JPH0647657B2 - Formazan compound and method for dyeing cellulose fiber using the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a formazan compound and a method for dyeing a cellulosic fiber characterized by using the same.

2. Description of the Related Art Generally, metal-containing formazan dyes are widely used because of their clear color tone and excellent fastness, especially fastness to sunlight. Suitable formazan dyes for dyeing cellulose fibers are Japanese Patent Publication No. 55-33777.
C. I. No. Reactive Blue 182, C.I. I. No. Reactive Blue
52, the C.I. I. No.R
There are eactive Blue 212, etc., but these dyes are
When dyeing in a dyeing bath, the property of causing agglomeration which is not preferable for dyeing, and C.I. I. No. Reactive Red 120,
C. I. When used in combination with No. Reactive Yellow 138 or the like, there are problems that the absorption behavior is not uniform when the intermediate color is produced and the leveling property is not good. In addition, Japanese Examined Japanese Patent Sho 58-5518
C.8. I. No. Reactive Blue 160 has a good leveling property, but has a problem that various fastnesses are poor.

Problems to be Solved by the Invention In the dyeing of cellulosic fibers, there is a demand for the development of a dye that satisfies the properties that the dyed product has various fastnesses and good levelness.

Means for Solving the Problems The present invention has been achieved as a result of intensive research to develop a formazan-based blue dye that is used for dyeing a cellulosic fiber and is excellent in various fastnesses and levelness. .

That is, the present invention has the formula (1) in the form of the free acid. [In the formula (1), X represents F or Cl, R ₁ represents hydrogen, a sulfonic acid group, a methyl group, a methoxy group, a hydroxyl group or chlorine,
R ₂ and R ₃ represent a methyl group or an ethyl group, and n is 0 or 1.
And m and l represent 0, 1, 2, or 3. However, n + m +
1 = 3 or 4. ] A formazan compound represented by the following and a method for dyeing a cellulosic fiber characterized by using the same are provided.

In order to obtain the formazan compound represented by the formula (1) of the present invention, first, the formula (2) [In the formula (2), R ₁ has the same meaning as described above. ] The formazan amino compound represented by these is synthesize | combined by the method described below, for example. That is, 2-amino-4-sulfobenzoic acid is diazotized by a conventional method, and its diazotized product is reduced with NaHSO ₃ or Na ₂ SO ₃ or the like to give 2-carboxy-5-sulfophenylhydrazine of the formula
(3) (In the formula (3), R ₁ has the same meaning as described above.) The compound represented by the formula is condensed in an aqueous solution at 80 to 95 ° C.
(Four) A 5-sulfo-2-carboxyphenylhydrazone represented by the following formula was obtained, and 6-acetylamino-2-aminophenol-4-sulfonic acid diazotized by a conventional method and 0
Coupling in aqueous solution at ~ 5 ° C in the presence of soda ash and the like.

Then, add copper sulfate, copper chloride, etc.
It is maintained at 9 to act to form a formazan copper complex salt.

Next, the acetylamino group is strongly alkaline at 60 to 90 ° C.
By hydrolyzing for 3 to 6 hours to give an amino group
The formazan amino compound (2) is obtained.

Next, the formazan compound of the formula (1) is synthesized, for example, according to the method described below.

I. The formazan amino compound represented by the formula (2) is 2,
1 mol of 4,6-trichloro-1,3,5-triazine or 2,4,6-trifluoro-1,3,5-triazine 1
Reaction with mol at pH 6-8, 0-10 ° C for 2-3 hours
(Five) [In the formula, R ₁ and X represent the same meaning as described above. ] To obtain a condensate, then the formula (6) _{(R 2, R 3, n} , m and l are the same meaning represents a) diamines 1 mole and represented by PH6～9,50～65 ° C.
Reaction for 8 to 24 hours with formula (7) To obtain a formazan compound of the formula (1) by reacting with 1 mol of the compound of the formula (5) at pH 6 to 9 and 50 to 65 ° C. for 8 to 24 hours.

Alternatively, 2 mol of the compound represented by the formula (5) and 1 mol of the diamine represented by the formula (6) are reacted in the water at a pH of 5 to 8 or 10 ° C. or lower for 2 to 4 hours to prepare the compound of the formula (1). Formazan compounds may be obtained.

II. 2,4,6-trichloro-1,3,5-triazine or 2,4,6-trifluoro-1,3,5-triazine 2 mol and diamine of the formula (6) 1 mol and pH 5 ~
Sequential condensation in water at 8 ° C or less and 10 ° C or less for 2 to 4 hours gives formula (8) (Wherein X, R ₂ , R ₃ , n, m and 1 have the same meanings as described above), and then a formazan amino compound represented by the formula (2) is added to pH 6-9, The compound of formula (1) can also be obtained by reacting at 50 to 65 ° C. for 2 to 4 hours.

