JPS6022108B2 - 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 purpose of the present invention is to color molded products such as fibers, thin films, plates, etc. made of organic polymeric materials, especially synthetic polymeric substances, in clear and bright clear to blue tones. . Therefore, for this purpose, according to the method of the present invention, the above-mentioned organic polymeric material can be prepared according to the following general formula or or represents an aralkyl group,
R2 represents an alkoxycarbonyl group that may have a substituent, a cyclohexyloxycarbonyl group, an aryloxycarbonyl group, a benzyloxycarbonyl group, an acyl group, a cyano group, or a carbamoyl group that may have a substituent, R3 represents a hydrogen atom, an alkyl group, an alkoxy group, a nitro group, a halogen atom, an acylamino group, or an alkyl-substituted amino group.

) is achieved by coloring using one type or a mixture of two or more types of polycyclic compounds.

To explain the present invention in more detail, general formulas {1} and {1
The compound represented by '} is a novel Enomoto ring-based dye, and in the formula, RI is not only a hydrogen atom but also an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, etc. Group; Trifluoromethyl group: Alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group: Methoxycarbonylmethyl group, ethoxycarbonylmethyl group, propoxycarbonylmethyl group, butoxycarbonylmethyl group, etc. alkoxycarbonylalkyl group; phenyl group: aralkyl groups such as penzyl group and phenylethyl group, and R2 includes methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyloxy Unsubstituted alkoxycarbonyl groups such as carbonyl group; methoxyshetoxycarbonyl group, ethoxyshethoxycarbonyl group, propoxyshethoxycarbonyl group, ptoxyshethoxycarbonyl group, methoxypropoxycarbonyl group, methoxyshethoxycarbonyl group, etoxycarbonyl group Shethoxycarbonyl group, propoxyshethoxycarbonyl group, butoxyshethoxycarbonyl group,
Alkoxycarbonyl group substituted with an alkoxy group such as dimethylaminoethoxycarbonyl group, dimethylaminoethoxycarbonyl group, alkoxyalkoxy group, alkylamino group, etc.; cyclohexyloxycarbonyl group: penzyloxycarbonyl group; tolyloxycarbonyl group , aryloxycarbonyl group such as phenoxycarbonyl group; acetyl group, benzoyl group, che/
Acyl groups such as yl group: cyano group; carbamoyl group; phenylcarbamoyl group, methylcarbamoyl group, ethylcarbamoyl group, propylcarbamoyl group, butylcarbamoyl group, dimethylcarbamoyl group, diethylcarbamoyl group group, a substituted carbamoyl group such as a morpholinocarbonyl group, etc., and R3 includes, in addition to a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group;
Alkoxy groups such as methoxy, ethoxy, propoxy and putoxy groups; nitro groups; halogen atoms such as chlorine and bromine; acylamino groups such as acetylamino and benzoylamino groups; methylamino and ethylamine groups;
Examples include alkyl-substituted amino groups such as a propylamino group, a butylamino group, a dimethylamino group, a diethylamino group, a dipropylamino group, and a dibutylamino group.

The compounds represented by the above general formulas {1} and {1'} used in the present invention are, for example, those represented by the general formula (wherein R1 and R2 are the above general formulas {1} and {1'}).
has the same meaning as in .

) and the general formula (wherein R2 has the same meaning as in the general formulas {1} and {1'} shown above).

) can be produced by combining with 3-hydroxyindazoles represented by:

The novel complex moat compound produced in this way includes two types of isomers as represented by the general formulas {1} and {1'}, and is included in the present invention. Although either one of these isomers can be used in carrying out the method, it is convenient to use the isomers as a mixture without separating them. Examples of organic polymer materials that can be applied in the present invention include polyester-based, polyamide-based, polyurethane-based, polyacrylonitrile-based,
Examples include fibers, thin films, plates, and other molded products made of synthetic polymer materials such as polyolefin, polyvinyl chloride, polystyrene, and polyacrylate; fibers made of semi-synthetic polymer materials such as cellulose acetate;
Other molded products may also be used, such as blends of semi-synthetic or synthetic fibers such as polyester fibers, polyamide fibers, cellulose acetate fibers, and blends of natural fibers such as cellulose and wool. It may also be a molded product made of a variety of blended products, or an English polymer such as AS-based or A-based polymers.

In order to color the organic polymer material according to the method of the present invention, when applied to fibers, the compounds represented by the general formulas {1} and {1'} used in the present invention are mixed with water. Since it is completely soluble in water, dyeing or printing paste can be prepared by dispersing it in an aqueous soot using a dispersing agent in a conventional manner, 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 or their blends can be produced with excellent fastness properties. Coloring can be applied. In addition, the compounds represented by the general formulas {1} and {1'} can be applied to the so-called stock solution coloring method, in which they are added during polymerization or during the thread production process of synthetic fibers such as polyester fibers to color them. can do. When coloring synthetic resin, the general formulas shown above {1} and {1}
The required amount of the compound represented by is blended into a synthetic resin, heated and kneaded to form a compression molding method, an injection molding method, a calendar molding method,
By applying a regular molding method such as extrusion molding, it is possible to apply durable coloring to films, sheets, pipes, and other molding methods.

