Note: Descriptions are shown in the official language in which they were submitted.
2301-1315
This invention relates to a particulate built
nonionic synthetic organic detergent composition. More
particularly, it relates to such a composition containing a
building proportion, in combination, of polyacetal carboxyl~te
and carbonate and bicarbonate builders for the nonionic
detergent. The invention also includes processes for
manufacturing such products.
Particulate nonionic detergent products are known
wherein base beads, comprised mostly of inorganic builder
saltts), e.g., carbonatesand bicarb~nates, obtained by ~pray
drying an aqueous crutcher mix or s].urry, have normally
solid nonionic detergent in li~uid state absorbed ~y them,
to produce free flowing particulate compositions. Poly-
acetal carboxylate builder salts suitable for use as builders
with various organic deterqents, primarily anionic organic
detergents, have been described in the literature and in
various U.S. and foreign patents. ~owever, before the
present invention, particulate built nonionic synthetic
organic detergent compositions containing carbonate and
bicarbonate builder salts and polyacetal carboxylate in a
~,~
~i~
3~
total building proportion had not been disclosed and the
advantages of such compositions and of processes for their
manufacture,wherein the polyacetal carboxylate and ~onionic
detergent were applied to base beads of carbonate and bi-
carbonate builder salts,were not known.
Particulate nonionic detergent compositions in
which the nonionic detergent is applied in liquid state to
porous base beads containing carbonate and bicarbonate
builder salts are referred to in U.S. patent 4,269,722, and
such compositions have been marketed under the trademark
FRESH START~ They are especially useful as non-phosphate
or limited phosphate content detergents in those areas where
high phosphate content detergent compositions are prohibited.
Polyacetal carboxylates are described in U.S. patents
4,144,226 and 4,315,092. U.S. patents 4,146,495 and 4,219,437
claim detergent compositions containing the polyacetal
carboxylate builder (4,146,495) and similar composi~ions
containing keto dicarboxylates (4,219,437), which can often
be employed in replacement of the polyacetal carboxylates.
Various other patents on similar builders include 4,141,676;
4,169,934; 4,201,858; 4,204,852; 4,224,420; 4,225,685;
4,226,960; 4,233,422; 4,233,423; 4,302,564; and 4,343,777.
Also relevant are European patent applications No's.
0 015 024; 0 021 491; and 0 063 399. Although in some such
patents and/or applications there are included broad teachings
~43~i~8 62301-1315
that polyacetal carboxylates may be included in various types
of detergent compositions, and although some such polyacetal
carboxylates are described as components of compositions con-
taininy nonionic detergents and cationic softening agents, none
of the references or combinations thereof describes or suggests
such polyacetal carboxylates as components of the nonionic
detergents of the present invention and none teaches the obtain-
ing of the described improved detergency of the invented compos-
itions and the free flowing nature of the products made. Also,
the present manufacturing processes are not described or fairly
suggested in any such reference or in any combination of the
references.
In accordance with the present invention a particulate
built, substantially phosphate-free synthetic organic detergent
composition which comprises 5 to 35% of a nonionic synthetic
organic detergent which is a condensation product of ethylene
oxide and a higher fatty alcohol, and 30 to 95%, in combination,
of polyacetal carboxylate builder for the nonionic detergent,
of weight average molecular weight in the range of 3,500 to
10,000, alkali metal carbonate, and alkali metal bicarbonate
with the ratio of polyacetal carboxylate to the combination of
alkali metal carbonate and alkali metal bicarbonate being in the
range of 1:5 to 2:1 and the ratio of sodium carbonate to sodium
bicarbonate being in the range of 1:3 to 3:1, and a balance of
the composition, if any being of filler or builder adjuvant or
moisture. Preferably, the product obtained is a free flowing
particulate built detergent composition of improved detergency
(or soil removing properties). Also within the invention are
processes for making such particulate detergents.
- 5 -
~3~
The polyacetal carboxylate may be considered to he
that described in U.S. patent 4,144,226 and may be made by
the method mentioned therein. A typical such produc~ will
be of the formula
Rl - (CHO)n - R2
COOM
wherein M is select~d from the group consisting of alkali
metal, ammonium, alkyl groups of 1 to 4 carbon atoms, tetra-
alkylammonium groups and alkanolamine groups, ~oth of 1 to 4
19 carbon a~oms in the alkyls thereof, n averages at least 4,
and Rl and R2 are any chemically stable groups which stabilize
the polymer against rapid depolymerization in alkaline
solution. Preferably the polyacetal carboxylate will ~e one
wherein M is alkali metal, e.g., sodium, n is from 50 to
15 200, Rl is
Cl~3CH2O MOOC
HCO- or H3C-CO-
~3C MOOC
or a mixture ~hereof, R2 is
OCH2CH3
CH
~3
and n averages from 20 to 100, more preferably 30 to 80.
~he calculated weight average molecular weights of the
polymers will normally be within the range of 2,~00 to
- 6 -
~43~4L8
20,000, preferably 3,500 to 10,000 and more preferably 5,000
to 9,000, e.g., about 8,000.
Although the preferred polyacetal carboxylates
have been described above, it is to be understood that they
may be wholly or partially replaced by other such polyacetal
carboxylate or related organic builder salts described in
the previously cited patents on such compounds, processes
for the manufacture thereof and compositions in which they
are employed. Also, the chain terminating groups described
10 in ~he various patents, especially U.S. 4,144,226, may be
utilized, providing that they have the desired stabilizing
properties, which allow the mentioned builders to be depoly-
merized in acid media, facilitating biodegradation thereof
in waste streams, but maintain their stability in alkaline
media, such as washing solutions.
The carbonate and bicarbonate builders are highly
preferably sodium salts but other water soluble alkali metal
carbonatesand bicarbonat~ may also be employed, at least
in part, such as those of potassium. Such may be in anhydrous,
hydrated or partially hydrated state. Sodium sesquicarbonate
may be used in partial or complete replacements of the
carbonate and bicarbonate. One of the advantages of the present
invention is that the sodium carbonate found in '~uilder U", the
available polyacetal carboxylate, is useful as a builder in the
detergent compositions made.
~Z'~3~
The fourthcomponent of the present detergent
compositions is a nonionic synthetic organic detergent or
mixture of ;uch detergents. While various suitable nonionic
detergents having the desired detersive properties and
physical char~c~eristics 5normally solid, at room tempera-
~ure, but liquefiable so as to be capable of being applied
to base beads in liquid form) may be employed, at least as a
part ~f suc,- de:ergent content of the invented compositions.
e-~ prefe~ ly the nonionic detergent will be a condensation
,odl t: oi e-~ le.le oxide and a higher fatty alcohol. The
e.thv ~ ne oxitle content of such det;ergents will be within the
- range o 3 to 20 moles, preferably 3 to 12 moles and more
prefer~ly 6 to 8 moles, e.g., about 6.5 or 7 moles of
ethylene oxide, per mole of fatty alcohol, and the fatty
alcohol will usually be of 10 to 18 carbon atoms, preferably
averaging 12 to 15 carbon atoms, e.g., about 13 or 14 carbon
atoms. Among other nonionic detergents that a~e also useful
are the ethylene oxide condensation products of alkylphenols
of 5 to 12 carbon atoms in the alkyl group, such as nonyl
~0 ?h~lol~ in which the ethylene oxide content is from 3 to 30
-- 8 --
~ 62301-1315
moles per mole, and condensation products of ethylene oxide
and propylene oxide, sold under the trademark Pluronic~.
Although essentially anhydrous products can be
manufactured and are useful, usually moisture will be present
in -the detergent composition, ei~her in free form or as a
hydrate, such as a hydrated carbonate. The presence of
such a hydrate helps to strengthen the detergent composition
particles and sometimes facilitates dissolving of such
particles in the wash water. For such ~easons, and to
facilitate manufacturing, moisture is preferably present in
the product.
In addition to the mentioned components, other
materials, such as a supplementing builder (sodium silicate)
and adjuvants may be employed. Also, in some cases condensa-
tion products of higher fatty alcohol and ethylene oxide of
greater ethylene oxide contents than 20 moles per mole may
be employed in substitution for some of the condensation
products of lesser ethylene oxide content. Thus, if it is
desirable to further improve flowability of a preferred
product a harder nonionic component, such as one of 21 to 50
ethylene oxide groups per mole, may be utilized in part, in
which case it will desirably be from 1 to 50%, usually more
preferably from 5 to 25% of the total nonionic detergent
content. Also, sodium silicate, which has a supplementing
building action and aids in inhibiting corrosion of aluminum
items in wash water containing the detergent composition,
.~
~Z'~3;~
will be of Na2O:SiO2 ratio in the range of about 1:1.6 to
1:3, preferably 1:2 to 1:2.6, e.g., 1:2.35 or 1:2.4.
