JPS6022110B2 - 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 object of the present invention is to color molded products such as fibers, thin films, plates, etc. made of organic polymeric materials, particularly synthetic polymeric substances, in a clear and robust yellow to light yellow color. However, for this purpose, according to the method of the present invention, the above organic polymeric material can be prepared by the following general formula and/or (where RI and R2 are hydrogen atoms, lower alkyl groups,
Represents a lower alkoxy group, a halogen atom, a nitro group, a cyano group, a lower alkoxycarbonyl group, a carbamyl group that may have a substituent, a sulfamoyl group that may have a substituent, or a lower dialkylamino group,
One of and Y represents a methine group and the other represents a nitrogen atom. ) is achieved by coloring using one or a mixture of two or more of the Enomoto ring compounds represented by: The present invention will be explained in further detail. In addition to hydrogen atoms, RI and R2 in general formula [1] include lower alkyl groups such as methyl, ethyl, propyl, and butyl; methoxy, ethoxy,
Lower alkoxy groups such as propoxy and butoxy groups;
Halogen atoms such as chlorine and bromine; nitro groups;
Cia/group; lower alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group; carbamoyl group; phenylcarbamoyl group, methylcarbamoyl group,
Substituted carbamoyl groups such as dimethylcarbamoyl group and morpholinocarbamoyl group; sulfamoyl group; phenylsulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, jetylsulfamoyl group, morpholinosulfamoyl group substituted sulfamoyl groups such as; lower dialkylamino groups such as dimethylamino, jetylamino, dipropylamino/dibutylami/groups; The compound represented by the general formula [1] used in the present invention is, for example, the following general formula:

Verynones represented by [0] (wherein RI and R2 have the same meanings as in the general formula [1] shown above) and 3-mercapto 1,2,4 represented by the following formula [m] or It can be produced by condensing with triazole. In addition, the novel Enomoto ring-based compound produced as described above includes 4 types, and in some cases 8 types of isomers, as shown in the general formula [1] above, Although any one of these isomers can be used in carrying out the method of the present invention, it is convenient to use them as a mixture without separating the isomers. Examples of organic polymer materials that can be applied in the present invention include fibers made of synthetic polymer materials such as polyester, polyamide, polyurethane, polyacrylonitrile, polyolefin, polyvinyl chloride, polystine, and polyacrylate. Examples include thin films, plates, and other molded products, but fibers made of semi-synthetic polymeric materials such as cellulose acetate, and other molded products may also be used, as well as polyester fibers, polyamide fibers, cellulose acetate fibers, etc. Various blended products such as semi-synthetic or synthetic fiber blends, blends with natural fibers such as cellulose and wool, and AS, AB
It may also be a molded product made of an S-based copolymer or the like. In order to color the organic polymeric material according to the method of the present invention, when it is applied to fibers, the compound represented by the general formula [1] used in the present invention is insoluble or soluble in water. Since it is a solution, dyeing paste or printing paste can be prepared by dispersing it in an aqueous paste using a dispersant by a conventional method, and then dyeing or printing can be carried out. 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 and their blends can have various fastness properties. Excellent coloring can be applied. In addition, the compound represented by the general formula [1] shown above is
It can be applied to the so-called stock solution coloring method, in which it is added during polymerization in the manufacturing process of synthetic fibers such as polyester fibers, or when it is added to paper yarn for coloring. When coloring a synthetic resin, the required amount of the compound represented by the general formula [1] shown above is blended into the synthetic resin, and the mixture is heated and braised to be molded by compression molding, injection molding, calendar molding, extrusion molding, etc. By applying the usual molding process, films, sheets, pipes, and other molded products can be colored with a strong color. Furthermore, liquid monomers and prepolymers are added to the general formula [1].
] It is also possible to obtain a molded article with a strong color by a cast molding method in which the compound shown in the following formula is blended, 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 the following examples unless it exceeds the gist thereof. Example 1 A mixture of a rear ring compound represented by the structural formula and its three isomers 0. A dye was prepared by dispersing the drumstick in 3 ml of water containing 1 g of naphthalene sulfonic acid-formaldehyde condensate and higher alcohol sulfate ester. When 10 female polyester fibers were soaked in this dyeing method and dyed at 130 pm for 60 minutes, soaped, washed with water and dried, a bright yellow color with good light fastness and sublimation fastness was obtained. Esther fibers were obtained. The heterocyclic compound used in this example was produced as follows. Verinone compound expressed by mechanical formula 3. The abbreviation was reacted with 1.1 g of 3-mercapto 1,2,4 triazole in 30% of pyridine under reflux for 3 hours, and after cooling, the precipitated crystals were placed in a furnace and washed with methanol and then water to give yellow crystals.
．． got him. Elemental analysis values C2oH90, N5S, mass vector parent ion peak m/e = 367 As a result of examination by thin layer chromatography, this product was found to be a mixture of four isomers. Example 2 A mixture of a silane ring compound represented by the structural formula and its seven isomers 0. Naphthalene sulfonic acid-formaldehyde condensate 1. Binary and higher alcohol sulfate esters 1
The chromophore was dispersed in 3.0 g of water, and methylnaphthalene carrier 1 chick was added thereto to prepare a chromatogram. 10 female polyester fibers were soaked in this dye, and 100
After dyeing at ℃ for 90 minutes, soaping, washing with water and drying resulted in a bright yellow dyed polyester fiber with good light fastness and sublimation fastness. The multi-ring compound used in this example was produced as follows. Verinone compound represented by the structural formula and 3. The flowers were reacted with 1.1 g of 3-mercapto-1,2,4 triazole in 30 minutes of pyridine under reflux for 3 hours, and after cooling, the precipitated crystals were filtered and washed with methanol and then water to give yellow crystals.
．． I got a bee. Elemental analysis value C2oH80,N5S,C and mass vector parent ion peak m/e = 401,403 This is the result of thin layer chromatography test 8
It was an isomer mixture of species. Example 3 Polyester fibers were dyed using the double Qin ring 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. (Note) Each dye is a mixture of eight isomers. Example 4 Double Qin ring compound used in Examples 3-7 0.
1g of naphthalenesulfonic acid-formaldehyde condensate
A dye was prepared by dispersing it in 3 waters containing 1 g of sodium higher alkylbenzenesulfonate. 10 female polyamide fibers were soaked in this dye, and
The fibers were dyed at O for 9 minutes, then soaped, washed with water, and dried to obtain polyamide fibers dyed in a bright greenish yellow color. Example 5 The rear ring compound used in Example 1 0. The latter is blended with polystyrene resin LK9, and the heating cylinder temperature is 200~
When melt-melted at 240 qo and injection molded by a conventional method, a solid polystyrene resin plate with a thickness of 2 and colored bright yellow was obtained. Example 6 Example 1 was added to the syrup obtained by adding a polymerization initiator to methyl methacrylate (monomer) lk9 and prepolymerizing it.
The same double Qin ring compound as used in 0. Males were added and dissolved.

Claims (1)

[Claims] 1 Organic polymer material is defined by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and/or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 and R^2 are hydrogen Atom, lower alkyl group, lower alkoxy group, halogen atom, nitro group, cyano group, lower alkoxycarbonyl group, optionally substituted carbamoyl group, optionally substituted sulfamoyl group or lower dialkyl group represents an amino group, one of X and Y represents a methine group, and the other represents a nitrogen atom. A method for coloring organic polymer materials.