JP4073202B2 - Colorant for laser light transmitting colored resin composition and related technology - Google Patents

Description

・・・（１）
［式（１）中、
Ｒ^２、Ｒ^３、及びＲ^５は、互いに独立的に、水素、又は
【化２１】

・・・・（１−ａ）
を示し、
Ｒ^１及びＲ^４は、互いに独立的に、水素、アルキル基、アルケニル基、アルコキシ基、アミノ基、水酸基、ハロゲン、又はスルホン酸基を示し、
Ｘ^１は、Ｏ又はＮＨを示し、
Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、及びＲ^１１は、互いに独立的に、水素、アルキル基、アルケニル基、アルコキシ基、アミノ基、水酸基、又はハロゲンを示し、
［ｌ］^ｂ＋は、脂肪族ジアミン誘導体、ロジンアミン誘導体、グアニジン誘導体、芳香族アミン誘導体、及び芳香族ジアミン誘導体からなる群から選ばれた少なくとも１つのアミンに起因するカチオン又は４級有機アンモニウムイオンを示し、
ｎ^１は０乃至４の整数を示し、
ｎ^３は０乃至４の整数を示し、
ｍ^１は１乃至６の整数を示し、
ａは１乃至４の整数を示し、
ｂは１又は２を示し、
Ｋ^２は１乃至６の整数を示す。］
【０００９】
式（２）で表されるアントラキノン系造塩染料は次の通りである。
【化２２】

・・・（２）
［式（２）中、
Ｒ^４７、Ｒ^４８、Ｒ^４９、Ｒ^５０、Ｒ^５１、及びＲ^５２は、互いに独立的に、水素、アルキル基、アリール基、アルケニル基、アルコキシ基、アミノ基、Ｎ−アルキルアミド基、Ｎ−アリールアミド基、水酸基、ハロゲン、アシル基、アシルオキシ基、アシルアミド基、アシル−Ｎ−アルキルアミド基、カルボキシル基、アルコキシルカルボニル基、又はスルホン酸基を示し、Ｒ^４７乃至Ｒ^５２の少なくとも１つはスルホン酸基を示すものであり、
結合子Ｊは、下記式（２−ａ）又は（２−ｂ）を示し、
【化２３】

・・・（２−ａ）
又は
【化２４】

・・・（２−ｂ）
（Ｆ）^ｈ＋は、脂肪族ジアミン誘導体、ロジンアミン誘導体、グアニジン誘導体、芳香族アミン誘導体、及び芳香族ジアミン誘導体からなる群から選ばれた少なくとも１つのアミンに起因するカチオン又は４級有機アンモニウムイオンを示し、
ｍ^４は１乃至６の整数を示し、
ｈは１又は２を示し、
Ｋ^３は１乃至６の整数を示し、
前記Ｒ^５３及びＲ^５４は、互いに独立的に、水素又はアルキル基を示す。］
【００１０】
式（３）で表されるアントラキノン系造塩染料は次の通りである。
【化２５】

・・・（３）
［式（３）中、
Ｒ^５８、Ｒ^５９、及びＲ^６０は、互いに独立的に、水素、アルキル基、アルケニル基、アルコキシ基、アミノ基、水酸基、ハロゲン、シクロヘキシルアミド基、又はスルホン酸基を示し、
Ｘ^２は、Ｏ又はＮＨを示し、
Ｒ^５５、Ｒ^５６、及びＲ^５７は、互いに独立的に、水素、アルキル基、アリール基、アルケニル基、アルコキシ基、アミノ基、Ｎ−アルキルアミド基、Ｎ−アリールアミド基、水酸基、ハロゲン、シアノ、アシル基、アシルオキシ基、アシルアミド基、アシル−Ｎ−アルキルアミド基、カルボキシル基、アルコキシルカルボニル基、又はスルホン酸基を示し、
［ｔ］^Ｚ＋は、脂肪族ジアミン誘導体、ロジンアミン誘導体、グアニジン誘導体、芳香族アミン誘導体、及び芳香族ジアミン誘導体からなる群から選ばれた少なくとも１つのアミンに起因するカチオン又は４級有機アンモニウムイオンを示し、
ｍ^２は１乃至６の整数を示し、
ｙは１乃至４の整数を示し、
Ｚは１又は２を示し、
Ｋ^４は１乃至６の整数を示す。］
【００１１】
本発明におけるアントラキノン系造塩染料は、例えばアントラキノン系酸性染料と有機アミンの反応により得ることが可能である。具体的には、アントラキノン系酸性染料中のスルホン酸基に起因するアニオンと有機アミンに起因するアンモニウムイオンとのイオン反応［一部混合］により得ることが可能である。
【００１２】
また、本発明のレーザー光透過性着色樹脂組成物用着色剤として好ましいのは、上記式（１）における［ｌ］^ｂ＋、上記式（２）における（Ｆ）^ｈ＋、及び上記式（３）における［ｔ］^Ｚ＋が、下記式（４−ａ）又は（４−ｂ）で表されるカチオンであるものである。
【化２６】

・・・（４−ａ）
［式（４−ａ）中、
Ｒ^４０及びＲ^４１は、互いに独立的に、Ｎ^＋Ｈ_３又はＮＨ_２を示し、Ｒ^４０及びＲ^４１は少なくとも１つがＮ^＋Ｈ_３を示すものであり、
ｎ^２は、１乃至１２の整数を示す。］
【化２７】

・・・（４−ｂ）
［式（４−ｂ）中、
Ｒ^４２、Ｒ^４３、及びＲ^４４は、互いに独立的に、炭素数１乃至１８のアルキル基、又はアリール基を示し、
Ｒ^４５は、置換若しくは非置換のアリール基又はベンジル基を示す。］
【００１３】
スルホン酸基を有するフェニル基をアントラキノン骨格のベンゼン環に有する上記式（１）乃至（３）で表されるアントラキノン系造塩染料は、ポリアミド樹脂等の熱可塑性樹脂に配合した場合に、樹脂との相溶性が良好で、その樹脂組成物は、良好な成形性、色相、耐ブルーミング性、及び耐ブリード性を示し、２００℃以上の樹脂成形温度領域における耐熱性、及び半導体レーザーによる８００ｎｍ付近からＹＡＧレーザーによる１１００ｎｍ付近にかけての波長のレーザー光の透過性に優れる。
【００１４】
【発明の実施の形態】
本発明におけるアントラキノン系造塩染料は、例えば下記式（１０）で表されるアントラキノン系酸性染料と有機アミン（脂肪族ジアミン誘導体、脂環族アミン誘導体、グアニジン誘導体、芳香族アミン、又は芳香族ジアミン誘導体）の反応（イオン反応）により得ることが可能である。この造塩化反応には、公知のイオン反応を用いることができる。
【００１５】
【化２８】

・・・（１０）
【００１６】
［式（１０）中、
Ｒ^２、Ｒ^３、及びＲ^５は、互いに独立的に（すなわち同じであっても異なっていてもよい）、水素、又は
【化２９】

・・・（１０−ａ）
を示し、
Ｒ^１及びＲ^４は、互いに独立的に、水素、アルキル基、アルケニル基、アルコキシ基、アミノ基、水酸基、ハロゲン、又はスルホン酸基を示し、
Ｘ^１は、Ｏ又はＮＨを示し、
Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、及びＲ^１１は、互いに独立的に、水素、アルキル基、アルケニル基、アルコキシ基、アミノ基、水酸基、又はハロゲンを示し、
ｎ^１は０乃至４の整数を示し、
ｎ^３は０乃至４の整数を示す。］
【００１７】
上記式（１）及び（１０）におけるＲ^１、Ｒ^４、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９、Ｒ^１０、又はＲ^１１が示すアルキル基、アルケニル基、アルコキシ基、及びハロゲンとしては、次のような具体例を挙げることができる。すなわち、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、ウンデシル、ドデシル等の炭素数１乃至２２の分岐していてもよいアルキル基； ビニル、アリル、プロペニル、ブテニル、イソブテニル等の炭素数２乃至８のアルケニル基；メトキシ、エトキシ、プロポキシ、ブトキシ等の炭素数１乃至１８の分岐していてもよいアルキルを有するアルコキシ基；Ｆ、Ｃｌ、Ｂｒ等のハロゲンである。
【００１８】
上記の式（１０）で示されるアントラキノン系酸性染料の具体例として下記の例を挙げることができる。但し、勿論本発明はこれらに限定されるものではない。
【００１９】
【化３０】

化合物例１０−１
【００２０】
【化３１】

化合物例１０−２
【００２１】
【化３２】

化合物例１０−３
【００２２】
【化３３】

化合物例１０−４
【００２３】
【化３４】

化合物例１０−５
【００２４】
【化３５】

化合物例１０−６
【００２５】
【化３６】

化合物例１０−７
【００２６】
【化３７】

化合物例１０−８
【００２７】
【化３８】

化合物例１０−９
【００２８】
【化３９】

化合物例１０−１０
【００２９】
【化４０】

化合物例１０−１１
【００３０】
【化４１】

化合物例１０−１２
【００３１】
【化４２】

化合物例１０−１3
【００３２】
【化４３】

化合物例１０−１4
【００３３】
本発明におけるアントラキノン系造塩染料を得る造塩化反応に用いることができる有機アミンとしては、脂肪族ジアミン誘導体、脂環族アミン誘導体、グアニジン誘導体、芳香族アミン誘導体、及び芳香族ジアミン誘導体を挙げることができる。より具体的には、エチレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン等の脂肪族ジアミン誘導体；ロジンアミン等の脂環族アミン（シクロヘキシルアミンを除く）；１，３−ジフェニルグアニジン、１−ｏ−トリルグアニジン、ジ−ｏ−トリルグアニジン、グアニジン等のグアニジン誘導体；アニリン、ベンジルアミン、ナフチルアミン、フェニルアミン、フェニレンジアミン、メチルフェニレンジアミン、キシレンジアミン等の芳香族アミン誘導体又は芳香族ジアミン誘導体が挙げられる。
本発明のアントラキノン系造塩染料における第４級有機アンモニウムイオンとしては、N-テトラメチルアンモニウムイオン、N-テトラブチルアンモニウムイオン、N-テトラオクチルアンモニウムイオン、N-トリブチル-N-オクチルアンモニウムイオン、N-トリメチル-N-ドデシルアンモニウムイオン、N-トリブチル-N-ドデシルアンモニウムイオン、N-トリブチル-N-フェニルアンモニウムイオン、N-トリメチル-N-ベンジルアンモニウムイオン、N-トリブチル-N-ベンジルアンモニウムイオン、N-トリオクチル-N-ベンジルアンモニウムイオン、N-トリフェニル-N-ベンジルアンモニウムイオン等が挙げられる。
【００３４】
本発明における上記式（１）乃至式（３）で表されるアントラキノン系造塩染料は、アントラキノン系酸性染料中のスルホン酸基に起因するアニオンの数と脂肪族ジアミン中のアミノ基に起因するアンモニウムイオンの数との関係によって、種々の結合構造をとり得る。
【００３５】
上記式（１）乃至式（３）で表される本発明におけるアントラキノン系造塩染料は、半導体レーザー及びＹＡＧレーザーのレーザー光の波長におけるレーザー光の透過性に優れ、波長９５０ｎｍのレーザー光と波長１０５０ｎｍのレーザー光は一定の高い透過率が維持される。上記式（１）乃至式（３）で表されるアントラキノン系造塩染料における波長９５０ｎｍのレーザー光の透過率であるＴ_{９５０ｎｍ}と波長１０５０ｎｍのレーザー光の透過率であるＴ_{１０５０ｎｍ}との比であるＴ_{９５０ｎｍ}／Ｔ_{１０５０ｎｍ}は、０．８乃至１．２、好ましくは０．９乃至１．１である。
【００３６】
上記式（１）乃至式（３）で表されるアントラキノン系造塩染料は、熱分析［ＴＧ／ＤＴＡ測定器（セイコーインスツルメンツ社製 商品名：ＳＩＩ ＥＸＳＴＡＲ６０００）を用い、Ａｉｒ（空気）で２００ｍｌ／分の雰囲気下、３０乃至５５０℃は昇温速度１０℃／分、５５０℃到達後２８分間は５５０℃の定温状態で行う熱分析。］において、２００℃と３００℃の間に発熱ピーク及び吸熱ピ−クの何れも示さないものであることが好ましい。２００℃と３００℃の間は、成形時に樹脂を溶融させる温度であるから、この間で染料が分解したり、不純物が生成することにより、成形樹脂の着色性、透明性、機械的物性等の低下が生じる。また、上記式（１）乃至式（３）で表されるアントラキノン系造塩染料は、前記熱分析において３３０℃以上の分解温度を示すものであることが好ましい。
【００３７】
上記式（１）乃至式（３）で表されるアントラキノン系造塩染料は、青色、紫色、緑色等の色相を示すものを有する。本発明の着色剤においては、各種色相を有する上記式（１）乃至式（３）で表されるアントラキノン系造塩染料の何れかを単独で、又はこれらの２種以上を混合して用いることができ、更に、上記式（１）乃至式（３）で表されるアントラキノン系造塩染料が有する可視光線吸収範囲以外にのみ又はその範囲以外にも吸収範囲を有し、８００ｎｍ乃至１２００ｎｍに透過性を有する染料を１種又は２種以上混合して用いることができる。
【００３８】
単一で黒色を呈する黒色染料は７００ｎｍと９００ｎｍの間にも吸収を有するものとなり易い。現在存在するそのような黒色染料は、半導体レーザーのレーザー光の波長付近に吸収があるため、レーザー光透過用の着色剤として使用し難い。そのため、単一で黒色を示さない染料を組み合せて黒色を示すよう調色した着色剤が重要である。例えば、上記式（１）乃至式（３）で表されるアントラキノン系造塩染料と下記式（５）乃至式（７）で表される染料等の赤色染料や黄色染料等を組み合わせることにより、黒色を呈する本発明の着色剤を製造することができる。各染料の使用割合は、用いる染料の色相、使用樹脂、使用濃度（又は樹脂の厚み）等に応じ適宜調整することができる。
【００３９】
上記式（１）乃至（３）で表されるアントラキノン系造塩染料は、水溶性が低く、油溶性染料に近い挙動（物性）を示す。このアントラキノン系造塩染料は、難水溶性染料であることがより好ましい。水溶性が低い染料、より好ましくは難水溶性の染料は、含有し得る水分量が少ないので、熱可塑性樹脂等の合成樹脂に配合して成形する際に発泡等の不都合な現象が起こり難く、表面外観が良好で透明性が高い成形物が得られ易い。
【００４０】
本発明の着色剤の無機塩は、２重量％以下であることが好ましい。より好ましくは、１重量％、更に好ましくは０．５重量％以下である。染料中に含まれ得る無機塩は、樹脂組成物中に混入すると、結晶の成長を阻害し、多い場合は特に樹脂成形物にクラックや機械的物性の低下を引き起こし易くなる。このような無機塩としては、アルカリ金属（Ｌｉ、Ｎａ、Ｋ等）やアルカリ土類金属（Ｂａ、Ｃａ、Ｓｒ等）の塩化物、硫酸塩、水酸化物等が挙げられる。
【００４１】
本発明の着色剤に用いる染料については、染料の原料中の金属を除く、生成した塩や反応に用いた触媒等を十分に取り除く必要がある。また水系反応においては、工業用水や水道水等の金属を除去したイオン交換水等を用いて反応させることにより、ＣａやＦｅ等の混入を防ぐことが好ましい。
【００４２】
本発明における上記式（１）で表されるアントラキノン系造塩染料の具体例としては、表１及び表２に示されるアントラキノン系酸性染料と有機アミンの反応により得られるアントラキノン系造塩染料を挙げることができる。但し、勿論本発明はこれらに限定されるものではない。
【００４３】
【表１】

【００４４】
【表２】

【００４５】
上記式（２）で表されるアントラキノン系造塩染料の具体例としては、表３に示されるものを挙げることができる。但し、勿論本発明はこれらに限定されるものではない。
【００４６】
【表３】

【００４７】
上記式（３）で表されるアントラキノン系造塩染料の具体例としては、表４に示すものを挙げることができる。但し、勿論本発明はこれらに限定されるものではない。
【００４８】
【表４】

【００４９】
上記式（１）乃至式（３）で表されるアントラキノン系造塩染料と混合して本発明の着色剤を構成し得る染料として、アントラキノン系造塩染料が有する可視光線吸収範囲以外にのみ又はその範囲以外にも吸収範囲を有し、８００ｎｍ乃至１２００ｎｍに透過性を有する染料を順次説明する。
【００５０】
本発明のレーザー光透過性着色樹脂組成物用着色剤は、下記式（５）で表されるペリノン系染顔料を含有することが好ましい。式（５）のペリノン骨格は、堅牢な骨格であるため熱安定性の良好な堅牢な染料を構成し易い。また、熱可塑性樹脂に配合した場合の樹脂成形性及び色相が良好である。特に、赤色染料として堅牢性が高い染料が少ないため有用である。
【００５１】
【化４４】

・・・（５）
【００５２】
［式（５）中、
ｍ^３は１又は２を示し、
Ａ及びＢは、互いに独立的に、次式（５−ａ）乃至（５−ｃ）の何れかを示し、
【００５３】
【化４５】

・・・（５−ａ）
【００５４】
【化４６】

・・・（５−ｂ）
【００５５】
【化４７】

・・・（５−ｃ）
［式（５−ａ）乃至（５−ｃ）中、Ｒ^１２乃至Ｒ^２７は、互いに独立的に、水素、ハロゲン（例えばＦ、Ｃｌ、Ｂｒ等）、アルキル基（メチル、エチル、プロピル、ブチル等の炭素数１乃至１８の分岐していてもよいアルキル基）、アルコキシ基（メトキシ、エトキシ、プロポキシ、ブトキシ等の炭素数１乃至１８の分岐していてもよいアルコキシ基）、アラルキル基（例えばベンジル、α，α−ジメチルベンジル、クミル、トルイル、フェネチル等）、又はアリール基（例えばフェニル及びナフチル等）を示す。］
【００５６】
このようなペリノン系染顔料の例としては、ＣＯＬＯＲ ＩＮＤＥＸに記載されている次のような染顔料、すなわち、
Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｏｒａｎｇｅ ６０、同７８、Ｃ．Ｉ．Ｖａｔ Ｏｒａｎｇｅ １５等の橙色染料；
Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ １３５、同１６２、同１７８、同１７９、Ｃ．Ｉ．Ｖａｔ Ｒｅｄ ７等の赤色染料；
Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ ２９等の紫色染料
を挙げることができる。
【００５７】
上記式（５）で表されるペリノン系染顔料の具体例として表５に示すものを挙げることができる。但し、勿論本発明はこれらに限定されるものではない。
【００５８】
【表５】

【００５９】
熱可塑性樹脂等の合成樹脂に対する相溶性及び分散性の良好度を考慮すると、このようなペリノン系染顔料中で染料の方が好ましい。
【００６０】
また本発明のレーザー光透過性着色樹脂組成物用着色剤は、下記式（６）で表されるアントラピリドン系造塩染料を含有することが好ましい。式（６）のアントラピリドン系造塩染料は、熱安定性の良好な堅牢な染料であり、樹脂との相溶性が高く、熱可塑性樹脂に配合した場合の樹脂成形性及び色相が良好である。特に、赤色染料として重要である。
【００６１】
【化４８】

・・・（６）
［式（６）中、
Ｒ^６８、Ｒ^６９、Ｒ^７０、及びＲ^７１は、互いに独立的に、水素、アルキル基（例えばメチル、エチル、プロピル、iso-プロピル、n-ブチル、tert-ブチル等の好ましくは炭素数１乃至５のアルキル基）、アリール基（例えばフェニル、ナフチル、低級アルキル置換フェニル、低級アルキル置換ナフチル、ハロゲン化フェニル、ハロゲン化ナフチル等の、炭素数１乃至３の低級アルキル又は塩素、臭素、ヨウ素、フッ素等のハロゲン等によって核置換されていてもよいアリール基）、アルケニル基（例えばビニル基、アリル基、プロペニル基、ブテニル基等の好ましくは炭素数２乃至１８のアルケニル基）、アルコキシ基（例えばメトキシ、エトキシ、プロポキシ、ブトキシ、ペンチルオキシ、ヘキシルオキシ等の好ましくは炭素数１乃至１８のアルコキシ基）、アミノ基、水酸基、ハロゲン（例えば塩素、臭素、ヨウ素、フッ素等）、アシル基（例えばホルミル、アセチル、プロピオニル、ブチリル、バレリル、ベンゾイル、トルオイル等）、アシルオキシ基、アシルアミド基、アシル−Ｎ−アルキルアミド基、カルボキシル基、アルコキシルカルボニル基、シクロヘキシルアミド基、スルホン酸基、又は
【００６２】
【化４９】

・・・（６−ａ）
【００６３】
を示し、Ｒ^６８乃至Ｒ^７１の少なくとも１つはスルホン酸基を示すものであり、Ｒ^６７は、水素、アルキル基、アリール基、アルコキシ基、アミノ基、水酸基、又はハロゲンを示し、
Ｐ^１は、Ｃ−Ｒ^７２又はＮを示し、
Ｒ^７２は、水素、アルキル基（例えばメチル、エチル、プロピル、iso-プロピル、n-ブチル、tert-ブチル等の好ましくは炭素数１乃至５のアルキル基）、アルコキシ基（例えばメトキシ、エトキシ、プロポキシ、ブトキシ、ペンチルオキシ、ヘキシルオキシ等の好ましくは炭素数１乃至１８のアルコキシ基）、アミノ基、水酸基、ハロゲン（例えば塩素、臭素、ヨウ素、フッ素等）、カルボキシル基、置換若しくは非置換のアリール基（例えばフェニル、ナフチル、低級アルキル置換フェニル、低級アルキル置換ナフチル、ハロゲン化フェニル、ハロゲン化ナフチル等の、炭素数１乃至３の低級アルキル又は塩素、臭素、ヨウ素、フッ素等のハロゲン等によって核置換されていてもよいアリール基）、置換（炭素数１乃至３の低級アルキル又は塩素、臭素、ヨウ素、フッ素等のハロゲン等による核置換）若しくは非置換のアラルキル基、又は置換（炭素数１乃至３の低級アルキル又は塩素、臭素、ヨウ素、フッ素等のハロゲン等による核置換）若しくは非置換のベンゾイル基を示し、
（Ｇ）^Ｓ＋は、脂肪族ジアミン誘導体、ロジンアミン誘導体、グアニジン誘導体、芳香族アミン誘導体、及び芳香族ジアミン誘導体からなる群から選ばれた少なくとも１つのアミンに起因するカチオン又は４級有機アンモニウムイオンを示し、
Ｓは１又は２を示し、
ｍ^５は１乃至４の整数を示し、
Ｋ^５は１又は２を示し、
前記Ｐ^２は、Ｏ又はＮＨを示し、
前記Ｒ^７３、Ｒ^７４、及びＲ^７５は、互いに独立的に、水素、アルキル基（例えばメチル、エチル、プロピル、iso-プロピル、n-ブチル、tert-ブチル等の好ましくは炭素数１乃至５のアルキル基）、アリール基（例えばフェニル、ナフチル、低級アルキル置換フェニル、低級アルキル置換ナフチル、ハロゲン化フェニル、ハロゲン化ナフチル等の、炭素数１乃至３の低級アルキル又は塩素、臭素、ヨウ素、フッ素等のハロゲン等によって核置換されていてもよいアリール基）、アルケニル基（例えばビニル基、アリル基、プロペニル基、ブテニル基等の好ましくは炭素数２乃至１８のアルケニル基）、アルコキシ基（例えばメトキシ、エトキシ、プロポキシ、ブトキシ、ペンチルオキシ、ヘキシルオキシ等の好ましくは炭素数１乃至１８のアルコキシ基）、アミノ基、水酸基、ハロゲン（例えば塩素、臭素、ヨウ素、フッ素等）、アシル基（例えばホルミル、アセチル、プロピオニル、ブチリル、バレリル、ベンゾイル、トルオイル等）、アシルオキシ基、アシルアミド基、アシル−Ｎ−アルキルアミド基、カルボキシル基、アルコキシルカルボニル基、シクロヘキシルアミド基、又はスルホン酸基を示す。］
【００６４】
上記式（６）で表されるアントラピリドン系造塩染料の具体例として、表６に示すものを挙げることができる。なお、これらの化合物例において式（６）中のｍ^５は１を示すものとする。但し、勿論本発明はこれらに限定されるものではない。
【００６５】
【表６】

【００６６】
本発明のレーザー光透過性着色樹脂組成物用着色剤は、下記式（７）で表されるモノアゾ含金染料を含有することが好ましい。式（７）のモノアゾ含金染料は、堅牢な骨格であるため熱安定性の良好な堅牢な染料を構成し易く、前記熱分析における染料の分解温度が約３００℃以上を示す。また、熱可塑性樹脂に配合した場合の樹脂成形性及び色相が良好である。特に、黄色乃至赤色染料として堅牢性が高い染料が少ないため有用である。
【００６７】
【化５０】

・・・（７）
【００６８】
［式（７）中、Ｋ^１は、０、１、又は２を示し、
（Ｄ）^ｒ＋は、水素イオン、アルカリ金属（Ｌｉ、Ｎａ、Ｋ等）に起因するカチオン、アンモニウムイオン、有機アミン（脂肪族第１級アミン、脂肪族第２級アミン、脂肪族第３級アミン等）に基づくカチオン、又は第４級有機アンモニウムイオンを示し、
ｍ^４は、０、１、又は２を示し、ｒは、１又は２を示し、Ｘは、１又は２を示し、
Ｌ_１及びＬ_３は、互いに独立的に、Ｏ又はＣＯＯを示し、
Ｌ_２及びＬ_４は、Ｏを示し、
Ｍ^１は、２乃至４価の金属（Ｃｒ、Ｃｏ、Ｃｕ、Ｎｉ、Ａｌ等）を示し、
Ｒ^２８及びＲ^２９は、互いに独立的に、水素、Ｃｌ、ＳＯ_２Ｒ^３０、又は
【化５１】

を示し、
前記Ｒ^３０は、直鎖又は分岐鎖のアルキル基（例えば炭素数１乃至４のアルキル基）を示し、
前記Ｒ^３１及びＲ^３２は、互いに独立的に、水素、又は直鎖若しくは分岐鎖のアルキル基（例えば炭素数１乃至４のアルキル基）を示し、
Ｂ^１及びＢ^２は、互いに独立的に、
【化５２】

・・・（８）
又は
【化５３】

・・・（９）
を示し、
前記Ｒ^３３及びＲ^３５は、互いに独立的に、水素、Ｃｌ、ＳＯ_２Ｒ^３７、又は
【化５４】

を示し、
前記Ｒ^３７は、直鎖又は分岐鎖のアルキル基（例えば炭素数１乃至４のアルキル基）を示し、前記Ｒ^３８及びＲ^３９は、互いに独立的に、水素、又は直鎖若しくは分岐鎖のアルキル基（例えば炭素数１乃至４のアルキル基）を示し、
前記Ｒ^３４及びＲ^３６は、互いに独立的に、水素、直鎖若しくは分岐鎖のアルキル基（例えば炭素数１乃至１８のアルキル基）、カルボキシル基、ヒドロキシ基、アルコキシ基（例えば炭素数１乃至１８のアルコキシ基）、アミノ基、又はハロゲン（例えばＦ、Ｃｌ、Ｂｒ等）を示す。］
【００６９】
式（７）中の（Ｄ）^＋の基となり得る有機アミンの例としては、公知の脂肪族アミン、脂肪族ジアミン、脂環族アミン、アルコキシアルキルアミン、アルカノール基含有アミン、グアニジン誘導体のアミンなどが挙げられる。
【００７０】
このような有機アミンの具体例としては、
ブチルアミン、ヘキシルアミン、ペンチルアミン、オクチルアミン、ラウリルアミン、ミリスチルアミン、パルミチルアミン、セチルアミン、オレイルアミン、ステアリルアミン、ジブチルアミン、ドデシルアミン、エチレンジアミン、テトラメチレンジアミン、ヘキサメチレンジアミン等の脂肪族アミン；
シクロヘキシルアミン、ジ−シクロヘキシルアミン、ロジンアミン等の脂環族アミン；
３−プロポキシプロピルアミン、ジ−（２−エチルヘキシル）アミン、ジ−（２−エチルヘキシル）アミン、２−エチルヘキシルアミン、ジ−（３−エトキシプロピル）アミン、３−ブトキシプロピルアミン、オクトオキシプロピルアミン、３−（２−エチルヘキシルオキシ）プロピルアミン等のアルコキシアルキルアミン；
ジメチルアミノプロピルアミン、ジブチルアミノプロピルアミン等のジアミン；
１，３−ジフェニルグアニジン、１−ｏ−トリルグアニジン、ジ−ｏ−トリルグアニジン、グアニジン等のグアニジン誘導体のアミン等を挙げることができる。
【００７１】
本発明に用いるモノアゾ含金染料の中心金属Ｍ^１としては、原子価が２価、３価又は４価の金属が挙げられる。その具体例としては、Ｚｎ、Ｓｒ、Ｃｒ、Ｃｕ、Ａｌ、Ｔｉ、Ｆｅ、Ｚｒ、Ｎｉ、Ｃｏ、Ｍｎ、Ｂ、Ｓｉ及びＳｎ等を挙げることができる。
前記式（７）で表されるモノアゾ含金染料の具体例としては、下記のような染料を挙げることができる。前記式（８）及び式（９）の基は、それぞれ下記染料例におけるようにアゾ基並びにＬ_２又はＬ_４に結合するものとすることができる。但し、勿論本発明はこれらに限定されるものではない。
【００７２】
前記式（７）で表されるモノアゾ含金染料であってＢ^１及びＢ^２が前記式（８）で表されるもの、すなわち式（７−ａ）のモノアゾ含金染料の具体例としては下記の構造が挙げられる。
【化５５】

・・・・・（７−ａ）
【００７３】
【表７】

【００７４】
前記式（７）で表されるモノアゾ含金染料であってＢ^１及びＢ^２が前記式（９）で表されるもの、すなわち式（７−ｂ）のモノアゾ含金染料の具体例としては下記の構造が挙げられる。
【化５６】

・・・・・（７−ｂ）
【００７５】
【表８】

【００７６】
また、本発明のレーザー光透過性着色樹脂組成物用着色剤は、下記の骨格を有する染料を用いることが好ましい。この骨格は、フェニル−ＮＨ−フェニルに比べ切れにくく、堅牢な染料を構成し易い。また、熱可塑性樹脂に配合した場合の樹脂成形性及び色相が良好である。特に、黄色染料として堅牢性が高い染料が少ないため有用である。
【００７７】
【化５７】

【００７８】
この式中のフェニル基は置換基を有するものであってもよく、その置換基同士が環状を形成しているものであってもよい。
この骨格を有する染料としては、置換基を有する又は有しない下記構造の黄色系アントラキノン系染料が好適である。本構造を有するアントラキノン系染料は、熱可塑性樹脂に対する相溶性が良好で、熱可塑性樹脂を鮮明に着色することができ、レーザー光（特にＹＡＧレーザー等による１０００乃至１２００ｎｍ又はその近傍の波長のレーザー光）の透過性が高い。また実用的に充分な耐熱性を示す。
【００７９】
【化５８】

【００８０】
この構造の染料の具体例としては、次のような染料を挙げることができる。但し、勿論本発明はこれらに限定されるものではない。
【００８１】
【化５９】

化合物例８−１
【００８２】
【化６０】

化合物例８−２
【００８３】
【化６１】

化合物例８−３
【００８４】
【化６２】

化合物例８−４
【００８５】
【化６３】

化合物例８−５
【００８６】
【化６４】

化合物例８−６
【００８７】
【化６５】

化合物例８−7
【００８８】
更に、本発明のレーザー光透過性着色樹脂組成物用着色剤は、下記の骨格を有する染料を用いることが好ましい。この骨格は、フェニル−ＮＨ−フェニルに比べ切れにくく、堅牢な染料を構成し易い。また、熱可塑性樹脂に配合した場合の樹脂成形性及び色相が良好である。特に、黄色染料として堅牢性が高い染料が少ないため有用である。
【００８９】
【化６６】

【００９０】
この式中のフェニル基は置換基を有するものであってもよく、その置換基同士が環状を形成しているものであってもよい。
前記骨格を有する染料の具体例としては、次のような染料（チアゾール環を有するアントラキノン誘導体）を挙げることができる。但し、勿論本発明はこれらに限定されるものではない。
【００９１】
【化６７】

化合物例９−１
【００９２】
【化６８】

化合物例９−２
【００９３】
【化６９】

化合物例９−３
【００９４】
【化７０】

化合物例９−４
【００９５】
【化７１】

化合物例９−５
【００９６】
また更に、本発明のレーザー光透過性着色樹脂組成物用着色剤は、下記の骨格を有する染料を用いることが好ましい。この骨格は、フェニル−ＮＨ−フェニルに比べ切れにくく、堅牢な染料を構成し易い。また、熱可塑性樹脂に配合した場合の樹脂成形性及び色相が良好である。特に、黄色染料として堅牢性が高い染料が少ないため有用である。
【００９７】
【化７２】

【００９８】
この式中のフェニル基は置換基を有するものであってもよく、その置換基同士が環状を形成しているものであってもよい。
【００９９】
前記骨格を有する染料の具体例としては、次のような染料（アントラキノンチオキサントン誘導体）を挙げることができる。但し、勿論本発明はこれらに限定されるものではない。
【０１００】
【化７３】

化合物例１１−１
【０１０１】
【化７４】

化合物例１１−２
【０１０２】
【化７５】

化合物例１１−３
【０１０３】
上記式（１）乃至式（３）で表されるアントラキノン系造塩染料と上記の他の染料を共に含有してなる本発明のレーザー光透過性着色樹脂組成物用着色剤の具体例として、次のような着色剤を挙げることができる。但し、勿論本発明はこれらに限定されるものではない。なお、以下の記述においては、「重量部」を「部」と略す。
【０１０４】
着色剤例
(a-1)：化合物例１−１のアントラキノン系造塩染料と化合物例５−３のペリノン系赤色染料と化合物例８−１のアントラキノン系黄色染料との組合せ。
（例えば、化合物例１−１のアントラキノン系造塩染料６０部と化合物例５−３のペリノン系赤色染料２０部と化合物例８−１のアントラキノン系黄色染料１０部との組合せ）。
(a-2)：化合物例１−１のアントラキノン系造塩染料と化合物例５−３のペリノン系赤色染料と化合物例５−１のペリノン系橙色染料との組合せ。
（例えば、化合物例１−１のアントラキノン系造塩染料３０部と化合物例５−３のペリノン系赤色染料２０部と化合物例５−１のペリノン系橙色染料１０部との組合せ）。
(a-3)：化合物例１−２のアントラキノン系造塩染料と化合物例５−３のペリノン系赤色染料と化合物例８−１のアントラキノン系黄色染料との組合せ。
（例えば、化合物例１−２のアントラキノン系造塩染料６０部と化合物例５−３のペリノン系赤色染料２０部と化合物例８−１のアントラキノン系黄色染料１０部との組合せ）。
(a-4)：化合物例１−１のアントラキノン系造塩染料と化合物例５−３のペリノン系赤色染料と化合物例９−１のアントラキノン系黄色染料との組合せ。
（例えば、化合物例１−１のアントラキノン系造塩染料６０部と化合物例５−３のペリノン系赤色染料２０部と化合物例９−１のアントラキノン系黄色染料１０部との組合せ）。
(a-5)：化合物例１−１のアントラキノン系造塩染料と化合物例７−１のモノアゾ含金赤色染料と化合物例７−３のモノアゾ含金黄色染料との組合せ。
（例えば、化合物例１−１のアントラキノン系造塩染料６０部と化合物例７−１のモノアゾ含金赤色染料２０部と化合物例７−３のモノアゾ含金黄色染料１０部との組合せ）。
(a-6)：化合物例１−１のアントラキノン系造塩染料と化合物例７−１のモノアゾ含金赤色染料と化合物例９−１のアントラキノン系黄色染料との組合せ。
（例えば、化合物例１−１のアントラキノン系造塩染料６０部と化合物例７−１のモノアゾ含金赤色染料２０部と化合物例９−１のアントラキノン系黄色染料１０部との組合せ）。
(a-7)：化合物例１−２のアントラキノン系造塩染料と化合物例７−１のモノアゾ含金赤色染料と化合物例８−１のアントラキノン系黄色染料との組合せ。
（例えば、化合物例１−２のアントラキノン系造塩染料６０部と化合物例７−１のモノアゾ含金赤色染料２０部と化合物例８−１のアントラキノン系黄色染料１０部との組合せ）。
(a-8)：化合物例１−２のアントラキノン系造塩染料と化合物例５−３のペリノン系赤色染料と化合物例７−３のモノアゾ含金黄色染料との組合せ。
（例えば、化合物例１−２のアントラキノン系造塩染料６０部と化合物例５−３のペリノン系赤色染料２０部と化合物例７−３のモノアゾ含金黄色染料１０部との組合せ）。
(a-9)：化合物例１−４のアントラキノン系造塩染料と化合物例５−３のペリノン系赤色染料との組合せ。
（例えば、化合物例１−４のアントラキノン系造塩染料３０部と化合物例５−３のペリノン系赤色染料１０部との組合せ）。
(a-10)：化合物例１−２０のアントラキノン系造塩染料と化合物例７−１のモノアゾ含金赤色染料との組合せ。
（例えば、化合物例１−２０のアントラキノン系造塩染料３０部と化合物例７−１のモノアゾ含金赤色染料１０部との組合せ）。
(a-11)：化合物例１−１０のアントラキノン系造塩染料と化合物例６−１のアントラピリドン系造塩赤色染料との組合せ。
（例えば、化合物例１−１０のアントラキノン系造塩染料３０部と化合物例６−１のアントラピリドン系造塩赤色染料１０部との組合せ）。
(a-12)：化合物例１−１８のアントラキノン系造塩染料と化合物例９−１のアントラキノン系黄色染料との組合せ。
（例えば、化合物例１−１８のアントラキノン系造塩染料３０部と化合物例９−１のアントラキノン系黄色染料１０部との組合せ）。
(a-13)：化合物例１−１９のアントラキノン系造塩染料と化合物例８−１のアントラキノン系黄色染料との組合せ。
（例えば、化合物例１−１９のアントラキノン系造塩染料３０部と化合物例８−１のアントラキノン系黄色染料１０部との組合せ）。
(a-14)：化合物例１−２４のアントラキノン系造塩染料と化合物例８−１のアントラキノン系黄色染料との組合せ。
（例えば、化合物例１−２４のアントラキノン系造塩染料３０部と化合物例８−１のアントラキノン系黄色染料１０部との組合せ）。
(a-15)：化合物例１−１１のアントラキノン系造塩染料と化合物例７−１のモノアゾ含金赤色染料と化合物例８−１のアントラキノン系黄色染料との組合せ。
（例えば、化合物例１−１１のアントラキノン系造塩染料６０部と化合物例７−１のモノアゾ含金赤色染料２０部と化合物例８−１のアントラキノン系黄色染料１０部との組合せ）。
(a-16)：化合物例２−２のアントラキノン系造塩染料と化合物例５−３のペリノン系赤色染料と化合物例９−１のアントラキノン系黄色染料との組合せ。
（例えば、化合物例２−２のアントラキノン系造塩染料６０部と化合物例５−３のペリノン系赤色染料２０部と化合物例９−１のアントラキノン系黄色染料１０部との組合せ）。
(a-17)：化合物例２−８のアントラキノン系造塩染料と化合物例５−３のペリノン系赤色染料と化合物例９−１のアントラキノン系黄色染料との組合せ。
（例えば、化合物例２−８のアントラキノン系造塩染料６０部と化合物例５−３のペリノン系赤色染料２０部と化合物例９−１のアントラキノン系黄色染料１０部との組合せ）。
(a-18)：化合物例２−５のアントラキノン系造塩染料と化合物例５−３のペリノン系赤色染料と化合物例８−１のアントラキノン系黄色染料との組合せ。
（例えば、化合物例２−５のアントラキノン系造塩染料６０部と化合物例５−３のペリノン系赤色染料２０部と化合物例８−１のアントラキノン系黄色染料１０部との組合せ）。
(a-19)：化合物例１−２２のアントラキノン系造塩染料と化合物例３−４のアントラキノン系造塩染料化合物例と化合物例６−１のアントラピリドン系造塩赤色染料との組合せ。
（例えば、化合物例１−２２のアントラキノン系造塩染料６０部と化合物例３−４のアントラキノン系造塩染料化合物例４０部と化合物例６−１のアントラピリドン系造塩赤色染料１０部との組合せ）。
(a-20)：化合物例１−２０のアントラキノン系造塩染料と化合物例３−４のアントラキノン系造塩染料化合物例と６−１のアントラピリドン系造塩赤色染料との組合せ。
（例えば、化合物例１−２０のアントラキノン系造塩染料５０部と化合物例３−４のアントラキノン系造塩染料化合物例４０部と化合物例６−１のアントラピリドン系造塩赤色染料１０部との組合せ）。
(a-21)：化合物例１−２０のアントラキノン系造塩染料と化合物例３−４のアントラキノン系造塩染料化合物例と化合物例５−２のペリノン系赤色染料との組合せ。
（例えば、化合物例１−２０のアントラキノン系造塩染料５０部と化合物例３−４のアントラキノン系造塩染料化合物例４０部と化合物例５−２のペリノン系赤色染料１０部との組合せ）。
(a-22)：化合物例３−１０のアントラキノン系造塩染料と化合物例５−３のペリノン系赤色染料と化合物例９−１のアントラキノン系黄色染料との組合せ。
（例えば、化合物例３−１０のアントラキノン系造塩染料６０部と化合物例５−３のペリノン系赤色染料２０部と化合物例９−１のアントラキノン系黄色染料１０部との組合せ）。
(a-23)：化合物例３−１１のアントラキノン系造塩染料と化合物例５−３のペリノン系赤色染料と化合物例８−１のアントラキノン系黄色染料との組合せ。
（例えば、化合物例３−１１のアントラキノン系造塩染料６０部と化合物例５−３のペリノン系赤色染料２０部と化合物例８−１のアントラキノン系黄色染料１０部との組合せ）。
(a-24)：化合物例３−１１のアントラキノン系造塩染料と化合物例５−３のペリノン系赤色染料と化合物例１１−１のアントラキノン系黄色染料との組合せ。
（例えば、化合物例３−１１のアントラキノン系造塩染料６０部と化合物例５−３のペリノン系赤色染料２０部と化合物例１１−１のアントラキノン系黄色染料１０部との組合せ）。
【０１０５】
本発明のレーザー光透過性着色樹脂組成物は、上記本発明のレーザー光透過性着色樹脂組成物用着色剤により熱可塑性樹脂が着色されてなるものである。本発明のレーザー光透過性着色樹脂組成物におけるレーザー光透過性着色樹脂組成物用着色剤の使用量は、熱可塑性樹脂に対し例えば０．０１乃至１０重量％とすることができる。好ましくは０．１乃至５重量％である。
【０１０６】
本発明の着色剤により着色されてなる熱可塑性樹脂である本発明のレーザー光透過性着色樹脂組成物における波長９５０ｎｍのレーザー光の透過率であるＴ_着色樹脂と、非着色の前記と同一の熱可塑性樹脂における波長９５０ｎｍのレーザー光の透過率であるＴ_{非着色樹脂}との比であるＴ_着色樹脂／Ｔ_{非着色樹脂}は、例えば０．８乃至１．２であるものとすることができ、好ましくは０．９乃至１．１である。
【０１０７】
また、本発明のレーザー光透過性着色樹脂組成物における波長９５０ｎｍのレーザー光の透過率であるＴ_{９５０ｎｍ}と波長１０５０ｎｍのレーザー光の透過率であるＴ_{１０５０ｎｍ}との比であるＴ_{９５０ｎｍ}／Ｔ_{１０５０ｎｍ}は、例えば０．８乃至１．２であるものとすることができ、好ましくは０．９乃至１．１である。
【０１０８】
本発明のレーザー光透過性着色樹脂組成物における熱可塑性樹脂の具体例としては、ポリアミド樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、ポリブチレンテレフタレート樹脂、ポリフェニレンスルフィド樹脂及びポリエーテルエーテルケトン樹脂、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、ポリフェニレンスルフィド樹脂、ポリカーボネート樹脂、非結晶（透明）ナイロン、液晶ポリマー、ポリスチレン樹脂、アクリル系樹脂、ポリアセタール樹脂、ポリフェニレンエーテル樹脂、アクリロニトリル・スチレン共重合樹脂、アクリロニトリル・ブタジエン・スチレン共重合樹脂、スチレン・メチルメタクリレート共重合樹脂、スチレン・ブタジエン共重合樹脂、スチレン・ブタジエン・メチルメタクリレート共重合樹脂等が挙げられる。これらの熱可塑性樹脂は、単独で、又は２種類以上を混合して用いることができる。また、これらの重合体を主体とする共重合体若しくは混合物；これらにゴム又はゴム状樹脂等のエラストマーを配合した熱可塑性樹脂；及びこれらの樹脂を１０重量％以上含有するポリマーアロイ等も挙げられる。
【０１０９】
これらの熱可塑性樹脂のうち好ましいのは、レーザー光透過性及び機械的強度の良好性等の点から、ポリプロピレン系樹脂、ポリエチレン系樹脂、ポリアミド系樹脂、ポリエステル系樹脂（ＰＥＴ及びＰＢＴを含む）、ポリカーボネート系樹脂、ポリスチレン樹脂、アクリル系樹脂、ポリアセタール樹脂である。
【０１１０】
本発明のレーザー光透過性着色樹脂組成物は、用途及び目的に応じ、各種の繊維状補強材を適量含有するものとすることができる。透明性を要求される樹脂の補強にはガラス繊維が好ましい。ガラス繊維としては、含アルカリガラス、低アルカリガラス、無アルカリガラスの何れを用いることもできる。好ましくはＥガラス及びＴガラスである。好適に用いることができるガラス繊維の繊維長は２乃至１５ｍｍであり繊維径は１乃至２０μｍである。ガラス繊維の形態については特に制限はなく、例えばロービング、ミルドファイバー等、何れであってもよい。これらのガラス繊維は、一種類を単独で用いるほか、二種以上を組合せて用いることもできる。その含有量は、熱可塑性樹脂１００重量％に対し５乃至１２０重量％とすることが好ましい。５重量％未満の場合、十分なガラス繊維補強効果が得られ難く、１２０重量％を超えると成形性が低下することとなり易い。好ましくは１０乃至６０重量％、特に好ましくは２０乃至５０重量％である。
【０１１１】
本発明のレーザー光透過性着色樹脂組成物は、必要に応じ種々の添加剤を配合することも可能である。このような添加剤としては、例えば助色剤、分散剤、充填剤、安定剤、可塑剤、改質剤、紫外線吸収剤又は光安定剤、酸化防止剤、帯電防止剤、潤滑剤、離型剤、結晶促進剤、結晶核剤、難燃剤、及び耐衝撃性改良用のエラストマー等が挙げられる。
【０１１２】
本発明のレーザー光透過性着色樹脂組成物は、原材料を任意の配合方法により配合することにより得ることができる。これらの配合成分は、通常、できるだけ均質化させることが好ましい。具体的には例えば、全ての原材料をブレンダー、ニーダー、バンバリーミキサー、ロール、押出機等の混合機で混合して均質化させて着色熱可塑性樹脂組成物を得たり、或は、一部の原材料を混合機で混合した後、残りの成分を加えて更に混合して均質化させて樹脂組成物を得ることもできる。また、予めドライブレンドされた原材料を加熱した押出機で溶融混練して均質化した後、針金状に押出し、次いで所望の長さに切断して着色粒状物（着色ペレット）として得ることもできる。
【０１１３】
また本発明のレーザー光透過性着色樹脂組成物のマスターバッチは、任意の方法により得られる。例えば、マスターバッチのベースとなる熱可塑性樹脂の粉末又はペレットと着色剤をタンブラーやスーパーミキサー等の混合機で混合した後、押出機、バッチ式混練機又はロール式混練機等により加熱溶融してペレット化又は粗粒子化することにより得ることができる。また例えば、合成後未だ溶液状態にあるマスターバッチ用熱可塑性樹脂に着色剤を添加した後、溶媒を除いてマスターバッチを得ることもできる。
【０１１４】
本発明のレーザー光透過性着色樹脂組成物の成形は、通常行われる種々の手順により行い得る。例えば、着色ペレットを用いて、押出機、射出成形機、ロールミル等の加工機により成形することにより行うこともでき、また、透明性を有する熱可塑性樹脂のペレット又は粉末、粉砕された着色剤、及び必要に応じ各種の添加物を、適当なミキサー中で混合し、この混合物を、加工機を用いて成形することにより行うこともできる。また例えば、適当な重合触媒を含有するモノマーに着色剤を加え、この混合物を重合により所望の熱可塑性樹脂とし、これを適当な方法で成形することもできる。成形方法としては、例えば射出成形、押出成形、圧縮成形、発泡成形、ブロー成形、真空成形、インジェクションブロー成形、回転成形、カレンダー成形、溶液流延等、一般に行われる何れの成形方法を採用することもできる。
【０１１５】
【発明の効果】
本発明のレーザー光透過性着色樹脂組成物用着色剤、その着色剤により着色されたレーザー光透過性着色樹脂組成物、並びにその着色樹脂組成物からなるレーザー光透過性カラーフィルター及びレーザー光透過性カラーフィルムは、半導体レーザーによる８００ｎｍ付近からＹＡＧレーザーによる１１００ｎｍ付近にかけての波長のレーザー光の透過性が高く、耐熱性や耐光性等の堅牢性が高く、また耐移行性や耐薬品性等が良好で、而も鮮明な色相を示す。
【０１１６】
【実施例】
次に実施例を挙げて本発明を具体的に説明するが、勿論本発明はこれらのみに限定されるものではない。
【０１１７】
製造例１乃至１１ではアントラキノン系造塩染料の合成について説明する。
【０１１８】
製造例１
化合物例１０−１のアントラキノン系酸性染料５０ｇを水５００ｍｌに分散させた。一方、水３００ｍｌに塩酸３０ｇとヘキサメチレンジアミン２０ｇを溶解させた。この溶液を、室温で前記アントラキノン系酸性染料の分散液に滴下し、その混合液のｐＨを３．５に調整して１時間撹拌した。その反応混合液を濾過して濾取物を水洗したところ、得られたアントラキノン系造塩染料の収量は６６．５ｇ（収率９５％）であった。
【０１１９】
製造例２
化合物例１０−１のアントラキノン系酸性染料５０ｇを水５００ｍｌに分散させた。一方、水３００ｍｌに塩酸３０ｇとヘキサメチレンジアミン１０ｇを溶解させた。この溶液を、室温で前記アントラキノン系酸性染料の分散液に滴下し、その混合液のｐＨを３．５に調整して１時間撹拌した。その反応混合液を濾過して濾取物を水洗したところ、得られたアントラキノン系造塩染料の収量は５７ｇ（収率９５％）であった。
【０１２０】
製造例３
化合物例１０−２のアントラキノン系酸性染料５０ｇを水５００ｍｌに分散させた。一方、水３００ｍｌに塩酸３０ｇとグアニジン１１ｇを溶解させた。この溶液を、室温で前記アントラキノン系酸性染料の分散液に滴下し、その混合液のｐＨを３．５に調整して１時間撹拌した。その反応混合液を濾過して濾取物を水洗したところ、得られたアントラキノン系造塩染料の収量は５９ｇ（収率９７％）であった。
【０１２１】
製造例４
化合物例１０−６のアントラキノン系酸性染料５０ｇを水５００ｍｌに分散させた。一方、水３００ｍｌに塩酸３０ｇとジフェニルグアニジン４０ｇを溶解させた。この溶液を、室温で前記アントラキノン系酸性染料の分散液に滴下し、その混合液のｐＨを３．５に調整して１時間撹拌した。その反応混合液を濾過して濾取物を水洗したところ、得られたアントラキノン系造塩染料の収量は８７ｇ（収率９７％）であった。
【０１２２】
製造例５
化合物例１０−７のアントラキノン系酸性染料５０ｇを水５００ｍｌに分散させた。一方、水３００ｍｌに塩酸３０ｇとヘキサメチレンジアミン１４ｇを溶解させた。この溶液を、室温で前記アントラキノン系酸性染料の分散液に滴下し、その混合液のｐＨを３．５に調整して１時間撹拌した。その反応混合液を濾過して濾取物を水洗したところ、得られたアントラキノン系造塩染料の収量は６２ｇ（収率９７％）であった。
【０１２３】
製造例６
化合物例１０−１のアントラキノン系酸性染料２５ｇと化合物例１０−２のアントラキノン系酸性染料２５ｇを水５００ｍｌに分散させた。一方、水３００ｍｌに塩酸３０ｇとグアニジン１０ｇを溶解させた。この溶液を、室温で前記アントラキノン系酸性染料の分散液に滴下し、その混合液のｐＨを３．５に調整して１時間撹拌した。その反応混合液を濾過して濾取物を水洗したところ、得られたアントラキノン系造塩染料の収量は５７ｇ（収率９５％）であった。
【０１２４】
製造例７
式（１２−１）で表されるアントラキノン系酸性染料３０ｇを水１５００ｍｌに分散させた。一方、水２５０ｍｌに塩化ベンジルトリメチルアンモニウム１２ｇを溶解させた。この溶液を、５０℃で保温した前記アントラキノン系酸性染料の分散液に滴下し、１時間撹拌した。その反応混合液を濾過して濾取物を水洗したところ、得られたアントラキノン系造塩染料の収量は３５ｇ（収率８３％）であった。
【０１２５】
【化７６】

・・・（１２−１）
【０１２６】
製造例８
式（１２−２）で表されるアントラピリドン系酸性染料２０ｇを水２０００ｍｌに分散させた。一方、水１８０ｍｌに塩化ベンジルトリメチルアンモニウム９ｇを溶解させた。この溶液を、５０℃で保温した前記アントラピリドン系酸性染料の分散液に滴下し、１時間撹拌した。その反応混合液を濾過して濾取物を水洗したところ、得られたアントラピリドン系造塩染料の収量は２１ｇ（収率７２％）であった。
【０１２７】
【化７７】

・・・（１２−２）
【０１２８】
製造例９
式（１２−３）で表されるアントラキノン系酸性染料３０ｇを水１０００ｍｌに分散させた。一方、水１００ｍｌに塩酸７ｇとヘキサメチレンジアミン４ｇを溶解させた。この溶液を、３５℃で保温した前記アントラキノン系酸性染料の分散液に滴下し、１時間撹拌した。その反応混合液を濾過して濾取物を水洗したところ、得られたアントラキノン系造塩染料の収量は２５ｇ（収率７４％）であった。
【０１２９】
【化７８】

・・・（１２−３）
【０１３０】
製造例１０
化合物例１０−１のアントラキノン系酸性染料５０ｇを水1５００ｍｌに分散させた。一方、水６００ｍｌに塩化ベンジルトリメチルアンモニウム３０ｇを溶解させた。この溶液を、５０℃で保温した前記アントラキノン系酸性染料の分散液に滴下し、１時間撹拌した。その反応混合液を濾過して濾取物を水洗したところ、得られたアントラキノン系造塩染料の収量は６２ｇ（収率７８％）であった。
【０１３１】
製造例１１
式（１２−３）で表されるアントラキノン系酸性染料３０ｇを水１０００ｍｌに分散させた。一方、水１２０ｍｌに塩化ベンジルトリメチルアンモニウム６ｇを溶解させた。この溶液を、４０℃で保温した前記アントラキノン系酸性染料の分散液に滴下し、１時間撹拌した。その反応混合液を濾過して濾取物を水洗したところ、得られたアントラキノン系造塩染料の収量は２７ｇ（収率７５％）であった。
【０１３２】
実施例１乃至８ではレーザー光透過性着色樹脂組成物用着色剤（混合配色）について説明する。
【０１３３】
実施例１
製造例１のアントラキノン系造塩染料５４ｇと化合物例５−３のペリノン系染料１８ｇと化合物例８−１のアントラキノン系染料９ｇとをステンレス製タンブラーに入れ、１時間撹拌混合して、レーザー光透過性着色樹脂組成物用着色剤の黒色粉末８０ｇを得た（収率９９％）。その後、イオンクロマトグラフ（日本ダイオネクス社製 ＤＸ−３００）にて、ガードカラム（イオンパック ＡＧ４Ａ−ＳＣ）と分離カラム（イオンパックＡＳ４Ａ−ＳＣ）を取り付け、黒色粉末を少量のメタノールで溶かして水で希釈し、その上澄み液を注入して、カラム温度３５℃、流速１．５ｍｌ／ｍｉｎで無機塩を測定したところ、塩素イオン、硫酸イオンともに０．０１％であった。
【０１３４】
実施例２
製造例３のアントラキノン系造塩染料５４ｇと化合物例５−３のペリノン系染料１８ｇと化合物例８−１のアントラキノン系染料９ｇとをステンレス製タンブラーに入れ、１時間撹拌混合して、レーザー光透過性着色樹脂組成物用着色剤の黒色粉末８０ｇを得た（収率９９％）。
【０１３５】
実施例３
製造例１のアントラキノン系造塩染料５４ｇと化合物例５−３のペリノン系染料１８ｇと化合物例９−１のアントラキノン系染料（バット染料）９ｇとをステンレス製タンブラーに入れ、１時間撹拌混合して、レーザー光透過性着色樹脂組成物用着色剤の黒色粉末８０ｇを得た（収率９９％）。
【０１３６】
実施例４
製造例１のアントラキノン系造塩染料５４ｇと化合物例７−１のモノアゾ含金染料１８ｇと化合物例７−２のモノアゾ含金染料９ｇとをステンレス製タンブラーに入れ、１時間撹拌混合して、レーザー光透過性着色樹脂組成物用着色剤の黒色粉末８０ｇを得た（収率９９％）。
【０１３７】
実施例５
製造例１のアントラキノン系造塩染料５４ｇと化合物例５−３のペリノン系染料１８ｇと化合物例５−１のペリノン系染料９ｇとをステンレス製タンブラーに入れ、１時間撹拌混合して、レーザー光透過性着色樹脂組成物用着色剤の黒色粉末８０ｇを得た（収率９９％）。
【０１３８】
実施例６
製造例１のアントラキノン系造塩染料５４ｇと化合物例７−１のモノアゾ含金染料１８ｇと化合物例９−１のアントラキノン系染料９ｇとをステンレス製タンブラーに入れ、１時間撹拌混合して、レーザー光透過性着色樹脂組成物用着色剤の黒色粉末８０ｇを得た（収率９９％）。
【０１３９】
実施例７
製造例１のアントラキノン系造塩染料５４ｇと化合物例５−３で表されるペリノン系染料１８ｇと化合物例７−３のモノアゾ含金染料９ｇとをステンレス製タンブラーに入れ、１時間撹拌混合して、レーザー光透過性着色樹脂組成物用着色剤の黒色粉末８０ｇを得た（収率９９％）。
【０１４０】
実施例８
製造例１のアントラキノン系造塩染料５４ｇと化合物例７−１のモノアゾ含金染料１８ｇと化合物例９−１のアントラキノン系染料（バット染料）９ｇとをステンレス製タンブラーに入れ、１時間撹拌混合して、レーザー光透過性着色樹脂組成物用着色剤の黒色粉末８０ｇを得た（収率９９％）。
【０１４１】
実施例９乃至２４、並びに比較例１乃至８では、レーザー光透過性着色樹脂組成物について説明する。
【０１４２】
実施例９
６ナイロン・・・・４００ｇ［非強化６ナイロン（デュポン社製のポリアミド樹脂）を真空乾燥装置を用いて１２０℃で８時間以上乾燥を行った後、計量したもの］
製造例１のレーザー光透過性着色樹脂組成物用着色剤・・・・０．８０ｇ
【０１４３】
上記配合物をステンレス製タンブラーに入れ、１時間撹拌混合した。得られた混合物を、射出成形機（川口鉄鋼社製 商品名：Ｋ５０−Ｃ）を用いて、シリンダー温度２５０℃、金型温度６０℃で通常の方法で射出成形したところ、外観及び表面光沢が良好で色むらがない均一な紺色の試験片［４８×８６×３（ｍｍ）］を得た。
【０１４４】
実施例１０
６ナイロン・・・・４００ｇ［非強化６ナイロン（デュポン社製のポリアミド樹脂）を真空乾燥装置を用いて１２０℃で８時間以上乾燥を行った後、計量したもの］
製造例３のレーザー光透過性着色樹脂組成物用着色剤・・・・０．８０ｇ
【０１４５】
上記配合物をステンレス製タンブラーに入れ、１時間撹拌混合した。得られた混合物を、射出成形機（川口鉄鋼社製 商品名：Ｋ５０−Ｃ）を用いて、シリンダー温度２５０℃、金型温度６０℃で通常の方法で射出成形したところ、外観及び表面光沢が良好で色むらがない均一な緑色の試験片［４８×８６×３（ｍｍ）］を得た。
【０１４６】
実施例１１
６ナイロン・・・・４００ｇ［非強化６ナイロン（デュポン社製のポリアミド樹脂）を真空乾燥装置を用いて１２０℃で８時間以上乾燥を行った後、計量したもの］
実施例１のレーザー光透過性着色樹脂組成物用着色剤・・・・０．８０ｇ
【０１４７】
上記配合物をステンレス製タンブラーに入れ、１時間撹拌混合した。得られた混合物を、射出成形機（川口鉄鋼社製 商品名：Ｋ５０−Ｃ）を用いて、シリンダー温度２５０℃、金型温度６０℃で通常の方法で射出成形したところ、外観及び表面光沢が良好で色むらがない均一な黒色の試験片［４８×８６×３（ｍｍ）］を得た。
【０１４８】
実施例１２
６ナイロン・・・・４００ｇ［非強化６ナイロン（デュポン社製のポリアミド樹脂）を真空乾燥装置を用いて１２０℃で８時間以上乾燥を行った後、計量したもの］
実施例２のレーザー光透過性着色樹脂組成物用着色剤・・・・０．８０ｇ
【０１４９】
上記配合物をステンレス製タンブラーに入れ、１時間撹拌混合した。得られた混合物を、射出成形機（川口鉄鋼社製 商品名：Ｋ５０−Ｃ）を用いて、シリンダー温度２５０℃、金型温度６０℃で通常の方法で射出成形したところ、外観及び表面光沢が良好で色むらがない均一な黒色の試験片［４８×８６×３（ｍｍ）］を得た。
【０１５０】
実施例１３
６ナイロン・・・・４００ｇ［非強化６ナイロン（デュポン社製のポリアミド樹脂）を真空乾燥装置を用いて１２０℃で８時間以上乾燥を行った後、計量したもの］
実施例４のレーザー光透過性着色樹脂組成物用着色剤・・・・０．８０ｇ
【０１５１】
上記配合物をステンレス製タンブラーに入れ、１時間撹拌混合した。得られた混合物を、射出成形機（川口鉄鋼社製 商品名：Ｋ５０−Ｃ）を用いて、シリンダー温度２５０℃、金型温度６０℃で通常の方法で射出成形したところ、外観及び表面光沢が良好で色むらがない均一な黒色の試験片［４８×８６×３（ｍｍ）］を得た。
【０１５２】
実施例１４
６ナイロン・・・・４００ｇ［非強化６ナイロン（デュポン社製のポリアミド樹脂）を真空乾燥装置を用いて１２０℃で８時間以上乾燥を行った後、計量したもの］
実施例８のレーザー光透過性着色樹脂組成物用着色剤・・・・０．８０ｇ
【０１５３】
上記配合物をステンレス製タンブラーに入れ、１時間撹拌混合した。得られた混合物を、射出成形機（川口鉄鋼社製 商品名：Ｋ５０−Ｃ）を用いて、シリンダー温度２５０℃、金型温度６０℃で通常の方法で射出成形したところ、外観及び表面光沢が良好で色むらがない均一な黒色の試験片［４８×８６×３（ｍｍ）］を得た。
【０１５４】
実施例１５
６ナイロン・・・・４００ｇ［非強化６ナイロン（デュポン社製のポリアミド樹脂）を真空乾燥装置を用いて１２０℃で８時間以上乾燥を行った後、計量したもの］
製造例６のレーザー光透過性着色樹脂組成物用着色剤・・・・０．８０ｇ
【０１５５】
上記配合物をステンレス製タンブラーに入れ、１時間撹拌混合した。得られた混合物を、射出成形機（川口鉄鋼社製 商品名：Ｋ５０−Ｃ）を用いて、シリンダー温度２５０℃、金型温度６０℃で通常の方法で射出成形したところ、外観及び表面光沢が良好で色むらがない均一な黒色の試験片［４８×８６×３（ｍｍ）］を得た。
【０１５６】
実施例１６
ＰＥＴ・・・・４００ｇ［非強化ＰＥＴ（デュポン社製のポリエチレンテレフタレート樹脂）を真空乾燥装置を用いて１２０℃で８時間以上乾燥を行った後、計量したもの］
実施例１のレーザー光透過性着色樹脂組成物用着色剤・・・・０．８０ｇ
【０１５７】
上記配合物をステンレス製タンブラーに入れ、１時間撹拌混合した。得られた混合物を、射出成形機（川口鉄鋼社製 商品名：Ｋ５０−Ｃ）を用いて、シリンダー温度２８０℃、金型温度４０℃で通常の方法で射出成形したところ、外観及び表面光沢が良好で色むらがない均一な黒色の試験片［４８×８６×３（ｍｍ）］を得た。
【０１５８】
実施例１７
ＰＥＴ・・・・４００ｇ［非強化ＰＥＴ（デュポン社製のポリエチレンテレフタレート樹脂）を真空乾燥装置を用いて１２０℃で８時間以上乾燥を行った後、計量したもの］
実施例６のレーザー光透過性着色樹脂組成物用着色剤・・・・０．８０ｇ
【０１５９】
上記配合物をステンレス製タンブラーに入れ、１時間撹拌混合した。得られた混合物を、射出成形機（川口鉄鋼社製 商品名：Ｋ５０−Ｃ）を用いて、シリンダー温度２８０℃、金型温度４０℃で通常の方法で射出成形したところ、外観及び表面光沢が良好で色むらがない均一な黒色の試験片［４８×８６×３（ｍｍ）］を得た。
【０１６０】
実施例１８
ＰＰ・・・・４００ｇ（トクヤマ社製ポリプロピレン樹脂 商品名：ポリプロＰＮ５１０Ｔ）
製造例１のレーザー光透過性着色樹脂組成物用着色剤・・・・０．８０ｇ
【０１６１】
上記配合物をステンレス製タンブラーに入れ、１時間撹拌混合した。得られた混合物を、射出成形機（川口鉄鋼社製 商品名：Ｋ５０−Ｃ）を用いて、シリンダー温度２３０℃、金型温度４０℃で通常の方法で射出成形したところ、外観及び表面光沢が良好で色むらがない均一な黒色の試験片［４８×８６×３（ｍｍ）］を得た。
【０１６２】
実施例１９
ＰＣ・・・・４００ｇ（三菱エンジニアプラスチック社製ポリカーボネイト樹脂７０２０Ａ）
実施例１のレーザー光透過性着色樹脂組成物用着色剤・・・・０．８０ｇ
【０１６３】
上記配合物をステンレス製タンブラーに入れ、１時間撹拌混合した。得られた混合物を、ベント式押出機（エンプラ産業社製 商品名：Ｅ３０ＳＶ）を用いて混練し、溶融物を冷却水にて急冷させ、その後ペレタイザーにて切断し、チップを得た。
【０１６４】
このチップを用いて、射出成形機（川口鉄鋼社製 商品名：Ｋ５０−Ｃ）により、直径５０ｍｍ厚さ１．５ｍｍの円板を有する金型にて、シリンダー温度２８０℃、金型温度８０℃で成形を行ったところ、外観が良好で色相が均一な黒色のレーザー透過フィルターが得られた。
【０１６５】
実施例２０
６６ナイロン・・・・４００ｇ［非強化６６ナイロン（デュポン社製のポリアミド樹脂）を真空乾燥装置を用いて１２０℃で８時間以上乾燥を行った後、計量したもの］
製造例７のレーザー光透過性着色樹脂組成物用着色剤・・・・０．６７ｇ
製造例８のレーザー光透過性着色樹脂組成物用着色剤・・・・０．１３ｇ
【０１６６】
上記配合物をステンレス製タンブラーに入れ、１時間撹拌混合した。得られた混合物を、射出成形機（川口鉄鋼社製 商品名：Ｋ５０−Ｃ）を用いて、シリンダー温度２８０℃、金型温度６０℃で通常の方法で射出成形したところ、外観及び表面光沢が良好で色むらがない均一な黒色の試験片［４８×８６×３（ｍｍ）］を得た。
【０１６７】
実施例２１
ＰＥＴ・・・・４００ｇ［非強化ＰＥＴ（デュポン社製のポリエチレンテレフタレート樹脂）を真空乾燥装置を用いて１２０℃で８時間以上乾燥を行った後、計量したもの］
製造例７のレーザー光透過性着色樹脂組成物用着色剤・・・・０．６７ｇ
製造例８のレーザー光透過性着色樹脂組成物用着色剤・・・・０．１３ｇ
【０１６８】
上記配合物をステンレス製タンブラーに入れ、１時間撹拌混合した。得られた混合物を、射出成形機（川口鉄鋼社製 商品名：Ｋ５０−Ｃ）を用いて、シリンダー温度２８０℃、金型温度４０℃で通常の方法で射出成形したところ、外観及び表面光沢が良好で色むらがない均一な黒色の試験片［４８×８６×３（ｍｍ）］を得た。
【０１６９】
実施例２２
６６ナイロン・・・・４００ｇ［非強化６６ナイロン（デュポン社製のポリアミド樹脂）を真空乾燥装置を用いて１２０℃で８時間以上乾燥を行った後、計量したもの］
製造例９のレーザー光透過性着色樹脂組成物用着色剤・・・・０．５３ｇ
化合物例５−３のペリノン系染料・・・・０．１８ｇ
化合物例８−１のアントラキノン系染料・・・・０．０９ｇ
【０１７０】
上記配合物をステンレス製タンブラーに入れ、１時間撹拌混合した。得られた混合物を、射出成形機（川口鉄鋼社製 商品名：Ｋ５０−Ｃ）を用いて、シリンダー温度２８０℃、金型温度６０℃で通常の方法で射出成形したところ、外観及び表面光沢が良好で色むらがない均一な黒色の試験片［４８×８６×３（ｍｍ）］を得た。
【０１７１】
実施例２３
６ナイロン・・・・４００ｇ［非強化６ナイロン（デュポン社製のポリアミド樹脂）を真空乾燥装置を用いて１２０℃で８時間以上乾燥を行った後、計量したもの］
製造例１０のレーザー光透過性着色樹脂組成物用着色剤・・・・０．５３ｇ
化合物例５−３のペリノン系染料・・・・０．１８ｇ
化合物例８−１のアントラキノン系染料・・・・０．０９ｇ
【０１７２】
上記配合物をステンレス製タンブラーに入れ、１時間撹拌混合した。得られた混合物を、射出成形機（川口鉄鋼社製 商品名：Ｋ５０−Ｃ）を用いて、シリンダー温度２５０℃、金型温度６０℃で通常の方法で射出成形したところ、外観及び表面光沢が良好で色むらがない均一な黒色の試験片［４８×８６×３（ｍｍ）］を得た。
【０１７３】
実施例２４
６６ナイロン・・・・４００ｇ［非強化６６ナイロン（デュポン社製のポリアミド樹脂）を真空乾燥装置を用いて１２０℃で８時間以上乾燥を行った後、計量したもの］
製造例１１のレーザー光透過性着色樹脂組成物用着色剤・・・・０．５３ｇ
化合物例５−３のペリノン系染料・・・・０．１８ｇ
化合物例９−１のアントラキノン系染料・・・・０．０９ｇ
【０１７４】
上記配合物をステンレス製タンブラーに入れ、１時間撹拌混合した。得られた混合物を、射出成形機（川口鉄鋼社製 商品名：Ｋ５０−Ｃ）を用いて、シリンダー温度２８０℃、金型温度６０℃で通常の方法で射出成形したところ、外観及び表面光沢が良好で色むらがない均一な黒色の試験片［４８×８６×３（ｍｍ）］を得た。
【０１７５】
比較製造例１
化合物例１０−１のアントラキノン系酸性染料５０ｇを水５００ｍｌに分散させた。一方、水３００ｍｌに塩酸３０ｇとエタノールアミン１０ｇを溶解させた。この溶液を、室温で前記アントラキノン系酸性染料の分散液に滴下し、その混合液のｐＨを３．５に調整して１時間撹拌した。その反応混合液を濾過して濾取物を水洗したところ、得られたアントラキノン系造塩染料の収量は５４ｇ（収率９０％）であった。その後、イオンクロマトグラフ（日本ダイオネクス社製 ＤＸ−３００）にて、ガードカラム（イオンパック ＡＧ４Ａ−ＳＣ）と分離カラム（イオンパックＡＳ４Ａ―ＳＣ）を取り付け、得られたアントラキノン系造塩染料を少量のメタノールで溶かして水で希釈し、その上澄み液を注入して、カラム温度３５℃、流速１．５ｍｌ／ｍｉｎで無機塩を測定したところ、塩素イオン７．５％、硫酸イオン５．５％であった。
【０１７６】
比較例１
６ナイロン ・・・・４００ｇ［非強化６ナイロン（デュポン社製のポリアミド樹脂）を真空乾燥装置を用いて１２０℃で８時間以上乾燥を行った後、計量したもの］
式（１２−４）で表されるアントラキノン系染料・・・・０．５３ｇ
化合物例５−３のペリノン系染料・・・・０．１８ｇ
化合物例８−１のアントラキノン系染料・・・・０．０９ｇ
【０１７７】
【化７９】

・・・（１２−４）
【０１７８】
上記配合物をステンレス製タンブラーに入れ、１時間撹拌混合した。得られた混合物を、射出成形機（川口鉄鋼社製 商品名：Ｋ５０−Ｃ）を用いて、シリンダー温度２５０℃、金型温度６０℃で通常の方法で射出成形したところ、外観及び表面光沢が良好で色むらがない均一な黒色の試験片［４８×８６×３（ｍｍ）］を得た。
【０１７９】
比較例２
６ナイロン ・・・・ ４００ｇ［非強化６ナイロン（デュポン社製のポリアミド樹脂）を真空乾燥装置を用いて１２０℃で８時間以上乾燥を行った後、計量したもの］
式（１２−５）で表されるアントラキノン系染料・・・・０．５３ｇ
化合物例５−３のペリノン系染料・・・・０．１８ｇ
化合物例８−１のアントラキノン系染料 ・・・・０．０９ｇ
【０１８０】
【化８０】

・・・（１２−５）
【０１８１】
上記配合物をステンレス製タンブラーに入れ、１時間撹拌混合した。得られた混合物を、射出成形機（川口鉄鋼社製 商品名：Ｋ５０−Ｃ）を用いて、シリンダー温度２５０℃、金型温度６０℃で通常の方法で射出成形したところ、外観及び表面光沢が良好で色むらがない均一な黒色の試験片［４８×８６×３（ｍｍ）］を得た。
【０１８２】
比較例３
６ナイロン ・・・・ ４００ｇ［非強化６ナイロン（デュポン社製のポリアミド樹脂）を真空乾燥装置を用いて１２０℃で８時間以上乾燥を行った後、計量したもの］
式（１２−４）で表されるアントラキノン系染料・・・・０．５３ｇ
式（１２−６）で表されるモノアゾ含金染料・・・・０．１８ｇ
化合物例８−１のアントラキノン系染料・・・・０．０９ｇ
【０１８３】
【化８１】

・・・（１２−６）
【０１８４】
上記配合物をステンレス製タンブラーに入れ、１時間撹拌混合した。得られた混合物を、射出成形機（川口鉄鋼社製 商品名：Ｋ５０−Ｃ）を用いて、シリンダー温度２５０℃、金型温度６０℃で通常の方法で射出成形したところ、外観及び表面光沢が良好で色むらがない均一な黒色の試験片［４８×８６×３（ｍｍ）］を得た。
【０１８５】
比較例４
６ナイロン・・・・４００ｇ［非強化６ナイロン（デュポン社製のポリアミド樹脂）を真空乾燥装置を用いて１２０℃で８時間以上乾燥を行った後、計量したもの］
比較製造例１で得たアントラキノン系造塩染料・・・・０．５３ｇ
化合物例５−３のペリノン系染料・・・・０．１８ｇ
化合物例８−１のアントラキノン系染料・・・・０．０９ｇ
【０１８６】
上記配合物をステンレス製タンブラーに入れ、１時間撹拌混合した。得られた混合物を、射出成形機（川口鉄鋼社製 商品名：Ｋ５０−Ｃ）を用いて、シリンダー温度２５０℃、金型温度６０℃で通常の方法で射出成形したところ、成形中に発泡が生じ、色むらがある黒色の試験片［４８×８６×３（ｍｍ）］を得た。
【０１８７】
比較例５
ＰＥＴ・・・・４００ｇ［非強化ＰＥＴ（デュポン社製のポリエチレンテレフタレート樹脂）を真空乾燥装置を用いて１２０℃で８時間以上乾燥を行った後、計量したもの］
式（１２−４）で表されるアントラキノン系染料・・・・０．５３ｇ
化合物例５−３のペリノン系染料・・・・０．１８ｇ
化合物例８−１のアントラキノン系染料・・・・０．０９ｇ
【０１８８】
上記配合物をステンレス製タンブラーに入れ、１時間撹拌混合した。得られた混合物を、射出成形機（川口鉄鋼社製 商品名：Ｋ５０−Ｃ）を用いて、シリンダー温度２８０℃、金型温度４０℃で通常の方法で射出成形したところ、色相が赤紫色系の試験片［４８×８６×３（ｍｍ）］を得た。
【０１８９】
比較例６
ＰＥＴ・・・・４００ｇ［非強化ＰＥＴ（デュポン社製のポリエチレンテレフタレート樹脂）を真空乾燥装置を用いて１２０℃で８時間以上乾燥を行った後、計量したもの］
式（１２−５）で表されるアントラキノン系染料・・・・０．５３ｇ
化合物例５−３のペリノン系染料・・・・０．１８ｇ
化合物例８−１のアントラキノン系染料・・・・０．０９ｇ
【０１９０】
上記配合物をステンレス製タンブラーに入れ、１時間撹拌混合した。得られた混合物を、射出成形機（川口鉄鋼社製 商品名：Ｋ５０−Ｃ）を用いて、シリンダー温度２８０℃、金型温度４０℃で通常の方法で射出成形したところ、色相が緑色系の試験片［４８×８６×３（ｍｍ）］を得た。
【０１９１】
比較例７
ＰＰ・・・・４００ｇ（トクヤマ社製ポリプロピレン樹脂 商品名：ポリプロＰＮ５１０Ｔ）
式（１２−４）で表されるアントラキノン系染料・・・・０．８０ｇ
【０１９２】
上記配合物をステンレス製タンブラーに入れ、１時間撹拌混合した。得られた混合物を、射出成形機（川口鉄鋼社製 商品名：Ｋ５０−Ｃ）を用いて、シリンダー温度２３０℃、金型温度４０℃で通常の方法で射出成形したところ、外観及び表面光沢が良好で色むらがない均一な黒色の試験片［４８×８６×３（ｍｍ）］を得た。
【０１９３】
比較例８
ＰＣ・・・・４００ｇ（三菱エンジニアプラスチック社製ポリカーボネイト樹脂７０２０Ａ）
式（１２−４）で表されるアントラキノン系染料・・・・０．５３ｇ
化合物例５−３のペリノン系染料・・・・０．１８ｇ
化合物例８−１のアントラキノン系染料・・・・０．０９ｇ
【０１９４】
上記配合物をステンレス製タンブラーに入れ、１時間撹拌混合した。得られた混合物を、ベント式押出機（エンプラ産業社製 商品名：Ｅ３０ＳＶ）を用いて混練し、溶融物を冷却水にて急冷させ、その後ペレタイザーにて切断し、チップを得た。
【０１９５】
このチップを用い、射出成形機（川口鉄鋼社製 商品名：Ｋ５０−Ｃ）により、直径５０ｍｍ厚さ１．５ｍｍの円板を有する金型にて、シリンダー温度２８０℃、金型温度８０℃で成形を行ったところ、色相が不均一な赤紫色系のレーザー透過フィルターを得た。
【０１９６】
実施例９乃至２４並びに比較例１乃至８で得たレーザー光透過性着色樹脂組成物について、下記方法により物性評価を行った。その結果を後記表９及び表１０並びに図１乃至図７に示す。
【０１９７】
（１）透過率測定
分光光度計（ＨＩＴＡＣＨＩ社製 Ｕ−３４１０形）に紫外可視近赤外域用の６０φ積分球装置を取り付け、試験片をセットして、波長範囲λ＝４００乃至１２００ｎｍで透過率Ｔを測定した。実施例１１の試験片、比較例１の試験片、及び非着色樹脂（実施例１１に用いた６ナイロン）の試験片についての透過率チャートを、それぞれ図１、図２及び図３に示す。
【０１９８】
本発明においては、波長λ＝９５０ｎｍのレーザー光（半導体レーザーの領域）と、波長λ＝１０５０ｎｍのレーザー光（ＹＡＧレーザーの領域）における透過率Ｔに着目し、次式の透過率比を判断の目安とした。なお、Ｔ_Ｂは波長λ＝９５０ｎｍのレーザー光についての透過率比である。
Ｔ_Ａ＝Ｔ_{９５０ｎｍ}／Ｔ_{１０５０ｎｍ}
Ｔ_Ｂ＝Ｔ_着色樹脂／Ｔ_{非着色樹脂}
【０１９９】
（２）外観試験と評価
外観については、透過・反射兼用濃度計（マクベス社製 商品名：ＴＲ−９２７）を用いて試験片の反射濃度（ＯＤ値）を測定した。
【０２００】
一般に、反射濃度（ＯＤ値）が高いものの方が、より表面の平滑性が高く、表面光沢が豊富であると判断される。
【０２０１】
（３）耐光性試験と評価
キセノンウェザメーター（東洋精機社製 商品名：アトラスＣＩ−４０００）を用い、下記００６の試験条件のサイクル［フェーズ１とフェーズ２の繰り返し］で、試験片に対し２００時間の照射を行った。その照射後の試験片と照射前の試験片との色差ΔＥを、分光色差計（ＪＵＫＩ社製 商品名：ＪＰ７０００）を用いて測定した。
【０２０２】

【０２０３】
一般に、色差ΔＥが大きいものの方が、試験片の色相の変退色がより進んでいるものと判断される。
【０２０４】
(4)熱安定性試験
オーブンに試験片を入れて１６０℃で２４０時間放置し、２４０時間後の試験片とオーブンに入れる前の試験片との色差ΔＥを、分光色差計（ＪＵＫＩ社製 商品名：ＪＰ７０００）を用いて測定した。
【０２０５】
一般に、色差ΔＥが高いものの方が、試験片の色相の変退色がより進んでいるものと判断される。
【０２０６】
(5)耐湿試験
恒温槽に試験片を入れて８０℃、湿度９５％で１週間放置した後の試験片と恒温槽に入れる前の試験片との色差ΔＥを、分光色差計（ＪＵＫＩ社製 商品名：ＪＰ７０００）を用いて測定した。
【０２０７】
一般に、色差ΔＥが大きいものの方が、試験片中の着色剤の表面析出の程度が大きいものと判断される。
【０２０８】
(6)熱分析（ＴＧ／ＤＴＡ）試験
ＴＧ／ＤＴＡ測定器（セイコーインスツルメンツ社製 商品名：ＳＩＩ ＥＸＳＴＡＲ６０００）を用い、Ａｉｒ（空気）で２００ｍｌ／分の雰囲気下、３０乃至５５０℃は昇温速度１０℃／分、５５０℃到達後２８分間は５５０℃の定温状態として試料（着色剤）について測定を行った。
【０２０９】
実施例１のレーザー光透過性着色樹脂組成物用着色剤（着色剤例１）のＴＧ／ＤＴＡチャートを図４に、製造例１のアントラキノン系造塩染料（化合物例１）のＴＧ／ＤＴＡチャートを図５に、比較例１の着色剤のＴＧ／ＤＴＡチャートを図６に、式（１２−４）で表されるアントラキノン系染料のＴＧ／ＤＴＡチャートを図７に、それぞれ示す。
【０２１０】
ＴＧ／ＤＴＡのチャートにおいて、２００乃至３００℃の間に吸熱ピークを含んでいると、成形機中で色素の結合が切断されてそれが耐湿試験において表面析出となって現れ、またこの温度範囲に発熱ピークを含んでいると、色素が分解されて樹脂に悪影響を及ぼすものと推測される。
【０２１１】
(7)耐溶剤試験
試験片をエタノール中に完全に浸した状態で密閉して恒温槽中で４０℃で４８時間放置した後の試験片と試験前の試験片との色差、並びに試験後のエタノールと試験前のエタノールとの色差ΔＥを、分光色差計（ＪＵＫＩ社製 商品名：ＪＰ７０００）を用いて測定した。
【０２１２】
試験片の色差ΔＥが高いほど、試験片中の着色剤の一部が溶け出し、それがエタノール中に拡散してエタノールの色差ΔＥとなって現れるものと推測される。
【０２１３】
【表９】

【０２１４】
【表１０】

【図面の簡単な説明】
【図１】実施例１１の試験片についての透過率チャートである。
【図２】比較例１の試験片についての透過率チャートである。
【図３】非着色樹脂の試験片についての透過率チャートである。
【図４】実施例１のレーザー光透過性着色樹脂組成物用着色剤（着色剤例１）のＴＧ／ＤＴＡチャートである。
【図５】製造例１のアントラキノン系造塩染料（化合物例１）のＴＧ／ＤＴＡチャートである。
【図６】比較例１の着色剤のＴＧ／ＤＴＡチャートである。
【図７】式（１２−４）で表されるアントラキノン系染料のＴＧ／ＤＴＡチャートである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a colorant for a laser light-transmitting colored resin composition, a laser light-transmitting colored resin composition, a laser light-transmitting color filter, and a laser light-transmitting color film, in particular, a laser beam of a semiconductor laser or a YAG laser. Colorant for laser light transmitting colored resin composition, laser light transmitting colored resin composition, laser light transmitting color filter, and laser light transmitting color Related to film.
[0002]
[Prior art and problems to be solved by the invention]
Typical examples of lasers include gas lasers, solid lasers, liquid lasers, YAG lasers (for example, wavelength 1064 nm), semiconductor lasers (for example, wavelengths 808, 820, 840, and 940 nm). . In recent years, as laser devices become cheaper, their applications have been expanded. Under such circumstances, it is important to use laser light having a wavelength from around 800 nm by a semiconductor laser to around 1100 nm by a YAG laser, and it is actively used or attempted to be used.
[0003]
For example, dyes that absorb semiconductor laser light are used as optical recording materials in electronic components such as certain electronic substrates and optical recording media such as optical disks. In such a case, in order to absorb only the target wavelength with high sensitivity, for example, it may be necessary to exhibit a filter effect that cuts visible light and transmits only the target wavelength. In addition, it may be necessary to increase the commercial value by coloring electronic components and optical recording media. For these purposes, attempts have been made to provide various laser light transmissive colored resin compositions colored with synthetic resins.
[0004]
Anthraquinone dyes are attracting attention as such pigments.
For example, as an example using an anthraquinone oil-soluble dye, a synthetic resin light filter composition using Solvent Green 23 (JP-A No. 54-159453), a near-infrared transmission filter using Solvent Green 20 Resin composition (JP 59-23307, JP 60-184541), infrared transmission filter (JP 55-62410) containing 4 kinds of anthraquinone dye, anthraquinone blue Examples thereof include blue dyes for filters which are dyes (JP-A-62-197459). However, since these anthraquinone dyes have difficulty in heat resistance, when blended with a synthetic resin and molded, especially in the case of engineering plastic molding, which is a molding condition at high temperatures, a decomposition product of the dye is generated. It is likely to cause discoloration and deterioration of physical properties. Moreover, the migration resistance and chemical resistance are insufficient, and the practicality is poor.
[0005]
Examples of using anthraquinone acid dyes or derivatives thereof include color filters using an anthraquinone acid dye alkylammonium salt as a thermosetting resin (Japanese Patent Laid-Open No. 5-333207) or a water solution of a specific anthraquinone compound. Salt and a color filter dyed thereby (JP-A-8-73758). These anthraquinone dyes are monoalkylamine or alkanolamine salts and have water solubility or hygroscopicity. Therefore, it is difficult to say that these are suitable for blending and coloring in a thermoplastic resin that dislikes moisture. That is, the miscibility with a thermoplastic resin is low, and when it is blended with a thermoplastic resin and molded, it tends to foam and it is difficult to obtain a molded product with high transparency.
[0006]
The present invention has been made in view of the above-mentioned problems existing in the prior art, and its object is to transmit laser light having a wavelength from about 800 nm by a semiconductor laser to about 1100 nm by a YAG laser. Colorant for laser light-transmitting colored resin composition, which has high properties, high fastness such as heat resistance and light resistance, good migration resistance and chemical resistance, etc. An object of the present invention is to provide a laser light transmitting colored resin composition colored with an agent, a laser light transmitting color filter and a laser light transmitting color film comprising the colored resin composition.
[0007]
[Means for Solving the Problems]
The colorant for laser light transmitting colored resin composition of the present invention that achieves the above object comprises at least one anthraquinone salt-forming dye represented by the following formulas (1) to (3). It is.
[0008]
The anthraquinone salt-forming dye represented by the formula (1) is as follows.
Embedded image

... (1)
[In Formula (1),
R², R³And R⁵Independently of one another, hydrogen, or
Embedded image

.... (1-a)
Indicate
R¹And R⁴Each independently represents hydrogen, an alkyl group, an alkenyl group, an alkoxy group, an amino group, a hydroxyl group, a halogen, or a sulfonic acid group;
X¹Represents O or NH;
R⁶, R⁷, R⁸, R⁹, R¹⁰And R¹¹Each independently represents hydrogen, an alkyl group, an alkenyl group, an alkoxy group, an amino group, a hydroxyl group, or a halogen;
[L]^{b +}Represents a cation or a quaternary organic ammonium ion derived from at least one amine selected from the group consisting of aliphatic diamine derivatives, rosin amine derivatives, guanidine derivatives, aromatic amine derivatives, and aromatic diamine derivatives;
n¹Represents an integer from 0 to 4,
n³Represents an integer from 0 to 4,
m¹Represents an integer from 1 to 6,
a represents an integer of 1 to 4,
b represents 1 or 2,
K²Represents an integer of 1 to 6. ]
[0009]
The anthraquinone salt-forming dye represented by the formula (2) is as follows.
Embedded image

... (2)
[In Formula (2),
R⁴⁷, R⁴⁸, R⁴⁹, R⁵⁰, R⁵¹And R⁵²Are independently of each other hydrogen, alkyl group, aryl group, alkenyl group, alkoxy group, amino group, N-alkylamide group, N-arylamide group, hydroxyl group, halogen, acyl group, acyloxy group, acylamide group, acyl group. -N-alkylamide group, carboxyl group, alkoxylcarbonyl group, or sulfonic acid group, R⁴⁷To R⁵²At least one of which represents a sulfonic acid group,
The connector J represents the following formula (2-a) or (2-b),
Embedded image

... (2-a)
Or
Embedded image

... (2-b)
(F)^{h +}Represents a cation or a quaternary organic ammonium ion derived from at least one amine selected from the group consisting of aliphatic diamine derivatives, rosin amine derivatives, guanidine derivatives, aromatic amine derivatives, and aromatic diamine derivatives;
m⁴Represents an integer from 1 to 6,
h represents 1 or 2,
K³Represents an integer from 1 to 6,
R⁵³And R⁵⁴Independently of one another represent hydrogen or an alkyl group. ]
[0010]
The anthraquinone salt-forming dye represented by the formula (3) is as follows.
Embedded image

... (3)
[In Formula (3),
R⁵⁸, R⁵⁹And R⁶⁰Each independently represents hydrogen, an alkyl group, an alkenyl group, an alkoxy group, an amino group, a hydroxyl group, a halogen, a cyclohexylamide group, or a sulfonic acid group,
X²Represents O or NH;
R⁵⁵, R⁵⁶And R⁵⁷Are independently of each other hydrogen, alkyl group, aryl group, alkenyl group, alkoxy group, amino group, N-alkylamide group, N-arylamide group, hydroxyl group, halogen, cyano, acyl group, acyloxy group, acylamide group. An acyl-N-alkylamide group, a carboxyl group, an alkoxylcarbonyl group, or a sulfonic acid group;
[T]^{Z +}Represents a cation or a quaternary organic ammonium ion derived from at least one amine selected from the group consisting of aliphatic diamine derivatives, rosin amine derivatives, guanidine derivatives, aromatic amine derivatives, and aromatic diamine derivatives;
m²Represents an integer from 1 to 6,
y represents an integer of 1 to 4,
Z represents 1 or 2,
K⁴Represents an integer of 1 to 6. ]
[0011]
The anthraquinone salt-forming dye in the present invention can be obtained, for example, by reacting an anthraquinone acid dye with an organic amine. Specifically, it can be obtained by an ionic reaction [partially mixed] between an anion caused by a sulfonic acid group in an anthraquinone acid dye and an ammonium ion caused by an organic amine.
[0012]
In addition, the colorant for the laser light transmitting colored resin composition of the present invention is preferably [l] in the above formula (1).^{b +}(F) in the above formula (2)^{h +}[T] in the above formula (3)^{Z +}Is a cation represented by the following formula (4-a) or (4-b).
Embedded image

... (4-a)
[In the formula (4-a),
R⁴⁰And R⁴¹Are independent of each other, N⁺H₃Or NH₂R⁴⁰And R⁴¹Is at least one N⁺H₃Indicates
n²Represents an integer of 1 to 12. ]
Embedded image

... (4-b)
[In the formula (4-b),
R⁴², R⁴³And R⁴⁴Each independently represents an alkyl group having 1 to 18 carbon atoms or an aryl group,
R⁴⁵Represents a substituted or unsubstituted aryl group or benzyl group. ]
[0013]
The anthraquinone salt-forming dyes represented by the above formulas (1) to (3) having a phenyl group having a sulfonic acid group on the benzene ring of the anthraquinone skeleton, when blended with a thermoplastic resin such as a polyamide resin, The resin composition exhibits good moldability, hue, blooming resistance, and bleed resistance, heat resistance in a resin molding temperature range of 200 ° C. or higher, and from around 800 nm by a semiconductor laser. It excels in the transmittance of laser light having a wavelength near 1100 nm by a YAG laser.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
The anthraquinone salt-forming dye in the present invention includes, for example, an anthraquinone acid dye represented by the following formula (10) and an organic amine (aliphatic diamine derivative, alicyclic amine derivative, guanidine derivative, aromatic amine, or aromatic diamine). Derivative) can be obtained by reaction (ionic reaction). A known ionic reaction can be used for this chlorination reaction.
[0015]
Embedded image

... (10)
[0016]
[In the formula (10),
R², R³And R⁵Are independently of each other (ie may be the same or different), hydrogen, or
Embedded image

... (10-a)
Indicate
R¹And R⁴Each independently represents hydrogen, an alkyl group, an alkenyl group, an alkoxy group, an amino group, a hydroxyl group, a halogen, or a sulfonic acid group;
X¹Represents O or NH;
R⁶, R⁷, R⁸, R⁹, R¹⁰And R¹¹Each independently represents hydrogen, an alkyl group, an alkenyl group, an alkoxy group, an amino group, a hydroxyl group, or a halogen;
n¹Represents an integer from 0 to 4,
n³Represents an integer of 0 to 4. ]
[0017]
R in the above formulas (1) and (10)¹, R⁴, R⁶, R⁷, R⁸, R⁹, R¹⁰Or R¹¹Specific examples of the alkyl group, alkenyl group, alkoxy group, and halogen represented by are as follows. That is, an alkyl group having 1 to 22 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, undecyl, dodecyl, etc .; vinyl, allyl, propenyl, butenyl, isobutenyl, etc. An alkenyl group having 2 to 8 carbon atoms; an alkoxy group having an optionally branched alkyl having 1 to 18 carbon atoms such as methoxy, ethoxy, propoxy and butoxy; and a halogen such as F, Cl and Br.
[0018]
The following examples can be given as specific examples of the anthraquinone acid dye represented by the above formula (10). However, of course, the present invention is not limited to these.
[0019]
Embedded image

Compound Example 10-1
[0020]
Embedded image

Compound Example 10-2
[0021]
Embedded image

Compound Example 10-3
[0022]
Embedded image

Compound Example 10-4
[0023]
Embedded image

Compound Example 10-5
[0024]
Embedded image

Compound Example 10-6
[0025]
Embedded image

Compound Example 10-7
[0026]
Embedded image

Compound Example 10-8
[0027]
Embedded image

Compound Example 10-9
[0028]
Embedded image

Compound Example 10-10
[0029]
Embedded image

Compound Example 10-11
[0030]
Embedded image

Compound Example 10-12
[0031]
Embedded image

Compound Example 10-13
[0032]
Embedded image

Compound Example 10-14
[0033]
Examples of organic amines that can be used in the chlorination reaction to obtain anthraquinone salt-forming dyes in the present invention include aliphatic diamine derivatives, alicyclic amine derivatives, guanidine derivatives, aromatic amine derivatives, and aromatic diamine derivatives. Can do. More specifically, aliphatic diamine derivatives such as ethylenediamine, tetramethylenediamine and hexamethylenediamine; alicyclic amines such as rosinamine (excluding cyclohexylamine); 1,3-diphenylguanidine, 1-o-tolylguanidine, Examples include guanidine derivatives such as di-o-tolylguanidine and guanidine; aromatic amine derivatives such as aniline, benzylamine, naphthylamine, phenylamine, phenylenediamine, methylphenylenediamine, and xylenediamine, or aromatic diamine derivatives.
The quaternary organic ammonium ion in the anthraquinone salt-forming dye of the present invention includes N-tetramethylammonium ion, N-tetrabutylammonium ion, N-tetraoctylammonium ion, N-tributyl-N-octylammonium ion, N -Trimethyl-N-dodecyl ammonium ion, N-tributyl-N-dodecyl ammonium ion, N-tributyl-N-phenyl ammonium ion, N-trimethyl-N-benzyl ammonium ion, N-tributyl-N-benzyl ammonium ion, N -Trioctyl-N-benzylammonium ion, N-triphenyl-N-benzylammonium ion and the like.
[0034]
The anthraquinone salt-forming dyes represented by the above formulas (1) to (3) in the present invention are derived from the number of anions attributed to the sulfonic acid group in the anthraquinone acid dye and the amino group in the aliphatic diamine. Depending on the number of ammonium ions, various bonding structures can be taken.
[0035]
The anthraquinone salt-forming dyes in the present invention represented by the above formulas (1) to (3) are excellent in laser beam transmissivity at the wavelength of the laser beam of the semiconductor laser and YAG laser, and have a laser beam wavelength of 950 nm and a wavelength of The laser beam of 1050 nm maintains a constant high transmittance. T which is the transmittance of laser light having a wavelength of 950 nm in the anthraquinone salt-forming dyes represented by the above formulas (1) to (3)_950nmAnd T which is the transmittance of laser light having a wavelength of 1050 nm_1050nmThe ratio of T_950nm/ T_1050nmIs 0.8 to 1.2, preferably 0.9 to 1.1.
[0036]
The anthraquinone salt-forming dyes represented by the above formulas (1) to (3) are thermally analyzed using a TG / DTA measuring instrument (trade name: SII EXSTAR6000, manufactured by Seiko Instruments Inc.) and 200 ml / air. Thermal analysis performed at a constant temperature of 550 ° C. for 28 minutes after reaching a temperature increase rate of 10 ° C./min at 550 ° C. in an atmosphere of 30 minutes to 550 ° C. ], It is preferable that neither an exothermic peak nor an endothermic peak is exhibited between 200 ° C and 300 ° C. Between 200 ° C. and 300 ° C. is the temperature at which the resin is melted during molding, so that the dye is decomposed or impurities are generated during this period, resulting in a decrease in the colorability, transparency, mechanical properties, etc. of the molded resin. Occurs. The anthraquinone salt-forming dyes represented by the above formulas (1) to (3) preferably exhibit a decomposition temperature of 330 ° C. or higher in the thermal analysis.
[0037]
The anthraquinone salt-forming dyes represented by the above formulas (1) to (3) have a hue such as blue, purple, or green. In the colorant of the present invention, any one of the anthraquinone salt-forming dyes represented by the above formulas (1) to (3) having various hues may be used alone or in combination of two or more thereof. Furthermore, it has an absorption range only outside or within the visible light absorption range of the anthraquinone salt-forming dyes represented by the above formulas (1) to (3), and transmits through 800 nm to 1200 nm. One or a combination of two or more dyes having properties can be used.
[0038]
A black dye having a single black color tends to have absorption between 700 nm and 900 nm. Such black dyes presently present are difficult to use as a colorant for laser light transmission because they absorb near the wavelength of the laser light of a semiconductor laser. Therefore, a colorant that is combined with a single dye that does not exhibit black and is color-tuned to exhibit black is important. For example, by combining an anthraquinone salt-forming dye represented by the above formulas (1) to (3) with a red dye such as a dye represented by the following formulas (5) to (7) or a yellow dye, The colorant of the present invention that exhibits a black color can be produced. The use ratio of each dye can be appropriately adjusted according to the hue of the dye used, the resin used, the use concentration (or resin thickness), and the like.
[0039]
The anthraquinone salt-forming dyes represented by the above formulas (1) to (3) are low in water solubility and exhibit behavior (physical properties) close to that of oil-soluble dyes. The anthraquinone salt-forming dye is more preferably a poorly water-soluble dye. Dyes with low water solubility, more preferably poorly water-soluble dyes, can contain less water, so that inconvenient phenomena such as foaming hardly occur when blended with a synthetic resin such as a thermoplastic resin and molded. A molded article having a good surface appearance and high transparency is easily obtained.
[0040]
The inorganic salt of the colorant of the present invention is preferably 2% by weight or less. More preferably, it is 1 weight%, More preferably, it is 0.5 weight% or less. When the inorganic salt that can be contained in the dye is mixed in the resin composition, the growth of crystals is inhibited, and when it is large, the resin molded product tends to cause cracks and deterioration of mechanical properties. Examples of such inorganic salts include chlorides, sulfates and hydroxides of alkali metals (Li, Na, K, etc.) and alkaline earth metals (Ba, Ca, Sr, etc.).
[0041]
About the dye used for the coloring agent of this invention, it is necessary to remove | eliminate sufficiently the produced | generated salt, the catalyst used for reaction, etc. except the metal in the raw material of dye. Further, in the aqueous reaction, it is preferable to prevent mixing of Ca, Fe, etc. by reacting with ion exchange water from which metals such as industrial water and tap water are removed.
[0042]
Specific examples of the anthraquinone salt-forming dyes represented by the above formula (1) in the present invention include anthraquinone salt-forming dyes obtained by reacting the anthraquinone acid dyes and organic amines shown in Tables 1 and 2. be able to. However, of course, the present invention is not limited to these.
[0043]
[Table 1]

[0044]
[Table 2]

[0045]
Specific examples of the anthraquinone salt-forming dyes represented by the above formula (2) include those shown in Table 3. However, of course, the present invention is not limited to these.
[0046]
[Table 3]

[0047]
Specific examples of the anthraquinone salt-forming dyes represented by the above formula (3) include those shown in Table 4. However, of course, the present invention is not limited to these.
[0048]
[Table 4]

[0049]
As a dye that can be mixed with the anthraquinone salt-forming dyes represented by the above formulas (1) to (3) to constitute the colorant of the present invention, or only outside the visible light absorption range of the anthraquinone salt-forming dyes or In the following, dyes having an absorption range other than that range and having transparency at 800 nm to 1200 nm will be described.
[0050]
The colorant for laser light transmitting colored resin composition of the present invention preferably contains a perinone dye / pigment represented by the following formula (5). Since the perinone skeleton of the formula (5) is a robust skeleton, it is easy to form a fast dye having good thermal stability. Moreover, the resin moldability and hue when blended with a thermoplastic resin are good. In particular, it is useful because there are few dyes having high fastness as red dyes.
[0051]
Embedded image

... (5)
[0052]
[In Formula (5),
m³Indicates 1 or 2,
A and B each independently represent one of the following formulas (5-a) to (5-c):
[0053]
Embedded image

... (5-a)
[0054]
Embedded image

... (5-b)
[0055]
Embedded image

... (5-c)
[In the formulas (5-a) to (5-c), R¹²To R²⁷Are independently of each other hydrogen, halogen (for example, F, Cl, Br, etc.), an alkyl group (an alkyl group having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, etc.), an alkoxy group (Alkoxy group optionally having 1 to 18 carbon atoms such as methoxy, ethoxy, propoxy, butoxy), aralkyl group (for example, benzyl, α, α-dimethylbenzyl, cumyl, toluyl, phenethyl, etc.) or aryl group (For example, phenyl and naphthyl). ]
[0056]
Examples of such perinone dyes and pigments include the following dyes and pigments described in COLOR INDEX:
C. I. Solvent Orange 60, 78, C.I. I. Orange dyes such as Vat Orange 15;
C. I. Solvent Red 135, 162, 178, 179, C.I. I. Red dyes such as Vat Red 7;
C. I. Purple dye such as Solvent Violet 29
Can be mentioned.
[0057]
Specific examples of the perinone dyes represented by the above formula (5) include those shown in Table 5. However, of course, the present invention is not limited to these.
[0058]
[Table 5]

[0059]
In consideration of the compatibility with the synthetic resin such as the thermoplastic resin and the good dispersibility, a dye is more preferable among such perinone dyes and pigments.
[0060]
Moreover, it is preferable that the colorant for laser light transmitting colored resin composition of the present invention contains an anthrapyridone salt-forming dye represented by the following formula (6). The anthrapyridone salt-forming dye of the formula (6) is a robust dye having good heat stability, high compatibility with the resin, and good resin moldability and hue when blended with a thermoplastic resin. . Particularly important as a red dye.
[0061]
Embedded image

... (6)
[In Formula (6),
R⁶⁸, R⁶⁹, R⁷⁰And R⁷¹Independently of one another, hydrogen, an alkyl group (for example, an alkyl group having preferably 1 to 5 carbon atoms such as methyl, ethyl, propyl, iso-propyl, n-butyl, tert-butyl, etc.), an aryl group (for example, phenyl, It may be nucleus-substituted by lower alkyl having 1 to 3 carbon atoms such as naphthyl, lower alkyl-substituted phenyl, lower alkyl-substituted naphthyl, halogenated phenyl, halogenated naphthyl or the like, or halogen such as chlorine, bromine, iodine, or fluorine. Aryl group), alkenyl group (for example, alkenyl group having 2 to 18 carbon atoms such as vinyl group, allyl group, propenyl group, butenyl group), alkoxy group (for example, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy) Preferably an alkoxy group having 1 to 18 carbon atoms), an amino group, a hydroxyl group, Logene (for example, chlorine, bromine, iodine, fluorine, etc.), acyl group (for example, formyl, acetyl, propionyl, butyryl, valeryl, benzoyl, toluoyl, etc.), acyloxy group, acylamide group, acyl-N-alkylamide group, carboxyl group, An alkoxycarbonyl group, a cyclohexylamide group, a sulfonic acid group, or
[0062]
Embedded image

... (6-a)
[0063]
R⁶⁸To R⁷¹At least one of which represents a sulfonic acid group, and R⁶⁷Represents hydrogen, alkyl group, aryl group, alkoxy group, amino group, hydroxyl group, or halogen;
P¹Is C-R⁷²Or N,
R⁷²Represents hydrogen, an alkyl group (for example, an alkyl group having 1 to 5 carbon atoms such as methyl, ethyl, propyl, iso-propyl, n-butyl, tert-butyl), an alkoxy group (for example, methoxy, ethoxy, propoxy, butoxy). , Pentyloxy, hexyloxy, etc., preferably an alkoxy group having 1 to 18 carbon atoms), amino group, hydroxyl group, halogen (eg, chlorine, bromine, iodine, fluorine, etc.), carboxyl group, substituted or unsubstituted aryl group (eg, Nuclearly substituted with lower alkyl having 1 to 3 carbon atoms such as phenyl, naphthyl, lower alkyl-substituted phenyl, lower alkyl-substituted naphthyl, halogenated phenyl, halogenated naphthyl, etc. or halogen such as chlorine, bromine, iodine, fluorine, etc. Aryl group), substituted (lower alkyl having 1 to 3 carbon atoms or chlorine), Nuclear substitution with halogen such as elemental, iodine or fluorine) or unsubstituted aralkyl group, or substitution (nuclear substitution with lower alkyl having 1 to 3 carbon atoms or halogen such as chlorine, bromine, iodine or fluorine) or unsubstituted Benzoyl group of
(G)^{S +}Represents a cation or a quaternary organic ammonium ion derived from at least one amine selected from the group consisting of aliphatic diamine derivatives, rosin amine derivatives, guanidine derivatives, aromatic amine derivatives, and aromatic diamine derivatives;
S represents 1 or 2,
m⁵Represents an integer from 1 to 4,
K⁵Indicates 1 or 2,
P²Represents O or NH;
R⁷³, R⁷⁴And R⁷⁵Independently of one another, hydrogen, an alkyl group (for example, an alkyl group having preferably 1 to 5 carbon atoms such as methyl, ethyl, propyl, iso-propyl, n-butyl, tert-butyl, etc.), an aryl group (for example, phenyl, It may be nucleus-substituted by lower alkyl having 1 to 3 carbon atoms such as naphthyl, lower alkyl-substituted phenyl, lower alkyl-substituted naphthyl, halogenated phenyl, halogenated naphthyl or the like, or halogen such as chlorine, bromine, iodine, or fluorine. Aryl group), alkenyl group (for example, alkenyl group having 2 to 18 carbon atoms such as vinyl group, allyl group, propenyl group, butenyl group), alkoxy group (for example, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy) Preferably an alkoxy group having 1 to 18 carbon atoms), an amino group, a hydroxyl group, Logene (for example, chlorine, bromine, iodine, fluorine, etc.), acyl group (for example, formyl, acetyl, propionyl, butyryl, valeryl, benzoyl, toluoyl, etc.), acyloxy group, acylamide group, acyl-N-alkylamide group, carboxyl group, An alkoxycarbonyl group, a cyclohexylamide group, or a sulfonic acid group is shown. ]
[0064]
Specific examples of the anthrapyridone salt-forming dyes represented by the above formula (6) include those shown in Table 6. In these compound examples, m in the formula (6)⁵Indicates 1. However, of course, the present invention is not limited to these.
[0065]
[Table 6]

[0066]
The colorant for laser beam transmitting colored resin composition of the present invention preferably contains a monoazo metal-containing dye represented by the following formula (7). Since the monoazo metal-containing dye of the formula (7) has a fast skeleton, it is easy to form a fast dye having good thermal stability, and the decomposition temperature of the dye in the thermal analysis is about 300 ° C. or higher. Moreover, the resin moldability and hue when blended with a thermoplastic resin are good. In particular, it is useful because there are few dyes having high fastness as yellow to red dyes.
[0067]
Embedded image

... (7)
[0068]
[In formula (7), K¹Represents 0, 1, or 2,
(D)^{r +}Is based on hydrogen ions, cations due to alkali metals (Li, Na, K, etc.), ammonium ions, organic amines (aliphatic primary amines, aliphatic secondary amines, aliphatic tertiary amines, etc.) Represents a cation or a quaternary organic ammonium ion,
m⁴Represents 0, 1, or 2, r represents 1 or 2, X represents 1 or 2,
L₁And L₃Independently of one another represents O or COO;
L₂And L₄Indicates O,
M¹Represents a divalent to tetravalent metal (Cr, Co, Cu, Ni, Al, etc.),
R²⁸And R²⁹Independently of one another, hydrogen, Cl, SO₂R³⁰Or
Embedded image

Indicate
R³⁰Represents a linear or branched alkyl group (for example, an alkyl group having 1 to 4 carbon atoms),
R³¹And R³²Each independently represents hydrogen or a linear or branched alkyl group (for example, an alkyl group having 1 to 4 carbon atoms);
B¹And B²Are independent of each other,
Embedded image

... (8)
Or
Embedded image

... (9)
Indicate
R³³And R³⁵Independently of one another, hydrogen, Cl, SO₂R³⁷Or
Embedded image

Indicate
R³⁷Represents a linear or branched alkyl group (for example, an alkyl group having 1 to 4 carbon atoms), and the R³⁸And R³⁹Each independently represents hydrogen or a linear or branched alkyl group (for example, an alkyl group having 1 to 4 carbon atoms);
R³⁴And R³⁶Independently of one another, hydrogen, a linear or branched alkyl group (for example, an alkyl group having 1 to 18 carbon atoms), a carboxyl group, a hydroxy group, an alkoxy group (for example, an alkoxy group having 1 to 18 carbon atoms), amino A group, or halogen (eg, F, Cl, Br, etc.). ]
[0069]
(D) in formula (7)⁺Examples of organic amines that can be used as the group include known aliphatic amines, aliphatic diamines, alicyclic amines, alkoxyalkylamines, alkanol group-containing amines, guanidine derivative amines, and the like.
[0070]
Specific examples of such organic amines include
Aliphatic amines such as butylamine, hexylamine, pentylamine, octylamine, laurylamine, myristylamine, palmitylamine, cetylamine, oleylamine, stearylamine, dibutylamine, dodecylamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine;
Cycloaliphatic amines such as cyclohexylamine, di-cyclohexylamine, rosinamine;
3-propoxypropylamine, di- (2-ethylhexyl) amine, di- (2-ethylhexyl) amine, 2-ethylhexylamine, di- (3-ethoxypropyl) amine, 3-butoxypropylamine, octoxypropylamine, Alkoxyalkylamines such as 3- (2-ethylhexyloxy) propylamine;
Diamines such as dimethylaminopropylamine and dibutylaminopropylamine;
Examples include amines of guanidine derivatives such as 1,3-diphenylguanidine, 1-o-tolylguanidine, di-o-tolylguanidine, and guanidine.
[0071]
Center metal M of monoazo metal-containing dye used in the present invention¹Examples of the metal include divalent, trivalent or tetravalent metals. Specific examples thereof include Zn, Sr, Cr, Cu, Al, Ti, Fe, Zr, Ni, Co, Mn, B, Si, and Sn.
Specific examples of the monoazo metal-containing dye represented by the formula (7) include the following dyes. The groups of formula (8) and formula (9) are azo groups and L as in the following dye examples.₂Or L₄Can be combined. However, of course, the present invention is not limited to these.
[0072]
A monoazo metal-containing dye represented by the formula (7):¹And B²Are represented by the above formula (8), that is, specific examples of the monoazo metal-containing dye of the formula (7-a) include the following structures.
Embedded image

(7-a)
[0073]
[Table 7]

[0074]
A monoazo metal-containing dye represented by the formula (7):¹And B²Are represented by the above formula (9), that is, specific examples of the monoazo metal-containing dye of the formula (7-b) include the following structures.
Embedded image

(7-b)
[0075]
[Table 8]

[0076]
Moreover, it is preferable to use the dye which has the following frame | skeleton for the coloring agent for laser beam transmissive coloring resin compositions of this invention. This skeleton is less likely to be cut than phenyl-NH-phenyl and easily constitutes a robust dye. Moreover, the resin moldability and hue when blended with a thermoplastic resin are good. In particular, it is useful because there are few dyes having high fastness as yellow dyes.
[0077]
Embedded image

[0078]
The phenyl group in this formula may have a substituent, and the substituents may form a ring.
As the dye having this skeleton, a yellow anthraquinone dye having the following structure with or without a substituent is preferable. The anthraquinone dye having this structure has good compatibility with the thermoplastic resin, can clearly color the thermoplastic resin, and laser light (especially laser light with a wavelength of 1000 to 1200 nm or near by a YAG laser or the like). ) Is highly transparent. In addition, it exhibits practically sufficient heat resistance.
[0079]
Embedded image

[0080]
Specific examples of the dye having this structure include the following dyes. However, of course, the present invention is not limited to these.
[0081]
Embedded image

Compound Example 8-1
[0082]
Embedded image

Compound Example 8-2
[0083]
Embedded image

Compound Example 8-3
[0084]
Embedded image

Compound Example 8-4
[0085]
Embedded image

Compound Example 8-5
[0086]
Embedded image

Compound Example 8-6
[0087]
Embedded image

Compound Example 8-7
[0088]
Furthermore, it is preferable to use the dye which has the following frame | skeleton for the coloring agent for laser beam transmissive coloring resin compositions of this invention. This skeleton is less likely to be cut than phenyl-NH-phenyl and easily constitutes a robust dye. Moreover, the resin moldability and hue when blended with a thermoplastic resin are good. In particular, it is useful because there are few dyes having high fastness as yellow dyes.
[0089]
Embedded image

[0090]
The phenyl group in this formula may have a substituent, and the substituents may form a ring.
Specific examples of the dye having the skeleton include the following dyes (anthraquinone derivatives having a thiazole ring). However, of course, the present invention is not limited to these.
[0091]
Embedded image

Compound Example 9-1
[0092]
Embedded image

Compound Example 9-2
[0093]
Embedded image

Compound Example 9-3
[0094]
Embedded image

Compound Example 9-4
[0095]
Embedded image

Compound Example 9-5
[0096]
Furthermore, it is preferable to use the dye which has the following frame | skeleton for the coloring agent for laser beam transmissive coloring resin compositions of this invention. This skeleton is less likely to be cut than phenyl-NH-phenyl and easily constitutes a robust dye. Moreover, the resin moldability and hue when blended with a thermoplastic resin are good. In particular, it is useful because there are few dyes having high fastness as yellow dyes.
[0097]
Embedded image

[0098]
The phenyl group in this formula may have a substituent, and the substituents may form a ring.
[0099]
Specific examples of the dye having the skeleton include the following dyes (anthraquinone thioxanthone derivatives). However, of course, the present invention is not limited to these.
[0100]
Embedded image

Compound Example 11-1
[0101]
Embedded image

Compound Example 11-2
[0102]
Embedded image

Compound Example 11-3
[0103]
As a specific example of the colorant for laser light transmitting colored resin composition of the present invention comprising both the anthraquinone salt-forming dye represented by the above formulas (1) to (3) and the above other dyes, The following colorants can be mentioned. However, of course, the present invention is not limited to these. In the following description, “parts by weight” is abbreviated as “parts”.
[0104]
Examples of colorants
(a-1)A combination of the anthraquinone salt-forming dye of Compound Example 1-1, the perinone red dye of Compound Example 5-3 and the anthraquinone yellow dye of Compound Example 8-1.
(For example, a combination of 60 parts of an anthraquinone salt forming dye of Compound Example 1-1, 20 parts of a perinone red dye of Compound Example 5-3 and 10 parts of an anthraquinone yellow dye of Compound Example 8-1).
(a-2)A combination of the anthraquinone salt-forming dye of Compound Example 1-1, the perinone red dye of Compound Example 5-3 and the perinone orange dye of Compound Example 5-1.
(For example, a combination of 30 parts of the anthraquinone salt-forming dye of Compound Example 1-1, 20 parts of the perinone red dye of Compound Example 5-3 and 10 parts of the perinone orange dye of Compound Example 5-1).
(a-3)A combination of the anthraquinone salt-forming dye of Compound Example 1-2, the perinone red dye of Compound Example 5-3 and the anthraquinone yellow dye of Compound Example 8-1.
(For example, a combination of 60 parts of an anthraquinone salt forming dye of Compound Example 1-2, 20 parts of a perinone red dye of Compound Example 5-3 and 10 parts of an anthraquinone yellow dye of Compound Example 8-1).
(a-4)A combination of the anthraquinone salt-forming dye of Compound Example 1-1, the perinone red dye of Compound Example 5-3 and the anthraquinone yellow dye of Compound Example 9-1.
(For example, a combination of 60 parts of an anthraquinone salt forming dye of Compound Example 1-1, 20 parts of a perinone red dye of Compound Example 5-3 and 10 parts of an anthraquinone yellow dye of Compound Example 9-1).
(a-5)A combination of the anthraquinone salt-forming dye of Compound Example 1-1, the monoazo metal-containing red dye of Compound Example 7-1, and the monoazo metal-containing yellow dye of Compound Example 7-3.
(For example, a combination of 60 parts of an anthraquinone salt-forming dye of Compound Example 1-1, 20 parts of a monoazo metal-containing red dye of Compound Example 7-1 and 10 parts of a monoazo metal-containing yellow dye of Compound Example 7-3).
(a-6)A combination of the anthraquinone salt-forming dye of Compound Example 1-1, the monoazo metal-containing red dye of Compound Example 7-1 and the anthraquinone yellow dye of Compound Example 9-1.
(For example, a combination of 60 parts of an anthraquinone salt-forming dye of Compound Example 1-1, 20 parts of a monoazo metal-containing red dye of Compound Example 7-1 and 10 parts of an anthraquinone yellow dye of Compound Example 9-1).
(a-7)A combination of the anthraquinone salt-forming dye of Compound Example 1-2, the monoazo metal-containing red dye of Compound Example 7-1 and the anthraquinone yellow dye of Compound Example 8-1.
(For example, a combination of 60 parts of an anthraquinone salt-forming dye of Compound Example 1-2, 20 parts of a monoazo metal-containing red dye of Compound Example 7-1 and 10 parts of an anthraquinone yellow dye of Compound Example 8-1).
(a-8)A combination of the anthraquinone salt-forming dye of Compound Example 1-2, the perinone red dye of Compound Example 5-3 and the monoazo metal-containing yellow dye of Compound Example 7-3.
(For example, a combination of 60 parts of an anthraquinone salt-forming dye of Compound Example 1-2, 20 parts of a perinone red dye of Compound Example 5-3 and 10 parts of a monoazo metal-containing yellow dye of Compound Example 7-3).
(a-9): A combination of the anthraquinone salt-forming dye of Compound Example 1-4 and the perinone red dye of Compound Example 5-3.
(For example, a combination of 30 parts of an anthraquinone salt forming dye of Compound Example 1-4 and 10 parts of a perinone red dye of Compound Example 5-3).
(a-10): Combination of the anthraquinone salt-forming dye of Compound Example 1-20 and the monoazo metal-containing red dye of Compound Example 7-1.
(For example, a combination of 30 parts of an anthraquinone salt-forming dye of Compound Example 1-20 and 10 parts of a monoazo metal-containing red dye of Compound Example 7-1).
(a-11): A combination of the anthraquinone salt-forming dye of Compound Example 1-10 and the anthrapyridone salt-forming red dye of Compound Example 6-1.
(For example, a combination of 30 parts of the anthraquinone salt forming dye of Compound Example 1-10 and 10 parts of the anthrapyridone salt forming red dye of Compound Example 6-1).
(a-12): A combination of the anthraquinone salt-forming dye of Compound Example 1-18 and the anthraquinone yellow dye of Compound Example 9-1.
(For example, a combination of 30 parts of an anthraquinone salt-forming dye of Compound Example 1-18 and 10 parts of an anthraquinone yellow dye of Compound Example 9-1).
(a-13): A combination of the anthraquinone salt-forming dye of Compound Example 1-19 and the anthraquinone yellow dye of Compound Example 8-1.
(For example, a combination of 30 parts of the anthraquinone salt-forming dye of Compound Example 1-19 and 10 parts of the anthraquinone yellow dye of Compound Example 8-1).
(a-14): Combination of the anthraquinone salt-forming dye of Compound Example 1-24 and the anthraquinone yellow dye of Compound Example 8-1.
(For example, a combination of 30 parts of the anthraquinone salt-forming dye of Compound Example 1-24 and 10 parts of the anthraquinone yellow dye of Compound Example 8-1).
(a-15)A combination of the anthraquinone salt-forming dye of Compound Example 1-11, the monoazo metal-containing red dye of Compound Example 7-1 and the anthraquinone yellow dye of Compound Example 8-1.
(For example, a combination of 60 parts of an anthraquinone salt-forming dye of Compound Example 1-11, 20 parts of a monoazo metal-containing red dye of Compound Example 7-1 and 10 parts of an anthraquinone yellow dye of Compound Example 8-1).
(a-16)A combination of the anthraquinone salt-forming dye of Compound Example 2-2, the perinone red dye of Compound Example 5-3 and the anthraquinone yellow dye of Compound Example 9-1.
(For example, a combination of 60 parts of an anthraquinone salt forming dye of Compound Example 2-2, 20 parts of a perinone red dye of Compound Example 5-3 and 10 parts of an anthraquinone yellow dye of Compound Example 9-1).
(a-17)A combination of the anthraquinone salt-forming dye of Compound Example 2-8, the perinone red dye of Compound Example 5-3 and the anthraquinone yellow dye of Compound Example 9-1.
(For example, a combination of 60 parts of an anthraquinone salt forming dye of Compound Example 2-8, 20 parts of a perinone red dye of Compound Example 5-3 and 10 parts of an anthraquinone yellow dye of Compound Example 9-1).
(a-18)A combination of the anthraquinone salt-forming dye of Compound Example 2-5, the perinone red dye of Compound Example 5-3 and the anthraquinone yellow dye of Compound Example 8-1.
(For example, a combination of 60 parts of an anthraquinone salt forming dye of Compound Example 2-5, 20 parts of a perinone red dye of Compound Example 5-3 and 10 parts of an anthraquinone yellow dye of Compound Example 8-1).
(a-19)A combination of the anthraquinone salt forming dye of Compound Example 1-22 and the anthraquinone salt forming dye compound example of Compound Example 3-4 and the anthrapyridone salt forming red dye of Compound Example 6-1.
(For example, 60 parts of an anthraquinone salt forming dye of Compound Example 1-22, 40 parts of an anthraquinone salt forming dye compound example of Compound Example 3-4 and 10 parts of an anthrapyridone salt forming red dye of Compound Example 6-1) combination).
(a-20)A combination of the anthraquinone salt-forming dye of Compound Example 1-20, the anthraquinone salt-forming dye compound example of Compound Example 3-4 and the anthrapyridone salt-forming red dye of 6-1.
(For example, 50 parts of the anthraquinone salt forming dye of Compound Example 1-20, 40 parts of the anthraquinone salt forming dye compound example of Compound Example 3-4 and 10 parts of the anthrapyridone salt forming red dye of Compound Example 6-1) combination).
(a-21)A combination of the anthraquinone salt forming dye of Compound Example 1-20 and the anthraquinone salt forming dye compound example of Compound Example 3-4 and the perinone red dye of Compound Example 5-2.
(For example, a combination of 50 parts of the anthraquinone salt forming dye of Compound Example 1-20, 40 parts of the anthraquinone salt forming dye compound example of Compound Example 3-4 and 10 parts of the perinone red dye of Compound Example 5-2).
(a-22)A combination of the anthraquinone salt-forming dye of Compound Example 3-10, the perinone red dye of Compound Example 5-3 and the anthraquinone yellow dye of Compound Example 9-1.
(For example, a combination of 60 parts of an anthraquinone salt forming dye of Compound Example 3-10, 20 parts of a perinone red dye of Compound Example 5-3 and 10 parts of an anthraquinone yellow dye of Compound Example 9-1).
(a-23)A combination of the anthraquinone salt-forming dye of Compound Example 3-11, the perinone red dye of Compound Example 5-3 and the anthraquinone yellow dye of Compound Example 8-1.
(For example, a combination of 60 parts of an anthraquinone salt-forming dye of Compound Example 3-11, 20 parts of a perinone red dye of Compound Example 5-3 and 10 parts of an anthraquinone yellow dye of Compound Example 8-1).
(a-24)A combination of the anthraquinone salt-forming dye of Compound Example 3-11, the perinone red dye of Compound Example 5-3 and the anthraquinone yellow dye of Compound Example 11-1.
(For example, 60 parts of an anthraquinone salt forming dye of Compound Example 3-11, 20 parts of a perinone red dye of Compound Example 5-3 and 10 parts of an anthraquinone yellow dye of Compound Example 11-1).
[0105]
The laser beam transmitting colored resin composition of the present invention is obtained by coloring a thermoplastic resin with the colorant for laser beam transmitting colored resin composition of the present invention. The amount of the colorant for laser light transmitting colored resin composition used in the laser light transmitting colored resin composition of the present invention can be, for example, 0.01 to 10% by weight with respect to the thermoplastic resin. Preferably, it is 0.1 to 5% by weight.
[0106]
T which is the transmittance of laser light having a wavelength of 950 nm in the laser light transmitting colored resin composition of the present invention, which is a thermoplastic resin colored with the colorant of the present invention._{Colored resin}And T which is the transmittance of laser light having a wavelength of 950 nm in the same uncolored thermoplastic resin as described above_{Non-colored resin}The ratio of T_{Colored resin}/ T_{Non-colored resin}Can be, for example, 0.8 to 1.2, preferably 0.9 to 1.1.
[0107]
Further, T which is the transmittance of the laser beam having a wavelength of 950 nm in the laser beam transmitting colored resin composition of the present invention._950nmAnd T which is the transmittance of laser light having a wavelength of 1050 nm_1050nmThe ratio of T_950nm/ T_1050nmCan be, for example, 0.8 to 1.2, preferably 0.9 to 1.1.
[0108]
Specific examples of the thermoplastic resin in the laser light transmitting colored resin composition of the present invention include polyamide resin, polyethylene resin, polypropylene resin, polybutylene terephthalate resin, polyphenylene sulfide resin and polyether ether ketone resin, polyethylene terephthalate resin, poly Butylene terephthalate resin, polyphenylene sulfide resin, polycarbonate resin, amorphous (transparent) nylon, liquid crystal polymer, polystyrene resin, acrylic resin, polyacetal resin, polyphenylene ether resin, acrylonitrile / styrene copolymer resin, acrylonitrile / butadiene / styrene copolymer resin , Styrene / methyl methacrylate copolymer resin, Styrene / butadiene copolymer resin, Styrene / butadiene / methyl methacrylate The polymerization resins. These thermoplastic resins can be used alone or in admixture of two or more. Further, a copolymer or mixture mainly composed of these polymers; a thermoplastic resin in which an elastomer such as rubber or rubber-like resin is blended; and a polymer alloy containing 10% by weight or more of these resins are also included. .
[0109]
Among these thermoplastic resins, the polypropylene resin, the polyethylene resin, the polyamide resin, the polyester resin (including PET and PBT), and the like from the viewpoints of laser light transmission and good mechanical strength, Polycarbonate resin, polystyrene resin, acrylic resin, and polyacetal resin.
[0110]
The laser beam transmitting colored resin composition of the present invention may contain appropriate amounts of various fibrous reinforcing materials according to the application and purpose. Glass fiber is preferable for reinforcing a resin that requires transparency. As the glass fiber, any of alkali-containing glass, low alkali glass, and non-alkali glass can be used. E glass and T glass are preferable. The fiber length of the glass fiber that can be suitably used is 2 to 15 mm, and the fiber diameter is 1 to 20 μm. There is no restriction | limiting in particular about the form of glass fiber, For example, any, such as roving and a milled fiber, may be sufficient. These glass fibers can be used alone or in combination of two or more. The content is preferably 5 to 120% by weight with respect to 100% by weight of the thermoplastic resin. If it is less than 5% by weight, it is difficult to obtain a sufficient glass fiber reinforcing effect, and if it exceeds 120% by weight, the moldability tends to deteriorate. It is preferably 10 to 60% by weight, particularly preferably 20 to 50% by weight.
[0111]
The laser beam transmitting colored resin composition of the present invention can be blended with various additives as required. Examples of such additives include auxiliary colorants, dispersants, fillers, stabilizers, plasticizers, modifiers, ultraviolet absorbers or light stabilizers, antioxidants, antistatic agents, lubricants, mold release agents. Agents, crystal accelerators, crystal nucleating agents, flame retardants, impact resistance improving elastomers, and the like.
[0112]
The laser beam transmitting colored resin composition of the present invention can be obtained by blending raw materials by any blending method. These blending components are usually preferably homogenized as much as possible. Specifically, for example, all raw materials are mixed with a blender such as a blender, kneader, Banbury mixer, roll, and extruder and homogenized to obtain a colored thermoplastic resin composition, or some raw materials After mixing with a mixer, the remaining components can be added and further mixed and homogenized to obtain a resin composition. Alternatively, a raw material that has been dry-blended in advance can be melt-kneaded and homogenized with a heated extruder, then extruded into a wire shape, and then cut into a desired length to obtain a colored granular material (colored pellet).
[0113]
Moreover, the masterbatch of the laser beam transmitting colored resin composition of the present invention can be obtained by any method. For example, after mixing the thermoplastic resin powder or pellets and the colorant with a mixer such as a tumbler or a super mixer, the mixture is heated and melted with an extruder, batch kneader or roll kneader. It can be obtained by pelletizing or coarsening. For example, after adding a coloring agent to the thermoplastic resin for masterbatches still in a solution state after synthesis, the masterbatch can be obtained by removing the solvent.
[0114]
Molding of the laser light transmitting colored resin composition of the present invention can be performed by various commonly performed procedures. For example, using colored pellets, it can also be performed by molding with a processing machine such as an extruder, an injection molding machine, a roll mill, etc. Also, a thermoplastic resin pellet or powder having transparency, a pulverized colorant, In addition, various additives can be mixed in a suitable mixer as necessary, and the mixture can be formed by using a processing machine. Further, for example, a colorant may be added to a monomer containing an appropriate polymerization catalyst, and the mixture may be polymerized to obtain a desired thermoplastic resin, which may be molded by an appropriate method. As a molding method, for example, any generally used molding method such as injection molding, extrusion molding, compression molding, foam molding, blow molding, vacuum molding, injection blow molding, rotational molding, calendar molding, solution casting, etc. should be adopted. You can also.
[0115]
【The invention's effect】
Colorant for laser light transmitting colored resin composition of the present invention, laser light transmitting colored resin composition colored by the colorant, laser light transmitting color filter comprising the colored resin composition, and laser light transmitting The color film has high transparency of laser light with a wavelength from around 800 nm by a semiconductor laser to around 1100 nm by a YAG laser, high fastness such as heat resistance and light resistance, and good migration resistance and chemical resistance. And it shows a clear hue.
[0116]
【Example】
EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
[0117]
Production Examples 1 to 11 describe the synthesis of anthraquinone salt-forming dyes.
[0118]
Production Example 1
50 g of the anthraquinone acid dye of Compound Example 10-1 was dispersed in 500 ml of water. On the other hand, 30 g of hydrochloric acid and 20 g of hexamethylenediamine were dissolved in 300 ml of water. This solution was added dropwise to the anthraquinone acid dye dispersion at room temperature, and the pH of the mixture was adjusted to 3.5 and stirred for 1 hour. The reaction mixture was filtered and the collected product was washed with water. The yield of the obtained anthraquinone salt-forming dye was 66.5 g (yield 95%).
[0119]
Production Example 2
50 g of the anthraquinone acid dye of Compound Example 10-1 was dispersed in 500 ml of water. On the other hand, 30 g of hydrochloric acid and 10 g of hexamethylenediamine were dissolved in 300 ml of water. This solution was added dropwise to the anthraquinone acid dye dispersion at room temperature, and the pH of the mixture was adjusted to 3.5 and stirred for 1 hour. The reaction mixture was filtered and the collected product was washed with water. The yield of the obtained anthraquinone salt-forming dye was 57 g (yield 95%).
[0120]
Production Example 3
50 g of the anthraquinone acid dye of Compound Example 10-2 was dispersed in 500 ml of water. On the other hand, 30 g of hydrochloric acid and 11 g of guanidine were dissolved in 300 ml of water. This solution was added dropwise to the anthraquinone acid dye dispersion at room temperature, and the pH of the mixture was adjusted to 3.5 and stirred for 1 hour. The reaction mixture was filtered and the collected product was washed with water. The yield of the obtained anthraquinone salt-forming dye was 59 g (yield 97%).
[0121]
Production Example 4
50 g of the anthraquinone acid dye of Compound Example 10-6 was dispersed in 500 ml of water. On the other hand, 30 g of hydrochloric acid and 40 g of diphenylguanidine were dissolved in 300 ml of water. This solution was added dropwise to the anthraquinone acid dye dispersion at room temperature, and the pH of the mixture was adjusted to 3.5 and stirred for 1 hour. The reaction mixture was filtered and the collected product was washed with water. The yield of the obtained anthraquinone salt-forming dye was 87 g (97% yield).
[0122]
Production Example 5
50 g of the anthraquinone acid dye of Compound Example 10-7 was dispersed in 500 ml of water. Meanwhile, 30 g of hydrochloric acid and 14 g of hexamethylenediamine were dissolved in 300 ml of water. This solution was added dropwise to the anthraquinone acid dye dispersion at room temperature, and the pH of the mixture was adjusted to 3.5 and stirred for 1 hour. The reaction mixture was filtered and the collected product was washed with water. The yield of the obtained anthraquinone salt-forming dye was 62 g (yield 97%).
[0123]
Production Example 6
25 g of the anthraquinone acid dye of Compound Example 10-1 and 25 g of the anthraquinone acid dye of Compound Example 10-2 were dispersed in 500 ml of water. On the other hand, 30 g of hydrochloric acid and 10 g of guanidine were dissolved in 300 ml of water. This solution was added dropwise to the anthraquinone acid dye dispersion at room temperature, and the pH of the mixture was adjusted to 3.5 and stirred for 1 hour. The reaction mixture was filtered and the collected product was washed with water. The yield of the obtained anthraquinone salt-forming dye was 57 g (yield 95%).
[0124]
Production Example 7
30 g of an anthraquinone acid dye represented by the formula (12-1) was dispersed in 1500 ml of water. Meanwhile, 12 g of benzyltrimethylammonium chloride was dissolved in 250 ml of water. This solution was added dropwise to the dispersion of the anthraquinone acid dye kept at 50 ° C. and stirred for 1 hour. The reaction mixture was filtered and the collected product was washed with water. The yield of the resulting anthraquinone salt-forming dye was 35 g (yield 83%).
[0125]
Embedded image

... (12-1)
[0126]
Production Example 8
20 g of an anthrapyridone acid dye represented by the formula (12-2) was dispersed in 2000 ml of water. On the other hand, 9 g of benzyltrimethylammonium chloride was dissolved in 180 ml of water. This solution was added dropwise to the dispersion of the anthrapyridone acid dye kept at 50 ° C. and stirred for 1 hour. The reaction mixture was filtered and the filtered product was washed with water. The yield of the obtained anthrapyridone salt-forming dye was 21 g (yield 72%).
[0127]
Embedded image

... (12-2)
[0128]
Production Example 9
30 g of an anthraquinone acid dye represented by the formula (12-3) was dispersed in 1000 ml of water. On the other hand, 7 g of hydrochloric acid and 4 g of hexamethylenediamine were dissolved in 100 ml of water. This solution was added dropwise to the dispersion of the anthraquinone acid dye kept at 35 ° C. and stirred for 1 hour. When the reaction mixture was filtered and the collected product was washed with water, the yield of the obtained anthraquinone salt-forming dye was 25 g (yield 74%).
[0129]
Embedded image

... (12-3)
[0130]
Production Example 10
50 g of the anthraquinone acid dye of Compound Example 10-1 was dispersed in 1500 ml of water. On the other hand, 30 g of benzyltrimethylammonium chloride was dissolved in 600 ml of water. This solution was added dropwise to the dispersion of the anthraquinone acid dye kept at 50 ° C. and stirred for 1 hour. The reaction mixture was filtered and the collected product was washed with water. The yield of the obtained anthraquinone salt-forming dye was 62 g (yield 78%).
[0131]
Production Example 11
30 g of an anthraquinone acid dye represented by the formula (12-3) was dispersed in 1000 ml of water. On the other hand, 6 g of benzyltrimethylammonium chloride was dissolved in 120 ml of water. This solution was added dropwise to the dispersion of the anthraquinone acid dye kept at 40 ° C. and stirred for 1 hour. The reaction mixture was filtered and the collected product was washed with water. The yield of the obtained anthraquinone salt-forming dye was 27 g (yield 75%).
[0132]
In Examples 1 to 8, the colorant (mixed color scheme) for the laser light transmitting colored resin composition will be described.
[0133]
Example 1
54 g of the anthraquinone salt-forming dye of Production Example 1, 18 g of the perinone dye of Compound Example 5-3, and 9 g of the anthraquinone dye of Compound Example 8-1 were placed in a stainless steel tumbler and mixed with stirring for 1 hour to transmit laser light. 80 g of a black powder of a colorant for a conductive colored resin composition was obtained (yield 99%). Then, with an ion chromatograph (DX-300 manufactured by Nippon Dionex), a guard column (ion pack AG4A-SC) and a separation column (ion pack AS4A-SC) are attached, and the black powder is dissolved in a small amount of methanol and water. After dilution and injection of the supernatant, the inorganic salt was measured at a column temperature of 35 ° C. and a flow rate of 1.5 ml / min, and both chlorine ion and sulfate ion were 0.01%.
[0134]
Example 2
54 g of the anthraquinone salt-forming dye of Production Example 3, 18 g of the perinone dye of Compound Example 5-3 and 9 g of the anthraquinone dye of Compound Example 8-1 were placed in a stainless steel tumbler and stirred and mixed for 1 hour to transmit laser light. 80 g of a black powder of a colorant for a conductive colored resin composition was obtained (yield 99%).
[0135]
Example 3
54 g of the anthraquinone salt-forming dye of Production Example 1, 18 g of the perinone dye of Compound Example 5-3, and 9 g of the anthraquinone dye (batt dye) of Compound Example 9-1 were placed in a stainless steel tumbler and stirred for 1 hour. As a result, 80 g of a black powder of a colorant for a laser light transmitting colored resin composition was obtained (yield 99%).
[0136]
Example 4
54 g of the anthraquinone salt-forming dye of Production Example 1, 18 g of the monoazo metal-containing dye of Compound Example 7-1 and 9 g of the monoazo metal-containing dye of Compound Example 7-2 were placed in a stainless steel tumbler and mixed with stirring for 1 hour. 80 g of black powder of a colorant for a light transmissive colored resin composition was obtained (yield 99%).
[0137]
Example 5
54 g of the anthraquinone salt-forming dye of Production Example 1, 18 g of the perinone dye of Compound Example 5-3, and 9 g of the perinone dye of Compound Example 5-1 were placed in a stainless steel tumbler and mixed with stirring for 1 hour to transmit laser light. 80 g of a black powder of a colorant for a conductive colored resin composition was obtained (yield 99%).
[0138]
Example 6
54 g of the anthraquinone salt-forming dye of Production Example 1, 18 g of the monoazo metal-containing dye of Compound Example 7-1, and 9 g of the anthraquinone dye of Compound Example 9-1 are placed in a stainless steel tumbler and mixed with stirring for 1 hour to produce laser light. 80 g of a black powder of a colorant for a transmissive colored resin composition was obtained (99% yield).
[0139]
Example 7
54 g of the anthraquinone salt-forming dye of Production Example 1, 18 g of the perinone dye represented by Compound Example 5-3 and 9 g of the monoazo metal-containing dye of Compound Example 7-3 were placed in a stainless steel tumbler and stirred for 1 hour. As a result, 80 g of a black powder of a colorant for a laser light transmitting colored resin composition was obtained (yield 99%).
[0140]
Example 8
54 g of the anthraquinone salt-forming dye of Production Example 1, 18 g of the monoazo metal-containing dye of Compound Example 7-1 and 9 g of the anthraquinone dye (Vat Dye) of Compound Example 9-1 were placed in a stainless steel tumbler and mixed with stirring for 1 hour. As a result, 80 g of a black powder of a colorant for a laser light transmitting colored resin composition was obtained (yield 99%).
[0141]
In Examples 9 to 24 and Comparative Examples 1 to 8, laser light transmitting colored resin compositions will be described.
[0142]
Example 9
6 nylon ··· 400 g [measured after drying non-reinforced 6 nylon (polyamide made by DuPont) at 120 ° C for 8 hours or more using a vacuum dryer]
Colorant for laser light transmitting colored resin composition of Production Example 1 ... 0.80 g
[0143]
The above blend was placed in a stainless steel tumbler and stirred for 1 hour. When the obtained mixture was injection molded by a normal method at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C. using an injection molding machine (trade name: K50-C, manufactured by Kawaguchi Steel), the appearance and surface gloss were A uniform amber-colored test piece [48 × 86 × 3 (mm)] having good color unevenness was obtained.
[0144]
Example 10
6 nylon ··· 400 g [measured after drying non-reinforced 6 nylon (polyamide made by DuPont) at 120 ° C for 8 hours or more using a vacuum dryer]
Colorant for laser light transmitting colored resin composition of Production Example 3 ... 0.80 g
[0145]
The above blend was placed in a stainless steel tumbler and stirred for 1 hour. When the obtained mixture was injection-molded by an ordinary method at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C. using an injection molding machine (trade name: K50-C, manufactured by Kawaguchi Steel), the appearance and surface gloss were A uniform green test piece [48 × 86 × 3 (mm)] having good color uniformity was obtained.
[0146]
Example 11
6 nylon ··· 400 g [measured after drying non-reinforced 6 nylon (polyamide made by DuPont) at 120 ° C for 8 hours or more using a vacuum dryer]
Colorant for laser light transmitting colored resin composition of Example 1 .... 0.80 g
[0147]
The above blend was placed in a stainless steel tumbler and stirred for 1 hour. When the obtained mixture was injection-molded by an ordinary method at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C. using an injection molding machine (trade name: K50-C, manufactured by Kawaguchi Steel), the appearance and surface gloss were A uniform black test piece [48 × 86 × 3 (mm)] with good color uniformity was obtained.
[0148]
Example 12
6 nylon ··· 400 g [measured after drying non-reinforced 6 nylon (polyamide made by DuPont) at 120 ° C for 8 hours or more using a vacuum dryer]
Colorant for laser light transmitting colored resin composition of Example 2 .... 0.80 g
[0149]
The above blend was placed in a stainless steel tumbler and stirred for 1 hour. When the obtained mixture was injection-molded by an ordinary method at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C. using an injection molding machine (trade name: K50-C, manufactured by Kawaguchi Steel), the appearance and surface gloss were A uniform black test piece [48 × 86 × 3 (mm)] with good color uniformity was obtained.
[0150]
Example 13
6 nylon ··· 400 g [measured after drying non-reinforced 6 nylon (polyamide made by DuPont) at 120 ° C for 8 hours or more using a vacuum dryer]
Colorant for laser light transmitting colored resin composition of Example 4 .... 0.80 g
[0151]
The above blend was placed in a stainless steel tumbler and stirred for 1 hour. When the obtained mixture was injection-molded by an ordinary method at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C. using an injection molding machine (trade name: K50-C, manufactured by Kawaguchi Steel), the appearance and surface gloss were A uniform black test piece [48 × 86 × 3 (mm)] with good color uniformity was obtained.
[0152]
Example 14
6 nylon ··· 400 g [measured after drying non-reinforced 6 nylon (polyamide made by DuPont) at 120 ° C for 8 hours or more using a vacuum dryer]
Colorant for laser light transmitting colored resin composition of Example 8 .... 0.80 g
[0153]
The above blend was placed in a stainless steel tumbler and stirred for 1 hour. When the obtained mixture was injection-molded by an ordinary method at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C. using an injection molding machine (trade name: K50-C, manufactured by Kawaguchi Steel), the appearance and surface gloss were A uniform black test piece [48 × 86 × 3 (mm)] with good color uniformity was obtained.
[0154]
Example 15
6 nylon ··· 400 g [measured after drying non-reinforced 6 nylon (polyamide made by DuPont) at 120 ° C for 8 hours or more using a vacuum dryer]
Colorant for laser light transmitting colored resin composition of Production Example 6 ... 0.80 g
[0155]
The above blend was placed in a stainless steel tumbler and stirred for 1 hour. When the obtained mixture was injection-molded by an ordinary method at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C. using an injection molding machine (trade name: K50-C, manufactured by Kawaguchi Steel), the appearance and surface gloss were A uniform black test piece [48 × 86 × 3 (mm)] with good color uniformity was obtained.
[0156]
Example 16
PET ··· 400 g [Unweighed PET (polyethylene terephthalate resin manufactured by DuPont) was dried at 120 ° C. for 8 hours or more using a vacuum drying apparatus and then weighed]
Colorant for laser light transmitting colored resin composition of Example 1 .... 0.80 g
[0157]
The above blend was placed in a stainless steel tumbler and stirred for 1 hour. When the obtained mixture was injection-molded by an ordinary method at a cylinder temperature of 280 ° C. and a mold temperature of 40 ° C. using an injection molding machine (trade name: K50-C, manufactured by Kawaguchi Steel), the appearance and surface gloss were A uniform black test piece [48 × 86 × 3 (mm)] with good color uniformity was obtained.
[0158]
Example 17
PET ··· 400 g [Unweighed PET (polyethylene terephthalate resin manufactured by DuPont) was dried at 120 ° C. for 8 hours or more using a vacuum drying apparatus and then weighed]
Colorant for laser light transmitting colored resin composition of Example 6 ... 0.80 g
[0159]
The above blend was placed in a stainless steel tumbler and stirred for 1 hour. When the obtained mixture was injection-molded by an ordinary method at a cylinder temperature of 280 ° C. and a mold temperature of 40 ° C. using an injection molding machine (trade name: K50-C, manufactured by Kawaguchi Steel), the appearance and surface gloss were A uniform black test piece [48 × 86 × 3 (mm)] with good color uniformity was obtained.
[0160]
Example 18
PP ··· 400g (trade name: Polypro PN510T manufactured by Tokuyama)
Colorant for laser light transmitting colored resin composition of Production Example 1 ... 0.80 g
[0161]
The above blend was placed in a stainless steel tumbler and stirred for 1 hour. When the obtained mixture was injection-molded by an ordinary method using an injection molding machine (trade name: K50-C, manufactured by Kawaguchi Steel Co., Ltd.) at a cylinder temperature of 230 ° C. and a mold temperature of 40 ° C., the appearance and surface gloss were A uniform black test piece [48 × 86 × 3 (mm)] with good color uniformity was obtained.
[0162]
Example 19
PC ... 400g (Mitsubishi Engineer Plastic Polycarbonate Resin 7020A)
Colorant for laser light transmitting colored resin composition of Example 1 .... 0.80 g
[0163]
The above blend was placed in a stainless steel tumbler and stirred for 1 hour. The resulting mixture was kneaded using a vent type extruder (trade name: E30SV, manufactured by Engineering Plastics Co., Ltd.), the melt was quenched with cooling water, and then cut with a pelletizer to obtain chips.
[0164]
Using this chip, a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. were obtained using an injection molding machine (trade name: K50-C, manufactured by Kawaguchi Steel Co., Ltd.) with a mold having a disc having a diameter of 50 mm and a thickness of 1.5 mm. As a result of molding, a black laser transmission filter having a good appearance and a uniform hue was obtained.
[0165]
Example 20
66 Nylon ... 400 g [Measured after drying non-reinforced 66 nylon (polyamide made by DuPont) at 120 ° C. for 8 hours or more using a vacuum dryer]
Colorant for laser light transmitting colored resin composition of Production Example 7 ... 0.67g
Colorant for laser light transmitting colored resin composition of Production Example 8 ... 0.13 g
[0166]
The above blend was placed in a stainless steel tumbler and stirred for 1 hour. When the obtained mixture was injection-molded by an ordinary method at a cylinder temperature of 280 ° C. and a mold temperature of 60 ° C. using an injection molding machine (trade name: K50-C, manufactured by Kawaguchi Steel), the appearance and surface gloss were A uniform black test piece [48 × 86 × 3 (mm)] with good color uniformity was obtained.
[0167]
Example 21
PET ··· 400 g [Unweighed PET (polyethylene terephthalate resin manufactured by DuPont) was dried at 120 ° C. for 8 hours or more using a vacuum drying apparatus and then weighed]
Colorant for laser light transmitting colored resin composition of Production Example 7 ... 0.67g
Colorant for laser light transmitting colored resin composition of Production Example 8 ... 0.13 g
[0168]
The above blend was placed in a stainless steel tumbler and stirred for 1 hour. When the obtained mixture was injection-molded by an ordinary method at a cylinder temperature of 280 ° C. and a mold temperature of 40 ° C. using an injection molding machine (trade name: K50-C, manufactured by Kawaguchi Steel), the appearance and surface gloss were A uniform black test piece [48 × 86 × 3 (mm)] with good color uniformity was obtained.
[0169]
Example 22
66 Nylon ... 400 g [Measured after drying non-reinforced 66 nylon (polyamide made by DuPont) at 120 ° C. for 8 hours or more using a vacuum dryer]
Colorant for laser light transmitting colored resin composition of Production Example 9 0.53 g
Perinone dye of Compound Example 5-3 ... 0.18g
0.09 g of anthraquinone dye of Compound Example 8-1
[0170]
The above blend was placed in a stainless steel tumbler and stirred for 1 hour. When the obtained mixture was injection-molded by an ordinary method at a cylinder temperature of 280 ° C. and a mold temperature of 60 ° C. using an injection molding machine (trade name: K50-C, manufactured by Kawaguchi Steel), the appearance and surface gloss were A uniform black test piece [48 × 86 × 3 (mm)] with good color uniformity was obtained.
[0171]
Example 23
6 nylon ··· 400 g [measured after drying non-reinforced 6 nylon (polyamide made by DuPont) at 120 ° C for 8 hours or more using a vacuum dryer]
Colorant for laser light transmitting colored resin composition of Production Example 10 0.53 g
Perinone dye of Compound Example 5-3 ... 0.18g
0.09 g of anthraquinone dye of Compound Example 8-1
[0172]
The above blend was placed in a stainless steel tumbler and stirred for 1 hour. When the obtained mixture was injection-molded by an ordinary method at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C. using an injection molding machine (trade name: K50-C, manufactured by Kawaguchi Steel), the appearance and surface gloss were A uniform black test piece [48 × 86 × 3 (mm)] with good color uniformity was obtained.
[0173]
Example 24
66 Nylon ... 400 g [Measured after drying non-reinforced 66 nylon (polyamide made by DuPont) at 120 ° C. for 8 hours or more using a vacuum dryer]
Colorant for laser light transmitting colored resin composition of Production Example 11 0.53 g
Perinone dye of Compound Example 5-3 ... 0.18g
0.09 g of anthraquinone dye of Compound Example 9-1
[0174]
The above blend was placed in a stainless steel tumbler and stirred for 1 hour. When the obtained mixture was injection-molded by an ordinary method at a cylinder temperature of 280 ° C. and a mold temperature of 60 ° C. using an injection molding machine (trade name: K50-C, manufactured by Kawaguchi Steel), the appearance and surface gloss were A uniform black test piece [48 × 86 × 3 (mm)] with good color uniformity was obtained.
[0175]
Comparative production example 1
50 g of the anthraquinone acid dye of Compound Example 10-1 was dispersed in 500 ml of water. On the other hand, 30 g of hydrochloric acid and 10 g of ethanolamine were dissolved in 300 ml of water. This solution was added dropwise to the anthraquinone acid dye dispersion at room temperature, and the pH of the mixture was adjusted to 3.5 and stirred for 1 hour. The reaction mixture was filtered and the collected product was washed with water. The yield of the obtained anthraquinone salt-forming dye was 54 g (yield 90%). Thereafter, a guard column (ion pack AG4A-SC) and a separation column (ion pack AS4A-SC) were attached with an ion chromatograph (DX-300 manufactured by Nippon Dionex Co., Ltd.), and the resulting anthraquinone salt forming dye was added in a small amount. After dissolving in methanol and diluting with water, the supernatant was injected, and the inorganic salt was measured at a column temperature of 35 ° C. and a flow rate of 1.5 ml / min. As a result, the chlorine ion was 7.5% and the sulfate ion was 5.5%. there were.
[0176]
Comparative Example 1
6 nylon ··· 400 g [non-reinforced 6 nylon (polyamide manufactured by DuPont) was dried at 120 ° C for 8 hours or more using a vacuum dryer and weighed]
Anthraquinone dye represented by the formula (12-4): 0.53 g
Perinone dye of Compound Example 5-3 ... 0.18g
0.09 g of anthraquinone dye of Compound Example 8-1
[0177]
Embedded image

... (12-4)
[0178]
The above blend was placed in a stainless steel tumbler and stirred for 1 hour. When the obtained mixture was injection-molded by an ordinary method at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C. using an injection molding machine (trade name: K50-C, manufactured by Kawaguchi Steel), the appearance and surface gloss were A uniform black test piece [48 × 86 × 3 (mm)] with good color uniformity was obtained.
[0179]
Comparative Example 2
6 nylon ··· 400 g [weighed after drying non-reinforced 6 nylon (polyamide made by DuPont) at 120 ° C for 8 hours or more using a vacuum dryer]
Anthraquinone dye represented by formula (12-5): 0.53 g
Perinone dye of Compound Example 5-3 ... 0.18g
Anthraquinone dye of Compound Example 8-1 0.09 g
[0180]
Embedded image

... (12-5)
[0181]
The above blend was placed in a stainless steel tumbler and stirred for 1 hour. When the obtained mixture was injection-molded by an ordinary method at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C. using an injection molding machine (trade name: K50-C, manufactured by Kawaguchi Steel), the appearance and surface gloss were A uniform black test piece [48 × 86 × 3 (mm)] with good color uniformity was obtained.
[0182]
Comparative Example 3
6 nylon ··· 400 g [weighed after drying non-reinforced 6 nylon (polyamide made by DuPont) at 120 ° C for 8 hours or more using a vacuum dryer]
Anthraquinone dye represented by the formula (12-4): 0.53 g
Monoazo metal-containing dye represented by formula (12-6): 0.18 g
0.09 g of anthraquinone dye of Compound Example 8-1
[0183]
Embedded image

... (12-6)
[0184]
The above blend was placed in a stainless steel tumbler and stirred for 1 hour. When the obtained mixture was injection-molded by an ordinary method at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C. using an injection molding machine (trade name: K50-C, manufactured by Kawaguchi Steel), the appearance and surface gloss were A uniform black test piece [48 × 86 × 3 (mm)] with good color uniformity was obtained.
[0185]
Comparative Example 4
6 nylon ··· 400 g [measured after drying non-reinforced 6 nylon (polyamide made by DuPont) at 120 ° C for 8 hours or more using a vacuum dryer]
Anthraquinone salt-forming dye obtained in Comparative Production Example 1 0.53 g
Perinone dye of Compound Example 5-3 ... 0.18g
0.09 g of anthraquinone dye of Compound Example 8-1
[0186]
The above blend was placed in a stainless steel tumbler and stirred for 1 hour. When the obtained mixture was injection-molded by an ordinary method at a cylinder temperature of 250 ° C. and a mold temperature of 60 ° C. using an injection molding machine (trade name: K50-C, manufactured by Kawaguchi Steel), foaming occurred during molding. As a result, a black test piece [48 × 86 × 3 (mm)] with uneven color was obtained.
[0187]
Comparative Example 5
PET ··· 400 g [Unweighed PET (polyethylene terephthalate resin manufactured by DuPont) was dried at 120 ° C. for 8 hours or more using a vacuum drying apparatus and then weighed]
Anthraquinone dye represented by the formula (12-4): 0.53 g
Perinone dye of Compound Example 5-3 ... 0.18g
0.09 g of anthraquinone dye of Compound Example 8-1
[0188]
The above blend was placed in a stainless steel tumbler and stirred for 1 hour. When the obtained mixture was injection-molded by an ordinary method using an injection molding machine (trade name: K50-C, manufactured by Kawaguchi Steel Co., Ltd.) at a cylinder temperature of 280 ° C. and a mold temperature of 40 ° C., the hue was reddish purple. The test piece [48 × 86 × 3 (mm)] was obtained.
[0189]
Comparative Example 6
PET ··· 400 g [Unweighed PET (polyethylene terephthalate resin manufactured by DuPont) was dried at 120 ° C. for 8 hours or more using a vacuum drying apparatus and then weighed]
Anthraquinone dye represented by formula (12-5): 0.53 g
Perinone dye of Compound Example 5-3 ... 0.18g
0.09 g of anthraquinone dye of Compound Example 8-1
[0190]
The above blend was placed in a stainless steel tumbler and stirred for 1 hour. When the obtained mixture was injection-molded by a normal method at a cylinder temperature of 280 ° C. and a mold temperature of 40 ° C. using an injection molding machine (trade name: K50-C, manufactured by Kawaguchi Steel), the hue was green. A test piece [48 × 86 × 3 (mm)] was obtained.
[0191]
Comparative Example 7
PP ··· 400g (trade name: Polypro PN510T manufactured by Tokuyama)
Anthraquinone dye represented by formula (12-4): 0.80 g
[0192]
The above blend was placed in a stainless steel tumbler and stirred for 1 hour. When the obtained mixture was injection-molded by an ordinary method using an injection molding machine (trade name: K50-C, manufactured by Kawaguchi Steel Co., Ltd.) at a cylinder temperature of 230 ° C. and a mold temperature of 40 ° C., the appearance and surface gloss were A uniform black test piece [48 × 86 × 3 (mm)] with good color uniformity was obtained.
[0193]
Comparative Example 8
PC ... 400g (Mitsubishi Engineer Plastic Polycarbonate Resin 7020A)
Anthraquinone dye represented by the formula (12-4): 0.53 g
Perinone dye of Compound Example 5-3 ... 0.18g
0.09 g of anthraquinone dye of Compound Example 8-1
[0194]
The above blend was placed in a stainless steel tumbler and stirred for 1 hour. The resulting mixture was kneaded using a vent type extruder (trade name: E30SV, manufactured by Engineering Plastics Co., Ltd.), the melt was quenched with cooling water, and then cut with a pelletizer to obtain chips.
[0195]
Using this chip, with an injection molding machine (trade name: K50-C manufactured by Kawaguchi Steel Co., Ltd.), a cylinder having a diameter of 50 mm and a thickness of 1.5 mm, a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. As a result of molding, a red-violet laser transmission filter having a non-uniform hue was obtained.
[0196]
The laser light transmitting colored resin compositions obtained in Examples 9 to 24 and Comparative Examples 1 to 8 were evaluated for physical properties by the following methods. The results are shown in Tables 9 and 10 below and FIGS.
[0197]
(1) Transmittance measurement
A 60φ integrating sphere device for ultraviolet visible near infrared region was attached to a spectrophotometer (HITACHI U-3410 type), a test piece was set, and transmittance T was measured in the wavelength range λ = 400 to 1200 nm. The transmittance charts for the test piece of Example 11, the test piece of Comparative Example 1, and the test piece of non-colored resin (6 nylon used in Example 11) are shown in FIG. 1, FIG. 2, and FIG. 3, respectively.
[0198]
In the present invention, paying attention to the transmittance T in the laser light having the wavelength λ = 950 nm (semiconductor laser region) and the laser light having the wavelength λ = 1050 nm (region of the YAG laser), the transmittance ratio of the following equation is determined. As a guide. T_BIs the transmittance ratio for laser light of wavelength λ = 950 nm.
T_A= T_950nm/ T_1050nm
T_B= T_{Colored resin}/ T_{Non-colored resin}
[0199]
(2) Appearance test and evaluation
Regarding the appearance, the reflection density (OD value) of the test piece was measured using a transmission / reflection densitometer (trade name: TR-927, manufactured by Macbeth).
[0200]
In general, it is judged that the one having a higher reflection density (OD value) has higher surface smoothness and rich surface gloss.
[0201]
(3) Light resistance test and evaluation
Using a xenon weather meter (trade name: Atlas CI-4000, manufactured by Toyo Seiki Co., Ltd.), the test piece was irradiated for 200 hours at a cycle of [006] (repetition of phase 1 and phase 2). The color difference ΔE between the test piece after irradiation and the test piece before irradiation was measured using a spectral color difference meter (manufactured by JUKI, product name: JP7000).
[0202]

[0203]
In general, it is determined that the color difference ΔE is larger when the hue color of the test piece is more advanced.
[0204]
(4) Thermal stability test
A test piece is put in an oven and allowed to stand at 160 ° C. for 240 hours, and the color difference ΔE between the test piece after 240 hours and the test piece before being put in the oven is measured using a spectrocolor difference meter (trade name: JP7000, manufactured by JUKI). It was measured.
[0205]
In general, it is determined that the color difference ΔE is higher in the hue of the test piece.
[0206]
(5) Moisture resistance test
The color difference ΔE between the test piece after placing it in a thermostatic bath and leaving it to stand at 80 ° C. and 95% humidity for 1 week, and the test piece before putting it in the thermostatic bath, is a spectral color difference meter (manufactured by JUKI, trade name: JP7000). It measured using.
[0207]
In general, it is judged that the color difference ΔE is larger when the surface of the colorant in the test piece is larger.
[0208]
(6) Thermal analysis (TG / DTA) test
Using a TG / DTA measuring instrument (trade name: SII EXSTAR6000, manufactured by Seiko Instruments Inc.), Air (air) is used in an atmosphere of 200 ml / min. Measured the sample (coloring agent) at a constant temperature of 550 ° C.
[0209]
FIG. 4 shows a TG / DTA chart of the colorant for laser light transmitting colored resin composition of Example 1 (Colorant Example 1), and FIG. 4 shows a TG / DTA chart of the anthraquinone salt-forming dye of Compound 1 (Compound Example 1). 5 is a TG / DTA chart of the colorant of Comparative Example 1, and FIG. 7 is a TG / DTA chart of the anthraquinone dye represented by the formula (12-4).
[0210]
In the TG / DTA chart, if an endothermic peak is included between 200 and 300 ° C., the bond of the dye is cut in the molding machine, which appears as surface precipitation in the moisture resistance test, and in this temperature range. If an exothermic peak is included, it is presumed that the dye is decomposed and adversely affects the resin.
[0211]
(7) Solvent resistance test
The test piece is completely immersed in ethanol, sealed, and left in a thermostat at 40 ° C. for 48 hours. The color difference between the test piece and the test piece before the test, as well as the ethanol after the test and the ethanol before the test. The color difference ΔE was measured using a spectral color difference meter (trade name: JP7000, manufactured by JUKI).
[0212]
It is presumed that as the color difference ΔE of the test piece is higher, a part of the colorant in the test piece dissolves and diffuses into ethanol and appears as the ethanol color difference ΔE.
[0213]
[Table 9]

[0214]
[Table 10]

[Brief description of the drawings]
1 is a transmittance chart for the test piece of Example 11. FIG.
2 is a transmittance chart for the test piece of Comparative Example 1. FIG.
FIG. 3 is a transmittance chart for a test piece of non-colored resin.
4 is a TG / DTA chart of a colorant for a laser light transmitting colored resin composition of Example 1 (Colorant Example 1). FIG.
5 is a TG / DTA chart of an anthraquinone salt-forming dye (Compound Example 1) of Production Example 1. FIG.
6 is a TG / DTA chart of the colorant of Comparative Example 1. FIG.
FIG. 7 is a TG / DTA chart of an anthraquinone dye represented by formula (12-4).

Claims (23)

At least one anthraquinone salt-forming dye represented by the following formulas (1) to (3):
And
Perinone red dyes and pigments represented by the following formula (5), anthrapyridone red salt-forming dyes represented by the following formula (6), and yellow to red monoazo metal-containing dyes represented by the following formula (7) at least one comprising a black colorant for coloring a resin composition having transparency to laser light having a wavelength of 800nm to 1100nm for.

... (1)
[In Formula (1),
R ² , R ³ , and R ⁵ are independently of each other hydrogen, or

.... (1-a)
Indicate
R ¹ and R ⁴ each independently represent hydrogen, an alkyl group, an alkenyl group, an alkoxy group, an amino group, a hydroxyl group, a halogen, or a sulfonic acid group;
X ¹ represents O or NH;
R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ each independently represent hydrogen, an alkyl group, an alkenyl group, an alkoxy group, an amino group, a hydroxyl group, or a halogen;
[L] ^{b +} represents a cation or a quaternary organic ammonium ion derived from at least one amine selected from the group consisting of aliphatic diamine derivatives, rosin amine derivatives, guanidine derivatives, aromatic amine derivatives, and aromatic diamine derivatives. ,
n ¹ represents an integer of 0 to 4,
n ³ represents an integer of 0 to 4,
m ¹ represents an integer of 1 to 6,
a represents an integer of 1 to 4,
b represents 1 or 2,
K ² is an integer of 1 to 6. ]

... (2)
[In Formula (2),
R ⁴⁷ , R ⁴⁸ , R ⁴⁹ , R ⁵⁰ , R ⁵¹ , and R ⁵² are independently of each other hydrogen, alkyl group, aryl group, alkenyl group, alkoxy group, amino group, N-alkylamide group, N- An arylamide group, a hydroxyl group, a halogen, an acyl group, an acyloxy group, an acylamide group, an acyl-N-alkylamide group, a carboxyl group, an alkoxylcarbonyl group, or a sulfonic acid group, and at least one of R ^{47 to} R ⁵² is a sulfone group An acid group,
The connector J represents the following formula (2-a) or (2-b),

... (2-a)
Or

... (2-b)
(F) ^{h +} represents a cation or a quaternary organic ammonium ion derived from at least one amine selected from the group consisting of aliphatic diamine derivatives, rosin amine derivatives, guanidine derivatives, aromatic amine derivatives, and aromatic diamine derivatives. ,
m ⁴ represents an integer of 1 to 6,
h represents 1 or 2,
K ³ represents an integer of 1 to 6,
R ⁵³ and R ⁵⁴ each independently represent hydrogen or an alkyl group. ]

... (3)
[In Formula (3),
R ⁵⁸ , R ⁵⁹ , and R ⁶⁰ each independently represent hydrogen, an alkyl group, an alkenyl group, an alkoxy group, an amino group, a hydroxyl group, a halogen, a cyclohexylamide group, or a sulfonic acid group;
X ² represents O or NH,
R ⁵⁵ , R ⁵⁶ , and R ⁵⁷ are independently of each other hydrogen, alkyl group, aryl group, alkenyl group, alkoxy group, amino group, N-alkylamide group, N-arylamide group, hydroxyl group, halogen, cyano. , An acyl group, an acyloxy group, an acylamide group, an acyl-N-alkylamide group, a carboxyl group, an alkoxylcarbonyl group, or a sulfonic acid group,
[T] ^{Z +} represents a cation or a quaternary organic ammonium ion derived from at least one amine selected from the group consisting of aliphatic diamine derivatives, rosin amine derivatives, guanidine derivatives, aromatic amine derivatives, and aromatic diamine derivatives. ,
m ² represents an integer of 1 to 6,
y represents an integer of 1 to 4,
Z represents 1 or 2,
K ⁴ represents an integer of 1 to 6. ]

... (5)
[In Formula (5),
m ³ represents 1 or 2,
A and B each independently represent one of the following formulas (5-a) to (5-c):

... (5-a)

... (5-b)

... (5-c)
[In the formulas (5-a) to (5-c), R ^{12 to} R ²⁷ each independently represent hydrogen, halogen, an alkyl group, an alkoxy group, an aralkyl group, or an aryl group. ]

... (6)
[In Formula (6),
R ⁶⁸ , R ⁶⁹ , R ⁷⁰ , and R ⁷¹ are independently of each other hydrogen, alkyl group, aryl group, alkenyl group, alkoxy group, amino group, hydroxyl group, halogen, acyl group, acyloxy group, acylamide group, acyl -N-alkylamide group, carboxyl group, alkoxycarbonyl group, cyclohexylamide group, sulfonic acid group, or

... (6-a)
Wherein at least one of R ^{68 to} R ⁷¹ represents a sulfonic acid group,
R ⁶⁷ represents hydrogen, an alkyl group, an alkoxy group, an amino group, a hydroxyl group, or a halogen;
P ¹ represents C—R ⁷² or N;
R ⁷² represents hydrogen, an alkyl group, an aryl group, an alkoxy group, an amino group, a hydroxyl group, a halogen, a carboxyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted benzoyl group. Show
(G) ^{S +} represents a cation or quaternary organic ammonium ion derived from at least one amine selected from the group consisting of aliphatic diamine derivatives, rosin amine derivatives, guanidine derivatives, aromatic amine derivatives, and aromatic diamine derivatives. ,
S represents 1 or 2,
m ⁵ represents an integer of 1 to 4,
K ⁵ represents 1 or 2,
P ² represents O or NH;
R ⁷³ , R ⁷⁴ and R ⁷⁵ are independently of each other hydrogen, alkyl group, aryl group, alkenyl group, alkoxy group, amino group, hydroxyl group, halogen, acyl group, acyloxy group, acylamide group, acyl-N. -Represents an alkylamide group, a carboxyl group, an alkoxycarbonyl group, a cyclohexylamide group, or a sulfonic acid group. ]

... (7)
[In Formula (7),
K ¹ represents 0, 1 or 2,
(D) ^{r +} represents a hydrogen ion, a cation derived from an alkali metal, an ammonium ion, a cation based on an organic amine, or a quaternary organic ammonium ion.
m ⁴ represents 0, 1 or 2,
r represents 1 or 2,
X represents 1 or 2,
L ₁ and L ₃ independently of one another represent O or COO;
L ₂ and L ₄ represent O,
M ¹ represents a divalent to tetravalent metal,
R ²⁸ and R ²⁹ are independently of each other hydrogen, Cl, SO ₂ R ³⁰ , or

Indicate
R ³⁰ represents a linear or branched alkyl group,
R ³¹ and R ³² each independently represent hydrogen or a linear or branched alkyl group;
B ¹ and B ² are independent of each other

... (8)
Or

... (9)
Indicate
R ³³ and R ³⁵ are independently of each other hydrogen, Cl, SO ₂ R ³⁷ , or

Indicate
R ³⁷ represents a linear or branched alkyl group,
R ³⁸ and R ³⁹ each independently represent hydrogen or a linear or branched alkyl group;
R ³⁴ and R ³⁶ each independently represent hydrogen, a linear or branched alkyl group, a carboxyl group, a hydroxy group, an alkoxy group, an amino group, or a halogen. ] Containing at least one anthraquinone salt-forming dye represented by the following formulas (1) to (3) and an anthraquinone yellow dye having the following skeleton (f1), (f2) or (f3) , black coloring agent for coloring the resin composition having transparency to laser light having a wavelength of 800nm to 1100 nm.

... (1)
[In Formula (1),
R ² , R ³ , and R ⁵ are independently of each other hydrogen, or

.... (1-a)
Indicate
R ¹ and R ⁴ each independently represent hydrogen, an alkyl group, an alkenyl group, an alkoxy group, an amino group, a hydroxyl group, a halogen, or a sulfonic acid group;
X ¹ represents O or NH;
R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ each independently represent hydrogen, an alkyl group, an alkenyl group, an alkoxy group, an amino group, a hydroxyl group, or a halogen;
[L] ^{b +} represents a cation or a quaternary organic ammonium ion derived from at least one amine selected from the group consisting of aliphatic diamine derivatives, rosin amine derivatives, guanidine derivatives, aromatic amine derivatives, and aromatic diamine derivatives. ,
n ¹ represents an integer of 0 to 4,
n ³ represents an integer of 0 to 4,
m ¹ represents an integer of 1 to 6,
a represents an integer of 1 to 4,
b represents 1 or 2,
K ² is an integer of 1 to 6. ]

... (2)
[In Formula (2),
R ⁴⁷ , R ⁴⁸ , R ⁴⁹ , R ⁵⁰ , R ⁵¹ , and R ⁵² are independently of each other hydrogen, alkyl group, aryl group, alkenyl group, alkoxy group, amino group, N-alkylamide group, N- An arylamide group, a hydroxyl group, a halogen, an acyl group, an acyloxy group, an acylamide group, an acyl-N-alkylamide group, a carboxyl group, an alkoxylcarbonyl group, or a sulfonic acid group, and at least one of R ^{47 to} R ⁵² is a sulfone group An acid group,
The connector J represents the following formula (2-a) or (2-b),

... (2-a)
Or

... (2-b)
(F) ^{h +} represents a cation or a quaternary organic ammonium ion derived from at least one amine selected from the group consisting of aliphatic diamine derivatives, rosin amine derivatives, guanidine derivatives, aromatic amine derivatives, and aromatic diamine derivatives. ,
m ⁴ represents an integer of 1 to 6,
h represents 1 or 2,
K ³ represents an integer of 1 to 6,
R ⁵³ and R ⁵⁴ each independently represent hydrogen or an alkyl group. ]

... (3)
[In Formula (3),
R ⁵⁸ , R ⁵⁹ , and R ⁶⁰ each independently represent hydrogen, an alkyl group, an alkenyl group, an alkoxy group, an amino group, a hydroxyl group, a halogen, a cyclohexylamide group, or a sulfonic acid group;
X ² represents O or NH,
R ⁵⁵ , R ⁵⁶ , and R ⁵⁷ are independently of each other hydrogen, alkyl group, aryl group, alkenyl group, alkoxy group, amino group, N-alkylamide group, N-arylamide group, hydroxyl group, halogen, cyano. , An acyl group, an acyloxy group, an acylamide group, an acyl-N-alkylamide group, a carboxyl group, an alkoxylcarbonyl group, or a sulfonic acid group,
[T] ^{Z +} represents a cation or a quaternary organic ammonium ion derived from at least one amine selected from the group consisting of aliphatic diamine derivatives, rosin amine derivatives, guanidine derivatives, aromatic amine derivatives, and aromatic diamine derivatives. ,
m ² represents an integer of 1 to 6,
y represents an integer of 1 to 4,
Z represents 1 or 2,
K ⁴ represents an integer of 1 to 6. ]

... (f1)

... (f2)

... (f3)
[In any of the formulas (f1), (f2) or (f3), the phenyl group may have a substituent, and the substituents form a ring. Also good. ] Following skeleton (f1), further black color colorant according to claim 1, further comprising the anthraquinone yellow dye having a (f2) or (f3).

... (f1)
Embedded image
... (f2)

... (f3)
[In any of the formulas (f1), (f2) and (f3), the phenyl group may have a substituent, and the substituents form a ring. Also good. ] It contains at least one anthraquinone salt-forming dye represented by the above formulas (1) to (3) and two monoazo metal-containing dyes represented by the above formula (7). The black colorant according to claim 1, wherein the hues are red and yellow, respectively. The black colorant according to any one of claims 1 to 4, wherein the hue of the anthraquinone salt-forming dye represented by the above formulas (1) to (3) is blue. The black colorant according to any one of claims 1 to 4, wherein the hue of the anthraquinone salt-forming dye represented by the above formulas (1) to (3) is purple. The black colorant according to any one of claims 1 to 4, wherein the hue of the anthraquinone salt-forming dye represented by the above formulas (1) to (3) is green. The black colorant according to any one of claims 1 to 4, comprising two anthraquinone dyes represented by the formula (1), wherein the hues of the anthraquinone dyes are blue and green, respectively. [L] ^{b + in} the above formula (1), (F) ^{h +} in the above formula (2), and [t] ^{Z +} in the above formula (3) are represented by the following formula (4-a) or (4-b). The black colorant according to any one of claims 1 to 8, which is a cation to be produced.

[Chemical 7]
... (4-a)
[In the formula (4-a),
R ⁴⁰ and R ⁴¹ independently of each other represent N ⁺ H ₃ or NH ₂ , and R ⁴⁰ and R ^{41 each} represent at least one N ⁺ H ₃ ;
n ² represents an integer of 1 to 12. ]

... (4-b)
[In the formula (4-b),
A represents N,
R ⁴² , R ⁴³ , and R ⁴⁴ each independently represent an alkyl group having 1 to 18 carbon atoms or an aryl group,
R ⁴⁵ represents a substituted or unsubstituted aryl group or a benzyl group. ] The black colorant according to any one of claims 1 to 9, wherein the anthraquinone salt-forming dyes of the above formulas (1) to (3) are poorly water-soluble dyes. The black colorant according to any one of claims 1 to 10, wherein the inorganic salt is 2% by weight or less. In the above anthraquinone salt-forming dye, T _{950 nm} / T _{1050 nm} which is a ratio of T _{950 nm} which is a transmittance of laser light having a wavelength of _{950 nm} and T _{1050 nm} which is a transmittance of laser light having a wavelength of 1050 _nm is 0.9 to 1. The black colorant according to any one of claims 1 to 11, which is 1. The black colorant according to any one of claims 1 to 12, wherein the anthraquinone salt-forming dye does not exhibit any exothermic peak or endothermic peak between 200 ° C and 300 ° C in thermal analysis. The black colorant according to any one of claims 1 to 13, wherein the anthraquinone salt-forming dye exhibits a decomposition temperature of 330 ° C or higher in thermal analysis. Thermoplastic resins, which are colored by a black colorant according to any one of claims 1 to 14, the colored resin composition having transparency to laser light having a wavelength of 800nm to 1100 nm. The T _{colored resin} , which is the transmittance of laser light having a wavelength of 950 nm in the thermoplastic resin colored with the black colorant, and the T, which is the transmittance of laser light having a wavelength of 950 nm, in the same thermoplastic resin as described above, which is not colored. T _{colored resin} / T _{non-colored resin,} which is the ratio of the _{non-colored resin,} claim 15 colored resin composition according 0.8 to 1.2. The ratio of T _{950 nm} / T _{1050 nm,} which is the ratio of T _{950 nm} , which is the transmittance of laser light having a wavelength of 950 nm, to T _{1050 nm} , which is the transmittance of laser light having a wavelength of 1050 _nm is 0.9 to 1.2 16. The colored resin composition according to 16. The coloring according to any one of claims 15 to 17, wherein the thermoplastic resin is at least one resin selected from the group consisting of a polypropylene resin, a polyethylene resin, a polyester resin, a polyamide resin, and a polycarbonate resin. Resin composition. Consisting colored resin composition according to any one of claims 15 to 18, a color filter having transparency to laser light having a wavelength of 800nm to 1100 nm. Color film having transparency to claim consisting claim 15 or 18 colored resin composition according to any one of, the laser beam having a wavelength of 800nm to 1100 nm.   The colored resin composition according to any one of claims 15 to 18, which is used by transmitting a laser beam having a wavelength of 800 nm to 1100 nm.   The color filter according to claim 19, which is used by transmitting laser light having a wavelength of 800 nm to 1100 nm.   The color film according to claim 20, which is used by transmitting a laser beam having a wavelength of 800 nm to 1100 nm.

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