JPH07108956B2 - Water-soluble monoazo dye and dyeing method using the same - Google Patents
Water-soluble monoazo dye and dyeing method using the sameInfo
- Publication number
- JPH07108956B2 JPH07108956B2 JP5149006A JP14900693A JPH07108956B2 JP H07108956 B2 JPH07108956 B2 JP H07108956B2 JP 5149006 A JP5149006 A JP 5149006A JP 14900693 A JP14900693 A JP 14900693A JP H07108956 B2 JPH07108956 B2 JP H07108956B2
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- JP
- Japan
- Prior art keywords
- dyeing
- group
- dye
- water
- dyeing method
- Prior art date
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- Expired - Fee Related
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Description
【０００１】[0001]
【産業上の利用分野】本発明は新規な構造を有する赤色
系の水溶性モノアゾ色素およびそれを用いた染色方法に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a red water-soluble monoazo dye having a novel structure and a dyeing method using the same.
【０００２】[0002]
【従来の技術】セルロースまたは含窒素繊維類を水溶性
の反応性染料を用いて染色する方法は古くから実施され
ており、種々の反応性染料が提案されている。その代表
的なものとして、例えばビニルスルホン型反応基を有す
るものが知られているが、このタイプの染料は一般的に
反応染着率は良好であるものの、耐塩素堅牢度（水道水
中の塩素による退色）に問題があり、さらに、浸染法で
染色する際に濃厚な被染物を得るためには、芒硝、食塩
等の電解質を染色浴１リットル当り５０〜１００ｇと多
量に用いる必要があった。このように多量の電解質を用
いると、染色廃水の処理にも影響を及ぼし、染色コスト
を増大させる結果となる。2. Description of the Related Art A method for dyeing cellulose or nitrogen-containing fibers with a water-soluble reactive dye has been practiced for a long time, and various reactive dyes have been proposed. As a typical one, for example, one having a vinyl sulfone type reactive group is known. Although this type of dye generally has a good reaction dyeing ratio, it has a high chlorine fastness (chlorine in tap water). In addition, it was necessary to use a large amount of electrolyte such as Glauber's salt and salt in an amount of 50 to 100 g per 1 liter of the dyeing bath in order to obtain a thick dyeing object when dyeing by the dip dyeing method. . The use of such a large amount of electrolyte also affects the treatment of dyeing wastewater, resulting in an increase in dyeing cost.
【０００３】例えば、特公昭３９−１８１８４号の実施
例４に挙げられた下記構造式で示される染料は、ビニル
スルホン基がトリアジン環を介して色素母体に結合して
いるため、耐塩素堅牢度はかなり向上しているが、浸染
染色時の電解質の使用量は５０ｇ／ｌ以上必要である。For example, the dye represented by the following structural formula, which is described in Example 4 of JP-B-39-18184, has a chlorine sulfone fastness because the vinyl sulfone group is bonded to the dye base through the triazine ring. Is considerably improved, but the amount of electrolyte used at the time of dip dyeing must be 50 g / l or more.
【０００４】[0004]
【化３】 [Chemical 3]
【０００５】一方、特公昭４６−８２４号の実施例１で
挙げられた下記構造式で示される染料は、浸染染色時に
おける電解質が２０〜３０ｇ／ｌという少量でも良好な
染色が実施できるものであるが、耐塩素堅牢度が著しく
不良である。On the other hand, the dye represented by the following structural formula given in Example 1 of Japanese Examined Patent Publication No. 46-824 can carry out good dyeing even with a small amount of the electrolyte at the dyeing dyeing of 20 to 30 g / l. However, the chlorine resistance is extremely poor.
【０００６】[0006]
【化４】 [Chemical 4]
【０００７】本出願人は上記実情に鑑み、浸染染色時に
おける電解質の使用量が少量ですみ、しかも耐塩素堅牢
度が優れているような反応性染料に関して検討を行な
い、下記構造式で示される染料を見出して先に出願を行
なった（特開昭６０−２６０６５４号）。In view of the above situation, the present applicant has conducted a study on a reactive dye which requires only a small amount of electrolyte used at the time of dip dyeing and has excellent chlorine fastness, and is represented by the following structural formula. A dye was found and an application was filed first (Japanese Patent Laid-Open No. 60-260654).
【０００８】[0008]
【化５】 [Chemical 5]
【０００９】[0009]
【発明が解決しようとする課題】上記の構造の染料は総
合的に極めて優れたものであるが、さらに引き続きこの
染料の周辺化合物を提供しようとするものである。Although the dyes having the above structure are excellent overall, it is intended to continue to provide peripheral compounds of the dyes.
【００１０】[0010]
【課題を解決するための手段】すなわち本発明は、遊離
酸の形で、下記一般式〔Ｉ〕That is, the present invention provides a compound represented by the following general formula [I] in the form of a free acid.
【化６】 （式中、Ｒ1 は水素原子またはメチル基を表わし、Ｒ2
は水素原子または低級アルキル基を表わし、Ｒ3 は低級
アルキル基を表わし、Ｘはハロゲン原子を表わし、Ｙは
−ＣＨ＝ＣＨ2 基または−ＣＨ2 ＣＨ2 ＯＳＯ3 Ｈ基を
表わす）で示される水溶性モノアゾ色素に関し、さらに
セルロースまたは含窒素系繊維を含有する繊維を電解質
の存在下、浸染法またはコールドパッドバッチ法により
染色するに当り、反応性染料として上記水溶性モノアゾ
色素を用いることを特徴とする染色方法に関する。[Chemical 6] (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2
Represents a hydrogen atom or a lower alkyl group, R 3 represents a lower alkyl group, X represents a halogen atom, and Y represents a —CH═CH 2 group or a —CH 2 CH 2 OSO 3 H group). Regarding the water-soluble monoazo dye, when the fiber containing cellulose or nitrogen-containing fiber is dyed by the dip dyeing method or the cold pad batch method in the presence of an electrolyte, the above water-soluble monoazo dye is used as a reactive dye. And the dyeing method.
【００１１】以下、本発明を詳細に説明する。前記一般
式〔Ｉ〕で示される水溶性モノアゾ色素において、Ｘで
表わされるハロゲン原子としては、通常、塩素原子、臭
素原子、弗素原子が挙げられ、一方、Ｒ3 で表わされる
低級アルキル基としては、例えば、メチル基、エチル
基、プロピル基等の炭素数１〜４の直鎖または分岐状の
アルキル基が挙げられる。The present invention will be described in detail below. In the water-soluble monoazo dye represented by the general formula [I], the halogen atom represented by X usually includes a chlorine atom, a bromine atom and a fluorine atom, while the lower alkyl group represented by R 3 includes Examples thereof include linear or branched alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group and a propyl group.
【００１２】本発明色素は遊離酸の形で、またはその塩
の形で存在するが、塩としては通常、アルカリ金属塩お
よびアルカリ土類金属塩であり、特にリチウム塩、ナト
リウム塩、カリウム塩が好ましい。The dye of the present invention exists in the form of a free acid or a salt thereof, and the salt is usually an alkali metal salt or an alkaline earth metal salt, particularly a lithium salt, a sodium salt or a potassium salt. preferable.
【００１３】前示一般式〔Ｉ〕で示される本発明のアゾ
色素は以下の方法により製造することができる。例え
ば、１−ヒドロキシ−３，６−ジスルホ−８−アミノナ
フタレンに、塩化シアヌルおよび一般式〔II〕The azo dye of the present invention represented by the above general formula [I] can be produced by the following method. For example, 1-hydroxy-3,6-disulfo-8-aminonaphthalene, cyanuric chloride and the general formula [II]
【化７】 （式中、Ｒ2 およびＸは前記定義に同じ）で表わされる
アニリン化合物を水性媒質中で順次縮合させ、[Chemical 7] (Wherein R 2 and X are as defined above) are successively condensed in an aqueous medium,
【００１４】下記一般式〔III 〕The following general formula [III]
【化８】 （式中、Ｒ2 およびＸは前記定義に同じ）で示される化
合物とし、さらにこの化合物に、[Chemical 8] (Wherein R 2 and X are the same as defined above), and this compound further comprises
【００１５】下記一般式〔IV〕The following general formula [IV]
【化９】 （式中、Ｒ3 およびＹは前記定義に同じ）で示される化
合物を水性媒質中で縮合させ、[Chemical 9] A compound of formula (wherein R 3 and Y are as defined above) is condensed in an aqueous medium,
【００１６】下記一般式〔Ｖ〕The following general formula [V]
【化１０】 （式中、Ｒ2 ，Ｒ3 およびＹは前記定義に同じ）で示さ
れるカップリング成分を合成する。[Chemical 10] (Wherein R 2 , R 3 and Y are as defined above) are synthesized.
【００１７】一方、下記一般式〔VI〕On the other hand, the following general formula [VI]
【化１１】 （式中、Ｒ1 は前記定義に同じ）で示される化合物を通
常の方法でジアゾ化し、これを前記〔Ｖ〕で示される化
合物とカップリングさせることにより、前示一般式
〔Ｉ〕のモノアゾ色素を製造することができる。なお反
応液から目的物を得るには通常の塩析法が用いられる
が、反応液をそのままスプレー乾燥することもできる。[Chemical 11] (Wherein R 1 is the same as defined above) is diazotized by a conventional method, and this is coupled with the compound represented by [V] to give the monoazo compound represented by the general formula [I]. Dyes can be produced. Although an ordinary salting-out method is used to obtain the desired product from the reaction solution, the reaction solution can be spray-dried as it is.
【００１８】[0018]
【作用】本発明のモノアゾ色素は、繊維、布を染色する
ための染料、紙、合成樹脂を着色するための色素、さら
に、インクジェット式プリンター用などの色素等として
広く利用することができるが、特に染料としての適性が
優れており、浸染染色法に用いる反応性染料として好適
である。The monoazo dye of the present invention can be widely used as dyes for dyeing fibers and cloths, papers, dyes for coloring synthetic resins, and dyes for ink jet printers. In particular, it has excellent suitability as a dye and is suitable as a reactive dye used in a dyeing dyeing method.
【００１９】本発明のモノアゾ色素を染料として用いる
場合に対象となる繊維としては、例えば木綿、ビスコー
スレーヨン、キュプラアンモニウムレーヨン、麻などの
セルロース系繊維、または、ポリアミド、羊毛、絹等の
含窒素繊維が挙げられる。なお、これらの繊維は例え
ば、ポリエステル、トリアセテートなどの混合繊維でも
差し支えない。Fibers to be used when the monoazo dye of the present invention is used as a dye include, for example, cellulosic fibers such as cotton, viscose rayon, cupraammonium rayon and hemp, or nitrogen-containing fibers such as polyamide, wool and silk. Fibers. These fibers may be mixed fibers of polyester, triacetate, etc., for example.
【００２０】本発明のモノアゾ色素を用いてセルロース
または含窒素繊維類を染色するには、通常、重炭酸ソー
ダ、炭酸ソーダ等の無機アルカリまたはトリエチルアミ
ン等の有機塩基よりなる酸結合剤の存在下、常法に従っ
て染色することができる。本発明においては、特に、浸
染法またはコールドバッチ法で染色する場合に、芒硝ま
たは食塩等の電解質の使用量を低減できるという優れた
効果を発揮することができるので好ましい。この場合の
電解質の使用量は通常、染色浴１リットル当り、５〜３
０ｇで差し支えない。このように本発明では、通常用い
られる電解質量の１／５〜１／１０程度で充分濃厚な染
色物を得ることができる。また、染色温度は通常、４０
〜８０℃程度が好適である。The dyeing of cellulose or nitrogen-containing fibers with the monoazo dye of the present invention is usually carried out by a conventional method in the presence of an acid binder comprising an inorganic alkali such as sodium bicarbonate and sodium carbonate or an organic base such as triethylamine. Can be dyed according to. In the present invention, particularly when dyeing by an immersion method or a cold batch method, an excellent effect that the amount of an electrolyte such as mirabilite or salt can be reduced can be exhibited, which is preferable. The amount of electrolyte used in this case is usually 5 to 3 per liter of the dyeing bath.
0 g is fine. As described above, in the present invention, it is possible to obtain a sufficiently dense dyed product at about 1/5 to 1/10 of the mass of the electrolyte that is usually used. The dyeing temperature is usually 40
It is preferably about 80 ° C.
【００２１】さらに、本発明のモノアゾ色素は、捺染
法、パッドスチーム法など、ビニルスルホン型反応性染
料が適用できるその他の染色法にも適用することができ
る。Further, the monoazo dye of the present invention can be applied to other dyeing methods to which vinyl sulfone type reactive dyes can be applied such as a printing method and a pad steam method.
【００２２】[0022]
【実施例】以下、本発明の方法を実施例によって具体的
に説明するが、本発明は、以下の実施例に限定されるも
のではない。EXAMPLES The method of the present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.
