NL8700193A - DETERGENT-SOFTENER COMPOSITIONS. - Google Patents

Description

* A

VO 9015

Title: Detergent fabric softener compositions.

The present invention relates to detergent compositions and in particular to detergent fabric softener compositions which can impart improved softness, detergent effects, redeposition of antifouling and anti-static properties to treated and particularly machine-treated tissues.

Compositions for simultaneously achieving cleaning power and a significant level of softness in machine washing fabrics, and thus suitable for use in the wash cycle, are known per se and are widely available on the market. The transient interaction between anionic surfactant, perhaps the most widely used type of surfactant of the available types, and cationic fabric softeners, especially those of the di-lower-di-higher alkyl quaternary ammonium type, is also well known in the patent literature. Such an interaction often results in the formation of unsightly deposits that become entrapped or otherwise deposited on the washed tissue. Discoloration or other aesthetically unpleasant effects are inevitable for the most part. The net result is often an exhaustion of the effective amount of anionic surfactant available for useful purposes, because the loss of anionic surfactant is the primary result of this interaction.

While the most effective types of cationic quaternary ammonium fabric softeners, such as, for example, the aforementioned di-higher alkyl-type quaternary compounds, such as, for example, distearyl dimethyl ammonium chloride, may function in the wash cycle in the presence of anionic surfactant, builder, etc., the amount needed to achieve effective fabric softening, usually in conjunction with amounts that promote undesired cationic-anionic interactions. As a general rule, at least about twice as much cationic surfactant is required for fabric softening as for anti-static activity. Representative prior art dealing with this problem is discussed below.

8700133 *. - 2 -

U.S. Pat. No. 3,325,414, which primarily deals with detergents having controlled foaming or sudsing ability, discusses the cationic-anionic problem and its associated deleterious effects in detail. Furthermore, this publication explains that certain quaternary ammonium compounds, from the class of cationic agents, are generally unstable when heated and in contact with basic builders, which instability is manifested in the development of strong amine odors and unwanted colors. The compositions according to said patent are limited to the use of quaternary ammonium halides with only one high alkyl group, the given structural formula for the cationic material being accordingly limited. Cationic compounds of this type are clearly inferior to the di-higher alkyl types, at least as far as tissue softening activity is concerned,

The problem of incompatibility of cationics in anionic detergents is also recognized in U.S. Pat. Nos. 3,936,537 and 4,141,841 and it proposes to use an organic dispersion inhibitor as an essential ingredient in combination with the cationic agent. An important property of such inhibitors is a maximum water solubility at 25 ° C of 50 ppm. Similar descriptions can also be found in U.S. Patents 4,113,630; 4,196,104 and 4,272,386.

US Patent 4,230,590 to Wixon discloses heavy duty detergents comprising conventional builders, predominantly anionic surfactant components, cationic fabric softeners and a mixture of fatty acid soap and cellulose ether. The soap-cellulose ether mixture is in the form of spaghetti, flakes or other form and is present in the composition in the form of substantially homogeneously dispersed discrete particles.

U.S. Patent 4,298,480 to Wixon discloses heavy duty detergents with compositions as described in the preceding paragraph, except that cellulose ether is excluded.

87 fl Λ -1 0 7 «* i - 3 -

U.S. Patent 4,329,237 to Wixon also describes heavy duty detergents as in the previous two paragraphs, except that the soap particles are mixed with nonionic surfactant.

In British Patent Application 2,133,813A to Taha, published on August 1, 1984, further improvements in the aforementioned Wixon patents - manifested in less greasy stains (spot staining) due to, for example, the cationic fabric softener - are obtained by additionally dispersed on and homogeneously by incorporating the anionic surfactant and the detergent builder discrete particles (eg prills) of a mixture of the cationic amine fabric softener and nonionic organic surfactant.

See also U.S. Patents 4,339,335; 4,326,971; 4,416,811; 4,411,803 and 4,450,085 to Wixon and Joshi U.S. Patent 4,414,129, which disclose all granular or powdered detergent-fabric softener compositions.

While the detergent / soap and cationic fabric softener containing detergent compositions noted above have desirable fabric softening, anti-static, and cleaning properties, still further improvements in these properties are desired as well as a simultaneous reduction in the overall cost of the product.

The present invention provides stable detergent fabric softener compositions which can impart improved fabric softening without staining, cleaning performance, antistatic properties and redeposition of anti-soiling properties to fabrics treated in a washing process in cold or hot water. The compositions generally comprise about 5-40% by weight of a water-soluble, non-soap anionic surfactant, about 10-60% by weight of water-soluble, neutral to basic builder salt, and substantially homogeneous in this composition dispersed in the form of discrete particles an intimate mixture of (i) about 2-20% by weight of the composition of a cationic amine fabric softener, such as (a) aliphatic, didageC1 -C1 alkyl, di- (higher) alkylquaternary ammonium salts, (b) heterocyclic compounds, and mixtures of (a) and (b), with (ii) a water-soluble ethoxylated tertiary 8700193 r-4-amine dispersant / fabric softener compound (preferably 2-50 wt%, based on the weight of the cationic fabric softener (i)), the percent concentration of the anionic surfactant being at least about (1.5 Cs + 5), where Cs is the percent concentration of the total of the fabric softeners (i) and (ii) proposes,

In certain other aspects, the invention includes both the methods of composition and those of using the aforementioned compositions.

As described in the aforementioned British Patent Application No. 2,133,813A, addition of the cationic material in an intimate mixture with nonionic organic surfactant in the form of flakes, granules and the like has the advantage that the staining of the clothing after drying in is greatly reduced. Since the nonionic surfactant functions as a dispersant promoting the uniform dispersion of the cationic fabric softener and thereby uniform deposition of the fabric softener on the treated fabrics, the nonionic surfactant also contributes to uniform softness and redeposition anti-fouling properties, especially in compositions without phosphates.

However, the nonionic ethoxylated fatty alcohol dispersant per se does not help to increase the softness level imparted by the cationic fabric softener. While the reason for the nonionic dispersant not providing stronger softening is not fully understood, it is believed that the reason may be that the nonionic dispersant does not bind or adhere to the washed tissues.

There are many known types and classes of fabric softening compounds, primarily nitrogen containing compounds, such as the quaternary ammonium salts and imidazolinium salts. To be a candidate for replacing the non-active dispersant in the fabric softener particles added later, for example, prills of the aforementioned British Patent Application, must be a compound of. fabric softening activity, however, meet several different criteria. The fabric softening compound must also function as a dispersant for the finely divided particles of cationic fabric softening compound once the grills are added to the wash bath and dissolve or disintegrate the prills upon insertion. in the washing bath. The successful candidate fabric softener / dispersant compound must of course also be compatible with, i.e., not react with, the 5 cationic fabric softener and must also be capable of incorporating into the prills or other discrete particulate forms, and must be compatible with the detergent, builder, and other ingredients of the detergent composition. The nonionic surfactant / dispersant substitute compound must also contribute to or at least not adversely affect the anti-static properties of the total detergent composition.

The present invention is based on the finding that by replacing the ethoxylated alcohol nonionic surfactant / dispersant with an equivalent amount of an ethoxylated tertiary amine, the total amount of the cationic fabric softener - in the form of its mixture with the ethoxylated amine can be significantly reduced without a corresponding reduction in the softness imparted to treated fabrics, and in some cases with an increase in softness. Nor does it adversely affect the anti-static properties of the treated fabrics. While the overall cleaning, fabric softening, anti-static, and re-fouling properties are improved or not adversely affected, the ability to reduce the amount of the cationic amine fabric softener, which normally represents the most expensive active ingredients in the composition, leads to a significant cost reduction.

Cationic fabric softeners useful herein are suitable known materials and belong to the type of the strong fabric softeners. These include the N, N-di- (higher) C 1 -C 2, N, N-di (lower) C 1 -alkyl quaternary ammonium salts with anions, which give solubility in water, such as halide, for example 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 defined by the formula 1 structural formula, wherein 8700193 f-6-R and R 4 each represent an alkyl group having 14-24 and preferably 14-22 carbon 2-3 atoms; R and R each represent a lower alkyl group having 1 to 4 and preferably 1 to 3 carbon atoms, X represents an anion which may give water solubility or water dispersibility, including the aforementioned chloride, bromide, iodide, sulfate and methosulfate anions.

Particularly preferred species of aliphatic quaternary compounds include: distearyl dimethyl ammonium chloride, di-hydrogenated tallow dimethyl ammonium chloride, di-tallow dimethyl ammonium chloride, distearyl dimethyl ammonium methyl sulfate, and di-hydrogenated tallow dimethyl ammonium methyl sulfate. Imidazolium type 15 heterocyclic imide fabric softeners can also be used and can be structurally defined 4 of Structural Formula 2 of the formula sheet, wherein R represents a lower alkyl group having 1 to 4 and preferably 1-3 carbon atoms; R and R each represent substantially linear higher alkyl groups having about 13 to 23 and preferably 13 to 19 carbon atoms and X has the aforementioned 20 meaning. Particularly preferred species of imidazolinium compounds are: 1-methyl-1-tallow amido ethyl-2-tallow imidazolinium methyl sulfate; commercially available from Sherex Chemical Co. under the trademark Varisoft 475 as a liquid, 75% active ingredient in isopropanol as a solvent, 1-methyl-1-oleylamidoethyl-2-oleylimidazolinium methyl sulfate; commercially available from Sherex Chemical Co., under the trademark Varisoft 3690, 75% active ingredient in isopropanol as a solvent.

