JPH0151472B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a time-prolonging composition for use in slow-fire electric detonators and other pyrotechnics, and its purpose is to provide a time-prolonging composition whose burning rate (hereinafter referred to as "burning rate") hardly changes over time. There is a particular thing. A time-prolonging drug composition is generally a mixture consisting of an oxidizing agent, a reducing agent, and other combustion modifiers and binders added as necessary. It is known that a chemical reaction occurs, causing the so-called time-dependent change in which the burning rate of the time-prolonging drug composition decreases from the originally designed burning rate value. This reaction also occurs due to humidity,
It is also known that it is accelerated by moisture and the like. If the time-delaying chemical composition undergoes such a change over time, it may cause variations in the delay time interval of delayed electric detonators and other pyrotechnics using the time-delaying chemical composition during blasting operations, making it difficult to perform efficient blasting. The problem arises that it is not possible to do this. Conventionally, as a countermeasure against moisture, moisture, etc., Japanese Patent Publication No. 31-9407 describes that a chromate salt is incorporated into a time delay drug composition to prevent moisture absorption. However, this method has the disadvantage that components other than chromate can absorb moisture. The present inventors have conducted repeated research to prevent and improve these shortcomings of time-prolonging drug compositions, and have found that by incorporating a specific surfactant into a time-prolonging drug composition, moisture resistance is improved and the burning speed due to changes over time is reduced. The present invention was completed based on the discovery that this decrease was reduced. The time-prolonging drug composition of the present invention contains a polyoxyethylene oxypropylene type nonionic surfactant containing 10 to 40% by weight of an oxyethylene group-added component.
It is characterized by containing 1% by weight. That is, the present invention comprises a conventional time-prolonging composition comprising a commonly used oxidizing agent, reducing agent, and combustion modifier, containing the above-mentioned specific surfactant. Examples of the conventional time delay drug composition include red lead,
Some contain iron silicon and antimony trisulfide as main components. The polyoxyethylene oxypropylene type nonionic surfactant used in the present invention is a surfactant containing an oxypropylene group as a hydrophobic group and an oxyethylene group as a hydrophilic group, and commercially available ones are usually polypropylene glycol. Manufactured by adding ethylene oxide. In the present invention, the content of oxyethylene groups in the surfactant is preferably 10 to 40% by weight, and if the content is less than 10% by weight, the effect of preventing a decrease in the burning speed due to changes over time in the time-prolonging drug composition is insufficient. If the content exceeds 40% by weight, the moisture resistance effect of the time delay drug composition will be insufficient, which is not preferable. The desired effect can be obtained by adjusting the amount of these surfactants added in the range of 0.05 to 1% by weight based on the total weight of the time-prolonging drug composition. If the amount added is less than 0.05% by weight based on the total weight of the time-prolonging drug composition, the desired effect cannot be expected. In addition, if it is added in an amount exceeding 1% by weight based on the total weight of the drug composition,
Since the surfactant itself is an organic substance, a large amount of combustion gas is generated. It should not be added in an amount exceeding 1% by weight since it may cause sensitivity to the atmosphere. The time-prolonging drug composition of the present invention comprising the above-mentioned components can be obtained by a conventional manufacturing method. First, the time-prolonging drug components other than the surfactant are mixed uniformly, and a binder in which the surfactant used in the present invention is dissolved is added to this mixture and mixed well. Then granulated, dried and classified,
A time-prolonging drug composition is obtained. The time delay drug composition of the present invention thus obtained has the following effects. The first effect is that a chemical reaction due to direct contact between an oxidizing agent and a reducing agent in the mixture system can be prevented, and a decrease in combustion speed over time can be prevented and improved. Moreover, as a second effect, it is possible to prevent the time-prolonging drug composition from absorbing moisture, and to eliminate the influence of moisture, which is a cause of acceleration of deterioration over time. This is particularly advantageous in the production of time-prolonging drug compositions during the summer or rainy season. Next, the time delay drug composition of the present invention will be specifically explained using Examples and Comparative Examples. Examples 1 to 6 Time-prolonging drug compositions as shown in Table 1 using a time-prolonging drug mixture consisting of 57% by weight of red lead, 6% by weight of iron silicon, and 37% by weight of antimony trisulfide and a surfactant. The product was manufactured as follows. That is, a predetermined ratio of the time-prolonging drug mixture and a cotton powder acetone solution containing a predetermined ratio of the surfactant shown in Table 1 are mixed, and then through the steps of granulation, drying, and classification, the time-prolonging drug mixture and the surfactant are mixed. A time-prolonging drug composition having a compounding ratio shown in Table 1 was obtained. A certain amount of this time delay drug composition was placed on the detonator of a raw material detonator (tube body filled with additives and detonator) and squeezed under a constant pressure to produce 30 raw material detonators containing time delay drug. . Ten of them were subjected to a moisture absorption test under 100% relative humidity for 10 days to measure the amount of moisture absorbed, and the results are shown in Table 2. For the remaining 20 raw material detonators containing time-delaying charges, embolizers with ignition parts were attached to create delayed-fire electric detonators. For this delayed electric detonator, a digital counter (manufactured by Takeda Riken Co., Ltd.) was used.
The delay time from energization to the delayed electric detonator to detonation was measured, and the burning speed of the time delay drug composition was determined from that value and the packed layer thickness of the time delay drug. The combustion speed was measured immediately after the sample was prepared and 3 years after the sample was prepared to examine changes in the combustion speed over time. The results of the change in combustion speed over time are shown in Table 3. Comparative Examples 1 to 7 Using time delay drug mixtures having the same formulations as in Examples 1 to 6, time delay drug compositions having the formulations shown in Table 1 were manufactured in the following manner. That is, a predetermined ratio of the time-prolonging drug mixture and a cotton powder acetone solution containing a predetermined ratio of the surfactant shown in Table 1 are mixed, and then through the steps of granulation, drying, and classification, the time-prolonging drug mixture and the surfactant are mixed. A sample of a time-prolonging drug composition having a compounding ratio shown in Table 1 was obtained.
Thereafter, raw material detonators containing time-prolonging medicine were prepared according to Examples 1 to 6, and moisture absorption tests were conducted according to Examples 1 to 6. The results of the moisture absorption test are shown in Table 2. Further, delayed electric detonators were manufactured according to Examples 1 to 6, and the combustion speeds were measured according to Examples 1 to 6. The results of the change in combustion speed over time are shown in Table 3.

【table】

[Table] To display the results of the moisture absorption test, the amount of moisture absorbed was measured, and the ratio of the amount of moisture absorbed to the amount of time-duration drug loaded per one raw material detonator containing a time-duration drug was determined as the moisture absorption rate. Further, assuming that the moisture absorption amount of Comparative Example 1 (no surfactant added) on the 5th day was 1.00, the moisture absorption amounts of other Examples and Comparative Examples were calculated as a percentage value and shown in Table 2. The method of displaying the change in combustion speed over time is to measure the delay time (delay time from energization to detonation) immediately after manufacturing the delayed electric detonator and 3 years later, and calculate the delayed charge length in the delayed electric detonator. (2.5mm) and
The combustion speed was determined by this delay time. Further, the combustion speed of Comparative Example 1 immediately after production was set as 1.00, and the combustion speeds of other Examples and Comparative Examples were determined as a ratio value to that value. As for the rate of change in combustion speed, the rate of decrease in combustion speed between 3 years after aging and immediately after manufacture was determined as follows and shown in Table 3. Rate of change in combustion speed (%) = B-A/A×100 A: Combustion speed immediately after manufacture (mm/sec) B: Combustion speed 3 years after manufacture (mm/sec)

【table】

【table】

[Table] As can be seen from Tables 1, 2, and 3 above, Comparative Examples 2 and 3 show values that are relatively close to the values of Examples in terms of moisture absorption rates in the moisture absorption test. However, the rate of change in fuel velocity shows a much larger value than in the example. Also, regarding Comparative Examples 1, 4, and 5, the moisture absorption test
and the rate of change in fuel velocity both show much larger values than in the example. Therefore, none of Comparative Examples 1 to 5 is effective in preventing a decrease in hygroscopicity and a decrease in combustion speed. In Comparative Example 6, the amount of Nitsusan Pronone 102 added was as high as 2.0%, so the amount of gas during combustion was large and the burning speed was significantly faster.
Therefore, it can be seen that Comparative Example 6 is also not practical. Regarding the amount of ethylene oxide added to polypropylene glycol, in Comparative Example 7, Nitsusanpronon 208 (80% ethylene oxide added to polypropylene glycol) was used.
When 1% by weight of is added, the decrease in combustion speed over time is small, but the moisture resistance effect is insufficient. On the other hand, in Examples 1 to 6, Nitsusanpronone with an oxyethylene group content of 10 to 40% was added to 0.05 to 1
It can be seen that the addition of % by weight has a remarkable effect on both prevention of moisture absorption and prevention of decrease in combustion speed over time.

Claims (1)

[Claims] 1. A time-prolonging drug composition characterized by containing 0.05-1% by weight of a polyoxyethylene oxypropylene type nonionic surfactant having an oxyethylene group-added component of 10-40% by weight.