JP2005036034A - Curable composition and sealing material composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition having excellent operating efficiency which is curable by moisture or the like in the air or the like to form a rubbery elastomer exhibiting excellent properties, prevents the surface of the cured product or the surface of a coating applied on the cured product from being stained and has a wide range of applications for a sealing material, an adhesive, a coating or the like. <P>SOLUTION: The curable composition and the sealing material composition each comprises a liquid urethane resin (A), which is obtained by reacting a polyoxyalkylene-based alcohol with an organic isocyanate, substantially contains neither an isocyanate group nor a hydroxy group and has a molecular weight distribution (Mw/Mn) of at most 1.6, and a curable resin (B). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

（式中、Ｒは炭化水素基であり、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基又は炭素数７〜２０のアラルキル基が好ましく、メチル基が最も好ましい。Ｘで示される反応性基はハロゲン原子、水素原子、水酸基、アルコキシ基、アシルオキシ基、ケトキシメート基、アミド基、酸アミド基、メルカプト基、アルケニルオキシ基及びアミノオキシ基より選ばれる加水分解性の基であり、Ｘが複数の場合には、Ｘは同じ基であっても異なった基であってもよい。このうちＸはアルコキシ基が好ましく、メトキシ基又はエトキシ基が最も好ましい。ａは０、１又は２の整数であり、０又は１が最も好ましい。）
【００３９】
架橋性シリル基の主鎖への導入は、例えば、以下の公知の方法で行うことができる。
（１）末端に水酸基などの官能基を有するポリオキシアルキレン系やビニル系などの重合体に、この官能基に対して反応性を示す活性基及び不飽和基を有する有機化合物（例えばアリルイソシアネート）を反応させ、次いで、得られる反応生成物に加水分解性基を有するヒドロシランを作用させてヒドロシリル化する。
（２）末端に水酸基、エポキシ基やイソシアネート基などの官能基を有するポリオキシアルキレン系やビニル系などの重合体に、この官能基に対して反応性を示す官能基及び架橋性シリル基を有する化合物を反応させる。
この反応性官能基及び架橋性シリル基を有する化合物としては、アミノ基含有シラン類、メルカプト基含有シラン類、エポキシ基含有シラン類、ビニル型不飽和基含有シラン類、塩素原子含有シラン類、イソシアネート基含有シラン類、ハイドロシラン類などが挙げられる。
（３）重合性不飽和結合と架橋性シリル基を有する化合物（例えば、ＣＨ_２＝ＣＨＳｉ（ＯＣＨ_３ ）_３ やＣＨ_２＝ＣＨＣＯＯ（ＣＨ_２）_２Ｓｉ（ＯＣＨ_３ ）_３）と（メタ）アクリル酸アルキルエステル単量体とを共重合させる。
（４）重合性不飽和結合と官能基を有する化合物（例えば、ヒドロキシエチル（メタ）アクリレート或いは（メタ）アクリル酸アリルなど）を（メタ）アクリル酸アルキルエステル単量体に添加して共重合させ、次いで生成する共重合体を前記の反応性官能基及び架橋性シリル基を有する化合物（例えば、イソシアネート基と−Ｓｉ（ＯＣＨ_３）_３ 基を有する化合物や、トリメトキシシラン、トリエトキシシランなどの加水分解性基を有するヒドロシラン類）と反応させる。
【００４０】
シリコーン樹脂、変成シリコーン樹脂の数平均分子量は１，０００以上、特に６，０００〜３０，０００で分子量分布の狭いものが、硬化性組成物の粘度が低いので取り扱い易く、硬化後の強度、伸び、モジュラスなどの物性が優れているので好適である。
【００４１】
架橋性シリル基含有樹脂として好ましい架橋性シリル基含有ポリオキシアルキレン系ウレタン樹脂は、具体的には、ポリオキシアルキレン系ポリオールと、架橋性シリル基含有イソシアネート化合物とを、反応させて得ることができる。
ポリオキシアルキレン系ポリオールは、前記液状ウレタン樹脂（Ａ）の製造におけるものと同様のものが挙げられ、得られる硬化性組成物及びシーリング材組成物の粘度が低く作業性が良好な点と、硬化後のゴム弾性物性や接着性が高い点で、前記と同様の数平均分子量が好ましく、また、１分子当たり平均のアルコール性水酸基の個数は２個以上、更に２〜１０個、特に２〜４個が好ましく、更にまた前記と同様の分子量分布（Ｍｗ／Ｍｎ）の狭いものが好ましい。
前記ポリオキシアルキレン系ポリオールと、架橋性シリル基含有イソシアネート化合物とは、イソシアネート基／水酸基の当量比が０．１〜１．５／１．０、更には０．５〜１．０／１．０となる範囲で反応させるのが好ましい。
この反応の際にも、金属と有機酸との塩、有機金属キレート化合物、有機金属と有機酸との塩などの有機金属化合物、有機アミンやその塩等の公知の前記ウレタン化触媒を用いることができる。これらのうち有機金属化合物が好ましい。
また、更に公知の有機溶媒を用いることもできる。
【００４２】
架橋性シリル基含有イソシアネート化合物は、分子内に１個以上のイソシアネート基と１個以上の架橋性シリル基を少なくとも含有すればよいが、反応の制御のしやすさ、硬化後のゴム弾性が良好な点から、分子内に１個のイソシアネート基と１個の架橋性シリル基を含有する化合物が好ましい。
架橋性シリル基含有イソシアネート化合物としては、具体的には、３−イソシアネートプロピルトリメトキシシラン、３−イソシアネートプロピルトリエトキシシラン、３−イソシアネートプロピルメチルジエトキシシラン、３−イソシアネートプロピルメチルジメトキシシラン、３−イソシアネートプロピルイソプロポキシシラン、イソシアネートトリメトキシシラン、ジイソシアネートジメトキシシランなどが挙げられ、これらは単独で或いは２種以上混合して使用できる。これらのうち、３−イソシアネートプロピルトリメトキシシランが好ましい。
【００４３】
前記ポリサルファイド樹脂は、ポリサルファイド骨格と末端にメルカプト基を有する重合体である。
メルカプト基を末端に有するポリサルファイド樹脂としては、一般式： ＨＳ−（Ｒ_１ −Ｓｘ ）ｎ −Ｒ_２ −ＳＨ で示される構造のものが好ましい。この一般式中のｘは１〜４の整数であり、その平均値は１．５ 〜２．５である。ｎは１〜１２０であり、好ましくは６〜５０である。また、この一般式中のＲ_１ 及びＲ_２ は２価の脂肪族基であり、具体的には−Ｃ_２ Ｈ_４ −、−Ｃ_３ Ｈ_６ −、−Ｃ_４ Ｈ_８ −等が挙げられるが、特にエーテル結合を有するものが好ましく、具体的には例えば以下のものが挙げられる。
−Ｃ_２ Ｈ_４ −Ｏ−Ｃ_２ Ｈ_４ −
−Ｃ_３ Ｈ_６ −Ｏ−Ｃ_３ Ｈ_６ −
−Ｃ_４ Ｈ_８ −Ｏ−Ｃ_４ Ｈ_８ −
−Ｃ_２ Ｈ_４ −Ｏ−ＣＨ_２ −Ｏ−Ｃ_２ Ｈ_４ −
−Ｃ_３ Ｈ_６ −Ｏ−ＣＨ_２ −Ｏ−Ｃ_３ Ｈ_６ −
−Ｃ_４ Ｈ_８ −Ｏ−ＣＨ_２ −Ｏ−Ｃ_４ Ｈ_８ −
上記メルカプト基を末端に有するポリサルファイド樹脂の数平均分子量は、２００〜２００００、特に１０００〜８０００の範囲が好ましい。
ポリサルファイド樹脂は、過酸化カルシウムなどの金属酸化物を配合したものを大気中に暴露することにより、湿気により過酸化水素が生成し、樹脂を室温で酸化、硬化させる一液硬化型として使用できるし、また、ポリサルファイド樹脂を主剤とし、二酸化鉛やポリイソシアネートなどを硬化剤とし、これらを使用の際に混合することにより硬化させる二液硬化型としても使用できる。
【００４４】
前記不飽和ポリエステル樹脂としては、無水マレイン酸やフマル酸などの不飽和二塩基酸とプロピレングリコールなどのグリコール類をエステル化した不飽和ポリエステル樹脂を、反応性希釈剤のスチレンモノマーなどの重合性モノマーに溶解したものなどが挙げられる。
硬化触媒として有機過酸化物を主としたものとコバルトなどの金属塩を混合することにより、室温でラジカル重合、硬化させる二液硬化型としても使用できる。
【００４５】
前記アルキッド樹脂としては、無水フタル酸などの多塩基酸とグリセリンなどの多価アルコールとのエステル化物を骨格とし、これを大豆油などの乾性油で変性した純アルキッド樹脂や、これを更にロジンなどで変性した変性アルキッド樹脂などが挙げられる。硬化剤としてナフテン酸コバルトなどの乾燥用触媒を混合することにより室温で酸化、硬化させる二液硬化型としても使用できる。
【００４６】
前記エポキシ樹脂としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂や、これらを水素添加したエポキシ樹脂、グリシジルエステル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、脂環式エポキシ樹脂、ノボラック型エポキシ樹脂、ウレタンプレポリマーの末端をエポキシ化したウレタン変性エポキシ樹脂、フッ素化エポキシ樹脂、ポリブタジエン或いはＮＢＲを含有するゴム変性エポキシ樹脂、テトラブロモビスフェノールＡのグリシジルエーテル等の難燃型エポキシ樹脂が挙げられる。
【００４７】
また、エポキシ樹脂の硬化剤としては、例えば、脂肪族アミン、脂環族アミン、芳香族アミン、ポリアミノアミド、イミダゾール、ジシアンジアミド、エポキシ変性アミン、マンニッヒ変性アミン、マイケル付加変性アミン、ケチミン、酸無水物、アルコール類、フェノール類が挙げられる。
【００４８】
更に、有機ポリイソシアネートに対し、ポリオールなどの活性水素化合物をイソシアネート基に対し活性水素（基）過剰の条件で反応して得られる活性水素（基）含有ウレタン系プレポリマーを主剤とし、前記有機ポリイソシアネートを硬化剤とした二液硬化型樹脂も挙げられる。
【００４９】
その他、水酸基などの活性水素（基）を有する含フッ素樹脂を主剤とし、前記有機ポリイソシアネートを硬化剤として室温で硬化させる二液硬化型樹脂も挙げられる。
【００５０】
前記溶剤揮散型樹脂としては、具体的には、天然ゴム、合成ゴム（例えば、スチレン−ブタジエンゴム、クロロプレンゴム、ニトリルゴム、ブチルゴム、アクリロニトリルゴム、塩化ゴム）、（メタ）アクリル系樹脂、塩化ビニル−酢酸ビニル共重合樹脂などが挙げられる。これらはトルエン、キシレン、酢酸エチル等の有機溶剤と共に使用する。
【００５１】
本発明における添加剤としては、硬化触媒、耐候安定剤、酸素硬化性不飽和化合物、充填剤、カップリング剤、接着性付与剤、揺変性付与剤、保存安定性改良剤（脱水剤）、着色剤、意匠性付与剤などが挙げられる。
【００５２】
硬化触媒は、室温硬化性樹脂の硬化を促進させるための触媒であり、イソシアネート基含有ウレタン系プレポリマーや架橋性シリル基含有樹脂の硬化を促進させるための触媒、、ポリサルファイド樹脂や不飽和ポリエステル樹脂の硬化を促進させるための（ラジカル重合）触媒、アルキッド樹脂の硬化を促進させるための乾燥用触媒などが挙げられる。
イソシアネート基含有ウレタン系プレポリマーや架橋性シリル基含有樹脂の硬化を促進させるための触媒としては、具体的には、有機金属化合物、アミン類等が挙げられ、例えば、オクチル酸錫、ナフテン酸錫等の２価の有機錫化合物、ジブチル錫ジオクトエート、ジブチル錫ジラウレート、ジブチル錫ジアセテート、ジブチル錫ジマレエート、ジブチル錫ジステアレート、ジオクチル錫ジラウレート、ジオクチル錫ジバーサテート、ジブチル錫オキサイド、ジブチル錫ビス（トリエトキシシリケート）、ジブチル錫オキサイドとフタル酸エステルとの反応物等の４価の有機錫化合物、ジブチル錫ビス（アセチルアセトナート）、錫系キレート化合物の旭硝子社製ＥＸＣＥＳＴＡＲ Ｃ−５０１、ジルコニウムテトラキス（アセチルアセトナート）、チタンテトラキス（アセチルアセトナート）、アルミニウムトリス（アセチルアセトナート）、アルミニウムトリス（エチルアセトアセテート）、アセチルアセトンコバルト、アセチルアセトン鉄、アセチルアセトン銅、アセチルアセトンマグネシウム、アセチルアセトンビスマス、アセチルアセトンニッケル、アセチルアセトン亜鉛、アセチルアセトンマンガン等の各種金属のキレート化合物、オクチル酸鉛等の有機酸鉛塩、テトラ−ｎ−ブチルチタネート、テトラプロピルチタネート等のチタン酸エステル類、オクチル酸ビスマス、ビスマスバーサテイト等の有機ビスマス化合物、ブチルアミン、オクチルアミン等の第１級アミン類、ジブチルアミン、ジオクチルアミン等の第２級アミン類、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアルカノールアミン類、ジエチレントリアミン、トリエチレンテトラミン等の第１級、第２級アミン類、トリエチルアミン、トリブチルアミン、トリエチレンジアミン、Ｎ−エチルモルフォリン等の第３級アミン類、或いはこれらのアミン類とカルボン酸等の塩類、カオリンクレー、塩酸等の無機系酸性化合物、エチルアシッドホスフェート、２−エチルヘキシルアシッドホスフェート等の有機燐酸系酸性化合物、或いはこれらとアミンとの塩類などが挙げられる。これらのうち、反応速度が高く、毒性及び揮発性の比較的低い液体である点から有機錫化合物や金属キレート化合物が好ましく、更に錫系キレート化合物が好ましく、ジブチル錫ビス（アセチルアセトナート）が最も好ましい。
ポリサルファイド樹脂や不飽和ポリエステル樹脂の硬化を促進させるための（ラジカル重合）触媒としては、二酸化鉛、二酸化マンガン、過酸化カルシウム、過酸化亜鉛、過ホウ酸ソーダ、パラキノンジオキシム、ジニトロベンゼン、メチルエチルケトンパーオキサイド−コバルト石鹸等が挙げられる。
アルキッド樹脂の硬化を促進させるための乾燥用触媒としては、ナフテン酸コバルト等が挙げられる。
硬化触媒は、硬化速度、硬化物の物性などの点から、硬化性樹脂（Ｂ）１００重量部に対して、０〜１０重量部、特に０．０１〜２重量部配合するのが好ましい。
【００５３】
耐候安定剤は、架橋性シリル基含有樹脂の硬化後の酸化や光劣化、熱劣化を防止して、耐候性だけでなく耐熱性を更に向上させるために使用する。耐候安定剤としては具体的には、酸化防止剤、紫外線吸収剤、光硬化性化合物などを挙げることができる。
【００５４】
酸化防止剤としては具体的には、ヒンダードアミン系やヒンダードフェノール系の酸化防止剤を挙げることができ、ヒンダードアミン系酸化防止剤としては、例えば、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）［［３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシフェニル］メチル］ブチルマロネート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）セバケート、メチル−１，２，２，６，６−ペンタメチル−４−ピペリジルセバケート、４−ベンゾイルオキシ−２，２，６，６−テトラメチルピペリジンなどが挙げられる。また、三共社製の商品名サノールＬＳ−２９２などの他、旭電化工業社製の商品名アデカスタブシリーズのＬＡ−５２、ＬＡ−５７、ＬＡ−６２、ＬＡ−６７、ＬＡ−７７、ＬＡ−８２、ＬＡ−８７などの分子量１，０００未満の低分子量ヒンダードアミン系酸化防止剤、同じくＬＡ−６３Ｐ、ＬＡ−６８ＬＤ或いはチバ・スペシャルティ・ケミカルズ社製の商品名ＣＨＩＭＡＳＳＯＲＢシリーズの１１９ＦＬ、２０２０ＦＤＬ、９４４ＦＤ、９４４ＬＤなどの分子量１，０００以上の高分子量ヒンダードアミン系酸化防止剤なども挙げられる。
ヒンダードフェノール系酸化防止剤としては、例えば、ペンタエリストール−テトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、オクタデシル−３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、Ｎ，Ｎ′−ヘキサン−１，６−ジイルビス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニルプロピオナミド）］、ベンゼンプロパン酸３，５−ビス（１，１−ジメチルエチル）−４−ヒドロキシＣ７−Ｃ９側鎖アルキルエステル、２，４−ジメチル−６−（１−メチルペンタデシル）フェノールなどが挙げられる。
【００５５】
紫外線吸収剤としては、例えば、２−（３，５−ジ−ｔｅｒｔ−ブチル−２−ヒドロキシフェニル）−５−クロロベンゾトリアゾール等のベンゾトリアゾール系紫外線吸収剤、２−（４，６−ジフェニル−１，３，５−トリアジン−２−イル）−５−［（ヘキシル）オキシ］−フェノール等のトリアジン系紫外線吸収剤、オクタベンゾン等のベンゾフェノン系紫外線吸収剤、２，４−ジ−ｔｅｒｔ−ブチルフェニル−３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンゾエート等のベンゾエート系紫外線吸収剤が挙げられる。
【００５６】
光硬化性化合物としては、アクリロイル基やメタクリロイル基等の光によって反応硬化する基を分子内に１個以上含有する化合物が挙げられ、具体的には例えば、イソシアネート基含有ウレタン樹脂に水酸基含有アクリレート化合物や水酸基含有メタクリレート化合物を反応させたウレタンアクリレートやウレタンメタクリレート、トリメチロールプロパントリアクリレートやトリメチロールプロパントリメタクリレート等のエステルアクリレートやエステルメタクリレート、ポリエチレンアジペートポリオールのアクリレートやメタクリレート等のポリエステルアクリレートやポリエステルメタクリレート、ポリエーテルポリオールのアクリレートやメタクリレート等のポリエーテルアクリレートやポリエーテルメタクリレート、或いはポリケイ皮酸ビニル類、アジド化樹脂などが挙げられ、分子量１０，０００以下、更に分子量５，０００以下の単量体、オリゴマーが好ましく、特にアクリロイル基及び／又はメタクリロイル基を１分子当たり平均して２個以上含有する物が好ましい。
【００５７】
耐候安定剤は、硬化性樹脂（Ｂ）１００重量部に対して、０．０１〜３０重量部、特に０．１〜１０重量部配合するのが好ましい。
【００５８】
酸素硬化性不飽和化合物は、空気中などの酸素により反応して硬化する不飽和基を分子内に有する化合物であり、硬化性組成物及びシーリング材組成物に配合することにより、硬化後の表面に移行して硬化被膜を形成することにより硬化物表面の粘着をなくすため、長期に渡る表面汚染防止効果を発揮するものである。
酸素硬化性不飽和化合物としては、具体的には、乾性油、乾性油の各種変性物、ジエン系化合物の重合体や共重合体（以下、「重合体や共重合体」を（共）重合体という。）、該（共）重合体の各種変性物（マレイン化変性物、ボイル油変性物など）などが挙げらる。
乾性油（広義に半乾性油も含む。）としては、桐油、大豆油、アマニ油、脱水ヒマシ油、ヤシ油、ヒマシ油などが挙げられ、乾性油の変性物としては、前記乾性油を変性して得られる各種アルキッド樹脂、乾性油により変性されたアクリル系重合体、エポキシ系樹脂、シリコーン樹脂などが挙げられる。
ジエン系化合物の（共）重合体としては、１，２−ブタジエン、１，４−ブタジエン、１，３−ペンタジエン、イソプレン、クロロプレン等のＣ_４〜Ｃ_８ジエン系化合物の重合体やこれら２種以上の共重合体、或いはこれらとスチレン、アクリロニトリル等の他の単量体との共重合体（ＳＢＲ、ＮＢＲなど）などが挙げられ、ジエン系化合物の（共）重合体の変性物としては、前記ジエン系化合物の（共）重合体のマレイン化物、ボイル化物、エポキシ化物などが挙げられる。
酸素硬化性不飽和化合物は、硬化性樹脂（Ｂ）１００重量部に対して０〜５０重量部、特に１〜２０重量部使用するのが好ましい。
【００５９】
充填剤、カップリング剤、接着性付与剤、揺変性付与剤、保存安定性改良剤（脱水剤）、着色剤、意匠性付与剤などは、それぞれ補強や増量、接着性向上、揺変性向上、貯蔵安定性向上、着色、硬化物の表面の艶消しや凹凸付与（ざらつき感付与）等の意匠性付与などのために使用することができる。
【００６０】
充填剤としては、例えば、マイカ、カオリン、ゼオライト、グラファイト、珪藻土、白土、クレー、タルク、スレート粉、無水ケイ酸、石英微粉末、アルミニウム粉末、亜鉛粉末、沈降性シリカなどの合成シリカ、重質炭酸カルシウム、軽質炭酸カルシウム、炭酸マグネシウム、アルミナ、酸化カルシウム、酸化マグネシウム等の無機粉末状充填剤、アスベスト、ガラス繊維、炭素繊維等の繊維状充填剤などの無機系充填剤、或いはこれらの表面を脂肪酸等の有機物で処理した充填剤、木粉、クルミ穀粉、もみ殻粉、パルプ粉、木綿チップ、ゴム粉末、さらにポリアミド樹脂、ポリエステル樹脂、ポリウレタン樹脂、シリコーン樹脂、塩化ビニル樹脂、酢酸ビニル樹脂、ポリエチレンやポリプロピレン等のポリオレフィン樹脂、アクリル樹脂、エポキシ樹脂、フェノール樹脂、ユリア樹脂、メラミン樹脂等の熱可塑性樹脂或いは熱硬化性樹脂の粉末などの有機系充填剤などの他、水酸化マグネシウムや水酸化アルミニウム等の難燃性付与充填剤なども挙げられ、粒径０．０１〜１，０００μｍのものが好ましい。
【００６１】
カップリング剤としては、シラン系、アルミニウム系、ジルコアルミネート系などの各種カップリング剤及び／又はその部分加水分解縮合物が挙げられる。これらのうちシラン系カップリング剤及び／又はその部分加水分解縮合物が接着性に優れている点で好ましい。
シランカップリング剤としては、メチルトリメトキシシラン、ジメチルジメトキシシラン、トリメチルメトキシシラン、ｎ−プロピルトリメトキシシラン、エチルトリメトキシシラン、ジエチルジエトキシシラン、ｎ−ブチルトリメトキシシラン、ｎ−ヘキシルトリエトキシシラン、ｎ−オクチルトリメトキシシラン、フェニルトリメトキシシラン、ジフェニルジメトキシシラン、シクロヘキシルメチルジメトキシシランなどの炭化水素基結合アルコキシシラン類、ジメチルジイソプロペノキシシラン、メチルトリイソプロペノキシシランなどの炭化水素基結合イソプロペノキシシラン類、３−グリシドキシプロピルメチルジメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、ビニルトリメトキシシラン、ビニルジメチルメトキシシラン、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−アミノプロピルメチルジメトキシシラン、３−メルカプトプロピルトリメトキシシラン、３−メルカプトプロピルメチルジメトキシシラン、３−グリシドキシプロピルメチルジイソプロペノキシシラン、３−グリシドキシプロピルトリエトキシシラン、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、３−ア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メトキシシラン、３−アクリロキシプロピルトリエトキシシラン、Ｎ−フェニル−３−アミノプロピルトリメトキシシラン等の官能基を有するアルコキシシラン類やイソプロペノキシシラン類などの分子量５００以下、好ましくは４００以下の低分子化合物及び／又はこれらシランカップリング剤の１種又は２種以上の部分加水分解縮合物で分子量２００〜３，０００の化合物が挙げられる。
【００６２】
接着性付与剤としては、エポキシ樹脂、フェノール樹脂、アルキッド樹脂、アルキルチタネート類、有機ポリイソシアネート等が挙げられる。
【００６３】
揺変性付与剤としては、コロイダルシリカ、石綿粉、前記脂肪酸処理炭酸カルシウム等の無機揺変剤、有機ベントナイト、変性ポリエステルポリオール、脂肪酸アマイド等の有機揺変剤が挙げられる。
【００６４】
保存安定性改良剤としては、組成物中に存在する水分と反応する、前記ビニルトリメトキシシランなどの低分子の架橋性シリル基含有化合物、酸化カルシウム、ｐ−トルエンスルホニルイソシアネートなどが挙げられる。
【００６５】
着色剤としては、酸化チタンや酸化鉄などの無機系顔料、銅フタロシアニンなどの有機系顔料、カーボンブラックなどが挙げられる。
【００６６】
意匠性付与剤は、硬化性組成物及びシーリング材組成物に配合することにより硬化物表面の艶を消す補助をしたり、表面の艶を消すと共に凹凸を付与し天然のざらついた岩石を模した外観を付与したりして意匠性を付与する効果を発揮させるものであり、具体的に、艶消しを付与するものとしては、例えば、蜜ロウ、カルナバワックス、モンタンワックス、パラフィンワックス等の各種ワックス類やステアリン酸アミド等の高級脂肪族化合物などが挙げられる。
表面の艶を消すとともに凹凸を付与するものとしては、粒状物やバルーンなどが挙げられ、粒状物としては前記充填剤として挙げたものと同様のもので、粒径が５０μｍ以上の大きなものが挙げられる。
バルーンは中空の物質であり、その形状は球状だけでなく、立方状、直方状、金平糖状など各種あり、また硬化性組成物及びシーリング材組成物に対する凹凸付与効果を消失させない程度にバルーンを少し破壊したものも挙げられるが、硬化性組成物及びシーリング材組成物の作業性の良さから球状が好ましい。具体的に例えば、ガラスバルーン、シラスバルーン、シリカバルーン、セラミックバルーン等の無機系バルーン、フェノール樹脂バルーン、尿素樹脂バルーン、ポリスチレンバルーン、ポリエチレンバルーン、サランバルーン等の有機系バルーン、或いは無機系化合物と有機系化合物を混合したり積層したりした複合化バルーンなどが挙げられる。
また、これらのバルーンをコーティングしたり表面処理したりしたものも使用でき、例えば、無機系バルーンを前記シランカップリング剤などで表面処理したもの、有機系バルーンを炭酸カルシウム、タルク、酸化チタンなどでコーティングしたものなども挙げられる。
これらのうち、意匠性付与効果の大きさの点から、粒状物及び／又はバルーンが好ましく、更に粒状無機系充填剤及び／又は無機系バルーンが好ましく、特に粗粒重質炭酸カルシウム及び／又はセラミックバルーンが好ましい。
粒状物及び／又はバルーンの粒径は、意匠性付与効果の大きさの点から５０μｍ以上、更には１００〜１，０００μｍが好ましい。
【００６７】
充填剤、カップリング剤、接着性付与剤、揺変性付与剤、保存安定改良剤（脱水剤）、着色剤及び意匠性付与剤の合計の配合量は、硬化性樹脂（Ｂ）１００重量部に対して、０〜５００重量部、特に１０〜３００重量部が好ましい。
【００６８】
本発明において、前記各添加剤成分はそれぞれ単独で或いは２種以上混合して使用することができる。
【００６９】
本発明においては、可塑剤は特に必要としないが、硬化性組成物の用途によっては本発明の目的を損なわない範囲で使用することができる。
可塑剤としては、例えば、ジブチルフタレート、ジヘプチルフタレート、ジオクチルフタレート、ジ（２−エチルヘキシル）フタレート、ブチルベンジルフタレート、ブチルフタリルブチルグリコレート等のフタル酸エステル類、ジオクチルアジペート、ジオクチルセバケート等の非芳香族２塩基酸エステル類、トリクレジルホスフェート、トリブチルホスフェート等のリン酸エステルが挙げられ、比較的高分子量タイプの可塑剤としては、例えば、２塩基酸と２価アルコールとからのポリエステル類等のポリエステル系可塑剤、ポリプロピレングリコールやそのエーテル化誘導体等のポリエーテル類、ポリ−α−メチルスチレン等のポリスチレン類、低粘度の（メタ）アクリル酸エステル系共重合体、その他、プロセスオイル類、アルキルベンゼン類が挙げられる。
【００７０】
本発明の硬化性組成物は粘度が低いため、有機溶剤は使用しなくてもよいか、使用しても極めて少ない量で済み、環境負荷物質を放出しないので安全性が高い。
有機溶剤としては、ｎ−ヘキサンなどの脂肪族系溶剤、シクロヘキサンなどの脂環族系溶剤、トルエンやキシレンなどの芳香族系溶剤など従来公知の有機溶剤が挙げられ、これらは組成物の各成分に反応しないものであればどのようなものでも使用することができる。
【００７１】
なお、本発明の硬化性組成物、シーリング材組成物は用途に応じて一液型としても、二液型としても使用できるが、主剤と硬化剤を混合する手間が無く、また混合不良による硬化不良などの不具合も無く作業性に優れているため、一液型の硬化性組成物が好ましく、更に一液湿気硬化型室温硬化性組成物が好ましい。
また、本発明の硬化性組成物及びシーリング材組成物は、使用する液状ウレタン樹脂（Ａ）が５０〜１００℃の高温雰囲気中でも揮発しないものであり、更に揮発性の高い有機溶剤を使用しなくても粘度が低く押出し作業性の良好なものとなるため、硬化途中においても硬化後においても揮発性物質を放散しないことより、食品、半導体、精密機器等の製造或いはこれらの試験などにおいて使用される、揮発性物質を放出しないことが要求されるクリーンルームの壁パネルや付帯設備の密封用或いは防水用のシーリング剤としても好適に使用することができる。
【００７２】
【実施例】
以下、本発明について実施例などにより更に詳細に説明する。
ここにおいて、硬化性組成物の例としてシーリング材組成物を示したが、これに限定されるものではない。
【００７３】
合成例１
攪拌機、温度計、窒素シール管及び冷却器の付いた加温反応容器に、窒素気流下で、ポリオキシプロピレンモノオール（旭硝子社製ＸＳ−Ｍ３０００、数平均分子量３，２４３、分子量分布（Ｍｗ／Ｍｎ）１．０〜１．１）３００ｇ（ＯＨ当量：０．０９２５）を仕込み、攪拌しながらジブチル錫ジラウレート０．１ｇとｍ−キシリレンジイソシアネート（武田薬品社製タケネート５００、分子量１８８）９．１ｇ（ＮＣＯ当量：０．０９６８）（Ｒ値（ＮＣＯ当量／ＯＨ当量）＝１．０５）を加えたのち、加温して７０〜８０℃で４時間攪拌して、イソシアネート基含有量が理論値（０．０６質量％）以下となった時点で反応を終了し、液状のウレタン樹脂Ｕ−１を製造した。
この液状ウレタン樹脂Ｕ−１は、滴定による実測イソシアネート基含有量０．０４質量％、粘度３，３００ｍＰａ・ｓ／２５℃、分子量分布（Ｍｗ／Ｍｎ）１．０〜１．１、常温で透明の液体であった。
【００７４】
合成例２
合成例１と同様の加温反応容器に、窒素気流下で、ポリオキシプロピレンジオール（旭硝子社製ＰＭＬ−４０１０、数平均分子量９，９３０、分子量分布（Ｍｗ／Ｍｎ）１．０〜１．１）８００ｇ（ＯＨ当量：０．１６１）を仕込み、攪拌しながらｎ−オクタデシルモノイソシアネート（保土谷化学工業社製ミリオネートＯ、分子量２９５）４９．９ｇ（ＮＣＯ当量：０．１６９）（Ｒ値（ＮＣＯ当量／ＯＨ当量）＝１．０５）とジブチル錫ジラウレート０．１ｇを加えたのち、加温して７０〜８０℃で４時間攪拌して、イソシアネート基含有量が理論値（０．０４質量％）以下となった時点で反応を終了し、液状のウレタン樹脂Ｕ−２を製造した。
この液状ウレタン樹脂Ｕ−２は、滴定による実測イソシアネート基含有量０．０３質量％、粘度６，８００ｍＰａ・ｓ／２５℃、分子量分布（Ｍｗ／Ｍｎ）１．０〜１．１、常温で半透明の液体であった。
【００７５】
合成例３
合成例１と同様の加温反応容器に、窒素気流下で、ポリオキシプロピレントリオール（旭硝子社製エクセノール−５０３０、数平均分子量５，０１０、分子量分布（Ｍｗ／Ｍｎ）１．０〜１．２）８８１．９ｇ（ＯＨ当量：０．５２８）を仕込み、攪拌しながらｎ−オクタデシルモノイソシアネート（保土谷化学工業社製ミリオネートＯ、分子量２９５）４１．５ｇ（ＮＣＯ当量：０．１４１）（Ｒ値（ＮＣＯ当量／ＯＨ当量）＝０．２６７）とジブチル錫ジラウレート０．１ｇを加えたのち、加温して７０〜８０℃で２時間攪拌を行い、ＦＴＩＲによりイソシアネート基のピークの消失を確認し、常温まで冷却した。次いでこの中に、４，４′−ジフェニルメタンジイソシアネート（日本ポリウレタン工業社製ミリオネートＭＴ、分子量２５０）９６．９ｇ（ＮＣＯ当量：０．７７５）（Ｒ′値（原料合計のＮＣＯ当量／ＯＨ当量）＝１．７３）を加えたのち、加温して７０〜８０℃で２時間攪拌して、イソシアネート基含有量が理論値（１．５９質量％）以下となった時点で反応を終了し、イソシアネート基含有ポリオキシプロピレン系ウレタンプレポリマーＯ−１を製造した。
このイソシアネート基含有ポリオキシプロピレン系ウレタンプレポリマーＯ−１は、滴定による実測イソシアネート基含有量１．５０質量％、粘度２８，３００ｍＰａ・ｓ／２５℃、常温で半透明の液体であった。
【００７６】
合成例４
合成例１と同様の加温反応容器に、窒素気流下で、ポリオキシプロピレンジオール（数平均分子量１６，０００、総不飽度０．０２ｍｅｑ／ｇ、旭硝子社製ＰＭＬ−４０１６、分子量分布（Ｍｗ／Ｍｎ）１．０〜１．２）８００ｇ（ＯＨ当量：０．１）を仕込み、攪拌しながら３−イソシアネートプロピルトリメトキシシラン（日本ユニカー社製Ｙ−５１８７、分子量２０５．４）１０．３ｇ（ＮＣＯ当量：０．０５）（Ｒ値（ＮＣＯ当量／ＯＨ当量）＝０．５）とジブチル錫ジラウレート０．０８ｇを加えたのち、加温して７０〜８０℃で１時間攪拌を行い、ＦＴＩＲによりイソシアネート基のピークの消失を確認し、常温まで冷却して反応を終了させた。
得られたトリメトキシシリル基含有ポリオキシプロピレン系ウレタン樹脂は、常温で透明の理論、滴定による実測イソシアネート基含有量０．００質量％、粘度１６，４００ｍＰａ・ｓ／２５℃の液体であった。この樹脂をＯ−２と称する。
【００７７】
実施例１
加熱、冷却装置及び窒素シール管付き混練容器に、窒素気流下で、合成例１で得た液状ウレタン樹脂Ｕ−１ ５０ｇ、合成例３で得たイソシアネート基含有ポリオキシプロピレン系ウレタンプレポリマーＯ−１ １００ｇ、ヒンダードフェノール系酸化防止剤：ペンタエリスリトール−テトラキス［３−（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］（チバ・スペシャルティ・ケミカルズ社製イルガノックス１０１０）１．０ｇ、脂肪酸（表面）処理炭酸カルシウム（丸尾カルシウム社製カルファン２００Ｍ）１４５ｇ及びトルエン１５ｇを仕込み、内容物が均一になるまで攪拌、混合し、次いで減圧脱泡し、容器に充填、密封して、シーリング材組成物を調製した。
【００７８】
実施例２
実施例１において、液状ウレタン樹脂Ｕ−１の代わりにＵ−２ ５０ｇを使用した以外は同様にして、シーリング材組成物を調製した。
【００７９】
比較例１
実施例１において、液状ウレタン樹脂Ｕ−１の代わりにジオクチルフタレート
５０ｇを使用した以外は同様にして、シーリング材組成物を調製した。
【００８０】
実施例３
実施例１と同様の混練容器に、窒素気流下で、合成例１で得た液状ウレタン樹脂Ｕ−１ ２００ｇ、合成例４で得たトリメトキシシリル基含有ポリオキシプロピレン系ウレタン樹脂Ｏ−２ ２００ｇ、ヒンダードアミン系酸化防止剤：下記化学式（Ａ）で示される化合物（三共社製サノールＬＳ−２９２）９ｇ、炭酸カルシウム（白石カルシウム社製ホワイトンＢ）２５５．７ｇ、脂肪酸（表面）処理炭酸カルシウム（丸尾カルシウム社製Ｎ−２）２６５．２ｇを仕込み、攪拌、混合しながら１００〜１１０℃で２時間減圧（２０〜７０ｈＰａ）脱水を行い、冷却後、ビニルトリメトキシシラン（チッソ社製サイラエースＳ２１０）１７．０ｇ及びジブチル錫ビス（アセチルアセトナート）（日東化成社製ネオスタンＵ−２２０）２．０ｇを仕込み、均一になるまで攪拌、混合し、次いで減圧脱泡し容器に充填、密封して、シーリング材組成物を調製した。
【００８１】
【化２】

【００８２】
実施例４
実施例３において、合成例４で得たトリメトキシシリル基含有ポリオキシプロピレン系ウレタン樹脂Ｏ−２ ２００ｇの代わりに、合成例４で得たトリメトキシシリル基含有ポリオキシプロピレン系ウレタン樹脂Ｏ−２ １００ｇと架橋性シリル基含有ポリオキシプロピレン系樹脂（鐘淵化学工業社製Ｓ３０３）１００ｇを使用した以外は同様にして、シーリング材組成物を調製した。
【００８３】
実施例５
実施例３において、液状ウレタン樹脂Ｕ−１の代わりにＵ−２ ２００ｇを使用した以外は同様にして、シーリング材組成物を調製した。
【００８４】
実施例６
実施例３において、合成例４で得たトリメトキシシリル基含有ポリオキシプロピレン系ウレタン樹脂Ｏ−２の代わりに、架橋性シリル基含有ポリオキシプロピレン系樹脂（鐘淵化学工業社製Ｓ３０３）２００ｇを使用した以外は同様にして、シーリング材組成物を調製した。
【００８５】
比較例２
実施例４において、液状ウレタン樹脂Ｕ−１の代りにポリオキシプロピレンジオール（数平均分子量３，２００）２００ｇを使用した以外は同様にして、シーリング材組成物を調製した。
【００８６】
比較例３
実施例４において、液状ウレタン樹脂Ｕ−１の代りにポリオキシプロピレントリオール（数平均分子量１２，０００）２００ｇを使用した以外は同様にして、シーリング材組成物を調製した。
【００８７】
比較例４
実施例４において、液状ウレタン樹脂Ｕ−１の代りにジオクチルフタレート ２００ｇを使用した以外は同様にして、シーリング材組成物を調製した。
【００８８】
〔性能試験〕
前記実施例１〜６と比較例１〜４で調製したシーリング材組成物それぞれを用いて、以下の試験を行った。
（１）スランプ
ＪＩＳ Ａ１４３９：１９９７「建築用シーリング材の試験方法」の「４．１スランプ試験」に準拠して、スランプ（縦）を測定した（測定温度２３℃）。
（２）作業性
作業性を評価する試験として、ＪＩＳ Ａ１４３９：１９９７「建築用シーリング材の試験方法」の「４．１４試験用カートリッジによる押出し試験」に準拠して押出し時間を測定した（測定温度２３℃）。
（３）タックフリー時間
ＪＩＳ Ａ１４３９：１９９７「建築用シーリング材の試験方法」の「４．１９タックフリー試験」に準拠して測定した。
（４）塗料汚染性
厚さ５ｍｍのスレート板を使用し、深さ５ｍｍ、幅２５ｍｍ、長さ１５０ｍｍの目地を作製し、その目地にシーリング材組成物を打設し、余分のシーリング材をヘラでかきとり、表面を平らにしたものを、２３℃、５０％相対湿度で７日間養生硬化した後、その表面に水性アクリル塗料（日本ペイント社製タイルラック水性トップスーパーホワイト）を塗布し、２３℃、５０％相対湿度で更に７日間養生して試験体を作製した。
養生後の試験体を５０℃の恒温器中に、別の試験体を７０℃の恒温器中に入れ、それぞれ７日間加熱処理した後、恒温器より取り出し、試験体の表面に黒色珪砂（粒径７０〜１１０μｍ）をふりかけ、直ちに試験体を裏返し、底面を手で軽く叩いて余分の黒色珪砂を落とした。表面に付着して残った黒色珪砂（汚れ）の状態を目視により観察し、汚染性を判定した。
判定基準
○：シーリング材の硬化表面に黒色珪砂の付着がなくきれいな状態
×：シーリング材の硬化表面に黒色珪砂が多量に付着し黒く汚れた状態
液状ウレタン樹脂の合成結果をまとめて表１に示し、シーリング材組成物の組成及びその性能をまとめて表２〜４に示す。
【００８９】
【表１】

【００９０】
【表２】

【００９１】
【表３】

【００９２】
【表４】

【００９３】
【発明の効果】
以上説明した通り、本発明における実質的にイソシアネート基又は水酸基を含有しない分子量分布（Ｍｗ／Ｍｎ）が１．６以下の液状ウレタン樹脂（Ａ）は、分子量分布が狭いため高分子のウレタン樹脂であっても粘度が低く、かつブリードしないものであるため、これを含有する硬化性組成物及びシーリング材組成物は、作業性に優れた性能と、特に夏場の高温時期においても硬化物の表面或いは硬化物表面に上塗り塗装した塗膜表面にブリードしない汚染防止性に優れた性能を両立することが可能となった。更に本発明の硬化性組成物及びシーリング材組成物は可塑剤や有機溶剤などの環境汚染物質を使用しなくても、或いは使用しても極めて少ない量で作業性に優れているため、最近益々高まっている、毒性がなくて環境を汚染しない安全かつ高性能な製品の供給という要求に対応できる。従って、本発明の硬化性組成物及びシーリング材組成物は、建築用、土木用、自動車用などの接着剤、防水材、シーリング材、特に建築物外壁目地用、土木目地用、自動車目地用などの作業性と表面汚染防止性に優れ、かつ安全で環境を汚染しない高性能のシーリング材に適している。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a curable composition having a wide range of application, such as a sealing material, which is cured by moisture in the air or the like to become a rubber-like elastic cured product having excellent workability and contamination resistance.
[0002]
[Prior art]
Curable resins such as crosslinkable silyl group-containing resins and isocyanate group-containing urethane prepolymers have good rubber elasticity and are used in many areas such as sealing materials for construction, civil engineering, and automobiles, adhesives, and paints. Has been. When used for sealing materials, paints, etc., it is particularly required from the viewpoint of work efficiency and aesthetics that the viscosity is low and that there is no surface contamination due to dust adhesion.
In order to adjust the viscosity and physical properties, for example, a low molecular weight plasticizer such as dioctyl phthalate is generally added, but on the other hand, the weather resistance is reduced. There is a disadvantage that it ends up. Furthermore, the plasticizer migrates (bleeds) to the surface of the cured product, or when the paint is further overcoated on the surface of the cured product, the plasticizer migrates to the surface of the paint, so that the surface becomes sticky and dusty. There is a disadvantage that contamination occurs due to adhesion.
[0003]
Various techniques have been proposed to remedy these drawbacks.
For example, a sealing material and an adhesive excellent in drying property, bleed resistance and adhesiveness have been proposed by blending a reaction product of polyalkylene ether monool and organic isocyanate with a urethane prepolymer (Patent Document 1). reference.). A urethane-based modifier excellent in plasticizing effect, physical property-modifying effect, and bleed resistance comprising a urethane compound obtained by reacting a monool having a molecular weight of 200 to 10,000 with an organic isocyanate has also been proposed (patent) Reference 2). A polyurethane-based curable composition excellent in migration resistance containing a diluent selected from a monool or diol having a specific hydroxyl value and a specific total unsaturation and a derivative thereof and an isocyanate group-terminated polyurethane prepolymer has also been proposed ( (See Patent Document 3). A plasticizer having a low viscosity composed of a reaction product of a polyether monool and an aliphatic isocyanate has also been proposed (see Patent Document 4). A technique has also been proposed in which a reaction product of a specific modified polyisocyanate and monool is blended with a base resin as a plasticizer to improve bleeding properties over a long period of time (see Patent Document 5).
However, in any of these technologies, if the molecular weight of a diluent or the like is lowered in order to reduce the viscosity, the base resin bleeds at a high temperature to reduce contamination, and if the molecular weight is increased for the purpose of preventing bleeding, the base The effect of reducing the viscosity of the resin cannot be exhibited, and it is very difficult to achieve both reduction in viscosity and prevention of bleeding.
[0004]
[Patent Document 1]
Japanese Patent Laid-open No. Sho 63-251459
[Patent Document 2]
JP-A-63-251472
[Patent Document 3]
JP 05-295073 A
[Patent Document 4]
JP 2000-119390 A
[Patent Document 5]
JP 2000-234014 A
[0005]
[Problems to be solved by the invention]
The present invention solves the above-mentioned problems of the prior art, cures with moisture in the atmosphere, etc., becomes a rubber-like elastic body having excellent physical properties, and is a coating of the coating on the surface of the cured product or the cured product. An object of the present invention is to provide a curable composition excellent in workability with a wide range of applications such as a sealing material, an adhesive and a paint, which prevents surface contamination.
[0006]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, urethane obtained by reacting a polyoxyalkylene alcohol and an organic isocyanate and having a narrow molecular weight distribution and containing substantially no isocyanate group or hydroxyl group at room temperature. By blending the resin with the curable resin, it has excellent properties such as low viscosity and excellent workability, and after curing, the liquid urethane resin does not bleed on the surface of the cured product even at high temperatures such as in summer. The present inventors have found that a curable composition and a sealing material composition having compatible properties can be obtained, and have reached the present invention.
That is, this invention is shown by the following (1)-(12).
[0007]
(1) a liquid urethane resin (A) having a molecular weight distribution (Mw / Mn) of 1.6 or less, substantially free of isocyanate groups or hydroxyl groups, obtained by reacting a polyoxyalkylene alcohol and an organic isocyanate; A curable composition comprising a curable resin (B).
[0008]
(2) The curable composition according to (1), wherein the liquid urethane resin (A) is a reaction product of a polyoxyalkylene monool and an organic isocyanate.
[0009]
(3) The curable composition according to (1), wherein the liquid urethane resin (A) is a reaction product of a polyoxyalkylene polyol and an organic monoisocyanate.
[0010]
(4) The curable composition according to (2), wherein the polyoxyalkylene monool has a molecular weight distribution (Mw / Mn) of 1.6 or less.
[0011]
(5) The curable composition according to (3), wherein the polyoxyalkylene polyol has a molecular weight distribution (Mw / Mn) of 1.6 or less.
[0012]
(6) The curable composition according to (1), wherein the curable resin (B) is an isocyanate group-containing urethane prepolymer.
[0013]
(7) The curable composition according to (1), wherein the curable resin (B) is a crosslinkable silyl group-containing resin.
[0014]
(8) The isocyanate group-containing urethane prepolymer is an isocyanate group-containing polyoxyalkylene urethane prepolymer obtained by reacting a polyoxyalkylene polyol and an organic isocyanate with hydroxyl group-excess conditions with respect to a hydroxyl group. The curable composition of (6).
[0015]
(9) Isocyanate group-containing polyoxyalkylene urethane obtained by reacting the isocyanate group-containing urethane prepolymer with a polyoxyalkylene polyol, an organic polyisocyanate, and an organic monoisocyanate in an excess of isocyanate groups with respect to hydroxyl groups. The curable composition according to (6), which is a prepolymer.
[0016]
(10) The crosslinkable silyl group-containing polyoxyalkylene urethane resin (a) and / or the crosslinkable silyl group-containing resin obtained by reacting a polyoxyalkylene polyol and a crosslinkable silyl group-containing isocyanate compound. The curable composition according to (7), which is a crosslinkable silyl group-containing polyoxyalkylene resin (b) other than the above.
[0017]
(11) The curable composition according to any one of (1) to (10), further containing an additive.
[0018]
(12) A liquid urethane resin (A) having a molecular weight distribution (Mw / Mn) of 1.6 or less, substantially free of isocyanate groups or hydroxyl groups, obtained by reacting a polyoxyalkylene alcohol and an organic isocyanate, A sealing material composition comprising a curable resin (B).
[0019]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below.
The liquid urethane resin (A) (hereinafter referred to as the liquid urethane resin (A)) having a molecular weight distribution (Mw / Mn) substantially not containing an isocyanate group or a hydroxyl group in the present invention is 1.6 or less is a polyoxyalkylene type. It is a high molecular weight resin substantially free of isocyanate groups or hydroxyl groups, obtained by reacting alcohol and organic isocyanate. Conventional urethane plasticizers and diluents have a wide molecular weight distribution, so the low molecular weight region is easy to bleed, so the anti-contamination property is poor, and the high molecular weight region is difficult to bleed, but the viscosity becomes high and workability is high. However, in the present invention, the molecular weight distribution (Mw / Mm) of the liquid urethane resin (A) is 1.6 or less, Particularly preferably, by making the width as narrow as 1.0 to 1.3, the liquid urethane resin (A) succeeded in keeping the viscosity low even when the liquid urethane resin (A) has a high molecular weight. In the sealing material composition, it was possible to achieve both the property excellent in workability, which is the object of the present invention, and the anti-bleeding anti-bleeding performance after curing, particularly the excellent anti-fouling performance at high temperatures in summer. A.
Specifically, a polyoxyalkylene alcohol and an organic isocyanate (preferably a polyoxyalkylene monool and an organic isocyanate, or a polyoxyalkylene polyol and an organic monoisocyanate) have an isocyanate group / hydroxyl equivalent ratio of 0. In the range of .9 to 1.1 / 1.0, the reaction can be preferably carried out by preferably reacting at 1/1. If the equivalent ratio is less than 0.9 / 1.0, the hydroxyl group content increases, so that the water resistance and stain resistance of the resulting curable composition and sealing material composition deteriorate, and 1.1 / 1. If it exceeds 0.0, the content of isocyanate groups increases, and the influence on the rubber elastic properties of the cured product cannot be ignored.
The molecular weight of the liquid urethane resin (A) is 1,000 to 200,000, more preferably 2,000 to 60,000, particularly preferably 2,000 to 20,000, and most preferably 2,000 to 10,000.
In the present invention, “substantially free of isocyanate groups or hydroxyl groups” means that the liquid urethane resin (A) has an extremely low isocyanate group / hydroxyl group equivalent ratio of 1/1 in the above range. Although a small amount of isocyanate groups or hydroxyl groups may be contained, it means that in order to achieve the object of the present invention, there is no inconvenience even if it is regarded as not containing isocyanate groups or hydroxyl groups.
[0020]
Specific examples of the polyoxyalkylene alcohol include polyoxyalkylene monools, polyoxyalkylene polyols, and mixtures thereof, but the liquid urethane resin (A) obtained in the present invention does not bleed. A polyoxyalkylene monool is preferred because of its excellent compatibility with low viscosity.
[0021]
Examples of the polyoxyalkylene monool include those obtained by ring-opening addition polymerization of alkylene oxide to an initiator such as an alkyl compound containing one active hydrogen. The number average molecular weight of the polyoxyalkylene monool is preferably 500 to 100,000, more preferably 1,000 to 30,000, and particularly preferably 1,000 to 10,000. If the number average molecular weight is less than 500, the resulting liquid urethane resin (A) tends to bleed, and if it exceeds 100,000, the viscosity of the liquid urethane resin (A) increases, and the curable composition and the sealing material composition work. Sexuality gets worse. Of these, polyoxypropylene monool is preferred.
Specific examples of the initiator include methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, tert-butanol, cyclohexanol, phenol, and a mixture of two or more thereof. . Of these, compounds having 5 or less carbon atoms such as methanol and ethanol are preferred.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, and a mixture of two or more thereof. Of these, propylene oxide is preferred.
Furthermore, the polyoxyalkylene monool is a catalyst used at the time of its production, as a cesium compound (cesium hydride, cesium methoxide, cesium alkoxide such as cesium ethoxide, cesium hydroxide, etc.), diethyl zinc, iron chloride, Total unsaturation of 0.1 meq / g or less obtained by using metalloporphyrin compounds, phosphazenium compounds, complex metal cyanide complexes, etc., among others, complex metal cyanide complexes such as zinc hexacyanocobaltate glyme complex and diglyme complex Furthermore, 0.07 meq / g or less, particularly 0.04 meq / g or less is preferable, and molecular weight distribution [weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene by gel permeation chromatography (GPC)] Ratio = Mw / Mn] is 1.6 or less, especially Narrow is preferred of .0～1.3. In particular, in order to obtain a low-viscosity liquid urethane resin (A), it is preferable to use a polyoxyalkylene monool having a narrow molecular weight distribution.
In the present invention, the polyoxyalkylene monool is 50% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more of the portion excluding the hydroxyl group of 1 mol of the molecule. Means that the remaining part may be modified with ether, urethane, ester, polycarbonate, polyamide, polyacrylate, polyolefin, etc., but in the present invention, 95% by mass of the molecule excluding the hydroxyl group. Most preferred is a monool composed of polyoxyalkylene.
[0022]
Polyoxyalkylene polyols include those obtained by ring-opening addition polymerization of alkylene oxide and those obtained by ring-opening addition polymerization of alkylene oxide in an initiator such as an organic compound containing two or more active hydrogens.
Initiators include low molecular weight compounds such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol, and diglycerin. Low molecular weight polyamines such as polyhydric alcohols, low molecular weight polyhydric alcohols such as bisphenol A and bisphenol F, low molecular weight polyamines such as ethylenediamine and butylenediamine, sorbitol, sucrose, glucose, lactose, sorbitan, etc. Low molecular amino alcohols such as monoethanolamine and diethanolamine, low molecular polycarboxylic acids such as adipic acid and terephthalic acid, and at least one of these are reacted with alkylene oxide. Than the polyoxyalkylene polyol obtained Te polyoxyalkylene polyol having a low molecular weight, a mixture of two or more of these mentioned.
Examples of the alkylene oxide include those in the production of polyoxyalkylene monools.
That is, the polyoxyalkylene polyol is specifically a polyoxyethylene polyol, a polyoxypropylene polyol, a polytetramethylene ether polyol, a poly (oxyethylene) -poly (oxypropylene) -copolymer polyol, Poly (oxypropylene) -poly (oxybutylene) -copolymerization type polyols can be mentioned, and these various polyols and organic polyisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, There may be mentioned those having a hydroxyl group at the molecular end by reacting with an isocyanate group in an excess of hydroxyl group.
These can be used alone or in combination of two or more. However, since the viscosity of the liquid urethane resin (A) obtained is low and does not bleed, the workability and resistance of the curable composition and the sealing material composition are reduced. A polyoxypropylene polyol is preferable in terms of good contamination.
The polyoxyalkylene-based polyol has a number average molecular weight of 500 to 100,000, more preferably 1,000 to 30,000, particularly 1,000 to 10,000 for reasons such as good workability and contamination resistance. The average number of alcoholic hydroxyl groups per molecule is preferably 2 or more, more preferably 2 to 4, and most preferably 2.
Further, the polyoxyalkylene-based polyol has a total unsaturation degree of 0. 0, which is obtained by using the same double metal cyanide complex as in the production of the polyoxyalkylene-based monool as a catalyst used in the production thereof. 1 meq / g or less, more preferably 0.07 meq / g or less, particularly preferably 0.04 meq / g or less. Molecular weight distribution [weight average molecular weight (Mw) and number average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) (Mn) ratio = Mw / Mn] is preferably 1.6 or less, and particularly preferably a narrow one of 1.0 to 1.3. In particular, in order to obtain a low-viscosity liquid urethane resin (A), it is preferable to use a polyoxyalkylene polyol having a narrow molecular weight distribution.
In the present invention, the polyoxyalkylene-based polyol is composed of 50% by mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more of the portion excluding 1 mol of hydroxyl group in the molecule. Means that the remaining part may be modified with ether, urethane, ester, polycarbonate, polyamide, polyacrylate, polyolefin, etc., but in the present invention, 95% by mass or more of the molecule excluding the hydroxyl group. Most preferred is a polyol consisting of polyoxyalkylene.
[0023]
Specific examples of the organic isocyanate include organic monoisocyanates, organic polyisocyanates, and mixtures thereof.
[0024]
The organic monoisocyanate may contain one isocyanate group in the molecule, but does not contain a crosslinkable silyl group. The organic group other than the isocyanate group of the organic monoisocyanate is preferably a hydrophobic organic group that does not contain a moisture-curable functional group such as moisture. Specifically, aliphatic monoisocyanates such as n-butyl monoisocyanate, n-hexyl monoisocyanate, n-tetradecyl monoisocyanate, n-hexadecyl monoisocyanate, octadecyl monoisocyanate, n-chloroethyl monoisocyanate, chlorophenyl monoisocyanate Isocyanate, 3,5-dichlorophenyl monoisocyanate, p-fluorophenyl monoisocyanate, 2,4-difluorophenyl monoisocyanate, o-trifluoromethylphenyl monoisocyanate, p-nitrophenyl monoisocyanate, p-isopropylphenyl monoisocyanate, 2 , 6-Diisopropyl monoisocyanate, p-toluenesulfonyl monoisocyanate, p-benzyloxyphenyl monoisocyanate Aromatic monoisocyanate such as, and other 2-methacryloyloxyethyl isocyanate. These can be used alone or in admixture of two or more.
Of these, aliphatic monoisocyanates are preferable, and octadecyl monoisocyanate is particularly preferable.
[0025]
The organic polyisocyanate may contain two or more isocyanate groups in the molecule, but does not contain a crosslinkable silyl group. Specifically, for example, diphenylmethane diisocyanates such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate, , 2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, chlorophenylene-2,4-diisocyanate, 4,4'-diphenyl ether diisocyanate 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, etc. Cyanate, 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, Aliphatic polyisocyanates such as decamethylene diisocyanate and lysine diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, xylylene diisocyanate such as p-xylylene diisocyanate, 1,4-cyclohexyl diisocyanate , Cyclophoric polydiiso, such as isophorone diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate Aneto and the like. Furthermore, organic polyisocyanates such as polyphenylene polymethylene polyisocyanate and crude toluene diisocyanate can also be used.
In addition, modified isocyanates containing one or more uretdione bonds, isocyanurate bonds, allophanate bonds, burette bonds, uretonimine bonds, carbodiimide bonds, urethane bonds, urea bonds, and the like obtained by modifying these organic isocyanates can also be used.
These can be used alone or in admixture of two or more.
Of these, aliphatic polyisocyanate, araliphatic polyisocyanate, and alicyclic polyisocyanate are preferable, and araliphatic polyisocyanate is more preferable, and xylylene diisocyanate in that the viscosity of the liquid urethane resin (A) to be obtained is low. Isocyanates are preferred, and m-xylylene diisocyanate is most preferred.
[0026]
For the synthesis of the liquid urethane resin (A), a metal such as zinc, tin, lead, zirconium, bismuth, cobalt, manganese and iron, such as tin octylate and zirconium octylate, and an organic acid such as octyl acid and naphthenic acid are used. Organic metal chelate compounds such as dibutyltin diacetylacetonate, zirconium tetraacetylacetonate, titanium tetraacetylacetonate, EXCESTAR C-501 (manufactured by Asahi Glass Co., Ltd.), and organic metals such as dibutyltin dilaurate and dioctyltin dilaurate Known urethanization catalysts such as organic metal compounds such as salts with acids, organic amines such as triethylenediamine, triethylamine and tri-n-butylamine, and salts thereof can be used. Of these, organometallic compounds are preferred, and dibutyltin dilaurate is more preferred.
Further, a known organic solvent can also be used.
[0027]
As curable resin (B) in this invention, room temperature curable resin, solvent volatilization type resin, etc. are mentioned, Since it can apply with respect to various uses among these, room temperature curable resin is preferable. Room temperature curable resins are crosslinked and polymerized at room temperature by reaction with moisture in the air, by radical polymerization or oxidative polymerization by mixing radical generators, or by crosslinking reaction between the main agent and curing agent. It cures. The solvent volatilization type resin is used by dissolving the resin in an organic solvent and volatilizing it.
Any of these may be used alone or in admixture of two or more.
[0028]
As the room temperature curable resin, specifically, a one-pack type comprising an isocyanate group-containing urethane prepolymer, a crosslinkable silyl group-containing resin, a polysulfide resin, an unsaturated polyester resin, an alkyd resin, and optionally further a catalyst, Alternatively, a two-component type including an epoxy resin, an active hydrogen-containing urethane resin, an active hydrogen-containing fluororesin, and a curing agent or a catalyst can be exemplified. Among these, a one-component moisture-curing type (including a catalyst in some cases) isocyanate group-containing urethane prepolymer and a crosslinkable silyl group-containing resin are preferable because of excellent workability.
[0029]
The isocyanate group-containing urethane prepolymer is one in which an isocyanate group reacts with moisture (moisture) to form a urea bond to crosslink and cure, and an active hydrogen compound and the organic isocyanate (organic monoisocyanate or organic polyisocyanate). ) In an excess of isocyanate groups with respect to the active hydrogen (groups) in total or simultaneously.
Specifically, an active hydrogen compound and an organic isocyanate, or an active hydrogen compound, an organic monoisocyanate, and an organic polyisocyanate, the equivalent ratio of isocyanate group / active hydrogen (group) of the total raw material is 1.3 to 5 / It can be suitably produced by reacting simultaneously or sequentially within a range of 1.0, and further 1.5 to 2.5 / 1.0. When the equivalence ratio is less than 1.3 / 1.0, the resulting urethane prepolymer has too few cross-linking points, and the curable composition and the sealing material composition are reduced in elongation, tensile strength, and the like. If the elastic properties and adhesiveness are poor and the equivalent ratio exceeds 5 / 1.0, the amount of carbon dioxide generated when reacting with moisture increases, which is not preferable.
In the reaction of the active hydrogen compound, the organic monoisocyanate, and the organic polyisocyanate, when the reaction is sequentially performed, the active hydrogen compound and the organic monoisocyanate are first, preferably 1 of the number of active hydrogens (groups) before the reaction. A monoisocyanate-modified active hydrogen compound in which active hydrogen (group) remains in the molecule is synthesized by reacting with -99%, further 10-90%, particularly preferably 10-50%. When the number of active hydrogens (groups) to be reacted with the organic monoisocyanate is less than 1%, the effect of lowering the viscosity of the resulting urethane prepolymer is lost, and the isocyanate group concentration increases to cause foaming. When the number exceeds 99% Further, the elastic properties and adhesiveness of rubber such as elongation and tensile strength after curing of the curable composition and the sealing material composition are low. Subsequently, the monoisocyanate-modified active hydrogen compound and the organic polyisocyanate have an equivalent ratio of isocyanate group / active hydrogen (group) of the total raw materials of 1.3 to 5 / 1.0, and more preferably 1.5 to 2. It can react suitably in the range used as 5 / 1.0, and can manufacture suitably.
In the present invention, it is preferable to react an active hydrogen compound, an organic monoisocyanate, and an organic polyisocyanate from the viewpoint of easy physical property adjustment of the resulting isocyanate group-containing urethane prepolymer and low viscosity.
[0030]
Examples of the active hydrogen compound include polyols, amino alcohols, and polyamines. Of these, polymeric polyols are preferred.
Examples of the polymer polyol include polyester polyol, polyester amide polyol, polyoxyalkylene polyol, polyether / ester polyol, polycarbonate polyol, poly (meth) acryl polyol, hydrocarbon polyol, and the like. That's all.
Examples of the polyester polyol and polyester amide polyol include known dicarboxylic acids such as succinic acid, adipic acid, and terephthalic acid, their acid esters, acid anhydrides, ethylene glycol, propanediol, butanediol, pentanediol, and hexane. Low molecular polyols such as diol, neopentyl glycol, trimethylol propane, glycerin, quadrol or bisphenol A ethylene oxide or propylene oxide adducts, low molecular polyamines such as ethylenediamine and diethylenetriamine, and amino alcohols such as monoethanolamine alone Or a compound obtained by a dehydration condensation reaction with a mixture thereof. Furthermore, a lactone polyester polyol obtained by cleavage polymerization of a cyclic ester (ie, lactone) monomer such as ε-caprolactone can be used. In addition, high molecular monoalcohols such as polyoxyalkylene monoalcohol, butyl alcohol, and octadecyl monoalcohol, and low molecular monoalcohols can be used for modifying the isocyanate group-containing urethane prepolymer.
Examples of the polyoxyalkylene-based polyol include those similar to those used in the production of the liquid urethane resin (A). The resulting curable composition and the sealing material composition have low viscosity and good workability. The number average molecular weight is preferably 500 to 100,000, more preferably 1,000 to 50,000, and particularly preferably 1,000 to 30,000, in terms of high rubber elastic properties and adhesion after curing. The average number of alcoholic hydroxyl groups per hit is preferably 2 or more, more preferably 2 to 10, and particularly preferably 2 to 4, more preferably those having a narrow molecular weight distribution (Mw / Mn) as described above.
Examples of the polyether ester polyol include compounds produced from the polyoxyalkylene polyol and the dicarboxylic acid, acid anhydride and the like.
Examples of the polycarbonate polyol include compounds obtained from a reaction between a low molecular polyol used for the production of the polyester polyol and diethyl carbonate, diphenyl carbonate, or the like.
Examples of the poly (meth) acrylic polyol include those obtained by copolymerizing hydroxyethyl (meth) acrylate containing a hydroxyl group with other (meth) acrylic acid alkyl ester monomers.
Examples of the hydrocarbon polyol include polybutadiene polyol and hydrogenated polybutadiene polyol.
Examples of the polyol further include low molecular weight polyols having a number average molecular weight of less than 500, which are cited as the raw materials for producing the polyester polyol.
Examples of the polyamine include polymer polyamines such as polyether polyamines having a number average molecular weight of 500 or more and a polyether polyol terminal having an amino group, such as a terminal diaminated product of polypropylene glycol.
Examples of the polyamine further include low molecular weight polyamines having a number average molecular weight of less than 500, such as ethylenediamine, hexamethylenediamine, isophoronediamine, diaminodiphenylmethane, and diethylenetriamine.
Examples of amino alcohols include monoethanolamine, diethanolamine, N-methyldiethanolamine, N-methyldipropanolamine, and N-phenyldiethanolamine.
In addition, polyamide resins, polyester resins and the like having a number average molecular weight of 500 or more, which generally contain active hydrogen groups known in the polyurethane industry, are also included.
These can be used singly or in combination of two or more. Among them, the isocyanate group-containing urethane prepolymer obtained has a low viscosity and good physical properties after curing. Therefore, a curable composition and a sealing material obtained therefrom are used. Polyoxyalkylene-based polyols and polyoxypropylene-based polyols are preferred from the viewpoint of low viscosity of the composition and good workability and high rubber elastic properties and adhesiveness after curing.
[0031]
As said organic isocyanate (organic monoisocyanate and organic polyisocyanate), the thing similar to the thing in manufacture of liquid urethane resin (A) is mentioned.
That is, the organic monoisocyanate is used for the purpose of adjusting the number of functional groups of the isocyanate group for adjusting the physical properties and the purpose of reducing the viscosity of the resulting isocyanate group-containing urethane prepolymer, and the viscosity of the resulting prepolymer is low. In this respect, an aliphatic monoisocyanate is preferable, and n-octadecyl monoisocyanate is particularly preferable.
The organic polyisocyanate is preferably an aromatic polyisocyanate or an araliphatic polyisocyanate in view of good rubber elastic properties such as elongation of the resulting curable composition and sealing material composition, and more preferably xylylene diisocyanates and the like. Diphenylmethane diisocyanates such as 4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate are preferred.
[0032]
When synthesizing an isocyanate group-containing urethane prepolymer, a known metal or organic acid salt, an organic metal chelate compound, an organic metal compound such as a salt of an organic metal and an organic acid, an organic amine or a salt thereof, and the like. A urethanization catalyst can be used. Of these, organometallic compounds are preferred.
Further, a known organic solvent can also be used.
[0033]
The isocyanate group content of the isocyanate group-containing urethane prepolymer is preferably 0.3 to 15.0% by mass, particularly preferably 0.5 to 5.0% by mass, and most preferably 0.5 to 2.5% by mass. is there. When the isocyanate group content is less than 0.3% by mass, there are few crosslinking points in the prepolymer, so that sufficient adhesiveness cannot be obtained. When the isocyanate group content exceeds 15.0% by mass, the number of crosslinking points in the prepolymer increases and the rubber elasticity deteriorates, and the amount of carbon dioxide generated by the reaction with moisture increases and the cured product foams. It is not preferable in terms.
[0034]
Isocyanate group-containing urethane prepolymers can be used as a one-part curable type by reacting and curing with moisture (humidity) in the atmosphere at room temperature, and are based on isocyanate group-containing urethane prepolymers and are active as polyamines and polyols. It can also be used as a two-component curing type using a hydrogen compound as a curing agent.
[0035]
Preferred examples of the crosslinkable silyl group-containing resin include those generally referred to as silicone resins and modified silicone resins, which are crosslinked to form rubber by reacting with moisture (water) to form siloxane bonds. It is a resin containing a crosslinkable silyl group in the molecule that forms a cured product. In the present invention, a modified silicone resin is preferred.
[0036]
The silicone resin is a resin having a main chain of organopolysiloxane and a crosslinkable silyl group in the molecule.
Specifically, a one-part silicone resin containing an organopolysiloxane having a silanol group at the terminal as a main component and a low-molecular compound containing a crosslinkable silyl group as a crosslinking component, and an organopolysiloxane having a silanol group at the terminal as a main component A typical example is a two-part silicone resin containing siloxane and an aminoxyalkylsilane as a curing agent. Examples of the crosslinkable silyl group-containing low molecular weight compound include acyloxyalkylsilane, aminoxyalkylsilane, and alkoxyalkylsilane.
[0037]
As the modified silicone resin, for example, JP-A-52-73998, JP-A-55-9669, JP-A-59-122541, JP-A-60-6747, JP-A-61-233043 JP, 63-6003, JP 63-112642, JP 3-79627, JP 4-283259, JP 5-287186, JP 11-80571. , JP-A-11-116663, JP-A-11-130931, specifically, a polymer containing a crosslinkable silyl group in the molecule, the main chain being a vinyl polymer, Aliphatic hydrocarbon polymers such as polyoxyalkylene polymers, polyisoprene, polyisobutylene, polybutanediene, polyester polymers, polysulfide Polymers, copolymers thereof, and mixtures thereof.
The main chain of the modified silicone resin is preferably a polyoxyalkylene polymer from the viewpoint of physical properties such as tensile adhesion after curing and modulus.
The number of crosslinkable silyl groups is 0.1 or more, more preferably 0.3 to 5.0, and particularly 0.3 to 2.0 in the molecule from the viewpoint of the curability of the composition and the physical properties after curing. Preferably.
Further, the crosslinkable silyl group is preferably one represented by the following general formula which is easily crosslinked and easy to produce.
[0038]
[Chemical 1]

Wherein R is a hydrocarbon group, preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and most preferably a methyl group. The reactive group is a hydrolyzable group selected from a halogen atom, hydrogen atom, hydroxyl group, alkoxy group, acyloxy group, ketoximate group, amide group, acid amide group, mercapto group, alkenyloxy group and aminooxy group, When X is plural, X may be the same group or different groups, among which X is preferably an alkoxy group, most preferably a methoxy group or an ethoxy group, and a is 0, 1, or 2. And is most preferably 0 or 1.)
[0039]
Introduction of the crosslinkable silyl group into the main chain can be performed, for example, by the following known method.
(1) An organic compound (for example, allyl isocyanate) having an active group and an unsaturated group which are reactive with this functional group in a polymer such as a polyoxyalkylene or vinyl polymer having a functional group such as a hydroxyl group at the terminal. Then, the resulting reaction product is hydrosilylated by allowing hydrosilane having a hydrolyzable group to act.
(2) Polyoxyalkylene and vinyl polymers having functional groups such as hydroxyl groups, epoxy groups and isocyanate groups at the ends have functional groups and crosslinkable silyl groups that are reactive with these functional groups. The compound is reacted.
Examples of the compound having a reactive functional group and a crosslinkable silyl group include amino group-containing silanes, mercapto group-containing silanes, epoxy group-containing silanes, vinyl type unsaturated group-containing silanes, chlorine atom-containing silanes, and isocyanates. Examples thereof include group-containing silanes and hydrosilanes.
(3) A compound having a polymerizable unsaturated bond and a crosslinkable silyl group (for example, CH₂= CHSi (OCH₃  )₃  And CH₂= CHCOO (CH₂)₂Si (OCH₃  )₃) And a (meth) acrylic acid alkyl ester monomer.
(4) A compound having a polymerizable unsaturated bond and a functional group (for example, hydroxyethyl (meth) acrylate or allyl (meth) acrylate) is added to the (meth) acrylic acid alkyl ester monomer and copolymerized. Then, the resulting copolymer is converted into a compound having a reactive functional group and a crosslinkable silyl group (for example, an isocyanate group and —Si (OCH₃)₃  And hydrosilanes having hydrolyzable groups such as trimethoxysilane and triethoxysilane).
[0040]
Silicone resins and modified silicone resins have a number average molecular weight of 1,000 or more, especially those having a narrow molecular weight distribution of 6,000 to 30,000, and are easy to handle because the viscosity of the curable composition is low, and the strength and elongation after curing. It is preferable because of its excellent physical properties such as modulus.
[0041]
Specifically, the crosslinkable silyl group-containing polyoxyalkylene urethane resin preferable as the crosslinkable silyl group-containing resin can be obtained by reacting a polyoxyalkylene polyol with a crosslinkable silyl group-containing isocyanate compound. .
Examples of the polyoxyalkylene-based polyol include those similar to those used in the production of the liquid urethane resin (A). The resulting curable composition and sealing material composition have low viscosity and good workability, and are cured. The number average molecular weight is the same as described above in view of high rubber elastic properties and adhesion later, and the average number of alcoholic hydroxyl groups per molecule is 2 or more, further 2 to 10, particularly 2 to 4. Those having a narrow molecular weight distribution (Mw / Mn) as described above are also preferred.
The polyoxyalkylene polyol and the crosslinkable silyl group-containing isocyanate compound have an isocyanate group / hydroxyl group equivalent ratio of 0.1 to 1.5 / 1.0, more preferably 0.5 to 1.0 / 1. The reaction is preferably performed within the range of 0.
Also in this reaction, a known urethanization catalyst such as a salt of a metal and an organic acid, an organic metal chelate compound, a salt of an organic metal and an organic acid, or an organic amine or a salt thereof is used. Can do. Of these, organometallic compounds are preferred.
Further, a known organic solvent can also be used.
[0042]
The crosslinkable silyl group-containing isocyanate compound may contain at least one isocyanate group and one or more crosslinkable silyl groups in the molecule, but it is easy to control the reaction and has good rubber elasticity after curing. From this point, a compound containing one isocyanate group and one crosslinkable silyl group in the molecule is preferable.
Specific examples of the crosslinkable silyl group-containing isocyanate compound include 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatepropylmethyldimethoxysilane, 3- Examples thereof include isocyanate propyl isopropoxy silane, isocyanate trimethoxy silane, diisocyanate dimethoxy silane and the like, and these can be used alone or in admixture of two or more. Of these, 3-isocyanatopropyltrimethoxysilane is preferred.
[0043]
The polysulfide resin is a polymer having a polysulfide skeleton and a mercapto group at the terminal.
The polysulfide resin having a mercapto group at the end may be represented by the general formula: HS- (R₁  -Sx) n-R₂A structure represented by —SH 2 is preferred. X in this general formula is an integer of 1 to 4, and the average value is 1.5 to 2.5. n is 1-120, preferably 6-50. In addition, R in this general formula₁  And R₂  Is a divalent aliphatic group, specifically -C₂  H₄  -, -C₃  H₆  -, -C₄H₈  In particular, those having an ether bond are preferable, and specific examples include the following.
-C₂H₄-OC₂H₄−
-C₃H₆-OC₃H₆  −
-C₄  H₈  -OC₄  H₈  −
-C₂H₄  -O-CH₂-OC₂  H₄  −
-C₃  H₆  -O-CH₂  -OC₃  H₆  −
-C₄  H₈-O-CH₂-OC₄H₈−
The number average molecular weight of the polysulfide resin having a mercapto group at the terminal is preferably 200 to 20000, particularly preferably 1000 to 8000.
Polysulfide resin can be used as a one-part curing type in which hydrogen peroxide is generated by moisture when a compound containing a metal oxide such as calcium peroxide is exposed to the atmosphere, and the resin is oxidized and cured at room temperature. Moreover, it can also be used as a two-component curable type in which polysulfide resin is used as a main ingredient and lead dioxide, polyisocyanate or the like is used as a curing agent, and these are cured by mixing at the time of use.
[0044]
Examples of the unsaturated polyester resin include unsaturated polyester resins obtained by esterifying unsaturated dibasic acids such as maleic anhydride and fumaric acid and glycols such as propylene glycol, and polymerizable monomers such as styrene monomer as a reactive diluent. And the like dissolved in
By mixing an organic peroxide mainly as a curing catalyst with a metal salt such as cobalt, it can be used as a two-component curing type in which radical polymerization and curing are performed at room temperature.
[0045]
As the alkyd resin, a pure alkyd resin in which an esterified product of a polybasic acid such as phthalic anhydride and a polyhydric alcohol such as glycerin is modified with a drying oil such as soybean oil, or a rosin is further used. And modified alkyd resins modified with 1. By mixing a drying catalyst such as cobalt naphthenate as a curing agent, it can be used as a two-component curing type that is oxidized and cured at room temperature.
[0046]
Examples of the epoxy resin include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AD type epoxy resin, a bisphenol S type epoxy resin, an epoxy resin obtained by hydrogenating these, a glycidyl ester type epoxy resin, and a glycidyl amine type. Epoxy resin, cycloaliphatic epoxy resin, novolak type epoxy resin, urethane modified epoxy resin with epoxidized end of urethane prepolymer, fluorinated epoxy resin, rubber modified epoxy resin containing polybutadiene or NBR, glycidyl of tetrabromobisphenol A Examples include flame retardant epoxy resins such as ether.
[0047]
Examples of the epoxy resin curing agent include aliphatic amine, alicyclic amine, aromatic amine, polyaminoamide, imidazole, dicyandiamide, epoxy-modified amine, Mannich-modified amine, Michael addition-modified amine, ketimine, and acid anhydride. , Alcohols and phenols.
[0048]
Furthermore, an active hydrogen (group) -containing urethane-based prepolymer obtained by reacting an active hydrogen compound such as polyol with an isocyanate group under an excess of active hydrogen (group) with respect to the organic polyisocyanate as a main component, A two-component curable resin using isocyanate as a curing agent is also included.
[0049]
In addition, a two-component curable resin in which a fluorine-containing resin having an active hydrogen (group) such as a hydroxyl group is a main component and the organic polyisocyanate is a curing agent is cured at room temperature.
[0050]
Specific examples of the solvent-volatile resin include natural rubber, synthetic rubber (for example, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, acrylonitrile rubber, chlorinated rubber), (meth) acrylic resin, vinyl chloride. -Vinyl acetate copolymer resin etc. are mentioned. These are used together with organic solvents such as toluene, xylene and ethyl acetate.
[0051]
Examples of the additive in the present invention include a curing catalyst, a weather resistance stabilizer, an oxygen curable unsaturated compound, a filler, a coupling agent, an adhesion imparting agent, a thixotropic agent, a storage stability improving agent (dehydrating agent), and coloring. Agents, designability-imparting agents, and the like.
[0052]
The curing catalyst is a catalyst for accelerating the curing of the room temperature curable resin, the catalyst for accelerating the curing of the isocyanate group-containing urethane prepolymer and the crosslinkable silyl group-containing resin, polysulfide resin and unsaturated polyester resin. (Radical polymerization) catalyst for accelerating the curing of the catalyst, and a drying catalyst for accelerating the curing of the alkyd resin.
Specific examples of the catalyst for accelerating the curing of the isocyanate group-containing urethane prepolymer and the crosslinkable silyl group-containing resin include organometallic compounds and amines. For example, tin octylate and tin naphthenate. Divalent organic tin compounds such as dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dimaleate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin diversate, dibutyltin oxide, dibutyltin bis (triethoxysilicate) EXCESTAR C-501 manufactured by Asahi Glass Co., Ltd., a tetravalent organic tin compound such as a reaction product of dibutyltin oxide and a phthalate ester, dibutyltin bis (acetylacetonate), and a tin-based chelate compound. G), titanium tetrakis (acetylacetonate), aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), acetylacetone cobalt, acetylacetone iron, acetylacetone copper, acetylacetone magnesium, acetylacetone bismuth, acetylacetone nickel, acetylacetone zinc, acetylacetone manganese Chelate compounds of various metals such as lead acid salts such as lead octylate, titanates such as tetra-n-butyl titanate and tetrapropyl titanate, organic bismuth compounds such as bismuth octylate and bismuth versatate, butylamine, Primary amines such as octylamine, secondary amines such as dibutylamine and dioctylamine, monoethanolamine, diethanol Alkanolamines such as amine and triethanolamine, primary and secondary amines such as diethylenetriamine and triethylenetetramine, tertiary amines such as triethylamine, tributylamine, triethylenediamine and N-ethylmorpholine, or Salts of these amines and carboxylic acids, inorganic acidic compounds such as kaolin clay and hydrochloric acid, organic phosphoric acid acidic compounds such as ethyl acid phosphate and 2-ethylhexyl acid phosphate, and salts of these with amines . Of these, organotin compounds and metal chelate compounds are preferred because of their high reaction rate and relatively low toxicity and volatility, and tin-based chelate compounds are more preferred, with dibutyltin bis (acetylacetonate) being the most preferred. preferable.
(Radical polymerization) catalysts for promoting curing of polysulfide resins and unsaturated polyester resins include lead dioxide, manganese dioxide, calcium peroxide, zinc peroxide, sodium perborate, paraquinone dioxime, dinitrobenzene, and methyl ethyl ketone. Examples include peroxide-cobalt soap.
Examples of the drying catalyst for accelerating the curing of the alkyd resin include cobalt naphthenate.
The curing catalyst is preferably blended in an amount of 0 to 10 parts by weight, particularly 0.01 to 2 parts by weight with respect to 100 parts by weight of the curable resin (B) from the viewpoints of curing speed and physical properties of the cured product.
[0053]
The weathering stabilizer is used to prevent oxidation, photodegradation, and thermal degradation after curing of the crosslinkable silyl group-containing resin and further improve not only the weather resistance but also the heat resistance. Specific examples of the weather resistance stabilizer include an antioxidant, an ultraviolet absorber, and a photocurable compound.
[0054]
Specific examples of the antioxidant include hindered amine-based and hindered phenol-based antioxidants. Examples of the hindered amine-based antioxidant include bis (1,2,2,6,6-pentamethyl). -4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) Examples include sebacate, methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine. In addition to Sanyo LS-292, trade names manufactured by Sankyo Co., Ltd., trade names Adeka Stub series LA-52, LA-57, LA-62, LA-67, LA-77, LA- 82, LA-87 and other low molecular weight hindered amine antioxidants with a molecular weight of less than 1,000, also LA-63P, LA-68LD or Ciba Specialty Chemicals' product names CHIMASSORB series 119FL, 2020FDL, 944FD, 944LD And high molecular weight hindered amine antioxidants having a molecular weight of 1,000 or more.
Examples of the hindered phenol antioxidant include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-). tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], benzenepropanoic acid Examples include 3,5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester, 2,4-dimethyl-6- (1-methylpentadecyl) phenol, and the like.
[0055]
Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers such as 2- (3,5-di-tert-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, and 2- (4,6-diphenyl- Triazine-based UV absorbers such as 1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, benzophenone-based UV absorbers such as octabenzone, 2,4-di-tert-butylphenyl Examples include benzoate-based ultraviolet absorbers such as -3,5-di-tert-butyl-4-hydroxybenzoate.
[0056]
Examples of the photocurable compound include a compound containing one or more groups that are reactively cured by light such as an acryloyl group or a methacryloyl group in the molecule. Specifically, for example, a hydroxyl group-containing acrylate compound is added to an isocyanate group-containing urethane resin. Polyester acrylate or polyester methacrylate such as urethane acrylate or urethane methacrylate, ester acrylate or ester methacrylate such as trimethylolpropane triacrylate or trimethylolpropane trimethacrylate, acrylate or methacrylate of polyethylene adipate polyol, etc. Polyether acrylate such as ether polyol acrylate or methacrylate, polyether methacrylate, or poly Examples thereof include vinyl cinnamates and azido resins, and monomers and oligomers having a molecular weight of 10,000 or less, and more preferably a molecular weight of 5,000 or less are preferred. Particularly, acryloyl groups and / or methacryloyl groups are averaged per molecule. The thing containing 2 or more is preferable.
[0057]
The weathering stabilizer is preferably blended in an amount of 0.01 to 30 parts by weight, particularly 0.1 to 10 parts by weight, based on 100 parts by weight of the curable resin (B).
[0058]
An oxygen curable unsaturated compound is a compound having in its molecule an unsaturated group that reacts and cures with oxygen, such as in the air, and is added to the curable composition and the sealing material composition to obtain a cured surface. In order to eliminate the adhesion of the surface of the cured product by forming a cured film by shifting to, the effect of preventing surface contamination over a long period of time is exhibited.
Specific examples of oxygen-curable unsaturated compounds include drying oils, various modified products of drying oils, polymers and copolymers of diene compounds (hereinafter referred to as “copolymers” and “copolymers”). And various modified products of the (co) polymer (maleinized modified products, boiled oil modified products, etc.).
Examples of drying oil (including semi-drying oil in a broad sense) include paulownia oil, soybean oil, linseed oil, dehydrated castor oil, coconut oil, castor oil, and the like. And various alkyd resins obtained, acrylic polymers modified with drying oil, epoxy resins, silicone resins, and the like.
Examples of (co) polymers of diene compounds include C 1,2,2-butadiene, 1,4-butadiene, 1,3-pentadiene, isoprene, chloroprene and the like.₄~ C₈Examples thereof include polymers of diene compounds and copolymers of two or more of these, or copolymers of these with other monomers such as styrene and acrylonitrile (SBR, NBR, etc.). Examples of the modified product of the (co) polymer include maleated products, boiled products, and epoxidized products of the (co) polymer of the diene compound.
The oxygen-curable unsaturated compound is preferably used in an amount of 0 to 50 parts by weight, particularly 1 to 20 parts by weight, based on 100 parts by weight of the curable resin (B).
[0059]
Fillers, coupling agents, adhesion-imparting agents, thixotropic agents, storage stability improvers (dehydrating agents), coloring agents, design-improving agents, etc. are reinforced, increased, improved adhesion, improved thixotropic properties, It can be used for improving the storage stability, coloring, imparting design properties such as matting of the surface of the cured product and imparting unevenness (giving a feeling of roughness).
[0060]
Examples of fillers include mica, kaolin, zeolite, graphite, diatomaceous earth, white clay, clay, talc, slate powder, anhydrous silicic acid, quartz fine powder, aluminum powder, zinc powder, and synthetic silica such as precipitated silica, heavy Inorganic fillers such as calcium carbonate, light calcium carbonate, magnesium carbonate, alumina, calcium oxide, magnesium oxide, inorganic fillers such as asbestos, glass fibers, carbon fibers, etc., or their surface Fillers treated with organic substances such as fatty acids, wood flour, walnut flour, rice husk flour, pulp powder, cotton chips, rubber powder, polyamide resin, polyester resin, polyurethane resin, silicone resin, vinyl chloride resin, vinyl acetate resin, Polyolefin resin such as polyethylene and polypropylene, acrylic resin In addition to organic fillers such as epoxy resin, phenolic resin, urea resin, melamine resin and other thermoplastic resins or thermosetting resin powder, flame retardant fillers such as magnesium hydroxide and aluminum hydroxide And a particle size of 0.01 to 1,000 μm is preferable.
[0061]
Examples of the coupling agent include various coupling agents such as silane, aluminum and zircoaluminate and / or partial hydrolysis condensates thereof. Of these, a silane coupling agent and / or a partially hydrolyzed condensate thereof is preferred because of its excellent adhesiveness.
As silane coupling agents, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, n-propyltrimethoxysilane, ethyltrimethoxysilane, diethyldiethoxysilane, n-butyltrimethoxysilane, n-hexyltriethoxysilane , N-octyltrimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, cyclohexylmethyldimethoxysilane and other hydrocarbon group-bonded alkoxysilanes, dimethyldiisopropenoxysilane, methyltriisopropenoxysilane and other hydrocarbon group-bonded Isopropenoxysilanes, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmeth Sisilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-glycidoxypropylmethyl Diisopropenoxysilane, 3-glycidoxypropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane , 3-acryloxypropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and other functional groups such as alkoxysilanes and isopropenoxysilanes having a molecular weight of 500 or less, preferably 400 or less. Compounds having a molecular weight 200 to 3,000 are exemplified in compound and / or one or more partially hydrolyzed condensate of the silane coupling agent.
[0062]
Examples of the adhesion-imparting agent include epoxy resins, phenol resins, alkyd resins, alkyl titanates, and organic polyisocyanates.
[0063]
Examples of the thixotropic agent include inorganic thixotropic agents such as colloidal silica, asbestos powder, and fatty acid-treated calcium carbonate, and organic thixotropic agents such as organic bentonite, modified polyester polyol, and fatty acid amide.
[0064]
Examples of the storage stability improver include low-molecular crosslinkable silyl group-containing compounds such as vinyltrimethoxysilane, calcium oxide, and p-toluenesulfonyl isocyanate, which react with moisture present in the composition.
[0065]
Examples of the colorant include inorganic pigments such as titanium oxide and iron oxide, organic pigments such as copper phthalocyanine, and carbon black.
[0066]
Designability-imparting agents can be used to aid in delustering the surface of the cured product by blending it into the curable composition and the sealing material composition, or to erase the surface luster and impart irregularities to simulate natural rough rocks. For example, various waxes such as beeswax, carnauba wax, montan wax, paraffin wax, etc. And higher aliphatic compounds such as stearamide.
Examples of the material that removes the gloss of the surface and imparts irregularities include granular materials and balloons, etc. The granular materials are the same as those mentioned as the filler, and large particles having a particle size of 50 μm or more are mentioned. It is done.
The balloon is a hollow substance, and the shape of the balloon is not only spherical, but also various shapes such as a cubic shape, a rectangular shape, and a confetti shape, and the balloon is slightly removed to the extent that the unevenness imparting effect on the curable composition and the sealing material composition is not lost. Although what was destroyed is also mentioned, spherical shape is preferable from the good workability | operativity of a curable composition and a sealing material composition. Specifically, for example, inorganic balloons such as glass balloons, shirasu balloons, silica balloons, ceramic balloons, organic balloons such as phenol resin balloons, urea resin balloons, polystyrene balloons, polyethylene balloons, saran balloons, or inorganic compounds and organic Examples thereof include a composite balloon in which a system compound is mixed or laminated.
Also, those coated or surface-treated with these balloons can be used. For example, inorganic balloons surface-treated with the silane coupling agent, etc., organic balloons with calcium carbonate, talc, titanium oxide, etc. Examples of coatings are also included.
Of these, from the viewpoint of the effect of imparting designability, granular materials and / or balloons are preferable, and granular inorganic fillers and / or inorganic balloons are more preferable, especially coarse heavy calcium carbonate and / or ceramics. A balloon is preferred.
The particle size of the granular material and / or balloon is preferably 50 μm or more, and more preferably 100 to 1,000 μm, from the viewpoint of the effect of providing designability.
[0067]
The total amount of filler, coupling agent, adhesiveness imparting agent, thixotropic imparting agent, storage stability improving agent (dehydrating agent), colorant and designability imparting agent is 100 parts by weight of curable resin (B). On the other hand, 0 to 500 parts by weight, particularly 10 to 300 parts by weight are preferred.
[0068]
In the present invention, each additive component can be used alone or in admixture of two or more.
[0069]
In the present invention, a plasticizer is not particularly required, but can be used within a range not impairing the object of the present invention depending on the use of the curable composition.
Examples of the plasticizer include phthalates such as dibutyl phthalate, diheptyl phthalate, dioctyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate, butyl phthalyl butyl glycolate, dioctyl adipate, dioctyl sebacate and the like. Non-aromatic dibasic acid esters, phosphate esters such as tricresyl phosphate, tributyl phosphate and the like, and relatively high molecular weight type plasticizers include, for example, polyesters from dibasic acids and dihydric alcohols. Polyester plasticizers such as polypropylene glycol and polyethers such as etherified derivatives thereof, polystyrenes such as poly-α-methylstyrene, low viscosity (meth) acrylic acid ester copolymers, and other process oils , Alkyl Benzene compounds and the like.
[0070]
Since the curable composition of the present invention has a low viscosity, it is not necessary to use an organic solvent, or even if it is used, it requires only a very small amount and does not release an environmentally hazardous substance, so it is highly safe.
Examples of the organic solvent include conventionally known organic solvents such as aliphatic solvents such as n-hexane, alicyclic solvents such as cyclohexane, aromatic solvents such as toluene and xylene, and the like. Anything that does not react to the above can be used.
[0071]
The curable composition and the sealing material composition of the present invention can be used as a one-pack type or a two-pack type depending on the application, but there is no need to mix the main agent and the curing agent, and curing due to poor mixing. Since there are no defects such as defects and excellent workability, a one-component curable composition is preferable, and a one-component moisture-curable room temperature curable composition is more preferable.
Moreover, the curable composition and the sealing material composition of the present invention are those in which the liquid urethane resin (A) to be used does not volatilize even in a high temperature atmosphere of 50 to 100 ° C., and does not use a highly volatile organic solvent. However, since it has low viscosity and good extrusion workability, it does not dissipate volatile substances during or after curing, so it is used in the manufacture of foods, semiconductors, precision equipment, etc. or in these tests. It can also be suitably used as a sealing agent for sealing or waterproofing clean room wall panels and incidental facilities that are required not to emit volatile substances.
[0072]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
Here, although the sealing material composition was shown as an example of a curable composition, it is not limited to this.
[0073]
Synthesis example 1
In a warming reaction vessel equipped with a stirrer, thermometer, nitrogen seal tube and cooler, under a nitrogen stream, polyoxypropylene monool (XS-M3000 manufactured by Asahi Glass Co., Ltd., number average molecular weight 3,243, molecular weight distribution (Mw / Mn) 1.0-1.1) 300 g (OH equivalent: 0.0925) was charged and 0.1 g of dibutyltin dilaurate and m-xylylene diisocyanate (Takenate 500, molecular weight 188, Takeda Pharmaceutical Co., Ltd.) with stirring. 1 g (NCO equivalent: 0.0968) (R value (NCO equivalent / OH equivalent) = 1.05) was added, and the mixture was heated and stirred at 70-80 ° C. for 4 hours. The reaction was terminated when the value (0.06% by mass) or less was reached, and liquid urethane resin U-1 was produced.
This liquid urethane resin U-1 has a measured isocyanate group content of 0.04% by mass, a viscosity of 3,300 mPa · s / 25 ° C., a molecular weight distribution (Mw / Mn) of 1.0 to 1.1, and is transparent at room temperature. It was a liquid.
[0074]
Synthesis example 2
A polyoxypropylene diol (PML-4010 manufactured by Asahi Glass Co., Ltd., number average molecular weight 9,930, molecular weight distribution (Mw / Mn) 1.0 to 1.1 in a warming reaction vessel similar to Synthesis Example 1 under a nitrogen stream. ) 800 g (OH equivalent: 0.161) was charged, and 49.9 g (NCO equivalent: 0.169) (R value (NCO) of n-octadecyl monoisocyanate (Millionate O, molecular weight 295, manufactured by Hodogaya Chemical Co., Ltd.) with stirring. Equivalent / OH equivalent) = 1.05) and 0.1 g of dibutyltin dilaurate were added, and the mixture was heated and stirred at 70-80 ° C. for 4 hours. The isocyanate group content was the theoretical value (0.04% by mass). ) The reaction was terminated when it became below, and liquid urethane resin U-2 was produced.
This liquid urethane resin U-2 has an isocyanate group content of 0.03% by mass measured by titration, a viscosity of 6,800 mPa · s / 25 ° C., a molecular weight distribution (Mw / Mn) of 1.0 to 1.1, and half at room temperature. It was a clear liquid.
[0075]
Synthesis example 3
Polyoxypropylene triol (Exenol-5030 manufactured by Asahi Glass Co., Ltd., number average molecular weight 5,010, molecular weight distribution (Mw / Mn) 1.0 to 1.2 in a warming reaction vessel similar to Synthesis Example 1 under a nitrogen stream. ) 881.9 g (OH equivalent: 0.528) was charged, and 41.5 g (NCO equivalent: 0.141) (R value) of n-octadecyl monoisocyanate (Millionate O, molecular weight 295, manufactured by Hodogaya Chemical Co., Ltd.) with stirring. (NCO equivalent / OH equivalent) = 0.267) and 0.1 g of dibutyltin dilaurate, and then heated and stirred at 70-80 ° C. for 2 hours, and confirmed the disappearance of the isocyanate group peak by FTIR. And cooled to room temperature. Next, 96.9 g (NCO equivalent: 0.775) (R ′ value (total NCO equivalent / OH equivalent) of raw materials) = 4,4′-diphenylmethane diisocyanate (Millionate MT manufactured by Nippon Polyurethane Industry Co., Ltd., molecular weight 250) = 1.73) was added, and the mixture was heated and stirred at 70 to 80 ° C. for 2 hours. When the isocyanate group content became the theoretical value (1.59% by mass) or less, the reaction was terminated. A group-containing polyoxypropylene-based urethane prepolymer O-1 was produced.
This isocyanate group-containing polyoxypropylene-based urethane prepolymer O-1 was a translucent liquid at room temperature with a measured isocyanate group content of 1.50% by mass and a viscosity of 28,300 mPa · s / 25 ° C.
[0076]
Synthesis example 4
A polyoxypropylene diol (number average molecular weight 16,000, total unsaturation 0.02 meq / g, PML-4016 manufactured by Asahi Glass Co., Ltd., molecular weight distribution (Mw / Mn) 1.0-1.2) 800 g (OH equivalent: 0.1) was charged and stirred with stirring 3-isocyanatopropyltrimethoxysilane (Y-5187, Nippon Unicar Co., Ltd., molecular weight 205.4) 10.3 g. (NCO equivalent: 0.05) (R value (NCO equivalent / OH equivalent) = 0.5) and 0.08 g of dibutyltin dilaurate were added, followed by heating and stirring at 70-80 ° C. for 1 hour. The disappearance of the isocyanate group peak was confirmed by FTIR, and the reaction was terminated by cooling to room temperature.
The obtained trimethoxysilyl group-containing polyoxypropylene urethane resin was a liquid having a theory of transparency at room temperature, an isocyanate group content of 0.00 mass% measured by titration, and a viscosity of 16,400 mPa · s / 25 ° C. This resin is referred to as O-2.
[0077]
Example 1
In a kneading vessel with a heating and cooling device and a nitrogen seal tube, under a nitrogen stream, 50 g of the liquid urethane resin U-1 obtained in Synthesis Example 1 and the isocyanate group-containing polyoxypropylene urethane prepolymer O- obtained in Synthesis Example 3 1 100 g, hindered phenolic antioxidant: pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Irganox 1010 manufactured by Ciba Specialty Chemicals) 0g, 145g of fatty acid (surface) -treated calcium carbonate (Calphan 200M manufactured by Maruo Calcium Co., Ltd.) and 15g of toluene, stirred and mixed until the contents were uniform, then degassed under reduced pressure, filled in a container, sealed, A sealant composition was prepared.
[0078]
Example 2
A sealing material composition was prepared in the same manner as in Example 1 except that 50 g of U-2 was used instead of the liquid urethane resin U-1.
[0079]
Comparative Example 1
In Example 1, instead of the liquid urethane resin U-1, dioctyl phthalate
A sealant composition was prepared in the same manner except that 50 g was used.
[0080]
Example 3
In a similar kneading container as in Example 1, 200 g of liquid urethane resin U-1 obtained in Synthesis Example 1 and 200 g of trioxysilyl group-containing polyoxypropylene-based urethane resin O-2 obtained in Synthesis Example 4 in a nitrogen stream Hindered amine antioxidant: 9 g of a compound represented by the following chemical formula (A) (Sanol LS-292 manufactured by Sankyo Co., Ltd.), 255.7 g of calcium carbonate (Whiteon B manufactured by Shiroishi Calcium Co., Ltd.), fatty acid (surface) treated calcium carbonate ( Maruo Calcium Co., Ltd. N-2) 265.2g was charged and dehydrated under reduced pressure (20-70 hPa) for 2 hours at 100-110 ° C. with stirring and mixing, and after cooling, vinyltrimethoxysilane (Chiasso Silaace S210) 17.0 g and 2.0 g of dibutyltin bis (acetylacetonate) (Neostan U-220 manufactured by Nitto Kasei Co., Ltd.) The mixture was stirred and mixed until uniform, then degassed under reduced pressure, filled in a container, and sealed to prepare a sealant composition.
[0081]
[Chemical formula 2]

[0082]
Example 4
In Example 3, instead of 200 g of the trimethoxysilyl group-containing polyoxypropylene urethane resin O-2 obtained in Synthesis Example 4, the trimethoxysilyl group-containing polyoxypropylene urethane resin O-2 obtained in Synthesis Example 4 was used. A sealing material composition was prepared in the same manner except that 100 g and 100 g of a crosslinkable silyl group-containing polyoxypropylene resin (S303 manufactured by Kaneka Chemical Co., Ltd.) were used.
[0083]
Example 5
In Example 3, a sealing material composition was prepared in the same manner except that 200 g of U-2 was used instead of the liquid urethane resin U-1.
[0084]
Example 6
In Example 3, instead of the trimethoxysilyl group-containing polyoxypropylene-based urethane resin O-2 obtained in Synthesis Example 4, 200 g of a crosslinkable silyl group-containing polyoxypropylene-based resin (S303 manufactured by Kaneka Chemical Industry Co., Ltd.) A sealant composition was prepared in the same manner except that it was used.
[0085]
Comparative Example 2
In Example 4, a sealing material composition was prepared in the same manner except that 200 g of polyoxypropylene diol (number average molecular weight 3,200) was used instead of the liquid urethane resin U-1.
[0086]
Comparative Example 3
In Example 4, a sealing material composition was prepared in the same manner except that 200 g of polyoxypropylene triol (number average molecular weight 12,000) was used instead of the liquid urethane resin U-1.
[0087]
Comparative Example 4
In Example 4, a sealing material composition was prepared in the same manner except that 200 g of dioctyl phthalate was used instead of the liquid urethane resin U-1.
[0088]
〔performance test〕
The following tests were performed using the sealing material compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 4, respectively.
(1) Slump
In accordance with “4.1 Slump Test” of JIS A1439: 1997 “Testing Method of Sealant for Building”, slump (longitudinal) was measured (measurement temperature 23 ° C.).
(2) Workability
As a test for evaluating workability, the extrusion time was measured according to “4.14 Extrusion Test with Cartridge for Testing” in JIS A1439: 1997 “Testing Method of Sealant for Building” (measurement temperature: 23 ° C.).
(3) Tack-free time
Measured in accordance with “4.19 Tack-free test” in JIS A1439: 1997 “Testing method for architectural sealing material”.
(4) Paint contamination
Using a slate plate with a thickness of 5 mm, create a joint with a depth of 5 mm, a width of 25 mm, and a length of 150 mm, place a sealing material composition on the joint, scrape off the excess sealing material with a spatula, and flatten the surface After curing for 7 days at 23 ° C. and 50% relative humidity, a water-based acrylic paint (Tile Rack aqueous top super white made by Nippon Paint Co., Ltd.) was applied to the surface, and at 23 ° C. and 50% relative humidity. The specimen was further cured for 7 days to prepare a test specimen.
Place the test specimen after curing in a 50 ° C. incubator and another test specimen in a 70 ° C. incubator for 7 days, then remove from the incubator and place black quartz sand (grains) on the test specimen surface. The test specimen was immediately turned over, and the bottom surface was lightly tapped by hand to remove excess black silica sand. The state of black silica sand (dirt) remaining on the surface was visually observed to determine the contamination.
Judgment criteria
○: Black silica sand does not adhere to the cured surface of the sealing material and is clean
X: A state in which a large amount of black silica sand adheres to the cured surface of the sealing material and is blackened
The synthesis results of the liquid urethane resin are summarized in Table 1, and the composition of the sealing material composition and the performance thereof are summarized in Tables 2 to 4.
[0089]
[Table 1]

[0090]
[Table 2]

[0091]
[Table 3]

[0092]
[Table 4]

[0093]
【The invention's effect】
As explained above, the liquid urethane resin (A) having a molecular weight distribution (Mw / Mn) substantially not containing an isocyanate group or a hydroxyl group in the present invention having a molecular weight distribution of 1.6 or less is a high molecular weight urethane resin. The curable composition and the sealing material composition containing this are low in viscosity and do not bleed. It has become possible to achieve both excellent anti-contamination performance that does not bleed on the surface of the coating that has been overcoated on the surface of the cured product. Further, since the curable composition and the sealing material composition of the present invention are excellent in workability even if they do not use or use environmental pollutants such as plasticizers and organic solvents, they are excellent in workability. It can meet the growing demand for safe and high-performance products that are non-toxic and do not pollute the environment. Therefore, the curable composition and the sealing material composition of the present invention are adhesives for construction, civil engineering, automobiles, etc., waterproofing materials, sealing materials, especially for exterior wall joints, for civil joints, for automobile joints, etc. It is excellent in workability and surface contamination prevention, and is suitable for high-performance sealing materials that are safe and do not pollute the environment.

Claims (12)

A liquid urethane resin (A) obtained by reacting a polyoxyalkylene alcohol and an organic isocyanate and having a molecular weight distribution (Mw / Mn) substantially not containing an isocyanate group or a hydroxyl group of 1.6 or less, and a curable resin A curable composition comprising (B). The curable composition according to claim 1, wherein the liquid urethane resin (A) is a reaction product of a polyoxyalkylene monool and an organic isocyanate. The curable composition according to claim 1, wherein the liquid urethane resin (A) is a reaction product of a polyoxyalkylene polyol and an organic monoisocyanate. The curable composition of Claim 2 whose molecular weight distribution (Mw / Mn) of the said polyoxyalkylene type monool is 1.6 or less. The curable composition of Claim 3 whose molecular weight distribution (Mw / Mn) of the said polyoxyalkylene-type polyol is 1.6 or less. The curable composition of Claim 1 whose said curable resin (B) is an isocyanate group containing urethane prepolymer. The curable composition of Claim 1 whose said curable resin (B) is crosslinkable silyl group containing resin. The isocyanate group-containing urethane prepolymer is an isocyanate group-containing polyoxyalkylene urethane prepolymer obtained by reacting a polyoxyalkylene polyol and an organic isocyanate with an isocyanate group-excess condition with respect to a hydroxyl group. The curable composition according to 1. The isocyanate group-containing urethane prepolymer is an isocyanate group-containing polyoxyalkylene urethane prepolymer obtained by reacting a polyoxyalkylene-based polyol, an organic polyisocyanate, and an organic monoisocyanate with a hydroxyl group-excessive condition. The curable composition according to claim 6. The crosslinkable silyl group-containing resin is a crosslinkable silyl group-containing polyoxyalkylene urethane resin (a) obtained by reacting a polyoxyalkylene polyol and a crosslinkable silyl group-containing isocyanate compound and / or other crosslinks. The curable composition according to claim 7, which is a functional silyl group-containing polyoxyalkylene resin (b). Furthermore, the curable composition as described in any one of Claims 1-10 containing an additive. A liquid urethane resin (A) obtained by reacting a polyoxyalkylene alcohol and an organic isocyanate and having a molecular weight distribution (Mw / Mn) substantially not containing an isocyanate group or a hydroxyl group of 1.6 or less, and a curable resin A sealing material composition comprising (B).