JP2004323633A - Silicone adhesive for vehicle and method for repairing sealing material for vehicle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a silicone adhesive for a vehicle, which simplifies an operation for installing a transparent base plate on a vehicle, its repair operation and to provide a method for repairing a sealing material for a vehicle. <P>SOLUTION: The silicone adhesive for a vehicle is equipped with an inner frame body 3 having an approximately inverted U-shaped cross section to be peripherally arranged on the peripheral part of an opening 2 for window glass of a body 1, a press edge body 4 having an approximately inverted U-shaped cross section which is peripherally arranged on the peripheral part of the opening 2 for the window glass and faces the inner frame body 3 through a gap 5, the approximately rectangular window glass 6 covering the opening 2 for the window glass and a plurality of silicone adhesives 10 for bonding the peripheral parts of the inner frame body 3, the press edge body 4 and the window glass 6. Each silicone adhesive 10 comprises a silicone adhesive composition 11 which is formed in a belt-like form and has 100-500 degree of plasticity at 25°C by a parallel plate plastometer and a film 12 peelably applied to one side of the silicone adhesive composition 11. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

（式中、Ｒは置換又は非置換の一価炭化水素基、Ｘは酸素原子又は炭素数１〜８の二価炭化水素基、ｎはジオルガノポリシロキサンの２５℃における粘度を１，０００，０００ｃｓ以上とする数である）
【００２０】
【化２】

（式中、Ｙは加水分解性基、ａは２又は３、Ｒ、Ｘ、ｎは上記と同様である）
【００２１】
ここで、Ｒは、メチル基、エチル基、プロピル基、ブチル基、２−エチルブチル基、オクチル基等のアルキル基、シクロヘキシル基、シクロペンチル基等のシクロアルキル基、ビニル基、プロペニル基、ブテニル基、ヘプテニル基、ヘキセニル基、アリル基等のアルケニル基、フェニル基、トリル基、キシリル基、ナフチル基、ジフェニル基等のアリール基、ベンジル基、フェニルエチル基等のアラルキル基、あるいはこれらの基の炭素原子に結合している水素原子の一部又は全部をハロゲン原子、シアノ基等で置換したクロロメチル基、トリフロロプロピル基、２−シアノエチル基、３−シアノプロピル基等から選択される同一又は異種の非置換若しくは置換の好ましくは炭素数１〜１２、特に１〜１０の一価炭化水素基である。
【００２２】
Ｘは酸素原子又は炭素数１〜８の二価炭化水素基であり、二価炭化水素基としては−（ＣＨ_２）_ｍ−（ｍは１〜８）で表される。これらの中でも酸素原子、−ＣＨ_２ＣＨ_２−が好ましい。ｎはジオルガノポリシロキサンの２５℃における粘度を１００〜１，０００，０００ｃｓ、好ましくは５００〜５００，０００ｃｓとする数である。また、Ｙは加水分解性基である。具体的には、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等のアルコキシ基、ジメチルケトオキシム基、メチルエチルケトオキシム基等のケトオキシム基、アセトキシ基等のアシルオキシ基、イソプロペニルオキシ基、イソブテニルオキシ基等のアルケニルオキシ基等があげられる。
【００２３】
このようなジオルガノポリシロキサンは、各種オルガノポリシロキサンの単量体である環状シロキサン若しくは線状オリゴマーを酸若しくは塩基触媒による平衡反応によって得る等の公知の方法により製造することができる。また、ジオルガノポリシロキサンに分岐構造を導入する場合、上記平衡化重合中にＳｉＯ_３／２単位、及び／又はＳｉＯ_４／２単位を含むシラン若しくはシロキサンをジオルガノポリシロキサンがゲル化しないレベルで添加するのが常法である。さらに、このジオルガノポリシロキサンは、ストリップや洗浄等により低分子シロキサンを除去しておくことが望ましい。このようなオルガノシロキサンを用いた場合、初期の汚れを低減することができる。
【００２４】
架橋剤
架橋剤としては、加水分解性の基を１分子中に２個以上、好ましくは３個以上有するシラン、あるいはその部分加水分解縮合物が使用される。この場合、その加水分解性の基としては、メトキシ基、エトキシ基、ブトキシ基等のアルコキシ基、ジメチルケトオキシム基、メチルエチルケトオキシム基等のケトオキシム基、アセトキシ基等のアシルオキシ基、イソプロペニルオキシ基、イソブテニルオキシ基等のアルケニルオキシ基、Ｎ−ブチルアミノ基、Ｎ，Ｎ−ジエチルアミノ基等のアミノ基、Ｎ−メチルアセトアミド基等のアミド基等があげられる。これらの中でも、アルコキシ基、ケトオキシム基、アシルオキシ基、アルケニルオキシ基が好ましい。架橋剤の配合量は、上記ジオルガノポリシロキサン１００部（質量部、以下同様）に対して１〜５０部、好ましくは２〜３０部、より好ましくは５〜２０部が良い。
【００２５】
硬化触媒
シリコーン接着性組成物１１には、硬化触媒を使用することにより硬化を促進することができる。この硬化触媒としては、ジブチル錫ジアセテート、ジブチル錫ジラウレート、ジブチル錫ジオクトエート等のアルキル錫エステル化合物、テトライソプロポキシチタン、テトラｎ−ブトキシチタン、テトラキス（２−エチルヘキソキシ）チタン、ジプロポキシビス（アセチルアセトナ）チタン、チタニウムイソプロポキシオクチレングリコール等のチタン酸エステル又はチタンキレート化合物、ナフテン酸亜鉛、ステアリン酸亜鉛、亜鉛−２−エチルオクトエート、鉄−２−エチルヘキソエート、コバルト−２−エチルヘキソエート、マンガン−２−エチルヘキソエート、ナフテン酸コバルト、アルコキシアルミニウム化合物等の有機金属化合物、３−アミノプロピルトリエトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン等のアミノアルキル基置換アルコキシシラン、ヘキシルアミン、リン酸ドデシルアミン等のアミン化合物及びその塩、ベンジルトリエチルアンモニウムアセテート等の第４級アンモニウム塩、酢酸カリウム、酢酸ナトリウム、蓚酸リチウム等のアルカリ金属の低級脂肪酸塩、ジメチルヒドロキシルアミン、ジエチルヒドロキシルアミン等のジアルキルヒドロキシルアミン、テトラメチルグアニジルプロピルトリメトキシシラン、テトラメチルグアニジルプロピルメチルジメトキシシラン、テトラメチルグアニジルプロピルトリス（トリメチルシロキシ）シラン等のグアニジル基を含有するシラン又はシロキサン等があげられる。これらは、１種に限定されず、２種若しくはそれ以上の混合物でも良い。
【００２６】
これら硬化触媒の配合量は、上記ジオルガノポリシロキサン１００部に対して０〜２０部、好ましくは０．００１〜１０部、より好ましくは０．０１〜５部が良い。
【００２７】
充填剤
シルコーン接着性組成物１１には、上記成分以外に補強等の目的で１種以上の充填剤を用いることが好ましい。このような充填剤としては、例えば、煙霧質シリカ、沈降性シリカ、これらのシリカ表面を有機珪素化合物で疎水化処理したシリカ、石英粉末、カーボンブラック、タルク、ゼオライト及びベントナイト等の補強剤、アスベスト、ガラス繊維、炭素繊維及び有機繊維等の繊維質充填剤、炭酸カルシウム、炭酸亜鉛、酸化亜鉛、酸化マグネシウム、セライト等の塩基性充填剤等が例示される。
【００２８】
これらの充填剤のうち、シリカ、炭酸カルシウム、ゼオライト等が好ましく、特に表面を疎水化処理した煙霧質シリカ、炭酸カルシウムが最適である。充填剤の配合量は、目的や充填剤の種類により選択すれば良いが、後述するベースポリマーのジオルガノポリシロキサン成分１００部に対して１〜５００部、特に５〜１００部が良い。
【００２９】
接着剤賦与成分
接着促進剤としては、γ−アミノプロピルトリメトキシシラン、γ−（２−アミノエチル）アミノプロピルトリメトキシシラン等のアミノ基含有オルガノアルコキシシラン、γ−グリシドキシプロピルトリメトキシシラン等のエポキシ基含有オルガノアルコキシシラン、γ−メルカプトプロピルトリメトキシシラン等のメルカプト含有オルガノアルコキシシラン、アミノ基含有オルガノアルコキシシランとエポキシ基含有オルガノアルコキシシランとの反応混合物が例示される。本成分の配合量は、通常、後述するジポリオルガノシロキサン成分１００質量部に対して０．１〜５質量部である。
【００３０】
（２）ヒドロシリル化反応硬化型シリコーン接着剤
このヒドロシリル化反応硬化型シリコーン接着剤の基本組成は、概ね以下のポリオルガノシロキサン、水酸化ポリオルガノシロキサン、硬化触媒、充填剤、接着性付与成分からなる。
【００３１】
ポリオルガノシロキサン
ヒドロシリル化反応硬化型シリコーン接着剤組成物の主剤であり、一分子中に平均２個以上のアルケニル基を有することを特徴とする。このアルケニル基としては、ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基が例示され、好ましくはビニル基である。また、本成分中のアルケニル基以外のケイ素原子に結合する有機基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等のアルキル基；フェニル基、トリル基、キシリル基等のアリール基；３−クロロプロピル基、３，３，３−トリフルオロプロピル基等のハロゲン化アルキル基が例示され、好ましくはメチル基が良い。本成分の分子構造としては、例えば、直鎖状、一部分枝を有する直鎖状、分枝鎖状、網状、樹枝状があげられる。本成分の２５℃における粘度は、１００，０００ｍＰａ・ｓ以上、好ましくは１，０００，０００ｍＰａ・ｓ以上である。
【００３２】
この成分のポリオルガノシロキサンとしては、分子鎖両末端ジメチルビニルシロキシ基封鎖ポリジメチルシロキサン、分子鎖両末端ジメチルビニルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体、分子鎖両末端トリメチルシロキシ基封鎖ジメチルシロキサン・メチルビニルシロキサン共重合体、式：（ＣＨ_３）_３ＳｉＯ_１／２で示されるシロキサン単位と式：（ＣＨ_３）_２（ＣＨ_２＝ＣＨ）ＳｉＯ_１／２で示されるシロキサン単位と式：ＳｉＯ_４／２で示されるシロキサン単位からなるポリオルガノシロキサン、これらのポリオルガノシロキサンのメチル基の一部又は全部をエチル基、プロピル基等のアルキル基；フェニル基、トリル基等のアリール基；３，３，３−トリフルオロプロピル基等のハロゲン化アルキル基で置換したポリオルガノシロキサン、これらのポリオルガノシロキサンのビニル基の一部または全部をアリル基、プロペニル基等のアルケニル基で置換したポリオルガノシロキサン、及びこれらのポリオルガノシロキサンの二種以上の混合物が例示される。
【００３３】
水素化ポリオルガノシロキサン
このポリオルガノシロキサンは、本組成物の硬化剤として作用するものであり、一分子中に平均２個以上のケイ素原子結合水素原子を有することを特徴とする。本成分中のケイ素原子に結合する有機基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等のアルキル基；フェニル基、トリル基、キシリル基等のアリール基；３−クロロプロピル基、３，３，３−トリフルオロプロピル基等のハロゲン化アルキル基が例示され、好ましくはメチル基が良い。本成分の分子構造としては、直鎖状、一部分枝を有する直鎖状、分枝鎖状、網状、樹枝状が例示される。本成分の２５℃における粘度は、限定されないが、好ましくは１〜１，０００，０００ｍＰａ・ｓの範囲内、より好ましくは１〜１０，０００ｍＰａ・ｓの範囲内である。
【００３４】
この成分のポリオルガノシロキサンとしては、分子鎖両末端ジメチルハイドロジェンシロキシ基封鎖ポリジメチルシロキサン、分子鎖両末端トリメチルシロキシ基封鎖ポリメチルハイドロジェンシロキサン、分子鎖両末端トリメチルシロキシ封鎖ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体、環状ポリメチルハイドロジェンシロキサン、式：（ＣＨ_３）_２ＨＳｉＯ_１／２で示されるシロキサン単位と式：ＳｉＯ_４／２で示されるシロキサン単位からなるポリオルガノシロキサン、これらのポリオルガノシロキサンのメチル基の一部または全部をエチル基、プロピル基等のアルキル基；フェニル基、トリル基等のアリール基；３，３，３−トリフルオロプロピル基等のハロゲン化アルキル基で置換したポリオルガノシロキサン、及びこれらのポリオルガノシロキサンの二種以上の混合物が例示され、得られる硬化物の機械的特性、特に伸びが向上することから、分子鎖両末端にのみケイ素原子結合水素原子を有するポリオルガノシロキサンと分子鎖側鎖にケイ素原子結合を有するポリオルガノシロキサンの混合物であることが好ましい。
【００３５】
本組成物において本成分の含有量は、ジオルガノポリシロキサン成分中のアルケニル基に対する本成分中のケイ素原子結合水素原子のモル比が０．０１〜２０の範囲内となる量であり、好ましくは０．１〜１０の範囲内となる量、特に好ましくは、０．１〜５の範囲内となる量である。これは、本成分の含有量が上記範囲の下限未満であると、得られる接着剤が十分に硬化しなくなる傾向があるからである。また、範囲の上限を超えると、得られる接着剤硬化物の機械的特性が低下する傾向があるからである。
【００３６】
本成分として、分子鎖両末端にのみケイ素原子結合水素原子を有するポリオルガノシロキサンと分子鎖側鎖にケイ素原子結合を有するポリオルガノシロキサンの混合物を用いる場合には、前者のポリオルガノシロキサンの含有量は、ジオルガノポリシロキサン成分中のアルケニル基に対する本成分中のケイ素原子結合水素原子のモル比が０．０１〜１０の範囲内となる量であることが好ましく、さらには０．１〜１０の範囲内となる量、特には０．１〜５の範囲内となる量であることが好ましい。後者のポリオルガノシロキサンの含有量は、ジオルガノポリシロキサン成分中のアルケニル基に対する本成分中のケイ素原子結合水素原子のモル比が０．５〜２０の範囲内となる量であることが好ましく、さらには０．５〜１０の範囲内となる量、より好ましくは０．５〜５の範囲内となる量が最適である。
【００３７】
硬化触媒
ヒドロシリル化反応用白金系触媒としては、白金微粉末、白金黒、塩化白金酸、アルコール変性塩化白金酸、白金とジケトンの錯体、塩化白金酸とオレフィン類の錯体、塩化白金酸とアルケニルシロキサンの錯体及びこれらをアルミナ、シリカ、カーボンブラック等の担体に担持させたものがあげられる。これらの中でも、塩化白金酸とアルケニルシロキサンの錯体がヒドロシリル化反応触媒としての触媒活性が高いので好ましく、特に特公昭４２−２２９２４号公報に開示されているような塩化白金酸とジビニルテトラメチルジシロキサン錯体が良い。本成分の添加量は、ジオルガノポリシロキサン成分１００万質量部に対して、白金金属原子として１〜１０００質量部、好ましくは１〜１００質量部である。
【００３８】
充填剤
充填剤は、本組成物の機械的強度を向上させるために添加されるものであり、通常シリコーンゴムの配合に用いられる化合物が用いられる。この成分としては、例えばヒュームドシリカ、沈降性シリカ、焼成シリカ、粉砕石英、及びこれらのシリカ粉末をオルガノアルコキシシラン、オルガノハロシラン、オルガノシラザン等の有機ケイ素化合物で表面処理した粉末があげられる。特に、得られる接着剤硬化物の機械的強度を十分に向上させるため、本成分としてＢＥＴ比表面積が５０ｍ^２／ｇ以上であるシリカ粉末を用いることが好ましい。
【００３９】
本組成物において、本成分の含有量は任意であるが、得られるシリコーンゴム硬化物の機械的強度を向上させるため、ジオルガノポリシロキサン成分１００質量部に対して１〜１０００質量部の範囲内であることが好ましく、さらには１〜４００質量部の範囲内が最適である。また、本組成物には、その他任意の成分として、例えばヒュームド酸化チタン、カーボンブラック、カーボンナノチューブ、ケイ藻土、酸化鉄、酸化アルミニウム、アルミノケイ酸塩、炭酸カルシウム、酸化亜鉛、水酸化アルミニウム、銀、金、ニッケル等の無機質充填剤、金又は銀メッキを施した無機及び有機充填剤；これらの充填剤の表面を上記有機ケイ素化合物で処理した充填剤を含有することも可能である。
【００４０】
接着性付与成分
本ヒドロシリル化反応硬化型シリコーン接着剤を接着剤として機能させるためにその接着性を賦与、向上させるためのものである。これには、メチルトリメトキシシラン、ビニルトリメトキシシラン、アリルトリメトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−アミノプロピルトリメトキシシラン、Ｎ−（２−アミノエチル）−３−アミノプロピルトリメトキシシラン、ビス（トリメトキシシリル）プロパン、ビス（トリメトキシシリル）ヘキサン等のシランカップリング剤及びこれらの部分加水分解物；エポキシ基、酸無水物基、αシアノアクリル基を有する有機化合物及びこれらの基を含有するシロキサン化合物、あるいはこれらの基とアルコキシシリル基を併有する有機化合物若しくはシロキサン化合物；テトラエチルチタネート、テトラプロピルチタネート、テトラブチルチタネート、テトラ（２−エチルヘキシル）チタネート、チタンエチルアセトネート、チタンアセチルアセトネート等のチタン化合物；エチルアセトアセテートアルミニウムジイソプロピレート、アルミニウムトリス（エチルアセトアセテート）、アルキルアセトアセテートアルミニウムジイソプロピレート、アルミニウムトリス（アセチルアセトネート）、アルミニウムモノアセチルアセトネートビス（エチルアセトアセテート）等のアルミニウム化合物；ジルコニウムアセチルアセトネート、ジルコニウムブトキシアセチルアセトネート、ジルコニウムビスアセチルアセトネート、ジルコニウムエチルアセトアセテート等のジルコニウム化合物を含有しても良い。これらの接着付与剤の含有量は、限定されないが、好ましくはジオルガノポリシロキサン成分１００質量部に対して０．０１〜１０質量部の範囲内である。
【００４１】
さらに、本組成物には、その硬化性を調整するため、３−メチル−１−ブチン−３−オール、３，５−ジメチル−１−ヘキシン−３−オール、３−フェニル−１−ブチン−３−オール等のアセチレン系化合物；３−メチル−３−ペンテン−１−イン、３，５−ジメチル−３−ヘキセン−１−イン等のエンイン化合物；１，３，５，７−テトラメチル−１，３，５，７−テトラビニルシクロテトラシロキサン、１，３，５，７−テトラメチル−１，３，５，７−テトラヘキセニルシクロテトラシロキサン、分子鎖両末端シラノール基封鎖メチルビニルシロキサン、分子鎖両末端シラノール基封鎖メチルビニルシロキサン・ジメチルシロキサン共重合体等の１分子中にビニル基を５重量％以上持つオルガノシロキサン化合物；ベンゾトリアゾール等のトリアゾール類、フォスフィン類、メルカプタン類、ヒドラジン類等の硬化抑制剤を含有することが好ましい。これらの硬化抑制剤の含有量は、限定されないが、ジオルガノポリシロキサン成分１００質量部に対して０．００１〜５質量部の範囲内が好適である。
【００４２】
本組成物を調製する方法は、限定されるものではなく、必要に応じてその他の任意の成分を混合して調製することができるが、予めジオルガノポリシロキサン成分と充填剤を加熱混合して調製したベースコンパウンドに、残余の成分を添加することが好ましい。その他の意の成分を添加する必要がある場合、ベースコンパウンドを調製する際に添加しても良い。また、これが加熱混合により変質する場合には、架橋剤、硬化触媒、充填剤成分の添加時に添加することが好ましい。また、このベースコンパウンドを調製する際、上記有機ケイ素化合物を添加し、充填剤の表面をｉｎ‐ｓｉｔｕ処理しても良い。本接着剤を調製する際、２本ロール、ニーダーミキサ、ロスミキサ等の周知の混練装置を用いることが可能である。
【００４３】
定形成形体の製造方法
上記により得られる本組成物を定形成形体に加工する場合には、通常の成形に使用される加工機を用いれば良い。例えば、カレンダーロール、Ｔダイ、あるいは異形ダイを備えた押出機、さらにはプレス機等によるプレフォームにより、未硬化の成形体が得られる。成形体の表面はそれぞれの加工速度、ジグの平滑性により制御されるが、この際、未硬化の成形体が接着機能を有することを考慮すれば、より強固な接着を得るため、成形体の表面の粗度や粘着性を適切に制御する必要がある。
【００４４】
そこで、成形体について検討した結果、成形体表面の粗度は、１．０ｍｍ以下が好ましい。これは、成形体表面の粗度が１．０ｍｍを超える場合には、本組成物の未硬化時の被着体に対する接着面積が低下して被着体に対する粘着力を低下させ、位置ずれや剥離が生じるからである。また、硬化後も被着体に対する十分な接触面積を得られていないことから、所定の接着力を得ることができず、剥離の原因となるからである。
【００４５】
