JPH0139457B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a disazo dye for polyester fibers, and more specifically, it dyes polyester fibers blue and examines various fastnesses, particularly light fastness, sublimation fastness, water fastness, as well as temperature stability and PH during dyeing. This relates to a disazo dye with excellent stability. The disazo dye for polyester fibers of the present invention has the following general formula [] (In the formula, D is a chlorine atom, a bromine atom, a phenyl group optionally substituted with a nitro group or a lower alkyl group: a pyridyl group optionally substituted with a chlorine atom: a bromine atom, a nitro group, a lower alkyl group, A thiazolyl group optionally substituted with a phenyl group or a lower alkylkoxycarbonyl group: or a thiadiazolyl group optionally substituted with a bromine atom, a lower alkylthio group, or a lower alkyl group, where X is a hydrogen atom, a chlorine atom, represents a methyl group or a lower alkylcarbonylamino group,
Y represents a hydrogen atom, a chlorine atom, a methyl group, or a methoxy group, and R ¹ and R ² are hydrogen atoms: cyano group, hydroxyl group, lower alkoxy group, allyloxy group, tetrahydrofuryl group, phenoxy group, lower alkoxycarbonyl group, benzyl A lower alkyl group optionally substituted with an oxycarbonyl group, an allyloxycarbonyl group, a lower alkoxycarbonyloxy group, a lower alkylcarbonyloxy group, or a chloro-lower alkylcarbonyloxy group: Cyclohexyl group: Represents a benzyl group or an allyl group. ) is a water-insoluble dye. Examples of the lower alkyl group as a substituent for the phenyl group, thiazolyl group, and thiazolyl group represented by D in the above general formula [] include methyl group, ethyl group, etc.; as the lower alkoxycarbonyl group as a substituent for the thiazolyl group, Examples of lower alkylthio groups in which an ethoxycarbonyl group is a substituent of a thiadiazolyl group include a methylthio group, an ethylthio group, and examples of a thiadiazolyl group include 1,
Examples of the lower alkylcarbonylamino group represented by X, which is a 3,4-thiadiazolyl group or a 1,2,4-thiadiazolyl group, include an acetylamino group. Examples of the unsubstituted lower alkyl group represented by R ¹ and R ² include a methyl group, an ethyl group, a linear or branched probyl group, a butyl group, a pentyl group, a hexyl group, and a substituted lower alkyl group. As a group, cyano lower alkyl groups such as cyanoethyl group; hydroxy lower alkyl groups such as hydroxyethyl group, hydroxypropyl group, hydroxybutyl group; lower alkoxy lower alkyl groups such as methoxyethyl group, ethoxyethyl group, butoxyethyl group; Allyloxy lower alkyl groups such as allyloxyethyl groups; tetrahydrofurfuryl-substituted lower alkyl groups such as tetrahydrofurfuryl groups; phenoxy lower alkyl groups such as phenoxyethyl groups; methoxycarbonylmethyl groups;
Lower alkoxycarbonyl lower alkyl groups such as ethoxycarbonylmethyl group; benzyloxycarbonyl lower alkyl groups such as benzyloxycarbonylmethyl group; allyloxycarbonyl lower alkyl groups such as allyloxycarbonylethyl group and allyloxycarbonylmethyl group; methoxycarbonyloxy Examples include lower alkoxycarbonyloxy lower alkyl groups such as ethyl group; lower alkylcarbonyloxy lower alkyl groups such as acetyloxyethyl group; chlorolower alkylcarbonyloxy lower alkyl groups such as chloroacetyloxyethyl group and chloropropionyloxyethyl group. It will be done. The disazo dye represented by the general formula [] is obtained by diazotizing the amine represented by the following formula [] D-NH ₂ ... [] (wherein, D is the same as the above definition) and is represented by the following formula []. Ami The following formula obtained by coupling with nothiophene [] (In the formula, D is the same as defined above.) The following formula obtained by reacting a compound represented by the formula with a rhodan salt such as NaSCN and a halogen such as bromine as a catalyst [] (wherein, D is the same as defined above) is diazotized to form the following general formula [] It can be produced by coupling with an aniline represented by the formula (wherein, X, Y, R ¹ and R ² are the same as defined above). As the amine represented by the general formula D- _NH2 ,
Benzene-based amines such as aniline; o-, m
-, or p-chloroaniline; o-, m-, or p-bromoaniline; 2,4-dichloroaniline, 2,3-dichloroaniline, 2-chloro-
4-bromoaniline, 2,4,6-trichloroaniline; o-, m-, or p-toluidine; o
-, m-, or p-ethylaniline; o-, m
-, or p-nitroaniline; 2-chloro-4
Examples of pyridine-based amines include 3-aminopyridine, 3-amino-6-chloropyridine, and 4,6-dichloro-3-aminopyridine. Examples of thiazole amines include 2-aminothiazole, 2-amino-4-methylthiazole, 2-amino-4-methyl-5-
Ethoxycarbonylthiazole, 2-amino-5
-Nitrothiazole, 2-amino-5-bromothiazole, 2-amino-4-methyl-5-bromothiazole, etc., and examples of thiadiazole-based amines include 2-amino-1,3,4-thiadiazole, -amino-5-methylthio-1,
3,4-thiadiazole, 2-amino-5-bromo-1,3,4-thiadiazole, 2-amino-
5-methyl-1,3,4-thiadiazole, 5-
Examples include amino-3-methyl-1,2,4-thiadiazole. Fibers that can be dyed with the disazo dye of the present invention include polyester fibers made of polyethylene terephthalate, polycondensates of terephthalic acid and 1,4-bis-(hydroxymethyl)cyclohexane, and natural fibers such as cotton, silk, and wool. Examples include blended products and blended products of fibers and 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 [] shown above 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, polyester fibers or their blends can be dyed with excellent fastness by applying ordinary dyeing methods such as high temperature dyeing, carrier dyeing, and thermosol dyeing. 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 [] used in the method of the present invention may be used in combination with dyes of the same type or dyes of other systems, and among these, the dyes represented by the general formula [] can be used in combination with each other. Depending on the combination, good results such as improved dyeability may be obtained. 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. Example 1 Structural formula below 0.5g of the dye shown in naphthalenesulfonic acid
100 g of polyester fiber was immersed in a dyeing bath prepared by dispersing it in water 3 containing 1 g of formaldehyde condensate and 2 g of higher alcohol sulfate,
After dyeing at 130°C for 60 minutes, soaping, washing and drying resulted in a navy blue dyed fabric. The light fastness, sublimation fastness and water fastness of the obtained dyed fabric, as well as the temperature stability and PH stability during dyeing of the above dye, were good. The dye used in this example was produced as follows. 9.3 g of aniline was dissolved in 150 ml of 4% hydrochloric acid, the solution was cooled to 2 DEG C., and then 50 ml of 2N sodium nitrite was added. At this time, the temperature was set not to exceed 5°C. The obtained aniline diazonium salt solution was added to a solution of 9.9 g of 2-aminothiophene dissolved in 100 ml of methanol at 2°C, stirred at the same temperature for 2 hours, and the precipitated monoazo compound was removed and washed with water. and dried. This monoazo compound (2-amino-5-phenylazothiophene) 20
g was added to 200 c.c. of glacial acetic acid, and further 20 g of sodium thiocyanate was added. Then, this reaction solution was heated to 10℃~
The temperature was maintained at 15°C, and 16 g of bromine was gradually added dropwise, followed by stirring at the same temperature for 3 hours, and the precipitate was separated to obtain 16 g of 2-amino-5-phenylazothienothiazole. Add 13.0 g of this monoazo compound to a mixture of 130 ml of acetic acid and 130 ml of phosphoric acid, and then slowly add nitrosyl sulfuric acid (prepared by dissolving 3.5 g of sodium nitrite in 20 g of 97% sulfuric acid) into this mixture at 0-5°C. The mixture was added and stirred at the same temperature for 30 minutes to prepare a diazo solution of a monoazo compound. N-(ethyl)-N-
10.5 g of (β-acetoxyethyl)aniline was dissolved in 200 ml of methanol and added to 200 g of ice and 100 ml of water. Add the diazo solution prepared above to this, and
The mixture was stirred at ~5°C for 2 hours, and the precipitated disazo dye was removed, washed with water, and dried. The λmax (acetone) of this product was 593 nm. Example 2 Structural formula below 0.5g of the dye shown in naphthalenesulfonic acid
A dyeing bath was prepared by dispersing it in water 3 containing 1 g of formaldehyde condensate and 2 g of higher alcohol sulfate. Polyester fibers are dyed in this dye bath.
After immersing 100 g and dyeing at 130° C. for 60 minutes, soaping, washing with water, and drying were performed, a green dyed fabric was obtained. The light fastness of the dyed fabric obtained,
The sublimation fastness and water fastness as well as the temperature stability and PH stability during dyeing of the above dye were good. The dye used in this example was produced according to Example 1. The λmax (acetone) of this product was 607 nm. Example 3 Structural formula below 0.5g of the dye shown in naphthalenesulfonic acid
A dyeing bath was prepared by dispersing it in water 3 containing 1 g of formaldehyde condensate and 2 g of higher alcohol sulfate. Polyester fibers are dyed in this dye bath.
After immersing 100 g and dyeing at 130° C. for 60 minutes, soaping, washing with water, and drying were performed, a green dyed fabric was obtained. The light fastness of the dyed fabric obtained,
The sublimation fastness and water fastness as well as the temperature stability and PH stability during dyeing of the above dye were good. The dye used in this example was produced according to Example 1. The λmax (acetone) of this product was 610 nm. Example 4 Structural formula below 0.5g of the dye shown in naphthalenesulfonic acid
A dyeing bath was prepared by dispersing it in water 3 containing 1 g of formaldehyde condensate and 2 g of higher alcohol sulfate. Polyester fibers are dyed in this dye bath.
After immersing 100 g and dyeing at 130° C. for 60 minutes, soaping, washing with water, and drying were performed, a green dyed fabric was obtained. The light fastness of the dyed fabric obtained,
The sublimation fastness and water fastness as well as the temperature stability and PH stability during dyeing of the above dye were good. The dye used in this example was produced according to Example 1. The λmax (acetone) of this product was 620 nm. Example 5 Structural formula below 0.5g of the dye shown in naphthalenesulfonic acid
A dyeing bath was prepared by dispersing it in water 3 containing 1 g of formaldehyde condensate and 2 g of higher alcohol sulfate. Polyester fibers are dyed in this dye bath.
After immersing 100 g of the fabric and dyeing it at 130°C for 60 minutes, soaping, washing with water, and drying were performed, a green dyed fabric was obtained. The light fastness of the dyed fabric obtained,
The sublimation fastness and water fastness as well as the temperature stability and PH stability during dyeing of the above dye were good. The dye used in this example was produced according to Example 1. The λmax (acetone) of this product was 613 nm. Example 6 Structural formula below 0.5g of the dye shown in naphthalenesulfonic acid
A dyeing bath was prepared by dispersing it in water 3 containing 1 g of formaldehyde condensate and 2 g of higher alcohol sulfate. Polyester fibers are dyed in this dye bath.
After immersing 100 g of the fabric and dyeing it at 130°C for 60 minutes, soaping, washing with water, and drying were performed, a green dyed fabric was obtained. The light fastness of the dyed fabric obtained,
The sublimation fastness and water fastness as well as the temperature stability and PH stability during dyeing of the above dye were good. The dye used in this example was produced according to Example 1. The λmax (acetone) of this product was 615 nm. Example 7 Structural formula below 0.5g of the dye shown in naphthalenesulfonic acid
A dyeing bath was prepared by dispersing it in water 3 containing 1 g of formaldehyde condensate and 2 g of higher alcohol sulfate. Polyester fibers are dyed in this dye bath.
After immersing 100 g of the fabric and dyeing it at 130°C for 60 minutes, soaping, washing with water, and drying were performed, a green dyed fabric was obtained. The light fastness of the dyed fabric obtained,
The sublimation fastness and water fastness as well as the temperature stability and PH stability during dyeing of the above dye were good. The dye used in this example was produced according to Example 1. The λmax (acetone) of this product was 651 nm. Example 8 Polyester fibers were dyed using the dyes shown in Table 1 below in the same manner as in Example 1 to obtain dyed products having the colors shown in the table.

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Claims (1)

[Claims] 1. General formula (In the formula, D is a chlorine atom, a bromine atom, a phenyl group optionally substituted with a nitro group or a lower alkyl group: a pyridyl group optionally substituted with a chlorine atom: a bromine atom, a nitro group, a lower alkyl group, A thiazolyl group optionally substituted with a phenyl group or a lower alkoxycarbonyl group: or a thiadiazolyl group optionally substituted with a bromine atom, a lower alkylthio group, or a lower alkyl group, where X is a hydrogen atom, a chlorine atom, a methyl group or a lower alkylcarbonylamino group, Y represents a hydrogen atom, a chlorine atom, a methyl group or a methoxy group, R ¹ and R ² are hydrogen atoms: a cyano group,
Hydroxyl group, lower alkoxy group, allyloxy group, tetrahydrofuryl group, phenoxy group, lower alkoxycarbonyl group, benzyloxycarbonyl group, allyloxycarbonyl group, lower alkoxycarbonyloxy group, lower alkylcarbonyloxy group or chloro-lower alkylcarbonyloxy group Optionally substituted lower alkyl group:
Cyclohexyl group: Represents a benzyl group or an allyl group. ) Disazo dye for polyester fibers.