JPS6022111B2 - 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 tone. Therefore, for this purpose, according to the method of the present invention, the above-mentioned organic polymeric material can be prepared by the following general formula (where RI is a hydrogen atom, an optionally substituted alkyl group, and RI).

It represents an alkyl group, an alkenyl group, an aryl group, a hydroxyl group, an acyloxy group, an alkoxy group, an acylamino group, or an optionally substituted amino group, and R2 and R3 are each a hydrogen atom, a halogen atom, a nitro group, or an alkoxy It represents a carponyl group or an optionally substituted carbamoyl group, X represents a hydrogen atom, a halogen atom, or a nitro group, and Y represents a hydrogen atom, an alkoxycarbonyl group, or an optionally substituted carbamoyl group. ) is achieved by coloring using one type or a mixture of two or more types of heterocyclic compounds.
To explain the present invention in detail, the compound represented by the general formula [1] is a novel multi-ring-based dye, and in the formula, RI is a methyl group, an ethyl group, an isopropyl group, in addition to a hydrogen atom, Alkyl groups such as butyl group and octyl group; hydroxyalkyl group, alkoxyalkyl group, alkoxyalkoxyalkyl group, aryloxyalkyl group, alkoxycarbonylalkyl group, cyanoalkyl group, dialkylaminoalkyl group, halogenoalkyl group, carboxyalkyl group, Substituted alkyl groups such as dialkylcarbamoyl alkyl groups, cyclohexyloxyalkyl groups, aralkyl groups; cycloalkyl groups such as cyclohexyl groups; alkenyl groups such as allyl groups; phenyl groups, tolyl groups, xylyl groups, coo-phenyl groups , Pu.

Aryl groups such as mophenyl group, alkoxyphenyl group, nitrophenyl group, cyanophenyl group: hydroxy group;
Acyloxy groups such as acetoxy groups and besoyloxy groups;
Alkoxy groups such as methoxy and ethoxy groups; acylamino groups such as acetylamino and benzoylamino groups; amino groups: substituted amino groups such as dimethylamino and phenylamino groups. In this formula, examples of the halogen atom represented by R2, R3 or and similarly substituted carbamoyl groups include phenylcarbamoyl group, p-methoxyphenycarbamoy group, methylcarbamoyl group,
Examples include carbamoyl groups substituted with aryl groups such as ethylcarbamoyl and diethylcarbamoyl groups, and alkyl groups. The compound represented by the above general formula [1] used in the present invention is, for example, the general formula (wherein R has the same meaning as in the above general formula [1]).

) and the 4,5-dichloronaphthalimides represented by the general formula (wherein R2, R3, X and Y have the same meanings as in the general formula [1] above).

) in the presence of a deoxidizing agent to form a pyran ring, and if necessary, it can be produced by further halogenating, nitrating, etc. Examples of organic polymer materials applicable to the present invention include polyester-based, polyamide-based, polyurethane-based, and polyacrylic.

Examples include fibers, thin films, plates, and other molded products made of synthetic polymer materials such as nitrile, polyolefin, polyvinyl chloride, polystyrene, and polyacrylate. It may also be a blend of semi-synthetic or synthetic fibers such as polyester fibers, polyamide fibers, cellulose acetate fibers, etc.
Alternatively, it may be a blended product such as a blended product with natural fibers such as cellulose or wool, or a molded product made of a copolymer such as AS type or ABS type. To color the organic polymeric material according to the method of the present invention,
When applied to fibers, the compound represented by the general formula [1] used in the present invention is insoluble or eluent-soluble in water, so it is added to an aqueous medium using a dispersant by a conventional method. What is necessary is to prepare a dispersed dyeing paste or printing paste and perform immersion dyeing or printing.

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 have various fastness properties. Excellent coloring can be applied. In addition, the compound represented by the general formula [1] can be applied to the so-called stock solution coloring method in which it is added and colored during polymerization or spinning during the manufacturing process of synthetic fibers such as polyester fibers. can. 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 compression molded.
By applying ordinary molding methods such as injection molding, calendar molding, and extrusion molding, films, sheets, pipes, and other molded products can be colored with a strong color.

Furthermore, the liquid monomer and prepolymer have the general formula [1
] It is also possible to obtain a molded article with strong coloring by a cast molding method in which a compound represented by the following formula is blended, polymerized and cured. Next, the present invention will be described in more detail with reference to examples, but the present invention will be described in more detail with reference to examples.
The present invention is not limited to these examples.

Example 1 A dyeing bath was prepared by dispersing 0.5 parts of a heterocyclic compound represented by the following structural formula in 3 parts of water containing 1 part of a condensate of naphthalene sulfonic acid and formaldehyde and 2 parts of higher alcohol sulfate ester.

