JP4195537B2 - Curable composition, coating composition, paint, antifouling paint, cured product thereof, and substrate antifouling method - Google Patents

Description

【００１６】
（式[α]中、Ｗは水酸基または加水分解性基を示し、Ｒ¹、Ｒは、それぞれ独立に炭素数１〜１２の非置換または置換の１価炭化水素基を示し、複数のＲ¹、Ｒは、それぞれ互いに同一でも異なっていてもよく、ｎは５以上の整数を示し、ａは０、１または２を示す。）で示される化合物であることが望ましい。
本発明においては、上記式[α]中のＷが水酸基であり、かつａが２である場合、このような成分（Ａ）と上記成分（Ｂ）とに加えて、さらに、
（Ｃ）式[I]：Ｒ¹ _bＳｉＸ_4-b（式[I]中、Ｒ¹は炭素数１〜８の非置換または置換の１価炭化水素基を示し、Ｘは加水分解性基を示し、ｂは０または１を示す。）で示されるオルガノシランまたはその部分加水分解物を含有することが望ましい。
【００１７】
本発明においては、疎水性シリカは、上記成分（Ａ）と１００℃以上の温度で加熱処理されていることが望ましい。本発明においては、上記成分（Ｂ）を、上記成分（Ａ）１００重量部に対して１〜１００重量部の量で含有することが望ましい。
また、上記成分（Ｃ）を、上記成分（Ａ）１００重量部に対して１〜２０重量部の量で含有することが望ましい。本発明では、さらに、シリコーンオイル（Ｄ）を、上記成分（Ａ）１００重量部に対して、０．１〜２００重量部の量で含有することが望ましい。
【００１８】
本発明では、さらに、触媒、防汚剤および／または着色剤を含むことが望ましい。
本発明に係るコーティング用組成物は、上記何れかに記載の硬化性組成物からなっている。
本発明では、上記コーティング用組成物は、塗料、防汚塗料として好ましく用いられる。
【００１９】
本発明に係る硬化物は、上記何れかに記載された硬化性組成物を硬化させてなる。
本発明に係る塗膜、防汚塗膜は、上記記載の塗料、防汚塗料を塗布・硬化させてなっている。
本発明に係る塗膜付き基材は、基材の表面が、上記のコーティング用組成物を硬化させてなる塗膜で被覆されていることを特徴としており、上記基材としては、電気部品、電子用品、建材、工芸用品、服飾産業用品、医療用品等が例示される。
【００２０】
本発明に係る基材表面への塗膜の形成方法は、上記電気部品などの基材の表面に、上記のコーティング用組成物を塗布あるいは含浸させ、次いで該コーティング用組成物を硬化させ、塗膜を形成させることを特徴としている。
本発明に係る防汚性基材は、海水または真水と接触する基材の表面が、上記防汚塗料を硬化させてなる塗膜にて被覆されていることを特徴としており、上記基材としては、水中構造物、船舶外板、漁網、漁具が好ましい。
【００２１】
本発明に係る基材の防汚方法は、上記水中構造物などの基材の表面に、上記防汚塗料を塗布あるいは含浸させ、次いで該防汚塗料を硬化させ、防汚塗膜を形成させることを特徴としている。
本発明によれば、低粘度、高チクソ性などにバランス良く優れ、一回の塗装で厚膜化が可能であり、しかも得られる硬化塗膜はゴム強度、表面平滑性などにもバランス良く優れているような硬化性組成物が提供される。
【００２２】
また本発明によれば、特にコーティング用組成物、塗料として用いると、スプレー塗装性に優れ、一回の塗装により厚膜化が可能で塗装工期を短縮でき、しかも該塗装により均一膜厚の塗膜が得られ、その上得られた塗膜は、塗膜強度、塗膜硬度に優れ、また特に防汚塗料として用いると、長期間良好な防汚性能が発揮され、さらに塗工前では保存安定性に優れている硬化性組成物が提供される。
【００２３】
このような硬化性組成物は、コーティング用組成物、特に、硬化性塗料組成物、防汚塗料組成物として好適に用いられる。
本発明に係る硬化物、特にコーティング硬化物は表面光沢、ゴム硬度、引張強さ等のゴム物性がバランス良く優れ、また、特に（防汚）塗膜、上記防汚塗膜で基材表面が被覆された水中構造物または船舶外板は、長期防汚性などの特性を有している。
【００２４】
本発明に係る硬化性組成物の製造方法によれば、１回の塗装で垂直に起立した基材表面などに、所望の厚膜塗装が可能であり、塗装効率が高いコーティング材、塗料、特に防汚塗料等の硬化性組成物を製造できる。
本発明に係る基材表面の防汚方法によれば、上記のような優れた特性の塗膜を水中構造物表面など各種基材の表面に、作業者にとって安全で、しかも環境汚染の恐れもなく、効率よく所望の塗膜を形成できる。
【００２５】
【発明の具体的説明】
以下、本発明に係る硬化性組成物、コーティング用組成物、塗料、防汚塗料、その硬化物、並びに基材の防汚方法について具体的に説明する。
＜硬化性組成物＞
本発明に係る硬化性組成物には、（Ａ）分子(鎖状分子あるいは分子主鎖）の両末端に縮合反応性基官能基を有するオルガノポリシロキサンと、
（Ｂ）疎水性シリカとが含有されており、この疎水性シリカ（Ｂ）は上記成分（Ａ）と加熱処理されている。この疎水性シリカ（Ｂ）は、用いられるオルガノポリシロキサン（Ａ）の一部と加熱処理されていてもよく、またオルガノポリシロキサン（Ａ）の全部と加熱処理されていてもよい。
【００２６】
以下、まずオルガノポリシロキサン（Ａ）について説明する。
＜オルガノポリシロキサン（Ａ）＞
上記オルガノポリシロキサン（Ａ）としては、特許第２５２２８５４号に記載されているようなオルガノシリコーンの主成分となる重合体、特に好ましくは液状重合体が用いられ、このようなオルガノポリシロキサン（Ａ）としては、下記式[α]:
【００２７】
【化３】

