NZ213225A

NZ213225A - Laundry detergent compositions containing nonionic detergents and quaternary ammonium softener

Info

Publication number: NZ213225A
Application number: NZ213225A
Authority: NZ
Inventors: A J Somers; G Bonnechere
Original assignee: Colgate Palmolive Co
Priority date: 1984-09-04
Filing date: 1985-08-23
Publication date: 1988-04-29
Also published as: FR2569717B1; KR920004718B1; DE3530464A1; SE8504061D0; AU587785B2; PT81067A; FI853381L; LU86066A1; BE903174A; MX162752A; IT8548516A0; ATA257985A; GR852121B; DK403785D0; FR2569717A1; AU4699585A; NO853465L; ZA856447B; FI86741B; FI853381A0

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number £13225 Q Priori:-/ Datsfs): .<f.-n:M'■ 213225 G: Ci rr.p.'ets Specification Fii«?d: Publication Date: A®.® .. P.O. JcLimsl, No: .. .4 NO DRAWINGS :>o3 ! J Patents Form No. 5 PATENTS ACT 1953 Number Dated COMPLETE SPECIFICATION WASH CYCLE DETERGENT-SOFTENER COMPOSITIONS )t/We COLGATE-PALMOLIVE COMPANY of 300 Park Avenue, New York, New York 10022, United States of America, a corporation organised under the laws of the State of Delaware, United States of America do hereby declare the invention for which rt/we pray that a Patent may be granted to ma/us. and the method by which it is to be perfonned, to be particularly described in and by the following statement: I - (followed by pagn la) 213225 This invention relates to a composition and a method for cleaning and softening fabrics in the wash cycle of a laundering operation. More specifically, the present invention relates to softening compositions adapted for use in the wash cycle of a laundering operation, especially using hot water, the composition including a cationic quaternary ammonium compound softening agent and a nonionic surfactant having a cloud point above the washing temperature. Compositions useful for treating fabrics to improve the softness and feel characteristics thereof are known in the art. When used in domestic laundering, the fabric softeners are typically added to the rinse water during the rinse cycle having a duration of only from about 2 to 5 minutes. Consequently, the consumer is required to monitor the laundering operation or take other precautions so that the fabric softener is added at the proper time. This requires the consumer to return to the washing machine either just prior to or at the beginning of the rinse cycle of the washing operation which is obviously burdensome to the consumer. In addition, special precaution has to be taken to use a proper amount of the fabric softener so as to avoid over dosage which may render the clothes water repellant by depositing a greasy film on the fabric surface, as well as imparting a certain degree of yellowness to the fabrics. As a solution to the above-noted problems, it has been known to use fabric softeners which are compatible with common laundry detergents so that the softeners can be combined with the detergents in a single package for use during the wash cycle of the laundering operation. Examples of such wash cycle added fabric softening compositions are shown in U.S. Patents 3,351,438, 3,660,286 and 3,703,480. In general, these wash cycle fabric softening compositions contain a cationic quaternary ammonium fabric softener and additional ingredients which render the softening compounds compatible with the common laundry deteregents. It is also known, however, that the cationic softening compounds added to the wash cycle, either as an ingredient in a detergent-softener composition or as a wash cycle softener, interfere with the brightening activity, as well as the cleaning efficiency of the detergent. As a result, it has been sought to offset to some degree this interference in detergent-softening compositions by using non-ionic surfactants, higher levels of brightener compounds, carboxymethylcellulose , anti-yellowing compounds, bluing agents, and so forth. However, little improvement has been made in wash cycle softening compositions using a variety of detergents, most of which are anionics. There have also, however, been many disclosures in the art relating to detergent compositions containing cationic softening agents, including the quaternary ammonium compound softening agents, and nonionic surface-active compounds. As representative of this art, mention can be made of U.S. Patents 4,264,457, 4,239,659, 4,259,217, 4,222,905, 3,537,993, 3,583,912, 3,983,079, 4,203,872, 4,264,479, 3,951,879, 3,360,470, 3,351,483, 3,644,203, etc. While many of these prior art formulations provide satisfactory cleaning and/or softening under many different '! conditions they still suffer from the defects of not ; providing adequate softening - e.g. comparable to rinse | cycle - added softeners - especially under hot water !! i| washing conditions, i.e. at temperature of 60°C and higher; » | requiring formation of complexes of the cationic compound; i j using lower softening performance water-soluble, e.g. | monohigher alkyl quaternary ammonium cationic compounds; I I being limited to liquid compositions; etc. ! Although it is not uncommon for present day laundry 1 detergent compositions and for conventional home automatic washing machines, especially in the United States, to be able to effect washing/cleaning of soiled fabrics using cold or warm wash water, specially for sensitive fabrics, wash-wear fabrics, permanent-press fabrics, and the like, it is nevertheless appreciated that more effective cleaning (soil removal) requires higher washing temperatures. Furthermore, in Europe and in other countries, the home washing machines operate at hot temperatures of 60°C or more, up to the boiling temperature of the wash water. While these high temperatures are beneficial for soil removal there is not an equal benefit for softening performance. The present invention is based on the discovery that softening performance of a detergent system based on a mixture of a nonionic detergent compound and a cationic quaternary ammonium compound softening agent is significantly enhanced by using a limited class of nonionics characterized by cloud points above the washing temperature. Furthermore, this enhancement of the softening performance is acheived without any, or at least without any significant, deterioration in washing (i.e. cleaning) performance. A relationship between cleaning performance and Che cloud point of a nonionic/cationic detergent mixture ; is known from U.S. Patents 4,222,905 - Cockrell, Jr., j and 4,259,217 - Murphy. More particularly, as stated i ! at column 5, lines 40-61 of the Murphy patent: j "Processes for laundering fabrics with the compositions of the present invention which provide superior greasy and oily