JPS58104953A - Water-insoluble monoazo compound and dyeing of hydrophobic fiber - Google Patents

Abstract

NEW MATERIAL:The compound of formulaI[X is H, halogen or cyano; Y is H, lower alkyl or lower alkoxy (lower alkoxy); R is H, lower alkyl or phenyl]. EXAMPLE:The compound of formula II. USE:A dye capable of dyeing a hydrophobic fiber, especially polyester fiber in fast violet-ultramarine-greenish blue color. It has excellent degree of exhaustion, decomposition resistance and pH sensitivity, and high fastness to sublimation, water, washing, light and rubbing. PROCESS:The objective compound can be prepared by diazotizing the diazo component of formula III (e.g. 2,4-dinitroaniline, etc.) and coupling with the coupling component of formula IV. The coupling component of formula IV can be obtained by alkylating the amine compound of formula V (e.g. 3-acetylaminoaniline) with 2-phenoxy-1-halogenoethane, etc. in the presence of an acid acceptor such as sodium carbonate.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel water-insoluble monoazo compound and a method for dyeing hydrophobic fibers using the same. More particularly, the present invention relates to a method for dyeing hydrophobic fibers, particularly polyester fibers, in a strong purple to navy blue to greenish-blue color using a new water-insoluble monoazo compound and dye. be.

In recent years, in the dyeing industry, there has been an extremely pronounced trend toward high added value as well as resource and energy conservation, particularly in the field of dyeing and processing hydrophobic fibers such as polyester fibers. For this reason, there is a demand for dyes used for dyeing that are easy to dye, have a good dyeing rate, and are also excellent in fastness.

In particular, when dyeing from purple to dark blue to greenish blue, there are many problems such as deep dyeing and poor dyeing properties and poor fastness.

Conventionally, introducing polar groups or increasing the molecular weight in order to improve fastness caused problems such as decreased dyeability and dye bath stability. However, when the number of polar groups is reduced, there is a problem that the fastness to sublimation etc. decreases. As a result of intensive study on these problems, the present inventors have found that the above-mentioned general formula CI] We have discovered that the above problems can be solved at once by using an undescribed novel monoazo compound, and have solved the present invention.
That is, the present invention relates to the general formula (I) No2
R represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkoxy group, and R represents a hydrogen atom, a lower alkyl group, or a phenyl group. ] This is a method for dyeing hydrophobic fibers that specifically uses the water-insoluble monoazo compound shown below and one or a mixture of two or more thereof.

The term "lower" as used in the present invention refers to the number of carbon atoms/~. In the general formula (R), the halogen atom represented by Fix can be a chlorine atom, a bromine atom, or an iodine atom.Y
Examples of lower alkyl groups represented by the above include methyl, ethyl, propyl, and butyl groups; examples of lower alkoxy groups include methoxy, ethoxy, propoxy, and butoxy groups, and lower alkoxy and lower alkoxy groups include methoxy. An ethoxy group or an ethoxyethoxy group (□ is a preferable Y group is a methoxy group, an ethoxy group, or a methoxyethoxy group.The lower alkyl group represented by R is a methyl group, an ethyl group, a propyl group, or a butyl group. are mentioned, but R is preferably a methyl group or an ethyl group.

The monoazo compound represented by the present invention a-general formula Xia] can be prepared by diazotizing the diazo component represented by the general formula (11) by a known method to obtain the monoazo compound represented by the general formula (II) [wherein Y and R have the above-mentioned meanings. It can be obtained by a coupling reaction with a coupling component represented by the general formula (l[1], the general formula (N) [wherein, YSR is the above-mentioned coupling component]. An amine compound represented by O) is converted into -17-enoxy- in the presence of a deoxidizing agent such as sodium carbonate or potassium carbonate.
/-halogenoethane or by alkylation with cophenoxyethyl ester of P-toluenesulfonic acid.

As a diazo component represented by the general formula (Il),
Gooji nitroaniline, cochrololi.

6-sinitroaniline, cobromo f, 4-dinitroaniline, coyododa, 6-sinitroaniline, -
Examples include monocyano-Q, A-dinitroaniline, and the like.

As the amine compound represented by the general formula (IV), 3-
7 Cetyl aminoaniline, 3-propionylaminoaniline, 3-benzoylaminoaniline, 3-butyrylaminoaniline, 3-formylaminoaniline, -1methoxyS-acetylaminoaniline, 2-ethoxy-5
-7cetylaminoaniline, comethoxyethoxy-yo-acetylaminoaniline, -ethoxy! -Propionylaminoaniline, Coethoxy! Examples include -benzoylaminoaniline, -methoxyj-benzoylaminoaniline, -methoxy-j-butylinyline, -1methyl-j-acetylaminoaniline, -1ethyl-3-propionylaminoaniline, and the like.

The monoazo compound of the present invention is specifically produced as follows: ◇ The diazo component represented by the general formula [Il] is mixed with a mineral acid such as sulfuric acid or hydrochloric acid or with acetic acid or propionic acid. It is dissolved or dispersed in an organic acid and diazotized using nitrosyl sulfuric acid at SO to 2°C.

On the other hand, the coupling component represented by general formula (III) is dissolved in a mineral acid such as agglomerate, an organic acid such as acetic acid, propionate, etc., or an organic solvent such as methanol or ethanol, and the The diazo solution is added when cold, preferably below IO"C, and coupled. After the reaction is complete, the precipitated product is separated, washed with water, and dried to form the general formula (
A monoazo compound represented by [I] is obtained.Also, a compound in which X is a cyano group can be obtained by using the following formula: The compound represented by the following formula can be obtained by substituting the bromine atom with a cyano group using cupric cyanide or the like in a polar solvent such as DM1P.

In the present invention, hydrophobic fibers include polyester fibers, polyamide fibers, polyolefin fibers, cellulose ester fibers, and blends of these fibers. The compounds of the invention are particularly suitable for polyester*
□When dyeing hydrophobic fibers using the monoazo compound of the present invention, which exhibits excellent dyeing properties for miscellaneous materials and blended products thereof, first, one or more monoazo compounds represented by the general formula The dye is pulverized into fine particles in an aqueous medium with a suitable dispersant and dispersed.The dispersed dye can be used as it is in liquid form or in powder form by spray drying. For dyeing, a dye bath is prepared by dispersing the differentiated dye in an aqueous medium by a method known per se, and the hydrophobic fibers are immersed in the dye bath under pressure at lθ5°C or higher, preferably 7)θ~/4Iθ°C. dyeing or dyeing in the presence of a carrier such as O-phenylphenol or trichlorobenzene at a relatively high temperature, e.g. at the boiling state of water, or by padding the fabric with a dye dispersion, ljσ~23θ℃
So 3θ~? Dyeing is done by the so-called thermosol dyeing method, which involves dry heat treatment for ρ seconds, or in the case of textile printing, the dye dispersion is kneaded with a suitable sizing agent, the fins are padded onto the cloth, and then steamed or thermosol dyed. It can be treated and dyed. Additionally, a solvent dyeing method 4 using an organic solvent such as trichlorethylene or perchloroethylene as a dyeing medium is possible.

The monoazo compound of the present invention is excellent in various dyeing properties, especially dyeing property, decomposition resistance, 11111 sensitivity, and has #1 color fastness such as sublimation fastness, water fastness, washing fastness, light fastness, and massaging fastness.
It showed good performance at all fastness levels.

In the following, features of the present invention will be described in relation to the prior art. As a dye similar to the dye used in the present invention, the following moat dye is described in the Special Publication USS Wata/Q Bulletin.

Known dyeing stitch, special public Shoda 7-+? The following dyes are described in the /A publication.

Compared to these dyes, the dye of the present invention exhibits superior performance in all aspects such as dyeing properties and fastness.

The results of comparative examples are shown below. (t4/Table) The present invention will be described in detail below with reference to Examples, but the present invention is not limited to these Examples. In the examples, parts and parts represent parts by weight and % by weight unless otherwise specified.

Example/11 Methoxy J-7 lt part of cetyl aminoaniline was heated and melted, 09470.6 parts of sodium carbonate was added, and then 70
2-phenoxy-/-promonitor at 0-770°C29.
A portion was added dropwise and reacted at the same temperature for 3 hours to obtain a portion of -1methoxy-j-,acetylamino-N,N-bis(-1phenoxyethyl)anilingue.

This was dissolved in 700 parts of methanol to obtain a coupling component. On the other hand, −1 bromoq.

