Note: Descriptions are shown in the official language in which they were submitted.
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HYDROPHOBIC PEROXYACID BLEACH PRECURSOR COMPOSITIONS
STABILISED WITH A WATER SOLUBLE CARBOXYLIC ACID
Technical field
The present invention relates to perozyacid bleach precursor compositions
and to detergent compositions containing them, which have improved
perhydrolysis rate as well as improved storage stability. More
particularly, it relates to bleach activators which in aqueous media
produce hydrophobic perozyacids.
Backeround to the invention
Under alkaline conditions, bleach activators are susceptible to hydrolysis
under alkaline conditions, which thus reduces the storage stability as well
as the perhydrolysis rate when in aqueous wash liquor.
The prior art contains numerous examples of organic perozyacid bleach
precursors coated or agglomerated so as to increase their stability on
storage in detergent compositions and/or to influence their solution
behaviour.
EP-A-0070474 discloses granulate organic perozyacid bleach precursors
prepared by spray drying an aqueous pumpable dispersion containing an
N-acyl or O-acyl compound together with at least one water soluble
cellulose ether, starch or starch derivative in a weight ratio of activator to
coati. of from 98:2 to 90:10.
GB-A-1507312 discloses the coating of organic perozyacid bleach
precursors with a mixture of alkali metal Cg - C22 fatty acid salts in
admixture with the corresponding fatty acids. GB-A-1381121 employs a
molten coating of inter alia C 14 - C 1 g fatty acid mixtures to protect solid
organic perozyacid bleach precursors. GB-A-1441416 discloses a
similar process employing a mixture of C 12 - C 14 fatty acids and C 10 -
C20 aliphatic alcohols. EP-A-0375241 describes stabilised organic
perozyacid bleach precursor eztrudates in which CS- C 1 g alkyl perozy
carboxylic acid precursors are mined with a binder selected from anionic
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and nonionic surfactants, film forming polymers fatty acids or mixtures of
such binders.
EP-A-0356700 discloses compositions comprising a organic peroxyacid
bleach precursor, a water soluble film forming polymer and 2-15 °~ of a
C3-C6 polyvalent carboxylic acid or hydroxycarboxylic acid for enhanced
stability and ease of dispersion/solubility. The carboxylic acid, of which
a preferred example is citric acid, is dry mixed with the organic
peroxyacid bleach precursor and then granulated with the film forming
polymer. Specifically disclosed is a granule comprising 88.1 l of TAED
of mean particle size of 0.01 to 0.8mm, 10.4 ~ of citric acid, 0.5 °t
polyacrylate and 1.0 °b of water. The citric acid is asserted to
provide an
enhanced rate of dissolution of the organic peroxyacid bleach precursor
granules.
EP-A-0382464 concerns a process for coating or encapsulation of solid
particles including bleaching compounds and organic peroxyacid bleach
precursors in which a melt is formed of coating material in which the
particles form a disperse phase, the melt is destabilised and then caused to
crumble to a particulate material in which the disperse phase particles are
embedded in the continuous (coating) phase. A variety of coating
materials are disclosed and certain materials such as polyacrylic acid and
cellulose acetate phthalate are taught as being useful where release of the
coated material is dependent on pH.
Notwithstanding the advances in the art represented by the above
disclosures, difficulties have still been encountered in providing
peroxyacid precursor particles having acceptable physical characteristics
for bulk storage and perhydrolysis rate, where the peroxyacid precursor is
selected from those producing hydrophobic peroxyacid in aqueous wash
liquor.
Furthermore, when hydrophobic cleaning of dingy, yellow stains is
needed, the use of precursors which are hydrophobic in nature is
necessary for providing excellent performance on dingy stains. Examples
of such precursors are 3,5,5-tri-methyl hexanoyl oxybenzene sulfonate,
nonanoyl oxybenzene sulfonate and derivatives of caproyl oxybenzene
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sulfonate. However, due to their hydrophobic character, a solubility
problem is encountered with the use of such activators.
Moreover, when derivatives of caproyl oxybenzene sulfonate such as (6-
octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxy
benzene sulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and
mixtures thereof are used, the Applicants have found that these problems
were exacerbated.
The applicants have found that the above mentioned problems can be
particularly troublesome when said peroxyacid bleach precursor is used
under high hardness conditions, resulting upon dissolution in the
formation of insoluble calcium salts.
The Applicants have now found that these problems can be overcome by
the provision of a peroxyacid bleach precursor of a specific maximum
size together with a water-soluble organic acid compound, where the
peroxyacid bleach precursor is selected from those producing upon
perhydrolysis hydrophobic peroxyacid.
~X
According to the invention, there is provided a peroxyacid bleach
precursor composition comprising:
ara particulate peroxyacid bleach precursor of a size less than
100~m and selected from precursors
which produce under perhydrolysis hydrophobic peroxyacid whose
parent carboxylic acid has a critical micelle concentration less than
0.5 moles/litre, and
b)-a water-soluble organic acid compound;
wherein said precursor and said organic acid are in close physical
proximity.
For the purpose of the present invention, the term close physical
proximity means one of the following:
i) an agglomerate or extrudate in which said precursor and said organic
acid are in intimate admixture;
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ii) a bleach precursor particulate coated with one or more layers wherein
at least one layer contains the organic acid;
iii) an organic acid compound coated with one or more layers wherein at
least one layer contains the bleach activator.
It has to be understood by close physical proximity that the precursor and
the organic acid are not two separate discrete particles in the detergent
composition.
Detailed description of the invention
An essential feature of the invention is a 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 20°-50°C. Preferably, the peroxyacid
backbone chain
contains at least 7 carbons which may be partly or totally branched,
chained or cyclic and any mixtures thereof.
Perox3racid bleach precursor
Peroxyacid bleach precursor compounds typically contain one or more N-
or O-acyl groups, which precursors can be selected from a wide range of
classes.
