JP2004269723A - Phosphorus-free magnesium hydroxide-based flame retardant, production method and flame retardant resin composition - Google Patents
Phosphorus-free magnesium hydroxide-based flame retardant, production method and flame retardant resin composition Download PDFInfo
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Description
【０００１】
【発明の技術分野】
本発明は、リンフリーの水酸化マグネシウム系難燃剤、およびそれを配合した難燃性樹脂組成物に関する。更に詳しくは、水酸化マグネシウム粒子を、炭素数（炭素原子数）が１８以上の飽和脂肪酸の、アルカリ金属塩、アンモニウム塩、モノ〜トリアルコールアミン塩で表面処理して第一層の被膜を形成し、更にシランカップリング剤で表面処理して第二層の被膜を形成した、リンフリーの水酸化マグネシウム系難燃剤や、その製造方法、および該難燃剤をリンフリーの樹脂に配合した耐水性に優れた難燃性樹脂組成物に関する。
【０００２】
【従来の技術】
ダイオキシン等の環境問題によって、樹脂のハロゲンフリー難燃化のために、ポリオレフィン系樹脂やエポキシ系樹脂等のハロゲンフリー樹脂等に、ハロゲンフリーの難燃剤である水酸化マグネシウムを添加する方法が一般に実施されている。水酸化マグネシウム系難燃剤を配合した樹脂組成物は、家庭電気製品や自動車等の電線被覆材用途や、ＩＣ封止材、積層板等の電気・電子部品用途等に広く使用されている。しかしながら、雨水や湿気に曝されたり、海岸近くの場所等に置かれると、樹脂組成物の耐水性・耐食塩水性は貧弱で、電気抵抗が大幅に低下する等、絶縁材料としての特性が損なわれる。この原因としては、雨水、湿気、海風等から来る水分や塩分を、樹脂組成物中の水酸化マグネシウム系難燃剤が引き付ける為、樹脂組成物中の水分や塩分が多くなり、電気抵抗が低下することが考えられる。従って、耐水性に優れた水酸化マグネシウム系難燃剤が望まれている。
【０００３】
【特許文献１】特公平６−２８４３号公報
水酸化マグネシウム系難燃剤の耐水性を改善するために、従来から種々の表面処理方法が提案されている。例えば、特公平６−２８４３号は、水酸化マグネシウムをアルコールリン酸エステルのジアルコールアミン塩またはアルカリ金属塩で表面処理する方法を提案し、これにより耐水性等はある程度改善される。しかし、リン酸エステル系の化合物は、燃焼時に有毒なホスフィンガスが発生すること、動物実験で強い生体有害性を示すこと、また焼却・埋立て処分後に、リン化合物が雨水によって河川へ流れるため、富栄養化等の環境汚染の原因となること等のため、人体や環境に優しい物質とは言い難い。このため、家電製品用の電線被覆材料などで、リンフリー化が迫られている。
【０００４】
【発明が解決しようとする課題】
本発明は、リンフリー水酸化マグネシウム系難燃剤とその製造方法、および該難燃剤を配合した耐水性に優れた難燃性樹脂組成物の提供を目的とする。
【０００５】
【課題を解決するための手段】
本発明のリンフリーの水酸化マグネシウム系難燃剤は、水酸化マグネシウム粒子を、炭素数が１８以上の飽和脂肪酸の、アルカリ金属塩、アンモニウム塩、モノアルコールアミン塩、ジアルコールアミン塩、及びモノ〜トリアルコールアミン塩の少なくとも一員で表面処理して、第一層の被膜を形成した後に、更にシランカップリング剤で表面処理して第二層の被膜を形成したことを特徴とする。更に、リンフリーの樹脂１００重量部に対し、上記難燃剤を５〜５００重量部配合すると、耐水性に優れたリンフリー難燃性樹脂組成物が得られる。
【０００６】
本発明で使用する水酸化マグネシウム粒子は、合成物あるいは天然物ブルーサイトのいずれでも良い。
【０００７】
本発明で使用する第一層の被膜を形成するための脂肪酸塩は、炭素数が１８以上の飽和脂肪酸の、アルカリ金属塩、アンモニウム塩、モノ〜トリのアルコールアミン塩である。その飽和脂肪酸としては、例えば、ステアリン酸（Ｃ１７Ｈ３５ＣＯＯＨ、陰イオンとしての式量２８４）、アラキン酸（Ｃ１９Ｈ３９ＣＯＯＨ）、ベヘニン酸（Ｃ２１Ｈ４３ＣＯＯＨ、陰イオンとしての式量３４０）、リグノセリン酸（Ｃ２３Ｈ４７ＣＯＯＨ）、セロチン酸（Ｃ２５Ｈ５１ＣＯＯＨ）、モンタン酸（Ｃ２８Ｈ５７ＣＯＯＨ）、メリシン酸（Ｃ２９Ｈ５９ＣＯＯＨ）等が挙げられる。炭素数が１８よりも少ないと、表面処理剤自体の撥水性効果が低く、難燃剤を混練した樹脂組成物の体積固有抵抗や耐水性は不十分である。なお飽和脂肪酸のアルカリ金属塩のアルカリ金属としては、例えば、Ｌｉ、Ｎａ、Ｋ、Ｒｂ等が用いられる。また、飽和脂肪酸のアルコールアミン塩でのアルコールアミンとしては、メタノールアミン、エタノールアミン、ｎ−プロパノールアミン、ｎ−ブタノールアミン、イソプロパノールアミン、イソブタノールアミン、ｓｅｃ−ブタノールアミン、ｔｅｒｔ−ブタノールアミン等が挙げられる。一方、炭素数が１８以上ではあるが、分子内に不飽和を１個以上含有する脂肪酸では、混練した樹脂組成物の耐水性は極端に劣る。
【０００８】
本発明で使用する第二層の被膜を形成するためのシランカップリング剤は、例えば、ジメチルジメトキシシラン、メチルトリメトキシシラン、ジメチルジエトキシシラン、メチルトリエトキシシラン、ジビニルジメトキシシラン、ビニルトリメトキシシラン、ジビニルジエトキシシラン、ビニルトリエトキシシラン、ビニルトリス（βメトキシエトキシ）シラン、γ−メタクリロキシプロピルメチルジメトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルメチルジエトキシシラン、γ−メタクリロキシプロピルトリエトキシシラン、β−（３、４エポキシシクロヘキシル）エチルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルメチルジメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、Ｎ−フェニル−γ−アミノプロピルトリメトキシシラン、γ−クロロプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシラン、等が挙げられる。
【０００９】
第一層の被膜は難燃剤粒子単位表面積当りに使用する飽和脂肪酸モル数が３μｍｏｌ／ｍ２が好ましく、より好ましくは３〜１５μｍｏｌ／ｍ２、特に好ましくは３〜１０μｍｏｌ／ｍ２とする。第二層の被膜は難燃剤粒子単位表面積当りに使用するシランカップリング剤モル数は２μｍｏｌ／ｍ２以上が好ましく、より好ましくは２〜３０μｍｏｌ／ｍ２、特に好ましくは２〜１５μｍｏｌ／ｍ２とする。飽和脂肪酸が３μｍｏｌ／ｍ２未満、あるいはシランカップリング剤が２μｍｏｌ／ｍ２未満の場合は、粒子表面を完全に被覆するための表面処理剤が不足し、初期の体積固有抵抗や耐水性のレベルが低くなる。
【００１０】
表面処理では例えば、水酸化マグネシウム水懸濁液に、第一層の被膜として調製した飽和脂肪酸塩水溶液を添加して１時間以上攪拌した後、第二層の被膜として調製したシランカップリング剤水溶液を添加して１２時間以上攪拌する。その後、水洗、脱水、乾燥、粉砕して水酸化マグネシウム系難燃剤を得ることができる。添加の順番が逆であったり、脂肪酸とシランカップリング剤を混合した水溶液を用いたりした場合は、樹脂組成物の初期の体積固有抵抗や耐水性のレベルは低下する。
【００１１】
水酸化マグネシウム系難燃剤を配合する樹脂は、ハロゲンフリー、且つリンフリーであれば制限はなく、熱可塑性樹脂でも熱硬化性樹脂でも良い。例えば、ポリエチレン、エチレン−酢酸ビニル共重合体、エチレン−アクリル酸エステル共重合体、エチレン−無水マレイン酸共重合体、ポリプロピレン、ポリスチレン、エポキシ樹脂、フェノール樹脂等が挙げられる。
【００１２】
本発明の難燃性樹脂組成物では、上記の合成樹脂１００重量部に対し、表面処理された水酸化マグネシウム５〜５００重量部を配合する。混練方法では、樹脂と水酸化マグネシウム粒子が加熱溶融して均一に混練できれば良く、加圧式ニーダー、プラストミル、ロール、バンバリーミキサー、１軸あるいは２軸押出機等を使用することができる。
【００１３】
本発明での試験方法を以下に示す。
・ ＢＥＴ比表面積の測定；水酸化マグネシウム粉末を窒素吸着法により測定した。
・ 平均粒子径はレーザー回折法により測定した。
・ 難燃剤粒子単位表面積当りに使用する処理剤モル数は式（４）を用いて求めた。
難燃剤粒子単位表面積当りに使用する処理剤モル数（ｍｏｌ／ｍ２）
＝［難燃剤１ｇ当りに使用する脂肪酸モル数（ｍｏｌ／ｇ）］÷［難燃剤粉末のＢＥＴ比表面積（ｍ２／ｇ）］ （４）
・ 初期の体積固有抵抗の測定および耐水試験；初期の体積固有抵抗は、ＪＩＳ Ｋ６９１１に準拠して混練物を１５０℃でプレス成形し、厚み１ｍｍ×縦１３０ｍｍ×横１３０ ｍｍのシートを作成し、温度３０℃、相対湿度５０ ％の雰囲気下で３時間放置してから、固有抵抗測定電極を用いて５００Ｖの電圧をかけ、１分間充電した後の体積抵抗値を測定し、体積固有抵抗値に換算した。また、耐水性は、シートを８０℃に加温した１０ｗｔ％濃度の食塩水中に９６時間浸せきした後、シート表面の水分を除去する目的で４０℃、８時間シートを乾燥し、前記と同様にして浸せき後の体積固有抵抗値を求めた。
【００１４】
【実施例】
【００１５】
【実施例１】
ＢＥＴ比表面積９．６ ｍ２／ｇ、平均粒子径０．９μｍの合成水酸化マグネシウム１ｋｇを含む水懸濁液５Ｌを撹拌下８０℃に加温し、第一層の被膜としてのモル数が３．５μｍｏｌ／ｍ２となるように、ベヘニン酸ナトリウム水溶液（温度８０℃、濃度１ｗｔ％）を添加して１時間撹拌した。その後、第二層の被膜としてのモル数が８．７μｍｏｌ／ｍ２となるように、酢酸でｐＨが約３に調整したビニルトリメトキシシラン水溶液（温度８０℃、濃度１ｗｔ％）を添加して１２時間攪拌した。その後、水洗、脱水、乾燥、粉砕して表面処理水酸化マグネシウム粉末を得た。次に、エチレン−酢酸ビニル共重合体１００重量部と表面処理された水酸化マグネシウム２００重量部をラボプラストミルにより１５０℃で５分間混練し、プレス成形して１３０×１３０×１ｍｍのサンプルシートを作成し、これを用いて耐水試験を行った。加えたベヘニン酸ナトリウムやビニルトリメトキシシランは、ほぼ全量が水酸化マグネシウム粒子に吸着し、ベヘニン酸ナトリウムやビニルトリメトキシシラン等の添加量は、仕込量と水洗により失われた量の差を示し、仕込量ではない。この点は実施例や比較例を通じて共通とする。
【００１６】
【実施例２】
第一層の被膜としてのモル数が５．５μｍｏｌ／ｍ２となるように、ステアリン酸ジエタノールアミン水溶液（温度８０℃、濃度１ｗｔ％）を添加した以外は、実施例１と同様の操作を行った。
【００１７】
【実施例３】
ＢＥＴ比表面積７．５ ｍ２／ｇ、平均粒子径４．５μｍの天然ブルーサイト１ｋｇを含む水懸濁液５Ｌを撹拌下８０℃に加温し、第一層の被膜としてのモル数が４．５μｍｏｌ／ｍ２となるように、ベヘニン酸アンモニウム水溶液（温度８０℃、濃度１ｗｔ％）を添加して１時間撹拌した。その後、第二層の被膜としてのモル数が２．５μｍｏｌ／ｍ２となるように、酢酸でｐＨが約３に調整したビニルトリメトキシシラン水溶液（温度８０℃、濃度１ｗｔ％）を添加して１２時間攪拌した。その後、実施例１と同様の操作を行った。
【００１８】
【比較例１】
第一層の被膜としてのモル数が２．０μｍｏｌ／ｍ２となるように、ベヘニン酸ナトリウム水溶液を添加した以外は、実施例１と同様の操作を行った。
【００１９】
【比較例２】
モル数が３．５μｍｏｌ／ｍ２となるように、ベヘニン酸ナトリウム水溶液単独で表面処理した以外は、実施例１と同様の操作を行った。
【００２０】
【比較例３】
モル数が８．７μｍｏｌ／ｍ２となるように、ビニルトリメトキシシラン水溶液単独で表面処理した以外は、実施例１と同様の操作を行った。
【００２１】
【比較例４】
第二層の被膜としてのモル数が１．０μｍｏｌ／ｍ２となるように、ビニルトリメトキシシラン水溶液を添加した以外は、実施例３と同様の操作を行った。
【００２２】
【比較例５】
ＢＥＴ比表面積９．６ ｍ２／ｇ、平均粒子径０．９μｍの合成水酸化マグネシウム１ｋｇを含む水懸濁液５Ｌを撹拌下８０℃に加温し、第一層の被膜としてのモル数が８．７μｍｏｌ／ｍ２となるように、酢酸でｐＨが約３に調整したビニルトリメトキシシラン水溶液（温度８０℃、濃度１ｗｔ％）を添加して１２時間攪拌した。その後、第二層の被膜としてのモル数が３．５μｍｏｌ／ｍ２となるように、ベヘニン酸ナトリウム水溶液（温度８０℃、濃度１ｗｔ％）を添加して１時間撹拌した。その後、実施例１と同様の操作を行った。
【００２３】
【比較例６】
ベヘニン酸ナトリウム水溶液（モル数３．５μｍｏｌ／ｍ２、温度８０℃、濃度１ｗｔ％）と、酢酸でｐＨが約３に調整したビニルトリメトキシシラン水溶液（モル数８．７μｍｏｌ／ｍ２、温度８０℃、濃度１ｗｔ％）を混合して調製水溶液を得た。その後、ＢＥＴ比表面積９．６ ｍ２／ｇ、平均粒子径０．９μｍの合成水酸化マグネシウム１ｋｇを含む８０℃に加温した水懸濁液５Ｌに、調製した表面処理剤の混合水溶液を撹拌下に添加し、１２時間攪拌した。その後、実施例１と同様の操作を行った。
【００２４】
【比較例７】
第一層の被膜としてラウリン酸ナトリウム水溶液を用いた以外は、実施例１と同様の操作を行った。
【００２５】
【比較例８】
第一層の被膜としてオレイン酸ナトリウム水溶液を用いた以外は、実施例１と同様の操作を行った。
【００２６】
【比較例９】
ＢＥＴ比表面積９．６ ｍ２／ｇ、平均粒子径０．９μｍの合成水酸化マグネシウム無処理品について、実施例１と同様にして耐水試験を行った。
【００２７】
初期の体積固有抵抗値は、２．０×１０１５Ω・ｃｍ以上（○）、１．０×１０１５Ω・ｃｍ以上２．０×１０１５Ω・ｃｍ未満（△）、１．０×１０１５Ω・ｃｍ未満（×）とした。また、耐水後の体積固有抵抗値は２．０×１０１４Ω・ｃｍ以上（○）、１．０×１０１４Ω・ｃｍ以上２．０×１０１４Ω・ｃｍ未満（△）、１．０×１０１４Ω・ｃｍ未満（×）とした。
【００２８】
【表１】
【表２】
【発明の効果】
本発明によれば、水酸化マグネシウムを炭素数が１８以上の飽和脂肪酸のアルカリ金属塩および／またはアンモニウム塩で表面処理して第一層の被膜を形成し、更にシランカップリング剤で表面処理して第二層の被膜を形成することにより、耐水性に優れたリンフリー難燃剤が提供され、該水酸化マグネシウム系難燃剤を配合することで耐水性の優れた樹脂組成物が提供される。また、この水酸化マグネシウム系難燃剤および該難燃剤を混練した樹脂組成物は、ハロゲンフリー、且つ、リンフリーであり、該樹脂組成物を燃焼させても有害なガスを発生しない等、環境や人体等への負荷が少ない。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a phosphorus-free magnesium hydroxide-based flame retardant and a flame-retardant resin composition containing the same. More specifically, magnesium hydroxide particles are surface-treated with an alkali metal salt, ammonium salt, or mono-to-trialcoholamine salt of a saturated fatty acid having 18 or more carbon atoms (carbon atoms) to form a first layer coating. And a phosphorus-free magnesium hydroxide-based flame retardant having a surface treated with a silane coupling agent to form a second layer coating, a method for producing the same, and a water-resistant resin prepared by blending the flame retardant with a phosphorus-free resin The present invention relates to a flame-retardant resin composition having excellent resistance.
[0002]
[Prior art]
Due to environmental problems such as dioxin, it is common practice to add halogen-free flame retardant magnesium hydroxide to halogen-free resins such as polyolefin resin and epoxy resin in order to make the resin halogen-free flame retardant. Have been. BACKGROUND ART A resin composition containing a magnesium hydroxide-based flame retardant has been widely used for electric wire covering materials for home electric appliances and automobiles, and for electric and electronic parts such as IC sealing materials and laminates. However, when exposed to rainwater or moisture, or placed near a coast, the water resistance and salt water resistance of the resin composition are poor, and the electrical resistance is greatly reduced, and the properties as an insulating material are impaired. It is. As a cause of this, since the magnesium hydroxide-based flame retardant in the resin composition attracts moisture and salt coming from rainwater, moisture, sea breeze, etc., the moisture and salt in the resin composition increase, and the electric resistance decreases. It is possible. Therefore, a magnesium hydroxide flame retardant having excellent water resistance has been desired.
[0003]
[Patent Document 1] Japanese Patent Publication No. 6-2843 In order to improve the water resistance of a magnesium hydroxide-based flame retardant, various surface treatment methods have been conventionally proposed. For example, Japanese Patent Publication No. 6-2843 proposes a method in which magnesium hydroxide is surface-treated with a dialcoholamine salt of an alcoholic phosphate or an alkali metal salt, whereby the water resistance and the like are improved to some extent. However, phosphate-based compounds generate toxic phosphine gas during combustion, exhibit strong biotoxicity in animal tests, and after incineration and landfill disposal, phosphorus compounds flow into rivers by rainwater. Since it causes environmental pollution such as eutrophication, it is hard to say that it is a substance that is friendly to the human body and the environment. For this reason, the use of phosphorus-free materials for electric wire coating materials for home appliances has been pressing.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a phosphorus-free magnesium hydroxide-based flame retardant, a method for producing the same, and a flame-retardant resin composition containing the flame retardant and having excellent water resistance.
[0005]
[Means for Solving the Problems]
The phosphorus-free magnesium hydroxide-based flame retardant of the present invention is characterized in that magnesium hydroxide particles are formed by adding a saturated fatty acid having 18 or more carbon atoms to an alkali metal salt, an ammonium salt, a monoalcoholamine salt, a dialcoholamine salt, and After a surface treatment with at least one member of a trialcoholamine salt to form a first layer film, the surface treatment is further performed with a silane coupling agent to form a second layer film. Furthermore, when 5 to 500 parts by weight of the above flame retardant is blended with respect to 100 parts by weight of the phosphorus-free resin, a phosphorus-free flame-retardant resin composition having excellent water resistance can be obtained.
[0006]
The magnesium hydroxide particles used in the present invention may be either synthetic or natural brucite.
[0007]
The fatty acid salt for forming the first layer film used in the present invention is an alkali metal salt, an ammonium salt or a mono to tri alcoholamine salt of a saturated fatty acid having 18 or more carbon atoms. Examples of the saturated fatty acids include stearic acid (C 17 H 35 COOH, formula weight 284 as an anion), arachiic acid (C 19 H 39 COOH), and behenic acid (C 21 H 43 COOH, a formula as an anion). the amount 340), lignoceric acid (C 23 H 47 COOH), cerotic acid (C 25 H 51 COOH), montanic acid (C 28 H 57 COOH), include melissic acid (C 29 H 59 COOH) and the like. When the number of carbon atoms is less than 18, the water repellency of the surface treatment agent itself is low, and the volume resistivity and the water resistance of the resin composition kneaded with the flame retardant are insufficient. As the alkali metal of the alkali metal salt of a saturated fatty acid, for example, Li, Na, K, Rb and the like are used. Examples of the alcoholamine in the alcoholamine salt of a saturated fatty acid include methanolamine, ethanolamine, n-propanolamine, n-butanolamine, isopropanolamine, isobutanolamine, sec-butanolamine, tert-butanolamine and the like. Can be On the other hand, with a fatty acid having 18 or more carbon atoms but containing one or more unsaturation in the molecule, the water resistance of the kneaded resin composition is extremely poor.
[0008]
The silane coupling agent for forming the second layer coating used in the present invention is, for example, dimethyldimethoxysilane, methyltrimethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, divinyldimethoxysilane, vinyltrimethoxysilane , Divinyldiethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryl Loxypropyltriethoxysilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-amino Propyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, etc. Is mentioned.
[0009]
The number of moles of saturated fatty acid used per unit surface area of the flame retardant particles is preferably 3 μmol / m 2 , more preferably 3 to 15 μmol / m 2 , and particularly preferably 3 to 10 μmol / m 2 . In the coating of the second layer, the number of moles of the silane coupling agent used per unit surface area of the flame retardant particles is preferably 2 μmol / m 2 or more, more preferably 2 to 30 μmol / m 2 , particularly preferably 2 to 15 μmol / m 2 . I do. If less than saturated fatty acids 3 [mu] mol / m 2, or a silane coupling agent is less than 2 [mu] mol / m 2, insufficient surface treatment agent for completely cover the particle surface, the initial volume resistivity and water resistance levels Becomes lower.
[0010]
In the surface treatment, for example, an aqueous solution of a saturated fatty acid salt prepared as a coating of the first layer is added to an aqueous suspension of magnesium hydroxide, and the mixture is stirred for 1 hour or more, and then an aqueous solution of a silane coupling agent prepared as a coating of the second layer. And stir for at least 12 hours. Thereafter, washing with water, dehydration, drying, and pulverization can provide a magnesium hydroxide-based flame retardant. When the order of addition is reversed or when an aqueous solution in which a fatty acid and a silane coupling agent are mixed is used, the initial volume resistivity and the level of water resistance of the resin composition decrease.
[0011]
The resin containing the magnesium hydroxide-based flame retardant is not limited as long as it is halogen-free and phosphorus-free, and may be a thermoplastic resin or a thermosetting resin. For example, polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, ethylene-maleic anhydride copolymer, polypropylene, polystyrene, epoxy resin, phenol resin and the like can be mentioned.
