JPH03773A - Formulation of reactive dye, manufacture thereof and method for dyeing fiber material using the same - Google Patents

Abstract

PURPOSE:To produce an aqueous liquid formulation of a reactive dye excellent in storage stability by causing components which are present in an aqueous solution of a crude reactive dye which contains by-products and are insoluble or hardly soluble in water to be adsorbed into an absorbent and separated, and then desalting and condensing the solution by the membrane separation method. CONSTITUTION:An adsorbent (e.g. activated clay) is added to an aqueous solution of a crude reactive dye (e.g. compounds of formulae I and II), thereby subjecting them to adsorption treatment to separate components which are present in the aqueous solution and are insoluble or hardly soluble in water. Then, the solution is desalted and condensed by the membrane separation method (e.g. the reverse osmotic membrane separation or electrodialysis method) to obtain an aqueous liquid formulation of the reactive dye. The resulting formulation can be stored for a long period of time without giving crystals, precipitates, etc. The solid formulation obtained by drying the aqueous liquid formulation is excellent in solubility, mechanical strength, flowability, etc., and can be suitable used for dyeing a fiber material, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a reactive dye formulation, a method for producing the same, and a method for dyeing textile materials, particularly cellulose fibers, using the same.

<Prior Art> Water-soluble reactive dyes are produced by salting out, filtration, drying, and pulverization by conventional methods after synthesis, or by directly drying the reaction solution containing the dye after synthesis, for example, It is manufactured as a solid formulation through a spray drying process. It is also produced as an aqueous liquid preparation through a process such as condensing the reaction solution.

<Problems to be Solved by the Invention> These dye preparations contain inorganic salts produced as by-products during the reaction and inorganic salts used in salting out. Another problem was that dyes, inorganic salts, etc. precipitated.

As a method to solve such problems, for example, as described in JP-A-47-16522 and JP-A-63-275669, inorganic salts are removed using membrane filtration technology. There are known ways to do this. However, these methods do not fully satisfy the needs of the dye industry, and a solution to this problem is strongly desired.

Furthermore, regarding solid preparations, for example, it is desired to develop granular preparations with a high degree of 1A having excellent mechanical strength, flow characteristics, etc., and an industrially advantageous manufacturing method thereof.

Means for Solving the Problems> The present inventors have conducted intensive studies on the preparation of reactive dyes that are highly desalted and purified and have poor solubility, stability, etc.
We have discovered that the objective can be achieved by removing water-insoluble or sparingly soluble components with a particle size of 0.05μ or less contained in a colloidal state in a crude reactive dye aqueous solution, and have completed the present invention. .

The present invention provides a highly desalted and purified reactive dye formulation with excellent solubility and stability.The present invention also provides a preparation of a reactive dye that is highly desalted and purified and has excellent solubility and stability. A method for producing an aqueous liquid preparation of a reactive dye, which comprises separating water-insoluble or sparingly soluble components, and then desalting and concentrating by a membrane separation method. A method for producing a solid preparation of a reactive dye, which is characterized by drying the obtained purified aqueous solution, and a four-component dyeing method for fibers, which is characterized by using the same.

The reactive dye in the present invention has at least one
fiber reactive groups.

The fiber reactive group is the 10H group or -N of the fiber under dyeing conditions.
It reacts with H-group to form a covalent bond, for example,
having at least one reactive substituent on a heterocyclic ring such as pyridine, pyrimidine, pyridazine, oxazine, triazine, or on a carbocyclic ring such as quinoline, phthalazine, quinazoline, quinoxaline, acridine, aliphatic Examples include reactive groups of the same group, or those in which these are bonded with a suitable linking group.

In these reactive dyes, the dye molecule contains the formula -3O2-YC
In the formula, Y is -CH=CH2 or -CH2CH2Z (
In the formula, Z represents a group that is eliminated by the action of an alkali. ) represents. Vinyl sulfone type reactive dyes having at least one group represented by the following are preferably used. In more detail, such nyl sulfone type reactive dyes are described below-
, (II) and (III).

Lower alkyl, phenyl, and benzyl which may independently have a hydrogen atom or a substituent [wherein, D+ is a residue of an organic dye having a sulfonic acid group, R, and R2 are each independently a hydrogen atom or A lower alkyl group which may have a substituent, Δ is a 02-C6 alkylene group, lower alkylene-* means a single bond, R is a hydrogen atom or a lower alkyl group, ■, and V, each independently represents a direct bond or an aliphatic linking group. ), or a phenylene or naphthylene group which may have a substituent; (represents a lower alkyl group) or a pyridinio group which may have a substituent, the Y position -CH=CH2 or 10HIGH2Zl (wherein, Zl represents a group that is eliminated by the action of an alkali) , n represents a number from 1 to 3. ] 1: h − (S 02 − Y2 ),
(II) [In the formula, D2 is a residue of an organic dye having a sulfonic acid group, Y2 is -CH=CHz or -CH2-CH
2Z2 (in the formula, Z2 represents a group that is eliminated by the action of an alkali), m represents 1-3. ]t(1lNYN ×.

[1] [In the formula, D is a residue of an organic dye having a sulfonic acid group,
R8 is a hydrogen atom or a lower alkyl group which may have a substituent, W is a nitrogen atom or a carbon atom having a chlorine atom as a substituent, X2 and X are each independently a halogen atom, a lower alkoxy group, a substituent In the formula, R1
1, R32, and R13 each independently represent a lower alkyl group. ) or a pyridinio group, Y, which may have a substituent, is -CH=CHz or -CH2CH
2Zs (in the formula, Z represents a group that is eliminated by the action of an alkali).

] In the above general formulas (I), (■) and (DI), the organic dye residues represented by D+, Dt and TRI are monoazo dyes, disazo dyes, trisazo dyes, anthraquinone dyes, respectively. phthalocyanine dye,
Metal complex azo dyes, formazan dyes, azomethine dyes,
Examples include residues of dioxazine dyes and phenazine dyes.

Examples of the lower alkyl group which may have substituents represented by R1, R3 and R- in the general formula (■) and (I[I) include hydroxy, cyano, CI to C4 alkoxy, halogen, carboxy , carbamoyl, C1~
Examples include C1-C4 alkyl groups which may be substituted with C, alkoxycarbonyl, C-C4 alkylcarbonyloxy, sulfo, sulfamoyl, and the like.

The lower alkylene-O-lower alkylene group represented by A is C2-C4 alkylene-〇-〇1-C41 71
．． - As an aliphatic linking group represented by - (CL) +
~6-CO--0-(C11,), ~6-CO-, etc. are represented by °, ■2 as an aliphatic linking group, -(CH
2) ,~,-(C)+2)1~*0-(CL)+
~, -, etc. are exemplified.

In addition, as substituents for phenyl and naphthyl groups that may have substituents represented by 8, methyl, ethyl,
Examples include methoxy, ethoxy, halogen, carboxyl, and sulfo.

The halogens represented by L, Xi and X include chlorine and fluorine, and the lower alkoxy groups include methoxy,
Ethoxy, n-propoxy, 1so-propoxy, n-
Examples include C1-C, alkoxy groups such as butoxy, β-methoxyethoxy, and 1so-butquine. The substituent of the phenoxy group which may have a substituent is C3-C
4 alkyl, C1-C4 alkoxy, nitro, sulfo,
Examples include carboxy and halogen.

has the meaning given above. ), examples of the lower alkyl group which may have a substituent represented by R,, R,, Rs and RIO include methyl, ethyl, n-propyl, 1
so-propyl, n-butyl, is.

-Methyl, 5ec-butyl, β-hydroxyethyl, β
-Sulfatoethyl, β-sulfoethyl, β-methoxyethyl, β-carboxymethyl, etc.; phenyl groups that may have substituents include phenyl, 2-3-
or 4-sulfophenyl, 2-34. or 4-carboxyphenyl, 2.3 or 4-chlorophenyl, 3
．． Examples of the benzyl group such as 4-3.5-1 or 3.6-disulfophenyl which may have a substituent include benzyl, 2-3-7: or 4-sulfobenzyl,
As the naphthyl group which may have a substituent, 2-
3- 4- 5- 6- 7- or 8-sulfo-1-
Naphthyl, 1-5-67- or 8-sulfo-2-
Naphthyl, 2゜4- 5.7- 6.8- 4.8-
4.7-3.8- 4.6- 3.7- or 3.6-
Disulfo-2-naphthyl, 4,6.8- 2.4゜7-
or 3,6.8~trisulfo-1-naphthyl, 1.5
．． 7. - 4.6.8- or 3,6°8-trisulfo-2-naphthyl, etc. are exemplified, respectively.

and R13 have the above meanings. ) and Rs.

Examples of the lower alkyl group represented by Re, Rq, R1, R12 and RI3 include methyl and ethyl, and examples of the substituent of the pyridinio group which may have a substituent include hydroxy-substituted lower alkyl, carbamoyl, sulfo, and carboxy. etc. are exemplified respectively.

Specifically, the vinyl sulfone type reactive dye represented by the above-mentioned -Sakatsu (I) is disclosed in, for example, Japanese Patent Publication No. 39-18184;
Special Publication No. 55-39672, Special Publication No. 58-18472, Special Publication No. 57-25672, Special Publication No. 58-48672, Special Publication No. 60-56836, Special Publication No. 60-36515
No., JP 62-1036, JP 59-15451
No., JP-A-61-155469, JP-A-61-225
No. 256, JP-A-63-77974, JP-A-63-19
It is described in many publications such as No. 6662.

Moreover, the vinyl sulfone type reactive dye represented by the above-mentioned -Sakatsu (II) is also specifically described in, for example, Japanese Patent Publication No. 1989-1989,
Special Publication No. 37-18081, Special Publication No. 37-8090,
Special Publication No. 38-5033, Special Publication No. 39-24649,
Special Publication No. 42-21022, Special Publication No. 42-4267,
Special Publication No. 43-3508, Special Publication No. 43-24790,
Special Publication No. 43-26372, Special Publication No. 10907, Special Publication No. 44-10907, Special Publication No. 10907, Special Publication No. 44-14107
No., Special Publication No. 14107, Special Publication No. 44-3062
No. 0, Special Publication No. 1977-8193, Special Publication No. 1977-8193
No., Special Publication No. 45-40182, Special Publication No. 45-63, Special Publication No. 18829, Special Publication No. 18829, Special Publication No. 46-23914,
Special Publication No. 19751, Special Publication No. 4 B-28902
No., Special Publication No. 46-37387, Special Publication No. 46-4341
No., Japanese Patent Publication No. 46-242.6, Japanese Patent Publication No. 60-377, and the like.

In addition, vinyl sulfone type reactive dyes represented by -sabatsu (I [
JP-A-61-118459, JP-A-61-181806
, JP-A-61-238857, JP-A-61-27856
8, JP-A-63-178168, JP-A-63-2256
65, JP-A-63-256660, and other publications.

Each of these reactive dyes is synthesized by a known method and is present in the form of an aqueous dye solution in the final step. In the present invention, this dye aqueous solution can be used as a crude reactive dye aqueous solution.

Alternatively, a wet cake obtained by salting out and filtering the dye aqueous solution by a conventional method may be dissolved in water to obtain a crude reactive dye aqueous solution, or a powdered dye obtained by a drying process by a conventional method may be dissolved in water. It is also possible to prepare a crude reactive dye aqueous solution by dissolving it in

The adsorbent used in the present invention is not particularly limited as long as it provides an interface that allows a large amount of adsorption to occur, and may include oxides and hydroxides of aluminum, silicon, iron, titanium, tin, etc. , calcium carbonate, clay minerals, and the like.

Among these, porous adsorbents such as bentonite, acid clay, activated clay, activated carbon, and diatomaceous earth are preferably used.

The amount of these adsorbents used is 0.01 to 10% by weight, preferably 0.05 to 3% by weight, based on the crude reactive dye aqueous solution.

In the present invention, adsorption treatment is performed by adding a predetermined amount of adsorbent to a crude reactive dye aqueous solution. Adsorption treatment is usually carried out for 1
This can be accomplished by stirring for 5 to 60 minutes at a temperature of 0 to 60°C.

Filtration is performed after adsorption treatment. Filtration can be performed using a filter press, pressure filter, leaf filter, centrifugal filter, rotary filter, belt filter, or the like. By performing adsorption treatment and filtration in this manner, water-insoluble or sparingly soluble components present in the crude dye solution and having a particle size of 0.05 μm or less can also be removed.

Next, the mother liquor is desalted and concentrated using a membrane separation method. Membrane separation methods that utilize membrane filtration technology are well known.
For example, dialysis methods that utilize a concentration gradient using an ion separation membrane, electrodialysis methods that use an ion exchange membrane as a diaphragm and apply voltage, ultrafiltration methods, reverse osmosis membrane methods, and the like are known.

In the present invention, any of these methods may be used.

Industrially, reverse osmosis membrane separation is advantageous. Materials for reverse osmosis membranes include natural, synthetic, and semi-synthetic materials such as cellulose, cellulose di- or triacetate, polyamide, polysulfone, polystyrene, polyimide, and polyacrylonitrile.

Among these, membranes such as cellulose diacetate, polyamide, polysulfone, and polyacrylonitrile are preferred, and membranes capable of retaining 98% or more of the dye are particularly preferably used. The shapes of the device, membrane, and module are not particularly limited, and any known shapes can be used. The pressure varies depending on the membrane used, the type and shape of the module, but is usually 5 to 70 kg/cffl.

The temperature and pH of the mother liquor subjected to reverse osmosis membrane separation are not critical for the membrane and module, but are determined by the stability of the mother liquor, and are usually pH 3-9, preferably 4-8,
The temperature is 15-60°C, preferably 20-50°C.

The obtained purified dye solution is added with water or further concentrated if desired, so that the dye content in the solution is usually reduced to 5 to 4.
An aqueous liquid preparation can be produced by adjusting the amount to 5% by weight and further adjusting the pH as desired.

According to the method of the present invention, fine particles are also removed by performing adsorption treatment and filtration prior to performing the membrane separation method, so membrane clogging can be avoided and a long membrane life is possible. It also becomes possible to shorten the membrane processing time.

The thus obtained aqueous liquid preparation, which is free of water-insoluble or sparingly soluble components and which is obtained by removing even microparticles with a particle size of 0.05 μm or less, has excellent storage stability.

In the present invention, dust scattering preventive agents, inorganic salts, dyeing aids, etc. are added as necessary to the purified dye aqueous solution obtained by the membrane separation method, and this is dried in a conventional manner to form powder or grain. Alternatively, a solid preparation in the form of granules such as granules can be produced. A powdery solid preparation can be made into a granule-like solid preparation by a conventional method. Drying can be performed by any known method, for example, using a spray dryer, a disk dryer, a fluidized bed apparatus, etc.

Among the solid preparations obtained in this way, the particle size is 70 μm.
The above-mentioned solid preparations, particularly vi4 granular solid preparations, are preferable from the viewpoints of prevention of environmental pollution due to dust scattering, automatic metering, etc.

Such a solid preparation can be easily produced from a highly desalted and purified dye solution using the above-mentioned drying apparatus, and its average particle size is preferably 150μ or more, with a maximum average particle size of can be appropriately determined in consideration of dust scattering, fluidity, solubility, etc.

In the present invention, a granular solid preparation with excellent mechanical strength and fluidity can be produced with or without using a known binder.

In this way it is possible to produce solid formulations with high dye contents of more than 80% by weight, in particular from 85 to 98% by weight.

These solid preparations have excellent solubility and can improve workability during dissolution.

The aqueous liquid and solid dye formulations of the invention are further characterized by good alkaline bath stability.

Cold pad dyeing is attracting attention as an energy-saving dyeing method.
In batch dyeing, alkali is usually added to the padding solution prepared in advance, so there is a problem that the dye may aggregate, precipitate, or gel in the padding solution before it is padded onto the fibers. The dye formulation of the present invention is free from such problems and can be used industrially to advantage in cold pad batch dyeing.

The aqueous liquid and solid dye formulations of the present invention can be applied to textile materials,
In particular, the cellulose UA fiber material is subjected to exhaust dyeing method, printing method,
Alternatively, it can be dyed by any conventionally known method, such as the continuous dyeing method including the cold-pour and batch-batch dyeing methods described above.

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples. In the example,
Parts and % represent parts by weight and % by weight, respectively.

Example 1 500 g of activated clay was added to 50 kg of a crude dye solution containing 10 kg of dye of the following formula (1) in the form of a free acid, and after stirring at 30 to 35°C for 30 minutes, undissolved solids were removed using a filter. did.

The dye solution from which undissolved matter had been removed was subjected to reverse osmosis for 3 hours while adding water equivalent to the permeate, and 120 kg of the permeate was discharged and desalted. Stop adding desalinated water and add 23k dye solution.
A concentrated dye solution with an inorganic salt content of 0.01% was obtained.

Reverse osmosis is performed at a pH of 5.0 to 5.5 and a temperature of 30 to 5.5.
Salt removal rate is approximately 50% at 35℃ and pressure 20kg/c111
The experiments were carried out in a laboratory reverse osmosis apparatus with a 1.6 m' membrane of polysulfone.

10 kg of water was added to the concentrated dye solution thus obtained to obtain an aqueous liquid preparation with a dye content of 30%. This preparation was stored at 0° C. for 6 months, but was stable without forming crystals.

To 23 kg of the concentrated dye solution obtained in the same manner as above, 0.8 kg of sodium sulfate was added for concentration adjustment, and the mixture was dried using a fluidized bed granulator to obtain dye granules having the following physical properties.

(Left below) This fine dye granule had high density, good abrasion resistance, free flowability, and extremely good solubility.

Example 2 1.0 part of the dye granules obtained in Example 1 was dissolved in 100 parts by volume of water, and 100 parts by volume of a 20% aqueous sodium sulfate solution was added.
20 parts of cotton as the material to be dyed was added and the temperature of the solution was adjusted to 50°C. After 20 minutes, 20 parts of a 20% soda ash aqueous solution was added and dyed at the same temperature for 60 minutes.

After dyeing, washing with water, sieving, and drying resulted in a dark blue dyed product with no staining spots.

This dyed product had good fastness properties such as fastness to sunlight and injection light.

(The following is a blank space) Example 3 Cold pad batch dyeing was carried out using the dye granules obtained in Example 1. After adding the alkali, the dye was stable in the prepared dye bath until it was padded onto the fibers, without any changes in properties such as precipitation, condensation, or gelation. As in Example 2, the dyed product was a dark blue color with no staining spots, and had good fastness properties such as fastness to sunlight and injection light.

Example 4 Activated carbon was added to 50 kg of a crude dye solution containing 15 kg of a dye of formula (2) below in the form of free acid.
After adding 5 g and stirring at 40 to 45°C for 30 minutes, undissolved solids were removed using a filter.

80 kg of water was added to the dye solution from which insoluble matters had been removed, and polyacryloni with a salt removal rate of 20% was added for 3 hours.
25-30°C in a laboratory reverse osmosis apparatus with a 1m” membrane
A pressure of 40 kg/cffI was applied, and 100 kg of the salt-containing permeate containing almost no dye was extracted to obtain a concentrated dye solution with an inorganic salt content of 0.2%.

To the thus obtained concentrated aqueous solution, 0.3 kg of sodium sulfate for concentration adjustment and 0.3 kg of sodium phosphate as mF17 agent were added, and then dried with a spray dryer to obtain an average particle size of 200μ and a bulk specific gravity of 0.58 kg. /
Dye granules were obtained which had self-flowing properties with It and dust scattering (Casella value) of 0.9.

When this dye granule was used for cold batch dyeing of cellulose fibers, a yellow dyed product was obtained.

Examples 5 to 23 By using the same method as in Example 4 and using dyes having the structural formulas shown in the table below, concentrated dye preparations each having excellent performance were obtained.

(Left below) Example 24 50 kg of crude dye solution containing 5 kg of dye of formula (24) of aili1 acid (7) Ji was added with 5 kg of activated carbon.
After stirring at 45 to 50°C for 30 minutes, undissolved solids were removed using a filter.

The dye solution from which undissolved matter has been removed is passed through a laboratory reverse osmosis device equipped with a 1 m thick polyamide membrane with a salt rejection rate of 50%.
A pressure of 25 kg/cd was applied at 0° C., and 175 kg of salt-containing permeate containing almost no dye was extracted while adding water equivalent to the permeate.

The addition of desalting water was stopped and the dye solution was concentrated to 25 kg.

An aqueous liquid formulation with a dye content of 20% was thus obtained. If necessary, a buffer, a solubilizing agent, a bactericidal agent, etc. may be added to the obtained liquid preparation, and the preparation may be diluted with water to a predetermined concentration to obtain a desired aqueous liquid preparation.

25 kg of the concentrated dye solution obtained in the same manner as above was dried in a spray dryer to obtain a free-flowing concentrated dye powder having high density and good abrasion resistance. This dye granule had excellent solubility and alkali stability in a concentrated state compared to conventional products, and when dyed cecilerose fiber, a yellow dyed product with no staining spots was obtained.

Examples 25 to 41 Dense dye granules were obtained in the same manner as in Example 24 using dyes satisfying the structural formulas shown in the table below.

(Margin below)

Claims (12)

[Claims] (1) A reactive dye characterized in that a crude reactive dye aqueous solution is treated with an adsorbent to separate water-insoluble or poorly soluble components present in the aqueous solution, and then desalted and concentrated by a membrane separation method. A method for producing an aqueous liquid formulation. (2) A purified aqueous dye solution obtained by treating a crude reactive dye aqueous solution with an adsorbent to separate water-insoluble or poorly soluble components present in the aqueous solution, and then desalting and concentrating it by a membrane separation method. A method for producing a solid preparation of a reactive dye, the method comprising drying a solid preparation of a reactive dye. (3) The method according to claim 1 or 2, wherein the membrane separation method is a reverse osmosis membrane separation method. (4) the reactive dye has at least one compound of the formula -S in its molecule;
O_2-Y [wherein, Y is -CH=CH_2 or -CH
_2CH_2Z (in the formula, Z represents a group that is eliminated by the action of an alkali). The method according to any one of claims 1 to 3, wherein the dye is a vinyl sulfone type reactive dye having a group represented by the following. (5) Vinyl sulfone type reactive dye has the following general formula (I)
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, D_1 is the residue of an organic dye having a sulfonic acid group, and R_1 and R_2 may each independently have a hydrogen atom or a substituent. Lower alkyl group, A is C_2-C
＿6 Alkylene group, lower alkylene-O-lower alkylene group, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, * means bonding to ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, R is a hydrogen atom or lower alkyl group, V_1
and V_2 each independently represent a direct bond or an aliphatic linking group. ), or a phenylene or naphthylene group which may have a substituent, X_1 is a halogen atom,
There are lower alkoxy groups, phenoxy groups that may have substituents, ▲mathematical formulas, chemical formulas, tables, etc.▼(In the formula, R_
3, R_4 each independently represents a hydrogen atom or a lower alkyl group which may have a substituent, phenyl, benzyl or naphthyl group. ), ▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_5, R_6 and R_7 each independently represent a lower alkyl group.) Or a pyridinio group which may have a substituent, Y_1 is -CH= CH_2 or -
CH_2-CH_2Z_1 (in the formula, Z_1 represents a group that is eliminated by the action of an alkali), n represents a number from 1 to 3. ] The method according to claim 4. (6) The vinyl sulfone type reactive dye has the following general formula (II),
D_2-(SO_2-Y_2)_m(II) [In the formula, D_2 is a residue of an organic dye having a sulfonic acid group, Y_2 is -CH=CH_2 or -CH_2-CH_
2Z_2 (in the formula, Z_2 represents a group that is eliminated by the action of an alkali), m represents 1-3. ] The method according to claim 4. (7) Vinyl sulfone type reactive dye has the following general formula (III)
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) [In the formula, D_3 is a residue of an organic dye having a sulfonic acid group, R_8 is a hydrogen atom or a lower alkyl group that may have a substituent, W is a nitrogen atom or a carbon atom with a chlorine atom as a substituent, X_2 and X_3 are each independently a halogen atom, a lower alkoxy group, a phenoxy group which may have a substituent, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_9 and R_1_0 independently represent a hydrogen atom or a lower alkyl, phenyl, benzyl, or naphthyl group that may have a substituent.), ▲Mathematical formula, chemical formula, table, etc.▼ (In the formula , R_1_1, R_1_2, and R_1_3 each independently represent a lower alkyl group) or a pyridinio group which may have a substituent, and Y_3 is -CH=C
H_2 or -CH_2CH_2Z_3 (in the formula, Z_3
represents a group that is eliminated by the action of an alkali. ) represents. ] The method according to claim 4. (8) Water-insoluble or poorly soluble components are removed and the particle size is 0.
．． An aqueous liquid preparation characterized in that it does not contain microparticles of 0.05 μm or less. (9) A solid preparation of a reactive dye having a dye content of 80% by weight or more. (10) The formulation according to claim 9, wherein the particle size of the reactive dye is 70 μm or more. (11) The formulation according to claim 9 or 10, wherein the formulation is in the form of granules. (12) Aqueous liquid preparation according to claim 8 or claim 9
A method for dyeing textile materials, characterized by using the solid formulation described in .