PT77608B

PT77608B - Process for preparing detergent softener compositions containing quternary ammonium or imidazolyne salts

Info

Publication number: PT77608B
Application number: PT77608A
Authority: PT
Inventors: Riad A Taha
Original assignee: Colgate Palmolive Co
Priority date: 1982-11-05
Filing date: 1983-11-04
Publication date: 1986-04-21
Also published as: MX159209A; AT394376B; DE3339050A1; NL8303810A; FI834044A; CA1223405A; FI834044A0; IT1171882B; SE8306058L; GB8329563D0; BR8306054A; ZW23183A1; AU572807B2; FR2539427B1; GR79087B; ES8504919A1; FR2539427A1; PT77608A; IT8349268A0; BE898167A

Abstract

Particulate heavy duty detergent compositions, particularly for imparting improved softness and detersive effects to fabrics laundered therewith, comprise in addition to conventional builder and principally anionic surfactant components, particulate cationic softener of the di- lower-di-higher alkyl quaternary ammonium and/or heterocyclic imide type, e.g. imidazolinium, in admixture with nonionic surfactant and optionally a mixture of fatty acid soap and nonionic organic surfactant, the weight ratio of soap to softener being about 8:1 to 1:3 preferably 5:1 to 1:2, more preferably 3:2:2:3, e.g. about unity. The soap-nonionic surfactant mixture as well as the cationic softener-nonionic mixture are in the form of a spaghetti, flake, or other shape and is present in the product composition as substantially homogeneously dispersed, discrete particles. A process of laundering fabrics using the above-mentioned composition is also described.

Description

Detailed description of the invention

According to the present invention it is possible to substantially reduce the formation of spots on the laundry after drying by adding the cationic material intimately mixed with the organic surfactant in the form of flakes, granules, or some other form. Further the softness of the fabrics washed with this detergent increases in a generally unexpected manner. The nonionic surfactant also contributes to the anti-redeposition of stains, especially in formulas which do not contain phosphates.

The inclusion of the nonionic organic surfactant in the cationic softener composition has the additional advantages set forth below. Usually nonionic surfactants are added post-spray detergent compositions.

As a result, the nonionic surfactant adding the latter will cause the detergent product to become stickier. In the present invention the nonionic surfactant is included in the " addition " cationic component, which leads to a significant improvement in the fluidity of the detergent composition.

people.

In the embodiment of the present invention wherein soap particles with or without cellulose ether or nonionic surfactant as proposed in the above-described Wixon patents are used, useful fatty acids generally include those which are derived from the acids natural or synthetic fatty acids having from 10 to 30 carbon atoms in the alkyl chain. Preferred are alkali metal, e.g., sodium and / or potassium, soaps of saturated fatty acids (Ο θ ^C 24 ' ¹ '), a particularly preferred class being the sodium and / or potassium salts of mixtures of fatty acids derived cobalt oil and tallow oils, for example, the combination of sodium sodium soap and potassium tallow and potassium soap in the mutual proportions respectively of 15-85. As known, as the molecular weight of the Thus, the choice of the fatty acid can be made herein in accordance with the level of foam to be obtained with the composition of the product. Generally, effective results are obtained Quan _F of at least about 5θ% of the fatty acid soap is of varied.. ^c ~ ity ^c qQ qg- Other soaps of fatty acids herein may 'be used include those derived from palm oils, peanut, fish dried, for example, cod liver, and shark, seal, perilla, linseed, walnut-seed, hemp seed, walnut, poppy seed, sunflower, maize, rapeseed, mustard seed, apricot, almond, beaver and olive oil, etc. other fatty acid soaps include those which are derived from the following acids: oleic, linoleic, palmitoleic, palmitic, linoleic, ricinoleic, capric, myristic and the like, other useful combinations of these acids including, without limitation, caprylic-lauric, / 20, capric-myristic 80/20, oleic-capric 50/50, capric-palmitic 90/10 and the like.

Useful surfactants in the soap particles and which are mixed with the cationic component are known materials. These nonionic surfactants can be generically defined as water soluble compounds produced by the condensation of the (hydrophilic) alkylene oxide groups with a hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any specific hydrophobic group can easily be adjusted so as to produce a water soluble compound with the desired degree of balance between the hydrophilic and hydrophobic elements.

For example, a well-known class of nonionic organic surfactants is available commercially under the trade name "Pluronic". These compounds are formed by condensation of ethylene oxide with a hydrophobic base formed by the condensation of propi oxide. with propylene glycol. The hydrophobic part of the molecule which, of course, is insoluble in water, has a molecular weight of about 1,500 to 1,800. The addition of polyoxyethylene radicals to this hydrophobic part tends to increase the water solubility of the molecule as a whole, the net nature of the product being retained to the point where the polyoxyethylene content is about 5θ per cent of the total weight of the condensation product.

Other synthetic surfactants

include:

1. The polyethylene oxide condensates of alkyl phenols, for example, the condensation products of the alkyl phenols having an alkyl group containing about six to 12 carbon atoms in a straight chain or branched chain configuration with of ethylene, said ethylene oxide being present in amounts equal to 5 ^to 25 moles of ethylene oxide per mole of alkyl phenol. 0

substituent in these compounds may be derived from

propylene, diisobutylene, octene, or nonene copolymers,

for example.