soil removal and fabric care benefits, are taught herein. In these processes, the laundry detergent compositions are used under temperature conditions such that the aqueous laundry solution is either at, or close to (i.e. within about 20°C. of) the cloud point (i.e., the temperature at which a phase rich in nonionic surfactant separates in the laundry solution) of the nonionic/cationic surfactant mixture. This can preferably be accomplished by formulating those nonionic/cationic surfactant mixtures so that their could point falls between about 0 to 95°C., particularly from about 10 to 70°C, especially between about 20° and 70°C., most especially from about 30 to about 50°C. During the washing operation, the temperature of the laundry solution is held within this temperature range and within 20° C. of the cloud point temperature. Performance is improved further where the temperature of the aqueous laundry solution is within about 15°C., more preferably within about 10°C., of the nonionic/cationic surfactant mixture cloud point temperature." Apparently, the requirement to operate at washing temperatures at or below the cloud point temperature is based on the premise that the cloud point of the surfactant mixture in the wash water corresponds to the temperature at which micelles of the surface-active agent aggregate to such an extent that these aggregates become so large that they come out of solution, and hence the observed cloudiness. Further temperature increase will lead to complete phase separation of the water and the nonionic surfactant and as a result their detersive action on the soiled fabrics and overall cleaning ability is lost. However, while it is stated by Murphy that the nonionic/cationic mixtures may, "depending on the identity and concentration of the cationic component ... provide the benefits known in the prior art for such cationics, e.g. ... softening effects for textile," is is nevertheless clear that there was no recognition or suggestion that the softening effects of the cationics can be significantly improved by using certain nonionics having high cloud point temperatures, per se. That is, whereas Murphy and Cockrell, Jr. teach a relationship between the cloud point of the nonionic/cationic mixture, washing temperature, and cleaning performance, it has now been discovered that it is the relationship between the cloud point of the nonionic alone (or the nonionic and any electrolytes present in the wash water) and the wash temperature which effects the softening performance of the water insoluble cationic quaternary ammonium compound softening agents. In contrast to the requirement of this invention to use high cloud point temperature (i.e. above about 60°C, especially above about 90°C, especially preferably, above about 100°C) nonionics each of Murphy and Cockrell, Jr. prefer nonionic surfactants having relatively low cloud points. Therefore, the nonionic surfactants used in the composition described in these patents are fatty alcohols ethoxylated with at most 12 moles ethylene oxide, preferably at most 9 moles ethylene oxide, and having hydrophilic-lipophilic balance (HLB) values of from about 5 to 17, preferably from about 6 to 15. Accordingly, it was totally unexpected that softening performance of the cationic softener could be dramatically improved without diminishing cleaning performance of the nonionic surfactant by using nonionic surfactants which include the higher fatty alcohols ethoxylated with at least 15 moles ethylene oxide and which have cloud -5- : points above the washing temperature. It was on the basis of this discovery that the ! present invention was completed. | Accordingly, it is an object of this invention :j to improve softening performance of detergent compositions • i ;| containing quaternary ammonium compound softening agents and nonionic detergent compounds without significantly adversely effecting overall cleaning performance. This and other objects of the invention which will become apparent from the following description are achieved by providing a laundry detergent composition capable of washing soiled fabrics in an aqueous wash liquid, at an elevated temperature of at least about 60°C up to the boiling temperature of about 100°C, which includes a nonionic surface active agent having a cloud point above the elevated temperature, and water insoluble quaternary ammonium compound capable of imparting softening to the washed fabric. In the preferred embodiment the detergent composition will include at least one additional detergent additive including detergent builders, thickeners, anti-redeposition agents, corrosion inhibitors, bleaches, enzymes, dyes, bluing agents, optical brighteners, perfumes, and the like. The nonionics which are contemplated are limited only by their water-solubility and by their cloud point temperature. Conveniently, these criteria are mutually compatible, the high alkylene oxide content contributing to both water solubility and high cloud point temperature. Suitable nonionic surface active agents are commercially available and are derived from the condensation of an alkylene oxide or equivalent reactant and a reactive- hydrogen hydrophobe. The hydrophobic organic compounds may be aliphatic, aromatic or heterocyclic, although the first two classes are preferred. The preferred types of hydrophobes are higher aliphatic alcohols and alkyl phenols, although others may be used such as carboxylic acids, carboxamides, mercaptans, sulphonamides, etc. The ethylene oxide condensates with higher-alkyl phenols or higher fatty alcohols represent preferred classes of nonionic compounds. Usually, the hydrophobic moiety should contain at least about 6 carbon atoms, and preferably at least about 8 carbon atoms, and may contain as many as about 50 carbon atoms or more, a preferred range being from about 8 to 22 carbon atoms, especially from 10 to 18 carbons for the aliphatic alcohols, and 12 to 20 carbons for the higher alkyl phenols. The amount of alkylene oxide will vary considerably depending upon the hydrophobe, but as a general guide and rule, at least about 15 moles of alkylene oxide per mole of hydrophobe up to about 30 moles of alkylene oxide per mole of hydrotrope should be used in order to obtain cloud point temperatures of at least about 60°C or higher. Accordingly, the preferred nonionic surfactants can be represented by the formula R0(CH2CH20)nH (I) wherein R is a primary or secondary alkyl chain of from about 8 to 22 carbon atoms and n is an average of from 15 to 30; or R'-©" 0-(CH2CH20)mH (II) wherein R' is a primary or secondary alkyl chain of from 4 to 12 carbon atoms, and m is an average -7- of 15 to 30. The preferred alcohols from which the compounds I of formula I are prepared include lauryl, myristyl, cetyl, : stearyl and oleyl and mixtures thereof. Especially preferred i j values of R are C^q to ^18 with the C\2 to C^5 alkyls J and mixtures thereof being especially preferred. The preferred values of R' are from Cg to C12, with Cg and c9, including octyl, isooctyl and nonyl being especially preferred. A typical example of a nonionic compound of formula (I) is lauryl alcohol condensed with 15 moles ethylene oxide. A typical example of a nonionic compound of formula II is isooctyl phenol condensed with 30 moles ethylene oxide. Other nonionic compounds which may be used include the polyoxyalkylene esters of the organic acids such as the higher fatty acids, the rosin acids, tall oil acids, acids from petroleum oxidation products, etc. These esters will usually contain from about 10 to about 22 carbon atoms in the acid moiety and from about 15 to about 30 moles of ethylene oxide or its equivalent. Still other nonionic surfactants are the alkylene oxide condensates with the higher fatty acid amides. The fatty acid group will generally contain from about 8 to about 22 carbon atoms and this will be condensed with about 15 to about 50 moles of ethylene oxide as the preferred illustration. The corresponding carboxamides and sulphonamides may also be used as substantial equivalents. The amounts of the nonionic can be any amount which when added to the wash water will provide adequate cleaning performance. Generally, amounts ranging from : about 6 to about 30%, preferably from about 7 to about ; 20%, and especially preferably from about 14 to 167c by | weight of the composition, can be used. j The compositions of the present invention are primarily intended for use in connection with those home | 1 and commercial laundry washing machines which operate i j at elevated washing temperatures, especially at water | temperatures in excess of about 60°C (140°F), preferably j in excess of 80°C (176°F), and especially preferably at-the-boil, i.e. at 100°C (212°F) or more. Naturally, i however, these compositions, while being particularly effective when used at these elevated washing temperatures, can also exert their improved softening performance at lower temperatures below 60°C down to about 20°C or lower. When the compositions are formulated for use at wash temperatures over a broad range of say, for example, 20°C to 60°C, as well as higher temperatures in order to be most useful for a broad range of fabrics including delicate natural and synthetic fibers, as well as more temperature insensitive fabrics such as cottons, etc., the nonionic can be selected to have a cloud point temperature which exceeds the wash water temperature by at least about 20°C, for example, a cloud point temperature of the nonionic in the range of 80° to 90°C. Where, however, the formulation is designed for uses limited primarily to elevated temperatures of 60°C or more, such as is generally the case in Europe, as well as when using industrial washing machines, then the nonionic can have substantially higher cloud points, for example, up to about 50°C above the washing temperature. Thus, for a washing temperature of 60°C, the nonionic should have a cloud point of at least about 65°C, preferably at least about 70°C and up to about 90°C, preferably in the range of from about 70°C to 85°C. For wash water temperatures of 100°C, the nonionic cloud point is chosen in the range of from about 105°C to about 150°C, preferably 105°C to 120°C. As used herein, the term "cloud point" means the temperature at which a graph which plocs the light scattering intensity of the composition versus wash solution temperature begins to sharply increase to its maximum value, under the following experimental conditions: The light scattering intensity is measured using a Model VM-12397 Photogoniodiffusometer, manufactured by Societe Francaise d'instruments de controle et d'analyses, France (the instrument being hereinafter referred to as (SOFICA). The SOFICA sample cell and its lid are washed with hot acetone and allowed to dry. The surfactant mixture is made and put into solution with distilled water at a concentration of 1000 ppm. Approximately a 15 ml. sample of the solution is placed into the sample cell using a syringe with a 0.2y nucleopore filter. The syringe needle passes through the sample cell lid so that the cell interior is not exposed to atmospheric dust. The sample is left in a variable temperature bath, and both the bath and the sample are subject to constant stirring. The bath temperature is heated using the SOFICA's heater and cooled by the addition of ice (heating rate = l°C/minute); the temperature of the sample is determined by the temperature of the bath. The light scattering (90° angle) intensity of the sample is then determined at various temperatures, using a green filter and no polarizer in the SOFICA. -10- 2 1 ^ — *L J In the present invention, cloud point measurements j are made for both solutions of the nonionic (at 1% by ] l | weight) in distilled water and in water containing 10% NaCl, although the latter generally far exceeds the amount of salts and electrolytes actually experienced in normal usage. Therefore, if the nonionic cloud point measured in 10% NaCl solution satisfies the cloud point requirement of this invention, then there will be no problem in formulating compositions containing very high concentrations of builder salts and other electrolytes, for example, up to about 85% of the composition. In this regard, it is known that the cloud point temperature for a given composition in the wash solution depends upon the physical and chemical properties (such as CMC and solubility) of the cationic, nonionic and additional components included in that composition, and may be lowered by increasing the alkyl chain lengths of the nonionic surface-active compound, by decreasing the degree of ethoxylation of the nonionic component, or by adding electrolytes, such as phosphates, polyphosphates, perborates, carbonates, sulfates, etc., particularly in relatively low amounts (such as from about 1 to about 15% of a given composition). Because water insoluble cationic softening compounds are used in this invention the cationics will have substantially no effect whatsoever on the cloud point of the total composition. Actually, because the softening cationic compounds used in this invention are water insoluble the cloud point temperature of the total formulation is very difficult to measure since the mixtures are naturally somewhat cloudy. Therefore, the cloud point of the nonionic, -11- with or without addition of electrolytes, is determined in the absence of the cationic compound, and this provides a sufficiently accurate measure of the cloud point of the total composition including the cationic. For washing temperatures of from about 60 to 70°C, all of the nonionic surfactants described above, especially those of formulae I and II, will provide cloud points in excess of the washing temperature. However, for higher washing temperatures of 71°C to 100°C, especially 80° to 100°C, it is necessary to use the more highly ethoxylated surfactants, for example 25 to 30 moles ethylene oxide per mole of hydrophobe. For these more highly elevated washing temperatures the most preferred nonionic surfactants are the C8-C9 alkyl phenols ethoxylated with from 25 to 30 moles, especially from 28 to 30 moles, and especially preferably about 30 moles, ethylene oxide. Alternatively, and as discussed in greater detail below it has also now been discovered that for any of the nonionics the cloud point can be raised by as much as about 40°C, generally about 5 to 20°C by adding to the composition an amphoteric surface-active compound, for example, a carboxyethylated higher fatty alkyl (e.g. coco) imidazoline amphoteric compound, generally in an amount of from about 0.5 to 307o, preferably 1 to 20%, especially preferably from about 1 to 10%, by weight of the composition. Therefore, in a preferred embodiment of the invention which is especially useful for washing soiled fabrics in an aqueous wash water at an elevated temperature in the range of from about 80°C to 100°C, the detergent -12- (Composition includes in addition to the nonionic surfactant j of formula I or formula II and the water insoluble quaternary j ammonium compound of formula III or formula IV an amphoteric point of the composition to above the elevated temperature of 80°C to 100°C. The second essential ingredient in the instant formulations is the cationic fabric softener. Generally, the cationic fabric softeners consist of at least one hydrophilic functional group bearing a negative charge and a hydrophobic group containing a quaternary ammonium atom which is positively charged. treated fabrics, it is essential that the cationic compound is water-insoluble. As used herein, a compound is considered water insoluble if its solubility in water at the washing temperature is less than about 1%, preferably less than about 1/2%. compound be included in the composition in a form to ensure a high dispersibility in the wash liquid and therefore maximum attachment to the treated fabric. Such dispersed particle sizes in the wash liquid range from about <10 to about 50 microns, preferably from about <10 to about 20 microns can be used for the cationic softening compound to achieve this effect. compound fabric softeners which are commercially known may be represented by the following formula: surfactant in an amount sufficient to raise the cloud In order to impart sufficient softness to the It is generally desired that the cationic softening Suitable water insoluble quaternary ammonium + X (III) -13- *>: /<-■, !. . .5 + *5 ^N] X (iv) N-l wherein Rj and R2 and R5 and Rg are each, independently, a long chain aliphatic radical having from 16 to 22 carbon atoms, r3 and r4 and r7 are, independently, lower alkyl radicals, or Rg may be the group -RgNHCRg wherein Rg 0 is a long chain aliphatic radical having from 16 to 22 carbon atoms, and R9 is a divalent alkyl group of 1 to 3 carbon atoms, and X is a water soluble salt forming anion such as a halide, i.e. chloride, bromide, iodide; a sulfate, acetate, hydroxide, methosulfate, ethosulfate, or similar inorganic or organic solubilizing mono- or dibasic radical. The carbon chain of the aliphatic radical containing 16 to 22 carbon atoms, especially 16 to 20 carbon atoms, may be straight or branched, and saturated or unsaturated. The lower alkyl radicals have from 1 to 4 carbon atoms and may contain a hydroxy radical. Preferably, the carbon chains are obtained from long chain fatty acids such as those derived from tallow and soybean oil. The terms "disoya," and "di-tallow," etc., as used herein refer to the source from which the long chain fatty alkyl chains are derived. Mixtures of the above, as well as other water insoluble quaternary ammonium surface active agents may also be used if desired. The preferred ammonium salt is a dialkyl dimethyl ammonium chloride wherein the alkyl group is derived from hydrogenated tallow or stearic acid, or a dihigheralkyl imidazolinium chloride. Specific examples of quaternary ammonium softening agents of the formula III suitable for use in the composition r -14- . of the present invention include the following: hydrogenated ditallow dimethyl ammonium chloride, dimethyl distearyl ; ammonium chloride, dimethyl stearyl cetyl ammonium bromide, | dimethyl dicetyl ammonium chloride, di-soya dimethyl :j ammonium chloride, the corresponding sulfate, methosulfate, li i ethosulfate, bromide and hydroxide salts thereof, etc. ■ Examples of quaternary ammonium softening agents ! j of formula IV include 1-methyl-l,2-diheptadecyl imidazolinium | chloride (bromide, methosulfate), 1,2-dieicosylalkylamidoethyl- 1-methyl imidazolinium chloride (bromide, methosulfate, ! etc), 2-hexadecyl-l-methyl-l[(2dodecoyl amido)ethyl] imidazolinium methylsulfate, 2-heptadecyl-l-methyl-l[2-stearoyl amido)ethyl] imidazolinium methylsulfate, 2-nonadecyl/heneicosyl-1-[(2-eicosoyi/docosoyl imido)ethyl] imidazolinium methyl chloride. Dimethyldistearyl ammonium chloride is especially preferred in view of its superior softening performance, biodegradability, low water solubility, availability and cost. The amount of the cationic fabric softener can generally range from about 1 to about 207=,, preferably from about 4 to about 1670, and especially preferably from about 6 to 97o, by weight of the composition. The weight ratio of the nonionic surface active agent to the cationic fabric softener will be within the range of from about 1:1 to 5:1, preferably from about 1.5:1 to 4.5:1. The detergent compositions of this invention are preferably provided as free flowing powders but may also be in liquid form. The invention detergent composition may also and generally does include water soluble builder salts. Water-soluble inorganic alkaline builder salts which -15- can be used alone with the detergent compound or in admixture with other builders are alkali metal carbonates, borates, phosphates, polyphophates, bicarbonates and silicates. (Ammonium or substituted ammonium salts can also be used.) Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, potassium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, sodium hexamethaphosphate, sodium ses-quicarbonate, sodium mono and diorthophosphate, and potassium bicarbonate. The alkali metal silicates are useful builder salts which also function to make the composition anti-corrosive to washing machine parts. Sodium silicates of Na20/Si02 ratios of from 1.6/1 to 1/3.2 especially about 1/2 to 1/2.8 are preferred. Potassium silicates of the same ratios can also be used. Another class of builders useful herein are the water-insoluble aluminosilicates, both of the crystalline and amorphous type. Various crystalline zeolites (i.e. aluminosilicates) are described in British Patent 1,504,168, U.S. patent 4,409,136 and Canadian Patents 1,072,835 and 1,087,477, all of which are hereby incorporated by reference for such descriptions. An example of amorphous zeolites useful herein can be found in Belgium Patent 835,351 and this patent too is incorporated herein by reference. The zeolites generally have the formula: (M20)x-(Al203)y-(Si02)z-WH20 wherein x is 1, y is from 0.8 to 1.2 and preferably 1, z is from 1.5 to 3.5 or higher and preferably 2 to 3 and w is from 0 to 9, preferably 2.5 to 6 and M is preferably sodium. A typical zeolite is type A or similar structure, with type 4A particularly preferred. The preferred aluminosilicates have calcium ion exchange capacities of about 200 milliequivalents per gram or greater, e.g. 400. -16- j! Other materials such as clays particularly of !j the water-insoluble types may be useful adjuncts in compositions of this invention. Particularly useful is bentonite. I This material is primarily montmorillonite which is a ■ i i| j hydrated aluminum silicate in which about l/6th of the i aluminum atoms may be replaced by magnesium atoms and with which varying amounts of hydrogen, sodium, potassium, calcium, etc., may be loosely combined. The bentonite in its more purified form (i.e. free from any grit, sand, etc.) suitable for detergents invariably contains at least 507e montmorillonite and thus its cation exchange capacity is at least about 50 to 75 meq. per 100 g. of bentonite. Particularly preferred bentonite are the Wyoming or Western U.S. bentonites which have been sold as Thixo-jels 1, 2, 3 and 4 by Georgia Kaolin Co. These bentonites are known to soften textiles as described in British Patent 401,413 to Marriott and British Patent 461,221 to Marriott and Dugan. Examples of organic alkaline sequestrant builder salts which can be used alone with the detergent or in admixture with other organic and inorganic builders are alkali metal, ammonium or substituted ammonium, amino-polycarboxylates, e.g. sodium and potassium ethylene diaminetetraacetate, sodium and potassium nitrilotriacetates and triethanolammonium N-(2-hydroxyethyl)-nitrilodiacetates. Mixed salts of these polycarboxylates are also suitable. Other suitable builders of the organic type include carboxymethylsuccinates, tartronates and glycollates. Of special value are the polyactal carboxylates. The Polyacetal carboxylates and their use in detergent compositions are described in U.S. Patents 4,144,226; 4,315,092 and 4 , 146,495. -17- ii'T. > 5 - V\A vO CO j Other U.S. patents on similar builders include 4 , 1 4 1 , 6-7.& ^ ,C j 4,169,934; 4,201,858;- 4,204,852; 4,224,420; 4,225,685; | 4,226,960; 4,233,422; 4,233,423; 4,302,564 and 4,303,777. i j Also relevant are European Patent Application Nos. 0015024; 0021491 and 0063399. Various other detergent additives or adjuvants may be present in the detergent product to give it additional desired properties, either of functional or aesthetic nature. Thus, there may be included in the formulation, minor amounts of soil suspending or anti-redeposition agents, e.g. polyvinyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxy-propyl methyl cellulose; optical brighteners, e.g. cotton, amine and polyester brighteners, for example, stilbene, triazole and benzidine sulfone compositions, expecially, sulfonated substituted triazinyl stilbene, sulfonated naphthotriazole stilbene, benzidine sulfone, etc., most preferred are stilbene and triazole combinations. Bluing agents such as ultramarine blue; enzymes, preferably proteolytic enzymes, such as subtilisin, bromelin, papain, trypsin and pepsin, as well as amylase type enzymes; bactericides, e.g. tetrachlorosalicylanilide, hexachlorophene; fungicides; dyes; pigments (water dispersible); preservatives; ultraviolet absorbers; anti-yellowing agents, such as sodium carboxymethyl cellulose, complex of Cj2 to ^22 alkyl alcohol with C^2 to ^18 alkylsulfate; pH modifiers and pH buffers; color safe bleaches, perfume, and anti-foam agents or suds-suppressors, e.g. silicon compounds. The bleaching agents are classified broadly, for convenience, as chlorine bleaches and oxygen bleaches. Chloride bleaches are typified by sodium hypochlorite (NaOCl), potassium dichloroisocyanurate (59% available ■18- 'V i ■3. 53 CO co chlorine), and trichloroisocyanuric acid (857= available chlorine). Oxygen bleaches are represented by sodium and potassium perborates and potassium monopersulfate. The oxygen bleaches are preferred. Bleach stabilizers and/or activators, such as, for example, tetraacetyl-ethylene diamine, can also be included. The proportions of components which may be present in the preferred total care compositions, in percent by weight (of actives) based on the total weight of the final product are as follows: nonionic detergent - about 57, to about 30%, preferably about 7% to about 207o, especially 14 to 167=.; quaternary ammonium salt - about 17. to about 20%, preferably about 4% to about 16%, especially preferably about 6 to 9%; alkali metal builder salts - about 20% to about 85% and preferably about 357» to about 80%, and especially preferably about 60 to 75%, the balance being detergent additives, fillers and moisture. Suitable ranges of the detergent additives are: enzymes - 0 to 2%, especially 0.7 to 1.3%; corrosion inhibitors - about 0 to 407o, and preferably 5 to 30%; anti-foam agents and suds-suppressors - 0 to 157., preferably 0 to 57», for example 0.1 to 3%; soil suspending or anti-redeposition agents and anti-yellowing agents - 0 to 10%., preferably 0.5 to 5%; colorants, perfumes, brighteners and bluing agents total weight 07. to about 2%. and preferably 0% to about 1%; pH modifiers and pH buffers - 0 to 57., preferably 0 to 2%; bleaching agent - 0% to about 40% and preferably 0% to about 257., for example 2 to 20%.; bleach stabilizers and bleach activators 0 to about 15%,, preferably 0 to 10%,, for example, 0.1 to 8%. In the selections of the adjuvants, they will be chosen to be compatible with the main constituents of the detergent composition. -19- While the high cloud point nonionics are preferably the sole surface-active detergent