KR20000050781A - A formazan dye compound including pyrimidine radical, and its preparing method - Google Patents

Abstract

PURPOSE: A formazan reactive dye compound containing a pyridine group and process for producing them are provided which show low temperature dyeing characteristics and are suitable for dyeing by a cold batch method. CONSTITUTION: A dye compound represented by the formula (1) in which X1,X2,X3 are each a sulfon group or H or halogen, a carboxy group, a phosphonic acid group; M is an alkali metal selected from lithium, sodium and potassium; A is fluorine atom or a benzene derivative containing methyl or amine group. The compound is excellent in adherence rate, solubility, printing suitability, cold pad batch property or the like.

Description

Formazan dye compound including pyrimidine radical, and its preparing method

The present invention is a light blue formazan-based reactive dye compound containing a pyrimidine group represented by the following general formula (I), which can be cold pad batch dyeing and having high dyeing yield, high dyeing yield, and also applicable to printing. It relates to a method for producing this compound.

… (Ⅰ)

Wherein X ₁ , X ₂ and X ₃ are each a sulfone group (SO ₃ M) or a carboxy group or phosphonic acid group which provides solubility in hydrogen atoms or halogenated elements, and M is selected from lithium, sodium and potassium. Alkali metal, A is a fluorine atom or a benzene derivative containing a methyl (CH ₃ ) or an amine group.

Conventional formazan-based reactive dyes have the disadvantage that the dyeing at a high temperature, low dyeing yield in dyeing, and is not suitable for printing.

Well-known formazan dyes include the compound represented by the following general formula (II) described in Japanese Patent Application Laid-Open No. 3-10669 and the following general formula described in Korean Patent Publication (Publication No. 96-37778). There is a compound represented by III).

… (Ⅱ)

… (Ⅲ)

An object of the present invention is a light blue formazan-based reactive dye containing a pyrimidine group represented by the following general formula (I), which is capable of cold pad batch dyeing with low temperature dyeing properties and high dyeing yield and is also applicable to printing. To provide a compound and a method for preparing the compound.

… (Ⅰ)

Wherein X ₁ , X ₂ and X ₃ are each a sulfone group (SO ₃ M) or a carboxy group or phosphonic acid group which provides solubility in hydrogen atoms or halogenated elements, and M is selected from lithium, sodium and potassium. Alkali metal, A is a fluorine atom or a benzene derivative containing a methyl (CH ₃ ) or an amine group.

The manufacturing method of the formazan derivative of the general formula (I)

The hydrazine derivative of the general formula (IV) is reacted with the benzaldehyde derivative of the general formula (V) to generate the hydrazone derivative of the general formula (VI). The reaction is possible at 5 ° C to 50 ° C.

… (Ⅳ)

… (Ⅴ)

… (Ⅵ)

The compound of formula (VI) is coupled with a diazonium ion compound of formula (VII) to obtain a pigment of formula (VII), wherein the coupling condition is carried out under strong alkali conditions to pH 11 or more, At this time, the color becomes orange.

… (Ⅶ)

… (Ⅷ)

CuSO ₄ 5H ₂ O is complexed with a general compound to complete the formazan pigment of the following general formula.

Deacetylation of the finished formazan pigment yields a compound of formula

… (Ⅸ)

… (X)

Condensation of a compound of formula (III) and a pyrimidine derivative of formula (XI) below with a reactor can yield the target compound of formula (I).

… (XI)

The preparation method of the formazan derivative of the present invention can be explained in more detail by the following examples.

<Example 1-Formazan derivative synthesis method>

After diazotizing 25.3 parts of aniline-2,5-disulfonic acid, a hydrazone compound was formed through a reduction process, and 11.0 parts of benzaldehyde, defined by the general formula (3), was added to the hydrazine compound, and the temperature was about 5 to 30 degrees and the pH was neutral. Stir to about 3 hours or more to produce a hydrazone compound defined by the general formula (4).

After adding 18.5 parts of acetylated 3-acetylamino-2-hydroxyaniline-5-sulfonic acid at 5 degrees C or less, caustic soda was added, pH was adjusted to 11 or more, and a coupling process is performed. The coupling takes 2-3 hours, the color of which is orange.

When the coupling is completed, 18.4 parts of copper sulfate is added to complete the production of light blue color formazan pigment, followed by salting with sodium chloride and filtering to obtain a cake.

The resulting cake was dissolved in 800 parts of water, 60 parts of caustic soda was added, and the temperature was maintained at about 100 ° C., stirred for about 5 hours, followed by deacetylation, neutralization, salting out with sodium chloride, and filtration to obtain the formazan pigment.

A solution obtained by mixing 17 parts of 5-chloro-2,4,6-trifluoropyrimidine, 100 parts of acetone and necalbiex (dispersant) defined above with the above pigments at 30 to 5 Add slowly over a minute and add sodium carbonate to maintain pH at neutral and terminate the reaction by inversion stirring for 3 hours.

Sodium chloride is added to the liquid compound to complete the reaction, followed by salting and filtering to obtain a cake of a compound having the following structural formula.

The above structure is a formazan reactive dye of light blue system having a maximum absorption wavelength of 600 ± 2 nm.

<Example 2-Formazan derivative synthesis method>

After diazotizing 25.3 parts of aniline-2,4-disulfonic acid, a hydrazone compound was formed through a reduction process, and 11.0 parts of benzaldehyde defined by the general formula (3) was added to the hydrazine compound, and the temperature was about 5 to 30 degrees and the pH was neutral. Stir to about 3 hours or more to produce a hydrazone compound defined by the general formula (4).

The above steps are the same as in <Example 1>.

<Example 3-Formazan derivative synthesis method>

After diazotizing 25.3 parts of aniline-2,4-disulfonic acid, a hydrazone compound was formed through a reduction process, and 19.0 parts of benzaldehyde-3-sulfonic acid defined by the general formula (3) was added to the hydrazine compound and the temperature was 5 to 30 degrees. The pH and the pH were stirred at about 3 hours or more to give a hydrazone compound defined by the general formula (4).

The above steps are the same as in <Example 1>.

<Example 4-Formazan derivative synthesis method>

4- (aniline-3-sulfonic acid) -5-chloro-2,6-difluoropyrimidine was added to the dye synthesized in the same manner as in Example 1, and the temperature was 30 to 40 ° C for about 3 hours at pH 7 to 8 By stirring, the formazan reactive dye for printing is prepared.

The above structure also shows almost the same color as in Example 1.

<Example 5-Infestation of Example 1>

5 g of white cloth was added to 30 ml of a 0.5% solution of 12% water, 12 g of water, and 4 g of forget-me-not, which were obtained from Bayer, Germany. The solution was slowly heated to 60 ° C., stirred for 30 minutes, and 8 ml of a 15% solution of sodium carbonate was added at ionicity.

The dyeing is completed by stirring for 60 minutes while keeping the temperature at 60 ° C.

Wash the dyed cloth with water, wash it in boiling soapy water for 10 minutes, wash it again with water, dry and compare the dyeing results.

As a result of comparing the dyeing performance of fixation rate, color fastness, light fastness, solubility, etc., using the formazan derivative obtained in Example 1 of the present invention as a reference material, As shown in Table (1), it shows that the comparative material showed excellent performance in the sticking rate, solubility, printing application, cold-pad batchability and the like.

Dyeing performance comparison Test Items Reference substance Comparative substance Fixation rate (%) Laundry fastness Sun light fastness Solubility (g / ℓ) Printing application Cold-pad Batch property (Cold-Pad Batch) Not applicable at 83.44 Grade 5 Grade 30 Applicable Hard Concentration Applies to Grade 5, Grade 100 and 86.04 ※ Test method ○ Washing fastness: According to JIS L 0844, Washing fastness test ○ Daylight fastness: According to JIS L 0843, daylight fastness test

In particular, when comparing the build-up properties, as shown in the graph below, the comparative material showed a higher dyeing yield at the entire dyeing concentration than the reference material, and the slope of the color concentration was continuously increased at a high concentration. It is excellent.

In the diagram above… … The line part represents the reference substance and the line part represents the reference substance.

Claims (2)

Formazan dyes represented by the following general formula (I) … (Ⅰ) Wherein X ₁ , X ₂ and X ₃ are each a sulfone group (SO ₃ M) or a carboxy group or phosphonic acid group that provides solubility in hydrogen atoms or halogenated elements, and M is selected from lithium, sodium and potassium. Alkali metal, A is a fluorine atom or a benzene derivative containing a methyl (CH ₃ ) or an amine group. In the method for producing a formazan dye compound containing a pyrimidine group, a benzaldehyde compound represented by the following general formula (V) is added to the hydrazine compound represented by the following general formula (IV) and represented by the following general formula (VI). Synthesizing the hydrazone compound and coupling it with the compound represented by the following general formula (Ⅶ) and complexed with CuSO ₄ · 5H ₂ O to obtain a pigment, and condensation of the reactor represented by the general formula (XI) The manufacturing method of the formazan dye containing the pyrimidine group represented by general formula (I). … (Ⅳ) … (Ⅴ) … (Ⅵ) … (Ⅶ) … (Ⅷ) … (XI) … (Ⅰ) Wherein X ₁ , X ₂ , X ₃ are each a sulphon group (SO ₃ M) or a carboxy group, a phosphonic acid group that provides solubility in hydrogen atoms or halogenated element water, and M is in lithium, sodium, potassium Alkali metal selected, A is a fluorine atom or a benzene derivative comprising a methyl (CH ₃ ) or an amine group.