Note: Descriptions are shown in the official language in which they were submitted.
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DETERGENT COMPOSITIONS
Field of the invention
The present invention relates to detergent compositions comprising a
bleaching system and a perfume composition for providing an effective
cleaning of soiled fabrics together with an effective residual perfume
scent on the laundered fabrics.
Background of the invention
The satisfactory removal of dingy stains from soiled/stained substrates is
a particular challenge to the formulator of a detergent composition,
which has been enabled by the use of bleach components of
hydrophobic type such as preformed hydrophobic peroxyacids or
hydrogen peroxide and hydrophobic peroxyacid precursors.
However, consumer acceptance of cleaning and laundry products is
determined not only by the performance achieved with these products
but the aesthetics associated therewith. The perfume systems are
therefore an important aspect of the successful formulation of such
commercial products.
They are used to cover up the chemical odours of the cleaning
ingredients and provide an aesthetic benefit to the wash process and,
prt:fera~ly the cleaned fabrics.
It has now been found that a problem encountered with detergent
compositions comprising the combination of a hydrophobic bleach
system and a perfume composition is that of the resulting laundered
fabric having a "bleachy' characteristic odour.
Not to be bound by theory, it is believed that the hydrophobic bleach
system which is a substantive bleach interacts with the perfume
deposited on the fabric surface by degrading said perfume.
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The potential for such a problem is enhanced when the detergent
composition comprises a high level of surfactants, said problem being
due to the ability of surfactants, especially anionic surfactants, to
transport the hydrophobic bleaching agent to the fabric surface.
The Applicant has found that the degradation of the perfume at the
fabric surface can be a particular problem when the fabric to be cleaned
has already build up of encrustated metal ions present. This problem can
also further be exarcerbated upon use of a detergent composition having
a low builder content and/or of a hard water medium.
The detergent formulator is thus faced with the dual challenge of
formulating a product which maximises the soil/stain removal
performance without compromising on the aesthetic aspect.
Co-pending application GB 9425876.1 describes perfume raw materials
in presence of a hydrophobic bleaching system wherein the source of
active oxygen is coated to prevent the oxidation of said perfume raw
materials upon storage.
Co-pending application GB 9505518.2 describes detergent compositions
comprising perfume raw materials having a strong resistance to oxidation
from hydrophobic bleaches.
W0 95/02681 describes sensitive materials such as chelating agents
(EDDS~, perfume components or hydrophobic bleaches protected from
oxidative environment by a specific package.
It is further known to the man skilled in the art that perfumes are
composed of volatile ingredients which are susceptible of oxidation upon
storage. Accordingly, the perfume composition may be protected from
the oxidative environment by encapsulation of the perfume with silica
material as described in EP 332258 or adsorption onto porous carrier as
disclosed in UK 2,066,839, US 4,539,135; US 4,713,193, US
4,304,675, W0 94/19449 and WO 94/28107. Although efficient to
protect the perfume from oxidation upon storage and/or to direct the
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perfume to the fabric, these materials will still release or leach the
perfume out of the material upon wash, exposing thus the perfume to
the bleach component at the fabric surface.
Notwithstanding the advance in the art there is stiil a need for a
detergent composition which provide effective soil/stain removal
performance together with an effective residual perfume scent on
laundered fabrics.
The Applicant has now found that this problem can be overcome by the
provision of a metal ion sequestrant present at high leveis within the
detergent composition.
The further addition of an organodiphosphonic component has been
found to be beneficial to the overall performance of the detergent
composition .
Summarv of the invention
The present relates to a deter~ent composition comprising:
a)-a hydrophobic bleaching system selected from
i)- hydrogen peroxide or a source thereof in amount of from 0.1%
to 60% by weight and combined with a hydrophobic peroxyacid
bleach precursor in amount of from 0.1% to 60% by weight,
a preformed hydrophobic peroxyacid in amount of from 0.1% to
60% by weight, and
iii) mixtures of i) and ii),
wherein a hydrophobic peroxyacid bleach precursor is defined as a
compound which produces under perhydrolysis a hydrophobic peroxyacid
whose parent carboxylic acid has a critical micelle concentration less
than 0.5 moles/litre measured in aqueous solution at 25~C and pH 7, and
wherein a hydrophobic preformed peroxyacid is defined as a compound
whose parent carboxylic acid has a critical micelle concentration less
than 0.5 moles/litre measured in aqueous solution at 25~C and pH 7,
b)-up to 5% by weight of a perfume composition, and
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c)-at least 0.6% by weight of a metal ion sequestrant selected from
aminocarboxylate compounds, aminophosphonates and mixtures thereof.
In a preferred embodiment, the present invention further comprises an
organo diphosphonic compound.
Detailed description of the invention
HvdroPhobic bleach svstem
An essential component of the invention is a hydrophobic bleach system
selected from hydrogen peroxide or a source thereof combined with a
hydrophobic peroxyacid bleach precursor, a preformed hydrophobic
peroxyacid and any mixtures thereof. Preferred sources of hydrogen
peroxide include perhydrate bleaches.
Perhvdrate bleach
The perhydrate is typically an inorganic perhydrate bleach, normally in
the form of the sodium salt, as the source of alkaline hydrogen peroxide
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 alkalimetal inorganic salts such as
perborate monohydrate or tetrahydrate, percarbonate, perphosphate and
persilicate salts but is conventionally an alkali metal perborate or
percarbonate.
-
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. 5
Sodium percarbonate, which is the preferred perhydrate, is an addition
compound having a formula corresponding to 2Na2C03.3H202, and is
avai!able commercially as a crystalline solid. Most commercially avaiiable
material includes a low level of a heavy metal seque:iLrallt such as EDTA,
1-hydroxyethylidene 1, 1-diphosphonic acid (HEDP) or an amino-
phosphonate, that is incorporated during the manufacturing process. For
the purposes of the detergent composition aspect of the present
invention, the percarbonate can be incorporated into detergent
compositions without additional protection, but preferred executions of
such compositions utilise a coated form of the material. A variety of
coatings can be used including borate, boric acid and citrate or sodium
silicate of SiO2:Na20 ratio from 1.6:1 to 3.4:1, preferably 2.8:1, applied
as an aqueous solution to give a level of from 2% to 10%, (normally
from 3% to 5%) of silicate solids by weight of the percarbonate.
However the most preferred coating is a mixture 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 approximately 500-
1 000 micrometers.
HvdroPhobic oeroxYacid bleach r recursor
One form of the essential hydrophobic bleach system component of the
invention is a hydrophobic peroxyacid bleach precursor which produces
upon perhydrolysis hydrophobic peroxyacid 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 snd pH 7.
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Preferably, the peroxyacid backbone chain contains at least 7 carbons
which may be linear or partly or totaily branched or cyclic and any
mixtures thereof.
The peroxyacid bleach precursors are norrnally 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 detergent composition.
Preferably, hydrophobic peroxyacid bleach precursor compounds are
selected from bleach precursor compounds which comprise at least one
acyl group forming the peroxyacid moiety bonded to a leaving group
through an
-0- or-N- linkage.
Suitable peroxyacid bleach precursors for the purpose of the invention
are the amide substituted compounds of the following general formulae:
R1 N(R5)C(O)R2C~O~L or Rl C(O~N~R5~R2C(O)L
wherein R1 is an aryl or alkaryl group with from 1 to 14 carbon atoms,
R2 is an alkylene, arylene, and alkarylene group containing from 1 to 14
carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group containing 1
to 10 carbon atoms and L can be essentially any leaving group. R 1
preferably contains from 6 to 12 carbon atoms. R2 preferably contains
from 4 to 8 carbon atoms. R1 may ~e straight chain or branched alkyl,
substituted aryl or alkylaryl containing branching, substitution, or both
and may be sourced from either synthetic sources or natural sources
including for example, tallow fat. Analogous structural variations are
permissible for R2. R2 can include alkyl, aryl, wherein said R2 may also
contain haiogen, 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.
