JPS60119281A - Dyeing of polyester fiber - 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 a method for dyeing or printing polyester fibers using a dye mixture.

[In formula (1), R1 and RQ each independently mean a methyl group or an ethyl group. ] Monoazo dye represented by 70 to 30% by weight and general formula (n) [In formula (II), 几8 and IL4 each independently mean a methyl group or an ethyl group. ] This invention relates to a method for dyeing polyester fibers, characterized in that a dye mixture containing the monoazo dye represented by the following formula is used in a proportion of 30 to 70 parts by weight.

Traditionally, disperse dyes that give a vivid red hue often have an anthraquinone as the structural matrix, but in recent years,
Primarily for economic reasons, the demand for azo red dyes has increased, and several red azo dyes are commercially available or
An application has been filed.

Among these, the dye of formula T (1) disclosed in JP-A No. 56-76456 is a bright red dye, and has good four-light, sublimation, washing, and water fastness. Although it is a dye with excellent discharge printing properties, it has the disadvantages of high temperature sensitivity, low dyeing rate, and insufficient build-up property, which is a basic property of dyes. As a result of intensive studies to solve these problems, the inventors found that if polyester fibers are dyed or printed using a mixture of dyes represented by formulas (1) and (11), all of these problems can be solved. Find the benevolence that will be solved,
We have arrived at the present invention.

In particular, when dyeing is carried out using the dye mixture of the present invention, the formula 1 of the dye disclosed in JP-A-56-76457
) Compared to dyeing using dyes, both dip dyeing and printing have excellent dyeing rate, build-up properties, and temperature sensitivity.
Moreover, the various fastnesses are the same, and the industrial value of the present invention is extremely large.

The results of these tests conducted by the present inventors are shown in the table below.

(Bones 1 to 0) The dye composition is the proportion of dyes belonging to the above general formulas (1) and (II) expressed in weight %.

2) Dyeability is] % o, w, f, (% by weight of fiber) and 3
The visual density of the dyed fabric when dyeing was carried out at 130° C. for 60 minutes at % o, w, f, dyeing density was compared with that of the dye concentration.

3) Ratio of concentrations of build-up 1% OT w-f- and 3% o, w, f, 4) Summer ITS (high temperature steaming) 3% o, w
, f, (% by weight of printing paste) was dyed at 175° C. for 7 minutes, and the visual density of the dyed fabric was compared with dye (A) and determined.

5) IIPS (high pressure steaming) 3% o, w, p
, when stained at 130°C for 20 minutes.

From the results shown in the table, it can be seen that the dye mixture of the present invention has extremely excellent dyeing properties, especially build-up properties.

The dyes used in the present invention can be prepared by separately synthesizing individual dyes represented by formula (+) or formula (11) and mixing them at the time of use, or by simultaneously combining the coupling component and diazo component of each dye. It can be obtained by a coupling method. The coupling component can advantageously be obtained by reacting m-acetylaminoaniline (or [n-propionylaminoaniline)] with a predetermined amount of methyl monochloroacetate or ethyl monochloroacetate in the presence of a deoxidizing agent. The diazo component can also be prepared by combining 2-amino-5,6-dichlorobenzothiazole 482-amino-6,7-1 dichlorobenzothiazole separately or simultaneously using a mixture of 2-amino-5,6-dichlorobenzothiazole and glacial acetic acid-phosphoric acid-sulfuric acid. It can be obtained by dissolving or suspending it in water or a mixture of glacial acetic acid and propionic acid, and diazotizing it with nitrosyl sulfuric acid.

The blending ratio of dye (1) and dye (II) is 70% to 30%.
to 30% to 70%, and when using the dye mixture of the present invention in this range, the effect is large, and the proportion of dye (1) is 70%.
If it is 0% or more or 30% or less, build-up properties and dyeing properties will decrease.

In order to dye polyester fibers using the dye mixture of the present invention, the dye is generally dispersed with a dispersant and mixed with a dyeing aid to form a dye composition.

The preparation method for this dye composition differs depending on the dyeing and printing method, but in general, the compound of the present invention is used as a formalin condensate of naphthalene sulfonic acid, lignin sulfonic acid, sulfated creosote oil, or a sulfate ester of an ethylene oxide condensate of alkylphenol. Anionic dispersants such as oxides, block copolymers of ethylene oxide and propylene oxide, block copolymers of alkylene diamine, proplene oxide and ethylene oxide, ethylene oxide adducts of alkylphenols, ethylene oxide adducts of polystyrenated phenols , a nonionic activator such as an ethylene oxide adduct of polybenzylphenol, and a small amount of water are thoroughly wet-pulverized using a grinder such as a ball mill or a sand mill.

