JP5711651B2 - Flame retardant composition - Google Patents
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- JP5711651B2 JP5711651B2 JP2011269724A JP2011269724A JP5711651B2 JP 5711651 B2 JP5711651 B2 JP 5711651B2 JP 2011269724 A JP2011269724 A JP 2011269724A JP 2011269724 A JP2011269724 A JP 2011269724A JP 5711651 B2 JP5711651 B2 JP 5711651B2
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- 239000000203 mixture Substances 0.000 title claims description 50
- 239000003063 flame retardant Substances 0.000 title claims description 38
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 37
- 239000003795 chemical substances by application Substances 0.000 claims description 38
- NDEMNVPZDAFUKN-UHFFFAOYSA-N guanidine;nitric acid Chemical compound NC(N)=N.O[N+]([O-])=O.O[N+]([O-])=O NDEMNVPZDAFUKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920001187 thermosetting polymer Polymers 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- 238000002485 combustion reaction Methods 0.000 description 16
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 16
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- -1 polyoxytetramethylene Polymers 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000249914 Hemigraphis reptans Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- UHCGLDSRFKGERO-UHFFFAOYSA-N strontium peroxide Chemical compound [Sr+2].[O-][O-] UHCGLDSRFKGERO-UHFFFAOYSA-N 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Description
本発明は、信号筒、発炎筒等に使用する発炎剤組成物に関する。特に、組成物中に過塩素酸塩類、塩化ゴム等の塩素原子を含む物質を含有しないことを特徴とし、製造作業及び使用時においてより安全に取り扱うことができると共に、環境面に配慮した発炎剤組成物に関する。 The present invention relates to a flame retardant composition used for a signal cylinder, a flame cylinder and the like. In particular, the composition is characterized by not containing substances containing chlorine atoms, such as perchlorates and chlorinated rubber, and can be handled more safely during manufacturing operations and use, and it is environmentally friendly. The agent composition.
発炎筒のように赤色の発色炎を発する組成物においては、酸素供給剤として過塩素酸カリウム、過塩素酸アンモニウム等の過塩素酸塩類を含有すること、又は可燃剤として塩化ゴム等の塩素原子を含む物質を含有することが知られている（特許文献１）。特許文献１においては、組成物は、発色剤として硝酸ストロンチウム等のストロンチウムを含む物質と塩素を含む物質を含有し、これらが燃焼した際に塩化ストロンチウムが生成し赤色炎を発するとされている。 In a composition that emits a red color flame like a flame cylinder, it contains perchlorates such as potassium perchlorate and ammonium perchlorate as an oxygen supply agent, or contains chlorine atoms such as chlorinated rubber as a combustible agent. It is known to contain a contained substance (Patent Document 1). In Patent Document 1, the composition contains a substance containing strontium such as strontium nitrate as a color former and a substance containing chlorine, and when these are burned, strontium chloride is generated and a red flame is emitted.
しかしながら、過塩素酸塩類は、一般的に熱、衝撃、摩擦等による感度が高く、それらを酸素供給剤として使用した場合、製造作業及び使用時における安全性の確保が課題となる。 However, perchlorates generally have high sensitivity due to heat, impact, friction, and the like, and when they are used as an oxygen supply agent, securing safety in manufacturing operations and use becomes a problem.
また、過塩素酸塩類は、燃焼時に塩素や塩化水素を発生する。塩素及び塩化水素は、人体や動植物に害を及ぼす物質として、大気汚染防止法において有害物質に指定されている。また、これらが空中や地中の水と反応すると、塩酸、過塩素酸等の酸が生じる。塩酸は、人体に対する影響は勿論、水素イオン濃度に大きく影響を及ぼす物質であり、水質汚濁の原因となる。また、過塩素酸類は、人体への毒性が懸念される物質であり、水道水質基準等の水質管理目標設定項目への適応について検討がなされている。 In addition, perchlorates generate chlorine and hydrogen chloride during combustion. Chlorine and hydrogen chloride are designated as hazardous substances in the Air Pollution Control Act as substances that cause harm to human bodies and animals and plants. Moreover, when these react with water in the air or in the ground, acids such as hydrochloric acid and perchloric acid are generated. Hydrochloric acid is a substance that not only affects the human body but also greatly affects the hydrogen ion concentration and causes water pollution. Perchloric acids are substances that are toxic to the human body, and are being studied for adaptation to water quality management target setting items such as tap water quality standards.
信号筒、発炎筒等は、緊急時に使用されるため、一度に大量の本数を燃焼させる頻度は少ないと思われるが、消費期限が切れた製品については、一度に大量の製品を焼却処分するため、上記のような人体への影響、環境問題等の課題が発生する。 Since signal tubes, flame tubes, etc. are used in an emergency, it seems that the frequency of burning a large number at a time is low, but for products whose expiration date has expired, a large amount of products are incinerated at a time, Issues such as the above-mentioned effects on the human body and environmental problems occur.
特許文献２には、特定の粒径を有する発色剤を用いることによって、過塩素酸塩類の配合割合の低減を図る方法が開示されているが、過塩素酸塩類が配合されている限り、上記課題の根本的な解決には至っていない。 Patent Document 2 discloses a method for reducing the blending ratio of perchlorates by using a color former having a specific particle size, but as long as perchlorates are blended, The fundamental problem has not been solved.
そこで本願出願人は、発色剤として硝酸ストロンチウムに加えて炭酸リチウムを使用し、発熱剤として金属粉を使用することにより、過塩素酸塩類を含有しなくても良好な発色及び光度が得られる発炎剤組成物を提案した。しかしながら、上記技術においても、炭酸リチウムの配合割合が多いと、燃焼中断を起こす等、燃焼状態が不安定になり、金属粉の配合割合が多いと、黄色や白色の発光の影響により赤色の発光が薄くなるという不具合が生じる可能性を有していた。また、多量の金属塩及び金属粉を使用しているため、燃焼後の残渣が比較的多くなる等の課題が残っていた。 Therefore, the applicant of the present invention uses lithium carbonate in addition to strontium nitrate as a color former, and uses metal powder as a heat generating agent, so that it is possible to obtain good color development and luminous intensity without containing perchlorates. A flame retardant composition was proposed. However, even in the above technique, if the mixing ratio of lithium carbonate is large, the combustion state becomes unstable, such as causing combustion interruption, and if the mixing ratio of the metal powder is large, red light emission due to the influence of yellow or white light emission. There was a possibility that the problem of thinning would occur. In addition, since a large amount of metal salt and metal powder are used, problems such as a relatively large residue after combustion remain.
本発明の目的は、過塩素酸塩類、塩化ゴム等の塩素原子を含む物質を含有せずに、従来の発炎剤組成物と同等の発色及び光度が得られ、製造作業及び使用時における安全性に優れると共に、燃焼残渣が少なく、安定した燃焼状態を維持することが可能な発炎剤組成物を提供することにある。 The object of the present invention is to produce a color and luminous intensity equivalent to those of conventional flame retardant compositions without containing substances containing chlorine atoms, such as perchlorates and chlorinated rubber, and are safe in manufacturing operations and use. An object of the present invention is to provide a flame retardant composition that is excellent in properties and has a small amount of combustion residue and can maintain a stable combustion state.
本発明者らは、環境への貢献という観点から、過塩素酸塩類等の塩素を含む物質を含有しない発炎剤組成物について鋭意検討を重ねた結果、可燃剤として硝酸グアニジンを使用することにより、上記課題を解決し得ることを見出し、本発明を完成するに至った。 From the viewpoint of contribution to the environment, the present inventors have conducted extensive studies on flame retardant compositions containing no chlorine-containing substances such as perchlorates, and as a result, by using guanidine nitrate as a combustible agent. The present inventors have found that the above problems can be solved, and have completed the present invention.
即ち、本発明の要旨は、
（１）可燃剤、発熱剤及び発色剤からなる発炎剤組成物において、可燃剤として硝酸グアニジンを含有し、且つ組成物中に塩素原子を有する物質を含有しないことを特徴とする発炎剤組成物、
（２）硝酸グアニジンの含有量が５〜３０重量％である、（１）に記載の発炎剤組成物、
（３）硝酸グアニジンの平均粒径が２０〜２００μｍである、（１）又は（２）に記載の発炎剤組成物、
（４）可燃剤として、さらに熱硬化性樹脂及びポリエーテルを含有する、（１）乃至（３）のいずれかに記載の発炎剤組成物、
（５）発熱剤の含有量が５〜２０重量％である、（１）乃至（４）のいずれかに記載の発炎剤組成物、
（６）発熱剤が平均粒径２０〜２００μｍのマグネシウム粉である、（１）乃至（５）のいずれかに記載の発炎剤組成物、
に存する。
That is, the gist of the present invention is as follows.
(1) A flame retardant composition comprising a flammable agent, a heat generating agent and a color former, wherein the flame retardant contains guanidine nitrate as a flammable agent and does not contain a substance having a chlorine atom in the composition. Composition,
(2) The flame retardant composition according to (1), wherein the content of guanidine nitrate is 5 to 30% by weight,
(3) The flame retardant composition according to (1) or (2), wherein the average particle diameter of guanidine nitrate is 20 to 200 μm,
(4) The flame retardant composition according to any one of (1) to (3), which further contains a thermosetting resin and a polyether as a combustible agent,
(5) The flame retardant composition according to any one of (1) to (4), wherein the content of the exothermic agent is 5 to 20% by weight,
(6) The flame retardant composition according to any one of (1) to (5), wherein the exothermic agent is magnesium powder having an average particle size of 20 to 200 μm,
Exist.
本発明により、発炎剤組成物を燃焼させ、赤色の発光を供する際に、発色及び光度を維持しながらも、塩素、塩化水素等の環境に悪影響を与える物質の排出を抑制することが可能となる。加えて、燃焼残渣が少なく、安定した燃焼状態を維持することも可能となる。 According to the present invention, it is possible to suppress the discharge of substances that adversely affect the environment such as chlorine and hydrogen chloride while maintaining color development and luminous intensity when burning the flame retardant composition and providing red light emission It becomes. In addition, there are few combustion residues and it is also possible to maintain a stable combustion state.
以下、本発明の方法を詳細に説明する。
本発明は、環境に配慮した発炎剤組成物に関する。
本発明の発炎剤組成物は、可燃剤、発熱剤及び発色剤を配合して得られる。
本発明においては、可燃剤として硝酸グアニジンが使用される。
Hereinafter, the method of the present invention will be described in detail.
The present invention relates to an environment-friendly flame retardant composition.
The flame retardant composition of the present invention is obtained by blending a combustible agent, a heat generating agent and a color former.
In the present invention, guanidine nitrate is used as a combustible agent.
本発明において、可燃剤として使用される硝酸グアニジンの含有量は、組成物全体に対して５〜３０重量％であることが好ましく、１０〜２０重量％であることが更に好ましい。硝酸グアニジンの平均粒径は、２０〜２００μｍであることが好ましく、５０〜１００μｍであることが更に好ましい。 In the present invention, the content of guanidine nitrate used as a combustible agent is preferably 5 to 30% by weight, more preferably 10 to 20% by weight, based on the entire composition. The average particle size of guanidine nitrate is preferably 20 to 200 μm, and more preferably 50 to 100 μm.
本発明においては、硝酸グアニジンの他に、バインダーを兼ねた可燃剤として、周知のものを使用可能である。可燃剤兼バインダーとしては、熱硬化性樹脂及びポリエーテルを使用することが好ましい。熱硬化性樹脂とポリエーテルとを組み合わせて使用することにより、燃焼炎が大きくなり、視認性が向上する。
熱硬化性樹脂及びポリエーテルは、液体であるか又は流動性があり、加熱、乾燥又は硬化剤の添加により硬化するものであれば、いずれも使用可能である。使用し得る熱硬化性樹脂の具体例としては、不飽和ポリエステル樹脂、フェノール樹脂、エポキシ樹脂等が挙げられる。使用し得るポリエーテルの具体例としては、ポリエチレングリコール、ポリプロピレングリコール、ポリオキシテトラメチレングリコール、ポリエチレンオキシド等が挙げられる。
In the present invention, in addition to guanidine nitrate, a well-known combustor that also serves as a binder can be used. As the combustible and binder, it is preferable to use a thermosetting resin and a polyether. By using a combination of a thermosetting resin and a polyether, the combustion flame becomes large and the visibility is improved.
Any thermosetting resin and polyether can be used as long as they are liquid or fluid and can be cured by heating, drying, or addition of a curing agent. Specific examples of thermosetting resins that can be used include unsaturated polyester resins, phenol resins, and epoxy resins. Specific examples of the polyether that can be used include polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, and polyethylene oxide.
さらに追加の可燃剤兼バインダーとして、木粉、澱粉、植物油、鉱物油、パラフィン、ポリエチレン、ポリプロピレン等を使用することができる。 Further, wood powder, starch, vegetable oil, mineral oil, paraffin, polyethylene, polypropylene and the like can be used as an additional combustible and binder.
本発明の発炎剤組成物において、必要により用いられる可燃剤兼バインダーの含有量は、組成物全体に対して１０〜３０重量％であることが好ましく、１５〜２５重量％であることが更に好ましい。 In the flame retardant composition of the present invention, the content of the combustible and binder used as necessary is preferably 10 to 30% by weight, more preferably 15 to 25% by weight, based on the entire composition. preferable.
本発明において、発熱剤としては、マグネシウム粉、アルミニウム粉等の金属粉のように、火炎温度を上げることにより発光強度を強くする効果を有するものであれば、いずれも使用可能である。発熱剤の含有量は、組成物全体に対して５〜２０重量％であることが好ましく、８〜１５重量％であることが更に好ましい。本発明において、発熱剤としては、平均粒径が２０〜２００μｍ、特に５０〜１００μｍのマグネシウム粉を使用することが好ましい。 In the present invention, any exothermic agent may be used as long as it has an effect of increasing the emission intensity by raising the flame temperature, such as metal powder such as magnesium powder and aluminum powder. The content of the exothermic agent is preferably 5 to 20% by weight, more preferably 8 to 15% by weight, based on the entire composition. In the present invention, it is preferable to use magnesium powder having an average particle size of 20 to 200 μm, particularly 50 to 100 μm, as the heat generating agent.
本発明において、発色剤としては、硝酸ストロンチウム、炭酸ストロンチウム、過酸化ストロンチウム、炭酸リチウム、炭酸カルシウム等を単独で又は２種類以上を混合して使用することができる。硝酸ストロンチウムを用いることが特に好ましい。発色剤は酸素供給剤の役割も果たしているが、追加の酸素供給剤として周知の硝酸カリウム等の硝酸塩類や過酸化物を添加することもできる。 In the present invention, as the color former, strontium nitrate, strontium carbonate, strontium peroxide, lithium carbonate, calcium carbonate and the like can be used alone or in admixture of two or more. It is particularly preferred to use strontium nitrate. The color former also serves as an oxygen supply agent, but nitrates such as potassium nitrate and peroxides known as additional oxygen supply agents can also be added.
発色剤の含有量は、組成物全体に対して好ましくは４０〜７５重量％、特に好ましくは５０〜６５重量％である。発色剤の平均粒径は、１０〜２００μｍ、特に３０〜１００μｍのものが好ましく使用される。 The content of the color former is preferably 40 to 75% by weight, particularly preferably 50 to 65% by weight, based on the entire composition. The average particle diameter of the color former is preferably 10 to 200 μm, particularly preferably 30 to 100 μm.
本発明の発炎剤組成物は、高速ミキサー又はボールミルのような混合機で、硝酸グアニジン、発熱剤及び発色剤を攪拌、混合することにより得られる。可燃剤兼バインダーを含有する場合、ニーダーのような混練機で、上記混合物及び常温液状の又は加熱溶融状態の可燃剤兼バインダーを混合することにより得られる。得られた発炎剤組成物を所定の紙筒に充填し、周知の方法により発炎筒を製造する。 The flame retardant composition of the present invention can be obtained by stirring and mixing guanidine nitrate, a heat generating agent and a color former in a mixer such as a high speed mixer or a ball mill. In the case of containing the combustible agent / binder, it can be obtained by mixing the above mixture and the combustible agent / binder in a liquid state at a normal temperature or in a molten state with a kneader such as a kneader. The obtained flame retardant composition is filled into a predetermined paper tube, and a flame tube is manufactured by a well-known method.
本発明を、実施例を挙げてさらに詳細に説明するが、本発明はこれらの実施例のみによって限定されるものではない。以下の実施例において、％は重量％を示す。 The present invention will be described in more detail with reference to examples, but the present invention is not limited only to these examples. In the following examples,% indicates% by weight.
（実施例１）
可燃剤である硝酸グアニジン（平均粒径：５０μｍ）１５％、発熱剤であるマグネシウム粉（平均粒径：７０μｍ）８％、発色剤である硝酸ストロンチウム５７％をボールミルで混合し、これを、可燃剤兼バインダーであるポリエチレン（軟化点：１２４℃）２０％を１６０℃に加温したニーダーで溶融したものに添加、混練して流動状の発炎剤組成物を得た。得られた発炎剤組成物８０ｇを内径２０ｍｍの紙筒に充填し、自然放冷により硬化させて発炎筒を作製した。
Example 1
A flammable guanidine nitrate (average particle size: 50 μm) 15%, a heat generating agent magnesium powder (average particle size: 70 μm) 8%, and a color former, strontium nitrate 57%, are mixed with a ball mill. A fluid flame retardant composition was obtained by adding and kneading 20% polyethylene (softening point: 124 ° C.), which is a flame retardant and binder, to a melted kneader heated to 160 ° C. 80 g of the obtained flame retardant composition was filled in a paper cylinder having an inner diameter of 20 mm and cured by natural cooling to produce a flame cylinder.
（実施例２）
可燃剤である硝酸グアニジン（平均粒径：５０μｍ）１８％、発熱剤であるマグネシウム粉（平均粒径：７０μｍ）１０％、発色剤である硝酸ストロンチウム５５％をボールミルで混合し、これを、可燃剤兼バインダーであるエポキシ樹脂１０％及びポリプロピレングリコール７％に添加し、さらにエポキシ樹脂に対して外割で１％の脂肪族ポリアミンを添加し、ニーダーで混練して流動状の発炎剤組成物を得た。得られた発炎剤組成物８０ｇを内径２０ｍｍの紙筒に充填し、室温で静置することにより硬化させて発炎筒を作製した。
(Example 2)
A flammable guanidine nitrate (average particle size: 50 μm) 18%, a heat generating agent magnesium powder (average particle size: 70 μm) 10%, and a color former strontium nitrate 55% are mixed in a ball mill. Add to 10% of epoxy resin and 7% of polypropylene glycol, which is a flame retardant / binder, and add 1% of aliphatic polyamine as an external ratio to the epoxy resin, and knead with a kneader to create a fluid flame retardant composition Got. 80 g of the obtained flame retardant composition was filled into a paper cylinder having an inner diameter of 20 mm and cured by standing at room temperature to produce a flame cylinder.
（比較例１）
発熱剤であるマグネシウム粉（平均粒径：７０μｍ）１０％、発色剤である硝酸ストロンチウム６４％及び炭酸リチウム６％をボールミルで混合し、これを、可燃剤兼バインダーであるパラフィンワックス（軟化点：１０１℃）１２％及びポリエチレン（軟化点：１２４℃）８％を１６０℃に加温したニーダーで溶融したものに添加、混練して流動状の発炎剤組成物を得た。得られた発炎剤組成物８０ｇを内径２０ｍｍの紙筒に充填し、自然放冷により硬化させて発炎筒を作製した。
(Comparative Example 1)
Magnesium powder (average particle size: 70 μm) as a heat generating agent, 64% strontium nitrate as a color former and 6% lithium carbonate are mixed with a ball mill, and this is mixed with paraffin wax (softening point: softening point and binder). (101 ° C.) 12% and polyethylene (softening point: 124 ° C.) 8% were added to a melted kneader heated to 160 ° C. and kneaded to obtain a fluid flame retardant composition. 80 g of the obtained flame retardant composition was filled in a paper cylinder having an inner diameter of 20 mm and cured by natural cooling to produce a flame cylinder.
（比較例２）
発熱剤であるマグネシウム粉（平均粒径：７０μｍ）２５％、発色剤である硝酸ストロンチウム５５％及び炭酸リチウム３％をボールミルで混合し、これを、可燃剤兼バインダーであるエポキシ樹脂１０％及びポリプロピレングリコール７％に添加し、さらにエポキシ樹脂に対して外割で１％の脂肪族ポリアミンを添加し、ニーダーで混練して流動状の発炎剤組成物を得た。得られた発炎剤組成物８０ｇを内径２０ｍｍの紙筒に充填し、室温で静置することにより硬化させて発炎筒を作製した。
(Comparative Example 2)
Magnesium powder (average particle size: 70 μm) 25% as exothermic agent, 55% strontium nitrate as color former and 3% lithium carbonate are mixed with a ball mill, and this is mixed with 10% epoxy resin as combustible and binder and polypropylene. It was added to 7% glycol, and 1% of an aliphatic polyamine was added to the epoxy resin, and kneaded with a kneader to obtain a fluid flame retardant composition. 80 g of the obtained flame retardant composition was filled into a paper cylinder having an inner diameter of 20 mm and cured by standing at room temperature to produce a flame cylinder.
実施例１及び２並びに比較例１及び２の組成と、これらの発炎剤組成物及び発炎筒についてＪＩＳ−Ｄ５７１１「自動車用緊急保安炎筒」に規定されている方法により試験した結果とを表１に示す。 Tables 1 and 2 show the compositions of Examples 1 and 2 and Comparative Examples 1 and 2 and the results of testing these flame retardant compositions and flame retardants according to the method defined in JIS-D5711 “Emergency Safety Flame Shield for Automobiles”. Shown in
表１の結果から明らかなように、可燃剤として硝酸グアニジンを使用している実施例１及び２の発炎剤組成物は、ＪＩＳ規格を満足する性能を有しており、且つ、燃焼残渣が少なく、燃焼中断を起こすことがなかった。これに対し、可燃剤として硝酸グアニジンを未使用の比較例１の組成物は、燃焼残渣が比較的多く、燃焼中断を起こし、燃焼状態が不安定であった。また、発熱剤の量が多く、可燃剤として硝酸グアニジンを未使用の比較例２の組成物は、燃焼残渣が比較的多く、燃焼中断を起こし、光度は高いが、マグネシウム粉の燃焼色が強く、赤色発色が薄くなる傾向があった。 As is apparent from the results in Table 1, the flame retardant composition of Examples 1 and 2 using guanidine nitrate as a combustible has performance satisfying JIS standards, and the combustion residue is There were few, and there was no burning interruption. On the other hand, the composition of Comparative Example 1 in which guanidine nitrate was not used as a combustible agent had a relatively large amount of combustion residue, caused combustion interruption, and the combustion state was unstable. In addition, the composition of Comparative Example 2, which contains a large amount of exothermic agent and does not use guanidine nitrate as a combustible agent, has a relatively large amount of combustion residue, causes combustion interruption, and has high luminous intensity, but the combustion color of magnesium powder is strong. There was a tendency for the red color to become lighter.
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