Note: Descriptions are shown in the official language in which they were submitted.
WO 91/17234 PCr/US91/03101
Granular laundry detergent compositions containing chlorine
scavengers
2081357
Technical F~eld
The present invention relates to low pH, granular laundry
detergent compositions. Certain prefer,ed compositions herein
contain a low level of a chlorine scavenger, preferab1y an
~10 ammonium salt. The compositions minimize Fading of fabric colors
sensitive to higher wash water plls and to the low levels of
chlorine present in ~he wash and rinse water. Other prefsrred
compositions herein are dense, low or no phosphate detergents
containing a specific aluminosilicato, ci ~,î ic acid 3nd carbonate
builder system. Tnese compositiolls provide good cleaning
performance while maintaining good physical properties.
Bac~qround Art
Granular laundry detergents typically are formulated to
provide a wash water pH of about 9.8 to 10.5. This pH range can
cause fading of some fabric dyes after multiple laundry cycles.
When the wash solution is diluted in the rinse, the pH is lowered
to a range of about 7 to 9 where some fabric dyes are generally
less sensitive to pH.
Chlorine is used in many parts of the world to purify water.
To make sure that the water is safe, a small residual amount,
typically about 1 part per million (ppm), of chlorine is left in
the ~ater. It has been found that even this small amount of
chlorine can cause fading of chlorine-sensitive fabric dyes. In a
typical wash, there is usually enough soil on the fabrics to
scavenge residual chlorine and minimize damage to
chlorine-sensitive dyes. However, in the rinse the soil levels
are greatly reduced, as is the pH, and chlorine-sensitive dyes can
~ fade-after multiple laundering cycles. Chlorine is also more
;~ aggressive to dyes at the lower pHs. Thus, fading of fabric
colors over time is a result of both the high pH of typical
~ granular laundry detergents and the presence of residual chlorine
-~ in the wash and rinse water.
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Delivering good cleaning performance from a low or no
phosphate condensed detergent is difficult due to limitations in
conventional spray dry processing. Additionally, trying to
compensate i~ith higher levels of actives (surfactant and builder)
is limited witnout signiFicantly diminishing product physical
properties (solllbility, lumping/caking, scoopability).
Summar~/ or the invention
The ~,es2nt in~ention encompasses granular laundry detergent
composi.,ons co,i~prising:
(a) an e;;~c.ive amounL o; a chlorine scavenger; and
(b) ~he balal1ce consiscing essentially of derergent
components selected from the group consisting of
.ntsnic, nonionic, ~.witterionis, ampholytic, and
~3tionic surfactan~s, de~ergellt builders, inert
; materials, detergent adjuvants, and mixtures thereof;and being essentially free of bleaches;
said composition having a pH of from about 7 to about 9.3 at
a concentration of 1% by weight in water at 20-C.
; 20 The chlorine scavenger of the present composit10ns is
; employed in an effective amount to control residual chlorine in
the wash and rinse water. The amount of chlorine scavenging
material needed will vary, but only a small amount is used to
avoid destroying 'nypochlori-te bleacn that may be added
' 25 deliberately to treat bleach-sensitive stains.
Detailed DescriDtion of the Invention
The granular laundry detergent compositions of the present
invention comprise a chlorine scavenger and detergent additives.
The compositions are formulated to provide a pH of from about 7 to
about 9.3, preferably from about 8 to about 9.1, more preferably
from about 8.5 to about 9.0, at a concentration of 1% by weight in
~ water at 20 C. The individual components of the compositions
;~ herein are described in detail below.
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Chlorine Scavenqer
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The chlorine scavengers should not be used in a large excess
since they will interfere with normal hypochlorite bleaches added
to the wash water for stain removal and whitening. Tne level
should be from about 0.01% to about 10%, preferably from about
0.05% to about 5%, most preferably from about o.oa to about 2%,
based on the molar amount equivalent to react with about 0.5 to
about 2.5, typically about 1, ppm or available chlorine, per
average rinse. If both the cation and t'ne anion of ths sca~/enger
react ~ith chlorine,-which is desirable, ~he le~el is adjus'~ed to
react with an equivalent amount Ot a`/ailable ÇhlOriile.
Suitable chlorine scavengers include che ,^oïlo~ing polym2rs
; which can be divided into four groups according to their
structural construction: polysth~leneimlnss, pslyaml.nec,
polyamineamides and polyacrylamides, o~ w,lich th2
polyethyleneimines, the polyamines and polyamineamides are
especially preferred.
; Suitable polyethyleneimines are obtained by acid-catalyzed
polymerkation of ethyleneimine and can be modified by urea and
epichlorhydrin or dichlorethane. Polyethyleneimines can contain
primary, secondary or tertiary amino groups as well as quaternary
ammonium groups. Aqueous solutions of polyethyleneimines show
basic reaction. The molecular weight can amount up to about
1, 000, 000 .
Polyamines are addition -or condensation products from
multivalent aliphatic amines and compounds with several groups
capable of reacting, for example, epichlorhydrin or alkylene
dihalides. Therefore, they always contain several secondary,
tertiary or even quaternary nitrogen atoms, as well as evencually
also hydroxyl groups in the molecule. They are accordingly
hydrophilic, polar compounds, which behave as polyelectrolytes and
:~ are water soluble, inasmuch as they do not contain large
hydrophobic groups in the molecule. The polyamines exhibit basic
reaction in aqueous solution. Suitable compounds, for example,
are described in U.S. Patent 2,969~302.
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Polyamineamides contain amino- and amido groups in the
molecule at the same time. T'ney are made, for example, by
condensation of multibasic acids, for example, dibasic, saturated,
aliphatic C3 to Cg acids and polyamines, as well as with
compounds, which contain s~veral groups capable oF reacting, such
as, for example, epichlorhydrin. These compounds also demonstrate
basic reaction in aqueous SolUCiOIl. Suitable polyamineamidss are
described, for exampl2, in IJ S Patent 2,925,l5~1.
Polyacrylainides having aimi"o g('OUpS aild molecular weights up
to sev~ral million are suitable for use hersin. By building in
carboxyl groups, 'il~iCi7 ~r~ ~ormed, ,or e:(ample, by partial
hydrolysis, anionic polyacrylamides are obtained in addition to
amido grouDs. "Ihile polyarrylamides ciontaining amin~ groups
exhibit basic ,eûct-,on in aqueous solutiGn. Alnino groups can be
; introduced, for example, by reaction with alkali and hypobromite
or hypochlorite.
It is common to all polymers that they are water soluble.
li Such polymers are cammercial products. Compounds especially well
sui~ted as inserts to the detergents conforming to the d;scovery
are the polyethyleneimines and polyamines, which exhibit strong
basic reaction in water. Examples of commercially available
polyethyleneimines, which are particularly appropriate, are
'iEpomin SP-003" rrom Mippon Sho'~ubai, "Lugalvan G20 and G35" from
;25 BASF, and "Ethyleneamine E-lOO" from Dow Chemical. These polymers
can be added either alone or together with water soluble polymers
ifrom melamine or urea and formaldehyde. Other polymers suitable
for the detergents conforming to the discovery are, for example,
;~.
- the water soluble polymers based on alkyleneimines, acrylamides as
well as melamine or urea and formaldehyde, which are described in
the "Encyclopedia of Polymer Science and Technology", John Wiley &
Sons, Inc., New Yor~, 1968, Yol. 9, p. 762. An addition of these
polymers to the detergents conforming to the discovery in
combination with the amino- and/or amido group-containing polymers
causes an intensification of the dy--protective effect.
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Preferred polymers for use .in the preferred anionic
surfactant containing compositions herein are polyethyleneimines.
Polyethyleneimines are believed to be particularly efficient
chlorine scavengers because they adsorb to cotton fibers. In an
anionic surfactant matrix, ion pairing of the amines with
surfactant or polymeric carboxylates tends to dramatically lower
the solubility of the polymeric amine. The solubility oF 'L'ne
polymeric amine complexes can be maintained by utilizing materi21s
0 of relatively low molecular weight. The molecular ,~eigh-t of tha
chosen amine polymer should be control1?d co acnieve a rabric
substantivity of preferably at least 50%. A Io~ s~bstantivity
will not allow efficient carryover into the rinse. ~re;erred
polyethyleneimines have a molecular ~eight of less ~han abolIt 800,
more preferably from about 200 to about 400.
The cationic charge and the solubility of the polymeric amine
allow the deposition of the polymer onto cotton fabric. The
affinity the polymer has for fabric increases with lower pH, or
higher molecular weight. Thus, a balance oi these properties
(solubility, solution pH, and polymer molecular weight) controls
the efficiency of the chlorine scavenger on fabric and in
solution. The optimal composition will allow a balance of polymer
on fabric (for carryover from wash to rinse) and in solution (for
an efficiency rate of reaction with chlorinej.
Other chlorine scavengers herein are-anions selected from the
group consisting of reducing materials like sulfite, bisulfite,
thiosulfite, thiosulfate, iodide, nitrite, etc. and antioxidants
~`~ like carbamate, ascorbate, etc. and mixtures thereof.
;~ Conventional non-chlorine scavenging anions like sulfate,
bisulfate, carbonate, bicarbonate, nitrate, chloride, borate,
- phosphate, condensed phosphate, acetate, benzoate, citrate,
formate, lactate, salicylate, etc. and mixtures thereof can be
used with ammonium cations.
Other chlorine scavengers useful herein include ammonium
sulfate (preferred), and primary and secondary amines of low
volatility such as ethanolamines, amino acids and their salts,
polyamino acids and their saits, fatty amines, glucoseamine and
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other aminated sugars. Specific examples include tris(hydroxy-
methyl) aminomethane, monoethanol amine, diethanol amine,
sarcosine, glycine, iminodiacetic acid, lysine, ethylenediamine
diacetic acid, 2,2,~5-tetramethyl piperinol, and
2,2,6,6-tetramethyl piperinone.
Other chlori ne scavens2rs i ncl ude phenol, phenol sulronate,
2,2-biphenol, tiron, and t-butyl h~droquinone. Preferred are
meta-pol~phenols âuch as r sorcinol, resorcinol monoacetate,
; 10 2,4-dihydroxybenzoic acid, ~,5-dinydroxybenzoic acid, and
2,4-dihydroxyacetophenone.
Peroxide bleach sources, e.g perboratc, percarbonate and
other persalts, can also be used in minor amounts (less 'ch2n 3~/~ by
~; weight, prererably 1ess ~hall abou~ 2'~',) as a ch10rine scav~ng2r
herein. However, peroxides are not efficient chlorine scavengers
because they cannot be used at high enough levels to carry over to
; the rinse water without risk of bleach damage to colors.
Detergent compositions comprising the chlorine scavenger and
the detergent component can be provided having various ratios and
proportions of these two materials. Of course, the amount of thè
~, chlorine scavenger can be varied, depending upon the level ofresidual chlorine expected by the formulator. Moreover, the
amount of detergent component can be varied to provide either
heavy-duty or light-duty products, as desired. This invention
relates primarily to detergent compositions that contain
essentially no additional ingredients which are chlorine
.
scavengers. For example, the other materials present should not
provide any substantial additional amounts of ammonium cations in
; the wash solution.
Deterqent Additives
The amount of the detergent surfactant component can, as
noted hereinabove, vary over a wide range which depends on the
desires of the user. In general, the compositions contain from
about 5% to about 50%, preferably from about 10% to about 30% by
weight, of detergent surfactant, which preferably is an anionic
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The detergent compositions of the instant invention can
contain all manner of organic, water-soluble detergent surfactant
compounds. A typical listing of the classes and species of
5detergent compounds useful herein appear in U.S. Patent 3,6~4,961,
incorporated herein by reference. The following list of detergent
compounds and mixtures which-can be used in the instant compo-
sitions is representative of such materials, but is not intended
to be limiting.
10Water-soluble salts of the higher fatty acids, i.e.~ "sGaps"~
are useful 2S the detergent component of the composition harein.
This class of detergents includes ordinary alkali metal soaps sucn
as the sodium, potassium, salts of higher fatty acids containing
from about 8 to about 24 carbon atoms and pre-,-erabl~ ,-ro"l about 10
to about 20 carbon atoms. Soaps can be made oy direct
; saponification of fats and oils or by the neutralization of fre~
fatty acids. Particularly useful are the sodium and potassium
salts of the mixtures of fatty acids derived from coconut oil and
tallow, i.e., sodium or potassium tallow and coconut soap.
20Another class of de~ergents includes water-soluble salts,
particularly the alkali metal salts of organic sulfuric reaction
products having in their molecular structure an alkyl group
containing from about 8 to about 22 carbon atoms and a sulfonic
acid or sulfuric acid ester group. (Included in the term "alkyl"
is the alkyl portion of acyl groups.) Examples of this group of
synthetic detergents which form a part of the detergent
compositions of the present invention are the sodium and potassium
alkyl sulfates, especially those obt2ined by sulfating the higher
; alcohols (Cg-C1g carbon atoms) produced by reducing the glycerides
of tallow or coconut oil; and sodium and potassium alkylbenzene
sulfonates, in which the alkyl group contains from about 9 to
- about 15 carbon atoms, in straight chain or branched chain
configuration, e.g. those of the type described in United States
; Patents 2,220,099 and 2,477,383, incorporated herein by reference.
~ 35 Especially valuable are linear straight chain alkylbenzene
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sulfonates in which the average of the alkyl groups is about 12
carbon atoms, abbreviat~d as C12 LA~-
Other anionic detergent surfactant compounds herein include5 the sodium alkyl glyceryl ether sulfon2tes, especially those
ethers of higher alcohols derived from tallo,w and coconut oil;
sodium coconut oil fatty acid munoglyceride sulfonates and
sulfates; and sodium or potassium salts o~ alkyl phenol ethylene
oxide ether sulfat2 containii1g frcln aoout 1 o about 10 units of
0 ethylene oxide per molerule and ~:lherein ~he alkyl groups contain
about 8 to about 13 carbon atoms.
ater-soluble nonionic synlha~ic detergqnt surfactants are
also useful as the deterrent component of the instant composition.
Such~ nonionic detergelt ma!~-,ial, ca,l b2 b~^Oadl~ ci2l^1n2d as
compounds produced oy ~he condensa-cion oF etnylene oxide groups
(hydrûphilic in nature) with an organic hydrophobic compound,
which may be aliphatic or alkyl aromatic in nature. The length of
` the polyoxyethylene gro.up which is condensed with any particular
hydrophobic group can be readily adjusted to yield a water-soluble
compound having the desired degree of balance between hydroph;lic
and hydrophobic elements.
For example~ a well-known class of nonionic synthetic deter-
,
gents is made available on the market under the trade name of"Pluronic". These compounds are formed by condensing ethylene
oxide with a hydrophobic base formed by the condensation of
propylene oxide with propylene glycol. Other suitable nonionic
synthetic detergents include the polyethylene oxide condensates of
alkyl phenols, e.g., the condensation products of alkyl phenols
having an alkyl group containing from about 6 to about 13 carbon
atoms in either a straight chain or branched chain configuration,
with ethylene oxide, the said ethylene oxide being present in
amounts equal to from about 4 to about 15 moles of ethylene oxide
per mole of alkyl phenol.
The water-soluble condensation products of aliphatic alcohols
having from about 8 to about 22 carbon atoms, in either straight
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2081357
chain or branched configuration, with ethylene oxide, e.g., a
coconut alcohol-ethylene oxide condensate having from about 3 to
about 30 moles of ethylene oxide per mole of coconut alcohol, the
coconut alcohol fraction having from about 10 to about 14 carbon
atoms, are also useful nonionic detergents herein.
Semi-polar nonionic detergent surfactants include
~ water-soluble amine oxides containing one alkyl moiety of from
- about 10 to 20 carbon atoms and 2 moieties selected from the group
consisting of alkyl groups and hydroxyalkyl groups containing ;rom
1 to about 3 carbon atoms; water-soluble phosphine o~ide
detergents containing one alkyl moiety of from about 10 to 20
carbon atoms and 2 moieties selected from the group consisting of
~` al~yl groups and hydroxyalkyl groups containing from l to 2bout 3
carbon atoms; and water-soluble sulfoxide detergents containing
one alkyl or hydroxyalkyl moiety of from about 10 to about 20
carbon atoms and a moiety selected from the group consisting of
alkyl and hydroxyalkyl moieties of from 1 to about 3 carbon atoms.
Ampholytic detergent surfactants include derivatives of
aliphatic or aliphatic derivatives of heterocyclic secondary and
tertiary amines in which the aliphatic ~oiety can be straight
chain or branched and wherein one of the aliphatic substituents
contains from about 8 to about 18 carbon atoms and at least one
aliphatic substituent contains an anionic water-solubilizing
group.
Zwitterionic detergent surfactants include derivatives of
aliphatic quaternary ammonium, phosphonium and sulfonium compounds
in ~hich the aliphatic moieties can be straight chain or branched,
; and wherein one of the aliphatic substituents contains from about
8 to about 18 carbon atoms and one contains an anionic water-
solubilizing group. The quaternary compounds, themselves, e.g.
cetyltrimethyl ammonium bromide, can also be used herein.
Other useful detergent surfactant compounds herein include
the ~ater-soluble salts of esters of alpha-sulfonated fatty acids
`~ 35 containing from about 6 to about 20 carbon atoms in the fatty acid
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group and from 1 to about 10 carbon atoms in the ester group;
water-soluble salts of 2-acyloxy-alk3ne-l-sulfonic acids
containing from about 2 to about 9 carbon atoms in the acyl group
and from about 9 to about 20 carbon atoms in the alkane moiety;
alkyl ether sulfates containing From abouc 10 to about 20 carbon
atoms in the alkyl group and from about 1 to about 1~ moles of
ethylene oxide; water-soluble salcs or 012;in sulfonates
containing from about 12 to 20 -arbon atoms; ~nd beta-alkyloxy
alkane sulfonates containing from abcll~ 1 ;o 3 carbon a-coms in ~he
: alkyl group and from about ~ to Z0 carbon atoms in the al!~ane
moiety.
Preferred water-soluble organic detergent compounds herein
include linear alkylbenzen2 .;ulfona~s contai~ g r..,m abJut 11 to
about l3 carbon atoms in the alkyl group; Cio l8 al~yl sulrates;
the C1o-l6 alkyl glyceryl sulfonates; Clo l~ 21kyl ether sulfates,
especially wherein the alkyl moiety contains from about 14 to 1
carbon atoms and wherein the average degree of ethoxylation
between 1 and 6; C10-l8 alkyl dimethyl amine oxides, especially
wherein the alkyl group contains from about 11 to 16 carbon atoms;
; alkyldimethyl ammonio propane sulfonates and alkyldimethyl ammonio
hydroxy propane sulfonates wherein the alkyl group in both types
contains from 14 to 1~ carbon atoms; soaps, as hereinabove
lj defined; and the condensation proàuct or C10-l8 fatty alcohols
:, 25 with from about 3 to about 15 moles of ethylene oxides.
, . Specific preferred detergents for use herein include: sodium
: linear C10 13 alkylbenzene sulfonates; sodium C12 18 alkyl sul-
fates; sodium salts of sulfated condensation product of C12-i8
:: . alcohols with from about 1 to about 3 moles of ethylene oxide; the
condensation product of a C1o-l8 fatty alcohols with from about 4
~ . . to-about 10 moles of ethylene oxide; and the water-soluble sodium
: and potassium salts of higher fatty acids containing from about 10
:~ to about 18 carbon atoms.
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It is to be recognized that aiy of the foregoing detergents
can be used separately herein, or as mixtures. Examples of
preferred detergent mixtures herein are as follo~s.
An especially preferred alkyl ether sulfate detergent compo-
nent of the instant compositions is a mixture of alkyl ether sul-
fates, said mixture having an average (arithmetic mean) carbon
chain.length within the range of from about 12 to 16 carbon atoms,
preferably From about 14 to 15 carbon atoms, and an a~lerage
(arithmetic mean) degree of ethoxylation of from about 1 to ~
moles of ethylene oxide, preferably from about 1 to 3 moles of
ethylene oxide.
The detergent compositions of the present invention can
contain, in addition to the detergent surfactant, water-soluble or
~ water-insoluble builders such as those commonly taught for use in
; detergent compositions. Such auxiliary builders can be employed
to sequester hardness ions and to help adjust the pH of the
laundering liquor. Such builders can be employed in
concentrations of from about 5Y. to about 95X by weight, preferably
from about 10% to about 50% by weight, of the detergent
compositions herein to provide their builder and pH-controlling
functions. The builders herein include any of the conventional
inorganic and organic water-soluble builder salts.
~ Such builders can be, for example, water-solub'.e salts of
phosphates including tripolyphosphates, pyrophosphates, ortho-
` phosphates, higher polyphosphates, carbonates, silicates, and
organic polycarboxylates. Specific preferred examples of
inorganic phosphate builders include sodium and potassium
tripolyphosphates and pyrophosphates.
Nonphosphorus-containing materials can also be selected for
use herein as builders.
~ .
Specific examples of nonphosphorus, inorganic detergent
~ builder ingredients include water-soluble inorganic carbonate,
-~ bicarbonate, and silicate salts. The alkali metal, e.g., sodium
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WO91/17234 PCI/l'S91/03101
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and potassium, carbonates, bicarbonates, and silicates are parti-
cularly useful herein.
Aluminosilicate ion exchange materials useful in the practice
of this invention are commercially available. The
aluminosilicates useful in this invention can be crystalline or
amorphous in structure and can be naturally-ocrurrins
aluminosilicates or synthetically derived. A me~hod for prqducing
aluminosilicate ion exchange materials is discussed in U.S. Pat.
No. 3,985.669, Krummel et al, issued Oct. 12, 197r, incorr~rated
herein by reference. Prererred synchecic crystalline
aluminosilicate ion exchange materials userul h2rein are a~/ailable
under the designations Zeolite A, Zeolite B, and Zeol~te X. In an
especially preferred embodiment, the cr~st-allin? alei,~,nosilic3L.e
ion exchange material in Zeolite A and has the i~3rmula
Nal2[A102)12.(SiO2)l2]-xH2o
wherein x is from about 20 to about 30, especially about 27.
Water-soluble, organic builders are also useful herein. For
example, the alkali metal, polycarboxylates are useful in the
present compositions. Specific examples of the polycarboxylate
builder salts include sodium and potassium, salts of ethylene-
diaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic
acid, mellitic acid, benzene polycarboxylic acid, poly2crylic
: acid, polymaleic acid, and citric acid.
Other desirable polycarboxylate builders are the builders set
: forth in U.S. Patent 3,308,067, Diehl, incorporated herein by
reference. Examples of such materials include the water-soluble
salts of homo- and co-polymers of aliphatic carboxyllc acids such
as maleic acid, itaconic acid, mesaconic acid, fumaric acid,
aconitic acid, citraconic acid, and methylenemalonic acid.
Other suitable polymeric polycarboxylates are the polyacetal
carboxylates described in U.S. Pat. No. 4,144,226, issued Mar. 13,
1979 to Crutchfield et al, and U.S. Pat. No. 4,246,495, issued
Mar. 27, 1979 to Crutchfield et al, both incorporated herein by
reference. These polyacetal carboxylates can be prepared by
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; bringing together under polymerization conditions an ester of
glyoxylic acid and a polymerization initiator. The resulting
polyacetal carboxylate ester is then attached to chemically stable
end groups to stabilize the polyacetal carboxylate against rapid
depolymerization in alkaline solution, converted to the
corresponding salt, and added to a surfactant.
Preferred builders herein are polycarbo~ylic acids,
especially citric acid, which preferably are used at a level of
From about 5% to about 10% by weight, and sodium acid
pyrophosphate, which preferably is used at a level of irom about
5% to about 15% by weight. Such materials function as both
builder and acid source to adjust pH to the desired range.
Deteraent Adiuvants
The detergent compositions herein can contain all manner of
additional materials, detergent adjuvants, commonly found in
laundering and cleaning compositions. For example, the
compositions can contain thickeners and soil-suspending agents
such as carboxymethylcellulose and the like. Various enzymes,
enzyme stabilizers, suds suppressors~, perfumes, optical bleaches,
fillers, anticaking agents, fabric softeners and the like can be
present in the compositions to provide the usual benefits
occasioned by the use of such materials in detergent compositions.
Ihe compositions herein are essentially free of oxygen
;~ 25 bleaching agents, since if they are present, there is no need for
;~ the chlorine scavenger. Similarly, there should be no chlorine
bleaching agent present since the chlorine scavenger wnuld not be
~ effective against a large amount of available chlorine.
A finished detergent composition of this invention can con-
tain minor amounts of materials which make the product moreattractive. The following are mentioned by way of example: a
tarnish inhibitor such as benzotriazole or ethylene thiourea can
be added in amounts up to 2% by weight; fluorescers, perfumes and
dyes, while not essential, can be added in small amounts. An
alkaline material such as sodium or potassium carbonate or~
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hydroxide can be added in minor amounts as supplementary pH
adjusters. There may also be mentioned, as suitable addi~ives:
bacteriostats, bactericides, corrosion inhibitors such as soluble
5 alkali silicates (preferably sodium silicates having an SiO~/N220
ratio of from 1:1 to 2.8:1), and textile softening agents.
Particularly preferred compositions herqin are g,anular
laundry detergents comprising by ~eight:
~` (a) from about 15% co about 25%, prel-erlDl~ -130U'C 13~, 50
about Z3%, of a mixture o~ a Cll-C13 (prq~
C12-C13) alkylben~ene sulfonate su.factan' and i C,~-C",
(preferably C1~-C1s) al'~yl sulfate surfactant in
weight ratio of sulfonatq surf~ctant to su',rate
surfactant of from ~bout ':1 o bou- ': , ln., ~ra~)~
about 2 :1;
(b) from about 1% to about 3%, preferably about 1.5% to
about 2.5%~ of an alkali metal (preferably sodium)
si-licate having a molar ratio of SiO2 to alkali metal
oxide of from about 1.0 to about 2.4, preferably about
1.4 to about 2.0;
(c) from about 20% to about 30%, preferably about 22% to
about 28%, more preferably about 25% to about 28%, of a
finely divided aluminosilicate ion exchange matPrial
selected from the group consisting of:
(i) crystalline aluminosilicate material of the
formula:
Naz[(A102)z. (SiO2)y] XH20
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
from 10 to 264, said material having a
particle size diameter of from about 0.1
micron to about 10 microns, a calcium ion
exchange capacity of at least about 200 mg
CaC03 eq./g and a calcium ion exchange rate of
at least about 2 grains Ca++/gallon/min-
ute/gram/gallon;
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W O 91/17?34 PC~r/US91/03101
2~1357
- 15 -
(ii) amorphous hydrated aluminosilicate material of
the empirical formula:
M~(ZAlO2-YSio2)
wherein M is sodium, potassium, ammonium, or
substituted ammonium, z is from about 0.5 to
about 2 and y is 1, said material having a
magnesium ion exchange ion exchange capacity
of at least about 50 milligram equivalents of
CaC03 hardness per gram of anhydrous
aluminosilicate and a Mg++ exchange rate of at
least about 1 grain/gallon/minute/gram/gallon;
and
mixturPs theroof;
~d) from about 4/0 to about 10%, preferably about 5% to about
8%, of citric acid;
(e) from about 5% to about 20X~ preferably fro~ about 8% to
- about 12%, of an alkali metal (preferably sodium)
carbonate;
said composition having a pH of from about 7 to about
9.3, preferably about 8 to about 9.1, mare preferably
about 8.5 to about 9.0, at a concentration of 1% by
weight in water at 20-C, and said composition having a
density of from about 500 to about 600 grams per liter.
