Note: Descriptions are shown in the official language in which they were submitted.
WO 95/27775
~8~I 69
BLEACH COMPOSITIONS CO~RISING METAL-CONTAINING BLEACH
CATALYSTS
TECHNICAL F~F.T n
The present invention relates to bleaching ~.u .~ (e.g., granular
detergent c~.~n~ , iiquid bleach additive ~r~ -) useful for laundering
fabrics comprising a metai bleach cataiyst and a peroxy compound, wherein the molar
ratio of hydrogen peroxide to peracids is less than about 4:1.
BA-'T~ OUND OF T~F INVF.~TION
Metai-containing cataiysts have been described in bleach ~
including _ -containing catalysts such as those described in EP 549,271; EP
549,272; EP 458,397; US 5,244,594; US 5,246,621; EP 458,398; US 5,194,416; and
US 5,114,611. These bleach cataiysts are described as being active for cataiyzing the
20 bleaching action of peroxy: . ' against various stains. Several of these
bleaching systems are said to be effective fûr use in washing and blcaching of
substrates, including laundry and hard surfaces (such as machine li;ai~. '' g,
general cleaning) and in the textile, paper and wood pulp industries.
It has been discovered that these metal-containing bleach catalysts, especially
25 the ~ containing cataiysts, have the particularly undesirable property, when
us~d with textiies, of damaging the fabric resulting in loss of tensile strength of the
fibers and/or producing color damage to the fabric. Obviously, such properties for
is a Breat drawback to the general use of these ~ , in the
laundry area.
It has now been SU~ ;a;l~ y discovered that controiing the ratio of the
bleaching agent that is a source of hydrogen peroxide to the bleach activator in such
laundry ~ comprising metal-containing bleach catalysts reduces the fabric
damage resulting from these cataiysts in the laundry process.
These and other objects are secured herein, as will be seen from the following
disclosures.
BACKGROUr~D ART
wo ss/2777s 2 1 8 7 1 6 9 ; ~ 2 ~ P~
The use of amido-derived bleach activators in laundry detergents is described
in U.S. Patent 4,634,551. Arlother. class of bleach activators comprises the
benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued
October 30, 1990. The use of manganese vvith various complex ligands to enhance
bleaching is reported in the following United States Patents: 4,430,243; 4,728,455;
5,246,621; 5,244,594; 5,284,944; 5,194,416; 5,246,612; 5,256,779; 5,280,1 17;
5,274,147; 5,153,161; 5,227,084; 5,114,606; 5,114,611. Seealso: EP 549,271 Al;
EP 544,490 Al; EP 549,272 Al; and EP 544,440 A2.
SUMMARY OF THE INVENTION
The present invention relates to laundry bleaching ~1.. ,l,,,~;l;,.. ~ having
reduced metal-containirlg bleach catalyst-induced fabric damage, said ~ 1'~
comprising:
(a) a peroxy compound selected from the group consisting of preformed
organic p_.~,albu~li_ acids, bleaching mixtures coMaining a bleaching agent that is a
source of hydrogen peroxide and one or more bleach activators, and mixtures thereof
present in an effective amount to cause bleaching;
(b) a metal-containing bleach catalyst (preferably a manganese bleach
catalyst) present in an effective amount to activate the peroxy compound; and
wherein further the molar ratio of hydrogen peroxide to peracid, from the
preformed organic p~ llbU~I;~. acids or the bleach activator, is less than about 4:1.
All ~ CIIlL~ , ratios and IJl u~ul ~;ull~ herein are by weight, unless other vise
specified. All documents cited are, in relevant part, ;Il~,ullJola~td herein by reference.
DET~rr Fn DESCRIPTION OF THF. INVENTION
Metal-C, Rl~zlrh (`~t~lyst
One type of bleach catalyst is a catalyst system comprising a heavy metal
cation of defined bleach catalytic activity, such as copper, iron or manganese cations,
an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or
aluminum cations, and a sequestrant having defined stability constants for the
catalytic and auxi~iary metal cations, particularly e~ t ~ acid,
elhJ~ ' '.,.e~ acid) and water-soluble salts thereof.
Such catalysts are disclosed in U.S. Pat. 4,430,243.
Other types of bleach catalysts include the _ -based complexes
disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of
these catalysts include MnlV2(u-O)3(1,4,7-trimethyl-1,4,7-~-;a,a~, 't )2-
(PF6)2, Mnm2(u-0)1(u-OAc)2(1,4,7-trimethyl-1,4,7-ll;a~a~Y~lvlll~ )2(clo4)2~
MlllV4(U-0)6(1,4,7-~ A y~Iù"'-lf)4(C104)4~ MnlllMnlV4(u-)l(u-OAC)2-
(l~4~7-trimethyl-l~4~ l;a~al~y~lullu~ -)2(clo4)3~ and mixtures thereûf Others are
WO951~7775 ~ ,I/U~,; ,r
1 3
described in European patent application publication no. 549,272. Other ligands
suitable for use herein include l,5,9-trimethyl-1,5,9~ ,y.'c~d~ , 2-methyl-
1,4,?-Lli~.,y,' 2-methyl-1,4,7-l.i~,y,' ~, 1,2,4,7-tetramethyl-
1,4,7-~l;~,' , and mixtures thereo Also included are the . ~
S manganese (IV) complexes suçh as MnIV(1,4,7-trimethyl-1.4,7-
.;~,lo~o.. ~)(OCH3)3(PF6) as described in U.S. Pat. 5,194,416.
Still another type of bleach catalyst, as disclosed in U.S. Pat. 5, 114,606, is a
water-soluble complex of manganese (Il), (m), andlor (IV) with a ligand which is a
non-carboxylate pGlyh~.l.u~y compound having at least three Cu...,~ ive C-OH
groups. Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol,
adonitol, meso-erythritol, ' 1, lactose, and mixtures thereof.
U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of
transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand.
Said ligands are of the forrnula:
R2 R3
Rl-N=C-B-CSN-R4
wherein Rl, R2, R3, and R4 can each be selected from H, substituted alkyl and aryl
groups such that each Rl-N=C-R2 and R3-C=N-R4 form a five or six-membered
ring. Said ring can further be substituted. B is a bridging group selected from 0, S.
CR5R6, NR7 and CsO, wherein R5, R6, and R7 can each be H, alkyl, or aryl
groups, including substituted or llncllhstitllt~ groups. Preferred ligands include
pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings.
Optionally, said rings may be substituted with ~u~ such as alkyl, aryl, alkoxy,
halide, and nitro. Particularly preferred is the ligand 2,2'-b;~ .;Jy' Preferredbleach cahlysts mclude Co, Cu, Mn, Fe,-b;~ .i.ly' ' and -b;a~ hl~' '
complexes. Highly preferred catalysts include C0(2,2-~;atJ~l;.l~ )C12,
Di(- ~, )b;a~ cobalt (II), ~,ia.l;l,~l;J~lalll;..e-cobalt(II)
perchlorate, Co(2,2-b;a~J~.hlyl~ll...l.~)202C104, Bis-(2,2'-~;a~,~.id~h...,i.l~) copper(lI)
~.,.1 ' ' ', tris(di-2-~,J.id~' -) iron(II) perchlorate, and mixtures thereof
Other examples include Mn gluconate, Mn(CF3S03)2, Co(NH3)sCI, and the
binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including
N4Mnm(u-0)2MnlVN4)+and [Bipy2Mnlll(u-0)2MnlVbipy2]-(C104)3
The bleach catalysts of the present invention may also be prepared by
combining a water-soluble ligand with a water-soluble manganese salt in aqueous
media and ~u,. l.~ the resulting mixture by evaporation Any convenient
water-soluble salt of manganese can be used herein. Manganese (II), (III), (IV)
and/or (V) is readily available on a commercial scale. In some instances, sufficient
,,,, ... ,, .. ,, , .. , .. .. _, , , _
wo 9s/27775 2 1 8 7 1 6 9 ,~
manganese may be present in the wash liquor. but, in general, it is preferred to add
Mn cations in the c- i~u~;f~ to ensure its presence in ~d~dlyliL..') cffective
amounts. Thus, the sodium salt of the ligand and a member selected from the group
consisting of MnSO4, Mn(ClO4)2 or MnC12 (least preferred) are dissolved in water5 at molar ratios of ligand:Mn salt in the range of about 1:4 to 4:1 at neutral or slightly
alkaline pH. The water may first be de-oxygenated by boiling and cooled by sparging
with nitrogen. The resulting solution is evaporated (under N2, if desired) and the
resulting solids are used in the bleaching and detergent f ,J".~ c herein without
further p~-rifif ~iinn
In an alternate mode, the water-soluble manganese source, such as MnSO4, is
added to the bll,a~ or to the aqueous Ih~c;u~ bath
which comprises the ligand. Some type of complex is apparently formed in sltu, and
improved bleach p, ~ is secured. In such an in situ process, it is convenient
to use a ~ . .-- - -l ,-l ~lt molar excess of the ligand over the manganese, and mole ratios
of ligand:Mn typically are 3 :1 to 15 :1. The additional ligand also serves to scavenge
vagrant metal ions such as iron and copper, thereby protecting the bleach from
,l~ ,- One possible such system is described in European patent
application, publication no 549,271.
While the structures of the bleach-catalyzing Illàll,~;a~ ,ul~ L".~ of the
present invention have not been elucidated, it may be speculated that they comprise
chelates or other hydrated l,uuld;l,aL;ul, complexes which result from the interaction
of the carboxyl and nitrogen atoms of the ligand with the manganese cation
Likewise, the oxidation state of the manganese cation during the catalytic process is
not known with certainty, and may be the (+II), (+III), (+IV) or (+V) valence state.
Due to the ligands' possible six points of attachment to the manganese cation, it may
be reasonably speculated that multi-nuclear species and/or "cage" structures mayexist in the aqueous bleaching media Whatever the form of the active Mn-ligand
species which actually exists, it functions in an âpparently catalytic manner to provide
improved bleaching ~"fu. on stubborn stains such as tea, ketchup, coffee,
blood, and the like.
Other bleach catalysts are described, for example, in Eurûpean patent
application, publication no. 408,131 (cobalt complex catalysts), European patent1" ' , publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts),
U.S. 4,728,455 (1llL~ 5all1)l~ Uf Iigand catalyst), U.S 4,711,748 and
European patent application, publication no. 224,952, (absorbed manganese on
catalyst), U.S 4,601,845 (:' " support with manganese
and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S
.. .. _ _ _ _
1 6 ~
~ wo s5l2777s
4,119,557 (ferric complex catalyst), German Pat ~ ;.". 2,054,019 (cobalt
chelant catalyst) Canadian 866,191 . ~transition metai-containing salts), U.S.
4,430,243 (chelants with manganese cations and non-catalytic metal cations), and
U.S. 4,728,455 (manganese gluconate catalysts).
The bleach catalyst is used in a catalyticaUy effective amount in the
and processes herein By '`~al~ , effective amount" is meant an
amount which is sufficient, under whatever comparative test conditions are
employed, to enhance bleaching and removal of the stain or stains of interest from the
target substrate. Thus, in a fabric laundering operation, the target substrate will
typicaily be a fabric stained with, for example, various food stains. The test
conditions wiU vary, depending on the type of washing appliance used and the habits
of the user. Thus, front-loading laundry washing machines of the type employed in
Europe generally use less water and higher detergent uull.,c,~ Liu..., than do top-
loading U.S.-style machines. Some machines have l,ù....i~,.al~ longer wash cycles
15 than others. Some users elect to use very hot water; others use warm or even cold
water in fabric laundering operations. Of course, the catalytic p.,.ru,.,.a..~,~ of the
bleach cataiyst will be affected by such cc,,...:~c.~,lU~...., and the ievels of bleach
cataiyst used in fully-formulated detergent and bleach .,~ ,.. can be
4~ lû~J~;at~,lJ adjusted. As a practical matter, and not by way of limitation, the
20 r.u ~ and processes herein can be adjusted to provide on the order of at least
one part per ten 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
preferably from about I ppm to about 500 ppm, of the catalyst species in the laundry
liquor. To illustrate this point &rther7 on the order of 3 I.u~,lulllOlal manganese
25 catalyst is effective at 40C, pH 10 under European conditions using perborate and a
bleach activator (e.g., benzoyl .,~.~,. ula.,~ ). An increase in of 3-5 fold
may be required under U.S. conditions to achieve the same results. Conversely, use
of a bleach activator and the manganese catalyst with perborate may allow the
formulator to achieve equivalent bleaching at lower perborate usage levels than
30 products without the manganese catalyst.
The, , herein will therefore typically comprise from about I ppm
to about 1200 ppm of the metal-containing bleach catalyst, preferably from about 5
ppm to about 800 ppm, and more preferably from about 10 ppm to about 600 ppm.
Most preferred ~ ` comprise the bleach catalyst MnlV2(u-O)3(1,4,7-
35 trimethyl-1,4,7-LI;~.,lu.. ull~ulc~)2-(PF6)2 in a ~.ull~ iull of from about 30 ppm
to about 1000 ppm, preferably from about 50 ppm to about 650 ppm. more
... ......... ....... , _ . . .
wo95/27775 r~".,. .
6~ 6
.~,
preferably from about 50 ppm to about SoO ppm, and most preferably from about
120 ppm to about 400 ppm.
Peroxv l~nnlpm-n,~c
It is to be appreciated that the bleach catalyst does not function as a bleach by
5 itself. Rather, it is used as a catalyst to enhance the p~r
bleaches and~ in particular, oxygen bleaching agents such as perborate, P~ JUII~persulfate, and the like, especially in the presence of bleach activators. Accordingly,
the ~ herein also contain peroxy compounds which as used herein
includes bleaching agents and bleaching mixtures containing a bleaching agent and
10 one or more bleach activators, in an amount sufficient to provide bleaching oF the
stain or stains of interest (e.g., tea stains; wine stains).
However, for purposes of the present invention, the peroxy compound must
be selected from the group consisting of preformed organic ~ .,bu~lk, acids,
bleaching mixtures containing a bleaching agent that is a source of hydrogen peroxide
15 and one or more bleach activators, and mixtures thereo Further, when a bleaching
agent that is a source of hydrogen peroxide is present in the ~ u ~ of the
present invention, said ru .~ further have a molar ratio of hydrogen peroxide
to bleach activator is less than about 4 :1.
Bleaching agents will typically be at levels of from about 1% to about 80%,
more typically from about 5% to about 20%, of the detergent .. ~,.. 1.~,~;1;.,, especially
for fabric laundering. Bleach and pre-soak ~ may comprise from 'i% to
99% of the bleaching agent. If present, the amount of bleach activators will typically
be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of
the bleaching mixture comprising the bleaching agent-plus-bleach activator.
1. ~ srrntc
The bleaching agents used herein can be any of the bleaching agents useful for
detergent or bleaching, . in textile cleaning, hard surface cleaning, or
other cleaning purposes that are now known or become known, and are useful for
bleaching f~ -h~;l;h as used in the present invention to treat fabrics. These
include oxygen bleaches as well as other bleaching agents. Perborate bleaches, e.g.,
sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
a. Rl~srhi~ nt thgt iS a Source of Hvdro~en Peroxide:
Peroxygen bleaching agents that are a source of hydrogen peroxide may be
used in the c.~. p .~:l;...,~ Suitable peroxygen bleaching compounds include sodium5 carbonate ~ u~yhJd~ and equivalent "p~ ,al~ull~l~e" bleaches, sodium
u~ lla~, urea p.,.U~.ylly.ll~ , and sodium peroxide. Persulfate
bleach (e.g., OXONE, ~ td l;ul~ lly by DuPont) can also be used.
. _ _ . _ _ _ ., : , ,,,, _, , ~ , .. ............ ...... .... . . . ........
WO ss/2777s ~ 6 g 7 P ~ S/A~ ~
A preferred ~ IJOI~ bleach comprises dry particles having an average
particle size in the range from about 500 ilf~ ulll~ to about 1,0û0 ..u~,.u...~t~
not more than about 10% by weight of said particles being smaller than about 200llf~.,lu~lLt~ and not more than about l00~A by weight of said particles being larger
5 than about 1,250 ~u~ . Optional~y, the ~.,,.,~,.I,o..~ can be coated with
silicate, bûrate or water-soluble surfactants. Ftll,albûll~lL~ is available from varjous
commercial sources such as FMC7 Solvay and Tokai Denka.
b. Preforrn~l OrFA~nirE~tl~ vA~il;c Ari~c
As used herei4 bleaching agents also comprise preformed organic
10 ~ ul,u~l;c acids. Such bleaching agents that can be used without restriction
encompass ~ I,albu~lic acid bleaching agents and salts thereof. Suitable examples
of this class of agents include magnesium r- u~y~l-LIl~ h~ L~dldL~
(INTEROX), the msgnesium salt of metachloro perbenzoic acid, 4-~1ull~' 1
UAU~J~IU~LIt,~l;U acid and d;~ IUA~ ' . 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 û,l33,354, Banks et al, published February 20, 1985, and U.S. Patent4,412,934, Chung et al, issued November 1, 1983. Highly preferred bleaching agents
also include 6-.-o..,' - 6-UAU~ .U~aIJIU;I~ acid (NAPAA) as described in U.S.
20 Patent 4,634,551, issued January 6, 1987 to Burns et al.
Such materials nûrmally have a general formula:
HO-O-C(O)-R-Y
25 wherein R is an alky~ene or substituted alkylene group containing from I to about
22 carbon atoms or a phenylene ûr substituted phenylene group, and Y is
hydrogen, halogen, alkyl, aryl or
-C(O)-OH or -C(O)-O-OH
The organic p~,.,,c.l~UA~, acids usable in the present invention can contain
either one or two perûxy groups and can be either aliphatic or aromatic. When the
organic p~ UA.~, acid is aliphatic, the ~ J acid has the general
formula:
HO-O-C(O)-(CH2)n~Y
WO 95127M5 21 g 716 ~ `
where Y can be, for example, X CH3, CH2CI, COOH, or COOOH; and n is an
integer from I to 20.
When the organic p~,~UO,~l/UA,~, acid is aromatic, the ~ lrrl acid has
the genera5 formula:
HO-O-C(O)-C6H4-Y
wherein Y is hydrogen, alkyl, ~ lv~, .., halogen, or COOH or COOOH.
Typical ~ P~.U~IIIJUA~5;- acids useful herein include alkyl
10 p.,~w~bu~l;., acids and aryl p.lu~hbuAyL acids such as:
(i) p.,.UA~.,.~v;., acid and ring-substituted ~J~,.UA~,.LViC acids, e.g.,
peroAy-o-naphthoic acid;
(ii) aliphatic, substituted.aliphatic and arylalkyl nlvl.u~,.uAy acids, e.g.
p~..UAyl..,,.i., acid, p~.uA~al~u;., acid, and N~N-~l~Ll~aluJ~ r UA~ U;C acid
I S (PAP).
Typical diperoxy ~ u~l;~, acids useful herein include alkyl diperoAy
acids and luyldl;~J.,.uAy acids, such as:
(iii) 1,12-J;~,.,.vA.yJ~ i;v;~ acid;
(iv) 1,9-.5;1,~,.u~ ' - acid;
(v) d;~,.uA~ aa~ ;., acid; .I;IJ~U~D~ C;C acid and .I;".,,UA~ , ' ' '
acid;
(Vi) 2-d~ ..,,UA~ -1,4-dioic acid;
(vii) 4,4-aul~.l~l/;alJ.,.uA~,.~u;~, acid.
The present invention may further encompass bleaching ~.~, 1...':;.,
25 comprising an effective amount of a ' ' '1~, insoluble organic p~ ,lbv
acid bleaching agent having the general formula:
O O O O
Il 11 11 11
R~C--N--R2-C--OOH, R~N--C--R2-C--OOH
Rs Rs
wherein Rl is an alkyl, aryl, or alkaryl group containing from about I to about 14
carbon atoms, R2 j5 an alkylene, arylene or alkarylene group containing from about
30 I to about 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group
containing from about I to about 10 carbon atoms.
Peroxygen bleaching agents, the perborates, the p~ lll)u~ ta, etc., are
preferably combined with bleach activators, which lead to the in situ production in
aqueous solution (i.e., during the washing process) of the ~.,.w~lJuA~l;c acid
35 ~,u~ u...l;.,~ to the bleach activator.
~ wogsm77s ~ 8~9
2. RlP~i~h Activ~tnrc
B1each activators are known and amply described in literature, such as in the
GB Patents 836,988; 864,798; 907,356; 1,003,310 and 1,519,351; Gemman Patent
3,337,921; EP-A-0185522; EP-A-0174132i EP-A-0120591; and U.S. Pat. Nos.
1,246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393.
A class of bleach activators is that of the quatemary ammonium substituted
peroxyacid activators as disclosed in U.S. Pat. Nos. 4,751,015 and 4,397,757, inEP-A-284292, EP-A-331,229 and EP-A-03520. Examples of peroxyacid bleach
activators of this class are:
2-(N,N,N-trimethyl ~n~n-; ~nn) ethyl-4~ carbonate--(SPCC),
N-octyl,N,N-dimethyl-N 10-cali,u~ uAy decyl ammonium chloride--
(ODC);
3-(N,N,N-trimethyl: ) propyl sodium4 ~l ~r yl ~aliJuAyla
and
N,N,N-trimethyl ammonium toluyloxy benzene sulphonate.
Other activators include sodium-4-benzoyloxy benzene sulphonate;
N,N,N',N'-tetracetyl ethylene diamine; sodium-l-methyl-2-benzoyloxy benzene-4-
sulphonate; 50~ 1 'YI-3-~ UYIUAY benzoate; sodium nonanoyluAy~
sulphonate; sodium 3,5,5,-trimethyl h~AGl~ loAyl/~ e sulphonate; glucose
~ and tetraacetyl xylose.
Bleach activators of also useful in the present invention are amide substituted
compounds of the general formulas:
O O O O
Il 11 11 11
R1~C--N--R2-C--L, R1--N--C--R2-C--L
Rs Rs
or mixtures thereof, wherein Rl is an alkyl, aryl, or alkaryl group containing îrom
25 about I to about 14 carbon atoms, R2 ;5 an alkylene, arylene or alkarylene group
contairiing from about I to about 14 carbon atoms, R5 is H or an alkyl, aryl, oraikaryl group containing from about I to about 10 carbon atoms, and L can be
essentiaily any suitable leaving group. A leaving group is any group that is
displaced i-rom the bleaching activator as a rnnCPqllpn~e of the l~ attack
30 on the bleach activator by the p~" IIJ ~ii uAide anion. This, the p.,. Ilyiil ul,~;a reaction,
results in the formation of the p~uAyuGlbuA~lh, acid. Generally, for a group to be
a suitable leaving group it must exert an electron attracting effect. It should also
fomm a stable entity so that the rate of the back reaction is negligible. This
faci~iitates the ., .~ attack by the ~ lUAi~i., anion.
wo ss/2777s ~ 6 9 ~ P ~ A ~ ~
The L group must be sufficiently reactive for the reaction to occur within the
optimum time frame (e.g., a wash cycle). However, if L is too reactive, this
activator will be difficult to stabilize for use in a bleaching ~ 9~ These
,L~ L;.,~ are generally paralleled by the pKa of the conjugate acid of the
5 leaving group, although exceptions to this convention are known. Ordinarily,
leaving groups that exhibit such behavior are those in which their conjugate acid
has a pKa in the range of from about 4 to about 13, preferably from about 6 to
about 11 and most preferably from about 8 to about l l.
Preferred bleach activators are those of the above general formula wherein
10 Rl, R2 and R5 are as defned for the peroxyacid and L is selected from the group
consisting of:
--o~, --O~Y, and --0~5
--N--C--R1 --N N 1l
R3. Y
-O-CH=C--CH=CH2 --O--CH=C--CH=CH2
-O--C--R1 _N~ NR4 , ~C~NR4
O O
R3 Y
--O--C=CHR4 , and O
and mixtures thereof, wherein Rl is an alkyl, aryl, or alkaryl group containing from
about I to about 14 carbon atoms, R3 is an alkyl chain containing from I to about
8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group.
The preferred solubilizing groups are -SO3-M , -CO2-M+, -SO4-M+,
20 -N (R3)4X- and O<--N(R3)3 and most preferably -SO3-M and -CO2-M
, t ~ .
wo ss/2777s ~ ~ ~ 7 ~ ~ g I ~ l, u~ sir~ -
wherein R3 is an alkyl chain containing from about I to about 4 carbon atoms, M is
a cation which provides solubility to the bleach acti~ator and X is an anion which
provides solubLiity to the bleach activator. Preferably, M is an aikali metal,
ammonium or substituted ammonium cation, with sodium and potassium being
5 most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion. It
should be noted that bleach activators with a leaving group that does not contain a
solubilizing groups should be well dispersed in the bleaching solution in order to
assist in their dissolution.
Preferred bleach activators are those of the above generai formula wherein L
10 is selected from the group consisting of:
~ O~Y , and --0~
wherein R3 is as defined above and Y is -SO3 M or -CO2 M wherein M is as
defined above.
Preferred examples of bleach activators of the above formulae include (6-
, U~ Ay~ , (6--~ r.~ U;¦)UAy~ ~r
nate, (6-~ . uyl)u~yb. ~1 r , and mixtures thereof.
Another important class of bleach activators provide organic peracids as
described herein by ring-opening as a c.,... 1 ~ ~ of the, ~ pi.il ~ attack on the
carbonyl carbon of the cyclic ring by the perhydroxide anion. For instance, thisring-opening reaction in certain activators involves attack at the lactam ring
carbonyl by hydro~en peroxide or its anion. Since attack of an acyl lactam by
hydrogen peroxide or its anion occurs preferably at the exocyclic carbonyl,
obtairling a significant fraction of ring-opening may require a catalyst. Another
example of ring-opening bleach activators can be found in other activators, such as
those disclosed in U.S. Patent 4,966,723, Hodge et al, issued Oct. 30, 1990.
Such activator ro~rol~n~i~ disclosed by Hodge include the activators of the
type, having the formula:
o
~N~8 R1
including the substituted 1,.. ,... A~ ~ of the type
W0 95/27775 ,~
2~8rt~6g '~2 ~--
R2
R4J~ ;
wherein Rl is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4, and R5may be the same or different ~ selected from H, halogen, alkyl, alkenyl,
aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR6 (wherein R6 iS H or an alkyl
S group) and carbonyl functions.
A preferred activator of the benzoxazin-type is:
1l
"C~
When the activators are used, optimum surface bleaching p~,.rOI is
obtained with washing solutions wherein the pH of such solution is between about8.5 and 10.5 and preferably between 9.5 and 10.5 in order to facilitate the
~ hJd~ul~ reaction. Such pH can be obtained with substances commonly
known as buffering agents, which are optional cu,l.r of the bleaching
systems herein.
Still another class of preferred bleach activators includes the acyl lactam5 activators, especially acyl ~,~"" ul,,~l,.ll.~ and acyl valerolactams of the formulae:
O O
O C--CH2--CH2 O C--CH2--CH2
R6--C--N CH R6--C--N
`CH2--CH2~ 2 `CH2--CH2
wherein R6 ;5 H, an alkyl, aryl, alkoxyaryl, or alkaryl group containing from I to
about 12 carbon atoms, or a substituted phenyl group containjng from about 6 to
about 18 carbons. See also U.S. Patent 4,545,784, issued to Sanderson, October 8,
20 1985, il~cul~ led herein by reference, which discloses acyl L~ luk.cL~ s, including
benzoyl ~ ' , adsorbed into sodium perborate.
Various nonlimiting examples of additional activators which may comprise
the bleach ~....1,,,~:l;.,..~ disclosed herein include those in U.S. Patent 4,915,854,
issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934. The
~ ,.~.".c sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED)
wossl2777s ~ 9 `; `~ P~l/u~
13
activators are typical, and mixtures thereof can also be used. See also U.S.
4,634,551 for other typical bleaches and .activators useful herein.
The superior blc~luu~l.,D~ullg action of the present ~ is also
preferably achieved with safety to natural rubber machine parts and other natural
S rubber articles, including fabrics Cu..h;lu~ .,f Lul~l rubber and natural rubber elastic
materials. The bleaching mechanism and, in particular, the surface bleaching
mechanism are not completely understûod However, it is generally believed that
the bleach activator undergoes, ' . ' ' attack by a I~.l.rJ~u~dc anion, which
is generated from the hydrogen peroxide evolved by the peroxygen bleach, to formlû a p~.u~.,~ul.u~.~lh, acid. This reaction is commonly referred to as perhydrolysis.
The amido-derived and lactam bleach activators herein can also be used in
' with preferably rubber-safe, enzyme-safe, hydrophilic activators such
as TAED, typically at weight ratios of amido-derived or .,~
activators:TAED in the range of 1:5 to 5:1, preferably about 1:1.
15 R ~tinc Of (~, ~
For purposes of the present invention, it is important to control the molar
ratio of hydrogen peroxide to peracids (preformed or from bleach activators) is less
than about 4:1 and preferably is within a specified limit, in order to obtain the desired
reduction in fabric damage from the metal-containing bleach catalyst. It is further
20 preferred that the molar ratio of hydrogen peroxide to heavy metal ions from the
bleach catalyst be controlled.
The molar ratio of hydrogen peroxide to peracid is defined herein to be the
molar ~,n~ of hydrogen peroxide obtained from the bleaching agent that is a
source of hydrogen peroxide ([H202]) to the theoretical molar ,u..~ lalion of
peracids generated by the bleach activator plus any preformed peracid compounds
present in the cv ~ u~ ([Peracid]). For example, one mole of p~,l a.l,u~ , will
provide 1.5 moles of hydrogen peroxide and one mole of perborate viill generate one
mole of hydrogen peroxide; the FI202] from such sources are therefore calculatedbased on these values and the molar Cull~ lliu~ of the bleaching agent that is asource of hydrogen peroxide being used. Similarly, for the bleach activators used in
the f,., .~ u~ the [Peracid] is calculated l~,urlu~ ; that, for example, one mole
of TAED ll.~,u.~ will provide two peracids; thus the [Peracid] is 2 times the
molar ~ . f I ~ of TAED.
The molar ratio of [H202]:1Peracid] is therefore less than about 4:1,
preferably between 1:1 and 3 :1, and most preferably between I .û2: 1 and 2.5 :1.
Also preferred for the present c....~ , when the ~ contain
more than about 20 ppm heavy metal ions sourced by the bleach catalyst (therefore,
, .. . ..... . ..
W0 95127775 ~1 ~ 7 1 ~ 9! ~
14
does not include non-cataiytic heavy metal ions in the rn~rocitir~nc or heavy metal
ions fortuitously present in the wash solution), is controlling the molar ratio of
hydrogen peroxide to heavy metal ions sourced by the bleach catalyst
(i-H202]:[E~]) to be less than about 1200 1.
Aiso preferred is controlling the molar ratio of peracid to heavy metal ions
from the bleach cataiyst (~Peracid]:i~IMI]) to be more than about 350:1, preferably
greater than about 500:1, and most preferably greater than about 700:1. The molar
rl~ IIAI;~I of the heavy metai ions from the bleach catalyst ([HMI]) is obtainedfrom the molar, of the bleach catalyst times the number of heavy metai
ions per catalyst. For example, the preferred catalyst ~inIv2(u-O)3(1,4,7-trimethyl-
1,4,7-~ ,y~lu~u~ e)2-(pF6)2 provides 2 moles of Mn per mole of cataiyst, thus
the i~] for the Mn sourced by this catalyst equals 2 times the molar
of the cataiyst.
Finaiiy, it is further preferred for the present invention that ~
comprise less than about 50 ppm of heavy metai ions sourced by the catalyst, andmost preferably iess than about 40 ppm.
Adjunct In~rPrliPntc
The ~ :l;,. - herein can optionally include one or more other detergent
adjunct materials or other materials for assisting or enhancing cleaning p~,.ru.,....,,~.c,
20 treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent
(e.g., perfumes, colorants, dyes, etc.). Preferably, the adjunct
ingredients should have good stability with the bleaches employed herein. Preferably,
the detergent ~ ;"--- herein should be boron-free and phosphate-free.
Additionaily, dishcare f( ' are preferably chlorine-free. The following are
25 iiiustrative examples of such adjunct materials.
Free Radical r~r~ven~ing Antioxidant Iviaterials:
"Free radicai scaYenging antioxidant materials", as used herein, means those
materiais which act to prevent oxidation in products by functioning as free radical
scavengers. Examples of A..l;.,~ that can be added to the ur~ of this
30 invention include a mixture of ascorbic acid, ascorbic palmitate, propyl gallate,
available from Eastman Chemical Products, Inc., under the trade names TenoxR PG
and Tenox S-1; a mixture of BHT (butylated l~y~i~u~yluh~.,.lc), BHA (butylated
h~i-UA~ ~ ), propyl gailate, and citric acid, available from Eastman Chemical
Products, Inc., under the trade name Tenox-6; butylated hydlu~y~ulu.,.~." available
35 from UOP Process Division under the trade name SustaneR BHT; tertiary
L~ , e, Eastman Chemical Products, Inc., as Tenox TBHQ; natural
~o,,oph~,.uls, Eastman Chemicai Products, Inc., as Tenox GT-1/GT-2; and butylated
wO 95/2777~ 6 ~3 ~ ` ~ ` . IIU~,SlO~ .
h~ u~. -'e, Eastman Chemical Products, Inc., as BHA; long chain esterS (C8-
C22) of gallic 2cid, e.g., dodecyl gallate; lrganoxR 1010; IrganoxR 1035; IrganoxR
B 1171; IrganoxR 1425; IrganoxR 3114; IrganoxR 3125; mono-tert-butyl
hr~ ~ (MTBHQ); benzoic acid and salts thereof; toluic acids and salts
5 thereof; t-butyl catechol; l, I ,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl) butane
(Topanol CA available from ICI); monoalkyl ethers of Iydl~, ~ (e.g., 4-
' ~, ' '); and mixtures thereof.
Preferred are BHT, BHA, TBHQ, propyl gallate, ascorbic acid, and mixtures
thereo
It is to be recognized that for purposes of the present invention, materiais
othervvise useful as ' which do not act as free radical scavengers, such as
those materials which function solely by chelating metais which can initiate oxidation
reactions are not "free radical scavenging antioxidant materials" herein, but are
preferred optional material to be used with the free radical scavenging antioxidant
materiais.
The term " ' effective amount", as used herein, means an amount of
a free radical scavenging antioxidant material effective for reducing, under whatever
~,u~ alaliv~ test conditions are employed, the extent of any fabric damage (including,
for example, tensile strength loss and/or color damage) observed by the presence of
the metal-containing bleach catalyst in the l_UllllJV~ iUII. Such fabric damage may be
evaluated under any typical wash conditions, including the greater than 40 C wash
conditions common in Eurûpe. Levels of free radical scavenging antioxidant
materiais to be used in products are therefore easily ~f t~rrnin~i and are typicaily
present in the ~ , according to the present invention within the range of
from about I ppm to about 2%, preferably from about 20 ppm to about 6000 ppm,
and most preferably from about 50 ppm to about 2000ppm. Further, in a powder
~ ' , the antioxidant may be introduced into the ~ - as a powder or
through d~ oln~aliull or granulation or any other process to keep the catdlyst and
dntioxidant close to each other and thereby allow quick interaction in the wash.
Buiiders - Detergent buiiders can optionally be included in the ~ ;n..c
herein to assist in controlling mineral hardness. Inorganic as well as organic builders
can be used. Builders are typically used in fabric laundering ~ .o~ to assist in the removal of particulate soils.
The level of builder can vary widely depending upon the end use of the
.,., 1 1 o~ and its desired physical forrn When present, the ~ulllpoa;iiolls will
typically comprise at least about 1% builder. Liquid rullllul~Liul~a typically comprise
... . . .
_ _ ... .. . .
woss/2777~ 218~69 ~ P ~
from about 5% to about 50%, more typically about 5% to about 30%, by weight, of
detergent builder. Granular ~ "~ typically comprise from about 10% to
about 80%, more typically from about 15% to about 50% by weight, of the deter8ent
builder. Lower or higher levels of builder, however, are not meant to be excluded.
Examples of silicate builders are the alkali metal silicates, particularly thosehaving a SiO2:Na2O ratio in the range 1.6:1 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 H. P. Rieck. NaSKS-6 is the trademark for a crystalline layered silicate marketed
by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the
Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-
Na2SiOs lllul~ lu~ form of Isyered 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 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 delta-Na2SiOs (NaSKS-6 form) is most preferred for use herein. Other
silicates may also be useful such as for example magnesium silicate, which can serve
as a crispening agent in granular ru~ ulaLiull~, as a stabilizing agent for oxygen
bleaches, and as a component of suds control systems.
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates as disclosed in German Patent Application No. 2,321,001 published on
November 15, 1973.
~l ' builders are useful in the present invention. ~l "
builders are of great importance in most currently marketed heavy duty granular
detergent ~ , and can also be a significant builder ingredient in liquid
detergent 1;- -~ - - ' builders include those having the empirical
forrnula:
Mz(zAlO2)y] xH2O
wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from
1.0 to about 0.5, and x is an integer from about 15 to about 264.
Useful ' " ion exchange materials are cu"",.~, "y available.
These ' ' can be crystalline or amorphous in structure and can be
naturally-occurring ~ ' - ' or synthetically derived. A method for
producing ' ' ion exchange materials is disclosed in U.S. Patent
3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline
WO9~J27775 ~ 9 ` P~ JJI~71
17
' " ion exchange materials useful herein are available under the
A~ :;c,r~ Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especialiy
preferred el,.l,u ' t, the crystailine ' - ' ion exchange material has the
formula:
Nal2[(Alo2)l2(sio2)l2] xH2o
wherein x is from about 20 to about 30, especially about 27. This material is known
as Zeûlite A. Dehydrated zeoiites (x = 0 - 10) may also be used herein. Preferably,
the l ' ' 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 variety of pGly.~ uAyl~ v~ As
used herein, "l~ul~ GAy6~" refers to compounds having a plurality of ~ bUA.~h. ~,
groups, preferably at least 3 c.llbùA~ld~ . PulyL~liJuAyLIle builder can generally be
added to the ~ u~ in acid form, but can also be added in the form of a
neutralized sait. When utilized in salt form, alkali metals, such as sodium, potassium,
and iithium, or " ' salts are preferred.
Included among the pc~ uiJuAyL~ builders are a variety of categories of
useful materiais. One important category of ~.,lJ~IbuAyl~Le builders; n~
the ether pGl~ uAjk~, including UAr; :, as disclosed in Berg, U.S.
Patent 3,128,287, issued April 7, 1964, and Lamberti et ai, U.S. Patent 3,635,830,
issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,û71,
issued to Bush.et al, on May 5, 1987. Suitable ether pOly..,ll,uArl.lLcs aiso include
cyciic . . ', particularly alicyclic .u...,. 's, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Citrate builders, e.g., citric acid and soluble salts thereof ~particularly sodium
sait), are ~ul.~ iJuAy' builders of particular importance for detergent ru~ lllul.Lu~s
due to their availability from renewable resources and their l);1~1F~ .'l' y, Citrates
. can be used in liquids or in granular ~ ., especially in ~ with
aeolite and/or layered silicate builders. Ar~ are also especially useful in
such c~ and ~
Fatty acids, e.g., C12-CIg ll~ollûL~l~uA.ylic acids, can also be ~u~dl~d
into the ~ aione, or in ~.u~ with the aforesaid builders, especially
citrate and/or the succinate builders, to provide additional buiider activity. Such use
of fatty acids will generally result in a diminution of sudsing, which should be taken
into account by the formulator.
In situations where pllu~ lu~-based builders can be used, and especially in
the r.., . ,~ of bars used for hand-laundering operations, the vanous alkali metal
.. . ... ... . . . .
WO95/27775 2~8~ 18
phosphates such as the well-known sodium L. ;IJùly~ n~ , sodium 1..~.~ . ' . '
and sodium U~ PI '`1~ can be used.
('hPl~ino A ~o~ntc - Although builders can be used. the detergent ~,.J~
herein preferably do not contain those manganese chelating agents which abstract the
5 manganese from the bleach catalyst cpmplex. In particular, I,I..~l,I,n ~ ,,
l ' , ' , and the ~r' . ' chelating agents such as DEQUEST are
preferably not used in the .,u ~l.ù,;l;....~ However, nitrogen-based manganese
chelating agents, such as ~ J' ' N,N'-disuccinate (EDDS), are useful.
Detersive Surfactants - ~ ' ~ examples of surfactants useful herein
10 typically at levels from about 1% to about 55%, by weight, include the Cv.l._l.L;ù..~l
Cll-CIg alkyl benzene sulfonates ("LAS") and primary, branched-chain and random
Clo-C20 alkyl sulfates ("ASn), the Clo-CIg secondary (2,3) alkyl sulfates of theformula CH3(CH2)X(CHOSO3-M+)CH3 and CH3(CH2)y(CHOS03~M+) CH2CH3
where x and (y + I) are integers of at least about 7, preferably at least about 9, and
15 M is a water-solubilizing cation, especially sodium7 ....~ 1 sulfates such as oleyl
sulfate, the Clo-CIg alkyl alkoxy sulfates ("AExS"; especially EO 1-7 ethoxy
subfates), Clo-CIg alkyl alkoxy ~ buAyLIle~ (especially the EO 1-5
~ UA~ IJUAYL~S)~ the ClO I8 glycerol ethers, the CIO CI8 alkyl pvl~dl~,u~id~,,.
and their ~ulle~ul~d;~lg sulfated poly~ .,u~;d~,~, and C12-CIg alpha-sulfûnated fatty
20 acid esters. If desired, the ~u...~iiun~l nonionic and amphoteric surfactants such as
the C12-CIg alkyl ethoxylates ("AE") including the so-called narrow peaked alkylethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed
~LIIUA~I~JIUYUAY), C12-CIg betaines and c~lfobPt~inps ("sultaines"), CI0 CI8 amine
oxides, and the like, can also be included in the overall ~,....l..~:l;.- ~ The C10-C18
25 N-alkyl pGl~ UA~ fatty acid amides can also be used. Typical c-Aamples include
the C12-C18 N-~ h~'~' ' See WO 9,206,154. Other sugar-derived
surfactants include the N-alkoxy polyhyd,uAy fatty acid amides, such as Clo-CIg N-
(3 ' ~IU~I) glucamide. The N-propyl through N-hexyl Cl2-CI8 glucamides
can be used for low sudsing. Cl o-c20 conventional soaps may also be used. If high
30 sudsing is desired, the branched-chain Clo-cl6 sûaps may be used. Mixtures ofanionic and nonionic surfactants are especially useful. Other cu,.~ ..iu,.~l useful
surfactants are listed in standard texts.
Suitable nonionic surfactants particularly suitable for dishcare are the low-
foaming or non-foaming ethoxylated straight-chain alcohûls such as PlurafacTM RA35 series, supplied by Eurane Co., LutensolTM LF series, supplied by BASF Co.,
TritonTM DF series, supplied by Rohm & Haas Co., and SynperonicTM LF series,
supplied by ICI Cû.
wo gsl27775
Clav sOa RemovaVAnti-lcd~ o~ ull Aoents - The ~ , of the
present invention ean aiso optionally. contain water-soluble ethoxylated amines
having elay soil re--moval and ~ , properties. Granular detergent
which eontain these romrolln~ic typically contain from about 0.01% to
5 about 10.0% by weight of the water-soluble ethoxylates amines; liquid detergent
c-- I-c~ typieaiiy eontain about 0.01% to about 5%.
The most preferred soil release and anti--r~ agent is ethoxylated
tLt~ LI~I r~ ' ' Exemplary ethoxylated amines are further deseribed in U.S.
Patent 4,597,898, VailLi.l~i`.., issued July 1, 1986. Another group of preferred elay
10 soii removal-ài,Li,e i~ua;~iu,, agents are the cationic ~r~mrol.n~ic disclosed in
European Patent Application 111,965, Oh and Gosselink, published June 27, 1984.
Other elay soil ICI~IUV ~ tilCi~iL,jJU~ iUII agents whieh ean be used inelude the
ethoxylated amine polymers disclosed in European Patent Application 111,984,
Gosselink, published June 27, 1984; the ~;.LLI;OIUC polymers disclosed in ~uropean
Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides
disclosed in U.S. Patent 4,548,744, CoMOr, issued October 22, 1985. Other clay
soil removai and/or anti .ed~uiiLio" agents known in the art can aiso be utilized in
the, . ~ herein. Another type of preferred ~L.l.ilrri ~ ... agent includes
the carboxy methyl cellulose (CMC) materials. These materials are well icnown in20 the art.
Polvmeric l~ic~nprcin~ A~ents - polymeric dispersing agents can
a i.. _ '~/ be utiiized at levels from about 0.1% to about 7%, by weight, in ther~-lF- herein, especially in the presence of zeolite and/or layered silicate
builders. Suitable polymeric dispersing agents include polymeric p
and pGI~ Li~!L~lL glycols, although others known in the art can also be used. it is
beiieved, though it is not intended to be limited by theory, that poly--m-eric dispersing
agents eMance overall detergent builder p.,.ru~ allLe, when used in ~.r~
with other buiiders (including lower molecular weight j'JUI~iliJU~l~LLL.~) by crystal
growthiMibition,particulatesoilreleasepPrti7~tirn, andanti-,ei~,.u~:l;.~
Polyrneric ~ul~ bu~.yld~ materials can be prepared by pLJlyll~ iLillg or
Cu~jJU~ , suitable I _ ' monomers, preferably in their acid form.
- TT ' monomeric acids that can be pcl~.. ,.. ,i~.;i to form suitable polymeric
pUIyLaibU~ ' include acrylic acid, maleic acid (or maleie anhydride), fumaric aeid,
itaeonie aeid, aeonitic aeid, mesaconic acid, citraconic acid and lil.~l.y~. .~. ~,.. :
35 acid. The presence in the polymei-ic pOl,yLal bù~ LI:a herein or monomeric segments,
containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is
, .. . .... . ... .. . .. . _ .
wossl2777s ~ ~711ig ~ ,1IL..,~'^'~ ~
suitable provided that such segments do not constitute more than about 40% by
weight.
Particularly suitable polymeric puly~ bu~ can be derived from acrylic
acid. Such acrylic acid-based polymers which are useful herein are the water-soluble
5 saits of pul~....,.i~ acrylic acid. The average molecular weight of such polymers in
the acid form preferably ranges from about 2,00û to 10,000, more preferably fromabout 4,000 to 7,000 and most preferably from about 4,000 to 5,00û Water-solublesaits of such acrylic acid polymers can include, for example, the aikali metal,
ammonium and substituted ammonium salts. Soluble polymers of this type are
10 known materiais. Use of POI~ G;~ of this type in detergent ~ J~ has
been disclosed, for example, in Diehi, U.S. Patent 3,308,067, issued march 7, 1967.
A~,lyl;~/ ' -based copolymers may also be used as a preferred component
of the ~ c~ u~;l;ull agent. Such materials include the water-soluble
saits of copolymers of acrylic acid and maleic acid. The average molecular weight of
such copolymers in the acid form preferably ranges from about 2,000 to 100,000,
more preferably from about 5,000 to 75,000, most 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 about 1:1, more preferably from about 10:1 to 2:1. Water-
soluble saits of such acrylic acid/maleic acid copolymers can inciude, for example, the
20 aikaii metal, ammonium and substituted ammonium saits. Soluble a~,~' ! '
copolymers ofthis type are icnown materials which are described in European Patent
Application No. 66915, published December 15, 1982.
Another polymeric materiai which can be included is polyethylene glycol
(PEG). PEG can exhibit dispersing agent i,~,ru,."~l"..c as weii as act as a clay soil
removai-a.,~ilt i~p~ ;u" agent. Typical molecular weight ranges for these purposes
range from about 500 to about 100,00~, preferably from about 1,000 to about
50,000, more preferably from about 1,500 to about 10,000.
rul~ ui and pGI~,,' ' ' dispersing agents may also be used,
especially in conjunction with zeolite builders. Dispersing agents such as
pc,l~ preferably have a molecular weight (avg.) of about 10,000.
Enzvmes - Enzymes can be included in the r~ herein for a wide
variety of fabric laundering purposes, including removal of protein-based,
.,~bu~ Llc-based, or ~ ,;d. -based stains, for example, and for the prevention
of refugee dye transfer, and for fabric restoration The enzymes to be il~cullJO.~led
include proteases, amylases, lipases, cellulases, and ~J."u~i~Lls~, as well as mixtures
thereo Other types of enzymes may also be included. They may be of any suitableorigin, such as vegetable, animal, bacterial, 1ngai and yeast origin. However, their
_ . . _ . _ . _ _
~ woss/27775 ,~7~f~9
21
choice is governed by several factors such as pH-activity and/or stability optima,
ib ' ' ~, stability versus active detergents, builders and so on. In this respect
bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases,
and fungal cellulases.
5 Enzymes are normally il.. ,ù.po.dLed at levels sufficient to provide up to about
5 mg by weight, more typically about 0.01 mg to about 3 mg, of active en2yme pergram of the ~ .. Stated otherwise, the "r. ~ ;...,c herein will typically
comprise from about 0.001% to about 5%, preferably 0.01%-1% by weight of a
commercial enzyme preparation. Protease enzymes are usually present in such
10 commercial l~lC,Ud~dLiU.... at leve]s sufficient to provide from 0.005 to 0.1 Anson urlits
(AU) of activity per gram of ~ ;rn~
Suitable examples of proteases are the subtilisins which are obtained from
particular strains of B. subtilis and B. l,. l.. ,;~.., ~ Another suitable protease is
obtaincd from a strain of Bacillus, having maximum activity throughout the pH range
15 of 8-12, developed and sold by Novo Industries A/S under the registered trade name
ESPERASE. The preparation of this enzyme and analogous enymes is described in
British Patent Sp~rifir~ n No. 1,243 ,784 of Novo. Proteolytic enzymes suitable for
removing protein-based stains that are ~,~.,..,~., "y available include those sold
under the tradenames ALCALASE and SAVINASE by Novo Industries AtS
(Denmark) and MAXATASE by IllLel~ u~ldl Bio-Syn'thetics, Inc (The
N ' ~ ~ ). Other proteases include Protease A (see European Patent Application
130,756, published ~anuary 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).
Amylases include, for example, o-amylases described in British Patent
S~ t;.... No. 1,296,839 (Novo), RAPIDASE, I..L~ , L;o..,,l Bio-Synthetics, Inc.
and TERMA~L, Novo Industries.
The cellulase usable in the present invention include both bacterial or fungal
cellulase. Preferably, they will have a pH optimum of between 5 and 9.5.
Suitable lipase enzymes for detergent usage include those produced by
....-uulL of the r~ ~ g~oup, such as r~v lu~ c stutzeri ATCC
19.154, as disclosed in British Patent 1,372,034. See also lipases in Japanese Patent
Application 53,20487, laid open to public inspection on February 24, 1978. This
- lipase is available from Amano rl.,,.,.,,~ L;.,dl Co. Ltd., Nagoya, Japan, under the
trade name Lipase P "Amano," hereinafter referred to as "Amano-P." Other
commercial lipases include Amano-CES, lipases ex Cl"u.l.ul,~ - viscosum, e.g.
Chromobacter viscosum var. Iipolyticum NRRLB 3673, Cul}~ ,y available from
, , , , , ., . .. . _ , .. . ., . _ . _ _ , _
wo gs/27775 2 1 8 7 1 6 ~1 22 P
Toyo Jozo Co., Tagata, Japan; and further Cluu~ub~ el viscosum lipases from U.S.Fn~ Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex
r ~ ~adioli. The LIPOLASE enzyme derived from Humicola lanuginosa
and , ".~, available from Novo (see also EPO 341,947) is a preferred lipase
5 for use herein.
Peroxidase enzymes are used in .~...,1, ~;.,.. with oxygen sources, e.g.,
p~ ,al~ , perborate, persulfate, hydrogen peroxide, etc. They are used for
"solution bleaching," i.e. to prevent transfer of dyes or pigments removed from
substrates during wash operations to other substrates in the wash solution.
10 Peroxidase enzymes are known in the art, and include, for example, horseradish
peroxidase, ligninase, and llâlu~ uAidà~e such as chloro- and bromo-peroxidase.
Peroxidase-containing detergent ~ c;~ are disclosed, for example, in PCT
l,.t~ --'1 Application WO 89/099813, published October 19, 1989, by O. Kirk,
assigned to Novo Industries AIS.
A wide range of enzyme materials and means for their ;.. ~,ul~Ju,~liu.~ into
synthetic detergent ~ :l;u -- are also disclosed in U.S Patent 3,553,139, issuedJanuary 5, 1971 to McCarty et al Enzymes are fiurther disclosed in U.S. Patent
4,101,457, Place et al, issued July 18, 1978, and in U.S. Patent 4,5û7,219, Hughes,
issued March 26, 1985, both. Enzyme materials usefiul for liquid detergent
r.. ~ and their I,u,.. liu.. into such ru~ ulaL;ull~, are disclosed in U S.
Patent 4,261,868, Hora et al, issued April 14, 1981 Enzymes for use in detergents
can be stabilized by various techniques Enzyme ~ ' - 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. 8~7no586 ~, published October 29, 1986, Venegas. Enzyme
' ' systems are also described, for example, in U.S. Patent 3,519,570.
Enzvme Stabilizers - The enzymes employed herein may be stabilized by the
presence of water-soluble sources of calcium and/or magnesium ions in the finished
which provide such iûns to the enzymes. (Calcium ions are generally
somewhat more effective than magnesium ions and are preferred herein if only onetype of cation is being used.) Additionâl stability can be provided by the presence of
various other art-disclosed stabilizers, especially borate species: see Severson, U.S.
4,537,706. Typical detergents, especially liquids, will comprise from about I toabout 30, preferably from about 2 to about 20, more preferably from about 5 to
about 15, and most preferably from about 8 tû about 12, millimoles of calcium ion
per liter of finished ~ .., This can vary somewhat, depending on the amount
of enzyme present and its response to the calcium or magnesium ions. The level of
wo ss~2777~ 2 ~ ~ 7 1 ~9 23 - ~
calcium or magnesium ions should be selected so that there is always some minimum
level available for the enzyme, aAer allowing for ~..,,..i,!..~l;~., with builders, fatty
acids, ete., in the ~ ) Any water-soluble calcium or magnesium salt can be
used as the source of calcium or magnesium ions, including, but not limited to,
5 calcium chloride, calcium sulfate, caleium malate, calcium maleate, calcium
hydroxide, ealcium formate, and calcium acetate, and the cu..c~.ùl.l;.,~ magnesium
salts. A smaD amount ûf calcium ion, generally from about û.û5 to about 0.4
miDimoles per liter, is oAen also present in the c~ Q- l;r~A due to calcium in the
enzyme slurry and formula water. In solid detergent . , - the lù.~..uL.lio~l
may include a suffieient quantity of a water-soluble calcium ion source to provide
such amounts in the laundry liquor. In the alternative, natural water hardness may
sufiice.
It is to be understood that the foregoing levels of caleium and/or magnesium
ions are sufficient to provide enzyme stability. More calcium and/or magnesium ions
can be added to the ~ to provide an additional measure of grease removal
~. ~ Aeeordingly, as a general proposition the .,. .~ - herein will
typicaDy eomprise from about 0.05% to about 2% by weight of a water-soluble
source of caleium or magnesium ions, or both. The amount can vary, of course, with
the amount and type of enyme employed in the ~ ~p~
The r -- herein may also optionally, but preferably, contain various
additional stabilizers, especially borate-type stabilizers. Typically, such stabilizers
will be used at levels in the ~ ..c from about 0.25% to about 10%, 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 eompound capable of forming boric acid in the
, , - (calculated on the basis of boric acid). Boric acid is preferred, althoughothet ~ , ' such as boric oxide, borax and other alkali metal borates (e.g.,
sodium ortho-, meta- and pyroborate, and sodium ~ r) are suitable.
Substituted boric acids (e.g.,, ' rlbolu"h acid, butane boronic acid, and p-bromo
pl~ bu~u~u~, acid) can also be used in place of boric acid.
~gh~ - Any optical brighteners or other brightening or whitening agents
known in the art can be ;II~,UIIJUl~ d at levels typically from about 0.05% to about
- 1.2%, by weight, into the detergent c.. ~ herein. Commercial optical
brighteners which may be useful in the present invention can be classified into
- subgroups, which include, but are not necessarily limited to, derivatives of stilbene,
35 pyrazoline, coumarin, carboxylic acid, I".,;h;...,.,~.,.f"l.,~, ' l ', ' ~-5,5-dioxide,
azoles, 5- and 6-membered-ring ll~ u~ , and other 1~ llc agents.
Examples of such brighteners are disclosed in "The Production and Application of
, , ,, ,, . . . . _ .. .. . . . . .
wo 95/27775 2187 ~ ~ 9 24 ~ 7 ' -
Fluorescent ~righ~l~nin~ Agents", M. Zahradnik, Published by John Wiley & Sons,
New York (1982).
Specific examples of opticai brighteners which are useful in the present
c.. ~ are those identified in U.S. Patent 4,790,856, issued to Wixon on
S December 13, 1988. These brighteners include the PHORWHITE series of
brighteners from Verona. Other brighteners disclosed in this reference include:
Tinopai UiiPA, Tinopai CBS and Tinopal SBM; available from Ciba-Geigy; Artic
White CC and Artic White CWD, available from Hilton-Davis, located in Italy; the 2-
(4-stryi-phenyl)-2H-napthol[1,2-d]triazoles; 4,4'-bis- (1,2,3-triazol-2-yl)-stilbenes;
4,4'-bis(stryl)bisphenyls; and the ~ -cu~ Specific examples of these
brighteners include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(.- ~ -2-
yl)ethylene; 1,3-diphenyl-,' " 2,5-bis(bexazol-2-yl)thiophene; 2-stryl-
napth-[1,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho- [1,2-d]tria_ole. See aiso
U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton. Anionic brightenersare preferred herein.
~--Ac Suppressors - Cnn~rollnr c for reducing or su~",-c~ the formation of
suds can be i~l~,ul~Jula~e~i into the , of the present invention. Suds
DU~ ~ J~ can be of particular importance in the so-called "high,
cleaning process" and in front-loading E.ll r ~ style washing machines.
2û A wide variety of materials may be used as suds ~u~ vl~, and suds
~u~y.c:.~ul~ are well known to those skilled in the art. See, for example, Kirk
Othmer ~ y~ - of Chemical Technology, Third Edition, Volume 7, pages 430-
447 (John ~ley & Sons, Inc., 1979). One category of suds suppressor of particular
interest c ~ JAyliC fatty acid and soluble salts therein. See U.S.
Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The
~!k, fatty acids and salts thereof used as suds suppressor typicaily have
il~J.U~ l chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon
atoms. Suitable saits include the alkali metal salts such as sodium, potassium, and
iithiumsaits, and ammonium and " ' salts.
The detergent ~.~. l.. ~; ;.. ~ herein may also contain non-surfactant suds~U~,~..,~Vl~. These include, for example: high molecular weight lly~ilu~ liJull~ such
as paraffin, fatty acid esters (e.g., fatty acid ~ .cl;d~ ), fatty acid esters of
v ' aicohols, aliphatic Clg-C40 ketones (e.g., stearone), etc. Other suds
inhibitors include N-alkylated amino triazines such as tri- to hexa-~ yll...,la..~i...,s or
35 di- to tetra . " yl~ ll...lG ~,I iu. formed as products of cyanuric chioride with
two or three moles of a primary or secondary amine containing I to 24 carbon atoms,
propylene oxide, and l..vllostG~.yl phosphates such as lllvllù~è~llyl alcohol phosphate
. ., ,! ' . .!
W095127775 ~71 ~9 ~ _~11....~1P7
ester and ~I di-alkali metai (e.g., K, Na, and Li) phosphates and phosphate
esters. The h~ ùcallJvll~ such as paraffin and I ~ald~ l can be utilized in liquid
form. The liquid IIJJlu~,al~ will be liquid at room ttllly~"dLulc and All...~l/~. .;~,
pressure, and wiii have a pour point in the range of about -40C and about 50CC, and
5 a minimum boiiing point not less than about 110OC (AI~ pressure). It is also
known to utiiize waxy h~ iluuali~ulla, preferably having a melting point below about
lû0C. The ll.~J~u~,aliJu..~ constitute a preferred category of suds suppressor for
detergent ~ .,c 1IrJ~vc~lJoll suds su,u~ avla are described, for example,
in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. The i~ ilvcalbv~10 thus, include aliphatic, aiicyclic, aromatic, and l.~Ltlu~,yl,l;C saturated or,
hyJIul,albu..~ having from about 12 to about 70 carbon atoms. The term "paraffin,"
as used in this suds suppressor discussion, is intended to include mixtures of true
paraffins and cyclic i~J~ilu~,al~
Another preferred category of non-surfactant suds aU,UlJIe:~ùl~ comprises
15 siiicone suds auylJI'e~ a. This category includes the use of pulyu-~,- ,- ~a l ~ - ' oils,
such as p~l~." ' ,' ' , dispersions or emulsions of pvlyul~;r~ - ûils or
resins, and ~ ' of pvlyu,~ --- with silica particles wherein the
pvl,v,~ - l( ~ is ch~ "i,.,d or fused onto the silica. Silicone suds
~Uy~Jlcv~.vlS are well known in the art and are, for example, disclosed in U.S. Patent
4,265,779, issued May 5, 1981 to Gandûlfo et al and European Patent Application
No. 89307851.9, published February 7, 1990, by Starch, M. S.
Other siiicone suds auyyl~,vl~ are disclosed in U.S. Patent 3,455,839 which
relates to ~...,, I .- ~;-,~-c and processes for defoaming aqueous solutions by
~ ,, therein smaii amounts of p~lyd;..l~,lh~' ' - fluids.
Mixtures of silicone and silanated silica are described, for instance, in GermanPatent Application DOS 2,124,526 Silicone defoamers and suds controlling agents
in granular detergent, , f~n~ are disclosed in U.S. Patent 3,933,6?2, Bartolottaet 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 is a suds
30 auyyl~ ~ amount of a suds contrûlling a8ent consisting essentially o
(i) pul.~.' ' ,' ' ~ fluid having a viscosity of from about 20 cs. to
about 1,500 cs. at 25C;
(ii) from about 5 to about 50 parts per 10û parts by weight of (i) of siloxane
resin composed of (CH3)3SiO112 units of SiO2 units in a ratio of from
(CH3)3 SiO112 units and to SiO2 units of from about 0.6:1 to about
1.2:1; and
. .
wo ss/2777s 2 1 ~ 7 1 6 g 26
(iii~ from about I to about 20 parts per 100 parts by weight of (i) of a solid
silica gel.
In the preferred silicone suds suppressor used herein, the solvent for a
continuous phase is made up of certain pG~ . glycols or polyelhylene-
5 pol~,.ul.J!~ e giycol copolymers or mixtures thereof (preferred), or polyl,.u~"l~,.,~,giycol. The primary silicone suds suppressor is branchedU,,Iu~;.lil~c~ and preferably
not linear.
To iDustrate this point further, typical liquid laundry detergent 40.~ ..C I;....
with controlled suds will optionally comprise from about 0.001 to about 1, 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 l~u, ~y ...~ emulsion of a
primary antifoam agent which is a mixture of (a) a pol~v~ ..r, (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)
15 and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3)
p~ "!~,.le giycol or a copolymer of pOI~ -pulJ~Jlu~ , glycol having a
solubility in water at room L~ ,.dlul c: of more than about 2 weight %; and without
PU~ UIJJ!~ giycol. Similar amounts can be used in granular ..J...r~ -., 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,G39,489 and 4,749,740, Aizawa et al at columr. 1, line
46 through column 4, line 35.
The siiicone suds suppressor herein preferably comprises p.,l~lhyl~ , glycol
and a copolymer of PUIJ~Ih~ glycoUpvl~u.u~ , glycol, all having an average
molecular weight of less than about 1,000, preferably between about 100 and 800.The p~l~.,ih~!~,..., glycol and pvl~ J!~ p~ lu~ e copolymers herein have a
solubility in water at room ~ J."alul~ of more than about 2 weight %, preferablymore than about 5 weight %.
The preferred solvent herein is pGI~LI.~!.,"~, glycol having an average
moiecular weight of less than about 1,000, more preferably between about 100 and800, most preferably between 200 and 400, and a copolymer of PUIJ~;IIJI~
giyCoUI,ul~,lulJJ~ c glycol, preferably PPG 2001PEG 300. Preferred is a weight
ratio of between about 1:1 and 1:10, most preferably between 1:3 and 1:6, of
pvl~,h~ glycol:copolymer of pcl~ ,,l.".e-polypropylene glycol.
The preferred silicone suds suppressors used herein do not contain
JIU~JJ~ C glycol, particularly of 4,000 molecular weight. They also preferably
woss/27775 2~ 69 ; ,~
27
do not contain bloek copolymers of ethylene oxide and propylene oxide, like
PLURONIC L101.
Other suds ~u~ ula useful hetein comprise the secondary alcohols (e.g.,
2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones
disclosed in U.S. 4,198,679, 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 ISOFOL 12.
Mixtures of secondary alcohols are available under the trademark ISALCHEM 123
from Enichem. Mixed suds ~u~ ~aul~ typically comprise mixtures of alcohol +
silicone at a weight ratio of 1:5 to 5:1.
For any detergent c~ ;nr~ to be used in automatic laundry washing
machines, suds should not form to the extent that they overfiow the washing
macbine. Suds ~u~ S, when utilized, are preferably present in a Usuds
,.. ,, amount. By "suds ~Up~..l,~S;llg amount" is meant that the formulator of
15 the ~ , can select an amount of this suds controlling agent that will
sufticiently control the suds to result in a low-sudsing laundry detergent for use in
automatic laundry washing machines.
The c~ herein will generally comprise from 0% to about 5% of
suds suppressor. When utilized as suds ~u~ u.~ lul~ llbu~yl;~, fatty acids, and
20 salts therein, will be present typically in amounts up to about 5%, by weight, of the
detergent ~ml~o :1;~ Preferably, from about 0.5% to about 3% of fatty
1JUA.J` suds suppressor is utilized. Silicûne suds ~uy~lc~ùl~ are typiwlly
utilized in amounts up to about 2.0%, by weight, of the detergent c.. ~
although higher amounts may be used. This upper limit is practical in nature, due
25 primarily to concern with keeping costs minimized and c~,L;~ of lower
amounts for effectively controlling sudsing. Preferably from about 0.01% to about
1% of silieone 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
utilized in .u ~ with pOIyul~ Y.- c, as well as any adjunct materials that
30 may be utilized. M~llcia~ yl phosphate suds :~UyUlC~.~Ul~ are generally utilized in
amounts ranging from about 0.1% to about 2%, by weight, of the ~
II~dluwlbu~, suds :iUIJlJlC:~:>Ul:> are typically utilized in amounts ranging from about
0.01% to about 5.0%, although higher levels can be used. The alcohol suds
1~u~ ul ~ are typically used at O.2%-3% by weight of the finished c.~.. .1 ~.~ l ;. . -
Fabric S~ n~s - Various through-the-wash fabric softeners, especially the
impalpable smectite clays of U.S. Patent 4,û62,647, Storm and Nirschl, issued
December 13, 1977, as well as other softener clays known in the art, can optionally
,, . . , ., . , .. . _, . .. . . . . . . . . .
wo ss/2777s 2 ~ 8 rt 1 ~ ~1 28 ~
be used typically at levels offrom about 0.5/0 to about 10% by weight in the present
.. l.. ~:l;.. --- to provide fabric sofiener benefits concurrently with fabric cleaning.
Clay sof~eners can be used in ' with amine and cationic softens as
disclosed, for example, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S.
Patent 4,291,071, Harris et al, issued September 22, 1981.
Dve Transfer Inhibitin~ A~ntc - The ~ 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 U,~ ' ' polymers, polyamine N-oxide10 polymers, copolymers of N .;~ ,., '' ' and N ~ c, manganese
1' ' ' _,. , p.~UAl~aSe~, and mixtures thereof. If used, these agents typically
comprise from about 0.01% to about 10% by weight of the . ~ .", 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
pu~ .iLabl. unit to which an N-O group can be attached or the N-O group can
form part of the POI~ ~abl~ 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, Il~ uc~ . or alicyclic groups or
any . ' ' thereof to which the nitrogen of the N-O group can be attached or
the N-O group is part of these groups. Preferred polyamine N-oxides are those
wherein R is a h.,,elu~ , group such as pyridine, pyrrole, imidazole, pyrrolidine,
piperidine and derivatives thereo
The N-O group can be represented by the following general structures:
1 o
(R~)X--I--(R2)y ; =N--(R~)x
(R3)z
wherein Rl, R2, R3 are aliphatic, aromatic, ..~c.u."y.,l;., or alicyclic groups or
thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be
attached or form part of any of the d['Ul c~ ;u~,d groups. The amine oxide unit of
the polyamine N-oxides has a pKa <10, preferably pKa <7, more preferred pKa <6.
Any 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, polyimides, pul~a~,l~l..`~,., and mixtures thaeof. These polymers include
random or block copolymers where one monomer type is an amine N-oxide and the
i
2777~ g 29 r~"~
other monomer type is an N-oxide. The amine N-oxide polymers typically have a
ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of
amine oxide groups present in the polyamine oxide polymer can be varied by
appropriate cupu~ ..i~liu.. or by an appropriate degree of N-oxidation. The
S polyamine oxides can be obtained in almos~ any degree of polymerization. Typically,
the average molecular weight is within the range of 500 to 1,000,000; more preferred
1,000 to 500,000; most preferred 5,000 to 100,000.
The most preferred polyamine N-oxide useful in the detergent ~.r...~l.,.- l;.,
herein is poly(~ Ih " -N-oxide) which as an average molecular weight of
10 about 50,000 and an amine to amine N-oxide ratio of about 1:4.
Copolymers of N . Jl~oJI~ ~ and N ~ .r' ' ' polymers (referred to
as a class as "PVPVI") are also preferred for use herein. Preferably the PVPVI has
an aversge 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
15 molecular weight range is determined by light scattering as described in Barth, et al.,
Vol 113. "ModernMethodsofPolymer ('h ~ r~ the
disclosures of which are ~ i,u.~ herein by reference ) The PVPVI LUP;)I~
typically have a molar ratio of N-~ to N ~ J.I~ ' ~ ~ from 1:1 to
0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1.20 These copolymers can be either linear or branched.
The present invention ,,.. I.. ,;l;.,.. c also may employ a pGly~ rolidone
("PVP") having an average molecular weight of from about 5,000 to about 400,000,preferably from about 5,000 to about 200,000, 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, ~,u. ~d herein by reference.
C.. ~ -- containing PVP can also contain pGl~.hrl...., glycol (~PEG~) having
an average molecular weight from about 500 to about 100,000, preferably from about
1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered
in wash solutions is from about 2:1 to about 50:1, and more preferably from about
30 3:1 toabout 10:1.
The detergent ~ I.ù~ herein may also optionally contain from about
0.005% to 5% by weight of certain types of hydrophilic optical brighteners whichalso provide a dye transfer inhibition action If used, the ru,..l ~ herein will
preferably comprise from about 0.01% tO 1% by weight of such optical l,. _'
The hydrophilic optical brighteners useful in the present invention are those
having the structural formula:
.. ... .. . . ... . . .. ..
WOg5/27775 ~8 30 p~~ 9r
N~ ~H~ I ~NI ~ON
R2 SO3M SO3M Rl
wherein Rl is selected from anilino, N-2-bis-llyJ.u~.,ll,yl and NH-2-l~yJ.u~.~ .h~l;
R2 is selected from N-2-bi~ JJIu~.,Ll~l, N-2-llyJIu~.Lllyl-N-l~l~.Lh~lallullO~
morphilino, chloro and amino; and M is a salt-forming cation such as sodium or
5 potassium.
When in the above formula, Rl is anilino, R2 is N-2-bis-llyJluA~ ' and M
is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-
llyJ~u~lyl)-s-triazine-2-yl)amino]-2,2'- 'L ~ r ' acid and disodium salt.
This particular brightener species is l~UI~U~ / marketed under the tradename
10 Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred
hydrophilic optical brightener useful in the detergent ~ herein.
When in the above forrnula, Rl is anilino, R2 is N-2.~rJ~u~.~..llyl-N-2-
....,.hJ' ' and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-
(N-2-l-~Jlu~,lllyl-N ' ylc~u~u)-s-triazine-2-yl)amino]Z~2~ ''` acid
15 disodium salt. This particular brightener species is cullull~ ,;allr marketed under the
tradename Tinopal 5BM-GX by Ciba-Geigy Corpûration.
When in the above formula, Rl is anilino, R2 iS morphilino and M is a cation
such as sodium, the brightener is 4,4'-bis[(4-anilino-6-...u.l ~ ~ r triazine-2-yl)amino]2,2'-cti'' ~ - ' "` acid, sodium salt. This particular brightener species is
20 cu~u...,.l,;.~ marketed under the tradename Tinopal AMS-GX by Ciba Geigy
Corporation.
The specific optical brightener species selected for use in the present invention
provide especially effective dye transfer inhibition p.,. f~ benefits when used in
with the selected polymeric dye transfer inhibiting agents l..,lL;.Ib.,f~
25 described. The ~ ' of such selected polymeric 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 s;~;.uL.,zu.ily better dye transfer
inhibition in aqueous wash solutions than does either of these two detergent
"J` I""' fU"'I""' 'I` when used alone. Without being bound by theory, il is
30 believed that such brighteners work this way because they have high affnity for
fabrics 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
~, wogsl2777/C ~8~1fi~ 31
generaA as the ratio of a) the brightener material deposited on fabric to b) the initial
brightener ~ in the wash. Iiquor. 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, CU~ ;OII~AI optical brightener
types of ~ , ' can optionaAly be used in the present r~ u~:l;ù c to provide
cu..~ iol~l fabric "I,liollLl.~,.a" benefits, rather than a true dye transfer inhibiting
effect. Such usage is cu~ tiUll~l and well-known to detergent rul Illul. liulla.Other ~ ntc - A wide variety of other ingredients useful in detergent
lu~ can be included in the ~ , herein, including other active
~, ' , carriers, ~IrJ~u~lu~.~, processing aids, dyes or pigments, solvents for
liquid 1~ ., solid fillers for bar cu~ , etc. If high sudsing is desired,
suds boosters such as the Clo-C16 " ' ~ can be i~l.,u~u~cd into the
V~ , typically at 1%-10% levels. The C10-C14 . .~ ,l and diethanol
amides illustrate a typicaA class of such suds boosters. Use of such suds boosters
with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines
noted above is aAso ad~ LO~,uua. If desired, soluble magnesium salts such as
MgC12, MgSO4, arAd the like, can be added at levels of, typically, 0.1%-2%, to
provide additionaA suds and to enhance grease removal ~, '`
Various detersive ingredients employed in the present ~.,J ~
optionaAly can.be fiurther stabilized by absorbing said ingredients onto a porous
}l~J~u~ u~i~, substrate, then coating said substrate with a ~.~J.u~lllul,ic coating.
Preferably, the detersive ingredient is admixed with a surfactant before being
absorbed into the porous substrate. In use, the detersive ingredient is released from
the substrate into the aqueous washing liquor, where it performs its intended
detersive fiunction.
To illustrate this technique in more detail, a porous llydl~r'~': silica
(trademark S~ERNAT D10, Degussa) is admixed with a proteolytic enzyme
solution containing 3%-5% of C13 1s ethoxylated aAcohol (EO 7) nonionic
30 surfactant. TypicaAly, the ~ u-r~ AL 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 other~vise added to the final detergent matrix. By this
means, ingredients such as the ~ru~c~ Liul~d enzymes, bleaches, bleach activators,
35 bleach catalysts, photoactivators, dyes, fluorescers, fabric ' ~ and
~IyJluly~l~ surfactants can be "protected" for use in detergents, including liquid
laundry detergent ~
... ... _
. _ _ _ _ _ . .. . .. . . .
' ~ _ P ~ r7~-
woss/2777s ~ 6~ 32`
Liquid detergent ~ can contain water and other solvents as
carriers. Low molecular weight primary or secondary aicohols exemplified by
methanol, ethanol, propanol, and i u~lvpGl~ol are suitable Monohydric alcohols are
preferred for solubilizing surfactant, but polyols such as those containing from 2 to
about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-~,v, ' 1,
ethylene glycoi, giycerine, and 1,2~ ' ') can also be used. The ~ o~
may contain from 5% to 90%, typically 10% to 50% of such carriers.
The detergent r(~ v~ herein will preferably be formulated such 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. Automatic
~' ' Gi L...~ product r ~ '' preferably have a pH between about 8 and about
I l. Laundry products are typicaiiy at pH 9-11. Techniques for controlling pH atusage levels include the use of buffers, alkalis, acids, etC., and are well
known to those skilled in the art.
The following examples illustrate ~.,~,...... l-,,,,l;,. ~ according to the invention,
but are not intended to be iimiting thereo
The following detergent ~.,,,,,l,"~ l;,~..c are prepared (parts by weight).
MPr.F I
Wei~2ht %
Zeolite 38.0%
Silicate 2.0R 6.0%
Carbonate (Sodium) 9.0%
~thylene Diamine Tetra
Methylene ~' , ' 0.2%
Brightener 47 (Tirlopai DMS) 0.1%
Brightener 49 (Tinopal CBS) 0.05%
r~ ,G,I, 8.0%
TAED 7.0%
Mn Catalyst~vppm) 350
Savinase (4.0 KNPU/g) 2.0%
Lipolase (100,000 LU/g) 0.22%
C12 14 Aikyl Sulphate 5.6%
C12 14 AE4.2 nonionic 11.6%
Soap 1.0%
~7I6g
WO gs/2777~ .'^7 '
33
~- " /Moist.
Balance 100%
*Mnlv2(u-o)3(l74~7-trimethy~ 4~7-L~ y~lullull~ )2(pF6)2
ExAMPLF n
Weight %
Zeo&te 38.0%
Si&cate 2.0R 6.0%
Carbonate (Sodium) 7.0%
Ethylene Diamine Tetra
Methylene r~ , ~ 0.2%
Brightener 47 (Tinopal DMS) 0.1%
Brightener 49 (Tinopal CBS) 0.05%
r~5.0%
TAED 2.0%
Mn Catalyst*(ppm) 350
Savinase (4.0 KNPU/g) 2.0%
Lipolase (100,000 LU/g) O.æ%
C12 14 Alkyl Sulphate 5.6%
C12 14 AE4.2 nonionic 11.6%
Soap 1.0%
Persulfate 1 0.0%
M C., 11 -- - v ~lMoist.
Balance 100
*Mnlv2(u-0)3(1,4,7-trimethyl-1,4,7-Ll;~ )2(PF6)2
S EXAMP~.F 111
Wei~ht %
Zeolite 38.0%
Silicate 2.0R 6.0%
Carbonate (Sodium) 7.0%
Ethylene Diamine Tetra
Methylene pl , ' 0.2%
Brightener 47 (Tinopal DMS) 0.1%
Brightener 49 (Tinopal CBS) 0.05%
W095/27775 2~ g 34 r~
rLI ~,c~l 5.0%
TABD 2.0%
Mn Catalyst*(ppm) 350
Savinase (4.0 KNPU/g) 2.0%
Lipolase (100,000 LU/g) 0.22%
C 12 14 Alkyl Sulphate 5.6%
C12 14 AE4.2 nonionic 11.6%
Soap 1.0%
PAP4~ 10.0
~' " 'Moist. 100
Balance
~MnlV2(u-0)3(1,4,7-trimethyl-1,4,7-~1;c~"~, ' -)2(PF6)2
~N,N-I' ' ' ,' , u~.y~,c~lu;cacid
All of the foregoing granular ~ u~ may be provided as srpay-dried granules
or high density (above 600 g/liter) granules or ,.~1.,.. n~ In ~xample III, the
PAP may be replaced by 6-llUII~' 6-u~ulJ~U~.y~ u;~, acid (NAPAA).
