JP2590778B2 - Triazine compound and method for dyeing or printing fiber material using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel triazine compound in the field of dyeing or printing fiber materials as reactive dyes.

[0002]

2. Description of the Related Art Conventionally, various reactive dyes have been widely used for dyeing and printing textile materials. For example, Japanese Patent Publication No. 39-18
No. 184 discloses a reactive dye comprising a vinylsulfone-based and monochlorotriazine-based reactive group.

[0003]

However, the known reactive dyes have a dyeing performance (eg, solubility, build-up property,
In view of the high demands on the market in terms of wash-off property, temperature sensitivity) and various fastnesses (eg, acid hydrolysis fastness, chlorine fastness), it is insufficient, and it is strongly desired to provide further improved dyes. ing. The present inventors have satisfactorily studied for the purpose of satisfying such demands, improving the drawbacks of the above-mentioned known dyes, and further finding new compounds that can widely satisfy the requirements required for the dyes. completed.

[0004]

SUMMARY OF THE INVENTION The present invention has been found as a compound having a specific performance by combining two vinyl sulfone-type reactive groups optimally with anionic dye residues using a specific crosslinking group. It is a thing. That is, the present invention provides the following formula (I)

[0005]

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Wherein R _{1 to} R ₄ are each independently hydrogen or an optionally substituted alkyl; X ₁ and X ₂ are each independently chloro, fluoro, optionally substituted aliphatic or aromatic Amino, C _1-4 alkoxy or optionally substituted phenoxy, Y ₁ and Y ₂ independently of one another
₂ CH ₂ L (L is a group removable by the action of an alkali) or vinyl, D is azo anionic dye residues, off Taroshianin based anionic dyes residues, the formazan anionic dye residue or dioxazine based anionic dye residues Express. And a method for dyeing or printing a fiber material using the same.

In the formula (I), D represents-as an anion.
SO ₃ ^- a dye residue having a metal-containing or non-metal complex azo, is preferably containing gold phthalocyanine or formazan or dioxazine based. X ₁ and
X ₂ is preferably a group that acts as a leaving group when reacting with a fibrous material such as chloro or fluoro, or a non-reactive group, such as an optionally substituted anilino It is. From the viewpoint of producing the triazine compound represented by the formula (I), X ₁ and X ₂ are preferably the same. When R _{1 to} R ₄ are optionally substituted alkyl, such groups include, for example, the groups shown in JP-A-59-122549, preferably methyl or ethyl. Preferably, R ₁ and R ₂ are identical to each other. Further, at least one of R ₃ and R ₄ is preferably hydrogen. Y ₁ and Y ₂ are −
L in the case of CH ₂ CH ₂ L is a group which is eliminated by the action of an alkali, such as OSO ₃ H, SSO ₃ H, PO
₃ H ₂ , Cl or OCOCH ₃ . Among them O
SO ₃ H is preferred. More specifically, D is preferably the following.

[0008]

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Wherein acyl is, for example, acetyl or
Means optionally substituted benzoyl. )

[0010]

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[0011]

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[0012]

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[0013]

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[0014]

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Wherein MePc is a Cu- or Ni-lid
Means rusocyanine residue, and metal phthalocyanine residue
The number of substituents on the group is 3 to 4 on average. ) Of the following structural formula
Dioxazine-dye:

[0016]

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(In the formula, R ″ represents an aliphatic or alicyclic residue.
To taste. )

[0018]

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In the above formula, an asterisk indicates -NR ₁ -or
Is -NR ₂ - represents that it is bound to.

A 1: 2-metal complex of a dye of the following structure:

[0021]

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[0022]

