Note: Descriptions are shown in the official language in which they were submitted.
~ WO 95/16016 2 1 7 7 6 7 8 PCTNS94/14274
I
DETERGENT COMPOSITION CONTAINING AMINE OXIDE SURFACTANT IN THE
FORM OF AGGLOMERATES
FIELD OF THF LNvFNTloN = - -
The present in~erltion is generally directed to a detergent composition in the form of
~ ' having improved ' ' ~ and cleaning, especially in cold temperature
laundenng solutions. More particularly~ the invention is directed to an: __' 1. i .
detergent composition containing an amine oxide surfactant as the pnnciple surfactant and reduced
levels of linear alkylbenzene suhfonate su¢actant (also referenced herein as "LAS") so as to improve
the overall ' ' ~ J of the detergent composition. The detergent composition also achieves
improved cleaning by increasing the solubility of the amine oxide surfactant and LAS~ especially in
cold temperature washing soluhons (e.g. 5C to 30C) and high water hardness conditions (e.g. 7
,, ',, " ) For purposes of producing a high densit~, compact detergent composition~ and i~
order to achieve the benefils discussed herein, the detergent of tlle invention is in the form of
detergent: __' rather than spray dned granules.
BAC}~GRO~ID O~ l~IF INvFl`lTloN
Typically, conventional detergent compositions contain mixtures of various surfactants in
order to remove a wide variety of soils au~d stains from surfaces. For example, various anionic
surfactants, especially the alkyl benzene sulfonates, are useful for remo~ing particulate soils. and
various nonionic surfactants, such as the alkyl ethoxylates and alkylphenol ethoxylates. are useful
for removing greas~ soils.
While the art is replete witll a wide variety of surfactants for those skilled in the art of
detergent forrnulation, most of the available surfactants are specialty chemicals which are not
suitable for routine use in lo~ cost items such as l~ome laundenng ~ . The fact remains
that many home-use laundry detergents shll compnse one or more of the convenbonal alkyl benzene
sulfonates or pnmary alk~l sulfate surfactants. While the convenbonal alkyl benzene sulfonates
exhibit acceptable solubility properties in aqueous larlndenng solutions, they are generally regarded
as possessing poor ~ ~ i c - ~ The pnmary alkyl sulfates~ on t~le other hand.
have acceptable I ' ,, ' ' ' ~ traits but generally do not exhibit acceptable solubilit~ properties,
especially in cold temperature washing solutions,
Another class of surfactants which has found use in vanous compositions where
' ~ is desired compnses the secondary alhyl suhfates (also referenced herein as "SAS").
The conventional secondary aL~cyl sulfate surfactants are available as generaliy pasty, randolll
mixtures of sulfated linear and/or partially branched alkanes. For example, Rossall et al. U. S .
Patent No. 4.235.752. disclose a detergent surfactant which is a C10-l8 secondary aikyl sulfate
containing 50% of 213 sulfate isomers and ~0% of various other effective isomers. The surfactallt
materiais disclosed by Rossall et al is for use primarily in dishwashing operations. Such materjals
SULS~ME SHEET (RUL~ 26)
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WO 95116016 PCT/US94/14274
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have not come into widespread use in laundry detergents. since they do not offer any advantages
over alkyl benzene suifonates. especially witil respect to water solubility and cleaning performance.
Accordingly. i~ossail et al do not provide a high densit~ laundry detergent llaving improved
solubility in either cold temperature wash solutions or iligh hardness water conditions.
Tosaka et ai, U. S. Patent No. 5,096,~;21 (E~ao Corp.), is directed to a detergent compositio
containing an amine oxide surfactant, anionic surfactant and a nonionic surfaciant, togetller wllicl
achieve improved cleaning performance. Tosaka et al aiso exemplifies only "liquid" dishwashing
detergent compositions and hard surface cleaning , although powdered forms of sucll
compositions are aiso , ' ' Moreover, the Tosaka et ai patent does not incorporatc amille
oxide surfactants directiy into detergent ~' for increased solubiiity in cold temperature
washing solutions. itather, Tosai~a et al combine discrete amine oxide particles v~ith spray dned
granules to form their detergent composition. Tbus, the Tosai~a et ai patent does not speak to tile
solubility problem associated with cold temperature laundenng solutions, a problem particuiarl~
prevalent when using detergents having suifate-based (i.e. AS, SAS, Ai~S, etc.) surfactant systellls
compnsing less than about 30/0 of LAS.
The limited solubility of aikyl sulfate surfactants including botll pnmar)~ and secondar~
alkyl sulfates is especiaily prevalent in modern granular laundry detergents which are typicaiiy used
in cold temperature (e.g. 5C to 30C) washing solutions and are formulated in "condensed" or
"compact" form for low dosage usage. For the consumer, the smaller package size attendant with
compact deoergent products provides for easy storage and handling. For the , unit
storage costs, silipping costs and packaging costs are lowered.
The manufacture of acceptable compact or condensed granular detergents has its
difficulties. In a t~picai compact detergent iormulation, the so-called "inert" ingredients such as
sodium sulfate are substantiall~ eliminated. However, such ingredients do play a role in enirancing
solubilit~ of conventional detergents. As a consequence, compact detergents often suffer from
solubilit~ problems, especially in cold temperature laundering solutions. Moreover. conventional
compact or low density detergent granuies are usually prepared by spray drying processes v.~hicll
resuit in extremely porous detergent particles that are qujte amenable to being dissolved in aqueous
washing solutions. B~ contrast, compact detergents are typicaily comprised of less porous. higi
density detergent particles ~hich are less wluble. Thus. since the compact form of granuiar
detergents typicaily compnse particles or granules which contain high leveis of detersive ingredients
with little or no room for solubilizing agents. and since such particles are intentionaily
- - ' at high bulk densities, the net resuit can be a substantial problem with regard to ill-
use solubilit~.
Accoraingly, despite the disclosnres in the art, there remains a need for a detergent
composibon which has improved cleaning performance, especiaily in cold temperature washing
solutions. This need is especiaily prevaient in the art of compact or high density detergents
SUSStlTlJTE SHEET (RULE 26)
~ 21 77678
~WO 9S/16016 PCTIUS94/14274
-3--
currently being used by consumers. There is also a need for such a detergent composition which
achieves these benefits by wa~ of exhibiting improved solubilily of the surfactants in tlle
composition under lligh hardness and cold temperature water conditions, Also, there is a need for
such a detergent composition which exhibits improved ~
SUMMARY OF T~F INYE~I( )1`1
The present invenhon meets the needs identified above by providing a detergent
composition in the fotm of agglomerates which exhibit imptoved solubiliy or dissoluhon of the
surfactants in cold tempetature washing solutions as well as under high water hardness condjtions
Tlle detergent composition compnses a surfactant system having a high level of an amine oxide
surfactant in combination with a low level of linear alkylbenzene sulfonate surfactant. The low
level, i.e. Iess than about 30% of the sutfactant system~ and the omission of phosphates in the
detergent composition is maintained for purposes of achieving impro~ed l,;.vl,~ , Other
adjunct detergent ingredients may also be included in the ~ ~' which fotm the detergent
composition. For example, high acbve (high surfactant levels) patticles (e.g. SAS and AS) may be
optionally included to enhance cleaning.
As used herein. the plurase "imptoved solubiliy" means that the solubiliy of the surfactants
of the detergent composition is enhanced by at least 5% in the laundenng solution when employed
in the manner of this invention, as compared to the solubiliy of Ihe same surfactants per se, under
the same test conditions (i.e. water temperature and pH, sbmng speed and time, particle size, ~vater
hatdness, amd the like). As used herein, the term "~ ~' " refers to patticles formed by
particles which typically have a smaller mean particle size than the fotmed
~,",' All percentages, tatios and propottions used herein are by weight, unless other~ise
specified. All documents including patents and publications cited herein are incorporated herein by
reference.
In accordance ~hith one aspect of the inventio4 a detergent composition in fotm of
~' is provided herein. The detergent composition compnses from about 1% to 50% by weigl~t
of a detersive surfactant system. Tbe surfactant system itsebf comprises, by weight of the surfactant
system, (i) at least about 50% of an amine oxide surfactant, and (ii) less than about 30% of a linear
alkylbenzene sulfonate surfactant. Also, the detergent composition includes at least about 1% by weigbt
3 0 of a detergency builder to enhance cleaning. The sulfactant system and the builder are I ,,,,' ' to
form detergent ,",' which ate substantially free of phosphates. The surfactants in the detergent
composition have improved solubility in an aqueous laundering soluhon. Thus, the solubility of tl~e
e amine oxide surfactant. the LAS suufactant and other surfactants, if included. is enhanced by at least 5/O_
preferably 10 to 50~O, over those same surfactants alone under the sarne test conditions in aqueous
washing solutions at cold i , i.e. 5C to 30C.
In accordance with amother aspect of tbe invenoon, a method for laundenng soiled fabrics is
ptovided. The method compnses the step of contacting soiled fabncs ~ith an effective amouult of a
SU~STITUTE SHEET (~PI~LE 26)
21 77678
WO 95/16016 PCTNS94114274
detergent compositbon as descnbed herein in an aqueous laundering solution. An effective amount is
typicaii~ on tlle order of 1000 to 1500 ppm,
Accordingly, it is an object of the present invention to pro~qde a detergent composition
which has improYed cleaning performance as a resuit of increasillg the solubility of tile surfactants.
5 especiaily in cold temperature ~vashing solubons. It is aiso am object of the invenbon to provide
such a detergent composition wllicll has improved ' ' ' ~ ' ' ' ' ' ~ . These and other objects,
features amd attendant advantages of the present invention will become apparent to those skilled in
the an from a reading of tlle following detailed descnption of the preferred embodiment and tlle
appended claims.
DETAiLED DESCRIPTION OF Ti iE Pi~FEi~RED EMBODIMENT
The invention is directed to a detergent composition having improved solubility in coid
temperature laundenng solubons. A muititude of consumers around Ule world launder soiled
clothes in convenbonal washing machines unique to their panicular geographic locabon. Typicall~
these conventional washing machines launder the soiled clothes in water supplied at relativel~ cold
15 i . ' , for example in range of 5C to 30C, and at higll hardness ' " , e,g, 7
grains/gallon (ncll ~itll Ca and Mg ions), Most of tile modern day consumers aiso use compact or
condensed laundr~ detergellts to accomplish their laundenng needs. Under the ~ "condiholls. solubility of current detergents in aqueous laundenng solutions has been a problem.
This problem is especiall~ exacerbated ~hen tile detergent composition has high levels of aikyl
20 suifates, aikyl etho.Yy suifate and/or secondary aikyl suifates which are not pariicularly amenable to
dissolution in cold aqueous laumdenng solutions, Such surfactants are panicularly useful in moder
laundry detergents since they minimize the nee~i for linear alkylbenzene suifate surfactants wiucl
generaily have poor' ' ' _ ' ' '''~, Anotiler approach to this problenl has been to use cationic
surfactants such as amine oxide but such surfactants ar~ generaily included as a separate
~5 component, i,e. admi~, apan from the detergent granules uilich have been spray dned,
It has now heen found that the solubility of a detergent composition can be increased by
" ~, amine oxide snrfactant with a minimai amount (less than 30% of the surfactant
system) of linear aii~lbenzene suifonate surfactant directiy into the detergent by way of
~' ' By having the detergent composition in the form of: _~' , the solubility of30 the overall surfactant system in the laundering solution is improved. especially those solubons kept
at cold temperatures (e.g. 5C to 30C). To that end, the preferred detergent composition of the
invention compnses from about 1% to about 50%, preferably from about 15% to about 40%, by
weight a surfactant system of which at least 50%, preferabl~ from about 50% to about 100%, is an
amine oxide surfactant and less tilan about 30%, preferably from about n% to about 15%. is a linear
35 aikylbenzene sulfonate (LAS) surfactant, Optionally, the surfactant system may include nonionic
surfact,mts and/or anionic surfactants such as those selected from the group consisting of aikyl
suifates, aii~yl etho,~ suifates. secondary aikyl suifates and mi.Ytures thereof While the level of
SUBSTITIJTE St~EET ~'RliLE 261
~ 2177
WO95/16016 6 ~ 8 PCTIUS94/14274
-5-
these adjunct surfactants can vary, generally they comprise from about 0.01% to about 50% of the
surfactant system.
Preferably. the detergent composition of tlle illvention also compnses at least about 1%.
preferably from about 10% to about 40%. of a detergency builder. The detergent composition may
5 also include one or more of adjunct detergent ingredients. Nonlimibng e.Yamples of tlle detergency
builder and such adjunct ingredients are described in detail hereinafter. Preferably, the detergellt
composition herein is formulated and processed to achieve a density of at least G50 gll for purposes
of producing a "compact" detergent product.
For purposes of enhancing I ' " ' ' ' ~. tlle detergent agglomerates wllicll forn~ tl~e
10 detergent composition of the invenhon preferably do not contain phosphates and contain little or no
LAS. Funher~ it is imponant for tlle detergent composition to be in the form of " ~' " as
opposed to spray dned granules. This is panicularly imponant since most amine oxide surfactants
cannot be readily subjected to spray drying processes ~itllout causing or creatillg extremely adverse
plumes from the spray dr~ing towers. The same is true for alkyl sulfate and alkyl etho.~y sulfate
15 surfactamts. As a consequenoe, past as well as current detergents only incorporate amine oxide
surfactants as a "separate" adjunct ingredient. This, however, does not provide the detergent
composition with satisfactor~ solubilit~ . h
By contrast, the detergent composition of the preseM invention incorporates tlle amine
o.Yide directly "into" the individual ~_' by v~ay of an ~' prooess tecllluque as20 descnbed hereinafter. While not intending to be limited by theory, it is believed that the amine
oxide is brought into the aqueous laundenng solution more rapidly and more completely as a result
of being intimately bound within the 1~' In: ~' ' form, the amine oxide
apparently is extremely hygroscopic and has very little crystallinity tendencies so as to be ver~
soluble, especially in cold temperature washing solubons. Funhermore, by utilizing an amine oxide
25 surfactant along with other adjunct surfactants such as AS, AES and SAS, the o~erall solubility of
the detergent 1~' in cold washing soluhons and high hardness conditions is improved,
thereby resulhng in improved cleaning performance.
The "improved solubility" achieved by the detergent composibon is concerned Witll
enhanoed solubility of the surfactant system of which at least 50% is am amine oxide surfactant.
30 Preferably, the , . represents at least a 5% increase in solubility of the sunfactant system
in the wash solution over the solubilit~ of the same surfactants if they were dissolved alone or
without being contained in a detergent composition as deflned herein. More preferabl~. the
solubility improvement is from about 10% to about 50%. As those shlled in the an ~ill appreciate.
an~ comparison of the surfactant system solubiliy should be completed under tbe same laundering
35 conditions, e.g. water temperature, hardness and pH, stimng speed and hme. and panicle size.
Typical surfactant system solubility , . are set fonh in the Examples hereinaner.
SUBS71TUTE SHEET (RULE 26)
21 77678
WO 9~116016 PCTIUS94114274
Those skilled in the art should also appoeciate the numerous ways in which the amoullt Or
tlle surfactant s~stem in ti~e washing solution can be determined. For example. the amoullt of anline
oxide surfactant dissol~ed can be determine by way of a titration teclmique during whicb samples of
the aqueous laundenng solution containing the detergent composition are taken after one minute
5 and filtered with 0.45 mm nylon filter paper, after which a cabonic titrant, which can be
' "~ purchased, e.g. from Sigma Chemical Company under the trade name Hyamine. is
added to the filtered solution. The filtered solution is then titrated vith an anionic titrant sucll as
sodium dodecyl sulfate. From the foregoing, the amount of cationic surfactant. i.e. amine oxide.
which was dissolved in the ~vashing solution can be determined. The solubilih,~ of the other optional
10 surfactauts contained in the surfactant system c~m be deoermined by well known techniques such as
tlle so~alled "catSO3" titratiou technique. Tlle E,Yamples presented hereinafter illustrate the
improved solubilih of tlle amine oxide surfactant as well as the ' ' ' titration teclmique
Surfactant Svstem
In the broadest aspect of the invention. the __' ' detergent compositioll contains a
5 snrfactant system including at least 50% of an amine oxide surfactant and less than about 3 0% of
LAS. Optionally. the surfactant syslem may include additional surfactants, nonlimiting examples of
which are provided hereinafter.
The amine oxide surfactants suitable for nsed herein have the general formula
R2
Rl (OC2H~)n N O
P`3
wherein Rl is a Cg 24 aik) l group or a subsbtuted Cg 24 alkyl group. R2 and R3 are H, a C l 3
alkyl group or a substituted C l 3 alkyl group, and n is from 0 to about 10.
NonlimitingexamplesoftheamineoxidesurfactantincludeC10 IgamineoYides.
secondary amine oxides, and teniary amine oxides. The tertiar~ amine oxide surfactant may be i
hydrated form and have tlle general formula RIR2R3NO nH2O whereln Rl, R2 and R3 are tlle
25 same as above and n is I or 2. Examples ot other tertiary amines suitable ~or use herein include
those containing one or two short-chain groups ' ', ' ' ~y selected from methyl, ethyl, and 2-
hydroxyethyl groups, with the remaining valences of the amino nitrogen being satisfled witll long-
chain groups ' ', ' 'y selected from pnmary alkyl groups containing 8-24 carbons, e.g.. octyl.
decyl, dodecyl, tetradecyi, hexadecyl, octadecyl, eicos~l, docosyl, and tetracosyl groups. Tile
30 primary aikyl groups may be branched-chain groups, but the preferred amines are those in which at
least most of the pnmary aik~ l groups have a straight chain.
Exemplary of these ten-amines are N-u~ ' " '' ' ' , N,N :'' ' , ' ", ' ' , N-
decyl-N~iu~ic~l.~.,' ' , N-dod.~' '' ' ,' , N ...1~,l.~' '' ' ,' , i~l ~,-~i..~l N
',' ',' ' N~ N:",1 2-~lJIIU~ N,Ndi ~ i~yl-2-
35 ~I~JIU.~J~ I, ' ' , N h_,...~i~' '' ' ' ' , N h_.~t~yld; 2- I.~.,.~y~ ' ' N-
SUBSTITUTE SH~ET (~ULE 26~
-- -- -- ~
~ WO 95/16016 2 1 7 7 6 7 8 P~/US94114274
-7-
~i~.L"J.. ~' ' ' ,' N~N~L.;~u~h,~' N-docosyl-N-2 ~J ~ L~ hylamine~ N-
;.ti,l.u_,'' ',' etc,
Other examples of tertiar~ as well as secondar~ amille oxides suitable for use herein
include~' ',IJ~,1,~1' oxide, ' ','I ' ,' oxide,ell-,' 'yl ~k,LI~J~'
oxide, ~.~' " ', ' oxide, ~ ' oAide, .,.,l~l.,L~ ,, ' oxide,
' ~IJu '~.~' oxide~ ~' ' yll.,.l~J~ oxide~ :'i, "~I.,J~: oxide. bis-(2-
hydroxyethyl) Ivl~.y ` oxide~ bis(2 ~ .,1)-3 -dodeco.Yy-2 ~ J~ r~ Jr~ ' oxide~
(2~ r-."1! 'fIL~,t~ y' oxide, " 'ylul.,~' oxide,dimethyl-(2-
~., J~ l)amine oxide~ and tlle ~ , ' ,, decyl, hexadecyl amd octadecyl homologs of the
10 above compounds. Preferred amine oxide surfactants for use herein include C12 ~4 ' ' ,'
oxides. Mostpreferred is " ' ,' ' ' ,' oxide.
Additional amine oxide surfactants and methods of making Ihe same, all of whicll are
suitable for use herein~ are disclosed by Borland et al~ U.S. Patent No. 5,071,594 and Tosaka et al,
U S Patent No 5~096,621, incorporated herein by reference. Further amine oxides suitable for use
herein are described by Almstead et al, U S. Patent No, 3,351.557. Davis, U,S Patent No.
3,341~459~ Zimmerer et al. U,S. Patent No. 3~202,714: Drew et al, U,S. Patent No. 3~441,611: alld,
Drew~US.PatentNo.3,441612,allofwhichareincorporatedhereinbyreference,
Optionally, the surfactant system can include conventional Cl l-CIg alkyl ben~ene
sulfonates (also referenced llerein as "LAS) as long as the level does not exceed about 30% of tlle
surfactant system. While tlle ' ' ,, ' ' "~ of the so-called "LAS" surfactants have been the
subject of some concern, tne surfactant system herein may include a small amount of (i.e. Iess than
30/O) LAS for purposes of improving the o~erall solubility of the detergent composition without
substanhally decreasing the overall ' ' " ' ' ' ~ of the present detergent compositioll.
Adjunct,cl r . .
The surfactant system may also include a vanety of adjunct surfactants wherein the
aggregate amount of the adjuncts do not exceed 50/O of the surfactant system Nonlimiting
examples are presented herein and include conventional pnmary alkyl sulfate surfactants have the
general formula
ROSO3-M+
whereirl R is typically a linear C10-C20 ùydrocarbyl group and M is a water-solubillzing cation.
Branched-chain primary alkyl sulfate surfactants (i,e., branched-chain "PAS") ha~ing 10-20 carbon
atoms can also be used herein; see. for example, European Patent Application 439~316, Smith et at~
filed 21.01.91~ tlle disclosure of which is incorporated herein by reference (tncluded in tlle term
"alkyl " is the alkyl portion of acyl gronps) Included in the smfactant system are the C I o-C 18 alk~ l
al;Yoxy sulfates (''AEXS'': especially EO 1-7 ethoAy sutfates),
SU~Srl~UTE SHE~T (RU~E 26)
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--8--
Conventionai secondary aikyl suifate surfactants can also be used herein and include those
matenais which have ti~e suifate moiety distributed randomiy along ti~e hydrocarbyl ''backbone" of
the molecuie. Such materials may be depicted by the structure
CH3(cH2)n(cHoso3 M ~(CH2)mCH3
5 wilerein m and n are integers of 2 or greater and the sum of m + n is typicaily about 9 to 17, and M
is a water-solubilizing cation.
More preferably~ a selected secondary ~2,3) aikyl suifate surfac~ant is used herein wllicl
comprises structures of fonmulas A and B
(A) CH3(CH2)X(CHOSO3-M+) CH3 and
lo (B) CH3(CH2)y(cHOso3-M+)cH2cH3
for the 2-sulfate and 3-suifate, respectively. Mixtures of the 2- and 3-sulfate can be used herein. 1
formulas A and B. x and (y+ I ) are, respectively, integers of at least about 6, and c~m range from
about 7 to about 20, preferably about 10 to about 16. M is a cation~ such as an aikali metal,
ammonium, " ' . aikaline earth metal, or tlle like. Sodium is typicai for use as M to
prepare the water-soluble (2,3) alkyl suifates, but: ' ' ' ' ' ,
, potassium~ ammonium, and the like~ can also be used. It is prefened that the
secondary (2,3) aik~l suifates be substantially free (i.e, contain less than about 20%, more
preferably less than about 10%, most preferably less than about 5%) of such random secondary alk~l
suifates.
The preparation of the secondary (2,3) aikyl suifates of the type useful herein can be canied
out by the addihon of H2S04 to olefins. A typical syntbesis using o -olefins and suifunc acid is
disclosed in U.S Patent 3,234,258, Moms, or in U~S. Patent 5,075,041, Lutz, granted December 24.
1991, both of u hich are incorporated herein by reference. The synthesis, conducted in solvents
which afford the secondary (2.3) aikyl sulfates on cooling, yields products which. when punfied to
remove the unreacted matenais. randomiy suifated materials, unsuifated by-products sucll as C 1O
and higher aicohols, secondary olefln suifonates, and the like, are typicaily 90+% pure mixtures of
2- and 3-suifated materials (up to 10% sodium suifate is typically present) and are white, non-tacky,
apparentiy crystalline, solids. Some 2,3-disulfates may aiso be present. but generally compnse no
more than 5% of the mi~ture of secondary (2,3) aikyl '~ Such matenals are available
30 as under the name "DAN", e.g"DAN 200" from Shell Oil Company.
if increased solubility of the "crystailine" secondari~ (2,3) aikyl suifate surfactants is
desired, tile fonmuiator may wish to employ mixtures of such surfactants having a mixture of alkyl
chain lengths. Thus, a mixture of C 12-c 18 aikyl chains uill provide an increase in solubility over a
secondary (2,3) aikyl suifate wherein the alkyl chain is. say, entirely C16. The solubilily of tlle
secondary (2,3) aikyl suifates can also be enhanced by the addition thereto of otiler surfactamts sucl
as the material which decreases the crystallinity of the secondar~ a,3) aikyl suifates~ Sucll
SUBSTITU~E S~iELT (~llLE 26~
~ 2177678
~ WO95/16016 PCT/US94/14274
g
,, matenais are t~picaily effective at levels of 20%, or less. of the secondar~
(2,3) aikyl suifate.
Additionai noniimiting examples of surfactants useful in conjunction witll tlle surfactallts
described herein are the C10-C18 aikyl aikoxy carboxylates (especiaiiy the i~O 1-5
CtllUA~ JU~ the C~0 ~8 glycerol ethers, the Clo-C18 aikyl pG~ o~ . arld titeir
" ' _ suifated ~/ul~ ,u~d~, and C12-Cl8 ~ fatt~ acid esters. If desired.
the conventional nonionic and amphotenc surfactants such as the C12-C 18 aikyl etho.~ylates ("AE")
including the so-called narrow peaked alkyl ethoAylates and C6-C12 aikyl phenol alkoxylates
(especially etitoAylates and mixed ' ~/1 . y), C12-C18 betaines and sulfobetaines
("suitaines"), can also be included in the overall ~ , The C10~18 N-ali~yl polyhydro.
fatty acid amides can also be used. rypiQI examples include the C12-C18 i~
See WO 9,20G,15~. The N-propyl through N-heAyl C~2-C18 glucamides can be used for lo-~
sudsing. C lo-C20 conventionai soaps may aisû be used. If high sudsing is desired. the branched-
chain C10-C16 soaps may be used. Mixtures of anionic and nonionic surfactants are especiall~
useful. Other conventional useful surfactants are listed in standard teAts.
Builder
The detergent composition of the invention aiso includes a detergency builder matenal to
asslst in controlling mineral hardness. inorganic as well as organic builders can be used. Builders
are typically used in fabnc laundenng compositions to assist in the removal of particulate soils.
Inorganic detergent builders include, but are not limited to, the aikaii metai, ammonium and
" ' saits of phytic acid, silicates, carbonates (including bicarbonates and
` sulphates, and
Examples of siiicate builders are tlle aikali metal silicates, particuiarly those having a
SiO2:Na2O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium
siiicates descnbed in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. i~ieck. NaSKS-6 is t~le
trademark for a crystalline layered silicate marketed by Hoechst (commoniy abbreviated herein as
"SKS-6"). Urliike zeolite builders, the Na SKS-6 silicate builder does not contain aiuminum.
NaSKS-6 has the delta-Na2SiO5 morphology form of layered silicate. It can be prepared by
methods such as those described in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a
highly preferred layered silicate for use herein, but other such layered siiicates, such as thoSe havillg
the general formula Nai~fSi~ 02x+ 1 yH20 wherein M is sodiunl or hydrogen, x is a number fron
1.9 to 4, preferabl~ 2, and ~ is a number from 0 to 20, preferably 0 can be used herein. Vanous
other layered silicates from Hoechst include NaSKS-5. NaSKS-7 and NaSKS- 11, as the alpha. beta
and gamma forms. As noted above. the delta-Na2SiOs (NaSKS~ form) is most preferred for use
herein. Other silicates may aiso be usefui such as for example magnesium silicate, whjch can ser-e
as a crisping agent in granular ~ ' . as a stabili~ing agent for o.Yygen bleaches, and as a
component of suds control systemS.
al~SrllUTE SHE~ (RULE 2fi~
WO 95/16Ui~ 2 1 7 7 6 7 8 PCT/US94/14274
--lo-
Examples of carbonate builders are the alkaline eardl and aikali metal carbonates as
disclosed in Gennan Patent Application No. 2.321,001 publisbed on November 15, 1973.
A I " builders are useful in the present invention. ~ ~ ' builders are of great
importance in most currently marketed lleavy duy granuiar detergent , , and can also be
a significant builder ingredient in liquid detergent fonmulations. Al builders include
those ha~ing the empincal fonnula:
MZ(ZA102)yl 'AH2
wherein z auld y are integers of at least 6, tile molar ratio of z to y is in tlle raulge from 1.0 to about
0.5. and x is an integer from about 15 to about 264.
Useful ' ' ion exchange matenals are "~, available. Tilese
: ' ' can be crystalline or amorphous in structure and can be naturally-occuning or synthetically deri~ed. A method for producing ' " ion exchange
materials is disclosed in U.S. Patent 3.985.669, iCrummel. et al, issued October 12, 1976. Preferrcd
synthetic crystalline ' " ion exchange materials usefui herein ane available under the
designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially prefened
embodiment, t}le crystalline ' ' ion exchange material has the formuia:
Nal2¦(AiO2)12(sio2)l2] x~i2o
wherein x is from about 20 to about 30, especiall~ about 27. This material is known as Zeolite A.
Dehydrated zeolites ~x = 0 - 10) may also be used herein. Preferably, the ' ' has a
particle size of about 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the present invention include, but
are not restricted to, a wide vanety of ,/UIJ~I.UAy compounds. As used herein, "poly-
carboxylate" refers to compounds having a pluraiity of carboxylate groups, preferably at least 3
carboAylates. Pul~ . builder cam generally be added to the composition in acid form but
can also be added in the fonm of a neutraiiæd sait. When utilized in salt fonm, aikali metais, such
as sodium, potassium, and lit~lium, or ~" ' saits are preferred.
included among the POI~ builders are a variety of categories of usefui materials.
One important category-of ~JulJ~buA~' builders encompasses the ether IJ~/IJ~ JUA~
including UA~' ' , as disclosed in Berg. U.S. Patent 3,128.287, issued Apnl 7, 1964, and
Larnberti et al. U.S. Pater t 3,635.830, issued January 18, 1972. See aiso "TMS/TDS" builders of
U.S. Patent 4,663 071. issued to Bush et al, on May 5, 1987. Suitable ether ~ul) ' ~: aiso
include cyclic compounds, particularly aiicyclic compounds. such as those descnbed in U.S. Patents
3~923,679; 3,835,163; 4,158,635; 4,120.874 and 4,102,903.
Other useful detergency builders include the ether I ' ~ J~IJUA~ , copolymers ofmaieic anhydride with ethylene or vinyl methyl ether, 1, 3, 5~trihydroxy benæne-2, 4, 6-
trisulphonic acid. and ~.~u l.u.~ ', Iu.~ . acid, the various alkali metai, ammonium and
substituted ammonium salts of polyacetic acids such as elhJ' ' tetraacetic acid and
SUB~lTUrE SHEET (~ULE 2~)
WO 95/16016 ~ 1 7 7 6 7 8 PCT/US94114274
' " acid~ as well as pul~ such as mellitic acid, succirlic acid. UA~ '
acid, polymaleic acid. benzene 1.3,5-tricarboAylic acid, .~ubu~ ", lu~ ' acid. and soluble
salls thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are
5 uul~ ' ' bvuilders of particular importance for heavy duty liquid detergent formulations due
to their availabilit~ from renewable resources and their 1- ' ,, ' ' ' ~ . Citrates can also be used,
however, in granular ~ 1, especially in combination with zeolite and/or layered silicate
builders. OA~ ' are also especially useful in sucl~ compositions and ~ ' '
Also suitable in tlle detergem compositions of the present invention are the 3,3-dicarboA~-
4-oAa-1,6 ' ' and the related compounds disclosed in U.S. Patent 4.566,984. Bush,
issued lanuary 28. 1986. Useful succinic acid builders include the C5-C20 alkyl and alkenyl
succinic acids and salts thereo A particularly preferred compound of this type is duJ~
acid. Specific eAamples of succinate builders include~
' ~' 2-:' ' ,' (preferred), 2-~u~ ~..,' ' and the like.
T ~ ' are the preferred builders of this group, and are described in European Patent
Application 86200690 5/0.200.263, published November 5, 1986. Other suitable ,UU~ bVA~
aredisclosedinU.S.Patent~,144,226,Crutchfieldetal,issuedMarchl3.1979andinU.S.Patent
3,308,067, Diehl. issued March 7, 1967. See also Diehl U.S. Patent 3,723,322.
Fatty acids. e-g, C12-C18 ' ' ,1... acids, can also be incorporated into the
compositvons alone, or in combination with the aforesaid builders, especially citrate and/or the
succinate builders, to provide additional builder activity. Such use of fatty acids will generatly result
in a diminution of sudsing, which shoutd be taken into account b~ the formnlator.
Detert~ent Adiunct In~r rli, n~c , . .
The detergent composition can also include any number of additional ingredients in an amount
from 0% to about 75% by weight of the detergent composition. These ingredients inclnde bleaches.
bleach activators, suds boosterc or suds suppressers, anti-tarnish and . . agents, soil
suspending agents, soil release agents, germicides, pH adjusting agents, nonbuilder alkalinity sources,
chelating agents. smectite clays, enzymes, ~ agents and perfumes. See U.S. Patent
3,936,537, issued Febrr,ar~ 3, 1976 to Baskerville, ~r. et al., incorporated herein by reference.
Bleaching agents and activators are descnbed in U.S. Patent 4,412,934, Chung et at., issued
No~ember 1, 1983. and in U.S. Patent 4,483,781, Hartman, issued November 20, 1984. both of wluch
are incorporated herein by reference. Chelating agents are also descnbed in U.S. Patent 4,663,071.
Bush et al., from Column 17, line 54 through Column 18. Iine 68. incorporated herein by reference.
Suds modifiers are also optional ingredients and are described in U.S. Patents 3,933,672, issued
January20. 1976toBartolettaetal.,and4,136,045,issuedJanuary23, 1979toGaultetal.,both
incorporated herein by reference.
rllUTE SHEET (RULE ~
. WO95/16016 2 1 77678 pCTlUS94/14274
-12-
Snitable smectite clays for use herein are descnbed in U.S. Palent 4,762.645, Tucker et al.
issued August 9, 1988, Coluu~ 6, line 3 througll Column 7, line 24, incorporated herein by reference.
Suitable additional detergency builders for use hereln are enumerated in the Baskerville patent, Column
13, line 54 througil Column 16, line 16, and in U.S. Patent 4,663,071, Bush et al, issued May 5, 1987,
5 both incorporated herein b~ reference.
Enzymes can be included in the formulations herein for a wide variety of fabnc laundering
purposes, including removal of ~ - b~rA Wbv~lJ.' ! ~ or ~ , ' ' b~ stains, for
example, and for the pre~elltion of refugee dye transfer. and for fabric restoration. The enzymes to
be incorporated include proteases, amylases, lipases. cellulases and peroxidases, as well as mixtures
10 tllereof Other types of enzymes may also be included. The~ may be of an~ suitable ongill, sucll as
vegetable. animal~ bacterial, fungal and yeast ongin. However, their choice is go ~erned by several
factors such as pH-activity and/or stability optima, ll..,., ' ' ~, stabilit~ versus active detergellts.
builders and so on. In this respect bactenal or fungai enzymes are preferred. such as bactenal
amylases and proteases, and fungal cellulases.
Suitable examples of proteases are the s2 btili~ins which are obtained from particu ar stMills
of B.st2btiDs and B. Iichenifon12s. Another suitable protease is obtained fronl a strain of Bacillus.
having maYimum activit~ throughout the pH range of 8-12, developed and sold by Novo Illdustries
A/S under the registered trade name ESPEilASE. The preparation of this enz~me and analogous
ereymes is descnbed in British Patent Specification No. 1,243,784 of Novo. Proteolytic errzymes
suitable for removing protein-based stains that are, '1~ available include those sold under
the trade names Ai,CALASE and SAVINASE by No~o Industries A/S (Denm2trk) and
MAXATASE by Internabonal Bio-Synthetics, Inc. (The Netherlands). Other proteases include
Protease A ~see European Patent Application 130,756, published Januar~ 9, 1985) and Protease B
(see European Patent Application Serial No. 87303761.8, filed Apnl 2X, 1987, and Europe1n Patent
Application 130.756, Bott et al, published Januar~ 9, 1985).
Amylases include, for example, ~-amylases descnbed in Britisll Patent Specifica'don No.
1,296,839 (Novo), i~APiDASE, International Bio-Synthetics, Inc. and TE~MAMYL, Novo
Industries.
The cellulase usable in the present invention include both bactenai or fungal cellulase.
Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in
U.S. Patent 4.435~307, Barbesgoard et ai, issued March 6, 1984. which discloses fungal celluiase
producedfromHumicolainsolensauldHumicolastrainDSMlSOOoracellulase212-producing
fungus belonging to the genus Aeromonas, and cellulase extracted from the ' , ', of a
marine mollusk (Dolabella Auncula Solander). suitable cellulases are also disclosed ill GB-A-
2.075.028; GB-A-2.095.275 and DE-OS-2.247.832
Suitable lipase enzymes for detergent usage include those produced by ,, of
the ~2 ' group, such as F ' stutzeri ATCC 19.154, as disclosed in Bntish Patent
SUBSTITUTE SHEET fllULE 261
WO 95/16016 2 1 7 7 6 7 8 PCI/~JS94/14274
-13-
1,372.034. See also lipases ill lapanese Patent Application 53.20487, laid open to public inspectio
on February 24, 1978. This lipase is available from Amano r~ ~ cO. Ltd., Nagoya,JaparL under tlle trade name Lipase P "Amano," hereiltafter referred to as "Amano-P." Other
commercial lipases include Amano-CES. Iipases ex ('' ' viscosum, e.g. (''
5 viscosum var. Iipolyticum NRRLB 3673" 1~ available from Toyo Jozo Co., Tagata,
Japan; and furtl~er (`! ' ' ~tscosum lipases from U.S. Biochemical Corp., U.S.A. and
Disoynth Co., The Netherlands. and lipases ex r ~ gladioli. The LIPOLASE enylne
denved from Humicola lanuginosa and . "~ available from Novo (see also EPO 341.947)
is a preferred lipase for use herein.
Pero.xidase enzymes are used in combination witl~ oxygen sources, e.g., percarbollate.
perborate, persulfate, hydrogen peroxide, etc. Tlley are used for "solution bleaching," i.e. to preveni
transfer of dyes or pigments removed from substrates dunng wash operations to otller substraoes i
the wash solution. Peroxidase enymes are known in the art. and include, for example. horseradisl
peroxidase, ligninase, and I ' . ' such as chloro- and :. r_.v,~ld~. Peroxidase-containing detergent compositions are disclosed. for example. in PCT International Applicatioll WO
89/099813. published October 19. 1989, by O. Kirk. assigned to Novo Industries A/S.
A wide range of enzyme matenals and means for their , into synthetic
detergent compositions are also disclosed in U.S. Patent 3.553,139. issued Januar~ 5, 1971 to
McCart~etal. EnymesarefurtherdisclosedinU.S.Patent-1,101,457,Placeetal,issuedJulyl8,
1978, and in U.S. Patent 4,507,219. Hughes, issued March 26, 1985, both. Enyme materials useful
for liquid detergent r ' " , and their i , into such r ~ " , are disclosed in
U.S. Patent 4,261,868, Hora et al, issued Apnl 14, 1981. Enzymes for use in detergents cim be
stabilized by various techniques. Enyme stabilization techniques are disclosed and exemplified in
U.S. Patent 3,600,319, issued August 17, 1971 to Gedge. et al. and European Patent Application
Publication No. 0 199 405, Application No. 86200586.5. published October 29, 1986, Venegas.
Enyme stabilization systems are also descnbed, for example, in U.S. Patent 3,519,570.
Additionally, dye transfer inhibittng agents may also be included, for example,
~IJ . ;.., ~P, . . ` ' polyamine N-oxide, copolymers of N . ;.., !,,, . ' ' and N . , ' ' ' are
a suitable dye transfer inhibiting polymers for use in the present detergent composition. Tlle le~el of
30 such additional dye transfer inhibiting agents may vary, but typically will be from about 0.01% to aboul
10% by weight of the detergent composibon.
prn~cc
The following descnbes and exemplifies the I ' process by whicll tl~e detergel~tcomposition of tlle inventioll is produced. The parameters noted herein are exemplary only alld
35 should not be considered as limiting in any way.
SteD A - Preparation of Surfactant P~c'~ - The objective is to combine the surfactants
including the amine oxide surfactant and liquids in the compositions into a common mix in order to
SUBSrllUTE SH~ ~JLE 26)
WO95116016 2 1 7; ~7~ pCI/US94/14274
aid in surfactant ' ' '' and ~ ~ ' In this Step, the su~factants and other liquid
components in tlle composition are miYed together in a Sigma Mixer at 140F (60C~ at about 40
rpmtoabout75rpmforaperiodoffrom 15minutestoabout30minutestopro~ideapastehaYing
the general coPsistency of 20.000-40,000 centipoise. Once thoroughly mixed, the paste is stored at
5 140F (60C) until lv_' ' Step (B) is rQdy to be conducted.
Step B - ~ r.; ' " of Powders with Surfactant Paste - The purpose of this Step is to
transform the base formula ingredients into flowable detergent ag~elomerates having a mean particle
size range of from about 800 microns to about 1600 microns. In this Slep, the powders (includillg
materials such as zeolite, citrate, citric acid builder, layered silicate builder (as SKS-6), sodiun~
10 carbonate, ~ " ' magnesium sulfate and optical bnghtener) are charged into
the Einch Mixer (R-Series) and mixed bnefly (ca. 5 seconds - 10 seconds) at about 1500 rpln to
about 3000 rpm in order to mix the various dry powders fully. The surfactant paste frol~l Step A is
t~len char~ed into the miYer and the mixing is continued at about 1500 rpm to about 3000 rpm for a
penod from about I minute to about 10 minutes, preferably 1-3 minutes. at ambient temperature.
The mixing is stopped when course agglomerates (average particle size 800-1600 mdcrons) are
formed.
SteP C - The purpose of this Step is to reduce the lw' ' stickiness by
v moisture and to aid in particle size reduction to the target pardcle size (in the
mQn particle size range from about 800 to about 1600 microns, as mQsured by sieve ana~ysis). In
this Step, the wet agglomerates are charged into a f uidized bed at an air strQm temperature of froln
about 41C to about 60C and dried to a final moisture content of the particles from about 4% to
about 10%.
SteP D - Coat Aeelomerates and Add Free-Flow Aids - The objective in this Step is to
achieve tbe final target agglomerate size range of from about 800 microns to about 1600 microns~
and to admix materials which coat the lw' reduce the ' _' . v tendency of the
particles and help maintain acceptable flowability. In this Step. the dried agglomerates from Step C
are charged into the Eirich Mixer (R-Series) and mixed at a rate of about 1500 rpm to about 300()
rpm while adding 2~6% Zeolite A (median particle size 2-5~Lm) dunng the mixing. The mixing is
continued until the desired median particle size is achieved (typically from about 5 seconds to about
45 seconds). At this point, from about 0.1% to about 1.5% b~ weight of precipitated silica (average
particle size 1-3 microns) is added as a nOw aid arld the mixing is stopped.
In order to make the present invention more readily understood, referenc~ is made to tlle
following examples, ~hich are intended to be illustrative only and not intended to be limiting i
scope.
SU~7TIJIE SHET (RULE 26)
21 77678
WO 95/16016 PCTIUS94/14274
--15--
EXAMPLE I
Sevetal detergent compositions (A-E) ate made in accordance witb the q,,_' '
process described abo-~e. t~: , ' A~ B and C ate within tlle scope of the invention and
compositions D and E are outside of the invention and are presented for purposes of comparison as
5 desctibed in Example 11 hereinafter. The relative proportions of compositions A-E, in agglometate
form, qre listed in Table I belou.
A B C D E
Component Surfactants % (wt.) % (wt.~ ~ 1 % (wt.~ % (wt.)
C14 l5 primary alkyl sulfate - 2.5 19.2 16.9
C12-CIs alkyl etho.~y (1-3) sulfate - 1.5 - 10.8 9 5
C10 Islinearalkylbenzenesulfonate~l~a - - - _ 3.6
Nonionicl 3 3
Amine Oxide2 24.7 23 5 31.7
Builders
Zeolite 4A 37.9 36.9 37.0 40.0 40.0
Carbonate(Na) 18.3 17.8 17.9 16.1 16.1
Additives
Polyethylene glycol (M.W. 4000) - 1.0 1.2
Misc. (water, petfume and minors~ 15.8 16 8 12 2 13,9 13.9
100.0 100.0 100.0 100,0 100.0
Inonionic smfactant commercially available from Sh~ll Chemicql Company und¢ the trade ~ame Neodol
(23-9).
2dimethyl amine oxide sulfactant commercially available from Procter ~ Gamble.
10 EXAMPLE 11
This Example illustrates the surpnsingly improved solubility achieved by the detergent
Composibon of the invention. Specifically. standatd dosages of compositions A-E ( 1170 ppm) are
dissol~ed in an aqueous laundering solution having a waler temperature of 10C and a water
hardnessof7grainslgallon(Ca:Mgratioof3:1). Thelaundenngsolutionisconhnuouslyagitated
15 at a rate of 75 rpm and samples of the wash solution were taken at vanous time intervals as shown
in Table I below. For putposes of iDustrahng the improved solnbility of the detergent compositioD
according to the invention. the amonnt of surfactant in the laundering solutioll is determined b!
conducting the btration techniqne descnbed previously wherein samples are taken from individual
wash solutions containing one of the compositions A-E and titrated to determine the cationic
20 surfactant More specifically. the amount of cationic surfactant dissol ed in tlle
lanndering solution is determined by filtering the ' ' samples throngh 0.45 nylon filt~r
paper to remove the insolubles and thereafter, adding a cationic titrant, suclt as Hyaminer" whicll is
' ''~ available from Sigma Chemical Company. to tbe filtered solution. The filtered
21 77678
Wo 95/16016 PCTIUS94/14274
-16-
solution is then utrated with an anionic titrant to determine the cabonic From the
foregoing, the relative amount of surfactant dissolved in the wash solution can be determined. This
teclunique is well isnown and others may be used if desired, especiaily if ~ of anionic
and nonionic surfactants are desired. The resuits are shown in Table 11 below.
T~BLE n
(% total of cahonic or anionic dissolved)
Time (Minutes) A ~ C D " E
O0.0% 0.0% 0.0% 0.0% 0,0%
88.~% 71.0% 80.0% 22.0% 30.0%
392.3% 90,0% 97.0% 34.0% 39.0%
1093.3% 97.0% 97.0% 34.0% ~8.0%
From tile results ill Table 11. it is quite clear that compositions A, B and C which are within the
scope of the invention surprisi~lgly have improved solubility over compositions D and i_ whicil are0 outside the scope of the invention.
i~aving thus descnbed the invention in detail, it will be obvious to those sicilled in the an
that varjous changes may be made without departing from the scope of the invention and tile
invenbon is not to be considered limited to what is described in the specification.
-
~BSrlN~E SHET (RULE 2~
