JPS6086168A - Azo compound and dyeing of fiber material using the same - Google Patents
Azo compound and dyeing of fiber material using the sameInfo
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- JPS6086168A JPS6086168A JP19435683A JP19435683A JPS6086168A JP S6086168 A JPS6086168 A JP S6086168A JP 19435683 A JP19435683 A JP 19435683A JP 19435683 A JP19435683 A JP 19435683A JP S6086168 A JPS6086168 A JP S6086168A
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Abstract
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)
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−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:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP19435683A JPS6086168A (en) | 1983-10-19 | 1983-10-19 | Azo compound and dyeing of fiber material using the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP19435683A JPS6086168A (en) | 1983-10-19 | 1983-10-19 | Azo compound and dyeing of fiber material using the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6086168A true JPS6086168A (en) | 1985-05-15 |
JPH0420948B2 JPH0420948B2 (en) | 1992-04-07 |
Family
ID=16323215
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP19435683A Granted JPS6086168A (en) | 1983-10-19 | 1983-10-19 | Azo compound and dyeing of fiber material using the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6086168A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0818513A1 (en) * | 1996-07-10 | 1998-01-14 | Zeneca Limited | Reactive dyes, their preparation and use |
US7172631B2 (en) | 2001-06-12 | 2007-02-06 | L'oreal S.A. | Dyeing composition for human keratinous fibers with oxidation dyes and dicationic compounds |
CN102286217A (en) * | 2011-06-29 | 2011-12-21 | 天津德凯化工股份有限公司 | Yellow active dye for hair and preparation method thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5126386A (en) * | 1974-08-24 | 1976-03-04 | Mitsubishi Chem Ind | Seruroosukeisenino senshokuhoho |
JPS564784A (en) * | 1979-06-18 | 1981-01-19 | Ici Ltd | Dyeing of cellulose or wool fiber material |
-
1983
- 1983-10-19 JP JP19435683A patent/JPS6086168A/en active Granted
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5126386A (en) * | 1974-08-24 | 1976-03-04 | Mitsubishi Chem Ind | Seruroosukeisenino senshokuhoho |
JPS564784A (en) * | 1979-06-18 | 1981-01-19 | Ici Ltd | Dyeing of cellulose or wool fiber material |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0818513A1 (en) * | 1996-07-10 | 1998-01-14 | Zeneca Limited | Reactive dyes, their preparation and use |
US7172631B2 (en) | 2001-06-12 | 2007-02-06 | L'oreal S.A. | Dyeing composition for human keratinous fibers with oxidation dyes and dicationic compounds |
CN102286217A (en) * | 2011-06-29 | 2011-12-21 | 天津德凯化工股份有限公司 | Yellow active dye for hair and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
JPH0420948B2 (en) | 1992-04-07 |
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