2. Og derived from the condensation of ethylene oxide with the product resulting from the reaction of the propylene oxide with the ethylene diamine. For example, compounds containing about 40 percent to about 80 percent polyoxyethylene by weight and having a molecular weight of about 5,000 to about 1,000,000 resulting from the reaction of ethylene oxide groups with a base hydrophob comprising the reaction product of ethylene diamine with excess propylene oxide, said base having a molecular weight in the range of 2,500 to 3,000.

3. The condensation product of

aliphatic alcohols having eight to 30 carbon atoms, in straight or branched chain configuration, with 2 to 100 moles of ethylene oxide, for example a condensation of coconut alcohol ethylene oxide with 5 ^to 5 moles moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol moiety having 10 to 14 carbon atoms.

Nonionic surfactants include nonyl phenol condensed with about 10 or about 30 moles of ethylene oxide per mole of phenol and the condensation products of coconut alcohol having a modulus of about 5.5 or about 15 moles of ethylene oxide per mole of alcohol and the condensation product of about 15 moles of ethylene oxide with one mole of tridecanol.

Other examples include dodecylphenol condensed with 12 moles of ethylene oxide per mole of phenol; 0 dinonylphenol condensed with 15 moles of ethylene oxide per mole of phenol; dodecyl mercaptan condensed with 10 moles of ethylene oxide per mole of mercaptan; 0

-11-

bis- (N-2-hydroxyethyl) lauramide; the nonyl-phenol condensed with 20 moles of ethylene oxide per mole of nonyl-phenol; the myristyl alcohol condensed with 10 moles of ethylene oxide per mole of myristyl alcohol; lauramide condensed with 15 moles of ethylene oxide pon mole of lauramide; and di-isooctylphenol condensed with 15 moles of ethylene oxide.

Among the foregoing nonionic surfactants, the condensation product of the aliphatic alcohols having 8 to 22 carbon atoms with ethylene oxide is preferred. Typical examples of such nonionic surfactants Neodol 25-7, a product of Shell Chemical Co., which comprises the condensation product of alcohol ^with 2-15 ^C ^? ^m0 -'- OE ethylene oxide and Neodol 23-6.5 which is the product of condensing an alcohol with 6.5 moles of ethylene oxide.

The cationic softeners used herein are known materials and are of the high melt type. These include the N, N-di-lower alkyl (C 1 -C 4) -alkyl (quaternary) ammonium quaternary ammonium salts with soluble anions in water such as the halide, for example, chloride, bromide and iodide; sulfate, methosulfate and the like and the heterocyclic imides such as the imidazolinium salts.

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

F ¹

3

in which R 1 and R 2 represent alkyl having 14 to 24 carbon atoms and preferably having 14 to 22 carbon atoms; R 2 and R 3 represent lower alkyl having 1 to 4 carbon atoms and preferably 1 to 3 carbon atoms, X represents an anion capable of obtaining water solubility or dissersibility including the aforementioned chloride, bromide, iodide, sulfate and methosulphate. Particularly preferred species of quaternary components include the following:

distearyl dimethyl ammonium chloride

hydrogenated dimethyl ammonium dichloride

di-tallow dimethyl ammonium chloride

Distearyl dimethyl ammonium methylsulfate

hydrogenated dimethyl-ammonium di-tallow methylsphosphate

The imidazolin-type heterocyclic imide softeners may also, for convenience, be structurally defined as follows:

wherein R1 is lower alkyl of 1 to 4 carbon atoms and

preferably with 1 to 3 carbon atoms; R ^ and Εθ are, each

one, substantially linear lower alkyl groups with

about 13 to 19 carbon atoms and X has the same meaning as previously assigned.

Particularly preferred species of imidazoliniums include the following:

1-methyl-1-tallowamidoethyl-2-tallowimidazolinium

marketed by Sherex Chemical Co. under the trademark TJ

of Varisoft 475 5 in the form of a liquid; 75% active ingredient in isopropanol solvent;

1-methyl-2-oleylamidoethyl-2-oleylimidazolinium

marketed by Sherex Chemical Co. under the trade mark E

Varisoft 3690, 75% active ingredient in isopropanol solvent.

According to one aspect of the present invention, when the soap and the nonionic surfactant are used in combination, it is preferred that the soap be used with a quantity at most equal and preferably less of surfactant, for example, from about 2% to about 50% of the blend, preferably about 5% ^to about 40%, more preferably about 8 to about 30%, and most preferably about 8 to about 20%, based on the blend total non-ionic surfactant soap in order to be incorporated into the final detergent composition, usually by subsequently blending both the soap and the cationic component-non-ionic component blend with dry detergent. The soap and the nonionic surfactant when combined may first be mixed in the desired amounts so as to form a substantially homogeneous mass which may

