Note: Descriptions are shown in the official language in which they were submitted.
CA 02189751 1999-09-07
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DETERGENT COMPOSTTIONS HAVING SUDS SUPPRESSING
PROPERTIES
FIELD OF THE INVENTION
The present invention relates to detergent compositions having suds
suppressing properties. More particularly, the present invention relates to
new suds suppressor compounds.
BACKGROUND OF THE INVENTION
Detergent compositions containing high levels of surfactants are known in
the art. Surfactants such as anionic, nonionic or cationic are required to
aid grease removal and maintain soil suspension from fabrics. More
particularly, high levels of anionic surfactants are desirable to provide
whiteness maintenance. However, a problem encountered with the use of
some high levels of surfactants, especially high foaming anionic
surfactants, is the propensity of the surfactant to give high levels of
sudsing; this problem being particularly more acute at high temperature.
Traditionally, the suppression of suds has been enabled by the use of high
level of suds suppressor such as silicones, fatty acids and twin chain
alcohols. However a problem encountered by such use is their expensive
cost for few detergency benefits
Peracid precursors are also known for providing more effective
bleaching. Particularly effective are the hydrophobic bleach precursor
such as Nonanoyl Oxy Benzene Sulphonate (HOBS), which generates a
fatty acid by-product in the wash liquor. However, this is ineffective at
controlling suds in high temperatures wash conditions.
Further hydrophobic bleach precursors known in the art are described in
EP 699,230 and EP 0170386.
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EP 699,230 teaches an amidoperoxy compound and its precursors
such as (6-octanamidocaproyl) oxybenzenesulphonate, (6-
nonamidocaproyl) oxybenzene sulphonate, (6-
decanamidocaproyl)oxybenzene sulphonate and mixtures thereof
compatible with enzyme which has a bleach cleaning and enzyme
cleaning performance. It discloses a detergent composition with nil-LAS
surfactant, and teaches that the amidoperoxy compound can be formulated
with hydrophilic activators such as TAED.
EP 0170386 teaches amidoperoxy compound and their precursors in a
peroxygen bleaching composition which provide effective bleaching of
textiles over a wide range of temperatures.
It has now been found that amidoperoxy compounds and their precursors
such as described is EP 699,230 and EP 0170386 gives further
enhanced suds suppressing properties.
Furthermore, it has also been found that amidoacid compounds have suds
suppressing properties.
It is an object of the invention to provide a detergent composition
comprising new suds suppressor compounds selected from amidoacid and
mixtures of amidoacid and amidoperacid.
It is further object of the invention to provide an aqueous wash liquor
containing a detersive surfactant comprising a Clp-C20 alkyl sulphate,
optionally together with builders, detergent adjuncts and a suds
suppressor wherein said suds suppressor is formed from a suds
suppressor precursor.
SUMMARY OF THE INVENTION
The present invention encompasses a detergent composition formulated
with conventional detersive surfactants, optional builders, detergent
adjuncts and a suds suppressor, wherein said suds suppressor is an
amidoacid of formula
R~ -C-N-R2-COOH or R~ -N-C-R2-COOH
O R5 R5 O
or its alkali metal, alkaline earth metal salts or mixture thereof,
WO 95/32268 2 ~ 8 9 7 51 P~~S95/04758
3
wherein Rl is an alkyl, aryl or alkaryl group containing from 1 to
14 carbon atoms, R2 is an alkylene, arylene or alkarylene group
containing from 1 to 14 carbon atoms, RS is H or an alkyl, aryl, or
alkaryl group containing from 1 to 10 carbon atoms.
DETAILED DESCRIPTION OF THE INVENTION
The present invention contemplates detergent compositions having suds
suppressing properties.
An essential component useful for the purpose of the invention is a suds
suppressor compound in a detergent composition formulated with
conventional detersive surfactants, optional builders, detergent adjuncts,
wherein said suds suppressor is selected from amidoacid and mixtures of
amidoacid and amidoperacid.
Levels of said surfactants in the detergent composition will typically be
from 1 % to 80% by weight of the detergent composition and levels of
said suds suppressor from 0.025 k to 20 l by weight of the detergent
composition.
The described compounds, i.e. amidoacid and mixture of amidoacid and
amidoperacid, exhibit excellent suds suppressing properties and may be
used as a 'detergent active' suds suppressor or as a co-suds suppressor
agent.
By 'detergent active', it is meant that further to its suds suppressing
activity, the amidoacid or the mixture of amidoacid and amidoperacid
gives also a bleaching activity with or without a bleaching agent.
When used as a co-suds suppressor agent, the development encompasses
two advantages:
Firstly, it enhances the suds suppressing properties of the detergent
composition.
Secondly, it allows the use of lower than conventional levels of expensive
suds suppressors such as silicone, fatty acid, twin-chain alcohols; thus
reducing the cost of the product.
Additionally, the suds suppressing properties of this development are
retained in the presence of organic peroxyacid bleaches derived from
mixtures of perhydrates and precursors which contain one or more N-acyl
or O-acyl group such as TAED, NOBS, acyl lactam and cationic
precursors, or preformed peracids such as amido peracids or diperacids.
WO 95132268 218 9 7 51 PCT~S95104758
4
The presence of such peroxyacid bleaches permits the use of a widest
range of stains bleaching.
Furthermore, the amidoacid and the mixture of amidoacid and
amidoperacid show a good suds suppressing activity with surfactants
selected from anionic, cationic, nonionic ampholytic, amphoteric and .
zwitterionic surfactants and mixtures thereof. Especially preferred
surfactants are those selected from anionic, nonionic, cationic surfactants
and mixtures thereof.
Most preferred surfactants for an enhanced reduction of suds formed from
surfactants are nil-LAS surfactants.
A main component useful for providing the suds suppressing properties is
an amidoacid of formula
R.~ -C-N-R2-COOH or R~ -N-C-R2-COOH
0 R5 R5 O
or its alkali metal, alkaline earth metal salts or mixture thereof,
wherein Rl is an alkyl, aryl or alkaryl group containing from 1 to
14 carbon atoms, R2 is an alkylene, arylene or alkarylene group
containing from 1 to 14 carbon atoms, RS is H or an alkyl, aryl, or
alkaryl group containing from 1 to 10 carbon atoms.
Another suds suppressor component useful for the present invention is a
mixture of amidoacid as described above and amidoperacid of formula
R~-C-N-R2-C-OOH or R~ -N-C-R2-C-OOH
O RS 0 R5 0 O
or its alkali metal, alkaline earth metal salts or mixture thereof,
wherein Rl is an alkyl, aryl or alkaryl group containing from 1 to
14 carbon atoms, R2 is an alkylene, arylene or alkarylene group
containing from 1 to 14 carbon atoms, RS is H or an alkyl, aryl, or
alkaryl group containing from 1 to 10 carbon atoms.
Preferred suds suppressors such as described herein before are those
wherein Rl is an alkyl group containing from 6 to 12 carbon atoms, R2
contains from 1 to 8 carbon atoms, and RS is H or methyl. Particularly
WO 95!32268 PCTIUS95104758
2189731
s
preferred suds suppressers are those of the above general formulas
wherein Rl is an alkyl group containing from 7 to 10 carbon atoms and
R2 contains from 4 to s carbon atoms.
Level of said suds suppresser in the detergent composition are normally
added at a level of from 0.02s I to 20%, preferably from O.OS~ to ls~,
more preferably from 0.06 to 12% and most preferably from 0.06°k to
7~ by weight of the composition.
The detergent compositions in which said suds suppressers can be used
include compositions which are to be used for cleaning substrates, such as
fabrics, fibers, hard surfaces, skin, etc.; for example hard surface
cleaning compositions (with or without abrasives), laundry detergent
compositions, automatic and non-automatic dishwashing compositions.
Suds suppresser precursors
Another aspect of the present invention comprises an aqueous wash liquor
containing a detersive surfactant comprising a C10-C20 alkyl sulphate,
optionally together with builders, detergent adjuncts and a suds
suppresser compound wherein said suds suppresser is formed from a suds
suppresser precursor of formula
Ri -C-N-R2-C-L or R~ -N-C-R2-C-L
O R5 0 R5 O O
or mixtures thereof,
wherein Rl is an alkyl, aryl or alkaryl group containing from 1 to
14 carbon atoms, R2 is an alkylene, arylene or alkarylene group
containing from 1 to 14 carbon atoms, RS is H or an alkyl, aryl, or
alkaryl group containing from 1 to 10 carbon atoms, and L is a
leaving group.
L can be essentially any suitable leaving group. A leaving group is any
group that is displayed from the suds suppresser precursor as a
consequence of the nucleophilic attack on the suds suppresser precursor
by the perhydroxide anion. This, the perhydrolysis reaction, results in the
formation of the percarboxylic acid suds suppresser. A competing
reaction can also occurs which is the hydrolysis reaction. This hydrolysis
WO 95132268 PCT/US95/04758
6
reaction results in the formation of the carboxylic acid suds suppressor. In
absence of the perhydroxide anion, the nucleophilic attack is provided by
the hydroxide anion which provide as for the competing reaction cited
above an hydrolysis reaction. This results in the formation of the
carboxylic acid suds suppressor. ,
Generally, for a group to be a suitable leaving group it must exert an
electron attracting effect. It should also form a stable entity so that the
rate of the back reaction is negligible. This facilitates the nucleophilic
attack by the perhydroxide anion or the hydroxide anion.
The L group must be sufficiently reactive for the reaction to occur within
the optimum time frame (e.g., a wash cycle). However, if L is too
reactive, this precursor will be difficult to stabilise in detergent
composition. These characteristics are generally paralleled by the pKa of
the conjugate acid of the leaving group, although exceptions to this
convention are known. Ordinarily, leaving groups that exhibit such
behaviour are those in which their conjugate acid has a pKa in the range
of from 4 to 13, preferably from 6 to 11 and most preferably from 8 to
11.
Preferred suds suppressor precursors are those of the above general
formula wherein Rl, R2 and RS are as defined for the suds suppressor
(amidoacid and amidoperacid) and L is selected from
W095132268 ~ PCT/QT595/04758
7
O
_' ~i)R3Y _ iR3 _ /Y -N_~_R1
0~ O~~ O~ i
Y , , R3
i
Y
O
-N ~N -N-C-CH-R4
a
' R3 Y
O Y O
~I
O CH -C ~C~ 4
-p-~-R~ , -~2/NR4 -N\ /NR
\C '
0 0
R3 Y
i i
0-CH = C-CH = CH2 , -O-CH = C-CH = CH2 ,
R3 O Y
-O-C = CHR4 , and-N-S-CH-R4
R3 0
and mixtures thereof, wherein Rl is an alkyl, aryl or alkaryl group
containing from 1 to 14 carbon atoms, R3 is an alkyl chain containing
from 1 to $ carbon atoms, R4 is H or R3, and Y is H or a solubilising
group.
The preferred solubilising groups are -S03-M+', -C02-M-~-, -S04-M-~',
-N+(R3)qX- and O <--N(R3)3 and most preferably -S03-M+ and -C02-
M'1' wherein R3 is an alkyl chain containing from 1 to 4 carbon atoms, M
is a cation which provides solubility to the suds suppressor precursor and
X is an anion which provides solubility to the suds suppressor precursor.
' Preferably, M is an alkali metal, ammonium or substituted ammonium
cation, with sodium and potassium being most preferred, and X is a
halide, hydroxide, methylsulphate or acetate anion. It should be noted that
suds suppressor precursors with a leaving group that does not contain a
solubilising group should be well dispersed in the detergent composition
in order to assist in their dissolution.
WO 95/32268 PCTIUS95104758
g
Preferred suds suppressor precursors are those of the above general
formula wherein L is selected from
Y R3 R3Y
-0~~ -0~\ and -
~/Y
wherein R3 is as defined above and Y is -S03-M-~' or -C02'M'~' wherein
M is as defined above.
Preferably, L has the general formula:
O~SOg M+
The suds suppressor precursors defined herein before will comprise at
least 0.1 ~, preferably from 0.19b to 50~, more preferably from 0.29b to
309&, most preferably from 0.5 % to 25l , by weight of the detergent
composition.
Another embodiment of the present invention is the addition to the
detergent composition of the invention of other suds suppressor agents
and/ or detersive surfactants.
When the detergent composition of the present invention is used with
additional suds suppressors such as 'silicone' and anionic surfactants,
both described herein after; the ratio of said anionic surfactant to said
silicone is preferably from at least 10 to 1, more preferably from at least
15 to 1.
Furthermore, if the anionic surfactant is alkyl sulphate, the preferred ratio
of said alkyl sulphate to said silicone is from at least 20 to 1.
Arlrlitinnal c"ds su,Rpressors
A wide variety of materials, well known to those skilled in the art, may
be used as additional or co-suds suppressors. See, for example, Kirk
Othmer Encyclopaedia of Chemical Technology, Third Edition, Volume
7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category of suds
WO 95132268 ~ ~ g g 7 51 PCTlUS95104758
9
suppressor of particular interest encompasses monocarboxylic fatty acid
and soluble salts therein. See U.S. Patent 2,954,347, issued September
27, 1960 to Wayne St. John. 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 Clg-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 haloparaffin 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
suppressors are described, for example, in U.S. Patent 4,265,779, issued
May 5, 1981 to Gandolfo et al. 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 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
known in the art and are, for example, disclosed in U.S. Patent
4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent
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1~
Publication No. 354,016 published February 7, 1990, by Starch, M. S.
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, Bartolotta et al, and in U.S. Patent 4,652,392,
Baginski et ai, issued March 24, 1987.
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 ~ units of Si02 units in a ratio
of from (CH3)3 SiOI~ 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 giycols or
polyethylene-polypropylene glycol copolymers or mixtures thereof
(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; aad (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
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granular compositions, gels, etc. See also U.S. Patents 4,978,471,
Starch, issued December 18, 1990, and 4,983,316, Starch, issued January
8, 1991, 5,288,431, Huber et al., issued February 22, 1994, 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 ~,. 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 200IPEG 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 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-C16 alkyl
alcohols having a C 1-C 16 chain. A preferred alcohol is 2-butyl octanol,
whsch 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.
Another highly preferred foam regulator system is described in WO
93/17772, which system is a granular free flowing foam regulator
containing carrier flee from surfactant. The surfactant component is
preferably a C12-C22 alkyl sulphate, an alkyl polyglycoside especially
based on glucose with a C 12-C 18 alkyl group andlor an alkali salt of a
sulphonation product of a (m)ethyl ester of a C 12-C22 fatty acid. The
WO 95132268 21$ 9 7 51 PCT~S95/04758
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system is free from Si02, the carrier is free from phosphate and is water-
soluble or -dispersible, and the paraffin wax is solid at room temperature
and up to 100% by weight liquid at below 90°C.
By antifoam compound it is meant herein any compound or mixtures of ,
compounds which act such as to depress the foaming or sudsing produced
by a solution of a detergent composition, particularly in the presence of
agitation of that solution.
An exemplary foam regulator system for use herein is granular, free-
flowing foam regulator which contains:
1-a granular, surfactant-free carrier, and
2-an adsorbed uniform defoamer mixture free from siloxane polymers and
emulsifying or dispersant tensides, containing
a)-70-95 % by weight of a paraffin wax or mixture and
b)-30-5 % of a bisamide from C2-C7 diamines and C12-C22
saturated carboxylic acids.
Another highly preferred antifoam controller is described in WO
94100547, which antifoam controller is lecithin, preferably soya-lecithin.
The compositions herein will generally comprise from 096 to 5% of
additional suds suppressers. When utilized as suds suppressers,
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 396 of fatty monocarboxylate suds suppresser is utilized.
Silicone suds suppressers 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 minimised and effectiveness of lower amounts for
effectively controlling sudsing. Preferably from 0.0136 to 196 of silicone
suds suppresser is used, more preferably from 0.25%O to 0.596. 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 suppressers
are generally utilized in amounts ranging from 0.1 % to 2%, by weight, of
the composition. Hydrocarbon suds suppressers are typically utilized in
amounts ranging from 0.01 % to 5.0~, although higher levels can be
WO 95/32268 PCT/US95/04758
13
used. The alcohol suds suppressors are typically used at 0.2%-3~ by
weight of the finished compositions.
Detersive surfactants
~ Nonlimiting examples of surfactants useful herein typically at levels from
1°Xo to 55~, by weight, include the conventional C11-Clg alkyl benzene
sulphonates ("LAS") and primary, branched-chain and random C10-C20
alkyl sulphates ("AS"), the C10-Clg secondary (2,3) alkyl sulphates of
the formula CH3(CH~)x(CHOS03 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 sulphates such as oleyl sulphate, the
Cl0-Clg alkyl alkoxy sulphates ("AEXS"; especially EO I-7 ethoxy
sulphates), Cl0-Clg alkyl alkoxy carboxylates (especially the EO 1-S
ethoxycarboxylates), the C10-18 glycerol ethers, the C10-Clg alkyl
polyglycosides and their corresponding sulphated polyglycosides, and
C12-Clg alpha-sulfonated fatty acid esters.
Preferably, the detergent composition is substantially free of LAS
surfactant (i.e. less than 1 k, preferably less than 0.5~ of LAS surfactant
by weight of the composition and most preferably contains no LAS
surfactant).
If desired, the conventional nonionic and amphoteric surfactants such as
the C12-Clg alkyl ethoxylates ("AE") including the so-called narrow
peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially
ethoxylates and mixed ethoxy/propoxy), C12-Clg betaines and
sulfobetaines ("sultaines"), Ci0-Clg amine oxides, and the like, can also
be included in the overall compositions.
Amine oxide is a useful detersive surfactant for the purpose of the
invention as it gives a strong cleaning benefit in combination with other
detersive surfactants such as Oleyl sarcosinate. Especially preferred,
when used in combination with other surfactants, is the C14 amine oxide.
The C10-Clg N-alkyl polyhydroxy fatty acid amides can also be used.
Typical examples include the C12-Cig N-methylglucamides. See WO
92/06154. Other sugar-derived surfactants include the N-alkoxy
polyhydroxy fatty acid amides, such as Clp-Clg N-(3-methoxypropyl)
glucamide. The N-propyl through N-hexyl C12-Clg glucamides can be
used for low sudsing. C10-C2p conventional soaps may also be used.
Mixtures of anionic and nonionic surfactants are especially useful.
WO 95132268 PCTlUS95/04758
2189751
14
Cationic surfactants can also be used in the detergent compositions herein.
Preferred cationic surfactants suitable for the purpose of the invention are
Coco N-hydroxyethyl-N,N-dimethyl ammonium salts and choline ester.
Other conventional useful surfactants are listed in standard texts.
Additional detP~ .n ompon nt
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.
When formulated as 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
detergent components selected from bleach activators and preformed
peracids, bleaching agents and mixtures thereof.
When preformed peracids are used, they may be selected from
amidoperacid, diperacid and mixtures thereof.
Bleach activators _
If present, the amount of bleach activators will typically be from 0.13b to
60%, more typically from 0.5 % to 403'0 of the detergent composition.
These activators contains one or more N- or O-acyl groups and can be
selected from a wide range of classes.
Various nonlimiting examples of activators are disclosed in U.S. Patent
4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent
4,412,934. The nonanoyloxybenzene sulfonate (HOBS) and tetraacetyl
ethylene diamine (TAED) activators are typical, and mixtures thereof can
also be used. Also included as bleach activators are the benzoyl
oxybenzene sulfonate as disclosed in, for example, EP-A-0341947 and
cationic derivatives of the benzoyl oxybenzene sulphonates. See also U.S.
4,634,551 for other typical bleaches and activators useful herein.
CA 02189751 1999-09-07
IS
A useful class of bleach activators is the amido suds suppressor
precursors of the invention, which may also function as an activator.
These activators can additionally be used with other activators such as
described herein (NOBS, TAED, benzoxazin activators, acyl lactam
activators and cationic activators and mixtures thereof)
Another class of bleach activators comprises the benzoxazin-type
activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued
October 30, 1990. A highly preferred activator of the benzoxazin-type is:
0
11
C
N
Still another class of preferred bleach activators includes the acyl lactam
activators, especially acyl caprolactams and acyl valerolactams of the
formulae:
O
It -CH - p ~-CH
s
s-O C 2 C~ R -C ~ 2~H2
R C N~,C~-C~~Ct'12 t~CHZ-Ct'i2
wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing
from 1 to 12 carbon atoms. Highly preferred lactam activators include
benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl
caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl
caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl
valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-
trimethylhexanoyl valerolactam and mixtures thereof. See also-U.S.
Patent 4,545,784, issued to Sanderson, October 8, 1985 which discloses acyl
caprolactams, including benzoyl caprolactam, adsorbed into sodium
perborate.
Another class of preferred bleach activators include the cationic bleach
activators, derived from the valerolactam and acyl caprolaetam
compounds, of formula:
CA 02189751 1999-09-07
16
X_ R", N,R 0
CH O IC (CH2)x
O CI -N ~CH2
CH2 - CH2-CH2
wherein x is 0 or 1, substituents R, R' and R" are each C 1-C 10 alkyl or
C2-C4 hydroxy alkyl groups, or [(CyH2y) O]n-R"' wherein y=2-4,
n=1-20 and R"' is a C1-C4 alkyl group or hydrogen and X is an anion.
~leang ag.; nts
The detergent compositions herein may optionally contain bleaching
agents. When present, bleaching agents will typically be at levels of from
1°~ to 3090, more typically from Sg& to 20°k, of the detergent
composition, especially for fabric laundering.
The bleaching agents used herein can be any of the bleaching agents
useful for detergent compositions in textile cleaning, hard surface
cleaning, or other cleaning purposes that are now known or become
known. These include oxygen bleaches as well as other bleaching agents.
Alkali metal perborate bleaches, e.g., sodium perborate (e.g., mono- or
tetra-hydrate) can be used herein.
Peroxygen bleaching agents can also be used. Suitable peroxygen
bleaching compounds include sodium carbonate peroxyhydrate and
equivalent "percarbonate" bleaches, sodium pyrophosphate
peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulphate
bleach (e.g., OXONE~, manufactured commercially by DuPont) can also be
used.
A preferred percarbonate bleach comprises dry particles having an
average particle size in the range from 500 micrometers to 1,000
micrometers, not more than 109 by weight of said particles being smaller
than 200 micrometers and not more than 109 by weight of said particles
being larger than 1,250 micrometers. Optionally, the percarbonate can be
coated with silicate, borate or water-soluble surfactants. Percarbonate is
available from various commercial sources such as FMC, Solvay and
Tokai Denka.
Mixtures of bleaching agents can also be used.
Another category of bleaching agent that can be used without
restriction encompasses percarboxylic acid bleaching agents and salts
thereof. Suitable examples of this class of agents include magnesium
CA 02189751 1999-09-07
17
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.
Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent
No. 4,634,551, Burns et al, filed June 3, 1985, European Patent
Application 0,133,354, Banks et al, published February 20, 1985, and
U.S. Patent 4,412,934, Chung et al, issued November 1, 1983. Highly
preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic
acid and nonyl amido peroxy adipic acid as described in U.S. Patent
4,634,551, issued January 6, 1987 to Burns et al.
Bleaching agents other than oxygen bleaching agents are also
known in the art and can be utilized herein. One type of non-oxygen
bleaching agent of particular interest includes photoactivated bleaching
agents such as the sulfonated zinc and/or aluminum phthalocyanines. See
U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used,
detergent compositions will typically contain from 0.025 ~ to 1.25 ~6, by
weight, of such bleaches, especially sulfonate zinc phthalocyanine.
If desired, the bleaching compounds can be catalysed by means of a
manganese compound. Such compounds are well known is the art and
include, for example, the manganese-based catalysts disclosed in U.S.
Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat.
5,114,606; and European Pat. App. Pub. Nos. 549,271A1, 549,2?2A1,
544,440A2, and 544,490A1; Preferred examples of these catalysts
include MnN2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF~2,
Ma~2(u-O) 1 (u-OAc~(1,4,7-trimethyl-1,4,7-triazacyclononane~
(C104)2, Mn~4(u-O)6(1,4,7-triazacyclononane)4(C104)4, Mn Mn~e~
(u-O~ (u-OAc)2_(1,4,7-trimethyl-1;4,7-triazacyclononanen(C104)3,
Mn (1,4,7-trimethyl-1,4,7-triazacyclononane)- (OCH3)3(PF(~, and
mixtures thereof. Other metal-based bleach catalysts include those
disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The use of
manganese with various complex ligaads to enhance bleaching is also
reported in the following United States Patents: 4,728,455; 5,284,944;
5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; 5,227,084.
As a practical matter, and not by way of limitation, the
compositions and processes herein can be adjusted 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 ppm, more preferably from 1 ppm to 500 ppm, of the catalyst species
is the laundry liquor.
WO 95/32268 PCT/US95104758
18
Adjunct Ingredients
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., perfumes,
colorants, dyes, etc.). The following are illustrative examples of such
adjunct materials.
Builders - Detergent builders can optionally be included in the
compositions herein to assist in controlling mineral hardness. Inorganic
as well as organic builders can be used. Builders are typically used in
fabric 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. Liquid
formulations typically comprise from 5 % to SO l , more typically 5 °lo
to
30 l , by weight, of detergent builder. Granular formulations typically
comprise from lOlo to 80°k, more typically from 159& to 50°o by
weight,
of the detergent builder. Lower or higher levels of builder, however, are
not meant to be excluded.
Inorganic or P-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), phosphonates, phytic acid,
silicates, carbonates (including bicarbonates and sesquicarbonates),
sulphates, and aluminosilicates. However, non-phosphate builders are
required in some locales. 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.
Examples of silicate builders are the alkali metal silicates,
particularly those having a Si02:Na20 ratio in the range 1.6:1 to 3.2:1
and layered silicates, such as the layered sodium silicates described in
U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck. 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-b silicate builder does not contain aluminum. NaSKS-6 has the
w0 95132268 PCT/US95/04758
218951
19
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[(A102)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, Krummel, et al, issued October 12,
1976. 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:
Nal2f(A102) 12(Si02) 12l ~ 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.
WO 95132268 PCT/US95/04758
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 Berg, U.S. Patent 3,128,287, issued April
7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18,
1972. See also "TMSITDS" builders of U.S. Patent 4,663,071, issued to
Bush et al, on May 5, 1987. 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, 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
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 detergent compositions of 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, Bush, issued January 28, 1986.
Useful succinic acid builders include the Cg-C20 alkyl and alkenyl
succinic acids and salts thereof. A particularly preferred compound of
WO 95132268 ~ ~ g 9 7 51 PCT~S95104758
21
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 European Patent Application 86200690.5/0,200,263,
published November 5, 1986.
Other suitable polycarboxylates are disclosed in U.S. Patent
4,144,226, Crutchfield et al, issued March 13, 1979 and in U.S. Patent
3,308,067, Diehl, issued March 7, 1967. See also Diehl U.S. Patent
3,723,322.
Fatty acids, e.g., C12-Clg 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 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.
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.
CA 02189751 1999-09-07
22
Amino phosphonates are also suitable for use as chelating agents in
the compositions of the invention when at lease low levels of total
phosphorus are permitted in detergent compositions, and include
ethylenediaminetetrakis (methylenephosphonates) as DEQUESTTM.
Preferred, these amino phosphonates to 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 3,812,044, issued
May 21, 1974, to Connor et al. Preferred compounds of this type in acid
form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-
disulfobenzene.
A preferred biodegradable chelator for use herein is
ethylenediamine disuccinate ("EDDS "), especially the [S,S] isomer as
described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and
Perkins.
If utilized, these chelating agents will generally comprise from
0.196 to 1096 by weight of the detergent compositions herein. More
preferably, if utilized, the chelating agents will comprise from 0.1 ~% to
3.096 by weight of such compositions.
Mmes - Enzymes can be included in the formulations herein for a wide
variety of fabric laundering purposes, including removal of protein-based,
carbohydrate-based, or triglyceride-based stains, for example, and for the
prevention of refugee dye transfer, and for fabric restoration. 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
choice is governed by several factors such as pH-activity and/or stability
optima, thermostability, stability versus active detergeats, builders and so
on. In this respect bacterial or fungal enzymes are preferred, such as
bacterial amylases and proteases, and fungal cellulases.
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 0.00196 to 5 fib, preferably 0.01 f6-1 % by
weight of a commercial enzyme preparation. Protease enzymes are
usually present in such commercial preparations at levels sufficient to
CA 02189751 1999-09-07
23
provide from 0.005 to 0.1 Anson units (AU) of activity per gram Qf
composition.
Suitable examples of proteases are the subtilisins which are
obtained from particular strains of B. subtilis and B, licheniforms.
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 mark ESPERASE.
The preparation of this enzyme and analogous enzymes is described in
British Patent Specification No. 1,243,784 of Novo. Proteolytic enzymes
suitable for removing protein-based stains that are commercially available
include those sold under the trademarks ,~,C~ASE and SAVINASE by
Novo Industries A/S (Denmark) and MAXATASE by International Bio-
Synthetics, Inc. (The Netherlands). Other proteases include Protease A
(see European Patent Application 130,756, published January 9, 1985)
and Protease B (see European Patent Application 251,446 published January
7, 1988, and European Patent Application 130,756, Bott et al, published
January 9, 1985).
Amylases include, for example, a-amylases described in British
Patent Specification No. 1,296,839 (Novo), RAPIDASETM, International
Bio-Synthetics, Inc. and TERMAMYLTM, Novo Industries. FUNGAMYLTM
(Novo) is especially useful.
The cellulase usable in the present invention include both bacterial
or fungal cellulase. Preferably, they will have a pH optimum of between
and 9:5. Suitable cellnlases are disclosed in U.S. Patent 4,435,307,
Barbesgoard et al, issued March 6, 1984, which discloses fungal cellulase
produced from Humicola insolens and Humicola strain DSM1800 or a
cellulase 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. CAREZYME
(Novo) is especially useful.
Suitable lipase enzymes for detergent usage include those produced
by microorganisms of the Pseudomonas group, such as Pseudomonas
stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. See also
lipases in Japanese Patent Application 53,20487, laid open to public
inspection on February 24, 1978. This lipase is available from Amano
Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade mark Lipase P
"Amano," hereinafter referred to as "Amano-P." Other commercial
lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g.
CA 02189751 1999-09-07
24
Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially
available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter
viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth
Co., The Netherlands, and lipases ex Pseudomonas gladioli. The
LIPOLASE~'enzyme derived from Humicola lanuginosa and commercially
available from Novo (see also EPO 341,947) is a preferred lipase for use
herein.
Peroxidase enzymes are used in combination with oxygen sources,
e.g., percarbonate, perborate, persulphate, 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
subsErates 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 PCT
International Application WO 89/099813, published October 19, 1989, by
O. Kirk, assigned to Novo Industries A/S.
A wide range of enzyme materials and means for their
incorporation into synthetic detergent compositions are also disclosed in
U.S. Patent 3,553,139, issued January 5, 1971 to McCarty et al:
Enzymes are further disclosed in U.S. Patent 4,101,457, Place et al,
issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued
March 26, 1985, both. Eazyme materials useful for liquid detergent
formulations, and their incorporation into such formulations, are disclosed
in U.S. Patent 4,261,868, Hora et al, issued April 14, 1981. Enzymes
for use in detergents can be stabilised by various techniques. Enzyme
stabilisation techniques are disclosed and exemplified in U.S. Patent
3,600,319, issued August 17, 1971 to Gedge, et al, and European Patent
Application Publication No. 0 199 405, published October 29, 1986, Venegas.
Enzyme stabilisation systems are also described, for example, in U.S. Patent
3,519,570.
~,3r Soil Removal/Anti-redeposition A_eents - The compositions of 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 0.019 to l0.OR6 by weight of the water-soluble ethoxylates
amines; liquid detergent compositions typically contain 0.019~c to 5 96 .
WO 95132268 PGTIUS95104758
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 l,
1986. Another group of preferred clay soil removal-antiredeposition
agents are the cationic compounds disclosed in European Patent
Application 111,965, Oh and Gosselink, published June 27, 1984. Other
clay soil removallantiredeposition agents which can be used include the
ethoxylated amine polymers disclosed in European Patent Application
111,984, Gosselink, published June 27, 1984; the zwitterionic polymers
disclosed in European Patent Application 112,592, Gosselink, published
July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744,
Connor, issued October 22, 1985. 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 Di~ersin~ Agents - Polymeric dispersing agents can
advantageously be utilized at levels from 0.1 % to 7% , by weight, in the
compositions herein, especially in the presence of zeolite andlor layered
silicate builders. Suitable polymeric dispersing agents include polymeric
polycarboxylates and polyethylene glycols, although others known in the
art can also be used. It is believed, though it is not intended to be limited
by theory, that polymeric dispersing agents enhance overall detergent
builder performance, when used in combination with other builders
(including lower molecular weight polycarboxylates) by crystal growth
inhibition, particulate soil release peptization, and anti-redeposition.
Polymeric polycarboxylate materials can be prepared by
polymerising or copolymerizing suitable unsaturated monomers,
preferably in their acid form. Unsaturated monomeric acids that can be
polymerised to form suitable polymeric polycarboxylates include acrylic
acid, malefic acid (or malefic anhydride), fumaric acid, itaconic acid,
aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
The presence in the polymeric polycarboxylates herein or 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.
Particularly suitable polymeric polycarboxylates can be derived
from acrylic acid. Such acrylic acid-based polymers which are useful
WO 95!32268 PCTIUS95/U4758
26
herein are the water-soluble salts of polymerised acrylic acid. The
.average molecular weight of such polymers in the acid form preferably
ranges from 2,000 to 10,000, more preferably from 4,000 to 7,000 and
most preferably from 4,000 to 5,000. Water-soluble salts of such acrylic
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.
Acrylic/maleic-based copolymers may also be used as a preferred
component of the dispersing/anti-redeposition agent. Such materials
include the water-soluble salts of copolymers of acrylic acid and malefic
acid. The average molecular weight of such copolymers in the acid form
preferably ranges from 2,000 to 100,000, more preferably from 5,000 to
75,000, most preferably from 7,000 to 65,000. The ratio of acrylate to
maleate segments in such copolymers will generally range from 30:1 to
1:1, more preferably from 10:1 to 2:1. Water-soluble salts of such
acrylic acid/maleic acid copolymers can include, for example, the alkali
metal, ammonium and substituted ammonium salts. Soluble
acrylate/maleate copolymers of this type are known materials which are
described in European Patent Application No. 66915, published
December 15, 1982, as well as in EP 193,360, published September 3,
1986, which also describes such polymers comprising
hydroxypropylacrylate. Still other useful dispersing agents include the
maleic/acrylic/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 polymeric material which can be included is polyethylene
glycol (PEG). PEG can exhibit dispersing agent performance as well as
act as a clay soil removal-antiredeposition agent. Typical molecular
weight ranges for these purposes range from 500 to 100,000, preferably
from 1,000 to 50,000, more preferably from 1,500 to 10,000.
Polyaspartate and polyglutamate dispersing agents may also be
used, especially in conjunction with zeolite builders. Dispersing agents
such as polyaspartate preferably have a molecular weight (avg.) of
10,000.
Polymeric Soil Release Agent - Any polymeric soil release agent known
to those skilled in the art can optionally be employed in the compositions
WO 95132268 ~ PCTlUS95104758
27
and processes of this invention. Polymeric soil release agents are
characterised by having both hydrophilic segments, to hydrophilize 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.
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 polymerisation of at least 2, or (ii) oxypropylene or
polyoxypropylene segments with a degree of polymerisation 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 com-
prising at least 25 % oxyethylene units and more preferably, especially for
such components having 20 to 30 oxypropylene units, at least 50°6
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 2:1 or
lower, (ii) C4-C6 alkylene or oxy C4-C( alkylene segments, or mixtures
therein, (iii) poly (vinyl ester) segments, preferably polyvinyl acetate),
having a degree of polymerisation of at least 2, or (iv) C1-Cq. alkyl ether
or Cq. hydroxyalkyl ether substituents, or mixtures therein, wherein said
substituents are present in the form of C1-Cq. 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-Cq, alkyl ether and/or C4 hydroxyalkyl ether units to deposit upon
conventional polyester synthetic fiber surfaces and retain a sufficient level
of hydroxyls, once adhered to such conventional synthetic fiber surface,
to increase fiber surface hydrophilicity, or a combination of (a) and (b).
CA 02189751 1999-09-07
28
Typically, the polyoxyethylene segments of (a)(i) will have a degree
of polymerisation of from 200, although higher levels can be used,
preferably from 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 M03S(CH2)nOCH2CH20-,
where M is sodium and n is an integer from 4-6, as disclosed in U.S.
Patent 4,721,580, issued January 26, 1988 to Gosselink.
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). Cellulosic soil release agents
for use herein also include those selected from the group C 1-C4 alkyl and
C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December
28, 1976 to Nicol, et al.
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 European Patent
Application 0 219 048, published April 22, 1987 by Kud, et al.
Commercially 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, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued
July 8, 1975.
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 90-809 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 ZELCONTM 5126 (from
Dupont) andMILEASETM T(from ICI). See also U.S. Patent 4,702,857,
issued October 27, 1987 to Gosselink.
WO 95132268 PCT/US95104758
29
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, issued
November 6, 1990 to J.J. Scheibel and E.P. Gosselink. Other suitable
polymeric soil release agents include the terephthalate polyesters of U.S.
Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic
end-capped oligomeric esters of U.S. Patent 4,721,580, issued January
26, 1988 to Gosselink, and the block polyester oligomeric compounds of
U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
Preferred polymeric soil release agents also include the soil release
agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado
et al, which discloses anionic, especially sulfoarolyl, end-capped
terephthalate esters.
If utilized, soil release agents will generally comprise from 0.01 %
to 10.0%, by weight, of the detergent compositions herein, typically from
0.1 % to 5 % , preferably from 0.2 % to 3.0 % .
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)-ethanesulphonate. Said soil release
agent also comprises from 0.5 % to 20% , by weight of the oligomer, of a
crystalline-reducing stabiliser, preferably selected from the group xylene
sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
lyP Transfer Inhibiting Agents - The compositions of 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 10% by weight of the composition, preferably
from 0.01% to 5%, and more preferably from 0.05% to 2%.
WO 95132268 ~ PCT/U89510~1758
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 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-O group can be represented by the following general
structures:
O O
(Rihc- i -(Ry; =N-(Rthc
(R3)z
wherein Rl, 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-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 polymerisation. Typically, the average
molecular weight is within the range of 500 to 1,000,000; more preferred
1,000 to 500,000; most preferred 5,000 to 100,000. This preferred class
of materials can be referred to as "PVNO".
CA 02189751 1999-09-07
31
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., ~.t
Analysis, Vol 113. "Modern Methods of Polymer Characterization". The
PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-
vinylpyrrolidone from 1:1 to 0.2:1, more 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 of a ppm basis delivered in wash
solutions is from 2:1 to 50:1, and more preferably from 3:1 to 10:1.
The detergent compositions herein may also optionally contain from
0.005 °~ to 5 96 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 0.019 to 1 % by
weight of such optical brighteners.
The hydrophilic optical brighteners useful in the present invention
are those having the structural formula:
Ri
H H N
N / N ~ C=C ~ N--~~ N
I
g N--C
SO
RZ S03M ~M
wherein Rl is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-
CA 02189751 1999-09-07
32
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-Z-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)amino]-2,2'-
stilbenedisulfonic 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, Rl is anilino, R2 is N-2-hydroxyethyl-
N-2-methylamino and M is a cation such as sodium, the brightener is 4,4'-
bis[(~4-anilino-6-(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
5BM-GX by Ciba-Geigy Corporation.
When in the above formula, Ri is anilino, R2 is morphilino and M
is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-
morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt.
This particular brightener species is commercially marketed under the
trademark Tinopal AMS-GX by Ciba Geigy Corporation.
The specific optical brightener species selected for use 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
PVPVT) with such selected optical brighteners (e.g., Tinopal UNPA-GX,
Tinopal SBM-GX and/or Tinopal AMS-GX) provides significantly better
dye transfer inhibition in aqueous wash solutions than does either of these-
two detergent composition components when used alone. Without being
bound by theory, it is believed that such brighteners work this way
because they have high affinity for fabrics in the wash solution and
therefore deposit relatively quick on these fabrics. The extent to which
brighteners deposit on fabrics in the wash solution can be defined by a
parameter called the "exhaustion coefficient" . The exhaustion coefficient
is in general as the ratio of a) the brightener material deposited on fabric
to b) the initial brightener concentration in the wash liquor. Brighteners
with relatively high exhaustion coefficients are the most suitable for
inhibiting dye transfer in the context of the present invention.
CA 02189751 1999-09-07
33
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.
~ener - Any optical brighteners or other brightening or whitening
agents known in the art can be incorporated at levels typically from
0.05 l 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, 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 Brightening Agents", M. Zahradnik, Published
by John Wiley & 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, issued
to Wixon on December 13, 1988. These brighteners include the
)RWHITETMseries 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-
styryl-phenyl~2H-naptho[1,2-d]triazoles; 4,4' bis(1,2,3-triazol-2-yl)-
sdlbenes; 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-Biphenyl-pyrazolines;
2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naptho[1,2-d]oxazole; and 2-
(stilben-4-yl) 2H-naphtho[1,2-d]triazole. See also U.S. Patent 3,646,015,
issued February 29, 1972 to Hamilton. Anionic brighteners are preferred
herein.
Fabric Softeners - Various through-the-wash fabric softeners, especially
the impalpable smectite clays of U.S. Patent 4,062,647, Storm and
Nirschl, issued December 13, 1977, as well as other softener clays known
in the art, can optionally be used typically at levels of from 0.5 ~ to 1096
by weight in the present compositions to provide fabric softener benefits
concurrently with fabric cleaning. Clay softeners can be used in
WO 95!32268 PCT/US95/04758
34
combination with amine and cationic softeners as disclosed, for example,
in U.S. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent
4,291,071, Harris et al, issued September 22, 1981.
Q h r Ingredi nts - A wide variety of other ingredients usefulin detergent y
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.
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°I of C13-15 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 surfactants, 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
k to 90% , typically 10°b 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.
WO 95/32268 PCTIUS95104758
2i8975i
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 detergent composition of the present invention is effective in soft and
hard water and can be used in a well built formulation, wherein the
builder content is at least 125 ~ by weight of the formulation, as well as
in a low built formulation, wherein the builder content is less than 15 %
by weight of the formulation.
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:
LAS : Sodium linear C 12 alkyl benzene sulphonate
XYAS : Sodium C1X - Cly alkyl sulphate
APG : Allcyl polyglycoside surfactant of formula C12 -
(glycosyl)x, where x is 1.5,
24EY : A C12_14 Predominantly linear primary alcohol
condensed with an average of Y moles of
ethylene oxide
45EY : A C 14 - C I S Predominantly linear primary
alcohol condensed with an average of Y moles of
ethylene oxide
XYEZS : C 1X - C 1 y sodium alkyl sulphate condensed
. with an average of Z moles of ethylene oxide per
mole
CA 02189751 1999-09-07
36
NaSKS-6 : Crystalline layered silicate of formula 8
Na2Si205
Carbonate : Anhydrous sodium carbonate
MA/AA : Copolymer of 1:4 maleic/acrylic acid, average
molecular weight about 80,000
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
Citrate : Tri-sodium citrate dihydrate
Citric : 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
Protease . Proteolytic enzyme sold under the trademark
Savinase by Novo Industries A/S (approx 2%
enzyme activity).
Lipase : Lipolytic enzyme sold under the trademark
Lipolase by Novo Industries A/S (approx 2%
enzyme activity)
Cellulase : Cellulosic enzyme sold under the trademark
Carezyme by Novo Industries A/S.
CA 02189751 1999-09-07
37
Endo A : Trademark of a cellulosic enzyme sold by Novo
Industries A/S
PVNO : Polyvinyl pyridine N-oxide polymer of molecular
weight 10,000
MgS04 : Anhydrous Magnesium Sulphate
SRP : modified anionic polyester Soil Release Polymer
CMC : Sodium carboxymethyl cellulose
EDDS : Ethylenediamine -N, N- disuccinic acid, [S,S]
isomer in the form of the sodium salt.
silicone . 25% paraffn wax Mpt 50°C,17% hydrophobic
silica, 58% para~n oil.
1108 of the dete.,r., ~ent formulations described herein after are taken and
added to a Miele-b98 washing machine containing 1.5 kg of clean, new
terry towel ballast. The products are tested at 90°C, main wash cycle,
using soft water (3 ° Clark).
The ~% suds is measured and calculated using the following expression:
96 suds= right of suds visible Lhroueh yort hole * 10096
height of port hole
4 replicates of each product are completed.
i)-detergent compositions
WO 95/32268 PCTIUS95/04758
2j89751
38
The following compositions were prepared and tested for sudsing.
Composition A formed wash liquor in accordance with the prior art while
composition 1 formed wash liquor in accordance with the invention and
composition 2 embodiment of the invention show the suds suppression
effect of differing types of amidoacid and amidoperacid.
A 1 2
TAED 5
6-Octanamido/ - 5 -
6 Decanamido
Caproyl Oxy Benzene
Sulphonate (50:50
blend)
6-Octanamidol - -
6 Decanamido
Caproic Acid (50:50
blend)
C45AS 10 10 10
C25AE3S 2 2 2
C24E5 3 3 3
N-Methyl Glucamide 3 3 3
Zeolite A 17 17 17
SKS-6 12 12 12
Citric 3 3 3
MA/AA 5 5 5
CMC 0.4 0.4 0.4
PEG 0.5 0.5 0.5
Savinase 2.4 2.4 2.4
Lipolase 0.2 0.2 0.2
Cellulase 0.2 0.2 0.2
Endo A 0.2 0.2 0.2
SRP 0.4 0.4 0.4
PVNO 0.02 0.02 0.02
Carbonate
Zinc Phthalocyanine20 ppm 20 ppm 20 ppm
sulphonate
Silicone 0.4 0.4 0.4
Percarbonate 20 20 20
Water minors and to balance
miscellaneous
W 0 95/32268 , PCT/US95/04758
39
ii)-suds results
The above compositions are evaluated for sudsing with the suds method
described herein before in medium hard water (12° Clark).
A 1 2
96 suds (30mns) 85 28 6
The amidoacid alone gives a a very effective suds suppressing action at
the foaming from the surfactant system.
Example 2
i)-detergent compositions
The following compositions were prepared and tested for sudsing.
Compositions A, B, C formed wash liquors in accordance with the prior
art while composition 1, 2, 3, 4 formed wash liquors in accordance with
the invention show the suds suppression effect of differing levels of
amidoacid and amidoperacid.
A B C 1 2 3 4
LAS 10 - - 10 - - -
C45AS - 10 10 - 10 10 10
Silicone 0.3 0.3 0.3 0.3 - 0.3 0.3
TAED 5 5 - - - - 3
6- - - - 5 5 5 3
Octanamido/
6 Decanamido
Caproyl Oxy
Benzene
Sulphonate
(50:50 blend)
C45E7 4 4 4 4 4 4 4
Zeolite A 18 18 18 18 18 18 18
SKS-6 8 8 8 8 8 8 8
Citric 4 4 4 4 4 4 4
MA/AA 4 4 4 4 4 4 4
SRP 0.3 0.3 0.3 0.3 0.3 0.3 0.3
CMC 0.3 0.3 0.3 0.3 0.3 0.3 0.3
EDDS 0.4 0.4 0.4 0.4 0.4 0.4 0.4
MgS04 0.4 0.4 0.4 0.4 0.4 0.4 0.4
WO 95/32268 ~ ~ PCTIUS95/D4758
Percarbonate18 18 18 18 18 18 18
Carbonate 4.5 4.5 4.5 4.5 4.5 4.5 4.5
Savinase 1.2 1.2 1.2 1.2 1.2 1.2 1.2 -
Lipolase 0.4 0.4 0.4 0.4 0.4 0.4 0.4
Cellulase 0.1 0.1 0.1 0.1 0.1 0.1 0.1 ,
Water minorsand to balance
miscellaneous
ii)-suds
results
A B C 1 2 3 4
suds at 70 100 100 65 60 12 25
30
minutes
From the suds test above, it is seen that LAS is a lower foaming
surfactant than coco AS.
After 30 mns of stressed suds testing, the blend is perhydrolized in its
peracid form, said peracid giving the acid. The mixture, of amidoacid and
amidoperacid suds suppressor, obtained reduces the foaming of LAS and
AS. A better reduction is seen with the foaming of the AS surfactant.
i)-detergent compositions
The following compositions were prepared and tested for sudsing and
cleaning. Compositions A and B formed wash liquors in accordance with
the prior art while compositions I, 2, 3 formed wash liquors in
accordance with the invention show the suds suppression effect of
differing levels of amidoacid and amidoperacid.
A B 1 2 3
TAED - 6 - 4
6-Octanamido/ - - 5 3 3
6 Decanamido
Caproyl Oxy
Benzene
Sulphonate
(50:50 blend)
Benzoyl - - - - 4
Caprolactam
C45AS 10 10 10 10 10
WO 95132268 PCT/US95/04758
~ 2189751
41
C25AE3S 2 2 2 2 2
C24E5 3 3 3 3 3
N-Methyl 3 3 3 3 3
Glucamide
Zeolite A 17 17 17 17 17
SKS-6 12 12 12 12 12
Citric 3 3 3 3 3
MA/AA 5 5 5 5 5
CMC 0.4 0.4 0.4 0.4 0.4
PEG 0.5 0.5 0.5 0.5 0.5
Savinase 2.4 2.4 2.4 2.4 2.4
Lipolase 0.2 0.2 0.2 0.2 0.2
Cellulase 0.2 0.2 0.2 0.2 0.2
Endo A 0.2 0.2 . 0.2 0.2 0.2
SRP 0.4 0.4 0.4 0.4 0.4
PVNO 0.02 0.02 0.02 0.02 0.02
Carbonate 6 6 6 6 6
Zinc 20 ppm 20 ppm 20 ppm 20 20 ppm
Phthalocyanin ppm
a sulphonate
Silicone 0.4 0.4 0.4 0.4 0.4
Percarbonate 20 20 20 20 20
Water minors and miscel laneous balance
to
ii)-suds results
The above compositions are evaluated for sudsing with the suds method
described herein before and for performance on a range of hydrophobic
and body soils by using a launderometer at 40°C with hard water
(12°
Clark)
A B 1 2 3
96 suds 100 100 15 30 22
(30mns)
Performance A B 1 2 3
(psu vs A)
lipstick 0 +0.5 +4.Os +3.Os +3.Ss
shoe polish 0 +0.6 +4.Os +3.Os +3.6s
WO 95/32268 218 9 7 51 PCTlUS95104758
42
tea 0 +3.0 +1.5 +2.8 +3.3
coffee 0 +2.8 +1.3 +2.5 +3.1
The mixture obtained of amidoacid and amidoperacid gives a very
effective suds suppressing action at the foaming from the surfactant
system and also provides effective cleaning performance on hydrophobic
soils like lipstick and polish.
Furthermore, when the detergent composition of the invention is
formulated with additional precursor like TAED or benzoyl caprolactam,
the suds suppression properties and performance on hydrophobic stains as
well as the performance on hydrophilic stains like tea and coffee are
retained.
le
i)-detergent compositions
The following compositions were prepared and tested for sudsing.
Compositions A and B formed wash liquors in accordance with the prior
art while composition l, 2, 3 formed wash liquors in accordance with the
invention show the suds suppression effect of differing levels of
amidoacid and amidoperacid.
A B 1 2 3
TAED - 6 - 4 -
6-Octanamidol - - 5 3 3
6 Decanamido
Caproyl Oxy
Benzene
Sulphonate
(50:50 blend)
Benzoyl - - ' - 4
Caprolactam
C45AS 5 5 5 5 5
C12-C14 alkyl 5 5 5 5 5 '
(N-hydroxy
ethyl-N,N-
dimethyl
ammonium
bromide)
WO 95/32268 PCTIUS95104758
43
C25AE3S 2 2 2 2 2
C24E7 3 3 3 3 3
N-Methyl 3 3 3 3 3
Glucamide
Zeolite A 17 17 17 17 17
SKS-6 12 12 12 12 12
Citric 3 3 3 3 3
MA/AA 5 5 5 5 5
CMC 0.4 0.4 0.4 0.4 0.4
PEG 0.5 0.5 0.5 0.5 0.5
Savinase 2.4 2.4 2.4 2.4 2.4
Lipolase 0.2 0.2 0.2 0.2 0.2
Carezyme 0.2 0.2 0.2 0.2 0.2
Endo A 0.2 0.2 0.2 0.2 0.2
SRP 0.4 0.4 0.4 0.4 0.4
PVNO 0.02 0.02 0.02 0.02 0.02
Carbonate 6 6 6 6 6
Zinc 20 ppm 20 ppm 20 ppm 20 ppm 20 ppm
Phthalocyanin
a sulphonate
Silicone 0.4 0.4 0.4 0.4 0.4
Percarbonate20 20 20 20 20
Water minors balance
and miscellaneous
to
ii)-Suds results
The above compositions are evaluated for sudsing with the suds method
described herein before in medium hard water (12° Clark).
A B 1 2 3
~ suds 100 95 35 45 41
(30 mns)
The mixture of amidoacid and amidoperacid suds suppressors obtained
from the amido acid precursor is very effective at suppressing the suds of
a mixed AS/cationic surfactant system.
WO 95!32268 218 9 7 5 i PCT~S95/04758
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i)-Detergent compositions
The following compositions were prepared and tested for sudsing.
Composition A formed wash liquor in accordance with the prior art while
composition 1 and 2 formed wash liquors in accordance with the invention
show the suds suppression effect of differing levels/types of amidoacid
and amidoperacid.
A 1 2
TAED 4.5 - -
6-Nonanoyl - 3 -
Caproyl Oxy
Benzene
Sulphonate
(Mwt 287)
Nonyl Amido - - 1.9
Peroxy Adipic
Acid (Mwt 287)
C45AS 10 10 10
C25AE3S 2 2 2
C24E5 3 3 3
N-Methyl 3 3 3
Glucamide
Zeolite A 17 17 17
SKS-6 12 12 12
Citric 3 3 3
MA/AA 5 5 5
CMC 0.4 0.4 0.4
PEG 0.5 0.5 0.5
Savinase 2.4 2.4 2.4
Lipolase 0.2 0.2 0.2
Carezyme 0.2 0.2 0.2
Endo A 0.2 0.2 0.2
SRP 0.4 0.4 0.4
PVNO 0.02 0.02 0.02
WO 95/32268 218 9 7 51 PCT~S95104758
Carbonate 6 6 6
Zinc 20 ppm 20 ppm 20 ppm
' Phthalocyanine
sulphonate
Silicone 0.4 0.4 0.4
Percarbonate 20 20 20
Water minors and miscellaneous
to balance
ii)-Suds results
The above compositions are evaluated for sudsing with the suds method
described herein before in soft water (3° Clark) and in hard water
(18°
Clark).
% suds (20 mns) A 1 2
Soft water 80 35 49
Hard water 81 31 43
The mixture of ~midoacid and amidoacid suds suppressor obtained from
the amido acid precursor is an effective suds suppression agent of high
foaming surfactants in hard water, as well as in soft water. The mixture
of said suds suppressor agent also gives better suds suppression results
than the nonyl amido peroxy adipic acid.
i)-detergent compositions
The following compositions were prepared and tested for sudsing and
cleaning. Composition A formed wash liquor in accordance with the prior
art while compositions 1, 2, 3, 4, 5 formed wash liquors in accordance
with the invention show the suds suppression effect of differing
levels/types of amidoacid and amidoperacid.
A 1 2 3 4 5
Percarbonate 17 - 17 8 25 17
Additional - 12 - 6 - -
Carbonate
WO 95132268 ~ ~ g ~ 7 5 ~ PCT/US95104758
46
6-Octanamido/- 3 3 3 3 -
6 Decanamido
Caproyl Oxy
Benzene
Sulphonate '
(50:50 blend)
6 Decanamido - - - -
Caproyl Oxy
Benzene
Sulphonate
C45AS 10 10 10 10 10 10
C25AE3S 2 2 2 2 2 2
C24E5 3 3 3 3 3 3
N-Methyl 3 3 3 3 3 3
Glucamide
Zeolite A 17 17 17 17 17 17
SKS-6 12 12 12 12 12 12
Citric 3 3 3 3 3 3
MA/AA 5 5 S 5 5 5
CMC 0.4 0.4 0.4 0.4 0.4 0.4
PEG 0.5 0.5 0.5 0.5 0.5 0.5
Savinase 2.4 2.4 2.4 2.4 2.4 2.4
Lipolase 0.2 0.2 0.2 0.2 0.2 0.2
Carezyme 0.2 0.2 0.2 0.2 0.2 0.2
Endo A 0.2 0.2 0.2 0.2 0.2 0.2
SRP 0.4 0.4 0.4 0.4 0.4 0.4
PVNO 0.02 0.02 0.02 0.02 0.02 0.02
Carbonate 6 6 6 6 6 6
Zinc 20 ppm 20 ppm 20 ppm 20 ppm 20 20
Phthalocyanine ppm ppm
sulphonate
4 4 4 0.4 0.4
0 0 0
Silicone 0.4 . . .
Water minors and miscellaneous to balance
ii)-suds and performance results
The above compositions are evaluated for sudsing with the suds method
described herein before in medium hard water (12° Clark).
A 1 2 3 4 5
W O 95132268
PCTIUS95104758
47
~ suds 100 30 44 60 65 35
(25 mns)
Performance A 1 2 3 4 5
(40°C)
Lipstick 0 + 1.6 +3.8 +3.5 +3.6 +4.0
Polish 0 +1.4 +3.6 +3.2 +3.6 +4.0
Both the amidoacid or the mixture of amidoacid and amidoperacid
obtained from the amidoacid precursor act as a suds suppressor agent and
give effective cleaning performance on hydrophobic soils like lipstick and
polish.
From the results above, it is seen that the percarbonate:amido acid
precursor ratio may be varied without detracting significantly from its
performance or suds suppressing properties.
Example 7
i)-detergent compositions
The following compositions were prepared and tested for sudsing.
Compositions 1, 2, 3, 4, 5, 6, 7 formed wash liquors in accordance with
the invention show the suds suppression effect of amidoacid and
amidoperacid.
1 2 3 4 5 6 7
6-octanamido/ 3 3 3 3 3 3 3
6 Decanamido
Caproyl Oxy
Benzene
Sulphonate
r
(50:50 blend)
Benzoyl 4 4 4 4 4 4 4
Caprolactam
Percarbonate 17 17 17 17 17 17 17
C45 AS 12 6 - 9 12 14.3 10
C38 AS 3 3 - 2 3 3.7 3.7
WO 95/32268 PCT/US95J04758
218975
48
C25 AES 3 1.5 3 2 3 - -
C24 E3 5 - - - -
Palm N-Methyl 4 9 - 4 9 4 4
Glucamide
APG - - 9 5 - - - v
Oleyl - 7.5 15 5 - - -
Sarcosinate
Amine Oxide - - - - - - 4
Zeolite A 5 5 5 5 5 5 5
SKS-6
Citric Acid/ 3 3 3 3 3 3 3
Citrate
Carbonate 9 9 9 9 9 9 9
MA/AA 5 5 5 5 5 5 5
EDDS 0.25 0.25 0.25 0.25 0.25 0.25 0.25
Silicone 0.6 0:6 0.6 0.6 0.6 0.6 ~ 0.6
Water minors, enzymes and miscellaneous to balance
The mixture of amidoacid
and amidoperacid obtained
from the amidoacid
precursor acts as a veryeffective suds suppressing agent
with various
mixed surfactant system s and also gives a good bleaching
activity on
hydrophobic soils.
