JPS621036B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for dyeing cellulose fibers deep blue. More specifically, in the form of the free acid of the present invention, the following general formula () [In the formula, R is a hydrogen atom or _{a C1-4 alkyl} group, Y is a fluorine atom or a chlorine atom, n is 1, 2 or 3, and X is a 1-amino-8-hydroxynaphthalene mono- or disulfonic acid residue. represent Z is the formula −SO ₂ CH ₂ CH ₂ Cl, −SO ₂ CH=CH ₂ , −
SO ₂ CH ₂ CH ₂ OSO ₃ H, -SO ₂ CH ₂ CH ₂ OPO ₃ H ₂ or -N(R ₁ ) SO ₂ CH ₂ CH ₂ OSO ₃ H group (where R ₁
represents a hydrogen atom, methyl group or ethyl group)
represents a benzene ring or naphthalene ring residue which has the following and which may have other substituents. ] This is a method for dyeing cellulose fibers, which is characterized by using the dye shown below. It is already known that by coupling 2 moles of a benzene or naphthalene-based diazonium compound with 1 mole of 1-amino-8-naphtholsulfonic acids, a water-soluble dye that imparts a green to blue hue on textile materials can be obtained. There is. Among these dyes, dyes having a monohalogenotriazinyl group are well known as reactive dyes. However, these reactive dyes generally require high dyeing temperatures and lack suitability for exhaust dyeing, so they are only used for textile printing.Furthermore, they have the disadvantage of low acid stability of the dyed products obtained. Therefore, it could never be said to be sufficient for practical purposes. On the other hand, it is known that dyes having a β-sulfatoethylsulfonyl group can be applied to dyeing textile materials as so-called vinylsulfone type reactive dyes. However, dyed products using azo deep blue reactive dyes having a β-sulfatoethylsulfonyl group generally have low chlorine fastness, and fading due to chlorine contained in tap water is often a problem. For these reasons, the present inventors have found that the chlorine fastness is particularly excellent, and furthermore, the light fastness is sufficient.
As a result of extensive research in search of a deep blue vinyl sulfone type reactive dye that has sweat and sunlight fastness, we found that the dye represented by the general formula (), i.e., β-sulfatoethylsulfonyl group as the reactive group, We have found that disazo dyes containing monochloro or monofluorotriazinyl groups give deep blue dyeings that meet these conditions. It has also been found that the dye of the present invention can overcome the drawbacks of reactive dyes having monochloro or monofluorotriazinyl groups as described above. In the present invention, examples of cellulose fibers include natural or regenerated cellulose fibers such as cotton, linen, viscose human silk, and viscose cotton. In the case of the exhaust method, the dyeing of the present invention uses soda carbonate,
It is carried out at relatively low temperatures in a dye bath containing mirabilite or common salt in the presence of an acid binder such as tribasic sodium phosphate or caustic soda. In the case of printing, pastes such as, for example, sodium alginate, starch ethers or emulsifying pastes, and sodium carbonate, bicarbonate, caustic soda, tribasic sodium phosphate, sodium trichloroacetate or the corresponding potassium or alkaline earth compounds are used. applied to the fibers together with alkaline or alkali-releasing agents, optionally with the addition of customary printing aids or dispersants, such as urea, dried and heat treated, especially in the presence of water vapor. It can be dyed by applying it to. In the case of cold batch dyeing, caustic soda alone or in combination with sodium silicate, soda carbonate, or sodium phosphate is used as an acid binder, and if necessary, mirabilite or common salt is added, and if desired, a dissolving agent such as urea is used. Alternatively, it is padded onto the fibers at room temperature with the addition of a penetrant and rolled up into a roll.
After leaving it for an hour or overnight, it can be dyed by washing with water and drying. The dye of the present invention can be produced, for example, as follows. Metaphenylenediamine sulfonic acid and general formula () [In the formula, R and Z have the above-mentioned meanings] An amine represented by the general formula () [In the formula, Y has the above-mentioned meaning] Condensation with 2,4,6-trihalogeno-S-triazine represented by [In the formula, Z, R, and Y have the above-mentioned meanings] A diazonium compound obtained by diazotization by a conventional method and the general formula () (wherein, n has the above-mentioned meaning) A diazonium compound obtained by diazotizing a naphthylamine sulfonic acid compound represented by It can be obtained by coupling in any order with 1-amino-8-hydroxynaphthalene mono- or disulfonic acid represented by 1-Aminobenzene-2-, -3- or -4
-β-sulfatoethylsulfone, 1-aminobenzene-3-β-phosphatoethylsulfone, 1
-amino-4-methylbenzene-3-β-sulfatoethylsulfone, 1-aminobenzene-3-
β-chloroethylsulfone, 1-amino-4-methoxybenzene-3-β-sulfatoethylsulfone, 1-aminobenzene-4-β-sulfatoethylsulfone-2-sulfonic acid, 1-aminobenzene- 5-β-sulfatoethylsulfone-2
-sulfonic acid, 1-aminobenzene-5-β-sulfatoethylsulfone-2,4-disulfonic acid, 1-aminonaphthalene-4-β-sulfatoethylsulfone, 1-amino-2,5-dimethoxy Benzene-4-β-sulfatoethylsulfone, 1-aminobenzene-4-β-sulfatoethylsulfone-2-carboxylic acid, 1-aminobenzene-5-β-sulfatoethylsulfone-2-
Carboxylic acid, 1-amino-2-methoxybenzene-4-β-sulfatoethylsulfone, 1-amino-2-chlorobenzene-4-β-sulfatoethylsulfone, 1-amino-2-methoxybenzene- 5-β-sulfatoethylsulfone, 2-aminonaphthalene-8-β-sulfatoethylsulfone, 2-aminonaphthalene-8-β-sulfatoethylsulfone-6-sulfonic acid, 1-amino-2・5-dimethoxybenzene-4-vinylsulfone, 1-amino-2-methoxy-5-methylbenzene-4-β-sulfatoethylsulfone, 1
-amyl-2,5-diethoxybenzene-4-β
-sulfatoethylsulfone, 1-amino-2-
Bromobenzene-4-β-sulfatoethylsulfone, 1-amino-2-bromobenzene-4-vinylsulfone, 1-aminobenzene-5-vinylsulfone-2,4-disulfonic acid, 1-aminobenzene-5 -β-Phosphatoethylsulfone-
2,4-disulfonic acid, 1-aminobenzene-5
-β-chloroethylsulfone-2,4-disulfonic acid, 2-aminonaphthalene-8-β-phosphatoethylsulfone-6-sulfonic acid, 2-aminonaphthalene-8-vinylsulfone-6-sulfonic acid, 1- Amino-2-methoxy-5-methylbenzene-4-β-chloroethylsulfone, 2-aminophenol-4-β-sulfatoethylsulfone, 1-aminobenzene-3- or -4-vinylsulfone, 1- Amino-2-hydroxybenzene-4-β-sulfatoethylsulfone, 1-aminobenzene-5-vinylsulfone-2-sulfonic acid, 3-(N-methyl-β-sulfatoethylsulfonylamino)-1 -Aminobenzene, 3-
(N-ethyl-β-sulfatoethylsulfonylamino)-1-aminobenzene, 3-β-sulfatoethylsulfonylamino-1-aminobenzene. 1-(N-methyl or ethylamino)benzene-2,3 or 4-β-sulfatoethylsulfone, 1-(N-methylamino)benzene-3
-β-phosphate ethyl sulfone, 1-(N-
Methylamino)-4-methoxybenzene-3-β
-Sulfatoethylsulfone, 1-(N-methylamino)naphthalene-4-β-sulfatoethylsulfone, 2-(N-methylamino)naphthalene-8-β-sulfatoethylsulfone, 1
-(N-ethylamino)benzene-3-β-phosphatoethylsulfone, 1-(N-ethylamino)-4-methoxybenzene-3-β-sulfatoethylsulfone, 1-(N-ethylamino)
Naphthalene-4-β-sulfatoethylsulfone, 2-(N-ethylamino)naphthalene-8-
β-sulfate ethyl sulfone. Examples of the naphthylamine sulfonic acid compound represented by the general formula () include 1-aminonaphthalene-2, 3, 4, 5, 6, or 7-sulfonic acid;
1-aminonaphthalene-2, 4-, 2, 5-,
2.6-, 2.7-, 3.5-, 3.6-, 3.
7-, 4.6-, 4.7- or 5.7-disulfonic acid, 1-aminonaphthalene-2.4.6-,
2, 4, 7- or 3, 5, 7-trisulfonic acid, 2-aminonaphthalene-1, 3, 4, 5,
6, 7 or 8-sulfonic acid, 2aminonaphthalene-1,4-,1,5-,1,6-,1,7-,
3・5-, 3・6-, 3・7-, 3・8-, 4・
6-, 4.7-, 4.8-, 5.7-, 5.8-
or 6,8-disulfonic acid, 2-aminonaphthalene-1,4,6-, 1,4,7-, 3,5,7
-, 3.5.8-, 3.6.8- or 4.6.
8-trisulfonic acid is mentioned. Examples of the 1-amino-8-hydroxynaphthalene mono- or disulfonic acid represented by the general formula () include 1-amino-8-hydroxynaphthalene-3, 4, 5 or 6-sulfonic acid, 1-amino-8-hydroxy Examples include naphthalene-3,6- or 4,6-disulfonic acid. The thus obtained dye of the present invention can be dyed even at a lower dyeing temperature or at a higher dyeing temperature than the conventional azo deep blue reactive dye having a β-sulfatoethylsulfonyl group. A dyed product with almost constant color density can be obtained regardless of temperature. That is, the reproducibility of staining is excellent. Furthermore, the dye of the present invention has excellent level dyeing properties, in particular, does not bleed to washing liquids containing oxidizing agents, and is also excellent in chlorine fastness, light fastness, and sweat/sunlight fastness. Furthermore, since the dye of the present invention exhibits a high exhaustion rate, it is possible not only to obtain dyed products with high density, but also to have an advantage in terms of wastewater treatment since only a small amount of dye remains in the dye bath. has advantages. In addition, the dyed material using the dye of the present invention can be discharged in white, and excellent white areas can be reproduced. Among the dyes of the present invention, those in which the amino group is at the β position in the general formula () are particularly preferred in terms of color density. As a dye similar to the dye of the present invention, for example, Japanese Patent Laid-Open No. 52-98026 discloses The dye shown is described. However, the acid stability of dyed products obtained using this dye (the test method is to immerse the dyed fabric in 1% acetic acid for 30 minutes,
at a temperature of 37 ± 2 °C using a bar spirometer.
(treated at 125 g/cm ² for 6 hours) is inferior to the dye-dyed products of the present invention, and also has the disadvantages of requiring a high dyeing temperature and lacking in exhaustion dyeing suitability. Its practical value is small. Next, the method of the present invention will be explained with reference to examples. In the text, parts represent parts by weight. Example 1 Formula (1) in free acid form (λmax = 593 nm, however, in an aqueous solvent, hereinafter measured under the same conditions) Dissolve 0.3 part of the dye shown in 200 parts of water to obtain 20%
1 part, add 10 parts of cotton, and raise the temperature to 50℃. After 30 minutes, 4 parts of soda carbonate is added and dyed at the same temperature for 1 hour. After dyeing, washing with water and soaping were performed to obtain a deep blue dyed product with excellent chlorine, light, sweat and sunlight fastness. Reference Example 1 [Synthesis example of dye (1) of Example 1] 2-aminonaphthalene-1,5-disulfonic acid
Add 7.58 parts, 160 parts of water, 40 parts of ice and 3.7 parts of concentrated hydrochloric acid,
Diazotization is carried out by injecting 5.1 parts of 35% sodium nitrite solution at 0-5°C. After eliminating excess nitrite, 1-amino-8-hydroxynaphthalene
A neutral solution of 7.73 parts of 3,6-disulfonic acid from 0 to 10
It takes about 1 hour to inject at ℃ and couple at pH 1.0 to 2.0. After stirring this mixture for several hours,
Neutralize with caustic soda solution to pH 7 and salt out with sodium chloride at 30-35°C to obtain a monoazo dye. On the other hand, 4.61 parts of cyanuric chloride and 4.70 parts of m-phenylenediaminesulfonic acid were brought to pH 1.5 to 3.0 in 50 parts of an aqueous surfactant solution by keeping the temperature at 0 to 5°C for 1 to 2 hours to carry out the first condensation. A second condensation is carried out by adding 6.95 parts of 1-aminobenzene-3-β-sulfatoethylsulfone to the mixture and stirring overnight at 25 to 30°C while maintaining the pH at 5 to 5.5 with a 20% sodium carbonate solution. Then, after adding 50 parts of ice and 7.1 parts of concentrated hydrochloric acid,
Diazotization is carried out by adding 5.3 parts of % sodium nitrite solution. The diazotized solution from which excess nitrous acid has been removed is poured into a monoazo dye suspension made alkaline with sodium bicarbonate at 5 to 10°C, and the suspension is stirred for 1 to 2 hours to perform coupling. After adjusting the pH to 5.5 to 6.0 and the temperature to 50 to 55°C with dilute sulfuric acid, add sodium chloride to this solution to salt out, filter, wash, and dry at 60°C. 38.5 parts of dye (1) were obtained. Examples 2-18 In Example 1, instead of dye (1), the following (2)-
Dyeing was carried out in the same manner except that the dye (18) was used. A deep blue, intense dyeing with excellent fastness properties was obtained. The following dyes are Column A: 1-amino-8-hydroxynaphthalene mono- or disulfonic acid [compound of the above general formula ()] Column B: Diazo component of monoazo dye [compound of the above general formula ()] Column C: Disazo dye Amine constituting the diazo component [compound of the above general formula ()] [compound of the above general formula ()] Column D: 2,4,6-trihalogeno-S-triazine [compound of the above general formula ()] Column E : Characterized by the λmax of the disazo dye solution.

【table】

[Table] Example 19 Formula (19) in free acid form Dissolve 0.3 parts of the dye shown in 200 parts of water and add 20 parts of mirabilite.
1 part, add 10 parts of cotton, and raise the temperature to 50℃. After 30 minutes, 4 parts of soda carbonate is added and dyed at the same temperature for 1 hour. After dyeing, washing with water and soaping were performed to obtain a deep blue dye with high concentration and excellent fastness to chlorine, light, sweat, and sunlight. Reference Example 2 [Synthesis example of dye (19) of Example 19] Except for reversing the coupling order of two types of diazonium compounds to 1-amino-8-naphthalene-3,6-disulfonic acid in Reference Example 1. It was synthesized in the same manner. Examples 20 to 35 Dyeing was carried out in the same manner as in Example 19 except that the following dyes (20) to (35) were used instead of dye (19). A deep blue, intense dyeing with excellent fastness properties was obtained. The dyes listed below are characterized by: Column A: 1-amino-8-hydroxy mono- or disulfonic acid Column B: Amine constituting the diazo component of the monoazo dye [compound of the above general formula ()] [compound of the above general formula ()] Column C: 2.4・6-Trihalogeno-S-triazine [Compound of the above general formula ()] Column D: Diazo component of the disazo dye [Compound of the above general formula ()] Column E: λmax of the disazo dye solution

【table】

【table】

Claims (1)

[Claims] 1 The following general formula in the form of a free acid: [Wherein, R is a hydrogen atom or a C _1-4 alkyl group,
Y represents a fluorine atom or a chlorine atom, n represents 1, 2 or 3, and X represents a 1-amino-8-hydroxynaphthalene mono- or disulfonic acid residue. Z is the formula −
SO ₂ CH ₂ CH ₂ Cl, −SO ₂ CH=CH ₂ , −
SO ₂ CH ₂ CH ₂ OSO ₃ H, -SO ₂ CH ₂ CH ₂ OPO ₃ H ₂ or -N(R ₁ )SO ₂ CH ₂ -CH ₂ OSO ₃ H group (here
R ₁ represents a hydrogen atom, a methyl group, or an ethyl group), and represents a benzene ring or naphthalene ring residue which may also have a substituent. ] A method for dyeing cellulose fibers, characterized by using the dye shown below.