【００２３】（実施例１）遊離酸の形で下記構造式Example 1 The following structural formula in the form of free acid
【化１２】 [Chemical 12]
【００２４】で示されるアゾ染料０．２ｇを水２００ｍ
ｌに溶解し、芒硝２ｇを加え溶解して調製した染浴（芒
硝使用割合１０ｇ／ｌ）に、未シルケット綿メリヤス１
０ｇを浸漬し３０分を要して５０℃迄昇温した。次い
で、炭酸ソーダ３．０ｇを添加し５０℃で１時間染色し
た後、水洗、ソーピング、水洗、乾燥を行い、青味赤色
の染色物を得た。0.2 g of the azo dye represented by
1 g of mercerized cotton knitted cloth in a dyeing bath prepared by adding 2 g of Glauber's salt to 1 g and dissolving
0 g was immersed and the temperature was raised to 50 ° C. over 30 minutes. Then, 3.0 g of sodium carbonate was added and dyed at 50 ° C. for 1 hour, followed by washing with water, soaping, washing with water and drying to obtain a bluish red dyed product.
【００２５】本染料の染着度は芒硝の使用量が少ないに
も拘らず非常に高く、得られた染色物は極めて濃厚であ
り、また、耐塩素堅牢度（ＪＩＳ Ｌ−０８８４に準拠
し有効塩素２０ｐｐｍ）は５級と非常に優れ、耐光堅牢
度（ＪＩＳ Ｌ−０８４２）も５級と極めて良好であっ
た。The dyeing degree of this dye is very high in spite of the small amount of Glauber's salt used, the dyed product obtained is extremely thick, and the chlorine fastness (effective according to JIS L-0884 is effective). Chlorine (20 ppm) was extremely excellent in grade 5, and light fastness (JIS L-0842) was also excellent in grade 5.
【００２６】（実施例２）実施例１に準じた方法で、下
記構造式（遊離酸の形で示す）(Example 2) By the method according to Example 1, the following structural formula (shown in the form of free acid)
【化１３】 で示されるモノアゾ色素により綿布を染色し、青味赤色
の染色物を得た。[Chemical 13] A cotton cloth was dyed with a monoazo dye represented by the above to obtain a bluish red dyed product.
【００２７】[0027]
【発明の効果】本発明のモノアゾ色素はビニルスルホン
型反応基を有する新規水溶性モノアゾ色素であり、赤色
系の色素として有用なものである。The monoazo dye of the present invention is a novel water-soluble monoazo dye having a vinyl sulfone type reactive group and is useful as a reddish dye.
【００２８】特に、この色素を、セルロースあるいは含
窒素繊維類を浸染染色法またはコールドパッドバッチ法
により染色する際の反応性染料として用いた場合には、
耐塩素堅牢度などの各種堅牢度が良好な上、芒硝、食塩
などの電解質の添加量が少なくても優れた反応染着性を
示し、濃厚な染色物を得ることができる。したがって、
染色廃水中の電解質及び未反応染料の含有量が少なくな
るので廃水処理の面からも望ましい。In particular, when this dye is used as a reactive dye when dyeing cellulose or nitrogen-containing fibers by the dip dyeing method or the cold pad batch method,
Various fastnesses such as chlorine fastness are good, and excellent reaction dyeing properties are exhibited even when the amount of addition of an electrolyte such as mirabilite or salt is small, and a thick dyed product can be obtained. Therefore,
Since the contents of the electrolyte and unreacted dye in the dyeing wastewater are reduced, it is also desirable from the viewpoint of wastewater treatment.
Claims (4)
は水素原子または低級アルキル基を表わし、Ｒ3 は低級
アルキル基を表わし、Ｘはハロゲン原子を表わし、Ｙは
−ＣＨ＝ＣＨ2 基または−ＣＨ2 ＣＨ2 ＯＳＯ3 Ｈ基を
表わす）で示される水溶性モノアゾ色素。1. A compound represented by the following general formula [I] in the form of a free acid: (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2
Represents a hydrogen atom or a lower alkyl group, R 3 represents a lower alkyl group, X represents a halogen atom, and Y represents a —CH═CH 2 group or a —CH 2 CH 2 OSO 3 H group). Water-soluble monoazo dye.
る繊維を電解質の存在下、浸染法またはコールドパッド
バッチ法により染色するに当り、反応性染料として、遊
離酸の形で、下記一般式〔Ｉ〕 【化２】 （式中、Ｒ1 は水素原子またはメチル基を表わし、Ｒ2
は水素原子または低級アルキル基を表わし、Ｒ3 は低級
アルキル基を表わし、Ｘはハロゲン原子を表わし、Ｙは
−ＣＨ＝ＣＨ2 基または−ＣＨ2 ＣＨ2 ＯＳＯ3 Ｈ基を
表わす）で示される水溶性モノアゾ色素を用いることを
特徴とする染色方法。2. When dyeing a fiber containing cellulose or a nitrogen-containing fiber by an immersion dyeing method or a cold pad batch method in the presence of an electrolyte, the following general formula [I ] [Chemical 2] (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2
Represents a hydrogen atom or a lower alkyl group, R 3 represents a lower alkyl group, X represents a halogen atom, and Y represents a —CH═CH 2 group or a —CH 2 CH 2 OSO 3 H group). A dyeing method characterized by using a water-soluble monoazo dye.
り、５〜３０ｇである請求項２記載の染色方法。3. The dyeing method according to claim 2, wherein the amount of the electrolyte used is 5 to 30 g per liter of the dyeing bath.
記載の染色方法。4. The dyeing temperature is 20 to 80 ° C.
The dyeing method described.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61236110A JPH07103319B2 (en) | 1986-10-06 | 1986-10-06 | Water-soluble monoazo dye and dyeing method using the same |
| JP5149006A JPH07108956B2 (en) | 1986-10-06 | 1993-06-21 | Water-soluble monoazo dye and dyeing method using the same |
| JP5149007A JPH07108957B2 (en) | 1986-10-06 | 1993-06-21 | Water-soluble monoazo dye and dyeing method using the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61236110A JPH07103319B2 (en) | 1986-10-06 | 1986-10-06 | Water-soluble monoazo dye and dyeing method using the same |
| JP5149006A JPH07108956B2 (en) | 1986-10-06 | 1993-06-21 | Water-soluble monoazo dye and dyeing method using the same |
| JP5149007A JPH07108957B2 (en) | 1986-10-06 | 1993-06-21 | Water-soluble monoazo dye and dyeing method using the same |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61236110A Division JPH07103319B2 (en) | 1986-10-06 | 1986-10-06 | Water-soluble monoazo dye and dyeing method using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0649383A JPH0649383A (en) | 1994-02-22 |
| JPH07108956B2 true JPH07108956B2 (en) | 1995-11-22 |
Family
ID=27319665
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61236110A Expired - Fee Related JPH07103319B2 (en) | 1986-10-06 | 1986-10-06 | Water-soluble monoazo dye and dyeing method using the same |
| JP5149006A Expired - Fee Related JPH07108956B2 (en) | 1986-10-06 | 1993-06-21 | Water-soluble monoazo dye and dyeing method using the same |
| JP5149007A Expired - Fee Related JPH07108957B2 (en) | 1986-10-06 | 1993-06-21 | Water-soluble monoazo dye and dyeing method using the same |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61236110A Expired - Fee Related JPH07103319B2 (en) | 1986-10-06 | 1986-10-06 | Water-soluble monoazo dye and dyeing method using the same |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5149007A Expired - Fee Related JPH07108957B2 (en) | 1986-10-06 | 1993-06-21 | Water-soluble monoazo dye and dyeing method using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (3) | JPH07103319B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113150576B (en) * | 2021-03-02 | 2022-11-25 | 泰兴锦云染料有限公司 | Ink-jet printing active red dye and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60260654A (en) * | 1984-06-06 | 1985-12-23 | Mitsubishi Chem Ind Ltd | Reactive azo dye for cellulosic fiber |
| JPH0717856B2 (en) * | 1986-03-13 | 1995-03-01 | 住友化学工業株式会社 | Monoazo compound and method for dyeing or printing fiber material using the same |
-
1986
- 1986-10-06 JP JP61236110A patent/JPH07103319B2/en not_active Expired - Fee Related
-
1993
- 1993-06-21 JP JP5149006A patent/JPH07108956B2/en not_active Expired - Fee Related
- 1993-06-21 JP JP5149007A patent/JPH07108957B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0649383A (en) | 1994-02-22 |
| JPH07103319B2 (en) | 1995-11-08 |
| JPH0649384A (en) | 1994-02-22 |
| JPS6390571A (en) | 1988-04-21 |
| JPH07108957B2 (en) | 1995-11-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |