JPH0527662B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD OF THE INVENTION The present invention relates to monoazo dyes.
Specifically, the present invention relates to a monoazo dye having excellent wet fastness after post-processing. Prior Art Currently, dyed polyester cloth is then subjected to various post-processing processes such as water repellent processing, processing to improve texture (texture processing), antistatic processing, sanitary processing, etc.
Efforts are being made to add high value. Since the above-mentioned post-processing is carried out at a high temperature, there arises a problem that the dye bleeds and various fastnesses, especially wet fastness, are reduced.Therefore, a monoazo dye having good fastness after post-processing is desired. Conventionally, as a monoazo dye, the following general formula [A] (In the formula, R ³ represents a lower alkyl group, a lower alkoxyalkyl group, an allyl group, an aryl group, an aralkyl group that may have a substituent, a furfuryl group, a tetrahydrofurfuryl group, or a cyclohexyl group) Dyes for synthetic fibers (Unexamined Japanese Patent Publication 1973-
69381), and the following general formula [B] (In the formula, R ⁵ represents a phenoxymethyl group, a phenoxyethyl group, a benzyl group, or a tetrahydrofurfuryl group.) Monoazo dyes for polyester fibers are known (Japanese Patent Application Laid-Open No. 179268-1988).
Publication No.). However, when dyeing is carried out using the monoazo dyes represented by the above general formulas [A] and [B], and the resulting dyed fabric is subjected to post-processing, such as silicone processing, which is a type of water-repellent finishing, There were problems with wet fastness such as washing fastness, alkali sweat fastness, and water fastness after post-processing. Problems to be Solved by the Invention The present invention aims at dyeing synthetic fibers, particularly polyester fibers or fabrics produced therefrom, orange or blue, and improving the washing fastness of the dyed fabrics after post-processing. The object of the present invention is to provide a monoazo dye having excellent wet fastness such as alkali sweat fastness and water fastness. Means for Solving the Problems The present invention is based on the general formula [) (wherein D is a substituted or unsubstituted phenyl group,
represents a benzothiazolyl group, thiadiazolyl group, thienyl group or pyridyl group, X is a chlorine atom,
represents a methyl group, an alkoxy group or an alkoxyalkyl group, Y represents a hydrogen atom, a chlorine atom, a methyl group, a methoxy group or an acylamino group,
R represents a _C6 - _C13 alkyl group, a _C6 - _C13 alkoxyethyl group, a _C6 - _C13 alkoxyethoxyethyl group, phenylpropyl, phenethyl group or benzyloxyethyl group, and n represents 1 to 2. ) is the monoazo dye shown. In the monoazo dye of the present invention represented by the general formula [], the substituted or unsubstituted phenyl group, benzothiazolyl group, thiadiazolyl group, thienyl group or pyridyl group represented by D includes:
Phenyl group; fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, trifluoromethyl group, methoxy group, ethoxy group, phenylazo group, cyano group, nitro group, methylsulfonyl group, ethylsulfonyl group, allylsulfonyl group, Lower alkoxycarbonyl group, lower alkoxyethoxycarbonyl group, allyloxyelcarbonyl group, mono-lower alkylaminocarbonyl group, di-lower alkylaminocarbonyl group, diallylaminocarbonyl group, monoallylaminocarbonyl group, dimethylaminosulfonyl group, diethylaminosulfonyl group , a phenyl group substituted with a monomethylaminosulfonyl group, a monoethylaminosulfonyl group, an acetyl group, a phenyl group, etc.; a benzothiazolyl group; a methyl group, a chlorine atom, a bromine atom, a nitro group,
Lower alkoxycarbonyl group, methoxycarbonyl group, ethoxycarbonyl group, trifluoromethyl group, methylsulfonyl group, formyl group, β, β
- benzothiazolyl group substituted with dicyanovinyl group, β-cyano-β-alkoxycarbonylvinyl group, etc.; thiadiazolyl group; lower alkyl group,
Substituted with phenyl group, benzyl group, phenethyl group, cycloalkyl group, lower alkylthio group, lower alkylsulfinyl group, lower alkylsulfonyl group, cyano group, chlorine atom, arylthio group, arylsulfinyl group, arylsulfonyl group, etc. thiadiazolyl group; pyridyl group; pyridyl group substituted with a chlorine atom, bromine atom, nitro group, methyl group, methylsulfonyl group, cyano group, etc.; examples of the alkoxy group represented by X include methoxy group, ethoxy group; Examples of the alkoxyalkyl group include methoxyethyl group and ethoxyethyl group, and examples of the acylamino group represented by Y include acetylamino group, chloroacetyl group, benzoylamino group, methylsulfonylamino group, and chloropropionylamino group. group, ethoxycarbonylamino group, ethylaminocarbonylamino group, etc., and C ₆ represented by R
~ _C13 alkyl group, _C6 ~ _C13 alkoxy group, C6 _~
The C ₁₃ alkoxyethoxyethyl group may be linear or branched, preferably C ₇ -C ₁₀
Included are alkyl groups and _C6 - _C10 alkoxyethyl groups. The monoazo dye of the present invention represented by the above general formula [] is obtained by diazotizing an amine represented by the following formula [] D-NH ₂ ... [] (wherein D is the same as defined above), and then producing the monoazo dye represented by the following formula [] ] (In the formula, X, Y, R and n are the same as defined above)
It can be produced by coupling it 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 terephthalic acid and 1,4-bis-(hydroxymethyl)cyclohexane, 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 monoazo dye of the present invention, since the dye is insoluble or poorly soluble in water, a condensate of naphthalene sulfonic acid and formaltehyde, a higher alcohol, etc. are used as a dispersant, using a conventional method. Dyeing or printing may be carried out by preparing a dyeing bath or printing paste in which sulfuric acid 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. Furthermore, the above dye of the present invention may be used in combination with dyes of the same type or dyes of other types, and among these, good results such as improved dyeing properties can be obtained by combining the dyes represented by the general formula [] with each other. There may be cases where EXAMPLES 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 Structural formula 0.5g of the dye shown in naphthalenesulfonic acid
A dyeing bath was prepared by dispersing it in water 3 containing 1 g of formaldehyde condensate and 2 g of higher alcohol sulfate. Polyester fibers are dyed in this dye bath.
After immersing 100 g of the dye and dyeing it at 130°C for 60 minutes, soaping, washing with water and drying, a bright yellowish-red dyed fabric was obtained. The obtained dyed fabric was subjected to silicone processing according to the method (a) below, and then tested for washing fastness, alkali sweat fastness and water fastness according to the methods (b), (c) and (d) below. As a result of the fastness measurement, it showed excellent properties as shown in Table 1 below. In addition, the light fastness, sublimation fastness, and water fastness of the dyed fabric before silicone processing, as well as the temperature stability and PH stability during dyeing of the above dye, were good. (a) Silicone processing method Poron M-R (silicon, manufactured by Shin-Etsu Silicon Co., Ltd., trade name) 40g/Catalyst RZ-3
(Catalyst, manufactured by Shin-Etsu Silicon Co., Ltd., product name) 40
After immersing the sample in a solution of
It was dried at 160°C for 2 minutes. (b) Washing fastness A multi-fiber is attached to a dyed cloth that has been siliconized according to the method described in (a) above,
A washing test was carried out in accordance with AATCC washing method A, and the contamination of the nylon fibers of the multi-fiber was judged on a gray scale. (c) Alkali sweat fastness Tested on a dyed cloth treated with silicon according to the method described in (a) above, according to the JISL-0848A method, except that the attached cloth was a nylon cloth and a silk cloth. The degree of contamination of silk cloth was determined on a gray scale. (d) Water fastness A dyed cloth treated with silicone according to the method described in (a) above was tested in accordance with the JISL-0846A method, except that silk cloth was attached instead of nylon cloth. The degree of contamination of the cloth was determined on a gray scale. The dye used in this example was produced by the following method. 4.4 g of 2-amino-5,6-dichlorobenzothiazole in 40 ml of a 1:1 mixture of phosphoric acid and acetic acid,
Diazotization was carried out using 42% nitrosyl sulfuric acid at 0° C. for 1 hour. 5.8 g of N-2-ethylhexyloxycarbonylethyl-o-toluidine was dissolved in 300 ml of 5% dilute sulfuric acid at 0°C, and the above diazo solution was added dropwise. After stirring at 0 to 5°C for 3 hours, the precipitated crystals were filtered and washed with water. , obtained by drying (yield 92%). The maximum absorption wavelength λmax (acetone) of the obtained dye was 521 nm. Example 2 0.5g of the dye shown in naphthalenesulfonic acid
It was mixed with 0.5 g of formaldehyde condensate and pulverized in a paint shaker to obtain a finely divided dye.
Next, the resulting finely divided dye and a base paste having the composition shown below were thoroughly mixed to obtain a colored paste. Composition of base glue Carboxymethylcellulose based glue 30.0g Tartaric acid 0.2g Aromatic carrier (Sunfloren SN, manufactured by NICCA Chemical Industry Co., Ltd., trade name) 0.3g Water 68.5g Total 99.0g The obtained colored glue was applied to polyester fibers. stamped on
After performing intermediate drying at 100°C, the cloth was kept in superheated steam at 170°C for 7 minutes to develop color, and then soaped, washed with water, and dried to obtain a bluish-red dyed fabric. Next, according to methods (a), (b), (c), and (d) of Example 1, the washing fastness, alkali sweat fastness, and water fastness of the obtained dyed fabric after silicon processing were evaluated. The results of the measurements showed excellent properties as shown in Table 1 below. In addition, the dyed fabric before silicone processing was excellent in light fastness, sublimation fastness, and wet fastness. The dye used in this example was produced according to the method described in Example 1. The maximum absorption wavelength λmax (acetone) of the obtained dye was 543 nm. Comparative Examples 1 and 2 After dyeing polyester fibers according to the method of Example 1 using the dyes listed in Table 1 below, the dyes listed in (A), (B), (C), and (D) above were dyed. Washing fastness, alkali sweat fastness and water fastness after silicone processing were measured according to the method described in Table 1, and the results are shown in Table 1.

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[Table] Example 3 According to the method described in Example 1, polyester cloth was dyed using the dyes shown in Tables 2 and 3 below to obtain dyed cloth with the colors shown in the same table. Next, according to methods (a), (b), (c) and (d) of Example 1, the washing fastness, alkali sweat fastness and water fastness of the obtained dyed fabric after silicone processing were determined. All the measurements were good.

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[Table] Effects As shown in the examples above, the dyed fabric obtained by the above-mentioned dip dyeing or printing using the dye of the present invention has excellent dyeing properties such as dyeability, pill-up property, and temperature dependence. The resulting dyed fabric was subjected to silicone processing and its wet fastness, especially in deep colors, was measured and found to be excellent.

Claims (1)

[Claims] 1. General formula [] (wherein D is a substituted or unsubstituted phenyl group,
represents a benzothiazolyl group, thiadiazolyl group, thienyl group or pyridyl group, X is a chlorine atom,
Represents a methyl group, an alkoxy group, or an alkoxyalkyl group, Y represents a hydrogen atom, a chlorine atom, a methyl group, a methoxy group, or an acylamino group, and R represents a C ₆ to C ₁₃ alkyl group, a C ₆ to C ₁₃ alkoxyethyl group , _C6 - _C13 alkoxyethoxyethyl group,
A monoazo dye represented by a phenylpropyl group, a phenethyl group, or a benzyloxyethyl group, and n represents 1 to 2.