JP2949838B2 - Reactive dye composition and method for dyeing or printing fiber material using the same - Google Patents

Description

The present invention relates to a material containing a hydroxyl group and / or an amide group, especially a cellulose fiber, a natural or synthetic polyamide fiber, a polyurethane fiber or leather, and a blend thereof. The present invention relates to an improved reactive dye composition suitable for dyeing and printing fibers and enabling light-fast and wet-fast dyeing, and its application.

<Related Art> A compound having a vinylsulfone-based reactive group and a monochlorotriazine-based reactive group is useful as a reactive dye used for dyeing a material containing a hydroxyl group and / or an amide group. It is publicly known as described in, for example, US Pat.

<Problems to be Solved by the Invention> Conventionally, this type of reactive dye has been widely used in the field of dyeing and printing of fiber materials. However, the current state of the art is
It is not fully satisfactory in view of the high requirements for suitability for a particular dyeing process and the increasing demands for the fastness and dyeability of the dyed products.

It is strongly desired that the above-mentioned known reactive dyes be further improved in terms of build-up property, solubility, stability with time, and fastness.

The present inventors have made intensive studies to improve the above-mentioned known dyes and find a reactive dye which can widely satisfy the requirements required for the dye, and as a result, completed the present invention.

<Means for Solving the Problems> The present invention provides a compound represented by the following general formula (I) in the form of a free acid: [In the formula, Z represents CH ＝ CH ₂ or —CH ₂ CH ₂ Z ₁ , and Z ₁ represents a group which is eliminated by the action of an alkali. And a reactive dye represented by the formula:
In the form of the free acid, the following general formula (II) Wherein, Z 'represents -CH = CH ₂ or _{-CH 2 CH 2 Z 2, Z} 2
Represents a group capable of leaving by the action of an alkali. ] It is intended to provide a reactive dye composition characterized by containing the reactive dye represented by the formula (1), and a method for dyeing or printing a fiber material characterized by using the reactive dye composition.

The reactive dyes of the general formulas (I) and (II) in the compositions according to the invention are present in the form of the free acids or in the form of their salts, in particular the alkali metal and alkaline earth metal salts,
Among them, soda salts, potassium salts, and lithium salts are preferred.

The reactive dye represented by the general formula (I) is described in, for example,
-15481 and can be manufactured according to the method disclosed in EPC56975.

The reactive dye represented by the general formula (II) can be produced, for example, as follows. In an aqueous medium, 2-aminonaphthalene-3,6,8-trisulfonic acid is diazotized in a conventional manner, and then coupled with 1,3-diaminobenzene in a conventional manner. Ureidation using a metal cyanate such as To obtain a monoazo compound represented by the formula: The obtained monoazo compound, cyanuric chloride and (Wherein, Z ′ has the above-mentioned meaning). The reactive dye represented by the general formula (II) can be produced by condensing the compound represented by the general formula (II) in any order. The ureidation reaction can be carried out at a temperature of preferably from 0 to 70 ° C, more preferably from 10 to 40 ° C, while adjusting the pH to preferably 4 to 10, more preferably 6 to 8. In addition, the above-mentioned condensation reaction is carried out in an aqueous medium at a temperature of −10 to 50 ° C., preferably at 0 to 30 ° C., and at a pH of 1 to 10, preferably 2 to 7, while secondary. At 0-70 ° C, preferably at 10-50 ° C,
It can be carried out while adjusting the pH to 2 to 9, preferably to 3 to 6.

The reactive dye represented by the general formula (II) thus obtained is useful for dyeing or printing a fiber material containing a hydroxy group or a carbonamide group.

The dye composition of the present invention has the general formulas (I) and (I)
It is obtained by mixing the reactive dye represented by I), but the mixing amount of the reactive dye of the general formula (II) is
It is 1 to 30% by weight, preferably 2 to 15% by weight, based on the reactive dye of the formula (I).

In the present invention, the reactive dyes represented by the general formulas (I) and (II) may be mixed at the time of synthesis by being synthesized at the same time, or may be mixed separately after being synthesized. It may be. Furthermore, they may be mixed at the time of dyeing.

The dye composition of the present invention can be used for dyeing or printing a material containing a hydroxy group or a carbonamide group. The material is preferably used in the form of a fibrous material or a blend thereof.

The hydroxy group-containing material is a natural or synthetic hydroxy group-containing material such as a cellulose fiber material or a regenerated product thereof and polyvinyl alcohol. Cellulose fiber materials are cotton, other plant fibers such as linen,
Hemp, jute and ramie fibers are preferred. Regenerated cellulose fibers are, for example, viscose staples and filament viscose.

Carbonamide-containing materials are, for example, synthetic and natural polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal hair, silk, leather, polyamide-6,
6, polyamide-6, polyamide-11 and polyamide-
4 and so on.

The compound of the present invention can dye or print the above-mentioned materials, particularly the above-mentioned fiber materials, by a method according to physical and chemical properties.

For example, in the case of exhaust dyeing on cellulose fibers, sodium carbonate, tertiary sodium phosphate, in the presence of an acid binder such as caustic soda, optionally a neutral salt, for example, sodium sulfate or sodium chloride,
If desired, dissolution aids, penetrants or leveling agents may be used in combination at relatively low temperatures. Neutral salts which promote the exhaustion of the dye can be added only after the original dyeing temperature has been reached or before, optionally in portions.

When dyeing cellulose fibers according to the padding method,
After padding and drying at room temperature or elevated temperature, it can be fixed by steaming or dry heat.

When printing on cellulosic fibers, printing is carried out in one phase, for example with a printing paste containing baking soda or other acid binders, followed by steaming at 100-160 ° C., or in two phases, for example in medium. It can be carried out by printing with a neutral or weakly acidic printing paste and passing it through a hot electrolyte-containing alkaline bath, or over-padding with an alkaline electrolyte-containing padding solution, and steaming or heat-sensitive.

In the printing paste, a sizing or emulsifying agent such as sodium alginate or starch ether is optionally used,
For example, it is used in combination with a usual printing aid and / or dispersant such as urea.

Acid binders suitable for fixing the dye composition of the present invention on cellulose fibers are, for example, water-soluble basic salts of an alkali metal or alkaline earth metal with an inorganic or organic acid or a compound which releases alkali under heating. is there. In particular, mention may be made of hydroxides of alkali metals and alkali metal salts of inorganic or organic acids of weak to moderate strength, of which soda salts and potassium salts are particularly preferred. Such acid binders include, for example, caustic soda, caustic potash, sodium bicarbonate, sodium carbonate,
Examples include sodium formate, potassium carbonate, sodium primary, secondary or tertiary phosphate, sodium silicate, sodium trichloroacetate and the like.

The dyeing of synthetic and natural polyamide and polyurethane fibers is carried out by first exhausting the acid or weakly acidic dye bath under control of the pH value and then changing it to a neutral and possibly alkaline pH value for fixing. I can do it. Dyeing can usually be carried out at a temperature of 60 to 120 ° C, but in order to achieve levelness, a conventional leveling agent, for example, a condensation product of cyanuric chloride with 3 times mol of aminobenzenesulfonic acid or aminonaphthalenesulfonic acid or For example, an addition product of stearylamine and ethylene oxide can be used.

The dye composition of the present invention is characterized in that the fiber material exhibits excellent performance in dyeing and printing. It is particularly suitable for dyeing cellulose fiber materials, and has good light fastness and sweat and sun fastness, wet fastness, for example, washing fastness, peroxidative washing fastness, sweat fastness, chlorine fastness, oxidized water decomposability and It has Alcal resistance, better friction resistance and ironing resistance.

In addition, it has excellent build-up properties, solubility, level dyeing and wash-off properties, and also has good exhaustion and fixation properties.
It is characterized by the fact that it is hardly affected by fluctuations in the dyeing temperature and the dyeing bath ratio and a dyed product of stable quality can be obtained.

It is also characterized by little discoloration of the obtained dyed product during fixation or resin processing, and little change due to contact with a basic substance during storage.

Hereinafter, the present invention will be described in detail with reference to examples. In the example,
Parts and% represent parts by weight and% by weight, respectively.

Example 1 In the form of the free acid, the following structural formula (i) In the form of a free acid with 100 parts of a monoazo reactive dye represented by the following structural formula (ii) Was mixed with 10 parts of a monoazo reactive dye represented by the formula (1) to obtain a reactive dye composition. 0.1, 0.3 and 0.6 parts of each with 200
Then, 10 parts of sodium sulfate and 10 parts of cotton were added, the temperature was raised to 60 ° C., 4 parts of sodium carbonate was added, and the mixture was dyed for 1 hour. Washing with water,
After soaping, washing and drying, yellow dyeings having excellent fastnesses and good build-up properties were obtained.

The monoazo reactive dye represented by the above formula (ii) was produced as follows.

2-aminonaphthalene-3,6,8-trisulfonic acid 38.3
After diazotization in water in a conventional manner, 10.8 parts of 1,3-diaminobenzene was added and coupled in a conventional manner, sodium cyanate was added in an amount of 7.15 parts, and pN was added using a 2N HCl aqueous solution.
The ureation was terminated at room temperature while adjusting to H7, and 18.5 parts of cyanuric chloride was added to perform the first condensation, followed by 1-
After 28.1 parts of amino-3-β-sulfatoethylsulfonylbenzene was added to terminate the second condensation, the product was isolated to obtain a reactive dye represented by the above structural formula (ii).

Example 2 Obtained by blending 100 parts of the monoazo reactive dye represented by Structural Formula (i) used in Example 1 and 5 parts of the monoazo reactive dye represented by Structural Formula (ii) used in Example 1 0.1, 0.3 and 0.6 parts of each of the dye compositions dissolved in 200 parts of water,
10 parts of cotton and 10 parts of cotton were added, the temperature was raised to 60 ° C., 4 parts of sodium carbonate was added, and dyed for 1 hour. Washing, soaping, washing and drying were carried out to obtain yellow dyeings having excellent fastnesses and good build-up properties.

Example 3 In the form of the free acid, the following structural formula (iii) In the form of a free acid with 100 parts of a monoazo reactive dye represented by the following structural formula (iv) A dye composition obtained by blending 10 parts of a monoazo reactive dye represented by 0.1, 0.3 and 0.6 parts was dissolved in 200 parts of water,
10 parts of sodium sulfate and 10 parts of cotton were added, the temperature was raised to 60 ° C., 4 parts of sodium carbonate was added, and dyed for 1 hour. Washing, soaping, washing and drying were carried out to obtain yellow dyeings having excellent fastnesses and good build-up properties.

Example 4 In the form of the free acid, the following structural formula (v) In the form of a free acid with 100 parts of a monoazo dye represented by the following general formula (vi) 0.1, 0.3 and 0.6 parts of a dye composition obtained by blending with 5 parts of a monoazo reactive dye represented by are dissolved in 200 parts of water,
10 parts of sodium sulfate and 10 parts of cotton were added, the temperature was raised to 60 ° C., 4 parts of sodium carbonate was added, and dyed for 1 hour. Washing, soaping, washing and drying were carried out to obtain yellow dyeings having excellent fastnesses and good build-up properties.

Example 5 Using each reactive dye composition used in Examples 1-4, a color paste having the following composition was prepared.

Reactive dye composition 5 parts Urea 5 parts Sodium alginate (5%) base paste 50 parts Hot water 25 parts Baking soda 2 parts Balance 13 parts Steaming, washing, soaping, washing and drying. All of the obtained prints were excellent in various fastnesses and had good build-up properties.

Claims (2)

(57) [Claims] (1) The following general formula in the form of a free acid: Wherein, Z represents a -CH = CH ₂ or _{-CH 2 CH 2 Z 1, Z} 1 represents a group removable by the action of an alkali. And a reactive dye represented by the formula:
In the form of the free acid, the following general formula Wherein, Z 'represents a -CH = CH ₂ or _{-CH 2 CH 2 Z 2, Z} 2 represents a group capable of leaving by the action of an alkali. ] The reactive dye composition characterized by containing the reactive dye shown by these. 2. A method for dyeing or printing a fiber material, comprising using the reactive dye composition of claim 1.