Suitable peroxyacid bleach precursor for the purpose of the invention are
the amide substituted compounds of the following general formulae:
R1N(RS)C(O)R2C(O)L or R1C(O)N(RS)R2C(O)L
wherein R1 is an aryl or alkaryl group with from about 1 to about 14
carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing
from about 1 to 14 carbon atoms, and RS is H or an alkyl, aryl, or alkaryl
group containing 1 to 10 carbon atoms and L can be essentially any
leaving group. R1 preferably contains from about 6 to 12 carbon atoms.
R2 preferably contains from about 4 to 8 carbon atoms. R1 may be
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
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structural variations are permissible for R2. RZ can include alkyl, aryl,
wherein said R2 may also contain halogen, nitrogen, sulphur and other
typical substituent groups or organic compounds. RS is preferably H or
methyl. R1 and RS 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 su~ciently 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 di~cult
to stabilize for use in a bleaching composition.
Preferred L groups are selected from the group consisting of:
Y R3 R3Y
Y , and
O O
-N-C-R~ -N N -N-C-CH-R4
R3 ~ , R3 Y ,
I
Y
R3 Y
I I
-O-C H=C-C H=C Ii2 -O-C H=C-C H=C H2
O
_~-R~
3
R O Y
-O-C=C HR4 , and -N-S-C H-R4
R3 O
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and mixtures thereof, wherein R1 is an a3kyl, aryl, or alkaryl group
contalnlng from 1 to 14 carbon atoms, R is an alkyl chain containing
from 1 to 8 carb In at3oms, R~ is H or R3, and Y is H or a solubilizing
group. Any of R , R and R may be substituted by essentially any
functional group including, for example alkyl, hydroxy, alkoxy, halogen,
amine, nitrosyl, amide and ammonium or alkyl ammmonium groups
N+pre3ferred solubilizing g3 ups are -S03-M+, -C02-M+, -S04 M+,
(R ) X- and O < -N(R )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
cation, with sodium and potassium being most preferred, and X is a
halide, hydroxide, methylsulfate or acetate anion.
Preferred e~camples of bleach activators of the above formulae include
derivatives of caproyl oxybenzene sulfonate selected from (6-octanamido-
caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxy benzene sul-
fonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof
as described in EP-A-0170386.
Still another preferred class of bleach activator is the class of alkyl
percarboxylic acid bleach precursors.
Preferred alkyl percarboxylic acid precursors include nonanoyl oxy
benzene sulphonate (NOBS described in US 4,412,934) and 3,5,5-tri-
methyl hexanoyl oxybenzene sulfonate (ISONOBS described in
EP120,591) and salts thereof.
Mixture of any of the peroxyacid bleach precursor, herein before
described, may also be used.
The peroxyacid bleach precursors are normally incorporated at a level of
from 20 °.b to 95 °6 by weight of the bleach precursor
composition,
preferably at least 50 °.b and most preferably at least 60 °~ by
weight
thereof.
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In absolute terms the peroxyacid bleach precursor is typically from 1 % to
20 °~ by weight, more preferably from 1 l to 10 % by weight, most
preferably from 1 R6 to 7 % by weight of the detergent compositions.
Water-soluble organic acid com ound
The composition of the invention contains as another essential component
a water-soluble organic acid compound.
Organic acids compounds suitable for incorporation as agglomerating
agents of the particles of the invention comprise aliphatic or aromatic
carboxylates. The carboxylates may be monomeric, oligomeric or
polymeric in nature and preferably comprise aliphatic carboxylic acids.
Examples of monomeric aliphatic acid compounds are glycolic, glutamic,
citraconic, succinic, 1-lactic, malonic, glutaric, adipic, malefic, malic,
tartaric, citric, diglycolic and carboxymethyl succinic acids. Examples of
polymeric acid compounds include poly(meth)acrylic acids and
copolymeric derivatives with malefic anhydride. Preferably, the organic
acid is a monomeric or oligomeric carboxylate and more preferably a
monomeric aliphatic carboxylic acid. Preferred monomeric aliphatic acids
are 1-lactic, citric and glycolic acids while preferred polymeric acids
include polyacrylic acids of MWt 3000-5000, especially about 4500 and
acrylic acid malefic anhydride copolymers of MWt 40,000-90,000.
A preferred organic acid is citric acid.
The organic acid is incorporated at levels of from 5 96 to 50 °6 by
weight
of the particulate to be agglomerated, more preferably from 5 9b to 25
°b
by weight and most preferably from 7°6 to 2096 by weight.
The incorporation of other ingredients additional to the organic
peroxyacid bleach precursor compound and organic acid compound can
be advantageous particularly in the processing of the bleach precursor
particulates and also in enhancing the stability of detergent compositions
in which the particulates are included. In particular, certain types of
agglomerates may require the addition of one or more binder agents in
order to assist in binding the organic peroxyacid bleach precursor
compound and organic acid compound so as to produce particulates with
acceptable physical characteristics. The binder agents may be present at a
level of from 096 to 4096 by weight of the particulate. Preferably, the
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g
binder agents will be in intimate admixture with the organic peroxyacid
bleach precursor compound and organic acid compound. Preferred
binder agents have a melting point between 30°C-70°C. The binder
agents are preferably present in amounts from 1-30°~ by weight of the
particulate and most preferably from 2-20 % by weight of the particulate.
Preferred binder agents include the C 10-C2p alcohol ethoxylates
containing from 5-100 moles of ethylene oxide per mole of alcohol and
more preferably the C 15-C20 Primary alcohol ethoxylates containing from
20-100 moles of ethylene oxide per mole of alcohol. Of these tallow
alcohol ethoxylated with 25 moles of ethylene oxide per mole of alcohol
(TAE25) or 50 moles of ethylene oxide per mole of alcohol (TAE50) are
preferred.
Other preferred binder agents include certain polymeric materials.
Polyvinylpyrrolidones with an average molecular weight of from 12,000
to 700,000 and polyethylene glycols with an average weight of from 600
to 10,000 are examples of such polymeric materials. Copolymers of
malefic anhydride with ethylene, methylvinyl ether, methacrylic acid or
acrylic acid are further examples of polymeric materials useful as binder
agents. Of these, copolymers of malefic anhydride with acrylic acid are
preferred. These polymeric materials may be used as such or in
combination with solvents such as water, propylene glycol and the above
mentioned Clp-C20 alcohol ethoxylates containing from 5-100 moles of
ethylene oxide per mole. Further examples of binder agents include the
C 10 -C20 mono- and diglycerol ethers and also the C l p-C20 fatty acids.
Solutions of certain inorganic salts including sodium silicate are also of
use for this purpose.
Cellulose derivatives such as carboxymethylcellulose, and homo- or co-
polymeric polycarboxylic acid or their salts are other examples of suitable
binder agents.
Other additives that are compatible with the peroxyacid precursors may
also be included in detergent additive compositions in accordance with the
invention. Examples of such additives include surfactants, fluorescers,
enzymes, suds suppressors, dye transfer inhibition agents, soil suspending
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9
agents, water soluble builders and chelating agents. Specific
embodiments of such additives and their levels of incorporation are
described hereinafter but the total level of the additives normally lies in
the range of from S 9b to 509to by weight of the additive composition. The
peroxyacid precursors) should substantially form the major component of
the precursor composition, ie. from 20 °~ to 95 ~O by weight of the
agglomerate, preferably at least SO Xo by weight and most preferably at
least 60 °l~ by weight thereof.
In preferred agglomerate embodiments of the invention the diameter of
the pores forming the spaces between the agglomerated particles is
selected by controlling the levels of compaction and shear applied during
the agglomeration process. Too large a pore size results in an
agglomerate of inadequate strength and a tendency to disintegrate during ,
handling. Too small a pore size results in an agglomerate having a slow
rate of dissolution. It has been found that a satisfactory agglomerate has a
% of porosity of at least 12 corresponding to a mean pore diameter of at
least O.Spm and preferably in the range of from 0.6 to 5 micrometers.
The porosity is measured according to the following technique, using a
Micromeritics Poresizer 9320.
This equipment is manufactured by Micromeritics Instrument
Corporation, One Micromeritics Drive, Norcross GA 30093-1877, USA
and comprises a Penetrometer;MAnalyser and printer.
For this analysis the Penetrometer bulb is filled with a known weight (to
4dp) of particulate material. The Penetrometer is then fully assembled
with the insulator seal, spring and retaining collar. This is then fitted into
the low pressure port of the porosity analyser. The Penetrometer is then
evacuated and the sample analysed under the following set point
conditions:
Maumum measurable volume 0.387 ml
Total stem volume 0.412 ml
Ma~cimum head pressure 4.68 psi (porosity pressure
readings)
Penetrometer constant 10.79 l/pf (litres/pico farad)
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at the following pressures: 2, 3, 4, 5.5, 7, 8.5, 10.5, 13, 16, 20, 23, 25
psia.
After this analysis the Penetrometer bulb is installed in the high pressure
chamber and analysed under the same set point conditions and the printer
then gives the median pore diameter and pore intrusion volumes for the
sample. For the preferred pore diameter of at least 0.5 micrometers, the
pore intrusion volume is at least 0.2 ml/g
Detergent compositions incorporating the peroxy acid bleach precursor
particulates will normally contain from 1 °~ to 209 of the precursor,
more
frequently from 1 °b to 10 ~'o and most preferably from 1 % to 7 % , on
a
composition weight basis.
Such detergent compositions will, of course, contain a source of alkaline
hydrogen peroxide necessary to form a peroxyacid bleaching species in
the wash solution and preferably will also contain other components
conventional in detergent compositions. 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.
When incorporated in compositions suitable for use in a machine washing
method, eg: machine laundry and machine dishwashing methods, the
compositions of the invention preferably contain one or more additional
detersive components.
Thus preferred detergent compositions will incorporate one of more of
surfactants, organic and inorganic builders, soil suspending and anti-
redeposition agents, suds suppressors, enzymes, fluorescent whitening
agents photo activated bleaches, perfumes and colours.
Detergent compositions incorporating the particulate peroxyacid
precursors of the present invention will include an inorganic perhydrate
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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 3 °6 to 40 % by weight, more preferably
from 5 ab to 35 °6 by weight and most preferably from 8 % to 30 %n 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.
Sodium percarbonate, which is the preferred perhydrate, is an addition
compound having a formula corresponding to 2Na2C03.3H202, and is
available commercially as a crystalline solid. Most commercially
available material includes a low level of a heavy metal sequestrant 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 Si02: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 °r~ to 10 % ,
(normally from
3 9b to 5 9~) 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 500-1000
micrometers.
A wide range of surfactants can be used in the detergent compositions. A
typical listing of anionic, nonionic, ampholytic and zwitterionic classes,
and species of these surfactants, is given in USP 3,929,678 issued to
Laughlin and Heuring on December, 30, 1975. A list of suitable cationic
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surfactants is given in USP 4,259,217 issued to Murphy on March 31,
1981.
Nonlimiting examples of surfactants useful herein typically at levels from
1 °~ to 55 % , by weight, include the conventional C 11-C 1 g alkyl
benzene
sulfonates ("LAS") and primary, branched-chain and random Clp-C20
alkyl sulfates ("AS "), the C lp-C 1 g secondary (2,3) alkyl sulfates of the
formula CH3(CH2)x(+HOS03-M+) CH3 and CH3
(CH2)y(CHOS03-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 C10-C18
alkyl alkoxy sulfates ("AEXS"; especially EO 1-7 ethoxy sulfates),
C lp-C 1 g alkyl alkoxy carboxylates (especially the EO 1-5
ethoxycarboxylates), the C 1 ~ 1 g glycerol ethers, the C l p-C 1 g alkyl
polyglycosides and their corresponding sulfated polyglycosides, and
C 12-C 1 g alpha-sulfonated fatty acid esters. If desired, the conventional
nonionic and amphoteric surfactants such as the C 12-C 1 g alkyl
ethoxylates ("AE") including the so-called narrow peaked alkyl
ethoxylates and C6-C 12 alkyl phenol alkoxylates (especially ethoxylates
and mixed ethoxy/propoxy), C 12-C 1 g betaines and sulfobetaines
("sultaines"), C l p-C 1 g amine oxides, and the like, can also be included in
the overall compositions. The C l p-C 1 g N-alkyl polyhydroxy fatty acid
amides can also be used. Typical examples include the C 12-C 1 g N-
methylglucamides. See WO 9,206,154. Other sugar-derived surfactants
include the N-alkoxy polyhydroxy fatty acid amides, such as C l p-C 1 g N
(3-met6oxypropyl) glucamide. The N-propyl through N-hexyl C 12-C 18
glucamides can be used for low sudsing. Clp-C2p conventional soaps
may also be used. If high sudsing is desired, the branched-chain C l p-
C16 soaps may be used. Other suitable surfactants suitable for the
purpose of the invention are the anionic alkali metal sarcosinates of
formula:
R-CON(R1)CH2COOM
wherein R is a Cg-C17 linear or branched alkyl or alkenyl group, R1 is a
C1-C4 alkyl group and N is an alkali metal ion. Preferred examples are
the lauroyl, cocoyl (C 12-C 14) ~ mYristyl and oleyl methyl sarcosinates in
the form of their sodium salts. Mixtures of anionic and nonionic
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surfactants are especially useful. Other conventional useful surfactants
are listed in standard texts.
The compositions herein can optionally include one or more other
additional detergent compounds or other compounds for assisting or
enhancing cleaning performance, treatment of the substrate to be cleaned,
or to modify the aesthetics of the detergent composition (e.g., perfumes,
colorants, dyes, etc.). The following are illustrative examples of such
additional detergent compounds.
il r - 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 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 °b builder. Liquid
formulations typically comprise from 5 °~ to 50 % , more typically 5
°~ to
30 °6 , by weight, of detergent builder. Granular formulations
typically
comprise from 10 °b 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 excluded.
Inorganic or phosphate-containing detergent builders include, but
are not limited to, the alkali 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, homo or copolymeric polycarboxylic acids
or their salts in which the polycarboxylic acid comprises at least two
carboxylic radicals separated from each other by not more than two
carbon atoms, organic phosphonates and aminoalkylene poly (alkylene
phosphonates). Importantly, the compositions herein function surprisingly
well even 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.
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Examples of silicate builders are the so called ' amorphous' alkali
metal silicates, particularly those having a Si02:Na20 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-
Na2Si205 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
NaMSix02x+ 1'YH20 wherein M is sodium or hydrogen, x 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 gamma forms.
As noted above, the delta-Na2Si205 (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.
Examples of carbonate builders are the alkaline earth and alkali
metal carbonates as disclosed in German Patent Application No.
2,321,001 published on November 15, 1973.
Aluminosilicate builders are useful in the present invention.
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(Si02)y~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. Patent 3,985,669. Preferred synthetic crystalline
aluminosilicate ion exchange materials useful herein are available under
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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 12 ((A102) 12(Si02) 12) ~ X20
wherein x 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
polycarboxylate compounds. As used herein, "polycarboxylate" refers to
compounds having a plurality of carboxylate groups, preferably at least 3
carboxylates. Polycarboxylate builder can generally be added to the
composition in acid form, but can also be added in the form of a
neutralised salt. When utilized in salt form, alkali metals, such as
sodium, potassium, and lithium, or alkanolammonium salts are preferred.
Included among the polycarboxylate builders are a variety of
categories of useful materials. One important category of polycarboxylate
builders encompasses the ether polycarboxylates, including
oxydisuccinate, 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 4,663,071.
Suitable ether polycarboxylates 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 detergency builders include the ether
hydroxypolycarboxylates, copolymers of malefic 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,
carboxymethyloxysuccinic 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 detergent formulations due to their
availability from renewable resources and their biodegradability. Citrates
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16
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.
Also suitable in the compositions containing the present invention
are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates 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 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. Patent
4,144,226 and in U.S. Patent 3,308,067. See also U.S. Pat. 3,723,322..
Fatty acids, e.g., C 12-C 1 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.
In situations where phosphorus-based builders can be used, and
especially in the formulation of bars used for hand-laundering operations,
the various alkali metal phosphates such as the well-known sodium
tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can
be used. Phosphonate builders such as ethane-1-hydroxy-1,1-
diphosphonate and other known phosphonates (see, for example, U.S.
Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can
also be used.
Chelating Agents - The detergent compositions herein may also
optionally contain one or more iron and/or manganese chelating agents.
Such chelating agents can be selected from the group consisting of amino
carboxylates, amino phosphonates, polyfunctionally-substituted aromatic
chelating agents and mixtures therein, all as hereinafter defined. Without
intending to be bound by theory, it is believed that the benefit of these
materials is due in part to their exceptional ability to remove iron and
manganese ions from washing solutions by formation of soluble chelates.
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17
Amino carboxylates useful as optional chelating agents include
ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,
nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetra-
aminehexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines,
alkali metal, ammonium, and substituted ammonium salts therein and
mixtures therein.
Amino 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
ethylenediaminetetrakis (methylenephosphonates) available under the
trademark DEQUEST from Monsanto. Preferably, these amino
phosphonates do not contain alkyl or alkenyl groups with more than 6
carbon atoms.
