JP4424523B2 - Formazan compound and staining method using the same - Google Patents

Description

【０００６】
（式（１）においてＲ₁は水素原子、スルホン酸基、水酸基、クロル基、メトキシ基、カルボキシル基またはアルキル基を、Ｒ₂及びＲ₃の一方は水素原子で他方はスルホン酸基を、Ｘはモルホリノ基、２−ヒドロキシエチルアミノ基またはビス（２−ヒドロキシエチル）アミノ基を、Ｙは式（２）
【０００７】
【化４】

【０００８】
（式（２）においてＲ₄はスルホン酸基またはカルボキシル基を表す。）
で示されるフェニレンジイミノ基をそれぞれ表す。）
で表されるホルマザン化合物又はその塩、
（２）式（１）において、Ｒ₁は水素原子、Ｒ₂及びＲ₃の一方は水素原子で他方はスルホン酸基、Ｘはモルホリノ基、２−ヒドロキシエチルアミノ基またはビス（２−ヒドロキシエチル）アミノ基、Ｙは式（２）において２つのイミノ基がフェニレン基を介してパラ位に結合している基である（１）記載のホルマザン化合物又はその塩、
【０００９】
（３）式（１）において、Ｒ₁は水素原子、Ｒ₂は水素原子、Ｒ₃はスルホン酸基、Ｘはモルホリノ基またはビス（２−ヒドロキシエチル）アミノ基を、Ｙは式（２）において２つのイミノ基がフェニレン基を介してパラ位に結合している基である（１）記載のホルマザン化合物又はその塩、
（４）式（１）において、Ｒ₁は水素原子、Ｒ₂は水素原子、Ｒ₃はスルホン酸基、Ｘはモルホリノ基、Ｙは式（２）においてＲ₄がスルホン酸基でかつ２つのイミノ基がフェニレン基を介してパラ位に結合している基である（１）記載のホルマザン化合物又はその塩、
（５）（１）ないし（４）のいずれか１項に記載のホルマザン化合物又はその塩を使用することを特徴とするセルロース系高分子基材の染色方法、
（６）（１）ないし（４）のいずれか１項に記載のホルマザン化合物又はその塩で染色されたセルロース系高分子基材、
に関する。
【００１０】
【発明の実施の形態】
本発明の新規ホルマザン化合物は、前記式（１）で表される。前記式（１）において、Ｒ₁のアルキル基としては、例えばメチル基、エチル基、ｎ−プロピル基、ｎ−ブチル基等のＣ１〜Ｃ４のアルキル基があげられ、メチル基又はエチル基が好ましい。Ｒ₁の置換位置は２位又は４位が好ましい。
【００１１】
本発明の前記式（１）で示される新規ホルマザン化合物の代表的化合物の例を表１に示す。なお、表１のＹの項において、ＰＡＳは式（２）においてＲ₄がスルホン酸基でかつ２つのイミノ基がフェニレン基を介してパラ位に結合している基を、ＰＡＫは式（２）においてＲ₄がカルボキシル基でかつ２つのイミノ基がフェニレン基を介してパラ位に結合している基を、ＭＡＳは式（２）においてＲ₄がスルホン酸基でかつ２つのイミノ基がフェニレン基を介してメタ位に結合している基を、ＭＡＫは式（２）においてＲ₄がカルボキシル基でかつ２つのイミノ基がフェニレン基を介してメタ位に結合している基を、それぞれ表す。なお、式（２）において２つのイミノ基がフェニレン基を介してパラ位に結合している基の化学式（式（２−１））とメタ位に結合している基の化学式（式（２−２））を次に示す。
【００１２】
【化５】

【００１３】
（表１）

【００１４】
本発明の式（１）で示されるホルマザン化合物を得るには、まず下記式（３）で表されるホルマザンアミノ化合物を例えば以下に述べる方法により合成する。アミノ安息香酸類を常法によりジアゾ化し、そのジアゾ化物より得られるヒドラジン類１モルに対し、ベンズアルデヒド類１モルを、水溶液中８０〜９５℃で縮合してフェニルヒドラゾン類を得る。これに、６−アセチルアミノ−２−アミノフェノール−４−スルホン酸のジアゾ化物１モルを、水溶液中０〜５℃で、ソーダ灰の存在下でカップリングさせる。次いで、硫酸銅、塩化銅等を１〜１．５モル加え銅化し、その後アセチルアミノ基を強アルカリで６０〜９０℃で、３〜６時間処理して加水分解することにより、式（３）のホルマザンアミノ化合物が得られる。
【００１５】
【化６】

【００１６】
（式（３）において、Ｒ₁、Ｒ₂、Ｒ₃はそれぞれ前記と同じ意味を表す。）
次に１例として、以下に述べる方法によって式（１）のホルマザン化合物が合成される。
式（３）で表されるホルマザンアミノ化合物１モルに対し２，４，６−トリクロロ−１，３，５−トリアジン１モルを０〜１０℃、ｐＨ６〜８で、２〜３時間反応させて一次縮合物を得、次いでこの一次縮合物２モルに、Ｙに対応するジアミン類１モルを５０〜６５℃、ｐＨ６〜９、８〜２４時間反応させて二次縮合物を得、その後この二次縮合物１モルに、Ｘに対応するアミン類２モルを８０〜９５℃、ｐＨ６〜９、６〜１８時間反応させることにより三次縮合物である式（１）で表されるホルマザン化合物を得る。
【００１７】
本発明の式（１）で示されるホルマザン化合物は次の方法でも合成できる。
２，４，６−トリクロロ−１，３，５−トリアジン２モルに対し、Ｙに対応するジアミン類１モルを、０〜１０℃、ｐＨ５〜８、２〜４時間反応させて一次縮合物を得、次いでこの一次縮合物１モルに、式（３）で表されるホルマザンアミノ化合物２モルを、５０〜６５℃、ｐＨ６〜９、２〜４時間反応させて二次縮合物を得、その後この二次縮合物１モルに、Ｘに対応するアミン類２モルを、８０〜９５℃、ｐＨ６〜９、６〜１８時間反応させ、式（１）で表されるホルマザン化合物を得る。
【００１８】
本発明の前記式（１）で表される化合物は塩となっていても良い。塩は水溶性塩が好ましい。塩としては、例えばアルカリ金属塩、アルカリ土類金属塩、アルキルアミン塩、アルカノールアミン塩またはアンモニウム塩等があげられる。好ましくはナトリウム塩、カリウム塩、リチウム塩等のアルカリ金属塩、モノエタノールアミン塩、ジエタノールアミン塩、トリエタノールアミン塩、モノイソプロパノールアミン塩、ジイソプロパノールアミン塩、トリイソプロパノールアミン塩等のアルカノールアミン塩があげられる。
【００１９】
前記式（１）の上記各々の塩を得るには、例えば、得られたナトリウム塩の結晶を水に溶解させ、酸を添加して酸性とした後、場合によりろ過して得られるケーキを再び水に溶解させ、水酸化カリウム、水酸化リチウム、アンモニア水、ジエタノールアミン又はトリエタノールアミン等のアミンを添加することにより、それぞれカリウム塩、リチウム塩、アンモニウム塩、ジエタノールアミン塩又はトリエタノールアミン塩等のアミン塩とすることができる。式（１）で表されるホルマザン化合物は、通常の方法により、塩析により取り出しを行い乾燥製品として、また、反応液を希釈又は濃縮等の濃度調整をし、液状製品としても良い。
【００２０】
本発明のホルマザン化合物（１）は、直接染料として、天然または再生のセルロース系高分子基材の染色に使用される。染色の対象となるセルロース系高分子基材としては、例えば木綿、麻等の天然のセルロース系繊維、レーヨン等の再生のセルロース繊維、これらを含有する混紡繊維、紙、パルプ等があげられる。
【００２１】
天然または再生のセルロース系繊維の染色法としては、浸染法、捺染法、パディング法が適用されるが、最も好ましい方法は、浸染法である。
【００２２】
本発明の化合物（１）を用いて、天然または再生のセルロース系繊維を浸染により染着させる場合は、例えば被染物を浴比の比較的大きな条件で染浴の中に４０〜５０℃で導入し染浴の温度を８０〜１００℃に徐々に高め、そしてこの温度で２０〜６０分間染色することによって行われる。なお、その実際の染色温度に達する前に、または場合によってはその温度に達した後に、染料の吸収を促進するために塩化ナトリウム、硫酸ナトリウムのような中性塩を染浴に加えることができる。また、ポリエステル繊維とレーヨンとの混紡繊維を分散染料とともに一浴で染色する際には、高温染色法により１２０〜１３０℃で染色するが、その際、ｐＨ調整剤を用いてｐＨを中性〜アルカリに調整し染色することが好ましい。本発明の化合物（１）は、高温染色においても親和性が低下することがない。また、汎用の黄色染料、赤色染料などとの配合染色を行った場合、親和性が揃っているため再現性が良好である。そして、化合物（１）を使用して得られた染色物は耐光、洗濯、塩素水堅牢度に優れ、しかもカラーバリュー、ビルドアップ性が良好である。
【００２３】
次に本発明の化合物を用いて紙、パルプの染色を行う場合につき説明する。紙の染色法としては、（Ｉ）パルプの解離または叩解時に染料を添加して染色する内添法と、（ＩＩ）パルプのサイズプレス工程でサイズプレス液に染料を添加する外添法に大別されるが、その他、紙の表面に染料、無機白色顔料、バインダー等から調製された塗工液をオーバーコーティングする方法も採用される。式（１）のホルマザン化合物はいずれの方法にも適用可能であるが、より好ましい方法は内添法である。内添法においては、まずパルプをパルパー、リファイナー等によって通常４００〜４９０ｃ．ｃ．の叩解度に叩解してパルプスラリーとなし、これに温度１０〜４０℃において通常０．０１〜３．０％（乾燥紙重量あたり）の式（１）のホルマザン化合物を添加し更に通常の填料、サイズ剤、硫酸バンド、紙力増強剤、固着剤等を必要に応じて添加したあと常法により抄紙工程、乾燥工程を得て式（１）のホルマザン化合物で染色された紙を得る。式（１）の化合物は紙（セルロース系高分子基材）に対する親和性、カラーバリューが高く、かつ得られた染色紙の堅牢度（耐光性）が良好である。
【００２４】
【実施例】
次に実施例によって本発明を更に具体的に説明するが、本発明がこれらの実施例のみに限定されるものではない。実施例中「部」及び「％」はそれぞれ「重量部」及び「重量％」を示す。
【００２５】
実施例１
２，４，６−トリクロロ−１，３，５−トリアジン５．０部を、水１５部、氷１０部、１０％リパールＯＨ（アニオン性界面活性剤、ライオン製）水溶液０．５部からなる溶液中に撹拌下に加えた。３０分撹拌後、３℃以下に維持し、これを、上記式（３）のホルマザンアミノ化合物（上記式（３）において、Ｒ₁は水素原子、Ｒ₂は水素原子、Ｒ₃はスルホン酸基である化合物）１６．０部を水１８０部に完溶した溶液に注加した。その後、１０℃前後で１０％ソーダ灰水溶液を滴下しｐＨ６〜８に維持しながら２時間反応させて一次縮合物の反応液を得た。その後、１，４−ジアミノベンゼン−２−スルホン酸２．６部を水２５部中に弱酸性で溶解させた溶液を上記反応液中に添加した。この混合物を昇温し、５０〜６０℃の温度で１０％ソーダ灰水溶液によりｐＨ値を６〜８に維持しながら６時間反応させて、二次縮合物の反応液を得た。この反応液中にモルホリン３．５部を加え、昇温し、８５〜９０℃の温度でｐＨ値を７前後に維持しながら８時間反応させた。次いで同温度で対液５％の塩化ナトリウムにて塩析し、結晶を濾別、乾燥してＮｏ．１の化合物（上記式（１）において、Ｒ₁とＲ₂はいずれも水素原子、Ｒ₃はスルホン酸基、Ｘはモルホリノ基、ＹはＰＡＳである化合物，λmax：５９５ｎｍ）を含む粉末３３．５部を得た。
【００２６】
実施例２
２，４，６−トリクロロ−１，３，５−トリアジン５部を、水１５部、氷１５部、１０％リパールＯＨ水溶液０．０５部からなる溶液中に撹拌下に加え、４５分撹拌後した。これに、１，４−ジアミノベンゼン−２−スルホン酸２．５部を水４０部に完溶した溶液を、８℃以下に維持しながら注加し、１０％ソーダ灰水溶液によりｐＨを６〜８に維持しながら１１時間反応させて一次縮合物の反応液を得た。次に、式（３）のホルマザンアミノ化合物（実施例１で使用した化合物）１７．４を水１３０部に完溶させ上記反応液を添加した。この混合物を昇温し、５０〜６０℃の温度で１０％ソーダ灰水溶液によりｐＨ６〜８に維持しながら、４時間反応させて二次縮合物の反応液を得た。この二次縮合物を含む反応液中にモルホリン３．５部を加え、昇温し、８５〜９０℃の温度でｐＨ値を７前後に維持しながら８時間反応させた。次いで同温度で対液７％の塩化ナトリウムにて塩析し、結晶を濾別、乾燥してＮｏ．１の化合物を含む粉末４６．２部を得た。
【００２７】
実施例３
実施例１で得られたＮｏ．１の化合物を含む粉末１部を熱湯２００部に溶かし、無水硫酸ナトリウム１０部および水８００部を加え染浴とする。この中へ、ビスコースレーヨンの布５０部を浸漬し、撹拌しながら徐々に９０℃に昇温し、このまま４０分間染色する。その後、水洗乾燥し染着性良好な青色染色物を得た。上記方法で得られた染色物５０部をポリアミン系フィックス剤浴（フィックス剤〈スプラフィックスＤＦＣ（センカ製）〉２部を水１０００部に溶解して得た物）に入れ、６０℃の温度で２０分間浸漬した後、乾燥する。こうして得られた染色物のフィックス剤処理による変退色は認められなかった。この染色物は、耐光性が良好であり、耐洗濯性、耐塩素水性も優れていた。これらの評価結果を表２に示す。
【００２８】
比較例１
Ｃ．Ｉ．Ｄｉｒｅｃｔ Ｂｌｕｅ ２００（ジアニシジン系染料）を用いて、実施例３と同様にしてレーヨン布を染色、乾燥し青色染色物を得た。この染色物を、実施例３と同様にフィックス剤処理をおこなったところ、処理による変色が大きかった。諸堅牢度を表２に示す。
【００２９】
比較例２
特許第２５１０８７６号実施例１記載の染料（下記式（４））を用いて、実施例３と同様にしてレーヨン布を染色、乾燥し青色染色物を得た。この染色物を、実施例３と同様にしてフィックス剤処理をおこなった。諸堅牢度を表２に示す。
【００３０】
【化７】