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

The ethoxylated amine compounds found useful herein are the ethoxylated tertiary amine compounds which can be represented by the structural formula 3 of the formula sheet, wherein R is an organic fat group and x and y positive numbers such that the sum x + y equals 8700193 • Λ - 7 - is from about 2 to about 15.

As examples of the organic fatty group R, alkyl or alkenyl groups are preferred, which may be linear or branched (linear is preferred), and which may have about 8 to about 22 carbon atoms, preferably about 12 to 20 carbon atoms. The sum x + y is preferably about 5 to about 15. Specific 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, 10 mixtures of different alkyl chain lengths will be used, such as C12-15 'C14-16' C16-18 'Cj8-20' etc * stear? L 'tallow and hydrogenated tallow compounds are readily available commercially, such as

R

for example the Ethendom series from Armak Chemical Co., for example

Ethomen T / 25 (R-tallow, x + y = 15); Ethomen T / 15 (R = tallow, x + y = 5);

R

Ethynom 18/15 (R = octadecyl (stearyl), x + y = 5); and the Varonic series from Sherex Chemicals, for example 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 are preferred for use herein because of their high quality and relatively low costs.

In this invention, the ethoxylated fatty amines perform the dual function of a cationic fabric softener dispersant equivalent to the function of the ethoxylated fatty alcohol nonionic surfactant in the compositions of the aforementioned British Patent Application of Taha, as well as a fabric softening active. nitrogen compound by itself. In connection with this additional fabric softening benefit, the total amount of cationic fabric softener subsequently added to the detergent powder composition can be reduced to the same total level of fabric softening active compounds (cationic fabric softener + ethoxylated amine) to approximately the same softness and anti-static properties, or the amount of fabric softener / antistatic granules, prills, etc. added afterwards. kept at the same level to achieve further improvement in fabric softening and anti-static properties.

8700193 * * - 8 -

The mixture of cationic and nonionic is preferably prepared in the form of prills. The prills are prepared by spray-cooling a liquefied mixture of the cationic substance and the ethoxylated amine. In the most prepared embodiment 5, a liquid ethoxylated amine is used and added to the molten cationic material. A typical example of a cationic substance is Arosurf TA-100 (dimethyldistearylammonium chloride) and as supplied this material forms a very liquid liquid when melted and heated to 90 ° C. The liquid mixture of cationic material and ethoxylated amine in another preferred embodiment may be allowed to cool to room temperature or as needed to solidify. The solid can then be ground to a desired particle size and subsequently added to the other detergent ingredients.

Another possibility is that the cationic substance and the ethoxylated amine, when combined, are first mixed in the desired amounts to form a substantially homogeneous mass which can be processed, according to well known techniques, until it is sufficiently "doughy" or plastic to be in a suitable form for, for example, extrusion or other process, for example, pelleting, granulating, stamping or pressing. For example, the operation can be performed by roller milling, although this is not essential, followed by extrusion into a conventional soap mixer ("plodder") with the desired type of extrusion head. The extrusion head is selected in accordance with the shape, ie geometric shape, desired in the extrudate.

Extrusion in the form of spaghetti or noodles is preferred. Other shaped shapes such as flakes, tablets, pellets, ribbons, threads and the like are suitable alternatives. Special extruders for the above mentioned purposes are known per se and include, for example, the Elanco models EXD-60; EXCD-100? EX-130 and EXD-180, a Buhler extruder and the like. In general, the spaghetti extrudate is a shape retaining mass, i.e., semi-solid and substantially non-tacky at room temperature, so that in most cases no further treatment such as water removal is required.

If desired, the latter can be carried out by simple drying techniques 8700103 * a - 9 -. The spaghetti preferably has an average length of about 2 to 20 mm with about 95% thereof being within a tolerance of 0.5-20 mm and an average diameter or width of about 0.2 to 2.00 mm with the preferred a range from 0.4 to 0.8 mm. The bulk density of the spaghetti will usually be about 0.9 to 1.3 g / cm3. Flakes will have a length and width of about 4 mm and a thickness of about 0.2 mm, while pellets will have a diameter of 2.5 mm and tablets will have a diameter of 2.5 mm and a thickness of 2.5 mm to have.

Generally, 1 to 20% by weight of ethoxylated amine is considered based on the weight of the cationic fabric softener. Preferably, the ethoxylated amine is used in amounts from 5 to 15%, with particular preference being from about 8-9%.