Among th~ various adjuvants that may be employed
are colorants, such as dyes and pigments, perfumes, enzymes,
stabilizers, antioxidants, fluorescent brighteners, buffers,
fungicides, germicides, and flow promoting agents. If
desired, fillers, such as sodium sulfate and/or sodium
chloride, may also be present. Also among the "adjuvants"
are included various fillers and impurities in other components
of the compositions, such as Na2CO3 in the polyacetal
carboxylate (Builder U).
The proportions of the various components that
will result in the desired improved detersive properties
(pre-~iously mentioned) will normally be from 5 to 35% of
nonionic detergent, and from 30 to 95~ of a combination of
polyacetal carboxylate and carbonate and bicarbonate builders.
The ratio of the polyacetal carboxyLate to combined carbonate
and bicarbonate will be in the range of 1:5 to 2;1, prefer-
ably 1:5 to 3:2, and more preferably 1:4 to 1:1, e.g., about
1:2.2. Any balances of such compositions will be filler(s~,
other builder(s), adjuvant(s) and moisture. Usually the
nonionic detergent content willbe at least 5~ of the product
and the carbonate plus bicarbonate builders content will be
at least 15~, preferably at least 25~ thereof. The nonionic
detergent content will preferably be 10 to 30%, more prefer-
ably 10 to 20~, e.g., about 16~, the polyacetal carboxylate
will preferably be 10 to 40~, more preferably 12 to 30~, e~g.,
ab~ut 18 or 23%, and the total of carbonate and bicarbonate
will preferably be from 20 to 75%, more preferably 25 to 55~,
-- 10 --
~L2'~3~
e.g., about 41~,of the detergent composition. The ratio of
carbonate to bicarbonate will be within the range of 1:3 to
3:1, preferably 1:2 to 2:1 and more preferably 1:2 to 1:1,
e.g., about 1:1.5. Prefera~ly the percentages of carbonate
and bicarbonate will be within the ranges of 10 to 30% and
10 to 40b ~ respectiv~ly, more preferably being 10 to
20'~ and 15 to 35~, e.g., about 17;~ and about 24~. The moisture
content of the product will usually be from 1 ~o 20%, prefer-
ably 3 to 15~ and more preferably from 3 to 8%, e.g., about
4 or 5~. Such moisture content includes that which is remov-
able from the product in standard oven drying (105C. for two
hours). The sodium silicate content, when sodium silicate is
present, will be from 1 to 18~, preferably 5 to 15% and more
preferably 8 to 14~, e.g., about 13~. The total percentage of
adjuvants may range from 0 to 20~ but normally will be at the
lower end of such range, 1 to 10%, preferably 2 to 6~, e.g.,
about 4 or 5%, with individual adjuvant percentages usually being
~rom 0.1 to 5%, preferably 0.2 to 3%. In the foregoing descrip-
tion and elsewhere in the specification the percenta~es of
carbonate and bicarbonate given are on an "anhydrous" basis, and
do not include moisture that is removable by oven drying, as
described above. The content of filler(s) may be as high as 40g
in some instances but usually, if filler is present, the propor-
tion thereof will be in the range of 5 to 30%, often 10 to 25%.
The particulate detergent product of th~s invention
may be made by the method described in U.S. patent 4,269,722
and U.S. patent 4,144,226. Following such method, an aqueous
slurry is made which includes the particulate sodium carbonate
and sodium bicarbonate, sodium silicate, usually added as an aqueous
3~
solution, water, and any suitable fillers and adjuvants, such
as fluorescent brigh~ener and pigment, which are heat stable.
Sodium sulfate has been found to adversely affect flowability
of the detergent composition, when added to base beads with
nonionic deterqent,so its presence is sometim~s avoided. In
some instances the polyacetal carboxylate builder may be added
in the crutcher but because it has sometimes been found to be
of limited stability when processed at elevated ~emperature,
such builder is often post-added. Generally the crutcher
mix is at a solids content in the range of 40 to 70~ and is
heated to a temperature in the range of 40 to 70C. Anhydrous
or hydrated bicarbonate and carbonate or other suitable combined
form thereof, such as sodium sesquicarbonate, may be employed.
However, a major proportion of the nonionic detergent component
will not be preser.t in the crutcher; instead, it will be post-
added, and preferably the proportion of nonionic detergent
in the crutcher will be limited to about 4%, preferably 2~ or
less lon a final product basis), and most preferably, none, so
as to avoid loss of such detergent during the spray drying
operation. If agitation to produce uniformity of the slurry is
difficult, because of excessive gelation or thickening of the
mix, viscosity control agents, such as citric acid, magnesium
sulfate and/or magnesium citrate may be employed. Such thin-
ning agents will be considered to be within the group
designated "adjuvants". After thorough mixing in the crutcher
which may take from 10 minutes to an hourt the crutcher slurry
is pumped to a conventional spray drying tower~ either con-
current or countercurrent, in which it is dried by heated
- 12 -
L3~8
drying air at a temperature in the range of 200 to 500C~,
preferably ~00 to 350C. if the mix contains polyacetal
carboxylate, to produce globular spray dried particles of
sizes in the ra~ge of No's. 8 to 100 sieves, U.S. Sieve
Series. Such base beads are desirably porous, so as to be
capable of absorbing nonionic detergent, and such porosity
is due at least in part to the dccomposition of bicarbonate to
carbonate during spray drying, which produces "puffing" carbon
dioxide. Normally, from 20 to 80~ of the bicarbonate converts
to carbonate, depending on spray tower conditions.
The porous base beads resulting are introduc~d
into a suitable batch or continuous mixer or blender, such
as an inclined rotary drum (batch), in which they are post
sprayed at a suitable temperature at which the nonionic
detergent is liquid, usually in the range of 45 to 60C.,
preferably 45 to 50C. In one embodiment of the invented
process all the nonionic detergent, in liquid state and prefer-
ably at elevated temperature in the described preferred
range, is sprayed onto the moving surfaces of the mass of
base beads by means of an atomizing nozzle of conventional
type, and during mixing it penetrates into the interiors of
the beads, with some of nonionic detergent being near the
surface thereof. Then, without cooling to the solidification
point of the detergent, the polyacetal carboxylate builder,
in finely divided powdered form, as of particle sizes in the
- 13 -
~Z~3~8 62301-1315
range of 200 to 400 mesh (although coarser parti.cles as
large as No. 100, U.S. Sieve Series, may also be used),
is dusted onto the moving base beads, which now contain
absorbed nonionic detergent. Some of the finely divided
polyacetal carboxylate particles are drawn into the inter-
stices and cavities of the beads by the still liquid nonionic
detergent and others adhere to such detergent near the
surfaces of the beads, and are held to the beads as the
detergent is cooled to solidification. In such operation
the polyacetal carboxylate which is held to the base beads
inhibits the production of tacky product. At the same time,
the holding of it to the beads prevents stratification of
the product in its end use package during shipment and
storage.
Various adjuvants of the types that would normally
be post-added, such as enzyme powders and perfumes, may be
aclded with the polyacetal carboxylate powder or before or
after the powder addition. Usually, as with the nonionic
detergent, itis preferred to spray liquid components onto
the surfaces of the intermediate detergent composition
particles but in some instances, as is also the case witih
application of the nonionic detergent in liquid state to the
base beads, spraying is unnecessary and dripping of the
liquid also serves to distribute it satisfactorily and to
promote absorption of it into the porous particles. Powdered
-14-
~3~
materials being added are preferably in finely divided
powdered foxm, as described above for the polycarboxylate
builder~ but other particle size ranges may also be utilized
(as they may be for the builder), although in such cases the
results may not be as satisfactory. Also, instead of spraying
the liquid material onto spray dried base beads for absorption,
in some instances one may apply the liquid to granular (not
spray dried or agglomerated) mixed carbonate and bicarbonate
particles, but such is not usually as satisfactory because
such particles do not normally have the absorbing capacity
of spray dried base beads and are less uniform.
Instead of having post-applied powdered polyacetal
carboxylate particles adhered to liquid detergent that has
been applied to base beads, in another and preferred process
of this invention the builder is applied to the base beads
as a dispersion of ~he polyacetal carboxylate in the normally
solid nonionic detergent at elevated temperature and in
liquid state. In such application, some of the polyacetal
carboxyla~e builder may be dissolved in the li~uid nonionic
detergent but normally more of it is dispersed therein,
preferably in finely divided particles, such as those smaller
than 200 mesh, and preferably larger than 400 mesh. In such
applications the base beads may be heated initially to a
temperature like that of the liquid state detexgent being
applied but it has been found that although theoretically
- 15 -
~ 3~ 62301-1315
such an operation would be thought topromote greater absorption
of the detergent and polyacetal carboxylate builder, in practice
it is sufficient for the base beads to be at room temperature,
at which satisfactory absorption and quick cooling of the
product result. The dispersion of polyacetal carboxylate
builder particles in liquid state nonionic detergent is pre-
ferably sprayed onto a moving bed of base beads but sometimes
spraying is unnecessary, and mere dripping of the liquid
medium onto the base beads is satisfactory, and in some
instances it is enough merely to admix the base beads and
the dispersion together without any concern for the mode of
application of the liquid dispersion to the base beads being
required.
The temperature of the dispersion of polyacetal
carboxylate particles in a nonionic detergent may be such as
has been found to be suitable for use in the application
process described. Normally such temperature will be in the
range of 45 to 95C. but preferably, so as better to maintain
stability of the polyacetal carboxylate and to promote
quicker cooling after application thereof to the base parti-
cles, the temperature of application will be in the range of
45 to Ç0C., most preferably about 45 to 50 or 55C.
However, this depends on the solidification point of the
nonionic detergent, which will be the same as or lower than
the lowest temperature of such a range. Of course, with
-16-
-- ~2'~3;~
higher melting nonionic detergents the lower limit of the
range will be adjusted accordingly, usually being at least 2
and preferably at least 5 or 10 higher than the solidifica-
tion point. The polyacetal carboxylate will preferably be
of particle sizes, substantially all (usually more than 90~,
preferably more than 95~ and more preferably more than 98%)
of which are no larger than that which will pass through a
No. 200 sieve, U.S. Sieve Series (or a 200 mesh sieve).
However, larg~r sized particles may be employed but generallysuch
10 are not larger than 100 or 160 mesh. Preferably ~he particles
will be in the 200 to 400 mesh range, e.g., 200 to 325 mesh,
to promote penetrations into interstices of the base beads
and to promote better holdings to the surfaces thereof.
In the dispersions mentioned, in w~ich some of the
polyacetal carboxylate may be in solution, the proportion of
polyacetal carboxylate to nonionic detergent will normally
be in the range of 1:20 to 3:2, preferably 1:10 o 1:1 and
more preferably 1:2 to 1:1. However, such proportions may
be adjusted, depending on the formula proportions of the
polyacetal carboxylate and nonionic detergent desired to be
in the end product. Still, normally no more than three
parts of polyacetal carboxylate will be present with two
parts of nonionic detergent, and preferably such upper limit
will be 1:1. If more polyacetal carboxylate is desired in the
product formula it may be post-applied, as previously described,
- 17 ~
12~3~48
after absorption of some of the polyacetal carboxylate and
the liquid state nonionic detergent. While other materials,
including particulate materials, such as enzymes, may be
post-added, sometimes they may also be dissolved and/or
dispersed in the nonionic detergent, with the polyacetal
carboxylate and may be applied to the base beads together
with such builder and detergent.
In some cases, some (sometimes all) of the poly-
acetal carboxylate may be spray dried with the carbonate and
bicarbonate builders but in such instances the employment of
mild conditions will be desired, with special care being
taken not to allow buildup of product on the spray tower
interior walls, where the polyacetal carboxylate could be
decomposed. So long as the spray tower conditions are such
that the bead temperatures do not rise to a destabilizing
temperature for the polyacetal carboxylate employed, sp~ay
drying is feasible but because this cannot always be assured
in commercial spray drying processes, as a pra~tical matter
it is often preferable to post apply the polyacetal
carboxylate.
The product of the formulations given, prsduced by
any of the methods described, is satisfactorily free Plowing,
non-tacXy and non-caking despite its contents of nonionic
detergent and polyacetal carboxylate. The particles thereof
are regular in shape, approximating the spherical, and the
product is of desired bulk density (higher than the bulk
- 18 -
~ 3~'~8
density of usual spray dried products, which tends to be in
the range of 0.25 to 0.4 g./ml.), normally beil-g in the
range of about 0.5 to 0.8 g./ml., such as 0.6 to 0.7 g./ml.
Thus, smaller packages may ba employed, creating more avail-
able supermarket shelf space and facilitating home laundrystorage. The detergent composition made is an excellent
detergent, with improved cleaning power against a variety of
soils. Its detergency is greater than that of a control
detergent without the polyacetal carboxylate. Surprisingly,
the detergency of the present compositions is better than
that of a control, despite the fact that the proportion of
nonionic detergent in the control is higher. It should be
pointe~ out that the total ratio of builder is greater in
the "experimental" product, but then too, the ratios of
carbonate, bicarbonate and silicate builders are lower.
The following examples illustrate but do not 'imit
the invention. Unless otherwise indicated all temperatures
are in C. and all parts are by weight in the examples,
elsewhere in the specification, and in the claims.
-- 19 --
3~
EXAMPLE 1
Component Parts
Sodium carbonate (anhydrous) 16.6
Sodium bicarbonate 24.7
5 Higher fatty a].cohol polyethoxylate nonionic 15.2
detergent(l)
`~ Sodium polyacetal carboxylate [Builder U](2) 23.1
Sodium silicate solids tNa2O:SiO2 = 1:2.4) 12.9
Moisture 4.S
10 Enzyme powder (proteolytic enzyme, 200 mesh) 1.02
Fluorescent brightener (Tinopal*5sM Conc.) 1.53
Blue pigment (ultramarine blue) 0.16
Perfume 0.19
100.O
(1) Condensation product of 6.5 moles of ethylene oxide and
one mole of higher fatty alcohol of 12 - 13 carbon
atoms sold as Neodol 23-6.5 by Shell Chemical Company
(2) Supplied by Monsanto Company (as Builder U), having a
calculated weight average molecular weight of about
8,000, and of about 80~ active polymer content.
The particulate detergent composition of the above
formula is made by spray drying some of the formula, includ-
ing the sodium carbonate and sodium bicarbonate to produce
base beads, and then post-blending with such bas~ beads
other components of the formula, including the nonionic
* Trade Mark
- 20 -
3Z~S
detergent, polyacetal carboxylate, enzyme and perfume. The
crutcher mix or slurry is made by sequentially adding to a
detergent crutcher 35.6 parts of water (preferably deionized
water but city water of up to 150 p.p.m. CaCO3 equivalent
may be employed), 7.0 parts of natural soda ash, 32.3 parts
of industrial grade sodium bicarbonate, 23.6 parts of a 47.5%
aqueous solution of sodlum silicate of Na2O:SiO2 ratio of
about 1:2~4, 1.3 parts of fluorescent brightener (Tinopal
5BM Conc.) and 0.3 part of ultramarine blue pigment, and
mixing at a temperature of about 45C. during such additions
and for about 20 minutes thereafter, after which th~ crutcher
slurry, of a solids content of about 45~, is dropped to a
high pressure pump which pumps it through atomizing nozzles
at the top of a countercurrent spray drying tower, in which
heated drying air at a temperature of about 325C. dries it
to essentially globular porous particles of sizes in the
No's. 10 to 100 sieves (U.S. Sieve Series) range, and of a
moisture content of about 7.6g. In some instances a minor
proportion of r~cycled base beads tor final product) may be
included in the crutcher mix for reworking, with appropriate
modifications of the formula to allow for such.
The base beads resulting, usually at about room
temperature but in some cases still at a temperature between
the tower bottom air temperature and room temperature, nearer
to room temperature (sometimes 5 to 30C. above it), are
charged to a blending apparatus, in this case an inclined
~Z~324~3
rotary drum, in which there are successively added to 78.41
parts of the base beads, 20.02 parts of the ethoxylated
alcohol nonionic detergent, 30 parts of ~uilder U~ 0.32
parts of enzyme and 0.25 part of perfume. The ethoxylated
alcohol is sprayed onto the moving bed of base beads at an
elevated temperature, 50C., at which it is in liquid state.
The Builder U and proteolytic enzyme (mixtures of amylolytic
and proteolytic enzymes, e.g., 1:1 mixtures, may also be
used) are "dusted" onto the moving bed of base beads after
absorption thereby of the nonionic detergent (which usually
occurs within about 2 to 10 minutes), after which th~ perfume
is sprayed onto such moving intermediate product. The
particulate detergent composition resulting is of particle
sizes in the range of No's. 10 to 100 sieves, U.S. Sieve
Series, and is of a bulk density of 0.65 g./ml. At room
temperature it is free flowing, non-tacky and non-caking.
After cooling and screening, if that is desired, to obtain
all or substantially all of the particles in the desired
No's. 10 to 100 sieve range, the pro~uct is packed, cased,
warehoused and shipped. It is found to be of uniform compo-
sition throughout the package and the contents of various
pac~ages are also uniform. It is also non-settling during
shipping and storage.
A comparative product is made in the same manner
as previously described except for the omission of the
22 -
62301-1315
sodium polyacetal carboxylate (Builder U) from it. Thus,
instead of 100.0 parts of product, 76.9 parts are made, and the
~roporations of the various components in the product are 30
greater than those given in the above formula. When the
"experimental" product is tested against the "control" for
detergency, in a standard soil removal test which utilizes
different soils deposited on a variety of substrate fabrics, the
invented product is found to be significantly better in soil
removal activity (or detergency) than the control.
In the detergency tests employed an automatic
washing machine containing ~7 liters of water at 49C. has
charged to it four pounds of clean clothes and three swatches
each of five different test fabrics. The first and second such
test fabrics are obtained from Test Fabric Company. The first
has a soil of graphite, mineral oil and thickener on nylon and
the second has a soil of sebum, particulate material and kaolin
on cotton. The third test fabric is cotton soiled with New
Jersey clay and the fourth fabric is a cotton-dacron blend
soiled with such clay. The fifth test fabric, identified as
EMPA 101, is of cotton and it is soiled with a mixture of sebum
soil, carbon black and olive oil.
After washing of sets of the test fabric swatches,
one set being washed in an automatic washing machine, to the
wash water of which the invented composition has been charged,
with the concentration thereof in the wash water being 0.07~,
the wash water being of a hardness of about 150 p.p.m., calcium
carbonate equivalent (Ca:Mg ratio of 3:2), and with the time
for the washing portion of the cycle being about 10 minutes,
-23-
~7-
~ 2'~3~
and the other set, to the wash water of which the control
composition has been charged, being washed subsequently in
the same machine, and after dryings, reflectances of the
swatches are measured and the averages for each soiled test
fabric are taken. ~tilizing different factors that have
been found by experience to be representative of human
evaluations of the importance of a detergent's cleaning
powers against the various soils, the final soil removal
indices are obtained for the experimental and control deter-
gent compositions. The soil removal index for the inventedpxoduct is 12.6 points higher than that for the control,
indicating a significant improvement in detergency for the
invented composition.
When, in the formulation of the invented product o~her
nonionic detergents are employed, such as Neodo~ 25-7, Alfonic~
1618-65, or a suitable ethylene oxide-propylene oxide condensa-
tion product such as those marketed under the trademark
Pluronic~, similar improved detergency results, compared to
a control from which the polyacetal carboxylate has been omi~ted.
Also, when parts of the sodium carbonate and sodium bicarbonate
are replaced by equivalent sesquicarbonate,e.g., 10 tQ 50~l
comparable results are obtained. ~his is also the situation
when the silicate employed is of Na2O:SiO~ ratio of about
1:2. Changes in the adjuvants utilized, such as omission
of the enzyme or replacement of it with amylolytic
- ~4 -
~Z43~
enzyme, or addition of relatively small proportions of
filler, such as NaCl and Na2SO4, or the presence of other
builders, such as zeolites, will result in the invented
products also showing the described type of improvement over
the control. This is also true when different polyacetal
carboxylates, such a~ those of potassium, ammonium, lower
alkyl and alkanolamine are present, of 1 to 4 carbon atoms
in the alkyls thereof, when the end terminating groups em-
ployed are others than the present ones, given in the preceding
formula, such others being those described in U.SO patent
4,144,226, and when the calculated weight average molecular
weights of the polyacetal carboxylate are 5,000 or other
weights within the described preferred range of 3,500 to
10,000. Of course, when the less desirable components are
employed the difference in detergency may not be as great.
Similarly, comparable results are obtained when
the manufacturing of tha product i9 effected in oth~r ways,
under different conditions, as previously described, and
utilizing components in different proportions, also as
previously described. For example, when the composition of
the formula is varied by ohanging the proportion8 o compo~ents
~10, +20 and +30~, while maintaining them within the ranges
given, similar results are ohtained.
EXAMPLE 2
Ten parts of Neodol 25-7 (a condensation product
of 7 moles oE ethylene oxide and one mole of higher fatty
- 25 ~
alcohol of 12 to 15 carbon atoms, on the averagP), and ten
parts of Builder U, of calculated weight average molecular
weight o about 8,000, are converted to a liquid state
dispersion-solution by first mixing them together and then
heating to about 49C. The builder powder, of particle
sizes in the range of 325 to 400 mesh, does not dissolve in
the hot nonionic detergent but disperses well therein. The
dispersion thus made is applied as a ~pray to or is dripped
(or sprayed) onto, at an elevated temperature within the
range of 45 to 55C., preferably about 50C., 30 parts of
base beads (in a moving bed) comprising 47% of sodium bi-
carbonate, 34% of sodium carbonate, 13% of sodium
silicate (Na2O:Sio2 = 1:2.4), 1.6% of magnesium sulfate,
0.6~ of sodium citrate (thinner), and 3.8~of water, The product
resulting is free flowing, non-caking and non-tacky, and
is of excellent appearance. When tested against a control,
from which the Builder U has been omitted, it is found to
be of significantly better detergency.
Similar results are obtainable when other carbonates,
bicarbonates nonionic detergents and polyacetal carboxylates
are employed, and in different proportions, within the
descriptions previously given.
To improve flowability, non-tackiness and non-
caking properties further, if desired, there may be dusted
onto the beads, after absorption of the nonionic detergent
- 26 -
~ ZL~ 4 8
and suilder U, about 5 parts of finely divided Zeolite 4A
or other suitable zeolite, or the zeolite, of particle
sizes like those of the builder, may also be dispersed in
the nonionic detergent and applied to the base beads with
the nonionic and builder. If zeolite is employed (and it
may be spray dried with the polyphosphate or dispersed in
the nonionic detergent, too) it will preferably be a Zeolite
A (4A is most preferred) of particle size of 200 to 400
mesh, preferably 325 to 400 mesh (if dispersed in nonionic
or post-applied) and the proportion thereof will ~e from
5 to 40%, preferably 10 to 20%, and the zeolite:nonionic
ratio will be from 1:20 to 1:1. The ratio of the sum of
~eolite and polyacetal carboxylate to nonionic detergent
will preferably be in the range of 1:10 to 1.1:1 or 1.2:1.
EXAMPLE 3
The procedure of Example 2 is repeated but the
composition is made by applying the Neodol 25-7, in liquid
state, at a temperature o 49C., to the moving base beads
by dripping (or spraying) it thereon, after which a finely
divided Builder U powder (200 to 400 mesh) is admixed with
the intermediate product. The powder adheres to the surface
of the nonionic detergent and the product resulting is free
f lowing, non-tacky, non-caking and non-settling on storage,
although without the addition of the Builder U the particles
are tacky and lazy. The detergency of the final product is
- 27 -
-
a3~
essentially the same (superior), compared to a control, as
that of ~he same composition of Example 2.
Variations in the formula of Examples 2 and 3 may
be made, as by utilizing different nonionic detergents, such
as those which have been described previously, and polyacetal
carboxylates of other types, previously mentioned. Variations
also can be made in the base bead formulations, as have been
described e~rlier. In all such instances, the product
xesulting will be satisfactory and will be of improved
detergenc~, compared to a control from which the polyacetal
carboxylate component has been omitted. In some instances,
as when the proportion of Builder U and/or nonionic detergent
employed is sufficiently high so that flowability could
desirably be improved, flow improving agents (zeolite
lS builders can perform such function? may be incorporated in
the final product, preferably by mixing them with the Builder
U and applying the mixture thereof to the base beads, already
containing deposited nonionic detergent in liquid state and
at elevated temperature, or by applying the flow-improving
agent after absorption by the base beads of the nonionic
detergent-polyacetal carboxylate dispersion. Alternatively,
some zeolite, e.g., 10 to 20% of the product, may be dispersed
in the nonionic detergent, too.
The mixing procedures and apparatuses may be changed
too. For example, instead of mixing for twenty minutes in a
- 2~ -
12~3~ 3
batch process employing an inclined drum, mixing time may be
changed to fxom 5 to 40 minutes! and other apparatuses may be
used, such as V-blenders, fluid beds, Schugi mixers and Day
mixers. The results from such changes will still be accept-
able product of the desired characteristics and washingproperties, with a desired bulk density being in the range of 0.6
to 0.8 g./ml., as in these working examples.
The invention has been described with respect to
various illustrations and working embodiments thereof but it
is to be understood that it is not limited to these because
one of skill in the art, with the present specification before
him or her, will be able to utilize substitutes and equivalents
without departing from the invention.
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