JPH0619039B2 - Indoaniline dyes for polyester fibers - Google Patents

Description

TECHNICAL FIELD The present invention relates to an indoaniline dye for polyester fibers.

2. Description of the Related Art Conventionally, an indoaniline dye for hair dyeing represented by the following general formula [A] is known (West German Published Patent No. 2429959).
issue).

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention An object of the present invention is to provide an indoaniline-based dye capable of dyeing polyester fiber in a vivid blue color.

Means for Solving the Problems The present invention has the general formula [I] (Where K is Or R ¹ represents a hydrogen atom, —A—R ¹⁰ , or Represents -NH-, -NHCO-, -NHCOO-,-
_{NHSO 2 -, - NHCONH -,} - NHCSNH-,
Represents -NHCSO- or -CONH-, Is Or The stands, R ¹⁰ is an alkyl group, perfluoroalkyl group, perfluoroalkyl group, hydroxyalkyl group, alkoxyalkyl group, cyanoalkyl group, an allyl group, a cyclohexyl group, a phenyl group, a bromophenyl group, R ² represents a hydrogen atom, R ³ represents a hydrogen atom,
Alkyl group, perfluoroalkyl group, perfluoroalkylalkyl group, halogen atom, alkoxy group, or -N
HCO-R ¹¹ represents, R ¹¹ represents an alkyl group, R ⁴ represents a hydrogen atom, an alkyl group or a halogen atom, and R ³ and R ⁴ are a benzene ring or pyridine which may be substituted with an alkyl group. It may form a ring. R ⁵ and R ⁶ are a hydrogen atom, an alkyl group, an allyl group,
Hydroxyalkyl group, halogenoalkyl group, cyanoalkyl group, phenylalkyl group, alkoxyalkyl group, phenoxyalkyl group, alkoxyalkoxyalkyl group, alkylcarbonyloxyalkyl group, alkoxycarbonylalkyl group, alkoxycarbonyloxyalkyl group, phenyl group, chlorophenyl Group, or -NHSO ₂ R ¹² represents an alkyl group substituted with -NHCOR ¹² , R ¹² represents an alkyl group or a phenyl group, R ⁷ , R ⁸ and R ⁹ represent a hydrogen atom or a methyl group, and X represents a hydrogen atom. , Alkyl group, perfluoroalkyl group, alkoxy group, halogen atom or -NH
CO-R ¹³ , R ¹³ represents a hydrogen atom, an alkyl group, a perfluoroalkyl group or a phenyl group, and Y
Represents a hydrogen atom, an alkyl group, an alkoxy group, a perfluoroalkyl group or a halogen atom. ) Is the indoaniline dye for polyester fibers.

In the general formula (I) shown above, examples of the alkyl group represented by R ¹⁰ include a methyl group, ethyl group, propyl group and butyl group, and examples of the perfluoroalkyl group include a trifluoromethyl group, a perfluoroethyl group, Examples include perfluoropropyl group, examples of the perfluoroalkylalkyl group include 2,2,2-trifluoroethyl group,
Examples of the hydroxyalkyl group include a hydroxyethyl group, examples of the alkoxyalkyl group include a methoxyethyl group and ethoxyethyl group, and examples of the cyanoalkyl group include a cyanoethyl group.

Examples of the alkyl group represented by R ³ include lower alkyl groups such as methyl group, examples of the perfluoroalkyl group include trifluoromethyl group and perfluoroethyl group, and examples of the perfluoroalkylalkyl group include 2, Two
Examples thereof include 2-trifluoroethyl group, the halogen atom includes fluorine atom, chlorine atom, bromine atom or iodine atom, and the alkoxy group includes methoxy group and ethoxy group.

Examples of the alkyl group represented by R ¹¹ include a lower alkyl group such as a methyl group.

Examples of the alkyl group represented by R ⁴ include lower alkyl groups such as methyl group, and examples of the halogen atom include chlorine atom, bromine atom and the like. In addition, examples of the substituted alkyl group of the benzene ring or the pyridine ring formed by combining R ³ and R ⁴ include a lower alkyl group such as a methyl group.

Examples of the alkyl group represented by R ⁵ or R ⁶ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and an octyl group, and examples of the hydroxyalkyl group include a hydroxyethyl group and a 2-hydroxybutyl group. The halogenoalkyl group includes a chloroethyl group, the cyanoalkyl group includes a cyanoethyl group, and the phenylalkyl group includes a benzyl group.
Examples include phenylethyl group, examples of alkoxyalkyl group include methoxyethyl group and hexoxyethyl group, examples of phenoxyalkyl group include phenoxyethyl group, and examples of alkoxyalkoxyalkyl group include methoxyethoxyethyl group and butoxyethoxy group. Examples thereof include an ethyl group, examples of the alkylcarbonyloxyalkyl group include an acetylethyl group, examples of the alkoxycarbonylalkyl group include a methoxycarbonylethyl group, a pentoxycarbonylethyl group, and the like.
Examples of the alkoxycarbonyloxyalkyl group include an ethoxycarbonyloxyethyl group.

Examples of the alkyl group represented by R ¹² include a lower alkyl group such as a methyl group.

Examples of the alkyl group represented by X include a lower alkyl group such as a methyl group, examples of the perfluoroalkyl group include a trifluoromethyl group, and examples of the alkoxy group include a lower alkoxy group such as a methoxy group. Examples of the atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the alkyl group represented by R ¹³ include lower alkyl groups such as methyl group and ethyl group, and examples of the perfluoroalkyl group include trifluoromethyl group.

Examples of the alkyl group represented by Y include lower alkyl groups such as methyl group, examples of the alkoxy group include lower alkoxy groups such as methoxy group and ethoxy group, and examples of the perfluoroalkyl group include trifluoroalkyl group and the like. As a halogen atom, a fluorine atom, a chlorine atom,
Examples thereof include bromine atom and iodine atom.

The indoaniline dye represented by the general formula [I] shown above is
For example, the following general formula [II] (In the formula, R ¹ , R ² , R ³ and R ⁴ are the same as defined above.), And the following general formula [III] H ₂ NK ... [III] (wherein K is Is the same as the above definition.) And an aniline or a salt thereof represented by the formula (1) are treated with an oxidizing agent according to a known method.

Polyester fibers that can be dyed with the indoaniline dye of the present invention include polyethylene terephthalate,
Examples include polyester fibers made of polycondensation products of terephthalic acid and 1,4-bis- (hydroxymethyl) cyclohexane, and further, natural fibers such as cotton, silk and wool,
Examples include mixed-spun products and mixed-woven products of the above polyester fibers with acetate fibers such as diacetate fibers and triacetate fibers.

As a method for dyeing the polyester fibers, a dye may be dispersed in an aqueous medium using a dispersant to prepare a dyeing bath or a printing paste, and the dyeing or printing may be performed according to a known method. For example, in the case of dip dyeing, polyester fibers or a blended product thereof can be dyed with excellent fastness by applying an ordinary dyeing treatment method such as a high temperature dyeing method, a carrier dyeing method and a thermosol dyeing method.

Examples of the dispersant used in the present invention include a condensate of naphthalene sulfonic acid and formaldehyde, anionic surfactant such as higher alcohol sulfate ester, higher alkylbenzene sulfonate, and nonionic surface active agent such as polyalkylene glycol ether. Usual agents such as agents can be mentioned.

The amount of dispersant used is 0.5 to 4 with respect to the dye.
The range of weight times is included.

Further, known additives such as a leveling agent and a pH adjusting agent may be added, if necessary.

Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples.

Example Example 1 The following structural formula 3.0 g of 2-acetamido-phenol represented by 200 g of methanol was added to 5.1 g of the compound represented by
The mixture was stirred at room temperature, and then an aqueous solution prepared by dissolving 3.4 g of silver nitrate in 15 ml of water was added dropwise. Then, 15 ml of 28% ammonia water was added, and an aqueous solution prepared by dissolving 10.5 g of silver nitrate in 10 ml of water was added dropwise, and the reaction was carried out at 30 to 40 ° C. for 3 hours. After completion of the reaction, extract with chloroform, evaporate the solvent and purify the column with chloroform. 5.3 g (yield 73%) of a purified product of the indoaniline dye represented by

The maximum absorption wavelength (chloroform) of the obtained dye is 652.
was nm.

Next, 0.5 g of the obtained dye of this Example was dispersed in water 3 containing 1 g of a naphthalenesulfonic acid-formaldehyde condensate and 2 g of a higher alcohol sulfate, and 100 g of polyester fiber was immersed in the dyeing bath at 130 ° C. for 6 hours.
After dyeing for 0 minutes, soaping, washing with water and drying were carried out to obtain a blue dyed cloth. The obtained dyed cloth had good light fastness and various fastnesses.

Example 2 The following structural formula 2.9 g of 8-hydroxyquinoline represented by 150 ml of ethanol was added to 4.3 g of the compound represented by
The mixture was stirred at room temperature, and then an aqueous solution prepared by dissolving 3.4 g of silver nitrate in 15 ml of water was added dropwise. Then, 15 ml of 28% ammonia water was added, and an aqueous solution prepared by dissolving 10.5 g of silver nitrate in 10 ml of water was added dropwise, and the reaction was carried out at 30 to 40 ° C. for 3 hours. After completion of the reaction, extract with chloroform, distill off the solvent, and purify the column with chloroform. 5.1 g of a purified product of the indoaniline dye represented by

The melting point of the obtained dye was 158 to 160 ° C., and the maximum absorption wavelength (chloroform) was 630 nm.

Then, after dyeing the polyester fiber according to the method of Example 1 using 0.5 g of the above dye obtained in this Example instead of the dye used in Example 1, soaping,
After washing with water and drying, a blue dyed fabric was obtained. The obtained dyed cloth had good light fastness and various fastnesses.

Example 3 The following structural formula 5-methyl-2-acetamidophenol represented by
3.28g and the following structural formula Using 5.24 g of the sulfate of the compound represented by the following, according to the method described in Example 2, the following structural formula 5.6 g (yield 82%) of a purified product of the indoaniline dye represented by

The maximum absorption wavelength (chloroform) of the obtained dye is 637.
was nm.

Next, instead of the dye used in Example 1, the polyester fiber was dyed according to the method of Example 1 except that 0.5 g of the above dye obtained in this Example was used, and then soaping, washing with water and drying were performed. A blue dyeing was obtained. The obtained dyed cloth had good light fastness and various fastnesses.

Example 4 The following structural formula 2-methylsulfonylamino-phenol represented by
3.7g and the following structural formula Using 5.24 g of the compound represented by the following and following the method described in Example 2, 5.27 g (yield 76%) of a purified product of the indoaniline dye represented by

The obtained dye had a melting point of 135 to 137 ° C. and a maximum absorption wavelength (chloroform) of 640 nm.

Next, instead of the dye used in Example 1, the polyester fiber was dyed according to the method of Example 1 except that 0.5 g of the above dye obtained in this Example was used, and then soaping, washing with water and drying were performed. As a result, a blue dyed cloth was obtained. The obtained dyed cloth had good light fastness and various fastnesses.

Example 5 The following structural formula 5.26 g of the compound represented by 50 ml of ethanol was added to 5.24 g of the compound represented by and stirred at room temperature, and an aqueous solution of 3.4 g of silver nitrate and 15 ml of water was added dropwise at room temperature.

Then, 15 ml of 28% ammonia water was added, and an aqueous solution prepared by dissolving 10.5 g of silver nitrate in 10 ml of water was added dropwise.
The reaction was carried out at 0 ° C for 2 hours. After completion of the reaction, extract with chloroform, evaporate the solvent, and perform column purification with chloroform.
The following structural formula 5.16 g of a purified product of the indoaniline dye represented by

The obtained dye had a melting point of 185 to 187 ° C. and a maximum absorption wavelength (chloroform) of 689 nm.

Next, instead of the dye used in Example 1, the polyester fiber was dyed according to the method of Example 1 except that 0.5 g of the above dye obtained in this Example was used, and then soaping, washing with water and drying were performed. As a result, a blue dyed cloth was obtained. The obtained dyed cloth had good light fastness and various fastnesses.

Example 6 The following structural formula 3.0 g of acetamide phenol represented by Using 4.3 g of the compound represented by the following formula and following the method described in Example 2, 5.2 g (yield 80%) of a purified product of the indoaniline dye represented by

The melting point of the obtained dye was 128 to 130 ° C., and the maximum absorption wavelength (chloroform) was 656 nm.

Then, Example 1 is repeated except that 0.5 g of the above dye obtained in this Example is used instead of the dye used in Example 1.
After dyeing the polyester fiber according to the method of 1., soaping, washing with water and drying were carried out to obtain a blue dyed cloth. The obtained dyed cloth had good light fastness and various fastnesses.

Example 7 Polyester fibers were dyed with the dyes shown in Table 1 below in the same manner as in Example 1 to obtain a dyed product having the color tone shown in the table.

Effect The indoaniline-based dye of the present invention can dye polyester fibers in a vivid blue color, and the resulting dyed cloth has excellent light fastness.

Claims (1)

[Claims] 1. A general formula [I] (Where K is Or R ¹ represents a hydrogen atom, —A—R ¹⁰ , or Represents -NH-, -NHCO-, -NHCOO-,-
_{NHSO 2 -, - NHCONH -,} - NHCSNH-,
Represents -NHCSO- or -CONH-, Is Or The stands, R ¹⁰ is an alkyl group, perfluoroalkyl group, perfluoroalkyl group, hydroxyalkyl group, alkoxyalkyl group, cyanoalkyl group, an allyl group, a cyclohexyl group, a phenyl group, a bromophenyl group, R ² represents a hydrogen atom, R ³ represents a hydrogen atom,
Alkyl group, perfluoroalkyl group, perfluoroalkylalkyl group, halogen atom, alkoxy group, or -N
HCO-R ¹¹ , R ¹¹ represents an alkyl group, R ⁴ represents a hydrogen atom, an alkyl group or a halogen atom, and R ³ and R ⁴ are bonded to each other and are optionally substituted with an alkyl group. It may form a ring or a pyridine ring. R ⁵ and R ⁶ are a hydrogen atom, an alkyl group, an allyl group, a hydroxyalkyl group, a halogenoalkyl group,
Cyanoalkyl group, phenylalkyl group, alkoxyalkyl group, phenoxyalkyl group, alkoxyalkoxyalkyl group, alkylcarbonyloxyalkyl group,
Alkoxycarbonylalkyl group, alkoxycarbonyloxyalkyl group, phenyl group, chlorophenyl group,
Or -NHSO ₂ R ¹² represents an alkyl group substituted with -NHCOR ¹² , R ¹² represents an alkyl group or a phenyl group, R ⁷ , R ⁸ and R ⁹ represent a hydrogen atom or a methyl group, and X represents a hydrogen atom. , Alkyl group, perfluoroalkyl group, alkoxy group, halogen atom or -NH
CO-R ¹³ , R ¹³ represents a hydrogen atom, an alkyl group, a perfluoroalkyl group or a phenyl group, and Y
Represents a hydrogen atom, an alkyl group, an alkoxy group, a perfluoroalkyl group or a halogen atom. ) An indoaniline-based dye for polyester fibers represented by.