JPS6022112B2 - How to dye or print hydrophobic fibers - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a method for dyeing or printing hydrophobic fibers using a penzothiazole monoazo dye.

More specifically, the present invention relates to the following general formula (1) (wherein R
I is an alkyl group having 5-6 carbon atoms, R2 is an alkyl group having 6 or less carbon atoms, or an alkyl group having 6 or less carbon atoms substituted with a cyano group or a chlorine atom, R3 is a hydrogen atom, a lower alkyl group, or a phenyl group, YI is a hydrogen atom or a halogen atom, and Y2 is a lower alkoxy group, a halogen atom, or a nitride atom.

group, cyano group, thiocyanate group or alkylsulfonyl group. The position of YI is the 4th or *5th position. ) is a method for dyeing or printing hydrophobic fibers, which is characterized by using a monoazo dye shown in the following.

Recently, as hydrophobic fibers, especially polyester fibers, have become more fashionable, sophisticated, and have high added value, the dyeing and discharging method has been growing in dyeing processing technology.

The characteristics of this method are that the printed pattern can be expressed delicately and boldly, and combined with the vividness of the colors, it is unique and can be applied to a variety of fabrics. The dyes used in this method include dyes for ground* that can be discharged and dyes for difference colors that cannot be discharged. Existing non-removable differential dyes do not pose any major problems as they have good fastness, but with dischargeable pond dyes, the dyes either completely decompose during the discharge process and become colorless, or they decompose. Even if the dye is colored, it can be easily removed, and it is also necessary to meet various fastness requirements, so dyes are selected from existing dyes or newly developed. . For example, as a red dye, a dye having the following structural formula described in Jikko No. 36-16039 is used, but it cannot be said to be sufficient in terms of hue and fastness, and it is not possible to use a red or purple dye that can be discharged. It is desired to develop a dye with good dyeability and various fastness properties, especially wet fastness after resin processing.

The present inventors have conducted extensive studies on the development of red to purple dyes for ground dyeing that can be discharged, and have found that the dye represented by general formula (1) has excellent dischargeability, dyeability, hue, build-up property, and light fastness. , fastness of sublimation, potting, etc., washing after resin processing,
It was found that the product had extremely good fastness properties in home washing and water, etc., and was published. The dye used in the present invention has, for example, the general formula (where Y, , Y2M has the above-mentioned meaning).

) A penzothiazole compound represented by the formula (m) is diazotized by a conventional method to form a compound represented by the general formula (m) (wherein R,, R2, and R3 have the above-mentioned meanings).

) can be produced by coupling with a coupling component shown in Specific examples of the diazo component of general formula (0) include the following compounds.

2-amino-6-nitrobenzothiazole 2-amino-6-methylsulfonylbenzothiazole 2-amino-6
-Methoxybenzothiazole 2-amino/-6-ethoxybenzothiazole 2-amino-6-chlorobenzothiazole 2-amino-6-bromobenzothiazole 2-amino-6-iodobenzothiazole 2-amino-6-cyanobenzothiazole 2-amino-6-thiocia/pen Zothiazole 2-amino-4,6-dichlorobenzothiazole 2-amino-4,6-dibromobenzothiazo-nole 2-amino-4-6-nitrobenzothiazole 2-amino-4-bromo-6-nitro Benzothiazole 2-amino-5,6-dichlorobenzothiazole 2
-Ami/-5,6-dibromobenzothiazo-'Re The following are specific examples of the coupling component of the general formula (m).

3-dibentylaminoacetanilide 0 3-di(n-hexyl)aminoacetanilide 3-(N-bentyl-N-ethyl)aminoacetanilide 3
-(N-pentyl-N-8-cyanoethyl)aminoacetanilide 5 3-(N-pentyl-N-B-chloroethyl)aminoacetanilide 3-propionylaminodibentylaniline 3-propionylaminodi(n-
hexyl)aniline 0 3-formylamino-dibentylaniline 3-di(iso-bentyl)aminoacetanilide 3-(N-butyl-N-bentyl)aminoacetanilide 3-(N-propyl-N-n-hexyl)
Aminoacetanilide Specific examples of dyes of general formula (1) obtained by combining these are shown in Table 1.

Table 1 The dye represented by the general formula (1) obtained by the above method is suitable for dyeing or printing hydrophobic fibers, especially polyester fibers, and has a bright red to purple color and good general fastness to light and sublimation. It has excellent home washing and water fastness after resin processing, and what should be noted is that it has extremely excellent performance as a ground color dye for dyeing and discharging.

Further, the dye represented by the general formula (1) has extremely high molar absorbance. To explain the method of the present invention in more detail, the dye of general formula (1) is pulverized into fine particles in an aqueous medium together with a suitable dispersant to prepare a powder beam agent in the form of a paste or by spray drying.

Using this beam agent, the fibers are dyed in a mashed aqueous medium under pressure at 10 g C or higher, preferably at 110-140° C., at a relatively high temperature in the presence of a carrier such as 0-phenylphenol or trichlorobenzene. For example, dyeing is carried out in a boiling state of water, or by a so-called thermosol method in which a dye dispersion is patted onto cloth and dry heat treated at 150 to 230 q0 for 30 to 6 blocks during papermaking. Further, a solvent dyeing method is also possible in which dyeing is performed using a dye bath system mainly containing an organic solvent such as trichloroethylene or perchloroethylene as the dye bath solvent. In addition, when printing is performed, the dye dispersion is kneaded with a suitable paste, and this is printed using a steaming or thermosol method to achieve the purpose. Next, the results of a comparative test between the dye of the present invention and similar known dyes will be shown.

From Table 2, the dye of the present invention has a higher hue and color than known dyes.
It can be seen that it has excellent discharge printing properties and fastness after resin processing. Table 2 Note) (1) Dyeing method; High temperature dyeing Material to be dyed: Polyester processed fabric Dyeing concentration: 3.0% OWF Dyeing conditions: pH 5.0 (acetic acid-sodium acetate buffer system) 120°C 60 minutes Hue can be judged with the naked eye did.

(◎: Very good, 〇: Good, △: Slightly poor, ×: Poor) (2) Resin processing (finishing)・Sumista
t F-1 (Sumitomo Chemical antistatic agent) 10
Evening/Z・Sumitex Softener LK-1
(Sumitomo Chemical Fabric Softener) 10th evening/Mu・Issuing Bonds and Shibori 2
Repeat times.

．． Heat setting intermediate drying conditions: 80°C for 2 minutes Heat setting conditions: 160°C for 2 minutes (3 fastness, washing fastness: AATOC Modification 0-A water fastness JISL0846-1967A method Q) whiteness whiteness glue prescription (chloride No. Tin method) Stannous chloride
10 parts urea 3 parts Tetron p-300 3 parts Gliescin A 3 parts 12 parts Polymer Brogum NP60 60 parts Hot water
21 copies, total 100 copies White blanking process: printing → drying → steaming (130° C. for 30 minutes) → water washing → reduction cleaning → water washing → drying judgment The degree of coloring of the blank areas was determined using a gray scale for contamination.

(◎: Very good, ◯: Good, △: Slightly poor, ×: Poor) The present invention will be specifically described below with reference to Examples.

The middle part of the sentence indicates parts by weight. Example 1 Ship shown in Table-1. 1 dye powder 1. Tabe's condensate of naphthalene sulfonic acid and formaldehyde 2. Add Eyato,
Grind and disperse finely in an aqueous medium.

The dye obtained by drying this dispersion is 0. One base portion of the polyethylene terephthalate fiber is immersed in a dye bath containing the group portions and dyed under pressure at 130 to 135 qo for 60 minutes. after that,
This fiber was soaped at 90° C. and dried to obtain a polyester fiber dyed bright wine red with excellent sunlight, sublimation, washing fastness, washing after resin processing, water fastness, and beam stability. Note that the M. Dye No. 1 was obtained by diazotizing 2-amino-4,6-dichlorobenzothiazole with sodium nitrite in 85% phosphoric acid.
3-dibentylaminoacetanilide was dissolved and dispersed in ice water for coupling, and the resulting crystals were obtained by furnace separation. The melting point of this crystal was 167-1 total degrees Celsius. Moreover, the molar absorbance of this dye cake was extremely high at 6.7×l. Example 2 In Example 1, shame. No.1 dye instead of No.1 dye. Polyester fibers were dyed in the same manner except that dyes 2 to 4 were used, and were dyed a bright wine red with excellent sunlight, sublimation, washing fastness, washing after resin processing, water fastness, and dyeing stability. I got it.

Example 3 Table 1. 5 dye powder 1. Part' Sodium ligninsulfonate 2. Add part of the mixture and finely crush and disperse in the aqueous medium.

Using 0.3 parts of the dye obtained by drying this dispersion as a carrier, 1. In addition to the beam structure including the foundation shell, there are 10 polyethylene terephthalate fibers in it.
The sample is soaked and dyed at 98-100°C for 9 minutes. This fiber was then soaped at 90 oo to obtain a polyester fiber dyed in a vivid dark violet color with excellent sunlight, sublimation, wash fastness, wash after resin processing, water fastness and beam bath stability. Ta.

In the above, M. No. 5 dye instead of No. A wine red dyed product with excellent fastness was obtained in exactly the same manner except that dye No. 10 was used.

Example 4 Taiichi's shame. 13 dye powders 1. Condensate of naphthalene sulfonic acid and formaldehyde 2.
Add the base and finely crush and disperse in the aqueous medium.

The obtained dispersion paste was kneaded with a suitable glue and water, and dried by patting it on a polyester fabric.
Steam for a minute. Thereafter, this fabric was soaped at 90° C. to obtain a dyed product with a clear solid pattern excellent in sunlight, washing, washing fastness, washing after resin processing, water fastness, and beam stability. In the above, M. Lung instead of dye 13. Polyester fibers dyed in bright red were obtained in exactly the same manner except that dye No. 14 was used.

Claims (1)

[Claims] 1. General formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 is an alkyl group having 5-6 carbon atoms, R^2
is an alkyl group having 6 or less carbon atoms or a cyano group or an alkyl group having 6 or less carbon atoms substituted with a chlorine atom, R^3 is a hydrogen atom, a lower alkyl group or a phenyl group, Y^1 is a hydrogen atom or a halogen atom, Y ^2 represents a lower alkoxy group, a halogen atom, a nitro group, a cyano group, a thiocyanate group or an arsulfonyl group. The position of Y^1 is the 4th or 5th place. ) A method for dyeing or printing hydrophobic fibers, characterized by using a monoazo dye represented by: 2. The method according to claim 1, wherein in the general formula (I), R^1 and R^2 are pentyl groups and R^3 is a methyl group. 3 In general formula (I), R^1 is a pentyl group, R^
2. The method according to claim 1, wherein 2 is a cyanoethyl group and R^3 is a methyl group. 4. The method according to claim 2, which uses the following formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 5. The method according to claim 2, which uses the following formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 6. The method according to claim 3, which uses the following formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼.