CA2121792A1 - An improved cleaning composition which includes a sulfonated alkylated aromatic surfactant and a nonionic surfactant - Google Patents

Abstract

This invention is directed to cleaning compositions and methods useful in removing soils, particularly those of oil and grease, from surfaces particularly those of fabric. The composition includes a sulfonated alkylated aromatic surfactant and a nonionic surfactant. The class of sulfonated alkylated aromatic surfactant analogs used in the cleaning composition of the present invention will comprise at least one benzene ring wherein additional benzene rings can be attached in various forms, for example polycyclic aromatic(s) such as naphthalene, anthracene and the like, or via an ether linkage or other linking atoms. The sulfonated alkylated aromatic (SAA) will include at least one sulfonate group; wherein for aromatics consisting of more than one benzene ring, disulfonate is present in less than 50 percent of the total sulfonated alkylated aromatic. The SAA will also contain at least one alkyl group attached to the aromatic moiety of from about C18 up to about C30.

Description

W094/~5759 2 ~ 2 1 ~ 9 2 PcTJus93/O~O~O

--1 -- ! ; `",1 AN IMPRO~ED CLEANING COMPOSITION
WHICH INCLU~ES A SULFONATED ALKYLATED AROMATIC
SURFACTANT A~D A NnNJONIC SURFA~TANT
~', BACKGROUND OF THE INVENTION
This invention is directed to cleaning compositions and methods useftul in remo~ing ~oils, particularly those of oil and grease, from surface~
The ~omposition~ useful in the present invention contain a sulfonated alkylated aromatic ~"SAA") ::~
surfactant and a nonionic sur~aotank.
The largest group of SAA surfactants in use in cleaning compositions are based on dodecyl benzene sulfonate; a predominately monoalkylated mono~lfonated ~:
(MAMS) benzene. Another family of SAA ~ur~actant analogs are based~on diphenyl oxide and are -~
predominately monoalkylated having a relatively short : (less than:C16) alkyl chain and are predomina~ely di~ulfonated (MADS ~PO). The SA~ ~urfactants o~ the present invention,~on khe other hànd, are comprised of : at least one longer alkyl side chain (greater than or :~
;~ equal to C18)t are predomlnantly monosul~onat~d, and may :~ contain one or more phenyl: grQups.

,. ..

WO 94/05759 P~/US93/080$0 2I2~ 7~2 -2-SUMMARY OF THE I NVENT I ON .::
:,' .
One aspect of the present invention is an improved cleaning composition which offers superior cleaning of soil~ especially those of oil and grea~e.
More specifically, the removal of oily particulate stains or soils from surfaces by nonlonio surfae~ant~
can be ~ubstantially improved throu~h the addition of cerkain ~ulfonated alkylated aromatic ("SAA") surfactants to the nonionic surfactant.
- The class o~ SAA surfa¢tant analog~ used in the , cleaning composition of the present invention aontain an ~
aromatic moiety comprising at least one benzene ring. -The aromatic moiety may contain up to three benzene ;
rings attached in variou~ ~orms. For example ? the ;
aromatic moiety may contain polyoyclic aromatic(~) such a~ naphthalene, anthracene, and the like~ Additionally, the aromatic moiety may contain an ethe~ linkage as in diphenyl oxide or biphenylphenyl ether, or other linking atoms. Preferred aromatic moietie~ are benzen~
toluene, xylene, naphthalene, dipheny~ oxide, biphenyl, ~ and biphenylphenyl ether.
The SAA oP the present invention contains at least one~ alkyl group from a C1g up to about C30. For the purposes of t~his invention, a m~noalkylated SAA
refers to a SAA having one alkyl group with a chain length of C18 up~to about C30 per aromatic mo;ety and a 30 dialkylated SAA refers to a SAA having two alkyl groups ~`
with chain lengths~;o~ C18 up to about C30 per aromatic moitety. Thus, a monoalkylated~xylene~has one alkyl group~of chain length of Clg up to~about C30 and two ,: ~
. ~, ' !
' ' ~ ' ;' .
' ; '''' ': ~ ' ~ ,`~' W094/05759 PCT/US~3/080X0 212~7~2 methyl groups. The SAA of the present invention may be monoalkylated or dialkylated.

The SAA of the present invention al~o includes at least one sulfonate group; wherein ~or aromatics i`
con~isting of more than one benzene ring, disulfonate i~
present in less than 50 percent of the total SAA. Thus, the aromatic moiety in the present invention is sulfonated to at least about 100 percent and no more than about 150 percent.
- ~he more pre~erred sulPonated alkylated ^~`
, aromatics ar~ monoalkylated or dialkylated, monosulfonated benzene, toluene, xylene, naphthalene~
diphenyl oxide, biphenyl, and biphenylphenyl ether. The SAA of the present invention can be used in its acid or salt/neutralized form. Thus, the SAQ ~urfactant is represented by the following formula: -(R) " ~ r~ so3 X~)n, ~20 where: , Ar i5 an aromatic moiety which may be, but is not limited to, benzene, toluene, xylene, naphthalene, diphenyl oxide, biphenyl, or ~ , , CJ biphenylphenyl ether;
R is an alkyl group having a chain length of ~;
from 18 up to about 30;
.
X~ is hydrogen or a compatible counterion, which may be, but is not limited to NH4, Na, Ca~2~, protonated~diethanol amine, or protonated triethanol;amine;
1 < n' ~ 1~5; and 1 ~ n'l < 2.

~¢, ......

, :
~: .
.. .

WOg4/05759 PCT/US93/080~0

2 1 2 1 1 9 ~ --4~

The present invention also includes a method of cleaning a tain from a surface of fabric characterized by contacting the stain with the cleaning composition of the present invention comprising a ~ulfonated alkylated aromatic surfactant and a nonionic ~urfactant.

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 is a graph showing the influence of the per ent of disulfonation o~ one embodiment of the pre~ent invention on pretreatment cleaning.
Figure 2 is a graph showing the influe~ce o~
the percent of dialkyla~ion of one embodiment o~ the present invention on pretreatment cleaning.
Figure 3 is a graph showing the influe~ce of the ratio of the sulfonated alkylated aromatic ;~
surfactant to nonionic surfactant in one embodiment of the present invention.
Figure 4 i~ a graph showing the influence o~
the type of countsrion on cleaning performance of one embodiment of the present invention.

Figure 5 is a graph ~howing the influence of water on the cleaning performance of one embodiment of the present invention.

Figure 6 is a graph showing the in~luence of water on the cleaning performance o~ another embodiment of the present inventio .

~' "~.

; ;,~

~12~792 `

DETAILED DESCRIPTION OF THE INVENTION ;;
The sulfonated alkylated aromatic surfactant Commercially available monophenyl sulfonated alkylated aromatic surfactants useful in the present invention include Ari~tol F sulfonic acid (available from Pilot Chemical Company) 7 which is a monosulfonated, C20-24 alkyltoluene (monoaromatic~ and is greater than 90 percent monoalkylated.

Commeroially available alkylated aromatic compounds may be predominantly mono~ul~onated to be included as SAA surfaotants o~ the presenk invention.
An example of such compounds includes Aristol A
synthetic sulfonata~le oil available ~rom Pilot Chemical Company. Ariitol A is a C20-24 alkylbenzene (monoaromatic) which is at least 80 p~rcent monoalkylated.

The SAA surfactant o~ the pre~ent invention ~ will be monoalkylated or dialkylated and monosulfonated tor no more than 50 mole peroent disulfonated for the polyaromatics). The SAA surfaotants o~ the present inven~ion can be prepared by a Friedel-Craft~ reac~ion of an alp~a olefin with an aromatic moiety such as diphenyl oxide. The weight percent of the monoalkylated and dialkylated d~iphenyl~oxide (DPO) is determined by -~
gas chromatography~of the distilled alkylated diphenyl ~
oxide~(ADPO). The alkylates~(ADPO)~can then be ~`;
sul~ona~ted wikh;either chlorosulfonic acid or sulfur trioxide and can be u~ed in the acid ~r salt/neutralized ~orm. The~preferred polyaromatic SAA surfactant analog of the~present invention has a greater mole percent of ~monosulfonation relative~to~disul~onation. The pre~erred sulfonating agen~ choqen to produce such an , ::

: ~

W094/05759 pcr/uss3/o~oBo 21217~

analog in a laboratory environment is chlorosu~fonic ~;
acid. However, a different sulfonating agent, ~or e example sulfur trioxide, may be preferred in a ;
produotion environment. The percentage of the various sulfonated components (for example disulfonated to unsulfonated, monosulfonated and higher sulfonated) is determined by liquld chromatography.

The Nonionic Surfactant .:
Nonionic surfactants suitable for inclusion in the present cleaning compositions and methods are cho~en to impart compatibility and enhance interfacial interrelations between the cleaning ¢omposition, the stain, and the surface from which the stain is to be removed. Suitable nonionic aurfaotants include, but are not limited to: ethylene oxide adducts of alcohols, alkyl phenols~ fatty acids~ Patty acid amides and fatty acid esters.
The nonionic surfaotant may be monomeric or polymeric. Suitable nonionic surfactants include those ;~
taught in the EncyclopediaofChemicalTechnology, 3rd ;:
Edition, Vol. 22, pages 360-377. Preferred surfactants ~25 are ethylene oxide~adducts of alcohols and alkyl phenols~ Preferred nonionic surfactants selected for " .
inclusion in clean;ing compositions of the pre~ent .
invention will preferably have a hydrophilic lipophilic ~-balance (HLB) value in the~range of~from 8 to 15, more pre~erably 8 to 13, most preferably 9 to 13. ~;
j ~ .
ExàmpIes of commercially available nonionic surPactants suitable for the present invention include:
Neodol alcohol ethoxylates avallable from Shell Chemical; Igepal nonylpnenol ethoxylates available from .'' , WO ~4/0575~ ~'Cr/US93/080X() Rhone Poulenc; and Tergitol nonylphenol ethoxylates '~
available from Union Carbide.
The Cleanin~ Composition The SAA surfactant and nonionic surfac~ant ("NS") are typically present in a weight percen~ of about 5~ ~ SAAt(SAA ~ NS) < 60%. The more preferred weight percent for sulfonated alkylaked aromatîc to nonionic surfactant is about lO~ ~ SAA/~SAA ~ NS) ~
50%; the mo~t preferred weight p~cent is about 15% s SAA/(SAA ~ NS) ~ 30~. Thus, the weight ratio of' sulfonated alkylated aroma~ic surfactant present to nonionic surfactant pre~ent i5 typi¢ally from about 1:19 to about 3-2. Preferably, thi~ weight ratio i~ from about 1:9 to abou~ 1:1, and more preferably from abdut 1.5:8.5 to about 3:7.
`:
The optimal cleaning per~ormance of the -.
composition occurs when the water con~ent o~ the composition remains below ~bout 30 weight p~r¢ent of the total oompo~ition. Also the addition o~ hydrocarbon, such as hexadecane, to the formulation in an amount of ;
about 60 weight percent organic solvent (ba~ed on the total ~ormulation weight compri~ed o~nonionic 25 ~urfactant, SAA surfaotant:and~organic solvent) may `;
enhance cleaning performance but the addition of hydrocarbon unpredictably affects:the cleaning per~ormance e~ficacy of the~ur~actant system.
30 Compositions according to the present invention ~:
: may take the form~of~a liquid,:emulsioni dispersion or solution, semi-solid or scft solid or stick. Solid : stick compositions may be formed by dispersing the : various disclo3~ed compositions into a semi-hard carrier mediurn. An example of a~semi-hard carrier medium is ~ :

WOg4/05759 PCT/~S93/~8080 2~21792 8 '~
sodium ~tearate. Solid stick pre-spotting in stain rsmoving compositions and methods ~or making and using such a solid stick are described in the U.S. Patents 4,842,762; 4,396,521; and 37664,962~
Methods for cleaning a ioil or sta.in on a surface or fabric are characterized by conta¢ting the soil or stain with any of the cleaning compositions of the present invention described hereinabove. Contaoting ;
the 90il or ~tain with the cleaning composition ma~ mean contacting the area of the sur~ace or fabric where the stain or ioil re~ides, in addition ~o directly upon the , stain itielf. The term "stain" includes any substance which i~ embedded or not embedded, solid or li~uid, wet or dry, and at or beneath the surface or fabric~
After any of the cleaning composit~ons of the present invention have been applied to~ or contacted with the ~tain, the stain m~y be removed by wiping with a substrate, ~uch as a wet cloth or sponge; or by contacting the stain with water, such as by wash.ing with -~
a substantially aqueous media~ In the caQe of fabric ;~:
the composition treated stain i~ preferably laundered with water and more preferably with an aqueous ~olution of mostly water and a conventional laundry detergent~
, The cleaning formulations of the present .
: invention are evaluated by measuring thei efficacy of the formulation as a prewash staln remover treatment ~or 30 soiled fabric. The cleaning formulation i~ applied to ~.
: ' prestainedlfabric and the fabric is washed and evaluàted for cleaning efficacy by~a reflectance measurement of the washed fabric compared to that of the unstained fabric:and the stained fabric.

, .
: ~, WOgq/05~59 2 1 2 1 7 9 2 PCT/US93/08080 _g _ -.~ ~ ,. .

The following examples illustrate (1) the preparation of the SAA surfactants of the pre~ent invention; (2) the performance o~ these surfactants with nonionio ~urfactants as a~clèaning composition and (3) the performance ~f commercially available SAA
surfactant~ with nonioni~ ~urfaetants as compone~ts o~
the cleaning compositîon.

Examples The SulPonated Alkvlated Aromakic Surfactants I. PREPARATION OF DIPHEN~L OXIDE OR BIPHENYL
SULFONATED ALKYLATED:AROMATIC SURFACTANTS (SAA). ;
Alkylates prepared (percentages are by weight):
'15 ~ C6 monoalkylated diphenyl oxide (DPO) (comparative:example - not an:example of the ;
invention) * C14 dialkylated DPO (oomparative example ~ not ~:~
: an example of the invention) : 20 * C16 monoalkylated DPO ~comparative example -not an example of the inven:tlon) ; * C18 dialkylated DPO
* C20-24 monoalkylated DPO
* C20-24 75%/25% mono/di~:alkylated DPO
* C24_28 80%/20% mono/di a~lkylated DPO
: ~ : * C30+ 80%/20% mo~no/di alkylated DPO
* C20 2~ 80%:/20% mono/di alkylated biphenyl (BP) ::
, (IAll of the alpha olefins used to prepare the above alkylates were obtained from Chevron Corporation, : therefore, the chain length:specifications are those furnlshed by Chevron.) ~

,:

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

:
WOg4/057s() PCT/US93/08080 2121 7~ -10-General procedure to prepare alkylated aromatic compounds:
Preparation of C20-24 monoalkylated diphenyl oxide (DPO): Into a 5 liter round-bottomed flask (RBF) equipped with a magnetic stirrer, an addition funnel, a conden3er, and a nitrogen inlet is placed warm DPO, (2.040 kg, 12.00 moles, 3 mole equivalents with re~pect to the olefin). To this light yellow solution is added the Lewis acid catalyst~ aluminum chloride~ AlCl3, (24.0 g, 0.180 moles, 0.045 mole equivalents with respect to 1~ the olefin). This i~ then ~ea~ed to 70-7S C with stirring ~or 45 minutes ~o a~ to completely di~olve the AlCl~. The color vf the reaction mixture will gradually darken during this time until it is red brown.
Concurrently, the C20-24 alpha olefin (1.185 kg9 4.0d moles) is melted and placed into a~ addition funnel that has been wrapped with heating tape. The addition o~ the olefin i begun once all o~ the AlCl3 dissolves into the DPO. The rate of olefin addition is to maintain the temperat~re at 70-75 C (over about 5 hour~).

Once all of the olefin i9 added, external heating is reapplied and the reaction mixture is post ~;
reacted at 70 C for an additional hour. At the end of the hour~ heating is discontinued and a 25% aqueous sodium hydroxide ~olution (349 g~ is introduced. The ~;
reaction mixture is allowed to cool and stir overnight during which time the color changes from a rather dark red brown to a light yellow.
The stirring is discontinued and the phase~ àre allowed to separate. The organic phase is decanted away from the basic aqueous phase, lS placed into several 2 ~"
liter ~eparatory funnels and is washed several times with distilled water until the pH of the resulting water .. ...
'. ' ~
- ';
"
. ..

W o 94/057s9 ~ 1 21 7 9 ~ Pcr/uss3/ososo - 1 1- 1 .,;, is neutral. The organic phases are then combined and -~;
~to~ed in plastic con~ainers unt~l ~eeded.
General procedure ~or topping alkylated aromatic compounds 7 simple distillation:
The removal of the unreacted DP0 (diphenyl oxide) (ca. 1.3 kg, 2.0 mole equivalents) ls accompli~hed through the use o~ a simple vacuum distillation. The wa~hed organic phase portion from above (ca 3.5 liters) is placed into a 5 liter RBF
equipped with a magnetic stirrer, a simple distillation head apparatu~ and a vacuum take o~ adapter. The , reaction mixture is stirred and the vacuum is slowly ~ ;
applied in order to minimize bumping. rhe distillation ~;;
proceeds as follows (Table 1): , .
2~
: ~, :: : :
: : ~
: .:
l; 30 : l~

W~ 94/057~;9 PCI/IJS93/OXO~O 21217Y~

o c a E~ a ~ ., o .~:
a ~ ~ ~ ~ ~ ~ ~

~ E , W ~; ' o ~ Z; a ~1 e. ~ ~" ", ' o O a _~ ~ a` x ~ z ;c x z (n u~ 0 0 ,:
o W ~ 3 ~ 3 :-O ~ Z O O O O
o o o o C U~ ~ U ~ ~ U
o ~ ~
p~ ,.
0 ~ ~ 0 U U U

o o o ~ , a~ o E ~D ol~ ~rZ ~r 'I r.l ~ a~ o ." ~ o U~ O

ol z 4 N ~ ~~ 7~ ~ N N

I~ ~ V O ~ r~ rl ~ N ~ æ
o ~
~ N ~ .n O ~ ~ :

~ o ~I , ¢ '' , , '; ~
~, .;

~0~4/0575~ PCT/~S93/0~080 2~2:1792 The pot material is then used as the topped material in subsequent sulfonation reactions or alternatively could be fractionally distilled to obtain ~ractions that conkain varying degree~ vf alkylated materials (i.e. mono/di/higher alkylate).

General procedure for the isolation o~
mono/di/higher alkylated aromatic compound3 using a vacuum frac~ional distillation:
Topped material (0.9 liter~ placed into a 2 liter RBF equipped with a magnetic stirrer, a 14 inch vigreux ~ractionating column and a vacuum distillation head, The contents are stirred and the vacuum i~
applied. The distillation proceeds a~ follow~ (Table 2): :.
~

;::~
, :.

WO 94/05759 PCI/US93/0~ 8~ ~
2 1 2 1 7 9 2 --1 4-- !

O ,¢ ~ a ~ ~ ~ c, ;
E~ a ; i;
V~ .
o O '.
~ O O~ Q
u ~" oc~o~cr~ I` ~ 117 :~;
O ~ ~ "
31 ~ X
0 2;~5i; O O ~ ~ X ,,~
O "
.u ~
~ , ,~
c~ ~ Z ~ ~ ; æ v O a U ~ -.
V I U ~
10 0 ~1 ~ I G
_~ N ~¢ Q~ 3 ` ' :~ V ~ ~ ~ ~ 0:
_~ ~D ~ v v v v ,~ ~

d X .
L~ a ~ , 0 -- , .
LO , . ,', ~u ~6~ ~u~
,,, .~: , .;
0 ~
_I,~ rl , o ,,, ,_1 G r~ N N N N N N
N N N D N ~ N

.. . .
N~

Ij" :~ ~,'' " ~
';''`
.~ `'.

.~

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~g4/0575g PCT/US93/0~080 2~2~7~

The pot material is used as dialkylated DP0 based material in subse~uent sulfonation reactions and in the GC standard solution.

Sulfonates prepared:
* C6 monoalkylated monosul~onated DP0 (comparative example - not an example of the invention) 14 dialkylated, monosulfonated DP0 ~oomparative example - not an example of the inventio~) * C16 monoalkylated, monosulfonated DP0 (comparative example - not an exampl~ of the invention) * C1~ monoalkylated, monosulfonated DP0 * C18 dialkylated, monosulfonated DP0 * C20~24 topped material, monosulfonated DP0 * C20-24 monoalkylated, disulfonated DP0 ::
(comparative example - not an example of the invention) * C20-24 monoalkylated, monosul~onat0d DP0 * C2~_28 topped material, monosulfonated DP0 * C30+ topped material, mono.~ulfonated DP0 * C20-24 topped material, monosulPonated BP :~

General procedure for the monosulfonation of aroma~ic materials~
C20-24 monosulfonated monoalkyl~ted ~P0: Into a 1 liter RBF equipped with a magnetic stirrer, additional ~unnel, Claisen adapter, water condenser, nitrogen inlet and a h~drochloric ~cid exit i~ placed ; Ithe C20-24 monoalkylated DP0 (t75.0 g, 0.380 moles).
This is diluted with chloro~orm (350 mL) and cooled to O~C via an ice bath. To the addition funnel is added chloroform (50 mL) and chlorosulfonic acid 525.3 mL, :~
0.380 moles). The oontents oP the addition ~unnel are .....

WO 9'1/0575g PCI /US93/~)8081) 2~2~7~2 -16- . !

mixed and added lnto the reaction vessel over a 2 h ~;
period. ~uring this time the reaction mixture's color goes ~rom nearly colorless to red-brown. Once all the ;~
the chlorosulfonic acid .solution is added, the reaction mixture i~ allowed to 510wly warm to ambient temperature and stir overnight. The following day an aliquot is removed and analyzed by liquid chromatography to determine the degree o~ ~ulfonation. When it is apparent that the reactlon i~ complete, the sitir bar is removed and the contents are ¢oncentrated in ~acuo (5~10 tor~) utilizing a rotary evaporator. The sample is then subjected to reduced presisures (0.1-0.5 torr, vacuum pump) and a final sample is analyzed b~ liquid chromatography. Both liquid chromatography analyses are consistent~and show that the percent~of unsul~onated and monosulfonated p~oduct to the disulfonated material i9 about 96 to 4.

General procedure for the purification of monoal.~ylated, monosulfonated aromatic materials (example C20~24 DPO based MAMS)~

C20~24 DPO~based MAMS: ~A portion of the crude reaction mixture described above is taken (70 g) and dis~olved in methylene chloride, Me~l2, (300 mL) and ~;
placed on top oP~a Plash silica gel column (10 inch x 2 inch) that has been packed u~ing MeCl2. Some solid material may ~ail~to dissolve into the MeCl2~ and is assume~ to be inorganic salts ~uch as sodium sulfate and sodium chloride.~ The elusion;method and the subsequent analysis (TLC, elusion with MeC12;ior liquid chromatogriaphy) o~ the Practions obtained are shown in ;~
Table 3. `

, :
:

WC) g4/1)575g PCr/US93/080~021217~2 :

_l :
a X

a ,,'' ~d W ~

o M e z Z ~ ~ ;C 5 ~ e , ~
~ .
~n ,~C
. E~ ~ ~ N 0 ~ ~ If) In o O C~ :
8 ~ ~ ~ ~ ~ z o 3 Z o 0~

o : .
W
~; O C~ O O O O o o o c:~ o o , O O O O O O ~ o o ~ W , ':.
, ~.

a N
~ ^ ~ ~ ~ U U U U
a ~ N S aE
e Z~ U~ U ~ o: O O x W o: - ' , 13 ; , ' ~
o .,-.:
O IS: , , ~
.
, W094/0s7ss PClIUS93/~OXO
2~217~

The column chromatograph is discontinued when the MADS component is detected eluding from the column.
Fractions are combined based upon their purity.
Fractions 1 through 7 contain unreacted alkylate and are di~carded. Fraction 8 through 11 contain only pure C2~_24 MAMS and are combined to afford 45 g of product.
General procedure for the disulfonation reaction of aromatic materials: ; ;
C2a_24 disulfonated monoalkylated DPO: To a 125 mL addition funnel is added liquefied ~ulfur trioxi~e, S03, (56.6 g, 0.707 moles, 2.3 equivalents , based on ADPO talkylated diphenyl oxide)). This is ~ealed and transferred to a bottom outle~, stopcock controlled, 500 mL 3-necked RBF that i5 equipped with a stlr rod, a nitrogen inlet and contains MeC12 (150 mL).
The amount of the C20-2l~ monoalkylated DPO (143.6 g7 0.308 moles, 1/2.3 equiv~lents) i~ calculated based on the amount o~ the S03 weighed out and i5 placed into a 1 20 liter 3-necked RBF equipped with a nitrogen in,et and overhead stirrer. The alkylate i~ diluted with MeC12 (350 mL) and the 1 liter 3-necked RBF is attached to the outlet of the S03/MeC12 RBF. The reaction vessel is cooled to O C via an ice bath. The alkylated DPO
25 solution is stirred and the S03tMeC12 so~Lutlon is slowly added over 1-5 h being careful not to allow the reaction s temperature to rise above 4 C. During thi~ time, the reaction darkens from light yellow to red brown. An aliquo~ is removed after a post r~action time af 0.5

3~ hours at OiC and is concentrated, neutralized and dissolved in a water/meShanol mixture. This is analyzed by liquid chromatography. ~This analysis indicated that the ratio of unsulfonated/monosulfonated ADPO to disulfonated ADPO is about 2 to 98.

WO 94/0575') PCI /US93/08080 - ~
2~2i7;~2 For the cleaning formulations of the present invention the purity of the monoalkylated, disul~onated DPO ba~ed species are generally pure enough that no further puri~ication techniques are required. ;
General procedure for the analys1s of the alkylates:
The analysi.~ of the alkylates is done uqing a gas chromatography system comprised of a Hewlett Packard GC; HP 7673 A autosampler; HP33g6A integrator; HP g114B
external disk drive and a J&W DB~ 15m x 0.32 mm, 0.1 um ;, film column. The flow rate o~ helium i~ 8~7 ml/min~
The instrument i~ calibrated with an internal standard and a standard ~olution of components. The percentage3 reported ar,e in weight percent. Each different ~DPO, (differing by chain length) prepared required development of a eeparate GC system.
General procedure ~or the analysis of the sulfonate~ aromati¢ speoies: ~
The analysis o~ the sulfonated aromatic species ~;
is done using a liquid chromato6raphy s~stem compri ed of a Milton Roy piston pump7 a single port injector, a 250 mm x 4.6 mm glass column packed with Yydac's 301SC
~200 mm) anion exchange resin, ~ LDC UV III monitor (254 ~5 nm filter), and a Spectra Phy~ics~Chrom Jet integrator.
The solvent system is a 1:1 methanol ;~
(MeOH):tetrahydro~uran (THF); buffered with 0.2 M acetic acid (AcOH),~0.2 M~sodium acetate (NaOAc), and 0.1 M
sodium perchlorate (NaCl04).~ The operating pressure is l kept between 50-80 psi with dampening. The~percentages ; ~-reported are in area percent.
. . .

., ',.

W~94/0575g PCT/US93/080~0 ~121792 -20~

II. PREPARATION OF CLEANING COMPOSITION/ STAINED
FABRICS/EVALUATION OF CLEANING
Preparation of cleanin~ composition The cleaning samples prepared all contained 5 alkylated t sulfonated aromatic materials and nonionic ~:
surfactants in various ratios according to ~he figures and tables which follow in the results section. The alkylated, ~ulfonated aroma~ic component is the Pormula as stipulated in the Pigures and table~ which follow.
~ he nonionic surfactant ~omponent o~ the cleaning formulation is either Neodol alcohol ethoxylate~
available from ~hell Chemical; Igepal nonylphenol ethoxylateq available from Rhone Poulenc; Ter~itol nonylphenol ethoxylates available ~rom Union Carbide or one of three blends prepared from Neodol to impart various HLB surfactant solutions. Blend one (HLB v~lue approximately 9) consist~ of approximately 77 weight percent Neodol 25-3 and approximatelr 23 weight percent Neodol 25-9; blend two (HLB value approximately 10) consists of approximately 50 weight percent Neodol 23-3 and approximately 50 weight percent Neodol 23-6.5 ;
blend three ~HLB value approximately 11.4) consi~ts of approximately 32 weight percent Neodol 25-3 and approximately 6a weight percent Neodol 25-9.

Prepara~ion o~ fabric Test ~abrics are:
1!~) Cottsn: #405, Bleached Cotton Sheeting, 48" wide, obtained from Test Fabric Incorporated, Middlesex, NJ
2) Polyester/Cotton: #7436, Dacron 54W~Cotton, 65/35, Poplin, 60" wide, '''':

W09~/057s9 P~T/US93/080XO
21217!J~

obtained ~rom Test Fabric Incorporated, Middlesex~ NJ

The ~abric is prewashed three times to remove sizing in a General Electric Washer Model ~WWA8340G. Settings used for a~l cycles are as follow~:
Regular/Normal cycle Warm wash/cold rinse Load si~e: large Generally, one piece of cotton fabric, 45" x 96", and one piece of polycotton fabric, 6~" x 72~', are laundered per wash load. Zero pho3phsrous content TIDE0powdered laundry detergent (Proctor & Gamble) is used for this prewash and in all phases o~ testing. For each wa~h 15 cycle, 15~-0.5 grams o~ TIDE is used. The fabric is not .
dried between wa~h cycles. After the third wash cycle, the fabri~ is dried in a General Electric Dryer Model ~
#DDE8200GBLAD on high heat for 70 minutes. After ~`
drying, the fabric is referred to as prewashed ~abric~
The fabric is removed promptly from the dryer and smoothed with clean hands to remove wrinkles. The `;
prewashed fabric is not ironed. If it is not used in a test within six weeks it is discarded.
. ~, Cuttin~ swatches After drying, the prewashed ~abric is cut into swatches approximately 3" x 4.5". An Eastman Chick-a- `
dee Model D2 rotary shear ~(MJ Feley Company, Ro~evîlle, MI) is used for the cutting~procedure. Metal templates of cleaned aluminum or cleaned galvanized ~heeting are used as guides for the rotary shear. Fabric salvages are permissible on the final test ~watch. Once cut into the 3" x 4.5" test size the prewashed ~abric is referred i:

'`~

W~g4/0575~ Pcr/us93/o8o~o 2~2~7~2 -22-to as a swatch or a test swatch. All swatches are ~tored away ~rom light.

Staining o~ swatches Staining o~ swatches i~ done in the afternoon s o~ the day before a cleaning test. A 2l~ hours set time between staining and te~ting i5 recommended to allow the stain to wick out across the swatch. The ~watches to be stained are laid out on a bench top on a double thickness o~ Scott Utllity Wipes ~re~erred to as Soott wipes)~. All swatches should be ~rom the same prewa~hed , fabric.

Number of swatches_to st.~}n: Generally ~or' :
each cleaning formulation te~ted two stained cotton swatches and kwo stained poly~otton swat¢hes are treated and washed with TIDE and two stained cotton swatches and two stained polyaotton swatches are treated and washed without TIDE. Controls are two ~tained cotton swatches ~ and two stained polycotton swatches washed in TIDE only.
Also, three stained ~watches oP each fabric type are needed as 100% Dirty Standards.

Stain material: The stain material is Wolf' 3 Head~SAE 30W motor oil ~Wol~'s Head Oil Compan~, Qil City,:PA) used approximately 30 hours in an .. :`
International three cylinder diesel tractor. Sin~e the stain contai~s parti~ulates, the stock bottle is shaken at high speed on a reciprocation shaker for five minutes before it is~applied. If the ~talning process takes longer than 15 minutes 7 the stock bottle will be reshaken after 15 minutes.
.:
_~plyinj~ the stain: The stain can be applied in one of' three ways. All th~ee methods result in , : ~ '' WOg4/0575~ PCT/~S93/08080 2~2:~ 7 92 approximately 0.18 grams of staîn material being ;
applied. Method 2 or 3 is reco~mended.

1) Plastic disposable pipet (Fisher Scientific C~mpany, Fisherbrand Catalog ~13-711-5).
Fill pipet and hold ik at 45angle about one inch above the center o~ the ~watah.
Slowly drip on seven drops at the center of each swatGh.
2) NichirYo Ox~ord model 810C s~ringe pipet ~;
~ (Fi~her S¢ientific Company) with a 6 milli ;~
liter syringe on the end. Di3penser setting at 2 to give 200 microliters (+
0.8% accuracy as manufactured~ volume dispensed. Slowly di~pense the stain material at the center of the swatch with the tip of the syringe about one inch above it. , 3) Weighed amo _ t, Tare out the swatch on a Scott Wipe on a two decimal place balance and apply 0.18g ~ 0.02 of stain material slowly~by pipet to the center of the swatch.
After~staining: After applying the oil stain, the swatch~s sit undisturbed overnight on a bench top.
The swatches are~now referred to as stained swatcheq, 30~ l Stained swatches will sit a minimum of 16 hours after staining before being u~ed in a test. This îs to allow the stain to 'set'/wick out into the swatch.
Stained swatches not used within 28 hours o~ staining are disoarded.

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,~':''' W094/05759 PCT/US~3/08080 21~1792 -24- ~

Preparation of stained swatches for testin~
:
Stained swatches are inspected before testing.
Any that look unu~ual, i.e. the oil stain did not spread ou~ or only spread unevenly, are discarded. Extra stained swatches will not be held over to be used in another cleaning test.

Two c~tton and two polycotton stained swatches are laid out on a new clean Scott wipe. If possible, the technical cleaning formulation is ~tirr~d with a woode~ applicator stick. A stained ~watch is tared.
The stained swatch is removed to a Scott wipe and :~
approximately 1.5 grams of the technioal cleaning formulation is applied. A wooden applicator stick i~
15 used to gently spread it over the sur~ace of the stained ;-area. A rubbing motion i3 .not used. High viscosity technical cleaning Pormulation may require more sample and more work to spread them. Low vi~cosity technical cleaning Pormulatiol1s may be transferred to the stained swaSch by volum~tric syringe.
. ,~
The technical cleaning formulations is spread ~;
to cover a diameter of 1.5 inches at the center o~ the stained area and~at least 90% of the full stained area.
The treated stained swa~ch is placed on the balance and the amount o~ technical cleanlng ~ormulation applied recorded. The amount applied should be 1.5 ~ 0.2 g.
The balance pan is cleaned and the next stained ~watch 30~ !in the s~et of four lS proces~ed in the same way. Once the technical cleaning formulation i~ applied~ the stained swatch is referred to as~ a treated stained swatch. ~ ~ ~

:~' :~ ~

:

WOg~/0575g 2 1 2 :l 7 9 2 Pcr/us~3/0~080 -25- i ;;

In order to keep the contact time between stain and technîcal cleaning ~ormulation in the selected range of a minimum of 5 minutes and a maximum af 30 minutes, no more than 25 minutes should lapse between the first swa~eh and the l~st qwatch in the set is treated.
Ideally, no more than ten minute~ should lapse before all stained swatches in the set are treated. Five minutes after the last stained swatch in the set iq treated~ the treated stained swatches are put into a ;' prepared a~itator pot of a Terg-O-Tometer ~SEE
PREPARATION OF TERG-O-TOMETER SECTION). The treated stained swatches are introduced into the wash water in the order in which they were treated.

15Th~ above process is ~enerally done twice ~or each technical cleaning formulation with one set wa~hed in water with TIDE present and the second ~et wa~hed in water without TIDE present. Stained swatches treated with different teehnical cleaning formulations are not washed together.

Preparation of controls .,~
For each te~t day, control~ are run with TI~E
only. Two cotton stained swatches and two polycotton stained ~watches are introduced into an agitator pot prepared with 2.00 ~ 0.01 g TIDE in the water. Controls are processed the same as technical cleaning formulation treated ~tained swatches.
Preparation of ter~-o-tométer and testinF~ with ter~-o-tometer Deionized water is used in all phases of testing after the initial prewash o~ the fabric.

..,~

WVg4/05759 PCr/US~3/0~080 ~ 2 -26-A six place Terg-0-Tometer model ~7243S
(Research and Testing Company, Inc. Fairfield, NJ) is A~
used. The Terg-0-Tometer bath is preheated to 120F.
The agitator pots are ~illed with 1700 ~ S0 mL of deionized water. The wa~h and rinse cycles are run at 120~F and the agitatio~ r~te is 100 rpm. The temperature is checked in each a~itator pot.

Wash cYcle Unle~ specified otherwise7 stained ~watche~
are w~shed with TIDE in the water: 0.5 grams of TIDE is used ~or each swatch. Generally four swatches are washed in 2 + 0.01 grams o~ TIDE per agitator p~t. The lot code o~ the TIDE ~ox is recorded. TIDE is added to the agitator pot, with agitakion on, for approxlmately two minutes before the swatche~ are added.
For stained swatches with or wi~hout TIDE in the water: treated stained swatches are added one at a time to the agitator pot, wikh agitation on, in the order in whioh they were treated with the treated side facing away fro~ the agitator shaft. After all the swatches are a~ded to a pot, a timer is set for 15 minutes. At the end of 15 minutes, agitation is stopped. The contents of the agitator pot are poured -through a ~ieve, retaining the washed treated ~tained swatches (washed swatches). The washed swatches are retrieved and the excess water ~queezed out o~ them by hand. They are rinsed for 3-5 second with deionized water. The washed swatches are then ~eparated from each other.

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' ', : :',."' W~g4/~5759 PCT/US93/080~0 2~2~792 -27- , Rinse cycle The rinse cycle is the same ~or all ~watches whether washed with or without TIDE.

The ~eparated washed swatches are immediately added one at a time to a rinse agitator pot. A rînse agitator pot contain~ 1700 ~ 50 ~L deionized water at 120F. There is no specific order of addition ~or a rinse cycle. Agitation and water temperature is the same as for a wash ¢ycle. A rin~e cycle is five minute~
in length. At the end o~ the five minute~, the contents of ~he rinse agitator pot is poured through a sieve, retaining the washed and rin~ed swatches (rinsed swatches).~ Rinsed swa~ches are separated by hand and rinsed 3-5 ~econds with deionized water. Excess water is squeezed out oP the rin~ed swatche~ by hand. The rinsed swatches of each s0t are smoothed ~lat by hand onto a single thickness oP Scott wipe. A se¢ond Scott wipe is u~ed to lightly cover the rin~ed ~watches. The rinsed swatches are not ironed and are allowed to dry overnight. --- ~, Determination o~ nercent clean , .
Percent clean is calculated from reflected light readings. Reflecta~ce readings are rep~rted as three coordinates tha~ define a specific point in the ;~
cubic space that is used to described color and hue. ~, Reflected light readings from a set of 100% Clean ! ~ !S~andardsland ~rom a set of 100% Dirty Standards are used to determine the range ~or zero to 100% clean. The reflectance of a rinsed swatch is then placed as a percentage along this range and~this percentage is reported as its percent clean.
. .

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wo94/~s7s~ P~T/US~3/08~80 2 ~r~ 28-Rin~ed swatches are air dried at least ,~
overnight (16 hours) before refle.ctance readings are ;' taken. Rinsed swatches not read within 24 hours of test will be stored in a dark place to prevent deterioration.
A MiniScan~ Spec~rocolorimeter version MS4500L (Hunter Lab, Reston VA) is used to make re~lectance measurem4nts and is standardized before each reading session. The Commission Internationale de l'Eclairage ~CIE) 1931 ''' Tristimulus XYZ Scale (CIE X~Z Sc~le) i~ used as the ' 10 reflectance scale with a CIE 1931 standard source '~'~
illuminant C and CIE 1931 2 standard observer. .',' At least two readings for each rinsed swatch is :,."
done with the sen~or of the MlniScan rotated 90 to minimize the effect of f.bric nap on the reflectance~ ~.
readings. The average of these readings is recorded, Readings are taken at the center of a rinsed swatch on the s~de to which the technioal cleaning formulation is applied. The rin~ed swatch is laid on a piece of white .:, : :: zo poster board to give a uniform background to all rinsed :~
swatches and to eliminate the tendency of the rinsed ~':
swatch to pillow up. Pillowing up would occur on a soft background and e~feot the re~leotance angle of the light '' and therefore the reflectance~reading.
Standards; will consist of:three unstained ~':
swatches of each;fabrio (100% Clean:Standards) from the ~;, ~ same prewashed cloth as ~the test set and three stained ',' ::: swatches of each~P~abric ~100% Dirty S~andard) from the .'~
3, s,ame skaining day as the ~test set and from the same j , .....: prewashed cloth. Readings are done using the same ~ method:as for the rinsed~swatches~

., ; . ~

WO9~/05759 2 ~ 217 ~9 2 Pcr/lJs~3/osnxl) ~2g- , Determination o~ percent clean is by the following equation: . :

(1) Percent Clean - .

1*{~(Xr-Xd)~(Yr-Yd)2+(Zr-Zd)2l1/Z / [(Xc~Xd)2~( Yd)2~c-zd)2]l/2}
Where: ;
Xc = clean standard swatch X value from MiniScan :~
Yc = clean ~tandard ~watch Y value from MiniScan ~c ~ clean standard swatch Z value from MiniScan Xd ~ dirty standard stained swatch X value from ~.
MiniScan Yd = dirty standard stained swatch Y value from .
MiniScan Zd = dirty standard sta;ned swakch Z value ~rom MiniScan Xr = Rinsed swatch X value for MiniS~an Yr - Rinsed swatch Y value for MiniScan Zr = Rinsed swatch Z value for MiniScan ~ :

:

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.

W~ 9q/05759 PCI`/US93/080~0 r~ 9 7 :

III. EVALUATION OF SAMPLESJCLEANING FORMULATION

Cleaning formulations to be tested are prepared by by combining the desired amount of a sulfonated alkylated aromatic surfactant, noniorlic ~ur~actant and any additional additives to be included in the formulation and mixing them until uniform. The formulations may require heating ~o facilitate mixing. ..

Formulation Variables .,.. ;
_ . , A. Type of Sulfonated Alkylated Aromatic Surfactant ;~,.
1) Alk~l chain length Table 4 summarizes the cleaning res~lts for a ~eries oP ~ubstantially monoalkylated monosulfonated diphenyl oxide (MAMS DPO) ~urfactants and variou~
alkylbenzene ~ul~onic acîds when used in a formulation consi~ting of 1 part of the ~ulfonated alkylated 2~ aromatic surfactant to 3 parts o~ Igepal C0-520 nsnionic surfactant. ~ata with TIDE deter~ent without any s~ain ~:
pretreatment are included in the table for compari~on.
A compari~on of the~data ~how that the percent cleaning obtained with a sulfonated alkylated aromatîc surfactant containing an alkyl group of C1~ or longer are considerably ~uperior to the cleanin~ obtained with ;~
the Comparative ExampIe~ or a typical detergent (TIDE~
- 30 The MAMS DPO demonstrates~:the most dramatic improvement in clea~ning;performance ~rom the C16 to C18 alkyl chain length. : .:
:
, ,.
'~ ',';', ,`'.' '' , ~, " .. : :
; ', , .
;-WO ~4/05759 2 ~ ~ 1 7 9 2 PCI`/VS~3/0811)8~
,~, .
- 3 1 - ! ~

, Table 4 The Influence of Alkyl Chain Length on Cleaning Performance monot mono/ Percent Clean Percent Clean 5Sulfonated di~ di- ~washed inTide) (Notwashed in Tide) alkylate sulfonate Surfactant (weight (areaPolyester/ C Polyester/
percent) percent) Cotton cottc~n Otton cotton C6MAMS DPO 100/0 84/16 36 2g 10Comparative ~
Example A :
.

Comparative Example B -C18 MAMS DPO 100/0 9713 ~,~1 401 57 26 C20~24 MAMS DPO 74126 86/14 752 4~z ~1 35 C30~ MAMSDPO 80/20 85/15 70 58 ~Toluene sulfonic 33 12 5 7 :
acid Compara~ive : .:
20Example C
C12 Benzene 34 27 37 23 :
sulfonic acid3 Comparative . ~ ~
Example D . .
C18Toluene 97/3 100/0 42 31 25sulfonic acid4 :
C20 24Toluene 93n~ 100/0 772 472 76 30 ~:.
sulfonic acid5 ........ ~......... :......... ........... O
Tide alone : 246 116 Control - not an ~:
example of the : .
3 invention I : ! ~.
1. Average of 2 tests. ~ . .
~: 2. Avera~eof6tests.
3. B!O SOFT S-1 ûQ~, Stepan

4. Aristoi (;, Pilot Chernical : ~ S. ~ristol F, Pilot Chemical 6. Averageof20tests.

WO 94/05759 PCr/USs3/0808~
2 ~ r~ 9 ~ 2 . .
--3 -- :.
:,"
Table 4 The Influence of Alkyl Chain Length on Cleaning Performance mono/ mono/ Percent Clean Percent Clean di- di- (washed in Tide) (Not washed in Tide) Sulfonated alky!ate sulfonate ~.
(welght (ar~a Polyester/ Polyester/
percent) percent) Cotton cotton Cotton cotton ' ",~
Igepal C0-520 25 23 ~ .
alone Control - not an :
exampl~ of ~he 10 invention 1. Average of ~ tests.
2. Average of 6 tests 3. BlOSOFTS-100~,Stepan 4. AristolG,PilotChemical

5. Aristol F, Pilot Chemical 15 6. Averageof20test5-In all ca~es the data show that cleaning with formulations containing the sulfonated alkylated .~;
aromatic ~ur~actant containing an alkyl group of 18 carbons or longer gave better performance than the ;~
nonionic surfactant by it~elf or the nonionic sur~acta~tcontainîng a commonly availa~re linear dodecylbenzene sulfonic acid ~BIO SOFT S-100~ from Stepan Chemi¢al Co.
Northfield ~L.~ or a commonl~ available h~drokrope (p-25 toluene sulfonic~acid). .

2) Percent of sulfonation ~.:
The percent of sulfonation is evaluated bypreparing cleaning:formulation~ of Igepal C0-520 with 3i SAA ~ur~jactants oontaining dif~rent ratios af mono- to d~sul~onated C20-24: alkylate diphenyl oxide that have ~-:been separa~ely pr~epared using the same batch of C20 24 monoa~kylated diphenyl oxide. The predominantly monosulfonated DPO is analyzed to be 100 percent monoalkylated~ 96 percent monosulfonated, and 4 percent ~

:.,' ' ' ~
,~ ~
,, W094/0s759 PCT/US93/08080 ~2179~ ;

disulfonated; the predominantly disulfonated DPO is ;~
analyzed to be 100 percent monoalkylated and 90 percent disulfonated. A puri~ied monosul~onated, monoalkylated DPO i~ prepared and analyzed to be 100 percent monoalkylated and 100 percent mono~iulfonated.
Figure 1 ~ummarizeQ the inPluence o~ the percent of sul~onation on the cleaning for a formulation consisting of 1 part of the mono- and di~ulfonated C20-24 monoalkylate diphenyl oxide sur~actant ~o 3 part~
by weight of Igepal C0-520 nonionic surfactant. Th~
cleanîng per~ormance beginsi to decrease a~ter about 30 percent by weight of the C20-24 monoalkylated diphenyl oxide is disulfonated.

% Monosulfonated ~ Clean Cot % Clean PEC ~52b~L}
10.0 36 ~2 90.0 31.~ 47 26 68~5 50.0 54 33 ~O.O `;
71.3 75 40 28.7 `
71.3 73 47 28.7 80.8 79 42 19 80.8 77 ~ 42 19.2 96.0 82 37 4.0 100.0 79 42 O.O

3) Percent of alk~lation The pereent of alkylation i~ evaluated by preparing ~ormulations with~different ratio~ of mono- to dialkylated C18 alkylated diphenyl oxide (DPO). The monoalkylated DPO i~i analyzed to be 99.9% monoalkylated and 97% monosulfonated; the dialkylated DPO i~ analyzed ~, :

W~g4/05759 PCT/~S93/08080 ~ 1 2 ~ 7 g 2 -34-to be 100% dialkylated and ~4~ monosulfonated. Figure 2 summarizes the percent of alkylation influence on the cleaning for a formulation consisting of 1 part of the mixture of the sulPonated mono~ and dialkylated C18 diphenyl oxide ~urfactant to 3 parts of Igepal C0-520 nonionic surfa¢tant; for polyester~cotton fabric the cleanin~ performance is essentially independent of the ratio of the degree of ~lkylation. However, for cotton ~abric, significantly better cleaning performanoe i9 obtained with the dialkylated surfa¢tant than with the mono~lkylated surfac~ant. Also, a minimum in the cleaning performance is observed at approximately 30 weight percent of dialkylation. ;~

The influence of increased chain lengkh on cleaning performance for monosulfonat~d dialkylated aromatic surfactants is shown in Table 5 for ~oth diphenyl oxide and benzene based surfactants. This table illustrates three trends, firstly, the data demonstrate that cotton cleaning per~ormance is enhanced by increasing the length of the alkyl group for both diphenyl oxide~and benzene~based surfactants. Secondly, ~uperiority of the cleaning is observed with the sodium , salt o~ C16 dialkylated DPO~compared to the sodium salt or acid form of the C16 monoalkylated DP0 and the dodecylbenzene su1fonic acid.~ Finally, a comparison of Table 4 with Table 5 shows c1eaning performance enhancement is~preferably obtained with a monosulfonated long chain monoalkylated~ arom~tic surfactant than by a similar iequiva1ent weight monosulfonated dialkylated aromatic surfactant in which its~two shorter alkyl chains are roughly one~half~the length of the long chain u~ed to prepare the monosu1fonated monoalkylated aromatic surfactant.

.,:
; ::

. .

W(~ ~4/OS759 Pl /US93/08080 2~2~7~

% Monoalkylation % Dialkylatiorl % Clean Cot % Clean PEC
, ~
100.0 0.0 59 39 100.0 0,0 62 llO
100.0 OoO 63 33 00.0 O.,0 60 32 94.4 5.6 57 38 94.4 5.6 61 32 :
89.9 10.1 54 38 ~ .
-8!~.9 10.1 55 36 80.8 19.,2 54 35 ::
80.~ 19.2 ~8 33 70.2~ 29.8 50 33 70 . 2 29 . 8 48 39 50~1 49 . 9 57 39 .:
50 .1 4 9 o 9 60 34 40-0 60.0 59 32 ?0 25.0 15.0 66 33 10.0 90.0 75 31 0.0 100.() 77 41 0.0 100.. 0 73 34 ;25 .
4) Type of Aromatic Moiety The in~luence of the type of aromatic moiety on cleaning performanoe is illustrated in Table 3A for C18 :~:
and C20-24 aljkyl chain lengths u~ed in formulations consist~ng of 1 part by weight of the monosul~onated monoalkylated aromatic surfactant to 3 parts by weight : of Igepal C0-520 nonionic ~urfactant. These data show that with the C20-24 alkyl:chain length, the type of aromatic moiety has little effect on the type of :

'-. . , . ~

W ~ ~/05759 ~'CT/~Sg3/080~0 2 ~ ~ 1 7 ~ ~ ~36-- !

Table 5 ~.
The Influence of ~ialkyl Chain Length on Cleaning Perormance mono/di- mono/di- Percent Clean alkylate sulfonate i.
Sulonated Surfactant .
(welght (a~ea Polyester~
perce~t) percent) Cotton cotton Cl~ DAMS DPOl 0/100 84/16 756 6 ~14 DAMS DPOl 0/100 9Z~ 54 2 (c~nparative example) Clo DAMS DPOl 0/977 9~/6 37 27 (comparative ~xample) C12 DA BSA2r3 ~90~ 100/0 716 266 :; ~comparative example) dialkylate Clo DA BSA2 100/0 l00/0 32 28 (comparative example) C16 MA~S DPo4 100/0 93/7 38 33 ~comparative example) C16 MAMS DPo4 Na ~alt 99.8/0.2 91/9 30 38 (comparative example) .:.
C16 DAMS DPo4 Na salt 3/97 89/11 466 qo6 (comparative example) :~
p-Toluene sulonic 33 12 '~
acid -:(comparative exampl~) ~ - ., .. - .. ~ ............................. ... ,..... , ~ ................... ,"
Dodecylbenzene : 35 286 sul~onic acid5 (comparative example) Tide alone ~ ~ 248 113 ~:(comparative example) 1. DAMS D20 - Dialkylated~monosulfonated~diphe yl oxide. ~.;
2. DA BSA - Dialkylated benzene sulEonic acid.
3.l Ari~tol E,IPiLot Chemical.
4. MAMS DPO ~ Monoalkylated monosulfonated diphenyl oxide.
5. BIO SOFT 5-10a'~, Stepan.

6. Average of 2 tests. : .:7. Contai~s 3% trialkylated or higher alkylates j~, c~ea~ing ob~alned. Ilowever, with the C18 alkyl chain '`'~'.

,`,~

W094/05759 pcr/uss3/oBo8l) :

length superior performance is observed with diphenyl oxide than with the MAMS toluene aromatic moiety.

Tahle 6 The In1uence of ~ype o~ Aromatic Moiety on Cleaning Performance Percent Cl~an Sulfonated Surfactantl CottonPolyester/cotton C20_24 ~AMS D.iphenyL oxide 756 466 C20_24 ~AMS Biphenyl , 787 507 C20_24 MAMS Toluene2 776 476 ,~..................... ".,..... ,.,... ~.. ,.... ~, C20_2~ MhMS ~enzene3 75 57 .................................... ~..... ,.. ,.,,.. ~,,........... ~
C20_24 MAMS Benzene4 77 52 Clg ~AMS Diphenyl oxide 606 406 Clg MAMS Toluene5 4Z 31 1. MAMS - monoalkylated monosul~onated 2. Aristol F, Pilot Chemical.
3. Aristol A alkylate, Pilot Chemical, sulfonated with one mole o chlorosulfonic acid per mole of al~ylat~.
4. Aristol A alkylate, Pllot Chemical, ~ul~onated with one mole of sulfurtrioxide per mole of alkylate~ :
5. Aristol G, Pilot Chemical.
6. Average of 6 tests.

7. Average of 2 tests.

B. Ratio of Sulfonated Alkylated Aromatio Sur~actant to Nonionic Surfactant ;,:
The influence o~ the ratio of the sul~onated `:-alkylated aromatic surfactant to nonionic ~urfactant is .
illustrated in Figure 3 for a MAMS diphenyl oxide which is 74.2 weight percent monoalkylated of C20-24 and 86 percent monosulfonation. The results in Figure 3 ..
clearly ~how that there is:a synergistie cleaning performance obtained with the mixed surfaetant system.
~ .

W~94/~s7s9 P~T/US93/08080 :
2 ~ 2 1~ t~ h -38- ' ' ,', The optimum performance is obtained with a weight ratio of about 1 part of the sulfonated alkylated aromatic surfactant to 3 parts of the nonionic surfactant.

C. Influence of Ionization of the Sulfonic Acid The anionic surfaotant~ in salt form are preferably used in cle~ning formulations for cleaning ~tain~ such as blood~ Cleaning formula~ion~ of the present inven~ion are prepared u~ing 1 part by weight monosulfonated monoalkylated aromatic surfactant to 3 parts by weight Igepal C0-520 in which the ~ul~oni¢ acid is neutralized with various bases. The mono~ulfonated monoalkylated aromatic ~urfactant consists of either C20-2~ MAMS toluene ~Aristol F sulfonic acid, Pilot ~, Chemical) or C20-2l~ MA~S DP0 twith a mono-/disulfonation ratio of 86/14 and a mono/ dialkylation ratio of 74.2/25.8)~ Each formulation contains 10 weight percent water based on the total formulation weight. The data 2~ is s~mmarized in Figure 4 and Table 7. The data .~:
demonstrates that neutralization of the sul~onated alkyl ;;~
aromatics in a cleaning composition results in a similar `i~`:
: cleaning performanoe to the unneutralized form~

D. Additlon oÇ Water The influence of water on~cleaning perÇormance ~:
is illustrated~ in Figures 5 and 6 for formulations containing Igepal C0-520 nonionic surfactant. Two ;::
dif~erent types~ of alkyl aromatic~surfaetants are used:
In Figùrle 5 the data were obtained Çor a formulation with 1 part by weight of a MAMS diphenyl oxide with a mono/disulfonation ra5io o~ 86/14 and a :~
mono/dialkylation ratio of 74.2/25.8 for 3 parts by :~.
weight Or I~epal C0-52Q. In Figure 6, 1 part by weight ' ''~.

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

~ ')4/057$9 ~ .L 21 7 9 2PCT/US93/08080 39_ Table 7 MAMSDP0 MAMS DP0 Toluene Toluene Counterion %Clean Cotton %Clean PEC %Clean ~Clean 2 Na 66 49 75 53 4 Ca/2 77 ~1 55 42 ~ DEA 69 45 72 57 of C20-24 monoalkylated toluene sulfonic aeid (Aristol F, Pilot Chemical) was used Por 3 parts by weight of Igepal cb-520.
Both Figure 5 and 6 show that cleaning better than that obtained with TIDE alone (Table 4) can be obtained with water levels o~ up to 80 wt% in the formulations. These figures also show that a small amount (about 10%) of water may be beneficial.

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3 0, , WVg~/05759 PCTt~S93/0~080 ~ 3~ _40~
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E. Type and HLB of Nonionic Surfactant The in~luence of the type and HLB o~ the nonionic surfactant is demonstrated in Tables 8 and 9. These Tables present the data on the cleaning of cotton ~watches in Table 8 and that oP polyester/cotton swatches in Table 9. The pretreatment formulation~
contain 1 part by weight oP ~ulfonated alkylated aromatic surfactant per 3 parts by weight nonionic :`~
surfactant. The data demonstrate that cleaning performance is enhanced by the oleaning oomposition~
comprised of the sulfonated alkylated aromatic surfac~ants of this invention in combination with eikher ~:
a nonylphenol ethoxylate (Tergitol or Igepal) or a `
linear alcohol ethoxylate (Neodol) over the HLB range of

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E. Stick Formulation A stick formulation is prepared with the following composition:

Norpar 15 4n g Neodo} 45-7 lZ g Igepal C0-520 12 g PEG E-900 (Dow)l 2 g Na2 C03 2 g DI Water 6 g . ~:
Aristol F (or ~or DDBSA this 5 g is BIOSOF~ 5-100~) Stearic Acid 2 g Cottonseed Oil 10 g Enzyme (Proteolytic) 2 g ~utal 93 g 1. Polyglycol E900 (Dow) polyethylene glycol :~

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W~94/057ss P~T/US93~08080 2~7~2 -4~

The comparisons in Tables 10 illu~trate that ;:
~imilar cleaning performance is obtained with compo~itions o~ this invention usinK a ~tick (solid) as well a~ liquid cleaning formulations.

.
Table l0 CLEANING PE~FORMANCE
OF STIC~ FORMULA~IONS
SAMP~ lZS
1 0 ''''''' ,I

S~PLE PERCENT C~EAN
IDENTIFICAT~ON COTTON PoLyEsTER/

Aristol ~F~ 74 51 ..
Stick : .', DDBSA Stick 40 29 Tide only no28 ll Pretreatment ~5 ;
:: ,, 3~

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W~94/057s~ PCT/US93/080X0 ,. 212117~2 Experimental Stick hardness i~ mea~ured in accordance with ASTM standard D-127. The procedure uses an ASTM
penetrometer equipped with a standard cone (150 g) without additional weight added. Stick hardness is reflected by the depth the cone penetrates into the stick in five seconds~ The depth is reported in 0.1 mm.
Thus a higher number de~cribes a softer stick. Each stick in this ex~mple ha~ a stick hardness of 92 ., ,'':

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Claims (20)

WHAT IS CLAIMED IS:

1. A cleaning composition, comprising:
a) a nonionic surfactant; and b) a sulfonated alkylated aromatic surfactant, said sulfonated alkylated aromatic surfactant containing an aromatic moiety having 1 to 3 benzene rings and having at least one sulfonate group, provided that when the aromatic moiety contains more than one benzene ring, disulfonate is present in legs than about 50 percent of the total sulfonated alkylated aromatic surfactant, said sulfonated alkylated aromatic surfactant having at least one alkyl group of from C18 up to about C30;
wherein the weight ratio of sulfonated alkylated aromatic surfactant to nonionic surfactant is about 1:19 to about 3:2.

2. The cleaning composition of Claim 1, wherein the aromatic moiety is benzene, toluene, xylene, naphthalene, diphenyl oxide, biphenyl, or biphenylphenyl ether.

3. The cleaning composition of Claim 1, wherein said nonionic surfactant has a hydrophilic lipophilic balance (HLB) value in the range of from about 8 to about 15.

4. The cleaning composition of Claim 1, wherein said nonionic surfactant has a hydrophilic lipophilic balance (HLB) value in the range of from about 8 to about 13.

5. The cleaning composition of Claim 1, wherein said nonionic surfactant has a hydrophilic lipophilic balance (HLB) value in the range of from about 9 to about 13.

6. The cleaning composition of Claim 1, wherein the weight ratio of said sulfonated alkylated aromatic surfactant to said nonionic surfactant is from about 1:9 to about 1:1.

7. The cleaning composition of Claim 1, wherein the weight ratio of said sulfonated alkylated aromatic surfactant to said nonionic surfactant is from about 1.5:8.5 to about 3:7.

8. The cleaning composition of Claim 1, further comprising water in an amount below about 80 weight percent of the total cleaning composition.

9. The cleaning composition of Claim 1, further comprising water in an amount below about 30 weight percent of the total cleaning composition.

10. The cleaning composition of Claim 1, further comprising water in an amount from about 5 to about 20 weight percent of the total cleaning composition.

11. A cleaning composition, comprising:
a) a nonionic surfactant; and b) a sulfonated alkylated aromatic surfactant, said sulfonated alkylated aromatic surfactant containing an aromatic moiety having 1 to 3 benzene rings and having at least one sulfonate group, provided that when the aromatic moiety consists of more than one benzene ring, disulfonate is present in less than about 50 percent of the total sulfonated alkylated aromatic surfactant, said sulfonated alkylated aromatic surfactant having at least one alkyl group of from C18 up to about C30;
wherein the cleaning composition is in the form of a solid stick.

12. The cleaning composition of Claim 11, wherein the solid-stick form is obtained by further comprising the cleaning composition of a sufficient amount of stearic acid and neutralent for the stearic acid.

13. The cleaning composition of Claim 11, wherein the weight ratio of said sulfonated alkylated aromatic surfactant to said nonionic surfactant is about 1:19 to about 3:2.

14. The cleaning composition of Claim 11, further comprising water in an amount below about 30 weight percent of the total cleaning composition.

15. The cleaning composition of Claim 11, further comprising water in an amount from about 5 to about 20 weight percent of the total cleaning composition.

16. A method of cleaning a soil from a surface or fabric, comprising the step of: contacting the soil with a cleaning composition comprising:
a) a nonionic surfactant;
b) a sulfonated alkylated aromatic surfactant, said sulfonated alkylated aromatic surfactant containing an aromatic moiety having 1 to 3 benzene rings and having at least one sulfonate group, provided that when the aromatic moiety consists of more than one benzene ring, disulfonate is present in less than about 50 percent of the total sulfonated alkylated aromatic surfactant, said sulfonated alkylated aromatic surfactant having at least one alkyl group of from C18 up to about C30; and c) water in amount below about 80 weight percent of the total cleaning composition.

17. The method of Claim 16, wherein said water is present in an amount below about 30 weight percent of the total cleaning composition.

18. The method of Claim 16, wherein said water is present in an amount from about 5 to about 20 weight percent of the total cleaning composition.

19. A method of cleaning a soil from a surface or fabric, comprising the step of: contacting the soil with the cleaning composition comprising:
a) a nonionic surfactant; and b) a sulfonated alkylated aromatic surfactant, said sulfonated alkylated aromatic surfactant containing an aromatic moiety having 1 to 3 benzene rings and having at least one sulfonate group, provided that when the aromatic moiety contains more than one benzene ring, disulfonate is present in less than about 50 percent of the total sulfonated alkylated aromatic surfactant, said sulfonated alkylated aromatic surfactant having at least one alkyl group of from C18 up to about C30;
wherein the weight ratio of sulfonated alkylated aromatic surfactant to nonionic surfactant is about 1:19 to about 3:2.

20. A method of cleaning a soil from a surface or fabric, comprising She step of: contacting the soil with the cleaning composition comprising:
a) a nonionic surfactant; and b) a sulfonated alkylated aromatic surfactant, said sulfonated alkylated aromatic surfactant containing an aromatic moiety having 1 to 3 benzene rings and having at least one sulfonate group, provided that when the aromatic moiety consists of more than one benzene ring, disulfonate is present in less than about 50 percent of the total sulfonated alkylated aromatic surfactant, said sulfonated alkylated aromatic surfactant having at least one alkyl group of from C18 up to about C30;
wherein the cleaning composition is in the form of a solid stick.