JPS63128078A - Triazine compound and dyeing or printing of fibrous material with said compound - Google Patents

Abstract

NEW MATERIAL:A compound having at least one group expressed by formula I [R is H or (substituted)alkyl; Y is -CH2CH2L (L is group eliminable by the action of alkali)]. EXAMPLE:The compound of formula II. USE:A reactive dye for dyeing a material containing OH group (e.g. cellulosic fiber) or a material containing carbonamide group (e.g. polyamide), especially a cellulosic fiber material. It has excellent in various fastnesses and is insensitive to the influence of dyeing temperature, amounts of alkaline agent and inorganic salt and variation of dyeing bath composition. PREPARATION:The objective compound can be produced e.g. by condensing 1-amino-8-hydroxy-7-(o-sulfophenylazo)-3,6-naphthalenedisulfonic acid Na salt with cyanuryl chloride and condensing the reaction product with 1- aminobenzene-8,4-di(beta-sulfatoethylsulfone).

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to novel triazine compounds in the field of dyeing or printing textile materials as reactive dyes.

BACKGROUND OF THE INVENTION Traditionally, reactive dyes have been widely used for dyeing and printing textile materials. For example, Japanese Patent Publication No. 39-18184 discloses a reactive dye comprising a vinyl sulfone-based and a monochlorotriazine-based reactive group.

However, the known reactive dyes meet the high demands of the market in terms of dyeing performance (e.g. solubility, build-up properties, wash-off properties, temperature sensitivity) and hardness properties (e.g. acid hydrolysis biotransformation, chlorine fastness). It is insufficient from this point of view, and there is a strong desire to provide a further improved dye.

The inventors of the present invention have conducted intensive studies with the aim of finding a new compound that satisfies the above-mentioned needs, improves the drawbacks of the above-mentioned known dyes, and further satisfies a wide range of requirements for dyes. Completed the invention.

Means for Solving the Problems The present invention has been discovered as a compound having specific performance by optimally combining two vinyl sulfone type reactive groups with an anionic dye residue using a specific bridging group. It is something.

That is, the present invention provides at least one of the following formulas (1) [wherein,
R is hydrogen or optionally substituted alkyl, Y is -C
It represents H, CH, L (L is a group that is eliminated by the action of an alkali) or vinyl. The present invention provides a triazine compound having a group represented by the following and a method for dyeing or printing fiber materials using the triazine compound.

As the triazine compound having at least one group represented by formula (I), preferably the following formula (If) [wherein R
1 and R are independently hydrogen or optionally substituted alkyl, xl is chloro, fluoro, optionally substituted aliphatic or aromatic amino, 01-4 alkoxy or optionally substituted phenoxy, Yl and Y2
are each independently -CH, CH, L (L is a group that is eliminated by the action of an alkali) or vinyl, and Dl represents an anionic dye residue. ] A compound represented by the following formula (DI) R□ [wherein R3, R4 and R6 are independently hydrogen or optionally substituted alkyl, Y3. Y4 and Y5 independently represent -CI (2CH2L (L is a group that is eliminated by the action of an alkali) or vinyl; D2 and D3 independently represent anionic dye residues), a compound represented by the following formula (IV ) [In the formula, R6* R7* R8 and R9 are independently hydrogen or optionally substituted alkyl, x2 and
are independently chloro, fluoro, optionally substituted aliphatic or aromatic amino, 01-4 alkoxy or optionally substituted phenoxy, Y6 and Yl are independently -CH4CH2L (L is due to the action of alkali) or vinyl, D4 represents an anionic dye residue. ] A compound represented by the following formula (V) [wherein R1゜e RIS e R11* RL! p
R14 and R18 are independently hydrogen or optionally substituted alkyl, W is a divalent bridging group, Y, , Y
, , Ylo and Y5. are independently of each other -CH2CH
2L (L is a group that is eliminated by the action of an alkali) or vinyl,
D and D6 independently represent anionic dye residues. ] Examples include compounds represented by the following.

In formulas (II) to (V), the anionic dye residues D1 to D6 are dye residues having -503e as an anion, and are typically metal-containing or non-metallic azo-based, anthraquinone-based, A metal-containing phthalocyanine type, formazan type, dioxazine type or stilbene type is preferable. Formula (1) and formula (Iv) niote, Xt −
Xs and HiXs 1. t, preferably a group that acts as a shedding group when reacting with the fiber material, such as chloro or fluoro, or a non-reactive group, such as a preferred group, even if substituted. It's a good Anilino. X, and X.

In formulas (■) to (V), when R and R1 to RI8 are optionally substituted alkyls, such groups include, for example, the groups shown in JP-A-59-122549. However, methyl or ethyl is preferred. R1 and R
,, R3, R4 and R8-R4 and R11s R1! and R1
In each group of 3pR14 and R15, at least one of the elements constituting each group is preferably hydrogen. Preferably, R6 and R7 and R1° and R11 are the same.

In formula (V), W is C2-6 alkylene, phenylene, mono- or disulfophenylene, 1°8, 5-
) methyl-4-sulfo-2,6-phenylene, 6-substituted-1,8,5-triazine-2°4-diyl or stilbene-4,4'-diyl.

L when Y and Y1 to Y11 are -CH2CH,L
is a group that is eliminated by the action of an alkali, for example, 0
50, H, 5SO3H, PO, H,, CI or OCOC
Examples include H3. Among them, 080. H is preferred.

More specifically, ~D6 in the compounds of formulas (1) to (V) is preferably the following.

cbu3m). .

(SOsH)1-s (SOsH). -2 in which R' =)i or CH, and acyl means, for example, acetyl or optionally substituted benzoyl).

(In the formula, MePc means a Cu- or N1-phthalocyanine residue, and the number of substitutions of the metal phthalocyanine residue is on average 8 to 4.) A dioxazine dye of the following structural formula: or alicyclic group).

(SO,H)1° (in this case 1:1-Cu-fil salt or 1:2-
Cr- and 1:2-Co-complex salts are preferred. ) The anionic dye residues shown in the above structural formulas are all -valent or divalent, but the valence of these structural formulas and Dl to D
Combinations in which the valences of 6 match correspond to each specific example. Therefore, in order to match the valences, hydrogen can be bonded to any of the bonds indicated by the cross-marks, and such anionic dye residues are also exemplified.

On the other hand, in the group represented by formula (1), SO2-Y(Y
has the meaning given above. ) on the benzene ring is 2.3-1, with the group -N- as the 1-position.
2.4-12,5- or 8°4- is preferred.

The compound of the present invention is preferably an alkali metal or alkaline earth metal salt, particularly sodium or potassium ±IX.

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 removing inorganic salts and adding stabilizers or dyeability improvers as necessary, or by evaporating or evaporating this liquid product or reaction solution. For example, it can be made into a powder product by spray drying, and it can also be made into a liquid or powder product through salting out separation by adding an electrolyte using a generally known method.

The compound of the present invention has fiber reactivity and can be used for dyeing or printing hydroxy group-containing or carbonamide group-containing materials. Preferably, the material is used in the form of a fibrous material or a blend thereof.

Hydroxy group-containing materials are natural or synthetic hydroxy group-containing materials, such as cellulose fiber materials or their regenerated products and polyvinyl alcohol. The cellulose a-fiber material is preferably cotton, but also other vegetable fibers such as linen, hemp, jute and porcelain fibers. Regenerated cellulose fibers are, for example, viscose staple and filament viscose.

Materials containing carbonamide groups are, for example, synthetic and natural polyamides and polyurethanes, especially in the form of fibers, such as wool and other animal hairs, silk, leather, polyamide-6,
6, Boria Shido 6, Boria Shiba Do 11, and Polyamide-4.

The compound of the present invention can be dyed or printed on the above-mentioned materials, particularly on the above-mentioned a-fiber materials, by a method depending on the physical and chemical properties.

For example, in the case of exhaust dyeing on cellulose fibers, in the presence of an acid binder such as soda carbonate, tribasic sodium phosphate, caustic soda, etc., optionally with the addition of a neutral salt, such as mirabilite or common salt,
If desired, solubilizers, penetrants or leveling agents are used in combination and the process is carried out at relatively low temperatures. The neutral salts which accelerate the exhaustion of the dyestuff can be added only after the actual dyeing temperature has been reached, or even before then, optionally in portions.

When dyeing cellulose m-fibers according to the padding method, it can be padded at room temperature or at an elevated temperature, dried and then fixed by steaming or dry heat.

When printing is carried out on cellulose fibers, either in one phase, e.g. by printing with a printing paste containing baking soda or other acid binders and then steaming at 100-160°C, or in two phases, e.g. Printing can be carried out by printing with an acidic or weakly acidic printing paste, passing it through a hot electrolyte-containing alkaline wash bath, or overpadding with an alkaline electrolyte-containing padding liquid and steaming or dry heat treatment.

In the printing pastes, lake agents or emulsifiers, such as, for example, sodium alginate or starch ethers, are used, if desired, in combination with customary printing auxiliaries and/or dispersants, such as, for example, urea.

Suitable acid binders for fixing the compounds of the present invention on the cellulose fringe fibers are, for example, water-soluble basic salts of alkali metals or alkaline earth metals with inorganic or organic acids or compounds that liberate alkali upon heating. Particular mention may be made of alkali metal hydroxides and alkali metal salts of weak to medium strength inorganic or organic acids, of which soda salts and potassium salts are particularly preferred. Such acid binders include, for example, caustic soda, caustic potash, baking soda, soda carbonate, sodium formate, potassium carbonate, and the like.

Examples include secondary or tertiary sodium phosphate, sodium silicate, and sodium trichloroacetate.

The dyeing of synthetic and natural polyamide and polyurethane fibers is carried out first by exhaustion under pH control from an acidic or slightly acidic dye bath, and then by changing to a neutral or even alkaline OpH value for fixation. I can do it. Dyeing can usually be carried out at a temperature of 60 to 120°C, but in order to achieve level dyeing properties, conventional leveling agents such as a condensation product of cyanuric chloride and 3 times the mole of aminobenzenesulfonic acid or aminobenzenesulfonic acid or For example, addition products of 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 textile materials. Particularly suitable for dyeing cellulose fiber materials, with high exhaustion, fastness and build-up properties, very good wet fastness properties, e.g. , excellent fastness to alkalis, acids, water and seawater;
It is also susceptible to scratch fastness, iron fastness, sunlight fastness, sweat-sunfastness, and sweat fastness. The compound of the present invention is also characterized in that it is not affected by changes in dyeing temperature, alkaline agent, amount of inorganic salt added, and dye bath ratio, and is capable of producing dyed products of stable quality.

The details of the present invention will be explained below with reference to Examples.

In the examples, parts and 610 mean parts by weight and % by weight, respectively.

Example 1 1-amino-8-hydroxy-7-(o-sulfophenylazo")-1,6-naphthalenedisulfonic acid 50.4
1 part of sodium salt was dissolved in 500 parts of water, 18.5 parts of cyanuric chloride was added, and the pH was adjusted to 0 to 8.
Stir at 5°C to complete the first condensation.

Next, 46.9 parts of 1-aminobenzene-8,4-di(β-sulfatoethyl sulfone) was added, and the pH was adjusted to 4-4.
5. Perform the second condensation at 40-50°C, salt out with sodium chloride, filter, wash and dry to obtain the triazine represented by the following formula (1)% formula %) in the form of free acid. The compound was obtained.

Example 2 1-Amino-8-hydroxy-7- used in Example 1
In place of (o-sulfophenylazo)-8,6-naphthalenedisulfonic acid and 1-aminobenzene-8,4-di(β-sulfatoethylsulfono), 84 equivalent moles of The corresponding triazine compounds were obtained in the same manner, and the color tone of the dyed soil was recorded in the right column. In the table, Q represents β-sulfate ethersulfonyl or vinylsulfonyl, and the It can also mean a group other than this, which can be converted into vinylsulfonyl by the action of an alkali.

Example 8 Instead of cyanuric chloride used in Examples 1 and 2,
Using equimolar amounts of cyanuric fluoride, the corresponding compounds of the present invention were obtained.

Example 4 Each of the compounds synthesized in Example 2 or 8 was subjected to third condensation with the following compounds in a conventional manner to obtain corresponding compounds of the present invention.

Aniline, N-methylaniline, N-ethylaniline,
Aniline-2-13- or 4-sulfonic acid, 2-18-
or 4-chloro-N-ethylaniline, 2-18- or 4-chloro-N-methylaniline, tallalin, N-methyltalaline, mono- or jetanolamine, phenol, ammonia, methanol, β-ethoxyethanol.

In addition, the above compound and the compound described in B8 could also be synthesized by appropriately performing the reaction in the reverse order.

Example 5 The compound described in Affa used in Example 2 was subjected to the first and second condensation with cyanuric chloride or cyanuric fluoride using twice the amount used in Example 2, and the compound described in column B was The compound of the present invention contained in formula 0 was obtained by third condensation with the compound of formula 0 by a conventional method.

Example 6 The compounds obtained in Examples 1.2 and 3 were subjected to a third condensation process using a conventional method to obtain a compound of the present invention contained in formula (V).

Ethylenediamine, metamine, paraamine, m- or 1
)-phenylenediaminesulfonic acid, 2.4.6-drimethyl-8,5-diaminobenzenesulfonic acid, 4.4
'-Diaminostilbene, 4,4'-diaminodiphenylurea, piperidine.

Example 7 71.5 parts of sodium salt of 1-amino-8-hydroxy-2,7-bis(5-amino-2-sulfophenylazo)-8,6-naphthalenedisulfonic acid was dissolved in t, ooo parts of water. Then, add 87.0 parts of cyanuric chloride to adjust the pH to 2~
The first condensation is completed by stirring at 0-5°C while adjusting the temperature to 5°C. Then, 1-aminobenzene-8,4-di(
Add 98.8 parts of β-sulfatoethyl sulfone,
Second condensation is carried out at pH 4 to 6.40 to 60°C, salted out with sodium chloride, filtered, washed and dried to give the free acid in the form of the following formula (2): A triazine compound was obtained.

Example 8 1-Amino-8-hydroxy-2, used in Example 7
7-bis(5-amino-2-sulfophenylazo)-8
, 6-naphthalenedisulfonic acid and 1-aminobenzene-3,4-di(β-sulfatoethyl sulfone), using equivalent moles of the compounds shown in columns A and Bl of the table below, Corresponding triazine compounds were obtained using the method described above, and the color tones on the dyed fabrics are recorded in the right column. In the table, Q is β-
It represents sulfatoethylsulfonyl or vinylsulfonyl, and can also mean other groups that can be converted into vinylsulfonyl by the action of an alkali.

Example 9 Each of the compounds synthesized in Examples 7 and 8 was subjected to a third condensation in the same manner as in Example 4 to obtain the corresponding compounds of the present invention.

Example 10 Instead of cyanuric chloride used in Examples 7 and 8,
Using equimolar amounts of cyanuric fluoride, the corresponding compounds of the present invention were obtained.

Dyeing Example 1 Each of the triazine compounds obtained in Examples 1 to 10 was 0.
Dissolve 8 parts in 200 parts of water, add 10 parts of mirabilite, and add 1 part of cotton.
Add 0 parts and raise the temperature to 60°C. After 20 minutes, 4 parts of soda carbonate was added and dyed at the same temperature for 1 hour. After finishing the dyeing, washing with water and soaping were carried out to obtain dyed products excellent in the above-mentioned dyeing performance and various fastnesses. Moreover, even if the dyeing temperature, bath ratio, and amount of inorganic salt added were slightly varied, dyed products of stable quality with good reproducibility were obtained.

Dyeing example 2 Color Lake composition Urea 5 parts Sodium alginate (5-10) Moto Lake 50 parts Hot water 25 parts Baking soda 2
Part balance: 13 parts The color lake containing the above composition is printed on a broad mercerized wire, and after intermediate drying, steaming is performed at 100°C for 5 minutes, followed by hot water washing, soaping, hot water washing, and drying to finish.

In this way, a printed material excellent in dyeing performance and various fastnesses as described above was obtained.

Staining Example 8 25 each of the triazine compounds obtained in Examples 1 to 10
part is dissolved in hot water and cooled to 25°C. 32.
Add 5.5 parts of 5% caustic soda aqueous solution and 150 parts of 50° Baume water glass, and then add water to bring the total volume to 2.
Immediately after making up to 1,000 parts at 5°C, a cotton fabric is wound up using this liquid as a padding liquid, sealed with polyethylene film and stored in a room at 20''C.

Cotton fabrics padded in a similar manner and sealed with rolled polyethylene film are stored in a 5'C room.

After each padding cloth has been left for 20 hours, the dyeing is finished by washing in cold and then hot water, soaping in boiling detergent, washing in cold water and drying.

When we investigated the difference in hue and density between dyed products left at 20°C for 20 hours and dyed products left at 5°C for 20 hours, we found almost no complaints.

In addition, a dyed product with good build-up properties was obtained by cold patch-up dyeing.

Claims (11)

[Claims] (1) At least one of the following formulas (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R is hydrogen or optionally substituted alkyl,
Y represents -CH_2CH_2L (L is a group that is eliminated by the action of an alkali) or vinyl. ] A triazine compound having a group represented by the following. (2) The triazine compound has the following formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) [In the formula, R_1 and R_2 are independently hydrogen or optionally substituted alkyl, X_1 is chloro, fluoro, optionally substituted aliphatic or aromatic amino,
C_1_-_4 alkoxy or optionally substituted phenoxy, Y, and Y_2 are each independently -CH_2C
H_2L (L is a group that is eliminated by the action of an alkali) or vinyl, and D_1 represents an anionic dye residue. ] The compound according to claim 1, which is represented by: (3) The triazine compound has the following formula (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) [In the formula, R_3, R_4 and R_3 are independently hydrogen or optionally substituted alkyl, Y_3, Y_4 and Y_5 are each independently -CH_2CH_2L (L is a group that is eliminated by the action of an alkali) or vinyl, D_2 and D
_3 independently represent anionic dye residues. ] The compound according to claim 1, which is represented by: (4) The triazine compound has the following formula (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) [In the formula, R_6, R_7, R_8 and R_9 are independently hydrogen or optionally substituted alkyl, X_2 and X_3 are each independently chloro, fluoro, optionally substituted aliphatic or aromatic amino, C_
1_~_4 alkoxy or optionally substituted phenoxy, Y_6 and Y_7 are each independently -CH_2CH
_2L (L is a group that is eliminated by the action of an alkali) or vinyl, and D_4 represents an anionic dye residue. ] The compound according to claim 1, which is represented by: (5) The triazine compound has the following formula (V) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (V) [In the formula, R_1_0, R_1_1, R_1_2, R_1
_3, R_1_4 and R_1_5 are each independently hydrogen or optionally substituted alkyl, W is a divalent crosslinking group,
Y_8, Y_9, Y_1_0 and Y_1_1 each independently represent -CH_2CH_2L (L is a group that is eliminated by the action of an alkali) or vinyl, and D_5 and D_6 each independently represent an anionic dye residue. ] The compound according to claim 1, which is represented by: (6) D_1, D_2, D_3, D_4, D_5 and D
Any one of claims 1 to 5, wherein _6 is independently a metal-containing or non-metallic azo-based, anthraquinone-based, metal-containing phthalocyanine-based or formazan-based, dioxazine-based, or stilbene-based. Compounds described. (7) The compound according to any one of claims 1, 2, and 4, wherein X_1, X_2, and X_3 are each independently chloro or fluoro. (8) The compound according to any one of claims 1, 2, and 4, wherein X_1, X_2, and X_3 are optionally substituted anilino. (9) R, R_1, R_2, R_3, R_4, R_5,
R_6, R_7, R_8, R_9, R_1_0, R_1
_1, R_1_2, R_1_3, R_1_4 and R_1
9. The compound according to any one of claims 1 to 8, wherein _5 is independently hydrogen, methyl or ethyl. (10) W is C_2_ to_6 alkylene, phenylene, mono- or disulfophenylene, 1,3,5-trimethyl-4-sulfo-2,6-phenylene, 6-substituted-1,
3,5-triazine-2,4-diyl or stilbene-
A compound according to claim 5 which is 4,4'-diyl. (11) At least one of the following formulas (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R is hydrogen or optionally substituted alkyl,
Y represents -CH_2CH_2L (L is a group that is eliminated by the action of an alkali) or vinyl. ] A method for dyeing or printing a fiber material, characterized by using a triazine compound having a group represented by the following.