JPS6343355B2 - - Google Patents
Info
- Publication number
- JPS6343355B2 JPS6343355B2 JP55124201A JP12420180A JPS6343355B2 JP S6343355 B2 JPS6343355 B2 JP S6343355B2 JP 55124201 A JP55124201 A JP 55124201A JP 12420180 A JP12420180 A JP 12420180A JP S6343355 B2 JPS6343355 B2 JP S6343355B2
- Authority
- JP
- Japan
- Prior art keywords
- emulsion explosive
- explosive composition
- ammonium nitrate
- sodium
- emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000203 mixture Substances 0.000 claims description 46
- 239000002360 explosive Substances 0.000 claims description 35
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical class OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 10
- 239000001993 wax Substances 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- 239000000295 fuel oil Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 229910052809 inorganic oxide Chemical class 0.000 claims description 5
- 150000005324 oxide salts Chemical class 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 239000007762 w/o emulsion Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 description 32
- 238000005474 detonation Methods 0.000 description 13
- -1 alkali metal chlorates Chemical class 0.000 description 9
- 239000002666 chemical blowing agent Substances 0.000 description 8
- 230000005484 gravity Effects 0.000 description 8
- 239000007800 oxidant agent Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000004200 microcrystalline wax Substances 0.000 description 3
- 235000019808 microcrystalline wax Nutrition 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000001235 sensitizing effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 2
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000001593 sorbitan monooleate Substances 0.000 description 2
- 235000011069 sorbitan monooleate Nutrition 0.000 description 2
- 229940035049 sorbitan monooleate Drugs 0.000 description 2
- CUNWUEBNSZSNRX-RKGWDQTMSA-N (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;(z)-octadec-9-enoic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O CUNWUEBNSZSNRX-RKGWDQTMSA-N 0.000 description 1
- DSEKYWAQQVUQTP-XEWMWGOFSA-N (2r,4r,4as,6as,6as,6br,8ar,12ar,14as,14bs)-2-hydroxy-4,4a,6a,6b,8a,11,11,14a-octamethyl-2,4,5,6,6a,7,8,9,10,12,12a,13,14,14b-tetradecahydro-1h-picen-3-one Chemical compound C([C@H]1[C@]2(C)CC[C@@]34C)C(C)(C)CC[C@]1(C)CC[C@]2(C)[C@H]4CC[C@@]1(C)[C@H]3C[C@@H](O)C(=O)[C@@H]1C DSEKYWAQQVUQTP-XEWMWGOFSA-N 0.000 description 1
- USVVENVKYJZFMW-ONEGZZNKSA-N (e)-carboxyiminocarbamic acid Chemical compound OC(=O)\N=N\C(O)=O USVVENVKYJZFMW-ONEGZZNKSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000283153 Cetacea Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- SNIOPGDIGTZGOP-UHFFFAOYSA-N Nitroglycerin Chemical compound [O-][N+](=O)OCC(O[N+]([O-])=O)CO[N+]([O-])=O SNIOPGDIGTZGOP-UHFFFAOYSA-N 0.000 description 1
- 239000000006 Nitroglycerin Substances 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 239000004147 Sorbitan trioleate Substances 0.000 description 1
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- TTZKGYULRVDFJJ-GIVMLJSASA-N [(2r)-2-[(2s,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-[(z)-octadec-9-enoyl]oxyethyl] (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1O TTZKGYULRVDFJJ-GIVMLJSASA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910001485 alkali metal perchlorate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012164 animal wax Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000019961 diglycerides of fatty acid Nutrition 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 229960003711 glyceryl trinitrate Drugs 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- PTIUDKQYXMFYAI-UHFFFAOYSA-N methylammonium nitrate Chemical compound NC.O[N+]([O-])=O PTIUDKQYXMFYAI-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000012184 mineral wax Substances 0.000 description 1
- 235000019960 monoglycerides of fatty acid Nutrition 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- 239000005332 obsidian Substances 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229940083254 peripheral vasodilators imidazoline derivative Drugs 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 description 1
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 239000001587 sorbitan monostearate Substances 0.000 description 1
- 235000011076 sorbitan monostearate Nutrition 0.000 description 1
- 229940035048 sorbitan monostearate Drugs 0.000 description 1
- 229960005078 sorbitan sesquioleate Drugs 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 150000003438 strontium compounds Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Landscapes
- Colloid Chemistry (AREA)
Description
本発明は油中水型エマルシヨン爆薬組成物（以
下Ｗ／Ｏ型エマルシヨン爆薬組成物と略記する）
に係り、特にＷ／Ｏ型エマルシヨン爆薬組成物の
起爆感度を改良するために従来から用いられてい
る火薬類、非火薬類、爆轟触媒的鋭感剤もしくは
アンモニウムまたはアルカリ金属の塩素酸塩また
は過塩素酸塩等の鋭感性酸化剤を含有しないＷ／
Ｏ型エマルシヨン爆薬組成物において、特定の化
合物を配合することにより、小口径および低温に
おける起爆感度の経時安定性を大幅に改良せしめ
たＷ／Ｏ型エマルシヨン爆薬組成物に関するもの
である。
従来からニトログリセリン等の火薬類鋭感剤、
モノメチルアミン硝酸塩等の非火薬類鋭感剤（以
上の鋭感剤を以下鋭感性物質と略記する）、原子
番号13以上でかつ周期律表の第１族、第２族以外
の金属の化合物または水溶性ストロンチウム化合
物等の爆轟触媒的鋭感剤、もしくはアンモニウム
またはアルカリ金属の過塩素酸塩等の鋭感性酸化
剤（以上の鋭感剤を以下補助鋭感性物質と略記す
る）を配合して小口径で低温における起爆感度を
改良したＷ／Ｏ型エマルシヨン爆薬組成物は数多
く知られている。しかし、これらのＷ／Ｏ型エマ
ルシヨン爆薬組成物を製造するには、前記の鋭感
性物質もしくは補助鋭感性物質を輸送しかつ配合
する必要があるが、それらの取扱い上の危険性が
大きいものもあり、またそれらを用いた爆薬の製
造時の揮発ガスおよび使用後の爆発ガスの不快性
または毒性等が問題になることも多い。さらに
又、原材料費として高価なものになる場合も多
い。従つて、すべての爆薬組成物について言える
ことであるが、一切の鋭感性物質もしくは補助鋭
感性物質を配合しないものが望ましい。このよう
な意味から、前記の様な鋭感性もしくは補助鋭感
性物質を含有させないで、小口径で６号***もし
くは８号***で起爆可能なＷ／Ｏ型エマルシヨン
爆薬組成物も過去に２〜３発表されている。
例えば米国特許第4110134号明細書によれば、
気泡保持剤としてガラス微小中空球体を配合して
約1.25インチ（31.8mm）の薬径で６号***で最高
1.25の仮比重まで完爆する旨のことが記載されて
いる。また、米国特許第4149917号明細書によれ
ば、気泡保持物質は含有しないで微小気泡により
仮比重を0.95に調整し、1.25インチ（31.8mm）で
製造から２ケ月経過しても６号***で完爆し（爆
薬温度21.1℃）、８ケ月経過後で８号***で完爆
する（爆薬温度21.1℃）ことが記載されている。
以上のように前記の鋭感性もしくは補助鋭感性
物質を含有しない従来のＷ／Ｏ型エマルシヨン爆
薬組成物は、小口径（1.25インチ）で６号***も
しくは８号***で完爆するが、より小口径（1.25
インチ以下）および低温時の起爆感度もしくは、
それらの経時安定性が十分でない等の問題があつ
た。
本発明は前記の様な問題点、即ちより小口径
（１インチ）および低温時（−５℃）の起爆感度
およびそれらの経時安定性の不良を解消するた
め、鋭意研究した結果得られたものである。
即ち、本発明のＷ／Ｏ型エマルシヨン爆薬組成
物は、(イ)硝酸アンモニウムまたは硝酸アンモニウ
ムと他の無機酸化酸塩(ロ)水および(ハ)炭酸ナトリウ
ム、酢酸ナトリウム、ケイ酸アンモニウム、クエ
ン酸ナトリウム、エチレンジアミン四酢酸および
酒石酸からなる群から選ばれる少なくとも１種を
全組成に対して0.3〜３重量％含んでなる酸化剤
水溶液の分散相、(ニ)燃料油および／またはワツク
ス類からなる可燃剤の連続相、(ホ)乳化剤および(ヘ)
微小中空球体または微小気泡を含有させてなるこ
とを特徴とする油中水型エマルシヨン爆薬組成物
である。
本発明のＷ／Ｏ型エマルシヨン爆薬組成物の酸
化剤水溶液は、硝酸アンモニウムを主成分とし必
要に応じて他の無機酸化酸塩を含有させてなるも
のである。ここで他の無機酸化酸塩とは、例えば
硝酸ナトリウム、硝酸カルシウム等のアルカリ金
属または、アルカリ土類金属の硝酸塩である。こ
れらの無機酸化酸塩は、１種または２種以上の混
合物として用いる。硝酸アンモニウムの配合量
は、一般に全体の40％〜90％（重量基準、以下同
様）であり、必要に応じて他の無機酸化酸塩を硝
酸アンモニウムを含む無機酸化酸塩全体の40％以
下で含有させても良い。
燃料油および／またはワツクス類の燃料油は炭
化水素、例えばパラフイン系炭化水素、オレフイ
ン系炭化水素、ナフテン系炭化水素、芳香族炭化
水素、飽和または不飽和炭化水素、石油、精製鉱
油、潤滑油、流動パラフイン等および炭化水素誘
導体、例えばニトロ炭化水素等である。またワツ
クス類は石油から誘導される未精製マイクロクリ
スタリンワツクス、精製マイクロクリスタリンワ
ツクス、パラフインワツクス等、鉱物性ワツクス
であるモンタンワツクス、オゾケライト等、動物
性ワツクスである鯨ロウ等、および昆虫ワツクス
である蜜ロウ等である。これらの燃料油および／
またはワツクス類は１種または２種以上の混合物
として用いる。燃料油および／またはワツクス類
の配合量は一般に１％〜10％である。
乳化剤は特に限定するものでなく、従来から知
られているＷ／Ｏ型エマルシヨンを形成するすべ
ての乳化剤を包含する。例えばソルピタン脂肪酸
エステル、即ちソルビタンモノラウレート、ソル
ピタンモノオレエート、ソルビタンモノパルミテ
ート、ソルピタンモノステアレート、ソルビタン
セスキオレエート、ソルビタンジオレエート、ソ
ルビタントリオレエート等、脂肪酸のモノまたは
ジグリセライド、即ちステアリン酸モノグリセラ
イド等、ポリオキシエチレンソルビタン脂肪酸エ
ステル、即ちポリオキシエチレンソルビタンモノ
ラウレート、ポリオキシエチレンソルビタンモノ
ステアレート等、オキサゾリン誘導体、イミダゾ
リン誘導体、リン酸エステル、脂肪酸のアルカリ
金属塩またはアルカリ土類金属塩、一級、二級お
よび三級アミンまたは一級、二級、三級アミンの
硝酸塩または酢酸塩である。これらの乳化剤は１
種または２種以上の混合物として用いる。乳化剤
の配合量は、一般には0.5％〜５％である。
本発明に用いられる特定の化合物は、炭酸ナト
リウム、酢酸ナトリウム、ケイ酸アンモニウム、
クエン酸ナトリウム、エチレンジアミン四酢酸お
よび酒石酸である。
これらの化合物は、使用に際し、１種または２
種以上の混合物として用いられる。またこれら化
合物の配合量は、0.3〜３重量％である。0.3重量
％未満では、小口径および低温における起爆感度
の経時安定性を大幅に改良することができなく、
また３重量％を越えても、それに見合うだけの効
果が得られなく、経済的に不利である。
また本発明のＷ／Ｏ型エマルシヨン爆薬組成物
は仮比重調整剤により、その仮比重を0.80〜1.35
（好ましくは1.00〜1.15）に調整される。その仮
比重調整剤は、微小中空球体または微小気泡であ
り、微小中空球体とは、例えばガラス、アルミ
ナ、頁岩、シラス、珪砂、火山岩、ケイ酸ナトリ
ウム、ホウ砂、真珠岩、黒曜岩等から得られる無
機質系微小中空球体、ピツチ、石炭等から得られ
る炭素質系微小中空球体、フエノール樹脂、ポリ
塩化ピニリデン、エポキシ樹脂、尿素樹脂等から
得られる合成樹脂系微小中空球体等であり、これ
らの微小中空球体は１種または２種以上の混合物
として用いる。微小中空球体の配合量は一般に１
％〜10％である。微小気泡とは、例えば化学発泡
剤を含有させて発泡させて得られる微小気泡、ま
たはＷ／Ｏ型エマルシヨンの形成時または形成後
の工程で機械的に空気またはその他のガスを吹き
込んで得られる微小気泡等である。化学発泡剤と
は、例えばアルカリ金属ホウ素水素化物や亜硝酸
ナトリウムと尿素とを組合せて用いるもの等の無
機系化学発泡剤、またはＮ，N′―ジニトロソペ
ンタメチレンテトラミン、アゾジカルボン酸アミ
ド、アゾビスイソブチロニトリル等の有機系化学
発泡剤等である。これらの化学発泡剤は１種また
は２種以上の混合物として用いる。化学発泡剤の
配合量は、一般に0.01％〜２％である。
以上のような本発明のＷ／Ｏ型エマルシヨン爆
薬組成物は、前記のような特定の化合物を含有す
ることにより、乳化状態の経時安定性が向上し、
その結果、小口径および低温における起爆感度の
経時安定性が大幅に改良されたものである。
本発明のＷ／Ｏ型エマルシヨン爆薬組成物の製
造方法は、例えば次のとおりである。即ち硝酸ア
ンモニウムまたは硝酸アンモニウムと他の無機酸
化酸塩との混合物に特定の化合物を配合したもの
を約80℃〜90℃で水に溶解させた酸化剤水溶液を
得る。一方、乳化剤と燃料油および／またはワツ
クス類とを80℃〜90℃で溶融混合させた混合物
（以下可燃剤混合物と略記する）を得る。次に一
定容量の保温可能な容器内にまず可燃剤混合物を
入れ、酸化剤水溶液を徐々に添加しながら通常使
用されるプロペラ羽根式撹拌機を用いて約
1600rpmで約５分間混合撹拌して約85℃のＷ／Ｏ
型エマルシヨンを得る。次に微小中空球体または
化学発泡剤を前記のＷ／Ｏ型エマルシヨンに縦型
捏和機を用いて約30rpmで混合することにより
Ｗ／Ｏ型エマルシヨン爆薬組成物を得る。なお微
小中空球体または化学発泡剤による微小気泡の代
りに空気等のガスによる微小気泡を含有させる場
合には、前記のＷ／Ｏ型エマルシヨンに空気等の
ガスを吹き込みながら撹拌することによつてＷ／
Ｏ型エマルシヨン爆薬組成物を得る。
次に本発明のＷ／Ｏ型エマルシヨン爆薬組成物
を実施例および比較例によつて具体的に説明す
る。なお各例中の部数および％はすべて重量基準
である。
実施例 １
第１表に示すような配合組成のＷ／Ｏ型エマル
シヨン爆薬組成物を下記のようにして製造した。
まず、硝酸アンモニウム377.90部（75.58％）
および硝酸ナトリウム22.65部（4.53％）および
炭酸ナトリウム4.80部（0.96％）を水54.70部
（10.94％）に加えて加温することにより溶解さ
せ、約85℃の酸化剤水溶液を得た。一方、ソルビ
タンモノオレエート8.65部（1.73％）と未精製マ
イクロクリスタリンワツクス16.85部（3.37％）
との混合物を加温して溶融させ約85℃の可燃剤混
合物を得た。保温可能な容器内にまず前記の可燃
剤混合物を入れ、次に前記の酸化剤水溶液を徐々
に添加しながら、プロペラ羽根式撹拌器を用い
て、約1600rpmで約５分間、混合撹拌して、約85
℃のＷ／Ｏ型エマルシヨンを得た。次に平均粒径
75μのカラス微小中空球体14.45部（2.99％）を前
記のＷ／Ｏ型エマルシヨンに縦型捏和機を用いて
約30rpmで混合することによりＷ／Ｏ型エマルシ
ヨン爆薬組成物を得た。このＷ／Ｏ型エマルシヨ
ン爆薬組成物は、直径25mm、長さ約180mmで薬量
100grになるように成形し、ビスコース加工紙で
包装した薬包となし各性能試験に供した。性能試
験としては(イ)製造１日後の仮比重の測定、(ロ)試料
薬包を60℃で24時間保ちその後−15℃で24時間保
つて、これを１サイクルとした温度サイクルを繰
返して行なうという強制劣化貯蔵試験を行なつた
後、６号***を用いて−５℃で起爆試験を行なつ
た時に完爆しうる温度サイクル回数を求め、その
回数を常温（10〜30℃）放置貯蔵における完爆可
能貯蔵月数として推定（前記１温度サイクルが常
温放置貯蔵のほぼ１ケ月に相当することを実験的
に確認したことから推定した。）した起爆感度経
時安定性試験、および(ハ)前記(ロ)の起爆試験時の仮
比重測定を行つた。その結果は第１表に示すとお
りであつた。
実施例 ２〜10
第１表に示すような配合組成のＷ／Ｏ型エマル
シヨン爆薬組成物を実施例１に準じて製造した。
このＷ／Ｏ型エマルシヨン爆薬組成物を実施例１
に記載されている方法と同一方法にて、試料薬包
を作成し、同一項目の性能試験を行つた。その結
果は、第１表に示すとおりである。また実施例10
においては、前記の試料薬包を約50℃の恒温槽で
２時間加温して配合した化学発泡剤（Ｎ，N′―
ジニトロソペンタメチレンテトラミン）を分解発
泡させ仮比重を調整したものについて、実施例１
と同一項目の性能試験を行つた。
実施例 11
第１表に示すような配合組成のＷ／Ｏ型エマル
シヨン爆薬組成物を、以下のような方法で製造し
た。即ちまず実施例１に準じてＷ／Ｏ型エマルシ
ヨンを得た。次に前記のＷ／Ｏ型エマルシヨンに
空気を細いノズルから吹き込みながらプロペラ羽
根式撹拌器を用いて、約1600rpmで２分間混合撹
拌を行ない空気の微小気泡を導入し、所要の仮比
重のＷ／Ｏ型エマルシヨン爆薬組成物を得た。こ
のＷ／Ｏ型エマルシヨン爆薬組成物を実施例１に
記載されている方法と同一方法にて、試料薬包を
作成し、同一項目の性能試験を行つた。その結果
は、第１表に示すとおりである。
The present invention relates to a water-in-oil emulsion explosive composition (hereinafter abbreviated as W/O emulsion explosive composition).
In particular, explosives, non-explosives, detonation catalytic sensitizers or ammonium or alkali metal chlorates or W/ does not contain sensitive oxidizing agents such as perchlorate
The present invention relates to a W/O emulsion explosive composition in which the stability over time of detonation sensitivity at small diameters and low temperatures is significantly improved by incorporating a specific compound into the O emulsion explosive composition. Traditionally, explosive sensitizers such as nitroglycerin,
Non-explosive sensitizers such as monomethylamine nitrate (the above sensitizers are hereinafter abbreviated as sensitizers), compounds of metals with an atomic number of 13 or higher and other than Groups 1 and 2 of the periodic table, or A detonation catalytic sensitizer such as a water-soluble strontium compound, or a sensitizing oxidizing agent such as an ammonium or alkali metal perchlorate (the above sensitizers are hereinafter abbreviated as auxiliary sensitizers) is added. Many W/O emulsion explosive compositions are known that have small diameters and improved detonation sensitivity at low temperatures. However, in order to manufacture these W/O type emulsion explosive compositions, it is necessary to transport and blend the above-mentioned sensitizing substances or auxiliary sensitizing substances, but there are some that are highly dangerous in handling. However, there are often problems with the volatile gas produced during the production of explosives using them and the unpleasantness or toxicity of the explosive gas after use. Furthermore, raw materials are often expensive. Therefore, as with all explosive compositions, it is desirable not to include any sensitizers or supplementary sensitizers. In this sense, several W/O emulsion explosive compositions have been developed in the past that do not contain the above-mentioned sensitive or auxiliary sensitive substances and can be detonated with a small diameter detonator No. 6 or No. 8 detonator. It has been announced. For example, according to US Pat. No. 4,110,134,
Contains glass microscopic hollow spheres as a bubble retaining agent, and has a diameter of approximately 1.25 inches (31.8 mm), which is the highest for a No. 6 detonator.
It is stated that it will completely explode up to a tentative specific gravity of 1.25. In addition, according to US Pat. No. 4,149,917, the tentative specific gravity is adjusted to 0.95 using microbubbles without containing a bubble-retaining substance, and the No. It is stated that the bomb will be completely detonated (explosive temperature 21.1℃), and after 8 months it will be completely detonated using No. 8 detonator (explosive temperature 21.1℃). As mentioned above, conventional W/O emulsion explosive compositions that do not contain the above-mentioned sensitive or auxiliary sensitive substances are small in diameter (1.25 inches) and can be completely detonated with a No. 6 detonator or a No. 8 detonator; Caliber (1.25
inch or less) and detonation sensitivity at low temperatures or
There were problems such as insufficient stability over time. The present invention was obtained as a result of intensive research in order to solve the above-mentioned problems, that is, the detonation sensitivity at smaller diameters (1 inch) and at lower temperatures (-5°C), and the poor stability over time. It is. That is, the W/O emulsion explosive composition of the present invention comprises (a) ammonium nitrate or ammonium nitrate and other inorganic oxide salts, (b) water, and (c) sodium carbonate, sodium acetate, ammonium silicate, sodium citrate, A dispersed phase of an oxidizing agent aqueous solution containing 0.3 to 3% by weight of at least one selected from the group consisting of ethylenediaminetetraacetic acid and tartaric acid based on the total composition; (d) a combustible agent consisting of fuel oil and/or waxes; continuous phase, (e) emulsifier and (f)
A water-in-oil emulsion explosive composition characterized by containing microscopic hollow spheres or microbubbles. The aqueous oxidizing agent solution of the W/O emulsion explosive composition of the present invention contains ammonium nitrate as a main component and contains other inorganic oxidizing acid salts as necessary. Here, other inorganic oxide salts are, for example, nitrates of alkali metals or alkaline earth metals such as sodium nitrate and calcium nitrate. These inorganic oxidized acid salts may be used alone or as a mixture of two or more. The amount of ammonium nitrate is generally 40% to 90% of the total (by weight, the same applies hereinafter), and if necessary, other inorganic oxide salts may be included at 40% or less of the total amount of inorganic oxide salts including ammonium nitrate. It's okay. Fuel oils and/or wax fuel oils include hydrocarbons, such as paraffinic hydrocarbons, olefinic hydrocarbons, naphthenic hydrocarbons, aromatic hydrocarbons, saturated or unsaturated hydrocarbons, petroleum, refined mineral oils, lubricating oils, Liquid paraffin and the like and hydrocarbon derivatives such as nitrohydrocarbons. Waxes include unrefined microcrystalline wax derived from petroleum, refined microcrystalline wax, paraffin wax, mineral waxes such as montan wax and ozokerite, animal waxes such as whale wax, and insect waxes. These include beeswax, which is wax. These fuel oils and/or
Alternatively, waxes may be used alone or as a mixture of two or more. The amount of fuel oil and/or waxes is generally 1% to 10%. The emulsifier is not particularly limited, and includes all conventionally known emulsifiers that form W/O emulsions. For example, mono- or diglycerides of fatty acids, such as sorbitan fatty acid esters, i.e. sorbitan monolaurate, sorbitan monooleate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan dioleate, sorbitan trioleate, etc. Stearic acid monoglyceride, etc., polyoxyethylene sorbitan fatty acid esters, i.e. polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, etc., oxazoline derivatives, imidazoline derivatives, phosphoric acid esters, alkali metal salts or alkaline earth metals of fatty acids salts, primary, secondary and tertiary amines or nitrates or acetates of primary, secondary and tertiary amines. These emulsifiers are 1
Used as a seed or a mixture of two or more. The amount of emulsifier added is generally 0.5% to 5%. Specific compounds used in the present invention include sodium carbonate, sodium acetate, ammonium silicate,
Sodium citrate, ethylenediaminetetraacetic acid and tartaric acid. When using these compounds, one or two types may be used.
Used as a mixture of more than one species. Further, the blending amount of these compounds is 0.3 to 3% by weight. If it is less than 0.3% by weight, the stability over time of detonation sensitivity at small diameters and low temperatures cannot be significantly improved;
Moreover, even if the amount exceeds 3% by weight, the corresponding effect cannot be obtained, which is economically disadvantageous. Further, the W/O type emulsion explosive composition of the present invention has a temporary specific gravity of 0.80 to 1.35 by using a temporary specific gravity adjusting agent.
(preferably adjusted to 1.00 to 1.15). The temporary specific gravity adjusting agent is a micro hollow sphere or a micro bubble, and the micro hollow sphere is made of, for example, glass, alumina, shale, shirasu, silica sand, volcanic rock, sodium silicate, borax, nacre, obsidian, etc. The resulting inorganic micro hollow spheres, the carbonaceous micro hollow spheres obtained from pitch, coal, etc., the synthetic resin micro hollow spheres obtained from phenolic resins, polypinylidene chloride, epoxy resins, urea resins, etc. The micro hollow spheres may be used alone or as a mixture of two or more. The amount of micro hollow spheres is generally 1
%~10%. Microbubbles are, for example, microbubbles obtained by foaming a chemical foaming agent, or microbubbles obtained by mechanically blowing air or other gas during or after the formation of a W/O emulsion. Air bubbles, etc. Chemical blowing agents include, for example, inorganic chemical blowing agents such as alkali metal boron hydrides, those using a combination of sodium nitrite and urea, or N,N'-dinitrosopentamethylenetetramine, azodicarboxylic acid amide, azo These include organic chemical blowing agents such as bisisobutyronitrile. These chemical blowing agents may be used alone or as a mixture of two or more. The amount of chemical blowing agent added is generally 0.01% to 2%. By containing the above-mentioned specific compounds, the W/O emulsion explosive composition of the present invention improves the stability of the emulsified state over time,
As a result, the stability over time of detonation sensitivity at small diameters and low temperatures has been significantly improved. The method for producing the W/O emulsion explosive composition of the present invention is, for example, as follows. That is, an oxidizing agent aqueous solution is obtained by dissolving ammonium nitrate or a mixture of ammonium nitrate and other inorganic oxidizing acid salts with a specific compound in water at about 80°C to 90°C. On the other hand, a mixture (hereinafter abbreviated as combustible mixture) is obtained by melting and mixing the emulsifier and fuel oil and/or wax at 80°C to 90°C. Next, first put the combustible mixture in a heat-insulating container with a certain volume, and gradually add the oxidizing agent aqueous solution, using a commonly used propeller blade stirrer to approx.
Mix and stir at 1600 rpm for about 5 minutes to bring the W/O temperature to about 85℃.
Obtain a mold emulsion. Next, a W/O emulsion explosive composition is obtained by mixing micro hollow spheres or a chemical blowing agent into the W/O emulsion using a vertical kneader at about 30 rpm. In addition, when containing microbubbles made of gas such as air instead of microbubbles caused by microscopic hollow spheres or a chemical blowing agent, W/O emulsion can be mixed while blowing gas such as air into the W/O emulsion. /
A type O emulsion explosive composition is obtained. Next, the W/O type emulsion explosive composition of the present invention will be specifically explained with reference to Examples and Comparative Examples. Note that all parts and percentages in each example are based on weight. Example 1 A W/O type emulsion explosive composition having the formulation shown in Table 1 was manufactured as follows. First, ammonium nitrate 377.90 parts (75.58%)
Then, 22.65 parts (4.53%) of sodium nitrate and 4.80 parts (0.96%) of sodium carbonate were added to 54.70 parts (10.94%) of water and dissolved by heating to obtain an oxidizing agent aqueous solution at about 85°C. Meanwhile, sorbitan monooleate 8.65 parts (1.73%) and unrefined microcrystalline wax 16.85 parts (3.37%)
The mixture was heated and melted to obtain a combustible mixture at about 85°C. First, the combustible agent mixture is placed in a heat-insulating container, and then the oxidizing agent aqueous solution is gradually added, using a propeller blade stirrer to mix and stir at approximately 1600 rpm for approximately 5 minutes. about 85
A W/O type emulsion of 0.degree. C. was obtained. Next, the average particle size
A W/O emulsion explosive composition was obtained by mixing 14.45 parts (2.99%) of 75 μm glass micro hollow spheres into the W/O emulsion using a vertical kneader at about 30 rpm. This W/O type emulsion explosive composition has a diameter of 25 mm and a length of approximately 180 mm.
It was molded to a size of 100g and wrapped in viscose-processed paper and subjected to various performance tests. Performance tests included (a) measurement of provisional specific gravity one day after production, and (b) repeated temperature cycles in which the sample cartridge was kept at 60℃ for 24 hours and then kept at -15℃ for 24 hours, with this as one cycle. After conducting a forced deterioration storage test, the number of temperature cycles that would result in a complete detonation when a detonation test was performed at -5℃ using a No. Detonation sensitivity aging stability test estimated as the number of months of storage for complete detonation (estimated from the experimental confirmation that one temperature cycle described above corresponds to approximately one month of storage left at room temperature); ) Temporary specific gravity measurements were made during the detonation test described in (b) above. The results were as shown in Table 1. Examples 2 to 10 W/O emulsion explosive compositions having the formulations shown in Table 1 were produced according to Example 1.
This W/O type emulsion explosive composition was prepared in Example 1.
A sample drug package was prepared using the same method as described in 2013, and performance tests were conducted on the same items. The results are shown in Table 1. Also Example 10
In this method, a chemical blowing agent (N, N′-
Example 1 was prepared by decomposing and foaming (dinitrosopentamethylenetetramine) and adjusting the tentative specific gravity.
Performance tests were conducted on the same items. Example 11 A W/O type emulsion explosive composition having the formulation shown in Table 1 was produced by the following method. That is, first, a W/O type emulsion was obtained according to Example 1. Next, while blowing air into the above-mentioned W/O type emulsion through a thin nozzle, mixing and stirring was performed at approximately 1600 rpm for 2 minutes using a propeller blade type stirrer to introduce microbubbles of air. An O-type emulsion explosive composition was obtained. Sample cartridges were prepared from this W/O emulsion explosive composition in the same manner as described in Example 1, and performance tests were conducted on the same items. The results are shown in Table 1.
【表】【table】
Claims (1)
と他の無機酸化酸塩(ロ)水および(ハ)炭酸ナトリウ
ム、酢酸ナトリウム、ケイ酸アンモニウム、クエ
ン酸ナトリウム、エチレンジアミン四酢酸および
酒石酸からなる群から選ばれる少なくとも１種を
全組成に対して0.3〜３重量％含んでなる酸化剤
水溶液の分散相、(ニ)燃料油および／またはワツク
ス類からなる可燃剤の連続相、(ホ)乳化剤および(ヘ)
微小中空球体または微小気泡を含有させてなるこ
とを特徴とする油中水型エマルシヨン爆薬組成
物。1 (a) ammonium nitrate or ammonium nitrate and other inorganic oxide salts (b) water and (c) at least one member selected from the group consisting of sodium carbonate, sodium acetate, ammonium silicate, sodium citrate, ethylenediaminetetraacetic acid, and tartaric acid. (d) a continuous phase of a combustible agent consisting of fuel oil and/or waxes, (e) an emulsifier, and (f) an emulsifier.
A water-in-oil emulsion explosive composition containing microscopic hollow spheres or microbubbles.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12420180A JPS5747791A (en) | 1980-09-08 | 1980-09-08 | Water-in-oil type emulsion explosive composition |
| US06/293,094 US4394198A (en) | 1980-08-25 | 1981-08-17 | Water-in-oil emulsion explosive composition |
| SE8104902A SE8104902L (en) | 1980-08-25 | 1981-08-18 | THE WATER-IN-OIL EMULSION OF EXPLOSIVE COMPOSITION |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12420180A JPS5747791A (en) | 1980-09-08 | 1980-09-08 | Water-in-oil type emulsion explosive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5747791A JPS5747791A (en) | 1982-03-18 |
| JPS6343355B2 true JPS6343355B2 (en) | 1988-08-30 |
Family
ID=14879480
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12420180A Granted JPS5747791A (en) | 1980-08-25 | 1980-09-08 | Water-in-oil type emulsion explosive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5747791A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0099695B1 (en) * | 1982-07-21 | 1988-01-27 | Imperial Chemical Industries Plc | Emulsion explosive composition |
| JPS6090888A (en) * | 1983-10-21 | 1985-05-22 | 日本油脂株式会社 | Manufacture of water-in-oil emulsion explosive |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56109890A (en) * | 1980-02-05 | 1981-08-31 | Nippon Kayaku Kk | Waterrinnoil type emulsion explosive |
| JPS56155087A (en) * | 1980-04-28 | 1981-12-01 | Nippon Kayaku Kk | Stable explosive composition |
-
1980
- 1980-09-08 JP JP12420180A patent/JPS5747791A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56109890A (en) * | 1980-02-05 | 1981-08-31 | Nippon Kayaku Kk | Waterrinnoil type emulsion explosive |
| JPS56155087A (en) * | 1980-04-28 | 1981-12-01 | Nippon Kayaku Kk | Stable explosive composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5747791A (en) | 1982-03-18 |
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