JPS63230510A - Stabilized red phosphorus and production thereof - Google Patents
Stabilized red phosphorus and production thereofInfo
- Publication number
- JPS63230510A JPS63230510A JP6407887A JP6407887A JPS63230510A JP S63230510 A JPS63230510 A JP S63230510A JP 6407887 A JP6407887 A JP 6407887A JP 6407887 A JP6407887 A JP 6407887A JP S63230510 A JPS63230510 A JP S63230510A
- Authority
- JP
- Japan
- Prior art keywords
- red phosphorus
- zirconium
- particles
- cobalt
- salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000002245 particle Substances 0.000 claims abstract description 52
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 239000007900 aqueous suspension Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 238000000151 deposition Methods 0.000 claims abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 3
- 150000002823 nitrates Chemical class 0.000 claims abstract description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims abstract 2
- GNEMDYVJKXMKCS-UHFFFAOYSA-N cobalt zirconium Chemical compound [Co].[Zr] GNEMDYVJKXMKCS-UHFFFAOYSA-N 0.000 claims description 14
- 150000001868 cobalt Chemical class 0.000 claims description 13
- 150000003754 zirconium Chemical class 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 150000003840 hydrochlorides Chemical class 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 239000003518 caustics Substances 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- 238000003756 stirring Methods 0.000 abstract description 15
- 238000000576 coating method Methods 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 abstract description 9
- 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 abstract description 5
- 239000003063 flame retardant Substances 0.000 abstract description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 abstract description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 abstract description 4
- 229920003002 synthetic resin Polymers 0.000 abstract description 4
- 239000000057 synthetic resin Substances 0.000 abstract description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 abstract description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 abstract description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 150000003841 chloride salts Chemical class 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 abstract 1
- 235000017550 sodium carbonate Nutrition 0.000 abstract 1
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract 1
- 238000005979 thermal decomposition reaction Methods 0.000 abstract 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 29
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 15
- 239000000243 solution Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005137 deposition process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 2
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- 241000243321 Cnidaria Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017974 NH40H Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- NNSIWZRTNZEWMS-UHFFFAOYSA-N cobalt titanium Chemical class [Ti].[Co] NNSIWZRTNZEWMS-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- TUXJTJITXCHUEL-UHFFFAOYSA-N disperse red 11 Chemical compound C1=CC=C2C(=O)C3=C(N)C(OC)=CC(N)=C3C(=O)C2=C1 TUXJTJITXCHUEL-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 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
- 239000006228 supernatant Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- -1 zirconium ions Chemical class 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、赤リンの粒子表面にジルコニウム−コバルト
化合物の複合皮膜を被覆してなる安定化赤リン及びその
製造法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to stabilized red phosphorus in which the surface of red phosphorus particles is coated with a composite film of a zirconium-cobalt compound, and a method for producing the same.
本発明にかかる安定化赤リンは、特に合成樹脂の難燃剤
として有用であり、樹脂、塗料おるいは接着剤の分野に
利用することができる。The stabilized red phosphorus according to the present invention is particularly useful as a flame retardant for synthetic resins, and can be used in the fields of resins, paints, and adhesives.
〈従来の技術〉
赤リンが合成樹脂に対しすぐれた離燃効果を付与するこ
とは周知のことであり、実際にも難燃剤として使用され
ている。<Prior Art> It is well known that red phosphorus imparts an excellent flame retardant effect to synthetic resins, and is actually used as a flame retardant.
しかしながら、赤リンはそのま疼使用する場合、水分と
反応してホスフィンガスの光生を伴う加水分解反応を生
ぜしめるので、従来より赤リンを有機又は無機の材料に
より被覆して改質赤リンとして使用しており、数多くの
赤リン改質が提案されている。However, when red phosphorus is used as it is, it reacts with moisture and causes a hydrolysis reaction accompanied by photogeneration of phosphine gas. Many red phosphorus modifications have been proposed.
例えば、硫酸アルミニウムと炭酸水素ナトリウムを用い
て赤リン表面上に水酸化アルミニウムを沈積させる方法
［グメリン著「ハンドブラフ デル アノルガニシェン
ケミ１１８版（１９６４年）゛″ホスホラスＩＦ８部
、８３頁（Ｑｍｅｌｉｎ、ｒＨａｎｄｂｕｃｈｄｅｒ
ａｎｏｒｇａｎｉｓｃｈｅｎ ＣｈｅｍｉｅＪ
８ｔｈ Ｅｄｔｉｏｎ （１９６４）、ｖｏｌ Ｐ
ｈｏｓｐｈｏｒｕｓ、ＰａｒｔＳ ８．Ｐａｇｅ
８３）］が報告さレテイる。For example, a method of depositing aluminum hydroxide on the surface of red phosphorus using aluminum sulfate and sodium bicarbonate [Qmelin, rHandbuchder, 118th edition (1964), Phosphorus IF, Part 8, p.
anorganischen ChemieJ
8th Edition (1964), vol P
phosphorus, Part S 8. Page
83)] is reported.
しかしながら、この赤リンの改質方法は、赤リンの完全
な安定化のためには大組の水酸化アルミニウムを被覆し
なければならないため、赤リン難燃剤としての効果を低
めるばかりか、用途によっては悪影響を与えることがあ
る。However, in this method of modifying red phosphorus, in order to completely stabilize red phosphorus, it is necessary to coat it with a large amount of aluminum hydroxide, which not only reduces the effectiveness of red phosphorus as a flame retardant, but also may have adverse effects.
また、赤リンの改質方法の他の例として、水酸化アルミ
ニ１クムと亜鉛又はマグネシウムの水酸化物を複合しＣ
被覆する方法（米国特許第２６３５９５３号明細閤）、
熱硬化性樹脂で被覆した改質赤リン（特開昭５１−１０
５９９６号公報）、赤リン表面を金属リン化物した後に
熱硬化性樹脂で被覆した改質赤リン（特開昭５２−１２
５４８９号公報）、みリン表面をチタンの水和酸化物に
より被覆した改質赤リン（米国特許第４４２１７８２＠
明細閤）、あるいは赤リン表面をチタンの水和酸化物に
より被覆した上、更に熱硬化性樹脂で被覆した改質赤リ
ン等が提案されている。In addition, as another example of a red phosphorus reforming method, 1 cum of aluminum hydroxide and zinc or magnesium hydroxide are combined to produce carbon dioxide.
Coating method (US Pat. No. 2,635,953),
Modified red phosphorus coated with thermosetting resin (JP-A-51-10
No. 5996), modified red phosphorus in which the red phosphorus surface was coated with a thermosetting resin after metal phosphide (Japanese Patent Laid-Open No. 52-12
5489), modified red phosphorus whose surface was coated with a hydrated oxide of titanium (US Patent No. 4421782@
There have been proposals for modified red phosphorus in which the surface of the red phosphorus is coated with a hydrated oxide of titanium and then further coated with a thermosetting resin.
〈発明が解決しようとする問題点〉
前述のとおり、赤リンの改質による安定化は数多くの提
案がなされているが、いずれも一長一短が必り、尚いく
つかめ重要な問題がある。特に赤リンは、水分の存在で
加水分解され易くホスフィンガスの発生を伴い、極く少
弗であっても右奥有毒であるため、このガスの発生を完
全に抑制することは極めて困難であった。<Problems to be Solved by the Invention> As mentioned above, many proposals have been made for stabilizing red phosphorus through modification, but all of them have advantages and disadvantages, and there are still some important problems. In particular, red phosphorus is easily hydrolyzed in the presence of moisture, resulting in the generation of phosphine gas, which is highly toxic even in very small amounts, so it is extremely difficult to completely suppress the generation of this gas. Ta.
このため発生したホスフィンガスをホスフィンガスと親
和性の高い金属、例えば銅、ニッケル等の重金属を共存
させる事により抑制しようとする提案がなされているが
、重金属の多くは赤リンの加水分解を促進させる欠点が
あるため、耐湿性を低下させてホスフィンガスの発生を
促す結果となる。For this reason, proposals have been made to suppress the generated phosphine gas by coexisting metals that have a high affinity with phosphine gas, such as heavy metals such as copper and nickel, but many heavy metals promote the hydrolysis of red phosphorus. This has the disadvantage of reducing moisture resistance and promoting the generation of phosphine gas.
また、前記特開昭５２−１２５４８９号公報による改質
赤リンは、いわゆるガルバニック法によるめっき皮膜の
一種と考えることができるが、極く簿くしかも不完全な
金属リン −化物皮膜である。Furthermore, the modified red phosphorus disclosed in JP-A-52-125489 can be considered to be a type of plating film formed by the so-called galvanic method, but it is a metal phosphide film that is extremely cumbersome and incomplete.
本発明は、赤リンの分解に伴うホスフィンガスの発生を
実質的に完全に抑制すべく、種々の安定化方法を探索し
て鋭意研究を行ってきたところ、赤リン粒子にジルコニ
ウム−コバルト系複合水和酸化物の皮膜を施したところ
、驚くべきことに安定な赤リン粉末が得られることを知
見し本発明を完成した。In order to virtually completely suppress the generation of phosphine gas that accompanies the decomposition of red phosphorus, the present invention has conducted intensive research searching for various stabilization methods, and as a result, we have developed a zirconium-cobalt composite into red phosphorus particles. The present invention was completed based on the discovery that surprisingly stable red phosphorus powder could be obtained by applying a film of hydrated oxide.
く問題を解決するための手段〉
および〈作用〉
すなわち、本発明は赤リンの粒子表面にジルコニウム−
コバルト系複合水和酸化物を沈積被覆してなることを特
徴とする安定化赤すン、およびジルコニウム塩とコバル
ト塩との混合塩水溶液に分散させた赤リンの水性懸濁体
にアルカリ剤を添加して中和し、生成するジルコニウム
−コバルト系複合水和酸化物の微細な沈澱を赤リンの粒
子表面に沈積処理した後、分離回収することを特徴とす
る安定化赤リンの製造法に係るものである。Means for Solving the Problems> and <Operation> That is, the present invention provides zirconium on the surface of red phosphorus particles.
Stabilized red phosphorus characterized by being deposited and coated with a cobalt-based composite hydrated oxide, and an aqueous suspension of red phosphorus dispersed in an aqueous mixed salt solution of a zirconium salt and a cobalt salt, in which an alkaline agent is applied. A method for producing stabilized red phosphorus, which comprises adding and neutralizing fine precipitates of the resulting zirconium-cobalt composite hydrated oxide, depositing them on the surface of red phosphorus particles, and then separating and recovering them. This is related.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本光明における赤リンの粒子は、大ぎくとも１００μｍ
以下にあり、かつ平均粒子径としては５〜３０μｍ、好
ましくは１０〜２０μｍの範囲のものが好適である。ま
た、微粉末は、粒子の表面積を大きくし、又不安定にな
り易いので約１μ７７Ｌ以下の粒径のものは出来るだけ
カットしたものがよい。The red phosphorus particles in this light are at most 100 μm.
