JPS6037145B2 - Monoazo compound and method for dyeing hydrophobic fibers using it - Google Patents

Description

【発明の詳細な説明】 本発明は式 （｛１｝式中Ｒは炭素数１から４のアルキル基を意味す
る）で表わされるモノアゾ化合物及びそれを用いる疎水
性繊維の染色法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a monoazo compound represented by the formula ({1} in which R means an alkyl group having 1 to 4 carbon atoms) and a method for dyeing hydrophobic fibers using the monoazo compound.

近年疎水性繊維とりわけポリエステル繊維は、その染色
物の付加価値をたかめるべく、従来の無地染色だけでな
く、複雑又は縞簾細な模様柄のえられる捺染又は防抜染
による染色方式が多くなってきた。In recent years, in order to increase the added value of hydrophobic fibers, especially polyester fibers, in addition to the conventional plain dyeing, there has been an increase in the number of dyeing methods using printing or resist discharge printing, which can produce complex or striped patterns. .

このうち捺染による方法においては従来の無地梁に用い
られていた染料を用いても十分満足すべき結果がえられ
るが、防抜染による方法においては抜染剤によって染料
母体の一部又は骨格が分解されポリエステル繊維に染着
を示さなくなるような構造であることが要求される。さ
らに得られた抜染物が満足な実用性を有するためには充
分な諸堅牢度を示すことが必要である。防抜染のされや
すさ則ち抜染性と堅牢度との間には相反する面があり、
良好な抜染性をもち、かつ種々の堅牢度が良好な染料を
作り出す事は非常に困難であった。例えば特公昭４３一
鼠５６号に記載の染料は抜染性はすぐれているが昇華堅
牢度及び染色物の湿潤堅牢度が十分でない。Among these methods, in the printing method, a sufficiently satisfactory result can be obtained even if the dye used for conventional plain beams is used, but in the method of resist discharge printing, a part or skeleton of the dye matrix is decomposed by the discharge agent. It is required that the structure is such that the polyester fibers do not show dyeing. Furthermore, in order for the obtained discharge prints to have satisfactory practicality, it is necessary that they exhibit sufficient fastness properties. There is a conflict between ease of discharge printing, discharge printing performance, and fastness.
It has been extremely difficult to create dyes that have good discharge properties and various fastnesses. For example, the dye described in Japanese Patent Publication No. 1973-1-56 has excellent discharge printing properties, but the sublimation fastness and the wet fastness of dyed products are insufficient.

又特開昭５７−４９６６１号の染料は抜染性及び昇華堅
牢度はすぐれているが染色物の湿潤堅牢度が十分でない
。又両者ともに染料の熱分解性が不良である。そこで本
発明者らは良好な抜染性と十分な諸堅牢度を兼ね具えた
染料を開発すべ〈鋭意研究した結果式‘１１で表わされ
るモノアゾ化合物（染料）が抜染性、諸堅牢度において
きわめて良好な性質を有する染料である事を見出し、本
発明を完成した。表ｍに示す通り本発明の染料は公知の
染料に比べて殊に水堅牢度、熱分解性がはるかにすぐれ
ていることは明白である。Furthermore, although the dye disclosed in JP-A-57-49661 has excellent discharge printability and sublimation fastness, the wet fastness of the dyed product is not sufficient. In addition, both dyes have poor thermal decomposition properties. Therefore, the inventors of the present invention should develop a dye that has both good dischargeability and sufficient various fastnesses.As a result of intensive research, the monoazo compound (dye) represented by formula '11 has been found to have extremely good dischargeability and various fastnesses. They discovered that it is a dye with unique properties, and completed the present invention. As shown in Table m, it is clear that the dyes of the present invention are far superior in water fastness and thermal decomposition properties, especially compared to known dyes.

・−・１ 縦 ＊１ 特公昭４３−５４５６号の染料 ＊２ 侍閥昭５７−４９６６１号の染料 ＊３ 炭酸ナトリウムを抜染剤に用いた場合の抜染部分
の白度の視感判定◎ 白度良好 ○ 白度不十分 ＊４ 後加工処理後の水堅牢度（絹の汚染度で判定）１
級 （不良） ど ５級 （良好） ＊５ 染料液を１３ぴ○で６０分前処理したのちのポリ
エステル繊維への染着性で判定。・-・1 Vertical *1 Dye of Special Publication No. 43-5456 *2 Dye of Samurai No. 57-49661 *3 Visual judgment of whiteness of discharged area when sodium carbonate is used as discharge printing agent ◎ Whiteness Good ○ Insufficient whiteness *4 Water fastness after post-processing (determined by degree of silk contamination) 1
Grade (Poor) Grade 5 (Good) *5 Judged by dyeing property on polyester fibers after pre-treating the dye solution at 13 P○ for 60 minutes.

×× 不良 ◎ 非常に優れる 本発明の式‘１１で示されるモノアゾ染料はＰ−アミノ
安息香酸フェノキシェチルェステルを塩酸、硫酸等の鍵
酸中で亜硝酸ソーダでジアゾニウム塩となし次いで式（
式中Ｒは前記と同じ意味を表わす） で示される化合物とアルカリ媒体中でカップリングする
ことによって容易にえられる。× × Poor ◎ The very excellent monoazo dye represented by the formula '11 of the present invention is obtained by converting P-aminobenzoic acid phenoxychetyl ester into a diazonium salt with sodium nitrite in a key acid such as hydrochloric acid or sulfuric acid, and then converting it into a diazonium salt of the formula (
(wherein R represents the same meaning as above) can be easily obtained by coupling with a compound represented by the following formula in an alkaline medium.

本発明の染料により染色しうる疎水性繊維材料としては
ポリアミド繊維、アセテート繊維、ポリエステル繊維等
があげられるがポリエステル繊維に使用した場合特にす
ぐれた結果が得られるものである。Hydrophobic fiber materials that can be dyed with the dye of the present invention include polyamide fibers, acetate fibers, polyester fibers, etc., and particularly excellent results can be obtained when used with polyester fibers.

なお染色にあたっては式○ーで示される染料を単独に又
は任意の割合に混合して用いることも出来る。次に染色
方法について説明する。For dyeing, dyes represented by the formula ○- can be used alone or in combination in any proportion. Next, the dyeing method will be explained.

式【１｝で示されるモノアゾ化合物をナフタレンスルホ
ン酸のホルマリン縮合物、リグニンスルホン酸等のァニ
オン性分敵剤又はアルキルアミンのエチレンオキサイド
付加物、アルキルフェノールのエチレンオキサィド付加
物等の非イオン性分散剤の存在下少量の水で溜債機又は
サンドミルで充分粉砕し必要に応じてペースト状である
いは乾燥して粉末状で使用に供される。The monoazo compound represented by the formula [1} can be used as an anionic dividing agent such as a formalin condensate of naphthalenesulfonic acid, ligninsulfonic acid, or a nonionic agent such as an ethylene oxide adduct of an alkylamine or an ethylene oxide adduct of an alkylphenol. It is thoroughly ground in a distiller or sand mill with a small amount of water in the presence of a dispersant, and is used as a paste or dried as a powder, if necessary.

実際の染色にあたっては例えば次のようなそれ自体公知
の方法が採用される。For the actual dyeing, for example, the following method known per se is employed.

‘１｝ 高温染色法 水媒体中で加圧下１２０〜１４０℃で染色を行う。‘1} High temperature dyeing method Dyeing is carried out in an aqueous medium under pressure at 120-140°C.

｛２１ キヤリャ−染色法メチルナフタレン、モノクロ
ルベンゼン等の勤剤の存在下で水媒体中１００℃で染色
を行う。{21 Carrier dyeing method Dyeing is carried out at 100°C in an aqueous medium in the presence of a dye such as methylnaphthalene or monochlorobenzene.

｛３｝ サーモゾル染色法粉砕染料を含む液に布をパッ
ディングし次いで中間乾燥し引き続き乾燥処理を施す。{3} Thermosol dyeing method Cloth is padded in a liquid containing pulverized dye, then intermediately dried and then subjected to drying treatment.

‘４１ 捺染法 粉砕染料及びその他の薬剤からなる捺染糊を印捺し引き
続きＨＴスチーミング又はＨＰスチーミングを行う。'41 Printing method A printing paste consisting of a pulverized dye and other chemicals is printed, followed by HT steaming or HP steaming.

‘５）抜染法 前記‘１’又は‘２｝によってえられた染色布に塩化第
１錫等を含有する抜染剤を所望の模様に印捺し次いでＨ
Ｔスチーミング又はＨＰスチーミングを行う。'5) Discharge printing method A discharge printing agent containing stannous chloride etc. is printed on the dyed cloth obtained in the above '1' or '2} in a desired pattern, and then H
Perform T steaming or HP steaming.

■ 防抜染法 塩化第１錫又は炭酸ナトリウム、炭酸カリウムのような
防染剤を含んだ糊剤をあらかじめ所望の模様に印捺して
おき次いで粉砕染料を含んだ色糊を印捺して、ＨＴスチ
ーミング又はＨＰスチーミングを行う。■ Anti-discharge printing method A paste containing a resist dye such as tin chloride, sodium carbonate, or potassium carbonate is printed in advance in the desired pattern, and then a color paste containing a pulverized dye is printed. Perform teaming or HP steaming.

これらの方法は最も代表的な例をあげたものであり、本
発明の適用法はこれらの方法に限定されるものではない
。These methods are the most typical examples, and the application of the present invention is not limited to these methods.

本発明によってえられる染色物はいずれも黄色の色相で
あり、その堅牢度は耐光、昇華堅牢度等にすぐれ殊に後
加工処理又はヒートセット後の湿潤堅牢度が非常に良好
である。以下に実施例をあげて本発明を具体的に説明す
る。例中「部」及び「％」はそれぞれ重量部及び重量％
である。実施例 １ 濃塩酸５２部、氷水１５碇部よりなる溶液にＰ−アミ／
安息香酸フェノキシェチルェステル２５．技都を加え５
℃以下にて亜硝酸ソーダ７．２部を３の都の水に溶解し
た溶液を加えた。All of the dyed products obtained by the present invention have a yellow hue, and their fastness is excellent in light fastness, sublimation fastness, etc., and in particular, very good wet fastness after post-processing or heat setting. The present invention will be specifically explained below with reference to Examples. In the examples, "parts" and "%" are parts by weight and % by weight, respectively.
It is. Example 1 P-Ami/
Benzoic acid phenoxychetyl ester 25. Add Gito 5
A solution prepared by dissolving 7.2 parts of sodium nitrite in 3 miyako water was added at a temperature below .degree.

約２時間損枠後過剰の亜硝酸イオンをスルフアミン酸に
よって除去しジアゾ液を得た。炭酸ナトリウム４２部を
３０碇都の水に溶解した溶液に１ーフェニル−３ーカル
ボェトキシピラゾロン２３．森部を溶解し１０二０以下
で前記のジアゾ液を燈梓下徐々に滴下した。After about 2 hours of loss, excess nitrite ions were removed with sulfamic acid to obtain a diazo solution. Add 23.1-phenyl-3-carbethoxypyrazolone to a solution of 42 parts of sodium carbonate dissolved in 30 parts of water. Moribe was dissolved and the above diazo solution was gradually added dropwise to the solution at a temperature of 1020 ml or less.

えられた結晶を炉別し乾燥して次の式で示されるモノア
ゾ化合物４＄部を得た。The obtained crystals were separated in a furnace and dried to obtain 4 parts of a monoazo compound represented by the following formula.

（理論量の９８％）このものをジオキサンから再結晶し
たものの入ｍａｘは４１仇血（アセトン溶液）であった
。又融点は１６９．５〜１７１．５ｑ○であった。実施
例 ２ 炭酸ナトリウム４２都を３０の郭の水に溶解した溶※液
に１−フェニル−３ーカルボブトキシピラゾロン２６部
を溶解し１び０以下で実施例１と同様にして得られたジ
アゾ液を蝿梓下徐々に滴下した。(98% of the theoretical amount) When this product was recrystallized from dioxane, the maximum content was 41 kg (acetone solution). Moreover, the melting point was 169.5-171.5q○. Example 2 Diazo was obtained in the same manner as in Example 1 by dissolving 26 parts of 1-phenyl-3-carbobutoxypyrazolone in a solution of 42 parts of sodium carbonate dissolved in 30 parts of water. The solution was gradually dropped into the flask.

えられた結晶を炉別し乾裸して次の式で示されるモノア
ゾ化合物５１．技部を得た。（理論量の聡％）このもの
をジオキサンから再結晶したものの入ｍａｘは４１仇ｍ
（アセトン溶液）であった。又融点は１４０．０〜１４
２．５００であった。実施例 ３実施例１でえられた式
｛３丁のモノアゾ化合物３部をデモールＮ（花王アトラ
ス社製、陰イオン分散剤）４部とデモールＣ（同）３部
とで湿潤状態にて５時間階濃処理した後乾燥して微粒子
化染料をえた。The obtained crystals were separated by furnace and dried to form a monoazo compound 51. Got the technical department. (Satoshi% of the theoretical amount) The maximum content of this product recrystallized from dioxane is 41 m
(acetone solution). Also, the melting point is 140.0-14
It was 2.500. Example 3 3 parts of the monoazo compound of formula {3 parts obtained in Example 1 was mixed with 4 parts of Demol N (manufactured by Kao Atlas Co., Ltd., an anionic dispersant) and 3 parts of Demol C (same) in a wet state. After being concentrated for several hours, it was dried to obtain a finely divided dye.

この微粒子化染料０．１部を１０碇部の水に分散せしめ
酢酸でｐＨ５に調整した後ポリエステル繊維製布５部を
加え１３０ｑｏに６０分保ったあと取り出し水洗し次い
で水１，０００部中にカセィソーダ２部、ハイドロサル
フアィト２部、モノゲン（第一工業薬品製）１部を溶か
した液１００部で８０ｑ０１５分間処理した。水洗、乾
燥後黄色の染色物をえた。このものは昇華堅牢度、耐光
堅牢度にすぐれ殊に帯電防止加工又はヒートセットを施
した後の水堅牢度、マサッ堅牢度がすぐれていた。実施
例 ４ 実施例２でえられた式｛４’のモノアゾ化合物を用いて
実施例３とほぼ同様に処理して微粒子化染料をえた。Disperse 0.1 part of this micronized dye in 10 parts of water, adjust the pH to 5 with acetic acid, add 5 parts of polyester fiber cloth, keep it at 130 qo for 60 minutes, take it out, wash it with water, and then add it to 1,000 parts of water. The sample was treated with 100 parts of a solution containing 2 parts of caustic soda, 2 parts of hydrosulfite, and 1 part of Monogen (manufactured by Daiichi Kogyo Yakuhin) for 80 minutes. After washing with water and drying, a yellow dyed product was obtained. This product had excellent sublimation fastness and light fastness, and especially excellent water fastness and mass fastness after antistatic processing or heat setting. Example 4 The monoazo compound of formula {4' obtained in Example 2 was treated in substantially the same manner as in Example 3 to obtain a finely divided dye.

次いで上記微粒子化染料 １０．の郭カルポキシ
メチルセルローズ系糊剤 ６０．碇部塩素酸ソーダ
０．５部酒 石 酸
０．郷均 梁 剤
２，郷湯 ２５．岱部
の組成からなる色糊を調整した。この色糊をポリエステ
ル繊維上に印捺し８０℃において乾燥を行った後１７０
ｑｏの過熱蒸気中で５分間保持し次いで水洗し還元洗浄
、水洗、乾燥を行った。色糊を印捺した部分が黄色に発
色した染色物をえた。この染色物の諸堅牢度がすぐれて
いた。実施例 ５ 塩化第１錫１碇部、芳香族キャＩＪャー１碇都、ローカ
ストビーンガム（安達糊料製）１２％水溶液６０部、水
２碇部よりなる抜染剤をポリエステル繊維布上に印捺し
１００００で５分間乾燥した。Next, the above-mentioned finely divided dye 10. Carpoxymethylcellulose adhesive 60. Ikaribe Sodium Chlorate
0.5 part alcoholic acid
0. Go Hitoshi Liangjia
2. Local hot springs 25. We adjusted the color paste consisting of the composition of the part. After printing this color paste on polyester fiber and drying it at 80℃,
The sample was kept in superheated steam at qo for 5 minutes, and then washed with water, followed by reduction washing, washing with water, and drying. A dyed product was obtained in which the area printed with colored paste turned yellow. This dyed product had excellent various fastnesses. Example 5 A discharge printing agent consisting of 1 part of stannous chloride, 1 part of aromatic carrier IJ, 60 parts of a 12% aqueous solution of locust bean gum (manufactured by Adachi Paste Co., Ltd.), and 2 parts of water was printed on a polyester fiber cloth. It was printed and dried at 10,000 for 5 minutes.

次いで実施例３でえられた微粒子化染料 ３．碇
都６０‐〇部（富士化学製） よりなる水性糊剤 酒 石 酸 ０．５部塩素
酸ソーダ ０．５部水
３６．の郭の組成よりなる
色糊をこの乾燥した布にオーバープリントした。Next, the micronized dye obtained in Example 3 3. Ikarito 60-〇 parts (manufactured by Fuji Chemical) Water-based thickening liquor consisting of stone acid 0.5 parts sodium chlorate 0.5 parts water
36. This dried cloth was overprinted with a colored paste of the following composition.

次いで乾燥処理後１７０ｑｏで５分間過熱蒸気によるス
チーミングを行った。次いで水洗し還元洗浄することに
より抜染糊印捺部分の白度がすぐれた黄色の染色物がえ
られた。Next, after the drying process, steaming using superheated steam was performed at 170 qo for 5 minutes. Then, by washing with water and reduction washing, a yellow dyed product with excellent whiteness in the area where the discharge paste stamp was printed was obtained.

実施例 ６ 炭酸ナトリウム ５部グリセリン
１礎部ソルビトーゼＣ−
５ ５％スノーアルギンＳＳＬ６％ よりなる水性糊剤 ５５部水
３礎部の組成よりなる
アルカリ防梁糊をテトロン布に印捺し中間乾燥後実施例
５で用いたのと同じ色糊をオーバープリントした。Example 6 Sodium carbonate 5 parts glycerin
1 cornerstone sorbitose C-
5 Aqueous glue consisting of 5% Snow Algin SSL 6% 55 parts water
An alkaline beam-proofing paste having the composition of the base part 3 was printed on Tetron cloth, and after intermediate drying, the same colored paste as used in Example 5 was overprinted.

Claims (1)

【特許請求の範囲】 １ 式 ▲数式、化学式、表等があります▼ （式中Ｒは炭素数１から４のアルキル基を意味する）
で表わされるモノアゾ化合物。 ２ 式 ▲数式、化学式、表等があります▼ （式中Ｒは炭素数１から４のアルキル基を意味する）
で表わされるモノアゾ化合物を用いることを特徴とする
疎水性繊維の染色法。[Claims] 1 Formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R means an alkyl group having 1 to 4 carbon atoms)
A monoazo compound represented by 2 Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R means an alkyl group with 1 to 4 carbon atoms)
A method for dyeing hydrophobic fibers, characterized by using a monoazo compound represented by