JPS6086168A - Azo compound and dyeing of fiber material using the same - Google Patents

Abstract

NEW MATERIAL:The water-soluble azo compound of formula I [X is H, methyl, methoxy or 2-methoxyethoxy; Y is H, methyl, methoxy, acetylamino or ureido; R1 and R2 are H or methyl; n is 2 or 3; Z is group of formula II (COOH is bonded to 3- or 4-position), Cl or F; B is -(CH2)m- (m is 2 or 3), -C2H4OC2H4-, (substituted) p-phenylenediamine residue, etc.; the COOH of pyridine ring is bonded to 3- or 4-position] as a free acid. EXAMPLE:The compound of formula III. USE:Dye for dyeing cellulosic fibers such as cotton, regenerated viscose fiber, flax, etc. or blend of polyester fiber, etc. and cotton, etc., in yellowish color having excellent fastness to moisture, chlorine, light, sweat and sunlight. PREPARATION:For example, the objective compound can be produced by (1) coupling the diazo compound of formula IV with the compound of formula V, (2) reacting the coupled product with the compound of formula VI in water, (3) reacting the reaction product with the compound of formula VII, and (4) reacting with (iso)nicotinic acid in water at 50-100 deg.C.

Description

【発明の詳細な説明】 本発明は水溶性アゾ化合物及びそれを用いる緻維拐料の
染色法に関する。更に詳しくは式（す乞 （式（１）中Ｘは水素原子、メチル基、メトキシ基又は
２−メトキシエトキシ基ｅ、Ｙは水素原子、メチル基、
メトキシ基、アセチルアミノ基又はウレイド基を、Ｒ１
，Ｒ２は各々独立して水素原子又ｄメチル基を、ｎは２
又は５の数を、ｚｌは結合しているものとする）、クロ
ル原子又はフッ素原子を、Ｂは−（ＣＨ２）、−（ｍは
２又は３を表わす）　：　−Ｃ２Ｈ４０Ｃ２Ｈ４：　ｃ
Ｈ２占ＨＣＨ２−：　Ｊ　ｆ　ｔｖ基、メトキシ基、ス
ルホン酸基、カルボン酸基又はクロル原子で置換されて
いてもよいｐ−フェニレンジアミン残基又はｍ−フェニ
レンジアミン残基：（）◎−（Ｑは一〇　−、−８ｏ２
．−ＮＨＣＯ−、又はカルボキシル基は３−又は４−位
に結合しているものとする。） で表わされる水溶性アゾ化合物及びこれを用いるセルロ
ース又はセルロース含有繊維材料の染色法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-soluble azo compound and a method for dyeing fiber pellets using the same. More specifically, the formula (formula (1), where X is a hydrogen atom, a methyl group, a methoxy group, or a 2-methoxyethoxy group e, Y is a hydrogen atom, a methyl group,
methoxy group, acetylamino group or ureido group, R1
, R2 each independently represent a hydrogen atom or a methyl group, and n is 2
or the number of 5, zl is a bond), chlorine atom or fluorine atom, B is -(CH2), -(m represents 2 or 3): -C2H40C2H4: c
H2-occupied HCH2-: J f p-phenylenediamine residue or m-phenylenediamine residue optionally substituted with tv group, methoxy group, sulfonic acid group, carboxylic acid group, or chlorine atom: ()◎-(Q is 10 -, -8o2
．． -NHCO- or a carboxyl group shall be bonded to the 3- or 4-position. ) and a method for dyeing cellulose or cellulose-containing fiber materials using the water-soluble azo compound.

セルロース繊維用反応性染相ハ他のセルロース繊維用染
料に比べ、堅牢度、鮮明度が優れているので大量に使用
されている。Reactive dye phases for cellulose fibers are used in large quantities because they have superior fastness and sharpness compared to other dyes for cellulose fibers.

例えば、ジクロルトリアジニル、モノクロロトＩＪ　７
ジニル、フロロクロロピリミジニル、ジクロロキノキザ
ジニル、メチルスルホニルクロルピリミジニル、ビニル
スルホニル、スルファトエチルスルホニル等の反応基を
有する反応性染料を用いて酸結合剤又は熱等の作用によ
り酸結合剤を放出する物質（例えば、炭酸ナトリウム、
炭酸カリウウム、トリクロル酢酸ナトリウム）を単独又
は２１１以上を混合して用いて染浴のｐＨが１０以上に
なるように調整し、塩化ナトリウム、硫酸ナトリウム等
の中性電解質の存在下１００℃以下の温度でセルロース
繊維の染色がおこなわれている。For example, dichlorotriazinyl, monochlorotriazinyl, monochlorotriazinyl
Using a reactive dye having a reactive group such as di-nyl, fluorochloropyrimidinyl, dichloroquinoxazinyl, methylsulfonylchloropyrimidinyl, vinylsulfonyl, sulfatoethylsulfonyl, etc., the acid binder is released by the action of an acid binder or heat. substances (e.g., sodium carbonate,
Adjust the pH of the dye bath to 10 or higher using potassium carbonate, sodium trichloroacetate) alone or in a mixture of 211 or higher, and at a temperature of 100°C or lower in the presence of a neutral electrolyte such as sodium chloride or sodium sulfate. Cellulose fibers are dyed in

