JP3803557B2 - Flame retardant, method for producing the same, and flame retardant resin composition - Google Patents
Flame retardant, method for producing the same, and flame retardant resin composition Download PDFInfo
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- JP3803557B2 JP3803557B2 JP2001090615A JP2001090615A JP3803557B2 JP 3803557 B2 JP3803557 B2 JP 3803557B2 JP 2001090615 A JP2001090615 A JP 2001090615A JP 2001090615 A JP2001090615 A JP 2001090615A JP 3803557 B2 JP3803557 B2 JP 3803557B2
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/028—Compounds containing only magnesium as metal
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/14—Macromolecular materials
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
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Description
【０００１】
【発明の属する技術分野】
本発明は、樹脂に混合して難燃化する目的に使用される難燃剤および該難燃剤を樹脂に配合した難燃性樹脂組成物に関する。より詳しくは、家電製品の筐体、電線、ケーブル、自動車車両、船舶、航空機、鉄道車両、建築材料、電子機器やプリント基板等に使用されている高分子材料を火災などの熱による災害から保護する目的で使用される難燃剤および難燃性樹脂組成物に関するものである。
【０００２】
【従来の技術】
従来、樹脂に混合して該樹脂を難燃化する目的に使用される難燃剤として、ハロゲン系化合物、三酸化アンチモン、リン系化合物、水和金属化合物などが使用されている。また、近年、シリコーン化合物を表面処理剤として用いて難燃剤の難燃性の向上を計る技術が提案されている。例えば、特開昭５８−１８５６４５号公報にはアルコキシシラン表面処理による三酸化アンチモン、特開昭５８−１７９２６９号公報にはポリシロキサン表面処理によるアンチモン化合物、特開昭５８−６３７４７号公報にはメチルハイドジエンポリシロキサン表面処理による水酸化アルミニウム、特開平５−２９５２６６号公報にはオルガノシロキサン表面処理による水酸化マグネシウムなどが開示されている。ハロゲン化合物や三酸化アンチモンは、ダイオキシン等の環境問題から敬遠されつつある。一方、リン系化合物はコスト単価が高いことが問題視されている。ポリマー物性の低下を伴う水和金属化合物とコストの高いリン系化合物を使用しているのが現状である。
【０００３】
【発明が解決しようとする課題】
難燃剤として使用されている水和金属化合物では、その他の有機系難燃化合物と比較して同等の難燃性を達成するためにより多量の配合量を必要とし、そのためポリマー物性を著しく低下させる。また、難燃剤として水和金属化合物と難燃助剤としてシリコーン化合物を併用して配合したポリマー難燃性組成物は、該難燃特性を若干向上させることが知られているものの、その他の有機系難燃化合物と比較して同等の難燃性を得るために多量の配合量を必要することには変りなく、該配合量を減量することは難しい。いずれも難燃剤として使用した場合、上記のごとき問題点は解決されていない。本発明は、これを防ぐために、水和金属化合物の低充填化を目的とするものである。
【０００４】
【課題を解決するための手段】
本発明者らは、前記課題を解決するべく鋭意研究を重ねた結果、水ガラスで被覆した水酸化マグネシウム粒子に分子構造内にＳｉＨ基を持つシリコーン化合物によってさらに被覆した水酸化マグネシウム粒子をポリマーに配合した所、該表面処理を行わない難燃剤と比較して、低充填でも良好な難燃性が可能であることを見いだし、本発明を完成させるに至った。
すなわち、本発明によれば、水ガラスにて被覆した水酸化マグネシウム粒子を、分子構造内にＳｉＨ基を有するシリコーン化合物で表面処理したことを特徴とする難燃剤が提供される。
また本発明によれば、前記した水酸化マグネシウム粒子の表面に水ガラス層とシリコーン層の２つの被覆層を形成させた本発明の難燃剤を、樹脂に配合した難燃性樹脂組成物が提供される。
【０００５】
以下本発明の難燃剤、その製造方法および難燃性樹脂組成物についてさらに具体的に説明する。
本発明における水酸化マグネシウム粒子は、樹脂の難燃剤として使用されるものであれば何ら制限されない。合成および天然のいずれであっても差し支えない。
水酸化マグネシウム粒子は、結晶がよく成長したものが好ましく、かつ凝集が少ないものが好ましい。水酸化マグネシウム粒子の平均粒子径は、２０μｍ以下、好ましくは０.５〜５μｍが適当であり、ＢＥＴ比表面積は２０ｍ2／ｇ以下、好ましくは２〜１０ｍ2／ｇが適当である。
【０００６】
水酸化マグネシウム粒子の表面に被覆される水ガラスは、１号、２号または３号水ガラスの他に、無定形シリカをＮａＯＨで溶解したものが使用される。水酸化マグネシウム粒子を水ガラスで表面処理するに際し、使用する溶媒は、水もしくはアルコール系溶媒を単独もしくは混合であるのが有利である。水酸化マグネシウム粒子１００重量部に対する被覆された水ガラスの量は、０.１〜１０重量部、好ましくは０.５〜７重量部が適当である。
水ガラスで表面処理された水酸化マグネシウム粒子は、さらにその表面にシリコーン化合物によって表面被覆される。
本発明で使用するシリコーン化合物としては、例えば下記一般式（１）に示す基本構造を有し、分子構造内にＳｉＨ基を有するポリオルガノシロキサンがあげられる。
【０００７】
【化２】
一般式（１）において、Ｒは飽和または不飽和の一価の炭化水素基、Ｒ’およびＲ’ ’は同一もしくは異なり、水素原子、飽和または不飽和の一価の炭化水素基、ｎまたはｍは各々０〜１０万の整数を表わし、それぞれ０〜５万の整数が好ましい。ＳｉＨ当量が４０〜１０００の範囲が好ましく、４０〜５００の範囲がさらに好ましく、４０〜１００の範囲が最も好ましい。ここで、ＳｉＨ当量とは、シリコーン化合物の分子中のＳｉＨ基１個当りに換算した分子量をいう。つまり分子量をＳｉＨ基の個数で割った値をいう。好ましいＲとしては、メチル基、エチル基またはフェニル基などの飽和または不飽和の一価の炭化水素基。好ましいＲ’およびＲ’ ’としては、Ｒと同じ基、あるいは水素原子を含む群から選ばれる飽和または不飽和の一価の炭化水素基等が挙げられる。
