Note: Descriptions are shown in the official language in which they were submitted.
~Z~;28S2
GRANULAR DETERGENT COMPOSiTlONS
CONTAINING AN INTIMATELY ADMIXED ANIONIC
SURFACTANT AND AN ANIONIC POLYMER
Brian D. Barford
.
.
r~, . T ECHN I C:AL F I ELD
The present invention relates to granular detergent compo-
sitions containing an anionic surfactant and an anionic water-
soluble polymer in intimate admixture. The compositions herein
disperse and dissolve more rapidly in the laundering solution than
simila~ compositions with surfactant alone.
The dispersibility and solu~ility of ~ranular detergent
compositions presents a challenge anc~ dilemma to those who
formulate and process such compositions. The spray-dried form
of such compositions has provided generally satisfactory
dispersibility and solubili~y if the individual components are
` soluble or dispersible in water~ The spray-dried form, however~
- 20 requires acceptance of a relatively iow density no higher than
- about 0.4-0~5 grams per milliliter to obtain substantial porosity.
The porosity, of course, provide a speed of solubllity benefit.
Higher density granular detergent compositions can be made by
various mechanical mixing and agglomeration processes but
; 25 solubility rate generally becomes less satisfactory. It is an object
~l of this invention to improve the dispersibility and solubiiity of
granular Idetergent compositions that are made by processes that
provide higher densities than are available from conventional
spray-drving processesO
BACKGROUND ART
U.S. Patent 4,072,621, Rose, issued Feb. 7, 1978, discloses
the addition of a water-soluble copolymer of a vinyl compound and
maleic anhydride to granular detergents containing aluminosilicate
builders .
British Patent 2,048,B41, Burzlo, published Dec. 17, 1980,
/:
i21)Z8~Z
discloses the use of polymeric acrylamides to stabilize aqueouS
suspensions of zeolites~ The suspensions are said to be suitable
. .
-~ for spray-drying to obtain detergent compositions.
UOS. Patent 3,933,673, Davies, issued Jan. 20, 1976, de-
s scribes the use of partial alkali metal salts of homo- or copolymers
of unsaturated aliphatic mono- or polycarboxylic acids as builders
which provide improved storage properties.
U.S. Patent 3,794,605, Diehl, issued Feb. 26, 1974, relates
to the use of from OOI~ to ~0% of a mixture of salts of cellulose
sulfate esters and copolymers of a vinyl compound with maleic
anhydride to provide whiteness maintenance benefits to de~ergent
compositions .
~2, U.S. Patent 3~380,9220 Shields, issued Apr. 30, 1968~ dis-
closes film-forming resinous polymers useful as binders te improve
~-` 15 mechanical properties of detergents.
lJoS~ Patent 3~803,285, Jensen~ issued Apr. 9, 1974, de-
scribes granular detergents containing various starch derivatives~
The granules are said to be free-flowing and cake resistant, and
- to dissolve rapidly in water.
UOS. Patent 3,922,230~ Lamberti et al, issued November 25,
1975, discloses detergent compositions containing oligomeric poly-
acrylates.
UOS. Patent 4,031,022, Vogt et al~ issued June 21; 1977,
discloses detergent compositions containing copolymers of alpha-
2~ hydroxyacrylic acid and acrylic acid.
UOSO Patent 4,076,643; Brahm et al, issued February 28,
i978, discloses the preparation of free-flowing particulate premixes
intended for use in detergent compositions. The premix contains
one or more liquid or paste-like surfactants and a water-soluble
- 30 hydroxycarboxylic polymer or copolymer.
British Patent 1,333 j915~ published Oct. 17, 1973, discloses
that polyacrylic acids of molecular weight greater than 1000 and
,!i having from 5-55% of its carboxyl groups neutralized as the
sodium salt are free-flowing powders useful as detergent builders.
British Patent 1,380,4û2, Pritchard et al, published Jan. 15,
.
Z8S2
- 3 -
1975, relates to the addition of low levels of reactive
and non-reactive polymers to provide free-flowing
granular detergents containing nonionic surfactants.
U.S. Patent 3,920,570, Mulders, issued
November 18, 1975, relates to the use of poly-~-
hydroxyacrylates as sequestering agents for detergent
compositions.
U.S. Patent No. 4,379,080, Murphy, issued
April 5, 1983, discloses the addition of soluble film-
forming polymers to aluminosilicate-built, low
phosphate and silicate granular detergents to provide
free-flowing and solubility characteristics.
European Application No. 0063399, Kassamali
et al, published October 27, 1982, discloses granular
detergent compositions containing an organic surfactant,
a water-soluble salt, an aluminosilicate ion exchange
material, a low ratio silicate and film-forming
copolymer of acrylamide and acrylate.
SUMMARY OF THE INVENTION
The pres~nt invention encompasses a granular
detergent composition prepared by agglomeration and dry
mixing comprising an intimate admixture of (a) and (c)
below:
(a) from about 3% to about 40% of a non-soap
anionic surfactant;
(b) from about 5% to about 85% by weight of
a water-soluble neutral or alkaline salt
and mixtures thereof; and
(c) from about 1% to about 50% by weight of
the non-soap anionic surfactant of a
water-soluble anionic polymer having an
average molecular weight of from about
300 to about 15,000 and at least
1 ionizable site per 200 units of
molecular weight, w~erein the intimate
admixture o~ (a) and (c) is accomplished
:;
:~LZ~lZ85;~
- 3a ~
by drying a solution or slurry
containing the surfactant and the acid
or salt of the polymer prior to contact
with the other major ingredients.
DETAILED DESCRIPTION OF THE INVENTION
The granular detergent compositions of the
present invention contain the following essential
components:
~.
28~;~
- 4 ~
1) non-soap anionic surfactant,
2) water-soluble saltsi and
3) water-soluble anionic polymer.
The compositions herein are prepared by any
suitable process that will result in the intimate
admixture of surfactant and polymer. The intimate
admixture can be accomplished by drying a solution of
slurry containing the polymer and surfactant or their
precursors. Subsequent processing including
incorporation of water-soluble salts and optional
ingredients should avoid steps that result in
appreciable solution of the polymer/surfactant mixture
in the presence of other water-soluble components.
Agglomeration and dry mixing techniques are particularly
suitable in the practice of the present in~ention for
producing complete granular detergent compositions ~ile
maintaining an intimate admixture of surfactant and
polymer.
While not bound by any particular theory, it
is believed that the polymers which are useful in the
compositions of this invention provide their benefit by
eliminating or retarding the formation of a highly
viscous 'gum' phase of anionic surfactant and water which
acts to retard granule dissolution.
Surfactant
The detergent compositions herein contain
from about 3% to about 40% by weight of non-soap
anionic surfactant, preferably from about 4% to about
35%, and more preferably from about 5% to about 30%.
In relatively high sudsing detergent compositions the
non-soap anionic surfactant generally represents from
about 10% to about 35%, and preferably from about 12%
to about 30%, by weight of the detergent composition.
Surfactants useful herein are listed in U.S, Patent
35 3,664,961, Norris~ issued May 23, 1972, and in U.S.
Patent 3,919,678, Laughlin et alt issued December 30, 1975.
Usefui non-soap anionic surfactants also include the water-
~ soluble salts~ preferably the alkali metal, ammonium and alkyl-
`~; olammonium salts, of organic sulfuric reaction products having in-~ their molecular structure an alkyl group con~aining from about 10
~- 5 to about 20 carbon atoms and a sulfonic acid or suifuric acid
ester group, (Included in the term "alkyl" is the alkyl portion of
aryi groups. ) Examples of this ~roup of synthetic surfactants
. are the sodium and potassium alkyl sulfates, especially those
obtained by sulfating the higher alcohols ( C8-CI8 carbon atomsl
such as those produced by reducing the glycerides of taliow or
COGOnut oil; and the sodium and potassium alkylbenzene sul~onates
in which the alkyl group contains from about 9 to about !5 carbon
atoms, In straight chain or branched chain confi~3uration, e.~3~O
those of the typa described in IJnited States Patents 2,220,099
~- 15 and 2D477~3830 Especially valuable are linear straight chain
alkylbenzene sulfonates in which the average number of carbon
atoms in the alkyl group is from about 11 to 13, abhreviated as
C11_13LA~ o
Other anionic surfactants herein are the sodium alkyl gly-
.~ 20 ceryl ether sulfonates~ especially ~hose ethers of higher alcohols
derived from taliow and coconut oil; sodium coconut oil fatty acid
monoglyceride sulfonates and sulfates; sodium or potassium salts
- of alkyl phenol ethylene oxide ether sulfates containing from
about I to about 10 units of ethylene oxide per molecule and
wherein the alkyl groups contain from aboul: 8 to about t2 carbon
atoms; and sodium or potassium salts of allcyl ethylene oxide ether
:., sulfates containing about I to about 10 units of ethylene oxide per
molecule and wherein the alkyl group contains , rom about 10 to
about 20 carbon atomsO
Other useful anionic surfactants herein include the water-
soluble salts of esters of oL-sulfonated fatty acids containing from
about 6 to 20 carbon atoms in the fatty acid group and from
about I to 10 carbon atoms in ~:he ester group; water-soluble salts
3 of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9.. ~. 35 carbon atoms in the acyl group and from about 9 to about 23
-
. ,~"
i~)Z8S2 1
....
. .
.
.. "
- 6 -
carbon atoms in the alkane moiety; alkyl ether sulfates containing
from about 10 to 20 carbon atoms in the alkyl group and from
about i to 30 moles of ethylene oxide; water-soluble salts of olefin
sulfonates containing from about 12 to 24 carbon atoms; and
~-alkyloxy alkane sulfonates containing from about I to 3 carbon
atoms in the alkyl group and from about ~ to 20 carbon atoms in
the alkane moiety.- P~nionic sulfonate surfactants are particularly
~;~
preferred In the compositions of the invention in that a very
substantial solubility benefit is provided.
Par~icularly preferred anionic surfactants herein include
- linear alkylbenzene sulfonates containing an average of from about
Il to 14 carbon atoms in the alkyl group; talluwalkyl sulfat2s;
~r coconutalkyl glyceryl ether sulfonates; alkyi ether sulfates
wherein the alkyl moiety contains from about 12 to 18 carbon atoms
~-~ 15 and wherein the average degree of ethoxylation is from about I to
4 and olefin or paraffin sulfonates containing from about 12 to 16
carbon atomsO
- Specific preferred surfactants for use herein include sodium
linear Cll 13 alkylbenzene sulfonate and the sodium salt of a sul-
fated condensation product of a C12 18 alcohol with about I to 4
moles cf ethylene oxide. The advantages obtained with the
compositions and the process of ~he invention are particularly
apparent when said COmpOsitiQns comprise a non-soap anionic
` surfactant selected from the group comprising alkyl benzene
2 5 su If onates, olefi n 5U I fonate~: and pa raffi n su I fonates .
- Y/ater-Soluble Neutrai or Alkaline Salt
,, The granular detergents of the present Invention contain
~~ from about ~% to about 85%, preferably from a~out 10% to about
70%, and more preferably from about 30% to about 65~, by weight
of water-soluble neutral or alkaline salts. The neutral or alkaline
salt has a pH in solution of seven or greater, and can be either
organic or inorganic in nature~ The salt assists in providing the
desired density and bulk to the detergent granules here;n. While
-~ some of the salts are inert, many of them aiso function as a
detergency builderD
The neutral or alkaline water-soluble salts useful in ~he
~.,
8S;~:
practice of the invention are materials consistent with use in
granular detergent compositions from such standpoints as biologi-
cal safety, effect on environment, and physical and chemical
propertiesO Sodium and potassium salts are particularly useful
- 5 for reasons of cost and physical properties. Suitable salts may
be inorganic or organic, monomeric or polymeric.
Examples of neutral water soluble salls include the alkali
metai, ammonium or substituted ammonium chlorides and sulfates.
The alkali metal, and especially sodiumr salts of the above are
preferred. Sodium sulfate is typically Lised in detergent granules
and is a particularly preferred salt herein.
;r; Other useful water-soiuble salts include the compoundscommoniy known as detergent builder materials. Builders are
generally selected from the various water-soluble, alkaii metal,
ammonium or substituted ammonium phosphates, poiyphosphates,
phosphonates, polyphosphonatesc carbonates, siiicates, borates,
poiyhydroxy sulfonates, polyacetates, carboxylates, and polycar-
boxyiates~ Preferred are the alkali metal, especialiy sodium, salts
of the above.
- 20 Specific exarnpies ot inorganic phosphate builders are sodium
and potassium tripolyphosphate, pyrophosphal:e, polymeric meta-
phosphate having a degree of polymerization of from about 6 to
21, and orthophosphate. Examples of polyphosphonate builders
are the sodiurn and potassium saits of e1:hylene di,Q~osphonic acid,
the sodium and potassium salts of ethane l-hydroxy-l,l-diphos-
phonic acid and the sodium and potassium salts of ethane, 1,1,2-
triphosphonic acid. Other phosphorus builder compounds are
disclosed in U.S. Patents 3,159,581; 3,213,030, 3,422,021
3,422,137; 3,4û0,176 and 3,400,148
Examples of nonphosphorus, inorganic builders are sodium
and potascium carbcnate, bicarbonate, sesquicarbonate, tetra-
borate decahydrate~ and silicates havin~3 a weight ratio of SiO2 to
alkali metal oxide of from about 0.5 to about 4.0, preferably from
about 1.0 to about 2.40
)Z8~;Z
Water-soluble, nonphosphorus organic builders useful herein
include the various alkali metal, ammonium and substituted ammon-
ium polyacetates, carboxylates, polycarboxylates and polyhydroxy
sulfonates. Examples of polyacetate and polycarboxylate builders
are the sodium, potassium, lithium, ammonium and substituted
ammonium satts of ethylene diamine tetraacetic acid, nltrilotriacetic
acid, oxydisuccintc acid, mellitic acid, benzene polycarboxylic
acids, and citric acid. Salts of nitrilotriacetic acid, such as
sodium nitrilo~riacetate, are particularly preferred.
Puiyrrleric polycarboxylate builders are set ~orth in U.S.
Patent 3,308,067, Diehl, issued March 7, 1967,
Such materiais include the water-soluble salts of
homo- and copciymers of aliphatic carboxylic acids such as maleic
acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid,
citraconic acid an~ methyienemalonic acid. Some of these materi-
als are useful as the water-soluble anionic polymer as hereinafter
described, but only if in intlmate admixture with the non-soap
anionic surfactant.
