Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 0221~669 1997-09-16
W O96/29281 PCTrUS96/02768
PERFUMED BLEACHING COMPOSITIONS
Field of the invention
The invention relates to perfumed bleaching compositions. More
specifically, it relates to bleaching compositions comprising a
hydrophobic bleach system and a stabilised perfume composition.
Background of the invention
Perfumes are an important and desirable part of detergent
compositions. They are used to cover up the chemical odours of the
cle~ning ingredients and provide an aesthetic benefit to the wash
process and, plefe~ably the cleaned fabrics. EP 430315, which
discloses the use of a laundry detergent composition cont~ining a lipase
and a perfume having specific fragrance materials, e~cemplifies such
use. In said patent, the perfume composition is said to counteract the
problem of the residual malodour of lipase treated laundry.
A problem encountered with perfumes is their volatility and many
perfume ingredients can be destroyed or ~l~m~ged in presence of
cle~ning ingredients, especially alkali and bleaches.
Hydrophobic bleach systems selected from a source of hydrogen
pero~cide combined with a hydrophobic pero~cyacid bleach precursor
and a hydrophobic pero~yacid bleach are known in the art as effective
soil removal agents of dingy stains.
The Applicants have found that the problem of perfume o~idation may
be particularly troublesome with hydrophobic pero~cyacid bleach
precursors which on perhydrolysis produce a pero~yacid which is an
CA 0221~669 1997-09-16
W O96/29281 PCTrUS96/02768
amido substituted pero~cyacid. Precursor compounds as well as
pero~cyacid compounds per se of the amido substituted type, in
particular, have also been found to give rise to the problem.
One solution to this problem is encapsulation of the perfume. This
increases the e~cpense and comple~city of the formulation and does not
always provide sufficient protection. EP 332259 teaches the use of a
liquid detergent composition cont~inins~ pero~yacid bleach and
perfumed silica particles which protect the perfume from o~idation by
the bleach.
Another solution to this problem is the reduction in the level of the
hydrophobic bleach system. Whilst reducing the level of the
hydrophobic bleach system employed in the wash tends to ameliorate
these problems, this is accompanied by a marked negative effect on the
dingy stains/soil removal ability.
The detergent form~ tor thus faces the challenge of forml-l~tin~ a
product which ma~imises soil/stain removal, which avoids degradation
of the detergent components, which covers up the chemical odours of
the cle~ning ingredients, which provides an aesthetic benefit and which
is also ine~cpensive.
The Applicants have now surprisingly found that the provision of a
minimllm amount of specific perfume raw materials allows the use of
stabilised perfumed compositions in presence of a hydrophobic bleach
system.
The Applicants have also suprisingly found, that delivery of the
perfume on the fabric is enhanced with hydrophobic pero~cyacid
precursor. Not to be bound by theory, it is believed that the
hydrophobic pero~cyacid precursor serves as a carrier material for the
perfume composition.
It is therefore an object of the present invention to provide
compositions suitable for use in laundry washing methods which
produces an e~ccellent perfume fragrance on fabrics as well as an
CA 0221~669 1997-09-16
W O96/29281 PCTrUS96/02768
e~cellent perfume stability in presence of the hydrophobic bleaching
system in the wash liquor and in the product during storage.
It is a further object of the invention to provide compositions suitable
~ for use in laundry w~hin~ methods which produce effective dingy soil
removal.
S~-mm~ry of the invention
The present invention relates to a perfumed bleaching composition
cont~inin
a-a hydrophobic bleaching system selected from
i)-a perhydrate in amount of from 0.1 % to 60% by weight and
combined with a hydrophobic pero~yacid bleach precursor in
amount of from 0.1% to 60% by weight,
ii)-a hydrophobic preformed pero~yacid in amount of from 0.1 %
to 60% by weight, and
iii)-mi~tures of i) and ii),
wherein a hydrophobic pero~cyacid bleach precursor is defined as a
compound which produces under perhydrolysis a hydrophobic
pero~yacid whose parent carbo~ylic acid has a critical micelle
concentration less than O.S moles/litre, and wherein a hydrophobic
efo,llled pero~cyacid is defined as a compound whose parent
carbo~ylic acid has a critical micelle concentration less than 0.5
moles/litre, and
b- a perfume composition in amount from 0.05% to 2% by weight
which comprises one or more aroma chemicals selected from: tertiary
alcohols, nitriles, lactones, ketones, ~-et~l~, ethers, schiff bases, esters
and mi~ctures thereof, wherein the total sum of the weight of said
aroma chemicals in the perfume is at least 40% by weight of the
perfume.
Detailed description of the invention
An essential component of the invention is a hydrophobic bleach
system selected from a perhydrate combined with a hydrophobic
CA 0221~669 1997-09-16
W O96/29281 PCTÇUS96/02768
pero~cyacid bleach precursor, a preformed hydrophobic pero~cyacid and
any mi~ctures thereof.
Perhydrate bleach
The perhydrate is typically an inorganic perhydrate bleach, normally in
the form of the sodium salt, as the source of ~lk~line hydrogen
pero~ide in the wash liquor. This perhydrate is normally incorporated
at a level of from 0.1% to 60%, preferably from 3 % to 40% by
weight, more preferably from 5% to 35% by weight and most
preferably from 8% to 30% by weight of the composition.
The perhydrate may be any of the ~lk~limetal inorganic salts such as
perborate monohydrate or tetrahydrate, percarbonate, perphosphate
and persilicate salts but is conventionally an alkali metal perborate or
percarbonate.
Sodium percarbonate, which is the prefelled perhydrate, is an addition
compound having a formula corresponding to 2Na2CO3.3H2O2, and
is available commercially as a crystalline solid. Most commercially
available material includes a low level of a heavy metal sequestrant
such as EDTA, l-hydro~cyethylidene 1, l-diphosphonic acid (HEDP)
or an amino-phosphonate, that is incorporated during the
m~nllf~cturing process. For the purposes of the detergent composition
aspect of the present invention, the percarbonate can be incorporated
into deter~;ent compositions without additional protection, but ~refelled
e~cecutions of such compositions utilise a coated form of the material.
A variety of co~tin~ can be used including borate, boric acid and
citrate or sodium silicate of SiO2:Na2O ratio from 1.6:1 to 3.4:1,
,refelably 2.8:1, applied as an aqueous solution to give a level of from
2% to 10%, (normally from 3% to 5%) of silicate solids by weight of
the percarbonate. However the most preferled coating is a mi~cture of
sodium carbonate and sulphate or sodium chloride.
The particle size range of the crystalline percarbonate is from 350
micrometers to 1500 micrometers with a mean of appro~imately 500-
1000 micrometers.
CA 0221~669 1997-09-16
PCTrUS96/02768
W O 96/292~1
Hydrophobic pero~cyacid bleach precursor
One form of the essential hydrophobic bleach system component of the
invention is a hydrophobic pero~cyacid bleach precursor which
produces upon perhydrolysis hydrophobic peroxyacid whose parent
carbo~ylic acid has a critical micelle concentration less than 0.5
moles/litre and wherein said critical micelle concentration is measured
in aqueous solution at 25~C.
Preferably, the pero~yacid backbone chain contains at least 7 carbons
which may be linear or partly or totally branched or cyclic and any
mi~ctures thereof.
The pero~yacid bleach precursors are normally incorporated at a level
of from 0.1 % to 60%, preferably from 3 % to 40% and most
preferably 3 to 25 % by weight of the perfumed bleaching composition.
Preferably, hydrophobic pero~yacid bleach precursor compounds are
selected from bleach precursor compounds which comprise at least one
acyl group forming the pero~yacid moiety bonded to a leaving group
through an
-O- or-N- linkage.
Suitable pero~yacid bleach precursors for the purpose of the invention
are the amide subst~ te~l compounds of the following general
formulae:
R1N(R5)C(o)R2C(o)L or RlC(o)N(R5)R2C(o)L
wherein Rl is an aryl or alkaryl group with from about 1 to about 14
carbon atoms, R2 is an alkylene, arylene, and alkarylene group
cont~inin~ from about 1 to 14 carbon atoms, and R5 is H or an alkyl,
aryl, or alkaryl group cont~inin 1 to 10 carbon atoms and L can be
essentially any leaving group. R1 preferably contains from about 6 to
12 carbon atoms. R2 ~ef~rably contains from about 4 to 8 carbon
atoms. Rl may be straight chain or branched alkyl, subs~ J~ aryl or
alkylaryl cont~inin~ branching, substitution, or both and may be
,
CA 0221~669 1997-09-16
W O96/29281 PCTrUS96102768
sourced from either synthetic sources or natural sources including for
e~ample, tallow fat. Analogous structural variations are permissible
for R2. R2 can include alkyl, aryl, wherein said R2 may also contain
halogen, nitrogen, sulphur and other typical substituent groups or
organic compounds. R5 is preferably H or methyl. R1 and R5 should
not contain more than 18 carbon atoms total. Amide substituted bleach
activator compounds of this type are described in EP-A-0170386.
The leaving group, hereinafter L group, must be sufficiently reactive
for the perhydrolysis reaction to occur within the optimum time frame
(e.g., a wash cycle). However, if L is too reactive, this activator will
be dif~lcult to stabilize for use in a bleaching composition.
Preferred L groups are selected from:
--O~, O~Y, and --O~
--N--C--R1 --N N --N--C--CH--R4
R3 L=l ' R3 Y
R3 Y
--O--CH--C--CH=CH2 --O--CH=C--CH=CH2
-O C--R1 --N~ NR4 Y ~
O O
R3 0 Y
--O--C=CHR4 , and I ;--CH--R4
R3 o
CA 0221~669 1997-09-16
W O96/29281 PCTrUS96102768
and mi~tures thereof, wherein R1 is an alkyl, aryl, or aL~aryl group
cont~inin~ from 1 to 14 carbon atoms, R3 is an alkyl chain con~inin~
from 1 to 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing
group. Any of Rl, R3 and R4 may be substituted by essentially any
filnctional group including, for e~ample alkyl, hydro~y, alko~y,
halogen, amine, nitrosyl, amide and ammonium or alkyl ~mmmonium
groups
The preferred solubilizing groups are -SO3-M+, -CO2-M+,
-SO4-M +, -N+(R3)4X- and O < --N(R3)3 and most preferably
-SO3-M+ and -CO2-M+ wherein R3 is an alkyl chain cont~ininE
from 1 to 4 carbon atoms, M is a cation which provides solubility to
the bleach activator and X is an anion which provides solubility to the
bleach activator. Preferably, M is an alkali rnetal, ammonium or
substituted ammonium cation, with sodium and potassium being most
preferred, and X is a halide, hydro~ide, methylsulfate or acetate anion.
Other suitable L group for use herein, include a leaving group selected
from a caprolactam leaving group, a valerolactam leaving group and
mi~cture thereof.
Preferred e~camples of bleach precursors of the above formulae include
amide substit~lte~l pero~cyacid precursor compounds selected from (6-
oct~n~mirlo-caproyl)o~cybenzenesulfonate, (6-non~n~mitlocaproyl)o~y
benzene sulfonate, (6--lec~n~mi~lo-caproyl)o~cybenzenesulfonate, and
mi~ctures thereof as described in EP-A-0170386.
Still another class of bleach precursor is the class of alkyl
percarbo~cylic acid bleach precursors. Preferred aL~yl percarbo~cylic
acid precursors include nonanoyl o~cy benzene sulphonate (NOBS
described in US 4,412,934) and 3,5,5-tri-methyl he~canoyl o~ybenzene
sulfonate (ISONOBS described in EP120,591) and salts thereof.
Mi~ctures of any of the pero~cyacid bleach precursor, herein before
described, may also be used.
CA 0221~669 1997-09-16
W O96/29281 PCTrUS96/02768
In addition, conventional pero~yacid bleach precursors such as the
tetraacetyl ethylene ~ mine (TAED) bleach precursor may be added to
the bleaching composition of the invention so as to produce an
enhanced soil removal performance.
Preformed hydrophobic pero~cyacid compound
Another form of the essential hydrophobic bleach system component of
the invention is a preformed hydrophobic pero~cyacid bleaching agent
and salt thereof whose parent carboxylic acid has a critical micelle
concentration less than 0.5 moles/litre and wherein said critical micelle
concentration is measured in aqueous solution at 25~C.
Preferably, the pero~yacid backbone chain contains at least 7 carbons
which may be linear, partly or totally branched, or cyclic and any
mi~ctures thereof.
Preferably, hydrophobic pero~yacid bleach compounds are selected
from pero~yacid bleach compounds which comprise at least one acyl
group forming the pero~yacid moiety bonded to a leaving group
through an -O- or-N- linkage.
Preformed hydrophobic pero~cyacid compounds will typically be in
amount of from 0.1 % to 60%, preferably from 3 % to 20% by weight.
Suitable e~amples of this class of agents include (6-octylamino)-6-o~co-
caproic acid, (6-nonylamino)-6-o~o-caproic acid, (6-decylamino)-6-
o~o-caproic acid, m~ne~ium monopero~cyphtl~ te he~cahydrate, the
m~nesium salt of metachloro perbenzoic acid, 4-nonylamino~
o~copero~cybutyric acid and dipero~ydo~lec~n~lioic acid. Such
bleaching agents are disclosed in U.S. Patent 4,483,781, U.S. Patent
4,634,551, EP 0,133,354, U.S. Patent 4,412,934 and EP 0,170,386.
A preferled hydrophobic preforllled pero~cyacid bleach compound for
the purpose of the invention is monononylamido pero~cycarbo~ylic
acid.
Perfume composition
The other essential component of the invention is a perfume
composition comprising one or more aroma chemicals selected from
CA 0221~669 1997-09-16
W O 96/29281 PCTrUS96/02768
tertiary alcohols, nitriles, lactones, ketones, acetals, ethers, schiff
bases, esters and mi~tures thereof.
The perfume composition is incorporated in the bleaching composition
of the invention at a level of from 0.05% to 2% by weight, preferably
from 0.01% to 1% by weight of the bleaching composition.
The total sum of the weight of said aroma chemicals present in the
perfume composition is at least 40%, preferably at least 50% and more
preferably at least 60% by weight of the perfume.
For the purpose of the invention, aroma chemicals selected from
tertiary alcohols, nitriles, lactones, ketones, acetals, ethers and schiffs
bases can be either saturated or lln~tllrated. When in lm~hlrated
form, they comprise a group selected from an aromatic ring and an
alkenyl group and mi~ctures thereof.
For the purpose of the invention, aroma chemicals of the ester class
can be saturated or lln~ rated. When in lln~lrated form, they either
comprise an alkenyl group or are esters of salicylic acid.
Non-limitin~ tertiary alcohols suitable for the purpose of the invention
include tetrahydro linalool, tetrahydro myrcenol, tetrahydro muguol
and tetrahydro geraniol compounds and mi~ctures thereof.
When used such tertiary alcohol compounds will be at a level of up to
50%, ~referably at a level of up to 30% and more prefelably up to
20% by weight of the perfume composition.
Non-limiting e~camples of nitriles suitable for the purpose of the
invention include lauric nitrile, myristic nitrile and tridecene-2-nitrile
compounds, and mi~tures thereof.
When used such nitrile compounds will be at a level of up to 10%,
preferably at a level of up to S ~ by weight of the perfume
composition.
CA 0221~669 1997-09-16
PCTrUS96/02768
W 096/29281
Non-limiting examples of lactones suitable for the purpose of the
invention include undecalactone, hexadecanolide and
cyclopentadecanolide compounds.
When used such lactones will be at a level of up to 30%, preferably at
a level of up to 20% by weight of the perfume composition.
Non-limiting e~camples of ketones suitable for the purpose of the
invention include methyl beta naphtyl ketone, methyl phenyl ethyl
ketone and 7-acetyl 1,2,3,4,5,6,7,8 octanhydro 1,1,6,7 tetra methyl
naphtalene compounds.
When used such ketones will be at a level of from up to 40%,
preferably at a level of up to 30% and more preferably up to 20% by
weight of the perfume composition.
Non-limiting e~camples of ~cet~l~ suitable for the purpose of the
invention include (indan-alpha-ole, 2-hydro~cymethylene) formald
acetal, ~ret~klehyde phenyl ethyl propyl acetal and 4-phenyl-2,4,6-
trimethyl-1-3-dio~ane compounds.
When used such acetals will be at a level of up to 20%, preferably at a
level of up to 10% by weight of the perfume composition.
Non-limitin e~camples of ethers suitable for the purpose of the
invention include iso-amyl phenyl ethyl ether, phenyl ethyl methyl
ether, cedryl methyl ether and 3,3,5 trimethyl cyclohe~cyl ethyl ether
compounds.
When used such ethers will be at a level of up to 20%, preferably at a
level of up to 10% by weight of the perfume composition.
Non-limitin e~amples of schiffs bases suitable for the purpose of the
invention include lyral/methyl anthr~nil~te, helionallmethyl
anthr~nil~te and triplal/methyl anthr~nil~te.
CA 0221~669 1997-09-16
W O96/29281 PCTrUS96/02768
When used such schiffs bases will be at a level of up to 15 %,
preferably at a level of up to 10% and more preferably up to 5% by
weight of the perfume composition.
Non-limiting e~amples of esters suitable for the purpose of the
invention include 2-tertiary butyl cyclohe~yl acetate, 4-tertiary butyl
cyclohe~yl acetate, he~cahydro 4-7-methano-inden-5-yl acetate,
he~cahydro 4-7-methano-inden-6-yl acetate, he~ahydro 4-7-methano-
inden-5-yl propionate, he~cahydro 4-7-methano-inden-6-yl propionate,
he~yl salicylate and amyl salicylate compounds.
When used such esters will be at a level of up to 60%, preferably at a
level of up to 40% and more preferably up to 30% by weight of the
perfume composition.
For the purposes of the present invention, a perfumed bleaching
composition consists of a bleaching composition and a perfume
composition, wherein said perfume is incorporated by any means in a
composition selected from:
i)-the bleaching composition as a fini.~he~1 product,
ii)-the bleaching composition during its m~kin~ process,
or any mi~tures thereof.
For the purposes of the invention, a detergent composition
incorporating a perfumed bleaching composition consists of a
bleaching composition, a perfume composition, one or more
surf~ct~nts, one or more builders and optionally other conventional
deteLgent ingredients, wherein said perfume is incorporated by any
means in a composition selected from:
iii) a detergent composition, as a fini~he-l product, and incorporating
a bleaching composition,
iv) a detergent composition, during its m~kin~: process, and
incorporating a bleaching composition,
CA 0221~669 1997-09-16
W O96/29281 PCTrUS96102768
v) a bleaching composition as defined hereinbefore in i) and/or ii)
and further incorporated in a detergent composition and any
mi~ctures thereof.
Processes for incorporating the perfume in the bleaching composition
are not critical to the present invention. This can be done by spray-on,
admi~cture with one or more components of the bleaching composition
or other means known to the man skilled in the art. A yrefelled
process, for cost and practicability reasons, is a spray-on process.
The bleaching composition of the invention may also contain additional
components which are not detrimental to the perfume composition.
Such additional compounds may include fillers such as sodium
sulphate.
The detergent composition aspect of the invention comprises the
incorporation of the herein before described perfumed bleaching
composition together with a surfactant material, a builder, and
optionally other components conventional in detergent compositions.
Detergent compositions incorporating the perfumed bleaching
composition will normally contain from 0.1% to 60% of said perfumed
bleaching composition, more frequently from 2~o to 40% and most
preferably from 5% to 30%, on a composition weight basis.
Such detergent compositions will contain a surf~ct~nt material, a
builder and preferably will also contain other components conventional
in detergellt compositions. Thus, prererled delergent compositions will
incorporate one or more surfactants, builders together with one or
more soil suspending and anti-redeposition agents, suds suppressors,
enzymes, fluorescent whitening agents, photoactivated bleaches and
colours.
Surfactants
Deterge,lt compositions incorporating the perfumed bleaching
composition of the invention of the present invention will include one
or more surf~ct~nt~.
CA 0221~669 1997-09-16
W O 96/29281 PCTrUS96/02768
The total amount of surfactants will be generally up to 70%, typically
1 to 55%, preferably 1 to 30%, more preferably 5 to 25% and
especially 10 to 205'o by weight of the total composition.
Nonlimiting examples of surfactants useful herein include the
conventional C1 1-cl8 alkyl benzene sulfonates ("LAS") and primary,
branched-chain and random C1o-C20 alkyl sulfates ("AS"), the
C1o-C1g secondary (2,3) alkyl sulfates of the formula
CH3(CH2)~c(CHOS03-M + ) CH3 and CH3(CH2)y (CHOSO3-M + )
CH2CH3 where ~c and (y + 1) are integers of at least 7, preferably at
least 9, and M is a water-solubilizing cation, especially sodium,
n.c~lrated sulfates such as oleyl sulfate, the C1o-C1g alkyl alko~y
sulfates ("AE~S"; especially EO 1-7 etho~y sulfates), C10-cl8 alkyl
alko~y carbo~ylates (especially the EO 1-5 etho~cycarbo~ylates), the
C10-l8 glycerol ethers, the C10-cl8 alkyl polyglycosides and their
corresponding ~-llf~te-l polyglycosides, and C12-C1g alpha-sulfonated
fatty acid esters. If desired, the conventional nonionic and amphoteric
surfactants such as the C12-C1g alkyl etho~ylates ("AE"), including
the so-called narrow peaked alkyl etho~ylates and C6-C12 alkyl phenol
alko~cylates (especially etho~cylates and mi~ed etho~cy/propo~cy),
C12-C1g betaines and sulfobetaines ("slllt~ines"), C1o-C1g amine
o~ides, and the like, can also be included in the overall compositions.
The C1o-C1g N-alkyl polyhydro~y fatty acid amides can also be used.
Typical e~amples include the C12-C1g N-methylgl~-c~mi~es. See WO
9,206,154. Other sugar-derived surfact~nts include the N-alko~y
polyhydro~cy fatty acid amides, such as C1o-C1g N-(3-metho~cypropyl)
gll-c~mitle. The N-propyl through N-he~cyl C12-C1g gll-c~mi-les can
be used for low s---l~ing. Clo-C20 conventional soaps may also be
used. If high s~ in~ is desired, the branched-chain Clo-C16 soaps
may be used.
Other suitable surf~ct~nt~ suitable for the purpose of the invention are
the anionic alkali metal sarcosin~tes of formula:
R-CON(Rl )CH2COOM
wherein R is a Cg-C17 linear or branched alkyl or alkenyl group, R
is a C1-C4 alkyl group and M is an alkali metal ion. ~rerelred
e~camples are the lauroyl, cocoyl (C12-C14), myristyl and oleyl methyl
sarcosinates in the form of their sodium salts.
CA 0221~669 1997-09-16
W O96/29281 PCTrUS96/02768
Still another class of surfactant which may be suitable for the purpose
of the invention are the cationic surfactant. Suitable cationic surfactants
include the quaternary ammonium surfactants selected from mono C6-
C16, preferably C6-C1o N-alkyl or alkenyl ammonium surfactants
wherein the rem~inin~ N positions are substituted by methyl,
hydro~yethyl or hydro~ypropyl groups.
Mi~ctures of anionic and nonionic surfactants are especially useful.
Other conventional useful surfactants are listed in standard te~ts.
Builders - Detergent builders can optionally be included in the
compositions herein to assist in controlling mineral hardness.
Inorganic as well as organic builders can be used. Builders are
typically used in fabric l~llntlering compositions to assist in the
removal of particulate soils.
The level of builder can vary widely depending upon the end use
of the composition and its desired physical form. Granular
formulations typically comprise from 10% to 80%, more typically
from 15% to 50% by weight, of the detergent builder. Lower or
higher levels of builder, however, are not meant to be e~ccluded.
Inorganic or phosphate-cont~inin~ deter~ellt builders include, but
are not limited to, the alkali metal, ammonium and alkanolammonium
salts of polyphosphates (e~emplified by the tripolyphosphates,
pyrophosphates, and glassy polymeric meta-phosphates).
Non-phosphate builders may also be used. These can include, but are
not restricted to phytic acid, silicates, alkali metal carbonates
(including bicarbonates and sesquicarbonates), sulphates,
aluminosilicates, monomeric polycarbo~ylates, homo or copolymeric
polycarbo~ylic acids or their salts in which the polycarbo~cylic acid
comprises at least two carbo~cylic radicals separated from each other
by not more than two carbon atoms, organic phosphonates and
aminoaL~cylene poly (alkylene phosphonates).
The compositions herein also function in the presence of the so-called
"weak" builders (as compared with phosphates) such as citrate, or in
the so-called "underbuilt" situation that may occur with zeolite or
layered silicate builders.
CA 0221~669 1997-09-16
W O 96/29281 PCTrUS96/02768
E~camples of silicate builders are the so called 'amorphous' alkali
metal silicates, particularly those having a SiO2:Na2O ratio in the
~ range 1.6:1 to 3.2:1 and crystalline layered silicates, such as the
layered sodium silicates described in U.S. Patent 4,664,839. NaSKS-6
is the trademark for a crystalline layered silicate marketed by Hoechst
(commonly abbreviated herein as "SKS-6"). Unlike zeolite builders,
the Na SKS-6 silicate builder does not contain aluminium. NaSKS-6
has the delta-Na2Si2Os morphology form of layered silicate. It can be
prepared by methods such as those described in German DE-A-
3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred layered
silicate for use herein, but other such layered silicates, such as those
having the general formula NaMSix02~+ 1 ~yH20 wherein M is
sodium or hydrogen, ~c is a number from 1.9 to 4, preferably 2, and y
is a number from 0 to 20, preferably 0 can be used herein. Various
other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and
NaSKS-11, as the alpha, beta and ~mm~ forms. As noted above, the
delta-Na2Si2Os (NaSKS-6 form) is most preferred for use herein.
Other silicates may also be useful such as for e~cample magnesium
silicate, which can serve as a crispening agent in granular
formulations, as a stabilising agent for o~cygen bleaches, and as a
component of suds control systems.
E~camples of carbonate builders are the ~lk~line earth and alkali
metal carbonates as disclosed in German Patent Application No.
2,321,001 published on November lS, 1973. Such carbonate builders
act as builders to remove divalent metal ions such as calcium and
additionally provides ~lk~linity and aids in soil removal.
Aluminosilicate builders are useful in the present invention.
minosilis~te builders are of great importance in most currently
marketed heavy duty granular detergellt compositions, and can also be
a significant builder ingredient in liquid detel~;el.t formulations.
~l~lminosilicate builders include those having the empirical formula:
Nazt(Alo2)z(sio2)y] ~cH2o
wherein z and y are integers of at least 6, the molar ratio of z to y is in
the range from 1.0 to 0.5, and ~c is an integer from 15 to 264.
Useful aluminosilicate ion e~cchange materials are commercially
available. These ~ minosilicates can be crystalline or amorphous in
structure and can be naturally-occurring ~ minosilicates or
CA 0221~669 1997-09-16
W O96129281 PCTrUS96/02768
16
synthetically derived. A method for producing aluminosilicate ion
e~change materials is disclosed in U.S. Patent 3,985,669. Preferred
synthetic crystalline aluminosilicate ion e~cchange materials useful
herein are available under the designations Zeolite A, Zeolite P (B),
Zeolite MAP and Zeolite X. In an especially preferred embodiment,
the crystalline aluminosilicate ion e~cchange material has the formula:
Nal2[(A102)12(SiO2)12] ~H20
wherein ~c is from 20 to 30, especially 27. This material is known as
Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein.
Preferably, the aluminosilicate has a particle size of 0.1-10 microns in
diameter.
Organic detergent builders suitable for the purposes of the
present invention include, but are not restricted to, a wide variety of
polycarbo~ylate compounds. As used herein, "polycarbo~cylate" refers-
to compounds having a plurality of carbo~cylate groups, preferably at
least 3 carbo~ylates. Polycarbo~ylate builder can generally be added
to the composition in acid form, but can also be added in the form of a
neutralised salt. When l1tili7erl in salt form, alkali metals, such as
sodium, potassium, and lithium, or alkanolammonium salts are
prefel-red.
Included among the polycarbo~ylate builders are a variety of
categories of useful materials. One important category of
polycarbo~ylate builders encompasses the ether polycarbo~ylates,
including o~cydisuccinate, as disclosed in U.S. Patent 3,128,287 and
U.S. Patent 3,635,830. See also "TMS/TDS" builders of U.S. Patent
4,663,07L. Suitable ether polycarbo~cylates also include cyclic
compounds, particularly alicyclic compounds, such as those described
in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and
4,102,903.
Other useful deter~;e~cy builders include the ether
hydro~cypolycarbo~cylates, copolymers of maleic anhydride with
ethylene or vinyl methyl ether, or acrylic acid, 1, 3, 5-trihydro~cy
benzene-2, 4, 6-trisulphonic acid, and carbo~cymethylo~cysuccinic acid,
the various alkali metal, ammonium and substitlltetl ammonium salts of
polyacetic acids such as ethylen~i~mine tetraacetic acid and
nitrilotriacetic acid, as well as polycarbo~ylates such as mellitic acid,
succinic acid, o~ydisuccinic acid, polymaleic acid, benzene 1,3,5-
CA 0221~669 1997-09-16
W O96/29281 PCTrUS96/02768
17
tricarbo~ylic acid, carbo~ymethyloxysuccinic acid, and soluble salts
thereof.
Citrate builders, e.g., citric acid and soluble salts thereof
(particularly sodium salt), are polycarbo~ylate builders of particular
~ importance for heavy duty liquid detergent formulations due to their
availability from renewable resources and their biodegradability.
Citrates can also be used in granular compositions, especially in
combination with zeolite and/or layered silicate builders.
O~ydisuccinates are also especially useful in such compositions and
combinations.
Also suitable in the compositions cont~inin~ the present
invention are the 3,3-dicarbo~y-4-o~ca-1,6-he~anedioates and the
related compounds disclosed in U.S. Patent 4,566,984. Useful
succinic acid builders include the Cs-C20 alkyl and alkenyl succinic
acids and salts thereof. A particularly prefe,ied compound of this type
is dodecenylsuccinic acid. Specific e~amples of succinate builders
include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-
dodecenylsuccinate (preferred), 2-pent~lecenylsuccinate, and the like.
Laurylsuccinates are the ~refelled builders of this group, and are
described in EP 0,200,263.
Other suitable polycarbo~ylates are disclosed in U.S. Patent
4,144,226 and in U.S. Patent 3,308,067. See also U.S. Pat.
3,723,322.
Fatty acids, e.g., C12-C1g monocarbo~ylic acids, can also be
incorporated into the compositions alone, or in combination with the
aforesaid builders, especially citrate and/or the succinate builders, to
provide additional builder activity. Such use of fatty acids will
generally result in a ~iiminlltion of sl~lsin~, which should be taken into
account by the formulator.
In situations where phosphorus-based builders can be used, and
especially in the formulation of bars used for hand-l~lln~iering
operations, the various alkali metal phosphates such as the well-known
sodium tripolyphosphates, sodium pyrophosphate and sodium ortho-
phosphate can be used. Phosphonate builders such as ethane-1-
hydro~y-1,1-diphosphonate and other known phosphonates (see, for
e~ample, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148
and 3,422,137) can also be used.
CA 0221~669 1997-09-16
W O96/29281 PCTrUS96102768
18
Conventional deter~ent in redients
Chelants
Chelating agents generally comprise from 0.1% to lo~ by
weight of the compositions herein. ~ore preferably, if utilized, the
chelating agents will comprise from 0.1 % to 3.0% by weight of such
compositions.
A chelating agent can be selected from amino carbo~cylate, organic
phosphonate, polyfunctionally-substit~lte~l aromatic compound,
nitriloacetic acid and mi~cture thereof. Without intending to be bound
by theory, it is believed that the benefit of these materials is due in part
to their e~cceptional ability to remove transition metal ions such as iron
and m~n~nese ions from washing solutions by formation of soluble
chelates.
Amino carbo~ylates useful as optional chelating agents include
ethylene~ minetetracetates, ethylene~ mine disuccinate, N-
hydro~cyethylethylene~ minetri~cet~tes, 2-hydro~ypropylene Ai~mine
disuccinate, nitrilotriacetates, ethylene~ minP telr~roplionates,
triethylenetetr~min~.he~acetates, ethylene tri~mine pentaacetate,
diethylenetri~minepentaacetates, and ethanoldiglycines, alkali metal,
ammonium, and substit~lteA ammonium salts therein and mi~ctures
therein.
PreÇelled amino carbo~cylates chelants for use herein are
ethylen~li~mine disuccinate ("EDDS"), especially the [S,S] isomer as
described in U.S. Patent 4,704,233, ethyleneAi~min~-N,N'-diglllt~m~te
(EDDG) and 2-hydro~cypropylene-~ mine-N,N'-disuccinate (HPDDS)
compounds.
A most ple~elred amino carbo~cylate chelant is ethyleneAi~mint~
disuccinate.
Organic phosphonates are also suitable for use as chelating
agents in the compositions of the invention when at least low levels of
total phosphorus are permitted in detergent compositions, and include
ethyleneAi~mine.tetrakis (methylenephosphonates) available under the
trademark DEQUEST from Monsanto, diethylene tri~mine penta
(methylene phosphonate), ethylene tli~mine tri (methylene
CA 0221~669 1997-09-16
W O96t29281 PCTrUS96/02768
19
phosphonate), he~amethylene ~ mine tetra (methylene phosphonate),
a-hydroxy-2 phenyl ethyl diphosphonate, methylene diphosphonate,
hydroxy l,l-he~ylidene, vinylidene 1,1 diphosphonate, 1,2
dihydro~yethane 1,1 diphosphonate and hydro~y-ethane 1,1
diphosphonate.
Preferably, these amino phosphonates do not contain alkyl or alkenyl
groups with more than 6 carbon atoms.
Preferred chelants are the diphosphonate derivatives selected from a-
hydro~y-2 phenyl ethyl diphosphonate, methylene diphosphonate,
hydro~y l,l-he~ylidene, vinylidene 1,1 diphosphonate, 1,2
dihydro~yethane 1,1 diphosphonate and hydro~cy-ethane 1,1
diphosphonate. A most preferred is hydro~cy-ethane 1,1 diphosphonate.
Polyfunctionally-substitllte-l aromatic chelating agents are also useful in
the compositions herein. See U.S. Patent 3,812,044. Preferred
compounds of this type in acid form are dihydro~ydisulfobenzenes
such as 1 ,2-dihydro~y-3,5-disulfobenzene.
En7ymes - En_ymes can be included in the formulations herein
for a wide variety of fabric l~lln~1ering purposes, including removal of
protein-based, carbohydrate-based, or triglyceride-based stains, for
e~cample, and for the prevention of fugitive dye transfer, and for fabric
restoration. The en_ymes to be incorporated include proteases,
amylases, lipases, cellulases, and pero~cidases, as well as mi~ctures
thereof. Other types of enzymes may also be included. They may be
of any suitable origin, such as vegetable, ~nim~l~ bacterial, fungal and
yeast origin. However, their choice is governed by several factors
such as pH-activity and/or stability optima, thermostability and
stability versus active detergenl~ and builders. In this respect bacterial
or fungal enzymes are preferred, such as bacterial amylases and
proteases, and fungal cellulases.
Enzymes are normally incorporated at levels sufflcient to
provide up to 5 mg by weight, more typically 0.01 mg to 3 mg, of
active enzyme per gram of the composition. Stated otherwise, the
compositions herein will typically comprise from 0.001% to 5% by
weight of a commercial enzyme preparation.
CA 0221~669 1997-09-16
W O96/29281 PCTrUS96/02768
Suitable e~amples of proteases are the subtilisins which are
obtained from particular strains of B. subtilis and B. Iicheniforms.
Another suitable protease is obtained from a strain of Bacillus, having
ma~cimum activity throughout the pH range of 8-12, developed and
sold by Novo Industries A/S under the registered trade name
ESPERASE. The preparation of this enzyme and analogous enzymes
is described in GB 1,243,784 of Novo. Proteolytic enzymes suitable
for removing protein-based stains that are commercially available
include those sold under the tradenames ALCALASE and SAVINASE
by Novo Industries A/S (Denmark) and MAXATASE by International
Bio-Synthetics, Inc. (The Netherlands). Other proteases include
Protease A (see EP 130,756) and Protease B (see EP257189).
Preferred levels of proteases are from 0.01% to 4.0% by weight of the
detergent composition herein.
Amylases include, for e~cample, a-amylases described in GB
1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and
TERMAMYL, Novo Industries. Fungamyl (Novo) is especially useful.
Preferred levels of amylases are from 0.01 % to 2.0% by weight of the
detergent composition herein.
The cellulases usable in the present invention include both
bacterial or fungal cellulase. Preferably, they will have a pH optimum
of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent
4,435,307, which discloses fungal cellulase pro~ ce-l from Humicola
insolens and Humicola strain DSM1800 or a cellulase 212-producing
fungus belonging to the genus Aeromonas, and cellulase e~ctracted
from the hepatopancreas of a marine mollusk (Dolabella Auricula
Solander). Suitable cellulases are also disclosed in GB-A-2.075.028;
GB-A-2.095.275 and DE-OS-2.247.832. ENDO A, CAREZYME both
from Novo ~n~ stries A/S are especially useful. P1ererred levels of
cellulases are from 0.01 % to 1.0% by weight of the detergellt
composition herein.
Suitable lipase enzymes for detergent usage include those
produced by microorE~ni~m~ of the Pseudomonas group, such as
Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1,372,034.
See also lipases in Japanese Patent Application 53,20487, laid open to
public inspection on February 24, 1978. This lipase is available from
Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name
CA 0221~669 1997-09-16
W O 96/29281 PCTrUS96/02768
Lipase P "Amano," hereinafter referred to as "Amano-P." Other
commercial lipases include Amano-CES, lipases e~ Chromobacter
~ viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB
3673, commercially available from Toyo Jozo Co., Tagata, Japan; and
further Chromobacter viscosum lipases from U.S. Biochemical Corp.,
U.S.A. and Disoynth Co., The Netherlands, and lipases ex
Pseudomonas gladioli. The LIPOLASE enzyme derived from
Humicola lanuginosa and commercially available from Novo (see also
EP 341,947) is a preferred lipase for use herein. Preferred levels of
lipases are from 0.01 % to 2.0% by weight of the detergent
composition herein.
Pero~idase enzymes are used in combination with o~cygen
sources, e.g., percarbonate, perborate, persulfate, hydrogen pero~ide,
etc. They are used for "solution bleaching," i.e. to prevent transfer of
dyes or pigments removed from substrates during wash operations to
other substrates in the wash solution. Pero~idase enzymes are known
in the art, and include, for e~cample, horseradish pero~idase, lignin~e,
and halopero~cidase such as chloro- and bromo-pero~cidase. Pero~idase-
cont~ining detergent compositions are disclosed, for e~ample, in PCT
International Application WO 89/099813, published October 19, 1989,
by O. Kirk, assigned to Novo Industries A/S.
A wide range of enzyme materials and means for their
incorporation into synthetic detergent compositions are also disclosed
in U.S. Patent 3,553,139. Enzymes are further disclosed in U.S.
Patent 4,101,457 and in U.S. Patent 4,507,219. Enzyme materials
useful for liquid detergent formulations, and their incorporation into
such formulations, are disclosed in U.S. Patent 4,261,868. Enzymes
for use in detergenls can be stabilized by various techniques. Enzyme
stabilisation techniques are disclosed and e~cemplified in U.S. Patent
3,600,319 and EP 0 199 405. Enzyme stabilisation systems are also
described, for e~ample, in U.S. Patent 3,519,570.
Fn7~me Stabilisers - The enzymes employed herein are
stabilized by the presence of water-soluble sources of calcium and/or
m~nesium ions in the fini.~hed compositions which provide such ions
to the enzymes. (Calcium ions are generally somewhat more effective
than m~gn~sium ions and are prefell~d herein if only one type of
CA 0221~669 1997-09-16
W O96/29281 PCTrUS96/02768
cation is being used.) Additional stability can be provided by the
presence of various other art-disclosed stabilisers, especially borate
species: see Severson, U.S. 4,537,706. Typical detergents, especially
liquids, will comprise from 1 to 30, preferably from 2 to 20, more
preferably from S to 15, and most preferably from 8 to 12, millimoles
of calcium ion per litre of finished composition. This can vary
somewhat, depending on the amount of enzyme present and its
response to the calcium or magnesium ions. The level of calcium or
magnesium ions should be selected so that there is always some
minimllm level available for the enzyme, after allowing for
comple~ation with builders, fatty acids, etc., in the composition. Any
water-soluble calcium or magnesium salt can be used as the source of
calcium or magnesium ions, including, but not limited to, calcium
chloride, calcium sulfate, calcium m~l~te, calcium maleate, calcium
hydro~ide, calcium formate, and calcium acetate, and the
corresponding m~gnesium salts. A small amount of calcium ion,
generally from 0.05 to 0.4 millimoles per litre, is often also present in
the composition due to calcium in the enzyme slurry and formula
water. In solid detergent compositions the formulation may include a
sufficient quantity of a water-soluble calcium ion source to provide
such amounts in the laundry liquor. In the alternative, natural water
hardness may suffice.
It is to be understood that the foregoing levels of calcium and/or
m~gnesium ions are sufficient to provide enzyme stability. More
calcium and/or m~nesium ions can be added to the compositions to
provide an additional measure of grease removal performance.
Accordingly, as a general proposition the compositions herein will
typically comprise from 0.05% to 2% by weight of a water-soluble
source of calcium or m~gnesium ions, or both. The amount can vary,
of course, with the amount and type of enzyme employed in the
composition.
The compositions herein may also optionally, but preferably,
contain various additional stabilizers, especially borate-type stabilizers.
Typically, such stabilizers will be used at levels in the compositions
from 0.25% to 10%, ~leferably from 0.5% to 5%, more ~rerelably
from 0.75 % to 3 5~, by weight of boric acid or other borate compound
capable of forming boric acid in the composition (calc~ te~l on the
CA 0221~669 1997-09-16
W O96/29281 PCT~US96/02768
basis of boric acid). Boric acid is preferred, although other compounds
such as boric o~ide, borax and other alkali metal borates (e.g., sodium
~ ortho-, meta- and pyroborate, and sodium pentaborate) are suitable.
Substituted boric acids (e.g., phenylboronic acid, butane boronic acid,
~ and p-bromo phenylboronic acid) can also be used in place of boric
acid.
Polymeric Dispersing Agents - Polymeric dispersing agents can
advantageously be lltili~e~i at levels from 0.5% to 8%, by weight, in
the compositions herein, especially in the presence of zeolite and/or
layered silicate builders. Suitable polymeric dispersing agents include
polymeric polycarbo~cylates and polyethylene glycols, although others
known in the art can also be used. It is believed, though it is not
intended to be limited by theory, that polymeric dispersing agents
enhance overall detergent builder performance, when used in
combination with other builders (including lower molecular weight
polycarbo~ylates) by particulate soil release peptization, and anti-
redeposition.
Polymeric polycarbo~ylate materials can be prepared by
polymerizing or copolymerizing suitable lln~tllrated monomers,
preferably in their acid form. Unsaturated monomeric acids that can
be polymerized to form suitable polymeric polycarbo~cylates include
acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic
acid, aconitic acid, mesaconic acid, citraconic acid and
methylenemalonic acid. The presence in the polymeric
polycarbo~ylates herein or monomeric segments, cont~inin~ no
carbo~ylate radicals such as vinylmethyl ether, styrene, ethylene, etc.
is suitable provided that such segments do not con~ti~lte more than
40% by weight.
Particularly suitable polymeric polycarbo~cylates can be derived
from acrylic acid. Such acrylic acid-based polymers which are useful
herein are the water-soluble salts of polymerized acrylic acid. The
average molecular weight of such polymers in the acid form preferably
ranges from 2,000 to 10,000, more preferably from 4,000 to 7,000 and
most pref~lably from 4,000 to 5,000. Water-soluble salts of such
acrylic acid polymers can include, for e~ample, the alkali metal,
ammonium and substi~lte~i ammonium salts. Soluble polymers of this
CA 0221~669 1997-09-16
W O96/29281 PCTrUS96/02768
24
type are known materials. Use of polyacrylates of this type in
detergent compositions has been disclosed, for example, in Diehl, U.S.
Patent 3,308,067, issued march 7, 1967.
Acrylic/maleic-based copolymers may also be used as a
preferred component of the dispersing/anti-redeposition agent. Such
materials include the water-soluble salts of copolymers of acrylic acid
and maleic acid. The average molecular weight of such copolymers in
the acid form preferably ranges from 2,000 to 100,000, more
preferably from 5,000 to 75,000, most preferably from 7,000 to
65,000. The ratio of acrylate to maleate segments in such copolymers
will generally range from 30:1 to 1:1, more preferably from 10:1 to
2: 1. Water-soluble salts of such acrylic acid/maleic acid copolymers
can include, for e~ample, the alkali metal, ammonium and substituted
ammonium salts. Soluble acrylate/maleate copolymers of this type are
known materials which are described in European Patent Application
No. 66915, published December 15, 1982, as well as in EP 193,360,
published September 3, 1986, which also describes such polymers
comprising hydro~cypropylacrylate. Still other useful dispersing agents
include the maleic/acrylic/vinyl alcohol terpolymers. Such materials
are also disclosed in EP 193,360, including, for e~ample, the 45/45/10
terpolymer of acrylic/maleic/vinyl alcohol.
Another polymeric material which can be included is
polyethylene glycol (PEG). PEG can e~hibit dispersing agent
performance as well as act as a clay soil removal-antiredeposition
agent. Typical molecular weight ranges for these purposes range from
500 to 100,000, preferably from 1,000 to 50,000, more ~rerel~ly
from 1,500 to 10,000.
Polyaspartate and polyglllt~m~te dispersing agents may also be
used, especially in conjunction with zeolite builders. Dispersing
agents such as polyaspartate preferably have a molecular weight (avg.)
of 10,000.
Clay Soil Removal/Anti-redeposition Apents - The compositions
according to the present invention can also optionally contain water-
soluble etho~ylated amines having clay soil removal and antire-
deposition properties. Granular detelgent compositions which contain
these compounds typically contain from 0.01 % to 10.0% by weight of
CA 0221~669 1997-09-16
W O96/29281 PCTrUS96/02768
the water-soluble etho~cylates amines; liquid detergent compositions
typically contain 0.01% to 5~o.
~ The most preferred soil release and anti-redeposition agent is
etho~ylated tetraethylenepent~mine. E~emplary etho~ylated amines
~ are further described in U.S. Patent 4,597,898, VanderMeer, issued
July 1, 1986. Another group of preferred clay soil removal-
antiredeposition agents are the cationic compounds disclosed in EP
111,965. Other clay soil removal/antiredeposition agents which can be
used include the etho~ylated amine polymers disclosed in EP 111,984;
the zwitterionic polymers disclosed in EP 112,592; and the amine
oxides disclosed in U.S. Patent 4,548,744. Other clay soil removal
and/or anti redeposition agents known in the art can also be l1tili7ed in
the compositions herein. Another type of prert;rred antiredeposition
agent includes the carboxy methyl cellulose (CMC) materials. These
materials are well known in the art.
Polymeric Soil Release A ent - Any polymeric soil release agent
known to those skilled in the art can optionally be employed in the
compositions and processes of this invention. Polymeric soil release
agents are characterised by having both hydrophilic segments, to hy-
drophilize the surface of hydrophobic fibers, such as polyester and
nylon, and hydrophobic se~m~ont~, to deposit upon hydrophobic fibers
and remain adhered thereto through completion of washing and rinsing
cycles and, thus, serve as an anchor for the hydrophilic segments. This
can enable stains occurring subsequent to treatment with the soil
release agent to be more easily cleaned in later washing procedures.
Soil release agents characterised by poly(vinyl ester)
hydrophobe segments include graft copolymers of poly(vinyl ester),
e.g., Cl-C6 vinyl esters, preferably poly(vinyl acetate) grafted onto
polyalkylene o~cide backbones, such as polyethylene o~cide backbones
(see EP 0 219 048). Commercially available soil release agents of this
kind include the SOKALAN type of material, e.g., SOKALAN HP-22,
available from BASF (VVest Germany).
One type of preferred soil release agent is a copolymer having
random blocks of ethylene terephth~l~te and polyet_ylene o~ide (PEO)
terephth~l~te. The molecular weight of this polymeric soil release
CA 0221~669 1997-09-16
W O 96/29281 PCTrUS96/02768
26
agent is in the range of from 25,000 to 55,000. See U.S. Patent
3,959,230 to Hays and U.~. Patent 3,893,929.
Another preferred polymeric soil release agent is a polyester
with repeat units of ethylene terephth~l~te units which contains 10-155'o
by weight of ethylene terephth~l~te units together with 90-80% by
weight of polyo~cyethylene terephth~l~te units, derived from a
polyo~cyethylene glycol of average molecular weight 300-5,000.
E~camples of this polymer include the commercially available material
ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also
U.S. Patent 4,702,857.
Another preferred polymeric soil release agent is a sulfonated
product of a subst~nti~lly linear ester oligomer comprised of an
oligomeric ester backbone of terephthaloyl and o~yalkyleneo~y repeat
units and terminal moieties covalently attached to the backbone. These
soil release agents are described fully in U.S. Patent 4,968,451. Other
suitable polymeric soil release agents include the terephth~l~te
polyesters of U.S. Patent 4,711,730, the anionic end-capped
oligomeric esters of U.S. Patent 4,721,580 and the block polyester
oligomeric compounds of U.S. Patent 4,702,857.
P'leferred polymeric soil release agents also include the soil
release agents of U.S. Patent 4,877,896, which discloses anionic,
especially sulfoarolyl, end-capped terephth~l~te esters.
If lltili7e~1, soil release agents will generally comprise from
0.01 % to 10.0%, by weight, of the compositions herein, typically from
0.1% to 5%, ~refe~ably from 0.2% to 3.0%.
Still another preferred soil release agent is an oligomer with
repeat units of terephthaloyl units, sulfoisoterephthaloyl units,
o~cyethyleneo~y and o~y-1,2-propylene units. The repeat units form the
backbone of the oligomer and are preferably termin~te~l with modified
isethionate end-caps. A particularly l~referled soil release agent of this
type comprises one sulfoisophthaloyl unit, 5 terephthaloyl units,
o~cyethyleneo~cy and o~cy-1,2-propyleneo~y units in a ratio of from 1.7
to 1.8, and two end-cap units of sodium 2-(2-hydro~cyetho~cy)-
eth~nesulfonate. Said soil release agent also comprises from 0.5 % to
20%, by weight of the oligomer, of a crystalline-reducing stabilizer,
preferably selected from ~cylene sulfonate, cumene sulfonate, toluene
sulfonate, and mi~ctures thereof.
CA 0221~669 1997-09-16
W 096/29281 PCTrUS96/02768
Dye Transfer Inhibiting A~ents
The compositions according to the present invention may also include
one or more materials effective for inhibiting the transfer of dyes from
~ one fabric to another during the cle~nin.~ process. Generally, such dye
transfer inhibiting agents include polyvinyl pyrrolidone polymers,
polyamine N-o~ide polymers, copolymers of N-vinylpyrrolidone and
N-vinylimidazole, m~n~nese phthalocyanine, pero~idases, and
mi~ctures thereof. If used, these agents typically comprise from 0.01%
to 10% by weight of the composition, preferably from 0.01% to 5%,
and more preferably from 0.05% to 2%.
More specifically, the polyamine N-oxide polymers preferred for
use herein contain units having the following structural formula: R-AX-
P; wherein P is a polymerizable unit to which an N-O group can be
attached or the N-O group can form part of the polymerizable unit or
the N-O group can be attached to both units; A is one of the following
structures: -NC~O)-, -C(O)O-, -S-, -O-, -N=; ~c is 0 or 1; and R is
aliphatic, etho~cylated aliphatics, aromatics, heterocyclic or alicyclic
groups or any combination thereof to which the nitrogen of the N-O
group can be attached or the N-O group is part of these groups.
Pre~erled polyamine N-o~cides are those wherein R is a heterocyclic
group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and
derivatives thereof.
The N-O group can be represented by the following general
structures:
N--(R2)y; =N (Rl)x
~R3)Z
wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic
groups or combinations thereof; ~, y and z are 0 or 1; and the nitrogen
of the N-O group can be attached or form part of any of the
aforementioned groups. The amine o~cide unit of the polyamine N-
o~ides has a pKa < 10, ~referably pKa <7, more ~refel~ed pKa <6.
Any polymer backbone can be used as long as the amine o~cide
polymer formed is water-soluble and has dye transfer inhibiting
properties. E~camples of suitable polymeric backbones are polyvinyls,
CA 0221~669 1997-09-16
W O96129281 PCTrUS96/02768
28
polyalkylenes, polyesters, polyethers, polyamide, polyimides,
polyacrylates and mi~tures thereof. These polymers include random or
block copolymers where one monomer type is an amine N-o~ide and
the other monomer type is an N-o~ide. The amine N-o~ide polymers
typically have a ratio of amine to the amine N-o~ide of 10:1 to
1:1,000,000. However, the number of amine o~ide groups present in
the polyamine o~ide polymer can be varied by appropriate
copolymerization or by an appropriate degree of N-o~idation. The
polyamine o~cides can be obtained in almost any degree of
polymerization. Typically, the average molecular weight is within the
range of 500 to 1,000,000; more preferred 1,000 to 500,000; most
preferred 5,000 to 100,000. This preferred class of materials can be
referred to as "PVNO".
The most preferred polyamine N-o~ide useful in the
compositions herein is poly(4-vinylpyridine-N-o~ide) which as an
average molecular weight of 50,000 and an amine to amine N-o~ide
ratio of 1:4.
Copolymers of N-vinylpyrrolidone and N-vinylimi~1~7ole
polymers (refelred to as a class as "PVPVI") are also preferred for use
herein. Preferably the PVPVI has an average molecular weight range
from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and
most preferably from 10,000 to 20,000. Cl he average molecular
weight range is determined by light scattering as described in Barth, et
al., Chemical Analysis, Vol 113. "Modern Methods of Polymer
Characterization".) The PVPVI copolymers typically have a molar
ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1,
more ~referably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to
0.4:1. These copolymers can be either linear or branched.
The present invention compositions also may employ a poly-
vinylpyrrolidone ("PVP") having an average molecular weight of from
5,000 to 400,000, L,refelably from 5,000 to 200,000, and more
prefelably from 5,000 to 50,000. PVP's are known to persons skilled
in the deter~ellt field; see, for e~cample, EP-A-262,897 and EP-A-
256,696. Compositions cont~ininf~ PVP can also contain polyethylene
glycol ("PEG") having an average molecular weight from 500 to
100,000, preferably from 1,000 to 10,000. P~ererably, the ratio of
CA 0221~669 1997-09-16
W O96129281 PCTrUS96/02768
29
PEG to PVP on a ppm basis delivered in wash solutions is from 2:1 to
50:1, and more preferably from 3:1 to 10:1.
The detergent compositions herein may also optionally contain
from 0.005% to 5% by weight of certain types of hydrophilic optical
brighteners which also provide a dye transfer inhibition action. If used,
the compositions herein will preferably comprise from 0.01% to 1.2%
by weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present
invention are those having the structural formula:
R, R2
~N I ~ ~ I N(~
R2 SO3M SO3M Rl .
wherein Rl is selected from anilino, N-2-bis-hydro~cyethyl and NH-2-
hydroxyethyl; R2 is selected from N-2-bis-hydro~cyethyl, N-2-
hydro~cyethyi-N-methyiamino, morphiiino, chioro and amino, and M is
a salt-forming cation such as sodium or pot~csi~lm
When in the above formula, R1 is anilino, R2 is N-2-bis-
hydro~cyethyl and M is a cation such as sodium, the brightener is 4,4',-
bis[(4-anilino-6-(N-2-bis-hydro~cyethyl)-s-triazine-2-yl)amino]-2,2'-
stilbenedisulfonic acid and disodium salt. This particular brightener
species is commercially marketed under the tradename Tinopal-UNPA-
GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the pleferred
hydrophilic optical brightener useful in the compositions herein.
When in the above formula, R1 is ~nilino, R2 is N-2-
hydro~yethyl-N-2-methylamino and M is a cation such as sodium, the
brightener is 4,4'-bis[(4-anilino-6-(N-2-hydro~yethyl-N-methylamino)-
s-triazine-2-yl)amino~2,2'-stilbenedisulfonic acid disodium salt. This
particular brightener species is commercially marketed under the
- tradename Tinopal SBM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is ~nilino, R2 is morphilino and
M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-
morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium
salt. This particular brightener species is commercially marketed
under the tr~1en~m~ Tinopal AMS-GX by Ciba Geigy Corporation.
CA 0221~669 1997-09-16
W O96/29281 PCTAUS96/02768
Other specific optical brightener species which may be used in
the present invention provide especially effective dye transfer inhibition
performance bene~lts when used in combination with the selected
polymeric dye transfer inhibiting agents hereinbefore described. The
combination of such selected polymeric materials (e.g., PVNO and/or
PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-
GX, Tinopal SBM-GX and/or Tinopal AMS-GX) provides significantly
better dye transfer inhibition in aqueous wash solutions than does either
of these two detergent composition components when used alone.
Without being bound by theory, it is believed that such brighteners
work this way because they have high affinity for fabrics in the wash
solution and therefore deposit relatively quick on these fabrics. The
e~ctent to which brighteners deposit on fabrics in the wash solution can
be defined by a parameter called the "e~haustion coefficient". The
e~haustion coefficient is in general as the ratio of a) the brightener
material deposited on fabric to b) the initial brightener concentration in
the wash liquor. Brighteners with relatively high e~haustion
coefficients are the most suitable for inhibiting dye transfer in the
conte~ct of the present invention.
Of course, it will be appreciated that other conventional optical
brightener types of compounds can optionally be used in the present
compositions to provide conventional fabric "bri~htness" benefits,
rather than a true dye transfer inhibiting effect. Such usage is
conventional and well-known to deterge-lt formulations.
Conventional optical brighteners or other brightening or
whitening agents known in the art can be incorporated at levels
typically from 0.005% to 5%, prefelably from 0.01% to 1.2% and
most preferably from 0.05% to 1.2%, by weight, into the deter~ e.lt
compositions herein. Commercial optical brighteners which may be
useful in the present invention can be classified into subgroups, which
include, but are not necessarily limiterl to, derivatives of stilbene,
pyrazoline, coumarin, carbo~cylic acid, methinecyanines,
dibenzothiophene-5,5-dio~cide, azoles, 5- and 6-membered-ring
heterocycles, and other miscellaneous agents. E~camples of such
brighteners are disclosed in "The Production and Application of
Fluorescent Brightening Agents", M. Zahradnik, Published by John
CA 0221~669 1997-09-16
W O 96/29281 PCTrUS96/02768
Wiley & Sons, New York (1982). Further optical brightener which
may also be used in the present invention include naphth~limicle,
benzoxazole, benzofuran, benzimidazole and any mi~tures thereof.
Specific e~camples of optical brighteners which are useful in the
~ present compositions are those identified in U.S. Patent 4,790,856.
These brighteners include the PHORWHITE series of brighteners from
Verona. Other brighteners disclosed in this reference include: Tinopal
UNPA, Tinopal CBS and Tinopal SBM; available from Ciba-Geigy;
Artic White CC and Artic White CWD; the 2-(4-styryl-phenyl)-2H-
naptho[l,2-d]triazoles; 4,4'-bis(1,2,3-triazol-2-yl)-stilbenes; 4,4'-
bis(styryl)bisphenyls; and the aminocoumarins. Specific e~camples of
these brighteners include 4-methyl-7-diethyl- amino coumarin; 1,2-
bis(-ben7imicl~7:01-2-yl)ethylene; 1,3-diphenyl-pyrazolines; 2,5-
bis(benzo~azol-2-yl)thiophene; 2-styryl-naptho-[1,2-d]o~cazole; and 2-
(stilbene-4-yl)-2H-naphtho[1,2-d]triazole. See also U.S. Patent
3,646,015.
Suds Suppressors - Compounds for reducing or suppressing the
formation of suds can be incorporated into the compositions of the
present invention. Suds suppression can be of particular importance in
the so-called "high concentration cle~nin~ process" and in front-
loading European-style w~hin~ machines.
A wide variety of materials may be used as suds suppressors,
and suds ~u~-essors are well known to those skilled in the art. See,
for e~cample, Kirk Othmer Encyclopedia of Chemical Technology,
Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc.,
1979). One category of suds ~u~ressor of particular interest
encompasses monocarbo~cylic fatty acid and soluble salts therein. See
U.S. Patent 2,954,347. The monocarbo~cylic fatty acids and salts
thereof used as suds ~uppressor typically have hydrocarbyl chains of
10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts
include the alkali metal salts such as sodium, potassium, and lithillm
salts, and ammonium and ~lk~nol~mml)niurn salts.
The detergent compositions herein may also contain non-
surf~t~nt suds ~ressors. These include, for e~cample: high
molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g.,
fatty acid triglycerides), fatty acid esters of monovalent alcohols,
CA 0221~669 1997-09-16
W O96/29281 PCT~US96/02768
aliphatic C1g-C40 ketones (e.g., stearone), etc. Other suds inhibitors
include N-alkylated amino triazines such as tri- to he~ca-alkylmel~mines
or di- to tetra-alkyltli~mine chlortriazines formed as products of
cyanuric chloride with two or three moles of a primary or secondary
amine cont~inin~ l to 24 carbon atoms, propylene o~ide, and
monostearyl phosphates such as monostearyl alcohol phosphate ester
and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and
phosphate esters. The hydrocarbons such as paraffin and haloparaffin
can be l~t~ ed in liquid form. The liquid hydrocarbons will be liquid at
room temperature and atmospheric pressure, and will have a pour
point in the range of -40~C and 50~C, and a minimum boiling point
not less than 110~C (atmospheric pressure). It is also known to utilize
wa~cy hydrocarbons, preferably having a melting point below 100~C.
The hydrocarbons constitute a preferred category of suds suppressor
for detergent compositions. Hydrocarbon suds suppressors are
described, for e~ample, in U.S. Patent 4,265,779. The hydrocarbons,
thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated
or lln~lrated hydrocarbons having from 12 to 70 carbon atoms. The
term "paraffin," as used in this suds suppressor discussion, is intended
to include mi~ctures of true paraffins and cyclic hydrocarbons.
Another preferred category of non-surfactant suds suppressors
comprises silicone suds suppressors. This category includes the use of
polyorganosilo~ane oils, such as polydimethylsilo~cane, dispersions or
emulsions of polyorganosilo~ane oils or resins, and combinations of
polyorganosilo~cane with silica particles wherein the
polyorganosilo~cane is chemisorbed or fused onto the silica. Silicone
suds su~ressors are well known in the art and are, for e~ample,
disclosed in U.S. Patent 4,265,779 and EP 354016.
Other silicone suds suppressors are disclosed in U.S. Patent
3,455,839 which relates to compositions and processes for defo~min~
aqueous solutions by incorporating therein small amounts of
poly-limet~ylsilo~cane fluids.
Mi~tures of silicone and ~ n~tefl silica are described, for
in~t~nce, in German Patent Application DOS 2,124,526. Silicone
defoamers and suds controlling agents in granular detergent
compositions are disclosed in U.S. Patent 3,933,672 and in U.S.
Patent 4,652,392.
CA 0221~669 1997-09-16
W O96/29281 PCTrUS96/02768
An e~cemplary silicone based suds suppressor for use herein is a
suds suppressing amount of a suds controlling agent consisting
essentially of:
(i) polydimethylsilo~ane fluid having a viscosity of from 20 cs.
tol,SOOcs.at25~C;
(ii) from S to 50 parts per 100 parts by weight of (i) of silo~cane
resin composed of (CH3)3SiO1/2 units of SiO2 units in a
ratio of from (CH3)3 SiOl/2 units and to SiO2 units of
from 0.6: 1 to 1.2: 1; and
(iii) from 1 to 20 parts per 100 parts by weight of (i) of a solid
silica gel.
In the preferred silicone suds suppressor used herein, the solvent
for a continuous phase is made up of certain polyethylene glycols or
polyethylene-polypropylene glycol copolymers or mi~ctures thereof
(preferred), or polypropylene glycol. The primary silicone suds
suppressor is branched/crosslinked and prefelably not linear.
To illustrate this point further, typical liquid laundry detergent
compositions with controlled suds will optionally comprise from 0.001
to 1, preferably from 0.01 to 0.7, most preferably from 0.05 to 0.5,
weight % of said silicone suds suppressor, which comprises (1) a
nonaqueous emulsion of a primary antifoam agent which is a mi~ture
of (a) a polyorganosilo~cane, (b) a resinous silo~ane or a silicone resin-
producing silicone compound, ~c) a finely divided filler material, and
(d) a catalyst to promote the reaction of mi~cture components (a), (b)
and (c), to form silanolates; (2) at least one nonionic silicone
surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-
polypropylene glycol having a solubility in water at room temperature
of more than 2 weight %; and without polypropylene glycol. Similar
amounts can be used in granular compositions, gels, etc. See also U.S.
Patents 4,978,471 and 4,983,316; 5,288,431 and U.S. Patents
4,639,489 and 4,749,740, Aizawa et al at column 1, line 46 through
column 4, line 35.
The silicone suds suppressor herein preferably comprises
polyethylene glycol and a copolymer of polyethylene
glycol/polypropylene glycol, all having an average molecular weight of
less than 1,000, preferably between 100 and 800. The polyethylene
glycol and polyethylene/polypropylene copolymers herein have a
CA 0221~669 1997-09-16
W O96/29281 PCTrUS96/02768
34
solubility in water at room temperature of more than 2 weight %,
preferably more than 5 weight %.
The preferred solvent herein is polyethylene glycol having an
average molecular weight of less than 1,000, more preferably between
100 and 800, most preferably between 200 and 400, and a copolymer
of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG
300. Preferred is a weight ratio of between 1: 1 and 1: 10, most
preferably between 1 :3 and 1 :6, of polyethylene glycol:copolymer of
polyethylene-polypropylene glycol.
The preferred silicone suds suppressors used herein do not
contain polypropylene glycol, particularly of 4,000 molecular weight.
They also preferably do not contain block copolymers of ethylene
o~ide and propylene o~cide, like PLURONIC L101.
Other suds suppressors useful herein comprise the secondary
alcohols (e.g., 2-alkyl alkanols) and mi~tures of such alcohols with
silicone oils, such as the silicones disclosed in U.S. 4,798,679,
4,075,118 and EP 150,872. The secondary alcohols include the C6-
C16 alkyl alcohols having a C1-C16 chain. A preferred alcohol is 2-
butyl octanol, which is available from Condea under the trademark
ISOFOL 12. Mi~ctures of secondary alcohols are available under the
trademark ISALCHEM 123 from Enichem. Mi~ed suds suppressors
typically comprise mi~ctures of alcohol + silicone at a weight ratio of
1:5 to 5:1.
For any detergent compositions to be used in automatic laundry
washing machines, suds should not form to the e~ctent that they
overflow ~he washing machine. Suds suppressors, when ~ltili7e~l~ are
prefeLably present in a "suds suppressing amount. By "suds
suppressing amount" is meant that the formlll~tor of the composition
can select an amount of this suds controlling agent that will sufficiently
control the suds to result in a low-sudsing laundry detel~ el.t for use in
automatic laundry washing machines.
The compositions herein will generally comprise from 0% to 5%
of suds suppressor. When lltili7~1 as suds ~uppressors,
monocarbo~cylic fatty acids, and salts therein, will be present typically
in amounts up to 5 %, by weight, of the detergent composition.
Preferably, from 0.5 % to 3 % of fatty monocarbo~cylate suds
~u~l~ressor is lltili7efl. Silicone suds suppressors are typically lltili7e-1
CA 0221~669 1997-09-16
W O96/29281 PCTrUS96/02768
in amounts up to 2.0%, by weight, of the detergent composition,
although higher amounts may be used. This upper limit is practical in
nature, due primarily to concern with keeping costs minimi7e~1 and
effectiveness of lower amounts for effectively controlling sudsing.
Preferably from 0.01% to 1% of silicone suds suppressor is used,
more preferably from 0.25% to 0.5~. As used herein, these weight
percentage values include any silica that may be lltili7erl in
combination with polyorganosilo~cane, as well as any adjunct materials
that may be ~ltili7e~1. Monostearyl phosphate suds suppressors are
generally lltili7e~ in amounts r~n~in~ from 0.1% to 2%, by weight, of
the composition. Hydrocarbon suds suppressors are typically lltili7erl
in amounts r~n~in~ from 0.01% to 5.0%, although higher levels can be
used. The alcohol suds suppressors are typically used at 0.2%-3% by
weight of the finished compositions.
Fabric Softeners - Various through-the-wash fabric softeners,
especially the impalpable smectite clays of U.S. Patent 4,062,647, as
well as other softener clays known in the art, can optionally be used
typically at levels of from 0.5% to 10%, preferably from 0.5% to 2%
by weight in the present compositions to provide fabric softener
benefits concurrently with fabric cle~nin~. Clay softeners can be used
in combination with amine and cationic softeners as disclosed, for
e~ample, in U.S. Patent 4,375,416 and U.S. Patent 4,291,071.
Other In~redients - A wide variety of other functional ingredients
useful in deter~ t compositions can be included in the compositions
herein, including other active ingredients, carriers, hydrotropes,
proces~in~ aids, dyes or pigments, solvents for liquid formulations,
solid fillers for bar compositions. If high s~ ing is desired, suds
boosters such as the Clo-C16 alkanol~mi~les can be incorporated into
the compositions, typically at 1%-10% levels. The C1o-C14
monoethanol and diethanol amides illustrate a typical class of such suds
boosters. Use of such suds boosters with high sudsing adjunct
surfactants such as the amine o~ides, betaines and s~lt~ines noted
above is also advantageous. If desired, soluble magnesium salts such
as MgCl2, MgSO4, and the like, can be added at levels of, typically,
CA 0221~669 1997-09-16
W O96/29281 PCTrUS96/02768
36
0.1%-25~, to provide additional suds and to enhance grease removal
performance.
Various detersive ingredients employed in the present
compositions optionally can be further stabilized by absorbing said
ingredients onto a porous hydrophobic substrate, then coating said
substrate with a hydrophobic coating. Preferably, the detersive
ingredient is admi~ed with a surfactant before being absorbed into the
porous substrate. In use, the detersive ingredient is released from the
substrate into the aqueous washing liquor, where it performs its
intended detersive function.
To illustrate this technique in more detail, a porous hydrophobic
silica (trademark SIPERNAT D10, DeGussa) is admi~ced with a
proteolytic enzyme solution cont~inin.~: 3%-5~ of C13 15 etho;~ylated
alcohol (EO 7) nonionic surfactant. Typically, the enzyme/surfactant
solution is 2.5 X the weight of silica. The resulting powder is
dispersed with stirring in silicone oil (various silicone oil viscosities in
the range of 500-12,500 can be used). The resulting silicone oil
dispersion is emulsified or otherwise added to the final detergent
matri~. By this means, ingredients such as the aforementioned
enzymes, bleaches, bleach activators, bleach catalysts, photoactivators,
dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can
be "protected" for use in deter~ ents.
The detergellt compositions herein will l~lefelably be formulated
such that, during use in aqueous cle~nin~ operations, the wash water
will have a pH of between 6.5 and 11, preferably between 7.5 and
10.5. T.~lln~lry products are typically at pH 9-11. Techniques for
controlling pH at recommended usage levels include the use of buffers,
alkalis, acids, etc., and are well known to those skilled in the art.
Other optional in~redients
Other optional ingredients suitable for inclusion in the compositions of
the invention include perfumes, colours and filler salts, with sodium
sulfate being a prefelred filler salt.
Form of the com~ositions
CA 0221~669 1997-09-16
W O 96/29281 PCTrUS96/02768
37
The detergent compositions of the invention can be form~ ted in any
desirable form such as powders, granulates, pastes, liquids, and gels.
Liquid compositions
The detergent compositions of the present invention may be form~ ted
as liquid detergent compositions. Such liquid detergent compositions
typically comprise from 94% to 35% by weight, preferably from 90%
to 40% by weight, most preferably from 80% to 50% by weight of a
liquid carrier, e.g., water, preferably a mi~ture of water and organic
solvent.
~el compositions
The detergent compositions of the present invention may also be in the
form of gels. Such compositions are typically form~ te~ with
polyakenyl polyether having a molecular weight of from about 750,000
to about 4,000,000.
Solid compositions
The detergent compositions of the invention may also be in the form of
solids, such as powders and granules.
The mean particle size of the components of granular compositions in
accordance with the invention should pre~rably be such that no more
that 5 % of particles are greater than 1 .4mm in diameter and not more
than 5 % of particles are less than 0.15mm in diameter.
The term mean particle size as defined herein is calculated by sieving a
sample of the composition into a number of fractions (typically 5
fractions) on a series of Tyler sieves. The weight fractions thereby
obtained are plotted against the aperture size of the sieves. The mean
particle size is taken to be the aperture size through which 50% by
weight of the sample would pass.
The bulk density of granular deter~;ellt compositions in accordance
with the present invention are particularly useful in concentlated
granular detergent compositions that are characterised by a relatively
high density in comparison with conventional laundry deter~ent
CA 0221~669 1997-09-16
W O96/29281 PCTrUS96/02768
38
compositions. Such high density compositions typically have a bulk
density of at least 600 g/litre, more preferably from 650 g/litre to 1200
g/litre, most preferably from 800g/litre to lOOOg/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 e~ctremity to allow the contents of the
funnel to be emptied into an a~cially aligned cylindrical cup disposed
below the funnel. The funnel is 130 mm high and has internal
diameters of 130 mm and 40 mm at its respective upper and lower
e~ctremities. It is mounted so that the lower e~tremity is 140 mm
above the upper surface of the base. The cup has an overall height of
90 mm, an internal height of 87 mm and an internal diameter of 84
mm. Its nominal volume is 500 ml.
To carry out a 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 e~cess powder
removed from the cup by passing a straight edged implement eg; a
knife, across its upper edge. The filled cup is then weighed and the
value obtained for the weight of powder doubled to provide a bulk
density in g/litre. Replicate measurements are made as required.
Making processes - granular compositions
In general, granular detergent compositions in accordance with the
present invention can be made via a variety of methods including dry
mi~ing, spray drying, agglomeration and gr~n~ tion.
The invention is illustrated in the following non limitin~ e~camples, in
which all percentages are on a weight basis unless otherwise stated.
In the bleaching compositions of the invention and detergent
compositions incorporating the bleaching compositions of the
invention, the abbreviated component identifications have the following
me~ning~;
CA 0221~669 1997-09-16
W O96/29281 PCT~US96/02768
39
CXYAS : Sodium C 14-C 15 predomin~n~ly linear alkyl
sulphate
TAE 50 : Tallow alcohol etho~ylated with 50 moles of
ethylene oxide per mole of alcohol
- C25E3S : Sodium C12-C1s branched alkyl sulphate
condensed with three moles of ethylene o~cide
C24 E5 : A C12 14 branched primary alcohol
condensed with an average of 5 moles of
ethylene o~ide
NaSKS-6 : Crystalline layered silicate of formula
~ -Na2Si205
Carbonate : Anhydrous sodium carbonate with a particle
size between 200~Lm and 900~1m
Zeolite A : Hydrated Sodium Aluminosilicate of formula
Nal2(Alo2sio2)l2- 27H20
having a primary particle size in the range
from 0.1 to 10 micrometers
MA/AA : Copolymer of 1:4 maleic/acrylic acid,
average molecular weight about 70,000.
Percarbonate : Sodium Percarbonate of nominal formula
2Na2C03.3H202
TAED : Tetraacetyl ethylene ~ mine (86% active)
agglomerated with MA/AA
Hydrophobic : (6-non~n~midocaproyl) o~cybenzene sulfonate
pero~cyacid (72% active) agglomerated with citric acid
and
precursor TAE 50
Brightener : Disodium 4,4'-bis(4-anilino-6-morpholino-
1.3.5-triazin-2-yl)amino) stilbene-2:2'-
disulphonate.
HEDP : Hydro~cy-ethane 1,1 diphosphonate
CA 0221~669 1997-09-16
W O96/29281 PCTrUS96/02768
DTPMP : Diethylene tri~mine penta (methylene
phosphonate), marketed by Monsanto under
the Trade name Dequest 2060
Silicone antifoam: Polydimethylsilo~ane foam controller with
Silo~ane-oxyalkylene copolymer as dispersing
agent with a ratio of said foam controller to
said
dispersing agent of 10:1 to 100:1.
Photoactivated: Sulphonated Zinc Phthalocyanine
encapsulated in bleach de~ctrin soluble polymer
Savinase : proteolytic enzyme of standard activity 10T/g
Cellulase : cellulytic enzyme of activity 1000 CEVU/g
Termamyl : Amylolytic enzyme of activity 60KNU~g
Lipolase : Lipolytic enzyme of activity 100kLU/g
Endolase : Endoghlc~n~e A of activity 2T/g
all sold by NOVO Industries A/S
PVNO : Polyvinylpyridine N-o~cide
PVPVI : Copolymer of polyvinylpyrolidone and
vinylimitl~7.ole
CMC : Sodium carbo~cymethyl cellulose
~ SRA : Sulfobenzoyl end capped esters with
o~yethylene
(Soil Release : o~cy and terephthaloyl backbone
Agents)
F~ample 1
The following perfume formulation was prepared:
Aroma chemicals %
He~yl Salicylate 20
Tetrahydromuguol 10
Tetrahydrogeraniol 6
Phenyl ethyl alcohol 8
CA 0221~669 1997-09-16
W O96/29281 PCTrUS96102768
41
Cyclopentadecanolide 10
4-tertiary butyl cyclohe~yl acetate 10
7-acetyl 1,2,3,4,5,6,7,8 9
octanhydro 1,1,6,7 tetra methyl
naphthalene
He~cahydro 4-7-methano-inden-5-yl 5
acetate
Methyl phenyl ethyl ketone 4
Acetaldehyde:Phenyl ethyl propyl 7
acetal
Iso-amyl phenyl ethyl ether 5
2-tertiary butyl cyclohe~yl acetate 4
Phenyl ethyl methyl ether 0.5
Lauric nitrile 0.5
Cis-3-He~enyl Acetate 0.5
Dynascone 10% 0.5
E~ample 2
The following detergent compositions according to the invention were
prepared, where the perfume is as defined in E~cample 1.
Components A B
AgglomerateC25 AS/C45 AS 6.44 6.44
C25 E3S 1.61 1.61
ZeoliteA 4.61 4.61
Carbonate 2.10 2.10
MA/AA 2.51 3.44
CMC 0.28 0.28
PVNO/PVPVI 0.02 0.02
TAED 1.75
Hydrophobic 3.70 4.79
pero~cyacid
bleach
DTPMP 0.38 0.38
MgSO4 0.38 0.38
Dry additiveZeolite A 6.90 7.14
CA 0221~669 1997-09-16
W O96/29281 PCTrUS96/02768
42
SKS-6/citric 8.50 8.50
Carbonate 8.25 8.25
MA/AA 0.65 0.93
SRA 0.20 0.20
Savinase 0.60 0.60
Lipolase 0.14 0.14
Cellulase 0.19 0. 19
Termamyl 0.40 0.40
Endolase 0.15 0.15
Percarbonate 13.25 13.25
HEDP 0.40 0.40
Brightener 0.21 0.21
Photoactivated 0.002 0.002
bleach
Silicone 2.00 2.00
antifoam
Spray on C24 E5 3.10 3.10
C16-C18 1.33 1.33
polyhydro~cy
fatty acid amide
Perfume 0.44 0.44
Minors and miscellaneous to balance
The compositions in accordance with the invention were all seen
having an enhanced perfume stability as well as producing an effective
soil removal performance.