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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
difficult to stabilize for use in a detergent composition.
Preferred L groups are selected from:
--~~ . --~~Y a nd --O~$R3Y
--N--C--R1 _N N --N--C--CH--R4
R3 L~ R3 Y
y
~:~3 r
--o--C H =c--C I I--C H 2 --o--c H =C--C H =C H 2
Il Y 11
--O--C--R1 ,C H2--C~ --N>--~NR
O O
R3 0 Y
--O--C =C H R4 , and R3 o
and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group
containing from 1 to 14 carbon atoms, R3 is an alkyl chain containing
from 1 to 8 carbon atoms, R4 is H-or R3, and Y is H or a solubilizing
group. Any of ~1, R3 and R4 may be substituted by essentially any
functionsl group including, for example alkyl, hydroxy, alkoxy, halogen,
amine, nitrosyl, amide and ammonium or alkyl ammmonium groups
The preferred solubilizing groups are -S03-M +, -C02-M +, -S04-M +,
-N + (R314X- and O <--N(R3)3 and most preferably -S03-M + and
-C02-M+ wherein R3 is an alkyl chain containing 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 metal, ammonium or substituted ammonium
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cation, with sodium and potassium being most preferred, and X is a
halide, hydroxide, methylsulfate or acetate anion.
Other suitable L groups for use herein, include a leaving group selected
from a caprolactam leaving group, a valerolactam leaving group and
mixture thereof.
Preferred examples of bleach precursors of the above formulae include
amide substituted peroxyacid precursor compounds selected from (6-
octanamido-caproyl)oxybenzenesulfonate, ~6-nonanamidocaproyl)oxy
benzene sulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and
mixtures thereof as described in EP-A-0 1 70386.
Still another class of bleach precursor is the class of alkyl percarboxylic
acid bleach precursors. Preferred alkyl percarboxylic acid precursors
include nonanoyl oxy benzene sulphonate tNOBS described in US
4,412,934) and 3,5,5-tri-methyl hexanoyl oxybenzene sulfonate
(ISONOBS described in EP120,591) and salts thereof.
Still another class of hydrophobic bleach activators are the N-acylatedprecursor compounds of the lactam class disclosed generally in GB-A-
955735. Preferred materials of this class comprise the caprolactams.
Suitable caprolactam bleach precursors are of the formula:
o
Il
O C CH2 CH2
! I CH2
R 1 C N
CH2 CH2
wherein R1 is an alkyl, aryl, alkoxyaryl or alkaryl ~roup containing from 6
to 12 carbon atoms. Preferred hydrophobic N-acyl caprolactam bleach
precursor materials are selected from benzoyl caproiactam, octanoyl
caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl
=
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caprolactam, 3,5,5-trimethylhexanoyl caprolactam and mixtures thereof.
A most preferred is nonanoyl caprolactam.
Suitable valero lactams have the formula:
.
o
O C C E~ 2 C H 2
R 1 -- C N
CH2 CH2
wherein R1 is an alkyl, aryl, alkoxyaryl or alkaryl group containing from 6
to 12 carbon atoms. More preferably, R1 is selected from phenyl,
heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl and mixtures thereof.
Mixtures of any of the peroxyacid bleach precursor, herein before
described, may also be used.
~ tional co-Precursors
Other bleach precursors may be used in addition to the hydrophobic
bleach precursor so as to provide a detergent composition with a broader
spectrum of soil removal. These may include cationic bleach precursors,
hydrophilic bleach precursors and mixtures thereof.
Suitable cationic bleach precursors are described in U.S. 4,904,406;
4,751,015; 4,988,451; 4,3g7,757; 5,269,962; 5,127,852;
5,093,022; 5,106,528; GB 1,382,594; EP 475,512, 458,396 and
284,292; and in JP 87-318,332. Examples of preferred cationic
peroxyacid precursors are described in GB Patent Application No.
9407944.9 and US Patent Application Nos. 08/298903, 08/298650,
08/298904 and 08/298906.
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Suitable cationic peroxyacid precursors include any of the ammonium or
alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-
acylated caprolactams, N-acylated valerolactams and
monobenzoyltetraacetyl glucose benzoyl peroxides.
Preferred cationic bleach precursors are derived from the valerolactam
and acyl caprolactam compounds, of formula:
+
R~ R'
X- N
C H ~,_ o c--( c H 2 ) x--C H~ 2
CH2--CH2
wherein x is 0 or 1, substituents R, R' and R" are each C1-C10 alkyl or
C2-C4 hydroxy alkyl groups, or {(CyH2y)0]n~R~ wherein y=2-4, n=1-
20 and R"' is a C1-C4 alkyl group or hydrogen and X is an anion.
Suitable hydrophilic peroxyacid bleach precursors include the tetraacetyl
ethylene diamine (TAED) bleach precursor.
Highly preferred among these additional activators is the hydrophilic
peroxyacid bleach precursor tetraacetyl ethylene diamine (TAED) bleach
precursor.
When present, said co-precursors will norrnally be incorporated at a level
of from 0.1% to 60%, preferably from 1% to 40% and most preferably
3 to 25% by weight of the perfumed detergent composition.
,
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$till other suitable bleaching compounds to be used in addition to the
hydrophobic bleaching agents are organic or metal based bleach
catalysts.
Suitable metal based bleach catalysts include the manganese-based
complexes disclosed in U.S. 5,246,621 and U.S. 5,244,594. Preferred
examples of these catalysts include MnlV2(u-0)3(1,4,7-trimethyl-1,4,7-
triazacyclononane)2-(PF6)2, IVlnlll2(u-0) 1 (u-OAc)2(1,4,7-trimethyl-1,4,7-
triazacyclononane)2-(C10432, MnlV4(u-0)6(1,4,7-triazacyclononane~-
(C104)2, MnlllMnlV4(u-031 (u-OAc)2 (1,4,7-trimethyl-1,4,7-
triazacyclononane)2-(CI04)3, and mixtures thereof. Others are described
in EP 549,272. Other iigands suitable for use herein include 1,5,9-
trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane,
2-methyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-
triazacyciononane, and mixtures thereof.
For examples of suitabie bleach catalysts see U.S. 4,246,612 and U.S.
5,227,084. See also U.S. 5,194,416 which teaches mononuclear
manganese ~IV) complexes such as Mn(1,4,7-trimethyl-1,4,7-
triazacyclononane)(OCH3)3 (PF6). Other types of bleach catalyst are
disclosed in U.S. 5,114,606 and U.S. 5,114,611
Still other bleach catalysts are described, for example, in EP 408,131
(cobalt complex catalysts), EP 384,503, and 306,089 (metallo-porphyrin
catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst),
U.S. 4,711,748 and EP 224,952, (absorbed manganese on
aluminosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with
manganese and zinc or magnesium salt), U.S. 4,626,373
~manganese/ligand catalyst), U.S. 4,119,557 (ferric complex catalyst),
German Pat. specification 2,054,019 (cobalt chelant catalyst) Canadian
866,191 (transition metal-containing salts), U.S. 4,430,243 (chelants
with manganese cations and non-catalytic metal cations), and U . S.
4,728,455 tmanganese gluconate catalysts~.
Typical levels of catalysts are such as to provide on the order of at least
one part per ten million of the active bleach catalyst species in the
aqueous washing liquor, and will preferably provide from 0.1 ppm to 700
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12
ppm, more preferably from 1 ppm to 500 ppm, of the catalyst species in
the laundry liquor.
Still other suitable bleaching compounds to be used in addition to the
hydrophobic bleaching agents are bleaching agents of the hypohalite
type that are oxidative bleaches and subsequently lead to the formation
of halide ion. Common among these types of bleaches are the alkaline
metal and alkaline earth metal hypochlorites, hypobromites and
hypoiodites although other bleaches that are organic based sources of
halide, such as chloroisocyanurates, are also applicable.