be worked in accordance with a well-known technique, until it is sufficiently pasty or plastic enough to be in a suitable weak state, preferably undergoing an extrusion process, for example small pellet processing, granulating, printing and pressing. The work can be carried out, for example, by rolling, although this is not essential, followed by extrusion in a conventional soap extruder equipped with the type of extruder head that is desired. The latter is chosen according to the shape, i.e., the geometric shape, which the extruded product is intended to exhibit. Extrusion in the form of spaghetti or noodles is particularly preferred. Other forms such as flakes, tablets, small pills, tapes, wires and the like are suitable alternatives. Special extruders for the above purposes are known in the art, among which are included for example Elanco EXD-SO, EXCD-100, EX-I50 and EXD-180, a Buhler extruder and the like. Typically, the spaghetti extruded product forms a dough which retains its shape, is semi-solid and essentially non-sticky at room temperature, with no further treatment requiring, for example, removal of water in most cases. If necessary, this water removal treatment may be carried out by simple drying techniques. The spaghetti should have an average length of about 2 to 20 mm, with about 95% being said spaghetti within a tolerance of 0.5 to 20 mm and having a mean diameter or a mean width of about 0.2 to 2.0 mm, preferably in the range of 0.4 to 0.8 mm. The density of a spaghetti filler should, depending on the type of fatty acid soap and nonionic surfactant used, normally be about 0.9 to 1.5 g / cm @ 3. The flakes should measure about 4 mm in length and width and 0.2 mm in diameter, the small tablets should have a cross-section with a diameter of 2.5 mm, whereas the tablets should have a cross-section with a diameter of 2.5 mm and a

77, 77, 77;

7

7777

thickness of 2.5 mm.

The nonionic component cationic component blend may be prepared in a manner similar to that which was used to prepare the soap-nonionic component mixture. However, it is preferable to use the mixture in the form of "prills" (spherical particles the size of a hunting lead). The prills are produced by spray-cooling a liquefied mixture of the cationic component and the nonionic component. In the preferred embodiment, a liquid nonionic component (e.g., Neodol 25-6.5) is used which is added to the molten cationic component. A typical cationic component is Afosurf TA-100 (dimethyl distearyl ammonium chloride) and confor. this material forms a very fluid liquid when melted and heated to 90 ° C. The liquid mixture of cationic component and nonionic component may, in another preferred embodiment, be allowed to cool to room temperature or to the temperature necessary to solidify the solid product thus obtained may then be milled until particles of size and then added to the other detergent ingredients.

Usually 1 to 20% by weight of nonionic component is included, based on the weight of the cationic softener. The nonionic component should preferably be used in amounts of 5 to 15%, the amount of 10% in the case of Neodol 23-6.5 being particularly preferable.

While conventional surfactants may be used herein, it is preferred that at least about 90%, and preferably at least about 95%, of the total surfactant or detergent are of the amionic type , these products being particularly suitable for detergents of enhanced action suitable for washing fabrics. The own anionic products

for use herein generally include the water-soluble salts of organic reaction products which have in their molecular structure a group which solubilizes anions such as SO2 H, SO2 H, COOH and HO4 H and an alkyl or about 8 to 22 carbon atoms in the alkyl group or moiety. Suitable detergents are anionic detergent salts having alkyl substituents of 8 to 22 carbon atoms such as water-soluble, sulfated and sulphonated, anionic alkali metal and alkaline-earth metal salts and anionic, water-soluble detergent salts containing a higher hydrophobic hydrophobic alkyl moiety, such as higher alkyl aryl mono- or poly-nuclear sulphonates salts having about 8 to 18 carbon atoms in the alkyl group which may have a straight chain (preferred) or branched structure , preferred species including, but not limited to: sodium linear tridecyl benzene sulfonate, sodium linear dodecyl benzene sulfonate, sodium linear or sodium dodecyl benzene sulfonate, or lithium or potassium pentapropylene benzene sulfonate; alkali metal salts of sulphated condensation products of ethylene oxide, for example containing from 3 to 20 and preferably from 3 to 10 moles of ethylene oxide, with aliphatic alcohols containing from 8 to 10 carbon atoms or from -phenols with alkyl groups containing 6 to 8 carbon atoms, for example nonyl phenol pentaethoxamero sulfate and sodium lauryl alcohol triethoxamero, and alkali metal salts of saturated alcohols containing about 8 to 18 carbon atoms, for example sodium lauryl sulfate and sodium stearyl sulfate; alkali metal salts of higher fatty acid esters of lower alkylsulfonium acid, for example fatty acid esters of the solid salt of isethionic acid; fatty ethanolamide sulphates; fatty acid amides of amino-alkylsulfonic acids, for example taurine lauric acid amide; alkali metal salts of hydroxy alkanoesulphonic acids having 8 to 18 carbon atoms in the alkyl group, for example sodium O-hydroxyhexadecylsulphonates.

The anionic compound or the mixture thereof is used under the

alkali metal or alkaline earth metal salts thereof.

The anionic compound is preferably of the non-soap type, it being preferred that the soap component is used as described herein. However, small amounts of soap, for example up to about 35%, and preferably up to 20%, based on the total amount of anionic compound may be added, for example, to the mixture obtained in a soap blending machine.

The concentration of component

anionic non-soap should preferably be chosen so as to provide an excess with respect to the cationic softener in accordance with the following empirical relationship.

% concentration = 1.5X + 5

where X is the concentration of cationic softener. This guarantees the minimum excess of anionic compound needed to obtain optimum overall yield values for detergency, softening, etc. of the composition. of the product.

