Note: Descriptions are shown in the official language in which they were submitted.
7~
This invention relates, in general, to bleaching and laundering
compositions and their application to laundering operations. ~lore
speclElcally, this invention relates to bleachlng and la~mderlng
composltions comprising monopero~yphthalic acid and/or a water-soluble
salt thereof, a chelatlng agent capable of formlng a water-soluble metal
complex ln aqueous solution, a peroxygen compound and an organic
activator for said peroxygen compound comprising phthalic anhydride.
Bleaching compositions which release active oxygen in the laundry
solution are extensively described in the prior art and commonly used in
laundering operations. In general, such bleaching compositions contain
peroxygen compounds, such as, perborates, percarbonates, perphosphates
and the like which promote the bleaching activity by forming hydrogen
peroxide in aqueous solution. A major drawback attendant to the use of
such peroxygen compounds is that they are not optimally effective at
the relatively low washing temperatures employed in most household
washing machines in the United States, i.e., temperatures in the range
of 80 to 130F. By way of comparison, European wash temperatures are
generally substantially higher extending over a range, typically, from
90 to 200F. However, even in Europe and those other countries which
generally presently employ near boiling washing temperatures, there is
a trend towards lower temperature laundering.
In an effort to enchance the bleaching activity of peroxygen
bleaches, the prior art has employed materials called ac~ivators ln
comblnation with the peroxygen compounds. It
L r~
is generally believed that the interaction of the peroxygen com-
pound and the activator results in the formation of a peroxyacid
which is the active species for bleaching. Numerous compounds
have been proposed in the art as activators for peroxygen
bleaches among whieh are ineluded earboxylie aeid anhydrides
sueh as those diselosed in U.S. Patent Nos. 3,928,775; 3,338,839;
and 3,352,634; carboxylie esters sueh as diselosed in U.S.
Patent No. 2,995,905; N-aeyl compounds such as those described
in U.S. Paten~ Nos. 3,912,648 and 3,919,102; cyanomines such as
deseribed in U.S. Patent No. 4,199,466; and acyl sulfoamides
sueh as diselosed in U.S. Patent No. 3,245,913.
Pre-formed peroxyaeids have also been used to effeet
bleaehing in laundry wash solutions. U.S. Patent Nos. 3,770,816;
4,170,453; and 4,259,201 are illustrative of prior art diselo-
sures relating to bleaehing eompositions eomprising a peroxyacid
compound.
It is generally recognized in the art that metal ions
are capable of acting as decomposition catalysts for inorganic
peroxygen compounds and organic peroxyacids. In an effort to
stabilize such bleaching species in the wash solution, chelating
agents have been ineorporated into bleaehing detergent composi-
tions. U.S. Patent No. 3,243,378 to Stoltz, for example, dis-
closes a bleaching composition containing a peroxygen bleaching
compound and a chelating agent to sequester metal eations. In
general, the chelating agents which have been used for this pur-
pose fall into one or two categories: (a) materials such as
heteroeyclic compounds and ketones, notably 8-hydroxyquinoline,
whieh tie up metal eations in the laundry wash by precipitating
them from solution; and (b) materials such as aminopolyearboxy-
lates and aminopolyphosphonate compounds which form water-
soluble metal complexes with the cations present in the washsolution. Accordingly, U.S. Patent No. 4,005,029 discloses that
selected aldehydes, ketones and compounds which yield aldehydes
or ketones in aqueous solution (e.g., 8-hydroxyquinoline) can be
used to activate aliphat.ic peroxyacids, such as, diperazelaic
acid, diperadlpi.c acid and aromatic peroxyacids (and water-
soluble salts thereof) including monoperoxyphthalic acid and
diperoxyterephthalic acid. In U.S. Patent No 4,170,453, a mix-
ture of 8hydroxyquinoline, phosphoric acid and sodium pyrophos-
phate is disclosed as a preferred chelating system to stabilizethe active oxygen generated in wash solutions containing
diperoxydodecandioic acid. U.S. Patent No. 4,225,452 to Leigh
discloses the combination of specified classes of chelating
agents (among which are phosphonate compounds) with inorganic
peroxygen compounds and an organic activator for the purpose of
suppressing the decomposition of the peroxygen compound in the
bleach composition~ Specifically, the chelating agent is said
to inhibit the unwanted side reaction of the peroxygen compound
with the peroxyacid formed by the primary reaction of the per-
oxygen compound and the activator, the effect of the side reac-
-tion being to deplete the peroxyacid bleaching species from solu-
tion. The Leigh patent, however, discourages the use of such
chelating agents in solutions wherein the peroxyacid has a
double bond between the carbon atoms in the ~,~' position to the
carbonyl group. Specifically, a-t column 2 of the patent, beginn-
ing at line 63, the patentee excludes phthalic anhydride as an
activator for the disclosed bleaching composition because of in-
stability. Inasmuch as the peroxyacid formed by the reaction of
phthalic anhydride and an inorganic peroxygen compound is mono-
peroxyphthalic acid, the Leigh patent apparently discourages the
7 ~
use of monoperoxyphthalic acid in the bleaching compositions ofthe patent.
European Patent Publica-tion No. 0,027,693, published
~pril 29, 1981, discloses the use of magnesium monoperoxyphtha-
la-te as an effective bleaching agent. There is also disclosed
the optional combination oE a bleaching agent wi-th an "aldehyde
or ketone peroxyacid activator as described in U.S. Patent
4,005,029, e.g., 8-hydroxyquinoline which is a known peroxygen
stabilizer". The Publication also discloses organic phosphonate
compounds, along with a wide variety of other compounds, as
being useful detergent builders which optionally may be included
in the described washing compositions. No disclosure is made,
however, concerning the beneficial effects at-tendant to the use
of a small amount of organic phosphonate compounds to serve as
chelating agents in bleaching compositions and par-ticularly~ in
compositions containing magnesium monoperoxyphthalate.
The aforementioned European Patent Publication also
discloses that peroxygen compounds may optionally be included in
the laundering compositions containing the described peroxyacid
bleaching agents in order to provide bleaching a-t higher washing
temperaturesO However, no suggestion is made concerning the use
of an organic activator in combination with such peroxygen com-
pounds, and in particular, about the desirability of using a per-
oxygen compound in combination with phthalic anhydride as an
activator in a bleaching sys-tem containing monoperoxyphthalic
acid and/or a salt thereof and a chelating agent of the type
herein described.
SlJMMARy OF THE INVENTION
The present invention provides a bleaching and launder-
ing composition comprising monoperoxyphthalic acid and/or a
water-soluble salt thereof and a chelating agent consisting
essentially of diethylene triamine pentamethylene phosphonic
acid and/or a water-soluble salt thereof; a peroxygen compound
other than monoperoxyphthalic acid; and an activator for said
peroxygen compound consisting essentially of phthalic anhydride.
In another aspect, the present invention provides a
bleaching detergent composition comprising: (a) from about 5
to 50%, by weight, of a composition comprising monoperoxyphthalic
acid and/or a water-soluble salt thereof; a chelating agent
consisting essentially of diethylene triamine pentamethylene
phosphonic acid and/or a water-soluble salt thereof; a peroxygen
compound other than monoperoxyphthalic acid; and an activator
for said peroxygen compound consisting essentially of phthalic
anhydride; (b) from about 5 to 50%, by weight, of one or more
detergent surface active agents selected from the group
consisting of anionic, cationic, nonionic, ampholytic and
zwitterionic detergents; (c) from about 5 to 80~, by weight,
of a detergent builder salt; and, (d) the balance comprising
water and optionally a filler salt.
In accordance with the process of -the invention,
bleaching of stained and/or soiled materials is effected by
contacting such materials with an aqueous solution of the
above-defined compositions.
The term "chelating agent" as used herein refers to
organic compounds which, in small amounts, are capable of bind-
ing transition metal cations, (e.g., iron, nickel and cobalt)
~`~
which are ]cnown to adversely affect the stability of peroxygen
compounds and/or peroxyacids in aqueous bleaching solutions.
The chelating agents employed hereln therefore exclude inorganic
compounds ordinarily used in detergent formulations as builder
salts. The chelating agents useful for the present invention
are of the type capable of forming a substantially water-
soluble, rather than a precipitated, metal complex in aqueous
solutions with metal ions, most notably, transition metal
cations such as those referred to above. Suitable chelating
agents therefore include ethylene diamine tetraacetic acid
(EDTA); nitrilotriacetic acid (NTA); diethylene triamine
pentaacetic acid; ethylene diaminetetramethylene phosphonic
acid (EDITEMPA); amino
- 6a -
77~
trimethylene phosphonic acid (ATMP); diethylene triamine pent-
acetic acid (DETPA), all of the above-mentioned compounds being
preferably employed in the form of the sodium salt.
