JPH02209970A - Asymmetric dioxazine compound and dyeing or pringing of fiber material using the same - Google Patents

Abstract

NEW MATERIAL:A compound in the form of free acid shown by formula I [X is halogen; W is crosslinkable group of (substituted) aliphatic group or aromatic group; Q is (substituted) amino or group shown by formula II; R1 to R6 are H or (substituted) lower alkyl) Y1 and Y2 are (substituted) alkylene, phenylene or naphthylene; Z1 and Z2 are -SO2CH=CH2 or -SO2CH2CH2Z' (Z' is group eliminable by action of alkali)]. EXAMPLE:A compound shown by formula III. USE:Dyeing materials containing OH group or amide group. Especially suitable for dyeing cellulosic fiber materials. Having excellent light resistance, sweat and sunlight resistance, wetting resistance, alkali resistance, wear resistance and ironing resistance. PREPARATION:An asymmetric dioxazine intermediate shown by formula IV is condensed with an amine shown by formula V and an amine shown by the formula H-Q or an amine shown by formula VI into 2,4,6-trihalogeno-s-triazine.

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 fibers, natural or synthetic polyamide fibers, polyurethane fibers, leather, etc., and blends thereof. The present invention relates to improved novel asymmetric dioxazine compounds suitable for dyeing and printing fibers and allowing light-fast and wet-fast dyeing, 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.

<Problems to be Solved by the Invention> The fastness of dyed or printed products of materials containing hydroxyl groups and/or amide K is not at a satisfactory level, especially in the case of hydroxyl group-containing fibers, and the present inventors worked diligently to improve this level and discovered an asymmetric dioxazine compound that could solve the above problems.

[Means for Solving the Problems] The present invention provides the following in the form of a free acid - Margin (I) (hereinafter referred to as a blank) [In the formula, X is a halogen, and W is an optionally substituted aliphatic or Q is an aromatic crosslinking group, R6 is an optionally substituted amino group or a group represented by the formula -Y, -Z, and R,, R,, R,, R4, R, and R6 are Yl and Y2 independently represent hydrogen or a lower alkyl group that may have a substituent; Yl and Y2 independently represent an alkylene, phenylene, or naphthylene group that may have a substituent; Zl and Z2 independently represent , -5O2CH-C
It represents H, or -3o, CH, CH2Z'(Z' 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.

Here, the halogen represented by X is preferably chlorine or bromine.

Examples of the amino group represented by Q which may have a substituent include alkylamino, N, N-dialkylamino, dichloroalkylamino, aralkylamino, arylamino, mixed substituted amino, for example, N- Alkyl-N-
cyclohexylamino and N-alkyl-N-arylamino, as well as amino containing heterocyclic groups (which cyclic groups can also have addition-fused carbocyclic rings), and their amino nitrogen atoms. Examples include amino in which is an N-heterocyclic ring member (this N-heterocycle may further contain another heteroatom depending on the case). The alkyl in the above may be linear or branched, and may be of low molecular weight or high molecular weight, but
Preferred is alkyl of 01 to C4. 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. Amino nitrogen atom is N-
Preferred amino as a ring member of a heterocyclic ring is 6@
is an N-heterocyclic ring compound which may further contain nitrogen, oxygen and sulfur as petro atoms. The above alkyl, cycloalkyl, aralkyl, aryl, heterocyclic ring and N-heterocyclic ring may further be halogen, nitro, cyano, trifluoromethyl, sulfamoyl,
Carbamoyl, C1-, C,-alkyl, C1-C4
may be replaced. Examples of the amino group represented by Q include -NH, methylamino, ethylamino, propylamino, butylamino, hexylamino, β-methoxyethylamino, β-ethoxyethylamine, r-
Methoxypropylamino, N, N-dimethylamino, N
, N-diethylamino, β-chloroethylamino, β-
Cyanoethylamino, N,N-di-β-hydroxyethylamino, β-hydroxyethylamino, r-hydroxypropylamino, benzylamino, phenethylamino, cyclohexylamino, N-methyl-N-phenylamino, N-ethyl- N-phenylamino, N-propyl-N-phenylamino, N-butyl-N-phenylamino, N-β-cyanoethyl-N-phenylamino, N-
Ethyl-2-methylphenylamino, N-ethyl-4-
Methylphenylamino, N-ethyl-8-sulfophenylamino, N-ethyl-4-sulfophenylamino, phenylamino, toluidino, xylidino, chloranilino, anisidine, phenetidine, 2-8- and 4-sulfoanilino, 2.4- and 2,5-disulfoanilino, sulfomethylanilino, N-sulfomethylanilino, B- and 4-carboxyphenylamino, 2-carboxy-5-sulfophenylamino, 2-carboxy-
4-Sulfophenylamino, 2-methoxy-5-sulfophenylamino, 2-methyl-5-sulfophenylamino, 4-sulfonaphthyl-(1)-amino, fonaphthyl-(2)-amino, 4,8-disulfonylamino Naphthyl (2)
-amino,8.6.8-trisulfonaphthyl-(2)-
Amino, 4.6.8-trisulfonaphthyl-(2+-amino, pyridyl<21-amino, morpholino, piperidino, piperazino, ethanolamino, methanolamino, N,N-jetanolamino, N,N-dimethatol amino, N-ethanol-N-methylamino and N
Examples include -ethyl-N-methanolaminocarboxyethylamino, β-sulfoethylamino, and N-(β-sulfoethyl)-N-methylamino.

As the alkylene group which may have a substituent represented by Yl, Y2, (CH2) 2 (C
Hz)s-(CH2)10 (CH2)! - etc. are exemplified. Furthermore, the phenylene group or naphthylene group which may have a substituent is preferably substituted with 1 or 21 substituents from the group consisting of methyl, ethyl, methoxy, ethoxy, chlorine, bromine and sulfo. phenylene which may be substituted with phenylene or naphthylene which may be substituted with one sulfo group, and means, for example, a continuous bond. ), etc.

Examples of the group represented by Z which is eliminated by the action of an alkali include sulfuric acid ester, thiosulfuric acid ester, phosphoric acid ester, ester acetate, and halogen.

As the lower alkyl which may have a substituent for R,, R, %R,, R4, R, and R-, 01-C4 alkyl is preferable, and as the optionally substituted group, hydroxy , Cyano1. Preferred are a, alkoxy, halogen, carbamoyl, carboxy, alkoxycarbonyl, alkylcarbonyloxy, sulfo and sulfamoyl.

Hydrogen is particularly preferred as RhRhR and R1.

Particularly preferable R and R are, for example, hydrogen, methyl, ethyl, n-propyl, 1so-propyl, n-
Butyl, 1so-butyl, 5ec-butyl, 2-hydroxyethyl, 2-hydroxypropyl, 8-hydroxypropyl, 2-hydroxybutyl, 8-hydroxybutyl, 4-hydroxybutyl, 2.8-dihydropropyl, 8.4 -dihydroxybutyl, cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 8-methoxypropyl, 8-ethoxypropyl, 2
-hydroxy-8-methoxypropyl, chloromethyl,
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-carbamoyl Ethyl, 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, sulfamoylmethyl, 2-sulfobutyl Famoylethyl, 8-sulf 1 moylpropyl, and 4-sulf 1 moylbutyl can be mentioned.

Examples of the optionally substituted aliphatic crosslinking group represented by W include C2 to C4 alkylene groups, with ethylene and propylene being particularly preferred.

Each carbon of the alkyl group represented by R1 may be bonded to an adjacent nitrogen to form a heterocyclic bridging group such as -NN-.

The optionally substituted aromatic crosslinking group represented by W includes a phenylene group or a naphthylene group substituted with 0.1.2 or 8 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, as follows. An asymmetric dioxazine intermediate represented by the following general formula (If) So, H (in the formula, *X, R2, R3, R4, R8 and W have the above-mentioned meanings) and the following general formula (@ R7 H-NysZ( ta (wherein R,, Y, and Z have the above meanings.

) and the following general formula (5)% formula% (5
) (wherein, Q has the above-mentioned meaning) or the following general formula (V) R1 starch H-N-Y, -Z, (V) (wherein, R,
, Y, and Z have the meanings given above. ) and 2.4.6-trihalogeno-S-triazine in any order.

In the condensation reaction with 2.4.6-trihalogeno-S-triazine, the order is not particularly limited,
Also, the reaction conditions are not particularly limited, but - secondly, temperature -
pH 2 to 9 at 10°C to 40°C, secondarily at temperature r7o
I) R2 to 9 at a temperature of 70°C to 70°C, and in the case of tertiary reaction, condensation at a temperature of 11fjlO to 100°C while adjusting the pH to 2 to 7 to obtain an asymmetric dioxazine compound represented by general formula (I) or a salt thereof. Can be done.

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

The following - Tsuzuriyo (b) obtained by condensing the corresponding aniline compound and chloranil (in the formula, X, R2,
Rs, Ra -Rs Oyohi W +, t ntr
) have meaning. ) is chemically treated, optionally in the presence of an oxidizing agent, to obtain an asymmetric dioxazine intermediate of the general formula (2).

Furthermore, when R4 and/or the island is a lower alkyl group which may have a substituent, the corresponding R4 and/or
Alternatively, it can also be obtained by alkylating an asymmetric dioxazine intermediate of general formula (n) or an asymmetric dioxazine compound of general formula (I) in which RII is hydrogen by a conventional 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.

Cellulose fiber material is cotton, as well as other vegetable fibers,
For example, linen, hemp, jute and ramie fibers are preferred. 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, polyamide-6, polyamide-11 and polyamide-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, in the case of exhaust dyeing on cellulose fibers, in the presence of an acid binder such as soda carbonate, sodium phosphate or caustic soda, a neutral salt such as mirabilite or common salt is optionally added, and if desired, a solubilizer is added. , use a penetrant or leveling agent together,
It is carried out at relatively low temperatures. The neutral salts which accelerate the exhaustion of the dyestuff can be added only after or before the actual dyeing temperature has been reached, optionally in portions.

When dyeing cellulose a-fibers according to the bazing 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, it can be carried out in one phase, e.g. by printing with a printing paste containing heavy or other acid binders and then steaming at 100-160°C, or in two phases, e.g. Printing with a neutral or slightly acidic printing paste and passing this through a hot electrolyte-containing alkaline bath or alkaline electrolyte I! i! ! It can be carried out by over-padding with a padding liquid containing quality, followed by steaming or dry heat treatment.

The printing paste may optionally contain thickening agents or emulsifiers, such as, for example, sodium alginate or starch ether.
It is used in combination with conventional printing aids and/or dispersants, such as 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, silicate soda, 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 pH value for fixation. I can do it. Dyeing can usually be carried out at a warm 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 8 times the mole of aminobenzenesulfonic acid or aminonaphthalenesulfonic acid are used. Alternatively, for example addition products of stearylamine and ethylene oxide can 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 good light fastness, sweat and sunlight resistance, and excellent moisture resistance, such as washing resistance, overwashing resistance, sweat resistance, and layer hydrolysis resistance. It has good alkali resistance, scratch resistance and iron resistance.

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 provides dyed products with stable quality that is less affected by fluctuations in dyeing temperature and dye bath ratio. 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! 18 parts of the asymmetric dioxazine intermediate represented by the above structural formula in free acid form are added to 200 parts of water and 5.5 parts of cyanuric chloride is added.
200 parts of an aqueous solution 1IJj containing a condensate obtained by reacting 1 part with 7.6 parts of 7-niline-1 disulfonic acid was added, and the mixture was stirred at pH 7-9.10-80°C until the reaction was completed. Furthermore, 8.4 m of aniline-3-β-sulf-1-toethyl sulfone was added, and the pH was adjusted to 2-6.80-70.
By stirring at °C until the reaction was completed, an asymmetric dioxazine compound represented by the following structural formula was obtained in the form of a free acid.

21.5 parts of the asymmetric dioxazine intermediate represented by the above structural formula in the form of free acid were added to 200 parts of water and mixed with cyanuric chloride 6.
．． 6 parts were added and stirred at pH 4-7.0-20°C until the reaction was completed. Thereafter, 5.2 parts of sulfanilic acid was added, and the mixture was stirred at pH 5-7.10-40° C. until the reaction was completed. Furthermore, aniline-3-! -Add 8.4 parts of sulus 1-toethylsulfone, pH 2~G, 80-70℃
By stirring until the reaction was completed, an asymmetric dioxazine compound represented by the following structural formula was obtained in the form of a free acid.

(λmax = 6201 m, however, in an aqueous medium, the same applies below): bu, ti (λmax = 680 nm) Example 8 In place of sulfanilic acid in Example 2, aniline-4-I
Example 2 using equimolar amounts of -sulf-1-toethylsulfone
In the form of the free acid, by doing in a similar manner as below! An unpaired hexadioxazine compound represented by the formula IIt was obtained.

(λmax-m610 nm) Example 4 The same mole as in Example 1 was used except that in place of the asymmetric dioxazine intermediate in Example 1, equimolar amounts of the asymmetric dioxazine intermediate represented by the following structural formula in the form of free acid were used. An asymmetric dioxazine compound represented by the following structural formula was obtained in the form of a free acid.

