JPH04106160A - Unsymmetrical dioxazine compound and method of dyeing or printing fibrous material by using it - Google Patents

Abstract

PURPOSE:To obtain an unsymmetrical dioxazine compound suitable for dyeing and printing material containing hydroxyl and/or amide group and excellent in the fastness to light, moisture, and chlorine by forming a compound having a specified structural formula. CONSTITUTION:An unsymmetrical dioxazine compound shown by formula 1 in free acid form. In the formula 1, x1 and x2 are each independently H, halogen, lower alkyl, etc.; W is an aliphatic or aromatic crosslinking group which may have a substituent; Q1 and Q2 and each independently lower alkyl, optionally substituted amino, etc.; Y1 and Y2 are each indepedently an alkylene, phenylene or naphthylene group which may have a substituent; R1, R2, R3, and R4 are each independently H or optionally substituted lower alkyl; and Z1 and Z2 are each independently -SO2CH=CH2 or -SO2CH2CH2Z'' (wherein Z'' is a group that will be eliminated by an alkali).

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention is directed to materials containing hydroxyl groups and/or amide groups, particularly cellulose 1ml#! Suitable for dyeing and printing natural or synthetic polyamide fibers, polyurethane pongee or leather, as well as their blends 11M, an improved novel asymmetric dyeing system that enables light-fast, wet-fast and chlorine-fast dyeing. This invention relates to dioxazine compounds and their applications.

<Prior art> Reactive dyes having a dioxazine skeleton in the molecular structure of the dye are known, but they are insufficient in terms of dyeing performance, such as level dyeing, build-up property, dyeing speed, or fastness, especially chlorine fastness. Therefore, further improvement is desired.

<Problem to be solved by the invention> The fastness of dyed or printed products of materials containing hydroxyl groups and/or amide groups, especially the fastness to chlorine, is not at a satisfactory level, especially in the case of hydroxyl group-containing fibers. The inventors of the present invention have endeavored to improve this level and have discovered an asymmetric dioxazine compound that can solve the above problems.

Means for Solving the Problems> The present invention provides the following - maximum (I) [in the formula, χ1
．． χ2 independently represents hydrogen, halogen, lower alkyl group, lower alkoxy group, or phenoxy group, W represents an aliphatic or aromatic crosslinking group which may have a substituent, Qs
, Ql are each independently Uζ lower alkoxy group, an optionally substituted amino group or -N-Ys-Zs (wherein Rs? is hydrogen or an optionally substituted lower alkyl group) , Ys is an alkylene group which may have a substituent, phenylene or naphthylene group, zl is -8OsCH-CHg
Also represents bar 5OiCH*CHgZ' (in the formula, 2' represents a group that is eliminated by the action of an alkali). ), and Yl and Y2 each independently represent an optionally substituted alkylene, phenylene or naphthylene group,
R1, R1, Rs and R4 each independently represent hydrogen or a lower alkyl group which may have a substituent; represents a group that is eliminated by the action of an alkali.] The present invention provides an asymmetric dioxazine compound represented by the following and a method for dyeing or printing a fiber material using the same.

Examples of the lower alkoxy group represented by Ql and Ql include a methoxy group and an ethoxy group.

Ql and a [
Examples include alkylamino, N, N-dialkylamino, cycloalkylamino, aralkyl, arylamino, mixed substituted amino groups such as N-furkyl-N-cyclohexylamino and N-furkyl-N
- arylamino, an amino group further containing a heterocyclic group (this cyclic group can further have an additionally fused carbocyclic ring), and whose 7-aryl nitrogen atom is an N-heterocyclic group; (This N-heterocycle may further contain another heteroatom depending on the case.) and the like. The alkyl mentioned above may be straight or branched, and may be of low molecular weight or high molecular weight, but C1 to C4 alkyl is preferred. As cycloalkyl, aralkyl and aryl, groups such as cyclohexyl, benzyl, phenethyl, phenyl and naphthyl are particularly preferred. Examples of heterocyclic groups include furan, thiophene, pyrazole, pyridine, pyrimidine, quinoline, benzimidazole, benzthiazole and benzoxazole. Preferred as amino groups in which the amino nitrogen atom is a ring member of an N-heterocyclic ring are 6-membered N-heterocyclic ring compounds which further contain nitrogen, oxygen and sulfur as heteroatoms. Good too. The above alkyl, cycloalkyl, aralkyl, aryl, heterocyclic ring and N-heterocyclic ring may further be halogen, nitro, cyano, trifluoromethyl, sulfamoyl, carbamoyl, 01-C4-alkyl, 01
~04-Optionally substituted by alkoxy, acylamino, ureido, hydroxy, carboxy, sulfomethyl and sulfo. Examples of Ql and the amino group represented by Ql include -NHg, methylamino, hydroxymethylamino, ethylamino, propylamino, butylamino, N,N-dihydroxymethylamino, hexylamino, β-methoxyethyl Amino, β-! Toxyether, γ-methoxypropylamino, NlN-dimethyl, N,N-diethylamino, β-chloroether, β-cyanoethylamino, N,N-diβ-hydroxypropylamino, β -Hydroxyether
T-hydroxypropylamino, benzylamino, phenethyl amino, cyclohexylamino, N-methyl-N
-phenylamino, N-ethyl-N-phenyla [no,
N-propyl-N-phenylamino, N-butyl-N-
Phenylamino, N-β-cyanoethyl-N-phenylamino, N-ethyl-2-methylphenylamino, N-
Ethyl-4-methylphenyla[no,N-ethyl-8-
Sulfophenylamino, N-ethyl-4-sulfophenylamino, phenylamino, toluidino, xylidino, chloranilino, anisidine, phenetidine, 2-. 8-
and 4-sulfoanilino, 2.4- and 2.6-disulfoanilino, sulfomethylanilino, N-sulfomethylanilino, 8- and 4-carboxyphenylamino, 2-carboxy-6-sulfophenylamino, 2-
Carboxy-4-sulfophenylamino, 2-methoxy-6-sulfophenylamino, 2-methyl-6-sulfophenylamino, 4-sulfonaphthyl-(1)-a[no, 8,6-cissulfonaphthyl] Ru(1)-amino, 8.6
．． 8-trisulfonaphthyl-(1)-amino, 4,6.
8-trisulfonaphthyl-(1)-amino, 6-sulfonaphthyl-(2)-amino, 4.8-disulfonaphthyl-(2)-amino, 8.6.8-trisulfonaphthyl-
(2)-amino, 4.6.8-trisulfonaphthyl-(
2)-Amino, pyridyl-(2)-amino, morpholino, piperidino, piperazino, N-β-hydroxyethyl-N-methylamino and N-ethyl-N-hydroxymethylamino, β-carboxyethyl-(2)-amino, β- Examples include sulfoethylamine 2% N-(β-sulfoethyl)-N-methylamino.

Although Ql and Ql can independently represent different groups, they are preferably the same groups from a synthetic standpoint.

As 11.1g, halogen is particularly preferable, among which
Chlorine and bromine are preferred.

The alkylene group which may have a substituent represented by Yl, Yl and Ys includes -(CH, -(C
Hri, -, -(CH2), 0(CIG)! - etc. are exemplified. The phenylene group or naphthylene group which may have a substituent is preferably one or two substituents selected from methyl, ethyl, methoxy, ethoxy, chlorine, bromine, and sulfo. A phenylene group which may be substituted with a phenylene group or a naphthylene group which may be substituted with one sulfo group, and means a bond leading to, for example, RJll -N-. ), etc.

Examples of the groups 1 and 2'' which are eliminated by the action of an alkali include sulfuric esters, thiosulfuric esters, phosphoric esters, acetic esters, and halogens.

Rt, Rg, Rs, R4 and RIS (
7) The lower alkyl group which may have a substituent is preferably C1 to C4 alkyl, and the optionally substituted group is hydroxy, cyano, alkoxy, halogen, carbamoyl, carboxy, alkoxycarbonyl, Alkylcarbonyloxy, sulfo and sulfamoyl are preferred. Hydrogen is particularly preferred as fluorine and R8. Preferred Rr, R4 and R6 are:
For example, hydrogen, methyl, ethyl, n-propyl, 1so
-propyl, n-butyl, is.

-butyl, 5ee-butyl, 2-hydroxyethyl, 2
-Hydroxypropyl, 8-hydroxypropyl, 2-
Hydroxybutyl, 8-hydroxybutyl, 4-hydroxybutyl, 2.8-dihydroxypropyl, 8.4-
Dihydroxybutyl, cyanomethyl, 2-cyanoethyl, 8-cyanopropyl, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 8-methoxypropyl, 8-ethoxypropyl, 2-hydroxy-8-methoxypropyl, chloro Methyl, bromomethyl, 2-chloroethyl, 2-bromoethyl, 8-chloropropyl, 8-bromopropyl, 4-chlorobutyl, 4
-bromobutyl, carboxymethyl, 2-carboxyethyl, 8-carboxypropyl, 4-carboxybutyl, 1,2-dicarboxyethyl, carbamoylmethyl,
2-carbamoylethyl, 8-carbamoylpropyl,
4-carbamoylbutyl, methoxycarbonylmethyl,
Ethoxycarbonylmethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl, 8-methoxycarbonylpropyl, 8-ethoxycarbonylpropyl,
4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, methylcarbonyloxymethyl, ethylcarbonyloxymethyl, 2-methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl, 8-methylcarbonyloxypropyl, 8-ethylcarbonyloxypropyl , 4-methylcarbonyloxybutyl, 4-ethylcarbonyloxybutyl, sulfomethyl, 2-sulfoethyl, 8-sulfopropyl, 4-sulfobutyl, 1-moylsulfomethyl, 2-moylethyl sulfo, 8-
Examples include 1-moylpropyl sulfur and 1-moylbutyl 4-sulfur, among which hydrogen, methyl and ethyl are particularly preferred.

The aliphatic crosslinking group which may have a substituent represented by W is C! -C4 fullkylene groups are mentioned, of which ethylene and propylene are particularly preferred.

Aromatic ○ which may have a substituent represented by W. Examples of the crosslinking group include violet, a phenylene group or a naphthylene group substituted with a 1.2 or 84m sulfo group, and among them, one or two Particularly preferred are phenylene groups substituted by sulfo groups.

The compounds of the invention are present in the form of the free acid or in the form of its salts, in particular the alkali metal and alkaline earth metal salts, especially the soda, potassium and lithium salts.

The compound of the present invention can be produced, for example, in the following manner. The dioxazine intermediate represented by the following - maximum (n) (wherein Rg, Rs, χ1. -Z! (IN)H-N-Y2-
72 (IV) H-Ql (V) H-Ql (VI) (wherein Rs, R4, Ys, Yz, Zx, Z1
! , Ql o and Q2 have the meanings given above. ) with the compound represented by 2,4.6-dolihalogeno S
-) obtained by condensing each with riazine in any order.

In the condensation reaction with 2.4.6-dolyhalogeno-8-triazine, the order is not particularly limited,
Also, the reaction conditions are not particularly limited, but - secondly, temperature -
The general formula (I ) An asymmetric dioxazine compound or a salt thereof can be obtained.

The dioxazine intermediate represented by the formula (Shu) can be synthesized by a method known per se. For example, it can be synthesized as follows.

The following - maximum (■) C formula obtained by condensing a corresponding aniline compound with chloranil: In the formula, R1, Rs and W have the above-mentioned meanings. )
A dioxazine intermediate of general formula (ff) is obtained by cyclizing the asymmetric dianilide compound represented by, optionally in the presence of an oxidizing agent.

The compound of the present invention has fiber reactivity and can be used for dyeing or printing hydroxy group-containing or carbonanido 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.

Cellulose fiber material is cotton, as well as other vegetable fibers,
For example, linen, hemp, jute and ramie are preferred. Regenerated cellulose fibers are, for example, viscose stable and filament viscose.

Materials containing carbonate 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, boria fibers, etc.6.
6, polyamide-6, polyamide-11 and boria 1
It is Do 4.

The compounds of the present invention can be dyed or printed on the above-mentioned materials, in particular on the above-mentioned fiber materials, in a manner depending on their physical and chemical properties.

For example, when carrying out exhaust dyeing on cellulose pongee, in the presence of a neutral salt such as mirabilite or common salt, add an acid binder such as sodium hypochlorite, sodium tertiary phosphate, caustic soda, or sodium bicarbonate, and if desired, It is carried out at a temperature of 100° C. or lower using a solubilizing agent, a penetrating agent, or a leveling agent. The neutral salt that promotes dye exhaustion can optionally be added in portions.

When staining cellulose taU according to the padding method,
After padding and drying at room temperature or elevated temperature, it can be fixed by staging or dry heat.

When printing is carried out on cellulose fibers, it can be carried out in one phase by printing with a printing paste containing e.g. Printing can be carried out by printing with a neutral or weakly acidic printing paste, passing it through a hot alkaline bath containing an electrolyte, or overpadding with a padding liquid containing an alkaline electrolyte, followed by steaming or dry heat treatment.

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

Acid binders suitable for immobilizing 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 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. Examples of such acid binders include caustic soda, caustic potash, 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 boria fibers 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 pH value for fixation. It can be done by Dyeing can usually be carried out at a temperature of 60 to 120°C, but in order to achieve level dyeing properties, a condensation product of a common leveling agent, such as cyanuric chloride, and 8 times the mole of a[nobenzenesulfonic acid or aminonaphthalenesulfonic acid] is used. It is also possible to use compounds or, for example, addition products of stearyl chloride and ethylene oxide.

The compound of the present invention is characterized in that it exhibits excellent performance in dyeing and printing IIa fiber materials.

Particularly suitable for dyeing cellulose fiber materials, with good light fastness and sweat-sun fastness, excellent wet fastness, such as wash fastness, peroxide wash fastness, sweat fastness, acid hydrolysis fastness and alkali fastness. It also has good chlorine fastness, rub fastness and iron fastness.

In addition, it has excellent build-up properties, level dyeing properties, and wash-off properties, as well as good solubility, exhaustion and fixation properties, and is less susceptible to fluctuations in dyeing temperature and dye bath ratio, resulting in dyed products of stable quality. It has characteristics in certain points.

Another characteristic of the dyed product is that there is little discoloration during fix treatment or resin processing, and there is little change due to contact with basic substances during storage.

Hereinafter, the present invention will be explained in detail with reference to Examples.

In the examples, parts and % represent parts by weight and % by weight, respectively.

Example 1 An asymmetric dioxazine compound represented by the following structural formula was obtained in the form of a free acid.

5OsHcj (λmax: 606 nm in aqueous medium) Asymmetric dioxazine intermediate 17.7 of the above structural formula in the free acid form
1 part is suspended in 200 parts of water, and to this suspension is added a reaction solution in which 11 parts of cyanuric chloride and 15.2 parts of 1-aminobenzene-2,5-disulfonic acid are condensed. pH8-10
, perform secondary bonding at a temperature of 80 to 50°C, and after completion of the reaction,
1-A[Nobenzene-8-β-sulfur 1-toethylsulfone 16.8 parts was added and the 8th combination was further carried out (λmax
:E16nm+ in aqueous medium) Example 2 In place of the dioxazine intermediate and l-aminobenzene-8-β-sulfatoethylsulfone used in Example 1, the compounds in columns 2 and 8 of the table below were used. Synthesis was carried out in the same manner as in Example 1 to obtain the corresponding asymmetric dioxazine compound. These compounds were dyed to give dyed products in the shades shown in Table 4s below.

Example 8 1-Aminobenzene-2 used in Examples 1 and 2
, 5-disulfonic acid and the following amines were used to obtain corresponding asymmetric dioxazine compounds by carrying out the same operations as in Examples 1 and 2, respectively.

