JPH07331099A - Azo dye - Google Patents

Abstract

PURPOSE:To obtain a water-insoluble azo dye useful for dyeing orange or blue synthetic textile fibers, esp., ultra-fine polyester fibers with high fastness to washing, alkaline sweat and light. CONSTITUTION:The objective azo dye of formula I [D is of formula II (A<1> is nitro, cyano, methylsulfonyl, etc.; A<2> is H, a halogen, nitro, etc.; A<3> is H, a halogen or cyano), etc.; X is H, a halogen, OH, etc.; Y is H, a halogen, methyl, etc.; R is H, a halogen, nitro, etc.], e.g. a disperse dye of formula III. This azo dye is obtained by diazotizing an amine of formula D-NH2 followed by coupling with an aniline of formula IV.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a water-insoluble azo dye. The present invention also relates to a water-insoluble dye that dyes synthetic fibers in orange to blue color with excellent fastness. The present invention also relates to a water-insoluble dye suitable for dyeing polyester ultrafine fibers in orange or blue color, which has excellent fastness to washing and fastness to alkaline sweat.

[0002]

2. Description of the Related Art In recent years, various researches have been conducted on polyester fibers with the aim of developing high value-added products. Among them, research on ultrafine fibers has been advanced mainly to produce products with excellent texture, and from fibers of 1 denier or less,
Ultrafine fibers of 0.3 denier or less (also called ultramicrofibers) have been developed and come into production.

These polyester fibers have produced products with a good texture not seen in the past, but these ultra-microfibers with a finer diameter are wash-fast when dyed with conventional disperse dyes. This causes a problem that the wet fastness such as the degree is significantly reduced.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an orange to blue disperse dye having good washing fastness and alkali fastness to sweat and light fastness. .

[0005]

The present invention has the following general formula [I]:

[0006]

[Chemical 11]

[Wherein D is i)

[0008]

[Chemical 12]

(Here, A ¹ represents a nitro group, a cyano group, a methylsulfonyl group, a C ₁ -C ₂ alkyl group or a phenylazo group, and A ² represents a hydrogen atom, a halogen atom, a nitro group, a cyano group or trifluoro group. Represents a methyl group, A ³
Represents a hydrogen atom, a halogen atom or a cyano group. ) Ii)

[0010]

[Chemical 13]

(Here, A ⁴ represents a halogen atom or a nitro group, and A ⁵ represents a hydrogen atom or a halogen atom.) Iii)

[0012]

[Chemical 14]

(Here, A ⁶ is a hydrogen atom, a halogen atom, a C ₁ -C ₂ alkyl group, a phenyl group or a C ₁ -C ₂ group.
It represents an alkylsulfonyl group, A ⁷ represents a formyl group, a nitro group or a cyano group, and A ⁸ represents a cyano group, a nitro group or a C ₁ -C ₂ alkylcarbonyl group. ) Iv)

[0014]

[Chemical 15]

(Here, A ⁹ represents a halogen atom or a nitro group, and A ¹⁰ represents a hydrogen atom or a halogen atom.) Or v)

[0016]

[Chemical 16]

(Here, A ¹¹ represents a hydrogen atom, a halogen atom or a nitro group, A ¹² represents a hydrogen atom or a halogen atom, and A ¹³ represents a hydrogen atom or a methyl group.)
X represents a hydrogen atom, a halogen atom, a hydroxyl group, a methyl group or an NHZ group (wherein Z is a C ₁ -C ₄ alkylsulfonyl group, a phenylsulfonyl group, a C ₁ -C ₄ alkylcarbonyl group, C ₁ -C ₂ An alkoxy C ₁ -C ₂ alkylcarbonyl group, a phenylcarbonyl group or an aminocarbonyl group), Y represents a hydrogen atom, a halogen atom, a methyl group or a C ₁ -C ₂ alkoxy group, R represents a hydrogen atom, Halogen atom, nitro group, C ₁ -C
_{4 represents} an alkyl group or a C ₁ -C ₄ alkoxy group. ]
The subject is an azo dye represented by.

