JPS6219457B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the following general formula () (In the formula, X represents a chlorine atom or a bromine atom, and n and m are each an integer of 0, 1, or 2. R represents a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, a phenyl group, or a benzo nucleus. ) is related to a dye for coloring organic polymer materials. Conventionally, when coloring highly transparent organic polymer materials (such as polystyrene, polyacrylic, polyester, or polyvinyl chloride resins), it has been difficult to achieve clear coloring without impairing its transparency. So-called pigments were inappropriate, and compounds belonging to low molecular weight oil colors, some dyes, and some pigments were used, but the physical properties of colored materials such as color tone, colorant bleed, light resistance, etc. There were few compounds that were excellent in all respects. In particular, when a bright fluorescent color tone is required, there are almost no compounds that can satisfy this requirement. As a result of intensive studies on the coloring of organic polymer compounds that require transparency, the present inventors found that the compound represented by the general formula () has a clear color tone with strong fluorescence suitable for the above coloring purpose. The present invention was completed based on the knowledge that red colored products could be produced. In the present invention, the compound in which R is a hydrogen atom and n=m=O is a known substance, but it has not been previously known that it is suitable for coloring transparent polymers. Compounds other than this and compounds having a bromine atom in the indigo residue are new substances. The compound of general formula () of the present invention can be easily obtained by heating indigo or a derivative thereof with an acid chloride of phenyl acetic acid or a derivative thereof in an inert high-boiling solvent according to the following reaction formula. Examples of indigo derivatives used here include indigo, 5,5'-dichloroindigo, and 5.5'-dichloroindigo.
Examples include 5', 7, 7'-tetrachlorindigo, 5, 5'-dibromine indigo, 5, 5', 7-tribromine indigo, and 5, 5', 7, 7'-tetrabromine indigo. In addition, as phenyl acetic acid derivatives, phenyl acetic acid, O-chlorophenyl acetic acid, m-chlorophenyl acetic acid, P-chlorophenyl acetic acid, 2,4-dichlorophenyl acetic acid, 2,5-dichlorophenyl acetic acid, 3,4-dichlorophenyl acetic acid, O-methylphenyl acetic acid, acetic acid, m-methylphenyl acetic acid, P-
Methylphenyl acetic acid, 2,4-dimethylphenyl acetic acid, 2,5-dimethylphenyl acetic acid, 3,4-
Examples include dimethylphenyl acetic acid, 2-methyl-5-chlorophenyl acetic acid, 4-phenyl phenyl acetic acid, and α-naphthyl acetic acid. Inert high-boiling solvents include nitrobenzene,
Suitable are O-nitrotoluene, O-dichlorobenzene, trichlorobenzene, tetralin or decalin. The organic polymer materials targeted by the present invention include:
For example, polyolefin, polyacrylic,
Polyamides, styrene polymers and their copolymers (e.g. AS resin, ABS resin, etc.), vinyl chloride polymers and their copolymers, vinylidene chloride polymers and their copolymers, methacrylic acid ester polymers and their copolymers Polymers, urea-formaldehyde series, sulfonamide series, melamine-formaldehyde series,
Examples include polyacetal-based, polyester-based (including semi-synthetic types such as cellulose acetate, cellulose butyrate, or nitrocellulose), and polyether-based polymer compounds. The dye of the present invention has excellent light resistance, migration resistance, heat resistance, and chemical resistance in fields where clear coloring with fluorescence while maintaining transparency is required for use in such organic polymeric materials. It is extremely excellent. The dye of the present invention may be applied to color an organic polymer material in accordance with a general coloring method for organic polymer materials. For example, in the case of a thermoplastic resin, it may be mixed with a monomer, A method of obtaining a colored resin by polymerization, or a method of blending the resin before molding, heating and kneading, and molding this by an appropriate method to obtain a colored product in the form of a molded article, pipe, sheet or film is applied. . Further, in the case of a thermoplastic resin, the colored resin can be obtained by blending the dye of the present invention with a suitable prepolymer or a mixture thereof with a curing agent, and heat molding or forming it into a film. In these coloring methods, the dye of the present invention can be applied at various concentrations, but generally 0.005% to 1% OWR (OWR means per weight of resin) is suitable. Table 1 shows the relationship between the chemical structure of the dye and the colorability when the dye of the present invention is added to polystyrene resin for coloring.

【table】

[Table] Move. (The same is true for methyl group-substituted products.) Substitution of indigo nuclei also tends to decrease fluorescence and deepen the hue. The dyes of the present invention generally have a high boiling point of 360
Does not melt at °C. Therefore, the identification of the compound was based on infrared absorption spectra. Table 2 below shows polystyrene colored products using the dye of the present invention (Toporex 525-51, 190°C, 0.02%
The fluorescence and absorption maximum wavelengths of OWR (colorant formulation) are listed. All of these pigments give a red coloring, and it is difficult to express subtle changes in tone lexically.

[Table] The position numbers of substituents X and R shown in Table 2 are shown below. The fluorescence spectrum was measured with a Hitachi EPS-2U machine, and the visible absorption spectrum was measured with a Shimadzu MPS-50L machine. The infrared absorption spectra of the dyes shown in Figure 1 and below were measured using an IR-A machine manufactured by JASCO Corporation. For example, when polystyrene is colored with the dye of the present invention, at a dye concentration of 0.02%,
It is stable after heating for 1 minute, and shows only slight discoloration when irradiated with a carbon arc fade meter for 100 hours. In addition, the bleed resistance, acid resistance, alkali resistance, water resistance, and other resistances are very good. The method of using the dye of the present invention will be explained in detail with reference to Examples below. In the examples, "parts" means "parts by weight." Example 1 One part of the compound of colorant No. 1 shown in Table 2 was made into powder, and polystyrene pellets (Toporex-
525-51) and 2000 parts of the pellets were thoroughly shaken in a bag and thoroughly mixed with the pellets. Next, the mixture was kneaded in a cylinder heated to 190°C, and injection molded at the same temperature to obtain a bright red molded product with orange fluorescence. Example 2 In Example 1, AS resin or ABS resin pellets were used instead of polystyrene pellets,
240℃ for AS resin, 230℃ for ABS resin
Injection molding was carried out using the same method as in Example 1, and a brightly colored product having the same fluorescence as in Example 1 was obtained. Example 3 The same coloring as in Example 1 or 2 was carried out using the coloring agents with dye numbers 2 to 14 in Table 2, respectively,
A brightly colored product with fluorescence was obtained. Example 4 1 part of the colorant of dye number 5 of Table 2 was kneaded with a mixture consisting of 100 parts of polyvinyl chloride and 100 parts of dioticle phthalate at 150°C for 10 minutes and then kept at a temperature of 160°C. It was pressed between metal plates for 5 minutes to form a sheet with a thickness of 1 mm. The resulting sheet exhibited a bright red color with good fastness and strong orange-yellow fluorescence. Example 5 Take 0.5 part of dye number 8 in Table 2, add 100 parts of dimethyl terephthalate, and ethylene glycol.
62 parts, zinc acetate 0.015 parts and antimony trioxide
0.02 part of the mixture was added, the air was excluded, and the mixture was heated to 220° C. for 4 hours to distill off the methanol produced. Next, 1 part titanium oxide is mixed with 1 part ethylene glycol.
After stirring well, the mixture was heated under reduced pressure for 4 hours, and finally heated to 275°C to complete the polycondensation reaction. The thus obtained polymer was extruded from a die at 260°C to 280°C and spun to obtain a brightly fluorescent red polyester fiber. Example 6 To 50 parts of sulfonamide resin melted at 120°C,
Add 20 parts of unmodified melamine-formaldehyde resin, raise the temperature to 170-180°C, add 0.5 part of dye No. 7 in Table 2, completely dissolve, cool, solidify, and then crush to form an orange color. A bright red fluorescent pigment that emits fluorescence was obtained. Example 7 70 parts of ethylene glycol ester of acrylic acid-methacrylic acid copolymer, 20 parts of butylated methylolmelamine, 10 parts of cellulose acetate butyrate
Add 1 part of pigment number 4 in Table 2 as a fine powder to a xylene-butanol (4; 1) solution containing It was applied to a metal plate in the form of a film with a thickness of 25μ, and baked at 140℃ for 30 minutes to obtain a clear red film. At this time, a short oil type modified phthalkyd resin was used in place of the acrylic acid ester, and titanium dioxide was used in place of the aluminum pigment to obtain a clear red opaque film. A bright red film was similarly obtained using a lacquer made of nitrocellulose-dioctyl phthalate-alkyd resin. Example 8 5% of the finely divided pigment of pigment No. 1 in Table 2 was added to a rosin maleic acid-modified polyester resin.
Add, thoroughly knead with boiling oil and solvent,
This was used as a printing ink and printed on a suitable substrate to obtain a bright red print. Printing inks prepared in the same manner using a long oil alkyd resin or a modified phenolic resin in place of the rosin maleic acid modified polyester resin gave a bright red printed surface when printed and baked onto a metal surface. Example 9 Add 0.05% OW of dye number 9 in Table 2 to polypropylene or high-density polyethylene pellets.
R., and kneaded and injection molded at 190°C to obtain a bright red colored molded product with fluorescence. Example 10 Manufacturing method for dye number 11 in Table 2 1 part of 2,4-dichlorophenoxyacetic acid and 1 part of thionyl chloride were heated with 3 parts of nitrobenzene at 100°C for 30 minutes,
Then, 0.5 part of indigo was added and boiled for 1 hour. This was cooled to 100°C, 0.5 part of thionyl chloride was added, and after boiling for an additional 3 hours, it was allowed to cool to room temperature. The precipitated crystals were filtered, washed with acetone, and recrystallized from nitrobenzene to obtain the desired product as bright red fine columnar crystals. The other dyes shown in Table 2 above can also be synthesized by substantially the same manufacturing method as in this example.

[Brief explanation of the drawing]

FIGS. 1 to 14 show infrared absorption spectrum diagrams corresponding to dyes numbered 1 to 14 shown in Table 2 of the specification, respectively.

Claims (1)

[Claims] 1. General formula (In the formula, X represents a chlorine atom or a bromine atom, and n and m each represent an integer of 0, 1 or 2,
R is a hydrogen atom, a chlorine atom, a bromine atom, a methyl group,
Represents a phenyl group or a benzo nucleus. ) A dye for coloring organic polymer materials.