Note: Descriptions are shown in the official language in which they were submitted.
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DETERGENT COMPOSITIONS IN COMPACTED SOLID FORM
Pield of the Invention
The present invention relates to detergent cou~l~osilionc in comp~ctçd solid form
cu~ ing an ~lk~linity system and a crystal growth inhibitor.
Bach~.ou-~d of the Invention
Det~.~enl cc"~,po~ilions for use in dUlOIlldtic dishwashing or laundry m~r,hin~s are
often in gr~n~ r or ~wd~. form. Such CG.. l~osilionc are "~ea_ul~d and dosed by
the u~nc--m~r and placed in the dic~n~çr of the n~chine which is located in the
door in the case of dishwashing m~hines or the ~licpencin~ tray of an aulo,..aLic
laundry washing m~clline.
In order to simplify the dosing of d~,t~.genls for ~Iu,..~l;c w~h~g ...~ -PS
however, many of the aul~",dlic w~l,ing det~ nt con.~;l;ol-c are now provided
in co-..?A~I~ solid forrns, such as bars, tablets or briquettes. This provides al.u,..b~ . of advantages to both the cor C~mer and m~n--f~ctl~rer. Firstly, suchcornr~t~ forrns allow for easier h~ndling of the d~,t~E;ent co.. l o~;l;on. .Se~ lly,
the comp~ ~ solids are generally sized to meet dosage l_.lUilC~ , Thirdly, the
use of co.~ d solid forms ...;.~ s the contact by the concumer with the
col~ c;~ion ~
It is highly desirable that the comr~cted solid forms possess a certain degree of
}~lncss and sl-~n~ . In particular they should be s~fficiently hard to meet safety
u~ . Det~.~e1 l co~ po~;l;onc are typically highly ~lk~line and thus oral
~n~ r ~ n must be avoided. However, comr~te~ solid forms, particularly
tablets often appear attractive to children, who may attempt to cuncllmp them.
Fll,ll.e1111ore, it is also desirable that the comractP~ solids should be strong enough
~ that they are not s~sceptible to damage upon packing, ~ldl s~o1l or stor~ge~
Comp~tP~ form d~ E,enl compocitionc for use in laundry and m~hinP
disl.w~l.ing meth~c typically cont~in~ for cl~ning effectiveness, an ~lk~linity
system. Silicate is an especially common CO---pOl ent of such ~lk~linity systems. In
addition to providing cle~ning ~1Ço1111atlce, silicate salts have the ability to
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~nh~nce the hardness and strength of the compacted form products. It is beli~vedthat such ability is due to its tendency to form stren~thPning water bridges ~l~n
silicate particles. However, it has been established that to achieve the effective
formation of the silicate-water bridges, a high l,rupo ~ion of water must be present
in the ~.o.l.l-;l matrix, which can be undesirable from a product stability
st~n~ oin~ particularly if the matrix co~t~ins components, which are susceptible to
hydrolytic de~r~ tion on storage (e.g. bleach compollen~).
It has also, been established that the presence of high levels of silicate (typically >
12% by weight SiO2) can ~t~ ly lead to problems with the corrosion of
~,las;,w~e in the ",~ ;nf. dishwashing load. In view of both product stability and
~l~C~c~e con~ ;olls it is thus l,lereldble to keep the amount of silicate salts
below a certain level. It is also however, n~.~e~.y to .~ - a high ~ linity to
achieve ~ti~f~rtory rle~ning ~Irollllance. Partial or full rep~ Tn~ont of silicate
salts by c~l,onate salts addresses each of these perforrnance r~ e...~
The p-~c~ of c~ul,ondle salts can however give rise to a problem with the
form~tion of white ~epo;,;L~, as spots and films, on the articles in the m~rhin.~
disl,~asl~.ng load. The strength and ha.dlless of the co..~p~. i~ product can also be
r~luced when silicate salts are r~placed by call,ollate salts in a co...~ ;ol-
The ~rplil~nt has now found that the white depocit.c problem can be ~m~ ~t~by inclusiol~ of a crystal growth inhibitor colllpoulld into the de~f~ent
cc,...l~;t;on. The Applicant has also found that the ~ng~, and haldnei.s of the
~1U.;L, and its ~cil~ to retain the desired physical slluclu-~ on aging may be
inc~d if at least part of the ~ linity system is made up of particles coated at
certain levels with an organic binder m~t.o.ri~l, particularly a polyethylene glycol
m~t~ri~l The use of such an organic binder also aids p.oducl dic;n~ ility in thewash which assists cl~ning ~.Ço.lnance. Thus, in accord with the invention a
product having rk~ning effectiveness, minimi7ed tendency to form white depo;,i~,and which has suitably hard and strong comp~rted form may be ob~ined at low
~.~si,.l-~s.
R~ nd Art
EP-A-522,766"l;~l~ses at Fl~mrle 2 a tabletted deL.~ nt co-..l o~;t;on formed
from a base ~-vde CQnli~;ning 4% sodium silicate, 14.3% sodium ca l,onate and
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other dele~ent ingredients. The base powder is sprayed with PEG 1500 at a
coating level of 3% prior to tablet compaction. The co...~ ;on cont~ins no
crystal growth inhihjt()r co-,lponent.
EP-A-466,484 de~ribes tabletted dc;~~ t compositionc- Polyethylene glycol is
des~ribe~ as a lJlf fe.l~ binder/di~in~ t Crystal growth inhibitor co
are not described.
E~P-A-628,627 ~lescrihes a tablet cont~inin~ polyethylene glycols of molpcul~r
weight from 1000 to 6000 as tabletting ~nxilli~riP$ Crystal growth inhibitor
colllpoll~,n~ are not dese,il)e~.
WO 93/00419 ~ ;bf s eall,onal~o~ -ing d~t~.gent tablet forrn~ tionc which
include HEDP as a ~lerell~d cc,l-,~nent. Low foaming suff~rt~nts, in~lullin~
p~felably C12-Clg alkylpolyethylene glycol-polypropylene glycol ethers with up
to 8 moles of ethylene oxide and propylene oxide units in the molf-~ul~ are
descrihed a_ pl~fe,led ~llxilli~ry ingredient . Organic binder co...l~Qnf~ are not
~ifirz~lly ~f~ e~.
GB-A-2285052 de,~;l~s at F~ 3, a formulation con~ g 14% _odium
ca,l~nate and 0.6% HEDP, but no organic binder col,.l)onent.
None of the id~-~l;lir~ prior art docum~nts provide specific ~ fe of a
comr~rtçd solid for n d~te,~ t product co~ ining a crystal growth inhibitor and
an z-lk~linity system wh~,~;n at least part of the ~Ik~linity system comprises
particulate ~ ine salts coated with an organic binder.
Fu,ll,~."..)n, none of these do.;.~ e-~l~; address the problem of providing a suitably
hard and strong c4~.r~ d form ~lk~linP d~_te~.;nl co",po~iLion having good
cl~n;..g ~.Çu""ance, and having a reduced tendency to form white deposits on
the articles in a m~hine dishwashing load. Nor do any of them dçsc-ribe the
solution a~s provided by the present invention.