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(In this case, 1: 2-Cr- and 1: 2-
Co-complex salts are preferred. These 1: 2-complex salts are Cr or
Means that the residue represented by each structural formula is 2 for one Co atom.
Bond, resulting in a divalent anionic dye residue
is there. In addition , the position at which _two of SO ₂ Y ₁ and SO ₂ Y ₂ (Y ₁ and Y ₂ have the above-mentioned meaning) are bonded on the benzene ring is the same as the group of —NR ₃ — and —NR ₄ —. -As position 2,
3-, 2,4-, 2,5- or 3,4- are preferred. The compound of the present invention is preferably a salt of an alkali metal or an alkaline earth metal, particularly preferably a sodium or potassium salt. The compound of the present invention can be produced by a known method or a method analogous thereto. The produced compound of the present invention may be removed into a liquid form by removing an inorganic salt in some cases and adding a stabilizer or a dyeing property improver as necessary, or the liquid form or the reaction solution is evaporated. ,
For example, a powdery product can be obtained by spray drying, and further a liquid product or a powdery product can be obtained through salting-out separation by addition of an electrolyte by a generally known method. The compound of the present invention has a fiber reactivity and 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. The cellulosic fiber material is preferably cotton and other vegetable fibers such as linen, hemp, jute and ramie fibers. Regenerated cellulose fibers are, for example, viscose staples and filament viscose. Materials containing carbonamide groups 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. The compound of the present invention can be dyed or printed on the above-mentioned material, particularly on the above-mentioned fiber material, by a method depending on physical and chemical properties. For example, when exhaustion dyeing on cellulose fiber,
In the presence of an acid binder such as sodium carbonate, sodium tertiary phosphate, and caustic soda, a neutral salt such as sodium sulfate or salt may be added, if necessary, and a dissolution aid, a penetrant or a leveling agent may be used in combination. Performed 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, they can be padded at room temperature or at an elevated temperature, dried, and then fixed by steaming or dry heat. When printing on cellulose fibers, printing is carried out in one phase, for example with a printing paste containing baking soda or other acid binders, and then from 100 to 160.
By steaming at 2 ° C. or in two phases, for example with a neutral or weakly acidic printing paste, which is passed through a hot electrolyte-containing alkaline bath, or overpadded with an alkaline electrolyte-containing padding solution, and steamed. Alternatively, it can be performed by dry heat treatment. In the printing paste, a sizing or emulsifying agent such as, for example, sodium alginate or starch ether is used, if desired, in combination with a usual printing aid and / or dispersant such as, for example, urea.
Acid binders suitable for fixing the compounds of the invention on cellulose fibers are, for example, water-soluble basic salts of alkali metals or alkaline earth metals with inorganic or organic acids or compounds which liberate alkali under heating. 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, sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, sodium formate,
Potassium carbonate, primary, secondary or tertiary sodium phosphate, sodium silicate, sodium trichloroacetate and the like. The dyeing of synthetic and natural polyamide and polyurethane fibers is effected by first exhausting the acid or weakly acidic dye bath under controlled pH values and then neutralizing, and possibly alkaline, pH to fix.
This can be done by changing the value. Staining is usually 60-120
Although it can be carried out at a temperature of ° C., in order to achieve leveling properties, customary leveling agents such as condensation products of cyanuric chloride with three times the molar amount of aminobenzenesulfonic acid or aminonaphthalenesulfonic acid or, for example, stearylamine and ethylene oxide Can also be used. The compound of the present invention is characterized in that it exhibits excellent performance in dyeing and printing on fiber materials. It is particularly suitable for dyeing cellulose fiber materials, has high exhaustion, fastness and build-up properties, and has very good wet fastness, for example, washing fastness in the presence and absence of peroxide, alkali, It has excellent fastness to acids, water and seawater, and also has excellent fastness to friction, fastness to iron, fastness to sunlight, sweat-sunlight and sweat fastness. The compound of the present invention is also characterized in that it is hardly affected by fluctuations in the dyeing temperature, the amount of the alkali agent, the amount of the inorganic salt, and the ratio of the dyeing bath, and a stable quality dyed product can be obtained.

[0024]

The present invention will be described below with reference to examples. In the examples, parts and% mean parts by weight and% by weight, respectively.

[0025] EXAMPLE 1 1-amino-8-hydroxy-2,7-bis (5-amino-2-sulfophenylazo) -3,6-sodium salt of 71.5 parts of naphthalene disulfonic acid are dissolved in 1000 parts of water ,
While adjusting the pH to 2 to 5 by adding 37.0 parts of cyanuric chloride, the mixture is stirred at 0 to 5 ° C. to complete the first condensation. Next, 93.8 parts of 1-aminobenzene-3,4-di (β-sulfatoethylsulfone) was added, and the mixture was adjusted to pH 4-6, 40-60.
A second condensation was carried out at ℃, salting out with sodium chloride, filtration, washing and drying were performed to obtain a triazine compound represented by the following formula (1) in the form of a free acid.

[0026]

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[0027] were used in Example 1 1-amino-8-hydroxy-2,
7-bis (5-amino-2-sulfophenylazo)-
In place of 3,6-naphthalenedisulfonic acid and 1-aminobenzene-3,4-di (β-sulfatoethylsulfone), the compounds shown in columns A and B in the following table were used in equimolar amounts. The corresponding triazine compounds were obtained by the above method, and the color tone on the dyed cloth is shown in the right column. In the table, Q represents β-sulfatoethylsulfonyl or vinylsulfonyl, and may also mean other groups that can be converted to vinylsulfonyl by the action of an alkali.

[0028]

[Table 1]

[0029]

[Table 2]

[0030]

[Table 3]

[0031] For each of the compounds synthesized in Example 3 Example 1 or 2, by bringing together the third condensation with further conventional method the following compounds, to obtain a corresponding compound of the present invention. Aniline,
N-methylaniline, N-ethylaniline, aniline-
2-, 3- or 4-sulfonic acid, 2-, 3- or 4-chloro-N-ethylaniline, 2-, 3- or 4-chloro-N-methylaniline, taurine, N-methyltaurine, mono or Diethanolamine, phenol, ammonia, methanol, β-ethoxyethanol. Example 4 Instead of cyanuric chloride used in Examples 1 and 2, an equimolar amount of cyanuric fluoride was used to obtain a corresponding compound of the present invention. Dyeing Example 1 0.3 part of each of the triazine compounds obtained in Examples 1 to 4 was
Dissolve in 0 parts of water, add 10 parts of Glauber's salt, add 10 parts of cotton and add 60 parts
Heat to ° C. Then, after a lapse of 20 minutes, 4 parts of sodium carbonate was added and dyed at the same temperature for 1 hour. After completion of the dyeing, washing and soaping were performed to obtain dyed articles excellent in the above-mentioned dyeing performance and various fastnesses, respectively. Even if the dyeing temperature, the bath ratio and the amount of inorganic salt added were slightly varied, dyestuffs of stable quality with good reproducibility were obtained. Dyeing example 2 Color paste composition Each of the triazine compounds obtained in Examples 1 to 5 5 parts Urea 5 parts Sodium alginate (5%) original paste 50 parts Hot water 25 parts Baking soda 2 parts Balance 13 parts Color paste of the above composition is mercerized. Print on cotton broad, dry in the middle, steam at 100 ° C for 5 minutes,
Wash, soap, wash and dry. In this way, a printed matter having excellent dyeing performance and various fastnesses as described above was obtained. Dyeing Example 3 25 parts of each of the triazine compounds obtained in Examples 1 to 4 were dissolved in hot water and cooled to 25 ° C. To this, 5.5 parts of a 32.5% aqueous solution of caustic soda and 150 parts of 50 ° beaume water glass were added, and water was further added to bring the total amount to 1000 parts at 25 ° C.
Using this liquid as padding liquid, wind up the cotton fabric,
Store in a room at 20 ° C sealed with polyethylene film. The cotton fabric is padded and wound up in the same manner, and the cotton fabric sealed with a polyethylene film is stored in a room at 5 ° C.
In each case, after leaving the padding cloth for 20 hours, the dyed material is washed with cold water, then with hot water, soaped in a boiling detergent,
After washing with cold water, dry and finish. When the color difference and density difference between the dyed product left at 20 ° C. for 20 hours and the dyed product left at 5 ° C. for 20 hours were examined, almost no difference was observed. In addition, a dyed product having good build-up properties was obtained by cold batch-up dyeing.

Claims (4)

(57) [Claims] (1) The following formula (I): Wherein R _{1 to} R ₄ are independently hydrogen or optionally substituted alkyl, X ₁ and X ₂ are independently chloro,
Fluoro, optionally substituted aliphatic or aromatic amino, C _1-4 alkoxy or optionally substituted phenoxy, Y ₁ and Y ₂ are each independently —CH ₂ CH ₂ L
(L is a group which desorbs under the action of an alkali) or vinyl, D is expressed azo anionic dye residues, off Taroshianin based anionic dyes residues, the formazan anionic dye residue or dioxazine based anionic dye residues. A triazine compound represented by the formula: 2. The compound according to claim _1, wherein X ₁ and X ₂ are independently chloro or fluoro. 3. The compound according to claim _1, wherein X ₁ and X ₂ are independently anilino which may be substituted. 4. The compound according to claim 1, wherein R _{1 to} R ₄ are each independently hydrogen, methyl or ethyl .