Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~ 21 66~61
WO 95/02390 PCT/US94/06943
~URFACTANT ~Y~STF.~
This invention relates to a surf~ct~nt system derived from natural sources
for incorporation into detelgellt compositions suitable for use in cleaning
processes, especially fabric cleaning and more especially to high density
granular d~lergent compositions comprising said surf~ct~nt system.
Granular detergelll compositions cont~ining synthetic detergen~,
particularly linear allyl benzene sulfonate salts are well known in the art
and are in widespread commercial use. Conventionally the linear alkyl
benzene sulfonate salt forms part of a surf~c~nt mixture in association
with one or more o~er anionic or nonionic surf~ct~ntc.
Current environmental concern has focussed on the undesirability of
deriving detefgent coml)o.lents from non-renewable hydrocarbon sources.
Interest has ther~fole increased in the fonn~ tion of well-pelrolnling
deterg~t compositions comprising surf~ct~nt systems derived from
natural sources.
An example of an anionic surf~ct~nt which is readily biodegradable and
which could replace the alkyl benzene sulfonate component either
partially or in toto is alkyl sulfate surf~et~nt
Detergelll compositions including alkyl sulfate surfactant derived fromnaliurally occuring fats and oils are known in the art. For example, GB-
A-1,399,966, in the name of the Procter & Gamble Company, discloses a
de~er~,ent composition cont~inin~ alkyl sulfate surfactant derived from
tallow oil, or from eoconut oil.
WO 95/02390 2 ~ ~ 6 8 ~ I PCT/US94/06943 ~
Natural oils and fats provide feedstock material encompassing a range of
alkyl chain lengths. The alkyl chains are predomin~ntly linear, in contrast
to the branched nature of feedstock obtained from synthetic sources. For
example, tallow fat contains a high proportion (typically about 70%) of
C1g alkyl chains. Coconut and palm oil on the other hand contain a high
proportion of C12 alkyl chains (typically about 55%) and lesser
proportions of C14, C16 and C1g alkyl chain lengths.
The deter~,el,cy performance characteristics of surf~ct~ntc having allyl
chains are known to depend on the nature and length of the alkyl chain.
In general, surf~t~nt~ having shorter alkyl chains are more hydrophillic,
hence more water soluble, and thus tend to pelrorlll better at lower wash
temperatures. Those with longer alkyl chains conversely tend to pelro.l.
well at higher wash t~ elal~lres. The form~ tor of a natural surf~et~nt
system is hence faced with the problem of how to formulate a surfactant
system which provides good detergellcy over a wide range of wash
tem~el~lules derived from feedstock material, which as provided by
nature, contains a non-opLill.um distribution of alkyl chain lengths for this
purpose.
EP-A-342,917 describes a surf~ct~nt system, derived preferably from
natural feedstock material, comprising an anionic surf~ct~nt the major
ingredient of which is an alkyl sulfate of mixed alkyl chain length such
that at least 10% by weight of the alkyl chains present in the alkyl sulfate
are C12 chains and at least 20% by weight of the alkyl chains are C1g
chains.
The Applicants have found that a surf~ct~nt system cont~ining allyl
sulfate surf~ct~nt of mixed allyl chain length such that the level of C12
and C1g alkyl chain lengths is minimi~e~ and wherein the C14 and C16
alkyl chain lengths form the major part, provides good detergency
pelÇollnance over a wide range of temperatures.
The Applicants have also found that when form~ te~l with an alkyl
ethoxysulfate cosurf~ct~nt, and preferably a nonionic surf~ct~nt, such a
surfactant system provides good detergency in the presence of cationic
WO 95/02390 2 1 6 6 8 6 1 PCT/US94/06943
fabric softener compounds even when the total ~evel of anionic surfactant
in the composition is at a low level, namely from 5% to 10% by weight of
the eomposition.
According to one aspect of the present invention the~e is provided
surf~ct~nt system cont~inin~
(a) alkyl sulfate surfactant derived from natural sources
comprising a mixture of alkyl chain lengths wherein the weight
distribution of the alkyl chain lengths is such that less than 20% by
weight of the alkyl chain lengths are C12, from 30æ to 80% by
weight of the alkyl chain lengths are C14~ from 30% to 50% by
weight of the alkyl chain lengths are C16 and less than 10% by
weight of the alkyl chain lengths are Clg.
Said anionic surfactant system prefelably also contains alkyl ethoxysulfate
surf~ nt. Said alkyl ethoxysulfate surf~et~nt is pleferably a water
soluble C12-Clg alkyl ethoxysulfate salt cont~inin~ an average of from 1
to 7 ethoxy groups per mole derived from the condensation product of a
C12-Clg alcohol wherein said C12-Clg alcohol is most preferably
derived from a natural source.
To provide good dissolution characteristics for the alkyl sulfate surfactant
and provide robust pelrollllallce in the presence of cationic fabric softener
components in the wash it is highly ~leferably that where present in said
surf~ct~nt system the alkyl ethoxysulfate surf~ct~nt is most preferably in
intinn~t~ admi~ture with the alkyl sulfate surf~et~nt The weight ratio of
the alkyl sulfate surfactant to the alkyl ethoxysulfate surf~ct~nr is
~lefefably from 2:1 to 19:1.
Most preferably said surfactant system is essentially free of alkyl benzene
sulfonate.
.
The total level of alkyl sulfate and alkyl ethoxysulfate surf~ct~nt in the
granular detergellt composition is preferably from 5% to 10% by weight
of tlhe composition, more preferably from 6% to 9% by weight of the
composition and most preferably from 6.5 % to 8 % by weight of the
composition. Said granular detel~ent composition provides good
2~86t
WO 95/02390 PCT/US94/06943 ~
d~tergellcy performance even when used in wash solutions where cationic
fabric softener components are present. Examples of cationic fabric
softener components include the well known ~uaternary ammonium
compounds. Cationic fabric softeners are disclosed for example in EP-A-
0125,122, and co-pending European Application 91-202881.8 which
discloses water-soluble quaternary ammonium compounds.
It is an essential aspect of the invention that the alkyl sulfate surfactant is
derived from natural sources. By derived from natural sources it is meant
herein that the alkyl chain portion of the surf~ct~nt is derived from
naturally occuring fats and oil. Allyl chains derived from such natural
oils and fats are typically linear and have alkyl chains with even numbers
of carbon atoms, most typically C12, C14, C16 and C1g. The alkyl
chains may contain a small proportion of lln~tllrated, e.g.: alkenyl,
chains which if desired may be hydrogenated, or "hardened" to minimi
these in4,ulily levels. Typically the alkyl sulfate surfactant is produced
from alcohols obtained by reduction of the natural oils and fats.
Examples of natural oils and fats include those derived from coconut,
babassu, palm kernel, beef tallow, kapok, olive, peanut, ses~me and
te~ee~l.
It is also an essential aspect of the present invention that the alkyl sulfate
surf~ct~nt comprises a mixture of alkyl chain lengths. It is preferred that
the level of C12 and C1g alkyl chain lengths is minimi7~ and that the
major proportion of the allyl sulfate surfactant comprises C14 and C16
alkyl chain lengths. More particularly the alkyl sulfate surf~ct~nt
comprises such surf~ct~nt with a mixture of alkyl chain lengths wherein
the weight distribution of the alkyl chain lengths is such that less than
20%, most preferably less than 15% of the alkyl chains are C12, from
30 % to 80 %, ~refel~bly from 35 % to 70 %, most preferably from 40 % to
60% of the alkyl chains are C14, from 30% to 50%, preferably from
30% to 40%, most pl~ferably from 32% to 38% of the alkyl chains are
C16, less than 10%, preferably less than 5%, most preferably less than
3 % of the alkyl chains are C18
Alkyl sulfate surf~et~nt of the desired alkyl chain length distribution is
obtained from natural feedstock, mP~ning natural oils or fats, or any
WO 95/02390 2 ~ 6 6 ~ ~ ~ PCT/US94/06943
.
s
mixtures thereof, or the natural alcohols derived therefrom, by any
suitable physical process which allows for the separation of such
feedstock into different components with the desired alkyl chain length
distributions. Suitable physical processes would include, for example,
~i~till~tion processes. The separation of feedstock ;~aterial into different
components of desired composition is often referred to in the industry as
"cutting" of the feedstock (into desired "cuts"). The dirrelent components
(or cuts) may then be used as such, or blended, as a~ropliate to allow
for derivation of the alkyl sulfate surf~ct~nt with the desired alkyl chain
length distribution in accord with the invention.
In a preferred execution of the invention the surf~ct~nt system also
comtains alkyl ethoxysulfate surf~cf~nt prefel~bly C12-Clg alkyl
ethoxysulfate surfactant cont~ining an average of from 1 to 7 moles
ethylene oxide per mole derived from the condensaion product of a C12-
Cl~ alcoho~ wherein said C12-C1g alcohol is most ~reftrably derived
from natural sources. Fx~mples of naturally occurring materials from
which the alcohols can be derived are coconut oil and palm kernel oil and
the corresponding fatty acids. Preferred are C12-C14 alkyl ethoxy-rS~ate
salts with an average of from one to five ethoxy groups per mole, and
most preferably with an average of from one to three ethoxy groups per
mole.
The weight ratio of the alkyl sulfate surf~ct~nt to the alkyl ethoxysulfate
surf~ct~nt is ~referably from 2:1 to 19:1 more preferably from 3:1 to 12:1
and most ~leferably from 3.5:1 to 10:1.
It is prefell~d that the alkyl sulfate surfactant and the alkyl ethoxysulfate
surfactant are in intim~te admixture. Where incorporated in a particulate
composition they should be mixed prior to the formation of any
part;culate component of which they may form a part. In the case of a
spray dried granule, this mixing can take place in the slurried mixture fed
to the spray drying equipment. Where another type of granule is formed
an intim~tt? mixlture of the surfactants should be made before
agglomeration, milling, fl~king, prilling or any other particulate forming
process takes place.
WO 95/02390 PCT/US94/06943 ~
The surf~çt~nt system of the invention may contain as non-essential
components other anionic surfactant components including alkane
sulfonate and alkyl ester sulfonate surfactants.
.
Use of alkane sulfonate salts as anionic surfactants is well known in the
art, being disclosed for example in US Patent 3 929 678. Aliphatic
alkane sulfonate salts may be obtained from the reaction of an aliphatic
hydrocarbon, which may include the iso-, neo-, meso- and n-paraffins,
having 12 to 24 carbon atoms and a sulfonating agent which may for
example be SO3, H2SO4 or oleum the reaction being carried out
according to known sulfonation methods, including bleaching and
hydrolysis. In accord with the present invention the aliphatic C12-C20
alkane sulfonate salts are preferred with the aliphatic C14-C20 alkane
sulfonate salts being most preferred. Prefelled as cations are the alkali
metal and ammonium cations.
Alkyl ester sulfonate surf~rt~nt~ hereof include linear esters of C12-C20
carboxylic acids (ie. fatty acids) which are sulfonated with gaseous SO3
according to "The Journal of the American Oil Chemists Society," 52
(1975), pp. 323-329. Suitable starting materials include natural fatty
subs~nre~ as derived from tallow, palm oil, etc.
The preferred alkyl ester sulfonate surf~rt~nt~ in accord with the
invention comprise methyl ester sulfonate surf~ct~nts of the structural
forrnula:
o
R3--CH--C oR4
Sl3M
wherein R3 is a C12-C20 alkyl, R4 is methyl and M is a cation which
forms a salt with the methyl ester sulfonate. Suitable salt-forming cations
include metals such as sodium, pot~sil-m, and lithium, and substituted or
unsubstitllte~i ammonium cations, such as monoeth~nt lamine,
diethanolamine, and triethanolamine. Most preferably, R3 is C14-C20
alkyl.
~ wo gs/~239~ 2 ~ ~ ~ 8 ~ t PCT/US94/06943
The surfactant system of the invention is desirably incorporated as part of
a detergent or cleaning composition for use in, for example, laundry,
m~nll~l and automatic dishwashing, and hard-surface cleaner applications.
The level of incorporation of the surf~ct~nt system, and of any further
ingredients, will depend upon the nature of the detelgellL or cleaning
composition, and in particular its desired application.
The compositions may in addition comprise in general terms those
ingredients commonly found in detergent products which may include
organic surf~ct~nt~, deler~elll builders, anti-redepo~ition and soil
suspension agents, suds suppressors, enzymes, optical brighteners,
pholtoactivated bleaches, perfumes, filler salts, anti-corrosion agents and
colours.
T.~lln-lry deter~ellt compositions may also comprise fabric softening and
~nti~tatic agents.
The surfact~nt system of the invention may include as a preferred
additional component a nonionic surf~ct~nt. Preferably the nonionic
surf~ct~nt is incorporated such that the weight ratio of nonionic surfactant
to anionic surfactant is from 1:4 to 4:1, ~leferably 1:2 to 2:1.
In one preferred aspect of the invention the surf~rt~nt system of the
invention is incorporated within a laundry detergelll composition at a level
of from 3% to 50% by weight, preferably from 5% to 30%, mos~
preferably from 7% to 15% by weight of the detergen~ composition.
Machine dishwashing detergellt compostions incorporating the anionic
surfactant system of the invention comprise from 0.5% to 10% by weight,
preferably from 1% to 10% by weight, most preferably from 1% to 5%
of the surfactant system by weight of the invention. Prefera~ly said
machine dishwashing compositions also contain a nonionic surfactant
system. Most ~refelled are low-fo~ming nonionic surfactants, especially
the water soluble ethoxyleted C6-C16 fatty alcohols and C6-C16 mixed
ethoxylated/propoxylated fatty alcohols and mixtures thereof. Preferably,
the ethoxylated fatty alcohols are the C10-C16 ethoxylated fatty alcohols
WO 95/02390 ~ 6 ~ PCT/US94/06943 ~
with a degree of ethoxylation of from 5 to 50, most preferably these are
C12-C16 ethoxylated fatty alcohols with a degree of ethoxylation from 8
to 40. Preferably the mixed ethoxylated/propoxylated fatty alcohols have
an alkyl chain length of from 10 to 16 carbon atoms, a degree of
ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to
10.
Suitable nonionic surf~ct~nt~ for incorporation as part of a nonionic
surfactant system include polyhydroxy fatty acid amide surf~ct~ntc,
alcohol ethoxylate surf~ct~nt~ and allyl polyglucoside surf~ct~nt~.
Additionally detergenL compositions in accord with the invention may
optionally contain cationic, amphoteric, zwitterionic and semi-polar
surf~ct~t~.
The polyhydroxy fatty acid amide surf~ct~ntc in accord with the presentinvention comprise compounds of the structural formula:
O R5
R6--C--N Z
wherein: R5 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-
hydroxypropyl, or a mixture thereof, preferably C1 or C2 alkyl, most
preferably C1 alkyl (ie. methyl); and R6 is a C11-C31 hydrocarbyl,
~referably straight chain C 1 1-C 19 alkyl, or alkanyl most preferably
straight chain C16-C1g alkyl or alkenyl, or mixture ~ereof; and Z is a
polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3
hydroxyls directly connecte~ to the chain, or an alkoxylated derivative
(preferably ethoxylated or propoxylated) thereof. Z prefelably will be
derived from a reducing sugar in a reductive ~-"i~ ion reaction; more
preferably Z is a glycityl. Suitable reducing sugars include glucose,
fructose, maltose, lactose, g~ tose, mannose, and xylose.
As raw materials, high dextrose corn syrup, high fructose corn syrup, and
high maltose corn syrup can be l)tilise~3 as well as the individual sugars
listed above. These corn syrups may yield a mix of sugar components for
~ WO 95/0~910 ~ 1 6 ~ PCTAUS94/06943
Z. It should be understood that it is by no means intended to exclude
other suitable raw materials. Z preferably will be selected from the group
consisting of-CH2-(CHOH)n-CH2OH, -CH(CH2OH)-(CHOH)n l-
CH:2OH, i-CH2-(CHOH)2(CHOR')(CHOH)-CH2OH, where n is an
integer from 3 to 5, inclusive, and R' is H or a cycl c or aliphatic
monosaccharide, and alkoxylated derivatives thereof. Most ~.eferled are
gly,cityls wherein n is 4, particularly -CH2-(CHOH)4-CH2OH.
R5 can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-
butyl, N-2-hydroxy ethyl, or N-2-hydroxypropyl.
R6 CO-N< can be, for example, coc~mi~le, stearamide, oleamide,
lauramide, myristamide, capric~mi-le, p~lmh~mide, tallowamide, etc.
Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-
deoxylactityl, 1-deoxy~ ctityl, 1-deoxym~nnityl, 1-deoxymaltotriotityl,
etc.
The most preferred polyhydroxy fatty acid amide has the general formula
O CH3
~, I
R6--C --N CH2 (CHOH)4CH2OH
wherein R6 is a C11-C1g straight-chain alkyl or alkenyl group.
Methods for m~king polyhydroxy fatty acid ~mi~les are known in the art.In general, they can be made by re~ctin~ an alkyl amine with a reducing
sugar in a reductive ~min~tion reaction to form a corresponding N-alkyl
polyhydroxyamine, and then re~ctin~ the N-alkyl polyhdroxyamine with a
fatty aliphatic ester or triglyceride in a condensation/amidation step to
form the N-alkyl, N-polyhydroxy fatty acid amide product. Processes for
m~king compositions cont~inin~ polyhydroxy fatty acid amides are
disclosed, for e~ample, in GB Patent Specification 809 060, published
FeblUary 18,1959, by Thomas Hedley & Co Ltd, US Patent 2 965 576,
issued December 20,1960 to E R Wilson, and US Patent 1 985 424,
issued December 25, 1934 to Piggott, each of which is incorporated
herein by reference.
W095/0~90 ~ 1 ~ 6 8 6 1 PCT~S94/06943
One class of nonionic surf~ct~nts useful in the present invention comprises
condensates of ethylene oxide with a hydrophobic moiety, providing
surfactants having an average hydrophilic-lipophilic balance (HLB) in the
range from 8 to 17, ~lefeiably from 9.5 to 13.5, more preferably from 10
to 12.5. The hydrophobic (lipophilic) moiety may be aliphatic or
aromatic in nature and the length of ~e polyoxyethylene group which is
condensed with any particular hydrophobic group can be readily adjusted
to yield a water-soluble compound having the desired degree of b~l~nre
between hydrophilic and hydrophobic elements.
Especially preferred additional nonionic surf~ct~nt~ of this type are the
C12-C20 primary alcohol ethoxylates cont~inin~ an average of from 3-11
moles of ethylene oxide per mole of alcohol, particularly the C12-C16
primary alcohol ethoxylates cont~inin~ an average of from 3-7 moles of
ethylene oxide per mole of alcohol and most prefer~bly the C12-C16
primary alcohol ethoxylates cont~ining an average of 3 moles of ethylene
oxide per mole of alcohol.
Another class of nonionic surfact~nt~ comprises alkyl polyglucoside
compounds of general formula
RO (cnH2no)tzx
wherein Z is a moiety derived from glucose; R is a saturated hydrophobic
alkyl group ~at contains from 12 to 18 carbon atoms; t is from 0 to 10
and n is 2 or 3; x is from 1.3 to 4, the compounds including less than
10% unreacted fatty alcohol and less than 50% short chain alkyl
polyglucosides. Compounds of ~is type and ~eir use in detergent
compositions are disclosed in EP-B 0 070 074
0 070 077,0 075 996 and 0 094 118.
A further class of surf~ct~nt~ are the semi-polar surf~ct~nt~ such as amine
oxides. Suitable amine oxides are selected from mono Cg-C20,
~refelably Clo-C14 N-alkyl or alkenyl amine oxides and propylene-1,3-
rli~mine dioxides wherein the rem~inin~ N positions are substituted by
methyl, hydroxyethyl or hydroxpropyl groups.
~wogs/n1lgO ~66~6~ PCT/US94/06943
Cationic surfactants can also be used in the detergent compositions herein
and suitable quaternary ammonium surfactants are selected from mono
Cg-C16, preferably C1o-C14 N-alkyl or alkenyl ammonium surfactants
wherein rem~ining N positions are substituted by methyl, hydroxyethyl or
hydroxypropyl groups.
Where form~ te~l as a granular composition any particulate components
may have any suitable physical form, i.e. it may take the form of flakes,
pril~s, marumes, noodles, ~;~bons, or granules which may be spray-dried
or non spray-dried agglomerates.
Another highly preferred component deter~,el.L or cleaning compositions
in accord with the invention is a detergellt builder system comprising one
or more other detergent builders. These can include, but are not
restricted to, phosphates, crystalline layered sodium silicates, carbonates
borates, alkali metal aluminosilic-~te~, monomeric polycarboxylates, homo
or copolymeric polycarboxylic acids or their salts in which the
polycarboxylic acid comprises at least two carboxylic radicals seperated
from each other by not more than two carbon atoms, carbonates, silicates
and Imixtures of any of the foregoing.
The builder system is preferably present in the detergent or cleaning
compositions in an amount from 1% to 95 % by weight.
When ~e detergelll composition is a laundry or m~t~hin~ dishwashing
deLel~,e.l~ composition the level of builder system is preferably from 1
to 8~% by weight, more preferably 20% to 70% by weight of the
compostion.
Suitable silicates are those having an SiO2:Na2O ratio in the range from
1.6 to 3.4, the so-called amorphous silicates of SiO2: Na2O ratios from
2.0 to 2.8 being employed where addition to the mixture of ingredients
that are spray dried is required. Where alumiT~osilicates con~tit Ite an
ingredient of the mixture to be spray dried, siiicates should not be present
in the mixture but can be incorporated in the form of an aqueous solution
serving as an agglomerating agent for other solid components, or, where
wo 95/02390 ;~ f 6 6 8 6 1 PCT/US94/06943 ~
the silicates are themselves in particulate form, as solids to the other
particulate components of the composition. However, for compositions in
which the percentage of spray dried components is low i.e. 305~, it is
preferred to include the amorphous silicate in the spray-dried components.
Whilst a range of aluminosilic~t~ ion exchange materials can be used,
preferred sodium aluminosilicate zeolites have the unit cell formula
Naz [(A102 ) z (SiO2 )y ] xH 2
wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5
and x is at least S, ~Lefelably from 7.5 to 276, more ~Leferably from 10
to 264. The aluminosilicate materials are in hydrated form and are
preferably crystalline, cont~inin~ from 10% to 28%, more preferably
from 18 % to 22% water in bound form.
The above aluminosilicate ion exchange materials are further
characterised by a particle size ~ m~oter of from 0.1 to 10 micrometers,
preferably from 0.2 to 4 micrometers. The term "particle size diameter"
herein represents the average particle size diameter of a given ion
exchange rnaterial as determined by conventional analytical techniques
such as, for example, microscopic detelmillation lltili7in~ a SC~nning
electron microscope or by means of a laser granulometer. The
aluminosilicate ion exchange materials are further characterised by their
calcium ion exchange capacity, which is at least 200 mg equivalent of
CaC03 water hardness/g of alumino~iliç~t~, calculated on an anhydrous
basis, and which generally is in the range of from 300 mg eq./g to 352
mg eq./g. The aluminosilicate ion exchange materials herein are still
further characterised by their calcium ion exch~nge rate which is at least
130 mg equivalent of CaCO3/litre/mimlte/(g/litre) [2 grains Ca+ +/
gallon/mimlte/gram/gallon)] of aluminosilicate (anhydrous basis), and
which generally lies within the range of from 130 mg equivalent of
CaCO3/litre/minllte/(gram/litre) [2 grains/gallon/minllte/ (gram/gallon)]
to 390 mg equivalent of CaCO3/litre/mimlte/ (gram/litre) [6
grains/gallon/min~lte/(gram/gallon)], based on calcium ion hardness.
~WO 95/02390 ~ PCT/US94/06943
13
Optimum aluminosilicates for builder purposes exhibit a calcium ion
exchange rate of at least 260 mg equivalent of CaC03/litre/ minnte/
(gram/litre) [4 grains/gallon/minnte/(gram/gallQn)].
Aluminosilicate ion exchange materials useful in the~practice of this
invention are commercially available and can be naturally occurring
materials, but are preferably synthetically derived. A method for
producing aluminosilicate ion exchange materials is ~iiec~esed in US
Pate~t No. 3,985,669. Preferred synthetic cryst~llin~ aluminosilicate ion
exchange materials useful herein are available under the designations
Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mixtures thereof. In an
especially preferred embodiment, the cryst~lline aluminosilicate ion
exchange material is Zeolite A and has the formula
Na 12 [(A102 ) 12 (SiO2)12 ]- xH2 0
wherein x is from 20 to 30, especially 27. Zeolite X of formula Na86
t(A102)86(SiO2)106]. 276 H20 is also suitable, as well as Zeolite HS of
forrnula Na6 [(Alo2)6(sio2)6~ 7-5 H2 )-
Suitalble water-soluble monomeric or oligomeric carboxylate builders can
be selected from a wide range of compounds but such compounds
pleferably have a first carboxyl loga,i~ ic acidity/constant (pKl) of less
than 9, I)refe,~bly of between 2 and 8.5, more preferably of between 4
and 7.5.
The l~garithmic acidity constant is defined by ,efere"ce to the equilibrium
H+ + A- ~ 'H A
where A- is the fully ionized carboxylate anion of the builder salt.
The equilibrium constant is therefore
K1 = (H A)
(H+) (A-)
and pK1 = lglOK-
For the purposes of this specification, acidity conet~nt.e are defined at25C and at zero ionic strength. Literature values are taken where
WO 95/02390 ~ 8 ~ 1 PCT/US94/06943
14
possible (see Stability Constants of Metal-Ion Complexes, Special
Publication No. 25, The Chemical Society, London): where doubt arises
they are determined by potentiometric titration using a glass electrode.
Preferred carboxylates can also be defined in terms of their calcium ion
stability constant (pKCa+ +) defined, analogously to pKl, by the
equations
PKCa+ + = loglOKCa+ +
where KCa+ + = (Ca+ + A)
(Ca+ +) (A)
Preferably, the polycarboxylate has a pK Ca+ + in the range from about
2 to about 7 especially from about 3 to about 6. Once again literature
values of stability constant are taken where possible. The stability
constant is defined at 25C and at zero ionic strength using a glass
electrode method of measurement as described in Complexation in
Analytical Chemistry by Anders Ringbom (1963).
The carboxylate or polycarboxylate builder can be momomeric or
oligomeric in type although monomeric polycarboxylates are generally
preferred for reasons of cost and pelrollnance.
~ wo 9~,02390 ~ 8 ~ 1 PCT/US94/06943
Monomeric and oligomeric builders can be selected from acyclic,
alicyclic, heterocyclic and aromatic carboxylates having the general
formulae
y
(a)
R1 X C R2
Z m
(b)
X C
z
(C) yp - O--~- Zq
\/
wherein Rl lc~resents H,Cl 30 alkyl or alkenyl optionally substitllte~l by
hydroxy, carboxy, sulfo or phosphono groups or ~tt~che~l to a
polyethylenoxy moiety cont~ining up to 20 ethyleneoxy groups; R2
represents H,Cl~ alkyl, alkenyl or hydroxy alkyl, or alkaryl, sulfo, or
phosphono groups;
X represents a single bond; O; S; SO; SO2; or NR1;
Y represents H; carboxy;hydroxy; carboxymethyloxy; or
Cl 30 alkyl or alkenyl optionally substit~lte~ by hydroxy or carboxy
groups;
Z represents H; or carboxy;
m is an integer from 1 to 10;
n is an integer from 3 to 6;
8 ~ 1
WO 9~/02390 PCT/US94/06943
16
p, q are integers from 0 to 6, p + q being from 1 to 6; and wherein, X,
Y, and Z each have the same or dirre~ representations when repeated
in a given molecular formula, and wherein at least one Y or Z in a
molecule contain a carboxyl group.
Suitable carboxylates cont~inin~: one carboxy group include lactic acid,
glycolic acid and ether derivatives tnereof as disclosed in Belgian Patent
Nos. 831 368, 821 369 and 821 370.
Polycarboxylates cont~inin~ two carboxy groups include the water-soluble
salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic
acid, diglycolic acid, tartaric acid, ~llrol~ic acid and fumaric acid, as well
as the ether carboxylates described in German Offenlegenschrift 2 446
686, and 2 446 687 and US Patent No.
3 935 257 and the sulfinyl carboxylates described in Belgian Patent No.
840 623. Polycarboxylates cont~inin~ three carboxy groups include, in
particular, water-soluble citrates, acGnillates and citraconates as well as
succinate derivatives such as the carboxymethyloxysuccinates described in
British Patent No. 1 379 241, lactoxysuccinates described in British Patent
No. 1 389 732, and arninosuccinates described in Netherlands Application
7 205 873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-
propane tricarboxylates described in British Patent No. 1 387 447.
Polycarboxylates cont~ininp four carboxy groups include oxydisuccinates
disclosed in British 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 cont~inin~ sulfo substituents include
the sulfosuccinate derivatives disclosed in British Patent Nos. 1 398 421
and 1 398 422 and in US Patent No.
3 936 448, and the sulfonated pyrolysed citrates described in British
Patent No. 1 439 000.
Alicyclic and heterocyclic polycarboxylates include cyclopentane-
cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates,
2,3,4,5-tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2,5-
tetrahydrofuran - cis - dicarboxylates, 2,2,5,5-tetrahydrofuran -
tetracarboxylates, 1,2,3,4,5,6-hexane - hexacarboxylates and
WO 95/02390 2 ~ I PCT/US94/06943
17
carboxymethyl derivatives of polyhydric alcohols such as sorbitol,
ma~nitol and xylitol. ~romatic polycarboxylates include mellitic acid,
pyromellitic acid and the phthalic acid derivatives disclosed in British
Patent No. 1 425 343.
Of the above, the preferred polycarboxylates are hydroxycarboxylates
cont~inin~ up to three carboxy groups per molecule, more particularly
citrates.
The parent acids of the monomeric or oligomeric polycarboxylate
chelating agents or mixtures thereof with their salts, e.g. citric acid or
citrate/citric acid mixtures are also con~ lated as components of builder
systems of dete.gent compositions in accordance with the present
inve~ntion.
Other suitable water soluble organic salts are the homo- or co-polymeric
polycarboxylic acids or their salts in which the polycarboxylic acid
comprises at least two carboxyl r~iic~l~ separated from each other by not
more than two carbon atoms. Polymers of the latter type are disclosed in
GB-A-l 596 756. Examples of such salts are polyacrylates of MWt 2000-
500~ and their copolymers with maleic anhydride, such copolymers
having a molecular weight of from 20 000 to 100 000, especially from 70
000 to 90 000. These materials are normally used at levels of from 0.5%
to lG % by weight more preferably from 0.75 % to 8 %, most preferably
from 1 % to 6 % by weight of the composition.
Organic phosphonates and amino alkylene poly (alkylene phosphonates)
inclu,de alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene
phosphonates, ethylene ~ mine tetra methylene phosphonates and
diethylene tri~minç penta methylene phosphonates, although these
materials are less preferred where the minimi.c~tion of phosphorus
compounds in the compositions is desired.
These phosphonate materials are normally present at levels less than 5 %
by weight, more preferably less than 3 % by weight and most preferably
less than 1% by weight of the compositions.
WO 95/02390 2 1 6 6 ~ 6 1 PCT/US94/06943
18
The detergent compositions can also include miscellaneous ingredients
preferably in a total amount of from 0% to 45 % by weight, examples of
such ingredients being optical brighteners, anti-redeposition agents,
photoactivated bleaches (such as tetrasulfonated zinc phthalocyanine) and
heavy metal sequestering agents. -
When form~ te~l as a granular compostion the particle size of theparticulate components of any dete~ or cleaning composition
cont~inin~ the surf~rt~nt system of the invention is conventional and
preferably not more than 5 % by weight should be above 1 .4mm, while
not more than 10% by weight should be less than 0.15 mm in maximum
dimension. Preferably at least 60%, and most plefelably at least 80%, by
weight of the powder lies between 0.7 mm and 0.25 mm in size.
Preferred granular delergell~ compositions in accordance with the
invention comprise at least one spray dried granular
surfactant-cont~inin~: partic~ te component and at least one surf~-t~nt-
cont~ining particulate agglomerate component.
For spray dried powders, the bulk density of the particles from the spray
drying tower is conventionally in the range from 400 to 450 g/litre and
this is then enh~nce~l by further processin~ steps such as size reduction in
a high speed cutter/mixer followed by compaction preferably to achieve a
final density of greater than 550 g/litre. Alternatively, processes other
than spray drying may be used to form a high density particulate directly.
Where the partic~ te components are particulate agglomerates the bulk
density of these components will be a function of their mode of
preparation. However, the preferred form of such components is a
mechanically rnixed agglomerate which may be made by adding the
ingredients dry or with an agglomerating agent to a pan agglomerator, Z
blade mixer or more preferably an in-line mixer such as ~ose
m~mlf~tured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS,
Lelystad, Netherlands and Gebruder Lodige MaschinenbanGmbH, D-
4790 Paderborn 1, Elsenerstrasse 7-9, Postfach 2050 F.R.G. By this
means the second component can be given a bulk density in the range
from 650 g/litre to 1190 g/litre more preferably from 700 g/litre to 850
g/litre.
~WO 95/0239C~ t PCT/US94/06943
19
Preferably any particulate agglomerate components include sodium
carbonate at a level of from 20 % to 40 % by weight of the component.
PreiFerably, the composition includes from 3% to 18% sodium carbonate
by weight of the composition, more preferably from S~ to 15% by
weight.
A highly ~refelred ingredient of any particulate agglomerate components
is also a hydrated water insoluble aluminosilicate ion exchange material of
the synthPti~ zeolite type, described hereinbefore, present at from 10% to
SS % by weight of the second component. The amount of water insoluble
aluminosilicate material incorporated in this way is from 1% to 15% by
weight of the composition, more prefel~bly from 2% to 10% by weight.
In one process for prepa,illg the particulate agglomerate col,~ollent, the
surf~ct~nt salt is formed in situ in an inline mixer. The li~uid acid form
of the surf~r-t~nt is added to a mixture of particulate anhydrous sodium
carbonate and hydrated sodium aluminosilicate in a continuous high speed
blender, such as a Lodige KM mixer, and neutralised to form the
surfactant salt whilst m~int~ining the particulate nature of the mixture.
The resl~lt~nt agglomerated mixture forms the second component which is
then added to other components of the product. In a variant of this
process, the surfactant salt is pre-neutralised and added as a viscous paste
to the mixture of the other ingredients. In the variant, the mixer serves
merely to agglomerate the ingredients to form the second component.
Where there is only one surf~ct~nt-cont~inin~ co",ponent in the
composition one or more other ingredients will be added as particulate
components and will preferably also be present where more than one
surfactant-cont~ininp: particulate components forms part of the
composition. Thus one or more of oxygen bleaches, photoactivated
bleaches, bleach activators, builder salts, de~ergell~ enzymes, suds
suppressors, fabric softening agents, soil suspension and anti-redeposition
agents, soil release polymers, and optical brighteners can be added as
solids.
WO 95/02390 PCT/US94/06943
Suitable oxygen bleaches include the inorganic perhydrates such as
sodium perborate monohydrate and tetrahydrate, sodium percarbonate,
sodium perphosphate and sodium persilicate. Sodium percarbonate and
the sodium perborate salts are most preferred. These materials are
normally added as cryst~llin~o solids and, in the case of sodium
percarbonate, may be coated with e.g. silic~te in order to aid stability.
Usage levels range from 3 % to 22 % by weight, more preferably from 8 %
to 18% by weight.
Photoactivated bleaches include the zinc and aluminium salts of tri and
tetra sulfonated phthalocyanine which are normally added as dispersions
in other materials bec~l)se of their low levels of usage, typically from
0.0005 to 0.01 % by weight of the composition.
Bleach activators or peroxy acid bleach precursors can be selected from a
wide range of classes and are preferably those cont~inin~ one or more N-
or O- acyl groups.
Suitable classes include anhydrides, esters, imides and acylated
derivatives of imi~ oles and oximes, and examples of useful materials
within these classes are disclosed in GB-A-1586789. The most preferred
classes are esters such as are disclosed in
GB-A-836 988, 864 798, 1 147 871 and 2 143 231 and imides such as are
disclosed in GB-A-855 735 & 1 246 338. Levels of incol~o,~lion range
from 1% to 10% more generally from 2% to 6% by weight of the
composition.
Particularly preferred precursor compounds are the N-,N,N1Nl tetra
acetylated compounds of formula
O O
Il ll
CH3 - C . ~ C - CH3
N - (CH2)x - N ~
CH3 C ~ C - CH3
O O
~ WO 95102390 ~ 8 ~ ~ PCT/US94/06943
wherein x can be O or an integer between 1 & 6.
Examples include tetra ace~l methylene ~i~min~ (TAMD) in which x= 1,
tetra acetyl ethylene ~ min~ (TAED) in which x=2 and tetraacetyl
he~;ylene ~ mine (TAHD) in which x=6. These and analogous
compounds are described in GB-A-907 356. The most prefel,ed
peroxyacid bleach precursor is TAED.
Solid peroxyacid bleach precursors useful in compositions of the present
invention have a Mpt~30C and preferably >40C. Such precursors
wil:l normally be in fine powder or cryst~llin~ form in which at least 90%
by weight of the powder has a particle size > 150 micrometers.
This powder is usually agglomerated to form particulate material, at least
85 % of which has a particle size between 400 and 1700 micrometers.
Suilable agglomerating agents include aliphatic mono and polycarboxylic
acids,C12-Clg aliphatic alcohols condensed with from 10 to 80 moles of
ethylene oxide per mole of alcohol, cellulose derivatives such as methyl,
carboxymethyl and hydroxyethyl cellulose, polyethylene glycols of MWt
4,000 - 10,000 and polymeric materials such as polyvinyl pyrrolidone.
The precursors are preferably coated with an organic acid compound such
as citric or glycolic acid, as disclosed in the commonly assigned
copending British Patent Application No. 9102507.2 filed February 6
1991.
Builder salts that can ~ vantageously be added as solid particulates
include silic~t~s and certain polycarboxylate builders such as citrates.
Dry mix addition of amorphous sodium silir~tes, particularly those of
SiO2:Na2O ratio of from 2.0: 1 to 3.2: 1 is employed where
aluminosilicates form part of a spray dried component, in order to avoid
the ~ormation of insoluble reaction products. Furthermore the
incorporation of cryst~llin~, so called 'layered' silic~tes into detergenl
compositions necessitates their addition as solids.
g 6 1
WO 95/02390 PCT/US94/06943
22
These crystalline layered sodium silicates have the general formula
NaMSix02x+ 1.YH20
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a
number from 0 to 20. Crystalline layered sodium silicates of this type are
disclosed in EP-A-0 164 514 and methods for their preparation are
disclosed in DE-A-3 417 649 and DE-A-3 742 043. For the purposes of
the present invention, x in the general formula above has a value of 2, 3
or 4 and is prefefably 2. More pleferably M is sodium and y is 0 and
preferred examples of this formula comprise the ~ and ~ forms of
Na2Si2Os. These materials are available from Hoechst AG FRG as
respectively NaSKS-11 and NaSKS-6. The most ple~erled material is
~-Na2Si2Os, (NaSKS-6). Crystalline layered silicates are incorporated
either as dry mixed solids, or as solid components of agglomerates with
other components.
Anti-redeposition and soil-suspension agents suitable herein include
cellulose derivatives such as methylcellulose, carboxymethylcellulose and
hydroxyethycellulose, and homo-or co-polymeric polycarboxylic acids or
their salts. Polymers of this type include copolymers of maleic anhydride
with ethylene, methylvinyl ether or meth~rrylic acid, the maleic
anhydride concti1~ltin~ at least 20 mole percent of the copolymer. These
materials are normally used at levels of from 0.5% to 10% by weight,
more p~efelably from 0.75% to 8%, most ~leferably from 1% to 6% by
weight of the composition.
Other useful polymeric materials are the polyethylene glycols, particularly
those of molecular weight 1000-10000, more particularly 2000 to 8000
and most preferably about 4000. These are used at levels of from 0.20%
to 5 % more preferably from 0.25 % to 2.5 % by weight. These polymers
and the previously mentioned homo- or co-polymeric polycarboxylate
salts are valuable for improving whiteness m~intenance, fabric ash
deposition, and cleaning performance on clay, proteinaceous and
oxidizable soils in the presence of transition metal impurities.
~WO 95/02390 2 1 6 6 8 6 1 PCT/US94/06943
23
Preferred optical brighteners are anionic in character, examples of which
are disodium 4,41-bis-(2-diethanolamino-4-~nilino -s- triazin-6-
yl~rnino)stilbene-2:2 1 disulphonate, disodium 4,4 1-bis-(2-morpholino -4-
~nilino-2-triazin-6-ylaminostilbene-2:21-disulphonate,disodium 4, 41-bis-
(2,4-~ nilino-s-triazin-6-ylamino)stilbene-2:21 - dislllphonate,
monosodium 41,41 1-bis-(2,4-~ nilino-s-triazin-6 yl~mino)stilbene-2-
sulphonate, disodium 4,4 1-bis-(2-~nilint -4-(N-methyl-N-2-
hydroxyethyl~mino)-2-triazin-6-yl~minQ)stilbene-2,2 1 - disulphonate,
disodium 4,41-bis-(4-phenyl-2, 1 ,3-triazol-2-yl)stilbene-2,2 1 disulphonate,
disodium 4,41bis(2-anilino~-(1-methyl-2-hydroxyethylamino)-s-triazin-6-
yl~mino)stilbene-2,21disulphonate and sodium 2(stilbyl-411-(naphtho-
l1,Z.1:4,5)-1,2,3 - triazole-211- sulphonate.
Soil-release agents useful in detergent or cleaning compositions in accord
with the present invention are conventionally copolymers or terpolymers
of terephthalic acid with ethylene glycol and/or propylene glycol units in
various arrangements. Examples of such polymers are disclosed in the
commonly assigned US Patent Nos. 4 116 885 and 4 711 730 and
European Published Patent Application No. 0 272 033. A particular
preferred polymer in accordance with EP-A-O 272 033 has the formula
(cH3(pEG)43)o.7s(poH)o.2s(T-po)2.8(T-pEG)o.4)T(po-H)o 2s((PEG)43cH3)o 75
where PEG is -(OC2H4)0-,PO is (OC3H60) and T is (pCOC6H4CO).
Certain polymeric materials such as polyvinyl pyrrolidones typically of
MWt 5000-20000, preferably 10000-15000, also form useful agents in
preventing the transfer of labile dyestuffs between fabrics during the
washing process.
Another optional detelgent composition ingredient is a suds suppressor,
exemplified by silicones, and silica-silicone mixtures. Silicones can be
generally represented by alkylated polysiloxane materiats while silica is
normally used in finely divided forms, typified by silica aerogels and
xerogels and hydrophobic silicas of various types. These materials can be
inco1porated as partic~ tes in which the suds suppressor is
advantageously releasably incorporated in a water-soluble or water-
dispersible, subst~nti~lly non-surface-active deLeLgellt-imperrneable
,
21 ~8~ 1
WO 95/02390 PCT/US94/06943
24
carrier. Alternatively the suds suppressor can be dissolved or dispersed
in a liquid carrier and applied by spraying on to one or more of the other
components.
As mentioned above, useful silicone suds controlling agents can comprise
a mixture of an allylated siloxane, of the type referred to hereinbefore,
and solid silica. Such mixtures are plepaled by ~ffixing the silicone to the
surface of the solid silica. A preferred silicone suds controlling agent is
represented by a hydrophobic ~ n~t~-l (most preferably trimethyl-
sil~n~te~l) silica having a particle size in the range from 10 nanometers to
20 nanometers and a specific surface area above 50 m2/g, intim~tely
admixed with dimethyl silicone fluid having a molecular weight in the
range from about 500 to about 200,000 at a weight ratio of silicone to
n~tt?~l silica of from about 1: 1 to about 1 :2.
Suitable silicone suds controlling agents are disclosed in US Patent
3 933 672 and DTOS 2 646 126, an example of the latter being DC0544,
a self emulsifying siloxane/glycol copolymer commercially available from
Dow Corning. A particularly preferred suds suppressor system based on
a silica silicone mixture comprises 78% starch, 12% stearyl alcohol
binder and 10% of a silica/silicone blend available from Dow Corning
under the reference X2/3419. This system is the subject of European
Patent No. 0 210 721.
The p~efe,led metho~l.s of incorporation comprise either application of the
suds ~uy~lessors in liquid form by spray-on to one or more of the major
CO~ lltS of the composition or al~ ati-~ely the formation of the suds
~u~lessors into separate particulates that can then be mixed with the
other solid components of the composition. A preferred example of such
a particulate is a cryst~llin~ or amorphous alumino~ilic~te zeolite on to
which the suds suppressor is absorbed. Suds suppressor particulates of
this type are the subject of the commonly assigned copending European
Application No. 91201343Ø The incorporation of the suds modifiers as
separate particulates also permits the inclusion therein of other suds
controlling materials such as C20-C24 fatty acids, microcrystalline waxes
and high MWt copolymers of ethylene oxide and propylene oxide which
would otherwise adversely affect the dispersibility of the matrix.
~WO 95/0239C1 ~ 8 ~ ~ PCT/US94/06943
Techniques for forming such suds modifying particulates are disclosed in
the previously mentioned US Patent No. 3 933 672.
An especially preferred suds suppressor system comprises in combination
a paLrticulate suds suppressing component and a spray-on suds-suppressing
component.
The suds suppressors described above are normally employed at levels of
fronn 0.01 % to 5.0% by weight of the composition, preferably from
0.01 % to 1.5% by we~ght, and most ~1efeldbly from 0.1 % to 1.2% by
weight.
Another optional ingredient useful in the present invention is one or more
enzymes.
Preferred enzymatic materials include ~e commercially available
amylases, neutral and ~ lin~ proteases, lipases, esterases and cellulases
conventionally incorporated into deLer~elll compositions. Suitable
enzymes are discll~se~l in US Palell~ 3 519 570 and
3 533 139.
~ablic softening agents can also be inc~l~ol~Led into del~rg~llt
compositions in accordance with the present invention. These agents may
be inorganic or organic in type. Inorganic softening agents are
exeI:nplified by the smectite clays disclosed in GB-A-1 400 898. Organic
fabric softening agents include the water insoluble tertiary amines as
discLosed in GB-A-1 514 276 and EP-B-0 011 340.
Their combination with mono C12-C14 quatell~y ammonium salts is
discLosed in EP-B-0 026 527 & 0 026 528. Other useful organic &bric
softening agents are the dilong chain ~mil1es as disclosed in EP-B-0 242
919. Additional organic ingredients of fabric softening systems include
high molecular weight polyethylene oxide materials as disclosed in EP-A-
0 299 575 and 0 313 146.
Levels of sm~ctit~ clay are normally in the range from 5% to 15%, more
preferably from 8 % to 12 % by weight, with the material being added as a
-
WO 95/02390 2 t ~ 6 8 ~ ~ PCT/US94/06943 ~
26
dry mixed component to the rem~in-ler of the formulation. Organic fabric
softening agents such as the water-insoluble tertiary amines or dilong
chain amide materials are incorporated at levels of from 0.5% to 5% by
weight, normally from 1% to 3 % by weight, whilst the high molecular
weight polyethylene oxide materials and the water soluble cationic
materials are added at levels of from 0.1 % to 2 %, normally from 0.15 %
to 1.5 % by weight. Where a portion of the composition is spray dried,
these materials can be added to the aqueous slurry fed to the spray drying
tower, although in some in~nces it may be more convenient to add them
as a dry mixed particulate, or spray them as a molten liquid on to other
solid components of the composition.
In a particularly ~lefellcd process for m~kin~ deLergellt compositions in
accordance with the invention, part of the spray dried product comprising
one of the granular components is diverted and subjected to a low level of
nonionic surf~rt~nt spray on before being reblended with the rem~in~er.
A second granular compollent is made using the picfel~ed process
described above. The first and second components together with
perhydrate bleach, bleach precursor partic~ te, other dry mix ingredients
such as any carboxylate chelating agent, soil-release polymer, silicate of
conventional or cryst~ np layered type, and enzyme are then fed to a
conveyor belt, from which they are tral~r~llcd to a horizontally rotating
drum in which pelrull'e and silicone suds ~u~lessor are sprayed on tO the
product. In highly ~Ic~llcd compositions, a further drum mixing step is
employed in which a low (approx. 2 % by weight) level of finely divided
cryst~llin~ material is introduced to increase density and improve granular
flow characteristics.
The conce~lllated granular compositions of the present invention have abulk density of at least 550g/litre, prefelably at least 650g/litre more
usually about 700 g/litre.
Bulk density is measured by means of a simple funnel and cup device
consisting of a conical funnel moulded rigidly on a base and provided
with a flap valve at its lower extremity to allow the contellt~ of the funnel
to be emptied into an axially ~lign~-l cylindrical cup disposed below the
funnel. The funnel is 130 mm and 40 rnrn at its respective upper and
WO 95/0239C~ a ~ PCT/US94/06943
27
lower extremities. It is mounted so that the lower extremity is 140 mm
above the upper surface of the base. The cup has an overall height of 90
mnn, an internal height of 87 mm and an internal diameter of 84 mm. Its
nominal volume is 500 ml.
To carry out a measurement, 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 p~esin~ a straight edged implement e.g. a knife, across
its upper edge. The filled cup is then weighed and the value obtained for
the weight of powder doubled to provide the bulk density in g/litre.
Replicate measurements are made as required.
Subject to the above bulk density limit~tions, the compositions of the
invention can be made via a variety of methods including dry mixing,
spray drying, agglomeration and gr~n~ tion. A plefel.ed method of
m~kin~ the compositions involves a combination of spray drying,
agglomeration in a high speed mixer and dry mixing.
Co]npositions in accordance with the present invention comprise a
plurality of separate particulate components. The particulates can have
any suitable form such as granules, flakes, prills, marumes or noodles but
are preferably granular. The granules themselves may be agglomerates
formed by pan or drum agglomeration or by an in-line mixer and also
may be spray dried particles pro~ re~ by atomi~in~ an aqueous slurry of
the ingredients in a hot air stream which removes most of the water. The
spray dried granules are then subjected to densification steps, e.g. by high
speed cutter mixers and/or compacting mills, to increase density before
being reagglomerated.
Preferred compositions in accordance with the invention comprise at least
one spray dried granular surfactant-cont~ining component and at ~Past one
suri~actant-cont~ining particulate agglomerate coll~ollent.
Where one or more surfactant-cont~ining particulate components are
spray dried granules these will preferably comprise in total at least 15 %,
more preferably from 25 % to 45 %, by weight of the composition. Where
WO 95/02390 ~ PCT/US94/06943--
28
one or more surfactant-cont~inin~ particulate components are particulate
agglomerates these will preferably comprise in total from 1% to 50%,
more preferably from 10% to 40% by weight of the composition.
Where the surf~ct~nt-cont~inin~ partic~ tes are the only multi ingredient
components, the rern~in~ier of the ingredients can be added individually as
dry solids, or can be sprayed on to either the particulate components or on
to any or all of the solid ingredients.
In preferred concentrated detergent products incorporating an alkali metal
percarbonate as the perhydrate salt it has been found n~cess~ry to control
several aspects of the product such as its heavy metal ion content and its
equilibrium relative hllmi-lity. Sodium percarbonate-cont~inin~
col,lposiLions of this type having enh~nre~l stability are disclosed in the
commonly assigned British Application No. 9021761.3 filed October 6
1990 Attorney's Docket No. CM343.
Preferred laundry detelgellt compositions of the invention are form~
to be used with delivery systems that provide transient loc~ e~l high
concentrations of product in the drum of an automatic washing machine at
the start of the wash cycle. These delivery systems avoid problems
associated with loss of product in the pipework or sump of the machine
and the high transient concentrations provide fabric cleaning benefits.
High transient concentrations require rapid dissolution/dispersion of the
composition but ~is is difficult with surf~ct~nt cont~ining particulate
colll~onents in which the alkyl sulfate surf~ct~nt is relatively insoluble and
hence make the component hydrophobic in nature. The incorporation of a
low level of a water soluble ethoxysulfate surf~ t~nt into the alkyl sulfate
surfactant cont~ining particulate has however been found to enable
acceptable rate of dissolution characteristics to be achieved whilst
ret~ining the deterge.lcy provided by surf~ct~nt
Delivery systems for introducing laundry detergell~ compositions in
accord with the invention into an automatic washing machine can take a
number of forms. Thus a composition can be incorporated in a bag or
container from which it is rapidly releasable at the start of the wash cycle
~WO 95/0239C1 ~ 1 6 6 8 6 1 PCT/US94/06943
29
in response to agitation, a rise in temperature or immersion in the wash
walter in the drum. Alternatively the washing machine itself may be
adapted to permit direct addition of the composition to the drum e.g. by a
dispensing arrangement in the access door.
Products comprising a laundry deLer~elll composition enclosed in a bag or
container are usually designed in such a way that container integrity is
m~int~inP~l in the dry state to prevent egress of the colllents when dry, but
are adapted for release of the container colllellts on exposure to a washing
environment, normally on immersion in an aqueous solution.
Usually the container will be flexible, such as a bag or pouch. The bag
ma~ be of fibrous construction coated with a water impermeable
pro~ective material so as to retain the co-llellts, such as is disclosed in
European published Patent Application No. 0 018 678. Allelllali~ely it
may be formed of a water-insoluble synthetic polymeric material provided
with an edge seal or cl~sure lesign~A to ru~lure in aqueous media as
disclosed in European published Patent Application Nos.
O 01~ 5~0, 0 011 S01, 0 011 502, and 0 011 968. A convenient form of
water frangible closure colll~lises a water soluble adhesive disposed along
and sealing one edge of a pouch formed of a water hQ~elllleable
polymeric film such as polyethylene or polypropylene.
In a variant of the bag or cont~inçr form, l~min~te(l sheet products can be
employed in which a central flexible layer is impregnated and/or coated
with a composition and then one or more outer layers are applied to
produce a fabric-like ~estlletic effect. The layers may be sealed together
so as to remain attached during use or may se~arate on contact with water
to facilitate the release of the coated or impregnated material.
An altelnalive l~min~te form comprises one layer embossed or deformed
to provide a series of pouch-like containers into each of which the
detergellt components are deposited in me~c~lred amounts, with a second
layer overlying the first layer and sealed thereto in those areas between
the pouch-like containers where the two layers are in contact. The
components may be deposited in particulate, paste or molten form and the
l~min~te layers should prevent egress of the conten~ of the pouch-like
cont~iners prior to their addition to water. The layers may separate or
WO 95/02390 2 1 6 6 8 6 I PCT/US94/06943--
may remain attached together on contact with water, the only requirement
being that the structure should permit rapid release of the contents of the
pouch-like containers into solution. The number of pouch-like containers
per unit area of substrate is a matter of choice but will normally vary
between 500 and 25,000 per square metre.
Suitable materials which can be used for the flexible l~min~te layers in
this aspect of the invention include, among others, sponges, paper and
woven and non-woven fabrics.
However the ~le~.~d means of carl~/in~ out the process of ~e invention
is to introduce the composition into the liquid surrolln~ling the fabrics that
are in the drum via a reusable dispensing device having walls that are
permeable to liquid but impermeable to the solid composition.
Devices of this kind are disclosed in Euro~an Patent Application
Publication Nos. 0 343 069 & 0 343 070. The latter Application discloses
a device comprising a fle~ible sheath in the form of a bag extending from
a support ring defining an orifice, the orifice being adapted to admit to the
bag sufficient product for one washing cycle of an aul~lllatic process. A
portion of the washing me~ m flows through the orifice into the bag,
dissolves the product, and the solution then passes outwardly through the
orifice into the washing me~ m The ~uppoll ring is provided with a
m~ckin~ arrangement to prevent egress of wetted, undissolved, product,
this arrangement typically comprising radially extending walls extending
from a central boss in a spoked wheel configuration, or a similar structure
in which ~e walls have a helical form.
Plefelled dispensing devices are reusable and are designed in such a way
that container integrity is m~int~inPr3 in both the dry state and during the
wash cycle. Especially ~referled disyensillg devices for use in accord
with the invention have been described in the following patents; GB-B-
2,157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345 and EP-
A-0288346. An article by J. Bland published in ~nllf~cturing Chemist,
November 1989, pages 41~6 also describes especially preferred
dispensing devices for use wi~ granular laundry produts which are of a
type commonly known as the "granulette".
WO 95/02390 2 1 6 ~ 8 ~ 1 PCT/US94/06943
31
In ~he detergent compositions, the abbreviated component identifications
have the following me~ning~:
246AS : Sodium alkyl sulfate surfactant cont~ining a
alkyl chain length weight distribution of 15~
C12 alkyl chains, 455~ Cl~ alkyl chains, 35%
C16 alkyl chains, 5% C1g alkyl chains
24AE3S : C12-C14 alkyl ethoxysulfate cont~ining an
average of three ethoxy groups per mole
TAEn : Tallow alcohol ethoxylated with n moles of
ethylene oxide per mole of alcohol
35E7 : A C13 15 primary alcohol condensed with an
average of 7 moles of ethylene oxide
25E3 : A C12-C1s primary alcohol condensed with an
average of 3 moles of ethylene oxide
NaSKS-6 : Cryst~llin~ layered silicate of formula
Na2Si2O5 (NaSKS-6)
Perborate : Sodiumperborate monohydrate
TAED : Tetraacetyl ethylene tli~mine
$ilicate : Amorphous Sodium Silicate (SiO2:Na2O ratio
normally follows)
Carbonate : Anhydrous sodium carbo~Le
lBicarbonate : Anhydrous so~ m bicarbonate
Zeolite A : Hydrated Sodium Al~ lo.sili~ ~te of formula
Nal2(Alo2sio2)l2- 27H20
having a pli,llaly particle size in the range from
1 to 10 micrometers
Citrate : Tri-sodium citrate dihydrate
MA/AA : Copolymer of 1:4 maleic/acrylic acid, average
molecular weight about 80,000.
Enzyme : Mixedproteolytic andamylolytic
enzyme sold by Novo Tn~ustries AS.
wo 95l02390 ~ ~ ~ 6 ~ ~ 1 PCT/rJSg4/06943~
Fx~TTple 1
The following low-sudsing granular detergellL composition was prepared
in accordance with the invention (percentage, parts by weight).
246AS 8.8
24AE3S 2.2
35E7 4.5
Zeolite A 24.8
Carbonate 15.5
MA/AA 4.6
Sulphate 5.0
Silicate 2.5
Citrate 11.4
Bicarbonate 7.0
Enzyme 1.6
sly~ressor system
Particulate anLifo~ll component 2.1
Spray-on antifoam component 2.0
Misc, minors, moisture to b~l~n~e
The particlll~te al~lifoalll component was an agglomerate comprising 11%
by weight of the component of polydimethylsiloxane, 14% by weight
TAE80, 5% by weight of a mixture of C12-C22 hydrogenated fatty acids
and 70 % by weight of starch.
The spray-on all~ifoalll component comprised 30% by weight of the
component of silicone/silica antifoam compound comprising 85 % by
weight of the antifoam compound of polydimethylsiloxane and 15 % by
weight of the antifoalll compound of silica, 3 ~ by weight of silicone
glycol rake copolymer (DCO544 from DOW Corning), and 67% by
weight of TAE11 carrier fluid.
~wo 9~,02390 ~ 8 ~ 1 PCT/US94/06943
F.x~ le ~
The following laundry detergelll compositions were prepared (parts by
weight) in accordance with the invention.
A B ' C D
246AS 7.6 6.5 4.8 6.8
24AlE3S 2.4 - 1.2 1.7
TAE11 1.10
TA]E50 - 0.4 0.4 0.4
35E,7 3.26
35E3 - 5.0 5.0 5.0
Zeolite A 19.5 13.0 13.0 13.0
Citrate 6.5
MA./AA 4.25 4.25 4.25 4.25
NaSKS-6* - 10.01 10.01 10.01
Citric Acid* - 2.73 2.73 2.73
TAlES0* - 0.26 0.26 0.26
Call,o~ e 11.14 9.84 9.84 9.84
Perboldte 16.0 16.0 16.0 16.0
TAlED 5.0 5.0 5.0 5.0
Enzyme 1.4 1.4 1.4 1.4
Silicate (2.0 ratio) 4.38
Waler and mi~cell~neous (Including suds ~uLpressor, sodium sulphate,
perfume) to b~l~n~e
* Present as components of crystalline layered silic~te particulates.