A preferred class of chelating agents are the organic
phosphonate compounds such as those disclosed in U.S. Patent No.
4,225,452, the formulae of which are set forth in Equations, I,
II and III in columns 3 and 4 of the patent. Among this class
of materials diethylene triamine pentamethylene phosphonic acid
(referred to herein as "DTPMP"), and/or a water-soluble salt
thereof is particularly preferred as a chelating agent for pur-
poses of the present invention. Among the salts of DTPMP, the
sodium, potassium and ammonium salts are generally preferred be-
cause of their relatively greater solubility and ease of prepara-
tion.
In general, the chelating agents employed in the
bleaching compositions of the invention are present in a weight
ratio relative to MPPA and/or its salts of from about 1:5 to
about 1:50, and more preferably, from about 1:7 to about 1:20.
In the built bleaching detergent compositions of the invention,
the concentration of chelating agent is generally below about 5%,
by weight, preferably below about 2~, by weight, and most prefer-
ably below about 1%, by weight, of such detergent composi-tions.
The chelating agents may be utilized alone or in combination
with one or more other chelating agents. Thus, for example,
DTPMP may be advantageously employed in combination with EDTA in
the compositions of the invention.
DETAILED DESCRIPTION OF THE INVENTION
Monoperoxyphthalic acid and/or one or more of its
water-soluble salts in combination with a peroxygen compound are
the bleaching agents in the compositions o~ the invention. Al-
'~
though MPPA provides acceptable bleaching activity, it has the
disadvantage of relatively poor stability when stored in admix-
ture with other components ordinarily present in household deter-
gent compositions. Hence, for purposes of stability, the magne-
sium salt of MPPA is preferably employed in the compositlons of
the invention, namely, magnesium monoperoxyphthalate. The
alkali metal, calcium or barium alkaline earth and/or ammonium
salts of MPPA may also be employed in the bleaching and launder-
ing compositions herein described, although such salts are gener-
ally less preferred from the standpoint of stability than the
aforementioned magnesium salt.
The production of MPPA is generally effected by the
reaction of hydrogen peroxide and phthalic anhydride. The resul-
tant MPPA can then be used to produce magnesium monoperoxyphtha-
late by reaction with a magnesium compound in the presence of an
organic solvent. A detailed description of the production of
MPPA and its magnesium salt is set forth on pages 7 to 10, inclu-
sive, of European Patent Publication No. 0,027,693, published
April 29, 1981.
The peroxygen compounds useful in the present inven-
tion include compounds that release hydrogen peroxide in aqueous
media, such as, alkali metal perborates, percarbonates, perphos-
phates and the like. Sodium perborate is particularly preferred
because of its commercial availability.
The peroxygen compound is generally present in the
bleaching composition relative to the phthalic anhydride
activator in a molar ratio of peroxygen compound to phthalic
anhydride of about 1:10 to about 10:1, the preferred ratio being
from abou-t 1:2 -to about 3:1. It will be appreciated that the
concentration of phthalic anhydride will depend on the concentra-
--8--
7 ~
tion of the peroxygen compound, which in turn is governed by the
degree of bleaching desired. The peroxygen compound is typic-
ally present in the bleaching composition in an amount ranging
from about 1% to abou-t 50%, by weight, preferably 3% -to 25%, and
most preferably, 5% to 20%, by weight, of the bleaching composi-
tion.
The amount of bleaching composition added to the wash
solution is generally selected to provide an amount of peroxygen
and peroxyacid compounds within the range corresponding to about
3 to 100 parts of active oxygen per million parts of the wash
solution.
MPPA and/or a water-soluble salt thereof in combina-
tion with the selected chelating agent, peroxygen compound and
phthalic anhydride may be formulated as a separate bleach pro-
duct, or alternatively may be employed in a built detergent com-
position. Accordingly, the bleaching composition of the inven-
tion may include conventional additives used in the fabric wash-
ing art, such as, binders, fillers, builder salts, proteolytic
enzymes, optical brighteners, perfumes, dyes corrosion inhibi-
tors, anti-redeposition agents, foam stabilizers and the like,
all of which may be added in varying quantities depending on the
desired properties of the bleaching composition and their com-
patability with such composition. Additionally, the bleaching
compositions of the invention may be incorporated into launder-
ing detergent compositions containing surface active agents,
such as, anionic, cationic, nonionic, ampholytic and
zwitterionic detergents and mixtures thereof.
