TW201302926A - Fibre-reactive dyes, their preparation and their use - Google Patents
Fibre-reactive dyes, their preparation and their use Download PDFInfo
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Abstract
Description
本發明係關於纖維反應性染料、其製備方法及其用於對紡織纖維材料進行染色或印刷之用途。 The present invention relates to fiber reactive dyes, processes for their preparation and their use for dyeing or printing textile fiber materials.
近來使用反應性染料進行染色之實踐使得對染色品品質及染色製程之經濟效益的要求較高。因此,不斷需要特性,尤其染料應用方面之特性得到改良之新穎反應性染料。 The recent practice of dyeing with reactive dyes has resulted in higher requirements for the quality of the dyeing and the economics of the dyeing process. Therefore, there is a continuing need for novel reactive dyes which have improved properties, particularly in terms of dye application.
現今染色需要具有足夠直接性且同時未固定之染料極易洗去之反應性染料。其亦應具有良好得色量及高反應性,目標尤其為提供具有高固定度之染色品。已知染料並不滿足所有特性之此等要求。 Today's dyeing requires a reactive dye that is sufficiently straightforward and at the same time unfixed, the dye is easily washable. It should also have a good color yield and high reactivity, and the object is particularly to provide a dyeing product having a high degree of fixation. It is known that dyes do not meet these requirements for all properties.
自JP-A-08-60017及US-A-6,537,332獲知之染料在以上所提及之特性方面仍具有某些缺點。 Dyes known from JP-A-08-60017 and US-A-6,537,332 still have certain disadvantages in terms of the properties mentioned above.
因此本發明之潛在問題為發現用於對纖維材料進行染色及印刷之具有上文特性化為高等級之品質的改良之新穎反應性染料。新穎染料之不同之處尤其應在於良好提昇(build-up)特性、高固定量及高纖維染料結合穩定性,且另外未固定至纖維之染料應有可能容易地洗去。染料亦應產生具有良好全面牢度特性之染色品,例如耐光牢度及耐洗牢度。 A potential problem with the present invention is therefore the discovery of improved novel reactive dyes having the qualities characterized above to a high grade for dyeing and printing fibrous materials. The novel dyes differ in particular by good build-up characteristics, high fixed amounts and high fiber dye binding stability, and additionally dyes that are not fixed to the fibers should be easily washed away. Dyes should also produce dyes with good overall fastness properties such as light fastness and wash fastness.
已發現所提出之問題主要藉由下文所定義之新穎染料來解決。 It has been found that the problems raised are mainly solved by novel dyes as defined below.
因此本發明係關於下式之反應性染料:
作為C1-C4烷基,對於R1、R2、R3、R4及R5考慮其各彼此獨立地為例如甲基、乙基、正丙基、異丙基、正丁基、第二丁基、異丁基及第三丁基,尤其為甲基及乙基。烷基R1、R2及R4可為未經取代之烷基或可經例如羥基、磺基、硫酸根絡基(sulfato)、氰基、羧基、C1-C4烷氧基或經苯基,較佳經羥基、磺基、C1-C4烷氧基或經苯基,且尤其經磺基取代。 As C 1 -C 4 alkyl, R 1 , R 2 , R 3 , R 4 and R 5 are each independently, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, The second butyl, isobutyl and tert-butyl groups are especially methyl and ethyl. The alkyl groups R 1 , R 2 and R 4 may be an unsubstituted alkyl group or may be, for example, a hydroxyl group, a sulfo group, a sulfato group, a cyano group, a carboxyl group, a C 1 -C 4 alkoxy group or a Phenyl, preferably via hydroxy, sulfo, C 1 -C 4 alkoxy or via phenyl, and especially substituted by sulfo.
在一個較佳具體實例中,基團R1及R2中之一者為氫且基團R1及R2中之另一者為一個以上所提及之未經取代或經取代之C1-C4烷基,例如甲基、乙基或式-CH2-SO3H之基團。 In a preferred embodiment, one of the groups R 1 and R 2 is hydrogen and the other of the groups R 1 and R 2 is one or more of the unsubstituted or substituted C 1 a -C 4 alkyl group such as a methyl group, an ethyl group or a group of the formula -CH 2 -SO 3 H.
在另一個較佳具體實例中,R1及R2為氫。 In another preferred embodiment, R 1 and R 2 are hydrogen.
在另一個較佳具體實例中,R1為氫且R2為氫、甲基或式-CH2-SO3H之基團。 In another preferred embodiment, R 1 is hydrogen and R 2 is hydrogen, methyl or a group of the formula -CH 2 -SO 3 H.
R4較佳為氫或未經取代之C1-C4烷基,例如甲基或乙基。 R 4 is preferably hydrogen or an unsubstituted C 1 -C 4 alkyl group such as a methyl group or an ethyl group.
作為C1-C4烷氧基,對於R3及R5考慮其為例如甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、異丁氧基及第三丁氧基,較佳為甲氧基及乙氧基,且尤其為甲氧基。 As the C 1 -C 4 alkoxy group, it is considered to be, for example, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, and a third group for R 3 and R 5 . Butoxy, preferably methoxy and ethoxy, and especially methoxy.
R3較佳表示n個選自甲基、甲氧基及磺基之群的相同或不同之取代基。 R 3 preferably represents the same or different substituents selected from the group consisting of methyl, methoxy and sulfo groups.
(R5)0-2較佳表示0至2個選自甲基、甲氧基及磺基之群的相同或不同之取代基。 (R 5 ) 0-2 preferably represents 0 to 2 of the same or different substituents selected from the group consisting of methyl, methoxy and sulfo groups.
作為離去基U,考慮其為例如-Cl、-Br、-F、-OSO3H、-SSO3H、-OCO-CH3、-OPO3H2、-OCO-C6H5、-OSO2-C1-C4烷基及-OSO2-N(C1-C4烷基)2。U較佳為下式之基團:-Cl、-OSO3H、-SSO3H、-OCO-CH3、-OCO-C6H5或-OPO3H2,尤其為-Cl或-OSO3H。 As the leaving group U, it is considered to be, for example, -Cl, -Br, -F, -OSO 3 H, -SSO 3 H, -OCO-CH 3 , -OPO 3 H 2 , -OCO-C 6 H 5 ,- OSO 2 -C 1 -C 4 alkyl and -OSO 2 -N(C 1 -C 4 alkyl) 2 . U is preferably a group of the formula: -Cl, -OSO 3 H, -SSO 3 H, -OCO-CH 3 , -OCO-C 6 H 5 or -OPO 3 H 2 , especially -Cl or -OSO 3 H.
因此適當基團Y之實例為乙烯基、β-溴-乙基或β-氯-乙基、β-乙醯氧基-乙基、β-苯甲醯氧基乙基、β-磷酸醯氧基乙基、β-硫酸根絡乙基及β-硫基硫酸根絡乙基。 Thus examples of suitable groups Y are vinyl, β-bromo-ethyl or β-chloro-ethyl, β-ethoxycarbonyl-ethyl, β-benzyloxyethyl, β-phosphonium oxide Base ethyl, β-sulfatoethyl and β-thiosulfatoethyl.
Y較佳獨立地為乙烯基、β-氯乙基或β-硫酸根絡乙基。 Y is preferably independently a vinyl group, a β-chloroethyl group or a β-sulfatoethyl group.
k較佳為數字1或2。 k is preferably a number 1 or 2.
m及p較佳各彼此獨立地為數字2或3。 m and p are preferably each independently of the number 2 or 3.
m尤其較佳為數字3。 m is particularly preferably a number 3.
n較佳為數字0或1。 n is preferably a number of 0 or 1.
p尤其較佳為數字2。 p is particularly preferably the number 2.
Z1較佳為式(4a)、式(4b)或式(4e)之基團,尤其為式(4a)或式(4e)之基團,且更尤其為式(4a)之基團,該等變數具有上文給出之定義及較佳含義。 Z 1 is preferably a group of the formula (4a), the formula (4b) or the formula (4e), especially a group of the formula (4a) or the formula (4e), and more particularly a group of the formula (4a), These variables have the definitions and preferred meanings given above.
在一個較佳具體實例中,D1與式(2)之基團對應且D2與式(3a)或式(3b)之基團對應,其中R3、Z1、Y、k、m及n各具有上文給出之定義及較佳含義。 In a preferred embodiment, D 1 corresponds to a group of formula (2) and D 2 corresponds to a group of formula (3a) or formula (3b), wherein R 3 , Z 1 , Y, k, m and n each have the definitions given above and preferred meanings.
在一個特定具體實例中,D2與式(3a)之基團對應,其中R3、Z1及n各具有上文給出之定義及較佳含義。 In a particular embodiment, D 2 corresponds to a group of formula (3a), wherein R 3 , Z 1 and n each have the definitions given above and preferred meanings.
在一個尤其較佳具體實例中,D2為下式之基團:
當T1為非纖維反應性取代基時,其可為例如羥基;C1-C4烷氧基;未經取代或經例如羥基、羧基或磺基取代之C1-C4烷基硫基;胺基;經C1-C8烷基單取代或雙取代之胺基,其中該烷基本身可經例如磺基、硫酸根絡基、羥基、羧基或經苯基,尤其經磺基或經羥基取代,且可經基團-O-間雜一或多次;環己胺基;嗎啉基;N-C1-C4烷基-N-苯胺基、苯胺基或萘胺基,其中該苯基或萘基未經取代或經例如C1-C4烷基、C1-C4烷氧基、C2-C4烷醯基胺基、羧基、磺基或經鹵素取代且該烷基未經取代或經例如羥基、磺基或經硫酸根絡基取代。 T 1 when a non-fiber-reactive substituents, which may be, for example, hydroxy; C 1 -C 4 alkoxy; unsubstituted or substituted, for example, the hydroxyl, carboxyl or sulfo C 1 -C 4 alkylthio An amine group; a mono- or di-substituted amine group via a C 1 -C 8 alkyl group, wherein the alkyl group itself may be, for example, a sulfo group, a sulfate group, a hydroxyl group, a carboxyl group or a phenyl group, especially a sulfo group or Substituted by a hydroxy group and may be heteroatomically one or more times via a group -O-; cyclohexylamino; morpholinyl; NC 1 -C 4 alkyl-N-anilino, anilino or naphthylamino, wherein the benzene Or a naphthyl group which is unsubstituted or substituted with, for example, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, a C 2 -C 4 alkylalkylamino group, a carboxyl group, a sulfo group or a halogen group, and the alkyl group Unsubstituted or substituted with, for example, a hydroxyl group, a sulfo group or a sulfate group.
適當非纖維反應性取代基T1之實例為胺基、甲胺基、乙胺基、β-羥基乙胺基、N-甲基-N-β-羥基乙胺基、N-乙基-N-β-羥基乙胺基、N,N-二-β-羥基乙胺基、β-磺基乙胺基、環己胺基、嗎啉基、2-氯苯胺基、3-氯苯胺基或4-氯苯胺基、2-甲基苯胺基、3-甲基苯胺基或4-甲基苯胺基、2-甲氧基苯胺基、3-甲氧基苯胺基或4-甲氧基苯胺基、2-磺基苯胺基、 3-磺基苯胺基或4-磺基苯胺基、2,5-二磺基苯胺基、2-羧基苯胺基、3-羧基苯胺基或4-羧基苯胺基、1-萘胺基或2-萘胺基、1-磺基-2-萘胺基、4,8-二磺基-2-萘胺基、N-乙基-N-苯基-胺基、N-甲基-N-苯胺基、甲氧基、乙氧基、正丙氧基或異丙氧基及羥基。 Examples of suitable non-fibrous reactive substituents T 1 are amine, methylamino, ethylamine, β-hydroxyethylamino, N-methyl-N-β-hydroxyethylamino, N-ethyl-N -β-hydroxyethylamino, N,N-di-β-hydroxyethylamino, β-sulfoethylamino, cyclohexylamino, morpholinyl, 2-chloroanilino, 3-chloroanilino or 4-chloroanilino, 2-methylanilino, 3-methylanilino or 4-methylanilino, 2-methoxyanilino, 3-methoxyanilino or 4-methoxyanilino , 2-sulfoanilino, 3-sulfoanilino or 4-sulfoanilino, 2,5-disulfoanilino, 2-carboxyanilino, 3-carboxyanilino or 4-carboxyanilino, 1-naphthylamino or 2-naphthylamino, 1-sulfo-2-naphthylamino, 4,8-disulfo-2-naphthylamino, N-ethyl-N-phenyl-amino, N-methyl-N-anilino, methoxy, ethoxy, n-propoxy or isopropoxy and hydroxy.
作為非纖維反應性取代基,T1較佳為C1-C4烷氧基;未經取代或經羥基、羧基或經磺基取代之C1-C4烷基硫基;羥基;胺基;未經取代或在一或多個烷基部分中經羥基、硫酸根絡基或經磺基取代之N-單-C1-C4烷基胺基或N,N-二-C1-C4烷基胺基;嗎啉基;未經取代或在苯環上經磺基、羧基、乙醯胺基、氯、甲基或經甲氧基取代之苯胺基;或N-C1-C4烷基-N-苯胺基,其未經取代或以與苯胺基同樣之方式在苯環上經取代且其中該烷基未經取代或經羥基、磺基或經硫酸根絡基取代;或未經取代或經1至3個磺基取代之萘胺基。 As a non-fiber-reactive substituent, T 1 is preferably C 1 -C 4 alkoxy; unsubstituted or substituted with hydroxyl, carboxyl or substituted by a sulfo group of C 1 -C 4 alkylthio group; a hydroxyl group; amine Unsubstituted or N-mono-C 1 -C 4 alkylamino group or N,N-di-C 1 - substituted by a hydroxyl group, a sulfate group or a sulfo group in one or more alkyl moieties C 4 alkylamino; morpholinyl; an anilino group which is unsubstituted or substituted with a sulfo group, a carboxyl group, an acetamino group, a chlorine group, a methyl group or a methoxy group on a benzene ring; or NC 1 - C 4 An alkyl-N-anilinyl group which is unsubstituted or substituted on the phenyl ring in the same manner as the anilino group and wherein the alkyl group is unsubstituted or substituted with a hydroxyl group, a sulfo group or a sulfate group; or Naphthylamino group substituted or substituted with 1 to 3 sulfo groups.
尤其較佳之非纖維反應性取代基T1為胺基、N-甲胺基、N-乙胺基、N-β-羥基乙胺基、N-甲基-N-β-羥基乙胺基、N-乙基-N-β-羥基乙胺基、N,N-二-β-羥基乙胺基、β-磺基乙胺基、嗎啉基、2-羧基苯胺基、3-羧基苯胺基或4-羧基苯胺基、2-磺基苯胺基、3-磺基苯胺基或4-磺基苯胺基、2,5-二磺基苯胺基及N-C1-C4烷基-N-苯胺基。 Particularly preferred non-fibrous reactive substituents T 1 are an amine group, an N-methylamino group, an N-ethylamino group, an N-β-hydroxyethylamino group, an N-methyl-N-β-hydroxyethylamino group, N-ethyl-N-β-hydroxyethylamino, N,N-di-β-hydroxyethylamino, β-sulfoethylamino, morpholinyl, 2-carboxyanilino, 3-carboxyanilinyl Or 4-carboxyanilino, 2-sulfoanilino, 3-sulfoanilino or 4-sulfoanilino, 2,5-disulfoanilino and NC 1 -C 4 alkyl-N-anilino .
X1為例如氟、氯或溴,尤其為氟或氯。 X 1 is, for example, fluorine, chlorine or bromine, especially fluorine or chlorine.
Hal為例如氯或溴,尤其為溴。 Hal is, for example, chlorine or bromine, especially bromine.
T1較佳為式(5a)之纖維反應性基團,該等變數具有上文 給出之定義及較佳含義。 T 1 is preferably a fiber-reactive group of the formula (5a), and the variables have the definitions given above and preferred meanings.
本發明之一個較佳具體實例係關於式(1)之反應性染料,其中R1為氫,R2為氫、甲基或式-CH2-SO3H之基團。 A preferred specific example of the present invention based on formula (1) of the reactive dye, wherein R 1 is hydrogen, R 2 is hydrogen, methyl or a group of formula -CH 2 -SO 3 H's.
D1與式(2)之基團對應且D2與式(3a)之基團對應,該等變數具有上文給出之定義及較佳含義;較佳,R3表示n個選自甲基、甲氧基及磺基,較佳選自磺基之群的相同或不同之取代基,Z1為如上文所定義之式(4a)之基團,Y為乙烯基、β-氯乙基或β-硫酸根絡乙基,k為數字1或2,m為數字2或3,較佳為3,且n為數字0、1或2,較佳為數字0或1。 D 1 corresponds to the group of the formula (2) and D 2 corresponds to the group of the formula (3a), and the variables have the definitions given above and preferred meanings; preferably, R 3 represents n selected from the group A The group, the methoxy group and the sulfo group are preferably selected from the same or different substituents of the group of sulfo groups, Z 1 is a group of the formula (4a) as defined above, and Y is a vinyl group, β-chloroethane Or a β-sulfate complex ethyl group, k is a number 1 or 2, m is a number 2 or 3, preferably 3, and n is a number 0, 1 or 2, preferably a number 0 or 1.
本發明之一個尤其較佳具體實例係關於式(1)之反應性染料,其中R1為氫,R2為氫、甲基或式-CH2-SO3H之基團。 A particularly preferred embodiment of the invention relates to a reactive dye of formula (1) wherein R 1 is hydrogen and R 2 is hydrogen, methyl or a group of the formula -CH 2 -SO 3 H.
D1與式(2)之基團對應、其中Y為乙烯基或β-氯乙基,k為數字1或2,m為數字3,且 D2為如上文所定義之式(3aa)之基團。 D 1 corresponds to a group of the formula (2), wherein Y is a vinyl group or a β-chloroethyl group, k is a number 1 or 2, m is a number 3, and D 2 is a formula (3aa) as defined above Group.
本發明亦係關於一種製備式(1)之染料的方法,其包含(i)以習用方式使約1莫耳當量之下式之胺重氮化:D2-NH2 (6),且與約1莫耳當量之下式化合物進行偶合反應(第一偶合反應):
以本身已知之方式使式(6)及式(9)之胺進行重氮化,例如在例如-5℃至40℃且較佳0℃至20℃之溫度下,在無機酸介質中,例如在鹽酸介質中,使用亞硝酸鹽,例如鹼金屬亞硝酸鹽,諸如亞硝酸鈉進行。 The amines of the formulae (6) and (9) are subjected to diazotization in a manner known per se, for example at a temperature of, for example, -5 ° C to 40 ° C and preferably 0 ° C to 20 ° C in a mineral acid medium, for example In a hydrochloric acid medium, a nitrite such as an alkali metal nitrite such as sodium nitrite is used.
在酸性或中性至弱鹼性pH值,例如0至8之pH值下且在例如-5℃至40℃,較佳0℃至30℃之溫度下以本身已知之方式與式(7)及式(8a)之偶合組分進行偶合。 In an acidic or neutral to weakly alkaline pH, for example at a pH of from 0 to 8, and at a temperature of, for example, -5 ° C to 40 ° C, preferably 0 ° C to 30 ° C, in a manner known per se and formula (7) The coupling component of the formula (8a) is coupled.
第一偶合反應(i)在酸性介質中,例如在0至4之pH值下進行,且第二偶合反應(ii)在升高之pH值下,在弱酸性、中性或弱鹼性介質中,例如4至8之pH值下進行。 The first coupling reaction (i) is carried out in an acidic medium, for example at a pH of 0 to 4, and the second coupling reaction (ii) is at a raised pH, in a weakly acidic, neutral or weakly basic medium. It is carried out, for example, at a pH of 4 to 8.
藉由如上文所述進行,但在方法步驟(i)及(ii)中,在各情況下使用約1莫耳當量之至少兩種,較佳兩種不相同胺之混合物,例如式(6)化合物與式(9)化合物之1:1莫耳混合物,而非使用約1莫耳當量之式(6)及式(9)之胺中之每一者,首先根據(i)獲得下式化合物之混合物:
因此本發明亦係關於染料混合物,其包含至少一種式(1)及式(1b)之染料以及至少一種式(1c)及式(1d)之染料,尤其包含式(1)、式(1b)、式(1c)及式(1d)中每一者之一種染料,其中D1、D2、R1及R2各具有上文給出之定義及較佳含義。 The invention therefore also relates to a dye mixture comprising at least one dye of the formula (1) and formula (1b) and at least one dye of the formula (1c) and the formula (1d), in particular comprising the formula (1), formula (1b) And a dye of each of formula (1c) and formula (1d), wherein D 1 , D 2 , R 1 and R 2 each have the definitions given above and preferred meanings.
混合物中式(1)、式(1b)、式(1c)及式(1d)之染料之比率可在寬範圍內變化且視根據(i)及(ii)所用之特定胺D1-NH2 與D2-NH2之比率而定。 The ratio of the dyes of the formula (1), the formula (1b), the formula (1c) and the formula (1d) in the mixture can be varied within a wide range and depending on the specific amine D 1 -NH 2 used in accordance with (i) and (ii) It depends on the ratio of D 2 -NH 2 .
上述染料混合物含有例如以混合物中式(1)、式(1b)、式(1c)及式(1d)之染料之總量計5重量%至95重量%,尤其10重量%至90重量%且較佳20重量%至80重量%之式(1)及/或式(1b)之染料。 The above dye mixture contains, for example, from 5% by weight to 95% by weight, especially from 10% by weight to 90% by weight, based on the total of the dyes of the formula (1), the formula (1b), the formula (1c) and the formula (1d). A dye of the formula (1) and/or the formula (1b) is preferably from 20% by weight to 80% by weight.
式(6)、式(7)及式(9)之化合物為已知的或可以本身已知之方式獲得。 The compounds of the formula (6), the formula (7) and the formula (9) are known or can be obtained in a manner known per se.
舉例而言,D2為上式(3a)之基團且Z1在式(4e)之基團之含義內之式(6)化合物可藉由在中性範圍內之pH值下且在例如0℃至5℃之低溫下使約1莫耳當量之2,4,6-三氯-均三或2,4,6-三氟-均三首先與約1莫耳當量之下式化合物縮合來製備:T1-H (10)。 For example, a compound of formula (6) wherein D 2 is a group of the above formula (3a) and Z 1 is within the meaning of the group of formula (4e) can be at a pH within the neutral range and is, for example, About 1 molar equivalent of 2,4,6-trichloro-all three at a low temperature of 0 ° C to 5 ° C Or 2,4,6-trifluoro-all three It is first prepared by condensation with about 1 mole equivalent of the compound below: T 1 -H (10).
該等縮合反應為已知的且描述於例如EP-A-0 260 227及US-A-4 841 049中。 Such condensation reactions are known and are described, for example, in EP-A-0 260 227 and US-A-4 841 049.
一些式(9)化合物為新型化合物。因此,本發明亦係關於下式化合物:
式(11)化合物之製備描述於實驗部分中。 The preparation of the compound of formula (11) is described in the experimental section.
本發明之式(1)之反應性染料、包含至少一種式(1)及式(1b)之染料以及至少一種式(1c)及式(1d)之染料的染料混合物以及式(11)化合物呈其自由酸形式或較佳呈其鹽形式。考慮之鹽為例如鹼金屬鹽、鹼土金屬鹽及銨鹽及有機胺之鹽。可提及鈉鹽、鋰鹽、鉀鹽及銨鹽及單乙醇胺、二乙醇胺或三乙醇胺之鹽作為實例。 A reactive dye of the formula (1) of the present invention, a dye mixture comprising at least one dye of the formula (1) and the formula (1b), and at least one dye of the formula (1c) and the formula (1d), and a compound of the formula (11) It is in the form of a free acid or preferably in the form of its salt. Salts contemplated are, for example, alkali metal salts, alkaline earth metal salts and salts of ammonium salts and organic amines. Sodium, lithium, potassium and ammonium salts and salts of monoethanolamine, diethanolamine or triethanolamine may be mentioned as examples.
適當時,最終產物亦可進行轉化反應。該轉化反應為例如藉由用稀氫氧化鈉溶液處理使Z1或Y中所含之可乙烯基化反應性基團轉化成其乙烯基形式,例如使β-硫酸根絡乙基磺醯基或β-氯乙基磺醯基轉化成乙烯基磺醯基或使α,β-二鹵丙醯胺基轉化成α-鹵丙烯醯胺基。該等反應本身為已知的。轉化反應一般在中性至鹼性介質中,在例如20℃至70℃之溫度下,在例如6至14之pH值下進行。 The final product can also undergo a conversion reaction where appropriate. The conversion reaction is, for example, conversion of the vinylatable reactive group contained in Z 1 or Y to its vinyl form by treatment with a dilute sodium hydroxide solution, for example, β-sulfate ethyl sulfonyl group Or converting the β-chloroethylsulfonyl group to a vinylsulfonyl group or converting the α,β-dihalopropylamino group to an α-halopropenylamine group. These reactions are known per se. The conversion reaction is generally carried out in a neutral to basic medium at a temperature of, for example, 20 ° C to 70 ° C, for example, at a pH of 6 to 14.
本發明之染料及染料混合物具纖維反應性。纖維反應性染料應理解為能夠與纖維素之羥基、與羊毛及絲中之胺基、羧基、羥基或硫醇基或與合成聚醯胺之胺基及可能存在之羧基反應形成共價化學鍵之纖維反應性染料。 The dyes and dye mixtures of the invention are fiber reactive. A fiber-reactive dye is understood to be capable of reacting with a hydroxyl group of cellulose, with an amine group, a carboxyl group, a hydroxyl group or a thiol group in the wool and silk, or with an amine group of a synthetic polyamine and a carboxyl group which may be present to form a covalent chemical bond. Fiber reactive dye.
本發明之染料及染料混合物適用於對極其廣泛之材料 進行染色及印刷,諸如含羥基纖維材料或含氮纖維材料。實例為絲、皮革、羊毛、聚醯胺纖維及聚胺基甲酸酯以及尤其所有種類之纖維素纖維材料。該等纖維素纖維材料為例如天然纖維素纖維,諸如棉花、亞麻布及大麻纖維,以及纖維素及再生纖維素。本發明之染料及染料混合物亦適用於對混紡織物,例如棉花與聚酯纖維或聚醯胺纖維之混合物中存在之含羥基纖維進行染色或印刷。本發明之染料及染料混合物尤其適用於對纖維素纖維材料,尤其含棉花之纖維材料進行染色或印刷。其亦可用於對天然或合成之聚醯胺纖維材料進行染色或印刷。 The dyes and dye mixtures of the invention are suitable for a very wide range of materials Dyeing and printing, such as hydroxyl-containing fibrous materials or nitrogen-containing fibrous materials. Examples are silk, leather, wool, polyamide fibers and polyurethanes and especially all types of cellulosic fiber materials. Such cellulosic fibrous materials are, for example, natural cellulosic fibers such as cotton, linen and hemp fibers, as well as cellulose and regenerated cellulose. The dyes and dye mixtures of the present invention are also suitable for dyeing or printing hydroxy-containing fibers present in blended fabrics such as cotton and polyester fibers or polyamide fibers. The dyes and dye mixtures of the invention are especially suitable for dyeing or printing cellulosic fibrous materials, especially cotton-containing fibrous materials. It can also be used to dye or print natural or synthetic polyamide fibers.
本發明之染料及染料混合物可以多種方法,尤其以染料水溶液及染料印刷漿形式塗覆至纖維材料且固定於纖維上。其適用於浸染製程且適用於根據軋染製程進行染色,根據上述製程將物品用視情況含鹽之染料水溶液浸漬,且在用鹼處理之後或在鹼存在下,視情況在加熱作用下或因在室溫下保持數小時而使染料固定。固定後,染色品或印刷品視情況在添加具有分散作用且促進未固定染料擴散之試劑之情況下用冷水及熱水充分沖洗。 The dyes and dye mixtures of the present invention can be applied to the fibrous material and to the fibers in a variety of ways, particularly in the form of aqueous dye solutions and dye printing pastes. It is suitable for the dip dyeing process and is suitable for dyeing according to the padding process, according to the above process, the article is impregnated with the salt aqueous dye solution according to the condition, and after the treatment with alkali or in the presence of a base, as the case may be under heating or The dye is fixed by holding it at room temperature for several hours. After fixation, the dyed product or print is suitably rinsed with cold water and hot water, optionally with the addition of a dispersing agent that promotes the diffusion of the unfixed dye.
本發明之染料及染料混合物之不用之處在於高反應性、良好固定能力及極佳提昇能力。因此其可用於在低染色溫度下進行浸染製程,且在軋染汽蒸製程中僅需要短汽蒸時間。固定度高且未固定染料可輕易地洗去,浸染度與固定度之間的差異顯著較小,亦即皂洗損失極小。本發明之染料及染料混合物亦尤其適用於印刷,更尤其適用於對 棉花進行印刷,且亦適用於對含氮纖維,例如羊毛或絲或含有羊毛或絲之混紡織物進行印刷。 The dyes and dye mixtures of the present invention are used in the absence of high reactivity, good fixing ability and excellent lifting ability. It can therefore be used to carry out the dip dyeing process at low dyeing temperatures, and only requires a short steaming time in the pad dyeing steaming process. The high degree of fixation and the unfixed dye can be easily washed away, and the difference between the degree of impregnation and the degree of fixation is remarkably small, that is, the soaping loss is extremely small. The dyes and dye mixtures of the invention are also particularly suitable for printing, more particularly for Cotton is printed and is also suitable for printing on nitrogen-containing fibers such as wool or silk or blended fabrics containing wool or silk.
使用本發明之染料產生之染色品及印刷品在酸性與鹼性範圍內具有高著色強度及高纖維染料結合穩定性,以及良好耐光牢度及極佳耐濕牢度特性,諸如耐洗、耐水、耐海水、耐交叉染色及耐汗漬牢度,以及良好耐褶襇、耐熱壓及耐摩擦牢度。 Dyes and prints produced by using the dye of the present invention have high color strength and high fiber dye combination stability in the acidic and alkaline range, as well as good light fastness and excellent wet fastness properties, such as washable, water resistant, Water-resistant, cross-dyeing and perspiration fastness, as well as good pleating resistance, heat resistance and rubbing fastness.
本發明之式(1)之反應性染料及包含至少一種式(1)及式(1b)之染料以及至少一種式(1c)及式(1d)之染料之染料混合物宜與其他反應性染料組合應用,例如藏青色、深藍色或黑色染色染料(諸如C.I.反應性黑5),或US-A-4,622,390、US-A-6,458,936及WO 2004/088031中所述之染料(式(102)、式(104)、式(105)、式(106)及式(107)之染料),該等文獻以引用的方式併入本文中。 The reactive dye of the formula (1) of the present invention and the dye mixture comprising at least one dye of the formula (1) and the formula (1b) and at least one dye of the formula (1c) and the formula (1d) are preferably combined with other reactive dyes. Applications such as navy, dark blue or black dyes (such as CI Reactive Black 5), or dyes as described in US-A-4,622,390, US-A-6,458,936 and WO 2004/088031 (Formula (102), (104), Formula (105), Formula (106), and Dye of Formula (107), which are incorporated herein by reference.
本發明亦係關於包含式(1)之反應性染料之水性墨水,上文給出之各別定義及較佳含義適用於D1、D2、R1及R2。 The present invention is also directed to an aqueous ink comprising a reactive dye of formula (1), the respective definitions and preferred meanings given above being applicable to D 1 , D 2 , R 1 and R 2 .
墨水中所用之染料較佳應具有低鹽含量,亦即其鹽之總含量應小於以染料之重量計0.5重量%。因製備及/或因隨後添加稀釋劑而具有相對高鹽含量之染料可例如藉由諸如超濾、逆滲透或透析之膜分離程序去鹽。 The dye used in the ink should preferably have a low salt content, i.e., the total salt content should be less than 0.5% by weight based on the weight of the dye. Dyes having a relatively high salt content due to preparation and/or subsequent addition of a diluent can be desalted, for example, by a membrane separation procedure such as ultrafiltration, reverse osmosis or dialysis.
墨水之染料總含量較佳為以墨水之總重量計1重量%至35重量%,尤其1重量%至30重量%,且較佳1重量%至20重量%。作為下限,1.5重量%,較佳2重量%且尤其3重量%之界限較佳。 The total dye content of the ink is preferably from 1% by weight to 35% by weight, particularly from 1% by weight to 30% by weight, and preferably from 1% by weight to 20% by weight, based on the total weight of the ink. As a lower limit, a limit of 1.5% by weight, preferably 2% by weight and especially 3% by weight is preferred.
墨水可包含水可混溶有機溶劑,例如C1-C4醇,諸如甲醇、乙醇、正丙醇、異丙醇、正丁醇、第二丁醇、第三丁醇及異丁醇;醯胺,例如二甲基甲醯胺及二甲基乙醯胺;酮或酮醇,例如丙酮及二丙酮醇;醚,例如四氫呋喃及二噁烷;含氮雜環化合物,例如N-甲基-2-吡咯啶酮及1,3-二甲基-2-咪唑啶酮;聚伸烷二醇,例如聚乙二醇及聚丙二醇;C2-C6伸烷二醇及硫甘醇,例如乙二醇、丙二醇、丁二醇、三乙二醇、硫代二甘醇、己二醇及二乙二醇;其他多元醇,例如甘油及1,2,6-已三醇;及多元醇之C1-C4烷基醚,例如2-甲氧基-乙醇、2-(2-甲氧基乙氧基)乙醇、2-(2-乙氧基乙氧基)乙醇、2-[2-(2-甲氧基乙氧基)-乙氧基]乙醇及2-[2-(2-乙氧基乙氧基)乙氧基]乙醇;較佳為N-甲基-2-吡咯啶酮、二乙二醇、甘油,或尤其為1,2-丙二醇,其量通常為以墨水之總重量計2重量%至30重量%,尤其5重量%至30重量%,且較佳10重量%至25重量%。 The ink may comprise a water-miscible organic solvent such as a C 1 -C 4 alcohol such as methanol, ethanol, n-propanol, isopropanol, n-butanol, second butanol, third butanol and isobutanol; Amines such as dimethylformamide and dimethylacetamide; ketones or ketols such as acetone and diacetone; ethers such as tetrahydrofuran and dioxane; nitrogen-containing heterocyclic compounds such as N-methyl- 2-pyrrolidone and 1,3-dimethyl-2-imidazolidinone; polyalkylene glycols such as polyethylene glycol and polypropylene glycol; C 2 -C 6 alkylene glycol and thioglycol, for example Ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, thiodiglycol, hexanediol and diethylene glycol; other polyols such as glycerin and 1,2,6-hexanetriol; and polyol a C 1 -C 4 alkyl ether such as 2-methoxy-ethanol, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol, 2-[ 2-(2-methoxyethoxy)-ethoxy]ethanol and 2-[2-(2-ethoxyethoxy)ethoxy]ethanol; preferably N-methyl-2- Pyrrolidone, diethylene glycol, glycerol, or especially 1,2-propanediol, usually in an amount of from 2% by weight to 30% by weight based on the total weight of the ink %, especially 5% by weight to 30% by weight, and preferably 10% by weight to 25% by weight.
墨水亦可包含增溶劑,例如ε-己內醯胺。 The ink may also contain a solubilizing agent such as ε-caprolactam.
尤其為達到調節黏度之目的,墨水可包含天然或合成來源之增稠劑。 In particular, for the purpose of adjusting the viscosity, the ink may comprise a thickener of natural or synthetic origin.
可提及之增稠劑之實例包括市售海藻酸鹽增稠劑、澱粉醚或刺槐豆粉醚,尤其單獨或與改質之纖維素混合之海藻酸鈉,該等改質之纖維素為例如甲基纖維素、乙基纖維素、羧甲基纖維素、羥乙基纖維素、甲基羥乙基纖維素、羥丙基纖維素或羥丙基甲基纖維素,尤其與較佳20重量%至25重量%羧基甲基纖維素混合之海藻酸鈉。可提及之合 成增稠劑為例如基於聚(甲基)丙烯酸或聚(甲基)丙烯醯胺之增稠劑。 Examples of thickeners which may be mentioned include commercially available alginate thickeners, starch ethers or locust bean powder ethers, especially sodium alginate, alone or mixed with modified cellulose, which are modified cellulose. For example, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, hydroxypropyl cellulose or hydroxypropyl methyl cellulose, especially preferably 20 5% by weight to 25% by weight of sodium alginate mixed with carboxymethylcellulose. Can be mentioned The thickening agent is, for example, a thickener based on poly(meth)acrylic acid or poly(meth)acrylamide.
墨水中所包含之該等增稠劑之量為例如以墨水之總重量計0.01重量%至2重量%,尤其0.01重量%至1重量%,且較佳0.01重量%至0.5重量%。 The amount of such thickeners contained in the ink is, for example, from 0.01% by weight to 2% by weight, particularly from 0.01% by weight to 1% by weight, and preferably from 0.01% by weight to 0.5% by weight, based on the total weight of the ink.
墨水亦可包含緩衝物質,例如硼砂、硼酸鹽、磷酸鹽、聚磷酸鹽或檸檬酸鹽。可提及之實例包括硼砂、硼酸鈉、四硼酸鈉、磷酸二氫鈉、磷酸氫二鈉、三聚磷酸鈉、五聚磷酸鈉及檸檬酸鈉。其用量尤其為以墨水之總重量計0.1重量%至3重量%,較佳0.1重量%至1重量%,以確立例如4至9,尤其5至8.5之pH值。 The ink may also contain a buffer material such as borax, borate, phosphate, polyphosphate or citrate. Examples which may be mentioned include borax, sodium borate, sodium tetraborate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium tripolyphosphate, sodium pentapolyphosphate and sodium citrate. It is used in an amount of, for example, 0.1% by weight to 3% by weight, based on the total weight of the ink, preferably 0.1% by weight to 1% by weight, to establish a pH of, for example, 4 to 9, especially 5 to 8.5.
作為其他添加劑,墨水可包含界面活性劑或保濕劑。 As other additives, the ink may comprise a surfactant or a humectant.
適當界面活性劑包括市售陰離子型或非離子型界面活性劑。作為本發明墨水中之保濕劑,考慮例如脲或乳酸鈉(宜呈50%至60%水溶液之形式)與甘油及/或丙二醇之混合物,保濕劑之量較佳為0.1重量%至30重量%,尤其2重量%至30重量%。 Suitable surfactants include commercially available anionic or nonionic surfactants. As a humectant in the ink of the present invention, for example, a mixture of urea or sodium lactate (preferably in the form of a 50% to 60% aqueous solution) and glycerin and/or propylene glycol is considered, and the amount of the humectant is preferably from 0.1% by weight to 30% by weight. Especially from 2% by weight to 30% by weight.
墨水較佳具有1 mPa.s至40 mPa.s,尤其1 mPa.s至20 mPa.s且較佳1 mPa.s至10 mPa.s之黏度。 The ink preferably has 1 mPa. s to 40 mPa. s, especially 1 mPa. s to 20 mPa. s and preferably 1 mPa. s to 10 mPa. s viscosity.
墨水亦可包含習用添加劑,諸如消泡劑,或尤其包含抑制真菌及/或細菌生長之物質。該等添加劑之用量通常為以墨水之總重量計0.01重量%至1重量%。 The ink may also contain customary additives such as antifoaming agents or, in particular, substances which inhibit the growth of fungi and/or bacteria. These additives are usually used in an amount of from 0.01% by weight to 1% by weight based on the total weight of the ink.
墨水可以習用方式藉由將個別組分於所要量之水中混合於一起來製備。 The ink can be prepared in a conventional manner by mixing the individual components together in the desired amount of water.
本發明之墨水尤其適用於一種記錄系統,其中墨水自小口以小液滴形式擠出,導向至上面產生影像之基質上。適當基質為例如紙、紡織纖維材料或塑膠膜。適當記錄系統為例如市售用於紙或紡織物印刷之噴墨印表機或書寫工具,諸如自來水筆或圓珠筆,且尤其為噴墨印表機。 The inks of the present invention are particularly useful in a recording system in which ink is extruded as small droplets from a small opening and directed onto a substrate on which the image is produced. Suitable substrates are, for example, paper, textile fiber materials or plastic films. Suitable recording systems are, for example, ink jet printers or writing instruments commercially available for printing on paper or textile, such as fountain pens or ballpoint pens, and especially ink jet printers.
視用途性質而定,適當時可能需要改良例如墨水之黏度或其他物理特性,尤其影響對相關基質之親和力之彼等特性。 Depending on the nature of the application, it may be desirable to modify, for example, the viscosity or other physical properties of the ink, particularly the properties of the affinity to the relevant substrate, as appropriate.
作為可用本發明墨水印刷之紙的實例,可提及市售噴墨紙、相紙、釉紙、塗塑膠紙,例如Epson噴墨紙、Epson相紙、Epson釉紙、Epson釉膜、HP專用噴墨紙、Encad光面相紙及Ilford相紙。可用本發明墨水印刷之塑膠膜為例如透明或混濁/不透明塑膠膜。適當塑膠膜為例如3M透明膜。 As examples of papers which can be printed with the ink of the present invention, mention may be made of commercially available ink jet paper, photographic paper, glazed paper, plastic coated paper, such as Epson inkjet paper, Epson photographic paper, Epson glaze paper, Epson glaze film, HP-specific Inkjet paper, Encad glossy photo paper and Ilford photo paper. The plastic film which can be printed with the ink of the present invention is, for example, a transparent or turbid/opaque plastic film. A suitable plastic film is, for example, a 3M transparent film.
作為紡織纖維材料,考慮例如含氮纖維材料或含羥基纖維材料,例如纖維素、絲、羊毛或合成聚醯胺之紡織纖維材料,較佳為纖維素之紡織纖維材料。 As the textile fiber material, for example, a nitrogen-containing fiber material or a hydroxy-containing fiber material such as cellulose, silk, wool or synthetic polyamide fiber textile material, preferably a cellulose textile fiber material, is considered.
因此本發明亦係關於藉由噴墨印刷方法印刷紡織纖維材料、紙或塑膠膜,較佳紡織纖維材料或紙,且尤其紡織纖維材料之方法,其中使用包含式(1)之反應性染料之水性墨水,上文給出之各別定義及較佳含義適用於D1、D2、R1及R2。 The invention is therefore also directed to a method for printing textile fiber materials, paper or plastic films, preferably textile fiber materials or paper, and in particular textile fiber materials, by ink jet printing, wherein a reactive dye comprising formula (1) is used. For aqueous inks, the individual definitions and preferred meanings given above apply to D 1 , D 2 , R 1 and R 2 .
在噴墨印刷方法中,將墨水之個別小液滴以控制方式自噴嘴噴灑於基質上。為達到此目的,主要使用連續噴墨方法及按需滴墨(drop-on-demand)方法。在連續噴墨方法 中,連續產生小液滴且將印刷所不需要之任何小液滴輸送至收集槽中且再循環,而在按需滴墨方法中,視需要產生小液滴且進行印刷;亦即只有當印刷需要時才產生小液滴。小液滴可例如藉助於壓電噴墨頭或藉助於熱能(氣泡噴墨)來產生。較佳藉助於本發明方法之壓電噴墨頭進行印刷。另外,較佳根據本發明方法之連續噴墨方法來印刷。 In an inkjet printing process, individual droplets of ink are sprayed onto the substrate in a controlled manner from a nozzle. To achieve this, a continuous ink jet method and a drop-on-demand method are mainly used. Continuous inkjet method Medium, continuously generating small droplets and conveying any small droplets not required for printing into the collecting tank and recycling, and in the on-demand ink dropping method, small droplets are generated as needed and printed; that is, only when printing Small droplets are produced when needed. The droplets can be produced, for example, by means of a piezo inkjet head or by means of thermal energy (bubble inkjet). Printing is preferably carried out by means of a piezoelectric ink jet head of the method of the invention. Additionally, it is preferred to print according to the continuous ink jet method of the method of the present invention.
所產生之記錄(例如印刷品)之不同之處尤其在於高色度及高色輝度以及良好耐光牢度及耐濕牢度特性。 The resulting records (e.g., prints) differ in particular by high chroma and high color brightness as well as good light fastness and wet fastness characteristics.
以下實施例用以說明本發明。除非另外指出,否則溫度以攝氏度給出,份為重量份,且百分比指重量%。以公斤與公升之比表示重量份與體積份之關係。 The following examples are intended to illustrate the invention. Unless otherwise indicated, temperatures are given in degrees Celsius, parts are parts by weight, and percentages are by weight. The relationship between the parts by weight and the parts by volume is expressed in terms of the ratio of kilograms to liters.
藉助於60 ml氫氧化鈉水溶液(30%)在pH 6至7下將80.5 g 1,3-苯二胺-4,6-二磺酸溶解於300 ml水中。隨後,添加水將混合物之體積調節至500 ml。引入250 g碎冰,且緩慢添加189 g 4-(2-氯乙基磺醯基)-丁醯氯,同時劇烈攪拌該混合物。在添加期間,藉助於碎冰及蘇打水溶液(20%溶液)將反應混合物之溫度及pH值維持於0℃至3℃及pH 5。 80.5 g of 1,3-phenylenediamine-4,6-disulfonic acid was dissolved in 300 ml of water by means of 60 ml of aqueous sodium hydroxide (30%) at pH 6 to 7. Subsequently, water was added to adjust the volume of the mixture to 500 ml. 250 g of crushed ice was introduced, and 189 g of 4-(2-chloroethylsulfonyl)-butylphosphonium chloride was slowly added while vigorously stirring the mixture. During the addition, the temperature and pH of the reaction mixture were maintained at 0 °C to 3 °C and pH 5 by means of crushed ice and aqueous soda (20% solution).
反應完成之後,藉由過濾移除不可溶部分。藉助於鹽酸(32%)將所獲得之溶液調節至pH 1.5。在攪動下添加氯化鈉以使產物沈澱。分離沈澱物且懸浮於水中。添加蘇打水溶液(20%)以在pH 4下溶解沈澱物。藉助於鹽酸(32%)將所獲得之溶液調節至pH 1.5。在攪動下添加氯化鈉以使產物沈澱。分離沈澱物且懸浮於水中。添加蘇打水溶液
(20%)以在pH 6.5下溶解沈澱物。溶液含有與下式對應之呈自由酸形式之化合物作為主要產物:
藉助於30 ml氫氧化鈉水溶液(30%)在約pH 7下將80.5 g 1,4-苯二胺-2,6-二磺酸溶解於300 ml水中。藉由添加水將混合物之體積調節至400 ml。引入300 g碎冰,且逐步添加82 g 4-(2-氯乙基磺醯基)-丁醯氯,同時劇烈攪拌該混合物,且用蘇打水溶液(20%溶液)使pH值維持於7.0。添加期間,藉助於碎冰使反應混合物之溫度維持於0℃至5℃。反應完成之後,添加水以使混合物之體積增加至900 ml。藉由過濾分離不可溶部分。溶液含有與下式對應之呈自由酸形式之化合物作為主要產物:
藉助於120 ml氫氧化鈉水溶液(30%)在pH 7下將161 g 1,4-苯二胺-2,5-二磺酸溶解於800 ml水中。隨後,添加1000 g碎冰且藉由添加20 ml鹽酸(32%)將混合物調節至pH 4.8。接著緩慢添加245 g 4-(2-氯乙基磺醯基)-丁醯氯,同時劇烈攪拌該混合物。在添加期間,藉助於碎冰及蘇打水溶液(20%溶液)將反應混合物之溫度及pH值維持於0℃至10℃及pH 5。 161 by means of 120 ml of aqueous sodium hydroxide (30%) at pH 7. g 1,4-phenylenediamine-2,5-disulfonic acid was dissolved in 800 ml of water. Subsequently, 1000 g of crushed ice was added and the mixture was adjusted to pH 4.8 by the addition of 20 ml of hydrochloric acid (32%). Then, 245 g of 4-(2-chloroethylsulfonyl)-butylphosphonium chloride was slowly added while vigorously stirring the mixture. During the addition, the temperature and pH of the reaction mixture were maintained at 0 °C to 10 °C and pH 5 by means of crushed ice and aqueous soda (20% solution).
反應完成之後,藉由在約10℃下經Dicalite過濾分離不可溶部分。溶液含有與下式對應之呈自由酸形式之化合物作為主要產物:
可藉由透析溶液分離產物以移除鹽,且隨後藉由真空蒸發濃縮。 The product can be isolated by dialysis solution to remove salts and then concentrated by evaporation in vacuo.
(a)重氮化:將704 g根據實施例1所獲得之溶液冷卻至10℃且用15 ml鹽酸(32%)酸化。在10℃下,將12.5 ml 4 N亞硝酸鈉溶液添加至所得溶液中。攪拌反應混合物30分鐘且藉由添加胺磺酸消除過量亞硝酸鹽。獲得黃色懸浮液。 (a) Diazotization: 704 g of the solution obtained according to Example 1 was cooled to 10 ° C and acidified with 15 ml of hydrochloric acid (32%). 12.5 ml of 4 N sodium nitrite solution was added to the resulting solution at 10 °C. The reaction mixture was stirred for 30 minutes and excess nitrite was eliminated by the addition of amine sulfonic acid. A yellow suspension was obtained.
(b)第二偶合:將2.5 g磷酸氫二鈉引入385 g含有約30.6 g下式化合物之水溶液中:
將溶液之溫度調節至5℃,且緩慢添加根據上文步驟(a)獲得之黃色懸浮液,同時藉由添加蘇打水溶液(20%溶液)將混合物維持於pH 5。當偶合完成時,藉由透析使染料溶液不含鹽且藉由真空蒸發濃縮,獲得產物,該產物主要含有與下式對應之呈自由酸形式之化合物:
式(104)化合物可根據US-A-7,572,301之實施例21或US-A-6,537,332之實施例26中所述之方法(第一偶合反應)獲得。可類似於US-A-7,572,301及US-A-6,537,332中所述之方法(第一偶合反應),獲得與式(104)化合物類似之處於 本發明範疇內之單偶氮化合物。 The compound of the formula (104) can be obtained according to the method described in Example 21 of US-A-7,572,301 or Example 26 of US-A-6,537,332 (first coupling reaction). Similar to the method described in US-A-7,572,301 and US-A-6,537,332 (first coupling reaction), a compound similar to the compound of formula (104) is obtained. Monoazo compounds within the scope of the invention.
(a)重氮化:將382.6 g根據實施例2所獲得之溶液冷卻至10℃且用28 ml鹽酸(32%)酸化。在10℃下,將25 ml 4 N亞硝酸鈉溶液添加至所得溶液中。攪拌反應混合物30分鐘且藉由添加胺磺酸消除過量亞硝酸鹽。獲得黃色懸浮液。 (a) Diazotization: 382.6 g of the solution obtained according to Example 2 was cooled to 10 ° C and acidified with 28 ml of hydrochloric acid (32%). 25 ml of 4 N sodium nitrite solution was added to the resulting solution at 10 °C. The reaction mixture was stirred for 30 minutes and excess nitrite was eliminated by the addition of amine sulfonic acid. A yellow suspension was obtained.
(b)第二偶合:在5℃之溫度下將20 g磷酸氫二鈉水溶液(25%)添加至根據步驟(a)獲得之黃色懸浮液中。向此攪拌且冷卻之懸浮液中緩慢引入769.3 g含有約61.2 g式(104)化合物之水溶液,同時藉由添加蘇打水溶液(20%溶液)將反應混合物維持於pH 5。藉由繼續攪動且相繼藉由進一步添加蘇打水溶液(20%溶液)使反應混合物之pH值升高至pH 7.5來完成偶合。隨後,將所獲得之染料溶液調節至pH 6,藉由透析使其不含鹽且藉由真空蒸發濃縮,獲得產物,該產物主要含有與下式對應之呈自由酸形式之化合物:
(a)重氮化:將218.2 g下式之胺:
懸浮於500 ml水中且藉由進一步添加水將懸浮液之體積調節至2800 ml。添加196 g氯化鈉且用121 ml鹽酸(32%)酸化該混合物。在室溫下,在45分鐘內將136 ml 4 N亞硝酸鈉溶液添加至所得溶液中。攪拌所獲得之懸浮液直至反應完成為止,且藉由添加胺磺酸消除過量亞硝酸鹽。 The suspension was suspended in 500 ml of water and the volume of the suspension was adjusted to 2800 ml by further addition of water. 196 g of sodium chloride were added and the mixture was acidified with 121 ml of hydrochloric acid (32%). 136 ml of 4 N sodium nitrite solution was added to the resulting solution over 45 minutes at room temperature. The suspension obtained was stirred until the reaction was completed, and excess nitrite was eliminated by the addition of amine sulfonic acid.
(b)第二偶合:藉由添加蘇打水溶液(20%溶液)將3645 g含有約318 g式(104)化合物之水溶液調節至pH 6.5。緩慢添加3192 g根據上文步驟(a)獲得之懸浮液,同時藉由添加蘇打水溶液(20%溶液)將混合物維持於pH 6.5。完成偶合隔夜。藉助於鹽酸(32%)將反應混合物調節至pH 5.5。隨後,藉由透析使染料溶液不含鹽且藉由真空蒸發濃縮,獲得產物,該產物主要含有與下式對應之呈自由酸形式之化合物:
(a)重氮化:將26.3 g根據實施例3獲得之分離產物懸浮於200 ml水中。用10 ml鹽酸(32%)酸化該混合物。在15℃至25℃之溫度下,在40分鐘內將8.2 ml 4 N亞硝酸鈉溶液添加至所得溶液中。攪拌所獲得之懸浮液直至反應完成為止,且藉由添加胺磺酸消除過量亞硝酸鹽。 (a) Diazotization: 26.3 g of the isolated product obtained according to Example 3 was suspended in 200 ml of water. The mixture was acidified with 10 ml of hydrochloric acid (32%). 8.2 ml of a 4 N sodium nitrite solution was added to the resulting solution over 40 minutes at a temperature of 15 ° C to 25 ° C. The suspension obtained was stirred until the reaction was completed, and excess nitrite was eliminated by the addition of amine sulfonic acid.
(b)第二偶合:藉由添加蘇打水溶液(20%溶液)將298 g含有約20.1 g式(104)化合物之水溶液調節至pH 6.5。緩慢添加根據上文步驟(a)獲得之懸浮液,同時藉由添加蘇打水溶液(20%溶液)將混合物維持於pH 6.5至7.5。藉助於鹽酸(32%)將反應混合物調節至pH 5.5,且完成偶合隔夜。隨後,藉由透析使染料溶液不含鹽且藉由真空蒸發濃縮,獲得50.2 g產物,該產物主要含有與下式對應之呈自由酸形式之化合物:
(a)重氮化:將9.6 g下式之胺:
懸浮於100 ml水中且藉由進一步添加水將懸浮液之體積調節至125 ml。添加8.8 g氯化鈉且用5.4 ml鹽酸(32%)酸化該混合物。在室溫下,在45分鐘內將6.2 ml 4 N亞硝酸鈉溶液添加至所得溶液中。攪拌所獲得之懸浮液直至反應完成為止,且藉由添加胺磺酸消除過量亞硝酸鹽。 The suspension was suspended in 100 ml of water and the volume of the suspension was adjusted to 125 ml by further addition of water. 8.8 g of sodium chloride was added and the mixture was acidified with 5.4 ml of hydrochloric acid (32%). 6.2 ml of 4 N sodium nitrite solution was added to the resulting solution over 45 minutes at room temperature. The suspension obtained was stirred until the reaction was completed, and excess nitrite was eliminated by the addition of amine sulfonic acid.
(b)第二偶合:將183 g根據上文步驟(a)所獲得之懸浮液添加至193 g含有約12.2 g式(104)化合物之水溶液中,且藉由添加蘇打水溶液(20%溶液)將混合物調節至pH 7.5。偶合反應完成之後,藉助於鹽酸(32%)將反應混合物調節至pH 5.5。隨後,藉由透析使染料溶液不含鹽且藉
由真空蒸發濃縮,獲得23.7 g產物,該產物主要含有與下式對應之呈自由酸形式之化合物:
實施例9至實施例35:遵循類似於實施例4至實施例8中之一者所述之程序,但對於第一偶合反應使用等莫耳量之式D2xy-NH2之胺且對於第二偶合反應使用等莫耳量之式D1xy-NH2之另一胺,且視具體情況用2-甲胺基-5-萘酚-7-磺酸或2-磺基甲胺基-5-萘酚-7-磺酸替代2-胺基-5-萘酚-7-磺酸,獲得與通式(112)對應之呈自由酸形式之化合物,其中D1xy、D2xy及R2具有表1、表2及表3中所示之含義。 Example 9 to Example 35: Following procedures similar to those described in one of Examples 4 to 8, but using an equimolar amount of an amine of the formula D 2 xy -NH 2 for the first coupling reaction and for the first The di-coupling reaction uses another molar amount of another amine of the formula D 1 xy -NH 2 and, as the case may be, 2-methylamino-5-naphthol-7-sulfonic acid or 2-sulfomethylamino-5 -Naphthol-7-sulfonic acid instead of 2-amino-5-naphthol-7-sulfonic acid, obtaining a compound in a free acid form corresponding to the formula (112), wherein D 1xy , D 2xy and R 2 have The meanings shown in Table 1, Table 2 and Table 3.
浸染:在60℃下將經編棉織物引入液比為1:10之染浴水溶液中,該染浴水溶液含有如表4中所示之量的根據實施例6製備之式(108)之染料或下式之參考染料:
在60℃下45分鐘之後,添加表4中給定量之鍛燒碳酸鈉。持續染色45分鐘。接著用水沖洗染色物品,皂洗且再沖洗,且接著乾燥。 After 45 minutes at 60 ° C, a given amount of calcined sodium carbonate in Table 4 was added. Continue staining for 45 minutes. The dyed article is then rinsed with water, soaped and rinsed again, and then dried.
以光譜方式量測由染色液1至6獲得之染色品之著色強度。表5展示根據實施例6製備之染料及式(201)之參考染料之提昇特性。本發明之染料展示極佳之提昇特性。 The coloring intensity of the dyed product obtained from the dyeing liquids 1 to 6 was measured spectrally. Table 5 shows the lifting characteristics of the dye prepared according to Example 6 and the reference dye of formula (201). The dyes of the present invention exhibit excellent lifting characteristics.
對根據上文方法用0.8%式(108)之染料(參考深度:0.92)或用1.8%式(201)之參考染料(參考深度:0.96)染色之漂白經編棉織物進行色牢度測試(氙弧褪色性測試:照射72小時)。根據灰階測定顏色變化。用本發明之式(108) 之染料染色之織物評為4至5,而用式(201)之參考染料染色之織物僅評為3至4。 Color fastness test for bleached warp knitted fabric dyed with 0.8% dye of formula (108) (reference depth: 0.92) or 1.8% reference dye of formula (201) (reference depth: 0.96) according to the above method ( Xenon arc fading test: 72 hours of irradiation). The color change is determined according to the gray scale. Using the formula (108) of the present invention The dye-dyed fabric was rated 4 to 5, while the fabric dyed with the reference dye of formula (201) was rated only 3 to 4.
在60℃下將100份棉織物引入1500份含有45 g/l氯化鈉及2份根據實施例6獲得之反應性染料之染浴中。在60℃下45分鐘之後,添加20 g/l無水碳酸鈉。在彼溫度下再繼續染色45分鐘。接著沖洗染色物品,在沸點下用非離子型清潔劑皂洗一刻鐘,再沖洗且乾燥。 100 parts of cotton fabric was introduced into 1500 parts of a dye bath containing 45 g/l of sodium chloride and 2 parts of the reactive dye obtained according to Example 6 at 60 °C. After 45 minutes at 60 ° C, 20 g/l of anhydrous sodium carbonate was added. The dyeing was continued for another 45 minutes at the temperature. The dyed article is then rinsed, soaped with a non-ionic detergent at the boiling point for a quarter of an hour, rinsed and dried.
作為上文程序之替代程序,可在80℃而非60℃下進行染色。 As an alternative to the above procedure, dyeing can be carried out at 80 ° C instead of 60 ° C.
將0.1份實施例6之染料溶解於200份水中,且添加0.5份硫酸鈉、0.1份均染佐劑(基於高級脂族胺與環氧乙烷之縮合產物)以及0.5份乙酸鈉。接著使用乙酸(80%)將pH值調節至5.5之值。在50℃下加熱染浴10分鐘,且接著添加10份羊毛織物。接著經約50分鐘加熱至100℃之溫度且在彼溫度下染色60分鐘,此後將染浴冷卻至90℃且移出染色物品。用熱水及冷水洗滌羊毛織物,且接著離心且乾燥。 0.1 part of the dye of Example 6 was dissolved in 200 parts of water, and 0.5 part of sodium sulfate, 0.1 part of a leveling adjuvant (based on a condensation product of a higher aliphatic amine and ethylene oxide), and 0.5 part of sodium acetate were added. The pH was then adjusted to a value of 5.5 using acetic acid (80%). The dye bath was heated at 50 ° C for 10 minutes and then 10 parts of wool fabric was added. It was then heated to a temperature of 100 ° C over about 50 minutes and dyed at the temperature for 60 minutes, after which the dye bath was cooled to 90 ° C and the dyed articles were removed. The wool fabric was washed with hot and cold water and then centrifuged and dried.
在快速攪拌下,將3份根據實施例6獲得之染料噴灑於100份含有50份5%海藻酸鈉增稠劑、27.8份水、20份脲、1份間硝基苯磺酸鈉及1.2份碳酸氫鈉之原漿中。使用由此獲得之印刷漿印刷棉織物,且使所得印刷材料乾燥且 在102℃下於飽和蒸汽中汽蒸2分鐘。接著沖洗印刷織物,必要時在沸點下皂洗且再沖洗,且隨後乾燥。 3 parts of the dye obtained according to Example 6 were sprayed in 100 parts containing 50 parts of 5% sodium alginate thickener, 27.8 parts of water, 20 parts of urea, 1 part of sodium m-nitrobenzenesulfonate and 1.2 under rapid stirring. In the original slurry of sodium bicarbonate. Printing the cotton fabric with the printing paste thus obtained, and drying the resulting printing material and Steamed in saturated steam at 102 ° C for 2 minutes. The printed fabric is then rinsed, if necessary, soaped at the boiling point and rinsed again, and then dried.
(a)使用含有30 g/l碳酸鈉及50 g/l脲之液體軋染絲光棉緞(液體吸收率70%)且乾燥。 (a) Silk-dyed satin (liquid absorption rate 70%) was padded using a liquid containing 30 g/l sodium carbonate and 50 g/l urea and dried.
(b)使用按需滴墨噴墨頭(氣泡噴墨)用水性墨水印刷根據步驟(a)預先處理之棉緞,該水性墨水含有 (b) printing the cotton satin pre-treated according to the step (a) with an on-demand ink jet head (bubble ink jet) using an aqueous ink containing
- 15重量%實施例6之式(108)之反應性染料 - 15% by weight of the reactive dye of the formula (108) of Example 6
- 15重量% 1,2-丙二醇及 - 15% by weight of 1,2-propanediol and
- 70重量%水。 - 70% by weight of water.
使印跡完全乾燥且在102℃下在飽和蒸汽中固定8分鐘,冷沖洗,在沸點下洗滌,再沖洗且乾燥。 The blot was completely dried and fixed in saturated steam for 8 minutes at 102 ° C, cold rinsed, washed at the boiling point, rinsed again and dried.
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