Small amounts of other types of detergents may be included in conjunction with the anionic compound, and in any case their sum should not exceed about 10%, preferably about 2-5% of the total amount of detergent, i.e. of that other detergent plus anionic non-soap component. 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 amino, with ethylene oxide or the product thereof of polyhydration, polyethylene glycol. Included are condensation products of fatty alcohols from Οθ to C q tais such as the tridecyl alcohol with 3 to 100 moles of ethylene oxide; the alcohol C ^ to C g com with 11 to 50 moles of ethylene oxide; ethylene oxide adducts with polyhydric alcohol monoesters, for example hexahydric; condensation products of propylene glycol with 3 to 100 moles of ethylene oxide;

the condensation products of alkyl (straight chain or branched C Οθ _2Q) phenols with 3 to 100 moles of ethylene oxide and the like.

Suitable amphoteric detergents are generally those which contain both an anionic group and a cationic example as a hydrophobic organic group which is preferably a higher aliphatic radical having 10 to 20 carbon atoms; examples include long chain N-alkyl aminocarboxylic acids and N-alkyl long chain iminocarboxylic acids such as those described in U.S. Patent 3,828,189.

The compositions used herein preferably include an alkaline to neutral water-soluble "builder" salt in amounts of about 10 to 60% by weight relative to the total composition. Useful herein are organic and inorganic "bulking agents" including alkali metal and alkaline earth metal phosphates, particularly condensed phosphates such as pyrophosphates or tripolyphosphates, silicates, borates, carbonates and the like. Among these species there are included sodium tripolyphosphates, trisodium phosphate, tetrasodium pyrophosphate, sodium acid pyrophosphate, sodium monobasic phosphate, sodium dibasic phosphate, sodium hexametaphosphate; alkali metal silicates such as sodium metasilicate, sodium silicates: Na ₂ O / SiO ₂ of 1.6: 1 to 3.2: 1, sodium carbonate, sodium sulfate, borax (sodium tetrahorate), tetrasodium salt of ethylene diamine tetraacetic acid, trisodium nitrilotriacetate and the like and mixtures of the above-mentioned compounds. The "builder" salt may be chosen so as to provide phosphate-containing detergents without phosphates. As for the latter embodiments, sodium carbonate is particularly effective. Another product that was found to provide

-19-

good detergency effects is the metakaolin which is generally produced by heating the kaolinite network in order to expel the water, thereby producing a product which is substantially amorphous on examination by X-rays but which retains part of the structural order of kaolinite . Discussions on kaolin and metakaolin can be found in the U.S. patent

No. 4,075,280, columns 3 to 4, and in G-rimshaw's work "The Chemistry of Physics of Clays and Allied Ceramic Materials" (4th ed., Wiley-Interscience), pp. The metakaolin is also the subject of U.S. Pat. 9θ5 · 822 and 905,718, the relevant disclosures of which are hereby incorporated by reference. Metakaolin also appears to have softening properties. As above, the most effective metacaulines appear to be those which behave best in the reaction with sodium hydroxide to form zeolite 4A, as described in U.S. Patent 3,144,605 which refers to such products as "reactive kaolin" The metakaolin and / or zeolite is included in approximately the same amounts as the "scavenger" salt, and preferably in supplement thereto, for example zeolite / silicate in a ratio of A particularly useful form of metakaolin is that which is marketed under the desensitization of Satintone N2.

Among the preferred optional ingredients useful herein are perfume such as G-eny perfume; optical brighteners and "bluing" agents which may be composed of dyes or pigments and are included in dyestuffs or pigments, and Stilbene and Tinopal 5 BM brighteners are included among the suitable products for this type. particularly in combination with bluish agents Direct Brilliant Sky Blue 6B, Solophenyl Violet 4BL, Cibacete, Brilliant Blue RBL and Cibacete Violet B, Polar Brilliant Blue EAW and Calcocid Blue 2G. The fan can be

included in quantities up to 1% of the total composition.

-20-

such that the blending agents may be up to about 1%, preferably up to about 0.01%, of the total composition.

The "bluish" agent, for example Polar Brilliant Blue, may be included in the soap in the form of spaghetti. In any case the amount used to be effective need not be more than a minimal amount.

Among other ingredients of

great importance are included bleaching agents which may be of the type which promotes oxygen or chlorine release; oxygen bleaching substances include sodium and potassium perborate, potassium monopersulfate and the like, while bleaching substances which release chlorine are typified by sodium hypochlorite, potassium dichloroisocyanurate, trichloroisocyanuric acid and other similar compounds. The latter chlorine-releasing bleaching substances are representative of the broad category of solid, dry, organic and water-soluble bleaching substances known as N-chloro imides, including the respective alkali metal salts thereof. These cyclic imides have about 4 to 6 ring / ring elements and are described in detail in U.S. Patent 3,325,414. Each of the oxygen and chlorine releasing bleaching substances which have been previously disclosed is fully compatible with the compositions of this invention and has good stability in the presence of the anionic and cationic components. They are generally used in ratios of the order of 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.

Among the optional ingredients there is further included a cellulosic, colloidal, hydrophobic and soluble and / or water dispersible bleach suspending agent. Methyl cellulose, for example Methocel, is particularly effective. Polyvinyl alcohol is equally effective

is © $ o®à1 |

IΊοφοο i

[ESOUOO] j

and especially in washing cotton and synthetic fibers such as nylon, dacron and resin-treated cotton. The additional stain suspending agent may be included in amounts up to about 4% based on the total detergent composition. However it should be noted that the organic nonionic surfactant component of the spaghetti soap performs at least most of the anti-redeposition function with respect to this aspect significantly enhanced by the soap product as previously explained.

In addition to the above-mentioned ingredients agents of such as sodium sulfate, sodium chloride and the like may also be included. The amount of filler should be on the order of up to 40% of the total composition.

The detergent composition is prepared by a conventional process such as, for example, spray-drying in a mixture, obtained in a mixer of surfactant soap, "dressing agent", filler etc. , with volatile ingredients such as perfume or with ingredients otherwise negatively affected by the spray-drying process such as peroxygen bleach, for example sodium perborate. The ingredients of this type are preferably mixed at a later stage. As previously stated, the spaghetti soap (when used) and the cationic softener composition with nonionic component are simply dry mixed with the dry detergent and in the form of small particles by means of simple mechanical mixing which is more than adequate to achieve a homogeneous product. As previously explained, part or all of the soap in the form of spaghetti may alternatively be added to the blend obtained in an aqueous soap mixing machine. A typical procedure will be as follows: water is added to a machine to mix soap and then

in sequential order, in anionic component, sodium silicate, optional ingredients, such as Satintone // 2, where a filler such as sodium sulfate is required, and a "builder" salt. The blend obtained from a soap blending machine is heated to about 60 ° C. (140 ° E) prior to the addition of the structuring agent, for example sodium tripolyphosphate, the solids content of the blend obtained in the soap blending machine before spray drying of about 55-65%. Spray drying may be carried out in a conventional manner by pumping the soap mixture from the soap mixing machine to a spray tower where the mixture is passed through a spray nozzle into a hot evaporated atmosphere. The bleaching agent and further products to be added are incorporated into the mass of the dry detergent by any suitable process such as in the case of a simple mechanical mixing.

For use a sufficient amount of the detergent composition is added to the wash cycle in order to provide a concentration of cationic softener in the wash medium of from about 1.5 to about 8.0 g / 3500 g of laundry having a range of temperature of about _t DE21 ° C (70 ° E) until boiling / "ie, about 100 ° C (212 ° E) 7 in this respect it should be understood that" cold " is meant a washing temperature up to 21 0 ° (70 ° ^to) and "hot wash" means a temperature above 21 ° C (7O ° E) to boil.

Certain types of aliphatic quaternary ammonium compounds although relatively ineffective with regard to softening are however quite effective as antistatic agents in the compositions of this invention and particularly so long as they are physically compatible with an anionic surfactant in liquid environments. These products generally include ethoxidized / or propoxylated quaternary ammonium compounds

(I.e.

and / or the following formula

^c 'i ₃

in

7 P>

wherein R 'and R ° are ethoxy or propoxy, m and n are integers from 1 to 50 being the same or different and R representa is alkyl of 14 to 24 carbon atoms. Included among the compounds of this type are (a) methyl bis (2-hydroxyethyl) -octanoammonium chloride, a 75% liquid active ingredient in an isopropanol / water solvent and available in the market under the designations of Ethoqua c / 12, Armak and Variquat ® 638, Sherex Chemical Co.; (B)

Ethoquad w / 25-0 same as in (a) but having 15 moles of ethylene oxide (m + n) and available as a 95% active ingredient; _/ (C) methyl chloride, bis (2-hydroxy-ethyl) liquid active ingredient ammonium -octadecil a solvent of 75% isopropanol / water and which is commercially available under the name ETHOQUAD 18/12, Armak and (d) the same as (c) but had 15 moles of ethylene oxide (m + n), 75% liquid active ingredient and commercially available as Ethoquad 18/15, Armak. These products may be used in amounts up to about 10% by weight of the total composition.

only for the purpose of mitigate in some way the charges are ponderous.

The following examples are for illustrative purposes and are not intended to All parts and percenΕΧΕΗΡΕΟ 1

A) 100 g of Arosurf TA (dimethyl distearyl ammonium chloride) powder are heated to 90 ° C resulting in a melt in the fluid state. To this molten product is added 10 g of the liquid nonionic component Neodol 23-5.5 (linear alcohol C ₁₂ condensed with 5.5 moles of ethylene oxide). The mixture is well stirred and then cooled to room temperature. A white solid is obtained. This solid is then milled to give a powder (0% on US 8 sieve and US 100 <10% sieve). The product

resembles the original Arosurf powder.

B) Operation A is repeated except that only 5 g of non-ionic component is used.

EXAMPLE 2

The products of Example 1 as well as only the cationic powder component (the same as that used in Example 1 to produce the co-fused product), having a particle size equal to that of Example 1, are each tested separately for uniformity of water dispersion by the following process:

In a tergitometer equipped as

with an alternative stirrer, 0.15 g of a detergent (13.4% of alkyl benzene sulphonate) is added to 500 ml of water (hardness of 15 ° ppm) at 21 ° C (70 ° E). % of sodium tripolyphosphate, 30% sodium sulfate, 4.5% sodium carbonate, 6.3% water soluble silicate solids, 7% moisture, 4% soap, small amounts of fan, methocel and perfume) which also contains 4.5% of the particles of Example 1. The stirrer is run for 5 minutes at

100 rpm and then the aqueous composition is filtered under vacuum through a new soft blue twill fabric. In the case of the fluid substances of Example 1 - containing detergent there is no visible evidence (i.e., no white spots) of any residue. When the process is repeated using the same conditions with the same composition, except that instead of 4.5% of the products of Example 1, only 4.5% of the cationic component is used, a very visible distribution of white spots on the twill appears. This is very evident proof of the important advantages offered by the products of the Example.

EXAMPLE 5

while the compositions described in Example 2 are used to wash stained white towels in a washing machine which are then dried in an automatic drying machine, the clothes are acceptably soft despite those which are washed with the detergent containing the softener combination of the Example 1 are slightly softer.

In addition, towels washed with detergent containing only cationic component powder (i.e. not combined with nonionic component) have some visible but slight spots (i.e., greasy stains) apparently caused by the cationic product while the others do not .

EXAMPLE 4

4,

.7 " ^:

4W

Examples IA & IB & 3 are repeated except that instead of Neodol 23-6.5 the following non-tonics are used:

a) Neodol 25-7

(An alkyl alcohol (0.5 mol% ethylene oxide)

b) Igepal CO-63O

(Nonyl-phenol + 10 moles of ethylene oxide)

c) Neodol 45-13

(A linear alcohol of (+) - 13 mol of ethylene oxide)

EXAMPLE 5

There is provided a spray-dried enhanced detergent action having the following composition:

Component

Tridecyl linear benzene sulfonate (LTBS)

Sodium Tripolyphosphate (NaTPP)

% weight

Silicate

(Stilbene & Tinopal 5BM) Sodium sulfate and water QS

15

33

7

0.48

100.00

to 90 g of the above composition are added,

of the 4 grams of the powder consisting of cationic component - compound.

ion of Example 1 (B).

results.

EXAMPLE 6

Repeating Example 3 except that the detergent also contains a spaghetti-shaped soap (4.5% detergent).

EXAMPLE 7

Example 6 is repeated except that the spaghetti soap contains 20% by weight Neodol 25-7 ·

In Examples 6 & 7 the soap in the form of a soap is a tallow / coconut soap 85/15

EXAMPLE 8

Example 3 is repeated but using a detergent composition with the following approximate analysis:

Component

Ϊ0§00]

'♦ íátrÃ & j

-28%

Lodecil linear-benzenesulfonate 23

In the CO, 20

2 3

Silicate 15

Borax 3

Nonionic surfactant 1

Soap 2

Carboxymethyl Cellulose 1

Satintone 1

* 0.48

NagSO4 and water QS

* Stilbene and Tinopal 5 *

To 75 grams of the preceding composition 5S of the product of Example 1B is added.

EEEKPLO 9

Example 8 is repeated except that β g of a nonionic soap in the form of spaghetti (similar to Example 7) is used.

'AA'; · - - · -

6 weight

9

8

2

24

17

QS

are added

EXAMPLE 10

Example 6 is repeated except that the spaghetti soap which is used also contains 4% by weight of carboxymethyl cellulose.

EXAMPLE 11

The following strengthened detergent composition is prepared:

Component j

Linear alkyl benzene sulfonate

Alcohol ether sulfate

Nonionic surfactant

Sodium Tripolyphosphate

Zeolite A

PRICE / INFO

To this composition

5.0 g of the cationic product of Example 1B.

-30-

EXAMPLE 12

Example 11 is repeated except that the spaghetti soap / surfactant of Example 6 is added to give 4% detergent.

EXAMPLE 15

A composition is prepared in the form of a non-perfumed powder and having the following formulation:

Component weight%

Linear-benzene-sulfonate tridecyl 14.8 Sodium Tripolyphosphate 26.5 Silicate 6.9 (Stilbene and Tinopal 5BM) 0.4? Sodium carbonate 4.9 Carboxymethylcellulose 0.25 Metocel 0.6 Sodium sulfate, moisture QS 90.6 parts in detergent in the form of non-perfumed powder are weight of the previous added:

Mixture of cationic component-non-ionic component of Ex. IB 4.0 parts

Spaghetti-shaped soap (90% tallow / coconut 85 / 15j 10% Neodol 25-7 Shell Chemical Co.). length of spaghetti = 15 mm, diameter

= 0.5 mm 4.0 parts

Borax pentahydrate 0.7 parts

• F-FF

Nonionic surfactant (Neodol 25-7)

0.5 parts

Perfume 0.2 parts

The following examples illustrate the production and use of the combination cationic component-nonionic component in the form of "prills" (spherical particles of the size of game leads).

EXAMPLE 14

Five hundred kilograms of dimethyl distearyl ammonium chloride containing about 4% water are heated to 90 ° C and form a melt. To this hot melt is added 25 kilograms of Neodol 23-6.5. This co-fused product is then sprayed top-down from the top of a tower with about 24 meters (75 feet) in height and 5 meters (16 feet) in diameter. At the same time cool air is passed at about 10 ° C (50 ° E) from the bottom up (i.e., countercurrent to the falling spray) at a flow rate of about 850,000 liters per minute (30,000 cubic feet per minute).

The frozen product is collected at the bottom of the tower. The product particles are white in appearance, are loose, are generally spherical and solid. These particles have a porous surface (blubbery appearance). The solum mass of the prill

is about 0.37 g / cm @ ³ .

EXAMPLE 15

To 95.5 g of the detergent of Example 2 (without the particles of Example 1) is added 4.5 g of the prills of Example 14.

EXAMPLE 16

Each of the

Examples 5 to 13 except that the cationic component-nonionic component mixture used in those Examples is replaced by the prills of Example 14. '

EXAMPLE 17

Repeated each of the above Examples except that the nonionic component of the cationic component-nonionic component mixture is used in the amounts of 2%, 7%, 12%, 15%, 20%.