Examples of hypohalite bleaches include sodium hypochlorite, potassium
hypochlorite, calcium hypochlorite, magnesium hypochlorite, sodiurn
hypobromite, potassium hypobromite, calcium hypobromite, magnesium
hypobromite, sodium hypoiodite and potassium hypoiodite.
Preformed hYdroPhobic l)eroxyacid compound
Another form of the essential hydrophobic bleach system component of
the invention is a preformed hydrophobic peroxyacid bleaching agent and
salt thereof whose parent carboxylic acid has a critical micelle
concentration less than 0.~ moles/litre and wherein said critical micelle
concentration is measured in aqueous solution at 25~C and pH 7.
Preferably, the peroxyacid backbone chain contains at least 7 carbons
which may be linear, partly or totally branched, or cyclic and any
mixtures thereof.
Preferably, hydrophobic peroxyacid bleach compounds are selected from
peroxyacid bleach compounds which comprise at least one acyl group
forming the peroxyacid moiety bonded to a leaving group through an -O-
or-N- iinkage.
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Preformed hydrophobic peroxyacid compounds will typically be in
amount of from 0.1% to 60%, preferably from 3% to 20% by weight.
Suitable examples of this class of agents include (6-octylamino)-6-oxo-
caproic acid, (6-nonylamino)-6-oxo-caproic acid, ~6-decylamino)-6-oxo-
caproic acid, magnesium monoperoxyphthalate hexahydrate, the
magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-
oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching
agents are disclosed in U.S. 4,483,781, U.S. 4,634,551, EP 0,133,354,
U.S. 4,412,934 and EP 0,170,386. A preferred hydrophobic preformed
peroxyacid bleach compound for the purpose of the invention is
monononylamido peroxycarboxylic acid.
Perfume comr osition
Another essential component of the invention is a perfume composition.
The compositions of the invention comprise said perfume composition,
or mixtures thereof, in amounts of up to 5.0%, preferably 0.01% to 2%,
most preferably from 0.05% to 1% by weight of the detergent
composition.
Suitable perfumes herein include materials which provide an olfactory
aesthetic benefit and/or cover any "chemical" odor that the product may
have.
Preferably the perfume composition comprises aroma chemicals selected
from primary and secondary alcohols, aliphatic aldehydes, hydrocinnamic
aldehydes, esters excluding salicylates, unsaturated ketones and
mixtures thereof.
Primary alcohols suitable for the purpose of the invention are 3,7-
dimethyl-6-octen-1-ol, 3,7-dimethyl-2,6-octadien-1-ol, phenyl ethyl
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alcohol, 1-pentanol, 3-methyl-5-phenyl and cyclohexyl ethyl alcohol.
Preferred primary alcohols are 3,7-dimethyl-6-octen-1-ol, 3,7-dimethyl-
2,6-octadien-1-ol and phenyl ethyl alcohol.
Secondary alcohols suitable for use in the perfume composition are
cyclohexanol,2-tertiary butyl, 4-methyl-3-decen-5-ol, cyclohexanol,4-
tertiary butyl and 4-iso propyl cyclohexanol. Preferred secondary alcohols
are cyclohexanol,2-tertiary butyl and 4-methyl-3-decen-5-ol. When used
such alcohols compounds will be at a level of from 1% to 50%,
preferably at a level of from 20% to 45% and more preferably from 25%
to 35% by weight of the perfume composition.
Aliphatic aldehydes suitable for the purpose of the invention are octanal,
nonanal, decanal, undecanal, dodecanal, 1 0-undecenal, 2-methyl
undecanal and 2-methyl decanal.
Hydrocinnamic aldehydes suitable for the purpose of the invention are 2-
methyl-3-(4-tertiary butyl phenyl) propanal and 2-methyl-3-(4-iso propyl
phenyl) propanal. When used such aliphatic and hydrocinnamic
aldehydes will be at a level of up to 30%, preferably at a level of up to
20% and more preferably up to 10% by weight of the perfume
compositlon.
Esters, excluding salicylates, suitable for the purpose of the invention are
benzyl acetate, benzyl propionate, phenyl ethyl acetate, citronellyl
acetate, geranyl acetate, 2-methyl-3-phenyl-propan-2-yl acetate, 4-
tertiary butyl cyclohexyl acetate, 2-tertiary butyl cyclohexyl acetate,
hexahydro-4,7-methano-inden-5-yl - acetate, hexahydro-4,7-methano-
inden-6-yl acetate, hexahydro-4, 7-methano-inden-5-yl propionate,
hexahydro-4,7-methano-inden-6-yl propionate and methyl benzoate.
Preferred esters, excluding salicylates, are 2-methyl-3-phenyl-propan-2-yl
acetate, 2-tertiary butyl cyclohexyl acetate, hexahydro-4,7-methano-
inden-5-yl acetate, hexahydro-4,7-methano-inden-6-yl acetate,
hexahydro-4,7-methano-inden-5-yl propionate, hexahydro-4,7-methano-
inden-6-yl propinate and methyl benzoate. When used such esters
excluding salicylates will be at a level of from 5% to 50%, preferably at
a level of from 10% to 40% and more preferably from 25% to 35% by
weight of the perfume composition.
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Unsaturated ketones suitable for the purpose of the invention are 7-
acetyl 1,2,3,4,5,6,7,8-octanhydro 1,1,6,7 tetra methyl naphtalene, 3-
buten-2-one 3-methyl-4-~2,6,6, trimethyl-2- cyclohexen-1-yl), 3-buten-2-
one 4-~2,6,6-trimethyl-1-cyclohexen-1-yl), 3-buten-2-one 4-~2,6,6-
trimethyl-2-cyclohexen-1-yl) and ketone cedr-8-enyl methyl. When used
such unsaturated ketones will be at a level of from up to 30%,
preferably at a level of up to 25 % by weight of the perfume
composition .
The total sum of the weight of said aroma chemicals, described herein
before, present in the perfume composition is at least 30%, preferably at
least 50% and more preferably at least 80% by weight of the perfume.
Additional perfume ingredients which may be of use herein are given in
"Perfume and Flavor Chemicals (Aroma Chemicals)," Steffen Arctander,
published by the author, 1969, along with their odor character, and their
physical and chemical properties, such as boiling point and molecular
weight, .
If necessary, the perfume composition may further be protected from the
oxidative environment which arise upon storage. This may be done by
encapsulation of the perfume with silica material as described in EP
332259 or adsorption onto porous carrier as disclosed in UK 2,066,839,
US 4,539,135; US 4,713,193, US 4,304,675, W0 94/19449 and W0
94/28107.
Metal ion sequestrants
The other essential component of the invention is a metal ion
sequestrant. By metal ion seques Lr ants it is meant components which
act to sequester (chelate) me1:al ions. These components may also have
calcium and magnesium chelation capacity, but ,~,referentially they bind
heavy metal ions such as iron, manganese and copper.
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1 6
Metal ion sequestrants are preferabiy present at a level of from 0.6% to
20%, more preferably from 0.8% to 10%, most preferably from 1% to
5% by weight of the compositions.
Metal ion sequestrants, which are acidic in nature, having for example
phosphonic acid or carboxylic acid functionalities, may be present either
in their acid form or as a complex/salt with a suitable counter cation
such as an alkali or alkaline metal ion, ammonium, or substituted
ammoniun~ ion, or any mixtures thereof. Preferably any salts/complexes
are water soluble. The molar ratio of said counter cation to the metal ion
sequestrant is preferably at least 1:1.
Suitable metal ion sequestrants for use herein include the or~ano
aminophosphonates, such as the amino alkylene poly (alkylene
phosphonates) and nitrilo trimethyfene phosphonates. Preferred organo
aminophosphonates are diethylene triamine penta (methylene
phosphonate) and hexamethylene diamine tetra (methylene
phosphonate) .