When the instant bleaching compositions are incorpor-
ated into a conventional laundering composition and are thus pro-
vided as a fully formulated bleaching detergent composition, the
latter compositions will comprise the following: from about 5to 50%, by weight, of the instant bleaching composition; from
about 5 to 50%, by weight, of a detergent surface active agent,
preferably from about 5 to 30%, by weight; and from about 5 to
80%, by weight, of a detergent builder salt which can also func-
tion as a buffer to provide the requisite pH range when the
laundering composition is added to water. The aqueous wash solu-
tions will have a p~I range of from about 7 to 12, preferably
from about 8 to 10, and most preferably from about 8.5 to 9. A
preferred amount of the builder salt is from about 20% to about
65%, by weight, o-E the composition. The balance of the composi-
tion will predominantly comprise water, filler salts, such as,
sodium sulfate, and optionally, minor additives, such as,
optical brighteners, perfumes, dyes, anti-redeposition agents
and the like.
Among the anionic surface active agents useful in the
present invention are those surface active or detergent com-
pounds which contain an organic hydrophobic group containing
generally from about 8 to 26 carbon atoms and preferably 10 to
18 carbon atoms in their molecular structure and at least one
water-solubili2ing group selected from -the groups of sulfonate,
sulfate, carboxylate, phosphonate and phosphate so as to form a
water-soluble detergent.
Examples of suitable anionic detergents include soaps,
such as, the water-soluble salts (e.g., -the sodium, potassium,
ammonium and alkanolammonium salts) of higher fatty acids or re-
sin salts containing from about 8 to 20 carbon atoms and prefer-
ably 10 to 18 carbon atoms. Suitable fatty acids can be ob-
tained from oils and waxes of animal or vegetable origin, for
example, -tallow, grease, coconut oil and mixtures thereof. Part-
--10--
icularly useful are the sodium and potassium salts of the fatty
acid mixtures derived from coconut oil and tallow, for example,
sodium coconut soap and potassium tallow soap.
The anionic class of detergents also includes the
water~soluble sulfated and sulfonated detergents having an alkyl
radical containing from about 8 -to 26, and preferably from about
12 to 22 carbon atoms. Examples of the sulfonated anionic deter-
gents are the higher alkyl mononuclear aromatic sulfonates such
as the higher alkyl benzene sulfonates containing from about 10
to 16 carbon atoms in the higher alkyl group in a straight or
branched chain, such as, for example, the sodium, potassium and
ammonium salts of higher alkyl benzene sulfonates, higher alkyl
toluene sulfonates and higher al]cyl phenol sulfonates.
Other suitable anionic detergents are the olefin sul-
fonates including long chain alkene sulfonates, long chain
hydroxyalkane sulfonates or mixtures of a~kene sulfonates and
hydroxyalkane sulfonates. The olefin sulfonate detergents may
be prepared in a conven-tional manner by the reaction of SO3 with
long chain olefins con-taining from about 8 to 25, and preferably
from about 12 to 21 carbon atoms, such olefins having the
formula RCH=CHRl wherein R is a higher alkyl group of 6 to 23
carbons and Rl is an alkyl group con-taining from about 1 to 17
carbon atoms or hydrogen to form a mixture of sultones and
alkene sulfonic acids which is then treated to convert the sul-
tones to sulfona-tes. Other examples of sulfate or sulfonate
detergents are paraffin sulfonates containing from about 10 to
20 carbon atoms, and preferably from abou-t 15 to 20 carbon atomsO
The primary paraffin sulfonates are made by reacting long chain
alpha olefins and bisulfites. Paraffin sulfonates having the
sulfonate group distributed along the paraffin chain are shown
in U.S. Nos. 2,503,280; 2,507,088; 3,260,741; 3,372,188 and
German Patent No. 735,096. Other useful sulfate and sulfonate
detergents include sodium and potassium sulfates oE higher
al.cohols containing from about 8 to 18 carbon atoms, such as,
for example, sodium lauryl sulfate and sodium tallow alcohol
fate, sodium and potassium salts of alpha-sulfofatty acid esters
containing about 10 to 20 carbon atoms in the acyl group, for
example, methyl alpha-sulfomyristate and methyl alpha-sulfo-
tallowate, ammonium sulfates of mono~ or di- glycerides of
higher (C10 - C18) fatty acids, for example, stearic monogly-
ceride monosulfate; sodium and alkylol ammonium salts of alkyl
polyethenoxy ether sulfates produced by condensing 1 to 5 moles
of ethylene oxide with 1 mole of hi~her (C8 - Clg) alcohol;
sodium higher alkyl (C10 - C18) glyceryl ether sulfonates; and
sodium or potassium alkyl phenol polyethenoxy ether sulfates
with about 1 to ~ oxyethylene groups per molecule and in which
the alkyl radicals contain abou-t 8 to 12 atoms~
The most highly preferred water-soluble anionic deter-
gent compounds are the ammonium and substituted ammonium (such
as mono, di and -tri-ethanolamine), alkali metal (such as, sodium
and potassium) and alkaline earth metal (such as, calcium and
magnesium) salts of the higher alkyl benzene sulfonates, olefin
sulfonates and higher alkyl sulfates. Among the above-listed
anionics, the most preferred are the sodium linear alkyl benzene
sulfonates (LABS).
The nonionic synthetic organic detergents are charac-
terized by the presence of an organic hydrophobic group and an
organlc hydrophilic group and are typically produced by the con-
densation of an organic aliphatic or alkyl aromatic hydrophobic
compound with ethylene oxide (hydrophil.ic in nature). Practic-
7~
ally any hydrophobic compound having a carboxy, hydroxy, amidoor amino group with a free hydrogen attached to the nitrogen can
be condensed with ethylene oxide or with the polyhydration pro-
duct thereof, polyethylene glycol, to form a nonionic detergent.
The length of the hydrophilic or polyoxyethylene chain can be
readily adjusted to achieve the desired balance between the
hydrophobic and hydrophilic groups.
The nonionic detergents include the polyethylene oxide
condensate of 1 mole of alkyl phenol containing from about 6 to
12 carbon atoms in a straight or branched chain configuration
with about 5 to 30 moles of ethylene oxide, for example, nonyl
phenol condensed with 9 moles of ethylene oxide; dodecyl phenol
condensed with 15 moles of ethylene oxide; and dinonyl phenol
condensed with 15 moles of ethylene oxide. Condensation pro-
ducts of the corresponding alkyl thiophenols with 5 to 30 moles
of ethylene oxide are also suitable.
Of the above-described types of nonionic surfactants,
those of the ethoxylated alcohol type are preferred. Particul-
arly preferred nonionic surfactants include the condensation pro-
duct of coconut fatty alcohol with about 6 moles of ethyleneoxide per mole of coconut fatty alcohol, -the condensation pro-
duct of tallow fatty alcohol with abou-t 11 moles of ethylene
oxide per mole of tallow fatty alcohol, -the condensation product
of a secondary fatty alcohol containing about 11-15 carbon atoms
with about 9 moles of ethylene oxide per mole of fatty alcohol
and condensation products of more or less branched primary
alcohols, whose branching is predominantly 2-methyl, with from
about 4 to 12 moles of ethylene oxide.
Zwitterionic detergen-ts such as -the betaines and sulfo-
betaines having the following formula are also useful:
/ 1 4
wherein R is an alkyl group containing from about 8 to 18 carbonatoms, R2 and R3 are each an alkylene or hydroxyalkylene group
containing about 1 to 4 carbon atoms, R4 is an alkylene or
hydroxyalkylene group containing 1 to 4 carbon atoms, and X is
C or S:O. The alkyl group can contain one or more intermediate
linkages such as amido, ether, or polyether linkages or non-
functional substituents such as hydroxyl or halogen which do not
substantially affect the hydrophobic character of the group.
When X is C, the detergent is called a betaine; and when X is
S:O, the detergent is called a sulfobetaine or sultaine.
Cationic surface active agents may also be employed.
They comprise surface active detergent compounds which contain
an organic hydrophobic group which forms part of a cation when
the compound is dissolved in water, and an anionic group.
Typical cationic surface active agents are amine and quaternary
ammonium compounds.
Examples of suitable syn-thetic cationic detergents
include: normal primary amines of the formula RNH2 wherein R is
an alkyl group containing from about 12 to 15 atoms; diamines
having the formula RNHC2H4NH2 wherein R is an alkyl group con-
taining from about 12 to 22 carbon atoms, such as N-2-aminoethyl-
stearyl amine and N 2-aminoethyl myristyl amine; amide~linked
amines, such as those having the formula RlCONHC2H~NH2 wherein
Rl is an alkyl group containing about 8 to 20 carbon atoms, such
as N-2-amino ethylstearyl amide and N-amino ethylmyristyl amide;
quaternary ammonium compounds wherein typically one of the
groups ]inked to the nitrogen atom is an alkyl group containing
--1'1--
7~
about 8 to 22 carbon atoms and three of the yroups linked to the
nitrogen atom are alkyl groups which contain 1 to 3 carbon atoms r
including alkyl groups bearing inert substituents, such as
phenyl groups, and there is present an anion such as halogen,
acetate, methosulfate, etc. The alkyl group may contain inter-
mediate linkages such as amide which do not substantially affect
the hydrophobic character of the group, for example, stearyl
amido propyl quaternary ammonium chloride. Typical quaternary
ammonium detergents are ethyl-dimethyl-stearyl-ammonium chloride,
benzyl-dimethyl-stearyl ammonium chloride, trimethyl-stearyl
ammonium chloride, trimethyl-cetyl ammonium bromide, dimethyl-
ethyl-lauryl ammonium chloride, dimethyl-propyl-myristyl
ammonium chloride, and the corresponding methosulfates and
acetates.
Ampholytic detergents are also suitable for the inven-
tion. Ampholytic detergents are wel] known in the art and many
operable detergents of this class are disclosed by A. M.
Schwartz, J. W. Perry and J. Birch in "Surface Active Agents and
Detergents," Interscience Publishers, New York, 1958, vol. 2.
Examples of suitable amphoteric detergents include: alkyl
betaiminodipropionates, RN(C2H4COOM)2; alkyl beta-amino propio-
nates, RN(H)C2H4COOM and long chain imidazole derivatives having
the general foxmula:
1~" ~2CH
R-~ CH2CH2OCH2COOM
OH CH2COOM
wherein in each of the above formulae R is an acyclic hydro-
phobic group containing from about 8 to 18 carbon atoms and M is
7~7~
a cation to neutralize the charge of the anion. Specific oper-
able amphoteric detergents include the disodium salt of
undecylcycloimidiniumethoxyethionic acid-2-ethionic acid,
dodecyl beta alanine, and the inner salt of 2-trimethylamino
lauric acid.
The laundry detergent composition of the invention
optionally contain a detergent builder of the type commonly used
in detergent formulations. Useful builders include any of the
conventional inorganic water-soluble builder salts, such as, for
example, water-soluble salts o-f phosphates, pyrophosphates,
orthophosphates, polyphosphates, silicates, carbonates, and the
like. Organic builders include water-soluble phosphonates, poly-
phosphonates, polyhydroxysulfonates, polyacetates, carboxylates,
polycarboxylates, succina-tes and the like.
Specific examples of inorganic phosphate builders in-
clude sodium and potassium tripolyphosphates, pyrophosphates and
hexametaphosphates. The organic polyphosphonates specifically
include, for example, the sodium and potassium salts of ethane
l-hydroxy-l, l-diphosphonic acid and the sodium and po-tassium
salts of ethane-l, 1, 2-triphosphonic acid. Examples of these
and other phosphorous builder compounds are disclosed in U.S.
Patent Nos. 3,213,030; 3,~22,021; 3,~22,137 and 3,~00,17~.
Pentasodium tripolyphosphate and tetrasodium pyrophosphate are
especially preferred water-soluble inorganic builders.
Specific examples of non-phosphorous inorganic
builders include water-soluble inorganic carbona-te, bicarbonate
and silicate salts. The alkali metal, for example, sodium and
potassium, carbonates, bicarbonates and silicates are particul-
arly useful herein.
Water-soluble organic builders are also useful. For
-16-
example, the alkali metal, ammonium and substitu-ted ammonium
polyacetates, carboxylates, polycarboxylates and polyhydroxy-
sulfonates are useful builders for the compositions and pro-
cesses of the invention. Specific examples of polyacetate and
polycarboxylate builders include sodium, potassium, lithium,
ammonium and substituted ammonium salts of ethylene diamine-
tetracetic acid, nitrilotriacetic acid, benzene polycarboxylic
(i.e. penta- and tetra-) acids, carboxymethoxysuccinic acid and
citric acid.
The bleaching compositions of the invention are pre-
pared by admixing the ingredients as hereinafter illustrated.