The average particle diameter is preferably in the range of 5 to 30 μm, preferably 10 to 20 μm. Further, since fine powder increases the surface area of the particles and tends to become unstable, it is preferable to use particles with a particle size of about 1 μ77L or less, which are cut as much as possible.
したがって、本発明における赤・リンの粒子は、実質的
に粒径１Ａ−１００μｍの範囲にあるものが好ましく、
また前記艶聞以外の粒径の粒子が含有されていても、粒
径１μＴｒＬ以下および１００μＴｒＬ以上のものの含
有量が５重量％以下のものが望ましい。Therefore, it is preferable that the red/phosphorus particles in the present invention have a particle size substantially in the range of 1A to 100 μm.
Further, even if particles having a particle size other than the above-mentioned gloss are contained, it is desirable that the content of particles having a particle size of 1 μTrL or less and 100 μTrL or more is 5% by weight or less.
尚、粒径および平均粒子径はコルターカウンター法によ
り測定された値を示す。Note that the particle size and average particle size are values measured by the Coulter counter method.
本発明に係る安定化赤リンは赤リン粒子の表面にジルコ
ニウムとコバルトの可溶性塩の加水分解生成物であるジ
ルコニウム−コバルト系複合水和酸化物が沈積して被覆
形成されたものである。The stabilized red phosphorus according to the present invention is formed by depositing a zirconium-cobalt complex hydrated oxide, which is a hydrolysis product of a soluble salt of zirconium and cobalt, on the surface of red phosphorus particles to form a coating.
この沈積物はＺｒＯ２・ｎＨ２０，Ｃｏ。This deposit is ZrO2.nH20, Co.
・ｎ）−１２Ｑと思われるが、共沈物であることから、
これらの単なる水酸化物の混合物ではないものと推定さ
れる。・It seems to be n)-12Q, but since it is a coprecipitate,
It is presumed that it is not simply a mixture of these hydroxides.
また、ジルコニウム−コバルト系複合水和酸化物の赤リ
ン粒子への沈積被覆ｆｌμ、安定化赤リンの用途等によ
り異なるけれども、多くの場合赤リン粒子に対し全重量
当りＺｒ＋Ｃｏとして０．５〜１０重珊％好ましくは１
〜６重量％の範囲にあることが望ましい。In addition, although it varies depending on the deposition coating flμ of the zirconium-cobalt composite hydrated oxide on the red phosphorus particles, the use of the stabilized red phosphorus, etc., in most cases, the amount of Zr+Co per total weight of the red phosphorus particles is 0.5 to 10. Heavy coral% preferably 1
It is desirable that the content be in the range of 6% by weight.
この理由は、０．５重量％未満では、ホスフィンガスの
抑制が不完全であり、１０ｆｆｉｆｉ％をこえると実用
的な見地からみて不適当である。The reason for this is that if the content is less than 0.5% by weight, the suppression of phosphine gas is incomplete, and if it exceeds 10% by weight, it is inappropriate from a practical standpoint.
また、ジルコニウム−コバルト系複合水和酸化物中にお
けるジルコニウムとコバルトのＩＩ比はＺｒ ： Ｃｏ
−１： ０．０１〜０．５の範囲にあるものが好ましい
。In addition, the II ratio of zirconium and cobalt in the zirconium-cobalt composite hydrated oxide is Zr:Co
-1: Preferably in the range of 0.01 to 0.5.
本発明にかかる安定化赤リンは、顕微鏡観察により、沈
積液留が粒子表面に形成されていることを確認でき、原
体の赤リンと比較して容易に識別することができる。The stabilized red phosphorus according to the present invention can be confirmed by microscopic observation to have deposited liquid deposits formed on the particle surface, and can be easily identified in comparison with the original red phosphorus.
本発明にかかる改質赤リンは、はぼ完全にホスフィンガ
スの発生を抑制した安定化赤リンであるが、その抑１１
１１Ｊｉ構の詳細については不明である。また、ジルコ
ニウム−コバルトの組み合わせが何故に良好な結果を示
すのかについでも詳らかではない。この組み合わせは数
多くの実験の結果見出されたもので、その一部を、比較
例４〜１３に示す様に、他の元素との組み合わせでは到
達できない特異な効果が、ジルコニウム−コバルトの組
み合せにおいては１ｑることができる。The modified red phosphorus according to the present invention is a stabilized red phosphorus that almost completely suppresses the generation of phosphine gas.
Details of the 11Ji structure are unknown. It is also not clear why the zirconium-cobalt combination shows good results. This combination was discovered as a result of numerous experiments, some of which are shown in Comparative Examples 4 to 13. can be 1q.
次に、本発明に係る安定化赤リンを製造する方法を説明
する。Next, a method for producing stabilized red phosphorus according to the present invention will be explained.
まず、ジルコニウム塩とコバルト塩との混合塩水溶液に
赤リンを分散させ、得られた赤リン懸濁体に撹拌しなが
らアルカリ剤を添加して中和し、ＰＨ６，５〜８．５に
調整する。First, red phosphorus is dispersed in a mixed salt aqueous solution of a zirconium salt and a cobalt salt, and an alkali agent is added to the resulting red phosphorus suspension while stirring to neutralize it and adjust the pH to 6.5 to 8.5. do.
