Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
w0 95/33029 2 1 9 1 3 1 3 J ~
BUILT DETERGENT COMPOSITlO~iS COi~PRISING
OLEOYL SARCOSINATE
FTFT.n QF ~ INVE~TION
S The present invention relates to the use of oleoyl sarcosinate in detergentl.u~ Oa;~iull~ built with zeolite andlor silicate builder materials to pro~ide improved
cleaning benefits.
BACKGROUNl~) OF T~F INVENTIQN
The fnrm~ tinn of effective laundry detergent .,UIIllJOa;~iulla which are
10 sufficiently robust to remove a wide variety of soils and stains from fabrics under a
vanety of usage conditions remains a u ulla;deldbl~ challenge to the indusIr~l. This is
especially true since the advent of legislation which limits the use of effective
phosphate builders in many regions of she world.
Various laundry detergent uulll~Joa;Liull~ which are designed not only to clean
15 fabrics, but also to provide additional fabric care benefits, have been described in the
literature and have entered the I~ ke~pl~,c v~ith very substantial commercia.l success.
Whiie a review of the literature would seem to suggest that a wide sellection ofsurfactants is available to the detergent r el, the reaGty is that many such
materials are specialty chemicais which are not suitable for routine use in low unit
20 cost items such as home laundering l.u..,~ ;."~ The fact remains that most home-
use detergents still comprise one or more of the uu..i~,., ;u..~l ethoxylated nonionic
and alkyl sulfate or aikyi benzene sulfonate anionic surfactants, presumably ~iue to the
economic and ~ ul~ é ..(~
By the present invention, oleoyl sarcosinate is employed as an anionic
25 detersive surfactant in granular laundry detergent , '" built with
_' ''' andlor silicate builder materials, The resulting r.. i-~;.,, ~ exhibit
excellent solubiGty even at cold water L.,(.(~,~,...Lh.,_~, excellent cleaning of both
particulate soils and greasy and oily soils, and provide excellent ~ ( "''~y andcleaning benefits with other detergent adjuncts, including enzymes. The Cu~pOa;L;ulli~
30 also provide excellent color care for dyed fabrics and excellent skin mildness for
handwash operations. These and other advantages of the present invention will beseen firom the disclosures hereinafter.
BACKGRQUND ART
Oleoyl sarcosinate is described in the fûllowing patents and publications: U.S.
35 2,54~,385; U.S. 3,40'',990; U.S. 3,639,568; U S. 4~772.424; U.S. 5,186,855;
European Patent Publication 505,129; British Patent PubGcation 1,211.545; Japanese
Patent Publication 591232194; Japanese Patent Publication 62/295997; Japanese
W09~/33029 2 9 ~ 3 1 3 PCTIIJS95106821
Patent Publication 02/180811. and ~hemical Abstracts Service abstracts No.s
~1.3244q~ 70:~8865x. and 83:181020p.
SU~A~ 9F T~ VENTION
The present invention cl~u~ ~ac~ detergent compositions comprising:
S (a~ at least about 0.1% by weight of oleoyl sarcosinate surfactant,
(b) at least about 0.001% by weight of one or more detergency buiiders
selected from the group corlsisting of r' - ' , silicate builders,
and mixtures thereof; and
(c) the balance comprising detersive adjuncts and carrier materials.
Preferred eulll;/Oa;~iOI~a herein additionally comprise at least about 0.001%~ b~
weight, of an enzyme, especially an enzyme selected from the group consisting ofproteases, amylases, Iipases, cellulases, and ~,~. u~u klaca. as well as mixtures thereof
Fully-formulated c~mrhcitinne herein may additionally comprise at least about
1%, by weight, of a non-oleoyl sarcosinate detersive sufiaàant~ especially surfactants
15 selected from the group consisting of alkyl sulfates~ alkyl ethoxy sulfates,
pol~ d,u,.y fatty acid amides, ethoxylated alcohols, and mixtures thereof.
Preferred granuiar laundry detergents provided by this invention comprise:
(a) from about 0.1% to about 55%, by weight, of oleoyl sarcosinate
sufiactant;
(b) from about 1% to about 80%, by weight, of one or more detergency
builders selected from the group consisting of ~ .... ,lh~ , silicate,
and mixtures thereof;
(c) from 1% to about 35%, by weight, of a non-oleoyl sarcosinate
detersive sufiactant;
~5 (d) from about 0.001% to about 5%, by weight, of enzymes selected from
the group consisting of protease, cellulase, amylase, lipase,
peroxidase, and mixtures thereof; and
(e) the balance of the ~ lh~ comprising detersive adjunct
ingredients.
The invention aiso ~ u .; ---. a method for cleaning soiled fabrics,
comprising contacting said fabrics with an aqueous medium which contains at least
about 50 ppm, preferably from about lû0 ppm to about 10,000 ppm, of a
according to the above, preferably with agitation.
Aii ~ ,c.-t ,,_~, ratios and Inu~vlLiu~la herein are by weight, uniess otherwise3 5 specif ed. Ail documents ated are, in relevant part, i~,u- ~,v, a~ed herein by reference
DETAILED DESrRIPTIoN OF T~F. I~ENTIQN
OleoYI S~
1~ woss/33029 219131 3 r~.,u~
. 3
The present invention ~ comprise oleoyl sarcosinate, in its acid
andior salt form selected as desired for the ~,ullly~a;li~1ll5 and uses herein~ having the
following formula:
O
CH3 O
wherein M is hydrogen or a cationic moiety. Preferred M are hydrogen and alkali
metal salts, especially sodium and potassium. Oleoyl sarcosinate is ~Olll~ 'ly
available, for example as Hamposyl O suppiied by W. R. Grace & Co. r. l ,.o~.,;
according to the present invention typically comprise from about 0.1% to about 55%~
preferably from about 1% to about 20%, and most preferably from about 3% to
about 15%, of oleoyl sarcosinate by weight of the ~,ulllyOa;L;u~l.
In addition to the C~ .,;ally-available oleoyl sarcosinate, oleoyl
sarcosinate useful herein can aiso preferably be prepared from the ester (preferably
the methyl ester) of oleic acid and a sarcosine salt (preferably the sodium salt) under
anhydrous reaction conditions in the presence of a base catalyst with a basicity equal
to or greater than alkoxide catalyst (preferabiy sodium methoxide). For example. the
reaction may be illustrated by the scheme:
OCH3
ICH3 0
H'N~ONa
NaOCH3 (cat)
CH~
w095133029 ~ 21 91313 r~ r~
This salt may optionally be neutrali~ed to form the oleoyl sarcosinate in its acid
form.
The preferred method for preparing oleoyl sarcosinate is conducted at a
t~ ,.d~UI ~ from about 80C to about 200C~ especially from about 120C to about5 2D0C It is preferred to conduct the reaction without solvent although alcoholSolvents which have a boiling point of at least 100C and are stable to the reaction
conditions (ie. glycerol is not acceptable) can be used. The reaction may proceed in
about 85% yield with a molar ratio of methyl ester reactant to sarcosine salt reactant
to basic catalyst of about 1:1:0.05-0.2.
Methyl ester mixtures derived from high oleic content natural oils (preferably
having at least about 60%. more preferably at least about 75%, and most preferably
at least about 90% oieic content) are especially preferred as starting matenals.Examp~es include high-oleic sunflower and rapeseed/canola oil. In addition. a high-
oleic methyl ester fraction derived from either paim kernel oil or tallow is acceptable.
It is to be understood that such oils typically will contain some levels of impurities,
including some fatty acid impurities that may be converted to sarcosinate compounas
by this synthesis method. For example, commodity ., ll~ola/~a~ , ,d oil may comprise
a majority of oleic acid, and a mixture of fatty acid imi~urities such as palmitic,
stearic, linoleic, linolenic and~or eicosenoic acid, some or ail of which are converted
to the sarcosinate by this reaction method. If desired for fi ,. . ~ purposes, some
or all of such impurity materiais may be excluded from the starting oil before
preparing the oleoyl sarcosinate to be used in the present ~
Finaily, sarcosine remaining in the reaction mixture can be converted to an
amide by addition of maleic or acetic anhydride to the mixture, thereby minimizing
the sarcosine content and any potential for formation of undesired nitrogen-
containing impurities.
The synthesis of oleoyl sarcosinate may be carried out as follows to prepare
the sodium oleoyl bo.l I _'
SYnthr ic of Oleovl Amide of Sarrr~cinP Sodium Salt - A 2 L, 3-neck, round
bottom flask is fitted with Ll~ ul~c~, Dean-Stark trap with condenser, mechanical
stirring, and a gas inlet adapter through which nitrogen is passed over the reaction
mixture. The reaction vessel is charged with sarcosine (43.3 g, 0.476 mol), sodium
methoxide 25% in methanol (97.7 g, 0.452 mol), and methanol (400 mL). The
reaction is refluxed 15 min to neutralize the sarcosine and then methyl ester derived
from Carsill reguiar high-oleyl sunflower oil (l48.25 g, 0.5 mol) is added. After the
methanol is removed with the Dean-Stark trap, reaction mixture is heated to 170C
for I hr to drive off any water. The reaction is initiated by the addition of sodium
~ woss/3302s 21 913t3 P .,~
methoxide 25% in methanol (15 4 g, 0.0714 mol). Reaction is kept at 170C for 2.5
hr during which methanol is collected in the Dean-Stark trap The reaction is
aliowed to cool slightly and then methanol (200 g) is added. Maleic anhydride (9.43
g, 0.095 mol) is added to the methanol solution and the reaction is stirred at 60C for
5 0.5 hr. Then most ofthe methanol is removed by rotary cv~.~,u.~iu.. and acetone (2
L) is added to precipitate the product. The product is collected by suction filtration
and allowed to air dry to give an off-white solid. Analysis of the reaction mixture by
GC indicates the majority of the product is oleoyl sarcosmate, with minor amounts of
the following impurities: sarcosine, oleic acid, and the a(ll~,Ua;lld~ deri~ed from
10 palmitic acid, stearic acid, and linoleic acid.
Al""~ and SilicateBuilders The evel of I ' " and silicate
builder used in the present invention ~,.,."l,-,~:~i.."~ can vary widely depending upon
the end use of the ~ The present granular ~u l~u~ will typicail~
comprise at least about 1% of such builder, more typically from about 1% to about
80%, and most typically from about 5% to about 50% by weight ofthe ~
Lower or higher levels of builder, however, are not meant to be excluded.
Examples of silicate builders are the aikali metai silicates, particularly thosehaving a SiO2:Na2O ratio in the range 1.0:1 to 3.2:1 and layered silicates, such as the
layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to
20 H. P. ~ieck. NaSKS-6 is the trademark for a crystalline layered silicate marketed by
Hoechst (commoniy abbreviated herein as "SKS-6"). Uniike zeolite buildel s, the Na
SKS-6 siiicate builder does not contain aluminum. NaSKS-6 has the delta-Na2SiOs
,~vl~Jllolo~y 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
25 preferred layered silicate for use herein, but other such layered silicates, such as those
having the general formula NaMSixO2x+l yH2o wherein M is sodium or hydrogen,
x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0
can be used herein. Various other layered silicates from Hoechst include NaSKS-5,
NaSKS-7 and NaSKS-I 1, as the alpha, beta and gamma forms. As noted above, the
30 delta-Na2SiOs (NaSKS-6 form) is most preferred for use herein. Other silicates may
aiso be useful such as for example magnesium silicate, which can serve as a crispening
agent in granular ~u~ ul~iulla, as a stabilizing agent for oxygen bleaches, and as a
component of suds control systems,
r builders are also useful in the present invention.
35 ~1 ~~ ' builders are of great importance in most currently marketed heavy
duty granular detergent ~ , and can also be a significant builder ingredient
wo ss/3302s 2 1 9 1 3 1 3 . ~
in liquid detergent formulations Al~ r buiiders include those having the
empirical formula
MZ/n[(Aio2)z(sio2)y] xH2o
wherein z and y are integers usually of at least 6, the molar ratio of z to y is in the
range from 1.0 to 0. and x is an integer from 0 to about 264, and M is a Group IA or
IIA element, e."., Na, K, Mg, Ca with valence n.
Useful ' ' ion exchange materials are UC/~ , "y available
These '"";,~ can be crystalline or amorphous in structure and can be
naturally-occurring ~ min-~cilir~t~c or synthetically derived. ~ method for producing
~I~lmin~cilirRt~ ion exchange materials is disclosed in U.S. Patent 3,985,669,
Krummel. et al, issued October 1~, 1976. Preferred synthetic crystalline
ion exchange materiais useful herein are available under the
eolite A. Zeolite P ~B), Zeolite MAP and Zeolite X. In an especially
preferred CllliJV i;~ lL, the crystaliine 21~1m~ ' ion exchange material has the1 5 formula:
Nal2[(AiO2)12(SiO2)l2~ xH2o
wherein x is from about 20 to about 30, especiaily about 27. This material is icnown
as Zeolite A. Dehydrated zeolites (x = 0 - 10) may a~so ~e used herein. Preferably,
the ~1 ~;A~ has a particle size of about 0. i -10 m. icrons in diameter.
Various other optional adjunct ingredients may aiso be used in ........... ,.. 1, ---~;
with the oleoyl sarcosinate and builders herein to provide fully-formulated granular
detergent ~.v ~ The foiiowing ingredients are described for the cu~ ,.lk"~
of the formulator, but are not intended to be iim. iting thereof
Detersive Surf~t~ntc - N..' g exampies of surfactants useful herein
25 typicaily at levels from about 1% to about 55%, by weight, include the ~,u~.iul~Liu~
Cll-Cl~ aikyl benzene suifonates ("LAS") and primary, branched-chain at~d randomClo-c2o aiicyl sulfates ("AS"), the Clo-C18 secondary (2,3) aikyl suifates of the
formula CH3(CH2)X(CHOSO3-M ) CH3 and CH3 (CH2)y(CHOSO3-M )
CH2CH3 where x and (y + 1) are integers of at least about 7, preferably at least30 about 9, and M is a water-solubiiizing cation, especially sodium, unsaturated aiisyl
sulfates such as oleyl suifate, the Clo-cl8 aik~l alkoxy suifates (''AEXS''; especiaily x
up to about 7 EO ethoxy sulfates), Clo-Cig aiicyl alkoxy ~ IbuAyl~t~,~ (especlally the
EO 1-5 cLl~u~yu~ u.~ Lc~), the C10 18 glycerol ethers, the Clo-CIg aiicyi
p~ly~$1yuu~idcs and their uullcalfullu;.~7 sulfated ~)oly~ly~,ua;~l~s, and C12-C18
35 alpha-sulfonated fatty acid esters. If desired, the cu~ iiu~al nonionic and
amphoteric surfactants such as the C12-CIg aikyl ethoxylates (~AE") including the
so-called narrow peaked aikyl ethoxylates and C6-C12 alkyl phenol aikoxylates
wos~/33029 ~ ~ 9 1 31 3 r~".
~especiall~ ethoxylates and mixed ethu~y/l,,u~,u~y), Cl7-CI8 betaines and
sulfobetaines ("sultaines"), Clo-CIg amine oxides, and the like~ can also be included
in the overall ~.. ,1,,-~;, ;-"~c The C I o-C 18 N-alkyl polyhydroxy fatty acid amides can
also be used Typical examples include the Cl~-CIg N-methyh~ . ` See WO
9.Z06.154. Other sugar-denved surfactants include the N-alkoxy polyh,vdlroxy fatty
acid amides, such as C l o-C l 8 N-(3 -~ u~y~Jl u~uyl) glucamide. The N-propyl
through N-hexyl C12-CIg glucamides can be used for low sudsing Cl0-C2û
,u~ .liiul~dl soaps may also be used. If high sudsing is desired, the branched-chain
Clo-cl6 soaps may be used Mixtures of anionic and nonionic surfa~tants are
especiall~ useful. Other conventional useful surfactants are listed in standard texts.
Builders - Other detergent builders can optionally be included in the
,.~,,,.l,g~:l;,.,.~ herein to also assist in controlling mineral hardness. Inorganic as well
as organic builders can be used. Builders are typically used in fabric Illundering
..l " l ~l .~.~;. ;....~ to assist in the removal of particulate soils.
Inorganic or P-containing detergent builders in addition to thl present
invention silicate and zeolites include, but are not limited to, the alk;-li meta~,
ammonium and " ' salts of pol~, ' , ' (exemplifie~l by the
Lli~Julyl~ u~ r~ , ' ' , and glassy polymeric meta-phosphates),
F~ , phytic acid, carbonates (including b;~,alhullal~ and a~i~u,Ldual~ ).
and sulphates. However. non-phosphate builders are required in some locales.
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates as disclosed in German Patent Application No. 2,3~1,001 published on
November 15, 1973.
Organic detergent builders suitable for the purposes of the present invention
include, but are not restricted to, a wide variety of pGl,~,alhu~ ylaL~ romro,~c As
used herein, ''pcly~,a bu~;a~e~ refers to ~.u"", ' having a plurality of carboxylate
groups, preferably at least 3 carboxylates. rul.~,albu.~la~ builder can ge~lerally be
added to the i.~. l .,:l;o~, in acid form, but can also be added in the form of a
neutralized salt. When utilized in salt form, alkali metals, such as sodium, p,Dtassium.
and lithium, or ~ nl ~ salts are preferred.
Included among the puly~,albu~ lal~ builders are a variety of categories of
useful materials. One important category Of uoly~,albu~jlaLt: builders r~ C~r~
the ether ~cl,r_albuAyla~a~ including U~.yLi_ , as disclosed in B~:rg, U.S.
Patent 3,128,287, issued April 7, 1964. and Lamberti et al, U.S. Patent 3,635,830,
issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071,
issued to Bush et al, on May 5, 1987. Suitable ether ~u;~,albu~' alsD include
_ _ _ _ _ _ _ . . .. ........... .... .. .... ....... . . .. . . . . ..
wo ss/3302s 2 1 9 1 3 1 3 ~ c~
cyclic compounds, particularly alicyclic compounds. such as those described in U.S.
Patents 3,9~3,679, 3.835.163, 4,158,635; 4,120.874 and 4,10',903.
Other useful detergency builders mclude the ether hydroxypolycarboxylates,
copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, j-
5 trihydroxy benzene-2, 4, 6-1l;aJlpllu.l;c acid, and ualbu~ ",~ ylu7.yal~ ;c acid. the
vanous alkali metal, ammonium and substituted ammûnium salts of polyacetic acidssuch as eth~ lf tetraacetic acid and IdLIiluL~ia~,e~k: acid, as well as
poiyual~w~lr~L~a such as mellltic acid, succinic acid, oxydisuccinic acid, polymaleic
acid, benzene 1,3,5-LIh,all)w~ylic acid, ~ bv~yl~",Lllyloxysuccinic acid, and solubie
10 salts thereof.
Citrate builders, e.g ~ citric acid and soluble salts thereof ~particularly sodium
sait), are polycarboxylate builders may be used and are desirabie due to their
availabiiity from renewable resources and their i,iudc~ I ' " y. Also. citrates can be
used in granular uulllyOa;l;OI~5 in ..".,1: -~;..., with zeoiite andor layered silicate
1~ builders O~y~ are also especially useful in such ~.v~ l o~ and
Aiso suitable in the detergent ,,.,..~I.,.-'~;,..~c of tke present invention are the
3,3-dicarboxy-4-oxa-1,6-h~Y~r.. ''~ and the related compounds disclosed in U.S.
Patent 4,~66,984, Bush, issued january 28, 1986. Useful succinic acid builders
20 include the Cs-C20 alkyl and aikenyl succinic acids and salts thereof A particularly
preferred compound of this type is dOu~ :a,,.,.,;.lic acid. Specifc examples of
succinate builders include: laul.~' ' , myristylsuccinate, ~"I."iL~.u.,~,;..~t~, 2-
dodc~ preferred), 2-p~...~ic~.~i"~:.Jccinate, and the like.
Laulj' ' are the preferred builders of this group, and are described in
l~uropean Patent Application 86200690.5/0~200,263, published November ~, 1986.
Other suitable poly~ o~kt~," are disclosed in U.S. Patent 4,144,226,
Crutchfield et ai, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehi, issued
March 7, 1967. See also Diehl U.S. Patent 3,723.322.
Fatty acids, e.g., C12-CIg l~ullv~ iJu~ k, acids such as oleic acid and/or its
saits, can also be ill~,ul~JulaLtd into the ~v~ alone, or in ' ' with
the aforesaid builders, especially citrate and/or the succinate builders, to provide
additional builder activity. Such use of fatty acids will generally result in a
diminution of sudsing, wkich should be taken into account by the formulator.
In situations where phosphorus-based builders can be used, and especially in
the ru.~.~.lh.~;ull of bars used for hand ' ' ' ~ operations, the various alkali metal
phosphates such as the well-known sodium L.;~ ' , ' . sodium ~Jy,upllva~ L~
and sodium uli'. r' ,' can be used. Pl~ualJIlull~ builders such as ethane-l-
~ woss/3302s 2 ~ 9 1 3 ~ 3 ~I/lJ..,S,~C- 7~
hydroxy~ r and other known ~ r~ r~ (see~ for examl~le, U.S
Patents 3~159,581, 3~213,030~ 3.4?2~0 '1~ 3~400~148 and 3,422~137) can also be used
Enzymes - Enzymes may be included in the formulations herein for a wide
variety of fabric laundering purposeS~ including removal of protein-based,
5 carbohydrate-based~ or triglyceride-based stains, for exampie. and for the plevention
of refugee dye transfer, and for fabric restoration The enzymes to be in~ul~lula~c i
include proteases, amylases, lipases, cellulases, and p.,.u~d iGscs~ as well as mixtures
thereof Other types of enzymes may also be included. They may be of an~/ suitable
origin, such as vegetable, animal, bacterial, funga! and yeast origin. However, their
10 choice is governed by several factors such as pH-activity and/or stability optima,
L~ u~ iJ;liLy, stability versus active detergents, builders and so on. In this respect
bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases,
and fungai cellulases.
Enzymes are normally i~cul~u~dlcd at levels sufficient to provide up to about
5 mg by weight, more typically about 0.001 mg to about 3 mg, of active enzyme per
gram of the ~c.."l.., ~;,.l Stated otherwise, the ~."...l.~,~:l;...~ herein will typicaiiy
comprise from about 0.001% to about 5%~ preferably 0.01%-2% by weight of a
commercial enzyme preparation. Protease enzymes are usuaily present in such
commercial ,UlC~)Gl~lLiU..~. at levels sufficient to provide firom 0.005 to 0.1 Ar.son units
20 (AU) of activity per gram of CUII~IJU:I;L;Ull.
Suitable examples of proteases are the subtiiisins which are obtai:ned from
particular strains of B. subtilis and B. I . r 111:1, Anotùer suitable protease is
obtained from a strain of Bacillus, having ma~imum activity throughout the pH range
of 8-12, developed and sold by Novo Industries A/S under the registered trade name
25 ESPEiRASE. The ~"c~ iuofthis enzyme and analogous enzymes is described in
British Patent S~ No. 1,243,784 of Novo. Proteolytic enzymes s~litable for
removing protein-based stains that are ,UIIIIII.,.I' 'ly avaiiable include tllose sold
under the tradenames ALCALASE and SAVINASE by Novo Industries A/S
(Denmark) and MAXATASE by Ill~clll~liullal Bio-Synthetics~ Inc. (The
N.,.l.~,.' ' ). Other proteases include Protease A (see European Patent Application
130,756, published January 9, 1985) and Protease B (see Europea.n Patent
Application Serial No. 87303761.8, filed April 28, 1987, and Europe:m Patent
Application 130,756. Bott et ai. published January 9. 1985). Other proteaslos include
Protease A (see European Patent Application 130.756. published January 9, 1985)
and Protease B (see European Patent Application Serial No. 87303761.8, filed April
28. 1987. and European Patent Application 130,756~ Bott et al~ published January 9,
1985). Most preferred is what is cailed herein "Protease C", which is a variant of an
wo ss/33029 2 1 9 1 3 1 3 r~
alkaline senne proIease from Bacillus~ particularly Bqrillllc l-ntll~ in which arginine
repiaced Iysine at position ~7, tyrosine replaced valine al position 104~ serine replaced
asparagine at position 1'3, and alanine replaced threonine at position 274. Protease
C is described in EP 90915958:4; U.S. Patent No. 5,185,250, and U.S. Patent No.
5,204.015. Aiso preferred are protease which are descnbed in copending application
U.S. Serial No. 08/136.797. entitled Protease-containing Cleaning C~ o~;l;ul,~ and
copending Application U.S. Serial No. 08/136,626, entitled Bleaching Compositions
Comprising Protease Enzymes. which are i~luu~ul.lLed herein by reference.
Genetically modified variants, particularly of Protease C, are also included herein.
Amylases include, for example, o-amylases described in British Patent
Specification No. 1,296,839 ~Novo), i~APlDASE, III~ L;GII~I Bio-Synthetics, Inc.and TEi~MAM~, Novo Industries,
The cellulase usable in the present inveMion include both bacterial 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 al, issued March 6,
1984, which discloses fungal cellulase produced from Humicola insolens arld
Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the
genus Aeromonas, and cellulase extracted from the ' . r ci~ of a marine
mollusk (Dolabella Auricula Solander). suitable cellulases are also disclosed in GB-
A-2.075.028; GB-A-2.095.275 _nd DE-OS-2.247.832. Cellulases such as
CAi~EZYME (Novo) are especially usefill, since they provide additional softeningand appearance benefits to fabrics laundered in the present 1..l .~.~,~;1;"..
Suitable lipase enzymes for detergent usage include those produced by
IIU~,IUU~ of the rS ' group, such as r ~ stutzeri ATCC
19.154, as disclosed in British Patent 1,372,034. See aiso lipases in lapanese Patent
Application 53,20487, laid open to public inspection on February 24, 1978. This
iipase is availabie from Amano Pll~..,..~ci.lL;~,~l Co. Ltd., Nagoya, Japan, under the
trade name Lipase P "Amano." hereinafter referred to as "Amano-P." Other
commercial iipases include Amano-CES, lipases ex Cluul~lvi~ .t~,. viscosum, e.g.30 Cluvl~u~ viscosum var. Iipolyticum NRRLB 3673, .,o.,u...,.. "~ available fromToyo Jozo Co., Tagata, Japan; and further Cluu~ob~ ." viscosum iipases firom U.SRir)rh.omirql Corp., U.S.A. and Disoynth Co., The N~,.l.."l~YIJ~, and iipases exr,.. l.. -- ~ giadioii. The LIPOLASE enzyme derived from Humicola lanuginosa
and l,UIIUI~ y avaiiable from Novo (see aiso EPO 341,947) is a preferred lipase
35 for use herein.
Peroxidase enzymes are used in ~ ", with oxygen sources. e.g..
.,.~ , perborate, persuifate, hydrogen peroxide, etc. They are used for
2~9~3~3
W0 95133~29 I ~ v~
ll
"solution bleaching," i.e. to prevent transfer of dyes or pigments removed from
substrates dunng wash operations to other substrates in the wash solution
Peroxidase enzymes are known in the art, and include, for example. hcrseradish
peroxidase, ligninase, and l~_lu~ u~dJasf, such as chioro- and bromo-peroxidase.5 Peroxidase-containing detergent ~ ;c~ are disclosed, for example, in PCT
lI.L~ ;VII-I Application WO 89/099813, published October 19, 1989, by O. Kirk.
assigned to Novo Induslries A J, It may be desired to use, in ,,u.. L: ~vith these
p.,.v,i~ . materials viewed as being peroxidase d~ ,.dLol~ such as
rhPnl~lclllff~n~tp andlor ~ lVLIuA,i"~
A wide range of enzyme materials and means for their ;IIUUI~JOI~.I;VII into
synthetic detergent cnmr~Citil~nc are also disclosed in U.S. Patent 3,553,139~ issued
January i, 1971 to McCarty et al. Enzymes are further disclosed in U.S. Patent
4.101,457, Place et al, issued July 18, 1978, in U.S. Patent 4,507,219. Hughl~s, issued
March26, 1985,andinU.S.Patent4,261,868,Horaetal,issuedApril 14. 1981.
Enzvme Stabilizers - A preferred optional ingredient for use in thlo present
.vl~ v~ comprising enzymes is enzyme stabilizers. Enzymes for use m
detergents can be stabilized by various techniques. Enzyme ' ' techniques
are disclosed and ,.-r ~ in U.S. Patent 3,600,3i9, 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. Enz~me
systems are aiso described, for example, in U.S. Patent 3,519,570. The
enzymes employed herein can be stabilized by the presence of water-soluble sources
of calcium and/or magnesium ions in the finished . . which provide such
ions to the enzymes. (Calcium ions are generally somewhat more effective than
magnesium ions and are preferred herein if oniy one type of cation is being used.)
Addhional stability can be provided by the presence of various other art-
disclosed stabilizers, especiaily borate species: see Severson~ U.S. 4,537,706.
Typical detergents will compnse from about I to about 30, preferably fronl about ~
to about '20, more preferably from about 5 to about 15, and most prefer.ably from
about 8 to about 12, miliimoles of caicium ion per liter of finished . ~.. 1.. ~:1:.. ,. This
can vary somewhat, depending on the amount of enzyme present and its response tothe calcium or magnesium ions. The level of calcium or magnesium ions should be
seiected so that there is aiways some minimum level available for the enz~me, after
allowing for .,.. 1 l~ ;.. with builders, fatty acids, etc., in the ~ ................... Any
35 water-soluble caicium or magnesium salt can be used as the source of c.~lcium or
magnesium ions, including, but not iimited to, calcium chioride, caiciurn suhfate,
caicium maiate, caicium maleate, calcium hydroxide, calcium formate, and calcium
2 ~ 9 1 3 1 3
WO 95/33029 P~,l/U~ r
I'
acetate, and the uull~a~ lJ;llg magnesium salts A small amount of calcium ion,
generally from about û.û5 to about 0.4 mil!imoles per liter, is often also present in the
. ~.,,,1,..~;.l,,,, due to calcium in the enzyme slurry and formula water In solid
detergent r~ ,o,;~ the ru~lul~;ull may include a sufticient quantity of a water-
5 so]uble calcium ion source to provide such amounts in the laundry liquor. In thea~ternative. natural water hardness may suffice.
It is to be understood that the foregoing levels of calcium and/or magnesium
ions are sufficient to provide enzyme stability More calcium and/or magnesium ions
can be added to the i.. ", 1, ,~;l ;~ ~ ~ to provide an addilional measure of grease removal
lû p~,.ru~ . Accordingly, as a general proposition the l.l,l,.l,r,~ herein will
typically comprise from about û.05% to about 2% by weight of a water-soluble
source of calcium or magnesium ions, or both. The amount can vary, of course, with
the amount and type of enzyme employed in the uulll,uOa;L;u--.
The .... ".,~ herein may also optionally. but preferably, contain various
15 additional stabilizers, especially borate-type stabilizers. Typically, such stabilizers will
be used at levels in the .. "~ from about 0.25% to about lû%, preferably
from about 0.5% to about 5%, more preferably from about û.75% to about 3%, by
weight of boric acid or other borate compound capable of forming boric acid in the
...,.,.1..,~:l;.... (calculated on the basis of boric acid). Boric acid is preferred, although
2û other compounds such as boric oxide, borax and other alkali metal borates (e.g.,
sodium ortho-, meta- and pyroborate, and sodium p.,l.~..bu~ ~.Le) are suitable.
Substituted boric acids (e.g., pl~ .bu~u~h, acid, butane boronic acid, and p-bromo
~' ~:bulu-l-~, acid) can also be used in place of boric acid. It is to be recognized that
such materials may also be used in formulations as the sole stabilizer as well as being
25 used in ' with added calcium and/or magnesium ions.
Funally, it may be desired to add chlorine scavengers, especially to protease-
containing ~....1,~l~:l;. ~, to protect the enzymes from chlorine typically present in
municipal water supplies. Such materials are described, for example, in U.S. Patent
4,81û,413 to Pancheri et al.
3û p~ rhir~ Compounds - Bleachinr~ Aæ~nfc ~-rl Bleach Activators - The
detergent ~,.. 1.. ,~:l;~, herein may optionally contain bleaching agents or bleaching
~..,..1.~.~:l;..,.~ containing a bleaching agent and one or more bleach activators. When
present, bleaching agents will typically be at levels of from about 1% to about 30%,
more typically from about 5% to about 20%, of the detergent ~.~....1...~;1 ;l .l.. especially
35 for fabric laundering; If present, the amount of bleach activators will typically be
from about û. 1% to about 60%, more typically from about û.5% to about 4û% of the
bleaching ~. ..1-l ~l~;l;l ~- comprising the bleaching agent-plus-bleach activator.
~ w095133029 2 1 9 1 3 1 3 P~
The bleaching ~gents used herein can be any of the bleaching agents useful for
detergent Cu~ Oa;lit~ in textile cleaning or other cleaning purposes that are now
known or become known. These include oxygen bleaches as well as other bleaching
agents. Perborate bleaches, e.g., sodium perborate (e.g., mono- or tetra-hytlrate) can
5 be used herein.
Another category of bleaching agent that can be used without restriction
P."~ albw~ h, acid bleaching agents and salts thereof Suitable examples
of this class of agents include magnesium IllylluLJ~u~yl ' ' ' I ' ~d~aL~, the
magnesium salt of metachloro perbenzoic acid~ 4-nonylamino-4-u~u,u~.u,~y~uLyli-
10 acid and d;l~,.u~iy.ll~ .it acid. Such bleaching agents are disclosed in U.S.Patent 4,483~781~ Hartman, issued November 20, 1984, U.S. Patent Application
740,446, Burns et al, filed June 3, 1985. European Patent Application 0,133,354,Banks et al, published February 20, 1985, and U.S. Patent 4,417,934, Chung et al,
issued November 1, 1983. Highly preferred bleaching agents also irlclude 6-
nu~ldll~ o-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issuedJanuary 6, 1987 to Burns et al.
Peroxygen bledching agents can also be used. Suitable peroxygen bleaching
Ççmrolln~ include sodium carbonate p.,.u~yh~dla~t: and equivalent "~J~"L,Ilbull~L~"
bleaches, sodium pyluyllua~ t~ "uA,~ ,al~, urea ~,w-~h~lla~e, and sodium
20 peroxide. Persulfate bleach (e.g., OXONE" '' cd, , ' "~ by DuPont)
can also be used.
A preferred ~ ,~bù~ L~: bleach comprises dry particles having all average
particle size in the range from about 50û IlliLlUlll.,t~"~ to about 1,000 ' ull,.,L~la,
not more than about 10% by weight of said particles being smaller than about 20025 ~ ,lUII,~,t~"~ and not more than about 10% by weight of said particles being larger
than abûut 1,250 Illi~lUIII.,t~"~. Optionally, the ~,w.L can be co.ated with
silicate, borate or water-soluble surfactants. Pe.~,~,.L is available froln various
comtnercial sources such as FMC, Solvay and Tokai Denka.
Mixtures of bleaching agents can also be used.
Peroxygen bleaching agents, the perborates, the p......... ~.L , etc., are
preferably combined with bleach activators, which lead to the m si~u production in
aqueous solution (i.e., during the washing process) of the peroxy acid ~UII~
to the bleach activator. Various nonlimiting examples of activators are di~closed in
U.S. Patent 4,915,854, issued April 10. 1990 to Mao et al, and U.S. Patent
4,412,934. The ylu~y~ , sulfonate (NOBS) and tetraacetyl ethylene
diamine (TAED) activators are typical, and mixtures thereof can also be ~sed. See
also U.S. 4,634,551 for other typical bleaches and activators useful herein.
2 1 9 ~ 3 ~ 3
WO 95133029 P~,1/L.. ,5 ^'~
14
Highly preferred amido-derived bleach activators are those of the formuiae:
RIN(R5)C(o)R2C(o)L or RIC(o)N(R5)R2C(o)L
wherein Rl is an alkyl group containing froln about 6 to about 1~ carbon atoms, R~
is an alkylene containing from I to about 6 carbon atoms, R5 is H or alkyl, aryl~ or
5 alkaryl containing from about I to about 10 carbon atoms, and L is any suitable
leaving group. A leaving group is any group that is displaced from the bleach
activator as a ~U~ U~U~ of the llu~ o,cl~ attack on the bleach activator by the
perhydrolysis anion. A preferred leaving group is phenyl sulfonate.
Preferred examples of bleach activators of the above formulae include (6-
lû octanamido-caproyl)u,-yl~ r~ r, (6-,.n~ "uyl)oxybenzenesul-
fonate, (6-r~ m~ -caproyl)oxy~ r~ aDd mixtures thereof as
described in U.S. Patent 4,634,551, il,~,ul},uldLc;l herein by reference.
Another class of bleach activators comprises the benzoxazin-type activators
disclosed by Hodge et al in U.S. Patent 4,966.723, issued October 3û, 199û,
15 ;Il~Ul ,uu- dLcd herein by reference. A highly preferred activator of the benzoxazin-type
is: _
~(N"C~
Still another class of preferred bleach activators includes the acyl lactam
activators, especially acyl ca~.,ula~,Ld".~ and acyi \,lk,.ula~,lal..:. ofthe formulae:
O O
O C--CH2--CH2 0 C--CH2--C H2
CH2--CH2 R6--C--1~ l
wherein R6 js H or an alkyl, aryl~ alkoxyaryl. or alkaryl group contaiDing from I to
about 12 carbon atoms. Highly preferred lactam activators include beDzoyl
~,ap~ula~,~dlll~ octanoyl ~a~JIula.,Lal~, 3,5,5-11ill..,.lly..._,~allOyl ca~JIula~,La"~, nonanoyl
~,a~lulà~,Lalll, decanoyl ~,alJIula.,Lalll, undecenoyl ~,alnula~Ldll,~ benzoyl ~ ' ula~,Lalll,
25 octanoyl ~,_' uia~alll, decanoyl ~al~ula~,L~ l, undecenoyl v~l~"ula~,Lalll, nonanoyl
~.' ula~,~al~l, 3~5~5-LIill~ ylh~ uyl ~a~lula~,Lalll and mixtures thereof See also
U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, ill~,ul~JuldLcd herein by
reference, which discloses acyl ca!/lula~la~ jDCIUdjng benzoyl ~,~lulal,~
adsofbed into sodium perborate.
~, w0 95/33029 2 T 9 1 3 1 3 r~
Bleachjng agents other than oxygen bleaching agents are also known in the an
and can be utilized herein, One type of non-oxygen bleaching agent of pa.rticular
- iMerest includes photoactivated bleaching agents such as the sulfonated zinc and/or
aluminum phthalocyanines. See U.S. Patent 4.033~718, issued July 5. 1977 to
S Ho~combe et al. If used, detergent ~U~ ;LiUlls will typically contain from about
0.025% to about 1.''5%, by weight, of such bleaches, especially sulfonate zinc
phthalocyanine.
If desired, the bleaching compounds can be catalyzed by means of a
manganese compound. Such rnmrolln~lc are well known in the art and inclllde. forexample, the l"c"~a"cO~-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat.
5,244,594; U.S. Pât. 5,194,416; U.S. Pat. 5,114,606, and European Pat. App. Pub.Nos. 549,271A1, 549,272AI, 544,440A2, and 544,490AI; Preferred examples of
these catalysts include MnIv2(u-0)3(1~4,7-tnmeth~/1-1.4,7-
L~ y~lullullclle)2(pF6)27 Mnm2(u-O)I(u-OAc)2(1~4~7-trimeth~rl-1~4~7-
Ll;~y~lullùll~llc)2-(clo4)2~ MnlV4(u-o)6(l~4~7-~ y~ )4(C1O
MnlllMnlV4(u-O)l(u-OAc)2 (1,4,7-trimethyl-1,4,7-~ y 1.. -. )2(C104)3,
MnlV(1,4,7-trimethyl-1,4,7-Lli~.,y~,lur.~u..~.,,e)- (OCH3)3(PF6)~ and Inixtures
thereof Other metal-based bleach catalysts include those disclosed in U.S. Pat.
4,430,243 and U.S. Pat. 5,114,611. The use of manganese with various complex
20 ligands to enhance bleaching is also reported in the following United States Patents:
4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153~61; and
5,227,û84,
As a practical matter, and not by way of limitation, the çnmrn~itinnC and
processes herein can be adjusted to provide on the order of at least one part per ten
25 million of the active bleach catalyst species in the aqueous washing liquor. and will
preferably provide from about 0.1 ppm to about 700 ppm, more preferal~ly from
about I ppm to about 500 ppm, of the catalyst species in the laundry liquor.
Pûlvmeric Soil Release A~ent - Any polymeric soil release agent known to
those skilled in the art can optionally be employed in the .... ~.u~ and processes
30 of this invention. Polymeric soil release agents are ~ ,Lcl;~l by having both hydrophilic segments, to l~,y1lu~ ' the surface of ~ U~ U~ fibers~ such aspolyester and nylon. and hydrophobic segments, to deposit upon llydlu~ )lJ;r fibers
and remain adhered thereto through completion of washing and rinsing cycles and.
thus, serve as an anchor for the hydrophilic segments. This can enable stains
35 occurring subsequent to treatment with the soil release agent to be more easily
cleaned in later washing procedures.
. _ .. .. ... ..... . . .. ..... ..... .. . . _
WO 9i/33029 ~ ~ 9 1 3 ~ 3 r~ .. r~
1~
The polymeric soil release agents useful herein especially include those soil
release agents having. (a) one or more nonionic hydrophile . ..,,,1,.,,,, ..1~ consisting
essentially of (i) polyoxyethylene se~ments with a degree of polymerization of at least
', or (ii) u~y~,, u~yl. .l~, or polyoxvpropylene segments with a degree of
5 poiymerization offrom 2 to 10~ wherein said hydrophile segment does not encompass
any u~yl~uLJ~ ,e unit uniess it is bonded to adjacent moieties at each end by ether
linkages, or (iii) a mixture of oxyali~ylene units comprising u~ ...e and from I to
about 3û U~ylJlU~ LllC units wherein said mixture contains a sufficient amount of
oxyethylene units such that the hydrophile component has 11y~ , ' '' ' y great enough
10 to increase the lly~iluu;.,l.~,iLy of LUIIv~llLiUIIdl polyester synthetic flber surfaces upon
deposit of the soil release agent on such surface, said hydrophile segments preferably
comprising at least about 25% oxyethylene units and more preferably~ especially for
such LUIll~Oll~ having about 20 to 30 u~yl~lu~ c units, at least about 50%
w~ llJl~lle units; or (b) one or more ~Iy~ilu~ Jbe ...,...1,., .,1~ comprising (i) C3
15 oxyalkylene telqJ~ ala~e segments, wherein, if said IIYLiIU~JIIUI)C ~ also
comprise U,.,~.,LII~ ClC~JIl.llàld~, the ratio of u~,Lilrl~,..., ~clc~ llalaLc ~3
u~ '~ "L ~ClC~JIlLlldlaLc units is about 2:1 Dr lower, (ii) C4-C6 alkylene or oxy C4-
C6 alkylene segments. or mixtures therein, (iii) poly (vinyl ester) segments, preferably
polyvinyl acetate), having a degree of I)L~I~.1l.,.i~aLiull of at least 2, or (iv) CI-C4 alkyl
20 ether or C4 I~ u~y "~yl ether sU~ , or mixtures therein, wherein said
cllbStitlllontc are present in the form of Cl-C4 aikyl ether or C4 hydroxyaikyl ether
cellulose derivatives, or mixtures therein~ and such cellulose derivatives are
, ' ', ' ''', whereby they have a sufficient ievel of Cl-C4 alkyl ether and/or C4
hydroxyalkyl ether units to deposit upon LUII~II.iUIlài polyester synthetic fiber
25 surfaces and retain a sufficient level of hydroxyls, once adhered to such CU..~,..i...~dl
synthetic fiber surface, to rncrease fiber surface h,ll~u~ , or a .. 1 ' -~;./1~ of (a)
and (b).
Typicaiiy, the ~cl~ h,fle segments of (a~(i) will have a degree of
i~U~ atiùll of from about 20û, although higher levels can be used. preferabiy
3û from 3 to about 150, more preferably firom 6 to about 100. Suitable oxy C4-C6
aikylene llyLilu~llL~bc segments include, but are not limited to, end-caps of polymeric
soii release agents such as MO3S(CH2)nOCH2CH2O-, where M is sodium and n is
an integer firom 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988
to Gosselink.
Polymeric soil release agents useful in the present invention also include
cellulosic derivatives such as llr~ilU..~ " cellulosic polyrners. cu~,ulyl".,.;c blocks of
ethylene L~lc,ullLIlalaLc or propylene tclc~JhiilalaLe with pol~,.i-,rl~"~e oxide or
. ... .. .. . . ...... . . _ ... ......... ... . .
Wo s~/33029 1 9 1 3 1 3
polypropylene oxide ~eic~ LIl~ Le. and the like. Such agents are ~.UIIIIII~
available and include h~ i,U7.,~ of cellulose such as METHOCEL (Dow)
Ceiiulosic soil release agents for use herein also include those selected from the group
consisting of C l-C4 alkyl and C4 hydroxyalkyl cellulose, see U.S. Patent 4.ûû0,093.
issued December ~8, 1976 to Nicol, et al.
Soil release agents ,,Il~ild~L~ c~i by poly(vinyl ester) lly i~u~ u~ segments
include graft copolymers of poly(vinyl ester), e.g., Cl-C6 vinyl esters, preferably
poly(vinyl acetate) grafted onto polyalkylene oxide backbones. such as polyethylene
oxide backbones. See European Patent Application 0 219 048, pubiished April 22.
1987 by Kud~ et al. Cu,,u,,~l, ' "y available soil release agents ofthis kind include the
SOKALAN type of materiai, e.g., SOKALAN i~,P-22, available from BASF (West
Germany).
One type of preferred soil release agent is a copolymer having random blocks
of ethylene te~ h,;~ala~e and po'~.",~ ., oxide (PEO) Ltlc~llLII~il< Le. The molecular
weight of this polymeric soil release agent is in the range of from about ~.5,000 to
about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S.
Patent 3,893,929 to Basadur issued July 8, 1975.
Another preferred polymeric soil release agent is a polyester with rel~eat unitsof ethylene Lclc~ c units contains 10-15% by weight of ethylene ~el~, ' '' '
units together with 90-80% by weight of pvl~u~.,.lljh,.l~ Lcl c~ k~L~ units, derived
from a pvl,yv7~ 5u.l~ glycol of average molecular weight 300-5,000. Examples of
this polymer include the cu~u~ available materiai ZELCON 5126 (from
Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857, issued
October 27, 1987 to Gosselink.
Another preferred polymeric soil release agent is a sulfonated pro~iuct of a
' "y linear ester oligomer comprised of an oligomeric ester backbone of
Lelcr' ' ',,~1 and oxyalkyleneoxy repeat units and terminal moieties covaiently
attached to the backbone. These soil release agents are described fi,lly in U.S. Patent
4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselin,~. Other
suitable polymeric soil release agents include the Lelu~ Ll~ Lc polyesters of U.S.
Patent 4,711,730, issued December 8, 1987 to Gosseiink et al, the anionic end-
capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to
Gosseiink, and the block polyester oligomeric compounds of U.S. Patent 4.702,857,
issued October 27, 1987 to Gosselink.
Preferred polymeric soil release agents also include the soil release agents of
U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses
anionic, especiaily suifoaroyl, end-capped Lelc,uh.ll~ c esters.
wo ss/33029 ~ 1 9 1 3 1 3 P~ 5 L ~
18
Still another preferred soil release agent is an oligomer with repeat units of
terephthaloyl units~ ~ulru;~u~clc~ dvyl units, ox~c.l,Jk,,l~,v~y and oxy-1,2-
propylene units The repeat units form the backbone of the oligomer and are
preferably terminated with modifled isethionate end-caps A particularly preferred
5 soil release agent of this type comprises about one Clllf ljc~lphthl~l~yl unit, 5
terephthaloyl units, oxyethyleneoxy and oxy- 1,2-~, up,~l~..ev~y units in a ratio of from
about 1.7 to about 1 ~, and two end-cap units of sodium 2-(2-hydroxyethoxy)-
rl~ Said soil release agent also comprises from about 0.5% to about
20%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably10 selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene
sulfonate, and mixtures thereof
If utili~ed, soil release agents will generally comprise from about 0.01% to
about 10.0%, by weight, of the detergent ~...,.I,,. ~;,;v~ herein, typically from about
0,1% to about 5%, preferably from about 0.2% to about 3.0%.
Dye Transfer rnhihiti~ ~ ntc _ The ~ .v~ of the present
invention may also include one or more materials effective for inhibiting the transfer
of dyes from one fabric to another during the cleaning process. Generally, such dye
transfer inhibiting agents include polyvinyl ~"." '' ' polymers. polyamine N-oxide
polymers, copolymers of N ~ '` ' and N-~,;..," ' '~, manganese
20 1 ' ' ' ,.,~.u.l~ ,.u~-l~c~. and mixtures thereof If used, these agents typically
comprise from about 0.01% to about 10% by weight ofthe ~ , preferably
from about 0.01% to about 5%, and more preferably from about 0.05% to about 2%.
More specifically, the polyamine N-oxide polymers preferred for use herein
contain units having the following structural formula: R-AX-P: wherein P is a
25 pul~...~,.~l,l~ unit to which an N-O group can be attached or the N-O group can
form part of the pol~ ,..4~1e unit or the N-O group can be attached to both units; A
is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1; and
R is aliphatic, ethoxylated aliphatics, aromatics, I~Le-u~.,L~, or alicyclic groups or
any ro~ thereof to which the nitrogen of the N-O group can be attached or
30 the N-O group is part of these groups. Preferred polyamine N-oxides are thosewherein R is a II~LCIU~Y~I;C group such as pyridine, pyrrole, imidazole. pyrrolidine.
piperidine and derivatives thereof
The N-O group can be ,~,., ' by the following general structures:
O O
(Rl)x--I ~R2)y; =N--(Rl)x
(R3)2~
:: .
wo ss/3302s 2 ~ 9 ~ 3 ~ 3 1 ~
19
wherein R I, R7~ R3 are aliphatic~ aromatic~ heterocyclic or alicyclic groups orrnmhinqrinn~ thereof. x~ y and z are 0 or 1: and the nitrogen of the N-O groul~ can be
attached or form part of any of the drUltlll~...iUll~,~i groups. The amine oxide unit of
the polyamine N-oxides has a pKa <10~ preferably pKa <7~ more preferred pKa <6.
Ar~y polymer backbone can be used as long as the amine oxide polymer
formed is water-soluble and has dye transfer inhibiting properties. Examples of
suitable polymeric backbones are polyvinyls~ polyalkylenes~ polyesters~ polyethers.
polyamide~ poiyimides~ polyacrylates and mixtures thereof, These polymers include
random or block copolymers where one monomer type is an amine N-oxide and the
other monomer type is an N-oxide. The amine N-oxide polymers typicall~ have a
ratio of amine to the amine N-oxide of 10:1 to 1:1~000~000. However~ the nLlmber of
amine oxide groups present in the polyamine oxide polymer can be varied by
appropriate Cu~Jvly~ Liull or by an appropnate degree of N-oxidation. The
polyamine oxides can be obtained in almost any degree of polymenzation. Typically~
the average molecuiar weight is within the range of 500 to 1~000~000; more E~referred
1~000 to 500~000; most preferred 5~000 to 100~000. This preferred class of materiais
can be referred to as "PVNO".
The most preferred poiyamine N-oxide useful in the detergent ~u,.,l,u~;~iu..~
herein is poly(~i ~; yl~,~.iJ;..c-N-oxide) which as an average molecular ~eight of
2û about 50~000 and an amine to amine N-oxide ratio of about 1:4.
Copolymers of N-\,;..,'~,~l" '` ' and N-~,;ll,!;.l iJ~I~ polymers (referred to
as a class as "PVPV.i") are also preferred for use herein. Preferably the P~l'PVi has
an average molecular weight range from 5~000 to 1,000~000~ more preferably from
5~000 to 200~000~ and most preferably from 10~000 to 20~000. (The average
25 molecular weight range is determined by light scattering as described in Barth~ et al.~
Ch~mirql Analvsis~ Vol 113. "Modern Methods of Polymer r~ rll~.n;~ the
disclosures of which are ill-,UI,UUI dLt i herein by reference.) The PVPVI copolymers
typicaily have a molar ratio of N ~;..," ' '~ to N .;.l~ from 1:1 to
0.2:1~ more preferably from 0.8:1 to 0.3:1~ most preferably from 0.6:1 to 0.4:1.These ~,ulJulyll.~ can be either linear or branched.
The present invention ~ I,v~ also may employ a
("PVP") having an average molecular weight of from about 5~000 to about 400~000~preferably from about 5~000 to about 200~ûOO~ and more preferably from about 5~000
to about 50~000. PVP's are known to persons skilled in the detergent field; see~ for
example, EP-A-262,897 and EP-A-256,696, illCUl~vldLt~i herein by reference
C.,".~ contairling PVP can also contain pul~ glycol ("PEG") having
an average molecular weight from about ~00 to about 100~000~ preferably from about
W095133029 ~ ~ 91313 r~ c~
I,OoO to about 10~000: Preferably, the ratio of PEG to PVP on a ppm basis delivered
in wash solutions is from about ~:1 to about 50 1, and more preferabl,v from about
3:1 to about 10:1.
The detergent uu~ Jua;LiullS herein may also optionally contain from about
5 O.ODS% to 5~o by weight of certain types of hydrûphilic optical brighteners which
also provide a dye transfer inhibition action. If used. the compositions herein will
preferablv comprise from about 0.01% to 1% by weight of such optical brighteners.
The hvdrophilic optical brighteners useful in the present invention are those
having the structural formula~
N~ ~C=C~ ~ (N
R~ S03M S03M Rl
wherein Rl is selected from anilino, N-2-bis-hydroxyethyi and NH-2 ~ UA~ IIYI;
R2 iS selected from N-2-bis-hydroAyethyl, N-2-lly iluA.~,.llyl-N-ll~
morphilino, chioro and amino; and M is a salt-forming cation such as sodium or
potassium,
When in the above formula, Rl is anilino, R2 is N-2-bis-lly iluA,~.,.llyl and M
is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-
lly iluA,~ l)-s-triazine-2-yl)amino]-2,2'-~ ..lr~ ;. acid and disodium salt.
This particular brightener species is ~Ul~ , marketed under the tradename
Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred
20 hydrophilic optical brightener useful in the detergent c..,..l,o~;l;,. herein.
When in the above formula~ Rl is aniiino, R~ is N-2 h,ydlu~ yl-N-2-
.,..,.;.,~' ~, and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-
(N-2-hy iluA~,.lly~ N-l.~ ' )-s-triazine-2-yl)amino]2,2'-~ "ll`. 'r acid
disodium sait. This particular brightener species is . .,h.ll.~ marketed under the
25 tradename Tinopal SBM-GX by Ciba-Geigy Corporation.
When in the above formula, Rl is anilino, R2 iS morphilino and M is a cation
such as sodium, the brightener is 4,4'-bisi'(4-anilino-6-morphilino-s-triazine-2-
yl)amino]~,2'-~l;ll,.. l;~.. l~,.. ;. acid, sodium salt. This particular brightener species is
u;~lly marketed under the tradename Tinopal AMS-GX by Ciba Gei~y
3û Corporation.
The specific opticai brightener species selected for use in the present invention
provide especiaily effective dye transfer inhibition ~,.ru~ benefits when used in
with the selected polymeric dye transfer inhibiting a~gents ~ .V~UI~
. ~ WO95/33029 2 1 9 1 3 1 3 P~
descnbed. The cu,l.v;,,.lLio,~ of such selected polymenc materials (e.g., PVNO and/or
PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX. Tinopal
5BM-GX and or Tinopal AMS-GX) provides significantly better dve transfer
inhibition in aqueous wash solutions than does either of these two cletergent
5 ~UIll~JCva;Liull I u"~ when uâed alone. Without being bound by theory, it is
believed that such brighteners work this way because they have high affinity forfabrics in the wash solution and therefore deposit relatively quick on these fabrics.
The extent to which brighteners deposit on fabrics in the wash solution can be defined
by a parameter called the "exhaustion coefficient". The exhaustion coefficient is in
10 general as the ratio of a) the brightener material deposited on fabric to b) the initial
brightener culll,cllLl.lLiul~ in the wash liquor. Brighteners with relatively high
exhaustion coefficients are the most suitable for inhibiting dye transfer in the context
of the present invention.
Of course, it will be appreciated that other, I.u,,i~,.l.iu~l optical blightener15 types of compounds can optionally be used in the present ~u ~ to provide
~,ullv~,~lLiul~al fabric "b,i~llLll.,~" benefits, rather than a true dye transfer inhibitirlg
effect. Such usage is ~u~liu~ o~l and well-known to detergent l'ul '
Polymeric Dispersin~ AIJ~ntc - Polymeric dispersing agenlts can
a.lv.lllL~,~,vu~ly be utilized at levels firom about 0.1% to about 7%, by weight. .1. ~he
20 ~.u...~ herein. Suitable polymeric dispersing agents include po~yme tc
IJoly.,.,,bu~ylilt~,~ and pol~ yl.,.,~, glycols, although others known in the art c n
be used.
Polymeric ~ul~al~u7ylate materials can be prepared by pU~ illL 0-
~,u~vlylll."i~ suitable ~ lrll monomers, preferably in their acili fo~l
25 Unsaturated monomeric acids that can be pul~,.,.,.i~.,l to form suitable polymer~c
pvlyl,zllbu7~yLI~c~ include acrylic acid, maleic acid (or maleic anhydride), fiuma.ric acid,
itaconic acid, aconitic acid, mesaconic acid, citraconic acid and ll.~,L~,y'.. ,Al.",;r
acid. The presence in the polymenc pcvly~ u~k~ herein or monomeric s~,gments,
containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is
30 suitable provided that such segments do not constitute more than about 40% by weight.
Particularly suitable polymeric puly~ b~.ylates can be derived from acrylic
acid. Such acrylic acid-based polymers which are useful herein are the watel-soluble
salts of poly...~ ,.l acrylic acid. The average molecular weight of such polymers in
the acid form preferably ranges firom about 2,000 to 10,000, more preferal~ly from
about 4,000 to 7,000 and most preferably from about 4,000 to 5~000. Watel soluble
salts of such acrylic acid polymers can include, for example, the alkali metal.
Wogsl330 s 2 1 9 1 3 1 3 .~ L`-^71 ~ .
2~
ammonium and substituted ammonium salts. Solubie polymers of this type are
i~nown materials. Use of polyacrylates of this Iype in detergent ~,u..")o~;Liulls has
been disclûsed, for example, in Diehl~ U.S. Patent 3,308~067. issued March 7, 1967.
Acrylicimaleic-based copolymers may also be used as a preferred component
S of the d;~,u.,~ Li-lGd~lJO~;Liull agent. Such materials include the water-soluble
salts of copolymers of acrylic acid and maleic acid. The average molecular weight of
such copolymers in the acid form preferably ranges from about ~,0û0 to lo0.a00. A
preferred copolymer has an average molecular weight of about 2,000 to 15.000.
more preferably about 6,000 to about 13,000, and most preferably about 7 000 to
about 12,000. Other preferred copolymers have an average molecular weight from
about 5.000 to 75,00~1, rnost preferably from about 7,000 to 65,000. The ratio of
acrylate to maleate segments in such copolymers will generally range from about
30:1 to abûut I.''. more preferably from about 10:1 to I.1. and most preferably about
2.5:1 to 1:1. Water-soluble salts of such acrylic acid/maleic acid copolymers can
include, for example, the alkali metal, ammonium and substituted ammonium salts.Soluble a."~ e/ ' copolymers of this type are known mQterials which are
described in European Patent Application No. 66915, published December 15, 1982,as well as in EP 193,360. published September 3. 1986. which also describes suchpolymers comprising llr~ilu~y,ulu,u.yh~ ' Stiil other useful dispersing agents
include the ~ /a~ ;llyl alcûhol LGIIJUIYIII.,~. Such materials are also
disclosed in EP 193.360. including. for example. the 45/45/10 terpolymer of
,lyl;~ ' 'vinyl alcohol.
Particularly preferred dispersant polymers are low moiecular weight
modified polyacrylate copolymers. Such copolymers contain as monomer units: a)
from about 90% to about 10%, preferably from about 80% to about 20% by weight
acrylic acid or its saits and b) from about 10% to about 90%. preferably from about
20% to about 80% by weight of a substituted acrylic monomer or its salt and havethe general formula: -[(C(R2)C(RI)(C(o)oR3)]- wherein the incomplete vaiencies
inside the square braces are hydrogen and at least one ofthe ~1l1.~.;ll....1~ Rl, R2 or
R3. preferably Rl or R2. is a I to 4 carbon aikyl or II~ilU~Cli~yl group. Rl or R2
can be a hydrogen and R3 can be a hydrogen or alkali metai sait. Most preferred is a
substituted acrylic monomer wherein Rl is methyl. R2 is hydrogen and R3 is sodium.
The low molecular weight pul,~ Le dispersant polymer preferably has a
molecular weight of less than about 15.000. preferably from about 500 to about
10.000, most preferably from about 1,000 to about 5,000. The most preferred
pOl~a~ Le copolymer for use herein has a molecular weight of 3500 and is the fully
w09~133029 2 ~ 9 1 3 1 3 P~ 071
23
neutralized form of the polymer comprising about 70% by weight acrylic acid and
about 30% by weight methacrylic acid.
Other suitable modified polyacrylate copolymers include the low molecular
weight copolymers of unsaturated aliphatic carboxylic acids disclosed in U.S. Patents
4 530,766 and 5,084,535, both illl,ul~JuldLtd herein by reference.
Agglomerated forms ofthe present invention may employ aqueous solutions of
polymer dispersants as liquid binders for making the agglomerate (particularly when
the LUlll,Uo~;i;UII consists of a mbcture of sodium citrate and sodium carbonate)
Especially preferred are polyacrylates with an average molecular weight of from
about 1,000 to about 10,000, and acr~la~t/ ' or acrylate/ fumarate copolymers
with an average molecular weight of from about 2,000 to about 80~000 and (I ratio of
acrylate to maleate or fumarate segments of from about 30:1 to about 1:'. E,xamples
of such copolymers based on a mixture of u~a~u~dLtd mono- and dicarboxylate
monomers are disclosed in European Patent Application No. 66~915~ ~)ublished
December 15, 1982. ;lI~Ul~JUldLti herein by reference.
Other dispersant polymers useful herein include the polyethylene gl~cols arrd
pol~l u~,,~l. ,.~, glycols having a molecular weight of from about 950 to aboult 30,000
which can be obtained from the Dow Chemical Company of Midland~ ~lichigan.
Such compounds for example, having a melting point within the range of from about
30 to about 100C can be obtained at molecular weights of 1450, 3400~ 4500~ 6000~
7400, 9500~ and 20,000. Such, . ' are formed by the pul,r~ ;. ai;ùll of
ethylene glycol or propylene glycol with the requisite number of moles of etl1ylene or
propylene oxide to provide the desired molecular weight and melting poilnt of the
respective p~ ,.le glycol and ~OI~I U~ glycol. The polyethylene~
POI1~JIU~1YI~ and mr~ed glycols are referred to using the formula
HO(CH2CH2O)m(CH2CH(CH3)O)n(CH(CH3)CH2O)oH wherein m, n, and o are
integers satisfying the molecular weight and Lt--~ ,.dLul t~ u;lCll~ given above.
Yet other dispersant polymers useful herein include the cellulose sulfi!te esters
such as cellulose acetate sulfate, cellulose sulfate, .~IIU~,LIIYI cellulose sulfate,
30 I~,,i.yl~,ellulose sulfate, and ~.~ Ilu~y~lu~Jyl~,~llulose sulfate. Sodium cellulo~je sulfate
is the most preferred polymer of this group.
Other suitable dispersant polymers are the l,albu~ylaLtd pol~a.~lldl;ll~
particularly starches, celluloses and alginates, described in U.S. Pat. No. 3,723,32~,
Diehl, issued Mar. 27, 1973; the dextrin esters of pul~,albu~yl;~. acids disclosed in
U.S. Pat. No. 3,929,107~ Thompson. issued Nov. I l, 1975; the hydroxvall~yl starch
ethers, starch esters, oxidized starches, dextrins and starch llydlul~ait~ described in
U.S. Pat No. 3,803,285, Jensen, issued Apr. 9, 1974; the ~,dlbu~làLtli starches
21913~3
WO9~/33029 I~ U,,,_. "~1
74
described in U.S. Pat. No. 3,629.171, Eldib~ issued Dec. 71, 1971; and the dextrin
starches described in U.S. Pat. No. 4~141,841, McDanald. issued Feb. 77, 1979 all
~ ,ul~Jula~i herein by reference. Preferred cellulose-derived dispersant polymers
are the l,dl~u;cylll.,.llyl celluloses.
YeI another group of acceptable dispersants are the organic dispersant
polymers. such as polyaspartate.
Another polymeric materia1 which can be inciuded is polyethylene glycol
(PEG~. PEG can exhibit dispersing agent p~.rull...~ as well as act as a clay soil
removal-antiredeposition agent. Typical molecular weight ranges for these purposes
range from about 500 to about 100,000, preferably from about 1,000 to about
50,000, more preferably from about 1,500 to about 10,000.
Polyaspartate and polyglutamate dispersing agents may also be used,
especially in i.~..j.",..;.... with zeolite buiiders. In ~u~ u~;lio~ls containing detergent
builders, it is believed, though it is not intended to be limited by theory, that
15 polymeric dispersing agents enhance overall dctergent builder ~ ru~ e~
especially zeolite and/or silicate builders, when used in .~ ,. with other
buiiders (including lower molecular weight pùly~ bu7.yLi~) by crystal growth
inhibition, particulate soil release peptization, and anti-~ n~ - Dispersing
agents such as pOl,y/la"~La~ preferably have a molecular weight (avg.) of about
20 1 0,OOû. ~ ~ =
Suds Suppressors - Compounds for reducing or suppressing the formation of
suds can be ;.._ull~ulaL~ i into the ~ of the present invention. Suds
~u~JIJIea~;u~ can be of particular importance in the so-called "high ~,ull~ lL~aLiu~
cleaning process" as disclosed in U.S. 4,489,455 and 4,489,574 and in front-loading
25 European-style washing machines.
A wide vanety of materials may be used as suds :~U~ DUI~, and suds
~u~ ul S are well known to those skilled in the art. See, for example. iCirk Othmer
E~,y~,lul,.,Ji~ of Chemicai Technology, Third Edition, Volume 7, pages 430-447
(John Wiley & Sons, Inc., 1979). One category of suds suppressor of particular
30 interest ~ IllullO~ lbui'~yl;~ fatty acid and soluble salts therein. See U.S.Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The
monocarboxylic fatty acids and saits thereof used as suds suppressor typically have
ily~ilu~bjl chains of 10 to about 24 carbon atoms, preferabiy 12 to 18 carbon
atoms. Suitable salts include the alkali metal salts such as sodium, potassium. and
35 iithium saits, and ammonium and " ' ' salts.
The deter~ent ~ ;u~ herein may also contain non-surfactant suds
~UIJlJIU~:~UIS. These include, for example: high molecular weight ~Iy i~u~ UIl, such
2 1 9 ~ 3 ~ 3
wo gs/33029 r~
~s
as paraffin, fatty acid esters (e.g., fatty acid triglycendes), fatty acid esters of
l.lul.u~ lL alcohols, aliphatic Clg-C40 ketones (e.g., stearone), etc. Other suds
inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmeli~mines or
di- to tetra-alkyldiamine chlortriazines forn1ed as products of cyanuric chlonde with
5 two or three moles of a primary or secondary amine containing I to 7~ carbon atoms.
propylene oxide, and monostearyl phosphates such as monostearyl alcohol l~hosphate
ester and monostearyl di-alkali metal (e. ,., K, Na. and Li) phosphates and l~hosphate
esters. The hydluudll)oll~ such as paraffin and l~à~vpald~ can be utilizer~ in liquid
form. The liquid hydlu~all)OI~a will be liquid at room ~C~ ,ldLulc and d~llloa~
10 pressure, and will have a pour point in the range of about -40C and about 50C, and
a minimum boiling point not less than about 110C (~I ."h~ pressure). It is alsoknown to utilize waxy hydlul,dlllulla, preferably having a melting point below about
100C. The llydluuallJulla constitute a preferred category of suds supp~-essor for
detergent ~u..,l.v~ Ilydlu~,al~ull suds au~J~JIcaavla are descnbed, for example.in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. The ;~luual~v~5,thus, include aliphatic, alicyclic, aromatic, and h~ ..u.,~.,l;., saturated or ullsaturated
.,~llucdll)u... having from abûut 12 to about 70 carbon atoms. The term "paraffin."
as used in this suds suppressor discussion, is intended to include mixtur~:s of true
paraffins and cyclic ilydluual~ulla.
Another preferred category of non-surfactant suds aU~JlCaaUIa comprises
silicone suds au~ntaaula. This category includes the use of polyu,~ oils~
such as poly.l;ll.~"l.ylsiloxane, dispersions or emulsions of pûlrvl~ 'f oils orresins, and c....,l.;,.- ;.."~ of polyulr"..,..-~ with silica particles wtlerein the
PVIYUIL~ ~ jS I I 1,.,.1 or fused onto the silica. Silicone suds SU~ caaul a
are well known in the art and are, for example. disclosed in U.S. Patent 4,265,779,
issued May 5, 1981 to Gandolfo et ai and European Patent Appliclltion No.
89307851.9, published February 7, 199û, by Starch, M. S.
Other silicone suds au~ aDula are disclosed in U.S. Patent 3,455,~39 which
relates to .,.".I.v~ and processes for defoaming aqueous sollltions by
;lI~,Ul~JUldL;II~ therein smail amounts of pu~ ,L~ ' ' fluids.
Mixtures of silicone and silanated silica are described, for instance, in GermanPatent Application DOS 2,124,526. Silicone defoamers and suds controlling agentsin granular detergent ~. 1.-.~;l;., ~ are disclosed in U.S. Patent 3,933,672, Bartolotta
et ai, and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.
An exemplary silicone based suds suppressor for use herein i,s a suds
au~,ulcaa;l-g amouM of a suds controlling agent consisting essentiaily of:
W095133029 2 ~ 9 ~ 3 ~ 3 P~ J.. ,S~
26
(i) polydimethylsiloxane fiuid having a viscoSity of from about ~0 cs to
about 1.500 cs. at 25C~ ~
(ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siioxane
resin composed of (C1~3)3SiOI/2 units oF SiO2 units in a ratio of from
~CH3)3 SiOI/2 units and to SiO ~ units of from about 0 6 1 to about
1 2:1; and
(iii) from about l to about 20 parts per 100 parts by weight of Ii) of a soiid
silica gel ~=
In the preferred silicone suds suppressor used herein, the solvent for a
continuous phase is made up of certain polyethylene glycols or polyethylene-
p~l~p~u~ e glycol copolyrners or mixtures thereof (preferred). or po~ ulJyl~n~
glycol The primary silicone suds suppressor is branchedlcrossliniced and preferably
not linear
To illustrate this point further. typical liquid laundry detergent ~u."~
with controlled suds wiil optionaily comprise from about 0 001 to about l, preferably
from about 0 01 to about 0 7, most preferably from about 0 05 to about 0 5, weight
% of said silicone suds suppressor, which comprises (i) a n. . ~ emulsion of a
primary antifoam agent which is a mixture of (a) a polyu, ~ lf (b) a resinous
siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler
material, and (d) a catalyst to promote the reaction of mixture ( ,,".~ (a), (b)and (c), to form siianolates; (2) at least one nonionic siiicone surfactant; and (3)
PlY~ glycol or a copolymer of pol,r~"h~l~.,e-pcl~..u~,~l.,..~ glycol having a
solubility in water at room t~ dlUlC of more than about 2 weight %; and without
polJl.~u~ le glycol Similar amounts can be used in granular .,olll}J-a~;Liol~. gels.
etc. See aiso U.S Patents 4,978,471, Starch, issued December 18, 1990, and
4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et al., issued February
22, 1994, and U S. Patents 4,639,489 and 4,749,740, Aizawa et ai at column 1. Iine
46 through column 4, line 35
The silicone suds suppressor herein preferably comprises p~ "h~ , glycol
and a copolymer of polyethylene glycoi/~,uly~Jlu~ nc giycol, all having an average
molecular weight of less than about 1,000, preferably between about 100 and 800
The polyethylene glycol and pol~.,.l.yl~ ul,yl.lu~,yl~"., copolymers herein have a
solubility in water at room t~,,,llJ.,,dLUlc of more than about 2 weight %, preferably
more than about 5 weight %
The preferred solvent herein is pùl,y~,.l.yl~ glycol having an average
molecular weight of less than about 1,000, more preferably between about 100 and800, most preferably between 200 and 400, and a copolymer of ~IGl~ 'C~l~
... ... . ~
woss/33o29 ~ ~ 9 1 3 1 3 PC.A/US9~106821
'7
Aiycol/poly~,,u,u~;~"c glycol, preferably PPG 200/PEG 300. Preferred is a weightratio of between about 1:1 and 1~ , most preferably between 1:3 and 1.6, of
poiyethylene glycol:copolymer of polyei~yiene-poly~.lu~ , glycol.
The preferred silicone suds S]~ a~ul ~ used herein do not contain
5 poiyl"u~ c glycol, particularly of 4~000 molecular weight. They also l~referably
do not contain block copolymers of eihylene oxide and propylene o ~ide. Iike
PLURONIC L101.
Other suds suppressors useful herein compnse the secûndary alcohols (e.g., ''-
aikyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones
disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols
include the C6-C16 alkyl alcohols having a Cl-Cl6 chain. A preferred alcohol is 2-
butyl octanol, which is available from Condea under the trademark ISCFOL 17.
Mixtures of secondary alcohols are available under the trademark ISALCEIEM 123
from Enichem. Mixed suds ~U~ U.~aUl~ typically comprise mixtures of ~llcohol +
15 siiicone at a weight ratio of 1:5 to 5:1.
For any detergent ..~ ;v ~ to be used in automatic laundry washir~g
machines, suds should not form to the extent that they overfiow the washing machine.
Suds ~U~ Vl~, when utilized~ are preferably present in a "suds :~U~
amount. By "suds ~U~ lg amount" is meant that the formulator of the
2û ~ v~ can select an amount of this suds controlling agent that will s~lfficiently
control the suds to result in a low-sudsing laundry detergent for use in ~lutomatic
laundry washing machines.
The ~ r.~ herein will generally compnse from 0% to abol~t 5% of
suds suppressor. When utilized as suds :~U~ VI~, IIIUI~U~ JUAY~ fatty acids~ and25 saits therein, will be present typically in amounts up to about 5/0, by weiglnt, of the
detergent . .u, ..l .. .~ " . Preferably, from about 0.5% to about 3% of fatty
ullu~,~uiJv~ylal~ suds suppressor is utilized. Silicone suds ~u~ u~UI~ are typically
utiiized in amounts up to about 2.0%, by weight, of the detergent .... ~
aithough higher amounts may be used. This upper limit is practical in nature, due
30 primarily to concern with keeping costs minimized and effectiveness of lower
amounts for effectively controlling sudsing. Preferably from about 0.01% to about
1% of silicone suds suppressor is used, more preferably from about 0.25% to about
0.5%. As used herein, these weight percentage values include any silica that may be
utiiized in ~ ;IJ with uul~vl~ll ' as well as any adjunc~ matl,rials that
35 r~ay be utilized. M~ 1 phosphate suds ~UI.llUlU~,,vl:~ are gener~lly ~ d in
amounts ranging from about 0.1% to about 2%, by weig~ . of the ',VIII~V~ UII.
Hydrocarbon suds ~Up~ vl~ are typically utiiized in amounis ranging trQm about
21 9 131 3
WO 95M3029 P~ l/u_,r.
28
0.01% to about 5.0%~ although higher levels can be used. The alcohol suds
suppressors are typically used at 0.~%-3% by weight ofthe finished . .~ o~
Bri~htener - Any optical brighteners or other briohtening or whitening agents
known in the art can be i.lcu.,uu.~L~d at levels typically from about 0.05% to about
5 1.~%, by weight, into the detergent . ~ c herein. Commercial optical
brighteners which may be usefiul in the present invention can be classified intosubgroups, which inc~ude, but are not necessarily limited to, derivatives of stilbene.
pyrazoline, coumarin, carboxylic acid, ~ .S, i;b..~uLII;~ 5~5-dioxide.
azoies, 5- and 6-membered-ring l~c~ u~y..l~;~, and other ~ a~ents
10 Examples of such brighteners are disclosed in "The Production and Application of
Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons,
New York ( 1982).
Specific examples of optical brighteners which are useful in the present
are those identified in U.S. Patent 4,79û,856, issued to Wixon on
December 13, 1988. These brighteners include the PHORWHITE series of
brighteners firom Verona. Other brighteners disclosed in this reference include:Tinopal UNPA~ Tinopal CBS and Tinopal SBM, available firom Ciba-Geigy; Artic
White CC and Artic White CWD, aYailable firom Hilton-Davis, located in Itaiy; the 2-
(4-stryl-phenyl)-2H-napthol[1,2-d]triazoles; 4,4'-bis- (1,2,3-triazol-2-yl)-stil- benes;
2û 4,4'-bis(stryl)bisphenyls; and the _ Specific examples of these
brighteners include 4-methy~-7-diethyl- amino coumarin; 1,2-bis( v. ;,..;.1~,..1-2-
yl)ethylene; 1,3-diphenyl-1 .1" ~ ,- ,1 .. , 2,5-bis(benzoxazol-2-yl)thiophene: 2-stryl-
napth-[1,2-d]oxazole; and 2-(~1iliJ.ll. ~ yl)-2H-naphtho- [1,2-d]triazole. See also
U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton. Anionic brighteners25 are preferred herein.
('' ' A~nt~ - The detergent l u~ herein may also optionally
contain one or more iron and/or manganese chelating agents. Such chelating agents
can be selected from the group consisting of amino ~ U~y' amino
1' ,' , poly~ ubstituted aromatic chelating agents and mixtures
30 therein. all as hereinafter defined. Without intending to be bound by theory, it is
beiieved that the benefit of these materials is due in part to their exceptional ability to
remove iron and manganese ions from washing solutions by formation of soluble
chelates.
Amino .,~i,u,~yl~.L.~ useful as optional chelating agents include
35 ~Li.,~l~ ' a.,e~ , N ~ u~ h~ " nitrilo
triacetates, cL}.y' ' L~ .U.u~,,;u,,d~.,, L~ Ll-- h ~ .nr~
wo ssl3302s 2 T 9 ~ 3 ~ 3
diethyl~ ";". ~,..,l,....~lr,, and ethanoldiglycines. alkali metal. ammon:ium, and
substituted ammonium salts therein and mixtures therein.
Amino ~ ,",1~ are also suitable for use as chelating agents in the
, ~""l,.~;~;l...~ of the invention when at lease low levels of total phosphorus are
5 permitted in detergent Lo~ )u~;Liull~, and include ethyl~",c~i;a...;lletetrakis
(methyi~ ,o~ tr~) as DEQUEST. Preferred. these amino rl~ to not
contain aikyl or alkenyl groups with more than about 6 carbon atoms.
Polyfunctionally-substituted aromatic chelating agents are also usefi~l in the
Lul~l,L~L~;Livll~ herein. See U.S. Patent 3,812,û44, issued May 21, 1974, to Connor et
lû al. Preferred compounds ofthis type in acid form are Li;l~ u7.y~ .11r~1br.~ such
as 1.2-dihydroxy-3,5-~ r~lv ~
A preferred b;OLiC~I ~LLiCLIL chelator for use herein is ethyl.. 1 -,
disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent
4,7û4,233, November 3, 1981, to Hartman and Pericins.
If utilized, these chelating agents will generally compnse firom about û.l% to
about 10% by weight of the detergent ~.. l.. ,~;l;v~ herein. More preferably,if
utilized, the chelating agents will comprise from about 0.1% to about 3.0% by weight
of such f ~ l-O` l ~
F~hric Softenin~ Clav:
Various clay through-the-wash fabric softeners, especially the in~paipabie
smectite clays of U.S. Patent 4.062,647. Storm and Nlrschi, issued Decernber 13,1977, as well as other softener clays icnown in the art, can optionaily be used typically
at levels of from about 0.5% to about lû% by weight in the present ~ u~ ",c to
provide fabric softener benefits LVIILUIll,..~ly with fabric cleaning. Clay soft~ners can
be used in ~.v~ , with amine and cationic anti-static agents, as disclosed, for
example, in US. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent
4,291,071, Harris et al. issued September 22, 1981.
The clay softening system herein will typically comprise a fabric softelting clay
present in an amount of at least 0.5%, preferably from 4% to 30% by weight of the
detergent ~ .u~ The preferred clays are of the smectite type, although other
types of softening clays are known and may be used herein. The foDowing describes
non-limiting exampies of softening clays.
Smectite type clays are widely used as fabric softening ingredients in
detergent ~ Most of these clays have a cation exchange capacity of at
least 50 meq./100 g.
Smectite clays can be described as three-layer expandable materials, consisting
of ' silicates or magnesium silicates.
2 1 9 1 3 1 3
W0 95133029 ~ c-
There are two distincl classes of smectite-type clays; in the first, aluminum
oxide is present in the silicate crystal lattice, in the second class of smectites.
magnesium oxide is present in the silicate crystal lattice.
The general formulas of these smectites are A12~Si20s)2(0H)- and
5 Mg3(Si20s)~0E~i)2, for the aluminum and magnesium oxide type clay, respectively
The range of the water of hydration,can vary with the processing to which the clay
has been subjected. i urthermore, atom sllhctit~lti~-~n by iron and magnesium can occur
within the crystal lattice of the smectites, ~hile metal cations such as Na+, Ca2+, as
well as H+ can be co-present in the water of hydration to provide electrical neutrality
It is customary to distinguish between clays on the basis of one cation
pred~ or exclusively absorbed. For example, a sodium clay is one in which
the absorbed cation is ,u~do~ ly sodium. Such absorbed cations can become
involved in equilibrium exchange reactions with cations present in aqueous solutions.
In such equilibrium reactions, one equivalent weight of solution cation replaces an
equivalent of sodium, for example, and it is customary to measure clay cation
exchange capacity in terms of I '"' , 'v ' per 100 g of clay (meq/100 g).
The cation exchange capacity of clays can be measured in several ways,
including ~ ud;~lyai~, by exchange with ammonium ion followed by titration, or by
a methylene blue procedure, as set forth in Grimshaw, The Chemistry of Physics of
Clays, III~GI~ t Publishers, Inc. pp. 264-265 (1971), The cation exchange
capacity of a clay minerai relates to such factors as the expandable properties of the
clay, the charge of the clay, which in turn, is determined at least in part by the lattice
structure, and the like. The ion exchange capacity of clays vai-ies wideiy in the range
from about 2 meq/100 g for kaolinites to about 150 meq/100 g, and greater for
certain clays of the ill~, iLG variety. Illite clays have an ion exchange capacity
somewhere in the lower portion of the range, ca. 26 meqllOO g for an average illite
clay.
It has been determined that iliite and kaolinite clays, with their relatively low
ion exchange capacities, are not useful in the instant ..~ Indeed such illite
30 and kaoiinite clays constitute a major component of clay soiis. However, smectites,
such as nontronite having an ion exchange capacity of a~J~Jlw i~ 50 meq/100 g;
saponite, which has an i.,.. I._.. v, capacity greater than 70 meqllOO g, have been
found to be useful fabric softeners.
The smectite clays commoniy used for this purpose herein are all
~o.. ,~,.. ;llly available. Such clays include, for example, IllUllilllOI'" "'.
v~.l. 1 - -~.-;l, nontronite, hectorite, saponite. sauconite, and vermiculite. The clays
herein are avaiiable under commercial names such as "fooler clay" (clay found in a
.. ..
~ w0 95/33029 2 ~ 9 1 3 ~ 3
relatively thin vein above the main bentonite or IllUllLl,.ul '' veins in the Black
Hills) and various tradenames such as Thixogel #l (also. "Thixo-Jell") and Gelwhite
GP from Georgia Kaolin Co., Elizabeth, New Jersey; Volclay BC and Volcay i~325~
from American Colloid Co.. Skokie~ Illinois; Black Hills Bentonite BH 45û, from
5 IllL~ Liulldl Minerals and Chemicals; and Veegum Pro and Veegum F, from R, T.
Vanderbilt. It is to be recognized that such smectite-type minerals obtained Llnder the
foregoing commercial and trade names can comprise mixtures of the variûus discrete
mineral entities. Such mixtures ofthe smectite minerals are suitable for use herein.
Preferred for use herein are the Illul~ lul ll clays having an ion capacity
of 50 to 100 meq/100 g which ~,Vllta~Jull i~ to ca. 0.2 to 0.6 layer charge.
Quite suitable are hectorites of natural origin, in the form of particles havingthe general formula
m
[(Mg3-xLix)si4-yMeyolo(oH2-zFz)]-(x+y) ~ Mn+
wherein MelII is Ai, Fe, or B; or y=O~ Mm+ is a l~ùllù~/a5~,.1t (n=l) ûr divalent (n=2)
metal ion, for example, selected from Na, K, Mg, Ca or Sr.
in the above formula, the value of (x+y) is the layer charge of the l1ectorite
clay.
Such hectorite clays are preferably seiected on the basis of their layer charge
properties, i.e., at least 50% is in the range of from 0.23 to 0.31.
More suitable are hectorite clays of natural origin having a layel charge
distribution such that at least 65% is in the range offrom 0.23 to 0.31.
The hectorite clays suitable in the present ~ should preferably be
sodium clays, for better softening activity.
Sodium clayâ are either nawraiiy occurring, or are nawraily-occurring
caicium-clays which have been treated so as to convert them to sodium-clays. If
calcium-clays are used in the present ~.~.,,~,.,~-;1;,~ ., a sait of sodium can be a~dded to
the ~ in order to convert the caicium clay to a sodium clay. Preferably,
such a sait is sodium carbonate, typically added at levels of up to 5% of the total
amount of clay.
Examples of hectorite clays suitable for the present .,v~ include
Bentone EW and Macaloid, from NL Chemicals, N.J., U.S.A., and hectorites from
Industrial Mineral Ventures.
Other softening clays of varoius types and classes are disclosed in the
literature and may aiso be used herein.
` 2191313
Wo 95/33029 , r~ .
32
Anti-St:~ti~ ~p,~ntc - CPnsumers who use fabric soReners have come to expect
that fabrics treated therewith will also be provided with an anti-static benefit. Since
soRener clays are rather poor anti-stats. the formulator may wish to add an anti-static
agent to such . ~ Various anti-static agents are known in the art and may
S be used herein. so ~ong as they do not disadvantageously interact with the other
ingredients of the ~ Quite suitable water-soluble antistatic agents herein
include the wel~-known cationic and quaternary ammonium salts such as Cl0-C18
trimethyl ammonium chloride, the acid salts of the Clo-C14 dimethyl amines~ the
hydroxy-substituted quats~ such as the Clo-CIg dimethyl(l-yJlu~ yl)ammonium
10 chloride, Clo-clg(JillyJlu~ yl)~ lly~ nillrn chloride, lauryl
trimeth~l- ,.,.. ,.;.. chloride or bromide, and the like. Such optional anti-stats are
preferablyusedatlevelsfromaboutO.15%toabout2.5%ofthe~ull-lJva;Liu--a.
Other Inr~r~ ntc - A wide variety of other ingredients useful in detergent
,O~ c can be included in the "u~ ,ual~ivlls herein, including other active
15 ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for
liquid rullllul.~ lla, solid fillers for bar ~ , etc, If high sudsing is desire~,
suds boosters such as the Clo-C16 " ' `' can be ill~,ul~Julalt;J into the
.. l,.,c:l;.. -, typically at 1%-10% levels. The Clo-c14 .. u ' -' and diethanol
amides illustrate a typical class of such suds boosters, Use of such suds boosters with
20 high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines
noted above is also adval.~ ,vua If desired, soluble magnesium salts such as
MgC12, MgSO4, and the like, can be added at levels of, typically, 0.1%-2%, to
provide additional suds and to enhance grease removal p". ru,
Various detersive ingredients employed in the present .... l,..~ . - optionally
25 can be further stabilized by absorbing said ingredients onto a porous ~JIùpliui~lc
substrate, then coating said substrate with a ~.~J,u~,i.vl,i.. coating, Preferably, the
detersive ingredient is admixed with a surfactant before being absorbed into theporous substrate. In use, the detersive ingredient is released from the substrate into
the aqueous washing liquor, where it performs its intended detersive function.
To illustrate this technique in more detail, a porous llyJIulJllulJii silica
(trademark SrPERNAT D10, DeGussa) is admixed with a proteolytic enzyme
solution containing 3%-5% of C13 l5 ethoxylated alcohol (EO 7) nonionic
surfactant, Typically, the ~l~yll..,,'aulL,~ solution is 2.5 X the weight of silica.
The resulting powder is dispersed with stirring in silicone oil (various silicone oil
viscosities in the range of 500-12,500 can be used). The resulting silicone oil
dispersion is emulsified or otherwise added to the final detergent matrix. By this
means, ingredients such as the dru,e ,.-;...,~d enzymes, bleaches, bleach activators,
. _ .. . . _ _ . . _ . . _ _ _ _ _ _ _ _ _ _
WOg~/33029 ~191 313 r~,,uv~
33
bleach catalysts, photoactivators, dyes, fiuorescers. fabric ~,ullJiLiOll~la andhydlùly~lJic surfactants can be "protected" for use in detergents.
The detergent ~u~po~;Liull~ herein will preferably be formulated ~iuch that,
during use in aqueous cleaning operations, the wash water will have a pH of between
about 6.5 and about 11, preferably between about 7.5 and 10.5, Laundry products
are typically at pH 9-11. Techniques for controlling pH at ,~ us,~ge levels
include the use of buffers, alkalis, acids, etc., and are well known to those skilled in
the art.
Granuiar detergents can be prepared, for example, by spray-dryimg (final
product density about 520 g/l) or ~ (lm~rs~tin~ (final product density above about
600 g~l) the Base Granule. The remaining dry ingredients can then be acmixed in
granular or powder form with the Base Granule, for example in a rotary mixing drum,
and the liquid ingredients (e.g., nonionic surfactant and perfume) can be sprayed on.
The following examples illustrate the detergent ~ ;l;u ~ ofthis invention,
but are not intended to be limiting thereof
EXAMPLE I
A granular detergent l l." l.u~:l;.. ,. comprising a non-phosphorus builder
system is as follows:
In~redient % (wt.)
20Oleoyl Sarcosinate, Na 8.0
Tallowalkyl Sulfate, Na 2.5
C12 14N-~ plu~ ll.. dc 5.0
C 12-14 T ' yl - .. l " l. Chloride 1.2
Zeolite A (1-10 llf~ ull.~.~cil) 23
25Maleic/Acrylic Copolymer 5.0
Sodium P~ b~ t~ 12
TAED 4.0
Sodium Carbonate 10.6
Sodium Silicate (2.0) 5.0
30Glycerol 0.5
Savinase (enzyme) 1.6
Silicone (suds au~ aaUl) 0.5
Water, Perfume, Minors Balance
EXAMPr FlI
The, , of Example I is modified by replacing the sodium
~J.,.c,~..bu..~.~e with an equivalent amount of sodium perborate and deleting the N-
~` - 2191313
wo 95133029 . ~ . c
34
yl~lu~ llid~. In an alternate mode, all or part of the TAED bleach activator canbe replaced by NOBS bleach activator.
EX~LE III _ e _ r
A granular detergent ~ul~luOai~iull comprising a mixed, non-phosphorus
5 builder system is as follows:
In~redient % (wt.)
Oleoyl Sarcosinate, Na 8.0
Cl4 15 Alkyl Sulfate, Na 3.0
Sodium Citrate 5.0
10Zeolite A (1-10 ~u~-u~ ) 20.0
Sodium r.,l~,a~bu~ L~ 18.0
TAED NOBS (1:1) 5.0
Sodium Sulfate 12.0
Sodium Silicate 5.0
C12 14 Dimethyl (Hydroxyethyl) Ammonium Chioride 1.5
Polyacryiate (mw 4000-5000) ~ 3.0
Hydrogen Tallow Fatty Acid 0.5
CAREZYME 0 9
SAVINASE 0.75
TERMAM~ 0.75
Optical Brightener 0.2
Moisture, Minors Balance
F~AMPLF. IV . =
In the UU~ iUI~ of Example III, the Zeolite A may be replaced by an
25 equivalent amount of SKS-6. In an alternate mode~ the alkyl sulfate can be replaced
by a C 11-14 alkyl benzene sulfonate surfactant.
EXAMPLE V
A granular f.. . ~ . comprises the following ingrediçnts.
30In~rçdient % (wt.)
Oleoyl Sarcosinate, Na 19.0
Zeolite A (1-10 microns) 25.0
Sûdium Citrate 3.0
Sodium Pel~ 12.0
351'ul~ aLt: 5.0
EDDS 3 0
Protease 1.0
~ Wo 95/33029 ~ I 9 1 3 1 3 1 ~"1 c ~
Lipase 1.0
TAED 5 0
Sodium Carbonate 10.0
Sodium Silicate 3 0
Water and Minors Balance
EXA~r.F VI
The ~ c~ of Example V is modified by reducing the oleoyl sarcosinate
to 17% of the l,u~ va;iiOII and adding 2% by weight of coconutalkyl ethoxylate ( 1-
5 avg. ethoxylate) as NEODOL.
EXA~I F Vll
A detergent bar is prepared by compacting and extruding a ~ t/G~;l;
generally according to Example V.
