JP2002348492A - Novel cationic dye - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cationic dye which excels in dyeing speed and degree of exhaustion and which gives a dyed product having superior fastness to light and humidity. SOLUTION: The novel cationic dye is represented by general formula (1) D-(R<0> )n (1) [wherein n is 1, 2 or 3; D is a coloring matter matrix selected from azo, anthraquinone and phthalocyanine coloring matters; R<0> is an aminoethylsulfonylphenyl group represented by general formula (2) (wherein R<a> and R<b> are independently of each other a hydrogen, halogen, 1-3C alkyl, and 1-3C alkoxy, and R<1a> and R<1b> are independently of each other a 1-4C alkyl, 1-3C hydroxyalkyl and aminoalkyl); and R<0> may be identical or different if n is 2 or 3].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel cationic dye, and more particularly, to a cationic dye in which an aminoethylsulfonylphenyl group is introduced into a dye matrix and which has excellent dyeing rate and fastness.

[0002]

2. Description of the Related Art Various natural and synthetic dyes have hitherto been used.
It is used for dyeing various fiber materials, leather, paper, pulp and the like. As these dyes, azo dyes having an azo bond as a dye matrix, quinone dyes such as naphthoquinone and anthraquinone having a quinoid structure as a dye matrix, and phthalocyanine dyes having a phthalocyanine structure as a dye matrix are frequently used.

[0003]

These commonly used dyes have a certain level of dyeing properties such as dyeing speed and dyeing rate, light fastness and wet fastness.
Zero residual amount in dyeing wastewater, that is, 1
It is extremely difficult to achieve 00%, and they are extremely difficult to decompose, which imposes a heavy burden on wastewater treatment.

On the other hand, in the dyeing industry, there is a demand for rationalization such as a reduction in dyeing time and a reduction in wastewater treatment load, and the dyeing speed and dyeing rate are high, and the color fastness of the dyed material is good. The development of dyes is eagerly awaited. In particular, paper,
In pulp dyeing, from the viewpoint of paper preservability, corrosiveness of equipment and equipment, wastewater treatment, etc., from the acidic papermaking method using aluminum sulfate for fixing dyes and sizing agents, to neutral papermaking without using aluminum sulfate The transition to law has progressed rapidly and is now becoming mainstream. However, in the neutral papermaking method, a conventional dye has a low dyeing rate and a low dyeing rate, so that it is difficult to obtain a high-concentration dyed product. In addition, the escape of the dye into the wastewater is increased. In addition, these dyes have an unexpectedly low dyeing rate to bleached pulp, and a large amount of undyed dye remains in the dyeing wastewater. Furthermore, in the dyeing of other materials, for example, when dyeing wool, silk, leather, cotton, etc. with a conventional anionic dye such as a direct dye or an acidic dye alone in a dark color, the dyeing rate is naturally limited. If dyeing is carried out beyond the saturation dyeing, a large amount of undyed dye in wastewater will be present, and it will be difficult to carry out dark color dyeing.

[0005] The present invention has a high dyeing speed especially on paper and pulp, and has a high dyeing ratio, and can achieve rationalization such as shortening of dyeing time and load of wastewater treatment, and direct dye. Good dyeing properties that quickly produce salt even on materials dyed with anionic dyes such as dyes and acid dyes, and produce dyeings with high density, high gloss, and excellent wet fastness and light fastness. And a novel cationic dye having fastness.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that a dye matrix selected from the group consisting of azo dyes, anthraquinone dyes and phthalocyanine dyes has an aminoethylsulfonylphenyl group. Has been found to have a high dyeing rate on paper and pulp, and a high dyeing rate, and have excellent light fastness and wet fastness of the dyed product, and include direct dyes and acid dyes. Material dyed with an anionic dye, such as wool,
Even when used for topping (overlaying) dyeing of silk, leather, cotton, etc., it quickly forms a salt with an anionic dye with a small amount of use, and has a much higher concentration and high gloss than the case of dyeing with an anionic dye alone. In addition, they have found that a dyed article having excellent light fastness and wet fastness can be obtained, and thus the present invention has been completed.

The present invention relates to a compound represented by the following general formula (1): D- (R ⁰ ) _n (1) wherein n is 1, 2 or 3, and D is an azo dye, anthraquinone dye and phthalocyanine dye And R ⁰ represents the following general formula (2):

Embedded image [Wherein, R ^a and R ^b each independently represent hydrogen, halogen, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and R ^1a and R ^1b each independently represent hydrogen. An alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, a formula

Embedded image (Where Z ^a represents an alkylene group having 1 to 4 carbon atoms, R ^2a and R ^2b each independently represent hydrogen, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms). Represents an aminoethylsulfonylphenyl group represented by the following formula: wherein n is 2 or 3, each of R ⁰ may be the same or different.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the cationic dye of the present invention, in the general formula (1), D has at least one azo (-N = N-) bond in an atomic group constituting the dye compound. A dye base selected from the group consisting of an azo dye, an anthraquinone dye having an atomic group having a quinoid structure, and a phthalocyanine dye having an atomic group having a phthalocyanine structure.

In the above-mentioned general formula (1) of the azo dye compound, D
Can be represented by the formula X (-N = N-) _p (where X represents a skeleton of the pigment base and p is an integer of 1 to 5), and -N = The N-bond can be at the end of the backbone X, within the backbone X, or both.

Examples of the compound capable of constituting the skeleton X of the azo dye compound include a couple component represented by the following general formulas (3) to (10), a naphthol AS genus dip and a compound having a similar structure. be able to.

[0011]

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In the general formula (3), R ⁵ represents an amino group or a hydroxy group, and R ⁶ represents a hydroxy group, having 1 carbon atom.
Alkoxy or -NHR ¹⁰ (wherein the R ¹⁰ is hydrogen, an alkyl group having 1 to 3 carbon atoms, an acetyl group, a carbonyl group, a benzoyl group) of to 3 represent, R ⁷ is of 1 to 3 carbon atoms An alkyl group, an alkoxy group having 1 to 3 carbon atoms,
Represents a hydroxy group, a carboxy group, a nitro group, and a halogen group.

The above general formulas (4), (6) and (7)
In the formula, each of R ⁸ represents hydrogen, an alkyl group having 1 to 3 carbon atoms, an acetyl group or a carbonylamino group, and R ⁹ in the general formula (4) represents hydrogen or a hydroxy group.

[0014] In the general formula (5), Z ^b is a single bond (-), - CO- or an alkylene group.

In the above general formulas (9) and (10), R ³
Each represents hydrogen, an alkyl group having 1 to 3 carbon atoms, a carbonyl group or a carbomethyl group, and each of R ^4a and R ^4b independently represents hydrogen, a halogen, an alkyl group having 1 to 3 carbon atoms or a 1 to 1 carbon atom. 3 represents an alkoxy group.

In the above general formulas (6) and (7), Y is a group represented by the following formula (a) or (b).

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In the above formula (a), R ¹¹ and R ¹² independently represent a halogen, a hydroxy group, a carboxy group, an alkyl group, an alkoxy group or a nitro group.
R ¹¹ is the same as in (a), and each of ^13a and R ^13b independently represents hydrogen or an alkyl group having 1 to 3 carbon atoms.

In the general formula (1), as an anthraquinone dye compound which can constitute a dye matrix represented by D,
Examples thereof include 4-diaminoanthraquinone-2-sulfonic acid. Further, copper phthalocyanine and the like can be exemplified as the phthalocyanine dye compound.

As the aminoethylsulfonylphenyl group introduced into the dye matrix, R ^1a in the above formula (2)
And R ^1b is preferably a methyl group, an ethyl group, a hydroxyethyl group, an aminoalkyl group, preferred aminoalkyl groups Z ^a is ethylene in the formula (dimethylene), propylene (trimethylene), R ^2a and R ^2b Is a methyl group or an ethyl group. R ^a and R ^b are preferably a methyl group or a methoxy group.

The cationic dye compound represented by the general formula (1) of the present invention can be easily produced by a known method. The azo dye compound is, for example, represented by the following general formula (1)
1)

Embedded image (Wherein, R ^a , R ^b , R ^1a and R ^1b represent the same meaning as defined above) by diazotization of the amine by a known method, and then the above-mentioned general formulas (3) to (9) And a compound capable of constituting the skeleton X of the azo dye compound represented by the formula (1) by a known coupling reaction. Further, an amine of a compound capable of constituting the skeleton X of the azo dye compound containing a sulfatoethylsulfonyl group is diazotized, and then the compound is bonded to the compound represented by any one of the general formulas (3) to (9) by a known coupling reaction. Then, it can also be produced by binding with various alkylamines such as ethylamine, diethylamine or diethylaminoethylamine, and treating it by a known method.

The anthraquinone dye compound can be produced by binding various alkylamines such as ethylamine, diethylamine or diethylaminoethylamine to the sulfatoethylsulfonyl group of an anthraquinone derivative containing a sulfatoethylsulfonyl group. Further, the phthalocyanine dye compound can be easily produced by directly bonding the amine represented by the general formula (11) to the sulfonic acid group introduced into the phthalocyanine derivative.

Table 1 shows specific examples of the cationic dye compound represented by the general formula (1) of the present invention and their hues.

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

[Table 3]

[0026]

[Table 4]

The cationic dye compound of the present invention can be dried to be in a powdery or granular form, but is preferably in a concentrated liquid form dissolved in an organic acid and / or a water-soluble organic solvent. .

Examples of the organic acid include formic acid, acetic acid, lactic acid, citric acid, glycolic acid, methanesulfonic acid and the like. Examples of the water-soluble organic solvent include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, methyl cellosolve, carbitol, methyl carbitol, ethylene glycol dimethyl ether, and ethylene glycol monoethylene. Butyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, thioglycol, butyl lactone,
N-methyl-2-pyrrolidone, dimethylformamide, formamide, dimethylacetamide and the like can be mentioned.
These organic acids and water-soluble solvents are preferably used as a mixture of two or more.

[0029]

EXAMPLES The present invention will be described in more detail with reference to Examples. In the examples, “parts” and “%” are based on weight unless otherwise specified.

Example 1 Azo Dye Compound No. 3 4- (β-sulfatoethylsulfonyl) aniline 28.
One part was dissolved in 100 parts of water, and 28.0 ml of 2'-dimethylaminoethyl-2-diethylaminoethylamine was stirred.
Then, 4.0 parts of sodium hydroxide was added, and the mixture was reacted at 70 ° C. for 1 hour. After completion of the reaction, the reaction mixture was cooled to room temperature, and the precipitated product was separated by filtration, and in the general formula (11),
An amine of the following formula (12) in which R ^2a is —C ₂ H ₄ N (C ₂ H ₅ ) ₂ and R ^2b is —C ₂ H ₄ N (CH ₃ ) ₂ is obtained.

Embedded image

The obtained amine (37.0 parts) was sufficiently stirred with 150 parts of water and 32.0 parts of concentrated hydrochloric acid, and then diazotized at 5 to 10 ° C. using 25.0 parts of 4N sodium nitrite. Phenylenediamine-4-sulfonic acid 1
8.8 parts and 4.0 parts of sodium hydroxide were added to a coupling component dissolved in 100 parts of water while maintaining the temperature at 10 ° C. or lower. The pH is adjusted to 5.0 with an aqueous sodium hydroxide solution to complete the coupling reaction. After the reaction is completed, salting out is performed using 50 parts of sodium chloride, and the precipitated product is separated by filtration, dried, and dried according to the following formula (13). Compound number 3 represented by
An azo dye compound was obtained.

Embedded image

The azo dye compound obtained was readily soluble in water and dyed paper reddish yellow. This dyed product exhibited good light fastness and wet fastness, and was excellent in build-up properties in dyeing neutral papermaking, and no coloring of wastewater was observed.

Example 2 Azo Dye Compound No. 9 4- (β-sulfatoethylsulfonyl) aniline 28.
One part was thoroughly stirred with 100 parts of water and 20.0 parts of concentrated hydrochloric acid, and then 5 to 10 ° C using 25 parts of 4N sodium nitrite.
And then 2-amino-8-naphthol-6
23.9 parts of sulfonic acid and 5.3 parts of sodium carbonate are added to a solution of 150 parts of water. The pH was adjusted to 4.0 with an aqueous sodium carbonate solution to complete the coupling reaction.

The reaction solution was added with 2,2'-iminobis (N, N
20.7 parts of -dimethylethylamine) were added dropwise with stirring.
6.0 parts of sodium hydroxide was added and reacted at 70 ° C. for 1 hour. After the reaction solution was cooled to room temperature, 50.0 parts of sodium chloride was added for salting out, and the precipitated product was separated by filtration.
130 parts of a cake of the azo dye compound of compound No. 9 represented by the following formula (14) was obtained.

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To 130 parts of the obtained dye compound cake, 150 parts of acetic acid and 120 parts of water were added to obtain a concentrated solution containing 15% of the dye compound. This dye stains the paper a little bluish red. This dyed product exhibited good light fastness and wet fastness, and was excellent in build-up properties in dyeing neutral papermaking, and no coloring of wastewater was observed.

Example 3 Anthraquine Dye Compound No. 12 Vinyl Sulfone Reactive Dye (CI Reactive Blue 19)
60.3 parts are dissolved in 500 parts of water, and 2'-dimethylaminoethyl-3-dimethylaminopropylamine is 26.1.
Then, 4.0 parts of sodium hydroxide was added, and the mixture was reacted at 60 ° C. for 1 hour. After cooling the reaction solution to room temperature, the precipitated product was separated by filtration to obtain 98 parts of a wet cake.

To 98 parts of the obtained wet cake, 180 parts of acetic acid and 172 parts of water were added to obtain a concentrated solution containing 15% of an anthraquinone dye compound of the compound No. 12 represented by the following formula (15).

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The dye obtained dyes the paper in vivid blue. This dyed product exhibited good light fastness and wet fastness, and was excellent in build-up properties in dyeing neutral papermaking, and no coloring of wastewater was observed.

Example 4 Sodium salt of the azo dye compound of Compound No. 15 4- (β-sulfatoethylsulfonyl) aniline 28.
One part was thoroughly stirred with 100 parts of water and 20.0 parts of concentrated hydrochloric acid, and then 5 to 10 ° C using 25 parts of 4N sodium nitrite.
With 1-amino-8-naphthol-
34.1 parts of 3,6-sulfonic acid monosodium salt was added, and the mixture was adjusted to pH 2 and reacted at 10 to 15 ° C. for 3 hours to complete the coupling reaction.

The reaction mixture was added with 2,2'-iminobis (N, N-
(Dimethylamine) 20.7 parts and sodium hydroxide 8.
0 part was added and reacted at 70 ° C. for 1 hour.
A solution of the azo dye compound represented by 6) was obtained.

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33.7 parts of 4- (β-sulfatoethylsulfonyl) aniline are dissolved in 100 parts of water, 13.0 parts of a 50% aqueous solution of dimethylamine are added dropwise with stirring, and 5.0 parts of sodium hydroxide are further added. Was added and reacted at 60 ° C. for 1 hour. The reaction solution was cooled to room temperature, and the precipitated crystals were separated by filtration to obtain 45.0 parts of a wet cake of an amine of the following formula (17) in which both R ^1a and R ^1b in the general formula (11) are methyl groups.

Embedded image

35.0 parts of concentrated hydrochloric acid was added to 45.0 parts of the obtained wet cake of amine, and the mixture was sufficiently stirred, and then diazotized at 5 to 10 ° C. using 25.0 parts of 4N-sodium nitrite. Next, the diazotized product was dropped into the previously obtained azo dye compound solution over 1 hour, and adjusted to 10 to 15 while maintaining the pH at 9 using a 10% aqueous sodium hydroxide solution.
Coupling at ° C. After the completion of the coupling reaction, the precipitated product was separated by filtration to obtain 160 parts of a wet cake of a sodium salt of an azo dye compound of Compound No. 15 represented by the following formula (18).

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280 parts of acetic acid and 200 parts of water were added to 160 parts of the obtained wet cake to prepare a concentrated solution containing 15% of the above dye compound. The resulting dye dyes the paper in a clear bluish black. This dyed product exhibited good light fastness and wet fastness, and was excellent in build-up properties in dyeing neutral papermaking, and no coloring of wastewater was observed.

Dyeing Example 1 LBKP: NBKP (= 50: 50) having a beating degree of 25 ° SR
Of a 10% aqueous solution of the azo dye compound of Compound No. 3 obtained in Example 1 was added to a pulp slurry containing 500 parts of pulp (dry weight: 100 parts) and 3,000 parts of water, and stirred well for 5 minutes. Then, an aqueous solution of sodium carbonate is added to adjust the pH.
The value was adjusted to 7.0.

To this slurry was added 0.5 part of cationic starch (CATOF, manufactured by Oji National Co., Ltd.), and the mixture was stirred for 5 minutes. Then, an alkyl ketene dimer sizing agent (Harcon 40) was added.
B, manufactured by Dick Hercules Co., Ltd.) (0.1 parts (in terms of solid content)), and the mixture was further stirred for 10 minutes. More water 65
The mixture was diluted by adding 00 parts, and paper was made according to a conventional method. No coloring of the papermaking wastewater was observed, and the resulting dyed paper was a slightly reddish yellow with a color value, and had good sunlight fastness and wet fastness.

Dyeing Example 2 15.0 parts of chrome-tanned pig leather (7.5 parts by dry weight,
100 mm (w) x 200 mm (L) x 0.8 mm (t)) is placed in a rotary dyeing tank (cylindrical shape having an inner diameter of 200 mmφ and a height of 60 mmh). The washing operation of rotating for 10 minutes was performed twice to thoroughly wash the pig leather with water.

The washed pig leather is taken out of the dyeing tank,
Once again, put it in the same type of rotating dyeing tank, and use the direct dye (CI D
irect Black 169) Inject 4.5 parts of 10% solution and 40 ℃
For 30 minutes. Subsequently, 1.1 parts of a fatliquoring agent (Shincholine L, manufactured by Yoshikawa Oil Co., Ltd.) was added, and further added at 40 ° C.
After the addition of 0.2 part of formic acid, the mixture was rotated for 20 minutes to fix the dye. The dyed pig leather was taken out and washed with 38.0 parts of water at 40 ° C. for 10 minutes in the rotary dyeing tank.

Next, the pig leather was taken out and placed again in a rotary dyeing tank of the same type as the dyeing tank, and 23.0 parts of water and a black dye of sodium salt of the azo dye of compound No. 15 obtained in Example 4 were used. Inject 3.5 parts of a 10% aqueous solution of the concentrated solution, rotate at 40 ° C. for 20 minutes to dye, then add 0.04 parts of formic acid and rotate for another 20 minutes to fix the dye. (Overhang dyeing). The pig leather was taken out of the dyeing tank, washed with water in the same manner as described above, and air-dried for 15 hours.

This dyed pig leather is dyed in black at a much higher concentration than the pig leather dyed using only direct dyes or acid dyes, and the dye bleeds (color transfer to other materials).
There was no wet fastness and no sunlight fastness. No coloring of the topping dye waste liquid was observed.

[0050]

The cationic dye of the present invention has an extremely high dyeing speed, dyeing rate and dyeing density on a substrate, and the dyed product and the dyed substrate obtained using them have excellent light fastness and wet fastness. Having.

Further, since the dyeing waste liquid using the cationic dye of the present invention is colorless without coloration, it does not impose an excessive load on the treatment of the waste liquid, so that the dyeing process can be streamlined and the environmental preservation is great. Has advantages. The present invention provides a novel cationic dye, and its industrial significance is extremely large, particularly in the field of dyes and dyeing.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09B 62/517 C09B 62/517 // D06P 1/384 D06P 1/384 3/32 3/32 B

Claims (1)

[Claims] 1. The following general formula (1): D- (R ⁰ ) _n (1) wherein n is 1, 2 or 3, and D is selected from the group consisting of azo dyes, anthraquinone dyes and phthalocyanine dyes R ⁰ represents the following general formula (2): [Wherein, R ^a and R ^b each independently represent hydrogen, halogen, an alkyl group having 1 to 3 carbon atoms, or an alkoxy group having 1 to 3 carbon atoms, and R ^1a and R ^1b each independently represent hydrogen. An alkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, and a compound represented by the formula: (Where Z ^a represents an alkylene group having 1 to 4 carbon atoms, R ^2a and R ^2b each independently represent hydrogen, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group having 1 to 3 carbon atoms). Wherein, when n is 2 or 3, each of R ⁰ may be the same or different.].