JP4361676B2 - Method for producing pigment composition - Google Patents

Description

【０００９】
【発明の実施の形態】
次に好ましい実施の形態を挙げて本発明をさらに詳しく説明する。
【００１０】
本発明の顔料組成物は、成分Ａ（ε型）と成分Ｂ（成分Ａ以外の顔料）と成分Ｃ−１とを含む。また、本発明の顔料組成物の製造方法は、成分Ａ−１（α型）または成分Ａ−２（結晶型を問わない銅フタロシアニン）と成分Ｂと成分Ｃ−１との混合系の中で、成分Ａ−１または成分Ａ−２を結晶転移させて成分Ａとすることを特徴としている。
【００１１】
先ず、本発明の顔料組成物を構成する各成分について説明する。成分Ａ自体は公知である。成分Ａに混合する成分Ｂは、Ｃ．Ｉ．ピグメントバイオレット１９、Ｃ．Ｉ．ピグメントバイオレット２３およびＣ．Ｉ．ピグメントブルー６０から選ばれる少なくとも１種である。
【００１２】
本発明の顔料組成物は上記成分Ａと成分Ｂと、成分Ｃとして、ベンゼン環に置換基を有する銅フタロシアニン誘導体（成分Ｃ−１）とを必須成分として含む。
【００１３】
成分Ｃ−１を下記式（Ａ）に示す。
【００１４】

【００１５】
本発明の顔料組成物は、前記成分Ａと成分Ｂと成分Ｃ−１とからなり、成分Ａと成分Ｂとの重量比率がＡ：Ｂ＝１００：０．１〜５０、好ましくは１００：０．１〜２０であり、成分Ａと成分Ｃ−１との重量比率がＡ：Ｃ−１＝１００：０．１〜３０、好ましくは０．５〜２０である。
【００１６】
次に本発明の顔料組成物の製造方法を説明する。
（１）第１の製造方法
本発明の方法で使用する成分Ａ−１は、粗製銅フタロシアニンをアシッドペースト法、アシッドスラリー法などの湿式摩砕や、ソルトミリング法などの乾式摩砕などの従来公知の方法で処理して得られるものであり、成分Ａ−１の製造方法は特に限定されない。
【００１７】
成分Ａ−１と成分Ｂと成分Ｃ−１との混合物の摩砕時に使用する非芳香族系溶媒としては、ジエチレングリコールである。非芳香族系溶媒は、通常、成分Ａ−１と成分Ｂと成分Ｃ−１との合計量の５〜１０重量倍程度の量で使用されるが、この量に限定されるものではない。
【００１８】
上記湿式摩砕における各成分の使用割合は、前記の顔料組成物の説明で述べた通りである。成分Ａ−１に対する成分Ｂおよび成分Ｃの使用割合が少なくなるほど、成分Ａ−１の成分Ａへの結晶形態の転移は容易となり、成分Ａ−１に対する成分Ｂ、成分Ｃの使用割合が多くなるほど、上記結晶形態の転移は困難となる。ここで結晶形態の転移が困難ということは、結晶形態の転移に高温や長時間を要することであり、結晶形態の転移が容易ということは、転移が低温あるいは短時間で終了するということを意味する。しかし、結晶形態の転移が容易ということは転移が進み過ぎて、結晶型がα型からβ型になってしまう危険性も大きいことから、結晶形態転移の容易さ、結晶形態の安定性については、成分Ｂおよび成分Ｃの量によってバランスをとることが好ましい。
【００１９】
なお、上記湿式摩砕に際して、上記成分中に少量の成分Ａをシード（結晶種）として加えると、結晶形態の転移の時間を大幅に短縮させることができるので好ましい。シードとしての成分Ａの使用割合は、前記各成分の合計量に対しておよそ０．５〜２０重量％が好ましい。
【００２０】
湿式摩砕には、例えば、ボールミル、ビーズミル、サンドミル、縦型あるいは横型の連続媒体分散機、ニーダー、アトライターなどの、従来から顔料の湿式摩砕に使用されている装置がいずれも使用できる。摩砕装置は温度調節ができ、強力な剪断力を掛け得るものならばいかなる装置でもよい。
湿式摩砕に際して特に重要なことは、摩砕系にβ型がわずかでも混在すると、α型から最も安定なβ型への結晶転移が急速に起こるため、ε型が安定に存在することが困難となる。このために量の多少によらず、β型の混入は避けなければならない。
【００２１】
湿式摩砕に際しては、摩砕助剤としては、従来公知の食塩が使用可能である。湿式摩砕は、通常、６０〜１８０℃、好ましくは８０〜１５０℃で行われる。
【００２２】
（２）第２の製造方法
先ず、前記の成分Ａ−１と成分Ｂと成分Ｃ−１とを乾式摩砕し、次いで得られた乾式摩砕物を非芳香族溶媒中で湿式摩砕する。乾式および湿式摩砕を併用することで、湿式摩砕だけの本発明の第１の製造方法より各成分の混合がより完全となり、成分Ａ−１の成分Ａへの結晶形態の転移時間が短縮される。
一般に乾式摩砕は、β型を摩砕してα型とβ型との混合物を製造する際に使用されるが、本発明においては最初からα型だけを使用するので、α型およびβ型の混合物にはなり得ない。従って、乾式摩砕がβ型の発生の要因になることはなく、より短時間で成分Ａ−１の成分Ａへの結晶転移を完結させるのに優れた方法である。
【００２３】
第２の製造方法における前記の成分Ａ−１に対する前記の成分Ｂおよび成分Ｃの使用割合は、第１の製造方法の場合と同じである。先ず、これらの成分を乾式摩砕するが、各成分の使用全量を一括して摩砕することが、α型からε型への結晶形態の転移を効果的に行ううえで好ましい。また、各成分はその全使用量の少なくとも一部を使用して乾式摩砕することもできる。例えば、成分Ａ−１の全量と他の成分の一部を使用する態様や、各成分の一部だけを使用するなどの使用態様が挙げられるが、これら以外の各成分の使用態様であっても構わない。成分の使用全量の一部を乾式摩砕に使用する場合には、その成分の全量に対する使用割合は特に限定されず、０．１〜９９．９重量％の範囲、好ましくは３０〜７０重量％である。使用する摩砕装置は、第１の方法の湿式摩砕で使用する摩砕装置と同じである。乾式摩砕は、通常、２０〜１００℃、好ましくは３０〜７０℃の温度で行われる。乾式摩砕には、例えば、ボールミル、振動ミル、アトライターなどの公知の乾式摩砕装置が用いられる。また、乾式摩砕に際しても前記の摩砕助剤を使用することができる。
【００２４】
次いで、得られた乾式摩砕物を湿式摩砕するが、いずれかの成分の一部を乾式摩砕した場合には、その成分の残りとともに湿式摩砕する。溶媒は第１の製造方法における場合と同じ非芳香族系溶媒を使用する。湿式摩砕の実際は、第１の製造方法の場合と全く同じである。また、ε型を、必要によりシードとして添加することも第１の製造方法の場合と同様であり、α型からε型への結晶形態の転移時間を短縮することができる。
【００２５】
（３）第３の製造方法
銅フタロシアニンとして結晶形態を問わない、即ち、いずれの結晶形態であってもよい銅フタロシアニン（成分Ａ−２）を使用し、第１段階でアシッドペースト法やアシッドスラリー法に準じて成分Ｂおよび成分Ｃ−１の存在下に、形成させた微細なα型を使用する点で、前記の第１または第２の製造方法とは相違する。第２段階では湿式摩砕を行うが、この点は第１または第２の製造方法と同じである。成分Ａ−２としては、通常、製法の如何によらない粗製銅フタロシアニンが使用できるが、これに限定されるものではない。
【００２６】
第３の製造方法における成分Ａ−２に対する成分Ｂ、成分Ｃ−１の使用割合は、第１または第２の製造方法の場合と同じである。先ず、第１段階のα型の形成に際しては、成分Ａ−２と、成分Ｂおよび成分Ｃ−１を濃度が６０重量％以上の硫酸水溶液に添加する。各成分の使用の態様は、特に限定されない。例えば、全成分を全量使用する、成分Ａ−２の全量とともに成分Ｂの全量または一部と成分Ｃ−１の一部を使用するなどの使用態様が挙げられるが、成分Ａ−２とともに成分Ｂの全量または一部を使用することが好ましい。成分Ｂや成分Ｃの一部を使用する場合には、その全量に対する使用割合は特に限定されず、０．１〜９９．９重量％の範囲、好ましくは３０〜７０重量％である。
【００２７】
硫酸水溶液の使用量は、通常、成分Ａ−２の使用量の５〜３０重量倍程度である。上記各成分を添加する際の硫酸水溶液の温度は、特に限定されないが、通常、１０〜８０℃の範囲である。各成分の添加の仕方は特に限定されず、例えば、予め各成分を混合してから添加しても、同時に添加しても、あるいは任意の順序でそれぞれを別々に添加しても構わない。なお、成分Ｂおよび／またはＣは、それらが硫酸水溶液に溶解しない場合には、できる限り微細に分散できるように予め微細化したものを使用することが好ましいが、成分Ｂは硫酸に溶解するものを使用することが好ましい。また、これらの成分が、硫酸で変質する恐れのある場合には、かかる成分は硫酸水溶液には添加せずに、後述の湿式摩砕時に添加して使用することが好ましい。
【００２８】
次に、上記の硫酸水溶液を多量の水中に注入し、水中に成分Ａ−２をα型に結晶転移させて析出させる。即ち、硫酸水溶液中に溶解した成分Ａ−２と成分Ｂ、Ｃ−１は、微細で均質な混合物として析出する。この際、成分Ａ−２は成分Ａ−１に結晶転移する。これを濾過などの従来公知の分離手段で水溶液から分離し、十分に洗浄した後、乾燥する。
【００２９】
第２段階では、上記の第１段階で得られたα型を含む混合物を、非芳香族系溶媒中で湿式摩砕する。第１段階で成分ＢおよびＣ−１の一部を用いた場合には、これらの残部とともに湿式摩砕する。湿式摩砕の実施および非芳香族系溶媒は、前記第１の製造方法の場合と全く同じである。シードとしてのε型の使用および摩砕助剤の使用も同様である。
【００３０】
以上説明した第１〜３の製造方法における湿式摩砕により形成されたε型と成分Ｂおよび成分Ｃ−１を含む顔料組成物は、非芳香族系溶媒および分散メディア（これを使用した場合）から従来公知の方法で分離され、水洗、乾燥される。なお、本発明の顔料組成物においては、前記の各製造方法におけるいずれかの工程で、ロジン、脂肪族アミン、前記顔料誘導体、１，２−ヒドロキシステアリン酸ポリエステルや１，２−ヒドロキシオレイン酸ポリエステルなどおよびそれらのアミノアルキルアミド類、それらの塩類、上記ポリエステル類のナフチルオキシアルキルエステルなどの高分子分散剤などの従来公知の顔料処理剤、界面活性剤あるいは分散剤を添加することができる。
【００３１】
上記の如き本発明の方法で得られる顔料組成物（Ｘ）は、各成分を、本発明の顔料組成物と同一配合比で単に混合（例えば、乾式摩砕や調色時と同様な操作による混合など）して作製した顔料組成物（Ｙ）とは、熱的挙動が異なり、両者を明確に区別することが可能である。即ち、加熱減量も同時に測定可能な示差熱分析（ＴＧ／ＤＴＡ）装置を用いて、上記の二種の顔料組成物（Ｘ）および（Ｙ）を測定すると、これらの顔料組成物において成分Ｂ由来の減量を伴った弱い発熱ピークの温度域が相違し、本発明方法による顔料組成物（Ｘ）と単なる混合で作製した顔料組成物（Ｙ）とは明瞭に区別することができる。
【００３２】
本発明の顔料組成物（Ｘ）は、従来のε型顔料組成物（Ｙ）よりも光学的に低波長側（４２０〜４４０ｎｍ）での透過率が高く、しかも従来のε型顔料組成物（Ｙ）本来の透過率の減少を招かないことが特徴である。このため色調が赤味鮮明なブルーであり、かかる色調が要求されるカラーフィルターの着色剤として特に有用である。
用途によって着色剤を構成する成分は相違するが、本発明においては着色剤としての本発明の顔料組成物以外の成分（例えば、バインダー樹脂、分散剤、有機溶媒、水、ワニス、プラスチック、助剤など）は着色剤の用途に適したものが使用され、特に限定されるものではない。着色剤中における前記顔料組成物の含有量も特に限定されず、着色剤の用途に応じて適宜決めることができる。
【００３３】
【実施例】
次に実施例、比較例および使用例を挙げて本発明をさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、文中、部または％とあるのは特に断りのない限り重量基準である。なお、以下の実施例で製造された顔料組成物中の銅フタロシアニンがε型であることは、Ｘ線回折のブラッグ角より確認した。
【００３４】
＜比較例１＞
公知の方法で得たα型１００部、ベンゼン環に１〜２モルのフタルイミドメチル基が結合した銅フタロシアニン誘導体（以下「ＰＩＭ」と略す）（下記式（Ｉ）で表わされる）３部、シードとしてε型（Ｃ．Ｉ．ピグメントブルー１５：６、以下同じ）１０部、食塩３００部、およびジエチレングリコール（以下「ＤＥＧ」と略す）１１０部をニーダー中で、内容物の温度を１００〜１１０℃に保って１５時間湿式摩砕した。得られた内容物を２％の希硫酸水溶液中で加熱処理し、濾過、水洗、乾燥することによってε型を含む比較例の顔料組成物を得た。

【００３５】
ＴＧ／ＤＴＡ測定装置（セイコー電子工業社製 ＳＳＣ５２００熱分析システム）を用い、昇温スピード１０℃／分の条件で上記の顔料組成物を分析すると、４５０℃付近から減量を伴った銅フタロシアニンに特有な強大な発熱ピークが観測された。
【００３６】
＜実施例３＞
公知の方法で得たα型１００部、ＰＩＭ３部、ジオキサジンバイオレット顔料（Ｃ．Ｉ．ピグメントバイオレット２３、以下同じ）３部、シードとしてε型１０部、食塩３００部、およびＤＥＧ１１０部をニーダー中で内容物の温度を１００〜１１０℃に保持して１５時間湿式摩砕した。得られた内容物を２％の希硫酸水溶液中で加熱処理し、濾過、水洗、および乾燥し、本発明の顔料組成物を得た。
【００３７】
＜実施例４＞
公知の方法によるα型１００部、ＰＩＭ３部およびジオキサジンバイオレット顔料３部をアトライター中で１時間乾式摩砕し、得られた混合物、シードとしてε型１０部、食塩３００部、およびＤＥＧ１１０部をニーダー中で内容物の温度を１００〜１１０℃に保持して７時間湿式摩砕した。得られた内容物を２％の希硫酸水溶液中で加熱処理し、濾過、水洗、および乾燥し、本発明の顔料組成物を得た。
【００３８】
＜実施例６＞
公知の方法によるα型１００部、ＰＩＭ３部およびキナクリドンバイオレット（Ｃ．Ｉ．ピグメントバイオレット１９、以下同じ）顔料３部をアトライター中で１時間乾式摩砕した。得られた混合物、シードとしてε型１０部、食塩３００部、およびＤＥＧ１１０部をニーダー中で内容物の温度を８０〜９０℃に保って４０時間湿式摩砕した。得られた内容物を２％の希硫酸水溶液中で加熱処理し、濾過、水洗、および乾燥し、本発明の顔料組成物を得た。
【００３９】
＜実施例７＞
公知の方法によるα型１００部、ＰＩＭ１０部およびキナクリドンバイオレット顔料３部をアトライター中で１時間乾式摩砕した。得られた混合物、シードとしてε型１０部、食塩３００部、およびＤＥＧ１１０部をニーダー中で１１０〜１２０℃で３０時間湿式摩砕した。得られた内容物を２％の希硫酸水溶液中で加熱処理し、濾過、水洗、および乾燥し、本発明の顔料組成物を得た。
【００４０】
＜実施例８＞
公知の方法による粗製銅フタロシアニンブルー１００部およびキナクリドンバイオレット顔料３部を８００部の９８％硫酸中で溶解した後、得られた溶液を３２００部の水に注入してα型を含む混合物を析出させ、濾過、水洗、および乾燥した。得られたα型を含む混合物、ＰＩＭ３部、シードとしてε型１０部、食塩３００部、およびＤＥＧ１１０部をニーダー中で１００〜１１０℃で１０時間湿式摩砕した。得られた内容物を２％の希硫酸水溶液中で加熱処理し、濾過、水洗、および乾燥し、本発明の顔料組成物を得た。
【００４１】
＜実施例９＞
公知の方法による粗製銅フタロシアニンブルー１００部およびジオキサジンバイオレット顔料３部を２０００部の８１％硫酸中で溶解した後、得られた溶液を６０００部の水中に加えてα型を含む混合物を析出させ、濾過、水洗、および乾燥した。得られたα型を含む混合物、ＰＩＭ３部、シードとしてε型１０部、食塩３００部、およびＤＥＧ１１０部をニーダー中で１００〜１１０℃で１０時間湿式摩砕した。得られた内容物を２％の希硫酸水溶液中で加熱処理し、濾過、水洗、および乾燥し、本発明の顔料組成物を得た。この顔料組成物を比較例１と同様にして示差熱分析を行ったところ、３９５℃付近に減量を伴った弱い発熱ピークと、４５０℃付近から減量を伴った強大な発熱ピークが観測された。
【００４２】
＜実施例１０＞
公知の方法による粗製銅フタロシアニンブルー１００部およびジオキサジンバイオレット顔料１０部を２０００部の９８％硫酸中に溶解した後、得られた溶液を６０００部の水に注入してα型を含む混合物を析出させ、濾過、水洗、および乾燥した。得られたα型を含む混合物、ＰＩＭ３部、シードとしてε型１０部、食塩３００部、およびＤＥＧ１１０部をニーダー中で１００〜１１０℃で１０時間湿式摩砕した。得られた内容物を２％の希硫酸水溶液中で加熱処理し、濾過、水洗、および乾燥し、本発明の顔料組成物を得た。この顔料組成物を比較例１と同様にして示差熱分析を行ったところ、４０５℃付近に減量を伴った弱い発熱ピークと、４５０℃付近から減量を伴った強大な発熱ピークが観測された。
【００４３】
以下に本発明の顔料組成物を含む着色剤およびその使用例を示す。なお、本発明の顔料組成物が下記例示以外のいかなる用途においても着色剤として使用できることはいうまでもない。
【００４４】
＜参考例１＞
顔料組成物として実施例６で作製した顔料組成物を使用し、小型ビーズミルを用い、表１に記載の配合処方に従って濃色エナメルを、また、表２に記載の配合処方に従って白色エナメルを得た。得られた濃色エナメルと白色エナメルを、濃色エナメル／白色エナメル＝１／４の重量比で混合し青色淡彩色塗料を得た。
【００４５】

【００４６】

【００４７】
＜参考例２＞
実施例６の顔料組成物に代えて、実施例８で作製した顔料組成物を使用すること以外は参考例１と同様の方法で青色淡彩色塗料を得た。
【００４８】
＜比較例２＞
実施例６の顔料組成物に代えて、比較例１で作製した顔料組成物と、キナクリドンバイオレット顔料を実施例６の顔料組成物と同比率になるように混合したものを使用すること以外は参考例１と同様の方法で青色淡彩色塗料を得た。
【００４９】
参考例１、２および比較例２の青色淡彩色塗料の各々をスプレー粘度（フォードカップＮＯ．４にて１４秒）までシンナーで希釈し、エアースプレーガンにて下地処理を施したスチールパネルに吹き付け塗装を行なった。１５分間室温にて乾燥後、１４０℃、３０分間焼付硬化させてスチールパネルを作成した。
参考例１および２によるパネルの色調は、比較例２のパネルの色調と比較してより赤味鮮明であり、彩度および着色力に優れていた。これらのパネルの彩度および着色力について、スガ試験機社製の光電色彩計ＳＭカラーコンピューター（モデルＳＭ−４）にて測定した結果を表３に示した。
【００５０】
彩度は Ｃ^*＝〔(ａ^*)²＋(ｂ^*)²〕^1/2
着色力は ＴＳ＝〔１−(Ｖｙｅｘ−Ｖｙｓ)〕×１００
の計算値で示した。なお、Ｖｙｅｘは参考例１および２のｙ値、Ｖｙｓは比較例２のｙ値である。
【００５１】

【００５２】
＜参考例３＞
顔料組成物として実施例３で作製した顔料組成物を使用し、表４に記載の配合処方に従ってＤＯＰ（ジオクチルフタレート）と３本ロール上で４０℃以下で混練し、顔料分５０％のカラーペーストを作製する。このカラーペーストを２本ロール上で１６０〜１６５℃で、ゲル化したポリ塩化ビニルコンパウンドと混練し、取り出した混練物を１６５〜１７５℃で１５０ｋｇ／ｃｍ²の荷重をかけてシート化し、冷却して１ｍｍ厚の濃色シートを作製した。
【００５３】

【００５４】
次に得られた濃色シートと白色ポリ塩化ビニルコンパウンドを表５に記載の配合処方に従って２本ロール上で１６０〜１６５℃で混練し、取り出した混練物を１６０〜１６５℃で１５０ｋｇ／ｃｍ²の荷重をかけてシート化し、冷却して１ｍｍ厚の淡色シートを作製した。
【００５５】

【００５６】
＜参考例４および５＞
実施例３の顔料組成物の代わりに、それぞれ実施例４および９で作製した顔料組成物を使用すること以外は参考例３と同様の方法で濃色シートおよび淡色シートを作成した。
【００５７】
＜比較例３＞
実施例３の顔料組成物の代わりに、比較例１で作成した顔料組成物とジオキサジンバイオレットを実施例３の顔料組成物と同比率になるよう混合したものを使用する以外は参考例３と同様の方法で濃色シートおよび淡色シートを作成した。
【００５８】
参考例３、４、５および比較例３の濃色シートについて、色調の鮮明性および透明性を目視にて判定した。また、参考例３、４、５および比較例３の淡色シートについては、その着色力を前記と同様の装置にて測定し、同様の計算値にて示した。その結果を表６に示す。
【００５９】

【００６０】
＜参考例６＞
顔料組成物として実施例９で作製した顔料組成物を使用し、表７の配合処方にて分散させ、カラーフィルター用着色剤（ベースカラー）を作製した。
【００６１】

【００６２】
＜比較例４＞
実施例９で作製した顔料組成物に代えて、比較例１で作製した顔料組成物を使用する以外は参考例６と同様の方法でベースカラーを作製した。
【００６３】
＜比較例５＞
実施例９で作製した顔料組成物に代えて、比較例１で作製した顔料組成物とジオキサジンバイオレット顔料を実施例９の顔料組成物と同比率になるように混合したものを使用する以外は参考例６と同様の方法でベースカラーを作製した。
【００６４】
参考例６、比較例４および５のベースカラーそれぞれをスピンコーターにてガラス基板に塗布し、プリベークした。この塗布パネルを大日精化工業社製カラコムＣで光透過特性を測色したところ、表８に示す値が得られた。また、これらのプリベーク膜の分光光度計で測定した分光カーブを図１に示す。
【００６５】

【００６６】
塗布パネルの耐熱性を評価するために、上記の各塗布パネルを２５０℃の加熱雰囲気中に１時間放置後、測色した。耐熱性の指標として耐熱性試験前後の色差（ΔＥａｂ^*（耐熱性））を求めた。また、塗布パネルの耐光性を評価するために、参考例６、比較例４および５のベースカラーそれぞれをスピンコーターにてガラス基板に塗布し、プリベーク後、測色した。その各塗布パネルをメタルハライドランプ９０ｍＷ雰囲気に１２時間放置後、測色した。耐光性の指標としてメタルハライドランプ照射前後の色差（ΔＥａｂ^*（耐光性））を求めた。以上の結果を表９に示した。
【００６７】

参考例６で得られる青色ベースカラーは、比較例４および５の青色ベースカラーに比較して、耐熱性および耐光性について明らかな優位が認められた。
【００６８】
＜参考例７＞
ブルー（Ｂ）のカラーフィルター膜を得るために、参考例６のブルーベースカラーを使用し、表１０の配合処方にてＢの感光性顔料分散液を得た。
【００６９】
＜参考例８＞
レッド（Ｒ）のカラーフィルター膜を得るために、参考例６において、顔料として実施例９で作製した顔料組成物を使用する代わりに赤色顔料（Ｃ．Ｉ．ピグメントレッド１７７）を使用する以外は参考例６と同様の方法で作製したレッドベースカラーを使用し、表１０の配合処方にてＲの感光性顔料分散液を得た。
【００７０】
＜参考例９＞
グリーン（Ｇ）のカラーフィルター膜を得るために、参考例６において、顔料として実施例９で作製した顔料組成物を使用する代わりに緑色顔料（Ｃ．Ｉ．ピグメントグリーン３６）を使用する以外は参考例６と同様の方法で作製したグリーンベースカラーを使用し、表１０の配合処方にてＧの感光性顔料分散液を得た。
【００７１】

【００７２】
＜参考例１０＞
液晶カラーディスプレイのＲ、Ｇ、Ｂのカラーフィルターを得るために、シランカップリング剤処理を行ったガラス基板をスピンコーターにセットし、上記Ｒのカラーフィルター用感光性顔料分散液を最初３００ｒｐｍで５秒間、次いで１，２００ｒｐｍで５秒間の条件でスピンコートした。次いで８０℃で１０分間プリベークを行い、モザイク状のパターンを有するフォトマスクを密着させ、超高圧水銀灯を用い、１００ｍＪ／ｃｍ²の光量で露光を行った。次いで専用現像液および専用リンスで現像および洗浄を行い、ガラス基板上に赤色のモザイク状パターンを形成させた。
【００７３】
引き続いて緑色モザイク状パターンおよび青色モザイク状パターンを上記のＧおよびＢのカラーフィルター用感光性顔料分散液を用いて上記の方法に準じて塗布および焼付けを行って形成し、ＲＧＢのカラーフィルターを得た。上記で得られたカラーフィルターは、優れた分光カーブ特性を有し、耐光性、耐熱性などの堅牢性に優れ、また、光の透過性にも優れた性質を有し、特に青色が鮮明な赤味青色の色調および高透過性の特長を有する液晶カラーフィルターとして優れた性質を有していた。
【００７４】
【発明の効果】
本発明の顔料組成物は、あらゆる用途、例えば、プラスチック用着色剤、塗料、印刷インキ、捺染剤、電子写真トナー、カラーフィルター用カラー、インクジェット用インキ、熱転写インキなどの着色において、彩度、鮮明性の低下、透過率の減少を起こすことなく、従来の銅フタロシアニン顔料より赤味鮮明な色調を呈するとともに、耐熱性、耐溶剤性、耐光性、耐候性が向上した着色剤として有用である。
【図面の簡単な説明】
【図１】 参考例６、比較例４および５におけるプリベーク膜の分光カーブを示す図。[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a method for producing a pigment composition, and more specifically, a pigment mainly composed of reddish and clear ε-type copper phthalocyanine (hereinafter abbreviated as “component A” or “ε-type”) suitable for various coloring applications. The purpose is to provide a composition.
[0002]
[Prior art]
  Copper phthalocyanine blue pigment is particularly stable among all pigments, is excellent in various resistances, and has many crystal forms. Among them, the main ones that are actually industrialized are α-type copper phthalocyanine pigment (hereinafter abbreviated as “component A-1” or “α-type”), β-type copper phthalocyanine pigment (hereinafter abbreviated as “β-type”). ) And ε types are known. In general, the β type is used for coloring greenish blue, and the α type is used for coloring reddish blue. When it is required to be colored, the ε type is used.
[0003]
[Problems to be solved by the invention]
  However, in various coloring applications, there is a case where it is required to color a reddish blue further than the ε type, and such a strong reddish color tone cannot be realized with a single copper phthalocyanine pigment. For this reason, it is usually necessary to rely on the use of a mixture of copper phthalocyanine and a pigment that is more reddish than copper phthalocyanine. However, when two or more types of pigments are mixed and used in the state of powder or colorant as described above, it becomes subtractive color mixing, and the saturation and vividness decrease and the transmittance decrease in the color tone to be obtained. Was inevitable.
  In order to improve such a problem, the invention has been devised so that the resulting pigment mixture exhibits similar behavior to a single pigment by mixing two or more pigments in the process of conditioning the pigment. . For example, there is a method of dry grinding a copper phthalocyanine pigment and other pigments to obtain a pigment mixture. However, the pigment mixture obtained by this method still lacks coloring power and sharpness.
[0004]
  As a method for making up for the disadvantages of the above-mentioned dry milling and giving the obtained mixed pigment excellent homogeneity, a method of producing a pigment mixture by wet milling has also been proposed. The pigment mixture obtained by this method is excellent in dispersibility and sharpness, but does not exhibit particularly excellent properties in heat resistance, solvent resistance, light resistance, and weather resistance.
  Even if the pigment processing method by grinding as described above and other processing methods are performed, the crystal form of the copper phthalocyanine pigment after the basic treatment is an ε-type crystal form showing a reddish-purple blue color tone. If this method is not used, the pigment mixture that develops the reddish blue color cannot be obtained.
  Also known is a method in which a copper phthalocyanine pigment and other pigments are dissolved in sulfuric acid and co-precipitated in water to obtain a pigment composition. The copper phthalocyanine pigment in the pigment composition obtained by this method is also known. Are all α-type, and the color tone of the basic copper phthalocyanine pigment itself is greener than that of the ε-type, so that the above pigment mixture that develops a reddish blue color cannot be obtained.
[0005]
  Accordingly, an object of the present invention is to provide a copper phthalocyanine pigment composition that eliminates the disadvantages of the prior art and develops a reddish and bright blue color composed of a mixture of a more reddish ε-type and other pigments. It is.
  As a result of diligent research to achieve the above object, the inventors of the present invention have the ε type as a main component by crystal transition of the α type to the ε type in a pigment mixture of the α type and other pigments. The present inventors have found that a pigment composition that is a more homogeneous mixture can be obtained and completed the present invention.
[0006]
[Means for Solving the Problems]
  The above object is achieved by the present invention described below. That is, the present inventionContains ε-type copper phthalocyanineThe first production method of the pigment composition is the α type, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23 and C.I. I. At least one selected from CI Pigment Blue 60 (component B);A copper phthalocyanine derivative (component C-1) represented by the following formula (I):The weight ratio is a ratio of A-1: B = 100: 0.1-50,And the weight ratio of component A-1 and component C-1 is the ratio of A-1: C-1 = 100: 0.1-30,It is characterized by wet milling in diethylene glycol as a non-aromatic solvent in the presence of sodium chloride as a grinding aid.
[0007]
  Of the present inventionContains ε-type copper phthalocyanineThe second production method of the pigment composition includes the component A-1 and the component BComponent C-1 andThe weight ratio is a ratio of A-1: B = 100: 0.1-50,And the weight ratio of component A-1 and component C-1 is the ratio of A-1: C-1 = 100: 0.1-30,It is characterized by dry milling and then wet milling the resulting dry milled product in diethylene glycol as a non-aromatic solvent in the presence of sodium chloride as a grinding aid.
[0008]
  Of the present inventionContains ε-type copper phthalocyanineThe third production method of the pigment composition includes copper phthalocyanine (component A-2) regardless of crystal type, component B, andComponent C-1 andThe weight ratio of A-2: B = 100: 0.1-50,And the weight ratio of component A-2 and component C-1 is the ratio of A-2: C-1 = 100: 0.1-30,It is added to 60% by weight or more of an aqueous sulfuric acid solution, and the resulting aqueous sulfuric acid solution is poured into water to cause crystal transition of the component A-2 to the α type.Component C-1 andIs wet-milled in diethylene glycol as a non-aromatic solvent in the presence of sodium chloride as a grinding aid.

[0009]
DETAILED DESCRIPTION OF THE INVENTION
  Next, the present invention will be described in more detail with reference to preferred embodiments.
[0010]
  The pigment composition of the present invention comprises component A (ε type), component B (pigment other than component A),Component C-1 andincluding. In addition, the method for producing the pigment composition of the present invention comprises component A-1 (α type) or component A-2 (copper phthalocyanine of any crystal type) and component B.Component C-1 andIn the mixed system, component A-1 or component A-2 is crystallized into component A.
[0011]
  First, each component which comprises the pigment composition of this invention is demonstrated. Component A itself is known. Component B mixed with Component A isC. I. Pigment violet 19, C.I. I. Pigment violet 23 and C.I. I. At least one selected from Pigment Blue 60It is.
[0012]
  The pigment composition of the present invention comprises the above component A, component B, and,As component C, a copper phthalocyanine derivative having a substituent on the benzene ring (component C-1) andAs an essential ingredient.
[0013]
  Component C-1It is shown in the following formula (A).
[0014]

[0015]
  The pigment composition of the present invention comprises component A and component B.And component C-1And the weight ratio of component A to component B is A: B = 100: 0.1-50, preferably 100: 0.1-20, MatureMinute A and Component C-1The weight ratio is A: C-1= 100: 0.1-30, preferably 0.5-20is there.
[0016]
  Next, the manufacturing method of the pigment composition of this invention is demonstrated.
(1) First manufacturing method
  Component A-1 used in the method of the present invention is obtained by treating crude copper phthalocyanine by a conventionally known method such as wet grinding such as acid paste method or acid slurry method or dry grinding such as salt milling method. The manufacturing method of component A-1 is not particularly limited.
[0017]
  Component A-1 and Component BComponent C-1 andThe non-aromatic solvent used when the mixture is ground is diethylene glycol. Non-aromatic solvents are usually component A-1 and component B.AndMinute CWith -1Although it is used in an amount of about 5 to 10 times the total amount, it is not limited to this amount.
[0018]
  The use ratio of each component in the wet milling is as described in the description of the pigment composition. The smaller the proportion of component B and component C used relative to component A-1, the easier the transition of the crystal form of component A-1 to component A, and the greater the proportion of component B and component C used relative to component A-1. The transition of the crystal form becomes difficult. Here, the difficulty of transition of the crystal form means that the transition of the crystal form requires a high temperature and a long time, and that the transition of the crystal form is easy means that the transition is completed at a low temperature or in a short time. To do. However, the easy transition of the crystal form means that the transition is too advanced and there is a great risk that the crystal form will change from α form to β form. , Component B andBiseiIt is preferable to balance by the amount of the minute C.
[0019]
  In the wet milling, it is preferable to add a small amount of component A as a seed (crystal seed) to the components because the time for transition of the crystal form can be greatly shortened. The proportion of component A used as a seed is preferably about 0.5 to 20% by weight based on the total amount of each component.
[0020]
  For wet milling, any of the apparatuses conventionally used for wet milling of pigments such as a ball mill, bead mill, sand mill, vertical or horizontal continuous medium disperser, kneader, and attritor can be used. The milling apparatus may be any apparatus that can control the temperature and can apply a strong shearing force.
  Of particular importance during wet milling is that it is difficult for the ε-type to exist stably because the crystal transition from the α-type to the most stable β-type occurs rapidly if even a small amount of β-type is mixed in the grinding system. It becomes. For this reason, β-type contamination must be avoided regardless of the amount.
[0021]
  In wet grinding, conventionally known salt can be used as a grinding aid. The wet grinding is usually performed at 60 to 180 ° C, preferably 80 to 150 ° C.
[0022]
(2) Second manufacturing method
  First, component A-1 and component B described aboveAndMinute C-1And then dry milling the resulting dry milled product in a non-aromatic solvent. By using both dry and wet milling, the mixing of each component becomes more complete than the first production method of the present invention using only wet milling, and the transition time of the crystal form of component A-1 to component A is shortened. Is done.
  Generally, dry milling is used when milling β-form to produce a mixture of α-form and β-form. In the present invention, only α-form is used from the beginning, so α-form and β-form are used. Cannot be a mixture of Therefore, dry grinding does not cause the generation of β-form, and is an excellent method for completing the crystal transition of component A-1 to component A in a shorter time.
[0023]
  The use ratio of the component B and the component C with respect to the component A-1 in the second production method is the same as in the first production method. First, these components are dry-milled. However, it is preferable to grind all the used amounts of each component at once in order to effectively carry out the transition of the crystal form from α-type to ε-type. Each component can also be dry milled using at least a portion of its total usage. For example, there are modes in which the total amount of component A-1 and a part of other components are used, and modes of use in which only a part of each component is used. It doesn't matter. When a part of the total amount of the component is used for dry grinding, the ratio of the component to the total amount is not particularly limited, and is in the range of 0.1 to 99.9% by weight, preferably 30 to 70% by weight. It is. The milling device used is the same as that used in the wet milling of the first method. Dry milling is usually performed at a temperature of 20 to 100 ° C, preferably 30 to 70 ° C. For dry grinding, for example, a known dry grinding apparatus such as a ball mill, a vibration mill, or an attritor is used. Also, the above grinding aid can be used for dry grinding.
[0024]
  The resulting dry milled product is then wet milled, but if some of any component is dry milled, it is wet milled with the rest of the component. As the solvent, the same non-aromatic solvent as in the first production method is used. The actual wet milling is exactly the same as in the first manufacturing method. Further, the addition of the ε type as a seed as necessary is the same as in the case of the first manufacturing method, and the transition time of the crystal form from the α type to the ε type can be shortened.
[0025]
(3) Third manufacturing method
  Copper phthalocyanine may be in any crystal form, that is, copper phthalocyanine (component A-2), which may be in any crystal form, is used, and in the first stage, component B and component according to the acid paste method or acid slurry method are used.BiseiMinute C-1This method is different from the first or second manufacturing method in that the formed fine α-type is used in the presence of. In the second stage, wet grinding is performed, which is the same as the first or second manufacturing method. As component A-2, crude copper phthalocyanine which does not depend on the production method can be usually used, but is not limited thereto.
[0026]
  Component B and Component C with respect to Component A-2 in the third production method-1The ratio of use is the same as in the first or second manufacturing method. First, in forming the α-type in the first stage, component A-2, component B andBiseiMinute C-1Is added to an aqueous sulfuric acid solution having a concentration of 60% by weight or more. The mode of use of each component is not particularly limited. For example, all the components are used, and all or a part of component B and component C together with the total amount of component A-2.-1However, it is preferable to use all or part of Component B together with Component A-2. When using a part of component B or component C, the usage rate with respect to the whole quantity is not specifically limited, It is the range of 0.1-99.9 weight%, Preferably it is 30-70 weight%.
[0027]
  The usage-amount of sulfuric acid aqueous solution is about 5 to 30 weight times normally the usage-amount of component A-2. Although the temperature of the sulfuric acid aqueous solution at the time of adding each said component is not specifically limited, Usually, it is the range of 10-80 degreeC. The method of adding each component is not particularly limited. For example, each component may be added after being mixed in advance, may be added simultaneously, or may be added separately in any order. In addition, it is preferable to use components B and / or C that have been refined in advance so that they can be dispersed as finely as possible if they do not dissolve in the aqueous sulfuric acid solution, but component B is soluble in sulfuric acid. Is preferably used. Moreover, when there is a possibility that these components may be altered by sulfuric acid, it is preferable to add these components during wet milling described later without adding them to the sulfuric acid aqueous solution.
[0028]
  Next, the sulfuric acid aqueous solution is poured into a large amount of water, and component A-2 is crystallized into α-form and precipitated in water. That is, component A-2 and components B and C dissolved in sulfuric acid aqueous solution-1Precipitate as a fine and homogeneous mixture. At this time, component A-2 undergoes crystal transition to component A-1. This is separated from the aqueous solution by a conventionally known separation means such as filtration, thoroughly washed and then dried.
[0029]
  In the second stage, the mixture containing α-form obtained in the first stage is wet-ground in a non-aromatic solvent. In the first stage, component B andAnd C-1When a part of is used, wet milling is performed together with the remainder. The wet milling and the non-aromatic solvent are exactly the same as in the first production method. The same applies to the use of ε-type as seed and the use of grinding aids.
[0030]
  The ε-type formed by wet grinding in the first to third production methods described above, component B andBiseiMinute C-1Is separated from the non-aromatic solvent and the dispersion medium (when used) by a conventionally known method, washed with water and dried. In the pigment composition of the present invention, rosin, aliphatic amine, the pigment derivative, 1,2-hydroxystearic acid polyester, and 1,2-hydroxyoleic acid polyester are used in any of the above-described production methods. And conventionally known pigment treating agents, surfactants or dispersants such as aminoalkylamides, salts thereof, polymer dispersants such as naphthyloxyalkyl esters of the above polyesters, and the like can be added.
[0031]
  In the pigment composition (X) obtained by the method of the present invention as described above, each component is simply mixed at the same blending ratio as that of the pigment composition of the present invention (for example, by the same operation as in dry grinding or toning). The pigment composition (Y) prepared by mixing and the like has a different thermal behavior and can be clearly distinguished from each other. That is, when the above two types of pigment compositions (X) and (Y) are measured using a differential thermal analysis (TG / DTA) apparatus capable of simultaneously measuring loss on heating, the component B is derived from these pigment compositions. The temperature range of the weak exothermic peak accompanied by a decrease in the amount of is different, and the pigment composition (X) produced by the method of the present invention can be clearly distinguished from the pigment composition (Y) prepared by simple mixing.
[0032]
  The pigment composition (X) of the present invention has an optically higher transmittance on the lower wavelength side (420 to 440 nm) than the conventional ε-type pigment composition (Y), and the conventional ε-type pigment composition ( Y) The feature is that the original transmittance is not reduced. For this reason, the color tone is reddish and clear blue, and it is particularly useful as a colorant for a color filter that requires such a color tone.
  The components constituting the colorant differ depending on the use, but in the present invention, components other than the pigment composition of the present invention as the colorant (for example, binder resin, dispersant, organic solvent, water, varnish, plastic, auxiliary agent) Etc.) are suitable for the use of the colorant, and are not particularly limited. The content of the pigment composition in the colorant is also not particularly limited, and can be appropriately determined according to the use of the colorant.
[0033]
【Example】
  EXAMPLES Next, although an Example, a comparative example, and a usage example are given and this invention is demonstrated further more concretely, this invention is not limited to these Examples. In the text, “part” or “%” is based on weight unless otherwise specified. In addition, it confirmed from the Bragg angle | corner of X-ray diffraction that the copper phthalocyanine in the pigment composition manufactured in the following Examples was an epsilon type.
[0034]
<Comparative Example 1>
  100 parts of α-type obtained by a known method, 3 parts of a copper phthalocyanine derivative (hereinafter abbreviated as “PIM”) having 1 to 2 moles of phthalimidomethyl group bonded to a benzene ring, represented by the following formula (I), seed 10 parts of ε type (CI Pigment Blue 15: 6, hereinafter the same), 300 parts of salt, and 110 parts of diethylene glycol (hereinafter abbreviated as “DEG”) in a kneader, the temperature of the content is 100-110 ° C. And wet milling for 15 hours. The obtained contents were heat-treated in a 2% dilute sulfuric acid aqueous solution, filtered, washed with water, and dried to obtain a pigment composition of Comparative Example including ε type.

[0035]
  Using the TG / DTA measuring device (SSC5200 thermal analysis system manufactured by Seiko Denshi Kogyo Co., Ltd.), when the above pigment composition is analyzed under the condition of a heating rate of 10 ° C./min, it is peculiar to copper phthalocyanine with weight loss from around 450 ° C. A strong exothermic peak was observed.
[0036]
<Example 3>
  In a kneader, 100 parts of α form obtained by a known method, 3 parts of PIM, 3 parts of dioxazine violet pigment (CI Pigment Violet 23, the same applies hereinafter), 10 parts of ε form, 300 parts of salt and 110 parts of DEG as seeds And wet milling for 15 hours while maintaining the temperature of the contents at 100-110 ° C. The obtained content was heat-treated in a 2% dilute sulfuric acid aqueous solution, filtered, washed with water, and dried to obtain the pigment composition of the present invention.
[0037]
<Example 4>
  100 parts of α form, 3 parts of PIM and 3 parts of dioxazine violet pigment by a known method are dry-milled in an attritor for 1 hour, and the resulting mixture, 10 parts of ε form, 300 parts of salt and 110 parts of DEG as seeds In the kneader, the temperature of the contents was maintained at 100 to 110 ° C. and wet milled for 7 hours. The obtained content was heat-treated in a 2% dilute sulfuric acid aqueous solution, filtered, washed with water, and dried to obtain the pigment composition of the present invention.
[0038]
<Example 6>
  100 parts α form, 3 parts PIM and quinacridone violet by known methods(CI Pigment Violet 19, the same applies hereinafter)Three parts of the pigment were dry milled in an attritor for 1 hour. The obtained mixture, 10 parts of ε-type as seed, 300 parts of salt, and 110 parts of DEG were wet milled in a kneader for 40 hours while maintaining the temperature of the contents at 80-90 ° C. The obtained content was heat-treated in a 2% dilute sulfuric acid aqueous solution, filtered, washed with water, and dried to obtain the pigment composition of the present invention.
[0039]
<Example 7>
  100 parts of α-form, 10 parts of PIM and 3 parts of quinacridone violet pigment by a known method were dry milled in an attritor for 1 hour. The obtained mixture, 10 parts of ε-type as seed, 300 parts of salt, and 110 parts of DEG were wet-ground in a kneader at 110 to 120 ° C. for 30 hours. The obtained content was heat-treated in a 2% dilute sulfuric acid aqueous solution, filtered, washed with water, and dried to obtain the pigment composition of the present invention.
[0040]
<Example 8>
  After dissolving 100 parts of crude copper phthalocyanine blue and 3 parts of quinacridone violet pigment in a known method in 800 parts of 98% sulfuric acid, the resulting solution is poured into 3200 parts of water to precipitate a mixture containing α-form. Filtered, washed with water, and dried. The obtained mixture containing α-form, 3 parts of PIM, 10 parts of ε-type as seed, 300 parts of salt, and 110 parts of DEG were wet-ground in a kneader at 100 to 110 ° C. for 10 hours. The obtained content was heat-treated in a 2% dilute sulfuric acid aqueous solution, filtered, washed with water, and dried to obtain the pigment composition of the present invention.
[0041]
<Example 9>
  After dissolving 100 parts of crude copper phthalocyanine blue and 3 parts of dioxazine violet pigment in a known method in 2000 parts of 81% sulfuric acid, the resulting solution is added to 6000 parts of water to precipitate a mixture containing α-form. Filtered, washed with water, and dried. The obtained mixture containing α-form, 3 parts of PIM, 10 parts of ε-type as seed, 300 parts of salt, and 110 parts of DEG were wet-ground in a kneader at 100 to 110 ° C. for 10 hours. The obtained content was heat-treated in a 2% dilute sulfuric acid aqueous solution, filtered, washed with water, and dried to obtain the pigment composition of the present invention. When this pigment composition was subjected to differential thermal analysis in the same manner as in Comparative Example 1, a weak exothermic peak accompanied by a weight loss around 395 ° C. and a strong exothermic peak accompanied by a weight reduction from around 450 ° C. were observed.
[0042]
<Example 10>
  After 100 parts of crude copper phthalocyanine blue and 10 parts of dioxazine violet pigment are dissolved in 2000 parts of 98% sulfuric acid by a known method, the resulting solution is poured into 6000 parts of water to precipitate a mixture containing α-form. Filtered, washed with water, and dried. The obtained mixture containing α-form, 3 parts of PIM, 10 parts of ε-type as seed, 300 parts of salt, and 110 parts of DEG were wet-ground in a kneader at 100 to 110 ° C. for 10 hours. The obtained content was heat-treated in a 2% dilute sulfuric acid aqueous solution, filtered, washed with water, and dried to obtain the pigment composition of the present invention. When this pigment composition was subjected to differential thermal analysis in the same manner as in Comparative Example 1, a weak exothermic peak accompanied with a weight loss around 405 ° C. and a strong exothermic peak accompanied with a weight loss around 450 ° C. were observed.
[0043]
  The colorant containing the pigment composition of this invention and the example of its use are shown below. In addition, it cannot be overemphasized that the pigment composition of this invention can be used as a coloring agent in any uses other than the following illustration.
[0044]
<Reference Example 1>
  Using the pigment composition prepared in Example 6 as the pigment composition, using a small bead mill, dark enamel was obtained according to the formulation described in Table 1, and white enamel was obtained according to the formulation described in Table 2. . The dark enamel and white enamel thus obtained were mixed at a weight ratio of dark enamel / white enamel = 1/4 to obtain a light blue paint.
[0045]

[0046]

[0047]
<Reference Example 2>
  A blue pale paint was obtained in the same manner as in Reference Example 1 except that the pigment composition prepared in Example 8 was used instead of the pigment composition in Example 6.
[0048]
<Comparative Example 2>
  Reference was made except that instead of the pigment composition of Example 6, the pigment composition prepared in Comparative Example 1 was mixed with quinacridone violet pigment so as to have the same ratio as that of Example 6. A blue pale paint was obtained in the same manner as in Example 1.
[0049]
  Each of the blue light-colored paints of Reference Examples 1 and 2 and Comparative Example 2 is diluted with a thinner to a spray viscosity (14 seconds with Ford Cup No. 4), and sprayed onto a steel panel that has been subjected to ground treatment with an air spray gun. Painted. After drying at room temperature for 15 minutes, a steel panel was prepared by baking and curing at 140 ° C. for 30 minutes.
  The color tone of the panels according to Reference Examples 1 and 2 was clearer than the color tone of the panel of Comparative Example 2, and was excellent in saturation and coloring power. Table 3 shows the results of measuring the saturation and coloring power of these panels using a photoelectric colorimeter SM color computer (model SM-4) manufactured by Suga Test Instruments Co., Ltd.
[0050]
  Saturation is C^*= [(A^*)²+ (B^*)²]^1/2
  The coloring power is TS = [1- (Vyex−Vys)] × 100
It was shown by the calculated value. Vyex is the y value of Reference Examples 1 and 2, and Vys is the y value of Comparative Example 2.
[0051]

[0052]
<Reference Example 3>
  The pigment composition prepared in Example 3 was used as the pigment composition, and kneaded at 40 ° C. or lower on DOP (dioctyl phthalate) and three rolls according to the formulation described in Table 4, and a color paste having a pigment content of 50%. Is made. This color paste was kneaded with gelled polyvinyl chloride compound at 160 to 165 ° C. on two rolls, and the taken kneaded product was 150 kg / cm at 165 to 175 ° C.²A 1 mm thick sheet was produced by cooling to form a sheet.
[0053]

[0054]
  Next, the obtained dark sheet and white polyvinyl chloride compound were kneaded at 160 to 165 ° C. on two rolls according to the formulation described in Table 5, and the kneaded product taken out was 150 kg / cm at 160 to 165 ° C.²A 1 mm-thick light-colored sheet was produced by cooling to form a sheet.
[0055]

[0056]
<Reference Examples 4 and 5>
  A dark color sheet and a light color sheet were prepared in the same manner as in Reference Example 3 except that the pigment compositions prepared in Examples 4 and 9 were used instead of the pigment composition of Example 3, respectively.
[0057]
<Comparative Example 3>
  Reference Example 3 except that the pigment composition prepared in Comparative Example 1 and dioxazine violet were mixed in the same ratio as the pigment composition of Example 3 instead of the pigment composition of Example 3. A dark sheet and a light sheet were prepared in the same manner.
[0058]
  The dark color sheets of Reference Examples 3, 4, 5 and Comparative Example 3 were visually judged for color tone clarity and transparency. Moreover, about the light color sheet | seat of the reference examples 3, 4, 5 and the comparative example 3, the coloring power was measured with the apparatus similar to the above, and was shown with the same calculation value. The results are shown in Table 6.
[0059]

[0060]
<Reference Example 6>
  The pigment composition prepared in Example 9 was used as the pigment composition, and dispersed according to the formulation shown in Table 7 to prepare a color filter colorant (base color).
[0061]

[0062]
<Comparative example 4>
  A base color was produced in the same manner as in Reference Example 6 except that the pigment composition produced in Comparative Example 1 was used instead of the pigment composition produced in Example 9.
[0063]
<Comparative Example 5>
  Instead of using the pigment composition prepared in Example 9, the pigment composition prepared in Comparative Example 1 and the dioxazine violet pigment mixed in the same ratio as the pigment composition of Example 9 were used. A base collar was produced in the same manner as in Reference Example 6.
[0064]
  Each of the base colors of Reference Example 6 and Comparative Examples 4 and 5 was applied to a glass substrate with a spin coater and prebaked. When the light transmission characteristics of this coated panel were measured with Caracom C manufactured by Dainichi Seika Kogyo Co., Ltd., the values shown in Table 8 were obtained. Moreover, the spectral curve measured with the spectrophotometer of these prebaked films | membranes is shown in FIG.
[0065]

[0066]
  In order to evaluate the heat resistance of the coated panel, each of the coated panels was left in a heated atmosphere at 250 ° C. for 1 hour, and then the color was measured. Color difference before and after the heat resistance test (ΔEab) as an index of heat resistance^*(Heat resistance)). Further, in order to evaluate the light resistance of the coated panel, each of the base colors of Reference Example 6, Comparative Examples 4 and 5 was coated on a glass substrate with a spin coater, pre-baked, and then measured for color. Each coated panel was allowed to stand in a metal halide lamp 90 mW atmosphere for 12 hours and then measured for color. Color difference (ΔEab) before and after metal halide lamp irradiation as an indicator of light resistance^*(Light resistance)). The results are shown in Table 9.
[0067]

  The blue base color obtained in Reference Example 6 was clearly superior in heat resistance and light resistance compared to the blue base colors in Comparative Examples 4 and 5.
[0068]
<Reference Example 7>
  In order to obtain a color filter film of blue (B), the blue base color of Reference Example 6 was used, and a photosensitive pigment dispersion of B was obtained with the formulation shown in Table 10.
[0069]
<Reference Example 8>
  In order to obtain a red (R) color filter film, in Reference Example 6, a red pigment (C.I. Pigment Red 177) was used instead of the pigment composition prepared in Example 9 as the pigment. A red base color produced by the same method as in Reference Example 6 was used, and a photosensitive pigment dispersion of R was obtained according to the formulation shown in Table 10.
[0070]
<Reference Example 9>
  In order to obtain a color filter film of green (G), in Reference Example 6, a green pigment (CI Pigment Green 36) was used instead of the pigment composition prepared in Example 9 as the pigment. A green base color produced in the same manner as in Reference Example 6 was used, and a photosensitive pigment dispersion of G was obtained according to the formulation shown in Table 10.
[0071]

[0072]
<Reference Example 10>
  In order to obtain R, G, and B color filters for a liquid crystal color display, a glass substrate treated with a silane coupling agent was set on a spin coater, and the photosensitive pigment dispersion for the R color filter was first prepared at 300 rpm at 5 rpm. The film was spin coated for 1 second and then at 1200 rpm for 5 seconds. Next, prebaking is performed at 80 ° C. for 10 minutes, a photomask having a mosaic pattern is adhered, and 100 mJ / cm is used using an ultrahigh pressure mercury lamp.²The exposure was performed with a light amount of. Next, development and washing were performed with a dedicated developer and a dedicated rinse to form a red mosaic pattern on the glass substrate.
[0073]
  Subsequently, a green mosaic pattern and a blue mosaic pattern are formed by applying and baking according to the above method using the above-described photosensitive pigment dispersions for G and B color filters, thereby obtaining RGB color filters. It was. The color filter obtained above has excellent spectral curve characteristics, excellent fastness such as light resistance and heat resistance, and also excellent properties of light transmission, especially blue is clear. It had excellent properties as a liquid crystal color filter having the characteristics of reddish blue color tone and high transmittance.
[0074]
【The invention's effect】
  The pigment composition of the present invention can be used in various applications, for example, coloring of plastics, paints, printing inks, printing agents, electrophotographic toners, color for color filters, inkjet inks, thermal transfer inks, etc. It is useful as a colorant that exhibits a sharper reddish color tone than conventional copper phthalocyanine pigments and has improved heat resistance, solvent resistance, light resistance, and weather resistance without causing a decrease in properties and transmittance.
[Brief description of the drawings]
FIG. 1 shows spectral curves of prebaked films in Reference Example 6 and Comparative Examples 4 and 5.

Claims (5)

α-type copper phthalocyanine (component A-1); I. Pigment violet 19, C.I. I. Pigment violet 23 and C.I. I. The weight ratio of at least one selected from Pigment Blue 60 (component B) and the copper phthalocyanine derivative (component C-1) represented by the following formula (I) is A-1: B = 100: 0. Presence of sodium chloride as a grinding aid at a ratio of 1 to 50 and a weight ratio of component A-1 to component C-1 of A-1: C-1 = 100: 0.1-30 A method for producing a pigment composition containing ε-type copper phthalocyanine, characterized by wet milling in diethylene glycol as a non-aromatic solvent.

α-type copper phthalocyanine (component A-1); I. Pigment violet 19, C.I. I. Pigment violet 23 and C.I. I. The weight ratio of at least one selected from Pigment Blue 60 (component B) and the copper phthalocyanine derivative (component C-1) represented by the following formula (I) is A-1: B = 100: 0. Obtained by dry milling at a ratio of 1 to 50 and a weight ratio of component A-1 and component C-1 of A-1: C-1 = 100: 0.1-30 , and then obtained A method for producing a pigment composition containing ε-type copper phthalocyanine, characterized by wet milling a dry milled product in diethylene glycol as a non-aromatic solvent in the presence of sodium chloride as a grinding aid.

Copper phthalocyanine of any crystal form (component A-2), C.I. I. Pigment violet 19, C.I. I. Pigment violet 23 and C.I. I. The weight ratio of at least one selected from Pigment Blue 60 (component B) and the copper phthalocyanine derivative (component C-1) represented by the following formula (I) is A-2: B = 100: 0. 1 to 50, and the weight ratio of component A-2 to component C-1 is A-2: C-1 = 100: 0.1 to 30 and added to a 60% by weight or more sulfuric acid aqueous solution. Then, the obtained sulfuric acid aqueous solution was poured into water to crystallize the component A-2 to α-type copper phthalocyanine ( component A-1 ) , and the obtained component A-1, component B, component C-1 and A method for producing a pigment composition containing ε-type copper phthalocyanine, characterized in that the mixture of is pulverized wet in diethylene glycol as a non-aromatic solvent in the presence of sodium chloride as a grinding aid.

The manufacturing method of any one of Claims 1-3 which perform wet grinding at 60-180 degreeC. The manufacturing method according to any one of claims 1 to 4 , wherein ε-type copper phthalocyanine (component A) is added as a crystal seed (seed) and wet milled.

Images