【００３１】
（表２）

【００３２】
（堅牢度試験方法）
染色後、ポリアミン系フィックス剤にて処理を行った染布について実施。
耐光 ：ＪＩＳ Ｌ０８４２ カーボンアークフェードメーター ２０、４０時間照射
洗濯 ：ＪＩＳ Ｌ０８４４ Ａ−２法
塩素水 ：ＪＩＳ Ｌ０８８４ 弱
【００３３】
（判定及び結果の表示）

【００３４】
比較例１のジアニシジン系染料を用いた場合、染布の鮮明性は低く、フィックス剤処理による変色が大きかった。また、塩素水堅牢度も実施例３の場合と比較して劣るものであった。また、比較例２の染料を用いた場合は、１３０℃の高温において親和性が低下し、所望の濃度が得られなかった。また、染布の洗濯堅牢度は実施例３の場合と比較して非常に劣るものであった。
【００３５】
実施例４
実施例１で得られたＮｏ．１の化合物を含む粉末１部を熱湯２００部に溶かし、無水硫酸ナトリウム１０部、Ｋａｙａｋｕ Ｂｕｆｆｅｒ Ｐ−７（日本化薬製ｐＨ調整剤）２部、および水８００部を加えｐＨ７の染浴とする。この中へ、ビスコースレーヨンの布５０部を浸漬し、撹拌しながら徐々に１３０℃に昇温し、このまま６０分間染色する。その後、水洗乾燥した。高温においても親和性が低下することがなく、染着性良好な青色染色物を得た。
【００３６】
実施例５
下記組成で染浴を調製する。
実施例１で得られたＮｏ．１の化合物を含む粉末 ０．２５部
Ｋａｙａｃｅｌｏｎ Ｙｅｌｌｏｗ ＴＲ（日本化薬製直接染料）０．４０部
Ｋａｙａｃｅｌｏｎ Ｒｕｂｉｎｅ ＴＲ（日本化薬製直接染料）０．２５部
Ｋａｙａｋｕ Ｂｕｆｆｅｒ Ｐ−７（日本化薬製ｐＨ調整剤） ２部
無水硫酸ナトリウム １０部
純水 １０００部
この中へ、ビスコースレーヨンの布５０部を浸漬し、撹拌しながら徐々に１３０℃に昇温し、このまま６０分間染色する。その後、水洗乾燥した。染料の親和性がそろっているため、均一な茶色染色物を得た。
【００３７】
実施例６
実施例１で得られたＮｏ．１の化合物を含む粉末０．０５部と水６０部からなる染浴を調製し、この染浴にパルプ２部（乾燥重量）、無水硫酸ナトリウム０．０４部を加えて室温で１５分間撹拌する。その後、ＲＦ−サイズ８８０Ｌ−５０（商品名、サイズ剤、ミサワセラミックケミカル製）０．０２部を加え１０分撹拌し、結晶硫酸アルミニウム０．０６部を加えて、さらに２０分間撹拌する。次いでＪＩＳ ８２０９（パルプ試験用手スキ紙調製方法）に記載の方法に準じ抄紙、乾燥し、青色に着色された紙を得た。このものは、耐光堅牢度が良好であった。
【００３８】
【発明の効果】
本発明で得られるホルマザン化合物は環境衛生の面から安全性が高く、セルロース系高分子基材を染色した場合、カラーバリュー、ビルドアップ性、諸堅牢度の優れた染色物が得られる。また、繊維の染色において、セルロース系繊維とポリエステル繊維との混紡繊維を染色する際、高温染色を行っても親和性が低下することなく、また汎用の黄色染料、赤色染料との配合染色時も親和性が揃っているため、染色再現性が良好である。紙の染色においても、染着性、耐光性が良好であり、原料としてジアニシジン系化合物を用いることなく鮮明な青色染色物が得られる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a formazan compound and a cellulosic polymer substrate dyed using the formazan compound.
[0002]
[Prior art]
As a dye for dyeing a cellulosic polymer base material in a solid blue color, conventional C.I. I. Dianisidine dyes such as Direct Blue 200, 202, and 203 are known and have been used in large quantities in the fiber dyeing industry and the papermaking industry. However, dianisidine, which is the base material of these dyes, falls under the category of a specific chemical substance, and special considerations and restrictions on its use are inevitable in its manufacture and use.
Although various alternative products have been developed, no satisfactory results have been obtained yet. For example, Japanese Patent No. 2510876 describes formazan-based direct dyes, but has the disadvantage of poor high-temperature dyeability and washing resistance. From the viewpoint of environmental hygiene, there is a demand for a blue dye having higher safety and excellent dyeing effect. In addition, there is a demand for a dye that is dyed at a high temperature in blending with a polyester fiber or the like but does not decrease the affinity for cellulose fiber even at a high temperature.
[0003]
[Problems to be solved by the invention]
It is an important issue to develop a blue dye suitable for dyeing a cellulosic polymer base material having good color value, build-up property and various fastness properties without using a dianisidine compound as a raw material.
[0004]
[Means for Solving the Problems]
The inventor of the present invention has made the present invention as a result of intensive studies to solve the above-described conventional drawbacks.
That is, the present invention
(1) The following formula (1)
[0005]
[Chemical 3]

[0006]
(In the formula (1), R ₁ is a hydrogen atom, a sulfonic acid group, a hydroxyl group, a chloro group, a methoxy group, a carboxyl group or an alkyl group, one of R ₂ and R ₃ is a hydrogen atom and the other is a sulfonic acid group, Is a morpholino group, a 2-hydroxyethylamino group or a bis (2-hydroxyethyl) amino group, and Y is a formula (2)
[0007]
[Formula 4]

[0008]
(In the formula (2), R ₄ represents a sulfonic acid group or a carboxyl group.)
Each represents a phenylenediimino group represented by )
A formazan compound represented by the formula:
(2) In the formula (1), R ₁ is a hydrogen atom, one of R ₂ and R ₃ is a hydrogen atom and the other is a sulfonic acid group, X is a morpholino group, 2-hydroxyethylamino group or bis (2-hydroxyethyl) ) Amino group, Y is a formazan compound or a salt thereof according to (1), wherein two imino groups in formula (2) are bonded to the para-position via a phenylene group,
[0009]
(3) In the formula (1), R ₁ is a hydrogen atom, R ₂ is a hydrogen atom, R ₃ is a sulfonic acid group, X is a morpholino group or bis (2-hydroxyethyl) amino group, and Y is a formula (2) A formazan compound or a salt thereof according to (1), wherein two imino groups are bonded to the para-position via a phenylene group in
(4) formula (1), R ₁ represents a hydrogen atom, R ₂ is a hydrogen atom, R ₃ is a sulfonic acid group, X is a morpholino group, Y has the formula (2) in R ₄ is and the two sulphonic acid groups The formazan compound or a salt thereof according to (1), wherein the imino group is a group bonded to the para-position via a phenylene group;
(5) A method for dyeing a cellulosic polymer substrate, comprising using the formazan compound or a salt thereof according to any one of (1) to (4),
(6) A cellulosic polymer substrate dyed with the formazan compound or salt thereof according to any one of (1) to (4),
About.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The novel formazan compound of the present invention is represented by the formula (1). In the formula (1), examples of the alkyl group for R ₁ include C1-C4 alkyl groups such as a methyl group, an ethyl group, an n-propyl group, and an n-butyl group, and a methyl group or an ethyl group is preferable. . The substitution position of R ₁ is preferably the 2-position or the 4-position.
[0011]
Examples of representative compounds of the novel formazan compound represented by the above formula (1) of the present invention are shown in Table 1. In the Y section of Table 1, PAS is a group in which R ₄ is a sulfonic acid group and two imino groups are bonded to the para-position via a phenylene group in the formula (2), and PAK is a formula (2 ) In which R ₄ is a carboxyl group and two imino groups are bonded to the para-position via a phenylene group, MAS is a group in which R ₄ is a sulfonic acid group and two imino groups are phenylene in formula (2) MAK represents a group bonded to the meta position through a group, and MAK represents a group in which R ₄ is a carboxyl group and two imino groups are bonded to the meta position through a phenylene group in formula (2). . In the formula (2), the chemical formula of the group in which two imino groups are bonded to the para position via the phenylene group (formula (2-1)) and the chemical formula of the group bonded to the meta position (formula (2) -2)) is shown below.
[0012]
[Chemical formula 5]

[0013]
(Table 1)

[0014]
In order to obtain the formazan compound represented by the formula (1) of the present invention, a formazan amino compound represented by the following formula (3) is first synthesized by, for example, the method described below. Aminobenzoic acids are diazotized by a conventional method, and 1 mol of benzaldehyde is condensed in an aqueous solution at 80 to 95 ° C. with respect to 1 mol of hydrazine obtained from the diazotized product to obtain phenylhydrazones. To this, 1 mol of 6-acetylamino-2-aminophenol-4-sulfonic acid diazotate is coupled in an aqueous solution at 0-5 ° C. in the presence of soda ash. Next, 1 to 1.5 mol of copper sulfate, copper chloride or the like is added to form copper, and then the acetylamino group is hydrolyzed by treatment with a strong alkali at 60 to 90 ° C. for 3 to 6 hours to obtain the formula (3). The formazan amino compound is obtained.
[0015]
[Chemical 6]

[0016]
(In the formula (3), R ₁ , R ₂ and R ₃ each have the same meaning as described above.)
Next, as an example, the formazan compound of formula (1) is synthesized by the method described below.
1 mol of 2,4,6-trichloro-1,3,5-triazine is reacted at 0 to 10 ° C. and pH 6 to 8 for 2 to 3 hours with respect to 1 mol of the formazan amino compound represented by the formula (3). A primary condensate is obtained, and then 2 mol of this primary condensate is reacted with 1 mol of a diamine corresponding to Y at 50 to 65 ° C., pH 6 to 9, and 8 to 24 hours to obtain a secondary condensate. A formazan compound represented by the formula (1), which is a tertiary condensate, is obtained by reacting 2 mol of amines corresponding to X with 1 mol of the subcondensate at 80 to 95 ° C., pH 6 to 9, and 6 to 18 hours. .
[0017]
The formazan compound represented by the formula (1) of the present invention can also be synthesized by the following method.
The primary condensate is obtained by reacting 2 mol of 2,4,6-trichloro-1,3,5-triazine with 1 mol of a diamine corresponding to Y at 0 to 10 ° C., pH 5 to 8 for 2 to 4 hours. Then, 1 mol of the primary condensate is reacted with 2 mol of the formazan amino compound represented by the formula (3) at 50 to 65 ° C., pH 6 to 9 for 2 to 4 hours to obtain a secondary condensate, 1 mol of this secondary condensate is reacted with 2 mol of an amine corresponding to X at 80 to 95 ° C., pH 6 to 9, and 6 to 18 hours to obtain a formazan compound represented by the formula (1).
[0018]
The compound represented by the formula (1) of the present invention may be a salt. The salt is preferably a water-soluble salt. Examples of the salt include alkali metal salts, alkaline earth metal salts, alkylamine salts, alkanolamine salts, and ammonium salts. Preferred are alkali metal salts such as sodium salt, potassium salt and lithium salt, alkanolamine salts such as monoethanolamine salt, diethanolamine salt, triethanolamine salt, monoisopropanolamine salt, diisopropanolamine salt and triisopropanolamine salt. It is done.
[0019]
In order to obtain each of the above-mentioned salts of the formula (1), for example, the obtained sodium salt crystals are dissolved in water, acidified by adding an acid, and the cake obtained by filtration in some cases is again obtained. Amine such as potassium salt, lithium salt, ammonium salt, diethanolamine salt or triethanolamine salt by dissolving in water and adding amine such as potassium hydroxide, lithium hydroxide, aqueous ammonia, diethanolamine or triethanolamine, respectively It can be a salt. The formazan compound represented by the formula (1) may be taken out by salting out by a conventional method to give a dry product, or the reaction solution may be diluted or concentrated to adjust the concentration to be a liquid product.
[0020]
The formazan compound (1) of the present invention is used as a direct dye for dyeing natural or regenerated cellulose polymer substrates. Examples of the cellulosic polymer base material to be dyed include natural cellulosic fibers such as cotton and hemp, regenerated cellulose fibers such as rayon, blended fibers containing these, paper, and pulp.
[0021]
As a dyeing method for natural or regenerated cellulosic fibers, a dyeing method, a printing method, and a padding method are applied, and the most preferable method is a dyeing method.
[0022]
When natural or regenerated cellulosic fibers are dyed by dip dyeing using the compound (1) of the present invention, for example, the article to be dyed is introduced into the dye bath at a temperature of 40 to 50 ° C. under a relatively large bath ratio. This is done by gradually increasing the temperature of the dyeing bath to 80-100 ° C. and dyeing at this temperature for 20-60 minutes. It should be noted that neutral salts such as sodium chloride and sodium sulfate can be added to the dye bath to promote dye absorption before or after reaching the actual dyeing temperature. . In addition, when dyed polyester fiber and rayon blended fiber together with disperse dye in one bath, dyeing is performed at 120 to 130 ° C. by a high temperature dyeing method. It is preferable to adjust to an alkali and dye. The affinity of the compound (1) of the present invention does not decrease even at high temperature dyeing. In addition, when compounding dyeing with a general-purpose yellow dye, red dye or the like is performed, reproducibility is good because the affinity is uniform. And the dyeing | staining obtained by using the compound (1) is excellent in light fastness, washing and fastness to chlorine water, and also has good color value and build-up property.
[0023]
Next, the case of dyeing paper and pulp using the compound of the present invention will be described. Paper dyeing methods include (I) an internal addition method in which a dye is added and dyed at the time of pulp dissociation or beating, and (II) an external addition method in which a dye is added to the size press solution in the pulp size pressing step. In addition, a method of overcoating a coating liquid prepared from a dye, an inorganic white pigment, a binder and the like on the surface of paper is also employed. The formazan compound of the formula (1) can be applied to any method, but a more preferable method is an internal addition method. In the internal addition method, first, the pulp is usually 400 to 490 c. c. A pulp slurry is obtained by beating to a degree of beating, and 0.01 to 3.0% (per dry paper weight) of the formazan compound of the formula (1) is added at a temperature of 10 to 40 ° C. Then, a sizing agent, a sulfuric acid band, a paper strength enhancer, a fixing agent and the like are added as necessary, and then a papermaking process and a drying process are obtained by a conventional method to obtain a paper dyed with the formazan compound of formula (1). The compound of the formula (1) has high affinity and color value for paper (cellulosic polymer base material) and good fastness (light resistance) of the dyed paper obtained.
[0024]
【Example】
EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited only to these Examples. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.
[0025]
Example 1
5.0 parts of 2,4,6-trichloro-1,3,5-triazine is composed of 15 parts of water, 10 parts of ice and 0.5 part of an aqueous solution of 10% Lipar OH (anionic surfactant, manufactured by Lion). Added to the solution under stirring. After stirring for 30 minutes, the temperature is maintained at 3 ° C. or lower, and this is replaced with the formazan amino compound of the above formula (3) (in the above formula (3), R ₁ is a hydrogen atom, R ₂ is a hydrogen atom, R ₃ is a sulfonic acid group). 16.0 parts of this compound was poured into a solution completely dissolved in 180 parts of water. Thereafter, a 10% soda ash aqueous solution was dropped at around 10 ° C., and the mixture was reacted for 2 hours while maintaining the pH at 6 to 8, thereby obtaining a reaction solution of a primary condensate. Thereafter, a solution prepared by dissolving 2.6 parts of 1,4-diaminobenzene-2-sulfonic acid in 25 parts of water with weak acidity was added to the reaction solution. This mixture was heated and reacted at a temperature of 50-60 ° C. for 6 hours while maintaining the pH value at 6-8 with a 10% aqueous soda ash solution to obtain a reaction solution of a secondary condensate. To this reaction solution, 3.5 parts of morpholine was added, the temperature was raised, and the reaction was carried out for 8 hours while maintaining the pH value at around 7 at a temperature of 85 to 90 ° C. Subsequently, salting out was performed with 5% sodium chloride solution at the same temperature, and the crystals were separated by filtration and dried. 33. A powder comprising 1 compound (in the formula (1), R ₁ and R ₂ are both hydrogen atoms, R ₃ is a sulfonic acid group, X is a morpholino group, Y is a PAS, λmax: 595 nm). 5 parts were obtained.
[0026]
Example 2
2,4,6-Trichloro-1,3,5-triazine (5 parts) was added to a solution consisting of 15 parts of water, 15 parts of ice and 0.05 part of a 10% aqueous Lipar OH solution and stirred for 45 minutes. did. To this, a solution in which 2.5 parts of 1,4-diaminobenzene-2-sulfonic acid was completely dissolved in 40 parts of water was added while maintaining the temperature at 8 ° C. or lower, and the pH was adjusted to 6 to 6 with a 10% soda ash aqueous solution. The mixture was allowed to react for 11 hours while maintaining the temperature of 8, to obtain a reaction solution of a primary condensate. Next, the formazan amino compound of formula (3) (compound used in Example 1) 17.4 was completely dissolved in 130 parts of water, and the reaction solution was added. The mixture was heated and reacted at a temperature of 50 to 60 ° C. for 4 hours while maintaining a pH of 6 to 8 with a 10% aqueous soda ash solution to obtain a reaction solution of a secondary condensate. To this reaction solution containing the secondary condensate, 3.5 parts of morpholine was added, the temperature was raised, and the reaction was carried out for 8 hours while maintaining the pH value at around 7 at a temperature of 85 to 90 ° C. Subsequently, salting out was performed with 7% sodium chloride solution at the same temperature, and the crystals were separated by filtration and dried. 46.2 parts of a powder containing 1 compound were obtained.
[0027]
Example 3
No. 1 obtained in Example 1. 1 part of powder containing 1 compound is dissolved in 200 parts of hot water, and 10 parts of anhydrous sodium sulfate and 800 parts of water are added to form a dye bath. In this, 50 parts of viscose rayon cloth is immersed, gradually heated to 90 ° C. while stirring, and dyed for 40 minutes as it is. Thereafter, it was washed with water and dried to obtain a blue dyed product with good dyeability. 50 parts of the dyed product obtained by the above method is placed in a polyamine-based fixing agent bath (fixed agent <suprafix DFC (manufactured by Senka)> 2 parts dissolved in 1000 parts of water) at a temperature of 60 ° C. Immerse for 20 minutes and then dry. The dyed dyeing thus obtained was not discolored by the fixer treatment. This dyed article had good light resistance, and was excellent in washing resistance and chlorine water resistance. These evaluation results are shown in Table 2.
[0028]
Comparative Example 1
C. I. Using Direct Blue 200 (dianisidine dye), a rayon cloth was dyed and dried in the same manner as in Example 3 to obtain a blue dyed product. When this dyed product was treated with a fixing agent in the same manner as in Example 3, discoloration due to the treatment was large. Various fastnesses are shown in Table 2.
[0029]
Comparative Example 2
Patent No. 2510876 Using the dye described in Example 1 (the following formula (4)), a rayon cloth was dyed and dried in the same manner as in Example 3 to obtain a blue dyed product. This dyed product was treated with a fixing agent in the same manner as in Example 3. Various fastnesses are shown in Table 2.
[0030]
[Chemical 7]

[0031]
(Table 2)

[0032]
(Fastness test method)
After dyeing, it is carried out on dyed fabrics that have been treated with a polyamine-based fixing agent.
Light resistance: JIS L0842 Carbon arc fade meter 20, 40 hours irradiation washing: JIS L0844 A-2 method chlorinated water: JIS L0884 weak [0033]
(Judgment and result display)

[0034]
When the dianisidine dye of Comparative Example 1 was used, the clearness of the dyed fabric was low and the discoloration due to the fixing agent treatment was large. Further, the fastness to chlorine water was inferior to that in Example 3. Further, when the dye of Comparative Example 2 was used, the affinity decreased at a high temperature of 130 ° C., and a desired concentration could not be obtained. Further, the fastness to washing of the dyed fabric was very inferior to that of Example 3.
[0035]
Example 4
No. 1 obtained in Example 1. 1 part of powder containing 1 compound is dissolved in 200 parts of hot water, and 10 parts of anhydrous sodium sulfate, 2 parts of Kayaku Buffer P-7 (Nippon Kayaku pH adjuster) and 800 parts of water are added to obtain a pH 7 dyeing bath. . In this, 50 parts of a viscose rayon cloth is immersed, gradually heated to 130 ° C. while stirring, and dyed for 60 minutes. Thereafter, it was washed with water and dried. Even at high temperatures, the affinity did not decrease, and a blue dyed product with good dyeability was obtained.
[0036]
Example 5
A dye bath is prepared with the following composition.
No. 1 obtained in Example 1. Powder containing 1 compound 0.25 part Kaycelon Yellow TR (direct dye manufactured by Nippon Kayaku) 0.40 part Kaycelon Rubin TR (direct dye manufactured by Nippon Kayaku) 0.25 part Kayaku Buffer P-7 (manufactured by Nippon Kayaku) pH adjuster) 2 parts anhydrous sodium sulfate 10 parts pure water 1000 parts In this, 50 parts of a viscose rayon cloth is immersed, gradually heated to 130 ° C. with stirring, and dyed for 60 minutes. Thereafter, it was washed with water and dried. A uniform brown dyeing was obtained because of the affinity of the dyes.
[0037]
Example 6
No. 1 obtained in Example 1. A dyebath consisting of 0.05 part of powder containing 1 compound and 60 parts of water is prepared, 2 parts of pulp (dry weight) and 0.04 part of anhydrous sodium sulfate are added to this dyebath and stirred at room temperature for 15 minutes. . Thereafter, 0.02 part of RF-size 880L-50 (trade name, sizing agent, manufactured by Misawa Ceramic Chemical) is added and stirred for 10 minutes, 0.06 part of crystalline aluminum sulfate is added, and the mixture is further stirred for 20 minutes. Next, papermaking and drying were carried out according to the method described in JIS 8209 (Method for preparing hand skim paper for pulp test) to obtain blue colored paper. This product had good light fastness.
[0038]
【The invention's effect】
The formazan compound obtained in the present invention is highly safe from the viewpoint of environmental hygiene, and when a cellulose polymer base material is dyed, a dyed product having excellent color value, build-up property, and various fastnesses can be obtained. In addition, when dyeing fiber blends of cellulosic fibers and polyester fibers in the dyeing of fibers, affinity does not decrease even when high-temperature dyeing is performed, and also when compounding dyeing with general-purpose yellow dyes and red dyes Since the affinity is uniform, dyeing reproducibility is good. Also in the dyeing | staining of paper, dyeing property and light resistance are favorable, and a clear blue dyeing | staining thing is obtained, without using a dianisidine type compound as a raw material.

Claims (6)

Following formula (1)

(In the formula (1), R ₁ represents a hydrogen atom, a sulfonic acid group, a hydroxyl group, a chloro group, a methoxy group, a carboxyl group or an alkyl group, one of R ₂ and R ₃ represents a hydrogen atom and the other represents a sulfonic acid group, Is a morpholino group, a 2-hydroxyethylamino group or a bis (2-hydroxyethyl) amino group, and Y is a formula (2)

(In Formula (2), R ₄ represents a sulfonic acid group or a carboxyl group), and each represents a phenylenediimino group. Formazan compound or a salt thereof which is a direct dye represented by In formula (1), R ₁ is a hydrogen atom, one of R ₂ and R ₃ is a hydrogen atom and the other is a sulfonic acid group, X is a morpholino group, a 2-hydroxyethylamino group or a bis (2-hydroxyethyl) amino group Y is a formazan compound or a salt thereof as a direct dye according to claim 1, wherein Y is a group in which two imino groups are bonded to the para-position via a phenylene group in the formula (2). In the formula (1), R ₁ is a hydrogen atom, R ₂ is a hydrogen atom, R ₃ is a sulfonic acid group, X is a morpholino group or bis (2-hydroxyethyl) amino group, Y is two iminos in the formula (2) The formazan compound or a salt thereof as a direct dye according to claim 1, wherein the group is a group bonded to the para position via a phenylene group. In formula (1), _{R 1} is a hydrogen atom, _{R 2} is a hydrogen atom, _{R 3} is a sulfonic acid group, X is a morpholino group, Y is _{R 4} is a sulfonic acid group and two imino groups in the formula (2) The formazan compound or a salt thereof which is a direct dye according to claim 1, which is a group bonded to the para-position via a phenylene group. A method for dyeing a cellulose-based polymer substrate, characterized by dyeing with a formazan compound or a salt thereof which is a direct dye according to any one of claims 1 to 4. A cellulose polymer substrate dyed with a formazan compound or a salt thereof which is a direct dye according to any one of claims 1 to 4.