JPS6059936B2 - Coloring method for organic polymer materials - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for coloring organic polymer materials.

Specifically, the present invention provides a method for coloring molded products such as fibers, thin films, plates, etc. made of organic polymeric materials, particularly synthetic polymeric substances, into a greenish-yellow tone with clear and robust fluorescence. This purpose is to prepare the above organic polymer material according to the method of the present invention with the following general formula N--R゛゜・, 1′ [N”'10 [I] ・■ / N, vN, .

) is achieved by coloring using a heterocyclic compound shown in the following.

To explain the present invention in more detail, the compound represented by the general formula [I] is a novel heterocyclic dye, in which R''
Examples of the hydrogen atom include alkyl groups such as methyl, ethyl, propyl and butyl groups, and phenyl groups.

In addition, R'' and R3 are hydrogen atoms, alkyl groups such as methyl group, ethyl group, propyl group, butyl group,
Examples include aryl groups such as phenyl group and tolyl group, and aralkyl groups such as benzyl group and phenethyl group. The compound represented by the above general formula [1] used in the present invention is, for example, the following general formula [formula (formula, where Rl, R2 and R3 have the same meanings as in the above general formula [1], R4 represents an alkyl group.

) The ester moiety of the compound represented by the formula [■] is hydrolyzed to perform a decarboxylation reaction, or the following general formula [■] (wherein R1 has the same meaning as in the above general formula [1], R4 has the same meaning as in the general formula [■].

) is represented by the following general formula [■] (wherein R2 and R3 have the same meanings as in the above general formula [1]).

) can be produced by reacting with the ureas shown in (1) and perimidonizing it in one step accompanied by a hydrolysis reaction and a decarboxylation reaction.

In order to carry out the above-mentioned hydrolysis and decarboxylation reactions more efficiently, R4 in the general formulas [formerly and [■]] is preferably a lower alkyl group such as a methyl group or an ethyl group.

The organic polymeric materials used in the method of the present invention include fibers made of synthetic polymeric substances such as polyester, polyamide, polyurethane, polyacrylonitrile, polyolefin, polyvinyl chloride, polystyrene, and polyacrylate. Alternatively, molded products such as thin films and plates may be mentioned, but fibers or molded products made of semi-synthetic polymer substances such as cellulose acetate fibers may also be used, and polyester fibers, polyamide fibers, and cellulose acetate fibers may also be used. Blends of semi-synthetic or synthetic fibers such as A, or blends of natural fibers such as cellulose or wool with the above semi-synthetic or synthetic fibers, or A
It may also be a molded article made of a copolymer such as S-based or ABS-based.

In order to color fibers by the method of the present invention, the general formula [1
] A dye bath or printing paste is prepared by dispersing the compound represented by in an aqueous medium using a dispersant by a conventional method,
Dip dyeing or printing may be performed.

For example, in the case of dip dyeing, if disperse dye dyeing methods such as ordinary dyeing method, high temperature dyeing method, carrier dyeing method, thermosol dyeing method, etc. are applied as they are, semi-synthetic or synthetic fibers or their blends can be produced with excellent fastness properties. Coloring can be applied. Further, the compound represented by the above general formula [1] 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 a synthetic resin, the required amount of the compound represented by the general formula [1] shown above is blended with the synthetic resin, heated and kneaded, and then molded using a compression molding method, injection molding method, calendar molding method, extrusion molding method, etc. By applying ordinary molding methods, it is possible to apply strong coloring to films, sheets, vibrators, and other molded products. 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 [1] shown above is blended with a liquid monomer or prepolymer, and then 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 A dyeing bath was prepared by dispersing 0.5y of a heterocyclic compound represented by the following structural formula in water 3e containing a condensate of naphthalene sulfonic acid and formaldehyde 1da and higher alcohol sulfate 2y.

Polyester fiber 100V was immersed in this dyeing bath, and 13
After 6 times powder dyeing at 0°C, the fibers were soaped, washed with water, and dried to obtain polyester fibers dyed in bright fluorescent greenish-yellow color with good light fastness and sublimation fastness.

The heterocyclic compound used in this example was produced by the following method.

14.6 g of a perinone compound represented by the structural formula was reacted with 53y of 1,3-dimethylurea in 30 ml of nitrobenzene under reflux for 15 hours, and after cooling, 500 ml of methanol was added.
The solution was diluted with 100ml and stirred for about 5 hours to precipitate crystals.

The precipitated crystals were filtered, washed with methanol and then with water to obtain yellow crystals 6y with a melting point of 352-356°C. Elemental analysis value Example 2 0.5y of a heterocyclic compound represented by the following structural formula is dispersed in water 3' containing 1.5f of a condensate of naphthalene sulfonic acid and formaldehyde and higher alcohol sulfate 1y,
Methylnaphthalene carrier 15y was added to this to prepare a dyeing bath.

100y of polyester fibers were immersed in this dyeing bath,
After powder dyeing at 0° C., the fibers were soaped, washed with water, and dried to obtain a bright fluorescent greenish-yellow dyed polyester fiber with good light fastness and sublimation fastness.

The heterocyclic compound used in this example was produced by the following method.

A perinone compound 10.5V represented by the structural formula is p-tolu7
React with 2f of ensulfonic acid in 80 ml of nitrobenzene under reflux for 2 hours, and after cooling, add 500 ml of methanol.
diluted with water and stirred.

After stirring for about 5 hours, the mixture was filtered, washed with methanol, and then washed with water to obtain yellow crystals 5f5 with a melting point of 292-294°C. Elemental analysis value 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.

In addition, the compound used in this example was manufactured according to the manufacturing method described in Examples 1 and 2.

Example 4 0.5y of the heterocyclic compound used in Example 2 was mixed with water 3' containing a condensate of naphthalene sulfonic acid and formaldehyde 1y and a sorter of higher alkylbenzenesulfonic acid 1y.
A dyeing bath was prepared by dispersing the fibers in
The polyamide fibers were soaped, washed with water, and dried to obtain a polyamide fiber dyed in a bright fluorescent greenish-yellow color.

Example 5 0.2 da of the heterocyclic compound used in Example 1 was blended with polystyrene resin 1k9, and the heating cylinder temperature was 200.
When the mixture was melt-kneaded at ~240°C and injection molded by a conventional method, a robust polystyrene resin plate having a thickness of 2 Tnm and colored in a bright greenish-yellow fluorescent color was obtained.

Example 6 A polymerization initiator was added to 1k9 of methyl methacrylate (monomer) for preliminary polymerization, and 0.2 da of the same heterocyclic compound used in Example 1 was added and dissolved in the resulting syrup. The colored syrup was poured into a glass cell and polymerized at 50-70°C for 6 hours, then at 100-120°C for 3 hours, and then peeled off to give a robust bright fluorescent greenish-yellow color. A polymethyl methacrylate resin plate (plate thickness 5wr1n) was obtained.

Claims (1)

[Claims] 1 Organic polymer material is defined by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ^2 and R^3 are hydrogen atoms, alkyl groups,
Represents an aryl group or an aralkyl group. ) A method for coloring an organic polymer material, characterized in that it is colored using a heterocyclic compound represented by: