KR830001370B1 - Process for preparing pyridone disperse dyestuff - Google Patents

Abstract

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Description

Manufacturing method of pyridone disperse dye

The present invention relates to a method for producing a pyridone dispersion dye of the following general formula (I).

The compound of general formula (I) exists in four different crystal modifications.

The diazotized p-amino benzoic acid benzyl ester is prepared in an aqueous medium preferably at pH 3 to 6 according to a method known as 1-n-butyl-3-cyano-4-methyl-6-hydroxy-pyridone-2. Coupling at temperatures between 0 and 10 ° C. yields α-strain. β-modification can be obtained by recrystallizing dry α-modification from 2-ethoxy ethanol.

γ-modification can be obtained by heating an α-modified aqueous suspension adjusted to pH 2-4 at a temperature of 80-100 ° C. for 1-5 hours. Preferably the cooled dye suspension is adjusted to pH 3 and heated at a temperature of 90-95 ° C. for about 2 hours. In addition, the suspension suitably contains an anionic surfactant. The suspension may be formed into a dried, isolated α-strain or as a wet press cake and optionally, an unfiltered coupling suspension may be used without undergoing separation and isolation process steps.

γ-modification can also be obtained by repeating recrystallization of pure anhydrous α-modification from 2-methoxy or 2-ethoxy ethanol. α-modification can be obtained by heating an aqueous suspension of any other crystal formation to about 130 ° C. warm in an autoclave. Heating is carried out for 1 to 4 hours. It is suitable to again contain the anionic surfactant in this suspension. It is advantageous to add nuclei to the suspension before heat treatment to prepare the δ-form obtained.

Four variants of the compound of formula (I) can be determined by X-ray diffraction spectrum. Table 1 shows the crystallographic distances (d-measurements) in A units of the lines observed on the X-ray diffraction spectrum measured with a Guierer / De Wolf camera using Cu-K _α1 -radiation. will be. The intensity (I) of the line was evaluated by a four step index.

s: strong

m: middle

w: weak

v _w : very weak

The diffusion line is indicated by "d".

TABLE 1

아세테이트, 셀룰로오즈 트리아세테이트 및 합성 폴리아미드로 구성되어 있거나 또는 이들을 함유하는 것들이다. 상기 지지물은 이완된 섬유사 또는 직물 형태로 존재할 수 있다. 염색할시 염료를 분산제 등의 존재하에 분쇄하는 것과 같은 기지의 방법에 따라 염색제제로 만든다. 염색 및 날염은 기지의 방법에 따라 수행할 수 있다. 그러나, α- 및 β-변형은 고온(즉, 100℃ 이상 온도) 및 압력 하에서 큰 결정을 형성하는 경향이 있기 때문에 염색하는 데 적합하지 않으므로 고온 염색에 염료를 사용할 때는 α- 및 β-변형을 γ- 및 δ-변형으로 전환시키거나 또는 임의적으로 안정한 γ- 및 δ-변형의 중량에 최소한 10배로 미리 혼합시켜야만 한다.Compounds of general formula (I) are useful for dyeing and printing synthetic or semisynthetic, high molecular weight hydrophobic organic supports from aqueous suspensions. Preferred supports are linear aromatic polyester, cellulose

Acetates, cellulose triacetates and synthetic polyamides or those containing them. The support may be in the form of a loose fibrous yarn or fabric. When dyeing, the dye is prepared according to a known method such as grinding the dye in the presence of a dispersant or the like. Dyeing and printing can be carried out according to known methods. However, α- and β-strains are not suitable for dyeing because they tend to form large crystals under high temperatures (i.e. temperatures above 100 ° C) and pressures. It should be converted to γ- and δ-modification or premixed at least 10 times to the weight of the optionally stable γ- and δ-modifications.

The dyes of the present invention, in particular γ- and δ-strains, have good hydrolysis resistance and stable strains have excellent enhancement and exceptional fastnesses on the support, in particular, light fastness, wet fastness, sublimation fastness and fastness to solvents and dry shearing. Imparting dyeability to these materials. Unstable α- and β-modifications adversely affect the fastness of such dyeing because the dyes do not accumulate to the extent that the dye is well mixed on the fiber. Therefore, these forms must be converted to γ- and δ-modifications for use as dyes.

The following examples are intended to illustrate the invention in more detail. In the examples all parts are by weight and temperatures are in degrees Celsius.

Example 1

18.25 parts of P-aminobenzoic acid benzyl ester (97%) are dissolved in 70 parts of glacial acetic acid at 50 ° C. and then reacted with 20 parts of concentrated hydrochloric acid and 40 parts of concentrated hydrochloric acid and 20 parts of concentrated hydrochloric acid. The fine crystalline suspension is quickly reacted with 22 parts of 4N-sodium nitrite solution at 4 to 6 ° C. and then the mixture is stirred at 10 to 12 ° C. for 10 minutes and then cooled to 0 to 5 ° C. using ice. Excess nitrous acid is removed with amido sulfuric acid and the product is filtered off.

A solution of 16.2 parts 1-n-butyl-3-cyano-6-hydroxy-4-methylpyridone- in 200 parts water having a pH of 5-7 is stirred with a diazo solution at 0-5 ° C. for 1 hour. The reaction was carried out while sodium hydroxide solution and ice were added to keep the pH and temperature constant. A slight excess of diazonium compound remains, with stirring of the mixture bringing the temperature of the suspension to room temperature and eliminating excess diazonium compound. Filtration followed by washing and drying in vacuo at 60 ° C. gave pure dyes with very good yields. The dye obtained is an α-crystalline variant.

Example 2

Preparation of γ-Modification

10 g of the dye prepared in the method of Example 1, either in dried form or in a wet compressed cake form, is stirred with water to form a thin dough. 1 g of a surfactant (eg sodium dinaphthylmethanedisulfonate) is added and the pH is adjusted to 3 with hydrochloric acid and the mixture is heated to 85-95 ° C. for 2 hours. After filtration, washing and drying, a γ-modified dye is obtained.

Coupling suspensions of unfiltered dyes may also be heat treated to yield stable γ-modifications.

Stable γ-modification can also be obtained by repeatedly recrystallizing the dye dried from methyl or ethyl glycol.

Example 3

Preparation of δ-strain

Ten parts of the dye prepared by the method of Example 1, either in dried form or in the form of a wet compressed cake, are made lightly kneaded with water. One part of an anionic surfactant (eg, sodium dinaphthal methane disulfonate) is added to the material and the mixture is heated to 130-132 ° C. for 2 hours in an autoclave. Cooling, filtration, washing and drying give δ-modification.

Coupling suspensions of unfiltered dye of Example 1 may also be used and the treatment temperatures described above are used.

Dye Example A

The stable variant of Example 2 or 3 was ground in the presence of a dispersant (e.g., thignin sulfonate) and spray dried to obtain a dye formulation having a particle size of about 1 micron or smaller, and the dye formulation contained three parts of the dye and the dispersant. 7 parts are mixed.

Ten parts of the finely dispersed folate are added to 1000 parts of water, followed by 30 parts of ammonium sulfate 30 parts formic acid and the rest to a 13,000 parts circulating bath containing water. A pre-washed cross-wound spool polyester 1000 parts is placed in the bath. The autoclave is sealed and heated at 60-130 ° C. for 35 minutes. After 15 minutes at 130 ° C. the autoclave is cooled to 80 ° C. and the salt bath is stopped, then the dyed supports are washed thoroughly with cold water. The support is then spun and dried in a drying cabinet. A rich (almost second degree of standard) advantage is obtained in particles insoluble in the surface with good wetting and friction fastness, and the yellowish green color of the bacterium is obtained. The dyeing apparatus is also advantageous from the precipitation of the dye and can be used as such in the next dyeing step. Drainage is substantially colorless, indicating a good enhancement of the dye.

Example B

7 parts of the dye prepared according to Example 1 was ground under a bowl for 4 hours with 4 parts of sodium dinaphthylmethane disulfonate, 4 parts of sodium cetyl sulfate or 5 parts of anhydrous sodium sulfate, and then 1 part of the dye preparation was used to prepare a water-based medicament. Was added through a salt bath containing 4000 parts of sodium sulfolicinorate (8% sulfonated) in 1 part of water and 8 parts of anhydrous sodium sulfate. The salt bath is adjusted to pH 5 with formic acid. 100 parts of polyester fibers are added to a room temperature bath and the salt bath is heated to 100 ° C. for at least 30 minutes (the oxo-phenylphenol carrier is added at 60 ° C.) and the support is dyed at this temperature for 2 hours. The fibers dyed in yellowish green are washed, sieved and then washed again and dehydrated. Thus, a leveling salt having good fastness is obtained.

Claims (1)

Pyridone dispersion of the following general formula (I) characterized by coupling a diazotized para-aminobenzoic acid benzyl ester to 1-n-butyl-3-cyano-4-methyl-6-hydroxypyridone-2 Method of making the dye.