Polyfunctionally-substituted aromatic chelating agents are also
useful in the compositions herein. See U.S. Patent 3,812,04.4. Preferred
compounds of this type in acid form are dihydroxydisulfobenzenes such as
1,2-dihydroxy-3,5-disulfobenzene.
Preferred biodegradable non-phosphorus chelants for use herein are
ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as
described in U.S. Patent 4,704,233, ethylenediamine-N,N'-diglutamate
(EDDG) and 2-hydroxypropylene-diamine-N,N'-disuccinate (HPDDS)
compounds.
If utilized, these chelating agents will generally comprise from
0.1 ab to 10°ro by weight of the detergent compositions herein. More
preferably, if utilized, the chelating agents will comprise from 0.1 °6
to
3.0 ~ by weight of such compositions.
Cla3r Soil Removal/Anti-redeposition A ents - The compositions
according to the present invention can also optionally contain water-
soluble ethoxylated amines having clay soil removal and antiredeposition
properties. Granular detergent compositions which contain these
compounds typically contain from 0.01 °b to 10.0° by weight of
the
water-soluble ethoxylates amines; liquid detergent compositions typically
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. Patent 4,597,898, VanderMeer, issued July 1,
CA 02204153 2000-OS-09
18
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
ethoxylated 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 utilized in the compositions herein. Another
type of preferred antiredeposition agent includes the carboxy methyl
cellulose (CMC) materials. These materials are well known in the art.
Polymeric Soil Release Aeent - 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 hydrophiIize the
surface of hydrophobic fibers, such as polyester and nylon, 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.
Soil release agents characterised by polyvinyl ester) hydrophobe
segments include graft copolymers of polyvinyl ester), e.g., C1-C6 vinyl
esters, preferably polyvinyl acetate) grafted onto polyalkylene oxide
backbones, such as polyethylene oxide backbones (see EP 0 219 048).
CommereialMly available soil release agents of this kind include the
SOKALAN type of material, e.g., SOKALAN 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. Patent 3,959,230 to
Hays and U.S. Patent 3,893,929.
Another preferred polymeric soil release agent is a polyester with
repeat units of ethylene terephthalate units contains 10-15 ~ by weight of
ethylene terephthalate units together with 90-8096 by weight of
polyoxyethylene terephthalate units, derived from a polyoxyethylene
glycol of average molecular weight 300-5,000. Examples of this polymer
CA 02204153 2000-OS-09
19
TM
include the commercially aM ailable material ZELCON 5126 (from
Dupont) and MILEASE T (from ICn. See also U.S. Patent 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 fully in U.S. Patent 4,968,451. Other
suitable polymeric soil release agents include the terephthalate 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.
Preferred polymeric soil release agents also include the soil release
agents of U.S. Patent 4,877,896, which discloses anionic, especially sul-
foarolyl, end-capped terephthalate esters.
If utilized, soil release agents will generally comprise from 0.01 f6
to 10.096, by weight, of the detergent compositions herein, typically from
0.1 ~ to 5 °6, preferably from 0.296 to 3.096.
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 0.596 to 2096, by weight of the oligomer, of a
crystalline-reducing stabilizer, preferably selected from xylene sulfonate,
cumene sulfonate, toluene sulfonate, and mixtures thereof.
jZve Transfer Inhibiting~Eents
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 cleaning process. Generally, 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 0.01 ~ to 1096 by
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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=; 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-O group can be
attached or the N-O group is pan 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-O group can be represented by the following general
structures:
O O
I I
~i~c- ~ ~2hr~ =N~l~c
(R3h
wherein R1, RZ, 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-O 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-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
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21
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-oxide useful in the detergent
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
Anal3rsis, 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.
The detergent compositions herein may also optionally contain from
0.005 9b to 5 °6 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 % by
weight of such optical brighteners.,
The hydrophilic optical brighteners useful in the present invention
are those having the structural formula:
CA 02204153 2000-OS-09
22
R~ R
2
>--N H H N
N N C-
C N N
/ N H H N \
RZ S03M S03M
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-
hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a
salt-forming ration such as sodium or potassium.
When in the above formula, Rl is anilino, R2 is N-2-bis-
hydroxyethyl and M is a ration such as sodium, the brightener is 4,4',-
bis[(4-anilino-b-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-
stilbenedisulfoaic acid and disodium salt. This particular brightener
species is commercially marketed under the trademark Tinopal-UNPA-
GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred
hydrophilic optical brightener useful in the detergent compositions herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-
N-2-methylamino and M is a ration such as sodium, the brightener is 4,4'-
bis[(4-anilino-b-(N-2-hydroxyethyl-N-methylamino~s-triazine-2-
yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particular
brightener species is commercially marketed under the trademark Tinopal
SBM-GX by Ciba-Geigy Corporation.
When in the above formula, R~ is anilino, R2 is morphilino and M
is a ration such as sodium, the brightener is 4,4'-bis[(4-anilino-~
morphilino-s-triazine-2-yl)amino]2,2'-sdlbenedisulfonic acid, sodium salt.
'This particular brightener species is commercially marketed under the
trademark Tinopal AMS-GX by Ciba Geigy Corporation.
Other specific optical brightener species which may be used in the
present invention provide especially effective dye transfer inhibition
performance benefits 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
PVPVn 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
CA 02204153 2000-OS-09
23
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 extent to which
brighteners deposit on fabrics in the wash solution can be defined by a
parameter called the "exhaustion coefficient". The exhaustion coe~cient
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 exhaustion coefficients are the most suitable for
inhibiting dye transfer in the context 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 "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 brightening or whitening
agents known in the art can be incorporated at levels typically from
0.05 % to 1.2 %, by weight, into the detergent compositions herein.
Commercial optical brighteners which may be useful in the present
invention can be classified into subgroups, which include, but are not
necessarily limited to, derivatives of stilbene, pyrazoline, coumarin,
carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, S-
and 6-membered-ring heterocycles, and other miscellaneous agents.
Examples of such brighteners are disclosed in "The Production and
Application of Fluorescent Brightening Agents", M. Zahradnik, Published
by John Wiley 8~ Sons, New York (1982).
Specific examples of optical brighteners which are useful in the
present compositions are those identified in U.S. Patent 4,790,856.
These brighteners include the PHORWHTTETseries 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, available from Hilton-Davis, located in
Italy; the 2-(4-stryl-phenyl)-2H-napthol[1,2-d]triazoles; 4,4'-bis- (1,2,3-
triazol-2-yl~stil- benes; 4,4'-bis(stryl)bisphenyls; and the
aminocoumarins. Specific examples of these brighteners include 4-
methyl-7-diethyl- amino coumarin; 1,2-bis(-venzimidazol-2-yl)ethylene;
1,3~ipheayl-phrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-stryl-
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24
napth-[1,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho- [1,2-d]triazole.
See also U.S. Patent 3,646,015. Anionic brighteners are preferred herein.
Suds Sunnressors - 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 cleaning process" and in front-loading European-style
washing machines.
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, 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. Patent
2,954,347. The monocarboxylic fatty acids and salts thereof used as suds
suppressor 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 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 C 1 g-C4p
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 haloparafFm can be utilized 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
SO°C, and
a minimum boiling point not less than 110°C (atmospheric pressure). It
is also known to utilise waxy hydrocarbons, preferably having a melting
point below 100°C. The hydrocarbons constitute a preferred category of
suds suppressor for detergent compositions. Hydrocarbon suds
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suppressors are described, for example, in U.S. Patent 4,265,779. The
hydrocarbons, thus, include aliphatic, alicyclic, aromatic, 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 para~ns 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
known in the art and are, for example, 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 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. Patent 3,933,672 and in U.S. Patent 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)3Si01/2 units of Si02 units in a ratio
of from (CH3)3 Si01/2 units and to Si02 units of from 0.6:1
to 1.2:1; and
(iii) from 1 to 20 parts per 100 parts by weight of (i) of a solid
silica gel.
In the 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
CA 02204153 2000-OS-09
26
(preferred), or polypropylene glycol. The primary silicone suds
suppressor is branched/crosslinked and preferably 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 mixture of (a) a
polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing
silicone compound, (c) a finely divided filler material, and (d) a catalyst
to promote the reaction of mixture 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 4,97$,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
solubility in water at room temperature of more than 2 weight 9~ ,
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 oxide and
propylene oxide, like PLURONIG~L101.
Other suds suppressors useful herein comprise the secondary
alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with
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27
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.
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 preferably
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 su~ciently 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°b of
suds suppressor. When utilized as suds suppressors, monocarboxylic
fatty acids, and salts therein, will be present typically in amounts up to
°.b , by weight, of the detergent composition. Preferably, from 0.5 9b
to
3 °b of fatty monocarboxylate suds suppressor is utilized. Silicone
suds
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 °b of silicone suds
suppressor is used, more preferably from 0.25 °6 to 0.5 °~ . As
used
herein, 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 l 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 ~0-3 % by
weight of the finished compositions.
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~tlT.v
Another optional ingredient useful in the present invention is one or more
enzymes.
Preferred enzymatic materials include the commercially available
amylases, neutral and alkaline proteases, lipases, peroxidases, esterases
and cellulases conventionally incorporated into detergent compositions.
Suitable proteolytic enzymes are described in GB-A-1243784, EP-A-
0130756 and USP 5185250 and 5204015. Suitable amylases are disclosed
in GB-A-1296839 while cellulases are disclosed in USP 4435307, GB-A-
2075028 and 2095275. Lipases for use in detergent compositions are
disclosed in GB-A-1372034 and EP-A-0341947. A suitable peroxidase is
disclosed by W089/099813. A wide range of enzyme materials and
means for their incorporation into synthetic detergent granules is also
discussed in US Patents 3,519,570 and 3,533,139.
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 °b to 10 °~ 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. Patent 4,375,416 and U.S. Patent
4,291,071.
Other InQr~edienrs - A wide variety of other functional ingredients useful
in detergent compositions can be included in the compositions herein,
including other active ingredients, carriers, hydrotropes, processing aids,
dyes or pigments, solvents for liquid formulations, solid fillers for bar
compositions, etc. If high sudsing is desired, suds boosters such as the
C l p-C 16 alkanolamides can be incorporated into the compositions,
typically at 1 %-10 l levels. The C lp-C 14 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 oxides,
betaines and sultaines noted above is also advantageous. If desired,
soluble magnesium salts such as MgCl2, MgS04, and the like, can be
added at levels of, typically, 0.1 %-2%, to provide additional suds and to
enhance grease removal performance.
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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 admixed 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 admixed with a
proteolytic enzyme solution containing 3 % -5 % of C 13-15 ethoxylated
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 matrix. 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
detergents, including liquid laundry detergent compositions.
Liquid detergent compositions can contain water and other solvents
as carriers. Low molecular weight primary or secondary alcohols
exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
Monohydric alcohols are preferred for solubilizing surfactant, but polyols
such as those containing from 2 to 6 carbon atoms and from 2 to 6
hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and
1,2-propanediol) can also be used. The compositions may contain from
% to 90 % , typically 10 % to 50 % of such carriers.
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.
Liquid dishwashing product formulations preferably have a pH between
6.8 and 9Ø Laundry 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.
The bulk density of granular detergent compositions is typically at least
450 g/litre, more usually at least 600 g/litre and more preferably from
650 g/litre to 1000 g/litre.
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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, the abbreviated component identifications
have the following meanings:
XMAS . Sodium C1X - Cly alkyl sulfate
25EY . A 012-15 Predominantly linear primary alcohol
condensed with~an average of Y moles of
ethylene oxide
C 12LAS . Sodium linear C 12 alkyl benzene
sulphonate
TAS . Sodium tallow alcohol sulphate
TAEn . Tallow alcohol ethoxylated with n moles
of
ethylene oxide per mole of alcohol
C25E3S . Sodium C 12-C 15 branched alkyl sulphate
condensed with three moles of ethylene oxide
45E7 . A 014-15 Predominantly linear primary alcohol
condensed with an average of 7 moles of
ethylene oxide
TFAA . C 1 (-C 1 g alkyl N-methyl glucamide
Silicate . Amorphous Sodium Silicate (Si02:Na20 ratio
normally follows)
NaSKS-6 . Crystalline layered silicate of formula
-Na2Si205
Carbonate . Anhydrous sodium carbonate
CMC . Sodium carboxymethyl cellulose
Zeolite A . Hydrated Sodium Aluminosilicate of formula
Nal2(A102Si02)12~ 2~H20
having a primary particle size in the range from
1 to 10 micrometers
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Polyacrylate . Homopolymer of acrylic acid of MWt 4000
Citrate . Tri-sodium citrate dihydrate
MA/AA . Copolymer of 1:4 maleic/acrylic acid,
average
molecular.weight about 70,000.
Perborate . Sodium perborate tetrahydrate of nominal
formula NaB02.3H20.H202
Perborate . Anhydrous sodium perborate bleach
Monohydrate empirical formula NaB02.H202
Percarbonate . Sodium Percarbonate of nominal formula
2Na2C03.3H202
SavinaseMM . proteolytic enzyme activity 4KNPU/g
Alcalase MT . proteolytic enzyme activity 3AU/g
Cellulase IT . cellulytic enzyme activity 1000 SCEVU/g
LipalaseTM . Lipolytic enzyme activity 100kLU/g
all sold by NOVO Industries AS
DETPMP . Diethylene triamine penta (Methylene
phosphoric acid), marketed by Monsanto
under
the Trade mark bequest 2060
EDDS . Ethylenediamiae disuccinate
PVNO . Poly (4-vinylpyridine)-N-oacide copolymer of
vinylimidazole and vinylpyrrolidone having an
average molecular weight of 10,000
Mixed Suds . 25 9~ paraffin wax Mpt 50 °C, 17 R~
Suppressor hydrophobic silica, 58 ~ paraffin oil.
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32
An agglomerate having the following formulation was made in a
Kenwood food mixer
wt °b
(6-octanamido-caproyl) 60
oxybenzenesulfonate/
(6-decanamido-caproyl)
oxybenzenesulfonate
citric acid 25
TAE 25 15
100
A blend of (froctanamido-caproyl) oxybenzenesulfonate/ (6-decanamido-
caproyl) oxybenzenesulfonate in fine powder form (particle size less than
100 micrometers) and citric acid were added to the Kenwood food miner
and pre-mixed. The temperature of the powders was 25°C. The molten
nonionic binder TAE25 was added to the powder mix over a period of 2
minutes. The resulting mass was further mixed for 30 seconds. The
mixing was then stopped and the agglomerate removed from the Kenwood
food mixer and cooled to ambient temperature.
The product was then sieved and materials that were greater than 1180
micrometers and smaller than 250 micrometers were removed.
~r
The same procedure as above was repeated with the exception of the
blend of (6-octanamido-caproyl) oxybenzenesulfonate/ (6-decanamido-
caproyl) oxybenzenesulfonate being replaced in the same amounts with a
benzoyl caprolactam.
Exam
Further experiment was carried out with the peroxyacid bleach precursor
of example 1 and 2 taken respectively in their raw material form.
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Example 44
For the purpose of the present invention, unrestrained dissolution
conditions are defined as those existing in the Beaker Perhydrolysis Test
as carried out using a Sotax Dissolution Tester Model AT6 supplied by
Sotax AG CH-4008 BASEL Switzerland. This Apparatus comprises an
array of polycarbonate beakers, each capable of holding 1 litre of water,
supported in a thermostatically controlled water bath. Each beaker is
provided with a paddle stirrer whose speed can be controlled.
Two beakers in the Sotax Tester are employed in the perhydrolysis
procedure using the following method:
1- Set water bath to required temperature (40°C).
2- Add llitre of water (12° Clark) to each Sotax beaker and allow to
equilibrate to required temperature.
3- Sample accurately 2 x lOg samples of detergent and precursor.
4- Prepare a number of titration beakers by adding:
25m13:2 glacial acetic acid distilled water solution together
with 2 ice cubes
5- Set the stirring speed of the Sotax to 150 rpm.
6- Add the first sample to Sotax beaker No.l and start the clock (t=0
minutes). Add Sml potassium iodide solution to the first titration
beaker.
7- Take a lOml aliquot from Sotax beaker No. 1 and discharge into the
first titration beaker at t=1 minute.
8- Add the second sample to Sotax beaker No.2 at t= 1 minute and
add 5 ml potassium iodide to a second titration beaker.
9- Titrate the first aliquot against 0.005 M sodium thiosulphate
solution until the solution is first decolourised (The colour is slowly
regenerated as the solution warms and the perhydrate reacts with
the iodide).
10- Take a 10 ml aliquot from Sotax beaker No.2 at t= 2 minutes and
discharge into the second titration beaker and repeat step .
11- Take further aliquots at the following times (t= minutes)
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Beaker No. 1 Beaker No.2
t) (t)
1 2
3
6
11
The aliquots from Beaker No. 1 at 1 minute and from Beaker No. 2 at 2
minutes constitutes replicates and the results are averaged to give a figure
from which the % perhydrolysis is calculated.
Material from each example was then incorporated into a model detergent
formulation having the composition in % by weight.
45AS/25AS 3:1 ) 9.1
35AE3S 2.3
24E5 4.5
TF~ 2.0
Zeolite A 10.2
Na SKS-6/citric acid (79:2110.6
)
Carbonate 7.6
Peroxyacid bleach precursor4.16
com sition
Percarbonate 22.5
EDDS 0.5
0.55
Li ase 0.15
Cellulase 0.28
Am lase 0.27
MA/AA 3.1
CMC 0.4
PVNO 0.03
Granular suds su ressor 1.5
Minors/misc to 100 %
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The four formulations were then subjected to a Beaker Perhydrolysis Test
as hereinbefore described and gave the peroxyacid yields shown in Table
1. Results are given for l, 3, 5 & 10 minutes elapsed time and are
expressed in percent of the theoretically available weight of peracid.
Table I
(Temperature = 40C)
minutes from start of perhydrolysis
Product with peroxyacid 1 3 5 10
fraction of exam le
3 43 42 34 32
C8:C10 ox benzenesulfonate
1 45 58 66 62
3 14 37 52 71
(benzo 1 ca rolactam)
2 20 31 40 55
It can be seen that the perhydrolysis rate of the blend of (6-octanamido-
caproyl) oaybenzenesulfonate/ (6-decanamido-caproyl)
oxybenzenesulfonate is significantly enhanced by the agglomeration with
citric acid. No such enhancement can be seen when benzoyl caprolactam
is similarly agglomerated.
~a~~ile 5
The same experiment as above was carried out but in a hard water
environment (25° Clarck) at 60°C with only product with
peroxyacid
fraction of e~cample 3(C8:C10 oxybenzenesulfonate) and 1.
The two formulations were then subjected to a Beaker Perhydrolysis Test
as hereinbefore described and gave the peroxyacid yields shown in Table
II. Results are given for 1, 3, 5 & 10 minutes elapsed time and are
expressed in percent of the theoretically available weight of peracid.
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pCTIUS95115494
Table II
(Temperature = 60C)
minutes from start of perhydrolysis
Product with peroxyacid 1 3 5 10
fraction of exam le
3 58 66 71 53
C8:C10 ox benzenesulfonate
1 86 88 87 66
It can be seen that the enhancement in perhydrolysis of the blend of (6-
octanamido-caproyl) oxybenzenesulfonate/ (6-decanamido-caproyl)
oxybenzenesulfonate is consistent over the temperature range and also in
very hard water.
m 1
The same experiment as in example 5 was conducted in a hard water
environment (25° Clarck) at 30°C with the exception of the
peroxyacid
bleach precursor being replaced by (6-decanamido-caproyl)
oxybenzenesulfonate with different % of porosity and different mean pore
diameter.
The two formulations were then subjected to a Beaker Perhydrolysis Test
as hereinbefore described and gave the peroxyacid yields shown in Table
BI. Results are given for 3, 5 & 10 minutes elapsed time and are
expressed in percent of the theoretically available weight of peracid.
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Table III
(Temperature = 30C)
b of mean minutes
from
start
of
Product with porositypore perhydrolysis
diameter
m) 3 5 10
C 10 - - 25 31 34
oxybenzenesulfonate
(raw material)*
C 10 15 .2 0. 8 45 70 75
oxybenzenesulfonate
a lomerate)**
C 10 11.9 0.4 36 38 42
oxybenzenesulfonate
a lomerate)**
C10 11.8 0.3 12 15 19
oxybenzenesulfonate
extrudate)
* according to Example 3
** as made according to Example 1
It can be seen that (6-decanamido-caproyl) oxybenzenesulfonate in
agglomerate form affords a way of improving the perhydrolysis versus (6-
decanamido-caproyl) oxybenzenesulfonate in raw material form.
Furthermore, it can also be seen that (6-decanamido-caproyl)
oxybenzenesulfonate particles having a % of porosity > 12 and a mean
pore diameter > O.S~m show enhanced perhydrolysis.
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38
exam in ~ ~
The following detergent compositions are in accordance with the
invention.
A B C D
C 12LAS . 6.5 6.5 7 . 6 6. 9
TAS . 3.0 3.0 1.3 2.0
C~E3S . 0.15 0.15 0.15 0.15
C45E7 . 4.0 5.0 1.3 4.0
Zeolite : 18.0 17.0 17.0 20
Citrate . - - 1.5 5.5
Citric Acid . 2.3 1.8 2.6 -
SKS-6 . 8.7 6.5 9.5 -
Carbonate . 16.0 15.5 7.0 15.4
Silicate (2.0 ratio)0.5 0.5 0.5 3.0
:
Bicarbonate . 4.5 7.5 1.5 -
MA/AA Copolymer: 4.0 4.5 3.2 4.0
CMC . 0.3 0.3 0.2 0.3
Savinase . 0.4 - 0.4 1.4
Lipolase . 0:2 0.1 0.1 0.3
Cellulase . 0.15 0.15 - 0.1
Alcalase . - 0.3 - -
Perborate . - - 9.0 11.6
Perborate
Monohydrate . - - 5.0 8.7
Percarbonate . 17.5 16.5 - -
DETPMP . 0.4 0.4 0.4 0.4
MgS04 0.4 0.4 0.4 0.4
Fluorescer . 0.19 0.19 0.15 0.19
Suds Suppressor 0.8 0.8 0.8 0.8
.
Perfume . 0.35 0.4 0.35 0.4
Peroxyacid
precursor
composition (1) 4.5 - 3.4 -
.
Peroxyacid
precursor
composition (2) - 2.5 - 5.0
.
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39
Sulphate
Minors etc. to . 100 100 100 100
(1) as in Example 1
(2) as in Example 6 (6-decanamido-caproyl) oxybenzenesulfonate
agglomerate having a °b of porosity = 15.2 and a mean pore diameter =
0.8~m)
