JPS6114276B2 - - Google Patents
Info
- Publication number
- JPS6114276B2 JPS6114276B2 JP56094556A JP9455681A JPS6114276B2 JP S6114276 B2 JPS6114276 B2 JP S6114276B2 JP 56094556 A JP56094556 A JP 56094556A JP 9455681 A JP9455681 A JP 9455681A JP S6114276 B2 JPS6114276 B2 JP S6114276B2
- Authority
- JP
- Japan
- Prior art keywords
- fibers
- post
- fastness
- dyed
- water
- 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
- 239000000835 fiber Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 150000003839 salts Chemical group 0.000 claims description 12
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical class C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 10
- 229920003043 Cellulose fiber Polymers 0.000 claims description 8
- 229920006317 cationic polymer Polymers 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000985 reactive dye Substances 0.000 claims description 8
- 238000004043 dyeing Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229920001519 homopolymer Polymers 0.000 claims description 5
- 239000002657 fibrous material Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims 1
- 238000012805 post-processing Methods 0.000 claims 1
- 239000000047 product Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 239000007787 solid Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 229920000768 polyamine Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 229920000742 Cotton Polymers 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 239000011345 viscous material Substances 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 6
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 6
- 238000009472 formulation Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003623 enhancer Substances 0.000 description 3
- 238000005562 fading Methods 0.000 description 3
- 229920002972 Acrylic fiber Polymers 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 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
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- SPSSDDOTEZKOOV-UHFFFAOYSA-N 2,3-dichloroquinoxaline Chemical group C1=CC=C2N=C(Cl)C(Cl)=NC2=C1 SPSSDDOTEZKOOV-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- SUPFNMXTAGSTIP-UHFFFAOYSA-N 2-chloro-4,6-difluoropyrimidine Chemical group FC1=CC(F)=NC(Cl)=N1 SUPFNMXTAGSTIP-UHFFFAOYSA-N 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- IHDBZCJYSHDCKF-UHFFFAOYSA-N 4,6-dichlorotriazine Chemical group ClC1=CC(Cl)=NN=N1 IHDBZCJYSHDCKF-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ORLGPUVJERIKLW-UHFFFAOYSA-N 5-chlorotriazine Chemical group ClC1=CN=NN=C1 ORLGPUVJERIKLW-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 description 1
- 125000005265 dialkylamine group Chemical group 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical group C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- MKGDCBYWZMUECD-UHFFFAOYSA-N ethanesulfonamide;sulfuric acid Chemical group OS(O)(=O)=O.CCS(N)(=O)=O MKGDCBYWZMUECD-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 210000004243 sweat Anatomy 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
Landscapes
- Coloring (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
本発明はセルロース系繊維染色物の後処理法に
関する。更に詳しく述べるならば、本発明はセル
ロース系繊維又はセルロース系繊維と他の繊維か
らなる繊維材料を反応性染料で染色した染色物を
後処理して、その染色堅牢度を向上せしめる方法
に関する。
従来よりセルロース系繊維染色物の湿潤堅牢度
を増進させる方法としては、湿潤堅牢度増進剤を
使用する方法があり、ポリアルキルポリアミンと
ジシアンジアミド等を縮合させて得られるポリア
ミン系カチオン樹脂型のものが最も多く用いられ
ている。ポリアミン系カチオン樹脂としては、既
に米国特許第2649354号に記載されてる如くポリ
エチレンポリアミンとジシアンジアミドとから加
熱縮合してなる縮合樹脂や、特公昭36−1736号に
記載されている如くポリエチレンポリアミン、ジ
シアンジアミド、尿素の三者の縮合樹脂がある。
これらはいずれも湿潤堅牢度の増進効果において
優れている。しかしながら、ポリアミン系カチオ
ン樹脂により後処理された反応性染料染色物は、
反応性染料の最大の特徴である色相の鮮明さを損
う（色相変化）ことがしばしば認められる。また
水道水やプール水に含まれる塩素イオンによつて
染色物が変退色する現象（耐塩素堅牢度不良）も
しばしば認められ、更には日光堅牢度においても
劣るものであつた。
これらポリアミン系カチオン樹脂の欠点を解消
するために近年、ジアルキルアミンとエピハロヒ
ドリンとの反応によつて得られるカチオン性ポリ
マーで染色物を後処理する方法が開発された。し
かしながらこのカチオン性ポリマーで染色物を後
処理した場合、ポリアミン系カチオン樹脂の欠点
であつた、色相変化、日光堅牢度不良の問題につ
いてはほぼ解消されるものの、湿潤堅牢度増進効
果はポリアミン系カチオン樹脂に比べ相当に劣
り、耐塩素堅牢度についても不十分である。その
ために高湿潤堅牢度を要求される染色物にはポリ
アミン系カチオン樹脂を、そしてそれ程高い湿潤
堅牢度を要求されない染色物には、カチオン性ポ
リマーをというように使いわけされているのが現
状である。
本発明者らは従来のかかる欠点を改良して、使
いわけの必要のないすぐれた後処理剤について鋭
意研究を重ねた結果、ある種のカチオン性ポリマ
ーが染色物の色相の鮮明さを損うことなく、良好
な湿潤堅牢度増進効果を発揮するとともに、耐塩
素堅牢度、日光堅牢度に優れていることを発見
し、本発明を完成した。
即ち本発明によれば、セルロース系繊維又はこ
れと他の繊維からなる繊維材料の反応性染料によ
る染色物を、ビニルイミダゾールの酸塩もしくは
第四級塩の単独重合体及び／又はこれと共重合可
能なコモノマーとの共重合体、又は前記単独重合
体及び／又は共重合体と下記一般式(2)で示される
カチオン性ポリマーとの混合物よりなる後処理剤
を用いて後処理することを特徴とするセルロース
系繊維染色物の後処理が提供されるのである。
上式中、R3及びR4は同一又は相異るものであ
つてよく、それぞれ低級アルキル基を表わし、Ｘ
はハロゲン原子又はHSO4を表わす。
本発明に係るビニルイミダゾールの酸塩を構成
する酸類としては、塩酸、硫酸、燐酸などの無機
酸及び酢酸、ギ酸、酪酸などの有機酸がある。四
級化剤としては、塩化メチル、塩化ベンジル、ジ
メチル硫酸、ジエチル硫酸、エチレンクロルヒド
リンなどがある。また、中和又は四級化反応は全
て公知の方法で行える。ビニルイミダゾールの酸
塩又は四級塩と共重合させる化合物としては、ジ
メチルアミノエチルメタクリレート、ジエチルア
ミノエチルメタクリレート、ヒドロキシエチルメ
タクリレート、酢酸ビニル、アクリルアミド、ア
ルキルメタクリレート、クロルメチル化スチレ
ン、ビニルピリジンなどを用いることができる
が、これらに限定されるものではない。これらの
コモノマーは任意の割合で用いることができる。
ビニルイミダゾールの酸塩または第四級塩の重合
物及び、他のコモノマーとの共重合物は従来公知
の方法で製造できる。例えば、ビニルイミダゾー
ルの酸塩又は四級塩と水とが共存する混合液を過
硫酸カリウムの様な重合触媒の存在下で重合させ
ることにより容易に得られる。
本発明に使用する一般式(2)のカチオンポリマー
は次の一般式(3)
（式中、R3，R4及びＸは前記規定に同一のも
のを表わす）で表わされる化合物を公知の方法で
重合することによつて製造できる。例えば、ジア
リルジメチルアンモニウムクロリドと水とが共存
する混合液を過硫酸カリウムの様な重合触媒の存
在下で環化重合させることにより容易に得られ
る。ビニルイミダゾールの酸塩もしくは四級塩の
単独重合体及び／又は他のコモノマーとの共重合
体と一般式(2)で表わされるカチオンポリマーとの
配合は任意の割合で行うことができるが、前者を
主成分とした方が好ましい。
本発明の処理法は従来公知の湿潤堅牢度増進剤
に用いられる方法と同様に実施することができ
る。本発明における後処理剤の使用濃度は0.01％
〜５％の範囲でよいが、0.05〜２％であるのが好
ましい。染色物に対しては１％〜10％の範囲が良
い。なお処理液のPHは、PH３〜11の範囲で自由に
選択できるが、PH７〜９とするのが好ましい。ま
た処理時の温度は20〜70℃でよく、時間は10分な
いし30分でよい。処理後の乾燥は自然乾燥、加熱
乾燥のいずれでもよい。
本発明が適用されるセルロース系繊維及び該繊
維と他繊維との混合繊維としては、木綿、ビスコ
ースレーヨン、木綿とポリエステルとの混合繊
維、木綿とポリアミド繊維の混合繊維、ビスコー
スレーヨンとポリエステル繊維との混合繊維、木
綿とアクリル繊維との混合繊維等があげられる。
また反応性染料の例をあげると、ビニルスルホン
基、ジクロロトリアジン基、モノクロロトリアジ
ン基、ジクロロキノキサリン基、モノクロロジフ
ルオロピリミジン基、サルフエートエチルスルホ
ンアミド基等を有する有機染料があげられる。
以下本発明について例をあげ説明するが、本発
明はこれらのものに限定されるものではない。ま
た例中の部及び％はそれぞれ重量部及び重量％を
示す。
合成例 １
撹拌器、温度計、冷却器、滴下ロートを備えた
反応容器に１―ビニルイミダゾール85ｇ（0.904
モル）を仕込み、発熱に注意しながら111.8ｇ
（0.886モル）のジメチル硫酸を55〜60℃の温度を
保ちつつ、２時間を要して滴下する。滴下後、55
〜60℃で１時間撹拌反応を続け、次いで130ｇの
水を加え、80〜85℃とし、過硫酸カリウム1.5ｇ
の存在下で窒素ガスを通じながら４時間撹拌重合
を行ない、黄褐色の粘稠物を得た。この生成物
200ｇを200mlのアセトン中に注いで淡黄色沈澱を
生じさせ、この沈澱を別し、更に300mlのアセ
トンで２回洗うと吸湿性の有る淡黄色固体ポリマ
ー117.6ｇが得られた。この淡黄色固体ポリマー
40ｇを水160ｇにて溶解し、生成物Ａとした（黄
色透明で微粘稠液状）。
合成例 ２
撹拌器、温度計、冷却器、滴下ロートを備えた
反応容器に１―ビニルイミダゾール64.5ｇ
（0.686モル）、ジメチルアミノエチルメタクリレ
ート28ｇ（0.17モル）を投入し、発熱に注意しつ
つ、107ｇ（0.84モル）のジメチル硫酸を55〜60
℃の温度にて２時間を要して滴下し、滴下後55〜
60℃で１時間撹拌反応を続けた。次いで200ｇの
水を加え80〜85℃とし、過硫酸カリウム1.5ｇの
存在下で窒素ガスを通じながら４時間撹拌重合を
行ない、黄褐色の粘稠物を得た。この粘稠物200
ｇを200mlのアセトン中に注いで淡黄色沈澱を得
る。この沈澱を別して、更に300mlのアセトン
で２回洗うと吸湿性のある淡黄色固体ポリマー99
ｇが得られた。この淡黄色固体ポリマー40ｇを水
160ｇに溶解して、生成物Ｂとした（黄色透明粘
稠液状）。
合成例 ３
撹拌器、温度計、冷却器、滴下ロートを備えた
反応容器に１―ビニルイミダゾール43ｇ（0.45モ
ル）、ジメチルアミノエチルメタクリレート56ｇ
（0.357モル）を投入し、発熱に注意しながら
100.5ｇ（0.797モル）のジメチル硫酸を55〜60℃
の温度を保ちつつ２時間を要して滴下し、滴下後
55〜60℃で１時間撹拌反応を続けた。次いで200
ｇの水を加え80〜85℃とし、過硫酸カリウム1.5
ｇの存在下で窒素ガスを通じながら４時間撹拌重
合を行ない、黄褐色の粘稠物を得た。この粘稠物
200ｇを2000mlのアセトン中に注ぐと淡黄色沈澱
が生じた。沈澱を別して更に300mlのアセトン
で２回洗うと吸湿性の有る淡黄色固体ポリマー
97.6ｇが得られた。この淡黄色固体ポリマー40ｇ
を水160ｇにて溶解し、生成物Ｃとした（淡黄色
透明で粘稠液状）。
合成例 ４
撹拌器、温度計、冷却器、滴下ロートを備えた
反応容器にジアリルアミン97.2ｇ（11モル）を投
入し、発熱に注意しながら123.7ｇ（0.98モル）
のジメチル硫酸を55〜60℃の温度に保ちつつ２時
間を要して滴下し、滴下後55〜60℃で１時間撹拌
反応を続けた。次いで水95ｇを加え50〜55℃と
し、過硫酸カリウム1.7ｇの存在下で窒素ガスを
通じながら８時間撹拌重合を行ない、淡黄色の粘
稠物を得た。この粘稠物200ｇを2000mlのアセト
ン中に注ぐと白色沈澱が生じた。この沈澱を別
して更に300mlのアセトンで２回洗うと吸湿性の
有る白色固体ポリマー97.3ｇが得られた。この白
色固体ポリマー40ｇを水160ｇにて溶解し、生成
物Ｄとした（無色透明で微粘稠液状）。
配合例 １
合成例１で得られた淡黄色固体ポリマー30ｇ
と、合成例４で得られた白色固体ポリマー10ｇと
を水160ｇにて溶解し、配合物Ｅとした（黄色透
明、微粘稠液状）。
配合例 ２
合成例１で得られた淡黄色固体ポリマー20ｇと
合成例４で得られた白色固体ポリマー20ｇとを水
160ｇにて溶解し配合物Ｆとした（黄色透明、微
粘稠液状）。
配合例 ３
合成例３で得られた淡黄色固体ポリマー30ｇと
合成例４で得られた白色ポリマー10ｇとを水160
ｇで溶解し、配合物Ｇとした（淡黄色透明粘稠液
状）。
試験例 １
本発明品を反応性染料にて染色した綿布に適用
した場合の染色堅牢度を下記の方法に従つて試験
した。
(1―1) 染色物の調製
綿メリヤスを反応性染料にて常法に従つて染色
し、次いでリポトールRK―５〔日華化学(株)社
製〕の２ｇ/水溶液で90℃にて10分間洗浄後、
水洗、乾燥した。
The present invention relates to a method for post-treatment of dyed cellulosic fibers. More specifically, the present invention relates to a method for improving the color fastness of a dyed product obtained by dyeing cellulosic fibers or a fibrous material composed of cellulosic fibers and other fibers with a reactive dye by post-treating the dyed product. Conventionally, there is a method to improve the wet fastness of dyed cellulose fibers by using a wet fastness enhancer, and a polyamine-based cationic resin type obtained by condensing a polyalkyl polyamine with dicyandiamide, etc. Most commonly used. Examples of polyamine-based cationic resins include condensation resins obtained by heating and condensing polyethylene polyamine and dicyandiamide as already described in U.S. Pat. No. 2,649,354, and polyethylene polyamine, dicyandiamide, There is a tripartite condensation resin of urea.
All of these are excellent in improving wet fastness. However, reactive dye dyeings post-treated with polyamine-based cationic resins
It is often observed that the sharpness of hue, which is the most characteristic of reactive dyes, is impaired (hue change). Furthermore, the phenomenon of discoloration and fading of dyed products due to chlorine ions contained in tap water or pool water (poor chlorine fastness) was often observed, and furthermore, the fastness to sunlight was also poor. In order to overcome the drawbacks of these polyamine-based cationic resins, a method has recently been developed in which dyed products are post-treated with a cationic polymer obtained by the reaction of dialkylamine and epihalohydrin. However, when dyed items are post-treated with this cationic polymer, the disadvantages of polyamine-based cationic resins, such as hue change and poor sunlight fastness, are almost eliminated; It is considerably inferior to resins, and its chlorine fastness is also insufficient. For this reason, at present, polyamine-based cationic resins are used for dyed products that require high wet fastness, and cationic polymers are used for dyed products that do not require such high wet fastness. be. The inventors of the present invention improved the conventional drawbacks and conducted extensive research into an excellent post-treatment agent that does not need to be used selectively.As a result, we found that certain cationic polymers impair the sharpness of the hue of dyed products. The present invention was completed based on the discovery that it exhibits a good wet fastness enhancing effect without any problems, and has excellent chlorine fastness and sunlight fastness. That is, according to the present invention, dyeings of cellulose fibers or fiber materials made of cellulose fibers and other fibers with reactive dyes are dyed with a homopolymer and/or a copolymer of an acid salt or a quaternary salt of vinylimidazole. It is characterized by post-treatment using a post-treatment agent consisting of a copolymer with a possible comonomer, or a mixture of the homopolymer and/or copolymer and a cationic polymer represented by the following general formula (2). A post-treatment of dyed cellulose fibers is provided. In the above formula, R 3 and R 4 may be the same or different and each represents a lower alkyl group, and
represents a halogen atom or HSO 4 . The acids constituting the vinyl imidazole acid salt according to the present invention include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, and organic acids such as acetic acid, formic acid, and butyric acid. Examples of quaternizing agents include methyl chloride, benzyl chloride, dimethyl sulfate, diethyl sulfate, and ethylene chlorohydrin. Further, all of the neutralization or quaternization reactions can be performed by known methods. As the compound to be copolymerized with the acid salt or quaternary salt of vinylimidazole, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, hydroxyethyl methacrylate, vinyl acetate, acrylamide, alkyl methacrylate, chloromethylated styrene, vinylpyridine, etc. can be used. However, it is not limited to these. These comonomers can be used in any proportion.
Polymers of acid salts or quaternary salts of vinylimidazole and copolymers with other comonomers can be produced by conventionally known methods. For example, it can be easily obtained by polymerizing a mixed solution in which an acid salt or quaternary salt of vinylimidazole and water coexist in the presence of a polymerization catalyst such as potassium persulfate. The cationic polymer of general formula (2) used in the present invention has the following general formula (3). It can be produced by polymerizing a compound represented by the formula (wherein R 3 , R 4 and X are the same as defined above) by a known method. For example, it can be easily obtained by cyclopolymerizing a mixture of diallyldimethylammonium chloride and water in the presence of a polymerization catalyst such as potassium persulfate. The homopolymer and/or copolymer of vinylimidazole acid salt or quaternary salt and/or copolymer with other comonomers and the cationic polymer represented by general formula (2) can be blended in any proportion, but the former It is preferable to use as the main component. The processing method of the present invention can be carried out in a manner similar to that used for conventionally known wet fastness enhancers. The concentration of post-treatment agent used in the present invention is 0.01%
The content may range from 5% to 5%, but preferably from 0.05 to 2%. For dyed products, a range of 1% to 10% is good. Note that the PH of the treatment liquid can be freely selected within the range of PH3 to 11, but is preferably PH7 to 9. Further, the temperature during treatment may be 20 to 70°C, and the time may be 10 to 30 minutes. Drying after treatment may be either natural drying or heat drying. Cellulose fibers and mixed fibers of these fibers and other fibers to which the present invention is applied include cotton, viscose rayon, mixed fibers of cotton and polyester, mixed fibers of cotton and polyamide fibers, and viscose rayon and polyester fibers. Examples include mixed fibers with cotton and acrylic fibers, and mixed fibers with cotton and acrylic fibers.
Further, examples of reactive dyes include organic dyes having a vinyl sulfone group, a dichlorotriazine group, a monochlorotriazine group, a dichloroquinoxaline group, a monochlorodifluoropyrimidine group, a sulfate ethyl sulfonamide group, and the like. The present invention will be explained below by giving examples, but the present invention is not limited to these. Further, parts and % in the examples indicate parts by weight and % by weight, respectively. Synthesis Example 1 85 g of 1-vinylimidazole (0.904
mol) and add 111.8g while being careful not to generate heat.
(0.886 mol) of dimethyl sulfate was added dropwise over 2 hours while maintaining the temperature at 55-60°C. After dripping, 55
Continue the stirring reaction at ~60°C for 1 hour, then add 130g of water to bring the temperature to 80-85°C and add 1.5g of potassium persulfate.
Polymerization was carried out with stirring in the presence of nitrogen gas for 4 hours to obtain a yellowish brown viscous substance. this product
200 g was poured into 200 ml of acetone to form a pale yellow precipitate, which was separated and washed twice with 300 ml of acetone to yield 117.6 g of a hygroscopic pale yellow solid polymer. This pale yellow solid polymer
40g was dissolved in 160g of water to obtain Product A (transparent yellow, slightly viscous liquid). Synthesis Example 2 64.5 g of 1-vinylimidazole was placed in a reaction vessel equipped with a stirrer, thermometer, condenser, and dropping funnel.
(0.686 mol) and 28 g (0.17 mol) of dimethylaminoethyl methacrylate, and while being careful not to generate heat, 107 g (0.84 mol) of dimethyl sulfuric acid was added to 55 to 60 g of dimethyl sulfate.
Dropped at a temperature of ℃ for 2 hours, after dropping 55 ~
The reaction was continued with stirring at 60°C for 1 hour. Next, 200 g of water was added and the temperature was raised to 80 to 85° C., and polymerization was carried out with stirring for 4 hours while passing nitrogen gas in the presence of 1.5 g of potassium persulfate to obtain a yellowish brown viscous material. This viscous substance 200
Pour g into 200 ml of acetone to obtain a pale yellow precipitate. Separate this precipitate and wash it twice with 300 ml of acetone to form a hygroscopic pale yellow solid polymer99.
g was obtained. Add 40g of this pale yellow solid polymer to water.
It was dissolved in 160 g to give product B (yellow transparent viscous liquid). Synthesis Example 3 43 g (0.45 mol) of 1-vinylimidazole and 56 g of dimethylaminoethyl methacrylate were placed in a reaction vessel equipped with a stirrer, thermometer, condenser, and dropping funnel.
(0.357 mol), being careful not to generate heat.
100.5g (0.797mol) dimethyl sulfate at 55-60℃
It took 2 hours to drip while maintaining the temperature of
The reaction was continued with stirring at 55-60°C for 1 hour. then 200
Add 1.5g of water and bring to 80-85℃, add 1.5g of potassium persulfate.
Polymerization was carried out with stirring for 4 hours while passing nitrogen gas in the presence of 100 g, to obtain a yellowish brown viscous substance. this viscous substance
When 200 g was poured into 2000 ml of acetone, a pale yellow precipitate formed. Separate the precipitate and wash twice with 300ml of acetone to obtain a hygroscopic light yellow solid polymer.
97.6g was obtained. 40g of this pale yellow solid polymer
was dissolved in 160 g of water to obtain Product C (light yellow, transparent, viscous liquid). Synthesis Example 4 97.2 g (11 mol) of diallylamine was added to a reaction vessel equipped with a stirrer, thermometer, condenser, and dropping funnel, and 123.7 g (0.98 mol) was added while being careful not to generate heat.
dimethyl sulfuric acid was added dropwise over a period of 2 hours while maintaining the temperature at 55-60°C, and after the dropwise addition, the stirring reaction was continued at 55-60°C for 1 hour. Next, 95 g of water was added, the temperature was raised to 50-55°C, and polymerization was carried out with stirring for 8 hours while passing nitrogen gas in the presence of 1.7 g of potassium persulfate, to obtain a pale yellow viscous substance. When 200 g of this viscous material was poured into 2000 ml of acetone, a white precipitate formed. The precipitate was separated and washed twice with 300 ml of acetone to obtain 97.3 g of a hygroscopic white solid polymer. 40 g of this white solid polymer was dissolved in 160 g of water to obtain Product D (colorless and transparent, slightly viscous liquid). Formulation Example 1 30g of pale yellow solid polymer obtained in Synthesis Example 1
and 10 g of the white solid polymer obtained in Synthesis Example 4 were dissolved in 160 g of water to obtain Compound E (yellow transparent, slightly viscous liquid). Formulation Example 2 20g of the pale yellow solid polymer obtained in Synthesis Example 1 and 20g of the white solid polymer obtained in Synthesis Example 4 were mixed with water.
It was dissolved in 160 g to give Formulation F (yellow transparent, slightly viscous liquid). Formulation Example 3 30 g of the pale yellow solid polymer obtained in Synthesis Example 3 and 10 g of the white polymer obtained in Synthesis Example 4 were mixed with 160 g of water.
g to give Formulation G (pale yellow transparent viscous liquid). Test Example 1 The color fastness of the product of the present invention applied to cotton cloth dyed with a reactive dye was tested in accordance with the following method. (1-1) Preparation of dyed product Cotton knitted fabric was dyed with a reactive dye according to a conventional method, and then dyed with a 2 g/aqueous solution of Lipotol RK-5 (manufactured by Nicca Chemical Co., Ltd.) at 90°C for 10 minutes. After washing for a minute,
Washed with water and dried.
【表】【table】
【表】
(1―2) 堅牢度増進剤処理
本発明品及び比較品を染色物の重量に対し５％の
量で用い、浴比１：30で約60℃にて20分間処理
し、水洗した後乾燥した。
(1―3) 堅牢度試験方法
(a) 洗たくに対する染色堅牢度試験
JIS Ｌ―0844 Ａ―３法
(b) 汗に対する染色堅牢度試験
JIS Ｌ―0848 Ａ法 アルカリ性
(c) 経時変化後の染色堅牢度試験
試験布をHPスチーマーにて115℃で60分間ス
チーミングした後JIS Ｌ―0846 Ａ法 の水に
対する染色堅牢度試験に供する。
(d) 耐塩素堅牢度試験
有効塩素20ppm（次亜塩素酸ソーダ使用）
の液に浴比１：200で室温にて２時間、試験布
を浸漬する。
(e) 日光堅牢度試験
フエード・オ・メーターにて試験布を63℃で
20時間露光する。
(1―4) 判定方法
染色堅牢度は添付白布（綿及び絹）の汚染度を
汚染用グレースケールにて級数判定した。耐塩素
堅牢度試験及び日光堅牢度試験は退色度を変退色
用グレースケールにて級数判定した。
(1―5) 試験結果
＜染色堅牢度試験＞[Table] (1-2) Fastness enhancer treatment The products of the present invention and comparative products were used in an amount of 5% based on the weight of the dyed product, treated at a bath ratio of 1:30 for 20 minutes at approximately 60°C, and washed with water. Then it was dried. (1-3) Fastness test method (a) Dyeing fastness test against washing JIS L-0844 Method A-3 (b) Dyeing fastness test against sweat JIS L-0848 Method A Alkaline (c) Dyeing after aging Fastness test The test fabric was steamed for 60 minutes at 115°C using an HP steamer, and then subjected to a color fastness test against water according to JIS L-0846 Method A. (d) Chlorine fastness test Available chlorine 20ppm (using sodium hypochlorite)
The test cloth is immersed in this solution at a bath ratio of 1:200 for 2 hours at room temperature. (e) Sunlight fastness test Test fabric at 63°C in a fade-o-meter.
Expose for 20 hours. (1-4) Judgment method Color fastness was determined by evaluating the degree of contamination of the attached white cloth (cotton and silk) using a gray scale for contamination. In the chlorine fastness test and the sunlight fastness test, the degree of fading was evaluated using a gray scale for fading. (1-5) Test results <Color fastness test>
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
以上の様に各種堅牢度及び色相変化において従
来法と比べて本発明による方法がすぐれているこ
とがわかる。[Table] As shown above, it can be seen that the method according to the present invention is superior to the conventional method in terms of various fastnesses and hue changes.
Claims (1)
る繊維材料の反応性染料による染色物をビニルイ
ミダゾールの酸塩もしくは第四級塩の単独重合体
及び／又はこれと共重合化能な単量体との共重合
体、あるいは前記単独重合体及び／又は共重合体
と下記一般式(2)で示されるカチオン性重合体との
混合物よりなる後処理剤を用いて後処理すること
を特徴とするセルロース系繊維染色物の後処理
法。 上式中、R3及びR4は同一又は相異るものであ
つてよく、それぞれ低級アルキル基を表わし、Ｘ
はハロゲン原子又はHSO4を表わす。[Scope of Claims] 1. Dyeing of cellulose fibers or fiber materials made of cellulose fibers and other fibers with reactive dyes by copolymerizing them with homopolymers and/or quaternary salts of vinylimidazole. post-treatment using a post-treatment agent consisting of a copolymer with a functional monomer, or a mixture of the homopolymer and/or copolymer and a cationic polymer represented by the following general formula (2). A method for post-processing dyed cellulose fibers, characterized by: In the above formula, R 3 and R 4 may be the same or different and each represents a lower alkyl group, and
represents a halogen atom or HSO 4 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56094556A JPS57210083A (en) | 1981-06-20 | 1981-06-20 | Post-treatment of cellulosic fiber dyed article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56094556A JPS57210083A (en) | 1981-06-20 | 1981-06-20 | Post-treatment of cellulosic fiber dyed article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57210083A JPS57210083A (en) | 1982-12-23 |
| JPS6114276B2 true JPS6114276B2 (en) | 1986-04-17 |
Family
ID=14113587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56094556A Granted JPS57210083A (en) | 1981-06-20 | 1981-06-20 | Post-treatment of cellulosic fiber dyed article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57210083A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3703293A1 (en) * | 1987-02-04 | 1988-08-18 | Cassella Ag | WET FASTNESS IMPROVEMENT OF SULFUR DYE COLORS |
| FR2746808B1 (en) * | 1996-03-27 | 1998-05-07 | Protex Manuf Prod Chimiq | AGENT AND METHOD FOR IMPROVING THE FRICTION STRENGTH OF DYES OR PRINTS |
| EP0812949A3 (en) * | 1996-06-11 | 1998-07-22 | Ciba SC Holding AG | Process for the treatment of dyed fibrous cellulosic materials |
| CN101500655B (en) | 2006-08-11 | 2013-09-18 | 巴斯夫欧洲公司 | The use of cationic copolymerization from amine-holding acrylates and N-vinyl imidazolium salts in hair cosmetic products |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5370178A (en) * | 1976-12-01 | 1978-06-22 | Nippon Senka Kougiyou Kk | Improving of dyeing fastness |
-
1981
- 1981-06-20 JP JP56094556A patent/JPS57210083A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5370178A (en) * | 1976-12-01 | 1978-06-22 | Nippon Senka Kougiyou Kk | Improving of dyeing fastness |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57210083A (en) | 1982-12-23 |
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