Other suitable metal ion sequestrants for use herein include
polyaminocarboxylic acids such as ethylenediamine-N,N'-disuccinic acid
(EDDS), ethylenediamine tetraacetic acid (EDTA), N-
hydroxyethylenediamine triacetic acid, nitrilotriacetic acid (NTA),
ethylene diamine tetrapropionic acid, ethylenediamine-N,N'-diglutamic
acid, 2-hydroxypropylenediamine-N,N'-disuccinic acid,
triethylenetetraamine hexacetic acid, diethylenetriamine pentaacetic acid
(DETPA), trans 1,2 diaminocyclohexane-N,N,N',N'-tetraacetic acid or
ethanoldiglycine. Especially preferred is ethylenediamine-N,N'-disuccinic
acid (EDDS), most preferably present in the form of its S,S isomer,
which is preferred for its biodegradability profile.
Still other suitable metal ion sequestrants for use herein are iminodiacetic
acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino
diacetic acid, described in EP-A -0,317,542 and EP-A-0,399,133.
In a particular embodiment, the detergent composition of the invention
has further been found to produce an enhanced perfume scent benefit in
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presence of one or more crystal growth inhibitor compound of the
organo diphosphonic acid type. Salts or complexes of these
diphosphonic compounds are also considered herein.
Crvstal growth inhibitor
The organo diphosphonic acid component is an optional ingredient herein
preferably present at a level of from 0.1% to 20%, more preferably from
0.15% to 1~;%, most preferably from 0.2% to 2% by weight of the
compositions .
By organo diphosphonic acid it is meant herein an organo diphosphonic
acid which does not contain nitrogen as part of its chemical structure.
This definition therefore excludes the organo aminophosphonates, which
however may be included in compositions of the invention as heavy
metal ion sequesLtants.
The organo diphosphonic acid component may be present in its acid form
or in the form of one of its salts or complexes with a suitable counter
cation. Preferably any salts/complexes are water soluble, with the alkali
metal and alkaline earth metal salts/complexes being especially preferred.
The organo diphosphonic acid is preferably a C1-C4 diphosphonic acid
and more preferably a C2 diphosphonic acid selected from ethylene
diphosphonic acid, a-hydroxy-2 phenyl ethyl diphosphonic acid,
methylene diphosphonic acid, vinylidene 1, 1 diphosphonic acid, 1, 2
dihydroxyethane 1,1 diphosphonic acid and hydroxy-ethane 1,1
diphosphonic acid and any salts thereof and mixtures thereof.
A most preferred organo diphosphonic acid is hydroxy-ethane 1,1
diphosphonic acid (H~DP).
Surfactants
The detergent composition of the invention will also comprise optionally
but preferably one or more surfactants selected from anionic, cationic,
nonionic, ampholytic, amphoteric and zwitterionic surfactants and
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18
mixtures thereof. A typical listing of anionic, nonionic, ampholytic, and
zwitterionic classes, and species of these surfactants, is given in U.S.P.
3,929,678 issued to Laughlin and Heuring on December 30, 197~.
Further examples are given in "Surface Active Agents and Detergents"
(Vol. I and ll by Schwartz, Perry and Berch). A list of suitable cationic
surfactants is given in U.S.P. 4,259,217 issued to Murphy on March 31,
1981 .
Nonlimiting examples of surfactants useful herein include the
conventional C1 1-C1g alkyl benzene sulfonates ~"~AS") and primary,
branched-chain and random C1o-C20 alkyl sulfates ("AS"~, the C10-C1g
secondary (2,3) alkyl sulfates of the formula
CH3(CH2)X(CHOSO3 M~)CH3 and CH3 (CH2)y(CHOSO3 M+) CH2CH3
where x and (y + 1 ) are integers of at least 7, preferably at least 9, and
M is a water-solubilizing cation, especially sodium, unsaturated sulfates
such as oleyl sulfate, the C1 0-C1 8 alkyl alkoxy sulfates (''AEXS'';
especially EO 1-7 ethoxy sulfates~, C10-C18 alkyl alkoxy carboxylates
(especially the EO 1-~ ethoxycarboxylates), the C10-18 glycerol ethers,
the C1 0-C1 8 alkyl polyglycosides and their corresponding sulfated
polyglycosides, and C1 2-C1 8 alpha-sulfonated fatty acid esters. If
desired, the conventional nonionic and amphoteric surfactants such as
the C1 2-C1 8 alkyl ethoxylates ("AE"), including the so-called narrow
peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially
ethoxylates and mixed ethoxy/propoxy), C1 2-C1 8 betaines and
sulfobetaines ("sultaines"), C1o-C1g amine oxides, and the like, can also
be included in the overall compositions. The C 1 o-C 1 8 N-alkyl
polyhydroxy fatty acid amides can also be used. Typical examples
include the C1 2-C1 8 N-methylglucamides. See WO 9,206,154. Other
sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid
amides, such as C1o-C1g N (3-methoxypropyl) glucamide. The N-propyl
through N-hexyl C12-C1g glucamides can be used for low sudsing. Clo-
C20 conventional soaps may also be used. If high sudsing is desired, the
branched-chain C 1 o-C 1 6 soaps may be used.
Other suitable surfactants suitable for the purpose of the invention are
the anionic alkali metal sarcosinates of formula:
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19
R-~ON(R1 )CH2COOM
wherein R is a Cg-C17 linear or branched alkyl or alkenyl group, R1 is a
- C1-C4 alkyl group and M is an alkali metal ion. Preferred examples are
the lauroyl, cocoyl ~C12-C14~, myristyl and oleyl methyl sarcoslnates in
the form of their sodium salts.
Mixtures of anionic and nonionic surfactants are especially useful. Other
conventional useful surfactants are listed in standard texts.
The total amount of surfactants will be generally up to 70%, typically 1
to 55% by weight of the detergent composition. Preferably, high levels
of surfactants present in a to1:al amount of at least 11% by weight, more
preferably 20% by weight of the detergent composition have been found
to be beneficial to the cleaning performance of the detergent
composition. Most preferably, a better cleaning performance is observed
where at least one of the surfactant component is an anionic surfactant.
The detergent compositions of the invention may also contain additional
detergent components. The precise nature of these additional
components and levels of incorporation thereof will depend on the
physical form of the composition, and the nature of the cleaning
operation for which it is to be used.
The compositions of the invention may, for example, be formulated as
hand and machine laundry detergent compositions, including laundry
additive compositions and compositions suitable for use in the
pretreatment of stained fabrics and machine dishwashing compositions.
Additional otional detergent comPonents
Builders
Detergent builders can optionally be included in the compositions herein
to assist in controlling mineral hardness. Inorganic as well as organic
-
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builders can be used. Builders are typically used in fabric laundering
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. When present, the
compositions will typically comprise at least 1% builder. Granular
formulations typically comprise from 5% to 80%, more preferably less
than 25% by weight, of the detergent builder. Lower or higher levels of
builder, however, are not meant to be excluded.
~uilders, especially non phosphorus containing builders, present at low
levels such as less than 25% by weight of the detergent composition
have been found to provide a fabric encrustation problem, which thus
reduces the amount of perfume deposition on the fabric. The detergent
composition of the invention has surprisingly been found to be beneficial
to the scent of laundered fabric even in the presence of such low level of
builders.
Inorganic or phosphàte-containing detergent builders include, but are not
limited to, the alkaii metal, ammonium and alkanolammonium salts of
polyphosphates (exemplified 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 polycarboxylates. Examples of silicate builders are the
crystalline layered silicates, such as the layered sodium silicates
described in U.S. 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-Na2Si20~ morphology form
of layered silicate. It can be prepared by methods such as those
described in DE-A-3,417,649 and DE-~-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 NaMSix02x+ 1 .YH20 wherein
M is sodium or hydrogen, x is a number from 1.~ to 4, preferably 2, and
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21
y is a number from O to 20, preferably O can be used herein. Various
other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and
NaSKS-11, as the alpha, beta and gamma forms. As noted above, the
delta-Na2Si20s (NaSKS-6 form) is most preferred for use herein. Other
silicates may also be useful such as for example magnesium silicate,
which can serve as a crispening agent in granular formulations, as a
stabilising agent for oxygen bleaches, and as a component of suds
control systems.
Aluminosilicate builders are of great importance in most currently
marketed heavy duty granular detergent compositions, and can also be a
significant builder ingredient in liquid detergent formulations.
Aluminosilicate builders include those having the empirical formula:
Naz[(Alo2)z(sio2)yl ~XH20
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 x is an integer from 15 to 264.
Useful aluminosilicate ion exchange materials are commercially available.
These aluminosilicates can be crystalline or amorphous in structure and
can be naturally-occurring aluminosilicates or synthetically derived. A
method for producing aluminosilicate ion exchange materials is disclosed
in U.S. 3,985,669. Preferred synthetic crystalline aluminosilicate ion
exchange 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 exchange
material has the formula:
Na 1 2l(AI02) 1 2~Si~2) 1 2]-XH20
wherein x is from 20 to 30, especially 27. This material is known as
Zeolite A. Dehydrated zeolites ~x = O - 10) may also be used herein.
F'referably, the aluminosilicate has a particle size of 0.1-10 microns in
diameter.
-
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22
Suitable organic detergent builders include, but are not restricted to, a
wide variety of polycarboxylate compounds. As used herein,
"polycarboxylate" refers to compounds having a plurality of carboxylate
groups, preferably at ieast 3 carboxylates. Polycarboxylate builder can
generally be added to the composition in acid forrn, but can aiso be
added in the form of a neutralised salt. When utilized in salt form, alkali
metals, such as sodium, potassium, and lithium, or alkanolammonium
salts are preferred.
Included among the polycarboxylate builders are a variety of categories
of useful materials. One important category o~ polycarboxylate builders
encompasses the ether polycarboxylates, including oxydisuccinate, as
disclosed in U.S. 3,128,287 and U.S. 3,635,830. See also "TMS/TDS"
builders of U.S. 4,663,071. Suitable ether polycarboxylates also include
cyclic compounds, particularly alicyclic compounds, such as those
described in U.S. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and
4,102,903.
Other useful detergency builders include the ether
hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene
or vinyl methyl ether, or acrylic acid, 1, 3, 5-trihydroxy benzene-2, 4, 6-
trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali
metal, ammonium and substituted ammonium salts of polyacetic acids
such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well
as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic
acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,
carboxymethytoxysuccinic acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly
sodium salt), are polycarboxylate builders of particular importance for
heavy duty liquid deter~ent 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. Oxydisuccinates are also especially useful in
such compositions and combinations.
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23
Also suitable in the compositions of the invention are the 3,3-dicarboxy-
4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S.
4,566,984. Useful succinic acid builders include the Cs-C20 alkyl and
alkenyl succinic acids and salts thereof. A particularly preferred
compound of this type is dodecenylsuccinic acid. Specific examples of
- succinate builders include: laurylsuccinate, myristylsuccinate,
palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-
pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred
builders of this group, and are described in EP 0,200,263.
Other suitable polycarboxylates are disclosed in U.S. 4,144,226 and in
U.S. 3,308,067. See also U.S. 3,723,322.
Fatty acids, e.g., C12-C1 g monocarboxylic 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 diminution of sudsing, which should be taken into account by
the formulator.
Deteraent adiunct materials
The compositions herein can optionally include one or more other
detergent adjunct materials or other materials for assisting or enhancing
cleaning performance, treatment of the substrate to be cleaned, or to
modify the aesthetics of the detergent composition (e.g. colorants, dyes,
etc.). The following are illustrative examples of such adjunct materials.
Enzvmes
The enzymes to be incorporated include proteases, amylases, lipases,
cellulases, and peroxidases, as well as mixtures thereof. Other types of
enzymes may also be included. They may be of any suitable origin, such
as vegetable, animal, bacterial, fungal and yeast origin. However, their
cho;ce is governed by several factors such as pH-activity and/or stability
optima, thermostability and stability versus active detergents and
builders. In this respect bacterial or fungal enzymes are preferred, such
as bacterial amylases and proteases, and fungal cellulases.
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Enzymes are normally incorporated at levels sufficient 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%, preferably 0.01 %-1 % by weight
of a commercial enzyme preparation.
Suitable examples 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 maximum activity
throughout the pH range of 8-12, developed and sold by Novo Industries
A/S under the registered trade name ESPERASE. The preFaration 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).
Amylases include, for example, o~-amylases described in GB 1,296,839
(Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL,
Novo Industries. Fungamyl (Novo) is especially useful.
The cellulases usable in the present invention include both bacterial or
fungal cellulase. P~eferably, they will have a pH optimum of between 5
and 9.5. Suitable cellulases are disclosed in U~S. 4,435,307, which
discloses fungal cellulase produced from Humicola insoiens and Humicola
strain DSM1800 or a celll~lase 212-producing fungus belonging to the
genus Aeromonas, and cellulase extracted 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 Industries A/S are especially
useful .
Suitable lipase en~ymes for detergent usage include those produced by
microorganisms of the Pseudomonas group, such as Pseudomonas
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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
~o. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,"
hereinafter referred to as "Amano-P." Other commercial lipases include
Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter
viscosum var. Iipolyticum 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.
Peroxidase enzymes are used in combination with oxygen sources, e.g.,
percarbonate, perborate, persulfate, hydrogen peroxide, 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. Peroxidase enzymes are known in the
art, and include, for example, horseradish peroxidase, ligninase, and
haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-
containing detergent compositions are disclosed, for example, in WO
89/09981 3.
A wide range of enzyme materials and means for their incorporation into
synthetic detergent compositions are also disclosed in U.S. 3,553,139.
Enzymes are further disclosed in U.S. 4,101,457 and in U.S. 4,507,219.
Enzyme materials useful for liquid- detergent formulations, and their
incorporation into such formulations, are disclosed in U.S. 4,261,868.
Enzymes for use in detergents can be stabilized by various techniques.
Enzyme stahilisation techniques are disclosed and exemplified in U.S.
3,600,319 and EP 0,199,405. Enzyme stahilisation systems are also
described, for example, in U.S. 3,519,570.
Polvmeric DisPersing Aqents
Polymeric dispersing agents can be utilized at levels from 0.5~/O to 8%,
by weight, in the compositions herein, especially in the presence of
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26
zeolite and/or layered silicate builders. Suitable polymeric dispersing
agents include polymeric polycarboxyiates and polyethylene glycols,
although others known in the art can also be used.
Polyrneric polycarboxylate materials can be prepared by polymerizing or
copolymerizing suitable unsaturated monomers, preferably in their acid
form. Unsaturated monomeric acids that can be polymerized to form
suitable polymeric polycarboxylates are selected from 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 polycarboxylates herein of monomeric
segments, containing no carboxylate radicals such as vinylmethyl ether,
styrene, ethylene, etc. is suitable provided that such segments do not
constitute more than 40% by weight.
Polymeric polycarboxylate materials can also optionally include further
monomeric units such as nonionic spacing units. For exampie, suitable
nonionic spacing units may include vinyl alcohol or vinyl acetate.
Particularly preferred polymerio polycarboxylates are co-polymers derived
from monomers of acrylic acid and maleic acid. The average molecular
weight of such polymers in the acid form preferal,ly ranges from 2,000
to 10,000, more preferably from 4,000 to 7,000 and most preferably
from 4,000 to 5,000. Water-soluble salts of such acrylic/maleic acid
polymers can include, for example, the alkali metal, ammonium and
substituted ammonium salts. Soluble polymers of this 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. 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. Soluble acrylate/maleate copolymers of this type are known
materials which are described in EP 66915 as well as in EP 193,360,
which also describes such polymers comprising hydroxypropylacrylate.
Of these acrylic/maleic-based copolymers, the water-soluble salts of
copolymers of acrylic acid and maleic acid are preferred.
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27
Another class of polymeric polycarboxylic acid compounds suitable for
use herein are the homo-polymeric polycarboxylic acid compounds
derived from acrylic acid. The average molecular weight of such homo-
polymers in the acid form preferably ranges from 2,000 to 100,000,
more preferably from 3,000 to 75,~00, most preferably from 4,000 to
65,000.
A further example of polymeric polycarboxylic compounds which may be
used herein include the maleic/acryiic/vinyl alcohol terpolymers. Such
materials are also disclosed in EP 193,360, including, for example, the
45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.
Another example of polymeric polycarboxylic compounds which may be
used herein include the biodegradable polyaspartic acid and polyglutamic
acid compounds.
Clav Soil Removal/Anti-redePosition Aqents
Granular detergent compositions which contain these compounds
typically contain from 0.01% to 10.0% by weight of the water-soluble
ethoxylates amines; liquid detergent compositions typicaliy contain
0.01 % to 5%.
The most preferred soil release and anti-redeposition agent is ethoxylated
tetraethylenepentamine. Exemplary ethoxylated amines are further
described in U.S. 4,597,898. 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 ethoxylated amine polymers disclosed in EP
111,984; the zwitterionic polymers disclosed in EP 112,592; and the
amine oxides disclosed in U.S. 4,548,744 and the carboxy methyl
cellulose ~CMC) materials. These materials are well known in the art.
Polvmeric Soil Release Aaent
Polymeric soil release agents are characterised by having both
hydrophilic segments, to hydrophilize the surface of hydrophobic fibers,
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28
~ such as polyester and nylonr and hydrophobic segments, 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.
The polymeric soil release agents useful herein especially include those
soil release agents having: (a) one or more nonionic hydrophile
components consisting essentially of (i) polyoxyethylene segments with
a degree of polymerization of at least 2, or (ii) oxypropylene or
polyoxypropylene segments with a degree of polymerization of from 2 to
10, wherein said hydrophile segment does not encompass any
oxypropylene unit unless it is bonded to adjacent moieties at each end by
ether linkages, or (iii) a mixture of oxyalkylene units comprising
oxyethylene and from 1 to 30 oxypropylene units wherein said mixture
contains a sufficient amount of oxyethylene units such that the
hydrophile component has hydrophilicity great enough to increase the
hydrophilicity of conventional polyester synthetic fiber surfaces upon
deposit of the soil release agent on such surface, said hydrophile
segments preferably comprising at least 25% oxyethylene units and
more preferably, especially for such components having 20 to 30
oxypropylene units, at least 50% oxyethylene units; or (b) one or more
hydrophobe components comprising (i) C3 oxyalkylene terephthalate
segments, wherein, if said hydrophobe components also comprise
oxyethylene terephthalate, the ratio of oxyethylene terephthalate:C3
oxyalkylene terephthalate units is 2:~ or lower, (ii) C4-C6 alkylene or oxy
C4-C6 alkylene segments, or mixtures therein, (iii) poly (vinyl ester)
seyme~ I ls, preferably polyvinyl acetate), having a degree of
polymerization of at least 2, or (iv) C1-C4 alkyl ether or C4 hydroxyalkyl
ether substituents, or mixtures therein, wherein said substituents are
present in the form of C 1 -C4 alkyl ether or C4 hydroxyalkyl ether
cellulose derivatives, or mixtures therein, and such cellulose derivatives
are amphiphilic, whereby they have a sufficient level of C1-C4 alkyl ether
and/or C4 hydroxyalkyl ether units to deposit upon conventional
polyester synthetic fiber surfaces and retain a sufficient level of
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29
hydroxyls, once adhered to such conventional synthetic fiber surface, to
increase fiber surface hydrophilicity, or a combination of (a) and (b).
Typicaliy, the polyoxyethylene segments of (a)(i) will have a degree of
polymerization of from 200, although higher ievels can be used,
preferably ~rom 3 to 150, more preferably from 6 to 100. Suitable oxy
C4-C6 alkylene hydrophobe segments include, but are not limited to,
end-caps of polymeric soil release agents such as
MO3S(CH2)nOCH2CH2O-, where M is sodium and n is an integer from
4-6, as disclosed in U.S. 4,721,580.
Polymeric soil release agents useful in the present invention also include
cellulosic derivatives such as hydroxyether cellulosic polymers,
copolymeric blocks of ethylene terephthalate or propylene terephthalate
with polyethylene oxide or polypropylene oxide terephthalate, and the
like. Such agents are commercially available and include hydroxyethers
of cellulose such as METHOCEL (Dow) and carboxy alkyl of cellulose
such as \/letolose (Shin Etsu). Cellulosic soil release agents for use herein
also include those selected from C1-C4 alkyl and C4 hydroxyalkyl
cellulose; see U.S. 4,000,093.
Soil release agents characterised by poly(vinyl ester) hydrophobe
segments include graft copolymers of poly(vinyl ester~, e.g., C1-C6 vinyl
esters, preferably poly~vinyl acetate) grafted onto polyalkylene oxide
backbones, such as polyethylene oxide backbones (see EP O 219 048).
Commercially available soil release agents of this kind include the
SOKALAN type of material, e.g., S~KALAN HP-22, available from BASF
(West Germany).
One type of preferred soil release agent is a copolymer having random
blocks of ethylene terephthalate and polyethylene oxide (PEO)
terephthalate. The molecular weight of this polymeric soil release agent
is in the range of from 25,000 to 55,000. See U.S. 3,959,230 and U.S.
3,893,929.
Another preferled polymeric soil release agent is a polyester with repeat
units of ethylene terephthalate units which contains 10-15% by weight
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of ethylene terephthalate units together with 90-80% by weight of
polyoxyethylene terephthalate units, derived from a polyoxyethylene
glycol of average molecular weight 300-5,000. Examples of this polymer
include the commercially available material ZELCON 5126 (from Dupont)
and MILEASE T (from ICI). See also U.S. 4,702,857.
Another preferred polymeric soil release agent is a sulfonated product of
a substantially linear ester oligomer comprised of an oligomeric ester
backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal
moieties covalently attached to the backbone. These soil release agents
are described in U.S. 4,g68,451. Other suitable polymeric soil release
agents include the terephthalate polyesters of U.S. 4,711,730, the
anionic end-capped oligomeric esters of U.S. 4,7~ 80 and the block
polyester oligomeric compounds of U.S. 4,702,857.
Still another preferred soil release agent is an oligomer with repeat units
of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and
oxy-1,2-propylene units. The repeat units form the backbone of the
oligomer and are preferably terminated with modified isethionate end-
caps. A particularly preferred soil release agent of this type comprises
one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and
oxy-1,2-propyleneoxy units in a ratio of from 1.7 to 1.8, and two end-
cap units of sodium 2-~2-hydroxyethoxy)-ethanesulfonate. Said soil
release agent also comprises from 0.5% to 20%, by weight of the
oligomer, of a crystalline-reducing stabilizer, preferably selected from
xylene sulfonate, cumene sulfonate, toluene sulfonate and mixtures
thereof.
Preferred polymeric soil release agents also include the soil release
agents of U.S. 4,877,8~6, which discloses anionic, especially sulfoaroyl,
end-capped terephthalate esters.
If utilized, soil release agents will generally comprise from 0.01 % to
10.0%, by weight, of the compositions herein, typically from 0.1% to
5%, preferably from 0.2% to 3.0%.
Dve Transfer Inhibitina Aqents
,
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~1
Generaily, such dye transfer inhibiting agents include polyvinyl
pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-
~ vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine,peroxidases, and mixtures thereof. If used, these agents typically
comprise from 0.C)1% 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 struct~ral formula: R-AX-P;
wherein P is a polymerizable unit to which an N-0 group can be attached
or the N-0 group can form part of the polymerizable unit or the N-0
group can be attached to both units; A is one of the following structures:
-NC(0)-, -C(0)0-, -S-, -0-, -N=; x is 0 or 1; and R is aliphatic,
ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any
combination thereof to which the nitrogen of the N-0 group can be
attached or the N-0 group is part of these groups. Preferred polyamine N-
oxides are those wherein R is a heterocyclic group such as pyridine,
pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
The N-0 group can be represented by the following general structures:
(Rl)x--N--(R2)y; N--(Rl)x
(R3)z
wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic
groups or combinations thereof; x, y-and z are 0 or 1; and the nitrogen of
the N-0 group can be attached or form part of any of the aforementioned
groups. The amine oxide unit of the polyamine N-oxides has a pKa < 10,
preferably pKa <7, more preferred pKa <6.
Any polymer backbone can be used as long as the amine oxide polymer
formed is water-soluble and has dye transfer inhibiting properties.
Examples of suitable polymeric backbones are polyvinyls, polyalkylenes,
polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures
thereof. These polymers include random or block copolymers where one
monomer type is an amine N-oxide and the other monomer type is an N-
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32
oxide. The amine N-oxide polymers typically have a ratio of amine to the
amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine
oxide groups present in the polyamine oxide polymer can be varied by
appropriate copolymerization or by an appropriate degree of N-oxidation.
The polyamine oxides 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 "PVN0".
The most preferred polyamine N-oxide useful in the compositions herein
is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of
50,000 and an amine to amine N-oxide ratio of 1 :4.
Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred
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. (The average molecular weight range is determined
by light scattering as described in Barth, et al., Chemical Analvsis, 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 preferably 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 polyvinyl
pyrrolidone ("PVP") having an average molecular weight of from 5,000 to
400,000, preferably from 5,000 to 200,000, and more preferably from
5,000 to 50,000. PVP's are known to persons skilled in the detergent
field; see, for example, EP-A-262,897 and EP-A-256,696. Compositions
containing PVP can also contain polyethylene glycol ("PEG") having an
average molecular weight from 500 to 100,000, preferably from 1,000
to 10,000. Preferably, the ratio of 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.
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33
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 preferabiy 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:
Rl~ R2
N O~N~ I I ~ ~N~(
~N H H N~
R2/ SO3M S03M Rl
wherein R1 is seiected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-
hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a
salt-forming cation such as sodium or potassium.
When in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and
M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-
bis-hydroxyethyl)-s-triazine-2-yl)aminol-2,2'-stilbenedisulfonic acid and
disodium salt. This particular brightener species is commercially marketed
under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-
methylamino and M is a cation such as sodium, the brightener is 4,4'-
bisl(4-anilino-6-(N-2-hydroxyethyl-N-rnethylamino)-s-triazine-2-
yl)amino]Z,2'-stilbenedisulfonic acid disodium salt. This particular
t,rigtltener species is commercially marketed under the tradename Tinopal
5BM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is anilino, R2 is morphilino and M is a
cation such as sodium, the brightener is 4,4'-bisl(4-anilino-6-morphilino-
s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This
particular brightener species is commercially marketed under the
tradename Tinopal AMS-GX by Ciba Geigy Corporation.
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34
Other conventional optical brightener types o~ compounds can optionally
be used in the present compositions to provide conventional fabric
"brightness" benefits, rather than a true dye transfer inhibiting effect.
Such usage is conventional and well-known to detergent formulations.
Conventional optical brighteners or other brightenin~ or whitening agents
known in the art can be incorporated at levels typically from 0.005% to
5%, preferably from 0.01% to 1.2% and most preferably from 0.05% to
1.2%, by weight, into the detergent compositions herein. Commercial
optical brighteners which may be useful can be classified into subgroups,
which include, but are not necessarily limited to, derivatives o~ stilbene,
pyrazoline, coumarin, carboxylic acid, methinecyanines,
dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ring
heterocycles, and other miscellaneous agents. Examples of such
brighteners are disclosed in "The Production and Application of
Fluorescent Bri~htening Agents", M. Zahradnik, Published by John Wiley
& Sons, New York ~1982). Further optical brightener which may also be
used include naphthalimide, benzoxazole, benzofuran, benzimidazole and
any mixtures thereof.
Specific examples of optical brighteners which are useful in the present
compositions are those identified in U.S. 4,790,856. These brighteners
include the PHORWHITE series of brighteners from Verona. Other
brighteners disclosed in this reference include: Tinopal UNPA, T;nopal
CBS and Tinopal 5BM; available from Ciba-Geigy; Artic White C{~ and
Artic White CWD; the 2-(4-styryl-phenyl)-2H-napthor1,2-d~triazoles;
4,4'-bis(1,2,3-triazol-2-yl)-stilbenes;~4,4'-bis(styryl)bisphenyls; and the
aminocoumarins. Specific examples of these brighteners include 4-
methyl-7-diethyl- amino coumarin; 1,2-bis(-benzimidazol-2-yl)ethylene;
1 ,3-diphenyl-pyrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-
naptho-[1,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho[1,2-d]triazole.
See also U.S. 3,646,01 5 .
Suds Suooressors
A wide variety of materials may be used as suds suppressors, and suds
suppressors are well known to those skilled in the art. See, for example,
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Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume
7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category of
suds suppressor of particular interest encompasses monocarboxylic fatty
acid and soluble salts therein. See U.S. 2,954,347. The monocarboxylic
fatty acids and salts thereof used as suds suppressor typically have
hyclrocarbyl 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 lithium salts, and ammonium and
alkanolammonium salts.
The detergent compositions herein may also contain non-surfactant suds
suppressors. These include, for example: high molecular weight
hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid
triglycerides), fatty acid esters of monovalent alcohols, aliphatic C1 8-
C40 ketones (e.g., stearone), etc. Other suds inhibitors include N-
alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to
tetra-alkyldiamine chlortriazines formed as products of cyanuric chloride
with two or three moles of a primary or secondary amine containing 1 to
24 carbon atoms, propylene oxide, 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 haloparalFfin can be utilized in liquid form. It is also
known to utilize waxy 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 example, in U.S. 4,265,779. The hydrocarbons, thus,
include aliphatic, alicyclic, aromabc, and heterocyclic saturated or
unsaturated hydrocarbons having from 12 to 70 carbon atoms. The term
"paraffin," as used in this suds suppressor discussion, is intended to
include mixtures of true paraffins and cyclic hydrocarbons.
Another preferred category of non-surfactant suds suppressors
comprises silicone suds suppressors. This category includes the use of
polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or
emulsions of polyorganosiloxane oils or resins, and combinations of
polyorganosiloxane with silica particles wherein the polyorganosiloxane is
chemisorbed or fused onto the silica. Silicone suds suppressors are well
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36
known in the art and are, for example, disclosed in U.S. 4,265,779 and
EP 354016.
Other silicone suds suppressors are disclosed in U.S. 3,456,839 which
relates to compositions and processes for defoaming aqueous solutions
by incorporating therein small amounts of polydimethylsiloxane fluids.
Mixtures of silicone and silanated silica are described, for instance, in
German Patent Application DOS 2,124,526. Silicone defoamers and
suds controlling agents in granular detergent compositions are disclosed
in U.S. 3,933,672 and in U.S. 4,652,392.
An exemplary silicone based suds suppressor for use herein is a suds
suppressing amount of a suds controlling agent consisting essentially of:
(i) polydimethylsiloxane fluid having a viscosity of from 20 cs.
to 1,500 cs. at 25 ~C;
(ii) from 5 to 50 parts per 100 parts by weight of (i) of siloxane
resin composed of (CH3)3SiO1 /2 units of SiO2 units in a
ratio of from (CH3)3 SiO1/2 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 mixtures thereof
(preferred), or polypropylene glycok The primary silicone suds suppressor
is branched/crosslinked and preferably not linear.
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 solubility in water
at room temperature of more than 2 weight %, preferably more than 5
weight %.
=
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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 giycol/polypropylene glycol, preferably PPG 200/PEG 300.
Preferred is a weight ratio of between 1 :1 and 1 :1 O, most preferably
between 1:3 and 1:6, of polyethylene giycol: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 oxide and
propylene oxide, like PLURONIC L101.
Other suds suppressors useful herein comprise the secondary alcohols
(e.g., 2-alkyl alkanols) and mixtures 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-C1 6 alkyl alcohols
having a C1-C16 chain. A preferred alcohol is 2-butyl octanol, which is
available from Condea under the trademark ISOFOL 12. Mixtures of
secondary alcohols are available under the trademark ISALCHEM 123
from Enichem. Mixed suds suppressors typically comprise mixtures 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 extent that they overflow the
washing machine. Suds suppressors, when utilized, are p~eferably
present in a "suds suppressing amount. By "suds suppressing amount" is
meant that the formulator 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 detergent for use in automatic laundry washing
machines.
The compositions herein will generally comprise from 0% to 5% of suds
suppressor. When utilized as suds suppressors, monocarboxylic 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 monocarboxylate suds suppressor is utilized. Silicone suds
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38
suppressors are typically utilized 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 minimized 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
nerein, these weight percentage values include any silica that may be
utilized in combination with polyorganosiloxane, as well as any adjunct
materials that may be utilized. Monostearyl phosphate suds suppressors
are generally utilized in amounts ranging from 0.1% to 2%, by weight,
of the composition. Hydrocarbon suds suppressors are typically utilized
in amounts ranging 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. ~,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
cleaning. Clay softeners can be used in combination with amine and
cationic softeners as disclosed, for example, in U.S. 4,375,416 and U.S.
4,291 ,071 .
Other Ingredients
A wide variety of other functional ingredients useful in detergent
compositions can be included in the compositions herein, including other
active inyredients, carriers, hydrotropes, processing aids, dyes or
pigments, solvents for liquid formulations, solid fillers for bar
compositions. The detergent compositions herein will preferably be
formulated such that, during use in aqueous cleaning operations, the
wash water will have a pH of between 6;5 and 11, preferably between
7.5 and 10.5. Laundry products are typically at plt ~-11. Techniques for
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39
controlling pH at recommended usage levels include the use of buffers,
alkalis, acids, etc., and are weJI known to those skilled in the art.
Other ol~tional ingredients
Other optional ingredients suitable for inclusion in the compositions of
the invention include colours and filler salts, with sodium sulfate being a
preferred filler salt.
Form of the com~ositions
The detergent compositions of the invention can be formulated in any
desirable form such as powders, granulates, pastes, liquids, and gels.
Liauid comPositions
The detergent compositions of the present invention may be formulated
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, preferabiy a mixture of water and organic solvent.
Gel comnositions
The detergent compositions of the present invention may also be in the
form of gels. Such compositions are~typically formulated with polyakenyl
polyether having a molecular weight of from 750,000 to 4,000,000.
Solid comoositions
The detergent compositions of the invention may also be in the form of
solids, such as powders and granules.
Preferably, the mean particie size of the components of granular
compositions in accordance with the invention should be such that no
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more that ~% of particles are greater than 1.4mm in diameter and not
more than 5% of particles are less than 0.1 5mm in diameter.
The term mean particle size as defined herein is determined by sieving a
sample of the composition into a number of fractions ~typically ~i
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 detergent compositions in accordance with
the present invention are particularly useful in concentrated granular
detergent compositions that are characterised by a relatively high density
in comparison with conventional laundry detergent compositions. Such
high density compositions typically have a bulk density of at least 400
g/litre, more preferably from 650 g/litre to 1200 g/litre, most preferably
from 800g/litre to 1 OOOg/litre.
Making orocesses - aranular compositions
In general, granular detergent compositions in accordance with the
present invention can be made via a variety of methods including dry
mixing, spray drying, agglomeration and granulation.
The invention is illustrated in the following non limiting examples, in
which all percentages are on a weight basis unless otherwise stated.
In the detergent compositions of the invention, the abbreviated
component identifications have the following meanings:
XYAS : Sodium C1x- C1y alkyl sulfate
XYEZ : A C1X 1Y predominantly linear primary alcohol
condensed with an average of Z rnoles of
ethylene oxide
XYEZS : C1x - C1y sodium alkyl sulphate condensed with
an average of Z moles of ethylene oxide per mole
_
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.TFAA : C 1 6-C 1 8 alkyl N-methyl glucamide
NaSKS-6 : Crystalline layered silicate of formula ~-Na2Si20s
Carbonate : Anhydrous sodium carbonate
Silicate : Amorphous sodium silicate (SiO2:Na20 )
MA/AA : Copolymer of 1:4 maleic/acrylic acid, average
molecular weight about 80,000
Zeolite A : Hydrated Sodium Aluminosilicate of formula
Na1 2(A1 ~2Sio2)l 2- 27H20 having a primary
particle size in the range from 1 to 10
micrometers
Citric acid : Anhydrous Citric Acid
Percarbonate : Anhydrous sodium percarbonate bleach of
empirical formula 2Na2C03.3H202 coated with
a mixed salt of formula Na2S04.n.Na2C03
where n is 0.29 and where the weight ratio of
percarbonate to mixed salt is 39:1
TAED : Tetraacetyl ethylene diamine
DETPMP : Diethylenetriamine penta (Methylene phosphonic
acid~ marketed by Monsanto under the Trade
name Dequest 2060.
ExamPle
The following perfume ~ormulations were prepared
Perfume 1 %
Hexyl cinnamic aldehyde 10
Hexyl salicylate 20
Phenyl ethyl alcohol 20
Citronellol 1 2
Geraniol 8
2-Methyl-3-(4-tertiary butyl phenyl) propanal 10
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42
Phenyl ethyl acetate 2
Benzyl acetate 5
4-tertiary butyl cyclohexyl acetate 5
3-Buten-2-oner 4-(2,6,6-trimethyl-1-cyclohexen-1-yl) 3
10-undecenal ~10% in DPG) 5
Per~umc 2 %
Benzyl salicylate 5
Hexyl salicylate 10
Phenyl ethyl alcohol 15
4-lso propyl cyclohexanol 5
Citronellol 1 0
3-Buten-2-one, 4-~2,6,6-trimethyl-1-cyclohexen-1-yl) 15
Heliotropine 4
7-Acetyl, 1, 2, 3, 4, 5, 6, 7, 8-octahydro 1, 1, 6, 7 5
tetra methyl naphtalene
Benzyl acetate 7
4-tertiary butyl cyclohexyl acetate 20
2-Methyl-3-phenyl propan-2-yl acetate 4
The following formulations A, B and C in accordance with the invention
were prepared. Either of perfume 1 or perfume 2 formulations was used.
~ 5AS 12 2
25E3S - 3 3 3
24E5 4 4 4
TFAA 8 8 8
Zeolite A 10.5 10.5 10.5
NaSKS-6 8.5 8.5 8.5
Citric Acid 2.5 2.5 2.5
Percarbonate 17 17 17
Carbonate 13 13 13
MAIAA 2.5 2.5 2.5
DETPMP 1.6 0.95 0.95
HEDP - 0.65 0.65
TAED - - 2. 3
=
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43
6 ~-nonanamidocaproyl) oxybenzene 6.0 6.0 4.7
sulphonate
Perfume (*) 0.5 0.5 0.5
Minors to balance
(*)-perfume composition as defined above