Soak 100 grams of polyester fiber in this dyeing bath,
After dyeing at 0° C. for 60 minutes, soaping, washing with water and drying were performed, a polyester fine dyed in a bright greenish yellow color with good light fastness and sublimation fastness was obtained.

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

8 naphthol 14 days and potassium hydroxide 14 days were reacted at 15,000 °C for 3 hours under a nitrogen stream, the produced water was distilled off, and after cooling, 4,5-dichloronaphthalic acid-N-
(y-methoxypropyl)imide was added 3.4 times;
React for 3 hours at 00 to 210 0, then cool to 80°C, dilute with ethanol, incubate at 70 to 75 qo for 1 hour, cool to room temperature, filter the precipitated crystals,
Melt point 205-206℃ after washing with methanol and water.
Yellow crystals of 3.0% were obtained.

Elemental analysis value C: 26 days, 904 NI Example 2 0.5 parts of a double ring compound represented by the following structural formula was added to 3 parts of water containing 1.5 parts of a naphthalene sulfonic acid-formaldehyde condensate and 1 part of a higher alcohol sulfate ester. The mixture was dispersed, and a methylnaphthalene carrier was added thereto to prepare a dye.

100% polyester fiber was soaked in this dye, and 10%
After dyeing at 0° C. for 90 minutes, soaping, washing with water and drying, a polyester fiber dyed in a bright greenish yellow color with good light fastness and sublimation fastness was obtained.

The Enomoto ring-based compound used in this example was prepared using 4,5-dichloronaphthalic acid-N-(
It was produced using 4,5-dichloronaphthalic acid-N-methylimide instead of y-methoxypropylimide.

The obtained crystals were yellow crystals and had a melting point of 300 qo or more. Elemental analysis value C: 23 days, 303 N. Example 3 Polyester fibers were dyed using the polycyclic compounds shown in the table below to obtain dyed products having the colors shown in the table.

Example 4 A dyeing bath was prepared by dispersing a double ring compound represented by the following structural formula in 3 waters containing 1 part of a thanaphthalenesulfonic acid-formaldehyde condensate and 1 part of sodium higher alkylbenzenesulfonate, In this dyeing grade, polyamide fiber 100
After soaking and dyeing at 100° C. for 9 minutes, soaping, washing with water and drying were performed, polyamide fibers dyed in a bright greenish yellow color were obtained.

The heterocyclic compound used in this example was 2-hydroxy-4,5-dichloronaphthalic acid methylimide.
3-naphthoic acid anilide 2.92 and potassium carbonate 1
．． The reaction was carried out under reflux in 20°C of N-methylpyrrolidone for 4 days, and after cooling, it was diluted with methanol. It was recrystallized from N-dimethylformamide and was a clear-colored crystal with a melting point of 300 oo or more.

Elemental analysis value C3oH, 9C4N2 Example 5 0.2 mm of a heterocyclic compound represented by the following structural formula was blended into polystyrene resin LK9, and the heating cylinder temperature was 200 to 240.
When the mixture was melted and kneaded at a temperature of 0.degree. C. and injection molded using a conventional method, a robust polystyrene plate having a thickness of 2 yen and colored in a bright greenish-yellow color was obtained.

The heterocyclic compound used in this example was prepared according to the method described in Example 1, and 4,5-dichloronaphthalic acid-N-(
It is produced using 4,5-dichloronaphthalic acid-N-(8-phenoxyethyl)imide instead of y-methoxypropyl)imide, and has a melting point of 247 to 248 qo.
It was a clear color crystal.

Elemental analysis value C3oH, 904N, Example 6 A polymerization initiator was added to methyl methacrylate monomer-lk9 to prepolymerize it, and 0.2% of the same double Qin ring compound used in Example 2 was added to the resulting syrup. Add and dissolve syrup and inject this colored syrup into a glass cell.
After polymerizing at 0 to 70°C for 6 hours and then at 100 to 120 qo for 3 hours, it was cooled and peeled off, resulting in a polymethyl methacrylate resin plate (plate thickness: 5 fences) colored in a strong bright greenish yellow color. was gotten.

Claims (1)

[Claims] 1 The organic polymer material is defined by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 is a hydrogen atom, an optionally substituted alkyl group, cycloalkyl group, alkenyl group) , represents an aryl group, a hydroxy group, an acyloxy group, an alkoxy group, an acylamino group, or an optionally substituted amino group, and R^2 and R^3 are each a hydrogen atom, a halogen atom, a nitro group, an alkoxycarbonyl group, or a substituted X represents a hydrogen atom, a halogen atom or a nitro group, and Y represents a hydrogen atom, an alkoxycarbonyl group or an optionally substituted carbamoyl group. A method for coloring an organic polymer material, characterized by coloring using one type or a mixture of two or more types of compounds.