JP3834948B2 - fiber - Google Patents

Description

【００３１】
（式中、Ｘはハロゲン原子、アルコキシ基、アシロキシ基、アミノキシ基、フェノキシ基、チオアルコキシ基、アミノ基等の加水分解性基または水酸基を示し、Ｒ⁸は水素原子、炭素数１〜１０のアルキル基または炭素数１〜１０のアラルキル基を示し、ｉは１〜３の整数である。）で表される。
（Ｃ２）成分としては、例えば、
（イ）前記一般式（４）に対応するヒドロシラン化合物（以下、「ヒドロシラン化合物（イ）」という。）を、炭素−炭素二重結合を有するビニル系重合体（以下、「不飽和ビニル系重合体」という。）中の該炭素−炭素二重結合に付加反応させる方法、
（ロ）下記一般式（５）
【００３２】
【化２】

【００３３】
（式中、Ｘ、Ｒ⁸、ｉは一般式（４）におけるそれぞれＸ、Ｒ⁸、ｉと同義であり、Ｒ⁹は重合性二重結合を有する有機基を示す。）で表されるシラン化合物（以下、「不飽和シラン化合物（ロ）」という。）と、他のビニル系単量体とを共重合する方法等により製造されるものを挙げることができる。
【００３４】
前記（イ）の方法に使用されるヒドロシラン化合物（イ）としては、例えば、メチルジクロルシラン、トリクロルシラン、フェニルジクロルシラン等のハロゲン化シラン類；メチルジエトキシシラン、メチルジメトキシシラン、フェニルジメトキシシラン、トリメトキシシラン、トリエトキシシラン等のアルコキシシラン類；メチルジアセトキシシラン、フェニルジアセトキシシラン、トリアセトキシシラン等アシロキシシラン類；メチルジアミノキシシラン、トリアミノキシシラン、ジメチル・アミノキシシラン等のアミノキシシラン類等を挙げることができる。
これらのヒドロシラン化合物（イ）は、単独でまたは２種以上を組み合わせて使用することができる。
【００３５】
また、前記（イ）の方法に使用される不飽和ビニル系重合体は、水酸基を有する重合体以外であれば特に限定されず、例えば、下記（イ−１）や（イ−２）の方法あるいはこれらの組み合わせ等によって製造することができる。
即ち、
（イ−１）官能基（以下、「官能基（α）」という。）を有するビニル系単量体を（共）重合したのち、該（共）重合体中の官能基（ｉ）に、該官能基（α）と反応しうる官能基（以下、「官能基（β）」という。）と炭素・炭素二重結合とを有する不飽和化合物を反応させることにより、重合体分子鎖の側鎖に炭素−炭素二重結合を有する不飽和ビニル系重合体を製造することができる。
（イ−２）官能基（α）を有するラジカル重合開始剤（例えば４，４−アゾビス−４−シアノ吉草酸等）を使用し、あるいはラジカル重合開始剤と連鎖移動剤の双方に官能基（α）を有する化合物（例えば４，４−アゾビス−４−シアノ吉草酸とジチオグリコール酸等）を使用して、ビニル系単量体を（共）重合して、重合体分子鎖の片末端あるいは両末端にラジカル重合開始剤や連鎖移動剤に由来する官能基（α）を有する（共）重合体を合成したのち、該（共）重合体中の官能基（α）に、官能基（β）と炭素・炭素二重結合とを有する不飽和化合物を反応させることにより、重合体分子鎖の片末端あるいは両末端に炭素−炭素二重結合を有する不飽和ビニル系重合体を製造することができる。
【００３６】
（イ−１）および（イ−２）の方法における官能基（α）と官能基（β）との反応の例としては、カルボキシル基と水酸基とのエステル化反応、カルボン酸無水物基と水酸基との開環エステル化反応、カルボキシル基とエポキシ基とのエステル化反応、カルボキシル基とアミノ基とのアミド化反応、カルボン酸無水物基とアミノ基との開環アミド化反応、エポキシ基とアミノ基との開環付加反応、水酸基とイソシアネート基とのウレタン化反応や、これらの反応の組み合わせ等を挙げることができる。
【００３７】
官能基（α）を有するビニル系単量体としては、例えば、（メタ）アクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸等の不飽和カルボン酸；無水マレイン酸、無水イタコン酸等の不飽和カルボン酸無水物；２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、３−ヒドロキシプロピル（メタ）アクリレート、Ｎ−メチロール（メタ）アクリルアミド、２−ヒドロキシエチルビニルエーテル等の水酸基含有ビニル系単量体；２−アミノエチル（メタ）アクリレート、２−アミノプロピル（メタ）アクリレート、３−アミノプロピル（メタ）アクリレート、２−ジメチルアミノエチル（メタ）アクリレート、２−ジエチルアミノエチル（メタ）アクリレート、２−ジメチルアミノプロピル（メタ）アクリレート、３−ジメチルアミノプロピル（メタ）アクリレート、２−アミノエチルビニルエーテル、Ｎ，Ｎ−ジメチルアミノ（メタ）アクリルアミド、Ｎ，Ｎ−ジエチルアミノ（メタ）アクリルアミド等のアミノ基含有ビニル系単量体；１，１，１−トリメチルアミン（メタ）アクリルイミド、１−メチル−１−エチルアミン（メタ）アクリルイミド、１，１−ジメチル−１−（２−ヒドロキシプロピル）アミン（メタ）アクリルイミド、１，１−ジメチル−１−（２’−フェニル−２’−ヒドロキシエチル）アミン（メタ）アクリルイミド、１，１−ジメチル−１−（２’−ヒドロキシ−２’−フェノキシプロピル）アミン（メタ）アクリルイミド等のアミンイミド基含有ビニル系単量体、グリシジル（メタ）アクリレート、アリルグリシジルエーテル等のエポキシ基含有ビニル系単量体等を挙げることができる。
これらの官能基（α）を有するビニル系単量体は、単独でまたは２種以上を組み合わせて使用することができる。
【００３８】
官能基（α）を有するビニル系単量体と共重合させる他のビニル系単量体としては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリル酸ｉ−プロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸ｔ−ブチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリルアミド、クロトンアミド、マレイン酸ジアミド、フマル酸ジアミド、イタコン酸ジアミド、α−エチルアクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミド、（メタ）アクリロニトリル、スチレン、α−メチルスチレン、塩化ビニル、酢酸ビニル、プロピオン酸ビニル等を挙げることができる。
これらの他のビニル系単量体は、単独でまたは２種以上を組み合わせて使用することができる。
【００３９】
官能基（β）と炭素・炭素二重結合とを有する不飽和化合物としては、例えば、官能基（α）を有するビニル系単量体と同様のビニル系単量体や、前記水酸基含有ビニル系単量体とジイソシアネート化合物とを等モルで反応させることにより得られるイソシアネート基含有不飽和化合物等を挙げることができる。
【００４０】
また、前記（ロ）の方法に使用される不飽和シラン化合物（ロ）の具体例としは、
ＣＨ₂＝ＣＨ（ＣＨ₃）Ｓｉ（ＯＣＨ₃）₂ 、
ＣＨ₂＝ＣＨＳｉ（ＯＣＨ₃）₃、
ＣＨ₂＝ＣＨ（ＣＨ₃）ＳｉＣｌ₂、ＣＨ₂＝ＣＨＳｉＣｌ₃、
ＣＨ₂＝ＣＨＣＯＯ（ＣＨ₂）₃Ｓｉ（ＯＣＨ３）₂ 、
ＣＨ₂＝ＣＨＣＯＯ（ＣＨ₂）₃Ｓｉ（ＣＨ₃）（ＯＣＨＲ₃）₃ 、
ＣＨ₂＝ＣＨＣＯＯ（ＣＨ₂）₃Ｓｉ（ＣＨ₃）Ｃｌ₂、
ＣＨ₂＝ＣＨＣＯＯ（ＣＨ₂）₃ＳｉＣｌ₃、
ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯＯ（ＣＨ₂）₃Ｓｉ（ＣＨ₃）（ＯＣＨ₃）₂ 、
ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯＯ（ＣＨ２）₃Ｓｉ（ＣＨ₃）（ＯＣＨ₃）₂ 、
ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯＯ（ＣＨ₂）₃ＳｉＣｌ₂ 、
ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯＯ（ＣＨ₂）₃ＳｉＣｌ₃ 、
【００４１】
【化３】

【００４２】
【化４】

【００４３】
【化５】

【００４４】
【化６】

【００４５】
等を挙げることができる。
これらの不飽和シラン化合物（ロ）は、単独でまたは２種以上を組み合わせて使用することができる。
また、不飽和シラン化合物（ロ）と共重合させる他のビニル系単量体としては、例えば、前記（イ−１）の方法について例示した官能基（α）を有するビニル系単量体や他のビニル系単量体等の１種以上を挙げることができる。
【００４６】
以上のようにして得られる（Ｃ２）成分の好ましい例を、より具体的に示すと、下記一般式（６）
【００４７】
【化７】