【００２８】
（式[α]中、Ｗは縮合反応性官能基であり、水酸基（−ＯＨ）または加水分解性基を示し、Ｒ¹、Ｒは、それぞれ独立に炭素数１〜１２の非置換または置換の１価炭化水素基を示し、複数のＲ¹、Ｒは、それぞれ互いに同一でも異なっていてもよく、ｎは５以上の整数を示し、ａは０、１または２を示す。）
で表されるものが望ましい。
【００２９】
この式[α]において、ａ＝０、１である場合には、縮合反応性官能基のＷは加水分解性基であり、ａ＝２である場合には、Ｗは水酸基（−ＯＨ）であることが望ましい。
本発明においては、上記式[α]中のＷが水酸基であり、かつａが２である場合には、このような成分（Ａ）と、上記成分（Ｂ）とに加えて、さらに、後述するような（Ｃ）式[I]：Ｒ¹ _bＳｉＸ_4-b（式[I]中、Ｒ¹は炭素数１〜８の非置換または置換の１価炭化水素基を示し、Ｘは加水分解性基を示し、ｂは０または１を示す。）で示されるオルガノシランまたはその部分加水分解物が含有されていることが好ましい。
【００３０】
以下、上記式[α]で表される上記オルガノポリシロキサン（Ａ）について初めに説明する。
上記式[α]中のｗが加水分解性基である場合、このような加水分解性基としては、例えば、アルコキシ基、アシロキシ基、アルケニルオキシ基、イミノキシ基、アミノ基、アミド基、アミノオキシ基等が挙げられ、アルコキシ基が好ましい。
【００３１】
上記アルコキシ基としては、総炭素数が１〜１０のものが望ましく、また炭素原子間に１箇所以上酸素原子が介在していてもよく、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、メトキシエトキシ基、エトキシエトキシ基等が挙げられる。
アシロキシ基としては、式：ＲＣＯＯ-（式中、Ｒは炭素数１〜１０のアルキル基、炭素数６〜１２の芳香族基）で示される脂肪族系または芳香族系のものが望ましく、例えば、アセトキシ基、プロピオノキシ基、ブチロキシ基、ベンゾイルオキシ基等が挙げられる。
【００３２】
アルケニルオキシ基としては、炭素数３〜１０程度のものが望ましく、例えば、イソプロペニルオキシ基、イソブテニルオキシ基、１−エチル−２−メチルビニルオキシ基等が挙げられる。
ケトオキシム基としては、炭素数３〜１０程度のものが望ましく、例えば、ジメチルケトオキシム基、メチルエチルケトオキシム基、ジエチルケトオキシム基、シクロペンタノキシム基、シクロヘキサノキシム基等が挙げられる。
【００３３】
アミノ基としては、炭素数１〜１０のものが望ましく、例えば、Ｎ−メチルアミノ基、Ｎ−エチルアミノ基、Ｎ−プロピルアミノ基、Ｎ−ブチルアミノ基、Ｎ，Ｎ−ジメチルアミノ基、Ｎ，Ｎ−ジエチルアミノ基、シクロヘキシルアミノ基等が挙げられる。
アミド基としては、総炭素数２〜１０のものが望ましく、例えば、Ｎ−メチルアセトアミド基、Ｎ−エチルアセトアミド基、Ｎ−メチルベンズアミド基等が挙げられる。
【００３４】
アミノオキシ基としては、総炭素数２〜１０のものが望ましく、例えば、Ｎ，Ｎ−ジメチルアミノオキシ基、Ｎ，Ｎ−ジエチルアミノオキシ基等が挙げられる。
Ｒ¹、Ｒは、それぞれ独立に、炭素数が１〜１２、さらに好ましくは１〜１０、特に好ましくは１〜８の非置換または置換の１価炭化水素基を示し、このような１価炭化水素基としては、例えば、アルキル基、アルケニル基、アリール基、シクロアルキル基、アラルキル基等が挙げられる。
【００３５】
上記アルキル基としては、直鎖状、分岐状または脂環状の何れタイプのアルキル基であってもよく、その炭素数が１〜１０、好ましくは１〜８程度の直鎖状または分岐状アルキル基が好ましい。
このような直鎖状あるいは分岐状のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、２−エチルブチル基、オクチル基等アルキル基、特に好ましくはメチル基が挙げられる。
【００３６】
アルケニル基としては、炭素数が２〜１０、好ましくは２〜８程度のものが望ましく、例えば、ビニル基、ヘキセニル基、アリル基等が挙げられる。
アリール基としては、炭素数が６〜１５、好ましくは６〜１２程度のものが望ましく、例えば、フェニル基、トリル基、キシリル基、ナフチル基、ジフェニル基等が挙げられ、特にフェニル基が好ましい。
【００３７】
シクロアルキル基としては、炭素数３〜８のものが望ましく、例えば、シクロヘキシル基、シクロペンチル基等が挙げられる。
アラルキル基としては、総炭素数が７〜１０、好ましくは７〜８程度のものが望ましく、例えば、ベンジル基、２−フェニルエチル基等が挙げられる。
これらの基Ｒ¹中の炭素原子に結合した水素原子の一部あるいは全部は、Ｆ、Ｃｌ、Ｂｒ、Ｉ等のハロゲン原子、シアノ基等で置換されていてもよく、ハロゲン化アルキル基としては、例えば、クロロメチル基、３，３，３−トリフルオロプロピル基、２−シアノエチル基等が挙げられる。
【００３８】
なお、Ｒとしては、なかでも未置換の１価炭化水素基が好ましく、特にメチル基、フェニル基が好ましい。
なお、このような式[α]で表されるオルガノポリシロキサン（Ａ）中に、複数個のＲ¹、複数個のＲが存在する場合、これら複数個のＲ¹同士、複数個のＲ同士、あるいはＲ¹とＲとは、互いに同一でも異なっていてもよい。
【００３９】
このようなオルガノポリシロキサン（Ａ）の２５℃における粘度は、用いられる硬化性組成物の用途によっても異なり一概に決定されないが、得られる組成物の塗装性、得られる組成物を溶剤希釈した時のタレ防止などの観点を考慮すると、通常、２５ｃＳ〜１，５００，０００ｃＳ（１５０万ｃＳ）、好ましくは２５〜５００，０００ｃＳ、さらに好ましくは５００〜２００，０００ｃＳ、特に好ましくは１，０００〜１００，０００ｃＳであることが望ましい。
【００４０】
＜疎水性シリカ（Ｂ）＞
疎水性シリカには、疎水性湿式シリカ、疎水性フュームドシリカ等がある。
本発明では、シリカ成分（Ｂ）として、上記のようにオルガノポリシロキサンＡ）と加熱処理された疎水性シリカが用いられる。本発明に係る硬化性組成物には、オルガノポリシロキサン（Ａ）と共に、該成分（Ａ）と加熱処理された疎水性シリカ（Ｂ）が含まれているため、得られる硬化性組成物をコーティング材（コーティング用組成物）、塗料、特に防汚塗料等に用いると、調製・保管・貯蔵時の安定性に優れ、十分なチクソ性を有し、一回の塗装で厚膜化可能であり、得られる塗膜は、硬さ、引張強さ、伸び等のゴム物性にバランス良く優れ、しかも、防汚塗膜として用いると防汚性などにも優れている。
【００４１】
本発明で用いられるシリカ成分は、後で詳述するように、疎水性シリカを、上記成分（Ａ）の一部または全部と熱処理したものである。
なお、シリカには、湿式法シリカ、乾式法シリカなどの親水性シリカと、疎水性シリカとがあり、これらシリカのうちで、親水性シリカの１種である湿式法シリカは、通常、吸着水分含量（水分含量とも言う。）が４〜８％程度であり、嵩密度は２００〜３００ｇ／Ｌであり、１次粒子径は１０〜３０ｍμであり、比表面積（ＢＥＴ表面積）は、１０ｍ²／ｇ以上であればよいが、好ましくは５０〜８００ｍ²／ｇ、さらに好ましくは１００〜３００ｍ²／ｇ程度である。
【００４２】
乾式法シリカ（フュームドシリカ）は、水分含量が通常、１．５％以下である。なお、この乾式法シリカは、製造直後など初期の水分含量は例えば、０．３％以下と低いが、放置しておくと次第に吸湿して水分含量が増加し、製造後数ヶ月経過後の時点では、例えば、０．５〜１．０％程度になる。またこのような乾式法シリカの嵩密度はその種類により異なり一概に決定されないが、例えば、５０〜１００ｇ／Ｌであり、１次粒子径は８〜２０ｍμであり、比表面積（ＢＥＴ表面積）は、１０ｍ²／ｇ以上であればよいが、好ましくは１００〜４００ｍ²／ｇ、さらに好ましくは１８０〜３００ｍ²／ｇ程度である。
【００４３】
疎水性シリカは、これらの親水性シリカをメチルトリクロロシラン、ジメチルジクロロシラン、ヘキサメチルジシラザン、ヘキサメチルシクロトリシロキサン、オクタメチルシクロテトラシロキサン等の有機珪素化合物で表面処理したものである。この中でも疎水性フュームドシリカが好ましく、疎水性フュームドシリカは、経時的な水分吸着は少なく、水分含量は通常０．３％以下、多くの場合０．１〜０．２％であり、比表面積は１０ｍ²／ｇ以上であればよいが、好ましくは１００〜３００ｍ²／ｇ、さらに好ましくは１２０〜２３０ｍ²／ｇであり、１次粒子径は５〜５０ｍμであり、嵩密度は５０〜１００ｇ／Ｌである。
【００４４】
なお、成分（Ａ）と共に熱処理された疎水性フュームドシリカ（熱処理疎水性ヒュームドシリカ）では、疎水性シリカの表面に吸着されている水分が物理的に低減・除去されており、水分含量が通常、０．２％以下、好ましくは０．１％以下、特に０．０５〜０．１％であり、嵩密度等のその他の物性値は、上記疎水性シリカと同様である。
【００４５】
このような成分（Ｂ）は、上記成分（Ａ）１００重量部に対し、通常、１〜１００重量部、好ましくは２〜５０重量部、特に好ましくは５〜３０重量部の量で本発明の硬化性組成物中に含有されていることが望ましい。
このような量でシリカ成分（Ｂ）が硬化性組成物中に含まれていると、塗膜強度、塗膜硬度に優れ、チクソ性が良好で、適度の粘度を有し、良好に塗装特にスプレー塗装でき、例えば、垂直に起立した基材面等であっても１回の塗装で塗膜の厚膜化を図ることができるため好ましい。
【００４６】
なお、上記成分（Ｂ）が上記範囲より少ないと、十分な塗膜強度、塗膜硬度が得られず、所望のチクソ性が得られず１回の塗装特にスプレー塗装で所望の厚膜化が図れないことがあり、また、上記成分（Ｂ）が上記範囲より多いと塗料の粘度が過度に高くなり、塗装に適した適正粘度までシンナーなどの溶剤で希釈する必要が生じ、１回のスプレー塗装による厚膜化が図れないことがある。
【００４７】
＜オルガノシランまたはその部分加水分解物（Ｃ）＞
本発明においては、前記成分（Ａ）が前記式[α]で表され、式[α]中のＷが水酸基であり、かつａが２である場合には、このような成分（Ａ）と、上記成分（Ｂ）とに加えて、さらに、
（Ｃ）式[I]：Ｒ¹ _bＳｉＸ_4-b（式[I]中、Ｒ¹は炭素数１〜８の非置換または置換の前記式[α]中のＲ、Ｒ¹等と同様の１価炭化水素基を示し、Ｘは前記式[α]中のＷと同様の加水分解性基を示し、ｂは０または１を示す。）で示されるオルガノシランまたはその部分加水分解物が含有されていることが好ましい。
【００４８】
すなわち、本発明においては、上記成分（Ａ）として、その分子（鎖状分子、分子鎖）の両末端が水酸基（−ＯＨ）であるオルガノポリシロキサン、具体的には、分子鎖両末端がシラノール基（≡Ｓｉ−ＯＨ）で封鎖された硬化性オルガノポリシロキサンを用いる場合には、このような成分（Ａ）と架橋剤・硬化剤などとしての成分（Ｃ）とを併用することが特に好ましい。また例えば、上記成分（Ａ）として、その分子両末端が加水分解性基で封鎖された硬化性オルガノポリシロキサンを用いる場合には、硬化剤成分（Ｃ）が存在しなくとも充分に硬化可能であるが、このような場合にも成分（Ｃ）を含むことがより好ましい。
【００４９】
上記Ｘは、前記式[I]におけるＷと同様の加水分解性基である。
このような式[I]で表されるオルガノシランまたはその（部分）加水分解物としては、具体的には、例えば、メチルトリメトキシシラン、メチルトリ（メチルエチルケトオキシム）シラン、メチルトリプロペニルオキシシラン、メチルトリアセトキシシラン及びこれらのシラン化合物のメチル基をビニル基、フェニル基、トリフルオロプロピル基等で置換したシラン化合物、さらにはこれらの部分加水分解物が挙げられる。この場合加水分解性基としてはケトオキシム基が好ましい。
【００５０】
これらのオルガノシランまたはその加水分解物（Ｃ）は、上記オルガノポリシロキサン（Ａ）１００重量部に対して、１〜６０重量部の量で使用可能であるが、通常、１〜２０重量部の量で、好ましくは２〜１０重量部の量で本発明の硬化性組成物中に含まれていることが望ましい。
このような量でオルガノシランまたはその加水分解物（Ｃ）が上記組成物中に含まれていると、成分（Ａ）の架橋反応が良好に進行し、得られた塗膜は、適度の硬度を有し、経済性に優れる傾向がある。
【００５１】
＜シリコーンオイル（Ｄ）＞
本発明に係る硬化性組成物は、シリコーンオイル（Ｄ）を含んでいてもよく、このようなシリコーンオイル（Ｄ）としては、非反応性（非縮合性）のシリコーンオイルや硬化性組成物の硬化物中からブリードアウトしていくシリコーンオイルなら特に制限されないが、好ましくは（Ａ）成分と異なる（Ｄ）成分、さらには下記式[II]、[IV]で示されるシリコーンオイル、下記式[III]で示され基を有するようなシリコーンオイルが好ましい。
【００５２】
このようなシリコーンオイル（Ｄ）のうちでシリコーンオイル[II]、[IV]は、前記成分（Ａ）などとの反応性や自己縮合性を示さず、塗膜表面（層）に防汚機能層（膜）を形成する働きを有していると考えられ、またシリコーンオイル[III]は、塗膜形成成分となる成分（Ａ）などと反応し、硬化塗膜を形成し、長期間海水に浸漬されていると経時的に加水分解され、末端基がアルコール性水酸基を有する基「≡ＳｉＲ⁴ＯＨ」等となって塗膜表面にブリードアウトし、海中生物付着防止効果を発揮するのであろうと考えられる。
【００５３】
（Ｒ²）₃ＳｉＯ（ＳｉＲ³ ₂Ｏ）_nＳｉ（Ｒ²）₃ ・・・・・[II]
（式[II]中、複数個のＲ²は互いに同一または異なってもよく、炭素数１〜１０のアルキル基、アリール基、アラルキル基またはフルオロアルキル基を示し、複数個のＲ³は互いに同一または異なってもよく、各Ｒ³は、炭素数１〜１０のアルキル基、アリール基、アラルキル基またはフルオロアルキル基を示し、ｎは０〜１５０の数を示す。）
≡ＳｉＲ⁴ＯＳｉＲ⁵ _bＹ_3-b ・・・・・[III]
（式[III]中、Ｒ⁴は非置換または置換の２価炭化水素基またはエーテル結合を含む２価炭化水素基を表し、Ｒ⁵は非置換または置換の１価炭化水素基、Ｙは加水分解性基、ｂは０，１または２である。）
Ｒ⁶ _xＳｉ（Ｒ⁷−Ｚ）_yＯ_(4-x-y)/2 ・・・・・[IV]
（式[IV]中、Ｒ⁶は、水素原子、それぞれ炭素数１〜１０のアルキル基、アリール基またはアラルキル基を示し、Ｒ⁷は、エーテル基、エステル基または−ＮＨ−が介在していてもよい炭素数１〜１０の２価脂肪族炭化水素基を示し、Ｚは、アミノ基、カルボキシル基、エポキシ基または末端が炭素数１〜６のアルキル基もしくはアシル基で封鎖されていてもよいポリエチレングリコールまたはポリプロピレングリコール基である１価の極性基を示し、ｘ、ｙは、それぞれ０．０１≦ｘ＜３．９９、０．０２≦ｙ＜４であり、かつ、０．０２≦ｘ＋ｙ＜４を示す。）。
【００５４】
上記シリコーンオイル（Ｄ）のうち、シリコーンオイル[II]としては、特開平１０−３１６９３３号公報に記載されているようなものが使用でき、数平均分子量が１８０〜２０，０００好ましくは１，０００〜１０，０００であり、粘度が２０〜３０，０００センチストークス好ましくは５０〜３，０００センチストークスであるものが望ましい。
【００５５】
このようなシリコーンオイル[II]としては、例えば、Ｒ²、Ｒ³の全てがメチル基であるジメチルシリコーンオイル、これらのジメチルシリコーンオイルのメチル基の一部がフェニル基に置換されたフェニルメチルシリコーンオイルが挙げられ、なかでもメチルフェニルシリコーンオイルが好ましい。
このようなメチルフェニルシリコーンオイルとしては、具体的には、例えば、「ＫＦ−５４、ＫＦ−５６、ＫＦ−５０」（信越化学工業社製品）、「ＳＨ５１０、ＳＨ５５０」（東レダウコーニングシリコーン社製）、「ＴＳＦ４３１、ＴＳＦ４３３」（東芝シリコーン社製）等の商品名で上市されているものが挙げられる。
【００５６】
また、上記式[III]で示され基を有するシリコーンオイル（シリコーンオイル[III]）としては、本願出願人らの提案した特許第２５２２８５４号公報に記載されているものが使用でき、数平均分子量が２５０〜２０，０００好ましくは１，０００〜１０，０００であり、粘度が２０〜３０，０００センチストークス、好ましくは５０〜３０００センチストークスのものが望ましい。
【００５７】
≡ＳｉＲ⁴ＯＳｉＲ⁵ _bＹ_3-b ・・・・・[III]
（式[III]中、Ｒ⁴は非置換または置換の２価炭化水素基またはエーテル結合を含む２価炭化水素基を表し、Ｒ⁵は非置換または置換の１価炭化水素基、Ｙは加水分解性基、ｂは０，１または２である。）
上記Ｒ⁴としては、具体的には、例えば、メチレン基、エチレン基、プロピレン基、ブチレン基、ヘキサメチレン基等のような非置換または置換の２価炭化水素基；または、
「−（ＣＨ₂）_p−Ｏ−（ＣＨ₂）_q−」（式中、ｐ、ｑはそれぞれ独立に１〜６の整数を示す。）等で示されるエーテル結合を含む２価炭化水素基；
等が挙げられる。
【００５８】
Ｒ⁵としては、上記成分（Ｃ）の式[I]におけるＲ¹と同様に、炭素数１〜８の非置換または置換の１価炭化水素基を示す。Ｙは、上記成分（Ｃ）の式[I]における加水分解性基Ｘと同様の基を示す。
このような式[III]で示される基を少なくとも１個有するシリコーンオイル[III]としては、具体的には、例えば、上記特許第２５２２８５４号公報に記載されているような、
（ＣＨ₃）₃ＳｉＯ［（ＣＨ₃）₂ＳｉＯ］_m［Ｒ⁷Ｒ⁸ＳｉＯ］_n（ＣＨ₃）₂ＳｉＣ₃Ｈ₆−ＯＨ、
ＨＯ−Ｃ₃Ｈ₆−［（ＣＨ₃）₂ＳｉＯ］［（ＣＨ₃）₂ＳｉＯ］_m［Ｒ⁷Ｒ⁸ＳｉＯ］_n−（ＣＨ₃）₂Ｓｉ−Ｃ₃Ｈ₆−ＯＨ、
（ＣＨ₃）₃ＳｉＯ［（ＣＨ₃）₂ＳｉＯ］_m［Ｒ⁷Ｒ⁸ＳｉＯ］_n［（ＣＨ₃）（Ｃ₃Ｈ₆−ＯＨ）ＳｉＯ］_l［（ＣＨ₃）₂ＳｉＣＨ₃］、
で表されるシリコーンオイルの水酸基を加水分解基で封鎖したもの等が挙げられる。但し、上記各式中、Ｒ⁷、Ｒ⁸としては、フェニル基、トリル基等のアリール基；ベンジル基、β−フェニルエチル基等のアラルキル基；トリフルオロプロピル基等のハロゲン化アルキル基；等のように、Ｒ⁷、Ｒ⁸のうち少なくとも一方がメチル基以外の基から選択される非置換または置換の１価炭化水素基が挙げられる。ｍ、ｎ、ｌは何れも正数を示す。
【００５９】
また、得られる組成物の保存安定性の点から、下記に例示するように、上記のシリコーンオイルを、式：「Ｒ⁵ _bＳｉＹ_3-b」（Ｒ⁵、Ｙ、ｂは式[III]の場合と同様。）で示されるオルガノシランと反応させたものでもよい。
（ＣＨ₃）₃ＳｉＯ［（ＣＨ₃）₂ＳｉＯ］_m［Ｒ⁷Ｒ⁸ＳｉＯ］_n（ＣＨ₃）₂ＳｉＣ₃Ｈ₆−Ｏ−Ｒ⁵ _bＳｉＹ_3-b、
ＨＯ−Ｃ₃Ｈ₆−［（ＣＨ₃）₂ＳｉＯ］［（ＣＨ₃）₂ＳｉＯ］_m［Ｒ⁷Ｒ⁸ＳｉＯ］_n−（ＣＨ₃）₂Ｓｉ−Ｃ₃Ｈ₆−Ｏ−Ｒ⁵ _bＳｉＹ_3-b、
（ＣＨ₃）₃ＳｉＯ［（ＣＨ₃）₂ＳｉＯ］_m［Ｒ⁷Ｒ⁸ＳｉＯ］_n［（ＣＨ₃）（Ｃ₃Ｈ₆−Ｏ−Ｒ⁵ _bＳｉＹ_3-b）ＳｉＯ］_l［（ＣＨ₃）₂ＳｉＣＨ₃］など。
【００６０】
シリコーンオイル［ＩＶ］としては、具体的には、特開平１０−３１６９３３号公報に記載されているようなものが使用でき、数平均分子量が２５０〜３０，０００好ましくは１，０００〜２０，０００であり、粘度が２０〜３０，０００センチストークス好ましくは５０〜３，０００センチストークスであるものが望ましい。
【００６１】
Ｒ⁶ _xＳｉ（Ｒ⁷−Ｚ）_yＯ_(4-x-y)/2 ・・・・・[IV]
（式[IV]中、Ｒ⁶は、水素原子、それぞれ炭素数１〜１０のアルキル基、アリール基またはアラルキル基を示し、Ｒ⁷は、エーテル基、エステル基または−ＮＨ−が介在していてもよい炭素数１〜１０の２価脂肪族炭化水素基を示し、Ｚは、アミノ基、カルボキシル基、エポキシ基または末端が炭素数１〜６のアルキル基もしくはアシル基で封鎖されていてもよいポリエチレングリコールまたはポリプロピレングリコール基である１価の極性基を示し、ｘ、ｙは、それぞれ０．０１≦ｘ＜３．９９、０．０２≦ｙ＜４であり、かつ、０．０２≦ｘ＋ｙ＜４を示す。）。
【００６２】
このようなシリコーンオイル[IV]としては、好ましくは、上記式[IV]において、Ｒ⁶が、メチル基またはフェニル基であり、Ｒ⁷が、メチレン基、エチレン基またはプロピレン基であるものが望ましい。またＺとしては、末端が炭素数６以下のアルキル基もしくはアシル基で封鎖されていてもよいポリエチレングリコールまたはポリプロピレングリコール基である場合、繰り返し単位としてのオキシエチレン、オキシプロピレンの数は１０〜６０が好ましい。また、末端封鎖用の上記アルキル基としては、メチル基、エチル基、プロピル基、ブチル基等が挙げられ、末端封鎖用の上記アシル基としては、ケトオキシム基、アセチル基、プロピオニル基等が挙げられる。
【００６３】
具体的には、極性基Ｚがアミノ基であるシリコーンオイルとしては、「ＳＦ８４１７」（東レダウコーニング社製）、「ＩＳＩ４７００、ＩＳＩ４７０１」（東芝シリコーン社製）、「ＦＺ３７１２、ＡＦＬ−４０」（日本ユニカー社製）等が挙げられる。極性基Ｚがカルボキシル基であるシリコーンオイルとしては、「ＸＩ４２−４１１」（東芝シリコーン社製）、「ＳＦ８４１８」（東レダウコーニングシリコーン社製）、「ＦＸＺ４７０７」（日本ユニカー社製）等が挙げられる。また極性基がエポキシ基であるシリコーンオイルとしては、「ＳＦ８４１１」（東レダウコーニングシリコーン社製）、「ＸＩ４２−３０１」（東芝シリコーン社製）、「Ｌ−９３，Ｔ−２９」（日本ユニカー社製）等が挙げられる。極性基Ｚがアルキル基またはアシル基であるシリコーンオイルとしては、「ＩＳＩ４４６０，ＩＳＩ４４４５、ＩＳＩ４４４６」（東芝シリコーン社製）、「ＳＨ３７４６、ＳＨ８４００、ＳＨ３７４９、ＳＨ３７００」（東レダウコーニングシリコーン社製）、「ＫＦ６００９」（信越シリコーン社製）等が挙げられる。
【００６４】
本発明においては、このようなシリコーンオイル（Ｄ）好ましくは、シリコーンオイル[II]、シリコーンオイル[III]及びシリコーンオイル[IV]のうちの何れか１種または２種以上が、上記成分（Ａ）１００重量部に対して、合計で、０．１〜２００重量部、好ましくは２０〜１００重量部の量で含有されていることが望ましい。
【００６５】
このシリコーンオイル（Ｄ）量が上記範囲にあると、例えば、防汚塗料として用いる場合に、防汚性、塗膜強度共に優れた（防汚）塗膜が得られる傾向があり、上記範囲より少ないと防汚性が低下し、また上記範囲を超えて多いと塗膜強度が低下することがある。
［硬化性組成物の製造］
このような本発明に係る硬化性組成物、特に、コーティング用組成物、硬化性塗料組成物および防汚塗料組成物は、予め、成分（Ａ）の一部または全部と、疎水性シリカとを、常圧下または減圧下に、１００℃以上で配合成分の分解温度以下、好ましくは１００〜３００℃、さらに好ましくは１４０℃〜２００℃程度の温度で、通常３０分〜３時間程度加熱処理した後、残部の成分（Ａ）と、必要により用いられる成分（Ｃ）とに加えて、必要によりさらに成分（Ｄ）を配合することによって製造することができる。また、従来より公知のオルガノシロキサン硬化触媒、防汚剤、チクソトロピー性付与剤、可塑剤、無機脱水剤（安定剤）、タレ止め・沈降防止剤（増粘剤）、着色顔料、染料、その他の塗膜形成成分、溶剤（例：キシレン）、殺菌剤、防カビ剤、老化防止剤、酸化防止剤、帯電防止剤、難燃剤、熱伝導改良剤、接着性付与剤などとを所定の割合で一度にあるいは任意の順序で加えて撹拌・混合し、溶媒に溶解・分散することもできる。
【００６６】
このように疎水性シリカを、成分（Ａ）と加熱処理すると、得られる組成物中の成分（Ａ）と成分（Ｂ）とは親和性に優れ、成分（Ｂ）などの充填剤成分の凝集がなく、例えば、得られるコーティング用組成物、例えば、防汚塗料組成物は適度の流動性、チクソ性等を示し、垂直塗装面などに対しても、所望の充分な厚みの塗膜を１回塗りなどの少ない塗装回数で形成できる。
【００６７】
なお、上記のような配合成分の攪拌・混合の際には、ロスミキサー、プラネタリーミキサー、万能品川攪拌機など、従来より公知の混合・攪拌装置が適宜用いられる。
上記触媒としては、例えば、特許第２５２２８５４号公報に記載されているものを好適に使用でき、具体的には、例えば、ナフテン酸錫、オレイン酸錫等のカルボン酸錫類；
ジブチル錫ジアセテート、ジブチル錫ジオクトエート、ジブチル錫ジラウレート、ジブチル錫ジオレート、ジブチル錫オキサイド、ジブチル錫ジメトキシド、ジブチルビス（トリエトキシシロキシ）錫等の錫化合物類；
テトライソプロポキシチタン、テトラｎ-ブトキシチタン、テトラキス（２−エチルヘキソキシ）チタン、ジプロポキシビス（アセチルアセトナト）チタン、チタニウムイソプロポキシオクチルグリコール等のチタン酸エステル類あるいはチタンキレート化合物；
等の他、
ナフテン酸亜鉛、ステアリン酸亜鉛、亜鉛−２−エチルオクトエート、鉄−２−エチルヘキソエート、コバルト−２−エチルヘキソエート、マンガン−２−エチルヘキソエート、ナフテン酸コバルト、アルコキシアルミニウム化合物等の有機金属化合物類；
３−アミノプロピルトリメトキシシラン、Ｎ−β（アモノエチル）γ−アモノプロピルトリメトキシシラン等のアミノアルキル基置換アルコキシシラン類；
ヘキシルアミン、リン酸ドデシルドデシルアミン、ジメチルヒドロキシルアミン、ジエチルヒドロキシルアミン等のアミン化合物及びその塩類；
ベンジルトリエチルアンモニウムアセテート等の第４級アンモニウム塩；
酢酸カリウム、酢酸ナトリウム、臭酸リチウム等のアルカリ金属の低級脂肪酸塩類；
テトラメチルグアニジルプロピルトリメトキシシラン、テトラメチルグアニジルプロピルメチルジメトキシシラン、テトラメチルグアニジルプロピルトリス（トリメチルシロキシ）シラン等のグアニジル基を含有するシラン又はシロキサン類；
等が挙げられる。
【００６８】
これらの触媒は、成分（Ａ）１００重量部に対して、１０重量部以下、好ましくは５重量部以下、さらには１重量部以下の量で用いられ、該触媒を使用する場合の好ましい下限値は０．００１重量部以上、特に０．０１重量部以上である。
＜任意成分＞
上記のように本発明に係る硬化性組成物が、例えば、コーティング用組成物、特に塗料組成物あるいは防汚塗料組成物、なかでも硬化性防汚塗料組成物（防汚塗料）として用いられる場合には、上記成分（Ａ）、（Ｂ）および、必要により用いられる成分（Ｃ）に加えて、必要により、さらに、以下に詳述するような防汚剤、可塑剤、無機脱水剤、カルボン酸金属塩、タレ止め・沈降防止剤（搖変剤）、顔料、その他の塗膜形成成分、その他の充填剤、難燃剤、チクソトロピー性付与剤、熱伝導改良剤、溶剤、防カビ剤、抗菌剤、艶消し剤、香料などの各種成分が含まれていてもよい。
【００６９】
＜防汚剤＞
防汚剤としては、無機系、有機系の何れであってもよく、無機系防汚剤としては、従来より公知のものを使用できるが、中でも銅、無機銅化合物が好ましい。
有機防汚剤
有機防汚剤としては、下記式(vi)で示される金属−ピリチオン類［式中Ｒ¹〜Ｒ⁴は、それぞれ独立に水素、アルキル基、アルコキシ基、ハロゲン化アルキル基を示し、Ｍは、Ｃu、Ｚｎ、Ｎａ、Ｍｇ、Ｃａ、Ｂａ、Ｐｂ、Ｆｅ、Ａｌ等の金属を示し、ｎは価数を示す］：
【００７０】
【化４】

【００７１】
、テトラメチルチウラムジサルファイド、カーバメート系の化合物（例：ジンクジメチルジチオカーバメート、マンガン-２-エチレンビスジチオカーバメート）、２，４，５，６−テトラクロロイソフタロニトリル、Ｎ，Ｎ−ジメチルジクロロフェニル尿素、４，５−ジクロロ-２-ｎ-オクチル-３（２Ｈ）イソチアゾリン、２，４，６−トリクロロフェニルマレイミド、２−メチルチオ−４−ｔ−ブチルアミノ−６−シクロプロピルＳトリアジン等を挙げることができる。
【００７２】
上記有機防汚剤のうちでは、銅ピリチオン（式(vi)中、Ｍ＝Ｃu）、ジンクピリチオン（式(vi)中、Ｍ＝Ｚｎ）、Ｎ，Ｎ−ジメチルジクロロフェニル尿素、２，４，６−トリクロロフェニルマレイミド、２−メチルチオ−４−ｔ−ブチルアミノ−６−シクロプロピルＳトリアジン、４，５−ジクロロ-２-ｎ-オクチル-４−イソチアゾリン−３−オン、２，４，５，６−テトラクロロイソフタロニトリルが好ましい。
【００７３】
これらの有機防汚剤の内では、金属ピリチオン類および／または４，５−ジクロロ−２−ｎ−オクチル−４−イソチゾリン−３−オンが好ましく、さらにはこれらを併用すると防汚性能が優れるので好ましく、特に銅ピリチオンおよび／または４，５−ジクロロ−２−ｎ−オクチル−４−イソチアゾリン−３−オンを用いることが好ましく、これらを併用することが一層好ましい。
【００７４】
このような有機防汚剤を含む防汚塗料組成物においては、例えば、銅および／または無機銅化合物以外に、上記有機防汚剤が通常、０．１〜２０重量％、好ましくは０．５〜１０重量％の量で含まれていることが望ましい。また塗料組成物中に含まれる固形分１００重量部に対して、該有機防汚剤は、固形分として、通常、０．１〜１５０重量部、好ましくは０．１〜１００重量部の量で含まれていることが望ましい。
【００７５】
＜可塑剤（塩素化パラフィン）＞
可塑剤としては、ＴＣＰ（トリクレジルフォスフェート）、塩素化パラフィン、ポリビニルエチルエーテル等が挙げられる。これらの可塑剤は、１種または２種以上組み合わせて用いることができる。
これらの可塑剤は、得られる防汚塗料組成物からなる塗膜（「防汚塗膜」とも言う。）の耐クラック性の向上に寄与する。
【００７６】
＜無機脱水剤＞
無機脱水剤は、安定剤としても機能し、防汚塗料組成物の貯蔵安定性を一層向上させることができ、このような無機脱水剤としては、無水石膏（ＣａＳＯ₄）、合成ゼオライト系吸着剤（商品名：モレキュラーシーブ等）、シリケート類等が挙げられ、無水石膏、モレキュラーシーブが好ましく用いられる。このような無機脱水剤は、１種または２種以上組み合わせて用いることができる。
【００７７】
このような無機脱水剤を含む硬化性塗料組成物においては、この無機脱水剤は、本発明の非錫系塗料組成物中に、通常、０．１〜１０重量％、好ましくは０．１〜５重量％程度の量で含まれていてもよい。
＜カルボン酸金属塩＞
なお、本発明に係る硬化性塗料組成物には、さらに、カルボン酸金属塩が含まれていてもよい。
【００７８】
カルボン酸金属塩としては、その分子量が通常５０〜１０００、好ましくは１００〜６００のものが用いられる。
このようなカルボン酸金属塩を構成するカルボン酸としては、脂環構造を有するカルボン酸（例：ナフテン酸）、芳香環構造を有するカルボン酸（例：α-（２-カルボキシフェノキシ）ステアリン酸）、ロジン系樹脂酸、脂肪酸等が挙げられ、ナフテン酸、ロジン系樹脂酸、脂肪酸が好ましい。
【００７９】
＜タレ止め・沈降防止剤（搖変剤）＞
タレ止め・沈降防止剤（搖変剤）としては、有機粘土系Ａｌ、Ｃａ、Ｚｎのステアレート塩、レシチン塩、アルキルスルホン酸塩などの塩類、ポリエチレンワックス、アマイドワックス、水添ヒマシ油ワックス系、ポリアマイドワックス系および両者の混合物、合成微粉シリカ、酸化ポリエチレン系ワックス等が挙げられ、好ましくは、ポリアマイドワックス、合成微粉シリカ、酸化ポリエチレン系ワックス、有機粘土系が用いられる。このようなタレ止め・沈降防止剤としては、楠本化成（株）製の「ディスパロン305」、「ディスパロン4200-20」等の他、「ディスパロンA630-20X」等の商品名で上市されているものが挙げられる。
【００８０】
このようなタレ止め・沈降防止剤は、この硬化性塗料組成物中に、例えば、０．１〜１０重量％の量で配合される。
＜顔料＞
顔料としては、従来公知の有機系、無機系の各種顔料を用いることができる。
有機系顔料としては、カーボンブラック、フタロシアニンブルー、紺青等が挙げられる。無機系顔料としては、例えば、チタン白、ベンガラ、バライト粉、シリカ、タンカル、タルク、白亜、酸化鉄粉等のように中性で非反応性のもの；亜鉛華（ＺｎＯ、酸化亜鉛）、鉛白、鉛丹、亜鉛末、亜酸化鉛粉等のように塩基性で塗料中の酸性物質と反応性のもの（活性顔料）等が挙げられる。なお、染料等の各種着色剤も含まれていてもよい。このような各種顔料は、硬化性組成物、特に硬化性塗料組成物中に、例えば、合計で０．５〜４５重量％程度の量で配合される。
【００８１】
＜その他の塗膜形成成分＞
塗膜形成成分としては、上記したオルガノポリシロキサン（Ａ）など以外の塗膜形成成分が本発明の目的に反しない範囲で含まれていてもよく、このような「その他の塗膜形成成分」としては、例えば、アクリル樹脂、アクリルシリコーン樹脂、不飽和ポリエステル樹脂、フッ素樹脂、ポリブテン樹脂、シリコーンゴム、ウレタン樹脂（ゴム）、ポリアミド樹脂、塩化ビニル系共重合樹脂、塩化ゴム（樹脂）、塩素化オレフィン樹脂、スチレン・ブタジエン共重合樹脂、エチレン-酢酸ビニル共重合樹脂、塩化ビニル樹脂、アルキッド樹脂、クマロン樹脂、トリアルキルシリルアクリレート（共）重合体（シリル系樹脂）、石油樹脂等の難あるいは非水溶性樹脂（以下、難／非水溶性樹脂ともいう）が挙げられる。
【００８２】
＜その他の充填剤、難燃剤、チクソトロピー性付与剤、熱伝導改良剤、接着成分など＞
上記した以外の充填剤としては、けいそう土、酸化鉄、酸化亜鉛、酸化チタン、アルミナ等の金属酸化物あるいはこれらの表面をシラン化合物で表面処理したもの；
炭酸カルシウム、炭酸マグネシウム、炭酸亜鉛等の金属炭酸塩；
その他、アスベスト、ガラス繊維、カーボンブラック、石英粉、水酸化アルミ、金粉、銀粉、表面処理炭酸カルシウム、ガラスバルーン等が挙げられる。これらの充填剤は、１種または２種以上併用してもよい。
【００８３】
チクソトロピー性付与剤としては、ポリエチレングリコール、ポリプロピレングリコール及びこれらの誘導体等が挙げられる。
難燃剤としては、酸化アンチモン、酸化パラフィンなどが挙げられる。
熱伝導改良剤としては、窒化ホウ素、酸化アルミニウム等が挙げられる。
接着成分としては、アルコキシシリル基、エポキシ基、ヒドロシリル基、（メタ）アクリル基等の基を１種または２種以上含有するシランカップリング剤等の物質あるいはこれらの物質の混合物が挙げられる。
【００８４】
＜溶剤＞
本発明の硬化性塗料組成物等の硬化性組成物には、溶剤が含まれていてもよく、また含まれていなくともよいが、上記のような各種成分は、必要に応じて、溶剤に溶解若しくは分散して用いることができる。ここで使用される溶剤としては、例えば、脂肪族系、芳香族系、ケトン系、エステル系、エーテル系、アルコール系など、通常、防汚塗料に配合されるような各種溶剤が用いられる。上記芳香族系溶剤としては、例えば、キシレン、トルエン等が挙げられ、ケトン系溶剤としては、例えば、ＭＩＢＫ、シクロヘキサノン等が挙げられ、エーテル系溶剤としては、例えば、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート（ＰＭＡＣ）等が挙げられ、アルコール系溶剤としては、例えば、イソプロピルアルコール等が挙げられる。
【００８５】
このような溶剤は、任意の量で使用可能であるが、上記成分（Ａ）１００重量部に対して例えば、０．１〜９９９９重量部の量で、好ましくは１〜５０重量部の量で用いられる。また、本発明の硬化性組成物中に１〜９９重量％、好ましくは５〜５０重量％となるような量で用いられる。
このような溶剤にて必要により希釈された硬化性塗料組成物等の硬化性組成物の粘度（２５℃、Ｂ型粘度計、３号ローター）は、塗工性（タレ性）、１回塗りで得られる膜厚などを考慮すると、例えば、０．０１〜５００ポイズ／２５℃、好ましくは０．１〜２００ポイズ／２５℃程度である。換言すれば、０．００１〜５０Ｐａ・ｓ、好ましくは０．０１〜２０Ｐａ・ｓ程度である。
【００８６】
本発明の硬化性組成物は、電気部品、電子部品、建材、工芸用品、服飾産業用品、医療用品などの各種基材の表面被覆用のコーティング材（コーティング用組成物）として、また、海水または真水と接触する基材、例えば、水中構造物、船舶外板、漁網、漁具等の基材の表面防汚用の防汚塗料として好適に用いられる。その他、着氷防止塗料、撥水剤などとしても用いられる。このように本発明の硬化性組成物は、電気・電子、建材・工芸、服飾産業、医療、農林・水産業、発電、港湾・土木建設、造船あるいは船舶の修理特に船舶塗装などの広範な産業分野で用いられる。
【００８７】
特に、上記硬化性組成物をコーティング用組成物として、電気部品、電子用品、建材、工芸用品、服飾産業用品、医療用品などの基材表面に塗布・硬化させる場合、該組成物は低粘度と高チクソ性の両者のバランスが優れ、従って、一回の塗装で厚膜化が可能で塗装作業性が良好であり、このような組成物の塗布硬化により例えば、難燃性、ゴム強度、表面平滑性等に優れた塗膜付きの基材が得られる。
【００８８】
特に、上記のような硬化性組成物を塗料、特に防汚塗料（防汚塗料組成物）として、例えば、火力・原子力発電所の給排水口等の水中構造物、海水利用機器類（例：海水ポンプなど）、メガフロート、湾岸道路、海底トンネル、港湾設備、運河・水路等のような各種海洋土木工事の汚泥拡散防止膜、船舶特に船舶外板、漁業資材（例：ロープ、漁網、浮き子、ブイ）などの各種成形体の表面に、常法に従って１回〜複数回塗布、硬化すれば防汚性に優れ、防汚剤成分が長期間に亘って徐放可能であり、厚塗りしても適度の可撓性を有し耐クラック性に優れた防汚塗膜被覆船舶または水中構造物などの防汚性基材が得られる。このような塗装の際には、刷毛、ロール、スプレー、ディップコーター等、従来より公知の塗装手段が広く用いられる。
【００８９】
このような本発明に係る硬化性防汚塗料組成物を各種成形体（基材）の表面に塗布硬化してなる防汚塗膜は、アオサ、フジツボ、アオノリ、セルプラ、カキ、フサコケムシ等の水棲生物の付着を長期間継続的に防止できるなど防汚性に優れている。
特に、該硬化性防汚塗料組成物は、原子力発電所の給排水口、メガフロート、船舶等の素材が、ＦＲＰ、鋼鉄、木、アルミニウム合金などである場合にもこれらの基材（素材）表面に良好に付着する。また、該硬化性防汚塗料組成物は、既存の防汚塗膜表面に上塗してもよい。
【００９０】
また例えば、該硬化性防汚塗料組成物を海中構造物表面に塗布・硬化させれば、海中生物の付着防止を図ることができ、該構造物の機能を長期間維持でき、漁網に塗布すれば、漁網の網目の閉塞を防止でき、しかも環境汚染の恐れが少ない。
なお、この本発明に係る硬化性防汚塗料組成物は、直接漁網に塗布してもよく、また予め防錆剤、プライマーなどの下地材が塗布された船舶または水中構造物等の表面に塗布してもよい。さらには、既に従来の防汚塗料による塗装が行われ、あるいは本発明発明の硬化性防汚塗料組成物による塗装が行われている船舶、特にＦＲＰ船あるいは水中構造物等の表面に、補修用として本発明の硬化性防汚塗料組成物を上塗りしてもよい。このようにして船舶、水中構造物等の表面に形成された防汚塗膜の厚さは特に限定されないが、例えば、３０〜１５０μｍ／回程度である。
【００９１】
上記のようにして得られる本発明に係る防汚塗膜、あるいは船舶・水中構造物の接水部表面の塗膜は、前述したような硬化性防汚塗料組成物から形成されており環境汚染の虞が少なく広汎な船舶・水中構造物付着生物に対して長期防汚性に優れている。
【００９２】
【発明の効果】
本発明に係る硬化性組成物を、コーティング用組成物、特に塗料、防汚塗料組成物などとして用いると、低粘度と高チクソ性とをバランス良く発揮し、ノズルの詰まりや乱れがないなどスプレー塗装性に優れ、一回の塗装による厚膜化が可能で塗装工期を短縮でき、しかも該塗装により塗膜表面の均一性（膜厚の均一性あるいは表面平滑性）に優れた塗膜などの硬化物が得られ、その上得られた塗膜は、塗膜強度（ゴム強度）、塗膜硬度にも優れ、また防汚塗料として用いると、得られる塗膜は長期間優れた防汚性能を発揮でき、また塗工前には保存安定性に優れており、従ってコーティング用組成物特に、硬化性塗料組成物、防汚塗料組成物などとして好適な硬化性組成物が提供される。
【００９３】
また、本発明によれば、上記のように塗膜強度、塗膜硬度にも優れ、長期間優れた防汚性能が発揮されるような塗膜、コーティング硬化物等の各種硬化物、特に防汚塗膜、並びに該塗膜で被覆され、これら特性を備えた水中構造物、船舶外板などが提供される。
さらに本発明によれば、上記のような優れた特性を有する塗膜を水中構造物表面など各種基材の表面に、作業者にとって安全で、しかも環境汚染の恐れもなく、効率よく塗膜形成できるような、電子部品などの基材表面への塗膜の形成方法及び、水中構造物などの基材表面の防汚方法を提供することができる。
【００９４】
【実施例】
以下、本発明について実施例、比較例によりさらに具体的に説明するが、本発明は係る実施例、比較例により何等限定されるものではない。
なお、以下の合成例、実施例、比較例中に記載の組成値等は、重量部表示である。
（シリコーンオイル（Ｄ）の合成）
【００９５】
【合成例１】
下記式：
【００９６】
【化５】

【００９７】
で示されるアルコール性水酸基を含むオルガノポリシロキサン１９３ｇと、メチルトリ（メチルエチルケトオキシム）シラン６０ｇとを室温で混合して反応させ、 式：
【００９８】
【化６】

【００９９】
で示されるシリコーンオイル（Ｄ）を得た。このシリコーンオイルは、未反応原料のメチルトリ（メチルエチルケトオキシム）シランを含んでいた。
【０１００】
【オルガノポリシロキサン塗料組成物（Ａ）〜（Ｈ）の調製】
表１に記載された、分子両末端がシラノール基で封鎖されており、その粘度が２００００ｃｓｔ（２万ｃｓｔ）のジメチルポリシロキサンに、ヘキサメチルジシラザンで表面処理された疎水性ヒュームドシリカを１５０℃で２時間混合攪拌し熱処理したもの（※２参照）、表１に記載された同疎水性シリカをこれと同様にオルガノポリシロキサンに室温で混合攪拌したもの（※３参照）、及び表１に記載された親水性シリカをオルガノポリシロキサンと１５０℃で２時間混合攪拌し、熱処理したもの（※４参照）を、表１に示す配合量で配合し攪拌装置で均一になるよう十分混合し分散させた。さらに架橋剤および触媒を表１に示す配合量で添加し均一に混合して、（Ａ）〜（Ｈ）で示すような組成を有する硬化性オルガノポリシロキサン系塗料組成物を得た。
【０１０１】
これらの性状値、塗膜物性を表１に示す。なお表１中の※１，２，３，４および試験方法は下記の通りである。
また、表中、各種シリカは、塗料組成物中の総オルガノポリシロキサン（Ａ）１００重量部に対するシリカの量（重量部）である。
※１：オルガノポリシロキサン：信越化学工業社製、
化学式：「ＨＯ（ＣＨ₃・ＣＨ₃・ＳｉＯ）_mＨ」（２５℃における粘度 ２００００ｃｓ）
※２：熱処理疎水性ヒュームドシリカ：
表１に記載された疎水性ヒュームドシリカと上記オルガノポリシロキサンとを１５０℃で２時間混合攪拌により加熱処理したシリカ（信越化学工業社製、シリカの水分含量０．０５％、嵩密度５０ｇ／Ｌ、１次粒子径１０ｍμ、比表面積（ＢＥＴ表面積）１８０ｍ²／ｇ）である。
※３：疎水性ヒュームドシリカ：
表１に記載された疎水性ヒュームドシリカと上記オルガノポリシロキサンとを２時間、室温で混合攪拌したシリカ（信越化学工業社製、水分含量０．２％、嵩密度５０ｇ／Ｌ、１次粒子径１０ｍμ、比表面積（ＢＥＴ表面積）１８０ｍ²／ｇ）である。
※４：（表面）未処理シリカ：
表１に記載された未処理シリカと上記オルガノポリシロキサンとを１５０℃で、２時間混合攪拌したシリカ（信越化学工業社製、水分含量１．０％、嵩密度６０ｇ／Ｌ、１次粒子径１２ｍμ、比表面積（ＢＥＴ表面積）１９０ｍ²／ｇ）である。
【０１０２】
［試験方法］
(イ)粘度：
粘度は、表１で得られたオルガノポリシロキサン塗料組成物の粘度（Ｐａ・ｓ／２５℃）をＢ型粘度計（３号ローター）にて測定して求めた。
（ロ）塗膜物性：
塗膜物性は、各オルガノポリシロキサン塗料組成物（Ａ）〜（Ｈ）をステンレス板上に塗布し、２５℃、５５％ＲＨで７日間放置し硬化させて厚さ２ｍｍの塗膜を作成して調べた。
【０１０３】
表１に結果を示す。
【０１０４】
【表１】

【０１０５】
【実施例１〜４および比較例１〜４】
表１で得られた各オルガノポリシロキサン塗料組成物（Ａ）〜（Ｈ）１００重量部に、表２に示す配合組成でシリコーンオイル、キシレンを添加混合し均一になるまで攪拌して、各防汚塗料組成物を得た。
各防汚塗料についての性状値および塗装作業性を調べた。
【０１０６】
結果を表２に示す。
さらに調製直後の各防汚塗料について防汚試験を行った。
結果を表３に示す。
なお、表２中の※７，８，９，１０および試験方法は下記の通りである。また、各種シリコーンオイル量などの（カッコ）書きは、オルガノポリシロキサン（Ａ）１００重量部に対する配合量（重量部）である。
※７：「ＳＨ５５０」：メチルフェニルシリコーンオイル、粘度：１３０センチストークス、東レダウコーニングシリコーン社製。
※８：「ＴＳＦ４３１」：メチルフェニルシリコーンオイル、粘度：１００センチストークス、東芝シリコーン社製。
※９：「ＫＦ５０」：メチルフェニルシリコーンオイル、粘度：１００センチストークス、信越化学工業社製。
※１０：「ＫＦ６０１６」：ポリエーテル変性シリコーンオイル、粘度：１５０センチストークス、信越化学工業社製。
【０１０７】
【表２】

【０１０８】
【表３】

【０１０９】
［試験方法］
(イ)塗料性状値：
塗料性状値は、実施例（Ａ）などの場合と同様にして測定した。
塗装作業性、防汚試験は下記の通りである。
(ロ)塗装作業性：
大きさ１０００ｍｍ×１０００ｍｍ×１ｍｍ（厚）のブリキ板中央に、７０ｍｍ×１５０ｍｍ×１ｍｍ（厚）の軟鋼板を貼り付け、ブリキ板を垂直に立て掛けた状態でエアレススプレー塗装を行い、スプレー時の器具のツマリの有無の確認および膜のタレが生じる限界膜厚を塗膜乾燥後測定した。
(ハ)防汚試験：
１００ｍｍ×３００ｍｍ×５ｍｍ（厚）の塩ビ板にエポキシ系下塗塗料を２００μｍ厚で塗装し、この塗膜上に各防汚塗料を乾燥膜厚が１５０μｍになるよう刷毛塗りし、３日間乾燥した後、宮島湾にて３０ヶ月静置浸漬を行い目視観察にて防汚性評価を行った。
(ニ)塗料安定性、塗装作業性の評価：
また、各防汚塗料を調製後、５０℃、３ヶ月経過後の塗料状態（安定性）および塗装作業性について試験を行った。
【０１１０】
結果を前記表２に併せて示す。
(ホ)防汚試験：
さらに防汚塗料を調製後、５０℃、３ヶ月経過後の防汚塗料について防汚試験を行った。
結果を表４に示す。
【０１１１】
試験方法は下記の通りである。
［試験方法］
塗料状態（安定性）：
表２に示す各防汚塗料を缶の中に入れ、密閉した状態で３ヶ月間、５０℃恒温器内に放置し、開缶後塗料を入念に攪拌しツブゲージにて検査した。
【０１１２】
【表４】

【０１１３】
【実施例５】
１分子中に５モル％のジフェニルシロキシ単位（−Ｐｈ₂ＳｉＯ−，Ｐｈ：フェニル基）を有する、分子鎖（分子）両末端が水酸基で封鎖された、２５℃での粘度が２０，０００ｃＳのジメチルポリシロキサン５０重量部、表面をヘキサメチルジシラザンで処理したＢＥＴ比表面積１３０ｍ²／ｇの疎水性フュームドシリカ２０重量部を、１５０℃にて２時間攪拌混合した。その後、１分子中に５モル％のジフェニルシロキシ基を有する、分子両末端が水酸基で封鎖された２５℃での粘度が２０，０００ｃＳのジメチルポリシロキサン５０重量部で希釈し、メチルトリブタノキシムシラン１０重量部、ジブチルスズジオクトエート０．１重量部、アミノプロピルトリメトキシシラン１．０重量部を脱泡混合した。この組成物へ更に４０重量部のキシレンを添加し、２８ｍＰａ・ｓの硬化性シリコーン溶液とした。これを塗装用ロールにてアルミ製壁面に塗装したところ、４００ミクロンの塗膜厚みを得ることができた。この組成物を２３℃／５５％ＲＨ／７日の条件で硬化させたところ、表面に光沢を有し、透明性良好で、デュロメーター・タイプＡの硬度：５８、引っ張り強さ４．５ＭＰａの良好なゴム物性を有するコーティング硬化物が得られた。
【０１１４】
【比較例５】
１分子中に５モル％のジフェニルシロキシ単位を有する、分子鎖両末端が水酸基で封鎖された、２５℃での粘度が２０，０００ｃＳのジメチルポリシロキサン５０重量部、ＢＥＴ比表面積２００ｍ²／ｇのフュームドシリカ２０重量部を、１５０℃にて２時間攪拌混合した。その後、１分子中に５モル％のジフェニルシロキシ基を有する、分子鎖両末端が水酸基で封鎖された２５℃での粘度が２０，０００ｃＳのジメチルポリシロキサン５０重量部で希釈し、メチルトリブタノキシムシラン１０重量部、ジブチルスズジオクトエート０．１重量部、アミノプロピルトリメトキシシラン１．０重量部を脱泡混合した。この組成物へ更に４０重量部のキシレンを添加し１３ｍＰａ・ｓの硬化性シリコーン溶液とした。これを塗装用ロールにてアルミ製壁面に塗装したところ、１００ミクロンの塗膜厚みを得るのが限界であり、それ以上の厚みを得ようとするとタレが発生してしまった。
【０１１５】
【実施例６】
分子鎖両末端が水酸基で封鎖された２５℃での粘度が２０，０００ｃＳ（２万ｃＳ）のジメチルポリシロキサン５０重量部、表面をヘキサメチルジシラザンで処理したＢＥＴ比表面積１３０ｍ²／ｇの疎水性フュームドシリカ１０重量部を、１５０℃にて２時間攪拌混合した。その後、分子鎖両末端が水酸基で封鎖された２５℃での粘度が２０，０００ｃＳ（２万ｃＳ）のジメチルポリシロキサン５０重量部で希釈し、メチルトリブタノキシムシラン１０重量部、ジブチルスズジオクトエート０．１重量部、アミノプロピルトリメトキシシラン１．０重量部を脱泡混合し、２０重量部のメチルエチルケトンを添加して粘度調整し、粘度４５ｍＰａ・ｓの硬化性シリコーン組成物を得た。この組成物を電子基板の上にディスペンサーにてコーティングし、２３℃／５５％ＲＨ／７日の条件で硬化させたところ、基板上に非常に外観が良好なシリコーン膜が形成された。この膜は、デュロメーター・タイプＡの硬度：３５、引っ張り強さ２．７ＭＰａの良好なゴム物性を有していた。
【０１１６】
【比較例６】
分子鎖両末端が水酸基で封鎖された２５℃での粘度が２０，０００ｃＳ（２万ｃＳ）のジメチルポリシロキサン５０重量部、表面をジメチルジクロロシランで処理したＢＥＴ比表面積１３０ｍ²／ｇの疎水性フュームドシリカ１５重量部を室温にて混合した。
【０１１７】
その後、分子鎖両末端が水酸基で封鎖された２５℃での粘度が２０，０００ｃＳのジメチルポリシロキサン５０重量部で希釈し、メチルトリブタノキシムシラン１０重量部、ジブチルスズジオクトエート０．１重量部、アミノプロピルトリメトキシシラン１．０重量部を脱泡混合し、２０重量部のメチルエチルケトンを添加して粘度調整し、粘度８０ｍＰａ・ｓの硬化性シリコーン組成物を得た。
【０１１８】
この組成物を電子基板の上にディスペンサーにてコーティングしたが、ノズルからの吐出性に劣り、２３℃／５５％ＲＨ／７日の条件で硬化させたところ、基板上には乳濁した表面艶消しのシリコーン膜が形成された。
【０１１９】
【実施例７】
分子鎖両末端が水酸基で封鎖された２５℃での粘度が５，０００ｃＳのジメチルポリシロキサン５０重量部、表面をヘキサメチルジシラザンで処理したＢＥＴ比表面積１３０ｍ²／ｇの疎水性フュームドシリカ１０重量部を、１５０℃にて２時間攪拌混合した。その後、分子鎖両末端が水酸基で封鎖された２５℃での粘度が５，０００ｃＳのジメチルポリシロキサン５０重量部で希釈し、次いで炭酸亜鉛２．０重量部、ビニルトリブタノキシムシラン１０重量部、アミノプロピルトリメトキシシラン１．５重量部、また白金触媒を白金原子の濃度が３００ｐｐｍになるように混合し、粘度１５ｍＰａ・ｓの硬化性シリコーン組成物を得た。ガラスファイバーにこの組成物をディプコートし、２３℃／５５％ＲＨ／７日の条件で硬化させたところ、約１ｍｍのほぼ均一な膜厚の良好な難燃コート膜が得られた。
【０１２０】
【比較例７】
分子鎖両末端が水酸基で封鎖された２５℃での粘度が５，０００ｃＳのジメチルポリシロキサン５０重量部、ＢＥＴ比表面積２００ｍ²／ｇのフュームドシリカ１０重量部を１５０℃にて２時間攪拌混合した。その後、分子鎖両末端が水酸基で封鎖された、２５℃での粘度が５，０００ｃＳのジメチルポリシロキサン５０重量部で希釈し、次いで炭酸亜鉛２．０重量部、ビニルトリブタノキシムシラン１０重量部、アミノプロピルトリメトキシシラン１．５重量部、また白金触媒を白金原子の濃度が３００ｐｐｍになるように混合し、粘度４Ｐａ・ｓの硬化性シリコーン組成物を得た。ガラスファイバーにこの組成物をディップコートし、２３℃／５５％ＲＨ／７日の条件で硬化させたところ、硬化中にタレやしずくが生じ、均一な膜厚の難燃硬化物は得られなかった。
【０１２１】
【実施例８】
分子鎖両末端が水酸基で封鎖された２５℃での粘度が１，０００，０００ｃＳのジメチルポリシロキサン１００重量部、表面をジメチルジクロロシランで処理したＢＥＴ比表面積１３０ｍ²／ｇの疎水性フュームドシリカ４５重量部、分子鎖両末端が水酸基で封鎖された平均重合度１３ジメチルポリシロキサン１０重量部を、１５０℃にて２時間攪拌混合した。この組成物へさらにビニルトリブタノキシムシラン１０重量部、アミノプロピルトリメトキシシラン１．５重量部、キシレン６５重量部を添加したところ、ＢＬ回転粘度計での粘度が４回転では１００Ｐａ・ｓ、２０回転では１５Ｐａ・ｓと、高いチクソ性を示す組成物が得られた。この組成物を２３℃／５５％ＲＨ／７日で硬化させると、透明性良好で、デュロメーター・タイプＡの硬度：６５、引っ張り強さ６．５ＭＰａの良好なゴム物性を有するコーティング硬化物が得られた。
【０１２２】
【比較例８】
分子鎖両末端が水酸基で封鎖された２５℃での粘度が１，０００，０００ｃＳのジメチルポリシロキサン１００重量部、ＢＥＴ比表面積２００ｍ²／ｇのフュームドシリカ４５重量部、分子鎖両末端が水酸基で封鎖された平均重合度１３のジメチルポリシロキサン１０重量部を、１５０℃にて２時間攪拌混合した。この組成物へ更にビニルトリブタノキシムシラン１０重量部、アミノプロピルトリメトキシシラン１．５重量部、キシレン６５重量部を添加したところ、ＢＬ回転粘度計での粘度が４回転では１２Ｐａ・ｓ、２０回転では９Ｐａ・ｓと、かなりチクソ性が低かった。
【０１２３】
【比較例９】
分子鎖両末端が水酸基で封鎖された２５℃での粘度が１，０００，０００ｃＳのジメチルポリシロキサン１００重量部、表面をジメチルジクロロシランで処理したＢＥＴ比表面積２００ｍ²／ｇの疎水性フュームドシリカ４５重量部、分子鎖両末端が水酸基で封鎖された平均重合度１３のジメチルポリシロキサン１０重量部を、室温にて２時間攪拌混合した。この組成物へ更にビニルトリブタノキシムシラン１０重量部、アミノプロピルトリメトキシシラン１．５重量部、キシレン６５重量部を添加したところ、ＢＭ回転粘度計での粘度が４回転では８５０Ｐａ・ｓ、２０回転では１８０Ｐａ・ｓと、チクソ性は高いものの極めて高粘度となってしまった。
【０１２４】
【実施例９】
分子鎖両末端がトリメトキシシロキシ基（−Ｏ−Ｓｉ−（ＯＣＨ₃）₃）で封鎖された２５℃での粘度が２０，０００ｃＳ（２万ｃＳ）のジメチルポリシロキサン５０重量部、表面をヘキサメチルジシラザンで処理したＢＥＴ比表面積１３０ｍ²／ｇの疎水性フュームドシリカ１０重量部を、１５０℃にて２時間撹拌混合した。その後、分子鎖両端末がトリメトキシシロキシ基で封鎖された２５℃での粘度が２０，０００ｃＳ（２万ｃＳ）のジメチルポリシロキサン５０重量部で希釈し、メチルトリメトキシシラン５重量部、ジブチルスズジオクトエート０．１重量部、アミノプロプルトリメトキシシラン１．０重量部を脱泡混合し、２０重量部のメチルエチルケトンを添加して粘度調整し、粘度４００ｍＰａ・ｓの硬化性シリコーン組成物（Ｌ）（硬化性組成物Ｌ）を得た。この組成物を２３℃／５５％ＲＨ／７日の条件で硬化させたところ、基板上に非常に外観が良好なシリコーン膜が形成された。またこの硬化物は、デュロメーター・タイプＡの硬度：４０、引っ張り強さ２．０ＭＰａの良好なゴム物性を有していた。（JIS 6249による）
【０１２５】
【比較例１０】
分子鎖両末端がトリメトキシシロキシ基で封鎖された２５℃での粘度が２０，０００ｃＳ（２万ｃＳ）のジメチルポリシロキサン５０重量部、ＢＥＴ比表面積２００ｍ²／ｇの疎水性フュームドシリカ１０重量部を、室温にて２時間撹拌混合した。その後、分子鎖両端末がトリメトキシシロキシ基で封鎖された２５℃での粘度が２０，０００ｃＳのジメチルポリシロキサン ５０重量部で希釈し、メチルトリメトキシシラン５重量部、ジブチルスズジオクトエート０．１重量部、アミノプロプルトリメトキシシラン１．０重量部を脱泡混合し、２０重量部のメチルエチルケトンを添加して粘度調整し、粘度４８０ｍＰａ・ｓの硬化性シリコーン組成物（Ｍ）を得た。この組成物（Ｍ）を電子基板の上にディスペンサーにてコーティングしたが、実施例９の組成物に比べてノズルからの吐出性に劣り、２３℃／５５％ＲＨ／７日の条件で硬化させたところ、基板上には乳濁した表面艶消しのシリコーン塗膜が形成された。またこの硬化物は、デュロメーター・タイプＡの硬度：３５、引っ張り強さ２．０ＭＰａであった。（JIS 6249による）このように実施例５〜９、比較例５〜比較例１０によれば、本発明の硬化性組成物は、低粘度と高いチクソ性とを有し、コーティング時の作業性に優れ、塗膜強度、表面平滑性などに優れていることが分かる。
【０１２６】
【実施例１０〜１５及び、比較例１１〜１４】
実施例１において、オルガノポリシロキサン組成物（Ａ）に代えて、実施例１０〜１５では上記実施例９に記載の硬化性シリコーン組成物（Ｌ）を、また比較例１１〜１４では比較例１０に記載の硬化性シリコーン組成物（Ｍ）を用い、またシリコーンオイル、キシレンをそれぞれ表５に示すような量で用いた以外は、実施例１と同様にして防汚塗料組成物を調製し、実施例１と同様にして各種物性を評価した。
【０１２７】
結果を表５〜表８に示す。
なお、表５は、表２と同様に塗料化したときの性状値、塗装作業性を示し、表６は、表３と同様に塗料化後の防汚性を示し、表７は、表２と同様に所定期間貯蔵後の塗料の性状値を示し、表８は、表４と同様に貯蔵後の塗料の防汚性を示す。
【０１２８】
【表５】

【０１２９】
【表６】

【０１３０】
【表７】

【０１３１】
【表８】

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a curable composition, a coating composition, a paint, an antifouling paint, a cured product thereof, and a substrate antifouling method. More specifically, the present invention is, for example, excellent in spray coating properties, can be thickened by a single coating, can shorten the coating period, and can obtain a coating film having a uniform thickness by the coating. The resulting coating film is excellent in coating film strength, coating film hardness, rubber physical properties, etc., exhibits excellent antifouling performance for a long period of time, and further has excellent storage stability before coating, The present invention relates to a coating composition, a paint, an antifouling paint, a cured product thereof, and an antifouling method for a substrate such as an underwater structure or a ship outer plate.
[0002]
TECHNICAL BACKGROUND OF THE INVENTION
Conventionally, in the production of a curable silicone rubber composition, whether it is a one-component type or a two-component type, in order to fully exhibit various properties after curing, such as surface smoothness and rubber strength, hydrophilic silica, Alternatively, hydrophobic silica surface-treated with hexamethyldisilazane or the like is blended.
[0003]
However, hydrophilic silica has poor affinity with silicone oil, and aggregates of fillers such as silica are formed in the curable silicone rubber composition, and excellent characteristics are obtained even when such a composition is cured. Rubber cannot be obtained. In addition, the hydrophobic silica has a good affinity with silicone oil, does not cause much aggregation in the composition, silica is relatively well dispersed, has a good thixotropy, and is suitable for vertical surfaces. Can be expected to be thickened by a single coating. However, this composition has a high viscosity and poor spray coating properties, and when diluted with a solvent, the thixotropy is suddenly lost, and the coating film sags or the smoothness of the coating film decreases. There is.
[0004]
For example, (1): JP-A-10-316933 discloses (a) a room temperature curable silicone rubber having a number average molecular weight of 20,000 to 100,000, and (b) a room temperature curable resin having a number average molecular weight of 500 to 20,000. A coating composition containing silicone rubber and (c) silicone oil as main components is disclosed, and a coating composition containing hydrophobic fumed silica (d) is also shown. In this way, with a coating composition in which hydrophobic fumed silica is blended with two types of silicone rubbers having different molecular weights, it is possible to increase the film thickness by only one coating, but the storage stability of the coating is lacking and preparation is possible. Agar-like agglomeration is thought to be caused by secondary aggregation of silica during storage, so spray coating properties during painting are poor, and the coating surface is non-uniform during coating formation (thickness, color tone, etc. are uneven and smeared) There is a problem that a good coating film such as film thickness and rubber strength cannot be formed.
[0005]
By the way, underwater structures, fishing nets, etc. are used for a long time in the water, especially in the seawater. If attached or propagated, the original functions of underwater structures and fishing nets may be impaired. Among them, underwater structures such as water supply and drainage outlets of thermal power and nuclear power plants are constructed and fixed at predetermined positions in the sea, and aquaculture nets and stationary nets are left in the seawater for a long time. Breeding is remarkable, and frequent replacement, removal and cleaning must be performed, resulting in a large economic loss.
[0006]
In order to solve such problems, antifouling paints are widely applied to the surface of underwater structures, fishing nets, seawater equipment, etc. for the purpose of preventing adhesion of marine organisms.
For example, (2): Japanese Examined Patent Publication No. 63-2959 discloses a non-toxic antifouling antifouling paint composition comprising a chemically reaction-curing silicone rubber, a petrolatum or liquid paraffin mixture, and a low viscosity silicone oil. In this publication, it is described that if this composition is applied to the wetted part of an underwater structure, the growth of marine organisms can be prevented over a long period of time. However, with this non-toxic antifouling paint composition, it is difficult to obtain a sufficiently thick film just by applying it once, and the obtained coating film is inferior in strength and hardness and easily damaged. is there.
[0007]
The applicant previously proposed (3): Japanese Patent No. 2522854 discloses (A) an organopolysiloxane in which both ends of a molecular chain are blocked with silanol groups or hydrolyzable groups; R¹ _aSiX_4-a(Where R is¹Represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, X represents a hydrolyzable group, and a represents 0 or 1. ) Or a partial hydrolyzate thereof, and (C) in one molecule the formula: ≡SiR²OSiR^Three _bY_3-b(Wherein R²Represents an unsubstituted or substituted divalent hydrocarbon group or a divalent hydrocarbon group containing an ether bond, R^ThreeIs an unsubstituted or substituted monovalent hydrocarbon group, Y is a hydrolyzable group, and b is 0, 1 or 2. However, R²Is a divalent hydrocarbon group containing an ether bond, except for an organopolysiloxane in which two or more trimethylsiloxy groups are bonded to a Si atom in which a carbon atom of the hydrocarbon group is directly bonded. A curable organopolysiloxane composition mainly comprising at least one organopolysiloxane and a cured product thereof are disclosed. In addition, the publication describes that as a filler, fine powder silica, fumed silica, precipitated silica, and the like, and those whose surfaces are hydrophobized with silane or the like may be blended. In addition, the publication describes that the cured product has no fear of environmental pollution and the antifouling effect lasts for a long time. However, the curable organopolysiloxane composition described in the publication has room for improvement in terms of thickening the coating film, strength, hardness, and the like, and has a problem that it is easily damaged.
[0008]
The antifouling paint composition described in {circle around (1)} JP-A-10-316933 can be thickened only by being applied once as described above, but it has storage stability as a paint. The coating surface is poor and the surface of the coating film is not uniform (the film thickness, color tone, etc. are uneven and have uneven spots), and a good coating film can be formed. In particular, there is a problem that it is inferior in long-term antifouling properties when used as an antifouling coating.
[0009]
OBJECT OF THE INVENTION
The present invention is intended to solve the problems associated with the prior art as described above, and is excellent in balance with low viscosity, high thixotropy, etc., and can be thickened by a single coating, The obtained cured coating film is intended to provide a curable composition having excellent balance in rubber strength, surface smoothness and the like.
[0010]
In addition, the present invention, when used as a coating material, particularly as a paint, is excellent in spray paintability, can be thickened by a single coating, can shorten the coating period, and is excellent in coating film surface uniformity by the coating. A good coating film is obtained, and the obtained coating film is excellent in coating film strength and coating film hardness, and when used as an antifouling paint, exhibits excellent antifouling performance for a long period of time. The object of the present invention is to provide a curable composition having excellent storage stability, in particular, a coating composition, a curable coating composition, and an antifouling coating composition.
[0011]
In addition, the present invention provides electrical parts, building materials, crafts, clothing industrial products, and medical products that are excellent in coating film strength, coating film hardness, surface smoothness, etc. when used as a coating material, particularly a paint as described above. And providing an antifouling coating film that exhibits excellent antifouling performance for a long period of time when used as an antifouling paint, or an underwater structure coated with the coating film, a ship skin, etc. It is an object.
[0012]
It is an object of the present invention to provide a method for producing a curable composition, a coating composition, and a curable (antifouling) coating composition so that a thick film having the above characteristics can be obtained by a single coating. It is said.
Furthermore, the present invention is capable of forming a coating film having excellent properties as described above on the surface of various substrates such as the surface of an underwater structure, which is safe for an operator and can be efficiently formed without fear of environmental pollution. It is an object of the present invention to provide a method for forming a coating film on the surface of an electrical component or the like and a method for preventing the surface of a substrate such as a ship outer plate, an underwater structure, or a fishing net.
[0013]
[Summary of the Invention]
  According to the present inventionThe antifouling paint composition comprises the following curable composition,The curable composition is a curable composition containing (A) an organopolysiloxane having a condensation-reactive functional group at both ends of a molecule and (B) a hydrophobic silica, wherein the hydrophobic silica ( B) is heat-treated with organopolysiloxane (A). This hydrophobic silica (B) may be heat-treated with a part of the organopolysiloxane (A), or may be heat-treated with all of the organopolysiloxane (A).
[0014]
In the present invention, the organopolysiloxane (A) is represented by the following formula [α]:
[0015]
[Chemical 2]

[0016]
(In the formula [α], W represents a hydroxyl group or a hydrolyzable group, R¹, R each independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R¹, R may be the same as or different from each other, n represents an integer of 5 or more, and a represents 0, 1 or 2. It is desirable that it be a compound represented by
In the present invention, when W in the formula [α] is a hydroxyl group and a is 2, in addition to the component (A) and the component (B),
(C) Formula [I]: R¹ _bSiX_4-b(In the formula [I], R¹Represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, X represents a hydrolyzable group, and b represents 0 or 1. It is desirable to contain an organosilane represented by the above or a partial hydrolyzate thereof.
[0017]
In the present invention, the hydrophobic silica is desirably heat-treated with the component (A) at a temperature of 100 ° C. or higher. In this invention, it is desirable to contain the said component (B) in the quantity of 1-100 weight part with respect to 100 weight part of said components (A).
Moreover, it is desirable to contain the said component (C) in the quantity of 1-20 weight part with respect to 100 weight part of said component (A). In the present invention, the silicone oil (D) is preferably contained in an amount of 0.1 to 200 parts by weight with respect to 100 parts by weight of the component (A).
[0018]
In the present invention, it is desirable to further include a catalyst, an antifouling agent and / or a colorant.
The coating composition according to the present invention comprises any one of the curable compositions described above.
In the present invention, the coating composition is preferably used as a paint or an antifouling paint.
[0019]
The cured product according to the present invention is obtained by curing any of the curable compositions described above.
The coating film and antifouling coating film according to the present invention are formed by applying and curing the above-described coating material and antifouling coating material.
The base material with a coating film according to the present invention is characterized in that the surface of the base material is coated with a coating film obtained by curing the above-mentioned coating composition. Examples include electronic supplies, building materials, craft supplies, clothing industry supplies, medical supplies, and the like.
[0020]
In the method for forming a coating film on the surface of a substrate according to the present invention, the coating composition is applied or impregnated on the surface of the substrate such as the electrical component, and then the coating composition is cured and applied. It is characterized by forming a film.
The antifouling substrate according to the present invention is characterized in that the surface of the substrate in contact with seawater or fresh water is coated with a coating film obtained by curing the antifouling paint, Are preferably underwater structures, ship skins, fishing nets and fishing gear.
[0021]
The antifouling method for a substrate according to the present invention comprises applying or impregnating the antifouling paint onto the surface of the substrate such as the underwater structure, and then curing the antifouling paint to form an antifouling coating film. It is characterized by that.
According to the present invention, low viscosity, high thixotropy, etc. are excellent in a good balance, thickening is possible with a single coating, and the resulting cured coating is excellent in good balance in rubber strength, surface smoothness, etc. A curable composition is provided.
[0022]
In addition, according to the present invention, particularly when used as a coating composition or paint, it is excellent in spray coating properties, can be thickened by a single coating, can shorten the coating period, and can be applied with a uniform film thickness. A film is obtained, and the obtained coating film is excellent in coating film strength and coating film hardness. In particular, when used as an antifouling paint, it exhibits good antifouling performance for a long period of time, and is further preserved before coating. A curable composition having excellent stability is provided.
[0023]
Such a curable composition is suitably used as a coating composition, particularly as a curable coating composition or an antifouling coating composition.
The cured product according to the present invention, particularly the cured coating product, has excellent balance of rubber properties such as surface gloss, rubber hardness, and tensile strength. The coated underwater structure or ship skin has characteristics such as long-term antifouling properties.
[0024]
According to the method for producing a curable composition according to the present invention, a desired thick film coating can be performed on the surface of a substrate standing upright by a single coating, and the coating material and paint, particularly high coating efficiency. A curable composition such as an antifouling paint can be produced.
According to the antifouling method for a substrate surface according to the present invention, a coating film having excellent characteristics as described above is applied to the surface of various substrates such as the surface of an underwater structure, which is safe for an operator and may cause environmental pollution. And a desired coating film can be formed efficiently.
[0025]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the curable composition, the coating composition, the paint, the antifouling paint, the cured product thereof, and the antifouling method of the substrate according to the present invention will be specifically described.
<Curable composition>
The curable composition according to the present invention includes (A) an organopolysiloxane having a condensation-reactive group functional group at both ends of a molecule (chain molecule or molecular main chain);
(B) Hydrophobic silica is contained, and this hydrophobic silica (B) is heat-treated with the component (A). This hydrophobic silica (B) may be heat-treated with a part of the organopolysiloxane (A) used, or may be heat-treated with all of the organopolysiloxane (A).
[0026]
Hereinafter, the organopolysiloxane (A) will be described first.
<Organopolysiloxane (A)>
As the organopolysiloxane (A), a polymer as a main component of an organosilicone as described in Japanese Patent No. 2522854, particularly preferably a liquid polymer is used. Such an organopolysiloxane (A) As the following formula [α]:
[0027]
[Chemical 3]

[0028]
(In the formula [α], W is a condensation-reactive functional group, which represents a hydroxyl group (—OH) or a hydrolyzable group, R¹, R each independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R¹, R may be the same as or different from each other, n represents an integer of 5 or more, and a represents 0, 1 or 2. )
The one represented by is desirable.
[0029]
In this formula [α], when a = 0, 1, W of the condensation-reactive functional group is a hydrolyzable group, and when a = 2, W is a hydroxyl group (—OH). It is desirable to be.
In the present invention, when W in the formula [α] is a hydroxyl group and a is 2, in addition to the component (A) and the component (B) described above, (C) Formula [I]: R¹ _bSiX_4-b(In the formula [I], R¹Represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, X represents a hydrolyzable group, and b represents 0 or 1. It is preferable that the organosilane shown by (4) or its partial hydrolyzate is contained.
[0030]
Hereinafter, the organopolysiloxane (A) represented by the formula [α] will be described first.
When w in the formula [α] is a hydrolyzable group, examples of such hydrolyzable group include an alkoxy group, an acyloxy group, an alkenyloxy group, an iminoxy group, an amino group, an amide group, an aminooxy group. Group etc. are mentioned, An alkoxy group is preferable.
[0031]
As the alkoxy group, those having 1 to 10 carbon atoms are desirable, and one or more oxygen atoms may be interposed between carbon atoms. For example, methoxy group, ethoxy group, propoxy group, butoxy group, A methoxyethoxy group, an ethoxyethoxy group, etc. are mentioned.
The acyloxy group is preferably an aliphatic group or an aromatic group represented by the formula: RCOO- (wherein R is an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 12 carbon atoms), for example, , Acetoxy group, propionoxy group, butyroxy group, benzoyloxy group and the like.
[0032]
The alkenyloxy group preferably has about 3 to 10 carbon atoms, and examples thereof include an isopropenyloxy group, an isobutenyloxy group, and a 1-ethyl-2-methylvinyloxy group.
The ketoxime group preferably has about 3 to 10 carbon atoms, and examples thereof include a dimethyl ketoxime group, a methyl ethyl ketoxime group, a diethyl ketoxime group, a cyclopentanoxime group, and a cyclohexanoxime group.
[0033]
The amino group is preferably one having 1 to 10 carbon atoms, for example, N-methylamino group, N-ethylamino group, N-propylamino group, N-butylamino group, N, N-dimethylamino group, N , N-diethylamino group, cyclohexylamino group and the like.
The amide group preferably has 2 to 10 carbon atoms, and examples thereof include an N-methylacetamide group, an N-ethylacetamide group, and an N-methylbenzamide group.
[0034]
The aminooxy group preferably has 2 to 10 carbon atoms in total, and examples thereof include an N, N-dimethylaminooxy group and an N, N-diethylaminooxy group.
R¹, R each independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 8 carbon atoms, and such monovalent hydrocarbon group Examples of the alkyl group include an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, and an aralkyl group.
[0035]
The alkyl group may be any type of linear, branched or alicyclic alkyl group, and the linear or branched alkyl group having 1 to 10, preferably about 1 to 8 carbon atoms. Is preferred.
Examples of such a linear or branched alkyl group include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a 2-ethylbutyl group, and an octyl group, and particularly preferably a methyl group.
[0036]
The alkenyl group preferably has 2 to 10 carbon atoms, preferably about 2 to 8 carbon atoms, and examples thereof include a vinyl group, a hexenyl group, and an allyl group.
The aryl group preferably has 6 to 15 carbon atoms, preferably about 6 to 12 carbon atoms, and examples thereof include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a diphenyl group, and the like, and a phenyl group is particularly preferable.
[0037]
As a cycloalkyl group, a C3-C8 thing is desirable, for example, a cyclohexyl group, a cyclopentyl group, etc. are mentioned.
The aralkyl group preferably has a total carbon number of 7 to 10, preferably about 7 to 8, and examples thereof include a benzyl group and a 2-phenylethyl group.
These groups R¹Some or all of the hydrogen atoms bonded to the carbon atoms therein may be substituted with halogen atoms such as F, Cl, Br, and I, cyano groups, etc. Examples of the halogenated alkyl groups include chloromethyl Group, 3,3,3-trifluoropropyl group, 2-cyanoethyl group and the like.
[0038]
R is preferably an unsubstituted monovalent hydrocarbon group, particularly preferably a methyl group or a phenyl group.
In the organopolysiloxane (A) represented by the formula [α], a plurality of R¹, When there are a plurality of R, the plurality of R¹Between each other, a plurality of Rs, or R¹And R may be the same as or different from each other.
[0039]
The viscosity at 25 ° C. of such an organopolysiloxane (A) varies depending on the use of the curable composition to be used and is not generally determined. However, the coating properties of the resulting composition, and when the resulting composition is diluted with a solvent In view of prevention of sagging, etc., it is usually 25 cS to 1,500,000 cS (1.5 million cS), preferably 25 to 500,000 cS, more preferably 500 to 200,000 cS, particularly preferably 1,000 to 100. 1,000 cS is desirable.
[0040]
<Hydrophobic silica (B)>
Hydrophobic silica includes hydrophobic wet silica and hydrophobic fumed silica.
In the present invention, the organopolysiloxane A) and the heat-treated hydrophobic silica as described above are used as the silica component (B). Since the curable composition according to the present invention contains the component (A) and the heat-treated hydrophobic silica (B) together with the organopolysiloxane (A), the resulting curable composition is coated. When used in materials (coating compositions) and paints, especially antifouling paints, it has excellent stability during preparation, storage and storage, has sufficient thixotropy, and can be thickened by a single coating. The obtained coating film is excellent in balance in rubber physical properties such as hardness, tensile strength, and elongation, and is excellent in antifouling property when used as an antifouling coating film.
[0041]
The silica component used in the present invention is obtained by heat-treating hydrophobic silica with a part or all of the component (A), as will be described in detail later.
The silica includes hydrophilic silica such as wet method silica and dry method silica, and hydrophobic silica. Among these silicas, wet method silica which is one type of hydrophilic silica is usually adsorbed moisture. The content (also referred to as moisture content) is about 4-8%, the bulk density is 200-300 g / L, the primary particle size is 10-30 mμ, and the specific surface area (BET surface area) is 10 m.²/ G or more, preferably 50 to 800 m²/ G, more preferably 100 to 300 m²/ G or so.
[0042]
Dry process silica (fumed silica) usually has a moisture content of 1.5% or less. This dry silica has a low initial moisture content of, for example, 0.3% or less, such as immediately after production. However, the moisture content gradually increases if left untreated, and after several months have passed since production. Then, for example, it becomes about 0.5 to 1.0%. In addition, the bulk density of such dry process silica varies depending on the type and is not determined unconditionally. For example, it is 50 to 100 g / L, the primary particle diameter is 8 to 20 mμ, and the specific surface area (BET surface area) is: 10m²/ G or more, preferably 100 to 400 m²/ G, more preferably 180 to 300 m²/ G or so.
[0043]
Hydrophobic silica is obtained by surface-treating these hydrophilic silicas with an organosilicon compound such as methyltrichlorosilane, dimethyldichlorosilane, hexamethyldisilazane, hexamethylcyclotrisiloxane, and octamethylcyclotetrasiloxane. Of these, hydrophobic fumed silica is preferred, and hydrophobic fumed silica has little moisture adsorption over time, and the moisture content is usually 0.3% or less, often 0.1 to 0.2%. Surface area is 10m²/ G or more, preferably 100 to 300 m²/ G, more preferably 120 to 230 m²/ G, the primary particle diameter is 5 to 50 mμ, and the bulk density is 50 to 100 g / L.
[0044]
In the hydrophobic fumed silica (heat treated hydrophobic fumed silica) heat-treated with the component (A), the moisture adsorbed on the surface of the hydrophobic silica is physically reduced and removed, and the water content is reduced. Usually, it is 0.2% or less, preferably 0.1% or less, particularly 0.05 to 0.1%, and other physical property values such as bulk density are the same as those of the hydrophobic silica.
[0045]
Such component (B) is usually used in an amount of 1 to 100 parts by weight, preferably 2 to 50 parts by weight, particularly preferably 5 to 30 parts by weight, based on 100 parts by weight of the component (A). It is desirable to be contained in the curable composition.
When the silica component (B) is contained in such a quantity in the curable composition, the coating film strength and coating film hardness are excellent, the thixotropy is good, the viscosity is appropriate, and the coating is particularly good. Spray coating can be performed, and for example, even on a vertically erected substrate surface, it is preferable because the coating film can be thickened by a single coating.
[0046]
In addition, when the said component (B) is less than the said range, sufficient coating-film intensity | strength and coating-film hardness are not obtained, but desired thixotropy is not obtained, but desired thickening is carried out by one coating especially spray coating. If the amount of the component (B) exceeds the above range, the viscosity of the paint becomes excessively high, and it is necessary to dilute with a solvent such as thinner to an appropriate viscosity suitable for coating. Thickening by painting may not be possible.
[0047]
<Organosilane or its partial hydrolyzate (C)>
In the present invention, when the component (A) is represented by the formula [α], W in the formula [α] is a hydroxyl group, and a is 2, such a component (A) In addition to the above component (B),
(C) Formula [I]: R¹ _bSiX_4-b(In the formula [I], R¹Is a C 1-8 unsubstituted or substituted R, R in the formula [α]¹And X represents a hydrolyzable group similar to W in the formula [α], and b represents 0 or 1. It is preferable that the organosilane shown by (4) or its partial hydrolyzate is contained.
[0048]
That is, in the present invention, as the component (A), an organopolysiloxane in which both ends of the molecule (chain molecule, molecular chain) are hydroxyl groups (—OH), specifically, both ends of the molecular chain are silanols. When using a curable organopolysiloxane blocked with a group (≡Si—OH), it is particularly preferable to use such a component (A) in combination with a component (C) as a crosslinking agent / curing agent. . Further, for example, when a curable organopolysiloxane having both molecular ends blocked with hydrolyzable groups is used as the component (A), it can be sufficiently cured even without the curing agent component (C). In such a case, it is more preferable to include the component (C).
[0049]
X is a hydrolyzable group similar to W in the formula [I].
Specific examples of the organosilane represented by the formula [I] or a (partial) hydrolyzate thereof include, for example, methyltrimethoxysilane, methyltri (methylethylketoxime) silane, methyltripropenyloxysilane, methyl Examples include triacetoxysilane and silane compounds obtained by substituting methyl groups of these silane compounds with vinyl groups, phenyl groups, trifluoropropyl groups, and the like, and partial hydrolysates thereof. In this case, the hydrolyzable group is preferably a ketoxime group.
[0050]
These organosilanes or hydrolysates thereof (C) can be used in an amount of 1 to 60 parts by weight with respect to 100 parts by weight of the organopolysiloxane (A), but usually 1 to 20 parts by weight. It is desirable that it is contained in the curable composition of the present invention in an amount of preferably 2 to 10 parts by weight.
When organosilane or its hydrolyzate (C) is contained in the composition in such an amount, the crosslinking reaction of component (A) proceeds well, and the resulting coating film has an appropriate hardness. There is a tendency to be excellent in economic efficiency.
[0051]
<Silicone oil (D)>
The curable composition according to the present invention may contain a silicone oil (D). Examples of such a silicone oil (D) include non-reactive (non-condensable) silicone oils and curable compositions. It is not particularly limited as long as it is a silicone oil that bleeds out from the cured product, but it is preferably a component (D) different from the component (A), a silicone oil represented by the following formulas [II] and [IV], A silicone oil having a group represented by [III] is preferred.
[0052]
Among these silicone oils (D), silicone oils [II] and [IV] do not exhibit reactivity or self-condensation with the component (A), and have an antifouling function on the coating surface (layer). The silicone oil [III] is considered to have a function of forming a layer (film), and the silicone oil [III] reacts with the component (A) as a coating film forming component to form a cured coating film. When the substrate is immersed in the group, it is hydrolyzed with time, and the terminal group having an alcoholic hydroxyl group “≡SiR”^FourIt is thought that OH "or the like bleeds out to the surface of the coating film and exhibits an effect of preventing the adhesion of marine organisms.
[0053]
(R²)_ThreeSiO (SiR^Three ₂O)_nSi (R²)_Three・ ・ ・ ・ ・ [II]
(In the formula [II], a plurality of R²May be the same or different from each other, and represents an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or a fluoroalkyl group, and a plurality of R^ThreeMay be the same or different from each other, and each R^ThreeRepresents an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or a fluoroalkyl group, and n represents a number of 0 to 150. )
≡SiR^FourOSiR^Five _bY_3-b・ ・ ・ ・ ・ [III]
(In the formula [III], R^FourRepresents an unsubstituted or substituted divalent hydrocarbon group or a divalent hydrocarbon group containing an ether bond, R^FiveIs an unsubstituted or substituted monovalent hydrocarbon group, Y is a hydrolyzable group, and b is 0, 1 or 2. )
R⁶ _xSi (R⁷-Z)_yO_{(4-xy) / 2}・ ・ ・ ・ ・ [IV]
(In the formula [IV], R⁶Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group, and R⁷Represents an ether group, an ester group or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be intervened by —NH—, and Z represents an amino group, a carboxyl group, an epoxy group or a terminal carbon number. 1 represents a monovalent polar group which is a polyethylene glycol or polypropylene glycol group which may be blocked with an alkyl group or an acyl group, and x and y are 0.01 ≦ x <3.99 and 0.00, respectively. 02 ≦ y <4 and 0.02 ≦ x + y <4. ).
[0054]
Among the silicone oils (D), as the silicone oil [II], those described in JP-A-10-316933 can be used, and the number average molecular weight is 180 to 20,000, preferably 1,000. It is desirable that the viscosity is from 10,000 to 10,000 and the viscosity is from 20 to 30,000 centistokes, preferably from 50 to 3,000 centistokes.
[0055]
Examples of such silicone oil [II] include R², R^ThreeExamples thereof include dimethyl silicone oils in which all of them are methyl groups, and phenyl methyl silicone oils in which some of the methyl groups of these dimethyl silicone oils are substituted with phenyl groups. Of these, methyl phenyl silicone oils are preferred.
Specifically, as such methylphenyl silicone oil, for example, “KF-54, KF-56, KF-50” (manufactured by Shin-Etsu Chemical Co., Ltd.), “SH510, SH550” (manufactured by Toray Dow Corning Silicone) ), “TSF431, TSF433” (manufactured by Toshiba Silicone Co., Ltd.), etc.
[0056]
Further, as the silicone oil having a group represented by the above formula [III] (silicone oil [III]), those described in Japanese Patent No. 2522854 proposed by the present applicants can be used, and the number average molecular weight can be used. Is from 250 to 20,000, preferably 1,000 to 10,000, and a viscosity of 20 to 30,000 centistokes, preferably 50 to 3000 centistokes.
[0057]
≡SiR^FourOSiR^Five _bY_3-b・ ・ ・ ・ ・ [III]
(In the formula [III], R^FourRepresents an unsubstituted or substituted divalent hydrocarbon group or a divalent hydrocarbon group containing an ether bond, R^FiveIs an unsubstituted or substituted monovalent hydrocarbon group, Y is a hydrolyzable group, and b is 0, 1 or 2. )
R above^FourSpecifically, for example, an unsubstituted or substituted divalent hydrocarbon group such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexamethylene group, or the like; or
“-(CH₂)_p-O- (CH₂)_q-"(Wherein p and q each independently represents an integer of 1 to 6) or the like, and a divalent hydrocarbon group containing an ether bond;
Etc.
[0058]
R^FiveAs R in formula [I] of component (C) above.¹Similarly, it represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms. Y represents the same group as the hydrolyzable group X in the formula [I] of the component (C).
As the silicone oil [III] having at least one group represented by the formula [III], specifically, for example, as described in the above-mentioned Japanese Patent No. 2522854,
(CH_Three)_ThreeSiO [(CH_Three)₂SiO]_m[R⁷R⁸SiO]_n(CH_Three)₂SiC_ThreeH₆-OH,
HO-C_ThreeH₆-[(CH_Three)₂SiO] [(CH_Three)₂SiO]_m[R⁷R⁸SiO]_n-(CH_Three)₂Si-C_ThreeH₆-OH,
(CH_Three)_ThreeSiO [(CH_Three)₂SiO]_m[R⁷R⁸SiO]_n[(CH_Three) (C_ThreeH₆-OH) SiO]_l[(CH_Three)₂SiCH_Three],
And the like in which the hydroxyl group of the silicone oil represented by the formula is blocked with a hydrolytic group. However, in each of the above formulas, R⁷, R⁸As aryl groups such as phenyl group and tolyl group; aralkyl groups such as benzyl group and β-phenylethyl group; halogenated alkyl groups such as trifluoropropyl group;⁷, R⁸An unsubstituted or substituted monovalent hydrocarbon group in which at least one of them is selected from a group other than a methyl group. m, n, and l are all positive numbers.
[0059]
In addition, from the viewpoint of storage stability of the resulting composition, the silicone oil is represented by the formula: “R” as exemplified below.^Five _bSiY_3-b(R^Five, Y and b are the same as in the formula [III]. It may be reacted with an organosilane represented by
(CH_Three)_ThreeSiO [(CH_Three)₂SiO]_m[R⁷R⁸SiO]_n(CH_Three)₂SiC_ThreeH₆-O-R^Five _bSiY_3-b,
HO-C_ThreeH₆-[(CH_Three)₂SiO] [(CH_Three)₂SiO]_m[R⁷R⁸SiO]_n-(CH_Three)₂Si-C_ThreeH₆-O-R^Five _bSiY_3-b,
(CH_Three)_ThreeSiO [(CH_Three)₂SiO]_m[R⁷R⁸SiO]_n[(CH_Three) (C_ThreeH₆-O-R^Five _bSiY_3-b) SiO]_l[(CH_Three)₂SiCH_Three]Such.
[0060]
As the silicone oil [IV], specifically, those described in JP-A-10-316933 can be used, and the number average molecular weight is 250 to 30,000, preferably 1,000 to 20,000. It is desirable that the viscosity is 20 to 30,000 centistokes, preferably 50 to 3,000 centistokes.
[0061]
R⁶ _xSi (R⁷-Z)_yO_{(4-xy) / 2}・ ・ ・ ・ ・ [IV]
(In the formula [IV], R⁶Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group, and R⁷Represents an ether group, an ester group or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be intervened by —NH—, and Z represents an amino group, a carboxyl group, an epoxy group or a terminal carbon number. 1 represents a monovalent polar group which is a polyethylene glycol or polypropylene glycol group which may be blocked with an alkyl group or an acyl group, and x and y are 0.01 ≦ x <3.99 and 0.00, respectively. 02 ≦ y <4 and 0.02 ≦ x + y <4. ).
[0062]
As such a silicone oil [IV], preferably, in the above formula [IV], R⁶Is a methyl group or a phenyl group, and R⁷Is preferably a methylene group, an ethylene group or a propylene group. In addition, as Z, when the terminal is a polyethylene glycol or polypropylene glycol group optionally blocked with an alkyl group or acyl group having 6 or less carbon atoms, the number of oxyethylene and oxypropylene as a repeating unit is 10 to 60. preferable. Examples of the alkyl group for end-capping include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the acyl group for end-capping include a ketoxime group, an acetyl group, and a propionyl group. .
[0063]
Specifically, as silicone oils in which the polar group Z is an amino group, “SF8417” (manufactured by Toray Dow Corning), “ISI4700, ISI4701” (manufactured by Toshiba Silicone), “FZ3712, AFL-40” (Japan) Unicar) and the like. Examples of the silicone oil in which the polar group Z is a carboxyl group include “XI42-411” (manufactured by Toshiba Silicone), “SF8418” (manufactured by Toray Dow Corning Silicone), “FXZ4707” (manufactured by Nippon Unicar), and the like. . Moreover, as silicone oil whose polar group is an epoxy group, “SF8411” (manufactured by Toray Dow Corning Silicone), “XI42-301” (manufactured by Toshiba Silicone), “L-93, T-29” (Nihon Unicar Company) Manufactured) and the like. Examples of the silicone oil in which the polar group Z is an alkyl group or an acyl group include “ISI4460, ISI4445, ISI4446” (manufactured by Toshiba Silicone), “SH3746, SH8400, SH3749, SH3700” (manufactured by Toray Dow Corning Silicone), “KF6009”. (Made by Shin-Etsu Silicone Co., Ltd.).
[0064]
In the present invention, such a silicone oil (D), preferably any one or more of silicone oil [II], silicone oil [III] and silicone oil [IV] is the above component (A ) It is desirable that the total amount is 0.1 to 200 parts by weight, preferably 20 to 100 parts by weight, based on 100 parts by weight.
[0065]
When the amount of this silicone oil (D) is in the above range, for example, when used as an antifouling paint, there is a tendency to obtain a (antifouling) coating film excellent in both antifouling properties and coating film strength. If it is less, the antifouling property is lowered, and if it is more than the above range, the coating strength may be lowered.
[Production of curable composition]
Such a curable composition according to the present invention, in particular, a coating composition, a curable coating composition, and an antifouling coating composition are prepared by previously containing part or all of the component (A) and hydrophobic silica. After heat treatment at normal temperature or under reduced pressure at a temperature of 100 ° C. or higher and below the decomposition temperature of the blended components, preferably 100 to 300 ° C., more preferably 140 to 200 ° C., usually for about 30 minutes to 3 hours. In addition to the remaining component (A) and the component (C) used as necessary, the component (D) can be further blended as necessary. In addition, conventionally known organosiloxane curing catalysts, antifouling agents, thixotropy imparting agents, plasticizers, inorganic dehydrating agents (stabilizers), anti-sagging / anti-settling agents (thickening agents), coloring pigments, dyes, other Coating composition components, solvents (eg xylene), bactericides, fungicides, anti-aging agents, antioxidants, anti-static agents, flame retardants, heat conduction improvers, adhesion promoters, etc. They can be added at once or in any order, and stirred and mixed, and dissolved and dispersed in a solvent.
[0066]
When the hydrophobic silica is heat-treated with the component (A) in this way, the component (A) and the component (B) in the resulting composition have excellent affinity, and aggregation of filler components such as the component (B) For example, the resulting coating composition, for example, an antifouling paint composition, exhibits appropriate fluidity, thixotropy, etc. It can be formed with a small number of coatings such as coating.
[0067]
In the case of stirring and mixing the above-described blending components, conventionally known mixing and stirring devices such as a loss mixer, a planetary mixer, and a universal Shinagawa stirrer are appropriately used.
As the catalyst, for example, those described in Japanese Patent No. 2522854 can be suitably used. Specifically, for example, tin carboxylates such as tin naphthenate and tin oleate;
Tin compounds such as dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dioleate, dibutyltin oxide, dibutyltin dimethoxide, dibutylbis (triethoxysiloxy) tin;
Titanic acid esters or titanium chelate compounds such as tetraisopropoxy titanium, tetra n-butoxy titanium, tetrakis (2-ethylhexoxy) titanium, dipropoxy bis (acetylacetonato) titanium, titanium isopropoxy octyl glycol;
Etc.,
Zinc naphthenate, zinc stearate, zinc-2-ethyl octoate, iron-2-ethylhexoate, cobalt-2-ethylhexoate, manganese-2-ethylhexoate, cobalt naphthenate, alkoxyaluminum compound Organometallic compounds such as;
Aminoalkyl group-substituted alkoxysilanes such as 3-aminopropyltrimethoxysilane and N-β (amonoethyl) γ-amonopropyltrimethoxysilane;
Amine compounds such as hexylamine, dodecyldodecylamine phosphate, dimethylhydroxylamine, diethylhydroxylamine and salts thereof;
Quaternary ammonium salts such as benzyltriethylammonium acetate;
Lower fatty acid salts of alkali metals such as potassium acetate, sodium acetate and lithium odorate;
Silanes or siloxanes containing a guanidyl group such as tetramethylguanidylpropyltrimethoxysilane, tetramethylguanidylpropylmethyldimethoxysilane, tetramethylguanidylpropyltris (trimethylsiloxy) silane;
Etc.
[0068]
These catalysts are used in an amount of 10 parts by weight or less, preferably 5 parts by weight or less, and more preferably 1 part by weight or less with respect to 100 parts by weight of component (A), and a preferred lower limit value when using the catalyst. Is 0.001 part by weight or more, particularly 0.01 part by weight or more.
<Optional component>
As described above, the curable composition according to the present invention is used as, for example, a coating composition, particularly a coating composition or an antifouling paint composition, particularly a curable antifouling paint composition (antifouling paint). In addition to the components (A) and (B) and the component (C) used as necessary, the antifouling agent, plasticizer, inorganic dehydrating agent, and Acid metal salts, anti-sagging / anti-settling agents (fading agents), pigments, other film forming components, other fillers, flame retardants, thixotropic agents, heat conduction improvers, solvents, antifungal agents, antibacterial agents Various components such as an agent, a matting agent and a fragrance may be contained.
[0069]
<Anti-fouling agent>
The antifouling agent may be either inorganic or organic. As the inorganic antifouling agent, conventionally known antifouling agents can be used, and among these, copper and inorganic copper compounds are preferable.
Organic antifouling agent
Examples of organic antifouling agents include metal-pyrithiones represented by the following formula (vi) [wherein R¹~ R^FourEach independently represents hydrogen, an alkyl group, an alkoxy group, or a halogenated alkyl group, M represents a metal such as Cu, Zn, Na, Mg, Ca, Ba, Pb, Fe, or Al, and n represents a valence. Show]:
[0070]
[Formula 4]

[0071]
, Tetramethylthiuram disulfide, carbamate compounds (eg, zinc dimethyldithiocarbamate, manganese-2-ethylenebisdithiocarbamate), 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyldichlorophenylurea 4,5-dichloro-2-n-octyl-3 (2H) isothiazoline, 2,4,6-trichlorophenylmaleimide, 2-methylthio-4-tert-butylamino-6-cyclopropyl S-triazine, etc. Can do.
[0072]
Among the above organic antifouling agents, copper pyrithione (in formula (vi), M = Cu), zinc pyrithione (in formula (vi), M = Zn), N, N-dimethyldichlorophenylurea, 2,4,6- Trichlorophenylmaleimide, 2-methylthio-4-tert-butylamino-6-cyclopropyl S-triazine, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2,4,5,6- Tetrachloroisophthalonitrile is preferred.
[0073]
Among these organic antifouling agents, metal pyrithiones and / or 4,5-dichloro-2-n-octyl-4-isothizolin-3-one are preferable, and further, when used in combination, antifouling performance is excellent. It is particularly preferable to use copper pyrithione and / or 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, and it is more preferable to use these in combination.
[0074]
In the antifouling paint composition containing such an organic antifouling agent, for example, in addition to copper and / or an inorganic copper compound, the organic antifouling agent is usually 0.1 to 20% by weight, preferably 0.5%. It is desirable that it be contained in an amount of -10% by weight. Moreover, with respect to 100 weight part of solid content contained in a coating composition, this organic antifouling agent is 0.1-150 weight part normally as solid content, Preferably it is the quantity of 0.1-100 weight part. It is desirable that it be included.
[0075]
<Plasticizer (chlorinated paraffin)>
Examples of the plasticizer include TCP (tricresyl phosphate), chlorinated paraffin, polyvinyl ethyl ether, and the like. These plasticizers can be used alone or in combination of two or more.
These plasticizers contribute to the improvement of crack resistance of a coating film (also referred to as “antifouling coating film”) comprising the resulting antifouling coating composition.
[0076]
<Inorganic dehydrating agent>
The inorganic dehydrating agent also functions as a stabilizer and can further improve the storage stability of the antifouling coating composition. As such an inorganic dehydrating agent, anhydrous gypsum (CaSO_Four), Synthetic zeolite-based adsorbent (trade name: molecular sieve, etc.), silicates and the like, and anhydrous gypsum and molecular sieve are preferably used. Such inorganic dehydrating agents can be used alone or in combination.
[0077]
In the curable coating composition containing such an inorganic dehydrating agent, this inorganic dehydrating agent is usually 0.1 to 10% by weight, preferably 0.1 to 10% by weight, in the non-tin coating composition of the present invention. It may be contained in an amount of about 5% by weight.
<Carboxylic acid metal salt>
The curable coating composition according to the present invention may further contain a carboxylic acid metal salt.
[0078]
As the carboxylic acid metal salt, those having a molecular weight of usually 50 to 1000, preferably 100 to 600 are used.
Examples of the carboxylic acid constituting such a carboxylic acid metal salt include a carboxylic acid having an alicyclic structure (eg, naphthenic acid) and a carboxylic acid having an aromatic ring structure (eg, α- (2-carboxyphenoxy) stearic acid). , Rosin resin acid, fatty acid, and the like, and naphthenic acid, rosin resin acid, and fatty acid are preferable.
[0079]
<Anti-sagging / Anti-settling agent (fading agent)>
Anti-sagging and anti-settling agents (fading agents) include organoclay Al, Ca, Zn stearate salts, lecithin salts, alkyl sulfonate salts, polyethylene wax, amide wax, hydrogenated castor oil wax system Polyamide wax and mixtures thereof, synthetic fine powder silica, oxidized polyethylene wax, and the like. Polyamide wax, synthetic fine powder silica, oxidized polyethylene wax, and organic clay are preferably used. Examples of such anti-sagging and anti-settling agents are those marketed under the trade names such as “DISPARON 305” and “DISPARON 4200-20” manufactured by Enomoto Kasei Co., Ltd. and “DISPARON A630-20X”. Is mentioned.
[0080]
Such an anti-sagging / anti-settling agent is blended in the curable coating composition in an amount of 0.1 to 10% by weight, for example.
<Pigment>
As the pigment, various conventionally known organic and inorganic pigments can be used.
Examples of organic pigments include carbon black, phthalocyanine blue, and bitumen. Examples of inorganic pigments are neutral and non-reactive materials such as titanium white, bengara, barite powder, silica, tankal, talc, chalk, iron oxide powder; zinc white (ZnO, zinc oxide), lead Examples include basic (active pigments) that are basic and reactive with acidic substances in the paint, such as white, red lead, zinc dust, and lead oxide powder. Various colorants such as dyes may also be included. Such various pigments are blended in the curable composition, particularly in the curable coating composition, for example, in an amount of about 0.5 to 45% by weight in total.
[0081]
<Other coating film forming components>
As the coating film forming component, a coating film forming component other than the above-described organopolysiloxane (A) may be contained within a range not contrary to the object of the present invention. For example, acrylic resin, acrylic silicone resin, unsaturated polyester resin, fluorine resin, polybutene resin, silicone rubber, urethane resin (rubber), polyamide resin, vinyl chloride copolymer resin, chlorinated rubber (resin), chlorinated Olefin resin, styrene / butadiene copolymer resin, ethylene-vinyl acetate copolymer resin, vinyl chloride resin, alkyd resin, coumarone resin, trialkylsilyl acrylate (co) polymer (silyl resin), petroleum resin, etc. Examples thereof include water-soluble resins (hereinafter also referred to as difficult / non-water-soluble resins).
[0082]
<Other fillers, flame retardants, thixotropic agents, heat conduction improvers, adhesive components, etc.>
As fillers other than those described above, diatomaceous earth, iron oxide, zinc oxide, titanium oxide, alumina and other metal oxides, or surfaces thereof treated with a silane compound;
Metal carbonates such as calcium carbonate, magnesium carbonate, zinc carbonate;
Other examples include asbestos, glass fiber, carbon black, quartz powder, aluminum hydroxide, gold powder, silver powder, surface-treated calcium carbonate, and glass balloon. These fillers may be used alone or in combination of two or more.
[0083]
Examples of the thixotropic property-imparting agent include polyethylene glycol, polypropylene glycol, and derivatives thereof.
Examples of the flame retardant include antimony oxide and paraffin oxide.
Examples of the heat conduction improver include boron nitride and aluminum oxide.
Examples of the adhesive component include substances such as silane coupling agents containing one or more groups such as an alkoxysilyl group, an epoxy group, a hydrosilyl group, and a (meth) acryl group, or a mixture of these substances.
[0084]
<Solvent>
The curable composition such as the curable coating composition of the present invention may or may not contain a solvent, but the various components as described above may be added to the solvent as necessary. It can be used by dissolving or dispersing. As the solvent used here, for example, various solvents such as aliphatic, aromatic, ketone, ester, ether, alcohol and the like which are usually blended in antifouling paints are used. Examples of the aromatic solvent include xylene and toluene. Examples of the ketone solvent include MIBK and cyclohexanone. Examples of the ether solvent include propylene glycol monomethyl ether and propylene glycol monomethyl. Ether acetate (PMAC) etc. are mentioned, As an alcohol solvent, isopropyl alcohol etc. are mentioned, for example.
[0085]
Such a solvent can be used in any amount, but for example, in an amount of 0.1 to 9999 parts by weight, preferably in an amount of 1 to 50 parts by weight with respect to 100 parts by weight of the component (A). Used. The curable composition of the present invention is used in an amount of 1 to 99% by weight, preferably 5 to 50% by weight.
The viscosity (25 ° C., B-type viscometer, No. 3 rotor) of a curable composition such as a curable coating composition diluted as necessary with such a solvent is coatability (sagging property), applied once In consideration of the film thickness obtained in the above, for example, it is about 0.01 to 500 poise / 25 ° C., preferably about 0.1 to 200 poise / 25 ° C. In other words, the pressure is about 0.001 to 50 Pa · s, preferably about 0.01 to 20 Pa · s.
[0086]
The curable composition of the present invention is used as a coating material (coating composition) for surface coating of various substrates such as electric parts, electronic parts, building materials, craft supplies, clothing industrial articles, medical supplies, seawater or It is suitably used as an antifouling paint for surface antifouling of substrates that come into contact with fresh water, for example, substrates such as underwater structures, ship skins, fishing nets, and fishing gear. In addition, it is also used as an anti-icing paint and a water repellent. Thus, the curable composition of the present invention has a wide range of industries such as electricity / electronics, building materials / crafts, clothing industry, medical care, agriculture / forestry / fishery industry, power generation, port / civil engineering construction, shipbuilding or ship repair, especially ship painting. Used in the field.
[0087]
In particular, when the curable composition is applied as a coating composition to a substrate surface such as an electrical component, electronic article, building material, craft article, clothing industrial article, or medical article, the composition has a low viscosity. The balance between high thixotropy is excellent, so thickening can be achieved with a single coating and coating workability is good. By coating and curing such a composition, for example, flame retardancy, rubber strength, surface A substrate with a coating film excellent in smoothness and the like is obtained.
[0088]
In particular, curable compositions as described above are used as paints, particularly antifouling paints (antifouling paint compositions), for example, underwater structures such as thermal and nuclear power plants, seawater use equipment (eg seawater) Pumps, etc.), megafloats, bay roads, submarine tunnels, harbor facilities, canals, waterways, etc. for various civil engineering works such as sludge diffusion prevention films, ships, especially ship skins, fishing materials (eg ropes, fishing nets, floats) , Buoys, etc.) on the surface of various molded products according to a conventional method once to multiple times and cured, it is excellent in antifouling property, and the antifouling agent component can be gradually released over a long period of time. However, an antifouling substrate such as an antifouling film-coated ship or an underwater structure having moderate flexibility and excellent crack resistance can be obtained. In such coating, conventionally known coating means such as brushes, rolls, sprays, dip coaters and the like are widely used.
[0089]
The antifouling coating film obtained by applying and curing the curable antifouling coating composition according to the present invention on the surface of various molded bodies (base materials) is a water tank such as Aosa, Barnacle, Aonori, Cell plastic, Oyster, Fusakomushi. It has excellent antifouling properties such as being able to prevent organisms from sticking for a long time.
In particular, the curable antifouling paint composition is used for the surface of these base materials (materials) even when the material of the water supply / drainage port, mega float, ship, etc. of nuclear power plants is FRP, steel, wood, aluminum alloy, etc. Adheres well. The curable antifouling coating composition may be overcoated on the surface of an existing antifouling coating film.
[0090]
Also, for example, if the curable antifouling coating composition is applied and cured on the surface of an underwater structure, adhesion of marine organisms can be prevented, and the function of the structure can be maintained for a long period of time. For example, it is possible to prevent the mesh of the fishing net from being blocked and to reduce the risk of environmental pollution.
The curable antifouling paint composition according to the present invention may be applied directly to a fishing net, or applied to the surface of a ship or an underwater structure or the like on which a base material such as a rust preventive agent or primer has been applied in advance. May be. Furthermore, the surface of a ship that has already been coated with a conventional antifouling paint or that has been coated with the curable antifouling paint composition of the present invention, particularly an FRP ship or an underwater structure, is used for repair. The curable antifouling coating composition of the present invention may be overcoated. Thus, although the thickness of the antifouling coating film formed on the surface of a ship, an underwater structure, etc. is not specifically limited, For example, it is about 30-150 micrometers / time.
[0091]
The antifouling coating film according to the present invention obtained as described above, or the coating film on the surface of the water contact part of the ship / underwater structure, is formed from the curable antifouling coating composition as described above, and is an environmental pollution. It has excellent long-term antifouling properties against a wide range of ships and underwater structures.
[0092]
【The invention's effect】
When the curable composition according to the present invention is used as a coating composition, particularly a paint, an antifouling paint composition, etc., it exhibits a good balance between low viscosity and high thixotropy, and there is no nozzle clogging or disturbance. Excellent paintability, can be thickened by a single coating, shortens the coating period, and the coating film surface uniformity (film thickness uniformity or surface smoothness) A cured product is obtained, and the obtained coating film is excellent in coating film strength (rubber strength) and coating film hardness. When used as an antifouling paint, the resulting coating film has excellent antifouling performance for a long period of time. And is excellent in storage stability before coating. Therefore, a curable composition suitable as a coating composition, particularly as a curable coating composition or an antifouling coating composition is provided.
[0093]
In addition, according to the present invention, as described above, the coating film strength and coating film hardness are excellent, and various cured products such as coating films and coating cured products that exhibit excellent antifouling performance for a long period of time, Provided are an antifouling coating film, an underwater structure coated with the coating film and having these characteristics, a ship skin, and the like.
Furthermore, according to the present invention, a coating film having excellent properties as described above can be efficiently formed on the surface of various substrates such as the surface of an underwater structure, safely for the operator, and without fear of environmental pollution. It is possible to provide a method for forming a coating film on the surface of a substrate such as an electronic component and a method for preventing soiling of a substrate such as an underwater structure.
[0094]
【Example】
Hereinafter, although an example and a comparative example explain the present invention still more concretely, the present invention is not limited at all by the example and comparative example which concern.
In addition, the composition value etc. which are described in the following synthetic examples, examples, and comparative examples are parts by weight.
(Synthesis of silicone oil (D))
[0095]
[Synthesis Example 1]
Following formula:
[0096]
[Chemical formula 5]

[0097]
193 g of an organopolysiloxane containing an alcoholic hydroxyl group represented by the formula and 60 g of methyltri (methylethylketoxime) silane are mixed and reacted at room temperature.
[0098]
[Chemical 6]

[0099]
The silicone oil (D) shown by was obtained. This silicone oil contained unreacted raw material methyltri (methylethylketoxime) silane.
[0100]
[Preparation of organopolysiloxane coating compositions (A) to (H)]
In Table 1, hydrophobic fumed silica surface-treated with hexamethyldisilazane was added to dimethylpolysiloxane having both molecular ends blocked with silanol groups and a viscosity of 20000 cst (20,000 cst). Mixed and stirred at ℃ for 2 hours and heat-treated (see * 2), the same hydrophobic silica listed in Table 1 mixed with organopolysiloxane at room temperature (see * 3), and Table 1 Mix and agitate the hydrophilic silica described in 2 with organopolysiloxane at 150 ° C for 2 hours and heat-treat (see * 4) in the blending amounts shown in Table 1 and mix thoroughly with a stirrer. Dispersed. Further, a crosslinking agent and a catalyst were added in the blending amounts shown in Table 1 and mixed uniformly to obtain a curable organopolysiloxane coating composition having a composition as shown in (A) to (H).
[0101]
These property values and physical properties of the coating film are shown in Table 1. In Table 1, * 1, 2, 3, 4 and test methods are as follows.
Moreover, in the table | surface, various silica is the quantity (weight part) of a silica with respect to 100 weight part of total organopolysiloxane (A) in a coating composition.
* 1: Organopolysiloxane:Manufactured by Shin-Etsu Chemical Co., Ltd.
Chemical formula: “HO (CH_Three・ CH_Three・ SiO)_mH ”(viscosity at 25 ° C. 20000 cs)
* 2: Heat treated hydrophobic fumed silica:
Silica (Shin-Etsu Chemical Co., Ltd., manufactured by Shin-Etsu Chemical Co., Ltd., water content 0.05%, bulk density 50 g / L, primary particle diameter 10mμ, specific surface area (BET surface area) 180m²/ G).
* 3: Hydrophobic fumed silica:
Silica prepared by mixing and stirring the hydrophobic fumed silica described in Table 1 and the above organopolysiloxane at room temperature for 2 hours (manufactured by Shin-Etsu Chemical Co., Ltd., moisture content 0.2%, bulk density 50 g / L, primary particles) Diameter 10mμ, specific surface area (BET surface area) 180m²/ G).
* 4: (Surface) Untreated silica:
Silica prepared by mixing and stirring untreated silica described in Table 1 and the above organopolysiloxane at 150 ° C. for 2 hours (manufactured by Shin-Etsu Chemical Co., Ltd., moisture content 1.0%, bulk density 60 g / L, primary particle size 12mμ, specific surface area (BET surface area) 190m²/ G).
[0102]
[Test method]
(A) Viscosity:
The viscosity was determined by measuring the viscosity (Pa · s / 25 ° C.) of the organopolysiloxane coating composition obtained in Table 1 with a B-type viscometer (No. 3 rotor).
(B) Coating physical properties:
The coating properties are as follows: each organopolysiloxane coating composition (A) to (H) is applied on a stainless steel plate and allowed to stand for 7 days at 25 ° C. and 55% RH to be cured to form a coating film having a thickness of 2 mm. I investigated.
[0103]
Table 1 shows the results.
[0104]
[Table 1]

[0105]
Examples 1-4 and Comparative Examples 1-4
In 100 parts by weight of each of the organopolysiloxane coating compositions (A) to (H) obtained in Table 1, silicone oil and xylene were added and mixed with the composition shown in Table 2 and stirred until uniform. A dirty paint composition was obtained.
The property values and paint workability of each antifouling paint were investigated.
[0106]
The results are shown in Table 2.
Further, each of the antifouling paints immediately after the preparation was subjected to an antifouling test.
The results are shown in Table 3.
In Table 2, * 7, 8, 9, 10 and test methods are as follows. Moreover, (parentheses) such as various silicone oil amounts are blending amounts (parts by weight) with respect to 100 parts by weight of the organopolysiloxane (A).
* 7: “SH550”: methylphenyl silicone oil, viscosity: 130 centistokes, manufactured by Toray Dow Corning Silicone.
* 8: “TSF431”: methylphenyl silicone oil, viscosity: 100 centistokes, manufactured by Toshiba Silicones.
* 9: “KF50”: methylphenyl silicone oil, viscosity: 100 centistokes, manufactured by Shin-Etsu Chemical Co., Ltd.
* 10: “KF6016”: polyether-modified silicone oil, viscosity: 150 centistokes, manufactured by Shin-Etsu Chemical Co., Ltd.
[0107]
[Table 2]

[0108]
[Table 3]

[0109]
[Test method]
(I) Paint properties:
The paint property value was measured in the same manner as in Example (A).
The painting workability and antifouling test are as follows.
(B) Paint workability:
70mm x 150mm x 1mm (thick) mild steel plate is attached to the center of a 1000mm x 1000mm x 1mm (thick) tin plate, and airless spray painting is performed while the tin plate is leaned vertically, and equipment during spraying The thickness of the film was confirmed after the coating film was dried.
(C) Antifouling test:
An epoxy base coat is applied to a 100 mm x 300 mm x 5 mm (thickness) PVC plate to a thickness of 200 µm, and each antifouling paint is brush-coated on the coating to a dry film thickness of 150 µm and dried for 3 days. The soil was immersed for 30 months in Miyajima Bay, and the antifouling property was evaluated by visual observation.
(D) Evaluation of paint stability and paint workability:
Moreover, after preparing each antifouling paint, it tested about the paint state (stability) and coating workability | operativity after 50 degreeC and three-month progress.
[0110]
The results are also shown in Table 2 above.
(E) Antifouling test:
Further, after preparing the antifouling paint, an antifouling test was conducted on the antifouling paint after 3 months at 50 ° C.
The results are shown in Table 4.
[0111]
The test method is as follows.
[Test method]
Paint state (stability):
Each antifouling paint shown in Table 2 was put in a can, and left in a 50 ° C. incubator for 3 months in a sealed state. After opening the can, the paint was carefully stirred and inspected with a tab gauge.
[0112]
[Table 4]

[0113]
[Example 5]
5 mol% diphenylsiloxy unit (-Ph per molecule)₂SiO-, Ph: phenyl group), molecular chain (molecules) both ends blocked with hydroxyl groups, 50 parts by weight of dimethylpolysiloxane having a viscosity of 20,000 cS at 25 ° C., and the surface treated with hexamethyldisilazane BET specific surface area 130m²20 parts by weight of hydrophobic fumed silica / g was stirred and mixed at 150 ° C. for 2 hours. Thereafter, it is diluted with 50 parts by weight of dimethylpolysiloxane having 5 mol% of diphenylsiloxy group in one molecule and having both molecular ends blocked with hydroxyl groups and a viscosity of 20,000 cS at 25 ° C. to give methyltributanoxime silane. 10 parts by weight, 0.1 part by weight of dibutyltin dioctoate and 1.0 part by weight of aminopropyltrimethoxysilane were defoamed and mixed. To this composition, 40 parts by weight of xylene was further added to obtain a curable silicone solution of 28 mPa · s. When this was coated on an aluminum wall surface with a coating roll, a coating thickness of 400 microns could be obtained. When this composition was cured under conditions of 23 ° C./55% RH / 7 days, it had gloss on the surface, good transparency, durometer type A hardness: 58, and tensile strength of 4.5 MPa. A cured cured product having excellent rubber properties was obtained.
[0114]
[Comparative Example 5]
50 parts by weight of dimethylpolysiloxane having 5 mol% diphenylsiloxy unit in one molecule, having both ends of the molecular chain blocked with hydroxyl groups and a viscosity of 20,000 cS at 25 ° C., and a BET specific surface area of 200 m²20 parts by weight of fumed silica / g was stirred and mixed at 150 ° C. for 2 hours. Thereafter, it is diluted with 50 parts by weight of dimethylpolysiloxane having 5 mol% diphenylsiloxy group in one molecule and having both molecular chain ends blocked with hydroxyl groups and a viscosity of 20,000 cS at 25 ° C. 10 parts by weight of silane, 0.1 part by weight of dibutyltin dioctoate and 1.0 part by weight of aminopropyltrimethoxysilane were defoamed and mixed. To this composition, 40 parts by weight of xylene was further added to obtain a curable silicone solution of 13 mPa · s. When this was coated on an aluminum wall surface with a coating roll, it was the limit to obtain a coating thickness of 100 microns, and sagging occurred when attempting to obtain a thickness greater than that.
[0115]
[Example 6]
50 parts by weight of dimethylpolysiloxane having a viscosity of 20,000 cS (20,000 cS) at 25 ° C. in which both ends of the molecular chain are blocked with hydroxyl groups, and a BET specific surface area of 130 m treated with hexamethyldisilazane on the surface²10 parts by weight of hydrophobic fumed silica / g was stirred and mixed at 150 ° C. for 2 hours. Then, the molecular chain is blocked with hydroxyl groups at both ends and diluted with 50 parts by weight of dimethylpolysiloxane having a viscosity of 20,000 cS (20,000 cS) at 25 ° C., 10 parts by weight of methyltributanoxime silane, and dibutyltin dioctoate. 0.1 parts by weight and 1.0 part by weight of aminopropyltrimethoxysilane were defoamed and mixed, and 20 parts by weight of methyl ethyl ketone was added to adjust the viscosity to obtain a curable silicone composition having a viscosity of 45 mPa · s. When this composition was coated on an electronic substrate with a dispenser and cured under conditions of 23 ° C./55% RH / 7 days, a silicone film having a very good appearance was formed on the substrate. This film had good rubber properties with a durometer type A hardness of 35 and a tensile strength of 2.7 MPa.
[0116]
[Comparative Example 6]
50 parts by weight of dimethylpolysiloxane having a viscosity of 20,000 cS (20,000 cS) at 25 ° C. with both ends of the molecular chain blocked with hydroxyl groups, and a BET specific surface area of 130 m treated with dimethyldichlorosilane on the surface²/ G hydrophobic fumed silica (15 parts by weight) was mixed at room temperature.
[0117]
Thereafter, the mixture is diluted with 50 parts by weight of dimethylpolysiloxane having a viscosity at 20,000 cS and sealed at both ends with hydroxyl groups, and 10 parts by weight of methyltributanoxime silane and 0.1 parts by weight of dibutyltin dioctate. Then, 1.0 part by weight of aminopropyltrimethoxysilane was defoamed and mixed, 20 parts by weight of methyl ethyl ketone was added to adjust the viscosity, and a curable silicone composition having a viscosity of 80 mPa · s was obtained.
[0118]
Although this composition was coated on an electronic substrate with a dispenser, it was inferior in dischargeability from a nozzle and was cured under the conditions of 23 ° C./55% RH / 7 days. An erased silicone film was formed.
[0119]
[Example 7]
50 parts by weight of dimethylpolysiloxane having a viscosity of 5,000 cS with both ends blocked with hydroxyl groups and a viscosity at 5,000 cs, and a BET specific surface area of 130 m treated with hexamethyldisilazane²10 parts by weight of hydrophobic fumed silica / g was stirred and mixed at 150 ° C. for 2 hours. Thereafter, the mixture was diluted with 50 parts by weight of dimethylpolysiloxane having a viscosity of 5,000 cS having both ends blocked with hydroxyl groups and having a viscosity at 25 ° C., then 2.0 parts by weight of zinc carbonate, 10 parts by weight of vinyltributanoxime silane, A curable silicone composition having a viscosity of 15 mPa · s was obtained by mixing 1.5 parts by weight of aminopropyltrimethoxysilane and a platinum catalyst so that the concentration of platinum atoms was 300 ppm. When this composition was dip-coated on glass fiber and cured under the conditions of 23 ° C./55% RH / 7 days, a good flame-retardant coating film having a substantially uniform film thickness of about 1 mm was obtained.
[0120]
[Comparative Example 7]
50 parts by weight of dimethylpolysiloxane having a viscosity of 5,000 cS with both ends of the molecular chain blocked with hydroxyl groups and a viscosity at 5,000 cS, and a BET specific surface area of 200 m²10 parts by weight of fumed silica / g was stirred and mixed at 150 ° C. for 2 hours. Thereafter, the mixture is diluted with 50 parts by weight of dimethylpolysiloxane having a viscosity of 5,000 cS at 25 ° C., both ends of which are blocked with hydroxyl groups, and then 2.0 parts by weight of zinc carbonate and 10 parts by weight of vinyltributanoxime silane. Then, 1.5 parts by weight of aminopropyltrimethoxysilane and a platinum catalyst were mixed so that the concentration of platinum atoms was 300 ppm to obtain a curable silicone composition having a viscosity of 4 Pa · s. When this composition is dip-coated on glass fiber and cured under conditions of 23 ° C./55% RH / 7 days, dripping or dripping occurs during curing, and a flame-retardant cured product with a uniform film thickness cannot be obtained. It was.
[0121]
[Example 8]
100 parts by weight of dimethylpolysiloxane having a viscosity of 1,000,000 cS at 25 ° C. with both ends of the molecular chain blocked with hydroxyl groups, and a BET specific surface area of 130 m treated with dimethyldichlorosilane on the surface²45 parts by weight of hydrophobic fumed silica / g and 10 parts by weight of 13-dimethylpolysiloxane having an average polymerization degree of 13 with both molecular chains blocked with hydroxyl groups were stirred and mixed at 150 ° C. for 2 hours. When 10 parts by weight of vinyltributanoxime silane, 1.5 parts by weight of aminopropyltrimethoxysilane, and 65 parts by weight of xylene were added to this composition, the viscosity with a BL rotational viscometer was 100 Pa · s, 20 A composition having a high thixotropy of 15 Pa · s was obtained by rotation. When this composition is cured at 23 ° C./55% RH / 7 days, a cured coating product having good rubber properties with good transparency, durometer type A hardness: 65, and tensile strength of 6.5 MPa is obtained. It was.
[0122]
[Comparative Example 8]
100 parts by weight of dimethylpolysiloxane having a viscosity of 1,000,000 cS at 25 ° C. in which both ends of the molecular chain are blocked with hydroxyl groups, and a BET specific surface area of 200 m²45 parts by weight of fumed silica / g and 10 parts by weight of dimethylpolysiloxane having an average polymerization degree of 13 in which both molecular chain ends are blocked with hydroxyl groups were stirred and mixed at 150 ° C. for 2 hours. When 10 parts by weight of vinyltributanoxime silane, 1.5 parts by weight of aminopropyltrimethoxysilane and 65 parts by weight of xylene were further added to this composition, the viscosity with a BL rotational viscometer was 12 Pa · s, 20 at 20 rpm. In rotation, it was 9 Pa · s and the thixotropy was quite low.
[0123]
[Comparative Example 9]
100 parts by weight of dimethylpolysiloxane whose molecular chain both ends are blocked with hydroxyl groups and whose viscosity at 25 ° C. is 1,000,000 cS and whose surface is treated with dimethyldichlorosilane is 200 m.²45 parts by weight of hydrophobic fumed silica / g and 10 parts by weight of dimethylpolysiloxane having an average degree of polymerization of 13 with both molecular chain ends blocked with hydroxyl groups were stirred and mixed at room temperature for 2 hours. When 10 parts by weight of vinyltributanoxime silane, 1.5 parts by weight of aminopropyltrimethoxysilane and 65 parts by weight of xylene were further added to this composition, the viscosity with a BM rotational viscometer was 850 Pa · s, 20 In rotation, the viscosity was 180 Pa · s, but the viscosity was extremely high although the thixotropy was high.
[0124]
[Example 9]
Both ends of the molecular chain are trimethoxysiloxy groups (—O—Si— (OCH_Three)_Three) Blocked at 25 ° C. and having a viscosity of 20,000 cS (20,000 cS), 50 parts by weight of dimethylpolysiloxane, and a BET specific surface area of 130 m treated with hexamethyldisilazane on the surface.²10 parts by weight of hydrophobic fumed silica / g was stirred and mixed at 150 ° C. for 2 hours. Thereafter, the molecular chain ends are blocked with trimethoxysiloxy groups and diluted with 50 parts by weight of dimethylpolysiloxane having a viscosity of 20,000 cS (20,000 cS) at 25 ° C., 5 parts by weight of methyltrimethoxysilane, dibutyltin 0.1 part by weight of octoate and 1.0 part by weight of aminopropyltrimethoxysilane are defoamed and mixed, 20 parts by weight of methyl ethyl ketone is added to adjust the viscosity, and a curable silicone composition having a viscosity of 400 mPa · s (L ) (Curable composition L) was obtained. When this composition was cured under the conditions of 23 ° C./55% RH / 7 days, a silicone film having a very good appearance was formed on the substrate. The cured product had good rubber properties with a durometer type A hardness of 40 and a tensile strength of 2.0 MPa. (According to JIS 6249)
[0125]
[Comparative Example 10]
50 parts by weight of dimethylpolysiloxane having a viscosity of 20,000 cS (20,000 cS) at 25 ° C. in which both ends of the molecular chain are blocked with a trimethoxysiloxy group, and a BET specific surface area of 200 m²10 parts by weight of / g hydrophobic fumed silica was stirred and mixed at room temperature for 2 hours. Thereafter, both ends of the molecular chain are blocked with trimethoxysiloxy groups and diluted with 50 parts by weight of dimethylpolysiloxane having a viscosity of 20,000 cS at 25 ° C., 5 parts by weight of methyltrimethoxysilane, 0.1% of dibutyltin dioctoate 0.1% Part by weight and 1.0 part by weight of aminopropyltrimethoxysilane were defoamed and mixed, and the viscosity was adjusted by adding 20 parts by weight of methyl ethyl ketone to obtain a curable silicone composition (M) having a viscosity of 480 mPa · s. Although this composition (M) was coated on the electronic substrate with a dispenser, it was inferior in dischargeability from the nozzle as compared with the composition of Example 9, and was cured under conditions of 23 ° C./55% RH / 7 days. As a result, a milky surface-matte silicone coating film was formed on the substrate. This cured product had a durometer type A hardness of 35 and a tensile strength of 2.0 MPa. Thus, according to Examples 5-9 and Comparative Examples 5 to 10 (according to JIS 6249), the curable compositions of the present invention have low viscosity and high thixotropy, and workability during coating. It can be seen that the coating film strength and surface smoothness are excellent.
[0126]
Examples 10 to 15 and Comparative Examples 11 to 14
In Example 1, instead of the organopolysiloxane composition (A), the curable silicone composition (L) described in Example 9 was used in Examples 10 to 15, and Comparative Example 10 was used in Comparative Examples 11 to 14. An antifouling coating composition was prepared in the same manner as in Example 1 except that the curable silicone composition (M) described in 1 was used, and silicone oil and xylene were used in amounts as shown in Table 5, respectively. Various physical properties were evaluated in the same manner as in Example 1.
[0127]
The results are shown in Tables 5-8.
Table 5 shows the property values and paint workability when made into a paint as in Table 2, Table 6 shows the antifouling property after paint, as in Table 3, and Table 7 shows in Table 2 Similarly to Table 4, the property values of the paint after storage for a predetermined period are shown, and Table 8 shows the antifouling property of the paint after storage as in Table 4.
[0128]
[Table 5]

[0129]
[Table 6]

[0130]
[Table 7]

[0131]
[Table 8]

Claims (14)

(A) A curable composition containing an organopolysiloxane having a condensation-reactive functional group at both ends of a molecule and (B) hydrophobic silica, wherein the hydrophobic silica (B) is an organopolysiloxane ( An antifouling paint composition comprising A) and a heat-treated curable composition . The organopolysiloxane (A) has the following formula [α]:

(Wherein, W represents a hydroxyl group or a hydrolyzable group, R ¹ and R each independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and a plurality of R ¹ , R represents respectively may be the same or different, n represents indicates an integer of 5 or more, a is an antifouling coating composition according to claim 1 which is a compound represented by.) indicating 0, 1 or 2 Thing . In addition to the component (A) in which W in the formula [α] is a hydroxyl group and a is 2 and the component (B), the formula (I): R ¹ _b SiX _4-b (In the formula [I], R ¹ represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, X represents a hydrolyzable group, and b represents 0 or 1) The antifouling paint composition according to claim 2, comprising an organosilane represented by the formula (1) or a partial hydrolyzate thereof . The antifouling paint composition according to any one of claims 1 to 3, wherein the hydrophobic silica is heat-treated with the component (A) at a temperature of 100 ° C or higher. The antifouling paint composition according to any one of claims 1 to 4, wherein the component (B) is contained in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the component (A). The antifouling paint composition according to claim 3, comprising the component (C) in an amount of 1 to 20 parts by weight based on 100 parts by weight of the component (A). Furthermore, the silicone oil (D) is contained in an amount of 0.1 to 200 parts by weight in total with respect to 100 parts by weight of the component (A). The antifouling paint composition as described. The antifouling paint composition according to any one of claims 1 to 7, further comprising a catalyst, an antifouling agent and / or a colorant. An antifouling coating film comprising the antifouling paint composition according to any one of claims 1 to 8 . An antifouling property characterized in that the surface of a base material in contact with seawater or fresh water is coated with a coating film obtained by curing the antifouling paint composition according to any one of claims 1 to 8 . Base material. The antifouling substrate according to claim 10 , wherein the substrate is any one of an underwater structure, a ship outer plate, a fishing net, and fishing gear. A base material characterized in that a surface of the base material is coated or impregnated with the antifouling paint composition according to any one of claims 1 to 8 , and then the composition is cured to form a coating film. A method for forming a coating film on a surface. An antifouling paint composition according to any one of claims 1 to 8 is applied or impregnated on the surface of a substrate, and then the antifouling paint is cured to form an antifouling coating film. , Antifouling method for substrate. The antifouling method for a base material according to claim 13 , wherein the base material is any one of an underwater structure, a ship outer plate, a fishing net, and fishing gear.