United States Patent (19) 1 4,414,044

Takeuchi et al. 45) Nov. 8, 1983

54) WATER-IN-OIL EMULSION EXPLOSIVE 56) References Cited
COMPOSITION U.S. PATENT DOCUMENTS
(75. Inventors: Fumio Takeuchi; Masao Takahashi, 3,765,964 10/1973 Wade ...................................... 149/2
both of Aichi, Japan 4,110,34 8/1978 Wade ......... ... 49/2
4,218,272 8/1980 Brockington ..... ... 149/2
4,322,258 3/1982 Sudweeks et al. r 49/2
73) Assignee: Nippon Oil and Fats, Co., Ltd., 4,326,900 4/1982 Hattori et al. .......................... 149/2
Tokyo, Japan
Primary Examiner-Stephen J. Lechert, Jr.
21 Appl. No.: 372,131 Attorney, Agent, or Firm-Parkhurst & Oliff
57 ABSTRACT
22 Filed: Apr. 27, 1982 A water-in-oil emulsion explosive composition compris
30 Foreign Application Priority Data ing an aqueous solution of ammonium nitrate alone or in
admixture with the other inorganic oxidizer salt, fuel oil
May 11, 1981 JP Japan .................................. 56-69282 and/or wax, an emulsifier of dipentaerythritol fatty acid
May 12, 1981 JP Japan ... ... 56-7O181 ester, polyoxyalkylenedipentaerythritol fatty acid ester,
May 12, 1981 JP Japan .................................. 56-7082 sugar fatty acid ester, polyoxyalkylenesugar fatty acid
ester or sorbitol fatty acid ester, and hollow micro
51) Int. Cl. .............................................. CO6B 45/00 spheres or microbubbles, has excellent storage stability
52 U.S.C. .......................................... 149/2; 149/21; in the detonation sensitivity in a small diameter car
149/46; 149/41; 149/60, 149/61 tridge and at low temperature.
58) Field of Search ................... 149/2, 21, 46, 60, 61,
149/41 8 Claims, No Drawings
 1.
4,414,044
WATER-IN-OIL EMULSION EXPLOSIVE
COMPOSITION
BACKGROUND OF THE INVENTION
(1) Field of the Invention
The present invention relates to a water-in-oil emul
sion explosive composition (hereinafter, abbreviated as
W/O emulsion explosive composition), and more par
ticularly relates to a W/O emulsion explosive composi
tion containing a novel emulsifier, which can form
W/O emulsion, and having a performance superior to
conventional W/O emulsion explosive compositions
containing a commonly known emulsifier in the storage
stability in the detonation sensitivity in a small diameter
cartridge (diameter: 25 mm) and at low temperature.
(2) Description of the Prior Art
There have been variously investigated W/O emul
sion explosive compositions for a long period of time.
However, W/O emulsion explosive compositions pro
duced in the early stage investigation are unstable in
their emulsion state (that is, the contact area of the
disperse phase and the continuous phase is relatively
small), and therefore in almost all of the initial stage
W/O emulsion explosive compositions, their detonation
sensitivity in a small diameter cartridge was improved
by compounding thereto an explosive sensitizer, such as
nitroglycerine or the like, or a nonexplosive sensitizer,
such as monomethylamine nitrate or the like (hereinaf 30
ter these explosive sensitizer and nonexplosive sensitizer
are referred to as sensitive substances), a detonation
catalytic sensitizer, such as a compound of metals hav
ing an atomic number of at least 13 and being other than
the metals of Groups I and II in the Periodic Table, a are
35 sensitivity in a small diameter cartridge (diameter: 25
strontium compound or the like, or a sensitive oxidizer,
such as perchlorate or the like of ammonium or alkali
metals (hereinafter, these detonation-catalytic sensitizer
and sensitive oxidizer are referred to as auxiliary sensi
tive substances). However, W/O emulsion explosive scribed problems, and found out that an aqueous solu
compositions containing the above described sensitive 40 tion consisting of water and ammonium nitrate, or a
substance or auxiliary sensitive substance have the dan
gerous property that, when the sensitive substance or
auxiliary sensitive substance is separated at the produc
tion of the W/O emulsion explosive composition or
during the use thereof, the explosive composition be
comes very sensitive, or the toxic property of the sensi
tive or auxiliary sensitive substance appears. In order to
obviate these drawbacks, there have been proposed
W/O emulsion explosive compositions having an im
proved detonation sensitivity in a small diameter car 50
tridge (capable of being detonated by a blasting cap)
without containing any of the above described sensitive
substances and auxiliary sensitive substances.
For example, U.S. Pat. No. 4,110,134 discloses that
W/O emulsion explosive compositions, which contain
an emulisifier of sorbitan fatty acid ester, glycerine fatty
acid ester, polyoxyethylene sorbitol fatty acid ester,
polyoxyethylene ether, polyoxyalkylene oleic acid es
ter, polyoxyalkylene lauric acid ester, phosphoric acid
oleic acid ester, substituted oxazoline or phosphoric
acid ester and which further contain a gas-retaining
agent of glass microballoon, can be completely deto
nated up to a density of maximum 1.25 in a cartridge
diameter of about 1.25 inches (31.8 mm) by means of a
No. 6 blasting cap. . 65
U.S. Pat. No. 4,149,917 discloses that W/O emulsion
explosive compositions, which contain an emulsifier of
sorbitan fatty acid ester, glycerine fatty acid ester, poly
2
oxyethylene sorbitol fatty acid ester, polyoxye
thylene(4) lauryl ether, polyoxyethylene(2) ether, po
lyoxyethylene(2) steary ether, polyoxyalkylene oleic
acid ester, polyoxyalkylene lauric acid ester, phos
5
phoric acid oleic acid ester, substituted oxazoline, phos.
phoric acid ester or their mixture and whose density has
been adjusted to 0.95 by microbubbles without the use
of a gas-retaining agent can be completely detonated
10 (explosive temperature: 21.1' C.) in a cartridge diameter
of 1.25 inches (31.8 mm) by means of a No. 6 blastic cap
even after the lapse of time of 2 months and by means of
a No. 8 blasting cap even after the lapse of time of 8
months after the production of the explosive composi
15 tion.
Therefore, it is commonly known that various emulsi
fiers are used in a W/O emulsion explosive composition
not containing the above described sensitive substance
or auxiliary sensitive substance. Further, there are
20
known various emulsifiers capable of forming W/O
emulsion. However, W/O emulsion explosive composi
tions using an emulsifier other than that disclosed in the
above described U.S. patents use the above described
25 sensitive substance or auxiliary sensitive substance. This
fact shows that the W/O emulsion is poor in storage
stability, and the W/O emulsion explosive composition
is very poor in storage stability in detonation sensitivity
in a small diameter cartridge (diameter: 25 mm) and at
low temperature.
The W/O emulsion explosive composition using the
emulsifier described in the above described U.S. patents
still insufficient in storage stability in detonation
mm) and at low temperature.
The inventors have made various investigations for a
long period of time in order to solve the above de
mixture of ammonium nitrate and the other oxidizer
salt, and a combustible material consisting of fuel oil/-
wax can be formed into a W/O emulsion by the use of
a compound which has not hitherto been considered as
45
an emulsifier for W/O emulsion explosive composition;
and further found out that the resulting W/O emulsion
explosive composition is superior to W/O emulsion
explosive compositions containing a commonly known
emulsifier in storage stability in detonation sensitivity in
a small diameter cartridge and at low temperature. As a
result, the present invention has been accomplished.
SUMMARY OF THE INVENTION
55 The feature of the present invention is the provision
of a water-in-oil emulsion explosive composition, com
prising a disperse phase formed of an aqueous oxidizer
solution consisting of (a) ammonium nitrate or a mixture
of ammonium nitrate and the other inorganic oxidizer
salt and (b) water; a continuous phase formed of a com
bustible material consisting of (c) fuel oil and/or wax;
(d) at least one emulsifier selected from the group con
sisting of dipentaerythrytol fatty acid ester, polyoxyalk
ylenedipentaerythritol fatty acid ester, sugar fatty acid
ester, polyoxyalkylenesugar fatty acid ester and sorbitol
fatty acid ester; and (e) hollow microspheres or micro
bubbles.
 3.
4,414,044
DESCRIPTION OF THE PREFERRED
EMBODIMENT
The aqueous oxidizer solution of the W/O emulsion
explosive composition according to the present inven
tion contains ammonium nitrate as a main component
and may optionally contain another inorganic oxidizer
salt. As the other inorganic oxidizer salt, use is made of,
for example, nitrates of alkali metal or alkaline earth
metal, such as sodium nitrate, calcium nitrate and the
like. These inorganic oxidizer salts are used alone or in
admixture. The compounding amount of ammonium
nitrate is generally 50-94.7% by weight (hereinafter%
means % by weight) based on the total amount of the
resulting explosive composition, and the other inor
ganic oxidizer salts may be occasionally, added to am
monium nitrate in an amount of not more than 40%
based on the total amount of the ammonium nitrate and
the other inorganic oxidizer salt. . .
When the compounding amount of ammonium ni
trate is less than 50%, the oxygen balance (the relation
between the amount of oxygen in the oxidizer and the
amount of the combustible material) is improper (that is,
the amount of oxygen is too small), and the resulting
explosive composition is poor in the detonability and is 25
large in the amount of after-detonation fume. While,
when the compounding amount of ammonium nitrate
exceeds 94.7%, a temperature required in the dissolving
of ammonium nitrate into water is excessively high, the
productivity of explosive composition is poor, and the 30
explosion reactivity of ammonium nitrate is poor, and
accordingly the resulting explosive composition is poor
in the detonation sensitively. . ..
The use of a small amount of the other inorganic
oxidizer salt increases the feed amount of oxygen and 35
can lower the dissolving temperature of ammonium
nitrate in water, resulting in the improvement of detona
bility and productivity. While, when the amount of the
other inorganic oxidizer salt exceeds 40%, the amount
of remaining solid residue after explosion increases, and
the strength of the resulting explosives composition is
poor and the production of the explosive composition is
expensive. . . . . ."
The compounding amount of water to be used in the
aqueous oxidizer solution is generally 5-25% based on
the total amount of the resulting explosive composition.
When the compounding amount of water is less than
5%, an excessively high temperature is required in dis
solving ammonium nitrate or a mixture of ammonium
nitrate and the other inorganic oxidizer salt in water to
lower the productivity of the explosive composition
and to deteriorate the explosion reactivity thereof, and
the detonation sensitivity of the resulting explosive
composition is poor.
While, when the compounding amount of water ex
ceeds 25%, ammonium nitrate or a mixture of ammo
nium nitrate and the other inorganic oxidizer salt can be
dissolved in water at a low temperature, and therefore
the productivity of the explosive composition can be
improved. However, the amount of gas and the heat.
generated due to explosion are small, and therefore the
resulting explosive composition is poor in the detona
tion sensitivity and in the strength. . . .
The fuel oil of the fuel oil and/or wax includes, hy
drocarbons, for example, paraffinic hydrocarbon, ole
finic hydrocarbon, naphthenic hydrocarbon, aromatic
hydrocarbon, other saturated or unsaturated hydrocar
bon, petroleum, mineral oil, lubricant, liquid paraffin
4.
and the like; and hydrocarbon derivatives, such as ni
trohydrocarbon and the like. The wax includes unpuri
fied microcrystalline wax, purified microcrystalline
wax and the like, which are derived from petroleum;
mineral waxes, such as montah wax, ozokerite and the
like; animal waxes, such as whale wax and the like; and
insect waxes, such as beeswax and the like. These fuel
oil and/or wax are used alone or in admixture. The
compounding amount of these fuel oil and/or wax is
10 generally 0.1-10% based on the total amount of the
resulting explosive composition. When the compound
ing amount of the fuel oil and/or wax is less than 0.1%,
the resulting W/O emulsion explosive composition is
poor in the stability. While, when the compounding
5 amount exceeds 10%, the oxygen balance is improper
and a large amount of after-detonation fume is formed.
The dipentaerythritol fatty acid ester and polyox
yalkylenedipentaerythritol fatty acid ester to be used as
20 an emulsifier for the W/O emulsion explosive composi
tion of the present invention are represent by the fol
lowing general formula (I), and include, for example,
dipentaerythritol fatty acid esters, such as dipentaery
thritol lauric acid monoester, dipentaerythritol isos
tearic acid monoester, dipentaerythritol oleic acid
monoester, dipentaerythritol linoleic acid monoester,
dipentaerythritol erucic acid monoester, dipentaery
thritol linolenic acid tetraester and the like; and polyox
yalkylenedipentaerythritol fatty acid esters, such as
polyoxyethylene(4)-dipentaerythritol isostearic acid
tetraester, polyoxyethylene(6)-dipentaerythritol lin
oleic acid tetraester, polyoxypropylene(10)-dipentaery
thritol erucic acid tetraester and the like.
hoa HOCOR (I)
AOHC-C-CH2-O- CH-i-Choa
CH2OA CH2OA
wherein A represents H, RCO- or (OR")m.H
(m=0-20), R represents CnH2n+1, CnH2n-1, CnH2n-3
or CH2-5 (n=9-24), and R' represents
-CH2CH2- or -HCH
45 CH3
The sugar fatty acid ester and polyoxyalkylenesugar
fatty acid ester to be used as an emulsifier for the W/O
emulsion explosive composition of the present invention
50 are represented by the following general formulae (II)
and (III), and include, for example, sugar fatty acid
mono-, di- and tri-esters, such as sugarlauric acid mono
ester, sugar isostearic acid monoester, sugar oleic acid
diester, sugar oleic acid triester, sugar erucic acid tri
55 ester, sugar linoleic acid triester and the like; polyox
yalkylenesugar fatty acid triesters, such as polyoxye
thylene(4)-sugar oleic acid triester, polyoxyethylene(4)-
sugar linoleic acid triester, polyoxypropylene(6)-sugar
erucic acid triester and the like; and polyoxyalk
ylenesugar fatty acid diesters,
ROCOCH2 (ii)
/ H XOH, H . .. .
65
OH. H. H OHA - . . .
OH O CH2OX .
H OH OH. H.
 5
4,414,044
-continued
ROCOCH2 (III)
H H YOCH2 - O
O(R'O)H H H HOR).o
H(OR").O CH2OCOR
H b(RO).H O(R'O)H H
wherein X represents H or RCO-, Y represents H,
RCO- or (R'O)?h, R represents CnH2n-1, CnH2n-1,
CnH2n-3 or CnH2n-5 (n=9–24), and R' represents
-CH2CH2- or
-HCH- .
CH3
and a, b, c, d, e and frepresent integers of 0-20.
The sorbitol fatty acid ester to be used as an emulsi
fier for the W/O emulsion explosive composition of the
present invention is represented by the following gen
eral formula (IV), and includes, for example, sorbitol
fatty acid mono-, di-, tri- and tetra-esters, such as sorbi
tol lauric acid monoester, sorbitol oleic acid monoester,
sorbitol isostearic acid monoester, sorbitol linoleic acid
monoester, sorbitol oleic acid diester, sobitol oleic acid
triester, sorbitol oleic acid tetraester and the like.
CHOCOR (IV)
CHOX
CHOH
CHOH
CHOX
CH2OX
wherein X represents H or RCO-, and R represents
CnH2n+1, CnH2n-1, CnH2n-3 or CnH2n-5 (n=9–24).
The emulsifiers are used alone or in admixture. The
compounding amount of these emulisifiers is generally
0.1-5%, and preferably 0.5-4%, based on the total
amount of the resulting W/O emulsion explosive com
position. When the compounding amount of the emulsi
fier is less than 0.1%, the resulting W/O emulsion ex
plosive composition is poor in the storage stability in the
detonation sensitivity in a small diameter cartridge and
at low temperature. While when the compounding
amount exceeds 5%, the oxygen balance is improper,
and a large amount of after-detonation fume is formed,
and the use of such large amount of emulsifier is not
advantageous for commercial purpose.
Further, the density of the W/O emulsion explosive
composition of the present invention is adjusted to
0.80–1.35, preferably 1.00- 1.15, by using a density ad
justing agent. The density adjusting agent includes hol
low microspheres and/or microbubbles. As the hollow
microspheres, use is made of inorganic hollow micro
spheres obtained from, for example, glass, alumina,
shale, shirasu (shirasu is a kind of volcanic ash), silica,
volcanic rock, sodium silicate, borax, perlite, obsidian
and the like; carbonaceous hollow microspheres ob
tained from pitch, coal and the like; and synthetic resin
hollow microspheres obtained from phenolic resin,
polyvinylidene chloride, epoxy resin, urea resin and the
like. These hollow microspheres are used alone or in
6
admixture. The compounding amount of the hollow
microspheres is generally 0.1-10% based on the total
amount of the resulting W/O emulsion explosive com
position. The microbubbles include microbubbles ob
tained by foaming a chemical foaming agent, microbub
bles obtained by blowing mechanically air or other
gases into the explosive composition during or after the
formation of W/O emulsion, and the like.
O
As the chemical foaming agent, use is made of inor
ganic chemical foaming agents, such as alkali metal
borohydride, a mixture of sodium nitrite and urea, and
the like; and organic chemical foaming agents, such as
N,N'-dinitrosopentamethylenetetramine, azodicarbon
15. amide, azobisisobutyronitrile and the like. These chemi
cal foaming agents are used alone or in admixture. The
compounding amount of the chemical foaming agent is
generally 0.01-2% based on the total amount of the
resulting W/O emulsion explosive composition. When
20 the compounding amount of the above described hol
low microspheres is less than 0.1% or that of the chemi
cal foaming agent is less than 0.01% or the blown
amount of air or other gas is such a small amount that
the resulting W/O emulsion explosive composition has
25 a density of higher than 1.35, the resulting explosive
composition is poor in the detonation sensitivity and
further is low in the detonation velocity even when the
explosive composition is detonated.
While, when the compounding amount of the hollow
30 microspheres exceeds 10% or that of the chemical
foaming agent exceeds 2% or the blown amount of air
or other gas is such a large amount that the resulting
W/O emulsion explosive composition has a density of
less than 0.80, the resulting explosive composition has a
35 good detonation sensitivity but is poor in the strength.
The W/O emulsion explosive composition of the
present invention is produced, for example, in the fol
lowing manner. That is, ammonium nitrate or a mixture
of ammonium nitrate and the other inorganic oxidizer
salt is dissolved in water at a temperature of about
80°-90° C. to obtain an aqueous oxidizer solution. Sepa
rately, an emulsifier defined in the present invention is
melted at 80°-90° C. together with fuel oil and/or wax
to obtain a combustible material mixture. Then, the
45
combustible material mixture is firstly charged into a
heat-insulating vessel of a certain capacity, and then the
aqueous oxidizer solution is gradually added thereto
while agitating the resulting mixture by means of a
commonly used propeller blade-type agitator. After
50
completion of the addition, the resulting mixture is
further agitated at a rate of about 1,600 rpm for about 5
minutes to obtain a W/O emulsion kept at about 85 C.
Then, the W/O emulsion is mixed with hollow micro
55 spheres or chemical foaming agent in a vertical type
kneader while rotating the kneader at a rate of about 30
rpm, to obtain an aimed W/O emulsion explosive com
position. When it is intended to produce a W/O emul
sion explosive composition containing microbubbles of
60 air or other gas in place of the production of a W/O
emulsion explosive composition containing hollow mi
crospheres or microbubbles formed by the decomposi
tion of a chemical foaming agent, the above described
W/O emulsion is agitated, while blowing air or other
65 gas into the emulsion, to obtain an aimed W/O emulsion
explosive composition.
The following examples are given for the purpose of
illustration of this invention and are not intended as
 4,414,044
7 8
limitations thereof. In the examples, "parts" and "%" substantially to one month storage at room tempera
mean by weight. ture).
EXAMPLE 1 The obtained results are shown in the following
Table 1.
A W/O emulsion explosive composition having a EXAMPLES 2-11
compounding recipe shown in the following Table 1
was produced in the following manner. A W/O emulsion explosive composition having a
To 55.25 parts (11.05%) of water were added 381.5 compounding recipe shown in Table 1 was produced
parts (76.30%) of ammonium nitrate and 22.85 parts according to Example 1, except that the dipentaery
(4.57%) of sodium nitrate, and the resulting mixture was 10 thritol lauric acid monoester used in Example 1 was
heated to about 85 C. to dissolve the nitrates in water replaced by dipentaerythritol isostearic acid monoester,
and to obtain an aqueous solution of the oxidizer salts. dipentaerythritol oleic acid monoester, dipentaery
While, a mixture of 8.75 parts (1.75%) of dipentaery thritol linoleic acid monoester, dipentaerythritol erucic
thritol lauric acid monoester defined in the present in acid diester, dipentaerythritol linolenic acid tetraester,
vention and 17.05 parts (3.41%) of unpurified micro 15 polyoxyethylene(4)-dipentaerythritol isostearic acid
crystalline wax was heated and melted to obtain a com tetraester, polyoxyethylene(6)-dipentaerythritol lin
bustible material mixture kept at about 85 C. oleic acid tetraester, polyoxypropylene(10)-dipentaery
Into a heat-insulating vessel was charged the above thritol erucic acid tetraester or their mixture.
described combustible material mixture, and then the A sample cartridge was produced from the above
above described aqueous solution of the oxidizer salts 20 obtained W/O emulsion explosive composition in the
was gradually added thereto while agitating the result same manner as described in Example 1, and subjected
ing mixture by means of a propeller blade-type agitator. to the same performance tests as described in Example
After completion of the addition, the resulting mixture 1. The obtained results are shown in Table 1.
was further agitated at a rate of about 1,600 rpm for 5 EXAMPLE 12
minutes to obtain a W/O emulsion kept at about 85°C. 25
Then, the W/O emulsion was mixed with 14.60 parts A W/O emulsion explosive composition having a
(2.92%) of glass hollow microspheres having an aver compounding recipe shown in Table 1 was produced
age particle size of 75 um in a vertical type kneader according to Example 1, except that the glass hollow
while rotating the kneader at a rate of about 30 rpm, to microspheres used in Example 1 was replaced by N,N'-
obtain a W/O emulsion explosive composition. The 30 dinitrosopentamethylenetetramine. A sample cartridge
resulting W/O emulsion explosive composition was was produced from the W/O emulsion explosive com
molded into a shaped article having a diameter of 25 position in the same manner as described in Example 1.
mm and a length of about 180 mm and having a weight The sample cartridge was heated in a thermostat kept at
of 100 g, and the shaped article was packed with a about 50 C. for 2 hours to decompose and foam the
viscose-processed paper to form a cartridge, which was 35 foaming agent (N,N'-dinitrosopentamethylenetetra
used in the following performance tests. The perfor mine) contained therein, whereby the density of the
mance tests are (1) the measurement of density one day emulsion explosive composition was adjusted. The
after the production of the explosive composition, (2) above treated sample cartridge was subjected to the
the storage stability test for the detonation sensitivity, same performance tests described in Example 1. The
and (3) the measurement of the density at the detonation 40 obtained results are shown in Table 1.
test in the storage stability test described in the above EXAMPLE 13
item (2). The storage stability test for detonation sensi
tivity described in the above item (2) was carried out in A W/O emulsion explosive composition having a
the following manner. A sample cartridge was kept at compounding recipe shown in Table 1 was produced by
60° C. for 24 hours and then kept at -15° C. for 24 45 the following method. That is, a W/O emulsion was
hours, which was referred to as one temperature cycle. produced according to Example 1, and then the W/O
This temperature cycle was repeated to deteriorate emulsion ws agitated at a rate of about 1,600 rpm for 2
compulsorily the sample cartridge, and then the sample minutes by means of a propeller blade-type agitator,
cartridge was subjected to a detonation test at -5° C. while blowing air into the emulsion through a nozzle
by using a No. 6 blasting cap. The number of repeated 50 having a small diameter, to introduce microbubbles into
temperature cycles, within which the sample cartridge the emulsion and to obtain a W/O emulsion explosive
was able to be completely detonated, was counted, and composition having a given density.
this number of the repeated temperature cycles was A sample cartridge was produced from the above
estimated as the number of storage months, within obtained W/O emulsion explosive composition in the
which the sample cartridge can be completely deto 55 same manner as described in Example 1, and subjected
nated, in the storage at room temperature (10-30 C.). to the same performance tests as described in Example
(It has been ascertained from experiments that the 1. The obtained results are shown in Table 1.
above described one temperature cycle corresponds
TABLE 1(a)
Example
2 3 4. 5 6 7 8 9 10 12 13
Compound- Aqueous Ammonium nitrate 76.30 76.30 76.30 76.30 76.30 76.30 76.30 76.30 76.30 49.70 49.70 78.44 78.60
ing oxidizer Sodium nitrate 4.57 4.57 4.57 4.57 4.57 4.57 4.57 4.57 4.57 12.40 12.40 4.70 4.7
recipe solution Calcium nitrate - - - --- - - --- - - 12.40 12.40 - -
(%) Water 1.05 11.05 105 11.05 1.05 11.05 05 11.05 105 120 11.20 11.36 11.38
Combus- Unput ified 3.4 3.41 3.41 3.41 3.41 3.41 3.41 3.41 3.41 - - 3.50 3.51
tible microcrystalline wax
material Liquid paraffin - - - --- - - - - - 4.30 4.30 - -
Ernul- Dipentaerythritol 1.75 - ---- - - - - - -- -- - -
 4,414,044
TABLE 1 (ap-continued
Example
sifier lauric acid monoester
Dipentaeryl thritol - .75 - - - - ----- - - - -

isostearic acid
Onoester
Dipentaerythritol - - is - - - - - - - 0.80 - --
oleic acid monoester
Dipentaerythritol - - --- i.75 - - - --- - - - - -

inoleic acid
monoester
Dipentaerythritol - --- - 1.75 - -- --- m 2.50 0.80 180 180
erucic acid diester
Dipentaerythritol --- - . -- 75 - --- -- - -- -

inolenic acid
tetraester

Compound- Emul- Polyoxyethylene(4)- - - - - - - 1.75 - ------ - - - -

ing sifier dipentaerythritol

recipe isostearic acid
(%) tetraester
Polyoxyethylene(6)- ----- - -- - - - --- 1.75 - --- - - wn

dipentaerythritol
linoleic acid
tetraester
Polyoxypropylene(10)- - --- --- - - -- - r 1.75 - 0.90 - ---
dipentaerythritol
erucic acid
tetraester
Others Glass hollow 2.92 2.92 2.32 2.92 2.92 2.92 2.92 2.92 2.92 - - - -
micropheres -
Silica hollow - - - - - - - - 7.50 7.50 - -

microspheres
N,N'-Dinitrosopenta- -- --- - - - --- - - --- 0.20 -

methylenetetramine
Perform- Density one day after the .06 1.05 9 .07 1.07 .08 1.06 1.06 1.07 109 .08 1.09 .09
aCe production
Storage stability in detona- 23 25 25 26 27 27 23 24 26 32 33 2. 20
tion sensitivity (number of
complete detonation months)
Density at the final complete 1.08 06 09 .09 108 1.08 109 .08 .07 1.10 1,09 1.11 1.10
detonation

... . . A sample cartridge was produced from the above

EXAMPLES 14-24 45 obtained W/O emulsion explosive composition in the
A W/O emulsion explosive composition having a same manner as described in Example 1, and subjected
compounding recipe shown in Table 2 was produced to the same performance tests as described in Fxample
according to Example 1, except that the dipentaery- 1. The obtained results are shown in Table 2.
thritol lauric acid monoester used in Example 1 was
replaced by sugar lauric acid monoester, sugar isos- EXAMPLES 25 and 26
tearic acid monoester, sugar oleic acid diester, sugar 50 A W/O emulsion explosive composition having a
oleic acid triester, sugar erucic acid triester, sugar lin- compounding recipe shown in Table 2 was produced
oleic acid triester, polyoxyethylene(4)-sugar oleic acid according to Examples 12 and 13. A sample cartridge
triester, polyoxyethylene(4)-sugar linoleic acid triester, was produced from the above obtained W/O emulsion
polyoxypropylene(6)-sugar erucic acid triester or their 55 explosive composition according to Examples 12 and
mixture. 13, and subjected to the same performance tests as de
... . . scribed in Example 1. The obtained results are shown in
. .. Table 2.

TABLE 2(a)
Example
14 15 6 7 18 19 20 21 22 23 24 25 26
Compound- Aqueous Ammonium nitrate 76.30 76.30 78.30 76.30 76.30 76.30 76.30 76.30 76.30 49.70 49.70 78.44 78.60
ing oxidizer Sodium nitrate 4.57 4.57 c.57 4.57 4.57 4.57 4.57 4.57 4.57 12.40 2.40 4.70 4.71
recipe solution Calcium nitrate - --- --- - - - -- - 12.40 12.40 - -
(%) Water 11.05 11.05 05 105 11.05 .05 11.05 1.05 .05 11.20 120 11.36 .38
Combus- Unpurified 3.4 3.41 3.41 3.41 34t 3.4 3.4 3.4 3.41 - - 3.50 3.51
tible microcrystalline wax
material Liquid paraffin -- ---- - - - - ----- - 4.30 4.30 - re
Emul- Sugar lauric acid .75 - - - - - - - - - - - w
 4,414,044 . :
11 12
TABLE 2(a)-continued
- Example
20 2 22 23 24 25 26
sifier nonOester
Sugar isostearic acid
monoester
Sugar oleic acid
diester
Sugar oleic acid
triester
Sugar erucic acid
triester
Sugar linoleic acid
triester

Compound. Emul- Polyoxyethylene(4)- - C- - - - - 1.75 - - - 1.25 - -

ing sifier sugar oleic acid- "...rs. . . . . . . is r- it
recipe triester
(%) Polyoxyethylene(4)- -- - - - - - 1.75 - - - - -
sugar linoleic acid
triester
Polyoxypropylene(6)- - - - - - - - 1.75 - - - -
sugar erucic acid
triester
Others Glass hollow 2.92 2.92 2.92 2.92 2.92 2.92 2.92 2.92 2.92 - - - - -
microspheres
Silica hollow - m - - - - - - - 7.50 7.50 - -
microspheres
N,N'-Dinitrosopenta- - or - - - - - - - - - - - 0.20 -
methylenetetramine
Perform- Density one day after the 1.08 1.05 1.07 .08 1,06 1.08 105 1.07 1.09 .08 1.05 .06 1.08
Ce production
Storage stability in detona- 23 24 26 28 27 29 25 26 27 33 3 19 20
tion sensitivity (number of
complete detonation months) .
Density at the final complete 09 08 09 1,08 1.07 .0 1.07 109 110 09 108 .09 E.O
detonation

EXAMPLES 27-33 40 to the same performance tests as described in Example

A W/O emulsion explosive composition having a 1. The obtained results are shown in Table 3.
compounding recipe shown in Table 3 was produced EXAMPLES 34 and 35
according to Example 1, except that the dipentaery A W/O emulsion explosive composition having a
thritol lauric acid monoester used in Example 1 was 45 compounding recipe shown in Table 3 was produced
replaced by sorbitol lauric acid monoester, sorbitol according to Examples 12 and 13. A sample cartridge
isostearic acid monoeser, sorbitollinoleic acid monoes was produced from the above obtained W/O emulsion
ter, sorbitol oleic acid diester, sorbitol oleic acid triester explosive composition according to Examples 12 and
or sorbitol oleic acid tetraester. V 13, and subjected to the same performance tests as de
A sample cartridge was produced from the above 50 scribed in Example 1. The obtained results are shown in
obtained W/O emulsion explosive composition in the Table 3.
same manner as described in Example 1, and subjected
TABLE 3(a)
Example
27 28 29 30 3. 32 33 34 35
Compounding Aqueous Ammonium nitrate 76.30 76.30 76.30 76.30 76.30 76.30 49.70 78.44 78.60
recipe oxidizer Sodium nitrate 4.57 4.57 4.57 4.57 4.57 4.57 1240 4.70 4.71
(%) solution Calcium nitrate wer - m --- - - 2.40 - -
Water 11.05 i.05 11.05 li.05'11.05 1.05 11.2011.36 11.38
Combustible Unpurified 3.41 3.4 3.41 3.4 3,41 3.41 - 3.50 3.5
material microcrystalline wax s: . . . . m .
- .. - Liquid paraffin, - - - - - - , 4.30 - -
Emulsifier Sorbitol lauric acid monoester 1.75 - m --- - a- - - - win - -
Sorbitol isostearic acid monoester - i.75 - - u- - " -r - -
Sorbitol linoleic acid monoester - - 1.75 - - - - - - -
Sorbitol oleic acid diester - --- m 1.75 -; 2.50 180 180
Sorbitol oleic acid triester - - m - 1.75 - w- m -
Sorbitol oleic acid tetraester --- - --- - m 75 - - -
 4,414,044
3 4.
TABLE 3(b)
Example
27 28 29 30 3. 32 33 34 35
Compounding Others Glass hollow microspheres 2.92 2.92 2.92 2.92 2.92 2.92 - -- -
recipe Silica hollow microspheres w- - -- -- -- 7.50 - ---
(%) N,N'-Dinitrosopenta- - - - - - - - 0.20 -
methylenetetramine
Performance Density one day after the production 1.07 1.07 1.06 1.08 .07 1.09 10 1.05 1.07
Storage stability in detonation sensitivity 23 25 27 29 26 28 31 21 21
(number of complete detonation months)
Density at the final complete detonation 1.09 1.08 109 1.08 1.10 1.09 1.10 1.09 1.10

COMPARATIVE EXAMPLES 1-8 the present invention, dipentaerythritol lauric acid

monoester, dipentaerythritol isostearic acid monoester,
A W/O emulsion explosive composition having a 15 dipentaerythritol oleic acid monoester, dipentaery
compounding recipe shown in Table 4 was produced thritol linoleic acid monoester, dipentaerythritol erucic
according to Example 1. A sample cartridge was pro acid diester, dipentaerythritol linolenic acid tetraester,
duced from the above obtained W/O emulsion explo polyoxyethylene(4)-dipentaerythritol isostearic acid
sive composition in the same manner as described in tetraester, polyoxyethylene(6)-dipentaerythritol lin
Example 1, and subjected to the same performance tests 20 oleic acid tetraester or polyoxypropylene(10)-dipenta
as described in Example 1. The obtained results are erythritol erucic acid tetraester, had a storage life of
shown in Table 4. 23-27 months, within which the explosive composition
COMPARATIVE EXAMPLES 9 and 10 was able to be completely detonated at -5° C. by
means of a No. 6 blasting cap.
A W/O emulsion explosive composition having a 25 The W/O emulsion explosive compositions (Exam
compounding recipe shown in Table 4 was produced ples 14-20), which contained, as an emulsifier defined in
according to Examples 12 and 13. A sample cartridge the present invention, sugar lauric acid monoester,
was produced from the above obtained W/O emulsion sugar isostearic acid monoester, sugar oleic acid diester,
explosive composition in the same manner as described sugar oleic acid triester, sugar erucic acid triester, sugar
in Example 1, and subjected to the same performance 30 linoleic acid triester, polyoxyethylene(4)-sugar oleic
tests as described in Example 1. The obtained results are acid triester, polyoxyethylene(4)-sugar linoleic acid
shown in Table 4. triester or polyoxypropylene(6)-sugar erucic acid tri
TABLE 4(a)
Comparative example
l 2 3 4 5 6 7 8 9 10
Compounding Aqueous Annonium nitrate 76.30 76.30 76.30 76.30 76.30 76.30 76.30 49.70 78.44 78.60
recipe oxidizer Sodium nitrate 4.57 4.57 4.57 4.57 4.57 4.57 4.57 12.40 4.70 4.71
(%) solution Caicium nitrate - - - - - 12.40 - -
Water 11.05 .05 105 11.05 11.05 05 11.05 21.20 11.36 11.38
Combus- Unpurified 3.41 3.41 3.41 3.41 3.41 3.41 3.41 - 3.50 3.51
tible microcrystalline wax
material Liquid paraffin - m- -- - - - 4.50 - -
Emulsifier Sorbitan monooleic acid ester 1.75 - - - - - 2.50 1.80 1.80
Polyoxyethylene(1)-sorbitol - 1.75 - - -- - --- - -
monooleic acid ester
Glycerine monooleic acid ester - - 1.75 - - - - - - -
Polyoxyethylene(2) oleyl ether - m- m 1.75 - -- - -- - ---
Polyoxyethylene(2) oleic --- - 1.75 - - --- - -
acid ester
Phosphoric acid oleic - -m- --- 1.75 - - -- -
acid ester
4,4-Bishydroxy-2-oleyl-2- - - - - - 1.75 - - -
oxazoline

TABLE 4(b)
Comparative example
2 3 4 5 6 7 8 9 10
Compounding Others Glass hollow microspheres 2.92 2.92 2.92 2.92 2.92 2.92 2.92 - -
recipe Silica hollow microspheres - --- - - -- - - 7.50 - ---
(%) N,N'-Dinitrosopenta- - - - - - - - 0.20 -
methylenetetramine
Performance Density one day after the production 108 1.12 .07 09 109 108 .07 109 1.05 1.09
Storage stability in detonation 19 6 17 3 12 18 18 24 14 3
sensitivity (number of complete
detonation months)
Density at the final complete detonation 109 3 1.09 1.10 1.09 10 1.08 i. 1.11 1.3

The results of Examples will be explained in compari- 65

son with the results of Comparative examples. ester, had a storage life of 23-29 months, within which
The W/O emulsion explosive compositions (Exam the explosive composition was able to be completely
ples 1-9), which contained, as an emulsifier defined in detonated at -5° C. by means of a No. 6 blasting cap.
 15
4,414,044
The W/O emulsion explosive compositions (Exam
ples 27-32), which contained, as an emulsifier defined in
the present invention, sorbitol lauric acid monoester,
sorbitol isostearic acid monoester, sorbitol linoleic acid
monoester, sorbitol oleic acid diester, sorbitol oleic acid
triester or sorbitol oleic acid tetraester, had a storage
life of 23-29 months, within which the explosive com
position was able to be completely detonated at -5°C.
by means of a No. 6 blasting cap.
While, the W/O emulsion explosive compositions O
(Comparative examples 1-7) containing a commonly
known emulsifier had a storage life of 6-19 months,
within which the explosive composition was able to be
completely detonated at -5° C. by means of a No. 6
blasting cap. 15
The W/O emulsion explosive composition of Com
parative example 8, which contained sodium nitrate and
calcium nitrate as an inorganic oxidizer salt other than
ammonium nitrate, liquid paraffin as a plasticizer, silica
hollow microspheres as a gas-retaining agent, and 20
2.50% of sorbitan monooleic acid ester as an emulsifier,
had a storage life of 24 months, within which the explo
sive composition was able to be completely detonated at
–5° C. by means of a No. 6 blasting cap; while the W/O
emulsion explosive composition of Example 10, which
had the same composition as that of the explosive com
position of Comparative example 8, except that 2.50%
of dipentaerythritol erucic acid diester as an emulsifier
defined in the present invention was contained in place
of the sorbitan monooleic acid ester used in Compara
tive example 8, had the life of 32 months; the W/O
emulsion explosive composition of Example 23, which
had the same composition as that of the explosive com
position of Comparative example 8, except that 2.50%
of sugar oleic acid triester was contained in place of the
sorbitan monooleic acid ester, had the life of 33 months;
the W/O emulsion explosive composition of Example
33, which had the same composition as that of the ex
plosive composition of Comparative example 8, except
that 2.50% of sorbitol oleic acid diester was contained
in place of the sorbitan monooleic acid ester, had the life
of 31 months; the W/O emulsion explosive composition
of Example 11, which had the same composition as that
of the explosive composition of Comparative example 8,
except that 0.80% of dipentaerythritol oleic acid mono 45
ester, 0.80% of dipentaerythritol erucic acid diester and
0.90% of polyoxypropylene(10)-dipentaerythritol eru
cic acid tetraester were contained in place of the sorbi
tan monooleic acid ester, had the life of 33 months; and
the W/O emulsion explosive composition of Example 50
24, which had the same composition as that of the ex
plosive composition of Comparative example 8, except
that 1.25% of sugar oleic acid triester and 1.25% of
polyoxyethylene(4)-sugar oleic acid triester were con
tained in place of the sorbitan monooleic acid ester, had 55
the life of 31 months.
The W/O emulsion explosive composition of Com
parative example 9, whose density was adjusted by
adding thereto 0.20% of a chemical foaming agent of
N,N'-dinitrosopentamethylenetetramine without the
use of a gas-retaining agent and which contained 1.80%
of sorbitan monooleic acid ester as an emulsifier, had a
storage life of 14 months, within which the explosive
composition was able to be completely detonated at
-5 C. by means of a No. 6 blasting cap; while the W/O
emulsion explosive composition of Example 12, which
had the same composition as that of the explosive com
position of Comparative example 9, except that 1.80%
16
of dipentaerythritol erucic acid diester as an emulsifier
defined in the present invention was contained in place
of the sorbitan monooleic acid ester used in Compara
tive example 9, had the life of 21 months; the W/O
emulsion explosive composition of Example 25, which
had the same composition as that of the explosive com
position of Comparative example 9, except that 1.80%
of sugar oleic acid triester was contained in place of the
sorbitan monooleic acid ester, had the life of 19 months;
and the W/O emulsion explosive composition of Exam
ple 34, which had the same composition a that of the
explosive composition of Comparative example 9, ex
cept that 1.80% of sorbitol oleic acid diester was con
tained in place of the sorbitan monooleic acid ester, had
the life of 21 months.
Further, the W/O emulsion explosive composition of
Comparative example 10, whose density was adjusted
by blowing mechanically microbubbles thereinto with
out the use of a gas-retaining agent, and which con
tained 1.80% of sorbitan monooleic acid ester as an
emulsifier, had a storage life of 13 months, within which
the explosive composition was able to be completely
detonated at -5 C. by means of a No. 6 blasting cap;
25 while the W/O emulsion explosive compositions of
Examples 13, 26 and 35, which had the same composi
tion as that of the explosive composition of Compara
tive example 10, except that 1.80% of dipentaerythritol
erucic acid diester, sugar oleic acid triester and sorbitol
30 oleic acid diester as an emulsifier defined in the present
invention were contained in place of the sorbitan mo
nooleic acid ester used in Comparative example 10, had
the lifes of 20, 20 and 21 months, respectively.
It can be seen from the above described comparison
35 of the Examples with the Comparative examples that
the W/O emulsion explosive composition containing
the emulsifier defined in the present invention is re
markably superior to the W/O emulsion explosive com
position containing a conventional emulsifier in the
40 storage stability in the detonation sensitivity in a small
diameter cartridge (diameter: 25 mm) and at low tem
perature.
We claim:
1. A water-in-oil emulsion explosive composition,
comprising a disperse phase formed of an aqueous oxi
dizer solution consisting of (a) ammonium nitrate or a
mixture of ammonium nitrate and sodium nitrate and (b)
water; a continuous phase formed of a combustible
material consisting of (c) fuel oil and/or wax; (d) at least
one emulsifier selected from the group consisting of
dipentaerythritol fatty acid ester, polyoxyalk
ylenedipentaerythritol fatty acid ester, sugar fatty acid
ester and polyoxyalkylenesugar fatty acid ester; and (e)
hollow microspheres or microbubbles.
2. A water-in-oil emulsion explosive composition
according to claim 1, wherein said dipentaerythritol
fatty acid ester and polyoxyalkylenedipentaerythritol
fatty acid ester are represented by the following general
60 formula (I)
HOA fHocOR (I)
65
Aotic--CH-O-CH-i-Choa
CH2OA CH2OA
wherein A represents H, RCO- or (OR").H
(m = 0-20) and R represents CnH2n-1, CnH2n-1,
 17
4,414,044
18
CnH2n-3 or CnH2n-5 (n=9-24), and R' represents ROCOCH2 (III)
-CH2CH2- or H 'H. YoCH, -o H
H(OR")O
9(R'OH H/Lo NH HOR"). CH2OCOR
H O(R'O)H O(R'O).H. H.
-HCH
CH3 10 wherein Y represents H, RCO- or (R'O)/H, R repre
sents CnH2n+1, CnH2n-1, CnH2n-3 or CnH2n-5
3. A water-in-oil emulsion explosive composition (n=9-24), and R' represents -CH2CH2- or
according to claim 1, wherein said sugar fatty acid ester 15 -HCH
CH3
is represented by the following general formula (II)
and a, b, c, d, e and frepresent integers of 0-20.
5. A water-in-oil emulsion explosive composition
ROCOCH2 (II)
20 according to claim 1, 2, 3 or 4, which comprises
50-94.7% by weight of ammonium nitrate or a mixture
H/ 'h XOGHzo H of ammonium nitrate and sodium nitrate, the amount of
said sodium nitrate being not larger than 40% by weight
OH
pH /lo-NH OH CHOX based on the amount of the mixture of ammonium ni
25 trate and sodium nitrate, 5-25% by weight of water,
H OH OH H 0.1-10% by weight of fuel oil and/or wax, 0.1-5% by
weight of an emulsifier and 0.1-10% by weight of hol
low microspheres.
wherein X represents H or RCO-, R represents 6. A water-in-oil emulsion explosive composition
30 according to claim 1, 2, 3, 4 or 5, wherein the amount of
CCH2n+1, CnH2n-1, CnH2n-3 or CnH2n-.5 (n=9-24). the emulsifier is 0.5-4% by weight based on the total
amount of the explosive composition.
4. A water-in-oil emulsion explosive composition 7. A water-in-oil explosive composition according to
claim 1, wherein said composition has a density of
according to claim 1, wherein said polyoxyalk 35 0.8-1.15.
8. A water-in-oil explosive composition according to
ylenesugar fatty acid ester is represented by the follow claim 1, wherein said composition has a density of
1.00- 1.15.
ing general formula (III) is k k h :

45

50

55

65