Summary of the Invention
Acording to the present invention there is provided a del~,~;e"t co",posilion inc~mrartçd solid fornn col-~ .ining
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(a) an organo diphosrhon~t~ crystal growth inhibitor; and
(b) an ~lk~linity system comprising ~lk~line salts $Plçrt~l from the group
c~nci~tin~ of alkali and s~ line earth carbonates, bicar~onates, hydroxides and
~ilir~t~s
wherein at least part of the ~lk~linity system comprises particulate ~ line salts
coated with an organic binder and the weight ratio of organic binder to ~ linitysystem in the dt;lcr~ent col.lposilion is from 1: 100 to 1:1.
Als ~ , weights, ratios and pele~nl~ges are as a % weight of the de~.~,_nt
CQ...l~S;I;Oll unless otherwise stated.
All dQC~ cited in the present des.;,i5~lion are, in relevant part, incol~l sled
herein by s~fer~ nce.
D~t~ A Des~ ion of the Invention
In an P~ l aspect the dt;~ryent con-l~o~ Qn is in solid comp~t~ form. As
used herein the term solid cQm~rtçd form refers to a solid pr~lucl form obtainedby c~ or c~,llS, ~i~sion, typically of a particulate or pasty CO~l~c;l;on By
pasty colllposilioll it is meant herein a paste-like cGIu5~osilion~ of typicaUy
relatively high viscosity, comS~ri~ing particul~tes s~lsren~e~d or dispersed within a
fluid mass. Suitable c~mr~rted solid forms include bars, bsiu5u~,~s~ cakes or
tablets.
Tablets, in accord with the invenffon, can be of e~Pnl;~lly any suitable shape, but
are dçcigned to have the optimum weight/surface area ratio, and are preferably
~""nf~.;r~l to aid di~sQl~ltion. I~re~ cd tablet shapes include discs, ç$5~i~11ythose having a di~meter of from 25 to 45mm, and a thiC~l~ness of from 10 to
20mm.
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Crystal Growth Inhibitor
An e;~~ co~ on~,nl of the dete.~ent co...poc;l;onc in acco.dance with the
invention is an organo ~lirhosph~n~t~-, that is an organo ~1irhs)srhonic acid or one
of its salts/co r' es Pl~f~ly any salts/cornrle~es are water so1uh1e~ with the
alkali metal and ~ ine earth metal salts/comp1eYes being e.c~i~11y pr~rel.~d.
By organo ~lirhospllonic acid it is meant herein an organo diphosrhorlic acid which
does not contain niL,ugen as part of its chemir~l structure. This d-~ril-;l;oll the~re
exc1u(1es the organo a.,lino~hocrhorl~t~s, which however may be ine~lld~ in
CQ...l os;liol c of the invention as heavy metal ion sequestrants.
The organo ~irhosphon~t~ co~ one-lt is preferably present at a level of from
0.005% to 20%, more preferably from 0.1% to 10%, most pl~f~.ably from 0.2%
to 5% by weight of the detel~,cnt cGlll~o~;l;ons
The organo ~ ho~l~horl~t~ is preferably derived from a Cl-C4 f~ hosl~honic acid,more ~-~ f~.dbly a C2 flil ho~ onie acid, such as ethylene ~ ho~.ho~ acid, or
most pief~ ably ethane l-hydroxy-l,l-diphosphonic acid (HEDP). Also S~-it~h~~
are alpha hydroxy-2 phenyl ethyl dil.hn~l.hc~ e, methylidene ~;l.h~.hon~
hydl~JAy 1, l-he~cylidene and vinylidene 1, 1 diphocl,1-o~
A1k~linity System
In an ec~ l aspect the col~l~c;~ c contain an ~1k~1inity system compricinE
co~ e~ capable of providing ~lk~linity species in sol~tion. By ~lk~1inity
species it is meant for the ~ Joses of this invention: c~ulJol~ate~ bic~l,onale,hydroxide and the various silicate anions. Such ~lk~linity species can be formed for
e-~mple, when ~ line salts sP1c~1ed from alkali metal or ~lk~linf~. earth carbonatc,
bicarbonate, hydro~ide or silicate, in~lu-ling crystalline layered cilir~tr, salts and
any ~ L~l.,S thereof are dissolved in water. Alkali metal ~.~L onate and
persilicate salts are also suitable sources of ~lk~lini~y spe~ie~s.
The ~lk~linity system is p~cf~.dbly present at a level of from 1.5% to 95%,
cf~.~bly from 5% to 60%, most preferably from 10% to 40% by weight of the
de~~ nl co...po:,iLion.
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To enable practical comparison of the relative capacity of coul~s;lionc CO~ g
different ~lk~line colllponents to deliver alkalinity to a wash sQll~tion it is useful to
express the ~lk~linity released on addition of the col~ ;l;onc to the wash solution
in terms of % weight equivalent of NaOH. That is, in terms of the % weight of
NaOH which would have equivalent '~Ik~line effect', e. g. in n-outr~licin~ acid
cpecieS, to that of the ~ linity species actually released when the co,nposilion is
added to the wash. For uniform co,.ll, ll ;cf~n it is also then useful to define standard
wash solution char~rtçrictirs. Thus, the capacity to deliver ~lk~linity to a wash
solution is herein ch~ct~;7ed by reference to a lcpl~csc~ e test method now
~es~rihç~
Alk~linity Release Test Method
A lg sample of d~,te gcnl col-,~silion is added to 100 ml of ~istillp~l water at a
tc~ Ill.e of 30~C with stirring at 150 rpm using a m~gn~PtiG stirrer of size 2cm,
thus providing a 1% delt;~ e~t solution, as would be a typical co~cPntration of a
laundry wash solutiom The sollltion is titrated against a standard HCl sollltionusing any suitable titration mçthod. Commonly known acid-base iLlalion mPthor1c
employing col~,;ll~eh;c end-point del~llu~ t;on m-oth~c, for eY~mpl~ using
rhemir~l end-point in~lic~t~rs are particularly suitable. Thus, the nu~l~b~r of moles
of HCl which the det~ t sol~tion is capable of nPut~licing is o~ ed. For the
av~ ~n~ of doubt, InP~lt~li~ingl in this context is defined to mean titr~ting to pH
7. This llulnl~ will be equivalent to the number of moles of ~ linity, e,~
as NaOH equivalent, present in the detergent solution Thus, the % weight
equivalent NaOH present in the sample of the dete.~nt coll-po~;l;o~ may be
c~lc~ t~ as:
9to weight equivalent NaOH =
100 ~c number of moles NaOH equivalent in sol~ltion x Mw of NaOH
Alk~linity Delivery ~it~
In a ~.efe.l~d aspect, the ~lk~linity system is present in the de~.~ ,nt col~poc;l;on
such that the ca~;ily to deliver ~Ik~linity to a wash solution l..e~uled by the
given test method is such that the weight NaOH equivalent of the colnposilion is
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greater than 3%, preferably greater than 5%, most p.efel~bly greater than 8% by
weight of the co~ osilion.
Allcaline Coml~onents
Examples of c~ubonates are the ~ lin-o earth and alkali metal carbonates,
inc~ in~ sodium call,onate and any I~ L~ s thereof with ultra-fine c~lçium
c~hln~na~e such as are rliscl~se~ in German Patent Appli~tion No. 2,321,001
published on November 15, 1973. Alkali metal pe.ca,l/onate salts are also suitable
sources of carbonate species and are cl~scrihed in more detail in the section
'ino~,anic perhydrate salts' herein.
Suitable ~ilir~t~s include the water soluble sodium ~ c~f~s with an SiO2: Na20
ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.0 being plefelled, and 2.0
ratio being most p~f~.l~. The ~ at~s may be in the form of either the
anhyd-~us salt or a hy-ilat~ salt. Sodi-~m silicate with an SiO2: Na20 ratio of 2.0
is the most ~ ft;~ t~ Alkali metal per~ilie~tPs are also suitable sources of
silicate herein.
Pl~r~ led crystalline layered ~ilin~t~s for use herein have the general formula
NaMSix02x~ 1-YH20
wl,e~n M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number
from 0 to 20. Crystalline layered sodium ~ t~s of this type are ~ osed in EP-
A-0164514 and methoris for their prep~r~tion are ~ closP~ in DE-A-3417649 and
DE-A-3742043. Herein"c in the general formula above ~l~felably has a value of
2, 3 or 4 and is yl~f~ .ably 2. The most yl~f~ m~t~ri~l is ~-Na2Si20s, availablefrom ~h~t AG as NaSKS-6.
The crystalline layered silicate material is preferably present in granular d~ ,ent
Co~ ;ollc as a particulate in intim~te ~dmixhlre with a solid, water-soluble
ionisable m~eri~l The solid, water-soluble ionisable m~t~ri~l is sel~ted from
organic acids, organic and inorganic acid salts and Illixlurcs thereof.
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Silicate salts are ~r-c~elàbly present in an amount of less than 12%, preferably less
than 105o, most ~)rerelably less than 9% active silicate (i. e. SiO2) by weight of
the de~l~ ent co...l os;l;()n
In a highly ~l~ fe.l~d aspect, the ~lk~linity system consists of both ~bunalc and
silicate salts to provide a weight ratio of active carbonate (i. e. C032-) to active
silicate (i. e. SiO2) of from 1:4 to 4:1, more preferably 1:3 to 3:1, most
pl~ fc~ably from 1:2 to 2:1.
Coatin~ of Alkaline Co~ ents
The ~ linity system comprises at least in part, particulate ~lk~line salts coated
with an organic binder. The weight ratio of organic binder to ~lk~linity system in
the d~ nt composition is from 1: 100 to 1:1, pr~rc.ably from 1: 40 to 1:3,
most pr~reldl)ly from 1:20 to 1:5, the most ~lerc.lcd range being ~lcre.lcd from a
tablet hanlness st~ndpoint
Orpanic Binder
The overall level of organic binder in the detergent composition should not exceed
20%, and is ~ler~.ably less than 10%.
FSp~i~lly p.cfe.-~ organic binders herein are the polyethylene glycols (PEG)
with an average average mrle:ul~r weight of from 600 to 10,000, preferably from
1,000 to 8,000, more pr~fe.ably from 1200 to 5,000, most preferably 1,500 (i. e.PEG 1500).
Further e li'es of sllit~hle organic binders include the water soluble organic
homo- or co-polymeric polycarboxylic acids or their salts in which the
pol~c~l,uA~lic acid comrri~s at least two carboxyl ratlic~l~ ~p~alcd from each
other by not more than two carbon atoms. Polymers of the latter type are
d in G~A-1,596,756. P~ led examples of such compounds are the
polymers which contain acrylic acid, that is to say homopolymers of acrylic acidand copolymers with any suitable other monom~r units, and which have a average
mo~ r weight of from 2,000 to 100,000. Suitable other monomer units include
m ~lifi ~ acrylic, fumaric, maleic, it~-onic, aconitic, mP~cQnic~ cillaconic andmethyl~n~m~lonic acid or their salts, maleic anhydride, acrylamide, alkylene,
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vinylmethyl ether, styrene and any mixtures thereof. Preferred are the copolymers
of acrylic a~id and maleic anhydride having a average molecular weight of from
20,000 to 100,000.
P.~rell~l acrylic acid cv~ in~ polymers have an average molecular weight of
less than 15,000, and include those sold under the tr~len~me ~ok~l~n PA30,
PA20, PA15, PA10 and Sokalan CP10 by BASF GmbH, and those sold under the
n~m~o Acusol 45N by Rohm and Haas.
Other p~ red acrylic acid co~ in~ copolymers include those which contain as
monomer units: a) from 90% to 10%, preferably from 80% to 20% by weight
acrylic acid or its salts and b) from 10% to 90%, preferably from 20% to 80% by
weight of a s.,~ ed acrylic monomer or its salts having the general formula -
tCR2-CRl(CO-O-R3)]- wherein at least one of the ~Lb~ Rl, R2 or R3,
~lef l~bly Rl or R2 is a 1 to 4 carbon alkyl or hydroxyalkyl group, Rl or R2 canbe a hydrogen and R3 can be a hydrogen or alkali metal salt. Most pl~f~,led is aYt~ acrylic monomer wherein Rl is methyl, 1~2 is hydrogen (i.e. a
.ylic acid m--no..~fr). The most p-~felled copolymer of this type has a
average molecular weight of from 4500 to 3000 and cont~in~ 60% to 80% by
weight of acrylic acid and 40% to 20% by weight of ,.~ lic acid.
The polyamino co.l~poL~nds are useful as organic binders herein inclu~lin~ thosederived from aspartic acid such as those ~ o~ed in EP-A-305282, EP-A-305283
and EP-A-351629.
Other ~.,ilablc binders include the Clo-C20 alcohol ethoxylates c4,.1; i..;n~ from 5 -
100 moles of ethylene oxide per mole of alcohol and more preferably the Cls-C20
primary alcohol ethoxylates conl~in;n~ from 20 - 100 moles of ethylene oxide permole of alcohol.
Polyvinylpyrroli~on~s with an average mo]ec~ r weight of from 12,000 to
700,000 are sl~it~ble ploymeric binders herein~ Copolymers of maleic anhydride
with ethylene, methylvinyl ether or meth~rylic acid, the maleic anhydride
col.~ ing at least 20 mole percent of the polymer are further examples of
polymeric materials useful as binder agents~ These polymeric m~tPri~lc may be
used as such or in combin~tion with solvents such as water, propylene glycol andthe above m~ntion~ Clo-C20 alcohol ethoxylates cont~inin,~ from 5 - 100 moles
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- 10
of ethylene oxide per mole. Further eY~mI~les of binders include the Clo-C20
mono- and diglycerol ethers and also the Clo-C20 fatty acids.
~dditional Det~;~el~t In~redients
The cG~.po~;l;onC herein can optionally include one or more other dele.~.,n~
adjunct m~t~ri~lc or other m~tPri~lc for ~ccicting or çnh~ncing cle~ning
~,çu~lllance~ trç~tm~nt of the substrate to be cl-o~nç~, or to modify the ~f~-sthetic~
of the ~ct~ r~_-ll ~Illpo~ilion (e.g., perfumes, colo~ntc, dyes, etc.). The following
are illlJct~tive eY~ s of such adjunct materials.
Water-soluble builder co,l,?ou"d
The c~...lx~s;l;onc of the present invention may contain as a highly ~,~f~ d
colllponc.~l a water-soluble builder c~lllpoulld, typically present at a level of from
1% to 80% by weight, ~ felably from 10% to 70% by weight, most l)r~re~ably
from 20% to 60% by weight of the dele,~,_nl collll~osilion.
Suitable water-soluble builder co,l,~unds include the water soluble monomeric
polyc~ul,oAylatcs, or their acid forms, homo or copolymeric polywl,oAylic acids
or their salts in which the polycarboxylic acid comprises at least two carboxylic
r~lic~lc se~t-d from each other by not more that two carbon atoms, bûrates,
~hosl.h-t~ s, and IIPi~LlU~CS of any of the ~OlCgOillg
Ille c~l,o.~yl~le or poly~l,oAyl~te builder can be momomeric or oligomeric in
type ~lthou~h ...O~ poly~ul,uAylates are gene~ally preferred for reasons of
cost and ~ ce.
Suitable c~l,o,~yl~t~s co~ h~ one carboxy group include the water soluble salts
of lactic acid, glycolic acid and ether derivatives thereof. Polyc~l,oAylates
c~ ;ni~ two carboxy groups include the water-soluble salts of sucçinic acid,
m~lonic acid, (ethylen~lioxy) ~ tic acid, maleic acid, diglycolic acid, tarta~icacid, tartronic acid and fumaric acid, as well as the ether carboxylates and thesulfinyl carboxyla~es. Polyc~l~oAylates con~1ining three carboxy groups include, in
particular, water-soluble çit~t~S~ aconitr~tes and citr~con~tes as well as succin~
derivatives such as the carboxymethyloxysuccin~tes described in British Patent No.
1,379,241, lactoxysuccin~s described in British Patent No. 1,389,732, and
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- 11
~minosuc.~h-~tt 5 descAbed in Netherlands Application 7205873, and the
oxypolycarboxylate m~teri~lC such as 2-oxa-1,1,3-propane tricarboxylates
~- des.ilibed in BAtish Patent No. 1,387,447.
Polyc~l,o,-~lates co .I;~h~ g four carboxy groups include oXy~iicllccin~ 5 di~losed
in BAtish Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane
tetracarboxylates and 1,1,2,3-propane tetracarboxylates. Polycarboxylates
CQn~in;l~ sulfo substitllents include the sulfosuccin~tç derivatives ~ rlos~ in
British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448,
and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.
Alicyclic and heterocyclic polyc~l,o,~ylates include cyclopent~le cis,cis,cis-
tetracarboxylates, cyclopent~liPni-ie pentacarboxylates, 2,3,4,5-tetrahydrofuran -
cis, cis, cis-tetracarboxylates, 2,5-tetlahydrofuran - cis - dicarboxylates, 2,2,5,5-
tetrahydrofuran - t~L-dcall,o~ylates, 1,2,3,4,5,6-hexane - h~y~rboxylates and
carboxymethyl derivatives of polyhydric alcohols such as sorbitol, ...~nn;lol and
xylitol. Aromatic polycarboxylates include mellitic acid, pyr~...elliti~ acid and the
phth~liC acid deAvatives ~li~lQse~ in BAtish Patent No. 1,425,343.
Of the above, the p~Ç~led polycarboxylates are hydroxyc~l,oxylates col.~ .;np
up to three carboxy groups per molecule, more particularly cit~tes
The parent acids of the monorn~ic or oligomeAc poly~hl,o~ylate ch~l~tin~ agents
or ~ lu~s thereof with their salts, e.g. citAc acid or citrate/citAc acid ~ni~lur~s
are also c~nlt~ t~ as useful builder co"~ncnls.
Borate builders, as well as builders CO~ lg borate-forming m~ter~ that can
produce borate under detcr~,c.lt storage or wash con~iitions can also be used but are
not p~f~.-cd at wash con~litions less that 50~C, es~ y less than 40~C.
Specific ,.~n~l,les of water-soluble phosphate builders are the alkali metal
tripolyphQ~yh~tes~ sodium, pot~ium and ammonium p~f~hosl,h~e, sodium and
pot~ lm and ~ ....on~ pyropho~ph~t~, sodium and pot~ m orthophosrh~t~,
sodium polymeta/phosph~te in which the degree of polym~ri7~tion ranges from 6
to 21, and salts of phytic acid.
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Partially soluble or insoluble builder compound
The co.,.po~;lisn~ of the present invention may less preferably contain a partially
soluble or insoluble builder co,-lpou..d. F-~mples of largely water insoluble
builders include the sodium ~h~minosilir~tçs~ inCl~lding Zeolite A, Zeolite B,
Zeolite P, Zeolite X, Zeolite MAP, Zeolite HS and mixtures thereof.
Sllrf~rt~nt
A highly prefe.~ co..~ t of the co.~pos;lionc of the invention is a surfactant
system compri~ing aulrd~ l sel~ct~ from anionic, c~tionic, nonionic ampholytic
and zwittPrionic sllrf~rt~ntc and l~ lures thereof. Preferably the surfactant system
comprises low foaming surfactant, which is typically nonionic in cl~ cte.. The
surfactant system is typically present at a level of from 0.2% to 30% by weight,more p~f~.dbly from 0.5% to 10% by weight, most preferably from 1 % to 5% by
weight of the co...l os;l;on~
A typical listing of anionic, nonionic, ampholytic and zwitt~ionic classes, and
species of these surf~rt~nt~, is given in U.S.P. 3,929,678 issued to T~ughlin and
~nrin~ on Dec~ .l~r, 30, 1975. A list of suitable cationic surf~t~nt~ is given in
U.S.P. 4,259,217 issued to Murphy on March 31,1981. A listing of surfactants
typically in~lu~1~ in aululllalic dishwashing detergent co-..posilions is given for
eY~mp'~, in EP-A-0414 549 and PCT Applications No.s WO 93/08876 and WO
93/08874.
N ninnir surf~t~-it
~;~nti~lly any nonionic surf~<t~nt~ useful for detersive pu,~oscs can be incll~d~
in the co~ GC;~;ons. r~cfc.-ed, non-limiting classes of useful nonionic surfactants
are listed below.
Nonionic ethoxylated alcohol surfactant
The alkyl ethoxylate conden~tion products of ~liph~ti~ alcohols with from 1 to
25 moles of ethylene oxide are suitable for use herein. The alkyl chain of the
irh?~tis~ alcohol can either be straight or br,mrhecl, primary or s~on~l~ry, and~en~orally cont~in~ from 6 to 22 carbon atoms. Particularly ~l~rell~d are the
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13
col-denc~tion products of ~lcoholc having an alkyl group cont~ining from 8 to 20carbon atoms with from 2 to 10 moles of ethylene oxide per mole of ~lr~h~-l.
.
Nonionic ethu~yla~çd/yl~Aylated fatty alcohol surfa t~nt
The ethu~-ylaled C6-Clg fatty zllcoholc and C6-Clg mixed
ethoxylated/~ro;?o~ylated fatty alcohols are suitable surf~Pnt~ for use herein,
particularly where water soluble. Preferably the ethoxylated fatty ~lroholc are the
Clo-Clg etho~cylated fatty alcohols with a degree of ethoxylation of from 3 to 50,
most p~f~dbly these are the C12-Clg ethoxylated fatty alcohols with a degree of
ethoxylation from 3 to 40. ~f~dbly the mixed etho,~ylated/~ro~ylated fatty
al~Qhol~ have an alkyl chain length of from 10 to 18 carbon atoms, a degree of
ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10.
Nonionic EO/PO condens~tes with propylene ~Iycol
The cond~nc~tion products of ethylene oxide with a hydrophobic base forrned by
the cond~on~tinn of propylene oxide with propylene glycol are suitable for use
herein, The hydrophobic portion of these compounds prGfc.dl)ly has a mol~ ~ r
weight of from 1500 to 1800 and exhibits water insolubility. Examples of
co...poun~lc of this type include certain of the commPrcially-available PluronicTM
surf~t~ntc, ~ u~cted by BASF.
Nonionic FO condens7~tion products with propylene oxide/ethylene d;a~l,;ne
adducts
The co--d~ ;on ~l~lu~i~ of ethylene oxide with the product res~lting from the
reaction of propylene oxide and ethylen~i~ nr are suitable for use herein. The
hyd~hobic moiety of these products concictc of the reaction product of
ethyle~ nl;..e and excess propylene oxide, and generally has a molecular weight
of from 2500 to 3000. Examples of this type of noninnic surfactant include
certain of the commercially available TetronicTM compounds, ...~ ~ by BASF.
Or~nic polymeric co~ d
Organic polymeric cc,-.-po~ s may be added as plGfcll~d s~dle colllponcnts of
the COI~pO ;I;o~c in accord with the invention. In addition such organic polymeric
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14
co,nl)o~ ds may find use as organic binders in accord with the invention as
described hereinbefore. By organic polymeric compound it is meant ç~s~nt~ y any
polymeric organic co---pound commonly used as dispersants, and anti-rçdepositionand soil s~pen~ion agents in detelgellt compo~ition~
FX~ S of organic polymeric compounds include the water soluble organic
homo- or co-polymeric polycarboxylic acids or their salts in which the
polycarboxylic acid comprises at least two carboxyl radicals sep~dled from each
other by not more than two carbon atoms. Polymers of the latter type are
disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of averagemolecular weight 2000- 10000 and their copolymers with any suitable other
mono---cl units inclu~ing modified acrylic, fumaric, maleic, it~or-ic, a~onitiC~meS~corliC, citraconic and methylen~om~lonic acid or their salts, maleic anhydride,
acrylamide, alkylene, vinylmethyl ether, styrene and any llu~lul~s thereof.
P~f~lvd are the copolymers of acrylic acid and maleic anhydride having a
average mo~ r weight of from 20,000 to 100,000.
Plefe.l~d commercially available acrylic acid co~ ining polymers having a
average mol~ul~r weight below 15,000 include those sold under the tr~-len~m~.
.So~ n PA30, PA20, PAl5, PA10 and Sokalan CP10 by BASF GmbH, and those
sold under the tr~dpn~me Acusol 45N by Rohm and Haas.
~r,_fe.l~d acrylic acid cont~ ;ng copolymers include those which contain as
monomer units: a) from 90% to 10%, ~-~Çe.dbly from 80% to 20% by weight
acrylic acid or its salts and b) from 10% to 90%, preferadbly from 20% to 80% byweight of a s.ll~sLiluled acrylic monomer or its salts having the general formula -
tCR2-CRl(CO-~R3)]- wherein at least one of the ~-lb~ u~; Rl, R2 or R3,
pf~fe.~ly Rl or R2 is a 1 to 4 carbon alkyl or hydroxyalkyl group, Rl or R2 can
be a hydrogen and R3 can be a hydrogen or allcali metal salt. Most ~r~f~ d is a
sul,~ ~ acrylic .nono.-.e~ wherein Rl is methyl, R2 is hydrogen (i.e. a
c,ylic acid .--ono--ler). The most pl~re.led copolymer of this type has a
average mol-cul~r weight of 3500 and contains 60% to 80% by weight of acrylic
acid and 40% to 20% by weight of mPth~rylic acid.
The polyamino co.-l~unds are useful herein including those derived from asparticacid such as those ~licclos~ in EP-A-305282, EP-A-305283 and EP-A-351629.
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Chel~ting ~gents
The detergent co...l o~;tionC herein may also optionally contain one or more iron
and/or n~ltg~f'5e Chf~l~lt;~ agents. Such ch~l~tin~ agents can be scl~ed from the
group c~nci~ting of amino carboxylates, amino phosphon~tPs polyfiln-~tic-n~lly-
s.lb~Lilutcd aromatic chf~ g agents and ~ lulcs therein, all as hereinafter
definP~. Without jntenr1in,~ to be bound by theory, it is believed that the benefit of
these m~tP,ri~lc is due in part to their exceptional ability to remove iron and
m~ng~nPsp ions from washing solutions by formation of soluble eh~ s.
Amino carboxylates useful as optional chf l~t;.-g agents include
ethylçnPAi~ el~tPs~ N-hydroxyethylethylene ~ minetri~t~t~tf C, nitrilo-
~ " ethyk-~f~ ine teLIdpioplionS~tec~ triethyl~ teLld~~ e- h~PY~ret~t~s~
diethylent~t~;~.-.;llPp~nl~tet~t~Ps, and ethanoldiglycines, alkali metal, ~mm-)nit-m,
and ~'b~ UIPA ~mmOnium salts therein and mixtures therein.
Amino phosphonates are also suitable for use as ch~Pl~tin~ agents in the
cGI,l~siLions of the invention when at least low levels of total pho~ ol.ls are
~,ll~ilt~ in d~t~ nt cc ~po~;tionc~ and include ethylt ne~ lll;tlf l~ ~,.kic
(methylf ~ hos~hon~t s) as DEQUEST. Plefe.led, these amino phocphon~tPs to
not contain alkyl or alkenyl groups with more than 6 carbon atoms.
Polyfunrti~n~lly-s.~l,s1ilu~ed aromatic chel~ting agents are also useful in the
co..~ ;on~ herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connoret al. Pr~;L,lGd co,-l~u-lds of this type in acid form are dihyd~Aydisulfobf l~t-.fs
such as 1,2-dihydroxy-3,5-disulfoben7f ~~t~
A ~l~f~,l~ biodegradable chelator for use herein is ethylentAi~mint~
(~EDDSn)~ es~ y the [S,S] isomer as described in U.S. Patent 4,704,233,
NGV~ bf~ 3, 1987, to Hartman and Perkins.
If uti~ these chtJl~;n~ agents will generally comprise from 0.1% to 10%,
preferably from 0.1% to 3.0% by weight of the detergent compositio~ herein.
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Enzymes
Enzymes can be includP~ in the formulations herein for a wide variety of stain/soil t
removal ~ulposes, incl~ n~ removal of protein-based, carbohydrate-based, or
triglyceride-based stains. The enzymes to be incorporated include proteases,
amylases, lipases, c~llul~c~s and peroxi~ces~ as well as ~lliA~ules thereof. Other
types of enzymes may also be included. They may be of any suitable origin, such
as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is
governed by several factors such as pH-activity and/or stability optima,
thermostability, stability versus active d~ enLs, builders and so on. In this
respect b~ l or fungal enzymes are pl~f~.led, such as bacterial amylases and
prùteases, and fungal c~llul~s
Enzymes are normally in~l~n3ldled at levels sufficient to provide up to S mg by
weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the
co",~G~ilion. Stated otherwise, the cornpocitionc herein will typically comprisefrom 0.001% to 10%, ~lefe.dbly 0.01% to 5% by weight of a com.nF--;al
enzyme pl~dnd~;o~ Prùlease enzymes are usually present in such co~ lle~;ial
tiol-s at levels sufficiPnt to provide from 0.005 to 0.1 Anson units (AU) of
activity per gram of co..-l~;c;l;-~n
Suitable e~camples of pl~,teases are the subtilisins which are ob~ned from
particular strains of B. subtilis and B. licheniforms. Another suitable protease is
ob~i~ed from a strain of R~cill~lc, having Ind~ilnl~.n activity th.ùugllout the pH
range of 8-12, developed and sold by Novo Industries A/S under the registered
trade name ESPERASE. The ~rt~.dtior of this enzyme and analogous enzymes is
describe~ in British Patent Spe~ifi~tion No. 1,243,784 of Novo. Proteolytic
enzymes suitable for removing protein-based stains that are commp-rcially available
include those sold under the tradPn~mps ALCALASE and SAVINASE by Novo
TT~II.CI~;FS A/S (Denm~rk) and MAXATASE by Tnt~ ;On~1 Bio-SynthPti~s~ Inc.
(The N~hF-l~n~lc). Other ~loleases include Protease A (see European Patent
Application 130,756, published January 9, 1985) and Protease B (see Elllol)ean
Patent Appli''~tioll Serial No. 87303761.8, filed April 28, 1987, and E-lu~a
Patent Applic~tion 130,756, Bott et al, published January 9, 1985).
-
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Amylases include, for example, a-amylases described in British Patent
Specifir~tion No. 1,296,839 (Novo), RAPIDASE, Intern~tion~l Bio-SynthPtics,
Inc. and TERMAMYL, Novo Industries.
The cell~ ce usable in the present invention include both b~tP~i~l or fungal
ce]l~ ce. P~ef~ .ably, they will have a pH optimum of between S and 9.5. Suitable
cç~ cP~ are ~li~losP~l in U.S. Patent 4,435,307, L~l,csgo~hd et al, issued March
6, 1984, which ~l;c~1os~os fungal cPllul~ce produced from Humicola in~ol~pnc andHumicola strain DSM1800 or a cell~ ce 212-producing fungus belonging to the
genus Aeromonas, and celll~ e extracted from the hepatopallcreas of a marine
mollusk (Dolabella Auricula Solander). Suitable cellulases are also ~iicrlQs~ inGB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME (Novo)
is Ps~i~lly useful.
Suitable lipase C~IL~yllleS for d~ t~.~ent usage include those produced by
mie,ool~;a~-ic...c of the Pseudolnonas group, such ac PseudoTnon~c stutzeri ATCC19.154, as ~1icclosed in British Patent 1,372,034. See also lipases in J~ e~
Patent Application 53,20487, laid open to public inCpection on ~ebruary 24, 1978.
This lipase is available from Amano Pharma~eutir~l Co. Ltd., Nagoya, Japan,
under the trade name Lipase P "Amano," hereinafter referred to as "Amano-P."
Other COIll~ ial lipases include Amano-CES, lipases ex Chr~.~.ob~tçr viccosum~
e.g. Chr~ ol~ t~ ~ viccosum var. lipolyticum NRRLB 3673, co,llll-e.c;ally
available from Toyo Jozo Co., Tagata, Japan; and further Chlo-..ob~t. . viccQs-lm
lipases from U.S. n;Q~ ";-~I Corp., U.S.A. and Disoynth Co., The N~thPrl~n<ls,
and lipases ex Pseudomon~c gladioli. The LIPOLASE enzyme derived from
~llmit~la l;.n..gil-o~ and commercially available from Novo (see also EPO
341,947) is a ~l~f~.lcd lipase for use herein.
Peroxidase en~,--es are used in combination with oxygen sources, e.g.,
pe.cdlbunate, perborate, persulfate, hydrogen peroxide, etc. They are used for
"sollJtion bl-p~ n~ i.e. to prevent transfer of dyes or pigmPntc removed from
~.,l.sn ~ s during wash operations to other substr~tPs in the wash solution.
Peroxidase enzymes are known in the art, and inclllde~ for eY~mrkP, horcpra~lichperoxidase, li~nin~cP" and haloperoxidase such as chloro- and bromo-peroxi~cf.
Peroxidase-col.l~il-ing detergent compositions are disclosed, ~or example, in PCT
Intern~tion~l Application WO 89/099813, published October 19, 1989, by O.
Kirk, ~ccignPf~ to Novo Industries A/S.
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A wide range of enzyme materials and means for their inco,~ tion into synthetic
dele.~;en~ co,..~os;Lionc are also disclosed in U.S. Patent 3,553,139, issued January
5, 1971 to McCarty et al. Enzymes are further Ai~los~ in U.S. Patent
4,101,457, Place et al, issued July 18, 1978, and in U.S. Patent 4,507,219,
~ghrs, issued March 26, 1985, both. ~nzyme m~teri~lc useful for liquid
deLcl~cnt form~ tion~, and their inco~ Lion into such fonn~ tio~s, are
~i~los~ in U.S. Patent 4,261,868, Hora et al, issued April 14, 1981. Enzymes
for use in de~r~.,b can be stabilized by various techniques. Enzyme stabili7~tir,n
techniques are Aicclosed and eYemplified in U.S. Patent 3,600,319, issued August17, 1971 to Gedge, et al, and Eulupean Patent Application Publication No. 0 199
405, Application No. 86200586.5, published October 29, 1986, Venegas. Enzyme
stabili7~tion ~y~lcllls are also described, for example, in U.S. Patent 3,519,570.
Enzyme Stabilizers
The e~ ll,es employed herein are stabilized by the pl~sence of water-soluble
sources of c~lcium and/or m~ oSi~m ions in the finich~A colllpcs!;l;onc which
provide such ions to the enzymes. (c~ llm ions are genrrally so"~.hat more
effective than ll~ .e~ .l ions and are ~lcrclled herein if only one type of cation is
being used.) AdAi~io~l stability can be provided by the ~cs~ nce of various other
art-~ rlosecl stabilizers, ec~i~lly borate sI~erilos see Scve.~on, U.S. 4,537,706.
Ble~chin~ C~ mds - l~le~ching ~ents and Bleach Activators
The d~te.~ent co~llpo~ ons herein may optionally contain ble~rhing agents or
bl~ohin~ colll~;~;onc cont~ining a ble~ching agent and one or more bleach
activators. When present, ble~rhing agents will typically be at levels of from
0.1% to 30%, more typically from 1% to 20%, of the delc,~ent co,..po~ilion,
~Cpeci~lly for fabric l~llnAe~ing. If present, the amount of bleach activators will
typically be from 0.1% to 60%, more typically from 0.5% to 40% of the
ble~hin~ co-"posilion comprising the ble~rhing agent-plus-bleach activator.
The blearhin~ agents used herein can be any of the ble~chin~ agents useful for
det~.gent co~po~ n~ in textile rle~ninE, hard surface clr~ninP~ or other cleanin~
~u ~ses that are now known or become known. These include oxygen bleaches as
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19
well as other ble~rhing agents. Perborate bleaches, e.g., sodium pe~lJul~te (e.g.,
mono- or tetra-hydrate) can be used herein.
Another categol y of ble~rhing agent that can be used without restric.*on
encomp~es percarboxylic acid ble~hinE agents and salts thereof. Suitable
~Y~mple~ of this class of agents include m~gnecillm monoperoxyphth~l~te
hexahydrate, the m~neSi~lm salt of met~hloro perbenzoic acid, 4-nonylamin~4-
oxo~ro~ylJutyric acid and di~rw~ydo~ec~n~ioic acid. Such bl.~o~rhinE agents are
~ rlnsed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S.
Patent Applic~*or~ 740,446, Burns et al, filed June 3, 1985, Lùn,~all Patent
Applica*on 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent
4,412,934, Chung et al, issued November 1, 1983. Highly ~lcr~ d ble~hinE
agents also include 6-nonylamino-6-oxoperoxycaproic acid as ~lesGribe~ in U.S.
Patent 4,634,551, issued January 6, 1987 to Burns et al.
r,.uAy~;cn bl~ E agents can also be used. Suitable peroxygen blP~hing
con~,ounds include sodium ~,a.l,on~t~ peroxyhydrate and equivalent "p~rca,bona~e"
b~ hes, sodium pyro~hosph~t~ peroxyhydrate, urea peroxyhydrate, and sodium
peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by
DuPont) can also be used.
M~l~n_s of ble~rhinE agents can also be used. Peroxygen ble~rhinE agents, the
p~,bol~t~s, etc., are pl~f~,~bly co.l~bined with bleach activators, which lead to the
in sin ~iod~lc~ n in aqueous solution (i.e., during the washing process) of the
peroAy acid ccsll~ ~n~ g to the bleach activator. Various nonlimiting eY~
of activators are ~i~los~ in U.S. Patent 4,915,854, issued April 10, 1990 to Maoet al, and U.S. Patent 4,412,934. The nonanoyloxybenzene sulfonate (NOBS) and
r~lyl ethylene ~ ine (TAED) activators are typical, and ~ lun_s thereof
can also be used. See also U.S. 4,634,551 for other typical bleaches and activators
useful herein.
Highly l,r~ f~ d atnido-derived bleach activators are those of the formulae:
R1N(R5)C(O)R2C(O)L or R1C(O)N(R5)R2C(O)L
wh~ R1 is an alkyl group cont~ining from 6 to 12 carbon atoms, R2 is an
alkylene cQ~ ng from 1 to 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl
CC~ ~I; ;ning from 1 to 10 carbon atoms, and L is any suitable leaving group. A
leaving group is any group that is dicpI~ce~l from the bleach activator as a
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consequence of the nucleophilic attack on the bleach activator by the perhydrolysis
anion. A ~rcrcllcd leaving group is phenyl sulfonate.
Pr~f~.l~ examples of bleach activators of the above formulae include (6-
oct~n~mido-caproyl)oxybçn7pnpsulfonate~ (6-non~n~midoc~proyl)oxybel-7.~i-e,,.~
fonate, (6-de~n~mido-caproyl)oxyb~n7~ones~llfonate~ and mixtures thereof as
described in U.S. Patent 4,634,551, incorporated herein by reference.
Another class of bleach activators comprises the be.~zo~.n-type activators
~ clos~ by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990,
incoll,uldted herein by lcrc~nce. A highly prcrellcd activator of the ben7~x~7in-
type is:
~N~C~
Still another class of pr~fe.l~ bleach activators jnrll~des the acyl lactam activators,
espe$i~lly acyl caprol ~t~m~ and acyl valerol~rt~m~ of the formulae:
O O
~I C--CH2--CH2 0 C--CH2--CH2
R6 C N ,CH2 R6--C--N
~CH2--CH2 ~CH2--CH2
R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group con~ g from 1
to 12 carbon atoms. Highly plcÇclled lactam activators include benzoyl
caprol~rPm, octanoyl caprolactam, 3,5,5-trimethylh~Y~noyl caprolactam,
nonanoyl caprol~~t~m~ decanoyl caprol~rt~m~ l~nde~noyl caprol~rPm~ benzoyl
valerol~rt~m, octanoyl valero!~rt~m, decanoyl valerol~ct~m, ImdPc~i-o~
valerol~rt~m, nonanoyl valer~l~rt~m, 3~s~s-trimethylhpy~noyl valerol~ct~m and
ib~lul~s thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8,
1985, inco.~ld~d herein by ~ fcr~nce, which di~rlosPs acyl caprol~rt~m~,
including benzoyl cap~ m, adsorbed into sodium ~.bOld~C.
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R~ hing agents other than oxygen bleaching agents are also known in the art and
can be utilised herein. One type of non-oxygen ble~ching agent of particular
interest includp~s phl~to~tivated bl~nhing agents such as the sulfonated zinc and/or
nh. ..inillln phth~locyanines. See U.S. Patent 4,033,718, issued July 5, 1977 toHolcombe et al. If used, detergent compositions will typically contain from
0.025% to 1.25%, by weight, of such blP~çh~c~ çcpe~ lly sulfonate zinc
phthalo~y~ine.
If desired, the bl~P~çhin~ c~ ~unds can be catalyzed by means of a ,,.~n~ Pse
co.l,pu.lnd. Such co,..~ounds are well known in the art and include~ for e~n-p'-,
the m~ng~nes~ based catalysts ~ osed in U.S. Pat. 5,246,621, U.S. Pat.
5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and European Pat. App.
Pub. Nos. 549,271Al, 549,272Al, 544,440A2, and 544,490Al; Preferred
c~ es of tbese catalysts include MnIV2(u-0)3(1,4,7-trimethyl-1,4,7-triaza-
cy~lonnll~n~o-)2(PF6)2, Mnm2(u-O)l(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclono-
nane)2 (C104)2, M[nIV4(u-0)6(1,4,7-triazacyclonon~ne)4(Cl04)4, MnIIIMnIV4
(u-O)l(u-OAc)2 (1,4,7-trimethyl-1,4,7-triazacyeloi-on~ne)2(C104)3, MnIV(1,4,7-
lli.,.~ll,~l-1,4,7-L~ elo~ n~ne)- (OCH3)3(PF6), and ".i,~Lu.~s thereof. Other
metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and
U.S. Pat. 5,114,611. The use of m~ng~nese with various complex ligands to
enh~nce b~ hing iS also repolled in the following United States Patents:
4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161;
5,227,084;
Corrosion Inhibitor Co~ )ol~nd
The cQI~ nc may contain corrosion inhibitors pler~l~ably sel~t~ from
organic silver coating agents, particularly paraffin, nill~t:n-co~t;~h~;n~ corrosion
inhibitor c~ ounds, bismuth compounds and Mn(II) compounds, particularly
MnaI) salts of organic lig~n~s
Organic silver coating agents are described in PCT Publication No. WO94/16047
and c4p n.l;ng UK Application No. UK 9413729.6 (allol.i~'s docket no.
CM750F). Nill~ge.~ conl;~;n;n~ corrosion inhibitor compoun~ls are ~li~lose~ in
c4pen.1ing Eufo~l Appli~tior~ no. EP 93202095.1 (attorney's docket no.
CM571F). Mn(II) co.npounds for use in corrosion inhibition are described in
C~pf n~ling UK Application No. 9418567.5 (attorney's docket no. CM719FM).
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Other Tn~redients
A wide variety of other ingredients useful in detergent co"~;lion~ can be
inr1ul1ed in the co",~o;,it;~ nc herein, inclufling other active ingredientc, carriers,
hydroL~s, plvce~ g aids, dyes or pigments, etc. Ingredients may also be
incorporated to assist in the tabletting process such as lubric~ting agents, sodium
acetate and nonionic surfact~ntc
~ompact Solid P~c;y~ ;on
Another aspect of the present invention relates to the p~epa,dLion of the comp~rtçd
solid del~r~ent co",po~;t;ons The comr~rt~ solids may be m~nllfactllred using
any suitable comr~rting process, such as tabletting, briquetting or extrusion,
preferably tabletting. Preferably tablets are manufactured using a standard rotary
tabletting press using COIllpleS5iOll forces of from S to 13KN/cm2, more preferably
from S to 1 lKN/cm2-
A ~f~lt;d process for making the dele,gent ~",~c;l ;o~c of the inventioninrllldç~s the step of spraying of the organic binder m~tPri~l onto at least a portion
of the ~ linity system.
According to a prc;re.l~ d process aspect of the present invention the comp~ct~
solids are pre~ ed by the following process.
1. Organic binder m~teri~l is sprayed onto at least a portion of the ~ linity
system which cQmrr~ s particles of suitable ~lk~line salts, particularly silicate
salts, until a suit~hle coating level is achieved.
2. The reclllting coated ~ nity system is dry added to other ingredients
particularly any builder salts, in a tumbling mixer.
3. The organo ~ .hosl)hon~te crystal growth inhibitor and optionally other
ingredients such as nonionic surf~ct~ntc, ch~l~nts and silvercare additives are
sprayed on to the .,.i~luç~,.
-
CA 02227772 1998-01-23
W O 97~05226 PCT~US96/11582
23
4. The resnlt~nt mixture is passed through a second mixer for a short final mixing
period.
5. Comr~,tion of the Illi~tl~lC.
A time inteNal may be left belwPel~ completion of step 1 and commPn~emPnt of
step 2.
In an ~ltPrn~tive aspect to the process the organo diphosrho~te crystal growth
inhibitor is dry added in step 2, as an agglomerate particle.
According to another pr~Ç."led process aspect of the present invention the
comp~ted solids are prepared by the following process.
1. The ~lk~linity system which comprises particles of suitable ~ linP salts,
particularly silicate salts, and optionally other ingredients particularly any builder
salts, are dry mixed in a tumbling mixer.
2. The organo diphos~hc~n~t~ crystal growth inhibitor, the organic binder and
optionally other in~-~lie.,ls such as nonionic surf~t~ntc, chel~ntc and silvercare
additives are sprayed on to the mixture.
3. The re~l~lt~nt mixture is passed through a second mixer for a short final mixing
period.
4. ~~" ~ ;nn of the Illi~lUl~,.
In an ~ltern~tive aspect to the process the organo diphosphon~t~o crystal growthinhibitor is dry mixed in step 1, as an agglomerate particle.
The co.~-p~ ;oll step is achieved by convçnti~n~l means, for çy~mrl~ on a 12 head
rotary press under a co",~lesaion force of 5-13KN/cm2 so that the comp~rted solid
has a minimum hd-~lness of 176N to 245N, prefel~bly from 195N to 275N,
measured by a C100 ha,~lness test as supplied by I. Holland In~llUI~ . This
process may be used to prepare homogenous or layered comp~cted forms,
particularly tablets of any size or shape. Preferably, tablets are symm~tric~l to
ensure the uniro~ coll~tion of the tablet in the wash liquor.
CA 02227772 1998-01-23
W O 97/05226 PCTAUS96/11582
24
According to the present invention the comp~ct~l form del~gcnt compositions
may find utility in all types of ~ltom~tic dish- and laundry washing m~hin~s
in~lurling inr~ tri~l and domestic m~l-h
Abbreviations used in Examples
In the dele.gent compocitions, the abbreviated co-ll~onent identific~tions have the
following mlo~nin~s
Nonionic : A mixture of C13 15 predominantly linear primary
~lf ohol~ con~len~ed with an average of 2 moles of
propylene oxide and 6 moles of ethylene oxide
Silicate : Granular sodium silicate (SiO2:Na2O ratio =
2.0)
PEG : Polyethylene glycol with an average molecular
weight of 1500 (i.e. PEG 1500)
Sulphate : Anhydrous sodium s~l1rh~t~
Polymer/HEDP/Sulphate : Aggloll,e.ate particle cont~ining at a weight ratio
~glon.e.dl~ of 6:1:18, a random copolymer of 3:7
acrylic/mP!th~-rylic acid (Mw = 3,500); HEDP;
and sodium sulph~t~.
Citrate : Tri-sodium citrate dihydrate
D~MP : Diethylene tri~mine penta (Methylene phosphonic
acid), mal~eLed by Mon~ntc) under the Tr~ n~m~
Dequest 2060
TAED : Tetr~ etyl ethylene ~ mine
PBl : Anhydrous sodium perborate monohydrate bleach
CA 02227772 1998-01-23
W O 97/05226 PCTnJS96/1158
Silvercare additive : 1:2 mixture of benzotriazole and a p~raffin oil sold
under the tr~-len~me Winog 70 by Wintershall
F.Y~n1~1e
J
The following tabletted detergent cou~iLions A to B suitable for use in an
~ulc~ldLic disl-w~l-ing m~hine were prepared by the following process in accord
with the invention:
1. PEG lS00 was sprayed onto the granular silicate until a suitable coating level
was achieved, optimally providing a weight ratio of granular silicate to PEG 1500
of from 10:1 to 3:1.
2. The re~ltin~ coated silicate particles were dry added to all of the other
ingre~ nt~, inclu~ g HEDP co,-~ining agglcu~ dle particles, except those added
in the spray on step 3., in a tumbling mixer.
3. The nonionic s~-rf~t~nt DETPMP and silvercare additive in~ iient~ were
sprayed on to the dry mix.
4. The resl-lt~nt .l~lu-~ was passed through a second mixer for a short final
mi~ing peAod.
5. The IIIi~IUie~ was then comr~ct~ using a 12 head rotary press under a
co---~ ion force of 5-13KN/cm2 so that the comr~cted solid Pr~1UUl~ had a
minimllm har~nei;, of l95N, measured by a C100 ha~ ess test as supplied by I.
The tablets so formed were disc shaped having a ~ . of 38mm and thick
of 14mm.
The reference product, denoted 'Ref', was p~cpa~d by an identic~l process, otherthan that the initial silicate coating step was absent, and thus the unco~ted silicate
was simply dry added as in step 2. of the process for compo~i~ion~ A to C.
CA 02227772 1998-01-23
WO 97/05226 PCT~US96/11582
26
The tabletted co"lposition C was p,~felled by an idPntic~l process other than that
the HEDP was added as a spray on in step 3., rather than as a co~ oaent of an
agglon-e.dle particle. ?
Tablet Ref A B C
Citrate 13.6 13.6 17.1 26.4
Carbonate 14.0 14.0 17.5 15.0
Silicate 10.5 10.9 13.6 11.8
PEG - 2.0 2.0 1.5
~et~ te 2.0 2.0 2.5
Polymer/HEDP/ 21.0 21.0 26.3
s-llph:.t~
!Qm-~.nb~
HEDP (sprayed on) - - - O 7
PBl 7.8 7.8 9.7 1.5
PB4 - - - 6.9
T AE~ 2.2 2.2 2.7 4.3
Enzymes 1.8 1.8 2.2 3.0
Silvercare additive 0.64 0.64 0.8 0.6
~TQnioni~ 1.6 1.6 2.0 1.2
Sulphate 19.7 19.7 - 18.1
Misc/balance to
100%
Product Hardness
The har~n~ (e,~ sed in units of Kg) of the reference product was co,-,~ed to
that of (~o.l.l o~;l;on A after first m~nuf~rt~e and after storage at 40~C. ~,
Ref A
Freshly made 25.4 37.2
1 week storage 25.1 48.6
2 weeks storage 26.2 45.2
