TWI261604B - Dye composition and their use - Google Patents

Abstract

A dye composition, which comprising: (A) at least one azo dye selected from the formula (I) or (II), wherein R, R1, R2, D1 and D2 are defined the same as the specification; and (B) a diazo dye of the formula (III), wherein (R9)0 to 2, (R10)0 to 2, Q1 and Q2. These kinds of dye composition with high fixation and good build-up. They are distinguished also by high washing off and a low nylon stain and they are suitable for dyeing and printing of materials containing either cellulose fibers, such as cotton, artificial cotton, linen, and artificial linen, or synthetic polyamide, such as wool, silk, and nylon etc. Dyed materials with excellent properties can be obtained, showing especially outstanding performance in of washing off, level-dyeing, build-up, wet fastness and light fastness.

Description

1261604 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a dye composition, and more particularly to a black or dark blue reactive dye composition. 5 [Prior Art] Reactive dyes used for dyeing cellulosic fiber materials or cellulose-containing fibrous materials and printing palladium must have excellent performance in various properties, such as leveling and reproducibility ( Repr〇ducibility), solubility (solubility) and fastness (fastness). 10 In the market, there is the economic efficiency of dyeing quality and dyeing method. The dyeing with reactive dyes is in need of practice. Therefore, it is possible to improve the speciality, and the special J is a new application. The reaction of the ten dyes is still urgently needed. In the demand for dyeing applications, dyes having excellent coloring ratios and inter-reactivity are particularly required, and dyes which can sufficiently and easily wash off unfixed portions are required. Conventional dyes appear to be difficult to satisfy all of the properties of these elements. In the existing reactive dye composition, there is a dye which is well dyed and cleaned and has low nylon (Nyl〇n) contamination, so that when dyeing on nylon 20/cotton (N/C), It is impossible to overcome the problem of poor dyeing and poor cleansing. It is desirable to provide a novel dye composition having high coloration ratio and high fiber-dye binding stability, and having the property of easily washing away unfixed dye. 1261604 SUMMARY OF THE INVENTION The present invention provides a dye composition mainly comprising the azo dye of the following composition (A) and the bisazo dye of the component @). The component (A) in the dye composition of the present invention is at least one selected from the group consisting of the following formula (1) or (π), in an amount of from i to 99% by weight (wt%), 〇1

R is a hydrogen atom or a Wei group; preferably, 卞 is also an earth day g, and r is a carboxyl group;

<^~4 burning base; preferably, R

Ri and R2 are independently hydrogen atoms and R2 are hydrogen atoms; D! and D2 are independently selected from the group consisting of Xiaok (la), (lb), (lc), (ld) or (le) Group 15 1261604 螬

(lb)

(Id) 8 1261604 (^6)0-2

(le) Preferably, D1 and D2 are groups of formula (la) or (lc); wherein 5 (^士~3 and (RAJ are individually independent, 〇 to 3 identical or different from the 匕a group consisting of a halogen, a carboxyl group, a sulfonium group, a sulfonium group, a sulfonium group, and a c 4 alkoxy group; preferably, (Ru(r^ is 〇 to 3 identical or not) The same group selected from the group consisting of (4) (8), methyl and methoxy of the rhein; 10 R5 is a hydrogen atom or a Ch-alkyl group which is unsubstituted or substituted by a base, a dibasic group, a thiol group or a cyano group; Preferably, I is a hydrogen atom, a methyl group or an ethyl group, and (R6)o~2疋0 to 2 are the same or different and are selected from the group consisting of a sulfo group, a c1-4 alkyl group and a Cl-4 group. a group in the group consisting of alkoxy groups; ruthenium, (reverse 6) 〇~2 is 〇 to 2 identical or different selected from the group consisting of sulfonic acid groups 15 (sulf0), fluorenyl groups and methoxy groups. a group; R7 is a chlorine atom, a sulfonic acid group, a Cl 4 alkyl group or a 〇 4 alkoxy group; preferably, R 7 is a hydrogen atom, a sulfonic acid group, a methyl group or a methoxy group; (ureido), sulfonic acid group, Ci_4 alkyl group, Cly alkoxy group or C2-4 alkanoylamino group (alkan0ylamin) Preferably, Rs is a 〇2〇 atom, a ureido group, a lysyl group, a methyl group, a methoxy group or a ethyl (tetra) group; the second 1261604 v is a group of a non-reactive amine group; Q and Q' are individually independent It is -NH-C0_CH(Hal)-CH2(Hal), -NH-CO-C(Hal)=CH2 or -S02-Y; preferably, Q and Q are -S〇2-Y; Y is - Ch=ch2, -CH2CH20S03H or -CH2CH2-U; u is the basis for the departure of the cockroach;

Hal is halogen; m is ο or 1; preferably, m is 1. The component (B) in the dye composition of the present invention is a disazo dye represented by the following formula (in) in an amount of 99 to 9% by weight (wt%),

(III)

Wherein 15 (R9) 0 to 2 and (Ri0) 0 to 2 are independently independent of two or the same group selected from the group consisting of a sulfo group, a Cl 4 alkyl group and a Cl 4 alkoxy group. Preferably, (Do~2 and (Ri〇)〇~2 are 相同 to 2 identical or different groups selected from the group consisting of sulfonate, methyl and methoxy groups ;

