JP2005145780A - Slurry explosive composition - Google Patents
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- JP2005145780A JP2005145780A JP2003387833A JP2003387833A JP2005145780A JP 2005145780 A JP2005145780 A JP 2005145780A JP 2003387833 A JP2003387833 A JP 2003387833A JP 2003387833 A JP2003387833 A JP 2003387833A JP 2005145780 A JP2005145780 A JP 2005145780A
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- 239000002360 explosive Substances 0.000 title claims abstract description 71
- 239000002002 slurry Substances 0.000 title claims abstract description 52
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 22
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims abstract description 22
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims abstract description 22
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 229920002907 Guar gum Polymers 0.000 claims description 28
- 239000000665 guar gum Substances 0.000 claims description 28
- 229960002154 guar gum Drugs 0.000 claims description 28
- 235000010417 guar gum Nutrition 0.000 claims description 28
- 239000002562 thickening agent Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000006266 etherification reaction Methods 0.000 abstract description 17
- 239000003795 chemical substances by application Substances 0.000 abstract description 8
- 230000032683 aging Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 25
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 24
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 12
- PTIUDKQYXMFYAI-UHFFFAOYSA-N methylammonium nitrate Chemical compound NC.O[N+]([O-])=O PTIUDKQYXMFYAI-UHFFFAOYSA-N 0.000 description 12
- 235000010344 sodium nitrate Nutrition 0.000 description 12
- 239000004317 sodium nitrate Substances 0.000 description 12
- 239000008235 industrial water Substances 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 7
- 101000637835 Homo sapiens Serum amyloid A-4 protein Proteins 0.000 description 7
- 102100032016 Serum amyloid A-4 protein Human genes 0.000 description 7
- 239000003925 fat Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229920002472 Starch Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- 239000004088 foaming agent Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 3
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000013112 stability test Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 241000282372 Panthera onca Species 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 239000000446 fuel Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000002123 temporal effect Effects 0.000 description 2
- WHQOKFZWSDOTQP-UHFFFAOYSA-N 2,3-dihydroxypropyl 4-aminobenzoate Chemical compound NC1=CC=C(C(=O)OCC(O)CO)C=C1 WHQOKFZWSDOTQP-UHFFFAOYSA-N 0.000 description 1
- HTKIMWYSDZQQBP-UHFFFAOYSA-N 2-hydroxyethyl nitrate Chemical compound OCCO[N+]([O-])=O HTKIMWYSDZQQBP-UHFFFAOYSA-N 0.000 description 1
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 244000131415 Zanthoxylum piperitum Species 0.000 description 1
- 235000008853 Zanthoxylum piperitum Nutrition 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910001964 alkaline earth metal nitrate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- GAPFWGOSHOCNBM-UHFFFAOYSA-N isopropyl nitrate Chemical compound CC(C)O[N+]([O-])=O GAPFWGOSHOCNBM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- GWKNUWRKJUDXAY-UHFFFAOYSA-N n,n-dimethylmethanamine;nitric acid Chemical compound CN(C)C.O[N+]([O-])=O GWKNUWRKJUDXAY-UHFFFAOYSA-N 0.000 description 1
- KTAFYYQZWVSKCK-UHFFFAOYSA-N n-methylmethanamine;nitric acid Chemical compound CNC.O[N+]([O-])=O KTAFYYQZWVSKCK-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、砕石、採掘、トンネル掘削などの産業発破に用いられる爆薬組成物に関する。 The present invention relates to an explosive composition used for industrial blasting such as crushed stone, mining, tunnel excavation and the like.
含水爆薬にはスラリー爆薬とエマルション爆薬の２つのタイプがある。スラリー爆薬は厳密にはスラリー爆薬とウォータージェル爆薬に分けることができる。
現在国内においては、大抵の場合区別することなくウォータージェル爆薬もスラリー爆薬と呼ばれている。しかしながら、国際的には、スラリー爆薬は流動性があり、ポンピング可能なもので、水と混合可能なものとされている。一方、ウォータージェル爆薬は、架橋剤の添加により形態が安定しており、耐水性があるものと定義されている。（例えば、非特許文献１参照）いずれもその名称は爆薬の性状を素直に示しており、受け入れやすい。
There are two types of hydrous explosives: slurry explosives and emulsion explosives. Strictly speaking, slurry explosives can be divided into slurry explosives and water gel explosives.
At present, water gel explosives are also called slurry explosives in most cases without distinction. Internationally, however, slurry explosives are fluid, pumpable, and miscible with water. On the other hand, the water gel explosive is defined as having a stable form by adding a crosslinking agent and having water resistance. (For example, refer nonpatent literature 1) In any case, the name indicates the property of the explosive and is easy to accept.
従って、本明細書では、スラリー爆薬とウォータージェル爆薬を区別して記載する。
ウォータージェル爆薬は、水、硝酸アンモニウムや硝酸ナトリウムなどの酸化剤、モノメチルアミンナイトレートやアルミ粉などの鋭感剤、グアガムやでんぷんなどの粘稠剤、ガラスマイクロバルーンや樹脂バルーンなどの気泡剤、架橋剤などからなり（例えば非特許文献２参照）、架橋剤の添加により粘稠剤が架橋し、爆薬全体の形態が安定し、耐水性が付加される。スラリー爆薬は基本的にはこれらウォータージェル爆薬成分から架橋剤が除かれたもので、架橋しておらず流動性があるものである。
これまで、スラリー爆薬の性状に最も影響を与える成分である粘稠剤については、カルボキシメチルセルロースナトリウムのエーテル化度を限定したもの（例えば、特許文献１参照）や、成分分離の防止や耐水性を付加する目的でグアガムとでんぷんを組み合わせたもの（例えば、特許文献２参照）などが知られている。
Therefore, in this specification, a slurry explosive and a water gel explosive are distinguished and described.
Water gel explosives are water, oxidizing agents such as ammonium nitrate and sodium nitrate, sharpening agents such as monomethylamine nitrate and aluminum powder, viscous agents such as guar gum and starch, foaming agents such as glass microballoons and resin balloons, and crosslinking. The thickener is cross-linked by the addition of the cross-linking agent, the form of the entire explosive is stabilized, and water resistance is added. Slurry explosives are basically those obtained by removing the cross-linking agent from these water gel explosive components, and are not cross-linked and have fluidity.
So far, for thickeners, which are components that have the most influence on the properties of slurry explosives, those having a limited degree of etherification of sodium carboxymethylcellulose (for example, see Patent Document 1), prevention of component separation and water resistance A combination of guar gum and starch (for example, see Patent Document 2) for the purpose of addition is known.
しかし、エーテル化度０．８５を超えるカルボキシメチルセルロースナトリウムでは、経時安定性に問題があり、グアガムとでんぷんとの組み合わせでは、夏場に成分が分離する可能性があった。
本発明は、スラリー爆薬に関し、経時安定性に優れた爆薬組成物を提供することを目的とする。 The present invention relates to a slurry explosive and an object thereof is to provide an explosive composition having excellent temporal stability.
本発明者等は、前記課題を解決するため鋭意研究を重ねた結果、スラリー爆薬の粘稠剤の添加量や種類を調整することにより、本発明を完成するに至った。
即ち、本発明は、下記のとおりである。
１．酸化剤、水、粘稠剤を含有するスラリー爆薬組成物であって、水の含有量が１０〜３５重量％であり、粘稠剤にエーテル化度０．５５〜０．８５、１重量％水溶液の粘度が２，０００〜２０，０００ｍＰａ・ｓ（温度２５℃、Ｂ型粘度計）のカルボキシメチルセルロースナトリウムを含有することを特徴とするスラリー爆薬組成物。
２．粘稠剤がグアガムとカルボキシメチルセルロースナトリウムを含むことを特徴とする１．に記載のスラリー爆薬組成物。
３．粘稠剤がカルボキシメチルセルロースナトリウムをグアガムに対して１．５〜３．０重量倍含有することを特徴とする１．または２．に記載のスラリー爆薬組成物。
４．グアガムを水に対して０．０２〜０．１０重量倍、カルボキシメチルセルロースナトリウムをグアガムに対して１．５〜３．０重量倍含有することを特徴とする１．、２．または３．に記載のスラリー爆薬組成物。
As a result of intensive studies to solve the above-mentioned problems, the present inventors have completed the present invention by adjusting the amount and type of the slurry explosive thickener.
That is, the present invention is as follows.
1. A slurry explosive composition containing an oxidizing agent, water, and a thickener, wherein the water content is 10 to 35% by weight, and the degree of etherification is 0.55 to 0.85 and 1% by weight. A slurry explosive composition comprising sodium carboxymethylcellulose having an aqueous solution viscosity of 2,000 to 20,000 mPa · s (temperature 25 ° C., B-type viscometer).
2. 1. The thickener contains guar gum and sodium carboxymethylcellulose. 4. A slurry explosive composition as described in 1.
3. 1. The thickener contains sodium carboxymethylcellulose 1.5 to 3.0 times by weight with respect to guar gum. Or 2. 4. A slurry explosive composition as described in 1.
4). 1. Gua gum is contained 0.02 to 0.10 times by weight with respect to water, and sodium carboxymethylcellulose is contained 1.5 to 3.0 times by weight with respect to guar gum. 2. Or 3. 4. A slurry explosive composition as described in 1.
本発明によれば、経時安定性に優れたスラリー爆薬組成物を得ることができる。 According to the present invention, a slurry explosive composition having excellent temporal stability can be obtained.
以下、本願発明について、特にその好ましい形態を中心に、具体的に説明する。
カルボキシメチルセルロースナトリウムは、それが持つチクソトロピー性を利用し、長期貯蔵や夏場での貯蔵における水や比重の異なる成分の分離防止、流動性の改善、耐水性付加などの目的に使用される。カルボキシメチルセルロースナトリウムは、エーテル化度０．５５〜０．８５、好ましくは、０．６５〜０．７５、粘度２，０００〜２０，０００ｍＰａ・ｓ（１重量％水溶液、温度２５℃、Ｂ型粘度計）、好ましくは、３，０００〜１８，０００ｍＰａ・ｓ、更に好ましくは４，０００〜１７，０００ｍＰａ・ｓのものが使用される。また、カルボキシメチルセルロースナトリウムは、グアガムと組み合わせて使用すると尚良い。グアガムは、より水の分離防止の役割をする。水に対してグアガムを０．０２〜０．１０重量倍好ましくは０．０２〜０．０７重量倍、更に好ましくは０．０２〜０．０５重量倍含有する。カルボキシメチルセルロースナトリウムはグアガムに対して１．５〜３．０重量倍添加する。又、水に対してグアガムとカルボキシメチルセルロースナトリウムの総添加量が０．０５〜０．１５重量倍とすると尚良い。
Hereinafter, the present invention will be specifically described with a focus on preferred embodiments.
Sodium carboxymethylcellulose utilizes its thixotropic properties and is used for purposes such as preventing separation of water and components having different specific gravities, improving fluidity, and adding water resistance during long-term storage and summer storage. Sodium carboxymethylcellulose has a degree of etherification of 0.55 to 0.85, preferably 0.65 to 0.75, a viscosity of 2,000 to 20,000 mPa · s (1 wt% aqueous solution, temperature 25 ° C., B-type viscosity). In total), preferably 3,000 to 18,000 mPa · s, more preferably 4,000 to 17,000 mPa · s. Moreover, it is still better to use sodium carboxymethylcellulose in combination with guar gum. Guam gum plays a role in preventing water separation more. The guar gum is contained 0.02 to 0.10 times by weight, preferably 0.02 to 0.07 times by weight, more preferably 0.02 to 0.05 times by weight with respect to water. Sodium carboxymethylcellulose is added 1.5 to 3.0 times by weight with respect to guar gum. The total addition amount of guar gum and sodium carboxymethylcellulose is preferably 0.05 to 0.15 times by weight with respect to water.
グアガムは天然グアガム、グアガム加水分解品、ヒドロキシエチルまたはヒドロキシプロピル化グアガム、カルボキシメチル・ヒドロキシプロピル化グアガム、カチオン化グアガム、酸化グアガムなど一般にスラリー爆薬に使用されるものを使用できる。製造時の粘度上昇率等による製造性の問題、爆薬成分特に水の分離などの問題、爆薬の粘度調整など総合的に勘案され種類が決定される。例えば、メイホール社製メイプログアーＣＳＡＡＭ−１７５、ＣＳＡＡＭ−８０、ジャガーシリーズが良い。
その他本発明のスラリー爆薬組成物に使用できる粘稠剤としては、でんぷん、メチルセルロース、ポリアクリルアミドやポリアクリル酸ソーダなどのポリアクリルアミド系の高分子凝集剤に使用されているものを使用する事ができる。
As the guar gum, natural guar gum, guar gum hydrolyzate, hydroxyethyl or hydroxypropylated guar gum, carboxymethyl / hydroxypropylated guar gum, cationized guar gum, oxidized guar gum and the like which are generally used for slurry explosives can be used. The type is determined by comprehensively considering the problem of manufacturability due to the rate of increase in viscosity at the time of manufacture, the problem of separation of explosive components, particularly water, and the adjustment of the viscosity of explosives. For example, MAYPROGAR CSAAM-175, CSAAM-80 and Jaguar series manufactured by Mayhall are good.
In addition, as the thickening agent that can be used in the slurry explosive composition of the present invention, those used in polyacrylamide-based polymer flocculants such as starch, methylcellulose, polyacrylamide, and sodium polyacrylate can be used. .
本発明のスラリー爆薬組成物に使用できる鋭感剤としては、モノメチルアミンナイトレート、ジメチルアミンナイトレート、トリメチルアミンナイトレート、エチレングリコールモノナイトレート、イソプロピルナイトレートなどが好ましい。鋭感剤は、スラリー爆薬組成物中、０〜３５重量％含有することが好ましい。
本発明のスラリー爆薬組成物に使用される水は、一般に含水爆薬に使用される物で良い。含有量は、５〜４０重量％、好ましくは、１０〜３５重量％である。
As the sharpening agent that can be used in the slurry explosive composition of the present invention, monomethylamine nitrate, dimethylamine nitrate, trimethylamine nitrate, ethylene glycol mononitrate, isopropyl nitrate and the like are preferable. The sharpening agent is preferably contained in the slurry explosive composition in an amount of 0 to 35% by weight.
The water used in the slurry explosive composition of the present invention may be the one generally used for hydrous explosives. Content is 5 to 40 weight%, Preferably, it is 10 to 35 weight%.
本発明のスラリー爆薬に使用できる酸化剤は、アルカリ金属及びアルカリ土類金属の硝酸塩、過塩素酸塩などが使用され、例えば、硝酸アンモニウム、硝酸ナトリウム、硝酸カルシウム、過塩素酸アンモニウム、過塩素酸ナトリウム、過塩素酸カルシウムなどがある。酸化剤の含有量は、爆薬１００ｇの酸素バランスが好ましくは５〜-５ｇ／１００ｇ、より好ましくは３〜-３ｇ／１００ｇ、更に好ましくは１〜-１ｇ／１００ｇである。
気泡剤は、ガラスマイクロバルーン、樹脂バルーン、パーライト、シラスマイクロバルーン、バーミキュライト、軽石の内１種又は２種以上の混合物が好ましい。これらの気泡剤の含有量は、好ましくは０〜１５重量％である。
As the oxidizing agent that can be used in the slurry explosive of the present invention, alkali metal and alkaline earth metal nitrates, perchlorates and the like are used. For example, ammonium nitrate, sodium nitrate, calcium nitrate, ammonium perchlorate, sodium perchlorate. And calcium perchlorate. The content of the oxidizing agent is preferably 5 to -5 g / 100 g, more preferably 3 to -3 g / 100 g, and still more preferably 1 to -1 g / 100 g in terms of oxygen balance of 100 g of explosive.
The foaming agent is preferably one or a mixture of two or more of glass microballoons, resin balloons, perlite, shirasu microballoons, vermiculite and pumice. The content of these foaming agents is preferably 0 to 15% by weight.
また、必要に応じて可燃剤、界面活性剤を添加することもできる。
可燃剤は、アルミ粉やマグネシウム粉などがあり、ステアリン酸などの疎水性物質でコーティングされたものが良い。これらの可燃剤の含有量は、スラリー組成物中０〜５重量％、好ましくは１〜３重量％である。また、その他水溶性燃料としてメタノール、エタノールやエチレングリコールなどを含有することができる。水溶性燃料の含有量は、０〜３０重量％、好ましくは１〜１０重量％である。
Moreover, a combustible agent and surfactant can also be added as needed.
Combustible agents include aluminum powder and magnesium powder, and those coated with a hydrophobic substance such as stearic acid are preferable. The content of these combustibles is 0 to 5% by weight, preferably 1 to 3% by weight in the slurry composition. Moreover, methanol, ethanol, ethylene glycol, etc. can be contained as other water-soluble fuels. The content of the water-soluble fuel is 0 to 30% by weight, preferably 1 to 10% by weight.
界面活性剤の含有量は、好ましくは０．０５〜２重量％、より好ましくは０．５〜１重量％、更に好ましくは０．１〜０．５重量％である。
本発明の爆薬の粘度は、７，０００Ｐａ・ｓ以下であれば機械装填が可能である。７，０００Ｐａ・ｓを超えると機械装填出来ない可能性がある。好ましくは、６，０００Ｐａ・ｓ以下である。粘度は、ブルックフィールド社のデジタル粘度計ＤＶ−Ｅを使用し、測定条件は、爆薬温度０℃、スピンドルＮＯ．７を使用、回転数は、０．３ｒ．ｐ．ｍで測定された値である。
次に、実施例および参考例によって本発明を説明する。
The content of the surfactant is preferably 0.05 to 2% by weight, more preferably 0.5 to 1% by weight, and still more preferably 0.1 to 0.5% by weight.
If the explosive of the present invention has a viscosity of 7,000 Pa · s or less, it can be mechanically loaded. If it exceeds 7,000 Pa · s, there is a possibility that the machine cannot be loaded. Preferably, it is 6,000 Pa · s or less. Viscosity was measured using a Brookfield digital viscometer DV-E. The measurement conditions were explosive temperature 0 ° C., spindle NO. 7 is used, and the rotational speed is 0.3 r. p. It is a value measured in m.
Next, the present invention will be described with reference to examples and reference examples.
以下、経時安定試験、流動性試験、耐水性試験を行ったので説明する。
[経時安定試験]
スラリー爆薬を製造し、厚さ４０μｍのポリ袋に約１００ｇ入れて５０℃に加温し、６０日後スラリー爆薬の状態を観察した。ほとんど変化が認められないものは◎とし、製造時に巻き込んだ数ミリ大の巻き込み気泡が抜けた程度のものは○、液体成分と気泡剤の分離が認められスラリー爆薬としても性能を維持していないものについては×とした。
[流動性試験]
スラリー爆薬を製造し、流動性試験を行った。測定には、ブルックフィールド社のデジタル粘度計ＤＶ−Ｅを使用し、測定条件は、爆薬温度０℃、スピンドルＮＯ．７を使用、回転数は、０．３ｒ．ｐ．ｍとした。粘度が６，０００Ｐａ・ｓ以下のものを◎、６，０００〜７，０００Ｐａ・ｓのものを○、７，０００Ｐａ・ｓ以上のものを×とした。
In the following, the time stability test, the fluidity test, and the water resistance test were conducted, which will be described.
[Stability test over time]
A slurry explosive was manufactured, about 100 g was put in a 40 μm thick plastic bag, heated to 50 ° C., and after 60 days, the state of the slurry explosive was observed. Those with almost no change are marked with ◎, those with a few millimeters of entrained air bubbles that were involved during production are removed, ○, separation of the liquid component and foaming agent is recognized, and the performance as a slurry explosive is not maintained The thing was set as x.
[Fluidity test]
Slurry explosives were manufactured and fluidity tests were performed. For the measurement, a Brookfield digital viscometer DV-E was used. The measurement conditions were explosive temperature 0 ° C., spindle NO. 7 is used, and the rotational speed is 0.3 r. p. m. Those having a viscosity of 6,000 Pa · s or less were rated as “◎”, those having a viscosity of 6,000 to 7,000 Pa · s as “◯”, and those having a viscosity of 7,000 Pa · s or more as “X”.
[耐水性試験]
スラリー爆薬を製造し、５０ｇを容量１００ｍｌのビーカーに入れ、１００ｍｌの基線の位置まで水をビーカー壁面に沿わせながら丁寧に入れた。１時間後と６時間後のスラリー爆薬の状態を観察し、スラリー爆薬にほとんど変化がなく、水面にもほとんど浮遊物がないものを◎、スラリー爆薬にわずかに変化があり、水面にわずかに浮遊物があるものを○、スラリー爆薬が大きく変化し、水面に浮遊物が多いものは耐水性が不良として×とした。
[エーテル化度]
エーテル化度試料１ｇを精秤し、ろ紙に包んで、磁製ルツボの中に入れ、６００℃で 灰化し、生成したナトリウム化合物を、０．１Ｎ硫酸により、フェノールフタレインを指示薬として滴定し、以下の式を用いてエーテル化度を計算した。以下の式中、
Ａは、中和に要した０．１Ｎ硫酸の量（ｍｌ）、
ｆは、０．１Ｎ硫酸の力価を示す。
エーテル化度＝（１６２×Ａ×ｆ）÷（１００００-８０×Ａ×ｆ）
[Water resistance test]
Slurry explosives were manufactured, 50 g was put into a beaker with a capacity of 100 ml, and water was carefully put up to the position of the 100 ml base line along the beaker wall surface. Observe the state of the slurry explosive after 1 hour and 6 hours, and the slurry explosive has almost no change, and there is almost no suspended matter on the water surface. The slurry explosive has a slight change and floats slightly on the water surface. The case where there was an object was marked as ◯, the case where the slurry explosive changed greatly, and the case where there was a lot of suspended matter on the water surface was marked as poor water resistance.
[Degree of etherification]
A 1 g etherification degree sample is precisely weighed, wrapped in filter paper, placed in a magnetic crucible, ashed at 600 ° C., and the resulting sodium compound is titrated with 0.1 N sulfuric acid using phenolphthalein as an indicator. The degree of etherification was calculated using the following formula: In the following formula:
A is the amount of 0.1N sulfuric acid (ml) required for neutralization,
f shows the titer of 0.1N sulfuric acid.
Degree of etherification = (162 × A × f) ÷ (10000−80 × A × f)
[実施例１]
容器にモノメチルアミンナイトレート（旭化成製）２５．６重量％と水（工業用水）２０．０重量％と硝酸アンモニウム（三菱化学製）３５．４重量％と樹脂バルーン（マツモト油脂製）０．８０重量％とガラスマイクロバルーン（３Ｍ社製）４．２重量％を入れ、３５℃の水浴中で溶解混合し、予め混合した硝酸ナトリウム（三菱化学製）１１．０重量％とカルボキシメチルセルロースナトリウム（第一工業製薬製、セロゲンＢＳＨ−１２（商品名）、エーテル化度０．７０、粘度６，０００〜８，０００ｍＰａ・ｓ）３．０重量％を添加し、２５０r.p.m.で５分間スクリュー型撹拌羽根を用いて混合し、スラリー爆薬を得た。
[Example 1]
In a container, monomethylamine nitrate (made by Asahi Kasei) 25.6% by weight, water (industrial water) 20.0% by weight, ammonium nitrate (made by Mitsubishi Chemical) 35.4% by weight, and resin balloon (made by Matsumoto Oil & Fats) 0.80% % And glass microballoon (made by 3M) 4.2% by weight, dissolved and mixed in a 35 ° C. water bath, premixed sodium nitrate (Mitsubishi Chemical) 11.0% by weight and sodium carboxymethylcellulose (first Industrial Pharmaceutical Co., Ltd., Celogen BSH-12 (trade name), etherification degree 0.70, viscosity 6,000 to 8,000 mPa · s) 3.0% by weight was added, and a screw type stirring blade at 250 rpm for 5 minutes To obtain a slurry explosive.
[実施例２]
容器にモノメチルアミンナイトレート（旭化成製）４０．０重量％と水（工業用水）１０．０重量％と硝酸アンモニウム（三菱化学製）３５．４重量％を入れ、５０℃の水浴中で溶解混合し、予め混合した硝酸ナトリウム（三菱化学製）１４．０重量％とカルボキシメチルセルロースナトリウム（第一工業製薬製、セロゲンＭＰ−５０（商品名）、エーテル化度０．７０、粘度１１，５００〜１６，５００ｍＰａ・ｓ）０．３５重量％とグアガム（三晶製ジャガー８１５８）０．２３重量％を添加し、２５０r.p.m.で５分間スクリュー型撹拌羽根を用いて混合し、スラリー爆薬を得た。
[Example 2]
Put 40.0% by weight of monomethylamine nitrate (Asahi Kasei), 10.0% by weight of water (industrial water) and 35.4% by weight of ammonium nitrate (Mitsubishi Chemical) in a container and dissolve and mix in a 50 ° C water bath. Sodium nitrate (Mitsubishi Chemical) 14.0% by weight and sodium carboxymethylcellulose (Daiichi Kogyo Seiyaku, Cellogen MP-50 (trade name), etherification degree 0.70, viscosity 11,500-16, (500 mPa · s) 0.35 wt% and guar gum (Tricrystal Jaguar 8158) 0.23 wt% were added and mixed at 250 rpm for 5 minutes using a screw type stirring blade to obtain a slurry explosive.
[実施例３]
容器にモノメチルアミンナイトレート（旭化成製）２０．３重量％と水（工業用水）３５．０重量％と硝酸アンモニウム（三菱化学製）２７．７重量％と樹脂バルーン（マツモト油脂製）０．８４重量％を入れ、３５℃の水浴中で溶解混合し、予め混合した硝酸ナトリウム（三菱化学製）１３．０重量％とカルボキシメチルセルロースナトリウム（第一工業製薬製、セロゲンＢＳＨ−１２（商品名）、エーテル化度０．７０、粘度６，０００〜８，０００ｍＰａ・ｓ）２．４重量％とグアガム（三晶製ＣＳＡＡ Ｍ−８０（商品名））０．８重量％を添加し、２５０r.p.m.で５分間スクリュー型撹拌羽根を用いて混合し、スラリー爆薬を得た。
[Example 3]
In a container, monomethylamine nitrate (made by Asahi Kasei) 20.3% by weight, water (industrial water) 35.0% by weight, ammonium nitrate (made by Mitsubishi Chemical) 27.7% by weight and resin balloon (made by Matsumoto Oil & Fats) 0.84% 1% by weight of sodium nitrate (Mitsubishi Chemical) 13.0% by weight and sodium carboxymethylcellulose (Daiichi Kogyo Seiyaku, Serogen BSH-12 (trade name), ether) The degree of conversion was 0.70, the viscosity was 6,000 to 8,000 mPa · s), 2.4% by weight, and 0.8% by weight of guar gum (CSAA M-80 (trade name) manufactured by Sansho) was added at 250 rpm. The mixture was mixed using a screw type stirring blade for 5 minutes to obtain a slurry explosive.
[実施例４]
容器にモノメチルアミンナイトレート（旭化成製）２６．１重量％と水（工業用水）２０．９重量％と硝酸アンモニウム（三菱化学製）３６．５重量％と樹脂バルーン（マツモト油脂製）０．８３重量％とシラスマイクロバルーン（アクシーズケミカル製）２．１重量％を入れ、３５℃の水浴中で溶解混合し、予め混合した硝酸ナトリウム（三菱化学製）１１．３重量％とカルボキシメチルセルロースナトリウム（第一工業製薬製、セロゲンＭＰ−５０（商品名）、エーテル化度０．７０、粘度１１，５００〜１６，５００ｍＰａ・ｓ）１．５重量％とグアガム（三晶製ＣＳＡＡ Ｍ−８０（商品名））０．７重量％を添加し、２５０r.p.m.で５分間スクリュー型撹拌羽根を用いて混合し、スラリー爆薬を得た。
[Example 4]
In the container, monomethylamine nitrate (Asahi Kasei) 26.1 wt%, water (industrial water) 20.9 wt%, ammonium nitrate (Mitsubishi Chemical) 36.5 wt%, and resin balloon (Matsumoto Oil & Fats) 0.83 wt% And 2.1% by weight of Shirasu microballoon (manufactured by Axes Chemical), dissolved and mixed in a 35 ° C. water bath, 11.3% by weight of sodium nitrate (manufactured by Mitsubishi Chemical) and carboxymethyl cellulose sodium (first Made by Kogyo Seiyaku, Serogen MP-50 (trade name), etherification degree 0.70, viscosity 11,500-16,500 mPa · s) 1.5% by weight and guar gum (CSAA M-80 (trade name) manufactured by Sanki) ) 0.7% by weight was added and mixed at 250 rpm for 5 minutes using a screw-type stirring blade to obtain a slurry explosive.
[実施例５]
容器にモノメチルアミンナイトレート（旭化成製）２１．８重量％と水（工業用水）２８．９重量％と硝酸アンモニウム（三菱化学製）３５．６重量％と樹脂バルーン（マツモト油脂製）０．７６重量％とシラスマイクロバルーン（アクシーズケミカル製）２．０重量％を入れ、３５℃の水浴中で溶解混合し、予め混合した硝酸ナトリウム（三菱化学製）８．５重量％とカルボキシメチルセルロースナトリウム（第一工業製薬製、セロゲンＭＰ−５０（商品名）、エーテル化度０．７０、粘度１１，５００〜１６，５００ｍＰａ・ｓ）１．８重量％とグアガム（三晶製ＣＳＡＡ Ｍ−８０（商品名））０．７重量％を添加し、２５０r.p.m.で５分間スクリュー型撹拌羽根を用いて混合し、スラリー爆薬を得た。
[Example 5]
In the container, monomethylamine nitrate (made by Asahi Kasei) 21.8% by weight, water (industrial water) 28.9% by weight, ammonium nitrate (made by Mitsubishi Chemical) 35.6% by weight and resin balloon (made by Matsumoto Oil & Fats) 0.76% by weight And 2.0% by weight of Shirasu microballoon (manufactured by Axes Chemical), dissolved and mixed in a 35 ° C. water bath, 8.5% by weight of sodium nitrate (manufactured by Mitsubishi Chemical) and carboxymethyl cellulose sodium (first Made by Kogyo Seiyaku, Cellogen MP-50 (trade name), etherification degree 0.70, viscosity 11,500-16,500 mPa · s) 1.8% by weight and guar gum (Sansei CSAA M-80 (trade name)) ) 0.7% by weight was added and mixed at 250 rpm for 5 minutes using a screw-type stirring blade to obtain a slurry explosive.
[比較例１]
容器にモノメチルアミンナイトレート（旭化成製）２５．６重量％と水（工業用水）２０．０重量％と硝酸アンモニウム（三菱化学製）３５．４重量％と樹脂バルーン（マツモト油脂製）０．８０重量％とガラスマイクロバルーン（３Ｍ社製）４．２重量％を入れ、３５℃の水浴中で溶解混合し、予め混合した硝酸ナトリウム（三菱化学製）１１．０重量％とカルボキシメチルセルロースナトリウム（第一工業製薬製、セロゲンＰＬ−１５（商品名）、エーテル化度０．５０、粘度１０〜２０）３．０重量％を添加し、２５０ｒ．ｐ．ｍ．で５分間スクリュー型撹拌羽根を用いて混合し、スラリー爆薬を得た。
[Comparative Example 1]
In a container, monomethylamine nitrate (made by Asahi Kasei) 25.6% by weight, water (industrial water) 20.0% by weight, ammonium nitrate (made by Mitsubishi Chemical) 35.4% by weight, and resin balloon (made by Matsumoto Oil & Fats) 0.80% % And glass microballoon (made by 3M) 4.2% by weight, dissolved and mixed in a 35 ° C. water bath, premixed sodium nitrate (Mitsubishi Chemical) 11.0% by weight and sodium carboxymethylcellulose (first Manufactured by Kogyo Seiyaku Co., Ltd., Serogen PL-15 (trade name), degree of etherification of 0.50, viscosity of 10-20), 3.0% by weight, 250 r. p. m. For 5 minutes using a screw-type stirring blade to obtain a slurry explosive.
[比較例２]
容器にモノメチルアミンナイトレート（旭化成製）２２．０重量％と水（工業用水）２７．２重量％と硝酸アンモニウム（三菱化学製）３２．５重量％と樹脂バルーン（マツモト油脂製）０．６８重量％とシラスマイクロバルーン（アクシーズケミカル製）６．８重量％を入れ、５０℃の水浴中で溶解混合し、予め混合した硝酸ナトリウム（三菱化学製）８．３重量％とでんぷん２．０重量％とグアガム（三晶製ＣＳＡＡ Ｍ−８０（商品名））０．８重量％を添加し、２５０r.p.m.で５分間スクリュー型撹拌羽根を用いて混合し、スラリー爆薬を得た。
[Comparative Example 2]
In a container, monomethylamine nitrate (Asahi Kasei) 22.0 wt%, water (industrial water) 27.2 wt%, ammonium nitrate (Mitsubishi Chemical) 32.5 wt%, and resin balloon (Matsumoto Oil & Fats) 0.68 wt% And 6.8% by weight of Shirasu microballoon (manufactured by Axes Chemical), dissolved and mixed in a 50 ° C. water bath, 8.3% by weight of sodium nitrate (manufactured by Mitsubishi Chemical) and 2.0% by weight of starch And 0.8% by weight of guar gum (manufactured by CSAA M-80 (trade name) manufactured by Sanki) were mixed at 250 rpm for 5 minutes using a screw type stirring blade to obtain a slurry explosive.
[比較例３]
容器にモノメチルアミンナイトレート（旭化成製）４０．０重量％と水（工業用水）１０．０重量％と硝酸アンモニウム（三菱化学製）３５．５重量％を入れ、３５℃の水浴中で溶解混合し、予め混合した硝酸ナトリウム（三菱化学製）１４．０重量％とカルボキシメチルセルロースナトリウム（第一工業製薬製、セロゲンＨＥ−１５００Ｆ（商品名）、エーテル化度１．１５、粘度２，５００〜３，５００）０．２３重量％とグアガム（三晶製ＣＳＡＡ Ｍ−１７５（商品名））０．２３重量％を添加し、２５０r.p.m.で５分間スクリュー型撹拌羽根を用いて混合し、スラリー爆薬を得た。
[Comparative Example 3]
Put 40.0% by weight of monomethylamine nitrate (Asahi Kasei), 10.0% by weight of water (industrial water) and 35.5% by weight of ammonium nitrate (Mitsubishi Chemical) into a container and dissolve and mix in a 35 ° C water bath. Sodium nitrate (Mitsubishi Chemical) 14.0% by weight and sodium carboxymethyl cellulose (Daiichi Kogyo Seiyaku, Serogen HE-1500F (trade name), etherification degree 1.15, viscosity 2,500-3, 500) 0.23% by weight and 0.23% by weight of guar gum (CSAA M-175 (trade name) manufactured by Sanki) are added and mixed at 250 rpm for 5 minutes using a screw-type stirring blade, and the slurry explosive is added. Obtained.
[比較例４]
容器にモノメチルアミンナイトレート（旭化成製）１９．９重量％と水（工業用水）３５．０重量％と硝酸アンモニウム（三菱化学製）２７．７重量％と樹脂バルーン（マツモト油脂製）０．８４重量％を入れ、３５℃の水浴中で溶解混合し、予め混合した硝酸ナトリウム（三菱化学製）１３．０重量％とカルボキシメチルセルロースナトリウム（第一工業製薬製、セロゲンセロゲンＥＰ（商品名）、エーテル化度０．９０、粘度２，５００〜４，０００ｍＰａ・ｓ）２．８０重量％とグアガム（三晶製ＣＳＡＡ Ｍ−８０（商品名））０．８重量％を添加し、２５０r.p.m.で５分間スクリュー型撹拌羽根を用いて混合し、スラリー爆薬を得た。
[Comparative Example 4]
19.9% by weight of monomethylamine nitrate (Asahi Kasei), 35.0% by weight of water (industrial water), 27.7% by weight of ammonium nitrate (Mitsubishi Chemical) and 0.84% by weight of resin balloon (made by Matsumoto Oil) 1% by weight, sodium nitrate (Mitsubishi Chemical) 13.0% by weight and sodium carboxymethylcellulose (Daiichi Kogyo Seiyaku, Serogen Serogen EP (trade name), degree of etherification 0.90, viscosity of 2,500 to 4,000 mPa · s) 2.80% by weight and 0.8% by weight of guar gum (CSAA M-80 (trade name) manufactured by Sanki) were added at 250 rpm for 5 minutes. The mixture was mixed using a screw type stirring blade to obtain a slurry explosive.
[比較例５]
容器にモノメチルアミンナイトレート（旭化成製）２６．４重量％と水（工業用水）２０．９重量％と硝酸アンモニウム（三菱化学製）３６．５重量％と樹脂バルーン（マツモト油脂製）０．８３重量％とシラスマイクロバルーン（アクシーズケミカル製）２．１重量％を入れ、３５℃の水浴中で溶解混合し、予め混合した硝酸ナトリウム（三菱化学製）１１．３重量％とカルボキシメチルセルロースナトリウム（第一工業製薬製、セロゲン４Ｈ（商品名）、エーテル化度０．６０、粘度１，４００〜１，８００ｍＰａ・ｓ）１．５重量％とグアガム（三晶製ＣＳＡＡ Ｍ−８０（商品名））０．４重量％を添加し、２５０r.p.m.で５分間スクリュー型撹拌羽根を用いて混合し、スラリー爆薬を得た。
上記スラリー爆薬製造方法により製造し、経時安定試験、流動性試験、耐水性試験を行た。結果を表１に示す。
[Comparative Example 5]
Monomethylamine nitrate (made by Asahi Kasei) 26.4% by weight, water (industrial water) 20.9% by weight, ammonium nitrate (made by Mitsubishi Chemical) 36.5% by weight and resin balloon (made by Matsumoto Oil & Fats) 0.83% by weight And 2.1% by weight of Shirasu microballoon (manufactured by Axes Chemical), dissolved and mixed in a 35 ° C. water bath, 11.3% by weight of sodium nitrate (manufactured by Mitsubishi Chemical) and carboxymethyl cellulose sodium (first Made by Kogyo Seiyaku, Cellogen 4H (trade name), Degree of etherification 0.60, Viscosity 1,400-1,800 mPa · s 1.5% by weight and Gua gum (Sansei CSAA M-80 (trade name)) 0 4 wt% was added and mixed at 250 rpm for 5 minutes using a screw-type stirring blade to obtain a slurry explosive.
Manufactured by the above slurry explosive production method, a time-dependent stability test, a fluidity test, and a water resistance test were conducted. The results are shown in Table 1.
表１より、本発明のスラリー爆薬は、経時安定性に優れた爆薬であることが分かる。 From Table 1, it can be seen that the slurry explosive of the present invention is an explosive excellent in stability over time.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2009163015A (en) * | 2008-01-07 | 2009-07-23 | Kyocera Mita Corp | Image forming apparatus |
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| JP2009163015A (en) * | 2008-01-07 | 2009-07-23 | Kyocera Mita Corp | Image forming apparatus |
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