JPH04211457A - Trisazo compound and its use - Google Patents

Abstract

PURPOSE:To provide the subject new compound which is a black dye having excellent solubility, dyeing affinity, various fastnesses, etc., and useful as black ink, etc., for the dyeing of fibers having hydroxy group or amino group or for ink-jet recording. CONSTITUTION:A trisazo compound of formula I (Q1 and Q2 are phenyl or naphthyl ; m is 0 or 1). The compound can be produced by diazotizing 1- aminobenzene of formula II, etc., by conventional process, coupling the diazo compound in the form of a free acid to 1-amino-8-naphthol-4-sulfonic acid of formula III, etc., in an aqueous medium in acidic state, coupling the coupling reaction product with tetrazotized 4,4'-diaminobenzanilide-3'-sulfonic acid of formula IV in the form of a free acid and coupling the obtained disazo-diazo compound with a compound of formula V.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION This invention relates to trisazo compounds. More specifically, the present invention relates to a trisazo compound having a hydroxyl group or an amino group and useful for dyeing fibers, paper, leather, etc., and useful for inkjet inks.

0002

[Prior Art] Japanese Unexamined Patent Publication No. 61-51064 discloses, for example, the following formula:

0003

[C7]

The dye shown below is shown.

[0005]

[Problems to be Solved by the Invention] Conventionally, polyazo dyes based on benzidine and its derivatives have been used as direct dyes or acid dyes to dye fibers having hydroxyl groups or amide groups, or compositions and materials containing these. It was getting worse. However, benzidine is a prohibited substance, and benzidine derivatives such as orthotolidine and dianisidine are designated as specified chemical substances, and there are restrictions on their manufacture and use.

[0006] For this reason, various compounds have been proposed as non-benzidine dyes, but at present they do not meet the needs of consumers in terms of the performance required as dyes, and furthermore, The provision of improved compounds is highly desirable.

As a result of extensive studies, the present inventors have discovered a new compound that can broadly satisfy the requirements for dyes without using benzidine or benzidine derivatives, and have completed the present invention.

[0008]

[Means for Solving the Problems] The present invention provides the following general formula (I) in the form of a free acid:

[0009]

[Chemical formula 8]

The present invention provides a trisazo compound represented by the formula (wherein Q1 and Q2 are phenyl or naphthyl groups which may each independently have a substituent, and m represents 0 or 1).

Among the trisazo compounds of the present invention represented by the general formula (I), the following general formulas (II) and (I
The trisazo compounds represented by II) are particularly preferred.

0012

[Chemical formula 9]

(In the formula, Q1 and Q2 have the above meanings.)

[0014]

[Chemical formula 10]

(In the formula, m, Q1 and Q2 have the meanings given above.) In particular, in the form of the free acid, the following general formula (
Trisazo compounds represented by IV) are preferred.

[0016]

[Chemical formula 11]

(In the formula, Q1 and Q2 have the above-mentioned meanings.) In the general formula (I), when Q1 is a phenyl group which may have a substituent, the following formula

001
8]

[Chemical formula 12]

(wherein R1 and R2 are each independently hydrogen, nitro, sulfo, sulfamoyl, alkyl,
It represents an alkoxy, substituted or unsubstituted amino, carboxy or halogeno group. ) is preferable, and a phenyl group optionally substituted with nitro, sulfo, sulfamoyl, methyl, ethyl, methoxy, ethoxy, carboxy or chloro is particularly preferable.

In the general formula (I), when Q1 is a naphthyl group which may have a substituent, the following formula

00
21]

[Chemical formula 13]

A naphthyl group represented by the formula (wherein R3, R4 and R5 each independently represent hydrogen, hydroxy or sulfo group) is preferred.

In the general formula (I), when Q2 is a phenyl group which may have a substituent, it is substituted with one or two substituted or unsubstituted amino groups, and is further substituted with hydroxy, sulfo, alkyl , a phenyl group optionally substituted with an alkoxy or carboxy group, or 1 to 3
Preferred is a phenyl group which is substituted with one hydroxy group and may be further substituted with a substituted or unsubstituted amino, sulfo, alkyl, alkoxy or carboxy group. Examples of substituted amino groups include amino groups substituted with methyl, ethyl, hydroxyethyl, cyanoethyl, acetyl, or carbamoyl groups, and examples of alkyl and alkoxy include methyl, ethyl, methoxy, and ethoxy.

In the general formula (I), when Q2 is a naphthyl group which may have a substituent, it is substituted with one or two hydroxy groups, and is further substituted with sulfo, unsubstituted amino, acetyl, a naphthyl group optionally substituted with phenyl, sulfophenyl, disulfophenyl, benzoyl or methyl substituted amino, or with 1 or 2 unsubstituted amino or methyl, ethyl, hydroxyethyl, cyanoethyl, acetyl or carbamoyl substituted amino Preference is given to naphthyl groups which are substituted and may be further substituted with hydroxy or sulfo.

The compounds of the invention are in the free acid form or preferably as alkali metal salts, ammonium salts and organic amine salts. Examples include lithium salt, sodium salt, potassium salt, monoethanolamine salt, diethanolamine salt, and triethanolamine salt.

These trisazo compounds represented by the general formula (I) can be produced, for example, in the following manner. The following general formula (V) Q1 -NH2
(V) (In the formula, Q1 represents the above meaning.)
The compound represented by is diazotized by a conventional method to obtain the following general formula (VI) in the form of a free acid.

[0027]

[Chemical formula 14]

The compound represented by the formula (wherein m represents the above-mentioned meaning) is coupled with the compound represented by the following general formula ( VII)

[0029]

[Chemical formula 15]

A tetrazotized compound obtained by tetrazotizing the compound represented by the following formula (VIII) Q2 -H (V
A trisazo compound represented by general formula (I) can be obtained by coupling with a compound represented by III) (wherein Q2 represents the above-mentioned meaning).

[0031] As the compound represented by the general formula (V),
For example, 1-aminobenzene, 1-amino-2-, 3-
or 4-nitrobenzene, 1-amino-2-, 3- or 4-benzenesulfonic acid, 5-aminobenzene-1,3
-disulfonic acid, 6-aminobenzene-1,4-disulfonic acid, 4-aminobenzene-1,2-disulfonic acid,
1-Amino-2-, 3- or 4-sulfamoylbenzene, 1-amino-2-, 3- or 4-benzoic acid, 1-amino-2-, 3- or 4-chlorobenzene, 1-amino -2,5-dichlorobenzene, 1-amino-2-,3-
or 4-bromobenzene, 1-amino-2-, 3- or 4-methylbenzene, 1-amino-2-, 3- or 4-
Ethylbenzene, 1-amino-2-, 3- or 4-methoxybenzene, 1-amino-2-, 3- or 4-ethoxybenzene, 1,4-diaminobenzene-2-sulfonic acid, 4-di(β- hydroxyethyl)-1-amino-benzene, 1-aminonaphthalene-4-, 5-, 6-, 7
- or 8-sulfonic acid, 2-aminonaphthalene-1-,
8-, 7-, 6- or 5-sulfonic acid, 1-aminonaphthalene-4,7-, 4,6-, 3,7-, 3,8- or 3,6-disulfonic acid, 2-aminonaphthalene -4,8
-, 6,8-, 3,6-, 1,5- or 5,7-disulfonic acid, 1-aminonaphthalene-3,6,8-trisulfonic acid, 2-aminonaphthalene-3,6,8- or 4,
Examples include 6,8-trisulfonic acid.

Examples of the compound represented by the general formula (VI) include 1-amino-8-naphthol-4-sulfonic acid, 1-amino-8-naphthol-3,6- or 4,6-disulfonic acid. can be mentioned. Particularly preferred among these is 1-amino-8-naphthol-3,6-disulfonic acid.

Examples of the compound represented by the general formula (VII) include 4,4'-diaminobenzanilide-3'
-Sulfonic acid, 4,4'-diaminobenzanilide-2
'-Sulfonic acid is mentioned. Especially preferably,
4,4'-diaminobenzanilide-3'-sulfonic acid is mentioned.

Examples of the compound represented by the general formula (VIII) include aniline derivatives, phenol derivatives,
Examples include aminophenol derivatives, naphthol derivatives, naphthylamine sulfonic acid derivatives, naphthol sulfonic acid derivatives, and the like. Among them, 1-hydroxybenzene, 1-hydroxy-2-, 3- or 4-methylbenzene, 1,3-dihydroxybenzene, 1-hydroxy-3-methoxybenzene, 1-hydroxy-3-aminobenzene, 3 -di(β-hydroxyethyl)amino-
1-Hydroxybenzene, 1-di(β-hydroxyethyl)aminobenzene, 1,3-diamino-4-methylbenzene, 1-hydroxy-2-benzoic acid, 1,3-diaminobenzene-6-sulfonic acid, 1 -acetylamino-
4-methoxy-3-di(β-hydroxyethyl)aminobenzene, 3-diethylamino-1-hydroxybenzene, 1-hydroxynaphthalene, 1-hydroxynaphthalene-4-, 5- or 3-sulfonic acid, 1-hydroxynaphthalene -3,8- or 3,6-disulfonic acid, 1-
hydroxynaphthalene-3,6,8-trisulfonic acid,
2-hydroxynaphthalene, 2-hydroxynaphthalene-8-, 7- or 6-sulfonic acid, 2-hydroxynaphthalene-6,8- or 3,6-disulfonic acid, 2-amino-, methylamino-, ethylamino, acetylamino-, propylonylamino-, benzoylamino-, carbamoylamino-, sulfamoylamino- or phenylamino-8-hydroxynaphthalene-6-sulfonic acid, 3-amino-, methylamino-, ethylamino-, Propionylamino-, acetylamino-, benzoylamino-, carbamoylamino-, sulfamoylamino- or phenylamino-8-hydroxynaphthalene-6
-sulfonic acid, 1-amino- or acetylamino-8-
Hydroxynaphthalene-3,6-disulfonic acid, 1-amino- or acetylamino-8-hydroxynaphthalene-4,6-disulfonic acid, 1-amino-8-hydroxynaphthalene-2,4-disulfonic acid, 1,8- Examples include dihydroxynaphthalene-3,6-disulfonic acid.

The trisazo compounds of the present invention, alone or in the form of a mixture, are particularly useful for dyeing cellulose fibers such as rayon, cotton, paper, leather, silk and synthetic polyamides. Dyeing can be carried out by various methods such as exhaust dyeing and printing methods. The compounds of the present invention exhibit excellent performance in such dyeing and are generally useful as black dyes. In particular, it has good solubility and high dyeability, and can give deep black dyed products. Further, it has good build-up properties and is further characterized in that it provides dyed products with excellent fastness. Furthermore, the compounds of the present invention can provide stable liquid compositions, which are particularly suitable for dyeing rayon and paper, and are also suitable as inks, and can be applied, for example, to inkjet methods. In particular, the compound of the present invention has excellent solubility, has good ink storage stability, which has been a problem with conventional inkjet inks, does not clog nozzles due to precipitates, and has good ink characteristics. For example, it has the characteristic of forming a deep black image with excellent clarity, water resistance, and light resistance.

[0036]

EXAMPLES The present invention will be explained in detail with reference to Examples below. In the examples, parts mean parts by weight.

Example 1 9.3 parts of aniline is diazotized by a conventional method and coupled with 31.9 parts of 1-amino-8-naphthol-3,6-disulfonic acid at 0 to 5° C. under acidic conditions. Then 4
,4'-diaminobenzanilide-3'-sulfonic acid 3
A tetrazotized product obtained by tetrazotizing 0.7 part by a conventional method is injected, and coupling is carried out at 0 to 10° C. under neutral conditions. Next, 10.9 parts of 1-hydroxy-3-aminobenzene was added to complete the reaction, salted out and isolated by a conventional method, and the free acid was converted into the following structural formula:

[0038]

[Chemical formula 16]

A trisazo compound represented by (λmax = 605 nm, in an aqueous medium) was obtained.

Example 2 In place of the 1-hydroxy-3-aminobenzene used in Example 1, the compound in column 2 of the table below (general formula (V
Compound III) was synthesized in the same manner as in Example 1 to obtain corresponding trisazo compounds. In addition,
In the table, λmax is the value in an aqueous medium.

[0041]

[Table 1]

[0042]

[Table 2]

[0043]

[Table 3]

Example 3 Synthesis was performed in the same manner as in Example 1, using the compound in the second column of the table below (compound of general formula (V)) in place of the aniline used in Example 1, and the corresponding A trisazo compound was obtained. Note that λmax in the table is a value in an aqueous medium.

[0045]

[Table 4]

[0046]

[Table 5]

[0047]

[Table 6]

Example 4 In place of the aniline and 1-hydroxy-3-aminobenzene used in Example 1, the compound of general formula (V) used in Example 3 and the general formula used in Example 2 were used in order. By synthesizing in the same manner as in Example 1 using the compound (VIII), the corresponding trisazo compounds can be obtained.

Example 5 In place of 1-amino-8-naphthol-3,6-disulfonic acid and 4,4'-diaminobenzanilide-3'-sulfonic acid used in Example 1, 1-
It was synthesized in the same manner as in Example 1 using amino-8-naphthol-4,6-disulfonic acid and 4,4'-diaminobenzanilide-2'-sulfonic acid, and the following structural formula was obtained in the form of free acid.

[0050]

[Chemical formula 17]

A trisazo compound having the following formula (λmax = 610 nm, in an aqueous medium) was obtained.

Example 6 0.25 parts of the trisazo compound obtained in Example 1 was added to 2 parts of water.
5.0 parts of viscose rayon cotton yarn is immersed in a dye bath dissolved in 0.00 parts, and kept warm at 90°C for 10 minutes, then 0.25 parts of anhydrous sodium sulfate is added and dyed at the same temperature for 40 minutes. washing with water,
dry. The dyed product obtained had a black tone and excellent fastness.

Example 7 LBKP 20g/m beaten to CF400ml
0.5 parts of the trisazo compound obtained in Example 3 (No. 19) was added to 500 parts of the pulp solution, and after stirring for 10 minutes, Size Pine E (sizing agent, manufactured by Arakawa Chemical Industries) was added.
After 10 minutes, 0.3 part of crystalline aluminum sulfate was added, and stirring was continued for 20 minutes for dyeing. This is made into paper and dried. This made paper exhibited a black color tone and had excellent fastness.

Example 8 The following composition was heated to about 50° C., stirred and dissolved, and then filtered through a Teflon filter with a pore size of 0.45 μm to prepare an ink. Trisazo compound obtained in Example 1
5 parts ion exchange water
75 parts diethylene glycol
25 parts Sodium dehydroacetate
Using 0.05 parts of this ink, inkjet recording was performed on commercially available high-quality paper using a recording apparatus having an on-demand recording head that ejects ink using a piezo vibrator. The obtained image had good water resistance, light resistance, density, and clarity.

Example 9 In place of the aniline and 1-hydroxy-3-aminobenzene used in Example 1, the compound in column 2 of the table below (compound of general formula (V)) and the compound in column 3 of the table below (Compound of general formula (VIII)) was synthesized in the same manner as in Example 1 to obtain corresponding trisazo compounds. Note that λmax in the table is a value in an aqueous medium.

[0056]

[Table 7]

[0057]

[Table 8]

[0058]

[Table 9]

[0059]

[Table 10]

[0060]

[Table 11]

[0061]

[Table 12]

[0062]

[Table 13]

[0063]

[Table 14]

Example 10 An ink was prepared from the following composition in the same manner as in Example 8. Trisazo compound of Example 9 (No. 42)
3.0 parts triethylene glycol
5.5 parts polyethylene glycol #200
10.0 parts Sodium dehydroacetate
0.1 part ion exchange water

81.4 parts This ink was hermetically sealed in a glass container, and the quality was stable with no crystal precipitation even when it was left at 20°C for 6 months and at 50°C for 2 weeks.

Example 11 An ink was prepared from the following composition in the same manner as in Example 8. Trisazo compound of Example 9 (No. 62)
3.0 parts diethylene glycol
10.0 parts glycerin

3 parts Sodium dehydroacetate
0.1 part ion exchange water
83.9 parts Using this ink, inkjet recording was performed continuously in the same manner as in Example 8, and the recording was stable without clogging of the nozzles.

Claims (12)

[Claims] Claim 1: In the form of a free acid, the following general formula (I) [Formula 1] (wherein Q1 and Q2 are phenyl or naphthyl groups each independently optionally having a substituent, m is 0 or 1). 2. The trisazo according to claim 1, which is represented by the following general formula (II) in the form of a free acid: Compound. Claim 3: The following general formula (III) in the form of a free acid:
] where m, Q1 and Q2 have the meanings given in claim 1. ) The trisazo compound according to claim 1. 4. The trisazo according to claim 1, which is represented by the following general formula (IV) in the form of a free acid: Compound. Claim 5: Q1 is a compound of the following formula:
Represents a substituted or unsubstituted amino, carboxy or halogeno group. ) Claims 1 to 4 are phenyl groups represented by
The trisazo compound according to any one of. 6. Any one of claims 1 to 4, wherein Q1 is a naphthyl group represented by the following formula: (wherein R3, R4 and R5 each independently represent hydrogen, hydroxy or a sulfo group) A trisazo compound described in Crab. Claim 7: Q2 is a phenyl group substituted with 1 to 3 hydroxy groups and optionally substituted with a substituted or unsubstituted amino, sulfo, alkyl, alkoxy, or carboxy group. 6. The trisazo compound according to any one of 6. 8. Q2 is substituted with one or two substituted or unsubstituted amino groups, and furthermore, hydroxy, sulfo,
The trisazo compound according to any one of claims 1 to 6, which is a phenyl group optionally substituted with an alkyl, alkoxy, or carboxy group. 9. Claims 1 to 9, wherein Q2 is a naphthyl group substituted with one or two hydroxy groups and optionally substituted with a substituted or unsubstituted amino or sulfo group.
6. The trisazo compound according to any one of 6. Claim 10: Claim 1 wherein Q2 is a naphthyl group substituted with one or two substituted or unsubstituted amino groups and optionally substituted with a hydroxy or sulfo group.
7. The trisazo compound according to any one of . 11. A method for dyeing fibers or paper, which comprises using the trisazo compound according to any one of claims 1 to 10. 12. An ink containing the trisazo compound according to any one of claims 1 to 10.