また、成形体表面の粘着性、いわゆる未硬化物の表面タックがＪＩＳ Ｚ ０２３７〔球転法〕により測定して３〜２１の範囲に制御することが有用である。これは、３未満の場合には、被着体に対する粘着力が十分に得られなくなり、本組成物と被着体の間で位置ずれや剥離が発生しやすくなるからである。逆に、２１を超える場合には、組成物の表面に離型フィルム等を貼着した場合、離型フィルムの剥離時に剥離性が著しく低下し、組成物の破損を招くという理由に基づく。
【００４６】
本発明においては、被着体にプライマーを塗布することにより、シリコーン接着剤１０の接着性を高めることができる。プライマーは、各種の物質を含む表面処理剤を溶媒に分散したものが殆どである。このプライマーにおいて、上記表面処理剤は、シランカップリング剤であることが好ましい。このシランカップリング剤は、上記溶媒１００質量部に対して１〜５０質量部配合すると良い。ここで、シランカップリング剤の好ましい配合量を上記分散媒１００質量部に対して１〜５０質量部の範囲としたのは、この範囲を下回る場合には、十分な接着力が得られないという弊害が生じるからである。逆に、この範囲を上回る場合には、加工性が低下するという弊害が生じるからである。
【００４７】
上記シランカップリング剤としては、エポキシ基含有シラン又はそれらの部分加水分解縮合物、（メタ）アクリル基含有シラン又はそれらの部分加水分解縮合物、ビニル基含有シラン又はそれらの部分加水分解縮合物、環状シロキサン、鎖状シロキサン、及び、シアヌル環含有有機ケイ素化合物、からなる群から選択される１又は２以上の物質を用いるのが好ましい。上記エポキシ基含有シランの例としては、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルトリエトキシシラン、３−グリシドキシプロピル（メチル）ジメトキシシラン、２−（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、２−（３，４−エポキシシクロヘキシル）エチルトリエトキシシラン、２−（３，４−エポキシシクロヘキシル）エチル（メチル）トリエトキシシラン等があげられる。
【００４８】
上記（メタ）アクリル基含有シランの例としては、３−メタクリロキシプロピルトリメトキシシラン、３−メタクリロキシプロピルトリエトキシシラン、３−メタクリロキシプロピル（メチル）ジメトキシシラン等があげられる。上記ビニル基含有シランの例としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（２−メトキシエトキシ）シラン等があげられる。
【００４９】
上記環状シロキサンの例としては、３−グリシドキシプロピル基含有メチルハイドロジェン環状テトラシロキサン、３−メタクリロキシプロピル基含有メチルハイドロジェン環状テトラシロキサン、３−グリシドキシプロピル基含有メチルメトキシ環状シロキサン、３−グリシドキシプロピル基と２−（トリメトキシシリル）エチル基を有するメチルハイドロジェン環状シロキサン、３−メタクリロキシプロピル基と２−（トリメトキシシリル）エチル基を有するメチルハイドロジェン環状シロキサン、２−［（３−トリメトキシシリル）プロピルオキシカルボニル］プロピル基含有メチルハイドロジェン環状シロキサン等があげられる。
【００５０】
上記鎖状シロキサンの例としては、３−グリシドキシプロピル基含有メチルメトキシシロキサン、３−グリシドキシ基とビニル基を有するメチルハイドロジェンシロキサン、３−グリシドキシ基と２−（トリメトキシシリル）エチル基を有するメチルシロキサン等があげられる。上記シアヌル環含有有機ケイ素化合物の例としては、トリス（３−トリメトキシシリルプロピル）イソシアヌレート等があげられる。これらのプライマーは、被着体に対し刷毛等を用いて塗布することから、スプレーコータやロールコータ等のコーティング機によって塗布するか、あるいはプライマー溶液中に被着体をディッピングして塗布させると良い。
【００５１】
フィルム１２は、通常、断面板形の薄いポリプロピレン、ポリエチレンテレフタレート、ポリエチレン等のプラスチックフィルムからなる。このフィルム１２は、シリコーン接着剤１０を保持する役目を果たすが、この他にも、直線性の付加による作業性の向上、塵埃及び黴の付着防止、目地部の損傷防止、表面の平滑性、表面の硬度、自由な着色及び表面加工が可能等、意匠性に優れるという種々の機能も具備する。
【００５２】
上記構成において、鉄道車両に窓ガラス６を設置する場合には、窓枠を構成する内部骨組み体３と押縁体４との間に、窓ガラス６を固定片７を介して挿入し、定形の各シリコーン接着剤１０からフィルム１２を剥離しながら内部骨組み体３・押縁体４と窓ガラス６の周縁部との間に圧入し、その後、未硬化の各シリコーン接着剤１０を常温で放置して硬化接着すれば、鉄道車両に窓ガラス６を設置することができる。
【００５３】
上記構成によれば、液状ではなく、定形の各シリコーン接着剤１０を使用するので、従来、内部骨組み体３・押縁体４と窓ガラス６との間に介在させていた樹脂製のシール材、すなわちバックアップ材８が不要となる。したがって、作業工程や部品点数を削減して作業の著しい円滑化、簡素化、迅速化、容易化を図ることができる。
【００５４】
なお、上記実施形態では内部骨組み体３と押縁体４との間に、窓ガラス６を固定片７を介して挿入したが、何らこれに限定されるものではない。例えば、図３に示すように、押縁体４を省略するとともに、内部骨組み体３を断面略Ｚ字形に形成してその下端部には窓ガラス６を固定片７を介し支持させ、シリコーン接着剤１０からフィルム１２を剥離しながら内部骨組み体３と窓ガラス６の周縁部との間に圧入した後、未硬化のシリコーン接着剤１０を常温で放置して硬化接着しても良いのはいうまでもない。
【００５５】
次に、図４は本発明に係る車両用シーリング材の補修方法の実施形態を示すもので、この場合には、鉄道車両を構成する車体１の窓ガラス用開口２の全周縁部に周設された内部骨組み体３と、窓ガラス用開口２の全周縁部に周設されて内部骨組み体３に隙間５を介して対向した押縁体４と、車両の窓ガラス用開口２を被覆して内部骨組み体３と押縁体４との間に介在した窓ガラス６と、内部骨組み体３・押縁体４と窓ガラス６の周縁部との間に介在した複数のバックアップ材８と、内部骨組み体３・押縁体４と窓ガラス６の周縁部とを接着したポリサルファイド系の複数のシーリング材９とを備え、経時的に損傷したシーリング材９の損傷部９ａをシリコーン接着剤１０により補修するようにしている。
【００５６】
シリコーン接着剤１０は、上記と同様、帯状等の定形に形成されて平行板可塑度計による２５℃の可塑度が１００〜５００の範囲のシリコーン接着性組成物１１と、このシリコーン接着性組成物１１に剥離可能に貼着される離型用のフィルム１２とから構成される。このシリコーン接着剤１０は、時間の経過に伴い部分的に損傷したシーリング材９の損傷部９ａに適宜充填されて平滑仕上げされ、常温放置あるいは加熱されることにより、硬化してシーリング材９と一体化される。その他の部分については、車両用シリコーン接着剤１０の実施形態と同様であるので説明を省略する。
【００５７】
上記構成によれば、液状ではなく、定形の各シリコーン接着剤１０を使用するので、作業を簡素化して作業の著しい円滑化、迅速化、容易化を図ることができる。さらに、補修作業の際、ポリサルファイド系のシーリング材９を使用するものではないので、マスキングテープの貼着や剥離作業を省略することができ、補修作業の著しい円滑化、簡素化、迅速化、容易化を図ることが可能になる。
【００５８】
【実施例】
以下、本発明に係る車両用シリコーン接着剤及び車両用シーリング材の補修方法の実施例について比較例と共に説明する。
実施例１
ヒドロシリル化反応シリコーン接着剤
先ず、混練り器（ニーダ）中で珪素原子に結合した全置換基に対する炭素数２以上の置換基（ビニル基）の割合が０．４４モル％の無色透明流動性固体両末端ビニルジメチルシロキシ基封鎖ジメチルシロキサン、ビニルメチルシロキサン共重合体（粘度２０００万ｍＰａ・ｓ、ウィリアムス可塑度９０）を１００質量部と表面がジメチルジクロロシランで処理された乾式シリカ〔日本アエロジル製；商品名アエロジルＲ９７２〕３０質量部、両末端ジメチルヒドロキシシリル基封鎖の重合度が約１０のジメチルポリシロキサン２質量部を均一に混合し、窒素通気雰囲気下で１５０℃／１時間加熱しながら混合し、冷却した。
【００５９】
次いで、ミキシングロールを使用し、冷却状態にて上記混練物１００質量部に対して、ジメチルシロキサン・メチルハイドロジェンシロキサン共重合体（メチルハイドロジェンシロキサンの量は、０．７モル／１００ｇ）１．７２質量部、塩化白金酸溶液（塩化白金酸５質量部を２−エチルヘキサノールに希釈したもの）０．２７質量部、ビニルトリエトキシシラン１質量部、３−メチル−１−ブチン−３−オール０．０５質量部を均一に混練し、組成物を調製した。
【００６０】
可塑度の測定
上記組成物の混練直後のウイリアムス可塑度を、２５℃において平行板可塑度計（ウイリアムスプラストメータ）を使用して、ＪＩＳ Ｋ ６２４９〔未硬化及び硬化シリコーンゴムの試験方法〕に規定する測定方法に準じて測定したところ、測定値は１８３であった。すなわち、ポリオルガノポリシロキサン２ｇを球状の試験片とし、この試験片をセロハン紙に挟んでダイヤルゲージの付いた平行板可塑度計〔上島製作所製；商品名ウイリアムスプラストメータ〕中にセットし、５ｋｇの荷重を加えて３分間放置するとともに、ダイヤルゲージの目盛りをミリメートルの１／１００まで読み取り、試験片の厚さを記録し、その後、係る数値を１００倍してウイリアムス可塑度とした。
【００６１】
賦 形
上記組成物を２３℃ ５０％ＲＨの環境下で一軸押出機を用いてＯＰＰ（二軸延伸ポリエチレン）フィルム（４０μｍ）上に幅６ｍｍ、厚み５ｍｍの寸法に賦形した。
【００６２】
車両用窓ガラスの設置
先ず、窓ガラスのガラス板として複層ガラス（高さ９５０ｍｍ、幅１８００ｍｍ、厚さ１６ｍｍ）を使用し、この複層ガラスに適したスチール製の内部骨組み体の底面二箇所に、厚さ１０ｍｍの硬質ウレタン製の固定片を接着剤により接着固定した。こうして接着固定したら、図５（ａ）のようにシリコーン接着剤を内部骨組み体の内周面に貼着し、フィルム上から指先で軽く押し付け、その後、フィルムを剥離した。同様に、押縁体の所定箇所にもシリコーン接着剤を貼着してフィルム上から指先で軽く押し付けた後、フィルムを剥離した。
【００６３】
そして、複層ガラスを内部骨組み体に貼着したシリコーン接着剤の表面に圧着し、図５（ｂ）のようにシリコーン接着剤を備えた押縁体を複層ガラスの表面に貼着、圧着し、その後、押縁体を内部骨組み体に固定して図１に示す構造を得た。窓ガラスの施工作業に際しては、従来のシーリング材による施工時に必要不可欠とした複層ガラス、内部骨組み体、又は車体に対するマスキングテープの貼り付け、汚染防止用カバーの取り付け、取り外し等は一切不要であった。
【００６４】
実施例２
縮合反応シリコーン接着剤
先ず、密閉混練り器中で両末端水酸基封鎖ポリジメチルシロキサンを１００質量部と表面がジメチルジクロロシランで処理された乾式シリカ〔日本アエロジル製；商品名アエロジルＲ９７２〕３０質量部を均一に混合し、これにメチルトリスメチルエチルケトオキシムシラン４質量部、ジブチルスズジオクトエート０．０５質量部を減圧下で均一になるまで混合して組成物を調製した。
【００６５】
可塑度の測定
