Note: Descriptions are shown in the official language in which they were submitted.
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MAC~INE DISHWASHING COMPOSITION
Technical Field
The present invention relates to a detergent composition adapted for use in
a cleaning method exhibiting improved soil removal.
B~ k~round to the Invention
Compositions designed for use in cleaning, particularly in automatic
dishwashing and laundry methods are well known and a consistent effort
has been made by detergent manufacturers to improve the cle~ning and/or
rinsing efficiency of said compositions as reflected by many patent
publications.
Builder components are traditionally added to detergent compositions to
chelate cations (Ca2+ and Mg2+) that are the cause of water hardness.
Water hardness ions that are not chelated may form insoluble complexes
with anionic species or form inorganic white phosphate, carbonate or
silicate deposits on the articles in the wash that are unacceptable to the
consumer.
.
A further problem believed to result from the presence of water hardness
ions in the solution relates to the removal of hydrophilic soils from soiled
~ . .
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dishware. It is believed that water hardness ions adhere to the surface of
dishware by way of ionic attractions between the negatively charged groups
of the dishware and the positively charged hard water ions. It is further
believed that said hard water ions attract negatively charged hydrophilic
soils. Chemical interactions (calcium bridges) between the hard water ions
and the hydrophilic soils mal~e the soils harder to remove. Examples of
hydrophilic soils include tea, coffee and red wine soils.
It has been found that the formation of insoluble white calcium phosphate
complexes can be reduced by the addition of an amino tricarboxylic acid
(ATCA) to the builder systems. It has also been found that enhanced
removal of soils, particularly hydrophilic soils from the surface of dishware
can also be achieved by the addition of an amino tricarboxylic acid (ATCA)
to the builder systems. It is believed that ATCA chelates cations from the
wash solution thus minimi.~ing their availability to forrn calcium bridges
between the surface of the dishware and the hydrophilic soil.
S-lmm~ry of the Invention
According to the present invention there is provided a detergent
composition comprising
(a) a builder system comprising phosphate builder; and
(b) an amino tricarboxylic acid or salt thereof wherein said
amino tricarboxylic acid has the general formula:
Ho-c-R1\\ X O
N-CH~(R3)n-C-OH
O
HO-C-R2
where Rl, R2 and R3 are alkyl groups or substituted alkyl groups
of chain length C1 to C4; n is O or l; and
X is an organic substituent group.
.
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Detailed Description of the Invention
The present invention relates to a detergent composition adapted for use in
a cleaning method, exhibiting improved soil removal.
Builder system
The detergent composition described herein has as an essential component a
builder system comprising a phosphate builder. The phosphate builder
compound can be present at a level of from 1% to 80% by weight,
preferably from 10% to 70% by weight, most preferably from 20% to 60%
by weight of the detergent composition.
Specific examples of phosphate builder compounds include alkali metal
tripolyphosphates, sodium, potassium and ammonium pyrophosphate,
sodium and potassium and ammonium pyrophosphate, sodium and
potassium orthophosphate, sodium polymeta/phosphate in which the degree
of polymerisation ranges from about 6 to 21, and salts of phytic acid.
Amino Tricarboxyliç Acid (ATCA)
The amino tricarboxylic acid (ATCA) is selected from the group having the
general formula as shown below.
HO-C-R1~ X O
N - CH--(R3)n C - OH
O
HO-C-R2 '
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where R1, R2 and R3 are alkyl groups or substituted alkyl groups
of chain length C1 to C4; n is 0 or 1; and
X is an organic substituent group.
where Rl, R2 and R3 are an alkyl group or substituted alkyl group of chain
length C1 to C4, and n is 0 or 1. X is an organic substitutent group, that is
a substituent typically encountered in organic compounds, but excluding X
being a hydrogen substituent. X can thus for example be an alkyl, aryl,
alkenyl or alkaryl group optionally substituted by any functionality
including for example, amino, hydroxyl, amide and ether functionalities. X
may also be an organic functional group including for example an amine,
hydroxyl, amide, ester or ether group. X is preferably an alkyl group, most
preferably a methyl or ethyl group. ATCA is most preferably methyl
glycine diacetic acid, that is where R1 = R2 = a -CH2- group, n is 0 and
X = CH3.
ATCA can be present at levels of greater than 0.0001% by weight,
preferably from 0.001 % to 40% by weight, most preferably from 0.1% to
15% by weight of the detergent composition.
ATCA acts as a cation complexing chelant. ATCA forms water-soluble
chelates with calcium, m~FnPsium, lead, copper, zinc, cadmium, mercury,
m~ng~n~se, iron, aluminium and other cationic polyvalent ions. The
stability constant (measured as log K MeZ) of ATCA-calcium chelate is
greater than 5.0, preferably greater then 6Ø The stability constant of the
preferred ATCA compound, methyl glycine diacetic acid (MGDA) is 7Ø
The stability constant, log K MeZ is measured in a solution of ionic
strength of 0.1, at a temperature of 25~C. The figure of > 5.0 for
logKMez indicates that the ratio of the concentration of the undissociated
[CaATCA-] to the dissociated complex [Ca2+][ATCA3~~, is > 105:1
A preferred aspect of the present invention is a detergent composition
wherein the weight ratio of builder system to ATCA is from 5:1 to 25:1,
preferably 8:1 to 20:1, most preferably 10:1 to 15:1.
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Another preferred aspect of the present invention is a detergent composition
cont~ining an organo diphosphonic acid crystal growth inhibitor component
wherein the weight ratio of the organo diphosphonic acid to ATCA is from
1 :2 to 1 :20, preferably 1 :2.5 to 1 :8, most preferably 1 :3 to 1 :6.
Optional Deter~ent Components
The detergent composition may optionally contain various components
including surfactants, bleaching agents, ~lk~inity sources, water-soluble
builder compounds, lime soap dispersants, organic polymeric compounds
including polymeric dye transfer inhibiting agents, crystal growth
inhibitors, heavy metal ion sequestrants, enzymes and enzyme stabilisers,
corrosion inhibitors, suds suppressors, solvents, fabric softening agents,
optical brighteners and hydrotropes.
Surfactant
A highly preferred component of the compositions used in this invention is
a surfactant system comprising surfactant selected from anionic, cationic,
nonionic ampholytic and zwitterionic surfactants and mixtures thereof.
Automatic dishwashing machine products should be low foaming in
character and thus the fo~ming of the surfactant system must be suppressed
or more preferably be low fo~rning, typically nonionic in character. The
surfactant system is typically present at a level of from 0.2~ to 30% by
weight, more preferably from 0.5~ to 10% by weight, most preferably
from 1 ~ to 5 % by weight of the compositions.
A typical listing of anionic, nonionic, ampholytic and zwitterionic classes,
and species of these surfactants, is given in U.S.P. 3,929,678 issued to
Laughlin and Heuring on December, 30, 1975. A list of suitable cationic
surfactants is given in U.S.P. 4,259,217 issued to Murphy on March
-31,1981. A listing of surfactants typically included in automatic
dishwashing detergent compositions is given for example, in EP-A-0414
549 and PCT Applications Nos. WO 93/08876 and WO 93/08874.
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Nonionic surfactant
Essentially any nonionic surfactants useful for detersive purposes can be
included in the compositions. Preferred, non-limiting classes of useful
nonionic surfactants are listed below.
Nonionic ethoxylated alcohol surfactant
The alkyl ethoxylate condensation products of aliphatic alcohols with from
about 1 to about 25 moles of ethylene oxide are suitable for use herein. The
alkyl chain of the aliphatic alcohol can either be straight or branched,
primary or secondary, and generally contains from 6 to 22 carbon atoms.
Particularly preferred are the condensation products of alcohols having an
alkyl group cont~inin~ from 8 to 20 carbon atoms with from about 2 to
about 10 moles of ethylene oxide per mole of alcohol.
Nonionic ethoxylated/propoxylated fatty alcohol surfactant
The ethoxylated C6-C1g fatty alcohols and C6-C1g mixed
ethoxylated/propoxylated fatty alcohols are suitable surfactants for use
herein, particularly where water soluble. Preferably the ethoxylated fatty
alcohols are the Clo-C1g ethoxylated fatty alcohols with a degree of
ethoxylation of from 3 to 50, most preferably these are the C12-C1g
ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40.
Preferably the mixed ethoxylated/propoxylated fatty alcohols have an alkyl
chain length of from 10 to 18 carbon atoms, a degree of ethoxylation of
from 3 to 30 and a degree of propoxylation of from 1 to 10.
Nonionic EO/PO condensates with propvlene ~Iycol
The condensation products of ethylene oxide with a hydrophobic base
formed by the condensation of propylene oxide with propylene glycol are
suitable for use herein. The hydrophobic portion of these compounds
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preferably has a molecular weight of from about 1500 to about 1800 and
exhibits water insolubility. Examples of compounds of this type include
certain of the commercially-available PluronicTM surfactants, marketed by
BASF.
Nonionic EO condensation products with propylene oxide/ethylene diamine
adducts
The condensation products of ethylene oxide with the product resulting
from the reaction of propylene oxide and ethylene~i~mine are suitable for
use herein. The hydrophobic moiety of these products consists of the
reaction product of ethylene~ mine and excess propylene oxide, and
generally has a molecular weight of from about 2500 to about 3000.
Examples of this type of nonionic surfactant include certain of the
commercially available TetronicTM compounds, marketed by BASF.
Anionic surfactant
Essentially any anionic surfactants useful for detersive purposes are
suitable. These can include salts (including, for example, sodium,
potassium, ammonium, and substituted ammonium salts such as mono-, di-
and triethanol~min~ salts) of the anionic sulfate, sulfonate, carboxylate and
sarcosinate surfactants. Anionic sulfate surfactants are preferred.
Other anionic surfactants include the isethionates such as the acyl
isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl
succinates and sulfosuccinates, monoesters of sulfosuccinate (especially
saturated and lln~tnrated C12-C18 monoesters) diesters of sulfosuccinate
(especially saturated and nnc~ rated C6-C14 diesters), N-acyl sarcosinates.
Resin acids and hydrogenated resin acids are also suitable, such as rosin,
hydrogenated rosin~ and resin acids and hydrogenated resin acids present in
or derived from tallow oil.
... .
. _ ... .
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Anionic sulfate surfactant
Anionic sulfate surfactants suitable for use herein include the linear and
branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty
oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the Cs-
C17 acyl-N-(Cl-C4 alkyl) and -N-(Cl-C2 hydroxyalkyl) glucamine
sulfates, and sulfates of alkylpolysaccharides such as the sulfates of
alkylpolyglucoside (the nonionic nonsulfated compounds being described
herein).
Alkyl sulfate surfactants are preferably selected from the linear and
branched primary C10-cl8 alkyl sulfates, more preferably the C11-C1s
branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
Alkyl ethoxysulfate surfactants are preferably selected from the group
consisting of the Clo-C1g alkyl sulfates which have been ethoxylated with
from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the
alkyl ethoxysulfate surfactant is a C 1 1 -C 1 8, most preferably C 1 1 -C 15 alkyl
sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to
5, moles of ethylene oxide per molecule.
A particularly preferred aspect of the invention employs mixtures of the
preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures
have been disclosed in PCT Patent Application No. WO 93/18124.
Anionic sulfonate surfactant
Anionic sulfonate surfactants suitable for use herein include the salts of
Cs-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22
primary or secondary alkane sulfonates, C6-C24 olefin sulfonates,
sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl
glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures
thereof.
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Anionic carboxylate surfactant
Suitable anionic carboxylate surfactants include the alkyl ethoxy
carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the
soaps ('alkyl carboxyls'), especially certain secondary soaps as described
herem.
