JPH0516366B2 - - Google Patents
Info
- Publication number
- JPH0516366B2 JPH0516366B2 JP63113632A JP11363288A JPH0516366B2 JP H0516366 B2 JPH0516366 B2 JP H0516366B2 JP 63113632 A JP63113632 A JP 63113632A JP 11363288 A JP11363288 A JP 11363288A JP H0516366 B2 JPH0516366 B2 JP H0516366B2
- Authority
- JP
- Japan
- Prior art keywords
- red phosphorus
- titanium
- cobalt
- organic resin
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 131
- 239000002245 particle Substances 0.000 claims description 54
- 229920005989 resin Polymers 0.000 claims description 38
- 239000011347 resin Substances 0.000 claims description 38
- NNSIWZRTNZEWMS-UHFFFAOYSA-N cobalt titanium Chemical compound [Ti].[Co] NNSIWZRTNZEWMS-UHFFFAOYSA-N 0.000 claims description 34
- 239000011248 coating agent Substances 0.000 claims description 24
- 238000000576 coating method Methods 0.000 claims description 24
- 239000002131 composite material Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 150000001868 cobalt Chemical class 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- 239000007900 aqueous suspension Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 150000003608 titanium Chemical class 0.000 claims description 12
- 238000000151 deposition Methods 0.000 claims description 9
- 239000010410 layer Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000011247 coating layer Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000002002 slurry Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 17
- 239000007789 gas Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 239000010941 cobalt Chemical class 0.000 description 6
- 229910017052 cobalt Chemical class 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- 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 description 4
- 238000005137 deposition process Methods 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- -1 but among them Chemical class 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 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
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000003822 epoxy resin 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
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 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 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000007822 coupling agent Substances 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
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 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
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 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
- 238000011084 recovery Methods 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
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 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
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000000576 supplementary effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
Description
［産業上の利用分野］
本発明は、赤リンの粒子表面にチタン−コバル
ト化合物および有機樹脂の沈積被覆を施した安定
化赤リンおよびその製造法に関する。
本発明にかかる安定化赤リンは、特に合成樹脂
の難然剤として有用であり、樹脂、塗料あるいは
接着剤の分野に利用することができる。
［従来の技術］
従来、赤リンが合成樹脂に対しすぐれた難燃効
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。
しかしながら、赤リンはそのまま使用する場
合、水分と反応してホスフインガスの発生を伴う
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。
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「ハンドブツク デ
ル アノルガニシエン ケミエ」８版（1964年）
“ホスホラス”Ｂ部、83頁（Gmelin.「Handbuch
der anorganischen Chemic」8th Edtion
（1964）、vol Phosphorus、Parts B.Page 83）］
が報告されている。
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量の水酸化アルミ
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、用途によつ
ては悪影響を与えることがある。
また、赤リンの改質方法の他の例として、水酸
化アルミニウムと亜鉛又はマグネシウムの水酸化
物を複合して被覆する方法（米国特許第2635953
号明細書）、熱硬化性樹脂で被覆した改質赤リン
（特開昭51−105996号公報）、赤リン表面を金属リ
ン化物化した後に熱硬化性樹脂で被覆した改質赤
リン（特開昭52−125489号公報）、赤リン表面を
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号明細書）、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（特開昭60
−141609号公報）等が提案されている。
［発明が解決しようとする課題］
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
があり、尚いくつかの重要な問題がある。特に赤
リンは、水分の存在で加水分解され易くホスフイ
ンガスの発生を伴い、極く少量であつても有臭有
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つた。
このため発生したホスフインガスをホスフイン
ガスと親和性の高い金属、例えば銅、ニツケル等
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
低下させてホスフインガスの発生を促す結果とな
る。
また、前記特開昭52−125489号公報による改質
赤リンは、いわゆるガルバニツク法によるめつき
皮膜の一種と考えることができるが、極く薄くし
かも不完全な金属リン化物皮膜である。
本発明は、赤リンの分解に伴うホスフインガス
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つてきたところ、
赤リン粒子にチタン−コバルト系複合水和酸化物
および有機樹脂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。
［課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チタ
ン−コバルト系複合水和酸化物および有機樹脂を
沈積被覆してなることを特徴とする安定化赤リ
ン、およびチタニウム塩とコバルト塩との混合塩
水溶融中に分散させた赤リンの水性懸濁体にアル
カリ剤を添加し中和して生成するチタン−コバル
ト系複合水和酸化物の微細な沈殿を赤リンの粒子
表面に沈積処理すると同時に又は次いで有機樹脂
を被覆処理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。
以下、本発明を詳細に説明する。
本発明における赤リンの粒子は、大きくとも
100μｍ以下、好ましくは44μｍ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1μｍ以下の粒径のものは出来るだけカ
ツトしたものがよい。
したがつて、本発明における赤リンの粒子は、
実質的に粒径１〜100μｍの範囲にあるものが好
ましく、また前記範囲以外の粒径の粒子が含有さ
れていても、粒径1μｍ以下および100μｍ以上の
ものの含有量が５重量％以下のものが望ましい。
尚、粒径および平均粒子径は篩分法またはコー
ルターカウンター法により測定された値を示す。
本発明に係る安定化赤リンは、前記赤リン粒子
の表面にチタンとコバルトの可溶性塩の加水分解
生成物であるチタン−コバルト系複合水和酸化物
および有機樹脂を沈積被覆してなるものである。
この安定化赤リンの具体的な形態としては、赤
リンの粒子表面にチタン−コバルト系複合水和酸
化物の沈積被覆層を形成し、その上に有機樹脂層
を形成してなる二層構造からなる被覆層を形成し
たもの、または赤リンの粒子表面にチタン−コバ
ルト系複合水和酸化物と有機樹脂との配合物を沈
積被覆してなる単一層からなる被覆層を形成した
ものが挙げられる。
前記チタン−コバルト系複合水和酸化物の沈積
物はTiO2・nH2O、Co・nH2Oと思われるが、共
沈物であることから、これらの単なる混合物では
ないものと推定される。
また、チタン−コバルト系複合水和酸化物の赤
リン粒子への沈積被覆量は、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Ti＋Coとして0.5〜15重量％、
かつCoが0.05重量％以上、好ましくは１〜６重量
％、かつCoが0.2重量％以上の範囲にあることが
望ましい。この理由は、0.5重量％％では、ホス
フインガスの抑制が不完全であり、15重量％をこ
えると実用的に見地からみて不適当である。
また、チタン−コバルト系複合水和酸化物中に
おけるコバルトの含有量は、赤リン粒子に対し
Coとして0.05重量％以上であることが好ましい。
この理由は、0.05重量％未満では、ホスフインガ
スの抑制が不完全となるためである。
次に、有機樹脂は熱硬化性樹脂が用いられ、そ
の具体例を示すと、フエノール樹脂、尿素−ホル
ムアルデヒド樹脂、メラミン樹脂、ポリエステル
樹脂、シリコーン樹脂、エポキシ樹脂、ポリアミ
ド樹脂、アクリル樹脂等が挙げられる。
また、有機樹脂の赤リンの粒子表面への沈積被
覆量は、有機樹脂の種類および用途により異なる
が、多くの場合赤リン粒子に対し全重量当り、
0.1〜15重量％、好ましくは１〜５重量％が望ま
しい。この理由は、0.1重量％未満では、有機樹
脂の被覆量が少ないために赤リンの粒子表面を十
分に被覆することができず、15重量％をこえると
作用効果が飽和した経済的見地より実用的でなく
不適当である。
前記有機樹脂の沈積被覆量は、被覆して得られ
る安定化赤リンが赤リンの粒子表面にチタン−コ
バルト系複合水和酸化物の沈積被覆層と有機樹脂
層とからなる二層構造からなる場合には有機樹脂
層の形成に用いられるものを、或いは単一層から
なる被覆層の場合にはチタン−コバルト系複合水
和酸化物と有機樹脂との配合物に含有されるもの
を示す。
本発明にかかる安定化赤リンは、顕微鏡観察に
より、沈積被覆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。
本発明にかかる安定化赤リンは、ほぼ完全にホ
スフインガスの発生を抑制した改質、安定化され
赤リンであるが、その抑制機構の詳細については
不明である。
また、本発明にかかる安定化赤リンは、主とし
てチタン−コバルトの組み合わせによりホスフイ
ンガスの発生が抑制され、有機樹脂はその皮膚の
機械的強度を増加させるなど補足的作用を行なう
ものと推定されるが、チタン−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ては明
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あり、他の元素と組み合わ
せた場合では到達できない特異な効果が、チタン
−コバルトの組み合わせにおいては得ることがで
きる。
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。
まず、第一の方法として、チタニウム塩とコバ
ルト塩との混合塩水溶液に赤リンを分散させ、得
られた赤リンの水性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。
中和後、さらに撹拌しながら加熱し、生成するチ
タン−コバルト系複合水和酸化物の微細な沈殿を
赤リンの粒子表面に沈積処理した後、分離、洗浄
を行ないチタン−コバルト被覆赤リンスラリーを
得る。このチタン−コバルト被覆赤リンスラリー
に液状の有機樹脂を添加し、必要に応じPHを調整
した後、撹拌下で加熱して有機樹脂に硬化せしめ
て赤リン粒子表面に有機樹脂層を形成した後、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ることができる。
本発明において、赤リンの水性懸濁体は、重量
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チタニウム塩および
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得るこ
とができる。この場合、混合塩水溶液の水量が赤
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。
また、赤リンの水性懸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ーに、チタニウム塩
およびコバルト塩の混合塩水溶液を添加するか、
或いは所定のチタ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得
ることができる。但し、赤リンのアルカリスラリ
ーにチタ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。
また、混合塩水溶液の調製に用いられるチタニ
ウム塩およびコバルト塩は、水溶性のチタニウム
およびコバルト塩であれば特に限定することなく
使用することができるが、それ等の中で特に硫酸
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。
チタニウム塩およびコバルト塩の混合塩水溶液
の濃度は、特に限定することはないが、各塩の室
温における溶解度以下であればよい。
赤リンの水性懸濁体の調製に使用する装置とし
ては、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を用い、赤リンの粒子
のアグロメレートをできるだけ除去した一次粒子
に近い分散状態の懸濁体を調製することが望まし
い。
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。
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50ｇ／〜
500ｇ／、好ましくは70ｇ／〜300ｇ／の範
囲が望ましく、50ｇ／未満ではスラリー濃度が
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500ｇ／をこえ
ると粒子の分散性が悪くなるので好ましくない。
また、この水性懸濁体中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
して沈積処理を行つても差し支えはない。
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、NaHCO3、
Na2CO3、K2CO3、KHCO3、Ca（OH）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、副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。
中和の終点PHとしては、沈積処理終了時に液中
にコバルト及びチタンイオンの残存の少ないPHを
設定する必要がある。このPHは使用するチタン
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。また、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。
この際、赤リンはアルカリ性において加水分解
しやすいためにPH９をこえない方がよい。
赤リンの水性懸濁体にアルカリ剤を添加する
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、特に評面特性にも
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、沈積皮膚のむらの生じないようにアルカ
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。多くの場合徐々に定量的に添加
する方がよい。
この様な撹拌下における中和にともなつて常温
或いは加熱のいずれの場合でも、チタン−コバル
ト系複合水和酸化物の微細な沈殿が赤リンの粒子
表面に沈積し、均一かつ強固な沈積皮膚が形成さ
れてゆく。この際、液中のチタニウム塩とコバル
ト塩の存在量に応じて沈積皮膜の膜厚が変わるの
で、これを前記の被覆量になるような範囲におい
て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。
なお、沈積する際のスラリー濃度は、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。
沈積処理の終了後は、常法により母液を分離し
て、チタン−コバルト系複合水和酸化物を沈積被
覆した赤リンを過し、更に要すれば水洗した
後、水に分散してチタン−コバルト被覆赤リンス
ラリーを得る。
次いで、得られたチタン−コバルト被覆赤リン
スラリーに液状の有機樹脂、主として熱硬化性樹
脂を前記の被覆量の範囲になるような量をもつて
添加し、必要に応じPHを調整した後、撹拌下で加
熱して有機樹脂を硬化せしめて赤リン粒子表面に
有機樹脂層を形成する。
この様にして、有機樹脂の皮膜を赤リン粒子表
面に被覆した後、常法により過し、更に要すれ
ば水洗した後、分離及び加熱処理して回収する。
なお、有機被覆に際し適量のカツプリング剤や
界面活性剤などの補助剤を使用する事は差支えな
く、多くの場合好ましい結果を与える。
次に、第二の方法として、赤リンの粒子表面に
チタン−コバルト系複合水和酸化物と有機樹脂と
の配合物を沈積被覆してなる単一層からなる沈積
被覆層を形成した安定化赤リンの製造法について
説明する。
この方法は、チタニウム塩とコバルト塩との混
合塩水溶液に液状の有機樹脂を添加し均一に混合
した後、赤リンを均一に分散させ、得られた赤リ
ンの水性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。中和後、さ
らに撹拌しながら加熱し、生成するチタン−コバ
ルト系複合水和酸化物の微細な沈殿と有機樹脂と
を同時に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ることができる。
しかし、この製造法は、前記と第一の方法と同
様の赤リン被覆物を得る事が出来るが、副生する
塩化アンモニウムなどの不純物が皮膜内に残る事
があるので用途が限定される。
［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。
実施例 １
四塩化チタン溶液（昭和電工(株)製、Tiとして
8.5wt％）、2.94ｇ（赤リンに対しTiとして5wt
％）と、硫酸コバルト（試薬、関東化学社製、
CoSO4・7H2O）0.073ｇ（赤リンに対しCoとし
て0.3wt％）を水50ｇに溶解した。
これに予め水洗した赤リン（粒径３〜44μｍ、
平均粒子径15μｍ）５ｇを添加し、撹拌しながら
3wt％NH4OH溶液を添加しPHを7.0に調整した。
次いで、加熱して温度を90℃とし２時間、加熱
撹拌をつづけた後、過して滓を脱イオン水で
洗浄後、水50ｇに投入しチタン−コバルト被覆赤
リンスラリーとした。
このスラリーにフエノール樹脂（群栄化学製、
レヂトツプPL−2771）0.5ｇを加え、95℃で１時
間加熱撹拌後、過、水洗し、減圧乾燥（130℃、
５時間）し安定化赤リン5.6ｇを得た。得られた
安定化赤リンの試験結果は第１表に示す通りであ
つた。
実施例 ２
実施例１と同様に操作してチタン−コバルト被
覆赤リンスラリーを得た。
このスラリーにエポキシ樹脂（シエル油化エポ
キシ製、エピコート801）0.6ｇ、硬化剤（ヘンケ
ル白水製、バーサミド−150）0.01ｇ及び界面活
性剤（三洋化成製、イオネツトＳ−20）0.6ｇを
加え5wt％リン酸でPH５とした。
60℃に加熱して、２時間経過後別し、水洗
後、110℃の減圧乾燥を16時間行ない安定化赤リ
ン5.5ｇを得た。得られた安定化赤リンの試験結
果は第１表に示す通りであつた。
実施例 ３
実施例１と同様に操作してチタン−コバルト被
覆赤リンスラリーを得た。
このスラリーに5wt％リン酸を加えPH３とした
後、メラミン樹脂エマルジヨン（大日本インキ化
学製、ウオータ・ゾルＳ−695）0.15ｇを加え、
撹拌しながら95℃に加熱し１時間反応させた。反
応中、液性は5wt％リン酸を添加しPH３に保つ
た。
反応終了後、別し、水洗後、100℃の減圧乾
燥を16時間行ない安定化赤リン5.5ｇを得た。得
られた安定化赤リンの試験結果は第１表に示す通
りであつた。
実施例 ４
実施例１と同様に操作してチタン−コバルト被
覆赤リンスラリーを得た。
このスラリーに5wt％リン酸を加えPH３に調節
した後、尿素−ホルムアルデヒド樹脂エマルジヨ
ン（昭和高分子製、ポリフイツクスUC−30M）
0.15ｇを加え、撹拌しながら95℃に加熱し１時間
反応させた。反応中、液性は5wt％リン酸を添加
しPH３を保つた。
反応終了後、別し、水洗後、100℃の減圧乾
燥を16時間行ない安定化赤リン5.5ｇを得た。得
られた安定化赤リンの試験結果は第１表に示す通
りであつた。
実施例 ５
硫酸第二チタン溶液（試薬Ti（SO4）、として
24.0wt％のもの、関東化学社製）5.2ｇ（赤リン
に対しTiとして5wt％）と硫酸コバルト（試薬、
関東化学社製）0.073ｇ（赤リンに対しCoとして
0.3wt％）及びフエノール樹脂（群栄化学製、レ
ヂトツプPL−2771）0.5ｇを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20μｍの赤リン粉
末を５ｇ添加し、撹拌しながら5wt％のアンモニ
ア水溶液を添加し、PHを7.5に調整した。
次いで、撹拌しながら加熱し、温度を95℃と
し、２時間加熱撹拌をつづけた。この時の最終PH
は6.8であつた。冷却後、別した。滓を脱イ
オン水で液の電気伝導度が10μs／cm以下を示す
まで洗浄した後、過、水洗し、130℃の減圧乾
燥器中で５時間乾燥して安定化赤リン6.2ｇを得
た。得られた安定化赤リンの試験結果は第１表に
示す通りであつた。
比較例 １
実施例１と同様に操作してチタン−コバルト被
覆赤リンスラリーを得た。
このスラリーを別し、減圧乾燥（130℃、５
時間）し安定化赤リン5.5ｇを得た。得られた安
定化赤リンの試験結果は第１表に示す通りであつ
た。
比較例 ２
予め水洗した赤リン（粒径３〜44μｍ、平均粒
子径15μｍ）５ｇを水50ｇに懸濁させ赤リンスラ
リーを調整した。これに、フエノール樹脂（群栄
化学製、レヂトツプPL−2771）１ｇを加え、95
℃で１時間加熱撹拌後、過、水洗し、減圧乾燥
（130℃、５時間）し安定化赤リン5.5ｇを得た。
得られた安定化赤リンの試験結果は第１表に示す
通りであつた。
[Industrial Field of Application] The present invention relates to stabilized red phosphorus in which the surface of red phosphorus particles is coated with a deposited coating of a titanium-cobalt compound and an organic resin, and a method for producing the same. The stabilized red phosphorus according to the present invention is particularly useful as a retardant agent for synthetic resins, and can be used in the fields of resins, paints, and adhesives. [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. However, when red phosphorus is used as it is, it reacts with moisture and causes a hydrolysis reaction accompanied by the generation of phosphine gas. Many red phosphorus modifications have been proposed. For example, a method of depositing aluminum hydroxide on the surface of red phosphorus using aluminum sulfate and sodium hydrogen carbonate [Gmelin, Handbook der Anorganisien Chemier, 8th edition (1964)]
“Phosphorus” Part B, p. 83 (Gmelin. “Handbuch
8th Edition
(1964), vol Phosphorus, Parts B.Page 83)]
has been reported. However, this red phosphorus modification method requires coating a large amount of aluminum hydroxide in order to completely stabilize red phosphorus, which not only reduces its effectiveness as a flame retardant, but also reduces the effectiveness of red phosphorus depending on the application. It may have a negative effect. Another example of a red phosphorus reforming method is a method of coating aluminum hydroxide with a composite of zinc or magnesium hydroxide (U.S. Pat. No. 2,635,953).
specification), modified red phosphorus coated with a thermosetting resin (Japanese Patent Application Laid-Open No. 105996/1983), modified red phosphorus coated with a thermosetting resin after converting the red phosphorus surface into a metal phosphide (Japanese Patent Laid-Open No. 105996/1983) modified red phosphorus (US Pat. No. 4,421,782) in which the surface of red phosphorus is coated with a hydrated oxide of titanium; or modified red phosphorus in which the surface of red phosphorus is coated with a hydrated oxide of titanium. Modified red phosphorus coated with thermosetting resin
-141609) etc. have been proposed. [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 still have some important problems. In particular, red phosphorus is easily hydrolyzed in the presence of moisture and is accompanied by the generation of phosphine gas, which is odorous and toxic even in a very small amount, so it has been extremely difficult to completely suppress the generation of this gas. 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. However, many heavy metals have the disadvantage of accelerating the hydrolysis of red phosphorus. This results in a decrease in moisture resistance and promotes the generation of phosphine gas. Furthermore, the modified red phosphorus disclosed in Japanese Patent Application Laid-open No. 52-125489 can be considered to be a type of plating film by the so-called galvanic method, but it is an extremely thin and incomplete metal phosphide film. The present invention has been achieved through extensive research and exploration of various stabilization methods in order to substantially completely suppress the generation of phosphine gas accompanying the decomposition of red phosphorus.
When red phosphorus particles were coated with a titanium-cobalt composite hydrated oxide and an organic resin film, the present invention was completed based on the discovery that surprisingly stable red phosphorus powder could be obtained. [Means for Solving the Problem] and [Operation] That is, the present invention provides a stabilizing method characterized by coating the surface of red phosphorus particles with a titanium-cobalt complex hydrated oxide and an organic resin. Fine particles of titanium-cobalt complex hydrated oxide are produced by adding an alkaline agent to an aqueous suspension of red phosphorus and a mixed salt of titanium salt and cobalt salt to neutralize it. The present invention relates to a method for producing stabilized red phosphorus, which comprises depositing a precipitate on the surface of red phosphorus particles and simultaneously or subsequently coating the surface with an organic resin. The present invention will be explained in detail below. The red phosphorus particles in the present invention are at least as large as
100 μm or less, preferably 44 μm or less, and the average particle size is 5 to 30 μm, preferably 10 to
A thickness in the range of 20 μm is preferred. 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 μm or less that are cut as much as possible. Therefore, the red phosphorus particles in the present invention are
It is preferable that the particle size is substantially in the range of 1 to 100 μm, and even if particles with a particle size outside the above range are contained, the content of particles with a particle size of 1 μm or less and 100 μm or more is 5% by weight or less is desirable. Note that the particle size and average particle size are values measured by a sieving method or a Coulter counter method. The stabilized red phosphorus according to the present invention is obtained by coating the surface of the red phosphorus particles with a titanium-cobalt complex hydrated oxide, which is a hydrolysis product of soluble salts of titanium and cobalt, and an organic resin. be. The specific form of this stabilized red phosphorus is a two-layer structure in which a deposited coating layer of titanium-cobalt composite hydrated oxide is formed on the surface of red phosphorus particles, and an organic resin layer is formed on top of the deposited coating layer. or a single layer formed by depositing and coating a blend of titanium-cobalt composite hydrated oxide and organic resin on the surface of red phosphorus particles. It will be done. The precipitate of the titanium-cobalt complex hydrated oxide is thought to be TiO 2 · nH 2 O and Co · nH 2 O, but since it is a coprecipitate, it is presumed that it is not a mere mixture of these. . In addition, the amount of titanium-cobalt composite hydrated oxide deposited on red phosphorus particles varies depending on the purpose of the stabilized red phosphorus, but in most cases it is 0.5 to 15% Ti+Co based on the total weight of red phosphorus particles. %,
It is also desirable that Co be in a range of 0.05% by weight or more, preferably 1 to 6% by weight, and Co in a range of 0.2% by weight or more. The reason for this is that at 0.5% by weight, the suppression of phosphine gas is incomplete, and at more than 15% by weight, it is inappropriate from a practical standpoint. In addition, the content of cobalt in the titanium-cobalt composite hydrated oxide is
It is preferable that Co is 0.05% by weight or more.
