JPS6213461A - Disazo dye - Google Patents

Abstract

NEW MATERIAL:Compounds of formula I, wherein X is H, halogen, alkyl, alkoxy, NO2, CN2, CF3, SO2R<1>, COR<1>, COOR<1>; R<1> is H, a 1-8C alkyl (substd. by a 1-8C alkoxy, CN2, Cl, acyloxy or phenyl), alkenyl, aryl, tetrarydrofurfuryl; Y is H, Cl, CH3, lower alkoxy, acylamino; Z is H, CH3, lower alkoxy-(alkoxy), Cl, Br; R<2> is a 5-12C alkyl, aralkyl, phenoxyalkyl; n is 1-3. EXAMPLE:Compd. of formula II. USE:Disazo dyes which dye synthetic fibers, particularly polyester fibers orange to blue. PREPARATION:An amine of formula III is diazotized and then coupled with a compd. of formula IV.

Description

[Detailed description of the invention] C&) Purpose of the invention The present invention relates to a disazo dye with excellent fastness.

(Industrial Application Field) The dye of the present invention is advantageously used as a dye that provides a dyed product with excellent wet fastness, especially after post-processing after dyeing.

(Prior Art) Recently, various post-processing processes such as water-repellent processing, hand-improving processing, antistatic processing, sanitary processing, etc. have been carried out on polyester cloth.

Since the above-mentioned post-processing involves high-temperature treatment, the dye is deleted from the already dyed fibers, etc., resulting in a problem that the various fastnesses, especially the wet fastnesses, of the fibers, etc. are reduced.

For example, Japanese Patent Publication No. 47-9117 describes various benzothiazole-based disazo dyes, which have excellent light fastness. There was a drawback that the wet fastness after washing was extremely low.

(Problems to be Solved by the Invention) The present invention is a disazo dye capable of dyeing synthetic fibers, particularly I-lyester fibers, or fabrics produced from these in orange to blue. The purpose of the present invention is to provide a disazo dye that does not cause dye bleeding even after post-processing of dyed fabrics, etc., and has excellent wet fastness such as washing fastness, alkaline sweat fastness, and water fastness.

(b) Structure of the Invention (Means for Solving the Problems) As a result of repeated seeding research in order to solve the above-mentioned problems, the present inventors have developed a disazo dye of the present invention having a specific molecular structure. I was able to achieve that goal.

The disazo dye of the present invention has the general formula [wherein,
group (R is the same as R described later), COR' group (R1 is the same 0 as R1 described later), or C0OR' group (R1 is the same as R1 described later), and Y is a hydrogen atom or a chlorine atom. , represents a methyl group, a lower alkoxy group, or an acylamino group, and 2 represents a hydrogen atom, a methyl group, a lower alkoxy group, a lower alkoxyalkoxy group, a chlorine atom, or a bromine atom.R1 represents a hydrogen atom, a C1-8 alkyl group (
The alkyl group includes a C1,8 alkoxy group, a cyano group, a chlorine atom, an acyloxy group, a 01-6 alkoxyalkoxy group, a phenyl group, a phenyloxy group, an aralkyloxy group, a carbamoyl group, an alkoxycargenyl group, and a phenoxyalkoxycalde group. Nyl group, phenyl C12, alkoxycarnonyl group, alkoxyalkoxycargenyl group, allyl oxyne alkoxycar? by a nyl group, an alkoxycarbonyloxy group, a pen/zyloxycarzenyloxy group, a succinimide group, a phthalic acid imide group, a cyanoalkoxy group, or an aryl group substituted with a halogen atom, a methyl group, a methoxy group, or a nitro group. May be replaced. ], represents an alkenyl group, an aryl group, or a tetrahydrofurfuryl group.

R represents C5~, a 2-alkyl group, an aralkyl group, or a phenoxyalkyl group. n represents a number from 1 to 3. ] It is a dye shown by.

Examples of the halogen atom represented by X in the disazo dye of the present invention represented by the general formula (1) include a chlorine atom, a bromine atom, a hydrogen atom, and the like. Examples of the alkyl group represented by R include a methyl group, ethyl group, linear or branched globyl group, butyl group, pentyl group, hexyl group, hegtyl group, and octyl group, and In addition to these alkyl groups, examples of the alkyl groups include nonyl groups and decyl groups. Examples of the acylamino group represented by Y include acetylamino group, chloroacetylamino group, benzoylamino group, methylsulfonylamino group, chlorozolopionylamino group, chlorobutyrylamino group, ethoxycargenylamino group, and ethylamino group. Examples include carbonylamino group.

Examples of the alkoxy group represented by X include methoxy, ethoxy, linear or branched glopoxy, butoxy, hexyloxy, octyloxy, and the like. . Examples of the alkoxy group as a substituent in the alkyl group represented by R1 include the same alkoxy groups as these alkoxy groups represented by X, but C
Examples include 1-8 alkoxy groups. Examples of the alkyl group having an acyloxy substituent represented by R1 include an acetyloxyethyl group, a chloroacetyloxyethyl group, a chloroglobionyloxyethyl group, and a benzoyloxyethyl group. Examples of the alkyl group having an alkoxyalkoxy substituent represented by R include a methoxyethoxyethyl group, an ethoxyethoxyethyl group, and a hekynyloxyethoxyethyl group. Examples of the alkyl group having an aralkyloxy substituent represented by R include benzyloxyethyl group,
Examples of the alkenyl group represented by OR include a phenethyloxyethyl group, a chlorobenzyloxyethyl group, and a phenylglopyloxyethyl group, such as an allyl group and a crotyl group.As an aryl group represented by R1, Examples include phenyl group, chlorophenyl group, and tolyl group. C5~, represented by R;
The 2-alkyl group may be linear or branched.

Examples of the aralkyl group represented by R2 include p/
Examples include a nor group, a rin-oo-j group, a full group, a phenethyl group, and a phenylglobyl group.

Particularly preferred among the disazo dyes of the present invention represented by the general formula (1) are those in which X is a hydrogen atom, a chlorine atom, or a nitro group, and Y is a hydrogen atom, a chlorine atom, a methyl group, or an acetylamino group. 2 is a hydrogen atom, R
1 is a C4-4 alkyl group, a C1-6 alkoxyethyl group, a phenoxyethyl group, an allyl group, a phenyl C4-3 alkyl group, or (CH2)nC00R2 (in the formula, R2 is the same as the above R2), and R2 is 06~. . Examples include dyes having an alkyl group, a phenyl C1-3 alkyl group, or a phenoxyethyl group.

The disazo dye of the present invention represented by the general formula (r) is:
General formula [wherein, X is the same as X in the above general formula (r)]. ] The amine represented by the general formula is diazotized according to a conventional method, and then Y, Z, R, R and n are the same as those in the general formula (1). ] It can be easily produced by coupling with the compound shown below.

Fibers that can be dyed with the azo dye of the present invention include polyester fibers made of polyethylene terephthalate, polycondensates of 1,4-bis-(hydroxymethyl)cyclohexane terephthalate, and natural fibers such as cotton, silk, and wool. Examples include blended products and mixed fiber products of fibers and the above-mentioned polyester fibers.

In order to dye polyester fibers using the dye of the present invention, since the dye represented by the general formula (I) is insoluble or sparingly soluble in water, naphthalenesulfonic acid and formaldehyde are used as dispersants in a conventional manner. Dyeing or printing may be carried out by preparing a dyeing bath or printing paste in which a condensate, higher alcohol sulfuric ester, higher alkylbenzene sulfonate, etc. are dispersed in an aqueous medium. For example, in the case of dip dyeing, polyester fibers or their blends can be dyed with excellent fastness by applying ordinary dyeing methods such as high temperature dyeing, carrier dyeing, and thermosol dyeing. In this case, if an acidic substance such as ic acid, acetic acid, phosphoric acid or ammonium sulfate is added to the dyeing bath, even better results can be obtained.

Furthermore, the zosazo dye of the present invention represented by the general formula (1) may be used in combination with dyes of the same type or dyes of other types, among which the dyes are represented by the general formula (1).

(Examples, etc.) Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Example 1 2-amino-6-phenylazope/zothiazole5. I
I was dissolved in a mixture of 15 d of phosphoric acid and 15 m of acetic acid, and 0
Diazotized using 42-functional nitrosyl sulfuric acid at ~-3°C,
The obtained diazo solution was mixed with 5 liters of sulfuric acid, 400 dl of CN-methyl-N-phenoxyethoxycarbonylethylaniline, and 6
It was added dropwise to the solution in which 11 was dissolved at a temperature of 0 to 5°C.

The precipitated crystals were filtered and dried to obtain dark red crystals.

This crystal had a visible light absorption analysis value of λmaw (acetone) of 545 nm, had the following structural formula, and had a yield of 85 nm.

This disazo dye O,SII was mixed with naphthalenesulfonic acid-
A dyeing bath was prepared by dispersing formaldehyde condensate 11 and higher alcohol sulfate 2I in water 3j. Polyester fiber 10019 was immersed in this dyeing bath, dyed at 130° C. for 60 minutes, and then washed, washed with water, and dried to obtain a bright red dyed fabric. The light fastness, sublimation fastness and water fastness of the obtained dyed fabric, as well as the temperature stability and -stability during dyeing of the dye were good.

In addition, the wet fastness (washing fastness, alkali sweat fastness, and water fastness) after further polyurethane processing (handle improvement processing) of the obtained dyed fabric was determined according to the following method. As shown in the table.

(1) Polyurethane processing method After immersing in a 1% solution of Hytran F-24K (trade name of Dainippon Ink Co., Ltd.), curing is performed at 160° C. for 2 minutes.

(2) Washing fastness Multi-fi dyed fabric treated with pre-urethane
A fluid bed test was conducted in accordance with AATCC Method Laundry ■A, and contamination of the nylon fibers of the multi-fiber was determined on a gray scale.

(3) Alkaline sweat fastness JIS L-08 dyed fabric treated with polyurethane
Tests were conducted in accordance with Method 48A, except that nylon cloth and silk cloth were used as the attached cloths, and the degree of contamination of the silk cloths was determined on a gray scale.

(4) Water fastness: Dyed fabric treated with polyurethane according to JIS, L-084
The test was conducted according to method 6A except that silk cloth was attached instead of nylon cloth, and the degree of contamination of the silk cloth was determined by gray scale.Example 2 N-Methyl-N-phenoxy used in Example 1 In place of ethoxycarbonylethylaniline 611, 5.8g of N-methyl-N-2-ethylhexyloxycarbonylethylaniline was used, and otherwise the coupling reaction was carried out according to the method described in Example 1. . The obtained disazo dye had the following structural formula, and its visible light absorption analysis value was λmax (acetone) 545 nm.

This disazo dye o, sy was mixed with naphthalenesulfonic acid-formaldehyde condensate 0.5. The mixture was mixed with P and pulverized in a paint shaker to obtain a finely divided dye. The mixture was thoroughly mixed with a base paste having the composition shown below to obtain 100 g of colored paste.

Composition of base glue: Right shoulder xymethyl cellulose glue 30 g tartaric acid
0.29 aromatic carrier
0.3.9 (Sunfloren SN, manufactured by NICCA CHEMICAL INDUSTRY CO., LTD., trade name) Water 68.5
．． 9 total 99. OI! Printing was carried out on this sticky polyester fiber, intermediate drying was performed at 100°C, and then held in superheated steam at 170°C for 7 minutes to develop color, followed by soaping, washing with water, and drying. A red printed polyester cloth with good fastness, sublimation fastness and wet fastness was obtained.

Further, the wet fastness of the obtained dyed fabric after polyurethane processing was as shown in Table 1.

Comparative Examples 1 to 3 Wet fastness after dyeing polyester cloth using various dyes having the following structural formulas described in Japanese Patent Publication No. 47-9117 and subjecting the obtained dyed cloth to polyurethane processing The results of the investigation are shown in Table 1.

Table 1 Examples 3 to 132 Various amines represented by the above general formula (If) having various substituents and the above general formula (■) having various substituents
Various cis-sazo dyes represented by the general formula (1) having various substituents shown in Table 2 were obtained by force-pulling reaction using various compounds represented by the formula (1) according to the method described in Example 1. Manufactured.

λmaX (acetone) value of each disazo dye obtained,
The color tone of the 4-liester dyed fabric and the wet fastness (alkali sweat fastness) after polyurethane processing were as shown in Table 2.

(e) Effects of the Invention As shown in the above Examples, the disazo dye of the present invention not only has high fastness after dyeing, but also improves dyed fabrics by improving texture, waterproofing, and antistatic properties. The subsequent wet fastness (fastness after post-processing) after processing or silicone processing is extremely high.

Therefore, the cis-sazo dye of the present invention is particularly suitable as a dye for high-quality clothing that undergoes post-processing.

Claims (1)

[Claims] (1) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, X is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a nitro group, a cyano group, a CF_3 group, a SO_
2R^1 group (R^1 is the same as R^1 described later), CO
R^1 group (R^1 is the same as R^1 described later), or C
represents an OOR^1 group (R^1 is the same as R^1 described below), Y represents a hydrogen atom, a chlorine atom, a methyl group, a lower alkoxy group, or an acylamino group, and Z represents a hydrogen atom,
Represents a methyl group, lower alkoxy group, lower alkoxyalkoxy group, chlorine atom, or bromine atom. R^1 is a hydrogen atom, C_1_~_8 alkyl group (the alkyl group is C
_1_ to _8 alkoxy group, cyano group, chlorine atom, acyloxy group, C_1_ to _6 alkoxyalkoxy group,
Phenyl group, phenyloxy group, aralkyloxy group,
Carbamoyl group, alkoxycarbonyl group, phenoxyalkoxycarbonyl group, phenyl C_1_-_3 alkoxycarbonyl group, alkoxyalkoxycarbonyl group, allyloxyalkoxycarbonyl group, alkoxycarbonyloxy group, benzyloxycarbonyloxy group, succinimide group, phthalic acid imide may be substituted with a cyanoalkoxy group, or an aryl group substituted with a halogen atom, a methyl group, a methoxy group or a nitro group. ), alkenyl group, aryl group, or tetrahydrofurfuryl group. R^2 represents a C_5_ to_1_2 alkyl group, an aralkyl group, or a phenoxyalkyl group. n represents a number from 1 to 3. ] A disazo dye represented by.