compounds used in the ^ compositions of this invention, small amounts of other surface-active compounds, including other nonionics, anionics can also be used, preferably in amounts up to 20% by weight, especially up to 10% by weight, and especially preferably up to 5% by weight. Examples of other nonionics include all those mentioned above but which have less than 15 moles alkylene oxide per mole of hydrophobe, for example 5 to 12 moles ethylene oxide per mole of hydrophobe. Examples of suitable anionic detergents include the water-soluble salts, e.g. the sodium, potassium, ammonium alkylolammonium salts of higher fatty acids containing about 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms. Suitable fatty acids can be obtained from oils and waxes of animal or vegetable origin, e.g. tallow, grease, coconut oil, tall oil and mixtures thereof. Particularly useful are the sodium and potassium salts of the fatty acid mixtures derived from coconut oil and tallow, e.g. sodium coconut soap and potassium tallow soap. The anionic class of detergents also includes the water-soluble sulfated and sulfonated synthetic detergents having an alkyl radical of 8 to 26, and preferably about 12 to 22 carbon atoms, in their molecular structure. (The term alkyl includes the alkyl portion of the higher acyl radicals.) Examples of the sulfonated anionic detergents are the higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates containing from 10 to 16 carbon atoms in the higher alkyl group -20- ; > O in a straight or branched chain, e.g., the sodium, potassium and ammonium salts of higher alkyl benzene sulfonates, - higher alkyl toluene sulfonates, higher alkyl phenol sulfonates, and higher naphthalene sulfonate. A preferred sulfonate is linear alkyl benzene sulfonate having a high content of 3- (or higher) phenyl isomers and a corresponding low content (well below 507°) of 2- (or lower) phenyl isomers, i.e., wherein the benzene ring is preferably attached in large part at the 3 or higher (e.g. 4, 5, 6 or 7) position of the alkyl group and the content of isomers in which the benzene ring is attached at the 2 or 1 position is correspondingly low. Particularly preferred materials are set forth in U.S. Patent 3,320,174. sulfonates, including long-chain alkene sulfonates, long-chain hydroxyalkane sulfonates or mixtures of alkene-sulfonates and hydroxyalkane-sulfonates. These olefin sulfonate detergents may be prepared in a known manner by the reaction of SOj with long-chain olefins containing 8 to 25, preferably 12-21, carbon atoms and having the formula RCH-CHRj where R is a higher alkyl group of 6 to 23 carbons and Rj is an alkyl group of 1 to 17 carbons or hydrogen to form a mixture of sultones and alkene-sulfonic acids which is then treated to convert the sultones to sulfonates. Other examples of sulfate or sulfonate detergents are paraffin sulfonates containing about 10-20, preferably about 15-20 carbon atoms, e.g. the primary paraffin sulfonates made by reacting long-chain alpha olefins and bisulfites and paraffin sulfonates having the sulfonate groups distributed along the paraffin chain as shown in U.S. Patents 2,503,280; 2,507,088; 3,260,741; 3,372,188; sodium and potassium sulfates of higher alcohols containing 8 to 18 carbon atoms, such as sodium lauryl sulfate and Other suitable anionic detergents are the olefin -21- 7 f ^ ^' sodium tallow alcohol sulfate; sodium and potassimh salts of an alpha-sulfofatty acid esters containing about 10 j to 20 carbon atoms in the acyl group, e.g. methyl alpha-i sulfomyristate and methyl-alpha-sulfo-tallowate, ammonium I j' sulfates of mono- or diglycerides of higher (Cio-c18) !j fatty acids, e.g. stearic monoglyceride monosulfate; sodium and alkylolammonium salts of alkyl polyethenoxy ether sulfates produced by condensing 1 to 5 moles of ethylene oxide with one mole of higher (Cg-C^g) alcohol; sodium higher alkyl (CiQ-Cig) glyceryl ether sulfonates; and sodium or potassium alkyl phenol polyethenoxy ether sulfates with about 1 to 6 oxyethylene groups per molecule and in which the alkyl radicals contain about 8 to about 12 carbon atoms. The suitable anionic detergents include also the Cg-Cig acyl sarcosinates (e.g. sodium lauroyl sarcosinate), sodium and potassium salts of the reaction product of higher fatty acids containing 8 to 18 carbon atoms in the molecule esterified with isethionic acid, and sodium and potassium salts of the Cg-C^g acyl N-methyl taurides, e.g. sodium cocoyl methyl taurate and potassium stearoyl methyl taurate. The amphoteric surfactants are commercially known and include derivatives of aliphatic amines which contain a long chain of about 8 to 20 carbon atoms and an anionic water-solubilizing group such as carboxy, sulfo, sulfato and the like. Among these are the N-long chain alkyl aminocarboxylic acids, e.g. of the formula R2 R-N -Rl-COOM; the N-long chain alkyl iminodicarboxylic acids (e.g. of the formula RN(RlC00M)2), where R is a long chain alkyl -22- 2 \ - ' . !| group, Rl is a divalent radical joining the amino and I carboxyl portions of an amino acid (e.g. an alkylene ! | radical or 1-4 carbon atoms), M is hydrogen or a salt >j forming metal, is a hydrogen or another monovalent i; ; substituent (e.g. methyl or other lower alkyl). Examples ji ! of specific detergents are N-alkyl-beta-aminopropionic I i ' acid; N-alkyl-beta-iminodipropionic acid and N-alkyl, I | N-N-dimethyl glycine; the alkyl group may be, for example, i j derived from coco fatty alcohol, lauryl alcohol, myristyl i alcohol (or lauryl-myristyl mixture), hydrogenated tallow j alcohol, cetyl, stearyl or blends of such alcohols. The substituted amino propionic and iminodipropionic acids are often supplied in the sodium or other salt forms which may likewise be used in the practice of this invention. Specific amphoterics are sodium-3-dodecylaminopropionate and sodium-3-dodecylaminopropanesulfonate. The present inventors have also discovered that the amphoteric surfactants when included in the formulation with the nonionic surfactant and the water insoluble cationic softening agent serve to raise the cloud point by as much as about 5 to 40°C, depending on the nonionic, amphoteric and on the ratio of the two surfactants. Accordingly, especially where the detergent composition is intended for use with wash water at higher elevated temperatures, for example at wash water temperatures of 80°C to 100°C, the addition of an amphoteric surfactant is often preferred, and in some cases, for example, at especially high loading of electrolytes, may even be necessary to maintain a cloud point in excess of the washing temperature. It has further been discovered that the nonionic/ amphoteric surfactant mixture has unexpectedly improved cleaning performance as compared to an equal weight of the nonionic alone. For example, using carboxyethylated -23- j higher fatty alkyl imidazoline as the amphoteric about ! 