【００４８】
（式中、Ｒ¹⁰は水素原子またはメチル基を示し、Ｒ¹¹はメチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｉ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基等の炭素数１〜６のアルキル基を示し、Ｒ¹²はＲ¹⁰と同義であり、Ｒ¹³はメチレン基、エチレン基、プロピレン基、ブチレン基等の炭素数１〜４のアルキレン基を示し、Ｒ¹⁴はＲ¹¹と同義であり、ｋ／（ｊ＋ｋ）＝０．０１〜０．４、好ましくは０．０２〜０．２である。）で表されるトリアルコキシシリル基含有（メタ）アクリレート系共重合体を挙げることができる。
【００４９】
また、（Ｃ２）成分の他の具体例としては、特定シリル基含有エポキシ樹脂、特定シリル基含有ポリエステル樹脂、特定シリル基含有フッ素樹脂等を挙げることができる。
前記特定シリル基含有エポキシ樹脂は、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、脂肪族ポリグリシジルエーテル、脂肪族ポリグリシジルエステル等のエポキシ樹脂中のエポキシ基に、特定シリル基を有するアミノシラン類、ビニルシラン類、カルボキシシラン類、、グリシジルシラン類等を反応させることにより製造することができる。
また、前記特定シリル基含有ポリエステル樹脂は、例えば、ポリエステル樹脂中に含有されるカルボキシル基や水酸基に、特定シリル基を有するアミノシラン類、カルボキシシラン類、グリシジルシラン類等を反応させることにより製造することができる。
また、前記特定シリル基含有フッ素樹脂は、例えば、フッ化エチレン等の（共）重合体中に含有されるカルボキシル基や水酸基に、特定シリル基を有するアミノシラン類、カルボキシシラン類、グリシジルシラン類等を反応させることにより製造することができる。
【００５０】
（Ｃ２）成分のポリスチレン換算数平均分子量（以下、「Ｍｎ」という。）は、好ましくは２，０００〜１００，０００、さらに好ましくは４，０００〜５０，０００である。
第２組成物において、（Ｃ２）成分は、単独でまたは２種以上を組み合わせて使用することができる。
第２組成物における（Ｃ２）成分の使用量は、（Ａ２）成分におけるオルガノシラン（２）１００重量部に対して、通常、２〜９００重量部、好ましくは１０〜４００重量部、さらに好ましくは２０〜２００重量部である。この場合、（Ｃ２）成分の使用量が２重量部未満では、得られる塗膜の耐アルカリ性が低下する傾向があり、一方９００重量部を超えると、塗膜の耐候性が低下する傾向がある。
【００５１】
さらに、第１組成物および第２組成物には、下記する（Ｄ）〜（Ｇ）成分を配合することができる。
（Ｄ）成分
（Ｄ）成分は、第１組成物においては、（Ａ１）成分等の加水分解・縮合反応を促進し、また第２組成物においては、（Ａ２）成分、（Ｃ２）成分等の加水分解・縮合反応を促進する触媒からなる。
第１組成物および第２組成物においては、（Ｄ）成分を使用することにより、得られる塗膜の硬化速度を高めるとともに、使用されるオルガノシラン成分の重縮合反応により生成するポリシロキサン樹脂のＭｎが大きくなり、強度、長期耐久性等に優れた塗膜を得ることができ、かつ塗膜の厚膜化や塗装作業も容易となる。このような（Ｄ）成分としては、酸性化合物、アルカリ性化合物、有機金属化合物および／またはその部分加水分解物（以下、有機金属化合物および／またはその部分加水分解物をまとめて「有機金属化合物等」という。）が好ましい。
【００５２】
（Ｄ）成分のうち、酸性化合物としては、例えば、酢酸、塩酸、硫酸、リン酸、アルキルチタン酸、ｐ−トルエンスルホン酸、フタル酸等を挙げることができ、好ましくは酢酸である。
また、アルカリ性化合物としては、例えば、水酸化ナトリウム、水酸化カリウム等を挙げることができ、好ましくは水酸化ナトリウムである。
また、有機金属化合物等としては、例えば、下記一般式
Ｍ（ＯＲ¹⁵）ｐ（Ｒ¹⁶ＣＯＣＨＣＯＲ¹⁷）ｑ
（式中、Ｍはジルコニウム、チタンまたはアルミニウムを示し、Ｒ¹⁵およびＲ¹⁶は、それぞれ独立にエチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、シクロヘキシル基、フェニル基等の炭素数１〜６の１価の炭化水素基を示し、Ｒ¹⁷は、Ｒ¹⁵およびＲ¹⁶と同様の炭素数１〜６の１価の炭化水素基のほか、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｉ−プロポキシ基、ｎ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔ−ブトキシ基、ラウリルオキシ基、ステアリルオキシ基等の炭素数１〜１６のアルコキシル基を示し、ｐおよびｑは０〜４の整数で、（ｐ＋ｑ）＝（Ｍの原子価）である。）で表される化合物、あるいはこれらの化合物の部分加水分解物を挙げることができる。
【００５３】
有機金属化合物等の具体例としては、テトラ−ｎ−ブトキシジルコニウム、トリ−ｎ−ブトキシ・エチルアセトアセテートジルコニウム、ジ−ｎ−ブトキシ・ビス（エチルアセトアセテート）ジルコニウム、ｎ−ブトキシ・トリス（エチルアセトアセテート）ジルコニウム、テトラキス（ｎ−プロピルアセトアセテート）ジルコニウム、テトラキス（アセチルアセトアセテート）ジルコニウム、テトラキス（エチルアセトアセテート）ジルコニウム等の有機ジルコニウム化合物；テトラ−ｉ−プロポキシチタニウム、ジ−ｉ−プロポキシ・ビス（エチルアセトアセテート）チタニウム、ジ−ｉ−プロポキシ・ビス（アセチルアセテート）チタニウム、ジ−ｉ−プロポキシ・ビス（アセチルアセトン）チタニウム等の有機チタン化合物；トリ−ｉ−プロポキシアルミニウム、ジ−ｉ−プロポキシ・エチルアセトアセテートアルミニウム、ジ−ｉ−プロポキシ・アセチルアセトナートアルミニウム、ｉ−プロポキシ・ビス（エチルアセトアセテート）アルミニウム、ｉ−プロポキシ・ビス（アセチルアセトナート）アルミニウム、トリス（エチルアセトアセテート）アルミニウム、トリス（アセチルアセトナート）アルミニウム、モノアセチルアセトナート・ビス（エチルアセトアセテート）アルミニウム等の有機アルミニウム化合物や、これらの化合物の部分加水分解物等を挙げることができる。
これらのうち、トリ−ｎ−ブトキシ・エチルアセトアセテートジルコニウム、ジ−ｉ−プロポキシ・ビス（アセチルアセトナート）チタニウム、ジ−ｉ−プロポキシ・エチルアセトアセテートアルミニウム、トリス（エチルアセトアセテート）アルミニウム、あるいはこれらの化合物の部分加水分解物が好ましい。
（Ｄ）成分は、単独でまたは２種以上を組み合わせて使用することができる。
【００５４】
第１組成物および第２組成物における（Ｄ）成分の使用量は、有機金属化合物等以外の場合、前記（Ａ１）成分におけるオルガノシランの合計１００重量部あるいは前記（Ａ２）成分におけるオルガノシランの合計１００重量部に対して、通常、０〜１００重量部、好ましくは０．０１〜８０重量部、さらに好ましくは０．１〜５０重量部であり、有機金属化合物等の場合、前記（Ａ１）成分におけるオルガノシランの合計１００重量部あるいは前記（Ａ２）成分におけるオルガノシランの合計１００重量部に対して、通常、０〜１００重量部、好ましくは０．１〜８０重量部、さらに好ましくは０．５〜５０重量部である。この場合、（Ｄ）成分の使用量が１００重量部を超えると、組成物の保存安定性が低下したり、塗膜にクラックが発生しやすくなる傾向がある。
【００５５】
（Ｅ）成分
（Ｅ）成分は、下記一般式
Ｒ¹⁸ＣＯＣＨ₂ＣＯＲ¹⁹
（式中、Ｒ¹⁸およびＲ¹⁹は、前記金属キレート化合物における各一般式のそれぞれＲ¹⁶およびＲ¹⁷と同義である。）で表されるβ−ジケトン類およびβ−ケトエステル類、カルボン酸化合物、ジヒドロキシ化合物、アミン化合物ならびにオキシアルデヒド化合物からなる群から選択される少なくとも１種からなる。このような（Ｅ）成分は、前記（Ｄ）成分のうち有機金属化合物等を使用する場合に併用することが好ましい。
（Ｅ）成分は、第１および第２組成物の安定向上剤として作用するものである。即ち、(Ｅ）成分が前記有機金属化合物等の金属原子に配位することにより、該有機金属化合物等による前記（Ａ１）成分、（Ａ２）成分、（Ｃ２）成分等の縮合反応を促進する作用を適度にコントロールすることにより、得られる組成物の保存安定性をさらに向上させる作用をなすものと考えられる。
（Ｅ）成分の具体例としては、アセチルアセトン、アセト酢酸メチル、アセト酢酸エチル、アセト酢酸−ｎ−プロピル、アセト酢酸−ｉ−プロピル、アセト酢酸−ｎ−ブチル、アセト酢酸−ｓｅｃ−ブチル、アセト酢酸−ｔ−ブチル、ヘキサン−２，４−ジオン、ヘプタン−２，４−ジオン、ヘプタン−３，５−ジオン、オクタン−２，４−ジオン、ノナン−２，４−ジオン、５−メチルヘキサン−２，４−ジオン、マロン酸、しゅう酸、フタル酸、グリコール酸、サリチル酸、アミノ酢酸、イミノ酢酸、エチレンジアミン四酢酸、グリコール、カテコール、エチレンジアミン、２，２−ビピリジン、１，１０−フェナントロリン、ジエチレントリアミン、２−エタノールアミン、ジメチルグリオキシム、ジチゾン、メチオニン、サリチルアルデヒド等を挙げることができる。
これらのうち、アセチルアセトン、アセト酢酸エチル、２−エタノールアミンが好ましい。
（Ｅ）成分は、単独でまたは２種以上を組み合わせて使用することができる。第１組成物および第２組成物における（Ｅ）成分の使用量は、前記有機金属化合物等における有機金属化合物１モルに対して、通常、２モル以上、好ましくは３〜２０モルである。
【００５６】
（Ｆ）成分
（Ｆ）成分は、前記（Ｂ）成分以外の無機微粒子であり、塗膜の所望の特性に応じて配合される。
（Ｆ）成分の無機微粒子の具体例としては、ＳｉＯ₂、Ａｌ₂Ｏ₃、Ａｌ(ＯＨ)₃、Ｓｂ₂Ｏ₅、Ｓｉ₃Ｎ₄、Ｓｎ−Ｉｎ₂Ｏ₃、Ｓｂ−Ｉｎ₂Ｏ₃、ＭｇＦ、ＣｅＦ₃、ＴｉＯ₂、ＺｎＯ、ＣｅＯ₂、ＳｉＯ₂、Ａｌ₂Ｏ₃、３Ａｌ₂Ｏ₃・２ＳｉＯ₂、ＢｅＯ、ＳｉＣ、ＡｌＮ、Ａｌ₂Ｏ₃、Ｆｅ、Ｆｅ₂Ｏ₃、Ｃｏ、Ｃｏ−ＦｅＯＸ、ＣｒＯ₂、Ｆｅ₄Ｎ、Ｂａフェライト、ＳｍＣＯ₅、ＹＣＯ₅、ＣｅＣＯ₅、ＰｒＣＯ₅、Ｓｍ₂ＣＯ₁₇、Ｎｄ₂Ｆｅ₁₄Ｂ、ＺｒＯ₂、Ａｌ₄Ｏ₃、ＡｌＮ、ＳｉＣ、ＢｅＯ等を挙げることができる。
【００５７】
（Ｆ）成分は、(i)微粒子からなる粉体、(ii)微粒子が水中に分散した水系のゾルもしくはコロイド、(iii)微粒子がイソプロピルアルコ−ル等の極性溶媒やトルエン等の非極性溶媒中に分散した溶媒系のゾルもしくはコロイドとして存在する。溶媒系のゾルもしくはコロイドの場合、上記微粒子の分散性によってはさらに水や溶媒にて希釈して用いてもよい。
（Ｆ）成分が水系のゾルもしくはコロイドおよび溶媒系のゾルもしくはコロイドである場合の固形分濃度は、４０重量％以下が好ましい。
（Ｆ）成分は、単独でまたは２種以上を組み合わせて使用することができる。
（Ｆ）成分を第１または第２組成物中に配合する方法としては、これら組成物の調製後に添加してもよく、あるいは組成物の調製時に添加して、（Ｆ）成分を、第１組成物においては、前記（Ａ１）成分、（Ｂ）成分等と共に加水分解し、且つ共部分縮合させてもよく、また第２組成物においては、前記（Ａ２）成分、（Ｂ）成分、（Ｃ２）成分等と共に加水分解し、且つ共部分縮合させてもよい。
第１組成物および第２組成物における（Ｆ）成分の使用量は、前記（Ａ１）成分におけるオルガノシランの合計１００重量部あるいは前記（Ａ２）成分におけるオルガノシランの合計１００重量部に対して、固形分で、通常、０〜５００重量部、好ましくは０．１〜４００重量部である。
【００５８】
（Ｇ）成分
（Ｇ）成分は、前記（Ｄ）成分以外の硬化促進剤からなる。このような（Ｇ）成分を使用することにより、コーティング用組成物である第１組成物および第２組成物から形成される塗膜の硬化速度を高めることができ、しかも比較的低い温度で硬化させることができる。
（Ｇ）成分としては、例えば、ナフテン酸、オクチル酸、亜硝酸、亜硫酸、アルミン酸、炭酸等のアルカリ金属塩；エチレンジアミン、ヘキサンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ピペリジン、ピペラジン、メタフェニレンジアミン、エタノールアミン、トリエチルアミン、３−アミノプロピルトリエトキシシラン、３−（２−アミノエチル）−アミノプロピルトリメトキシシラン、３−（２−アミノエチル）−アミノプロピルメチルジメトキシシラン、３−アミノプロピルトリメトキシシランや、エポキシ樹脂の硬化剤として用いられる各種変性アミン等のアミン系化合物；（Ｃ₄Ｈ₉）₂Ｓｎ（ＯＣＯＣ₁₁Ｈ₂₃）₂、（Ｃ₄Ｈ₉）₂Ｓｎ（ＯＣＯＣＨ＝ＣＨＣＯＯＣＨ₃）₂ 、（Ｃ₄Ｈ₉）₂Ｓｎ（ＯＣＯＣＨ＝ＣＨＣＯＯ（Ｃ₄Ｈ₉）₂ 、（Ｃ₈Ｈ₁₇）₂Ｓｎ（ＯＣＯＣ₁₁Ｈ₂₃）₂、（Ｃ₈Ｈ₁₇）₂Ｓｎ（ＯＣＯＣＨ＝ＣＨＣＯＯＣＨ₃）₂ 、（Ｃ₈Ｈ₁₇）₂Ｓｎ（ＯＣＯＣＨ＝ＣＨＣＯＯ（Ｃ₄Ｈ₉）₂ 、（Ｃ₈Ｈ₁₇）₂Ｓｎ（ＯＣＯＣＨ＝ＣＨＣＯＯＣ₈Ｈ₁₇）₂、Ｓｎ(ＯＣＯＣＣ₈Ｈ₁₇）₂等のカルボン酸型有機錫化合物；（Ｃ₄Ｈ₉）₂Ｓｎ（ＳＣＨ₂ＣＯＯＣ₈Ｈ₁₇）₂、（Ｃ₄Ｈ₉）₂Ｓｎ（ＳＣＨ₂ＣＨ₂ＣＯＯＣ₈Ｈ₁₇）₂、（Ｃ₈Ｈ₁₇）₂Ｓｎ（ＳＣＨ₂ＣＯＯＣ₈Ｈ₁₇）₂、（Ｃ₈Ｈ₁₇）₂Ｓｎ（ＳＣＨ₂ＣＨ₂ＣＯＯＣ₈Ｈ₁₇）₂、（Ｃ₈Ｈ₁₇）₂Ｓｎ（ＳＣＨ₂ＣＯＯＣ₁₂Ｈ₂₅）₂、（Ｃ₈Ｈ₁₇）₂Ｓｎ（ＳＣＨ₂ＣＨ₂ＣＯＯＣ₁₂Ｈ₂₅）₂
【００５９】
【化８】

