JPH035426B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to pyridone disperse dyes. More specifically, the present invention is based on the following formula ()
Azo compound represented by: I will provide a. The compound of formula () exists in four different crystal forms (modifications). Diazotized para-aminobenzoic acid benzyl ester was converted into 1-n-butyl-3-cyano-methyl-
When coupled with 6-hydroxypyridone-2 according to a known method, preferably 3 to 6
α of the compound of formula () when coupled at a temperature of 0 to 10 °C in an aqueous medium with a pH value of
- You can get a metamorphosis. The β-modification can be obtained by recrystallizing the dried α-modification from 2-ethoxyethanol. The γ-modification can be obtained by heating an aqueous suspension of the α-modification whose pH value has been adjusted to 2 to 4 at a temperature of 80 to 100° C. for 1 to 5 hours. Preferably, the cold suspension of the dye is adjusted to PH=3 and heated at a temperature of 90-95°C for approximately 2 hours. Furthermore, it is suitable for the suspension to include anionic surfactants. Such suspensions may be prepared using a dry and separated α-modification, or alternatively may be prepared using a wet presscake, or optionally a The separation or isolation step may be omitted by using an uncoupled suspension. The α-modification can also be obtained by repeated recrystallization of the pure α-modification from 2-methoxyethanol or 2-ethoxyethanol. The δ-modification can be obtained by heating an aqueous suspension of any other crystalline form in an autoclave at a temperature of approximately 130°C. Heating can be carried out for 1 to 4 hours. Here too, it is appropriate to include anionic surfactants in the suspension. Once the crystals of the δ-form have been obtained, it is advantageous to sparge the suspension before carrying out the heat treatment to further prepare them. The modifications (4 types) of the compound represented by the preceding formula () can be distinguished by the X-ray diffraction spectra of those modifications. Table 1 below shows the interplanar spacing (d value) of the measured lines in angstroms in the X-ray diffraction spectrum measured with a Guinier/De Wolff camera using the CuK ₁ line. In the table, the strength of the line () is divided into four levels: strong (s), moderate (m),
It was evaluated as weak (w) and very weak (vw). The diffusion line is labeled with the symbol d.

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The compounds of () above are useful for dyeing and printing synthetic or semi-synthetic polymeric hydrophobic organic substrates from the form of an aqueous suspension. Preferred substrates consist of or include linear aromatic polyesters, cellulose 21/2 acetate, cellulose triacetate, and synthetic polyamides.
The substrate may be in the form of loose fibers, threads or fabrics. For dyeing, a dyeing composition is prepared from the dye according to known techniques, for example by grinding in the presence of a dispersant or the like. Dipping and printing can be carried out according to known techniques. However, the α- and β-modifications are unsuitable for dyeing under pressure and at high temperatures, for example temperatures above 100°C. This is because such transformations have a tendency to form large crystals under conditions such as those mentioned above, and for that reason such modifications are necessary if the dye is intended to be subjected to high temperature dyeing. The α- and β-modifications should be converted to the γ- and/or δ-modifications, or optionally, at least 10 times their weight of stable γ
- and δ-modifications should be mixed. The dyes of the invention (in particular the γ- and δ-modifications) have good resistance to hydrolysis and good build-up properties on substrates as mentioned above, and have remarkable fastness properties, especially lightfastness. It is possible to provide a dyeing having good properties, wet fastness (particularly perspiration fastness, water fastness and washing fastness), heat set fastness and sublimation fastness, solvent fastness and dry rub fastness. can. The following examples serve to further explain the invention. In the examples, all parts are parts by weight and temperatures are in degrees Celsius (°C). Example 1 18.25 parts of p-aminobenzoic acid benzyl ester (97% purity) are dissolved in 70 parts of glacial acetic acid at a temperature of 50°C, and to this are added 20 parts of concentrated hydrochloric acid, 40 parts of ice and a further 20 parts. of concentrated hydrochloric acid was mixed. The suspension of fine crystals was quickly reacted with 22 parts of 4N sodium nitrite solution at a temperature of 4-6°C. mix 10-12
It was stirred for 10 minutes at a temperature of 0.degree. C. and then cooled to 0-5.degree. C. by adding ice. Amidosulfonic acid was added to destroy excess nitrite and the solution was filtered clear. A solution obtained by dissolving 16.2 parts of 1-n-butyl-3-cyano-6hydroxy-4-methylpyridone-2 in 200 parts of water and having a pH of 5 to 7 and a temperature of 0 to 5°C was stirred. The mixture was allowed to react with the diazo solution for 1 hour, while the pH value and temperature were kept constant by adding an aqueous sodium hydroxide solution and ice, respectively. A small excess of diazonium salt remained. The mixture was stirred overnight, the temperature of the suspension rose to room temperature, and the excess diazonium compound disappeared. After filtering, washing and drying in vacuo at a temperature of 60° C., the pure dye was obtained in good yield. The dye obtained was in the form of the α-crystalline modification. Example 2 Preparation of the γ-modification: 10 g of the dye, either in dry or wet presscake, prepared as described in Example 1 above, were stirred with water to give a dilute paste. 1 g of surfactant (e.g. sodium dinaphthylmethane disulphonate) was added, the PH value was adjusted to 3 by adding hydrochloric acid, and the mixture was heated to 85-95° C. for 2 hours. After filtering, washing and drying, the γ-modification of the dye was obtained. In order to obtain a stable .gamma.-transformation, it was also possible to subject a neat coupling suspension of the dye described above to a heat treatment as described above. By repeatedly recrystallizing the dried dye from methyl or ethyl glycol, a stable
I was also able to get a pervert. Example 3 Preparation of the δ-modification: Water was added to 10 parts of the dye obtained as described in Example 1 above, either in the dry state or in the form of a wet presscake, to give a dilute paste. One part of an anionic surfactant (eg sodium dinaphthylmethane disulphonate) was added thereto and the resulting mixture was heated in an autoclave for 2 hours to a temperature of 130-132°C. cooling,
After filtering, washing and drying, the δ-modification was obtained. It was also possible to use a neat coupling suspension of the dye described in Example 1 above and subject it to the heat treatment as described above. Dyeing Example A The stable modifications according to Example 2 or Example 3 above are milled in the presence of a dispersant, such as a lignin sulfonate, and to obtain a dyeing composition having a particle size of less than or equal to 1 μ. , spray dried. This blend contained 3 parts dye and 7 parts dispersant. 10 parts of the fine dyestuff composition are added to 1000 parts of water and the whole is placed in a circulating bath at a temperature of 60°C (the total volume is 13000 parts, of which 30 parts ammonium sulfate, 0.3 parts formic acid, and (remaining water)
added to. A pre-cleaned crosswind spool (1000 parts of polyester thread) was immersed in this bath. Close the autoclave, and during 35 minutes 60
℃ to 130℃. After 15 min at 130 °C, cool the autoclave to 80 °C, drain the dye bath,
The dyed substrate was then thoroughly washed with cold water.
Subsequently, the substrate was subjected to spinning and dried in a dryer. A greenish-yellow deep (approximately twice the standard depth) level dyeing is obtained which has good wet and rub fastnesses. There were no insoluble particles on the surface of this level-dyed product. There were also no dye deposits found in the dyeing equipment, so
This staining device could be used as is for the next staining. The waste water was practically colorless, indicating good build-up properties of the dye. Dyeing Example B 7 parts of the dye prepared as described in Example 1 above are mixed with 4 parts of sodium dinaphthylmethane disulfonate, 4 parts of sodium cetyl sulfonate and 5 parts of anhydrous sodium sulfate in a ball mill for 48 hours. It was ground over a period of time. 1 part of the dye composition is combined with water to form a paste and this suspension is passed through a sieve into a dyebath (1:2 parts of sodium sulforisinolate (80% sulfonated) in 4000 parts of water and 8 of anhydrous ammonium sulfate). Formic acid was added to the dye bath to adjust the pH to 5. Add 100 parts of polyester fibers to a room temperature dyebath, heat the dyebath to 98°C for 30 minutes (addition of 12 parts o-phenylphenol carrier at 60°C), and at this temperature for 2 hours. The substrate was dyed over a period of time. The greenish-yellow colored fibers were washed, soaped, washed again and dried. A level dyed product with good fastness was obtained.

Claims (1)

[Claims] Azo compound having the primary formula () 2 The lines that are the γ-transformation of the compound of formula () and that produce the X-ray diffraction spectrum (CuKα ₁ line) are 11.5 (weak), 10.6 (weak), 8.0 (weak), 7.5 (
weak), 5.48 (moderate), 5.43 (moderate), 4.8 (weak), 4.6
2
(weak), 4.45 (weak), 3.4 (strong), 3.18 (moderate)
,
Azo compounds according to claim 1 having d values of 2.94 (weak) and 2.9 (weak) angstroms. 3 The lines that are the δ-transformation of the compound of formula () and that produce the X-ray diffraction spectrum (CuKα ₁ line) are 14.1 (moderate), 8.2 (moderate), 7.8 (moderate), 7.2 (weak), 5.08 ( Weak), 3.69 (Moderate), 3.48 (Weak), 3.
Four
Azo compounds according to claim 1 having d values of (moderate), 3.19 (weak) and 3.1 (weak) angstroms. 4 Azo compound having the following formula () for producing 1-n- diazotized para-aminobenzoic acid benzyl ester.
A process for the preparation of azo compounds, which consists of coupling with butyl-3-cyano-4-methyl-6-hydroxypyridone-2 in an aqueous medium having a PH value of 3 to 6 at a temperature of 0 to 10C. 5 The azo compound is γ of the compound of the formula ()
- Modified and diazotized para-aminobenzoic acid benzyl ester with 1-n-butyl-3-
Cyano-4-methyl-6-hydroxypyridone-
2, consisting of heating an aqueous paste (PH = 2-4) of a compound of formula () prepared by a method comprising coupling with 2. , the manufacturing method according to claim 4. 6 The azo compound has the δ of the compound of the formula ()
- modification, and α of the compound of formula ()
-, β- or γ-modification in an aqueous medium under pressure.
5. A process according to claim 4, comprising heating to a temperature of at least 130<0>C for a period of -4 hours. 7 Azo compound having the following formula (): 1. A method for dyeing or printing a substrate made of or containing a synthetic or semi-synthetic polymeric hydrophobic organic substrate, which comprises using as a dyeing or printing agent. 8 The azo compound is γ of the compound of the formula ()
- A method according to claim 7, which is a metamorphosis. 9 The azo compound is δ- of the compound of the formula ()
8. The method of claim 7, which is a metamorphosis.