JP3781466B2 - Near-infrared absorbing compound and method for producing the same - Google Patents

Description

〔式中、Ｘ¹は各々独立にハロゲン原子、置換または未置換のアルコキシ基、あるいは置換または未置換のアリールオキシ基、あるいは置換または未置換のアルキルチオ基、あるいは置換または未置換のアリールチオ基を表わし、ｎ²は０〜１４の整数を表わす。Ｒ¹，Ｒ²，Ｒ³，Ｒ⁴，Ｒ⁵，Ｒ⁶，Ｒ⁷，Ｒ⁸は各々独立に、水素原子、置換または未置換のアルキル基、あるいは置換または未置換のアリール基を表わし、Ｚ¹，Ｚ²は各々独立に、酸素原子、硫黄原子またはＮＹ基（Ｙは水素原子、置換または未置換のアルキル基、置換または未置換のアリール基、置換または未置換のアルキルカルボニル基、あるいは、置換または未置換のアリールカルボニル基を表わす。）を表わし、ｍは１〜８の整数、ｌは０〜７の整数を表わす。また、ｎ¹＋２ｌ＋２ｍは２〜１６の整数を表わす。Ｍは２価の金属原子あるいは３価または４価の置換金属またはオキシ金属を表わす。〕
【００１４】
【化６】

〔式中、Ｘ²は各々独立にハロゲン原子、置換または未置換のアルコキシ基、あるいは置換または未置換のアリールオキシ基、あるいは置換または未置換のアルキルチオ基、あるいは置換または未置換のアリールチオ基を表わし、ｎ²は８〜１６の整数を表わす。Ｒ⁵，Ｒ⁶，Ｒ⁷，Ｒ⁸，Ｍは各々独立に、水素原子、置換または未置換のアルキル基、あるいは置換または未置換のアリール基を表し、Ｚ²は酸素原子、硫黄原子またはＮＹ基（Ｙは水素原子、置換または未置換のアルキル基、あるいは、置換または未置換のアリール基、置換または未置換のアルキルカルボニル基、あるいは、置換または未置換のアリールカルボニル基を表わす。）を表わし、ｌは０〜７の整数を表わす。また、ｎ²＋２ｌは１０〜１６の整数を表わし、Ｍは２価の金属原子あるいは３価または４価の置換金属またはオキシ金属を表わす。〕
【００１５】
【化７】

〔式中、Ｒ¹，Ｒ²，Ｒ³，Ｒ⁴は各々独立に、水素原子、置換または未置換のアルキル基、あるいは置換または未置換のアリール基、Ｚ¹は酸素原子、硫黄原子またはＮＹ基（Ｙは水素原子、置換または未置換のアルキル基、あるいは、置換または未置換のアリール基を表わす。）を表わす。〕
【００１６】
本発明は、耐光性を有する溶解型フタロシアニン系の近赤外線吸収化合物を、簡便に提供するものである。
【００１７】
【発明の実施の形態】
以下、本発明における近赤外線吸収化合物、及びその製造方法の好ましい様態を詳述する。
【００１８】
本発明における近赤外線吸収化合物は一般式（１）で表わされ、式中Ｘ¹で表わされるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、沃素原子が挙げられ、特に好ましくは塩素原子、臭素原子が挙げられる。
【００１９】
一般式（１）式中、Ｘ¹で表わされる置換または無置換のアルコキシ基として好ましくは炭素数１〜１０の直鎖または分岐のアルコキシ基であって、より好ましくはメトキシ基、エトキシ基、ｎ−プロポキシ基、ｉｓｏ−プロポキシ、ｎ−ブトキシ基、ｉｓｏ−ブトキシ基、ｓｅｃ−ブトキシ基、ｎ−ペンチルオキシ基、ｉｓｏ−ペンチルオキシ基、１，２−ジメチル−プロポキシ基、ｎ−ヘキシルオキシ基、１，３−ジメチル-ブトキシ基、１，２−ジメチルブトキシ基、ｎ−ヘプチルオキシ基、１，４−ジメチルペンチルオキシ基、１−エチル−３−メチルブトキシ基、ｎ−オクチルオキシ基、２−エチルヘキシルオキシ基；
ベンジルオキシ基、ｓｅｃ−フェニルエトキシ基、２−フェニルエトキシ基、２−メチルベンジルオキシ基、４−メチルベンジルオキシ基；
３−ジメチルアミノプロポキシ基、２−ジメチルアミノエトキシ基、２−ジイソプロピルアミノエトキシ基、２−ジエチルアミノエトキシ基、２，２，２−トリフルオロ−１−（トリフルオロメチル）エトキシ基等が挙げられる。
【００２０】
一般式（１）式中、Ｘ¹で表わされる置換または無置換のアリールオキシ基として好ましくは炭素数６〜２０の置換または無置換のアリールオキシ基であって、より好ましくはフェニルオキシ基、２−メチルフェニルオキシ基、３−メチルフェニルオキシ基、４−メチルフェニルオキシ基、ナフチルオキシ基等が挙げられる。
【００２１】
一般式（１）式中、Ｘ¹で表わされる置換または無置換のアルキルチオ基としては、好ましくは炭素数１〜１０の直鎖または分岐のアルキルチオ基であって、より好ましくはメチルチオ基、エチルチオ基、ｎ−プロピルチオ基、ｉｓｏ−プロピルチオ基、ｎ−ブチルチオ基、ｉｓｏ−ブチルチオ基、ｓｅｃ−ブチルチオ基、ｎ−ペンチルチオ基、ｉｓｏ−ペンチルチオ基、１，２−ジメチル−プロピルチオ基、ｎ−ヘキシルチオ基、１，３−ジメチル-ブチルチオ基、１，２−ジメチルブチルチオ基、ｎ−ヘプチルチオ基、１，４−ジメチルペンチルチオ基、１−エチル−３−メチルブチルチオ基、ｎ−オクチルチオ基、２−エチルヘキシルチオ基；
ベンジルチオ基、ｓｅｃ−フェニルエチルチオ基、２−フェニルエチルチオ基、２−メチルベンジルチオ基、４−メチルベンジルチオ基、２−アミノエチルチオ基、２−メチルアミノエチルチオ基、２−エチルアミノエチルチオ基、２−プロピルアミノエチルチオ基、２−ブチルアミノエチルチオ基、２−ペンチルアミノエチルチオ基、２−ヘキシルアミノエチルチオ基、２−ヘプチルアミノエチルチオ基、２−オクチルアミノエチルチオ基、２−ベンジルアミノエチルチオ基、２−（２−フェニルエチル）アミノエチルチオ基；
３−ジメチルアミノプロピルチオ基、２−ジメチルアミノエチルチオ基、２−ジイソプロピルアミノエチルチオ基、２−ジエチルアミノエチルチオ基、２，２，２−トリフルオロ−１−（トリフルオロメチル）エチルチオ基等が挙げられる。
【００２２】
一般式（１）式中、Ｘ¹で表わされる置換または無置換のアリールチオ基としては好ましくは炭素数６〜２０の置換または無置換のアリールチオ基であって、より好ましくはフェニルチオ基、２−メチルフェニルチオ基、３−メチルフェニルチオ基、４−メチルフェニルチオ基、２−アミノフェニルチオ基、３−アミノフェニルチオ基、４−アミノフェニルチオ基、２−メチルアミノフェニルチオ基、３−メチルアミノフェニルチオ基、４−メチルアミノフェニルチオ基、２−エチルアミノフェニルチオ基、２−プロピルアミノフェニルチオ基、ナフチルチオ基等が挙げられる。
【００２３】
Ｘ¹として特に好ましくは、ハロゲンまたは、下記一般式（２）で表される置換基である。
【００２４】
【化８】

〔式中、Ｒ¹〜Ｒ⁴、Ｚ¹は一般式（１）と同様の原子または置換基を表す。〕
一般式（１）において、ｎ¹は０〜１４の整数を表わすが、より好ましくは０〜８の整数を表わす。
【００２５】
また、式中Ｒ¹，Ｒ²，Ｒ³，Ｒ⁴，Ｒ⁵，Ｒ⁶，Ｒ⁷，Ｒ⁸で表わされる置換または未置換のアルキル基の例としては、メチル基、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル基、ｎ−ブチル基、ｉｓｏ−ブチル基、ｓｅｃ−ブチル基、ｎ−ペンチル基、ｉｓｏ−ペンチル基、１，２−ジメチル−プロピル基、ｎ−ヘキシル基、１，３−ジメチル-ブチル基、１，２−ジメチルブチル基、ｎ−ヘプチル基、１，４−ジメチルペンチル基、１−エチル−３−メチルブチル基、ｎ−オクチル基、２−エチルヘキシル基、ｎ−ノニル基、ｎ−デシル基、ｎ−ウンデシル基、ｎ−ドデシル基、ｎ−トリデシル基、ｎ−テトラデシル基、ｎ−ペンタデシル基、ｎ−ヘキサデシル基、ｎ−ヘプタデシル基、ｎ−オクタデシル基、ｎ−ノナデシル基、ｎ−エイコシル基；
ベンジル基、ｓｅｃ−フェニルエチル基、２−メチルベンジル基、３−メチルベンジル基、４−メチルベンジル基、２−フェニルエチル基；
２−ヒドロキシエチル基、３−ヒドロキシプロピル基；
３−ジメチルアミノプロピル基、２−ジメチルアミノエチル基、２−ジイソプロピルアミノエチル基、２−ジエチルアミノエチル基、２，２，２−トリフルオロ−１−（トリフルオロメチル）エチル基、２−（１−ピペリジニル）エチル基、３−（１−ピペリジニル）プロピル基、３−（４−モルフォリニル）プロピル基、３−（４−モルフォリニル）エチル基、２−（１−ピロリジニル）エチル基、２−ピリジルメチル基、フルフリル基等が挙げられる。
【００２６】
置換または未置換のアリール基としては、フェニル基、２−メチルフェニル基、３−メチルフェニル基、４−メチルフェニル基、ナフチル基等が挙げられる。
【００２７】
これらの中でも特に好ましいのは炭素数が５〜２０のアルキル基である。生成物が有機溶媒、樹脂等に高い溶解度を示し、近赤外線吸収フィルター樹脂中での曇り現象が生じないためには、炭素数が５以上の置換基が少なくとも一つ置換している必要がある。しかし、炭素数が２０を越えると生成物が液体となり、フィルター用色素としては不適当になることがある。
【００２８】
さらに、式中Ｚ¹、Ｚ²で表わされる原子あるいは置換基としては、酸素原子、硫黄原子あるいはＮＹ基などが挙げられ、Ｙは水素原子、総炭素数１〜２０の置換または未置換のアルキル基、総炭素数６〜２０の置換または未置換のアリール基、総炭素数１〜２０の置換または未置換のアルキルカルボニル基、あるいは、総炭素数６〜２０の置換または未置換のアリールカルボニル基が挙げられる。
【００２９】
Ｙで表される置換または未置換のアルキル基の例としては、メチル基、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル基、ｎ−ブチル基、ｉｓｏ−ブチル基、ｎ−ペンチル基、ｉｓｏ−ペンチル基、１，２−ジメチル−プロピル基、ｎ−ヘキシル基、ｎ−ヘプチル基、１−エチル−３−メチルブチル基、ｎ−オクチル基、２−エチルヘキシル基、ｎ−ノニル基、ｎ−デシル基、ｎ−ウンデシル基、ｎ−ドデシル基、ｎ−トリデシル基、ｎ−ペンタデシル基、ｎ−オクタデシル基；ベンジル基、ｓｅｃ−フェニルエチル基、３−メチルベンジル基、４−エチルベンジル基、２−フェニルエチル基；
３−ジメチルアミノプロピル基、２−ジイソプロピルアミノエチル基、２−ジエチルアミノエチル基、２，２，２−トリフルオロ−１−（トリフルオロメチル）エチル基、２−（１−ピペリジニル）エチル基、３−（４−モルフォリニル）プロピル基、２−（１−ピロリジニル）エチル基、２−ピリジルメチル基、フルフリル基等が挙げられ、より好ましくは、ｉｓｏ−ブチル基、ｉｓｏ−ペンチル基、ｎ−オクチル基、２−エチルヘキシル基、２−フェニルエチル基、２−ジイソプロピルアミノエチル基等が挙げられる。
【００３０】
Ｙで表される置換または未置換のアリール基の例としては、フェニル基、２−メチルフェニル基、３−メチルフェニル基、４−メチルフェニル基、４−メトキシフェニル基、１−ナフチル基等が挙げられる。
【００３１】
ｍは１〜８の整数を表わし、より好ましく２〜６の整数を表わす。
【００３２】
ｌは０〜７の整数を表わし、より好ましく０〜４の整数を表わす。
【００３３】
また、ｎ¹＋２ｌ＋２ｍは２〜１６の整数を表わし、より好ましくは８〜１６の整数を表わす。
【００３４】
また、Ｍは２価の金属原子あるいは３価または４価の置換金属またはオキシ金属が挙げられ、好ましくはＣｕ、ＡｌＣｌ、ＴｉＯまたはＶＯ、より好ましくはＣｕが挙げられる。
【００３５】
本発明で用いる一般式（３）で表わされるフタロシアニンにおいて、Ｘ²で表わされるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、沃素原子が挙げられ、好ましくは塩素原子、臭素原子が挙げられる。該フタロシアニンの入手法としては、Ｘ²が塩素原子、臭素原子等のものについては工業的に入手可能であるし、Ｘ²が沃素原子のものは、これらのものを、沃化カリ、沃化ナトリウム等で定法に従い処理して沃素原子と置換することにより入手できる。また、フッ素化フタロシアニンは、フッ素化フタロニトリルを Dyes and Pigment 91 頁(1992年)記載の方法で製造できる。
【００３６】
さらに、Ｘ²がアルコキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基については、上述のハロゲン化フタロシアニンに、対応するアルコールまたはチオールを反応させることにより製造できる。
【００３７】
Ｒ⁵，Ｒ⁶，Ｒ⁷，Ｒ⁸，Ｚ²，Ｍは、一般式（１）中と同様のものが挙げられる。
【００３８】
一般式（３）で表わされるフタロシアニンにおいて、特に好ましい化合物は、Ｃ．Ｉ．ピグメントグリーン ７（フタロシアニン グリーン）、Ｃ．Ｉ．ピグメントグリーン ３６、あるいはＣ．Ｉ．ピグメントグリーン ３８であり、ハロゲン化フタロシアニンとして工業的に入手容易な化合物である。
【００３９】
本発明で用いる一般式（４）で表わされるエタンチオールにおいてＲ¹，Ｒ²，Ｒ³，Ｒ⁴，Ｚ¹は、一般式（１）中と同様のものが挙げられる。
【００４０】
一般式（３）で表わされるフタロシアニンと一般式（４）で表わされるエタンチオール誘導体との反応は、通常の求核置換反応の条件、すなわち、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、水素化ナトリウム等の無機塩基、あるいはピリジン、トリエチルアミン、キノリン等の有機塩基存在下で行うことができる。
【００４１】
この反応は、溶媒の存在下で行ってもよく、その際の溶媒としては、ジメチルホルムアミド（ＤＭＦ）、ジメチルスルホキシド（ＤＭＳＯ）、Ｎ，Ｎ’−ジメチルイミダゾリジノン（ＤＭＩ）、スルホラン、ピリジン等の極性溶媒、アセトン、メチルエチルケトン等のケトン溶媒、トルエン、キシレン、モノクロルベンゼン、ジクロルベンゼン等の芳香族炭化水素溶媒が挙げられる。
【００４２】
本発明の近赤外線吸収化合物の製造方法は、通常、一般式（３）で表わされるフタロシアニンと塩基（フタロシアニンに対して４〜１００倍当量）を、溶媒（フタロシアニンに対して、１〜１０００重量倍）に溶解、あるいは懸濁させて、攪拌しながら、一般式（４）で表わされるエタンチオール誘導体（フタロシアニンに対して、４〜４０倍当量）を添加し、５０〜２２０℃で反応させる。エタンチオール誘導体の添加は、昇温前におこなっても、昇温途中、あるいは昇温後に行ってもよい。また、一度に添加してもよく、分割添加してもよい。また、エタンチオール誘導体自身を溶媒として用い、塩基を加えた後に、フタロシアニンを添加してもよい。
【００４３】
反応の際、触媒として、金属銅、塩化銅、臭化銅、沃化銅、酸化銅等の銅触媒を添加することも出来る。反応は、常圧下でも、加圧下で行ってもよい。
【００４４】
反応の進行度合いは、例えば、反応液のλmaxを測定することにより判断することができる。
【００４５】
反応終了後、反応混合物を冷却した水、あるいは、メタノール、エタノール、プロパノール、ブタノール、ペンタノール等のアルコール溶液中に排出することにより、目的化合物を析出させる。析出した目的物を吸引濾過して分離し、さらに水洗浄、アルコール洗浄して、塩分、残塩基、未反応のエタンチオール誘導体等を除去し、乾燥して、本発明の近赤外線吸収化合物を単離する。得られた本発明の近赤外線吸収化合物は、トルエン、キシレン、酢酸エチル等の有機溶媒によく溶解するため、必要により、カラムクロマトグラフィーにて精製することもできる。
【００４６】
本発明の方法で製造した近赤外線吸収化合物は、更に、ヨウ化メチル、ブロモエチル、１−ブロモプロパン、２−ブロモプロパン、１−クロロブタン、２−ブロモブタン、１−ブロモ−２−メチルブタン、１−ブロモ−３−メチルブタン、１−クロロペンタン、１−ブロモヘキサン、１−ブロモ−２−エチルヘキサン、１−ブロモオクタン、ベンジルクロリド等のハロゲン化アルキルと、上記と同様の条件下で反応させる、
あるいは、無水酢酸、トリフルオロアセチルクロリド、アセチルクロリド、１−ブチルクロリド、イソブチルクロリド、２−エチルヘキサノイルクロリド等のアルキル酸クロリド、または、ベンゾイルクロリド、４−メトキシベンゾイルクロリド、ナフチルクロリド等のアリール酸クロリドを塩基の存在下に反応させることにより、更にλmaxが長波長化、あるいは短波長化される近赤外線吸収化合物を得ることができる。
【００４７】
この場合、上記方法で単離した近赤外線吸収化合物と塩基（近赤外線吸収化合物に対して、１〜１００重量倍）を溶媒（近赤外線吸収化合物に対して、１〜１０００重量倍）に溶解、あるいは懸濁させて、攪拌しながら、ハロゲン化アルキル（近赤外線吸収化合物に対して、１〜１００重量倍）を添加して、５０〜２２０℃で反応を行う。
【００４８】
また、近赤外線吸収化合物を単離することなく、フタロシアニンとエタンチオール誘導体を反応させた反応混合物に、直接、ハロゲン化アルキルまたは酸ハロゲン化物を添加し、さらに反応を続けることもできる。
【００４９】
反応後は、上記の方法と同様に処理することができる。
【００５０】
本発明の近赤外線吸収化合物の製造法は、出発物質が安価で、耐光性も良く、樹脂、溶媒等への溶解性のある化合物が簡単に得られる方法である。
【００５１】
更に、本発明の方法で得られる生成物は単一化合物ではなく、数種類の混合物として得られるため、吸収波長がブロードになり、近赤外線領域を幅広く吸収するため、近赤外線吸収フィルター等への応用が容易であり、熱線吸収用として優れた化合物である。
【００５２】
【実施例】
以下、本発明を実施例により、更に詳細に説明するが、本発明は、これによりなんら制限されるものではない。
【００５３】
実施例１
Ｃ．Ｉ．ピグメントグリーン ７（フタロシアニン グリーン）（７．０ｇ、６．２１ｍｍｏｌ）、２−アミノエタンチオール（９．５７g、１２４ｍｍｏｌ、２０倍当量）、炭酸カリウム（３０．９ｇ、２２３ｍｍｏｌ、３６倍当量）を、ジメチルイミダゾリジン（２００ｍｌ）中、１５０℃で、３時間反応させた。この反応液に、さらにｎ−オクチルブロミド（７．４３ｇ、３８．４７ｍｍｏｌ）を加えて、１時間反応させた。反応混合物は、室温に冷却後、メタノール（８００ｍｌ）中に排出した。析出物を吸引濾過により回収後、メタノール洗浄、水洗後、乾燥させ、下記式（５）の化合物を含有する近赤外線吸収混合物（８．１３ｇ）を得た。該混合物はトルエン、ベンゼン等の芳香族溶媒、クロロホルム等のハロゲン化炭化水素溶媒に溶け、λmaxは８４６ｎｍ（クロロホルム溶媒）であった。
【００５４】
【化９】

