JPS6154759B2 - - Google Patents
Info
- Publication number
- JPS6154759B2 JPS6154759B2 JP6928481A JP6928481A JPS6154759B2 JP S6154759 B2 JPS6154759 B2 JP S6154759B2 JP 6928481 A JP6928481 A JP 6928481A JP 6928481 A JP6928481 A JP 6928481A JP S6154759 B2 JPS6154759 B2 JP S6154759B2
- Authority
- JP
- Japan
- Prior art keywords
- emulsion explosive
- explosive composition
- acid amide
- cnh
- fatty acid
- 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 74
- 239000002360 explosive Substances 0.000 claims description 57
- 239000003995 emulsifying agent Substances 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 16
- 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 14
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 13
- 239000000194 fatty acid Substances 0.000 claims description 13
- 229930195729 fatty acid Natural products 0.000 claims description 13
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 239000001993 wax Substances 0.000 claims description 8
- 150000004665 fatty acids Chemical class 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000000295 fuel oil Substances 0.000 claims description 6
- 229910052809 inorganic oxide Chemical class 0.000 claims description 6
- 150000005324 oxide salts Chemical class 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007762 w/o emulsion Substances 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 description 62
- 238000005474 detonation Methods 0.000 description 21
- -1 sorbitan fatty acid ester Chemical class 0.000 description 15
- 230000005484 gravity Effects 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- 230000035945 sensitivity Effects 0.000 description 12
- 239000002666 chemical blowing agent Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 238000011056 performance test Methods 0.000 description 7
- SFIHQZFZMWZOJV-HZJYTTRNSA-N linoleamide Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(N)=O SFIHQZFZMWZOJV-HZJYTTRNSA-N 0.000 description 6
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 6
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001593 sorbitan monooleate Substances 0.000 description 5
- 235000011069 sorbitan monooleate Nutrition 0.000 description 5
- 229940035049 sorbitan monooleate Drugs 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 238000004880 explosion Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229940049964 oleate Drugs 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 230000001235 sensitizing effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KZVIUXKOLXVBPC-UHFFFAOYSA-N 16-methylheptadecanamide Chemical compound CC(C)CCCCCCCCCCCCCCC(N)=O KZVIUXKOLXVBPC-UHFFFAOYSA-N 0.000 description 3
- ORAWFNKFUWGRJG-UHFFFAOYSA-N Docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(N)=O ORAWFNKFUWGRJG-UHFFFAOYSA-N 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 235000010344 sodium nitrate Nutrition 0.000 description 3
- 239000004317 sodium nitrate Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000003504 2-oxazolinyl group Chemical class O1C(=NCC1)* 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 229940070765 laurate Drugs 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 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
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- HBXWUCXDUUJDRB-UHFFFAOYSA-N 1-octadecoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCCCC HBXWUCXDUUJDRB-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 206010021143 Hypoxia Diseases 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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000004163 Spermaceti wax Substances 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
- 239000000654 additive Substances 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
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth 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
- 150000001408 amides Chemical class 0.000 description 1
- 239000012164 animal wax Substances 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 229960003711 glyceryl trinitrate Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 238000005259 measurement Methods 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
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000005332 obsidian Substances 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 230000009257 reactivity Effects 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
- 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
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 235000019385 spermaceti wax Nutrition 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
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、W/O型エマルシヨンを形成する新規な
乳化剤を含む爆薬組成物に関するものであつて、
特に、高級脂肪酸アミドを乳化剤として使用する
ことにより小口径(25mm)及び低温における起爆
感度の経時安定性に於て従来の公知の乳化剤以上
の性能を有するW/O型エマルシヨン爆薬組成物
に関するものである。
W/O型エマルシヨン爆薬組成物については、
古くから研究されており、初期のものはW/O型
エマルシヨンの形態が不安定であつたため(即ち
分散相と連続相の接触面積が比較的小さかつたた
め)ニトログリセリン等の火薬類鋭感剤又はモノ
メチルアミン硝酸塩等の非火薬類鋭感剤等(以下
鋭感性物質等と略記する)あるいは、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
の化合物又は水溶性ストロンチウム化合物等の爆
薬触媒的鋭感剤又はアンモニウム又はアルカリ金
属の過塩素酸塩等の鋭感性酸化剤等(以下補助鋭
感性物質等と略記する)を配合して小口径におけ
る起爆感度を改良したものがほとんどであつた。
しかしこの様な鋭感性物質もしくは補助鋭感性物
質等を配合したW/O型エマルシヨン爆薬組成物
は、例えば製造時、使用時に何等かの要因により
上記の様な鋭感性物質等が分離した場合には極め
て鋭感になつてしまうとかあるいは上記の様な鋭
感性物質等の毒性等の潜在的危険性があつた。こ
の様な意味で前記の鋭感性物質もしくは補助鋭感
性物質を一切含有させないで、小口径における起
爆感度を改良(***起爆可能に)にしたW/O型
エマルシヨン爆薬組成物も開示されている。
例えば、米国特許第4110134号明細書によれ
ば、乳化剤としてソルビタン脂肪酸エステル、グ
リセリン脂肪酸エステル、ポリオキシエチレンソ
ルビトール脂肪酸エステル、ポリオキシエチレン
エーテル、ポリオキシアルキレンオレイン酸エス
テル、ポリオキシアルキレンラウリル酸エステ
ル、リン酸オレイン酸エステル、置換オキサゾリ
ン及びリン酸エステルを配合しかつ気泡保持剤と
してガラスマイクロバルーンを配合して約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、乳
化剤としてソルビタン脂肪酸エステル、グリセリ
ン脂肪酸エステル、ポリオキシエチレンソルビタ
ン脂肪酸エステル、ポリオキシエチレン(4)ラウリ
ルエーテル、ポリオキシエチレン(2)エーテル、ポ
リオキシエチレン(2)ステアリルエーテル、ポリオ
キシアルキレンオレイン酸エステル、ポリオキシ
アルキレンラウリル酸エステル、リン酸オレイン
酸エステル、置換オキサゾリン、リン酸エステル
及びこれらの混合物を配合し、気泡保持物質を含
有せずに微小気泡により仮比重を0.95に調整し、
1.25インチ(31.8mm)の薬径で製造から2カ月経
過しても6号***で完爆し(薬温21.1℃)、8カ
月経過後でも8号***で完爆する(爆薬温度21.1
℃)ことが記載されている。
このように上記の様な鋭感性物質もしくは補助
鋭感性物質等を配合しないW/O型エマルシヨン
爆薬組成物に於て、各種の乳化剤が用いられるこ
とは公知であり、その他にもW/O型エマルシヨ
ンを形成する各種の乳化剤が知られている。とこ
ろが、上記米国特許明細書に記載されている以外
の乳化剤を用いたW/O型エマルシヨン爆薬組成
物は、上記のような鋭感性物質もしくは補助鋭感
性物質等を配合する事実からも判る様にそのW/
O型エマルシヨンの経時安定性が悪いため、小口
径(25mm径)及び低温に於ける起爆感度の経時安
定性が極めて悪かつた。
又、上記米国特許明細書に記載されている乳化
剤を用いたW/O型エマルシヨン爆薬組成物で
も、より小口径(25mm径)で低温に於ける起爆感
度の経時安定性が、十分満足できるものではなか
つた。
本発明者等は、前記の様な問題点を考慮しなが
ら、長期間に渡り鋭意研究した結果、従来、W/
O型エマルシヨン爆薬組成物の乳化剤として考え
られなかつた物質が、硝酸アンモニウム又は硝酸
アンモニウムと他の無機酸化酸塩と水からなる酸
化剤水溶液と、燃料油及び/又はワツクス類から
なる可燃剤とをW/O型エマルシヨンに形成し得
ることを見出し、しかもこれによつて得られた
W/O型エマルシヨン爆薬組成物は、小口径及び
低温における起爆感度の経時安定性において従来
の公知の乳化剤以上の性能を有するものであるこ
とが判明し本発明を完成した。
即ち、本発明のW/O型エマルシヨン爆薬組成
物は、(イ)硝酸アンモニウム又は硝酸アンモニウム
と他の無機酸化酸塩及び(ロ)水からなる酸化剤水溶
液の分散相、(ハ)燃料油及び/又はワツクス類から
なる可燃剤の連続相、(ニ)高級脂肪酸アミドからな
る乳化剤及び(ホ)微小中空球体又は微小気泡を含有
させてなることを特徴とするものである。
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
属又は、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種又は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50%〜94.7%(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塩全体の40%以下で含有
させてもよい。
前記硝酸アンモニウムの配合量が、下限未満だ
と酸素バランス(酸化剤と可燃剤との酸素の過不
足の関係)が悪く(酸素不足)なり過ぎて、爆発
性及び後ガスが悪くなる。上限を越えると硝酸ア
ンモニウムの水への溶解温度が高くなり過ぎて製
造性が悪くなるのと、硝酸アンモニウムの爆発反
応性が悪くなるため起爆感度が悪い。
又、前記の他の無機酸化酸塩については、若干
量配合することにより酸素供給量が増やせるし、
水への溶解温度も低下できるため爆発性及び製造
性が改善されるが、40%を越えると爆発後の固体
残渣が増えるため威力が低くなつたり、経済性の
面で不利となる。
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、及び昆虫ワツクスである蜜ロ
ウ等である。これらの燃料油・ワツクス類は1種
又は2種以上の混合物として用いる。燃料油及
び/又はワツクス類の配合量は一般に0.1%〜10
%である。
燃料油及び/又はワツクス類が、0.1%未満で
はW/O型エマルシヨン爆薬組成物の安定性が悪
く、10%を越えると酸素バランスが悪くなり過ぎ
て爆発性及び後ガスが悪くなる。
本発明のW/O型エマルシヨン爆薬組成物の乳
化剤である高級脂肪酸アミドは、例えば下記一般
式で示される脂肪酸アミドが好ましく、ラウリン
酸アミド、ステアリン酸アミド、イソステアリン
酸アミド、リノール酸アミド、リノレイン酸アミ
ド、ベヘン酸アミド、エルカ酸アミド等をあげる
ことができる。
RCONH2
〔R=CnH2o+1、CnH2o-1、CnH2o-3、又は
CnH2o-5
(n=9〜24)〕
これらの乳化剤は1種又は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0.1%
〜5%である。好ましくは0.5%〜4%である。
これらの各種乳化剤が、0.1%未満ではW/O
型エマルシヨン爆薬組成物の小口径及び低温にお
ける起爆感度の経時安定性が悪く、5%を越える
と酸素バランスが悪くなつて爆発性及び後ガスが
悪くなり、経済性の面でも不利となる。
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、微小中空球体又は微小気泡であ
り、微小中空球体とは、例えばガラス、アルミ
ナ、頁岩、シラス、硅砂、火山岩、ケイ酸ナトリ
ウム、ホウ砂、真殊岩、黒曜石等から得られる無
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
塩化ビニリデン、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種又は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0.1
%〜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、又
はW/O型エマルシヨンの形成時又は形成後の工
程で機械的に空気又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、又は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種又は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。
しかして、前記の仮比重調整剤については、微
小中空球体0.1%未満又は化学発泡剤0.01%未満
又はW/O型エマルシヨン爆薬組成物の仮比重が
1.35を越えるような空気又はその他のガスの量の
場合には、起爆感度が悪いことと爆発しても爆速
が低い。
微小中空球体が10%を越えると、又は化学発泡
剤が2%を越えると、又はW/O型エマルシヨン
爆薬組成物の仮比重が0.80未満となるような空気
又はその他のガスの量の場合には、起爆感度は良
好であるが爆速が低いため威力が小さい。
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
ンモニウム又は硝酸アンモニウムと他の無機酸化
酸塩との混合物を約80℃〜90℃で水に溶解させた
酸化剤水溶液を得る。一方、本発明で規定する乳
化剤と燃料油及び/又はワツクス類とを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
微小中空球体又は化学発泡剤を前記のW/O型エ
マルシヨンに縦型〓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。なお微小中空球体又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
を実施例及び比較例によつて具体的に説明する。
なお各例中の部数及び%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381.5部(76.30%)及
び硝酸ナトリウム22.85部(4.57%)を水55.25部
(11.05%)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、本発明
で規定するラウリン酸アミド8.75部(1.75%)と
未精製マイクロクリスタリンワツクス17.05部
(3.41%)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。
次に保温可能な容器内にまず可燃剤混合物を入
れ、次に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のガラス微小中空球
体14.60部(2.92%)を前記のW/O型エマルシ
ヨンに縦型〓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カ
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、及び(ハ)
前記(ロ)の起爆試験時の仮比重測定を行なつた。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
シヨン爆薬組成物は実施例1のラウリン酸アミド
に代えてイソステアリン酸アミド、オレイン酸ア
ミド、リノール酸アミド、ベヘン酸アミド及びエ
ルカ酸アミド及びそれらの混合物を用いた以外は
実施例1に準じて製造した。これらの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
目の性能試験を行なつた。その結果は第1表に示
すとおりであつた。
実施例 11
第1表に示すような配合組成のW/O型エマル
シヨン爆薬組成物は実施例1のガラス微小中空球
体に代えて、N・N′−ジニトロソペンタメチレ
ンテトラミンを用いた以外は実施例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、この試料薬包を約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なつた。
実施例 12
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なつた。その結
果は、第1表に示すとおりであつた。
比較例 1〜8
第2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なつた。その結
果は、第2表に示すとおりであつた。
比較例 9及び10
第2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12及び13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なつた。
その結果は、第2表に示すとおりであつた。
The present invention relates to a water-in-oil emulsion explosive composition (hereinafter abbreviated as W/O emulsion explosive composition).
The present invention relates to an explosive composition containing a novel emulsifier that forms a W/O emulsion,
In particular, it relates to a W/O emulsion explosive composition that uses a higher fatty acid amide as an emulsifier and has performance superior to conventional known emulsifiers in terms of stability over time of detonation sensitivity at small diameters (25 mm) and at low temperatures. be. Regarding the W/O type emulsion explosive composition,
It has been researched for a long time, and the initial ones were because the morphology of the W/O emulsion was unstable (that is, the contact area between the dispersed phase and the continuous phase was relatively small), so explosive sensitizers such as nitroglycerin were used. Or non-explosive sensitizing agents such as monomethylamine nitrate (hereinafter abbreviated as sensitizing substances), or atomic number 13
Compounds of metals other than Groups 1 and 2 of the periodic table, explosive catalytic sensitizers such as water-soluble strontium compounds, or sensitizers such as ammonium or alkali metal perchlorates, etc. Most of the bombs contained additives (hereinafter abbreviated as auxiliary sensitive substances, etc.) to improve detonation sensitivity at small diameters.
However, W/O type emulsion explosive compositions containing such sensitive substances or auxiliary sensitive substances, etc., may be susceptible to damage if, for example, the above-mentioned sensitive substances separate due to some factor during manufacturing or use. There was a potential danger of becoming extremely sensitive, or of the toxicity of the above-mentioned sensitive substances. In this sense, a W/O emulsion explosive composition has also been disclosed which does not contain any of the above-mentioned sensitive substances or auxiliary sensitive substances and has improved detonation sensitivity in small diameters (enabling detonation with a detonator). For example, according to U.S. Pat. No. 4,110,134, emulsifiers include sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene ether, polyoxyalkylene oleate, polyoxyalkylene laurate, and phosphorus. Contains acid oleate, substituted oxazoline, and phosphate ester, and contains a glass microballoon as a bubble retaining agent. It has a diameter of about 1.25 inches (31.8 mm) and can be completely detonated with a No. 6 detonator to a tentative specific gravity of up to 1.25. It is written that. Further, according to US Pat. No. 4,149,917, emulsifiers include sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene (4) lauryl ether, polyoxyethylene (2) ether, polyoxyethylene ( 2) By blending stearyl ether, polyoxyalkylene oleate, polyoxyalkylene laurate, phosphoric oleate, substituted oxazoline, phosphoric ester, and mixtures thereof, it is possible to form microbubbles without containing a bubble-retaining substance. Adjust the temporary specific gravity to 0.95,
With a diameter of 1.25 inches (31.8 mm), it can be completely detonated with a No. 6 detonator even after two months have passed since manufacture (explosive temperature 21.1℃), and can be completely detonated with a No. 8 detonator even after eight months have passed (explosive temperature 21.1
°C). It is well known that various emulsifiers are used in W/O type emulsion explosive compositions that do not contain the above-mentioned sensitizing substances or auxiliary sensitizing substances. Various emulsifiers that form emulsions are known. However, as can be seen from the fact that W/O type emulsion explosive compositions using emulsifiers other than those described in the above-mentioned US patent specification contain the above-mentioned sensitive substances or auxiliary sensitive substances, etc. That W/
Because the O-type emulsion has poor stability over time, the stability over time of detonation sensitivity at small diameters (25 mm diameter) and low temperatures is extremely poor. Furthermore, even with the W/O type emulsion explosive composition using the emulsifier described in the above-mentioned US patent specification, the stability over time of the detonation sensitivity at low temperatures is sufficiently satisfactory with a smaller diameter (25 mm diameter). It wasn't. The inventors of the present invention have conducted intensive research over a long period of time while taking into account the above-mentioned problems.
A substance that has not been considered as an emulsifier for an O-type emulsion explosive composition is a W/ It has been discovered that it can be formed into an O-type emulsion, and the W/O-type emulsion explosive composition thus obtained has performance superior to conventional known emulsifiers in terms of stability over time of detonation sensitivity at small diameters and low temperatures. The present invention was completed based on the discovery that the invention has the following properties. That is, the W/O emulsion explosive composition of the present invention comprises (a) a dispersed phase of an oxidizing agent aqueous solution consisting of (a) ammonium nitrate or ammonium nitrate and another inorganic oxide salt, and (b) water, (c) fuel oil and/or It is characterized by containing a continuous phase of a combustible agent made of waxes, (d) an emulsifier made of a higher fatty acid amide, and (e) 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, the 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 50% to 94.7% of the total (by weight, the same applies below)
If necessary, other inorganic oxide salts may be contained in an amount of 40% or less of the total inorganic acid salts containing ammonium nitrate. If the amount of ammonium nitrate is less than the lower limit, the oxygen balance (the relationship between excess and deficiency of oxygen between the oxidizing agent and the combustible agent) will be too poor (oxygen deficiency), resulting in poor explosiveness and aftergassing. If the upper limit is exceeded, the dissolution temperature of ammonium nitrate in water becomes too high, resulting in poor productivity, and the explosive reactivity of ammonium nitrate becomes poor, resulting in poor detonation sensitivity. In addition, the amount of oxygen supplied can be increased by adding a small amount of the other inorganic oxide salts mentioned above,
The dissolution temperature in water can also be lowered, which improves explosiveness and manufacturability, but if it exceeds 40%, the amount of solid residue after explosion increases, resulting in a decrease in power and disadvantages in terms of economy. These include tan wax, ozokerite, etc., animal waxes such as spermaceti wax, and insect waxes such as beeswax. These fuel oils/waxes may be used alone or as a mixture of two or more. The amount of fuel oil and/or waxes is generally 0.1% to 10%.
%. If the fuel oil and/or wax is less than 0.1%, the stability of the W/O emulsion explosive composition will be poor, and if it exceeds 10%, the oxygen balance will be too poor, resulting in poor explosiveness and aftergassing. The higher fatty acid amide which is the emulsifier of the W/O emulsion explosive composition of the present invention is preferably a fatty acid amide represented by the following general formula, for example, lauric acid amide, stearic acid amide, isostearic acid amide, linoleic acid amide, linoleic acid amide. Examples include amide, behenic acid amide, erucic acid amide, and the like. RCONH 2 [R=CnH 2o+1 , CnH 2o-1 , CnH 2o-3 , or
CnH 2o-5 (n=9 to 24)] These emulsifiers are used alone or as a mixture of two or more. The amount of emulsifier added is generally 0.1%.
~5%. Preferably it is 0.5% to 4%. If these various emulsifiers are less than 0.1%, W/O
The stability of the detonation sensitivity of the type emulsion explosive composition over time at small diameters and low temperatures is poor, and if it exceeds 5%, the oxygen balance becomes poor, resulting in poor explosiveness and aftergassing, which is also disadvantageous from an economic point of view. 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 obtained from, for example, glass, alumina, shale, shirasu, silica sand, volcanic rock, sodium silicate, borax, obsidian, etc. These include inorganic micro hollow spheres obtained from pitch, carbonaceous micro hollow spheres obtained from coal, etc., synthetic resin micro hollow spheres obtained from phenolic resin, polyvinylidene chloride, epoxy resin, urea resin, etc. The hollow spheres may be used alone or as a mixture of two or more. The amount of micro hollow spheres is generally 0.1
%~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 is
Generally 0.01% to 2%. However, regarding the temporary specific gravity adjusting agent, the temporary specific gravity of the micro hollow spheres is less than 0.1%, the chemical blowing agent is less than 0.01%, or the W/O type emulsion explosive composition is
If the amount of air or other gas exceeds 1.35, the detonation sensitivity will be poor and even if the explosion occurs, the detonation velocity will be low. If the microhollow spheres exceed 10%, or if the chemical blowing agent exceeds 2%, or if the amount of air or other gas is such that the tentative specific gravity of the W/O emulsion explosive composition is less than 0.80. The detonation sensitivity is good, but the detonation speed is low, so the power is small. 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 in water at about 80°C to 90°C. On the other hand, the emulsifier defined in the present invention and fuel oil and/or waxes were heated at 80°C to 90°C.
A mixture (hereinafter abbreviated as combustible mixture) is obtained by melting and mixing at °C. Next, first put the combustible mixture in a heat-retainable container with a certain volume, and mix and stir for about 5 minutes at about 1600 rpm using a commonly used propeller blade stirrer while gradually adding the oxidizing agent aqueous solution. Obtain a W/O type emulsion at 85°C. 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 mixer 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 by stirring while blowing gas such as air into the W/O type emulsion. /O type 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 emulsion explosive composition having the formulation shown in Table 1 was produced as follows. First, 381.5 parts (76.30%) of ammonium nitrate and 22.85 parts (4.57%) of sodium nitrate were added to 55.25 parts (11.05%) of water and dissolved by heating to obtain an oxidizing agent aqueous solution at about 85°C. On the other hand, a mixture of 8.75 parts (1.75%) of lauric acid amide defined in the present invention and 17.05 parts (3.41%) of unrefined microcrystalline wax was heated to melt at about 85°C.
A combustible mixture was obtained. Next, first put the combustible agent mixture in a heat-insulating container, then gradually add the oxidizing agent aqueous solution and mix and stir for 5 minutes at about 1600 rpm using a propeller blade stirrer to reach about 85°C. A W/O type emulsion was obtained. Next, a W/O emulsion explosive composition was prepared by mixing 14.60 parts (2.92%) of glass micro hollow spheres with an average particle size of 75μ into the W/O emulsion using a vertical mixer at approximately 30 rpm. Obtained. This W/O type emulsion explosive composition was molded to have a diameter of 25 mm, a length of approximately 180 mm, and a drug amount of 100 gr, and was subjected to various performance tests as a medicine package wrapped in viscose-treated paper. The performance tests included (a) measuring the temporary specific gravity one day after production, and (b) repeating the temperature cycle of keeping the sample cartridge at 60℃ for 24 hours, then keeping it at -15℃ for 24 hours, and making this one cycle. After conducting a forced deterioration storage test, a No. 6 detonator was used to
Determine the number of temperature cycles that can cause a complete explosion when performing an explosion test at 5℃, and calculate the number of temperature cycles at room temperature (10 to 30℃).
Detonation sensitivity aging stability test estimated as the number of months of storage for complete detonation in storage (estimated from the experimental confirmation that one temperature cycle described above corresponds to approximately one month of storage at room temperature), and ( C)
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 A W/O emulsion explosive composition having a composition as shown in Table 1 contains isostearamide, oleic acid amide, linoleic acid amide, behenic acid amide and It was produced according to Example 1 except that erucic acid amide and a mixture thereof were used. Sample cartridges were prepared from these W/O emulsion explosive compositions in the same manner as described in Example 1, and performance tests were conducted on the same items. The results were as shown in Table 1. Example 11 A W/O emulsion explosive composition having the composition shown in Table 1 was prepared as in Example 1 except that N·N'-dinitrosopentamethylenetetramine was used in place of the glass micro hollow spheres. Produced according to Example 1. A sample cartridge was prepared from this W/O emulsion explosive composition in the same manner as described in Example 1, and this sample cartridge was heated in a constant temperature bath at approximately 50°C for 2 hours to blend. Chemical blowing agent (N・
The same performance tests as in Example 1 were conducted on a product prepared by decomposing and foaming N'-dinitrosopentamethylenetetramine and adjusting its temporary specific gravity. Example 12 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 were as shown in Table 1. Comparative Examples 1 to 8 W/O emulsion explosive compositions having the formulations shown in Table 2 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 2012, and performance tests were conducted on the same items. The results were as shown in Table 2. Comparative Examples 9 and 10 W/O emulsion explosive compositions having the formulation shown in Table 2 were produced according to Examples 12 and 13. A sample cartridge was 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 were as shown in Table 2.
【表】【table】
【表】
本発明で規定する乳化剤として、ラウリン酸ア
ミド、イソステアリン酸アミド、オレイン酸アミ
ド、リノール酸アミド、リノレイン酸アミド、ベ
ヘン酸アミド及びエルカ酸アミドを配合したW/
O型エマルシヨン爆薬組成物(実施例1〜7)の
場合は6号***を用いて−5℃での完爆可能貯蔵
月数は24カ月〜28カ月であつた。
一方公知の乳化剤を配合したW/O型エマルシ
ヨン爆薬組成物(比較例1〜7)の場合はそれが
6カ月〜19カ月であつた。
又、硝酸アンモニウム以外の無機酸化酸塩とし
て硝酸ナトリウム及び硝酸カルシウム、可燃剤と
して流動パラフイン、気泡保持剤としてシリカ微
小中空球体及び乳化剤としてソルビタンモノオレ
イン酸エステルを2.50%配合したW/O型エマル
シヨン爆薬組成物(比較例8)の場合は、6号雷
管を用いて−5℃での完爆可能貯蔵月数は24カ月
であつたが本発明で規定される乳化剤としてオレ
イン酸アミドを2.50%配合したW/O型エマルシ
ヨン爆薬組成物(実施例8)のそれは31カ月であ
つた。又、本発明で規定される乳化剤としてオレ
イン酸アミド1.25%とリノール酸アミド1.25%と
を配合したW/O型エマルシヨン爆薬組成物(実
施例9)のそれは30カ月であつた。
又、気泡保持剤は配合せずに化学発泡剤として
N・N′−ジニトロソペンタメチレンテトラミン
を0.20%配合して仮比重を調整しかつ乳化剤とし
てソルビタンモノオレイン酸エステルを1.80配合
したW/O型エマルシヨン爆薬組成物(比較例
9)の場合は、6号***を用いて−5℃での完爆
可能貯蔵月数は14カ月であつたが、ソルビタンモ
ノオレイン酸エステルの代りに本発明で規定され
るオレイン酸アミド1.80%配合したW/O型エマ
ルシヨン爆薬組成物(実施例10)のそれは21カ月
であつた。
又、気泡保持剤は配合せずに機械的に微小気泡
を導入して仮比重を調整しかつ乳化剤としてソル
ビタンモノオレイン酸エステルを1.80%配合した
W/O型エマルシヨン爆薬組成物(比較例10)の
場合は、6号***を用いて−5℃での完爆可能貯
蔵月数は13カ月であつたが、ソルビタンモノオレ
イン酸エステルの代りに本発明で規定される乳化
剤としてオレイン酸アミドを1.80%配合したW/
O型エマルシヨン爆薬組成物(実施例11)のそれ
は19カ月であつた。
以上、各実施例及び各比較例に基づいて説明し
たように本発明で規定される乳化物を配合した
W/O型エマルシヨン爆薬組成物は、従来の乳化
剤を配合したW/O型エマルシヨン爆薬組成物に
較べ小口径(25mm径)及び低温に於ける起爆感度
の経時安定性が大巾に改善されたものである。[Table] W/ containing lauric acid amide, isostearic acid amide, oleic acid amide, linoleic acid amide, linoleic acid amide, behenic acid amide and erucic acid amide as emulsifiers defined in the present invention.
In the case of the O-type emulsion explosive compositions (Examples 1 to 7), the storage period for complete detonation at -5° C. using a No. 6 detonator was 24 to 28 months. On the other hand, in the case of W/O type emulsion explosive compositions containing known emulsifiers (Comparative Examples 1 to 7), the period was 6 to 19 months. Also, a W/O emulsion explosive composition containing sodium nitrate and calcium nitrate as inorganic oxide salts other than ammonium nitrate, liquid paraffin as a combustible agent, silica micro hollow spheres as a bubble retaining agent, and 2.50% of sorbitan monooleate as an emulsifier. In the case of the product (Comparative Example 8), the storage period for complete detonation at -5°C using a No. 6 detonator was 24 months, but 2.50% oleic acid amide was blended as an emulsifier specified in the present invention. That of the W/O emulsion explosive composition (Example 8) was 31 months. Further, the life of a W/O emulsion explosive composition (Example 9) containing 1.25% oleic acid amide and 1.25% linoleic acid amide as emulsifiers defined in the present invention was 30 months. In addition, a W/O was prepared in which the tentative specific gravity was adjusted by adding 0.20% of N・N'-dinitrosopentamethylenetetramine as a chemical blowing agent without adding a bubble retaining agent, and 1.80% of sorbitan monooleate was added as an emulsifier. In the case of the type emulsion explosive composition (Comparative Example 9), the storage period for complete detonation at -5°C using a No. 6 detonator was 14 months, but the composition of the present invention was used instead of sorbitan monooleate. The life of the W/O emulsion explosive composition (Example 10) containing 1.80% of the specified oleic acid amide was 21 months. In addition, a W/O emulsion explosive composition in which the tentative specific gravity was adjusted by mechanically introducing microbubbles without adding a bubble retaining agent, and 1.80% of sorbitan monooleate was added as an emulsifier (Comparative Example 10) In this case, the storage period for complete detonation at -5℃ using a No. 6 detonator was 13 months, but instead of sorbitan monooleate, oleic acid amide was used as an emulsifier specified in the present invention at 1.80%. % blended W/
That of the Type O emulsion explosive composition (Example 11) was 19 months. As explained above based on each Example and each Comparative Example, the W/O type emulsion explosive composition containing the emulsion specified by the present invention is different from the W/O type emulsion explosive composition containing the conventional emulsifier. The stability of detonation sensitivity over time at small diameters (25mm diameter) and low temperatures has been greatly improved compared to conventional detonators.
Claims (1)
他の無機酸化塩及び(ロ)水からなる酸化剤水溶液の
分散相、(ハ)燃料油及び/又はワツクス類からなる
可燃物の連続相、(ニ)高級脂肪酸アミドからなる乳
化剤及び(ホ)微小中空球体又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。 2 高級脂肪酸アミドが下記一般式で示される脂
肪酸アミドである特許請求の範囲第1項に記載の
油中水型エマルシヨン爆薬組成物。 RCONH2 〔R=CnH2o+1、CnH2o-1、CnH2o-3又はCnH2o-5 (n=9〜24)〕[Scope of Claims] 1. (a) a dispersed phase of an oxidizing agent aqueous solution consisting of ammonium nitrate or ammonium nitrate and other inorganic oxide salts, and (b) water, (c) a continuous phase of a combustible substance consisting of fuel oil and/or waxes. , (d) an emulsifier consisting of a higher fatty acid amide, and (e) a water-in-oil emulsion explosive composition containing microscopic hollow spheres or microbubbles. 2. The water-in-oil emulsion explosive composition according to claim 1, wherein the higher fatty acid amide is a fatty acid amide represented by the following general formula. RCONH 2 [R=CnH 2o+1 , CnH 2o-1 , CnH 2o-3 or CnH 2o-5 (n=9 to 24)]
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6928481A JPS57188484A (en) | 1981-05-11 | 1981-05-11 | Water-in-oil emulsion explosive composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6928481A JPS57188484A (en) | 1981-05-11 | 1981-05-11 | Water-in-oil emulsion explosive composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS57188484A JPS57188484A (en) | 1982-11-19 |
JPS6154759B2 true JPS6154759B2 (en) | 1986-11-25 |
Family
ID=13398161
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP6928481A Granted JPS57188484A (en) | 1981-05-11 | 1981-05-11 | Water-in-oil emulsion explosive composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS57188484A (en) |
-
1981
- 1981-05-11 JP JP6928481A patent/JPS57188484A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS57188484A (en) | 1982-11-19 |
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