U.S. patent number 3,929,679 [Application Number 05/410,185] was granted by the patent office on 1975-12-30 for particulate silicate-hydroxyalkyl iminodiacetate built detergent compositions of improved properties.
This patent grant is currently assigned to Colgate-Palmolive Company. Invention is credited to Francis R. Cala.
United States Patent |
3,929,679 |
Cala |
December 30, 1975 |
Particulate silicate-hydroxyalkyl iminodiacetate built detergent
compositions of improved properties
Abstract
A particulate heavy duty synthetic organic detergent which has
improved aging properties includes a synthetic organic detergent of
the anionic or nonionic type or a mixture thereof and a builder
which is a hydroxyalkyl iminodicarboxylate hydrate. In preferred
compositions the iminodicarboxylate hydrate is disodium
2-hydroxyethyl iminodiacetate hexahydrate, the detergent is a
mixture of linear higher alkyl benzene sulfonate and higher fatty
alcohol polyethoxylate and the detergent composition includes
sodium silicate, sodium carbonate, sodium carboxymethyl cellulose,
sodium sulfate and moisture. The described products are of better
storage and aging properties than products of similar formulas in
which the iminodicarboxylate is present but not as a hydrate. Also
within the invention are methods for the manufacture of the
described compositions in which all the formula except the
iminodicarboxylate hydrate is spray dried from an aqueous crutcher
mix to globular particles which are then mixed with
iminodicarboxylate hydrate particles of similar sizes.
Inventors: |
Cala; Francis R. (Somerville,
NJ) |
Assignee: |
Colgate-Palmolive Company (New
York, NY)
|
Family
ID: |
23623606 |
Appl.
No.: |
05/410,185 |
Filed: |
October 26, 1973 |
Current U.S.
Class: |
510/349; 510/351;
510/357; 510/361; 510/443; 510/442; 510/356 |
Current CPC
Class: |
C11D
11/0082 (20130101); C11D 3/33 (20130101) |
Current International
Class: |
C11D
3/00 (20060101); C11D 11/00 (20060101); C11D
3/33 (20060101); C11D 3/26 (20060101); C11D
003/066 () |
Field of
Search: |
;252/527,532,540,546,383,384 ;260/534E |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Padgett; Benjamin R.
Assistant Examiner: Parr; E. Suzanne
Attorney, Agent or Firm: Sylvester; Herbert S. Grill; Murray
M. Blumenkopf; Norman
Claims
What is claimed is:
1. A particulate heavy duty synthetic organic detergent composition
which comprises 5 to 30 parts of anionic detergent and/or 1 to 10
parts of nonionic detergent and, as a builder therefor, 15 to 50
parts of a water-soluble salt of a hydroxy C.sub.2 -C.sub.4 alkyl
iminodi C.sub.2 -C.sub.4 carboxylic acid hydrated by 3 to 10 moles
of water per mole of iminodicarboxylate.
2. A heavy duty detergent composition according to claim 1 wherein
the builder salt is a dialkali metal iminodiacetate
polyhydrate.
3. A detergent composition according to claim 2 wherein the
iminodiacetate polyhydrate is disodium 2-hydroxyethyl
iminodiacetate hexahydrate.
4. A detergent composition according to claim 3 wherein the
particles of synthetic organic detergent are in the form of spray
dried beads.
5. A detergent composition according to claim 1 which comprises
from 5 to 30 parts of anionic detergent and/or 1 to 10 parts of
nonionic detergent, 5 to 30 parts of alkali metal silicate, 4 to 20
parts of alkali metal carbonate, 0.3 to 3 parts of organic gum
anti-redeposition agent, 1 to 20 parts of moisture, 5 to 40 parts
of alkali metal sulfate and 15 to 50 parts of builder salt
hydrate.
6. A detergent composition according to claim 4 which comprises
from 5 to 30 parts of anionic detergent, 1 to 8 parts of nonionic
detergent, 5 to 30 parts of alkali metal silicate, 4 to 20 parts of
alkali metal carbonate, 0.3 to 3 parts or organic gum
anti-redeposition agent, 1 to 20 parts of moisture, 5 to 40 parts
of alkali metal sulfate in the beads and 15 to 50 parts of disodium
2-hydroxyethyl iminodiacetate hexahydrate.
7. A phosphate-free and NTA-free detergent composition according to
claim 6 which comprises from 5 to 30 parts of sodium linear alkyl
benzene sulfonate, 1 to 8 parts of higher fatty alcohol poly-lower
alkoxylate detergent, 5 to 15 parts of sodium silicate of an
Na.sub.2 O:SiO.sub.2 ratio in the range of 1:2.0 to 1:2.4, 4 to 20
parts of sodium carbonate, 0.3 to 3 parts of sodium carboxymethyl
cellulose, 1 to 15 parts of moisture and 5 to 40 parts of sodium
sulfate in the beads and 15 to 30 parts of disodium 2-hydroxyethyl
iminodiacetate hexahydrate, with the particles being within the
range of 6 to 100 mesh.
8. A method of making a free flowing, particulate heavy duty
synthetic organic detergent composition which comprises 5 to 30
parts of anionic detergent and/or 1-10 parts of nonionic detergent
and, as a builder therefor, 15 to 50 parts of a water-soluble salt
of a hydroxy C.sub.2 -C.sub.4 alkyl iminodi C.sub.2 -C.sub.4
carboxylic acid hydrated by 3 to 10 moles of water per mole of
iminodicarboxylate, which comprises making particles of the heavy
duty synthetic organic detergent composition components exclusive
of the said builder salt and admixing with them particles of said
builder salt hydrate.
9. A method according to claim 8 wherein the builder salt is a
di-alkali metal iminodiacetate polyhydrate.
10. A method according to claim 9 wherein the builder salt is
2-hydroxyethyl iminodiacetate hexahydrate.
11. A method according to claim 10 wherein the organic detergent is
spray dried and after spray drying the particles of 2-hydroxyethyl
iminodiacetate hexahydrate are post-added and mixed with such
particles.
12. A method according to claim 11 wherein the spray dried
particles of the detergent comprise from 5 to 30 parts of anionic
detergent and/or 1 to 10 parts of nonionic detergent, 5 to 30 parts
of alkali metal silicate, 4 to 20 parts of alkali metal carbonate,
0.3 to 3 parts of organic gum anti-redeposition agent, 1 to 10
parts of moisture and 5 to 40 parts of alkali metal sulfate and/or
alkali metal chloride, to which are post-added particles of about
the same size of 2-hydroxyethyl iminodiacetate hexahydrate, after
which addition the particles are mixed.
13. A method according to claim 12 wherein an aqueous detergent
composition crutcher mix is spray dried to detergent beads of
particle sizes in the 6 to 100 mesh range, which beads comprise
from 5 to 30 parts sodium linear higher alkyl benzene sulfonate, 1
to 8 parts of higher fatty alcohol poly-lower alkoxylated
detergent, 5 to 15 parts of sodium silicate of an Na.sub.2
O:SiO.sub.2 ratio in the range of 1:2.0 to 1:2.4, 4 to 20 parts of
sodium carbonate, 0.3 to 1 part of sodium carboxymethyl cellulose,
1 to 10 parts of moisture and 5 to 40 parts of sodium sulfate and
such spray dried beads resulting are admixed with 15 to 30 parts of
disodium 2-hydroxyethyl iminodiacetate hexahydrate of particle
sizes in the 6 to 100 mesh range.
14. A method according to claim 13 in which additional nonionic
detergent, sodium silicate and sodium carboxymethyl cellulose are
post-added to the spray dried product, the silicate as an aqueous
solution and thereafter nonionic detergent being sprayed onto the
product surfaces in liquid droplet form and the sodium
carboxymethyl cellulose being admixed therewith as a finely divided
powder, with particles in the range of 100 to 200 mesh, during
tumbling of the beads, the proportions of silicate, detergent and
sodium carboxymethyl cellulose added being such that the total
proportions thereof in the product are 1 to 8 parts of higher
alcohol poly-lower alkoxylate, 5 to 30 parts sodium silicate and
0.3 to 3 parts of sodium carboxymethyl cellulose.
Description
This invention relates to heavy duty synthetic organic detergent
compositions and methods for their manufacture. More particularly,
it is of such detergent compositions which are of reduced caking
tendencies despite their contents of an iminodicarboxylate builder
salt which would normally be expected to cause caking of the
detergent or aging.
Synthetic organic detergent compositions, whether based on anionic
or nonionic organic detergent products, usually include a builder
salt to improve detergency. Various phosphates, borax compounds,
carbonates and silicates have been found to have building
properties and of these, the phosphates, especially pentasodium
tripolyphosphate, until recent years was acknowledged to be far
superior. However, due to opinions that phosphates in detergents
contribute to eutrophication of inland waters, causing excessive
algae growths, and because of government regulations, efforts have
been made to produce non-phosphate detergents including substitutes
for pentasodium tripolyphosphate. One such substitute, trisodium
nitrilotriacetate (NTA), is not being used in the United States
because of an interpretation of certain test results as indicating
that it would, under certain circumstances, be carcinogenic.
Experiments have been run using iminodicarboxylates as builders for
anionic and nonionic detergents in non-phosphate compositions and
while such materials allow the production of detergents which wash
satisfactorily, they possess other disadvantages which have
interfered with their large scale acceptance. In another patent
application, entitled MANUFACTURE OF IMPROVED AQUEOUS ALKALI METAL
SILICATE-ALKALI METAL HYDROXYALKYL IMINODIACETATE COMPOSITIONS,
filed by me concurrently with the present application, a method of
avoiding production of gels and precipitates when admixing
iminodicarboxylates and silicate components of detergent
compositions has been described. In addition to the gelation or
precipitation problem it has also been noted that the
iminodicarboxylates tend to become tacky or to cake on storage,
possibly due to hydrate formation. Therefore, the product used by
the consumer may be in unacceptable physical condition, being caked
into a solid or exhibiting a lumpy appearance. Accordingly, efforts
have been made to improve the caking and flow properties of such
detergents, leading to the discovery of the present solution which,
surprisingly, allows the production of the desired phosphate-free
built heavy duty detergent compositions based on iminodicarboxylate
builder salts by utilization of a hydrate of such
iminodicarboxylate and post addition thereof to the rest of the
detergent composition.
In accordance with the present invention a particulate heavy duty
synthetic organic detergent composition of reduced caking tendency
(compared to a control composition containing anhydrous
iminodiacetate) comprises a synthetic organic detergent selected
from the group consisting of anionic and nonionic synthetic organic
detergents and mixtures thereof and, as a builder therefor, a
hydroxyalkyl iminodicarboxylate hydrate. Preferably, the detergent
is phosphate-free and NTA-free and includes from 5 to 30 parts of
sodium linear higher alkyl benzene sulfonate, 1 to 8 parts of
higher fatty alcohol poly-lower alkoxylate detergent, 5 to 30 parts
of sodium silicate of an Na.sub.2 O:SiO.sub.2 ratio in the range of
1:2.0 to 1:2.7, 4 to 20 parts of sodium carbonate, 0.3 to 3 parts
of sodium carboxymethyl cellulose, 1 to 15 parts of moisture and 5
to 40 parts of sodium sulfate in spray dried detergent beads and 15
to 50 parts of disodium 2-hydroxyethyl iminodiacetate hexahydrate
in separate particles, all of the particles being within the range
of 6 to 100 mesh, U.S. Standard Sieve Series.
A method of manufacture of the desired detergents comprises making
particles of the heavy duty synthetic organic detergent composition
components exclusive of the hydroxyalkyl iminodicarboxylate,
preferably by spray drying such materials, and admixing with them
particles of hydroxyalkyl iminodicarboxylate hydrate of
approximately the same particle size, usually within the 6 to 140
mesh range.
The detergent compositions of the present invention include as a
primary detersive constituent an anionic synthetic organic
detergent or a nonionic organic detergent but preferably, these are
employed in mixture. The anionic detergent may include the various
materials listed in that category, as described in McCutcheon's
Detergents and Emulsifiers 1969 Annual, in which such compounds are
listed by chemical formulas and trade names. They may also include
those anionic detergents described in the test Surface Active
Agents and Detergents, Vol. II, by Schwartz, Perry and Berch
(Interscience Publishers, 1958). In short, such materials include
hydrophilic and lipophilic groupings, the lipophilic portions
whereof normally contain a higher hydrocarbyl chain, usually of 10
to 20 carbon atoms and the hydrophilic portions of which include a
salt-forming ion, preferably an alkali metal salt. Most of such
useful detergents are sulfates or sulfonates but corresponding
phosphates, phosphonates and other suitable detergent salts are
also useful. Included among the anionic detergents, for example,
are the linear higher alkyl benzene sulfonates, the branched chain
higher alkyl benzene sulfonates (although these are not usually
sufficiently biodegradable to be acceptable in modern detergent
formulations), the higher fatty alkyl sulfates, the higher fatty
acid monoglyceride sulfates, the higher olefin sulfonates, the
higher alkyl sulfonates, the sulfated phenoxy polyethoxyethanols,
the sulfated higher fatty alcohol poly-lower alkoxy alkanols,
paraffin sulfonates and the corresponding phosphates and
phosphonates. The hydrocarbyls, alkyls and higher fatty acyl groups
of such compounds will generally be of 12 to 18 carbon atoms and
the salt-forming ions thereof will preferably be alkali metal,
although alkanolamines and alkylamines may also be utilized. The
sulfated nonionics are preferably those in which the alkyls are of
two or three carbon atoms per unit. Specific exemplifications of
such compounds include sodium linear tridecyl benzene sulfonate;
triethanolamine lauryl sulfate; potassium stearate; sodium phenoxy
polyethoxyethanol wherein the polyethoxyethanol chain is of 15
units; sodium coconut oil fatty acids monoglyceride sulfate; and
potassium tallow sulfonate. Of these materials it is highly
preferred to employ the linear higher alkyl benzene sulfonates
wherein the alkyls are of 12 to 15 carbon atoms, most preferably
about 13 carbon atoms, and in which the salt-forming ion is alkali
metal, preferably sodium. The sodium salts tend to make harder
detergent products which are more freely flowing than those of the
alkylamines, alkanolamines and potassium. They also tend to cake
less.
Instead of the anionic detergents or in addition to them nonionic
detergents may also be utilized. These include condensation
products of higher fatty alcohols with polyoxy-lower alkylene
glycols, such as Neodol 45-11, Plurafac B-26 and Alfonic 1618-65.
Also useful, normally as a proportion of a nonionic detergent
content, are Neodols 25-3 and 25-7. Such compounds are
hydroxy-containing linear polymers of lower (1-4 C's) alkylene
oxides and are normally liquid or semi-solid at room temperature.
Also useful are the block copolymers of propylene glycol, propylene
oxide and ethylene oxide, such as the Pluronics, e.g., Pluronic
L-44 and Pluronic F-68; and the middle alkyl phenyl polyoxyethylene
ethanols, such as those sold as Igepals. Normally, the content of
nonionic detergents, such as those which are condensation products
of higher fatty alcohol and alkylene oxide, e.g., the Neodols of 12
to 15 carbon atoms in the higher fatty alcohol and including from 3
to 15 moles of alkylene oxide per mole of fatty alcohol, will be
less than the anionic detergent content of the product and
preferably will be about one-half or less of such content, e.g., 10
to 50% thereof.
Although the anionic detergents may be employed alone and solid
forms of nonionic detergents may be utilized by themselves, the
nonionic detergents are normally liquid or pasty in nature and do
not make as satisfactory primary detergent constituents as the
anionic compounds. Yet, they do contribute desirable cleaning
properties and accordingly, are preferably employed in admixture
with the anionic detergents, normally with the nonionic component
being present to a greater extent.
An important constituent of the detergents is the alkali metal
silicate component. Such compounds are water soluble and are useful
as builders for the synthetic organic detergents. They exert
alkalizing effects, help to counteract water hardness and have both
an independent detersive effect and the property of improving the
effect of the anionic and nonionic detergents utilized, especially
when these are employed in mixture. When the particular higher
fatty alcohol-poly-lower alkylene oxide nonionic detergent
condensates of the present invention are employed with the
silicates and linear higher alkyl benzene sulfonates a product can
be made which is comparable to previously highly superior
phosphate-built linear alkyl benzene sulfonate (LAS) compositions.
Additionally, the silicates have a corrosion inhibiting effect.
The silicates employed are water soluble. Of the inorganic
silicates those which are water soluble are the silicates of alkali
metals, e.g., sodium, potassium. Silicates of M.sub.2 O:SiO.sub.2
ratios are available in the range of 1:1 to 1:4 but for practical
purposes those which are used for detergent compositions are
generally of such ratios of 1:1.6 to 1:3, preferably 1:2 to 1:2.4
and most preferably about 1:2.0. In the preceding formulas M stands
for alkali metal, preferably sodium or potassium. The sodium
silicates are preferred for use in solid or particulate detergent
products and the potassium silicates are generally preferred in
liquid compositions, although, especially when mixtures are
utilized, either may be employed in both types of compositions.
The various silicates described are usually supplied as aqueous
solutions although it is within the present invention to employ
solid or particulate silicates too, normally after dissolving them
in water. The concentrations of the aqueous solutions will usually
be those which are as high as possible and at which the solution is
readily pumpable. Normally, from 20 to 50% by weight of sodium
silicate will be employed, preferably from 35 to 45% by weight
thereof. With respect to a preferred silicate, that of Na.sub.2
O:SiO.sub.2 ratio of 1:2.4, the concentration will most preferably
be from 40 to 45%.
Another detergent builder found to be highly desirable in the
non-tacky and free flowing particulate compositions is alkali metal
carbonate. This will normally be utilized in the anhydrous form but
hydrates such as washing soda may also be employed, providing that
the excess moisture will be removed therefrom during the drying
process. Alkali metal sesquicarbonates and bicarbonates may be
employed as substitutes for the carbonates providing that the
crutching and drying operations will essentially convert these to
the alkali metal carbonate. Of the alkali metals, e.g., sodium,
potassium, it is generally preferable to employ the sodium salt.
Sodium carbonate has the useful effects of increasing the pH of the
crutcher mix before spray drying and of giving the detergent
product and the wash water desirable high pH's. It also helps to
improve product flow and storage properties, serving to sorb
moisture without objectionable caking.
To improve the cleaning power of the detergent and to help to
maintain the beads in smooth, regular, globular and stable form an
organic gum anti-redeposition agent such as sodium carboxymethyl
cellulose, polyvinyl alcohol, hydroxymethyl ethyl cellulose,
polyvinyl pyrrolidone, polyacrylamide or hydroxypropyl ethyl
cellulose or mixtures thereof may be utilized. Such materials are
well known in the art and other equivalents need not be described
at length here.
Also of importance in improving flowability of detergent particles,
in addition to the carbonates, are the filler salts, which are
often used. These include primarily sodium sulfate and sodium
chloride, although other such alkali metal sulfates chlorides,
nitrates, borates, acetates, gluconates, citrates and many other
water soluble salts may be employed as fillers and in some cases
may have additional functions in the detergent, e.g., sequestering,
solubilizing and buffering actions. Finally, suitable adjuvants may
also be utilized such as sanitizers, e.g., trichlorocarbanalide;
coloring agents, e.g., dyes and pigments; foam improvers, e.g.,
lauric diethanolamide; foam depressants, e.g., silicones;
fungicides, e.g., polyhalosalicylanilides; antioxidants, e.g.,
stannic chloride; stabilizers; chelating agents; optical bleaches
or fluorescent brighteners; solvents; hydrotropes; and
perfumes.
The materials previously described may for the most part be
compounded together in a mixture and spray dried into homogeneous
detergent beads absent any iminodicarboxylate. In some cases it may
be desirable to post-add some of these materials or proportions
thereof and such processing method will be described at greater
length later herein.
The iminodicarboxylate compounds of this invention are water
soluble hydroxylalkyl iminodicarboxylates wherein the carboxyls are
of 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms and most
preferably from actetic acid. Such materials are found to be
excellent builders for synthetic organic detergents and have
desirable sequestering effects against water hardness ions, such
calcium and magnesium, which might otherwise interfere with
detersive actions of the organic detergent. The hydroxyalkyl
iminodiacetates generally employed are alkali metal salts, usually
diacetates, although other solubilizing cations may also be
present, at least in partial substitution for the alkali metal
salts. Of the alkali metal salts the sodium and potassium salts are
preferred, with the sodium salt being that of greater preference
for solid or particulate compositions and the potassium salts being
better for liquid preparations. Exemplary of other solubilizing
cations are mono-, di- and tri-alkanolammonium and mono-, di- and
trialkylammonium, where the alkyls and alkanols are lower, usually
of 1 to 4 carbon atoms and preferably of 1 to 3 carbon atoms, most
preferably being of 2 carbon atoms. Examples of such materials are
di-triethanolammonium 2-hydroxyethyl iminodiacetate and
di-monoisopropylammonium 3-hydroxypropyl-N-iminodiacetate.
Di-ammonium iminodiacetates substituted with the hydroxyalkyls are
also used.
The hydroxyalkyl of the hydroxyalkyl iminodiacetate is
hydroxy-lower alkyl wherein the lower alkyl is of 1 to 4 carbon
atoms, preferably of 2 to 3 carbon atoms and most preferably,
ethanol. Although the hydroxyl needs not be terminal on the ethyl,
for best effects this positioning is desirable.
Although the described iminodicarboxylates are available in
solutions and sometimes as anhydrous solids and are useful in such
forms in various detergent compositions or processes, in accordance
with the present invention it is important that the anhydrous form
not be utilized and that the iminodicarboxylates be present in the
final detergent compositions as hydrates. Such hydrates are usually
polyhydrates, of which the most preferred is disodium
2-hydroxyethyl iminodiacetate hexahydrate. Generally, the various
polyhydrates will contain from 3 to 10 moles of water per mole of
iminodicarboxylate.
The non-iminodiacetate portion of the detergent composition will
usually comprise from 5 to 30 parts of the anionic detergent and/or
1 to 10 parts of nonionic detergent, 5 to 30 parts of alkali metal
silicate, 4 to 20 parts of alkali metal carbonate, 0.3 to 3 parts
of organic gum anti-redeposition agent, 1 to 20 parts of moisture
and 5 to 40 parts of alkali metal sulfate and/or alkali metal
chloride in the particles or spray dried beads thereof. The
proportions of adjuvants and supplementing materials present in
such beads will usually not exceed 20% of the total composition
(including iminodiacetate), normally will be less than 10% and
preferably will be less than 5% thereof, with none of the
constituents being more than 5%, preferably with each being less
than 2% and most preferably, less than 1% thereof. Of course, some
of the less stable components of the particular detergents or those
which might interfere with drying or flow properties if dried with
the major proportion of detergent composition, may be added after
drying is completed. Most preferred proportions and materials are
from 5 to 30 parts of sodium linear higher alkyl benzene sulfonate,
1 to 8 parts of higher fatty alcohol poly-lower alkoxylate
detergent, 5 to 30 parts of a sodium silicate of an Na.sub.2
O:SiO.sub.2 ratio in the range of 1:2.0 to 1:2.4, 4 to 20 parts of
sodium carbonate, 0.3 to 3 parts of sodium carboxymethyl cellulose,
1 to 10 parts of moisture and 5 to 40 parts of sodium sulfate.
The other component of the final detergent product, the
iminodicarboxylate hydrate, should usually constitute about 15 to
50 parts, preferably 20 to 40 parts thereof. Such material, most
preferably disodium-2-hydroxyethyl iminodiacetate hexahydrate, may
be in separate pure iminodicarboxylate particles or may have filler
salts or other suitable such components of the total composition
mixed with it. Generally, it is preferred that the pure
iminodicarboxylate material should be utilized. In some instances
some of the iminodicarboxylate may be in the major proportion of
the detergent even in anhydrous or lower hydrate form but for
better flow and caking properties this should be only a minor
proportion of the total iminodicarboxylate builder content, e.g.,
less than 30%.
To avoid separation during storage and shipment, it is highly
desirable that the particles of detergent composition constituents
and those of iminodicarboxylate hydrate should be of about equal
particle sizes. Although various ranges of particle sizes utilized
in the detergent industry may be employed it has been found that it
is preferable that the particles be in the 6 to 140 mesh range,
U.S. Standard Sieve Series, preferably from 6 to 100 mesh. That
means that the particles will pass through the 6 to 8 mesh sieve
and rest on the 100 or 140 mesh sieve. With particles of such sizes
and of approximately the same particle size distribution little
settling results and the finished detergent is flowable and of an
acceptable degree of tackiness and tendency to cake in contrast to
similar compositions in which the non-hydrated iminodicarboxylate
is employed or in which an iminodicarboxylate solution is spray
dried or otherwise dried with the rest of the detergent
composition.
The products of this invention are preferably made by spray drying
most of the detergent compositions, except for the hydroxyalkyl
iminodicarboxylate, in a conventional spray drying apparatus so as
to produce beads of the desired particle sizes, 6 to 140 and
preferably 8 to 100 mesh. Such a spray operation is usually
effected by crutching an aqueous mixture of the various components
at an elevated temperature, e.g., 50.degree. to 90.degree.C. for a
suitable period of time, e.g., three minutes to one hour, and then
forcing the crutcher mix at high pressure, e.g., 200 to 1,000
lbs./sq. in., through restricted orifices so as to result in a
production of a spray of crutcher mix droplets into a spray tower
in which the droplets fall while being contacted by a
countercurrent hot air flow, which dries them. The crutcher mix
will usually contain from 20 to 50% of water and may include some
small solid particles which are pumpable through the spray orifices
at the high pressure. The orifices will be of a cross-section
equivalent to a circular area of 1 to 5 millimeters in diameter.
The drying air entering the spray drying tower will be of an
initial temperature in the range of 200.degree. to 500.degree.C.
and at exit from the tower will usually be at a temperature of
110.degree. to 200.degree.C. The detergent particles removed will
be of a moisture content of 1 to 20% and more often will be 15% or
less in moisture. The drying operation will be controlled, as by
drying gas temperatures and tower throughput rates, to make
detergent beads of such moisture contents that together with the
moisture in the iminodicarboxylate hydrate the moisture of the
product will be in the 1 to 20% range, preferably 1 to 15% and most
preferably about 1 to 10%.
The spray nozzle sizes and spraying pressures or atomizing means
employed will be chosen so as to produce particles of the desired
sizes for detergent compositions. Oversize and fine particles may
be removed by screening or other classification technique so that
the product is correctly sized. Such off-size particles may be
size-reduced or reworked so as to avoid waste.
In the crutching operation the order of addition of the mentioned
components is not critical but it is preferred to dissolve the
anti-redeposition agent gum in water or in an aqueous solution of
other constituent before addition to the main crutcher mix, to
avoid lumping or the production of hard gel sections in the
crutcher mix. Generally, water, liquid detergent, anionic detergent
solution, silicate solution and carbonate may be added in that
order, followed by the gum solution or dispersion and various heat
stable adjuvants. Any components which exhibit an undesirable
reaction to the heat of the crutcher or the spray drying operation
are preferably post-added.
In some cases proportions of components are crutched and the
remainders are post-added. For example, it has been found that
larger proportions of nonionic detergents, silicate and
anti-redeposition gum than 2% of the detergent (Neodol 45-11), 15%
of sodium silicate and 0.5% of carboxymethyl cellulose, on a final
product anhydrous basis may interfere with drying, flow and
non-caking properties of the product. Therefore, such materials
will be preferably limited in the crutcher mix to the amounts
mentioned. However, additional nonionic detergent or surface active
agent and aqueous solution of sodium silicate may be sprayed onto
particles after manufacture and additional sodium carboxymethyl
cellulose or other gum, in powdered form, may be admixed with them.
These operations preferably take place in a tumbling drum shortly
after production of the detergent beads. Such tumbling is
preferably at room temperature but is suitably effected at
temperatures above that, e.g., 30.degree. to 50.degree.C.
The extra operation of blending in powdered anti-redeposition agent
may be avoided in the present processes by maintaining the limit of
anti-redeposition agent at 0.5% or thereabout. It has been noted
that good anti-redeposition effects are obtained with such small
proportion of the agent, apparently due to additional
anti-redeposition properties of the iminodicarboxylate builder in
the present compositions.
The iminodicarboxylate hydrate is preferably in globule form and of
the same size distribution as the spray dried particles of the
other detergent constituents. Particles of this type may be made by
drying an iminodicarboxylate solution or slurry in conventional
spray drying equipment and then hydrating it by treating it with
water or by subjecting it to air of a relative humidity about the
same as or higher than the equilibrium humidity for the hydrate.
For example, when exposed to a humidity of from 65 to 75% at room
temperature, a preferred iminodicarboxylate, disodium
2-hydroxyethyl iminodiacetate, will take up moisture until it
reaches the hexahydrate stage. At relative humidities of 80% or
more, which are rarely encountered, if by itself the hydrate may
absorb water but in the present compositions sorption is minimized
and caking problems are not common. Considering that almost all
storage is at humidities less than 80% and at temperatures of
20.degree. to 27.degree.C., the employment of a hexahydrate in the
present detergent compositions substantially prevents caking of the
iminodicarboxylate and allows the production of a free flowing
product.
Instead of adding moisture to the anhydrous form by subjecting
spray beads to air of higher relative humidities, controlled
addition of water thereto may also be practiced. Solutions of the
iminodicarboxylate may be spray cooled to the hexahydrate form
while maintaining globular particle shapes. Alternatively, granular
hexahydrate may be made in manners known in the art and the
granules may be size-reduced to the proper particle size range,
with oversize particles and fines being removed. In a less
preferred application of the invention a powdered
iminodicarboxylate hydrate may be employed. Although the use of the
hexahydrate in this form avoids some of the caking problems noted
with the anhydrous iminodicarboxylate particles it introduces a
disparity in particle sizes which may, under extreme conditions,
cause sifting or settling and could make a boxed detergent product
heterogenous, so that poor washing effects would be obtained
because product employed would not have the proper balance of
detersive and builder components. Such balance is important because
the iminodicarboxylates improve the cleaning power of the organic
detergents and other builders and with either an excess or
deficiency of the iminodicarboxylate less desirable cleaning
results.
Although the preferred forms of both the detergent base particles
and the iminodicarboxylate builder particles are globular and in
the particle size ranges mentioned it is within the broader ambit
of this invention to utilize more finely divided or powdered
components. Normally, such components do not flow as readily and
have a greater tendency to cake during storage and so are not
preferred but by using the process of this invention, with
post-addition of the iminodicarboxylate hydrate, improvements in
flow properties are obtained and there is less of a tendency toward
caking. The "base" powder is preferably produced by drying a mix of
all the detergent components except the iminodicarboxylate but the
use of individual powdered materials is also within the broad
invention of improving flowability and caking properties by
post-addition of the iminodicarboxylate hydrate. Of course, where
components are liquid, they may either be mixed with powdered
carriers initially or may be blended with the powdered product at a
later stage in the production. In some manufacturing processes a
proportion, usually a minor proportion, generally less than 30%, of
the iminodicarboxylate may be mixed in with the other detergent
components before drying but there is generally little advantage in
following such a procedure and it is highly preferred that the
detergent "base" beads be free of iminodicarboxylate since such
material can hydrate during the storage and cause caking and poor
flow. In fact, post-adding of the iminodicarboxylate avoids a
manufacturing problem for which another solution is described in my
concurrently filed patent application entitled MANUFACTURE OF
IMPROVED AQUEOUS ALKALI METAL SILICATE-ALKALI METAL HYDROXYALKYL
IMINODIACETATE COMPOSITIONS. In short, the gelation or
precipitation often noted when iminodicarboxylate and silicate are
admixed is avoided by initially raising the pH of the
iminodicarboxylate solution to above 12, preferably to 12.5 to
13.5.
The admixing of the detergent base beads or particles and the
hydrated iminodicarboxylate may be effected by any convenient
means, the most preferable of which is an inclined tumbling drum or
a twin shell blender. The main consideration is that the mixing
apparatus should not unduly fragment the particles. In the mixing
apparatus, as was previously indicated, other components of the
detergent composition may be added in liquid, droplet, powder or
other form and additional quantities of components may be added. In
such cases it would be desirable to utilize materials of the same
particle sizes, whenever possible. Materials such as sodium
carboxymethyl cellulose may be agglomerated to particles of the
correct size, although it has been found acceptable to utilize this
material, in the small proportion in which it is present, as a
finely divided powder having particles in the range of 100 to 200
mesh. Preferably, all mixing, spraying and other forms of
treatments in the mixer will be at about room temperature.
The iminodicarboxylate particles made are added to the base
particles before or after addition of post-addition materials. The
post-addition substances may be added to either the
iminodicarboxylate or the base composition particles first and then
the other component particles may be admixed. In some instances, as
where starting materials include fines or are of particle sizes
smaller than desired, partial agglomeration may take place in the
tumbling drum, aided by the application of solutions of gums or
silicates, or nonionic detergents or surface active agents. In any
such cases, care will be taken to maintain the particles in the
desired range of sizes and to prevent any dehydration of the
iminodicarboxylate hydrate.
After production of the final detergent product it may be stored
prior to filling into cartons or may be directly filled. The
cartons used may be of moisture barrier or non-barrier types and it
has been found that in the ordinary, non-barrier cardboard cartons,
stored at room temperature, detergent compositions containing the
post-added hexahydrate are of a lesser tendency to cake on storage
than similar products in which anhydrous iminodiacetate is present
(made from a spray dried crutcher mix).
In use it is found that the products are excellent detergents,
effectively washing out soils of the various types normally
encountered, such as particulate (clay) soils, sebum soils, greasy
and carbonaceous soils, from cotton and synthetic organic
fiber-based materials and articles made from them. The
iminodicarboxylate builders function better in this respect than
all of the builder substitutes for pentasodium tripolyphosphate and
trisodium nitrilotriacetate that have been tried and the detersive,
soil-suspending and whitening effects of the present detergent
compositions are comparable to those obtained with phosphate-based
formulations, even at much higher levels of the phosphate (with
compensating lower levels of synthetic organic detergent content).
The products are competitive in price with other commercial
detergent formulations. Additionally, they do not contain excessive
quantities of potentially toxic or harmful constituents.
The following examples illustrate the invention but do not limit
it. Unless otherwise indicated, all parts are by weight and all
temperatures are in .degree.C.
EXAMPLE 1
Parts by weight ______________________________________ * Higher
fatty alcohol poly-lower alkoxylate 5 nonionic surface active agent
** Higher fatty alcohol poly-lower alkoxylate 3 detergent Linear
tridecyl benzene sulfonate, sodium salt 15 (90% active ingredient)
Aqueous sodium silicate solution (Na.sub.2 O:SiO.sub.2 36 1:2.35;
solids content = 44%) Sodium carbonate, anhydrous 13 Sodium
carboxymethyl cellulose 0.7 (85% active ingredient) Sodium sulfate
20 Water 7 ______________________________________ * Neodol 25-3S, a
higher fatty alcohol polyisopropoxylate made by Shell Chemical
Company, wherein the higher fatty alcohol is of 12 to 15 carbon
atoms and there are present three moles of propylene oxide per mole
of higher fatty alcohol. ** Neodol 45-11, a higher fatty alcohol
polyethoxylate made by Shell Chemical Company, wherein the higher
fatty alcohol is of 14 to 15 carbon atoms and there are present
eleven moles of ethylene oxide per mole of higher fatty
alcohol.
About four parts of the water are added to a detergent composition
crutcher, followed by the silicate solution, sodium carbonate,
anionic detergent, nonionic surface active agent, nonionic
detergent, and sodium chloride and the contents are mixed over a
period of about five minutes. The sodium carboxymethyl cellulose is
dissolved and dispersed in the remaining water and the aqueous
solution-dispersion is admixed with the rest of the crutcher mix.
After continuing mixing for an additional 5 minutes after all the
materials are present in the crutcher the mix is pumped by a
Triplex pump at a pressure of 600 lbs./sq. in. through a plurality
of spray nozzles, each of which has an orifice of about 1.5
millimeter diameter, into the top of a countercurrent spray drying
tower wherein the falling droplets of detergent composition base
are dried in heated drying air which passes upwardly through the
tower. The drying air has an initial temperature of about
400.degree.C. and a final temperature of 130.degree.C. The dried
beads have a moisture content of about 3%. The resulting product,
in the form of spray dried globules, is screened and sized so the
particles thereof pass through a No. 8 sieve, U.S. Standard Sieve
Series, and rest on a No. 100 mesh sieve.
After removal from the spray tower and cooling to a temperature of
about 40.degree.C., 100 parts of the spray dried detergent base
beads are added to a tumbling drum and 23 parts of disodium
2-hydroxyethyl iminodiacetate hexahydrate, in granular form of
particle sizes in the 8 to 100 mesh range, are mixed with tumbling
so as to evenly distribute them throughout the particulate mass.
Next, 0.15% of perfume is sprayed onto the particles and mixing is
continued until the perfume is completely distributed, which takes
about an additional minute beyond the 5 minutes earlier mixing
time.
In use it is found that the above composition is comparable in
detergency with high phosphate compositions based on 10 to 25% of
active anionic detergent and 30 to 45% of pentasodium
tripolyphosphate. Yet, the product is non-eutrophying and does not
contain any phosphates nor does it contain unusual quantities of
surface active agents, detergents, builders or anti-redeposition
agents. Utilizing standard concentrations of detergents in
automatic washing machines, 0.15% of the particulate detergent, the
product is tested and found to be acceptable, good or superior in
washing ability in both hot and cold water, in both hard and soft
water, and when tested against varying types of soils, including
clay soils, carbon soils, greasy soils, and phospholipid or sebum
soils, as compared to phosphate-containing commercial
detergents.
Compared to formulations in which the anhydrous disodium
2-hydroxyethyl iminodiacetate is employed instead of the
hexahydrate (with the proportions thereof being diminished to allow
for the extra water content of the hexahydrate), the present
products are of reduced caking tendency in non-barrier boxes or
cartons when subjected to normal use and aging conditions. They
flow more freely than "control" compositions based on the anhydrous
iminodicarboxylate, after storage in ordinary non-barrier boxes at
room temperature (20-27.degree.C.) and ordinary humidities
(30-60%).
Variations in the formula to increase or decrease the various
components within the ranges previously given result in the
productions of satisfactory detergent compositions, which are or
improved flowability and anti-caking properties, compared to
control detergents. Similarly, changes in the processing whereby an
additional 15 parts of sodium silicate solution are sprayed onto
the tumbling detergent beads and an additional 0.5% of sodium
carboxymethyl cellulose powder, in finely divided form (100 to 200
mesh) is blended in with the product after application of the
sodium silicate solution, also result in a product of improved
flowability and anti-caking properties, compared to the control. In
such compositions the moisture content of the base detergent beads
may be reduced to 0.5 to 1% initially, to compensate for the
additional moisture post-added with the silicate solution. When, in
addition to the processing changes described, the Neodol 25-3S is
omitted from the crutcher mix and the same proportion of Neodol
45-11, in liquid form, at an elevated temperature, is sprayed onto
the detergent and iminodicarboxylate beads after application of the
silicate, an equivalent product is made. Such product avoids the
problem of pluming from the spray tower of some of the nonionic
surface active and detergent materials when higher nonionic content
formulations (greater than 2%) are spray dried. Replacement of the
sodium sulfate with the potassium sulfate or mixtures of sodium and
potassium sulfates also makes a good product but it may tend to
cake slightly more. Use of sodium chloride instead of sodium
sulfate is acceptable when corrosion of metal equipment is no
problem. The products are also satisfactory detergents against the
various mentioned soils on the different types of fabric
substrates.
EXAMPLE 2
Parts ______________________________________ 2-1 2-2 2-3
______________________________________ Neodol 25-3S 0 4 0 Neodol
45-11 6 2 2 Sodium linear tridecyl 11 11 11 benzene sulfonate
Aqueous sodium silicate 15 12 12 solids (applied as a solution with
Na.sub.2 O:SiO.sub.2 = 1:2, solids content = 44%) Sodium carbonate,
anhydrous 10 10 10 Moisture 4 4 4 Disodium 2-hydroxyethyl 15 12 25
iminodiacetate hexahydrate Adjuvants (0.5 part sodium 2.3 2.3 2.3
carboxymethyl cellulose, 0.5 part calcined aluminum silicate
flow-improving agent, 1.0% fluorescent brightener mixture, 0.2%
perfume and 0.1% stabilizer) Sodium sulfate, anhydrous 36.7 42.7
33.7 ______________________________________
Repeated experimentation indicates that the best concentrations for
the sodium linear tridecyl benzene sulfonate, sodium silicate,
sodium carbonate, moisture and adjuvants contents are about 11%,
12-15%, 10%, 4% and 2-3%, respectively, with nonionic detergent
contents in 2 to 6% range and other anionic organic detergent
contents of about 0 to 4%. Concentrations of iminodiacetate
hexahydrate in the product are preferably in the 10 to 30% range,
preferably 12 to 25%.
The detergent compositions described above are made substantially
as related in Example 1, with the spray drying of the intermediate
products being effected after the described pre-mixing and with no
more than 2% of Neodol 45-11 being incorporated in the product
during spray drying operations. The hexahydrate is post-added also,
following the procedure of Example 1 and producing products of
about the same size. In some experiments the nonionic detergent is
completely post-sprayed onto the other particles, optionally with
sodium carboxymethyl cellulose (or with it being pre-mixed with the
intermediate), and the calcined aluminum silicate is dusted onto
the product afterward. In other experiments a proportion of the
nonionic detergent is post-sprayed and another proportion, up to 2%
thereof, is spray dried with the balance of the detergent
composition formula. Control runs are also made, using the
iminodiacetate in the final product, holding the final product
moisture content essentially the same (except for hydrate
moisture). The iminodiacetate may be employed in any suitable form
but usually will be the alkali metal salt (or as ions form such a
salt) in the completed crutcher mix.
The products made are compared for tackiness and caking. It is
observed that when stored in normal containers, without barriers,
under normal storage conditions (not excessively high
temperatures), there is a noticeable improvement in characteristics
of the final product. Control products, not utilizing the
hexahydrate, cake significantly worse and are much more difficult
to pour out of cartons. On the other hand, the compositions to
which the hexahydrate is post-added, whether with post-addition of
nonionic detergent or not, are of improved aging characteristics.
Although they can sometimes produce noticeable lumping, they will
flow much more freely than the "controls", after storage.
When the formulations given above are changed, substituting the
corresponding iminodipropionate or hydroxypropyl iminodiacetate,
useful detergents are obtained for which the hydrated
iminodialkanoates are of improved non-caking and subsequent flow
properties. This is also the case when the previously named anionic
detergents are substituted for the sum of the Neodol 25-3S and
sodium linear tridecyl benzene sulfonate and when proportions of
these specific detergents are halved and/or doubled. Similarly,
when Neodol 45-11 is replaced by Neodol 25-7, in minor part or is
partially or completely replaced by Plurafac B-26, Alfonic or
Conoco 1618-65, a mixture of Pluronics L-44 and F-68 or other
suitable nonionic detergent, essentially the same type of result is
obtained. This is also true when in the various experiments
described the proportion of carbonate is increased to 15% and when
5% of bicarbonate is added to the 10% of carbonate. Of course,
changing of the silicates to Na.sub.2 O:SiO.sub.2 ratios of 1:2.35
and 1:2.2 yields essentially the same types of products, too.
Instead of the sodium salts, a minor proportion of the total of
builder, detergent and filler salts may be replaced by the
corresponding potassium salts without harm to the production of an
acceptable product.
Although the product obtained is better than corresponding
non-phosphate built detergents that are allowed to be marketed in
the United States, with respect to cleaning and brightening
abilities, as shown in comparative testings against controls
containing no iminoalkanoate, and although there is a decided
improvement in subsequent flow and aging properties in non-barrier
boxes on ordinary storage, efforts are being made to improve the
aging characteristics of the detergent further, to which end starch
or other additional flow improving agent may be utilized and, in
some cases, the iminodialkanoate, either as a hydrate or as a
mixture thereof with the corresponding anhydrous form, may be at
least partially encapsulated to further diminish any tendency
toward caking or lazy flow after packaging.
EXAMPLE 3
The formulation of Example 2-3 is followed with the exception that
the proportion of sulfate is diminished 5% and that of the
hydroxyethyl iminodiacetate hexahydrate is increased 5% and the
iminodiacetate and nonionic detergent are post-sprayed onto and
post-mixed with the rest of the previously spray dried detergent
constituents. In similar experiments, the entire mixture is blended
together, without intermediate spray drying. Products made are
compared to controls in which the entire compositions are spray
dried. Subsequently, the products are stored in open jars for 3 and
7 days at 100.degree.C. and 80% humidity, after which time they are
observed for caking characteristics. It is found that the control
products are very heavily caked and in essence, are brick-like,
whereas the "experimental" products flow but contain some medium
sized lumps. Utilizing plant production equipment, lower initial
moisture content, encapsulating means, favorable carton designs and
improved storage conditions, the proportion of such caking is
diminished further.
From this experiment, the various modifications of the processes
thereof which may be carried out in accordance with the teaching of
the previous specification and the results thereof it is evident
that the use in these detergent compositions of hydrated
iminodialkanoates improves storage and subsequent flow
characteristics of the detergents. It does so without harming the
washing abilities or otherwise affecting the products and those
resulting are superior in washing power to other permissible
non-phosphate detergents and sometimes are superior to comparable
heavy duty built detergents based on pentasodium
tripolyphosphate.
The invention has been desribed with respect to examples and
illustrations of embodiments thereof but is not to be considered as
limited to them, since it will be clear to one of skill in the art
how to substitute equivalents and modify the operations without
departing from the spirit of the invention.
* * * * *