EXAMPLE 18

As one of the previous Examples is repeated again except that the cationic softener of the cationic component-nonionic component mixture is replaced by the following:

(a) dimethyl-dibutylammonium methasulfate

(b) dimethyl-hydrogen hydrogen ammonium chloride

(c) 1-methyl-1-tallowamidoethyl-2-tallow-imadazolinium sulfate

(d) 1-methyl-1-oleylamidoethyl-2-oleylimidazolinium methosulphate.

EXAMPLE 19

In each of the foregoing Examples wherein the cationic component-nonionic component particles are used in mixtures with the detergent, the amount of the component to be provided is 2%, 7% and 10% thereof based on the weight of the detergent & softener .

Among the

ionic acids which are useful in the combination of the nonionic cationic component, it is apparent that there is a wide range of melting points. Thus Neodol 23-6.5 is a nonionic liquid component such as Igepal CO-630 (nonyl-phenol plus 10 moles of ethylene oxide) whereas Neodol 25-7 is a somewhat pasty solid and 0 Neodol 25-12 a soft white solid. For high contents of ethylene oxide (i.e., equal to or greater than 15 moles of ethylene oxide) the product becomes more solid and tactful and somewhat waxy in appearance.

Particularly when

is intended to utilize high (i.e., above about 5 to 10%) levels of nonionic component in the cationic co-melt product, it is usually advantageous to use a blend of a liquid nonionic component and a nonionic component alone.

read. In addition to the components other solid or pasty nonionic components such as glycerol mono- and di-glycerides fatty. Of particular interest in this regard are glycerol monostearate, glycerol monooleate and glycerol palmitate.

EXAMPLE 20

Example IA is repeated except that half of the nonionic Neodol component is replaced with glycerol monostearate. In the test procedure of Example 2 this product is equivalent to the product of Example IA.

EXAMPLE 21

Example 3 is repeated

using the product of Example 20 instead of the cationic products of Example 3. Excellent results are obtained.

EXAMPLE 22

Example 7 is repeated exoep. so that the detergent contains the tertiary softener combination of Example 20 in place of the binary combinations of Example 1. The results are as excellent as those of Examples 5 and 7.

EXAMPLE 23

Example 22 is repeated except that the

The nonionic component used is Neodol 45-11 (an alkanoyl

linear ethylene oxide, and an additional 11 moles of ethylene oxide).

B-15

EXAMPLE 24

2 was repeated Example 6 except that the spaghetti soap is replaced with an equal weight of Garbowax crystals (MW-3000-8000).

EXAMPLE 25

Repeat Example 24 except that the amount of Carbowax is varied as follows (% in detergent):

(The) 0.5 (B) 1.0 (W) 2.0 (d) 4.0

EXAMPLE 26

Repeated each of Examples 6, 7, 9, 10, 12, 13, 16, 17, 18, 19, 21, 22 and 23 except that in cases where soap was used in the form of spaghetti

This is replaced by the Carbowax used in the Examples

24 and 25 in the quantities indicated below (% based on

weight of detergent):

rtaSOO '. . ιο $ οο | -5- 3ΒΕ03Β ........... jggSSggj (I.e.

7.7 77 - 7.7 7.7

the κι

Eur-lex.europa.eu eur-lex.europa.eu

77

: •• 7

77-

(The) 0.2 (B) 0.4 (W) 0.8 (d) 1.0 (θ) 2.0 ω 2.0 (g) 5.0

EXEHPBO 2?

Examples 24, 25 and 26 are repeated using instead of Carbowax the following:

(A) Pluronic E-108 crystals

(B) spaghetti soap of high water solubility containing (a) 10% sodium xylene sulfonate; (b) 20% sodium xylene sulfonate; (c) 40%

of sodium xylene sulfonate.

The Carbowax product of Examples 24 to 26 is a polyethylene glycol. Pluronic E-108 of Example 27 is a polyoxypropylene and polyoxyethylene chain polymer containing 20% polyoxypropylene groups as hydrophobic and 80% polyoxyethylene groups. The hydrophobic base has a molecular weight of 3,250

, K.

77:77 .. 7 777 \

Pluronic Ρ-108 is also illustrative of the water-soluble nonionic components which are useful in the co-fused cationic component-nonionic component products of this invention. Of particular importance are the liquid Pluronics containing up to about 50% polyoxyethylene groups and a polyoxypropylene moiety base hydrophobic molecular weight of about 950 to 4,000. When a combination of, for example, Neodol 23-6.5 and Pluronics, it may be preferred to use solid or pasty Pluronics. These generally contain from 25% to 80% polyoxyethylene groups. Illustrative of Pluronic L-61, Pluronic L-64, Pluronic L-72 and Pluronic 101; of Pluronics pasty we find Pluronic P 85 and Pluronic P 105 among others; of solid products we can mention Pluronic P-87 and Pluronic P 27

EXAMPLE 28

As an illustration of the anti-stain benefits of the present invention a number of different stained white materials are washed at both 70Â ° F (21Â ° C) and 49Â ° C (120Â ° F) using on the one hand (A) detergent containing only cationic component , and on the other hand (B) the prill constituted by the cationic component-nonionic component of Example 14. The detergent is that which has been described in

Example 2.