中和優、さらに撹拌しながら加熱し、生成するジルコニ
ウム−コバルト系複合水和酸化物の微細な沈澱を赤リン
の粒子表面に沈積処理した後、分離、回収することによ
り工業的に有利に均質で安定な安定化赤リンを製造すこ
とができる。Neutralization is excellent, and the fine precipitates of the zirconium-cobalt complex hydrated oxide produced by heating with stirring are deposited on the surface of the red phosphorus particles, separated, and recovered, making it industrially advantageous and homogeneous. can produce stable stabilized red phosphorus.
本発明において、赤リンの水性懸濁体は、重僅比で、赤
リンの少なくとも２倍量以上、好ましくは５〜１０倍量
の水に所定量のジルコニウム塩およびコバルト塩を溶解
した混合塩水溶液に、撹拌下で赤リン粒子を添加して調
製することにより傳ることができる。この場合、混合塩
水溶液の水率が赤リンの２倍量未満では、赤リン濃度が
高くなり過ぎるために撹拌が不可能となる。In the present invention, the aqueous suspension of red phosphorus is a mixed salt obtained by dissolving a predetermined amount of zirconium salt and cobalt salt in water in an amount of at least twice, preferably 5 to 10 times, the amount of red phosphorus in a small weight ratio. It can be prepared by adding red phosphorus particles to an aqueous solution under stirring. In this case, if the water content of the mixed salt aqueous solution is less than twice the amount of red phosphorus, the red phosphorus concentration becomes too high and stirring becomes impossible.
また、赤リンの水性！９濁体の他の調製方法として、前
記とは反対に、あらかじめ赤リンを水に分散して調製し
た赤リンスラリ−に、ジルコニウム塩オよびコバルト塩
の混合塩水溶液を添加するか、或いは所定のジルコニウ
ム塩およびコバルト塩の結晶を添加して溶解することに
より水性懸濁体を青ることかできる。但し、赤リンのア
ルカリスラリーにジルコニウム塩およびコバルト塩の混
合塩の水溶液または結晶を添加すると赤リンの加水分解
が行なわれる危険性があるので避けた方がよい。Also, red phosphorus water-based! 9. As another method for preparing a turbid body, contrary to the above, a mixed salt aqueous solution of a zirconium salt and a cobalt salt is added to a red phosphorus slurry prepared by dispersing red phosphorus in water, or a predetermined solution is added. The aqueous suspension can be turned blue by adding and dissolving crystals of zirconium and cobalt salts. However, if an aqueous solution or crystals of a mixed salt of zirconium salt and cobalt salt is added to an alkaline slurry of red phosphorus, there is a risk that the red phosphorus will be hydrolyzed, so it is better to avoid this.
また、混合塩水溶液の調製に用いられるジルコニウム塩
およびコバルト塩は、特に限定することなく使用するこ
とができるが、それ等の中で特に！ｉｉＩ！酸塩、塩酸
塩又は硝酸塩から選ばれた少なくとも１種以上が好まし
い。他の塩として可溶性有ｇ４ｕｉ、金属アルコラード
であってもよい。In addition, zirconium salts and cobalt salts used in the preparation of the mixed salt aqueous solution can be used without particular limitation, but among them, especially! iii! At least one selected from acid salts, hydrochlorides, and nitrates is preferred. Other salts may include soluble g4ui and metal alcoholades.
ジルコニウム塩およびコバルト塩の混合塩水溶液の濃度
は、各基の室温における溶解度以下であれば特に限定さ
れない。The concentration of the mixed salt aqueous solution of zirconium salt and cobalt salt is not particularly limited as long as it is below the solubility of each group at room temperature.
赤リンの水性懸濁体の調製に使用する装置としでは、赤
リン粒子を均質に分散させるものであれば如何なるもの
でも用いることができるが、具体的には適宜所望の手段
、例えば、通常撹拌から高速撹拌、あるいはコロイドミ
ルまたはホモジナイザーの如きセン断分散装置等を用い
、赤リンの粒子のアグロメレートをできるだ【プ除去し
た一次粒子に近い分散状態の懸濁体を調製することが望
ましい。Any device can be used to prepare the aqueous suspension of red phosphorus as long as it can homogeneously disperse red phosphorus particles, but specifically, it can be carried out by any appropriate means, such as normal stirring. It is desirable to prepare a suspension in a dispersion state close to that of the primary particles by removing the agglomerates of red phosphorus particles by using high-speed stirring or a shear dispersion device such as a colloid mill or homogenizer.
また、赤リン粒子を分散させるに際し、例えば界面活性
剤やヘキサメタリン酸ソーダ等の分散剤を、必要に応じ
て、被覆条件を損なわない程度に少量用いることができ
る。Further, when dispersing the red phosphorus particles, a small amount of a dispersant such as a surfactant or sodium hexametaphosphate can be used as necessary to the extent that the coating conditions are not impaired.
赤リンの水性懸濁体中の赤リンの濃度は、特に限定する
理由はないが、多くの場合５０ｗ／ｌＬ〜７００ｇ／、
２ 、好ｔＬ、＜は１００ｆ？／又〜５００ ｑ ／
１の範囲が望ましく、５０９ ／１ 未満ではスラリー
′ａ度が低く沈積被覆濃度が低下するので処理容量が大
となるために経済的でなく、また７ ００ ！？／ＪＬ
をこえると赤リン粒子の分散性が悪くなるので好ましく
ない。There is no particular reason to limit the concentration of red phosphorus in the aqueous suspension of red phosphorus, but in most cases it is between 50 w/lL and 700 g/l,
2. Good tL, < is 100f? / ~ 500 q /
A range of 1 is desirable, and if it is less than 509/1, the slurry'a degree will be low and the deposited coating concentration will be lowered, so the processing capacity will be large, making it uneconomical. ? /JL
Exceeding this is not preferable because the dispersibility of the red phosphorus particles deteriorates.
また、この水性懸濁体の赤リンの粒子を沈積被覆するに
当り、沈積処理を効果的に実施するために昇温するが、
水性懸濁体の温度を沈積処理前に予め調節しておき、そ
の後にアルカリ剤を添加して沈積処理を行っても差し支
えはない。In addition, when depositing and coating the red phosphorus particles in this aqueous suspension, the temperature is raised to effectively carry out the deposition process.
There is no problem even if the temperature of the aqueous suspension is adjusted in advance before the sedimentation treatment, and then an alkaline agent is added to perform the sedimentation treatment.
アルカリ剤としてはアンモニアガス、アンモニア水、苛
性ソーダ、苛性カリ、Ｎａｆ−１ｃ０３ 、Ｎａ２００
３ 、Ｋ２ ＣＯ３、ＫＨＣＯ３、Ｃａ （Ｏ）−１＞
２等の無機アルカリ剤、またはエタノールアミン等の有
機アルカリ剤から選ばれた少なくとも１種以上のものが
用いられるが、♂Ｊ生物の洗浄除去が容易なアンモニア
ガス、アンモニア水が好ましい。As alkaline agents, ammonia gas, ammonia water, caustic soda, caustic potash, Naf-1c03, Na200
3, K2 CO3, KHCO3, Ca (O)-1>
At least one selected from inorganic alkaline agents such as No. 2, etc., and organic alkaline agents such as ethanolamine can be used, but ammonia gas and ammonia water are preferred, as they allow for easy cleaning and removal of male J organisms.
中和の終点ＰＨとしては、沈積処理終了時に液中にコバ
ルト及びジルコニウムイオンの残存の少ないＰ Ｈを設
定する必要がある。このＰＨは使用するジルコニウム塩
、コバルト塩の組み合わせにより異なるが、沈積処理終
了後の液性として、６〜８、好ましくは７゜０±０．５
の範囲に入ることが被覆を完全に行うために望ましい。As the end point PH of neutralization, it is necessary to set a PH at which less cobalt and zirconium ions remain in the solution at the end of the deposition process. This pH varies depending on the combination of zirconium salt and cobalt salt used, but the liquid property after the completion of the deposition treatment is 6 to 8, preferably 7°0±0.5.
For complete coverage, it is desirable to fall within this range.
また、酸性塩においては加熱によりＰＨは１〜１．５下
がるので、加熱前にＰＨを調整する場合には、６．５〜
８．５、好ましくは８．０±０．５の液性とする。In addition, the pH of acidic salts decreases by 1 to 1.5 when heated, so when adjusting the pH before heating, it is necessary to adjust the pH to 6.5 to 1.5.
The liquid property should be 8.5, preferably 8.0±0.5.
この際、赤リンはアルカリ性に６いて加水分解しやすい
ためにＰＨは９をこえない方がよい。At this time, since red phosphorus is alkaline (6) and easily hydrolyzed, the pH should not exceed 9.
赤リンの水性懸濁体にアルカリ剤を添り口すると、速や
かに沈積反応が始まるが、その際液濃度と共に添加速度
が反応に直接的に影響し、また、これらの要素は赤リン
の物性、特に表面特性にも著しく関係するのでこれらの
要素を十分に考慮した上で、沈積皮膜のむらの生じない
ようアルカリ剤の添加速度を設定して、制御して添加す
ることが必要である。When an alkali agent is added to an aqueous suspension of red phosphorus, a precipitation reaction begins immediately, but the addition rate as well as the liquid concentration directly affect the reaction, and these factors also affect the physical properties of red phosphorus. In particular, since it is significantly related to the surface characteristics, it is necessary to fully consider these factors and set and control the addition rate of the alkaline agent so as to prevent unevenness of the deposited film.
多くの場合徐々に定量的に添加する方がよい。In many cases it is better to add gradually and quantitatively.
この様な撹拌下に６ける中和にともなって常温或いは加
熱のいずれの場合でも、ジルコニウム−コバルト系複合
水和酸化物の微細な沈澱が赤リンの粒子表面に沈積し、
均一かつ強固な沈積皮膜が形成されてゆく。この際、゛
液中のジルコニウム塩とコバルト塩の存在量に応じて沈
積皮膜の躾厚が変わるので、これを調節することにより
各種の用途に適応した被覆を設定することができる。During the neutralization under such stirring, whether at room temperature or heating, fine precipitates of zirconium-cobalt complex hydrated oxide are deposited on the surface of the red phosphorus particles,
A uniform and strong deposited film is formed. At this time, the thickness of the deposited film changes depending on the amount of zirconium salt and cobalt salt present in the solution, so by adjusting this it is possible to set a coating suitable for various uses.
なお、沈積する際のスラリ一温度は、好ましくは６０℃
以上で、さらに好ましくは８０〜９０℃の範囲が望まし
い。Note that the slurry temperature during deposition is preferably 60°C.
Above, the temperature is more preferably in the range of 80 to 90°C.
沈積処理の終了後は、常法により母液を分離して、ジル
コニウム−コバルト系複合水和酸化物を沈積被覆した赤
リンを１過し、更に要すれば水洗、分離及び乾燥して回
収する。After the deposition process is completed, the mother liquor is separated by a conventional method, and the red phosphorus coated with the deposited zirconium-cobalt composite hydrated oxide is filtered and, if necessary, washed with water, separated, and dried to be recovered.
〈実施例〉 以下、実施例を示し本発明をさらに具体的に説明する。<Example> Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１〜６
硫酸ジルコニル溶液（Ｚｒ０２）、として２８．０３ｗ
ｔＸのもの、第−稀元素化学工業製）と硫酸コバルト（
試薬、関東化学社製）を下記の第１表に示す８吊を秤吊
し、５０ｇの水に溶解した。これに、予め水洗し真空乾
燥（１００℃）した粒径３〜４４μｍで、平均粒子径２
０μｍの赤リン粉末を５ｇ添加し、撹拌しなから５Ｗｔ
″Ｘのアンモニア水溶液を添加し、ＰＨを８．０に調整
した。Examples 1 to 6 Zirconyl sulfate solution (Zr02), 28.03w
tX, made by Kigenso Kagaku Kogyo Co., Ltd.) and cobalt sulfate (
Reagent (manufactured by Kanto Kagaku Co., Ltd.) was weighed in 8 volumes shown in Table 1 below and dissolved in 50 g of water. To this, particles with a particle size of 3 to 44 μm, which had been washed with water and dried in vacuum (100°C) in advance, had an average particle size of 2.
Add 5g of 0μm red phosphorus powder and add 5Wt without stirring.
An ammonia aqueous solution of "X" was added to adjust the pH to 8.0.
次いで、撹拌しながら加熱し、温度を８５℃とし、２時
間加熱撹拌をつづけた。冷加後、１別した。濾滓を脱イ
オン水で４液の電機伝導度が１０μＳ／α以下を示すま
で洗浄し、１２０℃の真空乾燥器中で３時間乾燥して安
定化赤リンを得た。Next, the mixture was heated with stirring to bring the temperature to 85° C., and heating and stirring were continued for 2 hours. After cooling, it was separated into portions. The filter cake was washed with deionized water until the electrical conductivity of the four liquids was 10 μS/α or less, and dried in a vacuum dryer at 120° C. for 3 hours to obtain stabilized red phosphorus.
得られた安定化赤リンのホスフィン発生量を測定した結
果は下記の第２表に示すとおりであった。The results of measuring the amount of phosphine produced in the stabilized red phosphorus obtained are shown in Table 2 below.
第２表
温度３０℃、相対湿度８３％の恒温恒湿器中に４８時間
保存した試料をＯ，！Ｍ採取し、Ｎ２ガス中で加熱（１
５０℃、３時間）する。Table 2 Samples stored for 48 hours in a constant temperature and humidity chamber at a temperature of 30°C and a relative humidity of 83%. M was collected and heated in N2 gas (1
50°C, 3 hours).
発生したＰ ）−１３ｆｆｉをガスクロマトグラフによ
り測定し、サンプル１ｇ当りの発生ＰＨ３（μｇ）に検
体した。The generated P)-13ffi was measured using a gas chromatograph and added to the generated PH3 (μg) per 1 g of sample.
瓜箆五１ニュ
実施例１〜３において、硫酸ジルコニル溶液のみを用い
て赤リン粒子を被覆した。その他の条件は実施例１と同
様に行った。硫酸ジルコニルの添加量とホスフィン発生
量の試験結果を下記の第３表に示す。In Examples 1 to 3, only the zirconyl sulfate solution was used to coat the red phosphorus particles. Other conditions were the same as in Example 1. The test results for the amount of zirconyl sulfate added and the amount of phosphine generated are shown in Table 3 below.
第３表
裏車」ＢＬユ上ユ
実施例６の硫酸コバルトに代えて下記の第４表に示す各
種の金属塩を用いて、実施例６と同等の操作で赤リンの
被覆を行なった。金属塩の種別と添加量、および得られ
た金属塩被覆赤リンのホスフィン発生量の試験結果を下
記の第４表に示す。Red phosphorus coating was carried out in the same manner as in Example 6, using various metal salts shown in Table 4 below in place of the cobalt sulfate in Example 6. The test results for the type and amount of metal salt added and the amount of phosphine generated from the obtained metal salt-coated red phosphorus are shown in Table 4 below.
友亙亘ｌ
塩化ジルコニル溶液（Ｚｒ０２として２５６ｇ／ＪＬ）
１．３ｍ１（赤リンに対しｌｒとＬテ５ＷｔＸ ） ト
硫酸コバルト（ＣｏＳＯ４−７Ｈ２０）０．１２ＳＦ
（赤リンに対しＣＯとしてＱ、 ５ｗｔ％ ）を水５０
ｇに溶解した。Wataru Yuuki Zirconyl chloride solution (256g/JL as Zr02)
1.3m1 (lr and Lte5WtX for red phosphorus) Cobalt tosulfate (CoSO4-7H20) 0.12SF
(Q as CO to red phosphorus, 5wt%) to 50% water
Dissolved in g.
これに予め水洗し真空乾燥（１００℃）した赤リン（粒
径３〜４４μｍ、平均粒子径１５μｍ＞５ｙを添加し、
撹拌しながら５ ＷｔＸのＮａＯＨ溶液を添加し、ＰＨ
を８．０に調整した。To this, red phosphorus (particle size 3 to 44 μm, average particle size 15 μm>5y) that had been washed with water and vacuum dried (100 ° C.) was added,
Add 5 WtX NaOH solution with stirring and adjust the pH
was adjusted to 8.0.
次いで、加熱し温度を８５℃とし、２時間、加熱撹拌を
つづけた。この時の最終ＰＨは７゜０であった。冷却後
、濾別した。濾滓を脱イオン水で洗浄し、１２０℃の真
空乾燥器中で３時間乾燥して安定化赤リンを青だ。Next, the mixture was heated to a temperature of 85° C. and continued to be heated and stirred for 2 hours. The final pH at this time was 7°0. After cooling, it was filtered. The filter cake was washed with deionized water and dried in a vacuum oven at 120° C. for 3 hours to remove the stabilized red phosphorus.
臀られた安定化赤リンのホスフィン発生層試験の結果は
不検出であった。The results of the phosphine generation layer test for stabilized red phosphorus were non-detectable.
友ｉ璽１
塩化ジルコニル溶液（Ｚｒ０２として２５６ｇ／Ｌ）ｏ
、ａｍ、＋２− （赤リンに対しｚｒとして３ＷｔＸ）
と塩化コバルト（Ｑｏｃ１２ ◆６Ｈ２０）０．０７ｇ
（赤リンに対しＣＯとしてＱ、 ３ＷｔＸ ）を水５０
ｇに溶解した。Friend 1 Zirconyl chloride solution (256g/L as Zr02) o
, am, +2- (3WtX as zr for red phosphorus)
and cobalt chloride (Qoc12 ◆6H20) 0.07g
(Q, 3WtX as CO for red phosphorus) to 50% water
Dissolved in g.
これに予め水洗し真空乾燥（１００℃）した赤リン（粒
径３〜４４μｍ、平均粒子径１５μｍ）！Ｍを添加し、
撹拌しながら５１Ａｔ％ＮＨ４０Ｈ溶液を添加し、ＰＨ
を８．０に調整した。Red phosphorus (particle size 3 to 44 μm, average particle size 15 μm) was washed with water and vacuum dried (100°C) in advance! Add M;
While stirring, add 51 At% NH40H solution and adjust the pH.
was adjusted to 8.0.
次いで、加熱して温度を８５℃とし、２時間加熱、撹拌
をつづけた。この時の最終ＰＨは６．８であった。冷Ｆ
ＡｖＩ！、濾別した。濾滓を脱イオン水で洗浄し、１２
０℃の真空乾燥器中で３時間乾燥して安定くヒ赤リンを
得た。Next, the mixture was heated to a temperature of 85° C., and heating and stirring were continued for 2 hours. The final pH at this time was 6.8. Cold F
AvI! , filtered. Wash the filter cake with deionized water,
The mixture was dried for 3 hours in a vacuum dryer at 0°C to obtain stable red phosphorus.
青られた安定化赤リンのホスフィン発生全試験の結果は
不検出であった。All tests for phosphine generation of stabilized red phosphorus were non-detectable.
ル」え旦二１４ （従来品の安定化赤リン）粒径３〜
４４μｍ、平均粒子径１５μｍの赤リン１００ｇを水２
５０ｇに懸澗させ赤リンのスラリーを［７した。次いで
。Ａｌ２Ｏ３として８ ＷｔＸの硫酸アルミニウムの水
溶液１２０ｇを添加した後、８０℃に昇温し、撹拌しな
がら１ＱＷｔＸのＮａＯＨ溶液を２時間にわたって滴下
しＰＨ６，６にＦｌ整した。更に、１時間加熱、撹拌を
つづけ、水酸化アルミニウムを赤リンの粒子表面に沈積
させた。Le'Etanji 14 (conventional stabilized red phosphorus) particle size 3~
44μm, average particle size 15μm red phosphorus 100g in water 2
A slurry of red phosphorus was suspended in 50 g. Next. After adding 120 g of an aqueous solution of 8 WtX aluminum sulfate as Al2O3, the temperature was raised to 80°C, and while stirring, a 1QWtX NaOH solution was added dropwise over 2 hours to adjust the pH to 6.6. Further, heating and stirring were continued for 1 hour to deposit aluminum hydroxide on the surface of the red phosphorus particles.
冷却、濾別後、濾滓を濾液の電気伝導度が２０μＳ／ｃ
１１以下になるまで洗浄した後、真交乾燥器中で１００
℃で５時間乾燥し安定化赤リンを得た。After cooling and filtering, the electrical conductivity of the filtrate is 20μS/c.
After washing until it becomes 11 or less, it is 100
Stabilized red phosphorus was obtained by drying at ℃ for 5 hours.
得られた安定化赤リンのホスフィン発生堡試験野結果は
１２．２μｇ／ｇであった。The result of the stabilized red phosphorus obtained in the phosphine formation field test field was 12.2 μg/g.
リンの皮 の 熱水試験
還流冷却器付の三角フラスコに、下記の第５表に示す各
実施例および比較例で群られた安定化赤リンのサンプル
１ｇと水１８０７７Ｌ又を入れ、煮沸状態で８時間加熱
した。その上澄液の加熱前、および加熱後のＰＨおよび
電気伝導度を測定した。その結果を第５表に示す。Hot water test on phosphorus skin In an Erlenmeyer flask equipped with a reflux condenser, 1 g of the stabilized red phosphorus sample grouped in each of the Examples and Comparative Examples shown in Table 5 below and 18,077 L of water were placed in a boiling state. Heated for 8 hours. The PH and electrical conductivity of the supernatant were measured before and after heating. The results are shown in Table 5.
第５表
〈発明の効果〉
以上説明した様に、本発明の安定化赤リンは従来前えら
れなかった耐熱分解性、耐加水分解性を示すことが見出
された。このチタン−コバルト複合被覆により赤リンの
水分の存在下及び高温下での加水分解反応はほぼ完全に
抑制されるので、各種合成樹脂の難熱剤として極めて有
用なものとすることができる。Table 5 <Effects of the Invention> As explained above, the stabilized red phosphorus of the present invention has been found to exhibit heat decomposition resistance and hydrolysis resistance that have not been seen before. This titanium-cobalt composite coating almost completely suppresses the hydrolysis reaction of red phosphorus in the presence of moisture and at high temperatures, making it extremely useful as a heat retardant for various synthetic resins.
Claims (9)
合水和酸化物を沈積被覆してなることを特徴とする安定
化赤リン。(1) Stabilized red phosphorus, characterized in that the surface of red phosphorus particles is deposited and coated with a zirconium-cobalt complex hydrated oxide.
ン粒子に対し、全重量当りＺｒ＋Ｃｏとして０．５〜１
０重量％である特許請求の範囲第１項記載の安定化赤リ
ン。(2) Zirconium-cobalt composite hydrated oxide contains 0.5 to 1 Zr+Co per total weight of red phosphorus particles.
Stabilized red phosphorus according to claim 1, which is 0% by weight.
コニウムとコバルトの重量比がＺｒ：Ｃｏ＝１：０．０
１〜０．５の範囲である特許請求の範囲第１項または第
２項記載の安定化赤リン。(3) Zirconium-cobalt composite hydrated oxide has a weight ratio of zirconium and cobalt of Zr:Co=1:0.0
Stabilized red phosphorus according to claim 1 or 2, which has a molecular weight of 1 to 0.5.
が１μｍ以下および１００μｍ以上のものの含有量が５
重量％以下である特許請求の範囲第１項記載の安定化赤
リン。(4) Red phosphorus has an average particle size of 5 to 30 μm, and the content of particles with particle sizes of 1 μm or less and 100 μm or more is 5
% or less by weight of the stabilized red phosphorus according to claim 1.
分散させた赤リンの水性懸濁体にアルカリ剤を添加して
中和し、生成するジルコニウム−コバルト系複合水和酸
化物の微細な沈澱を赤リンの粒子表面に沈積処理した後
、分離回収することを特徴とする安定化赤リンの製造法
。(5) Fine precipitates of zirconium-cobalt complex hydrated oxide produced by neutralizing an aqueous suspension of red phosphorus dispersed in a mixed salt aqueous solution of a zirconium salt and a cobalt salt by adding an alkaline agent A method for producing stabilized red phosphorus, which comprises depositing it on the surface of red phosphorus particles and then separating and recovering it.
ルト塩との混合塩水溶液に赤リン粉末を添加して調製す
る特許請求の範囲第５項記載の安定化赤リンの製造法。(6) The method for producing stabilized red phosphorus according to claim 5, wherein the aqueous suspension of red phosphorus is prepared by adding red phosphorus powder to an aqueous solution of a mixed salt of a zirconium salt and a cobalt salt.
塩又は硝酸塩から選ばれた少なくとも１種である特許請
求の範囲第５項又は第６項記載の安定化赤リンの製造法
。(7) The method for producing stabilized red phosphorus according to claim 5 or 6, wherein the zirconium salt and the cobalt salt are at least one selected from sulfates, hydrochlorides, and nitrates.
性ソーダ、苛性カリウムから選ばれた少なくとも１種で
ある特許請求の範囲第５項記載の安定化赤リンの製造法
。(8) The method for producing stabilized red phosphorus according to claim 5, wherein the alkaline agent is at least one selected from ammonia gas, aqueous ammonia, caustic soda, and caustic potassium.
ＰＨが６〜８で、かつ温度６０℃以上で行う特許請求の
範囲第５項記載の安定化赤リンの製造法。(9) The method for producing stabilized red phosphorus according to claim 5, wherein the deposition treatment of red phosphorus on the particle surface is carried out at a final pH of 6 to 8 in the reaction system and at a temperature of 60° C. or higher.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6407887A JP2514027B2 (en) | 1987-03-20 | 1987-03-20 | Stabilized red phosphorus and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6407887A JP2514027B2 (en) | 1987-03-20 | 1987-03-20 | Stabilized red phosphorus and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63230510A true JPS63230510A (en) | 1988-09-27 |
| JP2514027B2 JP2514027B2 (en) | 1996-07-10 |
Family
ID=13247692
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6407887A Expired - Fee Related JP2514027B2 (en) | 1987-03-20 | 1987-03-20 | Stabilized red phosphorus and its manufacturing method |
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| Country | Link |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111170292A (en) * | 2019-11-04 | 2020-05-19 | 湖北大学 | Preparation method and application of fiber-phase red phosphorus nanoparticles |
-
1987
- 1987-03-20 JP JP6407887A patent/JP2514027B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111170292A (en) * | 2019-11-04 | 2020-05-19 | 湖北大学 | Preparation method and application of fiber-phase red phosphorus nanoparticles |
| CN111170292B (en) * | 2019-11-04 | 2023-09-29 | 湖北大学 | Preparation method and application of fiber phase red phosphorus nano particles |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2514027B2 (en) | 1996-07-10 |
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