JP3959143B2 - Novel phthalocyanine compound, method for producing the same, and near-infrared absorbing material - Google Patents

Description

【００２２】
（ただし、式中、ＭはＳｎＣｌ_２、Ａは炭素原子数１〜８個の範囲の直鎖または分鎖状のアルコキシ基がオルソ位あるいはパラ位に少なくとも１個置換されているアニリノ基を表わす。）で示されフタロシアニン化合物。
【００２３】
（２） 前記一般式（１）において、Ａは下記一般式（２）
【００２４】
【化６】

【００２５】
（ただし、式中、Ｒ¹ およびＲ² は炭素原子数１〜８個の範囲のアルキル基を表わし、ｎは０〜２の整数を表わし、Ｒ¹ とＲ² の炭素数の総和は２以上である。）である前記（１）に記載のフタロシアニン化合物。
【００２６】
（３） 下記一般式（３）
【００２７】
【化７】

【００２８】
（ただし、式中、Ａ^１は置換可能な炭素原子数１〜８個の範囲の直鎖および分岐状のアルコキシ基がオルソ位あるいはパラ位に少なくとも１個置換されているアニリノ基を表わす。）で示されるフタロニトリル化合物と、ハロゲン化錫とを反応せしめることを特徴とする前記（１）または（２）に記載のフタロシアニン化合物の製造方法。
【００２９】
（４） 前記一般式（１）で示されるフタロシアニン化合物を、樹脂１００重量部に対して０．０００５〜２０重量部含有する樹脂からなる８００ｎｍ〜１０００ｎｍの近赤外線を吸収する近赤外線（熱線）吸収材および遮蔽材。
【００３３】
【発明の実施の形態】
本発明者らは、特開平５−３４５８６１号および特開平６−２６４０５０号に近赤外線を吸収する近赤外線（熱線）吸収および遮蔽材に適合するフタロシアニン化合物を提供した。本発明では、それらのフタロシアニン化合物を更に改良したものである。
【００３４】
すなわち、フタロシアニン化合物において、中心金属がハロゲン化錫でフタロシアニン骨格におけるベンゼン核にアニリノ基が４個置換されているフタロシアニン化合物は、比較的可視域の吸収が少なく透明性に優れているが、λｍａｘが比較的短波長側にあり、近赤外線吸収能が低い事が判明した。本発明者らは、この化合物に着目し透明性を保持して近赤外線吸収能を高めることができないか、鋭意検討を行った。その結果、アニリノ基のオルソ位あるいはパラ位に、炭素数１〜８の範囲の直鎖および分岐状のアルコキシ基を少なくとも１個置換させることによって、中心金属がハロゲン化錫でフタロシアニン骨格におけるベンゼン核にアニリノ基が４個置換されているフタロシアニン化合物の近赤外線吸収能を高めることができることを見出し本発明を完成させた。
【００３５】
本発明では、フタロシアニン骨格のベンゼン核のβ位にアニリノ基が置換された上記一般式（４）のフタロシアニン化合物が好ましい。β位にアニリノ基を置換させることによって耐光性を向上することができる。一般式（４）における炭素原子数１〜８個のアルキル基としてはメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、直鎖または分鎖のペンチル基、直鎖または分鎖のヘキシル基、直鎖または分鎖のヘプチル基、直鎖または分鎖のオクチル基、シクロヘキシル基等が挙げられる。
【００３６】
本発明では、更にフタロシアニン骨格のベンゼン核の残りの置換基が、ハロゲン原子であるのが、簡便な方法でフタロシアニン化合物を製造できるので好ましい。ハロゲン原子としては塩素原子、ブロム原子およびフッ素原子が挙げられる。ハロゲン原子の中でもフッ素原子が好ましい。フッ素原子を用いることによって樹脂との相溶性向上の効果をもたせられる。また、フッ素原子を用いることによって最も効率よくフタロシアニン化合物を製造できる。
【００３７】
本発明では、更に上記一般式（１）のフタロシアニン化合物が好ましく、また更に一般式（１）のフタロシアニン化合物におけるＡが、上記一般式（２）であるアニリノ基であることが特に好ましい。アニリノ基のオルソ位あるいはパラ位に、置換されているアルコキシ基の数が多い程近赤外線吸収能が高いので好ましい。また長鎖のアルコキシ基程透明性に寄与するので好ましい。長鎖になるとフタロシアニン化合物を製造する際に生産性が悪くなるので、アルコキシ中の炭素原子数としては、８個以下が好ましい。特に、アルコキシ中の炭素原子数としては、全てのアルコキシの総計として２〜４個が好ましい。
【００３８】
以下に本発明で使用するフタロシアニン化合物をより具体的に例示する。
【００３９】
４−テトラキス（Ｏ−メトキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニン、
略称：ＳｎＣｌ₂ Ｐｃ（２ｍＰｈＮＨ）₄ Ｆ₁₂
４−テトラキス（２，４−ジメトキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニン、
略称：ＳｎＣｌ₂ Ｐｃ（２４ｄｍＰｈＮＨ）₄ Ｆ₁₂
４−テトラキス（２，６−ジメトキシアニリノ）−３，５，６，−ドデカフルオロ塩化錫フタロシアニン、
略称：ＳｎＣｌ₂ Ｐｃ（２６ｄｍＰｈＮＨ）₄ Ｆ₁₂
４−テトラキス（２，４，６−トリメトキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニン、
略称：ＳｎＣｌ₂ Ｐｃ（２４６ｔｍＰｈＮＨ）₄ Ｆ₁₂
４−テトラキス（２，４−ジメトキシ−６−メチルアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニン、
略称：ＳｎＣｌ₂ Ｐｃ（２４ｍ６ｍＰｈＮＨ）₄ Ｆ₁₂
４−テトラキス（ｏ−エトキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニン、
略称：ＳｎＣｌ₂ Ｐｃ（２ｅＰｈＮＨ）₄ Ｆ₁₂
４−テトラキス（２，４−エトキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニン、
略称：ＳｎＣｌ₂ Ｐｃ（２４ｅＰｈＮＨ）₄ Ｆ₁₂
４−テトラキス（ｐ−エトキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニン、
略称：ＳｎＣｌ₂ Ｐｃ（４ｃＰｈＮＨ）₄ Ｆ₁₂
４−テトラキス（ｏ−エトキシアニリノ）−３，５，６−ドデカフルオロブロム化錫フタロシアニン、
略称：ＳｎＢｒ₂ Ｐｃ（２ｍＰｈＮＨ）₄ Ｆ₁₂
４−テトラキス（２−エトキシ−テトラフルオロアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニン、
略称：ＳｎＣｌ₂ Ｐｃ（２ｅｔｆＰｈＮＨ）₄ Ｆ₁₂
４−テトラキス（２−エトキシ−４−メトキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニン、
略称：ＳｎＣｌ₂ Ｐｃ（２ｅ４ｍＰｈＮＨ）₄ Ｆ₁₂
４−テトラキス（ｏ−プロポキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニン、
略称：ＳｎＣｌ₂ Ｐｃ（２ｐＰｈＮＨ）₄ Ｆ₁₂
４−テトラキス（ｏ−イソプロポキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニン、
略称：ＳｎＣｌ₂ Ｐｃ（２ｉｐＰｈＮＨ）₄ Ｆ₁₂
４−テトラキス（ｏ−ブトキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニン、
略称：ＳｎＣｌ₂ Ｐｃ（２ｂＰｈＮＨ）₄ Ｆ₁₂
４−テトラキス（ｏ−ｔｅｒｔブトキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニン、
略称：ＳｎＣｌ₂ Ｐｃ（２ｔｂＰｈＮＨ）₄ Ｆ₁₂
４−テトラキス（ｏ−オクチルオキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニン、
略称：ＳｎＣｌ₂ Ｐｃ（２ｏＰｈＮＨ）₄ Ｆ₁₂
４−テトラキス（４−エトキシアニリノ）−３，５，６−ドデカクロロ塩化錫フタロシアニン、
略称：ＳｎＣｌ₂ Ｐｃ（４ｅＰｈＮＨ）₄ Ｃｌ₁₂
４−テトラキス（４−エトキシアニリノ）塩化錫フタロシアニン、
略称：ＳｎＣｌ₂ Ｐｃ（４ｅＰｈＮＨ）₄
３−テトラキス（２−エトキシアニリノ）塩化錫フタロシアニン、
略称：ＳｎＣｌ₂ Ｐｃα（２ｅＰｈＮＨ）₄
本発明では、上記のフタロシアニン化合物の中で、特に
４−テトラキス（２，４−ジメトキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニン、
４−テトラキス（２，６−ジメトキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニン、
４−テトラキス（２，４，６−トリメトキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニン、
４−テトラキス（ｏ−エトキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニン、
４−テトラキス（２，４−エトキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニン、
４−テトラキス（ｏ−プロポキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニン、
４−テトラキス（ｏ−イソプロポキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニン、
４−テトラキス（ｏ−ブトキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニン、
４−テトラキス（ｏ−ｔｅｒｔブトキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニン、
が樹脂への相溶性が向上し、耐光性が向上するので好ましい。
【００４０】
特に原料のアニリンが入手し易く、安価という点で
４−テトラキス（２，４−ジメトキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニン、
４−テトラキス（ｏ−エトキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニン、
が好ましい。本発明のフタロシアニン化合物の中心金属は、好ましくは塩化錫であるが、これらに中心金属が酸化錫、水酸化錫等の中心金属の塩化錫の一部が変化したフタロシアニン化合物が混在していてもかまわない。
【００４１】
本発明の新規フタロシアニンの製造方法において、それらの出発原料である含フッ素フタロニトリルは、好ましくは下記のスキーム１のルートに従って合成できる。なお下記の各々のスキームにおいて合成する際の溶媒としては、ニトロベンゼン、アセトニトリル、ベンゾニトリル等の不活性溶媒、あるいはピリジン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリジノン、トリエチルアミン、トリ−ｎ−ブチルアミン、ジメチルスルホン、スルホランなどの非プロトン性極性溶媒などを用いることができる。特にアセトニトリルおよびベンゾニトリルが好ましい。
【００４２】
また縮合剤としてトリエチルアミン、トリ−ｎ−ブチルアミンなどの有機塩基類やフッ化カリウムを用いるのが好ましい。本発明では、原料として用いる各種のアニリン自身が縮合剤として働くので、特に新たな縮合剤を用いる必要がない。新たな縮合剤を用いない場合には、各種のアニリンは原料のフタロニトリル１モルに対して１５モル倍以上、好ましくは２．０〜３．０モル倍が良い。この合成方法については、本発明者らは既に特願昭６３−６５８０６号、特願平１−１０３５５４号、特願平１−１０３５５５号および特願平１−２０９５９９号、特願平４−２７４１２５、特願平８−２１５８２８号等に開示している。
【００４３】
【化９】

【００４４】
（式中、Ａ¹ は一般式（３）の場合と同じ意味を有する。）
本発明の新規フタロシアニンを製造する方法において使用する有機溶剤は、出発原料と反応性のない不活性な溶媒であればいずれでも良く、例えばベンゼン、トルエン、キシレン、ニトロベンゼン、モノクロロベンゼン、ジクロロベンゼン、トリクロロベンゼン、クロロナフタレン、メチルナフタレン、エチレングリコール、ベンゾニトリル等の不活性溶媒、あるいはピリジン、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリジノン、トリエチルアミン、トリ−ｎ−ブチルアミン、ジメチルスルホン、スルホランなどの非プロトン性極性溶媒などを用いることができ、好ましくは、クロロナフタレン、トリクロロベンゼン、ベンゾニトリル、Ｎ−メチル−２−ピロリジノンである。
【００４５】
本発明の一般式（１）で表わされる新規フタロシアニン化合物の製造方法においては、有機溶媒１００重量部に対して一般式（３）で示されるフタロニトリルは２〜３０重量部の範囲で仕込むことが好ましい。一般式（３）で示されるフタロニトリル１モルに対してハロゲン化錫は０．２０〜０．４５モルの範囲で仕込むことが好ましく、特に好ましくは０．３０〜０．４０の範囲である。ハロゲン化錫としては、塩化第２錫および臭化第２錫を用いるのがよく、特に塩化第２錫が好ましい。
【００４６】
好ましい反応温度としては、１００〜３００℃の範囲が好ましく、特に１５０〜２５０℃の範囲が好ましい。
【００４７】
なお、中心金属がハロゲン化錫であり、フタロシアニン骨格における４個のベンゼン核の各々が、炭素数１〜８の範囲の直鎖および分岐状のアルコキシ基がオルソ位あるいはパラ位に少なくとも１個置換されているアニリノ基で置換されているフタロシアニン化合物の製法は、一般式（１）の化合物と同様にして、つぎのスキーム２で得られたフタロニトリルから合成できる。
【００４８】
【化１０】

【００４９】
（ただし、式中、Ｘはフッ素原子、臭素原子、または塩素原子を表わし、Ｒ¹ は同一または異なっていてもよい水素原子、ハロゲン原子またはＲ² 基を表わし、Ｒ² は置換基を有してもよいアルキル基またはアリール基を表わし、ｎは１〜４の整数を表わし、Ａ¹ は一般式（３）の場合と同じ意味を有する。）
スキーム１およびスキーム２の方法で合成したフタロニトリル化合物としては、以下のものが具体的に挙げられる。
【００５０】
４−（ｏ−メトキシアニリノ）−３，５，６−トリフルオロフタロニトリル、
４−（２，４−ジメトキシアニリノ）−３，５，６−トリフルオロフタロニトリル、
４−（２，６−ジメトキシアニリノ）−３，５，６−トリフルオロフタロニトリル、
４−（２，４，６−トリメトキシアニリノ）−３，５，６−トリフルオロフタロニトリル、
４−（２，４−ジメトキシ−６−メチルアニリノ）−３，５，６−トリフルオロフタロニトリル、
４−（ｏ−エトキシアニリノ）−３，５，６−トリフルオロフタロニトリル、
４−（２，４−ジエトキシアニリノ）−３，５，６−トリフルオロフタロニトリル、
４−（ｐ−エトキシアニリノ）−３，５，６−トリフルオロフタロニトリル、
４−（２−エトキシテトラフルオロアニリノ）−３，５，６−トリフルオロフタロニトリル、
４−（２−エトキシ−４−メトキシアニリノ）−３，５，６−トリフルオロフタロニトリル、
４−（ｏ−プロポキシアニリノ）−３，５，６−トリフルオロフタロニトリル、
４−（ｏ−イソプロポキシアニリノ）−３，５，６−トリフルオロフタロニトリル、
４−（ｏ−ブトキシアニリノ）−３，５，６−トリフルオロフタロニトリル、
４−（ｏ−ｔｅｒｔブトキシアニリノ）−３，５，６−トリフルオロフタロニトリル、
４−（ｏ−オクチルオキシアニリノ）−３，５，６−トリフルオロフタロニトリル、
４−（ｐ−エトキシアニリノ）−３，５，６−トリクロロフタロニトリル、
４−（ｐ−エトキシアニリノ）フタロニトリル、
３−（ｏ−エトキシアニリノ）フタロニトリル、
本発明において使用する樹脂は、得られる近赤外線（熱線）の吸収材および遮蔽材の用いる用途によって適宜選択することができるが、実質的に透明であって吸収・散乱が大きくない樹脂が好ましい。その具体的なものとしては、ポリカーボネート樹脂；メチルメタクリレートなどの（メタ）アクリル樹脂；ポリスチレン、ポリ塩化ビニル、ポリ塩化ビニリデンなどのポリビニル樹脂；ポリエチレン、ポリプロピレンなどのポリオレフィン樹脂；ポリブチラール樹脂：ポリ酢酸ビニル樹脂；ポリエチレンテレフタレート等のポリエステル樹脂、ポリアミド樹脂などを挙げることができる。また、実質的に透明であれば、上記１種類の樹脂に限らず、２種以上の樹脂をブレンドしたものも用いることができ、透明性のガラスに上記の樹脂をはさみこんで用いることもできる。ただし、蓄熱・保温材として用いる場合には、必ずしも透明性の樹脂である必要がない。
【００５１】
これらの樹脂のうちで、耐候性、透明性に優れるポリカーボネート樹脂、（メタ）アクリル樹脂、ポリエステル樹脂、ポリエチレン樹脂、ポリスチレン樹脂あるいはポリ塩化ビニル樹脂が好ましく、特にポリカーボネート樹脂、メタクリル樹脂、ポリエチレンテレフタレート樹脂あるいはポリ塩化ビニル樹脂が好ましい。蓄熱保温繊維として使用する場合、ポリエチレンテレフタレート樹脂あるいはポリアミド樹脂が好ましい。
【００５２】
ポリカーボネート樹脂は、２価フェノールとカーボネート前駆体とを溶液法または溶融法で反応させて製造されるものである。２価フェノールの代表的な例として以下のものが挙げられる。
【００５３】
２，２−ビス（４−ヒドロキシフェニル）プロパン[ ビスフェノールＡ］、１，１−ビス（４−ヒドロキシフェニル）エタン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン、２，２−ビス（４−ヒドロキシ−３，５−ジメチルフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３，５−ジブロモフェニル）プロパン、２，２−ビス（４−ヒドロキシ−３−メチルフェニル）プロパン、ビス（４−ヒドロキシフェニル）スルフィド、ビス（４−ヒドロキシフェニル）スルホン等である。好ましい２価のフェノールはビス（４−ヒドロキシフェニル）アルカン系であり、特にビスフェノールを主成分とするものである。
【００５４】
アクリル樹脂としてはメタクリル酸メチル単独またはメタクリル酸メチルを５０％以上含む重合性不飽和単量体混合物またはその共重合物が挙げられる。メタクリル酸メチルと共重合可能な重合性不飽和単量体としては例えば以下のものが挙げられる。アクリル酸メチル、（メタ）アクリル酸エチル（アクリル酸メチルあるいはメタクリル酸メチルの意味。以下同じ）、（メタ）アクリル酸ブチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸メトキシエチル、（メタ）アクリル酸エトキシエチル、（メタ）アクリル酸２−ヒドロキシエチル、（メタ）アクリル酸Ｎ，Ｎ−ジエチルアミノエチル、（メタ）アクリル酸グリシジル、（メタ）アクリル酸トリブロモフェニル、（メタ）アクリル酸テトラヒドロキシフルフリール、エチレングルコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、トリメチロールエタンジ（メタ）アクリレート、ネオペンチルグルコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレートなどである。
【００５５】
塩化ビニル樹脂としては、塩化ビニルの単量体のみの重合体ばかりでなく、塩化ビニルを主成分とする共重合体も使用できる。塩化ビニルと共重合させることのできる単量体としては、塩化ビニリデン、エチレン、プロピレン、アクリロニトリル、酢酸ビニル、マレイン酸、イタコン酸、アクリル酸、メタクリル酸などが挙げられる。
【００５６】
本発明の実施にあたっては、使用する目的に応じ適宜好ましい添加剤を用いることができる。添加剤としては、例えば着色剤、重合調節剤、酸化防止剤、紫外線吸収剤、難燃剤、可塑剤、耐衝撃性向上のためのゴム、あるいは剥離剤などを挙げることができる。
【００５７】
本発明のフタロシアニン化合物を用いるにあたり、従来公知の近赤外線吸収剤と組合わせて用いることもできる。
【００５８】
前記フタロシアニン化合物を透明性樹脂に混合含有させ成形する方法としては、押出成形、射出成形、注型重合、プレス成形、カレンダー成形あるいは注型製膜法等が挙げられる。
【００５９】
さらに、フタロシアニン化合物を含有するフィルムを作成し、そのフィルムを透明樹脂板に熱プレスあるいは熱ラミネート成形することにより熱線遮蔽板を作成することも可能である。
【００６０】
また、フタロシアニン化合物を含有する樹脂インクまたは塗料等を透明樹脂板、透明硝子板、フィルム、繊維、紙等の基材に印刷またはコーティングすることにより近赤外線（熱線）の吸収板および遮蔽板、シート、フィルム、繊維、紙等を得ることもできる。
【００６１】
本発明に使用するフタロシアニン化合物は市販の赤外線吸収剤と比較して、耐熱性に優れているので、アクリル系樹脂、ポリカーボネート系樹脂、ポリエチレンテレフタレート樹脂を使用して射出成形、押出成形のような樹脂温度が２２０〜３５０℃という高温まで上昇する成形方法でも成形することが可能であり、透明感が良好で近赤外線の吸収能あるいは熱線遮蔽性能に優れた成形品を得ることができる。また、ポリエステル樹脂、ポリアミド樹脂等と２２０〜３５０℃で紡糸して、蓄熱保温繊維を得ることができる。と
２２０℃より下の成形温度で使用しても問題はない。
【００６２】
近赤外線（熱線）吸収材および熱遮蔽材の形状にも格別の制限はなく、最も一般的な平板状やフィルム状のほか波板状、球面状、ドーム状等様々な形状のものが含有される。
【００６３】
本発明において用いられるフタロシアニン化合物は、目的とする熱近赤外線（熱線）遮蔽材のシートあるいはフィルムの可視および近赤外域の透過率の設定および該材の厚みによってその量を変えることができるが、通常透明性樹脂１００重量部に対して０．０００５〜２０重量部、好ましくは０．００１５〜１０重量部である。
【００６４】
この配合量近赤外線（熱線）遮蔽材の形状によって異なり、例えば、厚さ３ｍｍの近赤外線（熱線）遮蔽板を作成する場合には、０．００２〜０．０６重量部の配合量が好ましく、さらに好ましくは０．００５〜０．０３重量部である。
【００６５】
厚さ１０ｍｍの近赤外線（熱線）遮蔽板を作成する場合には、０．０００５〜０．０２重量部の配合量が好ましく、さらに好ましくは０．００１５〜０．０１重量部である。厚さ１０μｍの近赤外線（熱線）遮蔽フィルムを作成する場合には、０．５〜２０重量部の配合量が好ましく、さらに好ましくは１．５〜１０重量部である。近赤外線（熱線）遮蔽材の厚さに関係なくフタロシアニン化合物の配合量を表示するとすれば、上方からの投影面積中の重量と考えて、０．０６〜２．４ｇ／ｍ² の配合量が好ましく、さらに好ましくは０．１８〜１．２ｇ／ｍ² である。
【００６６】
フタロシアニン化合物の配合量が０．０６ｇ／ｍ² より少ない場合には近赤外線（熱線）遮蔽効果の少ないものとなり、２．４ｇ／ｍ² を超える場合は著しく高価となり、また、可視光線の透過が少なくなり過ぎる場合がある。
【００６７】
波板等の異形のものは上方からの投影面積中の重量と考えればよい。また、外観上問題がない限りフタロシアニン化合物の濃度の分布にむらがあってもかまわない。また、フタロシアニン化合物は１種類以上のものを混合して使用することも可能であり、吸収波長の異なるものを２種以上使用した場合には近赤外線（熱線）吸収遮蔽効果が向上することがある。
【００６８】
また、フタロシアニン化合物とカーボンブラックを特定量使用することにより、フタロシアニン化合物を単独で使用した場合と比較して、近赤外線（熱線）吸収遮蔽効果は同等でフタロシアニン化合物の使用量を半分以下に減少させることができる。また、フタロシアニン化合物と染料を併用した場合と比較して近赤外線（熱線）吸収遮蔽効果が向上する。
【００６９】
【実施例】
つぎに、実施例を挙げて本発明をさらに具体的に説明する。
【００７０】
実施例１
４−（ｏ−エトキシアニリノ）−３，５，６−トリフルオロフタロニトリルの製造
１００ｍｌの四ツ口フラスコにテトラフルオロフタロニトリル１０．００ｇ（５０ミリモル）、ｏ−フェネチジン１６．４５ｇ（１２０ミリモル）およびアセトニトリル６０ｍｌを仕込み、還流下に４時間反応させた。反応終了後、反応混合物を水に投入し、生成した固形分を水、ついでヘキサンで洗浄することにより目的物の黄色ケーキを１４．２２ｇを得た（収率９３．８％）。
【００７１】
４−テトラキス（ｏ−エトキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニンの製造
１００ｍｌの四ツ口フラスコに、上記で得られた４−（ｏ−エトキシアニリノ）−３，５，６−トリフルオロフタロニトリル１０．００ｇ（３２ミリモル）、塩化錫（II）１．７９ｇ（９．４６ミリモル）およびベンゾニトリル３０ｍｌを仕込み、１７５℃で５時間反応させた。反応終了後、ベンゾニトリルを留去した反応混合物をテトラヒドロフランに溶解させ、ヘキサン中に投入することにより生成した固形分をヘキサンで洗浄することにより目的物の深青色ケーキ１０．５０ｇを得た（収率９１．３％）。
【００７２】

この化合物の赤外吸収スペクトルを図１に示す。
【００７３】
この化合物の熱分解温度ならびに耐光性のデータを表１に示す。
【００７４】
実施例２
４−テトラキス（２，４−ジメトシキアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニンの製造
１００ｍｌの四ツ口フラスコにテトラフルオロフタロニトリル１０．００ｇ（５０ミリモル）、２，４−ジメトキシアニリン１８．３７ｇ（１２０ミリモル）およびベンゾニトリル６０ｍｌを仕込み、８０℃で６時間反応させた。反応終了後、反応混合物を水に投入し、分液したベンゾニトリル層を水、塩酸水、ついで水で洗浄後、ベンゾニトリル層を分離して４−（２，４−ジメトキシアニリノ）−３，５，６−トリフルオロフタロニトリルのベンゾニトリル溶液５０ｇを得た。
【００７５】
ついで、上記で得られた４−（２，４−ジメトキシアニリノ）−３，５，６−トリフルオロフタロニトリルのベンゾニトリル溶液を、液体クロマトグラフで分析することにより該フタロニトリルの濃度は３０．１６重量％と決定した。１００ｍｌの四ツ口フラスコにその４−（２，４−ジメトキシアニリノ）−３，５，６−トリフルオロフタロニトリルのベンゾニトリル溶液５０ｇと塩化錫（II）２．５７ｇ（１４ミリモル）を仕込み、１７５℃で５時間反応させた。反応終了後、ベンゾニトリルを留去した反応混合物をテトラヒドロフランに溶解させ、ヘキサン中に投入することにより生成した固形分をヘキサンで洗浄することにより目的物の深青色ケーキ１０．８６ｇを得た（収率６３．０３％）。
【００７６】

この化合物の赤外吸収スペクトルを図２に示す。
【００７７】
この化合物の熱分解温度ならびに耐光性のデータを表１に示す。
【００７８】
実施例３
４−（２，４，６−トリメトキシアニリノ）−３，５，６−トリフルオロフタロニトリルの製造
実施例１の４−（ｏ−エトキシアニリノ）−３，５，６−トリフルオロフタロニトリルの製造において、ｏ−フェネチジンのかわりに、２，４，６−トリメトキシアニリン２１．９７ｇ（１２０ミリモル）を用いた以外は、実施例１の４−（ｏ−エトキシアニリノ）−３，５，６−トリフルオロフタロニトリルの製造と同様に操作して目的物の黄色ケーキ１５．５６ｇを得た（収率８５．７％）。
【００７９】
４−テトラキス（２，４，６−トリメトキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニンの製造
実施例１の４−テトラキス（ｏ−エトキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニンの製造において、４−（ｏ−エトキシアニリノ）−３，５，６−トリフルオロフタロニトリルのかわりに、４−（２，４，６−トリメトキシアニリノ）−３，５，６−トリフルオロフタロニトリル１０．００ｇ（２８ミリモル）を用いた以外は、実施例１の４−テトラキス（ｏ−エトキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニンの製造と同様の操作をして目的物の深青色ケーキ７．１０ｇを得た（収率６２．８％）。
【００８０】
可視吸収スペクトル

この化合物の熱分解温度ならびに耐光性のデータを表１に示す。
【００８１】
実施例４
４−（ｏ−イソプロポキシアニリノ）−３，５，６−トリフルオロフタロニトリルの製造
実施例１の４−（ｏ−エトキシアニリノ）−３，５，６−トリフルオロフタロニトリルの製造において、ｏ−フェネチジンのかわりに、ｏ−イソプロポキシアニリン１８．１４ｇ（１２０ミリモル）を用いた以外は、実施例１の４−（ｏ−エトキシアニリノ）−３，５，６−トリフルオロフタロニトリルの製造と同様に操作して目的物の黄色ケーキ２０．０５ｇを得た（収率９１．５％）。
【００８２】
４−テトラキス（ｏ−イソプロポキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニンの製造
実施例１の４−テトラキス（ｏ−エトキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニンの製造において、４−（ｏ−エトキシアニリノ）−３，５，６−トリフルオロフタロニトリルのかわりに、４−（ｏ−イソプロポキシアニリノ）−３，５，６−トリフルオロフタロニトリル１０．００ｇ（３０ミリモル）を用いた以外は、実施例１の４−テトラキス（ｏ−エトキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニンの製造と同様の操作をして目的物の深青色ケーキ１０．２２ｇを得た（収率８９．４％）。
【００８３】

この化合物の熱分解温度ならびに耐光性のデータを表１に示す。
【００８４】
比較例１
４−アニリノ−３，５，６−トリフルオロフタロニトリルの製造
実施例１の４−（ｏ−エトキシアニリノ）−３，５，６−トリフルオロフタロニトリルの製造において、ｏ−フェネチジンのかわりに、アニリン１１．１７ｇ（１２０ミリモル）を用いた以外は、実施例１の４−（ｏ−エトキシアニリノ）−３，５，６−トリフルオロフタロニトリルの製造と同様に操作して目的物の黄色ケーキ１２．５２ｇを得た（収率９１．７％）。
【００８５】
４−テトラキスアニリノ−３，５，６−ドデカフルオロ塩化錫フタロシアニン（略称：ＳｎＣｌ₂ Ｐｃ（ＰｈＮＨ）₄ Ｆ₁₂）の製造
実施例１の４−テトラキス（ｏ−エトキシアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニンの製造において、４−（ｏ−エトキシアニリノ）−３，５，６−トリフルオロフタロニトリルのかわりに、４−アニリノ−３，５，６−トリフルオロフタロニトリル１０．００ｇ（３７ミリモル）を用いた以外は、実施例１の４−テトラキス（ｏ−エトシキアニリノ）−３，５，６−ドデカフルオロ塩化錫フタロシアニンの製造と同様の操作をして目的物の深青色ケーキ１０．３５ｇを得た（収率８８．２％）。
【００８６】

