JPH0472861B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an azo dye for polyester fibers, and more particularly to a novel azo dye that dyes polyester fibers in bright yellow to blue colors and has excellent color fastness. The azo dye for polyester fibers of the present invention has the following general formula [] (In the formula, X ¹ represents a cyano group or a chlorine atom,
X ² represents a nitro group, a methyl group or a chlorine atom,
X ³ represents a hydrogen atom or cyano, R ⁶ represents a cyclohexyl group, alkenyl group; an optionally substituted alkyl group or phenyl group, R ⁷ represents a hydrogen atom, cyclohexyl group, alkenyl group; Represents a good alkyl group or phenyl group. ) is a new water-insoluble azo dye. The azo dye represented by the above general formula [] is the following formula [] (In the formula, X ¹ , X ² and X ³ are the same as the above definitions) is diazotized, and the following formula [] (In the formula, R ⁶ and R ⁷ are the same as defined above.) It can be produced by coupling with a 2-aminothiophene represented by the above formula. To explain the present invention in more detail, the alkyl groups represented by R ⁶ and R ⁷ in the general formula [] include a methyl group, an ethyl group, a linear or branched propyl group, a butyl group, and a pentyl group. , hexyl group, heptyl group, octyl group, etc. Substituted alkyl groups include methoxyethyl group,
Lower alkoxyalkyl groups such as ethoxyethyl group and ptoxyethyl group; lower alkoxyalkoxyalkyl groups such as methoxyethoxyethyl group and ethoxyethoxyethyl group; phenoxyalkyl groups such as phenoxyethyl group; benzyloxyethyl group and chlorobenzyloxyethyl group An optionally substituted aralkyloxy lower alkyl group such as;
Hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, hydroxyhexyl group, 2-
Optionally substituted hydroxyalkyl groups such as hydroxy-3-methoxypropyl group; cyano lower alkyl groups such as cyanomethyl group and cyanoethyl group; acetyloxyethyl group, chloroacetyloxyethyl group, chloropropionyloxyethyl group, benzoyloxy An optionally substituted acyloxy lower alkyl group such as an ethyl group; an alkoxycarbonyloxy lower alkyl group such as a methoxycarbonyloxyethyl group or a methoxyethoxycarbonyloxyethyl group; a carbamoyl lower alkyl group such as a carbamoylmethyl group or a carbamoylethyl group; Optionally substituted alkoxycarbonyl lower alkyl groups such as methoxycarbonylmethyl group, ethoxycarbonylmethyl group, methoxyethoxycarbonylmethyl group, and benzyloxycarbonylmethyl group; Substituted alkoxycarbonyl lower alkyl groups such as benzyl group, phenethyl group, and chlorobenzyl group; aralkyl groups, allyloxycarbonyl lower alkyl groups such as allyloxycarbonylethyl groups and allyloxycarbonylmethyl groups; tetrahydrofurfuryl groups; succinimide lower alkyl groups such as succinimideethyl groups; phthalic acids such as phthalimidoethyl groups; Imide lower alkyl group; Examples include cyanoalkoxy lower alkyl groups such as cyanoethoxyethyl group and cyanomethoxyethyl group, and halogen lower alkyl groups such as chloroethyl group. R ⁶
The optionally substituted phenyl group represented by R ⁷ and R ⁷ include phenyl group, chlorophenyl group, methylphenyl group, etc.
The alkenyl group represented by R ⁷ is an allyl group,
Examples include crotyl group. Fibers that can be dyed with the thienylazo dye of the present invention include polyethylene terephthalate, terephthalic acid and 1,4-bis-(hydroxymethyl).
Examples include polyester fibers made of polycondensates with cyclohexane, natural fibers such as cotton, silk, and wool; blended products and blended woven products of acetate fibers such as diacetate fibers and triacetate fibers with the above 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. In addition, the dyes 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 types, and among these, the dyes represented by the general formula [] may 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 The following structural formula 0.5g of the dye shown in naphthalenesulfonic acid
100 g of polyester fiber was immersed in a dyeing bath containing 1 g of formaldehyde condensate and 2 g of higher alcohol sulfate ester dispersed in water, and heated at 130°C.
After dyeing for 60 minutes, soaping, washing and drying yielded a burgundy dyed fabric. The dyed fabric obtained had good light fastness and various fastnesses. The dye used in this example was produced as follows. Add 20g of sodium nitrite to 28.8ml of 98% sulfuric acid.
Nitrosyl sulfuric acid was prepared by heating to 55°C and dissolving it. This reaction solution was cooled, and 9.12g of acetic acid was heated to 5-10℃.
was added, followed by dropping 40% sulfuric acid at 0-5°C. Furthermore, the following formula Add 3.26 (0.02 mol) g of the compound represented by -
After stirring for 2 hours at 2°C to 0°C, 1.0 g of urea was added to prepare a diazo solution. On the other hand, the following formula 3.04 (0.02 mol) g of the compound shown in methanol
It was dissolved in 500 ml and used as a coupling liquid. The diazo solution was added to this coupling solution over a period of 30 minutes at 0 to 5°C, and the mixture was further stirred for 5 hours. After separating the precipitated crystals, they were washed with water and dried, and the following formula was obtained. 5.7 g of monoazo dye represented by was obtained. The maximum absorption wavelength of this monoazo dye (in an 80% acetone aqueous solution) was 545 nm. The following formula used in this example A coupling component (3-cyano-N,
N-dimethylaminothiophene) was produced as follows. Add the following formula to 73.1g (1.02ml) of 2-butanone. Add 20 g (0.16 mol) of the compound shown (2-amino-3-cyanothiophene), further add 19.4 g (0.48 mol) of sodium hydroxide, then add 60.48 g (0.48 mol) of dimethyl sulfate, and stir at room temperature for 48 hours. Stirred. Water was added to the reaction solution, extracted with chloroform, and separated and purified using silica gel column chromatography.
A pale yellow oil was obtained. A molecular weight of 152 was confirmed from the mass spectrum. Example 2 Structural formula below A dyeing bath was prepared by dispersing 0.5 g of the dye represented by 3 in water 3 containing 1 g of naphthalene sulfonic acid-formaldehyde condensate and 2 g of higher alcohol sulfate. 100 g of polyester fibers were immersed in this dyeing bath and dyed at 130° C. for 60 minutes, followed by soaping, washing with water, and drying to obtain a red dyed fabric. The dyed fabric obtained had good light fastness and various fastnesses. The dye used in this example was produced according to Example 1. The λmax (acetone) of this product was 524 nm. The following formula used in this example The coupling component (N-hydroxyethylamino-3-cyanothiophene) represented by was produced as follows. The following formula Add ethylene oxide to 124g (0.1mol) of the compound (2-amino-3-cyanothiophene)
19.8 ml (0.4 mol), 4 ml of glacial acetic acid and 4 ml of water were added, and the mixture was left at room temperature for 48 hours. After extraction with chloroform, it was separated and purified using silica gel column chromatography.
Obtained the object. A molecular weight of 168 was confirmed from the mass spectrum. Example 3 Structural formula below A dyeing bath was prepared by dispersing 0.5 g of the dye represented by 3 in water 3 containing 1 g of naphthalene sulfonic acid-formaldehyde condensate and 2 g of higher alcohol sulfate. 100 g of polyester fibers were immersed in this dyeing bath and dyed at 130° C. for 60 minutes, followed by soaping, washing with water, and drying to obtain a blue dyed fabric. The dyed fabric obtained had good light fastness and various fastnesses. The dye used in this example was produced according to Example 1. The λmax (acetone) of this product was 585 nm. Example 4 Structural formula below A dyeing bath was prepared by dispersing 0.5 g of the dye represented by 3 in water 3 containing 1 g of naphthalene sulfonic acid-formaldehyde condensate and 2 g of higher alcohol sulfate. 100 g of polyester fibers were immersed in this dyeing bath and dyed at 130° C. for 60 minutes, followed by soaping, washing with water, and drying to obtain a red dyed fabric. The dyed fabric obtained had good light fastness and various fastnesses. The dye used in this example was produced according to Example 1. The λmax (acetone) of this product was 515 nm. Example 5 Structural formula below A dyeing bath was prepared by dispersing 0.5 g of the dye represented by 3 in water 3 containing 1 g of naphthalene sulfonic acid-formaldehyde condensate and 2 g of higher alcohol acid ester. 100 g of polyester fibers were immersed in this dyeing bath and dyed at 130° C. for 60 minutes, followed by soaping, washing with water, and drying to obtain a red dyed fabric. The dyed fabric obtained had good light fastness and various fastnesses. The dye used in this example was produced according to Example 1. The λmax (acetone) of this product was 520 nm. Example 6 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, X ¹ represents a cyano group or a chlorine atom,
X ² represents a nitro group, a methyl group or a chlorine atom,
X ³ represents a hydrogen atom or a cyano group, R ⁶ represents a cyclohexyl group, an alkenyl group; an optionally substituted alkyl group or a phenyl group, R ⁷ represents a hydrogen atom, a cyclohexyl group, an alkenyl group; represents an alkyl group or a phenyl group. ) Azo dyes for polyester fibers.