All white materials are also stained and the reflectance values of the washed materials are measured. The reflectance values (Rd) are as follows:

21 ° C (70 ° F)

49 ° C (120 °)?)

(THE) (B) (THE) (B)

Dacton spun 77.7 79.0 64.7 66.5 Lacton / Cotton (65/35) 81.4 81.5 73.9 7θ, 1 Cotton 87.8 87.8 87.3 87.3 Nylon 84.1 85.2 84.1 84.5

This clearly demonstrates that even after just one wash a significant improvement in the Dacron spun at both wash temperatures was found in the Dacron (Cotton at 49øC (120øE) and Nylon at 21øC (70ø E) A difference of 0.5 Rd units is significant in the sense that this difference can be discerned visually.

Claims

over there. A process for preparing a softening detergent composition in the form of small particles capable of imparting softness, detergency, anti-static and non-staining properties to the fabrics treated with it in a washing process, characterized in that it comprises said composition comprising about 5 to 40% by weight of a non-water-soluble organic surface-active agent, about 10 to 60% by weight of a "builder"

i.e.,

10 $ 00

w

From about 2 to 20% by weight of a mixture of cationic amino acid softener with nonionic component and about 0 to 20% by weight of a soluble or water dispersible fatty acid soap or a non-ionic surfactant mixture, the nonionic component constituting about 2 to 50% by weight of said soap-like mixture, and wherein the mixture of the cationic component with the nonionic component is dispersed in said composition in a substantially homogeneous manner and in the form of separate particles.

2ã. 2. A process as claimed in claim 1, wherein said cationic component is a quaternary halide and said nonionic component is a water-soluble ethoxylate.

3. A process according to claim 2, wherein said nonionic component consists of about 2 to 20% of said mixture and said mixture consists of about 2 to about 15% of said mixture detergent.

4- 3. A process as claimed in claim 3, wherein said cationic component is a di-alkyl halide of long chain di-alkyl of quaternary ammonium chain, said nonionic component being an aliphatic alcohol ethoxylate ( A thiophenol or alkylated phenol, or thiophenol containing about 3 - 100 moles of ethylene oxide, said nonionic component consisting of about 2% to about 15% by weight of said mixing the cationic component with nonionic component and said mixture consisting of from about 2 to about 10% of said detergent.

5-. 4. A process as claimed in claim 4, wherein said detergent is not an alkyl benzene sulfonate, in that said "builder" consists of a phosphate, in that said cationic component is a di- (C1 -C4) _yl _) alkyl-di (CL _i | _-C ^ g) alkyl ammonium, in that said nonionic component is an alcohol (Cg-C ^ g) linear aliphatic ethoxylate containing about 3 to about 5θ moles oxide of ethylene and in that said nonionic component comprises from about 3 to about 10% by weight of said cationic component mixture with nonionic component.

5 > 5. A process according to claim 5, wherein said cationic component mixture with nonionic component is a prill (spherical particle the size of a hunting lead).

7-. 5. A process according to claim 5, wherein said cationic component mixture with nonionic component is the finely ground product resulting from the combined melting of the cationic component and the nonionic component.

8 ". 5. A process according to claim 5, wherein said prill is a generally spherical, porous surface and solid core particle.

9 ^â . - Process according to claim 3, wherein the active agent itensio be a (Cg-C ^ g) alkylammonium benzenesulfonate liçear-amine by the cationic softener is selected from the group consisting of di-ÍG.j salts. Quaternary ammonium salts, imidazolinium salts and mixtures thereof, and the nonionic component of the cationic component mixture. nonionic component is an aliphatic linear (C--C g)) alkanol containing about 6 to about 20 moles of ethylene oxide.

10ã. 5. A process according to claim 9, wherein the nonionic component is

a non-ionic liquid and constitutes about 2-10% in

weight of the cationic component mixture with non-component

ionic.

-41 ''. 5. A process according to claim 10, wherein the mono- or di-ester of glycol or glycerol of a C ₈ -C ₁₈ fatty acid is included as an adjuvant.

12 ^. 11. A process according to claim 11, wherein the adjuvant is glycerol monostearate.

13 &. 11. A process according to claim 12 wherein the amount of glycerol monostearate is from about 1 to about 20% based on the weight of the cationic component blend with nonionic component and is included as a component of this blend.

14 &. A process for the preparation of a composition according to claim 1, characterized in that it comprises spray-drying the non-soap organic surfactant and the structuring salt and the subsequent addition to the spray dried material of the ingredients.

15ã. A process for the preparation of a spray-cooled softener composition comprising an intimate admixture of a cationic amine softener of about 2 to 20% based on the weight of said mixture of a soluble nonionic surfactant ethoxylate compound Water.

-4216 ^a . 8. A process according to claim 15, wherein the ethoxylate is a linear aliphatic (Og-Cg) alcohol and in that the amount of ethylene oxide combined is from about 5 to about 100 moles.

17 ^a . A process according to claim 16, wherein the amount of the nonionic compound ranges from about 2 to about 10%.

18 ^a . - Process according to claim 17, characterized by including from about 2 to 20% of a mono- or di-glycol or glycerol ester of a fatty acid ^(C l -C _8).

19 ^a . 2. A process according to claim 18, characterized in that about 2 to 10% of glycerol monostearate is included.

.