U.S. patent number 3,915,878 [Application Number 05/335,873] was granted by the patent office on 1975-10-28 for free flowing nonionic surfactants.
This patent grant is currently assigned to Colgate-Palmolive Company. Invention is credited to Bao-Ding Cheng, Robert E. Dickson, Pallassana Ramachandran, Joseph A. Yurko.
United States Patent |
3,915,878 |
Yurko , et al. |
* October 28, 1975 |
Free flowing nonionic surfactants
Abstract
A method for converting liquid nonionic surfactants to dry free
flowing form is disclosed. The new method includes the mixing of
the liquid nonionic material with specific particulate carrier
materials in amounts varying from 30 to 85 percent. Suitable
carrier materials include compounds having functional properties in
detergent formulations. The free flowing nonionic
surfactant-carrier pre-mix is very suitable for post-addition to
spray dried detergent formulations in order to increase their
content of nonionic surfactant.
Inventors: |
Yurko; Joseph A. (Bayonne,
NJ), Ramachandran; Pallassana (Robinsville, NJ), Cheng;
Bao-Ding (Highland Park, NJ), Dickson; Robert E.
(Bellemead, NJ) |
Assignee: |
Colgate-Palmolive Company (New
York, NY)
|
[*] Notice: |
The portion of the term of this patent
subsequent to October 30, 1990 has been disclaimed. |
Family
ID: |
26811801 |
Appl.
No.: |
05/335,873 |
Filed: |
February 26, 1973 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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114073 |
Feb 9, 1971 |
3769222 |
Oct 30, 1973 |
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Current U.S.
Class: |
510/349; 510/443;
510/506 |
Current CPC
Class: |
C11D
3/124 (20130101); C11D 1/72 (20130101); C11D
11/0082 (20130101) |
Current International
Class: |
C11D
3/00 (20060101); C11D 3/12 (20060101); C11D
11/00 (20060101); C11D 1/66 (20060101); C11D
3/26 (20060101); C11D 001/72 (); C11D 011/00 () |
Field of
Search: |
;252/89,99,135,546,DIG.1 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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918,499 |
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Feb 1963 |
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GB |
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709,515 |
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May 1954 |
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GB |
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807,640 |
|
Jan 1959 |
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GB |
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511,415 |
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Mar 1955 |
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CA |
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Other References
Schue, "Detergents and Specialties," 6, No. 3, pp. CT 18, 21, 22
& 24 (March 1969)..
|
Primary Examiner: Padgett; Benjamin R.
Assistant Examiner: Miller; E. A.
Attorney, Agent or Firm: Koch, Esq.; Kenneth A. Grill, Esq.;
Murray M. Sylvester, Esq.; Herbert S.
Parent Case Text
Related Applications
This application is a continuation-in-part of copending application
Ser. No. 114,073 filed Feb. 9, 1971 and entitled Free Flowing
Nonionic Surfactants, and now U.S. Pat. No. 3,769,222 issued Oct.
30, 1973.
Claims
We claim:
1. In the method of preparing a heavy duty detergent which includes
the step of spray drying a detergent slurry to form a dry, free
flowing powder, the improvement comprising adding to said spray
dried powder a free flowing premix consisting of from 62 to 85
percent by weight of a liquid nonionic surface active agent chosen
from the group consisting of ethoxylated alcohols having a 12 to 18
carbon atom chain and an average of from 10 to 19 ethylene oxide
units and at least 5% by weight of microsized silica particles,
said premix being prepared by mixing said liquid nonionic with a
sufficient quantity of silica particles to fully solidify said
liquid nonionic.
2. The improved method of claim 1, wherein said premix contains
from about 65 to about 75% by weight of said nonionic.
3. The improved method of claim 1, wherein said micro-sized silica
particles are chosen from the group consisting of silica gels,
silica aerogels, precipitated silicas and pyrogenic silicas.
4. The free flowing particulate product produced by the method of
claim 1.
Description
The invention pertains to heavy duty particulated detergent
formulations that include anionic, cationic, or nonionic surface
active agents and detergent builders. More specifically the
invention provides heavy duty detergents having a relatively high
content of nonionic surface active agent.
The most commonly used surface active agents in heavy duty
detergent formulations are anionic compounds having detersive
properties. Typical of these anionic compounds are the higher alkyl
mononuclear aromatic sulfonates such as the higher alkyl benzene
sulfonates. These synthetic detergents are very effective in
removing dirt from textile fabrics when utilized in conjunction
with phosphate builders which function to "soften" the water being
used and to provide detersive action. However, considerable
controversy exist today as to the efficacy of utilizing phosphate
compounds in detergent formulations due to their alleged causation
of the eutrophication process in lakes, rivers and streams.
Although the eutrophication process, wherein an excessive growth of
plant life is promulgated in natural water bodies, is not
completely understood, it is alleged that the phosphate compounds
present in detergent containing waste water are a prime factor in
promoting this phenomenon.
Although nonionic surfactants are not as effective as anionic
surfactants in the presence of large amounts of phosphate builders,
it has been discovered that when the phosphate content of a
detergent formulation is substantially reduced, the nonionic
surfactants appear to provide detergency properties that are
superior to anionics in the same reduced phosphate content
formulation. Apparently the detersive effectiveness of nonionic
surfactants is affected much less by water hardness than that of
the commonly used anionic surfactants. In the event that phosphate
builders are totally or partially removed from detergents, the
incorporation of greater and greater amounts of nonionic
surfactants into detergent formulations will become very
desirable.
At present, small amounts of nonionic surfactants are added to
detergent formulations, primarily to reduce the amount of foam
generated during the washing cycle. The most commonly used nonionic
surfactants are long carbon chain alcohols ethoxylated with
ethylene oxide. Typically, the nonionic ethoxamer used has a 12 to
18 carbon atom alkyl chain and an average of about 10 to 19
ethylene oxide units. The range of ethylene oxide content that
provides the greatest detergency in these surfactants usually
results in a nonionic material that is a viscous liquid at room
temperature and therefore unsuitable for direct addition to the dry
detergent powder. However, it has been found that when a
substantial amount, typically above about 5% by weight, of nonionic
surfactant is incorporated into the detergent slurry before spray
drying, a significant air pollution problem is encountered. This
problem, known in the industry as "pluming", is manifested as a
dense black smoke being discharged from the spray tower.
The primary objective of the present invention is to provide a
method for converting liquid nonionic surfactants to dry free
flowing particulate form so that they may be post added to spray
dried detergent formulations and thereby significantly increase the
nonionic surfactant content of the final detergent product. The
maximization of the nonionic surfactant content of the post addable
free flowing powder and the selection of particularly suitable
carriers for the nonionic materials are important further
objectives of the invention.
The present invention provides a method for obtaining free flowing
particulate materials having a nonionic surfactant content of up to
about 85% by weight, and preferably above 30% by weight, and most
preferably, between 62 and 85% by weight. The new materials are
very suitable for post addition to spray dried detergent powders in
order to substantially raise the nonionic surfactant content of the
finished detergent product. In order to achieve an optimum post
additive mixture for spray dried detergent fomulations, it is
desirable to maximize the loading of nonionic surfactant on the
chosen carrier and also to choose carriers that contribute to the
efficacy of the detergent product. The invention provides a
specific carrier materials for nonionic surfactants that are
capable of high nonionic loadings; some of which also contribute
functional characteristics to the detergent formulation.
In accordance with the invention, it has been found that
particulate silica substances in general, and microsized silicon
dioxide particles in particular, are capable of carrying a high
loading (about 85% by weight) of nonionic surfactant without losing
their free flowing characteristics. Pursuant to this aspect of the
invention, a method for preparing free flowing particulate premix,
including a high loading, preferably from 62 to about 85% by
weight, most preferably about 65 to 75% by weight, of liquid
nonionic surface active agent and microsized silica particles is
provided. The premix is particulary suitable for addition to a
detergent powder formed by spray drying a detergent slurry
according to well known procedures, to produce a final formulation
having a desirably high content of nonionic surface active agent.
The premix is advantageously produced by mixing the nonionic with a
sufficient amount of microsized silica particles to result in a
free flowing powder. The amount of microsized silica particles used
to solidify the nonionic into free flowing form is above 5% by
weight of the mixture, usually between more than about 5% by weight
up to about 38%, preferably about 25%, by weight.
Since microsized silicon particles are used as an anti-caking agent
in some detergent formulations, its use as a liquid nonionic
carrier provides anti-caking properties as well as higher nonionic
content to the detergent formulation it is ultimately combined
with. Further the aforementioned silica substances, when added to a
mixture of nonionic surfactant and other carriers, in accordance
with the invention, substantially increases the maximum nonionic
loading of the resulting post addable, free flowing mix.
Other desirable carriers for liquid nonionic surfactants are
substances having building properties in the detergent
formulations. In view of the desirability of reducing, and if
possible eliminating, the phosphate content of detergent
formulations, the use of other builders in conjunction with a
higher concentration of nonionic surfactant is advantageous. In
this regard it has been found that certain non-phosphate detergent
builders are suitable carriers for liquid nonionic surfactants.
Representative of these builder-carrier substances are the sodium
salts of nitrilotriacetic acid (NTA), sodium carbonate and sodium
citrate. Loadings of up to about 50% by weight of nonionic
surfactant have been obtained with these builder-carriers either
individually or in combination with each other in multi-component
systems. The nonionic loading of these builder-carriers can be
increased to over about 60 weight percent by adding a small amount,
typically about 5 percent by weight, of a silica substance,
preferably microsized silicon dioxide particles to the blend.
Although pyrogenic microsized silicon dioxide particles are
preferred in the practice of the invention other microsized silicon
dioxide particles such as silica gel and diatomaceous silica have
given satisfactory results.
In further accordance with the invention, certain peroxygen
bleaching agents have been found to be suitable carriers for
nonionic surfactants while still retaining their free flowing
properties. Peroxygen bleaching agents are advantageous carriers
for liquid nonionic surfactants when it is also desirable to
include a bleaching component in the final formulation. This is
particularly so when only one post addition operation can be
performed since both post additives can be added simultaneously in
accordance with this aspect of the invention.
In the following examples maximum loadings of liquid nonionic
surfactant were applied to various particulate carriers. The
maximum loading was determined by adding increasing amounts of
nonionic to a given amount of carrier until the resulting mixture
could not be solidified into a free flowing powder. In examples
1-14 the nonionic surfactant utilized was an ethoxylated long chain
alcohol having a chain of 12 to 16 carbon atoms and 10 to 12
ethylene oxide units. A suitable ethoxamer is available from the
Shell Chemical Company under the trademark NEODOL 45-11. NEODOL
45-11, according to its manufacturer, is a 14 to 15 carbon chain
ethoxylated fatty alcohol having an average of 11 ethylene oxide
units. The microzied silica particulate material used is available
under the trademark Cab-O-Sil, grade EH-5 from the Cabot Company.
Cab-O-Sil is a sub-microscopic particle size silica prepared by
vapor phase hydrolysis of silicon tetrachloride at 1100.degree.C.
All experimental runs were made at room temperature and atmospheric
pressure. Other suitable microsized silica materials are available
under the following trademarks: silica aerogel available from the
Monsanto Chemical Company, Quso which is a precipitated silica
which has a surface area of about 325 square meters per square
meters per gram and Syloid 244, which is a low density gel
available from W. R. Grace Company.
Example 1
Fifty grams of molten nonionic surfactant was heated to slightly
above room temperature until clear appearance and then sprayed onto
10 grams of colloidal pyrogenic silicon dioxide. The resulting
mixture was a free flowing powder having a nonionic loading of
83.3% by weight. The following techniques were used.