Suitable alkyl ethoxy carboxylates include those with the formula
RO(CH2CH20)X CH2C00-M+ wherein R is a C6 to C1g alkyl group, x
ranges from O to 10, and the ethoxylate distribution is such that, on a
weight basis, the amount of material where x is 0 is less than 20 % and M
is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include
those having the formula RO-(CHR1-CHR2-O)-R3 wherein R is a C6 to
C1g alkyl group, x is from 1 to 25, R1 and R2 are selected from the group
consisting of hydrogen, methyl acid radical, succinic acid radical,
hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from
the group consisting of hydrogen, substituted or unsubstituted hydrocarbon
having between 1 and 8 carbon atoms, and mixtures thereof.
Suitable soap surf~ct~nt.s include the secondary soap surfactants which
contain a carboxyl unit connected to a secondary carbon. Preferred
secondary soap surf~ct~ntc for use herein are water-soluble members
selected from the group consisting of the water-soluble salts of 2-meehyl-1-
lln-lec~noic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-
butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps may
also be included as suds suppressors.
Alkali metal sarcosinate surfactant
Other suitable anionic surfactants are the alkali metal sarcosinates of
formula R-CON (R1) CH2 COOM, wherein R is a Cs-C17 linear or
branched alkyl or all~enyl group, R1 is a Cl-C4 alkyl group and M is an
alkali metal ion. Preferred examples are the myristyl and oleoyl methyl
sarcosinates in the form of their sodium salts.
~ . . .
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~O
Oxy~en-releasin~ bleachin~ system
An optional component of the detergent composition is an oxygen-releasing
bleaching system. In one preferred aspect the bleaching system contains a
hydrogen peroxide source and an organic peroxyacid bleach precursor
compound. The production of the organic peroxyacid occurs by an in situ
reaction of the precursor with a source of hydrogen peroxide. Preferred
sources of hydrogen peroxide include inorganic perhydrate bleaches. In an
alternative preferred aspect a preforrned organic peroxyacid is incorporated
directly into the composition. Compositions cont~inin~ mixtures of a
hydrogen peroxide source and organic peroxyacid precursor in combination
with a preformed organic peroxyacid are also envisaged.
Inor~anic perhydrate bleaches
The compositions in accord with the invention preferably include a
hydrogen peroxide source, as an oxygen-releasing bleach. Suitable
hydrogen peroxide sources include the inorganic perhydrate salts.
The inorganic perhydrate salts are normally incorporated in the form of the
sodium salt at a level of from 1 % to 40 % by weight, more preferably from
2 % to 30% by weight and most preferably from 5 % to 25 ~ by weight of
the compositions.
Examples of inorganic perhydrate salts include 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 crystalllne solid without additional protection. For
certain perhydrate salts however, the preferred executions of such granular
compositions utilize a coated form of the material which provides better
storage stability for the perhydrate salt in the granular product.
Sodium perborate can be in the form of the monohydrate of nominal
formula NaBO2H202 or the tetrahydrate NaBO2H202.3H20.
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Alkali metal percarbonates, particularly sodium percarbonate are preferred
perhydrates for inclusion in compositions in accordance with the invention.
Sodium percarbonate is an addition compound having a formula
corresponding to 2Na2CO3.3H2O2, and is available commercially as a
crystalline solid. Sodium percarbonate, being a hydrogen peroxide addition
compound tends on dissolution to release the hydrogen peroxide quite
rapidly which can increase the tendency for localised high bleach
concentrations to arise. The percarbonate is most preferably incorporated
into such compositions in a coated form which provides in-product
stability.
A suitable coating material providing in product stability comprises mixed
salt of a water soluble alkali metal sulphate and carbonate. Such coatings
together with coating processes have previously been described in GB-
1,466,799, granted to Interox on 9th March 1977. The weight ratio of the
mixed salt coating material to percarbonate lies in the range from 1: 200 to
1: 4, more preferably from 1: 99 to 1: 9, and most preferably from 1:
49 to 1: 19. Preferably, the mixed salt is of sodium sulphate and sodium
carbonate which has the general forrnula Na2SO4.n.Na2CO3 wherein n is
from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is
from 0.2 to 0.5.
Other coatings which contain silicate (alone or with borate salts or boric
acids or other inorganics), waxes, oils, fatty soaps can also be used
advantageously within the present invention.
Potassium peroxymonopersulfate is another inorganic perhydrate salt of
utility in the compositions herein.
Peroxyacid bleach precursor
Peroxyacid bleach precursors are compounds which react with hydrogen
peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally
peroxyacid bleach precursors may be represented as
... .. .
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o
X C-L
where L is a leaving group and X is essentially any functionality, such that
on perhydrolysis the structure of the peroxyacid produced is
o
X-C-OOH
Peroxyacid bleach precursor compounds are preferably incorporated at a
level of from 0.5~ to 20~ by weight, more preferably from 1 % to 10%
by weight, most preferably from 1.5 % to 5 % by weight of the
compositions.
Suitable peroxyacid bleach precursor compounds typically contain one ormore N- or O-acyl groups, which precursors can be selected from a wide
range of classes. Suitable classes include anhydrides, esters, imides,
lactams and acylated derivatives of imidazoles and oximes. Examples of
useful materials within these classes are disclosed in GB-A-1586789.
Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231
and EP-A-0170386.
Leavlng groups
The leaving group, hereinafter L group, must be sufficiently reactive for
the perhydrolysis reaction to occur within the optimum time frame (e.g., a
wash cycle). However, if L is too reactive, this activator will be difficult to
stabilize for use in a bleaching composition.
Preferred L groups are selected from the group consisting of:
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0~ O~Y and --~~
--N--C--R1 _N N --N--C--CH--R4
R3 ~ R3 Y
R3 Y
-O--CH=C--CH=CH2 --O--CH--C--CH=CH2
O y O
-~C--R1 --N~C NR4 --N /NR4
Il 11
O O
R3 0 Y
--O--C=CHR4 , and I lv--CH--R4
R3 o
and mixtures thereof, wherein R1 is an alkyl, aryl, or alkaryl group
cont~inin,e~ from 1 to 14 carbon atoms, R is an alkyl chain cont~inin~ from
1 to 8 carbon atoms, R4 is H or R3, and Y is H or a solubilizing group.
Any of R1, R3 and R4 may be substituted by essentially any functional
group including, for example alkyl, hydroxy, alkoxy, halogen, amine,
nitrosyl, amide and ammonium or alkyl ammonium groups.
The preferred solubilizing groups are -S03-M+, -C02-M+, -S04-M+,
-N+(R3)~X- and O < --N(R3)3 and most preferably -S03-M + and
-C02-M wherein R3 is an alkyl chain cont~ining from 1 to 4 carbon
atoms, M is a cation which provides solubility to the bleach activator and X
is an anion which provides solubility to the bleach activator. Preferably, M
is an alkali metal, ammonium or substituted ammonium cation, with sodium
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and potassium being most preferred, and X is a halide, hydroxide,
methylsulfate or acetate anion.
Perbenzoic acid precursor
Perbenzoic acid precursor compounds provide perbenzoic acid on
perhydrolysis.
Suitable O-acylated perbenzoic acid precursor compounds include the
substituted and unsubstituted benzoyl oxybenzene sulfonates, including for
example benzoyl oxybenzene sulfonate:
o
~o~SO3-
Also suitable are the benzoylation products of sorbitol, glucose, and allsaccharides with benzoylating agents, including for example:
OAc
AcO~o
) ~,OAc
OAc
OBz
Ac = COCH3; Bz = Benzoyl
Perbenzoic acid precursor compounds of the imide type include N-benzoyl
succinimide, tetrabenzoyl ethylene ~i~min~ and the N-benzoyl substituted
- ureas. Suitable imidazole type perbenzoic acid precursors include N-
benzoyl imidazole and N-benzoyl benzimidazole and other useful N-acyl
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group-cont~ining perbenzoic acid precursors include N-benzoyl
pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
Other perbenzoic acid precursors include the benzoyl diacyl peroxides, the
benzoyl tetraacyl peroxides, and the compound having the forrnula:
O O
~0 O~COOH
Phthalic anhydride is another suitable perbenzoic acid precursor compound
hereln:
~0
Suitable N-acylated l~ct~m perbenzoic acid precursors have the formula:
O C--CH2--CH2
R6--C--N
--CH2~cH2 ]n
wherein n is from 0 to 8, preferably from 0 to 2, and R6 is a benzoyl
group.
.. .. _, -- , . ~
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/6
Perbenzoic acid derivative precursors
Perbenzoic acid derivative precursors provide substituted perbenzoic acids
on perhydrolysis.
Suitable substituted perbenzoic acid derivative precursors include any of the
herein disclosed perbenzoic precursors in which the benzoyl group is
substituted by essentially any non-positively charged (i.e.; non-cationic)
functional group including, for example alkyl, hydroxy, alkoxy, halogen,
amine, nitrosyl and amide groups.
A preferred class of substituted perbenzoic acid precursor compounds are
the amide substituted compounds of the following general formulae:
R1--C---N R2 C--- L R1 N C-- R2 C--L
O R5 O or R5 O o
wherein Rl is an aryl or alkaryl group with from 1 to 14 carbon atoms, R2
is an arylene, or alkarylene group cont~inin~ from 1 to 14 carbon atoms,
and R5 is H or an alkyl, aryl, or alkaryl group cont~inin~ 1 to 10 carbon
atoms and L can be essentially any leaving group. Rl preferably contains
from 6 to 12 carbon atoms. R2 preferably contains from 4 to 8 carbon
atoms. Rl may be aryl, substituted aryl or alkylaryl cont~inin~ branching,
substitution, or both and may be sourced from either synthetic sources or
natural sources including for example, tallow fat. Analogous structural
variations are permissible for R2. The substitution can include alkyl, aryl,
halogen, nitrogen, sulphur and other typical substituent groups or organic
compounds. R5 is preferably H or methyl. Rl and R5 should not contain
more than 18 carbon atoms in total. Amide substituted bleach activator
compounds of this type are described in EP-A-0170386.
- Cationic peroxyacid precursors
Cationic peroxyacid precursor compounds produce cationic peroxyacids on
perhydrolysis.
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Typically, cationic peroxyacid precursors are formed by substituting the
peroxyacid part of a suitable peroxyacid precursor compound with a
positively charged f~mctional group, such as an ammonium or alkyl
ammonium group, preferably an ethyl or methyl ammonium group.
Cationic peroxyacid precursors are typically present in the compositions as
a salt with a suitable anion, such as for example a halide ion or a
methylsulfate ion.
The peroxyacid precursor compound to be so cationically substituted maybe a perbenzoic acid, or substituted derivative thereof, precursor compound
as described hereinbefore. Alternatively, the peroxyacid precursor
compound may be an alkyl percarboxylic acid precursor compound or an
amide substituted alkyl peroxyacid precursor as described hereinafter
Cationic peroxyacid precursors are described in U.S. Patents 4,904,406;4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022;
5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP
87-318,332.
Suitable cationic peroxyacid precursors include any of the ammonium or
alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-
acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl
peroxides.
A preferred cationically substitllte~1 benzoyl oxybenzene sulfonate is the 4-
(trimethyl amrnonium) methyl derivative of benzoyl oxybenzene sulfonate:
~SO3-
/ ~
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A preferred cationically substituted alkyl oxybenzene sulfonate has theformula:
,,~ SO
,; ~,,- ', - "o '~ /
Preferred cationic peroxyacid precursors of the N-acylated caprolactam
class include the trialkyl ammonium methylene benzoyl caprolactams,
particularly trimethyl ammonium methylene benzoyl caprolactam:
o o
,-',~ ~' - - ~ - N
Other preferred cationic peroxyacid precursors of the N-acylated
caprolactam class include the trialkyl arnmonium methylene alkyl
caprolactams:
O o
N ~ '~
, N+ ~ ( 2)
where n is from 0 to 12, particularly from 1 to 5.
Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl
arnmonium) ethyl sodium 4-sulphophenyl carbonate chloride.
Alkyl percarboxylic acid bleach precursors
Alkyl percarboxylic acid bleach precursors form percarboxylic acids on
perhydrolysis. Preferred precursors of this type provide peracetic acid on
perhydrolysis.
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WO 97t36990 PCTrUS97/04953
~;
Preferred alkyl percarboxylic precursor compounds of the imide type
include the N-,N,N1N1 tetra acetylated alkylene diamines wherein the
alkylene group contains from 1 to 6 carbon atoms, particularly those
compounds in which the alkylene group contains 1, 2 and 6 carbon atoms.
Tetraacetyl ethylene ~ mine (TAED) is particularly preferred.
Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-
tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium
nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate
(ABS) and penta acetyl glucose.
Amide substituted alkyl peroxyacid precursors
Amide substituted alkyl peroxyacid precursor compounds are also suitable,
including those of the following general formulae:
R1--C N--R2 C L R1---N C---R2----C---L
O R5 0 or R5 0 0
wherein Rl is an alkyl group with from 1 to 14 carbon atoms, R2 is an
alkylene group cont~intng from 1 to 14 carbon atoms, and R5 is H or an
alkyl group cont~inin~ 1 to 10 carbon atoms and L can be essentially any
leaving group. Rl preferably contains from 6 to 12 carbon atoms. R2
preferably contains from 4 to 8 carbon atoms. Rl may be straight chain or
branched alkyl cont~ining branching, substitution, or both and may be
sourced from either synthetic sources or natural sources including for
example, tallow fat. Analogous s~ructural variations are permissible for
R2. The substitution can include alkyl, halogen, nitrogen, sulphur and
other typical substituent groups or organic compounds. R5 is preferably H
or methyl. Rl and R5 should not contain more than 18 carbon atoms in
total. Amide substituted bleach activator compounds of this type are
described in EP-A-0170386.
.
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Benzoxazin or~anic peroxvacid precursors
Also suitable are precursor compounds of the benzoxazin-type, as disclosed
for example in EP-A-332,294 and EP-A-482,807, particularly those having
the formula:
C
[~N"C R1
including the substituted benzoxazins of the type
R2 C
R3~N~~--R,
R5
wherein R1 is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R2, R3, R4,
and R5 may be the same or different substituents selected from H, halogen,
alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COOR6
(wherein R6 is H or an alkyl group) and carbonyl functions.
An especially preferred precursor of the benzoxazin-type is:
[~N' ~
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,~/
Preformed organic peroxyacid
The organic peroxyacid bleaching system may contain, in addition to, oras an alternative to, an organic peroxyacid bleach precursor compound, a
preformed organic peroxyacid, typically at a level of from 0.5% to 25~
by weight, more preferably from 1% to 10% by weight of the composition.
A preferred class of organic peroxyacid compounds are the amide
substituted compounds of the following general formulae:
R1 -C--N---R2-- C--OOH R1 N~C~ R2 C--OOH
O R5 O or R5 O O
wherein Rl is an allcyl, aryl or alkaryl group with from 1 to 14 carbon
atoms, R2 is an alkylene, arylene, and alkarylene group con~inin~ from 1
to 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group
con~inin~ 1 to 10 carbon atoms. R1 preferably contains from 6 to 12
carbon atoms. R2 preferably contains from 4 to 8 carbon atoms. Rl may
be straight chain or branched alkyl, substituted aryl or alkylaryl cont~ining
branching, substitution, or both and may be sourced from either synthetic
sources or natural sources including for example, tallow fat. Analogous
structural variations are permissible for R2. The substitution can include
alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups
or organic compounds. R5 is preferably H or methyl. Rl and R5 should
not contain more than 18 carbon atoms in total. Amide substituted organic
peroxyacid compounds of this type are described in EP-A-0170386.
Other organic peroxyacids include diacyl and tetraacylperoxides, especially
diperoxydo~lec~nP~ioc acid, diperoxytetradecanedioc acid, and
diperoxyhexadecanedioc acid. Dibenzoyl peroxide is a preferred organic
peroxyacid herein. Mono- and diperazelaic acid, mono- and diperbrassylic
acid, and N-phthaloyl~minoperoxicaproic acid are also suitable herein.
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Water-soluble builder compound
The compositions used in accord with this invention may optionally contain
an additional builder compound. Suitable water-soluble builder compounds
include the water soluble monomeric polycarboxylates, or their acid forms,
homo or copolymeric polycarboxylic acids or their salts in which the
polycarboxylic acid comprises at least two carboxylic radicals separated
from each other by not more that two carbon atoms, carbonates,
bicarbonates, borates, phosphates, and mixtures thereof.
The carboxylate or polycarboxylate builder can be monomeric or
oligomeric in type although monomeric polycarboxylates are generally
preferred for reasons of cost and performance.
Suitable carboxylates cont~inin~ one carboxy group include the water
soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
Polycarboxylates cont~inin~ two carboxy groups include the water-soluble
salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic
acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as ~vell
as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates
cont~ining three carboxy groups include, in particular, water-soluble
citrates, aconitrates and citraconates as well as succinate derivatives such as
the carboxymethyloxysuccinates described in British Patent No. 1,379,241,
lactoxysuccinates described in British Patent No. 1,389,732, and
aminosuccinates described in Netherlands Application 7205873, and the
oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates
described in British Patent No. 1,387,447.
Polycarboxylates cont~inin~; four carboxy groups include oxydisuccinates
disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates,
1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
Polycarboxylates cont~ining sulfo substituents include the sulfosuccinate
- derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in
U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described
in British Patent No. 1,439,000.
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Alicyclic and heterocyclic polycarboxylates include cyclopentane-
cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-
tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran - cis -
dicarboxylates, 2,2,5,5-tetrahydrofuran - tetracarboxylates, 1,2,3,4,5,6-
hexane - hexacarboxylates and carboxymethyl derivatives of polyhydric
alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates
include mellitic acid, pyromellitic acid and the phthalic acid derivatives
disclosed in British Patent No. 1,425,343.
Of the above, the preferred polycarboxylates are hydroxycarboxylates
cont~ining Up to three carboxy groups per molecule, more particularly
citrates.
The parent acids of the monomeric or oligomeric polycarboxylate chelating
agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric
acid mixtures are also contemplated as useful builder components.
Borate builders, as well as builders cont~inin~ borate-forming materials that
can produce borate under detergent storage or wash conditions can also be
used but are not preferred at wash conditions less that about 50~C,
especially less than about 40~C.
Examples of carbonate builders are the ~lk~lin~ earth and alkali metal
carbonates, including sodium carbonate and sesqui-carbonate and mixtures
thereof with ultra-fine calcium carbonate as disclosed in German Patent
Application No. 2,321,001 published on November 15, 1973.
Partially soluble or insoluble builder compound
The detergent compositions of the present invention may contain a partially
soluble or insoluble builder compound, typically present at a level of from
1% to 80% by weight, preferably from 10% to 70% by weight, most
preferably from 20% to 60% weight of the composition.
-
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o2y .,
Examples of largely water insoluble builders include the sodium
aluminosilicates .
Suitable aluminosilicate zeolites have the unit cell formula
Naz[(AlO2)z(SiO2)y]. xH2O wherein z and y are at least 6; the molar
ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to
276, more preferably from 10 to 264. The aluminosilicate material are in
hydrated form and are preferably crystalline, Cont~ining from 10% to 28%,
more preferably from 18% to 22% water in bound form.
The aluminosilicate zeolites can be naturally occurring materials, but are
preferably synthetically derived. Synthetic crystalline aluminosilicate ion
exchange materials are available under the designations Zeolite A, Zeolite
B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the
formula
Na 12 [Al~2) 12 (sio2)l2]. xH2O
wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na86
[(A1~2)86(Si~2)106]- 276 H2O. Zeolite MAP, as disclosed in P-B-
384,070 is a preferred zeolite builder herein.
Water-soluble bismuth compound
The compositions used in this invention may contain a water-soluble
bi~ml-t~l compound, preferably present at a level of from 0.005% to 20%,
more preferably from 0.01% to 5%, most preferably from 0.1 % to 1 % by
weight of the compositions.
The water-soluble bismuth compound may be essentially any salt or
complex of bismuth with essentially any inorganic or organic counter
anion. Preferred inorganic bismuth salts are selected from the bicmut~
trihalides, bismuth nitrate and bismuth phosphate. Bismuth acetate and
citrate are preferred salts with an organic counter anion.
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~S
Water-soluble sulfate salt
The compositions may optionally contain a water-soluble sulfate salt,
preferably present at a level of from 0.1 % to 40%, more preferably from
1 % to 30%, most preferably from 5 % to 25 % by weight of the
compositions.
The water-soluble sulfate salt may be essentially any salt of sulfate with any
counter cation. Preferred salts are selected from the sulfates of the alkali
and alkaline earth metals, particularly sodium sulfate.
Corrosion inhibitor compound
The compositions may contain corrosion inhibitors preferably selected from
organic silver coating agents, particularly paraffin, nitrogen-cont~ining
corrosion inhibitor compounds and Mn(II) compounds, particularly Mn(II)
salts of organic ligands.
Organic silver coating agents are described in PCT Publication No.
WO94/16047 and copending UK Application No. UK 9413729.6.
Nitrogen-cont~inin~ corrosion inhibitor compounds are disclosed in
copending European Application no. EP 93202095.1. Mn(II) compounds
for use in corrosion inhibition are described in copending UK Application
No. 9418567.5.
Organic silver coating agents
Organic silver coating agent may be incorporated in automatic dishwashing
compositions herein at a level of from 0.05% to 10%, preferably from
0.1 % to 5 % by weight of the total composition.
The functional role of the silver coating agent is to form 'in use' a
protective coating layer on any silverware components of the washload to
which the compositions of the invention are being applied. The silver
coating agent should hence have a high affinity for attachment to solid
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~G
silver surfaces, particularly when present in as a component of an agueous
washing and bleaching solution with which the solid silver surfaces are
being treated.
Suitable organic silver coating agents herein include fatty esters of mono-
or polyhydric alcohols having from 1 to about 40 carbon atoms in the
hydrocarbon chain.
The fatty acid portion of the fatty ester can be obtained from mono- or
poly-carboxylic acids having from 1 to about 40 carbon atoms in the
hydrocarbon chain. Suitable examples of monocarboxylic fatty acids
include behenic acid, stearic acid, oleic acid, palmitic acid, myristic acid,
lauric acid, acetic acid, propionic acid, butyric acid, isobutyric acid,
Valerie acid, lactic acid, glycolic acid and ~"B'- dihydroxyisobutyric acid.
Examples of suitable polycarboxylic acids include: n-butyl-malonic acid,
isocitric acid, citric acid, maleic acid, malic acid and succinic acid.
The fatty alcohol radical in the fatty ester can be represented by mono- or
polyhydric alcohols having from 1 to 40 carbon atoms in the hydrocarbon
chain. Examples of suitable fatty alcohols include; behenyl, arachidyl,
cocoyl, oleyl and lauryl alcohol, ethylene glycol, glycerol, ethanol,
isopropanol, vinyl alcohol, diglycerol, xylitol, sucrose, erythritol,
pentaerythritolt sorbitol or sorbitan.
Preferably, the fatty acid and/or ~atty alcohol group of the fatty ester
adjunct material have from 1 to 24 carbon atoms in the alkyl chain.
Preferred fatty esters herein are ethylene glycol, glycerol and sorbitan
esters wherein the fatty acid portion of the ester normally comprises a
species selected from behenic acid, stearic acid, oleic acid, palmitic acid or
myristic acid.
The glycerol esters are also highly preferred. These are the mono-, di- or
tri-esters of glycerol and the fatty acids as defined above.
.
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Specific examples of fatty alcohol esters for use herein include: stearyl
acetate, palmityl di-lactate, cocoyl isobutyrate, oleyl maleate, oleyl
dimaleate, and tallowyl proprionate. Fatty acid esters useful herein
include: xylitol monopalmitate, pentaerythritol monostearate? sucrose
monostearate, glycerol monostearate, ethylene glycol monostearate,
sorbitan esters. Suitable sorbitan esters include sorbitan monostearate,
sorbitan palmitate, sorbitan monolaurate, sorbitan monomyristate, sorbitan
monobehenate, sorbitan mono-oleate, sorbitan dilaurate, sorbitan
distearate, sorbitan dibehenate, sorbitan dioleate, and also mixed
tallowalkyl sorbitan mono- and di-esters.
Glycerol monostearate, glycerol mono-oleate, glycerol monopalmitate,
glycerol monobehenate, and glycerol distearate are preferred glycerol
esters herein.
Suitable organic silver coating agents include triglycerides, mono or
diglycerides, and wholly or partially hydrogenated derivatives thereof, and
any mixtures thereof. Suitable sources of fatty acid esters include
vegetable and fish oils and ~nim~l fats. Suitable vegetable oils include soy
bean oil, cotton seed oil, castor oil, olive oil, peanut oil, safflower oil,
sunflower oil, rapeseed oil, grapeseed oil, palm oil and corn oil.
Waxes, including microcrystalline waxes are suitable organic silver coating
agents herein. Preferred waxes have a melting point in the range from
about 35~C to about 110~C and comprise generally from 12 to 70 carbon
atoms. Preferred are petroleum waxes of the paraffin and microcrystalline
type which are composed of long-chain saturated hydrocarbon compounds.
Alginates and gelatin are suitable organic silver coating agents herein.
Dialkyl amine oxides such as C12-C20 methyl~mine oxide, and dialkyl
quaternary ammonium compounds and salts, such as the C12-C20
methylammonium halides are also suitable.
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Other suitable organic silver coating agents include certain polymeric
materials. Polyvinylpyrrolidones with an average molecular weight of from
~2,000 to 700,000, polyethylene glycols (PEG) with an average molecular
weight of from 600 to 10,000, polyamine N-oxide polymers, copolymers
of N-vinylpyrrolidone and N-vinylimidazole, and cellulose derivatives such
as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose are
examples of such polymeric materials.
Certain perfume materials, particularly those demonstrating a high
substantivity for metallic surfaces, are also useful as the organic silver
coating agents herein.
Soil release agent
Polymeric soil release agents can also be used as an organic silver coating
agent. Such soil release agents are also preferred ingredients of laundry
detergent compositions herein, for their soil release capability.
Suitable polymeric soil release agents include those soil release agents
having: (a) one or more nonionic hydrophile components consisting
essentially of (i) polyoxyethylene segments with a degree of polymerization
of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a
degree of polymerization of from 2 to 10, wherein said hydrophile segment
does not encompass any oxypropylene unit unless it is bonded to adjacent
moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene
units comprising oxyethylene and from 1 to about 30 oxypropylene units,
said hydrophile segments preferably comprising at least about 25 %
oxyethylene units and more preferably, especially for such components
having about 20 to 30 oxypropylene units, at least about 50 % oxyethylene
units; or (b) one or more hydrophobe components comprising (i) C3
oxyalkylene terephth~l~te segments, wherein, if said hydrophobe
components also comprise oxyethylene terephth~l~te, the ratio of
oxyethylene terephthalate:C3 oxyalkylene terephth~l~te units is about 2:1 or
lower, (ii) C4-C6 alkylene or oxy C4-C6 alkylene segments, or mixtures
therein, (iii) poly (vinyl ester) segments, preferably polyvinyl acetate,
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~q
having a degree of polymerization of at least 2, or (iv) C1-C4 alkyl ether or
C4 hydroxyalkyl ether substituents, or mixtures therein, wherein said
substituents are present in the form of Cl-C4 alkyl ether or C4
hydroxyalkyl ether cellulose derivatives, or mixtures therein, or a
combination of (a) and (b).
Typically, the polyoxyethylene segments of (a)(i) will have a degree ofpolymerization of from about 200, although higher levels can be used,
preferably from 3 to about 150, more preferably from 6 to about 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)nOC~I2CH20-, 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 herein also include cellulosic
derivatives such as hydroxyether cellulosic polymers, copolymeric blocks
of ethylene terephth~l~te or propylene terephth~l~te with polyethylene oxide
or polypropylene oxide terephth~l~te, 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 consisting of C1-C4 alkyl and C4
hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28,
1976 to Nicol, et al.
Soil release agents characterized by poly(vinyl ester) hydrophobe segments
include graft copolymers of poly(vinyl ester), e.g., C1-C6 vinyl esters,
preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones,
such as polyethylene oxide backbones. See European Patent Application
0 219 048, published April 22, 1987 by Kud, et al.
Another suitable soil release agent is a copolymer having random blocks of
ethylene terephthalate and polyethylene oxide (PEO) terephth~l~te. The
molecular weight of this polymeric soil release agent is in the range of from
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'~0
about 25,000 to about 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 suitable polymeric soil release agent is a polyester with repeat
units of ethylene terephth~l~te units contains 10-15 % by weight of ethylene
terephthalate units together with 90-80% by weight of polyoxyethylene
terephthalate units, derived from a polyoxyethylene glycol of average
molecular weight 300-5,000.
Another suitable polymeric soil release agent is a sulfonated product of a
subst~nri~lly 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 terephth~l~te 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. Other 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 sul-
foarolyl, end-capped terephth~l~te esters.
Another 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 termin~t~ocl with modified isethionate end-caps. A particularly
preferred soil release agent of this type comprises about one
sulfoisophthaloyl unit, S terephthaloyl units, oxyethyleneoxy and oxy-1,2-
propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-
cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate.
A preferred organic silver coating agent is a paraffin oil, typically a
predomin~ntly branched aliphatic hydrocarbon having a number of carbon
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~/
atoms in the range of from 20 to 50; preferred paraffin oil selected from
predominantly branched C2s 45 species with a ratio of cyclic to noncyclic
hydrocarbons of from 1: 10 to 2: 1, preferably from 1:5 to 1: 1 . A paraffin
oil meeting these characteristics, having a ratio of cyclic to noncyclic
hydrocarbons of about 32:68, is sold by Wintershall, Salzbergen,
Germany, under the trade name WINOG 70.
Nitrogen-cont~inin~ corrosion inhibitor compounds
Suitable nitrogen-cont~inin~ corrosion inhibitor compounds include
imidazole and derivatives thereof such as benzimidazole, 2-heptadecyl
imidazole and those imidazole derivatives described in Czech Patent No.
139, 279 and British Patent GB-A-1,137,741, which also discloses a
method for m~king imidazole compounds.
Also suitable as nitrogen-cont~ining corrosion inhibitor compounds are
pyrazole compounds and their derivatives, particularly those where the
pyrazole is substituted in any of the 1, 3, 4 or 5 positions by substituents
Rl, R3, R4 and Rs where Rl is any of H, CH20H, CONH3, or COCH3,
R3 and Rs are any of Cl-C20 alkyl or hydroxyl, and R4 is any of H, NH2
or NO2.
Other suitable nitrogen-cont~ining corrosion inhibitor compounds include
benzotriazole, 2-mercaptobenzothiazole, 1-phenyl-5-mercapto-1,2,3,4-
tetrazole, thionalide, morpholine, mel~min~, distearyl~mine, stearoyl
stearamide, cyanuric acid, aminotriazole, aminotetrazole and indazole.
Nitrogen-cont~ining compounds such as amines, especially distearylamine
and ammonium compounds such as ammonium chloride, ammonium
bromide, ammonium sulphate or (li~mmonium hydrogen citrate are also
suitable.
.
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Mn(II) corrosion inhibitor compounds
The compositions may contain an Mn(II) corrosion inhibitor compound.
The Mn(II) compound is preferably incorporated at a level of from 0.005%
to 5 ~ by weight, more preferably from 0.01 ~ to 1 %, most preferably
from 0.02% to 0.4~ by weight of the compositions. Preferably, the Mn(II)
compound is incorporated at a level to provide from 0.1 ppm to 250 ppm,
more preferably from 0.5 ppm to 50 ppm, most preferably from 1 ppm to
20 ppm by weight of Mn(II) ions in any bleaching solution.
The Mn (II) compound may be an inorganic salt in anhydrous, or any
hydrated forms. Suitable salts include m~n~nese sulphate, manganese
carbonate, m~n~nese phosphate, m~n~nese nitrate, m~n~nese acetate
and m~n~nese chloride. The Mn(II) compound may be a sall or complex
of an organic fatty acid such as manganese acetate or manganese stearate.
The Mn(II) compound may be a salt or complex of an organic ligand. In
one preferred aspect the organic ligand is a heavy metal ion sequestrant. In
another preferred aspect the organic ligand is a crystal growth inhibitor.
Other corrosion inhibitor compounds
.
Other suitable additional corrosion inhibitor compounds include,
mercaptans and diols, especially mercaptans with 4 to 20 carbon atoms
including lauryl mercaptan, thiophenol, thionapthol, thionalide and
thioanthranol. Also suitable are saturated or ~ n.c~ rated C lo-C20 fatty
acids, or their salts, especially aluminium tristearate. The C12-C20
hydroxy fatty acids, or their salts, are also suitable. Phosphonated octa-
rlec~ne and other anti-oxidants such as betahydroxytoluene (BHT) are also
suitable.
Copolymers of butadiene and maleic acid, particularly those supplied under
the trade reference no. 07787 by Polysciences Inc have been found to be of
particular utility as corrosion inhibitor compounds.
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'~
Total Available Oxygen (AvO) Level
It has been found that, for optimal anti-silver tarni~hin~ performance, the
level of available oxygen in the present compositions, measured in units of
% available oxygen by weight of the composition, is preferably controlled;
the level of available oxygen should hence preferably be in the range from
0.3 % to 2.5 %, preferably from 0.5 % to 1.7 %, more preferably from 0.6%
to 1.5%, most preferably from 0.7% to 1.2%, measured according to the
method described hereunder.
Rate of Release of AvO
The rate of release of available oxygen is preferably also controlled; the
rate of release of available oxygen from the compositions herein preferably
should be such that, when using the method described hereinafter, the
available oxygen is not completely released from the composition until after
3.5 minutes, preferably the available oxygen is released in a time interval
of from 3.5 minlltes to 10.0 minutes, more preferably from 4.0 min~ltes to
9.0 minlltes, most preferably from 5.0 minlltes to 8.5 minlltes.
Method for Measuring Level of Total Available Oxv~en (AvO) and Rate of
Release of AvO in a Deter~ent Composition
Method
1. A beaker of water (typically 2L) is placed on a stirrer Hotplate, and
the stirrer speed is selected to ensure that the product is evenly dispersed
through the solution.
2. The detergent composition (typically 8g of product which has been
sampled down from a bulk supply using a Pascal sampler), is added and
simultaneously a stop clock is started.
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3. The temperanlre control should be adjusted so as to m~int~in a
constant temperature of 20~C throughout the experiment.
4. Samples are taken from the detergent solution at 2 minllte time
intervals for 20 minlltes, starting after 1 minllte, and are titrated by the
"titration procedure" described below to determine the level of available
oxygen at each point.
Titration Procedure
1. An aliquot from the detergent solution (above) and 2ml sulphuric
acid are added into a stirred beaker
2. Approximately 0.2g arnmonium molybdate catalyst (tetra hydrate
form) are added
3. 3mls of 10% sodium iodide solution are added
4. Titration with sodium thiosulphate is conducted until the end point.
The end point can be seen using either of two procedures. First procedure
consists simply in seeing the yellow iodine colour fading to clear. The
second and preferred procedure consists of ~ldin~ soluble starch when the
yellow colour is becoming faint, turning the solution blue. More
thiosulphate is added until the end point is reached (blue starch complex is
decolourised).
The level of AvO, measured in units of ~ available oxygen by weight, for
the sample at each time interval corresponds to the amount of titre
according to the following equation
Vol S203(ml) x Molarity (S203) x 8
Sample mass (g)
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~vO level is plotted versus time to determine the maximum level of AvO,
and the rate of release of AvO
Controlled rate of release - means
A means may be provided for controlling the rate of release of oxygen
bleach to the wash solution.
Means for controlling the rate of release of the bleach may provide for
controlled release of peroxide species to the wash solution. Such means
could, for example, include controlling the release of any inorganic
perhydrate salt, acting as a hydrogen peroxide source, to the wash solution.
Suitable controlled release means can include coating any suitable
component with a coating designed to provide the controlled release. The
coating may therefore, for example, comprise a poorly water soluble
material, or be a coating of sufficient thickness that the kinetics of
dissolution of the thick coating provide the controlled rate of release.
The coating material may be applied using various methods. Any coatingmaterial is typically present at a weight ratio of coating material to bleach
of from 1:99 to 1:2, preferably from 1:49 to 1:9.
Suitable coating materials include triglycerides (e.g. partially)
hydrogenated vegetable oil, soy bean oil, cotton seed oil) mono or
diglycerides, microcrystalline waxes, gelatin, cellulose, fatty acids and any
mixtures thereof.
Other suitable coating materials can comprise the alkali and ~lk~lin~ earth
metal sulphates, silicates and carbonates, including calcium carbonate and
silicas.
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;;~3 6
A preferred coating material, particularly for an inorganic perhydrate salt
bleach source, comprises sodium silicate of SiO2: ~a2O ratio from 1.8: 1
to 3.0: 1, preferably 1.8:1 to 2.4:1, and/or sodium metasilicate, preferably
applied at a level of from 2~ to 10%, (normally from 35~O to 5%) of SiO2
by weight of the inorganic perhydrate salt. Magnesium silicate can also be
included in the coating.
Any inorganic salt coating materials may be combined with organic binder
materials to provide composite inorganic salt/organic binder coatings.
Suitable binders include the C10-c2o alcohol ethoxylates con~ining from 5
- 100 moles of ethylene oxide per mole of alcohol and more preferably the
C1s-C20 primary alcohol ethoxylates cont~inin$ from 20 - 100 moles of
ethylene oxide per mole of alcohol.
Other preferred binders include certain polymeric materials.
Polyvinylpyrrolidones with an average molecular weight of from 12,000 to
700,000 and polyethylene glycols (PEG) with an average molecular weight
of from 600 to 5 x 106 preferably 1000 to 400,000 most preferably 1000 to
10,000 are examples of such polymeric materials. Copolymers of maleic
anhydride with ethylene, methylvinyl ether or methacrylic acid, the maleic
anhydride constituting at least 20 mole percent of the polymer are further
examples of polymeric materials useful as binder agents. These polymeric
materials may be used as such or in combination with solvents such as
water, propylene glycol and the above mentioned C1o-C20 alcohol
ethoxylates cons~ining from 5 - 100 moles of ethylene oxide per mole.
Further examples of binders include the C1o-C20 mono- and diglycerol
ethers and also the C1o-C20 fatty acids.
Cellulose derivatives such as methylcellulose, carboxymethylcellulose and
hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or
their salts are other examples of binders suitable for use herein.
- One method for applying the coating material involves agglomeration.
Preferred agglomeration processes include the use of any of the organic
binder materials described hereinabove. Any conventional
.
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agglomerator/mixer may be used including, but not limited to pan, rotary
drum and vertical blender types. Molten coating compositions may also be
applied either by being poured onto, or spray atomized onto a moving bed
of bleaching agent.
Other means of providing the re~uired controlled release include
mechanical means for altering the physical characteristics of the bleach to
control its solubility and rate of release. Suitable protocols could include
compaction, mechanical injection, manual injection, and adjustment of the
solubility of the bleach compound by selection of particle size of any
particulate component.
Whilst the choice of particle size will depend both on the composition of
the particulate component, and the desire to meet the desired controlled
release kinetics, it is desirable that the particle size should be more than
500 micrometers, preferably having an average particle diameter of from
800 to 1200 micrometers.
Additional protocols for providing the means of controlled release include
the suitable choice of any other components of the detergent composition
matrix such that when the composition is introduced to the wash solution
the ionic strength environrnent therein provided enables the required
controlled release kinetics to be achieved.
Alk~linity system
The compositions preferably contain an ~Ik~linity system cont~ining sodium
silicate having an SiO2: Na2O ratio of from 1.8 to 3.0, preferably from
1.8 to 2.4, most preferably 2.0, present preferably at a level of less than
20%, preferably from 1% to 15~, most preferably from 3% to 12% by
weight of SiO2. The alkali metal silicate may be in the form of either the
anhydrous salt or a hydrated salt.
The ~lk~linity system also preferably contains sodium metasilicate, present
at a level of at least 0.4 % SiO2 by weight. Sodium metasilicate has a
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,~
nominal SiO2: Na2O ratio of 1Ø The weight ratio of said sodium silicate
to said sodium metasilicate, measured as SiO2, is preferably from 50:1 to
5:4, more preferably from 15:1 to 2:1, most preferably from 10:1 to 5:2.
Heavy metal ion sequestrant
The detergent compositions of the invention preferably contain as an
optional component a heavy metal ion sequestrant. By heavy metal ion
sequestrant it is meant herein components which act to sequester (chelate)
heavy metal ions. These components may also have calcium and
magnesium chelation capacity, but preferentially they show selectivity to
binding heavy metal ions such as iron, manganese and copper.
Heavy metal ion sequestrants are generally present at a level of from
0.005% to 20%, preferably from 0.1% to 10%, more preferably from
0.25 % to 7.5 % and most preferably from 0.5 % to 5 % by weight of the
compositions. The weight ratio of heavy metal ion sequestrant to ATCA is
preferably from 1:20 to 20:1, more preferably from 1:10 to 10:1, most
preferably from 5 :1 to 1:5.
Heavy metal ion sequestrants, which are acidic in nature, having for
example phosphonic acid or carboxylic acid functionalities, may be present
either in their acid form or as a complex/salt with a suitable counter cation
such as an alkali or ~lk~lin~ metal ion, ammonium, or substituted
ammonium ion, or any mixtures thereof. Preferably any salts/complexes
are water soluble. The molar ratio of said counter cation to the heavy metal
ion sequestrant is preferably at least 1:1.
Suitable heavy metal ion sequestrants for use herein include organic
phosphonates, such as the amino alkylene poly (alkylene phosphonates),
alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylene
phosphonates. Preferred among the above species are diethylene triamine
penta (methylene phosphonate), ethylene ~ mine tri (methylene
phosphonate) hexamethylene ~ mine tetra (methylene phosphonate) and
hydroxy-ethylene 1,1 diphosphonate.
.
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Other suitable heavy metal ion sequestrant for use herein include
nitrilotriacetic acid and polyaminocarboxylic acids such as
ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid,
ethylenecli~mine disuccinic acid, ethylene~ mine diglutaric acid, 2-
hydroxypropylene~ mine disuccinic acid or any salts thereof.
Especially preferred is ethylene~ mine-N,N'-disuccinic acid (EDDS) or
the alkali metal, ~lk~line earth metal, ammonium, or substituted ammonium
salts thereof, or mixtures thereof. Preferred EDDS compounds are the free
acid form and the sodium or magnesium salt or complex thereof.
Crvstal growth inhibitor component
The detergent compositions preferably contain a crystal growth inhibitor
component, preferably an organodiphosphonic acid component,
incorporated preferably at a level of from 0.01% to 5%, more preferably
from 0.1 % to 2% by weight of the compositions.
By organo diphosphonic acid it is meant herein an organo diphosphonic
acid which does not contain nitrogen as part of its chemical structure. This
definition therefore excludes the organo aminophosphonates, which
however may be included in compositions of the invention as heavy metal
ion sequestrant components.
The organo diphosphonic acid is preferably a C1-C4 diphosphonic acid,
more preferably a C2 diphosphonic acid, such as ethylene diphosphonic
acid, or most preferably ethane 1-hydroxy-1, 1-diphosphonic acid (HEDP)
and may be present in partially or fully ionized form, particularly as a salt
or complex.
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~f G
Enzyme
Another optional ingredient useful in the compositions is one or more
enzymes. Preferred enzymatic materials include the commercially available
lipases, amylases, neutral and ~lk~line proteases, esterases, cellulases,
pectinases, lactases and peroxidases conventionally incorporated into
detergent compositions. Suitable enzymes are discussed in US Patents
3,519,570 and 3,533,139.
Preferred commercially available protease enzymes include those sold
under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase
by Novo Industries A/S (Denmark), those sold under the tradename
Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by
Genencor International, and those sold under the tradename Opticlean and
Optimase by Solvay Enzymes. Protease enzyme may be incorporated into
the compositions in accordance with the invention at a level of from
0.0001% to 4% active enzyme by weight of the composition.
Preferred amylases include, for example, a-amylases obtained from a
special strain of B licheniformis, described in more detail in GB-1,269,839
(Novo). Preferred commercially available amylases include for example,
those sold under the tradename Rapidase by Gist-Brocades, and those sold
under the tradename Termamyl and BAN by Novo Industries A/S.
Amylase enzyme may be incorporated into the composition in accordance
with the invention at a level of from 0.0001% to 2% active enzyme by
weight of the composition.
Lipolytic enzyme (lipase) may be present at levels of active lipolytic
enzyme of from 0.0001% to 2 % by weight, preferably 0.001 % to 1 % by
weight, most preferably from 0.001 % to 0.5 % by weight of the
compositions. The lipase may be fungal or bacterial in origin. Lipase from
chemically or genetically modified mutants of these strains are also useful
- herein. A preferred lipase is described in Granted European Patent, EP-B-
0218272.
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~/ .
An especially preferred lipase herein is obtained by cloning the gene from
Humicola lanuginosa and expressing the gene in Asper~illus orvza, as host,
as described in European Patent Application, EP-A-0258 068, which is
commercially available from Novo Industries A/S, Bagsvaerd, Denmark,
under the trade name Lipolase. This lipase is also described in U.S. Patent
4,810,414, Huge-Jensen et al, issued March 7, 1989.
Enzyme Stabilizin~ System
Preferred enzyme-cont~ining compositions herein may comprise from about
0.001~ to about 10%, preferably from about 0.005% to about 8%, most
preferably from about 0.01% to about 6%, by weight of an enzyme
stabilizing system. The enzyme stabilizing system can be any stabilizing
system which is compatible with the detersive enzyme. Such stabilizing
systems can comprise calcium ion, boric acid, propylene glycol, short
chain carboxylic acid, boronic acid, chlorine bleach scavengers and
mixtures thereof. Such stabilizing systems can also comprise reversible
enzyme inhibitors, such as reversible protease inhibitors.
Organic polymeric compound
Organic polymeric compounds may be added as preferred components of
the compositions in accord with the invention. By organic polymeric
compound it is meant essentially any polymeric organic compound
commonly used as dispersants, and anti-redeposition and soil suspension
agents in detergent compositions. Organic polymer compounds, however,
have not been previously described as soil release agents in dishwashing.
Organic polymeric compound is typically incorporated in the de~ergent
compositions of the invention at a level of from 0.1 % to 30%, preferably
from 0.5% to 15%, most preferably from 1% to 10% by weight of the
compositlons.
. .
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Examples of organic polymeric compounds include the water soluble
organic homo- or co-polymeric polycarboxylic acids or their salts in which
the polycarboxylic acid comprises at least two carboxyl radicals separated
from each other by not more than two carbon atoms. Polymers of the latter
type are disclosed in GB-A-1,596,756. Examples of such salts are
polyacrylates of molecular weight 2000-10000 and their copolymers with
any suitable other monomer units including modified acrylic, fumaric,
maleic, itaconic, aconitic, mesaconic, citraconic and methylenemalonic
acid or their salts, maleic anhydride, acrylamide, alkylene, vinylmethyl
ether, styrene and any mixnlres thereof. Preferred are the copolymers of
acrylic acid and maleic anhydride having a molecular weight of from
20,000 to 100,000.
Preferred commercially available acrylic acid cont~ining polymers having a
molecular weight below 15,000 include those sold under the tradename
Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 by BASF GmbH,
and those sold under the tradename Acusol 45N by Rohm and Haas.
Preferred acrylic acid cont~ining copolymers include those which contain
as monomer units: a) from 90% to 10~, preferably from 80~ to 20% by
weight acrylic acid or its salts and b) from 10% to 90%, preferably from
20% to 80% by weight of a substituted acrylic monomer or its salts having
the general formula -[CR2-CR1(CO-O-R3)]- wherein at least one of the
substituents Rl, R2 or R3, preferably Rl or R2 is a 1 to 4 carbon alkyl or
hydroxyalkyl group~ R~ or R2 can be a hydrogen and R3 can be a
hydrogen or alkali metal salt. Most preferred is a substituted acrylic
monomer wherein R1 is methyl, R2 is hydrogen (i.e. a methacrylic acid
monomer). The most preferred copolymer of this type has a molecular
weight of 3500 and contains 60~ to 80~ by weight of acrylic acid and
40 % to 20 % by weight of methacrylic acid.
The polyamino compounds are useful herein including those derived from
aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and
EP-A-35 1629.
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Clay softening system
The detergent compositions where formulated for laundry usage may
contain a clay softening system comprising a clay mineral compound and
optionally a clay flocculating agent.
The clay mineral compound is preferably a smectite clay compound.
Smectite clays are disclosed in the US Patents Nos. 3~862,058, 3,948,790,
3,954,632 and 4,062,647. European Patents Nos. EP-A-299,575 and EP-
A-313,146 in the name of the Procter and Gamble Company describe
suitable organic polymeric clay flocc~ ting agents.
Lime soap dispersant compound
The compositions of the invention may contain a lime soap dispersant
compound, preferably present at a level of from 0.1 ~ to 40~ by weight,
more preferably 1 % to 20% by weight, most preferably from 2% to 10%
by weight of the compositions.
A lime soap dispersant is a material that prevents the precipitation of alkali
metal, ammonium or amine salts of fatty acids by calcium or m~gnesium
ions. Preferred lime soap dispersant compounds are disclosed in PCT
Application No. W093/08877.
Suds suppressing system
The compositions of the invention, when formulated for use in machine
washing compositions, preferably comprise a suds suppressing system
present at a level of from 0.01 % to 15 ~, preferably from 0.05 % to 10~,
most pre~erably from 0.1 % to 5 % by weight of the composition.
Suitable suds suppressing systems for use herein may comprise essentially
any known antifoam compound, including, for example silicone antifoam
compounds, 2-alkyl and alcanol antifoam compounds. Preferred suds
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Y~ ,.
suppressing systems and antifoam compounds are disclosed in PCT
Application No. W093/08876 and copending European Application No.
93870132.3.
Polymeric dye transfer inhibitin~ a~ents
The compositions herein may also comprise from 0.01% to 10 %,
preferably from 0.05~ to 0.5% by weight of polymeric dye transfer
inhibiting agents.
The polymeric dye transfer inhibiting agents are preferably selected from
polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-
vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.
a) Polyamine N-oxide polymers
Polyamine N-oxide polymers suitable for use herein contain units havingthe following structure forrnula:
Ax
wherein P is a polymerisable unit, and
O O O
A is NC, CO, C,--O -, --S--, --N--; x is O or l;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic
groups or any combination thereof whereto the nitrogen of the N-0 group
can be attached or wherein the nitrogen of the N-0 group is part of these
groups.
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The N-O group can be represented by the following general structures:
o
(R1)X --N---(R2)y
(R~)z or =N (R1)X
wherein Rl, R2 and R3 are aliphatic groups, aromatic, heterocyclic or
alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and
wherein the nitrogen of the N-O group can be attached or wherein the
nitrogen of the N-O group forms part of these groups. The N-O group can
be part of the polymerisable unit (P) or can be attached to the polymeric
backbone or a combination of both.
Suitable polyamine N-oxides wherein the N-O group forms part of the
polymerisable unit comprise polyamine N-oxides wherein R is selected
from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of
said polyamine N-oxides comprises the group of polyamine N-oxides
wherein the nitrogen of the N-O group forms part of the R-group.
Preferred polyamine N-oxides are those wherein R is a heterocyclic group
such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline,
acridine and derivatives thereof.
Other suitable polyamine N-oxides are the polyamine oxides whereto the
N-O group is attached to the polymerisable unit. A preferred class of these
polyamine N-oxides comprises the polyamine N-oxides having the general
formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups
wherein the nitrogen of the N-O functional group is part of said R group.
Examples of these classes are polyamine oxides wherein R is a heterocyclic
compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
The polyamine N-oxides can be obtained in almost any degree of
polymerisation. The degree of polymerisation is not critical provided the
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~'
material has the desired water-solubility and dye-suspending power.
Typically, the average molecular weight is within the range of 500 to
1,000,000.
b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole
Suitable herein are copolymers of N-vinylimidazole and N-vinylpyrrolidone
having an average molecular weight range of from 5,000 to 50,000. The
preferred copolymers have a molar ratio of N-vinylimidazole to N-
vinylpyrrolidone from 1 to 0.2.
c) Polyvinylpyrrolidone
The detergent compositions herein may also utilize polyvinylpyrrolidone("PVP") having an average molecular weight of from 2,500 to 400,000.
Suitable polyvinylpyrrolidones are commercially available from ISP
Corporation, New York, NY and Montreal, Canada under the product
names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30
(average molecular weight of 40,000), PVP K-60 (average molecular
weight of 160,000), and PVP K-90 (average molecular weight of 360,000).
PVP K-15 is also available from ISP Corporation. Other suitable
polyvinylpyrrolidones which are commercially available from BASF
Corporation include Sokalan HP 165 and Sokalan HP 12.
d) Polyvinyloxazolidone
The detergent compositions herein may also utilize polyvinyloxazolidones
as polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones
have an average molecular weight of from 2,500 to 400,000.
e) Polyvinylimidazole
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~j9
The detergent compositions herein may also utilize polyvinylimidazole as
polymeric dye transfer inhibiting agent. Said polyvinylimidazoles
preferably have an average molecular weight of from 2,500 to 400,000.
Optical brightener
The detergent compositions herein particularly where formulated for
laundry usage also optionally contain from about 0.005% to 5~ by weight
of certain types of hydrophilic optical brighteners.
Hydrophilic optical brighteners useful herein include those having the
structural formula:
~ N H ~C=C~ I ~I'o~2
R2 SO3M SO3M R~
wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-
hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-
hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a
salt-forming cation such as sodium or potassium.
When in the above formula, R1 is ~nilino, R2 is N-2-bis-hydroxyethyl and
M is a cation such as sodium, the brightener is 4,4',-bis[(4-~nilino-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 tradename 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 forrnula, R1 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-
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Y~ ,
yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particular
brightener species is commercially marketed under the tradename Tinopal
SBM-GX by Ciba-Geigy Corporation.
When in the above formula, R1 is 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 tradename
Tinopal AMS-GX by Ciba Geigy Corporation.
Cationic fabric softening agents
Cationic fabric softening agents can also be incorporated into compositions
in accordance with the present invention. Suitable cationic fabric softening
agents include the water insoluble tertiary amines or dilong chain amide
materials as disclosed in GB-A-1 514 276 and EP-B-0 011 340.
Cationic fabric softening agents are typically incorporated at total levels of
from 0.5% to 15~ by weight, normally from 1% to 55~ by weight.
Other optional ingredients
Other optional ingredients suitable for inclusion in the compositions of the
invention include perfumes, colours and ~Iller salts, with sodium sulfate
being a preferred filler salt.
pH of the compositions
The detergent compositions used in the present invention are preferably not
form~ te-l to have an unduly high pH, in preference having a pH measured
as a 1% solution in distilled water of from 8.0 to 12.5, more preferably
from 9.0 to 11.8, most preferably from 9.5 to 11.5.
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Form of the compositions
The detergent compositions used in this invention can be formulated in any
desirable form such as powders, granulates, pastes, liquids, gels, bars and
tablets, granular and tablet forms being preferred.
The bulk density of the granular detergent compositions in accordance with
the present invention is typically of at least 650 g/litre, more usually at
least 700 g/litre and more preferably from 800 g/litre to 1200 g/litre.
The particle size of the components of granular compositions in accordance
with the invention should preferably be such that no more that 5 % of
particles are greater than 1 .4mm in diameter and not more than 5 % of
particles are less than 0.15mm in diameter.
Compacted solids may be manufactured using any suitable compacting
process, such as tabletting, briqlletting or extrusion, preferably tabletting.
Preferably tablets are manufactured using a standard rotary tabletting press
using compression forces of from S to 13 KN/cm2, more preferably from 5
to 11KN/cm2 so that the compacted solid has a minimum hardness of 176N
to 275N, preferably from l95N to 245N, measured by a C100 hardness test
as supplied by I. Holland instruments. This process may be used tO prepare
homogeneous or layered tablets of any size or shape. Preferably tablets are
symmetrical to ensure the uniform dissolution of the tablet in the wash
solution.
According to the present invention the compacted solid form detergent
composition may find utility in all types of automatic dish and laundry
washing machines including industrial and domestic machines.
Generally, if the compositions are in liquid form the liquid should be
thixotropic (ie; exhibit high viscosity when subjected to low stress and
l~wer viscosity when subjected to high stress), or at least have very high
viscosity, for example, of from 1,000 to 10,000,000 centipoise.
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5-o
Machine dishwashing method
Any suitable methods for machine washing or cle~nin~ soiled tableware,
particularly soiled silverware are envisaged.
A preferred machine dishwashing method comprises treating soiled articles
selected from crockery, glassware, hollowware, silverware and cutlery and
mixtures thereof, with an aqueous liquid having dissolved or dispensed
therein an effective amount of a machine dishwashing composition in
accord with the invention. By an effective amount of the machine
dishwashing composition it is meant from 8g to 60g of product dissolved or
dispersed in a wash solution of volume from 3 to 10 litres, as are typical
product dosages and wash solution volumes commonly employed in
conventional machine dishwashing methods.
T ~untlry washing method
Machine laundry methods herein typically comprise treating soiled laundry
with an aqueous wash solution in a washing m~chinP having dissolved or
dispensed therein an effective amount of a machine laundry detergent
composition in accord with the invention. By an effective amount of the
detergent composition it is meant from 40g to 300g of product dissolved or
dispersed in a wash solution of volume from 5 to 65 litres, as are typical
product dosages and wash solution volumes commonly employed in
conventional m~chin~ laundry methods.
In a preferred use aspect a dispensing device is employed in the washing
method. The dispensing device is charged with the detergent product, and
is used to introduce the product directly into the drum of the washing
machine before the commencement of the wash cycle. Its volume capacity
should be such as to be able to contain sufficient detergent product as
would normally be used in the washing method.
Once the washing machine has been loaded with laundry the dispensing
device cont~inin~ the detergent product is placed inside the drum. At the
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~i
commencement of the wash cycle of the washing machine water is
introduced into the drum and the drum periodically rotates. The design of
the dispensing device should be such that it permits cont~inment of the dry
detergent product but then allows release of this product during the wash
cycle in response to its agitation as the drum rotates and also as a result of
its contact with the wash water.
To allow for release of the detergent product during the wash the device
may possess a number of openings through which the product may pass.
Alternatively, the device may be made of a material which is perrneable to
liquid but impermeable to the solid product, which will allow release of
dissolved product. Preferably, the detergent product will be rapidly
released at the start of the wash cycle thereby providing transient localised
high concentrations of product in the drum of the washing machine at this
stage of the wash cycle.
Preferred dispensing devices are reusable and are designed in such a way
that container integrity is m~int~ined in both the dry state and during the
wash cycle. Especially preferred dispensing devices for use with the
composition of the invention have been described in the following patents;
GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345 and
EP-A-0288346. An article by J.Bland published in Manufacturing
Chemist, November 1989, pages 41-46 also describes especially preferred
dispensing devices for use with granular laundry products which are of a
type commonly know as the l'granulette". Another preferred dispensing
device for use with the compositions of this invention is disclosed in PCT
Patent Application No. WO94/11562.
Especially preferred dispensing devices are disclosed in European Patent
Application Publication Nos. 0343069 & 0343070. The latter Application
discloses a device comprising a flexible sheath in the form of a bag
extending from a support ring defining an orifice, the orifice being adapted
to admit to the bag sufficient product for one washing cycle in a washing
process. A portion of the washing medium flows through the orifice into
the bag, dissolves the product, and the solution then passes outwardly
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~',',~Z
through the orifice into the washing medium. The support ring is provided
with a masking arrangement to prevent egress of wetted, undissolved,
product, this arrangement typically comprising radially extending walls
extending from a central boss in a spoked wheel configuration, or a similar
structure in which the walls have a helical form.
Alternatively, the dispensing device may be a flexible container, such as a
bag or pouch. The bag may be of fibrous construction coated with a water
impermeable protective material so as to retain the contents, such as is
disclosed in European published Patent Application No. 0018678.
Alternatively it may be formed of a water-insoluble synthetic polymeric
material provided with an edge seal or closure designed to rupture in
aqueous media as disclosed in European published Patent Application Nos.
0011500, 0011501, 0011502, and 0011968. A convenient forrn of water
frangible closure comprises a water soluble adhesive disposed along and
sealing one edge of a pouch formed of a water impermeable polymeric film
such as polyethylene or polypropylene.
Examples
Abbreviations used in Examples
In the detergent compositions, the abbreviated component identifications
have the following me~ning~:
LAS : Sodium linear C12 alkyl benzene sulfonate
TAS : Sodium tallow alkyl sulfate
C45AS : Sodium C14-C1s linear alkyl sulfate
CxyEzS : Sodium Clx-Cly branched alkyl sulfate
condensed with z moles of ethylene oxide
C45E7 : A C14 15 predomin~ntly linear primary
alcohol condensed with an average of 7 moles
- of ethylene oxide
C25E3 : A C14 15 ~ranched primary alcohol condensed
with an average of 3 moles of ethylene oxide
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C25E5 : A C12 15 branched primary alcohol condensed
with an average of 5 moles of ethylene oxide
CEQ : R 1 COOCH2CH2 . N + (CH3)3 with R 1 = C 1 1-
C13
QAS : R2.N+(CH3)2(C2H4OH with R2 = C12-C14
Soap : Sodium linear alkyl carboxylate derived from
an 80/20 mixture of tallow and coconut oils
TFAA : C 1 6-C 1 8 alkyl N-methy~ glucamide
TPKFA : C12-C14 topped whole cut fatty acids
Zeolite A : Hydrated Sodium Aluminosilicate of formula
Na12(A102SiO2)12.27H2O having a primary
particle size in the range from 0.1 to 10
micrometers
Zeolite MAP : Hydrated sodium aluminosilicate MAP having
a silicon to aluminium ratio of 1.07:1.
NaSKS-6 : Cryst~lline layered silicate of formula
~-Na2Si205
Citric Acid : Anhydrous citric acid
Bicarbonate : Anhydrous sodium bicarbonate with a particle
size distribution between 400 ~m and 1200 ~m
MA/AA : Copolymer of 1:4 maleic/acrylic acid, average
molecular weight about 70,000
CMC : Sodium carboxymethyl cellulose
Alcalase : Proteolytic enzyme of activity 3AU/g sold by
NOVO INdustries A/S
Cellulase : Cellulytic enzyme of activity 1000 CEVU/g
sold by NOVO Industries A/S under the
tradename Carezyme
Lipase : Lipolytic enzyme of activity 100kLU/g sold by
NOVO Industries A/S under the tradename
Lipolase
Endolase : Endoglucase enzyme of activity 3000 cEVU/g
sold by NOVO Industries A/S
Photoactivated bleach : Sulfonated Zinc Phythlocyanine encapsulated in
dextrin soluble polymer
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Brightener 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl
Brightener2 : Disodium 4,4'-bis (4-anilino-6-morpholino-
1 . 3 . 5-triazin-2-yl)amino) stilbene-2 :2 ' -
disulfonate
PVNO : Polyvinylpyridine N-oxide
PVPVI : Copolymer of polyvinylpyrolidone and
vinylimidazole
SRP 1 : Sulfobenzoyl end capped esters with
oxyethylene oxy and terephtaloyl backbone
SRP 2 : Diethoxylated poly (1, 2 propylene terephtlate)
short block polymer
Silicone antifoam : Polydimethylsiloxane foam controller with
siloxane-oxyalkylene copolymer as dispersing
agent with a ratio of said form controller to
said dispersing agent of 10:1 to 100:1
NOBS : Nonanoyloxybenzene sulfonate in the form of
the sodium salt
STPP : Sodium tripolyphosphate
MGDA : Methyl Glycine Diacetic acid
Citrate : Tri-sodium citrate dihydrate
Carbonate : Anhydrous sodium carbonate
Silicate : Amorphous Sodium Silicate (SiO2:Na2O ratio
= 2.0)
Metasilicate : Sodium metasilicate (SiO2:Na2O ratio = 1.0)
PB1 : Anhydrous sodium perborate monohydrate
PB4 : Sodium perborate tetrahydrate of nominal
formula NaBO2.3H2O.H2O2
Percarbonate : Anhydrous sodium percarbonate of nominal
formula 2 . Na2co3 . 3H2~2
Nonionic : C13-C1s mixed ethoxylated/propoxylated fatty
alcohol with an average degree of ethoxylation
of 3.8 and an average degree of propoxylation
- of 4.~ sold under the tradename Plurafac
LF404 by BASF GmbH (low fo~ming)
TAED : Tetraacetyl ethylene ~ mine
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HEDP : Ethane l-hydroxy-1,1-diphosphonic acid
DETPMP : Diethyltriamine penta (methylene)
phosphonate, marketed by monsanto under the
tradename Dequest 2060
PAAC : Pent~mine acetate cobalt (III) salt
BzP : Benzoyl Peroxide
Paraffin : Paraffln oil sold under the tradename Winog 70
by Wintershall.
Protease : Proteolytic enzyme of activity 4KNPU/g sold
under the tradename Savinase by Novo
Industries A/S
Amylase : Amylolytic enzyme of activity 60KNU/g sold
under tradename Termamyl 60T by Novo
Industries A/S
BTA : Benzotriazole
Bismuth nitrate : Bismuth nitrate salt
PA30 : Polyacrylic acid of average molecular weight
approximately 8,000
Terpolymer : Terpolymer of avera~e molecular weight
approx. 7,000, comprising
acrylic:maleic:ethylacrylic acid monomer units
at a weight ratio of 60:20:20
480N : Random copolymer of 3:7 acrylic/methacrylic
acid, average molecular weight about 3,500
Sulphate : Anhydrous sodium sulphate.
NaDCC : Sodium dichloroisocyanurate
KOH : 100% active solution of Potassium Hydroxide
BSA : Amylotic enzyme sold under the tradename
LE17 by Novo Industries A/S (approx 1%
enzyme activity)
pH : Measured as a 1% solution in distilled water at
20~C
....... . .. .. .
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In the following examples all levels are ~uoted as % by weight of the
composltlon:
Example 1
The following compact high density (0.96Kg/l) dishwashing detergent
compositions A to F were prepared. Composition A is a comparative
composition. Compositions B to F are in accord with the invention:
A B C D E F
STPP 24.80 24.80 25.00 28.39 28.50 20.00
Citrate - - - - 10.00 10.00
Carbona~e - - 17.50 17.50
MGDA - 2.50 2.00 2.00 3.00 2.00
Silicate 20.36 20.36 14.81 14.81 14.81
Metasilicate 2.50 2.50 2.50
PBl 7.79 7.79 9.74 14.28 9.74
PB4
Percarbonate - - - - - 6.70
Non-ionic 1.50 1.50 2.00 1.50 2.00 2.60
TAED 2.39 2.39 2.39 - - 4.00
HEDP 0.46 0.46 1.00 - 0.83
DETPMP - - 0.65
PAAC - - - 0.20
BzP - 4 44
Paraffin 0.50 0.50 0.50 0.50 - 0.20
Protease 2.20 2.20 2.20 2.20 2.00 0.50
Amylase 1.50 1.50 1.20 1.50 1.00 1.10
BTA 0.30 0.30 0.30 0.30
Bismuth Nitrate - - 0.30
PA30
- Terpolymer - - - 4.00
480N 2.77 2.77 6.00 - 6.67
Sulphate 8.44 8.44 20.77 - 23.24 1.00
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Misc inc moisture to
balance
pH (1% solution) 10.90 10.90 11.00 10.80 10.90 9.60
Comparative testin~ - Improved builder performance
The stain and soil removal of Composition B, in accord with the invention
was compared to that of comparative Composition A using the following
test procedure.
1) A representative hydrophilic tea st~inin~ solution was prepared by
stewing 15 grams PG tips (tradename) loose leaf tea in 2.5 Iitres of distilled
water at water hardness 20 grains per gallon (equivalent to 2.86 mmol
Ca2 + /litre) .
2) The dishware test samples (100 tea cups of rim diameter 8 cm) were
stained by pouring lOOml of the representative tea st~ining solution into
said test samples and placing them in a standard oven at 100~C for 1 hour.
