CA1059865A - Detergent compositions - Google Patents

Abstract

DETERGENT COMPOSITIONS
Abstract of the Disclosure Compositions utilizing linear primary alcohol ethoxylates having narrowly defined ranges of ethoxylation, alkyl chain length and HLB are disclosed for enhanced oil and grease stain removal from fabrics. The ethoxylates can be employed either alone or in combination with anionic or zwitterionic surfactants in granular or liquid detergent formulations.

Description

~ S~ 8 ~3 Background of the Invention This invention relates to compositions and processes for solubilizing and/or emulsifying oryanic hydrophobic soils - such as hydrocarbon oils, complex fats such as triolein and - other long-chain unsaturated and saturated glycerides, and body soils (lipid plus particulate).
More particulaxly the invention concerns the use of narrowly defined linear primary alcohol ethoxylates having a hydrophilic-lipophilic balance in the range 9.5-11.5 to remove such soils from fabrics Current laundry products and procedures exhibit deficiencies of one kind or another when used to clean oily stains, particuarly hydrocarbon stains, from fabrics, whilst f triglyceride and body soils are also difficult to remove.
.~ These deficiencies are particularly evident when a~ueous laundering processes are used to clean fabrics which are partially or wholly synthetic in nature such as polyester, polyamide and acrylic-fibre based materials.
The oil removal problem is so acute that Smith ,~
20 et al, Textile Chemicals Col. 5 #138 (1973) have concluded that a detergent formulation alone is very.unlikely to solve -the problem of effecting satisfactory release of any broad .. :~
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-1~ spectrum of oils from today's durable press fabrics unless ~.
the fabrics are specially treated with hydrophilic materials. :
Traditionally oil removal from fabrics has largely - : :
been accomplished by means of dry-cleaning procedures either by hand application for individual soil stains or by machine treatment of entire articles. Such procedures involve the . use of solvent-based formulations and have varying effective-'~ 30 ness depending on the nature of the stain, the type of fabric and the cleaning formulation used. However, dry-cleaning _ 2 --;:
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,~' ' ~ , ~sg8~is processes tend to be inconvenient and in most cases impracticable for domestic use, besides being relatively expensive~ Accordingly, compositions and processes which would provide the economical and efficient removal of oily -- soils and stains from fabrics, by means of conventional household laundry equipment, are desirable.
The present invention utilizes lin~ar or predomin-antly linear primary alcohol ethoxylates of carefully defined chain length, ethylene oxide content and distribution that have a hydrophilic-lipophilic balance (~LB) in a particular range to remove oily and fatty material from fabrics in an aqueous laundering process.
The ethoxylation of organic materials having a reactive hydrogen atom, such as primary alcohols, to product ethoxylates with surface~active properties is well known, being described in U.SO Patent 1,970,578, and the use of such materials as cleansing agents has been disclosed in many other patents, e.g., U.S. Patents 2,133,480 and 2,164,431 The disclosures of U.S. Pat:ent 1,970,578 teach the condensation products of aliphatic monohydric alcohols containing from 6-18 carbon atoms with at least 4 moles of ethylene oxide are useful surfactants and textile treating agents. U.S. Patents 2,133,480 and 2,164,431 disclose that primary aliphatic alcohols containing from 8 to 18 carbon atoms ethoxylated with from 1 to 3 moles of ethylene oxide ; are useful in combination with various anionic surfactants in washing operations and for emulsifying oils.
U.S. Patent 3,008,905 teaches that the products produced by the addition of from 1 to about 4 moles of an 30 alkylene oxide with alcohols containing, at most, 12 carbon -- atoms are suitable for use in detergent compositions.

- 3 _ , ~59~ 5 u.S~ Patent 3,342,739 broadly describes the use of nonionic surfactants comprising from about 3 to about 10 m~les of ethylene oxide per mole of C10-C20 aliphatic primary alcohol in combination with an ethoxylated C10-Cl4 fatty acid alkanolamide and a C10-Cl4 fatty acid, such compositions being useful as hard surface cleaning agents.
U.S. Patent 3,619,119 discloses compositions for the treatment of oil and fat spots on textiles which composi-tions comprise a mixture of two different primary alcohol ethoxylates, an alkyl polyethylene oxide sulfate and an aqueous hydrotrope. The alcohol ethoxylate mixture comprises a ~;~
C16-C18 alcohol condensed with 8 to 20 moles of ethylene oxide ; and a C14-Cl~ alcohol condensed with 1 to 5 moles of ethylene ; `~
oxide. ;
U.S. Patent 3,682~849 teaches the production, for surfactant use, of primary aliphatic Cll-C15 alcohol ethoxy-lates, in which the alcohol precursor contains up to 40~ of

2 alkyl branching. EthoxyIation is carried out to give a ~ ~ -mean of 4.5-9 moles of ethylene oxide per mole of alcohol 2Q and the mixture is then stripped to remove lower ethoxylates i~
and to raise the mean level to a value in the range 7-11 , moles ethylene oxide per mole of alcohol.
; Canadian Patent 860,898 describes the formulation of detergent compositions containing anionic or nonionic surfactants to which ethoxylated aliphatic C8-C15 alcohols containing 10-Sl~ by weight of ethylene oxide are added as detergency improvers.
Belgian Patent No 806,712 issued April 30, 1974, teaches the use, in laundering compositions, of condensation products of C10 15 fatty alochols with 3-10 moles of ethylene oxide, these condensates having an HLB of from about 10 to about 13.5, together with various anionic surfactants.

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U.S. Paterlt 3,983,078 issued September 29, 1976 teaches the combination of long chain and short chain water-soluble nonionic surfactants, each having different and defined HLB
ranges, to give a blend having a defined HLB range, the combination providing enhanced oily soil solubilization properties.
Additionally, copending Canadian ApplicationiNo.
211,261 filed October 11, 1974 and Belgian Patent No. 817,267 issued January 6, 1975, disclose respectively granular and liquid laundry detergent compositions in which ethoxylated aliphatic alcohols are employed as major surfactant materials.
- However whilst the use of various alkoxylated nonionic surfactants, either alone or in mixtures, is ~-known in detergent compositions, the detergency arts have not hitherto recognized that the specific materials disclosed herein provide superior removal of oily and fatty soils - from fabrics.
For example Canadian Patent 860,898 discloses 2~ nonionic detergency improvers whose ethylene oxide content lies within a range that does not includ~ the optimum of the present application. Furthermore these detergency improvers can themselves be combined with other nonionic materials of non-critical structure that comprise the surfactant of the composition, such combinations being in-capable of providing the level of oil and greasè removal performance achieved by the materials disclosed herein.
U.S. Patent 3,682,849 in fact teaches that the detergent properties of certain mixtures of alkoxylated nonionic detergents are improved when short-chain, less highly _ alKoxylated materials are removed, such materials including ~.
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some which are valuable in the present invention. Addition-ally, an article in Soap and Chemical Specialties, November --1963, at pages 52-54 entitled "Syndets with Alcohol Derivatives" indicates clearly that the key parameters in the optimization of the detergency performance of ethoxylated C6-C18 alcohols are average ethylene oxide content and average alkyl chain length as represented by alcohol molecular weight. In fact it has hitherto been considered essential for commercial ethoxylates to contain a broad range of species ln order to provide the desired performance.
The sum total of the prior art references is that - various nonionic surfactants and mixtures thereof in combina-tion with other surfactants can be utilized in detergent compositions~ However the prior art nowhere recognizes the improvements in grease- and oil-removal performance that can ;~
be obtained by the formulation of nonionic materials having the combination of ethylene oxide content and distribution, alkyl chain length and distribution and HLB displayed by the ;~
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ethoxylated nonionics of the present invention.
Compositions in accordance with the present ` invention are characterized by their effectiveness in - removiny oil and grease stains f~om fabrics~ particularly polyester and polyester-cotton blends, in the relatively ` limited time available in the wash cycle of a domestic laundry operation. Moreover the compositions herein can be employed alone to cleanse materials in a special treatment step or can be used as additives in conjunction with other laundry detergent products or can be formulated with other detergent ingredients to provide commercial laundry detergent composi-tions having enhanced oil and grease removal properties.
The compositions herein are useful for cleaning ,............................................................... .
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s and degreasing a variety oE surfaces other than textiles and are useful, for example, in the meta:L working trades and as hard surface cleaners for use on walls and floors.
Accordingly it is an object of the present invention ; to provide compositions for solubilizing oily soils and for removing such soils from surfaces.
A further object is to provide compositions for removing oily soils from fabrics in a domestic laundry ,operation.
An additional object of the invention is the provision of additive compositions which can be employed with commercial laundry detergents to enhance the oil removal efficacy thereof.
Summary ¢f the Invention In accordance with this invention a grease and oil--removing composition is provided that consists essentially of ~ ~
a base-catalyzed primary alcohol ethoxylate having the ~ -'' formula R - R - O(CH CH O) H
1 2 2 2 naV

wherein Rl i9 a linear alkyl residue and R2 has the formula :' ' CHR3CH2 ~, R3 being selected from the group consisting of hydrogen and ~' mixtures thereof with Cl-C4 alkyl groups, there being not ,', more than 70~ by weight of said alkyl groups in the mixtures, wherein R and R together form an alkyl residue having a ~ 1 2 ,' mean of 9 to 15 carbon atoms, at least 65~ by weight of said residue having a chain length within ~ 1 carbon atom of the mean, wherein 3.5 ~na~ <6.5, provided that the total ,~
~ amount by weight of ethoxylate components in which n = O

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shall be not greater than 5% ar-d the total ~mount by weight of components in which n = 2 to 7 lnclusive shall be not less than 63~, and wherein the hydrophilic-lipophilic balance (HLB) of the ethoxylate shall lie in the ranye 9.5-11.5, said composition being other~ise free of alkoxylated nonionic surfactants not meeting these specifications.
Preferred embodiments of this invention utilize blends of primary alcohols in which at least 90% and most preferably 95% by weight of the alcohol has a chain length within + 1 carbon atom of the mean, wherein the amount of unethoxylated alcohol is less than 1% by weight and wherein the amount of ethoxylated alcohols having 2 7 ethylene oxide groups is at least 70~ by weight. Preferably an ethoxylate having a mean o~ 12 or less carbon atoms in the alkyl group contains at least 55% by weight of material having 2-6 ethylene oxide groups while for an ethoxylate having a mean of 12-13 ;
carbon atoms in the alkyl group, at least 55% by weight -of the material has 3-7 ethylene oxide groups. An etho~ylate having a mean of 14-15 carbon atoms in the alkyl group preferably has at least 55~ by weight of E3-E8 material.
In the preferred embodiments of the invention the HLB of the ethoxylate is in the range 10.0-11.1.
The compositions herein can be employed as-is to remove grease- and oily-soils from surfaces by contacting the surfaces with an aqueous solution containing from about 0.005%
to about 0.50% by weight of said alcohol ethoxylates. This treatment may comprise the only cleansing step or may be followed or preceded by treatment with conventional commercial detergents. Alternatively the compositions of the invention may be incorporated in either built or unbuilt detergent _ compositions which may be granular or liquid in form.

~5~;5 Deta led Description of the Invent_ n The grease- and oily-soil removal compositions of the present invention comprise primary aliphatic alcohol ethoxy~
lates having a narrow range of ~ILB's together with narrowly defined ethylene oxide and alkyl chain length distributions.
The alcohol precursors of the ethoxylates of the invention are primary aliphatic alcohols of 9 to 15 carbon atoms having the formula Rl-R2-OEI wherein Rl is a linear alkyl residue and R2 has the formula CHR3-CH2-, R3 being selected from the group.consisting of hydrogen and lower alkyl, par-ticularly methyl, not more than 70% by weight of the alcohol being constituted by 2-alkyl branched material.
Examples of suitable primary aliphatic alcohols :
.
: are the linear primary alcohols obtained from the hydrogenation ~ of vegetable or animal oil fatty acids such as coconut, palm `~ kernel and tallow fatty acids, or by ethylene build-up reactions and subsequent hydrolysis of the terminal double bond using Ziegler type processes. Preferred alcohols are n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-myristyl, .;~ :
20 and n-capryl alcohols. : ~.
Suitable alcohol precursors also include primary ~ :
; alcohols having a proportion of branching on the ~ or 2- ;~
carbon atom, i.e. of formula ~ ~ `

CH3(CH2)n - fH - CH2H
(CH2)m ~ wherein m+n is in the range 6 to 13 and wherein m is O to 4.
;` In such alcohols at least 30% of the alcohol of . each specific chain length should be linear (i.e. m = O) and ; 3n the branching preferably comprises about 50~ oE methyl groups " .

~ ~ S~ ~35 with smaller amounts of ethyl propyl and butyl groups. These alcohols, or the aldehydes corresponding thereto are conven-iently produced by reaction o~ linear olefins haviny from 7 to 14 carbon atoms with carbon monoxide and hydrogen. The reaction can either be controlled to produce aldehydes (as in the well known Oxo process), which aldehydes are then hydro-genated to give alcohols, or can be carried out as a hydroformylation reaction in which the aldehydes are hydrogena-ted in situ to convert them to saturated Cg-Cl5 primary alcohols.
Both linear and branched chain alcohols are formed from these processes and the mixtures can either be used as such or can be separated into individual components and then recombined to ` give the desired blPnd.
Typical processes for producing "oxo" aldehydes which are then hydrogenated to alcohols are disclosed in U.S.
Patents 2,564,456 and 2,587,858 and the direct hydroformylation of olefins to give alcohols is disclosed in U.S. Patents -2,504,682 and 1,581,988.
It will be apparent that by using a single chain length olefin as starting material, a corresponding single chain alcohol will result, but it is generally more economic to utilize mixtures of olefins having a spread of carbon ~i chain length around the desired mean. This will of course provide a mixtu~e of alcohols having the same distribution ` of chain lengths around the mean.
Primary aliphatic alcohols derived from vegetable oils and fats and from other petroleum feedstocks having alkyl or alkylene groups as part of their structure will also contain a range of chain lengths. This range may extend over a range of C8-C20 and beyond and it is therefore normal practice to ~ separate the products from such feedstocks into different chain length ranges which are chosen with reference to their ~ 10 - ~' .

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ultimate use.
In such mixtures it is important for the purposesof the present invention that this distribution be as narrow as possible and therefore at least 65% and desirably 80% by weight of the alcohol mixture should be within ~ 1 carbon atoms of the mean chain length. Preferably at least 90%
and most preferably 95% should fall within 1 carbon atom of the mean chain length.
As mentioned previously, commercially available ;;
alcohol precursors normally comprise mixtures of alcohols, while materials suitable for the purposes of the present invention must have a narrow distribution of chain lengths around the given mean in order to minimize the range of HLB's produced upon ethoxylation. Commercially available primary alcohol blends satisfying this requirement include the alcohols marketed by Sheli International Chemicals Ltd. under the trade mar~. Dobanol and similar materials marketed under the trade mark Neodol by Shell Chemical Co., these alcohol blends having at least 95% by weight of the blend within the stated carbon chain length range. The Neodol/Dobanol materials are predominantly linear and have approximately 25~ 2-alkyl branching. Other suitable synthetic alcohols are marketed by Imperial Chemical Industries Ltd. under the trade name "Synperonic" and constitute primary alcohols having 51~ to 70% by weight of 2-alkyl branched material. Suitable alcohol blends derived from natural fats include the so-called "middle cut" fraction of coconut fatty alcohol composed of approximately 70% C12, 20~ C14 and 10~ C16 alcohol by weight-The ethoxylates useful in the present invention comprise ethylene oxide condensates of the alcohol precursors ~ defined above having a hydrophilic-lipophilic balance (HLB) .. ~ .
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~ sg8~6s in the range 9.5-11.5. Mvre particularly they comprise C9-C15 aliphatic primary alcohol ethylene oxide condensates in which the average numbex of moles of ethylene oxide per mole of alcohol lies within the range 3.5-6.5 and in which, or any given alkyl chain length, the total amount by weight of unreacted alcohol is less than 5g, preferably less than 2% and most preferably less than 1% and the amount by weight of ethoxylates haviny 2 to 7 moles ethylene oxide per mole of alcohol is greater than 63~, preferably greater than 70~.
Preferably also the HLB lies in the range of 10.0 to 11.1 and most preferably in the range 10.2 to 10.9.
Hydrophilic-lipophilic balance or HLB is a widely accepted measure of the polarity of a surfactant and of its relative affinity for aqueous or hydrocarbon media. Developed originally by W.C. Griffin (J. Soc. Cosmetic Chemists 1, 311, 1949) the concept permits numerical values to be gi~en to surfactant materials, the scale being such that hydrophilicity increases with increase in HLB value. For nonionic surfactants containing ethylene oxide the HLB va]ue can be expressed as HLB = E/5, where E is the percentage by weight of ethylene oxide in the compound.
It is generally held (see for example Nonionic Surfactants, edited`by Schick ~Marcel Dekker Inc. N.Y. 1967) pp. 606 608) that the HLB ranges for different surface~active functions are as follows:
' Water in oil emulsifier 3-6 - Wetting agent 7-9 Oil in water emulsi~ier 8~15 Detergent 13-15 - Soluhilize~ 15~18 ,, ' ~
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It should be noted that the range of HLB considered appropriate for detergency, viz. 13-lS, is noticeably different from that which has been found to be optimum in the present invention, namely (9.50-11 5). Furthermore an HLB above 12 has been considered necessary in order to raise the cloud point to a temperature above that at which aqueous solutions of the surfactant would normally be stored and, in some cases, used. The cloud point of a nonionic surfactant, conventionally measured at 0.5%, 1~ or 2~ wt.
concentration in water, i~ acknowledged to be an indication of its solubility and hence of its usefulness for detergent purposes. A low cloud point will give a low solubility rating under the conditions of the test, despite the fact that the nonionic surfactant may form an isotropic solution or a stable dispersion, both of which may be useful at the usage concentration. Consequently, the convention of the cloud point test and its relationship to surfactant solu-bility under the test conditions has tended to serve as a discouragement to the use of a material having an HLB in the 10-11 range as the sole or major surfactant component.
Whilst it is not intended to be bound by theory, it appears that, in order to achieve good oil and grease .; .
removal from a surface, the selected surfactant must be .
capable of ~apid transfer from the aqueous phase o~ the wash liquor into the hydrophobic phase of the grease or oil stain to give a low interfacial tension~ In order to achieve true solubilization of the soil, it is necessary that the surfactant give a zero interfacial tension at the water-hydrophobic soil interface, which in turn creates an 3Q unbalanced force tending to disperse the hydrophobic soil in the aqueous liquor, thereby removing the soil from thP ~ ;

surface.
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-Investigations of the interfacial tension reduction of surfactants intended for use in aqueous laundry processes have usually introduced the surfactant in the aqueous phase in order to match the conditions arising in actual practice.
Under these conditions the inter-phase transport of relatively oil-soluble nonionics of HLB 9.5-11.5 is very slow, sometimes taking days to weeks to establish equilibrium. In consequence true equilibrium values for interfacial tension of low HLB
nonionics have not been established.
However it has been found that incorporation of such surfactants into the hydrophobic phase prior to its introduction into the aqueous phase leads to a rapid approach ~-to equilibrium and hence true equilibrium interfacial tension values and therefore the Pendant Drop method of measuring interfacial tension ~i was adopted using the technique described by Andreas Hauser & Tucker in J. Phys. Chem. 42, 1001 (1938). In this method of interfacial tension measurement, a pendant droplet of one liquid is formed at the tip of a fine capillary tube mounted vertically in a bath of a second liquid immiscible with the first. The temperature of the bath is maintained at a constant value and the interfacial tension of the two liquids can be calculated from the droplet dimensions, which are recorded on an enlarged photograph to facilitate their measurement.

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Application of this techn:ique to a series of pure n-decyl and n~dodecyl polyoxylethylene glycol monoethers (pure CloExls and C12Ex's respectively) gave results which are summarized in Table I~ ~

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~5~8~i~5 TABIJE I

lTERFP~CIAL T~ISIONS BETI~EEN DODECANE/e~ATER
AS~
(Initial concentration of compound in Dodecane is 2~ unless stated otherwis~) ~i (hydrocarbon/water~ HLB
. 19~8 C~lOE2 lOol 7n2 Clo 3 2~5 9~1 ~10 4 0 ~D 15 10 ~ 5 ~ lOES 13 ~ 75 11~ 6 ClOE6 1~ 08 12 ~ 5 CloEg 3~75* 14~3 .

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1~5~5 It can be seen -that the minimum values of ~i occur at HLBs in the 10.2-10.9 range, the exact m.inimum being only slightly different for different oils. This corresponds to the following range of optimum values of mixtures of pure alkyl polyoxyethylene glycol monoe-thers.

9 3.4-3.9 13 4.7-5.4 10 3.7-4.3 14E5.1-5.8 11 4.1-4.7 C15E5.4-6.2 12E4.4-5.1 Above an alcohol chain length of approximately 15 carbon atoms, the very limited monomer solubility (very low cmc's) of these molecules has an adverse effect on the kinetics of the surfactant transfer between the hydrocarbon and aqueous phases. For this and other reasons to be explained hereinafter, the ethoxylates of alcohols having more than 15 carbon atoms in the chain are much less effective and do not form a part of the present invention.
On the basis of the reduction of interfacial tension (~i) it would be predicted that the grease and oily-soil removal performance of primary alcohol ethoxylates wouldbe at a ma~imum at the minimum value for ~i. Table II shows the soil removal results given by compositions containing the ethoxylates of Table I together with two commercially available products using three different hydrophobic soils on cloth swatches. The ethoxylate compositions were adjusted to provide 240 ppm surfactant and 85 ppm sodium silicate (SiO2:Na2O = 2.4:1) in solution. The soils were DMO (dirty - motor oil obtained from an automobile crankcase), OHT (a simulated soil comprising a 1:1:1 mixture by weight of ~ 18 -~C~5~1~6Si oleic acid, octadecane and triolein), and triolein.
The test procedure involved soiling 2" x 2-1/2"
polyester:cot-tvn blend cloth swatches with 0.01 ml. of a particular soil which was then aged for 3-6 hours before washing. The aging involved storage in covered containers at room temperature in a manner that avoided contact between the hydrophobic soil spot and any other surface. A mixture of soiled cloths was then placed in pots, each containing 1 litre of detergent solution so as to give a cloth:liquor ratio of 1:100 and a 10-minute wash in a Tergotometer at 100F was carried out with agitation at 85 RPM, followed by an individual rinse under distilled water at room temperature for each cloth. The cloths were then air dried at room temperature before being graded on a Gardner meter.
Grease/oil removal was measured by the difference in light reflectance readings before and after washing treatment using a Gardner meter. Because of the lighter -, color of the OHT and triolein soils, an oil-soluble red dye was dissolved in the oil, and the "a" reading on the Gardner meter was used as the indicator of their removal.
The Oil Removal Index is merely an arbitrary value (sum of QL's and Qa's) reflecting the overall soil removal performance of each sur~actant.
The commercial laundry detergents used as a comparison in the Table had the formulations (all percentages being by weight of the total).

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~5~165 Anionic surfactant 16.8%
Phosphate solids ~9.5 Silicate solids 5.~
Amide 1.6 Sodium sulfate 14.1 . Miscellaneous 2.1 Moisture 10.0 100. 0%

C14-C15 alcohol condensed 33.0%
with 7 moles of ethylene oxide Triethanolamine salt24.75 . of Cl2 LAS
; TEA 2.75 .
KCl 2.5 Ethanol 5.0 Water ~ miscellaneousBalance to 100~ ~ -. ~

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i5 It can be seen -that the performance of the various AE's on dirty motor oil ~DMo) removal correl~tes well with their interfacial tension lowering ability at a hydrocarbon/
water interface. This is predicted by the above theory since DMO is a hydrocarbon soil. On the basis of the teachings in the prior art, however, it would not be expected that the optimum material for DMO removal, i.e. CloE4, is also optimum for both OHT and triolein, soils which are much more polar in character. Nevertheless, as can be seen from Table I, the minimum value of ~i triolein/water occurs at almost the same HLB as that for ~i min (hydrocarbon/water) thus supporting the theory.
The Oil Removal Index valu~s in Table II also demonstrate the narrowness of the effective range of ethylene oxide distribution for a given carbon chain length and this is further emphasized in Table III which illustrates the effect of combining pairs of C10 ethoxylates, one being higher and one lower in ethylene oxide content than C1oE4.
The test conditions are identical to those in Table III.
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:~598~i5 The results show that oil and grease removal performance of blends of ethoxylates deteriorates progressively as the ethylene oxide contents of the individual components of the blends differ from that of the optimum composition.
A significant benefit can still be obtained for blends of materials in the E2 through E7 range having an optimum mixed HLB; however, if one of the materials forming a blend is outside this range, it causes a ~arked fall~off in performance.
In particular, it can be seen from Table III that the fall off in performance for blends of ethoxylates outside of the optimum range is greater for more polar lipids such as Triolein and OHT than for the hydrocarbon soils. Expressed another way, `
it appears that the limits of the permissible ethoxylate blends are more critical for good performance for the more polar soils.
Unethoxylated alcohol is particularly detrimental to performance. Normal commercial AE's in the optimum HLB
range (9.7-11.5) have quite high levels of free alcohol (see Table V) and therefore give much poorer performance than the ~' compositions herein. Thus, although a mixture of ethoxylates ~--can be formulated having the correct HLB for optimum grease and oil removal performance, poor grease and oil removal will be obtained unless the distribution of ethoxylates is controlled to provide at least 63~, preferably 70% of the ethoxylate with 2-7 ethylene oxide groups and the level of free alcohol is less than 5%.
However, the range of alkyl chain lengths useful in the present invention is such as to make it advantageous to maximize ethoxylate contents in different ranges depending on the mean alkyl chain length. This is in accord with th~
; 30- need to restrict of HLB's around the desired mean in order to max~imize the interfacial tension lowering effect.

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1~5~8S~i For alcohols having a mean chain length o:E 9-11 carbon atoms, preEerred ethoxylates for use in compositions in accordance with the invention have at least 55% by weight :
and preferably at least 60~ of material containing 2-6 ethylene oxide groups while for alcohols having 12-13 carbon atoms in the alkyl chain the ethoxylates preferably contain at least 55% by weight and preerably at least 60% of material having 3-7 ethylene oxide groups. Alcohol ethoxylates having 14-15 carbon atoms in the alkyl chain, whilst requiring at 10 least 63% by weight in the E2 7 range to have good oil and -~
grease removal, preferably have at least 55% by weight of material having 3-8 ethylene oxide groups.
Table IV demonstrates the good oil and grease removal performance that can be obtained for a range of ~ ~
blends of CloE3 and CloE6. It can be seen that soil removal ~ .
performance correlates well with HLB and that below approximately 9.5 and above 11.5 per:Eormance deteriorates markedly so that not only must there be a narrow distribution :
of ethoxylate specie~, but the HLB must be kept within narrow limit5.
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1~5~865 Mix-tures of C12E4 and C12E5 are found to display an optimum level of performance a-t about 50/50 blend o~ th~ two materials, which is in good agreement with the predictiorl based on interfacial tension values ~or the Cl2EX series in Table I~
~ t has also been found that valuable mixtures can be made of two materials having different chain lengths but the same level of ethoxylation, each material having an HLB
lying within the range found to be useful in the present invention. Once again, maximum grease and oil removal is achieved at the minimum predicted value for ~i for the hydrophobic soils.
Methods of producing ethoxylated primary aliphatic alcohols are disclosed hereinafter but should be understood as not forming part of the present invention.
The prior art, e.g. U.S. Patent No. 1,970,578, teaches that ethoxylation can be carried out using both acid and base catalysts, but the greater incidence o~ ;
side reactions and degradation products arising from acid-catalyzed ethoxylation makes this technique much less attractive in spite of the narrower distribution of ethoxylate t~pes that is potentially achievable. Accordingly, references to ethoxylation and ethoxylates in this Application are to be understood to represent the processes and materials produced therefrom using base catalysis.
As previously indicated~ commercially available materials useful in the present invention typically utilize the "Neodol" and "Dobanol" alcohol blends, sold respectively by the Shell Chemical Co. and Shell International Chemicals -30 ` Ltd., as alcohol precursors. These alcohol blends are condensed with 2.0-4 moles of ethylene oxide in the presence .

of a minor proportion of a strong ba;se such as sodium hydroxideor potassium hydroxide using a process such as that disclosed in U.S. Patent 3,682,849.
Alcohol blends haviny a mean chain length of 12 carbon atoms or less such as Dobanol 91 t Neodol 01, N~odol 12 are ethoxylated to give an uptake of about 2.0 to about 3.5 moles, preferably 2.0 to 3.0 moles of ethylene oxide per mole of alcohol. Neodol 23 typically requires 2.0-4.0 moles, preferably 2.5 to 3.5 moles of ethylene oxide per mole of alcohol while Neodol 45 is conveniently ethoxylated to giv~
an uptake of about 2.0 to about 4.0 moles, preferably 3.0-4.0 moles of ethylene oxide per mole of alcohol. The condensation products at this stage have a broad distribution of ethoxylates and a high level of free alcohol typical of base-catalyzed ethoxy lation reactions and are quite unsuitable for the purposes of the present invention. Accordingly clistillation, or evaporation under sub-atmospheric pressure, of the product to strip the ~ ~ ;
unreacted alcohol and desirably also a major portion of the lower ethoxylates is carried out in the manner disclosed in U.S. Patent 3,682,849 in order to maximize the proportion of ethoxylates lying within the range 2-7 ethylene oxide ;~
groups per molecule of alcohol. The narrower the distribution of carbon atoms around the mean alcohol chain length, the simpler will be the stripping process. Ideally the alcohol blends will be composed entirely of matexial falling in the stated chain length range so that there will be no overlap in boiling point between e.g. unethoxylated alcohol of the highest chain length in the blend (which is undesirable) and di- or tri-ethoxylated alcohol of the lowest chain length in the blend (which is useful). The amount of - material to be removed normally lies in the range of 10-60%

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by ~eight of the ethoxylated alcohol and desirably in the range of 20-30~ by weight in order to provide a narrow distribution of ethoxylates havin~ the desired HI,B, whilst maintaining an economic process.
- Table V gives some typical distributions of ethylene oxide content for ethoxylates of several commercial primary alcohol blends both "as ethoxylated" and also after stripping to provide alcohol ethoxylates in accordance with the invention. Data is present~d for ethoxylates based on C12 13 alcohols (columns 1-3), Cg 11 alcohols (columns 4-6) and Cl~ 15 alcohols (columns 7-9). Column 10 represents a comparative example.

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TABEE V

12-13 Cg_ll Alcohol . Ethox~_ateEthoxy~ate Welght ~
Ethoxylate l 2 3 4 5 6 .
5Eo 15.8 - 6.4 16.5 1.6 7.4 E1006 4.7 11.5 3.2 5.5 E2 1~.2 8.6 6.3 13.4 12~2 7~4 E312.2 18.0 7.8 13.816.3 9.1 E410.6 15.6 8.9 12.417.810.0 E58.6 1207 9.4 10.115.210.9 E6 6.49.49.4 7.811.7 9.9 E7 5.27.79.0 5.88.7 9.0 ~8 4.16.08.2 3.55.5 7.8 , Eg 3.24.77.1 2.33.5 6.5 E1o 2.53.76.0 1.62.4 5.1 ll 2.02.94.8 0.71.1 3.9 El2 1.42.13.7 0.50.8 2.8 El3 1.3l.92.7 0 0 l.9 El4 1.11.61.8 0 0 1.2 Others 3.45.13.8 0 0 2.3 Weight %
E2-E7 55.2 72.0 50.8 63.381.956.6 3 7 43.0 63.4 44.5 57.5* 73.2* 47.5 E average 3.0 4.9 4.9 2.54.1 4.32 Weight Removed 0 34.0 0 0 34.0 HLB 8.6 10.5510.55 8.110.710.7 . -,~ *E2-E6 :.

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~5~36~5 TABLE V_(Cont'd) Cl~ 15 Alcohol _ Ethoxylate Weight %
Ethoxylate 7 8 9 10 Eo 9.7 0.3 4.8 2.3 El 6.9 1.1 3.5 1.6 E2 8~8 4.6 4.8 2.6 E3 10.1 10.0 6.1 3.6 ~4 10.6 13.2 7.2 5.0 E5 10.4 1303 8.0 6.3 E6 9.6 1205 8.5 7.8 E7 8.3 10.9 8.5 8.8 -~
E8 6.9 9.2 8.4 8~7 ~9 5.6 7.4 7.8 8.5 Elo 4.2 5.5 7.1 8.2 Ell 3.0 4.0 6.1 7.
2.1 2.8 5.1 6.7 13 1.4 1.9 4.1 5~8 .
E14 0.8 1.1 3.1 16.3**
Others1.6 2.3 6.9 ;~- Weight %
2 757.8 64.6 43.1 34.1 E3-E7 56.9+ 69.2~ 46.7 30.5 E average 4.0 5.9 5.9 7.0 Weight %
Removed8.927.0 11.7 ~
HLB 10.8 10.8 :

**Includes others + E3-E8 1059865 ~ ~
It can be seen that a relatively low level of ¦ ethoxylation must be used in order to avoid appreciable quantities of higher ethoxylates which are of less v~lue, so that over-ethoxylation cannot be used to minimize the level of unethoxylated alcohol.
In general, for the range of alkyl chain lengths of interest in the present invention, the mean level of ethoxylation before stripping should not exceed 4 moles per molecule of alcohol and, as previously mentioned, lower levels are advisable for alcohols in the Cg 11 chain length range. If too high a level of initial ethoxylation is used, it may not be possible to meet the criteria for he weight percentage of desired etho~ylates in the mixture. On the other hand, if too low a level of ethoxylation is employed, the amount of material to be stripped off will be excessive and wlll raise the manufacturing cost of the ethoxylate to a prohibitive level.
Table VI exemplifies the balance which has to be struck in selecting a level of in:itial ethoxylation.
In the Table a Neodol 23 alcohol is ethoxylated to different levels of ethylene oxide content and then stripped to a constant HLB of 10.5. The total weight percentage of material in the E3-E7 range is given for each stripped alcohol together with - the weight percentage of starting ethoxylate that has to be removed to achieve the stated HLB. For comparison purposes, a Neodol 23 alcohol ethoxylated to an HLB of 10.5 without stripping is also included.
It will he seen that a high proportion of the stripped ethoxylate lies in the E3-E7 range if the initial level of ethoxylation is only 2 moles ethylene oxide per mole of alcohol. However, it is necessary to remove 61.7% of the , , ~S~38~5 starting material to obtain the desired HLs. If a level ofethoxylation of 4.0 moles per mole of alcohol is employed, then only 11.5% of the initial material must be removed to attain an Hl,B of 10.5 but the percentage of material within ~` the E3-E7 range has dropped to 55.0% by weight.
Thus performance considerations dictate the selec-tion of an upper limit of ethoxylation of about 4 moles of ethylene oxide per mole of alcohol while economic considerations make levels of ethoxylation of less than 2 moles per mole of 10 alcohol unattractive.

TABLE VI

_ i Wt. % of Stripped Starting Wt. % Final Product in E3-E7 MaterialStripped NLBRange Neodol 23 E2 0 61 7 lOj5 77 3

4.0 11.5 55.0 0 1 10-5 1~4-4 ~ ;

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In this context it should be understood that as the alkyl chain length of the precursor increases and the mean level of ethoxylation increases to provide the correct HLs after stripping, the distribution of ethylene oxide units becomes broader. Little decrease occurs in the level of unreacted alcohol but the "tail" ~ -of undesirable higher ethoxylates increases in extent and in the level of each ethoxylate present in the mixture; see for example Column 10 of Table V in which the ethoxylate distribution is set out for a C14 15 primary alcohol containing an average of seven moles of ethylene oxide. In consequence, although less material has to be stripped to remove unreacted alcohol and lower ethoxylates, the remaining material has a less pronounced peak in the desired range of ethoxylates and also higher levels of material outside of this range. Thus an increase in alkyl chain length not only slows the kinetics of interfacial tension reduction, but also leads to a less pronounced peak in the ranye of useful ethoxylates and consequently poorer oil and grease removal performance.
However it can also be seen ~hat for the shorter chain length alcohols (viz. Cg_ll alcohols) that require a lower initial level of ethoxylation, the weight percentage of material lying within the desired range of ethoxylate levels may already be high. Nevertheless stripping is still essential to xemove unreacted alcohol and low ethoxylates to minimize the interfacial tension value and thereby to maximize oil and grease removal ~
performance and this will reslllt in material having a very ;-30- high weight percentage of ethoxylate within the desired ~ -range of 2 to 6 ethylene oxide groups per molecule of - 34 ~

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alcohol.
It will be apparent from the foregoing that the grease and oil removal performance of the alcohol ethoxylates of the present inventlon is adversely affected by the presence of any other nonionic surfactant whose HLs and ethoxylate dis-tribution i5 not controlled so as to be close to tha composition having the minimum ~i for that other surfactant. Thus primary alcohols ethoxylated in the conventional manner without any subsequent stxipping cannot be blended with the ethoxylates of the present invention without a loss in grease and oil removal performance. This applies e~en to alcohols conven-tionally ethoxylated to a value that gives the ethoxylate the correct HLB for the mean alcohol chain length, because such ethoxylates will contain components that are undesirable in the context of the present invention, while at the ~ame time they contain lower levels of the useful components. A
comparison of columns 2 and 3 and also of columns 7 and 8 of Table V clearly illustrates the composition differences betw~en stripped ethoxylates of the invention and unstripped ethoxylates of the same alkyl chain length and HLB.
However, the present invention does contemplate blends of two or more optimized mixtures each having an HLB, ; ethoxylate distribution and alkyl chain length distribution satisfying the previously mentioned criteria. Blends of this type could be attractive economically or might become `~
necessary for reasons of~availability of the different alkyl chain length alcohols, or migh~ confer some other performance benefit (e.g. sudsing) not given by a single optimized mixture.
A non-limiting example of such a blend is a 50/50 mixture by weight of stripped Cg 11 alcohol having a mean of 4 ethylene - oxide groups in combination with stripped C14 15 alcohol ;

~ S9~1~,5 having a mean of 5.5 ethylene oxide groups.
Nonionic surfactants that are not alkoxylated may be present in amounts of up to 100~ by weight of the ethoxy-lates of the present invention. Examples of such nonionic surfactants are the Cl0-C16 alkyl di lower alkyl or hydroxy ` alkyl amine oxides and the alkyl amides including the mono-and di-alkanolamides.
Optional Components As noted above the nonionic surfactants of the present invention can be employed in a variety of compositions where solubilization of oil or grease is a desired property. Oil and grease removal capability is a highly desirable property for laundry detergent compositions, especially those designed for domestic use. In such situations the compositions of the present invention can be used on their own but are more commonly Pmployed together with other conventional detergent ingredients, such as surfactants and builders. The following list of such detergent ingredients that can be used in combination with the ethoxylated nonionic surfactants of the present invention is to be understood as being typical but not limiting with respect thereto.
Surfactants Optional surfactants other than the permissible non1onic surfactants previously mentioned include anionic, zwitterionic, ampholytic and cationic detergent compounds. ~ ~
Typical compositions for use as laundry detergents comprise ~ `
about 1% to about 99% (preferably 10% to 40~) by weight of the ethoxylated alcohols of the invention and from about 1%
30 to about 60~ (preferably l~ to 20%) of one or more of the ;~
above optional surfactant materials. Specific compounds .

' ' ' ', :

5~i5 and mixtures that can he used in the compositions of the present invention axe disclosed in U.S. Patent 3,664,961 issued May 23, 1972 to Russell l~orris, particularly at column 2, line 70 to column 4, line 62 and column 6, line 60 to column 9, line 3.
Alkyl e~her sulfates of value in compositions of the present invention are disclosed in Belgian Patents 807,262 and 807,263 issued on May 13, 1974.
Other useful detergent compounds herein include the water-soluble salts of esters of ~-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group;
water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to g carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety and ~-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon ~' atoms in the alkane moiety.
Alkane sulfonates useful in the present invention are usually mixed secondary alkyl sulfonates having from 10 to 20 carbon atoms in the alkyl chain. Pre~erably at ;, least,80~ and most preferably at least 90~ by weight of the alkyl group lies in the C10 17 chain leng~h range. Alkane '' sulfonates are preferably prepared by treating a selected paraffin material of the desired chain length distribution ' with sulfur dioxide and oxygen to give a secondary sulfonic acid, which is then neutralized with a suitable base. An alternative process utilizes chlorine and sulfur dioxide in the presence of UV light to give sulfuryl chlorides which are then hydrolyzed and neutralized to form the secondary ' alkyl sulfonates.

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Specific preferred detergents for use herein include: sodium linear ClO~C18 alkyl benzene sulfonate;
triethanolamine C10-C18 alkyl benzene sulfonate, sodium tallow alkyl sulfate, sodium coconut alkyl glyceryl ether sulfonate; the sodium salt of a sulfated condensation product of a tallow alcohol with from about 1 to about 3 moles of ethylene oxide; 3-(N,N-dimethyl-N-coconutalkyl-ammonio)-2-hydroxypropane-1-sulfonate; 3-(N,I~-dimethyl-N
coconut-alkylammonio)-propane-l-sulfonate; 6-(N-dodecyl-benzyl-N,N-dimethylammonio) hexanoate; and the water-soluble sodium and potassium salts of higher fatty acids containing 8 to 24 carbon atoms. ~;
It is to be recognized that any of the foregoing detergents can be used separately herein or as mixtures.
Detergency Builders The herein-disclosed compositions can contain, ;
in addition to the nonionic mixtures and optional organic ;~
detergent compounds, all manner of deteryency builders commonly taught for use in detergent compositions. Such builders can be optionally employed in the present composi-tions at concentrations of from about 5% to about 90~ by weight, preferably from about 10% to about 80% by weight . ~ .
and most preferably 25% to about 70% b~ weight, of said optional builders. Useful builders herein include any of the conventional inorganic and organic water~soluble ` - ;
; builder salts.
Such inorganic detergency builders can be, for - example, water-soluble salts of pyrophosphates, orthophosphates, polyphosphates, phosphonates, carbonates/ bicarbonates and silicates. Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, pyrophosphates :
and hexametaphosphates.

- ~8 -:. , :

~5~365 The polyphosphonates specifically include, for example, the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts o~ ethane l-hydroxy~
diphosphonic acid and the sodium and potassium salts of ethane-1,1,2-triphosphonic acid. Rxamples of these and other phosphorous builder compounds are disclosed in U.S. Patents 3,159,581, 3,213,030, 3,422,021, 3,422,137, 3,400,176, and 3,400,148.
Non-phosphorous-containiny builder salts such as the alkali metal carbonates, bicarbonates and silicates are also useful herein.
Water-soluble, organic builders are also useful ;~
herein. For example, the alkali me'cal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxy- ;~
lates and polyhydroxysulfonates are useful builders in the ` `
present compositions and processes. Specific examples of the polyacetate and polycarboxylate ~uilder salts include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
P~eferred examples of polycarboxylate builders are set forth in U.S. Patent 3,308,067, Diehl. Examples of such materials include the wa-ter-soluble salts of homo- -and copolymers of aliphatic carboxylic acids such as maleic - acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
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Additional preferred builders herein include the water-soluble salts, es~ecially the sodium and potassium salts, of carboxymethyloxymalonate, carboxymethyloxysuccinate, - cis-cyclohexanehexacarboxylate, cis~cyclopentanetetracarboxylate and phloroglucinol trisulfonate. ~:

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~ fur-ther class of detergency builder materials useful in the present invention are insoluble sodium alumino-silicates, particularly those disclosed in Belgian Patent 814,874 issued ~lovember 12, 1974 and incorporated herein by reference. This discloses and claims detergent compositions containing sodium aluminosilicates o formula Naz(Alo2)z(sio2~yxH2o wherein z and y are integers of at least 6, the molar ratio ' ' of z to 6 is in the range from l~O:l to about 0.5:1 and x is an integer from about 15 to about 264,~said aluminosilicates having a calcium ion exchange capacity of at least 200 mg. ~-eq./gr. and a calcium ion exchange rate of at least about 2 grains/gallon/minute/gram. A preferred material is Nal2(siO2~Alo2~l2 27 H2 Another t~pe of detergency builder material useful in the present compositions and processes comprises a water-soluble material capable of forming a water-insoluble reaction product with water hardness cations in combination with a crystallization seed which is capable of providing growth sites for said reaction product. Builder materials of this type are disclosed in Belgian Patent 798,856 issued October ; 29, 1973.
The compositions herein can optionally contain all manner of additional materials commonly found in laundering and cleaning compositions. Specifically, oxidizing bleaches such as sodium perborate, sodium percarbonate, optionally with bleach precursors such as phthalic anhydride, tetra acetyl ethylene diamine, tetra acetyl methylene diamine or tetra acetyl glycoluril may be incorporated at levels of 1% to 25%
of the composition~
~ 41 -.~

~5~ ii5 Suds suppressors such as blends of silanated silica and silicone fluids, C20 22 fatty acids and certain microcrystalline waxes, e.g. Mobilwax 2305 ~ may be employed alone or as mixtures at levels of 0.005~ to 5%, preferably 0.01% to 3% and most preferably 0.1% to 1~ of the composition.
Viscosity and anticaking acids such as sodium salts of lower alkyl aromatic sulphonic acids are conveniently employed at levels of 0.5% to 5%, particularly if anionic surfactan~s are used as part of the surfactant mixture. Other useful anticaking ingredients include the alkali metal salts of a-sulphosuccinic acid and benzene sulphonic a~id.
Soll suspending agents such as sodium carboxy methyl cellulose and hydroxyethyl ce:Llulose may also be used in amounts of 0.25% to 5% by weight. Other suitable materials useful for this purpose includ~ copolymers of maleic anhydride with ethylene or methyl vinyl ether and -certain polymeric glassy metaphosphates.
Enzymes such as the proteolytic enzymes sold under the trade marks "Alcalase" and "Esterase" (Novo ~ .
Industries A/S, Denmark) Maxatase and AZ-Protease (Gist-Brocades NV The Netherlands) may be incorporated at levels of up to 1~ by weight, preferably from 0.25% to 0.75~ by weight. Such enzymatic materials may be coated or prilled to aid their stability and to minimize the formation of dust during processing and subsequent storage.
Typical but non-limiting examples of granular compositions in accordance with the present invention comprise by weight of the composition: 2%-30%, preferably ~ 10~-25% and most preferably 15~-20~ surfactant; 10%-80%, preferably 25~-70% by weight of a detergent builder salt;

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and lS~-50% of other optional ingredients such as bleaches, suds suppressors~ viscosity and anticaking aids, anti-redeposition agents, fluorescers, enzymes, perfumes, colors, antibacterial agents.
The alkoxylated~nonionic mixtures herein can be used alone as detergent compositions, but are most often ~-incorporated in a liquid or solid carrier, which may in turn be used in combination with other optional ingredients such as those previously discussed. Conveniently the nonionic mixture comprises from about 5% to about 95% (preferably 8%-45%) by weight of the nonionic mixture: carrier combination.
Liquid carriers include water and water-alcohol mixtures, e.g., 90:10 (wt.) water-ethanol; 80:20 (wt.) water:n-propanol;
70:30 (wt.) water-isopropanol; 95:5 (wt.) water:n-butanol, and the like. Water~ethanol mixtures at weight ratios of water:ethanol of 95:5 to 1:1 are especially preferred liquid carriers herein. ~
Typical but non-limiting liquid detergent ~ ~;
compositions embodying the present invention comprise 2Q (by weight of the compositions) 5%-50~, preferably 20%-40% -and most preferably 25~-35~ of a primary alcohol ethoxylate - material in accordance with the present invention and 5%-35%, preferably 10%-30% and most preferably 10%-20% of a salt of ; an anionic surfactant. In a preferred embodiment, a source .
of alkalinity is included at a level sufficient to raise the pH to a value of at least 7.Q. For this purpose, free base should be added in excess of that necessary to provide the cation for the anionic surfactant. Any source of free alkalinity can be employed but preferred materials are sodium and potassium hydroxide and alkanolamines. Usage of the latter is normally 1%~20%, preferably 2%-15% and most ,., . - . '.
'' ',: ' ' preferably 5~10~ by weight of the composition. Optionally builder materials such as pyrophosphates, silicates, and the previously-described synthetic aluminosilicates, citrates, borates, or nitrilotriacetates may be present in solution or dispersed and suspended at levels of 5%-20% by weight of the composition. The balance of such compositions normally ~
comprise minor ingredients such as viscosity ana gel control ~ -agents, perfumes, brighteners, colors, pH control agents and water which conventionally is present at a le~el of at `~
least 25% by weight.
Solid, sorbent carriers for the present nonionic mixtures include any of the hereinabove disclosed watex-soluble solid builder materials, as well as water-insoluble solids such as the microfine silicas, clays, kieselguhr, vermiculites and the like. The nonionic mixtures are sorbed ~`
on such solid carriers at a weight ratio of nonionic:carrier from about 1:20 to 20:1 ~or use in dry detergent compositions.
The appropriate ratio will, of course, depend on the sorbency of the carrier, and can be readily determined experimentally.
.

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The copending application of Wise, Serial No.
406,412 filed october 13, 1973, incorporated herein by reference, discloses the use of kaolinite clay to proYide a crutcher-stable nonionic surfactant/clay mixture suitable for use in the preparation of spray-dried detergent granules.
Kaolinite clay employed for this manner is a preferred water-insoluble carrier for preparing spray-dried detergent granules containing the nonionic mixture of the present invention.
10Granular compositions embodying the nonionic surfactants of the present invention can also be prepared by agglomeration techniques and by utilization oE carrier-type systems in which the nonionic is incorporated by spraying or blending with a portion of absorbent granules that are ; subsequently mixed with the remainder of the detergent formulation. Such absorbent granules may either be specially formulated or may be part of the spray dried product.
The following examples illustrate various composi- -tions employing the nonionic oil solubilization systems of this invention. The materials employed in the formulation of said compositions are commercially available, or can be prepared by methods well-known in the art.

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EXAMPLE I
A primary aliphatic alcohol blend sold by Shell Chemical Company under the trade name Neodol 23 was ethoxylated using base catalysis to give an average of ~ moles ethylene oxide per molecule of alcohol. The distribution of ethoxylates was as shown in column 1 of Table V. This material was then "stripped" by vacuum distillation to remove unethoxylated alcohol, monoethoxylate and a fraction of the diethoxylate, the total amount removed being approximately 34% by weight ;
10 of the starting material. The stripped material had the -ethoxylate distribution shown in column 2 of Table V with an average ethoxylate level of 4.9 moles per molecule of alcohol and an HLB of 10.55.
This stripped material was incorporated into a product identified hereinafter as "A" and was compared with ; two commercial formulations identiied hereinafter as "B" -~
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and "C". The composition of the various products by weight ` was as follows: ~ -, ~ , : , ~; - 46 ~

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A B C
Stripped primary alcohol ethoxylate 20.0 - -Cl primary alcohol e~hoxylate containing 14 ethylene oxide groups - - 9.0 NaC linear alkyl be~ene sulfonate 0.9 14.5 Sodium tallow alkyl sulfate lol ~ ~ ; .
Soap - 2.0 1.0 Sodium tripolyphosphate 24.4 49.5 32.0 Sodium silicate (SiO2:Na2O = 2.0:1) 10.0 5.9 6.0 Sodium sulfate 27.4 14.9 36.0 Sodium perborate - - 1.0 Sodium toluene sulfonate 1.0 - -Bentonite clay 6.0 Water and miscellaneous 9.2 13.2 15.0 100. 0100. 0 100. 0 The cleaning performance of these products was then compared using a single cycle facial swatch test in :` :
which swatches of 65/35 polyester/cotton cloth were soiled with facial soil and then washed in an automatic miniature washer for 10 minutes, rinsed once at wash temperature and `~
then machine dried before being graded.
Compositions A and B were used at 0.12% product ; concentration. Composition C was used at 0.24% concentration, :
this being the mean concentration at which this product is used according to consumer research data. -., .
. .
: :

~1~59~
The grading of the clo-th swatches after cleaning was carried using a round robin test comparing every treat-ment with every other treatment and the soil removal was expressed in panel score difference units. In the results below each figure is the a~erage of at least three grades under the stated conditions and the poorest performance is expressed as a zero score.

Hardness*
grains/ F. Product ProductProduct 10 U.S. gallon Temp. A B _ C
- 2 100 0.81 0.45 0.0 7 100 0.37 0.30 0.0 12 100 0.48 0.0 0 31 7 80 0.31 0.0 0.0 7 120 0.73 0.28 0.0 ~-*Ca:Mg = 3~
~ '.
~ It can be seen that, in very instance the product ~;
.
embodying the nonionic sur~actants of the present invention was superior tc~ the other formulations in removing greasy facial soil.
EXAMPLE II
The stripped alcohol ethoxylate used in Example I
was incorporated into a product identified hereinafter as D' and was compared to Product B of Example I and a Product hereinafter identified as "E'. The products had the following composition by weight:

.'~' .

,: .

~5~8~
D B E
Stripped primary alcohol ethoxylate 20.0 - -NaCl2 linear alkyl benzene sulfonate 0.9 14.5 9.0 Sodium tallow alkyl sulfate l.l - -5Odium tallow alkyl ether sulfate containing an : average of 3 moles ~:
ethylene oxide ~ - ll.0 Sodium soap - 2.0 1.2 Sodium tripolyphosphate - 49.5 Sodium silicate : ~SiO2:Na2O = 2.0:1) lO.0 5.9 20.0 Sodium carbonate 25.0 - 20.0 Calcium carbonate 9.0 Sodium sulfate 18.1 14.9 30.1 Sodium toluene sulfonate l.0 - - ~ `
Kaolinit~ clay 6.0 - -; 20 Water and miscellaneous8.9 13.2 5.2 Anticaking agent - - 3.0 Proteolytic enlzyme - - 0.5 10~. ~100. 0100. 0 The products were subjected to a single cycle facial ~ ~ :
swatch test similar to that of Example I and the results are given in the table below wherein each column represents an :, .i average of at least two test results. The same washing, ~ :~
drying and grading procedures we~e used as in Example I, and the temperatures and water hardnesses are indicated in the -column headings.

..
~ 49 -:, .

.. . . ~, . .

: .

Hardness grains/ E'~ProductProductProduct U.S. ~allon Temp. D B E
2 100 0.61 0.80 0.00 7 100 1.03 0.88 0.00 1~ 100 0.83 0.00 0.15 7 80 0.78 0.45 0.00 ; 7 120 0.44 ~.31 0.00 ..
, In all instances Product D, which incorporated an ethoxylate having a composition in accordance with the present invention, was graded as superior to Product E ~ ~
and was also graded superior to Product B in all but one ~ ~:
instance, even though it contains no phosphate. :-. E~IPLE III `:
Two high density granular detergent formulations designated below as F and G were compared for oil and grëas~
removal. Composition F was ormulated in accordance with the present invention whilst composition G was a commercially available heavy-duty laundry detergent. The compositions (in ., 20 parts by weight) are given below:

': ' . `, :. -- 50 - ~

10~i98~i G

C primary alcohol ethoxylate ~ontaining 14 ethylene oxide groups ~ 9 0 C12~13 primary alcohol having an lnitial ethylene oxide ~ content of 3 moles per mole of alcohol, stripped to give an average oE 4.9 moles ethylene oxide per mole of alcohol 11.0 C16-18 soap 1.0 Sodium toluene sulfonate 1.0 - ~
Sodium tripolyphosphate 34.0 32.0 ~:

Sodium silicate (SiO2:Na2O = 2.0:1) 6.0 6.0 Sodium sulfate 38.4 36.0 Bentonite clay 4.0 -Sodium perborate - 1.0 20 Water and miscellaneous 5.6 15.0 -100. 0 100. 0 .~
Density oz./cup 5.0 5.4 ~ :

Two-inch square swatches of Dacron ~ , Kodel ~ , ~
65/35 Dacron ~ /cotton, 65/35 Kodel ~ /cotton and cotton :
were each soiled with dirty motor oil (DMO), a 1:1:1 mixture of oleic acid, octadecane and triolein (OHT) and three practical triglyceride soils (Clisco ~ oil, bacon grease and margarine) and were then washed with each of the above ; compositions at 100F for ten minutes in two water hardnesses.
Product F was used at 0.23% concentration whilst Product G
was used at 0.25~ concentration based on consumer research data.

, - 51 - ;
. : .

. . . - .

" 3~1[~S~i 365 After rinsing and machine dryiny the swatches were visually assessed by two graders to give an average value for each swatch using a grading scale of 0-100. Results are given belowO
VISUAL GRADES FOR GRF,ASE OIL REMOVAL
: FROM A NUMBER OF FABRICS AT 100F
.
F G F G
7 grains/gal.2 grains/gal Fabric Soilhaxdness* hardness*

Dacron DMO 60 40 50 25 Kodel DMO 30 15 35 20 Polyester O~T100 65 100 85 65/35 Dupont DMO 10 10 10 10 Dacron/Cotton OHT 40 30 70 65 ~Codel/Cotton OHT 65 45 75 55 Cotton DMO 35 25 45 40 ' OHT 80 70 90 90 *Ca:Mg = 3~
:`
It will be seen that composition F was equal or superior to composition G on every fabric and soil at both hardnesses.

,. .
~ ~ EXAMPLE IV
: .
A single cycle facial swatch test was carrled out to compare liquid detergent formulations identified hereinafter as M, N, O and P, respectively. Formulation M is in accordance with the present invention whilst formulations N and O contained ~ -the same level of nonionic surfactant but were not optimized -~
to produce an ethoxylate having the minimum value of interfacial tension for their respective alkyl chain lengths.

, : .

'`;~' ' ' `' ~ ' ~c~c~ 5 Eormulation P represented a commercially available heavy-duty liquid detergent product which contains 50% more anionic surfactant than formulation M.
The compositions of the formulations are gi~en below in parts by weight.
..
M N O P

Triethanolamine salt of C linear alkyl b~ene sulfonate 16.5 16.5 16.5 24.75 10 Triethanolarnine 5.5 5.5 5.5 2.75 95~ C /5% C fatty :~ alco~81 eth~xylated to an initial level of 3 EO
: groups per molecule of ~ ~
alcohol stripped to give ~ :
an average of 4.1 EO ~ ~:
groups per molecule of ::
alcohol 33.0 C linear primary - :::
a~co~ol ethoxylate having an average of 3 EO groups per molecule of alcohol - 33.0 Cl lS primary alcohol e~hoxylate derived from : OXO alcohols and having ~ :
3 EO groups per molecule . ~ ~
of alcohol - ~ 33.0 - .

Cl -15 linear primary alcohol e~hoxylate having 7 EO
groups per molecule of alcohol - - - 33.0 Water Balance to 100~ ~

" , ,:.

, ,~ ' , ' ' , - ~L10 S~36~
The tesk utilized cotton cloth swatches which were soiled with facial soil and then given a 10-minute wash in water containing 3 grains Ca per U.S. gallon at a temperature of 70F and a product concentration of 0.12%
by weight. The products were rinsed once at wash ~-temperature, dried and then visually graded using a round robin test comparing every treatment with every other treatment. The results are given below as panel score difference units, the poorest performance being expressed as a zero score.
.~
"
M - N O P
:
1.52 0.0 0.14 1.50 It can be seen that the formulations M and P
perform significantly better than formulations N and O.

., ' , . .
. ' ' ', - 5~ ;

,, EX~MPLE v A single cycle facial swatch test comparing the products hereinafter identified as "P", "Q", "R", and "S"
was run at a temperature of 50F in three water hardnesses (2, 5.5 and 9 grains/U.S. gallon) using ~he test procedur~
of Example I. The products had the following composition by weight:

P Q R S
.
Sodiun~ C lineax alkyl b~2zene sulfonate - 12.0 7.0 - ~;

Sodium Cl linear alkyl benzene ~ulfonate - - - 16.8 ~-Sodium C alkyl -ether sl~fa~e containing 1-3 ethylene groups - 8.0 5.5 -Sodium tallow alkyl sulfate - - 5.5 Stripped primary alcohol ethoxylate* 20.0 - -Sodium tripolyphosphate - ~24.4 49.4 ~ ~-~- Sodium pyrophosphate 25.0 25.0 - -.~
Sodium silicate (SiO2:Na2O = 2.0:1) 12.0 12.012.0 6.0 Sodium sulfate 41.0 41.0 37.015.2 Miscellaneous - - 2.62.6 :'; ., Moisture 2.0 2.0 6.010.0 l ;

:: 100. 0 100. 0 100. 0 100. 0 : ' *Material oibtained by stripping 30% by weight from a Neodol 23-3 ethoxylate. This material is characterized by the - following composition: 1.0% Eo~ E2-E7 76.2%, E3-E7 67.9%, EaV = 4.70 and a HLB = 10.25.

:, ' ,, .,, ' :
:
.,,~ ~.

.

,. .. . .
1. , . , , ~
: - - , . . . .

~C~5~86~i Product P was formulated in accordance with the invention while Product Q represented a composition utilizing anionic surfactants and a pyrophosphate detergent builder.
Products R and S are commercially available laundry detergents and it should be noted that Product S incorporates a much higher phosphate level than the others. Usage of all four products was at 0.12% concentration in the wash. The results of the test are given below in panel score difference ; ~-units, with the poorest performance being expressed as a zero score.

2 5.5 ..... _ __ ... _ P 0.95 1.43 2.44 Q 0.55 0.93 1.29 R 0.00 0.00 0.00 S 0.92 2.03 1.80 .. __ .... ... ... __ ,.
LSD 1.14 0.98 0.43 (0.05) _ It can be seen that at low temperatures, the product of the present invention is better than the anionic-based compositions Q and R having the same level of phosphate builder and is significantly better at the higher haxdness levels. At the highest hardness level a significant advantage is also shown for Product P relative to Product S which has two times as much phosphate.

.

, :

9~3~;5 EXAMPLE VI
5" x 5" swatches of three fabric types (cotton, 65/35 Polyester cotton blend and Polyester) w~re soiled : with one of five different hydrophobic stains (dirty motor oill, OHT , Crisco ~ oil, mineral oil and make-up3). The stained swatches were allowed to dry for one day prior to use.
: Five granular detergent products designated respectively T, U, V, X and Y were tested for their ability to remove these soils using the washing and grading techniques of Example I. The test employed a wash of ten minutes duration in 100F water of 7 grains per U.S. gallon hardness (Ca:Mg =
3:1) and a product concentration of 0.22~. The product CompoeitiOAs Were as follows in parts by weight:

~'.

., ' '.
~' - - ;
: As defined in Example III.
As defined in Example III.
3 "Eventone" manufactured by Avon Products Inc., New York ,.
-, ':

, . . . .. .
~" ~ ', ', ' ' .... . . .
., . ~ . . . , ~
' ..

~59~3~5 T U V X Y

Stripped primary alcohol ethoxylate of Ex. V - 11.0 - ~ 11.0 Primary C alcohol ~ with 14 e~hylene oxide groups - - 3.0 - -Sodium C12 linear alkyl benzene sulfonate 9.1 - - 9.1 10 Sodium soap 1.9 4 ~ . 9 1.1 Sodium tripolyphosphate32.0 32.032.058.6 32.0 Sodium carbonate - 10.0 - - 10.0 Sodium silicate* 5.8 8.0 6.05.88.0 Bentolite L - 5.0 - - 5.0 Sodium sulfate 43.025.5 36.013.424.4 Miscellaneous 3.2 0.4 0.91.21.5 Moisture 5.0 7.0 15.010.07.0 . 100.0 100.0 100.0lon.o100.0 *For V silicate ratio was 2.0:1 SiO2:Na2O
For T, U, X and Y silicate ratio was 1.6:1 SiO2:Na2O

Products T, V and X represented commercially available laundry detergents whilst products U and Y embodied the nonionic surfactants of the present invention.
The results are shown below, expressed as panel score difference units, the lowest score being given a zero rating.

. .

:

~C~5~ 5 MINERAL MAKE-DMO O~ITCRISCO OIL UP OVERALL
T 0.00 0.25 0.38 0.00 0.00 0.00 U 1.97 0.07 0.00 1.14 1.62 0.83 V 1.24 0.00 0.20 0.63 0.00 0.29 ~ X 0.33 1.76 0.62 0.25 1.00 0.~6 Y 1.66 0.38 0.25 1.3~ 1.38 0.87 LSD = 0.13 Q = 0.18 It can be seen that both on a majority of the individual stains and on an overall basis, products formulated in accordance with the invention (U and Y) were super~or to prior art products to a degree that was statistically ` significant. ` ., EXAMPLE VII
The procedure of Example VI was repeated using the four products designated hereinafter as H, J, X and L of the following composition by weight.

- :
,, ~ '.

~' , .
`' ' ' , :'. .
', . '-'~ ".

~'~'' ' . ~ ' , ' ' , " ' .' " . , ~1 I J K L
_ Stripped primary alcohol ethoxylate of Example V 11.0 11.0 - - 11.0 ` Sodium C12 linear alkyl benzene sulfonate - - 14.0 4.8 Sodium C -1 alkyl ether slu~fa~e containing 10 1-3 ethylene oxide groups - - 6.0 4.1 Sodium tallow alkyl sulfate - - - 1.9 -Sodium soap 1.1 1.1 - 1.7 Sodium silicate 10.0 10.0 20.0 13.1 10.0 Sodium sulfate 42.6 30.6 31.4 49.4 30.6 Sodium carbonate 20.0 25.0 20.5 18.8 25.A
Calcium carbonate - 7.0 - 7.0 Kaolinite clay 7.0 7.0 - - 7.0 ; 20 Sodium borate - ~ ~ ~ 5-0 ; Water and miscellaneous 8.3 8.3 8.1 6.2 4.0 Product concentration in the wash solution was 0.22%
in each instance. Products H, I, and L incorporated a nonionic surfactant in accordance with the present invention.
;~ Products J and K were two commercially available phosphate-free laundry detergents. Results obtained for the various hydrophobic stains are expressed below as panel score difference units, the lowest score being given a value of zero.
., ; . '~

~ .
- .

ii5 ~ MINERAL MAKE-DMO OHT CRISCO ~ _OIL UP OVERALL
~-1 1.62 2.65 ~).13 1.40 2.62 1.6d, 1. 04 2 . 63 0. 00 1. 32 3 . 29 1. 61 O . 11 O ~ 94 2 . 06 1 . 29 1 . 78 1 . 20 K ~ 0. 00 0. 22 0 . 00 0 . 00 0. 00 L 0.78 3.14 0.80 1.78 3.44 1.94 LSD = 0.17 Q - 0.25 It can be seen that products H, I, and L embodying :.
10 the invention have significantly superior performance to ;
the anionic-based non-phosphate products J and R.
EXAMPLE VIII
A primary aliphatic alcohol blend sold by Shell Chemical Co. under the trade name Neodol 45 was ethoxylated ;~
using base catalysis to give an average of 4.0 moles ethylene oxide per molecule of alcohol. This material was then : .
subjected to vacuum distillation to remove almost all the unethoxylated alcohol and monoethoxyl.ated alcohol together ~
with some diethoxylate material, a total of 27% by weight of ~ :
the ethoxyla~e charge being stripped. The distribution of , ~, . ethoxylate species before and after stripping is shown in columns 5 and 6 of Table V. The final average ethylene oxide level was 5.9 moles per molecule of alcohol and the : .
H~B was 10.8.

,~, . .
: ~ . .
:' ' ''~ ' ` ' ' - . ,.

/

, ' ' ' ' '~ ' ' ' ~ ` `
` ' '. `

~5~ 5 A granular detergent formulation incorporating the above material had the following composition:

~ Stripped primary alcohol ethoxylate 20.0 Sodium C12 linear alkyl ~
benzene sulfonate0.9 ~ -Sodium tallow alkyl sulfate 1.1 Sodium toluene sulfonate 0.5 -Sodium silicate (Sio2 Wa20 = 2 ~ 0 1) lOr O
Sodium tripolyphosphate 24~ 0 Sodium sulfate28 ~ O
Bentonite clay 6.0 Water, perfume and misc. 9~5 ',: ' ' The above composition possesses superior grease ;~
,~ and oil removing capabilityO .~`

;:
~ ~:
. : -1, ~ . . .
,. . . .

.. : .~
, ~ :

,, ' ~ ,:~' .:
: ,

- 6~ :~

'' '' ' ':

.~ . - . .
' ~. '

Claims (30)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A grease and oil-removing composition consisting essentially of a base-catalyzed primary alcohol ethoxylate having the formula R1 - R2 - O(CH2CH2O)navH
wherein R1 is a linear alkyl residue and R2 has the formula R3 being selected from the group consisting of hydrogen and mixtures thereof with C1-C4 alkyl groups, there being not more than 70% by weight of said groups in the mixtures, wherein R1 and R2 together form an alkyl residue containing a mean of 9 to 15 carbon atoms, at least 65%
by weight of said residue having a chain length within ?1 carbon atoms of the mean, wherein 3.5 <nav <6.5, provided that the total amount by weight of ethoxylate components in which n = 0 shall be not greater than 5% and the total amount by weight of components in which n = 2 to 7 inclusive shall be not less than 63%, and wherein the hydrophilic-lipophilic balance (HLB) of the ethoxylate shall lie in the range 9.5 to 11.5, said composition being otherwise free of alkoxylated nonionic surfactants.

2. A composition in accordance with claim 1 wherein R3 comprises a mixture of hydrogen and C1-C4 alkyl groups, the latter being present in an amount of 5% to 25%
by weight of the mixture.

3. A composition in accordance with claim 1 wherein R3 comprises a mixture of hydrogen and C1-C4 alkyl groups, the latter being present in an amount of 50% to 65%
by weight of the mixture.

4. A grease and oil removing composition consisting essentially of a base-catalyzed primary alcohol ethoxylate having the formula R1 - R2 - O(CH2CH2O)navH
wherein R1 is a linear alkyl residue and R2 has the formula R3 being selected from the group consisting of hydrogen and mixtures thereof with C1-C4 alkyl groups, there being not more than 25% of said groups in the mixtures, wherein R1 and R2 together form an alkyl residue having a mean chain length in the range of 10 to 15 carbon atoms, at least 80%
by weight of said residue having a chain length within ?1 carbon atoms of the mean, wherein 3.5 <nav <6.0 provided that the total amount by weight of components in which n = 0 shall be not greater than 5% and the total amount by weight of components in which n = 2 to 7 shall be not less than 63% and wherein the HLB of the ethoxylate shall lie in the range 9.9 to 11.3, said composition being otherwise free of alkoxylated nonionic surfactants.

5. A grease and oil-removing composition in accordance with claim 4 wherein R1 and R2 together form an alkyl residue having an average of about 10 carbon atoms, at least 90% of said residue being composed of alkyl groups having no less than 9 and no more than 11 carbon atoms wherein 3.4 <nav <4.5, provided that the total amount by weight of ethoxylate components in which n = O is not greater than 2% and the total amount by weight of components in which n = 2 to 6 shall be not less than 55% and wherein the HLB
shall lie in the range 9.7 to 11.2.

6. A composition in accordance with claim 5 wherein the ethoxylate is derived from a C9-C11 alcohol condensed with 2.0-3.0 ethylene oxide groups and then stripped of unreacted alcohol and lower ethoxylates to give an average of 3.6-4.5 ethylene oxide groups per mole of alcohol and an HLB in the range 10.0 11.1.

7. A grease and oil-removing composition in accordance with claim 4 wherein R1 and R2 together form an alkyl residue having an average of 12-13 carbon atoms, at least 90% of said residue being composed of alkyl groups having no less than 11 and no more than 14 carbon atoms, wherein 4.2 <nav <5.5 provided that the total amount by weight of ethoxylate components in which n = 0 is not greater than 1% and the total amount by weight of components in which n = 3-7 is not less than 55% and wherein the HLB shall lie in the range 9.7 to 11.1.

8. A composition in accordance with claim 7 wherein the ethoxylate is derived from a C12-C13 alcohol condensed with 2.5 - 3.5 ethylene oxide groups and then stripped of unreacted alcohol and lower ethoxylates to give an average of 4.4 - 5.5 ethylene oxide groups per mole of alcohol and an HLB in the range 10.0 to 11.1.

9. A grease and oil-removing composition in accordance with claim 4 wherein R1 and R2 together form an alkyl residue having an average of 10-15 carbon atoms, at least 90% of said residue being composed of alkyl groups having no less than 13 and no more than 16 carbon atoms, wherein 4.7 <nav<6.2 provided that the total amount of ethoxylate components in which n = O is not greater than 1%
and the total amount by weight of components in which n = 3-8 shall be not less than 55% and wherein HLB shall lie in the range 9.7 to 11.1.

10. A composition in accordance with claim 9 wherein the ethoxylate is derived from a C14-C15 alcohol condensed with 3.0 - 4.0 ethylene oxide groups and then stripped to remove unreacted alcohol and lower ethoxylates to give an average of 5.0 - 6.2 ethylene oxide groups per mole of alcohol and an HLB in the range 10.0 to 11.1.

11. A grease and oil-removing composition in accordance with claim 1 comprising a blend of two or more of the following ethoxylates:
(a) a mixture of individual compounds derived from a linear C9-11 primary alcohol which has been ethoxylated to give a mean of 2-3 ethylene oxide groups per mole of alcohol and then stripped of unreacted alcohol and lower ethoxylates -to give an average of 3.6-4.5 ethylene oxide groups per mole and an HLB in the range 10.0-11.1.
(b) a mixture of individual compounds derived from a linear C12-13 primary alcohol eth-oxylated to give a mean of 2.5-3.5 ethylene oxide groups per mole and then stripped of unreacted alcohol and lower ethoxylates to give an average of 4.4-5.5 ethylene oxide groups per mole and an HLB in the range 10.0-11.1.
(c) a mixture of individual compounds derived from a linear C14-15 primary alcohol which has been ethoxylated to give a mean of 3.0,4.0 ethylene oxide groups per mole of alcohol, and then stripped to remove unreacted alcohol and lower ethoxylates to give an average of 5.0 to 6.2 ethylene oxide groups per mole and an HLB in the range 10.0-11.1.

12. A liquid detergent composition especially adapted for grease and oil removal consisting essentially of:
(a) 5% - 50% by weight of the composition of a base-catalysed primary alcohol ethoxylate having the formula R1 - R2 - O(CH2CH2O)n avH

wherein R1 is a linear alkyl residue and R2 has the formula R3 being selected from the group consisting of hydrogen and mixtures thereof with C1-C4 alkyl groups, there being not more than 70% by weight of said groups in the mixtures, wherein R1 and R2 together form an alkyl residue having a mean of 10 to 15 carbon atoms, at least 65% by weight of said residue having a chain length with ?1 carbon atoms of the mean, wherein 3.5 <nav<6.5, provided that the total amount by weight of ethoxylate components in which n = O shall be not greater than 5% and the total amount by weight of ethoxylate components in which n = 2 - 7 inclusive shall be not less than 63% and wherein the hydrophilic-lipophilic balance (HLB) of the ethoxylate shall be in the range 9.5 to 11.5, said composition being otherwise free of alkoxylated nonionic surfactants;

(b) 5% - 35% by weight of the composition of a water soluble cosurfactant selected from the group consisting of anionic and zwitterionic surfactants, (c) the balance water.

13. A composition in accordance with claim 12 wherein the anionic surfactant is selected from the group consisting of alkali metal, alkali earth metal and alkanol-ammonium salts of C10-C14 linear alkyl aryl sulfonic acids C10-C16 .alpha.-olefin sulfonic acids, C10-C20 alkane sulfonic acids, C10-C18 alkyl sulfuric acids, C10-C18 polyglycol ether sulfuric acids, .alpha.-sulfonated C12-C18 fatty acids and C1-C8 alkyl esters thereof, and C10-C22 fatty acids.

14. A composition in accordance with claim 12 further including 5% - 20% by weight of the composition of a water soluble detergent builder selected from the group consisting of alkali metal silicates pyrophosphates, borates nitrilo-triacetates, ethylene diamine tetra acetates, citrates and mixtures thereof.

15. A composition in accordance with claim 12 further including 5%-20% by weight of the composition of a detergent builder selected from the group consisting of alkali metal borate pyrophosphates and synthetic alumino-silicates, part or all of which may be present as a solid suspension.

16. A composition in accordance with claim 12 wherein the ethoxylate is derived from a C9-C11 alcohol condensed with 2. -3.0 ethylene oxide groups and then stripped of unreacted alcohol and lower ethoxylates to give an average of 3.6-4.5 ethylene oxide groups per mole of alcohol and an HLB in the range 10.0 to 11.1.

17. A composition in accordance with claim 12 wherein the ethoxylate is derived from a C12-C13 alcohol condensed with 2.5-3.5 ethylene oxide groups and then stripped of unreacted alcohol and lower ethoxylates to give an average of 4.5-5.5 ethylene oxide groups per mole of alcohol and an HLB in the range 10.0 to 11.1.

18. A composition in accordance with claim 12 wherein the ethoxylate is derived from a C14-C15 alcohol condensed with 3.0-4.0 ethylene oxide groups and then stripped to remove unreacted alcohol and lower ethoxylates to give an average of 5.0-6.2 ethylene oxide groups per mole of alcohol and an HLB in the range 10.0 to 11.1.

19. A composition in accordance with claim 12 further including a source of alkalinity in an amount sufficient that the pH of a 0.1% solution of the composition is greater than 7.00

20. A composition in accordance with claim 19 wherein all or part of the source of alkalinity comprises a mono-, di- or tri- alkanolamine.

21. A composition in accordance with claim 20 consisting essentially of:
(a) 25% - 35% by weight of the composition of a base catalyzed primary alcohol ethoxylate having the formula R1 - R2 - O(CH2CH20)n avH

wherein R1 is a linear alkyl residue and R2 has the formula R3 being selected from the group consisting of hydrogen and mixtures thereof with C1-C4 alkyl groups, there being not more than 70%
by weight of said groups in the mixtures, wherein R1 and R2 together form an alkyl residue containing a mean of 9 to 15 carbon atoms, at least 65% by weight of said residue having a chain length within ?1 carbon atoms of the mean, wherein 3.5 <nav <6.5, provided that the total amount by weight of ethoxylate components in which n = O shall be not greater than 5% and the total amount by weight of components in which n = 2 to 7 inclusive shall be not less than 63%, and wherein the hydrophilic-lipophilic balance (HLB) of the ethoxylate shall lie in the range 9.5 to 11.5;
(b) 10% - 20% by weight of the composition of a water soluble salt of a linear C11-C13 alkyl benzene sulfonic acid;
(c) 2% - 15% by weight of the composition of an alkanolamine selected from the group consisting of mono-, di-, and tri- ethanolamine;
(d) 0.1% - 5% by weight of an alkali metal hydroxide;
(e) 0.1% - 2% by weight of oleic acid; and:
(f) not less than 25%, by weight of the composition of water.

22. A granular detergent composition especially adapted for grease and oil removal consisting essentially of:
(a) 2% - 25% by weight of the composition of a base-catalysed primary alcohol ethoxylate having the formula R1 - R2 - O(CH2CH2O)navH

wherein R1 is a linear alkyl residue and R2 has the formula R3 being selected from the group consisting of hydrogen and mixtures thereof with C1-C4 alkyl grouper there being not more than 70%
by weight of said groups in the mixtures, wherein R1 and R2 together form an alkyl residue having a mean of 9-15 carbon atoms, at least 65% by weight of said residue having a chain length ?1 carbon atoms of the mean, wherein 3.5<nav<6.5, provided that the total amount by weight of ethoxylate components in which n = O shall be not greater than 5% and the total amount by weight of components in which n = 2-7 inclusive shall be not less than 63% and wherein the hydrophilic-lipophilic balance (HLB) of the ethoxylate shall lie in the range 9.5-11.5; and (b) 10% - 80% by weight of a detergency builder salt said composition being otherwise free of alkoxylated nonionic surfactants.

23. A granular detergent composition in accordance with claim 22 wherein the ethoxylate is selected from the group consisting of (a) a mixture of individual compounds derived from a linear C9-11 primary alcohol which has been ethoxylated to give a mean of 2.0-3.0 ethylene oxide groups per mole of alcohol and then stripped of unreacted alcohol and lower ethoxylates to give an average of 3.6-4.5 ethylene oxide groups per mole and an HLB in the range 10.0-11.1;
(b) a mixture of individual compounds derived from a linear C12 13 primary alcohol ethoxylated to give a mean of 2.5-3.5 ethylene oxide groups per mole and then stripped of unreacted alcohol and lower ethoxylates to give an average of 4.4-5.5 ethylene oxide groups per mole and an HLB in the range 10.0-11.1; and (c) a mixture of individual compounds derived from a linear C14-15 primary alcohol which has been ethoxylated to give a mean of 3.0-4.0 ethylene oxide groups per mole of alcohol, and then stripped to remove unreacted alcohol and lower ethoxylates to give an average of 5.0 to 6.2 ethylene oxide groups per mole and an HLB in the range 10.0-11.1.

24. A granular detergent composition according to claim 23 wherein the detergency builder salt is selected from the group consisting of alkali metal salts of polyphosphates, carbonates, silicates, citrates, oxydisuccinates, carboxy methyloxy succinates, benzene tetra, penta and hexa carbox-ylates, benzene 1-3-5 tricarboxylates, 1-3-5 hydroxy benzene 2-4-6 trisulfonates, nitrilotriacetates, aluminosilicates of formula Na12(AlO2?SiO2)1227 H2O and mixtures thereof.

25. A granular detergent composition according to claim 23 additionally containing 0.5-30% by weight of bentonite or kaolinite clay based on the weight of the composition, the weight ratio of the ethoxylate to the clay being in the range 6:1 to 1:2.

26. A granular detergent composition according to claim 24 wherein the weight ratio of the ethoxylate to the clay is in the range 3:1 to 1:1.

27. A granular detergent composition according to claim 23 additionally containing from about 1% to 50% by weight of the composition, of an anionic or zwitterionic surfactant.

28. A granular detergent composition according to claim 27 wherein the anionic surfactant is selected from the group consisting of water-soluble salts of C10-14 linear alkyl aryl sulfonic acids, C10-16 .alpha.-olefin s acids, C10-20 alkane sulfonic acids, C10-18 alkyl sulfuric acids, C10-18 polyglycol ether sulfuric acids and .alpha.-sulfonated C12-18 fatty acids and lower alkyl esters thereof.

29. A granular detergent composition in accordance with claim 27 wherein the zwitterionic surfactant is selected from the group consisting of 3-(N,N-dimethyl-N-C10-18 alkyl (ammonio) propane-1-sulfonate, 3-(N,N-dimethyl-N-C10-18 alkyl (ammonio) -2-hydroxy propane 1-sulfonate and 6-(N-C10-14 alkyl benzyl-N, N-dimethyl ammonio) hexanoate.

30. A granular detergent composition consisting essentially of:
(a) 15-25% by weight of the composition of an ethoxylate material consisting essentially of a mixture of individual compounds derived from a substantially linear C12-13 primary alcohol ethoxylated to give a mean of not more than 3.8 ethylene oxide groups per mole of alcohol and then stripped of unreacted alcohol and lower ethoxylates to give an average of 4.4-5.5 ethylene oxide groups per mole and an HLB in the range 10.0-11.1;

(b) 25-40% by weight of the composition of a builder salt selected from the group consisting of alkali metal silicates, tripolyphosphates, pyrophosphates, carbonates, bicarbonates and mixtures thereof;
(c) 1-5% by weight of the composition of an anionic surfactant selected from the group cons.isting of alkali metal salts of C12 alkyl benzene sulfonic acids, tallow alkyl sulfuric acids, tallow alkyl ether sulfuric acids, C12-22 fatty acids, and mixtures thereof; and (d) 2-10% by weight of a clay selected from the group consisting of bentonite and kaolinite clays.