While conventional type surfactants can be used herein, it is preferred that at least about 90% and preferably at least about 95% of the total surfactant or detergent be of the anionic type, these materials being particularly advantageous in heavy duty detergents for washing fabrics. Anionics for use herein generally include the water-soluble salts of organic reaction products having in their molecular structure an anionic solubilizing group such as SOH, SOH, COOH and POH as well as an alkyl or alkyl group having about 8 -22 carbon atoms in the alkyl group or the alkyl portion. Suitable detergents are anionic detergent salts with alkyl substituents of 8 to 22 carbon-25 atoms such as water-soluble sulfated and sulfonated anionic alkali metal and alkaline earth metal and detergent salts containing a hydrophobic higher alkyl group, such as salts of higher alkyl mono or poly-nuclear aryl sulfonates with about 8 18 carbon atoms in the alkyl group which has a straight (preferred) or branched chain structure. Preferred, but not limited to, examples of compounds include sodium linear tridecylbenzene sulfonate, sodium linear dodecylbenzene sulfonate, sodium linear decylbenzene sulfonate, lithium, or potassium pentapropylene benzene sulfonate; alkali metal salts of sulfated condensation products of ethylene oxide, for example with 3 to 20 and preferably 3 to 10 mol ethylene oxide, 8700193 * - 10 - with aliphatic alcohols containing 8 to 18 carbon atoms or with alkyl phenols with alkyl groups containing 6 to 18 carbon atoms , for example sodium nonyl phenol pentaethoxamer sulfate and sodium lauryl alcohol triethoxamer sulfate; alkali metal salts of saturated alcohols having about 8 to 18 carbon atoms, for example sodium lauryl sulfate and sodium stearyl sulfate; alkali metal salts of higher fatty acid esters of low molecular weight alkylol sulfonic acids, for example, fatty acid esters of the sodium salt of isethionic acid; fatty ethanolamide sulfates; fatty acid amides of aminoalkyl sulfonic acids, for example lauric acid amine of taurine; alkali metal salts of hydroxyalkane sulfonic acids having 8 to 18 carbon atoms in the alkyl group, for example hexadecyl, alpha hydroxy sodium sulfonate. The anionic surfactant or mixture thereof is preferably used in the form of its alkali or alkaline earth metal salts. The anionic surfactant is preferably of the non-soap type. However, minor amounts of soap, e.g., about 35% total, and preferably 20%, based on the total amount of anionic, may, for example, be added to the crust mixture.

The concentration of non-soap anionic surfactant is preferably chosen to give an excess over cationic fabric softener according to the empirical relationship:% concentration = 1.5 Cs + 5 where Cs is the percentage concentration of the cationic fabric softener is. This ensures the minimum excess of anionic material required for optimum overall cleaning performance, fabric softening, etc., in the product composition.

Minor amounts of other detergent types may be included together with the anionic surfactant, their total in any case being no more than about 10% and preferably about 2-5% of the total amount of detergent, i.e. of this other detergent plus the non-soap anionic. Useful here are the nonionic surfactants containing an organic hydrophobic group and a hydrophilic group which is a reaction product of a solubilizing group such as carboxylate, hydroxyl, amido or 35 amino with ethylene oxide or with its polyhydration product, poly 8700193 • «- 11-ethylene glycol. This includes condensation products from C to C

o 3U

fatty alcohols such as tridecyl alcohol with 3 to 100 moles of ethylene oxide;

C / g to C / g alcohols with 11 to 50 moles of ethylene oxide; ethylene oxide adducts with monoesters of polyhydric, for example hexahydric, alcohol; condensation products of polypropylene glycol with 3 to 100 moles of ethylene oxide; the condensation products of alkyl (C, straight or branched chain) phenols with 3 to 100 moles of ethylene oxide and the like.

Suitable amphoteric detergent compositions generally include those comprising both an anionic group and a cationic group, and a hydrophobic organic group, which is preferably a higher aliphatic group having 10 to 20 carbon atoms; examples include the N long chain alkylaminocarboxylic acids and the N long chain alkyl imino dicarboxylic acids as described in U.S. Pat. No. 3,824,189.

