CA1037337A - Oil removal compositions - Google Patents

Abstract

OIL REMOVAL COMPOSITIONS
Jerome H. Collins ABSTRACT OF THE DISCLOSURE
Compositions and methods for dissolving oils and oily soils employing specific mixtures of short-chain and long-chain alkylene oxide nonionic surface active agents.
The compositions herein can be employed singly in aqueous laundry baths to remove oily materials from fabrics, or can be admixed with commercial detergent compositions to boost the oil removal properties thereof.

Description

- -:~37~
BACKGROUND OF T~IE INVENI`:[ON
This invention relates to compositions and processes for solubilizing oils. More particularly, the invention relates to the use of specific mixtures of long-chain alkylene oxide surfactants and short-chain alkylene oxide co-surfactants, said mixtures having a hydrophilic-lipophilic balance (HLB) in the range of from about 10 to about 12.5, to remove oil from fabrics and other surfaces.
Current laundry products and procedures exhibit one or more deficiencies when used to clean oily stains, particularly hydrocarbon stains, from fabrics. Fatty triglyceride soilsl especially those arising ~rom natural body secretions, present another type of oily stain which is difficult to remove from modern fabrics by means of simple aqueous laundering processes. Such deficiencies are especially apparent when polyester or polyester fabric blends soiled with various oily materials are laundered in a~ueous laundry baths. The oil removal problem is so acute that Smith, et al, Textile Chemicals, Col. 5, ~7, 138 (1973) have concluded that detergent formulation alone is very unlikely to solve the problem of effecting satisfactory release of any broad spectrum of oils from today's durable press fabrics, unless the fabrics are specially finished with hydrophilic materials.
Heretofore, effective oil removal from modern fabrics has largely been accomplished by means of relatively inconvenient and expensive methods involving non-aqueous dry cleaning processes. Accordingly, compositions and `
processes which would provide the economical and efficient removal of oily soils and stains from fabrics employing , .. ~ . . ...... . . . .

: .: . . .

:1~373~7 conventional household laundry equipment are desirable.
The present invention emp:Loys combinations oE
long-chain and short-chain alkoxylated nonionic materials to effect the removal oE oily mater:ials from fabrics in an aqueous laundering process. The use of alkoxylated nonionic detergent materials in cleansing operations has been described, for example, in U.S. Patents 2,133,~80 and 2,164,431.
The disclosures of these patents teach that the condensation products of aliphatic monohydric alcohols containing from 8 to abou~ 18 carbon atoms 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 3,679,608 discloses the use of the ethoxylates of random secondary alcohols in low sudsing detergent compositions.
U.S. Patent 3,008,905 teaches that the products produced by the addition of from 1 to about 4 moles of an - alkylene oxide with alcohols containing, at most, 12 carbon - atoms are suitable for use in detergent compositions.
U.S. Patent 3,342,739 broadly describes the use of condensates comprising from about 3 to about 10 moles of ethylene oxide per mole of higher aliphatic C10-C20 hydrocarbyl alcohol in detergent compositions in combination with various polyethyleneoxy ethers of alkyl phenols and alkylolamides.
V.S. Patent 3,619,119 discloses spot removal compositions containing mixed ethoxylates in combination with sulfated ethoxylate detergents for removing oily soils and stains from collars and cuffs of shirts and dresses.

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

~)3733'7 The Matheson and Richardson Canadian Patent No.
1,014,81~, issued April 2, 1977 teaches the use of condensa-tion products of fatty alcohols containing from 10 to 15 carbon atoms with 3 to 10 moles of ethylene oxide, said condensates having an ~ILB of from about 10 to about 13.5, together with various anionic detergents in laundering compositions.
While the use of various alkoxylated nonionic mixtures in detergent compositions is known, the detergency arts have not heretofore recognized that the combinations of short-chain and long-chain alkylene oxide condensates disclosed herein afford superior oily soil removal. For example, British Patent 1,241,754 broadly discloses nonionic mixtures having compositions which fall outside the limits of those compositions now found to be particularly advantageous for removing oil and grease from fabrics and - other surfaces. Indeed, U.S. Patent 3,682,849 suggests that the detergent properties of certain mixtures of ;~
alkoxylated nonionic detergents are improved when short-chain, less highly alkoxylated materials of the type employed herein are removed. Moreover, the article by Matson, "Syndets with Alcohol Derivatives", Soap and Chemical Specialities, November 1963 at page 52, 54, clearly indicates that the heavy duty detergency of alcohol polyalkoxylates resides in the C12 and higher ethoxylated alcohols, and that the C8 - Cll alkoxylates such as those employed in the instant compositions would be expected to exhibit very low detergency performance.
In view of the conflicting information in the ~1~373;~7 prior art, the most that can be said .is that various nonionic surEac tants and mixtures have been broadly ; suggested for use in detergent compositions. However, the prior art has not recognized the advantages which can ;

;-4 ~

_ _ .. . ..... . ... . . . ...... ..... . ... . .. ..... ...... ... ... .. .. . . ... . _ .. ... _ _ _ . ... _ _, ~L~3~337 be obtained by the proper formulation of nonionic mixtures comprising both short-chain and long-chain alkoxylated nonionic surface active agents oi the type disclosed - herein.
; It has now been discovered that prop~rl~
formulated mixtures of long-chain and short~chain alkoxy-lated nonionic surface active agents are especially useful in aqueous solutions for solubilizing oily soils and removing same from all manner of surfaces. Notably, the compositions herein are characterized by the speed with which they remove oils from fabrics, especially polyester and polyester blends; hence, they are useful for cleansing fabrics in the relatively limited time available in the deterging cycle :, ~
of a home laundry operation. Moreover, the compositions herein can be employed singly to cleanse materials such as fabrics, or can be added to various commercial laundry detergent compositions to enhance the oil removal properties ' thereof~
The compositions herein are useful for cleaning -~
, 20 and degreasing a variety of surfaces other than textiles and are uselful, for example, in the metal working trades and ` as hard surface cleaners for use on floors and walls.
It is an object of -the present invention to provide compositions for solubilizing oils and for removing oily soils from surfaces.
SUMMARY OF THE INVENTION
The instant invention encompasses granular deter-gent compositions especially adapted for removing oils and oily soil from fabrics consisting essentially of:
from about 15% to about 40% by weight of an ethoxylated nonionic surfactant mixture of which about 60-80% by weight of the mixture is a water-soluble Cg-C

,. . : ~ : . : . .

~37337 primary alcohol having an average of 10 carbon atoms in the alkyl chain condensed with an average of four ethylene oxide groups to give an HLB of about 10.5 and about 20%
to about 40% by weight ofthe mix~ure is the condensate of a secondary C10-C15 alcohol mixture having an average of 12-13 carbon atoms in the alcohol molecul~ with about 7-9 ethylene oxide groups to give an HLs of from 12.0 - 15.0, said surfactant mixture having an overall HLB of from 10.5 ~
12.0; from a~out 1% to about 20% by weightof a detergent compound selected from the group consisting of anionic, semipolar and zwitterionic surfactants; and from about 30 to about 70~ by weight of a detergency builder selected from the group consisting of organic and inorganic builder saits.
The composition herein can be employed singly to remove oils and oily soils from sur~aces by contacting same with an aqueous solution containing from about 0.02 to about 0.50% by weight of said compositions. ~oreover, the compositions herein can be added to both buil~ and unbuilt commercial-type detergent compositions in the ratios and proportions hereinafter disclosed to enhance the oil removal properties of said commercial detergent compositions.
DESCRIPTION OF T~IE DRAWING
The Figure herewith is a graphical illustration of the solubilization of dodecane in water by a typical mixture of a pure long-chain surfactant and a pure short-chain co-surfactant of the type employed herein. The Figure illustrates the synergistic solubilization effects which are achieved by proper selection of surfactant: co-surfactant ratios, and similar effects are noted for B

1~373~7 thc other mixtu.r~s herein, Moreover, the most strik.ing visual improvements in oily soil fabric deter~ency with both fat-ty and hydrocarbon soils parallels the dodecane solubilization and is optimum (for the specific mixtures of the Figure) within the range of points A and B, as shown.

DESCRIPTION OF T~E PREFERRED EMBODIMENTS
The oil solubilization and detergent additive compositions herein comprise two essential ingredients, a long-chain alkoxylated nonionic surfactant and a short-chain alkoxylated nonionic co-surfactant. While not intending to be limited by theory, it appears that the co-surfactant :
employed herein must be selected to provide rapid transport from the aqueous liquor into the oil which is to be removed from the surface being treated. Once established in the oil .. :
phase, the co-surfactant and surfactant twhich remains sub-stantially in the aqueous phase) co-act to produce a zero interfacial tension at the water-oil interface. A positive interfacial free energy is created and this force causes . :
the oil to disperse and dissolve in the aqueous liquor, thereby removing said oil from the surface.
While many surface active agents presumably will migrate from a water phase into an oil phase on long standing, they are kinetically slow, and are not useful in the relat-ively short time ~ca. 10-15 minutes) available in the :
deterging cycle of a home laundry operation or in hard surface cleaning. Moreover, surface active agents which do migrate relatively quickly will not, by themselves, cause the requisite lowering of the water-oil interfacial tension to provide a driving force for the formation of thermo-dynamically stable micellar solution (with the oil truly .~_ ......................... . .. ._.. ..... . . . .

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

:l~D373;37 solubilized). It is only when the proper combination of surfactant and co--surfactant is selected that rapid and effective solubili~ation of oil occurs.
From the foregoing it is seen that both thermo-dynamic and kinetic factors must be considered when formulating oil-dissolving compositions for use in aqueous media. It has been discovered that, by selecting alkoxylated nonionic surfactants of the type disclosed herein having the proper hydrophilic-lipophilic balance and combining them with alkoxylated nonionic co-surfactants of the type disclosed herein having the proper hydrophilic-lipophilic balance to provide mixtures having the proper overall hydrophilic-lipophilic balance, both the kinetic and thermodynamic requirements of a through-the-wash oil solubilizing detergent are satisfied.
MIXTURE COMPONENTS

.
The individual surface active agents employed in the mixtures herein are well known and are commonly thought of as constituting a hydrocarbyl chain condensed with an alkylene oxide chain. The hydrocarbyl portion of such materials gives rise to their lipophilic characteristics, whereas the alkylene oxide portion determines their hydrophilic characteristics. The overall hydrophilic-lipophilic characteristics of a given hydrocarbyl-alkylene oxide condensate are reflected in the balance of these two factors, i.e., the hydrophilic-lipophilic balance (HLB). The ~LB
of alkoxylated nonionics can be experimentally determined in well known fashion, or can be calculated as described more fully hereinafter. Conversely, specifying the alkoxyl content and the HLB of a hydrocarbyl alkoxylate fully ,: . ~: .. : :

~037337 charact~riz~s such compouncls since the hydrocarbyl content of the molecule can be approximatecl by reverse-calculation.
Alkoxylated nonionic surface active a~ents of the type used herein can be prepared by methods well known in the art. In general terms, a hydrocarbyl material having at least one -0~1 group is condensed with one or more moles of an alkylene oxide, e.g., ethylene oxide or propylene oxide.
Mixed alkoxylates can be formed by condensing the hydro-carbyl compound with mixtures of alkylene oxides, e.g., mixtures of e~hylene oxide and propylene oxide. The common terminology employed to designate the structures of such materials usually specifies both the nature of the hydrocarbyl group and the degree and type of alkylene oxide substitution. For example n-ClOEO(9), a preferred long-chain surfactant herein, is n-decanol condensed with 9 moles of ethylene oxide per mole of alcohol. Likewise, n-ClOEO(3), a preferred short-chain co-surfactant herein, is n-decanol condensed with 3 moles of ethylene oxide per mole of alcohol. An example of a mixed alkoxylate is ~0 CloEO(3)PO(2), wherein "PO" is the propylene oxide moiety.
The nonionic alkoxylates used herein both as surfactants and co-surfactants can be prepared from all manner of hydroxylated hydrocarbyl materials such as branched chain and straight chain alcohols and alkylphenols;
primary, secondary and tertiary alcohols; olefinic alcohols and the like, having the requisite number of carbon atoms disclosed herein. Glycols and poly-ols can also be used, but monohydric alcoholic and monohydric alkyl phenolic alkoxylates are preferred, with said alcohol alkoxylates being most preferred. Again, the names of such compounds g _ ~ _ . . . _ . , _ . . . . _ _ . .: . .

-103~337 often reflects the nature of bottl the hydrocarbyl group and the nature and molecular proportions of the alkylene oxide group. For example, Tergitol 15-S-9 is the commercial name of a preferred long-chain surfactant herein whlch is -the condensate of 9 moles of ethylene oxide with one mole of a secondary monohydric alcohol averaging 13 carbon atoms in ; length. Tergitol 13-S-5, which is a preferred short-chain co-surfactant herein, is the condensate of 5 moles of ethylene oxide with one mole of a C12 (avg.) secondary monohydric alcohol.
The long-chain surfactants used in the present compositons and processes are characterized by a hydro-philic chain of at least 5 alkylene oxide groups and an HLB
in the range of from 11.7 to about 17. The short-chain co-surfactants herein are characterized by a hydrophilic chain of 5 or less (preferably 2-4) alkylene oxide groups and an HLB in the range of from 7 to about 10.5. As noted, the carbon content of the lipophilic hydrocarbyl portion of the alkoxylated nonionic surfactants and co-surfactants can be approximately re~erse-calculated when the HLB and degree o alkoxylation are as specified~
A. Surfactant Component The term "long-chain" alkoxylated nonionic surfactant herein encompasses the hydrocarbyl alkylene oxide condensates of the formula:
R-O-(cyH2yo)a~(czH2zo)b Cw 2w wherein R is selected from the group consisting of primary, secondary and branched chain (primary and secondary) alkyl hydrocarbyl moieties; primary, secondary and branched chain (primary and secondary) alkenyl hydrocarbyl moieties; and ~o 3~ 33!;~
primary, secondary alld branch~d chain al]cyl- and alkenyl-substituted phenolic hydrocarbyl moieties, and having an HLs in the range disclosed hereinabove. In the general formula for the surfactants herein, y and z are each integers of from 2 to 3, preferably 2, and w is an integer of from

2 to 3, preferably 2.
In the genera~ surfactant formula, the carbon content of group R will vary somewhat, depending on whether R represents a primary or secondary alcohol or an alkyl- or alkenyl-phenolic group. When R is a primary alcohol, its carbon content is in the range of C8-C15, preferably C10-Cl3. When R is a secondary alcohol, its carbon content is in the range of Clo-C15, preferably C10 13 an alkyl phenol group, the carbon content of the alkyl portion is in the range of 7-9, preferably 8, carbon atoms.
Chain branching and points of unsaturation have no sub-stantial effect on the specified carbon content of group R.
In the general surfactant formula, a and b are each integers of o to about 11, the sum of a + b being in the range of from 4 to about 11. The formula of the surfactants encompasses ethylene oxide (EO) as well as mixed EO-PO alkoxylates, all of which are useful herein. The all-PO surfactants do not have the requisite HLB's and are not contemplated for use herein. The EO alkoxylates are preferred by virtue of their cost and availability.
Of course, by defining the hydrocarbyl content of group R and the HLB, the degree of alkoxylation (i.e., the sum of a + b) is necessarily defined. Again, however, this will vary somewhat, depending on the nature of R. For the preferred all-EO surfactants herein, when R is a primary '. .
. , ,' ' ' ~ , , ., ~ .

~37;~3'7 ~lcohol moiety, the sllm of a ~ b is ~~10 (preEerably 6-9) and the overall ethoxylate range i5 5-11, due to the presence of the terminal group in the hydrophilic portion of the molecule. When R is a secondary alcohol, the sum o~ a + b is 5-11 (preferably 6-9). When R is an alkyl phenol, the sum of a + b is 5-11 (preferably 6-9). When mixed Eo-Po surfactants are employed, the values of a and b can be calculated by assigning the disclosed hydrocarbyl ranges of R, the overall I~LB values, and by using hydrophilicity values for EO and PO groups obtainable Erom standard tables.
Specific examples of long-chain surfactants useful herein are as follows. The examples are only by way of exemplification and are not intended to be limiting of such materials.
~ i) Straight-chain, primary alcohol alkoxylates -. . . ~
The penta-, octa-, nona-, deca-, and undeca-alkoxylates of n-octanol, n-decanol, n-dodecanol, n-tetra-decanol, and n-pentadecanol having an HLB within the range recited herein are useful surfactants in the context of this invention; the respective ethylene oxide condensates are the most preferred alkoxylates. The n Cg_llEOn condensates are preferred. Exemplary alkoxylated primary alcohols - useful herein as the surfactant component of the mixtures are: n-ClOEO(6); n-ClOEO(9); n CllEO(9);
n-cl2EO(9); n-C14EO(10); n-ClOEO(10); n-CgEO(9); n-C15EO(ll);
and n-ClOEO(6)PO(2). The most preferred pure, straight chain, primary alcohol alkoxylates herein are n-clOEO(6) and n-CloEO(9).

' - , ,', .: ~ . :

1q~3'~'~3~7 (ii~ str.~glt-cha_n,_ econdary alcohol _lkoxylates -The hexa-, hepta-, oc~a-, nona-, cleca-, and undeca-alkoxylates of 2-decanol, 2-undecanol, 3-dodecanol, 2-dodecanol, 4-tridecanol ancl 2-pentadecanol haviny an HLs within the range recited herein are useful surfactants in the context of this invention; the respective ethylene oxide condensates are the most preferred alkoxylates. Exemplary alkoxylated secondary alcohols useful herein as the surfactant component of the mixtures are: 2-CloEO(9); 2-C12EO(9); 2-C14EO(10);
2-C15EO(11); 4-CloEO(9); 2-C15EO(12); and 2-CloEO(9)PO(3).
Preferred straight chain, secondary alcohol alkoxylates herein are the materials marketed under the trademark Tergitol 15-S-9 and Tergitol 15-S-7, which comprise a mixture of secondary alcohols having an average hydrocarbyl chain length of 13 carbon atoms condensed with an average of 9 ~ .
and 7 moles of ethylene oxide per mole equivalent of alcohol, respectively.
(iii) Alkyl phenolic alkoxylates -_ As in the case of the secondary alcohol alkoxylates, the hexa-through undeca-alkoxylates of alkylated phenols, ~
particularly monohydric alkylphenols, having an HLB within ~ -the range recited herein are useful as the surfactant compo-nent of the instant mixtures. The respective ethylene oxide condensates are the most preferred alkoxylates. The hexa-through undeca-alkoxylates of p-hexaphenol, m~octylphenol, p-octylphenol, p-nonylphenol and the like are useful herein;
most preferred are the ethoxylates of p-octylphenol and p-nonylphenol, inasmuch as these materials are readily available. Exemplary alkoxylated alkyl phenols useful as the surfactant component of the mixtures herein are: -~1~373~7 p-octylphenol EO(9); p-nonylphenol EO(9); p-dccylphenol EO(9);
p-dodecylphenol EO(10); and p-octylphenol Eot9)P0(2). The most preferred alkylphenol alkoxylates herein are p-octyl-phenol (nonoxyethylene) and p-nonylphenol (nonoxyethylene).
(iv) Olefinic alkoxylates -The alkenyl alcohols, both primary and secondary, and alkenyl phenols corresponding to those disclosed immed-iately hereinabove can be alkoxylated to an EILB within the range recited herein and used as the surfactant component of the instant mixtures. Typical alkenyl alkoxylates herein are 2-n-dodecenol EO(9); 3 n-tetradecenol EO(9); p-(2-nonenyl)-phenol EO(9)PO(2); and 2-tetradecen-4-ol EO~9).
(v) Branched chain alkoxylates -sranched chain primary and secondary alcohols which are available by the well known "OXO" process can be alkoxy-lated and èmployed as the surfactant component of mixtures herein. Exemplary branched-chain alkoxylates are as follows:
2-methyl-1-dodecanol EO(9); 3-ethyl-2-tetradecanol EO(9);
2-methyl-1-tetradecanol EO(9)PO(2) and the like. The ethylene oxide condensates of branched-chain alcohols having HLB's within the range specified for the surfactant component of the instant mixtures are preferred herein. Most preferred branched chain alkoxylates are commercial mixtures known as Dobanol 91-5, 91-6 and 91-8.
B. Co-Surfactant Component The term "short chain" alkoxylated nonionic co-surfactant herein encompasses the hydrocarbyl alkylene oxide condensates of the formula:
R -o-(CyH2yo)~(czH2zo)~-cwH2woH

.

3Lal37;~
herein ~ ls selected from th~ group consisting of primary, secondary and branched chain (primary and secondary) alkyl hydrocarbyl moieties; primary, secolldary and branched chain (primary and secondary) alkenyl hydrocarbyl moieties; and primary, secondary and branched chain alkyl- and alkenyl-substituted phenolic hydrocarbyl moieties, and having an HLs in the range disclosed hereinabove. In the general formula for the co-surfactants herein, y and z are each integers of from 2 to 3, preferably 2, and w is an integer of from 2 to

3, preferably 2.
In the general co-surfactant formula, the carbon content of group Rl will vary somewhat, depending on whether R represents a primary or secondary alcohol or an alkyl- or alkenyl-phenolic group. When Rl is a primary alcohol, its carbon content is in the range of C8-Cll, preferably Cg-Cll, most preferably C10. When Rl is a secondary alcohol, its carbon content is in the range of C10-Cl5, preferably C10-Cl3.
When R is an alkyl phenol group, the carbon content of the alkyl portion is in the range of 7-8, preferably 7, carbon atoms. Chain branching and points of unsaturation have no substantial effect on the specified carbon content of group Rl : .
In the general co-surfactant formula ~ and ~ are each integers of 0 to about 4, the sum of ~ + ~ being in the range of from 1 to about 4. The formula of the co-surfactants encompasses ethylene oxide (EO) as well as mixed EO-PO
alkoxylates, all of which are useful herein. The all-PO
surfactants do not have the requisite HLB's and are not contemplated for use herein. The EO alkoxylates are pre-ferred by virtue of their cost and availability.
~ 15 -.

~37337 Of course, by defining the hydrocarbyl content o~
group Rl and the ~ILB, the degree o~ alkoxylation (i.e., the sum of ~ + ~) is necessarily defined. Again, however, this will vary somewhat, depending on the nature of Rl. For the preferred all-EO surfactants herein, when Rl is a primary alcohol moietv, the sum of ~ + ~ is 1-3 (preEerably 2) and the overall ethoxylate range is 2-4, due to the presence of the terminal group in the hydrophilic portion of the molecule.
When Rl is a secondary alcohol, the sum of ~ + ~ is 1-4 (preferably 2-4). When R is an alkyl phenol, the sum of + ~ is 2-4 (preferably 3-4). When mixed EO-PO co-sur~actants are employed, the values of ~ and ~ can be calculated by assigning the disclosed hydrocarbyl ranges of Rl, the overall HLB values, and by using hydrophilicity values for EO and PO groups obtainable from standard tables.
Specific examples of short-chain co-surfactants useful herein are as follows. ~he examples are only by way of exemplification and are not intended to be limiting of such materials.
(i) Straight-chain, primary alcohol alkoxylates -----The di-, tri-, tetra-, and penta-alkoxylates of n-octanol, n-nonanol, n-decanol, and n-undecanol having an HLB within the range recited herein are useful co-surfactants in the context of this invention; -the respective ethylene oxide condensates are the most preferred alkoxylates.
Exemplary alkoxylated primary alcohols useful herein as the co-surfactant component of the mixtures are: n-C8EO(2);
n-C8EO(3); n-CgEO(3); n-ClOEO(3); n-CllEO(3); n-ClOEO(4);
n-ClOEO(3)PO(l); and n-ClOEO(2)PO(2). The most preEerred straight chain, primary alcohol alkoxylate co-surfactant r ~
. ~03~d~3;~7 herein is n-Cl oEO ( 3 ) .

tii) Straight-chain, secondary alcohol alkoxylates -, ~
The di-, tri-, tetra- and penta-alkoxylates of 2-nonanol, 3-decanol, 2-decanol, 3-tetradecanol, and S-penta-decanol having an HLB within the rarlge recited herein are useful co-surfactants in the context: of this invention:
the respective ethylene oxide condensates are the most preferred alkoxylates. Exemplary alkoxylated secondary alco-hols useful herein as the co-surfac-tant component o~ the 10 mixtures are: 2-CloEO(3); 2-C12Eo(5j; 2-CgEO(2); 2-CloEO(2)-PO(2); and 2-C12EO(3)PO(l). A highly preferred straight-chain, secondary alcohol alkoxylate herein is the material marketed under the tradename Tergitol 13-S-5, whi.ch comprises a mixture of secondary alcohols having an average hydrocarbyl chain length of 12 carbon atoms condensed with an average of 5 moles of ethylene oxide per mole equivalent of alcohol.
(iii) Alkyl phenolic alkoxylates -As in the case of the alcohol alkoxylates, the di-through penta-alkoxylates of alkylated phenols, particularly monohydric alkylphenols, having HLs's within the ranges recited herein are useful as the co-surfactant component of the mixtures herein. The respective ethylene oxide conden~
sates are the more preferred alkoxylates. The di- through penta-alkoxylates of p-heptylphenol, m-octylphenol, p-octylphenol, and the like are useful herein;
most preferred are the alkoxylates of p-octylphenol, inasmuch as this material is readily available. Exemplary ~ ~ ;
alkoxylates of alkyl phenols useful as the co-surfactant component of the mixtures herein include: p-octylphenol EOt3);

p-heptylphenol EO(3); p-octylphenol EO(5); p-octylphenol EO(4);

__.... . . .

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

~037337 and p-octyluhel)ol ~0(5)PO(2). The most preferred alkyl phenol alkoxylat~ co-surf~ctant herein is p-octylphenol EO(5) .
tiv) Olefinic alkoxylates -. .
The alkenyl alcohols, both primary and secondary,and alkenyl phenols corresponding to those disclosed immed-iately hereinabove can be alkoxylated to an HLs within the range recited herein and used as the co-surfactant component of the instant oil solubilizing mix-tures. Typical alkenyl alkoxylates useful herein are 2-n-decanol EO(3); 2-penta-decen-4-ol EO~5); and p~(2-octenyl)phenol EO(3).
(v) Branched-chain alkoxylates -Branched-chain primary and secondary alcohols which are available by the well-known "OXO" process can be alkoxy-lated to an HLB within the co-surfactant range noted herein and employed in -the instant mixtures. Exemplary branched-chain alkoxylated co-surfactants are as follows: 2-methyl-1-dodecanol EO(3); 3-ethyl-2-decanol EO(3); 2-methyl-1-decanol EO(3)PO(l) and the like. The ethylene oxide condensates of branched-chain alcohols are preferred herein.
The foregoing alkoxylates can be employed herein ~ -as the pure compounds or as mixtures. When prepared on a commercial scale, the alkoxylates are usually not the individual pure compounds listed, but rather comprise mixtures having an average degree of alkoxylation and average lipophilic hydrocarbon chain length corresponding to the ranges disclosed herein for the surfactants and co-surfactants. Moreover, fractional average values for the - alkoxylates occur in such mixtures, i.e., mixtures such as n-C10 5(EO)3 5. Such mixtures are fully contemplated for use herein.

.

. . .

~373~7 Commerclal mixtures oE the co-surfactants herein often contain portions of the non-alkoxylated parent alcohols or phenols, together with varying amounts of the mono-alkoxylated alcohols or phenols. It is preferred herein to "strip" the co-surfactants of these non-alkoxylated and mono-alkoxylated materials, inasmuch as they do not contribute to detergency performance in a significant way and have odor problems associated wi-th them. The stripping can be achieved by standard distillation procedures to provide preferred stripped co-surfactant mixtures containing less than about 3 by weight of the non- and mono-alkoxylated nonionics.
The compositions herein comprise mixtures of the aforesaid surfactants and co-surfactants. Such mixtures are characterized as having an HLB in the range of from 9 to 13.
The HLB' s of the surfactants, co-surfactants and mixtures herein can be calculated in the manner set forth in Becker, ;
"Emulsions Theory and Practice" Reinhold 1965 pp. 233 and 248. For example, the equation:
. ~ :
HLB = E/ 5 20 wherein E is the weight percentage of oxyethylene content, ~.
can be used to calculate the ~LB of the normal fatty alcohol ;~
ethyoxylates employed herein. -~
For mixtures of surfactant (A) and co-surfactant (B), the composite HLB is calculated as follows:
HLB (mi~) = wt. fraction A x HLBA +
wt. fraction B x HLBB.
Alternatively, the weight fraction of the co-surfactant which must be used with a given surfactant to provide a mixture having an EILB within the range recited herein can be calculated as follows:

. .
.
:. . - .. . . , . . . : . .

~u~

wt. fraction EILB surf. HLB mixt.
co-surfactant HLB surf. HLB co-surf.
On the basis of the foregoing, i-t is po~sible to calculate the weight of short chain co-surfactant of the type disclosed herein which must be combined with the long chain surfactant of the type disclosed herein to provide a mixture having a mixture HLs within the required range.
Moreover, such mixtures will provide an interfacial tension at a hydrocarbon/water interface of essentially zero. Accord-ingly, such compositions effect the solubilization of oilin aqueous media with rapid kinetics.
~ Oil solubili7ing mixtures of surfactant and co-- surfactant can be determined experimentally by measuring : .
the ability of test mixtures to provide a clear, aqueous ~-solution or clear dispersion of n-dodecane in water. In a typical procedure, n-dodecane is added to a 0.36 (wt.) aqueous solution of the surfactant/co-surfactant mixture at a ratio of said mixture:n-dodecane of about 1:0.5 to 1:1, ` with stirring. Stirring is continued for 30 minutes and the results observed visually. Under these test conditions, the mixtures herein result in a micellar solution (or clear stable dispersion) of the n-dodecane in water (sometimes - referred to as a "microemulsion") whereas other detergent systems result in a- cloudy emulsion, or unstable dispersion j of n-dodecane in water.
An alternate procedure for determining surfactant/
co-surfactant mixtures of the type disclosed herein comprises evaluating their ability to remove dirty motor oil (auto-mobile crankcase oil) from cloth swatches. In a typical test, 0.01 ml. of dirty motor oll is placed on a fabric, -.

~L03~3~7 which can be cotton, polyester or b:Lends. The swatch is then laundered in water at 100F to 140F containing 0.02 to 0.05~ of the mixtures herein. The oil removal is then evaluated visually, or by means of a Gardner meter. Typical mixtures herein remove up to 98~ of the dirty motor oil, whereas other detergent systems result in little, or no, oil removal.
Non limiting examples of preferred nonionic mix-tures herein appear in Table I.

: ~ ' .

.~
: :

:'.

-~373;3~7 T Lr. I
Mixture Components (wt.~) ~IL~ Mixture , 65% n-ClO(EO)3, 35~ n C10( 9 10.9 50% n-Clo(EO) 3, 50~ n-C'lO(EO)6 10.8 55~ n-ClO(Eo)3, 45~ TergitOl* 15-S-9 11.0 35% n-ClO(Eo)3, 65~ Dobanol** 91-5 10.8 50~ n-ClO(EO)3, 50% Dobanol 91-6 10.8 60~ n-ClO(EO)4, 40~ Tergitol 15-S 7 80~ stripped n-ClO(EO)3, 20% Tergitol 15-S-9+ 11.0 10 80% stripped Dobanol 91-3, 20% Tergitol 15-S-9 11.0 80% stripped Dobanol 91-3, 20~ Dobanol 91-6 10.9 65~ stripped n-C10(EO)2, 35% Tergitol 15-S-g+ 10.9 55% Tergitol 15-S-5, 45% Tergitol 15-S-9 11. 7 30% Tergitol 15-S-3, 70% Tergitol 15-S-9 11.7 25~ Tergitol 15-S-5, 75% Tergitol 15-S-7 11.7 30~ Tergitol 13-S-3, 70% Tergitol 15-S-9 11.8 55% Tergitol 13-S-5, 45% Tergitol 15-S-9 11.9 55% Tergitol 13-S-5, 45% Tergitol 13-S-9 11.8 * Tergitol is the trademark for alkoxylates of secondary alcohol mixtures. Tergitol 13 is based on a C -C 3 alcohol with an average hydrocarbon chain leng~h o~ 12; ~-Tergitol 15 is based on a Cl -C15 alcohol mixture with an average of 13 carbon atom~ in the chain. The S-3, S-5, S-7 and S-9 designations indicate an average degree of ethoxylation of 3, 5, 7 and 9, respectively.
** Dobanol is the trademar]c for alkoxylates of primary "oxo"
alcohol having an average alcohol molecular weight of 160.
The alcohols used to prepare the Dobanol alkoxylates are primarily Cg-Cll, with the major proportion being C10.
The final integers 3, 5 and 6 with the Dobanols indicates average degrees of ethoxylation of 3, 5 and 6, respectively.
+ Highly preferred based on performance and availability.

~L03~
Tlle ~orec~oing optimized mixtures can be used singly to clean and degrease fabrics, metals and other hard surfaces.
Alternatively, the mixtures can be employed as oil solubiliza-tion systems which can optionally be combined with adjuvant materials, as disclosed hereinafter.
The surfactants and co-surfactants employed herein can be prepared, for example, in the manner disclosed in U.S. Patent 2,164,431. Mixe~ materials, e.g., EO-PO surfac-tants and co-surfactants, can be prepared as described in 10 U.S. Patent 3,650,965. The Tergitol 13-S-5 and Tergitol 15-S-9 materials are available from the Union Carbide ` -Corporation. The Dobanols are available from the Shell Chemicals U.K. Ltd. U.S. Patent 2,355,823, teaches the preparation of secondary alcohol alkoxylates. U.S. Patent 2,508,035, teaches the preparation of branched chain secondary alkoxylates. U.S. Patent 2,508,036 teaches the preparation of branched chain primary alkoxylates. The a1koxylated phenolic alkoxylates are available from various commercial sources.
OPTIONAL DETERGENTS AND ADJUVANTS
As noted, the nonionic mixtures of the instant invention can be employed in a variety of compositions and processes where solubiiization of oil or grease is desired.
The most common situation calling for oil and grease solub-ilization is in the area of stain removal from fabrics during aqueous laundering operations. The instant nonionic oil solubilization systems can be utilized alone for fabric stain laundering, but are more commonly employed in combina-tion with other conventional detergent formulation materials.
Such optional materials include, for example, conventional ., ,; . ; , . . : :. :

~373~
surfactants and builders. The Eollowing list of suchdetergent adjuvants which can be used in combination with the alkoxylated nonionic long chain surfactant-plus-short - chain co-surfac-tant mixtures is typical of such adjuvant - materials, but is not intended to be limiting.
Detergents _ _ Optional detergents useful in the embodiments of the present invention include all manner of anionic, semi-polar, zwitterionic and amphoteric organic, water-soluble detergent compounds, inasmuch as the nonionic mixtures herein are compatible with all such materials. A typical listing of the classes and species of detergent compounds useful herein appears in ~.S. Patent 3,664,961. Compositions comprising from about 1% to about 99% (preferably 15~ to 40~) -by weight of the alkoxylated surfactant mixtures herein and from about 1% to about 60% (preferably 1-~ to 20~) of one or ~ -more optional detergent components are especially useful as heavy duty cleaning compositions. The following list of detergent compounds and mixtures which can be used in the instant compositions and processes is representative of such materials, but is not intended to be limiting.

-Water-soluble salts of the higher fatty acids, i.e., "soaps" àre useful as an optional detergent component herein. This class of detergents includes ordinary alkali metal soaps such as the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids containing Erom about 8 to about 24 carbon atoms and preferably from about 10 to about 20 carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Particularly useful are the sodium and - 2~ -~03733'~
potassium salts of thc mixtures of fatty acids derived fromcoconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
Another class of deteryents includes water-soluble salts, particularly the alkali metal, ammonium and alkylol-' a~nonium salts, of organic sulfuric reaction products having ' in their molecular structure an alkyl group containing from ~
about 8 to about 22 carbon atoms and a sulfonic acid or ~ 5 sulfuric acid ester ~roup. ~Included in the term "alkyl"
` 10 is the alkyl portion of acyl groups.) Examples of thisgroup of synthetic detergents which can be used in the ~' present invention are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C8 ~ C18 carbon atoms) produced by reducing the glycerides of tallow or coconut oil; and sodium and potassium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or ~ ' branched chain configuration, e.g., those of the type described in U.S. Patents, 2,220,099 and 2,477,383. Especially valuable are linear straight chain alkyl benzene sulfonates in which the average of the alkyl groups is about 13 carbon atoms, abbreviated as C13LAS.
Other anionic detergent'compounds herein include the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; and sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain about 8 to about 12 carbon atoms.

~, ~

~IV3~3~7 Seml-E~olar deterc3ents useful h~rei,n include water-soluble amine oxid~s con-taining one alkyl moiety of from about 10 to 28 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydrox~alk~l groups containing ~rom 1 to about 3 carbon atoms; water-soluble phosphine oxide detergents containing one alkyl moiety of about 10 to 28 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about l to 3 carbon atoms; and water-soluble sulfoxide detergents containing one alkyl moiety of from about 10 to 28 carbon atoms and a moiety selected ~ro~ the group consisting of alkyl and hydroxyalkyl moieties of from l to 3 carbon atoms.
Ampholytic detergents include derivatives of ;~
aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the a,liphatic substituents contains from about 8 to l~ carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
Zwitterionic detergents include derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds in which the aliphatic moieties can be straight ~ ' chain or branched, and wherein one of the aliphatic sub- ~ ' stituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubillzing group.
Other useful detergent compounds herein include the ' ' water-sol'uble salts of esters of ~-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty , acid group and from about l to 10 carbon atoms in the ester .- . . . . . . .
. : :;: . . . :. . .
,:: -. . ~ . .- . ~ . .

~L~373~Y7 group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about ~ to about 23 carbon atoms in the -alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; 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.
Preferred water-soluble organic detergent compounds - herein include linear alkyl benzene sulfonates containing from about 11 to 14 carbon atoms in the alkyl group, the tallow range alkyl sulfates, the coconut range alkyl glyceryl sulfonates; alkyl ether sulfates wherein the alkyl moiety :
contains from about 14 to 18 carbon atoms and wherein the average degree of ethoxylation varies between 1 and 6; the sulfated condensation products of tallow alcohol with from about 3 to 10 moles of ethylene oxide; olefin sulfonates containing from about 14 to 16 carbon atoms; alkyl dimethyl amine oxides wherein the alkyl group contains from about 11 to 16 carbon atoms; alkyldimethyl-ammonio-propane-sulfonates and alkyl-dimethyI-ammonio-hydroxy-propane-sulfonates wherein the alkyl group in both types contains from about 14 to 18 carbon atoms; and soaps, as hereinabove defined.
Specific preferred detergents for use herein include:
sodium linear C10 - C18 alkyl ben2ene sulfonate; triethano-lamine C10 - Cl~ alkyl benæene sulfonate; sodium tallow alkyl sulfate, sodium coconut alkyl glyceryl ether sulfonate; the sodium salt of a sulfated condensation product of a tallow -: - , ~ . . .

1~3Y~33'7 alcohol with from about 3 to about 10 moles of ethylene oxide;
- 3-tN,N-dimethyl-N-coconutalkyl-ammonio)-2-hydroxypropane-1-sulfonate; 3-(N,N-dimethyl-N-coconut-alkylammonio)-propane-l-sulfonate; 6-(N-dodecyl-benzyl-N,N-dimethylammonio)hexanoate;
dodecyl dimethyl amine oxide; coconut alkyl dimethyl amine oxide; 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.
Examples of preferred detergent mixtures herein are as follows.
An especially preferred alkyl ether sulfate deter-gent component useful in the instant compositions and processes is a mixture of alkyl ether sulfates, said mixture having an average (arithmetic mean) carbon chain length within the range of from about 12 to 16 carbon atoms, preferably from about 14 to 15 carbon atoms, and an average (arithmetic mean) degree of ethoxylation of from about 1 to

4 moles of ethylene oxide, preferably from about 2 to 3 moles of ethylene oxide.
Specifically, such preferred mixtures comprise from about 0.05% to 5% by weight of mixture of C12 13 com-pounds, from about 55% to 70~ by weight of mixture of C14 15 compounds, from about 25% to 40~ by weight of mixture of C16 17 compounds and from about 0.1~ to 5~ by weight of mixture of C18 19 compounds. Further, such preferred alkyl ether sulfate mixtures comprise from about 15% to 25% by weight of mixture of compounds having a degree of ethoxylation of 0, from about 50% to 65% by weiyht of mixture of compounds having a degree of ethoxylation from 1 to 4, from about 12%

; ~3~337 to 22~ by weight of mixture of compounds having a degree ofethoxylation from 5 to 8 and from about 0.5~ to 10~ by weight of mixture of compounds having a degree of ethoxy-lation greater than 8.
Examples of alkyl ether sulfate mixtures falling within the above-specified ranges are set for-th in Table II.

.. . . .
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.
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E~ ~ ~ ~ I` o;) ~I . a~ . ~
H H In ~ ~) ~1 11'1 ~ iZ
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~¢H 00 o~ o`~o\rA ~I a~ A Ao O~o ~H ' ~1 11~~)r-l . . U~ ~ ~1 (a t l H ~r ~D ~ ~1 (~I ~ ~-1 Z
U~ .

H _ __ _ _ ~ -H
p:; 00 U~ ~ ' :
I L~~1 ~ o\ r,\o o\ O\o ~ o\O o\ 0\ ~A /1~
1~1 p H ~1Ul t~ ~1 , ~I cn 1~ ~ Z ~7 ~ E~ H ~ ~ 7 t~ N 1~1 r l _ _ ., ~_ _ _....... _ . ~ , 1~1 ~D ~0 C~ o\O o\O o~O 0\o ~ o\ o\O o\O 0\0 H ~ 10 ~ Ll') . 11~ ~ ~I r~l ~;
.' ~ ~ Il') ~ ~1 r~ . ~:, __ _ .. __ . ., 0~o 0~o0~o 0~o ~ a~ a) . : ~
O ~) ~ ~ ~ X . ~ ~ .
H 3 3 3 3~ ^ r~ X X '~
E-l ~ ^ ~ _ _ _ ~ O ~1 0 0 X .
~n ~ a~ x o H (11 ~ U~ O a) a) p:; ~ O E~ 13 ~ ~ a ~ u ~ o .o o o o ~ ~
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c~ c~ æ ~ ~ æ au u~
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r~ ~ v t~ a~ u~
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:~c ~ ~ l l l l a~ o ~ ~-1 H ~ o ~ ~ ~D co ~ a 3 1 3 1 3 + 3 ~
~ ~ 1-1 . __ _ O-- r~ ~ V~

,................. . . .

:~03~33~7 Preferred "olefin sulfonat:e" detergent mixtures utilizable hereln comprise olefin sulfonates containin~ from about 10 to about 24 carbon atoms. Such materials can be produced by sulfonation of ~-olefins by means of uncomplexed sulfur dioxide followed by neutraliz:ation under conditions such that any sultones present are hydrolyzed to the corres-ponding hydroxy-alkane sulfonates. The ~-olefin starting materials preferably have from 14 to 16 carbon atoms. Said preferred a-olefin sulfonates are described in U.S. Patent 3,332,880.
Preferred a-olefin sulfonate mixtures herein consist essentially of from about 30% to about 70% by weight of a Component A, from about 20% to about 70% by weight of a Component B, and from about 2% to about 15% of a Component C, wherein (a) said Component A is a mixture of double-bond positional isomers of water-soluble salts of alkene-l-sulfonic acids containing from about 10 to about 24 carbon atoms, said mixture of positional isomers including about 10% to about 25% of an alpha-beta unsaturated isomer, about 30% to about 70% of a beta-gamma unsat-urated isomer, about 5% to about 25% of a gamma-delta unsaturated isomer, and abou-t 5%
to about 10% of a delta-epsilon unsaturated isomer;
(b) said Component B is a mixture of water-soluble salts of bifunctionally-substituted sulfur-containing saturated aliphatic compounds containing from about 10 to about 24 carbon . .

103~33'7 atoms, the functional units being hydroxy and sulfonate groups wi-th the sulfonate groups always being on the terminal carbon and the hydroxyl group being attached to a carbon atom at least two carbon atoms removed from the termi.nal carbon atoms at least 90~ of the hydroxy group substitutions being in 3, 4, and 5 positions; and (c) said Component C is a mixture comprising from about 30%-95~ water-soluble salts of alkene disulfonates containing from about 10 to about 24 carbon atoms, and from about 5% to about 70~ water-soluble salts of hydroxy disulfonates containing from about 10 to about 24 carbon atoms, said alkene disulfonates containing a sulfonate group attached to a terminal carbon atom and a second sulfonate group attached , - ~ ;to an internal carbon atom not more than about .::-six carbon atoms removed from said terminal -~ ~.
carbon atom, the alkene double bond being dis-tributed between the terminal carbon atom and about the seventh carbon atom, said hydroxy disulfonates being saturated aliphatic compounds ~
having a sulfonate group attached to a terminal --:
carbon, a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroxy group attached to a carbon atom ~hich is not more than about four carbon atoms removed from the site of ~3~3;~7 attachment o~ said second sulfonate group.
Adjuvan~ ~laterials The herein-disclosed compositions can contain, in addition to the nonionic mixtures and optional organic detergent compounds, all manner of detergency ~uilders commonly taught for use in detergent compositions. Such builders can be optionally employed in the present compositions at concentrations of from about 0% to about 90% by weight, preferably from about 30% to about 70~ by weight, of said optional builders. Useful builders herein include any of the conventional inorganic and organic water-soluble builder salts.
Such detergency builders can be, for example, water-soluble salts of phosphates, pyrophosphates, ortho-phosphates, polyphosphates, phosphonates, carbonates, polyhydroxysulfonates, silicates, polyacetates, carboxylates, polycarboxylates and succinates. Specific examples of - inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates and hexamethaphosphates. The polyphosphonates specifically include, for example, the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane l-hydroxy-l, l-diphosphonic acid and the sodium and potassium salts of ethane-1,1,2-triphosphonic acid. Es~amples of these and other phosphorous builder compounds are disclosed in U.S.
Patents 3,159,581; 3,Z13,030; 3,422,021; 3,422/137; 3,400,176 and 3,400,148.
Non-phosphorus containing sequestrants can also be selected for use herein as detergency builders.
Specific examples of non-phosphorus, inorganic . :, ~0373;3 7 builder ingredients include water-~oluble inorganic carbonate, bicarbonate, and silicate salts. The alkali metal, e.~., sodium and potassium, carbonates, bicar~onates, and silicates are particularly useful herein.
Water-soluble, organic builders are also useful herein. For example, the alkali metal, ammonium and sub-stituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates are useful builders in the present compositions and processes. Specific examples of the polyacetate and polycarboxylate builder 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.
Highly preferred non-phosphorus builder materials herein include sodium carbonate, sodium bicarbonate, sodium silicate, sodium citrate, sodlum oxydisuccinate, sodium mellitate, sodium nitrilotriacetate, and sodium ethylene-diaminetetraacetate, and mixtures thereof.
Other highly preferred builders herein are the polycarboxylate builders set forth in U.S. Patent 3,308,067, Diehl. Examples of such materials include the water-soluble salts of homo- and co-polymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, ~umaric acid, aconitic acidr citraconic acid and me-thylenemalonic acid.
Additional, preferred builders herein include the water-soluble salts, especially the sodium and potassiu~
salts, of carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexanehexacarboxylate, cis-cyclopentanetetracarboxy--: '. : . ~ , ~3733~
late and phloro~lucinol trisulfonate.
Another type of ~etergency builder material usefulin the present composltions and processes comprises a water-soluble material c~pable oE 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. Such "seeded builder" compositions are fully disclosed in the ~enjamin Canadian Patent 991,942.
More particularly, the seeded builders useful herein comprise a crystallization seed having a maximum particle dimension of less than 20 microns, preferably a particle diameter of fram about 0.01 micron to about 1 micron, in combination with a material capable of forming a water-insoluble reaction product with free metal ions.
Many builder materials, e.g, the water-soluble carbonate salts, precipitate water hardness cations, thereby performing a builder function. Unfortunately, many of the precipitating builders used in detergent compositions do not reduce the free metal ion content of laundry baths quickly, and such builders only compete with the organic detergent and the soil for the free metal ions.
The result is that while some of the free metal ions are removed from the solution, some ions do react with the organic detergent and the soil, thereby decreasing the deter-sive action. The use of the crystallization seed quickens the rate of precipitation of the metal hardness, thereby removing the hardness ions before they can adversely affect the detergency performance.

.;; . . - . .:; . ............ . . .
- .:. .

~3~ 7 By using a material capable of formin~ a water-insoluble product with free metal ions in combination with a crystallization seed, the combined free metal ion con-centration of an aqueous laundering liquor can be reduced to less tllan 0.5 grains of hardness within about 120 seconds.
In fact, the preferred seeded builders can reduce the free metal hardness to less than 0.1 grains/gallon within about 30 seconds.
Preferred seeded builders consist of: a water-soluble material capable of forming a reaction product having a solubility in water of less than about 1.4 x 10 wt.%
~at 25C) with divalent and polyvalent metal ions such as calcium, magnesium and iron; and a crystallization seed (0.001 20 micron diameter) which comprises a material which will not completely dissolve in water within 120 seconds at 25C.
Specific examples of materials capable of forming the water-insoluble reaction product include the water-soluble salts of carbonates, bicarbonates, sesquicarbonates, silicates, aluminates and oxalates. The alkali metal, especially sodium, salts of the foregoing materials are preferred for convenience and economy.
The crystallization seed employed in such seeded builders is preferably selected from the group consisting of calcium carbonate; calcium and magnesium oxalates;
barium sulfate; calcium, magnesium and aluminum silicates;
calcium and magnesium oxides; calcium and magnesium salts of fatty acids having 12 to 22 carbon atoms; calcium and magnesium hydroxides; calcium fluoride; and barium carbonate.
Specific examples of such seeded builder mixtures comprise:

., 1~3733~7 3:1 wt. mixtures of sodium car~onate and calcium carbonatehaving a 5 micron particle diameter; 2.7:1 wt. mixtures of sodium sesquicarbonate and calcium carbonate having ~
particle diameter of 0.5 microns; 20:1 wk. mixtures of sodium sesquicarbonate and calcium hydroxide having a particle diameter of 0.01 micron; and a 3:3:1 wt. mixture o~ sodium carbonate, sodium aluminate and calcium oxide having a particle diameter of 5 microns.
The compositions herein can optionally contain all manner of additional materials commonly found in laundering and cleaning compositions. For example, thick-eners and soil suspending agents such as carboxymethyl-cellulose and the like can be included in the compositions.
Enzymes, especially the thermally stable~proteolytic and lipolytic enzymes commonly used in high temperature laundry detergent compositions, can also be present herein.
Various perfumes, optical bleaches, fillers, anti-caking agents, fabric softeners and the like can be present to provide the usual benefits occasioned by the use of such materials in detergent compositions. Perborate bleaches commonly employed in European detergent compositions can also be present as a component of the compositions herein.
It is to be recognized that all such adjuvant materials are useful, inasmuch as they are compatible and stable in the -compositions herein.
The alkoxylated nonionic mixtures herein can be - used separately as detergent compositions, but are most often employed at a concentration of from about 5% to about 95% (preferably 8%-45%) by weight in combination with 0~ to 95% (preferably 55~-95%) by weight of a carrier. Liquid : :-......... . ............. .
~ , ' ~ , . . . ' ' ' ~C13 ~337 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 o~ 95:5 to 1:1 are especially preferred liquid carriers herein.
Solid, sorbent carriers for the present nonionic mixtures include any o~ the hereinabove disclosed water-soluble solid builder materials, as well as water-insoluble lO 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 for use in dry detergent compositions. The appropriate ratio will, of course, depend on the sorbency of the carrier, and can be readily determined experimentally.
The Wise British Patent 1,460,646, sealed rlay 4, 1977, discloses the use of kaolinite clay to provide a crutcher-stable nonionic surfactant/clay mixture suitable for use in the preparation of spray-dried detergent granules.
Kaolinite clay employed in this manner is a preferred water-insoluble carrier for preparing spray-dried detergent granules containing the nonionic mixtures of the present invention.
The followin~ examples illustrate various compo-sitions 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.

~0373~
EX ~lPLE I

A liquid oil dissolving composition is as follows:

Component Wt.~
., _ n-C10(EO)3 (stripped)* 80 Tergitol 15-S-9 20 *Stripping the unalkoxylated alcohols raises the average degree of alkoxylation to ca. 4.

The above composition is dissolved in water at a concentration of 0.11% by weight. Oily metal surfaces and oil-stained rags are cleansed by agitating same with the solution for periods of from about 1 minute to about 10 minutes, depending on the amount of oil to be removed.
In the above composition the nonionic mixture is replaced by the following mixtures: Tergitol 15-S-5/
p-octylphenol EO(9) 50:50 wt. ratio; n-C10EO(3)/n-C12EO(9) 60:40 wt. ratio; n-C8EO(2)~n-C10EO(9) 55:45 wt. ratio;
2-C10EO(3)/n-C10EO(9) 55:45 wt. ratio: p-hexylphenol EO(3)/

p-nonylphenol EO(9) 60:40 wt. ratio; and 3-ethyl-2-decanol (3)/3-ethyl-2-dodecanol(9) 55:45 wt. ratio, respectively, and oil solubili~ing compositions are thereby secured.

, . . . .

~03733 7 EXl~MPLE I I
, A granular detergent composition is formulated having the following composition.

Component Wt.%

Sodium silicate 86.0 (Na2O:SiO2 ratio 1:1.8;
Britesil (CA) n-ClOEO(3) 8.0 10 0(9) 6.0 The above composition is used in an aqueous sol-ution at a concentration of 0.12% wt. to launder fabrics.
The pH of the laundering liquor is 10.1. Improved hydro-carbon removal is secured; additionally, superior removal of lipid soils is noted.

, ' 4 0 - :

, . ' -1al3~933~7 EXArlPLE II.L

A spray-dried, granular detergent composition is as follows:

Crutcher Mix Ingredient Grams Sulfated tallow alcohol 2.0 Linear alkylbenzene sulfonate (alkyl = Cll 8 avg.) 2.0 Calcium carbonate (1.0 micron) 9.0 Sodi~ carbonate 30.0 Sodium sulfate 9.7 Sodium sulfosuccinate 2.0 Sodium toluene sulfonate 2.0 Sodium silicate (SiO2:Na2O = 2.0) 10.0 Water 45.0 Pre-Slurry Ingredient Grams Tergitol 15-S-9 9.0 Tergitol 13-S-5 11.0 Xaolinite clay (1.0 micron) 6.5 . .

: , . ,;,. . .

33~ .
~ l~he kaolinite~ clay ~nd the nonionic surfactants are admixed separately from the crut:cher mix as a pre-slurry at a temperature of 150F and blended thoroughly at this temperature for about 5 minutes until a smooth slurry is obtained. The crutcher mix ingredients are separately mixed and raised to a temperature of 150~. The hot kaolinite-nonionic slurry is then admixed witll the hot crutcher mix and blended. The resulting homogeneous crutcher mix is spray-dried at 200C to provide a granular detergent composition.
The foregoing composition is employed as a 0.1 aqueous solution and provides superior oil removal from polyester fabrics when laundered at 100F-110F.
In the foregoing composition the mixture of Tergitol 15-S-9 and Tergitol 13-S-5 is replaced by an equivalent amount of the other nonionic mixtures set forth herein in Table I, respectively, and equivalent results are secured.
In the foregoing composition, the anionic surfac-tant component of the crutcher mix comprising the sulfated tallow alcohol and the linear alkylbenzene sulfonate is replaced by an equivalent amount of sodium linear C10-Cl8 alkylbenzene sulfonate; triethanolamine C10-Cl8 alkylbenzene sulfonate; sodium tallow alkyl sulfate, sodium coconut alkyl glycerylether sulfona-te; the sodium salt of a sulfated condensation product of a tallow alcohol containing from about 3 to about 10 moles of ethylene oxide; 3-(N,N-dimethyl-N-coconutalkylammonio)-2-hydroxypropane-1-sulfonate; 3-(N,N-dimethyl-N-coconutalkylammonio)-propane-l-sulfonate; 6-(N-dodecylbenzyl-N,N-dimethylammonio)-hexanoate; dodecyl .,. . ~ ~, . . .

13~33~
dimethyl amine oxi~e; coconutalkyldimethyl amine oxide; andthe water-soluble sodium and potass:Lum salts of higher fatty acids containing 8 to 24 carbon atorns, respectively, and equivalent results are secured.
In the foregoing compositlon, the seeded builder comprising the mixture of sodium carbonate and calcium carbonate is replaced by a total of 40 grams of the following builders, respectively: sodium tripolyphosphate, sodium nitrilotriacetate; sodium citrate; sodium oxydisuccinate;
sodium mellitate; sodium ethylenediaminetetraacetate;
sodium carboxymethyloxymalonate; sodium carboxymethyloxy-succinate; sodium cis-cyclohexanehexacarboxylate; sodium cis-cyclopentanetetracarboxylate; and the sodium salt of phloroglucinol trisulfonate, respectively, and equivalent results are secured.
The foregoing compositions exhibit excellent removal of oll and clay soil from fabrics when employed in aqueous laundry baths at concentrations of 0.04~ (wt.), and greater. The compositions also provide excellent hard surface cleaners useful for scrubbing walls, floors and dishes.

~03~337 EXAMPLE IV

A spray-dried granular detergent composition prepared in the manner of this invention is as follows:

Ingredient Wt.%
Branch-chain alkylbenzene sulfonate (alkyl = C12 avg.) 20.0 Nonionic component consisting of 1:1 (wt.) mixture of n-ClO(Eo)3 and n C10( )6 Sodium tripolyphosphate 33.0 Sodium toluene sulfonate 2.0 ~ "
Carboxymethylcellulose 0.6 -Sodium sulfate 21.9 Kaolinite clay (0.5 micron diam.) 2.5 Sodium silicate (SiO2:Na20 = 2.0) 5.4 Colorants 0.1 Water 9~5 i ~; ,':

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

~3~3~7 The foregoing composition is prepared by pre-slurrying the kaolinite clay and the nonlonics at 150F
and admixing the pre-slurry with a crutcher mix comprising the remaining components set for-th, also at 150F. The resulting mix is spray-dried in a tower with an inlet air stream of 600F at about 300F to provide the detergent granules.

- 45 - :

. - . . . . . .

~CI 3733'~
E~~MPLE V

An unbuilt, heavy duty liquid detergent is formulated having the following composition:

Component Wt.%
~onionic oil solu~ilization system 33.0 comprising 80 wt.~ stripped n-Cl oEO ( 3) and 20 wt.% Tergitol Triethanolamine salt of linear 16.1 .
alkyl benzene sulfonic acid wherein the alkyl chain averages 12 carbon atoms in length , Triethanolamine (free form) 5.3 Ethanol 5.5 ~: -Potassium Chloride 2.5 Brighteners, Perfumes, Dye 1.2 Water Balance .

. :

.

;

... . .. . . . . . . .
::: ., , :: .
. . .

- ~.

~L~3~33~
The a~ove composition provides cxcellent removal of a wide variety of oily soils from cotton, polyester and polyester/cotton fabrics.
Substantially equivalent cleter~ency performance is realized when in the above-described composition the nonionic oil solubilization system i.s replaced by an equivalent amount of the other mixtures set forth herein in Table I, respectively.
In the foregoing composition the oil solubilization system is replaced by an equivalent amount of a mixture comprising 70 wt.% Tergitol 15-S-5 and 30 wt.% of a hepta-ethoxylate of a mixture of C14 15 primary alcohols, marketed as Dobanol 45-7 (total mixture EILB ca. 11), and equivalent results are secured.
, - ~7 -~037337 EXAMPLE VI
An automatic dishwashing detergent compos.ition prepared in the manner o~ this invention is as .Eollows:

Ingredient Grams Nonionic component* 25.0 Kaolinite clay (0.5 microns)15.0 .
Coconutalkyl EO(3) PO(6)** 2.0 Sodium tripolyphosphate 100.0 Sodium silicate 25.0 lO Potassium dichlorocyanurate 2.0 Water g.o ~ ~

* Comprising stripped n-ClO(EO)3 and Tergitol 15-S-9, ~ :-4:1 wt. ratio.
** Suds suppressing agent .

~03733~
~ e foregoiny composition is ~repared by admixing the nonionic component and kaolinite clay at a temperature of 150F and blending therewith the ethylene oxide-propylene oxide suds suppressing agent. The resulting mixture, at 150F, is admixed with the remaining components, also maintained at a temperature of 150F, -to provide a homo-geneous crutcher mix. The mix is sprayed through a drying tower to provide a homogeneous detergent composition especially adapted for use in automatic dishwashers.
As can be seen from the foregoing, detergent compositions in the manner oE the present invention com-prising from about 5% to about 100% (preferably about 8% to about 45%) by weight of thP surfactant/co-surfactant mixtures herein and from about 0% to about 95~ (preferably about 55%
to about 95%) by weight of a solid or liquid water-dispersible carrier, provide superior oil-dissolving detergent composi-tions for use in aqueous laundering baths. The mixtures herein can be added to commercial detergent formulations to impart improved oil removal properties thereto. Such compositions most preferably comprise from about 15% to about 40% by weight of the oil-dissolving mixtures herein, from about 1% to about 20% by weight of a detergent compound to optimize sudsing and to provide broad spectrum cleaning with a variety of fabrics and soil types, and, for heavy duty cleaning use, from about 30% to about 70% of detergency builders.
Fabric softener compositions comprising a major proportion of a quaternary ammonium surface active agent and minor amounts (ca. 1~) of alkoxylate mixtures are known in the art. When employed in such compositions, the .. : . . .~ - :

~373~7 alkoxylate mixtures act as emulsion stabilizers, rather than oil solubilizing agents. In contrast, the present composi-tions are characterized as being free from quaternary compounds.

,' ' :

.

Claims (9)

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

1. A granular detergent composition especially adapted for removing oil and oily soil from fabrics, said composition consisting essentially of:
a) from about 15% to about 40% by weight of an ethoxylated nonionic surfactant mixture of which about 60%-80% by weight of the mixture is a water soluble C9-C11 primary alcohol having an average of 10 carbon atoms in the alkyl chain condensed with an average of four ethylene oxide groups to give an HLB of about 10.5 and about 20%
to about 40% by weight of the mixture is the condensate of a secondary C10-C15 alcohol mixture having an average of 12-13 carbon atoms in the alcohol molecule with about 7-9 ethylene oxide groups to give an HLB of from 12.0-15.0, said surfactant mixture having an overall HLB of from 10.5-12.0;
b) from about 1% to about 20% by weight of a detergent compound selected from the group consisting of anionic, semipolar and zwitterionic surfactants; and c) from about 30% to about 70% by weight of a detergency builder selected from the group consisting of organic and inorganic builder salts.

2. A spray dried granular detergent composition containing:
1) about 20% of a sodium alkyl benzene sulfonate wherein said alkyl group contains an average of 12 carbon atoms;
2) about 5% of a mixture of (a) an ethoxylated primary oxo alcohol having an average molecular weight of 160 and a range of chain lengths between 9 and 11 carbon atoms with a major porportion containing 10 carbon atoms, said alcohol being ethoxylated with about four moles of ethylene oxide per mole of alcohol and (b) an ethoxylated secondary alcohol containing from 11 to 13 carbon atoms with an average chain length of 12 carbon atoms, said alcohol being ethoxylated with 9 moles of ethylene oxide per mole of alcohol;

3) about 33% sodium tripolyphosphate;

4) about 2% sodium toluene sulfonate;

5) about 0.6% sodium carboxymethyl cellulose;

6) about 21.9% sodium sulfate;

7) about 2.5% bentonite clay;

8) about 5.4% of sodium silicate having an SiO2:Na2O ratio of 2, and

9) the balance water.