この化合物の熱分解温度ならびに耐光性のデータを表１に示す。
【００８７】
比較例２
オクタフルオロオクタキスアニリノオキシバナジウムフタロシアニン（略称：ＶＯＰｃ（ＰｈＮＨ）₈ Ｆ₈ ）の製造
１００ｍｌの四ツ口フラスコ中にヘキサデカフルオキシバナジウムフタロシアニン５．１９ｇ（６ミリモル）、アニリン２６．８２ｇ（２８８ミリモル）を仕込み、還流温度で４時間反応させた。反応終了後、不溶分を濾別した後アニリンを留去し得られた固形分をｎ−ヘキサン３００ｍｌで洗浄することにより目的物の黒色ケーキ６．７２ｇを得た（収率７７．１％）。
【００８８】

この化合物の熱分解温度ならびに耐光性のデータを表１に示す。
【００８９】
【表１】

【００９０】
熱分解性は、示差熱熱重量分析装置で室温から温度を上昇させ、その重量が５％減少した時の温度でつぎの３段階の評価を行なった。
【００９１】
○ 重量が５％減少時の温度 ２５０℃超
△ 重量が５％減少時の温度 ２００℃超〜２５０℃
× 重量が５％減少時の温度 ２００℃以下
耐光性の評価は、以下の方法で行なった。
【００９２】
色素１ｇをエチルセルソルブ２０ｇに溶解させ、ガラス基板上にスピンコート法により色素薄膜を作成し試料とした。この試料をキセノン耐光性試験機（照射光量１２０，０００Ｌｕｘ）にセットし、経時での吸光度の減少を測定した。そして、１００時間経過後の吸光度の残存率によりつぎの３段階の評価を行なった。
【００９３】
○ １００時間経過後の吸光度の残存率 ８０％以上
△ １００時間経過後の吸光度の残存率 ３０％〜８０％未満
× １００時間経過後の吸光度の残存率 ３０％以下
なお、実施例および比較例における最大吸収波長の測定方法は以下に示す方法を用いて行なったものである。
【００９４】
溶液中でのデータは、溶媒としてエチルセルソルブを用い、各サンプル濃度を３．７５〜４．００×１０^-5モル／リットルの範囲に調節し、１０ｍｍ測定セルで島津制作所 ＵＶ−３１００紫外可視分光高度計を用いて測定した。
【００９５】
薄膜でのデータは、色素１ｇをエチレンセルソルブ２０ｇに溶解させ、ガラス基板上にスピンコート法により色素薄膜を作成したものを試料とし、その試料を島津制作所 ＵＶ−３１００紫外可視分光高度計を用いて測定した。
【００９６】
実施例５〜８
溶融したポリカーボネート樹脂（帝人化成株式会社製、パンライト１２８５、商品名）１００重量部に表１記載のフタロシアニン化合物を表２記載の量を添加し、Ｔダイ押出機で厚さ３ｍｍのシートを２８０℃で成形した。得られた板の可視光透過率および熱光線透過率を測定した。
【００９７】
なお、得られた熱線遮蔽板の透過スペクトルおよび透過率は分光光度計（島津製作所製：ＵＶ−３１００）で測定した。また、熱線遮蔽板の可視光透過率（４００〜８００ｎｍ）および熱光線部透過率（８００〜１，０００ｎｍ）の値はＪＩＳ Ｒ ３１０６の規格に準じて求めた。
【００９８】
すなわち、可視光透過率はＪＩＳ Ｒ ３１０６により求めた日射透過率の４００〜８００ｎｍの値を０．５４５で除算した値であり、熱光線透過率はＪＩＳＲ ３１０６により求めた日射透過率の８００〜１，０００ｎｍの値を０．１７３で除算した値である。なお、太陽光線のエネルギー分布は４００〜８００ｎｍの範囲が０．５４５、８００〜１，０００ｎｍの範囲が０．１７３である。なお、３４０〜４００ｎｍの範囲は紫外領域のため除外してある。
【００９９】
比較例３〜４
特開平５−３４５８６１号および特開平６−２６４０５０号に本発明者らが提案したフタロシアニン化合物を実施例５〜８と同様にして配合し、実施例５〜８と同様に操作して表２の結果を得た。
【０１００】
比較例５
実施例５〜８にフタロシアニン化合物を添加しない以外は、実施例５〜８と同様に操作して表２の結果を得た。
【０１０１】
【表２】

【０１０２】
表２の結果からわかるように、ＶＯＰｃ（ＰｈＮＨ）₈ Ｆ₈ は可視光線透過率は良くないが、８００〜１，０００ｎｍの近赤外線域の熱線はよく吸収する。一方、ＳｎＣｌ₂ Ｐｃ（ＰｈＮＨ）₄ Ｆ₁₂は可視光線透過率は高く透明性はあるが、８００〜１，０００ｎｍの近赤外線域の熱線の吸収率が悪い。本発明の実施例１〜４の化合物は、それらのものに比較して８００〜１，０００ｎｍの近赤外線域も良く吸収し、かつ可視光線の透過率も高い。
【０１０３】
かくして本発明では近赤外線（熱線）吸収材および遮蔽材として、本発明のフタロシアニン化合物を使う場合、フタロシアニン化合物を溶融したポリカーボネート樹脂に０．０１％添加して厚さ３ｍｍのシートを作成した。該シートの４００〜８００ｎｍの可視光線透過率が４５％以上であり（好ましくは５０％以上）、８００〜１，０００ｎｍの熱光線透過率が３０％以下（好ましくは２５％以下）のものを用いるのが良い。
【０１０４】
【発明の効果】
本発明にかかる新規なフタロシアニン化合物は、８００〜１０００ｎｍの近赤外線域に吸収を有し、有機溶媒に対しての溶解性に優れており、またフタロシアニンが元来保有している耐光性にも優れているので、近赤外線（熱線）遮蔽効果を利用するものとしての電子機器用赤外線カットフィルター、写真用赤外線フィルター、自動車あるいは建材向けの熱線遮蔽剤、農業用フィルム、保護メガネ、サングラスあるいは半導体レーザーを使う光記媒体、液晶表示素子、また近赤外線（熱線）の吸収効果を利用するものとしての光学文字読み取り機等における書き込みあるいは読み取りのための近赤外線吸収色素、テレビ・ビデオなどの近赤外線を感知するセンサー、写真用・電子写真用などの近赤外線光増感剤、感熱転写、感熱紙・感熱孔版等光熱変換剤、改ざん偽造防止用バーコード用インク等の近赤外線吸収インク、さらに繊維などの蓄熱保温剤として優れた効果を発揮するものである。
【０１０５】
また、本発明の近赤外線（熱線）吸収材および遮蔽材は近赤外線吸収に優れ、樹脂との相溶性に優れ、耐光性、耐熱性に優れ、かつ可視域の吸収の少ないフタロシアニン化合物を含有する樹脂からなり、建物あるいは乗り物の窓、天井窓、扉、電話ボックス、アーケード、カーポート、工場の屋根あるいは天井ドーム、園芸用温室、サングラスあるいは保護メガネなどの半透明ないし透明性を有しかつ熱線を遮蔽する目的の樹脂板、シート、フィルム、繊維あるいは塗料として用いることができるし、近赤外線を吸収し熱に変えることができるので蓄熱、保温を目的として樹脂板、シート、フィルム、繊維あるいは塗料として用いることができるし、また半導体受光素子、カラー固体撮像素子、ＣＲＴディスプレイ、プラズマディスプレイなどの半透明ないし透明性を有しかつ近赤外線を遮蔽する目的の樹脂板、シート、フィルム、繊維あるいは塗料として用いることができる。
【図面の簡単な説明】
【図１】 本発明の実施例１によるフタロシアニン化合物の赤外線吸収スペクトルである。
【図２】 本発明の実施例２によるフタロシアニン化合物の赤外線吸収スペクトルである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel phthalocyanine compound, a method for producing the same, and a near-infrared (heat ray) absorbing material and a shielding material having high near-infrared absorption capability and low absorption in the visible range and high compatibility with resins. is there.
[0002]
[Prior art]
In recent years, semiconductor lasers have been used as light sources for optical recording media such as compact discs, laser discs, optical memory discs, optical cards, etc., liquid crystal display devices, optical character readers, etc. Sensor, near-infrared photosensitizer, thermal transfer, photothermal conversion agent such as thermal paper and thermal stencil, near-infrared absorption cut filter, near-infrared absorbing ink such as anti-counterfeiting barcode ink, near-infrared cut There is an increasing demand for development of near-infrared absorbing pigments such as anti-eye strain agents, heat ray shielding materials for automobiles or building materials, and heat storage and heat-retaining agents such as fibers.
[0003]
In particular, the application of various near-infrared (heat ray) shielding materials utilizing the effect of absorbing near-infrared rays is active, and various materials have been proposed. However, there is still no one that satisfies all the characteristics, and there is a strong demand for one with better performance. The following are mentioned as main uses of the near-infrared (heat ray) shielding material which absorbs near-infrared rays.
[0004]
Conventional materials such as methacrylic resin and polycarbonate resin have excellent transparency and weather resistance, so they have windows, ceiling windows, doors, telephone boxes, arcades, carports, factory roofs or ceiling domes in buildings or vehicles. Although it has been used for so-called glazing applications, it has a disadvantage that the internal temperature rises significantly when exposed to direct sunlight, for example, because of its high heat ray transmittance in sunlight. Yes. For these reasons, it is desired to be able to suppress an increase in indoor temperature while sufficiently taking in visible light.
[0005]
Currently, in the cultivation of plants, greenhouses and greenhouses are actively used for the purpose of improving the harvest contents of crops or changing the harvest time. One of these problems is to prevent the indoor temperature from rising especially in summer. In addition, it is well known that light in the near-infrared region affects the growth of plants, but the purpose of the adjustment is to add an absorber in the near-infrared region to the film. For these reasons, an effective heat ray-shielding film is desired without substantially blocking visible light transmission necessary for plant growth.
[0006]
The above is mainly derived from the thermal action, but there are also uses derived from the optical action. Currently, near infrared rays are often used for driving, stopping, remote control or remote control of electrical products such as televisions, videos or magnetic tapes. However, it is necessary to cut off near-infrared rays from outside near-infrared rays or cut out near-infrared rays from the electrical products themselves to prevent malfunctions of each electrical product from driving, stopping, remote control or remote control. Usage is requested. In particular, the plasma display, which is attracting attention as a wall-mounted TV, has the problem of inducing malfunctions of various home appliance remote controls because a large amount of infrared light is emitted from the gas used for pixel light emission. A high near infrared absorption cut filter is required.
[0007]
Infrared light contained in sunlight or in light emitted during computer terminal displays or welding is harmful to the human eye. Therefore, there is a demand for sunglasses, general glasses, contact lenses, protective glasses, etc. that have an effect of blocking near infrared rays for the purpose of protecting human eyes.
[0008]
On the other hand, a heat storage material that utilizes the effect of absorbing near-infrared rays and converting it into heat, a film, sheet, fiber, or the like as a heat insulating material is also desired.
[0009]
Thus, several proposals have heretofore been made as near-infrared (heat ray) absorbing / shielding materials. As the resin used in that case, a transparent polycarbonate resin, acrylic resin, vinyl chloride resin, polyester resin or the like is used, and a resin plate, sheet, film, paint, fiber, or the like is used depending on the purpose. On the other hand, as additives that absorb near infrared rays, for example, many dyes and pigments that absorb near infrared rays are known, and many of them are also proposed. For example, Japanese Patent Publication No. 62-5190 proposes a method of adding a dye and using it as a heat ray shielding material. However, in order to obtain a heat ray shielding effect due to poor near infrared absorption ability, it is added in a large amount. Therefore, there is a problem that the transmittance of visible light is lowered and transparency is impaired. JP-A-51-135886, JP-A-61-80106, JP-A-62-903, etc. have proposed methods for adding pigments that absorb in the near-infrared region. There is a problem in uniformity due to the poor compatibility with the resin, and thus there is a problem that the application is limited.
[0010]
Japanese Patent Application Laid-Open No. 63-106735 proposes a method of blending an inorganic pigment and using it as a heat ray shielding material, but it has a heat ray shielding effect but does not transmit visible light at all. Is limited. Further, Japanese Patent Application Laid-Open No. 1-161036, Japanese Patent Application Laid-Open No. 3-227366, etc. also propose a method of containing tungsten hexachloride or the like. However, these methods have a disadvantage that the near-infrared absorption effect is good but the light stability is poor.
[0011]
Furthermore, as seen in Japanese Examined Patent Publication No. 43-25335, etc., use of an infrared absorber made of an organic dye is conceivable. An infrared absorbing plate using this infrared absorber has a sense of transparency and good workability. It is a thing. However, as described in Japanese Patent Publication No. 43-25533, generally, an organic infrared absorber decomposes at a temperature exceeding 200 ° C., and is practically usable only in cast polymerization, or a fiber spinning temperature. There are restrictions on handling such as being unusable.
[0012]
In order to solve the problem of heat resistance of the infrared absorber, for example, as seen in JP-A-3-161644, a film is formed by adding a low heat resistant infrared absorber to a transparent resin having a low molding temperature. A method of creating a laminated product that is prepared and heat-laminated on a transparent resin plate having a high molding temperature can be considered. However, this method does not substantially solve the heat resistance problem of the infrared absorber. Moreover, the film containing this infrared rays absorber is produced by cast polymerization, and is quite expensive.
[0013]
The present inventors have made various studies in order to solve these problems, and proposed various phthalocyanine dyes in JP-A-5-345686 and JP-A-6-264050 as dyes effective for them.
[0014]
In these already proposed phthalocyanine compounds, the central metal is vanadyl, the phthalocyanine skeleton has about 8 anilino groups substituted on the benzene nucleus, the central metal is tin chloride, and the benzene nucleus in the phthalocyanine skeleton has 4 anilino groups. Individually substituted phthalocyanine compounds have absorption in the near-infrared region and are excellent in light resistance, heat resistance, or solubility. Or kneading into a resin, and is useful as various near-infrared absorbing dyes.
[0015]
However, near-infrared absorption cut filter materials, near-infrared absorption inks such as anti-counterfeiting bar code inks, eye strain prevention materials that cut near-infrared rays, heat ray shielding materials for automobiles or building materials, etc. In addition to the effect of absorbing near-infrared rays, it is desirable to have as high a transparency as possible, but the former phthalocyanine dye in the above has high near-infrared absorptivity, but in terms of transparency. However, the latter phthalocyanine dye has a relatively good transparency but is inferior in near-infrared absorptivity and has a limited application. It turned out to have.
[0016]
[Problems to be solved by the invention]
This invention is made | formed in view of the said situation which a prior art has. That is, the object of the present invention is equal to or better than the solubility, light resistance, and heat resistance, which are the characteristics of the near-infrared absorbing dye proposed by the present inventors in JP-A-5-345861 and JP-A-6-264050. It is intended to provide a near-infrared (heat ray) absorbing / shielding material that has the above-mentioned performance, has a high absorption capability in the near-infrared region, and further improves the transmittance in the visible region.
[0017]
Further, the phthalocyanine dye of the present invention has good compatibility with various resins, and exhibits excellent effects as a near-infrared shielding material, a heat ray shielding material, or a heat storage / heat insulation material used by being contained in the resin. It is something to be offered.
[0018]
In addition, since the phthalocyanine compound of the present invention has good heat resistance, a near infrared (heat ray) absorbing / shielding material can be formed using various thermoplastic resins by a molding method having good productivity such as injection molding and extrusion molding. It is possible to create.
[0019]
[Means for Solving the Problems]
The various objects are achieved by the following (1) to (8).
[0020]
(1) The following general formula (1)
[0021]
[Chemical formula 5]

[0022]
(Where M is SnCl₂, A is a straight chain having 1 to 8 carbon atomsOrIt represents an anilino group in which at least one branched alkoxy group is substituted at the ortho or para position. ) Phthalocyanine compound.
[0023]
(2) In the general formula (1), A represents the following general formula (2)
[0024]
[Chemical 6]

[0025]
(However, in the formula, R¹And R²Represents an alkyl group having 1 to 8 carbon atoms, n represents an integer of 0 to 2, R¹And R²The total number of carbon atoms is 2 or more. The phthalocyanine compound according to (1) above.
[0026]
(3) The following general formula (3)
[0027]
[Chemical 7]

[0028]
(However, in the formula, A¹Represents an anilino group in which at least one linear or branched alkoxy group having 1 to 8 carbon atoms that can be substituted is substituted at the ortho or para position. The method for producing a phthalocyanine compound according to the above (1) or (2), wherein the phthalonitrile compound represented by (1) is reacted with a tin halide.
[0029]
  (4)Shown by the general formula (1)Phthalocyanine compounds,A near-infrared (heat ray) absorber and a shielding material that absorb near-infrared rays of 800 nm to 1000 nm, which are made of a resin containing 0.0005 to 20 parts by weight with respect to 100 parts by weight of resin.
[0033]
DETAILED DESCRIPTION OF THE INVENTION
The present inventors have provided phthalocyanine compounds suitable for near-infrared (heat ray) absorption and shielding materials that absorb near-infrared rays in JP-A-5-345861 and JP-A-6-264050. In the present invention, these phthalocyanine compounds are further improved.
[0034]
That is, in the phthalocyanine compound, the phthalocyanine compound in which the central metal is tin halide and the benzene nucleus in the phthalocyanine skeleton is substituted with four anilino groups has relatively low absorption in the visible region, but has excellent transparency, but λmax is It was found that it is on the relatively short wavelength side and has a low near-infrared absorbing ability. The inventors of the present invention focused on this compound and studied diligently whether it is possible to maintain transparency and increase near infrared absorption ability. As a result, by substituting at least one linear or branched alkoxy group having 1 to 8 carbon atoms at the ortho or para position of the anilino group, the central metal is tin halide and the benzene nucleus in the phthalocyanine skeleton The present inventors have found that the near-infrared absorptivity of a phthalocyanine compound in which four anilino groups are substituted can be enhanced.
[0035]
In the present invention, the phthalocyanine compound of the above general formula (4) in which an anilino group is substituted at the β-position of the benzene nucleus of the phthalocyanine skeleton is preferable. Light resistance can be improved by substituting an anilino group at the β-position. As the alkyl group having 1 to 8 carbon atoms in the general formula (4), a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a straight chain or a branched chain Pentyl group, linear or branched hexyl group, linear or branched heptyl group, linear or branched octyl group, cyclohexyl group and the like.
[0036]
In the present invention, it is further preferable that the remaining substituent of the benzene nucleus of the phthalocyanine skeleton is a halogen atom because a phthalocyanine compound can be produced by a simple method. Examples of the halogen atom include a chlorine atom, a bromine atom, and a fluorine atom. Of the halogen atoms, a fluorine atom is preferred. By using fluorine atoms, the effect of improving the compatibility with the resin can be obtained. Moreover, a phthalocyanine compound can be most efficiently produced by using a fluorine atom.
[0037]
In the present invention, the phthalocyanine compound represented by the general formula (1) is more preferable, and A in the phthalocyanine compound represented by the general formula (1) is particularly preferably an anilino group represented by the general formula (2). The greater the number of substituted alkoxy groups at the ortho or para position of the anilino group, the higher the near-infrared absorptivity, which is preferable. Long chain alkoxy groups are preferred because they contribute to transparency. When it becomes a long chain, productivity decreases when producing a phthalocyanine compound, so the number of carbon atoms in alkoxy is preferably 8 or less. In particular, the number of carbon atoms in alkoxy is preferably 2 to 4 as the total of all alkoxy.
[0038]
Specific examples of the phthalocyanine compound used in the present invention are shown below.
[0039]
4-tetrakis (O-methoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine,
Abbreviation: SnCl₂Pc (2mPhNH)_FourF₁₂
4-tetrakis (2,4-dimethoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine,
Abbreviation: SnCl₂Pc (24dmPhNH)_FourF₁₂
4-tetrakis (2,6-dimethoxyanilino) -3,5,6, -dodecafluorotin chloride phthalocyanine,
Abbreviation: SnCl₂Pc (26dmPhNH)_FourF₁₂
4-tetrakis (2,4,6-trimethoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine,
Abbreviation: SnCl₂Pc (246tmPhNH)_FourF₁₂
4-tetrakis (2,4-dimethoxy-6-methylanilino) -3,5,6-dodecafluorotin chloride phthalocyanine,
Abbreviation: SnCl₂Pc (24m6mPhNH)_FourF₁₂
4-tetrakis (o-ethoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine,
Abbreviation: SnCl₂Pc (2ePhNH)_FourF₁₂
4-tetrakis (2,4-ethoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine,
Abbreviation: SnCl₂Pc (24ePhNH)_FourF₁₂
4-tetrakis (p-ethoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine,
Abbreviation: SnCl₂Pc (4cPhNH)_FourF₁₂
4-tetrakis (o-ethoxyanilino) -3,5,6-dodecafluorobrominated tin phthalocyanine,
Abbreviation: SnBr₂Pc (2mPhNH)_FourF₁₂
4-tetrakis (2-ethoxy-tetrafluoroanilino) -3,5,6-dodecafluorotin chloride phthalocyanine,
Abbreviation: SnCl₂Pc (2etfPhNH)_FourF₁₂
4-tetrakis (2-ethoxy-4-methoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine,
Abbreviation: SnCl₂Pc (2e4mPhNH)_FourF₁₂
4-tetrakis (o-propoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine,
Abbreviation: SnCl₂Pc (2pPhNH)_FourF₁₂
4-tetrakis (o-isopropoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine,
Abbreviation: SnCl₂Pc (2ipPhNH)_FourF₁₂
4-tetrakis (o-butoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine,
Abbreviation: SnCl₂Pc (2bPhNH)_FourF₁₂
4-tetrakis (o-tertbutoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine,
Abbreviation: SnCl₂Pc (2tbPhNH)_FourF₁₂
4-tetrakis (o-octyloxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine,
Abbreviation: SnCl₂Pc (2oPhNH)_FourF₁₂
4-tetrakis (4-ethoxyanilino) -3,5,6-dodecachlorotin chloride phthalocyanine,
Abbreviation: SnCl₂Pc (4ePhNH)_FourCl₁₂
4-tetrakis (4-ethoxyanilino) tin chloride phthalocyanine,
Abbreviation: SnCl₂Pc (4ePhNH)_Four
3-tetrakis (2-ethoxyanilino) tin chloride phthalocyanine,
Abbreviation: SnCl₂Pcα (2ePhNH)_Four
In the present invention, among the above phthalocyanine compounds,
4-tetrakis (2,4-dimethoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine,
4-tetrakis (2,6-dimethoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine,
4-tetrakis (2,4,6-trimethoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine,
4-tetrakis (o-ethoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine,
4-tetrakis (2,4-ethoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine,
4-tetrakis (o-propoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine,
4-tetrakis (o-isopropoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine,
4-tetrakis (o-butoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine,
4-tetrakis (o-tertbutoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine,
Is preferable because the compatibility with the resin is improved and the light resistance is improved.
[0040]
In particular, the raw material aniline is easily available and inexpensive.
4-tetrakis (2,4-dimethoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine,
4-tetrakis (o-ethoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine,
Is preferred. The central metal of the phthalocyanine compound of the present invention is preferably tin chloride, but the central metal may be mixed with a phthalocyanine compound in which a part of the central metal tin chloride such as tin oxide and tin hydroxide is changed. It doesn't matter.
[0041]
In the novel phthalocyanine production method of the present invention, the fluorine-containing phthalonitrile as a starting material thereof can be preferably synthesized according to the route of the following scheme 1. In addition, as a solvent for synthesis in each of the following schemes, an inert solvent such as nitrobenzene, acetonitrile, benzonitrile, pyridine, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone, triethylamine, tri-n -Aprotic polar solvents such as butylamine, dimethylsulfone, and sulfolane can be used. Acetonitrile and benzonitrile are particularly preferable.
[0042]
Moreover, it is preferable to use organic bases, such as triethylamine and tri-n-butylamine, and potassium fluoride as a condensing agent. In the present invention, since various anilines used as raw materials themselves act as a condensing agent, it is not necessary to use a new condensing agent. When a new condensing agent is not used, various anilines are 15 moles or more, preferably 2.0 to 3.0 moles per mole of the starting phthalonitrile. With respect to this synthesis method, the present inventors have already disclosed Japanese Patent Application Nos. 63-65806, 1-103554, 1-103555, 1-209599, and 4-274125. And Japanese Patent Application No. 8-215828.
[0043]
[Chemical 9]

[0044]
(Where A¹Has the same meaning as in general formula (3). )
The organic solvent used in the method for producing the novel phthalocyanine of the present invention may be any inert solvent that is not reactive with the starting material. For example, benzene, toluene, xylene, nitrobenzene, monochlorobenzene, dichlorobenzene, Inert solvents such as chlorobenzene, chloronaphthalene, methylnaphthalene, ethylene glycol, benzonitrile, or pyridine, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone, triethylamine, tri-n- Aprotic polar solvents such as butylamine, dimethylsulfone, and sulfolane can be used, and chloronaphthalene, trichlorobenzene, benzonitrile, and N-methyl-2-pyrrolidinone are preferable.
[0045]
In the method for producing a novel phthalocyanine compound represented by the general formula (1) of the present invention, the phthalonitrile represented by the general formula (3) may be charged in the range of 2 to 30 parts by weight with respect to 100 parts by weight of the organic solvent. preferable. The tin halide is preferably charged in the range of 0.20 to 0.45 mol, particularly preferably in the range of 0.30 to 0.40, with respect to 1 mol of phthalonitrile represented by the general formula (3). As the tin halide, stannic chloride and stannic bromide are preferably used, and stannic chloride is particularly preferable.
[0046]
As a preferable reaction temperature, a range of 100 to 300 ° C is preferable, and a range of 150 to 250 ° C is particularly preferable.
[0047]
The central metal is tin halide, and each of the four benzene nuclei in the phthalocyanine skeleton is substituted with at least one linear or branched alkoxy group having 1 to 8 carbon atoms in the ortho or para position. A method for producing a phthalocyanine compound substituted with an anilino group can be synthesized from the phthalonitrile obtained in the following scheme 2 in the same manner as the compound of the general formula (1).
[0048]
[Chemical Formula 10]

[0049]
(Wherein, X represents a fluorine atom, a bromine atom, or a chlorine atom, R¹May be the same or different, a hydrogen atom, a halogen atom or R²Represents the group R²Represents an alkyl group or an aryl group which may have a substituent, n represents an integer of 1 to 4, and A¹Has the same meaning as in general formula (3). )
Specific examples of the phthalonitrile compound synthesized by the methods of Scheme 1 and Scheme 2 include the following.
[0050]
4- (o-methoxyanilino) -3,5,6-trifluorophthalonitrile,
4- (2,4-dimethoxyanilino) -3,5,6-trifluorophthalonitrile,
4- (2,6-dimethoxyanilino) -3,5,6-trifluorophthalonitrile,
4- (2,4,6-trimethoxyanilino) -3,5,6-trifluorophthalonitrile,
4- (2,4-dimethoxy-6-methylanilino) -3,5,6-trifluorophthalonitrile,
4- (o-ethoxyanilino) -3,5,6-trifluorophthalonitrile,
4- (2,4-diethoxyanilino) -3,5,6-trifluorophthalonitrile,
4- (p-ethoxyanilino) -3,5,6-trifluorophthalonitrile,
4- (2-ethoxytetrafluoroanilino) -3,5,6-trifluorophthalonitrile,
4- (2-ethoxy-4-methoxyanilino) -3,5,6-trifluorophthalonitrile,
4- (o-propoxyanilino) -3,5,6-trifluorophthalonitrile,
4- (o-isopropoxyanilino) -3,5,6-trifluorophthalonitrile,
4- (o-butoxyanilino) -3,5,6-trifluorophthalonitrile,
4- (o-tertbutoxyanilino) -3,5,6-trifluorophthalonitrile,
4- (o-octyloxyanilino) -3,5,6-trifluorophthalonitrile,
4- (p-ethoxyanilino) -3,5,6-trichlorophthalonitrile,
4- (p-ethoxyanilino) phthalonitrile,
3- (o-ethoxyanilino) phthalonitrile,
The resin used in the present invention can be appropriately selected depending on the use of the obtained near-infrared (heat ray) absorber and shielding material, but is preferably a resin that is substantially transparent and does not significantly absorb and scatter. Specific examples include polycarbonate resins; (meth) acrylic resins such as methyl methacrylate; polyvinyl resins such as polystyrene, polyvinyl chloride, and polyvinylidene chloride; polyolefin resins such as polyethylene and polypropylene; polybutyral resin: polyvinyl acetate. Resin; Polyester resin such as polyethylene terephthalate, polyamide resin, etc. can be mentioned. Moreover, as long as it is substantially transparent, not only the above-mentioned one kind of resin but also a blend of two or more kinds of resins can be used, and the above resin can be sandwiched between transparent glasses. . However, when used as a heat storage / heat insulating material, it is not necessarily required to be a transparent resin.
[0051]
Among these resins, polycarbonate resin, (meth) acrylic resin, polyester resin, polyethylene resin, polystyrene resin or polyvinyl chloride resin excellent in weather resistance and transparency are preferable, and polycarbonate resin, methacrylic resin, polyethylene terephthalate resin or Polyvinyl chloride resin is preferred. When used as a heat-retaining and warming fiber, a polyethylene terephthalate resin or a polyamide resin is preferable.
[0052]
The polycarbonate resin is produced by reacting a dihydric phenol and a carbonate precursor by a solution method or a melting method. The following are mentioned as a typical example of dihydric phenol.
[0053]
2,2-bis (4-hydroxyphenyl) propane [bisphenol A], 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4 -Hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis ( 4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, and the like. Preferred divalent phenols are bis (4-hydroxyphenyl) alkanes, particularly those containing bisphenol as the main component.
[0054]
Examples of the acrylic resin include methyl methacrylate alone, a polymerizable unsaturated monomer mixture containing 50% or more of methyl methacrylate, or a copolymer thereof. Examples of the polymerizable unsaturated monomer copolymerizable with methyl methacrylate include the following. Methyl acrylate, ethyl (meth) acrylate (meaning methyl acrylate or methyl methacrylate, the same shall apply hereinafter), butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth ) Methoxyethyl acrylate, ethoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, tribromo (meth) acrylate Phenyl, (meth) acrylic acid tetrahydroxyfurfuryl, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolethane di (meth) acrylate, neopenty Gurukoruji (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate and the like.
[0055]
As the vinyl chloride resin, not only a polymer of vinyl chloride monomer but also a copolymer mainly composed of vinyl chloride can be used. Examples of monomers that can be copolymerized with vinyl chloride include vinylidene chloride, ethylene, propylene, acrylonitrile, vinyl acetate, maleic acid, itaconic acid, acrylic acid, and methacrylic acid.
[0056]
In practicing the present invention, preferred additives can be appropriately used depending on the purpose of use. Examples of the additive include a colorant, a polymerization regulator, an antioxidant, an ultraviolet absorber, a flame retardant, a plasticizer, a rubber for improving impact resistance, and a release agent.
[0057]
In using the phthalocyanine compound of the present invention, it can be used in combination with a conventionally known near-infrared absorber.
[0058]
Examples of the method of molding by mixing the phthalocyanine compound with a transparent resin include extrusion molding, injection molding, cast polymerization, press molding, calender molding, cast film forming method, and the like.
[0059]
Furthermore, it is also possible to prepare a heat ray shielding plate by preparing a film containing a phthalocyanine compound and subjecting the film to a transparent resin plate by hot pressing or heat lamination molding.
[0060]
Also, near-infrared (heat ray) absorbing and shielding plates and sheets by printing or coating a resin ink or paint containing a phthalocyanine compound on a substrate such as a transparent resin plate, transparent glass plate, film, fiber, paper, etc. Films, fibers, papers, etc. can also be obtained.
[0061]
The phthalocyanine compound used in the present invention is superior in heat resistance as compared with commercially available infrared absorbers, and therefore, resins such as injection molding and extrusion molding using acrylic resins, polycarbonate resins, and polyethylene terephthalate resins. Molding can also be performed by a molding method in which the temperature rises to a high temperature of 220 to 350 ° C., and a molded article having good transparency and excellent near-infrared absorption ability or heat ray shielding performance can be obtained. Moreover, it can spin at 220-350 degreeC with a polyester resin, a polyamide resin, etc., and a thermal storage heat retention fiber can be obtained. When
There is no problem even if it is used at a molding temperature lower than 220 ° C.
[0062]
There are no particular restrictions on the shape of the near-infrared (heat ray) absorbing material and the heat shielding material, and it includes various shapes such as corrugated, spherical, and dome shapes as well as the most common flat plate and film shapes. The
[0063]
The amount of the phthalocyanine compound used in the present invention can be varied depending on the setting of the visible and near-infrared transmittance of the sheet or film of the target thermal near-infrared (heat ray) shielding material and the thickness of the material, Usually, it is 0.0005 to 20 parts by weight, preferably 0.0015 to 10 parts by weight with respect to 100 parts by weight of the transparent resin.
[0064]
This blending amount varies depending on the shape of the near-infrared (heat ray) shielding material. For example, when creating a near-infrared (heat ray) shielding plate having a thickness of 3 mm, a blending amount of 0.002 to 0.06 parts by weight is preferable. More preferably, it is 0.005-0.03 weight part.
[0065]
When a near-infrared (heat ray) shielding plate having a thickness of 10 mm is prepared, the blending amount is preferably 0.0005 to 0.02 parts by weight, and more preferably 0.0015 to 0.01 parts by weight. When a near infrared (heat ray) shielding film having a thickness of 10 μm is prepared, the blending amount is preferably 0.5 to 20 parts by weight, more preferably 1.5 to 10 parts by weight. If the blending amount of the phthalocyanine compound is displayed regardless of the thickness of the near-infrared (heat ray) shielding material, it is considered to be the weight in the projected area from above, and is 0.06 to 2.4 g / m.²The amount is preferably 0.18 to 1.2 g / m.²It is.
[0066]
The amount of the phthalocyanine compound is 0.06 g / m²If the amount is smaller, the effect of shielding near infrared rays (heat rays) is reduced and 2.4 g / m.²In the case where it exceeds 1, it becomes remarkably expensive, and the transmission of visible light may become too small.
[0067]
An irregular shape such as a corrugated plate may be considered as the weight in the projected area from above. Further, as long as there is no problem in appearance, the concentration distribution of the phthalocyanine compound may be uneven. Moreover, it is also possible to mix and use one or more types of phthalocyanine compounds. When two or more types of phthalocyanine compounds having different absorption wavelengths are used, the near-infrared (heat ray) absorption shielding effect may be improved. .
[0068]
Also, by using a specific amount of phthalocyanine compound and carbon black, compared to the case where the phthalocyanine compound is used alone, the near-infrared (heat ray) absorption shielding effect is equivalent and the amount of phthalocyanine compound used is reduced to less than half. be able to. Moreover, the near-infrared (heat ray) absorption shielding effect improves compared with the case where a phthalocyanine compound and dye are used together.
[0069]
【Example】
Next, the present invention will be described more specifically with reference to examples.
[0070]
Example 1
Production of 4- (o-ethoxyanilino) -3,5,6-trifluorophthalonitrile
A 100 ml four-necked flask was charged with 10.00 g (50 mmol) of tetrafluorophthalonitrile, 16.45 g (120 mmol) of o-phenetidine and 60 ml of acetonitrile, and reacted under reflux for 4 hours. After completion of the reaction, the reaction mixture was poured into water, and the resulting solid content was washed with water and then with hexane to obtain 14.22 g of the objective yellow cake (yield 93.8%).
[0071]
Preparation of 4-tetrakis (o-ethoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine
In a 100 ml four-necked flask, 10.00 g (32 mmol) of 4- (o-ethoxyanilino) -3,5,6-trifluorophthalonitrile obtained above and 1.79 g of tin (II) chloride ( 9.46 mmol) and 30 ml of benzonitrile were charged and reacted at 175 ° C. for 5 hours. After completion of the reaction, the reaction mixture from which benzonitrile was distilled off was dissolved in tetrahydrofuran, and the solid content produced by pouring into hexane was washed with hexane to obtain 10.50 g of the desired deep blue cake (yield). (Rate 91.3%).
[0072]

The infrared absorption spectrum of this compound is shown in FIG.
[0073]
The thermal decomposition temperature and light resistance data of this compound are shown in Table 1.
[0074]
Example 2
Preparation of 4-tetrakis (2,4-dimethoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine
A 100 ml four-necked flask was charged with 10.00 g (50 mmol) of tetrafluorophthalonitrile, 18.37 g (120 mmol) of 2,4-dimethoxyaniline and 60 ml of benzonitrile, and reacted at 80 ° C. for 6 hours. After completion of the reaction, the reaction mixture was poured into water, and the separated benzonitrile layer was washed with water, aqueous hydrochloric acid and then with water, and the benzonitrile layer was separated to give 4- (2,4-dimethoxyanilino) -3. Thus, 50 g of a benzonitrile solution of 5,6-trifluorophthalonitrile was obtained.
[0075]
Subsequently, by analyzing the benzonitrile solution of 4- (2,4-dimethoxyanilino) -3,5,6-trifluorophthalonitrile obtained above by liquid chromatography, the concentration of the phthalonitrile was 30. .16% by weight. A 100 ml four-necked flask was charged with 50 g of the benzonitrile solution of 4- (2,4-dimethoxyanilino) -3,5,6-trifluorophthalonitrile and 2.57 g (14 mmol) of tin (II) chloride. The reaction was carried out at 175 ° C. for 5 hours. After completion of the reaction, the reaction mixture from which benzonitrile was distilled off was dissolved in tetrahydrofuran, and the solid content produced by pouring into hexane was washed with hexane to obtain 10.86 g of the desired deep blue cake (yield). (Rate 63.03%).
[0076]

The infrared absorption spectrum of this compound is shown in FIG.
[0077]
The thermal decomposition temperature and light resistance data of this compound are shown in Table 1.
[0078]
Example 3
Preparation of 4- (2,4,6-trimethoxyanilino) -3,5,6-trifluorophthalonitrile
In the preparation of 4- (o-ethoxyanilino) -3,5,6-trifluorophthalonitrile of Example 1, instead of o-phenetidine, 21.97 g (120 mmol) of 2,4,6-trimethoxyaniline was used. ) Was used in the same manner as in the production of 4- (o-ethoxyanilino) -3,5,6-trifluorophthalonitrile of Example 1 to obtain 15.56 g of the objective yellow cake. (Yield 85.7%).
[0079]
Preparation of 4-tetrakis (2,4,6-trimethoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine
In the preparation of 4-tetrakis (o-ethoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine of Example 1, 4- (o-ethoxyanilino) -3,5,6-trifluorophthalonitrile Instead of 4- (2,4,6-trimethoxyanilino) -3,5,6-trifluorophthalonitrile 10.00 g (28 mmol) instead of 4-tetrakis ( o-Ethoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine was prepared in the same manner as described above to obtain 7.10 g of the desired deep blue cake (yield 62.8%).
[0080]
Visible absorption spectrum

The thermal decomposition temperature and light resistance data of this compound are shown in Table 1.
[0081]
Example 4
Production of 4- (o-isopropoxyanilino) -3,5,6-trifluorophthalonitrile
In the production of 4- (o-ethoxyanilino) -3,5,6-trifluorophthalonitrile of Example 1, 18.14 g (120 mmol) of o-isopropoxyaniline was used instead of o-phenetidine. Except for the above, the same operation as in the production of 4- (o-ethoxyanilino) -3,5,6-trifluorophthalonitrile of Example 1 was carried out to obtain 20.05 g of the objective yellow cake (yield 91 .5%).
[0082]
Preparation of 4-tetrakis (o-isopropoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine
In the preparation of 4-tetrakis (o-ethoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine of Example 1, 4- (o-ethoxyanilino) -3,5,6-trifluorophthalonitrile Instead of using 10.00 g (30 mmol) of 4- (o-isopropoxyanilino) -3,5,6-trifluorophthalonitrile instead of 4-tetrakis (o-ethoxyaniline of Example 1). Reno) -3,5,6-dodecafluorotin chloride The same procedure as in the production of tin phthalocyanine was performed to obtain 10.22 g of the desired deep blue cake (yield 89.4%).
[0083]

The thermal decomposition temperature and light resistance data of this compound are shown in Table 1.
[0084]
Comparative Example 1
Production of 4-anilino-3,5,6-trifluorophthalonitrile
The production of 4- (o-ethoxyanilino) -3,5,6-trifluorophthalonitrile of Example 1 was carried out except that 11.17 g (120 mmol) of aniline was used instead of o-phenetidine. The same operation as in Example 1 for producing 4- (o-ethoxyanilino) -3,5,6-trifluorophthalonitrile gave 12.52 g of the desired yellow cake (yield 91.7%). .
[0085]
4-tetrakisanilino-3,5,6-dodecafluorotin chloride phthalocyanine (abbreviation: SnCl₂Pc (PhNH)_FourF₁₂)Manufacturing of
In the preparation of 4-tetrakis (o-ethoxyanilino) -3,5,6-dodecafluorotin chloride phthalocyanine of Example 1, 4- (o-ethoxyanilino) -3,5,6-trifluorophthalonitrile Instead of using 10.00 g (37 mmol) of 4-anilino-3,5,6-trifluorophthalonitrile, 4-tetrakis (o-ethoxyanilino) -3,5,6- of Example 1 was used. The same operation as in the production of dodecafluorotin chloride phthalocyanine was carried out to obtain 10.35 g of the target deep blue cake (yield 88.2%).
[0086]

The thermal decomposition temperature and light resistance data of this compound are shown in Table 1.
[0087]
Comparative Example 2
Octafluorooctakis anilinooxyvanadium phthalocyanine (abbreviation: VOPc (PhNH))₈F₈)Manufacturing of
In a 100 ml four-necked flask, 5.19 g (6 mmol) of hexadecafluoxyvanadium phthalocyanine and 26.82 g (288 mmol) of aniline were charged and reacted at reflux temperature for 4 hours. After completion of the reaction, the insoluble matter was filtered off, and then the aniline was distilled off. The resulting solid was washed with 300 ml of n-hexane to obtain 6.72 g of the desired black cake (yield 77.1%). .
[0088]

The thermal decomposition temperature and light resistance data of this compound are shown in Table 1.
[0089]
[Table 1]

[0090]
The thermal decomposability was evaluated by the following three steps based on the temperature when the temperature was reduced by 5% by increasing the temperature from room temperature using a differential thermogravimetric analyzer.
[0091]
○ Temperature when weight decreases by 5% Over 250 ° C
△ Temperature when weight decreases by 5% Over 200 ℃ ~ 250 ℃
× Temperature when weight decreases by 5% 200 ° C or less
The light resistance was evaluated by the following method.
[0092]
1 g of the dye was dissolved in 20 g of ethyl cellosolve, and a dye thin film was prepared on a glass substrate by a spin coating method to prepare a sample. This sample was set in a xenon light resistance tester (irradiation light quantity 120,000 Lux), and the decrease in absorbance over time was measured. Then, the following three stages of evaluation were performed based on the residual rate of absorbance after 100 hours.
[0093]
○ Absence of absorbance after 100 hours 80% or more
△ Absorption rate after 100 hours 30% to less than 80%
× Absorption remaining rate after 100 hours 30% or less
In addition, the measuring method of the maximum absorption wavelength in an Example and a comparative example was performed using the method shown below.
[0094]
For the data in the solution, ethyl cellosolve was used as the solvent, and each sample concentration was 3.75 to 4.00 × 10.^-FiveIt adjusted to the range of mol / liter, and it measured using Shimadzu UV-3100 ultraviolet visible spectrophotometer with a 10-mm measuring cell.
[0095]
For thin film data, 1 g of dye was dissolved in 20 g of ethylene cellosolve and a dye thin film was prepared on a glass substrate by spin coating, and the sample was used with Shimadzu UV-3100 UV-visible spectrophotometer. Measured.
[0096]
Examples 5-8
To 100 parts by weight of molten polycarbonate resin (Teijin Kasei Co., Ltd., Panlite 1285, trade name), add the amount of the phthalocyanine compound shown in Table 1 as shown in Table 2, and use a T-die extruder to make a sheet of 3 mm thickness 280 Molded at ℃. Visible light transmittance and heat ray transmittance of the obtained plate were measured.
[0097]
In addition, the transmission spectrum and transmittance of the obtained heat ray shielding plate were measured with a spectrophotometer (manufactured by Shimadzu Corporation: UV-3100). Moreover, the values of visible light transmittance (400 to 800 nm) and heat ray part transmittance (800 to 1,000 nm) of the heat ray shielding plate were determined according to the standard of JIS R 3106.
[0098]
That is, the visible light transmittance is a value obtained by dividing the value of 400 to 800 nm of the solar radiation transmittance obtained by JIS R 3106 by 0.545, and the heat ray transmittance is 800 to 1 of the solar radiation transmittance obtained by JIS R 3106. , 000 nm value divided by 0.173. In addition, the energy distribution of sunlight rays is 0.545 in the range of 400 to 800 nm, and 0.173 in the range of 800 to 1,000 nm. Note that the range of 340 to 400 nm is excluded because of the ultraviolet region.
[0099]
Comparative Examples 3-4
The phthalocyanine compounds proposed by the present inventors in JP-A-5-345861 and JP-A-6-264050 are blended in the same manner as in Examples 5 to 8, and the same operations as in Examples 5 to 8 are performed. The result was obtained.
[0100]
Comparative Example 5
The results shown in Table 2 were obtained in the same manner as in Examples 5 to 8, except that no phthalocyanine compound was added to Examples 5 to 8.
[0101]
[Table 2]

[0102]
As can be seen from the results in Table 2, VOPc (PhNH)₈F₈Visible light transmittance is not good, but absorbs heat rays in the near infrared region of 800 to 1,000 nm well. Meanwhile, SnCl₂Pc (PhNH)_FourF₁₂Has a high visible light transmittance and transparency, but has a poor absorption factor for heat rays in the near infrared region of 800 to 1,000 nm. The compounds of Examples 1 to 4 of the present invention absorb well in the near infrared region of 800 to 1,000 nm and have high visible light transmittance as compared with those compounds.
[0103]
Thus, in the present invention, when the phthalocyanine compound of the present invention is used as a near-infrared (heat ray) absorber and a shielding material, a sheet having a thickness of 3 mm was prepared by adding 0.01% to a molten polycarbonate resin of the phthalocyanine compound. The sheet has a visible light transmittance of 400 to 800 nm of 45% or more (preferably 50% or more) and a heat light transmittance of 800 to 1,000 nm of 30% or less (preferably 25% or less). Is good.
[0104]
【The invention's effect】
The novel phthalocyanine compound according to the present invention has absorption in the near infrared region of 800 to 1000 nm, has excellent solubility in organic solvents, and is excellent in light resistance originally possessed by phthalocyanine. Therefore, the infrared ray filter for electronic equipment, the infrared filter for photography, the heat ray shielding agent for automobiles or building materials, the agricultural film, the protective glasses, the sunglasses or the semiconductor laser are used. Sensing near-infrared light such as optical recording media, liquid crystal display elements, and near-infrared absorbing dyes for writing or reading in optical character readers that use near-infrared (heat ray) absorption effects, television and video Sensors, near infrared photosensitizers for photography and electrophotography, thermal transfer, thermal paper and thermal stencil Photothermal conversion agent, the near infrared absorbing ink such as an ink for barcode tamper preventing forgery, in which further exhibits an excellent effect as a heat storage heat retaining agent such as fibers.
[0105]
Further, the near infrared (heat ray) absorbing material and shielding material of the present invention are excellent in near infrared absorption, excellent in compatibility with resin, excellent in light resistance and heat resistance, and contain a phthalocyanine compound with little absorption in the visible region. Made of resin, translucent or transparent and heat rays such as building or vehicle windows, ceiling windows, doors, telephone boxes, arcades, carports, factory roofs or ceiling domes, garden greenhouses, sunglasses or protective glasses It can be used as a resin plate, sheet, film, fiber or paint for the purpose of shielding, and can absorb near-infrared light and change it into heat, so it can be used for heat storage and heat insulation. It can also be used as a semiconductor photo detector, color solid-state image sensor, CRT display, plasma display, etc. The purpose of the resin plate for shielding a and near infrared transparency to semi-transparency not of a sheet, a film can be used as a fiber or coating.
[Brief description of the drawings]
FIG. 1 is an infrared absorption spectrum of a phthalocyanine compound according to Example 1 of the present invention.
FIG. 2 is an infrared absorption spectrum of a phthalocyanine compound according to Example 2 of the present invention.

Claims (5)

The following general formula (1)

(Wherein, M represents SnCl ₂ , and A represents an anilino group in which at least one linear or branched alkoxy group having 1 to 8 carbon atoms is substituted at the ortho or para position. A phthalocyanine compound represented by. In the general formula (1), A represents the following general formula (2)

(In the formula, R ¹ and R ² represent an alkyl group having 1 to 8 carbon atoms, n represents an integer of 0 to 2, and the total number of carbon atoms of R ¹ and R ² is 2 or more. The phthalocyanine compound according to claim 1, wherein The following general formula (3)

(In the formula, A ¹ represents an anilino group in which at least one linear or branched alkoxy group having 1 to 8 carbon atoms that can be substituted is substituted in the ortho or para position.) The method for producing a phthalocyanine compound according to claim 1 or 2, wherein the phthalonitrile compound represented by the formula (1) is reacted with a tin halide. The following general formula (1)

(Wherein, M represents SnCl ₂ , and A represents an anilino group in which at least one linear or branched alkoxy group having 1 to 8 carbon atoms is substituted at the ortho or para position. the phthalocyanine compound represented by.), absorbs near infrared 800nm~1000nm made of a resin containing 0.0005 parts by weight per 100 parts by weight of the resin near infrared (heat rays) absorbers and shielding materials. In the general formula (1), A represents the following general formula (2)

(In the formula, R ¹ and R ² represent an alkyl group having 1 to 8 carbon atoms, n represents an integer of 0 to 2, and the total number of carbon atoms of R ¹ and R ² is 2 or more. in a.) a near infrared of claim 4 which is (heat rays) absorbers and shielding materials.

Images