Qi and Q2 are independently -NH-CO-CH(Hal)-CH2(Hal), 20-NH-CO-C(Hal)=CH2 or -S02-Y; preferably, (^ and q2 are -S02-Y ; Y is -CH=CH2, -CH2CH20S03H or -CH2CH2-U; u is a group which is removed from the base ίο 1261604; Hal is a halogen. If Y is -CH2CH2-U, U can be exemplified as follows : -CM, -Br, -F, -SS〇3h, -OCO-CH3, -OP〇3H2, -〇c〇C6H5, -OSOrCw alkyl, -〇S〇2-Ν((^_4 :): Complete base) 2 or 5

Among them, the group V of the non-reactive amine group may, for example, be: an amine group, a mercaptoamine, an ethylamine, a/5-sulfonic acid ethylamine, a fluorene-anilinic acid anilide, and an m-acid group. Aniline, p-supply aniline, 2,4-dibasic aniline, 2 5-10 disulfonic phenylamine, 1-sulfonyl-2-naphthylamine, 1,5-disulfonyl naphthylamine or Morinolino. The dye composition of the present invention can be further represented as a dye composition comprising both the formula (I) and the formula (I) dye, wherein the component (a) comprises the dye of the formula (I) of 10 to 40 parts by weight and the dye of the formula (11) are 15 in an amount of 1 to 20% by weight, and the component (B) is a dye having a formula (ΙΠ) of 40 to 89% by weight. The dye composition of the present invention may be in the form of an acid or a salt, particularly an alkali metal or an alkaline earth metal salt, and is preferably used in the form of an alkali metal salt. The dye composition described in the present invention can be applied to cellulose fibers such as cotton, rayon, hemp and artificial hemp, as well as dyeing of polyamide fibers such as wool, silk and nylon, and can obtain various dyeing properties with good dyeing properties. The dye composition of the present invention has excellent dyeing depth, detergency, low nylon pollution and daylighting, and can be used in combination with other color dyes. L26l6〇4 [Embodiment] The compound of the formula (1) in the composition of the present invention can be synthesized by the following method. = First, the amine compound of the following formula (4) is subjected to heavy gasification, followed by the acid base value d "NH2" with the amine compound of the formula (b).

(a) diazonium salt coupled with l〇-2〇 °C, (b) should. Then, with the following formula (c), the amine compound 10 〇 2 - NH 2 15 , _ S under-base value, for example, the pH value of 2.0 to 5 C and the temperature of 10 to 20 ° C under the enthalpy coupling reaction The compound of the present invention - (1) can be obtained. Wherein R, D1, and D2 are as defined above. Month. The dye represented by the formula (1) is preferably an azo dye represented by the following formula / (wherein Di and D2 are defined)

COOH Di~N

n^n 〇2 as described. The most preferred is the even 12 20 1261604 nitrogen dye represented by the following formula (lb): (R3) 〇-3

Y-〇2S

(R3)〇-3

S〇2-Y wherein (R3) 0-3 and Y are as defined above. The compound of the formula (I) can be specifically exemplified by the formula (2), the formula (3), the formula (4), the formula (5), the formula (6) or the formula (7): ho3soh2ch2co2s-s〇3h-N=

COOH -N=N- -so2ch2ch2oso3h h2n^^^nh2 10 (2) h〇3s〇(h2c)2〇2s

N = N NH2

S〇2(CH2)2〇S03H 15 h〇3s〇(h2c)2〇2s

〇 II I Br (4) 13 1261604 h〇3s〇(h2c)2〇2s

Cl

(7) The compound of the formula (II) can be synthesized by the following method. First, the amine compound of the following formula (a) is subjected to diazotization, followed by an acid compound having the weak acidity (pH = l -5 ) with an amine compound of the following formula (d).

OH

D Factory ΝΗ2 Γ |Τ NR^

S〇3H 15 (a) (d) Coupling reaction at a temperature of 0-40 °C. Then, with the diazonium salt of the amine compound of the following formula (c), 14 1261604 D2-*-*NH2 is between the micro acid and the test acid value, for example, the acid value is 4.0 to 8 〇 ' and 20 to 6 ( The coupling reaction is carried out at a temperature of TC to obtain a compound of the present invention, wherein, as defined above, the dye represented by the formula (II) in the present invention is preferably an azo dye represented as follows:

OH D2—N two N

N=N— 〇1 ho3s

Nh2

S03H (Ila) 10 wherein 〇, and D2 are defined as described above. The most preferred is the azo dye represented by the following formula (nb):

(Hb) I5 wherein (R3) 0-3 and Y are as defined above. The compound of the formula (II) can be specifically exemplified by the formula (8), the formula (9), the formula (1〇), the formula (11), the formula (12), the formula (13) or the formula (14): 15 1261604

Ίο

S〇3H (Π)

16 (12) 1261604

S〇3h (14) The compound of the formula (III) can be synthesized by the following method. First, the amine compound of the following formula (e) is subjected to diazotization, followed by an acidic acid base number (pH = l -3 ) (Rl 〇) 〇 -2 - nh 2 with an amine compound of the following formula (f)

H〇3S^^\^\S〇3H

(e) (f) Coupling reaction at 10-20 °C. And then with the diazonium salt of the amine compound of the following formula (g),

17 15 1261604 (g) The compound of the formula (III) of the present invention can be obtained by performing a coupling reaction between an acid to a neutral acid value, for example, an acid value of 3.0 to 7.0, and a temperature of 10 to 20 °C. Wherein (R9)Q~2, (RlQ)Q~2, Ql and Q2 are as defined above. 5 The dye represented by the formula (III) of the present invention is preferably a disazo dye represented by the following formula (Ilia):

(Hla) 10 wherein Qi and Q2 are as defined above. The most preferred is the bisazo dye represented by the following formula (Illb): OH NH2

N=N—(Illb) 15 where Υ is as defined above. The compound of the formula (III) can be specifically exemplified by the formula (15): ho3soh2ch2co2s

S〇2ch2ch2os〇3h 18 (15) 1261604 The dye composition of the present invention, wherein the component (A) has a dye content of 1 to 99% by weight (wt%) and the component (B) has a dye content of 99, based on the total weight of the dye. Up to 1 weight percent (wt%). Preferably, the component (A) has a dye content of 5 to 95% by weight (wt%), and the component (B) has a dye content of 95 to 5 weight percent (wt%). Most preferably, the component (A) has a dye content of from 1 Torr to 90% by weight (wt%), and the component (B) has a dye content of from 9 Å to 1 Å by weight (% by weight). 10 15 20 The dye composition of the present invention can be further represented as a dye composition comprising both the dyes of the formula (I), the formula (II) and the formula (III), based on the total weight of the dye, wherein the component (A) The dye of the component (B) is a dye of the formula (III) in an amount of from 40 to 89% by weight, based on the dye content of the formula (I) being from 40 to 40% by weight and the dye content of the formula (II) being from 1 to 2% by weight. Preferably, wherein the component (A) comprises a formula (1) having a dye content of 15 to 4% by weight and the formula (II) having a dye content of 5 to 20% by weight, the component (Β) dye being a dye of the formula (III) The content is from 40 to 80% by weight. The dye composition of the present invention can be formulated by various methods, for example, by: formulating different individual (four) and then mixing them, the method of mixing: performing in a suitable mixer, for example, in a rotating barrel; In a suitable mill 2' such as a ball and sand mill, but also by agitation: mixing the individual dyes for the dye liquid; or controlling the reaction conditions in each dye: The desired composition may be produced at the same time as the preparation. In the process of dyeing or printing, the individual dyes may be mutually necessary. The dye of the present invention may also contain inorganic salts such as sodium sulphate, sodium chloride and the like; Methylnaphthalenesulfonic acid-methanol recombination: 'dot-naphthalenesulfonic acid formaldehyde condensate, aramidyl (tetra) compound, etc.; dust-proof sword (duStlngagent), for example

佶缒 you make 丨, T 3夂一 · 2_ethylhexyl ester, etc.; pH

Value buffers, such as sodium acetate, sodium phthalate, sodium hydrazine, water hydrating agents, such as polyphosphorus, or conventional dyeing agents. The type of the dye composition of the present invention is a powder, a fine powder, a granule or a liquid. In the present invention, for convenience of explanation, the compounds in the present invention are described in the form of free acid, and the dyes of the present invention exist in a large amount of ίο type, particularly It is preferred to test metal salts such as sodium salts, bell salts, and sodium salts. The dye composition of the invention is suitable for dyeing fibrous materials, especially cellulose fiber materials' and cellulose fiber-containing materials. The cellulose fiber material is not particularly limited and includes natural or regenerated cellulose fibers, such as pure cotton fibers, flax, hemp, numb, mucilage, or fibrous materials containing cellulose fibers. The dyeing of the present invention can be dyed according to a conventional and conventional method. Exhaustion dyeing is carried out by using well-known inorganic neutral salts (such as anhydrous sodium sulfate and sodium carbonate) and well-known acid binders (such as sodium carbonate). , 20 sodium hydroxide) used alone or in combination. The amount of inorganic neutral salt and alkali is not very important. The neutral salt and alkali can be added in one or several times according to the traditional method; In addition, dyeing assistants (such as leveling agents, retarding agents such as ton agents) can be added according to conventional methods, and the dyeing temperature is usually between 40 ° C and 90 ° C. A preferred dyeing temperature of 20 1261604 degrees is from 50 ° C to 70 ° C. θ [Cold pad batch-up dyeing method is used to make the object to be dyed; inorganic neutral salts (such as anhydrous sodium sulfate and sodium chloride) and well-known acid binders (such as sodium citrate) , sodium hydroxide) padding, and then the resulting material is wound into a roll at room temperature 5 for dyeing. The continuous dyeing method is dyeing by single bath dyeing, mixing with a well-known acid binder (such as sodium carbonate or sodium hydrogencarbonate) and a padding solution, and the material to be dyed is padded according to the usual method, and then the obtained substance is obtained. Drying or steam curing; two-bath padding is a dye dyeing of the material to be dyed, followed by well-known 10 inorganic neutral salts (such as anhydrous sodium sulphate and sodium chloride) and well-known acid binders ( For treatment with sodium hydroxide or sodium citrate, it is preferred to dry or steam solidify the treated material in the usual manner. Text printing (methile printing meth〇ds), for example, a single-phase printing 15 method, printed with a paste containing a well-known acid binder (such as sodium strontium carbonate), printed on the material to be printed, and dried or steamed Fixing; two-phase printing method consists of printing paste printing materials, immersing the material in high temperature (9 〇t or above) containing only inorganic neutral salts (such as sodium chloride) and well-known acid binders (such as strontium) Fix the color in a solution of sodium strontium or sodium sulphate. The method according to the invention is not limited to the dyeing or printing methods listed. The composition of the present invention has good color fixing ability and excellent dyeing property. It also has excellent color depth, leveling and detergency, as well as high solubility, high depletion ratio and high fixation ratio. It can therefore be used in dip dyeing methods at low dyeing temperatures and requires only a short steam treatment time in the rolling process. High fixing rate and easy to wash unless the fixing part, the difference between dyeing rate and fixing rate is very small, that is, the washing loss pole 21 21261604 low 0 The composition of the invention has high chroma for dyeing and printing of cellulose fiber material and High fiber-dye combined stability, in the range of acid and alkali, such as 疋, good resistance to light fastness, wet fastness and excellent resistance to 5 wet strength, such as washable, water resistant, resistant Seawater, cross-dyeing and perspiration fastness, as well as good crease fastness, ironing fastness and fastness to rubbing. Therefore, it is an industrially valuable black reactive dye for cellulose fibers, and it has excellent dyeing properties and light fastness in addition to dyes having good dyeing properties. 10 For the sake of further explanation, the following examples will be given for a more detailed description. The following examples are illustrative of the invention, and the scope of the invention is not intended to be limited. The compounds shown therein are in the dissociated acid form; usually they are mixed in the form of their alkali metal salts and used in their salt form for dyeing 15 colors. The following examples are given to illustrate the invention. Unless otherwise stated, the parts and percentages are by weight. The relationship between parts by weight and parts by volume is like the relationship between kilograms and liters. 20 Preparation Example 1 115.6-injured iota-aminobenzene-2-sulfonic acid-b sulfate sulfonate-am^n〇benZene'2*sulfonic acid -4-p-sulfatoethylsulfone) Dispersion in 1 〇 〇〇 冰 太 φ φ 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水 水