Furthermore, liquid monomers and prepolymers have the general formula {1
} and {1′} are blended, polymerization,
A solidly colored molded product can also be obtained by a cast molding method that involves curing. 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 thereof is exceeded.

Example 1 0.5 parts of a mixture of heterocyclic compounds represented by the following structural formula and are dispersed in 3 parts of water containing 1 part of a condensate of naphthalene sulfonic acid and formaldehyde and 2 parts of a higher alcohol sulfate ester to obtain a dye. was prepared.

Soak 100 pieces of polyester fiber in this beam color bath,
After dyeing at 0qo for 60 minutes, the fibers were soaped, washed with water, and dried to obtain polyester fibers dyed in bright red with good light fastness and sublimation fastness.

The double Hata ring compound used in this example was produced as follows.

20.4 hours of a berinone compound represented by the structural formula was reacted with 7 hours of 3-hydroxyindazole and 14 hours of potassium carbonate in 100 minutes of N-methylpyrrolidone under reflux for 3 hours, and after cooling, the precipitated crystals were heated in a furnace. After evaporation, the mixture was washed with methanol and then with water to obtain 16 red crystals with a melting point of 300°C or higher.

Elemental Analysis Value Example 7 0.5 parts of a mixture of heterocyclic compounds represented by the following structural formula was dispersed in 3 parts of water containing 1.5 parts of a naphthalene sulfonic acid/formaldehyde condensate and 1 part of a higher alcohol sulfate ester. A dye was prepared by adding 15 days of methylnaphthalene carrier.

100% polyester fiber was soaked in this dye, and 10%
After dyeing at 0oo for 90 minutes, it was soaped, washed with water, and dried to obtain a polyester fiber dyed in bright red with good light fastness and sublimation fastness. The heterocyclic compound used in this example was produced as follows.

17.3 days of a berinone compound represented by the structural formula was reacted with 7 days of 3-hydroxyindazole and 14 hours of potassium carbonate in 100 degrees of N-methylpyrrolidone under reflux for 3 hours, and after cooling, the precipitated crystals were filtered through a furnace. Thereafter, it was washed with methanol and then with water to obtain 14 red crystals with a melting point of 30,000 or more.

Elemental Analysis Value Example 3 Prepare dyeing and treat polyester fibers in the same manner as in Example 1, except that 0.52 of a mixture of double Qin ring compounds represented by the following structural formula and was used. A bright red colored polyester fiber with good light fastness and sublimation fastness was obtained.

The heterocyclic compound used in this example was produced according to the production method described in Example 1 by condensing a berynone compound represented by the structural formula with 3-hydroxyindazole.

The melting point was over 300°C. Elemental Analysis Value Example 4 Polyester fibers were dyed using the polycyclic 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.

Example 5 0.5 parts of the mixture of the compound having the above structural formula used in Example 3 was dispersed in 3 parts of water containing 1 part of naphthalene sulfonic acid/formaldehyde condensate and 1 part of sodium higher alkylbenzenesulfonate. A polyamide fiber was soaked in the dye for 90 minutes, then soaped, washed with water, and dried to obtain a polyamide fiber dyed in bright red. .

Example 6 0.2 parts of the mixture of the heterocyclic compound having the above structural formula used in Example 1 was blended with polystyrene resin LK9, melted and thickened at a heating cylinder temperature of 200 to 240 oo, and injection molded by a conventional method. A robust polystyrene resin plate colored bright red and having a thickness of two ribs was obtained.

Example 7 A polymerization initiator was added to 1 kg of methyl methacrylate (monomer) for prepolymerization, and the resulting syrup was mixed with 0.0 kg of the same double Qin ring compound used in Example 1.
The colored syrup was poured into a glass cell and heated at 50-70 qo for 6 hours, then at 100-1 qo.
After polymerizing at 20 qo for 3 hours, it was cooled and peeled off to obtain a robust polymethyl methacrylate resin plate (plate thickness: 5 skins) colored in bright red.

Claims (1)

[Claims] 1 Organic polymeric material can be defined by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R' is a hydrogen atom, an alkyl group, a trifluoro group, etc.) Represents a methyl group, an alkoxycarbonyl group, an alkoxycarbonylalkyl group, a phenyl group, or an aralkyl group, and R^2 is an alkoxycarbonyl group that may have a substituent, a cyclohexyloxycarbonyl group, an aryloxycarbonyl group, or a benzyloxycarbonyl group. R^3 represents a hydrogen atom, an alkyl group, an alkoxy group, a nitro group, a halogen atom, an acylamino group, or an alkyl-substituted amino group. .) A method for coloring an organic polymer material, which comprises coloring using one or a mixture of two or more of the heterocyclic compounds represented by the following.