AU598489B2 - Detergent composition of improved oily soil removing capability - Google Patents

Description

in, COMMONWEALTH OF AUSTRALIA D-a-n- 1 LU L~ SPECIF ICA 5 N 8 COMPLETE

(ORIGINAL)

6-1 g6186 Class Int. Class Application Number Lodged Complete Specification Lodged Accepted This document contains the amendments made under Section 49 and is correct for printing.

Published 15 November 1985 SPriority i Relate Art Name of Applicant Address of Applicant COLGATE-PALMOLIVE COMPANY 300 Park Avenue, New York New York 10022, United States of America Actual Inventorex Address for Service t Sunhee Choi F.B. RICE CO., Patent Attorneys, 28A Montague Street, BALMAIN 2041.

Complete Specification for the invention entitled: DETERGENT COMPOSITION OF IMPROVED OILY SOIL REMOVING CAPABILITY The following statement is a full description of this invention including the best method of performing it known to usAie:-

I

Ao This invention relates to detergent compositions.

More particularly, it relates to detergent compositions that are useful for washing laundry in cold water or in room temperature water, and for removing oily soils from laundry despite the fact that the wash water is at a lower' temperature than is usually considered to be desirable for good soil removal.

Various built heavy duty synthetic organic detergent compositions, both in particulate and liquid form, have been described in the literature and many of these have been and are now being commercially marketed for use in washing clothes, tO 0 t O *P usually by means of an automatic washing machine in a home laundry. Many discoveries have been made of modifications of the detergent composition formula to improve its detergency.

SAmong such discoveries was the synergistic detergency of nonionic and cationic surface active agents, especially when washing is effected at room temperature or lower. Such detersive synergism is described in an article by Rubingh et al. in 1982 Ind. Eng. Chem. Prod. Res. Dev. No. 21, pages 176-182. Also, U.S. patents 4,222,905 and 4,259,217 describe heavy duty detergent compositions comprising nonionic and caticnic surfactants. Such patents mention that the 2 compositions thereof are unusually effective in removing greasy and oily soils, including body soils, from fabrics, and are also effective in removing particulate soils.

C21 Dicarboxylic acid which is available from Westvaco Corporation as DIACID 1500, has been taught to possess hydrotropic properties and was said to have been used as soluble salts in detergents for its hydrotropic or solubilizing effect on detergents that would otherwise be less soluble than desired. In an article by Ward et al., entitled Industrial Utilization of C 2 1 Di-carboxylic Acid, published at Vol. 52, J.A.O.C.S. 219-224 (1975), and in the article Hydrotropic Function of a Fatty Di-carboxylic acid, at 20 Tenside Detergents No. 4 (1983), at pages 177-180, the solubilizing effect of C 21 dicarboxylic acid salts is mentioned. In those articles it was reported that such C 2 1 diacid salts are unique in the degree.of water solubility they possess, and that they are capable of assisting in greatly solubilizing other substances into aqueous systems in which such substances are normally quite insoluble. The same articles mention that the C 2 1 dicarboxylic salts supplement the activity of the other substance so that less is required to achieve the desired results. U.S. patent 3,965,161 teaches using

C

2 1 dicarboxylic acid salts as hydrotropes or solubilizing agents in combination with nonionics to form biodegradable and non-toxic cleaning compositions.

The art teaches that the presence of cationic 3 surfactant with nonionic detergent synergistically improves the detergency of the nonionic, and it states that C 21 dicarboxylic salt can act as a hydrotrope and as a solubilizing agent for various materials, including nonionic surface active agents. Applicant does not believe that C 2 1 dicarboxylic salt acts as a hydrotrope in the systenms of this invention. Applicant has found that when C 2 1 dicarboxylic salt is added to a nonionic detergent, without any cationic surfactant being present, it does not increase the detergency of the nonionic, and when too much dicarboxylic salt is added to cationic and nonionic mixtures of detergents cleaning action is reduced. One who knew such facts would have found it surprising that when the C 2 1 dicarboxylic salt is added to a mixture of nonionic detergent and cationic surface active agents, and the C 2 1 dicarboxylic salt concentration is kept relatively low, significant improvement in detergency is obtainable, especially at low wash water temperatures. Accordingly, the present invention is unobvious from the prior art and from knowledge of the adverse effects of the C 21 dicarboxylic salt on the nonionic detergent. Addtionally, when too much C 2 1 diacid salt is present, 1/2 as much C 2 1 diacid salt as detergent (nonionic cationic), soil solubilization and cleaning may be decreased.

In accordance with the present invention a detergent composition for removal of oily soil from substrates comprises a synthetic organic nonionic detergent, a cationic surface active agent, a water soluble C 21 dicarboxylic salt, and a water soluble salt and/or enzyme, with proportions of the first three such components being such that that of the combination of nonionic detergent and cationic surface active agent is a detersive proportion and that of the C 21 dicarboxylic salt is sufficient to improve the oily soil detergency of the combination of nonionic detergent and cationic surfactant, especially in cold water. Preferred detergent compositions are spray dried, particulate, heavy duty laundry detergent compositions in which substantially inorganic spray dried base beads are post sprayed with liquid state normally solid nonionic detergent, but heavy duty detergent compositions in mixed powder, agglomerate, cake, foam, gel, paste and liquid forms-arealso within the invention, as are processes for washing laundry at comparatively low temperatures with components of the invented compositions.

The nonionic detergents employed in the practice of this invention are condensation products of lower alkylene oxide with hydroxy-containing lipophiles. Normally, the lower alkylene oxide will be ethylene oxide and the detergents will be made by condensation of ethylene oxide with a lipophile-containing compound, such as a higher fatty or linear alcohol of 10 to 18, preferably 11 to 16,and more preferably 12 to 15, 14, 15,carbon atoms content (average). However, suitable mixtures of ethylene oxide and propylene oxide, sometimes with some butylene oxide, may also be employed as the hydrophile donors. Instead of the higher alcohol, higher alkyl-substituted phenols may be employed, such as those wherein the alkyl is linear and of 7 to 9 carbon atoms. Block copolymers of ethylene oxide (hydrophilic) with propylene oxide and/or butylene oxide (lipophilic) may also be employed, such as those sold unnpr ii-i the trademark Pluronic Pluronics F-68 and L-44.

When the nonionic detergent is a condensation product of ethylene oxide and higher fatty alcohol or alkyl phenol there will normally be from 3 to 20 moles of ethylenp oxide per mole of nonionic detergent product. Preferably such range will be from 5 to 20 and most preferably from 6 to 15, 7, 9, 11 or 12. Of course, the number of moles of lower alkylene oxide per mole of detergent is an average because such detergents are made as mixtures.

The cationic surface active agent utilized in the present invention is preferably a quaternary ammonium halide, although analogous phosphonium compounds may be S, employed under certain circumstances. Various quaternary ammonium halides may be utilized but those which are most satisfactory are those which contain a higher alkyl *substituent, preferably accompanied by a plurality of

S

t lower alkyl substituents. Thus, it may be of the formula

CH

3 SR. N X-

S/I

CH

3

CH

S3 3 wherein R is a hydrocarbyl chain from 8 to 22 carbon atoms and X is a halogen selected from the group consisting of chlorine and bromine. The higher alkyl, which may be of to 18 carbon atoms, is preferably a single higher alkyl, and three lower alkyls, of 1 to 3 carbon atoms, are also present. Still in some circumstances one of such lower alkyls may be replaced by another higher alkyl.

Preferred higher alkyls are those of 12 to 16 carbon atoms, and the preferred lower alkyl is unr: I LIII IA UCr i methyl. While all halogens may be used to make quaternary ammonium halides, normally employment of the fluoride and iodide will be avoided and the chlorides and bromides will be most effective. The following are representative of some of the preferred quaternary ammonium halides employed: myristyl trimethylammonium bromide, lauryl trimethylammonium bromide, cetyl trimethylammonium bromide, myristyl trimethylammonium chloride, lauryl trimethylammonium chloride and cetyl trimethylammonium chloride. Dimyristyl dimethylammonium bromide and the corresponding chloride are also operative but preferably the corresponding trimethylammonium derivatives will be used instead.

The C 21 dicarboxylic acid, which is usually employed in the form of its alkali metal, ammonium or lower (2 to 3 carbon atoms alkyl) alkanolamine salt, preferably a di-salt of sodium, potassium,ammonia or triethanolamine, is a cycloaliphatic dicarboxylic acid of the structure: CH

CH

CH

3

(CH

2 -CH CH(CH 2

-COOH

x /y CH- CH Z Z wherein x and y are integers from 3 to 9, x and y together equal 12, and wherein one Z is hydrogen and the other is a carboxylic acid group. The isomers wherein x is 5 and y is 7 form a preponderance of the acid composition but there are also present minor amounts of the C 21 dicarboxylic acid r~; wherein the cyclohexene ring varies in position along the carbon chain, and minor amounts of dicarboxylic acids of other molecular weights. Typically, the C 21 dicarboxylic acid is of a molecular weight of 352.5, a saponification number of 312, a refractive index at 250C. of 1.485, and a density at 25 0 C. of 1.024 g./ml. The C 21 dicarboxylic acid, the salts thereof, the physical characteristics thereof and methods for manufacturing it are described in U.S. patent 3,956,161, which is hereby inccrporated by reference. The

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21 dicarboxylic salts are made by neutralizing the C 21 dicarboxylic acid with a suitable neutralizing agent, such as ammonia, triethanolamine, diethanolamine, sodium hydroxide or potassium carbonate, and the products of such neutralization may be the corresponding mono- and/or di-salts. Of these, it is considered that the di-salts are best in the present compositions and processes, but in some cases the mono-salts are operative, too, and mixtures are also useful.

The various water soluble salts, such as builder and filler salts, which may be employed in the invented compositions, to improve low temperature washing characteristics.

thereof further, are those normally utilized in detergent compositions. Thus, in particulate heavy duty or built laundry detergent compositions it will be preferable to utilize water soluble builder salts, such as polyphosphates, pyrophosphates, carbonates,'bicarbonates, borates and silicates, b preferably as their sodium salts, and in such products there may also be present filler salts, such as sodium sulfate and sodium chloride. For unbuilt products, often the use of the filler salts alone will be preferred. For liquid heavy duty detergents the more soluble forms of builder salts, which may be potassium or sodium salts, will usually be employed, and the more soluble filler salts may be used in light duty or unbuilt liquid detergents, which are usually of lower pH.

Such filler salts, while usually of alkali metal, may be of other cations, such as magnesium, as in magnesium chloride and magnesium sulfate.

With the "active" components mentioned above there may also be included various other materials for producing special washing effects. Such adjuvants include: water insoluble builders, such as zeolites; fabric softening materials, such as bentonite; laundry whitening additives, such as fluorescent or optical brighteners; antibacterial materials, such as trichlorocarbanilide; soil suspending agents, such as sodium carboxymethyl cellulose; soil release promoting agents, such as polyethylene terephthalate-polyoxyethylene terephthalate copolymers; spray dried beads' properties control agents, such as sodium polyacrylate; colorants; foaming agents, such as lauric myristic diethanolamide; antifoams, such as dimethyl silicone; enzymes, such as proteases and amylases; whitening agents, such as

'LI

.~,~-,I.~I~C~,~4U3I.pnLlY-OUIUI sodium perborate; and perfumes (with the last three components normally being post-added to spray dried products). While ionizable inorganic salts are useful to improve detergency of the present particulate detergent compositions, sometimes the presence of such ionizable salts in liquid detergents can destabilize the detergent, and in such instances it will often be desirable to employ enzymes instead of such builder salts to increase detergency with respect to any proteinaceous and amylaceous soils. However, often the water soluble salts can be present in the heavy duty liquid detergent and will not destabilize such composition to an objectionable degree.

The proportions in the present detergent compositions of the nonionic detergent, cationic surface active agent and

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21 dicarboxylic salt are usually from 1 to 30 parts of nonionic detergent, 1 to 10 parts of cationic surface active agent, and 0.1 to 3 parts of C 21 dicarboxylic salt, and preferably the ratio of nonionic detergent cationic surface active agent (surfactant) will be in the range of 4:1 to 1:1. Preferably, especially in heavy duty laundry detergent compositions, there will also be present from 5 to 70 parts of water soluble salt, and in'heavy duty laundry detergent compositions such salt will be builder salt or a major .proportion thereof will preferably be builder salt. For better detergency improving results the C 21 dicarboxylic ~i -i 10 salt will be from 3 to 15%, more preferably 5 to 10% of the sum of the nonionic detergent and cationic surfactant. The proportions given will also be the proportions of the recited components in the wash water.

Such wash water solution of detergent composition components is preferably made by dissolving the detergent composition in the water, but alternatively, such components may be added to the water or the water may be added to them. In either case the result is improved detergency with respect to the removal of oily soil from the laundry, especially when it is washed at room temperature or lower. By "oily soil" in this specification are meant both oily and fatty soils, those which are in either liquid or solid state at room temperature. It has been found that the usual "oily" soils are mixtures of liquid oily material held inside solid fatty deposits. For convenience, and because it has been considered by some to be a standard for testing oily and fatty soil removal, triolein has been employed in some testings of the present detergent compositions, but sebum body soil and lard were also used in such testings. The invented compositions are also effective detergents for other oily soils, such as those including beef tallows, lards, hamburger greases, shortenings, cooking oils, mayonnaise, salad dressings, face and skin creams, salves and petroleum oils and greases.

