JPH0554511B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the following general formula () [In the formula, Z ₁ and Z ₂ are each independently,

[Formula] is chlorine or fluorine, but at least one of Z ₁ and Z ₂ is

[Formula] (wherein, X is a hydroxyl group, sulfo group or sulfate group). D is

[Formula] (wherein R is hydrogen or a C ₁ - C ₄ alkyl group) represents an organic dye residue having one or more water-soluble groups bonded to the triazine ring, and Y is an optionally substituted amino group. represents a group, a hydroxyl group, or a halogen atom. ] The present invention relates to a triazine compound shown in the following and a method for dyeing or printing using the same. Although reactive dyes are widely used for dyeing and printing textile materials, at present the known dyes are not yet satisfactory in terms of suitability for specific dyeing methods and high requirements regarding fastness.
There is a strong desire to provide further improved reactive dyes. An object of the present invention is to provide a novel compound that can broadly satisfy the requirements required for reactive dyes. Examples of the organic dye residue represented by D in formula () include azo, alloy azo, formazan, phthalocyanine, anthraquinone, etc.
These are those having at least one water-soluble group such as sulfonic acid or cacabonic acid. Examples of the optionally unsubstituted or substituted amino group or hydroxyl group represented by Y include the following. Amino, alkylamino (methylamino, ethylamino, propylamino, butylamino, dimethylamino, diethylamino, methylethylamino, octylamino, cyclohexylamino),
Hydroxyalkylamino (monoethanolamino, diethanolamino), cyanoalkylamino (β-cyanoethylamino, di-β-cyanoethylamino), β-sulfoethylamino, taurine residue, glycine residue, anilino, sulfo, chloro, lower Anilino (o-, m-
or p-sulfoanilino, 2,5-disulfoanilino, o-, m- or p-toluidino, o-, m
- or p-methoxyanilino, o-, m- or p
-chloroanilino, 2-methyl-4-sulfoanilino, 2-methoxy-4-sulfoanilino, p-
Nitroanilino, 2-sulfo-4-methylanilino, 4-chloro-2-sulfoanilino, o-, m
- or p-carboxyanilino, 2-carboxy-4-sulfoanilino), N-methylanilino,
N-ethyl-4-chloroanilino, alkoxy (methoxy, ethoxy, propoxy, butoxy),
Phenoxy, chloro, nitro, methyl, sulfo,
Phenoxy substituted with carboxy etc. (o-,
m- or p-chlorophenoxy, o-, m- or p-nitrophenoxy, o-, m- or p-sulfophenoxy, o-, m- or p-carboxyphenoxy, morpholino, piperidino, piperazino. The compound of general formula () is a dye in which Z ₁ and Z ₂ are chlorine or fluorine, preferably in an aqueous solution of 40 to 105
℃, PH4-9, the following formula () [In the formula, X has the above meaning. ] It can be produced by reacting with a compound represented by the following or an alkali metal salt thereof. The compound represented by the formula () includes α-,
β- or γ-(2hydroxyethyl)pyridine,
α-, β- or γ-(2-sulfoethyl)pyridine, α-β- or γ-(2-sulfatoethyl)
Examples include pyridine, of which α- and γ-isomers are particularly cited as raw materials with high industrial value. Preferred fiber materials that can be applied in the present invention include cellulose fibers such as cotton, viscose rayon, cuprammonium rayon, hemp, and polyesters containing cellulose fibers, triacetate, polyacrylonitrile, modified polyacrylonitrile, polyamide, wool, It is applicable to mixed fiber materials such as silk (cellulose-containing fiber materials) in any form such as yarn, fabric, skein, loose fiber, etc. In the present invention, dyes necessary for dyeing fiber materials other than cellulose, such as Color Index
Third edition and its Additions and Amendments
Dyeing can be carried out by simultaneously adding disperse dyes, basic dyes, cationic dyes, acidic dyes, acidic metal-containing dyes, etc. described in . In the present invention, in the general formula (), the group

A reactive dye (hereinafter referred to as a precursor) in which a halogen atom, particularly a halogeno-s-triazinyl group, which is a chlorine atom or a fluorine atom, is bonded to the bonded position of [Formula] (X has the above meaning) and a formula ( Dyeing can also be carried out by placing a compound represented by formula () or an alkali metal salt thereof in a dye bath to form a compound represented by general formula (). The amount of the compound of formula () or its alkali metal salt to be used is 0.5 per halogen atom of the reactive dye containing a halogeno-s-triazinyl group as a precursor.
-10 times the molar amount, preferably 1.0 to 5 times the molar amount. The dyeing according to the invention preferably prepares an aqueous dyebath containing 1 to 150 g of cellulose or cellulose-containing fiber material and optionally an electrolyte, preferably sodium chloride or sodium sulfate. Next, the pH value of this dye bath is maintained within the range of 4 to 10 during the entire dyeing process.
Staining is started at a temperature of 100°C or less, and the temperature is increased as the staining progresses, and staining is carried out at 100 to 150°C for 10 to 90 minutes. In the present invention, the pH during dyeing is maintained in the range of 4 to 10 as described above, but preferably the pH is maintained in the range of 5 to 9 from before the start of dyeing to the end of dyeing. Provides staining reproducibility. In that case, the above
In order that the pH range is maintained during the entire dyeing process, suitable substances exhibiting a buffering effect in the aqueous dyebath, such as acids such as sulfuric acid, hydrochloric acid, carbonic acid, boric acid, phosphoric acid, acetic acid, tartaric acid, citric acid, and their sodium Single salts, potassium salts or ammonium salts or mixtures thereof can be added. However, the present invention is not particularly limited to these. The amount of buffering agent mentioned above is advantageously between 0.5 and 5.0 g/
It is. In addition, reactive dyes, precursors of such dyes and compounds of formula () or their salts or dyes and electrolytes for dyeing textile materials other than cellulose may be added to the dyebath before the start of dyeing or It can also be added throughout the dyeing process. A reduction inhibitor such as sodium metanitrobenzenesulfonate, an anionic, nonionic or cationic leveling agent, a loosening agent, a dispersing agent, an anti-settling agent, etc. can be added to the dye bath. As mentioned above, cellulose-containing fiber materials can be dyed by a one-bath, one-step method in which cellulose and non-cellulose fiber materials are advantageously dyed simultaneously; A one-bath two-step method for dyeing one fiber material may be applied, or a two-bath method for dyeing a cellulose-containing fiber material from separate baths by combining the dyeing method of the present invention and a dyeing method for fibers other than cellulose. It can also be dyed by The dyeing machine suitable for the dyeing of the present invention is not particularly limited as long as it can dye by the exhaustion method at a dyeing temperature of 100 to 150°C, but generally equipment and equipment that can raise the temperature to a temperature of 100 to 150°C are used. A rotary dyeing machine, a jet dyeing machine, a cheese dyeing machine, a cake dyeing machine, an Obermeyer dyeing machine, a wince dyeing machine, a jitter dyeing machine, a jet dyeing machine and the like are suitable. When the compound of the present invention is used to dye or print cellulose fiber materials or cellulose-containing fiber materials by a padding method in the absence of an acid binder, for example, the compound may be treated with a punching liquid or printing paste that does not contain an acid binder. Fiber materials, if required, 80~
This can be done by drying at 100°C and then heating to 150°C or higher. Heating above 150 DEG C. is usually carried out at a temperature of 160 DEG to 250 DEG C., especially 180 DEG to 230 DEG C., for example by baking at about 200 DEG C. for a few minutes or by steaming at 180 DEG C. for 5 to 10 minutes. This dyeing method is particularly advantageous for printing cellulose/polyester mixed fiber materials. On the other hand, when dyeing or printing only the cellulose fiber material with the above compound (), it is also possible to carry out dyeing or printing by employing the dyeing conditions for ordinary reactive dyes. The compound of the present invention is suitable for printing, especially dyeing, fiber materials containing cellulose fiber materials,
It is distinguished from known reactive dyes. Next, the present invention will be explained according to examples, where "parts" in the examples are "parts by weight" unless otherwise specified. Example 1 A compound of the formula below, expressed in the form of a free acid, was prepared using the corresponding monochlorotriazine compound (a known reactive dye) to prepare γ-(β-sulfatoethyl)
It was obtained by stirring overnight at 80°C with pyridine and pH 4.0 to 4.5, and then filtering with salt using NaCl. Example 2 Using the reactive dyes listed in column 2 of the following table, a compound of formula () in column 3 - which is shown below a α-(2-hydroxyethyl)pyridine b β- hydroxyethyl)pyridine c γ-(2-hydroxyethyl)pyridine d α-(2-sulfoethyl)pyridine e β-(2-sulfoethyl)pyridine f γ-(2-sulfoethyl)pyridine g α-(2-sulfate ethyl)pyridine h β-(2-sulfatoethyl)pyridine i γ-(2-sulfatoethyl)pyridine represented by the symbols (a to i) is reacted in the same manner as in Example 1. The color tone of the obtained invention compound on the fiber is shown in the fourth column.