The reason for this is that if it is less than 0.05% by weight, the suppression of phosphine gas will be incomplete. Next, a thermosetting resin is used as the organic resin, and specific examples thereof include phenol resin, urea-formaldehyde resin, melamine resin, polyester resin, silicone resin, epoxy resin, polyamide resin, acrylic resin, etc. . In addition, the amount of red phosphorus deposited on the particle surface of organic resin varies depending on the type of organic resin and its purpose, but in most cases, the amount of red phosphorus deposited on the particle surface is
0.1 to 15% by weight, preferably 1 to 5% by weight. The reason for this is that if the amount is less than 0.1% by weight, the surface of the red phosphorus particles cannot be sufficiently covered due to the small amount of organic resin coating, and if it exceeds 15% by weight, the effect is saturated, which is not practical. It is inappropriate and inappropriate. The deposited coating amount of the organic resin is such that the stabilized red phosphorus obtained by coating has a two-layer structure consisting of a deposited coating layer of titanium-cobalt-based composite hydrated oxide and an organic resin layer on the red phosphorus particle surface. In some cases, it refers to the material used to form the organic resin layer, or in the case of a single-layer coating layer, it refers to the material contained in the blend of the titanium-cobalt complex hydrated oxide and the organic resin. The stabilized red phosphorus according to the present invention can be confirmed by microscopic observation to have a deposited coating formed on the particle surface, and can be easily identified in comparison with the original red phosphorus. The stabilized red phosphorus according to the present invention is a modified and stabilized red phosphorus that almost completely suppresses the generation of phosphine gas, but the details of the suppression mechanism are unknown. Furthermore, in the stabilized red phosphorus according to the present invention, the generation of phosphine gas is suppressed mainly by the combination of titanium and cobalt, and it is presumed that the organic resin has a supplementary effect such as increasing the mechanical strength of the skin. , it is not clear why the titanium-cobalt combination shows good results. This combination was discovered as a result of numerous experiments, and the combination of titanium and cobalt can produce unique effects that cannot be achieved when combined with other elements. Next, a method for producing stabilized red phosphorus according to the present invention will be explained. First, as a first method, red phosphorus is dispersed in a mixed salt aqueous solution of a titanium salt and a cobalt salt, and an alkali agent is added to the resulting aqueous suspension of red phosphorus while stirring to neutralize it. Adjust from .5 to 8.5.
After neutralization, heating is performed while stirring, and the resulting fine precipitates of titanium-cobalt complex hydrated oxide are deposited on the surface of red phosphorus particles, followed by separation and washing to produce titanium-cobalt coated red phosphorus slurry. get. A liquid organic resin is added to this titanium-cobalt coated red phosphorus slurry, the pH is adjusted as necessary, and the organic resin is cured by heating with stirring to form an organic resin layer on the surface of the red phosphorus particles. , separation and recovery, homogeneous and stable stabilized red phosphorus can be industrially advantageously produced. In the present invention, the aqueous suspension of red phosphorus is a mixed salt aqueous solution in which a predetermined amount of titanium salt and cobalt salt is dissolved in water in an amount of at least twice the amount of red phosphorus, preferably 5 to 10 times, by weight. It can be obtained by adding red phosphorus particles to the liquid under stirring. In this case, if the amount of water in 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. In addition, as another method for preparing an aqueous suspension of red phosphorus, contrary to the above, a mixed salt aqueous solution of a titanium salt and a cobalt salt is added to a red phosphorus slurry prepared by dispersing red phosphorus in water in advance. mosquito,
Alternatively, an aqueous suspension can be obtained by adding and dissolving crystals of predetermined titanium salts and cobalt salts. However, if an aqueous solution or crystals of a mixed salt of titanium 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. Furthermore, the titanium salts and cobalt salts used in the preparation of the mixed salt aqueous solution can be used without particular limitation as long as they are water-soluble titanium and cobalt salts, but among them, sulfates and hydrochlorides are particularly suitable. or at least one selected from nitrates
More than one species is preferred. The concentration of the mixed salt aqueous solution of a titanium salt and a cobalt salt is not particularly limited, but may be equal to or lower than the solubility of each salt at room temperature. 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, any desired means may be used as appropriate, such as normal stirring. It is desirable to use high-speed stirring or a shear dispersion device such as a colloid mill or homogenizer to prepare a suspension in a state of dispersion close to that of primary particles, with the agglomerates of red phosphorus particles removed as much as possible. 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. There is no particular reason to limit the concentration of red phosphorus in an aqueous suspension of red phosphorus, but it is often 50 g/~
A range of 500g/, preferably 70g/ to 300g/ is desirable; if it is less than 50g/, the slurry concentration will be low and the deposited coating concentration will decrease, making it uneconomical because the processing capacity will be large; if it exceeds 500g/, particles will This is not preferable because the dispersibility of the material becomes poor. In addition, in depositing and coating the red phosphorus particles in this aqueous suspension, the temperature is raised to effectively carry out the deposition process, but the temperature of the aqueous suspension is adjusted in advance before the deposition process. There is no problem in adding an alkaline agent and performing a deposition treatment after that. Alkaline agents include ammonia gas, aqueous ammonia, caustic soda, caustic potash, NaHCO 3 ,
At least one selected from inorganic alkaline agents such as Na 2 CO 3 , K 2 CO 3 , KHCO 3 , Ca(OH) 2 , and organic alkaline agents such as ethanolamine is used; Ammonia gas and ammonia water are preferred because they can be easily removed by washing. The end point pH of neutralization needs to be set at a pH at which cobalt and titanium ions remain in the solution at the end of the deposition process. This pH varies depending on the combination of titanium salt and cobalt salt used, but the pH after the completion of the deposition treatment is 6 to 8, preferably 6 to 8.
