JPS6256187B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula [In the formula; X is a hydrogen atom, a chlorine atom, a bromine atom, or a cyan group; R is unsubstituted or
or an alkyl group having 1 to 4 carbon atoms substituted by a halogen or a lower alkoxy group; R ₁ is a carbon atom which is unsubstituted or substituted by a lower alkoxy group or an aryl group; an alkyl group having 1 to 4 atoms; R ₂ is a carbon group that is unsubstituted or substituted with an acyloxy group, an aryl group, a halogen, an aryloxy group, a furfurylmethylene group, or a tetrahydrofurfurylmethylene group; an alkyl group having 1 to 4 atoms or a cyclohexyl group which is unsubstituted or substituted by a lower alkyl group; and Y is an alkyl group having 1 to 4 carbon atoms or a cyclohexyl group having 1 to 4 carbon atoms; It is an alkoxy group having ~4. This paper relates to valuable new blue, dark blue or violet monoazo dyes represented by the following, as well as their production methods and uses. In this specification, lower alkyl and lower alkoxy groups are alkyl and alkoxy groups having 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms, such as methyl, ethyl, methoxy or ethoxy. In the sense of alkyl radicals having 1 to 4 carbon atoms, R, R ₁ and R ₂ can be the same or different and unbranched or branched. This includes, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group,
It is a 2nd butyl group or a tertiary butyl group. These alkyl groups can be substituted, for example in the case of R, bromine or a halogen atom, mainly a chlorine atom, a lower alkoxy group, especially a methoxy group,
By an ethoxy or propoxy group, or an aryloxy group, especially a phenoxy group, in the case of R ₁ a lower alkoxy group, especially a methoxy or ethoxy group, an aryloxy group, especially a phenoxy group or an aryl group, especially a phenyl group. , and in the case of R ₂ can be substituted by an acyloxy group, especially an acetyloxy group, an aryl group, especially a phenyl group, or a heterocycle, especially an oxygen-containing heterocycle, such as a furfuryl or tetrahydrofurfuryl group. Mainly, R includes a methyl group, ethyl group, methoxymethyl group, ethoxymethyl group, or chloromethyl group, and R ₁ includes a methyl group, ethyl group, propyl group, isopropyl group, methoxyethyl group, phenoxyethyl group, benzyl group. or phenethyl group, and R ₂ is a methyl group, ethyl group, propyl group, isopropyl group, phenoxyethyl group, acetyloxyethyl group, chloroethyl group, benzyl group, furfuryl group, tetrahydrofurfuryl group or cyclohexyl group. Can be mentioned. Cycloalkyl radicals in which R ₂ may be substituted include in particular cycloalkyl radicals having 5 to 7 carbon atoms, such as methylcyclohexyl and especially cyclohexyl. Preferably, X is a chlorine or bromine atom. R is preferably an unsubstituted alkyl group, especially a methyl group. R ₁ is preferably an isopropyl group, an ethyl group or a methoxyethyl group, and especially a methyl group. R ₂ is preferably an aryloxy group, an acyloxy group, an aryl group or an alkyl group having 1 to 4 carbon atoms, which may be substituted with a heterocycle, or a cyclohexyl group, in particular a methyl group, an ethyl group, They are a propyl group, isopropyl group, phenoxyethyl group, acetyloxyethyl group, chloroethyl group, benzyl group, furfurylmethylene group, tetrahydrofurfurylmethylene group, or cyclohexyl group. In particular, R ₂ is an unsubstituted methyl or ethyl group. Preferably, Y is a methyl group or an ethyl group. In preferred monoazo dyes of formula (),
X is a chlorine or bromine atom, R is a methyl group,
methoxymethyl or ethoxymethyl, R ₁ is methyl, ethyl, isopropyl or methoxyethyl, Y is methyl or ethyl, and R ₂ is aryloxy, acyloxy, aryl or an alkyl group having 1 to 4 carbon atoms or a cyclohexyl group, which may be substituted with a heterocycle, especially a methyl or ethyl group. In particular, X in formula () is a chlorine or bromine atom, R and R ₁ are methyl groups, Y is a methyl group or an ethyl group, R ₂ is a methyl group,
Ethyl group, propyl group, isopropyl group, phenoxyethyl group, acetyloxyethyl group, chloroethyl group, benzyl group, furfurylmethylene group,
Monoazo dyes which are tetrahydrofurfurylmethylene or cyclohexyl groups are preferred. The dye of formula () is of the formula (In this formula, X has the meaning given above.) The diazo component of the amine represented by the formula (In this formula, R, R ₁ , R ₂ and Y have the meanings given above.) The coupling component represented by
Obtained by coupling in position. The diazo component of formula () is known. formula()
The coupling component of is novel and can be prepared by methods known per se, e.g. (In this formula, R and R ₂ have the meanings given above.) The ketone represented by the formula (in which R ₁ and Y have the meanings given above) by condensation with an amine of the formula and reduction of the condensation product. The diazo component is diazotized by a conventional method, preferably using a concentrated sulfuric acid solution of nitrosylsulfuric acid. The coupling reaction mentioned above is also carried out in a manner known per se, for example in a neutral or preferably acidic aqueous solution or suspension. That is, the resulting solution or suspension of the diazo compound is added to an aqueous solution of the coupling component, which solution contains an acid and/or a water-miscible organic solvent. Once coupling is complete, the dye formed can be easily separated from the coupling mixture, for example by filtration. This is because this dye is virtually insoluble in water. According to another method, the group in formula () -
Dyes of formula () can also be obtained by treating the corresponding dyes in which COY is a hydrogen atom with an acylating agent. Examples of acylating agents are acetic anhydride, acetyl chloride or propionyl chloride. This alternative method is suitably carried out in such a way that the reactants are reacted in the presence of a base such as pyridine. The new monoazo dyes according to the invention can be applied from aqueous dispersions to hydrophobic materials, especially synthetic textile materials in any form of production, such as fibers, filaments and fabrics of polyamides, but especially of aromatic polyesters such as polyethylene glycol terephthalate or terephthalic acid. and 1,4-(bis-hydroxymethyl)-cyclohexane or for dyeing or printing fabrics or fibers made of triacetylcellulose. In particular, the monoazo dyes according to the invention have very good dyeing and deposition properties on aromatic polyester textile materials, which makes it possible to obtain uniform, intense and reproducible shades using a homogeneous monoazo dye. Obtainable. The dark blue dyeings and prints obtained on said materials with the preferred dyes according to the invention in which X is a chlorine or bromine atom have good dark color and color strength and a high general fastness, in particular
It is characterized by high PH stability, high level dyeing property, and high sublimation and sunlight fastness. In this case, the usual conditions and additives commonly employed for applying disperse dyes on synthetic textile materials are used. For dyeing with the dyestuff of formula (), the material to be dyed is preferably introduced into an aqueous dispersion of the dyestuff at an elevated temperature, for example 40°C, and, if desired, the usual auxiliaries, such as sulfite cellulose decomposition products, are added. ethylene oxide adducts of higher alcohols, fatty acid amides or polyglycol ethers of alkyl phenols, etc., and an acidic agent, such as an organic acid such as formic acid or acetic acid or an inorganic acid such as phosphoric acid, is preferably added to the bath. This bath is then heated to an optimum dyeing temperature, preferably between 70 and 140 DEG C., depending on the type of fiber material to be dyed. Dye at this temperature until the desired color density is reached. The bath is cooled and the dyed fiber material is treated, for example after-treated with soap in the case of acetate fibers or reductively in the presence of alkali in the case of aromatic polyester fibers. When dyeing aromatic polyester or triacetate fibers at 105° C., customary carrier substances such as monochlorobenzene, dichlorobenzene, trichlorobenzene, benzoic acid, salicylic acid, o- or p-phenylphenol or benzyl alcohol are generally used in combination. is advantageous. To thermally fix the dye, it is suitable to heat the padded fabric to a temperature above 100 DEG C., for example from 180 DEG to 210 DEG C., after having previously dried it, for example in hot air. Printing is similarly carried out by a method known per se. This means that a printing paste containing the dye according to the invention in addition to the usual auxiliaries is applied to the textile material and then heat treated. It should be noted that good fastness properties are likewise achieved when the dyes according to the invention are applied from organic solvents, that is to say when they are applied to the substrates to be dyed from solvents containing the dyes as a solution or as a finely divided dispersion. Solvents include inter alia chlorinated hydrocarbons (eg perchlorethylene). It can be used alone or as a dispersion with water. Dyes, especially those whose at least 60% is converted to vapor state in less than 60 seconds at 150-220°C under atmospheric pressure, can also be used in transfer printing methods. . In this case, the dye is transferred from a temporary carrier, for example paper, onto the textile material. Generally, short-term heating (10-60 seconds) at atmospheric pressure or vacuum to 150-220°C is sufficient for this purpose. The dyes according to the invention are superior to comparable dyes in dyeing polyester materials by virtue of their high boiling resistance. Next, the present invention will be explained in more detail with reference to Examples. In these examples, all parts and percentages are by weight. Example 1 21.8 parts of 6-chloro-2,4-dinitroaniline are suspended in 110 parts of 88% sulfuric acid and 40%
diazotization by dropwise addition of 32 parts of nitrosyl sulfate over 30 minutes. After stirring for 2 hours at room temperature, this clear diazo solution was dissolved in a mixture of 12 parts of concentrated hydrochloric acid and 300 parts of water. 0 to 31 parts of a solution of the coupling component represented by
Add dropwise over 30 minutes while stirring at 5°C. The coupling reaction is completed immediately. The precipitated dye is filtered off, washed with warm water until neutral, and dried. Finely divided dyestuffs thus obtained, together with suitable auxiliaries such as sulfite waste liquor or dinaphthylmethane disulphonic acid, exhibit high buildup and leveling properties on polyethylene glycol terephthalate fibers and dye the fibers in dark blue shades.
This dyeing is fast to sublimation and to sunlight. The above coupling component is made by hydrogenation of the Schiff base obtained by condensing 4-propionylamino-2-aminoanisole with methyl acetoacetate by the following reaction step. In a similar manner the dyes listed in the table below are obtained from the corresponding diazo and coupling components. These dyes similarly dye dark blue tones on polyethylene glycol terephthalate fibers, except that Examples 29-33 produce pure blue and Examples 35 and 36 produce violet.

【table】

【table】

[Table] In the above table, example numbers 3, 4, 6, 7, 8, 9,
Dyes 11, 17, 19 and 20 have the following melting points, respectively. Example number Melting point 3 168-172℃ 4 160-166℃ 6 180-182℃ 7 156-159℃ 8 148-153℃ 9 154℃ 11 161-162℃ 17 132-134℃ 19 164-169℃ 20 154- 155℃ Dyeing Example Add 1 part of the dye obtained in Example 1 to 2 parts of a 50% aqueous solution of the sodium salt of dinaphthylmethane disulfonic acid.
Grind when wet with parts and dry. This dye formulation is mixed with 40 parts of a 10% aqueous solution of the sodium salt of N-butyl-.mu.-heptadecylbenzimidazole disulfonic acid and to this is added 4 parts of 40% acetic acid. Dilute this with water to prepare 4000 parts of a dyebath. 100 parts of purified polyester fiber material are introduced into this bath at 50 DEG C., the temperature is increased to 120 DEG -130 DEG C. in 30 minutes and dyeing is carried out at this temperature for 1 hour in a closed container. Then rinse. A uniform dark blue dyeing with favorable sunlight fastness and high sublimation fastness is thus obtained. Printing Example: 25 parts of the dyestuff according to Example 1, previously finely ground, 550 parts of an 8% aqueous dyestuff consisting of modified locust bean flour, and 50 parts of a 10% solution of the sodium salt of m-nitrobenzenesulfonic acid. , 10 parts of a mixture of potassium oleate and pine oil are mixed and made up to 1000 parts with water. This mixture is stirred using a high speed stirrer until a sufficient dispersion of dye is produced and the paste is used to print polyethylene glycol terephthalate fabric. After printing, the fabric is dried and soaked at 1.5 atmospheres for 20 minutes, rinsed with cold water for 10 minutes, soaped twice with hot water with a small amount of hydrosulfite, rinsed with cold water and dried. A fast, dark blue print is thus obtained.