[Table] Dyeing example 1 0.1, 0.3 and 0.6 of the dye produced according to Example 1
1 part of sodium chloride was dissolved in 200 parts of water, 10 parts of Glauber's salt and 10 parts of cotton were added, the temperature was raised to 120°C, 4 parts of soda carbonate was added,
Stain for 1 hour at the same temperature. By washing with water, soaping, washing with water and drying, a golden yellow dyed product having excellent fastness and good build-up properties was obtained. Furthermore, similar results were obtained for cotton/polyester 1:
It was also obtained on cotton with a blending ratio of 1. Dyeing Example 2 4.5 parts of dye prepared according to Example 1, 10.0 parts of urea
part, sodium alginate, 10% aqueous solution of glue
50.0 parts of sodium m-nitrobenzenesulfonate, 1.0 parts of sodium bicarbonate, and 1.0 parts of water were added to make 100 parts of printing paste, and the printed material was printed on cotton. After drying, the printed material was scanned at 102°C for 5 minutes. Teaming.
The printed material is washed with cold and hot water and dried. The prints obtained have excellent fastness properties.
Also, instead of steaming for 5 minutes at 102℃
A similar print was obtained by steaming at 175°C for 6 minutes. Furthermore, similar results were obtained with a cotton/polyester ratio of 1:1.
It was also obtained on cotton with a blending ratio of . Staining example 3 Sodium m-nitrobenzenesulfonate 0.5
2.0 parts of the dye obtained according to Example 1 by adding 100 parts of water. The cotton material is impregnated with the resulting solution to give a weight gain of 75% and then dried. Next, this dyed material was impregnated in a warm solution at 20°C containing 5 g of caustic soda and 300 g of common salt, squeezed to a weight increase of 75%, and the dyed material was heated at 200°C.
A golden yellow dyeing was obtained by steaming for 30 seconds, rinsing, soaping for 15 minutes in a 30% boiling solution of non-ionic detergent, rinsing and drying. Similar dyed products were obtained when steaming at 200° C. for 30 seconds after drying was replaced with any of the following. (a) Baking at 210°C for 1 minute (b) Baking at 180°C for 3 minutes (c) Baking at 150°C for 5 minutes Similar results were also obtained on cotton with a 1:1 cotton/polyester blend. . Dyeing example 4 2 parts of the dye according to example 1, Na ₂ SO ₄ 60
1 part, sodium m-nitrobenzenesulfonate
part, Na ₂ HPO _{4.2H 2} O2 part as buffering agent and
An aqueous dye bath was prepared consisting of 0.5 parts of KH ₂ PO ₄ and 934.5 parts of water. The pH value of the dye bath at this time was 7. 50 parts of scouring and bleaching unsilced cotton stockinette was added to this dye bath at room temperature, and the temperature was raised to 120°C over 30 minutes while stirring, and dyed at that temperature for 60 minutes. after staining
The pH was able to be maintained at 7, unchanged from before the start of staining. After dyeing, the fabric was washed with water, soaped with 1000 parts of an aqueous solution containing 2 parts of an anionic surfactant at 100°C for 10 minutes, and then washed with water and dried. The dyed product showed good dyeing power and a golden yellow dyed product with excellent color fastness was obtained. Dyeing Example 5 5 parts of dye prepared according to Example 1, 20 parts of urea
The printing paste was made by adding 50 parts of a 10% aqueous solution of sodium alginate paste to 100 parts, and the printed material was printed on cotton at 180℃ after drying.
Steam for 10 minutes. The printed material is washed with cold and hot water and dried. The print obtained shows a golden yellow dyeing with good washing fastness. A similar dyed product was also obtained by baking at 200°C for 1 minute instead of steaming at 180°C for 10 minutes. Furthermore, similar results were obtained on cotton with a 1:1 cotton/polyester blend ratio. Staining example 6 Sodium m-nitrobenzenesulfonate
Dye obtained according to Example 1 with addition of 0.5 parts 2.0
Dissolve 1 part in 100 parts of water. The cotton material is impregnated with the resulting solution to give a weight gain of 75% and then dried. A golden yellow dyeing was obtained by steaming the dyeing at 200° C. for 2 minutes, rinsing, soaping in an 80% boiling solution of a non-ionic detergent for 15 minutes, rinsing and drying. Similar dyed products were obtained when steaming at 200° C. for 2 minutes after drying was replaced with any of the following. (a) Baking at 210℃ for 3 minutes (b) Baking at 180℃ for 5 minutes (c) Baking at 150℃ for 7 minutes At this point, to obtain better dyeing reproducibility, add a buffer to adjust the pH to 4-10. Similar results were obtained when the temperature was kept at . Furthermore, similar results were obtained on cotton with a 1:1 cotton/polyester blend ratio. Dyeing Example 7 By using the dye of Example 2 in place of the dye of Example 1 and dyeing according to the method of Dyeing Examples 1 to 6, dyed or printed products with similar excellent performance can be obtained. It was done.

Claims (1)

[Claims] 1. The following general formula [In the formula, Z ₁ and Z ₂ are independently [Formula] chlorine or fluorine, but at least one of Z ₁ and Z ₂ is [Formula] (wherein, X is a hydroxyl group, a sulfo group, or a sulfate basis). D represents an organic dye residue having one or more water-soluble groups bonded to the triazine ring in the formula (wherein R is hydrogen or a C ₁ to C ₄ alkyl group), and Y is substituted or not. Represents a good amino group, hydroxyl group or halogen atom. ] A triazine compound represented by 2 General formula below [In the formula, Z ₁ and Z ₂ are independently [Formula] chlorine or fluorine, but at least one of Z ₁ and Z ₂ is [Formula] (wherein, X is a hydroxyl group, a sulfo group, or a sulfate basis). D represents an organic dye residue having one or more water-soluble groups bonded to the triazine ring in the formula (wherein R is hydrogen or a C ₁ to C ₄ alkyl group), and Y is substituted or not. Represents a good amino group, hydroxyl group or halogen atom. ] A method for dyeing or printing a fiber material, characterized by using a triazine compound shown in the following.