Note: Descriptions are shown in the official language in which they were submitted.
21 ~7303
WO 95/284G7 P.l/la.,_. /ul
DETERGENTS CONTAINING AN ENZYME AND A DELAYED RELEASE PEROXYACID
BLEACHING SYSTEM
This invention relates to detergent , containing an enzyme, preferably an
amylase enzyme, and an organic peroxyacid bleaching system, wherein a means is
provided for delaying the release to the wash solution of the organic peroxyacidbleach relative to the release of the ~nzyme.
The s~L,r~ul~ removal of coloured naturally derived soils/stains such as blood, egg,
chocolate, gravy from soiled/stau~ed substrates is a particular challenge to theformulator of a detergent ~ ... for use in a washing method such as a laundry
or machine di;.l.w~ , method.
Tr~iitinn~lly, the removal of such coloured soils/stains has been enabled by the use of
bleach . such as oxygen bleaches, including hydrogen peroxide and organic
u~ids, and also by enzyme ~ The organic peroxyacids are often
obtained by the in situ p. Il~yd~ ,;, reaction between hydrogen peroxide and an
organic peroxyacid bleach precursor.
A problem ~ ~ with the use of certain organic peroxyacid bleaches in laundry
washing methods is a tendency for these organic peroxyacid bleaches to affect the
colour stability of the fabrics being washed. Types of fabric damage can includefading of coloured dyes on the fabrics or localised areas of "patchy" colour bleaching.
A problem ~ J with the use of enzymes as ~ . of detergents is that
enzyme activity in the wash may be affected by the presence of other detergent
in the wash solution. Degradation of enzymes by bleach c- . has
been found to be a particular problem. Also ~ of the enzyme substrates by
the bleach has been found to reduce the activity of the enzyme, p~Li. uld.l~ amylase.
WO95/284i67 1'.~ vl
22~7~a3
The detergent formulator thus faces the dual challenge of r.."~ , a product which
maximises soillstain remoYal but minimises the occurrence of any . ~ enzyme
" or fabric colour stability effects of the bleach.
The Applicants have found that the occurrence of any . ~. ' fabric colour
stability or enzyme ~ l effects arising from the use of organic peroxyacid
bleaches in a washing method can be related to the rate of release of the peroA-yacid
bleach to the wash solution and also to the absolute level of peroA~yacid present in the
wash solution.
A fast rate of release of the peroxyacid bleach to the wash solution tends to heighten
the probability that u~ u~ fabric colour stability effects and enzyme ~
effects will occur, as does a high absolute level of the bleach in the wash solution.
Whilst reducing either the rate of release of the peroxyacid bleach, or the absolute
level of the bleach employed in the wash tends to arneliorate these problems, this can
be a~ by a negative effect on the bleachable stain/soil removal ability.
The Applicants have now however found that where a ~ A containing both an
enzyme and a pero~yacid bleach source is employed, and wherein a means is provided
for delaying the release to a wash solution of the peroxyacid bleach relative to the
release of the enzyme enhanced stain/soil removal, I ' 'y on coloured naturally
occurring stains/soils, may be obtained. The invention is lu~ut; ' 'y useful forcontaining proteases, lipases and most ~li ' ly amylases, cellulases
and pe~
Additionally, where the . ~ is used in a laundry washing method a reduction
in the propensity for negative fabric colour stability effects to be observed is also
obtained.
It is therefore an object of the present invention to provide CI~ suitable for
use in laundry and machine ~ h... ' ~ methods having enhanced stain removal.
It is also an object of the present invention to provide ~ u ~ for use in a
laundry washing rnethod wherein said ~ show less propensity to cause
negative fabric colour stability effects.
W0 9S128467 2 l 8 73 0 3 ~ u~
Summary of the Invention
According to one aspect of the present invention there is provided a detergent
r~ ,- ';r..\ containing
(a) an enzyme; and
~b) an organic peroxyacid bleaching system
wherein a means is provided for delaying the release to a wash solution of said
organic peroxyacid relatiYe to the release of said enzyme such that in the T50 test
method herein described the time to achieve a . that is 50% of the
ultimate C~. ~f .,~ ;"" of the enzyme is less than 120 seconds and the time to achieve
a c~ I;r n that is 50% of the ultimate ~n~~f 1~ of the organic peroxyacid is
more than 180 seconds.
According to another aspect of the present invention there is provided a detergent
~ . containing
(a) a enzyme; and
~b) an organic peroxyacid bleaching system
wherein a means is provided for delaying the release to a wash solution of said
organic peroxyacid relative to the release of said enzyme such that in the T50 test
method herein described the time to achieve a that is 50% of the
ultimate r~ of said enzyme is at least 100 seconds, preferably at least 120
seconds, more preferably at least 150 seconds less than the time to achieve a
that is 50~ of the ultimate - - ~ of said organic peroxyacid.
The organic peroxyacid bleaching system preferably comprises in .
(i) a hydrogen peroxide source; and
(ii) an organic peroxyacid bleach precursor compound
An essential component of the detergent , is an enzyme.
wo 95/28467 ' 2 1 8 7 3 ~ 3 ~ 707
Suitable enzymes include the: "y available lipases, amylases, neutral and
alkaline proteases, cellulases, pectinases, lactases and ~.u d~, that is enzymeshaving lipolytic, amylolytic, proteolytic, cellulolytic, pectolytic, lactolytic and
.hk/ly~ic activity lc*)~~ cu..~.lliu,.,lly ;.I.,ul~uldt~ into detergent
C Suitable enzymes are discussed in US Patents 3,519,570 and
3,533,139.
Protease enzymes are especially preferred as the enzyme f rm~ nPn~ Preferred
commercially available protease enzymes include those sold under the t ~
Alcalase, Savinase, Primase, Durazym, and Esper,se by Novo Industries A/S
~'Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by
Gist-Brocades, those sold by Genencor r ~ and those sold under the
tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be
' into the ~ in accordance with the invention at a level of from
0.0001% to 4% active enzyme by weight of the ~ ~p~
Preferred amylases include, for example, a-amylases obtained from a special strain of
B ' ' ~ , described in more detail in GB-1,269,839 ~'Novo). Preferred
.,;"lly available amylases include for example, those sold under the tradename
Rapidase by Gist-Brocades, and those sold under the tradename Termamyl and BAN
by Novo Industries A/S. Amylase enzyme may be i~l~ul; ' into the ~
in accordance with the invention at a level of from 0.0001% to 4% active enzyme by
weight of the ~
Lipolytic enzyme (!ipase) may be present at levels of active lipolytic enzyme of from
0.0001% to 4% by weight, preferably 0.001% to 1% by weight, most preferably
from 0.C101% to 0.5 % by weight of the ~ C
The lipase may be fungal or bacterial in origin being obtained, for example, from a
lipase producing strain of Humicola sp., Tl.~ sp. or ~"v~lO u. ~. sp.
including F~rJd~ J ~ f~ - -; or pSfll~if~ C fluorPc~n~ Lipase from
chemically or genetically modified mutants of these strains are also useful herein.
A preferred lipase is derived from r~ ~'JOI ~IV l~tS ~ ,Ju~ d i ~- A~ ~ . which is
described in Granted European Patent, EP-B~218272.
WO 95/28467 ~ 1 ~ 7 3 ~ 3 ~ u~
s
Another preferred lipase herein is obtained by cloning the gene from Humicola
lanu~inosa and expressing the gene in ACnpre~ c orvza, as host, as described in
Eu~opean Patent ArF~ EP-A-0258 068, which is, ~ly available from
Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase
is also described in U.S. Patent 4,810,414, Hu~_ J~ .l et al, issued March 7, 1989.
r~ni~ reroxy~ hlP~hir(~ system
An essential feature of the invention is an organic peroxyacid bleaching system. In
one preferred execution the bleaching system contains a hydrogen peroxide sour_e Dd
an organic peroxyacid bleach precursor compound. The production of the organic
peroxyacid occurs by an in situ reaction of the pre_ursor with a source of hydrogen
peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate
bleaches. In an alternative preferred execution a preformed organic peroxyacid is
-, I directly into the: . (' nl containing mixtures of a
hydrogen peroxide source and organic peroxyacid precursor in ' with a
preformed organic peroxyacid are also envisaged.
lnor~anic perhydrate bleaches
Inorganic Ferhydrate salts are a preferred source of hydrogen peroxide. These salts
are normally lJUI~ in the form of the alkali metal, preferably sodium salt at a
level of from 1% to 40% by weight, more preferably from 2% to 30% by weight and
most preferably from 5 % to 25 % by weight of the c. . .~
Examples of suitable inorganic perhydrate salts include Ferborate, ~ uL~, ' . ' , persulfate and persilicate salts and mixtures thereof. The inorganic
Ferhydrate salts are normally the all~i metal salts. The inorganic perhydrate salt may
be included as the cryst lline solid without additional protection. For certain
perhydrate salts however, the preferred executions of such granular
utilize a coated form of the material which provides better storage stability for the
perhydrate salt in the granular product.
Sodium perborate can be in the form of the l~u~ul~yl' ' of nominal formula
NaBO2H2O2 orthe i j NaB2H22 3H2
wo ss/2s467 2 1 8 7 3 0 3 r~ 707
lkali metal p~ u~ u li~ul~uly sodium ~ ul ~ are preferred
for inclusion in ~ in accordance with the invention.
C~ c containing p~l~bùllal~ have been found to have a reduced tendency to
form I ' ' ' gels in the presence of surfactants and water than similar
~" '1'"- ';"'`' which contain perborate. It is belieYed that this is because typicaLly
has a lower surface area and lower porosity than perborate l~u~ul~
This low surface area and low porosity acts to prevent the co-gelLing with fine
particles of surfactant ~ll . n~ and is therefore not ~tri~ r~l to dispensing.
Sodium p~u~ is an addition compound having a formula ~ ~ r e to
2Na2C03.3H202, and is available ~ "y as a crystalline solid. The
y.,.~ is most preferably il~ ' into such ~ u. . .l~ . c in a coated form
which provides in product stabiLity.
A suitable coating material providing in product stability comprises mixed salt of a
water soluble allcali metal sulphate and carbonate. Such coatings together with
coating processes have previously been described in GB-1,466,79g, granted to Interox
on 9th March 1977. The weight ratio of the mixed salt coating material to
.,,~u~ lies in the range from 1: 200 to 1: 4, more preferably from 1: 99 to I
: 9, and most preferably from 1: 49 to 1: 19. Preferably, the mixed salt is of
sodium sulphate and sodium carbonate which has the general formula
Na2SO4.n.Na2CO3 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and
most preferably n is from 0.2 to 0.5.
Other coatings which contain silicate (alone or with borate salts or boric acids or other
inorganics), waxes, oils, fatty soaps can also be used ad~. _ 1y within the
present invention.
Potassium ~,u,~y ~ '' is another inorganic perhydrate salt of use in the
detergent ~ ;. - herein.
pf roxyacid bleach ~recursor
Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a
~l~ydlul~ reaction to produce a peroxyacid. Generally peroxyacid bleach
precursors may be ~r ' as
WosS/28467 2~ ~7303 P~./l,~ /v7
X - C -L
where L is a leaving group and X is essentially any ru~ iùllalily, such that on
Pe~ YdIUIU.~5;D the structure of the peroxyacid produced is
1l
X-C-OOH
Peroxyacid bleach precursor ~ . ' are preferably . ' at a level ûf from0.5% to 20% by weight, mûre preferably frûm 1% tû 15% by weight, most
preferably from 1.5% to 10% by weight of the detergent ~ ;. ,A ~
Suitable peroxyacid bleach precursor . , ' typically contain one or more N- or
O-acyl groups, which precursors can be selected from a wide r^Dnge of classes.
Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of
imidazoles and oximes. Examples of useful materials within these classes are
disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798,1147871, 2143231 and EP-A-0170386.
The Applicants have found that 'patchy' danAage can be ~ ul~uly associav-d with
peroxyacid bleach precursor r which on ~h~lly.llUl~D;D provides a
peroxyacid which is
(i) a perbenzoic acid, or non-cationic substituted derivative thereof; or
(ii) a cationic peroxyacid.
n .,,... -,: precursors have also been found to be p~ ul~ul~ susceptible to the
problem.
Leavin~ ~roups
The leaving group, hereinafter L group, must be ~ reactive for the
p~lllJJIUl.~D;s reaction to occur within the optimum time frame (e.g., a wash cycle).
wo ssns467 F~ . Iul
~1 87303
However, if L is too reactive, this activator will be difficult to stabilize for use in a
bleaching ~
Preferred L groups are selected from the group consisting of:
--o~ --O~Y and --0~ Y
--N--8--R1 --N N --N--11--CH--R4
l3 ~ R3 Y
y
.
R3 Y
-O-CH=C--CH=CH2 --O--CH=C--CH=CH2
-O--C--R1 CH2-C --~j /NR4
O O
R3 g Y
--O--C=CHR4 , and --N-- --C,H--R4
R3 o
and mi~tures thereof, wherein Rl is an alkyl, aryl, or alkaryl group containing from I
to 14 carbon atoms, R3 is an alkyl chain containing from I to 8 carbon atoms, R4 is
H or R3, and Y is H or a: ' ' `1i7in~ group. Any of R1, R3 and R4 may be
substituted by essentially any functional group including, for example alkyl, hydroxy,
alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl - - groups
The preferred ~ l;,;,.g groups are -SO3 M+, -CO2 M+, -SO4 M+,
-N+~R3)4X- and o<--N(R3)3 and most preferably -S03-M+ and -C02 M+
wherein R is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation
, . _
W095/28467 ~1 8~3~3 P~ U
which provides solubility to the bleach activator and X is an anion which provides
solubility to the bleach activator. Preferably, M is an alkali metal, or
substituted ~ n- cation, with sodium and potassium being most preferred, and
X is a halide, hydroxide, mell.y'~ '' or acetate anion.
perhPn71lin ~ nri ~priv~tives thereof ~rPrllr~rc
Perbenzoic acid precursor: . ' provide perbenzoic acid on ~ vlul~
Suitable O-acylated perbenzoic acid precursor . ' include the substituted and
' benzoyl u,~y~ sulfonates, including for exarnple benzoyl
u~ nc sulfonate:
o
~o~S03-
Also suitable are the ~ V,~;dl.iUII products of sorbitol, glucose, and all
with b~ v~ agents, including for example:
OAc
AcO~o
/~,OAc
OBz
Ac = COCH3; Bz = Benzoyl
Perbenzoic acid precursor ~ ~ ' of the imide type include N-benzoyl
', t~ Lvyl ethylene diamine and the N-benzoyl substituted ureds.
Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and
N-benzoyl b. ..,; - 1 .~..lr and other useful N-acyl group-containing perbenzoic acid
precursors include N-benzoyl ~~ O, dibenzoyl taurine and benzoyl
y~lu~ lu~ acid.
_ _ _ .. .. .
w0 95/28467 P~ "1 ., _. Iu I
21 87303
Other perbenzoic acid precursors include the benzoyl diacyl peroxides, the benzoyl
tetraacyl peroxides, and the compound having the formula:
~0~ O~COOH
Phthalic anhydride is another suitable perbenzoic acid precursor compound herein:
o
~0
Suitable N-acylated lactam perbenzoic acid precursors have the formula:
X--CH2--CH2
~C H2~C H2 ]n
wherein n is from O to 8, preferably from O to 2, and R6 is an aryl, alkoxyaryl or
aL~ryl group containing from I to 12 carbon atoms, or a substituted phenyl groupcontaining from 6 to 1~ carbon atoms, preferably a benzoyl group.
Perbenzoic ~rifi derivative ~recursors
Perbenzoic acid derivative precursors provide substituted perbenzoic acids on
~uitable substituted perbenzoic acid derivative precursors include any of the herein
disclosed perbenzoic precursors in which the benzoyl group is substituted by
essentially any non-positively charged (ie; non-cationic) functional group including,
for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and amide groups.
... . . . .. . ..
W095l28467 2~73~3 P~ U~
11
A preferred class of substituted perbenzoic acid precursor cv-, ' are the amide
substituted . . ' of the following general formulae:
R1--C--N--R2--C--L R1--N--C--R2--C--L
Il 1 11 1 11 11 .
O R5 0 or R5 0 0
wherein Rl is an aryl or alkaryl group with from I to 14 carbon atoms, R2 is an
arylene, or alkarylene group containing from I to 14 carbon atoms, and R5 is H or an
alkyl, aryl, or alkaryl group containing I to 10 carbon atoms and L can be essentially
any leaving group. Rl preferably contains from 6 to 12 carbon atoms. R2 preferably
contains from 4 to 8 carbon atoms. Rl may be aryl, substituted aryl or alkylarylcontaining branching, ' or both and may be sourced from either synthetic
sources or natural sources including for example, tallow fat. Analogous structural
variations are p~ for R2. The ..~ 1 can include alkyl, aryl, halogen,
nitrogen, sulphur and other typical substituent groups or organic ~ 1, ' R5 is
preferably H or methyl. Rl and RS should not contain more than 18 carbon atoms in
total. Amide substituted bleach activator ~ . ' of this type are described in EP-
A-0170386.
('~fjn.lir peroxyacid precllrcnrs
Cationic peroxyacid precursor cu..,r ' produce cationic ~IU,~.Ci.l~ on
Typically, cationic peroxyacid precursors are formed by ' ~ the peroxyacid
part of a suitable peroxyacid precursor compound with a positively charged functional
group, such as an: or alkyl _ group, preferably an ethyl or
methyl group. Cationic peroxyacid precursors are typically present in the
solid detergent .~ ;,. c as a salt with a suitable anion, such as a halide ion.
The peroxyacid precursor compound to be so cationically substituted may be a
perbenzoic acid, or substituted derivative thereof, precursor compound as described
1., .~ :,.1.. f~,.~ ~1 "\..,1~, the peroxyacid precursor compound may be an alkyl
~ bu~ acid precursor compound or an amide substituted alkyl peroxyacid
precursor as described hereinafter
.. _ . , ... . . .. _ _ _ . . . .
wog~ 67 r~ . '/Q'707
221 87303 ~
Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015;
4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K.
1,382,594; EP 47S,512, 458,396 and 284,292; and in JP 87-318,332.
Examples of preferred cationic peroxyacid precursors are described in UK Patent
Application No. 9407944.9 ard US Patent Application Nos. 08/298903, 08/298650,
08/298904 and 08/298906.
uitable cationic peroxyacid precursors include any of the or alkyl
substituted alkyl or benzoyl UA~b~,llL~,I.., sulfonates, N-acylated
~,G~ 1,7 ' S, and ' ~' ~I glucose benwyl peroxides.
A preferred cationically substituted benzoyl UA,~lb~.l~ll~, sulfonate is the 4-(trimethyl
^~m~ ) methyl derivative of benzoyl UA~b.,~ sulfonate:
o
~40~S03-
~+
A preferred cationically substituted allcyl UA~b~.ll~.ll., sulfonate has the formula:
J~/ 3
Preferred cationic peroxyacid precursors of the N-acylated ,a~ ' class include
the trialkyl: methylene benzoyl ~G~lUla~kU~ GIIi~.U lUl~ trimethyl
mOylene benzoyl ~,G~Iula~uul~.
w0 95128467 ~ 1 ~3 7 3 ~ ui
13
\ ~ ~ N
Otha preferred cationic peroxyacid precursors of the N-acy~ated wlJIula~ uml class
includethetrialkyl methylenealkyl,~.",l, I A
O O
)lN
/N+ ~ (CH2)n
where n is from O to 12.
Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl
ethyl sodium 4 s li ' . ' yl carbonâte chloride.
Alkyl ~ uAylic ~rill h1r~rh ~\rlorllrcnrc
A~yl pclw-~u~ ;c acid bleach precursors form ~.wlbu~ylic âcids on ~llyJIul~
Preferred precursors of this type provide peracetic acid on ~.I.~JIul~
Preferred alkyl ~~ JU~lic precursor: of the imide type iAclude the N-
,N,NINl tetra acetylated alkylene diamines wherein the alkylene group contains from
1 to 6 carbon atoms, I,all;!_ulally those: . in which the alkylene group
contains 1, 2 and 6 carbon atoms. T~llaac~lylu;llJ ' (TA~D) is p~~ l~ly
preferred.
Other preferred alkyl ~.w lJu~lic acid precursors include sodium 3,5,5-tri-methyl
lu ~ u~luAylJ. .I~.l~ sulfonate (iso-NOBS), sodium rlulla~lu~lu~yl~ c sulfonate
(NOBS), sodium àc~ tu~yl~ sulfonate (ABS) and pentaacetyl glucose
-
woss/2s467 2 ~ ~ 73~3 ~ u~
14
Amide substituted alkyl perox~q~ rPr~sorS
Amide substituted alkyl peroxyacid precursor ~ E ' are also suitable, including
those of the following general formulae:
R1--C--N--R2--C--L R1--N--C--R2--C--L
O R5 0 or R5 0 0
wherein Rl is an alkyl group vith from I to 14 carbon atoms, R2 is an alkylene
group containing from I to 14 carbon atoms, and RS is H or an alkyl group
containing I to 10 carbon atoms and L can be essentially any leaving group. Rl
preferably contains from 6 to 12 c^qrbon atoms. R2 preferably contains from 4 to 8
carbon atoms. Rl may be straight chain or branched alkyl containing branching,
or both and may be sourced from either synthetic sources or natural
sources including for ex~mple, tallow fat. Analogous structural valiations are
;I,lr for R2. The ~ can include alkyl, halogen, nitrogen, sulphur
and other typical substituent groups or organic cnn~pol~n~lc R5 is preferably H or
methyl. Rl and R5 should not contain more than 18 carbon atoms in total. Amide
substituted bleach activator ~ of this type are described in EP-A-0170386.
r ~ ~erox~q~ precursors
Also suitable are precursor com~ C of the b~..~u~i,~ type, as disclosed for
example in EP-A-332,294 and EP-A482,807, ~ i.,uLl~ those having the formula:
o
~ ~o
Wos5/28467 21873~3 r~l,, 9,1 ,~"
including the substituted ~ of the type
R2 S'
R3~ - R
Rs
wherein Rl is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4, and
my be the same or different ` ~ f` selected from H, halogen, alkyl, alkenyl,
aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR6 (wherein R6 is H or an alkyl
group) and carbonyl functions.
An especially preferred precursor of the benzoxazin-type is:
1l
~ "C~
Preforn~ ero~y~
The organic peroxyacid bleaching system may contain, in addition to, or as an
alternative to, an organic peroxyacid bleach precursor compound, a preformed
organic peroxyacid, typically at a level of from 1% to 15% by weight, more
preferably from 1% to 10% by weight of the ~'J'"l~'` ';""
A preferred class of organic peroxyacid ' are the amide substituted
' of the following general for~nulae:
R1--C--N--R2--Cl--OOH R1--I--C--R2--Cl--OOH
O R5 0 or R5 o
wherein Rl is an allyl, aryl or alkaryl group with from I to 14 carbon atoms, R2 is
an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and
RS is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. Rl
W0 95/28467 2 1 ~ ~ 3 ~ ~ P.~ 707
16
preferably contains from 6 to 12 carbon atoms. R2 preferably eontains from 4 to 8
carbon atoms. Rl may be straight chain or branched alkyl, substituted aryl or
alkylaryl containing branching, ~ ,." or both and may be sourced from either
synthetic sources or natural sources including for example, tallow fat. Analogous
structural variations are ~ Ir for R2. The ' can inelude alkyl, aryl,
halogen, nitrogen, sulphur and other typical substituent groups or organic r
R5 is preferably H or methyl. Rl and R5 should not contain more than 18 carbon
atoms in total. Amide substituted organic peroxyacid . ' of this type are
described in EP-A-0170386.
Other organic p~.u~ ,ids indude diacyl and t~ u/L~, especially
dilJ~,.u~yJo-~ c acid, Ji~u~.y~ r. ~ c acid and
J;~.u,~ acid. Mono- and ~ acid, mono- and ~;~wb~ iC
acid and N-l ' ' 'C.~' r U~ U;C acid are also suitable herein.
('hl~lrinP hlP~lrh
The cu",~ herein are preferably free of chlûnne bleach.
nlr~rh r~t~¦ySt
The invention also ~ ,- containing a catalytically effective
amount of a bleach catalyst such as a water-soluble manganese salt.
The ~leac~ ~a~alyst is ~5P~l in a c~talytically effP tive am..o~JDt in. th5 ~
herein. By "~61~L~lly effective amount" is meant an amount which is suffieient,
under whatever ~,ul~.pcudLv~ test eonditions are employed, to enhanee bleaehing and
removal of the stain or stains of interest from the target substrate. Thus, in a fabric
laundering operation, the target substrate will typically be a fabric stained with, for
example, various food stains. For automatic di Ih.. ' ~, the target substrate may
be, for example, a porcelain cup or plate v~ith tea stain or a ~ul~ ..., plate stained
with tomato soup. The test eonditions will vary, depending on the type ûf washing
appliance used and the habits of the user. Thus, front-loading laundry washing
maehines of the type employed in Europe generally use less water and higher
detergent, - than do top-loading U.S.-style machines. Some maehines
have ~.U~Ji~ bly longer vash cycles than others. Some users eleet to use very hot
water; others use warm or even cold water in fabric laundering opera~ions. Of
~ Wos~2s467 2 ~ 3 ~ u~
17
course, the catalytic ~lr~ of the bleach catalyst will be affected by such
, and the levels of bleach catalyst used in fully-formulated detergent and
bleach ~ can be a~lul '~/ adjusted. As a practical matter, and not by
way of limitation, the ....~ 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 I ppm to about
200 ppm of the catalyst species in the laundry liquor. To illustrate this point further,
on the order of 3 ~ ol~ manganese catalyst is effective at 40C, pH 10 under
European conditions using perborate and a bleach precursor (e.g., benzoyl
~lula~ ). An increase in ~ "~ of 3-5 fold may be required under U.S.
conditions to achieve the same results. Conversely, use of a bleach precusor and the
manganese catalyst with perborate may allow the formulator to achieve equivalentbleaching at lower perborate usage levels than products without the manganese
catalyst.
The bleach catalyst material herein can comprise the free acid or be in the form of any
suitable salts.
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, anauxiliary 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 auxiliary metal cations, ~l;~,,,l,..ly, Lll~' " - acid,
'Il..,lh~k . ' ~' 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
includeMnlV2(u-0)3(1,4,7-trimethyl-1,4,7-~;~,' e)2-(PF6)2, Mnm2(U-
O)l(u-OAc)2(1,4,7-trimethyl-1,4,7-Lli~ (C104)2, MnIV4(u-
0)6(1,4,7-Ll~."r. 1( )4-(C1O4)2, MnmMnIv4(u-o)l(u-oAc)2-(l~4~7-
trimethyl-1,4,7-L~. ' )2-(C104)3. and mixtures thereof. Others are
described in European patent application publication no. 549,272. Other ligands
- suitable for use herein include l~5~9-trimethyl-l~s~9-Ll;~ ,YIO,1~ - .. , 2-methyl-
1,4,7-LI;~ , 2-methyl-1,4,7-L~ ,' , 1,2,4,7 '~ L-IIIY
1,4,7-LI;~, , and mixtures thereof.
.
w0 ssns467 2 18 7 3 0 3 r~ /vl ~
18
For examples of suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat.
5,227,084. See also U.S. Pat. 5,194,416 which teaches ,~ ..", 1. ~, manganese (IV)
complexes such as Mn(1,4,7-trimethyl-1,4,7-L i~y. ' )(OCH3)3 (PF6). Still
another type of bleach catalyst, as disclosed in U.S. Pat. 5,114,606, is a water-soluble
complex of manganese (II), (III), and/or (IV) with a ligand wbich is a non-
~UAy' ~ulyhydluAy compound having at least three . vt; C-OH groups.
Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol,
adonitol, meso ~1~;' 1, meso-inositol, ]actose, and mixtures thereof.
U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transitionmetals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said
ligands are of the formula:
R2 R3
R1 -N=C-B-C=N-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 ' ' B is a bridging group selected from O, S.
CRSR6, NR7 and C=O, wherein R5, R6, and R7 can each be H, alkyl, or aryl
groups, including substituted or ~ ' ' groups. Preferred ligands include
pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings.
Optionally, said rings may be substituted with ' such as alkyl, aryl, alkoxy,
halide, and nitro. lF ' 'y preferred is the ligand 2,2'-b;*~ylily' Preferred
bleach catalysts include Co, Cu, Mn, Fe,-1;~y.idyl...~LI.~.~ and -I,;~ylidyl~lficomplexes. Higbly preferred catalysts include Co(2,2 -~ ylidy ,C12.
D (;~v~l~iu~,y )b; .t~yliuJ' cobalt (II), i 'i ylidy' cobaltaI)
, Co(2,2-~;~y.i~y' )?02CI04, Bis-(2,2'-~i~y.idy' ~.) copper(II)
tris(di-2-~yli.lyl.ll..;..~) iron(lI) I ' ' , 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
N4MnIII(u-0)2MnIVN4)+and [Bipy2Mnm(u-0)2MnIVbipy2]-(C104)3.
The bleach catalysts may also be prepared by combining a water-soluble ligand with a
water-soluble manganese salt in aqueous media and ~ I ~, ,. _. .1~ ,~1'. .~, the resulting
~095/28467 2 1 87 3~3 1~
19
mixture by e~ ,u~ iul,. Any cûnvenient water-sûluble salt ûf manganese can be used
herein. Manganese (II), (III), (IV) and/or (V) is readily available on a rr~ rri~1
scale. In some instances, sufficient manganese may be present in the wash liquor,
but, in general, it is preferred to add Mn cations in the . . - to ensure its
presence in ~~ y-effective amounts. Thus, the sodium salt of the ligand and a
member selected from the group consisting of MnS04, Mn(C104)2 or MnC12 (least
preferred) are dissolved in water at molar ratios of ligand:Mn salt in the range ûf
about 1:4 to 4:1 at neutral or slightly alkaline pH. The water may first be de-
UA,~ ~ ' ' 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 ~ u ~ herein without further 1~
In an alternate mode, a water-soluble manganese source, such as MnS04, is added to
the bleach/cleaning ~ U ~ n or to the aqueous bleaching/cleaning bath which
comprises the ligand. Some type of complex is apparently formed in situ, and
improved bleach ~ rul ~ ul~ is secured. In such an in situ process, it is convenient
to use a cu ~ molar excess of the ligand over the ~ , and mole ratios
of ligand:Mn typically are 3:1 to 15:1. The additiûnal ligand also serves to scavenge
vagrant metal ions such as iron and copper, thereby protecting the bleach from
One possible such system is described in European patent ~rrli~ti~m
publication no. 549,211.
While the structures of some of the bleach-catalyzing ..,~ .,. c~ c described
herein have not been elucidated, it may be speculated that they comprise chelates or
other hydrated ~UIdil~ iUII complexes which result from the interaction of the
carboxyl and nitrogen atoms of the ligand with the manganese cation. Lilcewise, the
oxidation state of the manganese cation during the catalytic prc~cess is not known with
certainty, and may be the (+II), (+III), (+IV) or (+V) valence state. Due to theligands' possible six points of attachment to the manganese cation, it may be
reasonably speculated that multi-nuclear species and/or "cage" structures may exist in
the aqueous bleaching media. Whatever the form of the active Mn~igand species
which actually exists, it functions in an apparently catalytic manner to provideimproved bleaching ~. . r.." - ~ on stubborn stains such as tea, ketchup, coffee,
blood, and the like.
Other bleach catalysts are described, for example, in Europe~n patent ~rr1ir~-inn
publication no. 408,131 (cobalt complex catalysts), European patent ~
wo ss/2s467 2
ublication nos. 384,503~ and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455
ligand catalyst), U.S. 4,711,748 and ~uropean patent
:Ir~lir~tir~n publication no. 224,952, (absorbed manganese on -' '
catalyst), U.S. 4,601,845 (~' 1 support with manganese and zinc or
salt), U.S. 4,626,373 ( _ 'ligand catalyst), U.S. 4,119,557 (ferric
complex catalyst), German Pat. ~ 2,054,019 (cobalt chelant catalyst)
Canadian 866,191 (transition metal-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).
l~tive release kinetics
In an essential aspect of the inYention a means is provided for delaying the release to a
wash solution of the organic peroxyacid bleach relative to the release of the enzyme.
Said means may comprise a means for delaying the release of the organic peroxyacid
bleach to the wash solution.
Alternatively said means may comprise a means for enhancing the rate of release of
the enzyme to tbe solution.
A most preferred way is to delay the release of both the peroxyacid bleach and the
release of H22
I)elay~d r~t~ of release - rn.o~c
The means may provide for delayed release of an organic peroxyacid bleach sourceitself to the wash solution. Alternatively, where the organic peroxyacid source is a
peroxyacid precursor compound the delayed release means may comprise a means of
inhibiting, or preventing the in situ ~.I,~J~ reaction which releases the organic
peroxyacid into the solution. Such means could, for example, include delaying
release of the hydrogen peroxide source to the wash solution, by for example,
delaying release of any inorganic perhydrate salt, acting as a hydrogen peroxidesource, to the wash solution.
The delayed release means can include coating any suitable component with a coating
or mixture of coatings designed to provide the delayed release. The coating may
wo 95~w67 . ~l/L.__ _. IU7
2~ 873~3
21
therefore, for example, comprise a poorly water soluble material, or be a coating of
sufficient thickness that the kinetics of dissolution of the thick coating provide the
controlled rate of release.
The coating material may be applied using various methods. Any coating material is
typically present at a weight ratio of coating material to bleach of from 1:99 to 1:2,
preferably from 1:49 to 1:9.
Suitable coating materials include L~ ;dW (e.g. partially) ~ ,. ' vegetable
oil, soy bean oil, cotton seed oil) mono or ~;~ly~.i~,s, .~ alline waxes,
gelatin, cellulose, fatty acids and any mixtures thereof.
Other suitable coating materials can comprise the alkali and alkaline earth metal
sulphates, silicates and carbonates, including calcium carbonate.
Preferred coating material is sodium silicate of SiO2: Na2O ratio from 1.6: 1 to 3.4
: 1, preferably 2. 8: 1, applied as an aqueous solution to give a level of from 2 % to
10%, (normally from 3% to 5%) of silicate solids by weight of the p~L
silicate can also be included in the coating.
Any inorganic salt coating materials may be combined with organic binder materials
to provide composite inorganic adl;/l ~ binder coatings. Suitable binders include
the C1o-C20 alcohol CilL-~A.~' ' containing from 5 - 100 moles of ethylene oxide per
mole of alcohol and more preferably the C1s-C20 primary alcohol ethoxylatw
containing from 20 - 100 moles of ethylene oxide per mole of alcohol.
Other preferred binders include certain polymeric materials. r~
with an average molecular weight of from 12,000 to 700,000 and ~ hjl.,a~ glycols(PEG) with an average molecular weight of from 600 to 10,000 are examples of such
polymeric materials. Copolymers of maleic anhydride with ethylene, .r;t;llyl
ether or ,II~ lic acid, the maleic anhydride ~ ~ at least 20 mole percent
of the polymer are further examples of polymeric materials useful as binder agents.
These polymeric materials may be used as such or in . ' with solvents such
as water, propylene glycol and the above mentioned Clo-C20 alcohol ethoxylatws
containing from 5 - 100 moles of ethylene oxide per mole. Further examples of
binders include the Clo-C20 mono- and diglycerol ethers and also the Clo-C20 fatty
acids.
woss/2s467 21 87 303 ~ r~ u/ ~
22
Cellulose derivatives such as ~ ,LI~ lu~ Ll.~l~cllulose, ethyl
h~J~uA~Lll.ylcellulose and l~J~ .,Ll.~ llulose, and homo- or co-polymeric
ub~ yl;c acids or their salts are other examples of binders suitable for use
herein.
One method for applying the coating material involves ~ Preferred
~ ;. . processes include the use of any of the organic binder materials
described h~ll bove. Any w.. ~. I `LE~""'' ' ' ~' / ' may be used including,
but not limted to pan, rotary drum and vertical blender types. Molhen coating
c.. ~ c may also be applied either by being poured onto, or spray atomized onto
a moving bed of bleaching agent.
Other means of providing the required delayed release include mechanical means for
alhering the physical ~ h ;~ of the bleach to control its solubility and rate ofrelease. Suitable protocols could include cnnnp~ rinn mechanical injection, manual
injection, and adjustment of the solubility of the bleach compound by selection of
particle size of any particu~ate ~ ,
Whilst the choice of particle size will depend both on the c~ of the
particulate, . t, and the desire to meet the desired delayed release kinetics, it is
desirable that the particle size should be more than 500 I...~.,,,,,~h~,~, preferably
having an average particle diameter of from 800 to 1200
Additional protocols for providing the means of delayed release include the suitable
choice of any other ~ . of the detergent ~ ll ll l matrix such that when
the ~ , is introduced to the wash solution the ionic strength ~..~;..
therein provided enables the required delayed release kinetics to be achieved.
Fnh~lr~ of release - means
All suitable means for enhancing the rate of release of the enzyme to ~he solution are
envisaged.
The enhanced release means can include coating any suitable component with a
coating designed to provide the enhanced release. The coating may therefore, forexample, comprise a highly, or even ~rr~ , water soluble material.
W095128467 2~ ~73~3 P~l/u~ JP~707
23
Other means of providing the required delayed release include mechanical means for
altering the physical ~ c of the enzyme to enhance its solubility and rate of
- release.
A suitable protocol could include deliberate selection of the particle size of any
enzyme containing . The choice of particle size will depend both on the
cc ~ of the particulate r t, and the desire to meet the desired enhanced
release kinetics. It is desirable that Lhe particle size should be less than 1200
~fi~lu~ t~ , preferably having an average particle diameter of from 1100 to 500
Il.;~IUI~l~L~
Additional protocols for providing the means of delayed release include the suitable
choice of any other . of the detergent ~ matrix, or of any
particulate component containing the enzyme, such that when the . ~ is
introduced to the wash solution the ionic strength ~..vilu...l.~,-L therein provided
enables the required enhanced release kinetics to be achieved.
D,~l~yed r~lP~ kin~tir F~rPrn~t-~rS
The release of the organic peroxyacid bleach component from the peroxyacid
bleaching system relative to that of the enzyme component is such that in the T50 test
method herein described the time to achieve a ~u ~ ;.. that is 50% of the
ultimate ~a~ of said enzyme is less than 120 seconds, preferably less than 90
seconds, more preferably less than 60 seconds, and thG time o ac~hisve a
that is 50% of the ultimate ~ l of said peroxyacid bleach is
more than 180 seconds, preferably from 180 to 480 seconds, more preferably from
240 to 360 seconds. In another aspect, the T50 for the enzyme component is at least
100 seconds less than the T50 for the peroxyacid bleach.
In a highly preferred aspect of the invention the release of bleach is such that in the
T50 test method herein described the time to achieve a level of total available oxygen
(AvO) that is 50% of the ultimate level is more than 180 seconds, preferably from
180 to 480 seconds, more preferably from 240 to 360 seconds. A method for
AvO levels is disclosed in European Patent Application No. g3870004.4.
.
WO gS/28~67 P~ . IU I
21 87303 ~
24
In another preferred aspect of the invention, where the peroxyacid bleach source is a
peroxyacid bleach precursor, employed in ~ ;o,- with a hydrogen peroxide
source the kinetics of release to the wash solution of the hydrogen peroxide, relative
to those of the enzyme component is such that in the T50 test method herein described
the time to achieve a, that is 50% of the ultimate .~ ;..,. of said
enzyme is less than 120 seconds, preferably less than 90 seconds, more preferably less
tban 60 seconds, and the time to achieve a that is 50% of the ultimate
of said hydrogen peroxide and said peroxyacid bleach precursor is more
that 180 seconds, preferably from 180 to 480 seconds, more preferably from 240 to
360 seconds.
Where the enzyme is a protease, the ultimate amount in a typical wash solution is
from 0.1 to 100 KNPU, but preferably is from 0.5 to 50 ~PNU, more preferably
from 3 to 30 KNPU and most preferably from 6 to 30 KPNU.
Where the enzyme is an amylase, the ultimate amount in a typical wash solution is
from I to 200 KNU, but preferably is from 10 to 100 KNU, more preferably from 40to 80 KNU.
Where the enzyme is a lipase, the ultimate amount in a typical wash solution is from I
to 300 KLU, but preferably is from 10 to 200 KLU, more preferably from 10 to 100E~U.
Where the enzyme is a cellulase, the ultimate amount in the wash is typically from 10
to 1200 CEVU, but preferably is from 50 to 1000 CEVU, more preferably from 80 to500 CEVU.
The ultimate wash, of any inorganic perhydrate bleach is ,typically from
0.005% to 0.25% by weight, but preferably is more than 0.05%, more preferably
more than 0.075%-
The ultimate wash ~ of any peroxyacid precursor is typically 0.001% to0.08% by weight, but preferably is from 0.005% to 0.05%, most preferably from
0.015 % to 0.05 % .
yed r~ test m~th~l
wo ssl28467 2 1 87 3 ~ 3 ~ u~
The delayed release kinetics herein are defined with respect to a 'TA test method'
which measures the time to achieve A% of the ultimate ~ /level of that
component when a . , " containing the component is dissolved according to
the standard conditions now set out.
The standard conditions involve a I litre glass beaker filled with 1000 ml of distilled
water at 20C, to which lOg of , "' is added. The contents of the beaker are
agitated using a magnetic stirrer set at 100 rpm. The magnetic stirrer is pealovule-
shaped having a maximum dimension of l.5cm and a minimum dimension of O.Scm.
The ultimate ~ f ' ~ level is taken to be the c . ~ /level attained 10
minutes after addition of the nl ''' to the water-filled bealcer.
Suitable analytical methods are chosen to enable a reliable ~ ! of the
incidental, and ultimate in solution ,~ of the component of concern,
subsequent to the addition of the ~ , ' to the water in the beaLfer.
Such analytical methods can include those involving a continuous monitoring of the
level of . ~ ' of the ~ , t, including for example ~': .( ' and
methods.
Altematively, methods involving removing titres from the solution at set time
intervals, stopping the ~" ' ' process by an ~Yl ~ means such as by rapidly
reducing the; , of the titre, and then ~' ' ' ' _ the ' of the
component in the titre by any means such as chemical titrimetric methods, can beemployed.
Suitable graphical methods, including curve fitting methods, can be employed, where
~, , ' to enable calculation of the the TA value from raw analytical results.
The particular analytical method selected for ~ the . ' of the
---- r t~ will depend on the nature of that: . t, and of the nature of the
N~ containing that cnnlpnn~n~
- Addi~ion~ tf~pnt ~-r~ ,~.. ,, ,.t~
The detergent ~- . . ,1~ ,- ;. A C of the invention may also contain additional detergent
The precise nature of these additional . , and levels of
.
WO 95/28467 P~ u /
~1 87~Q3 ~
26
f. thereof will depend on the physical form of the ~ , and the
nature of the cleaning operation for which it is to be used.
The ~ , ~ of the invention may for example, be formulated as hand and
machine laundry detergent ~u~ u~ , including laundry additive ~ . - and
;-- suitable for use in the ~ of stained fabrics and machine
Ji l;-WCL~I-;-~, "
When formulated as ~ suitable for use in a machine washing method, eg:
machine laundry and machine J;~ methods, the ..- ~ of the invention
preferably contain one or more additional detergent ~ r ' selected from
c~ rt~r~tc builders, heavy metal ion --I organic polymeric Comro~n~lc,
suds :~U~IQ~UI:~ lime soap ~'-r ', soil suspension and anti~ u~;i;u,. agents
and corrosion inhibitors. Laundry: . can also contain, as additional
detergent . r - softening agents.
The detergent . - of the invention may contain as an optional detergentcomponent a surfactant selected from anionic, cationic, nonionic ampholytic,
~mrhf~tf nf and ~w;~t~.;u..;~ surfactants and mixtures thereof.
The surfactant is typically present at a level of from 0.1% to 60% by weight. More
preferred levels of; ..~ of surfactant are from 1% to 35% by weight, most
preferably from 1~ to 20% by weight.
The surfactant is preferably formulated to be compatible w~th any enzyme cu~
present in the, . In liquid or gel ~ , the surfactant is most
preferably formulated such that it promotes, or at least does not degrade, the stability
of any enzyme in thQe < .... ,l.. ,- ~ ;.. ~
A typical listing of anionic, nonionic, ampholytic, and ~W;~t~l;Ul~;~, classes, and
speciQ of these 5~rf~r~ntc, is given in U.S.P. 3,929,678 issued to Laughlin and
Heuring on December 30, 1975. Further examples are given in "Surface Active
Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of
suitable cationic surfactants is given in U.S.P. 4,259,217 issued to Murphy on March
31, 1981.
w09s~W67 ~ ~ ~73~3 P~ 707
27
Where present, ampholytic,: ~ ' and zwitteronic surfactant are generally used
in ~ ' with one or more anionic and/or nonionic c.. ~-
~voss/2s467 21873~3 ~ u~ ~
Anionic surfactant ~
~ssentially any anionic surfactants useful for detersive purposes can be included in the
~r,."~ ;.... These can include salts (including, for example, sodium, potassium,and substituted ammonium salts such as mono-, di- and;
salts) of the anionic sulfate, sulfonate, ~bu~y' and sarcosinate 51. fqrtq~tc
Other anionic surfactants include the ' such as the acyl ' N-acyl
taurates, fatty acid amides of methyl tauride, llcyl succinates and ''
monoesters of ,'( (especially saturated and i ' C12-C18
) diesters of ' (especially saturated and, ~ C6-C14
diesters), N-acyl ~, Resin acids and ;.ydl~ O ' resin acids are also
suitable, such as rosin, I.y.ll~ O ' rosin, and resin acids and l~y; O ' resin
acids present in or derived from tallow oil.
Anionic sulfate surfactant
Anionic sulfate surfactants suitable for use herein include the linear and branched
primary alhyl sulfates, alkyl ~ u~.y r ' , fatty oleyl glycerol sulfates, alkyl phenol
ethylene oxide ether sulfates, the Cs-C17 acyl-N-(cl-c4 alkyl) amd -N-(C1-C2
I~y~lu~y~lhyl) glucamine sulfates, and sulfates of alk~ùly~ such as the
sulfates of alhyl~lyol~l~ùs;dl: (the nonionic r ' ~ r I being described
herein).
Alkyl t~tllu~y Ir surfactants are preferably selected from the group consisting of
the C6-C1g alkyl sulfates which have been c~.u..y' ' with from about 0.5 to about
20 moles of etbylene oxide per molecule. More preferably, tne alkyl t;~l~w~y r
surfactant is a C6-C1g alkyl sulfate which has been t;Lllu~y' ' with from about 0.5
to about 20, preferably from about 0.5 to about 5, moles of ethylene oxide per
molecule.
Anirmi~ sulfonate cl~rfq~tqrlt
Anionic sulfonate surfactants suitable for use herein include the salts of Cs-C20
linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary
alkane sulfonates, C6-C24 olefin sulfonates, sulfonated poly~l,ù7.yli,, acids, alkyl
_ _ _ . .... . . _ .. .. . _ .. ... . . . .
wog5n8467 2 1 87303 1 11. . ~u~
glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and
any mixtures thereof.
A ~ ~I t~ S~f~
~nionic w~u,-.~' surfactants suitable for use herein include the alkyl ethoxy
wbu,~' , the alkyl polyethoxy ~ul~wbu~ t~ surfactants and the soaps ('alkyl
carboxyls'), especially certain secondary soaps as described herein.
Preferred alkyl ethoxy w~u~y' for use herein include those with the formula
RO(CH2CH20)x CH2COO-M+ wherein R is a C6 to Clg alkyl group, x ranges from
O to 10, and the ethoxylate J;~ ;n is such that, on a weight basis, the amount of
material where x is O is less than about 20 %, and the amount of material where x is
greater than 7, is less than about 25 %, the average x is from about 2 to 4 when the
average R is C13 or less, and the average x is from about 3 to 10 when the average R
is greater than C13, and M is a cation, preferably chosen from alkali metal, alkaline
earth metal,: . mono-, di-, and tri-; ' ~' ~ . most preferably
from sodium, potassium, and mixtures thereof with I I ions. The
preferred alkyl ethoxy wI,u,.~' are those where R is a C12 to C1g alkyl group,
Alkyl PUI~ UAY l~uly~b~J~' surfactants suitable for use herein include those
having the formula RO-(CHRl-CHR2-0)-R3 wherein R is a C6 to C1g alkyl group, x
is from I to 25, Rl and R2 are sdected from the group consisting of hydrogen,
methyl acid radical, succinic acid radical, llyJlU~ DUC~;.,iC acid radical, and mixtures
thereof, wherein at least one Rl or R2 is a succinic acid radical or I~JIu~
acid radical, and R3 is selected from the group consisting of hydrogen, substituted or
d~uwbu~ having between I and 8 carbon atoms, and mixtures
thereof.
~!!ninnir 5.~nn~ n~ ~lm'qnt~nt
Preferred soap surfactants are secondary soap surfactants which contain a carboxyl
unit connected to a secondary carbon. The secondary carbon can be in a ring
structure, e.g. as in p-octyl benwic acid, or as in alkyl-substituted cyclohexylc~l,u,.~Lt~D. The secondary soap surfactants should preferably contain no ether
linkages, no ester linkages and no hydroxyl groups. There should preferably be no
nitrogen atoms in the head-group ~ portion). The secondary soap
W095/28467 2 ~ ~7~D3
surfactants usually contain 11-15 total carbon atoms, although slightly more (e.g., up
to 16) can be tolerated, e.g. p-octyl benzoic acid.
The following general structures further illustrate some of the preferred secondary
soap surfactants:
A. A highly preferred class of secondary soaps comprises the secondary carboxyl
materials of the formula R3 CH(R4)CooM, wherein R3 is CH3(CH2)x and
R4 is CH3(CH2)y, wherein y can be O or an integer from I to 4, x is an integer
from 4 to 10 and the sum of (x + y) is 6-10, preferably 7-9, most preferably
8.
. Another preferred class of secondary soaps comprises those carboxyl
r ~ wherein the carboxyl substituent is on a ring II~YdIV~b~I unit,
i.e., secondary soaps of the formula R5-R6-CooM, wherein R5 is C7-C10,
preferably C8-C9, alkyl or alkenyl and R6 is a ring structure, such as benzene,
and ~J~ 1~ ' - (Note: R5 can be in the ortho, meta or para
position relative to the carboxyl on the ring.)
C. Still another preferred class of secondary soaps comprises secondary carboxyl --r-- ' of the formula CH3(CHR)k-(CH2)m-(CHR)n-
CH(COOM)(CHR)o~(CH2)p~(CHR)q~CH3~ wherein each R is C1-C4 alkyl,
wherein k, n, o, q are integers in the range of 0-8, provided that the total
number of carbon atoms (including the ~bv~y' ) is in the range of 10 to
18.
In each of the above forrnulas A, B and C, the species M can be any suitable,
especially water- ' ' ' ~ counterion.
Especially preferred secondary soap surfactants for use herein are water-solublemembers selected from the group consisting of the water-soluble salts of 2-methyl- 1-
undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-
octanoic acid and 2-pentyl-1-heptanoic acid.
Al~li mPr~l sarcosinate surfactant
w0 9s/28467 2 ~ ~ 7 3 ~ ~ r~l,u~ ~u~
31
Other suitable anionic surfactants are the alkali metal ~, of formula R-CON
~Rl) CH2 COOM, wherein R is a Cs-Cl7 linear or branched alkyl or alkenyl group,
Rl is a Cl-C4 alkyl group and M is an alkali metal ion. Preferred examples are the
myristyl and oleyl methyl in the form of their sodium salts.
Nonionic surfacta~t
Essentially any anionic surfactants useful for detersive purposes can be included in the
Exemplary, non-limiting classes of useful nonionic surfactants are listed
below.
Nonionic ~ol~ dluAy fatty acid amide c~rfact~Lt
Pol~hydlu~.y fatty acid amides suitable for use herein are those having the structural
formula R2CONRlZ wherein: Rl is H, C1-C4 h~dlu~l~l~ 2-hydroxy ethyl, 2-
hydroxy propyl, or a mixture thereof, preferable Cl-C4 alkyl, more preferably Cl or
C2 alkyl, most preferably Cl alkyl (i-e., methyl); and R2 is a Cs-C31 II.YdIU~IJI~
preferably straight-chain Cs-C1g alkyl or alkenyl, more preferably straight-chain Cg-
C17 alkyl or alkenyl, most preferably straight-chain C 1 1-Cl7 alkyl or alkenyl, or
mixture thereof; and Z is a polyh~dlu~-yh~Jlu~ll.yl having a linear II.rdlU~llb.~l chain
with at least 3 hydroxyls directly connected to the chain, or an " ~' ' derivative
(preferably uLI.u,~' ' or ~u.u~ ' ' I) thereof. Z preferably will be derived from a
reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.
Nonionic ~u ~ , of alkyl ~henols
The pol~ llyl~ , pclyl,lu~Jyl~n~, and polybuL~ oxide ' of alkyl
phenols are suitable for use herein. In general, the ,uul~ yl~ , oxide .
are preferred. These . . ' include the c~ products of alkyl phenols
having an alkyl group containing from about 6 to about 18 carbon atoms in either a
straight chain or branched chain, '., with the alkylene oxide.
lr~hr~l
The alkyl ethoxylate ~ ' products of aliphatic alcohols with from about l to
about 25 moles of ethylene oxide are suitable for use herein. The alkyl chain of the
aliphatic alcohol can either be straight or branched, primary or secondary, and
::
woss/2s467 21~733~3 r~l,u.. lu/ ~
enerally contains from 6 to 22 carbon atoms. Pal ' 'y preferred are the
products of alcohols haYing an alkyl group containing from 8 to 20
carbon atoms with from about 2 to about 10 moles of ethylene oxide per mole of
alcohol.
Nonionic ell~u~ /yluyv~.y~ J fatty alcohol surf~ t~nt
The cLl,u,.~' ' C6-C1g fatty alcohols and C6-CIg mixed eLllu~ Uyu~y'
fatty alcohols are suitable surfactants for use herein, ~ali ' ~y where water soluble.
Preferably the eLllu~ Lui fatty alcohols are the C1o-C1g ellluA~' ' faKy alcohols
with a degree of eLllu~ylaLion of from 3 to 50, most preferably these are the C12-C1g
;Ll~u~' ' fatty alcohols with a degree of eLllu~.~laLiull from 3 to 40. Preferably the
mixed l;Lllu~ lUIJV7~y' ' ' fatty alcohols haYe an alkyl chain length of from 10to 18 carbon atoms, a degree of eLIlu~laLiull of from 3 to 30 and a degree of
uyu~laLiu.. of from 1 to 10.
Nonionic EO/PO . ~ with pro~ylene ~lycol
The: ' products of ethylene oxide with a l~ydiuyllvb;c base formed by Khe
~.,..~1. ..- -';--.. of propylene oxide with propylene glycol are suitable for use herein.
The l~.ydluyllvlJic portion of these compounds preferably has a molecular weight of
from about 1500 to about 1800 and exhibits water insolubility. Examples of
' of this t,Ype include certain of Khe ~ 'ly-available PluronicTM
s rf~r~-~c marketed by BASF.
Nonionic E~O ~ roducts with proyylene u~d.~ h,.~ diamine adducts
The; ' products of ethylene oxide with the product resulting from the
reaction of propylene oxide and eL~ ' ' ' are suitable for use herein. The
, ' ' - moiety of these products consists of the reaction product of
eLII~ ' ~ and excess propylene oxide, and generally has a molecular weight of
from about 2500 to about 3000. Examples of this type of nonionic surfactant include
certain of the Ily available TetronicTM ~ . marketed by BASF.
Nonionic alh~l~,ol~ 8 surfactant
Suitable alkylyvly - ~ for use herein are disclosed in U.S. Patent 4,565,647,
Ilenado, issued January 21, 1986, having a llyd~ ' group containing from about
W095128467 2187303 r~l~u..
33
6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a
pol~.,.,halidc, e.g., a pù1.~61y~0~id~ yd~uyllilic group containing from about 1.3 to
about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to
about 2.7 saccharide units. Any reducing saccharide containing S or 6 carbon atoms
can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the
glucosyl moieties. (Optionally the l~dl.,' ' ~ group is attached at the 2-, 3-, 4-, etc.
positions thus giving a glucose or galactose as opposed to a glucoside or ~qlqrh~
The ' '~ bonds can be, e.g., between the one position of the additional
saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide
units.
The preferred alk~ 61~siJ~ have the formula
R20(CnH2nO)t(glycosyl)x
wherein R2 is selected from the group consisting of alkyl, alLylphenyl, l~d~u~lL~I,
hydroxyalL-ylphenyl, and mixtures thereof in which the alLyl groups contain from 10
to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3; t is from 0 to 10,
preferably 0, and X is from 1.3 to 8, preferably from 1.3 to 3, most preferably from
1.3 to 2.7. The glycosyl is preferably derived from glucose.
~nni~mir. fqtty qrir! ' ' ~llrfqr~
Fatty acid amide surfactants suitable for use herein are those having the formula:
R6CoN(R7)2 wherein R6 is an alkyl group containing from 7 to 21, preferably from9 to 17 carbon atoms and each R7 is selected from the group consisting of hydrogen,
Cl-C4 alkyl, Cl-C4 hydroxyalL-yl, and -(C2H40)XH, where x is in the range of from
I to3.
Am~hoteric ~llrfq,~tqnt
Suitable , ' - surfactants for use herein include the amine oxide surfactants and
the alkyl ~lph~bu~lic acids.
A suitable example of an alLyl ~ li. acid for use herein is Miranol(TM)C2M Conc. ' J by Miranol, Inc., Dayton, NJ.
..... . ...... . .
wos~28467 2~ ~3~3 r~l,Ov
3~
A Oxide ~ r~
Amine oxides useful herein include those compounds having the formula
R3(oR4)XNO(R5)2 wherein R3 is selected from an alhyl, hydroxyalkyl,
~,y' ' ' ~ ulJuyl and alhyl phenyl group, or mixtures thereof, containing from ~ to
26 carbon atoms, preferably 8 to 18 carbon atoms; R4 is an alhylene or
l~JIIu~y~hyl~llc group containing from 2 to 3 carbon atoms, preferably 2 carbon
atoms, or mixtures thereof; x is from O to 5, preferably from O to 3; and each R5 is
an alhyl or hydyroxyalkyl group containing from I to 3, preferably from I to 2
carbon atoms, or a ~ol~l,yl~l~c oxide group containing from 1 to 3, preferable 1,
ethylene oxide groups. The R5 groups can be attached to each other, e.g., through an
oxygen or nitrogen atom, to form a ring structure.
These amine oxide surfactants in particular include Clo-CIg aLkyl dimethyl amineoxides and Cg-CIg alkoxy ethyl ~"' ydlu~J~Lilyl amine oxides. Examples of such
materials include d;~ ylu~,Ly' - oxide, d;~,L;.jld~' oxide, bis-(2-
lly~lu~y~ l)dOd~.~' - oxide, ~ Idhle~y' ~ oxide,
yl.~ ' oxide, ' yl~_Lllylh~,A~l~Cy' oxide,
dod~y' ', u~Jyl dilY.~,Llly' o~ide, cetyl ~" ' y' oxide, stearyl
d;l~illylL~ c oxide, tallow ~;IIl.,Llly' oxide and dimethyl-2-
IIY(IIU~YU~L~C~YI~ ,c oxide. Preferred are Clo-CIg alhyl ~" ' yLIIIu~ oxide, andC10-l8 acylamido alhyl ~" ' y' oxide.
ZwilL~Iiull;c surfactant
Zwitterionic surfactants can also be i..cùl~ul.l~d into the detergent ~ C
hereof. These surfactants can be broadly described as derivatives of secondary and
tertiary amines, derivatives of h~,t~u~ secondary and tertiary amines, or
derivatives of quatemary: quaternary 1' . ' or tertiary sulfonium
Betaine and sultaine surfactants are exemplary Lw;~t~ n;~ surfactants for
use herein.
R~ surf~r~rl~ ,
The betaines useful herein are those compounds having the formula
R(R')2N+R2COO- wherein R is a C6-CIg I~Y'IIU~U~JI group, preferably a C10-C16
alhyl group or C10 16 acylamido aLlcyl group, each Rl is typically Cl-C3 alkyl,
. . .
W095128467 21873~3
preferably methyl,m and R2 is a Cl-Cs llyJ-uwbyl group, preferably a Cl-C3
alkylene group, more preferably a Cl-C2 alkylene group. Examples of suitable
betaines include coconut a~' ' r U~' ~- " yl betaine; hexadecyl dimethyl
betaine; C12 14 a.,yl~ u~.u~ ." Cg 14 a~ -,idùl.~,~yldiethyl betaule;
4tC14-16 ~ '7]-I~ JU~ C16-18
a~ ' ' Jl~ Cl2-l6 a~ J r ' ' yl betaine; tC12-16
a4~' ' ~' '( ' ' ~II",.,f...c. Preferred betaines are C12 18 ~
hexanoate and the C10-l8 a~' ~ . ~ r ~ (or ethane) dimethyl (or diethyl)
betaines. Complex betaine surfactants are also suitable for use herein.
Sultaine surf~t~.~t
The sultaines useful herein are those: , ' having the formula
(R(RI)2N+R2SO3- wherein R is a C6-Clg l~ydluwbyl group, preferably a C10-C16
alkyl group, more preferably a C12-C13 alkyl group, each Rl is typically Cl-C3
alkyl, preferably methyl, and R2 is a Cl-C6 llydluw~yl group, preferably a Cl-C3aLkylene or, prefera~71y, hydroxyalkylene group.
Am~holytic surfacta~
Ampholytic surfactants can be i~.~u.l ' irlto the detergent , herein.
These surfactants can be broadly described as aliphatic derivatives of secondary or
tertiary amines, or aliphatic derivatives of h~t~u~ ,lic secondary and tertiary amines
in which the aliphatic radical can be straight chain or branched.
('~tirmir 51'rf~rtallL
Cationic surfactants can also be used in the detergent , herein. Suitable
cationic surfactants include the quaternary surfactants selected from mono
C6-C16, preferably C6-CIo N-alkyl or alkenyl surfactants wherein the
remaining N positions are substituted by methyl, h~.l.u7.~ 1 or l~,~d~u7~ JIu~
groups.
W~tl-r-soluble h~ r com~ound
The detergent c~ of the present invention contain as a preferred optional
component a water-soluble builder compound, typically present at a level of from 1%
W095/2~'467 2187303 P~ u
36
to 80% by weight, preferably from 10% to 70% by weight, most preferably from
20% to 60% by weight of the ~
Suitable water-soluble builder compounds include the water soluble IllullUlll~,liC
~ JUA~- or their acid forms, homo or ~U~I~ .;C ,~uly~bvAJli~ acids or
their salts in which the puly~,~ul7uA~lic acid comprises at least two carboxylic radicals
separated from each other by not more that two carbon atoms, carbonates,
, borates, I ' ~. ' silicates amd mixtures of any of the foregoing.
Thel,~IJUA~' orPOIY~UAY ~ buildercanbel u~ .- oroligomericintype
although monomeric POIY~UA~ are generally preferred for reasons of cost and
r
Suitable C~UA.Y' containing one carboxy group include the water soluble salts oflactic acid, glycolic acid and ether derivatives thereof. rul.y~l.uAy' containing
two carboxy groups include the water-soluble salts of succinic acid, malonic acid,
Ay) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid
and fumaric acid, as well as the ether ~7UA~' and the sulfinyl ~I.UA~' '
roly~..uA~' contairling three carboxy groups include, in particular, water-soluble
citrates, aconitrates and c - as well as succinate derivatives such as the
uA~ ,tllyluAy ' described in British Patent No. 1,379,241,
IdcluA~ described in British Patent No. 1,389,732, and:
described in ~1~ ' ' ' Application 7205873, and the UA~JUI~.UI7UA~ materials
such as 2-oxa-1,1,3-propame ~li~7UUA~' described in British Patent No.
1,387,447.
rùl~l,uAy' containing four carboAy groups include UAy~ disclosed in
British Patent No. 1,261,829, 1,1,2,2-ethane t~t7~7JUAyl~t~,.7, 1,1,3,3-propane
~ buA~' and 1,1,2,3-propane ~t7~wbuA~' r~ly~uAJ' containing
sulfo ~ include the c--l~ ' derivatives disclosed in British Patent
Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated
pyrolysed citrates described in British Patent No. 1,439,000.
Alicyclic and ~.~t~..u."~.,li., ~ UI~17uA~' include ~ ' r ~ cis,cis,cis-
t~t7~ 7UAy ~ ~;J~ r ~ y ' , 2,3,4,5~ urul~ - cis,
cis, cis-l~tl.,~ul.uAy 2,5 ~tl~.J~IIur...a.. - cis - d;~u~uA~ 2,2,5,5-
~,dlurul~. - h~l~.~l.uA~' 1,2,3,4,5,6-heAane - II~A~UIJ~7~ and
... ... . _ . . .. .. . . .. .. ... .. .. .. . _ _ . _ . . . .
w0951~8467 2 1 8730~
~ubu~ derivatives ûf polyhydric alcûhols such as sorbitol, mannitol and
Aylitol. Aromatic L~ul~uL,v~l~ include mellitic acid, ~ylu,n~llili., acid and the
phthalic acid derivatives disclosed in British Patent No. 1,425,343.
Of the above, the preferred L~ul~ubuAy' are lI,~dIUA~ )U~ ' ' containing up
to three carboAy groups per molecule, more ~i.,ulGll~ citrates.
The parent acids of the or oligomeric ~uly~ubuA~ldt~, chdating agents or
mixtures thereof with thei~ salts, e.g. citric acid or, ~ acid miAtures are also. ' ' as useful builder .
Borate builders, as well as builders containing borate-forming materials that can
produce borate under detergent storage or wash conditions can also be used but are
not preferred at wash conditions less that about 50C, especially less than about
40C.
Examples of carbonate builders are the alkaline earth and all~ali metal ~uL
including sodium carbonate and sesqui-carbonate and miAtures thereof with ultra-fine
calcium carbonate as disclosed in German Patent Application No. 2,321,001
published on November 15, 1973.
Specific examples of water-soluble phosphate builders are the alkali metal
L-iL~l~L , , sodium, potassium and ~ r ~ ', sodiumand
potassium and a ~ .' , sodium and potassium Ul~
sodium polymeta~phosphate in which the degree of pol~.,.~,,i~liu.. ranges from about
6 to 21, and salts of phytic acid.
Suitable silicates include the water soluble sodium silicates with an SiO2: Na20 ratio
of from 1.0 to 2.8, with ratios of from 1.6 to 2.4 being preferred, and 2.û ratio being
most preferred. The silicates may be in the form of either the anhydrous salt or a
hydrated salt. Sodium silicate with an SiO2: Na20 ratio of 2.0 is the most preferred
silicate.
Silicates are preferably present in the detergent 1 in accord with the
invention at a level of from 5% to 50% by weight of the ~J-~ , more
preferably from 10% to 40% by weight.
wo g5n8467 . ~ 1 ~8 1 3 û 3 r~l,u~
38
p~rt~ y soluble or insoluble builder com~ound
The detergent ~ ;.., of the present invention may contain a partially soluble orinsoluble builder compound, typically preænt at a level of from 1% to 80% by
weight, preferably from 10% to 70% by weight, most preferably from 20% to 60%
weight of the ~ ~
Examples of partially water soluble builders include the crystalline layered silicates.
Examples of largely water insoluble builders include the sodium
Crystalline layered sodium silicates have the general formula
NaMSix02x+1 YH20
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number
from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-
0164514 and methods for their ~ are disclosed in DE-A-3417649 and DE-
A-3742043. For the purpose of the preænt invention, x in the general formula above
has a value of 2, 3 or 4 and is preferably 2. The most preferred material is o-
Na2Si20s, available from Hoechst AG as NaSKS-6.
The crystalline layered sodium silicate material is preferably present in granular
detergent 1, as a particulate in intimate admixture with a solid, water-
soluble ionisable material. The solid, water-soluble ionisable material is ælected
from organic acids, organic and inorganic acid salts and mixtures thereof.
Suitable -' ~ 1 zeolites have the unit cell formula Naz[(A102)z(SiO2)y].
XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and
x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. Theli material are in hydrated form and are preferably crystalline,
containing from 10% to 28%, more preferably from 18% to 22% wa~er in bound
form.
The -' 1 ion exchange materials can be naturally occurring materials, but
are preferably synthetically derived. Synthetic cr~vstalline r' ' ''' ' ion exchange
materials are available under the ~ .. - Zeolite A, Zeolite B, Zeolite P, Zeolite
X, Zeoilte MAP, Zeolite HS and mixtures thereof. Zeolite A has the formula
~v0 95/28467 ~ ~1 8 7 ~ u~
39
Na 12 [AIO2) 12 (si2)12] xH2O
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na86
t(Alo2)86(sio2)lo6]- 276 H2O.
Heavy metal ion se~uestrant
The detergent . , of the invention may contain as a preferred optional
component a heavy metal ion , By heavy metal ion sequestrant it is meant
herein ~ . which act to se~uester (chelate) heavy metal ions. These
C') ~ t` may also have calcium and v chelation capacity, but
,f~ lly they show selectivity to binding heavy metal ions such as irnvn,
manganese and copper.
Heavy metal ion ~ are generally present at a level of from 0.005% to 20%,
preferably from 0.1% to 10%, morepreferably from 0.25% to 7.5% and most
preferably from 0.5 % to 5 % by weight of the
Heavy metal ion . which are acidic in nature, having for example
1 ' ~ ' acid or carboxylic acid ' ' may be present either in their acid
form or as a complex/salt with a suitable counter cation such as an alkali or aLkaline
metal ion,: or substituted: ion, or any mixtures thereof.
Preferably any salts/complexes are water soluble. The molar ratio of said counter
cation to the heavy metal ion sequestrant is preferably at least 1:1.
Suitable heavy metal ion ~ for use herein include organic L
such as the amino alkylene poly (alkylene I " ' ), alkali metal ethane 1-
hydroxy ~", ' . ' and nitrilo i ' jl.,..~ I ' . '
Preferred among the above species are diethylene triainine penta (methylene
I ' . ' ), ethylene diamine tri (methylene I ' . ' ) I ' yl~ diamine
tetra (methylene ~ ) and hydroxy-ethylene 1,1 ~'ip~ . '
Other suitable heavy metal ion se~uestrant for use herein include ~ l; acid
and ~ li., acids such as ~,li.~' ' - acid,
W09s/28467 ' 21 ~î'3~3 p ", ,~,
yl~ pentacetic acid, ~ disuccinic acid, eL~I.y' ~ '
diglutaric acid, 2-llydluAy~lul~y' " ~ disuccinic acid or any salts thereof.
Especially preferred is t~ N,N'-disuccinic acid (EDDS) or the aLkalimetal, alkaline earth metal,: - or substituted ammonium salts thereof, or
mi-Atures thereof. Preferred EDDS: . ' are the free acid form and the sodium
or _ salt or complex thereof. E-Aamples of such preferred sodium salts of
EDDS include Na2EDDS and Na3EDDS. Examples of such preferred
complexes of EDDS include MgEDDS and Mg2EDDS.
Other suitable heavy metal ion ~- lu .~ for use herein are ,, ~ 1;. acid
derivatives such as 2-~ JIUA~ l diacetic acid or glyceryl iminû diacetic acid,
described in EP-A-317,542 and EP-A-399,133.
The - ' - acid-N-2-l-ydluAy~,lu~Jl sulfonic acid and aspartic acid N-~I)UA~ N-2-ll~d~uA.~ 1-3-sulfonic acid:, described in EP-A-
516,102 are also suitable herein. The 3-alanine-N,N'-diacetic acid, aspartic acid-
N,N'-diacetic acid, aspartic acid N ~ - acid and ' ~ acid
described in EP-A-509,382 are also suitable.
EP-A-476,257 describes suitable amino based ~, EP-A-510,331 describes
suitable ~ ~ derived from collagen, keratin or casein. EP-A-528,859
describes a suitable alkyl; . . . - ~1 -. . I ;. acid ~ ~ Dipicolinic acid and 2-
, 1,2,4-~.;wlbu~lic acid are alos suitable. Gl~, ' N,N'-
disuccimic acid (GADS) is also suitable.
Fnz~vme Shbilizing, System
Preferred enzyme-conhining ~J .~ nc herein may comprise from about 0.001%
to about 10%, preferably from about 0.005% to about 8%,most preferably from about
0.01% to about 6%, by weight of an enzyme shbilizing system. The enzyme
shbilizing system can be any stabilizing system which is compatible with the detersive
enzyme. Such stabilizing systems can comprise calcium ion, boric acid, propyleneglycol, short chain carboxylic acid, boronic acid, and mixtures thereof. Such
shbilizing systems can also comprise reversible enzyme inhibitors, such as reversible
protease inhibitors.
wo ss~28467 2 1 8 7 3 0 3 r~ /u7
41
The (,u~ herein may further comprise from 0 to about 10%, preferably from
about 0.01% to about 6% by weight, of chlorine bleach scavengers, added to prevent
chlorine species present in many water supplies from attacking and ~ the
enzymes, especially un~ ~kaline conditions. While chlorine levels in water may be
small, typically in the 1.~ ~ from about 0.5 ppm to about 1.75 ppm, the available
chlorine in the total volume of water that comes in contact with the enzyme during
washing is usually large; acc~ld;..~ly, enzyme stability in-use can be ~
Suitable chlorine seavenger anions are widely available, and are illustrated by salts
containing cations or sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc.such as carbamate, ascorbate, etc., organic amines such as
yl~ ~`A~ ;' acid (EDTA) or alkali metal salt thereof"
(MEA), and mixtures thereof can likewise be used. Other . u,.~,.iiu,.al scavengers
such as bisulfate, nitrate, chloride, souroes of hydrogen peroxide such as sodium
perborate Lt~ y,' , sodium perborate ' ~' and sodium p~L as
well as phosphate, condensed phosphate, aoetate, benzoate, citrate, formate, laetate,
malate, tartrate, salicylate, etc. and mixtures thereof can be used if desired.
C~ ~olvr~n~
rganic polymeric . . ' are ~ / preferred ;--~r of the detergent
in aceord with the invention. By organie polymerie eompound it is
meant essentially any polymerie organie compound eommonly used as rii~rPr~ c
and anti-lr~ and soil suspension agents in detergent ~ u
Organic polymeric compound is typically r ' in the detergent c~
of the invention at a level of from 0.1% to 30%, preferably from 0.5% to 15%, most
preferably from 1% to 10% by weight of the ~ . -
Examples of organie polymerie ~ . ' inelude the water soluble organie homo-
or co-polymeric ~UIr~UAyliC acids or their salts in which the ~l~ubuA~lic acid
comprises at least two carboxyl radicals separated from each other by not more than
two carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756.
Examples of such salts are pol~ ' of MWt 2000-5000 and their col,ul~
with maleic anhydride, sueh ~,u~l~ having a molecular weight of from 20,000 to
100,000, especially 40,000 to 80,000.
. . .
~vvoss/2s467 ~18~3~3 r~ /ul ~
42
Other suitable organic polymeric compounds include the polymers of acrylamide and
acrylate having a molecular weight of from 3,000 to 100,000, and the
acrylatetfumarate copolymers having a molecular weight of from 2,000 to 80,0û0.
The polyamino ~ r- are useful herein including those derived from aspartic
acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.
Terpolymers containing monomer units selected from maleic acid, acrylic acid,
ul~ ic acid and vinyl alcohol, l~dli ' ~.y those having an average molecular
weight of from 5,000 to 10,000 are also suitable herein.
ther organic polymeric cnmro -~lv suitable for ,UUld~iUI~ in the detergent
herein include cellulose derivatives such as methylcellulose,
~bu-~yl..~ l~llulu~ and l~llw~ h.y'
Further useful organic polymeric . are the ~JUI~ ..c glycols, ~ ulall~
those of molecular weight 1000-10000, more ~ ly 2000 to 8000 and most
preferably about 4000.
Tirn-~ ~n~ r~ nt compound
The ~ u~ of the invention may contain a lime soap dispersant compound,
which has a lime soap dispersing power (LSDP), as deflned hereinafter of no morethan 8, preferably no more than 7, most preferdbly no more than 6. The lime soapdispersant compound is preferably present at a level ûf from 0.1% to 40% by weight,
more preferably 1% to 20% by weight, most preferably from 2% to 10% by weight
of the u~
lime soap dispersant is a material that prevents the ~ l ;.... of allcali metal,
or amine salts of fatty acids by calcium or magnesium ions. A numerical
measure of the ~rf~tiv~ of a lime soap dispersant is given by the lime soap
disrersing power (LSDP) which is determined using the lime soap dispersion test as
described in an aTticle by H.C. Borghetty and C.A. Bergman, J. Am. Oil. Chem.
Soc., volume 27, pages 88-90, (1950). This lime soap dispersion test method is
widely used by r~ in this art field being referred to, for example, in the
following review articles; W.N. Linfield, Surfactant Science Series, Volume 7, p3;
W.N. Linfield, Tenside Surf. Det., Volume 27, pagesl59-161, (1990); and M.K.
. _ . . . . . _ .. . .. . .. .. .
Wogs/28467 ~ ~73~ P ~ u~
43
Nagarajan, W.F. Masler, Cosmetics and Toilet~ies, Volume 104, pages 71-73,
(1989). The LSDP is the % weight ratio of dispersing agent to sodium oleate
required to disperse the lime soap deposits formed by 0.025g of sodium oleate in30ml of water of 333ppm CaCO3 (Ca:Mg=3:2) equivalent hardness.
Surfactants having good lime soap dispersant capability will include certain amine
oxides, betaines, ~ . alkyl eLIlu~ '' and eLI-u~.y` ' alcohols.
Exemplary surfactants having a LSDP of no more than 8 for use in accord with theinvention include C16-C18 dimethyl amine oxide, C12-CIg alkyl ~Ll~u~y '' with
an average degree of ~Lllu~yl~Liull of from 1-5, p~Li~..l~l.y C12-Cls alkyl
~LIIu~ '' surfactant with a degree of ~ u~yl~LiOn of about 3 (LSDP=4), and the
C13-Cls eLllu~' ' alcohols with an average degree of eLllu~yl~Lio.~ of either 12(LSDP=6) or 30, sold under the trade names Lutensol A012 and Lutensol A030
`~t~Li~.,-y, by BASF GmbH.
Polymeric lime soap dispersants suitable for use herein are described in the article by
M.K. Nagarajan and W.F. Masler, to be found in Cosmetics and Toiletries, Volume
104, pages 71-73, (1989). Examples of such polymeric lime soap dispersants include
certain water-soluble salts of w~ly~ . . of acrylic acid"~..,lh~lyL~, acid or mixtures
thereûf, and an acrylamide or substituted ~.,ly' ' ~ where such polymers typically
have a molecular weight of from 5,000 to 20,000.
Suds suVvressing system
The detergent c~ c of the invention, when formulated for use in machinewashing , - . preferably comprise a suds . ~ system present at a
level of from 0.01% to 15%, preferably from 0.05% to 10%, most preferably from
0.1% to 5% by weight of the ~
Suitable suds ~ ; systems for use herein may comprise essentially any known
antifoam compound, including, for example silicone antifoam . ', 2-alkyl and
alcanol antifoam,
By antifoam compound it is meant herein any compound or mixtures of ~omro~ c
which act such as to depress the foaming or sudsing produced by a solution of a
detergent cc~ ~rc~ ~Li-,ul~uly in the presence of agitation of that solution.
_ . . . ... . . .. _ _ ... _ _ _ _ _ . . .
W095/28467 2:~ ~7~3 r~ ~707
44
P~iuuLuly preferred antifoam compounds for use herein are silicone antifoam
cnmro~ defined herein as any antifoam compound including a silicone
Such silicone antifoam . ~. ' also typically contain a silica r ' The
term "silicone" as used herein, and in general throughout the industry, ~ u~ a
variety of relatively high molecular weight polymers containing siloxane units and
l~ydlu~,~ul/yl group of various eypeS. Preferred silicone antifoam: , ' are the
siloxanes, p uLi~ul.uly the ~Iyd;~ ylsiloxanes having Llilnc~ ;lyl end blocking
units.
Other suitable antifoam compounds include the ~ ~u~u~yli~ fatty acids and soluble
salts thereof. These materials are described in US Patent 2,954,347, issued
September 27, 1960 to Wayne St. John. The - b~J~.ylic fatty acids, and salts
thereof, for use as suds suppressor typically have llydlu~lJ~I chains of 10 to about 24
carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the aLkali
metal salts such as sodium, potassium, and lithium salts, and: and
salts.
Other suitable antifoam ~----r ' include, for example, high molecular weight fatty
esters (e.g. fatty acid Ll;61y~.;~), fatty acid esters of monovalent a~cohols, aliphatic
Clg-C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to he~ca-
alky ' or di- to tetra alkyldiamine ' ' forrned as products of
cyanuric chloride with two or three moles of a primary or secondary amine containing
1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and l..~JIIolt~yl di-
alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.
Copolymers of ethylene oxide and propylene oxide, ~,~ui ' 'y the mixed
~ u~.y' '/~llu~ y' ' fatty alcohols with an alkyl chain length of from 10 to 16
carbon atoms, a degree of ~ u~yl,~iiull of from 3 to 30 and a degree of ~u~-~yl~liul.
of from 1 to 10, are also suitable antifoam ~ , ' for use herein.
Suitable 2-alky-alcanols antifoam ~ . ' for use herein have been described in
DE 40 21 265. The 2-alkyl-alcanols suitable for use herein consist of a C6 to C16
alkyl chain carrying a terminal hydroxy group, and said alkyl chain is substituted in
the a position by a Cl to Clo alkyl chain. Mixtures of 2-alkyl-alcanols can be used in
the ~ according to the present invention.
. , _ _ _ _
wo 95/28467 ~ 8,7,3,,~3 r~ u~
A preferred suds ~u~ ;..6 system comprises
(a) antifoam compound, preferably silicone antifoam compound, most preferably a
silicone antifoam compound comprising in
(i) poly~" ' yl siloxane, at a level of from 50% to 99%, preferably 75%to 95 % by weight of the silicone antifoam compound; and
(ii) silica, at a level of from 1% to 50%, preferably 5% to 25% by weight
of the silicone/silica antifoam compound;
wherein said silicalsilicone antifoam compound is . ' at a level of from 5%
to 50%, preferably 10% to 40% by weight;
(b) a dispersant compound, most preferably comprising a silicone glycol ra~e
copolymer with a polyu/~y~lLyl~ . content of 72-78% and an ethylene oxide to
propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10%,
preferably 1% to 10% by weight; a ~ ,uLul~ preferred silicone glycol rake
copolymer of this type is DCO544, 'Iy available from DOW
Corning under the tradename DCO544;
(c) an inert ca~ier fluid compound, most preferably comprising a C16-CIg
~II.v,.~' ' alcohol with a degree of ~ u~ Liv.l of from 5 to 50, preferably 8
to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight;
A preferred particulate suds suppressor system useful herein comprises a mixture of
an alkylated siloxane of the type h~ ùv~ disclosed and solid silica.
The solid silica can be a fumed silica, a I . ' silica or a silica, made by the gel
formation technique. The silica patticles suitable have an average particle siæ of
from 0.1 to 50 .";.,.u...~t~.~, preferably from l to 20 .-~ and a surface atea
of at least 50m2/g. These silica particles can be rendered I~Jd~u~hvb;~, by treating
them with dialkylsilyl groups and/or ~ l groups either bonded directly onto
the silica or by means of a silicone resin. It is preferred to employ a silica the
particles of which have been rendered h.~dlu~l~vb;c with dimethyl and/or trimethyl
silyl groups. A preferred patticulate antifoam compound for inclusion in the
detergent, . in accordance with the invention suitably contain an amount of
woss/2s467 ~ 7~13 ~ u~
46
silica such that the weight ratio of silica to silicone lies in the range from 1:100 to
3:10, preferably from 1:50 to 1:7.
Another suitable particulate suds ~u~ c~;..6 system is ~ I~ by a lly~
silanated (most preferably trimethyl-silanated) silica having a particle size in the range
from 10 1 to 20, and a specific surface area above 50m2/g,
intimately admixed with dimethyl silicone fluid having a molecular weight in therange from about 500 to about 200,000 at a weight ratio of silicone to silanated silica
of from about 1:1 to about 1:2.
A highly preferred particulate suds ~ g system is described in EP-A-0210731
and comprises a silicone antifoam compound and an organic carrier material having a
melting point in the range 50C to 85C, wherein the organic carrier material
comprises a monoester of glycerol and a fatty acid having a carbon chain containing
from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate suds
~u~ , systems wherein the organic carrier material is a fatty acid or alcohol
having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof,
with a melting point of from 45C to 80C.
Other highly preferred particulate suds ~ g systems are described in
copending European Application 91870007.1 in the name of the Procter and Gamble
Company which systems comprise silicone antifoam compound, a carrier material, an
organic coating material and glycerol at a weight ratio of glycerol: silicone antifoam
compound of 1:2 to 3:1. Copending European Application 91201342.0 also discloseshighly preferred ~ticulate suds , r ' 1~ systems comprising silicone antifoam
compound, a carrier material, an organic coating material and crystalline or
amorphous s ~ t~ at a weight ratio of ~ silicone antifoam
compound of 1:3 to 3:1. The preferred carrrier material in both of the above
described highly preferred granular suds controlling agents is starch.
n exemplary particulate suds ~ g system for use herein is a particulate
-~ r t, made by an ~ process, comprising in
,, ,.. ,1 .; .... ;....
(i) from 5% to 30%, preferably from 8% to 15% by weight of the component of silicone antifoam compound, preferably comprising in ~,O
poly~' ' yl siloxane and silica;
..... .. _ . _ . ..... . ......... ... ... .........
w095/28467 21 873~3 ~ u~ u~
47
(ii) from 50% to 90%, preferably from 60% to 80% by weight of the ~ r t~
of carrier material, preferably starch;
(iii) from 5% to 30%, preferably from 10% to 20% by weight of the component of
lgg' binder compound, where herein such compound can be any
compound, or mixtures thereof typically employed as binders for
__' most preferably said ~g' binder compound comprises a
C16-C1g ~ UAy' ' alcohol with a degree of ell.uA~ll,ion of from 50 to 100;
and
(iv) from 2% to 15%, preferably from 3% to 10%, by weight of C12-C22
I~J~u~ ~ fatty acid.
Polymeric dye transfer inhibitin~ a~ents
The detergent ~ -- "~ herein may also comprise from 0.01% to 10 %,
preferably from 0.05% to 0.5 % by weight of polymeric dye transfer inhibiting agents.
The polymeric dye transfer inhibiting agents are preferably selected from polyamine
N-oxide polymers, ~u~ulylll. ., of N .;~yl~yllulidO.I~ and N-v ylill.;J~I~,
polyv;..yl~,ylluliJo.~,ly...~l~ or ~ ' thereof.
a) Polyamine N-oxide volymers
Polyamine N-oxide polymers suitable for use herein contain units having the
following structure formula:
(I) I
R
wherein P is a poly ' ' unit, whereto the R-N-O group can be attached to, or
wherein the R-N-O group forms part of the ~71yIll~li~bl~ unit or a ~ of
both.
WO95/28467 7 1 873Q3 P~
48
00 0
Il 11 11
A is NC, CO, C, -O-, -S-, -N-; x is O or1;
R are aliphatic, ~LI,v,~' ' aliphatics, aromaùc, I.~ .,lic or alicyclic groups or
any . ' thereof whereto the nitrogen of the N-O group can be attached or
wherein the nitrogen of the N-O group is part of these groups.
The N-O group can be ,c, ' by the following general
structures:
o
O
(R~) X-N-tR2)Y
IR3)Z or --N-(R1)x
wherein Rl, R2, and R3 are aliphatic groups, aromatic, l~,t~u,~ or alicyclic
groups or ' thereof, x or/and y or/and z is 0 or I and wherein the
rlitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group
forms part of these groups~ The N-O group can be part of the pol~ ' ' unit (P)
or can be attached to the polymeric backbone or a .~ ;.... of both~
Suitable polyamine N-oxides wherein the N-O group forms part of the pol~ l;~lc
unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic,alicyclic or l,~ ,lic groups~ One class of said polyamine N-oxides comprises thegroup of polyamine N-oxldes wherein the nitrogen of the N-O group forms part of the
R-group~ Preferred polyarnine N-oxides are those wherein R is a l~ ,lic group
such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and
derivatives thereof.
Another class of said polyamine N-oxides comprises the group of polyamine N-oxides
wherein the nitrogen of the N-O group is attached to the R-group~
Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O groupis attached to the ~uly ' '~ unit.
,,, ,, , _ . , ,, . _ . _ ,, .. . , . ... ,,, . , . . ,, ,, , _ _ _
W095128467 21~3~ r~ ,u,
49
Preferrcd class of these polyamine N-oxides are the polyamine N-oxides having the
general formula (I) wherein R is an arn~ ir ll ~ u~,y~,lic or alicyclic groups wherein
the nitrogen of the N-0 functional group is part of said R group. Examples of these
classes are polyamine oxides wherein R is a ~..,t~,u."~.,li~. compound such as pyrridine,
pyrrole, imidazole and derivatives thereof.
Another preferred class of polyamine N-oxides are the polyamine oxides having the
general formula (I) wherein R are aromatic, h~,t~lu~ , or alicyclic groups wherein
the nitrogen of the N-0 functional group is attached to said R groups. ~xamples of
these classes are polyamine oxides wherein R groups can be aromatic such as phenyl.
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, puly ' pul,~a~ ' ' and mixturesthereof.
The amine N-oxide polymers of the present invention typically have a ratio of amine
to the amine N-oxide of 10:1 to 1:1000000. However the amount of amine oxide
groups present in the polyamine oxide polymer can be varied by 4~
Cu~l~ a~h~ll or by au~l~, degree of N-oxidation. Preferably, the ratio of
amine to amine N-oxide is from 2:3 to 1:1000000. More preferably from 1:4 to
l:lOOOOOO,mostpreferablyfroml:7tol:1000000.Thepolymersoftheprcsent
invention actually encompass random or block ~u~l~ where one monomer type
is an amine N-oxide and the other monomer type is either an amine N-oxide or not.
Tne amine oxide unit of the polyamine N-oxides has a PKa < lû, preferably PKa <
~, more preferred PKa < 6.
The polyamine o~ides can be obtained in almost any degree of ~Ig The
degree of pol.~ a~iùn is not critical provided the material has the desired water-
solubility and ~, , ' , power. Typically, the average molecular weight is
within the range of 500 to 1000,000; preferably from 1,000 to 50,000, more
preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.
b) Co~olyr-rs of N-vi~ v~ r ' N-vinylim~zQ~
Wo9sl2846~ 73~3 ~ u~
so
Preferred polymers for use herein may comprise a polymer selected from N-
vinylimidazole N-v...~ ..ulidu~,~, cu~ul,y~ wherein said polymer has an average
molccular weight range from 5,000 to 50,000 more preferably from 8,000 to 30,000,
most preferably from 10,000 to 20,000. The preferred N ~;.,~' ' '- N-
V;~ cu~l~ have a molar stio of N--v ~I;...;JdLul~ to N-
vil~ ulidu~c from I to 0.2, more preferably from 0.8 to 0.3, most preferably
fromO.6toO.4 .
c~ rVI~v;..Jl~yllul;du....
The detergent ~ herein may also utilize ~ul~v;~ PVP"
having an average molecular weight of from 2,500 to 400,000, preferably from 5,000
to 200,000, more preferably from 5,000 to 50,000, and most preferably from 5,000to 15,000. Suitable ~ v;~ ,y.-, "' are ~ .,;ally vailable from ISP
ion New York, NY and Montrcal, Canada under the product names PVP K-
15 (viscosity molecular weight of 10,000), PVP K-30 (average molccular wPight of40,000), PVP K-60 (average molccular weight of 160,000), and PVP K-90 (average
molecular weight of 360,000). PVP K-15 is also available from ISP l'~ n
Other suitable ~ulJv...~ ..ul;du.1~ which are . ly available from BASF
CoopP~inn include Sokalan HP 165 and Sokalan HP 12.
r~ ulid~ may be r ' ~ in the detergent ~ . herein at a
level of from 0.01% to 5% by weight of the detergent, preferably from 0.05% to 3%
by weight, and more preferably from 0.1% to 2% by weight. The amount of
POI~V;I~ I ' ' delivered in the wash solution is preferably from 0.5 ppm to 250
ppm, preferably from 2.5 ppm to 150 ppm, more preferably from 5 ppm to 100 ppm.
d) r~ lu-~ ul;du--~
The detergent ~ - herein may also utilize ~1~ v;ll,~l- .~ ~ ,- .li~l- - - - as
polymeric dye transfer inhibiting agents. Said polyvi~lv~ . have an average
molecular weight of from 2,500 to 400,000, preferably from 5,000 to 200,000, more
preferably from 5,000 to 50,000, and most preferably from 5,000 to 15,000.
The amount of ~ol~ v ;l. ~1~ ' '( ~ldt~ in the detergent ~ c may
be from 0.01% to 5% by weight, preferably from 0.05% to 3% by weight, and more
preferably from 0.1% to 2% by weight. The amount of pul~
.. . . . _ . .. .. .. . ~ . .. _ _
wossi28467 ~1 8~73~ /u~ ~u~
51
delivered in the wash solution is typically from 0.5 ppm to 250 ppm, preferably from
2.5 ppm to 150 ppm, more preferably from 5 ppm to 100 ppm.
e) r~lyv;llylilllid~ul~
The detergent ~ , herein may also utili2e ~Iy v;~ylil~;d~l~ as polymeric
dye transfer inhibiting agent. Said polyv;ll.~' ' ' preferably have an average
molecular weight of from 2,500 to 400,000, more preferably from 5,000 to 50,000,and most preferably from 5,000 to 15,000.
The amount of polyi yli~lid~l~ i..~.~t~ in the detergent cc~ may be
from 0.01% to 5% by weight, preferably from 0.05% to 3% by weight, and more
preferably from 0.1% to 2% by weight. The amount of ~Iyvi~ id~ delivered
in the wash solution is from 0.5 ppm to 250 ppm, preferably from 2.5 ppm to 150
ppm, more preferably from 5 ppm to 100 ppm.
Optical bripb~
The detergent: . herein may also optionally cont~in from about 0.005% to
5% by weight of certain typPs of l~yJI~ optical brighteners which also provide adye transfer inhibition action. If used, the ~ c herein will preferably
comprise from about 0.01% to 1% by weight of such optical bri~ht~nprc
The hydrophilic optical brighteners useful in the present invention are those having
the structural formula:
Rl R2
~ON~ IN~C=C~NI ~N
R2 SO3M SO3M R
wherein Rl is selected from anilino, N-2-bis-l-ydlu/~ hJl and NH-2-l~ydlu~
R2 is selected from N-2-bis-l.yd.u~"Li.yl, N-2-l~ydl~ yl N ' y' ~,
morphilino, chloro and amino; and M is a salt-forming cation such as sodium or
potassium.
Wo9!7/28467 ` ~ 3 P~ u~
~3
When in the above formula, Rl is anilino, R2 is N-2-7~;~ h~d~u~_L.~yl and M is acation such as sodium, the brightener is 4,4' ,-bis[(4-anilino-6-7~N-2-7J;s ~ u~ L.~yl)-
s-t7~iazine-2-yl)amino]-2,2'-~till ~ -- 7~ r.",:~ acid and disodium salt. Tbis particular
brightener species is ~,;ally marketed under the tradename Tinopa7i-UNPA-GX
by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred l,~_.u~,l.;lic optical
brightener useful in the detergent; , herein.
When in the above formula, Rl is anilino, R2 is N-2-1,~_1u,~ l N 2~
and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-
IlyLlv~vLll~l-N-ll~ ;llv)-s-t7iazine-2-yl)amino]2~2~-cti~ lrll :~acid
disodium sa7~t. This particular brightener species is ~ ~;ally mar~eted under the
tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a cation such as
sodium, the brightener is 4,4'-bis[(4-anilino-6-.1,ùll ' " s triazine-2-yl)amino]2,2'-
:till ... ,. ~7, ~, .l r~ ..., acid, sodium salt. This particular brightener species is~o..,..~ lly marketec under the tradename Tinopa7i AMS-GX by Ciba Geigy
Corporation.
The specific optica7i brightener species selected for use in the present invention
provide especially effective dye transfer inhibition pe.rullll~l.,_ benefits when used in
with the selected polymeric dye transfer inhibiting agents I ` r e
described. The .~ ;-... of such selected polymeric materials (e.g., PVNO and/or
PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal
SBM-GX and/or Tinopal AMS-GX) provides - _ ~ -ly better dye transfer
inhibition in aqueous wash solutions than does either of these two detergent
when used alûne. 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 ~rrlc;.,.,L . The exhaustion coef~lcient is in
general as the ratio of a) the bri~htener materiaL deposited on fabric to b) the initial
brightener in the wash liquor. r v~ with relatively high
exhaustion . ~ -~ are the mo$ suitable for inhibiting dye transfer in the context
of the present invention.
. _ . .. . _ . .
wo95/28467 21873~3 r~ ul
s3
f course, it will be ~ ' that other, cu~ optical brightener types of
can optionally be used in the present ~ I to provide . u..~. I
fabric ~ benefits, rather than a true dye transfer inhibiting effect. Such
usage is c~..v~.-Liu.lal and well-known to detergent r ~ -
Sof~
Fabric softening agents can also be i~lcull ' into laundry detergentin accordance with the present invention. These agents may be inorganic or organic
in type. Inorganic softening agents are ~.... jll;ri.~.i by the smectite clays disclosed in
GB-A-I 400 898. Organic fabric softening agents include the water insoluble tertiary
amines as disclosed in GB-A-I 514 276 and EP-B-0 011 340.
Levels of smectite clay are normally in the range from 5 % to 15 %, more preferably
from 8% to 12% by weight, with the material being added as a dry mixed componentto the remainder of the & ' Organic fabric softening agents such as the
water-insoluble tertiary amines or dilong chain amide materials are i .,,lu ,.. ~ l at
levels of from 0.5% to 5% by weight, normally from 1% to 3% by weight, whilst the
high molecular weight pUl.~Ll.~- .lc oxide materials and the water soluble cationic
materialsareaddedatlevelsoffromO.1% to2%, normallyfromO.15% to 1.5% by
weight.
OthP-o~ on~l inpr~
Other optional ingredients suitable for inclusion in the ~ of the invention
include perfumes, colours and filler salts, with sodium sulfate being a preferred filler
woss/28467 2187303 r~ ul
s4
FQrm of the ~u~ v~,7
The detergent c~ ; "-c of the invention can be formulated in any desirable form
such as powders, granulates, pastes, liquids and gels. The ~v ~ are
preferably not in tablet-form. Most preferably, the .u ~lr.~ . are in granular
form.
T. ' ~v.r~vva l;v ~
The detergent ~v ~ c of the present invention may be formulated as liquid
detergent f ~ '- ' ;"" ` Such liquid detergent . typically cQmprise from
94% to 35% by weight, preferably from 90% to 40% by weight, most preferably
from 80% to 50% by weight of a liquid catrier, e.g., water, preferably a mixture of
water and organic solvent.
Gel .
The detergent ... ~ ;.--, of the present invention may also be in the forrn of gels.
Such ~ c are typically formulated with polyakenyl polyether having a
molecular weight of from about 750,000 to about 4,^00,000.
Solid Sv~ cn;~ivl~i _
The detergent .v~ ;.., of the invention are preferably in the form of solids, such
as powders and granules.
The particle size of the . . of granular ~ in accordance with the
invention should preferably be such that no more that 5 % of particles are greater than
1.4mm in diameter and not more than 5% of particles are less than 0.15mm in
diameter.
The bulk density of granular detergent ""--~i - ';" - in accordance with the present
invention typically have a bulk density of at least 450 g/litre, more usually at least
600 g/litre and more preferably from 650 g/litre to 12vO g/litre.
Bulk density is measured by means of a simple funnel and cup device consisting of a
conical funnel moulded rigidly on a base and provided with a flap valve at its lower
_ . .. . . .. . .. . . . _
wo gs/28467 2 1 8 7 3 0 3 r~l"~ ~u~
ss
extremity to allow the contents of the funnel to be emptied into an axially aligned
cylindrial cup disposed below the funnel. The funnel is 130 mm and 40 mm at its
respective upper and lower extremities. It is mounted so that the lower extremity is
140 mm above the upper surface of the base. The cup has an overa,l height of 90
mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal
volume is 500 ml.
To carry out a t, the funnel is filled with powder by hand pouring, theflap valve is opened and powder allowed to overf~ll the cup. The filled cup is
removed from the frame and excess powder removed from the cup by passing a
straight edged implement e.g. a knife, across its upper edge. The filled cup is then
weighed and the value obt~ined for the weight of powder doubled to provide the bulk
density in g/litre. Replicate I are made a required.
prn~pccpc e~u~ com~Si~QPs
Ln general, granular detergent ~ - in accordance with the present invention
can be made via a variety of methods including dry mixing, spray drying,
-~ccln~r ~ and
W;lchin~ Pth~l~lc
The ~ of the invention may be used in essentially any washing or cleaning
method, including machine laundry and d;,llwa,l~ methods.
',.._ h "~ P~h~
A preferr~d machine .li~hw~h...~ method comprises treating soiled articles selected
from crocker,v, glassware, hollowware and cutlery and mixtures thereof, with an
aqueous liquid having dissolved or dispensed therein an effective amount of a machine
.1;,1.... ' ~ . , in accord with the invention. By an effective amount of the
machine d;,h~ it is typically meant from 8g to 60g of product
dissolved or dispersed in a wash solution of volume from 3 to 10 litres, as are typical
product dosages and wash solution volumes commonly employed in ~u
machine di,l... ' _ methods.
~hine I ~rY methods
wo sSr2s467 2 7 ~ ?3 r~ 07
s6
Machine laundry methods herein wmprise treating soiled laundry with an aqueous
wash solution in a washing machine having dissolved or dispensed therein an effective
amount of a machine laundry detergent c~ in accord with the invention. The
detergent can be adderl to the wash solution either via the dispenser drawer of the
washing machine or by a dispensing device. By an effective arnount of the detergent
,.... it is typically meant from 40g to 300g of product dissolved or dispersed
in a wash solution of volume from 5 to 65 litres, as are typical product dosages and
wash solution volumes commonly employed im w~ ...iu~l~l machine laundry
methods.
In a preferred washing method herein a dispensing device wntaining an effective
amount of detergent product is introduced into the drum of a, preferably front-
loading, washing machine before the: of the wash cycle.
The dispensing device is a container for the detergent product which is used to deliver
the product directly into the drum of the washing machine. Its volume capacity
should be such as to be able to contain sufficient detergent product as would normally
be used in the washing method.
Once the washing machine has been loaded with laundry the dispensing device
containing the detergent product is placed inside the drum. At the . of
the wash cycle of the washing machine water is introduced into the drum and the
drum periodically rotates. The design of the dispensing device should be such that it
permits of the dry detergent product but then allows release of this
product during the wash cycle in response to its agitation as the drum rotates and also
as a result of its immersion in the wash water.
To allow for release of the detergent product during the wash the device may possess
a number of openings through which the product may pass. Alternatively, the device
may be made of a material which is permeable tû liquid but ,~ lr to the solid
product, which wiU allow release of dissolved product. Preferably, the detergentproduct will be rapidly released at the start of the wash cycle thereby providing
transient localised high ~ of: . such as water-soluble builder
and heavy metal ion sequestrant ~ . in the drum of the washing machine at
this stage of the wash cycle.
. .
woss/2s467 21 8~3~
s7
Preferred dispensing devices are reusable and are designed in such a way that
container integrity is maintained in both the dry state and during the wash cycle.
Especially preferred dispensing devices for use in accord with the invention have been
described in the following patents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-
0201376, EP-A-0288345 and EP-A-0288346. An article by J.Bland published in
r~ Chemist, November 1989, pages 41-46 also describes especially
preferred dispensing devices for use with granular laundry products which are of a
type commonly know as the agranulette~.
Especially preferred dispensing devices are disclosed in European Patent Application
Publication Nos. 0343069 & 0343070. The latter Application discloses a device
comprising a flexible sheath in the form of a bag extending from a support ring
defining an orifice, the orifice being adapted to admit to the bag sufficient product for
one washing cycle in a washing process. A portion of the washing medium flows
through the orifice into the bag, dissolves the product, and the solution then passes
outwardly through the orifice into the washing medium. The support ring is provided
with a masking: ~ to prevent egress of wetted, u~J;~ l, product, this
typically comprising radially extending walls extending from a central
boss in ~ spoked wheel . '1, or a similar structure in which the walls have a
helical form.
In the detergent ~ . the ~u~ ' component i~lf liri. ~ have the
following meanings:
XYAS : Sodium Clx - Cly alkyl sulfate
24EY : A C12 14 l~ lly Iinear primary alcohol
condensed with an average of Y moles of ethylene
oxide
XYEZ : A Clx - Cly ~ , linear primary alcohol
condensed with an average of Z moles of ethylene
oxide
XYEZS : C1x - C1y sodium alkyl sulfate condensed with an
average of Z moles of ethylene oxide per mole
2 ~ 87303
WO 95/28467 P~ u
58
TFAA : C16-CIg alkyl N-methyl glucamide.
Silicate : Amorphous Scdium Silicate (SiO2:Na2O ratio = 2.0)
NaSKS-6 : Crystalline layered silicate of formula ~-Na2Si2Os
Carbonate : ADhydrous sodium carboDate
roly~L~uA~' : Copolymer of 1:4 ~ ;c/a.,.~Lc acid, average
molecular weight about ~0,000
Zeolite A : Hydrated Sodium ~1 1 ' of formula
Nal2(AlO2SiO2)12. 27H20 having a primary particle
size in the raDge from I to 10 ~ ,lu-ll.,t~.a
Citrate : Tri-sodium citrate dihydrate
r~,l~L (fastrelease : Anhydrous sodium ~ . L bleach of empirical
particle) formula 2Na2CO3.3H2O2 coated with a mixed salt of
formula Na2SO4.n.Na2CO3 where n is 0.29 and
where the weight ratio of p~.~L to mixed salt is
39: 1
r~ (slow release : Anhydrous sodium ~.~L bleach coatcd with a
particle) coating of sodium silicate (Si2O:Na2O ratio = 2:1) at
a weight ratio of ~l~uL to sodium silicate of
39:1
TAED : T~h~e~yl~
TAED (slow release : Particle formed by s",L;I~ g TAED with citric
particle) acid amd ~I~ ,.. , glycol (PEG) of Mw=4,000
with a wdght ratio of . of TAED:citric
acid:P~G of 75:10:15, coated with an exterDal coating
of citric acid at a weight ratio of ~g~lr-- citric
acid coating of 95:5.
, . . .
w095/28467 2~873~3 ~ u~
ss
Benzoyl Caprolactam (slow : Particle formed by ~ g benzoyl ~lul~uul-
release particle) (BzCI) with citric acid and ~I~ yl~ n~ glycol (PEG)
of Mw=4,000, with a weight ratio of ~ ~i of
BzCl:citric acid:PEG of 63:21:16, coated with an
external coating of citric acid at a weight ratio of
acid coating of 95:5
TAED (fast release : Particle formed by a~ TAED with partially
particle) neutralised l uly~bw~y' at a ratiû of
TAED.pf~ly~ubu~yl~ of 93:7, coated with an
external coating of poly~u,.~' at a weight ratio of
"~, . of 96:4
EDDS (fast release : Particle formed by spray-drying EDDS with MgS04 at
particle) a weight ratio of 26:74
Protease : Proteolytic enzyme sold under the tradename Savinase
by Novo Industries A/S with an activity of 13
KNPU/g.
Amylase : Amylolytic enzyme sold under the tradename
Termamyl 6ûT by Novo Industries A/S with an activity
of 300 KNU/g
Cellulase : Cellulosic enzyme sold by Novo Industries A/S with an
activity of 1000 CEVU/g
Lipase : Lipolytic enzyme sold under the tradename Lipolase by
Novo Industries A/S with an activity of 165 KLU/g
CMC : Sodium ~bu~ l cellulose
HEDP : 1,1 I~,~dlW~ ' ' acid
LDDS : ~ ' -N, N'- disuccinicacid, [S,S] isomer
in the form of the sodium salt.
wo ss/2s467 2 ~ ~ 7 3 ~ 3 ~ u~
pVNO : Poly (4~ G) N-oxide copolymerof
vi.~ ..;JdAul~ and v;~ ul;du.,~ having an average
molecular weight of 10,000.
ranular Suds Suppressor : 12% .~ ;li~, 18% stearyl alcohol,70% starch in
granular form
Nonionic C13-C1s mixed.,ll-u,~ u~y' ' fatty
alcohol with an average degree of G~huA~ldi~ of 3.8
and an average degrGe of ,ululJu~laLiua of 4.5 sold
under the tradename Plurafac LF404 by BASF Gmbh
(low foaming)
~: I : Sodium ' (SiO2:Na2Oratio = 1.0)
Phosphate : Sodium Lli~JUI~
480N : Random copolymer of 3:7 dc. ylic/l.l~ L., aeid,
average molecular weight about 3,500
PBl : Anydrous sodium perborate ' ~, - in
eompacted particulate form to retard release of
hydrogen peroxide
Cationie laetam . : Cationie peroxyacid bleaeh precursor salt of trialkyl
ammonium methylene Cs-alkyl c~ ul~.)) with
tosylate
DETPMP : Diethylene triamine penta (methylene .~' . '
acid), marketed by Monsanto under tae tradename
Dequest 2060
Bismuth nitrate : Bismuth nitrate salt
Paraffin : Paraffln oil sold under the tradename Winog 70 by
~.. . ..
woss/2s467 21 ~7303 P~ u~
61
BSA : Amylolytic enzyme sold under the tradename LE~17 by
Novo Industries A/S (approx 1% enzyme activity)
Sulphate : Anhydrous sodium sulphate.
pH : Measured as a 1% solution in distilled water at 20C.
wo 95/28467 ~ 1 8 7 3 ~ 3 r~l,~J ' ,
62
F ' 1
The following laundry detergent ~ Y.~ were prepared values being expressed
as ~..... ~ by weight of the ~ .llc ~ , ' A is a W~ Jalali~
B to E are in accord with the invention:
A B C D E
45AS/25AS (3:1) 9.1 9.1 9.1 9.1 7.0
35AE3S 2.3 2.3 2.3 2.3 4.0
24E5 4.5 4.5 4.5 4.5 3.0
TFAA 2.0 2.0 2.0 2.0 2.0
Zeolite A 13.2 13.2 13.2 13.2 15.0
Na SKS-61citric acid 15.6 15.6 15.6 15.6 13.0
(79:21)
Carbonate 7.6 7.6 7.6 7.6 8.0
TAED (fast release 6.3 - - - -
particle)
TAED (slow release - 5.0 - 2.3 5.0
particle)
Benzoyl Caprolactarn - - 5.0 2.7
(slow release particle)
re.~l,o.. a~ (fast 22.5 - - 22.5
release particle)
WO 95/28467 ~ ~ -
~ ~73D3 ~ ~u~
63
r~ ut (slow - 22.5 22.5
release particle)
PBI - - - - 16.0
DETPMP 0.5 0.8 - - -
EDDS (fastrelease - - 0.3 0.75 0.5
particle)
Protease 0.55 1.27 0.55 1.27 1.3
Lipase 0.15 0.15 0.15 0.15 0.2
Cellulase 0.28 0.28 0.28 0.28 0.3
Amylase 0.27 0.27 0.27 0.27 0.3
r~ y 5.1 5.1 5.1 5.1 5.1
CMC 0.4 0.4 0.4 0 4 0.4
PVNO 0.03 0.03 0.03 0.03 0.03
Granular suds suppressor 1.5 1.5 1.5 1.5 1.5
Minors/misc to 100%
The following T50 values (in seconds) were obtained for each of products A to D:
T50 A B C D
Protease < 60 < 60 < 60 < 60
Peroxyacid 130 190 205 240
W0 9S/28467 2 1 8 7 3 0 3 P~ ul
64
AVO 95 ¦ 225 ¦ 230 ¦ 115
CL dti.~ testin~
T~ method - stain removal
S ' pre~aration
Three white cotton sheets were prewashed in a non-biological bleachfree heavy duty
detergent. Sets of six test swatches of si_e ocm x ocm were cut from each sheet.Stains were evenly painted onto each swatch set.
Additionally, pre-prepared swatches obtained from the EMPA institute were also
employed.
In summary, the following sets of swatches were employed:
Fn7vmatic stains
Grass;
F- C'~
EMPA Blood;
~MPA Blood Milk and Ink;
GrPqcv stair~s
Milky coffee;
Lipstick;
WO 95128467 r~ A /u7
6~l ~73o3
The sets of fabric swatches were subjected to one wash cycle in an automatic washing
machine. The swatches were then assessed for removal of the stains by an ~xpert
panel using a four point Scheffe scale. The combined averaged paired results of each
of the sets of 1 are as set out below, with prior art cc, y~ A being
used as the common reference.
In more detail, a Miele 698 WM automatic washing machine was employed, and the
40C short cycle ~ILo selected. Water of 12 German hardness ( Ca: Mg = 3
: 1) was used. 75g of detergent, dispensed from a granulette dispensing device placed
in the middle of the load was employed. One swatch of each type was washed alongwith a ballast load of 2.7 Kg of lightly soiled sheets (I weeks domestic usage).
;Ye ~ct;no - St~;p remoYal
The above stain removal test method was followed in comparing the efficiency of
Cn~r ;tinn B with the reference prior art r-- .,~ A in removing different type
of stains.
The results obtained were as follows:
Stain type Stain remoYsl benerlt ~PSIJ)
EMPA blood +2.8~
EMPA BMl + 1.6#
Grass + 1.0
Milly coffee + I .1
Lipstick +0.8
~slO~.ir~ at 95 % confidence limit
Exann~le 2
The following bleach-contsining machine Lli~h.... ~ . . were prepared
(parts by weight) in accord with the invention.
w095/28467 2 1 87303 ~"~
66
A B C D E F G
Citrate 15.0 15.0 15.0 15.0 15.0 15.0
480N 6.0 6.0 6.0 6.0 6.0 6.0
Carbonate 17.5 17.5 17.5 17.5 17.5 17.5
Phosphate - - - - - - 38.0
Silicate (as 8.0 8.0 8.0 8.0 ~.0 8.0 14.0
sio~)
MPr~C;I 1.2 1.2 1.2 1.2 1.2 1.2 2.5
(as SiO2)
PBI1.2 1.2 1.5 1.5 1.5 2.2 1.2
TAED (slow 2.2 2.2 2.2 3.5 - 2.2 2.2
release particle)
Cationic lactam - - - - 3.3
Paraffin 0.5 0.5 0.5 0.5 0.5 0.5 0.5
Bismuth - 0.2 0.2 0.2 0.3 0.4 0.2
nitrate
Protease 2.0 2.0 2.0 2.0 2.0 2.0 2.0
Amylase 1.5 1.5 1.5 1.5 1.5 1.5
BSA - - - 1.5
DETPMP 0.13 0.13 0.13 0.13 0.13 0.13
HEDP 1.0 l.0 1.0 l.0 1.0 1.0
w0 ssn8467 2 1 8 7 3 ~ 3 F~ ul
67 ~f
Nonionic 2.0 2.0 2.0 2.0 2.0 2.0 1.5
Sulphate 23.0 22.8 22.4 22.7 22.2 21.5 0.3
misc inc
moisture to
balance
pH (1% 10.7 10.7 10.7 10.7 10.7 10.7 11.0
solution)