1. The liquid nonionic was sprayed onto a laboratory dish
containing the silicon dioxide carrier and mixed with a spatula to
produce a free flowing powder.
2. The liquid nonionic surfactant was sprayed into an air filled
plastic bag in which the silicon dioxide particles were suspended
by air currents.
3. The liquid nonionic surfactant was sprayed into a twin shell
rotating blender containing the silicon dioxide particles.
The solidification mechanism of the foregoing procedures is
believed to involve the coating of the liquid surfactant particles
by the microscopic silicon dioxide particles rather than the
absorption or adsorption of the liquid by the particles.
The free flowing powder produced by the foregoing method can be
post added to spray dried detergent powders or, detergent builders
and other detergent ingredients can be added to the nonionic powder
to produce a finished detergent formulation.
An example of the latter procedure is to first prepare a free
flowing powder consisting of 250.0 grams of a liquid nonionic
surfactant and 50.0 grams of silicon dioxide carrier (83.3 weight
percent nonionic). To this blend 100.0 grams of sodium salts of
(NTA) and 100.0 grams of sodium citrate when added and blended to
produce a finished deterent formulation having the following
approximate composition:
nonionic surfactant 50 weight percent silicon dioxide 10 weight
percent sodium salt of NTA 20 weight percent sodium citrate 20
weight percent
This later formula can be utilized as a detergent itself or as an
additive to other detergent systems.
Example 2
The liquid nonionic surfactant was slowly added to a laboratory
mortar containing any one or a combination of the following
inorganic particulate materials: sodium carbonate, clays (such as
bentonite and zeolite), diatomaceous earth (Celite Filteraid
available from Johns-Manville Company) or aluminum oxide. Upon
blending the liquid nonionic and the inorganic particulate material
with a pestle, partial solidification of the mixture occurs. Upon
setting at room temperature for about one hour a free flowing
powder is obtained.
Using the foregoing method, liquid nonionic loadings as high as 50%
by weight can be obtained without impairing the flowability of the
resulting solid particulate material.
Example 3
Colloidal pyrogenic silicon dioxide, in various amounts, was
thoroughly mixed into the partially solidified mixture of Example 2
before final setting. Nonoinic surfactant loadings of from 50 to 80
weight percent (based on the total inorganic content) were obtained
when from about 5 to 25 percent by weight pyrogenic silicon dioxide
was added to the mixture. Representative free flowing compositions
obtainable by this method are:
nonionic 58.9 weight percent bentonite 23.5 " SiO.sub.2 17.6 "
100.0 nonionic 60.0 weight percent sodium carbonate 35.0 "
SiO.sub.2 5.0 " 100.0
Example 4
From 50 to 80 weight percent of the liquid nonionic surfactant was
blended with a mixture of 15 to 45 weight percent of an organic
nitrogenous compound chosen from the group consisting of melamine,
glycine and iminodiacetic acid and from 0 to 50 percent by weight
of any one or a mixture of the inorganic carriers of Example 2.
Upon mixing, partial solidification occurs. The addition of at
least 5 percent by weight of colloidal pyrogenic silicon dioxide
and subsequent thorough blending results in solidification of the
mixture. The solidified mixture can be broken up into a free
flowing, non-caking powder. The following free flowing powder
compositions have been obtained by the foregoing method:
(1) nonionic 63.6 weight percent melamine 18.1 " SiO.sub.2 18.3 "
(2) nonionic 70 weight percent sodium salt of glycine or imino- 20
" diacetic acid SiO.sub.2 10 " (3) nonionic 80 weight percent
sodium salt of 3 " glycine or imino- diacetic acid bentonite 7 "
SiO.sub.2 10 " (4) nonionic 80 weight percent sodium salt of 10 "
glycine or imino- diacetic acid SiO.sub.2 10 " (5) nonionic 80
weight percent sodium salt of 3 " glycine or imino- diacetic acid
SiO.sub.2 15 "
Example 5
The procedures and compositions of Example 4 were followed except
that a non-nitrogenous organic material chosen from the group
consisting of sodium glycolate, glycolic acid, sorbitol, and
potassium sodium tartrate, was substituted for the nitrogen
containing organic compounds. The following free flowing powder
formulations were obtained by the foregoing method:
(1) nonionic 50 weight percent bentonite 30 " sodium glycolate 10 "
SiO.sub.2 10 " (2) nonionic 60 weight percent zeolite 13 " sodium
glycolate 10 " SiO.sub.2 17 " (3) nonionic 66.6 weight percent
potassium sodium 16.8 " tartrate SiO.sub.2 16.6 " (4) nonionic 50
weight percent sorbitol 24 " SiO.sub.2 26 " (5) nonionic 70 weight
percent glycolic acid 10 " SiO.sub.2 20 " (6) nonionic 80 weight
percent sodium glycolate 8 " bentonite 2 " SiO.sub.2 10 " (7)
nonionic 70 weight percent sodium glycolate 20 " SiO.sub.2 10 " (8)
nonionic 70 weight percent sodium glycolate 10 " aluminum oxide 10
" SiO.sub.2 10 "
Example 6
The liquid nonionic surfactant was mixed with trisodium
nitrilotriacetate and sodium citrate-2H.sub.2 O. Partial
solidification occurred on mixing. Pyrogenic silicon dioxide was
then added and thoroughly mixed with the partially solidified mass.
Full solidification of the mixture occurred. The resulting solid
was then broken up into a free flowing, non-caking powder. The
following composition has been obtained by the foregoing
method:
nonionic surfactant 56.6 weight percent sodium salt of NTA 13.0 "
sodium citrate 13.0 " SiO.sub.2 17.4 "
The resulting free flowing powder is very suitable for post
addition to a spray dried detergent powder. Similar free flowing
powder can be obtained without the addition of SiO.sub.2 by
reducing the nonionic content to about 30 percent by weight.
Example 7
The liquid nonionic surfactant was mixed with sodium carbonate and
the sodium salt of NTA. Partial solidification occurs on mixing.
Pyrogenic silicon dioxide was then added and thoroughly blended
with the partially solidified mass. Full solidification of the
mixture resulted. The resulting solid was then broken up into a
free flowing non-caking powder.
The following composition has been obtained by the foregoing
method:
nonionic surfactant 60.0 weight percent sodium salt of NTA 15.0 "
sodium carbonate 15.0 " SiO.sub.2 10.0 "
The resulting free flowing powder is very suitable for post
addition to a spray dried detergent powder.
Example 8
35 weight percent of liquid nonionic surfactant is blended together
with 65 weight percent sodium perborate monohydrate. The resulting
mixture is a free flowing powder suitable for post addition to
spray dried detergent formulations.
Attempts to use sodium perborate tetrahydrate as a carrier for the
liquid nonionic yielded a tacky non-flowable powder with a nonionic
liquid content of about 20 percent by weight.
Example 9
A free flowing particulate material having a nonionic surface
active agent content of 68% by weight can be prepared by the
following procedure: 68 grams of Neodol 45-11 was heated to
slightly above room temperature until molten and clear in
appearance. The molen nonionic surface active agent was slowly
added to 32 grams of Cab-O-Sil EH-5, a micro-sized silica powder,
and the combination was mixed by mechanical stirring for about 5
minutes. The resulting product is a free flowing powder.
Example 10
The procedure of Example 9 can be repeated using 62 grams of Neodol
45-11 and 38 grams of Cab-O-Sil EH-5 to produce a free flowing
powder having a nonionic loading of 62% by weight.
Example 11
The procedure of Example 9 is repeated using 75 grams of Neodol
45-11 and 25 grams of Cab-O-Sil EH-5 to produce a free flowing
powder having a nonionic loading of 75% by weight.
The free flowing products produced by Examples 9-11 are ideally
suitable for post addition to a detergent powder made by spray
drying a detergent slurry according to well known procedures in the
detergent art. Final detergent formulations produced by combining
spray dried detergents with the free flowing particulate pre-mixes
of the invention can comprise from about 10 to about 50% of the
post-added premix component to provide a wide range of nonionic
content depending on the nonionic loading of the premix and the
requirements of the particular application.
Example 12
320 grams of a particulate silica material sold under the trademark
Santocel, which is a silica aerogel, was introduced into a Hobart
mixer. The stirrer was turned on (low speed) and 680 grams of a
nonionic surface active agent (Neodol 45-11) in molten form was
slowly poured onto the silica material over a period of about 2
minutes. Sirring was continued for another 5 minutes at low speed.
The resulting product was a free flowing particulate material
having a nonionic loading of 68% by weight.
Example 13
The procedure of Example 12 was repeated using a particulate silica
material available under the trademark Quso. Quso is a precipitated
silica having a surface area of 325 m.sup.2 /gram and a 5% water
content. The resulting product was a free flowing particulate
material having a nonionic loading of 68% by weight.
Example 14
The procedure of Example 12 was repeated using a particulate silica
material available under the trademark Syloid 244. Syloid 244 is a
low density silica gel. The resulting product is a free flowing
particulate material having a nonionic loading of 68% by
weight.
Runs similar to Examples 1-14 can be made using liquid nonionic
surfactants having a longer alkyl chain than Neodol 45-11, i.e.
16-18 carbon atoms, and a higher ethylene oxide content, i.e. an
average of 19 ethylene oxide units. A suitable liquid nonionic
meeting these requirements is available from the Continental Oil
Company under the trademark Alfonic 1618-78. It was found that,
Alfonic 1618-78 can be solidified with less effort, i.e. in less
time, than Neodol 45-11 and to approximately the same loadings.
Functional carriers that can be heavily loaded with nonionic
surfactants and still remain free flowing, non-caking powders were
found to include pyrogenic silicon dioxide, which functions as an
anti-caking agent in the final formulation, and various detergent
builders such as NTA, sodium carbonate and sodium citrate. When it
is desired to incorporate a peroxygen bleach component into the
detergent formulation, in addition to a nonionic surfactant
component, it has been found that sodium perborate monohydrate is a
surprisingly good carrier for the nonionic component since both can
thereby be added in one post addition operation. Further, the
addition of a small amount of pyrogenic silicon dioxide to mixtures
of liquid nonionic surfactant and carrier material have been found
to significantly increase the nonionic loadings of the post addable
mixture while still retaining the necessary free flowing
characteristics.
Although phosphate detergent builders have also been found to be
very suitable carriers for liquid nonionic surfactants, their use
is not preferred at this time because of the alleged contribution
of phosphates to the eutrophication process in natural bodies of
water. However, in reduced phosphate content detergent
formulations, all or part of the phosphate builder can be added to
the formulation subsequent to spray drying as a carrier for
nonionic surfactants. In this regard, it has been found that
phosphate builders, such as the sodium tripolyphosphate can be
loaded with up to about 30 percent by weight liquid nonionic
surfactant while still retaining free flowing properties. In
accordance with the invention the nonionic loading on phosphate
carriers can be increased to about 50 percent by weight by adding
about 5 percent by weight of a microsized silica substance to the
nonionic-carrier mixture before final setting.
By providing a commercially feasible method for post adding liquid
nonionic surfactants to spray dried detergent formulations, the
invention represents a significant step towards the substantial
reduction of phosphate builders from detergent formulations without
a significant decrease in cleaning efficacy.
Although the foregoing specific embodiments are presently
preferred, they should not be considered as limiting the invention.
Accordingly reference should be made to the following claims to
determine the full scope of the invention.
* * * * *