JPH0135955B2 - - Google Patents
Info
- Publication number
- JPH0135955B2 JPH0135955B2 JP56052626A JP5262681A JPH0135955B2 JP H0135955 B2 JPH0135955 B2 JP H0135955B2 JP 56052626 A JP56052626 A JP 56052626A JP 5262681 A JP5262681 A JP 5262681A JP H0135955 B2 JPH0135955 B2 JP H0135955B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- parts
- dye
- acid
- amino
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000002253 acid Substances 0.000 claims description 30
- 238000004043 dyeing Methods 0.000 claims description 21
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- HMNPDEGBVWDHAR-UHFFFAOYSA-N 8-aminonaphthalen-1-ol Chemical group C1=CC(O)=C2C(N)=CC=CC2=C1 HMNPDEGBVWDHAR-UHFFFAOYSA-N 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001624 naphthyl group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 6
- 229920003043 Cellulose fiber Polymers 0.000 claims description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 239000000975 dye Substances 0.000 description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 13
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- -1 monofluorotriazinyl groups Chemical group 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 235000002639 sodium chloride Nutrition 0.000 description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 239000000985 reactive dye Substances 0.000 description 7
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 238000006193 diazotization reaction Methods 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- 210000004243 sweat Anatomy 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 150000001989 diazonium salts Chemical class 0.000 description 4
- 239000010446 mirabilite Substances 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000010014 continuous dyeing Methods 0.000 description 2
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 2
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 235000011008 sodium phosphates Nutrition 0.000 description 2
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 1
- VYZCFAPUHSSYCC-UHFFFAOYSA-N 2-amino-5-chloro-4-methylbenzenesulfonic acid Chemical compound CC1=CC(N)=C(S(O)(=O)=O)C=C1Cl VYZCFAPUHSSYCC-UHFFFAOYSA-N 0.000 description 1
- YAIKCRUPEVOINQ-UHFFFAOYSA-N 2-aminonaphthalene-1,5-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC2=C(S(O)(=O)=O)C(N)=CC=C21 YAIKCRUPEVOINQ-UHFFFAOYSA-N 0.000 description 1
- QNAAQOLWUDNQFY-UHFFFAOYSA-N 3-chloroaniline Chemical compound NC1=CC=CC(Cl)=C1.NC1=CC=CC(Cl)=C1 QNAAQOLWUDNQFY-UHFFFAOYSA-N 0.000 description 1
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 1
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 1
- AKOPUPHRJSONOI-UHFFFAOYSA-N 5-amino-4-chloro-2-methylbenzenesulfonic acid Chemical compound CC1=CC(Cl)=C(N)C=C1S(O)(=O)=O AKOPUPHRJSONOI-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- SAQSTQBVENFSKT-UHFFFAOYSA-M TCA-sodium Chemical compound [Na+].[O-]C(=O)C(Cl)(Cl)Cl SAQSTQBVENFSKT-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 238000010016 exhaust dyeing Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019794 sodium silicate Nutrition 0.000 description 1
- 235000019351 sodium silicates Nutrition 0.000 description 1
- 229940080313 sodium starch Drugs 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Coloring (AREA)
Description
本発明はセルローズ系繊維を濃青色に染色する
方法に関する。
更に詳しくは本発明は遊離酸の形で下記一般式
（）
〔式中、Ｒは水素原子、メチル基またはエチル
基、Ｙは弗素原子または塩素原子、環Ａはメチル
基、メトキシ基、カルボキシ基、塩素原子および
スルホ基の群より選ばれる１または２個の置換基
を有していてもよいフエニル基、または１〜３個
のスルホ基を有するナフチル基、Ｘは１−アミノ
−８−ヒドロキシナフタレンモノまたはジスルホ
ン酸残基を表わす。Ｚは−SO2CH＝CH2または
−SO2CH2CH2OSO3Hを有するフエニルまたは
ナフチル基を表わすが、該フエニル基は他にメチ
ル基、メトキシ基または塩素原子を有していても
よく、また、該ナフチル基は他にスルホ基を有す
る。〕
で示される染料を用いることを特徴とするセルロ
ーズ系繊維の染色法である。
ベンゼン又はナフタレン系のジアゾニウム化合
物２モルと１−アミノ−８−ナフトールスルホン
酸類１モルとをカツプリングすることにより繊維
材料上に緑から青色の色相を与える水溶性染料が
得られることは既に知られている。そして該染料
のうち、モノハロゲノトリアジニル基を有する染
料は反応染料としてよく知られている。しかしこ
れらの反応染料は、一般に染色温度に高温を要
し、また吸尽染色適性に欠けるため捺染用に使用
されるにすぎず、更に、得られた染色物の酸安定
性が低いという欠点を有しているため、実用的に
は決して充分とは言えなかつた。
一方、β−スルフアートエチルスルホニル基を
有する染料がいわゆるビニルスルホン型反応染料
として繊維材料の染色に適用されることは公知で
ある。しかし、β−スルフアートエチルスルホニ
ル基を有するアゾ系の濃青色反応染料による染色
物は、一般に塩素堅牢度が低く、水道水に含まれ
る塩素による退色現象がしばしば問題となつてい
る。
このようなことから、本発明者らは特に塩素堅
牢度がすぐれており、さらに充分な耐光堅牢度、
汗日光堅牢度をかねそなえた濃青色のビニルスル
ホン型反応染料を求めて鋭意検討を行なつた結
果、前記一般式（）で示される染料、すなわ
ち、反応基としてβ−スルフアートエチルスルホ
ニル基と、モノクロルまたはモノフルオロトリア
ジニル基を有するジスアゾ染料がこれらの条件に
合致する濃青色の染色物を与えることを見い出し
た。
また、本発明の染料は、前記のようなモノクロ
ルまたはモノフルオロトリアジニル基を有する反
応性染料の欠点をも解消できることを見い出し
た。
本発明において、セルローズ系繊維としてはた
とえば木綿、麻、ビスコース人絹、ビスコースス
フ等の天然あるいは再生セルローズ繊維をあげる
ことができる。
本発明染料の染色は酸結合剤、例えば苛性ソー
ダ、炭酸ナトリウム、燐酸塩、珪酸塩又は炭酸水
素ナトリウムを用いて行う。染色方法は、繊維の
性質、及び物理的形状によつて選択でき、たとえ
ば吸尽法、捺染法又は連続染色法を採用できる。
吸尽法の場合、炭酸ナトリウム、第三燐酸ナト
リウム、苛性ソーダ等の酸結合剤の存在下に芒硝
又は食塩を加えた染浴で比較的低い温度で行われ
る。捺染法の場合、例えばアルギン酸ナトリウム
又は澱粉エーテルのような糊料又は乳化糊料及び
炭酸ナトリウム、炭酸水素ナトリウム、苛性ソー
ダ、第三燐酸ナトリウム、トリクロル酢酸ナトリ
ウム又は相当するカリウムもしくはアルカリ土類
化合物のようなアルカリ性又はアルカリを放出す
る薬剤とともに、所望によつては、例えば尿素の
ような通常の捺染助剤又は分散剤の添加のもとに
繊維上に施し、乾燥し、そして特に水蒸気の存在
下で熱処理に付すことにより染色できる。
連続染色法の場合、例えば炭酸ナトリウム、炭
酸水素ナトリウム、苛性ソーダ、珪酸ソーダ、第
三燐酸ソーダ又は相当するカリウムもしくはアル
カリ土類化合物のようなアルカリ性薬剤を単独あ
るいは併用し、場合によつては芒硝又は食塩を加
えて、所望によつてはアルギン酸ソーダのような
通常のマイグレーシヨン防止剤、あるいは尿素な
どの溶解助剤又は浸透剤の添加のもとに繊維上に
施し、熱処理に付すことにより染色できる。
本発明の染料は、例えば次のようにして製造す
ることができる。メタフエニレンジアミンジスル
ホン酸と、一般式（）
〔式中、Ｒ、Ｚは前記の意味を有する〕
で示されるアミンを一般式（）
〔式中、Ｙは前記の意味を有する〕
で表わされる２、４、６−トリハロゲノ−ｓ−ト
リアジンと任意の順序で組合させて、遊離酸の形
で一般式（）
〔式中、Ｚ、Ｒ、Ｙは前記の意味を有する〕に導
びき、常法によりジアゾ化して得たジアゾニウム
化合物と、一般式（）
〔式中、環Ａは前記の意味を有する〕
で示されるアリールアミン化合物を常法によりジ
アゾ化して得たジアゾニウム化合物を、一般式
（）
Ｈ−Ｘ−Ｈ （）
〔式中、Ｘは前記の意味を有する〕
で示される１−アミノ−８−ヒドロキシナフタリ
ンモノまたはジスルホン酸と任意の順序でカツプ
リングすることにより得られる。
本発明において使用できる一般式（）で示さ
れるアミンとしては、例えば次の化合物があげら
れる。
１−アミノベンゼン−２−、−３−または−４
−β−スルフアトエチルスルホン、１−アミノベ
ンゼン−３−β−ホスフアトエチルスルホン、１
−アミノ−４−メチルベンゼン−３−β−スルフ
アトエチルスルホン、１−アミノベンゼン−３−
β−クロルエチルスルホン、１−アミノ−４−メ
トキシベンゼン−３−β−スルフアトエチルスル
ホン、１−アミノベンゼン−４−β−スルフアト
エチルスルホン−２−スルホン酸、１−アミノベ
ンゼン−５−β−スルフアトエチルスルホン−２
−スルホン酸、１−アミノベンゼン−５−β−ス
ルフアトエチルスルホン−２，４−ジスルホン
酸、１−アミノナフタリン−４−β−スルフアト
エチルスルホン、１−アミノ−２，５−ジメトキ
シベンゼン−４−β−スルフアトエチルスルホ
ン、１−アミノベンゼン−４−β−スルフアトエ
チルスルホン−２−カルボン酸、１−アミノベン
ゼン−５−β−スルフアトエチルスルホン−２−
カルボン酸、１−アミノ−２−メトキシベンゼン
−４−β−スルフアトエチルスルホン、１−アミ
ノ−２−クロルベンゼン−４−β−スルフアトエ
チルスルホン、１−アミノ−２−メトキシベンゼ
ン−５−β−スルフアトエチルスルホン、２−ア
ミノナフタリン−８−β−スルフアトエチルスル
ホン、２−アミノナフタリン−８−β−スルフア
トエチルスルホン−６−スルホン酸、１−アミノ
−２，５−ジメトキシベンゼン−４−ビニルスル
ホン、１−アミノ−２−メトキシ−５−メチルベ
ンゼン−４−β−スルフアトエチルスルホン、１
−アミノ−２，５−ジエトキシベンゼン−４−β
−スルフアトエチルスルホン、１−アミノ−２−
ブロムベンゼン−４−β−スルフアトエチルスル
ホン、１−アミノ−２−ブロムベンゼン−４−ビ
ニルスルホン、１−アミノベンゼン−５−ビニル
スルホン−２，４−ジスルホン酸、１−アミノベ
ンゼン−５−β−ホスフアトエチルスルホン−
２，４−ジスルホン酸、１−アミノベンゼン−５
−β−クロルエチルスルホン−２，４−ジスルホ
ン酸、２−アミノナフタリン−８−β−ホスフア
トエチルスルホン−６−スルホン酸、２−アミノ
ナフタリン−８−ビニルスルホン−６−スルホン
酸、１−アミノ−２−メトキシ−５−メチルベン
ゼン−４−β−クロルエチルスルホン、２−アミ
ノフエノール−４−β−スルフアトエチルスルホ
ン、１−アミノベンゼン−３−または−４−ビニ
ルスルホン、１−アミノ−２−ヒドロキシベンゼ
ン−４−β−スルフアトエチルスルホン、１−ア
ミノベンゼン−５−ビニルスルホン−２−スルホ
ン酸、３−（Ｎ−メチル−β−スルフアトエチル
スルホニルアミノ）−１−アミノベンゼン、３−
（Ｎ−エチル−β−スルフアトエチルスルホニル
アミノ）−１−アミノベンゼン、３−β−スルフ
アトエチルスルホニルアミノ−１−アミノベンゼ
ン、
１−（Ｎ−メチルまたはエチルアミノ）ベンゼ
ン−２、３または４−β−スルフアートエチルス
ルホン、１−（Ｎ−メチルアミノ）ベンゼン−３
−β−ホスフアートエチルスルホン、１−（Ｎ−
メチルアミノ）−４−メトキシベンゼン−３−β
−スルフアートエチルスルホン、１−（Ｎ−メチ
ルアミノ）ナフタリン−４−β−スルフアートエ
チルスルホン、２−（Ｎ−メチルアミノ）ナフタ
リン−８−β−スルフア−エチルスルホン、１−
（Ｎ−エチルアミノ）ベンゼン−３−β−ホスフ
アートエチルスルホン、１−（Ｎ−エチルアミノ）
−４−メトキシベンゼン−３−β−スルフアート
エチルスルホン、１−（Ｎ−エチルアミノ）ナフ
タリン−４−βスルフアートエチルスルホン、２
−（Ｎ−エチルアミノ）ナフタリン−８−β−ス
ルフアートエチルスルホン。
一般式（）で示されるアリールアミン化合物
としては、例えば、アニリン、アニリン−２，３
または４−スルホン酸、アニリン−２，５−また
は３，５−ジスルホン酸、アントラニル酸、パラ
トルイジンスルホン酸、３−アミノ−６−クロロ
トルエン−４−スルホン酸、２−クロロ−パラト
ルイジン−５−スルホン酸、パラアニシジンオル
トスルホン酸、２または３または４−クロロアニ
リン、１−アミノナフタリン−２，３，４，５，
６または７−スルホン酸、１−アミノナフタリン
−２，４−、２，５−、２，６−、２，７−、
３，５−、３，６−、３，７−、４，６−、４，
７−または５，７−ジスルホン酸、１−アミノナ
フタリン−２，４，６−、２，４，７−または
３，５，７−トリスルホン酸、２−アミノナフタ
リン−１、３、４、５、６、７または８−スルホ
ン酸、２−アミノナフタリン−１，４−、１，５
−、１，６−、１，７−、３，５−、３，６−、
３，７−、３，８−、４，６−、４，７−、４，
８−、５，７−、５，８−または６，８−ジスル
ホン酸、２−アミノナフタリン−１，４，６−、
１，４，７−、３，５，７−、３，５，８−、
３，６，８−または４，６，８−トリスルホン酸
があげられる。
一般式（）で示される１−アミノ−８−ヒド
ロキシナフタリンモノまたはジスルホン酸として
は、例えば１−アミノ−８−ヒドロキシナフタリ
ン−３、４、５または６−スルホン酸、１−アミ
ノ−８−ヒドロキシナフタリン−３，６−または
４，６−ジスルホン酸があげられる。
このようにして得られた本発明の染料は従来の
β−スルフアートエチルスルホニル基を有するア
ゾ系の濃青色反応染料に比して、それより低い染
色温度においても、あるいはそれより高い染色温
度においても温度に依存することなく、ほぼ一定
の色濃度の染色物が得られる。すなわち、染色の
再現性がすぐれている。また、本発明染料は均染
性にすぐれており、特に酸化剤を含む洗たく液に
対する染料のブリードが起らないこと、しかも塩
素堅牢度、耐光堅牢度、汗日光堅牢度等にもすぐ
れている。また本発明染料は、高い吸尽率を示す
ので、濃度の高い染色物を得ることができるのみ
ならず、染浴中に残存する染料分にもわずかであ
ることから廃浴処理の面でも有利である利点を有
する。また本発明染料による染色物は白色抜染で
き、すぐれた白場を再生することができる。
以下に本発明を実施例により詳細に説明する
が、本発明はこれらの実施例により何等限定され
るものではない。尚文中部は重量部、％は重量％
を表わす。
実施例 １
遊離酸の形で式(1)
（λmax＝596nｍ、但し水溶媒中、以下同条件で
測定）
で示される染料0.3部を200部に水に溶解し芒硝20
部を加え、木綿10部を加えて50℃に昇温する。つ
いで30分経過後、炭酸ソーダ４部を加え同温度で
１時間染色する。染色終了後、水洗、ソーピング
を行なつて塩素耐光、汗日光堅牢度のずれた濃青
色の濃度の高い染色物を得た。
参考例 １
〔実施例１の染料（）の合成例〕
２−アミノナフタリン−１，５−ジスルホン酸
7.58部と水160部、氷40部と濃塩酸3.7部を加え、
０〜５℃にて35％の亜硝酸ソーダ溶液5.1部を注
入してジアゾ化を行う。余剰の亜硝酸を消去した
後、１−アミノ−８−ヒドロキシナフタリン−
３，６−ジスルホン酸7.73部の中性溶液を０〜10
℃で約１時間を要して注入しPH1.0〜2.0でカツプ
リングを行う。この混合物を数時間撹拌した後、
苛性ソーダ溶液で中和しPH７とし、30〜35℃にて
塩化ナトリウムを入れて塩折しモノアゾ染料を得
る。
一方、塩化シアヌル4.61部とｍ−フエニレンジ
アミンジスルホン酸6.70部を界面活性剤水溶液50
部中でPH1.5〜3.0に１〜２時間、10〜15℃に保つ
ことにより第一縮合を行い次に１−アミノベンゼ
ン−３−β−スルフアートエチルスルホン6.95部
を加え、20％炭酸ソーダ溶液でPH５〜5.5に保ち
ながら25〜30℃で一晩撹拌することにより第二縮
合を行なう。
ついで氷50部、濃塩酸7.1部を加えてから、35
％の亜硝酸ソーダ溶液5.3部を加えてジアゾ化を
行う。余剰の亜硝酸を消去したジアゾ化液を、重
炭酸ソーダアルカリ性としたモノアゾ染料の懸濁
液に５〜10℃で注入し、１〜２時間撹拌してカツ
プリングを行なう。希硫酸でPHを5.5〜6.0とし温
度を50〜55℃とした後、この液に塩化ナトリウム
を加えて塩析し過、洗浄した後60℃で乾燥す
る。41.0部の染料(1)を得た。
実施例 ２〜18
実施例１において染料(1)の代わり下記(2)〜
（18）の染料を用いる他は同様に染色した。すぐ
れた堅牢度を有する濃青色の濃度の高い染色物が
得られた。
下記の染料は、
Ａ欄：１−アミノ−８−ヒドロキシナフタリンモ
ノまたはジスルホン酸〔前記一般式（）の
化合物〕
Ｂ欄：モノアゾ染料のジアゾ成分〔前記一般式
（）の化合物〕
Ｃ欄：ジスアゾ染料のジアゾ成分〔前記一般式
（）の化合物〕を構成するアミン〔前記一
般式（）の化合物〕
Ｄ欄：２，４，６−トリハロゲノ−ｓ−トリアジ
ン〔前記一般式（）の化合物〕
Ｅ欄：ジスアゾ染料溶液のλmaxによつて特徴づ
けられる。
The present invention relates to a method for dyeing cellulose fibers deep blue. More specifically, the present invention provides the following general formula () in the form of a free acid: [In the formula, R is a hydrogen atom, a methyl group or an ethyl group, Y is a fluorine atom or a chlorine atom, and ring A is one or two atoms selected from the group of a methyl group, a methoxy group, a carboxy group, a chlorine atom, and a sulfo group. A phenyl group which may have a substituent or a naphthyl group having 1 to 3 sulfo groups, and X represents a 1-amino-8-hydroxynaphthalene mono- or disulfonic acid residue. Z represents a phenyl or naphthyl group having −SO 2 CH=CH 2 or −SO 2 CH 2 CH 2 OSO 3 H, but the phenyl group may also have a methyl group, a methoxy group, or a chlorine atom. Often, the naphthyl group also has a sulfo group. ] This is a method for dyeing cellulose fibers, which is characterized by using the dye shown below. It is already known that by coupling 2 moles of a benzene or naphthalene-based diazonium compound with 1 mole of 1-amino-8-naphtholsulfonic acids, a water-soluble dye that imparts a green to blue hue on textile materials can be obtained. There is. Among these dyes, dyes having a monohalogenotriazinyl group are well known as reactive dyes. However, these reactive dyes generally require high dyeing temperatures and lack suitability for exhaust dyeing, so they are only used for textile printing.Furthermore, they have the disadvantage of low acid stability of the dyed products obtained. Therefore, it could never be said to be sufficient for practical purposes. On the other hand, it is known that dyes having a β-sulfatoethylsulfonyl group can be applied to dyeing textile materials as so-called vinylsulfone type reactive dyes. However, dyed products using azo deep blue reactive dyes having a β-sulfatoethylsulfonyl group generally have low chlorine fastness, and fading due to chlorine contained in tap water is often a problem. For these reasons, the present inventors have found that the chlorine fastness is particularly excellent, and furthermore, the light fastness is sufficient.
As a result of extensive research in search of a deep blue vinyl sulfone type reactive dye that has sweat and sunlight fastness, we found that the dye represented by the general formula (), i.e., β-sulfatoethylsulfonyl group as the reactive group, We have found that disazo dyes containing monochloro or monofluorotriazinyl groups give deep blue dyeings that meet these conditions. It has also been found that the dye of the present invention can overcome the drawbacks of reactive dyes having monochloro or monofluorotriazinyl groups as described above. In the present invention, examples of cellulose fibers include natural or regenerated cellulose fibers such as cotton, linen, viscose human silk, and viscose cotton. Dyeing of the dyes according to the invention is carried out using acid binders such as caustic soda, sodium carbonate, phosphates, silicates or sodium bicarbonate. The dyeing method can be selected depending on the properties and physical shape of the fiber, and for example, an exhaust method, a printing method, or a continuous dyeing method can be employed. In the case of the exhaust method, it is carried out at a relatively low temperature in a dye bath containing Glauber's salt or common salt in the presence of an acid binder such as sodium carbonate, trisodium phosphate, or caustic soda. In the case of printing processes, thickening agents or emulsifying thickening agents such as, for example, sodium alginate or starch ethers and sodium carbonate, sodium bicarbonate, caustic soda, sodium triphosphate, sodium trichloroacetate or the corresponding potassium or alkaline earth compounds are used. applied to the fibers together with alkaline or alkali-releasing agents, optionally with the addition of customary printing aids or dispersants, such as urea, dried and heat treated, especially in the presence of water vapor. It can be dyed by applying it to. In the case of continuous dyeing methods, alkaline agents such as sodium carbonate, sodium bicarbonate, caustic soda, sodium silicate, sodium phosphate or the corresponding potassium or alkaline earth compounds, alone or in combination, may be used, optionally with Glauber's salt or Dyeing can be achieved by applying common salt to the fibers, optionally with the addition of conventional anti-migration agents such as sodium alginate, or solubilizing agents or penetrants such as urea, and subjecting them to heat treatment. . The dye of the present invention can be produced, for example, as follows. Metaphenylenediamine disulfonic acid and general formula () [In the formula, R and Z have the above-mentioned meanings] An amine represented by the general formula () [wherein Y has the above-mentioned meaning] In combination with 2,4,6-trihalogeno-s-triazine represented by [In the formula, Z, R, and Y have the above-mentioned meanings] and a diazonium compound obtained by diazotization by a conventional method, and the general formula () [In the formula, ring A has the above-mentioned meaning] A diazonium compound obtained by diazotizing the arylamine compound represented by It can be obtained by coupling with 1-amino-8-hydroxynaphthalene mono- or disulfonic acid shown in the following in any order. Examples of the amine represented by the general formula () that can be used in the present invention include the following compounds. 1-Aminobenzene-2-, -3- or -4
-β-sulfatoethylsulfone, 1-aminobenzene-3-β-phosphatoethylsulfone, 1
-amino-4-methylbenzene-3-β-sulfatoethylsulfone, 1-aminobenzene-3-
β-chloroethylsulfone, 1-amino-4-methoxybenzene-3-β-sulfatoethylsulfone, 1-aminobenzene-4-β-sulfatoethylsulfone-2-sulfonic acid, 1-aminobenzene- 5-β-sulfatoethylsulfone-2
-sulfonic acid, 1-aminobenzene-5-β-sulfatoethylsulfone-2,4-disulfonic acid, 1-aminonaphthalene-4-β-sulfatoethylsulfone, 1-amino-2,5-dimethoxy Benzene-4-β-sulfatoethylsulfone, 1-aminobenzene-4-β-sulfatoethylsulfone-2-carboxylic acid, 1-aminobenzene-5-β-sulfatoethylsulfone-2-
Carboxylic acid, 1-amino-2-methoxybenzene-4-β-sulfatoethylsulfone, 1-amino-2-chlorobenzene-4-β-sulfatoethylsulfone, 1-amino-2-methoxybenzene- 5-β-sulfatoethylsulfone, 2-aminonaphthalene-8-β-sulfatoethylsulfone, 2-aminonaphthalene-8-β-sulfatoethylsulfone-6-sulfonic acid, 1-amino-2 , 5-dimethoxybenzene-4-vinylsulfone, 1-amino-2-methoxy-5-methylbenzene-4-β-sulfatoethylsulfone, 1
-amino-2,5-diethoxybenzene-4-β
-sulfatoethylsulfone, 1-amino-2-
Bromobenzene-4-β-sulfatoethylsulfone, 1-amino-2-bromobenzene-4-vinylsulfone, 1-aminobenzene-5-vinylsulfone-2,4-disulfonic acid, 1-aminobenzene-5 -β-Phosphatoethylsulfone-
2,4-disulfonic acid, 1-aminobenzene-5
-β-chloroethylsulfone-2,4-disulfonic acid, 2-aminonaphthalene-8-β-phosphatoethylsulfone-6-sulfonic acid, 2-aminonaphthalene-8-vinylsulfone-6-sulfonic acid, 1- Amino-2-methoxy-5-methylbenzene-4-β-chloroethylsulfone, 2-aminophenol-4-β-sulfatoethylsulfone, 1-aminobenzene-3- or -4-vinylsulfone, 1- Amino-2-hydroxybenzene-4-β-sulfatoethylsulfone, 1-aminobenzene-5-vinylsulfone-2-sulfonic acid, 3-(N-methyl-β-sulfatoethylsulfonylamino)-1 -Aminobenzene, 3-
(N-ethyl-β-sulfatoethylsulfonylamino)-1-aminobenzene, 3-β-sulfatoethylsulfonylamino-1-aminobenzene, 1-(N-methyl or ethylamino)benzene-2, 3 or 4-β-sulfatoethylsulfone, 1-(N-methylamino)benzene-3
-β-phosphate ethyl sulfone, 1-(N-
Methylamino)-4-methoxybenzene-3-β
-Sulfatoethylsulfone, 1-(N-methylamino)naphthalene-4-β-sulfatoethylsulfone, 2-(N-methylamino)naphthalene-8-β-sulfa-ethylsulfone, 1-
(N-ethylamino)benzene-3-β-phosphatoethylsulfone, 1-(N-ethylamino)
-4-Methoxybenzene-3-β-sulfatoethylsulfone, 1-(N-ethylamino)naphthalene-4-βsulfatoethylsulfone, 2
-(N-ethylamino)naphthalene-8-β-sulfatoethylsulfone. Examples of the arylamine compound represented by the general formula () include aniline, aniline-2,3
or 4-sulfonic acid, aniline-2,5- or 3,5-disulfonic acid, anthranilic acid, para-toluidine-sulfonic acid, 3-amino-6-chlorotoluene-4-sulfonic acid, 2-chloro-paratoluidine-5 -sulfonic acid, para-anisidine orthosulfonic acid, 2 or 3 or 4-chloroaniline, 1-aminonaphthalene-2,3,4,5,
6 or 7-sulfonic acid, 1-aminonaphthalene-2,4-, 2,5-, 2,6-, 2,7-,
3,5-, 3,6-, 3,7-, 4,6-, 4,
7- or 5,7-disulfonic acid, 1-aminonaphthalene-2,4,6-, 2,4,7- or 3,5,7-trisulfonic acid, 2-aminonaphthalene-1,3,4, 5, 6, 7 or 8-sulfonic acid, 2-aminonaphthalene-1,4-, 1,5
-, 1,6-, 1,7-, 3,5-, 3,6-,
3,7-, 3,8-, 4,6-, 4,7-, 4,
8-, 5,7-, 5,8- or 6,8-disulfonic acid, 2-aminonaphthalene-1,4,6-,
1,4,7-, 3,5,7-, 3,5,8-,
Examples include 3,6,8- or 4,6,8-trisulfonic acid. Examples of the 1-amino-8-hydroxynaphthalene mono- or disulfonic acid represented by the general formula () include 1-amino-8-hydroxynaphthalene-3, 4, 5 or 6-sulfonic acid, 1-amino-8-hydroxy Mention may be made of naphthalene-3,6- or 4,6-disulfonic acid. The thus obtained dye of the present invention can be used at a lower dyeing temperature or at a higher dyeing temperature than conventional azo deep blue reactive dyes having a β-sulfatoethylsulfonyl group. Also, dyed products with almost constant color density can be obtained regardless of temperature. That is, the reproducibility of staining is excellent. In addition, the dye of the present invention has excellent level dyeing properties, in particular, the dye does not bleed in washing liquids containing oxidizing agents, and it also has excellent chlorine fastness, light fastness, sweat and sunlight fastness, etc. . Furthermore, since the dye of the present invention exhibits a high exhaustion rate, it is possible not only to obtain dyed products with high density, but also to be advantageous in terms of waste bath treatment since only a small amount of dye remains in the dye bath. It has the advantage of being In addition, the dyed material using the dye of the present invention can be discharged in white, and excellent white areas can be reproduced. EXAMPLES The present invention will be explained in detail below with reference to Examples, but the present invention is not limited to these Examples in any way. Shobun Chubu is parts by weight, % is weight%.
represents. Example 1 Formula (1) in free acid form (λmax = 596 nm, however, in an aqueous solvent, hereinafter measured under the same conditions) Dissolve 0.3 part of the dye shown in 200 parts of water and 20
1 part, add 10 parts of cotton, and raise the temperature to 50℃. After 30 minutes, 4 parts of soda carbonate is added and dyed at the same temperature for 1 hour. After dyeing, washing with water and soaping were carried out to obtain a dyed product with a deep blue color and high density, with different light fastness to chlorine and sweat and sunlight. Reference example 1 [Synthesis example of dye () of Example 1] 2-aminonaphthalene-1,5-disulfonic acid
Add 7.58 parts, 160 parts of water, 40 parts of ice and 3.7 parts of concentrated hydrochloric acid,
Diazotization is carried out by injecting 5.1 parts of 35% sodium nitrite solution at 0-5°C. After eliminating excess nitrite, 1-amino-8-hydroxynaphthalene
A neutral solution of 7.73 parts of 3,6-disulfonic acid
It takes about 1 hour to inject at ℃ and couple at pH 1.0 to 2.0. After stirring this mixture for several hours,
Neutralize with caustic soda solution to pH 7, add sodium chloride at 30-35°C and salt to obtain a monoazo dye. On the other hand, 4.61 parts of cyanuric chloride and 6.70 parts of m-phenylenediamine disulfonic acid were added to 50% of an aqueous surfactant solution.
The first condensation was carried out by keeping the pH at 1.5 to 3.0 for 1 to 2 hours at 10 to 15°C in the same room, and then 6.95 parts of 1-aminobenzene-3-β-sulfatoethyl sulfone was added and 20% The second condensation is carried out by stirring overnight at 25-30° C. while maintaining the pH at 5-5.5 with a sodium carbonate solution. Then, after adding 50 parts of ice and 7.1 parts of concentrated hydrochloric acid,
Diazotization is carried out by adding 5.3 parts of % sodium nitrite solution. The diazotized solution from which excess nitrous acid has been removed is poured into a monoazo dye suspension made alkaline with sodium bicarbonate at 5 to 10°C, and the suspension is stirred for 1 to 2 hours to perform coupling. After adjusting the pH to 5.5 to 6.0 and the temperature to 50 to 55°C with dilute sulfuric acid, add sodium chloride to this solution to salt out, filter, wash, and dry at 60°C. 41.0 parts of dye (1) were obtained. Examples 2 to 18 In Example 1, instead of dye (1), the following (2) to
Dyeing was carried out in the same manner except that the dye (18) was used. A deep blue, intense dyeing with excellent fastness properties was obtained. The following dyes are as follows: Column A: 1-amino-8-hydroxynaphthalene mono- or disulfonic acid [compound of the above general formula ()] Column B: Diazo component of monoazo dye [compound of the above general formula ()] Column C: disazo Amine constituting the diazo component of the dye [compound of the above general formula ()] [compound of the above general formula ()] Column D: 2,4,6-trihalogeno-s-triazine [compound of the above general formula ()] E Column: Characterized by λmax of the disazo dye solution.
【表】【table】
【表】
実施例 19
遊離酸の形で式（19）
で示される染料0.3部を200部の水に溶解し芒硝20
部を加え、木綿10部を加えて50℃に昇温する。つ
いで30分経過後、炭酸ソーダ４部を加え同温度で
１時間染色する。染色終了後、水洗、ソーピング
を行なつて塩素耐光、汗日光堅牢度のすぐれた濃
青色の濃度の高い染色物を得た。
参考例 ２
〔実施例19の染料（19）の合成例〕
参考例１における２種類のジアゾニウム化合物
の１−アミノ−８−ナフタリン−３，６−ジスル
ホン酸へのカツプリング順序を逆転させること以
外は同様にして合成した。
実施例 20〜35
実施例19において染料（19）の代わりに下記
（20）〜（35）の染料を用いる他は同様に染色し
た。すぐれた堅牢度を有する濃青色の濃度の高い
染色物が得られた。
下記の染料は下記によつて特徴づけられる。
Ａ欄：１−アミノ−８−ヒドロキシモノまたはジ
スルホン酸
Ｂ欄：モノアゾ染料のジアゾ成分〔前記一般式
（）の化合物〕を構成するアミン〔前記一
般式（）の化合物〕
Ｃ欄：２，４，６−トリハロゲノ−Ｓ−トリアジ
ン〔前記一般式（）の化合物〕
Ｄ欄：ジスアゾ染料のジアゾ成分〔前記一般式
（）の化合物〕
Ｅ欄：ジスアゾ染料浴液のλmax[Table] Example 19 Formula (19) in free acid form Dissolve 0.3 parts of the dye shown in 200 parts of water and add 20 parts of mirabilite.
1 part, add 10 parts of cotton, and raise the temperature to 50℃. After 30 minutes, 4 parts of soda carbonate is added and dyed at the same temperature for 1 hour. After dyeing, washing with water and soaping were performed to obtain a deep blue dyed product with excellent chlorine light fastness and sweat/sunlight fastness. Reference Example 2 [Synthesis example of dye (19) of Example 19] Except for reversing the coupling order of two types of diazonium compounds to 1-amino-8-naphthalene-3,6-disulfonic acid in Reference Example 1. It was synthesized in the same manner. Examples 20 to 35 Dyeing was carried out in the same manner as in Example 19 except that the following dyes (20) to (35) were used instead of dye (19). A deep blue, intense dyeing with excellent fastness properties was obtained. The dyes listed below are characterized by: Column A: 1-amino-8-hydroxy mono- or disulfonic acid Column B: Amine constituting the diazo component of the monoazo dye [compound of the above general formula ()] [compound of the above general formula ()] Column C: 2,4 , 6-trihalogeno-S-triazine [compound of the above general formula ()] Column D: Diazo component of disazo dye [compound of the above general formula ()] Column E: λmax of the disazo dye bath solution
【表】【table】
【表】
実施例 36
式（36）
で示される染料0.3部を200部の水に溶解し芒硝20
部を加え、木綿10部を加えて40℃に昇温する。つ
いで30分経過後、炭酸ソーダ４部を加え同温度で
１時間染色する。染色終了後、水洗、ソーピング
を行なつて塩素耐光、汗日光堅牢度のすぐれた濃
青色の濃度の高い染色物を得た。
参考例 ３
〔実施例36の染料（36）の合成例〕
氷水25部にアニリン−４−スルホン酸4.33部と
濃塩酸3.7部を加え、０〜５℃にて35％の亜硝酸
ソーダ溶液5.1部を注入してジアゾ化を行う。余
剰の亜硝酸を消去した後１−アミノ−８−ヒドロ
キシナフタレン−３，６−ジスルホン酸モノナト
リウム塩7.81部の中性溶液を０〜10℃で約１時間
を要して注入しPH0.5〜1.5でカツプリングを行
う。この混合物を数時間撹拌した後、苛性ソーダ
溶液で中和しPH７とし、30〜35℃にて塩化ナトリ
ウムを入れて塩析しモノアゾ染料を得る。
一方、塩化シアヌル4.61部とｍ−フエニレンジ
アミンジスルホン酸6.70部を界面活性剤水溶液50
部中でPH６〜７に１〜２時間、10〜15℃に保つこ
とにより第一縮合を行い、次に１−アミノベンゼ
ン−３−β−スルフアートエチルスルホン6.95部
を加え、９％の重炭酸ソーダ溶液でPH５〜5.5部
に保ちながら25〜30℃で一晩撹拌することにより
第二縮合を行なう。
ついで氷50部、濃塩酸7.1部を加えてから、35
％の亜硝酸ソーダ溶液5.3部を加えてジアゾ化を
行う。余剰の亜硝酸を消去したジアゾ化液を、重
炭酸ソーダアルカリ性としたモノアゾ染料の懸濁
液に５〜10℃で注入し、１〜２時間撹拌してカツ
プリングを行なう。希硫酸でPH5.5〜6.0とし温度
を50〜55℃とした後、この液に塩化ナトリウムを
加えて塩析し過、洗浄した後60℃で乾燥する。
37.5部の染料（36）を得た。
実施例 37〜54
実施例36において染料（36）の代わりに下記
（37）〜（54）の染料を用いる他は同様に染色し
た。すぐれた堅牢度を有する濃青色の濃度の高い
染色物が得られた。
下記の染料は、アゾ成分〔前記一般式（）の
化合物〕染料のジアゾ成分〔前記一般式（）の
化合物〕：Ｂ欄、ジスアゾ染料のジアゾ成分
を構成するアニリン化合物〔前記一般式（）の
化合物〕Ｃ欄、並びにジスアゾ染料溶液のλmax
（Ｄ欄）により特徴づけられる。[Table] Example 36 Formula (36) Dissolve 0.3 parts of the dye shown in 200 parts of water and add 20 parts of mirabilite.
Add 10 parts of cotton and raise the temperature to 40℃. After 30 minutes, 4 parts of soda carbonate is added and dyed at the same temperature for 1 hour. After dyeing, washing with water and soaping were performed to obtain a deep blue dyed product with excellent chlorine light fastness and sweat/sunlight fastness. Reference Example 3 [Synthesis example of dye (36) of Example 36] Add 4.33 parts of aniline-4-sulfonic acid and 3.7 parts of concentrated hydrochloric acid to 25 parts of ice water, and prepare 5.1 parts of 35% sodium nitrite solution at 0 to 5°C. Diazotization is carried out by injecting After eliminating excess nitrous acid, 7.81 parts of a neutral solution of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid monosodium salt was injected over a period of about 1 hour at 0 to 10°C, and the pH was 0.5. Perform cupping at ~1.5. After stirring this mixture for several hours, it is neutralized with a caustic soda solution to a pH of 7, and salted out with sodium chloride at 30 to 35°C to obtain a monoazo dye. On the other hand, 4.61 parts of cyanuric chloride and 6.70 parts of m-phenylenediamine disulfonic acid were added to 50% of an aqueous surfactant solution.
The first condensation was carried out by keeping at 10-15° C. for 1-2 hours at pH 6-7 in a 100°C, then 6.95 parts of 1-aminobenzene-3-β-sulfatoethyl sulfone was added and 9% The second condensation is carried out by stirring overnight at 25-30° C. while maintaining the pH at 5-5.5 parts with sodium bicarbonate solution. Then, after adding 50 parts of ice and 7.1 parts of concentrated hydrochloric acid,
Diazotization is carried out by adding 5.3 parts of % sodium nitrite solution. The diazotized solution from which excess nitrous acid has been removed is poured into a monoazo dye suspension made alkaline with sodium bicarbonate at 5 to 10°C, and the suspension is stirred for 1 to 2 hours to perform coupling. After adjusting the pH to 5.5 to 6.0 with dilute sulfuric acid and bringing the temperature to 50 to 55°C, add sodium chloride to the solution for salting out, filter, wash, and dry at 60°C.
37.5 parts of dye (36) were obtained. Examples 37-54 Dyeing was carried out in the same manner as in Example 36, except that dyes (37) to (54) below were used instead of dye (36). A deep blue, intense dyeing with excellent fastness properties was obtained. The following dyes are azo component [compound of the above general formula ()] diazo component of the dye [compound of the above general formula ()]: Column B, diazo component of the disazo dye Aniline compound [compound of the above general formula ()] column C, and λmax of the disazo dye solution
(Column D).