50 to 90% of the nonionic can be replaced with only about :! j 10 to 40% of the amphoteric to achieve the same or superior I softening (depending on washing temperature) and the same or superior cleaning performance. The amount of amphoteric detergent may vary widely depending on the specific nature and intended use of the formulation, as well as on the nature and amounts of the other particular ingredients, especially the nonionic surfactant. Generally, however, from about 0.5-30%, preferably 2-20% by weight of the total formulation may be used. Furthermore, as noted above, since the amphoteric can act synergistically with the nonionic with respect to cleaning performance the total amount of nonionic and amphoteric in the detergent formula can be greatly reduced, for example, 1 to 20%, especially 5 to 10% of the composition. The ratio of nonionic to amphoteric is not particularly critical but for a given weight of nonionic the cloud point will increase as the amount of the amphoteric increases. Generally, ratios of nonionic to amphoteric of from about 1:4 to 6:1, preferably 1:2 to 5:1, especially preferably 1:2 to 4:1, will provide improved cleaning performance, as well as softening performanc (where necessary to increase the cloud point of the nonionic to above the washing temperature). Furthermore, within the above amounts and ratios, the mixed nonionic/amphoteric surfactant mixture will be fully compatible with the cationic quaternary ammonium softening compound. In addition to the so-called active materials of these compositions other important constituents are filler salt(s) and moisture. A filler salt helps to improve the mechanical properties of the product, usually -24- improving the flow rate and countering any tendency toward tackiness. It may also aid in promoting ready solution I j of the product in wash water. Among useful filler salts ] i the best is sodium sulfate, preferably in the anhydrous state. However, other fillers, including sodium chloride, sodium acetate, and the alkali metal salts of such acids, may also be used, as may be starches, talcs, silicas and various other fillers which perform a carrying or supporting function. The proportion of filler or mixture thereof will be within the 5 to 507» range, preferably being 10 to 307. and most preferably about 207o, especially when sodium sulfate, anhydrous, is the filler salt. The percentages of moisture will normally be from 1 to 157„, preferably 5 to 127o and most preferably about 87o. When such proportions are used a satisfactorily flowing particulate, pulverulent or granular product results, which, by control of particulate size and moisture content, can be prevented from being excessively dusty. Whatever the form of the laundry detergent, its use in the washing process is essentially the same. The particulate composition is usually added to wash water in an automatic washing machine so that the concentration thereof in the wash water may range from about 0.05 to 1.57=, usually 0.1 to 1.270. The water to which it is added will preferably be of medium or low hardness, e.g. from 30 to 120 parts per million of hardness, as calcium carbonate, but both softer and harder waters may be usefully employed. The water temperature can be from 20°C to 100°C and is preferably from 60° to 100°C in those cases where the textile or laundry is capable of withstanding high temperatures without deterioration or fading of dyes. When low temperature laundering is desired, the temperature may be held at 20° to 40°C, under which conditions ; good cleaning and softening are the result, although I the product may not be as clean as when washed at the i j higher temperatures. At the concentrations of detergent j 'j compositions mentioned the pH of the wash water will ; i j usually be from 7 to 11, preferably from 8 to 10. At l ! such pH's the composition is effective as a detergent, j not unduly harsh to the material being washed nor to ! human skin and effectively cleans and softens. The laundry:wash water weight ratio will usually be about 1:4 to 1:30 | or 1:10 to 1:30. The compositions of the present invention provide significantly improved softening performance, at washing temperatures of at least 60°C, as compared, for example, to identical formulations, except that the nonionic has a cloud point below 60°C, for example a straight chain higher fatty, e.g. C12-C15, alcohol with 7 to 13 ethylene oxide units. This effect could not have been predicted from the prior art since there was no known correlation between the nonionic surfactant cloud point and softening performance. Cloud point values (°C) for various nonionic surfactants at 1% by weight concentrations were measured in distilled water and in 10% NaCl. Nonionic Surfactant C12-C15 fatty alcohol EO 7:1 C12-C15 fatty alcohol EO 11:1 Cl2~Cl5 fatty alcohol EO 15:1 isoctylphenol EO 30:1 nonyl phenol EO 20:1 nonyl phenol EO 15:1 nonyl phenol EO 8:1 Distilled Water 107. NaCl 43±2 <25 85±2 59±2 >100 >60 >100 >60 >100 72 91 70 45 >30 -26- A typical formulation of a powdery detergent-softener composition according to the invention is given below, all parts and percents being on a weight basis: Composition A isooctylphenol E0 30:1 (70% AI) 21 .6 sodium metasilicate 8 .0 sodium tripolyphosphate 28 .0 sodium pyrophosphate-10 H20 24 .0 sodium orthophosphate 0 .5 nitrilotriacetate (NTA) 8 .0 dimethyl distearylammonium chloride (93% AI) 8 .0 minors and miscellaneous (e.g. perfume, optical brighteners, moisture, etc) Balance Soiled fabrics are washed at 60°C in about 20 liters of water containing 7 grains hardness ions per gallon using about 100 grams of the Composition A. The washed fabrics are evaluated for softness by a panel of 4 expert judges on multiple replicates after cumulative washing. For comparison, the identical composition is prepared except that in place of isooctylphenol EO 30:1 in Composition A an equal amount of isooctylphenol EO 8:1, Ci2~Ci5 fatty alcohol EO 11:1, or C12-C15 fatty alcohol EO 7:1 is used, and each of these composition are evaluated in the same way as Composition A. Each of the compositions are graded on a scale of 1 to 10 with "10" being the highest grading and representing the same detergent composition (without cationic softener) and a rinse cycle added softener (dimethyldistearyl ammonium chloride). On this scale Composition A achieved a rating of 5-6. Each of the comparative compositions received a rating of only 2-3. -27- </div>

Claims

<div class="application article clearfix printTableText" id="claims"> o When isooctylphenyl EO 30:1 is replaced by an ^ equal amount of nonyl phenol EO 15:1, nonyl phenol EO | 20:1 or Ci2"c15 fatty alcohol 20:1 a rating of 5-6 is i J also achieved. I Similarly good results are obtained by replacing dimethyl distearyl ammonium chloride with dimethyl hydrogenated ditallow ammonium chloride, diethyl disoya ammonium chloride, dimethyl stearyl cetyl ammonium chloride or 2-hexadecyl-l-methyl-1[2-dodecoyl amido)ethyl] imidazolinium methylsulfone, and the corresponding bromide, sulfate, and hydroxide salts, thereof. The methods for making the compositions described herein are generally well known in the art and in particular reference is made to U.S. Patent 4,269,722 of Joshi, wherein relatively high density, built non-ionic powders are produced from spray dried base beads which are over-sprayed with nonionic detergent (which may contain other minor conventional additives such as color, perfume, brightener, bleach, etc.). This entire patent disclosure is incorporated by reference. -28- WHAT WE CLAIM IS: |*

1. A laundry detergent composition capable of washing soiled fabrics in an aqueous wash liquid at an elevated washing temperature of at least substantially 60°C, said composition comprising a water-soluble nonionic surface-active agent having a cloud point above said elevated temperature, and a water insoluble cationic quaternary ammonium compound capable of imparting softening to the washed fabric, and being selected from the group consisting of compounds represented by the following formulae: N. r2" ■r4 x- (iii) and where in r5- N / \ R R (iv) Rl and R2 and R5 and Rg are each, independently, C^g to ^22 l°n8 chain aliphatic radical, r3 and R4 and r7 are each, independently, C^-Cg- alkyl radicals; or R5 may be the group -RgNHCRg wherein Rg is a long chain O aliphatic radical having from 16 to 22 carbon atoms, and r9 is a divalent alkyl radical of 1 to 3 carbon atoms, and X Is a salt forming anion; the ratio, by weight of the nonionic surface-active agent to the cationic compound being in the range of 1:1 to 5:1. 2d ?!. " ?/"■ —r ;;r s. !C l:. - 35 .•* CO • 00 6104

2. The composition of claim 1 wherein the nonionic surface-active agent is at least one compound selected from the group consisting of compounds represented by the following formula R0(CH2CH2O)nH (I) wherein R is a primary or secondary alkyl chain of from substantially 8 to 2 2 carbon atoms and n has an average value of 15 to 30; and R1-(O}-0- (CH2CH20)mH (ii) wherein R* is a primary or secondary alkyl chain of 4 to 12 carbon atoms, and m has an average value of 15 to 30.

3. The composition of claim 2 wherein R is an alkyl of from 12 to 15 carbon atoms and R* is an alkyl of from 8 to 9 carbon atoms.

4. The composition of claim 3 wherein the cationic compound is dimethyl distearyl ammonium chloride.

5. The composition of claim 1 wherein the cationic compound is dimethyl distearyl ammonium chloride.

6. The composition of claim 1 which further comprises at least one detergent additive selected from the group consisting of inorganic detergent builder salts, organic detergent builder salts, soil suspending agents, anti-redeposition agents, fatty amides, suds-suppressor agents, anti-foaming agents, optical brighteners, dyes, pigments, bluing agents, anti-yellowing agents, enzymes, corrosion inhibitors, pH modifiers, pH buffers, bactericides, fungicides, preservatives, bleaching agents, bleach stabilizers 30 11 MAR *988 1 -vl ^ ^.o C bleach activators, perfumes, ai

7. The composition of claim 1 weight basis (a) from substantially surface-active agent; (b) from substantially cationic softening agent; (c) from substantially detergent builder salts; (d) 0 to substantially (e) 0 to substantially activators, (f) 0 to substantially anti-redeposition agents; (g) 0 to substantially (h) 0 to substantially optical brighteners, colorants fungicides, and enzymes; (i) 0 to substantially and pH buffers; (k) balance water.

8. The composition of claim 4 weight basis, (a) from substantially surface active agent; (b) from substantially compound; (c) from substantially selected d water. which comprises, on an active 5 to 30% of the nonionic 1 to substantially 20% of the 20 to substantially 85% 40% of corrosion inhibitors; 4 0% of bleaching agents and 10% of soil suspending or 10% anti-yellowing agents; 2% of each of at least one of bluing agents, bactericides, 15% of each of pH modifiers which comprises, on an active 7 to 20% of said nonionic 4 to 16% of said cationic 35 to 80% of builder salts ^ from the group consisting of the alkali metal phosphates, i polyphosphates, nitrilotriacetate, and silicates and ! mixtures thereof, and | (c«) the balance detergent additives, fillers and moisture.

9. The composition of claim 8 which comprises: (a) substantially 14 to 16%; (b) substantially 6 to 9%; (c) -substantially 60 to 75%? and (d) " balance; wherein (c) is comprised predominantly of sodium tripolyphosphate and sodium orthophosphate.

10. A method for cleaning and softening soiled fabrics in an aqueous wash water at a temperature of at least substantially 60°C which comprises washing the fabrics in an aqueous solution of the composition of claim 1.

11. The method of claim 10 wherein the wash water temperature is substantially 100UC and wherein the nonionic surface-active agent is a Cg-Cg alkyl phenol condensed with from substantially 25 to 30 moles ethylene oxide.

12. A detergent composition for washing soiled fabrics in an aqueous wash liquid at an elevated temperature in the range of 80° to 100°C, said composition comprising (a) at least one water-soluble nonionic surface active compound of formula I or II RO(CH2CH20)nH (I) R10-{o3-(CH2CH20)mH (II) where R is a primary or secondary alkyl chain of from 1 ' substantially 8 to 22 carbon atoms, R is a primary or secondary alkyl chain of substantially 7 to 12 carbon atoms, and n and m are each, on the average a number of from 15 to 30; (b) at least one water-insoluble cationic quaternary ammonium compound of formulae III or IV: Ri. r2- r5. N .r3 *ra N-j N-l (HI) R7 (IV) wherein Rj and R2 and r5 and Rg are each, independently, C^g to C22 long chain aliphatic radicals. R3 and R4 and R7 are each, independently, <^-Cg alkyl radicals, or Rg may be the group -RgNHCRg wherein is a long O, chain aliphatic radical of 16 to 22 carbon atoms, and Rg is a divalent alkyl radical of 1 to 3 carbon atoms, and X is a salt-forming anion; and (c) at least one amphoteric surfactant in an amount such that the composition has a cloud point above the elevated temperature. per: WEST-WALKER, McCAEE ATTORNEYS FOR THE APPLICANT / * ".<CN . 0 '4 . 11 MAR 1988 33 </div>