The present compositions preferably comprise aqueous-15. releasable basic to neutral builder salts in amounts of from about 10 to 60% by weight of the total composition. Useful herein 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, silicates, borates, carbonates, bicarbonates and the like. Examples thereof are sodium tripolyphosphate, trisodium phosphate, tetrasodium pyrophosphate, sodium acid pyrophosphate, sodium monobasic phosphate, sodium dibasic phosphate, sodium hexametaphosphate; alkali metal silicates such as sodium metasilicate, sodium silicates, for example, with Na 2 O / SiC> 2 ratios from 1.6: 1 to 3.2: 1, preferably 1: 6 to 1: 3.4, more particularly 1: 2 to 1: 3, such as 1: 2.4, sodium carbonate, sodium sulfate, borax (sodium tetraborate), ethylenediamine tetraacetic acid tetrasodium salt, trisodium nitriloacetate and the like as well as mixtures thereof. The builder salt can be selected to yield either phosphate-containing or phosphate-free detergents . With regard to the latter embodiments, sodium carbonate is particularly effective. Another material that has been found to have good cleaning effects is metakaolin which is generally obtained by heating the kaolinite lattice to expel water to yield a material which is substantially amorphous by X-ray but which is 8 A * λ * * * U ij i 'j O' '• «- 12 - retains some of the structure of the kaolinite. Discussions of kaolin and metakaolin are found in U.S. Pat. No. 4,075,280, columns 3 and 4 and in Grimshaw, "The Chemistry and Physics of Clays and Allied Ceramic Materials" (4th Edition, Wiley-Interscience), 5 pp. 723- 727. Metakaolin is also the subject of U.S. Patent Applications 905,622 and 905,718, the relevant parts of which are to be incorporated herein by reference. The metakaolin has also been found to have utility as a fabric softener. With regard to the latter, the most effective metakaolin products appear to be those which behave best in a reaction with sodium hydroxide to form zeolite 4A as described in U.S. Pat. No. 3,114,603, which designates such materials as "reactive kaolin." As set forth in said publications, metakaolin is an aluminosilicate. The metakaolin and / or a zeolite is included in about the same amounts as the builder salt, and preferably in addition to it, for example zeolite: silicate in a ratio of 6: 1. A particularly useful form of the metakaolin is that which is commercially available as Satintone No. 2.

Preferred optional ingredients useful herein include perfumes such as Genie perfume; optical brighteners and bluing agents which may be dyes or pigments, in which regard suitable materials are stilbene and Tinopal 5BM brighteners, especially in combination, as well as Direct Brilliant Sky Blue 6B, Solophenyl Violet 4BL, Cibacete, Brilliant Blue RBL and Cibacete Violet B , Polar 25 Brilliant Blue RAW and Calcocid Blue 2G blue agents. The brightener can be included in amounts ranging up to about 1% of the total composition, while bluing agents can be present in amounts up to about 0.1%, preferably up to about 0.01% of the total composition. Blue agents, for example Polar Brilliant Blue, 30 can be included in the cationic prill. Either way, the amount need only be minimal to be effective.

Other preferred ingredients include bleaches which may be of the oxygen or chlorine releasing type; oxygen bleaches include sodium and potassium perborate, potassium mono-persulfate and the like, while chlorine bleaches are typically represented by 8700193 * - * * 13 - represented by sodium hypochlorite, potassium dichloroisocyanurate, trichloroisocyanuric acid and the like. The latter chlorine-relieving bleaches are representative of the broad class of water-soluble, organic, dry solid bleaches known as the 5-N-chloroimides including their alkali metal salts. These cyclic imides have about 4 to 6 members in the ring and are detailed described in U.S. Patent 3,325,414. Each of the oxygen and chlorine type bleaches discussed above are fully compatible with the compositions described herein and have good stability in the presence of the anionic and cationic components. They are generally used in amounts ranging from about 0.1 to 45% by weight of the total solids or from about 0.05% to about 40%, based on the total detergent composition.

Still other optional ingredients include water-soluble and / or dispersible hydrophobic colloidal cellulose-type soil suspending agents. Methyl cellulose, for example the brand name Methocel and carboxymethyl cellulose (CMC) are particularly effective. Polyvinyl alcohol is also effective and particularly in washing cotton and synthetic fibers such as nylon, dacron and resin treated cotton.

The additional soil suspending agent can be included in amounts up to about 2% based on the total amount of solids and up to about 4% based on the total detergent composition.

Fillers can also be included in addition to the aforementioned ingredients, such as sodium sulfate, sodium chloride and the like.

The amount will vary up to about 40% of the total composition.

The detergent composition is prepared by conventional processing methods, such as spray drying a surfactant, builder, filler, etc. crust mixture without volatile ingredients such as perfumes, or ingredients otherwise adversely affected by the spray drying process such as peroxygen bleaches, e.g., sodium perborate. Ingredients of this type are preferably mixed afterwards. As mentioned earlier, the mixture of cationic fabric softeners / ethoxylated amine is simply dry mixed with the dried detergent in particulate form by simple mechanical mixing 3700193-14 which is more than effective to obtain a homogeneous product. A normal procedure could be as follows: water is added to a crutcher, followed in sequence by anionic surfactant, sodium silicate, optional ingredients when used such as Satintone 5 No. 2 and fillers such as sodium sulfate and builder salt. The crutcher mixture is heated to about 60 ° C before the builder is added, for example sodium tripolyphosphate, and the solids content of the crutcher mixture before spray drying is about 55-65%. Spray drying can be performed in a conventional manner by pumping the hot mixture from the crutcher to a spray tower where the mixture passes through a spray nozzle in a hot evaporation atmosphere. Bleach and other materials to be added are incorporated into the cooled, dried detergent composition by any suitable method, for example, by simple mechanical mixing.

In use, sufficient amount of the detergent composition is added to the wash cycle to obtain a concentration of cationic fabric softener in the wash medium of about 1.5-8.0 g / 3500 g of laundry ranging from about 21 ° C to the boiling point of 100 ° C. In this connection, cold washing refers to a washing temperature of up to 21 ° C, while warm washing refers to a temperature of 21 ° C up to the boiling point.

Certain types of aliphatic quaternary ammonium compounds, although relatively ineffective in fabric softening properties, are nevertheless very effective as antistatic agents in the present compositions and in particular because they are physically compatible with anionic surfactants in liquid environments.

In general, such materials include the ethoxylated and / or propoxylated quaternary ammonium compounds of formula 4 of the formula 8 wherein R and R each represent an ethoxy or propoxy group, m and n are integers from 1 to 50 and the same or different. 30, and R represents an alkyl group having 14 to 24 carbon atoms, and X has the aforementioned meaning. Compounds of this type include (a) methylbis (2-hydroxyethyl) cocoammonium chloride, a liquid 75% active ingredient in isopropanol / water solvent and commercially available under the brand Ethoquad c / 12, Armak and the brand 35 Variquat 638 from Sherex Chemical Co.; (b) Ethoquad c / 25 - the same as 87 f! f * * fs' V V! ^ - 15 - 7 8 under (a} but with 15 moles of ethylene oxide (each of R and R - m and n each - 15) and available as a 95% active ingredient; (c) methyl bis- (2-hydroxyethyl) octadecylammonium chloride , a liquid 75% active ingredient in isopropanol / water solvent commercially available 5 as Ethoquad 8/12, Armak and (d) the same as (c) but with 15 mol 7 8 ethylene oxide (each of R and R - m and n each = 15), a liquid 95% active ingredient and commercially available as Ethoquad 18/15, Armak These materials can be used in amounts up to about 10% by weight of the total composition.

The present invention can be practiced in various ways and a number of specific embodiments will be described to further illustrate the invention, wherein in the following examples all parts and percentages are by weight.

EXAMPLES IA and IB

(A) 88 parts of powdered Arosurf TA (dimethyldistearyl ammonium chloride) were heated to 90 ° C to obtain a liquid melt. To this melt, 8 parts of Ethomaine T-25, 1 part of calcium silicate and 3 parts of water were added. The mixture was stirred well and then cooled to room temperature. A white solid was thereby obtained. The solid was then ground to a powder (0% passed through an American type sieve no. 8, less than 10% passed through an American type sieve no. 100, a sieve no. 8 has openings with a diameter of 2.38 mm, and a sieve No. 100 has 25 openings with a diameter of 149 µm). The product resembled the original * Arosurf powder.

(b) Example IA and Example IBA was repeated, except that 8 parts of an ethoxylated fatty alcohol nonionic dispersant was used in place of the ethoxylated amine.

EXAMPLE II

A spray dried heavy duty detergent of the following composition was prepared: 8700195 - 16 -

Component wt%

Linear tridecylbenzene sulfonate (LTBS) 14.5

Sodium tripolyphosphate (NaTPP) 26.0

Silicate (1: 2.4) 6.8 5 Na2 CO3 4.8

Brightening agent (Stilbene and Tinopal 5BM) 0.34

Borax 1.0

Methocell 0.5

Carboxymethyl cellulose 0.24 Sodium sulfate and water q.s. 100 100.00

4.1 g (4.1%) of the cationic powder of Example 1A or 4.5 g (4.5%) of the cationic powder of Example 1B were added to 100 g of the above-described composition to give compositions 2A. 2B respectively. Each of the compositions 2A and 2B was tested for fabric softening and anti-static properties. The results are shown in Table A. The softness was determined under the following conditions:

A fabric batch (total weight about 0.7 kg) consisting of 20 four terry towels, three 38 cm x 38 cm samples of each of the following seven fabric types: Banion, Dacron double knit. (DDK), Dacron / Cotton Blend (65/35), Cotton Batist, Acetate Jersey (AJ), Nylon Tricot, and Dacron Polyester Single Knit (DSK), and ten samples from each of three different soiled fabrics (Spinach at 50/50 Dacron / cotton) ; Sebum on DDK and Piscataway clay on 50/50 Dacron / cotton) was washed at 60 ° C with 60 liters of wash water (150 ppm) in a Maytag washing machine using 100 g of the cleaning composition. After a single wash cycle, the fabric load was dried in a commercially available tumble dryer for about 30 minutes and allowed to cool for about 2 hours.