【０００９】
本発明で使用する分子構造内にＳｉＨ基を有するシリコーン化合物とは、反応性シリコーン、シリコーンゴムの架橋剤などがあげられる。例えば、東レ・ダウコーニング・シリコーン社、信越化学工業社、東芝シリコーン社、ワッカーケミー社、バイエル社やローヌプーラン社製の室温２液硬化型のゴム架橋剤、信越化学株式会社の撥水処理用シリコーンオイル等があげられる。
シリコーン化合物の被覆量は、水酸化マグネシウム粒子１００重量部に対して０.１〜５０重量部、好ましくは０.５〜２０重量部が適当である。
【００１０】
本発明で使用する水酸化マグネシウム粒子を、水ガラスで表面処理した後にさらに水ガラス表面のＯＨ基とシリコーン化合物のＳｉＨ基を反応させる際、必要に応じて用いる触媒としては、ジブチルスズジラウリレート、ジブチルスズジアセテートなどの錫系触媒、テトラブチルチタネートなどのチタン系触媒、鉄オクトエートなど鉄系触媒、塩化白金酸などの白金系、この他に亜鉛系、モリブデン系触媒などが考えられる。特に好ましいのは錫触媒である。
該触媒の添加量は、分子構造内にＳｉＨ基を有するシリコーン化合物１００重量部に対して、０.１〜３０重量部を用いることが好ましく、さらに好ましくは５〜１０重量部用いる。
【００１１】
本発明で使用する水ガラスにて被覆した水酸化マグネシウム粒子に、分子構造内にＳｉＨ結合を有するシリコーン化合物を被覆する方法としては、例えば、有機溶媒中で湿式処理後乾燥もしくは、シリコーン化合物を噴霧する、または噴霧乾燥することをが挙げられ、その被覆する際の温度は、好ましくは０〜１００℃、より好ましくは室温から６０℃、特に好ましくは室温である。
本発明で使用する水ガラスにて被覆した水酸化マグネシウム粒子に、分子構造内にＳｉＨ結合を持つシリコーン化合物を被覆する際の反応雰囲気は、空気中もしくは不活性ガス雰囲気下どちらでもよいが、不活性ガス雰囲気下で行うことが望ましい。
【００１２】
上記例示の被覆方法において、本発明で使用する水酸化マグネシウム粒子を、水ガラスで表面処理した後にさらに分子構造内にＳｉＨ基を有するシリコーン化合物で表面処理する際の有機溶媒としては、例えば、メタノール、エタノール、シクロヘキサノール、ｎ−ブタノール、ｎ−ヘキサノール、イソプロピルアルコール、ｎ−アミルアルコール、エチレングリコールなどのアルコール系化合物；テトラヒドロフラン、ジエチルエーテルなどのエーテル化合物；エチルホルムアミド、ジメチルホルムアミド、グリセロールホルムアミドなどのアミド系化合物；ベンゼン、トルエン、キシレン、エチルベンゼン、アニリン、ピリジン、ベンゾニトリルなどの芳香族系化合物；アセトン、メチルエチルケトン、ジエチルケトン、メチルエチルケトン、メチルプロピルケトン、メチルイソピロピルケトンなどのケトン系化合物；酢酸エチル、酢酸ブチル、酢酸イソブチル、酢酸イソプロピルなどのエステル系化合物；ｎ−オクタン、ｎ−ヘプタン、シクロへキサンなどの炭化水素系化合物；メチルアミン、ジエチルアミンなどのアミン系化合物；四塩化炭素、クロロホルム、イソブチルクロリド、トリクロロエチレン、塩化メチレンなどのハロゲン系有機化合物、その他にニトロメタン、アクリル酸、アセトニトリル、ジメチルスルホキシド等が挙げられる。上記例示の有機溶媒は単独もしくは２種類以上で混合して用いられる。
【００１３】
本発明で使用する水酸化マグネシウム粒子を、水ガラスで表面処理した後にさらに分子構造内にＳｉＨ基を有するシリコーン化合物で表面処理する際の熱処理温度は０〜２００℃、好ましくは８０から１２０℃、特に好ましくは１００〜１２０℃である。
本発明で使用する水酸化マグネシウム粒子を、水ガラスで表面処理した後にさらに分子構造内にＳｉＨ基を有するシリコーン化合物で表面処理する際の熱処理雰囲気は、空気中または不活性ガス中どちらでもよい。
前述した水ガラス層およびシリコーン化合物層により被覆された水酸化マグネシウム粒子は、樹脂の難燃剤として優れている。
【００１４】
本発明の難燃樹脂組成物の樹脂とは、成型加工可能な任意の熱可塑性樹脂や熱硬化性樹脂である。このような樹脂の例としては、ポリエチレン、ポリプロピレン、ポリブテン-１、ポリ４-メチルペンテン、エチレン−プロピレン共重合体、エチレン−ブテン-１共重合体、エチレン−４-メチルペンテン共重合体、プロピレン−ブテン-１共重合体、プロピレン−４-メチルペンテン共重合体、エチレン-アクリル酸エステル共重合体、エチレン−酢酸ビニル共重合体などのオレフィン系の重合体または共重合体；ポリスチレン、アクリロニトリル−ブタジエン−スチレン共重合体、アクリロニトリル−スチレン共重合体、アクリロニトリル−スチレン−アクリル酸エステル共重合体などのスチレン系の重合体または共重合体；塩化ビニル樹脂、酢酸ビニル樹脂、塩化ビニリデン樹脂、エチレン−塩化ビニル共重合体などのビニル系の重合体または共重合体；フェノキシ樹脂、ブタジエン樹脂、フッ素樹脂、ポリアセタール樹脂、ポリアミド樹脂、ポリウレタン樹脂、ポリエステル樹脂、ポリカーボネート樹脂、ポリケトン樹脂、メタクリル樹脂、ジアリルフタレート樹脂、フェノール樹脂、エポキシ樹脂、メラミン樹脂、ユリア樹脂；その他に、エチレン−プロピレン−ジエン共重合体、ブタジエンゴム、スチレン−ブタジエンゴム、クロロプレンゴム、塩素化ポリエチレン、クロロスルホン化ポリエチレン、二トリルゴム、イソプレンゴム、ブチルゴム、フッ素ゴムなどのゴム類が例示できる。
【００１５】
これらの中で、ポリエチレン、ポリプロピレン、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等が好ましい。
本発明において、樹脂に配合される難燃剤の配合比としては、樹脂１００重量部当たり、例えば、０.１〜２００重量部であるが、好ましくは３０〜１５０重量部、さらに好ましくは、５０〜１２０重量部が最も好ましい。０.１重量部未満では、難燃性に劣り、２００重量部を越えると機械的特性を低下させるので好ましくない。
本発明の難燃性樹脂組成物は、ＪＩＳ Ｋ ７２０１で規定する酸素指数が２５以上であり、好適条件下では２６以上が、最も好ましくは２７以上が達成される。
【００１６】
本発明の難燃樹脂組成物は、上記本発明による難燃剤が樹脂中に配合されている。しかし本発明の難燃性樹脂組成物には、必要に応じて、他の難燃性物質がさらに併用して含まれてもよい。例えば、ホウ酸亜鉛水和物、メタホウ酸バリウム、ほう砂などのホウ酸を含有する化合物；リン酸アンモニウム、ポリリン酸アンモニウム、リン酸メラミン、赤燐、リン酸エステル、トリス（クロロエチル）ホスフェート、トリス（モノクロロプロピル）ホスフェート、トリス（ジクロロプロピル）ホスフェート、トリアリルフォスフェート、トリス（３−ヒドロキシプロピル）ホスフェート、トリス（トリブロモフェニル）ホスフェート、トリス・β―クロロプロピルホスフェート、トリス（ジブロモフェニル）ホスフェート、トリス（トリブロモネオペンチル）ホスフェート、テトラキス（２−クロロエチル）エチレン・ジフォスフェート、ジメチルメチルフォスフェート、トリス（２−クロロエチル）オルトリン酸エステル、芳香族縮合リン酸エステル、含ハロゲン縮合有機リン酸エステル、エチレン・ビス・トリス（２−シアノエチル）ホスフォニウム・ブロミド、ポリリン酸アンモニウム、β−クロロエチルアッシドフォスフェート、ブチルピロフォスフェート、ブチルアッシドフォスフェート、ブトキシエチルアッシドフォスフェート、２−エチルヘキシルアッシドフォスフェート、メラミンリン酸塩、含ハロゲンフォスソネート、フェニル・フォスフォン酸などのリンを含有する化合物；硫酸アンモニウムなどのアンモン系難燃化合物、フェロセンなどの酸化鉄系燃焼触媒、硝酸銅などの硝酸金属化合物、酸化チタンなどのチタンを含有する化合物、スルファミン酸グアニジンなどのグアニジン系化合物、その他、ジルコニウム系化合物、モリブデン系化合物、錫系化合物、炭酸カリウムなどの炭酸塩化合物、水酸化アルミニウム、水酸化マグネシウムなどの水酸和金属およびその変性物などの無機系難燃化合物；トリアジン環を有するシアヌレート化合物などのチッソを含有する難燃性化合物；塩素化パラフィン、パークロロシクロペンタデカン、ヘキサブロモベンゼン、デカブロモジフェニルオキシド、ビス（トリブロモフェノキシ）エタン、エチレンビス・ジブロモノルボルナンジカルボキシイミド、エチレンビス・テトラブロモフタルイミド、ジブロモエチル・ジブロモシクロヘキサン、ジブロモネオペンチルグリコール、２,４,６−トリブロモフェノール、トリブロモフェニルアリルエーテル、テトラブロモ・ビスフェノールＡ誘導体、テトラブロモ・ビスフェノールＳ誘導体、テトラデカブロモ・ジフェノキシベンゼン、トリスー（２,３−ジブロモプロピルー１−）−イソシアヌレート、２,２−ビス（４−ヒドロキシ−３,５−ジブロモフェニル）プロパン、２,２−ビス（４−ヒドロキシエトキシ−３,５−ジブロモフェニル）プロパン、ポリ（ペンタブロモベンジル・アクリレート）、トリブロモスチレン、トリブロモフェニルマレイニド、トリブロモネオペンチル・アルコール、テトラブロモジペンタエリスリトール、ペンタブロモベンジルアクリレート、ペンタブロモフェノール、ペンタブロモトルエン、ペンタブロモジフェニルオキシド、ヘキサブロモシクロドデカン、ヘキサブロモジフェニルエーテル、オクタブロモフェノールエーテル、オクタジブロモジフェニルエーテル、オクタブロモジフェニルオキシド、ジブロモネオペンチルグリコールテトラカルボナート、ビス（トリブロモフェニル）フマルアミド、Ｎ−メチルヘキサブロモジフェニルアミン、臭化スチレン、ジアリルクロレンデートなどのハロゲンを含有する難燃化合物；その他に無水クロレンド酸、無水フタル酸、ビスフェノールＡを含有する化合物、グリシジルエーテルなどのグリシジル化合物、ジエチレングリコール、ペンタエリスリトールなどの多価アルコール、変性カルバミドなどがあげられる。これらは、単独もしくは２つ以上で複合して用いられる。
【００１７】
本発明の難燃性樹脂組成物には、必要に応じて他の添加剤が含まれてもよい。例えば、橋掛け剤、橋掛け促進剤、橋掛け促進助剤、活性剤、橋掛け抑制剤、老化防止剤、酸化防止剤、オゾン劣化防止剤、紫外線吸収剤、光安定剤、粘着付与剤、可塑剤、軟化剤、補強剤、強化剤、発砲剤、発泡助剤、安定剤、滑剤、離型剤、帯電防止剤、変性剤、着色剤、カップリング剤、防腐剤、防カビ剤、改質剤、接着剤、付香剤、重合触媒、重合開始剤、重合禁止剤、重合抑制剤、重合調整剤、重合開始剤、結晶核剤、相溶化剤、分散剤、消泡剤などが挙げられる。これらは、単独もしくは２つ以上で複合して使用して用いられる。
【００１８】
本発明の難燃性樹脂組成物は、樹脂、難燃剤および必要によりその他の成分を、例えばロール、ニーダー、バンバリーミキサー、インターミックス、１軸押出機、２軸押出機の群より選ばれる１種以上の混練機で混練することによって調製され、さらに、該難燃性樹脂組成物は、例えばプレス成型機、インジェクション成型機、モールド成型機、ブロー成型機、押出成型機、紡糸成型機の群より選ばれる１種以上の成型機で成型することができる。
【００１９】
本発明の難燃性樹脂組成物は、電気、ガス、石油、石炭、原子力などの加熱源になりえる機械および装置のプラスチック部分、建築物のプラスチック部分、および車両のプラスチック部分などに使用される。例えば、エアコン、ラジオ、テレビ、ファン、皿洗機、電子レンジ、ジューサ・ミキサー、調理器、洗濯機、音響機器、ビデオなどの電化製品、スナップ・スイッチ、コード・ワイヤ、プラグ・リセプタクル、プリント基板、コードセット・電源コード、温度表示制御盤、トランスなどの電子部品、電線、コネクタ製品、カーテン、壁紙、壁、梁、床、カーペットなどの建築材料、座席、パネル、床、絶縁材などの車両材料などが挙げられる。
【００２０】
【実施例】
以下に本発明について実施例により具体的に説明する。但し、本発明は以下の実施例に限定されるものではない。
【００２１】
難燃剤合成例１〜９
合成例１（参考例）
水酸化マグネシウム粒子（協和化学製キスマ５）１００ｇに分子構造内にＳｉＨ結合を有するシリコーン化合物（アズマックス製ＤＭＳ−Ｈ２５：表１）１０ｇをテトラヒドロフラン３００ｍＬ中で室温、１時間攪拌させ、その後ロータリーエバポレーターにてテトラヒドロフラン（ＴＨＦ）を除去した。次に、溶媒を除去した物を乾燥機にて１２０℃で１２時間熱処理し、難燃剤を得た。
【００２２】
合成例２
水９００ｍＬに水酸化マグネシウム粒子（協和化学製キスマ５）１００ｇを攪拌し、水ガラス（（（株））トクヤマ製ケイ酸ソーダ＃３１）を水酸化マグネシウム粒子に対しＳｉＯ2換算で１ｇを添加し、３０分攪拌後、脱水し、乾燥させる。得られた水ガラス処理水酸化マグネシウム粒子１００ｇに分子構造内にＳｉＨ結合を有するシリコーン化合物（アズマックス製ＤＭＳ−Ｈ２５）１０ｇ、及びジブチルスズジラウリレート１ｇをテトラヒドロフラン３００ｍＬ中で室温、１時間攪拌させ、その後ロータリーエバポレーターにてテトラヒドロフラン（ＴＨＦ）を除去した。次に、溶媒を除去した物を乾燥機にて１２０℃で１２時間熱処理し、本発明の難燃剤を得た。
【００２３】
合成例３
ジブチルスズジラウリレートを添加しない以外は合成例２と同じ方法で本発明の難燃剤を得た。
【００２４】
合成例４〜９
添加するシリコーン化合物を下記表１の化合物を使用する以外は合成例３と同じ方法で本発明の難燃剤を得た。なお表１には合成例１〜３で使用したシリコーン化合物も併記した。
【００２５】
【表１】
