JP4120045B2 - Photosensitive planographic printing plate - Google Patents

Description

【００４３】
（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、Ｒ⁵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。
【００４４】
（Ｃ）成分としては、例えば、
（ａ）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（ｉ）」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、
（ｂ）下記一般式（５）
【００４５】
【化２】

【００４６】
（式中、Ｘ、Ｒ⁵、ｉは一般式（４）におけるそれぞれＸ、Ｒ⁵、ｉと同義であり、Ｒ⁶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（ｉｉ）」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。
【００４７】
前記（ａ）の方法に使用されるヒドロシラン化合物（ｉ）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（ｉ）は、単独でまたは２種以上を混合して使用することができる。
【００４８】
また、前記（ａ）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（ａ−１）や（ａ−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、（ａ−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。
（ａ−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。
【００４９】
（ａ−１）および（ａ−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。
【００５０】
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種以上を混合して使用することができる。
【００５１】
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種以上を混合して使用することができる。
【００５２】
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。
【００５３】
また、前記（ｂ）の方法に使用される不飽和シラン化合物（ｉｉ）の具体例として次が挙げられる。
ＣＨ₂＝ＣＨ（ＣＨ₃）Ｓｉ（ＯＣＨ₃）₂、ＣＨ₂＝ＣＨＳｉ（ＯＣＨ₃）₃、
ＣＨ₂＝ＣＨ（ＣＨ₃）ＳｉＣｌ₂、ＣＨ₂＝ＣＨＳｉＣｌ₃、
ＣＨ₂＝ＣＨＣＯＯ（ＣＨ₂）₃Ｓｉ（ＯＣＨ₃）₃、
ＣＨ₂＝ＣＨＣＯＯ（ＣＨ₂）₃Ｓｉ（ＣＨ₃）（ＯＣＨ₃）₂、
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）₂ＳｉＣｌ₃、
ＣＨ₂＝Ｃ（ＣＨ₃）ＣＯＯ（ＣＨ₂）₃ＳｉＣｌ₃、
【００５４】
【化３】

【００５５】
これらの不飽和シラン化合物（ｉｉ）は、単独でまたは２種以上を混合して使用することができる。
【００５６】
また、不飽和シラン化合物（ｉｉ）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（ａ−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。
【００５７】
以上のようにして得られる（Ｃ）成分の好ましい例を、より具体的に示すと、下記一般式（６）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。
【００５８】
【化４】

【００５９】
（式中、Ｒ⁷は水素原子またはメチル基を示し、Ｒ⁸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、Ｒ⁹はＲ⁷と同義であり、Ｒ¹⁰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、Ｒ¹¹はＲ⁸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。）
【００６０】
また、（Ｃ）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。
【００６１】
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。
【００６２】
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。
（Ｃ）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。
【００６３】
組成物（ロ）において、（Ｃ）成分は、単独でまたは２種以上を混合して使用することができる。
組成物（ロ）における（Ｃ）成分の使用量は、（Ａ２）成分におけるオルガノシラン（Ｉ）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。
さらに、組成物（イ）および組成物（ロ）には、下記の（Ｅ）〜（Ｌ）成分を配合することができる。
【００６４】
（Ｅ）成分
（Ｅ）成分は、組成物（イ）においては、（Ａ１）成分等の加水分解・縮合反応を促進し、また組成物（ロ）においては、（Ａ２）成分、（Ｃ）成分等の加水分解・縮合反応を促進する触媒からなる。
【００６５】
組成物（イ）および組成物（ロ）においては、（Ｅ）成分を使用することにより、得られる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、かつ膜の厚膜化やコーティング作業も容易となる。このような（Ｅ）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。
（Ｅ）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。
【００６６】
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。
【００６７】
また、有機金属化合物等としては、例えば、下記一般式
Ｍ（ＯＲ¹²）_p（Ｒ¹³ＣＯＣＨＣＯＲ¹⁴）_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、Ｒ¹²およびＲ¹³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、Ｒ¹⁴は、Ｒ¹²およびＲ¹³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。
【００６８】
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。
【００６９】
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。
（Ｅ）成分は、単独でまたは２種以上を混合して使用することができる。
【００７０】
組成物（イ）および組成物（ロ）における（Ｅ）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、（Ｅ）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、膜がわれやすくなる傾向がある。
【００７１】
（Ｆ）成分
（Ｆ）成分は、下記一般式
Ｒ¹⁵ＣＯＣＨ₂ＣＯＲ¹⁶
（式中、Ｒ¹⁵およびＲ¹⁶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Ｒ¹³およびＲ¹⁴と同義である。）
で表されるβ−ジケトン類および／またはβ−ケトエステル類からなる。このような（Ｆ）成分は、前記（Ｅ）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。
【００７２】
（Ｆ）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、アセト酢酸エチルが好ましい。
【００７３】
（Ｆ）成分は、単独でまたは２種以上を混合して使用することができる。
組成物（イ）および組成物（ロ）における（Ｆ）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。
【００７４】
（Ｇ）成分
（Ｇ）成分は、前記（Ｂ）成分以外の無機化合物の微粒子および／またはゾルもしくはコロイドからなり、塗膜の所望の特性に応じて配合される。
【００７５】
（Ｇ）成分をなす化合物の具体例としては、ＳｉＯ₂、Ａｌ₂Ｏ₃、Ａｌ(ＯＨ)₃、Ｓｂ₂Ｏ₅、Ｓｉ₃Ｎ₄、Ｓｎ−Ｉｎ₂Ｏ₃、Ｓｂ−Ｉｎ₂Ｏ₃、ＭｇＦ、ＣｅＦ₃、ＣｅＯ₂、３Ａｌ₂Ｏ₃・２ＳｉＯ₂、ＢｅＯ、ＳｉＣ、ＡｌＮ、Ｆｅ、Ｆｅ₂Ｏ₃、Ｃｏ、ＣｒＯ₂、Ｆｅ₄Ｎ、Ｂａフェライト、ＳｍＣｏ₅、ＹＣｏ₅、ＣｅＣｏ₅、ＰｒＣｏ₅、Ｓｍ₂Ｃｏ₁₇、Ｎｄ₂Ｆｅ₁₄Ｂ、ＺｒＯ₂、Ａｌ₄Ｏ₃等を挙げることができる。
【００７６】
（Ｇ）成分の存在形態には、微粒子からなる粉体、微粒子が水中に分散した水系のゾルもしくはコロイド、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がある。溶媒系のゾルもしくはコロイドの場合、半導体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。
【００７７】
（Ｇ）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。
（Ｇ）成分は、単独でまたは２種以上を混合して使用することができる。
【００７８】
（Ｇ）成分を組成物中に配合する方法としては、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、（Ｇ）成分を、第１組成物においては、前記（Ａ１）成分、（Ｂ）成分等と共加水分解・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、（Ｃ）成分等と共加水分解・部分縮合させてもよい。
組成物（イ）および組成物（ロ）における（Ｇ）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。
【００７９】
（Ｈ）成分
（Ｈ）成分は、前記（Ｅ）成分以外の硬化促進剤からなる。このような（Ｈ）成分を使用することにより、組成物（イ）および組成物（ロ）のコーティング用組成物から形成された塗膜の硬化速度を高めることができ、比較的低い温度で硬化させるためには、（Ｈ）をさらに添加する方が効果的である。
【００８０】
（Ｈ）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−アニリ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＝ＣＨＣＯＯＣ₄Ｈ₉）₂、
（Ｃ₈Ｈ₁₇）₂Ｓｎ（ＯＣＯＣ₁₁Ｈ₂₃）₂、
（Ｃ₈Ｈ₁₇）₂Ｓｎ（ＯＣＯＣＨ＝ＣＨＣＯＯＣＨ₃）₂、
（Ｃ₈Ｈ₁₇）₂Ｓｎ（ＯＣＯＣＨ＝ＣＨＣＯＯＣ₄Ｈ₉）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、
【００８１】
【化５】

【００８２】
等のメルカプチド型有機錫化合物；
（Ｃ₄Ｈ₉）₂Ｓｎ＝Ｓ、（Ｃ₈Ｈ₁₇）₂Ｓｎ＝Ｓ、
【００８３】
【化６】

【００８４】
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。（Ｈ）成分は、単独でまたは２種以上を混合して使用することができる。
【００８５】
（Ｈ）成分の使用量は、組成物（イ）においては、前記（Ａ１）成分におけるオルガノシラン（１）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。（Ｈ）成分の使用量が１００重量部を越えると、平版印刷版としての耐久性に劣る。
【００８６】
その他の成分（Ｊ）〜（Ｌ）
さらに、本発明に用いるコーティング組成物には、必要に応じて（Ｊ）染料、（Ｋ）可塑剤、（Ｌ）界面活性剤（レベリング剤）等の常套の添加剤を配合することもできる。
コーティング組成物の着色に使用される好ましい（Ｊ）染料としては、油溶性染料、塩基性染料を挙げることができる。
このような染料の具体例としては、クリスタルバイオレット、マラカイトグリーン、ビクトリアブルー、メチレンブルー、メチルバイオレット、エチルバイオレット、ローダミンＢ、ビクトリアピュアーブルーＢＯＨ（保土谷化学工業（株）製）、オイルブルー＃６１３（オリエント化学工業（株）製）、パーマネントブルー＃４７（大同化学工業（株）製）等を挙げることができる。
【００８７】
これらの染料の配合量は、全コーティング組成物の０．１〜５重量％が好ましい。０．１重量％以下では染料添加による着色効果に乏しく、また５重量％を越えると感光性平板印刷版として重要な特性である感度が低下する。
前記（Ｋ）可塑剤や（Ｌ）界面活性剤は、コーティング組成物の塗布性を良くしたり、コーティング組成物の支持体への接着性を向上させる目的で用いられる。
【００８８】
（Ｋ）可塑剤としては、例えばジメチルフタレート、ジエチルフタレート、ジ−ｎ−ブチルフタレート、ジ−ｎ−ヘプチルフタレート、ジ−２−エチルヘキシルフタレート、ジ−ｎ−オクチルフタレート、ジイソデシルフタレート、ｎ−ブチルベンジルフタレート、ジイソノニルフタレート、エチルフタリルエチルグリコール、ジメチルイソフタレート、トリ−ｎ−ブチルフォスフェート、トリクレジルフォスフェート、トリ−ｎ−オクチルフォスフェート、トリフェニルフォスフェート、トリ（２−クロロエチル）フォスフェート、クエン酸トリ−ｎ−ブチル等を挙げることができる。これらの可塑剤は、単独でまたは２種以上を混合して使用することができる。前記可塑剤の配合量は、全感光性組成物の０．５〜３重量％が好ましい。
【００８９】
（Ｌ）界面活性剤としては、陰イオン界面活性剤、フッ素系界面活性剤、シリコン系界面活性剤等を挙げることができる。
【００９０】
コーティング組成物の製造
組成物（イ）を製造するに際しては、（Ｅ）成分における有機金属化合物等と（Ｆ）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（Ｆ）成分とを使用する場合は、好ましくは、（Ａ１）〜（Ｆ）成分のうち（Ｆ）成分を除いた混合物を得たのち、これに（Ｆ）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（Ｅ）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、（Ｆ）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（Ｅ）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、（Ｆ）成分を添加する方法。
【００９１】
また、組成物（イ）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、組成物（イ）においては、（Ａ１）〜（Ｆ）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。
【００９２】
また、組成物（ロ）を調製するに際しては、（Ｅ）成分における有機金属化合物等と（Ｆ）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（Ｆ）成分とを使用する場合は、好ましくは、（Ａ２）〜（Ｆ）成分のうち（Ｆ）成分を除いた混合物を得たのち、これに（Ｆ）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、（Ｃ）成分、（Ｅ）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、（Ｆ）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（Ｃ）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、（Ｆ）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、（Ｅ）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（Ｃ）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。
【００９３】
また、組成物（ロ）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、組成物（ロ）においては、（Ａ２）〜（Ｆ）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。
【００９４】
感光性平版印刷版の製作
本発明の感光性平版印刷版は、本発明のコーティング組成物を支持体表面に塗布し、乾燥して製作する。前記支持体としては、紙、プラスチックフィルム、あるいは銅、亜鉛、アルミニウム、ステンレス等の金属板や、これらを二種以上組み合わせた複合材料を用いることができる。これらの中で、特に、ブラシ研磨またはボール研磨したアルミニウム板、ブラシ研磨したのち陽極酸化処理を施したアルミニウム板、電解研磨したのち陽極酸化を施したアルミニウム板が軽くて持ち運びやすいこと、形状安定性に優れること等から好ましい。
【００９５】
このような前処理を施したアルミニウム板には、さらに、ケイ酸アルカリ、リン酸ソーダ、フッ化ナトリウム、フッ化ジルコニウム、アルキルチタネート、トリヒドロキシ安息香酸等の単独液あるいは混合液による化成処理；ベーマイト処理、酢酸ストロンチウム、酢酸亜鉛、酢酸マグネシウム、安息香酸カルシウム等の水溶液による被覆処理；ポリビニルピロリドン、ポリアミンスルホン酸、ポリビニルスルホン酸、ポリ（メタ）アクリル酸、ポリ−２−ヒドロキシエチルアクリレート等による被覆処理等を後処理として行うこともできる。
【００９６】
更には、支持体とコーティング組成物との密着性向上を目的に支持体に各種シランカップリング剤処理を行うこともできる。使用されるカップリング剤としては、アミノ基、ヒドロキシル基、カルボキシル基、エポキシ基、ポリエチレノキシド基より選ばれる少なくとも一つの基を有するアルコキシシラン系カップリング剤が好ましい。
また、本発明の平版印刷板の耐磨耗性向上を目的として、まず基板に下層としてコーティング組成物のバインダー材料である、アルコキシシラン化合物を塗布して層を形成させ、その上層としてコーティング組成物を塗布、乾燥して平版とすることもできる。また、必要に応じて下層は各種有機ポリマー層を塗布利用することもできる。
コーティング組成物の塗布方法についても特に制約はなく、バーコーター、ディップコーター、ダイコーター等の各種塗布機あるいはスクリーン印刷等の各種印刷機を用いて塗布することができる。また、従来公知の方法、例えば回転塗布、押出し塗布、ワイヤーバー塗布、ロール塗布、エアーナイフ塗布、ディップ塗布、カーテン塗布等を採用することもできる。コーティング組成物の塗布量は、用途により異なるが、固形分として０．１〜１０ｇ／ｍ²が好ましい。
また塗布後の乾燥も、ホットプレート、オーブン、熱風乾燥機、赤外線乾燥機等の各種加熱型乾燥機であればいずれでも良く、基材にもよるが８０〜２００Ｃ、好ましくは８０〜１５０Ｃにて１〜３０分程度加熱することにより乾燥することができる。
【００９７】
平版印刷版の製作
感光性のコーティング組成物を塗布して得られた感光性平版印刷版に、所望のパターンに露光して平板印刷版を製作する。露光方法については、従来から感光性平版の露光に使用される各種露光装置を利用することができる。露光に使用される活性光線の光源としては、例えば水銀灯、メタルハライドランプ、キセノンランプ、ケミカルランプ、カーボンアーク灯、アルゴンレーザー、ヘリウム・カドミニウムレーザー、エキシマレーザー等を用いることができる。
露光の仕方としては、例えばまず感光性平版の表面に所望の印刷用マスクを置き、これに上記光源を利用して露光させることで潜像を得ることができる。この際、光照射された部分が親水部分であり、マスクされた部分が疎水性を示す。すなわち水性インキを用いるのであればマスクはネガマスクとなり、油性インキを用いるのであればマスクはポジマスクとなる。
必要露光量は通常１００ｍＪ〜５０００ｍＪであり、安定的にコントラストを得る意味で５００ｍＪ以上の露光が好ましい。
また、本感光性平版印刷版に直接レーザーを用いて潜像を直描で描くこともできる。レーザー露光の光量はレーザー波長にも依存さるが、上記露光量と同様の範囲が好ましい。露光面は、表面洗浄等を目的に、純水あるいはアルコール等で処理することも必要に応じて可能である。
露光後の平版の保存に特に制限はないが、可能な限り低温且つ暗所での保管が好ましい。
【００９８】
【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、その要旨を越えない限り、これらの実施例に何ら制約されるものではない。以下において部は重量部であり、％は重量％である。
コーティング組成物の製造（合成例の原料は表１に一覧した）
評価方法
解像性：line／space＝１／２のマスクで解像できた最小ライン幅で評価した。
汚れ ：印刷時に本来無地の部分にインキが付着しないものを“なし”とし、インキが付着したものを“あり”とした。
保存性：印刷特性（解像性と汚れ）の評価をした平版を、常温暗所で３カ月間保管後に再度印刷特性を評価した。その結果が３ヶ月前と変わらず、保存性が優れているものを「良好」とした。
【００９９】
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％〕、シリカの溶媒系ゾル７５部（シリカ含量３０％）、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２３％の透明コーテイング組成物（I-a）を製造した。
【０１００】
合成例２、３
原料を表１に示すとおりにした以外は合成例１と同様にして、固形分濃度２０％の、透明コーテイング組成物（I-b)および（I-c）を製造した。固形分濃度はそれぞれ２３％、２１％であった。
合成例４
合成例１において、塗料用酸化チタン（ルチル型）５０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４００部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２２％の着色コーテイング組成物（I-a')を製造した。
【０１０１】
合成例５
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％）、シリコン変性アクリル樹脂（鐘淵化学工業（株）製カネカゼムラック、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、固形分濃度３３％の透明組成物（II-a）を得た。
【０１０２】
合成例６
酸化チタンを配合せず、ｉ-プロピルアルコールを減量した他は合成例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）を製造した。
【０１０３】
実施例１
厚さ０．２４ｍｍの１Ｓ材のアルミニウム板をナイロンブラシと４００メッシュのバミストンの水性懸濁液を用いて表面研磨したのち、よく水洗した。
このアルミニウム板を、１０重量％水酸化ナトリウム水溶液中に、７０℃で６０秒間浸漬してエッチングし、流水で水洗したのち、塩酸（濃度３５ｇ／リットル）、ホウ酸（濃度２０ｇ／リットル）、およびアルミニウムイオン（濃度２０ｇ／リットル）からなる電解液中、４５℃にて、３０Ａ／ｄｍ²の電流密度で、３０秒間電解研磨し、その後水洗、乾燥させた。
【０１０４】
このようにして得たアルミニウム板に、合成例１の組成物（I-a）をバーコーターを用いて塗布し、１２０度にて１０分間乾燥して感光性平版印刷版を得た。これらの平版印刷版の感光層の乾燥重量は、それぞれ２．５ｇ／ｍ²であった。得られた感光性平版印刷版に、ネガフィルムおよびコダック社製ステップタブレットＮｏ．２を真空密着し、１００ｍＷの高圧水銀ランプを有するカールズース社製アライナーＭＡ１００型を用いて６０秒露光した。光量は４２０ｎｍ波長にて１８ｍＷ／ｃｍ²の照度であり、１０８０ｍＪの露光を行うことにより平版印刷版試料（１）を得た。
【０１０５】
得られた印刷版（１）を用いてスプリント印刷機にて印刷したところ、印刷汚れのない良好な印刷物が得られた。また、line／spaceが１／２の解像性評価用フィルムマスクを用いて、平版を試作し、印刷を行ったところ、解像できた最も細いライン幅は６０μｍであった。さらに、この平版印刷版を常温にて３ヶ月放置後に、再度印刷特性を評価した結果、ほぼ初期と同等の特性を有することから保存性もよいことが判明した。
また、感光性平版印刷版の片面をアルミホイルで覆い、先と同様にアライナーを用いて１１００ｍＪの露光を行った。本試料の露光部と非露光部（アルミホイルで覆われていた部分）について、純水による接触角を測定したところそれぞれ１０度と１５４度であった。
【０１０６】
実施例２〜５、比較例１
実施例１と同様に合成例２〜６で得た組成物の評価を行った。結果は表１に示す。なお、合成例６の組成物（III-a）は比較例１である。
【０１０７】
【表１】

【０１０８】
【発明の効果】
本発明の感光性平版印刷版は、光重合性組成物を必要とせず、したがってその現像が不要という画期的な特徴を有する環境に優しい技術である。本発明の感光性平版印刷版に露光して製作した平版印刷版は、耐汚染性、耐刷性および保存性に優れている。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a lithographic printing plate, and more particularly to a photosensitive lithographic printing plate that does not require a coating film made of a photopolymerizable composition and does not require development with a solvent or the like.
[0002]
[Prior art]
As the planographic printing plate, for example, as described in JP-A-9-169173, a photosensitive planographic printing plate in which a coating film made of a photopolymerizable composition is provided on an aluminum plate is generally used. Conventional photosensitive lithographic printing plates are of a negative type and a positive type, both of which form a photosensitive layer by applying a photopolymerizable composition on a support such as an aluminum plate, Actinic rays such as ultraviolet rays are irradiated through the negative image (hereinafter referred to as “exposure”). In the case of negative photosensitivity, the exposed portion is polymerized or crosslinked and then developed to remove the unexposed portion. In the case of positive photosensitivity, the exposed area is solubilized and then developed to remove the exposed area. The remaining coating layer repels water to become an image portion that receives ink, and the portion from which the coating film has been removed becomes a non-image portion that receives water and repels ink, thereby producing a lithographic printing plate.
[0003]
In negative photosensitive lithographic printing plates, a photosensitive layer comprising a diazo compound and a binder resin is widely used. As the diazo compound, a diazo resin typified by a condensate of 4-diazodiphenylamine and formaldehyde is generally used. It is commonly used. On the other hand, the binder resin is classified into an alkali developing type in which an unexposed portion is developed with an aqueous alkaline developer and a solvent developing type in which an unexposed portion is developed with an organic solvent developer.
[0004]
In recent years, alkali development type photosensitive lithographic printing plates have attracted attention from the viewpoint of safety and hygiene in the working environment, and as a binder resin therefor, for example, hydroxyalkyl (metabolites described in JP-B-52-7364). ) A copolymer mainly composed of acrylate, a copolymer mainly composed of hydroxyphenoxypropyl (meth) acrylate described in JP-B-57-51656, and the like are known. However, photosensitive lithographic printing plates using these (meth) acrylate copolymers are inferior in ink setting properties and printing durability, and the image area is dissolved or swelled by chemicals used in processing during printing. There are disadvantages. These disadvantages are derived from a hydrophilic binder for imparting developability, and are essentially inevitable problems in wet development. That is, a printing plate that does not require a wet development system has been considered ideal in terms of environment, safety, and energy saving.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel photosensitive lithographic printing plate that does not use a photopolymerizable composition. Another object of the present invention relates to development which is a problem in a photosensitive lithographic printing plate, and a photosensitive lithographic printing plate capable of obtaining a contrast between a hydrophilic portion and a hydrophobic portion by exposure without using a solvent or an alkaline water. It is to provide. A further object of the present invention is to provide a lithographic printing plate having high mechanical strength, chemical resistance, and ensuring stable printing characteristics even after storing the printing plate for a long time.
[0006]
[Means for Solving the Problems]
As a result of diligent research to obtain a photosensitive lithographic printing plate based on a novel idea that overcomes the above-described problems, the present inventors have applied the fact that a material having a photocatalytic function exhibits a high degree of hydrophilicity. The present inventors have found that the problem can be solved and have reached the present invention. That is, the gist of the present invention is obtained by applying (A) a film-forming substrate and (B) a composition containing fine particles and / or sol having photocatalytic activity (hereinafter also referred to as “coating composition”). Located on photosensitive lithographic printing plate. As the film-forming substrate, polyorganosiloxane is particularly preferable.
[0007]
Another gist of the present invention resides in a photosensitive lithographic printing plate, wherein the coating composition is selected from the following (A) and (B).
(A) (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 0, 1 or 2. )
A polyorganosiloxane which is a hydrolyzate and / or a partial condensate of an organosilane represented by
(B) Fine particles and / or sol having photocatalytic activity and
(D) Water and / or organic solvent
A composition containing
[0008]
(B) (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, 1 or 2. )
A polyorganosiloxane which is at least one component selected from the group consisting of an organosilane represented by the formula: a hydrolyzate of the organosilane and a partial condensate of the organosilane;
(B) fine particles and / or sol having photocatalytic activity,
(C) 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;
(D) Water and / or organic solvent
A composition containing
Further, the gist of the present invention resides in a lithographic printing plate in which the photosensitive lithographic printing plate is irradiated with light through a negative image to make the irradiated portion hydrophilic.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
(A) Film-forming base material: The film-forming base material used in the present invention has a component (B) that can be mixed, is hardly decomposed or deteriorated by the component (B), and is hydrophilic / hydrophobic. Must be in the middle region. Further, if the glass transition temperature is not high, there is a problem that paper dust is easily picked up during printing. Examples of the polymer that satisfies these conditions include polyorganosiloxane, thermosetting silicone, fluororesin, polyester resin, polyamide resin, urethane resin, epoxy resin, and phenol resin. Can be used.
Among these, polyorganosiloxane is preferable because it is chemically stable and has a proper hydrophilic / hydrophobic balance. In the present invention, polyorganosiloxane is mainly described as the film-forming base material. However, in the case of using the other resins, depending on the characteristics of each resin, the component (B) may be mixed to form a film. Good.
[0010]
(A) A polyorganosiloxane has the following repeating units.
[-Si (R)₂O-]
Here, R represents a hydrogen atom or a monovalent organic group, and 40 to 100% of R is preferably an alkyl group having 1 to 8 carbon atoms, but 40% or less of R is other than a hydrogen atom and the alkyl group. Or an organic group of
Preferred examples of the polyorganosiloxane are the following (A1) and (A2).
(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 0, 1 or 2. )
A hydrolyzate of organosilane and / or a partial condensate thereof.
(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, 1 or 2. )
At least one component selected from the group consisting of an organosilane, a hydrolyzate of the organosilane, and a partial condensate of the organosilane.
[0011]
(B) component: Fine particles and / or sol having photocatalytic activity
The component (B) is preferably composed of semiconductor fine particles and / or sol having photocatalytic activity. As a semiconductor having photocatalytic activity, for example, TiO₂TiO_Three, SrTiO_Three, FeTiO_Three, WO_Three, SnO₂, Bi₂O_Three, In₂O_ThreeZnO, Fe₂O_Three, RuO₂, CdO, CdFeO_Three, LaRhO_ThreeMetal oxides such as CdS, CdSe, GaP, GaAs, MoS₂Preferably metal oxides, particularly preferably TiO₂And ZnO. More preferably, anatase TiO₂It is. Since the present invention utilizes the photocatalytic ability of fine particles by external light irradiation, it is preferable to use fine particles that have not been subjected to a surface treatment that prevents photoactivity.
Component (B) is present in the form of a powder consisting of fine particles, an aqueous sol in which the fine particles are dispersed in water, a solvent sol in which the fine particles are dispersed in a polar solvent such as isopropyl alcohol or a nonpolar solvent such as toluene. There are three types. In the case of a solvent-based sol, depending on the dispersibility of the semiconductor fine particles, it may be further diluted with water or a solvent. The average particle diameter of the semiconductor 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.
[0012]
As a method of blending the component (B) in the composition,
(I) A composition comprising the component (A1) and the components (D) to (L) to be described later, or a composition comprising the component (A2) and the components (C) to (L) to be described later. A method of adding the component (B) after the preparation of
(Ii) There is a method of adding the component (B) when preparing the composition of the above (i). Further, when the component (B) is an aqueous sol, it is preferably added by the method (i), and also when the viscosity in the system increases due to the blending of the component (G) described later, (ii) It is preferable to add the component (B) at the time of preparing the composition (i) by the method (1).
In the composition (A) and the composition (B), the component (B) can be used alone or in combination of two or more.
[0013]
Hereinafter, each component which comprises the coating composition containing (A) component and (B) component used by this invention is demonstrated sequentially.
(A1) component
The component (A1) in the composition (A) comprises a hydrolyzate and / or partial condensate thereof of an organosilane represented by the general formula (1) (hereinafter referred to as “organosilane (1)”). Comprising a hydrolyzate and / or a partial condensate thereof containing at least one component in which n in the general formula (1) is an integer of 0, 1 or 2 and acting as a main binder in the composition (a) To do.
In the general formula (1), R¹Is preferably an organic group having 1 to 8 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an n-pentyl group, an n- Alkyl groups such as hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, vinyl group, allyl group, acyl group, glycidyl group, (meth) acryloxy group, ureido group, amide group, fluoroacetamide In addition to groups and isocyanate groups, substituted derivatives of these groups can be mentioned.
[0014]
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. However, R consisting of these substituted derivatives¹The carbon number of is 8 or less including the carbon atom in a substituent. R in general formula (1)¹May be the same as or different from each other.
[0015]
R²Is preferably an organic group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a valeryl group, and a caproyl group.
Multiple R's in general formula (1)²May be the same as or different from each other.
[0016]
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, cyclohexyltri Methoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxy Shi 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxy Silane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, vinyltriacetoxysilane, 3-chloropropyl Trimethoxysilane, 3-chloropropyltriethoxysilane, 3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrie Xysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, etc. In addition to the trialkoxysilanes, methyltriacetyloxysilane, methyltriphenoxysilane, and the like can be given.
[0017]
The said organosilane (1) whose n of the said General formula (1) is 1 can be used individually or in mixture of 2 or more types.
[0018]
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-pentyldiethoxysilane , Di-n Hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, dicyclohexyldimethoxysilane In addition to dialkoxysilanes such as 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 admixture of two or more.
[0019]
Specific examples of the organosilane in which n is 0 include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetraacetyloxysilane, tetraphenoxysilane, and the like. Can be mentioned.
Of these organosilanes, trialkoxysilanes are preferable, and methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane are more preferable.
Commercially available products of component (A1) include MKC silicate manufactured by Mitsubishi Chemical Co., Ltd., silicate manufactured by Tama Chemical Co., Ltd., silicon resin manufactured by Toray Dow Corning Silicone Co., and silicon resin manufactured by Toshiba Silicone Co., Ltd. There are silicon oligomers manufactured by Nihon Unika Co., Ltd., and these may be used.
These organosilanes can be used alone or in admixture of two or more.
[0020]
The organosilane (1) can be hydrolyzed and partially condensed in advance and used as the component (A1). However, as described later, the organosilane (1) is mixed with the remaining components to prepare a composition. At this time, it is preferable to hydrolyze and partially condense organosilane (1) by adding an appropriate amount of water (component (D)) to obtain component (A1).
[0021]
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.
[0022]
(A2) component
The component (A2) in the composition (b) is an organosilane represented by the general formula (2) (hereinafter referred to as “organosilane (2)”), a hydrolyzate of organosilane (2), and organosilane. It consists of at least one selected from the partial condensates of (2), and acts as the main binder in the composition (b).
[0023]
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.
[0024]
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. However, R consisting of these substituted derivatives^ThreeThe carbon number of is 8 or less including the carbon atom in a substituent.
R in general formula (2)^ThreeMay be the same as or different from each other.
[0025]
R^FourIs preferably an organic group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group. Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a valeryl group, and a caproyl group.
Multiple R's in general formula (2)^FourMay be the same as or different from each other.
[0026]
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.
[0027]
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.
Commercially available products of component (A2) include MKC silicate manufactured by Mitsubishi Chemical Co., Ltd., silicate manufactured by Tama Chemical Co., Ltd., silicone resin manufactured by Toray Dow Corning Silicone Co., and silicone resin manufactured by Toshiba Silicone Co., Ltd. There are silicon oligomers manufactured by Nihon Unika Co., Ltd., and these may be used.
(A2) A component can be used individually or in mixture of 2 or more types.
[0028]
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.
[0029]
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.
[0030]
In the composition (a) and the composition (b), the coating surface is made hydrophilic in a short time even by weak light due to the photocatalytic ability of the component (B). It was revealed that the stain resistance of the coating film can be remarkably improved without damaging the film. Moreover, in the coating film obtained from the composition (a) and the composition (b), the component (B) is co-condensed with the component (A1) or the component (A2), etc. Contamination resistance is maintained for a long time.
[0031]
As a method of blending the component (B) in the composition, the component (A1) or (A2) may be added after the preparation of the composition comprising the component other than the components (A) and (B) described later, Alternatively, it may be added during preparation of the composition, and the component (A1) or component (A2) may be hydrolyzed and partially condensed in the presence of the component (B). When the component (B) is added during the preparation of the composition, the semiconductor compound in the component (B) can be co-condensed with the component (A1) or the component (A2), and the resulting coating film has a long antifouling property. Durability is improved. Further, when the component (B) is an aqueous sol, it is preferably added at the time of preparing the composition, and also when the viscosity in the system increases due to the blending of the component (G) described later, the component (B) Is preferably added during preparation of the composition. In the compositions (A) and (B), the component (B) can be used alone or in admixture of two or more.
[0032]
(B) The usage-amount of a component is 1-500 weight part normally with a solid content with respect to 100 weight part of (A) component which is a film-forming base material, Preferably it is 5-400 weight part. If the amount of the component (B) is below this range, the degree of hydrophilization after light irradiation is insufficient for printing plates, and on the other hand, film formation becomes difficult above this range.
[0033]
(D) component
The component (D) in the compositions (A) and (B) consists of water and / or an organic solvent.
The amount of water used in the compositions (a) and (b) is usually 0.5 to 3 mol, preferably 0.7, per 1 mol of the total organosilane in the components (A1) and (A2). About 2 mol.
[0034]
The composition (b) contains the components (A2) and (B) and the component (C) described later, and contains the components (E) to (L) described later according to the purpose. However, usually, when preparing the composition, it is preferable to add water in order to cause the organosilane (2) or (D) component to undergo hydrolysis / partial condensation reaction or to disperse the particulate component.
[0035]
The amount of water used in the composition (b) is usually about 0.5 to 3 mol, preferably about 0.7 to 2 mol, per 1 mol of the organosilane (2) in (A2). The organic solvent (D) in the composition (a) is not particularly limited as long as the above components can be mixed uniformly. For example, alcohols, aromatic hydrocarbons, ethers, ketones, esters Or more.
[0036]
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.
[0037]
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.
[0038]
The coating composition (photosensitive composition) used in the present invention has a total solid content of preferably 5 to 50% by weight in both the composition (a) and the composition (b), and is appropriately adjusted according to the purpose of use. The For example, when it is intended to impregnate a thin film forming substrate, it is usually 5 to 30% by weight. When it is used for the purpose of forming a thick film, it is usually 20 to 50% by weight, preferably 30 to 45% by weight. %. When the total solid content concentration of the composition is less than 5% by weight, the formation of the coating film is inferior.
[0039]
The composition (A) contains the components (A1), (B), and (D) as essential, and optionally contains components (E) to (H) described later. The composition (b) contains the components (A2), (B), (D) and the component (C) described below, and optionally contains components (E) to (H) described later. . The component (D) water is added in order to hydrolyze the organosilane or partially condense, or to disperse the particulate component when preparing the composition.
[0040]
(C) component
The component (C) in the composition (b) 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”) at the end of the polymer molecular chain and / or It consists of a polymer in the side chain.
When such a component (C) cures the coating film obtained from the coating composition of the composition (b), 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 coating-film performance by co-condensing with a component.
The content of the specific silyl group in the component (C) is usually 0.001 to 20% by weight in terms of the amount of silicon atoms with respect to the polymer before the introduction of the specific silyl group.
[0041]
The specific silyl group is preferably the following general formula (4)
[0042]
[Chemical 1]

[0043]
(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;^FiveRepresents 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. )
It is represented by
[0044]
As the component (C), for example,
(A) A hydrosilane compound corresponding to the general formula (4) (hereinafter referred to as “hydrosilane compound (i)”) is converted into a vinyl polymer having a carbon-carbon double bond (hereinafter referred to as “unsaturated vinyl heavy weight”). A method of causing an addition reaction to the carbon-carbon double bond in
(B) The following general formula (5)
[0045]
[Chemical 2]

[0046]
(Where X, R^Five, I are X and R in the general formula (4), respectively.^Five, I and R⁶Represents an organic group having a polymerizable double bond. )
(Hereinafter referred to as “unsaturated silane compound (ii)”)
And those produced by a method of copolymerizing with other vinyl monomers.
[0047]
Examples of the hydrosilane compound (i) 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 (i) can be used alone or in admixture of two or more.
[0048]
The unsaturated vinyl polymer used in the method (a) is not particularly limited as long as it is other than a polymer having a hydroxyl group. For example, the following methods (a-1) and (a-2) Or it can manufacture by these combinations.
That is, after (a-1) vinyl monomer having a functional group (hereinafter referred to as “functional group (α)”) is (co) polymerized, functional group (i) in the (co) polymer And a functional group capable of reacting with the functional group (α) (hereinafter referred to as “functional group (β)”) and an unsaturated compound having a carbon / carbon double bond to react with the polymer molecular chain. An unsaturated vinyl polymer having a carbon-carbon double bond in its side chain can be produced.
(A-2) A radical polymerization initiator having a functional group (α) (for example, 4,4-azobis-4-cyanovaleric acid) 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.
[0049]
Examples of the reaction between the functional group (α) and the functional group (β) in the methods (a-1) and (a-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.
[0050]
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 admixture of two or more.
[0051]
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 admixture of two or more.
[0052]
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.
[0053]
Specific examples of the unsaturated silane compound (ii) used in the method (b) include the following.
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 (OCH_Three)_Three,
CH₂= CHCOO (CH₂)_ThreeSi (CH_Three) (OCH_Three)₂,
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)₂SiCl_Three,
CH₂= C (CH_Three) COO (CH₂)_ThreeSiCl_Three,
[0054]
[Chemical 3]

[0055]
These unsaturated silane compounds (ii) can be used alone or in admixture of two or more.
[0056]
Examples of other vinyl monomers copolymerized with the unsaturated silane compound (ii) include 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.
[0057]
More specifically, a preferable example of the component (C) obtained as described above is exemplified by a trialkoxysilyl group-containing (meth) acrylate copolymer represented by the following general formula (6). it can.
[0058]
[Formula 4]

[0059]
(Wherein R⁷Represents a hydrogen atom or a methyl group, R⁸Represents 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;⁹Is R⁷Is synonymous with R^TenRepresents an alkylene group having 1 to 4 carbon atoms such as a methylene group, an ethylene group, a propylene group or a butylene group;¹¹Is R⁸And k / (j + k) = 0.01 to 0.4, preferably 0.02 to 0.2. )
[0060]
Other specific examples of the component (C) include specific silyl group-containing epoxy resins, specific silyl group-containing polyester resins, and specific silyl group-containing fluororesins.
[0061]
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 is 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.
[0062]
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.
The number average molecular weight (hereinafter referred to as “Mn”) of the component (C) is preferably 2,000 to 100,000, and more preferably 4,000 to 50,000.
[0063]
In the composition (b), the component (C) can be used alone or in admixture of two or more.
The amount of the component (C) in the composition (b) is usually 2 to 900 parts by weight, preferably 10 to 400 parts by weight, more preferably 100 parts by weight of the organosilane (I) in the component (A2). Is 20 to 200 parts by weight.
Furthermore, the following (E)-(L) component can be mix | blended with a composition (I) and a composition (B).
[0064]
(E) component
In the composition (A), the component (E) promotes hydrolysis / condensation reaction of the component (A1), and in the composition (B), the component (A2), component (C), etc. It consists of a catalyst that promotes decomposition and condensation reactions.
[0065]
In the composition (A) and the composition (B), by using the component (E), the curing rate of the resulting film is increased and the polysiloxane resin produced by the polycondensation reaction of the organosilane component used The Mn of the film increases, and a coating film excellent in strength, long-term durability and the like can be obtained, and the film can be made thicker and the coating operation can be facilitated. Examples of such component (E) 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).
Among the components (E), 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, and preferably acetic acid.
[0066]
Moreover, as an alkaline compound, sodium hydroxide, potassium hydroxide etc. can be mentioned, for example, Preferably it is sodium hydroxide.
[0067]
Examples of the organometallic compound include the following general formula:
M (OR¹²)_p(R¹³COCHCOR¹⁴)_q
(Wherein M represents zirconium, titanium or aluminum, R¹²And R¹³Are 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, R¹⁴Is R¹²And R¹³As 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.
[0068]
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.
[0069]
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.
(E) A component can be used individually or in mixture of 2 or more types.
[0070]
The amount of the component (E) used in the composition (b) and the composition (b) is 100 parts by weight in total of the organosilane in the component (A1) or the organo 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 a total of 100 parts by weight of silane. Usually, 0 to 100 parts by weight, preferably 0.1 to 80 parts by weight, more preferably 100 parts by weight of organosilane in component A1) or 100 parts by weight of organosilane in component (A2). 0.5 to 50 parts by weight. In this case, when the amount of the component (E) used exceeds 100 parts by weight, the storage stability of the composition tends to be lowered or the film tends to be broken.
[0071]
(F) component
Component (F) has the following general formula
R¹⁵COCH₂COR¹⁶
(Wherein R¹⁵And R¹⁶Are each R in each general formula in the metal chelate compound.¹³And R¹⁴It is synonymous with. )
It consists of (beta) -diketone and / or (beta) -ketoester represented by these. Such a component (F) is preferably used in combination when an organometallic compound or the like is used among the components (E).
[0072]
Specific examples of the component (F) 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 and the like can be mentioned.
Of these, acetylacetone and ethyl acetoacetate are preferred.
[0073]
(F) A component can be used individually or in mixture of 2 or more types.
The amount of the component (F) used in the composition (I) and the composition (B) is usually 2 mol or more, preferably 3 to 20 mol, per 1 mol of the organometallic compound in the organometallic compound or the like. .
[0074]
(G) component
The component (G) comprises fine particles of inorganic compounds other than the component (B) and / or a sol or colloid, and is blended according to the desired properties of the coating film.
[0075]
As a specific example of the compound constituting the component (G), SiO₂, Al₂O_ThreeAl (OH)_Three, Sb₂O_Five, Si_ThreeN_Four, Sn-In₂O_Three, Sb-In₂O_Three, MgF, CeF_Three, CeO₂3Al₂O_Three・ 2SiO₂, BeO, SiC, AlN, Fe, Fe₂O_Three, Co, CrO₂, Fe_FourN, Ba ferrite, SmCo_Five, YCo_Five, CeCo_Five, PrCo_Five, Sm₂Co₁₇, Nd₂Fe₁₄B, ZrO₂, Al_FourO_ThreeEtc.
[0076]
Component (G) is present in the form of fine powder, a water-based sol or colloid in which the fine particles are dispersed in water, and a solvent in which the fine particles are dispersed in a polar solvent such as isopropyl alcohol or a nonpolar solvent such as toluene. There are sols or colloids of the system. 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 semiconductor fine particles.
[0077]
When the component (G) is an aqueous sol or colloid and a solvent sol or colloid, the solid content concentration is preferably 40% by weight or less.
(G) A component can be used individually or in mixture of 2 or more types.
[0078]
As a method of blending the component (G) in the composition, it may be added after the preparation of the composition, or it may be added during the preparation of the composition, and the component (G) It may be cohydrolyzed and partially condensed with (A1) component, (B) component, etc. In the second composition, it is cohydrolyzed with (A2) component, (B) component, (C) component, etc. -Partial condensation may be performed.
The amount of component (G) used in composition (A) and composition (B) is 100 parts by weight of the total organosilane in component (A1) or 100 parts by weight of organosilane in component (A2). The solid content is usually 0 to 500 parts by weight, preferably 0.1 to 400 parts by weight.
[0079]
(H) component
(H) component consists of hardening accelerators other than the said (E) component. By using such a component (H), the curing rate of the coating film formed from the composition (a) and the coating composition (b) can be increased and cured at a relatively low temperature. In order to achieve this, it is more effective to add (H) further.
[0080]
Examples of the component (H) 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-aniline Amine compounds such as linopropyltrimethoxysilane and various modified amines used as curing agents for epoxy resins;
(C_FourH₉)₂Sn (OCOC₁₁H_{twenty three})₂,
(C_FourH₉)₂Sn (OCOCH = CHCOOCH_Three)₂,
(C_FourH₉)₂Sn (OCOCH = CHCOOC_FourH₉)₂,
(C₈H₁₇)₂Sn (OCOC₁₁H_{twenty three})₂,
(C₈H₁₇)₂Sn (OCOCH = CHCOOCH_Three)₂,
(C₈H₁₇)₂Sn (OCOCH = CHCOOC_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,
[0081]
[Chemical formula 5]

[0082]
Mercaptide-type organotin compounds such as
(C_FourH₉)₂Sn = S, (C₈H₁₇)₂Sn = S,
[0083]
[Chemical 6]

[0084]
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. (H) component can be used individually or in mixture of 2 or more types.
[0085]
Component (H) is used in an amount of usually 0 to 100 parts by weight, preferably 0.1 to 80 parts by weight per 100 parts by weight of organosilane (1) in component (A1) in composition (A). Parts by weight, more preferably 0.5 to 50 parts by weight, and in the second composition, usually 0 to 100 parts by weight with respect to 100 parts by weight of the organosilane (2) in the component (A2), Preferably it is 0.1-80 weight part, More preferably, it is 0.5-50 weight part. When the amount of component (H) used exceeds 100 parts by weight, the durability as a lithographic printing plate is poor.
[0086]
Other components (J) to (L)
Furthermore, conventional additives such as (J) dyes, (K) plasticizers, and (L) surfactants (leveling agents) can be blended in the coating composition used in the present invention, if necessary.
Preferable (J) dyes used for coloring the coating composition include oil-soluble dyes and basic dyes.
Specific examples of such dyes include crystal violet, malachite green, Victoria blue, methylene blue, methyl violet, ethyl violet, rhodamine B, Victoria pure blue BOH (manufactured by Hodogaya Chemical Co., Ltd.), oil blue # 613 ( Orient Chemical Industry Co., Ltd.), and Permanent Blue # 47 (Daido Chemical Industry Co., Ltd.).
[0087]
The blending amount of these dyes is preferably 0.1 to 5% by weight of the total coating composition. If it is 0.1% by weight or less, the coloring effect due to the addition of the dye is poor, and if it exceeds 5% by weight, the sensitivity, which is an important characteristic of the photosensitive lithographic printing plate, is lowered.
The (K) plasticizer and (L) surfactant are used for the purpose of improving the coating property of the coating composition and improving the adhesion of the coating composition to the support.
[0088]
(K) Examples of the plasticizer include dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisodecyl phthalate, and n-butyl benzyl. Phthalate, diisononyl phthalate, ethyl phthalyl ethyl glycol, dimethyl isophthalate, tri-n-butyl phosphate, tricresyl phosphate, tri-n-octyl phosphate, triphenyl phosphate, tri (2-chloroethyl) phosphate And tri-n-butyl citrate. These plasticizers can be used alone or in admixture of two or more. The blending amount of the plasticizer is preferably 0.5 to 3% by weight of the total photosensitive composition.
[0089]
Examples of (L) surfactants include anionic surfactants, fluorine-based surfactants, silicon-based surfactants, and the like.
[0090]
Production of coating compositions
In producing the composition (A), when the organometallic compound or the like in the component (E) and the (F) component are not used, the mixing method of each component is not particularly limited, but the organometallic compound and the like (F In the case of using the component (A), preferably, after obtaining the mixture excluding the component (F) among the components (A1) to (F), the method of adding the component (F) to this, specifically, The following methods (1) to (2) are adopted.
(1) Hydrolysis and partial condensation reaction by adding a predetermined amount of water to a mixture comprising the organosilane (1), component (B), the necessary amount of organic solvent and component (E) constituting the component (A1). After performing, the method of adding (F) component.
(2) Hydrolysis / partial condensation reaction is carried out by adding a predetermined amount of water to a mixture composed of organosilane (1) and component (B) constituting component (A1) and a necessary amount of organic solvent, and then (E ) A component is added and mixed, and after further partial condensation reaction, the component (F) is added.
[0091]
In addition, the coating composition for the composition (I)
(3) The component (B) can be prepared by adding the component (B) after carrying out the method (1) or (2) using each component except the component (B).
In the composition (A), components other than the components (A1) to (F) can be added at an appropriate stage for adjusting the composition.
[0092]
In preparing the composition (b), when the organometallic compound in the component (E) and the component (F) are not used, the mixing method of each component is not particularly limited. In the case of using the component (F), it is preferable to obtain a mixture obtained by removing the component (F) from the components (A2) to (F), and then add the component (F) to the mixture. 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, (C) component, (E) component and the necessary amount of organic solvent constituting the component (A2). A method of adding the component (F) after performing a partial condensation reaction.
(5) A predetermined amount of water is added to a mixture comprising the organosilane (2) and the component (B) constituting the component (A2) and the necessary amount of organic solvent, followed by hydrolysis and partial condensation reaction, and then (C ) Component and (D) component are added and mixed, and further a partial condensation reaction is performed, and then (F) component is added.
(6) Hydrolysis and partial condensation reaction by adding a predetermined amount of water to a mixture comprising the organosilane (2), (B) component, (E) component and the necessary amount of organic solvent constituting the component (A2). Next, after adding (C) component and mixing and performing a partial condensation reaction, the method of adding (E) component.
[0093]
In addition, the composition (b)
(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 composition (b), components other than the components (A2) to (F) can be added at an appropriate stage for adjusting the composition.
[0094]
Production of photosensitive lithographic printing plates
The photosensitive lithographic printing plate of the present invention is produced by applying the coating composition of the present invention to the surface of a support and drying it. As the support, paper, plastic film, metal plates such as copper, zinc, aluminum, and stainless steel, or a composite material combining two or more of these can be used. Among these, in particular, brushed or ball-polished aluminum plates, brush-polished and anodized aluminum plates, and electrolytically-polished and anodized aluminum plates are light and easy to carry, shape stability It is preferable because of its superiority.
[0095]
The pretreated aluminum plate is further subjected to chemical conversion treatment with a single solution or a mixed solution of alkali silicate, sodium phosphate, sodium fluoride, zirconium fluoride, alkyl titanate, trihydroxybenzoic acid, etc .; boehmite Treatment, coating treatment with an aqueous solution of strontium acetate, zinc acetate, magnesium acetate, calcium benzoate, etc .; coating treatment with polyvinylpyrrolidone, polyaminesulfonic acid, polyvinylsulfonic acid, poly (meth) acrylic acid, poly-2-hydroxyethyl acrylate, etc. Etc. can also be performed as post-processing.
[0096]
Further, various silane coupling agent treatments can be performed on the support for the purpose of improving the adhesion between the support and the coating composition. As the coupling agent to be used, an alkoxysilane coupling agent having at least one group selected from an amino group, a hydroxyl group, a carboxyl group, an epoxy group, and a polyethylene oxide group is preferable.
For the purpose of improving the abrasion resistance of the lithographic printing plate of the present invention, first, an alkoxysilane compound, which is a binder material of the coating composition, is applied to the substrate as a lower layer to form a layer, and the upper layer is the coating composition. Can be applied and dried to form a lithographic plate. Moreover, various organic polymer layers can be applied and used as the lower layer as required.
There is no restriction | limiting in particular also about the coating method of a coating composition, It can apply | coat using various printing machines, such as various coating machines, such as a bar coater, a dip coater, and a die coater, or screen printing. Further, conventionally known methods such as spin coating, extrusion coating, wire bar coating, roll coating, air knife coating, dip coating, curtain coating and the like can also be employed. The coating amount of the coating composition varies depending on the application, but is 0.1 to 10 g / m as a solid content.²Is preferred.
Also, drying after coating may be any heating type dryer such as a hot plate, oven, hot air dryer, infrared dryer, etc., depending on the substrate, but 80 to 200C, preferably 80 to 150C. It can be dried by heating for about 1 to 30 minutes.
[0097]
Production of lithographic printing plates
A photosensitive lithographic printing plate obtained by applying a photosensitive coating composition is exposed to a desired pattern to produce a lithographic printing plate. As the exposure method, various exposure apparatuses conventionally used for exposure of photosensitive lithographic plates can be used. Examples of the active light source used for exposure include a mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a carbon arc lamp, an argon laser, a helium / cadmium laser, and an excimer laser.
As a method of exposure, for example, a desired printing mask is first placed on the surface of a photosensitive lithographic plate, and a latent image can be obtained by exposing it to the light source using the light source. At this time, the irradiated portion is a hydrophilic portion, and the masked portion is hydrophobic. That is, if water-based ink is used, the mask is a negative mask, and if oil-based ink is used, the mask is a positive mask.
The necessary exposure amount is usually 100 mJ to 5000 mJ, and exposure of 500 mJ or more is preferable in order to stably obtain contrast.
It is also possible to draw a latent image directly on the photosensitive lithographic printing plate using a laser. The amount of laser exposure depends on the laser wavelength, but the same range as the above exposure is preferable. The exposed surface can be treated with pure water or alcohol as needed for the purpose of surface cleaning or the like.
There is no particular limitation on the preservation of the lithographic plate after exposure, but it is preferable to store it in the dark as possible as possible.
[0098]
【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 unless it exceeds the gist. In the following, parts are parts by weight and% is% by weight.
Production of coating composition (synthetic raw materials are listed in Table 1)
Evaluation methods
Resolution: Evaluation was made with the minimum line width that could be resolved with a mask of line / space = 1/2.
Stain: “None” means that no ink adheres to a plain area during printing, and “Yes” means that ink adheres.
Preservability: The printing characteristics (resolution and stains) of the planographic plates were evaluated again after storage for 3 months in a dark room temperature. The result was the same as 3 months ago, and the one with excellent storage stability was defined as “good”.
[0099]
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 (silica content 30%) and 200 parts of i-propyl alcohol were added and mixed. The mixture was reacted at 60 ° C. for 4 hours with stirring. 20 parts of methoxysilane was added afterwards to produce a transparent coating composition (Ia) having a solid content concentration of 23%.
[0100]
Synthesis examples 2 and 3
Transparent coating compositions (I-b) and (I-c) having a solid concentration of 20% were produced in the same manner as in Synthesis Example 1 except that the raw materials were as shown in Table 1. The solid content concentrations were 23% and 21%, respectively.
Synthesis example 4
In Synthesis Example 1, solids were obtained in the same manner as in Synthesis Examples 1 to 3, except that 50 parts of titanium oxide for paint (rutile type) was further added and the reaction was carried out with 400 parts of i-propyl alcohol added. A colored coating composition (Ia ′) having a partial concentration of 22% was produced.
[0101]
Synthesis example 5
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%), silicon-modified acrylic resin (Kaneka Chemical Co., Ltd. Kanekazemulac, solid content concentration 50%) 50 parts, di-i-propoxy ethylacetoacetate aluminum 20 parts, i-propyl alcohol 200 Part was added and mixed, and the mixture was reacted at 60 ° C. for 4 hours with stirring. Subsequently, it cooled to room temperature and 20 parts of acetylacetone was post-added and the transparent composition (II-a) with a solid content concentration of 33% was obtained.
[0102]
Synthesis Example 6
A transparent coating composition (III-a) having a solid content concentration of 20% was produced in the same manner as in Synthesis Example 1 except that titanium oxide was not added and i-propyl alcohol was reduced.
[0103]
Example 1
A surface of an aluminum plate of 1S material having a thickness of 0.24 mm was polished with a nylon brush and an aqueous suspension of 400 mesh Bamiston, and then washed thoroughly with water.
This aluminum plate was etched by immersing it in a 10% by weight aqueous sodium hydroxide solution at 70 ° C. for 60 seconds, washed with running water, hydrochloric acid (concentration 35 g / liter), boric acid (concentration 20 g / liter), and 30 A / dm at 45 ° C. in an electrolytic solution composed of aluminum ions (concentration 20 g / liter)²Was electropolished at a current density of 30 seconds, then washed with water and dried.
[0104]
The aluminum plate thus obtained was coated with the composition (I-a) of Synthesis Example 1 using a bar coater and dried at 120 degrees for 10 minutes to obtain a photosensitive lithographic printing plate. The dry weight of the photosensitive layer of these lithographic printing plates was 2.5 g / m each.²Met. To the obtained photosensitive lithographic printing plate, a negative film and a Kodak step tablet No. 2 was vacuum-adhered and exposed for 60 seconds using an aligner MA100 model manufactured by Carlsose having a 100 mW high-pressure mercury lamp. The amount of light is 18mW / cm at 420nm wavelength.²The lithographic printing plate sample (1) was obtained by performing exposure at 1080 mJ.
[0105]
When the obtained printing plate (1) was used for printing on a sprint printing machine, a good printed matter without print stains was obtained. Further, when a lithographic plate was prototyped and printed using a film mask for resolution evaluation with a line / space of 1/2, the thinnest line width that could be resolved was 60 μm. Furthermore, after this lithographic printing plate was allowed to stand at room temperature for 3 months, the printing characteristics were evaluated again.
Further, one side of the photosensitive lithographic printing plate was covered with aluminum foil, and exposure was carried out at 1100 mJ using an aligner as before. When the contact angle with pure water was measured for the exposed part and the non-exposed part (the part covered with the aluminum foil) of this sample, they were 10 degrees and 154 degrees, respectively.
[0106]
Examples 2-5, Comparative Example 1
In the same manner as in Example 1, the compositions obtained in Synthesis Examples 2 to 6 were evaluated. The results are shown in Table 1. The composition (III-a) of Synthesis Example 6 is Comparative Example 1.
[0107]
[Table 1]

[0108]
【The invention's effect】
The photosensitive lithographic printing plate of the present invention is an environmentally friendly technology that does not require a photopolymerizable composition and therefore has an epoch-making feature that its development is unnecessary. The lithographic printing plate produced by exposing the photosensitive lithographic printing plate of the present invention is excellent in stain resistance, printing durability and storage stability.

Claims (2)

(A) Film-forming substrate and
(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, 1 or 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) fine particles and / or sol having photocatalytic activity,
(C) 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;
(D) A photosensitive lithographic printing plate obtained by applying a composition containing water and / or an organic solvent . A lithographic printing plate wherein the photosensitive lithographic printing plate according to claim 1 is irradiated with light in a desired shape to make the irradiated portion hydrophilic.