When printing, in addition to anionic dispersants and nonionic activators, general printing aids such as natural sizing agents, synthetic sizing agents,
Anti-reduction agents, pH adjusters, etc. are used, and in the case of padding dyeing, in addition to these agents, anti-migration agents such as sodium alginate are used.

When polyester fibers are dyed or printed using the dye of the present invention in a conventional manner, dyed products with excellent fastness to light, washing, sublimation, water, and washing after resin processing can be obtained. Furthermore, the dye of the present invention has excellent resistance dyeing and discharge properties with reducing agents or alkaline agents, and in order to create a resist pattern with the dye mixture of the present invention, for example, a dye dispersion containing the dye of the present invention can be used. Alternatively, padding or printing a color paste on a polyester cloth, and after intermediate drying, printing a paste containing an alkali (such as sodium carbonate, potassium carbonate or caustic soda) or a reducing agent, or applying an alkali or a reducing agent to the polyester cloth. After printing and intermediate drying with a glue containing
A colored paste containing the dye of the present invention is printed and steamed with Hp or 100 ml. In addition, in order to dye with a more complex pattern, the resist-dyed area is colored with another dye by adding the dye of the base color layer to a paste containing an alkali or reducing agent. is taken.

In addition, in order to create a discharge printing pattern using the dye mixture of the present invention, polyester cloth is dip-dyed or continuously dyed using the dye composition of the present invention, and a starch containing a discharge printing agent such as tin chloride is applied to the ground-dyed cloth. So-called 1-1 printing at 130°C for about 300 minutes.
P-steaming or steaming at 180℃ for about 5 minutes (
'l' Discharge by steaming. In order to dye with a more complex pattern, a method is used in which the dye of the above-mentioned insulating color layer is added to these colored pastes or discharge printing paste, and the discharge printing area is colored with another dye.

The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to this embodiment unless it exceeds the gist thereof.

In the examples, "parts" means "parts by weight."

~1 only ω2 [Example-1] 18 parts of dye of the following formula (a), 12 parts of dye of the following formula (b) Demol N (product of Kao Atlas Co., Ltd.; sodium salt of naphthalene sulfonic acid and formalin condensate) 70 parts and 100 parts water
A dye composition was obtained by atomizing and decomposing the part and spray drying it. Add 3 parts of this dye composition to 3000 parts of water and adjust the pH to 5.
100 parts of the Tetoron-treated yarn surface was immersed in water, heated to 130° C. under pressure, and dyed at the same temperature for 1 hour. When the dyed fabric was reductively washed, washed with water and dried, a red dyed fabric with excellent fastness was obtained.

Furthermore, it was determined that the dyeing rate was 94 cm based on the visible absorbance of the dyeing bath before and after dyeing.

The dye of the above formula (,) was synthesized as follows.

In 50 parts of 13% nitrosyl sulfuric acid, 64 parts of glacial acetic acid and 89 parts
% phosphoric acid and 32 parts of phosphoric acid was added dropwise at 10 to 15°C,
Cool to ℃. 2-amino-5,
Add 10.95 parts of 6-dichlorobenzothiazole little by little and stir at the same temperature for 3 hours. The diazo solution was mixed with 13 parts of 3-acetylamino-N,N-di(ethoxycarbonylmethyl)Ayurif, 1 part of sulfamic acid, and 50 parts of acetone.
7 parts of 98 Llb sulfuric acid, 500 parts of ice and water and adjust the pH of the mixture to 5 by adding sodium acetate. The mixture was stirred for 30 minutes, and then the precipitated dye was filtered out, washed with water, and dried to obtain 21 parts of the dye raw material.

Further, the dye of formula (b) above was produced in the same manner as the dye of (,) using 2-amino-6,7-dichlorobenzothiazole.

[Example-2] 30 parts of a dye mixture having a mixing ratio of the following formula (c) and the following formula (d) (60:40) and 10 parts of thymol N.

A mixture of 4 parts of a block copolymer of ethylene oxide and propylene oxide, 6 parts of glycerin, and 50 parts of water was atomized and dispersed to obtain a liquid dye composition.