25 Then, at 5 to 5 °c, hold the clock A F' and search for it to complete the diazotization. Next, 48.7 22 1261604 parts of 3,5-diaminobenzoic acid powder were added and stirred: the reaction mixture was mixed until the coupling reaction was completed. Finally, sodium chloride is added to the salt, and the mixture is removed by filtration to obtain the compound (P-1).

(P-1) 16.8 parts of 1-aminobenzene-4-p-sulfatoethylsulfone was dissolved and dispersed in 150 10 parts of ice water, followed by 8 parts. A 32% aqueous solution of HCl was thoroughly stirred therein, followed by addition of 4.3 parts of an aqueous solution of sodium nitrite, followed by continuous stirring at 0 to 5 ° C until diazotization was completed. Next, 30.5 parts of the compound (P-1) was added, and the mixture was stirred with sodium hydrogen carbonate to adjust the pH to 3.5 at a temperature of 10 to 15 ° C to complete the coupling reaction. Finally, salting out with sodium chloride and filtering out 15 times gives compound (2). Ho3soh2ch2co2s

So2ch2ch2oso3h (2) Preparation Example 2 20 Dissolve 3 3.8 parts of 1-aminobenzene-4-P-sulfatoethylsulfone in 200 23 1261604 parts of ice water, followed by dispersing 3 3.8 parts of 1-aminobenzene-4-P-sulfatoethylsulfone 16 parts of a 32% aqueous HCl solution was added thereto to be thoroughly stirred, and then 8.7 parts of an aqueous sodium nitrite solution was further added, followed by continuous stirring at 0 to 5 ° C until diazotization was completed. Then add 9.1 parts of 3,5-diaminobenzoic acid powder, and slowly adjust the pH to 3.5 with sodium argonate to stir the mixture at a temperature of 10-1 5 ° C to complete the coupling reaction. . Finally, salting out with sodium chloride is added, and the mixture is removed by filtration to obtain a compound (3). H〇3so(h2c)2o2s

S〇2(CH2)2〇S〇3H H2N^v^:^NH2

10 (3) Preparation Example 3

4 · 8 parts of 2-amino-4-((2,3 -di))amino-2-phenylsulfonate Benzene sulfonic 15 acid) was dissolved and dispersed in 60 parts of ice water, then added with 3.2 parts of 32% aqueous HCl solution, stirred well, followed by 0.9 parts of aqueous sodium sulfite solution, and then continuously stirred at room temperature until Complete diazotization. Next, 6.1 parts of the compound (P-1) was added, and the mixture was slowly adjusted with a sodium carbonate to 5.0 at room temperature to complete the coupling reaction. Finally, the vaporized sodium salt is added to the precipitate, and the mixture is removed by filtration to obtain the compound (4).

〉0 NH-C-CH-CH2Br 24 (4) 1261604 Preparation Example 4 19 parts of Cyanic chloride were stirred and dispersed in ice water 5 'receivers were added to 9 parts of 1-amine basic-3 - Β-aminobenzene-3-p-sulfatoethylsulfone powder, and slowly adjust the pH to 3.4 to 4.0 with sodium carbonate to continuously stir the mixture to complete the condensation reaction, followed by the addition of 19.4 parts of 2 , 2,4-Diaminobenzenesulfonic acid powder, and adjust the pH to 5.0 with sodium carbonate slowly to continuously stir the mixture to complete the second condensation reaction. Finally, potassium chloride salting is added to the 32% HCl, and the mixture is removed by filtration to obtain the compound (P-2).

CI (P-2) 15 Take 1/3 part of the above compound (P-2) dissolved in ice water, adjust the base to make it completely soluble, then add 2.0 parts of sodium nitrite to stir well: mix, then 8.4 parts of a 32% aqueous HCl solution was added thereto, and stirring was continued at a temperature of 5 to 10 ° C until diazotization was completed. Next, 14.3 parts of the compound 20 (P-1) was added, and the pH was slowly adjusted to 3.5 to 4.0 with sodium carbonate to stir the mixture at room temperature until the coupling reaction was completed. Finally, gasification nanosaltration is added, and the mixture is removed by filtration to obtain a compound (5). 25 1261604 (5) Preparation Examples 5 to 14 5 Referring to the procedures described in Preparation Example 1, Example 2, Example 3 and Example 4, the following reactive dyes can be prepared to dye cotton fibers in a specific color tone and have Good fastness. Preparation 5 10 so3h H〇3S〇(H2C)2〇2S —N 2 N h2n

CI is a compound of formula (6) and is orange. H〇3s〇(h2c)2〇2s

Preparation Example 6 15 The compound (7) was orange.

(7) Preparation Example 7 20 The compound (8) is red in color. 26 1261604

S〇3H 10 (8) Preparation Example 8 The compound of the formula (9) was red. ?H [Γ飞 HO3SOC2H4O2S—, —N=N, y—SO2C2H4OSO3H HO3S NH2 s〇3h (9) Preparation Example 9 If the compound formula (10) is a system J: color.

Plant - _/0CH3 oh =< H03s 7/ λ H〇3S〇C2H402Sh^ Gossip N=N^_ V-S02C2H40S03H ch3q H03s 丫人nh2 so3h (10) Preparation 1 ο As compound formula (11), It is red. 27 15 1261604 /〇CH3 h〇3s〇c2h4〇2s η3σ

OH

NHpH〇3S

N=N

S〇2c2h4os〇3h (11) Preparation Example 11 The compound of the formula (12) is red. /S〇3h ho3s 〇 II CH2CH—C—HN I I Br Br T I ^γ-Ν=:Ν 1 ^\Κ1Ι, H〇3S ΝΗ2 s〇3h

S02C2H40S03H (12) 10 Preparation Example 12 If the compound formula (13) is red

S02C2H40S03H Preparation Example 13 28 1261604 The compound of formula (14) is red.

S〇2c2h4os〇3h Preparation Example 14 The compound of the formula (16) is orange.

10

(16) Example 1 90 parts of the dye of the above formula (15) was obtained, and 10 parts of the dye of the above formula (2) were mixed, and a dye composition was obtained. Example 2 A dye composition was obtained by taking 75 parts of the dye of the above formula (15) and uniformly mixing with 25 parts of the dye of the above formula (2). 29 1261604 Example 3 60 parts of the dye of the above formula (15) and 40 parts of the dye of the above formula (2) were mixed and kneaded to obtain a dye composition. Example 4 90 parts of the dye of the above formula (15) and 10 parts of the dye of the above formula (3) were mixed and kneaded to obtain a dye composition.

10 Example 5 75 parts of the dye of the above formula (15) and 25 parts of the dye of the above formula (3) were uniformly mixed to obtain a dye composition. Example 6 15 A dye composition was obtained by uniformly mixing 60 parts of the dye of the above formula (15) with 40 parts of the dye of the above formula (3). Example 7 A dye composition was obtained by taking 90 parts of the above-mentioned formula (15) dye and uniformly mixing with the above-mentioned formula (4) dye 10 20 parts. Example 8 A dye composition was obtained by taking 75 parts of the dye of the above formula (15) and uniformly mixing with 25 parts of the dye of the above formula (4). 30 1261604 Example 9 Eight dyes of the above formula (1)) were dyed and uniformly mixed with the dye of the above formula (4) to obtain a dye composition. 5 Example 1 90 A 90% portion of the dye of the above formula (15) was mixed with the above-mentioned formula (5), and the dye was uniformly mixed to obtain a dye composition. Example 11 10 A dye composition was obtained by uniformly mixing 75 parts of the dye of the above formula (15) with 25 parts of the dye of the above formula (5). Example 12 A dye composition was obtained by taking 60 parts of the dye of the above formula (15) and uniformly mixing it with 4 parts of the dye of the above formula (5). Example 13 9 parts of the dye of the formula (15) just described was obtained, and the dye of the formula (6) was rubbed and uniformly mixed to obtain a dye composition. 20 Example 14 A dye composition was prepared by uniformly mixing 75 parts of the dye of the formula (15) and 25 parts of the dye of the above formula (6). 25 Example 1 5 31 1261604 A dye composition was obtained by taking 6 parts of the dye of the above formula (15) and kneading with the dye of the above formula (6). Example 16 A dye composition was obtained by uniformly mixing 9 parts of the dye of the above formula (15) with 10 parts of the dye of the above formula (7). Example 17 A dye composition was obtained by uniformly mixing 75 parts of the dye of the formula (15) described in the uranium with the above formula (7) dye 25 10 parts'. Example 18 A dye composition was obtained by uniformly mixing 60 parts of the dye of the formula (15) as described above and 40 parts of the dye of the above formula (7). 15 Example 19 A dye composition was obtained by taking 9 parts of the dye of the above formula (丨5) and uniformly mixing with the dye of the above formula (8). Example 20 The dye composition was prepared by uniformly mixing 75 parts of the dye of the formula (15) described above with the dye 2S of the above formula (8). (4) Example 21 25 A dye composition was obtained by uniformly mixing 60 parts of the above-mentioned formula (15) dye with the above-mentioned formula Μ) dye 40 32 1261604 parts. Example 2 2 A dye composition was obtained by taking 90 parts of the dye of the above formula (15) and mixing it with the above-mentioned formula (9). Example 23 A dye composition was obtained by taking 75 parts of the dye of the above formula (15) and uniformly mixing with 25 parts of the dye of the above formula (9). Example 24 A dye composition was prepared by uniformly mixing 60 parts of the dye of the formula (15) described above with 40 parts of the dye of the above formula (9). 15 Example 25 A dye composition was obtained by taking 90 parts of the dye of the above formula (15) and uniformly mixing it with 1 part of the above formula (1) dye. Example 26 2 75 75 parts of the dye of the above formula (15) and 25 parts of the dye of the above formula (10) were mixed and kneaded to obtain a dye composition. In the dye of the formula (10) of Example 27, 60 parts of the dye of the above formula (15) was used, and uniformly mixed with the above-mentioned parts to obtain a dye composition. 33 25 1261604 Example 28 A dye composition was obtained by taking 90 parts of the dye of the above formula (15) and mixing the dyes of the above formula (11). 5 Example 29 A dye composition was obtained by uniformly mixing 75 parts of the dye of the above formula (15) with the dye of the above formula (11). 10 Example 30 A dye composition was obtained by uniformly mixing 60 parts of the dye of the above formula (15) with the dye of the above formula (11). Example 31 15 A dye composition was obtained by uniformly mixing 90 parts of the dye of the above formula (15) with the dye of the above formula (12). Example 32 A dye composition was obtained by taking 75 parts of the dye of the above formula (15) and uniformly mixing with 20 parts of the dye of the above formula (12). Example 33 A dye composition was obtained by uniformly mixing 60 parts of the dye of the above formula (15) with the dye of the above formula (12). 34 1261604 Example 34 A dye composition was obtained by uniformly mixing 90 parts of the dye of the above formula (15) with the dye of the above formula (13). 5 Example 35 A dye composition was obtained by uniformly mixing 75 parts of the dye of the above formula (15) with the dye of the above formula (13). Example 36 10 A dye composition was obtained by uniformly mixing 60 parts of the dye of the above formula (15) with the dye of the above formula (13). Example 37 A dye composition was obtained by taking 90 parts of the above-mentioned formula (15) dye and uniformly mixing with the above-mentioned formula (14) dye 15 parts. Example 38 A dye composition was obtained by uniformly mixing 75 parts of the dye of the above formula (15) with the dye of the above formula (14). 20 Example 39 A dye composition was obtained by uniformly mixing 60 parts of the dye of the above formula (15) with the dye of the above formula (14). 25 Example 40 35 1261604 90 parts of the dye of the above formula (15), and the dye of the above formula (16) 10 were uniformly mixed to obtain a dye composition. Example 41 5 A dye composition was obtained by uniformly mixing 75 parts of the dye of the above formula (15) with the dye of the above formula (16), 25 Å. Example 42 A dye composition was prepared by uniformly mixing 60 parts of the dye of the formula (15) described above with 10 parts of the dye of the above formula (16) 40. Example 4 3 A dye composition was obtained by taking 9 parts of the dye of the following formula (17) and uniformly mixing it with 1 part of the dye of the above formula (2). 15 ho3soh2ch2co2s

(17) Example 44 A dye composition was obtained by uniformly mixing 9 parts of the dye of the following formula (18) with 1 part of the dye of the above formula (2). 36 1261604 h〇3soh2ch2c〇2s

S02CH2CH20S03H (18) Example 45 5 A dye composition can be obtained by taking 90 parts of the above-mentioned formula (yttrium) dye and uniformly mixing with 10 parts of the above formula (8). Example 4 6 A dye composition was obtained by taking 90 parts of the dye of the above formula (18) and uniformly mixing it with 10 parts of the above formula (8). According to Example 4, 55 parts of the dye of the above formula (15), 35 parts of the dye of the above formula (2), and 10 parts of the dye of the above formula (8) were uniformly mixed to obtain a dye 15 composition. Example 48 A dye 20 composition was obtained by taking 55 parts of the dye of the above formula (15), 35 parts of the dye of the above formula (2), and 1 part of the dye of the above formula (9). Example 49: 55 parts of the dye of the above formula (15) were mixed with the above formula (2) dye 35 37 !2616〇4 and the formula (10) dye 1 〇 part, and the dye was prepared. Composition. Application Example 1 5 + one first, 100 parts of urea, 10 parts of reducing inhibitor, 20 parts of baking soda, 55 parts of U Cannes, and 815 parts of warm water, 1 part of which can be assisted; 3 injury examples! The prepared dye was sprinkled in the above-mentioned (4) 97) wounded J paste' and quickly mixed. Cover the smear of 45-degree diagonally printed _mesh on a suitable size of mercerized cotton twill. After the color paste is over, put the scraped cloth into the price box for π 5 minutes for drying; Put a good dry cloth into the crate and steam it at atmospheric pressure for 1 〇2~1〇rc for 1 〇. Thereafter, the obtained black dye is first washed with cold water, washed with boiling hot water for 1 minute, and washed with boiling non-ionic detergent for 1 minute, and then washed once with cold water to dry. A black dye with excellent properties can be obtained. 15 Application Example 2 Take 3 parts of the dye prepared in Example 溶于 dissolved in 1 ml of water to prepare 30 parts / boost dye solution; take alkaline agent (using caustic soda "chemical ^ ml / liter and Glauber's salt 30 Parts/liter) is added to the dyeing solution (the amount of the alkaline agent is one quarter of the 20 dye solution), and the mixture is uniformly stirred. The resulting mixture is poured into a roller (R〇Uer) dyer, and then the cotton fabric is passed through a roller. After the dyeing, it is rolled into a shaft shape. The cotton fabric is stored at room temperature for 4 hours. After that, the obtained black dye is first washed with cold water, washed with boiling hot water for 10 minutes, and boiled with boiling nonionic detergent. After a minute, it was washed once with cold water and dried to obtain a black dye having 25 excellent properties. 38 1261604 Application Example 3 25 parts of the dye prepared in Example 1 dissolved in 25 G of water, = ΙΓ 1%) Take 40 ml of G1% mother liquor into the dyeing bottle, put 2 2 2 and then add 2·4 parts of thenardite, then put in the Jingji solution 2.5 ίο nightmare wooden bottle, the level of human 6GC shakes the dyeing machine, keeps 60 points Two: & the black dye is washed first by cold water, washed by boiling hot water 10, '(four) Tengzhi non-ionic cleaning The agent 4 was washed for H) minutes, and then washed with cold water. The obtained black dye had excellent characteristics. Application Example 4 0.25 parts of the dye prepared in Example 2 was used in 25 ml of water, = mother liquor (G. 1%), take 1% of the mother liquor 4G ml in the dyeing bottle, put 2: fabric, 'replace 2.4 parts of thenardite, then put 32% pure solution 2·5, put the bottle into 60 C The level is shaken in the dyeing machine, after 60 minutes of heat preservation = λ, after the household is transferred to the black dye, it is washed by cold water. After boiling hot water wash 10:1⁄2 'Fozen's non-ionic detergent 4 washes for iq minutes, then cold water Washed - once 'dry'. The obtained black dye has excellent properties. 20 Application Example 5 Take 0.25 parts of the dye prepared in Example 3 dissolved in 25 ml of water, called mother liquor (0.1%), 1 1% mother liquor 4 〇 ml in the dyeing bottle, put 2 = cotton fabric, then put 2.4 copies of mans, then put 32% pure solution 2.5 25 1 liter, put the dye bottle into 6 ° ° C In the horizontal shock dyeing machine, the heat is kept for 60 minutes. After that, the household dyed black dyed material was first washed with cold water and washed with boiling hot water for 1〇39 12616〇4~ times, :/Fo%Tengzhi non-ionic cleaning The dosage "first 10 minutes, then washed with cold water". The black dye obtained has excellent characteristics. 5 10 15 Applicable dye composition is a general-purpose dye composition, which can be dyed by dye fiber. The dyeing method used is the method used for general reactivity, such as dip dyeing, printing or continuous dyeing. Excellent characteristics. Water-soluble diterpene: The dye composition described is a commercial value: hibiscus, which can obtain various dyeing properties with good dyeing properties, especially in

...Excellent performance in dyeing depth, i-staining, low-nylon pollution, daylight fastness and heart, and light fastness. In summary, the present invention can indeed achieve the purpose of the invention by the disclosed technical idea, and the novelty and the progressiveness are consistent with the patentable elements available for the industry. However, the above-mentioned disclosures are not preferred, but the preferred embodiments, which are modified or modified locally, are derived from the technical ideas of the case and are easily inferred by those familiar with the technology. The scope of the patent right of the case. [Simple description of the map]

20【Main component symbol description】

Ml 40

Claims (1)

1261604 X. Patent Application Range: 1. A dye composition comprising: (A) at least one azo dye selected from the following formula (I) or (II) in an amount of from 1 to 99% by weight, RD" N=N —N=N - D2 ιΓ (I) OH D2— N=N—N=N — D! H03S NRiR2 S03H 10 (II) Wherein R is a hydrogen atom or a carboxyl group; R! and R2 are each independently a hydrogen atom or a <^~4 alkyl group; D! and 02 are independently selected from the group consisting of the following formulas (la), (lb), a group of (lc), (Id) 15 or (le) (R3)〇-3 41 1261604 (la) Ho3s (lb) 5 (lc) (S〇3H)〇_2 (le) 10 wherein 42 1261604 (R3) G~3 and (R4)g~3 are each independently selected from the group consisting of halogen, carboxyl, and sulfonic acid groups; For the same or different, the same or different, Cl-4 alkyl and CK4 alkoxy carboxyl or cyano group taken I 疋 hydrogen atom or unsubstituted or Ci_4 alkyl group substituted by hydroxy, sulfonic acid group 5; 2 is 0 to 2 identical or different groups selected from the group consisting of pyridylalkyl and C 4 alkoxy; - R? is a hydrogen atom, a repeating acid group, a burning group or a Ci_4 Alkoxy groups, · The heart is a hydrogen atom, a ureido group, a lysyl group, a Cl_4 alkyl group, a Ci_4 alkoxy group or a 10 C2_4 alkyl fluorenyl group; V is a group of a non-reactive amine group; Q and Q' are individually independent Is _NH_C0—CH(Hal)—CH2(Hai), -NH-CO-C(Hal)=CH2 or -S02-Y; Y is -ch=ch2, _CH2CH2〇s〇3H or _CH2CH2 U; u Is a group which leaves in the base; Hal is halogen; m is hydrazine or 1; and (B) a bisazo dye represented by the following formula (ΠΙ) in an amount of 99 to 1 by weight, S〇3h , (Ri〇)〇-2 Q2 43 1261604 wherein (Do~2 and (Ri〇)〇~2 are individually independent to 2 identical or different from the group consisting of sulfonic acid groups, d_4 alkane a group of 5 in the group consisting of alkoxy groups and alkoxy groups; Qi and Q2 are independently -NH-CO-CH(Hal)-CH2(Hal), -NH-CO-C(Hal)=CH2 or - S〇2-Y; Y is -CH=CH2, -CH2CH20S03H or _CH2CH2-U; U is a group which is easy to leave with a base; 10 Hal is an element. 2. A dye composition as in claim 1 And wherein the oxime 1 and the substituent on the azo dye of the component (A) or the oxime dye are a group of the formula (la) or (lc). a dye composition in which the formula (1) is a compound of the formula (1): COOH D broadly N=N ——Ν=Ν—D〇I H2N^^^NH2 (la) wherein D! and D2 are as defined in the patent application 4. The dye composition of claim 1, wherein the formula (π) 20 is a compound of the formula (Ila): 1261604 f S〇3H (Ila) wherein D! and D2 are as defined in claim 1 of the scope of the patent application. 5. The dye composition of claim 1, wherein the formula (III) is a compound of the formula (Ilia): OH NH2 N=N-N II Q/ H03S S〇3H Q2 (IHa) where h and Q2 are as defined in item 1 of the scope of the patent application. 6. The dye composition of claim 1, wherein the formula (1) is a compound of the formula (lb): for 3) 0-3. (^3) 〇-3 丨 Y-〇2S So plant Y (lb) where (R3)〇-3 and Y are as defined in item 1 of the scope of the patent application. 7. The dye composition of claim 1, wherein the formula (II) is a compound of the formula (lib): 45 15 1261604 (R3) 〇-3 Y-O2S (R3) 〇-3 SO plant Y so3H (lib) where (R3) 〇 _3 and Y are defined as described in item 1 of the patent application. 8. The dye composition of claim 1, wherein the formula (III) is a compound of the formula (mb): Y-02S S〇2—Y where γ is defined as described in item 1 of the scope of the patent application. Wherein the formula (lb) 9. The dye composition of claim 6 is the formula (2) HO3SOH2CH2CO2S -〇 SO2CH2CH2OSO3H Compound. 15 10. The dye composition of claim 6 wherein formula (lb) is formula (3) 46 1261604 h〇3s〇(h2c)2〇2s- C〇〇H • N = N, 丄N = N--s〇2(ch2)2〇s〇3h H2N/^^VNH2 (3) Compound. 11. The dye composition of claim 7 wherein the formula (lib) is formula (8) S〇2c2h4〇s〇3h s〇3h (8) Compound. 12. The dye composition of claim 7 wherein the formula (lib) 10 is formula (9) SO2C2H4OSO3H OH N=N^_^\ Γ^Ύ N=N nh2 H03S ΊΓ so3h HO3SOC2H4O2S- /=\ (9) Compound. 13. The dye composition of claim 7, wherein formula (lib) 15 is formula (10) 47 1261604 S〇2c2h4〇s〇3h (ίο) compound. 14. The dye composition of claim 7, wherein formula (lib) 5 is formula (11) Compound. 15. The dye composition of claim 8 wherein the formula (Illb) 10 is formula (15) So2ch2ch2oso3h compound. 16. The dye composition of claim 1, wherein formula (I) 15 is formula (16) 48 1261604 S02C2H40S03H S02C2H40S03H ho3s (16) Compound. 17. The dye composition of claim 1, wherein the component (A) has a dye content of from 5 to 95% by weight, and the component (B) has a dye content of from 95 to 5 weight percent. [1] The dye composition of claim 1, wherein the component (A) dye comprises a dye of the formula (I) in an amount of 10 to 40% by weight and a dye of the formula (II) in an amount of 1 to 20% by weight. The dye of the component (B) is a formula (III) 10 The dye content is 40 to 89% by weight. 19. The dye composition of claim 18, wherein the (I) dye content is 15 to 40 weight percent, the formula (II) dye content is 5 to 20 weight percent, and the formula (III) dye content is 40 to 80 weight percent. 49