6-dinitroaniline, u, s=? , diazotized with nitrosyl sulfuric acid at t3θ~qθ°C, and diazotized with 500 parts of ice water.
The mixture was added to the coupling component while cooling to below 0.degree. C., and a coupling reaction was carried out. The precipitated crystals were separated, washed with water, and dried to obtain 6.21 parts of the dye represented by formula (1). Yield θchiλ[(in IMF) S? 6 Sono NO2 old door 3 Example koExample/The formula obtained in Example/(Ha dye/part is naphthalene-θ
- Atomize and disperse with 1 part of formalin condensate of sulfonic acid and 1 part of lignin sulfonic acid, and uniformly disperse this and 3 parts of high alcohol sulfuric acid ester in R part of ink to prepare a dye bath. Tetron spun yarn (polyester fiber, Toshisha product)/θθ section was immersed in the dye bath, 73
After 6-part dyeing at 0°C, the dyed product was treated with a treatment solution consisting of 3 parts caustic soda, 3 parts hydrosulfide, 3 parts betaine-type amphoteric surfactant, and xr parts water at ts"c/
The original cleaning process was performed for θ minutes. Thereafter, it was washed with water and dried to obtain a dark blue dyed product with high density and excellent fastness.

Example 3 5 parts of 3-acetylamino sweetfish 9 fufu were heated and melted, and potassium carbonate/3. + part, /10~//3'C
Then, 7 parts of P-) luenesulfonic acid-17-enoxyethyl ester 7θ was added, and the reaction was briefly carried out for 3 hours at the same temperature to form 3-
7cetylamino-N,N-bis(cophenoxyethyl)aniline J part was obtained. This was dissolved in 700 parts of methanol to obtain a force/pull component.

On the other hand, -1bromo4(,A-dinitroanilinep1.
2 parts were diazotized in the same manner as in Example 1, and this was subjected to a coupling reaction with the coupling component to obtain 6 parts of the dye of formula Q). Yield for diazo volume 9 kots λ (in DMF) 363 nm ax r Example II using dye/part of formula (P2)! Dye I was prepared and dyed in the same manner as in Example A, and a purple dyed product with high density and excellent fastness was obtained.

t41. The following dyes were prepared in the same manner as in Example 1 and dyed in the same manner as in Example 1, and the results shown in Table 2 were obtained.

No2NHCOR Table - Example/No2N'HOOcH3 The dye of the above formula (3) was prepared in the same manner as in Example/,
7 parts of this was pulverized and dispersed with 70.5 parts of formalin condensate of naphthalene-R-sulfonic acid and 70.5 parts of lignin sulfonic acid, and the crushed dye composition was added to 95 parts of printing light having the following composition. , Mix well and evaluate the color paste.

Printing paste Sodium chlorate 0.6s Liquor stone acid 0.1
A total of 700 parts of 1M4 color paste is printed on polyester processed fabric, and after drying,
High pressure steamer (temperature/3θ~735℃, gauge pressure 3~
9. Steam for 30 minutes at a high temperature (Kv/d). After this, it was washed with water and subjected to reduction cleaning treatment in the same manner as in Example-.
After washing with water and drying, a dark blue dyed product with high density and fastness was obtained.0 Example/! 70 parts of the dye (formula) was dissolved in 0 parts of DMF/θ, and 3. ? The reaction was carried out at room temperature for S hours, filtered to remove inorganic salts, diluted with methanol, and the crystals
Separately, it was washed with water to obtain 3.1 parts of a dye of the formula ←).

A green-blue dyed product with high density and excellent fastness was obtained.

Example/6 0.5 part of the dye of the formula obtained in Example/ (parts of the dye θ, j and the formula Q obtained in Example 3) was mixed with part/part of a formalin condensate of naphthalene-β-sulfonic acid. A dye bath is prepared by atomizing and dispersing the lignin sulfone and 3 parts of sulfuric acid ester together with 3 parts of higher alcohol sulfur ester and uniformly dispersing it in a water reservoir. After immersing 700 parts of Tetoron Spun type (polyester fiber, Toshisha product) in this dye bath and dyeing in 6 parts at 730°C, the dyed product was mixed with 3 parts of caustic soda, 3 parts of hydrosulfide, and a betaine type amphoteric interface. The mackerel was photowashed for 10 minutes using a treatment solution consisting of 3 parts of an activator and 3 parts of water gloss at ffj'c. After that, wash with water, dry and use IIFI.
A blue dyed product with high L and excellent fastness was obtained.

Claims (1)

[Claims] (1) General formula (1) [wherein, X is a hydrogen atom, a halogen atom, or a cyano group,!
represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkoxy-lower alkoxy group, and R represents a hydrogen atom, a lower alkyl group, or a phenyl group. ) Water-insoluble monoazo compound represented by 0 t2) General formula [
1] [In the formula, X is a hydrogen atom, a halogen atom, or a cyano group, Y
represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a lower alkoxy group, a hydrogen atom, a lower alkyl group, or a phenyl group. ] A method for dyeing hydrophobic fibers, characterized by using one or a mixture of two or more of the water-insoluble monoazo compounds shown below.