一方、衣料用の繊維拐料としてセルロース繊維を含有し
７Ｆ混合繊維材料（混紡）を用いることが多くなり、中
でもポリエステル４べ維とセルロース繊維の混紡、とり
わけポリエステル繊維と木綿の混紡ｃ以下Ｔ／Ｃ混と略
す）が衣料適性にすぐれている、経済性にすぐれる等の
理由で多用されるようになった。干してＴ／Ｃ混を反応
性染料及び分散染料を用いて染色するには次のような方
法が一般に用いられている。On the other hand, 7F mixed fiber materials (blends) containing cellulose fibers are increasingly used as fiber additives for clothing, especially blends of polyester 4-beam fibers and cellulose fibers, and especially blends of polyester fibers and cotton below T/C. (abbreviated as "C blend") has come to be widely used for reasons such as its excellent suitability for clothing and its economical efficiency. The following method is generally used to dye the dried T/C blend using reactive dyes and disperse dyes.

（１）−浴二段法 分散染料によりまず、ポリエステル繊維側をキャリヤー
染色法、高温染色法等により染色し、次いで同一浴で反
応性染料でセルロース繊維側を染色する。(1) - Two-bath method First, the polyester fiber side is dyed with a disperse dye by a carrier dyeing method, a high temperature dyeing method, etc., and then the cellulose fiber side is dyed with a reactive dye in the same bath.

又はこの逆の順による。Or in the reverse order.

（１１）二浴法 まず、ポリエステル繊維側を前記のような方法で染色し
、次いで別浴でセルロース繊維側を染色する。(11) Two-bath method First, the polyester fiber side is dyed by the method described above, and then the cellulose fiber side is dyed in a separate bath.

又は、この逆の順による。Or, in the reverse order.

一方、染色時間の短縮、染色工程の合理化、省エネルギ
ー等の観点からＴ／Ｃ混を同浴でしかも１回の染色工程
で染色を終える工夫（−浴一段法）がはかられるように
なってきた。On the other hand, from the viewpoints of shortening dyeing time, rationalizing the dyeing process, and saving energy, efforts have been made to use the T/C mixture in the same bath and finish dyeing in one dyeing process (-bath one-step method). Ta.

ところで、Ｔ／Ｃ混を反応性染料と分散染料でもって一
浴一段で高温法等により染色するにはいくつかの障害が
ある。例えば反応性染料の染色に必要な酸結合剤又は熱
等により酸結合剤を放出する物質は染浴中の分散染料を
凝集きせ７ζす、分解でせたすすることが多い。又、ポ
リエステル繊維側を染色する為の例えば、１３０℃のよ
うな高温下の水媒体中では反応性染料は酸結合剤等によ
り加水分解されてしまい、セルロース繊維に染着しなく
なる等である。By the way, there are several obstacles to dyeing T/C blends with reactive dyes and disperse dyes in one bath and one step using a high temperature method or the like. For example, acid binders necessary for dyeing with reactive dyes or substances that release acid binders by heat or the like often cause disperse dyes in the dye bath to coagulate or decompose. Furthermore, in an aqueous medium at a high temperature such as 130° C. for dyeing polyester fibers, reactive dyes are hydrolyzed by acid binders and the like, and do not dye cellulose fibers.

従ってＴ／Ｃ混を二浴一段で染色することを可能ならし
めるような反応性染料の開発が強く要望されている。Therefore, there is a strong demand for the development of a reactive dye that makes it possible to dye T/C mixtures in two baths in one step.

本発明者らは、このような要望を満たすべく鋭意研究を
重ねた結果、式（１）で表わされる化合物がＴ／Ｃ混の
一浴一段染色法に対して極めて高い適性を有することを
見い出し本発明に至ったものである。As a result of intensive research to meet these demands, the present inventors discovered that the compound represented by formula (1) has extremely high suitability for the T/C mixed one-bath one-step dyeing method. This led to the present invention.

本発明の化合物はＴ／Ｃ混の一浴一段染色法に高い適性
を示すばかりでなく、セルロース繊維の通常の浸染法、
捺染法、パッシング法等による染色に対しても十分適性
を有するものであるが、特筆すべきは、本発明の新規化
合物は酸結合剤、若しくは酸結合剤を放出する物質を使
用しないか、或いは染浴をｐＨ４〜１０特に５〜９に保
つに必要な緩衝作用を有する薬剤を共存させるだけで１
分散染料の存在下に１００〜１５０℃の染色温度でＴ／
Ｃ混を一浴一段で染色できる点である。本発明の化合物
を用いて分散染料と共にＴ／Ｃ混の一浴一段染色を行っ
た場合、分散染料の凝集や分散染料、反応性染料の分解
をおこすこともな（Ｔ／Ｃ混を均一に染色することがで
きる。本発明の化合物はセルロース繊維を黄色系の色相
に染色し、その染色物の湿潤堅牢度、塩素堅牢度、側光
堅牢度、汗日光堅牢度がすぐれている。The compound of the present invention not only shows high suitability for the T/C mixed one-bath one-stage dyeing method, but also shows high suitability for the conventional dyeing method for cellulose fibers.
Although it is sufficiently suitable for dyeing by printing methods, passing methods, etc., it is noteworthy that the novel compound of the present invention does not use an acid binder or a substance that releases an acid binder, or Simply coexisting with a buffering agent necessary to maintain the pH of the dye bath at 4 to 10, especially 5 to 9,
T/ at a dyeing temperature of 100-150°C in the presence of disperse dyes.
The advantage is that C blend can be dyed in one step in one bath. When the compound of the present invention is used for one-bath dyeing of a T/C mixture with a disperse dye, there is no aggregation of the disperse dye or decomposition of the disperse dye or reactive dye (the T/C mixture is uniformly dyed). The compound of the present invention dyes cellulose fibers in a yellow hue, and the dyed product has excellent wet fastness, chlorine fastness, side light fastness, and sweat/sunlight fastness.

本発明の化合物は木綿、４」］生ビスコース繊維、麻等
のセルロース繊維及びＴ／Ｃ混の染色に供した時最も顕
著な効果が得られるものであるが、その他、セルロース
縁組とトリアセテート繊維、ポリアクリルニトリル繊維
、変性ポリアクリル繊維、ポリアミド繊維、羊毛、絹等
との混合Ｍａ　１０材料の染色に適用し、セルロース繊
維側の染色を行ってもすぐれた効果が得らｉ″Ｌる。The compound of the present invention has the most remarkable effect when used for dyeing cotton, raw viscose fiber, cellulose fiber such as hemp, and T/C blend, but it can also be used for dyeing cellulose fiber and triacetate fiber. It can be applied to the dyeing of mixed Ma 10 materials with polyacrylonitrile fibers, modified polyacrylic fibers, polyamide fibers, wool, silk, etc., and excellent effects can be obtained even when dyeing the cellulose fiber side.

これらの場合には塩基性東側、カチオン染料、酸性染料
、酸性含金染料等を併用することにより異種の繊維から
なる繊維材料が均一に染色された染色物を得ることがで
きる。In these cases, by using basic dyes, cationic dyes, acidic dyes, acidic metal-containing dyes, etc. in combination, it is possible to obtain uniformly dyed textile materials made of different types of fibers.

本発明の式（１）で表わされる化合物は例えば次の方法
によって合成される。まず式（２）（式（２）において
ｎは前記と同じ意味を表わす）の化合物１モルを常法で
ジアゾ化し式（５）Ｙ （式（６）中Ｘ、Ｙは前記と同じ意味を表わす）の化合
物１モルにカップリングし式（４）の化合物を？（１１
次いで式（５） ２ 〔式（５）中ｚ２は、クロル原子又はフン素原子を表わ
す） の化合物１モルと水中で反応し、弐〇６）の化合物を得
る。The compound represented by formula (1) of the present invention is synthesized, for example, by the following method. First, 1 mole of the compound of formula (2) (in formula (2), n represents the same meaning as above) is diazotized by a conventional method, and the compound of formula (5)Y (in formula (6), X and Y have the same meaning as above) is diazotized. The compound of formula (4) is coupled to 1 mole of the compound of formula (4). (11
Then, it is reacted with 1 mol of a compound of formula (5) 2 [in formula (5), z2 represents a chlorine atom or a fluorine atom] in water to obtain a compound 206).

０．５モルを式（６）の化合物に反応せしめ式（７）の
化合ム２ を得、これにニコチン酸又はイソニコチン酸１モルを水
中で５０〜１００℃で反応せしめ、式（１）の化合物を
得る。0.5 mol was reacted with the compound of formula (6) to obtain compound 2 of formula (7), which was reacted with 1 mol of nicotinic acid or isonicotinic acid in water at 50 to 100°C to obtain the compound of formula (1). The compound is obtained.

反応液から目的物を得るには通常の塩析法、酸析法が用
いられるが、反応液をそのまま噴霧乾燥することもでき
る。To obtain the desired product from the reaction solution, ordinary salting-out methods and acid precipitation methods are used, but the reaction solution can also be spray-dried as it is.

次に式（１）の化合物を製造するにあ７’ｃって用いら
れる式（２）で表わされる化合物、式（３）で表わされ
る例をあげる、但しいずれも遊離酸の形で表わすものと
する。Next, examples of compounds represented by formula (2) and formula (3) used as 7'c in the production of compounds of formula (1) will be given, provided that both are expressed in the form of free acids. shall be.

式（２）で表わされる化合物： 式（３）で聚わされる化合物： Ｈ２Ｎ−ｃＨ２ｇＨ’ＣＨ２Ｎ１（２ ＯＯＨ ＣＲ３ Ｈ２Ｎ＜Ｃし０（◇−ＮＨ２Ｈ２Ｎ−（６）−”０２＜
ＣンＮＨ２次に、本発明の化合物によるセルロース繊維
及びセルロース含有繊維材料（混紡）の−Ｗ染色法につ
いてのべる。Compound represented by formula (2): Compound represented by formula (3): H2N-cH2gH'CH2N1(2 OOH CR3 H2N<C0(◇-NH2H2N-(6)-"02<
Next, the -W dyeing method of cellulose fibers and cellulose-containing fiber materials (blended fibers) using the compound of the present invention will be described.

