JP3928080B2 - Composition comprising aromatic carboxylic acid compound - Google Patents

Description

【化７】

【化８】

（式中Ｘは、炭素数１から１６のアルキレン基、オキシアルキレン基、チオアルキレン基、下記構造式（５３）で表される基、下記構造式（５６）で表される基、下記構造式（IV）においてＡ＝オキシアルキレン基、Ｒ＝水素原子、ｎ＝４、Ｂ＝アルキレン基、ｍ＝１である基、及び、下記構造式（V）においてＡ＝オキシアルキレン基、Ｒ＝水素原子又は炭素数１から８のアルキル基、ｎ＝４である基から選択される基を示す。）
【化９】

【化１０】

【０００９】
【発明の実施の形態】
以下、本発明をさらに詳細に説明する。
一般式（Ｉ）（II）（III）より選ばれる少なくとも２種の芳香族カルボン酸化合物からなる組成物を用いた感熱記録材料が高耐可塑剤性、高耐油性を有する理由は明らかではないが、概ね次のような要素が寄与しているものと考えられる。
▲１▼電子吸引性基で置換された強い酸である芳香族カルボン酸が顕色能を持つ。
▲２▼芳香族カルボン酸を１分子中に２つ以上含有することにより分子量が大きくなり、油や可塑剤等の不揮発性溶剤に対する溶解性が低下する。
【００１０】
一般式（Ｉ）（II）（III）より選ばれる少なくとも２種の芳香族カルボン酸化合物からなる組成物は全く新規なものである。これらの化合物は、例えば下記に示されるトリメリット酸無水物とアルコール系化合物とのエステル化反応によって合成することができる。この場合、通常はカルボキシル基の置換位置の異なる少なくとも２種の化合物（異性体）の混合物として得ることができ、例えば前記一般式（Ｉ）と（II）、（II）と（III）、（Ｉ）と（III）といった２種の混合物、あるいは（Ｉ）と（II）と（III）といった３種の混合物がある。これらの混合物を感熱記録材料用の顕色剤として用いる場合には、少なくとも２種の異性体の混合物として用いることができる。また、必要に応じて再結晶、クロマト分離操作等による異性体の分離精製を行って単独品の混合物として用いることも可能である。
【化１１】

【００１１】
一般式（I）、（II）、（III）中のＸの具体例としては、炭素数１から１６のアルキレン基、オキシアルキレン基、チオアルキレン基、下記構造式（５３）で表される基、下記構造式（５６）で表される基、下記構造式（IV）においてＡ＝オキシアルキレン基、Ｒ＝水素原子、ｎ＝４、Ｂ＝アルキレン基、ｍ＝１である基、及び、下記構造式（V）においてＡ＝オキシアルキレン基、Ｒ＝水素原子又は炭素数１から８のアルキル基、ｎ＝４である基から選択される基が挙げられる。
【化１２】

【化１３】

【００１５】
本発明の一般式（Ｉ）（II）（III）で表される芳香族カルボン酸化合物の具体例について、官能基Ｘのみ記載したものを表１〜表７に示す。
ここで、例えば、官能基Ｘが（１）−Ｃ₂Ｈ₄−である場合、下記（１−Ｉ）（１−II）（１−III）の３種の異性体の構造式を表すものである。
【化１８】

【化１９】

【化２０】

官能基Ｘが他の（２）〜（８１）のものについても、それぞれ、（１）の場合と同様に３種の異性体の構造式を表すものとする。
なお、本発明はこれらに限定されるものではない。
【００１６】
【表１】

