mixture is the finely ground product of a fusion of the cationic and ethoxylated amine components. 8. Mixture according to claim 1, characterized in that the mixture of cationic amine and ethoxylated amine consists mainly of spherical particles with a solid core and porous surface. 9. Mixture according to claim 1, characterized in that the cationic amine (i) is a di-short-chain alkyl, di-long-chain alkyl, quaternary ammonium halide or an imidazolinium compound. 10. Mixture according to claim 1, characterized in that the cationic amine plasticizer (i) is a di-C1-C4 alkyl, di-C14-C18 alkyl, ammonium halide and the ethoxylated amine is a C8-C18 straight-chain, aliphatic, tertiary amine containing from 2 to 15 moles of ethylene oxide. 11. Mixture according to claim 1, characterized in that the cationic amine as plasticizer is selected from the group consisting of di-C-L-Qj-alkyl, di-C14-C18-alkyl, quaternary ammonium salts, imidazole-inium salts and mixtures thereof, and the ethoxylated amine is a C12-C18 straight chain , aliphatic, tertiary amine containing from 5 to 15 moles of ethylene oxide. 12. Mixture according to claim 1, characterized in that the non-soap, anionic detergent comprises an alkylbenzene sulphonate, and the builder comprises a phosphate. 13. Mixture according to claim 12, characterized in that the non-soap anionic detergent is a C8-C18 straight-chain alkylbenzene sulfonate. 14. Mixture according to claim 1, characterized in that the non-soap detergent comprises a C8-C18 straight chain alkylbenzene sulphonate, the builder comprises a phosphate, the cationic amine (ii) is a di-C^-C^-alkyl, di-C14-C18-alkyl, ammonium halide, the ethoxylated amine (ii) is a C12-C18 straight-chain, tertiary amine containing from 5 to 15 moles of ethylene oxide, and the ethoxylated amine constitutes from 3 to 10% by weight of the mixture of cationic plasticizer and ethoxylated amine.