When preparing laundering compositions containing the bleaching
composition in combination with a surface active de-tergent com-
pound and/or builder salts, the components of the bleaching com-
position can be mixed directly with the detergent compound,
builder and the like. Alternatively, -the peroxygen activator,
the MPPA and the peroxygen compound can be coated with a coa-ting
material to improve stability and/or prevent premature activa-
tion of the bleaching agent. The coating process is conducted
in accordance with procedures well known in the art. Suitable
coating materials include compounds such as magnesium sulfate,
polyvinyl alcohol, lauric acid or its salts and the like.
EXAMPLE 1
Test Procedure
Bleaching tests were carried out on standard stained
test swatches (described below) using the various bleaching and
laundering compositions described in Table 1 of this Example in
a Tergotometer vessel manufactured by the U.S. Testing Company.
The Tergotometer was malntained at a constant tempera-ture of
120F and operated at 100 rpm.
7~
Each of the test compositions described in Table 1 be-
low was added to one liter of tap water at 120F having a water
hardness of about 100 ppm, as calcium carbonate. The test com-
positions were agitated for about one minute and then a mixed
fabric load consisting of two swatches each (3" x 4") of the
stained fabrics described below was added to each wash recept-
acle. After a 15 minute wash at 120F, the test fabrics were
rinsed in lOOOF tap water and then dried. The percent stain
removal was measured by taking a reflectance reading for each
stained test swatch prior to and after the washing using a
Gardner Color Difference Meter, and the percent stain removal
(% S.R.) was calculated as follows:
(Rd after washing) - (Rd before washing)
% S . ~ . = x 100
(Rd before staining) - (Rd before washing)
wherein "Rd before washing" represents the Rd value after stain-
ing.
The value of percent staln removal calculated for all
five cloths were averaged for each test laundering composition.
A difference greater than 2% in the average of the five stained
cloths tested is considered significant.
At the end of each wash, the active oxygen content of
the wash solution was determined by acidification with dilute
sulfuric acid followed by treatment of the wash solution with
potassium iodide and a minor amount of ammonium molybdate, and
thereafter titration with standardized sodium thiosulfate using
starch as the indicator.
The respective stains and test swatches were as
follows:
--1~--
~ f~
Stain Test Cloth
1. Grape - 65 Dacron - 35 Cotton
2. Blueberry - Cotton
3. Sulfo Dye - EMPA 115 (Cotton)
4. Red Wine - EMPA 114 (Cotton)
5. Coffee/Tea - Cotton
Stained test cloths 1 and 2 are prepared by passing
rolls of unsoiled fabric -through a padding and drying apparatus
(manu-factured by Benz of Zurich, Switzerland) containing either
grape or blueberry solutions at 90 Fo After drying at 250 F,
the fabric is cut into 3" x 4" swatches. Eighty of these
swatches, impregnated with the same stain, are rinsed in 17 gal-
lons of 85F water in an automa-tic home washer. They are then
dried by a passage through a Beseler Print Dryer at a machine
temperature setting of 6 and a speed of 10.
Stained fabrics 3 and 4 are purchased from Testfabrics
Incorporated of Middlesex, New Jersey, and cut into 3" x 4"
swatches.
Stained fabric 5 is prepared by agitating and soaking
unsoiled cotton strips (18" x 36") in a washing machine filled
with a solution of coffee/tea (8:1 weight ratio) at 150F. The
machine is allowed to rinse-spin dry to remove the coffee/tea
solution. The stained fabric is then machine washed twice with
hot pyrophosphate-surfactant solution followed by two comple-te
water wash cycles at 140F. ~he strips are then dried by two
passes through an Ironrite machine set at 10 and then cut into
3" x 4" swatches.
A granular detergent composition (designated herein as
"HDD") was prepared by conven-tional spray-drying and had the
following approximate composition:
Trade Mark
~19--
Composition Weight Percent
Sodium tridecylbenzenesulfonate 15
Ethoxylated C12 - C15
primary alcohol (7 moles
~O/mo]e alcohol)
Sodium tripolyphosphate 33
Sodium carbonate 5
Sodium silicate 7
Sodium carboxymethylcellulose 0.5
Optical brighteners 0.2
Perfume 0.2
Water 11
Sodium sulfate balance
Detergent compositions A-D containing HDD were formu-
lated as set forth in Table 1.
Table 1
Componen-t Compo tion
A B
Detergent, HDD 4.50g 4.50g 4.50g 4-50g
H 48(1) __ __ 0.25 0.25 0.25
DTpMp(2) _____ _____ 0.02 0.09
Sodium perborate 0.32 0~16 0~16 0.16
Ph-thalic anhydride ----- 0.125 0.125 0.125
(1) A bleaching composition containing monoperoxy-
phthalic acid (as magnesium salt) obtained from
Interox Chemicals Houston, Texas and having an
active oxygen content of 5.1%.
(2) Sodium diethylene triamine pentamethylene phos-
phonate obtained from P.A. Hunt Chemical Corp.,
Lincoln, Rhode Island.
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7~
Compositions A through D were tes-ted in accordance
with the procedure described above and the results of the bleach-
ing tests are tabulated in Table 2 which sets forth the initial
and final values of the active oxygen (A.O.) in the wash solu-
tion (expressed as "initial grams" and "residual grams", respec-
tively) and the stain removal achieved for each of the 5 stains.
Table 2
Comparative Bleaching Performance
Composition
A _ C D
Initial grams 32.8 28.7 28.728.7
(A.O. x 103)
Residual grams 30.4 12.4 19.519.9
(A.O. x 103)
Grams consumed 2.4 16.3 9.2 8.8
(A.O. x 103)
Stain Removal % % % %
Grape 61 63 67 67
Blueberry 56 65 67 68
Sulfodye (EMPA 115) 3 4 4 4
Red Wine (EMPA 114) 41 46 49 53
Coffee/Tea 26 30 39 40
Avg. (%) 37 42 45 46
The results of Table 2 indicate that compositions C
and D consume substantially less active oxygen while providing
improved stain removal relative to composition B, a composition
similar to C and D except that it does not contain chelating
agent DTPMP.
. ,~
EXAMPLE 2
Detergent compositions E-J were formulated to contain
0.15% detergent concentration as shown below in Table 3.
Table 3
_ mponent Composition
_ F G _ I J
Detergent, HDD 1.50g 1.50g 1.50g 1.50g 1.50g 1.50g
H-48( ) 0.20 0.20 0.20 0.07 0.07 0.07
DTPMP(2) - 0.02 ----- ----- 0.02 -----
EDTA(3) ~~~~ ~~~-- 0.02 ____- ----- 0.02
Sodium perborate ----- ----- ----- 0.15 0.15 0.15
(10.1% A.O.)
Phthalic anhydride ----- ----- ----- 0.06 0.06 0.06
(1) A bleaching composition containing monoperoxy-
phthalic acid (as magnesium salt) obtained from
Interox Chemicals, Houston, Texas and having an
active oxygen content of 5.1%.
(2) Sodium diethylene triamine pentamethylene phos-
phonate obtained from P.A. Hunt Chemical Corp,,
Lincoln, Rhode Island.
(3) Ethylene diamine tetraacetic acid, disodium salt.
Compositions E through J were -tested in accordance
with the procedures described in Example 1 and the results of
the bleaching tests are tabulated in Table 4, the initial and
final values of the active oxygen in the wash solution and the
stain removal achieved for the five indicated s-tains being
expressed as in Table 2 of Example 1.
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7~
Table 4
Comparative Bleaching Performance
_ F _ H I J
Initial grams 10.210.2 10.218.6 18.618.6
(~o. x 103)
Residual grams 3.6 5.5 3.6 9.4 13.810.0
(A.O. x 103)
Grams consumed 6.6 4.7 6.6 9.2 4.8 8.6
(A.O. x 103)
Stain removal: % % % % % %
Grape 65 64 64 62 63 61
Blueberry 46 47 44 43 47 44
Sulfodye (EMPA 115) 3 4 4 4 5 5
Red Wine (EMPA 114) 37 35 35 33 34 33
Coffee/Tea 70 72 70 _3 82 86
Avg. (%) 44 44 43 45 46 46
The results of Table 4 indicate that the bleaching per-
formance provided by composition G is improved when using composi-
tions I and J in accordance with the invention which contain a
reduced amount of the MPPA bleaching component relative to F and
G but which additionally contain perborate and phthalic
anhydride activator. Further, a comparison of the performance
of I and J indicates -that composition I provides equivalent
bleaching effectiveness relative to composi-tion J while consum-
ing substantially less active oxygen, compositions I and J beingidentical except for the presence of DTPMP in the former and
EDTA in the latter.
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