本発明の化合物を用いてバッチ式浸染法でセルロース繊
維を染色する場合は、染浴を通常無機塩例えば硫酸ナト
リウム、又は塩化ナトリウムと本発明の化合物によって
仕立て、繊維を浸漬し、５０〜９０℃で１０〜６０分間
染色した後に、酸酸結合剤、例えば、炭酸水素ナトリウ
ム、炭酸ナトリウム、炭酸カリウム、水酸化ナトリウム
、水酸化カリウム、メタケイ酸ナトリウム、リン酸３ナ
トリウム、リン酸５カリウム、ピロリン酸ナトリウム、
ピロリン酸カリウム、トリクロル酢酸ナトリウムを単独
又は２種以上を混合して添加し、更に同温度で２０〜６
０分間染色をおこなう。When cellulose fibers are dyed by a batch dyeing process using the compounds of the present invention, the dyebath is usually prepared with an inorganic salt such as sodium sulfate or sodium chloride and the compound of the present invention, and the fibers are immersed at 50-90°C. After staining for 10-60 minutes with acid-acid binders such as sodium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium metasilicate, trisodium phosphate, pentapotassium phosphate, pyrophosphate. sodium,
Potassium pyrophosphate and sodium trichloroacetate were added alone or in a mixture of two or more, and the mixture was further heated for 20 to 60 minutes at the same temperature.
Perform staining for 0 minutes.

この場合酸結合剤は、最初から染浴中に加えてもよいし
又、中性で染色後に酸結合剤と無機塩を含む別浴で固着
をおこなうこともできる。In this case, the acid binder may be added to the dye bath from the beginning, or fixation may be carried out in a separate bath containing the acid binder and an inorganic salt after dyeing with neutrality.

又、本発明の化合物を用いて浸染法でＴ／Ｃ混を染色す
る場合には本発明の化合物及び分散染料と無機塩及び必
要に応じて染浴のｐＨ値を５〜９に保つ緩衝剤（例えば
、酢酸と酢酸ナトリウムの混合物、リン酸１カリウムと
リン酸２ナトリウムの混合物、リン酸１ナトリウムとリ
ン酸２ナトリウムの混合物）、界面活性剤、還元防止剤
等を使用して染浴を調製し、この染浴にＴ／Ｃ混を浸漬
し、１００〜１５０℃に加温し、２０〜９０分間染色を
おこなう。In addition, when dyeing a T/C mixture by the dip dyeing method using the compound of the present invention, the compound of the present invention, a disperse dye, an inorganic salt, and, if necessary, a buffer to maintain the pH value of the dye bath at 5 to 9. (For example, a mixture of acetic acid and sodium acetate, a mixture of monopotassium phosphate and disodium phosphate, a mixture of monosodium phosphate and disodium phosphate), a surfactant, a reduction inhibitor, etc. The T/C mixture is immersed in this dye bath, heated to 100 to 150°C, and dyed for 20 to 90 minutes.

又、１００％セルロース繊維の場合も前記同様に染色す
ることができる。Furthermore, 100% cellulose fibers can also be dyed in the same manner as described above.

本発明の化合物は分散染料の共存でＴ／Ｃ混を一浴一段
で染色することを可能にしたものであり、染色時間の短
縮、染色工程の合理化、省エネルギーの観点からその経
済効果が極めて大きい。The compound of the present invention makes it possible to dye T/C mixtures in one step in one bath by coexisting with a disperse dye, and its economic effects are extremely large in terms of shortening dyeing time, streamlining the dyeing process, and saving energy. .

次に実施例により本発明を具体的に説明する。Next, the present invention will be specifically explained with reference to Examples.

実施例中部は重量部で、スルホン酸基は遊離の形で表わ
す。The middle part of the examples is expressed in parts by weight, and the sulfonic acid group is expressed in free form.

実施例１ 式（８） で表わでれるクロルトリアジニル化合物８・６部を＊２
００部に：ａ解１−１これにニコチン酸２部、水酸化ナ
トリウム０・７部、水２部よりなる溶液を加えた。この
混合溶液を９０℃に加熱し、１０時間反応させた。Example 1 8.6 parts of chlortriazinyl compound represented by formula (8) *2
A solution consisting of 2 parts of nicotinic acid, 0.7 parts of sodium hydroxide, and 2 parts of water was added to 00 parts of solution 1-1. This mixed solution was heated to 90°C and reacted for 10 hours.

次いで食塩で塩析し、ｐ過、乾燥し１式（９）、式（１
０）で表わされるトリアジニル化合物（混合物λｍａＸ
　３９６　ｎｍ　（水中）１９部を得７ヒ。Next, salting out with common salt, p-filtration and drying yields formula 1 (9) and formula (1).
0) (mixture λmaX
396 nm (in water) 19 parts were obtained, 7 h.

’ｃｌ 高速液体クロマトグラフィー分析の結果（９）４８チ　
（１ａ）　４５．０％の混合物であった。'cl High performance liquid chromatography analysis results (9) 48
(1a) It was a 45.0% mixture.