合成例１〜９で得られた生成物の分子構造内にＳｉＨ基を有するシリコーン化合物と水ガラス処理した水酸化マグネシウム粒子の水ガラス処理水酸化マグネシウム粒子（Ｋ１）に対するＳｉＨ結合量及び非ＳｉＨ化学結合量（単位：ＰＰＨ）を調べた。３０ｍｌビーカー中に作製した生成物１ｇとＴＨＦ１０ｇを１時間常温にて攪拌する。その混合液をミリポアにてろ過し、ろ液を１２０℃×３時間真空オーブンで乾燥する。そのろ液乾固物の重量を測定する。ろ液乾固物の重量は、非化学結合量であることから、その値を仕込み量から差し引いた値を化学結合量とした。その結果を下記表２に示した。
【００２７】
【表２】
上記表２より、水ガラスによる処理を施していない水酸化マグネシウム粒子に分子構造内にＳｉＨ基を有するシリコーン化合物を処理した合成例１と水ガラス処理した水酸化マグネシウム粒子に分子構造内にＳｉＨ基を有するシリコーン化合物を処理した合成例２〜９を比較すると、合成例２〜９の粒子は、ＳｉＨ化学結合量が合成例１と比べて高かった。このことは水酸化マグネシウム粒子表面のＯＨ基とシリコーン化合物のＳｉＨ基の反応性より、水ガラス処理した水酸化マグネシウム粒子の水ガラス表面のＯＨ基とシリコーン化合物のＳｉＨ基の反応性が高いためであると考えられる。
【００２９】
実施例１〜８
上記合成例２〜９で作製した難燃剤１００重量部に対し、ポリエチレン樹脂１００重量部を配合した難燃性樹脂組成物を調製し難燃性試験を行った。試料の調製は、それぞれ２軸混練機とプレス成形機を用いて１５０ｍｍ×３ｍｍ×３ｍｍの試験片に成形加工した。２軸混練条件は、材料供給部１６０℃、混練部１９０℃、排出部１７０℃で行い、プレス成形は１８０℃×１０分の後水冷１０分でアニールし、難燃性試験用試験片を作製した。難燃性試験方法は、酸素指数測定 ＪＩＳ Ｋ ７２０１に準じて測定を行った。
【００３０】
比較例１
水ガラス処理した水酸化マグネシウム粒子１００重量部に対し、ポリエチレン樹脂１００重量部を配合した難燃性樹脂組成物を調製し難燃性試験を行った。試料の調製は、２軸混練機とプレス成形機を用いて１５０ｍｍ×３ｍｍ×３ｍｍの試験片に成形加工した。２軸混練条件は、材料供給部１６０℃、混練部１９０℃、排出部１７０℃で行い、プレス成形は１８０℃×１０分の後水冷１０分でアニールし、難燃性試験用試験片を作製した。難燃性試験方法は、酸素指数測定 ＪＩＳ Ｋ ７２０１に準じて測定を行った。
【００３１】
比較例２
水ガラス処理した水酸化マグネシウム１００粒子重量部、シリコーン化合物（アズマックス製 ＤＭＳ−Ｈ２５）１０重量部、及びポリエチレン樹脂１００重量部を配合した難燃性樹脂組成物を調製し難燃性試験を行った。試料の調製は、２軸混練機とプレス成形機を用いて１５０ｍｍ×３ｍｍ×３ｍｍの試験片に成形加工した。２軸混練条件は、材料供給部１６０℃、混練部１９０℃、排出部１７０℃で行い、プレス成形は１８０℃×１０分の後水冷１０分でアニールし、難燃性試験用試験片を作製した。難燃性試験方法は、酸素指数測定 ＪＩＳ Ｋ ７２０１に準じて測定を行った。
実施例１〜８および比較例１〜２の結果をまとめて下記表３に示した。
【００３２】
【表３】
上記表３の結果から下記（ａ）〜（ｄ）のことが理解される。
（ａ）ポリエチレン樹脂１００重量部に水ガラス処理のみした水酸化マグネシウム粒子１００重量部の比較例１とポリエチレン樹脂１００重量部に水ガラス処理のみの水酸化マグネシウム粒子１００重量部と分子構造内にＳｉＨ基を持つシリコーン化合物をその水酸化マグネシウム粒子に化学結合を伴わないで別々に混練した比較例２は、酸素指数が若干向上した（ポリエチレン樹脂の酸素指数は約１７である）。
【００３４】
（ｂ）さらに、水ガラス処理した水酸化マグネシウム粒子に分子構造内にＳｉＨ基を持つシリコーン化合物を被覆した実施例１〜８は、水ガラス処理した水酸化マグネシウム粒子に分子構造内にＳｉＨ基を持つシリコーン化合物を結合させない比較例２と比べて酸素指数が一様に高かった。
【００３５】
（ｃ）次に、水ガラスのＯＨ基とシリコーン化合物のＳｉＨ基の反応を促進させる触媒としてジブチルスズジラウリレートを添加した実施例１と添加しない実施例２を比較するとジブチルスズジラウリレートを添加した実施例１の酸素指数が高かった。
【００３６】
（ｄ）分子構造内にＳｉＨ基を持つシリコーン化合物の分子構造の異なる物質を水ガラス処理した水酸化マグネシウム粒子に化学結合させた実施例１〜８の中で特に分子構造内にＳｉＨ基を持つシリコーン化合物中のＳｉＨ当量が６５の実施例６は高い酸素指数を示した。このようにＳｉＨ当量の低いシリコーン化合物を結合させた水ガラス処理水酸化マグネシウム粒子を配合した難燃樹脂組成物の難燃特性が非常に良好なことは、予想外の結果であった。
【００３７】
【発明の効果】
本発明によれば、分子構造内にＳｉＨ基を持つシリコーン化合物を水ガラス処理した水酸化マグネシウム粒子に被覆して化学結合させた本発明の難燃剤は、以下の優れた効果が得られる。
（１）分子構造内にＳｉＨ基を持つシリコーン化合物を水ガラス処理した水酸化マグネシウム粒子に被覆し化学結合させた本発明の難燃剤は、水ガラス処理しない水酸化マグネシウム粒子に分子構造内にＳｉＨ基を持つシリコーン化合物を処理したものと比較して高い化学結合量を示す。
（２）分子構造内にＳｉＨ基を持つシリコーン化合物を水ガラス処理した水酸化マグネシウム粒子に化学結合させた本発明の難燃剤は、その化学結合性を持たせないものと比較して高い難燃性を示す。
（３）分子構造内にＳｉＨ基を持ちＳｉＨ当量の低いシリコーン化合物を水ガラス処理した水酸化マグネシウム粒子に化学結合させた本発明の難燃剤は、特に高い難燃性を示す。
（４）分子構造内にＳｉＨ基を持つシリコーン化合物を水ガラス処理した水酸化マグネシウム粒子に化学結合させた本発明の難燃剤は、水ガラスのＯＨ基とシリコーン化合物のＳｉＨ基の反応を促進させる触媒を添加することによりさらに高い難燃性を示す。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a flame retardant used for the purpose of making it flame retardant by mixing with a resin, and a flame retardant resin composition containing the flame retardant in a resin. More specifically, polymer materials used in housings for home appliances, electric wires, cables, automobiles, ships, aircraft, railway vehicles, building materials, electronic devices and printed circuit boards are protected from disasters caused by heat such as fire. The present invention relates to a flame retardant and a flame retardant resin composition.
[0002]
[Prior art]
Conventionally, halogen-based compounds, antimony trioxide, phosphorus-based compounds, hydrated metal compounds, and the like have been used as flame retardants used for the purpose of making the resin flame-retardant by mixing with the resin. In recent years, a technique for improving the flame retardancy of a flame retardant using a silicone compound as a surface treatment agent has been proposed. For example, JP-A-58-185645 discloses antimony trioxide by alkoxysilane surface treatment, JP-A-58-179269 discloses antimony compound by polysiloxane surface treatment, and JP-A-58-63747 discloses methyl. Aluminum hydroxide obtained by surface treatment with a hydrodiene polysiloxane, and magnesium hydroxide produced by surface treatment with an organosiloxane are disclosed in JP-A-5-295266. Halogen compounds and antimony trioxide are being avoided from environmental problems such as dioxins. On the other hand, phosphorus-based compounds are regarded as problematic because of their high cost unit cost. The present condition is using a hydrated metal compound accompanied by a decrease in polymer physical properties and a high-cost phosphorus compound.
[0003]
[Problems to be solved by the invention]
The hydrated metal compound used as a flame retardant requires a larger amount of blending in order to achieve the same flame retardancy as compared with other organic flame retardant compounds, and therefore the polymer physical properties are significantly reduced. Further, a polymer flame retardant composition containing a hydrated metal compound as a flame retardant and a silicone compound as a flame retardant aid is known to slightly improve the flame retardant properties, but other organic In order to obtain the same flame retardancy as compared with the system flame retardant compound, a large amount of blending is not changed, and it is difficult to reduce the blending amount. When both are used as flame retardants, the above problems are not solved. In order to prevent this, the present invention aims to reduce the filling of the hydrated metal compound.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have converted magnesium hydroxide particles coated with water glass into magnesium hydroxide particles further coated with a silicone compound having a SiH group in the molecular structure. When blended, it was found that good flame retardancy was possible even with low filling compared to a flame retardant not subjected to the surface treatment, and the present invention was completed.
That is, according to the present invention, there is provided a flame retardant characterized in that magnesium hydroxide particles coated with water glass are surface-treated with a silicone compound having a SiH group in the molecular structure.
According to the present invention, there is also provided a flame retardant resin composition in which the flame retardant of the present invention in which two coating layers of a water glass layer and a silicone layer are formed on the surface of the magnesium hydroxide particles is blended with a resin. Is done.
[0005]
Hereinafter, the flame retardant of the present invention, the production method thereof, and the flame retardant resin composition will be described more specifically.
The magnesium hydroxide particles in the present invention are not limited as long as they are used as a flame retardant for resins. It can be either synthetic or natural.
The magnesium hydroxide particles are preferably those in which crystals grow well and those in which aggregation is small. The average particle size of the magnesium hydroxide particles is 20 μm or less, preferably 0.5 to 5 μm, and the BET specific surface area is 20 m. 2 / G or less, preferably 2 to 10 m 2 / G is appropriate.
[0006]
As the water glass coated on the surface of the magnesium hydroxide particles, in addition to No. 1, No. 2 or No. 3 water glass, amorphous silica dissolved in NaOH is used. When the surface of the magnesium hydroxide particles is treated with water glass, it is advantageous that the solvent used is water or an alcohol solvent alone or in combination. The amount of the coated water glass with respect to 100 parts by weight of the magnesium hydroxide particles is 0.1 to 10 parts by weight, preferably 0.5 to 7 parts by weight.
Magnesium hydroxide particles surface-treated with water glass are further coated on the surface with a silicone compound.
Examples of the silicone compound used in the present invention include polyorganosiloxane having a basic structure represented by the following general formula (1) and having a SiH group in the molecular structure.
[0007]
[Chemical 2]
In the general formula (1), R is a saturated or unsaturated monovalent hydrocarbon group, R ′ and R ′ ′ are the same or different, a hydrogen atom, a saturated or unsaturated monovalent hydrocarbon group, n or m Each represents an integer of 0 to 100,000, preferably an integer of 0 to 50,000. The SiH equivalent is preferably in the range of 40 to 1000, more preferably in the range of 40 to 500, and most preferably in the range of 40 to 100. Here, SiH equivalent means the molecular weight converted per SiH group in the molecule | numerator of a silicone compound. That is, the value obtained by dividing the molecular weight by the number of SiH groups. R is preferably a saturated or unsaturated monovalent hydrocarbon group such as a methyl group, an ethyl group or a phenyl group. Preferred examples of R ′ and R ′ ′ include the same group as R, or a saturated or unsaturated monovalent hydrocarbon group selected from the group containing a hydrogen atom.
[0009]
Examples of the silicone compound having a SiH group in the molecular structure used in the present invention include reactive silicones and silicone rubber crosslinking agents. For example, Toray Dow Corning Silicone Co., Shin-Etsu Chemical Co., Ltd., Toshiba Silicone Co., Wacker Chemie Co., Bayer Co., Ltd. and Rhône-Poulenc, room temperature two-component curing rubber cross-linking agent, Shin-Etsu Chemical Co., Ltd. water repellent treatment Examples include silicone oil.
The coating amount of the silicone compound is suitably 0.1 to 50 parts by weight, preferably 0.5 to 20 parts by weight with respect to 100 parts by weight of the magnesium hydroxide particles.
[0010]
When the magnesium hydroxide particles used in the present invention are surface-treated with water glass and further reacting the OH group on the surface of the water glass with the SiH group of the silicone compound, the catalyst used as necessary is dibutyltin dilaurate, A tin-based catalyst such as dibutyltin diacetate, a titanium-based catalyst such as tetrabutyl titanate, an iron-based catalyst such as iron octoate, a platinum-based catalyst such as chloroplatinic acid, and a zinc-based or molybdenum-based catalyst may also be considered. Particularly preferred is a tin catalyst.
The added amount of the catalyst is preferably 0.1 to 30 parts by weight, more preferably 5 to 10 parts by weight with respect to 100 parts by weight of the silicone compound having a SiH group in the molecular structure.
[0011]
Examples of the method for coating the magnesium hydroxide particles coated with water glass used in the present invention with a silicone compound having a SiH bond in the molecular structure include, for example, drying after wet treatment in an organic solvent or spraying the silicone compound. The temperature at the time of coating is preferably 0 to 100 ° C., more preferably room temperature to 60 ° C., and particularly preferably room temperature.
The reaction atmosphere when the magnesium hydroxide particles coated with water glass used in the present invention are coated with a silicone compound having a SiH bond in the molecular structure may be either in air or in an inert gas atmosphere. It is desirable to carry out in an active gas atmosphere.
[0012]
In the above exemplified coating method, as the organic solvent when the magnesium hydroxide particles used in the present invention are surface-treated with water glass and then surface-treated with a silicone compound having a SiH group in the molecular structure, for example, methanol Alcohol compounds such as ethanol, cyclohexanol, n-butanol, n-hexanol, isopropyl alcohol, n-amyl alcohol and ethylene glycol; ether compounds such as tetrahydrofuran and diethyl ether; amides such as ethylformamide, dimethylformamide and glycerolformamide Compounds: aromatic compounds such as benzene, toluene, xylene, ethylbenzene, aniline, pyridine, benzonitrile; acetone, methyl ethyl ketone, diethyl ketone, methyl ethyl ketone Ketone compounds such as ethyl acetate, methyl propyl ketone and methyl isopropyl ketone; ester compounds such as ethyl acetate, butyl acetate, isobutyl acetate and isopropyl acetate; hydrocarbons such as n-octane, n-heptane and cyclohexane Compounds; amine compounds such as methylamine and diethylamine; halogen organic compounds such as carbon tetrachloride, chloroform, isobutyl chloride, trichloroethylene, and methylene chloride; nitromethane, acrylic acid, acetonitrile, dimethyl sulfoxide, and the like. The organic solvents exemplified above are used alone or in combination of two or more.
[0013]
The magnesium hydroxide particles used in the present invention are subjected to a surface treatment with water glass and then a surface treatment with a silicone compound having a SiH group in the molecular structure, the heat treatment temperature is 0 to 200 ° C., preferably 80 to 120 ° C. Especially preferably, it is 100-120 degreeC.
The heat treatment atmosphere when the magnesium hydroxide particles used in the present invention are surface-treated with water glass and then surface-treated with a silicone compound having a SiH group in the molecular structure may be either in air or in an inert gas.
The magnesium hydroxide particles coated with the water glass layer and the silicone compound layer described above are excellent as a flame retardant for the resin.
[0014]
The resin of the flame retardant resin composition of the present invention is any thermoplastic resin or thermosetting resin that can be molded. Examples of such resins include polyethylene, polypropylene, polybutene-1, poly-4-methylpentene, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-4-methylpentene copolymer, propylene. -Olefin-based polymers or copolymers such as butene-1 copolymer, propylene-4-methylpentene copolymer, ethylene-acrylic acid ester copolymer, ethylene-vinyl acetate copolymer; polystyrene, acrylonitrile- Styrene polymers or copolymers such as butadiene-styrene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-acrylate copolymer; vinyl chloride resin, vinyl acetate resin, vinylidene chloride resin, ethylene- Vinyl polymers such as vinyl chloride copolymers or Copolymer; Phenoxy resin, butadiene resin, fluororesin, polyacetal resin, polyamide resin, polyurethane resin, polyester resin, polycarbonate resin, polyketone resin, methacrylic resin, diallyl phthalate resin, phenol resin, epoxy resin, melamine resin, urea resin; In addition, rubbers such as ethylene-propylene-diene copolymer, butadiene rubber, styrene-butadiene rubber, chloroprene rubber, chlorinated polyethylene, chlorosulfonated polyethylene, nitrile rubber, isoprene rubber, butyl rubber, and fluorine rubber can be exemplified.
[0015]
Among these, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer and the like are preferable.
In the present invention, the blending ratio of the flame retardant blended in the resin is, for example, 0.1 to 200 parts by weight per 100 parts by weight of the resin, preferably 30 to 150 parts by weight, and more preferably 50 to 50 parts by weight. 120 parts by weight is most preferred. If it is less than 0.1 part by weight, the flame retardancy is inferior, and if it exceeds 200 parts by weight, the mechanical properties are deteriorated.
The flame retardant resin composition of the present invention has an oxygen index defined by JIS K 7201 of 25 or more, and 26 or more, most preferably 27 or more is achieved under suitable conditions.
[0016]
In the flame retardant resin composition of the present invention, the flame retardant according to the present invention is blended in the resin. However, the flame retardant resin composition of the present invention may contain other flame retardant materials in combination as necessary. For example, compounds containing boric acid such as zinc borate hydrate, barium metaborate, borax; ammonium phosphate, ammonium polyphosphate, melamine phosphate, red phosphorus, phosphate ester, tris (chloroethyl) phosphate, tris (Monochloropropyl) phosphate, tris (dichloropropyl) phosphate, triallyl phosphate, tris (3-hydroxypropyl) phosphate, tris (tribromophenyl) phosphate, tris β-chloropropyl phosphate, tris (dibromophenyl) phosphate, Tris (tribromoneopentyl) phosphate, tetrakis (2-chloroethyl) ethylene diphosphate, dimethyl methyl phosphate, tris (2-chloroethyl) orthophosphate, aromatic condensation Phosphoric acid ester, halogen-containing condensed organic phosphoric acid ester, ethylene bis-tris (2-cyanoethyl) phosphonium bromide, ammonium polyphosphate, β-chloroethyl acid phosphate, butyl pyrophosphate, butyl acid phosphate, Compounds containing phosphorus such as butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, melamine phosphate, halogen-containing phosphonate, phenyl phosphonate; ammon-based flame retardant compounds such as ammonium sulfate, ferrocene, etc. Iron oxide combustion catalysts, metal nitrate compounds such as copper nitrate, compounds containing titanium such as titanium oxide, guanidine compounds such as guanidine sulfamate, other zirconium compounds, molybdenum compounds, tin compounds , Inorganic flame retardant compounds such as carbonate compounds such as potassium carbonate, hydrated metals such as aluminum hydroxide and magnesium hydroxide, and modified products thereof; flame retardant containing nitrogen such as cyanurate compounds having a triazine ring Compound: Chlorinated paraffin, perchlorocyclopentadecane, hexabromobenzene, decabromodiphenyl oxide, bis (tribromophenoxy) ethane, ethylenebisdibromonorbornanedicarboximide, ethylenebistetrabromophthalimide, dibromoethyl dibromocyclohexane, Dibromoneopentyl glycol, 2,4,6-tribromophenol, tribromophenyl allyl ether, tetrabromo-bisphenol A derivative, tetrabromo-bisphenol S derivative, tetradecabromo- Diphenoxybenzene, tris (2,3-dibromopropyl-1-)-isocyanurate, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxyethoxy-) 3,5-dibromophenyl) propane, poly (pentabromobenzyl acrylate), tribromostyrene, tribromophenyl maleide, tribromoneopentyl alcohol, tetrabromodipentaerythritol, pentabromobenzyl acrylate, pentabromophenol, Pentabromotoluene, pentabromodiphenyl oxide, hexabromocyclododecane, hexabromodiphenyl ether, octabromophenol ether, octadibromodiphenyl ether, octabromodiphenyl oxide, dibromoneo Flame retardant compounds containing halogens such as n-tyl glycol tetracarbonate, bis (tribromophenyl) fumaramide, N-methylhexabromodiphenylamine, styrene bromide, diallyl chlorendate; in addition, chlorendic anhydride, phthalic anhydride, Examples thereof include compounds containing bisphenol A, glycidyl compounds such as glycidyl ether, polyhydric alcohols such as diethylene glycol and pentaerythritol, and modified carbamides. These may be used alone or in combination of two or more.
[0017]
The flame retardant resin composition of the present invention may contain other additives as necessary. For example, a crosslinking agent, a crosslinking accelerator, a crosslinking accelerator, an activator, a crosslinking inhibitor, an anti-aging agent, an antioxidant, an ozone degradation inhibitor, an ultraviolet absorber, a light stabilizer, a tackifier, Plasticizer, softener, reinforcing agent, reinforcing agent, foaming agent, foaming aid, stabilizer, lubricant, mold release agent, antistatic agent, modifier, coloring agent, coupling agent, antiseptic, antifungal agent, modified Examples include additives, adhesives, flavoring agents, polymerization catalysts, polymerization initiators, polymerization inhibitors, polymerization inhibitors, polymerization regulators, polymerization initiators, crystal nucleating agents, compatibilizing agents, dispersing agents, antifoaming agents, etc. It is done. These are used alone or in combination of two or more.
[0018]
The flame retardant resin composition of the present invention contains a resin, a flame retardant, and other components as necessary, for example, one selected from the group of rolls, kneaders, Banbury mixers, intermixes, single screw extruders, and twin screw extruders. The flame retardant resin composition is prepared by kneading with the above kneader, and the flame retardant resin composition is, for example, from the group of press molding machines, injection molding machines, mold molding machines, blow molding machines, extrusion molding machines, and spinning molding machines. It can be molded by one or more selected molding machines.
[0019]
The flame-retardant resin composition of the present invention is used for plastic parts of machines and devices, plastic parts of buildings, plastic parts of vehicles, and the like that can be heating sources such as electricity, gas, petroleum, coal, and nuclear power. . For example, air conditioners, radios, televisions, fans, dishwashers, microwave ovens, juicers, mixers, cookers, washing machines, audio equipment, video appliances, snap switches, cord wires, plug receptacles, printed circuit boards , Cord sets / power cords, temperature display control panels, electronic parts such as transformers, electric wires, connector products, curtains, wallpaper, walls, beams, floors, carpets and other building materials, seats, panels, floors, insulation materials, etc. Materials and the like.
[0020]
【Example】
The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the following examples.
[0021]
Flame retardant synthesis examples 1-9
Synthesis example 1 (reference example)
100 g of magnesium hydroxide particles (Kisuma 5 manufactured by Kyowa Chemical Co., Ltd.) 10 g of a silicone compound having an SiH bond in the molecular structure (AMS Max DMS-H25: Table 1) in 300 mL of tetrahydrofuran was stirred at room temperature for 1 hour, and then turned to a rotary evaporator. Then tetrahydrofuran (THF) was removed. Next, the thing from which the solvent was removed was heat-treated at 120 ° C. for 12 hours with a dryer to obtain a flame retardant.
[0022]
Synthesis example 2
To 900 mL of water, 100 g of magnesium hydroxide particles (Kisuma 5 manufactured by Kyowa Chemical Co., Ltd.) are stirred, and water glass (sodium silicate # 31 manufactured by Tokuyama Co., Ltd.) is mixed with SiO 2 on the magnesium hydroxide particles. 2 1 g in terms of conversion is added, stirred for 30 minutes, dehydrated and dried. 100 g of the obtained water glass-treated magnesium hydroxide particles were stirred with 10 g of a silicone compound having a SiH bond in the molecular structure (DMS-H25 manufactured by Azumax) and 1 g of dibutyltin dilaurate in 300 mL of tetrahydrofuran at room temperature for 1 hour, and then Tetrahydrofuran (THF) was removed with a rotary evaporator. Next, the product from which the solvent had been removed was heat-treated at 120 ° C. for 12 hours with a dryer to obtain the flame retardant of the present invention.
[0023]
Synthesis example 3
A flame retardant of the present invention was obtained in the same manner as in Synthesis Example 2 except that dibutyltin dilaurate was not added.
[0024]
Synthesis Examples 4-9
The flame retardant of this invention was obtained by the same method as the synthesis example 3 except using the compound of the following Table 1 for the silicone compound to add. In Table 1, the silicone compounds used in Synthesis Examples 1 to 3 are also shown.
[0025]
[Table 1]
SiH bond amount and non-SiH chemistry for water glass treated magnesium hydroxide particles (K1) of silicone compounds having SiH groups in the molecular structures of the products obtained in Synthesis Examples 1 to 9 and water glass treated magnesium hydroxide particles The binding amount (unit: PPH) was examined. 1 g of the product prepared in a 30 ml beaker and 10 g of THF are stirred at room temperature for 1 hour. The mixed solution is filtered through Millipore, and the filtrate is dried in a vacuum oven at 120 ° C. for 3 hours. The weight of the dried filtrate is measured. Since the weight of the dried filtrate was a non-chemical bond amount, the value obtained by subtracting the value from the charged amount was defined as the chemical bond amount. The results are shown in Table 2 below.
[0027]
[Table 2]
From Table 2 above, Synthesis Example 1 in which magnesium hydroxide particles not treated with water glass were treated with a silicone compound having a SiH group in the molecular structure and SiH groups in the molecular structure of magnesium hydroxide particles treated with water glass. In comparison with Synthesis Examples 2 to 9 in which a silicone compound having a hydrogen content was treated, the particles of Synthesis Examples 2 to 9 had a higher SiH chemical bond amount than Synthesis Example 1. This is because the reactivity of the OH group on the water glass of the water-treated magnesium hydroxide particle and the SiH group of the silicone compound is higher than the reactivity of the OH group on the surface of the magnesium hydroxide particle and the SiH group of the silicone compound. It is believed that there is.
[0029]
Examples 1-8
A flame retardant resin composition in which 100 parts by weight of a polyethylene resin was blended with 100 parts by weight of the flame retardant prepared in Synthesis Examples 2 to 9 was prepared, and a flame retardant test was performed. Samples were prepared and processed into 150 mm × 3 mm × 3 mm test pieces using a biaxial kneader and a press molding machine, respectively. The biaxial kneading conditions were a material supply unit of 160 ° C., a kneading unit of 190 ° C., and a discharge unit of 170 ° C., and press forming was annealed at 180 ° C. for 10 minutes and then with water cooling for 10 minutes to produce a flame retardant test specimen. did. The flame retardancy test method was measured according to oxygen index measurement JIS K 7201.
[0030]
Comparative Example 1
A flame retardant resin composition in which 100 parts by weight of polyethylene resin was blended with 100 parts by weight of magnesium hydroxide particles treated with water glass was prepared and subjected to a flame retardant test. The sample was prepared and processed into a test piece of 150 mm × 3 mm × 3 mm using a biaxial kneader and a press molding machine. The biaxial kneading conditions were a material supply unit of 160 ° C., a kneading unit of 190 ° C., and a discharge unit of 170 ° C., and press forming was annealed at 180 ° C. for 10 minutes and then with water cooling for 10 minutes to produce a flame retardant test specimen. did. The flame retardancy test method was measured according to oxygen index measurement JIS K 7201.
[0031]
Comparative Example 2
A flame retardant resin composition was prepared by blending 100 parts by weight of magnesium hydroxide treated with water glass, 10 parts by weight of a silicone compound (DMS-H25 manufactured by Azmax), and 100 parts by weight of a polyethylene resin, and subjected to a flame retardant test. . The sample was prepared and processed into a test piece of 150 mm × 3 mm × 3 mm using a biaxial kneader and a press molding machine. Biaxial kneading conditions were performed at a material supply unit of 160 ° C., a kneading unit of 190 ° C., and a discharge unit of 170 ° C., and press forming was annealed at 180 ° C. × 10 minutes and then water-cooled for 10 minutes to produce a flame retardant test specimen. did. The flame retardancy test method was measured according to oxygen index measurement JIS K 7201.
The results of Examples 1-8 and Comparative Examples 1-2 are summarized in Table 3 below.
[0032]
[Table 3]
From the results in Table 3, the following (a) to (d) are understood.
(A) Comparative Example 1 of 100 parts by weight of magnesium hydroxide particles treated only with water glass to 100 parts by weight of polyethylene resin, 100 parts by weight of magnesium hydroxide particles only treated with water glass for 100 parts by weight of polyethylene resin, and SiH in the molecular structure In Comparative Example 2 in which the silicone compound having a group was separately kneaded with the magnesium hydroxide particles without chemical bonding, the oxygen index was slightly improved (the oxygen index of the polyethylene resin was about 17).
[0034]
(B) Further, Examples 1 to 8 in which the water-glass-treated magnesium hydroxide particles were coated with a silicone compound having a SiH group in the molecular structure, the water-glass-treated magnesium hydroxide particles had SiH groups in the molecular structure. The oxygen index was uniformly high as compared with Comparative Example 2 in which the silicone compound was not bonded.
[0035]
(C) Next, comparing Example 1 in which dibutyltin dilaurate was added as a catalyst for promoting the reaction between the OH group in water glass and the SiH group in the silicone compound, and Example 2 in which dibutyltin dilaurate was not added, dibutyltin dilaurate was added. The oxygen index of Example 1 was high.
[0036]
(D) In Examples 1 to 8, in which substances having different molecular structures of silicone compounds having a SiH group in the molecular structure are chemically bonded to magnesium hydroxide particles treated with water glass, the molecular structure has a SiH group. Example 6 with a SiH equivalent of 65 in the silicone compound showed a high oxygen index. Thus, it was an unexpected result that the flame-retardant resin composition containing the water glass-treated magnesium hydroxide particles combined with the silicone compound having a low SiH equivalent was very good.
[0037]
【The invention's effect】
According to the present invention, the flame retardant of the present invention in which a silicone compound having a SiH group in its molecular structure is coated on and chemically bonded to magnesium hydroxide particles treated with water glass has the following excellent effects.
(1) The flame retardant of the present invention in which a silicone compound having a SiH group in the molecular structure is coated on and chemically bonded to magnesium hydroxide particles treated with water glass, is added to magnesium hydroxide particles not treated with water glass in the molecular structure. It shows a high chemical bond amount as compared with the processed silicone compound having a group.
(2) The flame retardant of the present invention in which a silicone compound having a SiH group in its molecular structure is chemically bonded to magnesium hydroxide particles treated with water glass has a higher flame resistance than those not having its chemical bonding properties. Showing gender.
(3) The flame retardant of the present invention in which a silicone compound having a SiH group in its molecular structure and having a low SiH equivalent is chemically bonded to magnesium hydroxide particles treated with water glass exhibits particularly high flame retardancy.
(4) The flame retardant of the present invention in which a silicone compound having a SiH group in the molecular structure is chemically bonded to magnesium hydroxide particles treated with water glass promotes the reaction between the OH group of water glass and the SiH group of the silicone compound. Higher flame retardancy is exhibited by adding a catalyst.
Claims (11)
Priority Applications (2)
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| JP2001090615A JP3803557B2 (en) | 2001-03-27 | 2001-03-27 | Flame retardant, method for producing the same, and flame retardant resin composition |
| PCT/JP2002/002557 WO2002077121A1 (en) | 2001-03-27 | 2002-03-18 | Flame retardant, method for preparation thereof and flame-retardant resin composition |
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| JP2001090615A JP3803557B2 (en) | 2001-03-27 | 2001-03-27 | Flame retardant, method for producing the same, and flame retardant resin composition |
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| JP3803557B2 true JP3803557B2 (en) | 2006-08-02 |
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| KR101131802B1 (en) | 2010-10-15 | 2012-03-30 | 주식회사 젠트로 | Functional paint composition, manufacturing method for the same and coating method using the same |
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| KR100846547B1 (en) * | 2004-07-13 | 2008-07-15 | 히다치 가세고교 가부시끼가이샤 | Epoxy resin molding material for sealing and electronic component device |
| JP4997704B2 (en) | 2005-02-24 | 2012-08-08 | 富士ゼロックス株式会社 | Surface-coated flame-retardant particles and production method thereof, and flame-retardant resin composition and production method thereof |
| JP4997705B2 (en) * | 2005-02-24 | 2012-08-08 | 富士ゼロックス株式会社 | Surface-coated flame-retardant particles and production method thereof, and flame-retardant resin composition and production method thereof |
| JP4935082B2 (en) | 2006-01-23 | 2012-05-23 | 富士ゼロックス株式会社 | Flame retardant resin composition and flame retardant resin molded product |
| JP2010031271A (en) * | 2008-07-02 | 2010-02-12 | Yazaki Corp | Silicone surface-treated magnesium hydroxide |
| CN102532948A (en) * | 2011-12-30 | 2012-07-04 | 大连亚泰科技新材料有限公司 | Preparation method and application of modified magnesium hydroxide flame retardant for copper clad plate |
| CN113493673A (en) * | 2020-03-19 | 2021-10-12 | 佛山市顺德区天采有机硅有限公司 | Flame-retardant silicone sealant and preparation method thereof |
| CN115651383B (en) * | 2022-10-20 | 2023-09-26 | 金发科技股份有限公司 | Polycarbonate alloy material and preparation method and application thereof |
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| JPS55160042A (en) * | 1979-05-30 | 1980-12-12 | Sumitomo Chem Co Ltd | Thermoplastic resin composition |
| JP2585052B2 (en) * | 1988-03-14 | 1997-02-26 | 神島化学工業株式会社 | Manufacturing method of inorganic flame retardant for thermoplastic resin |
| JP2645086B2 (en) * | 1988-06-23 | 1997-08-25 | 日本化学工業株式会社 | Silica-coated magnesium hydroxide and method for producing the same |
| JP2825500B2 (en) * | 1988-07-29 | 1998-11-18 | 日本ユニカー株式会社 | Flame-retardant polyolefin resin composition |
| JP3478607B2 (en) * | 1994-09-19 | 2003-12-15 | 株式会社資生堂 | Manufacturing method of treated powder |
| JP2001226676A (en) * | 2000-02-14 | 2001-08-21 | Kansai Research Institute | Flame retardant, method of producing the flame retardant, and flame-retarding resin composition |
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2001
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| KR101131802B1 (en) | 2010-10-15 | 2012-03-30 | 주식회사 젠트로 | Functional paint composition, manufacturing method for the same and coating method using the same |
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