JPS6114178B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for coloring organic polymer materials. Specifically, the present invention is characterized by coloring molded products such as fibers, thin films, plates, etc. made of organic polymeric materials, particularly synthetic polymeric substances, in vivid and robust yellow to red tones. However, for this purpose, according to the present invention, the above-mentioned organic polymeric material has the following general formula: (In the formula, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, cycloalkyl group, aralkyl group, aryl group, hydroxy group, acyloxy group, alkoxy group, amino group, acylamino group, alkylamino group, or arylamino group) and R ² is a hydrogen atom, an alkyl group, an alkoxy group, a nitro group,
Indicates a halogen atom, acylamino group or alkylamino group. ) This is achieved by coloring with a compound represented by: To explain the present invention in more detail, the general formula []
The compound represented by is a novel heterocyclic dye,
In the formula, R ¹ is, for example, a hydrogen atom; an alkyl group such as a methyl group, ethyl group, propyl group, butyl group, or octyl group; a hydroxy group, an alkoxy group, an alkoxyalkoxy group, an alkoxycarbonyl group, an acyloxy group, or a cyano group. a substituted alkyl group having a substituent such as a group, an amino group, an alkylamino group, a halogen atom, a carboxy group, or a morpholino group; a cycloalkyl group such as a cyclohexyl group; an aralkyl group such as a benzyl group or a β-phenylethyl group; Phenyl group, chlorophenyl group, bromophenyl group, alkoxyphenyl group, nitrophenyl group, tolyl group, xylyl group,
Aryl group such as N-alkylaminophenyl group; Hydroxy group; Acyloxy group such as acetoxy group, benzoyloxy group; Methoxy group,
Alkoxy group such as ethoxy group; Amino group; Acylamino group such as acetylamino group, benzoylamino group; Alkylamino group such as methylamino group, ethylamino group, dimethylamino group, diethylamino group; Anilino group, toluidino group Examples include arylamino groups such as. In addition, the substituents represented by ^R2 include a hydrogen atom; an alkyl group such as a methyl group, a propyl group, and a butyl group; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group; a nitro group; atoms, halogen atoms such as bromine atoms;
Acylamino groups such as acetylamino and benzoylamino groups; alkylamino groups such as methylamino, ethylamino, propylamino, butylamino, dimethylamino, diethylamino, dipropylamino and dibutylamino groups Examples include. The compound represented by the above general formula [] used in the present invention is, for example, the general formula (In the formula, R ¹ has the same meaning as in the above general formula []) A compound represented by the general formula (In the formula, R ² has the same meaning as in the general formula []). Examples of organic polymer materials that can be applied in the present invention include polyester-based, polyamide-based, polyurethane-based, polyacrylonitrile-based, polyolefin-based, polyvinyl chloride-based, polystyrene-based,
Examples include fibers, thin films, plates, and other molded products made of synthetic polymer materials such as polyacrylates.
Fibers made of semi-synthetic polymeric substances such as cellulose acetate-based fibers, and other molded products may be used, as well as blends of semi-synthetic or synthetic fibers such as polyester-based fibers, polyamide-based fibers, and cellulose acetate-based fibers; Alternatively, it may be a molded product made of various blended products such as a blended product with natural fibers such as cellulose and wool, or a copolymer such as ABS. In order to color the organic polymeric material according to the method of the present invention, when applying it to fibers, the compound represented by the general formula [] used in the present invention must be insoluble or poorly soluble in water. Since it is a solution, it is sufficient to prepare a dyeing bath or printing paste in which it is dispersed in an aqueous medium using a dispersing agent in a conventional manner, and perform dyeing or printing. For example, in the case of dyeing, ordinary dyeing method,
By directly applying a disperse dye dyeing method such as a high temperature dyeing method, a carrier dyeing method, a thermosol dyeing method, etc., semi-synthetic or synthetic fibers or their blends can be colored with excellent various fastnesses.
In addition, the compound represented by the general formula [] is
It can be applied to the so-called stock solution coloring method, in which it is added during polymerization or spinning during the manufacturing process of synthetic fibers such as polyester fibers. When coloring synthetic resin, use the general formula shown above []
By blending the required amount of the compound represented by into a synthetic resin, heating, kneading, and applying ordinary molding methods such as compression molding, injection molding, calendar molding, and extrusion molding, films, sheets, and pipes can be produced. Other molded products can be colored robustly. Furthermore, a molded article with a strong color can also be obtained by a cast molding method in which a compound represented by the general formula [] shown above is blended with a liquid monomer or prepolymer and polymerized and cured. Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples unless the gist of the invention is exceeded. Example 1 The following structural formula A dyeing bath was prepared by dispersing 0.5 g of the heterocyclic compound represented by 3 in water 3 containing 1 g of a condensate of naphthalene sulfonic acid and formaldehyde and 2 g of higher alcohol sulfate. 100g of polyester fibers were immersed in this dyeing bath, dyed at 130°C for 60 minutes, then soaked, washed with water, and dried to obtain polyester fibers dyed bright yellow with good light fastness and sublimation fastness. . The heterocyclic compound used in this example was produced as follows. 4,5-dichloronaphthalic acid methylimide 36g
and 200 g of N-methylpyrrolidone with 30 g of 3-hydroxyindazole and 20 g of potassium carbonate.
After cooling, the precipitated crystals were filtered and washed with methanol and then water to obtain 25 g of orange crystals with a melting point of 330°C or higher.

