JPS6242949B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to monoazo dyes for synthetic fibers. More specifically, the present invention relates to a monoazo dye that dyes synthetic fibers, particularly polyester fibers, in a robust and vivid red color. The present invention will be explained in detail below. The dye according to the present invention has the following general formula [] (In the formula, R ¹ is an alkyl group, an aralkyl group, an allyl group, a lower alkoxy lower alkyl group, a β-phenoxyethyl group, an alkoxycarbonyl lower alkyl group, a lower alkoxy lower alkoxycarbonyl lower alkyl group, a tetrahydrofurfuryl group, a furfuryl group, or Represents a phenyl group optionally substituted with a halogen atom, lower alkyl group, lower alkoxy group, or nitro group, and R ² and R ³ are an alkyl group, an aralkyl group, an allyl group, a lower alkoxy lower alkyl group, and a β-phenoxyethyl group. , represents a furfuryl group or a tetrahydrofurfuryl group, and X and Y are hydrogen atoms,
Represents a lower alkyl group or a halogen atom, n
is 1 or 2. ) is a water-insoluble monoazo dye. The dye represented by the above general formula [] is, for example, the dye represented by the following general formula [] The diazonium salt of 2- ^amino -1,3,4-thiadiazole represented by the following general formula [] (In the formula, R ² , R ³ , X and Y have the same meanings as in the above general formula []), or the following general formula [] (In the formula, R ¹ has the same meaning as in the general formula []).
The following general formula [] obtained by coupling a diazonium salt of 1,3,4-thiadiazole with an aniline represented by the above general formula [] (In the formula, R ¹ , R ² , R ³ , X and Y have the same meanings as in the general formula []). It can be produced by oxidizing with an oxidizing agent such as In the general formula [], R ¹ , R ² and R ³
Examples of the alkyl group represented by are methyl group,
Ethyl group, linear or branched propyl group,
Examples include butyl group, pentyl group, hexyl group, heptyl group, octyl group, and the like. R ¹ , R ² and
Examples of the aralkyl group represented by R ³ include a benzyl group, a phenethyl group, and a halogenobenzyl group such as a p-chlorobenzyl group and an o-chlorobenzyl group. The phenyl group which may be substituted with a halogen atom, lower alkyl group, lower alkoxy group or nitro group represented by R ¹ is a phenyl group, p-chlorophenyl group, o-chlorophenyl group, 2,4-dichlorophenyl group. group, o-tolyl group, m-tolyl group, p-tolyl group, o-methoxyphenyl group, p-methoxyphenyl group, 4-nitrophenyl group, 2,4-dinitrophenyl group, and the like. Examples of the lower alkoxy lower alkyl group represented by R ¹ , R ² and R ³ include β-methoxyethyl group, β-
Ethoxyethyl group, straight or branched β
-propoxyethyl group, β-butoxyethyl group, γ-methoxybutyl group, etc. R ¹
Examples of the alkoxycarbonyl lower alkyl group represented by are β-methoxycarbonylethyl group, β-ethoxycarbonylethyl group, linear or branched β-propoxycarbonylethyl group, β-butoxycarbonylethyl group, -hexyloxycarbonylethyl group and β-octyloxycarbonylethyl group, α-methyl-β
-Methoxycarbonylethyl group, α-methyl-β
- Ethoxycarbonylethyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, linear or branched propoxycarbonylmethyl group, butoxycarbonylmethyl group, hexyloxycarbonylmethyl group and octyloxycarbonylmethyl group, α-methoxycarbonyl Examples include ethyl group and α-ethoxycarbonylethyl group. Examples of the lower alkyl group represented by R ¹ include β-(β′-methoxyethoxycarbonyl)
Ethyl group, β-(β′-ethoxyethoxycarbonyl)ethyl group, linear or branched β-
(β′-propoxyethoxycarbonyl)ethyl group and β-(β′-butoxyethoxycarbonyl)ethyl group, α-methyl-β-(β′-methoxyethoxycarbonyl)ethyl group, α-methyl-
β-(β′-ethoxyethoxycarbonyl)ethyl group, β-methoxyethoxycarbonylmethyl group, β-ethoxyethoxycarbonylmethyl group,
Linear or branched β-propoxyethoxycarbonylmethyl group, β-butoxyethoxycarbonylmethyl group, α-(β′-methoxyethoxycarbonyl)ethyl group, α-(β′-ethoxyethoxycarbonyl)ethyl group etc. Examples of lower alkyl groups represented by X and Y include methyl and ethyl groups. X
Examples of the halogen atom represented by and Y include a chlorine atom, a bromine atom, and an iodine atom. Synthetic fibers that can be dyed with the dye of the present invention include fibers made of synthetic polymer substances such as polyester, polyester ether, polyamide, and polyurethane; fibers made of semi-synthetic polymer substances such as triacetate and diacetate; Examples include blends of synthetic fibers or blends of natural fibers such as cotton, silk, and wool, but especially polyethylene terephthalate, terephthalic acid, and 1,4-
Fibers made of polyester such as a polycondensate with bis-(hydroxymethyl)cyclohexane are preferred. In order to dye the synthetic fibers with the dye of the present invention, the dye represented by the above general formula using a dispersant,
Dyeing or printing may be carried out by dispersing it in an aqueous medium to prepare a dyeing bath or printing paste. For example, when dyeing is carried out, the synthetic fibers can be dyed with excellent fastness by applying ordinary dyeing methods such as high temperature dyeing, carrier dyeing, and thermosol dyeing. In some cases, even better results may be obtained by adding an acidic substance such as formic acid, acetic acid, phosphoric acid, or ammonium sulfate to the dyeing bath. Next, the present invention will be explained in more detail with reference to Examples. Example 1 The following structural formula A dyeing bath was prepared by dispersing 0.5 g of the monoazo dye represented by 3 in water 3 containing 1 g of naphthalene sulfonic acid-formaldehyde condensate and 2 g of higher alcohol sulfate. 100g of polyester fiber was immersed in this dyeing bath and dyed at 130°C for 60 minutes, then soaped, washed with water, and dried, resulting in a clear bluish red color with good light fastness and sublimation fastness. A polyester cloth was obtained. The dye used in this example was 2-amino-5-
(n-Butylthio)-1,3,4-thiadiazole was diazotized with nitrosyl sulfuric acid in an acetic acid-propionic acid mixture, and 3-chloro-N,N-di-
The following structural formula is obtained by coupling to (n-butyl)aniline using a conventional method. After producing the monoazo compound represented by, it was dissolved in concentrated sulfuric acid, and an aqueous hydrogen peroxide solution (30%) was added at a molar ratio of 3 to the azo compound under ice cooling.
After reacting at 0 to 5°C for 10 hours, the product was discharged into ice water and the precipitated crystals were collected. λmax (in acetone) = 533nm Example 2 Structural formula below 0.5 g of the monoazo dye represented by is dispersed in water 3 containing 1.5 g of naphthalene sulfonic acid-formaldehyde condensate and 1 g of higher alcohol sulfate ester, and a methylnaphthalene carrier 15
A dyeing bath was prepared by adding g. When 100g of polyester fiber was immersed in this dyeing bath and dyed at 100℃ for 90 minutes, soaped, washed with water and dried, it was dyed in a vivid yellowish red color with good light fastness and sublimation fastness. A polyester cloth was obtained. The dye used in this example was 2-amino-5-
(β-phenylethylthio)-1,3,4-thiadiazole was diazotized with nitrosyl sulfate in an acetic acid-propylene acid mixture, and 3-chloro-N,N-
The following structural formula was obtained by coupling to diethylalinine using a conventional method. Dissolve the azo compound shown in concentrated sulfuric acid, add hydrogen peroxide aqueous solution (30%) in equimolar amount to the azo compound under ice cooling, react at 0 to 5°C for 30 minutes, and then dissolve in ice water. The product was produced by discharging the liquid into a liquid and collecting the precipitated crystals. λmax (in acetone) = 520nm Example 3 Structural formula below A dyeing bath was prepared by dispersing 0.5 g of the monoazo dye represented by 3 in water 3 containing 1 g of naphthalene sulfonic acid-formaldehyde condensate and 2 g of higher alcohol sulfate. 100g of triacetate fibers were immersed in this dyeing bath, the temperature was gradually raised, and dyeing was carried out at 80-85℃ for 60 minutes, followed by soaping, water washing, and drying. A triacetate fabric dyed in red color was obtained. The dye used in this example was 2-amino-5-ethylthio-1,3,4-thiadiazole in acetic acid.
The following structural formula was obtained by diazotizing with nitrosyl sulfuric acid in a propionic acid mixture and coupling it to N,N-diethylaniline by a conventional method. It was obtained by oxidizing the azo compound represented by in the same manner as in Example 1. λmax (in acetone) = 533nm Example 4 Structural formula below A dyeing bath was prepared by dispersing 0.5 g of the monoazo dye represented by 3 in water 3 containing 1 g of naphthalene sulfonic acid-formaldehyde condensate and 1 g of sodium higher alkylbenzenesulfonate, and 100 g of polyamide fiber was immersed in this dye bath, and heated at 100°C. After dyeing for 90 minutes, soaping, washing with water, and drying, polyamide fibers dyed in a vivid bluish red color were obtained. The dye used in this example was 2-amino-5-ethylthio-1,3,4-thiadiazole in acetic acid.
The following structural formula was obtained by diazotizing with nitrosyl sulfuric acid in a propionic acid mixture and coupling with N,N-diethyl-m-toluidine by a conventional method. It was obtained by oxidizing the azo compound represented by in the same manner as in Example 1. λmax (in acetone) = 535 nm Example 5 Using the monoazo dye shown in Table 1, Example 1
When polyester fibers were dyed according to the method described above, dyed fabrics with the colors shown in the table were obtained.

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1. General formula (In the formula, R ¹ is an alkyl group, an aralkyl group, an allyl group, a lower alkoxy lower alkyl group, a β-phenoxyethyl group, an alkoxycarbonyl lower alkyl group, a lower alkoxycarbonyl lower alkyl group, a tetrahydrofurfuryl group, a furfuryl group, or a halogen atom. , represents a phenyl group which may be substituted with a lower alkyl group, a lower alkoxy group or a nitro group, and R ² and R ³ are an alkyl group, an aralkyl group, an allyl group, a lower alkoxy lower alkyl group, a β-phenoxyethyl group, a furfuryl group. or tetrahydrofurfuryl group, X and Y represent a hydrogen atom, a lower alkyl group or a halogen atom, and n is 1 or 2.