At the end of this period the test samples were removed from the oven,
emptied of their contents of representative tea st~inin~ solution and
returned to the oven for 2 hours to dry.
3) Twenty of the stained test samples were then placed in the upper rack of
each of five Bosch siemens SMS 6032 (tradename) machine dishwashers.
In addition, 70 g of DIN soil (comprising Breakfast oats, PG (tradename)
loose leaf tea, frozen spinach, UHT full cream milk, butter, Tyne brand
mince (tradename) and onions in gravy, 12 eggs in 4 litres of water) was
added to the machine dishwasher. The stained test samples were washed in
20g of detergent added by way of a standard dispenser mech~ni.cm. The
wash programme selected comprised washing and rinsing steps at a
temperature of between 50 and 60~C. The feed water hardness was 2.86
mmol Ca2+/litre.
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4) At the end of the wash the test samples were removed from the
machine dishwasher and graded. Grading was through visual inspection of
the washed test samples according to a scale of 1 to 10, wherein a score
of 1 indicates no tea stain removal and a score of 10 indicates all tea stain
removed.
Results were as follows: (average of the 4 gradings from the panellists)
Composition A Composition B
4.8 9.0
The improved builder performance profile of Compositions B is seen to
be better than that of related comparative Composition A, as measured by
the graded removal of tea stain from the test samples.
Example 2
The following granular dishwashing detergent compositions examples G
to L of bulk density 1.02Kg/L were prepared in accord with the
invention:
G H I J K L
STPP 30.00 30.00 30.00 27.90 34.50 26.70
Carbonate 30.50 23.50 30.50 23.00 30.50 2.80
MGDA - 2.00 2.00 5.00 5.00 2.00
Silicate 7.40 7.40 7.40 12.00 8.00 18.34
PB1 4.40 4.40 4.40 - 4.40
NaDCC - - - 2.00 - 1.50
Nonionic 0.75 0.75 0.75 1.90 1.20 0.50
TAED 1.00 1.00 - - 1.00
PAAC - - 0-004
BzP - 1.40
Paraffin 0.25 0.25 0.25
Protease 1.10 1.10 1.10 - 2.20
Amylase 0.38 0.38 0.38 - 0.80 -
BTA 0.15 - 0.15
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S-~
Sulphate 23.90 21.90 21.90 26.40 12.40
Misc inc
moisture to
balance
pH (1% solution) 10.80 10.80 10.80 10.70 10.70 12.30
Example 3
The following detergent composition tablets in accord with the present
invention of 25g weight were prepared by compression of a granular
dishwashing detergent composition at a pressure of 13KN/cm2 using a
standard 12 head rotary press:
M N O
STPP 45.00 38.80 32.50
Citrate - - 15.00
Carbonate - 5.00
MGDA 2.00 4.00 2.00
Silicate 26.40 14.80 25.00
Protease 1.76 2.20 0.60
Amylase 1.20 - 0.60
PB1 1.56 7.79
PB4 6.92 - 11.40
Nonionic 1.20 2.00 1.10
TAED 4.33 2.39 0.80
HEDP 0.67 0.67
DETPMP 0.6
Paraffln 0.42 0.50
BTA 0.24 0.30
PA30 3.2
Sulphate 25.05 12.70 1.20
Misc inc moisture to balance
pH (1% solution) 10.60 10.60 11.00
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Example 4
The following liquid detergent compositions in accord with the present
invention P to Q, of density 1.40Kg/L were prepared:
P Q
STPP 31.30 18.00
Carbonate 2.70 2.00
MGDA 2.00 2.00
Silicate - 4.40
NaDCC 1.10 1.15
Nonionic 2.50 1.0()
Paraffin 2.20
Protease 0.60 0.50
Amylase 0.80 0.40
480N 0.50 4.00
KOH - 6.00
Sulphate 1.60
Misc inc moisture to balance
pH (1% solution) 9.10 10.00
Example 5
The following granular laundry detergent compositions A' to C' of bulk
density 750 g/litre were prepared in accord with the invention:
A' B' C'
LAS 5.25 5.61 4.76
TAS 1.25 1.86 1.57
C45AS - 2.24 3.89
C25AE3S - 0. 76 1.1 8
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6/
C45E7 3.25 - 5.0
C25E3 - 5.5
CEQ 0.8 2.0 2.0
STPP 19.7 19.5 19.5
MGDA 0.2 0.3 10.0
Zeolite A - - 19.5
Zeolite MAP - 19 . 5
NaSKS-6/citric acid - 10.6 10.6
(79:21)
Carbonate 6.1 21.4 21.4
Bicarbonate - 2.0 2.0
Silicate 6 . 8
Sodium sulfate 39.8 - 14.3
PB4 5.0 12.7
TAED 0. 5 3 . 1
DETPMP 0.25 0.2 0.2
HEDP - 0 3 0-3
Protease 0.26 0.85 0.85
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Lipase 0.15 0.15 0.15
Cellulase 0.28 0.28 0.28
Amylase 0.1 0.1 0.1
M A/A A 0.8 1.6 1.6
C M C 0.2 0.4 0.4
Photoactivated bleach 15 ppm 27 pp m 27 pp m
(ppm)
Brightener 1 0.08 0.19 0.19
Brightener 2 - 0.04 0.04
Perfume 0.3 0-3 0-3
Silicone antifoam 0.5 2.4 2.4
Minors/misc to 100%
Example 6
The following detelgellt formulations, according to the present invention
were prepared:
D' E' F'
Blown Powder
STPP 24.0 - 24.0
~ Zeolite A - 24.0
M G D A 0.1 0.5 2.0
C45AS 9.0 6.0 13.0
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63
MA/AA 2.0 4.0 2.0
LAS 6.0 8.0 11.0
TAS 2.0 - -
Silicate 7.0 3.0 3.0
CMC 1.0 1.0 0.5
Brightener 2 0.2 0.2 0.2
Soap 1.0 1.0 1.0
DTPMP 0.4 0.4 0.2
Spray On
C45E7 2.5 2.5 2.0
C25E3 2.5 2.5 2.0
Silicone antifoam 0.3 0.3 0.3
Perfume 0.3 0.3 0.3
Dry additives
Carbonate 6.0 13 .0 15.0
PB4 18.0 18.0 10.0
PB1 4.0 4.0 0
TAED 3.0 3.0 1.0
Photoactivated bleach 0.02 0.02 0.02
Protease 1.0 1.0 1.0
Lipase 0.4 0.4 0.4
Amylase 0.25 0.30 0.15
Dry mixed sodium 3.0 3.0 5.0
sulfate
B~l~nre (Moisture & 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 630 670 670
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Example 7
The following nil bleach-cont~ining detergent formulations of particular use
in the washing of colored clothing, according to the present invention were
prepared:
G' H'
Blown Powder
STPP 15.0 15.0
MGDA 0.2 2.0
Sodium sulfate 0.0 5.0
LAS 3.0 3.0
DTPMP 0.4 0.5
CMC 0.4 0.4
MA/AA 4.0 4.0
Agglomerates
C45AS - -
LAS 6.0 5.0
TAS 3.0 2.0
Silicate 4.0 4.0
Zeolite A 10.0 15.0
CMC
MA!AA - -
Carbonate 9.0 7.0
Spray On
Perfume 0.3 0.3
C45E7 4.0 4.0
C25E3 2.0 2.0
Dry additives
MA/AA
NaSKS-6
Citrate 10.0
Bicarbonate 7.0 3.0
Carbonate 8.0 5.0
PVPVI/PVNO 0.5 0.5
Alcalase 0.5 0.3
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G5
Lipase 0.4 0.4
Amylase 0. 6 0. 6
Cellulase 0.6 0.6
Silicone antifoam 5.0 5.0
Dry additives
Sodium sulfate 0.0 9.0
Balance (Moisture and 100.0 100.0
Miscellaneous)
Density (g/litre) 700 700
Example 8
The following detergent formulations, according to the present invention
were prepared:
I' J' K' L'
LAS 20.0 14.0 24.0 22.0
QAS 0.7 1.0 - 0.7
TFAA - 1.0
C25E5/C45E7 - 2.0 - 0.5
C45E3S - 2.5 - -
STPP 30.0 18.0 30.0 22.0
Silicate 9.0 5.0 10.0 8.0
Carbonate 13.0 7.5 - 5.0
MGDA 2.0 2.0 2.0 2.0
Bicarbonate - 7.5
DTPMP 0.7 1.0
SRP 1 0.3 0.2 - 0.1
MA/AA 2.0 1.5 2.0 1.0
CMC 0.8 0.4 0.4 0.2
Protease 0.8 1.0 0.5 0.5
Amylase 0.8 0.4 - 0.25
- Lipase 0.2 0.1 0.2 0.1
Cellulase 0.15 0.05 - -
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~6
Photoactivated 70ppm 45ppm - 10ppm
bleach (ppm)
Brightener 1 0.2 0.2 0.08 0.2
PBl 6.0 2.0
NOBS 2.0 1.0
Balance 100 100 100 100
(Moisture and
Miscellaneous)
Example 9
The following detergent formulations, according to the present invention
were prepared:
M' N' O'
Blown Powder
STPP 30.0 22.0 6.0
M G D A 2.0 2.0 2.0
Sodium sulfate 19.0 5.0 7.0
M A/A A 3.0 3.0 6.0
L A S 14.0 12.0 22.0
C45A S 8.0 7.0 7.0
Silicate - 1.0 5.0
Soap - - 2.0
Brightener 1 0.2 0.2 0.2
Carbonate 8.0 16.0 20.0
D TP M P - 0.4 0.4
Spray On
C45E7 1.0 1.0 1.0
Dry additives
PVPVI/PVNO 0.5 0.5 0.5
Protease 1.0 1.0 1.0
- Lipase 0.4 0.4 0 4
Amylase 0.1 0.1 0.1
Cellulase 0.1 0.1 0.1
NOBS - 6.1 4.5
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G~
PB1 1.0 5.0 6.0
Sodium sulfate - 6.0
Balance (Moisture 100 100 100
and Miscellaneous)
Example 10
The following high density and bleach-cont~ining detergent formulations,
according to the present invention were prepared:
P Q' R'
Blown Powder
STPP 15.0 15.0 15.0
- MGDA 2.0 2.0 2.0
Sodium sulfate 0.0 5.0 0.0
LAS 3.0 3.0 3.0
QAS - 1.5 1.5
DTPMP 0.4 0.4 0.4
CMC 0.4 0.4 0.4
MA/AA 4.0 2.0 2.0
Agglomerates
LAS 5.0 5.0 5.0
TAS 2.0 2.0 1.0
Silicate 3.0 3.0 4.0
Zeolite A 8.0 8.0 8.0
Carbonate 8.0 8.0 4.0
Spray On
Perfume 0.3 0.3 0.3
C45E7 2.0 2.0 2.0
C25E3 2.0 - -
Dry additives
Citrate 5.0 - 2.0
- Bicarbonate - 3.0
Carbonate 8.0 15.0 10.0
TAED 6.0 2.0 5.0
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Co
PB1 14.0 7.0 10.0
Polyethylene oxide of MW - - 0.2
5,000,000
Bentonite clay - - 10.0
Protease l.0 1.0 1.0
Lipase 0.4 0.4 0.4
Amylase 0.6 0.6 0.6
Cellulase 0.6 0.6 0.6
Silicone antifoam 5.0 5.0 5.0
Dry additives
Sodium sulfate 0.0 3.0 0.0
Balance (Moisture and 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 850 850 850