It is desirable to fall within the range of 7.0±0.5 for complete coverage. In addition, heating lowers the PH by 1 to 1.5, so if you adjust the PH before heating, 6.5
The liquidity should be ~8.5, preferably 8.0±0.5. At this time, since red phosphorus is easily hydrolyzed in alkaline conditions, it is better not to exceed PH9. 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;
These factors are significantly related to the physical properties of red phosphorus, especially the surface characteristics, so after fully considering these factors, the addition rate of the alkaline agent should be set and controlled to avoid uneven deposited skin. It is necessary to add In many cases it is better to add gradually and quantitatively. As a result of neutralization under such stirring, fine precipitates of titanium-cobalt complex hydrated oxide are deposited on the surface of the red phosphorus particles, whether at room temperature or under heating, forming a uniform and firm deposited skin. is being formed. At this time, the thickness of the deposited film changes depending on the amount of titanium salt and cobalt salt present in the solution, so by adjusting this within the range that provides the above-mentioned coating amount, a coating suitable for various uses can be created. Can be set. Note that the slurry concentration during deposition is preferably 60°C or higher, more preferably in the range of 80 to 90°C. After the deposition process is completed, the mother liquor is separated by a conventional method, and the red phosphorus coated with the titanium-cobalt complex hydrated oxide is filtered, and if necessary, after washing with water, it is dispersed in water to obtain the titanium-cobalt composite hydrated oxide. Obtain a cobalt coated red rinse slurry. Next, a liquid organic resin, mainly a thermosetting resin, was added to the obtained titanium-cobalt coated red rinsing slurry in an amount that would be within the above coating amount range, and the pH was adjusted as necessary. The organic resin is cured by heating under stirring to form an organic resin layer on the surface of the red phosphorus particles. After the organic resin film is coated on the surface of the red phosphorus particles in this way, the red phosphorus particles are filtered by a conventional method, washed with water if necessary, and then separated and heated to be recovered. It should be noted that the use of an appropriate amount of auxiliary agents such as coupling agents and surfactants in forming the organic coating does not pose a problem and often gives favorable results. Next, as a second method, the stabilized red phosphorus particle surface is coated with a single layer of a mixture of a titanium-cobalt composite hydrated oxide and an organic resin. The method for producing phosphorus will be explained. In this method, a liquid organic resin is added to an aqueous mixed salt solution of a titanium salt and a cobalt salt, mixed uniformly, red phosphorus is uniformly dispersed, and the resulting aqueous suspension of red phosphorus is stirred. Add an alkaline agent to neutralize and adjust the pH to 6.5-8.5. After neutralization, heating is performed while stirring, and the resulting fine precipitates of titanium-cobalt composite hydrated oxide and organic resin are deposited on the red phosphorus particle surface at the same time, and then separated and recovered for industrial use. It is possible to advantageously produce homogeneous and stable stabilized red phosphorus. However, although this production method can produce a red phosphorus coating similar to the first method, its use is limited because impurities such as by-product ammonium chloride may remain in the coating. [Examples] Hereinafter, the present invention will be explained in more detail by showing examples. Example 1 Titanium tetrachloride solution (manufactured by Showa Denko Co., Ltd., as Ti
8.5wt%), 2.94g (5wt as Ti for red phosphorus)
%) and cobalt sulfate (reagent, manufactured by Kanto Kagaku Co., Ltd.,
CoSO 4 .7H 2 O) 0.073 g (0.3 wt% as Co relative to red phosphorus) was dissolved in 50 g of water. Add to this pre-washed red phosphorus (particle size 3-44μm,
Add 5g of average particle size 15μm) and add while stirring.
A 3wt% NH 4 OH solution was added to adjust the pH to 7.0. Next, the mixture was heated to a temperature of 90 DEG C. and continued to be heated and stirred for 2 hours, and the filtered residue was washed with deionized water and then added to 50 g of water to obtain a titanium-cobalt coated red rinsing slurry. Phenol resin (manufactured by Gunei Chemical Co., Ltd.,
Add 0.5 g of Resitop PL-2771), heat and stir at 95℃ for 1 hour, filter, wash with water, and dry under reduced pressure (130℃,
5 hours) to obtain 5.6 g of stabilized red phosphorus. The test results for the stabilized red phosphorus obtained were as shown in Table 1. Example 2 A titanium-cobalt coated red rinsing slurry was obtained in the same manner as in Example 1. Add 0.6 g of epoxy resin (Epicoat 801, manufactured by Ciel Yuka Epoxy), 0.01 g of hardening agent (Versamide-150, manufactured by Henkel Hakusui), and 0.6 g of surfactant (Ionet S-20, manufactured by Sanyo Kasei) to this slurry, and add 5 wt. % phosphoric acid to pH 5. The mixture was heated to 60°C, separated after 2 hours, washed with water, and dried under reduced pressure at 110°C for 16 hours to obtain 5.5 g of stabilized red phosphorus. The test results for the stabilized red phosphorus obtained were as shown in Table 1. Example 3 A titanium-cobalt coated red rinsing slurry was obtained in the same manner as in Example 1. After adding 5wt% phosphoric acid to this slurry to adjust the pH to 3, 0.15g of melamine resin emulsion (Water Sol S-695, manufactured by Dainippon Ink Chemical) was added.
While stirring, the mixture was heated to 95°C and reacted for 1 hour. During the reaction, the pH of the solution was maintained at 3 by adding 5 wt% phosphoric acid. After the reaction was completed, the mixture was separated, washed with water, and dried under reduced pressure at 100°C for 16 hours to obtain 5.5 g of stabilized red phosphorus. The test results for the stabilized red phosphorus obtained were as shown in Table 1. Example 4 A titanium-cobalt coated red rinsing slurry was obtained in the same manner as in Example 1. After adding 5wt% phosphoric acid to this slurry and adjusting the pH to 3, a urea-formaldehyde resin emulsion (Polyfix UC-30M, manufactured by Showa Kobunshi) was added.
0.15 g was added, and the mixture was heated to 95° C. with stirring and allowed to react for 1 hour. During the reaction, 5wt% phosphoric acid was added to maintain the pH of the solution at 3. After the reaction was completed, the mixture was separated, washed with water, and dried under reduced pressure at 100°C for 16 hours to obtain 5.5 g of stabilized red phosphorus. The test results for the stabilized red phosphorus obtained were as shown in Table 1. Example 5 Titanium sulfate solution (as reagent Ti(SO 4 ))
24.0wt%, manufactured by Kanto Kagaku Co., Ltd.) 5.2g (5wt% as Ti relative to red phosphorus) and cobalt sulfate (reagent,
Kanto Kagaku Co., Ltd.) 0.073g (as Co for red phosphorus)
0.3 wt%) and 0.5 g of phenolic resin (Regitop PL-2771, manufactured by Gunei Chemical Co., Ltd.) were dissolved in 50 g of water. To this, 5 g of red phosphorus powder with a particle size of 3 to 44 μm and an average particle size of 20 μm, which had been washed with water and vacuum dried (100°C), was added, and while stirring, 5 wt% ammonia aqueous solution was added, and the pH was adjusted to 7.5. did. Next, the mixture was heated with stirring to bring the temperature to 95°C, and heating and stirring were continued for 2 hours. Final PH at this time
was 6.8. After cooling, it was separated. The slag was washed with deionized water until the electrical conductivity of the liquid was 10 μs/cm or less, filtered, washed with water, and dried in a vacuum dryer at 130°C for 5 hours to obtain 6.2 g of stabilized red phosphorus. . The test results for the stabilized red phosphorus obtained were as shown in Table 1. Comparative Example 1 A titanium-cobalt coated red rinsing slurry was obtained in the same manner as in Example 1. This slurry was separated and dried under reduced pressure (130℃, 5
time) to obtain 5.5 g of stabilized red phosphorus. The test results for the stabilized red phosphorus obtained were as shown in Table 1. Comparative Example 2 A red phosphorus slurry was prepared by suspending 5 g of red phosphorus (particle size: 3 to 44 μm, average particle size: 15 μm), which had been washed in advance, in 50 g of water. Add 1 g of phenol resin (Resitop PL-2771, manufactured by Gunei Chemical Co., Ltd.) to this,
After heating and stirring at ℃ for 1 hour, the mixture was filtered, washed with water, and dried under reduced pressure (130 ℃, 5 hours) to obtain 5.5 g of stabilized red phosphorus.
The test results for the stabilized red phosphorus obtained were as shown in Table 1.
【表】
Γホスフイン発生量の測定
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0.5ｇ採取し、N2ガス中で
加熱（150℃、３時間）する。
発生したPH3量をガスクロマトグラフにより
測定し、サンプル１ｇ当り発生PH3量（μｇ）
換算した。
Γ安定化赤リンの被覆の耐熱水試験
還流冷却器付の三角フラスコに、上記の第１
表に示す各実施例および比較例で得られた安定
化赤リンのサンプル１ｇと水180ml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
する。
［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
来考えられなかつた耐熱分解性、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
合被覆および有機樹脂の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、各種合成樹脂の難燃剤として
極めて有用なものとすることができる。[Table] Measurement of the amount of Γphosphine generated.
Take 0.5g of the sample stored for a period of time and heat it in N2 gas (150°C, 3 hours). The amount of PH3 generated was measured using a gas chromatograph, and the amount of PH3 generated per 1g of sample (μg) was determined.
Converted. Hot water resistance test of Γ-stabilized red phosphorus coating In an Erlenmeyer flask equipped with a reflux condenser,
1 g of the stabilized red phosphorus sample obtained in each of the Examples and Comparative Examples shown in the table and 180 ml of water were added and heated at a boiling state for 8 hours. Measure the PH and electrical conductivity of the supernatant before and after heating. [Effects of the Invention] As explained above, it has been found that the stabilized red phosphorus of the present invention exhibits heat decomposition resistance and hydrolysis resistance that were hitherto unimaginable. This titanium-cobalt composite coating and organic resin coating almost completely suppress the hydrolysis reaction of red phosphorus in the presence of moisture and at high temperatures, making it extremely useful as a flame retardant for various synthetic resins. I can do it.
