JPS5846231B2 - Monoazo dye for polyester fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a monoazo dye for polyester fibers, and more specifically, it dyes polyester fibers in a vivid greenish-yellow color and improves various fastnesses, particularly light fastness, sublimation fastness, and water fastness. This invention relates to a monoazo dye that has excellent temperature stability and pH stability during dyeing.

The present invention will be explained in detail below.

The monoazo dye of the present invention has the following general formula [■] (where R
is lower alkoxy lower alkyl group, lower alkoxy lower alkoxy lower alkyl group, lower alkoxy lower alkoxy lower alkoxy lower alkyl group, halogeno lower alkyl group, lower alkoxycarbonyl lower alkyl group, lower alkoxy lower alkoxy carbonyl lower alkyl group, allyloxycarbonyl It represents a lower alkyl group, a benzyloxycarbonyl lower alkyl group, a cyano lower alkyl group, a hydroxy lower alkyl group, a lower alkanoyloxy lower alkyl group, or a halogenoacetyloxy lower alkyl group, and n is 1 or 2.

) is a monoazo dye for polyester fibers.

To explain the present invention in detail, in the general formula CI], R is a lower alkoxyalkyl group such as a methoxypropyl group or an ethoxypropyl group; a lower alkoxyalkoxyalkyl group such as a methoxyethoxyethyl group or an ethoxyethoxyethyl group; Lower alkoxyalkoxyalkoxyalkyl groups such as ethoxyethoxyethyl group and ethoxyethoxyethoxyethyl group; chloroethyl group,
Halogenoalkyl groups such as fromoethyl groups; lower alkoxycarbonylalkyl groups such as methoxycarbonylmethyl groups, ethoxycarbonylmethyl groups, methoxycarbonylethyl groups, and ethoxycarbonylethyl groups; methoxyethoxycarbonylmethyl groups, ethoxyethoxycarbonylmethyl groups, methoxy Lower alkoxyalkoxycarbonylalkyl groups such as ethoxycarbonylethyl group and ethoxyethoxycarbonylethyl group; Allyloxycarbonylalkyl groups such as allyloxycarbonylmethyl group and allyloxycarbonylethyl group; benzyloxycarbonylmethyl group, benzyloxycarbonylethyl group, etc. benzyloxycarbonylalkyl group; cyanoalkyl group such as cyanomethyl group, cyanoethyl group; hydroxyalkyl group such as hydroxyethyl group; lower alkanoyloxyalkyl group such as acetyloxyethyl group, propionyloxyethyl group; chloroacetyloxyethyl group, etc. Examples include halogenoacetyloxyalkyl groups.

The alkyl chain contained in these substituents has 1 to 1 carbon atoms.
4 lower alkyl.

The monoazo dye represented by the general formula [I] is, for example, a monoazo dye represented by the general formula [formula (formula, n is the same as defined above)].

) is represented by the general formula [■] X-R, [■] (wherein, X represents a halogen atom, and R is the same as defined above.

), or the general (IVI D-8O3R.[lV] (wherein, D represents an optionally substituted phenyl group, and R is as defined above).

) is produced by reacting with the compound shown in

(The above manufacturing method will be referred to as the former manufacturing method hereinafter.

) Further, the monoazo dye represented by the general formula [I] is, for example, the monoazo dye represented by the general formula [vlu H2 CH2= 0HOH20(02H40) n 00
...[V] (In the formula, n is the same as the above definition.

) is diazotized by a conventional method to obtain the general formula [■] cH3... [■] (wherein, R is the same as defined above.

) can also be produced by coupling with pyridones shown in

(The above manufacturing method is hereinafter referred to as the debtor's manufacturing method.

) Specific examples of the sulfonic acid esters represented by the general formula [IV], which are one of the raw materials of the present invention, include p-) toluenesulfonic acid-methoxypropyl ester, p-toluenesulfonic acid-ethoxypropyl ester ,p−+−
Luenesulfonic acid-methoxyethoxyethyl ester,
p-1-luenesulfonic acid-ethoxyethoxyethyl ester, p-toluenesulfonic acid-methoxyethoxyethoxyethyl ester, p-)luenesulfonic acid-ethoxyethoxyethoxyethyl ester, p-toluenesulfonic acid-chloroethyl ester, p-Toluenesulfonic acid-bromoethyl ester, p-Toluenesulfonic acid-cyanomethyl ester, p-Toluenesulfonic acid-
Examples include cyanoethyl ester, p-toluenesulfonic acid-chloroacetyloxyethyl ester, and the like.

In addition, specific examples of the halides represented by the general formula [llD] include methyl chloroacetate, bromol methyl ester, methyl iodoacetate, ethyl chloride acetate, methoxyethyl chloroacetate, and ethoxyethyl chloroacetate. Esters, allyl chloroacetate, hensyl chloroacetate, methyl chloropropionate, ethyl chloropropionate, methoxyethyl bromopropionate, ethoxyethyl bromopropionate, allyl ester chloropropionate chloropropionate Examples include acid benzyl ester, chloroethanol, furomonitanol, acetic acid bromoethyl ester, propionic acid bromoethyl ester, and the like.

According to the former method for producing the dye of the present invention, the general formula [v]
Anilines represented by the above are diazotized by a conventional method, and coupled with 3-cyano-6-hydroxy-4-methylpyrid-2-one or an alkali metal salt thereof by a conventional method to form an azo compound represented by the general formula The resulting azo compound is then mixed with an aromatic compound such as chlorobenzene, dichlorobenzene, nitrobenzene, or 0-nitrotoluene, an N-alkylformamide such as dimethylformamide, an N-alkylpyrrolidone such as N-methylpyrrolidone,
Presence of organic bases such as pyridine, piperidine, triethylamine or inorganic bases such as sodium carbonate, potassium carbonate, magnesium oxide, sodium hydroxide in an inert organic solvent such as ketones such as acetone, methyl ethyl ketone, alcohols such as methanol and ethanol. Below, the sulfonic acid ester represented by the general formula [■] or the general formula [■]
The pyridone-based azo dye represented by the general formula [I] can be obtained with good purity and high yield by heating the dye to 30 to 200° C. together with the halide represented by the formula [I].

Specifically, the anilines represented by the general formula [V] used as the diazo component in the latter manufacturing method of the dye of the present invention include 0-lm- or p-allyloxyethoxycarbonylaniline and 0, m- or p-allyloxyethoxyethoxycarbonylaniline.

The pyridones represented by the general formula [■] used as a coupling component can be obtained, for example, by condensing and cyclizing an acetoacetate, a dianoacetate, and an optionally substituted alkylamine.

In the manufacturing method of the present inventor, commonly used methods are used for diazotization and coupling reactions.

For example, allyloxyethoxycarbonylanilines are diazotized by adding them to nitrosyl sulfuric acid prepared from concentrated sulfuric acid and sodium nitrite, or dissolved or suspended in an aqueous hydrochloric acid solution, and diazotized by adding an aqueous sodium nitrite solution. This is carried out by adding cyano-4-methyl-6-hydroxypyridones to an alkaline aqueous solution such as sodium acetate, sodium carbonate, or sodium hydroxide.

Although the coupling reaction can be carried out in neutral or alkaline conditions, it is preferably carried out in acidic conditions.

Fibers that can be dyed with the monoazo dye of the present invention include:
Polyethylene terephthalate, terephthalic acid and 1,4
Examples include polyester fibers made of polycondensates with -bis-(hydroxymethyl)cyclohexane, and blends and blends of natural fibers such as cotton, silk, and wool with the above-mentioned polyester fibers.

In order to dye polyester fibers using the dye of the present invention, since the dye represented by the general formula [I] is insoluble or sparingly soluble in water, naphthalene sulfonic acid and formaldehyde are used as dispersants in a conventional manner. Dyeing or printing may be carried out by preparing a dyeing bath or printing paste in which a condensate, higher alcohol sulfuric ester, higher alkylbenzene sulfonate, etc. are dispersed in an aqueous medium.

For example, in the case of dip dyeing, if you apply normal dyeing methods such as high temperature dyeing, carrier dyeing, and thermosol dyeing,
Polyester fibers or their blends can be dyed with excellent fastness.

In this case, even better results can be obtained if an acidic substance such as formic acid, acetic acid, phosphoric acid or ammonium sulfate is added to the dyeing bath.

Furthermore, the dye represented by the general formula [■] of the present invention may be used in combination with dyes of the same family or dyes of the Ike family, and the dyeing properties can be improved by mixing the dyes represented by the general formula [■] of the present invention. Good results may be obtained, such as improved performance.

Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

Compound 33.2.9 shown in Reference Example 1 was dissolved in a mixed solution of 35 ml of concentrated hydrochloric acid and 300 ml of water, and this solution was
Cool on ice to ~5°C and add 11.4% of sodium nitrite to the resulting solution. ? 75m1 of water! was added dropwise.

After stirring at 0 to 5°C for 2 hours, a small amount of sulfamic acid was added to obtain a diazo liquid.

On the other hand, 22.5L of 3-cyano-6-hydroxy-4-methylpyrid-2-one, 43.1.9L of sodium acetate and 6.3g of 93wt.φ sodium hydroxide were added to 1800ml of water.
It was dissolved in A and used as a coupling solution.

Add 30% of the diazo solution to this campling solution at 0 to 5°C.
The mixture was added over several minutes and stirred for an additional 2 hours.

After separating the precipitated crystals from house to house, they are washed with water and dried.
54.4 g of yellow crystals of an azo compound represented by the following formula were obtained.

The maximum absorption wavelength of this Abu compound (in an 80 volume aqueous acetone solution) was 429 nm.

Next, the above azo compound 38.2&, sodium carbonate 12
．． 79. -n-octyl iodide 36°Og and *; and N
, a mixture of 150 ml of N-dimethylformamide
℃ and allowed to react for about 5 hours.

After the reaction, it was cooled to room temperature and discharged into 750 m of water.

The precipitated crystals were separated from each other, washed, and then dried to obtain 46.41i yellow crystals of a dye represented by the following formula.

The maximum absorption wavelength of this dye (in an 80 volume φ acetone aqueous solution) was 428 nm.

Furthermore, the elemental analysis values were in good agreement with the calculated values, as shown in the table below.

C027H34N405 ] A dyeing bath was prepared by dispersing 0.5 g of the dye obtained in this reference example in water 31 containing 1 g of naphthalene sulfonic acid formaldehyde condensate and 2 g of higher alcohol sulfate ester.

100g of polyester fiber was immersed in this dyeing bath,
After dyeing at 0° C. for 60 minutes, soaping, washing with water and drying were performed, a clear greenish-yellow dyed fabric was obtained.

The light fastness of the dyed fabric obtained and the temperature stability and pH stability of the dye were good.

Example 1 An experiment was carried out in the same manner as in Reference Example 1 except that chloroacetic acid methyl ester 2L'# was used in place of -0-octyl iodide. As a result, yellow crystals of the dye represented by the following formula 41. i was obtained.

The maximum absorption wavelength of this dye (in an 80 volume φ acetone aqueous solution) was 428 nm.

When polyester fibers were dyed at high temperature using the dye obtained in this example, a vivid greenish-yellow dyed fabric was obtained.

The light fastness* of the obtained dyed fabric was good.

Example 2 Chloroacetonitrile instead of n-octyl iodide 15.1. ? An experiment was carried out in the same manner as in Reference Example 1 except that 39.1.9 of yellow crystals of the dye represented by the following formula was obtained.

The maximum absorption wavelength of this dye (in an 80 volume aqueous acetone solution) was 428 nm.

When polyester fibers were dyed at high temperature using the dye obtained in this example, a vivid greenish-yellow dyed fabric was obtained.

The light fastness of the dyed fabric obtained was good.

Example 3 p-allyloxyethoxycarbonylaniline 22.1
．． ! l! was dissolved in a mixed solution of 23 ml of concentrated hydrochloric acid and 200 ml of water, cooled with water to 0 to 5°C, and 5 drops of a solution of 7.6 g of sodium nitrite dissolved in 50 ml of water were added.

After stirring at 0 to 5°C for 2 hours, a small amount of sulfamic acid was added to obtain a diazo liquid.

On the other hand, 22.2 g of 3-cyano-6-hydroxy-1-methoxypropyl-4-methylpyrid-2-one, 28.7 g of sodium acetate, and 4.2 g of sodium hydroxide were dissolved in 1200 m7 of water to prepare a coupling liquid.

Add 15% of the diazo solution to this coupling solution at 0-5°C.
The mixture was added over several minutes and stirred for an additional 2 hours.

After removing the precipitated crystals, wash with water and dry.
Yellow crystals of dye 42.2.9 represented by the following formula were obtained.

The maximum absorption wavelength of this dye (in an 80 volume aqueous acetone solution) was 428 nm.

Furthermore, the elemental analysis values were in good agreement with the calculated values, as shown in the table below.

When jelly ester fibers were dyed at high temperature (130° C.) using the dye obtained in this example, a vivid greenish-yellow dyed fabric was obtained.

The dyed fabric obtained had good light fastness and sublimation fastness.

Example 4 Polyester fibers were dyed using the dyes shown in Table 1 below in the same manner as in Reference Example 1 to obtain dyed products having the colors shown in the table.

Example 5 Polyester fibers were dyed using the dyes shown in Table 2 below in the same manner as in Reference Example 1 to obtain dyed products having the colors shown in the table.

Example 6 Polyester fibers were dyed using the dyes shown in Table 3 below in the same manner as in Reference Example 1 to obtain dyed products having the colors shown in the table.

Claims (1)

[Claims] 1 General formula (wherein R is a lower alkoxy lower alkyl group, a lower alkoxy lower alkoxy lower alkyl group, a lower alkoxy lower alkoxy lower alkoxy lower alkyl group, a halogeno lower alkyl group, a lower alkoxycarbonyl lower alkyl group) , lower alkoxy lower alkoxycarbonyl lower alkyl group, allyloxycarbonyl lower alkyl group,
It represents a benzyloxycarbonyl lower alkyl group, a cyano lower alkyl group, a hydroxy lower alkyl group, a lower alkanoyloxy lower alkyl group, or a halogenoacetyloxy lower alkyl group, and n is 1 or 2. ) monoazo dye for polyester fibers.