(λmax = 620 nm) Example 5 The corresponding asymmetric dioxazine compound was prepared by carrying out the same procedure as in Example 1, using equimolar amounts of the following amine in place of aniline-2,6-disulfonic acid in JllJ1. Obtained.

(1) Ortanilic acid (2) Metanilic acid (8) Sulfanilic acid (4) 1-aminonaphthalene-8,6-disulfonic acid (5) l-aminonaphthalene-4,6,8-trisulfonic acid (6) 2 -aminonaphthalene-1,5-disulfonic acid (7) 2-aminonaphthalene-4,8-disulfonic acid (8) 2-aminonaphthalene-8,6,8-trisulfonic acid (9) 2-aminonaphthalene-4 ,8,8-trisulfonic acid not Aniline-2,4-disulfonic acid αυ Aniline α21N-Methylaniline 0 N-Ethylaniline α m-Toluidine C9p-Toluidine C1m-Chloraniline C7) p-anisidine p-amino Benzoic acid a value Ammonia (4) Ethylamine Qυ β-Hydroxyethylamine (C) β-Alanine (C) Taurine Q N-Methyl taurine Example 6 In place of sulfanilic acid in Example 2, equimolar Example The corresponding asymmetric dioxazine compound was obtained by carrying out the same operation as in Example 2 using the amines (1) to C24) of Example 5.

Example 7 In place of aniline-8-β-sulfatoethyl sulfone in Example 1 and Actual Example 2, equimolar amounts of the following amines were used to carry out the same procedure as in Example 1 or Example 2. The corresponding asymmetric dioxazine compound was obtained.

Example 8 The corresponding asymmetric dioxazine compounds were obtained by replacing the asymmetric dioxazine intermediates used in Examples 1 and 2 with equimolar amounts of the asymmetric dioxazine intermediate represented by the following structural formula in the form of the free acid. Ta.

Practical Example 9 By replacing the asymmetric dioxazine intermediates used in Examples 5 to 7 with equimolar amounts of the asymmetric dioxazine intermediates used in Example 8, the corresponding asymmetric dioxazine intermediates were obtained.
A xazine compound was obtained.

Example 10 35 parts of the asymmetric dioxazine compound obtained in Example 1 were placed in 200 parts of water, 5 parts of ethylene chlorohydrin was added, and 1) H6~? The mixture was stirred at 40 to 90° C. until the reaction was completed to obtain an asymmetric dioxazine compound represented by the following structural formula in the form of a free acid.

Example 11 Each of the asymmetric dioxazine compounds 0.1, 0.8 and 0.6 obtained in Examples 1 to 10 was dissolved in 200 parts of water, 10 parts of Glauber's salt and 10 parts of cotton were added, and the mixture was heated to 60°C. The temperature was raised, 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 reddish blue dyed product having excellent fastness and good build-up properties was obtained.

Example 12 A colored paste having the following composition was prepared using each of the non-copper dioxazine compounds obtained in Examples 1 to 10.

Asymmetric dioxazine compound 5-part urea
5 parts Sodium alginate (5 parts
%) Motonori 50 parts boiling water
26 parts baking soda 2 parts balance 18 parts This color paste is printed on mercerized cotton broadcloth, and after intermediate drying, 1
Steaming was performed at 00°C for 5 minutes, followed by washing, soaping, washing in place, and drying. The obtained dyed product was excellent in various fastnesses and had good build-up properties.

(Margin below)

Claims (6)

[Claims] (1) In the form of a free acid, there are the following general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, An optionally substituted amino group or a group represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. Y_1 and Y_2 independently represent an optionally substituted alkylene, phenylene or naphthylene group; Z_1 and Z_2 independently represent -SO_2CH=CH_2 or -SO_2CH_
2CH_2Z'(Z' represents a group that is eliminated by the action of an alkali). ] An asymmetric dioxazine compound represented by (2) W is ethylene, propylene, phenylene or 1
2. The compound according to claim 1, which is phenylene having ~2 sulfo groups. (3) The compound according to claim 1 or 2, wherein R_2 and R_3 are hydrogen. (4) The compound according to any one of claims 1 to 8, wherein R_4 and R_5 are hydrogen. (5) The compound according to any one of claims 1 to 4, wherein X is chlorine or bromine. (6) A method for dyeing or printing a fiber material, which comprises using the asymmetric dioxazine compound according to any one of claims 1 to 5.