(1) Methanic acid (2) Sulfanilic acid (8) Ortanilic acid (4) Aniline (5) 1-7i Nobenzene-2,4-disulfonic acid (6) Ethylamine (7) Ammonia (8) O-Aminobenzoic acid ( 9) β-Hydroxyethylamine αCβ-alanine υ Taurine still N-Methyl taurine (I31-A[Nonaphthacine-4,6,8-trisulfonic acid Q4 2-aminonaphthalene-1,5-disulfonic acid α92-aminonaphthalene -8,6,8-trisulfonic acid N-methylaniline N-ethylaniline p~a (]benzoic acid 1-7minonaphthalene-8,6-disulfonic acid 2-7minonaphthalene-4,8-disulfonic acid 2-7minonaphthalene- 4.6.8-trisulfonic acid m
-chloroaniline m-toluidine p-toluidine p-anisidine (in an aqueous medium) 21.5 parts of the asymmetric dioxazine intermediate represented by the above structural formula in the form of the free acid, 2-methoxy-4°6-dichloro-8-triazine Add to the aqueous dispersion of 18 parts of 1O, pI
The condensation reaction is carried out at Is~8 and a temperature of 40 to 60°C. After the reaction is completed, 1-aminobenzene-8-β-sulfur 1
An eighth condensation reaction was carried out by adding 16.8 parts of -toethylsulfone to obtain an asymmetric dioxazine compound represented by the following structural formula in the form of a free acid.

Example 6 Cyanuric chloride and 1 used in Examples 1 and 2Iζ
- instead of the condensate with aminobenzene-2,5-disulfonic acid, equimolar 2-methoxy-4,6-dichloro-5
-) Using riazine, the reaction was carried out in the same manner as in Examples 1 and 2 to obtain the corresponding asymmetric dioxazine compounds.

Example 6 0.1, 0.8 and 0.6 parts of each of the asymmetric dioxazine compounds obtained in Examples 1 to 6 were dissolved in 200 parts of water, 10 parts of Glauber's salt and 10 parts of cotton were added, The temperature was raised to 60°C, 4 parts of soda carbonate was added, and dyeing was carried out for 1 hour. After washing with water, soaping, rinsing with water and drying, a blue dyed product was obtained which was excellent in various fastnesses, especially chlorine fastness, and had good build-up properties.

Example 7 Using each of the asymmetric dioxazine compounds obtained in Examples 1 to 5, colored pastes having the following compositions were made.

Asymmetric dioxazine compound 5-part urea
5 parts sodium alginate (5%) base glue 5 parts heat v
! ! I 25 parts baking soda
2 part balance
18 parts of this colored paste was printed on mercerized cotton broadcloth, and after intermediate drying, it was steamed at 100° C. for 5 minutes, washed with hot water, soaped, washed with hot water, and dried. The obtained dyed product has excellent fastness properties, especially chlorine fastness,
It had good build-up properties.

(Margin below)

Claims (5)

[Claims] (1) In the form of a free acid, there are the following general formulas ▲ mathematical formulas, chemical formulas, tables, etc. represents an aliphatic or aromatic crosslinking group which may have a substituent, and Q1 and Q2 are independently a lower alkoxy group, an amino group which may have a substituent, or ▲ a mathematical formula, a chemical formula, a table, etc. ▼{In the formula, R_5 is hydrogen or a lower alkyl group that may have a substituent, Y_3 is an alkylene, phenylene, or naphthylene group that may have a substituent, and Z_3 is -SO_2CH=CH_2 or -S
It represents O_2CH_2CH_2Z' (in the formula, Z' represents a group that is eliminated by the action of an alkali). } represents
Y_1 and Y_2 each independently represent an optionally substituted alkylene, phenylene or naphthylene group, and R_
1, R_2, R_3 and R_4 each independently represent hydrogen or a lower alkyl group which may have a substituent, and Z_
1 and Z_2 independently of each other -SO_2CH=CH_
2 or -SO_2CH_2Z'' (in the formula, Z'' represents a group that is eliminated by the action of an alkali). ] An asymmetric dioxazine compound represented by (2) The compound according to claim 1, wherein x_1 and x_2 are chlorine or bromine. (3) The compound according to claim 1 or 2, wherein R_2 and R_3 are hydrogen. (4) W is ethylene, propylene, phenylene or 1
Claim 1- which is phenylene having ~2 sulfo groups
3. The compound according to any one of 3. (5) A method for dyeing or printing a fiber material, which comprises using the asymmetric dioxazine compound according to any one of claims 1 to 4.