Claims (1)

[Claims] 1 formula [In the formula; X is a hydrogen atom, a chlorine atom, a bromine atom, or a cyan group; R is unsubstituted or
or an alkyl group having 1 to 4 carbon atoms substituted by a halogen or a lower alkoxy group; R ₁ is a carbon atom which is unsubstituted or substituted by a lower alkoxy group or an aryl group; is an alkyl group having 1 to 4 atoms; R ₂ is unsubstituted or substituted with an acyloxy group, an aryl group, a halogen, an aryloxy group, a furfurylmethylene group, or a tetrahydrofurfurylmethylene group an alkyl group having 1 to 4 carbon atoms, or a cyclohexyl group that is unsubstituted or substituted by a lower alkyl group; and Y
is an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms]. 2. The monoazo dye according to claim 1, wherein X is a chlorine atom or a bromine atom. 3 R is a methyl group, a methoxymethyl group or an ethoxyethyl group, R ₁ is a methyl group, an ethyl group, an isopropyl group or a methoxyethyl group, and Y is a methyl group or an ethyl group Claim 1 Monoazo dyes described in Section. 4 R ₂ is unsubstituted or acyloxy group, phenyl group, phenyloxy group, chlorine,
1 to carbon atoms substituted with furfurylmethylene group or tetrahydrofurfurylmethylene group
The monoazo dye according to any one of claims 1 to 3, which is an alkyl group having 4 or a cyclohexyl group that is unsubstituted or substituted with a methyl group. 5. The monoazo dye according to claim 1, wherein R ₂ is a methyl group or an ethyl group. 6 X is a chlorine or bromine atom, R and _R1 are a methyl group, Y is a methyl group or an ethyl group, and _R2 is a methyl group, ethyl group, propyl group, isopropyl group, phenoxyethyl group,
The monoazo dye according to any one of claims 1 to 5, which is an acetyloxyethyl group, a chloroethyl group, a benzyl group, a furfurylmethylene group, a tetrahydrofurfurylmethylene group, or a cyclohexyl group. 7 General formula (wherein; X is a hydrogen atom, a chlorine atom, a bromine atom, or a cyano group) [In the formula; R is an alkyl group having 1 to 4 carbon atoms, which is unsubstituted or substituted by a halogen or a lower alkoxy group; R ₁ is unsubstituted or a lower alkoxy group; an alkyl group having 1 to 4 carbon atoms substituted by a group or an aryl group;
R ₂ is unsubstituted or acyloxy group, aryl group, halogen, aryloxy group,
1 to carbon atoms substituted with furfurylmethylene group or tetrahydrofurfurylmethylene group
an alkyl group having 4 carbon atoms or a cyclohexyl group that is unsubstituted or substituted by a lower alkyl group; and Y is an alkyl group having 1 to 4 carbon atoms or a cyclohexyl group having 1 to 4 carbon atoms;
an alkoxy group having ~4 alkoxy groups] and a general formula characterized in that the coupling component is coupled at the p-position of an amino group. (In this formula, X, R, R ₁ , R ₂ and Y have the meanings given above.) A method for producing a monoazo dye represented by: 8. The method according to claim 7, wherein the amine of formula () in which X is a chlorine or bromine atom is used. 9 As a coupling component of formula (), R is a methyl group, a methoxymethyl group or an ethoxyethyl group, R ₁ is a methyl group, an ethyl group, an isopropyl group or a methoxyethyl group, and Y
The method according to claim 7, wherein is a methyl group or an ethyl group. 10 As the coupling component of formula (), R ₂
is unsubstituted or an acyloxy group,
an alkyl group having 1 to 4 carbon atoms substituted with phenyl, phenyloxy, chlorine, furfurylmethylene or tetrahydrofurfurylmethylene, or unsubstituted or substituted by methyl; The method according to claim 9, wherein a cyclohexyl group is used. 11 As the coupling component of formula (), R ₂
The method according to claim 7, wherein is a methyl group or an ethyl group. 12 As the diazo component of formula (), use one in which X is a chlorine or bromine atom, and as the coupling component of formula (), R and R ₁ are methyl groups, Y is a methyl group or ethyl group, and Patent claims in which R ₂ is a methyl group, ethyl group, propyl group, isopropyl group, phenoxyethyl group, acetyloxyethyl group, chloroethyl group, benzyl group, furfurylmethylene group, tetrahydrofurfurylmethylene group or cyclohexyl group The method described in scope item 7.