In order to separate the thus obtained target substance from the reaction solution, an ordinary separation method such as an acid precipitation method or a salting out method is applied.

Next, specific examples of the compounds represented by the formulas (3) and (6) will be given.

The formazan-based compound of the present invention is suitable for dyeing natural and regenerated cellulosic fibers and blended fibers containing these and fibers other than cellulosic fibers. The dyeing method includes a printing method, a dipping method, and a padding dyeing method. For example, a method usually used for dyeing with a reactive dye can be applied.

First, in the printing method, sodium alginate, emulsion paste, etc. are usually used as the base paste, and a dye, an acid binder,
A color paste to which urea or the like is added is prepared, printed on a fiber, and if necessary, intermediate drying is performed, and then steam or dry heat treatment is performed to fix the dye. In this case, the fibers impregnated with the acid binder solution are printed with a color paste containing no acid binder, or with a color paste containing no acid binder, and then a solution containing an acid binder is used. Then, the dye may be fixed by the same treatment as described above. Next, when the compound (dye) of the present invention is applied under the condition that the bath ratio is relatively large as in the dip dyeing method, 10 to 60 at 20 to 130 ° C. in the presence of an inorganic salt such as sodium chloride or sodium sulfate. After dyeing for 30 minutes, an acid binder is added and dyeing is further performed at 30 to 100 ° C. for 20 to 60 minutes. In this case, a method of adding an acid binder from the beginning of dyeing can also be used.

When the compound (dye) of the present invention is applied under conditions of relatively small bath ratio such as padding dyeing method, dye, acid binder, penetrant, urea as a solubilizer, sodium alginate as a migration inhibitor. The fibers are padded in a pad bath prepared from the above, and after squeezing, steam or dry heat treatment is performed to fix the dye.

Examples of the acid binder used in the above dyeing method include sodium hydrogen carbonate, sodium metaphosphate, and phosphoric acid 3
Examples thereof include sodium, ortho or sodium metasilicate, sodium carbonate, sodium hydroxide and the like.

The formazan-based compound (dye) of the present invention is a printing paste, and the stability of the dye when prepared as a pad bath is high.
The density fluctuation of the dyed product due to changes in steaming or dry heat treatment conditions in the padding dyeing process is small, and a dyeing product having a high fixation ratio similar to that of the usual dip dyeing process can be obtained. The obtained dyed product has good levelness and exhibits a blue hue excellent in light fastness, fastness to washing, water and chlorine water. Further, when dyeing by the dip dyeing method, the dyeing property is particularly excellent, and C.I. I. No. Reactive Red 120,
C. I. The absorption behavior is the same when blended with No. Reactive Yellow 138 and the like, and a dyeing product excellent in light fastness, sweat light fastness, washing, water and chlorine water fastness is obtained.

Next, the present invention will be described in detail with reference to Examples.

In the examples, parts represent parts by weight, and the sulfonic acid group in each formula is represented in the free form.

Example 1. 2 parts of the compound represented by the formula (9), 80 parts of sodium chloride,
A dyebath is prepared with 1000 parts of water, 50 parts of cotton knitted fabric is immersed in this dyebath and treated at 80 ° C. for 30 minutes, and then 20 parts of sodium carbonate is added, followed by treatment at the same temperature for 60 minutes for dyeing. I do. Then, after washing with water, 95 to 100 ° C. using 1000 parts of an aqueous solution containing 2 parts of an anionic activator.
By soaping for 10 minutes, washing with water and drying, a blue dyed product with good levelness was obtained. This product was excellent in light resistance, wetness and fastness to chlorine water.

The compound of formula (9) was synthesized as follows.

4-sulfo-2-hydrazinobenzenebenzoic acid represented by the formula (10) 85 parts of 4.7 parts and benzaldehyde 2.1 parts at pH 1 to 3
Hydrazone compound of formula (11) obtained by condensation in an aqueous solution at a temperature of ~ 95 ° C in the presence of soda ash 3-amino-4-hydroxy-5-acetylaminobenzenesulfonic acid formula (12) Was coupled with the diazo compound of. While maintaining the formed formazan at pH 6 to 7 with 10% aqueous soda ash solution, 5.3 parts of sulfuric acid (pentahydrate) was added and reacted at 10 to 30 ° C to form a copper complex salt, which was then salted out and taken out. rear,
After heating with dilute caustic soda water at around 90 ° C to hydrolyze, formula
A formazan amino compound of (13) was obtained.

Cyanuric chloride 3.8 parts water 20 parts, ice 40 parts, 10% Liponox NA (Lion Co., Ltd. dispersant) aqueous solution 0.5
It was added with stirring to a solution of 3 parts. After stirring for 30 minutes, 10
A solution containing 12.8 parts of the formazanamino compound of formula (13) was added while maintaining the temperature below ℃. Then, the reaction was carried out for 2 hours at around 10 ° C. while maintaining the pH value at 6 to 8 with a 10% soda ash aqueous solution. Then 3,5-diamino-2,
2.3 parts of 4,6-trimethylbenzenesulfonic acid was added to 2 parts of water.
A solution of 0 parts dissolved weakly alkaline was added to the above reaction solution. The temperature of this mixture was raised and reacted at a temperature of 55 to 60 ° C. for 20 hours while maintaining a pH value of 6 to 8 with a 10% aqueous soda ash solution. Then, salting out was carried out with sodium chloride at the same temperature, and the crystals were separated by filtration. After drying at 60 ° C., 22.0 parts of the compound of formula (9) was obtained. (Λ _max 625nm
20% pyridine aqueous solution) Examples 2-11. Using the formazan compound synthesized according to Example 1, cotton was dyed. These dyed products were excellent in levelness and fastness. Table 1 shows the structural formulas of the synthesized compounds, the hue when dyed with cotton, and the λ _max of the compounds in a 20% aqueous pyridine solution.

Example 12. 2 parts of the compound represented by the formula (14), 80 parts of sodium chloride,
A dyebath is made up with 1000 parts of water, 50 parts of cotton knitted fabric is immersed in this dyebath and treated at 70 ° C. for 30 minutes, then 15 parts of sodium carbonate is added and subsequently treated at the same temperature for 60 minutes. And stain. Then, after washing with water, using 1000 parts of an aqueous solution containing 2 parts of an anionic activator, 95-
By soaping at 100 ° C. for 10 minutes, washing with water and drying, a blue dyed product with good levelness was obtained. This product was excellent in light resistance, wetness, chlorine and water fastness. The compound of formula (14) was synthesized as follows.

2.3 parts of 3,5-diamino-2,4,6-trimethylbenzenesulfonic acid are added to 20 parts of water, 40 parts of ice, and 0.5 parts of 10% Ribonox NA (Lion Co., Ltd., a dispersant) aqueous solution. Add to the solution and adjust the pH value to 6-7 with soda ash to complete the bath. While maintaining the temperature below 5 ° C, 2.7 parts of 2,4,6-trifluoro-1,3,5-triazine (cyanuric fluoride) was added to the above solution, and the pH value was adjusted to 6 to 10 with a 10% soda ash solution. While maintaining at 8, react for 2 hours to obtain an intermediate having the following structure, Then, 12.8 parts of the formazan amino compound of the formula (13) was added, and the reaction was carried out for 1 hour while maintaining the pH value at 6 to 7 at a temperature of 30 to 40 ° C. Then, salting out was carried out with sodium chloride at the same temperature, and the crystals were separated by filtration. Dry at 60 ° C and then use the above formula (14).
21.0 parts of the compound of

(Λ _max 625 nm in 20% aqueous pyridine solution) Examples 13 to 22. According to Example 12, cotton was dyed using the synthesized formazan compound. These dyed products were excellent in levelness and fastness. Table 2 shows the structural formula of the synthesized compound, the hue when dyed on cotton, and 20% of the compound.
The λ _max in the aqueous pyridine solution is shown.

Example 23. Cotton gabardine is padded with 1000 parts of a pad bath consisting of 30 parts of the compound of formula (9) described in Example 1 and 970 parts of water, squeezed to a squeezing ratio of 60%, and intermediate drying is carried out. Subsequently, trisodium phosphate 20 parts, anhydrous sodium sulfate 200 parts, water 7
Fixing is performed by a Zicker dyeing tester at 80 ° C. for 60 minutes in a treatment bath consisting of 80 parts. Then, soaping was carried out in the same manner as in Example 1 and washing with water and drying were carried out to obtain a blue dyed product having good levelness.

Example 24. Using the compound of formula (15) (the compound obtained in Example 7),
1000 parts of color paste are prepared according to the following table.

[X represents 10, 30 and 60. Polymine Lnew is a reduction inhibitor made by Nippon Kayaku] The above color paste was printed on a mercerized cotton broad cloth, dried at 60 ° C for 10 minutes, steam-heated in saturated steam at 100 ° C, and then washed with water.

The steaming time was changed to 5 minutes, 10 minutes, and 20 minutes.

Then, after washing with warm water at 60 ° C. for 5 minutes, 1000 parts of a boiling bath containing 2 parts of an anionic surfactant was used for soaping for 15 minutes, followed by washing with water. By drying the printed material, a clear blue printed material having excellent leveling properties and build-up properties was obtained.

Comparative test A comparative test between the compound of the present invention and a known dye was carried out by the following method.

1) Level dyeing test As an example of a red reactive dye, C.I. I. No. Reactive Red
120, also as an example of a yellow reactive dye, C.I. I. No. Rea
A comparison of the level dyeing properties when using Ctive Yellow 138 (compound dyeing) was carried out as follows.

C. I. No. Reactive Red 120 1 part, C.I. I.
1 part of No. Reactive Yellow 138, 1 part of the compound of the present invention or a known dye shown in the comparative test result column, 80 parts of anhydrous sodium sulfate, 20 parts of anhydrous sodium carbonate and 100 parts of water.
A dyebath is prepared by using 0 part, and 50 parts of unmercured cotton knitted fabric is dipped in the dyebath for 30 minutes at 40 ° C. for 80 minutes.
The temperature was raised to ° C. At this time, 1 minute, 10 minutes, 20 minutes, and 30 minutes after the immersion of the article to be dyed, a small amount of the article to be dyed was taken out from the dye bath, and the balance of the absorption rates of the Red, Yellow, and Blue components was examined.

After the temperature was raised to 80 ° C., treatment was continued for 60 minutes at the same temperature for dyeing.

Then, after washing with water and hot water, 1000 parts of an aqueous solution containing 2 parts of an anionic activator was used for soaping at 100 ° C. for 10 minutes, and the dyed product was washed with water and dried. The level dyeing property of the obtained dyeing that accompanies the absorption behavior at the time of dyeing with the three primary colors as described above is not limited to the dyeing process with excellent dyeing reproducibility or the dyeing process with high quality and high quality. It is a very important issue in terms of reduction.

<Judgment and Display of Results> x: The absorption rate of the Blue component is significantly higher than that of the Red and Yellow components, and the levelness of the obtained dyed product is poor.
(Blue component is unevenly dyed or the dyed surface is poor) Good: The red, yellow, and blue components have the same absorption rate, and the dyed product obtained is excellent in levelness.

2) Fastness test First, a mercerized cotton knitted dyeing product having a density that matches the standard dyeing density was prepared. (Dyeing conditions other than the dye or the compound were dyed according to the item 1). ) Next, 50 parts of this dyed product is immersed in 1000 parts of an aqueous solution containing 4 parts of a quaternary ammonium salt-based fixing agent (liquid product), treated at 60 ° C for 20 minutes, washed with water and dried to obtain fastness. It was used as a test sample.

<Fastness test conditions> Light resistance: JIS L0842 (1971) Sweat light resistance: Artificial sweat fluid Adjusted to pH 8.0 with sodium hydroxide Other conditions were in accordance with JIS L0888 (1977).

Washing: JIS L0844 (1973) A-4 method <Judgment and display of results> Light resistance: Judgment of the degree of discoloration and fading by Blue Scale (Japanese Standards Association).

Sweat and light resistance: Gray scale for changing color and fading (JI
S L0804) determines.

Washing: The degree of contamination of the white cloth attached to the cotton is judged by a staining gray scale (JIS L0805).

From the above results, the compound of the present invention is compared with known dyes,
C. I. No. Reactive Red 120, C.I. I. No. Re
It can be seen that the absorption speed at the time of compound dyeing with active Yellow 138 is the same, and that the dyed product obtained is excellent in dyeability and various fastnesses.

EFFECTS OF THE INVENTION A formazan compound having good leveling properties and excellent dyeing fastness upon dyeing a cellulosic fiber was obtained.

Claims (2)

[Claims] 1. A formula (1) in the form of a free acid. [In the formula (1), X represents F or Cl, R ₁ represents hydrogen, a sulfonic acid group, a methyl group, a methoxy group, a hydroxyl group or chlorine,
R ₂ and R ₃ represent a methyl group or an ethyl group, and n is 0 or 1.
And m and l represent 0, 1, 2, or 3. However, n + m +
1 = 3 or 4. ] The formazan compound represented by these. 2. The formula (1) in the form of the free acid. [In the formula (1), X represents F or Cl, R ₁ represents hydrogen, a sulfonic acid group, a methyl group, a methoxy group, a hydroxyl group or chlorine,
R ₂ and R ₃ represent a methyl group or an ethyl group, and n is 0 or 1.
And m and l represent 0, 1, 2, or 3. However, n + m +
1 = 3 or 4. ] The dyeing method of the cellulose fiber characterized by using the formazan compound represented by these.