JPS60133064A - Disazo compound and dyeing process using the same - Google Patents

Abstract

NEW MATERIAL:A compound of formula I [X is H or SO3H; Y is of formula II(R1 is H, CH3 or C2H5; R2 and R3 are each H, Cl, CH3, SO3H or COOH); D is of formula III (R4 and R5 are each H, CH3 or OCH3; Z is -CONH-, -SO2NH-, etc.; R6 and R7 are each H, CH3 or Cl)] in the form of free acid. EXAMPLE:A compound of formula IV. USE:For dyeing red with high wash-fatness cellulose fiber such as cotton and mixed fabrics made of the same and other fiber(s). Capable of dyeing cotton component red in one-bath-one-step process even with a combination with other dye(s). PREPARATION:For example, cyanuric chloride and 2-amino-5-naphthol-1,7-disulfonic acid are condensed; furthermore, 6-amino-1-toluenesulfonyloxynaphthalene-3- sulfonic acid being condensed followed by coupling of 0-anisidine-5-sulfonic acid diazotized product, which is then condensed with a compound of formula V followed by introducing copper using a relevant agent, carrying out a hydrolysis, then coupling of a diazotized product from the formula V compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a disazo compound and a dyeing method using the same. More specifically, in the form of a free acid, the formula (1) [Formula (1) K OiteX bar H or bar 5O3H,
Y is the formula (2), R2 and R3 are each independent K-I-I, -CI, ,
-'! -Coo)] D represents formula (3), respectively.

(Formula (31K)
-, or -8O2NI-I-, R6,, R, and 7 each independently represent -1-1, -CfT3 or bar CI.)
This invention relates to a disazo compound represented by the following formula and a method for dyeing cellulose fibers using the disazo compound.

BACKGROUND OF THE INVENTION In recent years, blended products of polyester fiber/cellulose fiber have come into widespread use as fiber materials. When dyeing such a blend using a one-bath one-step method using disperse dyes and conventional direct dyes under acidic and high temperature conditions, which are the dyeing conditions for polyester fibers, it is difficult to dye the cellulose fibers with the direct dyes. Problems such as extremely low properties, coagulation of the direct dye in the dye bath, and failure to obtain uniform dyeing are likely to occur. Therefore, we are forced to use a two-bath dyeing method or a two-bath two-stage dyeing method, which is unfavorable from the standpoint of energy and labor savings. Among direct dyes, many red dyes in particular tend to exhibit the above-mentioned drawbacks, so we developed a red direct dye that exhibits good dyeability on cellulose fibers under dyeing conditions such as high temperature in an acidic bath. Production was strongly desired. The present inventors have developed polyester fiber/cellulose fiber, especially polyester fiber/
As a result of intensive research to find a red direct dye that exhibits good dyeing without causing the above-mentioned troubles even under dyeing conditions such as dyeing cotton blend products (T/C blend) in an acid bath at high temperature,
The present invention was completed based on the discovery that the compound represented by formula (I) has extremely excellent properties. The compound of formula (1) is characterized not only by its suitability for T/C mixed one-bath one-stage dyeing, but also by the fact that the cellulose fibers dyed with it have extremely high various fastnesses, especially washing fastness. Of course, the compound of Bunbu (1) can be used for the usual dyeing of cellulose fibers such as cotton, rayon, and hemp, but it can also be used as a blended product in addition to T/C blends, acrylic fiber/cotton, and polyamide fiber/cotton. It is also possible to dye the cotton side with a red pigment even if a wool/cotton blend is used in combination with dyes from other species to carry out one-bath one-step dyeing.

The present invention will be explained in more detail.

The disazo compound represented by formula (1) is generally produced as follows.

Cyanuric halides, such as cyanuric bromide, cyanuric fluoride or more preferably cyanuric chloride and 2-amino-5-
naphthol-1,7-disulfonic acid or 2-amino-
5-naphthol-7-sulfonic acid is condensed (first condensation), and 6-amino-1-toluenesulfonyloxynaphthalene-3-sulfonic acid is further condensed. (Two arrow lines)
The condensate thus obtained contains ortho-anisidine-
The diazotized 5-sulfonic acid is cambred. (First-order compling) (Equation (R, , R, in 2J
The compounds represented by 2 and I (3 represents the same meaning as above) are condensed. (Tertiary condensation) Next, after adding a copperization accelerator as necessary, a copperization agent is added to perform copperization, and then caustic alkali is added to make it strong alkaline and hydrolyzed to form a free acid. (4) A compound represented by (in formula (4), X and Y have the same meanings as above) is obtained. (The compound of formula (4) may be acid-salted out using a conventional method, separated from each other, and the product taken out as a cake, or the compound of formula (4) may be transferred to the next step as a solution.) Coupling a diazotized compound of the compound represented by formula (5) to the compound (secondary coupling (formula (5)
In 'f%4. R5, Ra, R7 and Z have the same meanings as above.) A compound of formula (1) is obtained.

Specific examples of the compound (tertiary condensation component) represented by formula (2) include S, O, J-T, and the like. (However, the sulfone group is expressed in the form of a free acid.) Specific examples of the compound represented by Bunmu (5) include the following.

The above-mentioned reactions such as primary, secondary and tertiary condensation, primary and secondary coupling reactions, copperization reactions and hydrolysis can be carried out by conventional methods, but suitable reaction conditions are described below. .

The temperature of the primary condensation is 0 to 25°C, pH 0.5 to 45, preferably 5 to 150°C, io5 to 5. Secondary condensation is carried out at a temperature of 30-70° Cpi-i 4-7, preferably at a temperature of 40
~ 50 ° CI) T (4,0 ~ 45, the first coupling with the secondary condensate is at temperature O ~ 30' CI) I (6 ~
9, preferably carried out at a temperature of 10-15° Cps - 17-8.

Tertiary condensation temperature 80-100cpI2-7, preferably temperature 90-95°Cpl-T 2-3 (L (2
1] When the compound has a sulfonic acid group) and pr-z
5 to 7 (when the compound of formula (2) does not have a sulfonic acid group). In the copperization reaction, copper sulfate, copper acetate, copper chloride, preferably copper sulfate is used as a copperization agent, and if necessary, aqueous ammonia, monoethanolamine, jetanolamine, N-methylethanolamine, It is carried out at a temperature of 90 to 100'C using ammonia water, etc. The hydrolysis reaction is carried out at a temperature of 60 to 90°C, preferably 60 to 70°C, using caustic soda or caustic potash as a caustic alkali to a strong alkali of PR-113 or higher.

As conditions for the secondary cambling step, a temperature of 10'C or less is used in the diazotization reaction, and a temperature of 5 to 15C and pT-19 to 1o is used in the coupling reaction.

The novel disazo compound of the present invention can be applied to cellulose fibers by a known dyeing method or by a printing method using a prepared color paste, or by dyeing polyester fibers with a disperse dye, such as a high-temperature dyeing method or a carrier dyeing method. It can be dyed to a red hue with excellent wash fastness under the dyeing conditions used in

The compound of the present invention can be used alone or in combination with a mixture of two or more kinds of dyes such as disperse dyes, basic dyes, acid dyes, etc. It should be noted that the compound has good high temperature acidity. Because of this suitability, T/C blends can be dyed in a single step using disperse dyes for polyester without any problems in terms of dyeing operations, fastness of dyed products, etc.

The compound of the present invention, which enables a one-bath one-step method in place of the two-bath method and two-bath two-step method conventionally carried out in T/C mixed dyeing, and the dyeing method using the same, are advantageous from the viewpoints of energy saving, process simplification, etc. Therefore, the economic effect is extremely large. - The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples. In the Examples, parts represent parts by weight, and carboxyl groups and sulfonic acid groups are: shall be expressed in free acid form.

Example 1 37 parts of cyanuric chloride was added to 30 parts of ice water containing 0.1 part of Liponox NA (dispersant manufactured by Lion Oil) and dispersed for 10 minutes. To this, 2-amino-5-naphthol-1
, 6.3 parts of 7-disulfonic acid was added to 40 parts of water with pi-17.
, 5 was added over a period of 20 minutes, stirred at a temperature of 10° C. for 2 hours, and one arrow was combined. (pt gradually decreased to 07) Next, this reaction solution was added to 6-amino-1-toluenesulfonyloxynaphthalene-3-
A solution prepared by dissolving 7.9 g of sulfonic acid in 50 parts of water at a pH of 8.0 was added all at once and the temperature was raised to 50°C. During temperature rise, the reaction solution was maintained at pH 4.5 using a 10% sorter solution in water,
The reaction was further carried out at the same temperature for 2 hours. (Secondary union) Separately O
-7 Nisidine-5-sulfonic acid 4.1 parts! 2.3 parts of hydrochloric acid was added to a solution containing 1 part of J Honox N A O suspended in 20 parts of water, and the temperature was brought to below 0°C with ice.
5 parts (about 30% solution) was added dropwise over about 20 minutes, and diazotization was further carried out at 10° C. or lower for 1 hour. Next, after eliminating excess nitrite ions with sulfamic acid, this diazo solution was added in batches to the binary condensate solution cooled to 10°C with ice, and rapidly reduced to pT-17.0 with a 10% aqueous soda ash solution. Neutralized. After maintaining the same temperature pJ-1 for 1 hour, the mixture was stirred overnight to decompose the excess diazo liquid. Add 37 parts of aniline to the leaked reaction solution and add 10% hydrochloric acid to pJ-i 5.
．． After neutralizing to 0, the temperature was raised to 95°C. The reaction was carried out at the same temperature for 3 hours.

(3 normals) Separately, 50 parts of copper sulfate was dissolved in 25 parts of warm water, and 10 parts of 28% ammonia water was added to react. This reaction solution was added to the ternary condensation solution and reacted at 95° C. for 3 hours to obtain a reaction solution containing the following compound.

(2) To this reaction solution, 12 parts of 48% caustic soda was added at 70°C, and the mixture was stirred for 2 hours while maintaining the same temperature, followed by hydrolysis. After completion of hydrolysis, neutralize with hydrochloric acid and chloride) IJ
About 75 parts of aluminum was added thereto, and after salting out, the mixture was separated to obtain a compound of the following formula (7).

Add the above compound (719.9 parts to 200 parts of warm water to 10%
After adjusting to pi-111,0 with a caustic soda aqueous solution and completely dissolving it, 30 parts of soda ash was added.

Add ice to this solution to keep it below 10°C and separate 3-amino-
2.9 parts of 4-methoxy-2'-methyl-3-chloropenguanilide was suspended in 20 parts of water containing 6 parts of hydrochloric acid, the temperature was brought to 0°C with the addition of ice, and 075 parts of sodium nitrite (approx. 30%
(as an aqueous solution) was added dropwise over about 5 minutes, treated at below 10°C for 1 hour, and then the diazo solution prepared by eliminating excess nitrite ions with sulfamino acid was heated at below 15°C for 1 hour.
A 0% aqueous soda ash solution was added in portions to maintain a pr-+ of 9-10. After stirring for 4 hours, the temperature was 80
The temperature was raised to 'C' and the mixture was separated in a furnace to obtain the following compound.

This compound dissolves red in water and its λmax (20
pyridine aqueous solution) had a wavelength of 532 nm.

This product dyed cotton in a red hue and had excellent washing fastness.

Example 2 2-amino-5-naphthol-7-sulfonic acid 4 instead of 2-amino-5-naphthol-1,7-disulfonic acid
The following compound corresponding to formula (7) of Example 1 was obtained by carrying out the same operation as in Example 1 except that 7 parts were used and one arrow combination was performed.

Hereinafter, in Example 1, instead of using compound (7), 1 part of the above compound (919) was used, and the same operation as in Example 1 was carried out to obtain the following compound.

(20% pyridine aqueous solution) was 534 nm.

This material was used for dyeing cellulose fibers and gave a reddish-purple dyed product that was fast after washing.

Example 3 The same operations as in Example 1 were performed up to the time before the three-component condensation reaction.

Next, 42 parts of methanic acid was added in powder form while being careful not to foam, and the temperature was raised to 95°C.

Next, the pI-( was adjusted to 20 with 10% hydrochloric acid, and the reaction was carried out at the same temperature for 3 hours.
The following compound corresponding to Compound 1 of 7) was obtained.

10.7 parts of the compound of the above formula (11) was added to 200 parts of warm water, adjusted to r)I (10.5 with a 10% aqueous solution of caustic soda, and after complete dissolution, 20 parts of soda ash was added. Separately, 20 parts of soda ash was added to this solution. 4124 parts of 3-amino-4-methoxybenguanilla were suspended in 20 parts of water containing 2.5 parts of hydrochloric acid, the temperature was brought to 0°C with the addition of ice, and 075 parts of 6 tbsp of sodium nitrite (7.30% Aqueous solution) was added dropwise over a period of about 5 minutes.
The diazo solution prepared by treating at 0°C or lower for 1 hour was heated at 15°C.
Below C 1) I-I 9 to 10 were added, stirred for 4 hours, and treated in the same manner as in Example 1 to obtain the compound of formula (13).

This compound dissolves red in water and its λmax (20
% pyridine aqueous solution) was 527 nm.

A compound of formula (14) was synthesized in the same manner as in Example 1.

Table 1 shows Y and I] of the compound of formula (14), λmax
(nm.

The hues when cotton was dyed using 20% pyridine aqueous solution) and each compound are shown.

Table 1 Example 14 Blended knitted fabric of polyester fiber and cotton (blending ratio 50:5
0) was placed in the following dye bath, heated from 50°C to 130'C in 40 minutes, held at 130°C for 40 minutes, and then
It was cooled to 0°C for 10 minutes and dyed at the same temperature for 15 minutes. After dyeing, wash with water, Sanyo Chemical Co., Ltd., Sanfix 5.
A fixing treatment for 20 minutes in a bath containing 2 P/A of 55 at 60 DEG C. gave a dyeing exhibiting excellent washfastness as shown in the table below.

・Dye bath composition 1 Anhydrous sodium sulfate 20 g/Swamp bath ratio 1:15 (adjusted to pT-I 4.5 with acetic acid and sodium acetate) Fastness results table Example J5 Cotton stockinette was placed in the following dye bath and carried out. The products dyed by the method of Example 14 and subjected to the fix treatment had extremely excellent washing fastness as shown in the table below.

・Dye bath composition・Bat ratio 1:20 Fastness results table Example 16 A blended muslin of polyester fiber and viscose rayon (blend ratio 65:35) was placed in the following dye bath and dyed using the method of Example 4. As shown in the table below, those treated with Inox showed extremely excellent washing fastness.

・Dye bath composition・Bath ratio 1:15 (Adjusted to PL-14,5 with acetic acid and sodium acetate) Fastness results table Comparative example Cotton knitted fabric Example 30 Using the compound of formula (13) and known dyes The washing fastness of the dyed products dyed by the method of Example 14 and then fixed was compared. As shown in the table below, it can be seen that the compounds of the present invention have extremely superior washing fastness compared to known dyes.

*1 According to JIS L-084-4-A2 *2 C
I Direct Red 89 (Special Publication No. 39-2397
1. , Example 1) N (CF-12CI-■2) 20 CI Direct Red 243 (Special Publication No. 52-
15712. Example 1) INI-1UH2Ul-1zυ
11

Claims (1)

[Claims] ('') Formula (1) in the form of free acid [Formula (1] Nioite X HaH or Ha803 Hwo, YR
,2,Rs h each h independent ICM ,'-CI,
7CI-T3. 5O3H or -〇〇OI-1 to 81
D represents formula (3). R17 (In formula (3), R4 and Rs are each independently -H9-C
I-I3 or -ocH;, Z is -CONH-, -NH
CO-. -8O2CI-12 or -80□NH-, Rs,
R7 each independently represents -H, CHa or -CI in the shell)] A disazo compound (2) in the form of a free acid of formula (1) [In formula (1), X is 10 or -8037-1 , Y
(In formula (2), R1 is -H, CHa or -C2H
5, R12 and R3 are each independently -H, -CI, -C
I-I3.5O3H or -COOH \Onibiwashu) D represents formula (3) respectively (formula (3) smell -CR4, us C each independently -H,
-crq3 or Haocr-x3, Z bar C0NH-,
-NI-ICO-, -802CH2- or -8O2NH
-, R6 and R7 are each independently -I-■, -crT3 or Hac+ wo camellia cold)] is used.