The present invention will be described in detail below. In the general formula [I], A ² , A ³ , A ⁴ , A ⁵ , A ⁶ ,
Examples of the halogen atom represented by A ⁹ , A ¹⁰ , A ¹¹ , A ¹² , X and Y include a chlorine atom or a bromine atom.
A chlorine atom is particularly preferable. C ₁ -C ₄ alkylsulfonyl group represented by Z of NHZ group as X, C ₁ -C ₄
As the alkylcarbonyl group, a methylsulfonyl group,
Ethylsulfonyl group, n-propylsulfonyl group, i-
Propylsulfonyl group, n-butylsulfonyl group, se
a C ₁ -C ₄ linear or branched alkylsulfonyl group such as a c-butylsulfonyl group, a methylcarbonyl group,
Ethylcarbonyl group, n-propylcarbonyl group, i-
Propylcarbonyl group, n-butylcarbonyl group, is
Examples thereof include a C _{1 to} C ₄ linear or branched alkylcarbonyl group such as an o-butylcarbonyl group.

Of these, a C ₁ -C ₂ alkylsulfonyl group and a C ₁ -C ₂ alkylcarbonyl group are particularly preferable.
Examples of the C ₁ -C ₂ alkoxy C ₁ -C ₂ alkylcarbonyl group represented by Z include a methoxymethylcarbonyl group, an ethoxymethylcarbonyl group, a methoxyethylcarbonyl group and an ethoxyethylcarbonyl group. A carbonyl group is preferred.

The C ₁ -C ₂ alkoxy group represented by Y includes a methoxy group or an ethoxy group. Among the dyes represented by the general formula [I], those enumerated below can be exemplified as particularly preferable ones.

[0021]

[Chemical 17]

(In the formula, X ¹ represents a hydrogen atom, a chlorine atom or a methyl group.)

[0023]

[Chemical 18]

(In the formula, X ² represents a hydrogen atom or a methyl group.)

[0025]

[Chemical 19]

(In the formula, A ^6-1 represents a hydrogen atom or a halogen atom, A ^7-1 represents a formyl group or a nitro group, and X ³ represents a C ₁ -C ₂ alkylcarbonylamino group or methoxymethylcarbonylamino group. Represents a group.)

[0027]

[Chemical 20]

(In the formula, A ^11-1 represents a hydrogen atom, a chlorine atom or a nitro group, and A ^12-1 represents a hydrogen atom or a chlorine atom.) The azo dye represented by the general formula [I] is, for example, An amine represented by the following general formula [VI] D-NH ₂ ... [VI] (wherein D has the same meaning as defined above) is diazotized by a conventional method, and then the following general formula [VII]

[0029]

[Chemical 21]

The compound can be produced by coupling with an aniline represented by the formula (wherein X, Y and R have the same meanings as defined above). Examples of fibers dyeable with the azo dye of the present invention include polyethylene terephthalate, polybutylene terephthalate, polyester fibers made of polycondensates of terephthalic acid and 1,4-bis- (hydroxymethyl) cyclohexane, polyamides such as nylon. Textile products such as a mixed fiber and a mixed woven product of the above-mentioned polyester fiber with a natural fiber such as a series fiber or cotton, silk, and wool. As the polyester fiber, not only regular fibers having a normal fineness of 1 denier or more, but also microfibers having a denier of 1 denier or less, and further,
Ultra microfibers having a denier of 3 denier or less are also mentioned as those which can be dyed well.

In carrying out dyeing with the dye of the present invention, a dispersant is used by a conventional method to disperse the azo dye represented by the general formula [I] in an aqueous medium to obtain a dye bath or printing. A paste may be prepared, and dyeing or printing may be performed. For example, in the case of dyeing, by applying a usual dyeing treatment method such as a high temperature dyeing method, a carrier dyeing method and a thermosol dyeing method, it is possible to dye a polyester fiber or a blended fabric or a woven fabric thereof with excellent fastness. Can be given. Further, depending on the case, more favorable results may be obtained by adding acidic physical properties to the dyeing bath.

The dyed fabric obtained by the above-mentioned dip dyeing or printing using the azo dye of the present invention has excellent fastness to washing, and also has fastness to alkali sweat, fastness to light, fastness to sublimation,
And excellent in various fastnesses such as water fastness. Further, even when the dyed cloth is post-processed, the wet fastness is not significantly lowered in the present invention. The azo dye of the present invention may be used in combination with a dye of the same system or a dye of another system.

[0033]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist. Example 1

[0034]

[Chemical formula 22]

Monoazo dye 0.02 represented by the above formula
5 g of 0.025 g of naphthalenesulfonic acid-formaldehyde condensate and 0.02 of higher alcohol sulfate ester
A dyebath was prepared by dispersing in 5 ml of 200 ml of water. In this dyeing bath, 10 g of a mixed woven fabric of polyester fibers having a diameter of 2 denier and 0.01 denier is immersed,
After dyeing at 30 ° C. for 30 minutes, soaping, washing with water, and drying were carried out, and a clear blue dyed fabric having good homogeneity and same density between different denier was obtained. The washing fastness of the above-mentioned interwoven fabric dyed with the above dye was excellent at 4-5 grade. Furthermore, the fastness to light was excellent at 5 ⁺ grade.

The fastness to washing was determined by determining the stain degree of the nylon cloth by the AATCC 2A method. The monoazo dye used in this example was produced by the following method. That is,
98 g of 4.2 g of 2,6-dichloro-4-nitroaniline
% Sulfuric acid at 30 ° C., and 43% nitrosyl sulfuric acid 6.5 g was added at 30 ° C., followed by stirring for 2 hours to obtain a diazo liquid.

Then, pyridine containing 9.8 g of N, N-di (4-methylphenylsulfonyloxyethyl) aniline was dissolved in 200 ml of methanol, and then the diazo solution was added dropwise at 0 to 5 ° C. and stirred for 2 hours. After filtering,
After washing with water and drying, the target dye was obtained. The maximum wavelength of the dye (λ
max acetone) was 416 nm.

N, N-di (4-methylphenylsulfonyloxyethyl) aniline as the coupling component of this example was synthesized by the following method. First, 18.1 g of N, N-di (2-hydroxyethyl) aniline was dissolved in 50 g of pyridine at room temperature, 40 g of 4-methylphenylsulfonyl chloride was added, and the reaction was performed at 60 ° C. for 7 hours to obtain the compound. Example 2

[0039]

[Chemical formula 23]

When the dye represented by the above formula was evaluated in accordance with Example 1, a clear blue dyeing cloth having good color and density characteristics between different denier was obtained. The washing fastness of the interwoven cloth dyed with the above dye was excellent at 4-5 ^- grade. The monoazo dye used in this example was produced by the following method.

2-amino-3-cyano-4-chloro-5
1.9 g of formylthiophene are added to a mixture of 1.5 g of glacial acetic acid / propionic acid (3: 1) and 5.0 g of 85% sulfuric acid, to which nitrosylsulfuric acid (43%) is added at 0-5 ° C.
3.2 g is added dropwise. Then stir at 0-5 ° C. for 4 hours. Urea was added to destroy the remaining nitrous acid, and 12 g of a pyridine solution containing 5.5 g of N, N-di (phenylsulfonyloxyethyl) aniline was added dropwise to 200 ml of methanol at 0 to 5 ° C. for 2 hours. After stirring, it was filtered, washed with water and dried to obtain the target dye. The maximum wavelength of the dye (λ max acetone) was 562 nm. Comparative Example 1 The following dyes described in JP-A No. 61-266466 and Example 6

[0042]

[Chemical formula 24]

The dyeing evaluation was also carried out in accordance with Example 1, and the fastness to washing was inferior to the 2-3 grade. Examples 3 to 76 The dyes shown in Table 1 were synthesized according to Example 1, and the ultra microfiber woven fabric was dyed in the same manner as in Example 1. As a result, the wash fastness was 4 ⁺ or more.

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

[Table 3]

[0047]

[Table 4]

[0048]

[Table 5]

[0049]

[Table 6]

[0050]

[Table 7]

[0051]

[Table 8]

[0052]

[Table 9]

[0053]

[Table 10]

[0054]

[Table 11]

[0055]

EFFECT OF THE INVENTION The dye of the present invention is excellent in wet fastness such as washing fastness even for polyester fibers, especially polyester ultrafine fibers, especially ultrafine fibers called ultramicrofiber having a denier of 0.3 or less, and fastness to alkali sweat. It can be dyed in orange or blue with good color and fastness to light.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location D06P 3/54

Claims (7)

[Claims] 1. The following general formula [I]: [Wherein D is i) (Here, A ¹ represents a nitro group, a cyano group, a methylsulfonyl group, a C ₁ -C ₂ alkyl group or a phenylazo group, and A ² represents a hydrogen atom, a halogen atom, a nitro group, a cyano group or a trifluoromethyl group. Where A ³ is a hydrogen atom,
Represents a halogen atom or a cyano group. ) Ii) [Chemical formula 3] (Here, A ⁴ represents a halogen atom or a nitro group,
A ⁵ represents a hydrogen atom or a halogen atom. ) Iii) [Chemical 4] (Here, A ⁶ is a hydrogen atom, a halogen atom, C _{1 to} C ₂
Alkyl group, phenyl group or C ₁ -C ₂ alkylsulfonyl group is represented, A ⁷ is formyl group, nitro group or cyano group, A ⁸ is cyano group, nitro group or C ₁ -C
₂ represents an alkylcarbonyl group. ) Iv) [Chemical 5] (Here, A ⁹ represents a halogen atom or a nitro group,
A ¹⁰ represents a hydrogen atom or a halogen atom. ) Or v) (Here, A ¹¹ represents a hydrogen atom, a halogen atom or a nitro group, A ¹² represents a hydrogen atom or a halogen atom,
A ¹³ represents a hydrogen atom or a methyl group. And X is a hydrogen atom, a halogen atom, a hydroxyl group, a methyl group or N
HZ group (where Z is a C ₁ -C ₄ alkylsulfonyl group,
It represents a phenylsulfonyl group, a C ₁ -C ₄ alkylcarbonyl group, a C ₁ -C ₂ alkoxy C ₁ -C ₂ alkylcarbonyl group, a phenylcarbonyl group or an aminocarbonyl group. And Y represents a hydrogen atom, a halogen atom, a methyl group or C ₁ -C ₂
Represents an alkoxy group, and R represents a hydrogen atom, a halogen atom, a nitro group, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. ] The azo dye shown by these. 2. The following general formula [II]: (In the formula, X ¹ represents a hydrogen atom, a chlorine atom or a methyl group). 3. The following general formula [III]: (In the formula, X ² represents a hydrogen atom or a methyl group.) A monoazo dye. 4. The following general formula [IV]: (In the formula, A ^6-1 represents a hydrogen atom or a halogen atom,
A ^7-1 represents a formyl group or a nitro group, and X ³ represents C ₁
~ C _{2 represents} an alkylcarbonylamino group or a methoxymethylcarbonylamino group. ) Monoazo dyes represented by. 5. The following general formula [V]: (In the formula, A ^11-1 represents a hydrogen atom, a chlorine atom or a nitro group, and A ^12-1 represents a hydrogen atom or a chlorine atom.). 6. A method for dyeing a synthetic fiber with the azo dye according to claim 1. 7. A method for dyeing an ultrafine polyester fiber having a denier of 0.3 or less by using the azo dye according to claim 1.