Six experienced testers were used to evaluate the softness of the towels treated with each test composition by one of two methods: for each test composition, each of the 4 towels 8700133 - 17 - a score was given against each with the other test composition -lingons of treated towels (in four separate groups) and ranked from the softest to the hardest; or each of the four towels for each test composition was scored on a scale from 1 (no wash-5 softening) to 10 (excellent softness) and an average of the four values was taken as the softness number. In the former test (fabric softening by comparison) for each test composition, the total number of first places (1 point), second places (2 points), third places (3 points) etc. were added and the lowest 10 total corresponds to the best fabric softener characteristics. In the latter test (sliding scale), the average softness number for each tester was averaged with the softness number assigned by the other testers to give a single softness number, with a higher number indicating better fabric softening properties.

Each of these methods has proven to be a statistically significant and reliable procedure for evaluating softness.

The anti-static properties were determined by measuring the static charge build-up (voltage) on samples from four different fabrics: Dacron / cotton (65/35); Dacron double knitted (DDK); acetate jersey 20 (AJ) and Banion polyester, which had been washed as described above. Each of the three washed and machine-dried samples from each of the four different fabrics was hung on a mounting frame. A small sample of wool, attached to the outer edge of a rotating circular container, was rotated on the container in contact with the tissue sample for 5 seconds. The temperature was kept at 21-22 ° C and the relative humidity at 21%. The voltages for each tissue (three different samples) were averaged together and the average voltages for the four different tissues were averaged to obtain the static charge number. The lower the static charge number, the better the anti-static properties of the cleaning composition. Generally, static charge numbers of less than about 5 kilovolts (kV) are considered very good and experienced by the user in the absence of static charge build-up.

8700) 33 - 18 -

TABLE A

Sample QUAT ethoxylated sliding scale static (g / wash amine (g / wash softness load number liquid) liquid)

2B 3.96 - 8 2.8 KV

5 (comp.)

2A 3.62 0.34 8 4.2 KV

(ex.)

In a comparative softness test, sample 2B received 11 first place votes (35 points) compared to 13 first place votes 10 (37 points) for sample 2A.

EXAMPLE III

Example 1A was repeated except that the mixture of dimethyl distearylammonium chloride, tallow amine adduct with 15 moles of ethylene oxide, calcium silicate and water was stirred and fed to the inlet 15 of a soap mixer extruder into which it is extruded in the form of spaghetti or noodles. When the spaghetti or noodles are added to the spray dried detergent shown in Example II, similar results are obtained as in Composition 2A.

EXAMPLE IV

Example 1A was repeated except that instead of Ethomen T / 25 the following ethoxylated tertiary amines were used: (a) polyoxyethylene (5) octadecylamine (b) polyoxyethylene (5) tallow amine (c) polyoxyethylene (10) tallow amine 25 (d) polyoxyethylene (15) tallow amine (e) polyoxyethylene (5) hydrogenated tallow amine (f) polyoxyethylene (15) hydrogenated tallow amine.

f

EXAMPLE V

To a spray dried detergent composition with approximately the following analysis: 8700193 - 19 -

Component wt% linear dodecylbenzene sulfonate 23

Na2 CO3 20

After silicate 15 5 Borax 3 fatty alcohol with 7 mol ethylene oxide (Neodol 25-7) 3

Carboxymethyl cellulose 1

Optical brightener 0.5 10 Satintone 1

Na2S ° 3 and water q.s. 100, 4% of the cationic fabric softener / ethoxylated amine fabric softener dispersant of Example 1A was added. Excellent cleaning and fabric softening properties were obtained.

EXAMPLE VI

4.5 g of the cationic fabric softener / ethoxylated amine powder of Example 1A were subsequently added to the spray-dried detergent powder of Example 2. Further improvements in the fabric softening were obtained (on the sliding scale, the softness number was 9-10).

The following examples show the production and use of the cationic-nonionic combination in the form of prills.

EXAMPLE VII

500 kg of dimethyldistearylammonium chloride containing about 4% water was heated to 90 ° C and formed a melt. To this hot melt, 25 kg of Ethomen T / 25 were added. This common melt was then sprayed down from the top of an approximately 24 meter high tower with a diameter of about 5 meters. At the same time, cool air with a temperature of about 10 ° G was directed upwards (i.e. in the opposite flow direction as the liquid sprayed down) at a rate of about 850 m3 per minute. The solidified product was collected at the bottom of the tower.

The product particles had a white appearance, were free-flowing, generally ball-shaped and solid. They had a porous surface (pockmarked appearance). The bulk density of the prills was about 0.37 g / cm3.

EXAMPLE VIII

4.0 g or 4.5 g of the prills according to example VII were added to 95.5 g of the detergent according to example II (without the 5 particles of example IA).

EXAMPLE IX

Each of the previous examples was repeated again except that the cationic fabric softener of the cationic ethoxylated amine mixture was replaced with the following: (a) dimethyl di-tallow ammonium methosulfate; (b) dimethyl, dihydrogenated tallow ammonium chloride; (c) 1-methyl-1-tallow amidoethyl-2-tallow imidazolinium methosulfate; (d) 1-methyl-1-oleylamidoethyl-2-oleylimidazolinium methosulfate.

i 3 7 η λ i η χ

Claims (20)

1. Particulate detergent-fabric softener composition, which can impart better softness, cleaning performance, anti-static and anti-soil re-targeting properties to fabrics treated therewith in a washing process, comprising about 5-40% by weight water-soluble non-soap, organic surfactant , about 10-60 wt% water soluble, neutral to basic builder salt, and dispersed substantially homogeneously in the composition in the form of discrete particles an intimate mixture of (i) about 2-20 wt%, based on the total composition, of a cationic amine fabric softener with (ii) a water-soluble ethoxyated tertiary amine dispersant / fabric softener, the percent concentration of anionic surfactant being at least about 1.5 Cs + 5, where Cs represents the percent concentration of the total fabric softener. 2. A composition according to claim 1, wherein the ethoxylated tertiary amine has formula 3 of the formula sheet wherein R represents alkyl or alkenyl of about 8 to about 22 carbon atoms, and x and y are positive numbers such that the sum x + y is about 2 to about 15. The composition of claim 2, wherein R represents C 1 -C 12 alkyl. The composition of claim 2, wherein R represents stearyl, cetyl, tallow, hydrogenated tallow or mixtures thereof. The composition of claim 2, wherein R represents C 1 -q-C 1 -q alkenyl and x + y represents about 5 to 15. The composition of claim 1, wherein the amount of ethoxylated tertiary amine (ii) is about 2 - 50% by weight of the mixture of (i) and (ii). The composition of claim 1, wherein the amount of ethoxylated tertiary amine is about 2-20% by weight of the mixture (i) and (ii) 30, said mixture comprising about 2-15% of the composition. The composition of claim 1, wherein the ethoxylated tertiary amine is about 2-15% by weight of the cationic amine (i) / ethoxyated tertiary amine (ii) mixture, and the mixture is about 2-10% by weight of the composition . 870 0193: • ψ - 22 - The composition of claim 1, wherein the cationic mixture is the finely ground product of a common melt of the cationic and ethoxylated amine components. The composition of claim 1, wherein the cationic / ethoxylated amine mixture is a prill. The composition of claim 10, wherein the prill is a generally spherical particle with a solid core and a porous surface. The composition of claim 1, wherein the cationic amine 10 (i) is a di-short chain alkyl, di-long chain alkyl quaternary ammonium halide or an imidazolinium compound. The composition of claim 1, wherein the cationic amine fabric softener (i) is a di-C 1 -alkyl, di-C 1 -alkyl ammonium halide, and the ethoxylated amine is a CQ Q linear aliphatic tertiary o-10 amine with about 2 to about 15 moles of ethylene oxide. The composition of claim 1, wherein the cationic amine fabric softener is selected from the group consisting of di-C 1-4 alkyl, di-C 1-4 quaternary ammonium salts, imidazolinium salts and mixtures thereof, and the ethoxylated amine a C 10 linear aliphatic 12- 10 is tertiary amine containing from about 5 to about 15 moles of ethylene oxide. The composition of claim 1, wherein the non-soap detergent comprises an alkyl benzene sulfonate and the builder comprises a phosphate. The composition of claim 15, wherein the non-soap detergent is a C linear alkyl benzene sulfonate. o-lo A composition according to claim 1, wherein the non-soap detergent comprises a C 8 -g linear alkyl benzene sulfonate, the builder comprises a phosphate, the cationic amine (ii) is a di-C 1-4 alkyl, di-alkyl ammonium halide, the ethoxylated amine (ii) is a C 1-4 linear tertiary amine containing from about 5 to about 15 moles of ethylene-30 oxide and the ethoxylated amine constitutes about 3 to about 10% by weight of the cationic fabric softener / ethoxylated amine mixture. 18. A method of preparing a composition according to claim 1 comprising spray drying the non-soap organic surfactant and builder salt and adding the discrete particles to the spray dried material afterwards. Λ Λ / y y i s ύ - · «- 23 - Particulate fabric softener composition comprising an intimate blend of a cationic amine fabric softener and 2-20% based on the weight of the mixture of a water-soluble nonionic ethoxylated tertiary amine fabric softener dispersant. A method of washing fabrics, comprising contacting the fabrics in an aqueous medium at a temperature of about 26-77 ° C with sufficient composition of claim 1 to a ratio of 1.5 to 3, 5 g of fabric softener per 3500 g of fabric. 870 0 1 9 3- 3- φ R1 + R - N - R2 X 'R3 2 N— CH2 * r5-C / I x- N + - CH2 / \ o R ^ CH2CH2NH - C - R6 3 (CH2CH20) xH R -1T \ (CH2CH20) yH h CH3 + t (R7) n * N - (R8) n x- _ R * _ B 7 η n 1 o ^