JPH0439504B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on polybutylene terephthalate (hereinafter referred to as
It concerns triazine dyes (abbreviated as PBT) for textiles. Specifically, it relates to triazine-based reactive disperse dyes that can dye PBT fibers in yellow to blue colors with excellent color fastness including washing fastness. Conventionally, when dyeing PBT fibers, disperse dyes used for dyeing polyester fibers and the like have been used. However, when PBT fibers are dyed using the disperse dye, the dyeing properties such as build-up properties, temperature dependence, and pH dependence are good, but there is a problem that various fastness properties such as washing fastness are poor. . An object of the present invention is to provide a dye having a specific structure that can dye PBT fibers and obtain a dyed fabric with excellent fastness to washing and other properties. That is, the present invention is based on the general formula [] (In the formula, D represents a dye residue, X represents an oxygen atom or -NH- group, Y represents a fluorine atom or a chlorine atom, and Z represents a chlorine atom, an alkoxy group or -NR ¹ R ² , R ¹ and R ² represent a hydrogen atom; an alkyl group optionally substituted with a cyano group, a hydroxy group, an alkoxy group or an alkoxyalkoxy group; an alkenyl group; a cyclohexyl group; an aryl group or an aralkyl group, and -NR ¹ R ² may be a combination of R ¹ and R ² to form a 5- or 6-membered nitrogen-containing heterocycle.) Triazine dye for polybutylene terephthalate fibers. It is. The dye of the present invention represented by the above general formula [] can be divided into the following types according to the structural formula. General formula [] Carbocyclic monoazo dyes, carbocyclic disazo dyes, heterocyclic monoazo dyes and heterocyclic disazo dyes represented by: In the above general formula [], X, Y and Z are the same as defined in the above general formula []. A is a substituted or unsubstituted phenyl group, imidazolyl group, pyridyl group, riazolyl group, thiadiazolyl group, thienyl group, benzisothiazolyl group,
Represents a pyridinoisothiazolyl group, thienoisothiazolyl group, thienothiazolyl group or benzothiazolyl group. In addition, substituents for substituted phenyl groups include fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group,
Trifluoromethyl group, methoxy group, ethoxy group, phenylazo group, cyano group, nitro group, methylsulfonyl group, ethylsulfonyl group, allylsulfonyl group, lower alkoxycarbonyl group, lower alkoxyethoxycarbonyl group, allyloxyethylcarbonyl group, mono Lower alkylaminocarbonyl group, di-lower alkylaminocarbonyl group, diallylaminocarbonyl group, monoallylaminocarbonyl group, dimethylaminosulfonyl group, diethylaminosulfonyl group, monomethylaminosulfonyl group, monoethylaminosulfonyl group, acetyl group, phenyl group, etc. Examples of the substituents of the substituted pyridyl group include a chlorine atom, a bromine atom, a nitro group, a methyl group, a methylsulfonyl group,
Examples of the substituents of the substituted thiazolyl group include methyl group, chlorine atom, bromine atom, nitro group, lower alkoxycarbonyl group, methoxyethoxycarbonyl group, ethoxyethoxycarbonyl group, trifluoromethyl group, methylsulfonyl group, etc. Examples of the substituent of the substituted 1,3,4-thiadiazolyl group include an alkylthio group, an arylthio group, an alkenylthio group, an aralkylthio group, a bromine atom, a chlorine atom, a trifluoromethyl group, an alkylsulfonyl group, etc. and permutation 1, 2, 4
Examples of the substituent of the -thiadiazolyl group include an alkylthio group, arylthio group, alkenylthio group, aralkylthio group, and alkoxycarbonyl group, examples of the substituted imidazolyl group include a dicyanoimidazolyl group, and examples of the substituent of the substituted thienyl group include Examples include cyano group, chlorine atom, bromine atom, acetyl group, formyl group, nitro group, alkoxycarbonyl group, sulfomethyl group, and arylazo group, and substituents of substituted benzisothiazolyl group include nitro group, bromine atom, and chlorine atom. , an acetyl group, an alkoxycarbonyl group, a sulfomethyl group, etc. Substituents for the substituted pyridinoisothiazolyl group include a cyano group, a methyl group, and a nitro group, and examples of the substituent for the substituted thienoisothiazolyl group include Examples of substituents for substituted thienothiazolyl groups include nitro group, bromine atom, chlorine atom, and cyano group; examples of substituents for substituted benzothiazolyl group include methyl group, chlorine atom, and bromine. Atom, nitro group, lower alkoxycarbonyl group, thiocyano group, trifluoromethyl group, methylsulfonyl group and the like. R ³ represents a hydrogen atom, a methyl group, a methoxy group, a chlorine atom, an acetylamino group, a chloroacetylamino group, a benzoylamino group, a methylsulfonylamino group, a chloropropionylamino group, an ethoxycarbonylamino group, or an ethylaminocarbonylamino group . R ⁴ represents a hydrogen atom, a methoxy group, an ethoxy group, or a chlorine atom. R ⁵ is a C ₁ to C ₈ linear or branched alkoxyethyl group; a phenoxyethyl group; a benzyloxyethyl group; an allyloxyethyl group; a C ₁ to _{C 8} linear or branched hydroxyalkyl group; Cyano lower alkyl groups such as cyanomethyl group and cyanoethyl group; optionally substituted acyloxy lower alkyl groups such as acetyloxyethyl group, chloroacetyloxyethyl group, chloropropionyloxyethyl group, benzoyloxyethyl group; methoxycarbonyloxyethyl group; alkoxycarbonyloxy lower alkyl group such as methoxyethoxycarbonyloxyethyl group; carbamoyl lower alkyl group such as carbamoylmethyl group, carbamoylethyl group; methoxycarbonylmethyl group,
An optionally substituted alkoxycarbonyl lower alkyl group such as an ethoxycarbonylmethyl group, a methoxyethoxycarbonylmethyl group, a benzyloxycarbonylmethyl group; an optionally substituted aralkyl group such as a benzyl group, a phenethyl group, a chlorobenzyl group; Allyloxycarbonyl lower alkyl groups such as allyloxycarbonylethyl group and allyloxycarbonylmethyl group; Tetrahydrofurfuryl group; Succinimide lower alkyl group such as succinimideethyl group; Phthalate imide lower alkyl group such as phthalate imidoethyl group represents a cyanoalkoxy lower alkyl group such as a cyanoethoxyethyl group or a cyanomethoxyethyl group; a halogen lower alkyl group such as a chloroethyl group; or an aryl group such as a phenyl group, a chlorophenyl group, or a methylphenyl group. R ⁶ is a −CH ₂ −CH ₂ − group,

[Formula] Base Taha

[Formula] represents a group. General formula [] Carbocyclic monoazo dyes, carbocyclic disazo dyes, heterocyclic monoazo dyes and heterocyclic disazo dyes represented by: In the above general formula [], X, Y and Z are the same as defined in the above general formula [], and A, R ⁴ and
R ⁵ is the same as defined in the general formula [] above. General formula [] A disazo dye represented by In the above general formula [], X, Y and Z are the same as defined in the above general formula []. X ¹ and X ² are hydrogen atoms, chlorine atoms, bromine atoms,
Represents a nitro group or a methoxy group. R ⁷ and R ⁸ represent a hydrogen atom, a methyl group or a methoxy group, and R ⁷ and R ⁸ may form a phenyl group via a carbon atom. R ⁹ represents a hydrogen atom, a methyl group, or a methoxy group. R ¹⁰ represents a hydrogen atom or a methyl group. General formula [] Heterocyclic monoazo dyes and heterocyclic disazo dyes represented by In the general formula [], X, Y and Z are the same as defined in the general formula []. X ³ represents a hydrogen atom, a chlorine atom, a bromine atom, an acyl group, a nitro group, an alkoxy group, or an arylazo group optionally substituted with a chlorine atom or a nitro group. B is

[expression] or

【formula】

Represents [formula]. R ¹¹ and R ¹² represent a hydrogen atom, a chlorine atom, a nitro group, a benzenesulfonyloxy group or a methyl group. R ¹³ is a hydrogen atom, a C ₁ to C ₄ alkoxyethyl group,
Represents a _C1 - _C4 alkoxypropyl group, hydroxyethyl group or aralkyl group, and ^R14 is _-CH2
−CH ₂ − or −CH ₂ −CH ₂ −CH ₂ −. General formula [] Anthraquinone dye represented by In the above general formula [], one of X ⁴ and X ⁵ is a hydrogen atom and the other is (In the formula, X, Y and Z are the same as defined in the above general formula [], and R ¹⁹ is a hydrogen atom, a methyl group,
represents an ethyl group, methoxy group, ethoxy group, chlorine atom or bromine atom). Y ¹ represents a linking group of -O- or -S-. n represents 0 or 1, and when X ⁵ is a hydrogen atom, n represents 0. R ¹⁵ represents a hydrogen atom, a chlorine atom, a bromine atom, a cyano group or -SO ₂ R ²⁰ (R ²⁰ represents a methyl group, an ethyl group or a phenyl group). R ¹⁶ represents an amino group or a hydroxyl group. R ¹⁷ and R ¹⁸ represent a hydrogen atom, an amino group, a hydroxyl group, a nitro group, a chlorine atom or a bromine atom. General formula [] A quinophthane dye represented by In the above general formula [], X, Y and Z are the same as defined in the above general formula []. X ⁶ represents a hydrogen atom, a chlorine atom or a bromine atom. n represents 0 or 1. General formula [] A quinophthalone dye represented by In the above general formula [], X, Y and Z are the same as defined in the above general formula []. X ⁷ is a hydrogen atom, chlorine atom, bromine atom, C ₁ ~
Represents a C ₄ alkoxy group or phenoxy group. The dye according to the present invention can be produced by a conventional method. In addition, when dyeing PBT fibers using the dye of the present invention, as in the usual dyeing method for synthetic fibers, since the dye represented by the general formula [] shown above is insoluble or sparingly soluble in water, Dyeing or printing can be carried out by preparing a dye bath or printing paste dispersed in an aqueous medium using a dispersing agent according to the method. For example, in the case of dip dyeing, dyeing with excellent fastness can be achieved by applying common dyeing methods such as high temperature dyeing, Geary dyeing, and thermosol dyeing.
In this case, if an acidic substance is added to the dyeing bath, even better results can be obtained. EXAMPLES The present invention will be explained in more detail with reference to examples below, but the present invention is not limited to the following examples. Example 1 Structural formula below 0.1g of anthraquinone dye shown by 0.2g of naphthalenesulfonic acid-formaldehyde condensate
10 g of PBT fiber was immersed in a dyeing bath containing 0.4 g of higher alcohol sulfate ester and dispersed in 300 ml of water, dyed at 130°C for 60 minutes, and then soaped.
After washing with water and drying, a vivid blue dyed fabric was obtained. The dyed fabric obtained had good light fastness, sublimation fastness, washing fastness and water fastness. The dye used in this example was synthesized by the following method. 1,5-diamino-4,8-dihydroxy-
2-(4-hydroxyphenyl)anthraquinone
3.62 g was dissolved in 50 ml of N-methyl-2-pyrrolidone, 20 g of triethylamine and 20 g of 2,4-difluoro-6-diethylaminotriazine were added, and the mixture was stirred at 40° C. for 3 hours to carry out a condensation reaction.
The resulting reaction solution was added dropwise to 500 ml of water to separate the resulting precipitate, which was washed with water and dried at room temperature in a vacuum dryer to obtain a dark blue powder of the dye represented by the above structural formula.
4.9g was obtained. The maximum absorption wavelength of this dye, λmax (acetone), is
It was 628nm. Comparative example 1 Structural formula below Example 1 using the anthraquinone dye shown in
A dyed product was obtained by dyeing PBT fibers according to the method described in . Table 1 shows a comparison of fastness with Example 1.

[Table] As described above, the dye of this patent has significantly improved fastness compared to conventional dyes. Note 1: According to JIS L-0842-1971 law. Note 2 Contamination of nylon cloth was determined using a contamination scale according to A-4 of JIS L-0844-1973. Note 2 According to method B of JIS L-0846-1976,
Contamination of nylon cloth was determined using a contamination scale. Example 2 PBT fibers were dyed using the dyes shown in Table 2 below according to the method of Example 1 to obtain dyed products having the colors shown in the table. Further, the washing fastness of the dyed product is shown in Table 2.

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Claims (1)

[Claims] 1. General formula [] (In the formula, D represents a dye residue, X represents an oxygen atom or -NH- group, Y represents a fluorine atom or a chlorine atom, and Z represents a chlorine atom, an alkoxy group or -NR ¹ R ² , R ¹ and R ² represent a hydrogen atom; an alkyl group optionally substituted with a cyano group, a hydroxy group, an alkoxy group or an alkoxyalkoxy group; an alkenyl group; a cyclohexyl group; an aryl group or an aralkyl group, and -NR ¹ R ² may be a combination of R ¹ and R ² to form a 5- or 6-membered nitrogen-containing heterocycle.) A triazine dye for polybutylene terephthalate fibers.