TWI308923B - - Google Patents

Description

1308923 IX. Description of invention: [Technical field to which Mao Ming belongs] Sexually, the Ming system has a new type of season money salt bisazo navy blue reaction 5 ,, 1 ' ; '; wood cellulose fiber has high coloring rate Excellent fast-washing properties and fastness to chlorine bleaching and oxidation bleaching. [Prior Art] A bisazo dye derived from the synthesis of citric acid. The dye precursor which is supplied by a diazo component and a ruthenium is formed in a blue dye precursor. The hue is most = 1 and It has a high molecular absorption coefficient and is widely used as a dye precursor for dyes used for color development such as navy and black. Among the bis-azo dye series, the cyan Reactive Black 5, which is developed by the Hoechst company in Germany in 1957 (Sulphat〇Ethyl Sulph〇ne; hereinafter referred to as SES), is the most 15 famous. This dye can dye the fabric into a very rich color and become black, so the Society of Dyeers and the Society of Dyeing

The dye color index (C0lcmr Iridex; C_I.) compiled by Colourists; SDC) is registered as Black Black. Although the C.I. Reactive Black 5 dye itself should be navy, 2〇/stra is the most commercially available dye in the reaction dyes. The following formula (II) is the structure of c.I. Reactive Black 5, and for convenience of explanation, if the dye salt is not specifically designated in the following description, the dye is represented by a free acid form. 1308923

H030H4C202S

N=N S03H -o

S02C2H40S03H However, the navy blue and black 5-color dyes based on CI Reactive Black 5 have the above characteristics, but their wet fastness has not been able to meet the market demand, especially the resistance to chlorine bleaching and oxidation bleaching. characteristic. In order to solve the fastness characteristics of C.I. Reactive Black 5 and the oxidative bleaching and washing, the following teams have been involved in development research. The introduction of fluorine (F), gas (C1), or the ortho-position at the ortho-acid position of the acid coupling of citric acid is disclosed in U.S. Patent No. 4,492,654 to Hoechst, 1985. When bromine (Br) atoms, the stability of copper ions during printing can be increased, wherein the dye can be as in formula (III)

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(III) The reaction group of the novel reactive group -CH3N-group plus SES and the S03H new reactive doubled at the ortho position on the benzene ring are disclosed in U.S. Patent No. 20 US5,102,993, issued to the disclosure of U.S. Pat. Nitrogen has a blue structure to increase the alkali stability of the dye paste and improve the fixation rate, and the 1308923 dye structure can be as shown in formula (IV).

10

N=N S03H

SO2C2H4OSO3H In 1992, Tzikas et al., in U.S. Patent No. 5,081,296, issued a new reactive group containing amidino group (-CONH-) and a sulfonic acid group (S03H) at the ortho position on the phenyl ring. The dye structure shown in (V) can improve the fastness of Black B. Cih4c2o2s_(h2c)3—HC-H2CTTN—C S〇2 ο c2h4ci (V) so3H OH NH2

S02C2H40S03H H03s so3h Due to the dyeing depth of the new structural dyes developed by the above research team, or the fastness to chlorine bleaching and oxidation bleaching, there is still room for improvement. In order to solve the above problems, there is a need for a novel reactive dye based on a quaternary ammonium salt derivative, which not only has high affinity and directness to cellulose fibers, but also improves the coloring rate of dyed cloth. It also has air fastness and fastness to oxidative bleaching. SUMMARY OF THE INVENTION The present invention provides a novel 20 1308923 reactive dye having a quaternary ammonium bisazo reactive group, and x # θ 士 > 友 〃 〃, not only has a coloring rate, high dyeing characteristics, and It is resistant to bleaching. Moreover, the novel reactive dyeing of the present invention is as high as the C.I. Reactive Black 5, but the 疋', the air rest and the oxidative bleach wash fastness are superior to the 匸丄Reacdve

Black 5 is up to level ι_2. The quaternary ammonium salt bisazo reactive dye of the present invention has the structural formula shown as follows: (I):

(I) 10 where,

Q is a S02—C2H4—〇S〇3H, a S〇2—CH=CH2, —CONH—(CH2)n—S02—C2H4—0S03H, —NH—CO—CH(Hai)—CHs—Ha! 15 —NH—C0—c (Ha0=CH 2 or the quaternary ammonium salt defined by U above;

Ha丨 is halogen; n is an integer from 1 to 6; R!, R2 and R3 are each independently hydrogen, thiol, halogen, acid group, (^ to C4 alkyl, or (: 丨 to C4 alkane) The quaternary ammonium salt bisazo reactive dye of the formula (1) of the present invention, wherein 20 is preferably S 〇 2 - C 2 H 4 - oso 3 h, - SO 2 - ch = ch 2 - -CONH - (CH 2 ) n - S 02 - C2H4 — OSO3H, 1308923 — NH — CO — CHCHad — d—Ha!, or —NH — CO — C(Hai) = CH2 ; Ha丨 is halogen, n is an integer from 1 to 6. More preferably, Q is —S 〇2~__c2H4-oso3h. The quaternary ammonium salt bisazo reactive dye of the formula (I) of the present invention, wherein the heart is preferably hydrogen, halogen, sulfonic acid group or alkoxy group; R2 is preferred. Is hydrogen, (^ to (: 4 alkyl, or (to) alkoxy; Rs is preferably hydrogen or a reductive acid group. The formula (I) Li ammonium salt bisazo reactive dye of the present invention , where U compares

The above reactive dye of the formula (I) of the present invention may be in the form of a free acid or a form of a salt, particularly an alkali metal and an alkaline earth metal salt. In the use of the dye, the reactive dye of the formula (I) is preferably present in the form of an alkali metal salt. When the reactive dye of the formula (I) of the present invention is represented by a free acid form, the reactive dye of the present invention is preferably a reactive dye compound of the following formulas (2) to (11).

HOOC

©n-h4c2o2s

So2c2h4oso3h 9 20 1308923

S02C2H40S03H

~Qr

SO2C2H4OSO3H

N=N so3h -o so2c2h4—Ne

COOH 10

NH-C〇-CH-CH2Br Br

So2c2h4oso3h 10 15 1308923 OH NH2 HOOC—(|N- H4C202S·

N = N S03H

s〇2C2H4〇s〇3H

-N=N- 'S03H

SO2C2H4OSO3H 10

When the quaternary ammonium salt bisazo reactive dye of the present invention is applied to a method of dyeing or printing a cellulose fiber material, the method may comprise treating the fiber material with an aqueous solution containing a reactive dye of the formula (1). Among them, the cellulose fiber material to which the reactive dye of the present invention is applied may be unlimited, and is preferably a cotton fiber material. For convenience of explanation, the reactive dye in this specification is represented by a free acid form. The reactive dye of the present invention may be present in the form of a water-soluble salt in the case of mass production, particularly a metal salt such as a sodium salt, a lithium salt, a clock salt or a salt, and among them, a sodium salt is preferred. The quaternary ammonium salt azo-reactive dyes of the present invention may also be mixed with one another to form a composition, and may be formulated by various methods, for example, 11 20 1308923

The dye of Si: is then mixed. Wherein, the method of reactive dyeing and mixing of the present invention can be carried out without limitation, and for example, it can be carried out in a suitable mixer, such as a squirting cylinder; or in a suitable mill, at: Γ 磨 。. The mixing methods described herein are also made by mixing the individual dyes with the dye liquid. Alternatively, this = the reaction conditions can be controlled in the preparation of each dye to produce the desired composition at the same time; or the mixing of individual dyes can be made during the dyeing or printing process. The quaternary salt bisazo reactive dyes of the invention can be used for cellulose ~ color and printing. Examples of suitable fibrous materials are: ',,, 'produced cellulose fibers such as cotton, hemp, and hemp; and fibers. Of course, the reactive dyes of the present invention can also be applied to the dyeing and printing of fiber blended fabrics of base fibers. 15 20 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. Further, the dye of the present invention can be dyed and printed by various methods such as secondary dyeing, continuous dyeing, cold press dyeing, or printing and dyeing. The dye of the invention can have green environmental protection, low salt, (4) and has excellent south coloring ability and excellent dyeing property, and has air fastness and oxidation resistance, and is suitable for a wide temperature range. Therefore, it can also be used for dyeing cotton/poly-mixed fabrics. Furthermore, the dye mixtures of the invention may also be suitable for use in printing dyes which are particularly suitable for use in cotton or blended fabrics containing wool or silk, and for use in τ/c one bath dyeing. The ammonium salt (IV) nitrogen reaction material of the invention can have the characteristics of high directness and high degree of dyeing 12 1308923 for the dyeing and printing on the cellulose fiber material, and also has a high fiber/dye in the acid test. Stability, and at the same time, it has excellent chlorine bleaching resistance and oxidative bleach wash fastness. For the convenience of further explanation, the following examples will be more specifically explained. Please note that the following examples are described in the following description. The scope of the present invention is not limited by the description of the present invention. [Embodiment] The following embodiments are merely illustrative of the invention, and unless otherwise specified, the temperature is 10 degrees C, and the weight is Parts and parts are expressed in grams and milliliters. Preparation Example 1 31.1 parts (2-methoxyl-4-p-Sulfatoethylsulfone) aniline 15 was dispersed in 〇 ° C, 150 parts of water, and 5 parts of NaOH was added. Adjust the pH of the above solution to 13' to maintain 1) 11 value for 15 minutes, then adjust the pH of the reaction solution to 5 to 6 with an aqueous solution of Ηα, and then add 12.7 parts of nicotine acid to the reaction solution. Then, the reaction solution is added. Temperature and holding temperature to 6〇〇c Bu 2 hours, i.e. to stop the reaction. Finally, via a commonly used NaC1 salting, filtration and washing procedure was filtered brine 20, i.e., to obtain a following formula (R1) of the product structure.

13 1308923 Preparation Example 2 36.1 parts of l-aminobenzene-4-(p-sulfatoethylsulfone)-2-sulfonicacid was dispersed in 0 ° C, 150 parts of water, and 4.5 parts of NaOH was added to adjust the pH of the above solution to 13 to maintain the pH stably. After the value of 15 minutes 5, the pH of the reaction solution was adjusted to 5 to 6 using an aqueous HCl solution, and 12.7 parts of nicotine acid was further added to the reaction liquid. Then, the reaction solution was heated to 60 ° C and maintained at a temperature of 1 to 2 hours, i.e., the reaction was stopped. Finally, a product of the following formula (R2) is obtained via the conventionally used NaCl salting out, filtration and brine filtration procedures. 10

Preparation Example 3 15 32. 5 parts of P.thoxyM-P-sulfatoethylsulfonej methyl)aniline was dispersed in (TC, 150 parts of water, and 45 parts of NaOH was added, the pH of the above solution was adjusted to 丨3, and the pH was kept stable for 5 minutes. After: adjust the pH of the reaction solution to 5 to 6 with HCl aqueous solution, and then add 12 7 parts of nicotine acid to the reaction solution. Then 'heat the reaction solution to 6 ° C and hold the temperature for 2 to 20 hours. Nacl salting, percolation and brine filtration procedures yield a product of the structure of formula (R3) below. 14 1308923

(R3) Preparation Example 4 5

10 After adding 0 ° C, 1 50 parts of water to 14.5 parts (4-P_sulfatoethylsulfone) aniline and 12.6 parts of 32% HCl solution to form a dispersion solution, then quickly add 3.6 parts of NaN02 aqueous solution to the dispersion solution. And it is controlled at a temperature of 0 to 5 ° C to carry out a diazotization reaction for about 1.5 hours. Next, 16.0 parts of d-amino-S-hydroxy-SJ-naphthalenedisulfonic acid powder was added, and the pH of the reaction solution was slowly adjusted to 3 using 10 parts of NaHC03 aqueous solution, and the coupling reaction was completed to form a compound containing the following formula (R4). Coupling solution.

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So2c2h4oso3h Example 1 0 ° C, 150 parts of water was added to 17.5 parts of the compound of Preparation Example 1 and 12.6 parts of 32% aqueous HCl solution to form a dispersion solution, and then 3.7 parts of NaN 2 aqueous solution was quickly added thereto. The solution was dispersed in a solution, and controlled at a temperature of 0 to 5 ° C to carry out a diazotization reaction for about 1 hour to complete a diazonium salt solution. Finally, the diazonium salt solution is added to the above coupling solution 15 1308923 ' and 5 parts of Na 2 C 〇 3 锾, fs 敕 敕 ρ; Α _ 3, and the ρ Η value of the lyophilized reaction solution is 5-6'. After the reaction is sufficiently carried out, the navy blue product having the structure of the following formula (2) is obtained by the process of batch, a < dan, analysis, filtration and drying.

Example 2 10 15 The synthesis step of the naphtha product of this example was carried out using the same synthetic procedure as in Example 1, except that the compound of the formula (I) of the preparation example i was replaced with the compound of the formula (R2) in the reactant. , wherein the reaction conditions and steps are the same as those shown in Example 1. The resulting solution is sufficiently reacted, and subjected to a salting out, filtration and drying process to obtain a navy product having the structure of the following formula (3).

The synthesis step of the naphtha product of this example is the same as the synthesis step of Example 1, except that the (R1) compound of Preparation Example 1 in the reactant is substituted with the (R3) compound of Preparation Example 3, wherein the reaction conditions are The steps 16 20 X308923 are the same as those shown in Embodiment 1. And the solution obtained by the reaction is fully reacted, salted out, dried and dried to form > ^ Du order, to obtain a navy product having the structure of the following formula (4). HOOC 〇CH3

^;n-h4c2o2s-/^__n= n 5 H3c H〇3s (4) Dyeing test: The above dye compound and αΐ·Reactive Biack 5 (commercially available from Yongguang Chemical 10) are dissolved! In the water, add 30 parts of thenardite and 1 part of unsilked cotton cloth, then keep the dye solution for 6 (rc stir for 3 minutes, then add 15 parts of soda ash, continue to keep 60 〇c for dyeing i After the dyeing is completed, 'washing, soaping and drying are carried out to obtain a dyed fabric. And the obtained dyed fabric is subjected to the following dyeing characteristics test. Among them, the results of various dyeing characteristics test will be as follows Table shows: Comparison of color ratio (K/S value at the same OD) Dye compound 1% 3% 5% 7% 9% cl Reactive Black 5 14.3 31.5 39.5 42.7 1 43.6 Example 1 14.4 31.1 39.1 43.0 45.1 Example 2 15.5 32.3 40.1 42.9 45.5 Example 3 - 15.0 32.3 39.2 44.0 43.9 17 1308923 Fastness test: according to ISO 105 E03, and C09A standard test method. Dye compound emulsion bleaching ISO 105-E03 Oxidation-resistant bleaching wash L (C09A^ λ max CI Reactive Black 5 1 —---- 2-3 600 Example 1 2-3 4 615 Example 2 3 4-5 611 Example 3 3 4-5 612 From the results of the dyeing characteristics test of the above table, The novel season recording sleep double 5 azo reservoir of the invention Color reactive dyes, which are used to dye cellulose fibers, have high coloring rate, excellent chlorine bleaching resistance and oxidative bleaching resistance, in addition to the southerly affinity and directness of cellulose fibers. The fastness characteristics such as water washing. Moreover, the novel reactive dye 10 of the quaternary ammonium salt bisazo reactive group of the present invention can be used as the high dyeing property of C·1·Reactive Black 5, but it is resistant to chlorine bleaching and oxidation bleaching. The degree is better than that of CI Reactive Black 5, which will meet the market demand for high dyeing and high fastness properties. In summary, the present invention can achieve the above-mentioned technical ideas. The purpose 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, and the technical idea of the case is derived from the fact that the P is further or modified. Anyone who is familiar with the technology can easily infer the scope of the patent. 18 1308923 [Simple description of the diagram] No [main symbol description]

Claims (1)

10 15 X. Patent application scope: 1. A reactive dye of the following formula (1): r3 N=N~^〇so3h ^(I) where 0/R| —N—r5 u is , Q is a so2—c2h4— 0S03H, a so2—ch=ch2, —CONH—(CH2)n—S〇2—C2H4—OSO3H′—NH—CO—CH(Ha,)—CH2—Ha, '—NH—CO—or the above U a quaternary ammonium salt as defined; Ha! is a halogen; n is an integer from 1 to 6; Ri, R2 and R3 are each independently hydrogen, thiol, halogen, acid group, C] to C4 alkyl, or c! Alkoxy to C4. 2. The reactive dye according to claim 1, wherein q is an S 〇 2 - C 2 H 4 - OSO 3H ' - SO 2 - CH = CH 2 —CONH—(CH2)n—S〇2—C2H4—OSO3H ' m—CQ-CHCHai^Hr-Ha!, or one NH—€0~~€(Η&1)=(3Η2; Hai is halogen, n 3. The reactive dye according to claim 1, wherein Q is -S〇2-C2H4-OSO3H. 4. The reactive dye according to claim 1 The reactive dye according to claim 1, wherein the reactive dye of the formula (I) is the following formula (4): 10 The reactive dye according to claim 1, wherein the reactive dye of the formula (I) is a dye compound of the following formula (5) to formula (11): 15 N=N so3h -ο S02C2H4—Ν 十 COOH 22 20 1308923 C0NHC2H4S02C2H4C1 (9), HOOC — H4C2O2 So2c2h4-n© COOH twenty three