JPH10338818A - Acid-resistant magnesium hydroxide particle flame retardant and flame-retardant resin composition - Google Patents
Acid-resistant magnesium hydroxide particle flame retardant and flame-retardant resin compositionInfo
- Publication number
- JPH10338818A JPH10338818A JP14939697A JP14939697A JPH10338818A JP H10338818 A JPH10338818 A JP H10338818A JP 14939697 A JP14939697 A JP 14939697A JP 14939697 A JP14939697 A JP 14939697A JP H10338818 A JPH10338818 A JP H10338818A
- Authority
- JP
- Japan
- Prior art keywords
- magnesium hydroxide
- acid
- flame retardant
- aluminum
- 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.)
- Granted
Links
Landscapes
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、樹脂に配合した場
合耐酸性並びに分散性に優れ、かつ樹脂の加工時に発泡
が抑えた加工特性を有する水酸化マグネシウム粒子より
なる難燃剤およびそれを含有した難燃性樹脂組成物に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame retardant comprising magnesium hydroxide particles having excellent acid resistance and dispersibility when incorporated into a resin, and having processing characteristics of suppressing foaming during processing of the resin, and a flame retardant containing the same. The present invention relates to a flame-retardant resin composition.
【０００２】[0002]
【従来の技術】人の多く集まる公共施設や排気が不十分
な地下施設等の火災時における有毒な燃焼ガスの発生は
問題視されており、この問題を軽減するため、非ハロゲ
ン系合成樹脂が使われ、またその難燃剤または難燃性充
填剤として水酸化マグネシウムや水酸化アルミニウムな
どの金属水酸化物を利用することは従来からよく知られ
ている。2. Description of the Related Art The generation of toxic combustion gas at the time of fires in public facilities where many people gather and underground facilities where exhaust is insufficient is regarded as a problem. To alleviate this problem, non-halogen-based synthetic resins are used. The use of metal hydroxides such as magnesium hydroxide or aluminum hydroxide as flame retardants or flame retardant fillers is well known in the art.
【０００３】水酸化マグネシウムの場合、基本的にはア
ルカリ物質であり、酸と反応し易く、そのため多量に配
合した樹脂成型体が長期間炭酸含有水、酸性雨等にさら
されると水酸化マグネシウム粒子が溶解してその跡にサ
ブミクロンの大きさのくぼみができ、可視光を散乱して
成型物表面が白く見えたり、または成型物表面に酸と反
応して生成した炭酸マグネシウム等が析出して白く見え
る（白化減少）という問題が起こる。[0003] Magnesium hydroxide is basically an alkali substance and easily reacts with an acid. Therefore, when a large amount of a resin molding is exposed to water containing carbonic acid, acid rain, etc. for a long time, magnesium hydroxide particles are formed. Dissolves to form submicron-sized dents in the traces, scatter visible light, and the molded product surface looks white, or magnesium carbonate generated by reaction with acid on the molded product surface precipitates The problem of white appearance (decrease in whitening) occurs.
【０００４】難燃剤グレイドとして現状使われている水
酸化マグネシウムは結晶欠陥を少なくし、結晶粒子サイ
ズを樹脂組成物の難燃性および物性を低下させない限度
で大きくし、酸反応性を小さくしており、さらに高級脂
肪酸塩やリン酸で表面処理して耐水性および耐酸性を付
与して実用に供されている。Magnesium hydroxide, which is currently used as a flame retardant grade, reduces crystal defects, increases the crystal particle size as long as the flame retardancy and physical properties of the resin composition are not reduced, and reduces acid reactivity. In addition, it is put to practical use by imparting water resistance and acid resistance by surface treatment with a higher fatty acid salt or phosphoric acid.
【０００５】しかしながら、炭酸ガスが存在する高温多
湿雰囲気下での用途や酸性雨にさらされる場所での用途
では、またより高難燃レベルが各用途分野から要求があ
り、これに対応するため配合量を多くすると、それだけ
樹脂組成物の耐酸性は低下するので、さらに耐酸性の強
化された水酸化マグネシウム粒子が望まれている。However, in applications under a high-temperature and high-humidity atmosphere where carbon dioxide gas is present or in locations exposed to acid rain, a higher flame-retardant level is required from each application field. When the amount is increased, the acid resistance of the resin composition is reduced accordingly. Therefore, magnesium hydroxide particles having further enhanced acid resistance are desired.
【０００６】白化現象を解決する方法として特開平１−
２３４４９３号公報には、水酸化マグネシウム粒子表面
をポリ塩化アルミニウム、ケイ酸ソーダおよびヘキサメ
タリン酸ソーダから選ばれる無機高分子組成物との混合
物にし、その無機系高分子はＡｌ2Ｏ3，ＳｉＯ2、Ｐ2Ｏ
5として合計で１から１０重量％とすることを特徴とし
た難燃剤を提供している。しかしながらこの方法では粒
子が凝集しやすく、付着水分も多くなるため、加工性、
外観および物性において十分満足のいく樹脂組成物が得
られない。As a method for solving the whitening phenomenon, Japanese Patent Laid-Open No.
No. 234493 discloses that the surface of magnesium hydroxide particles is made into a mixture with an inorganic polymer composition selected from polyaluminum chloride, sodium silicate and sodium hexametaphosphate, wherein the inorganic polymer is Al 2 O 3 , SiO 2 , P 2 O
5 provides a flame retardant characterized in that the total is 1 to 10% by weight. However, in this method, the particles are easily aggregated and the attached moisture increases, so that the processability and
A resin composition that is sufficiently satisfactory in appearance and physical properties cannot be obtained.
【０００７】また、特開平１−２４５０３９号公報に
は、水酸基を有する金属化合物１００重量部の粒子表面
に高級脂肪酸のアルカリ金属塩を０.５から１０重量部
添加し、なお被覆されていない部分にホウ酸またはケイ
酸の水不溶性塩を形成させることを特徴とした難燃化剤
を開示している。しかしながらこの方法でも表面に親水
性の無機化合物が存在し、樹脂への分散性が十分満足を
得ていない。Japanese Patent Application Laid-Open No. 1-245039 discloses that an alkali metal salt of a higher fatty acid is added in an amount of 0.5 to 10 parts by weight to the surface of 100 parts by weight of a metal compound having a hydroxyl group, Discloses a flame retardant characterized by forming a water-insoluble salt of boric acid or silicic acid. However, even in this method, a hydrophilic inorganic compound exists on the surface, and dispersibility in a resin is not sufficiently obtained.
【０００８】一方、水酸化アルミニウムは、水酸化マグ
ネシウムに比較して分解温度が低く、大気圧で加熱する
と約１８０℃から分解が始まり、３００℃までに結晶構
造の約８０％の水分が放出される。水酸化アルミニウム
を難燃剤として用いて２００℃以上の温度で加工すると
発泡現象を起こしたり、インジェクション加工時にはシ
ルバーストリークが発生する欠点があった。On the other hand, aluminum hydroxide has a lower decomposition temperature than magnesium hydroxide. When heated at atmospheric pressure, decomposition starts at about 180 ° C., and about 80% of the crystal structure of water is released by 300 ° C. You. When processing is performed at a temperature of 200 ° C. or more using aluminum hydroxide as a flame retardant, there are disadvantages that a foaming phenomenon occurs and silver streaks occur during injection processing.
【０００９】[0009]
【発明が解決しようとする課題】前記したように水酸化
マグネシウムを難燃剤とした樹脂組成物は、耐酸性、耐
炭酸ガス性に劣る。具体的には樹脂組成物中の水酸化マ
グネシウムが空気中の炭酸ガスと反応し成型物表面に炭
酸マグネシウムを析出させ、いわゆる白化現象を起こし
たり、また酸性雨による水酸化マグネシウムの溶出によ
る樹脂組成の変化等を起こし難燃性を低下させるという
問題点がある。近年、水酸化マグネシウムの耐酸性、耐
炭酸ガス性を改良する試みがなされているが、凝集性が
強くなり樹脂への分散性が悪いため、機械的物性、外観
ともに実用に耐えられない。本発明の目的は、これらの
問題点を改善できる難燃化剤および難燃性樹脂組成物を
提供することにある。As described above, a resin composition using magnesium hydroxide as a flame retardant is inferior in acid resistance and carbon dioxide gas resistance. Specifically, the magnesium hydroxide in the resin composition reacts with carbon dioxide in the air to precipitate magnesium carbonate on the surface of the molded product, causing a so-called whitening phenomenon, and the resin composition caused by elution of magnesium hydroxide due to acid rain. This causes a problem that the flame retardancy is reduced due to a change in the flame retardancy. In recent years, attempts have been made to improve the acid resistance and carbon dioxide resistance of magnesium hydroxide. However, since the cohesion is high and the dispersibility in the resin is poor, both the mechanical properties and the appearance are not practical. An object of the present invention is to provide a flame retardant and a flame retardant resin composition which can improve these problems.
【００１０】[0010]
【課題を解決するための手段】本発明者らの研究によれ
ば、前記本発明の目的は、水酸化マグネシウム粒子の表
面に、水酸化マグネシウム粒子に対してＡｌ2Ｏ3に換算
して０.０５〜５重量％に相当する量の水酸化アルミニ
ウムが被覆層として形成された耐酸性水酸化マグネシウ
ム粒子よりなる難燃剤およびその難燃剤の一定割合を含
有した難燃性樹脂組成物によって達成されることが見出
された。According to the study of the present inventors, the object of the present invention is to provide a surface of magnesium hydroxide particles having a particle diameter of 0% in terms of Al 2 O 3 with respect to the magnesium hydroxide particles. An amount of aluminum hydroxide equivalent to 0.05 to 5% by weight is achieved by a flame retardant comprising acid-resistant magnesium hydroxide particles formed as a coating layer and a flame retardant resin composition containing a certain proportion of the flame retardant. Was found.
【００１１】本発明で用いられる水酸化マグネシウム粒
子としては、 １.酸化マグネシウムを水和させて徐々に水酸化マグネ
シウムを生成させる。 ２.マグネシウム塩の水溶液とアルカリとの反応で合成
された物 ３.天然に産するブルース石を粉砕した物 等の方法で得られる。これらは特別限定されるものでは
なく、従来の公知の方法で得られたものでよい。例えば
特開昭５２−１１５７９９号公報に開示された、塩化マ
グネシウムもしくは硝酸マグネシウムとアルカリ性物質
を反応させマグネシウムの塩基性塩を得た後、加圧条件
下に加熱して水酸化マグネシウムを得る方法を例示する
ことができる。このようにして得られた水酸化マグネシ
ウムはＢＥＴ比表面積が２０ｍ2／ｇ以下、好ましくは
３〜１５ｍ2／ｇ、平均粒径５ミクロン（μｍ）以下、
好ましくは平均粒径０.１〜４ミクロン（μｍ）の難燃
剤として用いられる水酸化マグネシウムであればよく、
そのものに例えば下記の方法により水酸化アルミニウム
被覆を形成すればよい。The magnesium hydroxide particles used in the present invention are as follows: 1. Hydration of magnesium oxide to gradually produce magnesium hydroxide. 2. A product synthesized by the reaction of an aqueous solution of a magnesium salt with an alkali. 3. A product obtained by crushing a naturally occurring bruceite. These are not particularly limited, and may be obtained by a conventionally known method. For example, a method disclosed in JP-A-52-115799, in which magnesium chloride or magnesium nitrate is reacted with an alkaline substance to obtain a basic salt of magnesium, and then heated under pressure to obtain magnesium hydroxide. Examples can be given. The magnesium hydroxide thus obtained has a BET specific surface area of 20 m 2 / g or less, preferably 3 to 15 m 2 / g, and an average particle diameter of 5 μm (μm) or less.
Preferably, magnesium hydroxide used as a flame retardant having an average particle size of 0.1 to 4 microns (μm) may be used.
For example, an aluminum hydroxide coating may be formed thereon by the following method, for example.
【００１２】本発明の水酸化マグネシウム粒子の表面に
おける水酸化アルミニウム被覆層は次のようにして形成
される。その被覆方法としては、特別限定されるもので
はなく、水酸化マグネシウム粒子スラリー中で水酸化ア
ルミニウム化合物をその粒子表面に中和析出させればよ
く、例えば上記水酸化マグネシウムの水性スラリーに水
酸化ナトリウムを、後から添加する水溶性アルミニウム
塩の全部または一部を中和析出に要する必要量をあらか
じめ加えておき、徐々にアルミニウム塩水溶液を攪拌し
ながら添加する方法もしくは水酸化ナトリウム水溶液と
アルミニウム塩水溶液を定量ポンプを使って、水酸化マ
グネシウムスラリー中に同時に注下する方法が好まし
い。ここで用いるアルカリは、水酸化ナトリウムに限ら
ず、アンモニア水または消石灰等を用いてもよい。ま
た、アルミニウム塩は塩化物、硝酸塩、硫酸塩を用いる
ことができる。またアルミン酸ナトリウムを用いること
もできるが、この場合は水酸化マグネシウムスラリー中
に必要量のアルミン酸ナトリウムを添加し、さらに攪拌
下に塩酸、硝酸、硫酸等の希薄水溶液または酢酸などの
弱酸性の水溶液を徐々に添加する、またはそれらを別々
に同時注下する。水酸化アルミニウム被覆層形成条件と
しては、注下終了時のｐＨが約５〜１１好ましくは約６
〜１０、温度０〜１００℃の範囲であれば問題ないが通
常は約２０〜５０℃が好適である。The aluminum hydroxide coating layer on the surface of the magnesium hydroxide particles of the present invention is formed as follows. The coating method is not particularly limited, and the aluminum hydroxide compound may be neutralized and precipitated on the surface of the magnesium hydroxide particles in the magnesium hydroxide particle slurry. Is added in advance in a necessary amount for neutralization precipitation of all or a part of the water-soluble aluminum salt to be added later, and gradually adding the aluminum salt aqueous solution while stirring, or a sodium hydroxide aqueous solution and an aluminum salt aqueous solution Is simultaneously poured into a magnesium hydroxide slurry using a metering pump. The alkali used here is not limited to sodium hydroxide, but may be ammonia water or slaked lime. In addition, chlorides, nitrates, and sulfates can be used as the aluminum salt. Also, sodium aluminate can be used.In this case, a necessary amount of sodium aluminate is added to the magnesium hydroxide slurry, and further, a weak aqueous solution such as hydrochloric acid, nitric acid, sulfuric acid or a weak acidic solution such as acetic acid is added with stirring. Add the aqueous solution slowly or co-pour them separately. As the conditions for forming the aluminum hydroxide coating layer, the pH at the end of pouring is about 5 to 11, preferably about 6
There is no problem if the temperature is in the range of from 10 to 10 and the temperature is in the range of 0 to 100 ° C.
【００１３】被覆量としては、水酸化アルミニウム化合
物を水酸化マグネシウム表面に単分子層吸着させれば十
分効果を発揮でき、例えば、ＢＥＴ比表面積が７ｍ2／
ｇの水酸化マグネシウムであれば、水酸化アルミニウム
として計算して、水酸化マグネシウム１モルに対して約
７ミリモル添加すればよいことになる。しかしながら耐
酸性、耐炭酸ガス性を向上させるためには、必ずしも単
分子層でなくても、ある一定の範囲であれば十分効果を
発揮できる。すなわち水酸化マグネシウム粒子表面に、
水酸化アルミニウムをＡｌ2Ｏ3換算で０.０５重量％か
ら５.０重量％、好ましくは０.３重量％から１.０重量
％の被覆層を形成させればよく、０.０５重量％より少
ないと耐酸性の改善効果が小さく、一方５重量％より多
いとＢＥＴ比表面積が高くなり凝集するため、加工性が
悪く、発泡等による成型物の外観等が悪くなる。A sufficient effect can be obtained if the aluminum hydroxide compound is adsorbed on the surface of the magnesium hydroxide in a monomolecular layer, for example, the coating amount is 7 m 2 / cm 2 .
In the case of g of magnesium hydroxide, it is sufficient to add about 7 mmol per 1 mol of magnesium hydroxide, calculated as aluminum hydroxide. However, in order to improve the acid resistance and the carbon dioxide gas resistance, a sufficient effect can be exerted within a certain range even if the layer is not necessarily a monolayer. That is, on the surface of the magnesium hydroxide particles,
Aluminum hydroxide may be formed into a coating layer of 0.05 to 5.0% by weight, preferably 0.3 to 1.0% by weight in terms of Al 2 O 3 , and 0.05% by weight. When the amount is less than the above, the effect of improving the acid resistance is small. On the other hand, when the amount is more than 5% by weight, the BET specific surface area is increased and the particles are aggregated.
【００１４】次に得られた水酸化アルミニウムを被覆し
た水酸化マグネシウムは、そのまま利用することもでき
るが、高級脂肪酸、リン酸エステルまたはそれらのアル
カリ金属塩で表面処理して用いることにより、さらに耐
酸性が向上できかつ樹脂との相溶性、分散性をさらに向
上することができ、成形加工性が改良され、さらに成形
品の物理的性質の向上により好ましい結果を与えること
ができる。例えば、ステアリン酸ナトリウムの水溶液
に、上記水酸化マグネシウム粒子粉末を、十分な攪拌条
件下に添加したり、あるいはまた、上記水酸化マグネシ
ウム粒子粉末の懸濁液にステアリン酸ナトリウム水溶液
を十分な攪拌条件下に添加したりする手段で、本発明で
用いる水酸化マグネシウム難燃剤の表面上に、界面活性
剤を化学的に吸着させることができる。吸着させる界面
活性剤の量は、該水酸化マグネシウム難燃剤の重量に基
づいて約０.１〜約１０重量％、好ましくは０.５〜５重
量％程度がよい。高級脂肪酸またはそのアルカリ塩の具
体例としてはステアリン酸ナトリウム、ステアリン酸カ
リウム、オレイン酸ナトリウム、オレイン酸カリウム、
パルミチン酸ナトリウム、アラキジン酸ナトリウム、パ
ルミチン酸カリウム、ラウリン酸ナトリウム、ラウリン
酸カリウム、ベヘン酸カリウム等を挙げることができ
る。リン酸エステルの具体例としては、オレイルアルコ
ールリン酸エステルのナトリウム塩、ステアリルアルコ
ールリン酸エステルのナトリウム塩、エルカアルコール
リン酸エステルのナトリウム塩等のモノエステルまたは
ジエステルおよびこれらの混合物等を挙げることができ
る。また樹脂組成物のさらなる物性向上のため、シラン
カップリング剤、チタンカップリング剤等のカップリン
グ剤で処理して用いることもできる。The obtained magnesium hydroxide coated with aluminum hydroxide can be used as it is, but it can be further treated with a higher fatty acid, a phosphoric acid ester or an alkali metal salt thereof to obtain an acid-resistant material. The properties can be improved, the compatibility with the resin and the dispersibility can be further improved, the moldability can be improved, and more favorable results can be obtained by improving the physical properties of the molded article. For example, the magnesium hydroxide particle powder is added to an aqueous solution of sodium stearate under sufficient stirring conditions, or the sodium stearate aqueous solution is added to a suspension of the magnesium hydroxide particle powder under sufficient stirring conditions. The surfactant can be chemically adsorbed on the surface of the magnesium hydroxide flame retardant used in the present invention by means of addition below. The amount of the surfactant to be adsorbed is about 0.1 to about 10% by weight, preferably about 0.5 to 5% by weight, based on the weight of the magnesium hydroxide flame retardant. Specific examples of higher fatty acids or alkali salts thereof include sodium stearate, potassium stearate, sodium oleate, potassium oleate,
Examples thereof include sodium palmitate, sodium arachidate, potassium palmitate, sodium laurate, potassium laurate, and potassium behenate. Specific examples of the phosphate ester include monoesters or diesters such as sodium salt of oleyl alcohol phosphate, sodium salt of stearyl alcohol phosphate, sodium salt of eruka alcohol phosphate, and mixtures thereof. it can. In order to further improve the physical properties of the resin composition, the resin composition can be used after being treated with a coupling agent such as a silane coupling agent or a titanium coupling agent.
【００１５】本発明の前記水酸化マグネシウム粒子より
なる難燃剤は、合成樹脂中に配合して難燃性樹脂組成物
として使用される。合成樹脂としては特に制限されない
が、ポリオレフィン類、ポリアミド類、エポキシ樹脂な
どの熱可塑性樹脂または熱硬化性樹脂のいずれでもよ
く、特に前者であるのが適当である。配合割合は、合成
樹脂１００重量部に対して、本発明の水酸化マグネシウ
ム粒子よりなる難燃剤が２０〜２５０重量部、好ましく
は５０〜２００重量部の範囲である。The flame retardant comprising the magnesium hydroxide particles of the present invention is used as a flame retardant resin composition by blending it in a synthetic resin. The synthetic resin is not particularly limited, but may be any of a thermoplastic resin such as a polyolefin, a polyamide, and an epoxy resin or a thermosetting resin, and the former is particularly suitable. The mixing ratio is such that the flame retardant comprising the magnesium hydroxide particles of the present invention is in the range of 20 to 250 parts by weight, preferably 50 to 200 parts by weight, based on 100 parts by weight of the synthetic resin.
【００１６】合成樹脂として熱可塑性樹脂を使用する場
合、その例としては、例えばエチレン、プロピレン、ブ
テン−１その他のα−オレフィン類の重合体もしくは共
重合体；このようなαオレフィンの１種もしくは複数種
と共役もしくは非共役ジエン類との共重合体等のオレフ
ィン系樹脂が好ましい。具体的には、ポリエチレン、ポ
リプロピレン、エチレン−ブテンコポリマー、エチレン
−プロピレンコポリマー、エチレン−アクリル酸エチル
コポリマー、エチレン−酢酸エチルコポリマー、エチレ
ン酢酸ビニルコポリマー、エチレン−メタクリル酸メチ
ルコポリマー等を挙げることができ、単独で用いてもよ
く２種以上を混合して用いてもよい。When a thermoplastic resin is used as the synthetic resin, examples thereof include polymers or copolymers of ethylene, propylene, butene-1 and other α-olefins; one of such α-olefins or Olefin resins such as copolymers of a plurality of conjugated or non-conjugated dienes are preferred. Specifically, polyethylene, polypropylene, ethylene-butene copolymer, ethylene-propylene copolymer, ethylene-ethyl acrylate copolymer, ethylene-ethyl acetate copolymer, ethylene vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, and the like, They may be used alone or in combination of two or more.
【００１７】樹脂と水酸化マグネシウム粒子よりなる難
燃剤との配合方法には、特別な制約はなく、これら添加
剤を樹脂に均一に混合しうる任意の手段、例えば押し出
し混合、ロール混合、バンバリー混合等の公知の装置を
用いて加熱溶融・混練することができる。成形は、射出
成形、押し出し成形、カレンダーロール成形などの手段
で行なうことができる。There are no particular restrictions on the method of compounding the resin and the flame retardant comprising magnesium hydroxide particles, and any means capable of uniformly mixing these additives with the resin, such as extrusion mixing, roll mixing, Banbury mixing, etc. It can be heated and melted and kneaded using a known device such as The molding can be performed by means such as injection molding, extrusion molding, calender roll molding and the like.
【００１８】かくして得られた本発明の難燃性樹脂組成
物は、さらに他の慣用の添加剤類を含有することができ
る。その例としては、例えば、酸化防止剤、架橋剤、滑
剤、軟化剤、分散剤、充填剤、着色剤、難燃助剤、帯電
防止剤、光安定剤および紫外線吸収等の耐候性改善剤等
を挙げることができる。The flame-retardant resin composition of the present invention thus obtained can further contain other conventional additives. Examples thereof include, for example, antioxidants, crosslinking agents, lubricants, softeners, dispersants, fillers, coloring agents, flame retardant aids, antistatic agents, light stabilizers, and weather resistance improvers such as ultraviolet absorption. Can be mentioned.
【００１９】[0019]
【発明の効果】本発明によれば、水酸化マグネシウム粒
子の表面上に、水酸化アルミニウムの被覆層を形成させ
ることにより、耐酸性、耐炭酸ガス性が著しく改善さ
れ、樹脂成型品の炭酸ガスおよび酸性雨による白化現象
を起こさず、かつ少量の水酸化アルミニウム化合物の被
覆であるため発泡も起きず、表面外観の優れた難燃性樹
脂成型物が得られる。またアニオン性化合物で被覆処理
したものと比較して表面が水酸化アルミニウム層である
ため、高級脂肪酸アルカリ塩による表面処理が容易に行
われ、樹脂に対する分散性をさらに優れたものにするこ
とができる。According to the present invention, by forming a coating layer of aluminum hydroxide on the surface of magnesium hydroxide particles, acid resistance and carbon dioxide gas resistance are remarkably improved, and carbon dioxide gas of a resin molded product is improved. In addition, since a whitening phenomenon due to acid rain does not occur, and since a small amount of the aluminum hydroxide compound is used, foaming does not occur, and a flame-retardant resin molded product having an excellent surface appearance can be obtained. In addition, since the surface is an aluminum hydroxide layer as compared with that coated with an anionic compound, surface treatment with a higher fatty acid alkali salt is easily performed, and dispersibility in resin can be further improved. .
【００２０】[0020]
【実施例】次に実施例および比較例をあげ本発明をさら
に詳述する。 実施例１１−ａ〜１−ｅ ；ＢＥＴ比表面積６.７ｍ2／ｇ、平均粒
子径０.８ミクロンの水酸化マグネシウム粉末１.０ｋｇ
を含む懸濁液１５Ｌ中に、必要量のＮａＯＨを加え攪拌
分散させた試料液を調整し、十分な攪拌下、室温で、濃
度１０ｇ／Ｌの塩化アルミニウム・６水塩水溶液の必要
量を約１０〜３０分かけて徐々に注下した後、安定化さ
せるためさらに３０分間攪拌保持させ、水酸化アルミニ
ウムの被覆層形成処理を行った。得られた固形分を濾
別、洗浄後再び１５Ｌの水に分散させ、約８０℃まで加
熱し、十分な攪拌下に２０ｇのオレイン酸ナトリウムを
含む約８０℃の溶液１Ｌを加え約３０分攪拌した。その
後、脱水、乾燥、粉砕し難燃剤を作成した。耐酸性は、
サンプル０.１ｇの懸濁液のｐＨ４を維持するために消
費した０.１Ｎ塩酸量が５.１５ｍｌに至る時間（分）の
測定、および耐熱性は２００℃までの水分放出量を示差
熱天秤で測定し、表１に表した。Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. Example 1 1-a to 1-e ; 1.0 kg of magnesium hydroxide powder having a BET specific surface area of 6.7 m 2 / g and an average particle diameter of 0.8 μm
The required amount of an aqueous solution of aluminum chloride hexahydrate having a concentration of 10 g / L was added at room temperature under sufficient stirring at room temperature under sufficient stirring to prepare a sample solution prepared by adding a required amount of NaOH to 15 L of a suspension containing After gradually pouring over 10 to 30 minutes, the mixture was stirred and held for 30 minutes for stabilization, and a coating layer forming process of aluminum hydroxide was performed. The obtained solid content was separated by filtration, washed and then dispersed again in 15 L of water, heated to about 80 ° C., added with sufficient stirring, 1 L of a solution of about 80 ° C. containing 20 g of sodium oleate, and stirred for about 30 minutes. did. Then, it was dehydrated, dried and pulverized to prepare a flame retardant. Acid resistance is
Measurement of the time (minutes) required for the amount of 0.1N hydrochloric acid consumed to maintain pH 4 of the suspension of 0.1 g of the sample to reach 5.15 ml, and the heat resistance indicates the amount of water release up to 200 ° C. And are shown in Table 1.
【００２１】１−ｇ；１−ｇにおいてはＢＥＴ比表面積
１２.２ｍ2／ｇの水酸化マグネシウムを用いたほかは、
実施例１−ｄと同じように処理した。１−ｈ； １−ｈは公知の方法で得られた、ＢＥＴ６.７
ｍ2／ｇ、平均粒子径１.０ミクロンの実施例１−ａに共
した水酸化アルミニウム化合物で被覆処理する前の水酸
化マグネシウムを実施例１−ａと同様にオレイン酸ナト
リウムで表面処理し、耐酸性および耐熱性を測定した。１−ｉ； １−ｉはＢＥＴ５５ｍ2／ｇの水酸化マグネシ
ウムを実施例１−ａと同様に水酸化アルミニウム化合物
で被覆処理後、オレイン酸ナトリウム２０ｇで同様に表
面処理したものを例示した。 1-g; In 1-g, magnesium hydroxide having a BET specific surface area of 12.2 m 2 / g was used.
Treated in the same manner as in Example 1-d. 1-h; 1-h was obtained by a known method, BET 6.7
Magnesium hydroxide, before being coated with the aluminum hydroxide compound of Example 1-a having an m 2 / g average particle diameter of 1.0 μm, was surface-treated with sodium oleate in the same manner as in Example 1-a. , Acid resistance and heat resistance were measured. 1-i: 1-i exemplified those obtained by coating magnesium hydroxide having a BET of 55 m 2 / g with an aluminum hydroxide compound in the same manner as in Example 1-a and then surface-treating the same with 20 g of sodium oleate.
【００２２】[0022]
【表１】 [Table 1]
【００２３】実施例２ 実施例２−ａ、２−ｂおよび２−ｃはそれぞれ、実施例
１−ｃ、１−ｄおよび１−ｈにおいて、オレイン酸ナト
リウムをステアリン酸ナトリウム３０ｇに変更したほか
は、全て同じように処理した。Example 2 Examples 2-a, 2-b and 2-c are the same as Examples 1-c, 1-d and 1-h, except that sodium oleate was changed to 30 g of sodium stearate. , All treated the same.
【００２４】[0024]
【表２】 [Table 2]
【００２５】実施例３ 実施例１−ａ〜１−ｉで得られたそれぞれの難燃剤９０
０ｇと、エチレンプロピレンコポリマー（ＭＩ＝２.
７、比重０.９）６００ｇとを、ポリエチレン製袋中で
混合した後、温度２３０℃、回転数８０ｒｐｍに設定さ
れた２軸混練押し出し機にて混練し樹脂組成物を得た。
このペレットを１２０℃、２時間熱風乾燥後、２３０℃
に設定した射出成型機にて成形し各試験片を作成した。
ＪＩＳＫ７１１３の引っ張り試験片１号ダンベルにて、
引っ張り速度５０ｍｍ／分における引っ張り強さ、伸び
を測定。ＪＩＳＫ７１１０の２号Ａアイゾット試験片お
よび８分の１インチＵＬ９４垂直法試験片を作成し、ア
イゾット衝撃強度、難燃性ＵＬ試験、表面外観および耐
炭酸ガス性を調べた。結果を表３に示す。Example 3 Each of the flame retardants 90 obtained in Examples 1-a to 1-i
0 g and an ethylene propylene copolymer (MI = 2.
7, specific gravity 0.9) and 600 g were mixed in a polyethylene bag, and kneaded with a twin-screw kneading extruder set at a temperature of 230 ° C. and a rotation speed of 80 rpm to obtain a resin composition.
The pellets were dried at 120 ° C. for 2 hours with hot air, and then at 230 ° C.
Each test piece was prepared by molding with an injection molding machine set in the above.
With JIS K7113 tensile test piece No. 1 dumbbell,
The tensile strength and elongation at a tensile speed of 50 mm / min were measured. A JIS K 7110 No. 2 A Izod test piece and a 1/8 inch UL94 vertical test piece were prepared, and the Izod impact strength, flame retardant UL test, surface appearance, and carbon dioxide resistance were examined. Table 3 shows the results.
【００２６】評価方法は、ＪＩＳ、ＵＬ規格にそって測
定し、表面外観および耐炭酸ガス性は次の方法で行っ
た。 表面外観： 良好：シルバーストリークがなく、表面がつややかなもの。 ほぼ良好：僅かにシルバーストリークが発生しているが商品価 値を損なわない程度のもの。 不良：発泡や分散不良によるシルバーストリークが顕著に認め られる。 耐炭酸ガス性：ＵＬ９４法難燃試験の１／８インチのテストピースをイオン 交換水５００ｍｌの入ったビーカに浸漬して、２４℃４８時 間、炭酸ガスを１００ｍｌ／分の流量で導入した。イオン交 換水に溶出したマグネシウムの濃度をＩＣＰ発光分析法にて 定量し耐炭酸ガス性とした。The evaluation was carried out according to JIS and UL standards, and the surface appearance and carbon dioxide resistance were evaluated by the following methods. Surface appearance: good: glossy surface without silver streaks. Almost good: Silver streak is slightly generated but does not impair product value. Poor: Silver streaks due to foaming and poor dispersion are remarkably observed. Carbon dioxide resistance: A 1 / 8-inch test piece of the UL94 flame retardant test was immersed in a beaker containing 500 ml of ion-exchanged water, and carbon dioxide was introduced at a flow rate of 100 ml / min at 24 ° C. for 48 hours. The concentration of magnesium eluted in the ion-exchanged water was quantified by ICP emission spectrometry to determine carbon dioxide resistance.
【００２７】[0027]
【表３】 [Table 3]
【００２８】実施例４ 実施例２において得られた２−ａ、２−ｂおよび２−ｃ
のの難燃剤に変えたほかは実施例３と同様にテストピー
スの作成および測定を行った。結果を表４に表した。Example 4 2-a, 2-b and 2-c obtained in Example 2
A test piece was prepared and measured in the same manner as in Example 3 except that the flame retardant was changed. The results are shown in Table 4.
【００２９】[0029]
【表４】 [Table 4]
【００３０】実施例５ ＢＥＴ比表面積６.４ｍ2／ｇ、平均粒子径０.８μｍの
水酸化マグネシウム粉末１.０Ｋｇを含む懸濁液１５Ｌ
中に、アルミン酸ナトリウム（ＮａＡｌ3）２.０モル／
Ｌ水溶液を１００ｍｌ加え、十分混合した後、攪拌下に
１モル／Ｌの塩酸２００ｍｌを徐々に加え、水酸化アル
ミニウム被覆処理を行った。その後、その懸濁液を８０
℃に加温した。別に準備していた８０℃の温水１Ｌにス
テアリルアルコールリン酸エステルのナトリウム塩の３
０ｇを溶解した水溶液を、上記懸濁液に攪拌下に加えた
後、さらに３０分間攪拌し表面処理した。その後脱水、
乾燥、粉砕し、難燃剤を作成した。このものを分析した
結果Ａｌ2Ｏ3として１.０％含まれていた。Example 5 15 L of a suspension containing 1.0 kg of magnesium hydroxide powder having a BET specific surface area of 6.4 m 2 / g and an average particle diameter of 0.8 μm.
In it, sodium aluminate (NaAl 3 ) 2.0 mol /
After 100 ml of L aqueous solution was added and mixed well, 200 ml of 1 mol / L hydrochloric acid was gradually added with stirring to perform aluminum hydroxide coating treatment. Thereafter, the suspension is
Warmed to ° C. To 1 L of warm water at 80 ° C., prepared separately, add 3% of sodium salt of stearyl alcohol phosphate.
An aqueous solution in which 0 g was dissolved was added to the above suspension with stirring, and the mixture was further stirred for 30 minutes to perform surface treatment. Then dehydration,
Drying and crushing produced a flame retardant. As a result of analyzing this, 1.0% was contained as Al 2 O 3 .
【００３１】この難燃剤を９００ｇとポリプロピレンホ
モポリマー（ＭＩ＝５、比重０.９）６００ｇとを混合
し、温度２３０、回転数８００ｒ．ｐ．ｍ．に調整され
た２軸混練押出機にて混練し樹脂組成物を得た。このペ
レットを１２０℃、２時間熱風乾燥後、２３０℃に設定
した射出成形機にてテストピースを作成し、耐炭酸ガス
性を実施例３と同様に調べた。一方水酸化アルミニウム
被覆処理をしていない水酸化マグネシウムについても同
様にステアリルアルコールリン酸エステル処理を行い比
較例とした。結果を表５に示す。A mixture of 900 g of this flame retardant and 600 g of a polypropylene homopolymer (MI = 5, specific gravity 0.9) was prepared at a temperature of 230 and a rotation speed of 800 rpm. p. m. Was kneaded with a twin-screw kneading extruder adjusted to obtain a resin composition. The pellets were dried with hot air at 120 ° C. for 2 hours, and then test pieces were prepared with an injection molding machine set at 230 ° C., and carbon dioxide resistance was examined in the same manner as in Example 3. On the other hand, magnesium hydroxide not coated with aluminum hydroxide was similarly treated with stearyl alcohol phosphate ester to obtain a comparative example. Table 5 shows the results.
【００３２】[0032]
【表５】 [Table 5]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０９Ｃ 3/08 Ｃ０９Ｃ 3/08 Ｃ０９Ｋ 21/02 Ｃ０９Ｋ 21/02 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI C09C 3/08 C09C 3/08 C09K 21/02 C09K 21/02
Claims (7)
化マグネシウム粒子に対してＡｌ2Ｏ3に換算して０.０
５〜５重量％に相当する量の水酸化アルミニウムが被覆
層として形成された耐酸性水酸化マグネシウム粒子より
なる難燃剤。1. The surface of the magnesium hydroxide particles is 0.02 in terms of Al 2 O 3 with respect to the magnesium hydroxide particles.
A flame retardant comprising acid-resistant magnesium hydroxide particles formed as a coating layer with aluminum hydroxide in an amount corresponding to 5 to 5% by weight.
ありかつ平均粒子径が５μｍ以下である耐酸性マグネシ
ウム粒子である請求項１記載の難燃剤。2. The flame retardant according to claim 1, which is acid-resistant magnesium particles having a BET specific surface area of 20 m 2 / g or less and an average particle diameter of 5 μm or less.
Ｏ3に換算して０.３〜１重量％に相当する量の水酸化ア
ルミニウムが被覆層として形成された水酸化マグネシウ
ム粒子よりなる請求項１記載の難燃剤。3. The method according to claim 1, wherein the magnesium hydroxide particles are mixed with Al 2.
Flame retardant according to claim 1, wherein the amount of aluminum hydroxide in terms of O 3 corresponds to 0.3 to 1% by weight consisting of magnesium hydroxide particles formed as a coating layer.
高級脂肪酸、リン酸エステルまたはそれらのアルカリ金
属塩によりさらに表面処理された耐酸性水酸化マグネシ
ウム粒子よりなる請求項１記載の難燃剤。4. The surface of a coating layer of aluminum hydroxide,
2. The flame retardant according to claim 1, comprising acid-resistant magnesium hydroxide particles further surface-treated with a higher fatty acid, a phosphoric ester or an alkali metal salt thereof.
たはアルミン酸ソーダを使用することにより、水酸化マ
グネシウム粒子の表面に水酸化アルミニウムの被覆層を
形成させた耐酸性水酸化アルミニウム粒子よりなる請求
項１記載の難燃剤。5. An acid-resistant aluminum hydroxide particle having a coating layer of aluminum hydroxide formed on the surface of magnesium hydroxide particles by using aluminum chloride, aluminum sulfate or sodium aluminate. Flame retardants.
（ｂ）請求項１記載の難燃剤５０〜２５０重量部より実
質的になる難燃性樹脂組成物。6. A flame-retardant resin composition consisting essentially of (a) 100 parts by weight of a synthetic resin and (b) 50 to 250 parts by weight of the flame retardant of claim 1.
可溶性アルミニウム化合物の水溶液を中和し、該水酸化
マグネシウム粒子表面に水酸化アルミニウムを析出せし
めることを特徴とする請求項１記載の耐酸性水酸化マグ
ネシウム粒子よりなる難燃剤の製造法。7. The acid-resistant hydroxide according to claim 1, wherein the aqueous solution of the water-soluble aluminum compound in the magnesium hydroxide particle slurry is neutralized to precipitate aluminum hydroxide on the surface of the magnesium hydroxide particles. A method for producing a flame retardant comprising magnesium particles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14939697A JP3499716B2 (en) | 1997-06-06 | 1997-06-06 | Acid resistant magnesium hydroxide particle flame retardant and flame retardant resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14939697A JP3499716B2 (en) | 1997-06-06 | 1997-06-06 | Acid resistant magnesium hydroxide particle flame retardant and flame retardant resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10338818A true JPH10338818A (en) | 1998-12-22 |
| JP3499716B2 JP3499716B2 (en) | 2004-02-23 |
Family
ID=15474222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14939697A Expired - Fee Related JP3499716B2 (en) | 1997-06-06 | 1997-06-06 | Acid resistant magnesium hydroxide particle flame retardant and flame retardant resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3499716B2 (en) |
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| EP0949304A2 (en) * | 1998-04-10 | 1999-10-13 | Kyowa Chemical Industry Co., Ltd. | Method of stabilizing an unsaturated fatty acid-treated inorganic compound and use thereof |
| KR20000052086A (en) * | 1999-01-29 | 2000-08-16 | 권기만 | Synthesis of doublelayer hydroxy compound with coordinated carboxyanion |
| JP2005281402A (en) * | 2004-03-29 | 2005-10-13 | C I Kasei Co Ltd | Flame retardant polyester resin composition and film or sheet |
| WO2006006592A1 (en) * | 2004-07-13 | 2006-01-19 | Hitachi Chemical Co., Ltd. | Epoxy resin molding material for sealing and electronic component device |
| JP2007084689A (en) * | 2005-09-22 | 2007-04-05 | Tateho Chem Ind Co Ltd | Coated magnesium hydroxide, method for producing the same and resin composition containing the same and used for electronic part material |
| CN100398627C (en) * | 2006-05-17 | 2008-07-02 | 中国铝业股份有限公司 | Method for chemical preparation of aluminium hydroxide and magnesium hydroxide composite flame-retardant agent |
| US9663389B1 (en) * | 2008-12-17 | 2017-05-30 | Sandia Corporation | Use of MgO doped with a divalent or trivalent metal cation for removing arsenic from water |
| CN112341887A (en) * | 2020-11-26 | 2021-02-09 | 曾万祥 | Water-based flame-retardant coating and preparation method thereof |
| CN114316368A (en) * | 2021-12-30 | 2022-04-12 | 江西广源化工有限责任公司 | Preparation method of aluminum hydroxide/magnesium hydroxide composite inorganic flame retardant |
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1997
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CZ300525B6 (en) * | 1998-04-10 | 2009-06-10 | Kyowa Chemical Industry Co., Ltd. | Method for preparation of inorganic particles with modified surface, composition and product comprising thereof |
| EP0949304A3 (en) * | 1998-04-10 | 2002-07-10 | Kyowa Chemical Industry Co., Ltd. | Method of stabilizing an unsaturated fatty acid-treated inorganic compound and use thereof |
| EP0949304A2 (en) * | 1998-04-10 | 1999-10-13 | Kyowa Chemical Industry Co., Ltd. | Method of stabilizing an unsaturated fatty acid-treated inorganic compound and use thereof |
| KR20000052086A (en) * | 1999-01-29 | 2000-08-16 | 권기만 | Synthesis of doublelayer hydroxy compound with coordinated carboxyanion |
| JP4544889B2 (en) * | 2004-03-29 | 2010-09-15 | シーアイ化成株式会社 | Flame retardant polyester resin composition and film or sheet |
| JP2005281402A (en) * | 2004-03-29 | 2005-10-13 | C I Kasei Co Ltd | Flame retardant polyester resin composition and film or sheet |
| KR100846547B1 (en) | 2004-07-13 | 2008-07-15 | 히다치 가세고교 가부시끼가이샤 | Epoxy resin molding material for sealing and electronic component device |
| WO2006006592A1 (en) * | 2004-07-13 | 2006-01-19 | Hitachi Chemical Co., Ltd. | Epoxy resin molding material for sealing and electronic component device |
| JP2007084689A (en) * | 2005-09-22 | 2007-04-05 | Tateho Chem Ind Co Ltd | Coated magnesium hydroxide, method for producing the same and resin composition containing the same and used for electronic part material |
| CN100398627C (en) * | 2006-05-17 | 2008-07-02 | 中国铝业股份有限公司 | Method for chemical preparation of aluminium hydroxide and magnesium hydroxide composite flame-retardant agent |
| US9663389B1 (en) * | 2008-12-17 | 2017-05-30 | Sandia Corporation | Use of MgO doped with a divalent or trivalent metal cation for removing arsenic from water |
| CN112341887A (en) * | 2020-11-26 | 2021-02-09 | 曾万祥 | Water-based flame-retardant coating and preparation method thereof |
| CN114316368A (en) * | 2021-12-30 | 2022-04-12 | 江西广源化工有限责任公司 | Preparation method of aluminum hydroxide/magnesium hydroxide composite inorganic flame retardant |
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