【表】【table】
Claims (1)
基、Ｙは弗素原子または塩素原子、環Ａはメチル
基、メトキシ基、カルボキシ基、塩素原子および
スルホ基の群より選ばれる１または２個の置換基
を有していてもよいフエニル基、または１〜３個
のスルホ基を有するナフチル基、Ｘは１−アミノ
−８−ヒドロキシナフタレンモノまたはジスルホ
ン酸残基を表わす。Ｚは−SO2CH＝CH2または
−SO2CH2CH2OSO3Hを有するフエニルまたは
ナフチル基を表わすが、該フエニル基は他にメチ
ル基、メトキシ基または塩素原子を有していても
よく、また、該ナフチル基は他にスルホ基を有す
る。〕 で示される染料を用いることを特徴とするセルロ
ーズ系繊維の染色法。[Claims] 1 The following general formula in the form of a free acid: [In the formula, R is a hydrogen atom, a methyl group or an ethyl group, Y is a fluorine atom or a chlorine atom, and ring A is one or two atoms selected from the group of a methyl group, a methoxy group, a carboxy group, a chlorine atom, and a sulfo group. A phenyl group which may have a substituent or a naphthyl group having 1 to 3 sulfo groups, and X represents a 1-amino-8-hydroxynaphthalene mono- or disulfonic acid residue. Z represents a phenyl or naphthyl group having −SO 2 CH=CH 2 or −SO 2 CH 2 CH 2 OSO 3 H, but the phenyl group may also have a methyl group, a methoxy group, or a chlorine atom. Often, the naphthyl group also has a sulfo group. ] A method for dyeing cellulose fibers, characterized by using the dye shown below.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56052626A JPS57167462A (en) | 1981-04-07 | 1981-04-07 | Dyeing of cellulosic fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56052626A JPS57167462A (en) | 1981-04-07 | 1981-04-07 | Dyeing of cellulosic fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57167462A JPS57167462A (en) | 1982-10-15 |
| JPH0135955B2 true JPH0135955B2 (en) | 1989-07-27 |
Family
ID=12920017
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56052626A Granted JPS57167462A (en) | 1981-04-07 | 1981-04-07 | Dyeing of cellulosic fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57167462A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3205945A1 (en) * | 1982-02-19 | 1983-09-01 | Hoechst Ag, 6230 Frankfurt | WATER-SOLUBLE DISAZO COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS DYES |
| DE3217388A1 (en) * | 1982-05-08 | 1983-11-17 | Hoechst Ag, 6230 Frankfurt | WATER-SOLUBLE DISAZO COMPOUNDS, METHOD FOR THEIR PRODUCTION AND THEIR USE AS DYES |
| JPS5971120U (en) * | 1982-11-05 | 1984-05-15 | シ−ケ−デイコントロ−ルズ株式会社 | water flow meter |
| JPS59174652A (en) * | 1983-03-24 | 1984-10-03 | Sumitomo Chem Co Ltd | Bisazo compound and dyeing or textile printing using the same |
| CN101812245B (en) * | 2009-11-16 | 2013-06-19 | 天津德凯化工股份有限公司 | Dark blue dye for dyeing nylon |
| CN104195820B (en) * | 2014-08-06 | 2016-05-11 | 浙江理工大学 | A kind of cotton with anti wrinkling agent and its preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS502725A (en) * | 1973-05-11 | 1975-01-13 | ||
| JPS569483A (en) * | 1979-07-06 | 1981-01-30 | Sumitomo Chemical Co | Dyeing of cellulosic fiber |
-
1981
- 1981-04-07 JP JP56052626A patent/JPS57167462A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS502725A (en) * | 1973-05-11 | 1975-01-13 | ||
| JPS569483A (en) * | 1979-07-06 | 1981-01-30 | Sumitomo Chemical Co | Dyeing of cellulosic fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57167462A (en) | 1982-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0167219B1 (en) | Fiber-reactive compound having both pyridiniotriazinyl and vinylsulfone type groups | |
| US4548612A (en) | Halo-triazine and vinylsulfone reactive dye composition with buffer for storage stability | |
| JPS5848672B2 (en) | Dyeing method for cellulose fibers | |
| JPH02132160A (en) | Reactive dye, and its preparation and use | |
| JP3022673B2 (en) | Vinylsulfone / pyrimidine group-containing bifunctional reactive dye | |
| JPH0611869B2 (en) | Reactive dye and its manufacturing method and use | |
| EP1265964A2 (en) | Fiber-reactive disazo compounds | |
| KR100460561B1 (en) | REACTIVE DYE, METHOD OF PRODUCING THE SAME, AND METHOD OF DYEING OR TONING | |
| JPS621036B2 (en) | ||
| KR930009243B1 (en) | Process for the preparation of water soluble pyridone-monoazo compounds | |
| JPH0135955B2 (en) | ||
| KR960000176B1 (en) | Polyazo compound, the process for producing the same and the process for dyeing or printing fiber materials using the same | |
| CA2417234A1 (en) | Yellow reactive monoazo dyes, methods for their preparation and use thereof | |
| JPS6126995B2 (en) | ||
| KR100460822B1 (en) | Reactive dyes, their preparation and use | |
| JPS58204053A (en) | Water-soluble disazo compound, manufacture and use as dye | |
| JPS5880348A (en) | Water-soluble pyridone-azo compound, manufacture and use as dye | |
| KR940005834B1 (en) | Process for the preparation of watersoluble monoazo compounds | |
| JPH08209016A (en) | Reactive dyes,their production and their use | |
| CA2428086A1 (en) | Black dye mixtures of fiber-reactive azo dyes, methods for their preparation and use thereof for dyeing hydroxy- and/or carboxamido-containing fiber material | |
| GB2028360A (en) | Fibre-reactive azo dyes, processes for their manufacture and use thereof | |
| JPH0112787B2 (en) | ||
| JPH07258567A (en) | Disazo dye | |
| JPS59133261A (en) | Bifunctional reactive compound | |
| JPH02222461A (en) | Water-soluble, fiber-reactive dye, and its preparation and use |