TECHNICAL FIELD
[0001] The present invention is in the field of automatic dishwashing. In particular, it
relates to the use of organic complexing agents, in particular methyl glycine diacetic
acid for the removal of baked-on burnt-on soils.
BACKGROUND OF THE INVENTION
[0002] The automatic dishwashing detergent formulator is continuously looking for ways to
improve the performance of detergents. Baked-on, burnt-on soils are among the most
difficult soils to remove. In particular, baked-on, burnt-on soils containing proteins,
such as egg and cheese, more in particular baked-on, burnt-on soils containing eggs
are really difficult to remove. The removal of baked-on, burnt-on soils is more difficult
when the detergent is phosphate free.
SUMMARY OF THE INVENTION
[0003] The present invention is based on the use of an organic complexing agent, methyl
glycine diacetic acid, in an automatic dishwashing detergent composition. It has been
unexpectedly found that the complexing agent, methyl glycine diacetic acid, improves
the removal of baked-on burnt-on soils from dishware. The composition comprises 3
grams to 6 grams, more preferably from 3.5 grams to 5.5 grams of an organic complexing
agent, more preferably of methyl glycine diacetic acid.
[0004] The composition for the use of the invention is sometimes herein referred to as "the
composition of the invention".
[0005] This level of complexing agent favours the removal of baked-on, burnt-on soils, especially
soils containing proteins such as egg and/or milk. For the purpose of this invention
a "complexing agent" is a compound capable of binding polyvalent ions such as calcium,
magnesium, lead, copper, zinc, cadmium, mercury, manganese, iron, aluminium and other
cationic polyvalent ions to form a water-soluble complex. The complexing agent has
a logarithmic stability constant ([log K]) for Ca
2+ of at least 5, preferably at least 6. The stability constant, log K, is measured
in a solution of ionic strength of 0.1, at a temperature of 25° C.
[0006] The complexing agent for use herein is the three sodium salt of MGDA.
[0007] The composition comprises a high level of protease, from 0.1 to 50 mg of active protease,
more preferably from 0.1 to 40 mg of active protease and bleach. It seems that the
combination of the level of the complexing agent of the composition of the invention,
the tri-sodium salt of MGDA and this level of protease provides optimum removal of
baked-on, burnt-on soils, in particular proteinaceous soils, such as eggs and milk
based soils.
[0008] Preferably, the composition comprises more than 0.8, more preferably more than 1
and especially 1.2 or more grams of sulfonated polymer. Preferably, the sulfonated
polymer comprises 2-acrylamido-2-methylpropane sulfonic acid monomers. For the purpose
of this invention "dishware" encompasses tableware and cookware and anything that
it is usually washed in an automatic dishwasher.
[0009] For the purpose of this invention a "sulfonated polymer" is a polymer comprising
sulphur in any of its forms. The "sulfonated polymer" of the invention preferably
comprises carboxyl groups.
[0010] The composition herein is preferably phosphate free. By "phosphate-free" is herein
understood that the composition comprises less than 1%, preferably less than 0.1%
by weight of the composition of phosphate.
[0011] It has been observed that some phosphate-free automatic dishwashing compositions
can leave a coloured film on stainless steel items. This problem is avoided when the
composition of the invention is free of citrate, thus preferred for use herein are
citrate free compositions.
[0012] Preferably, the composition of the invention has a pH equal or greater than 9 to
12, more preferably equal or greater than about 10 to about 11.5 as measured in 1%
weight/volume aqueous solution in distilled water at 20°C.
[0013] Preferably the composition of the present invention has a reserve alkalinity of 10
or greater, preferably 12 or greater, most preferably 14 or greater. "Reserve alkalinity",
as used herein refers to, the ability of an automatic dishwashing composition to maintain
an alkali pH in the presence of acid. This is relative to the ability of an automatic
dishwashing composition to have sufficient alkali in reserve to deal with any added
acid -coming from the water and/or the soils on the dishware- while maintaining the
pH.
[0014] More specifically, it is defined as the grams of NaOH per 100 cc's, exceeding pH
9.5, in product. The reserve alkalinity for a solution is determined in the following
manner.
[0015] A pH meter (for example An Orion Model 720A) with a Ag/AgCl electrode (for example
an Orion sure flow Electrode model 9172BN) is standardized using pH 7 and pH 10 buffers.
A 1% solution of the composition to be tested is prepared in distilled water. The
weight of the sample is noted. The pH of the 1% solution is measured and the solution
is titrated down to pH 9.5 using a solution of 0.2N HCL. The reserve alkalinity is
calculated in the following fashion:
* Equivalent weight of NaOH in the % NaOH equation,
derived from:
[0016] Preferably, the composition of the invention is in unit-dose form. By "unit-dose
form" is herein meant that the composition is provided in a form sufficient to provide
enough detergent for one wash. Suitable unit dose forms include tablets, sachets,
capsules, pouches, etc. Preferred for use herein are compositions in unit-dose form
wrapped in water-soluble material, for example polyvinyl alcohol, more preferably
a polyvinyl alcohol film having a film of less than 100 µm tickness. The detergent
composition of the invention preferably weighs from about 8 to about 25 grams, more
preferably from about 10 to about 20 grams. This weight range fits comfortable in
a dishwasher dispenser. Even although this range amount to a low amount of detergent,
the detergent has been formulated in a way that provides all the benefits mentioned
herein above.
SUMMARY OF THE INVENTION
[0017] The present invention relates to the use of from about 3 to about 6 grams of an organic
complexing agent, in an automatic dishwashing composition to provide baked-on, burnt-on
removal benefits.
Detergent composition
[0018] The detergent composition of the invention can be presented in unit-dose form and
it can be in any physical form including solid, liquid and gel form. The composition
of the invention is very well suited to be presented in the form of a multi-compartment
pack, more in particular a multi-compartment pack comprising compartments with compositions
in different physical forms, for example a compartment comprising a composition in
solid form and another compartment comprising a composition in liquid form. The composition
is preferably enveloped by a water-soluble film such as polyvinyl alcohol, more preferably
the film has a thickness of less than 100 µm. The composition comprises an organic
complexing agent and optionally but preferably a sulfonated polymer, bleach, inorganic
builder (preferably carbonate and silicate), enzymes in particular protease enzymes,
non-ionic surfactant, etc.
[0019] The composition of the invention preferably has a pH as measured in 1% weight/volume
aqueous solution in distilled water at 20°C of from about 9 to about 12, more preferably
from about 10 to less than about 11.5 and especially from about 10.5 to about 11.5.
[0020] The composition of the invention preferably has a reserve alkalinity of from about
10 to about 20, more preferably from about 12 to about 18 at a pH of 9.5 as measured
in NaOH with 100 grams of product at 20°C.
Complexing agent
[0021] A complexing agent is a material capable of sequestering hardness ions, particularly
calcium and/or magnesium. The composition of the invention comprises from about 3
to about 6 grams, more preferably from about 3.5 grams to about 5 grams of a complexing
agent. The complexing agent is preferably selected from the group consisting of methyl-glycine-diacetic
acid, its salts and derivatives thereof, glutamic-N,N-diacetic acid, its salts and
derivatives thereof, iminodisuccinic acid, its salts and derivatives thereof, carboxy
methyl inulin, its salts and derivatives thereof and mixtures thereof. Especially
preferred complexing agent for use herein is a salt of MGDA, in particular the tri-sodium
salt of MGDA.
Sulfonated polymer
[0022] The polymer is used in any suitable amount from about 0.1% to about 30%, preferably
from 0.5% to about 20%, more preferably from 1% to 10% by weight of the composition.
The composition of the invention comprises at least 0.8 gram, preferably at least
1 gram, more preferably at least 1.2 grams of sulfonated polymer and preferably less
than 5 grams of sulfonated polymer. Sulfonated/carboxylated polymers are particularly
suitable for the composition of the invention.
[0023] Suitable sulfonated/carboxylated polymers described herein may have a weight average
molecular weight of less than or equal to about 100,000 Da, or less than or equal
to about 75,000 Da, or less than or equal to about 50,000 Da, or from about 3,000
Da to about 50,000, preferably from about 5,000 Da to about 45,000 Da.
