JP2004269807A - Thixotropic ordinary temperature-curable composition and process for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thixotropic ordinary temperature-curable composition that can impart sufficiently stable thixotropic properties to an ordinary temperature-curable resin by blending into the ordinary temperature-curable resin in a small amount even when a highly polar ordinary temperature-curable resin is used in combination with an additive or the like such as a weather-resistant stabilizer or the like or a catalyst; that has a low viscosity and can easily be dispersed; and that is excellent in storage stability and workability and to provide a process for producing the composition. <P>SOLUTION: The thixotropic ordinary temperature-curable composition comprises the ordinary temperature-curable resin and an alkylene oxy group-containing hydrocarbon group-bonded inorganic substance particle. The process for producing the composition comprises reacting an alkylene oxy group-containing hydrocarbon group and a crosslinkable silyl group-containing compound with a crosslinkable silyl group-reactive functional group-containing inorganic substance particle in the presence of the ordinary temperature-curable resin and in the presence of a reaction catalyst and/or an organic dispersion medium or in the absence thereof to synthesize the alkylene oxy group-containing hydrocarbon group-bonded inorganic substance particle. <P>COPYRIGHT: (C)2004,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。）
【００３７】
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）末端に水酸基等の官能基を有するポリオキシアルキレン系重合体に、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、アミノ基、エポキシ基、イソシアネート基等の官能基を有するポリオキシアルキレン系重合体に、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、ビニル型不飽和結合含有シラン類、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 ）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）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）と反応させる。
【００３８】
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、硬化前の粘度が低いので取り扱い易く、硬化後の強度、伸び、モジュラス等の物性が優れているので好適である。
変成シリコーン樹脂は、架橋性シリル基が大気中の湿気（水分）と常温で反応、硬化することにより、一液硬化型として使用できるし、また硬化剤として別途オクチル酸第２錫などの硬化触媒と可塑剤等を配合しておいたものを、主剤の変成シリコーン樹脂と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。
【００３９】
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′−Ｓｘ）ｙ−Ｒ″−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。ｙ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′及びＲ″は２価の脂肪族炭化水素基であり、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、２００〜２０，０００、特に１，０００〜８，０００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、樹脂を常温で酸化、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。
【００４０】
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、常温でラジカル重合、硬化させる二液硬化型としても使用できる。
【００４１】
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硬化触媒を混合することにより常温で酸化、硬化させる二液硬化型としても使用できる。
【００４２】
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、脂環族エポキシ樹脂、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などが挙げられる。
【００４３】
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、フェノール類などが挙げられる。
【００４４】
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、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。
【００４５】
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、ポリイソシアネートを硬化剤として常温で硬化させる二液硬化型樹脂も挙げられる。
【００４６】
次に、本発明において使用するアルキレンオキシ基含有炭化水素基結合無機系物質粒子について説明する。
このアルキレンオキシ基含有炭化水素基結合無機系物質粒子は、無機系物質粒子の表面に化学反応によりアルキレンオキシ基含有炭化水素基を導入したものであり、少量の使用で本発明の硬化性組成物に強力で安定した揺変性を付与するものである。具体的に例えば、下記一般式（２）に示されるものが好適に挙げられる。
【化２】

ここにおいてアルキレンオキシ基含有炭化水素基とは（２）式において、ＹとＺを除いた部分を示し、このアルキレンオキシ基の強力な水素結合と炭化水素基の絡み合いにより、安定した揺変性付与構造を形成するものと推測される。
また本発明において、アルキレンオキシ基を含有している基が炭化水素基であって、前述の常温硬化性樹脂とは常温で貯蔵中に反応しない基であるという点が重要である。理由は、仮にアルキレンオキシ基含有炭化水素基結合無機系物質粒子の炭化水素基にアミノ基などの官能基が付いていた場合、イソシアネート基含有ウレタンプレポリマーなどの常温硬化性樹脂と常温で貯蔵中に反応を起こして、得られる硬化性組成物が貯蔵中に揺変性付与構造が破壊されてしまうとともに増粘してしまうためである。
（２）式中のＲ^１としては、例えば、炭素数１〜１０のメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｎ−ヘキシル基、ｎ−オクチル基、ｎ−デシル基等の１価の脂肪族炭化水素基、フェニル基等の１価の芳香族炭化水素基、ベンジル基等の１価の芳香脂肪族炭化水素基、シクロヘキシル基等の１価の脂環族炭化水素基などが挙げられ、Ｒ^２としては、例えば、炭素数１〜５のエチレン基、プロピレン基、ブチレン基、テトラメチレン基等の２価のアルキレン基が挙げられ、Ｒ^３としては、例えば、炭素数１〜１０のメチレン基、エチレン基、ｎ−プロピレン基、イソプロピレン基、ｎ−ブチレン基、イソブチレン基、ｎ−ヘキシレン基、ｎ−オクチレン基、ｎ−デシレン基等の２価の脂肪族炭化水素基、フェニレン基等の２価の芳香族炭化水素基、シクロヘキシレン基等の２価の脂環族炭化水素基などが挙げられ、それぞれ製造のし易さと揺変性付与効果の大きさの点から、Ｒ^１としては炭素数１〜１０の１価の脂肪族炭化水素基が好ましく、更にメチル基又はエチル基が好ましく、Ｒ^２としてはエチレン基又はプロピレン基が好ましく、極性が大きな点でエチレン基が最も好ましい。Ｒ^３としては炭素数１〜１０の２価の脂肪族炭化水素基が好ましく、更にｎ−プロピレン基が好ましい。アルキレンオキシ基の個数ｎは１〜２０個であり、揺変性付与効果の大きさの点から、２〜２０個のポリアルキレンオキシ基が好ましい。
（２）式中の連結基Ｙは無機系物質粒子Ｚとアルキレンオキシ基含有炭化水素基Ｒ^１−Ｏ−（Ｒ^２Ｏ）ｎ−Ｒ^３とを結合する基であり、−ＴｉＯ−、−ＳｉＯ−などが挙げられるが（無機系物質粒子Ｚと連結したものは、−ＴｉＯ−Ｚ、−ＳｉＯ−Ｚと表わされる）、製造のし易さと揺変性付与効果の大きさの点から、−ＳｉＯ−（シロキサン結合）が好ましい。
また、無機系物質粒子に安定した揺変性付与能力を与えるために、アルキレンオキシ基含有炭化水素基は、この連結基Ｙにより無機系物質粒子の表面Ｚに１個以上結合されていればよい。
なお、（２）式において、連結基Ｙは無機系物質粒子の表面Ｚと１本の手で連結されているように模式的に示しているが、シロキサン結合を例として説明すると、−ＳｉＯ−、−Ｓｉ（Ｏ−）_２、−Ｓｉ（Ｏ−）_３の１〜３本の連結可能な手を有しており、そのうちの少なくとも１本の手で無機系物質粒子の表面Ｚと連結されていればよいことを示している。
【００４７】
前記のアルキレンオキシ基含有炭化水素基結合無機系物質粒子としては、具体的には、アルキレンオキシ基含有炭化水素基及び架橋性シリル基含有化合物の架橋性シリル基（反応性シリル基）と、架橋性シリル基反応性官能基含有無機系物質粒子とを反応させ、シロキサン結合（−ＳｉＯ−）を形成させることにより、無機系物質粒子表面にアルキレンオキシ基含有炭化水素基を導入した反応生成物を好適に挙げることができる。
このアルキレンオキシ基含有炭化水素基及び架橋性シリル基含有化合物としては、具体的には下記一般式（３）に示す化合物が好適に挙げられる。
【化３】

【００４８】
具体例としては、下記式（各式中、ｎは１〜２０の整数である。）で示される各化合物が挙げられ、これらは単独で或いは２種以上を組み合わせて使用できる。
【化４】

【００４９】
これらのうち、入手の容易さと反応して得られるアルキレンオキシ基含有炭化水素基結合無機系物質粒子の揺変性付与効果が大きい点から、下記式（各式中、ｎは１〜２０の整数である。）で示される各化合物が好ましく、特に好ましい代表的な市販品として日本ユニカー社製Ａ−１２３０や信越化学工業社製Ｘ−１２−６４１がある。
【化５】

【００５０】
前記架橋性シリル基反応性官能基含有無機系物質粒子は、粒子表面にアルキレンオキシ基含有炭化水素基及び架橋性シリル基含有化合物の架橋性シリル基に対して反応可能な官能基を有しているものであればどのようなものでもよい。このような架橋性シリル基反応性官能基としては具体的には例えば、Ｍｇ−ＯＨ、Ｃａ−ＯＨ、Ｔｉ−ＯＨ、Ｆｅ−ＯＨ、Ａｌ−ＯＨ、Ｓｉ−ＯＨ等の各種金属原子に結合した水酸基が挙げられる。また、前記架橋性シリル基反応性官能基を無機系物質の粒子表面に有しているならば、単一の無機系物質粒子が前記反応性官能基を有しているものであってもよく（例えば二酸化ケイ素粒子）、他の無機系物質粒子が前記反応性官能基を有している無機物質により被覆或いは混合等により複合化されているものでもよく（例えば、炭酸カルシウム粒子の表面を二酸化ケイ素粒子でコーティングしたもの）、また他の無機系物質粒子に不純物として前記反応性官能基を有している無機物質が含有されているものであってもよい（例えば、炭酸カルシウム粒子中に不純物として二酸化ケイ素を含有したもの）。
なお、ここにおいて、例えば二酸化ケイ素（ＳｉＯ_２）等の化学式では水酸基がないものでも、粒子表面は水分により反応を受け、水酸基を含有しているのである。また、金属粒子については、粒子表面が酸化され、次いで水分により反応を受け、使用の際には粒子表面に水酸基を含有しているのである。
また、前記無機系物質粒子には、炭素（カーボンブラック等）或いは（メタ）アクリル系重合体粒子、サランマイクロバルーン等の有機系物質粒子を、前記無機物質で被覆処理等加工したものも含まれる。
架橋性シリル基反応性官能基含有無機系物質粒子としては、石灰石、珪藻土、カオリンクレーなどの天然鉱物を微粉砕したものでもよいし、また沈降炭酸カルシウム、乾式法シリカ粒子等の合成品あってもよく、具体的に例えば、チタン、鉄、ニッケル、銅、亜鉛、アルミニウム等の金属粒子、酸化チタン、酸化鉄、酸化亜鉛、酸化アルミニウム、水酸化アルミニウム、二酸化ケイ素（シリカ）、含水ケイ酸等の金属酸化物粒子、水酸化マグネシウム、水酸化カルシウム、水酸化アルミニウム等の金属水酸化物粒子、重質炭酸カルシウムや沈降炭酸カルシウム（軽質炭酸カルシウム又はコロイド状炭酸カルシウム）等の炭酸カルシウム、塩基性炭酸マグネシウム等の金属炭酸塩粒子、ウォラストナイト等のケイ酸カルシウム、含水ケイ酸カルシウム、カオリンクレー等のケイ酸アルミニウム、天然マイカ等のケイ酸アルミニウム−カリウム、含水ケイ酸アルミニウム、タルク等のケイ酸マグネシウム等の金属ケイ酸塩粒子、ジルコニア等のセラミックス粒子、カリガラス等の各種ガラス粒子等が挙げられ、これらは単独で或いは２種以上組み合わせて使用できる。
更に、二酸化ケイ素（シリカ）としては、石英、ケイ砂、珪藻土等を粉砕した天然シリカ、また、沈降法シリカ等の湿式法シリカやフュームドシリカ等の乾式法シリカ等の合成シリカなどが挙げられる。
また、前記無機系物質粒子の形状はどんなものであってもよく、具体的には例えば、フュームドシリカ等の球状、セピオライト、ウォラストナイト等の繊維状或いは針状、マイカやタルク等のフレーク状（板状）、雲母等の鱗片状、シリカゲル等の多孔質状、シリカバルーン等のバルーン状、珪藻土等の管状など種々の形状が挙げられ、用途に応じて使い分けることができる。
本発明において、前記無機系物質粒子の平均（一次）粒子径（直径又は長径）は、１，０００，０００ｎｍ（１，０００μｍ）以下、更には１〜１００，０００ｎｍ（１００μｍ）、特に１〜１０，０００ｎｍ（１０μｍ）が好ましく、また更に、アルキレンオキシ基含有炭化水素基及び架橋性シリル基含有化合物を粒子表面で反応させた無機系物質粒子が常温硬化性樹脂に対して揺変性を付与する効果が大きい点で、前記無機系物質粒子の平均（一次）粒子径は１〜１，０００ｎｍのコロイド状と呼ばれるものが好ましく、更に１〜１００ｎｍが好ましく、特に５〜５０ｎｍが好ましい。またＢＥＴ比表面積（ｍ^２／ｇ）は、０．１以上、更には２０〜５００が好ましく、特に４０〜５００が好ましい。
本発明においては、前記のうち、金属酸化物粒子、金属水酸化物粒子、金属炭酸塩粒子、金属ケイ酸塩粒子が好ましく、更に二酸化ケイ素粒子が好ましく、特にアルキレンオキシ基含有炭化水素基及び架橋性シリル基含有化合物を反応させたとき、常温硬化性樹脂に対する揺変性付与効果が大きいことよりコロイド状のシリカが好ましく、親水性コロイド状シリカが最も好ましい。
また、前記無機系物質粒子は結晶水を持っていてもよいし、また持っていなくてもよいが、組成物が一液湿気硬化型の場合は、貯蔵安定性を向上させるためには結晶水を持っていない方が好ましい。
なお、無機系物質粒子は粉体状であってもよいし、あらかじめ水媒体、トルエン、キシレン等の有機溶媒、ＤＯＰ等の可塑剤などの液状媒体中に分散されたものであってもよいが、使用方法の自由度が高い点で粉体状の方が好ましい。
【００５１】
アルキレンオキシ基含有炭化水素基及び架橋性シリル基含有化合物は架橋性シリル基反応性官能基含有無機系物質粒子（の固形分）１００重量部に対して０．０１〜２００重量部、更に１〜５０重量部反応させるのが好ましい。０．０１重量部を下回ると硬化性組成物に安定した揺変性を付与することができにくくなり、２００重量部を上回っても揺変性付与効果に変化がなく、コストの高いものとなってしまうため好ましくない。
【００５２】
アルキレンオキシ基含有炭化水素基結合無機系物質粒子は、常温硬化性樹脂１００重量部に対して、０．１〜３００重量部、更に１〜１００重量部、特に５〜５０重量部配合するのが好ましい。配合量が０．１重量部を下まわると揺変性付与効果が小さくなり過ぎ、３００重量部を超えると作業性が悪くなる。
【００５３】
本発明において、揺変性常温硬化性組成物を製造する方法としては、常温硬化性樹脂の存在下で、かつ、反応触媒及び／又は有機分散媒の存在下又は不存在下で、アルキレンオキシ基含有炭化水素基及び架橋性シリル基含有化合物と架橋性シリル基反応性官能基含有無機系物質粒子とを５〜２００℃の温度で０．１〜１００時間、好ましくは３０〜８０℃の温度で０．５〜１０時間加熱し反応させて、アルキレンオキシ基含有炭化水素基結合無機系物質粒子を合成すると同時に、揺変性常温硬化性組成物を得る方法が挙げられる。反応触媒と有機分散媒は必要に応じて使用すればよいが、反応触媒は反応温度を低下でき、反応時間も短縮できるため使用するのが好ましい。なお、必要に応じて後述の添加剤を混合する。また、この反応の際には後述の添加剤が存在しなくてもよいが、存在していてもよい。
揺変性常温硬化性組成物を製造する他の方法としては、前記のアルキレンオキシ基含有炭化水素基及び架橋性シリル基含有化合物と架橋性シリル基反応性官能基含有無機系物質粒子とを、反応触媒及び／又は有機分散媒の存在下又は不存在下、５〜２００℃の温度で０．１〜１００時間、好ましくは３０〜８０℃の温度で０．５〜１０時間加熱し反応させてアルキレンオキシ基含有炭化水素基結合無機系物質粒子をあらかじめ合成し、次いで得られたアルキレンオキシ基含有炭化水素基結合無機系物質粒子（有機分散媒を使用したときは、有機分散媒混合体のままか、或いはロ過又は有機分散媒を揮発などして分離したもの）を、常温硬化性樹脂に添加、混合して揺変性常温硬化性組成物を得る方法が挙げられる。反応触媒と有機分散媒は必要に応じて使用すればよいが、反応触媒は反応温度を低下でき、反応時間も短縮できる点で、有機分散媒は反応を均一にできる点で使用するのが好ましい。なお、必要に応じて後述の添加剤を混合する。
本発明においては、前者の常温硬化性樹脂などの存在下、アルキレンオキシ基含有炭化水素基及び架橋性シリル基含有化合物と架橋性シリル基反応性官能基含有無機系物質粒子とを反応させる製造方法の方が、製造し易く低コストである点から特に好ましい。
なお、前記アルキレンオキシ基含有炭化水素基結合無機系物質粒子は、トリメチルクロロシランやヘキサメチルシラザンなどで親水性シリカなどの表面を処理した疎水性シリカなどにおいて、アルキレンオキシ基含有炭化水素基及び架橋性シリル基含有化合物を、残っている少量のＳｉ−ＯＨ基に、或いは少量の水の存在下に加水分解と同時に反応させることにより合成することもできる。
前記の必要に応じて使用するのが好ましい反応触媒は、前記のアルキレンオキシ基含有炭化水素基及び架橋性シリル基含有化合物の架橋性シリル基（反応性シリル基）と前記の架橋性シリル基反応性官能基含有無機系物質粒子の架橋性シリル基反応性官能基とが反応しシロキサン結合を形成するのを促進する触媒であり、例えば、有機金属化合物、アミン類等が挙げられ、具体的には例えば、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、これらは単独或いは２種以上を組み合わせて用いることができる。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）又は旭硝子社製ＥＸＣＥＳＴＡＲ Ｃ−５０１が最も好ましい。
前記反応触媒は、架橋性シリル基反応性官能基含有無機系物質粒子１００重量部に対して、０〜１０重量部、特に０．０５〜５重量部配合するのが好ましい。前記有機分散媒としては、後述の添加剤として例示した有機溶剤又は可塑剤で各成分と反応しないものであればどのようなものでも使用できる。
前記有機分散媒は、架橋性シリル基反応性官能基含有無機系物質粒子１００重量部に対して、０〜３，０００重量部、特に５０〜２，０００重量部配合するのが好ましい。
【００５４】
本発明における添加剤としては、硬化触媒、耐候安定剤、充填剤、可塑剤、カップリング剤、接着性付与剤、保存安定性改良剤（脱水剤）、着色剤、つや消し剤、有機溶剤などが挙げられる。
【００５５】
硬化触媒は、常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硬化触媒、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）硬化触媒、アルキッド樹脂の硬化を促進させるための乾燥用硬化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硬化触媒としては、具体的には、前述のアルキレンオキシ基含有炭化水素基及び架橋性シリル基含有化合物と架橋性シリル基反応性官能基含有無機系物質粒子との反応において必要に応じて使用する反応触媒として例示した化合物と同様のものが挙げられる。それらのうち、反応速度が高く、毒性及び揮発性の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）硬化触媒としては、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硬化触媒としては、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、常温硬化性樹脂１００重量部に対して、０〜１０重量部、特に０．０５〜２重量部配合するのが好ましい。
【００５６】
耐候安定剤は、常温硬化性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。
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、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。
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）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。
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。
耐候安定剤は、常温硬化性樹脂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。
【００５７】
充填剤、可塑剤、カップリング剤、接着性付与剤、保存安定性改良剤（脱水剤）、着色剤、つや消し剤等は、それぞれ補強や増量、粘度低下、接着性向上、貯蔵安定性向上、着色、硬化物の表面のつや消し等のために使用することができる。
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、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、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、熱可塑性或いは熱硬化性樹脂の微粉末、ポリエチレン等の粉末や中空体、サランマイクロバルーン等の有機系バルーン状充填剤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。
可塑剤としては、具体的には、フタル酸ジオクチル、フタル酸ジブチル、フタル酸ブチルベンジル等のフタル酸エステル類、アジピン酸ジオクチル、コハク酸ジイソデシル、セバシン酸ジブチル、オレイン酸ブチル等の脂肪族カルボン酸エステル類、ペンタエリスリトールエステル等のアルコールエステル類、リン酸トリオクチル、リン酸トリクレジル等のリン酸エステル類、塩素化パラフィン、前記のイソシアネート基含有ウレタンプレポリマーの合成に使用されるポリエーテルポリオールをエーテル化又はエステル化などしたポリオキシアルキレン類、中でもシュークロースなどの糖類多価アルコールにエチレンオキサイドやプロピレンオキサイドを付加重合したポリエーテルポリオールをエーテル化又はエステル化などした糖類系ポリオキシアルキレン類、ポリ−α−メチルスチレン、ポリスチレン等のポリスチレンのオリゴマー類、ポリ（メタ）アクリル系樹脂等の（メタ）アクリル系重合体、ポリブタジエン、ブタジエン−アクリロニトリル共重合体、ポリクロロプレン、ポリイソプレン、水素添加ポリブテン等のオレフィン系重合体などの可塑剤が挙げられる。
カップリング剤としては、前記のアルキレンオキシ基含有炭化水素基及び架橋性シリル基含有化合物以外の、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の化合物が好適に挙げられる。
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、ポリイソシアネート化合物等が挙げられる。
本発明において、アルキレンオキシ基含有炭化水素基結合無機系物質粒子は揺変性付与効果が大きなため、他の揺変剤は使用しなくても良いが、揺変性付与の補助として使用することもできる。このような揺変剤としては、例えば、コロイダルシリカ、石綿粉等の無機揺変剤、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。
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、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。
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。
つや消し剤は、本発明の揺変性硬化性組成物を例えばシーリング材として使用したときに、硬化後の表面光沢度を低下させ、表面を艶消しし、シーリングの目地を目立たせず、外壁材の特徴的美観を損なわなくし、また、硬化後の表面粘着をなくし、埃などの付着による汚染を防止することができる。つや消し剤としては、例えば、パラフィンワックスやステアリン酸アミドなどの高級脂肪族化合物、桐油や亜麻仁油などの乾性油に代表される空気中の酸素と反応する化合物、前記充填剤として例示したもので、粒径が１００〜１，０００μｍと大きなもの、水と反応して融点が３５℃以上の第１級及び／又は第２級アミンを生成する化合物或いは融点が３５℃以上の第１級アミンや第２級アミンなどが挙げられる。
水と反応して融点が３５℃以上の第１級及び／又は第２級アミンを生成する化合物としては、具体的には、ステアリルアミンやジステアリルアミンなどの融点が３５℃以上の第１級及び／又は第２級アミン化合物と、４−メチル−２−ペンタノンなどのケトン化合物或いはイソブチルアルデヒドなどのアルデヒド化合物などのカルボニル化合物とを脱水反応して得られる化合物が好適に挙げられる。融点が３５℃以上の第１級アミンや第２級アミンとしてはステアリルアミン等の第１級アミン、ジステアリルアミン等の第２級アミンなどが挙げられる。
【００５８】
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。
【００５９】
充填剤、可塑剤、カップリング剤、接着性付与剤、保存安定改良剤（脱水剤）、着色剤、つや消し剤、有機溶剤の合計の配合量は、常温硬化性樹脂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。
【００６０】
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種以上組み合わせて使用することができる。
【００６１】
なお、本発明の揺変性常温硬化性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、一液型の揺変性常温硬化性組成物が好ましく、更に一液湿気硬化型揺変性常温硬化性組成物が好ましい。
なお、二液型として使用する場合、前記のアルキレンオキシ基含有炭化水素基結合無機系物質粒子を主剤と硬化剤のどちらか一方に配合してもよいし、また両方に配合してもよい。
【００６２】
【実施例】
以下、本発明について実施例等により更に詳細に説明する。
ここにおいて、揺変性常温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。
【００６３】
〔イソシアネート基含有ウレタンプレポリマーの合成〕
合成例１
攪拌機、温度計及び窒素シール管の付いた加温、冷却装置付き反応容器に、窒素気流下にポリオキシプロピレンジオール（数平均分子量３，２００、旭硝子社製エクセノール３０２１）４５７．６ｇとポリオキシプロピレントリオール（数平均分子量４，０００、三井化学社製ＭＮ−４０００）２９１．７ｇとトルエン４４．７ｇを仕込み、攪拌しながら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）１９５．４ｇ（Ｒ値（ＮＣＯ当量／ＯＨ当量）＝３．１）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、イソシアネート基濃度が理論値（４．４９質量％）以下になった時点で、常温まで冷却して反応を終了させた（実測イソシアネート基濃度４．３８質量％）。
得られたイソシアネート基含有ウレタンプレポリマーは、常温で透明の粘度８，５００ｍＰａ・ｓ／２５℃の液体であった。
【００６４】
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、窒素気流下に合成例１で得たイソシアネート基含有ウレタンプレポリマーを８８９．０ｇと親水性コロイド状シリカ（トクヤマ社製レオロシールＱＳ−１０２、ＢＥＴ比表面積２００ｍ^２／ｇ、平均一次粒子径約１５ｎｍ）を６７．６ｇとアルキルオキシ（ポリアルキレンオキシ）アルキルトリアルコキシシラン（日本ユニカー社製Ａ−１２３０）を１５．０ｇと反応触媒として錫系キレート触媒（旭硝子社製ＥＸＣＥＳＴＡＲＣ−５０１）を０．９ｇ仕込み、６０℃で２時間攪拌、混合した後、常温まで冷却し、減圧脱泡した後、容器に充填、密封してシーリング材組成物を調製した。
【００６５】
実施例２
実施例１において、各原料を仕込んだ後、６０℃で２時間攪拌、混合する代わりに、３０℃で５時間攪拌、混合した以外は同様にして、シーリング材組成物を調製した。
【００６６】
実施例３
実施例２において、反応触媒として更にアミン系触媒を０．９ｇ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。
【００６７】
比較例１
実施例１において、アルキルオキシ（ポリアルキレンオキシ）アルキルトリアルコキシシランを使用しない以外は同様にして、シーリング材組成物を調製した。
【００６８】
比較例２
実施例２において、アルキルオキシ（ポリアルキレンオキシ）アルキルトリアルコキシシランを使用しない以外は同様にして、シーリング材組成物を調製した。
【００６９】
比較例３
実施例３において、アルキルオキシ（ポリアルキレンオキシ）アルキルトリアルコキシシランを使用しない以外は同様にして、シーリング材組成物を調製した。
【００７０】
比較例４
実施例１において、アルキルオキシ（ポリアルキレンオキシ）アルキルトリアルコキシシラン１５．０ｇを使用する代わりにメチルトリメトキシシラン１５．０ｇ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。
【００７１】
〔性能試験〕
前記実施例１〜３と比較例１〜４で調製した直後のシーリング材組成物について、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」及び「４．１９タックフリー試験」に準拠して、スランプ（縦）とタックフリー時間を測定した（測定温度２３℃）。
この結果とシーリング材組成物の組成などをまとめて表１及び２に示す。
【００７２】
【表１】

【００７３】
【表２】

【００７４】
【発明の効果】
以上説明した通り、本発明により、常温硬化性樹脂に対し十分に安定した揺変性を付与することができるため、結果として多様な組成を組むことができ、また低粘度で分散容易かつ貯蔵安定性、作業性に優れた揺変性常温硬化性組成物及びその製造方法を提供することができる。また、本発明により、遥変性を消失させることなく、硬化触媒を使用することができるため硬化速度が大きく、また内部硬化性に優れた揺変性常温硬化性組成物を提供することでができる。
すなわち、本発明の揺変性常温硬化性組成物は、建築物などの幅広の垂直目地などに塗布施工したとき垂れないような、重いタイルなどを壁面に接着するときずり落ちないような強い揺変性を発現することができる。そのため、建築物、土木、自動車用などの塗料、接着剤、塗膜防水塗料、塗り床材、パテ材、シーリング材などに特に適している。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a cold-curable composition having strong thixotropic properties and a method for producing the same.
[0002]
[Prior art]
Conventionally, resin components such as waterproofing sealing materials, adhesives, and paints for buildings, civil engineering, and automobiles have been used in modified silicone resins and isocyanate group-containing resins because of their excellent workability and adhesiveness. Room temperature curable resins such as polymers are widely used, and in some applications, it is necessary to impart thixotropic properties.
For example, with adhesives, do not slip down when gluing heavy tiles etc. to the building wall surface, and in coating film waterproof paint or coated flooring, do not drip when thickly applied to vertical wall surfaces or rising surfaces, The putty material has good spatula cutting properties, and the sealing material does not drip (do not slump) when applied to wide vertical joints and ceiling joints of buildings, etc. There has been a demand for a material having a higher curing speed and a material having a higher curing speed for shortening the working time.
As a method of imparting thixotropic properties to paints, adhesives, sealing materials, and the like, it is common to mix colloidal silica, fatty acid-treated calcium carbonate, and the like in a room temperature curable resin.
[0003]
However, in order to impart sufficient thixotropic properties to the room-temperature-curable resin, a large amount of the fatty acid-treated calcium carbonate needs to be used, and thus the degree of freedom of formulation is reduced. When blended with a resin, there are problems such as deterioration of storage stability due to moisture content and an increase in equipment size. In the case of colloidal silica, there is an advantage that a small amount of the colloidal silica is used, but an additive such as a weather resistance stabilizer is used in combination with a large-polarity room temperature curable resin, or a catalyst for accelerating the curing. And the addition of a large-temperature, room-temperature-curable resin or weather-resistant stabilizer, etc., or a catalyst interacts with -SiOH groups on the colloidal silica surface to destroy the structure that imparts thixotropic properties. It is presumed that thixotropic disappears and causes fluidization to cause sagging and slump, making it impossible to use additives or catalysts such as large polar room temperature curable resins and weathering stabilizers, and the composition is limited. There is a problem that is done.
In order to improve these drawbacks, hydrophilic colloidal silica is reacted with dimethyldichlorosilane or the like to make it hydrophobic, or a polyurethane resin is made of a hydrophobic colloidal silica and a reaction product of an aminosilane coupling agent and a polyisocyanate. Although a method of using it in combination (see Patent Document 1) and the like have been proposed, their effects are still insufficient, and in order to prevent sagging in a composition using a room-temperature-curable resin having a large polarity or a catalyst, the use of such a method is considered. There is still the problem that it is necessary to increase the amount, and as a result the viscosity increases and the workability deteriorates.
[0004]
[Patent Document 1]
JP-A-64-14269
[0005]
[Problems to be solved by the invention]
An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a sufficiently stable vibration even when an additive or a catalyst such as a weather resistance stabilizer or a catalyst is used in combination with a large amount of a room-temperature-curable resin having a small amount of compounding. Modification can be imparted, and as a result, a variety of compositions can be assembled according to the needs of customers, and a low-viscosity, easy-to-disperse, storage-stable, and thixotropic cold-curable composition excellent in workability and the like. It is to provide a manufacturing method. Another object of the present invention is to provide a thixotropic room-temperature curable composition that can use a curing catalyst, can increase the curing speed, and has excellent internal curability.
[0006]
[Means for Solving the Problems]
In order to achieve the above object, the present inventors have conducted intensive studies, and as a result, by using particles having an alkyleneoxy group-containing hydrocarbon group introduced on the surface of the inorganic material particles, they are strong and stable with respect to a room temperature curable resin. The present inventors have found that thixotropic properties can be imparted, and have reached the present invention. It is presumed that this stable thixotropic effect is brought about by forming a stable thixotropic structure by entanglement of the strong hydrogen bond of the alkyleneoxy group and the hydrocarbon group bonded thereto.
That is, the present invention includes the following (1) to (9).
[0007]
(1) A thixotropic cold-setting composition comprising a cold-setting resin and alkyleneoxy group-containing hydrocarbon group-bonded inorganic material particles.
[0008]
(2) reaction product of the alkyleneoxy group-containing hydrocarbon group-bonded inorganic substance particles with the alkyleneoxy group-containing hydrocarbon group-crosslinkable silyl group-containing compound and the crosslinkable silyl group-reactive functional group-containing inorganic substance particles; The thixotropic cold-setting composition according to the above (1).
[0009]
(3) Reaction of the alkyleneoxy group-containing hydrocarbon group-bonded inorganic material particles with a polyalkyleneoxy group-containing hydrocarbon group-crosslinkable silyl group-containing compound and a crosslinkable silyl group-reactive functional group-containing inorganic material particle. The thixotropic cold-setting composition of the above (1), which is a product.
[0010]
(4) The thixotropic modification of the above (1) or (2), wherein the alkyleneoxy group-containing hydrocarbon group is an alkyleneoxy group-containing hydrocarbon group having no functional group that reacts with a room temperature curable resin at room temperature. Room temperature curable composition.
[0011]
(5) The inorganic material particles having a crosslinkable silyl group-reactive functional group are selected from the group consisting of metal particles, metal oxide particles, metal hydroxide particles, metal carbonate particles and metal silicate particles. The thixotropic cold-setting composition according to the above (2) or (3), which is a seed or two or more kinds of particles.
[0012]
(6) The thixotropic cold-setting composition according to (2) or (3), wherein the crosslinkable silyl group-reactive functional group-containing inorganic substance particles are silicon dioxide particles.
[0013]
(7) The thixotropic cold-setting composition according to (1) or (4), wherein the cold-setting resin is an isocyanate group-containing urethane prepolymer.
[0014]
(8) The thixotropic cold-setting composition according to any one of (1) to (7), further containing an additive.
[0015]
(9) The method for producing a thixotropic cold-setting composition according to (1) above, wherein the alkylene is added in the presence of a cold-setting resin and in the presence or absence of a reaction catalyst and / or an organic dispersion medium. Reacting an oxy group-containing hydrocarbon group and a crosslinkable silyl group-containing compound with a crosslinkable silyl group-reactive functional group-containing inorganic material particle to synthesize an alkyleneoxy group-containing hydrocarbon group-bonded inorganic material particle; The method as described above.
[0016]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
Room temperature curable resin as a resin component in the present invention, at room temperature, by reaction with moisture in the air, by radical polymerization or oxidative polymerization by mixing a radical generator or the like, or by a cross-linking reaction between the main agent and the curing agent It crosslinks and polymerizes and cures.
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 a curing catalyst. Or a two-pack type composed of an epoxy resin, an active hydrogen-containing urethane-based resin, an active hydrogen-containing fluororesin, a curing agent, a curing catalyst, and the like. Among these, a one-pack moisture-curable (including a curing catalyst in some cases) isocyanate group-containing urethane prepolymer is preferred because of excellent workability.
These can be used alone or in combination of two or more.
[0017]
The isocyanate group-containing urethane prepolymer is one in which the isocyanate group reacts with moisture (moisture) to form a urea bond to crosslink and cure, and further extends the chain with the organic polyisocyanate and the high molecular polyol in some cases. Those obtained by reacting an agent with active hydrogen (group) under the condition of an excess of isocyanate group are preferable.
[0018]
Organic polyisocyanates include 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and 4,4'-diphenyl ether Diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,4 Aromatic diisocyanates such as naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, 1,6-hexamethylene Diisocyanates, 1,4-tetramethylene diisocyanate, aliphatic diisocyanates such as lysine diisocyanate methyl ester, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, araliphatic diisocyanates such as tetramethyl xylene diisocyanate, isophorone diisocyanate, Organic diisocyanates such as alicyclic diisocyanates such as hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated tetramethylxylene diisocyanate are preferred. Of these, aromatic diisocyanates are more preferred. Further, so-called modified isocyanates such as adduct-modified, burette-modified, isocyanurate-modified, uretonimine-modified, uretdione-modified and carbodiimide-modified organic diisocyanates can also be used. Further, a polyisocyanate called a so-called polymeric body such as polymethylene polyphenyl polyisocyanate, crude toluene polyisocyanate and the like can also be used.
These organic polyisocyanates can be used alone or in combination of two or more.
[0019]
Examples of the polymer polyol include a polyester polyol, a polyether polyol, a polycarbonate polyol, a polyolefin polyol, an acrylic polyol, an animal and plant polyol, a copolyol thereof, and the like, or a mixture of two or more thereof. Among these high molecular polyols, polyether polyols are preferred from the viewpoint of excellent workability, adhesiveness, water resistance, weather resistance, and the like.
[0020]
As polyester polyols, for example, succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid, naphthalenedicarboxylic acid, trimellit At least one kind of polycarboxylic acid such as acid, acid ester, or acid anhydride; ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butane Diol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonane Diol, diethylene glycol, dipropylene glycol, 1 4-cyclohexanedimethanol, ethylene oxide or propylene oxide adduct of bisphenol A, low molecular weight alcohols such as trimethylolpropane, glycerin, pentaerythritol, low molecular weight amines such as hexamethylenediamine, xylylenediamine, isophoronediamine, mono A polyester polyol or a polyesteramide polyol obtained by a dehydration condensation reaction with one or more low-molecular-weight amino alcohols such as ethanolamine and diethanolamine.
Also, for example, lactone-based polyester polyols obtained by ring-opening polymerization of cyclic ester (lactone) monomers such as ε-caprolactone and γ-valerolactone using low molecular alcohols, low molecular amines and low molecular amino alcohols as initiators Is mentioned.
[0021]
Examples of the polycarbonate polyol include, for example, a dehydrochlorination reaction of a low-molecular alcohol and phosgene used in the synthesis of the polyester polyol described above, or an ester of the low-molecular alcohol with diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, or the like. Examples include those obtained by an exchange reaction.
[0022]
As the polyether polyol, for example, low-molecular alcohols, low-molecular amines, and low-molecular amino alcohols used in the synthesis of the polyester polyol described above are used as initiators, and ethylene oxide, propylene oxide, and tetrahydrofuran are subjected to ring-opening polymerization. Polyoxyethylene polyols, polyoxypropylene polyols, polytetramethylene ether polyols, polyether polyols obtained by copolymerizing them, and polyester ether polyols using the above-mentioned polyester polyols and polycarbonate polyols as initiators. For the modification of an isocyanate group-containing urethane prepolymer, a polyoxyalkylene monool obtained by ring-opening polymerization of the propylene oxide or the like with a monoalcohol (initiator) such as methyl alcohol, ethyl alcohol, or propyl alcohol is also used. it can.
Of these, polyoxypropylene polyol is particularly preferred.
[0023]
Examples of the polyolefin polyol include hydroxyl group-containing polybutadiene, hydrogenated hydroxyl group-containing polybutadiene, hydroxyl group-containing polyisoprene, hydrogenated hydroxyl group-containing polyisoprene, hydroxyl group-containing chlorinated polypropylene, and hydroxyl group-containing chlorinated polyethylene.
[0024]
Examples of the acrylic polyol include a monomer and / or a hydroxyl group of an acrylic compound having a hydroxyl group such as 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and hydroxypropyl methacrylate. A methacrylic acid-based compound monomer and one or more other ethylenically unsaturated compounds in the presence or absence of a radical polymerization initiator, and in the presence or absence of a solvent in a batch polymerization or Examples thereof include those obtained by reacting by a known radical polymerization method such as continuous polymerization.
[0025]
Animal and plant polyols include, for example, castor oil diols.
[0026]
Further, if it has an active hydrogen group, for example, in addition to dimer acid diol, hydrogenated dimer acid diol, epoxy resin, polyamide resin, polyester resin, rosin resin, urea resin, melamine resin, phenol resin, Resins such as coumarone resin and polyvinyl alcohol can also be used as the polymer polyol.
[0027]
The number average molecular weight of these high molecular polyols is preferably from 500 to 30,000, particularly preferably from 1,000 to 20,000.
[0028]
As the chain extender, low-molecular alcohols, low-molecular amines, low-molecular amino alcohols and the like having a molecular weight of less than 500 used in the synthesis of the polyester polyol, or a mixture of two or more of these are preferable. Is exemplified.
[0029]
For the synthesis of isocyanate group-containing urethane-based prepolymers, such as zinc octenoate, salts of metals such as zinc, tin, lead, zirconium, bismuth, cobalt, manganese and iron with organic acids such as octylic acid and naphthenic acid; Known urethanization catalysts such as salts of organic acids with organic metals such as dibutyltin dilaurate and dioctyltin dilaurate, organic amines such as triethylenediamine, triethylamine and tri-n-butylamine and salts thereof can be used. Of these, dibutyltin dilaurate is preferred. Further, a known organic solvent can also be used.
[0030]
The isocyanate group-containing urethane prepolymer can be synthesized by either a batch charging reaction method or a multi-stage charging reaction method, but it is necessary to leave an isocyanate group in the molecule of the prepolymer. The equivalent ratio of isocyanate group / active hydrogen group of the isocyanate group of the organic polyisocyanate and the polymer polyol, and optionally the active hydrogen group of the chain extender is preferably 1.1 to 5.0, more preferably 1.3 to 2. 0 is preferred. The isocyanate group-containing urethane prepolymer thus obtained preferably has an isocyanate group content of 0.1 to 15.0% by mass, more preferably 0.3 to 10.0% by mass, and most preferably 0.4 to 10.0% by mass. To 5.0% by mass. When the isocyanate group content is less than 0.1% by mass, the molecular weight becomes too large, the viscosity increases, and the workability decreases. Further, since there are few crosslinking points in the resin, sufficient adhesiveness cannot be obtained. When the isocyanate group content exceeds 15.0% by mass, the molecular weight of the resin is too small, rubber elasticity is deteriorated, and foaming due to generation of carbon dioxide gas is caused.
[0031]
The isocyanate group-containing urethane-based prepolymer can be used as a one-part curing type by reacting and curing at room temperature with moisture in the air, and the isocyanate group-containing urethane-based prepolymer is used as a main component and active hydrogen such as polyamine and polyol. It can also be used as a two-part curing type using a compound as a curing agent.
[0032]
Examples of the crosslinkable silyl group-containing resin include those generally called a silicone resin and a modified silicone resin, and react with moisture (water) or polymerize (condensate) with a curing agent to form a siloxane bond. It is a resin containing one or more crosslinkable silyl groups in the molecule, which forms a rubber-like cured product by being crosslinked by being formed. Of these, modified silicone resins containing one or more crosslinkable silyl groups in the molecule are preferred.
[0033]
The silicone resin has an organopolysiloxane in the main chain and contains one or more crosslinkable silyl groups in the molecule.
Specifically, a one-pack type silicone resin containing an organopolysiloxane having a silanol group at a terminal as a main component and a crosslinkable silyl group-containing low molecular weight compound as a crosslinking component, and an organopolysiloxane having a silanol group at a terminal as a main component A typical example is a two-pack type silicone resin containing siloxane and an aminooxyalkylsilane as a curing agent. Examples of the crosslinkable silyl group-containing low molecular weight compound include acyloxyalkylsilane, aminoxyalkylsilane, and alkoxyalkylsilane.
[0034]
Modified silicone resins include, for example, JP-A-52-73998, JP-A-55-9669, JP-A-59-122541, JP-A-60-6747, and JP-A-61-233043. JP-A-63-112642, JP-A-3-79627, JP-A-4-283259, JP-A-5-70531, JP-A-5-287186, and JP-A-11-80571. And Japanese Patent Application Laid-Open Nos. 11-11663 and 11-130931. Specifically, a polyoxyalkylene-based polymer, a vinyl-modified polyoxyalkylene-based polymer, which contains one or more crosslinkable silyl groups in the molecule, and whose main chains may each contain an organosiloxane, Examples include vinyl polymers, diene polymers such as polyisoprene and polybutanediene, polyester polymers, (meth) acrylate-based polymers, polysulfide polymers, copolymers thereof, and mixtures thereof.
The main chain of the modified silicone resin may contain an organosiloxane from the viewpoint of physical properties such as tensile adhesion and modulus after curing, and may be a polyoxyalkylene polymer and / or a vinyl-modified polyoxyalkylene polymer. Are preferable, and a polyoxypropylene-based polymer and a (meth) acryl-modified polyoxypropylene-based polymer which may contain an organosiloxane are more preferable. Here, the modification includes not only modification by copolymerization or reaction, but also blending.
[0035]
It is preferable that 1 to 5 crosslinkable silyl groups are included in the molecule from the viewpoint of the curability of the composition and the physical properties after curing.
Further, the crosslinkable silyl group is preferably a compound represented by the following general formula (1) which is easily crosslinked and easily produced.
[0036]
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(In the formula, 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 group selected from a halogen atom, a hydrogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, a mercapto group, an alkenyloxy group and an aminooxy group. In this case, X may be the same or different groups, wherein X is preferably an alkoxy group, most preferably a methoxy group or an ethoxy group, and a is an integer of 0, 1 or 2. , 0 or 1 is most preferred.)
[0037]
The introduction of the crosslinkable silyl group into the main chain can be performed, for example, by the following known method.
(1) A polyoxyalkylene polymer having a functional group such as a hydroxyl group at the terminal is reacted with an organic compound having an active group and an unsaturated group (e.g., allyl isocyanate) having reactivity with the functional group. The hydrosilylation is carried out by reacting a hydrosilane having a hydrolyzable group on the obtained reaction product.
(2) A polyoxyalkylene polymer having a functional group such as a hydroxyl group, an amino group, an epoxy group, or an isocyanate group at a terminal, and a compound having a functional group having reactivity with the functional group and a crosslinkable silyl group. Let react.
Examples of the compound having the reactive functional group and the crosslinkable silyl group include silanes containing an amino group, silanes containing a mercapto group, silanes containing an epoxy group, silanes containing a vinyl-type unsaturated bond, silanes containing a chlorine atom, and isocyanates. Examples include group-containing silanes and hydrosilanes.
(3) A compound having a polymerizable unsaturated bond and a crosslinkable silyl group (eg, CH₂= CHSi (OCH₃  )₃  ) And an alkyl (meth) acrylate monomer are copolymerized.
(4) A compound having a polymerizable unsaturated bond and a functional group (for example, hydroxyethyl (meth) acrylate) is added to an alkyl (meth) acrylate monomer and copolymerized. Having a reactive functional group and a crosslinkable silyl group (for example, an isocyanate group and -Si (OCH₃)₃  Group-containing compound).
[0038]
Silicone resins and modified silicone resins having a number average molecular weight of 1,000 or more, particularly 6,000 to 30,000, and having a narrow molecular weight distribution are easy to handle because of low viscosity before curing, and have strength, elongation, and modulus after curing. It is preferable because of its excellent physical properties.
The modified silicone resin can be used as a one-part curing type by reacting and curing the crosslinkable silyl group with atmospheric moisture (moisture) at room temperature, or a curing catalyst such as stannic octylate separately as a curing agent And a plasticizer can be used as a two-part curing type in which the mixture is cured by mixing with a modified silicone resin as a main component.
[0039]
The polysulfide resin is a polymer having a polysulfide skeleton and a mercapto group at a terminal.
The polysulfide resin having a mercapto group at the terminal is preferably a resin represented by the general formula: HS- (R'-Sx) y-R "-SH. In the general formula, x is an integer of 1 to 4. And the average value is 1.5 to 2.5. Y is 1 to 120, preferably 6 to 50. In the formula, R ′ and R ″ are divalent aliphatic A hydrocarbon group, specifically -C₂  H₄  -, -C₃  H₆  -, -C₄H₈  And the like, but those having an ether bond are particularly 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 from 200 to 20,000, particularly preferably from 1,000 to 8,000.
Polysulfide resin can be used as a one-part curing type that generates hydrogen peroxide by moisture by exposing a compound containing a metal oxide such as calcium peroxide to the atmosphere, and oxidizes and cures the resin at room temperature. Further, it can also be used as a two-pack curing type in which a polysulfide resin is used as a main component, lead dioxide, polyisocyanate, or the like is used as a curing agent, and these are mixed and cured when used.
[0040]
As the unsaturated polyester resin, an unsaturated polyester resin obtained by esterifying an unsaturated dibasic acid such as maleic anhydride or fumaric acid and a glycol such as propylene glycol, a polymerizable monomer such as a styrene monomer as a reactive diluent; And the like.
By mixing a catalyst mainly composed of an organic peroxide and a metal salt such as cobalt as a curing catalyst, it can also be used as a two-part curing type for radical polymerization and curing at room temperature.
[0041]
As the alkyd resin, a skeleton of an esterified product of a polybasic acid such as phthalic anhydride and a polyhydric alcohol such as glycerin, and a pure alkyd resin obtained by modifying this with a drying oil such as soybean oil, and further rosin and the like And the like. By mixing a curing catalyst for drying such as cobalt naphthenate as a curing agent, it can also be used as a two-part curing type that oxidizes and cures at room temperature.
[0042]
Examples of the epoxy resin include a bisphenol A epoxy resin, a bisphenol F epoxy resin, a bisphenol AD epoxy resin, a bisphenol S epoxy resin, and an epoxy resin obtained by hydrogenating them, a glycidyl ester epoxy resin, and a glycidylamine epoxy resin. Epoxy resin, alicyclic epoxy resin, novolak type epoxy resin, urethane modified epoxy resin with epoxidized urethane prepolymer, fluorinated epoxy resin, rubber modified epoxy resin containing polybutadiene or NBR, glycidyl tetrabromobisphenol A Flame-retardant epoxy resins such as ether and the like can be mentioned.
[0043]
Examples of the curing agent for the epoxy resin include aliphatic amines, alicyclic amines, aromatic amines, polyaminoamides, imidazoles, dicyandiamides, epoxy-modified amines, Mannich-modified amines, Michael addition-modified amines, ketimines, and acid anhydrides. , Alcohols, phenols and the like.
[0044]
Furthermore, an active hydrogen (group) -containing urethane-based prepolymer obtained by reacting an active hydrogen compound such as a polyol with an organic polyisocyanate under an active hydrogen (group) excess condition with respect to an isocyanate group is used as a main component, And a two-component curable resin using a curing agent.
[0045]
In addition, a two-part curable resin which is mainly composed of a fluorine-containing resin having an active hydrogen (group) such as a hydroxyl group and cured at room temperature with a polyisocyanate as a curing agent may also be used.
[0046]
Next, the alkyleneoxy group-containing hydrocarbon group-bonded inorganic substance particles used in the present invention will be described.
The alkyleneoxy group-containing hydrocarbon group-bonded inorganic substance particles are obtained by introducing an alkyleneoxy group-containing hydrocarbon group by a chemical reaction onto the surface of the inorganic substance particles, and the curable composition of the present invention can be used in a small amount. To give strong and stable thixotropic properties to Specifically, for example, those represented by the following general formula (2) are preferred.
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Here, the alkyleneoxy group-containing hydrocarbon group means a portion excluding Y and Z in the formula (2), and the strong hydrogen bond of the alkyleneoxy group and the entanglement of the hydrocarbon group allow a stable thixotropic structure. Is presumed to form.
In the present invention, it is important that the group containing an alkyleneoxy group is a hydrocarbon group, which is a group that does not react with the above-mentioned room temperature curable resin during storage at room temperature. The reason is that if the hydrocarbon group of the alkyleneoxy group-containing hydrocarbon group-bonded inorganic substance particles has a functional group such as an amino group, it is stored at room temperature with a room temperature curable resin such as an isocyanate group-containing urethane prepolymer. This causes the curable composition obtained to break down the thixotropic structure during storage and increase the viscosity.
(2) R in the formula¹As 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl, n-octyl, n-decyl and the like. A monovalent aromatic hydrocarbon group such as a valent aliphatic hydrocarbon group, a phenyl group, a monovalent aromatic hydrocarbon group such as a benzyl group, and a monovalent alicyclic hydrocarbon group such as a cyclohexyl group; And R²Examples thereof include divalent alkylene groups such as an ethylene group having 1 to 5 carbon atoms, a propylene group, a butylene group, and a tetramethylene group.³Examples thereof include a methylene group having 1 to 10 carbon atoms, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, an n-hexylene group, an n-octylene group, and an n-decylene group. Examples thereof include a divalent aliphatic hydrocarbon group, a divalent aromatic hydrocarbon group such as a phenylene group, and a divalent alicyclic hydrocarbon group such as a cyclohexylene group. In terms of the magnitude of the effect, R¹Is preferably a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably a methyl group or an ethyl group.²Is preferably an ethylene group or a propylene group, and an ethylene group is most preferable because of its high polarity. R³Is preferably a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and more preferably an n-propylene group. The number n of the alkyleneoxy groups is 1 to 20, and 2 to 20 polyalkyleneoxy groups are preferable from the viewpoint of the effect of imparting the thixotropic property.
(2) The linking group Y in the formula is composed of the inorganic substance particles Z and the alkyleneoxy group-containing hydrocarbon group R¹-O- (R²O) n-R³And -TiO-, -SiO- and the like (the one linked to the inorganic substance particles Z is represented as -TiO-Z, -SiO-Z), but is easy to produce. -SiO- (siloxane bond) is preferable from the viewpoint of the effect of imparting the thixotropic property.
Further, in order to impart stable thixotropic ability to the inorganic material particles, at least one alkyleneoxy group-containing hydrocarbon group may be bonded to the surface Z of the inorganic material particles by the linking group Y.
In the formula (2), the linking group Y is schematically shown as being connected to the surface Z of the inorganic substance particles by one hand, but if a siloxane bond is taken as an example, -SiO- , -Si (O-)₂, -Si (O-)₃This indicates that it is sufficient that at least one of the hands is connected to the surface Z of the inorganic substance particles by at least one of the hands.
[0047]
Specific examples of the above-mentioned particles of the alkyleneoxy group-containing hydrocarbon group-bonded inorganic material include a crosslinkable silyl group (reactive silyl group) of the alkyleneoxy group-containing hydrocarbon group and the crosslinkable silyl group-containing compound. By reacting the reactive silyl group-reactive functional group-containing inorganic substance particles with each other to form a siloxane bond (—SiO—), a reaction product having an alkyleneoxy group-containing hydrocarbon group introduced to the surface of the inorganic substance particles is formed. It can be suitably mentioned.
As the alkyleneoxy group-containing hydrocarbon group and the crosslinkable silyl group-containing compound, specifically, compounds represented by the following general formula (3) are preferably mentioned.
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[0048]
Specific examples include compounds represented by the following formulas (in each formula, n is an integer of 1 to 20), and these can be used alone or in combination of two or more.
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[0049]
Among these, the following formulas (where n is an integer of 1 to 20), from the viewpoint that the thixotropic effect of the alkyleneoxy group-containing hydrocarbon group-bonded inorganic substance particles obtained by reacting with availability is large. Are preferred, and particularly preferred representative commercial products are A-1230 manufactured by Nippon Unicar and X-12641 manufactured by Shin-Etsu Chemical Co., Ltd.
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[0050]
The crosslinkable silyl group-reactive functional group-containing inorganic material particles have a functional group capable of reacting with the crosslinkable silyl group of the alkyleneoxy group-containing hydrocarbon group and the crosslinkable silyl group-containing compound on the particle surface. Anything can be used. Specifically, such a crosslinkable silyl group-reactive functional group is, for example, bonded to various metal atoms such as Mg-OH, Ca-OH, Ti-OH, Fe-OH, Al-OH, and Si-OH. And a hydroxyl group. Further, if the crosslinkable silyl group-reactive functional group has on the particle surface of the inorganic material, a single inorganic material particle may have the reactive functional group. (E.g., silicon dioxide particles) or other inorganic material particles may be composited by coating or mixing with the inorganic material having a reactive functional group (e.g., the surface of calcium carbonate particles It is also possible that other inorganic substance particles contain an inorganic substance having the reactive functional group as an impurity (for example, calcium carbonate particles). Containing silicon dioxide as).
Here, for example, silicon dioxide (SiO 2)₂In the chemical formulas such as (1) and (2), even if there is no hydroxyl group, the particle surface is reacted by moisture and contains a hydroxyl group. In addition, the metal particles are oxidized on the surface of the particles and then reacted by moisture. When used, the surfaces of the particles contain hydroxyl groups.
In addition, the inorganic material particles include those obtained by processing organic material particles such as carbon (carbon black or the like) or (meth) acrylic polymer particles, and Saran microballoons with the inorganic material, and performing processing such as coating. .
Crosslinkable silyl group-reactive functional group-containing inorganic substance particles may be finely pulverized natural minerals such as limestone, diatomaceous earth and kaolin clay, or may be synthetic products such as precipitated calcium carbonate and dry silica particles. Specifically, for example, metal particles such as titanium, iron, nickel, copper, zinc, and aluminum, titanium oxide, iron oxide, zinc oxide, aluminum oxide, aluminum hydroxide, silicon dioxide (silica), hydrated silica, and the like Metal oxide particles, metal hydroxide particles such as magnesium hydroxide, calcium hydroxide and aluminum hydroxide, calcium carbonate such as heavy calcium carbonate and precipitated calcium carbonate (light calcium carbonate or colloidal calcium carbonate), basic Metal carbonate particles such as magnesium carbonate, calcium silicate such as wollastonite, hydrous calcium silicate Metal silicate particles such as aluminum silicate such as aluminum and kaolin clay; aluminum-potassium silicate such as natural mica; hydrous aluminum silicate; magnesium silicate such as talc; ceramic particles such as zirconia; and various glasses such as potash glass And the like. These can be used alone or in combination of two or more.
Examples of the silicon dioxide (silica) include natural silica obtained by pulverizing quartz, silica sand, diatomaceous earth, and the like, and synthetic silica such as wet silica such as sedimentation silica and dry silica such as fumed silica. .
In addition, the shape of the inorganic substance particles may be any shape, specifically, for example, spheres such as fumed silica, fibrous or acicular such as sepiolite, wollastonite, and flakes such as mica and talc. And various shapes such as flakes such as mica, flakes such as mica, porous such as silica gel, balloons such as silica balloon, and tubing such as diatomaceous earth.
In the present invention, the average (primary) particle diameter (diameter or long diameter) of the inorganic substance particles is 1,000,000 nm (1,000 μm) or less, further 1 to 100,000 nm (100 μm), particularly 1 to 10 nm. 2,000 nm (10 μm) is preferable, and furthermore, the effect of imparting thixotropic properties to the room-temperature-curable resin by the inorganic substance particles obtained by reacting an alkyleneoxy group-containing hydrocarbon group and a crosslinkable silyl group-containing compound on the particle surface. The average (primary) particle diameter of the inorganic substance particles is preferably 1 to 1,000 nm, which is referred to as a colloidal form, more preferably 1 to 100 nm, and particularly preferably 5 to 50 nm. BET specific surface area (m²/ G) is preferably 0.1 or more, more preferably 20 to 500, and particularly preferably 40 to 500.
In the present invention, among the above, metal oxide particles, metal hydroxide particles, metal carbonate particles, and metal silicate particles are preferable, and silicon dioxide particles are more preferable, and particularly, an alkyleneoxy group-containing hydrocarbon group and a crosslink When a reactive silyl group-containing compound is allowed to react, colloidal silica is preferred, and hydrophilic colloidal silica is most preferred, since the effect of imparting thixotropic properties to a room temperature curable resin is large.
Further, the inorganic substance particles may or may not have water of crystallization, but when the composition is a one-part moisture-curable type, in order to improve storage stability, water of crystallization is required. It is preferable not to have.
The inorganic substance particles may be in a powder form, or may be previously dispersed in a liquid medium such as an aqueous medium, an organic solvent such as toluene and xylene, and a plasticizer such as DOP. The powder is more preferable in that the method of use is more flexible.
[0051]
The alkyleneoxy group-containing hydrocarbon group and the crosslinkable silyl group-containing compound are used in an amount of 0.01 to 200 parts by weight, more preferably 1 to 100 parts by weight, based on 100 parts by weight of the crosslinkable silyl group-reactive functional group-containing inorganic substance particles (solid content). It is preferable to react 50 parts by weight. If the amount is less than 0.01 part by weight, it becomes difficult to impart stable thixotropic property to the curable composition, and if the amount exceeds 200 parts by weight, the effect of imparting thixotropic property does not change and the cost becomes high. Therefore, it is not preferable.
[0052]
The alkyleneoxy group-containing hydrocarbon group-bonded inorganic material particles are blended in an amount of 0.1 to 300 parts by weight, more preferably 1 to 100 parts by weight, particularly 5 to 50 parts by weight, based on 100 parts by weight of the room temperature curable resin. preferable. If the amount is less than 0.1 part by weight, the effect of imparting thixotropic properties becomes too small, and if it exceeds 300 parts by weight, workability deteriorates.
[0053]
In the present invention, the method for producing the thixotropic cold-curable composition includes, in the presence of a cold-curable resin, and in the presence or absence of a reaction catalyst and / or an organic dispersion medium, an alkyleneoxy group-containing resin. The hydrocarbon group and the crosslinkable silyl group-containing compound and the crosslinkable silyl group-reactive functional group-containing inorganic material particles are mixed at a temperature of 5 to 200 ° C for 0.1 to 100 hours, preferably at a temperature of 30 to 80 ° C. 0.5 to 10 hours to react and synthesize the alkyleneoxy group-containing hydrocarbon group-bonded inorganic material particles, and at the same time, obtain a thixotropic cold-setting composition. The reaction catalyst and the organic dispersion medium may be used as needed, but the reaction catalyst is preferably used because the reaction temperature can be lowered and the reaction time can be shortened. In addition, additives described later are mixed as needed. At the time of this reaction, the additives described below may not be present, but may be present.
As another method for producing a thixotropic cold-setting composition, the alkyleneoxy group-containing hydrocarbon group and the crosslinkable silyl group-containing compound react with the crosslinkable silyl group-reactive functional group-containing inorganic material particles. In the presence or absence of a catalyst and / or an organic dispersion medium, the reaction is carried out by heating at a temperature of 5 to 200 ° C for 0.1 to 100 hours, preferably at a temperature of 30 to 80 ° C for 0.5 to 10 hours to react. Oxy group-containing hydrocarbon group-bonded inorganic material particles are synthesized in advance, and then the obtained alkyleneoxy group-containing hydrocarbon group-bonded inorganic material particles (when an organic dispersion medium is used, the mixture of the organic dispersion medium and Or an organic dispersion medium separated by volatilization or the like) is added to a room-temperature-curable resin and mixed to obtain a thixotropic room-temperature-curable composition. The reaction catalyst and the organic dispersion medium may be used as needed, but the reaction catalyst is preferably used because the reaction temperature can be reduced and the reaction time can be shortened. . In addition, additives described later are mixed as needed.
In the present invention, a production method in which an alkyleneoxy group-containing hydrocarbon group and a crosslinkable silyl group-containing compound are reacted with a crosslinkable silyl group-reactive functional group-containing inorganic material particle in the presence of the former cold-setting resin or the like. Is particularly preferable because it is easy to manufacture and low in cost.
In addition, the above-mentioned alkyleneoxy group-containing hydrocarbon group-bonded inorganic material particles may be formed of an alkyleneoxy group-containing hydrocarbon group and a cross-linkable inorganic material such as hydrophobic silica whose surface is treated with hydrophilic silica such as trimethylchlorosilane or hexamethylsilazane. It can also be synthesized by reacting the silyl group-containing compound with the remaining small amount of Si—OH group or simultaneously with hydrolysis in the presence of a small amount of water.
The reaction catalyst that is preferably used as necessary is the above-mentioned cross-linkable silyl group reaction (reactive silyl group) of the above-mentioned alkyleneoxy group-containing hydrocarbon group and cross-linkable silyl group-containing compound. A catalyst that promotes the formation of a siloxane bond by reacting with a crosslinkable silyl group-reactive functional group of a functional functional group-containing inorganic material particle, for example, an organometallic compound, an amine, and the like. For example, tin octylate, divalent organic tin compounds such as tin naphthenate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dimaleate, dibutyltin distearate, dioctyltin dilaurate, dioctyltin diversate, dibutyltin Oxide, dibutyltin bis (triethoxysilicate), dibutyltin oxide Tetravalent organotin compounds such as reaction products with tartrate, dibutyltin bis (acetylacetonate), tin-based chelate compounds EXCESTAR C-501 manufactured by Asahi Glass Co., Ltd., zirconium tetrakis (acetylacetonate), titanium tetrakis (acetyl) Acetonate), aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), acetylacetone cobalt, acetylacetone iron, acetylacetone copper, acetylacetone magnesium, acetylacetone bismuth, acetylacetonenickel, acetylacetonenickel, acetylacetonenickel, acetylacetonemanganese, and other chelating compounds. , Lead salts of organic acids such as lead octylate, titanates such as tetra-n-butyl titanate and tetrapropyl titanate, octyl Organic bismuth compounds such as bismuth acid and bismuth versatate; primary amines such as butylamine and octylamine; secondary amines such as dibutylamine and dioctylamine; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine , Primary and secondary amines such as diethylenetriamine and triethylenetetramine, tertiary amines such as triethylamine, tributylamine, triethylenediamine and N-ethylmorpholine, or these amines and carboxylic acids and the like. Salts, kaolin clay, inorganic acidic compounds such as hydrochloric acid, organic phosphoric acid acidic compounds such as ethyl acid phosphate and 2-ethylhexyl acid phosphate, or salts of these with amines, and the like, alone or in combination of two or more. It can be used in conjunction seen. Of these, organotin compounds and metal chelate compounds are preferable because they are liquids having a high reaction rate and relatively low toxicity and volatility, and tin chelate compounds are more preferable, and dibutyltin bis (acetylacetonate) or Asahi Glass EXCESTAR C-501 manufactured by the company is most preferred.
The reaction catalyst is preferably used in an amount of 0 to 10 parts by weight, particularly 0.05 to 5 parts by weight, based on 100 parts by weight of the inorganic material having a crosslinkable silyl group-reactive functional group. As the organic dispersion medium, any organic solvent or plasticizer exemplified as an additive described below that does not react with each component can be used.
The organic dispersion medium is preferably added in an amount of 0 to 3,000 parts by weight, particularly preferably 50 to 2,000 parts by weight, based on 100 parts by weight of the inorganic material having a crosslinkable silyl group-reactive functional group.
[0054]
Examples of the additives in the present invention include a curing catalyst, a weathering stabilizer, a filler, a plasticizer, a coupling agent, an adhesion-imparting agent, a storage stability improving agent (dehydrating agent), a coloring agent, a matting agent, and an organic solvent. No.
[0055]
The curing catalyst is a catalyst for accelerating the curing of the room-temperature curable resin, a curing catalyst for accelerating the curing of the isocyanate group-containing urethane prepolymer and the crosslinkable silyl group-containing resin, a polysulfide resin and an unsaturated polyester resin. (Radical polymerization) curing catalyst for accelerating the curing of alkyd resin, and drying curing catalyst for accelerating the curing of the alkyd resin.
As the curing catalyst for accelerating the curing of the isocyanate group-containing urethane prepolymer and the crosslinkable silyl group-containing resin, specifically, the above-mentioned alkyleneoxy group-containing hydrocarbon group and the crosslinkable silyl group-containing compound are crosslinkable with the above-mentioned compound. The same compounds as those exemplified as the reaction catalyst used as needed in the reaction with the silyl group-reactive functional group-containing inorganic substance particles may be used. Among them, organotin compounds and metal chelate compounds are preferable, tin-based chelate compounds are more preferable, and dibutyltin bis (acetylacetonate) is most preferable because they are liquids having a high reaction rate and low toxicity and volatility. .
Examples of (radical polymerization) curing catalysts for accelerating the curing of polysulfide resins and unsaturated polyester resins include lead dioxide, manganese dioxide, calcium peroxide, zinc peroxide, sodium perborate, paraquinone dioxime, dinitrobenzene, Methyl ethyl ketone peroxide-cobalt soap and the like.
Examples of the curing catalyst for drying 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 0.05 to 2 parts by weight, based on 100 parts by weight of the room temperature curable resin, in view of the curing speed, the physical properties of the cured product, and the like.
[0056]
The weathering stabilizer is used to prevent oxidation, light deterioration, and heat deterioration after curing of the room temperature curable resin, and to further improve not only weather resistance but also heat resistance. Specific examples of the weather resistance stabilizer include an antioxidant, an ultraviolet absorber, and a photocurable compound.
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] butylmalonate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) Sebacate, methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine and the like. In addition, low molecular weight of less than 1,000 such as LA-52, LA-57, LA-62, LA-67, LA-77, LA-82, LA-87 of Adeka stub series manufactured by Asahi Denka Kogyo Co., Ltd. High molecular weight hindered amine antioxidants having a molecular weight of 1,000 or more, such as 119 FL, 2020 FDL, 944 FD, and 944 LD of trade name CHIMASSORB series manufactured by LA-63P, LA-68LD or Ciba Specialty Chemicals Agents and the like.
Hindered phenolic antioxidants include, for example, pentaeristol-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 3,5-bis (1,1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester, 2,4-dimethyl-6- (1-methylpentadecyl) phenol and the like.
Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers such as 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, and 2- (4,6-diphenyl-1,3,3). Triazine-based ultraviolet absorbers such as 5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, benzophenone-based ultraviolet absorbers such as octabenzone, and 2,4-di-tert-butylphenyl-3,5. And benzoate ultraviolet absorbers such as -di-tert-butyl-4-hydroxybenzoate.
Examples of the photocurable compound include a compound containing one or more groups in the molecule that react and cure by light such as an acryloyl group or a methacryloyl group. Specifically, for example, a hydroxyl group-containing acrylate compound is added to an isocyanate group-containing urethane resin. Polyester acrylates and polyester methacrylates such as urethane acrylates and urethane methacrylates, trimethylolpropane triacrylate and trimethylolpropane trimethacrylate, etc. Polyether acrylates and polyether methacrylates such as acrylates and methacrylates of ether polyols; Examples thereof include vinyl cinnamate and azide resin, and preferred are monomers and oligomers having a molecular weight of 10,000 or less, and more preferably a molecular weight of 5,000 or less. In particular, acryloyl groups and / or methacryloyl groups are averaged per molecule. Those containing two or more are preferred.
It is preferable to add 0.01 to 30 parts by weight, particularly 0.1 to 10 parts by weight, of the weather resistance stabilizer to 100 parts by weight of the room temperature curable resin.
[0057]
Fillers, plasticizers, coupling agents, adhesion-imparting agents, storage stability improvers (dehydrating agents), coloring agents, matting agents, etc. are used to reinforce, increase, reduce viscosity, improve adhesion, improve storage stability, It can be used for coloring, matting the surface of a cured product, and the like.
As the filler, for example, mica, kaolin, zeolite, graphite, diatomaceous earth, clay, clay, talc, slate powder, silicic anhydride, quartz fine powder, aluminum powder, zinc powder, synthetic silica such as precipitated silica, calcium carbonate Inorganic powder fillers such as magnesium carbonate, alumina, calcium oxide, magnesium oxide, etc., fibrous fillers such as asbestos, glass fiber, carbon fiber, etc., and inorganic balloons such as glass balloon, shirasu balloon, silica balloon, ceramic balloon etc. Inorganic fillers such as fillers or fillers whose surfaces have been treated with organic substances such as fatty acids, wood flour, walnut flour, rice husk flour, pulp powder, cotton chips, rubber powder, thermoplastic or thermosetting resin Fine powder, polyethylene and other powders and hollow bodies, organic Other organic fillers such as chromatography emissions fillers, also listed and flame retardant fillers such as magnesium hydroxide and aluminum hydroxide, the particle diameter 0.01~1,000μm is preferred.
Specific examples of the plasticizer include phthalic acid esters such as dioctyl phthalate, dibutyl phthalate, and butylbenzyl phthalate; and aliphatic carboxylic acids such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate, and butyl oleate. Etherification of esters, alcohol esters such as pentaerythritol ester, phosphates such as trioctyl phosphate and tricresyl phosphate, chlorinated paraffins, and polyether polyols used in the synthesis of the isocyanate group-containing urethane prepolymer. Or polyoxyalkylenes such as esterified, especially saccharide-based polyethers obtained by etherifying or esterifying a polyether polyol obtained by addition polymerization of ethylene oxide or propylene oxide to a saccharide polyhydric alcohol such as sucrose. Oligomers of polystyrene such as xylene, poly-α-methylstyrene, polystyrene, (meth) acrylic polymers such as poly (meth) acrylic resin, polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene And plasticizers such as olefin polymers such as hydrogenated polybutene.
As the coupling agent, other than the alkyleneoxy group-containing hydrocarbon group and the crosslinkable silyl group-containing compound, various coupling agents such as silane-based, aluminum-based, and zircoaluminate-based compounds and / or partial hydrolysis condensates thereof Is mentioned. Among these, a silane coupling agent and / or a partially hydrolyzed condensate thereof are preferable because of excellent adhesiveness.
Examples of the silane coupling agent include 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, alkoxysilanes having a functional group such as N-phenyl-3-aminopropyltrimethoxysilane and isopropenoxysilanes having a molecular weight of 500 or less, preferably 400 or less. Compounds and / or one or compounds of molecular weight 200 to 3,000 in two or more partial hydrolysis condensate of the silane coupling agent is preferably used.
Examples of the adhesion imparting agent include an epoxy resin, a phenol resin, an alkyd resin, an alkyl titanate, and a polyisocyanate compound.
In the present invention, since the alkyleneoxy group-containing hydrocarbon group-bonded inorganic substance particles have a large thixotropic effect, other thixotropic agents do not need to be used, but they can also be used as an auxiliary for thixotropic imparting. . Examples of such thixotropic agents include inorganic thixotropic agents such as colloidal silica and asbestos powder, and organic thixotropic agents such as organic bentonite, modified polyester polyols, and fatty acid amides.
Examples of the storage stability improver include a low-molecular-weight crosslinkable silyl group-containing compound such as vinyltrimethoxysilane, which reacts with water present in the composition, calcium oxide, p-toluenesulfonyl isocyanate, and the like.
Examples of the coloring agent include inorganic pigments such as titanium oxide and iron oxide, organic pigments such as copper phthalocyanine, and carbon black.
The matting agent, when the thixotropic curable composition of the present invention is used, for example, as a sealing material, reduces the surface gloss after curing, matts the surface, does not make the sealing joints stand out, and reduces the outer wall material. It is possible to prevent the characteristic aesthetics from being impaired, to eliminate surface stickiness after curing, and to prevent contamination due to adhesion of dust and the like. As the matting agent, for example, higher aliphatic compounds such as paraffin wax and stearamide, compounds that react with oxygen in the air represented by drying oils such as tung oil and linseed oil, those exemplified as the filler, A compound having a particle size as large as 100 to 1,000 μm, a compound which reacts with water to form a primary and / or secondary amine having a melting point of 35 ° C. or more, or a primary amine or a secondary amine having a melting point of 35 ° C. or more And secondary amines.
Specific examples of the compound that reacts with water to form a primary and / or secondary amine having a melting point of 35 ° C. or more include primary and secondary compounds having a melting point of 35 ° C. or more, such as stearylamine and distearylamine. And / or a compound obtained by a dehydration reaction between a secondary amine compound and a carbonyl compound such as a ketone compound such as 4-methyl-2-pentanone or an aldehyde compound such as isobutyraldehyde. Examples of the primary amine and the secondary amine having a melting point of 35 ° C. or more include a primary amine such as stearylamine and a secondary amine such as distearylamine.
[0058]
Examples of the organic solvent include conventionally known organic solvents such as an aliphatic solvent such as n-hexane, an alicyclic solvent such as cyclohexane, and an aromatic solvent such as toluene and xylene. Any substance which does not react with the above can be used.
[0059]
The total amount of the filler, plasticizer, coupling agent, adhesion-imparting agent, storage stability improver (dehydrating agent), colorant, matting agent, and organic solvent is based on 100 parts by weight of the room temperature curable resin. The amount is preferably 0 to 500 parts by weight, particularly preferably 10 to 300 parts by weight.
[0060]
In the present invention, the respective additive components can be used alone or in combination of two or more.
[0061]
The thixotropic cold-setting composition of the present invention can be used as a one-part type or a two-part type depending on the application, but there is no need to mix the main agent and the curing agent, and there is also poor mixing due to poor mixing. A one-part thixotropic cold-curable composition is preferable, and a one-part moisture-curable thixotropic cold-setting composition is more preferable.
When used as a two-pack type, the aforementioned alkyleneoxy group-containing hydrocarbon group-bonded inorganic substance particles may be blended with either the base material or the curing agent, or may be blended with both.
[0062]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples and the like.
Here, a sealing material composition is shown as an example of the thixotropic cold-setting composition, but the composition is not limited to this.
[0063]
(Synthesis of isocyanate group-containing urethane prepolymer)
Synthesis Example 1
Under a nitrogen stream, 457.6 g of polyoxypropylene diol (number average molecular weight 3,200, Exenol 3021 manufactured by Asahi Glass Co., Ltd.) and polyoxypropylene were placed in a reaction vessel equipped with a stirrer, a thermometer, and a nitrogen-sealed tube. 291.7 g of triol (number-average molecular weight: 4,000, MN-4000 manufactured by Mitsui Chemicals, Inc.) and 44.7 g of toluene were charged, and 195.4 g of 4,4'-diphenylmethane diisocyanate (Millionate MT manufactured by Nippon Polyurethane Industry Co., Ltd.) was charged with stirring. (R value (NCO equivalent / OH equivalent) = 3.1) and 0.1 g of dibutyltin dilaurate were added, and the mixture was heated and stirred at 70 to 80 ° C. for 2 hours. .49 mass%) or less, the reaction was terminated by cooling to room temperature (actually measured isocyanate group concentration). .38% by mass).
The obtained isocyanate group-containing urethane prepolymer was a liquid having a transparent viscosity of 8,500 mPa · s / 25 ° C. at room temperature.
[0064]
Example 1
In a kneading vessel equipped with a heating and cooling device and a nitrogen sealing tube, 889.0 g of the isocyanate group-containing urethane prepolymer obtained in Synthesis Example 1 and a hydrophilic colloidal silica (Reoloseal QS-102 manufactured by Tokuyama Corporation, BET ratio) were introduced under a nitrogen stream. Surface area 200m²/ G, average primary particle diameter of about 15 nm), 65.0 g of alkyloxy (polyalkyleneoxy) alkyl trialkoxysilane (A-1230 manufactured by Nippon Unicar) and a tin-based chelate catalyst (Asahi Glass Co., Ltd.) 0.9 g of EXCESTARC-501) was stirred and mixed at 60 ° C. for 2 hours, cooled to room temperature, degassed under reduced pressure, filled in a container, and sealed to prepare a sealing material composition.
[0065]
Example 2
A sealing material composition was prepared in the same manner as in Example 1 except that the raw materials were charged and then stirred and mixed at 30 ° C. for 5 hours instead of stirring and mixing at 60 ° C. for 2 hours.
[0066]
Example 3
A sealing material composition was prepared in the same manner as in Example 2, except that 0.9 g of an amine catalyst was further used as a reaction catalyst.
[0067]
Comparative Example 1
A sealing material composition was prepared in the same manner as in Example 1, except that the alkyloxy (polyalkyleneoxy) alkyl trialkoxysilane was not used.
[0068]
Comparative Example 2
A sealing material composition was prepared in the same manner as in Example 2, except that the alkyloxy (polyalkyleneoxy) alkyl trialkoxysilane was not used.
[0069]
Comparative Example 3
A sealing material composition was prepared in the same manner as in Example 3, except that the alkyloxy (polyalkyleneoxy) alkyl trialkoxysilane was not used.
[0070]
Comparative Example 4
A sealing material composition was prepared in the same manner as in Example 1, except that 15.0 g of methyltrimethoxysilane was used instead of 15.0 g of alkyloxy (polyalkyleneoxy) alkyl trialkoxysilane.
[0071]
〔performance test〕
Regarding the sealing material compositions immediately after prepared in Examples 1 to 3 and Comparative Examples 1 to 4, "4.1 Slump test" and "4.19 tack" in JIS A1439: 1997 "Testing method for building sealing materials". Slump (vertical) and tack-free time were measured according to the "free test" (measuring temperature 23 ° C.).
Tables 1 and 2 summarize the results and the composition of the sealing material composition.
[0072]
[Table 1]

[0073]
[Table 2]

[0074]
【The invention's effect】
As described above, the present invention can impart sufficiently stable thixotropic properties to a room-temperature-curable resin. As a result, various compositions can be formed, and low-viscosity, easy-to-disperse and storage-stable. The present invention can provide a thixotropic cold-setting composition excellent in workability and a method for producing the same. Further, according to the present invention, a thixotropic room-temperature curable composition having a high curing rate and excellent internal curability can be provided because a curing catalyst can be used without losing much modification.
That is, the thixotropic room-temperature-curable composition of the present invention has a strong thixotropic property such that it does not drip when applied to a wide vertical joint of a building or the like and does not slip off when a heavy tile or the like is adhered to a wall surface. Can be expressed. Therefore, it is particularly suitable for paints for buildings, civil engineering, automobiles, etc., adhesives, waterproof paints, painted floor materials, putty materials, sealing materials, and the like.

Claims (9)

A thixotropic cold-setting composition, comprising: a cold-setting resin; and an alkyleneoxy group-containing hydrocarbon group-bonded inorganic material particle. The alkyleneoxy group-containing hydrocarbon group-bonded inorganic material particles are a reaction product of an alkyleneoxy group-containing hydrocarbon group and a crosslinkable silyl group-containing compound and a crosslinkable silyl group-reactive functional group-containing inorganic material particle. The thixotropic cold-setting composition according to claim 1. The alkyleneoxy group-containing hydrocarbon group-bonded inorganic material particles are a reaction product of a polyalkyleneoxy group-containing hydrocarbon group and a crosslinkable silyl group-containing compound and a crosslinkable silyl group-reactive functional group-containing inorganic material particle. The thixotropic cold-setting composition according to claim 1. The thixotropic cold-curable composition according to claim 1 or 2, wherein the alkyleneoxy group-containing hydrocarbon group is an alkyleneoxy group-containing hydrocarbon group having no functional group that reacts with a room temperature curable resin at room temperature. object. The crosslinkable silyl group-reactive functional group-containing inorganic substance particles are one or two selected from the group consisting of metal particles, metal oxide particles, metal hydroxide particles, metal carbonate particles and metal silicate particles. The thixotropic cold-curable composition according to claim 2 or 3, which is at least one kind of particles. 4. The thixotropic cold-curable composition according to claim 2, wherein the crosslinkable silyl group-reactive functional group-containing inorganic substance particles are silicon dioxide particles. The thixotropic cold-setting composition according to claim 1 or 4, wherein the cold-setting resin is an isocyanate group-containing urethane prepolymer. The thixotropic cold-setting composition according to any one of claims 1 to 7, further comprising an additive. A method for producing a thixotropic cold-curable composition according to claim 1,
An alkyleneoxy group-containing hydrocarbon group and a crosslinkable silyl group-containing compound, and a crosslinkable silyl group-reactive functional group in the presence of a room-temperature curable resin and in the presence or absence of a reaction catalyst and / or an organic dispersion medium. The method according to claim 1, wherein the method comprises reacting the group-containing inorganic material particles to synthesize alkyleneoxy group-containing hydrocarbon group-bonded inorganic material particles.