Claims (1)
水和酸化物および有機樹脂を沈積被覆してなるこ
とを特徴とする安定化赤リン。 ２ 赤リンの粒子表面にチタン−コバルト系複合
水和酸化物の沈積被覆層を形成し、その上に有機
樹脂層を形成してなる請求項１記載の安定化赤リ
ン。 ３ 赤リンの粒子表面にチタン−コバルト系複合
水和酸化物と有機樹脂からなる沈積被覆層を形成
してなる請求項１記載の安定化赤リン。 ４ 赤リンの粒子表面への沈積被覆量が、赤リン
粒子に対し全重量当り、チタン−コバルト系複合
水和酸化物量がTi＋Coとして0.5〜15重量％、か
つCoが0.05重量％以上および有機樹脂量が0.1〜
15重量％である請求項１、２または３記載の安定
化赤リン。 ５ チタニウム塩とコバルト塩との混合塩水溶液
中に分散させた赤リンの水性懸濁体にアルカリ剤
を添加し中和して生成するチタン−コバルト系複
合水和酸化物の微細な沈殿を赤リンの粒子表面に
沈積処理すると同時に又は次いで有機樹脂を被覆
処理することを特徴とする安定化赤リンの製造
法。 ６ 赤リンの粒子表面へのチタン−コバルト系複
合水和酸化物の沈積処理は、反応系の最終PHが６
〜８で、かつ温度60℃以上で行なう請求項５記載
の安定化赤リンの製造法。[Scope of Claims] 1. Stabilized red phosphorus, characterized in that the surface of red phosphorus particles is deposited and coated with a titanium-cobalt complex hydrated oxide and an organic resin. 2. The stabilized red phosphorus according to claim 1, wherein a deposited coating layer of a titanium-cobalt composite hydrated oxide is formed on the surface of the red phosphorus particles, and an organic resin layer is formed thereon. 3. The stabilized red phosphorus according to claim 1, wherein a deposited coating layer comprising a titanium-cobalt composite hydrated oxide and an organic resin is formed on the surface of the red phosphorus particles. 4. The amount of red phosphorus deposited on the particle surface is 0.5 to 15% by weight of titanium-cobalt composite hydrated oxide as Ti + Co, and 0.05% by weight or more of Co, and organic resin based on the total weight of red phosphorus particles. The amount is 0.1~
Stabilized red phosphorus according to claim 1, 2 or 3, which is 15% by weight. 5. A fine precipitate of titanium-cobalt complex hydrated oxide produced by adding an alkaline agent to an aqueous suspension of red phosphorus dispersed in an aqueous mixed salt solution of a titanium salt and a cobalt salt to neutralize it. A method for producing stabilized red phosphorus, which comprises depositing the surface of phosphorus particles and simultaneously or subsequently coating the surface with an organic resin. 6 The deposition treatment of titanium-cobalt composite hydrated oxide on the surface of red phosphorus particles is performed until the final pH of the reaction system is 6.
8. The method for producing stabilized red phosphorus according to claim 5, wherein the method is carried out at a temperature of 60° C. or higher.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63113632A JPH01286909A (en) | 1988-05-12 | 1988-05-12 | Stabilized red phosphorus and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63113632A JPH01286909A (en) | 1988-05-12 | 1988-05-12 | Stabilized red phosphorus and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01286909A JPH01286909A (en) | 1989-11-17 |
| JPH0516366B2 true JPH0516366B2 (en) | 1993-03-04 |
Family
ID=14617155
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63113632A Granted JPH01286909A (en) | 1988-05-12 | 1988-05-12 | Stabilized red phosphorus and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01286909A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69736026T2 (en) * | 1996-03-08 | 2006-12-07 | Tosoh Corp., Shinnanyo | FLAME-REDUCING PLASTIC COMPOSITION |
| JP4155448B2 (en) * | 2002-09-30 | 2008-09-24 | 日本化学工業株式会社 | Method for producing slurry containing red phosphorus particles and method for producing stabilized red phosphorus |
-
1988
- 1988-05-12 JP JP63113632A patent/JPH01286909A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01286909A (en) | 1989-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6120576A (en) | Method for preparing nickel fine powder | |
| KR20100031250A (en) | Method for manufacturing cupper nanoparticles and cupper nanoparticles using the same | |
| JPH09256007A (en) | Production of copper powder | |
| JPH09241709A (en) | Production of copper powder | |
| JPH02294414A (en) | Production of fine copper powder | |
| JP3073732B1 (en) | Nickel fine powder and method for producing the same | |
| JP3674009B2 (en) | Method for producing amorphous titanium oxide sol | |
| JP2855331B2 (en) | Stabilized red phosphorus and method for producing the same | |
| JPH0516366B2 (en) | ||
| JP2991700B2 (en) | Method for producing nickel fine powder | |
| JP2696232B2 (en) | Stabilized red phosphorus and method for producing the same | |
| JPS6320486A (en) | Production of silver or copper coated mica | |
| JP2835955B2 (en) | Stabilized red phosphorus and method for producing the same | |
| JP2023011705A (en) | Tantalic acid dispersion and tantalic acid compound | |
| JPH058125B2 (en) | ||
| KR100495698B1 (en) | A preparation method of Ag-doped Nano Zirconium Phosphate powders with improved antimicrobial property | |
| JP2514027B2 (en) | Stabilized red phosphorus and its manufacturing method | |
| JP2877821B2 (en) | Stabilized red phosphorus and its production | |
| US4374676A (en) | Heat stable yellow iron oxides containing antimony | |
| JPH0647449B2 (en) | Method for producing stabilized red phosphorus | |
| KR101314990B1 (en) | Manufacturing method of conductive copper powder | |
| JP4003222B2 (en) | Method for producing scaly nickel powder | |
| JP3444608B2 (en) | Production method of copper fine powder | |
| JP3254693B2 (en) | Preparation of hydrated zirconia sol and zirconia powder | |
| JP3505133B2 (en) | Surface conductive nickel oxyhydroxide and method for producing the same |