JPS598760A - Monoazo compound and dyeing or printing method using the same - Google Patents

Abstract

NEW MATERIAL:A compound of formula I [X is nitro or cyano; R1 and R2 are H, 1-6C alkyl, 1-6C alkoxyl(1-3C) alkyl, 1-6C alkoxyl(1-3C) alkoxyl(1-3C) alkyl, allyl, allyloxy(1-3C) alkyl, hydroxy(1-3C) alkyl or formula II (R3 is 1-4C alkyl or allyl)]. EXAMPLE:The compound of formula III. USE:Dyeing and printing hydrophobic fiber materials, e.g. polyester fibers, cellulose diacetate fibers, cellulose triacetate fibers, or acrylic fibers, etc. in blue color. PROCESS:An aromatic primary amine of formula IV (X is bromine; Y is cyano, nitro or bromine) is diazotized with a diazotizing reagent, e.g. nitrosylsulfuric acid, in sulfuric acid, and the resultant diazonium salt is then coupled with a quinoline derivative of formula V to give a monoazo compound of formula VI, which is then agitated with a cyano compound under heating to substitute the bromine atom with a cyano group.

Description

[Detailed description of the invention] [In the formula, X represents nitro or cyano, mountain, R.

are independently hydrogen, CC+~C-)-alkyl, (Cs~c
, )-alkoxy(to Cs(:3)-Yno1/kyl, (
C1~Ca)-alkoxy(6~(2-alkoxy(
C1~C,)-alkyl, allyl, oryloxy (mountain~
c-1 alkyl, doroxy(CI~03)-alkyl or -C112g: sweet 0k120 LLs < i 3
The present invention relates to a monoazo compound represented by (Cr-Ca)--representing alkyl or allyl) and a method for dyeing hydrophobic fibers using the monoazo compound.

Book Q 11 (',) The monoazo compound of the formula (I+) has various fastnesses that are semi-uniform, and in particular, the fastness of the formula (1) is 1 (□).

It is better if one of R2 is made of water thread.

7) Azotization of the present invention is prepared as follows.

The aromatic primary amine represented by the formula 1 (10) is prepared using the conventional method II (for example, nitrone + pf acid, etc.) The diazonium salt obtained in this way is subjected to a coupling reaction using the following formula (expressed as I loss) with a quinoline monolith in a conventional manner. Synthesize a monoazo compound having the following formula (6).
480. Pyridine, N The desired 17-noazo dye is obtained by heating and stirring the mixture with methylpyrrolidone and placing a bromine atom on the cyano group.

[In the formula, X is shellfish, Y is shea], nitro or [In the formula, Rs
, ni'L4 has the same meaning as above] [R in the formula,
It,, (Easily synthesized) by reacting with a lkylating agent or, in some cases, by carrying out a Bucherer reaction between 8-oxyquinoline and an aliphatic primary amine.

Also, when dyeing is used as a mixture of dyes, 8
- It can be obtained by reacting aminoquinoline with an alkylating agent, or by reacting 8-oxyquinoline with a number of aliphatic primary amines. Conversely, the diazo component is 2 Kashikawa (1!/Il is 2-bromo-4,6-sinitroaniline, 2-from-6-zoano-4-nitroaniline)
It is also 6'''rii5 by reacting. Furthermore, they can be mixed and used during staining or decontamination.

The thus obtained seven-noazo-dongboku can be used for dyeing or vermilion printing of hydrophobic fibers such as polynisder fiber, cellulose diacetate fiber, cellulose triacedate fiber, acrylic fiber, etc. in Indo-German or as a mixture. I can do it.

Especially excellent dyeing for polyester fibers.
, and a beautiful blue dyed product with excellent covering properties can be obtained.

The dyed product thus obtained has excellent fastness, and for example, in terms of light fastness, it is at the highest level, surpassing that of other fractional dyes. On the other hand, in recent years, dyed products are subjected to various post-processing in order to impart various quality characteristics, but in such cases, water fastness and synthetic washability are seen to deteriorate. It will be done. In the present invention, for example, when a textured finish is applied, a good fastness level is maintained and staining of silk or nylon fabrics is extremely low, which is required by the present invention and modern dyeing processes. Things! rUi, and it is estimated that the contribution to the rise of the dyeing industry will be significant.

The following table shows the dye of the present invention, the monoazo compound of Japanese Patent Publication No. 44-24707 containing a quinoline conductor as a coupling component as in the present invention, and the iodine-2,6-dicyano compound of the present invention.
Special Publication No. 47-3 containing 4-nitroaniline as a diazo component
The results of a comparative test with 0410 monoazo dye are shown.

The dye disclosed in Japanese Patent Publication No. 47-30410 is particularly poor in light fastness. On the other hand, the dye No. 44-24707 has excellent light fastness, but other fastness is poor.
- It is short and its properties are inferior when compared comprehensively with the embodiments of the present invention.

Also, the present invention has the value of dyes in general: ■ String brightness! f
-7, and this point enhances its cost-effectiveness as a dye.

Each test method in the table was performed using the following method. The advantageous foot is ×, △
, ○ was performed, and in the order of ××Δ〈○, ○ was considered the best.

Light fastness: Measured according to JISL-0842.

Sublimation fastness: Dyeing yield 2 rolls OWF bath ratio 130p) (4~
5 1301: Lightly cloth Tetron white cloth on Tetron cloth dyed under the dyeing conditions of 60 minutes at 200C, heat with an iron raster for 30 seconds, and check the degree of contamination of the attached cloth to JIS L-08.
Judgment was made using 05 gray scale.

Post-processing resistance: Treated with Hydran 24K 1% water bath solution (texture finish machining manufactured by Inu Nippon Inn-?) / Co., Ltd., JIS L-0846 and AAi" (:e
According to the ll method, Kao Ninowandafuru (Hanado Soap Synthetic Washing Moon) 5z/Numa 50c x 30 minutes with nylon 11
Contamination Lf was determined. - p14 Dependency: Judgment of dyeability at pH 4, 5, 7, and 9 using acetic acid and sodium acetate as a buffer.

Covering matter: Determination by dyeing a blend of polynis glue with different thermal history In the present invention, a compound represented by formula (11) and I7
For example, 2-bromo-6-no-γ-42-I-lowerin, 2-bromo-4,6-dinitroaniline, 2,6-dipromo-4-nitroaniline is expressed by the above formula (for). The following compounds are listed as
Ru. Koronakaide, 1t2 means the okiki group of the above formula (11).

C4HJ++1 1-, c・H・OC・H・(・) -C'21140C21140 (11! Seventh aspect of the present invention) The azo compound is a synthetic fiber, especially a fiber such as polyester cellulose acetate, cellulose triacedate, or polyacrylic. Suitable for dyeing or printing, dyeings in red, yellow, and k colors are more suitable than solid yellow-orange colors.

In this case, the formula (11-7) is an azo compound! It is preferable to use a dyeing composition which is made into a dye by melting and cutting, and if necessary, mixed with a dyeing aid. That is, the monoazo dye is mixed with a formalin condensate of naphcrene sulfonic acid, sulfated creosote oil, lignin sulfonate, and a 1-ton dispersion of anine.
Blocks of ethylene oxide, ethylene oxide, ethylene oxide, etc. may be prepared using a ball mill or sand mill in the presence or absence of water and a nonionic activator such as an ethylene oxide adduct of alkylphenol. The dye composition is prepared by thoroughly wet-pulverizing the dye before use, or spray drying it before use. This composition is subjected to Shimatsu dyeing, carrier dyeing, thermosol dyeing, and textile printing according to the trial judgment. In the case of textile printing, it is desirable to use a natural sizing agent, a synthetic sizing agent, a pH regulator, and a dyeing agent in combination. In addition, if a paste containing a discharge printing agent such as tin chloride, Rongalite, or alkali is printed over a color paste containing Insho Sumitomo and snarming, sharp discharge dyeing can be performed.

According to the present invention, it has become possible to obtain a dyed product of hydrophobic fibers having excellent average fastness and dyeability.

One example of the actual bII will be explained below. In the examples, all of the things that have Suzu taste like katana (W' @u).

Example 1゜(1) 17.4 kg of 8-hydroxyquinoline and 1 bl of 8-hydroxyquinoline (
Sodium oxyhydrogen 12.5i++, γ-methoxylazolamine 248b and 18 parts of water were placed in an autoclave and heated under 145CX for 20 hours. cooling thy gamma-
Distill off the methoxypropylene, pour the oil into 400 parts of water, and adjust the pH to 11 with caustic soda. Extract the oil with 50 parts of ethyl ether.
JU - The same operation was carried out, and the obtained needle bath solution was washed with water, and the pseudoether was distilled off.

This produces a pale yellow-brown oil) AI.

f2+ 151 tt of 96% sulfuric acid obtained by cooling 24.2 parts of 2-bromo-6-cya2-4nitroaniline to below 5C
Gradually increase the power (to 1) while stirring. I gave you 90 notes of southern acid containing 5 parts acetic acid and 1 part propionic acid.
Increases power by 11 when below OC. Next, add 31.1 parts of 43 (Jinitro Tsurutsukuda) acid and stir for 2 hours to cyanide.

(3+ (Add 11 ml of oil to 900 ml of water containing 96% and 10 parts of salt, add 1 ml of water, add 0.5 tslt of sulunamic acid to 1 ml), add b's water to 1 oz. EQ
Add the diazonium layer (2) while cooling to C. As a result, colored viscous crystals are precipitated. Next, this reaction solution was filtered with 60CX211 (extracted with stirring under heat). By drying the crystals, 44.7 parts of an azo compound was obtained.

(41 (5.0 parts of the monoazo compound obtained in step 31 and DMF
95 CX by mixing 15 carbon atoms and 1.4 parts of cuprous cyanide.
The reaction was carried out for 8 hours, then cooled to room temperature and added with methanol 1
The bales were stirred for 1 hour, filtered, washed with 20 parts of methanol, and then washed with water. Residue is 15% ammonia water 10
0 parts and stirred in a suspension pot for 4 hours at room temperature, then treated with 1N. Perform the turning operation again.

Then 5% sodium cyanide water bath g5ogh and 2 at room temperature.
time) Stir and filter. The same operation was performed once to completely remove the copper content. Finally, 2.0 parts of dark blue crystals represented by the following formula were obtained by thoroughly washing with water and drying. This heptanoazo dye had a lambda of 630 nrn in a 75% acetone water bath. Also 1.4
- Elemental analysis Iμ of a shield crystallized from dioxane is Ritsugu and Ai <-CJLy N70s N'=-f415 (
51 (18 parts of monoazo dye obtained in 41 and Demol C (@
Add water to 18 parts of Demol N (trade name, MMII manufactured by Kao Atlas Co., Ltd.) and 24 parts of Demol N (trade name, MMII manufactured by Kao Atlas Co., Ltd.)
Diversify the value in a sand mill as a slurry. Then, the mixture was spray dried to obtain a soft dispersion composition.

This composition vtJare(5) was added to 3000 mt of water, and the pH was adjusted to 5 with sodium acetate and acetic acid. 100 mt of polynisglu fiber was soaked in this and dyed for 60 minutes.The sasen cloth was soaped, washed with water, and dried. These steps were carried out sequentially to obtain polynisal east-colored products with a 4i11 degree of hardness.

The following description will be given in the same manner as Example-20.

In the table, R, and R2 represent the substituent groups of formula (II).

Example 21゜(118-7mi/-?/+) 714.4 tjl+
and water 2081i,! 1 ['Magnesium fluoride 4.0
5B and 85Ck (heat and stir, add 29 parts of allyl glycol tosylate to this in about 4 hours.
5iC~10 (Stir for 16 hours with JC.
Commonly understood as 0 parts and 10 parts of 96% sulfuric acid.

(Add 2196% acid to 40 parts of 6-bromo-2,4-dinitro7 = 1726.2 parts), then add 43%
Nitrosil Tsukuda acid 296 sweat power 11, 5 at 30'C
Stir for a while.

(3+ (11 sulfamine ao, 5 jil
Then add the diazonium salt (2) to 16% while keeping the temperature at OC while reducing the pressure on the crushed ice. At this time, the pH of the reaction mixture is adjusted to 4 by adding 4OSNaOHaq to 11. Crystals are precipitated in Shoken color as well (1)
-4). The bales were heated and stirred at 50C for 2 hours and washed with a dog's knife to remove the acid content.

By drying, a heptanoazo compound with 45 axes 1≦ is obtained.

Substitute elementary atoms with cyano. A mixture of heptanoazo dyes represented by a self-structure was obtained. The composition ratio was obtained by liquid chromatography. The structure was also confirmed by MM spectrum.

11% λ1llax 638 (5) The dye composition obtained in (4) was carried out and
Dyeing was carried out according to IJ (5) to obtain various fastness characteristics.
A blue IJ x sprue was obtained.

This will be shown in Example 251 below.

Example 26 200 parts of Makoin Groover 880 (product name; leveling improver manufactured by Yokohama Polymer Research Institute) and 1000 parts of lukewarm water were added and stirred well. 3. Print this color paste on a polynisal cloth, and after intermediate drying, perform lfT steaming using JA3i hot steam for 170cm x 5 minutes.3. After that, wash with water, wash with hot water, and wash with reduction (-D).
t> is obtained.

Special 1° out m1 person Composite beam H technique CFJ4ν first hand
Continuing Amendment (Method) November 5, 1980 Kazuo Wakasugi, Commissioner of the Japan Patent Office 1 Indication of the case Patent Application No. 116150 of 1982 2 Name of the invention Monoazo compound and dyeing or printing method using the same 6
Relationship with the case of the person making the amendment Patent applicant 4, agent 2-1 Marunouchi, Chiyoda-ku, Tokyo October 26, 1982

Claims (1)

[Scope of Claims] [In the formula,
Alkoxy(C1-C5)-alkyl, (c, ~C ring)
-Alkoxy(Cyu~C5)-Alkoxy(Cl5Cs
)-alkyl, allyl, oryloxy (Cs-C-aryl, hydroxy-tasting)] [wherein X is nitro or sia], R1゜R2 are independently hydrogen. , (C!~C6)-alkyl, (C1~C,)
-alkoxy(C1-C&)-alkyl, (C1-C5
)-alkoxy(Cs-Cm)-alkoxy(C1-C
3)-Alkyl, allyl, oryloxy (CIS-Cs
) alkyl, hydroxy(C1-c3)-alkyl or -OHFACHxOk%x<B, is (C1-C4
) - A method for dyeing or printing a hydrophobic fiber material, characterized by using one or more monoazo compounds represented by (n) representing alkyl or allyl.