等のメルカプチド型有機錫化合物；
【００６０】
（Ｃ₄Ｈ₉）₂Ｓｎ＝Ｓ、（Ｃ₈Ｈ₁₇）₂Ｓｎ＝Ｓ、
【００６１】
【化９】

【００６２】
等のスルフィド型有機錫化合物；
（Ｃ₄Ｈ₉）₂ＳｎＯ、（Ｃ₈Ｈ₁₇）₂ＳｎＯ等の有機錫オキサイドや、これらの有機錫オキサイドとエチルシリケート、マレイン酸ジメチル、マレイン酸ジエチル、フタル酸ジオクチル等のエステル化合物との反応生成物等を挙げることができる。
（Ｇ）成分は、単独でまたは２種以上を組み合わせて使用することができる。（Ｇ）成分の使用量は、第１組成物においては、前記（Ａ１）成分におけるオルガノシラン（Ｉ）１００重量部に対して、通常、０〜１００重量部、好ましくは０．１〜８０重量部、さらに好ましくは０．５〜５０重量部であり、また第２組成物においては、前記（Ａ２）成分におけるオルガノシラン（２）１００重量部に対して、通常、０〜１００重量部、好ましくは０．１〜８０重量部、さらに好ましくは０．５〜５０重量部である。
【００６３】
また、第１組成物または第２組成物には、得られる塗膜の着色、厚膜化等のために、別途充填材を添加・分散させることもできる。
このような充填材としては、例えば、非水溶性の有機顔料や無機顔料、顔料以外の、粒子状、繊維状もしくは鱗片状のセラミックス、金属あるいは合金、ならびにこれらの金属の酸化物、水酸化物、炭化物、窒化物、硫化物等を挙げることができる。
前記充填材の具体例としては、鉄、銅、アルミニウム、ニッケル、銀、亜鉛、フェライト、カーボンブラック、ステンレス鋼、二酸化ケイ素、酸化チタン（ルチル型等）、酸化アルミニウム、酸化クロム、酸化マンガン、酸化鉄、酸化ジルコニウム、酸化コバルト、合成ムライト、水酸化アルミニウム、水酸化鉄、炭化ケイ素、窒化ケイ素、窒化ホウ素、クレー、ケイソウ土、消石灰、石膏、タルク、炭酸バリウム、炭酸カルシウム、炭酸マグネシウム、硫酸バリウム、ベントナイト、雲母、亜鉛緑、クロム緑、コバルト緑、ビリジアン、ギネー緑、コバルトクロム緑、シェーレ緑、緑土、マンガン緑、ピグメントグリーン、群青、紺青、ピグメントグリーン、岩群青、コバルト青、セルリアンブルー、ホウ酸銅、モリブデン青、硫化銅、コバルト紫、マルス紫、マンガン紫、ピグメントバイオレット、亜酸化鉛、鉛酸カルシウム、ジンクエロー、硫化鉛、クロム黄、黄土、カドミウム黄、ストロンチウム黄、チタン黄、リサージ、ピグメントエロー、亜酸化銅、カドミウム赤、セレン赤、クロムバーミリオン、ベンガラ、亜鉛白、アンチモン白、塩基性硫酸鉛、チタン白、リトポン、ケイ酸鉛、酸化ジルコン、タングステン白、鉛亜鉛華、バンチソン白、フタル酸鉛、マンガン白、硫酸鉛、黒鉛、ボーン黒、ダイヤモンドブラック、サーマトミック黒、植物性黒、チタン酸カリウムウィスカー、二硫化モリブデン等を挙げることができる。
これらの充填材の使用量は、組成物の全固形分１００重量部に対して、通常、３００重量部以下である。
【００６４】
さらに、第１組成物および第２組成物（以下、「コーティング用組成物」ともいう）には、所望により、オルトギ酸メチル、オルト酢酸メチル、テトラエトキシシラン等の公知の脱水剤や、界面活性剤、シランカップリング剤、チタンカップリング剤、染料、分散剤、増粘剤、レベリング剤等の他の添加剤を配合することもできる。
【００６５】
第１組成物を調製するに際しては、（Ｄ）成分における有機金属化合物等と（Ｅ）成分とを使用しない場合は、各成分の混合方法は特に限定されないが、有機金属化合物等と（Ｅ）成分とを使用する場合は、好ましくは、（Ａ１）〜（Ｅ）成分のうち（Ｅ）成分を除いた混合物を得たのち、これに（Ｅ）成分を添加する方法、具体的には下記▲１▼〜▲２▼の方法が採用される。
▲１▼ （Ａ１）成分を構成するオルガノシラン（１）、（Ｂ）成分、必要量の有機溶剤および（Ｄ）成分からなる混合物に、所定量の水を加えて加水分解・部分縮合反応を行ったのち、（Ｅ）成分を添加する方法。
▲２▼ （Ａ１）成分を構成するオルガノシラン（１）、（Ｂ）成分および必要量の有機溶剤からなる混合物に、所定量の水を加えて加水分解・部分縮合反応を行い、次いで（Ｄ）成分を加えて混合して、さらに部分縮合反応を行ったのち、（Ｅ）成分を添加する方法。
また、第１組成物のコーティング用組成物は、場合により
▲３▼（Ｂ）成分を除いた各成分を用いて前記▲１▼あるいは▲２▼の方法を実施したのち、（Ｂ）成分を添加する方法
によっても調製することができる。
なお、第１組成物においては、（Ａ１）〜（Ｅ）成分以外の成分は、組成物を調整する適宜の段階で添加することができる。
【００６６】
また、第２組成物を調製するに際しては、（Ｄ）成分における有機金属化合物等と（Ｅ）成分とを使用しない場合は、各成分の混合方法は特に限定されないが、有機金属化合物等と（Ｅ）成分とを使用する場合は、好ましくは、（Ａ２）〜（Ｅ）成分のうち（Ｅ）成分を除いた混合物を得たのち、これに（Ｅ）成分を添加する方法、具体的には下記▲４▼〜▲６▼の方法が採用される。▲４▼ （Ａ２）成分を構成するオルガノシラン（２）、（Ｂ）成分、（Ｃ２）成分、（Ｄ）成分および必要量の有機溶剤からなる混合物に、所定量の水を加えて加水分解・部分縮合反応を行ったのち、（Ｅ）成分を添加する方法。
▲５▼ （Ａ２）成分を構成するオルガノシラン（２）、（Ｂ）成分および必要量の有機溶剤からなる混合物に、所定量の水を加えて加水分解・部分縮合反応を行い、次いで（Ｃ２）成分および（Ｄ）成分を加えて混合して、さらに部分縮合反応を行ったのち、（Ｅ）成分を添加する方法。
▲６▼ （Ａ２）成分を構成するオルガノシラン（２）、（Ｂ）成分、（Ｄ）成分および必要量の有機溶剤からなる混合物に、所定量の水を加えて加水分解・部分縮合反応を行い、次いで（Ｃ２）成分を加えて混合してさらに部分縮合反応を行ったのち、（Ｅ）成分を添加する方法。
また、第２組成物は、場合により
▲７▼（Ｂ）成分を除いた各成分を用いて前記▲４▼、▲５▼あるいは▲６▼の方法を実施したのち、（Ｂ）成分を添加する方法
によっても調製することができる。
なお、第２組成物においては、（Ａ２）〜（Ｅ）成分以外の成分は、組成物を調整する適宜の段階で添加することができる。
【００６７】
表面に、上記コーティング用組成物からなる塗膜が形成される、本発明の繊維の素材としては、各種の有機繊維、金属繊維および無機繊維を挙げることができる。有機繊維としては、綿、絹、毛、ポリエステル、ナイロンなどのポリアミド、アクリル、レーヨン、セルロースなどの繊維が挙げられる。金属繊維としては、鉄、ステンレス、真鍮、銅、金、銀などの繊維が挙げられる。無機繊維としては、グラスファイバーなどの各種セラミックスファイバーおよびウィスカーなどが挙げられる。また、これらの繊維は、繊維加工品、例えば不織布や紙製品であってもよい。以下、これらの本発明の繊維の素材を、単に「素材」ともいう。素材をコーティング用組成物に含浸することにより、または素材にコーティング用組成物を塗布することによって、塗膜が繊維表面に形成され、本発明の繊維が製造される。本発明において、素材に含浸または塗布されるコーティング用組成物の量は、素材の種類によって異なるが、素材に対して固形分換算で、通常０．５〜１００重量％である。素材にコーティング用組成物を塗布する際には、刷毛、ロールコーター、フローコーター、遠心コーター、超音波コーター等を用いたり、流し塗り、スプレー、スクリーンプロセス、電着、蒸着等の塗布方法により、１回塗りで乾燥後の厚さ１〜４０μｍ程度、２〜３回塗りで、乾燥後の厚さ２〜８０μｍ程度の塗膜を形成することができる。その後、常温で乾燥するか、あるいは３０〜２００℃程度の温度で１０〜６０分間程度加熱して乾燥することにより、各種の素材の表面に(共)縮合により（Ａ）ポリオルガノシランが生成し、硬化塗膜が形成される。素材に、コーティング組成物を含浸する際には、刷毛、ロールコーター、フローコーターを用いたり、流し塗り、ディッピング、スプレー等の塗布方法により、素材の表面に塗膜を形成することができる。なお、素材が繊維加工品の場合、繊維加工品の表面およびその近くの部分の繊維の表面に塗膜が形成されていれば、その繊維加工品は耐候性、耐汚染性、抗菌性、抗かび性等に優れる結果となる場合が多い。また、素材に予め他のコーティング材を塗布または含浸させた後、本発明のコーティング材を塗布または含浸してもよい。他のコーティング材としては、フッ素系コーティング材、アクリルシリコン系コーティング材、前記第１組成物および第２組成物から（Ｂ）成分を除いた組成を有するコーティング材等が挙げられる。
【００６８】
本発明の繊維は、衣類、マスク、シーツ、病院の白衣など；カーテン、壁紙などの家屋、病院、自動車、車両、航空機などの内装材；その他、空気清浄気・換気扇などのフィルター、血液の透析に使用される中空糸膜、包装材料、光学繊維、などに好適に使用することができる。
【００６９】
【実施例】
以下、実施例を挙げて、本発明の実施の形態をさらに具体的に説明する。但し、本発明はこれらの実施例に何ら制約されるものでない。
実施例および比較例中の部および％は、特記しない限り重量基準である。
実施例および比較例における各種の測定・評価は、下記の方法により行った。
（１）ＭｗおよびＭｎ
下記条件によるゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により測定した。

【００７０】
（２）耐候性
ＪＩＳ Ｋ５４００により、サンシャインウエザーメーターで３，０００時間照射試験を実施して、塗膜の外観（割れ、はがれ等）を目視により観察した。
（３）耐汚染性
繊維上に、カーボンブラック／灯油＝１／２（重量比）の混合物からなるペーストを塗り付け、室温で２４時間放置したのち、スポンジを用いて水洗して、塗膜の汚染状態を観察し、下記基準で評価した。
○：汚染なし
△：少し汚染されている
×：汚染が著しい
（４）抗菌性
AATCC100-1981に準じて大腸菌に対する抗菌性を評価した。滅菌生理食塩水（0.1%tritonＸ−１００添加）を用いて１ｍｌ当たりの生菌数が約１０6個になるように希釈しこれを菌液とした。約３ｃｍ×３ｃｍの大きさの試験片に菌液０．５ｍｌを接種し、接種直後および３５℃／６時間放置後の生菌数を測定した。すなわち、成形品をSCDLPブイヨン培地１００ｍｌで１分間振出した液中の生菌数をSCDLP寒天培地を用いる混釈平板培養法により計測した。抗菌力は生菌力は生菌数の減少率で表した。
（５）抗かび性
JIS-Z2911に準じて黒こうじカビに対する抗かび性を評価した。寒天培地で胞子を形成させた後、胞子を0.005％ジオクチルスルホコハク酸ナトリウム滅菌水に浮遊させ胞子懸濁液とした。寒天培地を高圧蒸気滅菌した後、シャーレ内に２５ｍｌづつ分注し凝固させ寒天平板を作成した。この寒天平板上に試験片をのせ、その上に胞子懸濁液１ｍｌを均一に散布した後、２８℃／１４日間培養し、寒天平板の表面に生じた菌の発育状態を調べ、カビ抵抗力の効果を下記３段階で判定した。

【００７１】
合成例１
還流冷却器、撹拌機を備えた反応器に、メチルトリメトキシシラン１００部、酸化チタンの水系ゾル１００部〔アナターゼ型酸化チタン含量４０％（平均粒径１０ｎｍ）、水４０％、アルコール２０％〕、固形分２０％のシリカの溶媒系ゾル７５部（溶液）、ｉ−プロピルアルコール２００部を加えて混合し、攪拌下、６０℃で４時間反応させたのち、室温まで冷却し、３−アミノプロピルトリメトキシシラン２０部を後添加して、固形分濃度約２０％の透明コーテイング組成物（Ｉ−ａ）を調製した。
【００７２】
合成例２、３
配合処方を表１に示すとおりとした以外は、合成例１と同様にして、各々固形分濃度約２０％の、透明コーテイング組成物（Ｉ−ｂ)および（１−ｃ）を調製した。
【００７３】
合成例４〜６
合成例１〜３において、顔料〔塗料用酸化チタン（ルチル型）〕５０重量部をさらに添加し、且つｉ−プロピルアルコールの添加量をそれぞれ４００部（合成例４）、３２５部（合成例６）、ｉ−ブチルアルコールの添加量を４００部（合成例５）として反応を行った以外は、合成例１〜３と同様にして、固形分濃度約２０％の着色コーテイング組成物（Ｉ−ａ')、（Ｉ−ｂ')および（Ｉ−ｃ'）を調製した。
【００７４】
合成例７
攪拌機、還流冷却器を備えた反応器に、メチルトリメトキシシラン１００部、ジメチルジメトキシシラン５０部、酸化チタンの水系ゾル２００部〔アナターゼ型酸化チタン含量４０％（平均粒径１０ｎｍ）、水１０％、アルコール５０％）、カネカゼムラック（商品名、鐘淵化学工業（株）製、主成分：シリコン変性アクリル樹脂、固形分濃度５０％）５０部、ジ−ｉ−プロポキシ・エチルアセトアセテートアルミニウム２０部、ｉ−プロピルアルコール２００部を加えて混合し、攪拌下、６０℃で４時間反応させた。次いで室温まで冷却し、アセチルアセトン２０部を後添加して、固形分約濃度３０％の透明コーテイング組成物（II−ａ）を得た。
【００７５】
合成例８
配合処方を表１に示すとおりとし、反応時間を３時間とした以外は合成例７と同様にして、固形分濃度約３０％の、透明コーテイング組成物（II−ｂ)を調製した。
【００７６】
合成例９，１０
合成例７，８において、顔料〔塗料用酸化チタン（ルチル型）〕１００重量部をさらに添加し、且つｉ−プロピルアルコールの添加量を６００部として反応を行った以外は、それぞれ合成例７，８と同様にして、固形分濃度約３０％の着色コーテイング組成物(II−ａ')および（II−ｂ')を調製した。
【００７７】
合成例１１
配合処方を表１に示すとおりとし、合成例１と同様にして反応を行い、固形分濃度２０％の透明コーテイング組成物（III−ａ）を調製した。
【００７８】
合成例１２
合成例１１において、顔料〔塗料用酸化チタン（ルチル型）〕５０重量部をさらに添加し、且つｉ−プロピルアルコールの添加量を２９０部として反応を行った以外は、合成例１１と同様にして固形分濃度約３０％の着色コーテイング組成物(III−ａ')を調製した。
【００７９】
実施例１〜７、比較例１
ポリエチレンテレフタレート繊維織布１００ｃｍ²を、上記で調製した組成物(I−a)、(I−b)、(I−ｃ)、(II−a)、(Ｉ−ａ')、(Ｉ−ｂ')、(II−ａ')および(III−ａ)のそれぞれ１００ｍLに室温で１０分間浸漬して、織布に組成物を含浸させた。その後、８０℃の温度で１０分間乾燥した処、織布を構成する単繊維の表面に、該織布に対して約１０重量％の塗膜が形成されていた。
これらの織布について、耐候性、耐汚染性、抗菌性および抗かび性について評価した。結果を表２に示した。
【００８０】
実施例１１〜１７、比較例２
アルミニウム繊維にスプレイコート法で上記組成物(I−a)、(I−b)、(I−ｃ)、(II−a)、(Ｉ−ａ')、（Ｉ−ｃ')、(II−ａ')および(III−ａ)のそれぞれを塗布した。その後、１５０℃の温度で１０分間乾燥した。アルミニウム繊維の表面に、該繊維に対して約５重量％の塗膜が形成されていた。
これらアルミニウム繊維の、耐候性、耐汚染性、抗菌性および抗かび性について評価した。結果を表３に示した。
【００８１】
実施例２１〜２７、比較例３
ガラス繊維織布の１００ｃｍ²を、上記組成物(I−a)、(I−b)、(I−ｃ)、(II−a)、(Ｉ−ａ')、（Ｉ−ｂ')、(II−ａ')および(III−ａ)のそれぞれ１００ｍLに室温で１０分間浸漬して、ガラス繊維織布に組成物を含浸させた。その後、１５０℃の温度で１０分間乾燥した処、ガラス繊維織布を構成する繊維の表面に、ガラス繊維織布に対して約３重量％の塗膜が形成されていた。
これらのガラス繊維織布の、耐候性、耐汚染性、抗菌性および抗かび性について評価した。結果を表４に示した。
【００８２】
実施例３１〜３７、比較例４
木綿織布にスプレイコート法で上記組成物(I−a)、(I−b)、(I−ｃ)、(II−a)、(Ｉ−ａ')、（Ｉ−ｂ')、(I−ｃ')および(III−ａ)それぞれを塗布した。その後、８０℃の温度で２０分間乾燥した処、木綿織布の繊維表面に、該織布に対して約５重量％の塗膜が形成されていた。
これら木綿織布の、耐候性、耐汚染性、抗菌性および抗かび性について評価した。結果を表５に示した。
【００８３】
実施例４１〜４７、比較例５
上質紙の１００ｃｍ²を、上記組成物(I−a)、(I−b)、(I−ｃ)、(II−a)、(Ｉ−ａ')、（Ｉ−ｂ')、(II−ａ')および(III−ａ)のそれぞれ１００ｍLに室温で１０分間浸漬して、上質紙に組成物を含浸させた。その後、８０℃の温度で１５分間乾燥した処、上質紙を構成する繊維の表面に上質紙に対して約１０重量％の塗膜が形成されていた。
これらの上質紙の、耐候性、耐汚染性、抗菌性および抗かび性について評価した。結果を表６に示した。
【００８４】
【表１】

【００８５】
【表２】

【００８６】
【表３】

【００８７】
【表４】

【００８８】
【表５】

【００８９】
【表６】

【００９０】
【発明の効果】
本発明の繊維は、耐候性、耐汚染性、抗菌性および抗かび性に優れる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a fiber, and more particularly to a fiber having a coating film formed on the surface thereof, which is formed from an organosilane composition containing inorganic fine particle components having photocatalytic activity.
[0002]
[Prior art]
Conventionally, the fiber has been subjected to various treatments in order to enhance the antifouling property, waterproof property, antibacterial property, antifungal property and the like of its surface.
However, it has been difficult for conventional surface treatment methods to obtain fibers having excellent weather resistance, stain resistance, antibacterial properties, antifungal properties, and the like.
In particular, in order to improve the stain resistance, it has been recognized that the surface of the coating film should be made hydrophilic. For example, a method of adding a hydrophilic substance or a water-soluble substance has been proposed. In this case, it is difficult to maintain the hydrophilicity of the coating film surface at a sufficient level for a long time because the hydrophilic substance and the water-soluble substance are gradually deteriorated by light or washed away with water.
[0003]
[Problems to be solved by the invention]
The present invention has been made against the background of the above-mentioned problems in the prior art, and is to provide a fiber excellent in weather resistance, stain resistance, antibacterial properties and antifungal properties.
[0004]
[Means for Solving the Problems]
  In the present invention, a coating film containing (A) polyorganosiloxane and (B) inorganic fine particles having photocatalytic activity is present on the surface.It is a fiber, and the coating film is formed from a specific compositionThe fiber characterized by the above is provided. The present invention will be described in detail below, but other objects, advantages and effects of the present invention will become apparent.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
  Present on the surface of the fiber of the present inventionThe coating film is formed from the following composition [1] or [2]..
[1]
(A1) The following general formula (1)
    (R¹)_nSi (OR²)_4-n . . . (1)
(Wherein R¹Represents a hydrogen atom or a monovalent organic group, R²Represents an alkyl group, an acyl group or a phenyl group, and n is an integer of 1 or 2. )
A hydrolyzate of organosilane and / or a partial condensate thereof,
(B) inorganic fine particles having photocatalytic activity, and
(C1) A composition containing water and / or an organic solvent (hereinafter referred to as “first composition”).
[2]
(A2) The following general formula (2)
    (R^Three)_mSi (OR^Four)_4-m . . . (2)
(Wherein R^ThreeRepresents an organic group, R^FourRepresents an alkyl group or an acyl group, and m is an integer of 0-2. )
At least one component selected from an organosilane represented by the formula: a hydrolyzate of the organosilane and a partial condensate of the organosilane;
(B) inorganic fine particles having photocatalytic activity, and
(C2) A composition containing a polymer having a hydrolyzable group and / or a silyl group having a silicon atom bonded to a hydroxyl group in the polymer molecular chain (hereinafter referred to as “second composition”).
[0006]
  Hereinafter, each component which comprises a 1st composition and a 2nd composition is demonstrated sequentially. (A1) component
  The component (A1) in the first composition comprises a hydrolyzate and / or partial condensate thereof of an organosilane represented by the general formula (1) (hereinafter referred to as “organosilane (1)”), When a coating film is formed from the first composition, it becomes a main binder by condensation and three-dimensionalization.
  In the general formula (1), R¹ Monovalent indicated byAs an organic group, a C1-C8 organic group is preferable, for example, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n -Alkyl groups such as heptyl group, n-octyl group, 2-ethylhexyl group, vinyl group, allyl group, acyl group, glycidyl group, (meth) acryloxy group, ureido group, amide group, fluoroacetamide group, isocyanate In addition to groups, substituted derivatives of these groups can be mentioned.
  R¹Examples of the substituent in the substituted derivative include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a ureido group, and an ammonium base. Here, R consisting of these substituted derivatives¹The number of carbon atoms is 1 to 8 including the carbon atoms in the substituent. R in general formula (1)¹When two are present, they may be the same or different from each other.
[0007]
R²The alkyl group is preferably an alkyl group having 1 to 5 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n -A pentyl group etc. can be mentioned, As a C1-C6 acyl group, an acetyl group, a propionyl group, a butyryl group, a valeryl group, a caproyl group etc. can be mentioned, for example.
Multiple R's in general formula (1)²May be the same as or different from each other.
[0008]
Specific examples of the organosilane (1) in which n in the general formula (1) is 1 include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n -Propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane,
n-pentyltrimethoxysilane, n-pentyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, vinyltrimethoxysilane, Nyltriethoxysilane, allyltrimethoxysilane, vinyltriacetoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltri Ethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanate In addition to trialkoxysilanes such as natopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane, methyltriacetyloxysilane, methyltriphenoxysilane, etc. Can be mentioned.
[0009]
Of these organosilanes, trialkoxysilanes are preferable, and methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane are more preferable.
The said organosilane (1) whose n of the said General formula (1) is 1 can be used individually or in combination of 2 or more types.
[0010]
Specific examples of the organosilane (1) in which n in the general formula (1) is 2 include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, Di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, n-pentylmethyldimethoxysilane N-pentyl methyldiethoxysilane, cyclohexyl methyldimethoxysilane, cyclohexyl methyldiethoxysilane, phenyl methyldimethoxysilane, phenyl methyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldi Ethoxysilane, -N-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, In addition to dialkoxysilanes such as dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane, dimethyldiacetyloxysilane, dimethyldiphenoxysilane, and the like can be given.
These organosilanes (1) in which n in the general formula (1) is 2 can be used alone or in combination of two or more.
[0011]
Furthermore, the organosilane (1) in which n in the general formula (1) is 1 and the organosilane (1) in which n is 2 may be used alone or in combination. .
[0012]
The first composition contains the component (A1), that is, a hydrolyzate of organosilane (1) represented by the general formula (1) and / or a partial condensate thereof. A hydrolyzate of organosilane (hereinafter referred to as “other organosilane”) in which is 0 and / or a partial condensate thereof may also be contained.
Specific examples of other organosilanes include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetraacetyloxysilane, and tetraphenoxysilane. be able to.
These other organosilanes can be used alone or in combination of two or more.
The amount of other organosilane used is usually 0 to 200 parts by weight, preferably 0 to 100 parts by weight, per 100 parts by weight of component (A1).
[0013]
The organosilane (1) and other organosilanes optionally used can be hydrolyzed and partially condensed in advance and used as the component (A1). However, as described later, the organosilane (1) is used as the remaining component. When preparing a composition in combination with the component, it is preferable to hydrolyze and partially condense the organosilane (1) by adding an appropriate amount of water (component (C1)) to obtain the component (A1). .
When the component (A1) is used as a partial condensate, the weight average molecular weight (hereinafter referred to as “Mw”) of the partial condensate is usually 8,000 to 10,000, preferably 1,000. It is in the range of ~ 50,000. The Mw of the component (A1) composed of the partial condensate is appropriately selected according to the film forming property of the composition, the hardness and flexibility of the coating film, and the like.
In addition, commercially available products of component (A1) include silicon resin manufactured by Toray Dow Corning, silicon resin manufactured by Toshiba Silicone Co., Ltd., silicon oligomer manufactured by Nihon Unica Co., Ltd., etc. Also good.
In the first composition, the component (A1) can be used alone or in combination of two or more.
[0014]
(A2) component
The component (A2) in the second composition is an organosilane represented by the general formula (2) (hereinafter referred to as “organosilane (2)”), a hydrolyzate of organosilane (2), and an organosilane ( It consists of at least one selected from the partial condensates of 2), and is condensed and three-dimensionalized when forming a coating film from the second composition to become the main binder of the coating film.
[0015]
In the general formula (2), R^ThreeAs the organic group, an organic group having 1 to 8 carbon atoms is preferable. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t -Alkyl groups such as butyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, vinyl group, allyl group, cyclohexyl group, phenyl group, acyl group, glycidyl group, (meth) In addition to an acryloxy group, a ureido group, an amide group, a fluoroacetamide group, an isocyanate group, etc., substituted derivatives of these groups can be exemplified.
R^ThreeExamples of the substituent in the substituted derivative include a halogen atom, a substituted or unsubstituted amino group, a hydroxyl group, a mercapto group, an isocyanate group, a glycidoxy group, a 3,4-epoxycyclohexyl group, a (meth) acryloxy group, A ureido group, an ammonium base, etc. can be mentioned. Here, R consisting of these substituted derivatives^ThreeThe number of carbon atoms is 1 to 8 including the carbon atoms in the substituent.
R in general formula (2)^ThreeMay be the same as or different from each other.
[0016]
R^FourAre preferably an alkyl group having 1 to 5 carbon atoms and an acyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, A t-butyl group, n-pentyl group, etc. can be mentioned, As a C1-C6 acyl group, an acetyl group, a propionyl group, a butyryl group, a valeryl group, a caproyl group etc. can be mentioned, for example.
Multiple R's in general formula (2)^FourMay be the same as or different from each other.
[0017]
As a specific example of such an organosilane (2),
Tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, Ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyl Trimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, cyclohexyltrimethoxysilane, Chlohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3 -Trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2- Hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxy Lan, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3-ureidopropyltri Trialkoxysilanes such as methoxysilane and 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane , Di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxy Silane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyl Dialkoxysilanes such as dimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane; trimethylmethoxysilane, trimethylethoxy Monoalkoxy such as silane In addition to silanes, methyl triacetyl silane, dimethyl acetyl silane, trimethyl acetyloxy silane.
Of these, trialkoxysilanes and dialkoxysilanes are preferable. As the trialkoxysilanes, methyltrimethoxysilane and methyltriethoxysilane are preferable. As dialkoxysilanes, dimethyldimethoxysilane and dimethyldimethoxysilane are preferable. Ethoxysilane is preferred.
[0018]
In the present invention, the organosilane (2) is particularly preferably a trialkoxysilane alone or a combination of trialkoxysilane 80 mol% or more and dialkoxysilane less than 20 mol%. By using dialkoxysilane in combination with trialkoxysilane, the resulting coating film can be softened and alkali resistance can be improved.
[0019]
Organosilane (2) is used as it is or as a hydrolyzate or partial condensate. When the organosilane (2) is used as a hydrolyzate and / or a partial condensate, it can be preliminarily hydrolyzed and partially condensed and used as the component (A2). However, as described later, the organosilane (2 ) Is mixed with the remaining components to prepare the composition, it is preferable to hydrolyze and partially condense organosilane (2) by adding an appropriate amount of water to obtain component (A2).
When the component (A2) is used as a partial condensate, the Mw of the partial condensate is preferably 800 to 100,000, more preferably 1,000 to 50,000.
In addition, commercially available products of component (A2) include MKC silicate manufactured by Mitsubishi Chemical Corporation, silicate manufactured by Tama Chemical Co., Ltd., silicon resin manufactured by Toray Dow Corning Co., Ltd., and silicon resin manufactured by Toshiba Silicone Co., Ltd. There are silicon oligomers manufactured by Nihon Unika Co., Ltd., and these may be used.
In the second composition, the component (A2) can be used alone or in combination of two or more.
[0020]
(B) component
The component (B) in the first composition and the second composition is inorganic fine particles having photocatalytic activity. Here, the inorganic fine particles having photocatalytic activity refer to inorganic fine particles that exhibit redox action when irradiated with light. Due to the presence of such component (B), the surface of the coating film is hydrophilized, resulting in a coating film having excellent stain resistance.
As inorganic fine particles having photocatalytic activity, for example, TiO₂TiO_Three, SrTiO_Three, FeTiO_Three, WO_Three, SnO₂, Bi₂O_Three, In₂O_ThreeZnO, Fe₂O_Three, RuO₂, CdO, CdS, CdSe, GaP, GaAs, CdFeO_Three, MoS₂, LaRhO_ThreeEtc., preferably TiO₂ZnO. Particularly preferably, anatase TiO₂It is. In addition, since the first composition and the second composition utilize the above-mentioned photocatalytic ability of the fine particles by light irradiation from the outside, the fine particles are not subjected to a surface treatment that prevents photoactivity. Use is preferred.
[0021]
Due to the photocatalytic ability of the component (B) contained in the first composition and the second composition, the surface of the coating film becomes hydrophilic in a short time even with weak light, and as a result, other coating film performance is substantially improved. The contamination resistance of the coating film can be remarkably improved without loss.
[0022]
Component (B) consists of (i) a powder comprising fine particles, (ii) an aqueous sol in which the fine particles are dispersed in water, and (iii) the fine particles in a polar solvent such as isopropyl alcohol or a nonpolar solvent such as toluene. It can be obtained as three existing forms of dispersed solvent-based sol.
In the case of a solvent-based sol, depending on the dispersibility of the fine particles, it may be further diluted with water or a solvent. The average particle diameter of the fine particles in these existing forms is preferably as small as possible from the viewpoint of photocatalytic activity, and is usually 1 μm or less, preferably 0.5 μm or less, particularly preferably 0.1 μm or less.
When the component (B) is an aqueous sol or a solvent sol, the solid content concentration is preferably 50% by weight or less, more preferably 40% by weight or less.
[0023]
As a method of blending the component (B) in the composition,
(A ′) Preparation of a composition comprising the component (A1) and the components (C1) to (G) described later, or a composition comprising the component (A2) and the components (C2) to (G) described later. A method of adding the component (B) later,
(B ') Method of adding component (B) when preparing the composition of (b') above
There is.
In addition, when the component (B) is an aqueous sol, it is preferably added by the method (b), and also when the viscosity in the system increases due to the blending of the component (F) described later, It is preferable to add the component (B) during the preparation of the composition (a) by the method ').
In the first composition and the second composition, the component (B) can be used alone or in combination of two or more.
[0024]
(B) The usage-amount of a component is 1-500 weight part normally in solid content with respect to 100 weight part of organosilane (1) in (A1) component in a 1st composition, Preferably it is 5-400. In the second composition, the solid content is usually 1 to 500 parts by weight with respect to 100 parts by weight of the organosilane (2) in the component (A2).
[0025]
(C1) component
The component (C1) of the first composition is water and / or an organic solvent.
A 1st composition makes the said (A1) component and (B) component essential, and contains the (D)-(G) component etc. which are mentioned later by the case. In preparing the first composition, water is usually added in order to cause the organosilane (1) and other organosilanes to undergo hydrolysis / partial condensation reaction or to disperse the particulate components.
The usage-amount of the water of a 1st composition is 0.5-3 mol normally with respect to the total of 1 mol of organosilane in (A1) component, Preferably it is about 0.7-2 mol.
[0026]
Further, the second composition essentially comprises the components (A2), (B), and (C2) described later, and optionally contains components (D) to (G) described later. In preparing the second composition, it is preferable to add water in order to cause the organosilane (2) or (C2) component to undergo hydrolysis / partial condensation reaction or to disperse the particulate component.
The usage-amount of the water in a 2nd composition is 0.5-3 mol normally with respect to 1 mol of organosilane (2) in (A2), Preferably it is about 0.7-2 mol.
[0027]
The organic solvent in the first composition is not particularly limited as long as the above components can be mixed uniformly. For example, one kind of alcohols, aromatic hydrocarbons, ethers, ketones, esters, etc. The above can be mentioned.
Among these organic solvents, specific examples of alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, n -Octyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, etc. can be mentioned.
Specific examples of aromatic hydrocarbons include benzene, toluene, xylene, etc., specific examples of ethers include tetrahydrofuran, dioxane, and the like, and specific examples of ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Specific examples of esters such as diisobutylketone and the like include ethyl acetate, propyl acetate, butyl acetate, and propylene carbonate.
These solvents can be used alone or in combination of two or more.
[0028]
The total solid concentration of the first composition and the second composition, which are coating compositions, is preferably 50% by weight or less, and is appropriately adjusted according to the purpose of use. For example, when used for the purpose of forming a thin film on the fiber surface by impregnation, it is usually 2 to 30% by weight, and when used for the purpose of forming a thick film on the fiber surface, it is usually 10 to 50% by weight. Preferably it is 20 to 45 weight%. When the total solid concentration of the composition exceeds 50% by weight, the storage stability tends to decrease.
[0029]
(C2) component
The component (C2) in the second composition includes a hydrolyzable group and / or a silyl group having a silicon atom bonded to a hydroxyl group (hereinafter referred to as “specific silyl group”) in the polymer molecular chain, for example, the molecular chain end. And / or a polymer having a side chain.
When such a component (C2) cures the coating film obtained from the second composition, which is a coating composition, the hydrolyzable group and / or hydroxyl group in the silyl group is the component (A2) and (B) It is a component which brings about the outstanding film performance by co-condensing with component.
The content of the specific silyl group in the component (C2) is usually 0.001 to 20% by weight in terms of the amount of silicon atoms with respect to the polymer before introduction of the specific silyl group.
The specific silyl group is preferably the following general formula (4)
[0030]
[Chemical 1]

[0031]
(Wherein X represents a hydrolyzable group such as a halogen atom, an alkoxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group, an amino group or a hydroxyl group;⁸Represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aralkyl group having 1 to 10 carbon atoms, and i is an integer of 1 to 3. ).
As the component (C2), for example,
(A) A hydrosilane compound corresponding to the general formula (4) (hereinafter referred to as “hydrosilane compound (a)”) is converted into a vinyl polymer having a carbon-carbon double bond (hereinafter referred to as “unsaturated vinyl heavy polymer”). A method of causing an addition reaction to the carbon-carbon double bond in
(B) The following general formula (5)
[0032]
[Chemical 2]

[0033]
(Where X, R⁸, I are X and R in the general formula (4), respectively.⁸, I and R⁹Represents an organic group having a polymerizable double bond. ) (Hereinafter referred to as “unsaturated silane compound (b)”) and other vinyl monomers, and the like.
[0034]
Examples of the hydrosilane compound (a) used in the method (a) include halogenated silanes such as methyldichlorosilane, trichlorosilane, and phenyldichlorosilane; methyldiethoxysilane, methyldimethoxysilane, and phenyldimethoxy. Alkoxysilanes such as silane, trimethoxysilane, triethoxysilane; methyldiacetoxysilane, phenyldiacetoxysilane, triacetoxysilane, and other acyloxysilanes; methyldiaminoxysilane, triaminoxysilane, dimethylaminoxysilane, etc. And aminoxysilanes.
These hydrosilane compounds (a) can be used alone or in combination of two or more.
[0035]
The unsaturated vinyl polymer used in the method (a) is not particularly limited as long as it is a polymer having a hydroxyl group. For example, the following methods (a-1) and (b-2) Or it can manufacture by these combinations.
That is,
(I-1) After (co) polymerizing a vinyl monomer having a functional group (hereinafter referred to as “functional group (α)”), the functional group (i) in the (co) polymer is subjected to By reacting an unsaturated compound having a carbon-carbon double bond with a functional group capable of reacting with the functional group (α) (hereinafter referred to as “functional group (β)”), the molecular chain side An unsaturated vinyl polymer having a carbon-carbon double bond in the chain can be produced.
(I-2) A radical polymerization initiator having a functional group (α) (for example, 4,4-azobis-4-cyanovaleric acid or the like) is used, or a functional group ( α)) (for example, 4,4-azobis-4-cyanovaleric acid and dithioglycolic acid) is used to (co) polymerize the vinyl monomer to form one end of the polymer molecular chain or After synthesizing a (co) polymer having a functional group (α) derived from a radical polymerization initiator or a chain transfer agent at both ends, a functional group (β) is added to the functional group (α) in the (co) polymer. ) And an unsaturated compound having a carbon / carbon double bond to produce an unsaturated vinyl polymer having a carbon-carbon double bond at one or both ends of the polymer molecular chain. it can.
[0036]
Examples of the reaction between the functional group (α) and the functional group (β) in the methods (a-1) and (ii-2) include esterification reaction between a carboxyl group and a hydroxyl group, a carboxylic anhydride group and a hydroxyl group. Ring-opening esterification reaction, carboxyl group and epoxy group esterification reaction, carboxyl group and amino group amidation reaction, carboxylic acid anhydride group and amino group ring-opening amidation reaction, epoxy group and amino group Examples thereof include a ring-opening addition reaction with a group, a urethanization reaction between a hydroxyl group and an isocyanate group, and a combination of these reactions.
[0037]
Examples of vinyl monomers having a functional group (α) include unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid; maleic anhydride, itaconic anhydride and the like. Unsaturated carboxylic acid anhydrides; hydroxyl groups such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, N-methylol (meth) acrylamide, 2-hydroxyethyl vinyl ether Containing vinyl monomer; 2-aminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) ) Acrylate, 2-dimethylaminopropyl ( Amino group-containing vinyl monomers such as acrylate, 3-dimethylaminopropyl (meth) acrylate, 2-aminoethyl vinyl ether, N, N-dimethylamino (meth) acrylamide, and N, N-diethylamino (meth) acrylamide 1,1,1-trimethylamine (meth) acrylimide, 1-methyl-1-ethylamine (meth) acrylimide, 1,1-dimethyl-1- (2-hydroxypropyl) amine (meth) acrylimide, 1, 1-dimethyl-1- (2′-phenyl-2′-hydroxyethyl) amine (meth) acrylimide, 1,1-dimethyl-1- (2′-hydroxy-2′-phenoxypropyl) amine (meth) acrylic Amide group-containing vinyl monomers such as imide, glycidyl (meth) acrylate, Examples thereof include epoxy group-containing vinyl monomers such as luglycidyl ether.
These vinyl monomers having a functional group (α) can be used alone or in combination of two or more.
[0038]
Examples of other vinyl monomers copolymerized with a vinyl monomer having a functional group (α) include methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl (meth) acrylate. , I-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylamide, croton Amides, maleic acid diamides, fumaric acid diamides, itaconic acid diamides, α-ethylacrylamide, N-butoxymethyl (meth) acrylamide, (meth) acrylonitrile, styrene, α-methylstyrene, vinyl chloride, vinyl acetate, vinyl propionate, etc. Can be mentioned.
These other vinyl monomers can be used alone or in combination of two or more.
[0039]
Examples of the unsaturated compound having a functional group (β) and a carbon / carbon double bond include, for example, vinyl monomers similar to the vinyl monomer having a functional group (α), and the hydroxyl group-containing vinyl type. An isocyanate group-containing unsaturated compound obtained by reacting the monomer and the diisocyanate compound in an equimolar amount can be exemplified.
[0040]
Moreover, as a specific example of the unsaturated silane compound (b) used in the method (b),
CH₂= CH (CH_Three) Si (OCH_Three)₂  ,
CH₂= CHSi (OCH_Three)_Three,
CH₂= CH (CH_Three) SiCl₂, CH₂= CHSiCl_Three,
CH₂= CHCOO (CH₂)_ThreeSi (OCH3)₂  ,
CH₂= CHCOO (CH₂)_ThreeSi (CH_Three) (OCHR_Three)_Three  ,
CH₂= CHCOO (CH₂)_ThreeSi (CH_Three) Cl₂,
CH₂= CHCOO (CH₂)_ThreeSiCl_Three,
CH₂= C (CH_Three) COO (CH₂)_ThreeSi (CH_Three) (OCH_Three)₂  ,
CH₂= C (CH_Three) COO (CH2)_ThreeSi (CH_Three) (OCH_Three)₂  ,
CH₂= C (CH_Three) COO (CH₂)_ThreeSiCl₂  ,
CH₂= C (CH_Three) COO (CH₂)_ThreeSiCl_Three  ,
[0041]
[Chemical Formula 3]

[0042]
[Formula 4]

[0043]
[Chemical formula 5]

[0044]
[Chemical 6]

[0045]
Etc.
These unsaturated silane compounds (b) can be used alone or in combination of two or more.
Examples of other vinyl monomers copolymerized with the unsaturated silane compound (b) include, for example, vinyl monomers having the functional group (α) exemplified for the method (a-1) and others. One or more types of vinyl monomers may be mentioned.
[0046]
More specifically, a preferred example of the component (C2) obtained as described above is shown by the following general formula (6).
[0047]
[Chemical 7]

[0048]
(Wherein R^TenRepresents a hydrogen atom or a methyl group, R¹¹Represents an alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, n-pentyl group and n-hexyl group;¹²Is R^TenIs synonymous with R¹³Represents an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a propylene group or a butylene group;¹⁴Is R¹¹And k / (j + k) = 0.01 to 0.4, preferably 0.02 to 0.2. ) Represented by a trialkoxysilyl group-containing (meth) acrylate copolymer.
[0049]
Other specific examples of the component (C2) include specific silyl group-containing epoxy resins, specific silyl group-containing polyester resins, and specific silyl group-containing fluororesins.
Examples of the specific silyl group-containing epoxy resin include epoxy groups in epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, hydrogenated bisphenol A type epoxy resins, aliphatic polyglycidyl ethers, and aliphatic polyglycidyl esters. And aminosilanes having a specific silyl group, vinylsilanes, carboxysilanes, glycidylsilanes, and the like.
The specific silyl group-containing polyester resin may be produced, for example, by reacting a carboxyl group or a hydroxyl group contained in the polyester resin with aminosilanes, carboxysilanes, glycidylsilanes or the like having a specific silyl group. Can do.
The specific silyl group-containing fluororesin includes, for example, aminosilanes, carboxysilanes, glycidylsilanes, etc., having a specific silyl group in a carboxyl group or hydroxyl group contained in a (co) polymer such as fluorinated ethylene. Can be made to react.
[0050]
  The number average molecular weight (hereinafter referred to as “Mn”) of the component (C2) in terms of polystyrene is preferably 2,000 to 100,000, and more preferably 4,000 to 50,000.
  In the second composition, the component (C2) can be used alone or in combination of two or more.
  The amount of component (C2) used in the second composition is organosilane in component (A2).(2)The amount is usually 2 to 900 parts by weight, preferably 10 to 400 parts by weight, and more preferably 20 to 200 parts by weight with respect to 100 parts by weight. In this case, when the amount of the component (C2) used is less than 2 parts by weight, the alkali resistance of the resulting coating film tends to decrease, whereas when it exceeds 900 parts by weight, the weather resistance of the coating film tends to decrease. .
[0051]
Furthermore, the following (D)-(G) component can be mix | blended with a 1st composition and a 2nd composition.
(D) component
In the first composition, the component (D) promotes hydrolysis / condensation reaction of the component (A1) and the like, and in the second composition, the component (A2) and the component (C2) are hydrolyzed / condensed. It consists of a catalyst that promotes the condensation reaction.
In the first composition and the second composition, by using the component (D), the curing rate of the obtained coating film is increased and the polysiloxane resin produced by the polycondensation reaction of the organosilane component used is used. Mn increases, a coating film excellent in strength, long-term durability, and the like can be obtained, and the coating film can be made thicker and painted easily. Examples of such component (D) include acidic compounds, alkaline compounds, organometallic compounds and / or partial hydrolysates thereof (hereinafter, organometallic compounds and / or partial hydrolysates are collectively referred to as “organometallic compounds, etc.”). Is preferred).
[0052]
Among the components (D), examples of the acidic compound include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, alkyl titanic acid, p-toluenesulfonic acid, phthalic acid, and the like, preferably acetic acid.
Moreover, as an alkaline compound, sodium hydroxide, potassium hydroxide etc. can be mentioned, for example, Preferably it is sodium hydroxide.
Examples of the organometallic compound include the following general formula:
M (OR¹⁵) P (R¹⁶COCHCOR¹⁷) Q
(Wherein M represents zirconium, titanium or aluminum, R¹⁵And R¹⁶Are each independently an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group, phenyl group, etc. Represents a monovalent hydrocarbon group having 1 to 6 carbon atoms, R¹⁷Is R¹⁵And R¹⁶As well as monovalent hydrocarbon groups having 1 to 6 carbon atoms, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, lauryl An alkoxyl group having 1 to 16 carbon atoms such as an oxy group and a stearyloxy group is shown, p and q are integers of 0 to 4, and (p + q) = (valence of M). ) Or a partial hydrolyzate of these compounds.
[0053]
Specific examples of organometallic compounds include tetra-n-butoxyzirconium, tri-n-butoxyethylacetoacetatezirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetate). Acetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium, and other organic zirconium compounds; tetra-i-propoxytitanium, di-i-propoxybis ( Organic titanium compounds such as ethyl acetoacetate) titanium, di-i-propoxy bis (acetylacetate) titanium, di-i-propoxy bis (acetylacetone) titanium; -Propoxy aluminum, di-i-propoxy ethyl acetoacetate aluminum, di-i-propoxy acetyl acetonato aluminum, i-propoxy bis (ethyl acetoacetate) aluminum, i-propoxy bis (acetyl acetonato) aluminum, Examples include organoaluminum compounds such as tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonate-bis (ethylacetoacetate) aluminum, and partial hydrolysates of these compounds.
Of these, tri-n-butoxy ethyl acetoacetate zirconium, di-i-propoxy bis (acetylacetonate) titanium, di-i-propoxy ethyl acetoacetate aluminum, tris (ethyl acetoacetate) aluminum, or these A partial hydrolyzate of the compound is preferred.
(D) component can be used individually or in combination of 2 or more types.
[0054]
The amount of the component (D) in the first composition and the second composition is 100 parts by weight in total of the organosilane in the component (A1) or the organosilane in the component (A2), except for the organometallic compound. It is usually 0 to 100 parts by weight, preferably 0.01 to 80 parts by weight, more preferably 0.1 to 50 parts by weight with respect to the total of 100 parts by weight. In general, 0 to 100 parts by weight, preferably 0.1 to 80 parts by weight, and more preferably 0.1 to 80 parts by weight with respect to 100 parts by weight of the organosilane in the component or 100 parts by weight of the organosilane in the component (A2). 5 to 50 parts by weight. In this case, when the amount of the component (D) used exceeds 100 parts by weight, the storage stability of the composition tends to be reduced, or cracks tend to occur in the coating film.
[0055]
(E) component
The component (E) has the following general formula
R¹⁸COCH₂COR¹⁹
(Wherein R¹⁸And R¹⁹Are each R in each general formula in the metal chelate compound.¹⁶And R¹⁷It is synonymous with. And β-diketones and β-ketoesters, carboxylic acid compounds, dihydroxy compounds, amine compounds, and oxyaldehyde compounds. Such component (E) is preferably used in combination when an organometallic compound or the like is used among the components (D).
The component (E) acts as a stability improver for the first and second compositions. That is, by coordinating the component (E) to a metal atom such as the organometallic compound, the condensation reaction of the (A1) component, (A2) component, (C2) component, etc. by the organometallic compound is promoted. It is considered that the effect of further improving the storage stability of the resulting composition is achieved by appropriately controlling the action.
Specific examples of the component (E) include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate-sec-butyl, acetoacetate -T-butyl, hexane-2,4-dione, heptane-2,4-dione, heptane-3,5-dione, octane-2,4-dione, nonane-2,4-dione, 5-methylhexane- 2,4-dione, malonic acid, oxalic acid, phthalic acid, glycolic acid, salicylic acid, aminoacetic acid, iminoacetic acid, ethylenediaminetetraacetic acid, glycol, catechol, ethylenediamine, 2,2-bipyridine, 1,10-phenanthroline, diethylenetriamine, 2-ethanolamine, dimethylglyoxime, dithizone, methionine, salicylua And the like can be given dehydrogenase.
Of these, acetylacetone, ethyl acetoacetate, and 2-ethanolamine are preferred.
(E) A component can be used individually or in combination of 2 or more types. The usage-amount of the (E) component in a 1st composition and a 2nd composition is 2 mol or more normally with respect to 1 mol of organometallic compounds in the said organometallic compound etc., Preferably it is 3-20 mol.
[0056]
(F) component
The component (F) is an inorganic fine particle other than the component (B), and is blended according to the desired properties of the coating film.
Specific examples of the inorganic fine particles of component (F) include SiO₂, Al₂O_ThreeAl (OH)_Three, Sb₂O_Five, Si_ThreeN_Four, Sn-In₂O_Three, Sb-In₂O_Three, MgF, CeF_ThreeTiO₂, ZnO, CeO₂, SiO₂, Al₂O_Three3Al₂O_Three・ 2SiO₂, BeO, SiC, AlN, Al₂O_Three, Fe, Fe₂O_Three, Co, Co-FeOX, CrO₂, Fe_FourN, Ba ferrite, SmCO_Five, YCO_Five, CeCO_Five, PrCO_Five, Sm₂CO₁₇, Nd₂Fe₁₄B, ZrO₂, Al_FourO_ThreeAlN, SiC, BeO and the like.
[0057]
Component (F) is (i) a powder comprising fine particles, (ii) an aqueous sol or colloid in which the fine particles are dispersed in water, and (iii) a polar solvent such as isopropyl alcohol or a nonpolar solvent such as toluene. It exists as a solvent-based sol or colloid dispersed therein. In the case of a solvent-based sol or colloid, it may be further diluted with water or a solvent depending on the dispersibility of the fine particles.
When the component (F) is an aqueous sol or colloid and a solvent sol or colloid, the solid concentration is preferably 40% by weight or less.
(F) A component can be used individually or in combination of 2 or more types.
(F) As a method of mix | blending component in a 1st or 2nd composition, you may add after preparation of these compositions, or it adds at the time of preparation of a composition, (F) component is 1st. In the composition, it may be hydrolyzed together with the component (A1), the component (B) and the like and co-condensed. In the second composition, the component (A2), the component (B), ( It may be hydrolyzed together with component C2) and co-condensed.
The amount of the component (F) used in the first composition and the second composition is 100 parts by weight of the organosilane in the component (A1) or 100 parts by weight of the organosilane in the component (A2). The solid content is usually 0 to 500 parts by weight, preferably 0.1 to 400 parts by weight.
[0058]
(G) component
  (G) A component consists of hardening accelerators other than the said (D) component. By using such component (G), it is possible to increase the curing rate of the coating film formed from the first composition and the second composition, which are coating compositions, and to cure at a relatively low temperature. Can be made.
  Examples of the component (G) include alkali metal salts such as naphthenic acid, octylic acid, nitrous acid, sulfurous acid, aluminate, and carbonic acid; ethylenediamine, hexanediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, piperidine, piperazine, Metaphenylenediamine, ethanolamine, triethylamine, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) -aminopropyltrimethoxysilane, 3- (2-aminoethyl) -aminopropylmethyldimethoxysilane, 3-aminoAmine compounds such as propyltrimethoxysilane and various modified amines used as curing agents for epoxy resins;_FourH₉)₂Sn (OCOC₁₁H_{twenty three})₂, (C_FourH₉)₂Sn (OCOCH = CHCOOCH_Three)₂ , (C_FourH₉)₂Sn (OCOCH = CHCOO (C_FourH₉)₂ , (C₈H₁₇)₂Sn (OCOC₁₁H_{twenty three})₂, (C₈H₁₇)₂Sn (OCOCH = CHCOOCH_Three)₂ , (C₈H₁₇)₂Sn (OCOCH = CHCOO (C_FourH₉)₂ , (C₈H₁₇)₂Sn (OCOCH = CHCOOC₈H₁₇)₂, Sn (OCOCC₈H₁₇)₂Carboxylic acid type organotin compounds such as C;_FourH₉)₂Sn (SCH₂COOC₈H₁₇)₂, (C_FourH₉)₂Sn (SCH₂CH₂COOC₈H₁₇)₂, (C₈H₁₇)₂Sn (SCH₂COOC₈H₁₇)₂, (C₈H₁₇)₂Sn (SCH₂CH₂COOC₈H₁₇)₂, (C₈H₁₇)₂Sn (SCH₂COOC₁₂H_{twenty five})₂, (C₈H₁₇)₂Sn (SCH₂CH₂COOC₁₂H_{twenty five})₂
[0059]
[Chemical 8]

Mercaptide-type organotin compounds such as
[0060]
(C_FourH₉)₂Sn = S, (C₈H₁₇)₂Sn = S,
[0061]
[Chemical 9]

[0062]
Sulfide type organotin compounds such as
(C_FourH₉)₂SnO, (C₈H₁₇)₂Examples thereof include organic tin oxides such as SnO and reaction products of these organic tin oxides with ester compounds such as ethyl silicate, dimethyl maleate, diethyl maleate, and dioctyl phthalate.
(G) A component can be used individually or in combination of 2 or more types. The amount of component (G) used is usually 0 to 100 parts by weight, preferably 0.1 to 80 parts by weight, based on 100 parts by weight of organosilane (I) in component (A1) in the first composition. Parts, more preferably 0.5 to 50 parts by weight, and in the second composition, usually 0 to 100 parts by weight, preferably 100 parts by weight of the organosilane (2) in the component (A2). Is 0.1 to 80 parts by weight, more preferably 0.5 to 50 parts by weight.
[0063]
In addition, a filler can be added and dispersed separately in the first composition or the second composition in order to color or thicken the resulting coating film.
Examples of such fillers include water-insoluble organic pigments and inorganic pigments, particulate, fibrous or scale-like ceramics, metals or alloys other than pigments, and oxides and hydroxides of these metals. , Carbides, nitrides, sulfides and the like.
Specific examples of the filler include iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide (rutile type, etc.), aluminum oxide, chromium oxide, manganese oxide, and oxidation. Iron, zirconium oxide, cobalt oxide, synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, clay, diatomaceous earth, slaked lime, gypsum, talc, barium carbonate, calcium carbonate, magnesium carbonate, barium sulfate , Bentonite, mica, zinc green, chrome green, cobalt green, viridian, guinea green, cobalt chrome green, chellet green, green soil, manganese green, pigment green, ultramarine, bitumen, pigment green, rock ultramarine, cobalt blue, cerulean blue , Copper borate, molybdenum blue, copper sulfide, copper Purple, Mars purple, Manganese purple, Pigment violet, Lead oxide, Calcium leadate, Zinc yellow, Lead sulfide, Chrome yellow, Ocher, Cadmium yellow, Strontium yellow, Titanium yellow, Resurge, Pigment yellow, Cuprous oxide, Cadmium red , Selenium red, chrome vermilion, bengara, zinc white, antimony white, basic lead sulfate, titanium white, lithopone, lead silicate, zircon oxide, tungsten white, lead zinc white, bunchison white, lead phthalate, manganese white, Examples thereof include lead sulfate, graphite, bone black, diamond black, thermostatic black, vegetable black, potassium titanate whisker, and molybdenum disulfide.
The amount of these fillers used is usually 300 parts by weight or less with respect to 100 parts by weight of the total solid content of the composition.
[0064]
Furthermore, for the first composition and the second composition (hereinafter also referred to as “coating composition”), a known dehydrating agent such as methyl orthoformate, methyl orthoacetate, tetraethoxysilane, or the like, or a surface activity, may be used. Other additives such as an agent, a silane coupling agent, a titanium coupling agent, a dye, a dispersant, a thickener, and a leveling agent can also be blended.
[0065]
In preparing the first composition, when the organometallic compound or the like in the component (D) and the (E) component are not used, the mixing method of each component is not particularly limited, but the organometallic compound and the like (E) When using a component, Preferably, after obtaining the mixture except (E) component among (A1)-(E) component, the method of adding (E) component to this, specifically, the following The methods (1) to (2) are adopted.
(1) Hydrolysis / partial condensation reaction is performed by adding a predetermined amount of water to a mixture composed of organosilane (1), component (B), necessary amount of organic solvent and component (D) constituting component (A1). The method of adding (E) component after performing.
{Circle around (2)} A predetermined amount of water is added to a mixture composed of the organosilane (1) and the component (B) constituting the component (A1) and the necessary amount of organic solvent, followed by hydrolysis and partial condensation reaction, and then (D ) A component is added and mixed, and after further partial condensation reaction, the component (E) is added.
In addition, the coating composition of the first composition may be
(3) Method of adding the component (B) after carrying out the method (1) or (2) using each component except the component (B)
Can also be prepared.
In the first composition, components other than the components (A1) to (E) can be added at an appropriate stage for adjusting the composition.
[0066]
In preparing the second composition, when the organometallic compound in the component (D) and the component (E) are not used, the mixing method of each component is not particularly limited. When the component (E) is used, it is preferable to obtain a mixture obtained by removing the component (E) from the components (A2) to (E), and then add the component (E) to this. The following methods (4) to (6) are adopted. (4) Hydrolysis by adding a predetermined amount of water to a mixture comprising the organosilane (2), (B) component, (C2) component, (D) component and the required amount of organic solvent constituting the component (A2). A method of adding the component (E) after performing a partial condensation reaction.
(5) Hydrolysis / partial condensation reaction is carried out by adding a predetermined amount of water to a mixture composed of organosilane (2) and component (B) constituting component (A2) and the necessary amount of organic solvent, and then (C2 ) Component and (D) component are added and mixed, and after further performing a partial condensation reaction, a method of adding component (E).
(6) A predetermined amount of water is added to a mixture comprising the organosilane (2), (B) component, (D) component and the necessary amount of organic solvent constituting the component (A2) to carry out hydrolysis and partial condensation reaction. And then adding the component (C2) and mixing to conduct a partial condensation reaction, and then adding the component (E).
In addition, the second composition may be
(7) A method of adding the component (B) after carrying out the method (4), (5) or (6) using each component except the component (B)
Can also be prepared.
In the second composition, components other than the components (A2) to (E) can be added at an appropriate stage for adjusting the composition.
[0067]
  On the surface, abovecoatingExamples of the fiber material of the present invention on which a coating film made of the composition is formed include various organic fibers, metal fibers, and inorganic fibers. Examples of organic fibers include fibers such as polyamide such as cotton, silk, hair, polyester, and nylon, acrylic, rayon, and cellulose. Examples of the metal fiber include iron, stainless steel, brass, copper, gold, and silver. Inorganic fibers include various ceramic fibers such as glass fiber andWhiskerEtc. These fibers may be processed fiber products, for example, non-woven fabrics and paper products. Hereinafter, the material of the fiber of the present invention is also simply referred to as “material”. MaterialcoatingBy impregnating the composition for use or in the materialcoatingBy applying the composition for coating, a coating film is formed on the fiber surface, and the fiber of the present invention is produced. In the present invention, the material is impregnated or applied.coatingThe amount of the composition for use varies depending on the type of material, but is usually 0.5 to 100% by weight in terms of solid content with respect to the material. MaterialcoatingWhen applying a composition for coating, use a brush, roll coater, flow coater, centrifugal coater, ultrasonic coater, etc., or apply once by flow coating, spraying, screen process, electrodeposition, vapor deposition, etc. The coating thickness of about 2 to 80 μm after drying can be formed by coating 2 to 3 times with a thickness of about 1 to 40 μm after drying. Then, it is dried at room temperature or heated at a temperature of about 30 to 200 ° C. for about 10 to 60 minutes and dried to produce (A) polyorganosilane by (co) condensation on the surface of various materials. A cured coating film is formed. In the material,coatingWhen impregnating the composition, use a brush, roll coater, flow coater, flow coating,DippingA coating film can be formed on the surface of the material by a coating method such as spraying. When the material is a processed fiber product, if the coating film is formed on the surface of the fiber processed product and the fiber in the vicinity thereof, the processed fiber product is weather resistant, stain resistant, antibacterial, In many cases, the result is excellent in moldability and the like. In addition, other materials in advancecoatingAfter applying or impregnating the material, the coating material of the present invention may be applied or impregnated. othercoatingAs material, fluorine-basedcoatingMaterial, acrylic siliconcoatingA composition obtained by removing the component (B) from the first composition and the second compositioncoatingMaterials and the like.
[0068]
The fibers of the present invention include clothes, masks, sheets, hospital lab coats, etc .; interior materials such as curtains, wallpaper, etc., hospitals, automobiles, vehicles, aircraft, etc .; Can be suitably used for hollow fiber membranes, packaging materials, optical fibers, and the like.
[0069]
【Example】
Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
Parts and% in Examples and Comparative Examples are based on weight unless otherwise specified.
Various measurements and evaluations in Examples and Comparative Examples were performed by the following methods.
(1) Mw and Mn
It measured by the gel permeation chromatography (GPC) method by the following conditions.

[0070]
(2) Weather resistance
According to JIS K5400, an irradiation test was conducted with a sunshine weather meter for 3,000 hours, and the appearance (cracking, peeling, etc.) of the coating film was visually observed.
(3) Pollution resistance
A paste made of a mixture of carbon black / kerosene = 1/2 (weight ratio) was applied on the fiber, left standing at room temperature for 24 hours, then washed with water using a sponge, and the contamination state of the coating film was observed. Evaluation was made according to the following criteria.
○: No contamination
Δ: Slightly contaminated
×: Significant contamination
(4) Antibacterial
Antibacterial activity against E. coli was evaluated according to AATCC100-1981. The solution was diluted with sterile physiological saline (added with 0.1% triton X-100) so that the number of viable bacteria per ml was about 10 6 and used as a bacterial solution. A test piece having a size of about 3 cm × 3 cm was inoculated with 0.5 ml of the bacterial solution, and the number of viable bacteria was measured immediately after inoculation and after being left at 35 ° C. for 6 hours. That is, the number of viable bacteria in the liquid obtained by shaking the molded product with 100 ml of SCDLP broth medium for 1 minute was measured by the pour plate culture method using SCDLP agar medium. Antibacterial activity was expressed as the rate of decrease in viable cell count.
(5) Antifungal property
The antifungal property against black mold was evaluated according to JIS-Z2911. After spore formation on an agar medium, the spore was suspended in 0.005% sodium dioctylsulfosuccinate-sterilized water to obtain a spore suspension. The agar medium was sterilized by autoclaving, then dispensed in 25 ml portions in a petri dish and solidified to prepare an agar plate. Place a test piece on this agar plate, spread 1 ml of the spore suspension uniformly on it, culture at 28 ° C / 14 days, and examine the growth state of the bacteria generated on the surface of the agar plate. The effect of was evaluated in the following three stages.

[0071]
Synthesis example 1
In a reactor equipped with a reflux condenser and a stirrer, 100 parts of methyltrimethoxysilane, 100 parts of an aqueous sol of titanium oxide [anatase type titanium oxide content 40% (average particle size 10 nm), water 40%, alcohol 20%] Then, 75 parts of a silica solvent sol having a solid content of 20% (solution) and 200 parts of i-propyl alcohol were added and mixed. After stirring, the mixture was reacted at 60 ° C. for 4 hours, cooled to room temperature, and 3-amino 20 parts of propyltrimethoxysilane was added afterwards to prepare a transparent coating composition (Ia) having a solid concentration of about 20%.
[0072]
Synthesis examples 2 and 3
Transparent coating compositions (Ib) and (1-c) each having a solid concentration of about 20% were prepared in the same manner as in Synthesis Example 1 except that the formulation was as shown in Table 1.
[0073]
Synthesis Examples 4-6
In Synthesis Examples 1 to 3, 50 parts by weight of pigment [titanium oxide for paint (rutile type)] was further added, and the amount of i-propyl alcohol added was 400 parts (Synthesis Example 4) and 325 parts (Synthesis Example 6), respectively. ), A colored coating composition (I-a) having a solid content concentration of about 20% in the same manner as in Synthesis Examples 1 to 3 except that the reaction was carried out with 400 parts of i-butyl alcohol added (Synthesis Example 5). '), (Ib') and (Ic ') were prepared.
[0074]
Synthesis example 7
In a reactor equipped with a stirrer and a reflux condenser, 100 parts of methyltrimethoxysilane, 50 parts of dimethyldimethoxysilane, 200 parts of an aqueous sol of titanium oxide [anatase type titanium oxide content 40% (average particle size 10 nm), water 10% , Alcohol 50%), Kanekazemulac (trade name, manufactured by Kaneka Chemical Industry Co., Ltd., main component: silicon-modified acrylic resin, solid content concentration 50%), 50 parts, di-i-propoxy ethyl acetoacetate aluminum 20 And 200 parts of i-propyl alcohol were added and mixed, and the mixture was reacted at 60 ° C. for 4 hours with stirring. Next, the mixture was cooled to room temperature and 20 parts of acetylacetone was post-added to obtain a transparent coating composition (II-a) having a solid content of about 30%.
[0075]
Synthesis example 8
A transparent coating composition (II-b) having a solid concentration of about 30% was prepared in the same manner as in Synthesis Example 7 except that the formulation was as shown in Table 1 and the reaction time was 3 hours.
[0076]
Synthesis Examples 9 and 10
In Synthesis Examples 7 and 8, except that 100 parts by weight of a pigment [titanium oxide for paint (rutile type)] was further added and the reaction was carried out with the addition amount of i-propyl alcohol being 600 parts, Synthesis Example 7, In the same manner as in No. 8, colored coating compositions (II-a ′) and (II-b ′) having a solid concentration of about 30% were prepared.
[0077]
Synthesis Example 11
The formulation was as shown in Table 1, and the reaction was carried out in the same manner as in Synthesis Example 1 to prepare a transparent coating composition (III-a) having a solid content concentration of 20%.
[0078]
Synthesis Example 12
In Synthesis Example 11, the same procedure as in Synthesis Example 11 was conducted, except that 50 parts by weight of pigment [titanium oxide for paint (rutile type)] was further added and the reaction was carried out with the addition amount of i-propyl alcohol being 290 parts. A colored coating composition (III-a ′) having a solid concentration of about 30% was prepared.
[0079]
Examples 1-7, Comparative Example 1
Polyethylene terephthalate fiber woven fabric 100cm²Are prepared in the composition (Ia), (Ib), (Ic), (II-a), (Ia ′), (Ib ′), (II-a) prepared above. ') And (III-a) were immersed in 100 mL of each at room temperature for 10 minutes to impregnate the woven fabric with the composition. Then, after drying for 10 minutes at a temperature of 80 ° C., a coating film of about 10% by weight was formed on the surface of the single fiber constituting the woven fabric.
These woven fabrics were evaluated for weather resistance, stain resistance, antibacterial and antifungal properties. The results are shown in Table 2.
[0080]
Examples 11-17, Comparative Example 2
The above composition (Ia), (Ib), (Ic), (II-a), (Ia ′), (Ic ′), (II) -A ') and (III-a) were applied. Then, it dried for 10 minutes at the temperature of 150 degreeC. About 5% by weight of a coating film was formed on the surface of the aluminum fiber.
These aluminum fibers were evaluated for weather resistance, stain resistance, antibacterial and antifungal properties. The results are shown in Table 3.
[0081]
Examples 21-27, Comparative Example 3
100cm of glass fiber woven fabric²And (I-a), (Ib), (Ic), (II-a), (Ia ′), (Ib ′), (II-a ′) and The glass fiber woven fabric was impregnated with the composition by immersing in 100 mL of each of (III-a) at room temperature for 10 minutes. Then, after drying for 10 minutes at a temperature of 150 ° C., a coating film of about 3% by weight with respect to the glass fiber woven fabric was formed on the surface of the fibers constituting the glass fiber woven fabric.
These glass fiber woven fabrics were evaluated for weather resistance, stain resistance, antibacterial properties and antifungal properties. The results are shown in Table 4.
[0082]
Examples 31-37, Comparative Example 4
The composition (Ia), (Ib), (Ic), (IIa), (Ia ′), (Ib ′), (Ib ′), (I Ic ′) and (III-a) were applied. Then, after drying for 20 minutes at a temperature of 80 ° C., a coating film of about 5% by weight was formed on the fiber surface of the cotton woven fabric.
These cotton fabrics were evaluated for weather resistance, stain resistance, antibacterial and antifungal properties. The results are shown in Table 5.
[0083]
Examples 41 to 47, Comparative Example 5
100cm of fine paper²And (I-a), (Ib), (Ic), (II-a), (Ia ′), (Ib ′), (II-a ′) and Each of (III-a) was immersed in 100 mL at room temperature for 10 minutes to impregnate the fine paper with the composition. Thereafter, after drying for 15 minutes at a temperature of 80 ° C., a coating film of about 10% by weight with respect to the fine paper was formed on the surface of the fibers constituting the fine paper.
These fine papers were evaluated for weather resistance, stain resistance, antibacterial and antifungal properties. The results are shown in Table 6.
[0084]
[Table 1]

[0085]
[Table 2]

[0086]
[Table 3]

[0087]
[Table 4]

[0088]
[Table 5]

[0089]
[Table 6]

[0090]
【The invention's effect】
The fiber of the present invention is excellent in weather resistance, stain resistance, antibacterial property and antifungal property.

Claims (4)

A coating film containing (A) polyorganosiloxane and (B) inorganic fine particles having photocatalytic activity is a fiber present on the surface,
The fiber, wherein the coating film is formed from any one of the following compositions [1] and [2].
[1]
(A1) The following general formula (1)
(R ¹ ) _n Si (OR ² ) _4-n . . . (1)
(In the formula, R ¹ represents a hydrogen atom or a monovalent organic group, R ² represents an alkyl group, an acyl group, or a phenyl group, and n is an integer of 1 or 2.)
A hydrolyzate of organosilane and / or a partial condensate thereof,
(B) A composition containing inorganic fine particles having photocatalytic activity, and (C1) water and / or an organic solvent.
[2]
(A2) The following general formula (2)
(R ³ ) _m Si (OR ⁴ ) _4-m . . . (2)
(In the formula, R ³ represents an organic group, R ⁴ represents an alkyl group or an acyl group, and m is an integer of 0 to 2.)
At least one component selected from an organosilane represented by the formula: a hydrolyzate of the organosilane and a partial condensate of the organosilane;
(B) A composition containing inorganic fine particles having photocatalytic activity and (C2) a polymer having a silyl group having a silicon atom bonded to a hydrolyzable group and / or a hydroxyl group in a polymer molecular chain.   The coating film is formed from the composition [1], and the composition [1] is composed of (A1) component and (A1) component organosilane (1) 100 parts by weight. The component (B) of 1 to 500 parts by weight in solid content and the component (C1) comprising 0.5 to 3 mol of water with respect to 1 mol of the organosilane (1) of the component (A1). Fiber as described in.   The coating film is formed from the composition [2], and the composition [2] is composed of (A2) component and (A2) component organosilane (2) 100 parts by weight. 2 to 900 parts by weight of (B) component in solid content, and (C2) component of 2 to 900 parts by weight with respect to 100 parts by weight of organosilane (2) of component (A2). fiber.   The fiber according to claim 3, comprising 0.5 to 3 moles of water with respect to 1 mole of the organosilane (2) as the component (A2).