JPS5813788A - Anthraquinon dye for cellulose containing fibers - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to anthraquinone dyes for cellulose-containing fibers. More specifically, the present invention relates to a reactive anthraquinone dye for dyeing cellulose-containing fibers, particularly cellulose fibers, and mixed fibers consisting of polyester fibers and cellulose fibers in a strong blue color.

The present invention will be explained in detail below.

The dye according to the present invention has the following general formula (1) [wherein, represents an alkyl group, alkenyl group, cyclohexyl group, aryl group or aralkyl group which may be polysubstituted with a dialkylamino group, or N
R'R'' represents an S-membered or FiZ-membered nitrogen-containing heterocycle formed by linking V and R2, and the total number of carbon atoms of R1 and V is not more than it.] Cellulose-containing fibers represented by Anthraquinone dye.

The compound represented by the above general formula (IF), the following general formula [13 [wherein, It can be easily produced by reacting with the same compound shown by ].

Further, an anthraquinone compound represented by the general formula [fl] can be obtained by condensing sodium I,j-dihydroxy-q,t-diamino-2,6-disulfonate with 7 enols in sulfuric acid in the presence of boric acid, for example. It can then be easily obtained by eliminating the sulfonic acid group.

The present invention will be explained in detail below.

Examples of the lower alkyl group represented by Examples of the halogen atom include a -propoxy group and an inpropoxy group, and examples of the halogen atom include a chlorine atom and a bromine atom.

In addition, in the general formula CI] and [Seal], R1 and B
Examples of the alkyl group represented by 2 include a methyl group, an ethyl group, and a linear or branched alkyl group having 3 to 1 g of carbon atoms.
Cyanomethyl group, 1-cyanoethyl group, 3-cyanoallyl group, cohydro p-xyethyl group, λ-hydroxyglobyl group, J-hydroxyallyl group, dehydroxybutyl group, 2-(cohydrooxyethoxy)ethyl group, tris(hydroxy) methyl) methyl group, 1-ethoxyethyl group, J-ingropoxypropyl group, J-(2-methoxyethoxy)propyl group, co-, cordiethoxychedel group,
-1 (N.

N-diethylamino)ether group, co(N,N-dimethylamino)ether group, J-(N,N-dimethylamino)
Examples include alkyl groups substituted with a cyano group such as a propyl group, a hydroxyl group, a lower alkoxy group, or a dialkylamino group.

Examples of alkenyl groups include ant group, cometer allyl group,
Examples of the substituted alkenyl group include a 3-methylallyl group, a straight-chain or branched-chain alkenyl group having many carbon atoms to /'f, and examples of the substituted alkenyl group include a J-cyanoallyl group, a 2-hydroxyallyl group, and a J-methoxyethoxyallyl group. , I-methyl-J-(
N.

N-diethylamino) 79 groups such as cyano groups, hydroxyl, groups substituted with lower alkoxy groups, -tolyl groups, p-7F terphenyl groups, nato, cyano groups,
Examples of the atomyl group substituted with a hydroxyl group, lower alkoxy group or dialkylamino group include ■-cyanophenyl group, p-hydroxyphenyl group, p-1 toxyphenyl group, p-(-1 methoxyethoxy ) phenyl group, co, S; -dimethoxyphenyl group, p -(N
, N-dimethylamino)phenyl group, and the like.

Aralkyl groups include benzyl group, phenethyl group,
Examples of the substituted aralkyl group include a metherpenzyl group and a II-methylphenethyl group, and examples of the substituted aralkyl group include a -monocyanobenzyl group, a p-hydroxybenzyl group, a cyhydroxyphenethyl group, and a -1-anisyl group.

Further, the nitrogen-containing heterocyclic group represented by Nll"l" includes l-pyrrolidinyl group, 3-methyl-l-pyrrolicinyl group, -1hydroxyether-7-pyrrolidinyl group, 2.
3-dimethyl-l-bio9dinyl group, J-thiazolidinyl group, l-pipril group, l-pyrazolyl group, l-imidazolyl group, morpholino group, piperidino group, 2,6-dimethylbiperidino group, Examples include 1-piperazinyl group, dermeter-1-piperazinyl group, and the like.

As NR'l'', a di-substituted amino group having a total of 6 to 12 carbon atoms is particularly desirable.

To produce the anthraquinone dye represented by the general formula [■], for example, in an organic solvent such as acetone, methyl ethyl ketone, toluene, nitrobenzene, thioxone, N, N-dimethylformamide, N-methelukopyrrolidone, dimethyl sulfoxide, etc. , for the anthraquinone compound represented by the general formula [1] and the monoantho2quinone compound /-1λ times □ mole of the general formula (1''!, 1,
. . .: Heru difluorotriacunes are mixed with an acid binder in an amount of I-1 times the mole of the anthraquinone compound, for example, 1.
It is sufficient to heat the resulting reaction product liquid to room temperature to 90°C for about 05 to 3 hours in the presence of triether and tributyl inorganic bases, and then filter the resulting precipitate by discharging it into water, for example. The anthraquinone dye #1 quantitatively represented by general formula CI) can be obtained by separation by a method such as centrifugation.

Cellulose-containing fibers dyed with the dye represented by the general formula [I] include natural fibers such as cotton and linen, semi-synthetic fibers such as viscose rayon and copper oxide rayon,
Examples of partially aminated Ti include fibers such as partially acylated modified cellulose fibers, woven and knitted fabrics, and nonwoven fabrics thereof. In addition, the above fibers may be spun or blended with other types of fibers such as polyester fibers, cationically dyeable polyester fibers, anionically dyeable polyester fibers, polyamide fibers, wool, acrylic fibers, urethane fibers, diacetate fibers, and triacetate fibers. Examples include textiles. Among these, it is particularly effective for cellulose fibers and blended or mixed fiber products of cellulose fibers and polyester fibers.

When carrying out dyeing, it is desirable to finely disperse the dye represented by the forefoot general formula [I] in a medium by about 1 fK of KajP-1μ, and the method for doing so is to use a nonionic agent, such as a pluronic type surfactant or an anionic dispersant. , for example, using a water-soluble dispersant such as sodium trininsulfonate or sodium salt of naphthalenesulfonic acid-formalin condensate, and finely dispersing it in water using a grinder such as a sand grinder or mill, sulfosuccinate ester, nonyl Using a poorly water-soluble or water-insoluble dispersant such as a compound with a low molar addition of ethylene oxide to y x / -# etc., a solvent other than water such as ethyl alcohol,
Alcohols such as isopropyl alcohol and polyethylene glycol, ketones such as acetone and methyl ethyl chloride, hydrogen sulfides such as hexane, toluene, xylene, and mineral turpentine, and halogenated carbons such as tetrachloroethylene. A method of finely dispersing it in hydrogens, esters such as ethyl acetate and butyl acetate, ethers such as dioxane and tetraethylene glycol dimethyl ether, or a mixed solvent thereof, or optionally mixing it with water among the above solvents. Examples include a method of finely dispersing it in a mixed system with a solvent to be obtained.

Furthermore, in the above-mentioned fine dispersion process, a polymer compound soluble in each dispersion medium or a surfactant having a function other than the dispersion effect may be added.

This fine dye dispersion can be used as it is as a padding bath in a padding dyeing method, or as a printing paste in a textile printing method, but the fine dye dispersion can be used as a padding bath or a textile dyeing paste with water or water. A mixed system of solvent and water that can be mixed arbitrarily, or an O7W type emulsion or a φ type emulsion system in which the oil layer is a petroleum hydrocarbon such as mineral turpentine or a halogenated hydrocarbon such as tetrachloroethylene, in proportions according to the desired dyeing density. A good diluted product is used.

In the preparation of padding baths and printing dyeing pastes, alkali metal compounds, organic epoxy compounds, organic vinyl compounds, etc. are used as cellulose fiber swelling agents or acid binders for the purpose of promoting the reaction between dyes and cellulose fibers in order to carry out dyeing advantageously. It can be added as In addition to alkali metal carbonates, alkali metal compounds include alkali metal heavy carbon salts, alkali metal phosphates, alkali metal borates, alkali metal silicates, alkali metal hydroxides,
Alkali metal fatty acid salts such as alkali metal acetates, or alkali precursor compounds that generate alkali when heated in the presence of water, such as sodium trictiW*ate and sodium acetoacetate, can be used. These usage amounts are
Usually 1, padding bath or textile dyeing-o pl [ga 1j
~, an amount that produces an r-voice is sufficient. Examples of organic epoxy compounds include ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether with an average molecular weight of 110 to 300, and examples of organic vinyl compounds include ethylene glycol diacrylate and polyethylene glycol with an average molecular weight of ISO to 00. diacrylate or dimethacrylate. The amount of these to be used is approximately 3 to 4 parts by weight (1°) to the padding bath or printing dyeing paste. KKl
A thickening agent, for example a water-soluble polymer such as sodium alginate, may be added to the 111-section rounding.

The preparation of the padding bath or printing dyeing paste is not limited to the above method, and the cellulose swelling agent and acid binder do not necessarily need to be present in the padding bath or printing dyeing paste, It may be left to exist.

As a cellulose fiber swelling agent, any substance that has the effect of swelling cellulose fibers at a boiling point of iso°C or higher can be used. For example, y, N, N', N'
Examples include ureas such as -tetramethylurea, polyhydric alcohols such as polyethylene glycol and polypropylene glycol, and their O derivatives. In particular, the average molecular weight is
Preferred as the cellulose fiber swelling agent are polyhydric alcohol derivatives such as polyethylene glycol and polypropylene glycol of about 200 g, which do not react with the reactive groups of dyes whose hydroxyl groups at both ends are dimethylated or diacetylated.

The amount of the cellulose fiber Wl@ agent to be used is approximately 3 to 10% by weight, preferably about 3 to 30% by weight, relative to the coating bath or textile dyeing paste.

To color the fibers with the dye represented by the general formula CI), for example, a padding bath or printing dyeing paste prepared by the above method is impregnated or printed on a cellulose fiber-containing material, and after drying, pcibo Heat treatment for 30 seconds to 10 minutes with hot air or superheated steam at ℃ to 0℃, or 3 to 30 minutes in Takada saturated steam at l-〇℃ to 130℃, and wash with hot water containing a surfactant. Alternatively, the oil layer may be washed with an O/W @ or ψ type emulsion washing bath in which the oil layer is a halogenated hydrocarbon such as tetrachloroethylene, or the washing may be completed using a conventional dry cleaning method.

Vivid and uniform dyeing with light fastness and humidity +1 by the above method! It is possible to obtain dyed products with good Il fastness.

Hereinafter, the present invention will be explained in more detail with reference to Examples. A is not limited to the following examples unless it exceeds the gist thereof.

In addition, "parts" in the examples indicate "parts by weight."

Example 1 15 parts of anthraquinone dye represented by the following structural formula, naphthalene sulfonic acid-formaldehyde product/! f part and water 7
A dye dispersion liquid was prepared from the dye composition □ consisting of 0 parts using a paint shaker as a fine dispersion machine. Using this dye dispersion, make the following composition: Dye dispersion 45 parts 596 Algi tetrasodium aqueous solution SS Hot water
Prepare a printing dyeing paste for polyester/cotton (warming ratio: 4).
jt/1! r) Printed using a blended fabric i-screen printing machine, intermediately dried at t0℃ for 3 minutes, and then dried at λiz℃ for 3 minutes.
It was fixed by dry heat for seconds. After washing it with water, use a nonionic surfactant (Scoreroll #ri00 (trademark), manufactured by Kao Soap ■).
20/l at a bath ratio l:30 using a cleaning solution containing 21/l
Soaping was carried out at t0° C. for minutes to obtain a blue dyeing with excellent light fastness and wet fastness.

The dye used in this example was synthesized by the following method. /,
! -Diaminoda, t-dihydroxyco-(Hydroxyphenyl)anthraquinone 36P is dissolved in N-methyl-2-pyrrolidone 50-trietheramine and co-,41-difluoro-dietheraminotriazine. 0? Add and incubate at IIoC.
The condensation reaction was carried out by stirring. The reaction solution obtained was 200 mL
- The precipitate produced was filtered, washed with water, and dried at room temperature in a vacuum dryer to obtain a dark blue powder of the dye represented by the above structural formula.

λma of this dye! (Acetone) U 42 t a
It was m.

Example 2 75 parts of anthraquinone dye represented by the following structural formula, Pluronic-type external surfactant Pluronic L4 (manufactured by Asahi Denka Kogyo) 1
A dye dispersion liquid was prepared from a dye composition consisting of 0 parts of water and 5 parts of water using a sand grinder as a fine dispersion machine.

Using this dye dispersion, make the dye dispersion with the following composition: -3 parts Algium ΔLedge sodium aqueous solution 3k parts water
A printing dyeing paste of 23 parts/DO @ (pH 1k) was prepared and printed on a mercerized nine-fine broad (number 3) using a screen printing machine.
After drying for 3 minutes at 0.degree. C., it was treated with superheated steam at tgs.degree. C. for 3 minutes. Thereafter, washing treatment was carried out according to the method described in Example 1, and a blue dyed product with excellent light fastness and wet fastness was obtained.

The dyes used in this example were i, s-diaminoder, t-
Obtained from K by reacting dihydroxyco-(3-)f-ruder-hydroxyphenyl)anthraquinone with difluoro-6-piperacinyltriazine in dimethyl sulfoxide with tri-n-butylamine as a deoxidizing agent.

This product was λwsax & 19am.

Example 3 Anthraquinone dye io@, polyoxyethylene clico, -runonylphenyl ether (uti+) represented by the following structural formula
zy) and 11 parts of diethylene glycol diacetate as a fine disperser.
A dye ink was prepared by grinding with a conditioner.

After mixing 70 parts of this dye ink and part of mineral turpentine Sj, this was stirred with a homomixer (&ooo ~2o
oo RPM) Shiratsu was gradually poured into 35 parts of an aqueous solution having the following composition and stirred until uniform, to prepare a viscous O/W type emulsion color paste.

Using 01 parts 3@ of Triku Shitou Sodium Acetate as a part, use this color paste to print on polyester/cotton □・1 (mixing ratio 44r/J!1) blended fabric using a screen printing machine, and print at IOO℃ for 1 minute. After drying, use superheated steam/? It was treated with fC for 7 minutes. - Then, when washed in a hot tetrachloroethylene bath containing a small amount of water and dried, a blue dyed product with excellent light fastness and wet fastness and no hot water stain was obtained.

The dyes used in this example were /, j-diaminode, l-
Dihydroxyco-(2-methoxydhydroxyphenyl)anthraquinone in methyl ethyl ketone with triethylamine and potassium carbonate as a deoxidizing agent, 4
It was obtained by reacting with L-difluoro-4-(N,N-di-n-butylamino)triazine at 60°C for 1 hour.

The λvaax (acetone) of this product was 6 to 1 m.

Example Tei Anthraquinone dye represented by the following structural formula, polyoxyethylene glycol) nylphenyl ether (IILII/
JJ) 7 parts, 3 parts of naphthalene sulfonic acid-formaldehyde condensate and sulfur sulfur.

A dye dispersion liquid was prepared by finely dispersing the dye composition consisting of the following parts using a sand grinder. Using this dye dispersion, a padding bath with the following composition: dye dispersion: 6 parts, water, 79 parts, 100 parts (νmto) was prepared, and it was impregnated into a polyester/cotton (mixing ratio of 6!/J!) blended fabric, and then the padding bath was made into a padding bath. Rate da! A blue dyeing with excellent light fastness and wet fastness was obtained.

The dye used in this example was synthesized according to the method described in Example.

The λmax (acetone) of the crystal was λmax.

In the example, the fiber is nylon/rayon (mixing ratio go, 7sro)
Printing was carried out in exactly the same manner as in Example 1 except that the blended fabric was used and the dry heat fixation temperature was changed by 1 tscK, and a blue print with good wet fastness and light fastness was obtained. Ta.

Example 6 Prints with good anthraquinone dye fastness and wet fastness shown in Table I and Table 1 were obtained.

Claims (1)

[Claims] (1) General formula [wherein, an optionally substituted alkyl group, alkenyl group, cyclohexyl group,
represents an aryl group or an aralkyl group, or N
R"R" represents a 3-membered or uA-membered nitrogen-containing heterocycle formed by linking R1 and V, and the total number of carbon atoms of V and V is not more than it. ] An anthraquinone dye for cellulose-containing fibers represented by: