JPS6213460A - 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. with a 1-8C alkoxy, CN2, Cl or phenyl), alkenyl, aryl, tetrahydrofurfuryl; Y is H, Cl, CH3, lower alkoxy, acylamino; Z is H, CH3, lower alkoxy-(alkoxy), Cl, Br; R<2> is halogenopropyl, a 5-8C alkyl, 1-10C alkoxy (when Y is acylamino, Z is a 4-10C alkoxy), aralkyloxy (alkoxy), phenoxy. 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 (a) Object of the Invention The present invention relates to a disazo dye having excellent fastness. (Conventional technology) Recently, various post-processing processes have been carried out on polyester cloth, such as water-repellent finishing, hand-improving finishing, anti-static finishing, and sanitary finishing. ing.

The post-processing described above is carried out at high temperatures, so
A problem arises in that the dye bleeds from already dyed fibers, etc., and the various fastnesses of the fibers, especially the wet fastnesses, decrease.

For example, Japanese Patent Publication No. 47-9117 describes a positive benzothiazole-based nosazo dye, which has excellent light fastness. It had the disadvantage that the wet fastness was extremely low when it was applied.

(Problems to be Solved by the Invention) The present invention is a disazo dye that can dye synthetic fibers, particularly polyester fibers, or fabrics made from these fibers in orange or blue, and the resulting dye. The purpose of the present invention is to provide a disazo dye that does not cause dye bleed even after post-processing of cloth, etc., and can therefore produce dyed products with excellent wet fastness such as washing fastness, alkali sweat fastness, and water fastness. be.

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

The cis-sazo dye of the present invention has the general formula [wherein,
1 group (R1 is the same as R1 described later), COR' group (R
1 is the same as R1 described later. ), or C0OR' group (R1
is the same as R1 described later. ), Y represents a hydrogen atom, chlorine atom, methyl group, lower alkoxy group, or acylamino group, and 2 represents a hydrogen atom, methyl group, lower alkoxy group, lower alkoxyalkoxy group, chlorine atom, or bromine atom . R is a hydrogen atom, a C4-8 alkyl group (
The alkyl group includes a C1-8 alkoxy group, a cyano group, a chlorine atom, an acyloxy group, a C1-6 alkoxyalkoxy group, a phenyl group, a phenyloxy group, an aralkyloxy group, a carnomoyl group, an alkoxycarnonyl group, and a phenoxyalkoxy group. Carbunyl group, phenyl C1~, alkoxycar? Nyl group, alkoxyalkoxycarbunyl group, allyloxyalkoxycarbunyl group, alkoxycargenyloxy group, penzyloxycargenyloxy group, succinimide group, phthalic imide group, cyanoalkoxy group, or halogen atom , a methyl group, a methoxy group, or an aryl group substituted with a nitro group. ), alkenyl group, aryl group,
Or it represents a tetrahydrofurfuryl group. R2 is Hero r
Nogrovir group, C5-8 alkyl group, C1-. Alkoxy group (However, if Y is an acylamino group, 04~.
. It is an alkoxy group. ), represents an aralkyloxy group, an aralkyloxydialkoxy group, or a phenoxy group. ] is the dye shown.

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, and a fluorine atom. Examples of the alkyl group represented by R include methyl groups, ethyl groups, linear or branched globyl groups, butyl groups, pentyl groups, hexyl groups, hezotyl groups, octyl groups, etc. Examples of the alkyl group represented by X include the same alkyl groups as those represented by R above, as well as nonyl groups and decyl groups. Examples of the acylamino group represented by Y include an acetylamino group, a chloroacetylamino group, a benzoylamino group, a methylsulfonylamino group, a chloropropionylamino group, a chlorobutyrylamino group, an ethoxycargenylamino group, and an ethylaminocargenylamino group. Examples include nylamino group. Examples of the alkoxy group represented by Examples of the alkoxy group as a substituent in the alkyl group represented include the same C1-8 alkoxy groups as in the alkoxy group represented by X. Examples of the alkyl group having an acyloxy substituent represented by R1 include an acetyloxyethyl group, a chloroacetyloxyethyl group, a chlorotetrapropionyloxyethyl group, and a hendiyloxyethyl group. Examples of the alkyl group having an alkoxyalkoxy substituent represented by R include a methoxyethoxyethyl group, an ethoxyethoxyethyl group,
Examples include hexyloxyethoxyethyl group. Examples of the alkyl group having an aralkyloxy substituent represented by R include a penciloxyethyl group, a phenethyloxyethyl group, a chlorobenzyloxyethyl group, a phenylpropyloxyethyl group, and the like. Examples of the alkenyl group represented by R include allyl group and crotyl group, and examples of the aryl group represented by R1 include phenyl group, chlorophenyl group, and tolyl group. The C5-8 alkyl group represented by R may be linear or branched. Examples of the aralkyloxy group represented by R include a benzyloxy group, a chlorobenzyloxy group, a phenethyloxy group, a quinylglopyroxy group, and the like. Examples of the aralkyloxydialkoxy group represented by R include a benzyloxyethoxy group and a phenethyloxyethoxy group.

Particularly preferable dyes among the cis-sazo dyes of the present invention represented by the general formula (1) include 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
is a C1-4 alkyl group, a C1-6 alkoxyethyl group,
phenoxyethyl group, allyl group, phenyl C1-3 alkyl group, or CH2CH20COR (in the formula, R is the same as R above), and R is a chloropropyl group, C5
Examples include dyes having a ~8 alkyl group, a 04-8 alkoxy group, a penciloxy group, or a phenoxy group.

The disazo dye of the present invention represented by the general formula (1) is:
For example, the general formula [wherein, X is the same as X in the general formula (1) above]. ] The amine represented by the general formula is diazotized according to a conventional method, and then the amine represented by the general formula [wherein Y, Z, R and R are the same as those in the above general formula (I), respectively. ] 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 polyethylene terephthalate, terephthalic acid,! : 1,4
- Polyester fibers made of polycondensed metals with bis-(hydroxymethyl)cyclohexane.

Some examples include blended products and mixed fiber products of natural fibers such as cotton, silk, and wool 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 (1) is insoluble or sparingly soluble in water, naphthalene sulfonic 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, even better results can be obtained if an acidic substance such as formic acid, acetic acid, phosphoric acid or ammonium sulfate is added to the dyeing bath.

Further, the disazo dye of the present invention represented by the general formula (I) may be used in combination with dyes of the same type or dyes of other types. By mutually blending two or more types, good results of improved dyeability may be obtained.

(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-phenylazopenzothiazozotization,
The obtained diazo liquid was added dropwise at a temperature of 0 to 5°C to a solution in which 5.1y of sulfuric acid, 400rILlKN-methyl-N-chloroglobylcaldenyloxyethylaniline, was dissolved. The precipitated crystals were filtered and dried to obtain dark red crystals.

The visible light absorption analysis value of this crystal was λmax (acetone) 548 am, it was confirmed that it had the following structural formula, and the yield was 87%.

These disazo dyes O, S, and V were combined with naphthalene sulpo/acid-
A dyeing bath was prepared by dispersing the mixture in 3 volumes of water containing formaldehyde metal condensate II and higher alcohol sulfate ester 2I. I-Reester fiber 100.9 was immersed in this dyeing bath and dyed at 130° C. for 60 minutes, followed by unwinding, washing with water and drying, resulting in 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. It was as shown in the table.

(1) Polyurethane processing method After immersing in a 100% solution of Hytran F-24K (trade name of Dainippon Ink Co., Ltd.), curing is performed at 160° C. for 2 minutes.

(2) Washing fastness A multi-fiber was attached to a dyed cloth treated with polyurethane, and a washing test was conducted according to AATCC washing method No. A, and the 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
48A method, but the attached cloth was tested using a method using nylon cloth and silk cloth, and the degree of contamination of the silk cloth was determined on a gray scale. 0 (4) Water fastness: Dyed cloth treated with polyurethane. JIS L-08
A test was conducted according to the 46A method except that silk cloth was attached instead of nylon cloth, and the degree of contamination of the silk cloth was determined on a gray scale.

Example 2 N-methyl-N-chlorozolopylcar? FCN-ethyl-N-n-butoxycar instead of 5.1 g of nyloxyethylaniline? 5. Nyloxyethyl-m-toluinone.
Using 4I, the reaction was otherwise carried out according to Example 1,
A disazo dye having the following structural formula was obtained. Its λma
x (acetone) +'z 5 s 5 nm.

This disazo dye 0.5I! Naphthalenesulfonic acid
The mixture was mixed with 0.5 y of formaldehyde metal shrinkage and pulverized in a paint shaker to obtain a finely divided dye. Color paste 1009 was obtained by thoroughly mixing with the base paste having the composition shown below.

Composition of original glue? Oxymethyl cellulose glue 30
& tartaric acid 0.2. F Aromatic Carrier 0.3.9 (Sunfloren SN1 manufactured by NICCA Chemical Industry Co., Ltd., trade name) The colored paste was broken and printed on the ester fiber, and intermediate drying was performed at 100°C, followed by 170°C. After being held in superheated steam for 7 minutes to develop a color, it was washed with water and dried, resulting in a red color with good light fastness, sublimation fastness, and wet fastness. /IJ ester cloth was obtained.The wet fastness of the obtained IJ ester dyed cloth after polyurethane processing was as shown in Table 1. Using various dyes with the structural formula below listed in? The wet fastness after dyeing the Lyester cloth and applying polyurethane processing to the obtained dyed cloth was examined, and the results are shown in Table 1.

0: Sendai Table 1 Examples 3 to 121 Various amines represented by the general formula (U) having various substituents and amines represented by the general formula (III) having various substituents
), the various disazo compounds represented by the general formula (1) having the substituents shown in Table 2 were prepared by force and pulling according to the method described in Example 1 of Example 2. produced dyes.

λmaw (acetone) value of each disazo dye obtained,
The color tone and wet fastness (alkali sweat fastness) of the dyed cloth with polyurethane were as shown in Table 2.

(e) Effects of the Invention The disazo dye of the present invention not only has high fastness after dyeing, but also has high durability when dyed fabric is treated with polyurethane or silicone to improve texture, waterproof, or prevent static electricity. The subsequent wet fastness (fastness after post-processing) is extremely high.

Therefore, the disazo 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
OOR^1 (R^1 is the same as R^1 described later), 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, a methyl group, a lower Represents an alkoxy group, lower alkoxyalkoxy group, chlorine atom, or bromine atom. R^1 is a hydrogen atom, C_1_ to_8 alkyl group (the alkyl group is C_
1_-_8 alkoxy group, cyano group, chlorine atom, acyloxy group, C_1_-_6 alkoxyalkoxy group, phenyl group, phenyloxy group, aralkyloxy group, carbimole group, alkoxycarbonyl group, phenoxyalkoxycarbonyl group, phenylC_1_-_3 alkoxy Carbonyl group, alkoxyalkoxycarbonyl group, allyloxyalkoxycarbonyl group, alkoxycarbonyloxy group, benzyloxycarbonyloxy group, succinimide group, phthalic acid imide group, cyanoalkoxy group, or halogen atom, methyl group, methoxy group or nitro It may be substituted with an aryl group substituted with a group. ), alkenyl group, aryl group, or tetrahydrofurfuryl group. R^2 is a halogenopropyl group, C_5_-_8 alkyl group, C_1_-_
It represents a 1_0 alkoxy group (however, when Y is an acylamino group, it is a C_4_ to_1_0 alkoxy group), an aralkyloxy group, an aralkyloxyalkoxy group, or a phenoxy group. ] A disazo dye represented by.