KR101154986B1 - Composition of reactive blue dyes - Google Patents

Abstract

(Ⅰ)
상기식에서 R₁, R₂, R₃는 각각 독립적으로 수소, 메틸, 에틸, 페닐, 할로겐, 메톡시, 에톡시, 하이드록시, 우레이도, 설포, 메틸아미노, 에틸아미노, 설파모일, 카르복시기이고 Me는 금속이온, Y는 할로겐원자, Q는 비닐설폰기 또는 일반식 -SO₂CH₂CH₂-L 로서 , L은 알칼리성 조건하에 분리될 수 있는 그룹으로. -Cl, -Br, -F, -OSO₃H, -SSO₃H, -OCOCH₃, -OPO₃H₂, -OCO-C₆H₅ 또는 -OSO₂-C₁~C₄ 알킬 이다.
A는

또는

이다.

(Ⅲ)
상기식에서 R₄, R₅, R₆, R₇ 은 서로 독립적으로 수소, 메틸, 에틸, 페닐, 할로겐, 메톡시, 에톡시, 하이드록시, 우레이도, 설포, 메틸아미노, 에틸아미노, 설파모일, 카르복시기이고 Me는 금속이온, Y는 할로겐원자, Q는 비닐설폰기 또는 일반식 -SO₂CH₂CH₂-L 로서 , L은 알칼리성 조건하에 분리될 수 있는 그룹으로. -Cl, -Br, -F, -OSO₃H, -SSO₃H, -OCOCH₃, -OPO₃H₂, -OCO-C₆H₅ 또는 -OSO₂-C₁~C₄ 알킬 이다.
A는

또는

이다.
본 발명의 염료조성물은 높은 세탁견뢰도를 갖는다.The present invention relates to a blue dye composition obtained by mixing 50 to 70% by weight of the compound represented by General Formula (I) and 30 to 50% by weight of the compound represented by General Formula (III).

(Ⅰ)
Wherein R ₁ , R ₂ , R ₃ are each independently hydrogen, methyl, ethyl, phenyl, halogen, methoxy, ethoxy, hydroxy, ureido, sulfo, methylamino, ethylamino, sulfamoyl, carboxyl group and Me Is a metal ion, Y is a halogen atom, Q is a vinylsulfone group or the general formula -SO ₂ CH ₂ CH ₂ -L, and L is a group which can be separated under alkaline conditions. -Cl, -Br, are _{-F, -OSO 3 H, -SSO 3} H, -OCOCH 3, -OPO 3 H 2, -OCO-C 6 H 5 or -OSO ₂ -C ₁ ~ C ₄ alkyl.
A is

or

to be.

(Ⅲ)
Wherein R ₄ , R ₅ , R ₆ , R ₇ are each independently hydrogen, methyl, ethyl, phenyl, halogen, methoxy, ethoxy, hydroxy, ureido, sulfo, methylamino, ethylamino, sulfamoyl, Me is a carboxyl group, Me is a metal ion, Y is a halogen atom, Q is a vinylsulfone group or a general formula -SO ₂ CH ₂ CH ₂ -L, and L is a group which can be separated under alkaline conditions. -Cl, -Br, are _{-F, -OSO 3 H, -SSO 3} H, -OCOCH 3, -OPO 3 H 2, -OCO-C 6 H 5 or -OSO ₂ -C ₁ ~ C ₄ alkyl.
A is

or

to be.
The dye composition of the present invention has a high wash fastness.

Description

Composition of reactive blue dyes

The present invention relates to a reactive blue dye composition suitable for cellulose fiber dyeing.

Specifically, a blue dye composition obtained by mixing 50 to 70% by weight of the compound represented by the general formula (I) and 30 to 50% by weight of the compound represented by the general formula (III) and the compound 50 represented by the general formula (II) It relates to a blue dye composition obtained by mixing ~ 70% by weight and 30 to 50% by weight of the compound represented by the general formula (III).

(Ⅰ)

(Ⅰ)

Wherein R ₁ , R ₂ , R ₃ are each independently hydrogen, methyl, ethyl, phenyl, halogen, methoxy, ethoxy, hydroxy, ureido, sulfo, methylamino, ethylamino, sulfamoyl, carboxyl group and Me Is a metal ion, Y is a halogen atom, Q is a vinylsulfone group or the general formula -SO ₂ CH ₂ CH ₂ -L, and L is a group which can be separated under alkaline conditions. -Cl, -Br, are _{-F, -OSO 3 H, -SSO 3} H, -OCOCH 3, -OPO 3 H 2, -OCO-C 6 H 5 or -OSO ₂ -C ₁ ~ C ₄ alkyl.

A is

or

to be.

(Ⅱ)

(Ⅱ)

Wherein Q is a vinyl sulfone group or a general formula -SO ₂ CH ₂ CH ₂ -L, L is a group that can be separated under alkaline conditions, -Cl, -Br, -F, -OSO ₃ H, -SSO ₃ H, -OCOCH ₃ , -OPO ₃ H ₂ , -OCO-C ₆ H ₅ or -OSO ₂ -C ₁ -C ₄ alkyl.

A is

or

to be.

(Ⅲ)

Wherein R ₄ , R ₅ , R ₆ , R ₇ are each independently hydrogen, methyl, ethyl, phenyl, halogen, methoxy, ethoxy, hydroxy, ureido, sulfo, methylamino, ethylamino, sulfamoyl, Me is a carboxyl group, Me is a metal ion, Y is a halogen atom, Q is a vinylsulfone group or a general formula -SO ₂ CH ₂ CH ₂ -L, and L is a group which can be separated under alkaline conditions. -Cl, -Br, are _{-F, -OSO 3 H, -SSO 3} H, -OCOCH 3, -OPO 3 H 2, -OCO-C 6 H 5 or -OSO ₂ -C ₁ ~ C ₄ alkyl.

A is

or

to be.

The compound represented by the general formula (I) and the compound represented by the general formula (II) are well known blue dyes.

Compounds of general formula (I) are well known as dyes useful for dyeing hydroxy group or amino group-containing materials as metal formalin dye compounds in Korean Patent Publication No. 1992-0001489.

The general formula (II) compound is a blue reactive dye compound that gloss on fabrics in Korea Patent Publication No. 10-0373997 is well known as an important reactive dye in the blue dye field.

Although the compounds of the general formula (I) and the general formula (II) are dye compounds having various characteristics, the fastness after dyeing, in particular, the wash fastness was somewhat poor. The present invention maintains the properties of general formula (I) or general formula (II) by forming a dye composition with the compound of general formula (I) or general formula (II) and the following general formula (III) It is intended to improve buildup and dyeing fastness after dyeing.

The compound of general formula (III) is a compound which is not yet known.

SUMMARY OF THE INVENTION An object of the present invention is to provide a dye composition having excellent buildup properties and fastness to washing after dyeing while maintaining the usefulness of the dye of the general formula (I) or (II).

The inventors of the present invention, while seeking to improve the wash fastness of the dye compounds of the general formula (I) and formula (II), the reactive blue dye compounds of the general formula (I) and formula (II) and the general formula ( Comprising the present invention by confirming that the dye composition of the reactive blue dye compound of Ⅲ) can improve the washing fastness after dyeing while maintaining the properties of the general formula (I) and the general formula (II) compound will be.

The composition of the present invention has the effect of improving the washing fastness of about 0.5 grades compared to the general formula (I) and general formula (II) compound.

The present invention relates to a blue dye composition suitable for dyeing cellulosic fibers.

Compounds of general formula (I) and general formula (II) used as the composition of the present invention are blue reactive dyes, which are widely used dyes, but are not particularly satisfactory in washing fastness after dyeing. There is a problem.

The present invention is useful for the dyes of general formula (I) or general formula (II) by forming a dye composition with a dye compound of general formula (I) or (II) and a dye compound of general formula (III). It is intended to provide a dye composition having excellent build-up properties and washing fastness after dyeing while maintaining.

The dye composition of the present invention has an effect of improving the laundry fastness by about 0.5 compared to the dye of the general formula (I), general formula (II) and general formula (III).

The proportion of each component of the dye composition used in the present invention may be slightly different depending on the synthesis method of the respective compounds, but in general, the desired dye can be obtained by mixing the compounds of (I) and (II) or (I) and (III). A dye having fastness or stability can be obtained. Among them, preferred weight ratios were 55-65: 35-45 for (I) :( III) and 60-70: 30-40 for (II) :( III).

The dyeing of the fiber reactive blue dye mixture according to the invention can be carried out in a suitable manner for the reactive groups present in the reactive dyes. For example, when dyeing cellulose fiber materials by adsorption, the weight ratio of water to dye under an aqueous medium is generally 1: 2 to 1:20 and dyes containing the acid binders sodium hydroxide, sodium bicarbonate, sodium carbonate and sodium sulfate or sodium chloride Dyeing is performed at 40-80 degreeC which is comparatively low temperature using etc.

Alternatively, a dye paste containing a flavor (sodium alginate or starch ether), an alkali or alkaline emulsion, a printing wetting aid (urea) and a dispersant may be prepared, and then dyed by steaming the paste with the paste on the fibers. Cold pad batch method is to pick up the fiber in a padding solution containing sodium hydroxide, sodium hydroxide and sodium silicate, sodium carbonate, sodium phosphate and urea and the preparation of an acid binder at room temperature, then picked up, and left for 3 to 48 hours After washing with water and dyed.

The dyeings dyed by the present invention have good buildup, leveling, reproducibility and wash fastness.

The present invention will be described in detail with reference to the following Examples.

Preparation Example 1-1

Preparation of the compound represented by the following structural formula (IV) contained in general formula (I)

(Ⅳ)

(Ⅳ)

To 50 mL of water, 24.6 g of 3-acetylamino-2-hydroxyaniline-5-sulfonic acid and 15 g of concentrated hydrochloric acid were added and cooled to 10 ° C or lower. To this solution, 30 g of water was added 7.1 g of sodium nitrite and dissolved sodium nitrite solution. Diazo and then stirred for about 2 hours, the excess of nitrous acid is broken down into sulfamic acid.

To this diazonium compound, 32 g of the hydrazone compound was added to 200 g of water, dissolved to pH 7.0, and then added dropwise to the mixture for about 30 minutes. The mixture was neutralized and stirred until the diazonium compound disappeared with sodium carbonate at 10 ° C or lower. The formazan-containing reaction mixture is adjusted to pH 6-7 and mixed with crystalline copper sulfate. The mixture was stirred at 40 DEG C or lower for about 4 to obtain a copper complex, then 3% sodium hydroxide was added to the total liquid amount, and the temperature was raised to 90 DEG C and stirred for about 8 hours.

The resulting mixture is adjusted to pH 7 and then added dropwise to 18.4 g of cyanuric chloride below 10 ° C. The mixture is stirred for 4 hours with sodium carbonate at 10 < 0 > C or lower, adjusting the pH to 7 or lower.

31 g of 1-N-ethylaminobenzene-3-β-selapitoethylsulfone was added to the reaction mixture, and the resulting mixture was heated to 60 ° C or lower while adjusting the pH to 6 or lower using sodium carbonate solution. Stir at temperature for 8 hours. Sodium chloride is added to the reaction mixture to precipitate crystals, suction filtration, washing and drying.

The reactive blue dye represented by the above structural formula (IV) is obtained.

Preparation Example 2-1

Preparation of the compound represented by the following structural formula (V) contained in general formula (II)

(Ⅴ)

(Ⅴ)

Disperse 19.1 g of bromine acid in 200 mL of water for 1 hour, add 15 g of sodium bicarbonate, add 15.1 g of 1-aminobenzene-3-β-hydroxyethylsulfone, and add the mixture until a homogeneous dispersion is formed. Stir for about 2 hours. 1 g of copper powder and 1.6 g of copper chloride are added and heated to 90-92 ° C. and stirred for about 15 hours. The reaction solution was cooled to 65-70 ° C., filter press or suction filtration, potassium chloride having a weight equivalent to 7% by weight of the total volume was salted out, and filtered to obtain a primary wet cake.

The primary wet cake was dissolved in 200 mL of water at 40 ° C. for about 1 hour, dissolved, dissolved in 14.0 mL of 35% hydrochloric acid, and then filtered to obtain a secondary wet cake.

The secondary wet cake was dissolved in 140 mL of 40 ° C. water for about 1 hour, dissolved, and dissolved in 5.4 mL of 35% hydrochloric acid, filtered, washed with 90 mL of 3% aqueous potassium chloride solution, and dried. 61 g of fuming sulfuric acid cooled to 10 ° C. or lower was dried at 30 ° C. or lower for 1 to 2 hours, stirred at 30 ° C. or lower for 12 hours, discharged into iced water, salted and filtered to obtain a tertiary wet cake.

Dissolve the tertiary wet cake in water, adjust the pH to 7.0 or less with sodium carbonate and spray-dry with sufficient stirring to obtain a reactive color blue dye represented by the above formula (V).

Preparation Example 3-1

Preparation of the compound represented by the following structural formula (VI) contained in general formula (III)

Add 48.51 g of 1-amino-4- (2 ′? Aminoethyl) aminobenzene-3-sulphonic acid to 200mL of water, adjust the pH to 7.0 with sodium carbonate, and add 24.6g of chloranil. The pH is adjusted to 6.0 or less while raising the temperature to 60 ° C. or less. In addition, the pH was adjusted to 6.0 or less while stirring for 5 hours or less at 60 ° C, and the precipitated product was suction filtered and dried.

63.5g of the above dried product was slowly added to 300g of fuming sulfuric acid at a concentration of 5% for the purpose of ring-closing with trifendioxazine compound, and stirred for 4 hours at 30 ° C or lower, and then discharged into a container containing ice and then calcium carbonate and sodium carbonate were used. The pH is adjusted to 6.0 or less, followed by suction filtration and drying.

9.2 g of cyanuric chloride is dispersed at 10 ° C. or lower, and 8.65 g of methalinic acid is dissolved in 100 mL of water to pH 7.0 or lower, and the primary condensation is adjusted to pH 5.0 or lower while dropping in the above dispersion. After the first condensation is completed, 15.75 g of the above-described tripfendioxazine base is dissolved, and then condensed at a pH of 9.5 or less. Tertiary condensation is carried out, keeping the following. When the reaction is completed and dried, a reactive blue dye represented by the following structural formula (VI) is obtained.

Preparation Example 3-2

In the same manner as in Preparation Example 3-1 replacing 12.65 g of 1-aminobenzene-2,5-disulfonic acid in place of 8.65 g of metanilic acid in Preparation Example 3-1, the metanilic group was represented by Formula (VI). A dye compound substituted with 1-aminobenzene-2,5-disulfone group is obtained.

 Preparation Example 3-3

In Production Example 3-1, instead of 14.1 g of 1-aminobenzene-4-β-sulfatoethylsulfone, 14.1 g of 1-aminobenzene-3-β-sulfatoethylsulfone was added thereto. When the dye was prepared in the same manner, the dye compound in which the 1-aminobenzene-4-β-sulfatoethylsulfone group was substituted with the 1-aminobenzene-3-β-sulfatoethylsulfone group in formula (VI) Obtained.

Preparation Example 3-4

In Preparation Example 3-1, 14.1 g of 1-aminobenzene-3-β-sulfatoethylsulfone was added instead of 14.1 g of 1-aminobenzene-4-β-sulfatoethylsulfone. 12.65 g of aminobenzene-2,5-disulfonic acid was added thereto, followed by the same method as in Preparation Example 3-1, to prepare a dye. In general formula (VI), 1-aminobenzene-4-β-sulfatoethyl A dye compound in which the sulfone group is each substituted with a 1-aminobenzene-3-β-sulfatoethylsulfone group and a metanilic group with a 1-aminobenzene-2,5-disulfone group is obtained.

Examples 1-8

Next, the dye composition and the dye fastness obtained in the preparation example according to the mixing ratio described in [Table 1] were measured and shown in the following table. Wash fastness was measured according to ISO-105-CO3 regulations.

Example Furtherance
ratio color Color fastness ingredient ingredient One
2
3
4
5
6
7
8 Dye of Preparation Example 1-1
Dye of Preparation Example 1-1
Dye of Preparation Example 1-1
Dye of Preparation Example 1-1
Dye of Preparation Example 2-1
Dye of Preparation Example 2-1
Dye of Preparation Example 2-1
Dye of Preparation Example 2-1 Dye of Preparation Example 3-1
Dye of Preparation Example 3-2
Dye of Preparation Example 3-3
Dye of Preparation Example 3-4
Dye of Preparation Example 3-1
Dye of Preparation Example 3-2
Dye of Preparation Example 3-3
Dye of Preparation Example 3-4 55:45
60:40
65:35
70:30
60:40
65:35
70:30
70:30 blue
blue
blue
blue
blue
blue
blue
blue 4.5
4.5
4.5
4.5
4.5
4.5
4.5
4.5

Claims (2)

Reactive blue dye composition which consists of 50-70 weight% of compounds represented by following General formula (I), and 30-50 weight% of compounds represented by following General formula (III) in dye composition.

(Ⅰ)

Wherein R ₁ , R ₂ , R ₃ are each independently hydrogen, methyl, ethyl, phenyl, halogen, methoxy, ethoxy, hydroxy, ureido, sulfo, methylamino, ethylamino, sulfamoyl, carboxyl group and Me Is a metal ion, Y is a halogen atom, Q is a vinylsulfone group or the general formula -SO ₂ CH ₂ CH ₂ -L, and L is a group which can be separated under alkaline conditions. -Cl, -Br, are _{-F, -OSO 3 H, -SSO 3} H, -OCOCH 3, -OPO 3 H 2, -OCO-C 6 H 5 or -OSO ₂ -C ₁ ~ C ₄ alkyl.
A is

or

to be.

(Ⅲ)

Wherein R ₄ , R ₅ , R ₆ , R ₇ are each independently hydrogen, methyl, ethyl, phenyl, halogen, methoxy, ethoxy, hydroxy, ureido, sulfo, methylamino, ethylamino, sulfamoyl, Is a carboxyl group, Me is a metal ion, Y is a halogen atom, Q is a vinylsulfone group or a general formula -SO ₂ CH ₂ CH ₂ -L, and L is a group which can be separated under alkaline conditions, -Cl, -Br,- _{F, -OSO 3 H, -SSO 3} H, -OCOCH 3, -OPO 3 H 2, -OCO-C 6 H ₅ is, or -OSO ₂ -C ₁ ~ C ₄ alkyl.

A is

or

to be.
The reactive blue dye composition of the dye composition comprising 50 to 70% by weight of the compound represented by the following general formula (II) and 30 to 50% by weight of the compound represented by the following general formula (III).

(Ⅱ)

Wherein Q is a vinylsulfone group or a general formula -SO ₂ CH ₂ CH ₂ -L, L is a group that can be separated under alkaline conditions, -Cl, -Br, -F, -OSO ₃ H, -SSO ₃ H, -OCOCH ₃ , -OPO ₃ H ₂ , -OCO-C ₆ H ₅ or -OSO ₂ -C ₁ -C ₄ alkyl.
A is

or

to be.

(Ⅲ)

Wherein R ₄ , R ₅ , R ₆ , R ₇ are each independently hydrogen, methyl, ethyl, phenyl, halogen, methoxy, ethoxy, hydroxy, ureido, sulfo, methylamino, ethylamino, sulfamoyl, Me is a carboxyl group, Me is a metal ion, Y is a halogen atom, Q is a vinylsulfone group or a general formula -SO ₂ CH ₂ CH ₂ -L, and L is a group which can be separated under alkaline conditions. -Cl, -Br, are _{-F, -OSO 3 H, -SSO 3} H, -OCOCH 3, -OPO 3 H 2, -OCO-C 6 H 5 or -OSO ₂ -C ₁ ~ C ₄ alkyl.

A is

or

to be.