U.S. patent number 3,925,226 [Application Number 05/483,806] was granted by the patent office on 1975-12-09 for process for improving granulated detergents.
This patent grant is currently assigned to Lion Fat & Oil Co., Ltd.. Invention is credited to Fusao Kondo, Norihiro Ohno, Kuniyoshi Takenouchi.
United States Patent |
3,925,226 |
Takenouchi , et al. |
December 9, 1975 |
Process for improving granulated detergents
Abstract
A process for improving the properties of granulated detergents,
comprising adding a liquid perfume or lower alcohol to the
granulated detergent produced by the spray drying method while
making the detergent grains roll over, and subsequently adding
thereto metallic soap powder having a mean particle diameter of
less than 100.mu. when the surface of detergent grain has been
imparted with a sufficient adhesive power by virtue of the adhesion
of said liquid perfume or lower alcohol thereto.
Inventors: |
Takenouchi; Kuniyoshi
(Funabashi, JA), Ohno; Norihiro (Chofu,
JA), Kondo; Fusao (Chiba, JA) |
Assignee: |
Lion Fat & Oil Co., Ltd.
(Tokyo, JA)
|
Family
ID: |
26416036 |
Appl.
No.: |
05/483,806 |
Filed: |
June 27, 1974 |
Foreign Application Priority Data
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|
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Jul 4, 1973 [JA] |
|
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48-74863 |
Jul 4, 1973 [JA] |
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48-74864 |
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Current U.S.
Class: |
510/101; 427/212;
510/102; 510/441; 510/443; 510/359; 510/106; 510/324; 252/384;
427/214 |
Current CPC
Class: |
C11D
3/2006 (20130101); C11D 17/0039 (20130101); C11D
3/2041 (20130101); C11D 11/02 (20130101); C11D
3/50 (20130101); C11D 11/0088 (20130101) |
Current International
Class: |
C11D
3/50 (20060101); C11D 11/02 (20060101); C11D
11/00 (20060101); C11D 3/20 (20060101); C11D
17/00 (20060101); C11D 017/00 () |
Field of
Search: |
;252/91,92,381,384
;21/60.5 ;106/226,243 ;117/100 ;427/212,214 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Schulz; William E.
Attorney, Agent or Firm: Woodhams, Blanchard and Flynn
Claims
what is claimed is:
1. A process for improving the properties of granulated detergents,
which comprises adding a lower alcohol or liquid perfume to an
ordinary hollow granular detergent produced by the spray drying
method when the temperature of the detergent is lower than the
boiling point of the alcohol or perfume while making the detergent
grains roll over, and subsequently adding thereto a powder of a
water insoluble metal soap having a mean particle diameter of less
than 100.mu. when the surface of the grains has been imparted with
sufficient adhesive power by the addition of the alcohol or
perfume.
2. A process according to claim 1, wherein said lower alcohol is at
least one member selected from the group consisting of monohydric
alcohols having 1-4 carbon atoms and dihydric alcohols having 2-3
carbon atoms and the amount of said lower alcohol added is in the
range of 0.1-1 part by weight relative to 100 parts by weight of
the detergent.
3. A process according to claim 1, wherein said liquid perfume is a
member selected from the group consisting of linalool, terpinneol,
geraniol, eugenol, phenylethyl alcohol, benzyl alcohol and mixtures
thereof and the amount of said liquid perfume added is in the range
of 0.05-1 part by weight relative to 100 parts by weight of the
detergent.
4. A process according to claim 1, wherein said metallic soap is
selected from the group consisting of calcium and magnesium salts
of saturated fatty acids having at least 16 carbons and the amount
of said metallic soap added is in the range of 0.3-15 parts by
weight relative to 100 parts by weight of the detergent.
Description
BACKGROUND OF THE INVENTION
a. Field of the Invention
The present invention relates to a process for improving the
properties of granulated detergents produced by the conventional
spray drying method so as to make them retain the excellent
fluidity, hygroscopic solidification preventability and stable
preservability over a long period of time and also stabilize the
imparted perfume.
B. Description of the Prior Art
The majority of the prevailing granulated detergents are those
manufactured by the spray drying method (that is, a method of
obtaining dried grains in a short time by contacting sprayed
particles of a material slurry with a hot air, which employs either
the parallel-current process or the counter-current process in
effecting the contact between said particles and hot air) suitable
for mass production. Among these granulated detergents, the
so-called detergents for domestic use are ones prepared by the
spray drying method and further adding some perfume by spraying in
the state of liquid thereafter. However, the thus prepared
detergents for domestic use have been defective in that the
fragrance is apt to diminish in a relatively short period of time
and fail to last long.
Besides, though the conventional granulated detergents of the
foregoing type have a satisfactory water-solubility, they are
attended with troubles in respect of the hygroscopic solidification
preventability thereof, entailing some trobles in respect of the
stable preservability. The `hygroscopic solidification
preventability` herein means the property of detergent grains to be
free of solidification of absorbing moisture in the air. In other
words, a granulated detergent superior in hygroscopic
solidification preventability means such one as will hardly absorb
or never absorb moisture in the air and will maintain a granular
shape without getting solidified over a long period of time. The
conventional granulated detergents are inferior in said hygroscopic
solidification preventability so that hygroscopic solidification
would take place even after packing thereof in a carton case. Even
in the case where such solidification is somehow controlled, the
fluidity of the detergent grains per se is poor, entailing in
troubles on the occasion of taking out of the storing silo or
packing in the carbon case.
As a measure for overcoming these defects in the prior art, the
specification for U.S. Pat. No. 3,472,784, for instance, has
disclosed a method of obtaining a granulated detergent by adding
surface active agent and water to such inorganic builders for use
in detergent as sodium tripoliphosphate, soda ash, etc. while
admixing them by a ribbon mixer. And it is proposed to coat the
surface of detergent grains uniformly with tripoliphosphate, soda
ash or sodium sulfate. However, even these method has failed to
produce a satisfactory granulated detergent as desired. Not only
that, it has made no contribution to the improvement of the
fragrancy required especially of the granulated detergents for
domestic use in general.
SUMMARY OF THE INVENTION
One object of the present invention is to provide a process for
improving the fluidity and the hygroscopic solidification
preventability of granulated detergents. Another object of the
present invention is to provide a process for an everlasting stable
fragrance to said granulated detergents.
In other words, the process for improving the properties of
granulated detergents according to the present invention is
characterized by the steps of adding a lower alcohol or liquid
perfume as the binder to the surface of every grain of an ordinary
granulated detergent prepared by the spray drying method while
making the grain roll over, and subsequently adding thereto a
specific metallic soap powder when the surface of detergent grain
has been thus imparted with a sufficient adhesive power, thereby
letting said metallic soap powder adhere to the surface of
detergent grain.
To be more precise, the application of said lower alcohol (mainly
by the spray method) to the granulated detergent is for the purpose
of imparting adhesive power to the surface of detergent grain so as
to facilitate satisfactory adhesion of said metallic soap powder
thereto. And, the application of said liquid perfume (mainly by the
spray method) to the granulated detergent is for the purpose of
imparting adhesive power to the surface of detergent grain to
thereby not only facilitate satisfactory adhesion of the metallic
soap powder thereto but also perpetuate the fragrance of the
granulated detergent. Employment of water as the binder in place of
said lower alcohol or in place of said liquid perfume with a view
to coating the detergent grains with metallic soap powder would
fail to achieve the aimed effect because the metallic soap is poor
in affinity with water so that a uniform coating of the surface of
detergent grains with metallic soap powder is infeasible. And,
employment of inorganic builders for use in detergent such as
sodium tripoliphosphate and sodium sulfate in place of said
metallic soap powder would also fail to achieve the aimed effect.
There have hitherto been proposed various methods for securing the
perpetuity of fragrance of granulated detergents, but none of these
methods has ever adopted the rolling-granulation process applied
for film coating like in the present invention and has been
successful in overcoming the above-mentioned defects
simultaneously.
The object of the present invention can be achieved subject to
application of a lower alcohol or liquid perfume as the binder and
application of metallic soap powder as the coating agent. The
reason why such as effect as in the present invention can be
brought about is yet to be clarified: nevertheless, it is presumed
that, by virtue of synergy between the water insolubility and water
repellency possessed by said metallic soap powder and the proper
affinity with metallic soap possessed by said lower alcohol and
liquid perfume, the metallic soap powder might uniformly adhere to
the surface of detergent grains to form a coating. Particularly in
the case where a liquid perfume is employed as the binder, said
perfume is distributed into the inner part of the product and
coated the surface so that the perpetuity of fragrance can be
secured. Besides, at the time of use of the product, as a result of
breakdown thereof, the fragrance becomes greater. Because of the
surface of every detergent grain having been uniformly coated with
metallic soap, the product granular detergent displays an improved
fluidity and hygroscopic solidification preventability.
The lower alcohol applicable to the present invention is monohydric
alcohol or dihydric alcohol having 1-4 carbon atoms. Such alcohols
may be used either individually or upon combining two or more of
them. The appropriate amount of the lower alcohol to be applied is
in the range of 0.1-1 part by weight relative to 100 parts by
weight of detergent grains: in case of application of less than 0.1
part by weight, the surface of detergent grain fails to get wet
sufficiently, while in case of application of more than 1 part by
weight, it is rather unfavorable as it will require such additional
processes as drying and recovering alcohol. As to the liquid
perfume for use in the present invention, any perfume commonly used
in the granulated detergents for domestic use is applicable as long
as it has a proper affinity with metallic soap to be coated on the
layer of perfume adhering to the detergent grain, and it includes,
for instance, terpene series (linalool, terpineol, geraniol) phenol
series (eugenol) and aromatic alcohol series (phenylethyl alcohol,
benzyl alcohol). Such liquid perfumes may be used either
individually or upon combining two or more of them. The appropriate
amount of the liquid perfume to be applied is in the range of
0.05-1 part by weight relative to 100 parts by weight of detergent
grains.
The metallic soap powder applicable to the present invention is
calcium salt or magnesium salt of saturated fatty acid having a
mean particle diameter of less than 100.mu.. However, in the case
where lower alcohol is employed as the binder, it is necessary to
apply a fatty acid salt having 16-20 carbon atoms. Application of a
metallic soap powder having a mean particle diameter of more than
100.mu. is inadvisable as it will not only necessitate the use of
metallic soap powder in great quantities in order to achieve the
intended effect but also spoil the appearances of the resulting
product. The foregoing metallic soap powders may be used either
individually or upon combining two or more of them. The appropriate
amount of the metallic soap powder to be applied is in the range of
0.3-15 parts by weight -- preferably 0.5-10 parts by weight --
relative to 100 parts by weight of detergent grains: in case of
application of less than 0.3 part by weight, the surface of
detergent grain fails to be uniformly coated therewith, while in
case of application of more than 15 parts by weight, the amount is
excessive and the water-insoluble metallic soap turns into a white
emulsion when the product granular detergent is dissolved in water,
so that it is undesirable.
The granulated detergent constituting a material for use in the
process according to the present invention suffices to be ordinary
hollow grains obtained by spraying and drying a detergent
composition, and is not limited to any particular detergent. In
other words, the material granulated detergent consists of the
surface active agent, inorganic or organic builder, fluorescent
agent and other additives.
The rolling apparatus for use in the process according to the
present invention is not limited to any particular one; that is,
any of the well-known apparatuses can be employed. For instance, it
will do employ the conventional rolling-drum for use in adding
perfume in the field of detergent-manufacturing industry. Addition
of the lower alcohol or liquid perfume may be performed by any
method as long as uniform addition can be effected thereby;
nevertheless, the spray method, and especially the nozzle-spray
method employing solid cone nozzle, hollow cone nozzle and the
like, are suitable. As to the method for adding the metallic soap
powder, any method will do as long as uniform coating can be
effected thereby; for instance, the sprinkling method may be
applied.
Next, the concrete procedures for obtaining an improved granulated
detergent as product according to the process of the present
invention will be elucidated in the following, but it will be
understood that variations and modifications thereof which lie
within the scope of the invention as defined by the appended claims
are fully contemplated.
To begin with, the material hollow-granular detergent is introduced
into a rolling-drum. Thereafter, a prescribed amount of lower
alcohol or liquid perfume is added to said granular detergent in
the drum by an appropriate method, such as nozzle-spraying, while
rolling the drum. When said lower alcohol or liquid perfume has
sufficietly adhered to the surface of all detergent grains to make
them wet, a prescribed amount of metallic soap powder is added to
the thus wetted detergent grains by an appropriate method, such as
sprinkling, so as to make said powder uniformly adhere to said
grains. The inside temperature of the drum should of course not be
so high as to permit said lower alcohol or liquid perfume to boil
or evaporate. Accordingly, on the occasion of employing a
granulated detergent immediately after being produced by the spray
drying method as the material for use in the present invention,
inasmuch the detergent grains still hold a high temperature, if
said temperature is so high as to permit the lower alcohol or
liquid perfume to boil or evaporate, the material granulated
detergent must be once cooled.
