KR20220066498A - Non-toxic retarder composition for detonator and delayed detonator comprising the same - Google Patents

Abstract

The present invention provides a non-toxic retardant composition for a detonator including Si, CuO and MnO_2 in a weight ratio of 35 to 55 : 38 to 52 : 7 to 25 and technology for manufacturing a delayed detonator including the same. The present invention can provide excellent thermal stability.

Description

Non-toxic retarder composition for detonator and delayed detonator comprising the same

The present invention relates to a non-toxic retarder composition for a primer and a delayed-type primer comprising the same.

Delayed gunpowder is used for military and industrial blasting, especially quarry blasting, coal mines, and civil engineering works in order to delay the time from the start signal from the electric or non-electric detonator to the triggering of main reactions such as detonation of the detonator or the blasting of the gunpowder. It is used in many fields including

The main requirement for retarding gunpowder is that it burns with a well-defined and stable combustion rate with very little time difference. In addition, the combustion rate should not be significantly affected by ambient conditions or aging. For this reason, there is a need for a combustion capable of producing an initial material, an intermediate, and a final product with low gas generation and stable properties.

In addition, the retarding powder should be easy to ignite and transmit the ignition to other materials well, but should not be excessively sensitive to shaking, vibration, friction, shock or static electricity. In addition, the explosive composition should be easy and safe to manufacture, use, and press-filled.

Retarding gunpowder can in principle be viewed as consisting of fuel and oxidizer and therefore many materials should be available, but the above requirements significantly limit the choice of suitable starting materials.

In conventional primers, compounds including lead such as lead dioxide, lead azide, lead chromate, and barium chromate, which are pyrotechnic materials, are generally used as retardants. However, lead is a toxic substance, and in particular, lead chromate and barium chromate have high harmful risks such as toxicity and explosiveness, so special attention is required in handling.

Recently, in the field of gunpowder, as interest in hazardous hazards affecting people and the environment increases, there is an increasing demand for not containing toxic substances. This is to avoid manufacturing/handling safety concerns, to reduce emission problems and also to reduce exposure problems at the point of end use.

However, while still meeting the above requirements, a satisfactory delayed explosive in terms of toxicity has not been sufficiently developed.

Republic of Korea Patent Registration No. 10-0272865

The present invention has been devised to solve the above problems of the prior art,

As a non-toxic retardant composition that has replaced the conventional lead and hexavalent chromium, it provides a wider range of combustion rates, it is possible to freely control the delay time according to the design intention, and it is possible to An object of the present invention is to provide a non-toxic retarder composition for primers that provides initiation reliability and can provide excellent thermal stability.

Another object of the present invention is to provide a delayed-type primer comprising the retarder composition.

the present invention

Si, CuO, and MnO ₂ It relates to a non-toxic retarder composition for a primer comprising a weight ratio of 35 to 55:38 to 52:7 to 25.

Also, the present invention

Provided is a delay-type primer comprising a tube body, an ignition means positioned at the top of the tube body, an initiator and an add-on agent positioned at the end of the tube body, and the non-toxic retarder composition for a primer of the present invention positioned in the middle of the tube body.

The non-toxic retarder composition for primers of the present invention provides a wider range of combustion rates than conventional lead-containing retardant compositions, can freely adjust the delay time according to the design intent, and has improved ultra-precision and detonation reliability. to provide. It also provides long-term storage stability.

Hereinafter, the present invention will be described in detail.

The present invention relates to a non-toxic retarder composition for a primer comprising Si, CuO and MnO ₂ in a weight ratio of 35 to 55:38 to 52:7 to 25. When Si, CuO and MnO ₂ are included in the above-mentioned weight ratio, a wide range of combustion rates is obtained, the delay time can be freely adjusted according to the design intention, improved ultra-precision and initiation reliability can be obtained, and storage stability is also provided.

In the retarder composition of the present invention, MnO ₂ has a low decomposition temperature of about 500° C. compared to other metal oxides, so it has good reactivity and excellent ignition properties, and has a catalyst property that is advantageous for the reaction rate, which contributes to the reliability of combustion of the retarder. It is used as an oxidizing agent.

The retarder composition of the present invention is a material for controlling the combustion rate, and the type of oxidizing agent was selected and used in consideration of the decomposition temperature, thermal conductivity, and harmfulness to the human body.

In one embodiment of the present invention, the retarder composition may further include 1 to 10 parts by weight of additives based on 100 parts by weight of the sum of Si, CuO, and MnO ₂ .

As the additive, at least one selected from the group consisting of clay, diatomaceous earth, calcium carbonate, magnesium carbonate, and magnesium bicarbonate may be used, and in particular, diatomaceous earth may be preferably used. The diatomaceous earth is an inert material used for the purpose of delaying the combustion rate, and slows the reaction by absorbing heat and isolating reactive materials.

In one embodiment of the present invention, the retarder composition may further include a binder in an amount of 0.05 to 1.0 parts by weight based on 100 parts by weight of Si, CuO, and MnO ₂ inclusive.

As the binder, at least one selected from methyl cellulose, ethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyvinyl acetate, and VAAR may be used.

In one embodiment of the present invention, the Si, CuO and MnO ₂ may have an average particle size of 1 μm to 10 μm, preferably 2 μm to 6 μm.

In one embodiment of the present invention, the non-toxic retarder composition for a primer may have a unit second time of 30 to 100 ms/mm, and 40 to 60 ms/mm.

The retarder composition of the present invention is prepared in a granular state by adding a binder dissolved in an organic solvent or water to facilitate filling and compression with a mixture of powder components. The granules may be prepared by methods known in the art.

The retarder composition of the present invention is charged directly into the metal tube for a primer or is charged in an internal metal tube and is ignited by the electric detonator igniter or the non-electric detonator shock tube and burns for a predetermined delay time, then the primary charge It has an ignition/detonation train characteristic that detonates the detonator and then the secondary charge is fully detonated and the detonator explodes.

The retarder composition of the present invention may be conventionally compression molded. The compression molding pressure varies depending on the length of the gunpowder and the shape of the element, and for example, it is preferable to be filled with a filling pressure in the range of 2000 to 3000 kgf/cm 2 .

In addition, the present invention,

It relates to a delayed-type primer comprising a tube body, an ignition means positioned at the top of the tube body, an initiator and an add-on agent positioned at the end of the tube body, and the non-toxic retarder composition for a primer of the present invention positioned in the middle of the tube body.

In the configuration of the delay-type primer, except for the non-toxic retarder composition for the primer, any configuration known in the art may be employed without limitation.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are provided to explain the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Examples 1 to 7: Preparation and Performance Evaluation of Retardant Compositions

(1) Preparation of retardant composition

The components in Table 1 below were weighed in the corresponding ratio and passed through a 60mesh standard sieve 6 times, followed by dry mixing. Based on 100 parts by weight of the dry mixture, 0.25 parts by weight of methyl cellulose as a binder was added, mixed and dried in a wet state, and passed through a 30 mesh standard sieve to prepare granules.

(2) Performance test of retardant composition

The sample prepared above confirmed the safety of the composition through friction sensitivity, drop sensitivity, static electricity sensitivity, and ignition point tests. The retarder composition was repeatedly filled and compressed in a metal tube to make a delay tube of about 10 mm in height, and the delay tube was inserted into the tube filled with the initiator and supplement to prepare a non-electrical primer.

The delay time was measured at room temperature to evaluate the ultra-precision, and the results are shown in Table 1 below.

In addition, in order to evaluate the detonation reliability under adverse conditions, inert primers that were not filled with initiators and excipients were prepared, and after low-temperature treatment of 20 shots each for 3 hours at minus 20 degrees Celsius, the detonation results are shown in Table 1 below.

Composition (% by weight) bad conditions
ignition test initial exam Si CuO MnO ₂ diatomaceous earth Average (ms) Standard Deviation Cv sample water Example 1 35 52 13 4 full blown 695.0 5.8 0.83 20 Example 2 37 48 15 5 full blown 654.6 7.3 1.12 20 Example 3 40 40 20 5 full blown 611.5 7.9 1.29 10 Example 4 42 43 15 7 full blown 684.5 19.6 2.86 20 Example 5 45 45 10 4 full blown 554.8 16.1 2.90 20 Example 6 45 40 15 6 full blown 673.7 10.2 1.51 20 Example 7 47 38 15 4 full blown 640.8 9.2 1.44 20

Note) Cv: (Coefficient of variation)

The average particle size of Si is 3.5㎛

The average particle size of CuO is 5.7㎛

The average particle size of MnO ₂ is 4.3㎛

The average particle size of diatomaceous earth is 36.7㎛

From the above experiment, it was confirmed that the retarder composition of the present invention satisfies initiation reliability and delay time precision (ultra-time precision).

(3) Scale-up test

Among the above examples, the composition of Example 5 was selected, mixed and prepared with a muller mixer of SIMPSON Technlogies in the United States, and filled in a metal tube (retardant pipe) using an automatic weighing and pressing machine (retardant filling equipment), and 3,000 kgf/cm2 of compressed with pressure. The delay tube was inserted into the tube filled with the initiator and the excipient, and a non-electric primer was prepared, and the delay time was measured at room temperature. The measurement results are shown in Table 2 below.

Classification of exams Abbreviation (mm) Average seconds (ms) Standard Deviation Cv Number of samples (foot) Primary 7.30 374.3 8.9 2.38 20 15.0 811.7 7.7 0.95 20 Secondary 7.40 368.2 7.6 2.07 20 15.10 779.0 9.7 1.25 20 18.40 952.9 7.3 0.77 20 tertiary 7.60 406.7 9.9 2.42 20 18.0 956.8 7.6 0.79 20

As shown in Tables 3 and 4 below, stability (storage safety) was confirmed through thermal shock test and long-term storage test.

to give Initial test result (about 18.0mm in height), 40 shots each) bad condition ignition test
(100 shots each) Average seconds (ms) Standard Deviation before test 956.8 7.58 full blown after test 959.2 8.40 full blown

to give Initial test result of long-term storage test (approx. 7.4mm high, 20 shots each)) immediately after manufacturing 1 month 6 months 12 months 24 months Average seconds (ms) 368.2 364.2 372.3 366.9 369.7

According to the above experimental results, the retarder composition of the present invention provides a wider range of combustion speed than the conventional retarder composition containing lead, it is possible to freely adjust the delay time according to the design intention, and improved ultra-precision and detonation reliability. Moreover, it turns out that Stability (storage stability) is also excellent.

Claims (8)

Si, CuO and MnO ₂ A non-toxic retarder composition for a primer comprising 35 to 55:38 to 52:7 to 25 in a weight ratio. According to claim 1,
The non-toxic retarder composition for a primer, wherein the retarder composition further comprises 1 to 10 parts by weight of additives based on 100 parts by weight of the sum of Si, CuO and MnO ₂ . According to claim 1,
The additive is a non-toxic retarder composition for a primer, characterized in that at least one selected from the group consisting of clay, diatomaceous earth, calcium carbonate, magnesium carbonate and magnesium bicarbonate. 3. The method of claim 2,
The retarder composition further comprises 0.05 to 1.0 parts by weight of a binder based on 100 parts by weight of the sum of Si, CuO and MnO ₂ . 5. The method of claim 4,
The binder is a non-toxic retarder composition for a primer, characterized in that at least one selected from methyl cellulose, ethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyvinyl acetate, and VAAR. According to claim 1,
The Si, CuO and MnO ₂ is a non-toxic retarder composition for a primer, characterized in that the average particle size is 1㎛ ~ 10㎛. According to claim 1,
A non-toxic retardant composition for a primer, characterized in that the unit second time is 30 to 100 ms/mm. The tube body, the ignition means located at the top of the tube body, the initiator and the add-on agent located at the end of the tube body, and the non-toxic retarder for the detonator of any one of claims 1 to 6 located in the middle of the tube body A delayed primer comprising the composition.