[0024] As noted herein, the sulfonated/carboxylated polymers may comprise (a) at least one
structural unit derived from at least one carboxylic acid monomer having the general
formula (I):
wherein R
1 to R
4 are independently hydrogen, methyl, carboxylic acid group or CH
2COOH and wherein the carboxylic acid groups can be neutralized; (b) optionally, one
or more structural units derived from at least one nonionic monomer having the general
formula (II):
wherein R
5 is hydrogen, C
1 to C
6 alkyl, or C
1 to C
6 hydroxyalkyl, and X is either aromatic (with R
5 being hydrogen or methyl when X is aromatic) or X is of the general formula (III):
wherein R
6 is (independently of R
5) hydrogen, C
1 to C
6 alkyl, or C
1 to C
6 hydroxyalkyl, and Y is O or N; and at least one structural unit derived from at least
one sulfonic acid monomer having the general formula (IV):
wherein R7 is a group comprising at least one sp2 bond, A is O, N, P, S or an amido
or ester linkage, B is a mono- or polycyclic aromatic group or an aliphatic group,
each t is independently 0 or 1, and M+ is a cation. In one aspect, R7 is a C2 to C6
alkene. In another aspect, R7 is ethene, butene or propene.
[0025] Preferred carboxylic acid monomers include one or more of the following: acrylic
acid, maleic acid, itaconic acid, methacrylic acid, or ethoxylate esters of acrylic
acids, acrylic and methacrylic acids being more preferred. Preferred sulfonated monomers
include one or more of the following: sodium (meth) allyl sulfonate, vinyl sulfonate,
sodium phenyl (meth) allyl ether sulfonate, or 2-acrylamido-methyl propane sulfonic
acid. Preferred non-ionic monomers include one or more of the following: methyl (meth)
acrylate, ethyl (meth) acrylate, t-butyl (meth) acrylate, methyl (meth) acrylamide,
ethyl (meth) acrylamide, t-butyl (meth) acrylamide, styrene, or α-methyl styrene.
[0026] Preferably, the polymer comprises the following levels of monomers: from about 40
to about 90%, preferably from about 60 to about 90% by weight of the polymer of one
or more carboxylic acid monomer; from about 5 to about 50%, preferably from about
10 to about 40% by weight of the polymer of one or more sulfonic acid monomer; and
optionally from about 1% to about 30%, preferably from about 2 to about 20% by weight
of the polymer of one or more non-ionic monomer. An especially preferred polymer comprises
about 70% to about 80% by weight of the polymer of at least one carboxylic acid monomer
and from about 20% to about 30% by weight of the polymer of at least one sulfonic
acid monomer.
[0027] The carboxylic acid is preferably (meth)acrylic acid. The sulfonic acid monomer is
preferably one of the following: 2-acrylamido methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic
acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allysulfonic acid, methallysulfonic
acid, allyloxybenzenesulfonic acid, methallyloxybenzensulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic
acid, 2-methyl-2-propene-1-sulfonic acid, styrene sulfonic acid, vinylsulfonic acid,
3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethylacrylamid, sulfomethylmethacrylamide,
and water soluble salts thereof. The unsaturated sulfonic acid monomer is most preferably
2-acrylamido-2-propanesulfonic acid (AMPS).
[0028] Preferred commercial available polymers include: Alcosperse 240, Aquatreat AR 540
and Aquatreat MPS supplied by Alco Chemical; Acumer 3100, Acumer 2000, Acusol 587G
and Acusol 588G supplied by Rohm & Haas; Goodrich K-798, K-775 and K-797 supplied
by BF Goodrich; and ACP 1042 supplied by ISP technologies Inc. Particularly preferred
polymers are Acusol 587G and Acusol 588G supplied by Rohm & Haas.
[0029] In the polymers, all or some of the carboxylic or sulfonic acid groups can be present
in neutralized form, i.e. the acidic hydrogen atom of the carboxylic and/or sulfonic
acid group in some or all acid groups can be replaced with metal ions, preferably
alkali metal ions and in particular with sodium ions.
Bleach
[0030] The composition of the invention preferably comprises from 1 to 3, preferably from
1.2 to 2.8 and especially from 1.5 to 2.5 grams of bleach.
[0031] Inorganic and organic bleaches are suitable for use herein. Inorganic bleaches include
perhydrate salts such as perborate, percarbonate, perphosphate, persulfate and persilicate
salts. The inorganic perhydrate salts are normally the alkali metal salts. The inorganic
perhydrate salt may be included as the crystalline solid without additional protection.
Alternatively, the salt can be coated. Suitable coatings include sodium sulphate,
sodium carbonate, sodium silicate and mixtures thereof. Said coatings can be applied
as a mixture applied to the surface or sequentially in layers.
[0032] Alkali metal percarbonates, particularly sodium percarbonate is the preferred bleach
for use herein. The percarbonate is most preferably incorporated into the products
in a coated form which provides in-product stability.
Potassium peroxymonopersulfate is another inorganic perhydrate salt of utility herein.
[0033] Typical organic bleaches are organic peroxyacids, especially diperoxydodecanedioc
acid, diperoxytetradecanedioc acid, and diperoxyhexadecanedioc acid. Mono- and diperazelaic
acid, mono- and diperbrassylic acid are also suitable herein. Diacyl and Tetraacylperoxides,
for instance dibenzoyl peroxide and dilauroyl peroxide, are other organic peroxides
that can be used in the context of this invention.
[0034] Further typical organic bleaches include the peroxyacids, particular examples being
the alkylperoxy acids and the arylperoxy acids. Preferred representatives are (a)
peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic
acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic
or substituted aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid,
ε-phthalimidoperoxycaproic acid[phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic
acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic
and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic
acid, diperoxysebacic acid, diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-dioic
acid, N,N-terephthaloyldi(6-aminopercaproic acid).
Preferably, the level of bleach in the composition of the invention is from about
0 to about 10%, more preferably from about 0.1 to about 5%, even more preferably from
about 0.5 to about 3% by weight of the composition.
Bleach Activators
[0035] Bleach activators are typically organic peracid precursors that enhance the bleaching
action in the course of cleaning at temperatures of 60° C and below. Bleach activators
suitable for use herein include compounds which, under perhydrolysis conditions, give
aliphatic peroxoycarboxylic acids having preferably from 1 to 12 carbon atoms, in
particular from 2 to 10 carbon atoms, and/or optionally substituted perbenzoic acid.
Suitable substances bear O-acyl and/or N-acyl groups of the number of carbon atoms
specified and/or optionally substituted benzoyl groups. Preference is given to polyacylated
alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine
derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT),
acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in
particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular
n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), decanoyloxybenzoic
acid (DOBA), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric
alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran
and also triethylacetyl citrate (TEAC). If present the composition of the invention
comprises from 0.1 to 2, preferably from 0.2 to 1 grams of bleach activator, preferably
TAED.
Bleach Catalyst
[0036] The composition herein preferably contains a bleach catalyst, preferably a metal
containing bleach catalyst. More preferably the metal containing bleach catalyst is
a transition metal containing bleach catalyst, especially a manganese or cobalt-containing
bleach catalyst.
Bleach catalysts preferred for use herein include the manganese triazacyclononane
and related complexes (
US-A-4246612,
US-A-5227084); Co, Cu, Mn and Fe bispyridylamine and related complexes (
US-A-5114611); and pentamine acetate cobalt(III) and related complexes(
US-A-4810410). A complete description of bleach catalysts suitable for use herein can be found
in
WO 99/06521, pages 34, line 26 to page 40, line 16.
[0037] Manganese bleach catalysts are preferred for use in the composition of the invention.
Especially preferred catalyst for use here is a dinuclear manganese-complex having
the general formula:
wherein Mn is manganese which can individually be in the III or IV oxidation state;
each x represents a coordinating or bridging species selected from the group consisting
of H2O, O22-, O2-, OH-, HO2-, SH-, S2-, >SO, Cl-, N3-, SCN-, RCOO-, NH2- and NR3,
with R being H, alkyl or aryl, (optionally substituted); L is a ligand which is an
organic molecule containing a number of nitrogen atoms which coordinates via all or
some of its nitrogen atoms to the manganese centres; z denotes the charge of the complex
and is an integer which can be positive or negative; Y is a monovalent or multivalent
counter-ion, leading to charge neutrality, which is dependent upon the charge z of
the complex; and q = z/[charge Y].
[0038] Preferred manganese-complexes are those wherein x is either CH
3COO
- or O
2 or mixtures thereof, most preferably wherein the manganese is in the IV oxidation
state and x is O
2-. Preferred ligands are those which coordinate via three nitrogen atoms to one of
the manganese centres, preferably being of a macrocyclic nature. Particularly preferred
ligands are:
- (1) 1,4,7-trimethyl-1,4,7-triazacyclononane, (Me-TACN); and
- (2) 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, (Me-Me TACN).
[0039] The type of counter-ion Y for charge neutrality is not critical for the activity
of the complex and can be selected from, for example, any of the following counter-ions:
chloride; sulphate; nitrate; methylsulphate; surfactant anions, such as the long-chain
alkylsulphates, alkylsulphonates, alkylbenzenesulphonates, tosylate, trifluoromethylsulphonate,
perchlorate (ClO
4-), BPh
4-, and PF
6-' though some counter-ions are more preferred than others for reasons of product property
and safety.
[0040] Consequently, the preferred manganese complexes useable in the present invention
are:
- (I) [(Me-TACN)MnIV(µ-0)3MnIV(Me-TACN)]2+(PF6-)2
- (II) [(Me-MeTACN)MnIV(µ-0)3MnIV(Me-MeTACN)]+(PF6-)2
- (III) [(Me-TACN)MnIII(µ-0)(µ-OAc)2MnIII(Me-TACN)]2(PF6-)2
- (IV) [(Me-MeTACN)MnIII(µ-O)(µ-OAc)2MnIII(Me-MeTACN)]2+(PF6-)2 which hereinafter may also be abbreviated as:
- (I) [MnIV2(µ-0)3(Me-TACN)2](PF6)2
- (II) [MnIV2(µ-0)3(Me-MeTACN)2](PF6)2
- (III) [MnIII2(µ-0)(µ-OAc)2(Me-TACN)2](PF6)2
- (IV) [MnIII2(µ-0)(µ-OAc)2(Me-TACN)2](PF6)2
[0041] The structure of I is given below:
abbreviated as [Mn
IV2(µ-0)
3(Me-TACN)
2](PF
6)
2.
[0042] The structure of II is given below:
abbreviated as [Mn
IV2(µ-0)
3(Me-MeTACN)
2](PF
6)
2.
[0043] It is of note that the manganese complexes are also disclosed in
EP-A-0458397 and
EP-A-0458398 as unusually effective bleach and oxidation catalysts. In the further description
of this invention they will also be simply referred to as the "catalyst".
[0044] Preferably the composition of the invention comprises from 0.001 to 1, more preferably
from 0.002 to 0.01 grams of bleach catalyst. Preferably the bleach catalyst is a manganese
bleach catalyst.
Inorganic builder
[0045] The composition of the invention preferably comprises an inorganic builder. Suitable
inorganic builders are selected from the group consisting of carbonate, silicate and
mixtures thereof. Especially preferred for use herein are sodium carbonate and silicate.
Preferably the composition of the invention comprises from 1 to 8, more preferably
from 2 to 6 and especially from 3 to 5 grams of sodium carbonate and from 0.05 to
2 grams of silicate.
Surfactant
[0046] Surfactants suitable for use herein include non-ionic surfactants, preferably the
compositions are free of any other surfactants. Traditionally, non-ionic surfactants
have been used in automatic dishwashing for surface modification purposes in particular
for sheeting to avoid filming and spotting and to improve shine. It has been found
that non-ionic surfactants can also contribute to prevent redeposition of soils.
[0047] Preferably the composition of the invention comprises a non-ionic surfactant or a
non-ionic surfactant system, more preferably the non-ionic surfactant or a non-ionic
surfactant system has a phase inversion temperature, as measured at a concentration
of 1% in distilled water, between 40 and 70°C, preferably between 45 and 65°C. By
a "non-ionic surfactant system" is meant herein a mixture of two or more non-ionic
surfactants. Preferred for use herein are non-ionic surfactant systems. They seem
to have improved cleaning and finishing properties and better stability in product
than single non-ionic surfactants.
[0048] Phase inversion temperature is the temperature below which a surfactant, or a mixture
thereof, partitions preferentially into the water phase as oil-swollen micelles and
above which it partitions preferentially into the oil phase as water swollen inverted
micelles. Phase inversion temperature can be determined visually by identifying at
which temperature cloudiness occurs.
[0049] The phase inversion temperature of a non-ionic surfactant or system can be determined
as follows: a solution containing 1% of the corresponding surfactant or mixture by
weight of the solution in distilled water is prepared. The solution is stirred gently
before phase inversion temperature analysis to ensure that the process occurs in chemical
equilibrium. The phase inversion temperature is taken in a thermostable bath by immersing
the solutions in 75 mm sealed glass test tube. To ensure the absence of leakage, the
test tube is weighed before and after phase inversion temperature measurement. The
temperature is gradually increased at a rate of less than 1°C per minute, until the
temperature reaches a few degrees below the pre-estimated phase inversion temperature.
Phase inversion temperature is determined visually at the first sign of turbidity.
[0050] Suitable nonionic surfactants include: i) ethoxylated non-ionic surfactants prepared
by the reaction of a monohydroxy alkanol or alkyphenol with 6 to 20 carbon atoms with
preferably at least 12 moles particularly preferred at least 16 moles, and still more
preferred at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol;
ii) alcohol alkoxylated surfactants having a from 6 to 20 carbon atoms and at least
one ethoxy and propoxy group. Preferred for use herein are mixtures of surfactants
i) and ii).
[0051] Another suitable non-ionic surfactants are epoxy-capped poly(oxyalkylated) alcohols
represented by the formula:
R1O[CH2CH(CH3)O]x[CH2CH2O]y[CH2CH(OH)R2] (I)
wherein R1 is a linear or branched, aliphatic hydrocarbon radical having from 4 to
18 carbon atoms; R2 is a linear or branched aliphatic hydrocarbon radical having from
2 to 26 carbon atoms; x is an integer having an average value of from 0.5 to 1.5,
more preferably about 1; and y is an integer having a value of at least 15, more preferably
at least 20.
[0052] Preferably, the surfactant of formula I, at least about 10 carbon atoms in the terminal
epoxide unit [CH2CH(OH)R2]. Suitable surfactants of formula I, according to the present
invention, are Olin Corporation's POLY-TERGENT® SLF-18B nonionic surfactants, as described,
for example, in
WO 94/22800, published October 13, 1994 by Olin Corporation.
[0053] Amine oxides surfactants are useful for use in the composition of the invention.
Preferred are C10-C18 alkyl dimethylamine oxide, and C10-18 acylamido alkyl dimethylamine
oxide.
[0054] Surfactants may be present in amounts from 0.1 to 10, more preferably from 0.5 to
5 and especially from 0.8 to 3 grams.
Enzymes
[0055] In describing enzyme variants herein, the following nomenclature is used for ease
of reference: Original amino acid(s):position(s):substituted amino acid(s). Standard
enzyme IUPAC 1-letter codes for amino acids are used.
Proteases
[0056] Suitable proteases include metalloproteases and serine proteases, including neutral
or alkaline microbial serine proteases, such as subtilisins (EC 3.4.21.62) as well
as chemically or genetically modified mutants thereof. Suitable proteases include
subtilisins (EC 3.4.21.62), including those derived from Bacillus, such as Bacillus
lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus
gibsonii.
[0057] Especially preferred proteases for the detergent of the invention are polypeptides
demonstrating at least 90%, preferably at least 95%, more preferably at least 98%,
even more preferably at least 99% and especially 100% identity with the wild-type
enzyme from Bacillus lentus, comprising mutations in one or more, preferably two or
more and more preferably three or more of the following positions, using the BPN'
numbering system and amino acid abbreviations as illustrated in
WO00/37627, which is incorporated herein by reference:V68A, N87S, S99D, S99SD, S99A, S101G,
S101M, S103A, V104N/I, G118V, G118R, S128L, P129Q, S130A, Y167A, R170S, A194P, V205I
and/or M222S.
[0058] Most preferably the protease is selected from the group comprising the below mutations
(BPN' numbering system) versus either the PB92 wild-type (SEQ ID NO:2 in
WO 08/010925) or the subtilisin 309 wild-type (sequence as per PB92 backbone, except comprising
a natural variation of N87S).
- (i) G118V + S128L + P129Q + S130A
- (ii) S101M + G118V + S128L + P129Q + S130A
- (iii) N76D + N87R + G118R + S128L + P129Q + S130A + S188D + N248R
- (iv) N76D + N87R + G118R + S128L + P129Q + S130A + S188D + V244R
- (v) N76D + N87R + G118R + S128L + P129Q + S130A
- (vi) V68A + N87S + S101G + V104N
[0059] Suitable commercially available protease enzymes include those sold under the trade
names Savinase®, Polarzyme®, Kannase®, Ovozyme®, Everlase® and Esperase® by Novozymes
A/S (Denmark), those sold under the tradename Properase®, Purafect®, Purafect Prime®,
Purafect Ox®, FN3®, FN4®, Excellase®, Ultimase® and Purafect OXP® by Genencor International,
those sold under the tradename Opticlean® and Optimase® by Solvay Enzymes, those available
from Henkel/ Kemira, namely BLAP.
[0060] Preferred levels of protease in the product of the invention include from about 0.1
to about 50, more preferably from about 1 to about 45 and especially from about 10
to about 40 mg of active protease.
Amylases
[0061] Preferred enzyme for use herein includes alpha-amylases, including those of bacterial
or fungal origin. Chemically or genetically modified mutants (variants) are included.
A preferred alkaline alpha-amylase is derived from a strain of Bacillus, such as Bacillus
licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, Bacillus subtilis,
or other Bacillus sp., such as Bacillus sp. NCIB 12289, NCIB 12512, NCIB 12513, DSM
9375 (USP
7,153,818) DSM 12368, DSMZ no. 12649, KSM AP1378 (
WO 97/00324), KSM K36 or KSM K38 (
EP 1,022,334). Preferred amylases include:
- (a) the variants described in US 5,856,164 and WO99/23211, WO 96/23873, WO00/60060 and WO 06/002643, especially the variants with one or more substitutions in the following positions
versus the AA560 enzyme listed as SEQ ID No. 12 in WO 06/002643: 9, 26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186, 193, 195,
202, 214, 231, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298, 299, 303, 304, 305,
311, 314, 315, 318, 319, 320, 323, 339, 345, 361, 378, 383, 419, 421, 437, 441, 444,
445, 446, 447, 450, 458, 461, 471, 482, 484, preferably that also contain the deletions
of D183* and G184*.
- (b) variants exhibiting at least 95% identity with the wild-type enzyme from Bacillus
sp.707 (SEQ ID NO:7 in US 6,093, 562), especially those comprising one or more of the following mutations M202, M208,
S255, R172, and/or M261. Preferably said amylase comprises one of M202L or M202T mutations.
[0062] Suitable commercially available alpha-amylases include DURAMYL®, LIQUEZYME®, TERMAMYL®,
TERMAMYL ULTRA®, NATALASE®, SUPRAMYL®, STAINZYME®, STAINZYME PLUS®, POWERASE®, FUNGAMYL®
and BAN® (Novozymes A/S, Bagsvaerd, Denmark), KEMZYM® AT 9000 Biozym Biotech Trading
GmbH Wehlistrasse 27b A-1200 Wien Austria, RAPIDASE®, PURASTAR®, ENZYSIZE®, OPTISIZE
HT PLUS® and PURASTAR OXAM® (Genencor International Inc., Palo Alto, California) and
KAM® (Kao, 14-10 Nihonbashi Kayabacho, 1-chome, Chuo-ku Tokyo 103-8210, Japan). Amylases
especially preferred for use herein include NATALASE®, STAINZYME®, STAINZYME PLUS®,
POWERASE® and mixtures thereof.
[0063] Preferably, the product of the invention comprises at least 0.01 mg, preferably from
about 0.05 to about 10, more preferably from about 0.1 to about 6, especially from
about 0.2 to about 5 mg of active amylase.
Additional Enzymes
[0064] Additional enzymes suitable for use in the product of the invention can comprise
one or more enzymes selected from the group comprising hemicellulases, cellulases,
cellobiose dehydrogenases, peroxidases, proteases, xylanases, lipases, phospholipases,
esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases,
oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases,
malanases, β-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, amylases,
and mixtures thereof.
[0065] Preferably, the protease and/or amylase of the product of the invention are in the
form of granulates, the granulates comprise less than 29% of sodium sulfate by weight
of the granulate or the sodium sulfate and the active enzyme (protease and/or amylase)
are in a weight ratio of less than 4:1.
Crystal growth inhibitor
[0066] Crystal growth inhibitors are materials that can bind to calcium carbonate crystals
and prevent further growth of species such as aragonite and calcite.
[0067] Especially preferred crystal growth inhibitor for use herein is HEDP (1-hydroxyethylidene
1,1-diphosphonic acid). Preferably, the composition of the invention comprises from
0.01 to 1, more preferably from 0.05 to 0.8 grams of a crystal growth inhibitor, preferably
HEDP.
Metal Care Agents
[0068] Metal care agents may prevent or reduce the tarnishing, corrosion or oxidation of
metals, including aluminium, stainless steel and non-ferrous metals, such as silver
and copper. Preferably the composition of the invention comprises from 0.001 to 0.01,
more preferably from 0.002 to 0.009 grams, preferably the metal care agent is benzo
triazole (BTA).
Glass Care Agents
[0069] Glass care agents protect the appearance of glass items during the dishwashing process.
Preferably the composition of the invention comprises from 0.001 to 1, more preferably
from 0.002 to 0.5 grams of a glass care agent, preferably the glass care agent is
a zinc salt.
[0070] The dimensions and values disclosed herein are not to be understood as being strictly
limited to the exact numerical values recited. Instead, unless otherwise specified,
each such dimension is intended to mean both the recited value and a functionally
equivalent range surrounding that value. For example, a dimension disclosed as "40
mm" is intended to mean "about 40 mm".
EXAMPLES
[0071] Two dual-compartment automatic dishwashing pouches were made comprising the ingredients
detailed herein below (Comparative composition 1 and composition 2). The pouches were
made of polyvinyl alcohol (Monosol 8630 available from Kuraray) with the solid and
liquid components in different compartments.
Ingredients (grams of active material) |
Comparative composition 1 |
Composition 2 |
Solid compartment |
|
|
Sodium carbonate |
6.42 |
6.42 |
Sodium silicate 2R |
0.14 |
0.14 |
MGDA |
2.84 |
3.58 |
Sodium percarbonate |
0.94 |
0.94 |
Sulfonated polymer |
1.07 |
1.07 |
Protease |
0.035 |
0.035 |
Amylase |
0.009 |
0.009 |
Bleach catalyst |
0.001 |
0.001 |
Miscellaneous |
Balance to 13.84 |
Balance to 13.84 |
Liquid compartment |
|
|
Lutensol TO7 |
0.70 |
0.70 |
Plurafac SLF-180 |
1.00 |
1.00 |
Miscellaneous |
Balance to 2.1300 |
Balance to 2.1300 |
MGDA Tri-sodium salt of methyl glycine diacetic acid
Protease Ultimase ® Supplied by Dupont
Amylase Stainzyme Plus ® Supplied by Novozymes
Lutensol TO7 Nonionic surfactant supplied by BASF
Plurafac SLF-180 Nonionic surfactant supplied by BASF |
Performance data
[0072] The cleaning power of the compositions was assessed by running a performance test
containing baked-on /burnt-on soils. Two different burnt soils were tested: Burnt
egg in ceramic containers and burnt Macaroni and Cheese in stainless steel pots.
[0073] To prepare 16 of ceramic bowls with burnt egg, 5 grams of butter are scooped onto
the bottom of each bowl and brought to room temperature to soften the butter. On a
large container 17, grade A, large eggs are then mixed and whisked, then 50 mL of
the mixture are added into each bowl and mixed with butter. The egg mixture is then
cooked in an 800W microwave. Four bowls at a time are then microwaved for 2 minutes
at high power until the 16 egg bowls are cooked. The Egg bowls are then put aside
and left to rest overnight. The following day the egg is scrapped and the bowls are
baked for 15 minutes at 200°C to burn the remaining egg.
[0074] To prepare 16 stainless steel pots with macaroni and cheese, 708ml of water are boiled
in a pan on a hob and 82.5g of Kraft macaroni and cheese dinner® dry pasta are added
to the boiling water. The pasta is allowed to cook for 7 minutes. In a separate container
118mL of full fat milk and 10g of margarine are mixed and microwaved for 1.3min at
high power to melt the margarine, once the pasta is cooked the water is drained and
the pasta along with the milk and dried cheese are added into a food processor and
blend for 2 minutes, ensuring the mixture is uniform. The 16 stainless steel copper
based pans are then prepared by painting 10g of the mixture on the bottom of the pan.
Then the pans are then baked in the oven at 180°C for 60 minutes.
[0075] Each dishwashing machine is then loaded with two egg bowls and two mac and cheese
pans in the bottom basket and clean ballast dishes.
[0076] The test was executed using Maytag dishwasher in a normal light cycle setting, without
prewash. The inlet water was preheated in a storage tank to 50°C and had a 127 ppm
of CaCO
3 as hardness; additional 50g of TMD soil were added from frozen at the start of the
wash. The test is repeated three more times for each composition.
[0077] To aid the visualisation of any egg residue the washed egg ceramic bowls are then
stained by pouring 100mL of a talcum powder/safranin O solution (1.275g of talcum
powder and 0.225g of Safranin O are dissolved in 3L of water) into the dish, swirling
around until any residue is stained. The solution can be reused in the next washed
egg bowl.
[0078] The items are then visually graded by three independent judges using a scale from
1 to 10, where 1 is the most soiled and 10 is the cleanest.
Results
[0079]
Treatment |
Egg |
MacCheese |
Composition 1 (Comparative) |
5.56 |
2.72 |
Composition 2 |
7.84 |
3.78 |
[0080] A great improvement of the removal of baked-on, burnt-on egg and macaroni cheese
takes place when the level of MGDA increases from 2.84 to 3.58 grams.