Preferred aluminosilicate ion exchange material is of the
formula Nal2[(A102)12(SiO2)12].xH2o~ wherein x is from about 20 to
about 30.
The above granular detergent compositions provide good
cleaning performance due to the relatively high levels of anionic
surfactants and aluminosilicate, citric acid, and carbonate
. .
builders~ Despite having a density of from about 500 to about 600
` grams per liter, the compositions have good physical properties,
i.e., they are free-flowing and are readily soluble in the
laundering solution. The citric acid and carbonate levels are
35 selected to obtain the required pH range and provide additional
builder functioh to the aluminosilicate material.
.
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W O 91/17234 PCT/US91/031U1
2~813~ - 16 -
All percentages, parts and ratios herein are by weight unless
otherwise specified.
The following examples illustrate the compositions herein.
EXAMPLES
Granular detergent compositions of the present in~ention
- comprise the following ingredients:
Inqredient Percent (',~t~
II III
Sodium 12.3 linear alkyl
benzene sulfonate 13.6 12.7 15.8
Sodium C14-C1s alkyl sulfate5.8 5.4 6.8
` C12-C13 alcohol ethoxylate
:~ (E0 6) 0 0 0.0 0.~
Citric acid 5.5 4.9 0.0
Sodium tripolyphosphate 0.0 0.0 6.8
Sodium pyrophosphate 0.0 0.0 13.1
Sodium acid pyrophosphate 0~0 0.0 12.4
Zeolite A, hydrate
(1-10 micron size) 2C.9 27.3 0.0
Sodium carbonate 10.3 8.9 0.0
Sodium silicate (1.6
ratio NaO/SiO2) 2.2 2.1 7.6
Polyethylene glycol 8000 1.4 1.3 0.6
Sodium polyacrylate (MW 45003 3.2 3.0 3.4
Protease enzyme* 1.8 1.7 0.7
Sodium perborate tetrahydrate 0.0 0.0 1.9
Ammonium sulfate 2.0 2.0 0.0
` ~ Sodium sulfate 18.3 17.1 14.4
: 30 Balance (including water, brightener,
perfumej suds suppressor) ---------- to 100.0 -------
pH 1% aqueous solution at 20~C 8.7 8.9 9.2
. *Activity of 1.8 Anson units per gram.
: Aqueous crutcher mixes of the detergent compositions are
: 35 prepared and spray-dried, except for the citric acid, sodium acid
~ pyrophosphate, enzyme, perfume, and ammonium sulfate or perborale,
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WO 91/17234 PCr/US91/03101
- 208~3~7
- 17 -
which are admixed, so that they contain the above ingredients at
- the levels shown.
Fabrics laundered using the above compositions retain their
color over time better than similar compositions not containing
the chlorine scavenger or formulated to provide a higher wash pH.
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