JP2014001128A - Ammonium nitrate particulate substance for gas generating agent, production method thereof, and gas generating agent pellet - Google Patents
Ammonium nitrate particulate substance for gas generating agent, production method thereof, and gas generating agent pellet Download PDFInfo
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- JP2014001128A JP2014001128A JP2013107632A JP2013107632A JP2014001128A JP 2014001128 A JP2014001128 A JP 2014001128A JP 2013107632 A JP2013107632 A JP 2013107632A JP 2013107632 A JP2013107632 A JP 2013107632A JP 2014001128 A JP2014001128 A JP 2014001128A
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- ammonium nitrate
- granular material
- gas generating
- water
- generating agent
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- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 title claims abstract description 206
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- 239000008188 pellet Substances 0.000 title claims description 18
- 239000000126 substance Substances 0.000 title abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 64
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 59
- 239000007788 liquid Substances 0.000 claims abstract description 50
- 238000001694 spray drying Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 239000008187 granular material Substances 0.000 claims description 100
- 230000007704 transition Effects 0.000 claims description 35
- 229920003169 water-soluble polymer Polymers 0.000 claims description 33
- 239000003381 stabilizer Substances 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 20
- 239000004816 latex Substances 0.000 claims description 18
- 229920000126 latex Polymers 0.000 claims description 18
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical group [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 16
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 12
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 10
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 10
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 10
- 239000004323 potassium nitrate Substances 0.000 claims description 8
- 235000010333 potassium nitrate Nutrition 0.000 claims description 8
- 239000012798 spherical particle Substances 0.000 claims description 8
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 claims description 7
- 229910001487 potassium perchlorate Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000012071 phase Substances 0.000 description 85
- 239000007789 gas Substances 0.000 description 56
- 230000000052 comparative effect Effects 0.000 description 21
- 238000005259 measurement Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 239000007790 solid phase Substances 0.000 description 14
- 230000008859 change Effects 0.000 description 13
- 238000000113 differential scanning calorimetry Methods 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 239000010419 fine particle Substances 0.000 description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 239000000654 additive Substances 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 8
- 229920000058 polyacrylate Polymers 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 239000012736 aqueous medium Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 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 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000016507 interphase Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 1
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920002907 Guar gum Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- BRUFJXUJQKYQHA-UHFFFAOYSA-O ammonium dinitramide Chemical compound [NH4+].[O-][N+](=O)[N-][N+]([O-])=O BRUFJXUJQKYQHA-UHFFFAOYSA-O 0.000 description 1
- DVARTQFDIMZBAA-UHFFFAOYSA-O ammonium nitrate Chemical class [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000003232 water-soluble binding agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
- C06B31/28—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate
- C06B31/30—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate with vegetable matter; with resin; with rubber
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0091—Elimination of undesirable or temporary components of an intermediate or finished product, e.g. making porous or low density products, purifying, stabilising, drying; Deactivating; Reclaiming
Abstract
Description
本技術は、ガス発生剤用硝酸アンモニウム粒状物およびその製造方法に関する。詳しくは、硝酸アンモニウムを主たる成分とする防湿性に優れたガス発生剤用の硝酸アンモニウム粒状物に関するものである。 The present technology relates to an ammonium nitrate granular material for a gas generating agent and a method for producing the same. More specifically, the present invention relates to an ammonium nitrate granular material for a gas generating agent that is excellent in moisture resistance and mainly contains ammonium nitrate.
自動車用エアバッグ等のガス発生剤の成分として知られている硝酸アンモニウムは、その高い吸湿性のために取り扱い性が悪いことや、そのような硝酸アンモニウムを含有するペレットとしたときにペレット強度が低いこと、または長期間保管する際にその強度が変化することなどが指摘されている。 Ammonium nitrate, which is known as a component of gas generating agents for automobile airbags, has poor handleability due to its high hygroscopicity, and low pellet strength when used as a pellet containing such ammonium nitrate. It has been pointed out that the strength changes when stored for a long time.
たとえば、特許文献１には、燃料およびバインダーとして作用する高分子化合物を特定の高分子化合物に限定することで、燃焼時に残渣生成量が少ないガス発生剤組成物が記載されている。しかし、当該文献に記載されているように、一般的なガス発生剤の成型方法は、その組成物を水や有機溶媒に添加し、蒸発乾固や押出成型、打錠機による成型を行うものであり、該成型方法で得られるガス発生剤ペレットは、強度にばらつきが出ることがあり、また経時変化するおそれがあるものであった。 For example, Patent Document 1 describes a gas generant composition that generates a small amount of residue during combustion by limiting a polymer compound that acts as a fuel and a binder to a specific polymer compound. However, as described in the document, a general method for molding a gas generating agent is a method in which the composition is added to water or an organic solvent, followed by evaporation to dryness, extrusion molding, or molding by a tableting machine. The gas generant pellets obtained by the molding method may vary in strength and may change over time.
また、特許文献２には、アミノテトラゾールを含有させることにより、安全で信頼性の高い硝酸アンモニウム系ガス発生剤が記載されている。当該文献には、賦形剤として水溶性粘結剤が記載されているが、成型体の形状保持の観点から付加されるものであることから、その成型性の観点からのみ選択されており、硝酸アンモニウムの吸湿性を改善するために選択されるものではない。 Patent Document 2 describes a safe and highly reliable ammonium nitrate gas generator by containing aminotetrazole. In this document, a water-soluble binder is described as an excipient, but since it is added from the viewpoint of maintaining the shape of the molded body, it is selected only from the viewpoint of its moldability, It is not selected to improve the hygroscopicity of ammonium nitrate.
硝酸アンモニウムの吸湿性を改善する方法として、たとえば、非特許文献１には、大気圧グロープラズマという技術の開発により、硝酸アンモニウム粒子をポリマーで被覆させる方法が紹介されている。しかし、このポリマー被覆方法は、安定して球状化およびポリマー被覆をする条件を見出すことが難しく生産性を改善する必要がある。 As a method for improving the hygroscopicity of ammonium nitrate, for example, Non-Patent Document 1 introduces a method of coating ammonium nitrate particles with a polymer by developing a technique called atmospheric pressure glow plasma. However, in this polymer coating method, it is difficult to find conditions for stably spheroidizing and polymer coating, and it is necessary to improve productivity.
さらに、自動車用エアバッグに用いられるようなガス発生剤用の原料には、さまざまな環境で使用される車の車内温度や湿度の変化に対する安定性が求められる。しかしながら、硝酸アンモニウムは、常温〜１００℃程度の間に相変化（固相間相転移）が生じることを指摘されている。 Furthermore, a raw material for a gas generating agent used in an automobile airbag is required to have stability against changes in the temperature and humidity of a vehicle used in various environments. However, it has been pointed out that ammonium nitrate undergoes a phase change (phase transition between solid phases) between room temperature and about 100 ° C.
特許文献３には、水溶性ポリマーのカリウム塩を相安定化剤とバインダーの両方の作用とすることで、相安定化剤を別途配合する必要のないガス発生剤組成物が記載されている。しかし、当該文献に記載されている水溶性ポリマーのカリウム塩の用い方も前記したようにバインダーとして用いるものであり、ガス発生剤の成型も、押出成型、打錠機による圧縮成型であり、これらにより得られるペレットは強度および経時変化の点から更なる改善が求められるものであった。 Patent Document 3 describes a gas generant composition in which a potassium salt of a water-soluble polymer serves as both a phase stabilizer and a binder, so that it is not necessary to add a phase stabilizer separately. However, the use of the potassium salt of the water-soluble polymer described in the document is also used as a binder as described above, and the molding of the gas generating agent is also an extrusion molding or a compression molding by a tableting machine. The pellets obtained by the above method are required to be further improved in terms of strength and aging.
このように従来のガス発生剤用硝酸アンモニウム粒状物には、吸湿性を改善する要求が強く、さらに優れた相安定性を有することが求められていた。相安定性について詳述すると、硝酸アンモニウムは、２０℃から２００℃の温度範囲に４つの相転移点（３５℃付近、８０℃付近、１２５℃付近、１６０℃付近の４つ。１６０℃付近は融点、その他は固相間相転移点）を持つことが知られており、この固相間相転移により体積が変化する。自動車は、夏期などにおいては、昼間の車内温度は優に５０℃を超えることがあり、昼夜の温度変化がこの硝酸アンモニウムの相転移点（３５℃付近と場合によっては８０℃付近）をまたぐこととなる。したがって、このような相変化が生じるものを原料として用いると、ペレットが温度や湿度の変化に伴い相変化することで体積が増減し、ペレットにひび割れが生じることがある。このひび割れや強度変化によって、ペレットが破砕すると、想定外のガス発生挙動をひきおこすなどして、安全性に支障をきたす恐れもある。 As described above, the conventional ammonium nitrate granular materials for gas generating agents are strongly required to improve the hygroscopicity, and further required to have excellent phase stability. The phase stability will be described in detail. Ammonium nitrate has four phase transition points (around 35 ° C., 80 ° C., 125 ° C., and 160 ° C. in the temperature range of 20 ° C. to 200 ° C. Others are known to have a phase transition point between solid phases), and the volume changes due to the phase transition between the solid phases. In the summer, etc., the temperature inside the car can easily exceed 50 ° C in the summer, and the temperature change during the day and night straddles this ammonium nitrate phase transition point (around 35 ° C and in some cases around 80 ° C). Become. Therefore, when a material that causes such a phase change is used as a raw material, the pellet may undergo a phase change with a change in temperature or humidity, whereby the volume may increase or decrease, and the pellet may crack. If the pellet is crushed due to the crack or strength change, it may cause an unexpected gas generation behavior, which may hinder safety.
そこで、硝酸アンモニウムの固相間相転移を抑制するため、硝酸カリウムや過塩素酸カリウム等のカリウム塩や酸化銅等の銅化合物などの相安定化剤を添加してなる相安定化硝酸アンモニウムが知られている。この相安定化剤による該相安定化硝酸アンモニウムは、２０℃から１００℃付近の相転移を抑制する。しかしながら、安定性をより高くするために、さらに、１２５℃付近にみられる相転移も抑制されることを含めた１５０℃以下の温度における相転移が起こらないものが望まれている。 Therefore, in order to suppress phase transition between solid phases of ammonium nitrate, phase-stabilized ammonium nitrate obtained by adding a phase stabilizer such as potassium salt such as potassium nitrate or potassium perchlorate or copper compound such as copper oxide is known. Yes. The phase-stabilized ammonium nitrate by this phase stabilizer suppresses the phase transition around 20 ° C to 100 ° C. However, in order to further increase the stability, it is further desired that the phase transition at a temperature of 150 ° C. or lower including that the phase transition around 125 ° C. is also suppressed does not occur.
かかる状況下、本発明は、防湿性に優れており、同時に広範な温度範囲で相安定性を有するガス発生剤用硝酸アンモニウム粒状物の製造方法を提供することを課題とする。 Under such circumstances, an object of the present invention is to provide a method for producing an ammonium nitrate granular material for a gas generating agent that is excellent in moisture resistance and at the same time has phase stability in a wide temperature range.
本発明者は、上記課題を解決すべく鋭意研究を重ねた結果、下記の発明が上記目的に合致することを見出し、本発明に至った。 As a result of intensive studies to solve the above problems, the present inventor has found that the following inventions meet the above object, and have reached the present invention.
すなわち、本発明は、以下の発明に係るものである。
＜１＞ 硝酸アンモニウムと、水溶性ポリマーおよび／または水分散性ポリマーとを、水を主たる成分とする溶媒に溶解または分散させて硝酸アンモニウム含有液を作製し、当該硝酸アンモニウム含有液を噴霧乾燥することを特徴とするガス発生剤用硝酸アンモニウム粒状物の製造方法。
＜２＞ 前記硝酸アンモニウム含有液が、さらに硝酸アンモニウムの相安定化剤を含む前記＜１＞記載のガス発生剤用硝酸アンモニウム粒状物の製造方法。
＜３＞ 前記硝酸アンモニウム含有液の固形物濃度が、５重量％以上６５重量％以下である前記＜１＞または＜２＞に記載のガス発生剤用硝酸アンモニウム粒状物の製造方法。
＜４＞ 前記硝酸アンモニウム含有液の固形物全量に対する硝酸アンモニウムの割合が、７０重量％以上９９．９重量％以下である前記＜１＞〜＜３＞のいずれかに記載のガス発生剤用硝酸アンモニウム粒状物の製造方法。
＜５＞ 前記硝酸アンモニウム含有液の固形物全量に対する前記水溶性ポリマーおよび水分散性ポリマーの割合が、０．１重量％以上２０重量％以下である前記＜１＞〜＜４＞のいずれかに記載のガス発生剤用硝酸アンモニウム粒状物の製造方法。
＜６＞ 前記硝酸アンモニウム含有液の固形物全量に対する前記相安定化剤の割合が、１重量％以上２０重量％以下である前記＜２＞〜＜５＞のいずれかに記載のガス発生剤用硝酸アンモニウム粒状物の製造方法。
＜７＞ 前記水溶性ポリマーが、カルボキシメチルセルロース塩である、前記＜１＞〜＜６＞のいずれかに記載のガス発生剤用硝酸アンモニウム粒状物の製造方法。
＜８＞ 前記水分散性ポリマーが、ラテックスとなるものである、前記＜１＞〜＜７＞のいずれかに記載のガス発生剤用硝酸アンモニウム粒状物の製造方法。
＜９＞ 前記相安定化剤が、硝酸カリウムおよび／または過塩素酸カリウムである前記＜２＞〜＜８＞のいずれかに記載のガス発生剤用硝酸アンモニウム粒状物の製造方法。
＜１０＞ 硝酸アンモニウムと、水溶性ポリマーおよび／または水分散性ポリマーとを、水を主たる成分とする溶媒に溶解または分散させて硝酸アンモニウム含有液を作製し、当該硝酸アンモニウム含有液を噴霧乾燥することにより得られることを特徴とするガス発生剤用硝酸アンモニウム粒状物。
＜１１＞ 前記ガス発生剤用硝酸アンモニウム粒状物の形状が、略球状粒子である前記＜１０＞に記載のガス発生剤用硝酸アンモニウム粒状物。
＜１２＞ 前記略球状粒子のモード粒子径が、１μｍ以上２００μｍ以下である前記＜１１＞に記載のガス発生剤用硝酸アンモニウム粒状物。
＜１３＞ 前記ガス発生剤用硝酸アンモニウム粒状物が、常温から１５０℃以下の温度範囲で相転移を有さない前記＜１０＞〜＜１２＞のいずれかに記載のガス発生剤用硝酸アンモニウム粒状物。
＜１４＞ 前記＜１０＞〜＜１３＞のいずれかに記載のガス発生剤用硝酸アンモニウム粒状物を用いてなるガス発生剤ペレット。
That is, the present invention relates to the following inventions.
<1> Ammonium nitrate-containing liquid is prepared by dissolving or dispersing ammonium nitrate and a water-soluble polymer and / or a water-dispersible polymer in a solvent containing water as a main component, and the ammonium nitrate-containing liquid is spray-dried. The manufacturing method of the ammonium nitrate granular material for gas generating agents.
<2> The method for producing an ammonium nitrate granular material for a gas generating agent according to <1>, wherein the ammonium nitrate-containing liquid further contains a phase stabilizer for ammonium nitrate.
<3> The method for producing an ammonium nitrate granular material for a gas generating agent according to <1> or <2>, wherein the solid concentration of the ammonium nitrate-containing liquid is 5% by weight or more and 65% by weight or less.
<4> The ammonium nitrate granular material for a gas generating agent according to any one of <1> to <3>, wherein the ratio of ammonium nitrate to the total amount of solids of the ammonium nitrate-containing liquid is 70 wt% or more and 99.9 wt% or less. Manufacturing method.
<5> The ratio according to any one of <1> to <4>, wherein a ratio of the water-soluble polymer and the water-dispersible polymer to the total amount of the solid in the ammonium nitrate-containing liquid is 0.1% by weight or more and 20% by weight or less. Of producing ammonium nitrate granular material for gas generating agent.
<6> Ammonium nitrate for gas generating agent according to any one of <2> to <5>, wherein the ratio of the phase stabilizer to the total amount of the solid in the ammonium nitrate-containing liquid is 1% by weight or more and 20% by weight or less. A manufacturing method of granular materials.
<7> The method for producing an ammonium nitrate granular material for a gas generating agent according to any one of <1> to <6>, wherein the water-soluble polymer is a carboxymethylcellulose salt.
<8> The method for producing ammonium nitrate granular materials for a gas generating agent according to any one of <1> to <7>, wherein the water-dispersible polymer is a latex.
<9> The method for producing an ammonium nitrate granular material for a gas generating agent according to any one of <2> to <8>, wherein the phase stabilizer is potassium nitrate and / or potassium perchlorate.
<10> Ammonium nitrate and a water-soluble polymer and / or water-dispersible polymer are dissolved or dispersed in a solvent containing water as a main component to prepare an ammonium nitrate-containing liquid, and obtained by spray drying the ammonium nitrate-containing liquid. Ammonium nitrate granular material for gas generating agents, characterized in that
<11> The ammonium nitrate granular material for gas generating agent according to <10>, wherein the shape of the ammonium nitrate granular material for gas generating agent is a substantially spherical particle.
<12> The ammonium nitrate granular material for gas generating agent according to <11>, wherein the mode particle diameter of the substantially spherical particles is 1 μm or more and 200 μm or less.
<13> The ammonium nitrate granular material for a gas generating agent according to any one of <10> to <12>, wherein the ammonium nitrate granular material for a gas generating agent does not have a phase transition in a temperature range from room temperature to 150 ° C. or less.
<14> A gas generant pellet using the ammonium nitrate granular material for gas generant according to any one of <10> to <13>.
本発明によれば、防湿性に優れておりかつ固相間相転移が少ないガス発生剤用硝酸アンモニウムが提供される。本発明の製造方法により得られるガス発生剤用硝酸アンモニウム粒状物は、防湿性に優れておりかつ固相間相転移が少ないため、これを用いたガス発生剤をペレットとしたとき、そのペレットは強度が高く、また体積変化も少ないものとなる。本発明の硝酸アンモニウムは、特に自動車用エアバッグ等に好適に使用することができる。また、本発明のガス発生剤用硝酸アンモニウム粒状物は、ガス発生剤ペレット等とするときにバインダーとして機能するポリマーを一体化しているため、取り扱い性に優れたものである。 ADVANTAGE OF THE INVENTION According to this invention, the ammonium nitrate for gas generants which is excellent in moisture resistance and there are few phase transitions between solid phases is provided. Since the ammonium nitrate granular material for gas generant obtained by the production method of the present invention is excellent in moisture resistance and has few phase transitions between solid phases, when the gas generant using this is used as a pellet, the pellet has strength. And the volume change is small. The ammonium nitrate of the present invention can be suitably used particularly for automobile airbags. In addition, the ammonium nitrate granular material for a gas generating agent of the present invention is excellent in handleability because it integrates a polymer that functions as a binder when forming a gas generating agent pellet or the like.
以下に本発明の実施の形態を詳細に説明するが、以下に記載する構成要件の説明は、本発明の実施態様の一例（代表例）であり、本発明はその要旨を超えない限り、以下の内容に限定されない。 DESCRIPTION OF EMBODIMENTS Embodiments of the present invention will be described in detail below. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention. It is not limited to the contents.
本発明は、硝酸アンモニウムと、水溶性ポリマーおよび／または水分散性ポリマーとを、水を主たる成分とする溶媒に溶解または分散させて硝酸アンモニウム含有液を作製し、当該硝酸アンモニウム含有液を噴霧乾燥して硝酸アンモニウム粒状物を得るガス発生剤用硝酸アンモニウム粒状物の製造方法にかかるものである。また、硝酸アンモニウムと、水溶性ポリマーおよび／または水分散性ポリマーとを、水を主たる成分とする溶媒に溶解または分散させて硝酸アンモニウム含有液を作製し、当該硝酸アンモニウム含有液を噴霧乾燥することにより得られてなる硝酸アンモニウム粒状物にかかるものである。 In the present invention, an ammonium nitrate-containing liquid is prepared by dissolving or dispersing ammonium nitrate and a water-soluble polymer and / or a water-dispersible polymer in a solvent containing water as a main component, and the ammonium nitrate-containing liquid is spray-dried to produce ammonium nitrate. The present invention relates to a method for producing an ammonium nitrate granular material for a gas generating agent to obtain a granular material. Also, it is obtained by dissolving or dispersing ammonium nitrate and a water-soluble polymer and / or water-dispersible polymer in a solvent containing water as a main component to prepare an ammonium nitrate-containing liquid, and spray-drying the ammonium nitrate-containing liquid. It relates to the ammonium nitrate granular material.
本発明の製造方法によれば、優れた防湿性を有する硝酸アンモニウム粒状物を得ることができるため、当該硝酸アンモニウム粒状物をガス発生剤用途に用いたとき有用である。
以下、本発明の製造方法につき、詳細に説明する。
According to the production method of the present invention, an ammonium nitrate granular material having excellent moisture-proof property can be obtained, which is useful when the ammonium nitrate granular material is used for a gas generating agent.
Hereinafter, the production method of the present invention will be described in detail.
［硝酸アンモニウム］
本発明において、硝酸アンモニウムは、ガス発生剤における酸化剤として用いられる。本発明で用いる硝酸アンモニウムは、純度、用途に関して、特に限定はなく、高純度のものを用いた方が好ましい。また、溶媒に溶解させるため粉状、粒状のいずれのものでもよいが、溶解しやすい形態である粉状の方が好ましい。
[Ammonium nitrate]
In the present invention, ammonium nitrate is used as an oxidizing agent in the gas generating agent. The ammonium nitrate used in the present invention is not particularly limited with respect to purity and use, and it is preferable to use a high-purity ammonium nitrate. Moreover, since it may be dissolved in a solvent, it may be either powdery or granular, but a powdery form that is easy to dissolve is preferred.
［水溶性ポリマーおよび／または水分散性ポリマー］
本発明の製造方法において、前記硝酸アンモニウム含有液は、硝酸アンモニウムと共に、水溶性ポリマーおよび／または水分散性ポリマーを必須成分として含む。
[Water-soluble polymer and / or water-dispersible polymer]
In the production method of the present invention, the ammonium nitrate-containing liquid contains a water-soluble polymer and / or a water-dispersible polymer as essential components together with ammonium nitrate.
本発明で用いる水溶性ポリマーとは、分子内に親水基を多く持ち、水に溶解する高分子を意味する。水溶性ポリマーは、架橋構造を有しない直鎖状の水溶性ポリマーを用いることが好ましい。また、水溶性ポリマーの分子量は、水溶性を示す物性であれば特に問題はないが、硝酸アンモニウム粒状物の製造効率等の観点から、重量平均分子量として５，０００以上で５００，０００以下であることが好ましい。 The water-soluble polymer used in the present invention means a polymer having many hydrophilic groups in the molecule and soluble in water. As the water-soluble polymer, a linear water-soluble polymer having no cross-linked structure is preferably used. The molecular weight of the water-soluble polymer is not particularly limited as long as it is a water-soluble physical property, but from the viewpoint of the production efficiency of ammonium nitrate particulates, the weight average molecular weight is 5,000 or more and 500,000 or less. Is preferred.
本発明に用いられる水溶性ポリマーとしては、例えば、ポリビニルアルコール、カルボキシメチルセルロースアンモニウム、カルボキシメチルセルロースナトリウム、ポリエチレングリコール、ポリプロピレングリコール、ポリビニルエーテル、ポリマレイン酸共重合体、ポリエチレンイミド、ポリビニルピロリドン、ポリアクリルアミド、ポリアクリル酸ナトリウム、ポリアクリル酸アンモニウム、デキストリンおよびその水和物、グアガム等が挙げられる。これらの中でも、水溶性ポリマーとしてポリビニルアルコール、カルボキシメチルセルロース塩、またはポリアクリル酸塩の使用が、相安定性に優れた硝酸アンモニウム粒状物を得ることができるため好ましい。特に好ましくは、ポリビニルアルコール、カルボキシメチルセルロースアンモニウム、またはポリアクリル酸アンモニウムである。 Examples of the water-soluble polymer used in the present invention include polyvinyl alcohol, carboxymethyl cellulose ammonium, sodium carboxymethyl cellulose, polyethylene glycol, polypropylene glycol, polyvinyl ether, polymaleic acid copolymer, polyethylene imide, polyvinyl pyrrolidone, polyacrylamide, and polyacrylic. Examples thereof include sodium acid, ammonium polyacrylate, dextrin and hydrates thereof, and guar gum. Among these, the use of polyvinyl alcohol, carboxymethyl cellulose salt, or polyacrylate as the water-soluble polymer is preferable because an ammonium nitrate granule excellent in phase stability can be obtained. Particularly preferred are polyvinyl alcohol, carboxymethyl cellulose ammonium or ammonium polyacrylate.
本発明に用いるポリビニルアルコールは、カルボン酸架橋剤、アセタール架橋剤、金属キレート剤等による架橋構造を有しない、直鎖状のポリビニルアルコールを用いることが好ましい。ポリビニルアルコールは、重合度が１００以上５，０００以下のポリビニルアルコール、または重量平均分子量が５，０００以上２００，０００以下のポリビニルアルコールを用いることが好ましい。カルボキシメチルセルロース塩を用いると、非常に優れた相安定性を有する粒状物を得ることができるため好ましい。カルボキシメチルセルロース塩としては、アンモニウム塩、ナトリウム塩が好ましい。特に好ましくはカルボキシメチルセルロースアンモニウムである。また、ポリアクリル酸塩を用いると、優れた相安定性を有する粒状物を得ることができるため好ましい。ポリアクリル酸塩としては、アンモニウム塩、ナトリウム塩が好ましい。特に好ましくはポリアクリル酸塩アンモニウムである。 As the polyvinyl alcohol used in the present invention, it is preferable to use linear polyvinyl alcohol that does not have a crosslinking structure formed by a carboxylic acid crosslinking agent, an acetal crosslinking agent, a metal chelating agent, or the like. As the polyvinyl alcohol, it is preferable to use polyvinyl alcohol having a degree of polymerization of 100 or more and 5,000 or less, or polyvinyl alcohol having a weight average molecular weight of 5,000 or more and 200,000 or less. The use of carboxymethyl cellulose salt is preferable because a granular material having very excellent phase stability can be obtained. As the carboxymethylcellulose salt, ammonium salt and sodium salt are preferable. Particularly preferred is carboxymethyl cellulose ammonium. Moreover, it is preferable to use a polyacrylate because a granular material having excellent phase stability can be obtained. As the polyacrylate, ammonium salt and sodium salt are preferable. Particularly preferred is ammonium polyacrylate.
本発明で用いる水分散性ポリマーとは、水中に散在して混合される高分子を意味する。この水分散性ポリマーを本発明に使用するにあたっては、例えば、水中に散在して混合される高分子体の微粒子等を適当な乳化剤を用いて乳化させた高分子の水系溶剤分散剤（分散液、一般的にラテックスと呼ばれる）の形態が挙げられる。本発明において、このようなラテックスの状態の水分散性ポリマーの分散液を用いて硝酸アンモニウム含有液を作製すると、硝酸アンモニウム含有液とする工程の混合性が良好となり、得られるガス発生剤用硝酸アンモニウムの吸湿性、相安定性も安定した良好なものとしやすい。好ましくは、高分子がポリスチレン微粒子である分散液（ポリスチレンラテックス）または高分子がスチレン-ブタジエン共重合体微粒子である分散液（スチレン-ブタジエン共重合体ラテックス）の形態で使用する。 The water-dispersible polymer used in the present invention means a polymer that is dispersed and mixed in water. When this water-dispersible polymer is used in the present invention, for example, a polymer aqueous solvent dispersant (dispersion liquid) obtained by emulsifying fine particles of a polymer dispersed and mixed in water using an appropriate emulsifier. , Generally called latex). In the present invention, when an ammonium nitrate-containing liquid is prepared using a dispersion of such a water-dispersible polymer in a latex state, the mixing ability in the step of making an ammonium nitrate-containing liquid is improved, and the resulting moisture absorption of ammonium nitrate for a gas generating agent is improved. It is easy to make the property and phase stability stable and good. Preferably, it is used in the form of a dispersion liquid (polystyrene latex) in which the polymer is a polystyrene fine particle or a dispersion liquid (styrene-butadiene copolymer latex) in which the polymer is a styrene-butadiene copolymer fine particle.
ポリスチレン微粒子やスチレン−ブタジエン共重合体微粒子等の高分子体微粒子は特に限定されるものではないが、その粒子径が０．０１μｍ〜１００μｍである高分子体微粒子が好ましく用いられる。より好ましくは粒子径が０．０１μｍ〜１．０μｍの高分子体微粒子である。一般的には、これらの高分子体微粒子を２０〜８０質量％の含量で、水系媒体に分散させた水分散性ポリマーの分散液を用いる。水分散性ポリマーは、水系媒体に分散させた分散液の粘度により物性規定されることが一般的であり、本発明で用いられる水分散性ポリマーの分散液としては、他の成分と混合し硝酸アンモニウム粒状物を製造するときの製造効率等の観点から、粘度１０〜５０，０００ｍＰａ・ｓのものを用いることが好ましい。スチレン-ブタジエン共重合体微粒子を用いたスチレン-ブタジエン共重合体ラテックスは、高いゴム弾性と接着強度を有するエマルジョン系ゴム質接着剤の物性を有する。 Polymer fine particles such as polystyrene fine particles and styrene-butadiene copolymer fine particles are not particularly limited, but polymer fine particles having a particle diameter of 0.01 μm to 100 μm are preferably used. More preferred are polymer fine particles having a particle size of 0.01 μm to 1.0 μm. Generally, a dispersion of a water-dispersible polymer in which these polymer fine particles are dispersed in an aqueous medium at a content of 20 to 80% by mass is used. The water-dispersible polymer is generally defined in terms of physical properties by the viscosity of the dispersion dispersed in an aqueous medium. The water-dispersible polymer dispersion used in the present invention is mixed with other components and mixed with ammonium nitrate. From the viewpoint of production efficiency when producing a granular material, it is preferable to use one having a viscosity of 10 to 50,000 mPa · s. Styrene-butadiene copolymer latex using styrene-butadiene copolymer fine particles has the properties of an emulsion rubber adhesive having high rubber elasticity and adhesive strength.
本発明において水分散性ポリマーは、粒子径０．０１μｍ〜１．０μｍのスチレン−ブタジエン共重合体微粒子を水媒体に２０〜８０重量％含有し、当該水媒体に分散させた分散液の粘度が３０〜１０，０００ｍＰａ・ｓとなるスチレン−ブタジエン共重合体をラテックスの状態で用いることが特に好ましい一例として挙げられる。また、本発明に水分散性ポリマーを用いると優れた防湿性が得られることから好ましく、水分散性ポリマーはラテックスの状態で用いることが好ましく、特にポリスチレンラテックスまたはスチレン−ブタジエン共重合体ラテックスを用いると、非常に優れた防湿性を得ることができるため好ましい。 In the present invention, the water-dispersible polymer contains 20 to 80% by weight of styrene-butadiene copolymer fine particles having a particle diameter of 0.01 to 1.0 μm in an aqueous medium, and the viscosity of the dispersion liquid dispersed in the aqueous medium is as follows. A particularly preferred example is the use of a styrene-butadiene copolymer in a latex state of 30 to 10,000 mPa · s. In addition, it is preferable to use a water-dispersible polymer in the present invention because excellent moisture-proof properties can be obtained. The water-dispersible polymer is preferably used in a latex state, and in particular, a polystyrene latex or a styrene-butadiene copolymer latex is used. It is preferable because very excellent moisture resistance can be obtained.
本発明の製造方法において、前記硝酸アンモニウム含有液は、水溶性ポリマーや水分散性ポリマーを含んでいればよく、複数の水溶性ポリマーや水分散性ポリマーを組み合わせて用いてもよい。 In the production method of the present invention, the ammonium nitrate-containing liquid only needs to contain a water-soluble polymer or a water-dispersible polymer, and a plurality of water-soluble polymers or water-dispersible polymers may be used in combination.
また本発明の目的を損なわない範囲で、水溶性ポリマーや水分散性ポリマー以外の疎水性のポリマー等（その他ポリマー）を含んでいてもよい。 In addition, a hydrophobic polymer other than the water-soluble polymer and the water-dispersible polymer (other polymers) may be included as long as the object of the present invention is not impaired.
［溶媒］
本発明の製造方法において、硝酸アンモニウム含有液における溶媒は、水を主たる成分とする溶媒である。ここで、「水を主たる成分とする」とは、溶媒全量に対し、水の割合が５０重量％以上、好ましくは、８０重量％以上（１００重量％含む）であることをいう。ガス発生剤の主原料である硝酸アンモニウムの反応性が高いこと、また噴霧乾燥により当該溶媒を乾燥する処理を行うことから、反応性の高い溶媒を使用すると安全面で問題が生じる場合がある。特に可燃性の有機溶媒を主成分とするとき問題となりやすい。これに対し、本発明の製造方法では、水を主たる成分とするため、このような問題が生じないという利点がある。
[solvent]
In the production method of the present invention, the solvent in the ammonium nitrate-containing liquid is a solvent containing water as a main component. Here, “with water as the main component” means that the ratio of water is 50% by weight or more, preferably 80% by weight or more (including 100% by weight) with respect to the total amount of the solvent. Since ammonium nitrate, which is the main raw material of the gas generating agent, is highly reactive, and the solvent is dried by spray drying, use of a highly reactive solvent may cause a safety problem. This is particularly problematic when combustible organic solvents are the main component. On the other hand, in the manufacturing method of this invention, since water is the main component, there exists an advantage that such a problem does not arise.
溶媒には、安全性に配慮したうえで、アルコール等の他の溶媒を加え、固形分の溶解性や分散性を調整することもできる。たとえば、アルコールとしては、メチルアルコールや、エチルアルコール、ブチルアルコール等を用いることができる。 In consideration of safety, other solvents such as alcohol can be added to the solvent to adjust the solubility and dispersibility of the solid content. For example, methyl alcohol, ethyl alcohol, butyl alcohol, or the like can be used as the alcohol.
［相安定化剤］
本発明の製造方法において、硝酸アンモニウム含有液にさらに硝酸アンモニウムの相安定化剤を添加してもよい。該相安定化剤を含むことで、製造される硝酸アンモニウム粒状物は、硝酸アンモニウム由来の相変化がより抑制される。
このような相安定化剤としては、例えば硝酸カリウム、過塩素酸カリウム、塩素酸カリウム、過マンガン酸カリウム、クロム酸カリウム、二クロム酸カリウム、塩化カリウム、硫酸カリウム、シュウ酸カリウム、硝酸ナトリウム、塩化アンモニウム、硝酸銅、硝酸セシウム、塩化セシウム等が挙げられる。この中でも、特に硝酸カリウムや過塩素酸カリウム等のカリウム塩が好ましく、中でも硝酸カリウムは、少量でも相安定化効果が大きいため、好ましく用いられる。従来、硝酸アンモニウムに相安定化剤を加える場合、相安定化剤および硝酸アンモニウムは水に溶けるため、これらを水に溶解させた後、蒸発乾固して相安定化硝酸アンモニウムを得ることが多かった。しかし本発明では、相安定化剤を添加する場合も、蒸発乾固を行わずとも、噴霧乾燥を行うため相安定化剤を一括混合し製造することができる。
[Phase stabilizer]
In the production method of the present invention, an ammonium nitrate phase stabilizer may be further added to the ammonium nitrate-containing liquid. By including the phase stabilizer, the phase change derived from ammonium nitrate is further suppressed in the produced ammonium nitrate granular material.
Examples of such phase stabilizers include potassium nitrate, potassium perchlorate, potassium chlorate, potassium permanganate, potassium chromate, potassium dichromate, potassium chloride, potassium sulfate, potassium oxalate, sodium nitrate, chloride Examples include ammonium, copper nitrate, cesium nitrate, and cesium chloride. Among these, potassium salts such as potassium nitrate and potassium perchlorate are particularly preferable. Among them, potassium nitrate is preferably used because it has a large phase stabilizing effect even in a small amount. Conventionally, when a phase stabilizer is added to ammonium nitrate, since the phase stabilizer and ammonium nitrate are soluble in water, they are often dissolved in water and then evaporated to dryness to obtain phase-stabilized ammonium nitrate. However, in the present invention, even when a phase stabilizer is added, the phase stabilizer can be mixed and produced for spray drying without performing evaporation to dryness.
［添加剤］
本発明の製造方法において、本発明の目的を損なわない範囲で、硝酸アンモニウム含有液に硝酸アンモニウム等の前記固形物成分以外の添加剤を添加してもよい。
このような添加剤としては、製造される硝酸アンモニウム粒状物をガス発生剤として用いたときに、その反応性を向上させる等の目的で添加される添加剤（たとえば硝酸ストロンチウム、塩基性硝酸銅等の硝酸塩やアンモニウムジニトラミド等）や、溶媒に溶解させたときの溶解性、分散性を向上させる添加剤等が挙げられる。
[Additive]
In the production method of the present invention, an additive other than the above-mentioned solid component such as ammonium nitrate may be added to the ammonium nitrate-containing liquid as long as the object of the present invention is not impaired.
Examples of such additives include additives that are added for the purpose of improving the reactivity when the produced ammonium nitrate granular material is used as a gas generating agent (for example, strontium nitrate, basic copper nitrate, etc.). Nitrates, ammonium dinitramide, etc.) and additives that improve solubility and dispersibility when dissolved in a solvent.
［硝酸アンモニウム含有液の組成］
上述のように、本発明の製造方法における硝酸アンモニウム含有液は、硝酸アンモニウム、水溶性ポリマー、水分散性ポリマー、および必要に応じて添加される相安定化剤や、添加剤といった固形物と、水を主たる成分とする溶媒から構成される。
硝酸アンモニウム含有液中の、固形物濃度は、５重量％以上６５重量％以下であることが好ましく、より好ましくは１０重量％以上３０重量％以下である。なお、ここでいう固形物濃度を計算するときの固形物には、硝酸アンモニウム、水溶性ポリマー、水分散性ポリマー、および必要に応じて添加される相安定化剤や、添加剤、その他ポリマー等を含む。
該固形物濃度が低すぎる場合、噴霧乾燥を行ったときに得られる硝酸アンモニウム粒状物の生産効率が低い、または水分量が多すぎるため乾燥しにくいことがある。固形物濃度が高すぎる場合、噴霧乾燥を行うのに適さないような溶液粘度となり、得られる硝酸アンモニウム粒状物の特性が十分なものとならないことがある。
[Composition of ammonium nitrate-containing liquid]
As described above, the ammonium nitrate-containing liquid in the production method of the present invention contains ammonium nitrate, a water-soluble polymer, a water-dispersible polymer, a solid substance such as a phase stabilizer and additives that are added as necessary, and water. Consists of a solvent as a main component.
The solid concentration in the ammonium nitrate-containing liquid is preferably 5% by weight to 65% by weight, and more preferably 10% by weight to 30% by weight. In addition, the solid when calculating the solid concentration referred to herein includes ammonium nitrate, a water-soluble polymer, a water-dispersible polymer, a phase stabilizer added as necessary, an additive, and other polymers. Including.
When the solid concentration is too low, the production efficiency of the ammonium nitrate granular material obtained when spray drying is performed may be low, or it may be difficult to dry due to too much water content. If the solid concentration is too high, the solution viscosity may be unsuitable for spray drying, and the resulting ammonium nitrate particulates may not have sufficient characteristics.
また、酸化剤としてガス発生剤に用いたときの反応性の調整を行いやすくするために、前記硝酸アンモニウム含有液中の固形物全量に対する硝酸アンモニウムの割合が７０重量％以上９９．９重量％以下であることが好ましく、より好ましくは、７０重量％以上９８重量％以下である。 Further, in order to facilitate the adjustment of reactivity when used as a gas generating agent as an oxidizing agent, the ratio of ammonium nitrate to the total amount of solids in the ammonium nitrate-containing liquid is 70 wt% or more and 99.9 wt% or less. More preferably, it is 70 to 98 weight%.
また、酸化剤としての反応性と、防湿性および相安定性の改善効果の両立の点で、前記硝酸アンモニウム含有液中の固形物全量に対する水溶性ポリマー及び水分散性ポリマーの割合は０．１重量％以上２０重量％以下であることが好ましい。０．１重量％よりも少ない場合、硝酸アンモニウム粒状物の特性を十分に改善することができないことがあり、２０重量％を超える場合、硝酸アンモニウムの量が少なくなるため、ガス発生剤用酸化剤としての反応性が低下するおそれがある。ポリマーの重量は好ましくは１重量％以上１５重量％以下であり、より好ましくは１重量％以上１２重量％以下である。 In addition, the ratio of the water-soluble polymer and the water-dispersible polymer to the total amount of solids in the ammonium nitrate-containing liquid is 0.1% in terms of both the reactivity as an oxidizing agent and the moisture-proof and phase-stability improving effects. % To 20% by weight is preferable. When the amount is less than 0.1% by weight, the characteristics of the ammonium nitrate particulate matter may not be sufficiently improved. When the amount exceeds 20% by weight, the amount of ammonium nitrate is reduced, so Reactivity may be reduced. The weight of the polymer is preferably 1% by weight or more and 15% by weight or less, more preferably 1% by weight or more and 12% by weight or less.
また、前記硝酸アンモニウム含有液に相安定化剤を添加する場合、相転移抑制効果の観点から、該硝酸アンモニウム含有液中の固形物全量に対する相安定化剤の割合は１重量％以上２０重量％以下であることが好ましく、より好ましくは３〜１５重量％である。
なお、相安定化剤を添加する場合には、あらかじめ、相安定化剤と硝酸アンモニウムとを混和させた相安定化硝酸アンモニウムを、本発明の硝酸アンモニウムおよび相安定化剤として使用することもできる。
In addition, when a phase stabilizer is added to the ammonium nitrate-containing liquid, the ratio of the phase stabilizer to the total amount of solids in the ammonium nitrate-containing liquid is 1% by weight or more and 20% by weight or less from the viewpoint of the effect of suppressing the phase transition. It is preferable that it is 3 to 15% by weight.
When a phase stabilizer is added, phase-stabilized ammonium nitrate obtained by mixing a phase stabilizer and ammonium nitrate in advance can also be used as the ammonium nitrate and phase stabilizer of the present invention.
［硝酸アンモニウム含有液の作製方法］
硝酸アンモニウム含有液の作製方法は、特に限定されず、その構成成分である硝酸アンモニウム、水溶性ポリマーおよび／または水分散性ポリマー、必要に応じて他の成分を、水を主たる成分とする溶媒に溶解または分散させればよい。混合方法としては、例えば、攪拌機で攪拌する方法や超音波振動を加えて撹拌する方法等がある。
混合順序も反応や沈殿物が発生するなど特段の問題がない限り任意であり、硝酸アンモニウム含有液の構成成分のうち、何れか２成分又は３成分以上を予め配合し、その後に残りの成分を混合してもよいし、一度に全部を混合してもよい。
[Method for preparing ammonium nitrate-containing liquid]
The production method of the ammonium nitrate-containing liquid is not particularly limited, and its constituent components, ammonium nitrate, a water-soluble polymer and / or a water-dispersible polymer, and other components as necessary are dissolved in a solvent containing water as a main component. What is necessary is just to disperse. Examples of the mixing method include a method of stirring with a stirrer and a method of stirring by applying ultrasonic vibration.
The mixing order is arbitrary as long as there is no particular problem such as reaction or precipitation, and any two or more components of the ammonium nitrate-containing liquid are mixed in advance, and then the remaining components are mixed. Or you may mix all at once.
［噴霧乾燥］
本発明の製造方法において、前記硝酸アンモニウム含有液を噴霧乾燥することにより硝酸アンモニウム粒状物を得る。
ここで、噴霧乾燥とは、乾燥対象となる溶液または分散液を気体中に噴霧して急速に乾燥させ、乾燥粉体を製造する手法である。本発明の製造方法では、噴霧乾燥で乾燥させることに特徴のひとつがあり、従来の押出成型や打錠機による圧縮成型等の乾燥方法と比較して、硝酸アンモニウムと水溶性ポリマーおよび水分散性ポリマーがより一体化するため、優れた防湿性や相安定性を有する硝酸アンモニウム粒状物とすることができる。
[Spray drying]
In the production method of the present invention, the ammonium nitrate-containing liquid is obtained by spray drying the ammonium nitrate-containing liquid.
Here, spray drying is a technique for producing a dry powder by spraying a solution or dispersion to be dried into a gas and drying it rapidly. The production method of the present invention has one of the features of drying by spray drying, and ammonium nitrate, a water-soluble polymer, and a water-dispersible polymer as compared with conventional drying methods such as extrusion molding and compression molding by a tableting machine. Therefore, it is possible to obtain an ammonium nitrate granular material having excellent moisture resistance and phase stability.
噴霧乾燥は、工業的には、例えば、溶液（本発明においては硝酸アンモニウム含有液）をノズル（ノズル噴霧方式）または遠心噴霧方式（ロータリーアトマイザー方式）で微粒化し熱風と接触させ、瞬間的に乾燥を行い粒子を製造する。ノズル噴霧方式で行う場合、ノズルはどのようなものでもよいが、一般のものとして、回転円盤ノズルと単流体圧力渦ノズル（ｓｉｎｇｌｅ−ｆｌｕｉｄ ｐｒｅｓｓｕｒｅ ｓｗｉｒｌ ｎｏｚｚｌｅ）などがある。あるいは、二流体ノズルまたは超音波ノズルを用いてもよい。遠心噴霧方式で行う場合、ディスクの形状や回転数を調整することで、粒子径を調整することができる。 In spray drying, industrially, for example, a solution (a solution containing ammonium nitrate in the present invention) is atomized by a nozzle (nozzle spray method) or a centrifugal spray method (rotary atomizer method) and brought into contact with hot air, and dried instantaneously. To produce particles. When the nozzle spraying method is used, any type of nozzle may be used, but general examples include a rotating disk nozzle and a single-fluid pressure swirl nozzle. Alternatively, a two-fluid nozzle or an ultrasonic nozzle may be used. In the case of the centrifugal spraying method, the particle diameter can be adjusted by adjusting the shape and rotation speed of the disk.
本発明の製造方法において、噴霧乾燥に用いる気体は、空気、または窒素等の噴霧乾燥を行う際に選択される一般的なものでよい。安全のために窒素のような不活性気体を選択することもできる。 In the production method of the present invention, the gas used for spray drying may be a general gas selected when spray drying such as air or nitrogen. An inert gas such as nitrogen can be selected for safety.
噴霧乾燥における乾燥温度は、主たる溶媒である水を乾燥することができればよいが、その他にも使用する噴霧乾燥機の大きさ、硝酸アンモニウム含有液に含まれる固形物成分、水以外の溶媒の種類や割合等を考慮して適宜設定される。
また、製造する硝酸アンモニウム粒状物の形状や粒径は、主に噴霧乾燥の条件でコントロールすることができる。硝酸アンモニウム粒状物は、好適な形状である略球状粒子や、好適な粒径範囲になるように、噴霧液滴サイズや乾燥条件の調整を行うことが好ましい。
The drying temperature in the spray drying is not limited as long as water, which is the main solvent, can be dried.In addition, the size of the spray dryer to be used, the solid component contained in the ammonium nitrate-containing liquid, the type of solvent other than water, It is appropriately set in consideration of the ratio and the like.
Moreover, the shape and particle size of the ammonium nitrate granular material to be manufactured can be controlled mainly by spray drying conditions. It is preferable to adjust the spray droplet size and the drying conditions so that the ammonium nitrate granular material has a substantially spherical particle having a suitable shape and a suitable particle size range.
なお、乾燥温度は、噴霧乾燥機における、熱風温度と、チャンバー温度のいずれか、または両方を調節する等の方法で管理することができるが、これらのそれぞれの温度には差が生じることがあり、通常チャンバー温度の方が低く、熱風温度や風量を調整することで全体の温度をコントロールする。具体的には、通常、熱風温度を８０℃〜２００℃の範囲程度、チャンバー内温度が、５０℃〜１５０℃程度である。 The drying temperature can be controlled by adjusting either the hot air temperature and / or the chamber temperature in the spray dryer, but there may be differences between these temperatures. The chamber temperature is usually lower, and the overall temperature is controlled by adjusting the hot air temperature and air volume. Specifically, the hot air temperature is usually in the range of 80 ° C. to 200 ° C., and the temperature in the chamber is about 50 ° C. to 150 ° C.
［粒状物の形状］
本発明にかかるガス発生剤用硝酸アンモニウム粒状物は、噴霧乾燥の条件を調整することで略球状粒子とすることが好ましい。粒状物の形状は、光学顕微鏡や電子顕微鏡で外観を観察すればよい。略球状粒子となる製造を行うことで、硝酸アンモニウムとポリマーや適宜添加した相安定化剤とが十分に混和した状態で乾燥されているものとなるため、防湿性や、相安定性といった目的とする特性をより達成することができるものとなる。
[Granular shape]
The ammonium nitrate granular material for a gas generating agent according to the present invention is preferably formed into a substantially spherical particle by adjusting the spray drying conditions. What is necessary is just to observe an external appearance with the optical microscope and the electron microscope about the shape of a granular material. By producing substantially spherical particles, the ammonium nitrate and the polymer and the phase stabilizer added as appropriate are dried in a sufficiently mixed state, so that the purpose is moisture proof and phase stability. The characteristics can be achieved more.
当該略球状粒子の粒子径は、光学顕微鏡や電子顕微鏡で観察したときに、そのモード粒子径が１〜２００μｍ、好ましくは５〜１００μｍである。モード粒子径は、観察像の硝酸アンモニウム粒状物を画像解析することにより測定する。モード粒子径がこれより大きいとき、噴霧乾燥時の溶液の拡散条件や、溶液自体の粘度が適切ではなく大きい粒径で乾燥されていると考えられる。このような条件で得られる粒状物は、乾燥過程が適しているとはいえないことから、目的とする防湿性や相安定性を発揮しないことがある。モード粒子径がこれより小さいときは、噴霧乾燥時の溶液中固形分濃度が少ないことや、ポリマー量が不足していることが考えられ、生産効率が低かったり、防湿性や相安定性といった特性が十分でなかったりすることがある。 When the particle diameter of the substantially spherical particles is observed with an optical microscope or an electron microscope, the mode particle diameter is 1 to 200 μm, preferably 5 to 100 μm. The mode particle diameter is measured by image analysis of ammonium nitrate granular material in the observed image. When the mode particle size is larger than this, the solution diffusion conditions during spray drying and the viscosity of the solution itself are not appropriate, and it is considered that the solution is dried with a large particle size. Since the granular material obtained under such conditions is not suitable for the drying process, it may not exhibit the desired moisture resistance and phase stability. If the mode particle size is smaller than this, the solids concentration in the solution during spray drying may be low, or the amount of polymer may be insufficient, resulting in low production efficiency or characteristics such as moisture resistance and phase stability. May not be enough.
本発明のガス発生剤用硝酸アンモニウム粒状物は、常温から１００℃以下の温度範囲で相転移点を有さないことが好ましく、より好ましくは１２０℃以下の温度で相転移点を示さないことであり、特に１５０℃以下の温度範囲で相転移点を有さないことが好ましい。また、本発明の硝酸アンモニウム粒状物は、−５０℃〜２５℃の低温領域においても相転移点を有さないことが好ましい。すなわち、−５０℃以上１００℃以下の温度範囲で相転移点を示さないことが好ましく、より好ましくは−５０℃以上１２０℃以下の温度範囲で相転移点を示さないことであり、特に好ましくは−５０℃以上１５０℃以下の温度範囲で相転移点を示さない。
ここで、「相転移点を有さない」とは、示差走査熱量測定（ＤＳＣ）において吸熱ピークが観測されないことを意味する。ＤＳＣの測定条件は、実施例にて後述する。
The ammonium nitrate granular material for gas generating agent of the present invention preferably has no phase transition point in the temperature range from room temperature to 100 ° C., and more preferably does not exhibit a phase transition point at a temperature of 120 ° C. or less. In particular, it is preferable not to have a phase transition point in a temperature range of 150 ° C. or lower. Moreover, it is preferable that the ammonium nitrate granular material of this invention does not have a phase transition point also in a low temperature range of -50 degreeC-25 degreeC. That is, it is preferable not to show a phase transition point in a temperature range of −50 ° C. or higher and 100 ° C. or lower, more preferably not to show a phase transition point in a temperature range of −50 ° C. or higher and 120 ° C. or lower, particularly preferably. No phase transition point is shown in the temperature range of −50 ° C. or higher and 150 ° C. or lower.
Here, “having no phase transition point” means that no endothermic peak is observed in differential scanning calorimetry (DSC). DSC measurement conditions will be described later in Examples.
また、本発明のガス発生剤用硝酸アンモニウム粒状物は、極めて低い結晶化度の物性を示す。本発明の硝酸アンモニウム粒状物は、粉末Ｘ線回折の測定により明確な回折ピークを示すものの、そのピーク強度が極めて弱く示されることでその低結晶化度が認められる。すなわち、硝酸アンモニウム試薬や水溶性高分子を含まない硝酸アンモニウムの噴霧乾燥により得られる硝酸アンモニウム粒状物の粉末Ｘ線回折測定の回折ピーク強度と比較して、本発明の硝酸アンモニウム粒状物の同条件でのＸ線回折ピーク強度は１／１０〜１／１００強度の回折像を示す。この原因は明らかではないが、本発明の硝酸アンモニウム粒状物と他の硝酸アンモニウムとを明確に区別される物性である。 Moreover, the ammonium nitrate granular material for gas generating agents of this invention shows the physical property of a very low crystallinity degree. The ammonium nitrate granular material of the present invention shows a clear diffraction peak by powder X-ray diffraction measurement, but its low crystallinity is recognized by showing its peak intensity very weakly. That is, compared with the diffraction peak intensity of powder X-ray diffraction measurement of ammonium nitrate granular material obtained by spray drying of ammonium nitrate not containing ammonium nitrate reagent or water-soluble polymer, X-rays under the same conditions of the ammonium nitrate granular material of the present invention The diffraction peak intensity shows a diffraction image of 1/10 to 1/100 intensity. The cause of this is not clear, but it is a physical property that clearly distinguishes the ammonium nitrate granular material of the present invention from other ammonium nitrates.
本発明の硝酸アンモニウム粒状物は、エアバッグ等に使用されるガス発生剤の酸化剤として好適に用いられる。このような用途では、通常、ペレットの形態で使用される。 The ammonium nitrate granular material of this invention is used suitably as an oxidizing agent of the gas generating agent used for an airbag etc. In such applications, it is usually used in the form of pellets.
［ペレット］
本発明によるガス発生剤用硝酸アンモニウム粒状物を用いて、ガス発生剤ペレットを作成することで、強度が高く、エアバッグ用などの使用環境下でのひび割れの発生が少ないガス発生剤とすることができる。ペレット化を行う場合、本発明にかかるガス発生剤用硝酸アンモニウム粒状物を酸化剤の一つとして用いて、さらに燃料、その他の酸化剤、バインダー、燃焼促進剤、圧力指数調整剤、添加剤等を混合し、押出成型、圧縮成型する等、公知の方法でペレット化することができる。ガス発生剤用原料の組成は、本発明にかかる硝酸アンモニウム粒状物中にも、燃料となり得るポリマーやその他添加剤も含むため、その成分比に応じて調整されるが、ガス発生剤組成物全体における、硝酸アンモニウム自体の濃度として、４０〜９０重量％程度である。
[pellet]
By using the ammonium nitrate granular material for gas generating agent according to the present invention to produce a gas generating agent pellet, it is possible to obtain a gas generating agent having high strength and less occurrence of cracks in use environments such as for airbags. it can. When pelletizing, the ammonium nitrate granular material for gas generating agent according to the present invention is used as one of the oxidizing agents, and further, fuel, other oxidizing agents, binders, combustion accelerators, pressure index adjusting agents, additives, etc. It can be pelletized by a known method such as mixing, extrusion molding or compression molding. The composition of the raw material for the gas generating agent includes the polymer and other additives that can be a fuel in the ammonium nitrate granular material according to the present invention, and is adjusted according to the component ratio. The concentration of ammonium nitrate itself is about 40 to 90% by weight.
以下、実施例により本発明を更に詳細に説明するが、本発明は、その要旨を変更しない限り以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is changed.
［硝酸アンモニウム］
硝酸アンモニウム（「ＡＮ」）は和光純薬工業株式会社製、特級試薬を用いた。
[Ammonium nitrate]
For ammonium nitrate (“AN”), a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. was used.
［相安定化剤］
相安定化剤として硝酸カリウム（「ＫＮ」）を用いた。この「ＫＮ」は和光純薬工業株式会社製、特級試薬を用いた。
[Phase stabilizer]
Potassium nitrate (“KN”) was used as a phase stabilizer. For this “KN”, a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. was used.
また、相安定化剤として、過塩素酸カリウム（「ＫＰ」）を用いた。この「ＫＰ」は和光純薬工業株式会社製、特級試薬を用いた。 In addition, potassium perchlorate (“KP”) was used as a phase stabilizer. For this “KP”, a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. was used.
［水溶性ポリマー／水分散性ポリマー］
水溶性ポリマーとして、ポリビニルアルコール（重合度４００）（「ＰＶＡ−（Ａ）」）、ポリビニルアルコール(重合度２０００)（「ＰＶＡ−（Ｂ）」）、カルボキシメチルセルロースナトリウム（「ＣＭＣＮ」）、カルボキシメチルセルロースアンモニウム（「ＣＭＣＡ」）を用いた。「ＰＶＡ−（Ａ）」、「ＰＶＡ−（Ｂ）」、「ＣＭＣＮ」、「ＣＭＣＡ」は和光純薬工業株式業株式会社製のものを用いた。
[Water-soluble polymer / water-dispersible polymer]
As a water-soluble polymer, polyvinyl alcohol (degree of polymerization 400) (“PVA- (A)”), polyvinyl alcohol (degree of polymerization 2000) (“PVA- (B)”), sodium carboxymethylcellulose (“CMCN”), carboxymethylcellulose Ammonium (“CMCA”) was used. “PVA- (A)”, “PVA- (B)”, “CMCN”, and “CMCA” manufactured by Wako Pure Chemical Industries, Ltd. were used.
また、水溶性ポリマーとして、さらに、ポリアクリル酸アンモニウム溶液（「ＰＡＡ」）を用いた。ＰＡＡは、和光純薬株式会社製の水溶液の状態のものであり、溶液としての粘度７０〜１１０ｍＰａ・ｓ、溶液中の蒸発残分４４質量％のものを用いた。 Further, an ammonium polyacrylate solution (“PAA”) was further used as the water-soluble polymer. PAA is in the form of an aqueous solution manufactured by Wako Pure Chemical Industries, Ltd., and a solution having a viscosity of 70 to 110 mPa · s as a solution and an evaporation residue of 44% by mass in the solution was used.
水分散性ポリマーとして、変性スチレン−ブタジエンラテックス（以下、「Ｌａｔｅｘ」。）である旭化成ケミカルズ株式会社製のＳＢラテックス“Ｌ−１６３８”を用いた。 As the water dispersible polymer, SB latex “L-1638” manufactured by Asahi Kasei Chemicals Corporation, which is a modified styrene-butadiene latex (hereinafter, “Latex”), was used.
（実施例１〜１２、比較例１）
前記した固形物を用いて、下記する溶解操作を行い、表１に示す組成で、実施例１〜１２および比較例１の硝酸アンモニウム含有液を調整した。当該硝酸アンモニウムを後述する噴霧乾燥することで、硝酸アンモニウム粒状物を得た。
(Examples 1 to 12, Comparative Example 1)
Using the above-described solid matter, the following dissolution operation was performed, and the ammonium nitrate-containing liquids of Examples 1 to 12 and Comparative Example 1 were prepared with the compositions shown in Table 1. The ammonium nitrate granular material was obtained by spray-drying the ammonium nitrate described later.
［試料の溶解］
前記ＡＮ、ＫＮ、ポリマーを表１に示す組成で、純水（ミリポア社の超純水製造装置：“ＭｉｌｌｉＱ”を用いて得た。）に溶解させて溶液を調整した。
[Dissolution of sample]
The AN, KN, and polymer were dissolved in pure water (obtained using MilliQ ultrapure water production apparatus: MilliQ) with the composition shown in Table 1 to prepare a solution.
（実施例１３〜１６）
前記した固形物を用いて、上述した比較例１および実施例１〜１２と同様の溶解操作を行い、表２に示す組成で、実施例１３〜１６の硝酸アンモニウム含有液を調整した。当該硝酸アンモニウムを後述する噴霧乾燥することで、硝酸アンモニウム粒状物を得た。
(Examples 13 to 16)
Using the solids described above, the same dissolution operation as in Comparative Example 1 and Examples 1 to 12 was performed, and the ammonium nitrate-containing liquids of Examples 13 to 16 were prepared with the compositions shown in Table 2. The ammonium nitrate granular material was obtained by spray-drying the ammonium nitrate described later.
［噴霧乾燥］
ディスク式スプレードライヤ（図１に概要図を示す。）を用いて調製した溶液を噴霧乾燥させた。装置および運転の主な条件を下記に示す。
・噴霧方式：ディスクアトマイザーφ５０（並流）
・チャンバー容量（図１中Ｄｒｙｉｎｇ Ｃｈａｍｂｅｒ部分の上部円柱部分の容量）：φ１１００ｍｍ，高さ６５０ｍｍ
・熱風温度：１６０−１７０℃（チャンバー内温度：９０−１００℃）
・ディスク回転数：１８０００あるいは２４０００ｒｐｍ
・フィード量：２．４−３．０ｋｇ／時（チャンバー内温度を９０から１００℃で維持するために適宜調製した。）
[Spray drying]
The solution prepared using a disk-type spray dryer (a schematic diagram is shown in FIG. 1) was spray-dried. The main conditions of equipment and operation are shown below.
・ Spraying method: Disc atomizer φ50 (parallel flow)
・ Chamber capacity (capacity of upper cylindrical part of Drying Chamber part in FIG. 1): φ1100 mm, height 650 mm
-Hot air temperature: 160-170 ° C (chamber temperature: 90-100 ° C)
-Disk rotation speed: 18000 or 24000 rpm
Feed amount: 2.4-3.0 kg / hour (adjusted appropriately to maintain the temperature in the chamber at 90 to 100 ° C.)
表３に硝酸アンモニウム粒状物の収率および含水率を示す。なお、表３の収率は図１の「Ｄｒｙｉｎｇ Ｃｈａｍｂｅｒ」下部から得られる粉体の収率である。また、図１中の「Ｃｙｃｌｏｎｅ ｓｅｐａｒａｔｏｒ」からも粒状物を得ることができ、これを合わせると、収率は約６０〜９０％程度となる。 Table 3 shows the yield and water content of ammonium nitrate granules. The yields in Table 3 are the yields of the powder obtained from the lower part of “Drying Chamber” in FIG. Moreover, a granular material can also be obtained from “Cyclone separator” in FIG. 1, and when combined, the yield is about 60 to 90%.
（比較例２、３）
下記する方法で、比較例２、３となる硝酸アンモニウム粒状物を得た。
［従来の硝酸アンモニウムおよびポリマー混合品］
本発明によらない硝酸アンモニウム試薬（和光純薬工業株式会社製、特級試薬）を比較例２として用いた。
また、硝酸アンモニウム、硝酸カリウム、カルボキシメチルセルロースアンモニウムを、それぞれ９０重量部：１０重量部：３重量部の割合で混合し、２０重量％水溶液としたものを、従来同様に恒温槽で１昼夜乾燥（蒸発乾固）して得た粒状物を比較例３として用いた。
(Comparative Examples 2 and 3)
The ammonium nitrate granular material used as the comparative examples 2 and 3 was obtained by the following method.
[Conventional ammonium nitrate and polymer mixture]
An ammonium nitrate reagent (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) not according to the present invention was used as Comparative Example 2.
Also, ammonium nitrate, potassium nitrate, and carboxymethyl cellulose ammonium were mixed at a ratio of 90 parts by weight: 10 parts by weight: 3 parts by weight, respectively, and a 20% by weight aqueous solution was dried in a constant temperature bath for a whole day (evaporation drying). The granular material obtained by solidification) was used as Comparative Example 3.
［硝酸アンモニウム粒状物の評価］
前記手法により得た、実施例１〜１２および比較例１〜３にかかる硝酸アンモニウム粒状物の評価方法は次の通りである。
[Evaluation of ammonium nitrate granules]
The evaluation method of the ammonium nitrate granular material concerning Examples 1-12 and Comparative Examples 1-3 obtained by the said method is as follows.
［表面観察］
噴霧乾燥後に得られる硝酸アンモニウム粒状物の外観をＳＥＭ（日本電子株式会社製「ＪＳＭ−６０６０型走査型顕微鏡」）およびＳＥＭ／ＥＤＸ（ＳＥＭ部分：ＦＥＩ社製「Ｑｕａｎｔａ ＦＥＧ−２００Ｆ」、ＥＤＸ部分：ＥＤＡＸ社製「ＸＬ−３０」)を用いて観察した。
[Surface observation]
The appearance of the ammonium nitrate granular material obtained after spray drying is SEM (“JSM-6060 scanning microscope” manufactured by JEOL Ltd.) and SEM / EDX (SEM part: “Quanta FEG-200F” manufactured by FEI, EDX part: EDAX). It was observed using “XL-30”).
噴霧乾燥により得られた本発明にかかる硝酸アンモニウム粒状物のＳＥＭ画像を図２、３に示す。図３は、図２に示したＳＥＭ画像を拡大した画像である。得られた硝酸アンモニウム粒状物は略球状であった。また、溶液中のポリマー濃度が高い試料は、粒径が大きくなる傾向があった。
ここで約５０μｍ以上の比較的大きな粒子は、粒子内部が中空様になっており、その内部にはより小径の粒子が充填されているが、その大粒子、内部の小粒子いずれも全体として、その外観は略球状である。
The SEM image of the ammonium nitrate granular material concerning this invention obtained by spray drying is shown to FIG. FIG. 3 is an enlarged image of the SEM image shown in FIG. The obtained ammonium nitrate granular material was substantially spherical. Further, the sample having a high polymer concentration in the solution tended to have a large particle size.
Here, the relatively large particles of about 50 μm or more have a hollow inside, and the inside is filled with smaller diameter particles, but both the large particles and the small particles inside as a whole, The appearance is substantially spherical.
撮影した粒子(任意の５００個)の粒径を計測して粒度分布を算出した結果を表４に示す。表４より、本実施例の噴霧乾燥法で得られた粒子のほとんどが１０〜５０μｍの範囲内に存在していることを確認することができる。 Table 4 shows the result of calculating the particle size distribution by measuring the particle size of the photographed particles (arbitrary 500 particles). From Table 4, it can be confirmed that most of the particles obtained by the spray drying method of the present example are in the range of 10 to 50 μm.
本発明によらない比較例２のＳＥＭ観察画像を図４に示す。また、比較例３のＳＥＭ観察画像を図５に示す。これらは、本発明の硝酸アンモニウム粒状物とは形状が明らかに異なるものであった。 The SEM observation image of the comparative example 2 which is not based on this invention is shown in FIG. Moreover, the SEM observation image of the comparative example 3 is shown in FIG. These were clearly different in shape from the ammonium nitrate granules of the present invention.
ＳＥＭ／ＥＤＸを用いて得られた硝酸アンモニウム粒状物表面の元素分析を行った。その結果を表５に示す。両者ともに固形物の化学構造から推察した理論値と近い元素分布を示していることから、ＡＮおよびＫＮとポリマーが一体化した粒子となっているものと考えられる。表５より、ポリマーが含まれていない比較例１（ＡＮ／ＫＮ）でも炭素が検出されたが、これは、台座に用いたカーボンテープの影響であると考えられ、他の試料でも同様に見かけ上、炭素が多く見積もられているものと考えられる。このことを勘案すれば、概ね理論値と近い値を示すことから、ＡＮ、ＫＮおよびポリマーが一体化した粒子であると考えられる。 The elemental analysis of the ammonium nitrate granular material surface obtained using SEM / EDX was performed. The results are shown in Table 5. Both of them show an element distribution close to the theoretical value inferred from the chemical structure of the solid substance, and thus it is considered that the particles are formed by integrating AN, KN, and polymer. From Table 5, carbon was also detected in Comparative Example 1 (AN / KN) containing no polymer, but this is considered to be due to the influence of the carbon tape used for the pedestal. In addition, it is thought that a lot of carbon is estimated. Considering this, since the value is almost the same as the theoretical value, it is considered to be a particle in which AN, KN and polymer are integrated.
［吸湿性の観察］
比較例１、実施例１（ＰＶＡ−（Ａ））、実施例３（ＰＶＡ−（Ａ））、実施例４（ＰＶＡ−（Ｂ））、実施例５（ＰＶＡ−（Ｂ））、実施例６（ＣＭＣＮ）、実施例７（ＣＭＣＮ）、実施例８（ＣＭＣＡ）、実施例９（ＣＭＣＡ）、実施例１０（Ｌａｔｅｘ）、実施例１１（Ｌａｔｅｘ）の溶液をスプレードライすることで得られた硝酸アンモニウム粒状物を９０℃の恒温槽内にて一昼夜放置し、試料を乾燥させた。同乾燥試料の吸湿性を確認するため、それぞれを湿度４０ＲＨ％に調製したデシケータ内に貯蔵し、貯蔵前後の重量変化から吸湿量を測定した。貯蔵温度は、３０℃とし、デシケータ内（底部）には、炭酸カリウム水溶液を配置して、湿度を４０ＲＨ％に保持した。
[Hygroscopic observation]
Comparative Example 1, Example 1 (PVA- (A)), Example 3 (PVA- (A)), Example 4 (PVA- (B)), Example 5 (PVA- (B)), Example 6 (CMCN), Example 7 (CMCN), Example 8 (CMCA), Example 9 (CMCA), Example 10 (Latex), and Example 11 (Latex) were obtained by spray drying. The ammonium nitrate granular material was left in a constant temperature bath at 90 ° C. for a whole day and night to dry the sample. In order to confirm the hygroscopicity of the dried sample, each was stored in a desiccator prepared at a humidity of 40 RH%, and the moisture absorption was measured from the change in weight before and after storage. The storage temperature was 30 ° C., and an aqueous potassium carbonate solution was placed in the desiccator (bottom) to maintain the humidity at 40 RH%.
各試料の吸湿量の時間変化を図６に示す。この図から、本発明にかかる硝酸アンモニウム粒状物は、比較例１のポリマー無添加の試料よりも防湿性が向上していることが分かる。特に、実施例１０、１１にかかるＬａｔｅｘを用いて作成した硝酸アンモニウム粒状物は、吸湿量が、ポリマー無添加の試料の約１／１０程度であり、防湿性が高いことがわかる。一方で、ＰＶＡ系ポリマーを用いて得られた粒状物は、従来の硝酸アンモニウム単独のものよりも吸湿率が改善されているが、他のポリマーを用いた粒状物よりもやや吸湿量が大きく、防湿性が低い。 The time change of the moisture absorption amount of each sample is shown in FIG. From this figure, it can be seen that the ammonium nitrate granular material according to the present invention has improved moisture resistance compared to the polymer-free sample of Comparative Example 1. In particular, the ammonium nitrate granular material prepared using Latex according to Examples 10 and 11 has a moisture absorption amount of about 1/10 of that of the sample to which no polymer was added, indicating that the moisture resistance is high. On the other hand, although the granular material obtained by using the PVA-based polymer has an improved moisture absorption rate compared with the conventional ammonium nitrate alone, the moisture absorption is slightly larger than that of the granular material using other polymers. The nature is low.
［固相間相転移の観察］
相安定性を調べるために固相間相転移の有無を調べた。ブランク試料として比較例２の硝酸アンモニウムを用いた。また、本発明にかかる硝酸アンモニウム粒状物を実施例１（ＰＶＡ−（Ａ））、実施例４（ＰＶＡ−（Ｂ））、実施例６（ＣＭＣＮ）、実施例８（ＣＭＣＡ）、実施例１０（Ｌａｔｅｘ）、実施例１２（ＣＭＣＡ）より得られたものを用いた。
[Observation of phase transition between solid phases]
In order to investigate the phase stability, the presence or absence of a phase transition between solid phases was examined. The ammonium nitrate of Comparative Example 2 was used as a blank sample. Moreover, the ammonium nitrate granular material concerning this invention is Example 1 (PVA- (A)), Example 4 (PVA- (B)), Example 6 (CMCN), Example 8 (CMCA), Example 10 ( Latex), obtained from Example 12 (CMCA).
［固相間相転移の測定条件］
ＤＳＣを用いて、下記測定条件における熱的挙動を観察し、吸熱ピークの有無から固相間相転移の有無を確認することで相安定性を評価した。
熱分析装置：セイコーインスツル株式会社製ＤＳＣ（ＤＳＣ２００）
昇温速度：２Ｋ／ｍｉｎ（空気雰囲気）
試料容器：セイコーインスツル株式会社製ステンレス製密閉型反応容器（容量１５μＬ）
[Measurement conditions for phase transition between solid phases]
Using DSC, the thermal behavior under the following measurement conditions was observed, and the phase stability was evaluated by confirming the presence or absence of a phase transition between solid phases from the presence or absence of an endothermic peak.
Thermal analyzer: DSC (DSC200) manufactured by Seiko Instruments Inc.
Temperature increase rate: 2K / min (air atmosphere)
Sample container: Seiko Instruments Inc. stainless steel sealed reaction container (capacity 15 μL)
ＤＳＣ測定結果を図７に示す。ＡＮ単独である比較例２では、３５℃、８０℃、１２５℃にそれぞれ固相間相転移に由来する吸熱ピークが観察された。一方、本発明にかかる硝酸アンモニウム粒状物である実施例１、実施例４、実施例６、実施例８、実施例１０、実施例１２では、いずれも１００℃以下に吸熱ピークは観察されなかった。
さらに、実施例８（ＣＭＣＡ）の場合では、ＫＮ添加のみでは抑制することができないとされる１２５℃の固相間相転移由来のピークも観察されなかった。また、ＫＮ無添加の実施例１２のＤＳＣ測定を行ったところ、１２５℃付近の相転移は確認されたが、ＡＮ単独で観察されるその他の相転移は観察されなかった。このように、相安定化剤を加えなくとも、相転移を抑制することもできるが、相安定化剤を加えることでより固相間相転移を抑制することができる。
The DSC measurement result is shown in FIG. In Comparative Example 2 which is AN alone, endothermic peaks derived from interphase transitions were observed at 35 ° C., 80 ° C. and 125 ° C., respectively. On the other hand, in Example 1, Example 4, Example 6, Example 8, Example 10, Example 12, which are ammonium nitrate granular materials according to the present invention, no endothermic peak was observed below 100 ° C.
Furthermore, in the case of Example 8 (CMCA), a peak derived from a phase transition between 125 ° C. at a solid phase, which cannot be suppressed only by adding KN, was not observed. Moreover, when DSC measurement of Example 12 without addition of KN was performed, a phase transition around 125 ° C. was confirmed, but other phase transitions observed with AN alone were not observed. Thus, although the phase transition can be suppressed without adding a phase stabilizer, the phase transition between solid phases can be further suppressed by adding a phase stabilizer.
また、図８に、比較例１、比較例２、比較例３および実施例８のＤＳＣ測定結果を示す。ＡＮ単独である比較例２は前述したように、３５℃、８０℃、１２５℃にそれぞれ固相間相転移に由来する吸熱ピークが観察された。ポリマーを用いない噴霧乾燥により得られる硝酸アンモニウム粒状物である比較例１では、１００℃以下の吸熱ピークは観察されないが、前述のとおりこの粒状物は吸湿性が高い。また、本発明によらない従来の乾燥方法によるＡＮ、ＫＮ、ポリマーの混合物から得られる粒状物である比較例３は、相安定性の改善効果が十分ではない。実施例８に代表されるように本発明により、従来の相安定性より優れた相安定性を達成することができることがわかる。 FIG. 8 shows DSC measurement results of Comparative Example 1, Comparative Example 2, Comparative Example 3, and Example 8. In Comparative Example 2, which is an AN alone, as described above, endothermic peaks derived from interphase transitions were observed at 35 ° C., 80 ° C., and 125 ° C., respectively. In Comparative Example 1, which is an ammonium nitrate granular material obtained by spray drying without using a polymer, no endothermic peak at 100 ° C. or lower is observed, but as described above, this granular material has high hygroscopicity. Further, Comparative Example 3 which is a granular material obtained from a mixture of AN, KN and polymer by a conventional drying method not according to the present invention does not have a sufficient effect of improving the phase stability. As represented by Example 8, it can be seen that the present invention can achieve phase stability superior to conventional phase stability.
また、図９に、実施例１３、実施例１４のＤＳＣ測定結果を示す。さらに、図１０に、実施例１５、実施例１６のＤＳＣ測定結果を示す。水溶性ポリマーとして、ポリアクリル酸アンモニウムを用いた実施例１３および実施例１４は、１００℃以下に吸熱ピークは観察されず、相安定化が達成されていた。また、相安定化剤として、過塩素酸カリウムを用いた実施例１５および実施例１６は、８０℃における固相間相転移に起因する吸熱ピークがなく、固相間相転移が抑制された。 FIG. 9 shows the DSC measurement results of Example 13 and Example 14. Further, FIG. 10 shows DSC measurement results of Example 15 and Example 16. In Examples 13 and 14 using ammonium polyacrylate as the water-soluble polymer, no endothermic peak was observed at 100 ° C. or lower, and phase stabilization was achieved. Moreover, Example 15 and Example 16 which used potassium perchlorate as a phase stabilizer did not have the endothermic peak resulting from the phase transition between solid phases at 80 degreeC, and the phase transition between solid phases was suppressed.
本発明の製造方法によれば、防湿性、相安定性に優れており、取り扱い性が向上したガス発生剤用硝酸アンモニウム粒状物を得ることができる。このガス発生剤硝酸アンモニウム粒状物を用いたペレットを成型すると、その優れた防湿性、相安定性によって、従来のペレット以上の強度、および温度変化に伴う体積変化が少ないためひび割れが生じないことが期待できるため、車載用エアバッグ等に好適に使用することができる。 According to the production method of the present invention, it is possible to obtain an ammonium nitrate granular material for a gas generating agent which is excellent in moisture resistance and phase stability and has improved handleability. Molding pellets using this gas generant ammonium nitrate granule is expected to prevent cracking because of its excellent moisture-proofing and phase stability, and strength change over conventional pellets, and volume change due to temperature changes is small. Therefore, it can be suitably used for a vehicle-mounted airbag or the like.
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| JPH10130086A (en) * | 1996-10-23 | 1998-05-19 | Nippon Kayaku Co Ltd | Gas generating agent for air bag |
| JP2000086378A (en) * | 1998-07-13 | 2000-03-28 | Nof Corp | Gas generator composition, formed material of gas generator and production of the formed material |
| JP2002097095A (en) * | 2000-09-22 | 2002-04-02 | Nof Corp | Gas generating agent |
| US6431597B1 (en) * | 2000-05-26 | 2002-08-13 | Trw Inc. | Reduced smoke gas generant with improved mechanical stability |
| JP2011516395A (en) * | 2008-04-10 | 2011-05-26 | オートリブ エーエスピー，インコーポレイティド | High performance gas generating composition |
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| JPH10130086A (en) * | 1996-10-23 | 1998-05-19 | Nippon Kayaku Co Ltd | Gas generating agent for air bag |
| JP2000086378A (en) * | 1998-07-13 | 2000-03-28 | Nof Corp | Gas generator composition, formed material of gas generator and production of the formed material |
| US6431597B1 (en) * | 2000-05-26 | 2002-08-13 | Trw Inc. | Reduced smoke gas generant with improved mechanical stability |
| JP2002097095A (en) * | 2000-09-22 | 2002-04-02 | Nof Corp | Gas generating agent |
| JP2011516395A (en) * | 2008-04-10 | 2011-05-26 | オートリブ エーエスピー，インコーポレイティド | High performance gas generating composition |
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