[Table] Example 2 The following structural formula 0.5 g of a heterocyclic compound represented by
A dye bath was prepared by adding 15 g. 100g of polyester fibers were immersed in this dyeing bath and dyed at 100°C for 90 minutes, followed by soaping, washing with water, and drying to obtain polyester fibers dyed bright yellow with good light fastness and sublimation fastness. . The heterocyclic compound used in this example was produced as follows. 28 g of 4,5-dichloronaphthalic acid γ-methoxypropylimide was added to 3-hydroxyindazole.
17 g and potassium carbonate in 200 ml of N-methylpyrrolidone for 1 hour at 130°C. After cooling, the precipitated crystals were filtered out and washed with methanol and then water to give 15 g of orange crystals with a melting point of 220° to 222°C.
I got it.

[Table] Example 3 Polyester fibers were dyed using the heterocyclic compounds shown in the table below to obtain dyed products having the colors shown in the table. The compound used in this example was manufactured by the same method as described in Example 1.

【table】

【table】

[Table] Example 4 0.5g of the heterocyclic compound used in Example 2 was added to 1g of naphthalenesulfonic acid formaldehyde condensate.
and higher alkylbenzenesulfonate sodium 1
A dyeing bath was prepared by dispersing polyamide fibers in water 3 containing
After dyeing for 90 minutes, polyamide fibers dyed bright yellow were obtained by soaping, washing with water, and drying. Example 5 0.2 g of the heterocyclic compound used in Example 1 was blended with 1 kg of polystyrene resin, melted and kneaded at a heating cylinder temperature of 200 to 240°C, and injection molded using a conventional method to form a solid yellow product with a thickness of 2 mm. A colored polystyrene resin was obtained. Example 6 A polymerization initiator was added to 1 kg of methyl methacrylate (monomer) for prepolymerization, and 0.2 g of the heterocyclic compound used in Example 1 was added to the resulting syrup.
This colored syrup was poured into a glass cell and heated at 50-70℃ for 6 hours, then at 100-120℃.
After polymerization at .degree. C. for 3 hours and cooling, a robust bright yellow colored polymethyl methacrylate resin plate (plate thickness: 5 mm) was obtained.

Claims (1)

[Claims] 1. An organic polymer material with a general formula (In the formula, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, cycloalkyl group, aralkyl group, aryl group, hydroxy group, acyloxy group, alkoxy group, amino group, acylamino group, alkylamino group, or arylamino group) and R ² is a hydrogen atom, an alkyl group, an alkoxy group, a nitro group,
Indicates a halogen atom, acylamino group or alkylamino group. ) A method for coloring an organic polymer material, characterized in that it is colored using a heterocyclic compound represented by: