Note: Descriptions are shown in the official language in which they were submitted.
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Detergent Composition Comprising Source of Hydrogen Peroxide and Protease Enzyme
Technical field
The pr~sent invention reiates to non-phosphate builder-containing detergent
compositions. More particularly, the invention relates to non-phosphate
detergent compositions, comprising a SL" ra~;tal ,t, a source of hydrogen
peroxide, an organic peroxyacid precursor, a proteolytic enzyme and an
alkalinity source, which provide effective soil/stain removal.
Back~round of the invention
The salisrdclGfy removal of soils/stains is a particular challenge to the
formulator of a deler~~e"1 co,nposition for use in a washing process such as
laundry or machine dishwashing process.
Traditionally, the removal of soils/stains has been achieved by the use of
bleach co",po,)ents such as oxygen bleaches, including hydrogen peroxide
and o~ ganic peroxyacids, and also by enzyme components.
Oxygen bleaches are known to effectively decolourise pigments from
soiled/s~ai"~d subsl,dles.
Enzymes are also known as effective soil/stain removal agents, for example,
in the removal of proteinaceous stains/soils such as blood, egg, chocolate,
gravy and the like.
rl,os~ l,oius containing compounds such as sodium tripolyphospl,~te have
effective builder properties; however environmental concems have made
the use of phosphorus containing compounds less attractive in detergent
compositions.
A problem encountered with the use of high levels of oxygen bleaches is the
propensity of these oxygen bleaches to lead to stain fixing and/or darkening.
FLII ll ,e", lOf'a, high levels of oxygen bleaches increase the cost of the
delergents to the consumer. On the other hand low levels of oxygen
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bleaches can lead to poor stain/soil removal ~.e,fo"-~ance especially when
used in a non-phos~,l ,ate builder containing co" ,position.
A problem encou,)lered with the use of peroxyacids in ",acl,ine dishwashing
methods is the ta,.,isl~ing/corrosion of any silverware co",~onel,ls of the
washload. Such a problem, ~liscl~sed in GB Patent Application No
9407533.0 is known in the art. Oxygen bleaches tend to give rise to more of
a problem of tamishing than chlorine bleaches. The level of tamishing
observed can range from slight r~iscolcralio, I of the silverware to the
formation of a dense black codli"g on the surface of the silverware.
A problem encountered with the use of enzymes as components of
d~ter~enls is that enzyme activity in the wash may be arrecled by the
presence of other deterge"l co,npo,)~nls in the wash solution. GB Patent
plic~tion No 9407533.0 discloses that enzymes may be degraded by
bleach COIll~Gl)e~nlS.
The detergenl formulator thus faces the challenge of formulating an
enviro,)",enlally friendly product which ",~in,ises soil/stain removal without
fixing and/or darkening stains/soils which avoids degradation of the
detergent cor"pG"el ,ts and which is also inex~,ensive.
Pending GB Patent Application No 9407536.3 that forms part of the state of
the art under Article ~4(3) EPC disclQses the use of a bleach containing
deterge, n col-lposilio-, which con~ains low levels of bleach and bleach
activator with higher levels of chelant and enzyme and defines a specific
Biological Bleach Index which provides stain removal p~,ror..,a,.ce. Specific
ki.lelics of bleach delivery are not disclosed nor are the means to achieve
such kinetics.
Pending GB Patent Application No 9407533.0 that forms part of the state of
the art under Article 54(3) EPC discloses the use of an enzyme together
with a source of peroxyacid bleach wherein a means is provided for
delaying the release to the wash solution of said peroxyacid bleach relative
to the release of said enzyme. The delayed release is provided by coali,-g
the source of peroxyacid bleach. The coating may occur on the hyd~oge"
-
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peroxide source itself and/or the peroxyacid bleach precursor itself. Specific
ratios of hydrogen peru,cide: precursor: pr~,lease are not ~isclose~
The Appli~rlts have found that the occurrence of soil/stain fixing and/or
darkening effects arising from use of peroxyacid bleaches in a washing
Illelhod is related to the rate of release of the hydluye~ peroxide source. A
fast rate of release of the hyd,oyeil peruxido source to the wash solution
~ tends to exac~rbale soil/stain fixing and/or darkening problems. Whilst
reducing the rate of release of the hyd~og~l"~eroxicJe source employed in
the wash tends to ameliorate these problems this is acco",pa"i l by a
marked negative effect on the bleachable stains/soil removal ability.
The Ar~plir~nts have now surprisingly found that the provision of an
alkalinity source which prorl~ces a speciric minimum amount of alkaline
salts into the wash solution ameliorate these problems when low rate of
release of the h~dlogen peroxide source to the wash sol~tion is used in
combination with organic peroxyacid bleach precursors and proteolytic
enzymes.
The Ap,ulical lls have also found that where a non-,c hosphate builder-
containing deterye"t composition containing a source of hyd~ oyen peroxide
an organic peroxyacid bleach precursor and a proteolytic enzyme defined
in term of an H~dloyell pe,oxide Precursor Proteolytic enzyme (HPP) index
which relates to the ratios of Hyd~oye,) peroxide precursor and proteolytic
enzyme togetl,er with a high level of an alkalinity source is employed an
o nl ,a"ced stain/soil removal may be obtained.
The ~pplic~lts have also found that the total available oxygen (Av02)
cGIltellt in the cGi"position should preferably be less than 1.5% by weight of
the composition.
The Applicants have also found that the the further addition of co,npounds
e~lhances the overall stain/soil removal performance. Such compounds may
be selected from amylases water-soluble oryanic polymeric polycarboxylic
c~""~ounds chelants and mixtures thereof
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It is thererore an object of the present invention to provide cG""~osilions
suitable for use in laundry and machine dishwashing " ,ell ,ods having
e, Ihanced stain removal.
It is a further object of the invention to provide co",positions for use in
laundry and machine dishwashing methods wherein said cG""~ositions show
less propensity to cause stains fixing and/or darkening as well as ~eterge"l
CC~ )G~ llS de~~(adalion.
Summalv of the invention
Accordi,)~a to the present invention there is provided a non-phosphate
builder- containing deterge, ll composition CG" ,prising a surfactant, and
a)- at least 0.5% by weight of a source of hydrogen peroxide,
b)- from 0.01% to 10% by weight of an organic peroxyacid bleach precursor,
c)- from 0.001% to 5% by weight of a proteolytic enzyme, and
d)- an alkalinity source having the capacity to deliver alkalinity to a wash
solution as measured by the alkalinity release test des~ibed herein, such
that the % weight NaOH equivalent of the composition is greater than 10.6%
by weight of the con"~osilion, and
wherein the detergen~ composition has an Hydrogen peroxide Precursor
Proteolytic enzyme (HPP) Index of at least 0.35 as defined by the formula
(%weight of precursor x %weight of proteolytic enzyme)
HPP =
(%AVO2)2
wherein the %weight of proteolytic enzyme in the formulation is based on an
enzyme activity of 13 knpu/g of the enzyme particle, and
wherein the %AvO2 is the total amount of available oxygen present in the
co"~osi(ion.
If the actual activities of these proteolytic enzymes in the detergent
cor,~position are dirrtren~ from their 13 knpu/g standard activities, the level
of proteolytic enzyme will be adjusted accordingly. The level of proteolytic
enzyme is defined as the actual level of the prill/granulate on a 13 knpu/g
Savinase particle.
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Non limiting examples of enzymes other than Savinase which can also be
used for the purpose of the invention include enzyme of the Bacillus Lentus
type L,achl,ol ,e such as M~x~c~l, Opticlean, Durazym and r, operase,
enzyme of the Bacillus Licheniformis type backbone such as Al~'~se and
.al~se and enzyme of the Bacillus Amyloliquefaciens type backbone
such as Pli",ase.
For example, if a protease is used having an activity of 26 knpu, the amount
of ~rolease will be red~ ~ced by a factor 2 to con ",e, .sale for the extra activity
of the protease.
For the purpose of the invention, proteases which are in other units of
activity should be converted according to the following steps:
1 conversion of the level of proteolytic enzyme used into the level of pure
enzyme, and
2-conversion from the level of pure enzyme to a 13 knpu/g Savinase particle
basis according to the following equation:
13 knpu/g = 33 mg pure enzyme/g of enzyme particle
It is to be un.lersloo~ that total amount of available oxygen present in the
co""~,osition includes available oxygen provided by the source of hydrogen
peroxide with or without peroxyacid bleach precursors.
Preferably the total available oxygen (Av02) content in the composition is
less than 1.5% by weight.
Alkalinity is the co"~Li.,ing power of a base measured by the maximum
number of equivalents of an acid with which it can react to form a salt. In
soll ~tion, it represents the carbonates and silicates in the water and is
determined by titration with standard datum points.
For the purpose of the invention, alkalinity is defined as the weight
equivalent of sodium hydroxide (NaOH) needed to be delivered into the
wash to neutralise an equivalent amount of hydrochloric acid.
Detailed descriPtion of the invention
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HPP index
The ~,ese,ll invention relates to the discovery of a Hydloge" peruxiJe
Precursor r~oteolytic enzyme (HPP) Index which de~ines a formula which
relates speciric ratios of hy-JI ogen peroxide: precursor: ~ oteolytic enzyme.
Accordi. ,g to this is provided a non-phospl ,ale builder~G, ~lai"ing detergent
CGI I .posiliol I having a Hydl uge n perùxicle Precursor Proteolytic enzyme
(HPP) Index of at least 0.35 as defi"e.l by the formula
(%weight of precursor x C6woi~1)l of proteolytic enzyme)
HPP =
(%AYO2)2
wherein the %weight of proteolytic enzyme in the formulation is based on an
enzyme activity of 13 knpu/g of the enzyme particle, and
wherein the %AvO2 is the total amount of available oxygen ~resel,l in the
CGrl l~oSiliGI~.
r, eren ~bly the HPP Index is of at least 0.40 and most pre~erably 0.50.
rl-erer;3bly the total available oxygen (Av02) content in the cûlnposition is
less than 1.5% by weight.
Source of hvdu~c~en oeroxide
An essential co""~onei ,L of the det~rgei ,l cGI",~osilion is a source of
hy.hog~n peroxide. The source of hyd,ogen , eroxide is normally
i,.co"~rdled at a level of at least 0.5% by weight, more plererdbly from 4%
to 15% by weight and most prefe,ably from 4% to 10% by weight of the
cû,, ~l ~osili~i ..
Said source of hyd,oyen peroxide is a slow releasing source. The slow
release of hydl o~ei, peroxide source relative to that of the protease is such
that the time to achieve a concenl, alio,) that is 50% of the ultimate
co"cenlralicji, of said enzyme is less than 120 secor,ds, prl3fe,ably less than
90 seconds, more p,e~rably less than 60 secol ,Js, and the time to achieve
a ~..~nl.alion that is 50% of the ultimate concel~lldliGIl of said hydrogen
peroxide source is more than 180 seconds, ~,,erefably from 180 to 480
seconds, more preferably from 240 to 360 secG"Js. rlefer~bly the time to
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achieve a coi~ce"l,dlion that is 50~/0 of the Lllli",ale cGncenl,ation of said
enyme is at least 100 secc "ds less than the time to achieve a
co"cer,l,alion that is 50% of the ulli",ate concel1lralion for the hyd~ugen
peroxide source.
Such slow release kinetic is more particularly des~il)ed in pe"di-,g GB
~ppli~Ption No. 9407533 0
In this respect, a preferred source of hyd,oyel~ peroxide is an i"organic
perhydrate. A ~,refel,ed perhydrate is pelLorate tetrahydrate of nominal
formula NaB02H202.3H2 0. The inorganic perhydrate will normally be in
the form of the sodium salt. More prererably, the source of hydl oge
peroxide consisls of at least 90% by weight of a pe, L,orale tetrahydrate.
Alle",dli-/ely, other perhydrate co",pounds may be used in addition or in
place of the pe,l,orale tetrahydrate togell,er with approp,iate means such
as ~ati"y or co~gglo" ,eralion, to obtain a slow release of hydrogen
,varoxide. Such COI "~unds can include pe, L.ol ale " ,onol ,ydrate
percd, 1~1 ,ale, pe" hospl ,ate persilicate salts and mixtures thereof.
Of these cGI~pounds a prerel,ed perhydrate is percarbonate. Coarse
per~s, L,onate materials of average particle size greater than 600
",icro",eters and preferdL,ly yl~dler than 750 micrometers may be used
rleferably, these perca,Li~"ale materials are coated with s~hsPnces which
are s~s,i,)gly soluble in water. Water insoluble codli"g materials may be
selected from fatty acid polymers hydl o~ L i c silicas, waxes and
magnesium silicates and mixtures thereof. Perca.bonate materials whicn are
~xcl- ~sively coated with water-soluble s~ ~~ ~sl~nces such as citrates
borosili~tes borate derivatives sodium c8~bonale or sodium/magnesium
sulphate are not preferred.
When ~,erca, bo. ,ate is used the source of hydrogen peroxide consists of at
least 90% by weight of a perca,bonate having a particle size of at least 600
micrometers and coated with water-insoluble materials.
Mixtures of any of the herein before described perhydrate
col~,pounds can also be used.
In a p(erelled embodiment of the invention the level of total available
oxygen (Av02) in the ccl"posilion is less than 1.5% by weight. A method for
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det~l " ,ining AvO2 levels is disclosed in European Patent ~pplir~tion
No.93870004.4.
Oraanic Peroxvacid bleach Drecursor
Peroxyacid bleach precursors are co",~ounds which react with hycJ,ogen
peroxide in a perhydrolysis reactioo to produce a peroxyacid. Generally
pero~yacid bleach precursors may be ,eprese,)led as
o
X-e-L
where L is a leaving group and X is essentially any fu..ctionalil~ such that
on perhydrolysis the structure of the peroxyacid produced is
o
X-e-OOH
Peroxyacid bleach precursor co""~ounds are ~referably i.,cG,~oraled at a
level of from 0.01% to 10% by weight more prereral,ly from 3% to 10% by
weight, most ~.referably from 5% to 9% by weight of the precursor
cc " I~osilio,~.
Leavina arouPs
The leaving group, hereindrler L group, must be sufficiently reactive for the
perhydrolysis Fes~ lion to occur within the optimum time frame (e.g. a wash
cycle). However if L is too reactive this activator will be difficult to stabilize
for use in a bleaching composition.
Prt7fe, led L groups are selected from the group consisting of:
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--0~, --O~Y, and --(~R3Y
--N C--R1 --NL~ --N--C--CH--R4
lR3 r
--0--C H=C--C H=C H2--0--C H=C--C H=C H2
-O--C--R1 CH~ Y11
O O
--0--C--CHR4 , and N S--CH--R4
and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group
containing from 1 to 14 carbon atoms, R3 is an alkyl chain containing from 1
to 8 carbon atoms, R4 is H or R3, and Y is H or a sclubili~ing 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 a,r,r"c)i,ium or alkyl ammmonium groups
The prefe" ed solubilizing groups are -S03-M+, -C02-M+, -S04-M+,
-N+(R3)4X- and 0~--N(R3)3 and most preferably -S03-M+ and -C02-M+
wherein R3 is an alkyl chain ~"taining from 1 to 4 carbon atoms, M is a
cation which provides solubility to the bleach activator and X is an anion
which provides solubility to the bleach activator. F,eferably, M is an alkali
metal, arn" ,ol ,ium or substituted ammonium cation, with sodium and
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pot~ssi~ln being most ~,refer,ed, and X is a halide, h~,dloxicle, methylsulfate
or ~c~ 1e anion.
Suitable peroxyacid bleach precursor materials are co, npounds which
com~rise at least one acyl group fo""iny the peroxyacid moiety bonded to a
leaving group through an -O- or-N- linkage.
These can be selecled from a wide range of cl~sses that include
anhydrides, esters, imides, laclar"s and acylated derivatives of imid~oles
and o~i",es. Examples of useful nlaterials within these c~~sses are disclosed
in GB-A-1586789. Suitable esters are disclose~i in GB-A-83l;9~, 864798,
1147871, 2143231 and EP-A-0170386.
A preferred class of bleach precursor is the class of N-acylated precursors
of which TAED is the prerel, e-J one.
Peroxyacid precursor ~" ,positions containing mixtures of any of the
precursors hereir,drler disrlosed are also contemplated by the present
invention.
relber.~ acid Drecursor
re.be., -i~ acid precursor ~",pounds provide pelL,e"~oic acid on
perhydrolysis.
Suitable O-acylated perbenzoic acid precursor compounds include the
substituted and unsubstituted benzoyl oxybenzene sulfonates, including for
example benzoyl oxybel ,~ene sulfonate:
o
(~O~SO3-
Also suitable are the benzoylation products of sorbitol, glucose, and all
sa~:ha, ides with benzoylating agents, including for example:
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OAc
AcO--~o
~,OAc
OAc~
OBz
Ac = COCH3; Bz = Benzoyl
Perbenzoic acid precursor co""~ounds of the imide type include N-benzoyl
succi,-i."ide tetrabenzoyl ethylene diamine and the N-benzoyl substituted
ureas. Suitable i,nid~ole type perbenzoic acid precursors include N-
benzoyl imid~ole and N-benzoyl be"~i",id~ole and other useful N-acyl
group-containing pe,b~"~oic acid precursors include N-benzoyl pyrrolidone
dibenzoyl taurine and benzoyl pyroglutamic acid.
Other perl3en~oic acid precursors include the benzoyl diacyl peroxides the
benzoyl tet,dacyl peroxides and the cor"pound having the formula:
O O
~O' O~COOH
Phthalic anhydride is anotl,er suitable perb6",0ic acid precursor compound
herein:
o
~0
Suitable N-acylated precursor compounds of the lactam class are disclosed
generally in GB-A~55735. Whilst the broadest aspect of the invention
CGI llel I ,plates the use of any lactam useful as a peroxyacid precursor
prefe"ed materials co",~rise the caprolactams and valerolactams.
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t~le caprolacld", bleach precursors are of the formula:
o
Il .
O C CH2 CH2
Il I \
6 CH2
R C - N
CH2 CH2
wherein R6 is H or an alkyl, aryl, alkoxyaryl or alkaryl group cc,nlaining from
1 to 12 ~, L,o" atoms, pref~,ably from 6 to 12 cal L,on atoms.
Suitable valero lacta",s have the formula:
O C CH2 CH2
Il I
R6 C N
CH CH
wherein R6 is H or an alkyl, aryl, alkoxyaryl or alkaryl group containing from
1 to 12 carbon atoms, ~,rererably from 6 to 12 ~Ibol~ atoms. In highly
,uref~"~d elllbodime~ls, R6 is selected from phenyl, heptyl, octyl, nonyl,
2,4,4-trimethylpentyl, decenyl and mixtures thereof.
The most prefel,ed materials are those which are normally solid at ~30~C,
particularly the phenyl derivatives, ie. benzoyl valerolactam, benzoyl
caprolactam and their substituted benzoyl a"alogues such as chloro, amino
alkyl, alkyl, aryl and alkyloxy derivatives.
Caprolactam and valerolactam precursor ",alerials wherein the R6 moietyconlai"s at least 6, p,eferdbly from 6 to about 12, carbon atoms provide
peroxyacids on perhydrolysis of a hydro~ hobic character which afford
-
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n~ philic and body soil clean-up. Precursor cG""~ounds wherein R6
col"~,rises from 1 to 6 carbon atoms provide hydrophilic bleaching species
which are particularly efficient for bleacl,iny beverage stains. Mixtures of
'hydro~hobic' and 'hydrophilic' caprolactar,~s and valero l~c~a",s, typically atweight ratios of 1:5 to 5:1, preferably 1:1, can be used herein for mixed stain
removal ben~ils.
Perbenzoic acid derivative Drecursors
Pell,e"~oic acid derivative precursors provide substituted p~,L,e"~oic acids
on perhydrolysis.
.SuiPhlQ substituted perbenzoic acid derivative precursors include any of
the herein dis-,losed pelLell ~ic precursors in which the benzoyl group is
s~ ~hstit~ed by essentially any non-positively chargecl (ie; non-cationic)
fu, I-,lio"al group including, for example alkyl, hydroxy, alkoxy, halogen,
amine, nitrosyl and amide groups.
A preferred class of substituted perl,e" oic acid precursor co"~,ounds are
the amide substituted compounds of the following general formulae:
R1 C--N R2- C L R1--N C--R2 C L
Il l 11 1 11 11 .
O R5 O or R5 O O
wherein R1 is an aryl or alkaryl group with from 1 to 14 calLGn atoms, R2 is
an arylene, or alkarylene group ccnlai"ing from 1 to 14 carbon atoms, and
R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms
and L can be ~ssel ,lially any leaving group. R1 p, ~f~rably contains from 6
to 12 carbon atoms. R2 prererdbly contains from 4 to 8 carbon atoms. R1
may be aryl, substituted aryl or alkylaryl containing branching, substitution,
or both and may be sourced from either synthetic sources or natural sources
including for e,~am~,le, tallow fat. Analogous structural variations are
permissible for R2. The substitution can include alkyl, aryl, halogen,
nil, oge", sulphur and other typical substituent groups or organic
co"",ounds. R5 is preferably H or methyl. R1 and R5 should not contain
more than 18 carbon atoms in total. Amide s~hstituted bleach activator
cc mpounds of this type are des~ ibed in EP-A4170386.
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_
14
Cationic Deroxvacid Precursors
Cationic peroxyacid precursor coh,pounds produce c liGl.ic peroxyacids on
perhydrolysis.
Typically, calio"i~ peroxyacid precursors are fo""e.l by substituting the
peroxyacid part of a suitable peroxyacid precursor co" ,~ound with a
positively charged ful .ctio"al group, such as an ammo"ium or alkyl
a" ,l "" ,onium group, I,, ererably an ethyl or methyl a" " "o"ium group.
Cationic peroxyacid precursors are typically present in the solid deterge"l
cG""~osilions as a salt with a suitable anion such as a halide ion.
The peroxyacid precursor cGI"pound to be so calionically substituted may
be a p61 6erlcoic acid, or s~ Ihstit~ Ited derivative thereof precursor compoundas described I ,erei. I6erore. Allel "ali-/ely the peroxyacid precursor
~,npound may be an alkyl per~r6Oxylic acid precursor cor"pound or an
amide substituted alkyl peroxyacid precursor as des~ ibed hereinafter
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.~ 1 382 594; EP 475 512 458 396 and 284 292; and in JP
87-31 8 332.
Exa."ples of prefer,ed calioni~ peroxyacid precursors are described in UK
Patent Application No. 9407944.9 and US Patent Application Nos.
08/298903 08/298650 08/298904 and 08/298906.
Suitable cationic peroxyacid precursors include any of the ammonium or
alkyl ammonium substituted alkyl or benzoyl oxybe"~e"e sulrl,nales N-
acylated caprolactams and monobenzoyltetraacetyl glucose benzoyl
peroxides.
A prer~"ed calionically substituted benzoyl oxybe,-~ene sulfonate is the 4-
(trimethyl a-"monium) methyl derivative of benzoyl oxybenzene sulfonate:
.
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O
\N+
A prere, ~ ~d cationically substituted alkyl oxyL,er,~e"e sulrondle has the
formula:
.
O ~ S~3
rl efer, ~ad ~lionic peroxyacid precursors of the N-acylated caprolactam
class include the trialkyl a,nl~,Gnium methylene benzoyl caprolactams
particularly t i,netl,yl a""nG"ium methylene benzoyl caprolactam:
o ~o
/ N ~
Other pr~fel, ecl cationic peroxyacid precursors of the N-acylated
caprolactam class include the trialkyl al "" ,onium methylene alkyl
caprolacta, ns.
O O
(CH2)n ~)
where n is from O to 12.
Another prerel,~d cationic peroxyacid precursor is 2-(N N N-trimethyl
a" " "o"ium) ethyl sodium 4-sulphophenyl ~a, L ol ,ate chloride.
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16
Be,~-o~;n G19dniC peroxyacid precursors
Also suitable are precursor co,~,pounds of the ~,e,~o),;A~;n-type, as ~:li5c~ seti
for example in EP-A-3~ 94 and EP-A482,807, particularly those having
the formula:
1~l
~C--R1
including the s~ Ihstit~ ~ted ben7ox~ s of the type
R5
wherein R1 is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4, and
R5 may be the same or clifrerent substituents selected from H, halogen,
alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR6 (wherein
R6 is H or an alkyl group) and carbonyl fiJn~,liGIls.
An especi-"y prefei red precursor of the bel ~,o.~ ;. ,-type is:
1~l
~N~C~
Alkvl ~er~, L,oxYlic acid bleach precursors
Alkyl per~a, I,oxylic acid bleach precursors form perca, boxylic acids on
perhydrolysis. r,efe~ d precursors of this type provide peracetic acid on
perhydrolysis.
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r~e~,.ed alkyl perc;3r60xylic precursor ~,npounds of the imide type include
the N N-N' N' tetra acetylated alkylene diar"ines wherein the alkylene group
cGntains from 1 to 6 Cal~GIl atoms particularly those con,pounds in which
the alkylene group contains 1, 2 and 6 carbon atoms. Tel,aacelyl ethylene
diamine (TAED) is particularly pre~
Other prefe..ed alkyl per~,boxylic acid precursors include sodium 3,5,5-tri-
methyl I ,exanoyloxyL.el .~e ne sulro,)ale (ISONOBS), sodium
nonanoyloxyL,e.,~ene sulro"ale (NOBS) sodium acetoxyl~e,)~ene sulr(,"ate
(ABS) and pe"taacelyl glucose.
Amide substituted alkYI Peroxyacid Precursors
Amide s~hstit~tecl alkyl peroxyacid precursor cGm~ounds are also suitable
including those of the following general formulae
R1 C N R2 C L R1 N C R2 C L
Il l 11 1 11 11
O R5 0 or R5 0 0
,erein R1 is an alkyl group with from 1 to 14 carbon atoms R2 is an
alkylene group col,tai--i,)g from 1 to 14 carbon atoms and R5 is H or an
alkyl group co.,laining 1 to 10 carbon atoms and L can be essentially any
leaving group. R1 prl3rerably contains from 6 to 12 c~,L,o" atoms. R2
prererably co,llai.-s from 4 to 8 carbon atoms. R1 may be sl.ai$~hl chain or
bral ,~ .ed alkyl containing branching substitution or both and may be
sourced from either synthetic sources or natural sources including for
ex;~.."~le, tallow fat. Analogous structural variations are permissible for R2.
The s~hstih~tion can include alkyl halogen nitrogen sulphur and other
typical s~hstituent groups or organic ~""~ounds. R5 is prefetably H or
methyl. R1 and R5 should not contain more than 18 carbon atoms in total.
Amide substituted bleach activator compounds of this type are described in
EP-A-01 70386.
r, efe" ed amide substituted alkyl peroxyacid precursor compounds are
(6~cldl ,a",ido-caproyl)oxybe"~, lesulfonate (6-, IG"a"ar"ido~proyl)oxy
be"~e"e sulfonate and (6-decanamido~aproyl)oxyLe"~ene sulronale and
mixture thereof.
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More p,er~ d peroxyacid bleach precursors co",pounds for use in the
invention are selected from N,N-N',N' tetra acetyl ethylene diamine, 3,5,5-tri-
methyl l,exa"oyl oxybe.-~e"e sulrondle".onanoyl oxyL.en~ane s--lronale,
amide s~ ~hstitute~ e. ~, ~~oic acid precursor cGr"pounds, amide substituted
alkyl peroxyacid precursors and mixtures ll.ereor.
A most p,ef~ d peroxyacid bleach precursor is N,N-N',N' tetra acetyl
ethylene diar"i"e:When used TAED will ~,r~rerably be at a level of from
0.5% to 2.5% by weight.
Bleachi"g agents other than oxygen bleachin~ agents are also known in the
art and can Gptionally be utili~ed herein. One type of non-oxygen bleaching
agent of particular interest incl~des pholo~ctivated bleaching agents such
as the sulrc,nal~d zinc andlor aluminum phthalocyanines. See U.S. Patent
4,033,718, issued July 5, 1977 to Holcombe et al. If used, delergent
co"~po~itio- ,s will typically contain from 0.025% to 1.25%, by weight, of such
bleaches, especially sulronate zinc phthalocyanine.
r"~teolvtic enzYme
An essenlial ~~ GI ,6nl of the deterger,l co",~osition is an enzyme showing
proteolytic activity.
For the purpose of the invention, the level of proleolytic enzyme in the
formulation is based on an enzyme activity of 13 knpu/g of the enzyme
~dl licla.
The cc,l"~osilions herein will typically comprise from 0.001% to 5% active
~rotease by weight of the composition.
Non limiting examples of enzymes other than Savinase which can also be
used for the purpose of the invention include enzyme of the Bacillus Lentus
type backbone such as M~ c~l, Opticlean, Durazym and Properase,
enzyme of the Bacillus Licheniformis type backbone such as AlG~'-se and
M~ se and enzyme of the Bacillus Amyloliquefaciens type backbone
such as r, i"~ase. Of these, M~Y~C~I jS a prere, .ed one.
Preferred co, . ,n ,el ~ially available ~,l v~ease enzymes include those sold
under the i.dda,-s",es Al~ se, Savinase, Pli,),ase, Durazym, and
Es,uerase by Novo Industries A/S (Der" "a, k), those sold under the
l~a~e~ar"e M~ 5e, M~Y~C~I and Maxapem by Gist-Broc~des, those sold
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19
by Genencor Intemational, and those sold under the tradename Opticlean
and Optimase by Solvay Enzymes. Mixture of the herein before des~ibed
proteases may be used.
A most pref~r~d ~rol~asl3 is Savinase.
Alkalinitv source
An essential cGIllpoll~l)l of the delerger,l composition is an alkalinity source.
For the purpose of the invention, alkalinity is defined as the weight
equivalent of sodium hydroxide (NaOH) needed to be delivered into the
wash to neutralise an equivalent amount of hydrochloric acid.
To enable practical colllpalisGn of the relative capacily of composilions
coi ,~ai,)ing dirrer~nl alkaline co",pGnents to deliver alkalinity to a wash
solution it is useful to e~ress the alkalinity released on addition of the
co""~osilions to the wash solution in terms of % weight equivalent of NaOH.
That is, in terms of the % weight of NaOH which would have equivalent
'alkaline effect', e. 9. in neutralising acid species, to that of the alkalinityspecies actually released when the co""~osition is added to the wash. For
uniform co""~a~ison it is also then useful to define standard wash solution
characleristics. Thus, the capacity to deliver alkalinity to a wash solution is
herein ~;haracteri~ed by rererei ,ce to a representative test method now
described.
Alkalinitv release test method
A 19 sample of detergent co,nposition is added to 100 ml of distilled water at
a temperature of 30~C with stirring at 150 rpm using a magnetic stirrer of
size 2cm, thus providing a 1% detergent solution, as would be a typical
concentration of a laundry wash solution. The solution is titrated against a
slandald HCI solution using any suitable titration method. Commonly known
acid-base titration methods employing colorimetric end-point dete""ination
methods, for example using chemical end-point indicalor:, are particularly
suitable. Thus, the number of moles of HCI which the detergent solution is
ca~atl of neutralising is obtained. For the avcidance of doubt,
'neutralising' in this context is defined to mean lilldling to pH 7. This numberwill be equivalent to the number of moles of alkalinity, expressed as NaOH
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equivalent prese.,l in the detergent solution. Thus the % weight equivalent
NaOH present in the sample of the delerge"l co- "posilion may be
c--~c~ ~I~'ed as:
% weight equivalent NaOH =
100 x number of moles NaOH equivalent in solution x Mw of NaOH
Theoretical maximum alkalinitv
Where the cG,npositional make up of a detergent product is known it is
rossibls to ~Ic~Jl~e the ll,eorelical ,.,axi-..um alkalinity eApressed as %
weight equivalent of NaOH which the product could provide to a solution as
the sum over each alkaline species of:
% weight (alkaline species) . Mw (NaOH . n / Mw(alkaline species)
where n is the formal negative charge carried by the alkaline species.
As an exa."pl a col.,posilion containing 15% sodium carbonate is
equivalent to a theoretical ma~ m of 11.32% NaOH obtained as (15 x 40
x 2)/106, since this amount of NaOH in the ~""~osition would theoretically
neutralise the same amount of acid as the 15% sodium carbonate alkaline
com~,onenl.
Alkalinitv reauirement
In accord with the present invention the alkalinity source is present in the
detergent ~mposilio., such that the capacity to deliver alkalinity to a wash
solution measured by the given test ~.,ethGd is such that the % weight NaOH
equivalent of the ~l~position is g,~dler than 10.6% ,c,rererably at least
14.6% by weight of the composition.
The alkalinity source is p,ererably selected from alkali metal carbonate
alkali metal silicate and mixture thereof.
-
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21
Suitable alkali metal ca,bGnales include the alkaline earth and alkali metal
carbonates, including sodium carbonate and sesqui~a,L.G"ale and mixtures
ll,~reor with ultra-fine calcium ca,l,onale as cJisclosed in German Patent
Application No. 2,321,001 published on Nov~r"ber 15, 1973.
Suitable silicates include the alkali metal siliçat~ SiO2:Na20 with a ratio of
from 1.0 to 2.8 and 1.6:1 ratio being more pr~fer-~d. The silicates may be in
the form of either the anhydrous salt or a hydrated salt. Sodium silicate with
an SiO2:Na2O ratio of 1.6:1 is the most prere"~d silic~te.
Other cG",pounds which provide free alkalinity in ~ eo~ ~s solution may also
be used. Such cGl"pounds include the crystalline layered silicate and/or
alu",inosilic~te c~""~ounds as clesuil,e.l herein after, but also the
bicarbonates, hydroxides, borates and ~l ,osphales.
Addilional CG~ onents
The ~leterg~"l co",position of the invention will, of course cGntain one or
more su,r~tanls and ad-Jilional con~pounds for er,ha"ci,.y the soil removal
p61 r~""a, Ice.
Such cc"..~Jounds include the water-soluble organic polymeric pol~ca,L,oxylic
oo" ,pounds, chelants, amylases, builders and con~enliG"al detersive
adjuncts.
Detersive Su, rac,tants
The total amount of su,ractants will be generally up to 70%, typically 1 to
55%, l~referal,ly 1 to 30%, more preferably 5 to 25% and especially 10 to
20% by weight of the total composition.
~J~nli.l~ililly examples of su,ra-,ta"ts useful herein include the conventional
C11-C1g alkyl benzene sulronates ("LAS") and primary, branched-chain and
randon, C10-C20 alkyl sulfates ("AS"), the C10-C1g seco"da,y (2,3) alkyl
sulfates of the formula CH3(CH2)x(CHOSO3-M+) CH3 and CH3(CH2)y
(CHOSO3-M+) CH2CH3 where x and (y + 1) are inteyers of at least 7,
~,ref~rably at least 9, and M is a water-solubilizing cation, especially sodium,unsaturated sulfates such as oleyl sulfate, the C10-C1g alkyl alkoxy sulfates
("AExS"; esreci~lly EO 1-7 ethoxy sulfates), C1 0-C1 8 alkyl alkoxy
ca, L,oxylates (especially the EO 1-5 ethoxy~, L oxylates), the C1 0-18
glycerol ethers, the C10-c18 alkyl polyglycosides and their co"esponding
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sulfated polyglycosicles and C12-C1g alpha-sulfonated fatty acid esters. If
desired, the conventional nonionic and an~pl)oleric su,rc-,ctanls such as the
C12-C18 alkyl ethoxylates ("AE"), including the so-called narrow peaked
alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especi 'Iy
ethoxylates and mixed ethoxy/l.r~o~y) C12-C18 betaines and
sulroL,etaines ("sultaines"), C10-C18 amine oxides, and the like, can also be
included in the overall coi.,posilions. The C10-C18 N-alkyl polyhydroxy
fatty acid amides can also be used. Typical exd""~les include the C12-C18
N-methylglucal.,ides. See WO 9 206,154. Other sugar-derived surfactants
include the N-alkoxy polyhydroxy fatty acid amides, such as C10-C1g N-(3-
methoxypropyl) glucamide. The N-propyl through N-hexyl C12-C1g
gluca,nicJes can be used for low sudsing. C10-C20 convenlional soaps may
also be used. If high sudsing is desired the b,ancl)ed-chain C10-C16
soaps may be used.
Other suitable sulrci-td,,ls suitable for the purpose of the invention are the
anionic alkali metal sarcosil~dles of formula:
R-CON(R1 )CH2COOM
wherein R is a Cg-C17 linear or branched alkyl or alkenyl group R1 is a C1-
C4 alkyl group and M is an alkali metal ion. Prerer,ed examples are the
lauroyl cocoyl (C12-C14) myristyl and oleyl methyl sarcosinates in the form
of their sodium salts.
Still another class of su, ra~;ta"t which may be suitable for the purpose of theinvention are the ~3lionic su~ractanL Suitable cationic su,rac~ar,l~ include
the quate")a,y a,nn,onium surfactants selected from mono C6-C16.
pr~3ferably C6-C10 N-alkyl or alkenyl a"""onium surfactants wherein the
r~l ~ ,aining N positions are substituted by methyl hydroxyethyl or
hydroxypropyl groups.
Mixtures of anionic and nonionic surfactants are especially useful. Other
conve, ItiGnal useful surractanls are listed in sta"dard texts.
Water-soluble oraanic Polvmeric polvca, L,oxvlic compounds
Suitable polymeric polycarboxylate co" "~ounds are the water-soluble
organic polymeric polycalLoxylic compounds. r~ferc,bly these co",pounds
are homo- or co-polymeric polycalrboxylic compounds and most pre~erably
co-polymeric polycalL-)~ylic compounds in which the acid monomer of said
polycarboxylic col"pound comprises at least two calL,oxyl groups separaled
_
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by not more than two carbon atoms. Salts of these polycarboxylic
co""~ounds are also considered herein.
Polymeric polyca~L,oxylate coi,.pounds can advant~geously be utilized at
levels from 0.1% to 7%, pr~rerably less than 3% and more prererably less
than 1 % by weight, in the CGIllpOSiliollS herein, especially in the pfesence ofzeolite and/or layered silicate builders and diphosphonate chelants.
Polymeric polycalL,oxylate materials can be p,epared by poly",eri~ing or
copoly" ,eri~i"g suitable unsaturated rl lGI IOI I lel s, p, ~rerably in their acid
form. Unsaturated monomeric acids that can be polymerized to form
suitable polymeric polyca,boxylates are selected from acrylic acid, maleic
acid (or maleic anhydride), fumaric acid, ilacGnic acid, aconitic acid,
",~s~n,ic acid, cil,aconic acid and methylenemalonic acid. The presence
in the polymeric polycarboxylates herein of monomeric segments,
containi,)y no ca. L,oxylate radicals such as vinylmethyl ether, styrene,
ethylene, etc. is suitable provided that such seg,nents do not conslilute
more than 40% by weight.
Polymeric polyc~rboxylate materials can also optionally include further
monomeric units such as nonionic spacing units. For example, suitable
nonionic spacing units may include vinyl alcohol or vinyl acetate.
Particularly prer~, . ed polymeric polycarboxylates are co-polymers
derived from monomers of acrylic acid and maleic acid. The average
mol~'-~ weight of such polymers in the acid form ~,refelably ranges from
2,000 to 10,000, more prererdbly from 4,000 to 7,000 and most preferably
from 4,000 to 5,000. Water-soluble salts of such acrylic/maleic acid
polymers can include, for example, the alkali metal, arr,mG"ium and
substituted ammonium salts. Soluble polymers of this type are known
",dlerials. Use of polyacrylates of this type in detergent compositions has
- been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued march
7, 1967. The ratio of acrylate to maleate segments in such copolymers will
gel,erally range from 30:1 to 1:1, more prererdbly from 10:1 to 2:1. Soluble
acrylate/maleate copolymers of this type are known ",alerials which are
cles~iLed in European Patent Application No. 66915, published Dece",ber
15, 1982, as well as in EP 193,360, published Septe,nber 3, 1986, which
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24
also des~-ibes such polymers comprising hydroxypropylacrylate. Of these
acrylic/maleic-based copolymers, the water-soluble salts of copolymers of
acrylic acid and maleic acid are prere, I,ad.
Another class of polymeric pol~ca,boxylic acid co""~ounds suitable
for the purpose of the invention are the homo-polymeric polycarboxylic acid
cc ""~ounds derived from acrylic acid. The average mole~ ~ weight of such
homo-polymers in the acid form preferably ra"5~es from 2,000 to 100,000,
more preferably from 3,000 to 75,000, most prl3f~rably from 4,000 to 65,000.
A further example of polymeric polycarboxylic compounds suitable for the
purpose of the invention include the malciclac. ~lic/vinyl alcohol terpolymers.
Such materials are also ~lisclose~ in EP 193,360, including, for example, the
45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
Another example of polymeric polycarboxylic cG",pounds suitable for the
purpose of the invention include the biodegradable polyaspa,lic acid and
polyglutamic acid ~mpounds.
Chelants
Chelating agents generally comprise from 0.1% to 10% by weight of
the ~mpositions herein. More preferably, if utilized, the chelating agents
will comprise from 0.1% to 3.0% by weight of such cGmpositions.
A chelating agent can be selected from amino ca, Loxylate, organic
pl ,osphol)ale, polyfunctionally-substituted aromatic co,~ "~ound, nitriloaceticacid and mixture II,ereor. Without intending to be bound by theory, it is
believed that the benefit of these materials is due in part to their exceplionalability to remove l.a"sition metal ions such as iron and ."anga,.ese ions
from washing solutions by formation of soluble chel~tes
Amino carboxylates useful as optional chelating agents include
ethylenedia..,i.,etel.acetales, ethylenediamine dis~cc;nale, N-
hydroxyethylethylenediaminetria~lates, 2-hydroxypropylene diamine
dis! ~cc;,)aLe, nitrilotriacetates, ethylenediamine tel. apro~rionates,
triethylenetetraamineh~x~cet~les, ethylene triamine pentaacetate,
diethylenetriamifie~,enlaaceta~es, and ethanoldiglycines, alkali metal,
a...,nonium, and substituted ammonium salts therein and mixtures therein.
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rlefei,ed amino carboxylates chelants for use herein are ethylanedia,nine
succindle ("EDDS"), especially the [S S] isomer as described in U.S.
Patent 4 704,233, ethylene.Jia",ine-N,N'-digll,~a",ate (EDDG) and 2-
hydroxypropylene-dia~ ~ ~ine-N N'~lisucc inale (HPDDS) cc " "~ounds.
A most prefer~ed amino cs,L,oxylate chelant is ethylenediamine ~isucc:inate.
Organic phospl-onates are also suitable for use as chelating agents
in the col ~ .posiliGns of the invention when at least low levels of total
P hOS~hOI IJS are ,c,el ")illed in detergent c~"~posilions, and include
ethylenedia,ninetetralcis (methylenephospl .onates) available under the
l.aclel.,a,k DEQUEST from Mor.sal.lo diethylene triamine penta (methylene
phos~l ,Gnate), ethylene diamine tri (methylene ~l ,OS~JI ,o"ate)
he,~a")elhylene diamine tetra (methylene phosphol .ale), a-hydroxy-2 phenyl
ethyl diphosphondle, methylene di,c)hospl)GI late, hydroxy 1,1 -hexylidene
vinylidene 1 1 diphospl,Gnate 12 dihydroxyethane 1 1 diphosphonate and
hydroxy-ethylene 1,1 diphosphonale.
r, efe. ably, these amino phospho,)ates do not contain alkyl or alkenyl
groups with more than 6 carbon atoms.
rl efe. . ~d chelants are the diphosphooate derivatives selected from a-
hydroxy-2 phenyl ethyl di~Jhosphonate methylene diphospl.G,.ale hydroxy
1,1-hexylidene vinylidene 1 1 dipl,os~Jl,o,)ale, 12 dihydroxyethane 1 1
di~l,os,vl,ol,ate and hydroxy-ethylene 1 1 cli~l,osphol)ate. A most preferred
is hydroxy-ethylene 1 1 diphosphonate.
Polyfunctionally-substituted arc,l"alic chelating agents are also useful in the
compositions herein. See U.S. Patent 3 812 044. rrefei,ed cGill~ounds of
this type in acid form are dihydroxydisulfobenzenes such as 1 2-dihydroxy-
3 ~disulfob~i~ei)e.
Amvlases
~, efe" ed amylases include for example a-amylases obtained from a
special strain of B licheniformis described in more detail in GB-1 269 839
(Novo). P,~fer,ed ccl"l"ercially available amylases include for example
those sold under the tradename Rapidase by Gist-Brocades and those sold
under the l,cdename Te,,,,c,nyl and BAN by Novo Industries A/S. Amylase
enzyme may be inco,po,aled into the col"position in accords,)ce with the
invention at a level of from 0.001% to 5% active enzyme by weight of the
composition.
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26
Builders
Detergent builders can oplio"ally be incl~ded in the c~""~osilions herein to
assist in controlling mineral I ,ardness. Inor~dnic as well as organic builders
can be used. Builders are typically used in fabric lau"deri"~ co",posilions
to assist in the removal of particulate soils.
The level of builder can vary widely depel,d;ng upon the end use of
the composition and its desired physical form. When present, the
cGIll~osiliol~s will typically cor"p,ise at least 1% builder. Granular
formulations typically cci""crise from 10% to 80%, more typically from 15%
to 50% by weight, of the ~eleryel~l builder. Lower or higher levels of
builder, however, are not meant to be excluded.
These can include, but are not resl, ic~ed to phytic acid, silicates, alkali metal
cal Llonates (including 6ica, l,Gnales and ses~Jic --- L,o,~ales), sul,vhates,
aluminosilicates, monomeric polycal L,oxylates, homo or copolymeric
poly~, l oxylic acids or their salts in which the polyca, L,oxylic acid COI "~, ises
at least two ca, L oxylic r~ic~s separaled from each other by not more than
two carbon atoms. Examples of silicate builders are the crystalline layered
sili-~tes, such as the layered sodium silicates described in U.S. Patent
4,664,839. NaSKS-6 is the ll ade,na, k for a crystalline layered silicate
~"a,l~ted by lloeol,sl (commo"ly abbreviated herein as "SKS-6"). Unlike
zeolite builders, the Na SKS-6 silicate builder does not contain aluminum.
NaSKS-6 has the delta-Na2Si2Os morphology form of layered silicate. It
can be l~repa,ecJ by methods sucn as those described in German DE-A-
3,417,649 and DE-A-3,742,043. SKS-6 is a highly prefe"ed layered silicate
for use herein, but other such layered silic~tes, such as those having the
~el ~rdl formula NaMSix02x+1 .yH20 wherein M is sodium or hyd,ogell, x is
a number from 1.9 to 4, pre~rably 2, and y is a number from 0 to 20,
pref~raL ly 0 can be used herein. Various other layered silicates from
Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and
ga""~a forms. As noted above, the delta-Na2Si2Os (NaSKS-6 form) is
most preferred for use herein. Other silicates may also be useful sucn as
for example magnesium silicate, which can serve as a crispening agent in
granular formulations, as a stabilising agent for oxygen bleaches, and as a
component of suds control systems.
Aluminosilicate builders are especially useful in the present
invention. Aluminosilicate builders are of great i""~o, lance in most currently
marketed heavy duty granular deteryellt compositions, and can also be a
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significant builder ingredient in liquid deter9e"l formulations.
Aluminosilicate builders inciude those having the empirical formula:
NaZ[(A102)Z(SiO2)y] XH20
~ whsrein z and y are illlegeis of at least 6, the molar ratio of z to y is in the
range from 1.0 to 0.5, and x is an inleyer from 15 to 264.
Useful aluminosilicate ion exchange r,al6,ials are cGi~"nercially
available. These aluminosilicates can be crystalline or a",or~,l ,ous in
structure and can be naturally-occurring aluminosilicates or sy,.ll,elically
derived. A method for producing aluminosilicAte ion exchange materials is
disclosed in U.S. Patent 3,985,669. r, efen ed synthetic crystalline
aluminosilicate ion exchange materials useful herein are available under the
desiy--aliGi-s Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an
especi ~'ly pre~, ~ eJ ei nbocJi, nent, the crystalline aluminosilicate ion
exchange ,..dl~.ial has the formula:
Na12[(Alo2)12(sio2)12] XH20
wherein x is from 20 to 30, especi-'ly 27. This material is known as Zeolite
A. Dehydlaled zeolites (x = O - 10) may also be used herein. Pleferably,
the aluminosilicate has a particle size of 0.1-10 microns in diameter.
Organic cJetergenl builders suitable for the purposes of the present
invention include, but are not restricted to, a wide variety of polyca,Lo~ylate
compounds. As used herein, "polycarboxylate" refers to compounds having
a plurality of ca, l,o..ylate groups, ~,referdbly at least 3 carboxylates.
Polycarboxylate builder can gei)erally be added to the c~lllposilio,) in acid
form, but can also be added in the form of a neutralised salt. When utilized
in salt form, alkali metals, such as sodium, potassium, and lithium, or
alkanola""..oni ~m salts are prefer.ed.
Inc~uded among the polyca, boxylate builders are a variety of
~lego,ies of useful materials. One important category of polycarboxylate
builders encGI~p~-sses the ether polycarboxylates, including oxydisuccinate,
as disclosed in U.S. Patent 3,128,287 and U.S. Patent 3,635,830. See also
'~MS/TDS" builders of U.S. Patent 4,663,071. Suitable ether
polyc~, L,o,sylates also include cyclic co"~pounds, particularly alicyclic
col."~ounds, such as those described in U.S. Patents 3,923,679; 3,835,163;
4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether
hydroxypolyca,boxylates, copolymers of maleic anhydride with ethylene or
vinyl methyl ether, or acrylic acid, 1, 3, 5-trihydroxy benzene-2, 4, 6-
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28
trisulphonic acid, and ca~ boxymethyloxysuccinic acid, the various alkali
metal, ammonium and substituted a"""onium salts of polyacetic acids such
as ethyle"ecJia. nine tet. ~Ac~lic acid and nitrilotriacetic acid, as well as
polyca.-,oxylates such as mellitic acid, succinic acid, oxy~is~ccinic acid,
polymaleic acid, L el ~ e"e 1 ,3,5-l, ica, L,oxylic acid, ca, L,oxymethyloxysuccinic
acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and scl Ihl~ salts thereof (particularly
sodium salt), are polyca,L,oxylate builders of particular i"" GIla"ce for heavy
duty liquid detergel)t formulations due to their availability from renewable
resouroes and their biodegradability. Citrates can also be used in granular
compositions, especially in combination with zeolite and/or layered silicate
builders. Oxy~isuocinales are also especially useful in such co""~osilions
and co"lbi,-ations.
Also suitable in the cor.~.osilions conlair.ing the present invention
are the 3,3~ic~,l,oxy-4-oxa-1,6-hexanedioates and the related compounds
dicclQsed in U.S. Patent 4,566,984. Useful succinic acid builders include
the Cs-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly
prefe u ed CGI I "~ound of this type is dodecenylsuccinic acid. Specific
examples of succinate builders include: laurylsuccinale, myristylsuccinate,
palmitylsucci"ate, 2- lodece"ylsucci"ale (preferred), 2-pent~de~n
nate, and the like. Laurylsuccinates are the pr~fe, led builders of this group,
and are described in EP 0,200,263.
Other suitable poly~rL,oxylates are disclosed in U.S. Patent
4,144,226 and in U.S. Patent 3,308,067. See also U.S. Pat. 3,723,322.
Fatty acids, e.g., C12-C18 monocarboxylic acids, can also be
inc~"~oraled into the col~"~ositions alone, or in co",binalion with the
aforesaid builders, espsci~'ly citrate and/or the succinale builders, to
provide additional builder activity. Such use of fatty acids will generally
result in a diminution of sudsing, which should be taken into account by the
formulator.
Conventional dete,~ive adiuncts
The compositions herein can optionally include one or more other
detergent adjunct materials or other materials for assisting or enhancing
cleaning pe,ror",a"ce, treatment of the substrate to be cleaned, or to modify
the aesthetics of the detergel ,l composition (e.g., perfumes, colorants, dyes,
etc.). The following are illustrative examples of such adjunct materials.
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29
EnzYmes
Other enzymes than proteases and amylases may be used. These include
cPll~ ses lirAses l~eroxidase endoglu~naseand mixturesthereof.
These enzymes may be incorporated into the con"~osition in acccrdance
with the invention at a level of from 0.001% to 5% active enzyme by weight
of the composition.
The cellulases usable in the present invention include both bacterial or
fungal cellulase. Preferably they will have a pH optimum of between 5 and
9.5. Suitable cell~ ses are disclosed in U.S. Patent 4435 307 which
discloses fungal cellulase prod~ced from Humicola insolens and Humicola
strain DSM1800 or a cellulase 212-producing fungus belonging to the genus
Aerc."lo"as, and cell~ se extracted from the hep~top~ncreas of a marine
mollusk (Dolabella Auricula Solander). Suitable cellulases are also
disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
ENDO A CAREZYME both from Novo Industries A/S are especially useful.
Suitable lipase enzymes for dete.ge"l usage include those produced
by ,.,icrool-ganis,ns of the Pseudomonas group such as Pseudomonas
stutzeri ATCC 19.154 as disclosed in GB 1 372 034. See also lipases in
Japanese Patent Application ~3 20487 laid open to public inspection on
February 24, 1978. This lipase is available from Amano Pha""aceutical Co.
Ltd. Nagoya Japan under the trade name Lipase P "Amano" hereinafter
referred to as "Amano-P." Other ~,~""ercial lip~ses include Amano-CES
I jPASeS ex Chromob~ctP~r viscosum e.g. Cl ,ru,,,o!~cter viscosum var.
Iipolyticum NRRLB 3S73 co",r"ercially available from Toyo Jozo Co.
Tagata Japan; and further Cl-,or"obacter viscosum lipases from U.S.
Biochemical Corp. U.S.A. and Disoynth Co. The Netherlands and lipases
ex Pseudomonas gladioli. The LIPOLASE enzyme derived from Humicola
lanuginosa and commercially available from Novo (see also EP 341 947) is
a preferred lipase for use herein.
Peruxidase enzymes are used in ~i.~b;,.ation with oxygen sources
e.g. ,cerca,L,o,)ate ~,e,L,orale persulfate hydrogen peroxide etc. They are
used for "solution bleaching" i.e. to prevent l-dnsfer of dyes or pigments
removed from su6sl,ales during wash operations to other suLsl,dles in the
wash solution. Peroxidase enzymes are known in the art and include for
-
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example, I,orser~dish peroxidase, ligninase, and haloperoxid~se such as
chloro- and bromo-pernxid~se. Pero.~ddA-se~"lai"i"y deterye- ,t
c~lllposiliGns are ~isclose~l, for exarr" l~, in EP-A~,424,398.
A wide range of enzyme ",alerials and means for their incG".~ralion
into synthetic deterge,)l compositions are also discls~se~l in U.S. Patent
3,553,139. Enzymes are further ~isclos6cl in U.S. Patent 4,101,457 and in
U.S. Patent 4,507,219. Enzyme n,alerials useful for liquid deteryent
formulations, and their i"cGIpGrdlion into such formulations, are riicclQse~l inU.S. Patent 4,261,868. Enzymes for use in ~lele,yenls can be stabilized by
various techniques. Enzyme stabilisation te.ih,.i~ues are ~isclQsed and
e~e""~lified in U.S. Patent 3,600,319 and EP 0 199 405. Enzyme
stabilisalio" systems are also desc. ibed, for e~ample, in U.S. Patent
3,519,570.
EnzYme Stabilizers - The enzymes employed herein are stabilized by
the ~,rese"ce of water-soluble sources of calcium and/or magnesium ions in
the finishe-J cc,l, "~osiliGns which provide such ions to the enzymes.
(Calcium ions are yenerally somewhat more effective than maynesium ions
and are prefe,.ed herein if only one type of cation is being used.) Additional
stability can be provided by the presence of various other art~isclosed
stabilizers, especi~"y borate species: see Severson, U.S. 4,537,706.
Typical deterge-,ls, especially liquids, will comprise from 1 to 30, ~rererably
from 2 to 20, more ~referdbly from 5 to 15, and most pre~erably from 8 to 12,
millimoles of calcium ion per liter of r~ Shed composili~n. This can vary
somewhat, ~e~ e ndi~ ~y on the amount of enzyme p, esenl and its response to
the calcium or magnesium ions. The level of calcium or magnesium ions
should be selected so that there is always some minimum level availabie for
the enzyme, after allowing for complexation with builders, fatty acids, etc., inthe cGn"~osilion. Any water-soluble calcium or ,naynesium salt can be used
as the source of calcium or magnesium ions, including, but not limited to,
calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium
hydroxide, calcium fc~,."ale, and calcium ~cet~l~, and the ~,(espG"ding
magnesium salts. A small amount of calcium ion, generally from 0.05 to 0.4
millimoles per liter, is often also present in the cc,mposilion due to calcium in
the enzyme slurry and formula water. In solid deterge"l ~mposilions the
formulation may include a sufficient quantity of a water-soluble calcium ion
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source to provide such amounts in the laundry liquor. In the alle,.,ali-/e
natural water I ,a, dl ,ess may suffice.
It is to be understood that the foreyoin9 levels of calcium and/or
magnesium ions are sufficient to provide enzyme stability. More calcium
and/or ",agnesium ions can be added to the co""~osilions to provide an
~W;lioi)al measure of grease removal pe,ru"..a"ce.
The cGm~-osiliu"s herein may also opliG"ally, but pre~rably, contain
~ various ~J-Iilio,~al stabilizers especially borate-type stabilizers. Typically
such stabilizers will be used at levels in ths co,-.posiliûns from 0.25% to
10% prereldbly from 0.5% to 5%, more ,,referably from 0.75% to 3% by
weight of boric acid or other borate compound capable of forming boric acid
in the cG.,.posi~ion (~IG~ ted on the basis of boric acid). Boric acid is
pnafel,ed although other co",pounds such as boric oxide borax and other
alkali metal borales (e.g., sodium ortho-, meta- and pyroborate, and sodium
pel~tabor~le) are suitable. Substituted boric acids (e.g. phenylLoro"ic acid
butane i~oronic acid, and p-bromo phenyl~orol ,ic acid) can also be used in
place of boric acid.
Polvmeric DisPersin~ Aqents - Polymeric dispersing agents can be utilized
at levels from 0.1% to 7% by weight in the compûsilions herein.
A polymeric material which can be included is polyethylene glycol (PEG).
PEG can exhibit d;spersi"g agent performance as well as act as a clay soil
removal-a,)ti.~le~Josilion agent. Typical molecular weight ranges for these
pu. poses range from 500 to 100 000 preferably from 1 000 to 50 000 more
p. eferably from 1 500 to 10 000.
Polyaspa. lale and polyglula- "ate dispersing agents may also be
used esp~ri?'ly in conjunction with zeolite builders. Dispersing agents
such as polyaspal late p, efe, ably have a molecul~r weight (avg.) of 10 000.
Clav Soil Removal/Anti-redePosition Aaents - The c~mposiliGns of the
present invention can also optionally contain water-soluble ethoxylated
amines having clay soil removal and antiredeposition properties. Granular
deterger,l cG",positions which co"lain these cc",pounds typically contain
from 0.01% to 10.0% by weight of the water-soluble ethoxylates amines;
liquid deterge"t co,-"~ositions typically contain 0.01% to 5%.
The most pl e~ ~ ed soil release and anti-redeposition agent is
ethoxylated tel- d~lhylenepentamine. Exemplary ethoxylated amines are
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further desc il,ed in U.S. Patent 4,597,898 VanderMeer, issued July 1
1986. Another group of prefer,ed clay soil removal-antire-~eposiliGi. agents
are the cationic co.-.pounds ~lisclosecl in Eu-opea.. Patent A~lj~t;GII
111,965 Oh and Gosselink, published June 27, 1984. Other clay soil
removal/antiredeposition agents which can be used include the ethoxylated
amine polymers disclosed in European Patent Application 111 984
~;osselink, published June 27 1984; the zwitterionic polymers disclosed in
European Patent Application 112,592 Gosselink published July 4 1984
and the amine oxides disclose~J in U.S. Patent 4,548,744 Connor, issued
October 22 1985. Other clay soil removal and/or anti re-le~osiliGn agents
known in the art can also be utili7ed in the colllposiliG"s herein. Another
type of prefer, ed antire~leposition agent includes the ca, ~,oxy methyl
cellulose (CMC) materials. These materials are well known in the art.
Polvmeric Soil Release Aqent - Any polymeric soil release agent known to
those skilled in the art can oplionally be employed in the compositions and
~,n~c~sses of this invention. Polymeric soil release agents are characterized
by having both hydrophilic segments to hydrophilize the surface of
hydl c pl ,ol~ic fibers such as polyester and nylon and hydrophobic
sey",enla, to depos;l upon hydlophoLic fibers and remain adhered thereto
through completion of washing and rinsing cycles and thus serve as an
a,)cl,or for the hydrophilic segments. This can enable stains occurring
sl~hse~uent to treatment with the soil release agent to be more easily
cleaned in laterwasl.iny proce.Jures.
J The polymeric soil release agents useful herein especially include
those soil release agents having: (a) one or more "o"io"ic hydrophile
~m~otl6nla consisting essentially of (i) polyoxyethylene segments with a
das~. ee of poly"~eri~dlion of at least 2 or (ii) oxypropylene or
polyoxypropylene segments with a degree of poly",eri~alion of from 2 to 10
wherein said hydrophile segment does not e"~r"pass any oxypropylene
unit unless it is bonded to ~j~c~nt moieties at each end by ether linkages
or (iii) a mixture of oxyalkylene units cc""~risi,lg oxyethylene and from 1 to
30 oxypropylene units wherein said mixture contains a sufficient amount of
oxyethylene units such that the hydrophile ccmponent has hydrophilicity
great enough to increase the hydrophilicity of con~,enlio"al polyester
sy"ll,etic fiber surfaces upon deposit of the soil release agent on such
surface said hydrophile segments preferably ccl",~,risi"g at least 25%
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33
oxyethylene units and more p,er~rably, especially for such co",poi,enls
having 20 to 30 oxypropylene units, at least 50% oxyethylene units; or (b)
one or more hyd~u~l-ol,e cG",po"ents co,.~prising (i) C3 oxyalkylene
terephll ~alate segments, wherein, if said hydl uphobe co, - .ponents also
cG..,prise oxyethylene tere~ hll.alate, the ratio of oxyethylene
terepl.ll)aldte:C3 oxyalkylene telepl,lllalate units is 2:1 or lower, (ii) C4-C6alkylene or oxy C4-C6 alkylene se~lllents, or mixtures therein, (iii) poly
(vinyl ester) seg..-e--ls, prefer~bly polyvinyl ~c~t~te), having a degree of
polymeri~dtiG.. of at least 2, or (iv) C1-C4 alkyl ether or C4 hydroxyalkyl
ether substituents, or mixtures ll .ere;, ., wherein said substituents are
~,resenl in the form of C1-C4 alkyl ether or C4 hydroxyalkyl ether cellulose
derivatives, or mixtures therein, and such cellulose derivatives are
amphiphilic, whereby they have a sufficient level of C1-C4 alkyl ether and/or
C4 hydroxyalkyl ether units to deposil upon conventional polyester synthetic
fiber surfaces and retain a sufficient level of hydroxyls, once adhered to
such convei)tior-al synthetic fiber surface, to increase fiber surface
hycll opl ~ilicil~, or a corrh:nalio. . of (a) and (b).
Typically, the polyoxyethylene seS~",ents of (a)(i) will have a degree
of polymerization of from 200, although higher levels can be used,
preferaLIly from 3 to 150, more preferably from 6 to 100. Suitable oxy C4-C6
alkylene hydlophobe segments include, but are not limited to, end~aps of
polymeric soil release agents such as MO3S(CH2)nOCH2CH2O-, where M
is sodium and n is an integer from 4-6, as disclosed in U.S. Patent
4,7211~80, issued January 26, 1988 to Gosselink.
Polymeric soil release agents useful in the present invention also
include cellulosic derivatives such as hydroxyether cellulosic polymers,
copolymeric blocks of ethylene terepl,tl,alate or propylene tereplltl,alate
with polyethylene oxide or polypropylene oxide tereplltl,alate, and the like.
Such agents are co"""ercially available and include hydroxyethers of
cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use
herein also include those selected from the group consisting of C1-C4 alkyl
and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued Decer"ber
28, 1976 to Nicol, et al.
Soil release agents characterized by poly(vinyl ester) hydrophobe
segments include graft copolymers of poly(vinyl ester), e.g., C1-C6 vinyl
esters, preferably poly(vinyl ~cePtP) grafted onto polyalkylene oxide
backbones, such as polyethylene oxide backbones. See European Patent
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34
~pplic~tion 0219048, published April 22,1987 by Kud, et al. Co"""e~ially
available soil release agents of this kind include the SOKALAN type of
",alerial, e.g., SOKALAN HP-22, available from BASF (West Germany).
One type of prefe" ~d soil release agent is a copolymer having
r~nclon, blocks of ethylene tere~Jl)l~ ,alate and polyethylene oxide (PEO)
tereplltl,alate. The molec~ weight of this polymeric soil release agent is
in the range of from 25,000 to 55,000. See U.S. Patent 3,959,230 to Hays,
issued May 25,1976 and U.S. Patent 3,893,929 to R~s~d~Jr issued July 8,
1975.
Another prerel,ed polymeric soil ,elease agent is a polyester with
repeat units of ethylene tert~cl,l~,alate units contains 10-15% by weight of
ethylene tere~htl ,alate units together with 90-80% by weight of
polyoxyethylene tere,c,l,lllalate units, derived from a polyoxyethylene giycol
of average molec~ r weight 300-5,000. EXdlllpleS of this polymer include
the co",.nercially available material ZELCON 5126 (from Dupont) and
MILEASE T (from ICI). See also U.S. Patent 4,702,857, issued October 27,
1987 to t~;osselink.
Another ~rerel . e.J polymeric soil release agent is a sulrona~ed
product of a s~ -lially linear ester oligomer comprised of an oligomeric
ester ~acl~l,one of terephll .aloyl and oxyalkyleneoxy repeat units and
terminal moieties covalently attached to the backbone. These soil release
agents are described fully in U.S. Patent 4,968,451, issued November 6,
1990 to J.J. Scheibel and E.P. Gosselink. Other suitable polymeric soil
release agents include the terephll ,alate polyesters of U.S. Patent
4,711,730, issued Decei"ber 8,1987 to ~osselink et al, the anionic end-
capped oligomeric esters of U.S. Patent 4,721,580, issued January 26,1988
to ~osselirlk, and the block polyester oli~o,.,eric compounds of U.S. Patent
4,702,857, issued October 27,1987 to Gosselink.
P,ere,.ed polymeric soil release agents also include the soil release
agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et
al, which discloses anionic, especially sulfoarolyl, end~a~"~ed terq~l,ll,alate
esters.
If ~-til;~g~l, soil release agents will generally comprise from 0.01% to
10.0%, by weight, of the deterge"l ccmposilions herein, typically from 0.1%
to 5 %, preferably from 0.2 % to 3.0%.
Still another prere"ed soil release agent is an oligomer with repeat
units of tere~l-ll,aloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and
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oxy-1,2-propylene units. The repeat units form the backboi)e of the
oligomer and are ,creferably te,."i.,ated with modified isetl,iondle end-caps.
A particularly prefe" ed soil release agent of this type CGI I ",rises one
sulfoisGphll,aloyl unit, 5 terq~lltl,aloyl units oxyethyle"eoxy and oxy-1,2-
propyleneoxy units in a ratio of from 1.7 to 1.8, and two end-cap units of
sodium 2-(2-hydroxyethoxy)~ll,anesulro"ate. Said soil r~lea-~.e agent also
co,oprises from 0.5% to 20% by weight of the oligomer of a crystalline-
reducing st~hili~er, ,~ refera~ly ~ le-l from the group collsisliny of xylene
sulro"dte, cumene sulrol ,ale, toluene sulfonate and mixtures ll ,ereof.
DYe Tral ,~rer Inhibitina Aqents - The cor"positions of the ,c resenl invention
may also include one or more materials effective for inhibiting the l,ansrer of
dyes from one fabric to another during the cleaning ~,ocess. Generally
such dye l,an~rer iullitlilillg agents include polyvinyl pyrrolidone polymers
polyamine N-oxide polymers, copolymers of N-vinylp)", olidone and N-
vinylimid~ole manganese phthalocyanine peroxidases and mixtures
ll,ereof. If used, these agents typically col"~rise from 0.01% to 10% by
weight of the cGlnposilion~ prererably from 0.01% to 5% and more
preferably from 0.05% to 2%.
More specifically, the polyamine N-oxide polymers prerel,ed for use
herein contai.- units having the following structural formula: R-AX-P; wherein
P is a poly",eri~able unit to which an N-O group can be attached or the N-O
group can form part of the pol~",e,i~able unit or the N-0 group can be
allacl)~i to both units; A is one of the following structures: -NC(O)- -C(O)O-
-S-, -O- -N=; x is 0 or 1; and R is ali~l ,alic ethoxylated aliphatics
aro",alics l,eterc~clic or alicyclic groups or any cG",bi"alion thereof to
which the rlilloyell of the N-O group can be alla~;l,ed or the N-O group is
part of these groups. Prere"ed polyamine N-oxides are those wherein R is
a heterocyclic group such as pyridine pyrrole imidazole pyrrolidine
piperidine and derivatives thereof.
The N-O group can be represented by the following general
structures:
O O
2~; = N ~ 1
~3~
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36
wherein R1, R2, R3 are aliphatic, aro",alic, I,ete,ucyclic or alicyclic groups
or cc,-~ lio,~s thereof; x, y and z are 0 or 1; and the ~-ilr~gen of the N-0
group can be aUacl.ed or form part of any of the arorer..e.,llo.-ed groups.
The amine oxide unit of the polyamine N-oxides has a pKa <10, ~referably
pKa ~7, more prer~ pKa c6.
Any polymer l,ac~L,one can be used as long as the amine oxide
polymer ~I~ed is water-sol~hlo and has dye l,an:irer inhibiting ptopellies.
Examples of suitable polymeric backbones are polyvinyls, polyalkylenes,
polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures
ll,~r~or. These polymers include random or block copolymers where one
.nono--,er type is an amine N-oxide and the other ..,o.,or..er type is an N-
oxide. The amine N-oxide polymers typically have a ratio of amine to the
amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide
groups ~resenl in the polyamine oxide polymer can be varied by appro~,riale
copoly. . .eri~alio., or by an a~.p. o~l iate degree of N~xiddliGn. The
polyamine oxides can be obtained in almost any degree of polymerization.
Typically, the average m ~l ec~ weight is within the range of 500 to
1,000,000; more prefel . ed 1,000 to 500,000; most ~,re~rre~ 5,000 to
100,000. This ,c,ref~..ed class of ...dterials can be referred to as "PVNO".
The most ~,refe(. ed polyamine N-oxide useful in the detergent
ccm~sitions herein is poly(4-vinylpyridine-N-oxide) which as an average
molecular weight of 50,000 and an amine to amine N-oxide ratio of 1:4.
Copolymers of N-vinylpyrrolidone and N-vinyli, niJa~ole polymers
(referred to as a class as "PVPVI") are also prer~l . ed for use herein.
r~eferdbly the PVPVI has an average molsall~r weight range from 5,000 to
1,000,000, more preferably from 5,000 to 200,000, and most preferably from
10,000 to 20,000. (The average molecular weight range is determined by
light sc~lleri--y as desc ibed in Barth, et al., Cl,elnical AnalYsis, Vol 113.
"Modern Methods of Polymer Ch~ra-;leri alion", the disclosures of which are
incorporated herein by reference.) The PVPVI copolymers typically have a
molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more
pfererably from 0.8:1 to 0.3:1, most p.ererdbly from 0.6:1 to 0.4:1. These
copolymers can be either linear or brdnd~ed.
The presel.l invention compositions also may employ a polyvinyl-
pyrrolidone ("PVP") having an average molec~ weight of from 5,000 to
400,000, p,efer,ably from 5,000 to 200,000, and more prefelably from S,000
to 50,000. PVP's are known to persons skilled in the detergent field; see,
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37
for exa",l~le, EP-A-262,897 and EP-A-256,696. Co",posilions containi"g
PVP can also conW,) polyethylene glycol ("PEG") having an average
moleu~ weight from 500 to 100,000, prererably from 1,000 to 10,000.
r,ef~rably, the ratio of PEG to PVP on a ppm basis delivered in wash
sol ~tions is from 2:1 to 50:1, and more ~r~f~rdbly from 3:1 to 10:1.
The datergent compositions herein may also optionally contain from
0.005% to 5% by weight of certain types of hydrophilic optical b,i~l,le-)ers
which also provide a dye l,ansrer inhibition action. If used, the ccmposilions
herein will prefer~bly comprise from 0.01% to 1% by weight of such optical
b. i~l .lel ,ers.
The hydrophilic optical bri~JI .leners useful in the p, ese, ll invention are
those having the structural formula:
Rl R2
N O~NI ~NI ~N
~N H H N~
R2' SO3M SO3M R
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-
methylamino, r"o"~l,ilino, chloro and amino; and M is a salt-forming cation
such as sodium or poPssi~ Im.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl
and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino~-(N-
2-bis-hydroxyethyl)-s-l, ia~ine-2-yl)amino]-2,2'-stilL,enedisulfonic acid and
disodium salt. This particular b,i~hlener species is commercially marketed
under the l,adena",e Tinopal-UNPA-GX by Ciba-Geigy Corporation.
Tinopal-UNPA-GX is the pr3re"ed hydrophilic optical brightener useful in
the detergel)l compositions herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-
2-methylamino and M is a cation such as sodium, the brightener is 4,4'-
bisl(4-anilino~-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-
yl)amino]2,2'-stilbenedisulfonic acid ~lisorliuln salt. This particular
brigl.tel,er species is commercially marketed under the l,ade,-a...e 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~-morphilino-s-
triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular
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38
briyl ,lener species is coi - "~ ,ercially marketed under the lralJe, .a, . ,e Tinopal
AMS-GX by Ciba Geigy CGI ,UOr;~I;G~ 1.
The s~e~ iric optical brigl ,te, .er specias sele~e- I for use in the present
invention provide especi~y effective dye l(dn~rer inhibition pelrol-"dnce
benefits when used in comb.. ~atiGn with the sele~1e-J polymeric dye lr~l ,srer
inl ,ibiling agents hereinberore desc, il,ed~ The combination of such selected
polymeric materials (e~g~, PVN0 and/or PVPVI) with such selected optical
b,i!Jl,leners (e~g. Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-
GX) provides significantly better dye l-ansrer inhibition in ~ eous wash
sol~tions than does either of these two delergent c~l..posilion cG",pGnents
when used alone. Without being bound by theory it is believed that such
briyl Itel ~ers work this way be~use they have high affinity for fabrics in the
wash solution and tl,ererore ~leposil relatively quick on these fabrics~ The
extent to which L,ri!Jl.te,)era cJe~sil on fabrics in the wash solution can be
d~ine~l by a para.,.eter called the "exh~ustion coefficient"~ The exhaustion
cG~rricie.,l is in general as the ratio of a) the brightener material de~osiled
on fabric to b) the initial brightener concenl, dlion in the wash liquor.
B- iyl ~lel)ers with relatively high exh~ Istion coefric;e. ,ts are the most suitable
for inhibiting dye transfer in the context of the present invention~ _
Of course, it will be appre~ ted that other conventional optical
briyl ,tener types of co""~ounds can optionally be used in the present
coi n~osilions to provide conventional fabric "bri~l ,l"ess" benefits rather
than a true dye t-d"arer inhibiting effect. Such usage is conventional and
well-known to deter~e"t formulations.
Conventiol,al optical brigl,lenera or other brightening or whitening agents
known in the art can be i"c~l~,o(aled at levels typically from 0.005% to 5%
pre~r~bly from 0.01% to 1.2% and most prefe,ably from 0.05% to 1.2% by
weight into the d-3terge,lt compositions herein. Coi "" ,ercial optical
bri5Jl,tenerà which may be useful in the present invention can be classified
into subgroups which include but are not necess--- ily limited to derivatives
of stilbene, pyrazoline coumarin ca,Loxylic acid ."ell,inecyanines
dibel- otl,io~,l,e"e-55~ioxide azoles 5- and 6~ner,bered-ring
heterocycles and other miscellaneous agents. Examples of such
brigl ,te"era are ~isclosed in '~he Production and Application of Fluorescent
Brightening Agents", M. Zah-adl,ik Published by John Wiley & Sons New
York (1982). Further optical brigl,Lener which may also be used in the
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present invention include naphthlimide, ben,o~ol3, benzofuran,
bell~illlid~No and any mixtures thereof.
Specific examples of optical L ri$~1,le, .ers which are useful in the
present cG"~posiliGns are those identified in U.S. Patent 4,790,856. These
brighle"efs include the PHORWHITE series of ~riyl,leners from Verona.
~ Other L.righl6l ,er~ ~lisclosed in this rerer~nce include: Tinopal UNPA,
Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artic White CC
and Artic White CWD; the 2~4-styryl-phenyl)-2H-I ,apl1 lo[1,2-d]tri~olcs;
4,4'-bis(1,2,3-triazol-2-yl)-stilbenes; 4,4'-bis(styryl)bisphenyls; and the
aminocou",arins. Specific e~a",,~ s of these bri~l ,teners include 4-methyl-
7-diethyl- amino coumarin; 1,2-bis(-benzimidazol-2-yl)ethylene; 1,3-
diphenyl-pyr~olines; 2,5-bis(ben7Ox~ol-2-yl)thiophene; 2-styryl-naptho-
~1,2-d'o.~-l~; and 2-(stilbene4-yl)-2H~)apl,lho[1,2-d]tri~ole. See also
U.S. Patent 3,646,015.
Suds SuPDressors - Compounds for reducing or suppressing the formation
of suds can be i,.ccl~.oraled into the composilions of the pr~senl invention.
Suds su~.r~ssiGn can be of particular i""~olla"ce in the so-called "high
concel-l, dlion cleaning ~,rc,cess" and in front-loading EUI upeal ,-style
~ashing ma~ ,i"es.
A wide variety of materials may be used as suds suppressors, and
suds su~ressGra are well known to those skilled in the art. See, for
example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition,
Volume 7, pages 430 447 (John Wiley 8 Sons, Inc., 1979). One category of
suds su~",r~ssor of particular interest enco"-p~sses monoca,Loxylic fatty
acid and sohlhle salts therein. See U.S. Patent 2,954,347, issued
Sept~",ber 27, 1960 to Wayne St. John. The monoca,L,oxylic fatty acids
and salts thereof used as suds suppressor typically have hydl oczi, byl chains
of 10 to 24 carbon atoms, preferdbly 12 to 18 carbon atoms. Suitable salts
include the alkali metal salts such as sodium, potassium, and lithium salts,
and a",mGnium and alkanol~n""onium salts.
The deterge"t cGillpositions herein may also contain non-surfactant
suds suppressor~. These include, for example: high molecular weight
hyclruca, L,ons such as pararri", fatty acid esters (e.g., fatty acid
triglycerides), fatty acid esters of monovalent alcohols, aliphatic C1g-C40
ketones (e.g., stearone), etc. Other suds inhibitors include N-alkylated
amino ll i~i"es such as tri- to hexa-alkylmelamines or di- to tetra-
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alkyldia,ni.le chlo,l,ia~ines formed as products of cyanuric chloride with two
or three moles of a primary or secondary amine conlaininy 1 to 24 carbon
atoms, propylene oxide, and ",Gnoslearyl phosphates such as ",o"ostea(yl
alcohol phosphate ester and ~nG.,oslea"~l di . ~k~li metal (e.g., K Na and Li)
pl,ospl,dtes and pl,ospl,ale esters. The hydn~calL,o,)s such as pa,~fin and
halGpararfin can be utilized in liquid form. The liquid hydloca,~Gns will be
liquid at room le",per~l-Jre and at",os~l,eric pressure, and will have a pour
~ point in the range of 40~C and 50-C and a minimum boiling point not less
than 110~C (al",ospl,~ric pressure). It is also known to utilize waxy
hyd~oca. L,ons, ,~,referably having a melting point below 1 00~C. The
hy.l~ o~. L,ons CGI ,slilute a preferred c~tegory of suds suppressor for
detergent cGmposili~lls. Hyd~oca,L,on suds supprdssGrs are des~i~ed for
exd""~le in U.S. Patent 4 265 779, issued May 5, 1981 to Gandolfo et al.
The h~d~oc ILolls, thus, include aliphatic, alicyclic arc"-,alic and
hetero~clic saturated or unsaturated hyd~o~,bons having from 12 to 70
ca, L,on atoms. The term pa, arfin," as used in this suds suppressor
~is~ ~ssion, is in~e, Ided to include mixtures of true pardfi"s and cyclic
hy~ GI)S.
Another p. er~l ~ ed c~tegory of non-su- ra~a"t suds suppressors
cGmp~ises silicG"e suds suppressors. This calegG,y inrl-~des the use of
pol~,orya,)osiloxa~le oils such as polydi"~ll)ylsiloxane dispersions or
emulsions of polyorga"osilo)~ne oils or resins and combinations of
polyorganosiluxa"e with silica particles wherein the polyorganosiloY~ne is
che",isG,bed or fused onto the silica. Silicone suds sup~ressors are well
known in the art and are for example ~isclosed in U.S. Patent 4 265 779
issued May 5, 1981 to GanJolro et al and Europea,) Patent Applicdlion No
89307851.9 published February 7 1990 by Starch M. S.
Other silicone suds suppressor~ are disclosed in U.S. Patent
3 455 839 which relales to compositions and processes for defoaming
eous solutions by incorporating Ll ,erei.l small amounts of
polydi"~ell)ylsiloxane fluids.
Mixtures of silicone and silanated silica are described for insta"ce in
German Patent Application DOS 2124 526. Silicone defoa"~e,a and suds
controlling agents in granular de~ergenl col"posilions are disclosed in U.S.
Patent 3 933 672 Bartolotta et al and in U.S. Patent 4 652 392 Baginski et
al issued March 24 1987.
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An exemplary silicone based suds suppressor for use herein is a
suds suppressing amount of a suds controlling agent c~nsisling esser,lially
of:
(i) polydimethylsiloxane fluid having a viscosily of from 20 cs. to 1,500
cs. at 25~C;
(ii) from 5 to 50 parts per 100 parts by weight of (i) of siloxane resin
cc,."posed of (CH3)3SiO1t2 units of SiO2 units in a ratio of from (CH3)3
SiO1/2 units and to si02 units of from 0.6:1 to 1.2:1; and
(iii) from 1 to 20 parts per 100 parts by weight of (i) of a solid silica gel.
In the prefe"ed silicone suds suppressor used herein, the solvent for
a continuous phase is made up of certain polyethylene glycols or
polyethylene-polypropylene glycol copolymers or mixtures thereof
.ere,.~d), or polypropylene glycol. The primary silicone suds suppressor
is ~ranel .edtcrossli. ,kec~ and prerer~bly not linear.
To illustrate this point further, typical liquid laundry detergent
co~ osilio..s with controlled suds will optionally c~,.,p,ise from 0.001 to 1,
~,ere,ably from 0.01 to 0.7, most preferably from 0.05 to 0.5, weight % of
said silicone suds suppressor, which comprises (1) a non~ eo~s emulsion
of a ~ri",a,y anliroan, agent which is a mixture of (a) a polyorganosiloxane,
(b) a resinous siloxane or a silicone resin-producing silicone compound, (c)
a finely divided filler material, and (d) a catalyst to proi"ote the reaction ofmixture cc"--~oneuls (a), (b) and (c), to form silanolates; (2) at least one
nonionic silicone su.ra.;ta.lt, and (3) polyethylene glycol or a copolymer of
polyethylene-polypropylene glycol having a solubility in water at room
temperature of more than 2 weight %; and without polypropylene glycol
Similar amounts can be used in granular cc,i."~ositions, gels, etc. See also
U.S. Patents 4,978,471, Starch, issued December 18, 1990, and 4,983,316,
Starch, issued January 8, 1991, 5,288,431, Huber et al., issued February
22, 1994, and U.S. Patents 4,639,489 and 4,749,740, Aizawa et al at
column 1, line 46 through column 4, line 35.
The silicone suds suppressor herein prereraL,ly comprises
polyethylene glycol and a copolymer of polyethylene glycol/polypropylene
glycol, all having an average molecular weight of less than 1,000, preferably
between 100 and 800. The polyethylene glycol and
polyethylene/polypropylene copolymers herein have a sol~hility in water at
room te--"~erdlure of more than 2 weight %, preferably more than 5 weight
%.
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42
The p, efer, ed solvent herein is polyethylene glycol having an
average molecular weight of less than 1,000, more preren31,1y between 100
and 800, most pref~rably between 200 and 400, and a copolymer of
polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300.
r, ere" ad is a weight ratio of between 1:1 and 1 :10, most prerer~L ly
between 1:3 and 1:6, of polyethylene glycol:copolymer of polyethylene-
polypropylene glycol.
The prefe"~d silicone suds suppressors used herein do not contain
polypropylene glycol, particularly of 4,000 molec~ weight. They also
,.,rere,ably do not contain block copolymers of ethylene oxide and propylene
oxide, like PLURONIC L101.
Other suds suppressor:, useful herein comprise the secondary
alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone
oils, such as the silicones (I;sclosed in U.S. 4,798,679, 4,075,118 and EP
150,872. The seconda(y al~hols include the C6-C16 alkyl alcohols having
a C1-C16 chain. A prere"ecl alcohol is 2-butyl octanol, which is available
from Condea under the l(ade,.,a,k ISOFOL 12. Mixtures of secondaly
alcohols are available under the trademark ISALCHEM 123 from Enichem.
Mixed suds su~.pressGrs typically comprise mixtures of alcohol + silicone at
a weight ratio of 1:5 to 5:1.
For any detergenl CGI I ,positions to be used in automatic laundry
washing machines, suds should not form to the extent that they overflow the
washing ",ac~,ine. Suds suppressors, when utilized, are prefe,ably present
in a "suds sL"~"~ressinSJ amount. By"suds s~"~pressing amount" is meant
that the formulator of the ccmposilion can select an amount of this suds
controlling agent that will sufficiently control the suds to result in a low-
sudsing laundry clelergenl for use in automatic laundry washing machines.
The compositions herein will generally comprise from 0% to 5% of
suds s~.~pressor. When ~tili~ed as suds suppressors, monoca,boxylic fatty
acids, and salts ll,erGi.), will be present typically in amounts up to 5%, by
weight, of the deteryent composition. P,ererably, from 0.5% to 3% of fatty
monoca,L,oxylate suds suppressor is utilized. Silicone suds suppressors
are typically utilized in amounts up to 2.0%, by weight, of the detergent
~mposiliGn, although higher amounts may be used. This upper limit is
practical in nature, due primarily to cGnce,n with ke~ping costs minimized
and effectiveness of lower amounts for effectively controlling sudsing.
P,~rerably from 0.01% to 1% of silicone suds suppressor is used, more
-
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43
prererably from 0.25% to 0.5%. As used herein, these weight percentage
values include any silica that may be utilized in COIllbi- IdliUn with
polyoryanosiloxane~ as well as any adjunct ",alerials that may be utili~e~
Monostearyl phospl,ale suds suppressGrs are ge"erally utili~ed in amounts
rang;. ,y from 0.1 % to 2%, by weight, of the co" ~ ~osilion. Hydl uca, bon sudssup,c"~ssor~ are typically utili~e~ in amounts ranging from 0.01% to 5.0%,
although higher levels can be used. The alcohol suds s~ ,essor:j are
typically used at 0.2%-3% by weight of the finished co" I~. osiliG~ ~s.
Fabric Softeners - Various through-the-wash fabric softeners, especially the
irnp~lpAble s",ectile clays of U.S. Patent 4,062,647, Storm and Nirschl,
issued Dec~,~,ber 13, 1977, as well as other softener clays known in the art,
can optionally be used typically at levels of from 0.5% to 10% by weight in
the present co",positions to provide fabric sonener benefils concurrently
with fabric cleaning. Clay s~flener~ can be used in cG",bi.)dlion with amine
and cationic sonenel~ as dis-,lQse~l. for example, in U.S. Patent 4,375,416,
Crisp et al, March 1, 1983 and U.S. Patent 4,291,071, Harris et al, issued
Septe" ,ber 22, 1981.
Other Inaredients - A wide variety of other functional ingredients useful in
deteryent compositions can be included in the ~" ,~ositions herein,
including other active ingredients, carriers, h~ rol,opes, processing aids,
dyes or piyn~el)ts~ solvents for liquid formulations, solid fillers for bar
compositions, etc. If high sudsing is desired, suds boosters such as the
C10-C16 alkanolamides can be incG"~G,aled into the com~siliu,,s, typically
at 1%-10% levels. The C10-C14 ",onoettlanol and diethanol amides
illustrate a typical class of such suds boosters. Use of such suds boosters
with high sudsing adjunct su,ra,,lanls such as the amine oxides, betaines
and sultaines noted above is also advantageous. If desired, soluble
magnesium salts such as MgCI2, MgS04, and the like, can be added at
levels of, typically, 0.1%-2%, to provide additional suds and to enhance
grease removal pe,ru""ance.
Liquid detelgent co",posilions can contain water and other
solvents as carriers. Low molecular weight primary or secc "da(y alcohols
exemplified by methanol, ethanol, pn~panol, and iso~ropanol are suitable.
Mo"ol"~dric alcohols are prere"ed for solubilizing surfactant, but polyols
such as those containing from 2 to 6 carbon atoms and from 2 to 6 hydroxy
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groups (e.g., 1 ,3-1,rol~. ~ediol, ethylene glycol, glycerine, and 1,2-
~rG~.a-lediol) can also be used. The comrositions may contain from 5% to
90%, typically 10% to 50% of such ca,.ie,a.
The deter~~enl colllposiliGIls herein will ~,,ererably be formulated such
that, during use in :3~UeO! IS cleaning operdlio"s, the wash water will have a
pH of between 6.5 and 11, ~ f~rably between 7.5 and 10.5. Liquid
dishwashing product formulations ,~referably have a pH between 6.8 and
9Ø Laundry products are typically at pH 9-11. Techniques for controlling
pH at reco...,-~er,d~J usage levels include the use of buffers, alkalis, acids,
etc., and are well known to those skilled in the art.
Form of the cGi-"~osilions
The det~.gel ,l co,..posilions of the invention can be formulated in any
deâil able form such as powders, granulates, pastes, liquids, and gels.
Liquid com~ositions
The .leler~enl compositions of the prese"l invention may be formulated as
liquid del~rgel~t co.nposilions. Such liquid detergent compositions typically
~..-~,,ise from 94% to 35% by weight, preferably from 90% to 40% by
weight, most prefefably from 80% to 50% by weight of a liquid carrier, e.g.,
water, prefe, ably a mixture of water and organic solvent.
Gel co..,i~osilions
The de~er~e, It co,."~ositions of the ~,resent invention may also be in the formof gels. Such comrosilions are typically formulated with polyakenyl
polyether having a molecular weight of from about 750,000 to about
4,000,000.
Solid co,~"~ositions
The Jeteryent cGI~"~osilions of the invention may also be in the form of
solids, such as powders and granules.
The mean particle size of the co" ,ponents of granular compositions in
accorda"ce with the invention should prererably 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.
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The term mean pa,licle size as defined herein is calc~ te-i by sieving a
sample of the c~s",posi~ion into a number of rl~~ions (typically 5 fractions)
on a series of Tyler sieves. The weight r,actions thereby obtained are
plotted against the aperture size of the sieves. The mean particle size is
taken to be the aperture size through which 50% by weight of the sample
would pass.
The bulk density of granular delerge,)l cor"posilions in accorda"ce with the
prese"l invention are also useful in concenl, dled granular deterge"l
composiliol ,s that are cl ,aracterisecJ by a relatively high density in
cGmpa~isGn with convenlio"al laundry deterger)l cGIllposilion3. Such high
density composilions typically have a bulk density of at least 600 g/litre
more p, ererably from 650 g/litre to 1200 g/litre most preferably from
800g/litre to 1 OOOg/litre.
Bulk density is measured by means of a simple funnel and cup device
consisting of a conical funnel mo! ~ded rigidly on a base and provided with a
flap valve at its lower exl,e",ily to allow the cGnlel)ls of the funnel to be
emptied into an axially aligned cylindrical cup disposed below the funnel.
The funnel is 130 mm high and has intemal dia",eters of 130 mm and 40
mm at its respective upper and lower extremities. It is mounted so that the
lower e~lre",ily is 140 mm above the upper surface of the base. The cup
has an overall height of 90 mm an intemal height of 87 mm and an intemal
dia",eter of 84 mm. Its nol"inal volume is 500 ml.
To carry out a measure",ellt the funnel is filled with powder by hand
pouring, the flap valve is opened and powder allowed to overfill the cup.
The filled cup is removed from the frame and excess powder removed from
the cup by passing a straight edged implement eg; a knife across its upper
edge. The filled cup is then weighed and the value obtained for the weight
of powder doubled to provide a bulk density in g/litre. Replicate
measurements are made as required.
Mahil ,q ~rocesses - aranular comPositions
- In yel)ernl~ granular detergent compositions in accordal)ce with the present
invention can be made via a variety of methods including dry mixing spray
drying agylol"eration and granulation.
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46
The invention is illustrated in the following non limiting e).a...~les, in whichall pe.c~"lages are on a weight basis unless otherwise stated.
In the bleaching compositions of the invention, the abbreviated ~m~o.-e"~
id6nliri~liGns have the following meanings:
LAS : Sodium linear C12 alkyl be"-ene
SU4JI ~C: I .al~
TAS : Sodiumtallowalcohol sulphate
C45AS : Sodium C14-C1 5 linear alkyl sulphate
C45E7 : A C14 15 predominantly linear primary alcohol
cc")de.)sed with an average of 7 moles of
ethylene oxide
C25 E3 A C12-15 ~rdl)~cl primary alcohol cc ndel ,sed
with an average of 3 moles of ethylene oxide
C25E5 : A C12 15 branched primary alcohol conde,)sed
with an average of 5 moles of ethylene oxide
NO.~;GI);C : (hydroxyethyl dimethyl) a""~,onium quatemary
Silicate : Amo",l ,ous Sodium Silicate (SiO2:Na20; 1.6
ratio)
NaSKS4 : Crystalline layered silicate offormula
~ -Na2Si205
Ca,bol,ate : Anhydrous sodium carbonate with a particle size
between 200~m and 9001lm
Sulphate : Anhydrous sodium sulphate
Zeolite A : Hydrated Sodium Aluminosilicate of formula
Na12(A102SiO2)12- 27H2~
having a primary particle size in the range from
0.1 to 10 mi~cnneters
MA/AA : Copolymer of 1:4 malciclacrylic acid, average
molecular weight about 70,000.
PB4 : Sodium perL,orale tetrahydrate of nominal
formula NaBo2~3H2o H2o2
PB1 : Anhydrous sodium perborate bleach of
nominal formula NaBo2.H2o2
TAED : Tetraacetyl ethylene diamine
~ AvO2 : Total amount of available oxygen present in the
~ composition
Bri-Jhlel ,er 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl
-
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47
Bri~l Itener 2 : Disodium 4,4'-bis(4-anilino~-",o"JI ,olino-1.3.5-
triazin-2-yl)amino) stilbene-2:2'-disul,ul ,onale.
HEDP : Hydroxy-ethylene 1 1 di~l ,os~hu. ,dle
DTPMP: Diethylene l,ia",;ne penta (methylene phos~Jl,onate)
marketed by Mlonsanto under the Trade name
st 2060
EDDS : Ethylenediamine -N, N'- dis~ ~ccinic acid, [S S] isomer
in the form of the sodium salt.
Silicone a"tiro~" ,; Polydimethylsiloxane foam controller with
Siloxane-oxyalkylene copolymer as ~ispe, ~ing
agent with a ratio of said foam controller to said
~isper~i,)g agent of 10:1 to 100:1.
Pl ,otû~ ated: Sulpl ,or,aled Zinc Phthalocyanine enc~rsu~ted in
bleach dextrin soluble polymer
Savinase : proteolytic enzyme of standard activity
1 3KNPU/g
Carezyme : cellulytic enzyme of activity 1000 CEVU/g
Te,l"a",yl : Amylolytic enzyme of activity 60KNU/g
ipol~se : Lipolytic enzyme of activity 1 00kLU/g
Endol~se : E:ndoglunaseA
all sold by NOVO Industries A/S
PVNO : Polyvinylpyridine N-oxide
PVPVI : Copolymer of polyvinylpyrolidone and
vinylimidazole
CMC : Sodium carboxymethyl cellulose
Metolose : Carboxy methoxyether
SRA : Sulfobenzoyl end carped esters with
oxyethylene
(Soil Release : oxy and lere~ lhaloyl bac~bone
t ' Agents)
ExamPle 1
-
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48
The following formulations were prepared where A and B are in accord with
the invention and 1 and 5 are prior art cc",~positions.
2009 from each formulaliGns A,B and 1 to 5 was taken and subjected each
to a full scale was~,i,.y machine test using a Miele autGn)atic w~sh;.,g
machine (Model WM W698) set to the short wash cycle at 40~C for each
formulation. Water of 12~ German hardl,ess ( = 1.8 mol Ca2+/litre) was
used.
Coin~0l~6~1t A B 1 2 3 4 5
(% by weight)
LAS -4 ~-4 -4 5-4 4 4 5-4
TAS ~9 ~9 ~9 ~9 9 9 9
C25 E3 ~.0 ~.0 ~.0 ~-.0 ~-.0 ~.0 ~.0
nonionic 0.60 0.60 G.60 C,.60 C,.60 C.60 0.60
Zeol te A 19.1 19.1 5.5 5.5 5.5 5.5 5.5
MA/AA 0.3 0.3 '.8 2.8 '.8 ~.8 7.8
PB4 9.25 9.25 4.1 4.1 4.1 '4.1 4.1
TAED .8 1.4 .6 - .8 . ~ 2.5
Av02 .02 1.93 .43 .53 .87 . ~9 7.11
Carbo~ ~ale '0.5 '0.5 8.6 8.6 8.6 8.6 8.6
silicate 7.8 2.8 ~-.7 ~.7 ~.7 ~.7 .7
Savinase ~.28 ~.33 C .12 0.15 0.19 C .13 0.28
Pl otease
Te".ldln~l 0.10 0.10 nil nil nil nil nil
~mylase
~TPMP Q.3 0.3 0 3 0 3 0 3 0 3 0 3
- EDP ~u.2 0.2 nil nil nil nil nil
~linors and miscel ~neoL s to bala ~ce
HPP Index ¦ 0.5 0.5 0.1 ¦ 0.0 ¦ 0.1 ¦ 0.05 ¦ 0.16
Two s~hatcl,es dGlllol)slfali.)y dirrering degrees of soil removal pelror",a,)cewere used as slanclard to est~hlish a 4 point scale in which '+' represents a
very poor soil removal pe,rc,.,.,allce and '+++' average soil removal
performance.
The two slancla,ds are used to define the mid points between the various
des~ i~Jtions of soil removal pel ror,nd, lce viz
+verypoorsoil removal pelrur"lance
++ poor soil removal pe, rGl Illance
+++ average soil removal performance
++++ good soil removal pe,ru"nance
Two expert panellists are used and their results are averaged.
=
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49
The results are as follows:
A B 1 2 3 4 5
Stain removal ++++ ++++ + + + + ++
pe. rGI ~ .~ance
It is seen that Compositions A and B produce ~,II,a-,ced stain removal
p~, ru",~ance over the prior art Composilions 1 to 5
ExamPle 2
The following laundry ~eter~e"t ccm~,osilio..s C, D and 6 were prepared
where C and D are in accord with the invention and 6 is a prior art
COl'llpOSiliGI ~;
Col . "~onent C D 6
(% by .reight)
LAS/--AS 54/1 9 54/1 954/1 9
C25E~ 4.0 40 40
. or,ion c 0 65 0 6 f 65
~eol te A 20 5 20 ~ ~0 5
UAI~A 0 95 0 9;~L 95
PB~- 92 - 92
PB - 64
Av~2 C 94 0 94 0 94
TAED 8 8 8
C~, ~"at~ ~0 5 '0 5 ~o 5
silicate ~9 ~9 29
Savinase Plolease ~ :~3 u _3 ~) 0
Tel.. ,al."~l Amylase 0 0 0 0 0 0
DTPMP o~
~EDP
~inors and miscellaneous to ba ance
HPP Index 0 67 1 0 671 0 20
It was seen that compositions having an HPP Index over 0 35 produced
e~lhanced soil removal ~.elrc,r..,al,ce Said performance is further e~lhanced
when the hyd~ u!aen peroxide consisled of at least 90% by weight of PB4
ExamPle 3
CA 02214397 1997-08-29
w 096/28534 PCTrUS96/02337
The following laundry dele.gelll compositions E, F and 7 were pre~ared,
where E and F are in accord with the invention and 7 is a prior art
osilio,):
CGII II~GI )~1 ll E F 7
(% by weight)
LAS /--AS 5.4 /1.9 5.4 /1.9 5.4 /1.9
C2 E~ 4.0 4.0 4 0
r on on c 0.60 0.60 0.60
eo te A 20.5 "0.5 20.5
VWAA 0.95 q.8 3.7
PB4 ~.6 8.6 ~5.6
TAED ~ .4 ~ .4 .0
Carbonate 20.5 ~0.5 ~ 8.6
silic~t~ -~ g ~ g ~ "
Savinase Protease ~.~3 0.~3 ~.~ 3
T~- .. a.. ,yl Amylase 0. ~ 0 0. ~ 0
DTPMP 0._ 0.~ 0 3
HEDP 0.2
Minors and mis~ll~neous to balance
HPP Index ¦ 0.6 10-6 10-05
Compositions E and F with HPP Index of 0.6 produce enhanced soil
removal pe-ro----a-,ce over the prior art refere,)ce composition 7 of HPP
Index 0.05.
It was also be seen that combination of polycarboxylic acids and
~I ,os~l ,o"ales c,helarlts further enhanced the soil removal pel rO, . . ,ance,esp~ci~"y when the polyc~,L,oxylic acid is present in low amount (e.g Iess
than 1% by weight).
Exal I "~la 4
The following detergent compositions according to the invention were
prepared:
CGI 1 II~OneI IlS G H
LAS 8.0 8.0
C25E3 4.10 4.10
Zeolite A 12.0 19.10
Na SKS-6 6.16
CA 02214397 1997-08-29
W 096/28534 PCTrUS96/02337
MA/AA 1.50 0.30
SRP 0.10
Metolose 0.30
PVNO/PVPVI 0.02
cdlLGndle 20.50 20.5
Silicate - 2.82
PB4 12.0 9.25
AvO--, 1.25 0.96
TAED 1.85 1.85
EDDS 0.19
DTPMP - 0.25
HEDP 0.20 0.22
MgS04 0.30 0.30
Savinase ~ otease 0.50 0.28
Lipolase lipase 0.12
Tel"~a",yl amylase 0.38 0.10
Carezyme Cellulase 0.08
En~ol~se 0.08
CMC - 0.22
Bl i~l ,lener 1 0.12
Brightener 2 - 0.11
Pl-otoactivated bleach 0.003 15ppm
Silicone alllirudlll 0.10 0.55
Sulphate 24.0 25.88
Perfume 0.25 0.27
Minors and miscellaneous to balance
HPP Index ¦ 0.6 ¦ 0.56
The above formulations were seen to produce effe. tive soil removal
p~l rul " ,a, ~
t
