JPH0335433B2 - - Google Patents
Info
- Publication number
- JPH0335433B2 JPH0335433B2 JP57071781A JP7178182A JPH0335433B2 JP H0335433 B2 JPH0335433 B2 JP H0335433B2 JP 57071781 A JP57071781 A JP 57071781A JP 7178182 A JP7178182 A JP 7178182A JP H0335433 B2 JPH0335433 B2 JP H0335433B2
- Authority
- JP
- Japan
- Prior art keywords
- dye
- group
- parts
- acid
- dyeing
- 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 - Lifetime
Links
- 238000004043 dyeing Methods 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- -1 β-chloroethyl Chemical group 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 229920003043 Cellulose fiber Polymers 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000000975 dye Substances 0.000 description 41
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 9
- 239000000985 reactive dye Substances 0.000 description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 5
- 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 5
- 210000004243 sweat Anatomy 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 4
- 235000010288 sodium nitrite Nutrition 0.000 description 4
- 125000001174 sulfone group Chemical group 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000010446 mirabilite Substances 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 229940001496 tribasic sodium phosphate Drugs 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 2
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 2
- 238000006193 diazotization reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- LUYAMNYBNTVQJG-UHFFFAOYSA-N 1-chloro-2-(2-chloroethylsulfonyl)ethane Chemical group ClCCS(=O)(=O)CCCl LUYAMNYBNTVQJG-UHFFFAOYSA-N 0.000 description 1
- KVWWLQUBOOFCCS-UHFFFAOYSA-N 1-ethylsulfonylethane;sulfuric acid Chemical compound OS(O)(=O)=O.CCS(=O)(=O)CC KVWWLQUBOOFCCS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- JVMSQRAXNZPDHF-UHFFFAOYSA-N 2,4-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C(N)=C1 JVMSQRAXNZPDHF-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-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
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-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
- TZBROGJRQUABOK-UHFFFAOYSA-N 4-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=C2C(O)=CC(S(O)(=O)=O)=CC2=C1 TZBROGJRQUABOK-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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000010016 exhaust dyeing Methods 0.000 description 1
- 239000004744 fabric Substances 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
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 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
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 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、Ｘはβ−スルフアートエチル、β−チオ
スルフアートエチル、β−ホスフアートエチル、
β−クロルエチル又はビニルを表わし、Ｒは水素
原子、塩素原子又はスルホン酸基を表わし、Ｙは
水素原子又はメチル基を表わし、Z1、Z2、Z3はそ
れぞれ水素原子、塩素原子、メチル基、メトキシ
基、スルホン酸基またはカルボン酸基を表わす。）
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ン基を有
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ン基
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
ン基、β−チオスルフアートエチルスルホン基、
β−スルフアートエチルスルホン基、β−クロル
エチルスルホン基又はビニルスルホン基と、モノ
クロル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。
本発明の染色は、吸尽法の場合、炭酸ソーダ、
第三リン酸ソーダ、苛性ソーダ等の酸結合剤の存
在下に芒硝または食塩を加えた染浴で比較的低い
温度で行なわれる。また、捺染の場合には、たと
えばアルギン酸ナトリウム、澱粉エーテルのよう
な糊料または乳化糊料および炭酸ソーダ、重炭酸
ソーダ、苛性ソーダ、第三リン酸ソーダ、トリク
ロル酢酸ナトリウムまた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ま
たはアルカリを放出する薬剤とともに、所望によ
つては、たとえば尿素のような通常の捺染助剤ま
たは分散剤の添加のもとに繊維上にほどこし、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。
本発明の染料は、たとえば次のようにして製造
することができる。
一般式（）
（式中、Z1、Z2およびZ3は前記の意味を有する。）
で示されるアニリン化合物を塩酸酸性下、０〜５
℃にて亜硝酸ソーダでジアゾ化し、１−アミノ−
８−ヒドロキシナフタレン−３，６−ジスルホン
酸とPH0.5〜3.5、０〜10℃の条件下でカツプリン
グさせて遊離酸の形で一般式（）
で示されるモノアゾ染料を得る。
一方、遊離酸の形で一般式（）
（式中、Ｙは前記の意味を有する）
で示されるフエニレンジアミンスルホン酸化合物
と一般式（）
（式中、ＸおよびＲは前記の意味を有する）
で示されるアニリン化合物とを塩化シアヌルと縮
合させて遊離酸の形で一般式（）
（式中、Ｘ、ＹおよびＲは前記の意味を有する）
で示されるアミノ化合物を得、このアミノ化合物
を塩酸酸性下０〜５℃にて亜硝酸ソーダでジアゾ
化し、これと先に得たモノアゾ染料（）を重炭
酸ソーダアルカリ中０〜10℃にてカツプリングさ
せることによつて一般式（）で示される染料を
得ることができる。
本発明において、使用できるアニリン化合物
（）としては、たとえばアニリン、アニリン−
２，３、又は４−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又は３又は４−クロルアニ
リンがあげられる。
ジアミン成分（）としてはメタフエニレンジ
アミンスルホン酸あるいはメタトルイレンジアミ
ンスルホン酸があげられる。
アミン成分（）としては、たとえばアニリン
−２−β−スルフアートエチルスルフオン、５−
クロルアニリン−２−β−スルフアートエチルス
ルフオン、５−スルホアニリン−２−β−スルフ
アートエチルスルフオン、アニリン−２−β−チ
オスルフアートエチルスルフオン、５−クロルア
ニリン−２−β−チオスルフアートエチルスルフ
オン、５−スルホアニリン−２−β−チオスルフ
アートエチルスルホン、アニリン−２−β−ホス
フアートエチルスルホン、５−クロルアニリン−
２−β−ホスフアートエチルスルフオン、５−ス
ルホアニリン−２−β−ホスフアートエチルスル
フオン、アニリン−２−ビニルスルフオン、５−
クロルアニリン−２−ビニルスルフオン、５−ス
ルホアニリン−２−ビニルスルホン、アニリン−
２−β−クロルエチルスルフオン、５−クロルア
ニリン−２−β−クロルエチルスルフオン、５−
スルホアニリン−２−β−クロルエチルスルフオ
ンがあげられる。
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ン基を有するア
ゾ系の濃青色反応染料に比して、特に塩素堅牢
度、耐光堅牢度、汗日光堅牢度にすぐれている。
特に最近一般家庭における洗濯に塩素系漂白剤を
使用することが普及してきていることを考える
と、塩素堅牢度にすぐれる本発明染料の価値は高
い。また、耐光、汗日光堅牢度にすぐれること
は、スポーツウエア等外装着の染色に好適であ
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もわずかであること
から廃水処理の面でも有利である利点を有する。
また、本発明染料は染色温度の影響を受けにく
いため、再現性にすぐれており、更に均染性、洗
たく時の堅牢性においてもすぐれる特徴を有して
いる。
本発明染料の中でも、特に一般式（）におい
てスルホン酸基がアミノ基に対してＰ−位にある
ものが色相的に好ましいものが得られ、又塩素堅
牢度もＯ−位にスルホン酸基を有するものに比べ
ても同等またはそれ以上にすぐれている。
本発明に近似する染料として、たとえば特公昭
39−11779号公報には
で示されるモノクロルトリアジニル型反応染料が
記載されている。
しかし、この染料を用いて得られた染色物の酸
安定性（試験法は染布を１％酢酸に30分浸漬後、
バースピロメータを使用して37±２℃の温度で
125ｇ／cm2で６時間処理する）は、本発明染料染
色物に比して劣つており、さらに染色温度に高温
を要し、また吸尽染色適性に欠けるという欠点を
有しているため、実用的には決して充分とは言え
ない。
次に本発明方法を実施例によつて説明する。
文中、部は重量部を表わす。
実施例 １
式(1)
（λmax＝600nｍ、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 １
〔実施例１の染料(1)の合成剤〕
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
アミンスルホン酸4.70部を界面活性剤水溶液50部
中でPH６〜７に１〜２時間、０〜５℃に保つこと
により第一縮合を行い、次にアニリン−２−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。35.4部の染料(1)を得た。
実施例 ２〜19
実施例１において染料(1)の代わりに下記(2)〜
（21）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：Ａ欄、モノアゾ染料
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。
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: (wherein, X is β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl,
β-chloroethyl or vinyl; R represents a hydrogen atom, a chlorine atom, or a sulfonic acid group; Y represents a hydrogen atom or a methyl group; Z 1 , Z 2 , and Z 3 represent a hydrogen atom, a chlorine atom, and a methyl group, respectively. , represents a methoxy group, a sulfonic acid group or a carboxylic acid group. ) This is a method for dyeing cellulose fibers, which is characterized by using the dye shown in the following. 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-sulfatoethyl sulfone group can be applied to dyeing textile materials as so-called vinyl sulfone type reactive dyes. However, dyed products using azo deep blue reactive dyes having a β-sulfatoethyl sulfone 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 above general formula (), that is, the β-sulfatoethyl sulfone group as the reactive group, , β-thiosulfatoethylsulfone group,
It has been found that disazo dyes having a β-sulfatoethylsulfone group, a β-chloroethylsulfone group or a vinylsulfone group and a monochlorotriazinyl group 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 a monochlorotriazinyl group 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. In the case of the exhaust method, the dyeing of the present invention uses soda carbonate,
It is carried out at relatively low temperatures in a dye bath containing mirabilite or common salt in the presence of an acid binder such as tribasic sodium phosphate or caustic soda. In the case of printing, pastes such as, for example, sodium alginate, starch ethers or emulsifying pastes and soda carbonate, bicarbonate soda, caustic soda, tribasic sodium phosphate, sodium trichloroacetate or corresponding potassium or alkaline earth compounds can also be used. along with an alkaline or alkali-releasing agent such as, optionally with the addition of customary printing aids or dispersants such as urea, drying and especially in the presence of water vapor. It can be dyed by subjecting it to heat treatment. The dye of the present invention can be produced, for example, as follows. General formula () (In the formula, Z 1 , Z 2 and Z 3 have the above-mentioned meanings.) The aniline compound represented by
Diazotized with sodium nitrite at ℃ to give 1-amino-
It is coupled with 8-hydroxynaphthalene-3,6-disulfonic acid under the conditions of pH 0.5 to 3.5 and 0 to 10°C to form a free acid with the general formula () A monoazo dye represented by is obtained. On the other hand, in the free acid form the general formula () (In the formula, Y has the above meaning) and a phenylenediamine sulfonic acid compound represented by the general formula () (wherein, X and R have the above-mentioned meanings) is condensed with cyanuric chloride to form a free acid of the general formula () (In the formula, X, Y and R have the above-mentioned meanings.) This amino compound was diazotized with sodium nitrite at 0 to 5°C under hydrochloric acid acidity, and this and the previously obtained The dye represented by the general formula () can be obtained by coupling the monoazo dye () in an alkali bicarbonate solution at 0 to 10°C. In the present invention, examples of the aniline compound () that can be used include aniline, aniline-
2, 3, or 4-sulfonic acid, anthranilic acid,
Examples include para-toluidine sulfonic acid, 3-amino-6-chlorotoluene-4-sulfonic acid, 2-chloro-para-toluidine-5-sulfonic acid, para-anisidine orthosulfonic acid, and 2-, 3-, or 4-chloroaniline. Examples of the diamine component (2) include metaphenylenediaminesulfonic acid and metatolylenediaminesulfonic acid. Examples of the amine component () include aniline-2-β-sulfatoethylsulfone, 5-
Chloraniline-2-β-sulfatoethylsulfone, 5-sulfoaniline-2-β-sulfatoethylsulfone, aniline-2-β-thiosulfatoethylsulfone, 5-chloroaniline-2 -β-thiosulfatoethylsulfone, 5-sulfoaniline-2-β-thiosulfatoethylsulfone, aniline-2-β-phosphateethylsulfone, 5-chloroaniline-
2-β-phosphatoethylsulfone, 5-sulfoaniline-2-β-phosphatoethylsulfone, aniline-2-vinylsulfon, 5-
Chloraniline-2-vinylsulfone, 5-sulfoaniline-2-vinylsulfone, aniline-
2-β-Chlorethylsulfon, 5-chloroaniline-2-β-chloroethylsulfon, 5-
Examples include sulfoaniline-2-β-chloroethylsulfon. The thus obtained dye of the present invention has particularly high chlorine fastness, light fastness, sweat and sunlight fastness, compared to conventional azo deep blue reactive dyes having a β-sulfatoethyl sulfone group. Excellent.
Especially considering that the use of chlorine bleach in household laundry has recently become widespread, the value of the dye of the present invention, which has excellent chlorine fastness, is high. Furthermore, the excellent light fastness, sweat fastness and sunlight fastness are suitable for dyeing external wear such as sportswear. Furthermore, since the dye of the present invention exhibits a high exhaustion rate,
Not only can dyed products with high density be obtained, but also a small amount of dye remains in the dye bath, which is advantageous in terms of waste water treatment. Furthermore, the dye of the present invention is not easily affected by dyeing temperature, so it has excellent reproducibility, and also has excellent characteristics in level dyeing property and fastness when washed. Among the dyes of the present invention, those in which the sulfonic acid group is located at the P-position with respect to the amino group in the general formula () are particularly preferable in terms of hue, and also have good chlorine fastness. It is as good as or better than what we have. As a dye similar to the present invention, for example,
Publication No. 39-11779 A monochlorotriazinyl type reactive dye represented by is described. However, the acid stability of dyed products obtained using this dye (the test method is to immerse the dyed fabric in 1% acetic acid for 30 minutes,
at a temperature of 37 ± 2 °C using a bar spirometer.
(processed at 125 g/cm 2 for 6 hours) is inferior to the dyed product of the present invention, and has the disadvantages of requiring a high dyeing temperature and lacking in exhaustion dyeing suitability. It can never be said to be sufficient in practical terms. Next, the method of the present invention will be explained with reference to examples. In the text, parts represent parts by weight. Example 1 Formula (1) (λmax = 600 nm, however, in an aqueous solvent, hereinafter measured under the same conditions) Dissolve 0.3 parts of the dye shown in 200 parts of water to obtain 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 1 [Synthesizing agent for dye (1) of Example 1] 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 4.70 parts of m-phenylenediaminesulfonic acid were brought to pH 6-7 in 50 parts of an aqueous surfactant solution and kept at 0-5°C for 1-2 hours to carry out the first condensation, and then Aniline-2-β-
Added 6.95 parts of sulfate ethyl sulfone, 9%
25 while keeping the pH between 5 and 5.5 with a bicarbonate of soda solution.
The second condensation is carried out by stirring overnight at ~30°C. 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 the temperature to 50 to 55°C, add sodium chloride to the solution for salting out, filter, wash, and dry at 60°C. 35.4 parts of dye (1) were obtained. Examples 2-19 In Example 1, instead of dye (1), the following (2)-
Dyeing was carried out in the same manner except that the dye (21) was used. A deep blue, intense dyeing with excellent fastness properties was obtained. The following dyes are azo component: A column, diazo component of monoazo dye [compound of the above general formula ()]: B
Column, diazo component of disazo dye Aniline compound [compound of the above general formula ()] column C, and λmax of the disazo dye solution
(Column D).
【表】【table】
【表】
実施例 22
実施例１において染料(1)のメタフエニレンジア
ミンスルホン酸の代わりにメタトルイレンジアミ
ンスルホン酸を使用して他は同様の方法で合成し
た得た式（22）
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20分経過後、第三リン酸ソーダ３部を加え
る。
その温度で１時間染色する。染色終了後、水
洗、ソーピングを行つて塩素、耐光、汗日光堅牢
度のすぐれた濃青色の染色物を得た。
染料（22）において、アニリン−２−β−スル
フアートエチルスルホンの代わりに、アニリン−
２−β−ホスフアート、クロル又はビニルスルホ
ン、５−スルホ又はクロルアニリン−２−β−ス
ルフアートエチルスルホンを、あるいはアニリン
−４−スルホン酸の代わりにアニリン−２、又は
３−スルホン酸あるいは３又は４−クロルアニリ
ンを使用して得られる染料も同様の性能を有する
染色物を与える。
比較例 １
実施例１において染料(1)のメタフエニレンジア
ミンスルホン酸の代わりにパラフエニレンジアミ
ンスルホン酸を使用して同様の方法で合成して得
た式（23）
で示される染料（λmax＝630nｍ）を用いて同様
に染色した。帯青緑色の染色物を与え、本発明染
料の様な青色の色調は得られなかつた。[Table] Example 22 The obtained formula (22) was synthesized in the same manner as in Example 1 except that meta-tolylene diamine sulfonic acid was used instead of meta-phenylene diamine sulfonic acid in dye (1). 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℃. Then, after 20 minutes, 3 parts of tribasic sodium phosphate is added. Dye for 1 hour at that temperature. After dyeing, washing with water and soaping were performed to obtain a deep blue dyed product with excellent fastness to chlorine, light, sweat, and sunlight. In dye (22), aniline-2-β-sulfatoethylsulfone was replaced with aniline-2-β-sulfatoethylsulfone.
2-β-phosphate, chloro or vinylsulfone, 5-sulfo or chloroaniline-2-β-sulfatoethylsulfone, or aniline-2, or 3-sulfonic acid or 3-sulfonic acid instead of aniline-4-sulfonic acid. Alternatively, dyes obtained using 4-chloroaniline also give dyeings with similar performance. Comparative Example 1 Formula (23) obtained by synthesizing in the same manner as in Example 1 using paraphenylenediaminesulfonic acid instead of metaphenylenediaminesulfonic acid in dye (1) It was dyed in the same manner using the dye shown in (λmax=630 nm). It gave a bluish-green dyeing, and no blue tones were obtained as with the dyes of the invention.
Claims (1)
スルフアートエチル、β−ホスフアートエチル、
β−クロルエチル又はビニルを表わし、Ｒは水素
原子、塩素原子又はスルホン酸基を表わし、Ｙは
水素原子又はメチル基を表わし、Z1、Z2、Z3はそ
れぞれ水素原子、塩素原子、メチル基、メトキシ
基、スルホン酸基またはカルボン酸基を表わす。） 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: (wherein, X is β-sulfatoethyl, β-thiosulfatoethyl, β-phosphatoethyl,
β-chloroethyl or vinyl; R represents a hydrogen atom, a chlorine atom, or a sulfonic acid group; Y represents a hydrogen atom or a methyl group; Z 1 , Z 2 , and Z 3 represent a hydrogen atom, a chlorine atom, and a methyl group, respectively. , represents a methoxy group, a sulfonic acid group or a carboxylic acid group. ) A dyeing method for cellulose fibers characterized by using the dye shown in the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57071781A JPS58187458A (en) | 1982-04-27 | 1982-04-27 | Dyeing of cellulosic fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57071781A JPS58187458A (en) | 1982-04-27 | 1982-04-27 | Dyeing of cellulosic fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58187458A JPS58187458A (en) | 1983-11-01 |
| JPH0335433B2 true JPH0335433B2 (en) | 1991-05-28 |
Family
ID=13470449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57071781A Granted JPS58187458A (en) | 1982-04-27 | 1982-04-27 | Dyeing of cellulosic fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58187458A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3420467A1 (en) * | 1984-06-01 | 1985-12-05 | Basf Ag, 6700 Ludwigshafen | REACTIVE DYES |
-
1982
- 1982-04-27 JP JP57071781A patent/JPS58187458A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58187458A (en) | 1983-11-01 |
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