JPH08109335A - Cationic dyestuff - Google Patents

Abstract

PURPOSE: To obtain a new cationic dyestuff advantageous also on the aspect of waste water regulation and environmental maintenance, because the exhaustion degree of the dyestuff to paper, pulp, etc., is extremely high and further because the waste water generated in a dyeing process is substantially colorless. CONSTITUTION: The cationic dyestuff of formula I (R1 , R2 are alkyl, aralkyl; R3 is H, alkyl; A<-> is anion), e.g. a compound of formula II. The dyestuff is obtained e.g. by condensing a compound of formula III such as 1-(2,3- dihydroxypropyl)pyridinium chloride with cyanoacetic acid and an aldehyde of formula IV such as 4-diethylaminobenzaldehyde in acetic anhydride at 70-90 deg.C. The quaternary compound of formula III is obtained e.g. by reacting pyridine with glycerol-α-monochlorohydrin at 120-130 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cationic dye useful for coloring or dyeing fibers such as paper, pulp, leather, printing ink, recording ink, or acrylic.

[0002]

2. Description of the Related Art Many cationic dyes are used for dyeing paper, pulp and the like. However, cationic dyes generally have weak dyeing power to paper, pulp and the like, and a considerable amount of undyed dye remains in the dyeing wastewater, which is a serious problem in environmental protection such as wastewater pollution. Therefore, many auxiliaries are used to enhance the dyeing property of the dye, but the satisfactory effect is not achieved at present. Therefore, there is a demand for the development of a dye which has a high dyeing property on paper, pulp and the like and makes the dyeing wastewater colorless or nearly colorless.

[0003]

The present invention has been made to solve the above environmental problems, and is a cation represented by the general formula (1) which has a high dyeing property on paper, pulp and the like. It is to provide a dye.

Embedded image (In the formula, R ₁ and R ₂ represent an alkyl group or an aralkyl group, R ₃ represents a hydrogen or an alkyl group, and A ⁻ represents an anion.)

[0004]

The compounds of general formula [Means for Solving the Problems] (1) anion A ^- example chloride, bromide, sulfate, nitrate, formic acid, acetic acid, propionic acid, methosulfate, ethosulfate, chloroacetic acid, The anions of citric acid, lactic acid, or rhodanic acid, R ₁ , R ₂ , the alkyl group is a methyl group, an ethyl group, a butyl group, the aralkyl group is a benzyl group, R ₃
The alkyl group is a methyl group or an ethyl group. The cationic dye represented by the general formula (1) has the following structural formula

[0005]

Embedded image (Wherein R ₃ and A ⁻ are as defined above), the quaternary compound is converted to cyanoacetic acid and the following structural formula in the presence of acetic anhydride.

[0006]

[Chemical 4] It can be produced by condensation with an aldehyde compound represented by the formula (R ₁ and R ₂ are as described above).

With respect to the above-mentioned quaternary compound, for example, pyridine and glycerol-α-monochlorohydrin are reacted at 120 to 130 ° C. without solvent or in a solvent such as isoamyl alcohol or ethylene glycol monomethyl ether. It is manufactured by

Condensation of this quaternary compound with cyanoacetic acid and the above-mentioned aldehyde compound is carried out in acetic anhydride at 70-
It proceeds by a dehydration reaction at a reaction temperature of 90 ° C. The amount of acetic anhydride used is preferably 5 to 7 molar equivalents. The cationic dye of the general formula (1) of the present invention can be produced from this reaction solution by a known method in the form of powder, granules, liquid or the like.

That is, the production of the compound of the general formula (1) is
A carboxylic acid obtained by condensing the above-mentioned aldehyde compound with cyanoacetic acid in pyridine in the presence of piperidine is treated with thionyl chloride in toluene to give the following formula:

[0010]

Embedded image It is also possible to obtain an acid chloride represented by the formula (wherein R ₁ and R ₂ are as described above) and to condense this with the above quaternary compound.

The cationic dye according to the present invention can be applied to a natural or synthetic material such as paper, pulp or acrylic fiber for dyeing or printing. In particular, according to the dye of the present invention, the dyeing wastewater is made almost colorless because it exhibits excellent dyeing property to paper and pulp, and great advantages can be obtained from the viewpoint of wastewater regulation and environmental protection. The dye of the present invention is also suitable for printing ink, recording ink and the like.

[0012]

EXAMPLES The production examples of the dye according to the present invention will be specifically described below with reference to examples, but the present invention is not limited to these.

Example 1

[Chemical 6] 9.57 g of acetic anhydride and 2.38 g of cyanoacetic acid were stirred at 50 ° C for 1 hour and then 2.66 g of 1- (2,3-dihydroxypropyl) pyridinium chloride and 4-
4.96 g of diethylaminobenzaldehyde was added,
After heating at 80 to 90 ° C for 6 hours, it was cooled to 50 ° C. After dissolving the reaction solution in 80 g of warm water at 50 ° C,
The dye is precipitated by adding 8 g of sodium chloride, and after liquid separation is dried in vacuum at 50 ° C., a yellow dye having a maximum absorption wavelength of 434 nm (DMF) represented by the above structural formula.
78 g are obtained. This product dyed paper and pulp in a vivid green-yellow color, and the wastewater was almost colorless. The quaternary compound used here was manufactured by the following method. Pyridine (6.33 g) and glycerol-α-monochlorohydrin (8.84 g) were reacted at 120 ° C for 5 hours. After cooling, acetone was added to precipitate crystals, which were then filtered and dried. Yield 12.
15g, melting point 100-102 ° C.

Example 2

[Chemical 7] After stirring 10.25 g of acetic anhydride and 2.55 g of cyanoacetic acid at 50 ° C. for 1 hour, 2.85 g of 1- (2,3-dihydroxypropyl) pyridinium chloride and 4.47 g of 4-dimethylaminobenzaldehyde were added, and 80
Heat to ~ 90 ° C. Stir at this temperature for 6 hours and then cool to 60 ° C to remove residual acetic anhydride with water 3
g was added, and the mixture was stirred for 2 hours and cooled to room temperature to obtain a thick liquid dye containing 7.92 g of the cationic dye represented by the above structural formula. This product dyes paper and pulp in a vivid green-yellow color, and coloring of wastewater is almost colorless. . The maximum absorption wavelength was 429 nm (DMF).

Example 3

Embedded image 8.19 g of acetic anhydride and 2.04 g of cyanoacetic acid were stirred at 50 ° C. for 1 hour, then 2.28 g of 1- (2,3-dihydroxypropyl) pyridinium chloride and and N-ethyl-N-benzyl-4-amino. 5.74 g of benzaldehyde was added and heated to 90 ° C. After stirring at this temperature for 8 hours, the mixture was cooled to 60 ° C., and 3 g of water was added to decompose residual acetic anhydride, and the mixture was stirred for 2 hours. When cooled to room temperature, it contained 8.22 g of the cationic dye represented by the above structural formula. A thick liquid dye was obtained. This dyes paper and pulp in a vivid green-yellow color, and wastewater is hardly colored. The maximum absorption wavelength was 447 nm (DMF).

[0016]

The cationic dye obtained according to the present invention has a very high dyeing property to paper and pulp, and the dyeing wastewater contains almost no dye.

Claims (1)

[Claims] 1. A cationic dye represented by the following general formula (1): (In the formula, R ₁ and R ₂ represent an alkyl group or an aralkyl group, R ₃ represents a hydrogen or an alkyl group, and A ⁻ represents an anion.)