【００５５】
分光特性；λmax=846 nm、εg=3.22×10⁴ml/g・cm（溶媒；クロロホルム）
元素分析; C₁₂₈H₂₁₂N₂₀S₁₂Cu
分析値(%) Ｃ：61.82 Ｈ：8.63 Ｎ：11.24 Ｓ：15.52 Ｃｕ：2.6
【００５６】
更に、該混合物を、ユニチカ製ポリエチレンテレフタレートペレット１２０３と重量比０．０２：１の割合で混合し、２６０〜２８０℃で溶融させ、押出機で厚み１００μｍのフィルムを作製した後、このフィルムを２軸延伸して厚み２５μｍの近赤外線吸収フィルターを作製した。該フィルターは７００〜１１００ｎｍの光をよく吸収した。ＪＩＳ−Ｒ−３１０６に従って、（株）島津製作所製分光光度計ＵＶ−３１００でＴV（可視光透過率）及びＴE（日射透過率）を測定したところ、それぞれ６８％、６５％であった。
【００５７】
実施例２
Ｃ．Ｉ．ピグメントグリーン ７（フタロシアニン グリーン）（１０．０ｇ、８．８７ｍｍｏｌ）、２−（ｎ−オクチルアミノ）エタンチオール（３３．６ｇ、１７７ｍｍｏｌ、２０倍当量）、炭酸カリウム（３９．２ｇ、２８３．６３ｍｍｏｌ、３２倍当量）を、ジメチルホルムアミド（２００ｍｌ）中、１２０℃で、５時間反応させた。反応混合物は室温に冷却後、メタノール（８００ｍｌ）中に排出した。析出物を吸引濾過により回収後、メタノール洗浄、水洗後、乾燥させ、下記式（６）の化合物を含有する近赤外線吸収混合物（１３．２ｇ）を得た。
【００５８】
【化１０】

【００５９】
該混合物はトルエン、クロロホルム等の溶媒に溶け、λmaxは８４３ｎｍ（クロロホルム溶媒）であった。
【００６０】
分光特性；λmax=843 nm、εg=3.14×10⁴ml/g・cm（溶媒；クロロホルム）
元素分析; C₁₅₂H₂₅₈N₂₀S₁₂Cu
分析値(%) Ｃ：60.72 Ｈ：8.92 Ｎ：9.30 Ｓ：12.62 Ｃｕ：2.1
【００６１】
更に、該混合物を、実施例１と同様にして、２５μｍの近赤外線吸収フィルターを作製し、ＴV（可視光透過率）及びＴE（日射透過率）を測定したところ、それぞれ６５％、６２％であった。
【００６２】
実施例３
Ｃ．Ｉ．ピグメントグリーン ７（フタロシアニン グリーン）（７．０ｇ、６．２１ｍｍｏｌ）、２−アミノエタンチオール（９．５７g、１２４ｍｍｏｌ、２０倍当量）、炭酸カリウム（３０．９ｇ、２２３ｍｍｏｌ、３６倍当量）を、ジメチルホルムアミド（２００ｍｌ）中、１３０℃で、３時間反応させた。この反応液を、室温に冷却後、さらにベンゾイルクロリド（１７．４ｇ、１２３．８ｍｍｏｌ）を加えて、１時間反応させた。反応混合物は、メタノール（８００ｍｌ）中に排出し、析出物を吸引濾過により回収後、メタノール洗浄、水洗後、乾燥させ、下記式（７）の化合物を含有する近赤外線吸収混合物（９．８１ｇ）を得た。
【００６３】
該混合物はトルエン、ベンゼン等の芳香族溶媒、クロロホルム等のハロゲン化炭化水素溶媒に溶け、λmaxは８６５ｎｍ（クロロホルム溶媒）であった。
【００６４】
【化１１】

【００６５】
分光特性；λmax=865 nm、εg=2.97×10⁴ml/g・cm（溶媒；クロロホルム）
元素分析; C₁₃₃H₁₁₂N₂₀S₁₂O₁₁Cu
分析値(%) Ｃ：61.22 Ｈ：4.33 Ｎ：10.52 Ｓ：14.77 Ｃｕ：2.4
【００６６】
更に、該混合物を、実施例１と同様にして、２５μｍの近赤外線吸収フィルターを作製し、ＴV（可視光透過率）及びＴE（日射透過率）を測定したところ、それぞれ６８％、６６％であった。
【００６７】
実施例４
Ｃ．Ｉ．ピグメントグリーン ７（フタロシアニン グリーン）（１０．０ｇ、８．８７ｍｍｏｌ）、２−（ｎ−オクチルアミノ）エタンチオール（１６．８ｇ、８８．７ｍｍｏｌ、１０倍当量）、２−アミノエタンチオール（６．８４ｇ、８８．７ｍｍｏｌ、１０倍当量）、炭酸カリウム（３６．８ｇ、２６６．１ｍｍｏｌ、３０倍当量）を、ジメチルホルムアミド（２００ｍｌ）中、１３０℃で、５時間反応させた。反応混合物は室温に冷却後、メタノール（８００ｍｌ）中に排出した。析出物を吸引濾過により回収後、メタノール洗浄、水洗後、乾燥させ、下記式（８）の化合物を含有する近赤外線吸収混合物（１５．４ｇ）を得た。
該混合物は、トルエン、クロロホルム等の溶媒に溶け、λmaxは８６２ｎｍ（クロロホルム溶媒）であった。
【００６８】
【化１２】

【００６９】
分光特性；λmax=862 nm、εg=2.84×10⁴ml/g・cm（溶媒；クロロホルム）
元素分析; C₁₂₀H₁₉₆N₂₀S₁₂Cu
分析値(%) Ｃ：61.02 Ｈ：8.22 Ｎ：11.68 Ｓ：16.22 Ｃｕ：2.7
【００７０】
実施例５
実施例４で得られたＣ．Ｉ．ピグメントグリーン７と２−（ｎ−オクチルアミノ）エタンチオール及び２−アミノエタンチオールを反応させて得られたフタロシアニン化合物（５．０ｇ）をピリジン（６０ｍｌ）溶媒中、ベンゾイルクロリド（７．０ｇ、４９．８ｍｍｏｌ）を添加（室温）後、室温で１時間反応させた。
【００７１】
反応混合物は水（３００ｍｌ）中に排出した。析出物を吸引濾過により回収後、水洗、メタノール洗浄後、乾燥させ、下記式（９）の化合物を含有する近近赤外線吸収混合物（７．４２ｇ）を得た。
該混合物は、トルエン、ベンゼン等の芳香族溶媒に溶け、λmaxは８７４ｎｍ（クロロホルム溶媒）であった。
【００７２】
【化１３】

【００７３】
分光特性；λmax=874 nm、εg=2.98×10⁴ml/g・cm（溶媒；クロロホルム）
元素分析; C₁₇₆H₂₂₈N₂₀S₁₂O₈Cu
分析値(%) Ｃ：67.22 Ｈ：7.03 Ｎ：8.25 Ｓ：12.01 Ｃｕ：2.0
【００７４】
実施例６
Ｃ．Ｉ．ピグメントグリーン ７（フタロシアニン グリーン）（７．０ｇ、６．２１ｍｍｏｌ）、２−アミノエタンチオール（９．５７g、１２４ｍｍｏｌ、２０倍当量）、炭酸カリウム（３０．９ｇ、２２３ｍｍｏｌ、３６倍当量）を、ジメチルホルムアミド（２００ｍｌ）中、１３０℃で、３時間反応させた。この反応液を、室温に冷却後、さらに２ーエチルヘキサノイルクロリド（２０．１ｇ、１２４ｍｍｏｌ）を加えて、１時間反応させた。反応混合物は、メタノール（８００ｍｌ）中に排出し、析出物を吸引濾過により回収後、メタノール洗浄、水洗後、乾燥させ、下記式（１０）の化合物を含有する近赤外線吸収混合物（１２．４ｇ）を得た。
該混合物はトルエン、ベンゼン等の芳香族溶媒、クロロホルム等のハロゲン化炭化水素溶媒に溶け、λmaxは８２６ｎｍ（クロロホルム溶媒）であった。
【００７５】
【化１４】

【００７６】
分光特性；λmax=826 nm、εg=2.89×10⁴ ml/g・cm（溶媒；クロロホルム）
元素分析; C₁₄₄H₂₂₂N₂₀S₁₂O₁₁Cu
分析値(%) Ｃ：61.55 Ｈ：7.76 Ｎ：9.59 Ｓ：13.52 Ｃｕ：2.2
【００７７】
実施例７
Ｃ．Ｉ．ピグメントグリーン ７（フタロシアニン グリーン）（７．０ｇ、６．２１ｍｍｏｌ）、２−アミノチオフェノール（３．１１g、２４．８ｍｍｏｌ、４倍当量）、炭酸カリウム（１７．２ｇ、１２４ｍｍｏｌ、２０倍当量）を、ジメチルホルムアミド（２００ｍｌ）中、１４０℃で、１０時間反応させた。さらにこの反応液に、炭酸カリウム（１７．２ｇ、１２４ｍｍｏｌ、２０倍当量）、２−アミノエタンチオール（７．１８g、９３ｍｍｏｌ、１５倍当量）を加えて、３時間反応させた。反応混合物は室温に冷却後、メタノール（８００ｍｌ）中に排出した。析出物を吸引濾過により回収後、メタノール洗浄、水洗後、乾燥させ、下記式（１１）の化合物を含有する近赤外線吸収混合物（１０．２ｇ）を得た。
該混合物はクロロホルム等のハロゲン化炭化水素溶媒に溶け、λmaxは８８２ｎｍ（クロロホルム溶媒）であった。
【００７８】
【化１５】

【００７９】
分光特性；λmax=882 nm、εg=3.61×10⁴ ml/g・cm（溶媒；クロロホルム）
元素分析; C₆₄H₄₂N₁₆S₈Cu
分析値(%) Ｃ：55.92 Ｈ：3.82 Ｎ：16.51 Ｓ：18.22 Ｃｕ：4.7
【００８０】
【発明の効果】
本発明は、溶解型フタロシアニン系近赤外線吸収化合物を、簡便かつ安価に製造する方法を提供するものであり、実用上極めて価値のある方法である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a simple method for producing a near-infrared absorbing compound having absorption in the near-infrared region and a near-infrared absorbing compound obtained by this method. Moreover, this invention relates to the near-infrared absorption resin composition and heat ray absorption filter containing this near-infrared absorption compound.
[0002]
The near-infrared absorbing compound can be used for a recording layer of an optical recording medium such as an optical disk, or can be used as a near-infrared absorbing ink that can be read by a near-infrared detector by forming an ink. In addition, a near-infrared absorbing filter can also be produced by combining with a binder resin to form a paint and coating on plastic or glass, or kneading with a resin.
[0003]
The near-infrared absorption filter can be used as a window material for buildings, cars, trains, ships, aircrafts, etc., to block heat rays from the outside and suppress temperature rise in the room and in the car. Moreover, by cutting a specific wavelength region, it can be used as a light quality selective use agricultural film for controlling plant growth, cutting infrared rays of a semiconductor light receiving element, and glasses for protecting human eyes from rays containing harmful infrared rays.
[0004]
In addition, since it absorbs laser light in the near infrared region efficiently and generates heat, application to a high-speed printing system is also considered.
[0005]
Among these, near-infrared absorption filters especially for the purpose of blocking heat rays are an area that is attracting attention because they contribute to energy saving.
[0006]
[Prior art]
As a window material for the purpose of heat ray blocking, a heat ray reflection filter in which metal oxides such as indium oxide and tin oxide and metals such as gold and silver are alternately laminated on PET film or glass is known. Along with the disadvantage that the product cost is high due to the manufacturing process, it causes radio interference. Compared to these inorganic heat ray reflective filters, near infrared absorbing filters using near infrared absorbing dyes are easy to manufacture and have no problem of radio interference, so they have a wide range of applications and have a large market need. However, the current situation is that the spread of dyes has not progressed due to problems of cost and durability (particularly stability to light).
[0007]
Conventionally, cyanine dyes are well known as organic dyes that absorb near infrared rays. However, since cyanine dyes have extremely low light fastness, there are many limitations when using them. In addition, the aminium salt type compounds described in JP-A-3-161644, or the metal complex compounds described in JP-B No. 54-25060, JP-A No. 50-51549, etc. are heat resistant and light resistant. It is insufficient. In addition, although anthraquinone compounds described in JP-A-3-115362 and JP-A-62-903 are also heat resistant, they are insufficient in terms of light resistance.
[0008]
As near-infrared absorbing dyes having high durability, JP-B-59-1311, JP-A-60-209583, JP-B-2-5155, JP-A-61-152685, JP-A-61- The phthalocyanines described in 223056, JP-A-3-62878 and the like are complicated and complicated in production process.
[0009]
Japanese Patent Application Laid-Open No. 60-23451 discloses a naphthalocyanine compound, but its production process is long and complicated, and it is an industrially expensive compound, so it is not sufficient for industrial use. there were.
[0010]
[Problems to be solved by the invention]
An object of the present invention is to provide a dissolved phthalocyanine-based near-infrared absorbing compound at low cost and simply. Moreover, the subject of this invention is providing the near-infrared absorption resin composition and heat ray absorption filter which used this near-infrared absorption compound.
[0011]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have reacted phthalocyanine having a leaving group such as a halogen atom, an alkoxy group, a phenoxy group, an alkylthio group, or an arylthio group with an ethanethiol derivative. Thus, the inventors have found that the intended near-infrared absorbing compound can be easily produced, and have completed the present invention.
[0012]
That is, the present invention provides a near-infrared absorbing compound represented by the general formula (1) and a phthalocyanine represented by the general formula (3) and at least one general formula (4) in obtaining the near-infrared absorbing compound. The ethanethiol derivative is made to react in the presence of a base. Further, the present invention relates to a near-infrared absorbing compound obtained by reacting this near-infrared absorbing compound with an alkyl halide, or an alkyl or aryl acid chloride.
[0013]
[Chemical formula 5]

[Where X ¹ Each independently represents a halogen atom, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted arylthio group, and n ² Represents an integer of 0-14. R ¹ , R ² , R ^Three , R ^Four , R ^Five , R ⁶ , R ⁷ , R ⁸ Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group; ¹ , Z ² Each independently represents an oxygen atom, a sulfur atom or an NY group (Y is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted group. M represents an integer of 1 to 8, and l represents an integer of 0 to 7. N ¹ + 2l + 2m represents an integer of 2 to 16. M represents a divalent metal atom, a trivalent or tetravalent substituted metal, or an oxy metal. ]
[0014]
[Chemical 6]

[Where X ² Each independently represents a halogen atom, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted arylthio group, and n ² Represents an integer of 8-16. R ^Five , R ⁶ , R ⁷ , R ⁸ , M each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group; ² Is an oxygen atom, sulfur atom or NY group (Y is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted aryl group) Represents a carbonyl group), and l represents an integer of 0 to 7. N ² + 2l represents an integer of 10 to 16, and M represents a divalent metal atom, a trivalent or tetravalent substituted metal, or an oxy metal. ]
[0015]
[Chemical 7]

[In the formula, R ¹ , R ² , R ^Three , R ^Four Each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group, Z ¹ Represents an oxygen atom, a sulfur atom or an NY group (Y represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group). ]
[0016]
The present invention simply provides a dissolved phthalocyanine-based near-infrared absorbing compound having light resistance.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, preferred embodiments of the near-infrared absorbing compound and the production method thereof in the present invention will be described in detail.
[0018]
The near-infrared absorbing compound in the present invention is represented by the general formula (1), where X ¹ Examples of the halogen atom represented by the formula include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, particularly preferably a chlorine atom and a bromine atom.
[0019]
In the general formula (1), X ¹ The substituted or unsubstituted alkoxy group represented by formula (1) is preferably a linear or branched alkoxy group having 1 to 10 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, iso-propoxy, n- Butoxy group, iso-butoxy group, sec-butoxy group, n-pentyloxy group, iso-pentyloxy group, 1,2-dimethyl-propoxy group, n-hexyloxy group, 1,3-dimethyl-butoxy group, 1 , 2-dimethylbutoxy group, n-heptyloxy group, 1,4-dimethylpentyloxy group, 1-ethyl-3-methylbutoxy group, n-octyloxy group, 2-ethylhexyloxy group;
Benzyloxy group, sec-phenylethoxy group, 2-phenylethoxy group, 2-methylbenzyloxy group, 4-methylbenzyloxy group;
Examples include 3-dimethylaminopropoxy group, 2-dimethylaminoethoxy group, 2-diisopropylaminoethoxy group, 2-diethylaminoethoxy group, 2,2,2-trifluoro-1- (trifluoromethyl) ethoxy group, and the like.
[0020]
In the general formula (1), X ¹ Preferably, the substituted or unsubstituted aryloxy group represented by the formula is a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, more preferably a phenyloxy group, a 2-methylphenyloxy group, or a 3-methylphenyl group. An oxy group, 4-methylphenyloxy group, a naphthyloxy group, etc. are mentioned.
[0021]
In the general formula (1), X ¹ The substituted or unsubstituted alkylthio group represented by is preferably a linear or branched alkylthio group having 1 to 10 carbon atoms, more preferably a methylthio group, an ethylthio group, an n-propylthio group, or an iso-propylthio group. , N-butylthio group, iso-butylthio group, sec-butylthio group, n-pentylthio group, iso-pentylthio group, 1,2-dimethyl-propylthio group, n-hexylthio group, 1,3-dimethyl-butylthio group, 1 , 2-dimethylbutylthio group, n-heptylthio group, 1,4-dimethylpentylthio group, 1-ethyl-3-methylbutylthio group, n-octylthio group, 2-ethylhexylthio group;
Benzylthio group, sec-phenylethylthio group, 2-phenylethylthio group, 2-methylbenzylthio group, 4-methylbenzylthio group, 2-aminoethylthio group, 2-methylaminoethylthio group, 2-ethylamino Ethylthio group, 2-propylaminoethylthio group, 2-butylaminoethylthio group, 2-pentylaminoethylthio group, 2-hexylaminoethylthio group, 2-heptylaminoethylthio group, 2-octylaminoethylthio group Group, 2-benzylaminoethylthio group, 2- (2-phenylethyl) aminoethylthio group;
3-dimethylaminopropylthio group, 2-dimethylaminoethylthio group, 2-diisopropylaminoethylthio group, 2-diethylaminoethylthio group, 2,2,2-trifluoro-1- (trifluoromethyl) ethylthio group, etc. Is mentioned.
[0022]
In the general formula (1), X ¹ The substituted or unsubstituted arylthio group represented by the above is preferably a substituted or unsubstituted arylthio group having 6 to 20 carbon atoms, more preferably a phenylthio group, a 2-methylphenylthio group, or a 3-methylphenylthio group. 4-methylphenylthio group, 2-aminophenylthio group, 3-aminophenylthio group, 4-aminophenylthio group, 2-methylaminophenylthio group, 3-methylaminophenylthio group, 4-methylaminophenyl A thio group, 2-ethylaminophenylthio group, 2-propylaminophenylthio group, naphthylthio group and the like can be mentioned.
[0023]
X ¹ Especially preferably, it is a halogen or a substituent represented by the following general formula (2).
[0024]
[Chemical 8]

[In the formula, R ¹ ~ R ^Four , Z ¹ Represents the same atom or substituent as in formula (1). ]
In general formula (1), n ¹ Represents an integer of 0 to 14, more preferably an integer of 0 to 8.
[0025]
In the formula, R ¹ , R ² , R ^Three , R ^Four , R ^Five , R ⁶ , R ⁷ , R ⁸ Examples of the substituted or unsubstituted alkyl group represented by the formula: methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, n-pentyl group , Iso-pentyl group, 1,2-dimethyl-propyl group, n-hexyl group, 1,3-dimethyl-butyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n -Pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group;
Benzyl group, sec-phenylethyl group, 2-methylbenzyl group, 3-methylbenzyl group, 4-methylbenzyl group, 2-phenylethyl group;
2-hydroxyethyl group, 3-hydroxypropyl group;
3-dimethylaminopropyl group, 2-dimethylaminoethyl group, 2-diisopropylaminoethyl group, 2-diethylaminoethyl group, 2,2,2-trifluoro-1- (trifluoromethyl) ethyl group, 2- (1 -Piperidinyl) ethyl group, 3- (1-piperidinyl) propyl group, 3- (4-morpholinyl) propyl group, 3- (4-morpholinyl) ethyl group, 2- (1-pyrrolidinyl) ethyl group, 2-pyridylmethyl Group, furfuryl group and the like.
[0026]
Examples of the substituted or unsubstituted aryl group include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, and a naphthyl group.
[0027]
Among these, an alkyl group having 5 to 20 carbon atoms is particularly preferable. In order for the product to have high solubility in organic solvents, resins, etc. and no clouding phenomenon occurs in the near infrared absorption filter resin, it is necessary that at least one substituent having 5 or more carbon atoms is substituted. . However, when the number of carbon atoms exceeds 20, the product becomes liquid and may be unsuitable as a filter dye.
[0028]
Furthermore, Z ¹ , Z ² Examples of the atom or substituent represented by the above include an oxygen atom, a sulfur atom or an NY group, and Y represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a 6 to 20 carbon atom. Examples thereof include a substituted or unsubstituted aryl group, a substituted or unsubstituted alkylcarbonyl group having 1 to 20 carbon atoms in total, or a substituted or unsubstituted arylcarbonyl group having 6 to 20 carbon atoms in total.
[0029]
Examples of the substituted or unsubstituted alkyl group represented by Y include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, n-pentyl group, iso- Pentyl group, 1,2-dimethyl-propyl group, n-hexyl group, n-heptyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group N-undecyl group, n-dodecyl group, n-tridecyl group, n-pentadecyl group, n-octadecyl group; benzyl group, sec-phenylethyl group, 3-methylbenzyl group, 4-ethylbenzyl group, 2-phenyl Ethyl group;
3-dimethylaminopropyl group, 2-diisopropylaminoethyl group, 2-diethylaminoethyl group, 2,2,2-trifluoro-1- (trifluoromethyl) ethyl group, 2- (1-piperidinyl) ethyl group, 3 -(4-morpholinyl) propyl group, 2- (1-pyrrolidinyl) ethyl group, 2-pyridylmethyl group, furfuryl group and the like are mentioned, more preferably iso-butyl group, iso-pentyl group, n-octyl group. , 2-ethylhexyl group, 2-phenylethyl group, 2-diisopropylaminoethyl group and the like.
[0030]
Examples of the substituted or unsubstituted aryl group represented by Y include phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-methoxyphenyl group, 1-naphthyl group and the like. Can be mentioned.
[0031]
m represents an integer of 1 to 8, more preferably an integer of 2 to 6.
[0032]
l represents an integer of 0 to 7, more preferably an integer of 0 to 4.
[0033]
N ¹ + 2l + 2m represents an integer of 2 to 16, more preferably an integer of 8 to 16.
[0034]
Further, M may be a divalent metal atom, a trivalent or tetravalent substituted metal, or an oxy metal, preferably Cu, AlCl, TiO or VO, more preferably Cu.
[0035]
In the phthalocyanine represented by the general formula (3) used in the present invention, X ² Examples of the halogen atom represented by the formula include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom and a bromine atom. As a method for obtaining the phthalocyanine, X ² Are chlorine atoms, bromine atoms, etc., which are industrially available and X ² Those having iodine atoms can be obtained by treating these with potassium iodide, sodium iodide or the like according to a conventional method and replacing them with iodine atoms. Fluorinated phthalocyanine can be produced by the method described in Dyes and Pigment page 91 (1992).
[0036]
In addition, X ² Can be prepared by reacting the above-mentioned halogenated phthalocyanine with the corresponding alcohol or thiol.
[0037]
R ^Five , R ⁶ , R ⁷ , R ⁸ , Z ² , M are the same as those in the general formula (1).
[0038]
In the phthalocyanine represented by the general formula (3), particularly preferable compounds are C.I. I. Pigment green 7 (phthalocyanine green), C.I. I. Pigment green 36, or C.I. I. Pigment Green 38, a compound that is industrially easily available as a halogenated phthalocyanine.
[0039]
In the ethanethiol represented by the general formula (4) used in the present invention, R ¹ , R ² , R ^Three , R ^Four , Z ¹ Is the same as in general formula (1).
[0040]
The reaction between the phthalocyanine represented by the general formula (3) and the ethanethiol derivative represented by the general formula (4) is performed under the usual nucleophilic substitution reaction conditions, that is, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate. In the presence of an inorganic base such as sodium hydride or an organic base such as pyridine, triethylamine, or quinoline.
[0041]
This reaction may be carried out in the presence of a solvent. Examples of the solvent include dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N, N′-dimethylimidazolidinone (DMI), sulfolane, pyridine and the like. Polar solvents, ketone solvents such as acetone and methyl ethyl ketone, and aromatic hydrocarbon solvents such as toluene, xylene, monochlorobenzene and dichlorobenzene.
[0042]
In the method for producing a near-infrared absorbing compound of the present invention, a phthalocyanine represented by the general formula (3) and a base (4 to 100 times equivalent to phthalocyanine) are usually used in a solvent (1 to 1000 times by weight with respect to phthalocyanine). The ethanethiol derivative represented by the general formula (4) (4 to 40 times equivalent to phthalocyanine) is added with stirring and the mixture is stirred and reacted at 50 to 220 ° C. The ethanethiol derivative may be added before the temperature rise, during the temperature rise or after the temperature rise. Moreover, you may add at once and may add by division | segmentation. Alternatively, the ethanethiol derivative itself may be used as a solvent, and after adding a base, phthalocyanine may be added.
[0043]
In the reaction, a copper catalyst such as metallic copper, copper chloride, copper bromide, copper iodide, copper oxide can be added as a catalyst. The reaction may be performed under normal pressure or under pressure.
[0044]
The progress of the reaction can be determined, for example, by measuring λmax of the reaction solution.
[0045]
After completion of the reaction, the target compound is precipitated by discharging the reaction mixture into cooled water or an alcohol solution such as methanol, ethanol, propanol, butanol, or pentanol. The precipitated target product is separated by suction filtration, and further washed with water and alcohol to remove salt, residual base, unreacted ethanethiol derivative, etc., and dried to obtain the near-infrared absorbing compound of the present invention. Release. The obtained near-infrared absorbing compound of the present invention dissolves well in organic solvents such as toluene, xylene, and ethyl acetate, and can be purified by column chromatography as necessary.
[0046]
The near-infrared absorbing compound produced by the method of the present invention further includes methyl iodide, bromoethyl, 1-bromopropane, 2-bromopropane, 1-chlorobutane, 2-bromobutane, 1-bromo-2-methylbutane, 1-bromo. Reacting with an alkyl halide such as -3-methylbutane, 1-chloropentane, 1-bromohexane, 1-bromo-2-ethylhexane, 1-bromooctane, benzyl chloride and the like under the same conditions as above.
Or alkyl acid chlorides such as acetic anhydride, trifluoroacetyl chloride, acetyl chloride, 1-butyl chloride, isobutyl chloride, 2-ethylhexanoyl chloride, or aryl acids such as benzoyl chloride, 4-methoxybenzoyl chloride, naphthyl chloride, etc. By reacting chloride in the presence of a base, a near-infrared absorbing compound in which λmax is further lengthened or shortened can be obtained.
[0047]
In this case, the near-infrared absorbing compound and the base isolated by the above method (1 to 100 times by weight with respect to the near-infrared absorbing compound) are dissolved in a solvent (1 to 1000 times by weight with respect to the near-infrared absorbing compound). Alternatively, the mixture is suspended and stirred, and an alkyl halide (1 to 100 times by weight with respect to the near-infrared absorbing compound) is added, and the reaction is carried out at 50 to 220 ° C.
[0048]
Moreover, alkyl halide or acid halide can be directly added to the reaction mixture obtained by reacting phthalocyanine and ethanethiol derivative without isolating the near infrared absorbing compound, and the reaction can be continued.
[0049]
After the reaction, it can be treated in the same manner as in the above method.
[0050]
The method for producing a near-infrared absorbing compound of the present invention is a method by which a starting material is inexpensive, has good light resistance, and can be easily obtained as a compound that is soluble in resins, solvents, and the like.
[0051]
Furthermore, since the product obtained by the method of the present invention is not a single compound but is obtained as a mixture of several kinds, the absorption wavelength becomes broad and the near infrared region is absorbed broadly. Is an excellent compound for absorbing heat rays.
[0052]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not restrict | limited at all by this.
[0053]
Example 1
C. I. Pigment Green 7 (phthalocyanine green) (7.0 g, 6.21 mmol), 2-aminoethanethiol (9.57 g, 124 mmol, 20 times equivalent), potassium carbonate (30.9 g, 223 mmol, 36 times equivalent), and dimethyl The reaction was carried out in imidazolidine (200 ml) at 150 ° C. for 3 hours. To this reaction solution, n-octyl bromide (7.43 g, 38.47 mmol) was further added and allowed to react for 1 hour. The reaction mixture was cooled to room temperature and then discharged into methanol (800 ml). The precipitate was collected by suction filtration, washed with methanol, washed with water, and dried to obtain a near-infrared absorbing mixture (8.13 g) containing a compound of the following formula (5). The mixture was dissolved in an aromatic solvent such as toluene and benzene, and a halogenated hydrocarbon solvent such as chloroform, and λmax was 846 nm (chloroform solvent).
[0054]
[Chemical 9]

[0055]
Spectral characteristics: λmax = 846 nm, εg = 3.22 × 10 ^Four ml / g · cm (solvent: chloroform)
Elemental analysis; C ₁₂₈ H ₂₁₂ N ₂₀ S ₁₂ Cu
Analytical value (%) C: 61.82 H: 8.63 N: 11.24 S: 15.52 Cu: 2.6
[0056]
Further, the mixture was mixed with unitika polyethylene terephthalate pellets 1203 at a weight ratio of 0.02: 1, melted at 260 to 280 ° C., and a film having a thickness of 100 μm was produced with an extruder. A near-infrared absorption filter having a thickness of 25 μm was produced by axial stretching. The filter absorbed light of 700-1100 nm well. According to JIS-R-3106, TV (visible light transmittance) and TE (sunlight transmittance) were measured with a spectrophotometer UV-3100 manufactured by Shimadzu Corporation, and were 68% and 65%, respectively.
[0057]
Example 2
C. I. Pigment Green 7 (phthalocyanine green) (10.0 g, 8.87 mmol), 2- (n-octylamino) ethanethiol (33.6 g, 177 mmol, 20 times equivalent), potassium carbonate (39.2 g, 283.63 mmol, 32 equivalents) was reacted in dimethylformamide (200 ml) at 120 ° C. for 5 hours. The reaction mixture was cooled to room temperature and then discharged into methanol (800 ml). The precipitate was collected by suction filtration, washed with methanol, washed with water, and dried to obtain a near-infrared absorbing mixture (13.2 g) containing a compound of the following formula (6).
[0058]
[Chemical Formula 10]

[0059]
The mixture was dissolved in a solvent such as toluene or chloroform, and λmax was 843 nm (chloroform solvent).
[0060]
Spectral characteristics: λmax = 843 nm, εg = 3.14 × 10 ^Four ml / g · cm (solvent: chloroform)
Elemental analysis; C ₁₅₂ H ₂₅₈ N ₂₀ S ₁₂ Cu
Analytical value (%) C: 60.72 H: 8.92 N: 9.30 S: 12.62 Cu: 2.1
[0061]
Further, a 25-μm near-infrared absorbing filter was produced from the mixture in the same manner as in Example 1, and the TV (visible light transmittance) and TE (solar radiation transmittance) were measured. The results were 65% and 62%, respectively. there were.
[0062]
Example 3
C. I. Pigment Green 7 (phthalocyanine green) (7.0 g, 6.21 mmol), 2-aminoethanethiol (9.57 g, 124 mmol, 20 times equivalent), potassium carbonate (30.9 g, 223 mmol, 36 times equivalent), and dimethyl The reaction was carried out in formamide (200 ml) at 130 ° C. for 3 hours. After the reaction solution was cooled to room temperature, benzoyl chloride (17.4 g, 123.8 mmol) was further added and reacted for 1 hour. The reaction mixture was discharged into methanol (800 ml), and the precipitate was collected by suction filtration, washed with methanol, washed with water and dried, and a near-infrared absorbing mixture containing a compound of the following formula (7) (9.81 g) Got.
[0063]
The mixture was dissolved in an aromatic solvent such as toluene and benzene, and a halogenated hydrocarbon solvent such as chloroform, and λmax was 865 nm (chloroform solvent).
[0064]
Embedded image

[0065]
Spectral characteristics: λmax = 865 nm, εg = 2.97 × 10 ^Four ml / g · cm (solvent: chloroform)
Elemental analysis; C ₁₃₃ H ₁₁₂ N ₂₀ S ₁₂ O ₁₁ Cu
Analytical value (%) C: 61.22 H: 4.33 N: 10.52 S: 14.77 Cu: 2.4
[0066]
Further, a 25-μm near-infrared absorption filter was produced from the mixture in the same manner as in Example 1, and when TV (visible light transmittance) and TE (sunlight transmittance) were measured, they were 68% and 66%, respectively. there were.
[0067]
Example 4
C. I. Pigment Green 7 (phthalocyanine green) (10.0 g, 8.87 mmol), 2- (n-octylamino) ethanethiol (16.8 g, 88.7 mmol, 10-fold equivalent), 2-aminoethanethiol (6.84 g) , 88.7 mmol, 10 times equivalent), potassium carbonate (36.8 g, 266.1 mmol, 30 times equivalent) were reacted in dimethylformamide (200 ml) at 130 ° C. for 5 hours. The reaction mixture was cooled to room temperature and then discharged into methanol (800 ml). The precipitate was collected by suction filtration, washed with methanol, washed with water, and dried to obtain a near-infrared absorbing mixture (15.4 g) containing a compound of the following formula (8).
The mixture was dissolved in a solvent such as toluene and chloroform, and λmax was 862 nm (chloroform solvent).
[0068]
Embedded image

[0069]
Spectral characteristics: λmax = 862 nm, εg = 2.84 × 10 ^Four ml / g · cm (solvent: chloroform)
Elemental analysis; C ₁₂₀ H ₁₉₆ N ₂₀ S ₁₂ Cu
Analytical value (%) C: 61.02 H: 8.22 N: 11.68 S: 16.22 Cu: 2.7
[0070]
Example 5
C.I obtained in Example 4 I. A phthalocyanine compound (5.0 g) obtained by reacting CI Pigment Green 7 with 2- (n-octylamino) ethanethiol and 2-aminoethanethiol was dissolved in pyridine (60 ml) in benzoyl chloride (7.0 g, 49 .8 mmol) was added (room temperature), followed by reaction at room temperature for 1 hour.
[0071]
The reaction mixture was drained into water (300 ml). The precipitate was collected by suction filtration, washed with water, washed with methanol, and dried to obtain a near-infrared absorbing mixture (7.42 g) containing a compound of the following formula (9).
The mixture was dissolved in an aromatic solvent such as toluene and benzene, and λmax was 874 nm (chloroform solvent).
[0072]
Embedded image

[0073]
Spectral characteristics: λmax = 874 nm, εg = 2.98 × 10 ^Four ml / g · cm (solvent: chloroform)
Elemental analysis; C ₁₇₆ H ₂₂₈ N ₂₀ S ₁₂ O ₈ Cu
Analytical value (%) C: 67.22 H: 7.03 N: 8.25 S: 12.01 Cu: 2.0
[0074]
Example 6
C. I. Pigment Green 7 (phthalocyanine green) (7.0 g, 6.21 mmol), 2-aminoethanethiol (9.57 g, 124 mmol, 20 times equivalent), potassium carbonate (30.9 g, 223 mmol, 36 times equivalent) and dimethyl The reaction was carried out in formamide (200 ml) at 130 ° C. for 3 hours. After the reaction solution was cooled to room temperature, 2-ethylhexanoyl chloride (20.1 g, 124 mmol) was further added and reacted for 1 hour. The reaction mixture was discharged into methanol (800 ml), and the precipitate was collected by suction filtration, washed with methanol, washed with water and dried, and a near infrared absorbing mixture (12.4 g) containing a compound of the following formula (10) Got.
The mixture was dissolved in an aromatic solvent such as toluene and benzene, and a halogenated hydrocarbon solvent such as chloroform, and λmax was 826 nm (chloroform solvent).
[0075]
Embedded image

[0076]
Spectral characteristics: λmax = 826 nm, εg = 2.89 × 10 ^Four ml / g · cm (solvent: chloroform)
Elemental analysis; C ₁₄₄ H ₂₂₂ N ₂₀ S ₁₂ O ₁₁ Cu
Analytical value (%) C: 61.55 H: 7.76 N: 9.59 S: 13.52 Cu: 2.2
[0077]
Example 7
C. I. Pigment Green 7 (phthalocyanine green) (7.0 g, 6.21 mmol), 2-aminothiophenol (3.11 g, 24.8 mmol, 4 times equivalent), potassium carbonate (17.2 g, 124 mmol, 20 times equivalent). , In dimethylformamide (200 ml) at 140 ° C. for 10 hours. Furthermore, potassium carbonate (17.2 g, 124 mmol, 20-fold equivalent) and 2-aminoethanethiol (7.18 g, 93 mmol, 15-fold equivalent) were added to the reaction solution and reacted for 3 hours. The reaction mixture was cooled to room temperature and then discharged into methanol (800 ml). The precipitate was collected by suction filtration, washed with methanol, washed with water, and dried to obtain a near-infrared absorbing mixture (10.2 g) containing a compound of the following formula (11).
The mixture was dissolved in a halogenated hydrocarbon solvent such as chloroform, and λmax was 882 nm (chloroform solvent).
[0078]
Embedded image

[0079]
Spectral characteristics: λmax = 882 nm, εg = 3.61 × 10 ^Four ml / g · cm (solvent: chloroform)
Elemental analysis; C ₆₄ H ₄₂ N ₁₆ S ₈ Cu
Analytical value (%) C: 55.92 H: 3.82 N: 16.51 S: 18.22 Cu: 4.7
[0080]
【The invention's effect】
The present invention provides a method for producing a dissolved phthalocyanine-based near-infrared absorbing compound in a simple and inexpensive manner, and is a practically extremely valuable method.

Claims (12)

A near-infrared absorbing compound represented by the general formula (1).

[In the formula, each X ¹ independently represents a halogen atom, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted arylthio group. , N ¹ represents an integer of 0-14. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group; Z ¹ and Z ² are each independently an oxygen atom, sulfur atom or NY group (Y is a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted group. Represents an arylcarbonyl group), m represents an integer of 1 to 8, and l represents an integer of 0 to 7. N ¹ + 2l + 2m represents an integer of 2 to 16. M represents a divalent metal atom, a trivalent or tetravalent substituted metal, or an oxy metal. ]   The near-infrared absorbing compound according to claim 1, wherein l is 0 in the general formula (1). The near-infrared absorbing compound according to claim 1 or 2, wherein in the general formula (1), X ¹ is halogen or represented by the general formula (2).

Wherein, R ¹ to R ^4, Z ¹ represents the same atom or substituent in formula (1). ] In the general formula (1), Z ¹ represents an NY group (Y represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylcarbonyl group, or a substituted or unsubstituted arylcarbonyl group. The near-infrared absorptive compound of any one of Claims 1-3 represented by this.   The near-infrared absorbing compound according to claim 4, wherein Y is a substituted or unsubstituted alkylcarbonyl group or a substituted or unsubstituted arylcarbonyl group.   In the general formula (1), M is Cu, AlCl, TiO, or VO. The near-infrared absorbing compound according to any one of claims 1 to 5. In obtaining the near-infrared absorbing compound according to any one of claims 1 to 6, a phthalocyanine represented by the general formula (3) and an ethanethiol derivative represented by at least one general formula (4) In the presence of phthalocyanine, the reaction is carried out at least 1 equivalent.

[Wherein each X ² independently represents a halogen atom, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted arylthio group. , N ² represents an integer of 8-16. R ⁵ , R ⁶ , R ⁷ , R ⁸ , Z ² , and M represent the same substituent or the same metal as in general formula (1), l represents the same integer as in general formula (1), and n ² + 2l represents an integer of 8-16. ]

[Wherein R ¹ , R ² , R ³ , R ⁴ and Z ¹ represent the same substituents as those in the general formula (1). ]   The phthalocyanine represented by the general formula (3) is C.I. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 37, C.I. I. The method for producing a near-infrared absorbing compound according to claim 7, which is CI Pigment Green 38. At least one of the ethanethiol derivatives is represented by the general formula (4), wherein R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or carbon It is a substituted or unsubstituted aryl group of several 6-20, The manufacturing method of the near-infrared absorption compound in any one of Claim 7 and 8.   The near-infrared absorption compound manufactured with the manufacturing method of any one of Claims 7-9.   The near-infrared absorption resin composition containing the near-infrared absorption compound of any one of Claims 1-6 and 10.   The heat ray absorption filter containing the near-infrared absorption compound of any one of Claims 1-6 and 10.