Add 10 parts of this dye composition to 90 parts of a printing base paste with the following composition and stir well to prepare a colored paste.

Printing base paste water 29 parts 0/W emulsion 17 parts Sodium chlorate 0.7 parts Alcoholic acid 0.3 parts This colored paste is stamped on polyester fabric, and after drying, it is heated in a high temperature steamer (HTS, 170-180℃). ) 5-10
Steamed for a minute. Next, the printed material was thoroughly washed with warm water at 40 to 50°C, and then subjected to reduction cleaning at 80 to 85°C for 10 to 20 minutes. Next, the dyed material was thoroughly washed with hot water, dehydrated and dried to obtain a strong, bright red dyed product with extremely high density and excellent build-up properties.

() The above dye mixture was produced as follows.

5 parts of a mixture of 2-amino-5,6-dichlorobenzothiazole (60%) and 2-amino-6,7-dichlorobenzothiazole (40%) was dissolved in 800 parts of glacial acetic acid. . 400 parts of 89% phosphoric acid and 366 parts of 98% sulfuric acid
After adding 50% of the mixture, the mixture was cooled to 0°C. 269 parts of 30% nitrosyl sulfuric acid was added and reacted for 2 hours to obtain a diazotization reaction solution.

150 parts of 3-acetylamino-N,N-di(methoxycarbonylmethyl)aniline, 1500 parts of methanol, 9
It was dissolved in a mixture of 500 parts of 8% sulfuric acid, 2000 parts of water and 4000 parts of ice. After adding the diazotization reaction solution at 0°C, the pH was adjusted to 4 with caustic soda, and the precipitated crystals were separated from each other to obtain the desired product.

[Example-3] 15 parts of the dye of the formula (c), 15 parts of the dye of the formula (d), 20 parts of thymol N, 10 parts of ethylene glycol, and 4 parts of water
0 parts and atomized and dispersed, the resulting dye formulation 10
1 part to 90 parts of a printing base paste with the following composition and stir well to make a colored paste.

Printing base size water 36 parts Sodium chlorate 0.7 parts Tartaric acid 0.3 parts This color paste was stamped on polyester fabric, and after drying, it was heated in a high-pressure steamer (abbreviated as H11S, temperature 13 (1-135℃, '
y' - Pressure 3~4 Ky/cr! ) f 30
Steamed for ~40 minutes.

Next, after thoroughly washing the stamped material with warm water of 40 to 50°C, hydrosulfide l i' / t Wj property: / - da t
r/z, Score Roll 400 (ampholytic surfactant) i y
Reduction washing was carried out at 80 to 85°C for 20 minutes in a solution of 80 to 85°C, followed by sufficient hot water washing, and dehydration and drying yielded a strong bright red dyed product with extremely high concentration and excellent build-up properties. Ta.

The dyes (c) and (d) used were produced in the same manner as in Example-1.

[Example 4] 30 parts of a mixture of dyes of formula (C) and formula (d) (40:60) were dispersed and dried in the same manner as in Example 1 to obtain a dye composition. Add 3 parts of this dye composition to 3,000 parts of water.
1 part of Tetro/N ((trade name, methylnaphthalene carrier)
100 parts of Tetron thread was added, and 100°C was heated.
After dyeing for 1 hour, the dyed product was reductively knoped, then thoroughly washed with water and dried to obtain a bright red dyed product.

[Example-5] 30 parts of a mixture of dyes of the following formulas (e) and (f) (70:30) was atomized in the same manner as in Example-2 to obtain a liquid dye composition. 20 parts of this dye composition was added to 1000 parts of water to form a dispersion solution.1 A Tetron cloth was immersed in this solution, then squeezed until the weight increased by 70%, and once intermediately dried at ioOoC.
Next, it was subjected to dry heat treatment at 210° C. for 30 seconds and then reductively soaped to obtain a bright red dyed cloth with good fastness properties.

The above dye mixture was produced in the same manner as in Example-2.

patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] General formula (1) [In formula (1), R1 and R2 each independently mean a methyl group or an ethyl group. ] 70 to 30% by weight of the monoazo dye represented by the formula (11) means an ethyl group. ] A method for dyeing polyester fibers, characterized in that a dye mixture comprising a monoazo dye represented by 30 to 70% by weight is used.