[0012]
In the flame-retardant resin composition of the present invention, 5-500 parts by weight of surface-treated magnesium hydroxide is blended with 100 parts by weight of the above synthetic resin. In the kneading method, it is sufficient that the resin and the magnesium hydroxide particles can be heated and melted to be uniformly kneaded, and a pressure-type kneader, a plast mill, a roll, a Banbury mixer, a single-screw or twin-screw extruder can be used.
[0013]
The test method in the present invention is shown below.
-Measurement of BET specific surface area: Magnesium hydroxide powder was measured by a nitrogen adsorption method.
-The average particle diameter was measured by a laser diffraction method.
-The number of moles of the treating agent used per unit surface area of the flame retardant particles was determined by using the formula (4).
Number of moles of treating agent used per unit surface area of flame retardant particles (mol / m 2 )
= [Molar number of fatty acids used per 1 g of flame retardant (mol / g)] ÷ [BET specific surface area of flame retardant powder (m 2 / g)] (4)
-Initial volume resistivity measurement and water resistance test: The initial volume resistivity was determined by press-molding the kneaded material at 150 ° C in accordance with JIS K6911 to form a sheet having a thickness of 1 mm × length 130 mm × width 130 mm. After leaving for 3 hours in an atmosphere at a temperature of 30 ° C. and a relative humidity of 50%, a voltage of 500 V was applied using a specific resistance measuring electrode, and the volume resistance after charging for 1 minute was measured. Converted. The water resistance was determined by immersing the sheet in a 10 wt% saline solution heated to 80 ° C. for 96 hours, and then drying the sheet at 40 ° C. for 8 hours in order to remove moisture on the sheet surface. The volume resistivity after immersion was determined.
[0014]
【Example】
[0015]
Embodiment 1
5 L of an aqueous suspension containing 1 kg of synthetic magnesium hydroxide having a BET specific surface area of 9.6 m 2 / g and an average particle diameter of 0.9 μm was heated to 80 ° C. with stirring, and the number of moles as a coating of the first layer was increased. An aqueous solution of sodium behenate (temperature: 80 ° C., concentration: 1 wt%) was added so that the concentration became 3.5 μmol / m 2, and the mixture was stirred for 1 hour. Thereafter, an aqueous solution of vinyltrimethoxysilane (temperature: 80 ° C, concentration: 1 wt%) whose pH was adjusted to about 3 with acetic acid was added so that the number of moles as the coating of the second layer became 8.7 µmol / m 2. Stir for 12 hours. Then, it was washed with water, dehydrated, dried and pulverized to obtain a surface-treated magnesium hydroxide powder. Next, 100 parts by weight of the ethylene-vinyl acetate copolymer and 200 parts by weight of the surface-treated magnesium hydroxide were kneaded by a laboplast mill at 150 ° C. for 5 minutes, and press-molded to obtain a 130 × 130 × 1 mm sample sheet. It was prepared and subjected to a water resistance test. Almost all of the added sodium behenate and vinyltrimethoxysilane are adsorbed on the magnesium hydroxide particles, and the added amount of sodium behenate and vinyltrimethoxysilane shows the difference between the charged amount and the amount lost by washing with water. , Not the charge. This point is common throughout the examples and comparative examples.
[0016]
Embodiment 2
The same operation as in Example 1 was performed except that an aqueous solution of diethanolamine stearate (temperature: 80 ° C., concentration: 1 wt%) was added so that the number of moles of the first layer film became 5.5 μmol / m 2 . .
[0017]
Embodiment 3
5 L of an aqueous suspension containing 1 kg of natural brucite having a BET specific surface area of 7.5 m 2 / g and an average particle diameter of 4.5 μm was heated to 80 ° C. with stirring, and the number of moles of the first layer coating film was 4 An aqueous solution of ammonium behenate (temperature: 80 ° C., concentration: 1 wt%) was added to the mixture so that the concentration became 0.5 μmol / m 2, and the mixture was stirred for 1 hour. Thereafter, an aqueous solution of vinyltrimethoxysilane (temperature: 80 ° C., concentration: 1% by weight) whose pH was adjusted to about 3 with acetic acid was added so that the number of moles of the second layer became 2.5 μmol / m 2. Stir for 12 hours. Thereafter, the same operation as in Example 1 was performed.
[0018]
[Comparative Example 1]
The same operation as in Example 1 was performed except that an aqueous solution of sodium behenate was added so that the number of moles of the first layer film became 2.0 μmol / m 2 .
[0019]
[Comparative Example 2]
The same operation as in Example 1 was performed except that the surface treatment was performed with the sodium behenate aqueous solution alone such that the number of moles became 3.5 μmol / m 2 .
[0020]
[Comparative Example 3]
The same operation as in Example 1 was performed, except that the surface treatment was performed with the vinyltrimethoxysilane aqueous solution alone so that the number of moles became 8.7 μmol / m 2 .
[0021]
[Comparative Example 4]
The same operation as in Example 3 was performed except that an aqueous solution of vinyltrimethoxysilane was added so that the number of moles of the second layer as a coating film was 1.0 μmol / m 2 .
[0022]
[Comparative Example 5]
5 L of an aqueous suspension containing 1 kg of synthetic magnesium hydroxide having a BET specific surface area of 9.6 m 2 / g and an average particle size of 0.9 μm was heated to 80 ° C. with stirring, and the number of moles as a first layer coating was increased. An aqueous solution of vinyltrimethoxysilane (temperature: 80 ° C, concentration: 1 wt%) whose pH was adjusted to about 3 with acetic acid was added so that the concentration became 8.7 µmol / m 2, and the mixture was stirred for 12 hours. Thereafter, an aqueous solution of sodium behenate (temperature: 80 ° C., concentration: 1% by weight) was added thereto such that the number of moles of the second layer became 3.5 μmol / m 2 , followed by stirring for 1 hour. Thereafter, the same operation as in Example 1 was performed.
[0023]
[Comparative Example 6]
A sodium behenate aqueous solution (3.5 mol / m 2 , temperature 80 ° C., 1 wt% concentration) and a vinyltrimethoxysilane aqueous solution adjusted to pH 3 with acetic acid (8.7 mol / m 2 , temperature 80) (C, 1 wt%) to obtain a prepared aqueous solution. Then, the mixed aqueous solution of the prepared surface treatment agent was stirred into 5 L of an aqueous suspension containing 1 kg of synthetic magnesium hydroxide having a BET specific surface area of 9.6 m 2 / g and an average particle diameter of 0.9 μm and heated to 80 ° C. Added below and stirred for 12 hours. Thereafter, the same operation as in Example 1 was performed.
[0024]
[Comparative Example 7]
The same operation as in Example 1 was performed except that an aqueous solution of sodium laurate was used as the first layer.
[0025]
[Comparative Example 8]
The same operation as in Example 1 was performed except that an aqueous solution of sodium oleate was used as the first layer.
[0026]
[Comparative Example 9]
A water resistance test was carried out in the same manner as in Example 1 for a synthetic magnesium hydroxide untreated product having a BET specific surface area of 9.6 m 2 / g and an average particle size of 0.9 μm.
[0027]
The initial volume resistivity is 2.0 × 10 15 Ω · cm or more (（), 1.0 × 10 15 Ω · cm or more and less than 2.0 × 10 15 Ω · cm (△), 1.0 × It was less than 10 15 Ω · cm (×). Further, the volume resistivity after water resistance is 2.0 × 10 14 Ω · cm or more (、), 1.0 × 10 14 Ω · cm or more and less than 2.0 × 10 14 Ω · cm (△), and 1. It was less than 0 × 10 14 Ω · cm (×).
[0028]
[Table 1]
[Table 2]
【The invention's effect】
According to the present invention, magnesium hydroxide is surface-treated with an alkali metal salt and / or ammonium salt of a saturated fatty acid having 18 or more carbon atoms to form a first layer film, and further surface-treated with a silane coupling agent. The formation of the second layer coating provides a phosphorus-free flame retardant excellent in water resistance, and the addition of the magnesium hydroxide-based flame retardant provides a resin composition excellent in water resistance. Further, the magnesium hydroxide-based flame retardant and the resin composition obtained by kneading the flame retardant are halogen-free and phosphorus-free, and do not generate harmful gas even when the resin composition is burned. The load on the human body is small.
Claims (5)
前記第一層の被膜を設けた水酸化マグネシウム粒子を、更にシランカップリング剤で表面処理して第二層の被膜を形成した、リンフリーの水酸化マグネシウム系難燃剤。
ＣａＨ２ａ＋１ＣＯＯ−Ｍ＋（ａ≧１７、Ｍ＋はアルカリ金属イオンを示す） （１）
ＣａＨ２ａ＋１ＣＯＯ−ＮＨ４ ＋（ａ≧１７） （２）
ＣａＨ２ａ＋１ＣＯＯ−［ＨｂＮ（ＣｃＨ２ｃＯＨ）４−ｂ］＋（ａ≧１７、１≦ｂ≦３、１≦ｃ≦４） （３）Surface treatment of the magnesium hydroxide particles with at least one member of an alkali metal salt of a saturated fatty acid of formula (1), an ammonium salt of a saturated fatty acid of formula (2), and an alcoholamine salt of a saturated fatty acid of formula (3) After forming the first layer coating,
A phosphorus-free magnesium hydroxide-based flame retardant, wherein the magnesium hydroxide particles provided with the first layer coating are further surface-treated with a silane coupling agent to form a second layer coating.
C a H 2a + 1 COO - M + (a ≧ 17, M + represents an alkali metal ion) (1)
C a H 2a + 1 COO - NH 4 + (a ≧ 17) (2)
C a H 2a + 1 COO - [H b N (C c H 2c OH) 4-b] + (a ≧ 17,1 ≦ b ≦ 3,1 ≦ c ≦ 4) (3)
ＣａＨ２ａ＋１ＣＯＯ−Ｍ＋（ａ≧１７、Ｍ＋はアルカリ金属イオンを示す） （１）
ＣａＨ２ａ＋１ＣＯＯ−ＮＨ４ ＋（ａ≧１７） （２）
ＣａＨ２ａ＋１ＣＯＯ−［ＨｂＮ（ＣｃＨ２ｃＯＨ）４−ｂ］＋（ａ≧１７、１≦ｂ≦３、１≦ｃ≦４） （３）Surface treatment of the magnesium hydroxide particles with at least one member of an alkali metal salt of a saturated fatty acid of formula (1), an ammonium salt of a saturated fatty acid of formula (2), and an alcoholamine salt of a saturated fatty acid of formula (3) A method for producing a phosphorus-free magnesium hydroxide-based flame retardant, comprising forming a first layer film and then treating the surface with a silane coupling agent to form a second layer film.
C a H 2a + 1 COO - M + (a ≧ 17, M + represents an alkali metal ion) (1)
C a H 2a + 1 COO - NH 4 + (a ≧ 17) (2)
C a H 2a + 1 COO - [H b N (C c H 2c OH) 4-b] + (a ≧ 17,1 ≦ b ≦ 3,1 ≦ c ≦ 4) (3)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007016153A (en) * | 2005-07-08 | 2007-01-25 | Konoshima Chemical Co Ltd | Magnesium hydroxide-based flame retardant with high heat resistance, flame retardant resin composition and molded product |
| CN101792674A (en) * | 2010-03-19 | 2010-08-04 | 大连理工大学 | Method for preparing nitrogen-phosphorus-magnesium compound fire retardant |
| US7816440B2 (en) | 2005-10-25 | 2010-10-19 | Konoshima Chemical Co., Ltd. | Flame retardant, flame-retardant resin composition and molded body |
| CN115558915A (en) * | 2022-10-08 | 2023-01-03 | 深圳市豪龙新材料技术有限公司 | Magnesium alloy high-corrosion-resistance hydrophobic sealant and preparation method thereof |
Families Citing this family (1)
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| CN104530584B (en) * | 2014-11-07 | 2016-03-30 | 安徽省三乐门窗幕墙工程有限公司 | Shock-resistant plastic-steel door window section bar of a kind of good flame resistance and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0238434A (en) * | 1988-07-29 | 1990-02-07 | Nippon Unicar Co Ltd | Flame-retarding polyolefin resin composition |
| JPH0565367A (en) * | 1991-09-05 | 1993-03-19 | Sumitomo Electric Ind Ltd | Acid-resistant flame-retardant composition |
| JP2000195336A (en) * | 1998-12-24 | 2000-07-14 | Furukawa Electric Co Ltd:The | Electric wire coating resin composition and insulated electric wire |
-
2003
- 2003-03-10 JP JP2003063182A patent/JP3773247B2/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0238434A (en) * | 1988-07-29 | 1990-02-07 | Nippon Unicar Co Ltd | Flame-retarding polyolefin resin composition |
| JPH0565367A (en) * | 1991-09-05 | 1993-03-19 | Sumitomo Electric Ind Ltd | Acid-resistant flame-retardant composition |
| JP2000195336A (en) * | 1998-12-24 | 2000-07-14 | Furukawa Electric Co Ltd:The | Electric wire coating resin composition and insulated electric wire |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007016153A (en) * | 2005-07-08 | 2007-01-25 | Konoshima Chemical Co Ltd | Magnesium hydroxide-based flame retardant with high heat resistance, flame retardant resin composition and molded product |
| US7816440B2 (en) | 2005-10-25 | 2010-10-19 | Konoshima Chemical Co., Ltd. | Flame retardant, flame-retardant resin composition and molded body |
| CN101792674A (en) * | 2010-03-19 | 2010-08-04 | 大连理工大学 | Method for preparing nitrogen-phosphorus-magnesium compound fire retardant |
| CN115558915A (en) * | 2022-10-08 | 2023-01-03 | 深圳市豪龙新材料技术有限公司 | Magnesium alloy high-corrosion-resistance hydrophobic sealant and preparation method thereof |
| CN115558915B (en) * | 2022-10-08 | 2023-06-09 | 深圳市豪龙新材料技术有限公司 | Magnesium alloy high corrosion-resistant hydrophobic sealing agent and preparation method thereof |
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