Other useful builders herein are sodium and potassium
carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclo-
hexanehexacarboxylate, cis-cyclopentanetetracarboxylate, phloro-
glucinol trisulfonate, and the copolymers of maleic anhydride with
vinyl methyl ether or ethylene.
Other suitable polycarboxylates for use herein are the poly-
acetal carboxylates described in U.S. Patent 4,144,226, issued
March 13, 1979 to rutchfield et al, and U.S. Patent 4,246,495,
issued March 27, 1979 to Crutchfield et al,
These polyacetal carboxylates can be pre-
pared by bringing together under polymerization conditions an
ester of glyoxylic acid and a polymerization initiator~ The re-
sulting polyacetal carboxylate ester is ~hen attached to chemically
stable end groups to stabilize the polyacetal carbox~ylate against
rapid depolymerization in alkaline solution, converted to the
corresponding salt, and added to a detergent composition.
Water-soluble silicate solids represen~ed by the formula
.
~ILZ0~85Z
.:. g
SiO~-M20, M being an alkali metal, and having a SiO2:M;~O weight
ratio of from about 0.5 ~o about 4.0~ are useful salts in the
composit;ons of the inventions at levels of from about 2% to about
15% on an anhydrous weight basis~ preferably from about 39~ to
5 about 8~6. Anhydrous or hydrated particulate silicate can be
- utilized. In one embodiment of the invention, a silicate water
soiution containing from about 35~ to about 55~ silicate solids can
be used as an agglomerating agent.
Water-Soluble Anionic Polymer
The compositions of the present invention aiso cont2in in
intimate admixture with the non-soap anionic detergent surfactant
from about 1% to about 50~6, preferably from about 3% to about
30%~ and more preferably from about 5% to about 2~%, by wei~3h.
of the non-sGap anionic detergent sur~actant of a water-soluble
15 anionic polyme~ wlth at leasi I ionizable site per 200 units of
molecular weight, preferably at least about I ionizable site per lO0
units of molecular weight. While some dispersion advantage is
-, obtained with average polymer molecular weights as iligh as SO~ûO0
average moiecular weight preferably is from about 300 to about
20 l5,000, and most preferably is from about lO00 to about 5,000.
Also, the wa~er soluble anionic polymers are preferably substan-
-:l tially or completely neutralized water soluble salts. As used
herein, average moiecular weight is on a polymer weight basis.
Suitat)le polymers G~erein include homopolymers and copoly-
25 mers of unsaturated aiiphatic mono- or polycarboxylic acids~
Preferred carboxylic acids are acrylic acid, hydroxyacrylic acid,
methacrylic acid, maleic acid, fumaric acid, itaconic acid, aconitic
acid, crotonic acid, and citraconic acid. The polycarboxylic acids
~e.g. maleic acidi can be polymertzed in the form of l:heir anhy-
- 30 drides and subsequently hydrolyzed. The copolymers can be
formed of rnixtures of the unsaturated carboxylic acids with or
without other copolymerizable monomers, or they can be formed
from single unsaturated carboxylic acids with other copolymeriz-
-`` able monomers. In either case, the percentage by wei~3ht of the
.~a~ 35 polymer units derived from noncarboxylic acids is preferably less
than about 50~. Suitable copolymerizable monomers include, for
-
85~
-- 10 --
example, vinyl chloride, vinyl alcohol, furan, acrylonitrile, vlnyl
acetate, methyl acrylate, methyl methacrylate, styrene, vinyl
methyl ether, vinyl ethyl ether, vinyl propyl ether, acrylamidec
ethylene, propylene and 3-butenoic acid.
Homo- and copolymers of sulfonates, sulfates and phosphates
of suitable monomers such as styrene, vinyl alcohol, vinyl chlor-
ide, etc., are particularly useful in the practice of the invention~
Polystyrene sulfonate with a molecular weight in the range of from
about 2û00 to about 6000 is particularly useful in the practice of
the invention.
Other preferred polymers are the homopolymers and copoly-
mers of acrylic acid~ hydroxyacrylic acid, or methacrylic acid,
and salts thereof, which in the case of the copolymers contain at
least about 50%, and preferably at leas~ about 8096, by weight of
units derived from the acid. Particularly preferred poiymers are
sodium polyacrylate and sodlum polyhydroxyacryiate. The most
preferred is sodium polyacrylate. Other specific preferred
polymer~ are the homopolymers and copolymers of maleic
anhydride, especially the copolymers with ethylene, styrene and
vinyl methyl ether. These polymers are commercially available
under trademarks such as, for example, Gantrez AN.
The polymerization of acrylic acid homo- and copolymers can
be accomplished using free-radical initiators, such as alkali metal
persulfates, acyl and aryl peroxides, acyl and aryl peresters and
aliphatic azocompounds. The reaction can be carried out in situ
or in aqueous or nonaqueous soiutions or suspensions. Chain-
terminating agents can be added to control the rnolecular wei~ht.
The copolymers of maleic anhydride can be synthesized using any
of the types of free-radical initiators mentioned above in suitable
solvents such as benzenc or acetone, or in the absence of a
solvent, under an inert atmosphere. These polymeri7ation tech-
niques are well known In the art. It will be appreciated that
instead of using a single polymeric aliphatic car~oxylic acid,
mixtures of two or more poly neric aliphatic carboxylic acids can
be used to prepare the above polymers.
~'
lZ~28S2
, .
, ij,
- 11 -
In general, natural polymers such as pectinr alginic acid,
gum arabic and carragheenan and cellulose derivatives such as
cellulose sulfate, carboxymethyl cellulose, hydroxypropyl cellulose
and hydroxybutyl cellulose are not particulariy effective in the
practice of the invention. Vinyl polymers without sufficient
ionizable sites are likewise not particularly effective. In general,
-` these deficiencies appear to be a result of a low ratio of ionizable
- sites to molecular weight or too high a molecular weight.
Optional Ingredients
Nonionic surfactants may be present in the compositions of
lthe inventio-~. Such nonionic materials include compounds pro-
duced by the condens3tion of alkyiene oxide groups ~hydrophilic
-` in nature~ with an organiG hydrophobiG compound, which may be
aliphatic or alkyE aromatic in nature. The len~th of the poly-
oxyalkylene group which is condensed with any particular hydro-
phobic group can be readily adjusted to yielcl a compound having
the desired degree of balance between hydrophilic and hydropho-
bic elements.
Suitable nonionic surfactants include the polyethylene oxide
condensates of alkyl phenois, e.g., the condensation products of
alkyl phenols having an alkyl group containin~3 from 6 to IS
- carbon atoms~ in either a straight chain or branched chain con-
figuration~ with from about 3 to about 12 moles of ethylene oxîde
per mole of alkyl phenol.
Preferred nonionics are the water-soluble condensation
products of aliphatic alcohols containing from ~ to 22 carbon
- I atoms, in either straight chain or branched configuration r with
from about 3 to about 12 moles of ethylene oxide per mole of
alcoholO Particularly preferred are the condensation products of
alcohols having an aikyl group containing from about 9 to 35
carbon atoms with from about 4 to 8 moles of ethylene oxide per
mole of alcoholL
Suitabie semi-polar nonionic surfactanls include: (1 ) wa~er-
soluble amine oxides containing one alkyl moiety of from about 10
to 18 carbon a~oms and 2 moieties selected from the group con-
sisting of alkyl groups and hydroxyalkyl groups containing from I
.,
- 12 -
- to about 3 carbon atoms, (2) water-soluble phosphine oxides con-
~, taining one alkyl moiety of about 10 to 18 carbon atoms and 2
-' moieties selected from the group consisting of alkyl groups and
hydroxyalkyl sroups containing from about I to 3 carbon atoms
and ~3) water-soluble sulfoxides containing one alkyl moiety of
from about 10 to 18 carbon atoms and a moiety selected from the
~-~ group consisting of alkyl and hydroxyalkyl moieties of from about I to 3 carbon atoms.
Water-soluble salts of the higher fatty acidsF i.e., "soapsl',
can be used In the composi~ions herein. This includes alkali
metal soaps such as the sodium, potasslum, ammonium, and alkyl-
olammonium salts of higher ~atty acids containing from about 8 to
about 24 carbon atoms~ and preferably from about 12 ~o about i8
car~son atoms. Soaps can be made by direcl: saponification of fats
-- is and oils or by the neutralization of free fatl:y acids. Particulariy
``~ useful are ~he sodium and potassium salts of the mixtures of ~at~yacids derived from coconu~ oil and tallow, i.e., sodium or potas-
sium tallow and coconut soap.
Cationic surfactants can be utilized in compositions of the
present invention. A preferred cationic surfactant iâ a quat-
ernary ammonium compound with one long chain alkyl and three
`~; short chain aikyl groups such as dodecyltrimethylammoni-sm chlor-
ide.
;j, Optional surfactants are ~referably separated from the inti-
mate admixture of non soap anionic surfactant and polymer but
may be present in the admlxture in non-interferin~ amounts such
~" that the overall anionic character of the admixture is maintained.The detergent compositions of the invention can optionally
contain water-insoluble aluminosilicate ion exchange material of the
3 0 formu la
Naz[ (AIO2)z (S jO2)y~ DxH2O
wherein ~ and y are at least about 6, the molar ratio of z to y is
rom about 1.0 to about ~.5 and x is trom about 10 to about 264.
Amorphous hydrated aluminosilicate materials useful herein have
the empirical formula
Mz(zAl02 ySiO2)
-~ wherein M is sodium, potassium, ammonium or substituted ammon-
.
.:~
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~Z~Z8S2
.
.
-- 13 --
~ . ium, z is from about 0 . 5 to about 2 and y is î, said material
- having a magnesium ion exchange capacity of at least about 50
-' milligram equivalents of CaC:O3 hardness per gram of anhydrous
`` aluminosilicate.
The aluminosilicate ion exchange builder materials herein are
in hydrated form and contain from about 10% to about 28% of water
by weight if crystalline, and potentially even higher amounts of
water if amorphous. Highly preferred crystalline aiuminosilicate
ion exchange materials contain from about 18g6 to about 22% water
in their crystal matrix. The crystalline aluminosilicate ion ex-
chanye material~ are hlrther characterized hy a particle size
diameter of from about 0.1 micron to about 10 microns~ Amor-
phous materials are often smallerr e~gO~ down to less than abou~
`~- OoOI micron. Preferred ion exchange materials have a particle
- 15 size diameter of from about 0.2 micron ~o abou~ 4 microns~ The
'.! term "particle size diameter" I:erein represents l:he average par--~ ticle size diameter of a given ion exchange material as determinedby conventional analytical techniques such as, for example,
microscopic determination utilizing a scanning electron microscope.
The crystalline aluminosilicate ion exchange materials herein are
: usually further characterized by their calcium ion exchange
~`'t capacity, which is at least about 200 mg. equivalent of CaCO3
water hardness/g. of aluminosilicate~ calculated on an anhydrous
basis, and which generally i5 in the range of from about 300 mg~
eq. /g . to about 352 mg O eq. /g . The aluminosilicate ion exchange
materials herein are still further characterized by their calcium
ion exchange rate which is at least about 2 grains Ca /gallon/
minute/gramlgallon of aluminosilicate (anhydrous basis~, and
generally lies within the range of from about 2 grains/gallon/
minute/gram/gallon to about 6 grainslgalion/minutel~ram/gaiion,
based on calcium ion hardness. Optimum aluminosilicate ~or
builder purposes exhibit a calcium ion exchange rate of at least
-~ about 4 grains/gallon/minu~e/gram/gallon.
- The amorphous aiuminosilicate ion exchange materials usually
35 have a Mlg exchange capacity of at least about 50 mg. eq.
CaCO3/g. (12 mg. Mg +/g. ~ and a Mg exchange rate of at least
abcut I grain/gallon/minute/gram/gallon. Amorphous materials do
, ~
,~
,~_
.
Z85Z
-- 14 --
not exhibit an observable diffraction pattern when examined by
Cu radiation (1.54 Angstrom Units).
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 struc-
ture and c2n be naturally-occurring aluminosilicates or synthet-
.~. ically derived. A method for producing aluminosilicate ion ex-
change materials is discussed in U.S. Patent 3,985,669, Krummei,
et al.~ issued October 12, 1976,
Preferred synthetic crystalline aluminosilicate ion exchange ma-
terials useful herein are available under the designations Zeolite
?~ A, Zeolite E~, and Zeolite XO In an especially preferred embodi-
ment, the cryst21iine aluminosillcate ion exchange material has the
~ormuia
Nal21AlO2)l2(sio2)l2] XH2
wherein x is from about 20 to about 30, especially about 27.
Other ingredients commonly used in detergent compositions
can be Included in the compositions of the present invention~
These include color speckles, bleaching agents such as perborates
and percarbonates and bleach activators, suds boosters or suds
suppressors, anti-tarnish and anti-corrosion agents, soil sus-
pendir)g agents, soil release agen1s, dyes, fillers, optical
brighteners~ germicides, pH adjusting agents, non-builder alka-
linity sources, hydrotropes such as toluene sulfonates and xylene
sulfonates, enzymes, enzyme-stabilizing agents, perfumes and
water.
The detergent compositions of the present invention can
comprise a portion of compositions containing a wide variety of
materials suitable for detergent or other uses.
The following non-iimiting examples illustrate the detergent
compositions of the present invention.
All percentages, partsO and ratios used herein are by weight
unless otherwise specified.
EXAMPLL I
A slurry was prepared containing 30g6 of the sodium salt of
linear C13 alkyl benzene sulfonate (sodium C13 ~AS~, 3~ of a
copolymer of acrylamide and acrylate having a molecular weight of
1~)28S2
- 15 -
approximately 15,000 and an acrylamide content of about 12%, 15%
sodium sulfate and 52% water. The slurry was spray dried to
produce a granule containing an intimate admixture of the sodium
C13 LAS and the copolymer of acrylamide and acrylate. Water
content was reduced to less than 10~ by weight.
A granular detergent compo~ition was prepared containing
the following components:
Sodium nitrilotriacetate (NTA) 44
Sodium carbonate 9
Sodium silicate (SiO2.Na20=2.4) 5
Cl?_~3 alcohoi etho~cyiated with 6. 5 6
'; moles of ethy!ene oxide per mole of
alcohol
Sodium C13 LAS 15
Acrylamide/Acrylate copolymer l / S
Sodium sulfate 8
Water 7
Hydrous silica ~Zeosyi 2~0J 3.0
Mîscellaneous Balance
The NTA, sodium carbonate and sodium silicate in dry
particula~e form were placed in a ~arion Mixer Model 203G. After
I minute of mixing, the C12 13 alcohol-6.5 ethoxylate was added as
a spray and acted as an aggiomerating agenl:. An appropriate
~5 quantity of the granular mixture of sodium C131 AS, polymer and
sodium su3fate was then added foliowed b~ the hydrous silica.
The resultant granuiar detergent product is screened to remove
large lumps, if any. ~he final product had a densi~y of 0.67
grams per milliliter.
Entrapment Test
This method is used to determine the entrapment potential of
a granular detergent product relative to another comparison
product, the comparison product being a pre-established standard
which preferably has a consumer validated entrapment profile.
~, 35 The test is designed with conditions of high stress (low agitation,
low temperature, high product-to-fabric ratio) in order to maxi-
mize visual differences between products.
.~, * Trademark
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lZ'~852
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~; The entrapment test measures the ability or inability of agranular detergent to dissolve and disperse out of an encl3sed
fabric pocket cluring the course of a gentle wash cycle in a full
scale washer,
Equipment
Full scale washer - 'Kenmore' or G. E.
- ~ Black fabric ~ c 6" rectangles
Stapler
Procedure
The entrapment test is carried out in a full-scale washer
~" ~17.5 gal. flll) in 60F city water over a 10 minute gentle wash
cycle '(Kenmore'- 4~ 48 RPM, GE = 50 RPM) .
ID Four ~abric pockets are to be constructed ~ Two 4" x
6" rectangles of the black fabric are stapled ogether
along three sides to form an open pocket.
2. One-fourth of the recommended usage of the product to
be tested is placed in each of the four fabric pockets.
- 3. Each of the fabric pockets is stapled sllut along the
- lFourth side to form a closed pocket.
4. The washer is filled with 60F city water and the four
- pockets are added to the washer as agitation be~ins.
`: 5. Two pockets are removed from the washer at the end of
the wash-spin cycle; the other two pockets are removed
at the end of the rinse-spin cycle.
6. Pockets are squeezed lightly to remove excess water
and are blotted between paper towels to remove addi-
`.;t tional water~
7. The pockets are opened along 3 sides and spread open
- to air dry. Comparisons between products are made
after the pockets have dried completely.
Using the entrapment test, visual comparisons can be made
between products to determine relative dissolu~ion and solubility.
- The composition of Example I was compared ~o a composition
made by the same procedure but without the inclusion of the
!,. 35 acrylamide/acrylatè copolymer. The composition of Example i had
a substantial advantage as measured by the entrapment testO
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: ~ EXAMPLE l l
The composition of Exampie I was produced on an Aeromatic
`~` Spray Granulator Fluid Bed.
:~ The slurry of Example I containin~ the Sodium C13 LAS and
acrylamide/acrylate copolymer was sprayed on a fluidized bed of
:~ the NTA and sodium carbonate suspended with heated air. The
bed was allowed to cool and the rernaining ingredients were
added .
The resuitant granular detergent composition has physical
properties~ including rate of dissolution and density equivaient to
the composition of Example I and a substantial advantage solu-
bility over a product made without inclusion of the polymer
EXAAAPLE l l l
Surfactant Dispersibility Test
~: 15 Samples of spray-dried Ci3LAS wi~h il:s accompanying sodium
sulFate, both with ~lûg6) and witi~out the acrylamide/acrylate
- copolymer of Exampla i were tested by adding I gram o~ granules
Into 400 rnl of room temperature wa~er which was stirred slowly
: with a magnetic stirrer. The time required to dissolve the sample
witho~lt the polymer wa~ twice as long ~25 minutes) as the sample
with the polymer ~12 minutes)~ Additional evaulations using the
same procedure showed the foliowing results:
Table I
:~.`. Cl3LAS
~6 Polyacrylic Acid~MW=2000) ~ispersion Time (min)
19
: 1302 ll
2601~
52.9 0.33
Table l l
30% tallow aikyl sulFate
..~.
- 40~6 C12 LAS
tD 30% C12 15 alkyl 2.25 ethoxy ether sulfate
:.
~Z~21~2
1~ -
% Polymer of Example I Dispersion Time (min.)
0 11
16.8 7 5
40.9 2
Table 111
30~ tallow alkyl sulfate
~9~ C~12 LAS
30~ C12 15 alkyl 2.25 ethoxy ether sulfate
9~ P~iyacrylic Acicl ~MW=2000) Dispersion Time ~min.)
0 11
7.8 7.5
15.6 0.67
31 0.33
48 0,17
EXAMPLE IV
At a concentration of 40 . 7% of polymer in the paste, the
following molecular weight dependence of the dispersib-.lity of
sodium C13LAS with polyacrylic acid was obser~ed,
MW of Dispersion
Polyacrylic AcidTime (min.)
1000 less than ~
2000 1/2
5000 4 1/2 _ .
' 28
1,250,00Q 75
EXAMPLE V
The following composition was prepared:
Sodium linear C1 2 alkylbenzene sulfona~e,
Sodium Polyacrylate, and sodium sulfate
ftake (LAS/SPA) 7.10
' Dobanol 45 E7 'nonion ic surfactant
C14-1s aiCohol polyethoxy (7) 12.g7
Sodium tripolyphosphate (anhydrous)~5.60
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Sodium carboxymethylcellulose (CMC)1.22
Sodium siljcate 7,41
Maleic anhydride methyl vinyl ether
copolymer (Mwt 250,000) ~.33
Sodium perborate tetrahydrate 28.8
Magnesium sulphate 0-74
Fluorescer 0. 34
Enzyme 1 . 33
Suds suppressor (15% silical85% silicone) 0.34
Water ~ miscellaneous Balance
The sodium silicateO sodium tripolyphosphate, maleic
anhydr ide copolymer, CMCo magnesium sulphate and fluorescer,
were first formed into a crutcher mix of moisture content 42% and
spray dried to give a granular powder of density 650-670 gllitre
and moisture content of 7%O
This granular base powder was fed into a 311 diameter
Patterson-lCelley zig-zag blender and the nonionic surfactant
sprayed on at a temperature of 40C over a ~eriod o~ two min-
utes. Mixing was allowed to continue for a further 8 minutes
after which the powder density was 800-830 g/litre.
The sodium perborate, suds suppressor ingredients and
enzyme were then dry mixed into the nonionic containing powder
by means of a Vertomix in-line mixer (made by Babcock Gardner
Ltd., Middleway, St. Bla2eyO Cornwall, l~ngland)- resulting in a
powder of density 790-800 gllitre. The product was passed
through a 2û mesh sieve and the oversize r ecycled for further
size reduction. The LAS/SPA flake was made from an aqueous
slurry of solids content 50% by weight, in which the solids com-
prise 90% LAS paste, 10% sodiurn polyacrylate (Goodrite 1~-759, a
sodium polyacrylate of molecular wt. 2100 made by Cioodrich
Chemical Group, Cleveland, Ohio, USA).
This slurry was dried on rollers heated by 35 psi steam and
removed as a flake of thickness 0. 25mm comprising 8G% LAS, 10%
sodium polyacrylate, 7% sodium sulfate, 3~6 moistureu The flake
was broken up by 10 minutes agitation in a cube mixer and the
* Trademark
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~ ~ J
52
-- 20 --
portion passing through a 20 mesh sieve was used as a dry
additive in the product. Addition of the LAS/SPA flake to the
remainder of the product was carried out in a Vertomix, using
the same procedure as for the dry mixing of the other ingre-
dients, to give a finished product density of 750 grams/liter.
The finished product had a particle size distribution as
fol lows: -
On 14 Mesh Tyler 0g6
On 20 Mesh 2 . 8%
1 n On 36 M~sh 18 . 596
On 72 Mesh 39.2~
On 100 Mesh 14 . ~ ~6
On 1 5C Mesh 18 . ~%
Thrcugh ? 50 Mesh 7 . 0%
Dispersion and solubility of the finished product in water
was excellent.
The product of Exampie V is prepared with a LASISPA Flake
thickness of 0~10 mm and a LAS/SPA flake thickness of 0,50 mm.
Comparable dispersion and solubiiity is obtained.
ExAMpLE VI
The present invention is also helpful in reducing product
loss in the sump or drain plug connection of front loading
washing macilines. In such machines, the sump comprises the
drain p!ug which is located at the lowest point of the machine and
a shori: lengl:h o~ piping which connects~ the plug either to the
external casing or to part of the wash water recirculation system~
Product is added to the washing machine via a dispenser, the
contents of which are flushed by a stream of cold water into the
external casing of the maclhine at the star~ of the cycle. Any
component of ~he product havtng a low rate of soiubility in cold
water tends to collect in the sump and this tendency is enhanced
by the formation of viscous surfactant phases which cause
aggregation of other components. This tendency is particuiarly
noticeable when anionic sur~actant is dry mixed with the
remainder of the formulation and compositions in accordance with
the present invention can be shown to overcome this problem.
~Z()2~35Z
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The following compositions were prepared:
(a) A flaked composition comprising
88 . 9g~ NaLAS
7.8% Na2SO4 + miscellaneous
3 . 3~ H2O
~b) A fiaked composition comprising
809s NaLAS
10% Sodium polyacrylate Mw = 2000
7% Na2SO4 + miscellaneous
3% H2C
Both fiake compositi~ns were prepared as in Examp~e v
above. In a model test using a funnel fitted with a length o~
tubing tc simulate a washin~ machine sump and adapted to trap
undissolvecl mat~rial, the percentage of the initial ~rmu3ation
remaininy as a residue in the sump was:
Sample ~a) 17.1%
Sample ~b) 4.5%