The present invention renders it possible to achieve the desired
effect by simple procedures, so that the operation can be performed
continuously and is therefore suitable for mass production.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
EXAMPLE 1.
100 parts by weight of a hollow-granular detergent having the
following composition as obtained by the spray drying method were
introduced into a rolling-drum. 0.5 part by weight of ethanol was
added to said detergent by the use of a spray nozzle at the inlet
of the drum while rolling it to see that said ethanol be applied to
the detergent grains uniformly. When the detergent grains were
sufficiently wetted with the prescribed amount of ethanol, 1 part
by weight of calcium stearate having a mean particle diameter of
less than 20.mu. was sprinkled over the thus wetted detergent to
make it adhere and form a coating thereon. The inside temperature
of the drum on this occasion was 35.degree.C.
When the fluidity and the hygroscopic solidification preventability
of the granular product thus obtained were examined after leaving
said product standing for 24 hours, the results were as shown in
Table-1 in the following.
Composition of the material hollow-granular detergent: sodium
linear alkylbenzene sulfonate 17 g sodium tripolyphosphate 25 g
sodium silicate 10 g sodium sulfate 38 g fluorescent agent 0.4 g
CMC (carboxymethyl cellulose) 0.6 g water 9 g
EXAMPLE 2.
A granular detergent product was obtained through the same
procedures as in Example 1 except for substituting a perfume
(namely, geraniol) for ethanol. When the fluidity and the
hygroscopic solidification preventability of thus product were
examined, the results were as shown in Table-1 in the following.
Example 3.
Through the same procedures as in Example 1, 100 parts by weight of
a hollow-granular detergent having the following composition were
coated with 2 parts by weight of calcium stearate having a mean
particle diameter of less than 20.mu. by applying 1 part by weight
of ethanol as the binder. The result of examination of the
properties of the product was as shown in Table-1 in the
following.
Composition of the material hollow-granular detergent:
sodium olefin sulfonate having 13-18 carbon atoms 17 g sodium
tripoliphosphate 20 g sodium silicate 10 g sodium sulfate 43 g
fluorescent agent 0.4 g CMC 0.6 g water 9 g
EXAMPLE 4.
Through the same procedures as in Example 1, 100 parts by weight of
a hollow-granular detergent having the following composition were
coated with 2 parts by weight of calcium stearate having a mean
particle diameter of less than 20.mu. by applying 0.2 part by
weight of a perfume (a mixture composed of geraniol and linalool at
the rate of 1:1 by weight) as the binder. The result of examination
of the properties of the product was as shown in Table-1 in the
following.
Composition of the material hollow-granular detergent:
sodium olefin sulfonate having 15-18 carbon atoms 18 g sodium
tripoliphosphate 20 g sodium silicate 10 g sodium sulfate 42 g
fluorescent agent 0.4 g CMC 0.6 g water 9 g
EXAMPLE 5.
Through the same procedures as in Example 1, 100 parts by weight of
a hollow-granular detergent having the same composition as in
Example 1 were coated with 3 parts by weight of calcium stearate
(consisting of 20 wt.% of particles having a mean diameter of
50-30.mu. and 80 wt.% of particles having a mean diameter of less
than 30.mu.) by applying 1 part by weight of ethanol. The inside
temperature of the rolling-drum on this occasion was 40.degree.C.
The result of examination of the properties of the product was as
shown in Table-1 in the following.
EXAMPLE 6.
Through the same procedures as in Example 1, 100 parts by weight of
a hollow-granular detergent having the same composition as in
Example 1 were coated with 1 part by weight of magnesium stearate
having a mean particle diameter of less than 10.mu. instead of
calcium stearate used in Example 1 and by applying 0.3 part by
weight of ethylene glycol instead of 0.5 part by weight of ethanol
used in Example 1. The result of examination of the properties of
the product was as shown in Table-1 in the following.
EXAMPLE 7.
Through the same procedures as in Example 1, 100 parts by weight of
a hollow-granular detergent having the following composition were
coated with 2 parts by weight of calcium stearate having a mean
particle diameter of less than 10.mu. by applying 0.5 part by
weight of methanol as the binder. The result of examination of the
properties of the product was as shown in Table-1 in the
following.
Composition of the material hollow-granular detergent:
sodium linear alkylbenzene sulfonate 30 g sodium sulfate 65 g water
5 g
EXAMPLE 8.
Through the same procedures as in Example 1, 100 parts by weight of
a hollow-granular detergent having the following composition were
coated with 3 parts by weight of calcium stearate having a mean
particle diameter of less than 20.mu. by applying 0.15 part by
weight of a perfume (a mixture composed of geraniol and linalool at
the rate of 1:1 by weight) as the binder. The result of examination
of the properties of the product was as shown in Table-1 in the
following.
Composition of the material hollow-granular detergent:
sodium linear alkylbenzene sulfonate 20 g sodium tripoliphosphate
22 g sodium silicate 10 g sodium sulfate 38 g fluorescent agent 0.4
g CMC 0.6 g water 9 g
EXAMPLE 9.
In the same way as in Example 2 except for substituting magnesium
stearate for calcium stearate, a hollow-granular detergent product
was obtained. The result of examination of the properties of this
product was as shown in Table-1 in the following.
EXAMPLE 10.
Through the same procedures as in Example 1, 100 parts by weight of
the same material hollow-granular detergent as in Example 1 were
coated with 3 parts by weight of calcium stearate having a mean
particle diameter of less than 20.mu. by applying 0.2 part by
weight of a perfume (namely, eugenol). The result of examination of
the properties of the product was as shown in Table-1 in the
following.
Table 1
__________________________________________________________________________
Example No. 1 2 3 4 5 6 7 8 9 10
__________________________________________________________________________
fluid- ity* (angle of repose) 37.degree. 36.degree. 35.degree.
35.degree. 34.degree. 38.degree. 35.degree. 35.degree. 37.degree.
35.degree. hygro- scopic solidi- fica- tion pre- venta- bility** 5
5 3 4 2 6 5 3 5 5 fra- grancy*** -- 38 -- 45 -- -- -- 47 38 48
__________________________________________________________________________
Remarks: *Measurement of the fluidity was conducted by setting the
temperature of the sample (product) at 35.degree.C. **The
hygroscopic solidification preventability was evaluated through the
procedure comprising leaving the sample standing with atmosphere of
95% i RH and 30.degree.C in 24 hrs, then sifting this sample by the
use of a 4-mesh sieve, and measuring the amount of sample left on
the sieve in terms of wt.%. ***The fragrancy was evaluated through
the procedure comprising packing the sample in a carbon case,
leaving the thus packed sample standing in a room of normal
temperature upon cutting open the prescribed outlet of the carton
case, and counting the number of days required for half decay of
the initial fragrancy after packing.
(The above procedures for measurement and evaluation will apply to
the following comparative examples too.)
Comparative Example 1.
The same material hollow-granular detergent as used in Example 1
was left standing for 24 hours without applying the treatment
according to the present invention, and was thereafter subjected to
examination of the fluidity and hygroscopic solidification
preventability thereof. The result was as shown in Table-2 in the
following.
Comparative Example 2.
In the same way as in Example 1 except for changing the amount of
calcium stearate from 1 part by weight to 2 parts by weight and the
particle diameter thereof to be less than 10.mu. and substituting
water for ethanol, coating of the material hollow-granular
detergent was effected. The result of examination of the properties
of the product was as shown in Table-2 in the following.
Comparative Example 3.
In the same way as in Example 1 except for substituting sodium
sulfate (applied amount: 2 parts by weight; mean particle diameter:
less than 100.mu.) for calcium stearate, coating of the material
hollow-granular detergent was effected. The result of examination
of the properties of the product was as shown in Table-2 in the
following.
Comparative Example 4.
In the same way as in Example 1 except for substituting sodium
sulfate (applied amount: 2 parts by weight) for calcium stearate
and 0.2 part by weight of geraniol for 0.5 part by weight of
ethanol, coating of the material hollow-granular detergent was
effected. The result of examination of the properties of the
product was as shown in Table-2 in the following.
Comparative Example 5.
0.2 part by weight of geraniol was added to 100 parts by weight of
the same material hollow-granular detergent as used in Example 1.
The result of examination of the properties of the product was as
shown in Table-2 in the following.
Table 2 ______________________________________ Comparative Example
No. 1 2 3 4 5 ______________________________________ fluidity *
(angle of repose) 42.degree. 40.degree. 38.degree. 40.degree.
42.degree. hygroscopic solidification 25 27 30 20 25 preventability
** fragrancy *** -- -- -- 32 30
______________________________________
* * * * *