尚、式（８）で表わでれる化合物は次のように製造した
。The compound represented by formula (8) was produced as follows.

２〜ナフチルアミン−４，８−ジスルホン酸１４．４部
水９０部にｐＨｌ、・５で溶解し、氷３［！部を加え、
次いで濃塩酸１”３部を加え戊。次いで亜硝酸ナトリウ
ム３．４部水５部よりなる溶液を加え１０’Ｃで１時間
ジアゾ化した。このジアゾニウム塩溶液を水１５０部、
３−アセチルアミノアニリン７・１部、ソーダ灰８部よ
りなる溶液へ、１０℃を保ち３゜分間で加えンヒ。2~Dissolve 14.4 parts of naphthylamine-4,8-disulfonic acid in 90 parts of water at a pH of .5, and add 3 [! add part,
Next, 1"3 parts of concentrated hydrochloric acid was added. Next, a solution consisting of 3.4 parts of sodium nitrite and 5 parts of water was added to diazotize at 10'C for 1 hour. This diazonium salt solution was mixed with 150 parts of water,
Add to a solution consisting of 7.1 parts of 3-acetylaminoaniline and 8 parts of soda ash over 3 minutes while maintaining the temperature at 10°C.

同温度で１時間反応せしめた。The reaction was continued at the same temperature for 1 hour.

次いでシアヌルクロライド８．１部を加え炭酸ナトリウ
ムを用いてｐＨ６，０〜６．５に保ちながら１０℃以下
で１時間反応させた。Next, 8.1 parts of cyanuric chloride was added, and the mixture was reacted for 1 hour at 10° C. or lower while maintaining the pH at 6.0 to 6.5 using sodium carbonate.

次いで、４，４′−ジアミノスチルベン−２，２′−ジ
スルホン酸７．６部を加え５０℃で２時間反応させた後
、食塩を加え塩析し、濾過、乾燥した。式（８）で表わ
される化合物３０部が得られた。Next, 7.6 parts of 4,4'-diaminostilbene-2,2'-disulfonic acid was added and reacted at 50°C for 2 hours, followed by salting out by adding common salt, filtering, and drying. 30 parts of a compound represented by formula (8) was obtained.

実施例２ 実施例１で得ら２″した化合物（混合物９２部、芒硝６
０部、リン酸２ナトリウム２部、リン酸１カリウム０．
５部、メタニトロベンゼンスルホン酸ナトリウム１部、
および水９３４．５部からなる染浴を調製した。この時
の染浴のｐＨ値は７であった。Example 2 The compound obtained in Example 1 (92 parts of mixture, 6 parts of Glauber's salt)
0 parts, disodium phosphate 2 parts, monopotassium phosphate 0.
5 parts, 1 part of sodium metanitrobenzenesulfonate,
and 934.5 parts of water. The pH value of the dye bath at this time was 7.

この染浴に精練漂白済みの無シルケット木綿メリヤス５
０部を入れ、攪拌しながら６０分間で１３０℃−１で昇
温し、その温度で６０分間染色した。Non-mercerized cotton stockinette that has been scoured and bleached in this dye bath 5
0 part was added, the temperature was raised to 130° C.-1 over 60 minutes while stirring, and dyeing was carried out at that temperature for 60 minutes.

染色後の染浴のｐＨ値は染色開始前と同様７であった。The pH value of the dye bath after dyeing was 7, the same as before the start of dyeing.

染色後水洗し、アニオン系界面活性剤２部を含む水浴液
１，０００部を用い１００℃で１０分間ソーピングし、
次いで水洗、乾燥して、黄色の染色物をイ！Ｉた。After dyeing, it was washed with water and soaped for 10 minutes at 100°C using 1,000 parts of a water bath solution containing 2 parts of anionic surfactant.
Next, wash with water, dry, and dye yellow! I was.

このものの湿潤堅牢度、塩素堅牢度、耐光堅牢度、汗日
光堅牢度がすぐれていた。This product had excellent wet fastness, chlorine fastness, light fastness, and sweat fastness to sunlight.

実施例６ 実施例１で得られた化合物（混合物）１部、カラーイン
デックスディスパースイエロー６４（］−５ｍ　、　芒
硝Ｂ　０部、メタニトロベンゼンスルホン酸ナトリウム
１部、ナフタリンスルホン酸のホルマリン縮金物（分散
剤）２部を含みリン酸２ナトリウム及びリン酸１カリウ
ムからなる緩衝剤でｐＨ７，０に調整された全容１００
０部の染浴にＴ／Ｃ（５０１５０）混紡布５０部を繰り
入れ２０分間で１５０℃迄昇温し、この温度で６０分間
染色した。Example 6 1 part of the compound (mixture) obtained in Example 1, Color Index Disperse Yellow 64(]-5m, 0 parts of Glauber's Salt B, 1 part of sodium metanitrobenzenesulfonate, formalin condensate of naphthalene sulfonic acid (dispersion) total volume 100, adjusted to pH 7.0 with a buffer consisting of disodium phosphate and monopotassium phosphate.
50 parts of T/C (50150) blended fabric was placed in a dye bath of 0 parts, heated to 150° C. over 20 minutes, and dyed at this temperature for 60 minutes.

水洗後、アニオン系界面活性剤２部、炭酸ナトリウム２
部を含む水１０００部中で１００℃で２０分間ソーピン
グし、次いで水洗、乾燥した。After washing with water, add 2 parts of anionic surfactant and 2 parts of sodium carbonate.
1000 parts of water at 100° C. for 20 minutes, then washed with water and dried.

ポリエステル繊維側、木綿側共に均一に黄色に染色され
た染色物が得られアヒ。A dyed product was obtained in which both the polyester fiber side and the cotton side were uniformly dyed yellow.

染色後の染浴に染料の凝集物、染料の分解生成物等の発
生は見られなかつンζ。No dye aggregates or dye decomposition products were observed in the dye bath after dyeing.

実施例４ 式（１１） で表わされるクロロトリアジニル化合物１２部を水３０
０部に溶解し、ニコチン酸４．５部を加えた。Example 4 12 parts of a chlorotriazinyl compound represented by formula (11) was mixed with 30 parts of water.
0 parts, and 4.5 parts of nicotinic acid was added.

次いで水酸化ナトリウムでｐＨ６，５にル嗣整したあと
９０℃に加熱し、同温度で種水酸化ナトリウム水溶液に
よりＩ）’Ｈ６，Ｏ〜６．５に保持しながら８時間反応
させた。次いで食塩で塩析し、濾過乾燥して次式（１２
）で表わされる化合物１３部を得た。After adjusting the pH to 6.5 with sodium hydroxide, the mixture was heated to 90° C. and reacted at the same temperature for 8 hours while maintaining I)'H6.0 to 6.5 with a seed sodium hydroxide aqueous solution. Next, it is salted out with common salt, filtered and dried to obtain the following formula (12
) was obtained.

（λｍａＸ、４４５　ｎｍ　（水中））尚、式（１１）
で表わされる化合物は次のようにして製造した。(λmax, 445 nm (in water)) Furthermore, formula (11)
The compound represented by was produced as follows.

次式（１６） で表わされるアミノアゾ化合物４９−５部’ｅ水ｉ、ｏ
ｏｏ部に溶解し、氷２００部を加えンヒ後、シアヌルク
ロライド１９部を加え、炭酸ナトリウムを用いて’ＰＨ
６，０〜６．５に保持しながら１０℃以下で１時間反応
させた。次いで、エチレンジアミン３部を加え炭酸ナト
リウムを用いてｐＨ５〜６に保持しながら５０℃で５時
間反応させンヒ。次いで食塩を加え塩析、濾過、乾燥し
た。Aminoazo compound represented by the following formula (16) 49-5 parts'e water i, o
After adding 200 parts of ice and cooling, 19 parts of cyanuric chloride was added and pH was adjusted using sodium carbonate.
The reaction was carried out for 1 hour at 10° C. or lower while maintaining the temperature at 6.0 to 6.5. Next, 3 parts of ethylenediamine was added, and the mixture was reacted at 50° C. for 5 hours while maintaining the pH at 5 to 6 using sodium carbonate. Next, salt was added, salted out, filtered, and dried.

式（１１）で表わされる化合物６５部が得られた。65 parts of a compound represented by formula (11) was obtained.

実施例５ 実施例４で得られた目的化合物１部、カラーインデック
ス　ディスパース　イエロー６４　０．ｓ部。Example 5 1 part of the target compound obtained in Example 4, Color Index Disperse Yellow 64 0. S part.

同ディスパースレッド６００．１部、芒硝６０部、メタ
ニトロベンゼンスルホン酸ナトリウム１部、ナフタリン
スルホン酸のホルマリン縮金物（分散剤）２部、テトロ
シンＫ（山川薬品製キャリヤー）５部を含み、実施例６
の緩衝剤でｐＨ７，０に調整されン勉全容＋、ｏｏｏ部
の染浴を作る。Ｔ／Ｃ（５０１５０）混メリヤス布５０
部を繰り入れ、１００℃に加熱し、同温度で６０分間染
色した。Example 6 Contains 600.1 parts of the same dispersion red, 60 parts of Glauber's salt, 1 part of sodium metanitrobenzenesulfonate, 2 parts of formalin condensed metal of naphthalene sulfonic acid (dispersant), and 5 parts of Tetrosin K (carrier manufactured by Yamakawa Pharmaceutical Co., Ltd.).
Adjust the pH to 7.0 with a buffer to make a dye bath. T/C (50150) blended knitted fabric 50
The sample was heated to 100°C and dyed at the same temperature for 60 minutes.

染色後、実施例５の方法で洗浄して、ポリエステル緻細
側、木綿側共に均一に黄金色に染色された染色物を得た
。After dyeing, it was washed by the method of Example 5 to obtain a dyed product in which both the fine polyester side and the cotton side were uniformly dyed in golden yellow.

この染色物は、湿潤堅牢度、耐光堅牢度、塩素堅牢度が
すぐれていた。This dyed product had excellent wet fastness, light fastness, and chlorine fastness.

実施例６ 式（１４） で表わ芒れるクロルトリアジニル化合物１０部を水３０
０部に溶解し、イソニコチン酸３部を加え７ζ。次いで
苛性ソーダでｐＨ６，５に訓読し８０℃に加熱した。同
温度で稲荷性ソーダ水溶液によりｐＨ６，０〜６．５に
保持しながら１５時間反応させ次。Example 6 10 parts of a chlortriazinyl compound represented by formula (14) was added to 30 parts of water.
0 parts and add 3 parts of isonicotinic acid to make 7ζ. Next, the pH was adjusted to 6.5 with caustic soda and heated to 80°C. The mixture was reacted for 15 hours at the same temperature while maintaining the pH at 6.0 to 6.5 with an aqueous Inari soda solution.

食塩で塩析し、濾過乾燥して式（１５）の化合物１２部
を得た。（入ｍａｘ　４ｔ　Ｏｎｍ　（水中））尚、式
（１４）の化合物は、実施例１．４に記載の方法に準じ
て製造しフ乞。Salting out with common salt, filtration and drying yielded 12 parts of the compound of formula (15). (Max 4t Onm (in water)) The compound of formula (14) was prepared according to the method described in Example 1.4.

実施例７ 実施例６で得られに目的化合物２部、芒硝８０部、水１
０００部を用いて染浴を調製し、との染浴に５０部の木
綿メリヤスを浸漬し、８０℃で５０分間染色した後、炭
酸ナトリウム２０部を添加し、引き続き同温度で６０分
間染色した。実施例２と同様にソーピングし、乾燥して
黄色の染色物が得られた。Example 7 2 parts of the target compound obtained in Example 6, 80 parts of Glauber's salt, 1 part of water
000 parts was used to prepare a dye bath, 50 parts of cotton stockinette was immersed in the dye bath, and dyed at 80°C for 50 minutes, then 20 parts of sodium carbonate was added and dyed at the same temperature for 60 minutes. . A yellow dyed product was obtained by soaping and drying in the same manner as in Example 2.

このものの湿潤堅牢度、４光堅牢度、塩素堅牢度がすぐ
れていた。This product had excellent wet fastness, four-light fastness, and chlorine fastness.

実施例８ 式（１６） で表わされるフロロトリアジニル染料１０部を水３００
部に溶解し、ニコチン酸３部を加え、次いで水酸化ナト
リウムを加えｐＨ６，５とレア’ｔ−０この溶液を６０
℃に加熱し、同温度で稀炭酸ナトリウム水溶液を加えて
ｐｌ（６，０〜６．５に保ちながら１０時間反応させた
。Example 8 10 parts of fluorotriazinyl dye represented by formula (16) was added to 300 parts of water.
1 part, add 3 parts of nicotinic acid, then add sodium hydroxide to pH 6.5 and raise this solution to 60%.
The mixture was heated to .degree. C., and a dilute aqueous sodium carbonate solution was added at the same temperature, and the mixture was reacted for 10 hours while maintaining the pl (pl) at 6.0 to 6.5.

食塩で塩析し濾過乾燥して 式（１７）及び（１８）で表わされるトリアジニル化合
物（混合物）１０部が得られ尼。（λｍａｘ　４５５　
ｎｍ（水中））高速液体クロマトグラフィー分析の結果
（１７）６８％（４８）　２３％の混合物であった。Salting out with common salt, filtration and drying yielded 10 parts of triazinyl compounds (mixture) represented by formulas (17) and (18). (λmax 455
As a result of high performance liquid chromatography analysis (nm (in water)), it was a mixture of (17) 68% (48) 23%.

実施例９ 実施例１で得られた化合物（混合物）１部、カラーイン
デックスディスパースイエロー６４０．５部、芒硝８０
部及び水から全治１０００部の染浴を調製した。そのｐ
Ｈ値は６・７であった。この染浴にＴ／Ｃ（ｓｏ／ｓ［
ｉ□）混紡布５０部を繰り入れ２０分間で１３０℃迄昇
温しこの温度で６０分間染色した。染色終了後の残浴の
ｐＨ値は５．８であつン１゜染色後実施例３と同様にソ
ーピングしポリエステル繊維側、木綿側共に均一に黄色
に染色されンヒ染色物が得られた。Example 9 1 part of the compound (mixture) obtained in Example 1, 640.5 parts of Color Index Disperse Yellow, 80 parts of Glauber's Salt
A dye bath of 1000 parts was prepared from 1000 parts and water. That p
The H value was 6.7. T/C(so/s[
i□) 50 parts of the blended fabric was introduced, heated to 130° C. over 20 minutes, and dyed at this temperature for 60 minutes. The pH value of the remaining bath after dyeing was 5.8, and after dyeing at 1°, soaping was carried out in the same manner as in Example 3, and both the polyester fiber side and the cotton side were uniformly dyed yellow, yielding a dyed product.

実施例１０〜４２ 実施例１．４．６．８　に準じて、化合物を製造し木綿
の染色を行った。Examples 10-42 According to Example 1.4.6.8, compounds were produced and cotton was dyed.

次表に式（２）で表わされる化合物、式（３）で表わさ
リジン核におけるカルボキシル基の結合位置、化合物の
λｍａｗ　（水中）及び製造した化合物で木綿を染色し
た時の色相を示した。The following table shows the compound represented by formula (2), the bonding position of the carboxyl group in the lysine nucleus represented by formula (3), the λmaw (in water) of the compound, and the hue when cotton was dyed with the produced compound.

手続・補正−１１１ 昭和５９年５月１０日 特、＋・１庁長官若杉和夫殿 １、　！ＩＴ件の表示 昭和５８年特許願第１９４３５６号 ２発明の名称 アゾ化合物及びそれを用いる繊維拐料の染色法３　補正
をする渚 事件との関係　特許出願人 東京都千代田区富士見−Ｆ目１１番２号（４０８）　日
本化薬株式会社 代表者　取締役社長　坂　野　′帛　和４代理人 東京都千代口］区富士見−丁口１１番２号（自　発） ６　補正により増加する発明の数 な　し ７　補ｉＥの対象 明細書の発明の詳細な説明の欄。Proceedings/Amendment-111 May 10, 1980 Special, +1 Office Commissioner Kazuo Wakasugi 1, ! Indication of IT matter Patent application No. 194356 of 1982 2 Name of the invention Azo compound and method for dyeing fiber additives using the same 3 Relationship with the Nagisa case to be amended Patent applicant No. 11 F, Fujimi, Chiyoda-ku, Tokyo No. 2 (408) Nippon Kayaku Co., Ltd. Representative Director and President Mr. Sakano Wa 4 Agent 11-2 Fujimi-Chome, Chiyoguchi, Tokyo (Voluntary) 6 No increase in the number of inventions due to amendment 7. Detailed description of the invention in the subject specification of Supplement iE.

８補正の内容 別紙の通り8. Contents of amendment As per attached sheet

Claims (2)

【特許請求の範囲】[Claims] （１）　遊離酸の形で式（１） （式（１）中Ｘは水素原子、メチル基、メトキシ基又は
２−メトキシエトキシ基を、Ｙは水素原子、メチル基、
メトキシ基、アセチルアミノ基又はウレイド基を、Ｒ１
・Ｒ２は各々独立して水素原子又はメチル基を、ｎは２
又は３の数を１．２は素原子を、Ｂは−（ＣＨ２）ｍ〜
（ｍは２又は５を宍わす）シ基、スルホン酸基、カルボ
ン酸基又はクロル原子で置換されていてもよいｐ−フェ
ニレンジアミン残基又はｍ−フェニレンジアミン残基：
核のカルボキシル基は６−又は４−位に結合しているも
のとする。） で表わされる水溶性アゾ化合物。(1) Formula (1) in the form of a free acid (In formula (1), X is a hydrogen atom, a methyl group, a methoxy group, or a 2-methoxyethoxy group, and Y is a hydrogen atom, a methyl group,
methoxy group, acetylamino group or ureido group, R1
・R2 each independently represents a hydrogen atom or a methyl group, and n represents 2
Or the number of 3 is 1.2 is an elementary atom, B is -(CH2)m ~
(m represents 2 or 5) p-phenylenediamine residue or m-phenylenediamine residue optionally substituted with a cy group, sulfonic acid group, carboxylic acid group, or chlorine atom:
It is assumed that the carboxyl group of the nucleus is bonded to the 6- or 4-position. ) A water-soluble azo compound represented by （２）　遊離酸の形で式（１） 乞 （式（１）中Ｘは水素原子、メチル基、メトキシ基又は
２−メトキシエトキシ基を、Ｙは水素原子、メチル基、
メトキシ基、アセチルアミノ基又はウレイド基を、Ｒ１
１Ｒ２は各々独立して水素原子又はメチル基を、ｎは２
又は５の数を、ｚｌは基台しているものとする）、クロ
ル原子又はフッ素原子を、Ｂは−（ＣＨ２）ｍ−（ｍは
２又は３を表わす）キシ基、スルホン酸基、カルボン酸
基又はクロル原子で置換されていてもよいｐ−フェニレ
ンジアミン残基又はｍ−フェニレンジアミン残基；核の
カルボキシル基は３−又は４−位に結合しているものと
する。） で表わされる水溶性アゾ化合物を用いることを特徴とす
るセルロース又はセルロース含有繊維材料の染色法。(2) Formula (1) in the form of a free acid (in formula (1), X is a hydrogen atom, a methyl group, a methoxy group, or a 2-methoxyethoxy group, and Y is a hydrogen atom, a methyl group,
methoxy group, acetylamino group or ureido group, R1
1R2 each independently represents a hydrogen atom or a methyl group, n is 2
or the number of 5, zl is a chlorine atom or a fluorine atom, B is -(CH2)m- (m represents 2 or 3) an xy group, a sulfonic acid group, a carboxyl group A p-phenylenediamine residue or m-phenylenediamine residue which may be substituted with an acid group or a chlorine atom; the carboxyl group of the nucleus is bonded to the 3- or 4-position. ) A method for dyeing cellulose or cellulose-containing fibrous materials, characterized by using a water-soluble azo compound represented by: