TWI326295B - Reactive dyes containing an alkylthio-s-triazinyl reactive grouping - Google Patents

Description

1326295 九、發明說明： 【發明所屬之技術領域】 本發明係有關一種新穎反應性染料，特別是關於一種 具有硫烧基-S -二氣。井之反應性染料。 【先前技術】 具有硫烧基-s-三氮〇井（alkylthio-s-triazine)單反應基 反應性染料技術開發從1960年代一直到1980年代早期。1326295 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a novel reactive dye, and more particularly to a sulphur-based-S-digas. The reactive dye of the well. [Prior Art] The alkylthio-s-triazine single reactive reactive dye technology was developed from the 1960s to the early 1980s.

主要是具有-s-三氮〇井（s-triazine)或嘴咬衍生物（pyramine) 的硫代/硫磺單反應基反應性染料之技術，如英國專利GB 923068所揭露》 1986年到1996年間雖有反應性染料的研究開發，但 是反應性染料研究開發只侷限在特定的染料發色團範圍， 如歐洲專利EP 0264878、日本專利JJM〇-〇〇i618所揭露。 以 '一亂均二σ井 (monochloro triazine)和乙稀颯Mainly a technique of thio/sulfur mono-reactive dyes having a s-triazine or a s-triazine or a pyramine, as disclosed in British Patent GB 923068, 1986-1996 Despite the research and development of reactive dyes, the research and development of reactive dyes is limited to a specific range of dye chromophores, as disclosed in European Patent EP 0264878, Japanese Patent JJM〇-〇〇i618. 'monochloro triazine and acethanide

(Vinylsulfone)作為雙反應基之反應性染料，為現今6〇〇c 中溫型反應性染料之市場主流，但由於兩個反應基的活性 相差很大，染色應用時，主要以乙烯颯反應基將染料固著 到纖維素纖維，而一氣均三。井反應基之利用率偏低，因為 一氯均三啩反應基是屬於80γ固色的反應基。如果用中 溫型一氟均三。井反應基取代一氣均三。井，雖然可以和乙烯 颯反應基的活性趨於一致，增加上色率，但三氟均三口井 ⑻fi_ triazine)的生產成本太高，染料產品的經濟= 低。本發明提供以魏基做H⑼的取代基提升反 5 1326295 應基活性與乙烯砜相當，有效增加反應基利用率，染料表 現高固著和優良染深性，而且比一氟均三〇井（monofluoro triazine)更具經濟效益。本發明之新穎反應性染料可以表 現出更好的反應性、固著率、染深性，以及具有更穩定的 纖維和染料鍵結、更優良的水洗牢度、日光牢度和濕牢度 特性。 利用本發明之硫烷基取代基提升一氣均三。井的活 性，搭配乙烯颯成為反應性一致的新雙反應基染料，反應 選擇性高，可以成為高經濟效益的高級中溫型染料。 【發明内容】 本發明提供一種如下式（I)之具有硫烷基-s-三氮。井反 應基之反應性染料，(Vinylsulfone) as a reactive dye for double-reactive groups, is the mainstream market for 6〇〇c medium-temperature reactive dyes today, but due to the large difference in activity between the two reactive groups, the dyeing application mainly uses ethylene ruthenium reactive groups. The dye is fixed to the cellulose fibers, and the gas is uniform. The utilization rate of the well reaction group is low because the monochlorotriazine reactive group is a reactive group belonging to 80 gamma fixation. If the medium temperature type is used, the fluorine is three. The well reaction group is replaced by one gas. Although the well can be consistent with the activity of the vinyl hydrazine reactive group and increase the coloring rate, the production cost of the trifluoron well (8) fi_ triazine is too high, and the economy of the dye product is low. The invention provides the substituent of H(9) with Wei group as the substituent, and the activity of the anti- 5 1326295 is equivalent to that of vinyl sulfone, which effectively increases the utilization ratio of the reaction group, the dye exhibits high fixation and excellent dyeing depth, and is better than the monofluoron well ( Monofluoro triazine) is more economical. The novel reactive dyes of the present invention can exhibit better reactivity, fixation, dyeing, and more stable fiber and dye bonding, better wash fastness, light fastness and wet fastness characteristics. . The use of the sulfanyl substituent of the present invention enhances one gas averaging. The activity of the well, together with ethylene oxime, becomes a new double-reactive dye with consistent reactivity, and has high reaction selectivity and can be a high-efficiency intermediate-temperature dye. SUMMARY OF THE INVENTION The present invention provides a sulfanyl-s-triazole having the following formula (I). Reactive dye of the well reaction group,

其中： X、Y和Z係各自獨立的選自由氫原子（hydrogen)、氯原子 (chlorine)、經基（hydroxy)、胺基（amino)、經取代之胺基、 磺酸鹽（sulfonate)、芳香族偶氣基（arylazo)、2-氣-4-炫硫三 氮 〇井-6-胺基（2-chloro-4-alkylthio-triazinyl- 6-amino)、烧 基（alkyl)、院氧基（alkoxy)、α，卢-鹵丙酿基 1326295 (M-hai〇propionyl)、α 齒丙烯酿基（a hai〇acryi〇州、 -B-S02CH2CH2W、-B-S02CH=CH2、-S02CH2CH2W 及 -S02CH=CH2所組成之群； B 為直鏈或 _C0NH-(CH2)丨-或-〇_(CH2)j-CONH- (CH2)k-，i、 j和k為各自獨立2到4的整數； W為用鹼處理可離去之基團，其係選自包括：c卜_〇s〇3h、 0R9 I ~NrR'°Wherein: X, Y and Z are each independently selected from the group consisting of a hydrogen atom, a chlorine atom, a hydroxy group, an amino group, a substituted amine group, a sulfonate group, Aromatic arylazo, 2-chloro-4-alkylthio-triazinyl-6-amino, alkyl, ortho-oxygen Alkoxy, α, Lu-halo-propyl 1326295 (M-hai〇propionyl), α-tooth acryl-based (a hai〇acryi 〇州, -B-S02CH2CH2W, -B-S02CH=CH2, -S02CH2CH2W and -S02CH=CH2 group; B is linear or _C0NH-(CH2)丨- or -〇_(CH2)j-CONH- (CH2)k-, i, j and k are independent 2 to 4 An integer of; W is a group which can be removed by treatment with a base, and is selected from the group consisting of: cBu_〇s〇3h, 0R9 I ~NrR'°

Lh、及季敍鹽R丨丨，其中R9、R10、R丨丨各自獨立分別Lh, and the seasonal salt R丨丨, wherein R9, R10, and R丨丨 are each independently

為C 1〜4烧基； Q為c | ·4燒基或經取代之c丨·4烧基； Α為一個或多個染料發色團，具有一個或多個項酸基； 汪為1或2 ; R為氫原子、c^4烷基、或經羥基、d~4烷氧基、或羧基 (carboxyl)所取代的Cl〜4烷基。 本發明之式（I)反應性染料，其包含一個或多個染料發 色團’可以連接一個或多個續酸基（sulf0)和至少兩個纖維 反應基，其中一個纖維反應基必為2_氣_4_硫烷基_s•三。井 基（2-chloro-4-alkylthio-s-triazinyl) 〇 本發明之式（I)反應性染料，其中Q，較佳的，為未取 代或經一至三個取代基取代之甲烷基或乙烷基，且該甲院 基、乙烧基上之取代基係分別選自包括：卣素（halo)、氫氧 基（hydroxyl)、續酸基、氰基（cyano)、胺基（amino)、幾醯 胺基（carbonamido)、缓基（carboxyl)、烧氧幾基 (alkoxycarbonyl)、醯氧基（acyloxy)及炫氧基。 1326295 本發明之式（I)反應性染料，其中該染料發色團A，較 佳的，係選自包括··甲腊(formazan)、蒽醌（anthraquinone)、 肽花青（phthalocyanine)、三苯二噁口井（triphendioxazine)、 單偶氮（monoazo)、雙偶氮（disazo)、多偶氮（polyazo)及金 屬錯合偶氮結構發色團所組成之群。 其中該肽花青（phthalocyanine)發色團’較佳的’為如 下式之結構者：Is a C 1~4 alkyl group; Q is c | · 4 alkyl or substituted c丨·4 alkyl; Α is one or more dye chromophores, having one or more acid groups; Or 2; R is a hydrogen atom, a C 4 alkyl group, or a C 4 alkyl group substituted by a hydroxyl group, a d 4 alkoxy group, or a carboxyl group. The reactive dye of the formula (I) of the present invention, which comprises one or more dye chromophores' may be bonded to one or more acid-reducing groups (sulf0) and at least two fiber reactive groups, wherein one fiber reactive group must be 2 _ gas _4_sulfanyl _s• three. 2-chloro-4-alkylthio-s-triazinyl 反应 a reactive dye of the formula (I) of the present invention, wherein Q, preferably, is unsubstituted or substituted with one to three substituents of methyl or ethyl An alkyl group, and the substituents on the phenyl group and the alkyl group are respectively selected from the group consisting of halo, hydroxyl, acid, cyano, and amino. , a carbonamido, a carboxyl group, an alkoxycarbonyl group, an acyloxy group, and a methoxy group. 1326295 A reactive dye of the formula (I) of the present invention, wherein the dye chromophore A, preferably selected from the group consisting of: formazan, anthraquinone, phthalocyanine, three A group of triphendioxazine, monoazo, disazo, polyazo, and metal-missing azo structure chromophores. Wherein the phthalocyanine chromophore 'better' is a structure of the formula:

(S02U)c(S02U)c

S〇2— NH-E- d 其中Pc為銅肽花青基（copper phthalocyanine)或錄肽花青 基（nickel phthalocyanine)，U 為-OH 和 /或-NH2，E 為苯基. 或乙稀基（ethylene) ; c + d S 4。 其中該三苯二°惡〇井（triphendioxazine)發色團，較佳S〇2—NH-E- d where Pc is copper phthalocyanine or nickel phthalocyanine, U is -OH and/or -NH2, and E is phenyl. or ethylene Ethylene; c + d S 4. Wherein the triphenyldioxazine chromophore is preferred

的，係選自包括：, selected from:

13262951326295

OHOH

OHOH

S03HS03H

1010

料trr之染料適用於纖維材料，尤指纖維素纖維材 材料並4=纖維之纖維材料的染色或印花。此纖維 二L、特殊限制，可以是天然或再生的纖維素纖維，例 /麻、亞麻、***、苧麻、黏液嫘縈，或是含纖維素 糸纖維的纖維材I本發明之染料同樣也適料含經基纖 維的纖維摻混織物的染色和印花。The dye of trr is suitable for dyeing or printing of fibrous materials, especially cellulose fiber materials and 4 = fiber materials of fibers. The fiber L, particularly limited, may be natural or regenerated cellulose fibers, such as hemp, flax, hemp, ramie, mucilage, or a fiber containing cellulose fiber. The dye of the present invention is also suitable. Dyeing and printing of fiber blended fabrics containing base fibers.

本發明之染料可以用各種方式固色於纖維上特別是 以水性染料溶液和印染糊形式。並以浸染、連染、冷壓染、 印染等方式進行染色與印花。 ” 明之染色或印染可照一般習知、慣用的方法進 行，汉染法（exhaustion dyeing)是採用熟知的無機中性鹽 j如無水硫酸鈉及氯化鈉）及熟知的酸結合劑（如碳酸鈉、氫 氧化鈉）單獨或混合使用。無機中性鹽和鹼的用量並不是很 重要，無機中性鹽和鹼可以依傳統方法一次或分次加入染 浴中。此外，也可以依傳統方法加入助染劑（如均染劑、缓 13 1326295 染劑等）’染色溫度通常是介於40。(：-90。(：，較佳的是40。(： -70〇C。 冷壓朱法疋使4染色的物質，利用熟知的無機中性鹽 (如無水硫酸鈉及氣化鈉）及熟知的酸結合劑（如碳酸鈉氫 氧化鈉）軋染，然後在室溫下，使所得的物質成捲置形式進 行染色。 連續染色法是使熟知的酸結合劑（如碳酸鈉或碳酸氫 鈉）和軋染液混合，依常法使欲染色之物質進行軋染，然後 • 使所得物質乾熱或汽蒸固色；兩浴軋染法是以染料使欲染 色之物質進行軋染，然後以熟知的無機中性鹽（如硫酸鈉或 矽酸鈉）處理，最好依常法將處理過的物質乾燥或汽蒸固 色。 織物印花法，例如有單相印花法，係以含有熟知酸結 合劑（如碳酸氫鈉）之印花漿，印在欲印花的物質上，並用 乾燥或汽蒸固色；兩相印花法包含以印花漿欲印花的物 質將所得物質浸入在高溫（90°C或以上）之含無機中性鹽 鲁（如氯化鈉）及熟知的酸結合劑（如氫氧化鈉或碳酸鈉）之溶 液中固色。依本發明之方法並不侷限前列之染色或印花法。 本發明之染料對纖維素纖維來講，它是一種具產業價 值的反應性染料，具備優良的gj色能力，和非常優異的染 冰’=，同時具備高度的洗淨能力，並適用於廣泛溫度範圍 =染色，因此也適用於棉/聚酯摻混織物的染色。本發明的 染料也適用於印染，特別適用於棉或含有毛或絲的摻混織 勿在纖維素纖維材料上所進行的染色和印染可以得到各 14 可得 種染色特性良好的染物；尤其在染深性及水洗牢度 阿品質的染色、印染或壓染產品。 【實施方式】 本發明之染料，可由習知的方法製備，其中重氮化反 =、偶合和縮合反應常見於此領域之文獻中，並且為熟悉 °亥項技術者可以據以實施。 為方便更進-步說明起見，將列舉以下實施例做更具 的說明。以下κ例在說明本發明，本發明之中請專利範 圍並不會因此而丈限制。其中化合物是以游離酸的形式表 不，但其實際的形式有可能是金屬鹽，更可能是鹼金屬鹽， 尤其疋鈉鹽，除非有特別說明，否則實施例中所使用的份 數或百分比皆以重量為單位，溫度以攝氏溫度。c為單位。 實施例1 (a) 取 19.45 份二聚氯氰（Cyanuric chi〇ride)分散於 150 份 之0°C水中，然後加入31.9份2-胺基-5-萘酚-1，7-二 磺酸（2-Amino-5-hydroxy-naphthalene- l，7-disulfonic acid)粉末，以15%碳酸鈉（Na2C03)水溶液將反應液pH 值調整為3，自然升溫至2〇〇C後持溫小時備用。 (b) 取9.7份硫乙醇酸（Thi〇giyC〇lic acid)加入上述⑷所得 之水；谷液中’在20°C以18份碳酸鈉（Na2C03)粉末將 反應液pH值調整為7〜7.5之間，保持15分鐘後用鹽 酸（HC1)水溶液調整反應液的pH值為6〜6.5，經過常 用的氣化鈉（NaCl)鹽析、過濾，取濾餅備用》 15 1326295 (c) 取150份、〇°C之水加入29.5份1-胺苯基-4-(β-乙烯 職）-2-石黃酸（1 -aminobenzene-4-(p-sulfatoethyl -sulfone)-2-sulfonic acid)和 30 份 32%鹽酸水溶液充分 攪拌分散’之後快速加入7.2份的亞硝酸鈉水溶液， 控制在0〜5°C下進行重氮化反應約1.5小時完成，加 入上述（b)所得之濾餅，用碳酸氫鈉緩慢調整反應pH 值達到6〜6.5，充分反應後經鹽析、過遽和乾燥得到 橘色產物的結構如下式（1)The dyes of the present invention can be fixed to the fibers in a variety of ways, particularly in the form of aqueous dye solutions and printing pastes. Dyeing and printing are carried out by means of dip dyeing, continuous dyeing, cold pressure dyeing, printing and dyeing. "Dyeing or printing can be carried out according to conventional and customary methods. Exhaustion dyeing is carried out using well-known inorganic neutral salts such as anhydrous sodium sulfate and sodium chloride) and well-known acid binders (such as carbonic acid). Sodium, sodium hydroxide) used alone or in combination. The amount of inorganic neutral salt and alkali is not very important, inorganic neutral salt and alkali can be added to the dye bath once or in part according to the traditional method. In addition, it can also be traditionally Add dye aids (such as leveling agent, mild 13 1326295 dye, etc.) 'The dyeing temperature is usually between 40. (: -90. (:, preferably 40. (: -70〇C. Cold pressed Zhu The 4 dyed material is padded with well-known inorganic neutral salts (such as anhydrous sodium sulfate and sodium carbonate) and well-known acid binders (such as sodium carbonate sodium hydroxide), and then obtained at room temperature. The material is dyed in a roll form. The continuous dyeing method is to mix a well-known acid binder (such as sodium carbonate or sodium hydrogencarbonate) with a padding solution, and the material to be dyed is padded according to the usual method, and then Material dry heat or steam solidification; two bath padding The dye to be dyed is dyed with a dye, and then treated with a well-known inorganic neutral salt such as sodium sulfate or sodium citrate, and the treated material is preferably dried or steam-fixed according to a usual method. The method, for example, has a single-phase printing method, which is printed on a material containing a well-known acid binder (such as sodium hydrogencarbonate), printed on a material to be printed, and dried or steamed; the two-phase printing method comprises a printing paste. The substance to be printed is immersed in a solution containing an inorganic neutral salt such as sodium chloride at a high temperature (90 ° C or higher) and a well-known acid binder (such as sodium hydroxide or sodium carbonate). The method according to the present invention is not limited to the preceding dyeing or printing method. The dye of the present invention is an industrially valuable reactive dye for cellulose fibers, has excellent gj color ability, and is excellent in dyeing. Ice '=, with high cleaning ability and suitable for a wide temperature range = dyeing, so it is also suitable for dyeing cotton/polyester blended fabrics. The dyes of the invention are also suitable for printing and dyeing, especially for cotton or contain hair Or dyeing of silk or woven fabrics, dyeing and printing on cellulose fiber materials can obtain dyes with good dyeing properties of 14 kinds; especially dyeing, printing or dyeing with dyeing fastness and washing fastness [Embodiment] The dye of the present invention can be produced by a conventional method in which diazotization, coupling, and condensation reactions are common in the literature in the field, and can be carried out by those skilled in the art. For the convenience of further description, the following examples will be further illustrated. The following κ examples illustrate the invention, and the scope of the invention is not limited thereby. The compound is free acid. The form is not, but the actual form may be a metal salt, more likely an alkali metal salt, especially a sodium salt, unless otherwise stated, the parts or percentages used in the examples are by weight. The temperature is in degrees Celsius. c is the unit. Example 1 (a) 19.45 parts of Cyanuric chi〇ride was dispersed in 150 parts of 0 ° C water, and then 31.9 parts of 2-amino-5-naphthol-1,7-disulfonic acid was added. (2-Amino-5-hydroxy-naphthalene- l,7-disulfonic acid) powder, the pH of the reaction solution was adjusted to 3 with a 15% sodium carbonate (Na2CO3) aqueous solution, and the temperature was naturally raised to 2 〇〇C, and the temperature was maintained for an hour. . (b) 9.7 parts of thioglycolic acid (Thi〇giyC〇lic acid) was added to the water obtained in the above (4); in the gluten solution, the pH of the reaction solution was adjusted to 7 at 18 ° C with 18 parts of sodium carbonate (Na 2 CO 3 ) powder. Between 7.5, after 15 minutes, adjust the pH of the reaction solution with hydrochloric acid (HC1) aqueous solution to 6~6.5. After salting out with common sodium (NaCl), filter, take the filter cake for use. 15 1326295 (c) 150 parts of water of 〇 °C was added to 29.5 parts of 1-aminophenyl-4-(β-vinyl-phenylene)-2-sulfonic acid (1-aminobenzene-4-(p-sulfatoethyl-sulfone)-2-sulfonic acid And 30 parts of 32% hydrochloric acid aqueous solution are thoroughly stirred and dispersed ', then quickly add 7.2 parts of sodium nitrite aqueous solution, control the diazotization reaction at 0~5 ° C for about 1.5 hours to complete, add the filter cake obtained in the above (b) Slowly adjust the pH of the reaction with sodium bicarbonate to 6~6.5. After fully reacting, salting out, hydrazine and drying to obtain the structure of the orange product is as follows (1)

實施例2 (a) 取19.45份三聚氣氰分散於150份的〇。〇水中，加入 31.5 份 1-萘盼-8-胺基-3,6-二績酸（i-Naphthol-8-amino -3，6-disulfonic acid)粉末’以15%碳酸納水溶液將反 應液pH值調整為3 ’自然升溫至20。(：後持溫i〜2小 時備用。 (b) 取9.7份硫乙醇酸加入上述（a)所得之水溶液中，在2〇 °C以18份碳酸鈉將反應液pH值調整為7〜7 5，保持 15分鐘後用鹽酸水溶液調整混合液的pH值為 6〜6.5 ’經過常用的氣化鈉鹽析、過濾，取濾餅備用。 16 1326295Example 2 (a) 19.45 parts of trimeric cyanogen were dispersed in 150 parts of hydrazine. In the hydrophobic water, 31.5 parts of 1-iphthol-8-amino-3,6-disulfonic acid powder was added to the reaction solution in 15% sodium carbonate aqueous solution. The pH is adjusted to 3 'naturally warmed to 20. (: After holding the temperature i~2 hours for standby. (b) Add 9.7 parts of thioglycolic acid to the aqueous solution obtained in the above (a), and adjust the pH of the reaction solution to 7~7 with 18 parts of sodium carbonate at 2 °C. 5, after 15 minutes, adjust the pH of the mixture with hydrochloric acid aqueous solution to 6~6.5 ' After the common gasification sodium salting out, filter, take the filter cake for use. 16 1326295

實施例 染料結構式 色相 4 C1 h〇3s. 1 \_ N^N H3C N=N-Y '^NH~^nJLSCH3 n\n/^oh s〇3H Φ SO2C2H4OSO3H (4) Brilliant Yellow 黃色 5 Cl so3h 1 /~~( /=\ HO3SOH4C2O2S—f y—N=N \—NH——SCH2CO2H H3COCHN (5) Yellow 黃色 6 ^-HNOC—^ ^N=N—KH-i^JLSCH2c〇2H HO3SOH4C2O2S H2N0CHN (6) Yellow 黃色 7 HO3SOH4C2O2S—〈〉—N—N —〉—NH——SCH2CO2H H2N0CHN ⑺ Yellow 黃色 8 Cl ,〇ch3 1 HO3SOH4C2O2S—i \—N=N—^ \—NH——SC2H5 h3c h2nochn (8) Yellow 黃色 19 1326295 9 Cl |〇3H __ N^'N HOsSORjCAS^^^^5^ H3C0CHN (9) Yellow 黃色 10 Cl h〇3SAC2°^ νΛ ^j^pN=N^^-NH-^NJLsc此 \ / h2nochn (10) Yellow 黃色 11 Ci X人 邮 ΗϊΝοαίΝ^ r^^N=N \__) HOzCHit^HN^S^ ^ S^H N^N Cl^^tr^SCHzCOzH (11) Yellow 黃色 12 —/S〇3H OH C1 ho3soh4c2o2s-^)-n=n-VyN L (12) Orange 橘色 13 OH 0-ηνχ^^ν=ν-Λ〇, X _)心哪厂 HOaS^^^^NH-i^/JL-S^H (13) Orange 橘色 14 Cl 严化 OH // \ /NH —^—SCH2CO2H H〇3SOH4C2Q2S-^ / N=N~T ll /7 Hn H3C0 H°3b (14) Orange 橘色 20 1326295EXAMPLES Dye structure hue 4 C1 h〇3s. 1 \_ N^N H3C N=NY '^NH~^nJLSCH3 n\n/^oh s〇3H Φ SO2C2H4OSO3H (4) Brilliant Yellow Yellow 5 Cl so3h 1 / ~~( /=\ HO3SOH4C2O2S—fy—N=N \—NH—SCH2CO2H H3COCHN (5) Yellow Yellow 6 ^-HNOC—^ ^N=N—KH-i^JLSCH2c〇2H HO3SOH4C2O2S H2N0CHN (6) Yellow Yellow 7 HO3SOH4C2O2S—<〉—N—N —〉—NH—SCH2CO2H H2N0CHN (7) Yellow Yellow 8 Cl ,〇ch3 1 HO3SOH4C2O2S—i \—N=N—^ \—NH—SC2H5 h3c h2nochn (8) Yellow Yellow 19 1326295 9 Cl |〇3H __ N^'N HOsSORjCAS^^^^5^ H3C0CHN (9) Yellow Yellow 10 Cl h〇3SAC2°^ νΛ ^j^pN=N^^-NH-^NJLsc this \ / h2nochn ( 10) Yellow Yellow 11 Ci X人邮ΗϊΝοαίΝ^ r^^N=N \__) HOzCHit^HN^S^ ^ S^HN^N Cl^^tr^SCHzCOzH (11) Yellow Yellow 12 —/S〇3H OH C1 ho3soh4c2o2s-^)-n=n-VyN L (12) Orange Orange 13 OH 0-ηνχ^^ν=ν-Λ〇, X _)Heart factory HOaS^^^^NH-i^/JL- S^H (13) Orange Orange 14 Cl Strict OH // \ /NH —^—SCH2CO2H H〇3SOH4C2Q2S-^ / N=N~T ll /7 Hn H3C0 H°3b (14) Orange Orange 20 1326295

21 132629521 1326295

22 132629522 1326295

23 1326295 得助劑糊。 取3份實施例2所製備的染料灑於上述1〇〇份的助劑糊 中，並快速攪拌。以l〇〇mesh的45度斜紋版印花網版覆蓋 在一適當大小的絲光棉斜紋布上，再將上述色糊置於網版 上並刮過。 將刮好的布放到65。(：烘箱内5分鐘烘乾；將烘乾好的布放 入蒸箱以常壓飽和蒸氣102〜1〇5^蒸處1〇分鐘。 然後將所得到玫瑰紅色染物先經冷水洗，再經沸騰熱水洗 1〇分鐘，然後再以沸腾之非離子清潔劑皂洗10分鐘，最 後再用冷水洗清一次’乾燥後可得到紅色染物具備優良的 染深性及上色率。 試驗例3 取3份貫施例3所製備的染料溶於1〇〇毫升水中，配製成 30伤/升壓染液，取鹼劑25毫升（使用苛性鈉μ毫升/升和 芒硝30份/升）加入於壓染液中均勻攪拌，所得混合液倒入 # 羅拉（R〇】ler)壓染器中，然後將棉織物經過羅拉壓染後，再 捲成軸狀。此形態棉織物在室溫下儲存4小時。然後，將所 付到橘色染物先經冷水洗，再經沸騰熱水洗1〇分鐘，然後 經沸騰之非離子清潔劑皂洗1〇分鐘，最後再用冷水洗清一 -人，乾燥後可得到深藍色染物具備優良的染深性及上色率。 綜上所述’本發明確能藉所揭露之技術思想以達到發 明目的，具新穎性、進步性與可供產業利用性，並與發明 專利要件相符合。惟以上所揭示者，乃較佳實施例，舉凡 28 1326295 局部之變更或修飾而源於本案之技術思想而為熟悉該項技 術之人士所易於推知者，倶不脫本案之專利權範圍。 【圖式簡單說明】 無 【主要元件符號說明】 無23 1326295 Get the assistant paste. Three parts of the dye prepared in Example 2 were sprinkled on the above-mentioned one-part auxiliary paste, and stirred rapidly. Cover the appropriate size of mercerized cotton twill with a 45 degree twill print screen of l〇〇mesh, and place the color paste on the screen and scrape it. Place the scraped cloth at 65. (: Dry in the oven for 5 minutes; put the dried cloth into the steamer and steam at 102~1〇5^ under normal pressure for 1 minute. Then the red rose stain is washed by cold water and then Wash in boiling hot water for 1 minute, then soap with boiling non-ionic detergent for 10 minutes, and then rinse again with cold water. 'After drying, the red dye can be obtained with excellent dyeing and coloring rate. Test Example 3 3 parts of the dye prepared in Example 3 was dissolved in 1 ml of water to prepare 30 wound/boost dye solution, and 25 ml of alkaline agent (using caustic soda μml/liter and thenardite 30 parts/liter) was added. Stir well in the dyeing solution, pour the mixture into #罗拉(R) ler) press, then press the cotton fabric through the roller and then roll it into a shaft. This form of cotton fabric at room temperature Store for 4 hours. Then, wash the orange dye first with cold water, then wash it with boiling hot water for 1 minute, then soap with boiling non-ionic detergent for 1 minute, then wash it with cold water. After drying, the dark blue dye can be obtained with excellent dyeing and coloring rate. 'The present invention can indeed achieve the purpose of the invention by the disclosed technical idea, which is novel, progressive and available for industrial use, and is in conformity with the patent requirements of the invention. However, the above disclosure is a preferred embodiment, 28 1326295 Partial changes or modifications resulting from the technical ideas of this case are easily inferred by those familiar with the technology, and do not deviate from the scope of patent rights in this case. [Simple description of the diagram] No [Major component symbol description] None

2929

Claims (1)

1326295 第95!294〇〇號，年11月修頭 十、申請專利範圍： 1種如下式⑴之具有硫烷基-S-三氮。井反應基之反 應性染料’其包含一個或多個染料發色團，其連接一個或 多個磺酸基（sulfo)和至少兩個纖維反應基，其中一個纖維1326295 No. 95!294 nickname, rectification in November of the year X. Patent application scope: One of the following formula (1) has a sulfanyl-S-trinitrogen. A well reactive reactive dye&apos; which comprises one or more dye chromophores which are attached to one or more sulfo groups and at least two fiber reactive groups, one of which is a fiber 反應基為 2-氣-4-硫烧基 _S -二 口井基（S-chloro-A-alkylthio-s-triazinyl) ，The reactive group is 2-sulfo-4-sulfothio-S-chloro-A-alkylthio-s-triazinyl. SQ /a (I) 其中： X、Y和Z係各自獨立的選自由氫原子、氯原子、羥基、 胺基、經取代之胺基、磺酸鹽、芳香族偶氮基、2_氣心烷 硫三氮。井_6_胺基、烷基、烷氧基、α，沒·齒丙醯基、α_SQ /a (I) wherein: X, Y and Z are each independently selected from the group consisting of a hydrogen atom, a chlorine atom, a hydroxyl group, an amine group, a substituted amine group, a sulfonate salt, an aromatic azo group, and a gas core. Alkyl sulfide. Well_6_amine, alkyl, alkoxy, α, · 齿 齿, α_ 鹵丙烯醯基、-b-so2ch2ch2w、-b-so2ch=ch2、 -so2ch2ch2w&amp;-so2ch=ch2 所組成之群； B 為直鏈或-CONJHCHJ-或_〇_(CH2)rC〇NH_ (cH2)k· , i、 j和k為各自獨立2到4的整數； W為用鹼處理可離去之基團，其係選自包括a group consisting of halopropenyl fluorenyl, -b-so2ch2ch2w, -b-so2ch=ch2, -so2ch2ch2w&amp;-so2ch=ch2; B is a straight chain or -CONJHCHJ- or _〇_(CH2)rC〇NH_ (cH2) k· , i, j and k are each an integer of 2 to 4 independently; W is a group which can be removed by treatment with a base, and is selected from the group consisting of 、及季銨鹽 烧基；And quaternary ammonium salts; 其中 R9、R1Q、Rn :Cl' -0S03H' 各自獨立分別 〇為Cm烧基或經取代之C|_4烷基； 30 1326295Wherein R9, R1Q, Rn:Cl'-0SO3H' are each independently Cm alkyl or substituted C|_4 alkyl; 30 1326295 a為1或2 ;a is 1 or 2; 所取代的Ci-4炫&gt;基β 2·如申請專利範圍第1項之反應性染料，其中Q為甲 炫基、乙&amp;基或經-至三個取代基取代之甲貌基、乙烧基， 且該曱烷基、乙烷基上之取代基係分別選自包括：齒素、 氫氧基、績酸基、氰基、胺基、M胺基、絲、烧氧幾 基、酿氧基及烧氧基。 ，，e a 必峨、肌化頁 '三笨二噁。井、單 多偶氮及金屬錯合偶氮結構發色團所組成 3.如申請專利範圍第1項之反應性染料，其中該染料 發色團A選自由曱月警、蒽醒、肽花青 '三笨二嗯。井、單 偶氮、雙偶氮、 之群。 4.如申請專利範圍第3項之反應性染料，其中該肽花 青發色團係為如下式之結構：Substituted Ci-4 Hyun&gt; base β 2·Reactive dye according to item 1 of the patent application, wherein Q is a methylidyl group, a B group or a methyl group substituted with three substituents, An alkyl group, and the substituents on the alkylene group and the ethane group are respectively selected from the group consisting of: dentate, hydroxyl group, acid group, cyano group, amine group, M amine group, silk, alkoxy group , brewing oxygen and alkoxy groups. ,, e a must, sputum page 'three stupid two evil. A well, a single polyazo and a metal mismatched azo structure chromophore. 3. The reactive dye according to claim 1, wherein the dye chromophore A is selected from the group consisting of 曱月警, awakening, peptide flower Qing 'three stupid two. Well, mono azo, disazo, group. 4. The reactive dye of claim 3, wherein the peptide cyanine chromophore is of the formula: 其中PC為銅肽花青基或鎳肽花青基，ϋ為-OH和/或-NH2， E為苯基或乙烯基；e + dg4。 5‘如申請專利範圍第3項之反應性染料，其中該三苯 二噁。井發色團選自包括·· ’ 31 1326295Wherein PC is a copper peptide cyanine or a nickel peptide cyanine group, deuterium is -OH and/or -NH2, E is a phenyl or vinyl group; e + dg4. 5 'Reactive dye as in claim 3 of the patent scope, wherein the triphenyl dioxine. Well chromophores are selected from including ·· 31' 所組成之族群，其中E為苯基或乙烯基。 6.如申請專利範圍第3項之反應性染料，其中該單偶 氮發色團選自包括：a group consisting of where E is phenyl or vinyl. 6. The reactive dye of claim 3, wherein the monoazo chromophore is selected from the group consisting of: 32 132629532 1326295 OHOH zy ㈣ ~(y (H03S)m (HOaS)^Zy (4) ~(y (H03S)m (HOaS)^ N=NN=N OH (S03H)〇OH (S03H)〇 N=N so3h 33 1326295N=N so3h 33 1326295 所組成之族群， 其中 R1為Cb4烷基、Ci 4烷氧基、缓基、磺酸基、_s〇2CH2CH2w 或-S〇2CH=CH2，W定義如申請專利範圍第1項所述； I為烷基’ Cl~4烷氧基，胺基，乙醯基胺基，脲基或 續基； R4為Cm烷基或羧基； m、〇及p個別獨立的分別為〇、1、2或3。 7.如申β專利範圍帛3項之反應性染料，其中該雙偶 氮及多偶氮發色團選自包括： 〃a group consisting of, wherein R1 is Cb4 alkyl, Ci 4 alkoxy, sulphonyl, sulfonate, _s〇2CH2CH2w or -S〇2CH=CH2, and W is as defined in claim 1; Alkyl 'Cl~4 alkoxy, amino, ethyl hydrazino, ureido or contig; R4 is Cm alkyl or carboxy; m, hydrazine and p are each independently 〇, 1, 2 or 3 . 7. The reactive dye according to claim 3, wherein the bisazo and polyazo chromophore are selected from the group consisting of: 34 132629534 1326295 (S03H),(S03H), 所組成之族群，其中： Rg為Cl〜4炫基、Cl-4.烧乳基、叛基、續酸基、乙酿基、乙 醯基胺基、脲基、-S02CH2CH2W或-S02CH=CH2，W定義 如申請專利範圍第1項所述； 9、1&quot;、3、1;及11各自獨立分別選自0、1、2或3; Ri'm'o及p定義如申請專利範圍第6項所述。 8.如申請專利範圍第3項之反應性染料，其中該金屬 錯合偶氮結構發色團選自包括： 35 1326295The group consisting of: Rg is Cl~4 炫, Cl-4. saponin, ruthenium, acid group, ethyl, acetamido, ureido, -S02CH2CH2W or -S02CH=CH2 , W is defined as in the scope of claim 1; 9, 1 &quot;, 3, 1; and 11 are each independently selected from 0, 1, 2 or 3; Ri'm'o and p are defined as the scope of the patent application 6 items mentioned. 8. The reactive dye according to claim 3, wherein the metal mismatched azo structure chromophore is selected from the group consisting of: 35 1326295 述。 9.如申請專利範圍第1項之反應性染料，其中該式（I) 係為如下式（1)Said. 9. The reactive dye according to claim 1, wherein the formula (I) is as follows (1) 10.如申請專利範圍第1項之反應性染料，其中該式（I) 係為如下式（2)10. The reactive dye according to claim 1, wherein the formula (I) is as follows (2) sch2cooh ho3soh2ch2co2s 36 (2) 1326295 11. 如申請專利範圍第1項之反應性染料，其中該式（I) 係為如下式（3) ho3soh2ch2co2sSch2cooh ho3soh2ch2co2s 36 (2) 1326295 11. The reactive dye according to claim 1, wherein the formula (I) is as follows (3) ho3soh2ch2co2s S03H oh NH2 H°3SvS03H oh NH2 H°3Sv 'ν=ντ^Ύ^ν=ν~^0 NH——SCH2COOH h〇3S/^l/^\^\s〇3H ' (3) 12. 如申請專利範圍第1項之反應性染料，其中該式（I) 係為如下式（36) ho2ch2cs'ν=ντ^Ύ^ν=ν~^0 NH——SCH2COOH h〇3S/^l/^\^\s〇3H ' (3) 12. The reactive dye according to item 1 of the patent application, wherein The formula (I) is as follows (36) ho2ch2cs Cl -sch2cooh 37Cl -sch2cooh 37