【００１７】
【表２】

【００１８】
【表３】

【００１９】
【表４】

【００２０】
【表５】

【００２１】
【表６】

【００２２】
【表７】

【００２３】
【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、本発明はこれら実施例に限定されるものではない。
また、純度は高速液体クロマトグラフィー（以下、ＨＰＬＣと略す）又は、ゲル浸透クロマトグラフィー（以下、ＧＰＣと略す）を用い、融点は示差走査熱量計を用いて測定した。化合物の同定は核磁気共鳴スペクトル（以下、ＮＭＲと略す）を測定して行った。
【００２４】
実施例１（具体例Ｎｏ．３８の化合物の合成）
反応容器にビス〔４−（２−ヒドロキシエトキシ）フェニル〕スルホン８４．５ｇ（０．２５ｍｏｌ）、無水トリメリット酸１１４．１ｇ（０．６０ｍｏｌ）、トリエチルアミン１５１．５ｇ（１．５０ｍｏｌ）をテトラヒドロフラン１５０ｇとジメチルホルムアミド５０ｇの混合液に懸濁させて仕込み、溶媒還流下約８３℃にて３時間反応させた。冷却後、反応混合物に水１００ｍｌを滴下し、約３０分撹拌させ、希塩酸をｐＨ２以下となるまで滴下した。静置により二層分離させ、有機層を結晶化が起こるまで水洗し、白色結晶１６３．０ｇを得た（収率９０％）。この生成物は、３種の構造異性体混合物で、３種合わせた純度は９５．３％（ＨＰＬＣ）、融点は１９５〜２１２℃であり、¹Ｈ−ＮＭＲ分析は、目的の化合物であることを示していた。そのＮＭＲスペクトルを以下に示す。
δ（ｐｐｍ）＝１３．５０（broad s），８．２２（４Ｈ，ｔ），７．７９（６Ｈ，ｔ），７．１７（４Ｈ，ｄ），４．６３（４Ｈ，broad s），４．４４（４Ｈ，broad s）．
【００２５】
実施例２（具体例Ｎｏ．４０の化合物の合成）
反応容器にビス〔３−メチル−４−（２−ヒドロキシエトキシ）フェニル〕スルホン９１．５ｇ（０．２５ｍｏｌ）、無水トリメリット酸１１４．１ｇ（０．６０ｍｏｌ）、トリエチルアミン１５１．５ｇ（１．５０ｍｏｌ）をテトラヒドロフラン１５０ｇとジメチルホルムアミド５０ｇの混合液に懸濁させて仕込み、溶媒還流下約８３℃にて３時間反応させた。冷却後、反応混合物に水１００ｍｌを滴下し、約３０分撹拌させ、希塩酸をｐＨ２以下となるまで滴下した。静置により二層分離させ、有機層を結晶化が起こるまで水洗し、白色結晶１７８．１ｇを得た（収率９５％）。この生成物は、３種の構造異性体混合物で、３種合わせた純度は９６．１％（ＨＰＬＣ）、融点は２１３〜２３２℃であり、¹Ｈ−ＮＭＲ分析は、目的の化合物であることを示していた。そのＮＭＲスペクトルを以下に示す。
δ（ｐｐｍ）＝８．２４（４Ｈ，ｔ），７．８５（２Ｈ，ｄ），７．７７（４Ｈ，ｄ），７．２２（２Ｈ，ｄ），４．７０（４Ｈ，ｔ），４．３８（４Ｈ，ｔ），２．２０（６Ｈ，ｓ）．
【００２６】
実施例３（具体例Ｎｏ．４１の化合物の合成）
反応容器にビス〔３，５−ジメチル−４−（２−ヒドロキシエトキシ）フェニル〕スルホン９８．５ｇ（０．２５ｍｏｌ）、無水トリメリット酸１１４．１ｇ（０．６０ｍｏｌ）、トリエチルアミン１５１．５ｇ（１．５０ｍｏｌ）をテトラヒドロフラン１５０ｇとジメチルホルムアミド５０ｇの混合液に懸濁させて仕込み、溶媒還流下約８３℃にて３時間反応させた。冷却後、反応混合物に水１００ｍｌを滴下し、約３０分撹拌させ、希塩酸をｐＨ２以下となるまで滴下した。静置により二層分離させ、有機層を結晶化が起こるまで水洗し、淡黄色結晶１６５．３ｇを得た（収率８５％）。この生成物は、３種の構造異性体混合物で、３種合わせた純度は９６．２％（ＨＰＬＣ）、融点は不明瞭であるが、¹Ｈ−ＮＭＲ分析は、目的の化合物であることを示していた。そのＮＭＲスペクトルを以下に示す。
δ（ｐｐｍ）＝８．２３（４Ｈ，ｔ），７．８５（２Ｈ，ｄ），７．７９（２Ｈ，ｔ），７．６２（４Ｈ，ｓ），４．５６（４Ｈ，ｔ），４．１２（４Ｈ，ｔ），２．５６（１２Ｈ，ｓ）．
【００２７】
実施例４（具体例Ｎｏ．３２の化合物の合成）
反応容器に２，２’−ビス〔４−（２−ヒドロキシエトキシ）フェニル〕プロパン７９．１ｇ（０．２５ｍｏｌ）、無水トリメリット酸１１４．１ｇ（０．６０ｍｏｌ）、トリエチルアミン１５１．５ｇ（１．５０ｍｏｌ）をテトラヒドロフラン１５０ｇとジメチルホルムアミド５０ｇの混合液に懸濁させて仕込み、溶媒還流下約８３℃にて３時間反応させた。冷却後、反応混合物に水１００ｍｌを滴下し、約３０分撹拌させ、希塩酸をｐＨ２以下となるまで滴下した。静置により二層分離させ、有機層を結晶化が起こるまで水洗し、白色結晶１３１．３ｇを得た（収率７８％）。この生成物は、３種の構造異性体混合物で、３種合わせた純度は８７．２％（ＧＰＣ）、融点は不明瞭であるが、¹Ｈ−ＮＭＲ分析は、目的の化合物であることを示していた。そのＮＭＲスペクトルを以下に示す。
δ（ｐｐｍ）＝１３．５３（broad s），８．２０（４Ｈ，ｔ），７．７７（２Ｈ，ｔ），７．７７（４Ｈ，ｄ），７．１２（４Ｈ，ｄ），６．８６（４Ｈ，ｄ），４５４（４Ｈ，broad s），４．２４（４Ｈ，broad s），１．５６（６Ｈ，ｓ）．
【００２８】
実施例５（具体例Ｎｏ．３６の化合物の合成）
反応容器にα，α−ビス〔４−（２−ヒドロキシエトキシ）フェニル〕−１，４−ジイソプロピルベンゼン８６．６ｇ（０．２５ｍｏｌ）、無水トリメリット酸１１４．１ｇ（０．６０ｍｏｌ）、トリエチルアミン１５１．５ｇ（１．５０ｍｏｌ）をテトラヒドロフラン１５０ｇとジメチルホルムアミド５０ｇの混合液に懸濁させて仕込み、溶媒還流下約８３℃にて３時間反応させた。冷却後、反応混合物に水１００ｍｌを滴下し、約３０分撹拌させ、希塩酸をｐＨ２以下となるまで滴下した。静置により二層分離させ、有機層を結晶化が起こるまで水洗し、白色結晶１９６．７ｇを得た（収率９７％）。この生成物は、３種の構造異性体混合物で、３種合わせた純度は９５．０％（ＧＰＣ）、融点は１００〜１７０℃、１９０℃であり、¹Ｈ−ＮＭＲ分析は、目的の化合物であることを示していた。そのＮＭＲスペクトルを以下に示す。
δ（ｐｐｍ）＝８．１９（４Ｈ，ｔ），７．６７（２Ｈ，ｔ），７．１２（４Ｈ，ｄ），７．０７（４Ｈ，ｓ），６．８４（４Ｈ，ｄ），４．５５（４Ｈ，broad s），４．２５（４Ｈ，broad s），１．５６（１２Ｈ，ｓ）．
【００２９】
実施例６（具体例Ｎｏ．５３の化合物の合成）
反応容器に１，４−ビス（ヒドロキシメチル）ベンゼン３４．５ｇ（０．２５ｍｏｌ）、無水トリメリット酸１１４．１ｇ（０．６０ｍｏｌ）、トリエチルアミン１５１．５ｇ（１．５０ｍｏｌ）をテトラヒドロフラン１５０ｇとジメチルホルムアミド５０ｇの混合液に懸濁させて仕込み、溶媒還流下約８３℃にて３時間反応させた。冷却後、反応混合物に水１００ｍｌを滴下し、約３０分撹拌させ、希塩酸をｐＨ２以下となるまで滴下した。静置により二層分離させ、有機層を結晶化が起こるまで水洗し、白色結晶１２５．８ｇを得た（収率９６％）。この生成物は、３種の構造異性体混合物で、３種合わせた純度は９４．２％（ＨＰＬＣ）、融点は１９１℃、２４９℃であり、¹Ｈ−ＮＭＲ分析は、目的の化合物であることを示していた。そのＮＭＲスペクトルを以下に示す。
δ（ｐｐｍ）＝８．２１（４Ｈ，ｔ），７．８１（２Ｈ，ｔ），７．４８（４Ｈ，ｓ），５．３３（４Ｈ，ｓ）．
【００３０】
実施例７（具体例Ｎｏ．５６の化合物の合成）
反応容器に１，４−ビス（２−ヒドロキシエトキシ）ベンゼン４９．６ｇ（０．２５ｍｏｌ）、無水トリメリット酸１１４．１ｇ（０．６０ｍｏｌ）、トリエチルアミン１５１．５ｇ（１．５０ｍｏｌ）をテトラヒドロフラン１５０ｇとジメチルホルムアミド５０ｇの混合液に懸濁させて仕込み、溶媒還流下約８３℃にて３時間反応させた。冷却後、反応混合物に水１００ｍｌを滴下し、約３０分撹拌させ、希塩酸をｐＨ２以下となるまで滴下した。静置により二層分離させ、有機層を結晶化が起こるまで水洗し、淡黄白色結晶１４４．０ｇを得た（収率９９％）。この生成物は、３種の構造異性体混合物で、３種合わせた純度は９２．２％（ＨＰＬＣ）、融点は２１８℃であり、¹Ｈ−ＮＭＲ分析は、目的の化合物であることを示していた。そのＮＭＲスペクトルを以下に示す。
δ（ｐｐｍ）＝１３．５８（broad s），８．２０（４Ｈ，ｔ），７．８５（２Ｈ，ｔ），６．９１（４Ｈ，ｓ），４．５４（４Ｈ，broad s），４．２５（４Ｈ，broad s）．
【００３１】
実施例８（具体例Ｎｏ．３の化合物の合成）
反応容器に１，４−ブタンジオール２２．５ｇ（０．２５ｍｏｌ）、無水トリメリット酸１１４．１ｇ（０．６０ｍｏｌ）、トリエチルアミン１５１．５ｇ（１．５０ｍｏｌ）をテトラヒドロフラン１５０ｇとジメチルホルムアミド５０ｇの混合液に懸濁させて仕込み、溶媒還流下約８３℃にて３時間反応させた。冷却後、反応混合物に水１００ｍｌを滴下し、約３０分撹拌させ、希塩酸をｐＨ２以下となるまで滴下した。静置により二層分離させ、有機層を結晶化が起こるまで水洗し、微黄白色結晶１０９．８ｇを得た（収率９３％）。この生成物は、３種の構造異性体混合物で、３種合わせた純度は９７．３％（ＨＰＬＣ）、融点は９９℃，１８３℃，２４２〜２５８℃であり、¹Ｈ−ＮＭＲ分析は、目的の化合物であることを示していた。そのＮＭＲスペクトルを以下に示す。
δ（ｐｐｍ）＝１３．４５（broad s），８．２５（２Ｈ，ｄ），８．１５（２Ｈ，ｍ），７．７９（２Ｈ，ｔ），４．３１（４Ｈ，broad s），１．８１（４Ｈ，broad s）．
【００３２】
実施例９（具体例Ｎｏ．７の化合物の合成）
反応容器に１，１０−デカンジオール４３．６ｇ（０．２５ｍｏｌ）、無水トリメリット酸１１４．１ｇ（０．６０ｍｏｌ）、トリエチルアミン１５１．５ｇ（１．５０ｍｏｌ）をテトラヒドロフラン１５０ｇとジメチルホルムアミド５０ｇの混合液に懸濁させて仕込み、溶媒還流下約８３℃にて３時間反応させた。冷却後、反応混合物に水１００ｍｌを滴下し、約３０分撹拌させ、希塩酸をｐＨ２以下となるまで滴下した。静置により二層分離させ、有機層を結晶化が起こるまで水洗し、白色結晶１３１．４ｇを得た（収率９４％）。この生成物は、３種の構造異性体混合物で、３種合わせた純度は９７．１％（ＨＰＬＣ）、融点は１６０℃，１８５℃，２２６℃であり、¹Ｈ−ＮＭＲ分析は、目的の化合物であることを示していた。そのＮＭＲスペクトルを以下に示す。
δ（ｐｐｍ）＝１３．４８（broad s），８．１９（４Ｈ，ｍ），７．７７（２Ｈ，ｔ），４．２３（４Ｈ，ｔ），１．６３（４Ｈ，broad s），１．２８（１２Ｈ，ｓ）．
【００３３】
実施例１０（具体例Ｎｏ．１６の化合物の合成）
反応容器にビス（２−ヒドロキシエチル）スルフィド３０．５ｇ（０．２５ｍｏｌ）、無水トリメリット酸１１４．１ｇ（０．６０ｍｏｌ）、トリエチルアミン１５１．５ｇ（１．５０ｍｏｌ）をテトラヒドロフラン１５０ｇとジメチルホルムアミド５０ｇの混合液に懸濁させて仕込み、溶媒還流下約８３℃にて３時間反応させた。冷却後、反応混合物に水１００ｍｌを滴下し、約３０分撹拌させ、希塩酸をｐＨ２以下となるまで滴下した。静置により二層分離させ、有機層を結晶化が起こるまで水洗し、淡黄褐色結晶９６．１ｇを得た（収率７６％）。この生成物は、３種の構造異性体混合物で、３種合わせた純度は９５．０％（ＨＰＬＣ）、融点は１６６℃であり、¹Ｈ−ＮＭＲ分析は、目的の化合物であることを示していた。そのＮＭＲスペクトルを以下に示す。
δ（ｐｐｍ）＝１３．４６（broad s），８．２１（４Ｈ，ｔ），７．７８（２Ｈ，ｔ），４．４２（４Ｈ，ｔ），２．９３（４Ｈ，ｔ）．
【００３４】
実施例１１（具体例Ｎｏ．１０の化合物の合成）
反応容器にトリ（エチレングリコール）３７．５ｇ（０．２５ｍｏｌ）、無水トリメリット酸１１４．１ｇ（０．６０ｍｏｌ）、トリエチルアミン１５１．５ｇ（１．５０ｍｏｌ）をテトラヒドロフラン１５０ｇとジメチルホルムアミド５０ｇの混合液に懸濁させて仕込み、溶媒還流下約８３℃にて３時間反応させた。冷却後、反応混合物に水１００ｍｌを滴下し、約３０分撹拌させ、希塩酸をｐＨ２以下となるまで滴下した。静置により二層分離させ、有機層を結晶化が起こるまで水洗し、淡黄色結晶６６．８ｇを得た（収率５０％）。この生成物は、３種の構造異性体混合物で、３種合わせた純度は９０．８％（ＨＰＬＣ）、融点は１６３℃，２１４〜２３４℃であり、¹Ｈ−ＮＭＲ分析は、目的の化合物であることを示していた。そのＮＭＲスペクトルを以下に示す。
δ（ｐｐｍ）＝１３．５３（broad s），８．１７（４Ｈ，ｔ），７．７７（２Ｈ，ｔ），４．３７（４Ｈ，ｔ），３．７１（４Ｈ，ｔ），３．５８（４Ｈ，ｓ）．
【００３５】
次に、前記化合物を感熱記録材料として用いた応用例を示す。ここでの部は重量基準である。
【００３６】
応用例１
下記組成よりなる混合物を磁性ボールミルで分散し〔Ａ液〕〜〔Ｅ液〕を調製する。
〔Ａ液〕
３−Ｎ，Ｎ−ジブチルアミノ−６−メチル−７−
アニリノフルオラン １０部
１０％ポリビニルアルコール水溶液 １０部
水 ３０部
〔Ｂ液〕
具体例Ｎｏ．３８の化合物 １０部
１０％ポリビニルアルコール水溶液 １０部
水 ３０部
〔Ｃ液〕
Ｐ５２７（水沢化学製シリカゲル） １０部
１０％ポリビニルアルコール水溶液 １０部
水 ３０部
〔Ｄ液〕
ステアリン酸亜鉛 １０部
１０％ポリビニルアルコール水溶液 １０部
水 ３０部
次に、下記組成の混合物をディスパーにで撹拌分散してＥ液を調製した。
〔Ｅ液〕
非発泡性プラスチック微小中空粒子
（固形分２４％、平均粒径３μｍ、中空度９０％） ４０部
スチレン／ブタジエン共重合体ラテックス １０部
水 ５０部
次に、〔Ａ液〕〜〔Ｅ液〕を用いて感熱発色層塗布液とアンダーコート塗布液を下記の混合比で調製した。
（感熱発色層塗布液）
〔Ａ液〕：〔Ｂ液〕：〔Ｃ液〕：〔Ｄ液〕＝１：４：４：０．５
（アンダーコート塗布液）
〔Ｅ液〕：〔Ｃ液〕＝２：１
〈各層の塗工〉
市販の上質紙（坪量６０ｇ／ｍ²）の表面に（アンダーコート塗布液）を乾燥重量が３ｇ／ｍ²となるように塗布乾燥して中間コート紙（アンダーコート層塗布済紙）を得た。このアンダーコート層上に感熱発色層塗布液をロイコ塗料の乾燥重量が０．５ｇ／ｍ²となるように塗布乾燥して感熱発色層を設けた。その後、１０ｋｇ／ｃｍ²の圧力でキャレンダー処理して本発明の感熱記録材料を得た。
【００３７】
応用例２
応用例１の〔Ｂ液〕において、化合物Ｎｏ．３８の化合物の代わりに具体例Ｎｏ．４０の化合物を用いた以外は、応用例１と同様にして調製し感熱記録材料を得た。
【００３８】
応用例３
応用例１の〔Ｂ液〕において、化合物Ｎｏ．３８の代わりに化合物Ｎｏ．３２の化合物を用いた以外は、応用例１と同様にして調製し感熱記録材料を得た。
【００３９】
応用例４
応用例１の〔Ｂ液〕において、化合物Ｎｏ．３８の代わりに化合物Ｎｏ．５３の化合物を用いた以外は、応用例１と同様にして調製し感熱記録材料を得た。
【００４０】
応用例５
応用例１の〔Ｂ液〕において、化合物Ｎｏ．３８の代わりに具体例Ｎｏ．５６の化合物を用いた以外は、応用例１と同様にして調製し感熱記録材料を得た。
【００４１】
応用例６
応用例１の〔Ｂ液〕において、化合物Ｎｏ．３８の代わりに具体例Ｎｏ．１６の化合物を用いた以外は応用例１と同様にして調製し感熱記録材料を得た。
【００４２】
応用例７
応用例１の〔Ｂ液〕において、化合物Ｎｏ．３８の代わりに具体例Ｎｏ．３の化合物を用いた以外は応用例１と同様にして調製し感熱記録材料を得た。
【００４３】
応用例８
応用例１の〔Ｂ液〕において、化合物Ｎｏ．３８の代わりに具体例Ｎｏ．７の化合物を用いた以外は応用例１と同様にして調製し感熱記録材料を得た。
【００４４】
応用例９
応用例１の〔Ｂ液〕において、化合物Ｎｏ．３８の代わりに具体例Ｎｏ．１０の化合物を用いた以外は応用例１と同様にして調製し感熱記録材料を得た。
【００４５】
比較例１
応用例１の〔Ｂ液〕において、化合物Ｎｏ．３８の代わりに、２，２−ビス（４−ヒドロキシフェニル）プロパン（ビスフェノールＡ）を用いた以外は応用例１と同様にして調製し感熱記録材料を得た。
【００４６】
以上のように作成した感熱記録材料について、次に示す試験を行った。その結果を表８に示す。
〈発色性試験〉
松下部品（株）製薄膜ヘッドを有するシュミレータ印字実験装置にて、ヘッド電力０．６８Ｗ／ｄｏｔ、１ライン記録時間１０ｍｓ／ライン、走査線密度８×３．８５ｄｏｔ／ｍｍの条件でパルス幅０．９ｍｓで印字を行い、得られた試験片に対して以下の存在性試験を行った。
【００４７】
＜耐可塑剤性試験＞
試験片に塩ビラップフィルム（信越ポリマー製）を３枚重ね、５ｋｇの加重を掛けて４０℃、１５時間放置後の画像濃度をマクベス濃度計で測定し耐可塑剤性を評価した。
＜耐油性試験＞
試験片に綿実油を塗布した後、４０℃、１５時間放置後の画像濃度をマクベス濃度計で測定し耐油性を評価した。
【００４８】
【表８】

表８の結果より、本発明の化合物を顕色剤として用いた感熱記録材料は画像の耐可塑剤性、耐油性に優れていることが明らかである。
【００４９】
【発明の効果】
本発明に係る芳香族カルボン酸化合物の２種以上の化合物からなる組成物は新規なものであり、このものは感熱記録材料の顕色剤として有利であり、このものを顕色剤として用いた感熱記録材料は耐可塑剤性、耐油性に優れた画像を与える。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a composition comprising a novel aromatic carboxylic acid compound useful as a developer having excellent image storage stability.
[0002]
[Prior art]
A heat-sensitive recording material generally comprises a heat-sensitive color-developing layer mainly comprising an electron-donating colorless or light-colored dye precursor and an electron-accepting developer on a support. By heating with a laser beam or the like, the dye precursor and the developer react instantaneously to obtain a recorded image, which is disclosed in Japanese Patent Publication Nos. 43-4160 and 45-14039. Yes.
Such a heat-sensitive recording material has advantages such that recording can be obtained with a relatively simple device, maintenance is easy, and noise generation is low. In recent years, electronic computers, facsimiles, ticket vending machines, label printers, It is used in a wide range of fields as a recording material for recorders.
However, the heat-sensitive recording material using such an electron-donating dye precursor and an electron-accepting developer has excellent properties such as good appearance, good touch, and high color density, The recorded image part is easy to come into contact with plastics such as polyvinyl chloride, and to be erased by plasticizers and additives contained in plastics, or in contact with chemicals contained in foods and cosmetics. In addition, the recording image portion is decolored or the background portion is colored, so that the storage stability as a recording material is inferior.
[0003]
Conventionally, the use of a highly reliable developer as a means for realizing high storage stability of a recorded image has been proposed. For example, JP-A-58-82788 and JP-A-60-13852 propose phenol sulfone compounds and JP-A-62-169681 proposes substituted salicylic acid compounds. When used as, it is insufficient in terms of fastness to the plasticizer, oil and the like in the image area.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a composition comprising a novel aromatic carboxylic acid compound that is useful as a developer that gives an image excellent in high storage stability of an image area, in particular, plasticizer resistance and oil resistance. .
[0005]
[Means for Solving the Problems]
According to the present invention, there is provided a developer composition comprising at least two aromatic carboxylic acid compounds selected from the following general formulas (I), (II) and (III).
[Chemical 6]

[Chemical 7]

[Chemical 8]

Wherein X is an alkylene group having 1 to 16 carbon atoms, an oxyalkylene group, a thioalkylene group, a group represented by the following structural formula (53), a group represented by the following structural formula (56), or the following structural formula In (IV), A = oxyalkylene group, R = hydrogen atom, n = 4, B = alkylene group, group in which m = 1, and in the following structural formula (V), A = oxyalkylene group, R = hydrogen atom Or a group selected from an alkyl group having 1 to 8 carbon atoms and a group where n = 4.)
[Chemical 9]

[Chemical Formula 10]

[0009]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
The reason why the heat-sensitive recording material using the composition comprising at least two aromatic carboxylic acid compounds selected from the general formulas (I), (II), and (III) has high plasticizer resistance and high oil resistance is not clear. However, the following factors are considered to be contributing.
(1) An aromatic carboxylic acid which is a strong acid substituted with an electron-withdrawing group has a color developing ability.
(2) Inclusion of two or more aromatic carboxylic acids in one molecule increases the molecular weight and lowers the solubility in non-volatile solvents such as oils and plasticizers.
[0010]
A composition comprising at least two aromatic carboxylic acid compounds selected from general formulas (I), (II) and (III) is completely novel. These compounds can be synthesized, for example, by an esterification reaction of trimellitic anhydride and an alcohol compound shown below. In this case, it can usually be obtained as a mixture of at least two compounds (isomers) having different substitution positions of the carboxyl group. For example, the compounds represented by the general formulas (I) and (II), (II) and (III), ( There are two mixtures such as I) and (III) or three mixtures such as (I), (II) and (III). When these mixtures are used as developers for heat-sensitive recording materials, they can be used as a mixture of at least two isomers. Further, if necessary, the isomers can be separated and purified by recrystallization, chromatographic separation, or the like, and used as a mixture of individual products.
Embedded image

[0011]
Specific examples of X in the general formulas (I), (II), and (III) include an alkylene group having 1 to 16 carbon atoms, an oxyalkylene group, a thioalkylene group, and a group represented by the following structural formula (53). A group represented by the following structural formula (56), a group in which A = oxyalkylene group, R = hydrogen atom, n = 4, B = alkylene group, m = 1 in the following structural formula (IV), and In the structural formula (V), A = oxyalkylene group, R = hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and a group selected from groups where n = 4.
Embedded image

Embedded image

[0015]
The specific examples of the aromatic carboxylic acid compounds represented by the general formulas (I), (II) and (III) of the present invention are shown in Tables 1 to 7 in which only the functional group X is described.
Here, for example, when the functional group X is (1) -C ₂ H ₄ —, it represents the structural formula of the following three isomers of (1-I) (1-II) (1-III) It is.
Embedded image

Embedded image

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As for the other functional groups X (2) to (81), the structural formulas of the three isomers are represented in the same manner as in (1).
The present invention is not limited to these.
[0016]
[Table 1]

[0017]
[Table 2]

[0018]
[Table 3]

[0019]
[Table 4]

[0020]
[Table 5]

[0021]
[Table 6]

[0022]
[Table 7]

[0023]
【Example】
EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
The purity was measured using high performance liquid chromatography (hereinafter abbreviated as HPLC) or gel permeation chromatography (hereinafter abbreviated as GPC), and the melting point was measured using a differential scanning calorimeter. The compound was identified by measuring a nuclear magnetic resonance spectrum (hereinafter abbreviated as NMR).
[0024]
Example 1 (Synthesis of compound of specific example No. 38)
In a reaction vessel, 84.5 g (0.25 mol) of bis [4- (2-hydroxyethoxy) phenyl] sulfone, 114.1 g (0.60 mol) of trimellitic anhydride, 151.5 g (1.50 mol) of triethylamine and 150 g of tetrahydrofuran. Suspended in a mixed solution of dimethylformamide and 50 g of dimethylformamide, and reacted at about 83 ° C. for 3 hours under reflux of the solvent. After cooling, 100 ml of water was added dropwise to the reaction mixture, and the mixture was stirred for about 30 minutes, and diluted hydrochloric acid was added dropwise until the pH became 2 or less. The organic layer was washed with water until crystallization occurred to obtain 163.0 g of white crystals (yield 90%). This product is a mixture of three kinds of structural isomers, and the combined purity of the three kinds is 95.3% (HPLC), the melting point is 195 to 212 ° C., and ¹ H-NMR analysis is the target compound. Was showing. The NMR spectrum is shown below.
δ (ppm) = 13.50 (broad s), 8.22 (4H, t), 7.79 (6H, t), 7.17 (4H, d), 4.63 (4H, broad s), 4.44 (4H, broad s).
[0025]
Example 2 (Synthesis of compound of specific example No. 40)
In a reaction vessel, bis [3-methyl-4- (2-hydroxyethoxy) phenyl] sulfone 91.5 g (0.25 mol), trimellitic anhydride 114.1 g (0.60 mol), triethylamine 151.5 g (1.50 mol) Was suspended in a mixed solution of 150 g of tetrahydrofuran and 50 g of dimethylformamide, and reacted at about 83 ° C. for 3 hours under reflux of the solvent. After cooling, 100 ml of water was added dropwise to the reaction mixture, and the mixture was stirred for about 30 minutes, and diluted hydrochloric acid was added dropwise until the pH became 2 or less. The organic layer was washed with water until crystallization occurred to obtain 178.1 g of white crystals (yield 95%). This product is a mixture of three kinds of structural isomers, the purity of the three kinds combined is 96.1% (HPLC), the melting point is 213 to 232 ° C., and ¹ H-NMR analysis is the target compound. Was showing. The NMR spectrum is shown below.
δ (ppm) = 8.24 (4H, t), 7.85 (2H, d), 7.77 (4H, d), 7.22 (2H, d), 4.70 (4H, t), 4.38 (4H, t), 2.20 (6H, s).
[0026]
Example 3 (Synthesis of compound of specific example No. 41)
In a reaction vessel, bis [3,5-dimethyl-4- (2-hydroxyethoxy) phenyl] sulfone 98.5 g (0.25 mol), trimellitic anhydride 114.1 g (0.60 mol), triethylamine 151.5 g (1 50 mol) was suspended in a mixed solution of 150 g of tetrahydrofuran and 50 g of dimethylformamide, and reacted at about 83 ° C. for 3 hours under reflux of the solvent. After cooling, 100 ml of water was added dropwise to the reaction mixture, and the mixture was stirred for about 30 minutes, and diluted hydrochloric acid was added dropwise until the pH became 2 or less. The organic layer was washed with water until crystallization occurred to obtain 165.3 g of pale yellow crystals (yield 85%). This product is a mixture of three structural isomers. The purity of the three combined is 96.2% (HPLC), and the melting point is unclear, but ¹ H-NMR analysis shows that the desired compound is obtained. Was showing. The NMR spectrum is shown below.
δ (ppm) = 8.23 (4H, t), 7.85 (2H, d), 7.79 (2H, t), 7.62 (4H, s), 4.56 (4H, t), 4.12 (4H, t), 2.56 (12H, s).
[0027]
Example 4 (Synthesis of compound of specific example No. 32)
In a reaction vessel, 79.1 g (0.25 mol) of 2,2′-bis [4- (2-hydroxyethoxy) phenyl] propane, 114.1 g (0.60 mol) of trimellitic anhydride, 151.5 g of triethylamine (1. 50 mol) was suspended in a mixed solution of 150 g of tetrahydrofuran and 50 g of dimethylformamide, and reacted at about 83 ° C. for 3 hours under reflux of the solvent. After cooling, 100 ml of water was added dropwise to the reaction mixture, and the mixture was stirred for about 30 minutes, and diluted hydrochloric acid was added dropwise until the pH became 2 or less. The organic layer was washed with water until crystallization occurred to obtain 131.3 g of white crystals (yield 78%). This product is a mixture of three structural isomers. The purity of the three combined is 87.2% (GPC) and the melting point is unclear, but ¹ H-NMR analysis shows that it is the desired compound. Was showing. The NMR spectrum is shown below.
δ (ppm) = 13.53 (broad s), 8.20 (4H, t), 7.77 (2H, t), 7.77 (4H, d), 7.12 (4H, d), 6 .86 (4H, d), 454 (4H, broad s), 4.24 (4H, broad s), 1.56 (6H, s).
[0028]
Example 5 (Synthesis of compound of specific example No. 36)
In the reaction vessel, α, α-bis [4- (2-hydroxyethoxy) phenyl] -1,4-diisopropylbenzene 86.6 g (0.25 mol), trimellitic anhydride 114.1 g (0.60 mol), triethylamine 151 0.5 g (1.50 mol) was suspended in a mixed solution of 150 g of tetrahydrofuran and 50 g of dimethylformamide, and reacted at about 83 ° C. for 3 hours under reflux of the solvent. After cooling, 100 ml of water was added dropwise to the reaction mixture, and the mixture was stirred for about 30 minutes, and diluted hydrochloric acid was added dropwise until the pH became 2 or less. The organic layer was washed with water until crystallization occurred to obtain 196.7 g of white crystals (yield 97%). This product is a mixture of three kinds of structural isomers, the purity of the three kinds combined is 95.0% (GPC), the melting points are 100-170 ° C. and 190 ° C., and ¹ H-NMR analysis shows the desired compound It was shown that. The NMR spectrum is shown below.
δ (ppm) = 8.19 (4H, t), 7.67 (2H, t), 7.12 (4H, d), 7.07 (4H, s), 6.84 (4H, d), 4.55 (4H, broad s), 4.25 (4H, broad s), 1.56 (12H, s).
[0029]
Example 6 (Synthesis of compound of specific example No. 53)
In a reaction vessel, 34.5 g (0.25 mol) of 1,4-bis (hydroxymethyl) benzene, 114.1 g (0.60 mol) of trimellitic anhydride, 151.5 g (1.50 mol) of triethylamine, 150 g of tetrahydrofuran and dimethylformamide The mixture was suspended in 50 g of a mixed solution and reacted at about 83 ° C. for 3 hours under reflux of the solvent. After cooling, 100 ml of water was added dropwise to the reaction mixture, and the mixture was stirred for about 30 minutes, and diluted hydrochloric acid was added dropwise until the pH became 2 or less. The organic layer was washed with water until crystallization occurred to obtain 125.8 g of white crystals (yield 96%). This product is a mixture of three kinds of structural isomers. The purity of the three kinds is 94.2% (HPLC), the melting point is 191 ° C., 249 ° C., and ¹ H-NMR analysis is the target compound. It showed that. The NMR spectrum is shown below.
δ (ppm) = 8.21 (4H, t), 7.81 (2H, t), 7.48 (4H, s), 5.33 (4H, s).
[0030]
Example 7 (Synthesis of compound of specific example No. 56)
In a reaction vessel, 49.6 g (0.25 mol) of 1,4-bis (2-hydroxyethoxy) benzene, 114.1 g (0.60 mol) of trimellitic anhydride, 151.5 g (1.50 mol) of triethylamine and 150 g of tetrahydrofuran were obtained. The mixture was suspended in a mixed solution of 50 g of dimethylformamide and reacted at about 83 ° C. for 3 hours under reflux of the solvent. After cooling, 100 ml of water was added dropwise to the reaction mixture, and the mixture was stirred for about 30 minutes, and diluted hydrochloric acid was added dropwise until the pH became 2 or less. The organic layer was washed with water until crystallization occurred to obtain 144.0 g of pale yellowish white crystals (yield 99%). This product is a mixture of three structural isomers, the purity of the three combined is 92.2% (HPLC), the melting point is 218 ° C., and ¹ H-NMR analysis shows that it is the desired compound. It was. The NMR spectrum is shown below.
δ (ppm) = 13.58 (broad s), 8.20 (4H, t), 7.85 (2H, t), 6.91 (4H, s), 4.54 (4H, broad s), 4.25 (4H, broad s).
[0031]
Example 8 (Synthesis of compound of specific example No. 3)
In a reaction vessel, 22.5 g (0.25 mol) of 1,4-butanediol, 114.1 g (0.60 mol) of trimellitic anhydride, 151.5 g (1.50 mol) of triethylamine, a mixed solution of 150 g of tetrahydrofuran and 50 g of dimethylformamide The mixture was suspended in the solution and reacted at about 83 ° C. for 3 hours under reflux of the solvent. After cooling, 100 ml of water was added dropwise to the reaction mixture, and the mixture was stirred for about 30 minutes, and diluted hydrochloric acid was added dropwise until the pH became 2 or less. The organic layer was washed with water until crystallization occurred to obtain 109.8 g of slightly yellowish white crystals (yield 93%). This product is a mixture of three kinds of structural isomers, the purity of the three kinds combined is 97.3% (HPLC), the melting points are 99 ° C., 183 ° C., 242-258 ° C., and ¹ H-NMR analysis is It was shown to be the target compound. The NMR spectrum is shown below.
δ (ppm) = 13.45 (broad s), 8.25 (2H, d), 8.15 (2H, m), 7.79 (2H, t), 4.31 (4H, broad s), 1.81 (4H, broad s).
[0032]
Example 9 (Synthesis of compound of specific example No. 7)
In a reaction vessel, 43.6 g (0.25 mol) of 1,10-decanediol, 114.1 g (0.60 mol) of trimellitic anhydride, 151.5 g (1.50 mol) of triethylamine, a mixed solution of 150 g of tetrahydrofuran and 50 g of dimethylformamide. The mixture was suspended in the solution and reacted at about 83 ° C. for 3 hours under reflux of the solvent. After cooling, 100 ml of water was added dropwise to the reaction mixture, and the mixture was stirred for about 30 minutes, and diluted hydrochloric acid was added dropwise until the pH became 2 or less. The organic layer was washed with water until crystallization occurred to obtain 131.4 g of white crystals (yield 94%). The product, in three structural isomer mixture, three combined purity 97.1% (HPLC), a melting point of 160 ° C., 185 ° C., was 226 ℃, ¹ H-NMR analysis, the objective It was shown to be a compound. The NMR spectrum is shown below.
δ (ppm) = 13.48 (broad s), 8.19 (4H, m), 7.77 (2H, t), 4.23 (4H, t), 1.63 (4H, broad s), 1.28 (12H, s).
[0033]
Example 10 (Synthesis of compound of specific example No. 16)
In a reaction vessel, 30.5 g (0.25 mol) of bis (2-hydroxyethyl) sulfide, 114.1 g (0.60 mol) of trimellitic anhydride, 151.5 g (1.50 mol) of triethylamine, 150 g of tetrahydrofuran and 50 g of dimethylformamide. The mixture was suspended in the mixed solution and reacted at about 83 ° C. for 3 hours under reflux of the solvent. After cooling, 100 ml of water was added dropwise to the reaction mixture, and the mixture was stirred for about 30 minutes, and diluted hydrochloric acid was added dropwise until the pH became 2 or less. The organic layer was washed with water until crystallization occurred to obtain 96.1 g of pale yellowish brown crystals (yield 76%). The product is a mixture of three structural isomers, the combined purity of the three is 95.0% (HPLC), the melting point is 166 ° C., and ¹ H-NMR analysis shows that it is the desired compound. It was. The NMR spectrum is shown below.
δ (ppm) = 13.46 (broad s), 8.21 (4H, t), 7.78 (2H, t), 4.42 (4H, t), 2.93 (4H, t).
[0034]
Example 11 (Synthesis of compound of specific example No. 10)
In a reaction vessel, 37.5 g (0.25 mol) of tri (ethylene glycol), 114.1 g (0.60 mol) of trimellitic anhydride, and 151.5 g (1.50 mol) of triethylamine were mixed in a mixed solution of 150 g of tetrahydrofuran and 50 g of dimethylformamide. The suspension was charged and reacted at about 83 ° C. for 3 hours under reflux of the solvent. After cooling, 100 ml of water was added dropwise to the reaction mixture, and the mixture was stirred for about 30 minutes, and diluted hydrochloric acid was added dropwise until the pH became 2 or less. The organic layer was washed with water until crystallization occurred to obtain 66.8 g of pale yellow crystals (yield 50%). This product is a mixture of 3 kinds of structural isomers, the purity of the 3 kinds combined is 90.8% (HPLC), the melting point is 163 ° C., 214-234 ° C., and ¹ H-NMR analysis shows the desired compound It was shown that. The NMR spectrum is shown below.
δ (ppm) = 13.53 (broad s), 8.17 (4H, t), 7.77 (2H, t), 4.37 (4H, t), 3.71 (4H, t), 3 .58 (4H, s).
[0035]
Next, application examples using the compound as a heat-sensitive recording material will be shown. The parts here are based on weight.
[0036]
Application example 1
A mixture having the following composition is dispersed with a magnetic ball mill to prepare [A liquid] to [E liquid].
[Liquid A]
3-N, N-dibutylamino-6-methyl-7-
Anilinofluorane 10 parts 10% polyvinyl alcohol aqueous solution 10 parts water 30 parts [Liquid B]
Specific Example No. 38 compounds 10 parts 10% polyvinyl alcohol aqueous solution 10 parts water 30 parts [Liquid C]
P527 (Mizusawa Chemical Silica Gel) 10 parts 10% polyvinyl alcohol aqueous solution 10 parts water 30 parts [Liquid D]
Zinc stearate 10 parts 10% polyvinyl alcohol aqueous solution 10 parts Water 30 parts Next, a mixture E having the following composition was stirred and dispersed in a disper to prepare solution E.
[E liquid]
Non-foaming plastic micro hollow particles (solid content 24%, average particle size 3 μm, hollowness 90%) 40 parts Styrene / butadiene copolymer latex 10 parts Water 50 parts Next, [Liquid A] to [Liquid E] A thermosensitive coloring layer coating solution and an undercoat coating solution were prepared at the following mixing ratio.
(Thermosensitive coloring layer coating solution)
[Liquid A]: [Liquid B]: [Liquid C]: [Liquid D] = 1: 4: 4: 0.5
(Undercoat coating solution)
[E liquid]: [C liquid] = 2: 1
<Coating of each layer>
(Undercoat coating solution) is coated on the surface of commercially available high-quality paper (basis weight 60 g / m ² ) so that the dry weight is 3 g / m ^2, and intermediate coated paper (paper with an undercoat layer coated) is obtained. It was. On this undercoat layer, a heat-sensitive coloring layer coating solution was applied and dried so that the dry weight of the leuco paint was 0.5 g / m ² to provide a heat-sensitive coloring layer. Thereafter, a calender treatment was performed at a pressure of 10 kg / cm ² to obtain the heat-sensitive recording material of the present invention.
[0037]
Application example 2
In Application Example 1 [Liquid B], compound no. Instead of the compound No. 38, specific examples No. A thermosensitive recording material was obtained in the same manner as in Application Example 1 except that 40 compounds were used.
[0038]
Application example 3
In Application Example 1 [Liquid B], compound no. Instead of compound 38, compound no. A thermosensitive recording material was obtained in the same manner as in Application Example 1 except that 32 compounds were used.
[0039]
Application example 4
In Application Example 1 [Liquid B], compound no. Instead of compound 38, compound no. A thermosensitive recording material was obtained in the same manner as in Application Example 1, except that 53 compounds were used.
[0040]
Application example 5
In Application Example 1 [Liquid B], compound no. Example No. 38 is used instead of 38. A thermosensitive recording material was obtained in the same manner as in Application Example 1 except that 56 compounds were used.
[0041]
Application example 6
In Application Example 1 [Liquid B], compound no. Example No. 38 is used instead of 38. A thermosensitive recording material was obtained in the same manner as in Application Example 1 except that 16 compounds were used.
[0042]
Application example 7
In Application Example 1 [Liquid B], compound no. Example No. 38 is used instead of 38. A thermosensitive recording material was obtained in the same manner as in Application Example 1 except that the compound No. 3 was used.
[0043]
Application example 8
In Application Example 1 [Liquid B], compound no. Example No. 38 is used instead of 38. A thermosensitive recording material was obtained in the same manner as in Application Example 1 except that the compound No. 7 was used.
[0044]
Application example 9
In Application Example 1 [Liquid B], compound no. Example No. 38 is used instead of 38. A thermosensitive recording material was obtained in the same manner as in Application Example 1 except that 10 compounds were used.
[0045]
Comparative Example 1
In Application Example 1 [Liquid B], compound no. A thermosensitive recording material was obtained in the same manner as in Application Example 1 except that 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) was used instead of 38.
[0046]
The following tests were conducted on the heat-sensitive recording material prepared as described above. The results are shown in Table 8.
<Color development test>
In a simulator printing experimental apparatus having a thin film head manufactured by Matsushita Parts Co., Ltd., a pulse width of 0. 8 with a head power of 0.68 W / dot, a line recording time of 10 ms / line, and a scanning line density of 8 × 3.85 dots / mm. Printing was performed at 9 ms, and the following existence test was performed on the obtained test piece.
[0047]
<Plasticizer resistance test>
Three plastic wrap films (manufactured by Shin-Etsu Polymer) were stacked on the test piece, and the weight of 5 kg was applied, and the image density after standing at 40 ° C. for 15 hours was measured with a Macbeth densitometer to evaluate the plasticizer resistance.
<Oil resistance test>
After applying cottonseed oil to the test piece, the image density after standing at 40 ° C. for 15 hours was measured with a Macbeth densitometer to evaluate the oil resistance.
[0048]
[Table 8]

From the results in Table 8, it is clear that the heat-sensitive recording material using the compound of the present invention as a developer is excellent in image plasticizer resistance and oil resistance.
[0049]
【The invention's effect】
The composition comprising two or more compounds of the aromatic carboxylic acid compound according to the present invention is a novel one, which is advantageous as a color developer for a heat-sensitive recording material, and this was used as a color developer. The heat-sensitive recording material gives an image excellent in plasticizer resistance and oil resistance.

Claims (1)

A developer composition comprising at least two aromatic carboxylic acid compounds selected from the following general formulas (I), (II), and (III).

Wherein X is an alkylene group having 1 to 16 carbon atoms, an oxyalkylene group, a thioalkylene group, a group represented by the following structural formula (53), a group represented by the following structural formula (56), or the following structural formula In (IV), A = oxyalkylene group, R = hydrogen atom, n = 4, B = alkylene group, group in which m = 1, and in the following structural formula (V), A = oxyalkylene group, R = hydrogen atom Or a group selected from an alkyl group having 1 to 8 carbon atoms and a group where n = 4.)