The detergent compositions of this invention will usually comprise from 2 to 35% of nonionic detergent, 1 to of cationic surface active agent, 0.1 to 4% of water soluble C 21 dicarboxylic salt, and 10 or 20 to 80% of water soluble salt, of which a major proportion is preferably of a builder salt for the nonionic detergent. Conventional adjuvants and fillers for such compositions, and solvents and dispersing media, when the product is a liquid, may make up any balances, to 100%. Preferred percentages of the mentioned components are 10 to 22, 1 to 10, 0.6 to 3, and 25 to respectively, with more preferred proportions for a particulate detergent composition being about 20%, and respectively. Any balances (to 100%) are made up by water and adjuvants. Liquid detergent cor'?ositions of the invention preferably contain 15 or 20 to 40% of nonionic detergent, 1 to 20% of cationic surface active agent, 1 to 5% of salt of C 21 dicarboxylic acid, and the balance of aqueous medium 00 0 00#: (which may be aqueous alcoholic), which may include water soluble salt and adjuvants, as previously described.

".0.0When laundry is washed with the invented compositions 0 (or with the components thereof in the described proportions)- :0*20 the concentration of the composition (or- the components) will normally be in the range of 0.02 to preferably 0.1 to and more preferably about 0.15 to While the lower concentrations within the above ranges are more frequently' used, that is for economic reasons; the more of the product that is employed, the better its performance. Normally the detergent compositions will be utilized in automatic washing machines of the home laundry type but they may also be useful 12 in commercial laundering. The machines employed typically include automatic washing and rinse cycles, and after completion of washing the laundry is usually dried in an automatic laundry dryer. The wash time, which will generally be from five minutes to an hour, is normally dependent on the type of material that constitutes the laundry, the extent to which it is soiled, and the nature of the soil. The wash water will preferably be relatively soft but the invented detergent compositions and the components thereof are capable of effectively washing laundry in waters up to 250 p.p.m. of mixed calcium and magnesium hardness, as calcium carbonate, although hardness is preferably in the 0 to 100 or 150 p.p.m.

range. Generally, the hotter (or warmer) the water the better the wash, because hot water tends to dissolve soils better and also helps to melt or liquefy low melting binding materials, such as fats and greases, which tend to hold the soil or dirt onto the fabrics of the laundry.

The compositions of this invention are useful for hot water washing but are especially useful for room temperature or cold water washing of laundry because, without the need for melting the fatty or greasy binder, the combination of active components of this invention significantly promotes the release of such oily binders and soils from laundry during washing in room temperature or cold water. While water temperatures up to boiling may be employed, if feasible, the normal washing temperature _Cij I r will be from 10 to 70 0 and often what is considered to be warm water, in conventional American home laundering by automatic washing machine, is in the temperature range of to 50 0 C. The present detergent compositions result in satisfactory removal from laundry of oily and other soils at lower temperatures, such as those in the range of 10 to While cleaning is not as good in the lower part of this range as in the upper part, it is feasible to conduct washing at temperatures in the range of 10 to 20 0 with the results obtainable being comparable to those obtained when washing at higher recommended temperatures with conventional commercial heavy duty laundry detergents. It is preferred that the wash water be at a temperature in the range of 20 or to 35 0 28 0 C. and 30 0 for best "room temperature" washing, in which significant improvements in detergency are obtained, compared to control commercial detergent compositions. Another advantage of the invented low temperature washing process, in addition to saving the cost of heating the wash water, is that the lower temperature of washing does not cause settings of stains and subsequent difficulties in removing them from the laundry, which can result from hot water washing of laundry containing certain stains.

The following examples illustrate but do not limit the invention. All parts in the examples and in the specification and claims are by weight and temperatures are in OC.

unless otherwise indicated.

i I i i: i: i ii It will be noted that in some of the working examples, which follow, washing concentrations ofthe present compositions are higher than that which is normally employed. Such higher concentrations were used to accentuate differences between experimental and control products but significant differences are also obtainable when conventional washing concentrations are employed, as was previously described. Also, in some instances comparatively long soaking times may be used to accentuate differences in oily soil solubilization between experimental 10 and control compositions, but significant differences are obtainable with shorter soaking periods and in washing operations that do not include pre-soakings.

EXAMPLE 1 ja 4 V 0 0 a '00 aa o 0 0 a 09 a a0 a 0 0O~ 9 6 0 0000 0* on C' 0 09 0 a 6 0 Component Nonionic detergent (Neodol 23-6.5)* Quaternary ammonium halide (myristyl trimethylammonium bromide)

C

2 1 dicarboxylic acid, potassium salt Sodium tripolyphosphate Water (100 p.p.m. hardness, as CaCO 3 Percent 0.08 0.02 0.01 0.2 99.69 9* 99 ou 9 0 9 100.00 Condensation product of higher fatty (linear alcohol of 12 to 13 carbon atoms per mole, with 6.5 moles of ethylene oxide.

99.69 Parts of wash water of 100 p.p.m. (as calcium carbonate) mixed calcium and magnesium hardness, at a temperature of 25 0 has dissolved in it the above listed four detergent composition components, to yield a 0.31% solution of the described 4-member composition. Such wash water is employed in a laboratory washing machine (Tergotometer), using a standard laboratory washing cycle, to wash out oily stains from various pre-stained normal laundry material (cotton, polyester and cotton-polyester blend [65:35]) swatches, stained with triolein. Approximately 72% of the oily material (triolein) I is found to be removed from the test swatches, which is considered to correspond to almost complete removal of normal oily (and fatty) soil on normal laundry. Such washing is significantly superior to that obtained by using commercial heavy duty detergent compositions at manufacturers' recommended concentrations, using wash water at the same temperature (25 0 To obtain similar oily soil removal by utilization of a hydrotrope instead of the C 21 dicarboxylic salt it is found that as much as 10 times as much or more of sodium cumene sulfonate, sodium xylene sulfonate or ammonium xylene sulfonate has to be employed.

Results similar to those of the invention of this example are obtained when, instead of employing triolein as the oily soil, lard or sebum soil is substituted. Also, even better results are obtainable when ammonium and triethanolamine tC._ salts of C 21 dicarboxylic acids are used. The corresponding sodium salt is expected to be as effective as the potassium salt.

Instead of the described quaternary ammonium compound, cocoyl trimethyl ammonium chloride, tallowyl trimethyl ammonium chloride, and cetyl trimethyl ammonium bromide may be substituted, as may be other quaternary ammonium bromides and chlorides, and in some instances, corresponding phosphonium compounds, and similar results are obtainable. While the presence of the sodium tripolyphosphate is important to the obtaining of a building function for the nonionic detergent, good oily soil removing activity results when other builders or mixtures thereof are substituted for all or part of the sodium tripolyphosphate, sodium pyrophosphate, sodium carbonate, sodium silicate, borax.

Alternatively, a portion of the builder content, such as up to half thereof, may be replaced by other electrolytes, such as sodium sulfate or sodium chloride, and good oily soil removing properties are noted. The described nonionic deter- 20 gent may be replaced by other nonionic detergents, such as: nonyl phenol polyoxyethylene ethanol, wherein the polyoxyethylene chain is of 3 to 20 ethylene oxide groups, 8 such groups; other condensation products of higher fatty alcohols and ethylene oxide, such as Neodol 25-7 and Neodol 45-11; and ethylene oxide-propylene oxide block copolymers, I r such as Pluronics L-44 and F-68, and the same type of improved cold water oily soil'removal and detergency for laundry will be obtained.

When the water temperature is increased to 60 0 C. even better oily soil removal characteristics are obtained but the difference in such property between the invented compositions (or wash water) and a "control", wherein a greater proportion of hydrotrope (twice as much) is employed instead of the salt of the C21 dicarboxylic acid, is not considered to be as significant as it is at lower temperatures, such as 25 0 30 0 C. and 0

C.

EXAMPLE 2 SComponent Neodol 23-6.5 15 Sodium tripolyphosphate Sodium pyrophosphate Sodium orthophosphate Sodium silicate 0 9 Proteolytic enzyme C I t 20 Fluorescent brightener (Tinopal 5BM Extra Conc.) Blue dye Perfume Myristyl trimethylammonium bromide

C

21 dicarboxylic acid, ammonium salt Water Percent 20.7 40.6 16.2 0.7 1.3 1.3 0.1 0.3 1.2 1.1 100.0 The above detergent composition, in particulate spray dried form, is made by spray drying an aqueous crutcher mix of all the components except the nonionic detergent, enzyme, perfume, myristyl trimethyl ammionium bromide, and

C

1 dicarboxylic diammonium salt, to base beads of sizes within the range of No's. 10 to 100 U.S. Sieve Series, after which the nonionic detergent, in molten form and at elevated temperature, is sprayed onto the base beads so as to be absorbed by them, and subsequently the enzyme, quaternary ammoniumn halide, C 1 dicarboxylic salt and perfume are blended with the product. Alternatively, the solid materials may be mixed with the base beads prior to application of the nonionic detergent, and the perfume may be applied afterward.

The detergent composition of this example, when tested against a control particulated&thergent of the same formula, but omitting the quaternary ammnonium halide and the

C

1 dicarboxylic acid salt, in a cold water wash, i21 B using a commercial automatic washing machine, removes more than 50% more lard from pre-soiled swatches of polyester, cotton and cotton:polyester blends than does the control, using the same washing machine and washing procedure. The concentration of detergent composition in the wash water is about 0.65% but appreciable improvement in oily and fatty soil removing capability, compared to a control, can be observed at concentrations of the detergent composition as low as 0.02%.

-i I-

I:

EXAMPLE 3 Component Water (essentially 0 hardness) Ethanol Triethanolamine dodecylbenzene sulfonate Neodol 23-6.5 Enzyme (Alcalase) Enzyme (Termamyl) Sodium formate Fluorescent brightener Dye Perfume Myristyl trimethyl ammonium bromide Ammonium salt of C 2 1 dicarboxylic acid 15 Percent 47.2 9.8 32.0 0.6 0.4 0.3 0.1 0.4 1.2 100.0 t L: 4a t I I A liquid detergent of the above formula is made by mixing the components together, which results in a product having a viscosity of about 125 centipoises, at 25 0

C.,

employing a Brookfield RV Viscometer, using Spindle No. 1 at 20 r.p.m. The pH of the product is about 7.7 and its specific gravity at 25 0 C. is 1.026. In a variation of the formula the anionic detergent component is omitted to avoid any interaction with the cationic surfactant, so that storage stability will be improved.

When the liquid detergent is used to wash mixed laundry containing test swatches pre-soiled with triolein, lard and sebumn (on polyester, cotton, and cotton-polyester blends), in room temperature water (25 0 against a control detergent composition containing '11 the components in the described proportions, except omitting the quaternary ammonium halide and C21 dicarboxylic salt, a significant improvement in fatty soil removal is obtained over the control, often with almost twice as much of the oily soil being removed by the "experimental" product in the same washing time. Normal use concentration of the liquid detergent (and the same concentration is employed in this experiment) is about 0.1% but such detergent is found to be effective at concentrations as low as 0.02%, although best results are obtained at higher concentrations, Similar results are obtainable for the formula omitting the anionic detergent.

In modifications of these formulas, potassium pyrophosphate (21% of the formula) is substituted 'or 10% of water, 10% of Neodol 23-6.5 and the 1% of enzyme, in both the formulas, containing and omitting anionic detergent. The results are built heavy duty liquid detergents of good cold water washing properties, useful to remove oily soil from laundry, and better in such respect than control products from which the quaternary ammonium halide and C 21 dicarboxylic salt were omitted.

-i L i- -iii--ll- ~-ulrxi EXAMPLE 4 A particulate built synthetic organic detergent composition is made by mixing together 40 parts of sodium tripolyphosphate, 3 parts of tallowalkyl trimethyl ammonium chloride, 2 parts of the diammonium salt of C 21 dicarboxylic acid and 25 parts of sodium sulfate (with 10 parts of water contained in such particulate materials, either absorbed or as a hydrate), after which 20 parts of Neodol 25-7, a nonionic detergent made by Shell Chemical Company, which is the condensation product of a molar proportion of a higher fatty alcohol of 12 to 15 carbon atoms with 7 moles of ethylene oxide, in molten state at 50 0 are sprayed onto the mixture so as to be absorbed by it. The resulting particulate product is tested against a control commercial particulate detergent product of the formula given in Example 2, but omitting the I quaternary ammonium salt and the C21 dicarboxylic salt. In such test, which utilizes automatic washing machine washing of laundry stained with normal oily stains, including fatty soil, greases, both animal and mineral, and sebum soil, the 20 detergent composition concentration in the wash water is 0.15% and the wash water temperature is 25 0

C.

The described invented composition washes the laundry significantly better (as can be established by comparisons of reflectance readings of washed laundry) than the control, apparently at least in part due to its superior capability of promoting the release of oily and -I i fatty binder materials from the substrate fibers of the laundry.

When a liquid composition of the same proportions of nonionic detergent, builder salt (STPP) and C 21 dicarboxylic ammonium salt, with 30 parts of deionized water and 5 parts of ethanol, is tested against a corresponding control in the same manner, using the same washing concentration of the composition, the same type of laundry, and operating at the same temperature, essentially the same S 10 significant improvement in detergency vs. the corresponding control will be obtained.

From the preceding description it is clear that I the subject of this patent application is a heavy duty detergent composition in which improved cleaning of laundry is obtained by use of nonionic detergent, cationic surface active agent, C 21 dicarboxylic salt and water soluble I21 builder and/or filler salt, preferably builder salt, and/or Senzyme. Preferably, water soluble inorganic builder salt and/or enzyme will be present to improve the detergency so that the composition will be "heavy duty", capable of washing out from laundry normally hard to removal soils. Of the builder salts the phosphates are preferred and it is often desirable that a major proportion of the builder salt present should be phosphate, more preferably, sodium tripolyphosphate.

Often the percentage of inorganic builder salt present will desirably be in the range of 5 to 25% in liquid detergent

I

I

compositions and the proportions of enzyme will be in the range of 0.5 to The "enzymes referred to are commercial enzyme preparations (which usually include only minor proportions of active enzyme material). Mixtures of enzymes and mixtures of builder salts may be employed, and, when in the specification reference is to the singular, with respect to any of the components of this invention, it is to be understood that mixtures are encompassed thereby.

In the foregoing examples particulate and liquid detergent compositions of the invention have been described, and such forms are usually preferred. However, the invented compos-itions may also be made in paste, gel, cream, agglomerate, briquette, bar and cake forms, or the individual components may be added separately to the water or may be admixed shortly before intended use.

,The invention has been described with respect to *t illustrations and working embodiments thereof but is not to rirrJ be limited to these because it is evident that one of skill in the art, with the present specification before him, will 20 be able to utilize substitutes and equivalents without departing from the invention.

Claims (14)

1. A detergent composition for removal of oily soil from substrates, which comprises a synthetic organic nonionic detergent; a cationic surface active agent; a water soluble salt of a C 2 1 dicarboxylic acid of the formula CH CH CH 3 (CH 2 )x -CH CH(CH 2 -COOH H 2 ,CO CH- CH z z wherein x and y are integers in the range of 3 to 9, x and y together equal 12, and wherein one Z is hydrogen and the other is a carboxylic acid group; and water soluble salt(s) and/or enzyme(s), the proportion of the combination of nonionic detergent and cationic surface active agent being detersive and the proportion of the C 21 dicarboxylic acid salt being sufficient to improve the oily soil detergency of the combination of nonionic detergent and cationic surfactant in co.2 water, relative to the detergency of the combination of nonionic detergent and cationic surfactant in colI water, excluding the C 21 dicarboxylic acid salt.

2. A detergent composition for removal of oily soil from substrates, which comprises 1 to 30 parts of a synthetic organic nonionic detergent, 1 to 10 parts of a cationic surface active agent, 0.1 to 3 parts of a water soluble salt of a C 21 dicarboxylic acid of the formula CH CH CH 3 (CH2)x -CH CH(CH 2 CH-- CH z z wherein x and y are integers in the range of 3 to 9, x and II arr r 25 y together equal 12, and wherein one Z is hydrogen and the other is a carboxylic acid group, and 5 to 70 parts of water soluble salt(s).

3. A detergent composition according to claim 2 wherein ,he water soluble salt(s) is/are inorganic.

4. A detergent composition according to claim 3, which is a heavy duty laundry detergent composition, in which the major proportion of the water soluble salt is a builder for the nonionic detergent.

A detergent composition according to claim 4 °0°0 comprising from 2 to 35% of nonionic detergent, 1 to 0 00 0 of cationic surface active agent, 0.1 to 4% of the C 21 diacid salt, and 10 to 80% of water soluble salt. a o o O

6. A detergent composition according to claim 5 wherein 0o gthe nonionic detergent is a condensation product of a lower alkylene oxide and a higher fatty alcohol or phenol, the cationic surface active agent is a quaternary ammonium halide, the dicarboxylic salt is a salt of a cation 0o9: selected from the group consisting of sodium, potassium, coot ammonium, lower alkylamine, and lower alkanolamine, the d water soluble salt is selected from the group consisting 0 s of sodium, potassium and soluble magnesium carbonates, bicarbonates, silicates, borates, phosphates, polyphosphates, chlorides and sulfates, and the builder n, 0salt is selected from che group consisting of alkali metal ocoo tripolyphosphate, pyrophosphate, carbonate, bicarbonate, borate and silicate.

7. A detergent composition according to claim 6 which comprises 10 to 22% of nonionic detergent, which is a condensation product of 3 to 20 moles of ethylene oxide with one mole of higher fatty alcohol of 11 to 16 carbon atoms per mole, 1 to 10% of 26 CH 3 R N X- CH 3 CH 3 wherein R is a hydrocarbyl chain of 8 to 22 carbon atoms and X is a halogen selected from the group consisting of chlorine and bromine, 0.6 to 3% of salt of C 21 diacid, selected from the group consisting of sodium, potassium, ammonium and triethanolamine salts, and mixtures thereof, and 25 to 60% of builder salt(s), which is/are sodium salt(s).

8. A detergent composition according to claim 7 which is in particulate form and comprises 20% of nonionic detergent which is a condensation product of 6 to 7 moles of ethylene oxide and a mole of higher fatty alcohol of 12 to 13 carbon atoms, 3% of tetradecyl, trimethyl ammonium bromide, 2% of ammonium salt of C 21 diacid, and 40% of sodium tripolyphosphate.

9. A detergent composition for removal of oily soil from substrates, which is a heavy duty liquid laundry detergent composition and comprises 15 to 40% of nonionic detergent, which is a condensation product of 3 to 20 moles of ethylene oxide with one mole of higher fatty alcohol of 11 to 16 carbon atoms per mole, 1 to 20% of CH3 R X- CH CH CH 3 CH 3 wherein R is a hydrocarbyl chain of 8 to 22 carbon atoms I 27 and X is a halogen selected from the group consisting of chlorine and bromine, 1 to 5% of a salt of a C 2 1 dicarboxylic acid of the formula CHC CH SCH 3 (C2) -H CH(CH 2 -COOH CH o Q S o0 a wherein x and y are integers in the range of 3 to 9, x and 8 y together equal 12, and wherein one Z is hydrogen and the other is a carboxylic acid group, and 5 to 25% of inorganic builder salt and/or 0.5 to 5% of enzyme, in an aqueous medium.

10. A liquid detergent composition according to claim 9 °a which comprises from 5 to 25% of inorganic builder salt. 0

11. A liquid detergent composition according to claim 9 which comprises from 0.5 to 5% of enzyme.

12. A process for cold water washing to remove oily soil(s) from laundry made from fibrous materials, which °comprises washing said laundry in wash water at a temperature in the range of 10 to 40 0 C, with a detergent composition in accordance with claim 2, at a concentration in the range of 0.02 to 0.7%.

13. A process for cold water washing of laundry to remove oily soil(s) from fibrous materials, which comprises washing such laundry in wash water at a temperature in the range of 20 to 35 0 C with 0.1 to 0.5% in the sh water of a detergent composition that comprises 10 to 22% of nonionic detergent, which is a condensation product of 3 to 20 moles of ethylene oxide with one mole of higher fatty alcohol of 11 to 16 carbon atoms per mole, 1 to I -28 CH 3 R N X- CH 3 CH 3 wherein R is a hydrocarbyl chain of 8 to 22 carbon atoms and X is a halogen selected from the group consisting of chlorine and bromine, 0.6 to 3% of a salt of a C 21 dicarboxylic acid of the formula CH CH CH3(CH 2 -CH C CH(CH 2 )y-COO CH CH z z wherein x and y are integers in the range of 3 to 9, x and y together equal 12, and wherein one Z is hydrogen and the other is a carboxylic acid group, with the salt being selected from the group consisting of sodium, potassium, Sammonium and triethanolamine salts, and 25 to 45% of builder salt(s) which is/are sodium salt(s).

14. A process according to claim 13 wherein a major proportion of the builder salt is sodium tripolyphosphate, the wash water temperature is in the range of 25 to 35 0 C and the detergent composition concentration is in the range of 0.15 to 0.3% DATED this 14th day of March 1990 COLGATE-PALMOLIVE COMPANY Patent Attorneys for the Applicant: F.B. RICE CO.