CN1066476C - 水不溶性单偶氮染料 - Google Patents
水不溶性单偶氮染料 Download PDFInfo
- Publication number
- CN1066476C CN1066476C CN95102997A CN95102997A CN1066476C CN 1066476 C CN1066476 C CN 1066476C CN 95102997 A CN95102997 A CN 95102997A CN 95102997 A CN95102997 A CN 95102997A CN 1066476 C CN1066476 C CN 1066476C
- Authority
- CN
- China
- Prior art keywords
- water
- hour
- dyeing
- dye
- temperature
- 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 - Fee Related
Links
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 9
- 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 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 11
- 238000006193 diazotization reaction Methods 0.000 claims description 11
- 229920004935 Trevira® Polymers 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- CFKZMYPOJOKAAD-UHFFFAOYSA-N 2-amino-5-nitrothiophene-3-carbonitrile Chemical compound NC=1SC([N+]([O-])=O)=CC=1C#N CFKZMYPOJOKAAD-UHFFFAOYSA-N 0.000 claims description 5
- ADCCXZRDYFZKTC-UHFFFAOYSA-N C(C)NC1=CC=CC=C1.[O] Chemical compound C(C)NC1=CC=CC=C1.[O] ADCCXZRDYFZKTC-UHFFFAOYSA-N 0.000 claims description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- 238000004043 dyeing Methods 0.000 abstract description 46
- 239000006185 dispersion Substances 0.000 abstract description 17
- 239000000975 dye Substances 0.000 description 68
- 230000006641 stabilisation Effects 0.000 description 9
- 238000011105 stabilization Methods 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- -1 Monoazo compound Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000004744 fabric Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229940056729 sodium sulfate anhydrous Drugs 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 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
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910016523 CuKa Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000005031 sulfite paper Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 238000009970 yarn dyeing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
- C09B29/08—Amino benzenes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0025—Crystal modifications; Special X-ray patterns
- C09B67/0028—Crystal modifications; Special X-ray patterns of azo compounds
- C09B67/0029—Crystal modifications; Special X-ray patterns of azo compounds of monoazo compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
- C09B29/0059—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing only sulfur as heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
- C09B29/08—Amino benzenes
- C09B29/0805—Amino benzenes free of acid groups
- C09B29/0807—Amino benzenes free of acid groups characterised by the amino group
- C09B29/0809—Amino benzenes free of acid groups characterised by the amino group substituted amino group
- C09B29/0811—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino
- C09B29/0813—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino substituted by OH, O-C(=X)-R, O-C(=X)-X-R, O-R (X being O,S,NR; R being hydrocarbonyl)
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0001—Post-treatment of organic pigments or dyes
- C09B67/0014—Influencing the physical properties by treatment with a liquid, e.g. solvents
- C09B67/0015—Influencing the physical properties by treatment with a liquid, e.g. solvents of azoic pigments
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/16—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using dispersed, e.g. acetate, dyestuffs
- D06P1/18—Azo dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/34—Material containing ester groups
- D06P3/52—Polyesters
- D06P3/56—Preparing azo dyes on the material
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Dispersion Chemistry (AREA)
- Coloring (AREA)
Abstract
一种如结构式(Ⅰ)所示的水不溶性单偶氮染料,
它具有由在约10.6°、14.1°和26.5°衍射角(2θ)处显示相当强的峰和在约5.2°、21.1°、24.1°和27.9°衍射角(2θ)处显示中等强度峰的X-射线衍射图表征的晶体结构。即使在高温和苛刻染色条件下,本发明染料的分散稳定性也极好。
Description
本发明涉及单偶氮染料,更具体地说,本发明涉及到具有新颖晶体结构的兰色单偶氮染料,该染料即使是在高温和苛刻染色条件下也能均匀地使聚酯纤维染色。
近年来,在染色工业中,对染色方法作了合理化改进。例如在,用分散染料给聚酯纤维染色时,一般用喷射式染色方法染织物,而用筒子纱染色方法染纱线。
这些染色方法采用一种体系,其中使液态染料分散体循环通过绕成多层的固定密度的纤维层。因此,这些染色方法总是要求染色浴中的染料颗粒以微粒分散,且在染色浴中的分散稳定性极好。如果染料颗粒较大,染料颗粒通过纤维层时就会被滤出,从而导致种种疵病,如由于染料不能渗透入纤维内层或由于缔合物的沉淀而产生如内层或外层的染色不匀问题;或由于染料及沉积在纤维表面而导致色坚牢度如摩擦牢度的降低等。
因此,要求用于这种染色方法的染料在染色浴中显示极好的分散度,且在室温至高温的很大的染色温度范围内其分散度不会降低。
然而,当染色浴被加热至高温时,染料的分散度常会降低,结果,缔合的染料以如上所述的过滤残留物的形式沉积于被染色物体的表面,多层的待染色物体会在外层部分和内层部分之间具有不同的染色深度。因此,几乎不可能得到均一染色的产品。
从节约能源和资源的观点出发,近来,出现采用苛刻染色条件的倾向,如①较低的染色浴的浴比(需染色物体对染液的比率从1∶30降至1∶10),②较低的分散剂比例(染料饼对分散剂的比率从1∶3降至1∶1),和③较短的染色时间和较高的染色温度(从130℃下1小时变为135℃下0.5小时)。这些条件又都影响染料的分散稳定性。因此,在常规染色条件下具有相当好分散稳定性的染料中,许多染料将会被视为在目前的苛刻染色条件下具有不良的分散稳定性。
这种单偶氮染料在常规的温和染色条件下可以均一地给聚酯纤维染色。而且它的各种坚牢度性质极好。然而当在上述的高温苛刻条件下进行染色时,染料的分散度的降低很多,以致使得很难获得具有均一染色度的染色产品。
另外,这种染料也存在与各种染色助剂相容性方面的问题。例如,在元明粉(Na2SO4)存在下它的高温分散稳定性非常不好。因此,当在元明粉存在下混合使用该染料和活性染料给聚酯/棉混纺的纱染色时,就会引起不均匀染色。此外,当它与其他染料混合使用时,由于它与相混合染料间不良的相容性会引起色调偏差或不规则染色。
本发明的目的是解决上述问题并提供一种染料,利用它即使在高温等苛刻条件下也能很好地进行染色。
本发明人对上述的问题进行了广泛的研究,结果发现,一种具有新颖晶体结构的结构式(1)所示的噻吩型单偶氮化合物的晶体,它不同于由常规合成反应制得的无定形固体,甚至在苛刻的高温染色条件下亦具有极好分散稳定性。
另外,发现在高温染色浴中分散的染料组合物的稳定性在很大程度上取决于染料的可结晶性和颗粒大小。当使用上述具有新颖晶体结构的染料时,首先可达到高温染色浴中染料组合物的分散稳定性。在这个发现的基础上完成了本发明。
因此,本发明提供了具有如结构式(Ⅰ)所示的水不溶性单偶氮染料:它具有由在约10.6°、14.1°和26.5°的衍射角(2θ)处显示出相当强的峰,在约5.2°、21.1°、24.1°和27.9°衍射角(2θ)处显示中等强度的峰的X射线衍射图表征的晶体结构。
现在,将结合特定的实施例详细说明本发明。
本发明的具有新颖晶体结构的单偶氮染料可用如下方法制备。即上述结构式(Ⅰ)所示的单偶氮化合物可用常规方法使2-氨基-5-硝基-3-氰基噻吩重氮化,随后再在-8至10℃,更好地为-5至5℃之间的某-温度和稀硫酸水介质中与偶联剂N-乙基-N-苯氧乙基苯胺偶合作用0.5至15小时。
用这种合成方法制得的单偶化合物滤饼具有无定形结构。本发明再以特定条件对之进行处理,结果得到具有上述晶体结构的结晶。
这种处理可用如下几种方法:①将无定形结构的滤饼分散于水介质中,并在60至130℃,最好在80至100℃间的某温度下搅拌0.5至30小时,更好地为1至10小时,必要时可加入分散剂,如萘磺酸和甲醛的缩合物或以木质素磺酸钠为主成份的亚硫酸纸泊废液的浓缩物;②将无定形结构的滤饼分散于有机溶剂中,如甲醇、乙醇或丁醇等醇类溶剂、二噁烷、乙二醇或乙二醇醚等醚类溶剂,在15至100℃,或更好在20至80℃间的某温度下搅拌0.5至10小时;③用常规方法使2-氨基-5-硝基-3-氰基噻吩重氮化,然后在醇介质(如甲醇或乙醇)中或在含醇量大于70%(体积)的水介质中以及,在-8至10℃,更好地在-5至5℃间的某个温度与为偶合剂N-乙基-N-苯氧乙基苯胺进行偶合,历时0.5至15小时。
在附图中:
附图1表示以实施例1制得的具有新颖晶体结构的单偶氮化合物的X-射线衍射图。
附图2表示依照实施例1制得的具有无定形结构的单偶氮染料的X-射线衍射图。
现在参照附图说明通式(Ⅰ)所示单偶氮化合物的晶体结构和无定形结构。附图1和2表示了用比例计数器记录粉未X-射线衍射方法中CuKa射线衍射状态而得到的X-射线衍射图。在每个附图中,横坐标表示衍射角(2θ),纵坐标表示衍射强度。附图1表示了本发明新颖的晶体结构,它可用约10.6°、14.1°和26.5°的衍射角(2θ)处的强峰和约5.2°、21.1°、24.1°和27.9°衍射角处的中等峰来表征。附图2表示了常规无定形结构,它明显不同于附图1中的晶体结构。用X-射线衍射方法测定的有相同晶形产品的衍射角误差应小于约±0.1°。因此,这二个附图清楚地表明了结晶状态的差别,由于结晶状态的差别,单偶氮化合物在染色操作中的性能是不同的。即在本发明情况下,即使使用高温和苛刻染色条件的染色方法也可以获极好的染色效果。
用本发明单偶氮染料染色的纤维可以是例如由聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯或对苯二甲酸和1,4-双(羟甲基)环己烷制成的聚酯纤维或这种聚酯纤维与其他纤维(如棉纤维、人造纤维-聚酰胺或羊毛纤维)的混纺纱产品或混合长丝纱线。为了用本发明单偶氮染料染聚酯纤维,染色浴或印花色浆是按照常规方法使用分散剂(如萘磺酸与甲醛的缩合物,高级醇硫酸酯或高级烷基苯磺酸酯)将染料分散于水介质中而加以制备的,随后进行浸染或印花。在浸染情况下,可以使用上述的高温染色法,载体染色方法或热溶染色方法。还有,即使在这些方法中使用苛刻的染色条件,也可以极好地使聚酯纤维或它的混纺产品染色。这是因为本发明的单偶氮染料的分散稳定性极好,特别值得一提的是,聚酯纤维可以在125℃至140℃之间的染色温度、染色浴比不超过15倍,分散剂对染料的重量比不超过3倍等苛刻条件下,在分散剂的存在下以及在水介质进行尽染。
另外,在染浴中掺入酸性物质,如甲酸、乙酸、磷酸或硫酸铵可以产生更好的结果。
本发明通式(Ⅰ)单偶氮染料可以和其他染料联合使用。在某些情况下由染料的联合使用可以得到更好的结果,如染色性的提高。
现在参照实施例更详细地说明本发明;然而,应该知道,本发明绝不仅局限于这些特定的实施例。
实施例1制备染料晶体
将12.1gN-乙基-N-苯氧乙基苯胺乳化在350ml5%硫酸水溶液中,以获得偶合剂组分溶液。然后将18.5g 43%的亚硝基硫酸加入到42.9g 98%的硫酸中,然后在-5至0℃温度间和搅拌下逐渐加入8.45g的2-氨基-5-硝基-3-氰基噻吩进行重氮化反应,以获得重氮化溶液。在0至5℃温度间将重氮化溶液滴加入上述混合剂组分溶液。在同温度下将混合物搅拌10小时。经过滤收集沉淀固体,经水洗涤、干燥后得到12.8g上述结构式(Ⅰ)所示的兰色化合物。由这种反应制得的单偶氮染料粉未用X-射线衍射方法进行分析,结果发现它是无定形物质。给出如附图2所示的X-射线衍射图。
另外,制备另一批重氮化溶液和偶合剂组分溶液的混合物。将其加热至7℃~80℃,而不经过滤收集沉淀固体。然后在相同温度下进行5小时热处理。然后冷却至室温。过滤收集沉淀固体并干燥之,所得物质用X-射线衍射光谱进行分析,结果发现它是结晶体,给出如附图1所示的X-射线衍射图谱。测试实施例1染色实例
将0.2g由实施例1制得的具有晶体结构的单偶氮染料分散于1升含0.2g萘磺酸-甲醛缩合物和0.2g高级醇硫酸酯的水中,以获得染色浴。
在这种染色浴中,浸入100g聚酯纤维布并在135℃染色30分钟。随后皂煮,水洗并干燥之,此时发现染料的分散性极好,织物染色均匀。所得染色布为兰色,它的耐光牢度极好,为6级,它的耐磨色牢度也极好,为5级。
使用在实施例1制备过程中获得的无定形结构的单偶氮染料进行相似的染色试验。其中在染色浴中出现染料的部分缔集,织物染色不匀。染色的布耐磨牢度不好,为1级。测试实施例2染色实例
除萘磺酸-甲醛缩合物和高级醇的硫酸酯的量都改为0.6g,水的量改为3升,染色条件改为130℃时60分钟(比测试实例1温和)以外按测试实例1相同的方法进行染色。其中当用本发明具有晶体结构的染料进行染色时,和测试实例1中一样其结果极好,所得染色布的耐光牢度极好,为6级,它的耐磨色牢度极好,为5级。反之,当使用具有无定形结构的染料时,可以观察到比试验实例1稍有改进,但布的染色仍不规则,耐磨色牢度为3级。
本发明的具有这种特定晶体结构的水不溶性单偶氮染料的分散稳定性即使在高温和在苛刻染色条件下,如染色物对染液的比例为1∶10,染料饼对分散剂的比率为1∶1以及染色条件为135℃、0.5小时也是极好的,这样得到的染色布的耐光牢度和耐磨牢度极好。因此,从节约能源和资源的观点来看本发明染料非常有用。
Claims (4)
1.一种如下述结构式(Ⅰ)所示的水不溶性单偶氮染料:其特征在于它具有由在10.6°、14.1°和26.5°衍射角(2θ)处显示相当强峰和在5.2°、21.1°、24.1°和27.9°衍射角(2θ)处显示中等强度峰的X-射线衍射图表征的晶体结构。
2.一种使聚酯纤维染色的方法,其特征在于使用如权利要求1所述的水不溶性单偶氮染料。
3.一种如权利要求1所述的水不溶性单偶氮染料的生产方法,其特征在于它包括使2-氨基-5-硝基-3-氰基噻吩重氮化,在-8至10℃温度间和在稀硫酸水溶液介质中使重氮化产物与N-乙基-N-苯氧乙基苯胺偶合,历时0.5至15小时,然后:
①在60至130℃温度间搅拌反应混合物0.5至30小时,或,
②分离反应混合物中的沉淀物,将沉淀物分散于(a)水介质中并在60至130℃温度间将所得的混合物搅拌0.5至30小时,或将沉淀物分散于(b)有机溶剂中并在20至80℃间将所得的混合物搅拌0.5至10小时,所述的有机溶剂选自甲醇、乙醇、丁醇、二噁烷、乙二醇或二乙醇醚。
4.一种如权利要求1所述的水不溶性单偶氮染料的生产方法,其特征在于它包括使2-氨基-5-硝基-3-氰基噻吩重氮化并在醇介质或在含超过70%(体积)醇的水介质中以及-8至10℃温度间使重氮化产物与N-乙基-N-苯氧乙基苯胺偶合,历时0.5至15小时。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP79712/1994 | 1994-03-25 | ||
JP07971294A JP3318109B2 (ja) | 1994-03-25 | 1994-03-25 | 水不溶性モノアゾ染料 |
JP79712/94 | 1994-03-25 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1112147A CN1112147A (zh) | 1995-11-22 |
CN1066476C true CN1066476C (zh) | 2001-05-30 |
Family
ID=13697827
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN95102997A Expired - Fee Related CN1066476C (zh) | 1994-03-25 | 1995-03-25 | 水不溶性单偶氮染料 |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0673977B1 (zh) |
JP (1) | JP3318109B2 (zh) |
KR (1) | KR100363925B1 (zh) |
CN (1) | CN1066476C (zh) |
DE (1) | DE69517225T2 (zh) |
ES (1) | ES2148368T3 (zh) |
TW (1) | TW321678B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09124966A (ja) * | 1995-10-30 | 1997-05-13 | Daisutaa Japan Kk | 青色系分散染料混合物 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4319880A (en) * | 1979-05-25 | 1982-03-16 | Hoechst Aktiengesellschaft | Monoazo dyestuff being stable under dyeing conditions; its manufacture and its use |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2007382A (en) * | 1932-08-16 | 1935-07-09 | Celanese Corp | Production of dispersions |
CH203952A (de) * | 1938-03-05 | 1939-04-15 | Chem Ind Basel | Verfahren zur Herstellung von Azofarbstoffen. |
DE2722768A1 (de) * | 1977-05-20 | 1978-11-30 | Cassella Farbwerke Mainkur Ag | Verfahren zur herstellung von azofarbstoffen |
JPS5996167A (ja) * | 1982-11-24 | 1984-06-02 | Gosei Senriyou Gijutsu Kenkyu Kumiai | 合成繊維用アゾ染料 |
DE4215495A1 (de) * | 1992-05-12 | 1993-11-18 | Basf Ag | Azofarbstoffe mit einer acetalisierten Diazokomponente aus der Thiophen- oder Thiazolreihe |
-
1994
- 1994-03-25 JP JP07971294A patent/JP3318109B2/ja not_active Expired - Fee Related
-
1995
- 1995-03-13 TW TW084102365A patent/TW321678B/zh active
- 1995-03-23 ES ES95104330T patent/ES2148368T3/es not_active Expired - Lifetime
- 1995-03-23 DE DE69517225T patent/DE69517225T2/de not_active Expired - Fee Related
- 1995-03-23 EP EP95104330A patent/EP0673977B1/en not_active Expired - Lifetime
- 1995-03-24 KR KR1019950006417A patent/KR100363925B1/ko not_active IP Right Cessation
- 1995-03-25 CN CN95102997A patent/CN1066476C/zh not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4319880A (en) * | 1979-05-25 | 1982-03-16 | Hoechst Aktiengesellschaft | Monoazo dyestuff being stable under dyeing conditions; its manufacture and its use |
Also Published As
Publication number | Publication date |
---|---|
ES2148368T3 (es) | 2000-10-16 |
DE69517225T2 (de) | 2000-11-30 |
EP0673977A3 (en) | 1996-05-15 |
EP0673977B1 (en) | 2000-05-31 |
KR100363925B1 (ko) | 2003-01-29 |
DE69517225D1 (de) | 2000-07-06 |
KR950032478A (ko) | 1995-12-20 |
JPH07258575A (ja) | 1995-10-09 |
CN1112147A (zh) | 1995-11-22 |
TW321678B (zh) | 1997-12-01 |
JP3318109B2 (ja) | 2002-08-26 |
EP0673977A2 (en) | 1995-09-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5100872B2 (ja) | セルロース染色形成物 | |
DE69510971T2 (de) | Monoazofarbstoffe | |
DE3686247T2 (de) | Mischung von monoazofarbstoffen und verfahren zuem faerben von polyester fasern unter verwendung derartiger farbstoffmischungen. | |
CN1066476C (zh) | 水不溶性单偶氮染料 | |
DE69902385T2 (de) | Dispersionsfarbstoffmischungen | |
JP3638306B2 (ja) | モノアゾ染料化合物 | |
JP3076651B2 (ja) | 水不溶性モノアゾ染料 | |
JP3742129B2 (ja) | 水不溶性青色系モノアゾ染料 | |
JP3725594B2 (ja) | 水不溶性モノアゾ染料及びその製造方法 | |
JP3746813B2 (ja) | 水不溶性赤色系モノアゾ染料の結晶 | |
EP0433693B1 (en) | Water-insoluble monoazo dyes and mixture thereof | |
DE69305871T2 (de) | Wasserunlöslicher Monoazofarbstoff und ein ihn verwendendes Färbeverfahren | |
JP3212778B2 (ja) | 水不溶性モノアゾ染料 | |
JP3725595B2 (ja) | 水不溶性モノアゾ染料及びその製造方法 | |
GB2099010A (en) | Dis-azo compound | |
US6388057B1 (en) | Crystalline modification of a water-insoluble monoazo dye | |
GB2123845A (en) | Crystalline monoazo dye and its production | |
JPH10298445A (ja) | 結晶形モノアゾ分散染料およびその適用 | |
JPH10298444A (ja) | 結晶形モノアゾ分散染料及びその適用 | |
JPS5817772B2 (ja) | モノアゾ化合物およびその製法 | |
JP2003501490A (ja) | 水不溶性のモノアゾ染料の結晶変態 | |
JPH03163170A (ja) | 水不溶性モノアゾ染料 | |
JPH11181318A (ja) | モノアゾ分散染料及びその適用 | |
MXPA01006956A (en) | Crystalline modification of a water-insoluble monoazo dye | |
JPH07304989A (ja) | 水不溶性モノアゾ染料 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |