JPS583067B2 - Senshiyokuhouhou - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for dyeing synthetic fibers.

More specifically, the object of the present invention is to dye synthetic fibers, particularly polyester fibers, in a strong and vivid greenish-yellow color.

However, the purpose of this is to produce synthetic fibers according to the method of the present invention with the following general formula (in the above general formulas [1] and [1'], R1 hydrogen atom, alkyl group, alkoxycarbonyl group, alkoxycarbonylalkyl group, aralkyl group). group, phenyl group, R2 is an alkoxycarbonyl group, alkoxyalkoxycarbonyl group, acyl group, cyano group, substituted or unsubstituted carbamoyl group, R3 is a substituted or unsubstituted alkyl group, aryl group, aralkyl group, and R4 is hydrogen atoms, halogen atoms,
Indicates a substituted or unsubstituted alkoxy group or aryloxy group.

The present invention, which is achieved by dyeing with a perinone compound represented by or a mixture thereof, will be explained in more detail.

R1 in general formulas [1] and [1'] is not only a hydrogen atom but also an alkyl group such as a methyl group or an ethyl group, or an alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, or a butoxycarbonyl group. alkoxycarbonylalkyl groups such as methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl groups. Examples include alkyl groups such as benzyl groups, phenyl groups, etc., and R2 includes methoxycarbonyl groups, ethoxycarbonyl groups, propoxycarbonyl groups,
Alkoxycarbonyl groups such as butoxycarbonyl groups, methoxyethoxycarbonyl groups, alkoxyalkoxycarbonyl groups such as ethoxyethoxycarbonyl groups, acetyl groups, acyl groups such as benzoyl groups, cyano groups, carbamoyl groups, phenylcarbamoyl groups, methylcarbamoyl group, ethylcarbamoyl group, propylcarbamoyl group, butylcarbamoyl group, dimethylcarbamoyl group, substituted carbamoyl group such as diethylcarbamoyl group, etc., and R3 is a methyl group, an ethyl group, a linear or branched propyl group, etc. group, alkyl group such as butyl group, pentyl group, hexyl group, methoxyethyl group, ethoxyethyl group, methoxyethoxyethyl group,
Ethoxyethoxyethyl group, dimethylamineethyl group,
Examples include substituted alkyl groups such as morpholinoethyl, aryl groups such as phenyl, methoxyphenyl, and chlorophenyl, and aralkyl groups such as benzyl and phenethyl. atom, halogen atom such as bromine atom, methoxy group, ethoxy group, linear or branched propoxy group, alkoxy group such as butoxy group, methoxyethoxy group, ethoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxy Examples include substituted alkoxy groups such as ethoxy group, dimethylaminoethoxy group, and morpholinoethoxy group; aryloxy groups such as phenoxy group, methoxyphenoxy group, and chlorophenoxy group; and arylalkoxy groups such as penzyloxy group and phenethyloxy group. It will be done.

The dye used in the present invention is a novel perinone-based dye, for example, the following general formula [4] (wherein R3 and R4 are the above-mentioned general formula [1] or [1
'] has the same meaning.

) naphthalic acid hydrazide represented by the general formula R1-COCH-R2... [3] (in the formula k
R' and R2 have the same meanings as in the general formula [1] or [1'].

) to obtain the general formula [2] (wherein Rl.R2, R3 and R4 have the same meanings as in the above general formula [1] or [1']).

) is then cyclized in the presence of a basic condensing agent.

The synthetic fibers to be applied in the present invention include fibers made of synthetic polymeric substances or semi-synthetic polymeric substances, particularly polyethylene terephthalate, terephthalic acid and 1,4-
Examples include polyester fibers made of polycondensates of bis(hydroxymethyl)cyclohexane, but may also include polyester ether fibers, polyamide fibers, polyurethane fibers, triacetate fibers, and diacetate fibers. It may be a blend of synthetic fibers or a blend of natural fibers such as cotton, silk, or wool.

In order to dye the above-mentioned synthetic fibers according to the method of the present invention, naphthalenesulfonic acid and formaldehyde are used as dispersants in a conventional manner, since the dyes of formulas [1] and [1'] are insoluble or sparingly soluble in water. Dyeing or printing can be carried out by preparing a dye bath or printing paste by dispersing it in an aqueous medium using a condensate of , higher alcohol sulfuric ester, higher alkylbenzene sulfonate, etc.

For example, in the case of dyeing, high temperature dyeing method, carrier dyeing method,
If ordinary dyeing methods such as thermosol dyeing method are applied, polyester fibers, triacetate fibers,
Polyamide fibers, diacetate 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.

Hereinafter, the dyeing method of the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples unless the gist thereof is exceeded.

In addition, "parts" in the examples indicate "parts by weight."

Example 1 A dyeing bath was prepared by dispersing 0.5 parts of a mixture of perinone compounds represented by the following structural formula in 3000 parts of water containing 1 part of naphthalene sulfonic acid/formaldehyde condensate and 2 parts of higher alcohol sulfate ester. .

100 parts of polyester fibers were immersed in this dyeing bath,
After dyeing at 0° C. for 60 minutes, the fibers were soaped, washed with water, and dried to obtain polyester fibers with good light fastness and sublimation fastness, and which were dyed in a bright greenish yellow color.

The mixture of perinone compounds used in this example was produced as follows.

24.2 g of 4-methoxynaphthalic acid hydrazide was stirred in 90.0 g of acetoacetic acid ethyl ester in the presence of 0.2 g of P-toluenesulfonic acid at 130 DEG C. for 2 hours with a weak flow of nitrogen.

The reaction solution was cooled to room temperature, diluted with 100 ml of methanol, and the precipitated hydrazone was collected by suction filtration, washed with methanol and water, and dried to give 29.0 g of pale yellow crystals (82% of theoretical value) with a melting point of 170-171°C. ) was obtained.

Obtained hydrazone 29.1, dimethylformamide 1
A mixture of 20 ml and 0.16 g of anhydrous potassium acetate was stirred for 1 hour under reflux cooling.

The reaction solution was cooled to room temperature, diluted with 100 ml of methanol, and the precipitated crystals were collected by suction and washed with methanol and water.
By drying, the above Perison compound has a melting point of 194.
Obtained as 23.4 g (85% of theory) of yellow crystals at ~195°C.

Example 2 0.5 part of a perinone compound represented by the following structural formula is dispersed in 3000 parts of water containing 1.5 parts of naphthalene sulfonic acid formaldehyde condensate and 1 part of higher alcohol sulfuric ester,
A dyeing bath was prepared by adding 15 parts of methylnaphthalene type carrier to this.

100 parts of polyester fibers were immersed in this dyeing bath,
After dyeing at 0° C. for 90 minutes, washing with soaping water and drying, polyester fibers having good fastness and being dyed in a clear greenish yellow color were obtained.

The perinone compound used in this case was manufactured as follows.

4,5-diphenoxynaphthalic acid hydrazide 39.6g
, 25.0 ml of acetylacetone to a mixture of 150 ml of inbutanol and 0.3 g of P-toluenesulfonic acid.
g was added thereto, and the mixture was stirred for 3 hours under reflux cooling.

The reaction solution was cooled to room temperature, the precipitated hydrazone was collected by suction filtration, washed with methanol and water, and dried to reduce the melting point to 2.
41.6 g of pale yellow crystals at 36-237°C (theoretical value of 87
%) was obtained.

A mixture of 41.6 g of the obtained hydrazone, 120 ml of dimethylformamide and 0.16 g of anhydrous potassium acetate was stirred for 1 hour under reflux cooling.

The reaction solution was cooled to room temperature, diluted with 100 ml of methanol, and the precipitated crystals were collected by suction filtration and washed with methanol and water.
By drying, the desired product was obtained as 37.6 g (94% of theory) of yellow crystals with a melting point of 184-185°C.

Example 3 Using 0.5 parts of a perinone compound represented by the following structural formula, a dyeing bath was prepared and polyester fibers were treated in the same manner as in Example 1, resulting in good fastness. Polyester fibers dyed in a bright greenish yellow color were obtained.

The perinone compound used in this example has a melting point of 264-2
It is a yellow crystal at 65°C, and hydrazone (melting point 227-229°C) was prepared in the same manner using 4,5-dimethoxynaphthalic acid hydrazide instead of 4-methoxynaphthalic acid hydrazide used in Example 1. It was produced by cyclization.

Example 4 Polyester fibers were dyed using the perinone compounds shown in the following table in the same manner as in Example 1 to obtain dyed products having the colors shown in the table.

Claims (1)

[Scope of Claims] 1 Synthetic fibers are defined by the general formula (in the above general formulas [1] and [1'], R1 is a hydrogen atom, an alkyl group, an alkoxycarbonyl group, an alkoxycarbonylalkyl group, an aralkyl L phenyl group, and R2 is a Alkoxycarbonyl group, alkoxyalkoxycarbonyl group, acyl group, cyano group, substituted or unsubstituted carbamoyl group R3 is a substituted or unsubstituted alkyl group, aryl group, aralkyl group, and R4 is a hydrogen atom, a halogen atom, a substituted or A method for dyeing synthetic fibers, characterized by dyeing using a perinone compound represented by (representing an unsubstituted alkoxy group or aryloxy group) or a mixture thereof.