JPH05239260A - Flame-retarding resin composition - Google Patents
Flame-retarding resin compositionInfo
- Publication number
- JPH05239260A JPH05239260A JP3913792A JP3913792A JPH05239260A JP H05239260 A JPH05239260 A JP H05239260A JP 3913792 A JP3913792 A JP 3913792A JP 3913792 A JP3913792 A JP 3913792A JP H05239260 A JPH05239260 A JP H05239260A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- flame
- red phosphorus
- resin composition
- retardant
- 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.)
- Pending
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は難燃性に優れた樹脂組成
物に関する。さらに詳しくは、特殊な安定化赤リンと熱
可塑性樹脂よりなる難燃樹脂組成物に関する。FIELD OF THE INVENTION The present invention relates to a resin composition having excellent flame retardancy. More specifically, it relates to a flame-retardant resin composition comprising special stabilized red phosphorus and a thermoplastic resin.
【0002】[0002]
【従来技術】家電部品、OA機器部品等において使用さ
れる熱可塑性樹脂は安全性の問題から、難燃性の要求が
高まってきており、種々の難燃規格が定められている。
上記用途分野において使用される樹脂としては、ゴム変
性ビニル芳香族樹脂、ポリオレフィン、ポリスチレン、
ABS樹脂、ポリカーボネート系アロイ、ポリフェニレ
ンエーテル系樹脂、ポリエステル樹脂、ポリアミド樹脂
等があるがいずれも易燃性であり、難燃性付与の方法が
種々提案されている。2. Description of the Related Art Thermoplastic resins used in home electric appliance parts, office automation equipment parts and the like are increasingly required to have flame retardancy due to safety issues, and various flame retardant standards have been established.
As the resin used in the above-mentioned field of application, rubber-modified vinyl aromatic resin, polyolefin, polystyrene,
There are ABS resins, polycarbonate alloys, polyphenylene ether resins, polyester resins, polyamide resins and the like, all of which are flammable, and various methods for imparting flame retardancy have been proposed.
【0003】ごく一般的には、難燃効果の高い臭素化合
物などのハロゲン化合物及び必要に応じて酸化アンチモ
ンを樹脂に添加する方法が採用されている。しかしなが
らこれらの難燃剤添加による方法では優れた難燃性が得
られるものの、衝撃強度や熱変形温度が低下し、場合に
よっては難燃剤が樹脂の成形品表面にブリードアウトし
て成形品外観を悪化させるなどの問題点を有していた。
また樹脂の成形時に、ハロゲン化合物が分解し人体に有
毒なガスを発生したり、金型およびスクリーンを腐食す
るなどの問題を有していた。Generally, a method has been adopted in which a halogen compound such as a bromine compound having a high flame retardant effect and, if necessary, antimony oxide are added to a resin. However, although the method of adding these flame retardants provides excellent flame retardancy, the impact strength and heat distortion temperature decrease, and in some cases, the flame retardant bleeds out on the surface of the resin molded product and the molded product appearance deteriorates. There was a problem such as causing it.
Further, during molding of the resin, there are problems that the halogen compound is decomposed to generate a toxic gas to the human body, and the mold and screen are corroded.
【0004】この為ハロゲン化合物を用いないで難燃化
する方法が検討されている。かかる方法としては樹脂に
水酸化マグネシュウム、水酸化アルミニュウムなどの水
和金属化合物を添加する方法が知られているが、充分な
難燃性をえるためには、上記水和化合物を大量に添加す
る必要があり、樹脂本来の性質が失われるという欠点を
有していた。一方、このような水和金属化合物を用いな
いで難燃化する方法として、熱可塑性樹脂にフェノール
・アルデヒド樹脂、有機窒素化合物、有機リン化合物を
配合してなる難燃性樹脂組成物(USP463294
6)、ABS樹脂に赤リン、メラミン、熱架橋硬化性樹
脂を配合してなる難燃性樹脂組成物(特開昭1−296
143)が開示されている。一方、米国特許第3663
654号明細書にはポリフェニレンエーテル、スチレン
系樹脂及び赤リンよりなる難燃性樹脂組成物が開示され
ている。本発明者らも先に赤リンを難燃剤として使用す
る樹脂組成物について特許出願した。(特願平2−13
0288、2−222455、2−222456、2−
222457、H3−182328、H3−25145
8、H3−264620、H3−304369、H3−
310807、H3−316070、H3−31575
4)しかしながら上記組成物はハロゲンを用いない有用
な難燃性樹脂材料ではあるが、赤リンを難燃剤として用
いる場合には、燐と水の反応により発生するホスフイン
ガスの毒性が強いため、作業環境の安全性確保に多大の
投資を必要として問題であった。また成形品に配合され
た赤リンが長い時間をかけて徐々に、樹脂中に浸透して
きた水分と反応し反応生成物が、成形品、製品の外観を
著しく損なうため工業的な用途が制限されるという問題
があった。For this reason, methods of flame retarding without using halogen compounds have been investigated. As such a method, a method of adding a hydrated metal compound such as magnesium hydroxide or aluminum hydroxide to a resin is known, but in order to obtain sufficient flame retardancy, a large amount of the above hydrated compound is added. It was necessary and had the drawback that the original properties of the resin were lost. On the other hand, as a method of flame-retarding without using such a hydrated metal compound, a flame-retardant resin composition obtained by blending a phenol / aldehyde resin, an organic nitrogen compound, and an organic phosphorus compound with a thermoplastic resin (USP463294).
6), a flame-retardant resin composition obtained by blending ABS resin with red phosphorus, melamine, and a heat-crosslinking curable resin (JP-A-1-296).
143) is disclosed. On the other hand, US Pat.
No. 654 discloses a flame-retardant resin composition comprising polyphenylene ether, a styrene resin and red phosphorus. The present inventors have previously filed a patent application for a resin composition using red phosphorus as a flame retardant. (Japanese Patent Application No. 2-13
0288, 2-222455, 2-222456, 2-
222457, H3-182328, H3-25145
8, H3-264620, H3-304369, H3-
310807, H3-316070, H3-31575
4) However, although the above composition is a useful flame-retardant resin material that does not use halogen, when red phosphorus is used as a flame retardant, the phosphine gas generated by the reaction of phosphorus and water is highly toxic, so that the working environment is This was a problem because a large amount of investment was required to secure the safety of. In addition, the red phosphorus compounded in the molded product gradually reacts with the moisture that has penetrated into the resin over a long period of time, and the reaction product significantly impairs the appearance of the molded product and the product, limiting industrial applications. There was a problem that
【0005】一方、赤リンと水との反応を抑制するため
種々の検討がなされている。赤リンを水和金属化合物で
被覆する方法、赤リンをフェノール樹脂等で樹脂コート
する方法または金属水和物で被覆した後、樹脂コートす
る方法等が提案されているが赤リンの安定化効果は充分
ではなく、ホスフイン発生を皆無にすることはできなか
った。また、赤リンの無電解メッキを行いニッケル等の
金属によって赤リンを被覆した場合にホスフインの発生
が完全に抑制される事が開示されている。(特開昭63
−69704)しかしながらこの発明により開示された
方法により無電解メッキされた安定化赤リンをもちい
て、熱可塑性樹脂の難燃化を行った例が開示されていな
い。On the other hand, various studies have been made to suppress the reaction between red phosphorus and water. A method of coating red phosphorus with a hydrated metal compound, a method of resin coating red phosphorus with a phenolic resin, or a method of coating red phosphorus with a metal hydrate and then resin coating has been proposed. Was not sufficient and could not eliminate phosphine generation. It is also disclosed that when electroless plating of red phosphorus is performed and the red phosphorus is coated with a metal such as nickel, generation of phosphine is completely suppressed. (JP-A-63
-69704) However, no example is disclosed in which flame retardation of a thermoplastic resin is carried out by using the stabilized red phosphorus electrolessly plated by the method disclosed by the present invention.
【0006】[0006]
【発明が解決しようとする課題】本発明の目的は、無電
解メッキにより安定化した赤リンを難燃剤として用い
て、熱可塑性樹脂を難燃化しようとするものである。SUMMARY OF THE INVENTION An object of the present invention is to make a thermoplastic resin flame-retardant by using red phosphorus stabilized by electroless plating as a flame retardant.
【0007】[0007]
【課題を解決するための手段】本発明者らは上記目的を
達成するため鋭意検討した結果、特定の安定化した赤リ
ンと熱可塑性樹脂を押し出し混練した場合に、ホスフイ
ンの発生もなく、良好な樹脂成形品をえることのできる
難燃樹脂組成物が得られる事を見いだし本発明を完成す
るに至った。Means for Solving the Problems The inventors of the present invention have made extensive studies to achieve the above object, and as a result, when a specific stabilized red phosphorus and a thermoplastic resin were extruded and kneaded, no phosphine was generated and good results were obtained. It was found that a flame-retardant resin composition capable of obtaining various resin molded products was obtained, and the present invention was completed.
【0008】すなわち本発明は、無電解メッキした赤リ
ンと熱可塑性樹脂からなる難燃樹脂組成物であり、さら
に詳しく言えば、上記熱可塑性樹脂がゴム変性ビニル芳
香族樹脂、ポリオレフイン、ポリスチレン、ABS樹
脂、ポリカーボネート系アロイ、ポリフェニレンエーテ
ル系樹脂、ポリエステル樹脂、ポリアミド樹脂の一種ま
たは二種以上の混合物であり、赤リンの無電解メッキ被
膜が鉄、コバルト、ニッケル、マンガン、スズであるこ
とを特徴とする難燃樹脂組成物である。That is, the present invention is a flame-retardant resin composition comprising electrolessly plated red phosphorus and a thermoplastic resin. More specifically, the thermoplastic resin is a rubber-modified vinyl aromatic resin, polyolefin, polystyrene, ABS. Resin, a polycarbonate-based alloy, a polyphenylene ether-based resin, a polyester resin, a polyamide resin is one or a mixture of two or more, the electroless plating film of red phosphorus is iron, cobalt, nickel, manganese, characterized in that Flame retardant resin composition.
【0009】本発明における無電解メッキした赤リン
は、赤リンの表面を還元触媒で処理した後、水中に懸濁
し錯化剤の存在下に、金属塩と燐酸系の還元剤を反応さ
せる事により得られる。本発明における赤リンの粒径は
5〜50μの範囲が好ましい。無電解メッキ被膜として
は特に限定するところではないがFe,Ni,Co,C
u,Zn,Mnまたはこれらの合金から選ばれた金属メ
ッキ被膜が好ましく特にNiまたはNiの合金が好まし
い。無電解メッキ被膜の好ましい厚みは、使用する金属
によって異なるがメッキ被膜の耐久性が充分に保てる範
囲であることが好ましい。ホスフィンガス発生の抑制を
完全にするためには5〜10μの厚みが好ましい。The electroless-plated red phosphorus in the present invention is obtained by treating the surface of red phosphorus with a reducing catalyst and then suspending it in water to react a metal salt with a phosphoric acid-based reducing agent in the presence of a complexing agent. Is obtained by The particle size of red phosphorus in the present invention is preferably in the range of 5 to 50 μm. The electroless plating film is not particularly limited, but Fe, Ni, Co, C
A metal plating film selected from u, Zn, Mn or an alloy thereof is preferable, and Ni or an alloy of Ni is particularly preferable. The preferable thickness of the electroless plating film varies depending on the metal used, but it is preferable that the durability of the plating film is sufficiently maintained. In order to completely suppress the generation of phosphine gas, a thickness of 5 to 10 μm is preferable.
【0010】本発明の難燃樹脂組成物100重量部に占
める赤リンの量は、1〜15重量部が好ましく、特に好
ましくは1〜5重量部である。本発明で用いる熱可塑性
樹脂としてはゴム変性ビニル芳香族樹脂、ポリオレフィ
ン、ポリスチレン、ABS樹脂、ポリカーボネート系ア
ロイ、ポリフェニレン、エーテ系樹脂、ポリエステル樹
脂、ポリアミド樹脂の一種または二種以上の混合物であ
るが、特にゴム変性ビニル芳香族樹脂単独、もしくはゴ
ム変性ビニル芳香族樹脂とポリフェニレンエーテルの混
合物が好ましい。The amount of red phosphorus in 100 parts by weight of the flame-retardant resin composition of the present invention is preferably 1 to 15 parts by weight, particularly preferably 1 to 5 parts by weight. The thermoplastic resin used in the present invention is a rubber-modified vinyl aromatic resin, polyolefin, polystyrene, ABS resin, polycarbonate alloy, polyphenylene, ete resin, polyester resin, polyamide resin, or a mixture of two or more thereof. Particularly, the rubber-modified vinyl aromatic resin alone or a mixture of the rubber-modified vinyl aromatic resin and polyphenylene ether is preferable.
【0011】本発明における難燃樹脂組成物には赤リン
の他にトリフェニルホスフェート、ヒドロキシフェニル
ジフェニルフォスフェート、ヒドロキシフェニル含有フ
ォスフェート、トリフェニルフォスフェートのダイマ
ー、ポリリン酸アンモニュウム等を用いることもでき
る。また燐系難燃剤と複合効果の高い窒素含有化合物を
併用した場合に高い難燃効果を得ることもできる。窒素
含有化合物としてはメラミン、メラミン樹脂、サクシノ
グアナミン、その他トリアジン環を持つ化合物が有効で
ある。In addition to red phosphorus, triphenyl phosphate, hydroxyphenyl diphenyl phosphate, hydroxyphenyl-containing phosphate, dimer of triphenyl phosphate, ammonium polyphosphate and the like can be used in the flame retardant resin composition of the present invention. .. Further, when a phosphorus-containing flame retardant and a nitrogen-containing compound having a high compounding effect are used together, a high flame retarding effect can be obtained. As the nitrogen-containing compound, melamine, melamine resin, succinoguanamine, and other compounds having a triazine ring are effective.
【0012】本発明における難燃樹脂組成物には、樹脂
の改質剤、例えば滑剤、熱安定剤、紫外線吸収剤、耐候
安定剤を用いることが出来る。In the flame-retardant resin composition of the present invention, a resin modifier such as a lubricant, a heat stabilizer, an ultraviolet absorber and a weather resistance stabilizer can be used.
【0013】[0013]
【0014】[0014]
【実施例1〜9】 無電解メッキにより安定化した赤リンの調整(P01、
P02) 平均粒子径20μ工業用赤リン100gを0.1g/1
の濃度の三塩化パラジウム−1規定塩酸溶液1Lの入っ
た3Lのビーカに入れ室温で10分反応させた後濾過、
乾燥した。Examples 1 to 9 Preparation of red phosphorus stabilized by electroless plating (P01,
P02) Average particle size 20μ Industrial red phosphorus 100g 0.1g / 1
Palladium trichloride-1N hydrochloric acid solution having a concentration of 1 L was placed in a 3 L beaker, reacted at room temperature for 10 minutes, and then filtered,
Dried.
【0015】錯化剤として塩化アンモニュウムを含む2
0g/1の水溶液1Lに、上記塩化パラジウムで処理し
た赤リンをいれ、攪拌し懸濁状態にする。60℃に加温
した後、224g/1の硫酸ニッケル41mlと還元液
として226g/l次亜燐酸ナトリウムと128g/l
の水酸化ナトリウム混合液41mlを別々にビーカー連
続フィードし、混合液に加え、30分反応させた。2 containing ammonium chloride as a complexing agent
The red phosphorus treated with the above palladium chloride is added to 1 L of a 0 g / 1 aqueous solution, and stirred to make a suspension. After heating to 60 ° C, 41 ml of 224 g / 1 nickel sulfate and 226 g / l sodium hypophosphite as a reducing solution and 128 g / l
41 ml of the sodium hydroxide mixed solution of was separately fed continuously in a beaker, added to the mixed solution, and reacted for 30 minutes.
【0016】得られた安定化された赤リン(p−O)を
光学顕微鏡で観察したところ、赤リンの粒子表面に完全
に均一に、金属光沢する被膜が形成されていた。使用し
たNiの98%、は被膜形成に使用されていた。When the stabilized red phosphorus (p-O) thus obtained was observed with an optical microscope, it was found that a film having a metallic luster was completely and uniformly formed on the surface of the red phosphorus particles. 98% of the Ni used was used for film formation.
【0017】[0017]
【難燃樹脂組成物】ここで得られた安定化赤リン(赤リ
ンとして98wt%)と熱可塑性樹脂を表1の様に配合
し20mm二軸押出機、シリンダー温度230℃押し出
し、難燃樹脂組成物としてペレットを得、評価した。表
1に難燃樹脂組成物の配合量、とその物性、難燃性をし
めす。[Flame-retardant resin composition] Stabilized red phosphorus (98 wt% as red phosphorus) obtained here and a thermoplastic resin are blended as shown in Table 1, and a 20 mm twin-screw extruder, cylinder temperature 230 ° C. extruded, flame-retardant resin Pellets were obtained as compositions and evaluated. Table 1 shows the blending amount of the flame-retardant resin composition, its physical properties and flame retardancy.
【0018】[0018]
【ホスフインの測定方法】サンプリング方法:押出機ベ
ントガス、燃焼試験時の燃焼ガスの真上にロートを置
き、フイルターを通して自動サンプラーで10mlのガ
スをガスクロマトグラフのカラムに導入した。ガステッ
クのクロマトテックGGC−01、検出器は定電位電解
式ガス検出器 PED、充電剤はポラパック−QSを用
いた。[Method of measuring phosphine] Sampling method: A funnel was placed directly above the vent gas of the extruder and the combustion gas at the time of the combustion test, and 10 ml of gas was introduced into the column of the gas chromatograph with an automatic sampler through the filter. Gastech's Chromatotech GGC-01, the detector used was a potentiostatic electrolysis gas detector PED, and the charging agent was Porapack-QS.
【0019】[0019]
【比較例1】 樹脂コートにより安定化された赤リンの
調整 赤リン200g、純水2Lをビーカに入れ、50℃に加
温した。半水溶性熱硬化型フェノール−ホルムアルデヒ
ド樹脂、三和ケミカル製PW701)200gを添加攪
拌し、温度を90℃にあげ1時間反応させた。濾過、洗
浄を行い60℃で乾燥させた。得られた樹脂コート赤リ
ンを150℃で30分間硬化反応させた。Comparative Example 1 Preparation of Red Phosphorus Stabilized by Resin Coating 200 g of red phosphorus and 2 L of pure water were placed in a beaker and heated to 50 ° C. 200 g of semi-water-soluble thermosetting phenol-formaldehyde resin, PW701, manufactured by Sanwa Chemical Co., Ltd. was added and stirred, and the temperature was raised to 90 ° C. and reacted for 1 hour. It was filtered, washed and dried at 60 ° C. The obtained resin-coated red phosphorus was cured at 150 ° C. for 30 minutes.
【0020】(P−02)得られた安定化赤リンを用い
て表1に示す評価を行った。(P-02) The obtained stabilized red phosphorus was evaluated as shown in Table 1.
【0021】[0021]
【比較例2】安定化操作をしていない赤リン(日本工業
製)(P−03)を用いて表1に示す評価を行った。Comparative Example 2 The evaluation shown in Table 1 was carried out using red phosphorus (manufactured by Nippon Kogyo Co., Ltd.) (P-03) which was not subjected to the stabilizing operation.
【0022】[0022]
【表1】 [Table 1]
【0023】[0023]
【発明の効果】表1により明らかなように、本発明の難
燃樹脂組成物は、安定化赤リンを用いることにより、難
燃性、加工性、耐衝撃性、耐熱性に優れた性能を示す。
その結果難燃性を要求するOA用途、TV等の家電用途
の樹脂成形部品として工業的に応用する事が可能であ
る。As is clear from Table 1, the flame-retardant resin composition of the present invention exhibits excellent flame retardancy, processability, impact resistance and heat resistance by using stabilized red phosphorus. Show.
As a result, it can be industrially applied as a resin molded component for OA applications requiring flame retardancy and home appliances such as TVs.
Claims (1)
塑性樹脂からなる難燃樹脂組成物。1. A flame retardant resin composition comprising an electroless plated red phosphorus flame retardant and a thermoplastic resin.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3913792A JPH05239260A (en) | 1992-02-26 | 1992-02-26 | Flame-retarding resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3913792A JPH05239260A (en) | 1992-02-26 | 1992-02-26 | Flame-retarding resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH05239260A true JPH05239260A (en) | 1993-09-17 |
Family
ID=12544722
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3913792A Pending JPH05239260A (en) | 1992-02-26 | 1992-02-26 | Flame-retarding resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH05239260A (en) |
-
1992
- 1992-02-26 JP JP3913792A patent/JPH05239260A/en active Pending
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