JPH0834932A - Triazine compound and method for dyeing or printing fiber material using the same - Google Patents

Abstract

PURPOSE:To obtain the compound, useful especially for dyeing or printing containing cellulosic fiber material, having high exhaustion, fixing and buildup properties and excellent in wet color fastness, color fastness to rubbing, etc. CONSTITUTION:This triazine compound of formula I [R1 to R4 are independently each H or a (substituted)alkyl; X1 and X2 are independently each chloro, fluoro, a (substituted)aliphatic, a (substituted)aromatic amino, etc.; Y1 and Y2 are independently each CH2CH2L (L is a group eliminative by the actions of an alkali) or vinyl; D is an azo-based anionic dye residue, an anthraquinone-based anionic dye residue, etc.], e.g. a compound of formula II. The triazine compound of formula I has reactivity with fibers and can be used for dyeing or printing a fiber material containing hydroxy or a carbonamide. For example, the exhaustion and dyeing on cellulosic fibers is carried out in the presence of an acid binder such as sodium carbonate at a relatively low temperature by using preferably a neutral salt, a dissolution assistant, etc., in combination.

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 fiber materials. For example, Japanese Patent Publication Sho 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 inventors of the present invention have made extensive studies in order to improve the drawbacks of the above-mentioned known dyes by satisfying such a demand, and further to find a novel compound that can widely satisfy the requirements required for 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 capable of leaving by the action of an alkali) or vinyl, D is an azo anion dye residue, an anthraquinone anion dye residue, a phthalocyanine anion dye residue, a formazan anion dye residue or dioxazine Represents an anionic dye residue. And a method for dyeing or printing a fiber material using the same.

In the formula (I), D represents-as an anion.
It is a dye residue having SO ₃ ⁻ and is preferably a metal-containing or non-metal-containing azo type, anthraquinone type, a metal containing phthalocyanine type, formazan type or dioxazine type. X ₁ and X ₂ are preferably groups which act as leaving groups when reacting with the fibrous material such as chloro or fluoro or are non-reactive groups, for example preferred groups are substituted It is a good Anilino. From the viewpoint of producing the triazine compound represented by the formula (I), X ₁ and X ₂ are preferably the same. R _{1 to} R ₄
When is an optionally substituted alkyl, examples of such a group include those described in JP-A-59-122549, and preferably methyl or ethyl. R
₁ and R ₂ are preferably the same as each other. Also, R
_At least one of ₃ and R ₄ is preferably hydrogen. L when Y ₁ and Y ₂ are -CH ₂ CH ₂ L
Is a group capable of leaving by the action of an alkali.
₃ H, SSO ₃ H, PO ₃ H ₂ , Cl or OCOCH ₃
Is mentioned. Of these, OSO ₃ H is preferable. More specifically, D is preferably the following.

[0008]

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[0009]

[Chemical 4]

[0010]

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Wherein acyl means, for example, acetyl or optionally substituted benzoyl.

[0012]

[Chemical 6]

[0013]

[Chemical 7]

(Wherein MePc means a Cu- or Ni-phthalocyanine residue, and the number of substitutions of the metal phthalocyanine residue is on average 3 to 4.) A dioxazine-dye of the following structural formula:

[0015]

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(In the formula, R "means an aliphatic or alicyclic residue.)

[0017]

[Chemical 9]

Metal complex salts of dyes of the following structure:

[0019]

[Chemical 10]

[0020]

[Chemical 11]

(In this case, 1: 1-Cu-complex or 1:
2-Cr- and 1: 2-Co-complex salts are preferred. ) All of the anionic dye residues represented by the above structural formulas are monovalent or divalent, but combinations in which the valences of these structural formulas and the valences of D match correspond to each specific example. Therefore, in order to match the valences, hydrogen can be bonded at any of the bonds indicated by *, and such anionic dye residues are also exemplified. On the other hand, the positions at which _two of SO ₂ Y ₁ and SO ₂ Y ₂ (Y ₁ and Y ₂ have the above-mentioned meanings) are bonded to the benzene ring are the groups —NR ₃ — and —NR ₄ — 2,
3-, 2,4-, 2,5- or 3,4- are preferred. The compound of the present invention is preferably an alkali metal or alkaline earth metal salt, and 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 can be made into a liquid product by optionally removing an inorganic salt and optionally adding a stabilizer or a dyeability improving agent, or evaporating the liquid product or the reaction solution. ,
For example, it can be made into a powder product by spray drying, and can also be made into a liquid product or a powder product 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 a cellulose fiber according to the padding method, it can be fixed by steaming or dry heat after padding and drying at room temperature or an elevated temperature. 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 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, steaming 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.
Suitable acid binders 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 with compounds which liberate alkali when heated. In particular, alkali metal hydroxides and weak to moderately strong inorganic or organic acid alkali metal salts are mentioned, 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,
Examples thereof include potassium carbonate, primary, secondary or tertiary sodium phosphate, sodium silicate, sodium trichloroacetate and the like. Dyeing of synthetic and natural polyamide and polyurethane fibers is carried out by first exhausting from an acidic or weakly acidic dyeing bath under control of the pH value, and then to a neutral, optionally alkaline pH for fixing.
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.

[0022]

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

Example 1 11.5 Amino-8-hydroxy-2,7-bis (5-amino-2-sulfophenylazo) -3,6-naphthalenedisulfonic acid 71.5 parts of sodium salt was 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-sulfatoethyl sulfone) was added to adjust the pH to 4 to 6 and 40 to 60.
Second condensation was carried out at ℃, salting out with sodium chloride, filtration, washing and drying to obtain a triazine compound represented by the following formula (1) in the form of a free acid.

[0024]

[Chemical 12]

Example 2 1-amino-8-hydroxy-2 used in Example 1
7-bis (5-amino-2-sulfophenylazo)-
Instead of 3,6-naphthalenedisulfonic acid and 1-aminobenzene-3,4-di (β-sulfatoethylsulfone), the compounds shown in Columns A and B of the following Tables in equimolar amounts were used, respectively. The corresponding triazine compounds were obtained by the method of 1. and the color tone on the dyed fabric 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.

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

[Table 3]

Example 3 The corresponding compound of the present invention was also obtained by subjecting each of the compounds synthesized in Example 1 or 2 to the third condensation of the following compounds by a conventional method. 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
Dissolve in 0 part of water, add 10 parts of Glauber's salt, add 10 parts of cotton and add 60 parts
Raise the temperature to ℃. 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 dyeing, washing with water and soaping were carried out to obtain dyed products excellent in dyeing performance and various fastnesses. Even when the dyeing temperature, the bath ratio and the addition amount of the inorganic salt were slightly changed, a dyed product with good reproducibility and stable quality was 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 material having excellent dyeing performance and various fastnesses 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.
Roll up a cotton fabric using this solution as a padding solution,
Seal with polyethylene film and store in a room at 20 ° C. The cotton fabric padded and rolled up in the same manner and 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. Further, a dyed product having good build-up property was obtained by cold batch-up dyeing.

Claims (5)

[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 capable of leaving by the action of an alkali) or vinyl, D is an azo type anion dye residue, an anthraquinone type anion dye residue, a phthalocyanine type anion dye residue, a formazan type anion dye residue or a dioxazine type anion dye residue. Represents a group. A triazine compound represented by the formula: 2. The compound according to claim _1, wherein X ₁ and X ₂ are independently of each other 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. 5. A method for dyeing or printing a fiber material, which comprises using the compound according to any one of claims 1 to 4.