上記組成物の混練直後の可塑度を平行板可塑度計（ウイリアムスプラストメータ）を使用して、ＪＩＳ Ｋ ６２４９〔未硬化及び硬化シリコーンゴムの試験方法〕に準じて測定したところ、３分間荷重をかけた状態で１７３の測定値を得た。
【００６６】
粘着性（球転法）の測定
ＪＩＳＺ０２３７：２０００〔粘着テープ・粘着シートの試験方法〕傾斜式ボールタックの試験方法の基づき、傾斜角３０°で実施したところ、最大のボールナンバーは１４だった。
賦 形
上記組成物を２３℃，１０％ＲＨの環境下一軸押出機を用いてＯＰＰ（二軸延伸ポリエチレン）フィルム（４０μｍ）上に幅６ｍｍ、厚み５ｍｍの寸法に賦形した。
【００６７】
取り付けシーリング材の補修
先ず、ポリサルファイド系のシーリング材の損傷部に本発明に係るシリコーン接着剤をＯＰＰフィルム上から適量押し込み、ＯＰＰを剥離した。シリコーン接着剤の食み出し部については、ヘラを用いることにより容易に除去することができた。これにより、補修部以外をシリコーン接着剤で汚染することなく、図４に示す構造を得ることができた。この補修作業の実施に際しては、従来のシーリング材による補修時に必要とした複層ガラス、内部骨組み体、又は車体に対するマスキングテープの貼着、汚染防止用カバーの取り付け、取り外し等を全て省略することができた。
【００６８】
比較例１
実施例１において、表面がジメチルジクロロシランで処理された乾式シリカ〔日本アエロジル社製 商品名エロジルＲ９７２〕７０質量部、両末端ジメチルヒドロキシシリル基封鎖の重合度が約１０のジメチルポリシロキサン４．５質量部を変更した以外は同様の方法で組成物を調製するとともに、同様の方法で測定評価したところ、可塑度は４５５、粘着性は２であった。
【００６９】
係る組成物を実施例１と同様に賦形して車両用窓ガラスを設置し、図５（ａ）に示すように内部骨組み体の内周面にシリコーン接着剤を貼着し、フィルム上から指先で軽く押し付け、その後、フィルムを剥離した。
すると、シリコーン接着剤の粘着力が不足していたため、内部骨組み体の内周面からシリコーン接着剤がフィルムと共に剥離してしまい、施工が不可能となった。
【００７０】
比較例２
実施例２において、表面がジメチルジクロロシランで処理された乾式シリカ〔日本アエロジル社製 商品名エロジルＲ９７２〕７５質量部、メチルトリスメチルエチルケトオキシムシラン１０質量部に変更した以外は同様の方法で組成物を調製するとともに、同様の方法で測定評価したところ、可塑度は５１０、粘着性は３であった。
【００７１】
係る組成物を実施例２と同様に賦形して図４に示すようにＯＰＰフィルム上から適量押し込もうとしたところ、シリコーン接着剤の可塑度が高く、損傷部の形状に変形せず、大きな隙間が多数発生した。また、シリコーン接着剤の食み出し部については、ヘラを用いて除去しようとしたところ、食み出し部と押し込まれていた部分とが全て取り除かれてしまい、補修が不可能だった。
【００７２】
比較例３
先ず、図６に示すように、固定片上に窓ガラスとして複層ガラス（高さ９５０ｍｍ、幅１８００ｍｍ、厚さ１６ｍｍ）を設置して押縁体をセットし、内部骨組み体と複層ガラス間、及び押縁体と複層ガラス間に樹脂製のシール材（バックアップ材）を周方向に貼着した。この際、シーリング材の食み出しを考慮して複層ガラス、内部骨組み体、及び押縁体の周囲にマスキングテープを貼着し、ペンギンシール１６９〔サンスター技研社製；２成分ポリサルファイド系シーリング材〕を打設した。
【００７３】
シーリング材の打設後の食み出し部については、ヘラを用いて除去した。この際、打設したシーリング材が液状なので、食み出し部の除去には、ヘラの押圧とかき取り速度とを一定にしないと、シーリング材の表面に凹凸が発生するため、十分に注意が必要であり、作業が慎重にならざるを得なかった。また、複層ガラス、内部骨組み体、及び押縁体の周囲に予め貼着しておいたマスキングテープを除去しなければならなかった。さらにその後、シーリング材が硬化するまで表面を僅かでも触れたり、強い衝撃を加えると、シーリング材の表面が凸凹になるので、仕上げ後の取り扱いには、十分注意しなければならなかった。
【００７４】
【発明の効果】
以上のように本発明によれば、車両に透明基板を設置する作業やその補修作業の簡素化等を図ることができるという効果がある。
【図面の簡単な説明】
【図１】本発明に係る車両用シリコーン接着剤の実施形態を示す模式断面説明図である。
【図２】本発明に係る車両用シリコーン接着剤及び車両用シーリング材の補修方法の実施形態におけるシリコーン接着剤を示す模式断面説明図である。
【図３】本発明に係る車両用シリコーン接着剤の他の実施形態を示す模式断面説明図である。
【図４】本発明に係る車両用シーリング材の補修方法の実施形態を示す模式断面説明図である。
【図５】本発明に係る車両用シリコーン接着剤の実施例を示す模式断面説明図である。
【図６】本発明に係る車両用シリコーン接着剤の比較例を示す模式断面説明図である。
【符号の説明】
１ 車体
２ 窓ガラス用開口（開口）
３ 内部骨組み体（支持体）
４ 押縁体（支持体）
５ 隙間
６ 窓ガラス（透明基板）
９ シーリング材
９ａ 損傷部
１０ シリコーン接着剤
１１ シリコーン接着性組成物
１２ フィルム[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a vehicle silicone adhesive and a method for repairing a vehicle sealing material, which can simplify a window glass installation operation of a vehicle and a repair operation of a sealing material.
[0002]
[Prior art]
Conventionally, as a method of installing a window glass on a railway vehicle, although not shown, for example, upper and lower stile members, left and right side column members, and corner members constituting a window glass opening, a window glass holding portion is integrally formed, and There is known a method of fixing and bonding a window glass to a window glass holding portion with a liquid sealing material (see Patent Document 1). In addition, an opening for window glass, a window frame, and a window glass are configured so that an external fitting type window glass can be slid vertically from the outer surface side of the railway vehicle and inserted. A method is also known in which a window glass is fixed and adhered to a vehicle outer panel and a window frame with a liquid sealing material so that the outer surfaces are substantially parallel (see Patent Document 2). In either method, the window glass is fixed and adhered using a sealing material, and as the sealing material, a polysulfide type is selected in view of the problem of the periphery of joints and outer plate contamination. .
[0003]
[Patent Document 1]
JP-A-61-155053
[0004]
[Patent Document 2]
JP-A-5-221212
[0005]
[Problems to be solved by the invention]
Conventionally, when a window glass is installed on a railway vehicle, a masking tape is attached to a predetermined portion such as an outer plate of the vehicle or a window glass, and a plastic sealing agent (backer agent) having a circular cross section is applied to a portion where the sealing material is cast. Is inserted and a two-liquid mixing type polysulfide-based sealing material is cast and leveled with a spatula, and then the masking tape is removed, so that the number of working steps is small and as a result, the work becomes extremely complicated. There is a problem.
[0006]
In addition, when the outer panel of a vehicle exposed to ultraviolet rays or the like and the window glass are fixed with a polysulfide-based sealing material, a partial loss occurs in the sealing material in about two to three years. Must be repaired. Regarding this repair work, a masking tape is again adhered to the outer plate of the vehicle and the window glass, a polysulfide-based sealing material is cast, and after smoothing with a spatula, the masking tape has to be peeled off. As a result, the operation becomes complicated as described above.
[0007]
The present invention has been made in view of the above, and provides a method of repairing a vehicle silicone adhesive and a vehicle sealing material that can simplify the work of installing a transparent substrate on a vehicle and the repair work thereof. It is an object.
[0008]
[Means for Solving the Problems]
In the present invention, in order to achieve the above object, a support is provided on the periphery of the opening of the vehicle, the opening of the vehicle is covered with a transparent substrate, and the support and the periphery of the transparent substrate are sealed with a silicone adhesive. To adhere,
The silicone adhesive was used as a standard silicone adhesive composition, and the plasticity of the standard silicone adhesive composition before curing at 25 ° C. with a parallel plate plastometer was set in the range of 100 to 500, and JIS Z 0237 The ball number is set in the range of 3 to 21 in the adhesion test based on the ball rolling method.
[0009]
In addition, the silicone adhesive composition can be cured by a condensation reaction.
Further, the silicone adhesive composition can be cured by a hydrosilylation reaction.
Further, it is preferable to provide a film that is releasably attached to the silicone adhesive composition.
[0010]
Further, in the present invention, in order to achieve the above object, a support provided on a peripheral portion of an opening of a vehicle, a transparent substrate covering the opening of the vehicle, and a sealing material for bonding the support and the peripheral portion of the transparent substrate A repair method for repairing a damaged portion of the sealing material with a silicone adhesive, comprising:
A silicone adhesive is formed from a silicone adhesive composition formed into a fixed form and having a plasticity at 25 ° C. in a range of 100 to 500 measured by a parallel plate plastometer and a film releasably attached to the silicone adhesive composition. It is characterized by comprising.
[0011]
Here, the vehicles in the claims include at least various types of railway vehicles and automobiles. The opening of this vehicle is mainly for windows, but may be used for other purposes. In addition, the support includes a single or a plurality of support plates having a substantially U-shaped cross section, a pressing member, a substantially I-shaped cross section, a substantially L-shaped cross section, and a substantially Z-shaped cross section. The transparent substrate is mainly a transparent window glass, but may be a transparent plastic plate or the like. Further, the silicone adhesive composition is formed into a shape such as a substantially linear shape, and specific examples of the shape include a band shape, a string shape, a ribbon shape, a sheet shape and the like.
[0012]
BEST MODE FOR CARRYING OUT THE INVENTION
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a preferred embodiment of the present invention will be described with reference to the drawings. As shown in FIG. 1 and FIG. 2, an inner frame 3 provided around the entire periphery of the window frame 2, a pressing member 4 provided around the entire periphery of the window glass opening 2 and facing the internal frame 3 via a gap 5, and a window of the vehicle. A plurality of silicone adhesives covering the glass opening 2 and interposing the window glass 6 interposed between the inner frame 3 and the edge 4 and the inner frame 3, the edge 4 and the periphery of the window 6. And an agent 10.
[0013]
The window glass opening 2 is formed in a substantially rectangular shape on the side surface of the vehicle body 1. As shown in FIG. 1, the inner frame 3 and the pressing member 4 are each formed in a substantially inverted U-shaped cross section, and a gap 5 for a window glass 6 is formed therebetween to form a window frame. I do. The window glass 6 is made of, for example, a double-layer glass having a substantially rectangular shape in a plane, and is inserted between the inner frame 3 and the pressing member 4 via a fixing piece 7.
[0014]
As shown in FIG. 2, the silicone adhesive 10 is formed in a band shape having a rectangular cross section before curing, and has a plasticity at 25 ° C. measured by a parallel plate plastometer at 25 ° C. in the range of 100 to 500. A release film 12 releasably adhered to one surface of the silicone adhesive composition 11, the peripheral portions of the inner frame 3 and the window glass 6, and the peripheral edges of the pressing member 4 and the window glass 6. Between the parts.
[0015]
The silicone adhesive composition 11, in other words, the silicone adhesive 10 must maintain its shape without deviating from the cross-linked rubber. For this reason, it is preferable that the plasticity of the silicone adhesive 10 is in the range of 100 to 500 as measured by a Williams plasticity meter. This is because when the plasticity is less than 100, the shape retention when the silicone adhesive 10 is formed into an uncured fixed-form body or the shape retention after molding is reduced, and an arbitrary shape is obtained. Is difficult.
[0016]
Conversely, if the plasticity of the silicone adhesive 10 exceeds 500, it is extremely difficult to remove air bubbles remaining at the interface when the silicone adhesive 10 is adhered to an adherend. Further, when the damaged portion of the sealing material is repaired using the silicone adhesive 10 having a plasticity exceeding 500, when the silicone adhesive 10 is pressed into the damaged portion of the sealing material, the silicone adhesive 10 is shaped into the damaged portion. This is because deformation does not follow, and a large number of voids are generated between the damaged portion of the sealing material and the pushed-in silicone adhesive 10. Further, the tackiness of the silicone adhesive 10 is preferably in the range of 3 to 21 in a ball number in a tackiness test based on the ball rolling method of JISZ0237.
[0017]
As the silicone adhesive 10, a silicone rubber adhesive 10 obtained by any crosslinking method such as a radical reaction, a hydrosilylation reaction using a platinum-based catalyst, a condensation reaction, ultraviolet light, and electron beam curing can be used. However, in practice, a cured product by an addition reaction or a cured adhesive by a condensation reaction is preferred from an economic and physical viewpoint.
[0018]
(1) Condensation-curable silicone adhesive
The basic composition of this condensation-curable silicone adhesive generally comprises the following polyorganosiloxane, crosslinking agent, curing catalyst, filler, and adhesive-providing component.
Polyorganosiloxane
It is a main component of the condensation-curable silicone adhesive and is a diorganopolysiloxane represented by the following chemical formula (1) or (2).
[0019]
Embedded image

(Wherein, R is a substituted or unsubstituted monovalent hydrocarbon group, X is an oxygen atom or a divalent hydrocarbon group having 1 to 8 carbon atoms, n is the viscosity of the diorganopolysiloxane at 25 ° C of 1,000, 000 cs or more)
[0020]
Embedded image

(Wherein, Y is a hydrolyzable group, a is 2 or 3, R, X, and n are the same as described above)
[0021]
Here, R is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a 2-ethylbutyl group, an octyl group, a cycloalkyl group such as a cyclohexyl group or a cyclopentyl group, a vinyl group, a propenyl group, a butenyl group, Heptenyl group, hexenyl group, alkenyl group such as allyl group, phenyl group, tolyl group, xylyl group, naphthyl group, aryl group such as diphenyl group, aralkyl group such as benzyl group, phenylethyl group, or carbon atom of these groups The same or different selected from chloromethyl, trifluoropropyl, 2-cyanoethyl, 3-cyanopropyl and the like in which part or all of the hydrogen atoms bonded to Unsubstituted or substituted is preferably a monovalent hydrocarbon group having 1 to 12, particularly 1 to 10 carbon atoms.
[0022]
X is an oxygen atom or a divalent hydrocarbon group having 1 to 8 carbon atoms. As the divalent hydrocarbon group,-(CH ₂ ) _m -(M is 1 to 8). Among these, an oxygen atom, -CH ₂ CH ₂ -Is preferred. n is a number that makes the viscosity of the diorganopolysiloxane at 25 ° C. 100 to 1,000,000 cs, preferably 500 to 500,000 cs. Y is a hydrolyzable group. Specifically, alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group, dimethyl ketoxime group, ketoxime group such as methyl ethyl ketoxime group, acyloxy group such as acetoxy group, isopropenyloxy group, isobutenyloxy group And alkenyloxy groups such as a group.
[0023]
Such a diorganopolysiloxane can be produced by a known method such as obtaining a cyclic siloxane or linear oligomer, which is a monomer of various organopolysiloxanes, by an equilibrium reaction using an acid or base catalyst. When a branched structure is introduced into the diorganopolysiloxane, SiO 2 may be added during the above equilibrium polymerization. _3/2 Unit and / or SiO _4/2 It is customary to add silane or siloxane containing units at a level at which the diorganopolysiloxane does not gel. Further, it is desirable that the low molecular siloxane is removed from the diorganopolysiloxane by stripping or washing. When such an organosiloxane is used, initial contamination can be reduced.
[0024]
Crosslinking agent
As the cross-linking agent, a silane having two or more, preferably three or more hydrolyzable groups in one molecule or a partially hydrolyzed condensate thereof is used. In this case, as the hydrolyzable group, a methoxy group, an ethoxy group, an alkoxy group such as a butoxy group, a dimethyl ketoxime group, a ketoxime group such as a methyl ethyl ketoxime group, an acyloxy group such as an acetoxy group, an isopropenyloxy group, Examples include an alkenyloxy group such as an isobutenyloxy group, an amino group such as an N-butylamino group and an N, N-diethylamino group, and an amide group such as an N-methylacetamido group. Among these, an alkoxy group, a ketoxime group, an acyloxy group, and an alkenyloxy group are preferred. The compounding amount of the crosslinking agent is 1 to 50 parts, preferably 2 to 30 parts, more preferably 5 to 20 parts with respect to 100 parts (parts by mass, the same applies hereinafter) of the diorganopolysiloxane.
[0025]
Curing catalyst
The use of a curing catalyst in the silicone adhesive composition 11 can promote curing. Examples of the curing catalyst include alkyltin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, and dibutyltin dioctoate; tetraisopropoxytitanium, tetran-butoxytitanium, tetrakis (2-ethylhexoxy) titanium, dipropoxybis (acetylacetate). Na) Titanate or titanium chelate compound such as titanium, titanium isopropoxyoctylene glycol, zinc naphthenate, zinc stearate, zinc-2-ethyl octoate, iron-2-ethylhexoate, cobalt-2-ethyl Organometallic compounds such as hexoate, manganese-2-ethylhexoate, cobalt naphthenate, and alkoxyaluminum compound, 3-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoate Aminoalkyl group-substituted alkoxysilanes such as xysilanes, amine compounds such as hexylamine, dodecylamine phosphate and salts thereof, quaternary ammonium salts such as benzyltriethylammonium acetate, and alkali metals such as potassium acetate, sodium acetate and lithium oxalate. Lower fatty acid salts, dialkylhydroxylamine such as dimethylhydroxylamine, diethylhydroxylamine, etc., tetramethylguanidylpropyltrimethoxysilane, tetramethylguanidylpropylmethyldimethoxysilane, tetramethylguanidylpropyltris (trimethylsiloxy) silane, etc. And a silane or siloxane containing a guanidyl group. These are not limited to one type, and may be a mixture of two or more types.
[0026]
The compounding amount of these curing catalysts is 0 to 20 parts, preferably 0.001 to 10 parts, more preferably 0.01 to 5 parts with respect to 100 parts of the diorganopolysiloxane.
[0027]
filler
In the sircone adhesive composition 11, it is preferable to use one or more fillers for the purpose of reinforcement or the like in addition to the above components. Such fillers include, for example, fumed silica, precipitated silica, silica obtained by hydrophobizing these silica surfaces with an organosilicon compound, quartz powder, reinforcing agents such as carbon black, talc, zeolite and bentonite, and asbestos. And fibrous fillers such as glass fiber, carbon fiber and organic fiber, and basic fillers such as calcium carbonate, zinc carbonate, zinc oxide, magnesium oxide and celite.
[0028]
Among these fillers, silica, calcium carbonate, zeolite and the like are preferable, and particularly, fumed silica and calcium carbonate whose surfaces are subjected to hydrophobic treatment are most suitable. The amount of the filler may be selected depending on the purpose and the type of the filler, but is preferably 1 to 500 parts, particularly 5 to 100 parts, per 100 parts of the diorganopolysiloxane component of the base polymer described below.
[0029]
Adhesive component
Examples of the adhesion promoter include an amino group-containing organoalkoxysilane such as γ-aminopropyltrimethoxysilane and γ- (2-aminoethyl) aminopropyltrimethoxysilane, and an epoxy group-containing such as γ-glycidoxypropyltrimethoxysilane. Examples thereof include a mercapto-containing organoalkoxysilane such as organoalkoxysilane and γ-mercaptopropyltrimethoxysilane, and a reaction mixture of an amino group-containing organoalkoxysilane and an epoxy group-containing organoalkoxysilane. The compounding amount of this component is usually 0.1 to 5 parts by mass with respect to 100 parts by mass of a dipolyorganosiloxane component described later.
[0030]
(2) Hydrosilylation reaction-curable silicone adhesive
The basic composition of this hydrosilylation reaction-curable silicone adhesive generally comprises the following polyorganosiloxane, polyorganohydroxide hydroxide, curing catalyst, filler, and adhesion-imparting component.
[0031]
Polyorganosiloxane
It is a main component of the hydrosilylation reaction-curable silicone adhesive composition, and has an average of two or more alkenyl groups in one molecule. Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group, and a vinyl group is preferable. The organic group bonded to a silicon atom other than the alkenyl group in this component includes an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; a phenyl group, a tolyl group, and a xylyl group. And aryl groups such as 3-chloropropyl group and 3,3,3-trifluoropropyl group, and preferably a methyl group. Examples of the molecular structure of this component include a straight chain, a partially branched straight chain, a branched chain, a network, and a dendrite. The viscosity of this component at 25 ° C. is 100,000 mPa · s or more, preferably 1,000,000 mPa · s or more.
[0032]
Examples of the polyorganosiloxane of this component include polydimethylsiloxane having a dimethylvinylsiloxy group at both ends of a molecular chain, a dimethylsiloxane / methylvinylsiloxane copolymer having both ends of a dimethylvinylsiloxy group at the molecular chain, and dimethyl having a trimethylsiloxy group at both ends of the molecular chain. Siloxane / methylvinylsiloxane copolymer, formula: (CH ₃ ) ₃ SiO _1/2 And a siloxane unit represented by the formula: (CH ₃ ) ₂ (CH ₂ = CH) SiO _1/2 And a siloxane unit represented by the formula: SiO _4/2 A polyorganosiloxane comprising a siloxane unit represented by the following formula: an alkyl group such as an ethyl group or a propyl group; or an aryl group such as a phenyl group or a tolyl group; Polyorganosiloxanes substituted with halogenated alkyl groups such as trifluoropropyl groups, polyorganosiloxanes in which some or all of the vinyl groups of these polyorganosiloxanes are substituted with alkenyl groups such as allyl groups and propenyl groups, and the like; And mixtures of two or more of these polyorganosiloxanes.
[0033]
Hydrogenated polyorganosiloxane
This polyorganosiloxane acts as a curing agent of the present composition, and is characterized by having an average of two or more silicon-bonded hydrogen atoms in one molecule. Examples of the organic group bonded to the silicon atom in this component include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group; an aryl group such as a phenyl group, a tolyl group and a xylyl group; Examples thereof include halogenated alkyl groups such as -chloropropyl group and 3,3,3-trifluoropropyl group, and a methyl group is preferable. Examples of the molecular structure of this component include a straight chain, a partially branched straight chain, a branched chain, a network, and a dendrite. The viscosity of this component at 25 ° C. is not limited, but is preferably in the range of 1 to 1,000,000 mPa · s, and more preferably in the range of 1 to 10,000 mPa · s.
[0034]
Examples of the polyorganosiloxane of this component include polydimethylsiloxane having dimethylhydrogensiloxy groups at both ends of molecular chains, polymethylhydrogensiloxane having trimethylsiloxy groups at both ends of molecular chains, and dimethylsiloxane / methylhydrogen having both ends of molecular chains at trimethylsiloxy end. Siloxane copolymer, cyclic polymethylhydrogensiloxane, formula: (CH ₃ ) ₂ HSiO _1/2 And a siloxane unit represented by the formula: SiO _4/2 A polyorganosiloxane comprising a siloxane unit represented by the following formula: an alkyl group such as an ethyl group or a propyl group; or an aryl group such as a phenyl group or a tolyl group; -Polyorganosiloxane substituted with a halogenated alkyl group such as trifluoropropyl group, and a mixture of two or more of these polyorganosiloxanes are exemplified, and the mechanical properties of the obtained cured product, particularly, the elongation is improved. It is preferable to use a mixture of a polyorganosiloxane having a silicon-bonded hydrogen atom only at both ends of a molecular chain and a polyorganosiloxane having a silicon-bonded side chain in the molecular chain.
[0035]
In the present composition, the content of this component is such that the molar ratio of silicon-bonded hydrogen atoms in this component to alkenyl groups in the diorganopolysiloxane component is in the range of 0.01 to 20, and is preferably The amount is in the range of 0.1 to 10, particularly preferably in the range of 0.1 to 5. This is because if the content of this component is less than the lower limit of the above range, the obtained adhesive tends not to be sufficiently cured. Also, when the upper limit of the range is exceeded, the mechanical properties of the cured adhesive obtained tend to decrease.
[0036]
When a mixture of a polyorganosiloxane having silicon atom-bonded hydrogen atoms only at both ends of the molecular chain and a polyorganosiloxane having silicon atom bonds at the side chains of the molecular chain is used as this component, the content of the former polyorganosiloxane is used. Is preferably an amount such that the molar ratio of silicon-bonded hydrogen atoms in this component to alkenyl groups in the diorganopolysiloxane component is in the range of 0.01 to 10, and more preferably 0.1 to 10 The amount is preferably in the range, particularly preferably in the range of 0.1 to 5. The content of the latter polyorganosiloxane is preferably such that the molar ratio of silicon-bonded hydrogen atoms in this component to alkenyl groups in the diorganopolysiloxane component is in the range of 0.5 to 20, Further, an amount in the range of 0.5 to 10, more preferably an amount in the range of 0.5 to 5, is optimal.
[0037]
Curing catalyst
Examples of platinum catalysts for hydrosilylation reaction include platinum fine powder, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of platinum and diketone, complexes of chloroplatinic acid and olefins, complexes of chloroplatinic acid and alkenylsiloxane. And those in which these are carried on a carrier such as alumina, silica, carbon black and the like. Among them, a complex of chloroplatinic acid and alkenylsiloxane is preferable because of its high catalytic activity as a hydrosilylation reaction catalyst. Particularly, chloroplatinic acid and divinyltetramethyldisiloxane as disclosed in JP-B-42-22924 are preferred. Complex is good. The amount of this component to be added is 1 to 1000 parts by mass, preferably 1 to 100 parts by mass, as platinum metal atoms, based on 1,000,000 parts by mass of the diorganopolysiloxane component.
[0038]
filler
The filler is added to improve the mechanical strength of the present composition, and a compound usually used for compounding silicone rubber is used. Examples of this component include fumed silica, precipitated silica, calcined silica, crushed quartz, and powders obtained by surface-treating these silica powders with an organosilicon compound such as organoalkoxysilane, organohalosilane, or organosilazane. In particular, in order to sufficiently improve the mechanical strength of the obtained cured adhesive, the BET specific surface area is 50 m as this component. ² / G or more is preferably used.
[0039]
In the present composition, the content of this component is optional, but in order to improve the mechanical strength of the cured silicone rubber obtained, the content is in the range of 1 to 1000 parts by mass relative to 100 parts by mass of the diorganopolysiloxane component. It is more preferable that the content be in the range of 1 to 400 parts by mass. In addition, the composition further includes other optional components such as fumed titanium oxide, carbon black, carbon nanotubes, diatomaceous earth, iron oxide, aluminum oxide, aluminosilicate, calcium carbonate, zinc oxide, aluminum hydroxide, and silver hydroxide. , An inorganic filler such as gold or nickel, an inorganic or organic filler plated with gold or silver; and a filler obtained by treating the surface of these fillers with the above-mentioned organosilicon compound.
[0040]
Adhesion imparting component
This is for imparting and improving the adhesiveness of the present hydrosilylation reaction-curable silicone adhesive so as to function as an adhesive. These include methyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- (2 Silane coupling agents such as -aminoethyl) -3-aminopropyltrimethoxysilane, bis (trimethoxysilyl) propane, bis (trimethoxysilyl) hexane and partial hydrolysates thereof; epoxy groups, acid anhydride groups, Organic compounds having an α-cyanoacrylic group and siloxane compounds containing these groups, or organic compounds or siloxane compounds having both these groups and alkoxysilyl groups; tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate, tetrabutyl titanate Titanium compounds such as (2-ethylhexyl) titanate, titanium ethyl acetonate, titanium acetyl acetonate; ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum tris (acetyl acetoacetate) Aluminum compounds such as zirconium acetylacetonate, zirconium butoxyacetylacetonate, zirconium bisacetylacetonate, and zirconium ethyl acetoacetate. . The content of these adhesion promoters is not limited, but is preferably in the range of 0.01 to 10 parts by mass based on 100 parts by mass of the diorganopolysiloxane component.
[0041]
Furthermore, in order to adjust the curability of the composition, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-phenyl-1-butyn- Acetylenic compounds such as 3-ol; enein compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; 1,3,5,7-tetramethyl- 1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, a methylvinylsiloxane having a silanol group at both ends of a molecular chain, Organosiloxane compound having a vinyl group in a molecule of 5% by weight or more such as methylvinylsiloxane / dimethylsiloxane copolymer having silanol groups at both ends of molecular chain; benzotriazole Triazoles, phosphines, mercaptans, preferably contains a curing inhibitor such as hydrazines. The content of these curing inhibitors is not limited, but is preferably in the range of 0.001 to 5 parts by mass with respect to 100 parts by mass of the diorganopolysiloxane component.
[0042]
The method for preparing the present composition is not limited, and can be prepared by mixing other optional components as necessary.However, the diorganopolysiloxane component and the filler are mixed by heating in advance. It is preferable to add the remaining components to the prepared base compound. If it is necessary to add other desired components, they may be added when preparing the base compound. Further, when this is deteriorated by heating and mixing, it is preferably added at the time of adding a crosslinking agent, a curing catalyst, and a filler component. When preparing this base compound, the above-mentioned organosilicon compound may be added and the surface of the filler may be subjected to in-situ treatment. When the present adhesive is prepared, a known kneading device such as a two-roller, a kneader mixer, and a ross mixer can be used.
[0043]
Manufacturing method of fixed shaped body
When the present composition obtained as described above is processed into a fixed form, a processing machine used for ordinary molding may be used. For example, an uncured molded product is obtained by an extruder provided with a calender roll, a T die, or a deformed die, or a preform using a press or the like. The surface of the molded body is controlled by the respective processing speed and the smoothness of the jig.At this time, in consideration of the fact that the uncured molded body has an adhesive function, to obtain stronger adhesion, It is necessary to appropriately control the roughness and tackiness of the surface.
[0044]
Then, as a result of examining the compact, the roughness of the compact surface is preferably 1.0 mm or less. This is because, when the roughness of the surface of the molded body exceeds 1.0 mm, the adhesive area of the present composition to the adherend when it is not cured is reduced, and the adhesive force to the adherend is reduced. This is because peeling occurs. In addition, since a sufficient contact area with the adherend is not obtained even after curing, a predetermined adhesive force cannot be obtained, which causes peeling.
[0045]
In addition, it is useful to control the adhesiveness of the surface of the molded body, that is, the so-called uncured surface tack, in the range of 3 to 21 as measured by JIS Z 0237 [Spherical Rolling Method]. This is because, if it is less than 3, sufficient adhesion to the adherend will not be obtained, and misalignment and peeling between the present composition and the adherend will easily occur. Conversely, if it exceeds 21, it is based on the reason that, when a release film or the like is adhered to the surface of the composition, the release property is remarkably reduced when the release film is peeled off, and the composition is damaged.
[0046]
In the present invention, the adhesion of the silicone adhesive 10 can be enhanced by applying a primer to the adherend. Most primers are obtained by dispersing a surface treating agent containing various substances in a solvent. In this primer, the surface treatment agent is preferably a silane coupling agent. The silane coupling agent is preferably blended in an amount of 1 to 50 parts by mass with respect to 100 parts by mass of the solvent. Here, the reason that the preferable amount of the silane coupling agent is in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the dispersion medium is that if the amount is less than this range, sufficient adhesive strength cannot be obtained. This is because adverse effects occur. On the other hand, if it exceeds this range, there is an adverse effect that workability is reduced.
[0047]
Examples of the silane coupling agent include an epoxy group-containing silane or a partially hydrolyzed condensate thereof, a (meth) acryl group-containing silane or a partially hydrolyzed condensate thereof, a vinyl group-containing silane or a partially hydrolyzed condensate thereof, It is preferable to use one or more substances selected from the group consisting of cyclic siloxanes, chain siloxanes, and cyanuric ring-containing organosilicon compounds. Examples of the epoxy group-containing silane include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl (methyl) dimethoxysilane, and 2- (3,4-epoxy). Examples thereof include cyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyl (methyl) triethoxysilane.
[0048]
Examples of the (meth) acryl group-containing silane include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-methacryloxypropyl (methyl) dimethoxysilane. Examples of the vinyl group-containing silane include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, and the like.
[0049]
Examples of the cyclic siloxane include 3-glycidoxypropyl group-containing methyl hydrogen cyclic tetrasiloxane, 3-methacryloxypropyl group-containing methyl hydrogen cyclic tetrasiloxane, 3-glycidoxypropyl group-containing methyl methoxy cyclic siloxane, Methyl hydrogen cyclic siloxane having 3-glycidoxypropyl group and 2- (trimethoxysilyl) ethyl group, methyl hydrogen cyclic siloxane having 3-methacryloxypropyl group and 2- (trimethoxysilyl) ethyl group, 2 And-[(3-trimethoxysilyl) propyloxycarbonyl] propyl group-containing methyl hydrogen cyclic siloxane.
[0050]
Examples of the above chain siloxane include methyl methoxy siloxane containing a 3-glycidoxypropyl group, methyl hydrogen siloxane having a 3-glycidoxy group and a vinyl group, and 3-glycidoxy group and 2- (trimethoxysilyl) ethyl group. And the like. Examples of the cyanuric ring-containing organosilicon compound include tris (3-trimethoxysilylpropyl) isocyanurate. Since these primers are applied to the adherend using a brush or the like, they may be applied by a coating machine such as a spray coater or a roll coater, or may be applied by dipping the adherend in a primer solution. .
[0051]
The film 12 is usually made of a thin plastic film such as polypropylene, polyethylene terephthalate, or polyethylene having a plate-shaped cross section. The film 12 serves to hold the silicone adhesive 10, but in addition to this, improves the workability by adding linearity, prevents dust and mold from adhering, prevents damage to joints, smoothes the surface, It also has various functions of excellent design such as surface hardness, free coloring and surface processing.
[0052]
In the above-described configuration, when the window glass 6 is installed on the railway vehicle, the window glass 6 is inserted between the inner frame body 3 and the pressing member 4 forming the window frame via the fixing piece 7, and the fixed shape is formed. While peeling the film 12 from each of the silicone adhesives 10, it is press-fitted between the inner frame 3 and the edge 4 and the periphery of the window glass 6, and then the uncured silicone adhesives 10 are left at room temperature. By curing and bonding, the window glass 6 can be installed on the railway vehicle.
[0053]
According to the above configuration, since each of the fixed silicone adhesives 10 is used instead of a liquid, a resin sealing material conventionally interposed between the internal skeleton 3 and the edge 4 and the window glass 6 can be used. That is, the backup material 8 becomes unnecessary. Therefore, it is possible to remarkably smooth, simplify, speed up, and facilitate the work by reducing the work process and the number of parts.
[0054]
In the above embodiment, the window glass 6 is inserted between the inner frame 3 and the pressing member 4 via the fixing piece 7, but the present invention is not limited to this. For example, as shown in FIG. 3, the ridge 4 is omitted, the inner frame 3 is formed in a substantially Z-shaped cross section, and a window glass 6 is supported at its lower end via a fixing piece 7, and a silicone adhesive is used. Needless to say, the uncured silicone adhesive 10 may be left at room temperature to be cured and bonded after being pressed between the inner frame 3 and the periphery of the window glass 6 while peeling the film 12 from the film 10. Nor.
[0055]
Next, FIG. 4 shows an embodiment of the method for repairing a vehicle sealing material according to the present invention. In this case, a vehicle body 1 constituting a railway vehicle is provided with a window glass opening 2 around the entire periphery thereof. A cover member 4 provided around the entire periphery of the window frame opening 2 and facing the internal frame member 3 with a gap 5 therebetween; and a window glass opening 2 for the vehicle. A window glass 6 interposed between the inner skeleton 3 and the ridge 4, a plurality of backup members 8 interposed between the inner skeleton 3, the ridge 4 and the periphery of the window glass 6, and an inner skeleton 3. A plurality of polysulfide-based sealing materials 9 in which the edge 4 and the periphery of the window glass 6 are bonded to each other, and the damaged portions 9a of the sealing materials 9 damaged with time are repaired by the silicone adhesive 10. ing.
[0056]
As described above, the silicone adhesive 10 is formed into a fixed shape such as a belt and has a plasticity at 25 ° C. of 100 to 500 measured by a parallel plate plastometer in the range of 100 to 500. And a release film 12 that is releasably attached to 11. The silicone adhesive 10 is appropriately filled into the damaged portion 9a of the sealing material 9 partially damaged with the passage of time, and is smooth-finished. When left at room temperature or heated, the silicone adhesive 10 is cured and integrated with the sealing material 9 Be converted to The other parts are the same as those in the embodiment of the vehicle silicone adhesive 10, and the description is omitted.
[0057]
According to the above configuration, since the fixed silicone adhesive 10 is used instead of the liquid, the operation can be simplified, and the operation can be significantly smoothed, speeded, and facilitated. Further, since the polysulfide-based sealing material 9 is not used at the time of the repair work, it is possible to omit the attaching and detaching work of the masking tape, and the repair work is remarkably smooth, simplified, speeded up, and easily performed. Can be achieved.
[0058]
【Example】
Hereinafter, examples of a method for repairing a vehicle silicone adhesive and a vehicle sealing material according to the present invention will be described together with comparative examples.
Example 1
Hydrosilylation reaction silicone adhesive
First, in a kneader (kneader), a ratio of a substituent (vinyl group) having 2 or more carbon atoms (vinyl group) to all substituents bonded to silicon atoms is 0.44 mol%, a colorless transparent fluid solid vinyl dimethylsiloxy group at both ends. Dry silica (manufactured by Nippon Aerosil; trade name: Aerosil R972) 30 in which 100 parts by mass of a blocked dimethylsiloxane / vinylmethylsiloxane copolymer (viscosity: 20,000,000 mPa · s, Williams plasticity: 90) and a surface thereof are treated with dimethyldichlorosilane 30 Parts by mass, 2 parts by mass of dimethylpolysiloxane having a polymerization degree of about 10 at both ends dimethylhydroxysilyl group blockade, were uniformly mixed, mixed while heating at 150 ° C. for 1 hour in a nitrogen atmosphere, and cooled.
[0059]
Then, using a mixing roll, a dimethylsiloxane / methylhydrogensiloxane copolymer (the amount of methylhydrogensiloxane is 0.7 mol / 100 g) with respect to 100 parts by mass of the kneaded material in a cooled state. 72 parts by mass, 0.27 parts by mass of chloroplatinic acid solution (5 parts by mass of chloroplatinic acid diluted in 2-ethylhexanol), 1 part by mass of vinyltriethoxysilane, 3-methyl-1-butyn-3-ol 0.05 parts by mass was uniformly kneaded to prepare a composition.
[0060]
Measurement of plasticity
The Williams plasticity immediately after kneading of the above composition was measured at 25 ° C. using a parallel plate plasticity meter (Williams plastometer) according to JIS K 6249 [Test method for uncured and cured silicone rubber]. As a result of measurement according to the above, the measured value was 183. That is, 2 g of a polyorganopolysiloxane was used as a spherical test piece, and this test piece was sandwiched between cellophane papers and set in a parallel plate plasticity meter (available from Ueshima Seisakusho; trade name: Williams Plastometer) with a dial gauge and 5 kg. Was left for 3 minutes while applying the load, and the scale of the dial gauge was read to 1/100 of the millimeter, the thickness of the test piece was recorded, and then the numerical value was multiplied by 100 to obtain the Williams plasticity.
[0061]
Shaping
The composition was formed into a size of 6 mm in width and 5 mm in thickness on an OPP (biaxially stretched polyethylene) film (40 μm) using a single screw extruder under an environment of 23 ° C. and 50% RH.
[0062]
Installation of vehicle window glass
First, a double glass (height: 950 mm, width: 1800 mm, thickness: 16 mm) is used as a glass plate for a window glass. A fixed piece made of hard urethane was bonded and fixed with an adhesive. After bonding and fixing in this manner, as shown in FIG. 5 (a), a silicone adhesive was stuck to the inner peripheral surface of the internal skeleton, and lightly pressed with a fingertip from above the film, and then the film was peeled. Similarly, a silicone adhesive was also adhered to a predetermined portion of the pressing member and lightly pressed with a fingertip from above the film, and then the film was peeled off.
[0063]
Then, the double-glazed glass is pressure-bonded to the surface of the silicone adhesive adhered to the inner skeleton, and as shown in FIG. 5 (b), the edge with the silicone adhesive is bonded to the surface of the double-glazed glass and pressed. Then, the tongue was fixed to the inner frame to obtain the structure shown in FIG. When installing window glass, there is no need to attach masking tape to the double-glazed glass, internal frame, or vehicle body, and attach or remove the pollution prevention cover, which was essential when applying conventional sealing materials. Was.
[0064]
Example 2
Condensation reaction silicone adhesive
First, 100 parts by mass of both ends hydroxyl-blocked polydimethylsiloxane and 30 parts by mass of dry silica (manufactured by Nippon Aerosil; trade name Aerosil R972) whose surface was treated with dimethyldichlorosilane were uniformly mixed in a closed kneader, 4 parts by mass of methyltrismethylethylketoxime silane and 0.05 parts by mass of dibutyltin dioctoate were mixed under reduced pressure until uniform to prepare a composition.
[0065]
Measurement of plasticity
The plasticity of the above composition immediately after kneading was measured using a parallel plate plastometer (Williams plastometer) according to JIS K 6249 [Test method for uncured and cured silicone rubber]. A reading of 173 was obtained while running.
[0066]
Measurement of adhesiveness (ball rolling method)
JISZ0237: 2000 [Testing method for pressure-sensitive adhesive tapes / sheets] The maximum ball number was 14 when the test was performed at a tilt angle of 30 ° based on the test method of the tilting ball tack.
Shaping
The composition was formed into a size of 6 mm in width and 5 mm in thickness on an OPP (biaxially stretched polyethylene) film (40 μm) using a single screw extruder under an environment of 23 ° C. and 10% RH.
[0067]
Repair of mounting sealant
First, an appropriate amount of the silicone adhesive according to the present invention was pushed into the damaged part of the polysulfide-based sealing material from above the OPP film, and the OPP was peeled off. The protruding portion of the silicone adhesive could be easily removed by using a spatula. Thereby, the structure shown in FIG. 4 could be obtained without contaminating the portion other than the repaired portion with the silicone adhesive. In carrying out this repair work, it is necessary to omit all the steps such as attaching the masking tape to the double-glazed glass, internal frame, or vehicle body, and attaching and removing the pollution prevention cover, which were required when repairing with the conventional sealing material. did it.
[0068]
Comparative Example 1
In Example 1, 70 parts by mass of dry silica (trade name: Erosil R972, manufactured by Nippon Aerosil Co., Ltd.) whose surface was treated with dimethyldichlorosilane, and a dimethylpolysiloxane 4.5 having a degree of polymerization of about 10 at which both ends dimethylhydroxysilyl groups were blocked was 4.5. A composition was prepared by the same method except that the parts by mass were changed, and the composition was measured and evaluated by the same method. As a result, the plasticity was 455 and the tackiness was 2.
[0069]
The composition was shaped in the same manner as in Example 1, a window glass for a vehicle was installed, and a silicone adhesive was attached to the inner peripheral surface of the internal framework as shown in FIG. The film was peeled off by light pressing with a fingertip.
Then, since the adhesive strength of the silicone adhesive was insufficient, the silicone adhesive was peeled off together with the film from the inner peripheral surface of the internal framework, and the construction became impossible.
[0070]
Comparative Example 2
A composition was prepared in the same manner as in Example 2 except that the surface was changed to 75 parts by mass of dry silica [trade name: Erosil R972 manufactured by Nippon Aerosil Co., Ltd.] treated with dimethyldichlorosilane, and 10 parts by mass of methyltrismethylethylketoxime silane. When prepared and measured and evaluated by the same method, the plasticity was 510 and the tackiness was 3.
[0071]
When such a composition was shaped in the same manner as in Example 2 and an appropriate amount was pressed from above the OPP film as shown in FIG. 4, the plasticity of the silicone adhesive was high, and the silicone adhesive did not deform into the shape of the damaged portion. Many large gaps occurred. When the protruding portion of the silicone adhesive was removed using a spatula, the protruding portion and the pushed-in portion were all removed, making repair impossible.
[0072]
Comparative Example 3
First, as shown in FIG. 6, a double-glazed glass (height: 950 mm, width: 1800 mm, thickness: 16 mm) is set as a window glass on a fixed piece, and a ridge is set. A sealing material (backup material) made of a resin was stuck in the circumferential direction between the edge member and the double-layer glass. At this time, a masking tape is stuck around the double-glazed glass, the inner frame, and the edge member in consideration of the protrusion of the sealing material, and a penguin seal 169 [manufactured by Sunstar Giken; two-component polysulfide-based sealing material is used. ] Was placed.
[0073]
The protruding part after the sealing material was cast was removed using a spatula. At this time, since the sealing material that has been cast is in a liquid state, care must be taken when removing the protruding portion, because if the pressing of the spatula and the scraping speed are not constant, irregularities will occur on the surface of the sealing material. It was necessary and the work had to be careful. Also, the masking tape that had previously been applied around the double glazing, the inner skeleton, and the ridges had to be removed. Furthermore, if the sealing material hardens or hardly touches the surface until the sealing material hardens, the surface of the sealing material becomes uneven.
[0074]
【The invention's effect】
As described above, according to the present invention, there is an effect that the work of installing the transparent substrate in the vehicle and the repair work thereof can be simplified.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional explanatory view showing an embodiment of a vehicle silicone adhesive according to the present invention.
FIG. 2 is a schematic cross-sectional explanatory view showing the silicone adhesive in the embodiment of the vehicle silicone adhesive and the method for repairing a vehicle sealing material according to the present invention.
FIG. 3 is a schematic sectional view showing another embodiment of the vehicle silicone adhesive according to the present invention.
FIG. 4 is a schematic sectional explanatory view showing an embodiment of a method for repairing a vehicle sealing material according to the present invention.
FIG. 5 is a schematic sectional view showing an example of the silicone adhesive for vehicles according to the present invention.
FIG. 6 is a schematic cross-sectional explanatory view showing a comparative example of the silicone adhesive for vehicles according to the present invention.
[Explanation of symbols]
1 Body
2 Window glass openings (openings)
3 internal framework (support)
4 ridges (support)
5 gap
6 Window glass (transparent substrate)
9 Sealants
9a Damaged part
10 Silicone adhesive
11 Silicone adhesive composition
12 films

Claims (5)

A silicone adhesive for vehicles, in which a support is provided at the periphery of the opening of the vehicle, the opening of the vehicle is covered with a transparent substrate, and the support and the periphery of the transparent substrate are bonded with a silicone adhesive.
The silicone adhesive was used as a standard silicone adhesive composition, and the plasticity of the standard silicone adhesive composition before curing at 25 ° C. with a parallel plate plastometer was set in the range of 100 to 500, and JIS Z 0237 A silicone adhesive for vehicles, wherein a ball number is in a range of 3 to 21 in an adhesion test based on a ball rolling method. The silicone adhesive for vehicles according to claim 1, wherein the silicone adhesive composition is cured by a condensation reaction. The silicone adhesive for vehicles according to claim 1, wherein the silicone adhesive composition is cured by a hydrosilylation reaction. 4. The silicone adhesive for vehicles according to claim 1, further comprising a film releasably attached to the silicone adhesive composition. A support provided on the periphery of the opening of the vehicle, a transparent substrate covering the opening of the vehicle, and a sealing material for bonding the support and the periphery of the transparent substrate, and a damaged portion of the sealing material is sealed with a silicone adhesive. A repair method for a vehicle sealing material to be repaired,
A silicone adhesive is formed from a silicone adhesive composition formed into a fixed form and having a plasticity at 25 ° C. in a range of 100 to 500 measured by a parallel plate plastometer and a film releasably attached to the silicone adhesive composition. A method for repairing a vehicle sealing material, characterized by comprising.

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