JPS5910391B2 - Yellow organic compound and method for coloring polymeric materials with yellow organic compound - Google Patents

Description

[Detailed description of the invention] The present invention relates to a novel yellow organic compound.

More specifically, the present invention relates to a phthalimidoquinophthalone yellow compound particularly suitable for use as a dye and pigment with excellent heat resistance, and its use as a coloring agent for polymeric materials. That is, the compound of the present invention is a novel yellow compound represented by the following general formula [I], and this compound has not been known so far.

? 〉Imeko 0=CC■ 011x Y.

Y0...[I] [However, X and Y in the formula represent a chlorine atom or a bromine atom.

] Many compounds have been known as quinophthalone compounds, but very few compounds with particularly excellent heat resistance and light resistance are suitable for use as dyes and pigments.

For example, Japanese Patent Publication No. 47-3476 states that a compound having the following structural formula is suitable as a pigment dye due to its insolubility in water and organic solvents, excellent light fastness, and remarkable thermal stability. The presented 0.9〉Honichi 0 4 hours”.

However, as described in the above specification, the compound represented by the structural formula [■] can be used as a pigment [■]C-dye, for example, for the production of varnishes and printing dyes, and for thermoplastic artificial materials such as polystyrene, polyvinyl chloride, etc. , polyamide, polyester, polyacrylonitrile, triacetate and acetate J ■■ Possible, but synthetic resins,
In particular, it does not have sufficient heat resistance to be used as a coloring pigment for synthetic resins that require high molding temperatures, such as polyolefins and polycarbonates.

On the other hand, pigments with a methyl group at the 4' position were
As described in Publication No. 7343, the present inventor used a polyethylene resin to compare the heat resistance of the compounds shown in [l] to [] from 240°C to 300°C using a color difference meter in terms of ΔE. The result is 45 as shown in the reference example.
It was found that the compounds [] and ], in which a methyl group was introduced at the position, were inferior in heat resistance compared to the compounds [I] and [v], respectively.

As a result, it was found that those having a methyl group at the 4' position have lower heat resistance than those having no methyl group. However,
As a result of intensive research into improving heat resistance, the present inventors found that a yellow organic compound in which a methyl group was introduced into the 4' position of a specific yellow halogen compound showed, surprisingly, a marked improvement in heat resistance, completely contrary to expectations. It is a new compound that has been
Moreover, they discovered that it is extremely useful as a coloring agent for polymeric materials, leading to the present invention.

That is, the present invention provides a yellow organic compound represented by the formula: [wherein X and Y represent a chlorine atom or a bromine atom].

and 2. A method for coloring a polymeric material, which comprises using a yellow organic compound represented by the general formula [1] [wherein x and Y represent a chlorine atom or a bromine atom] as a coloring agent for the polymeric material. .

The novel yellow organic compound represented by the general formula [1] of the present invention is produced by condensing 4-methyl-8-aminoquinaldine with tetrachlorophthalic acid or/and tetrabromophthalic acid or their acid anhydrides. be done.

The advantage of the novel compound [ ] of the present invention over compound [ ] in production is that the cyclization yield of 4-methylquinaldines as a starting material is higher than that of the corresponding quinaldine.

For example, the yield of 8-chloroquinaldine from o-chloroaniline and crotonaldehyde is about 55% (about 40% when paraaldehyde is used), whereas from -chloroaniline and pentanol-4-one-2 The yield of 8-chloro-4-methylquinaldine was found to reach 70%. 8-chloro-4-methylquinaldine is derived to 8-amino-4-methylquinaldine by treatment with aqueous ammonia in the presence of a copper catalyst.

The reaction of 4-methyl-8-aminoquinaldine and tetrachloromono- or tetrabromophthalic acid or their acid anhydrides can be carried out in the presence or absence of a solvent or diluent.

When the reaction is carried out in the presence of a diluent, the diluent used is an organic solvent inert to the reaction, such as nitrobenzene, 0-dichlorobenzene, trichlorobenzene, trimethylbenzene, decalin, tetralin, diphenyl ether, chlornaphthalene. , N-methylpyrrolidone, etc. are used. The amount of diluent used is 1 to 2 with respect to the reactant.
It may be 0 times by weight, and a large amount of diluent may be used, but
From the viewpoint of solvent recovery after the reaction, the amount may preferably be 2 to 10 times the weight. Further, the ratio of 4-methyl-8-aminoquinaldine to halogenated phthalic acid or anhydride thereof may be in any range, but is preferably in the range of 0.3 to 3.

The reaction is carried out at a temperature range of 100 to 300°C,
Preferably, the temperature is in the range of 150 to 260°C. The reaction is carried out by adding the raw material mixture in the presence or absence of the above solvent or diluent,
The process can proceed simply by heating at an appropriate temperature, but to make it more effective, a catalyst such as zinc chloride or aluminum chloride may be added.

After reacting in this way, in order to take out the desired quinophthalone-based yellow compound from the reaction mixture, the reaction mixture is separated by filtration while hot or after cooling. It may be cleaned with a suitable solvent such as acetone.

Alternatively, the above-mentioned solvent may be added to the reaction mixture before the reaction mixture is cooled and treated. If further purification is required, washing may be performed using a solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, α-chlornaphthalene, or the like. The quinophthalone-based organic compound thus obtained can be used after being further made into a pigment by a conventional pigmentation method, if necessary.

After pulverization, it can also be converted into a pigment by heat treatment with alcohols, ketones, amides such as dimethylformamide, aromatic hydrocarbons, chlorinated aromatic hydrocarbons, and the like. The novel compound of the present invention produced by the method detailed above has excellent heat resistance, light resistance, chemical resistance, and color tone, and is extremely useful as a coloring agent for polymeric materials.

Polymer materials that can be colored using the compound of the present invention include polyolefins such as polyethylene and polypropylene, polystyrenes, polyesters, polycarbonates, and AB.
Examples include materials such as Sl polyacrylonitrile, polyacrylate, polyvinyl chloride, polyacetal, amino resin, cellulose acetate, epoxy resin, and polyamide.

When coloring a polymeric material using the compound [1] of the present invention, the polymeric material containing the compound [1] is heated and kneaded, and then a conventional method such as compression molding, injection molding, or calendar molding is applied. Molding products such as films, sheets, fibers, pipes, and pellets can be colored yellow by the molding method, and a new compound represented by the general formula [1] can be blended with liquid monomers and prepolymers to polymerize them. It can also be colored by a cast molding method in which it is cured.

Also, as a coloring agent for paints, the general formula [
Coloring can also be achieved by blending the compound shown in 1]. Furthermore, by blending the novel compound represented by general formula [1] with a polymeric material used in printing ink, it can also be used as a coloring agent for ink. Furthermore, fibers and textiles can be colored by known dyeing methods using the novel compound represented by the general formula [1]. The novel compound represented by the general formula [1] of the present invention has light resistance,
It also has excellent migration resistance, and as shown in the Examples and Comparative Examples, it is particularly superior in terms of heat resistance compared to the compound represented by the general formula [Kawa].

Examples are shown below.

In addition, "part" in an example is "part by weight." Example 1 240 parts of α-chloronaphthalene was added to 34.4 parts of 4-methyl-8-aminoquinaldine and 143 parts of 1-tetrachlorophthalic anhydride, refluxed at the boiling point, and reacted for 5 hours while removing water from the system. After heat aging, a yellow reaction product was obtained.

This product was heated and stirred with 360 parts of α-chlornaphthalene, washed, and dried for one heat to obtain 113 parts of a yellow product having a melting point of 360°C or higher and having the structural formula [ ]. Ta. Elemental analysis values are C=45.95, H=1.08, N=
4.04, calculated value C-45.81 at Cl=40.25%
, H=1.14, N=3.96, Cl=40.06%. The infrared spectrum is shown in Figure 1. recognized. Moreover, the mass spectrum is shown in FIG.

The maximum wavelength of visible absorption λMas was 424 mμ (dimethylformamide solution). 1.5 parts of the new compound represented by the structural formula [] was blended with 1000 parts of polyethylene resin, and mixed and extruded at 230° C. using a melt-extruder to obtain pellets colored yellow.

This pellet was injection molded under the conditions shown in Table 1 below to obtain a molded plate, and using the molded plate obtained at 240°C for 1 minute as a reference, the Lab system of UCS (isochromatic color system) was measured using a color difference meter. Table 1 shows the results of measuring the color difference ΔE used. Comparative Example 1 in Table 1 shows the results of forming a molded plate under the same conditions using a compound having the following structural formula [] and measuring ΔE using a color difference meter.

As can be seen from Table 1, the novel compound [] of the present invention has a smaller color change (ΔE) due to temperature than the compound [], and has excellent heat resistance.

Reference Example 1 1.5 parts each of the following structural formulas [] and [] were blended into 1000 parts of polyethylene resin, and 23
Mixing and extrusion at 0°C gave yellow colored pellets.

The pellets were injection molded under the conditions shown in Table 2 below to obtain a molded plate, and ΔE was measured using a color difference meter using the molded plate obtained at 240° C. for 1 minute as a reference. Table 2 shows the results. As seen from Table 2, [] having a methyl group at the 4' position is [I]
The color changes greatly depending on temperature compared to , and the heat resistance is poor.

Reference Example 2 The same test as in Reference Example 1 was conducted using the following structural formulas [] and [], and the results shown in Table 3 were obtained.

As can be seen from Table 3, [ ] having a methyl group at the 4' position shows a larger change in color with temperature than [ ] and has poor heat resistance.

Example 2 A reaction was carried out in the same manner as in Example 1, using 232 parts of tetrabromophthalic anhydride instead of tetrachlorophthalic anhydride, to obtain 166 parts of a yellow compound having the following structural formula.

Elemental analysis values are C=30.55, H=0.82, N=2.
49, Br=60.34, calculated value C=30.48, H=
0.67, N==2.63, and Br=60.11.

The infrared spectrum of λMax=428 mμ (dimethylformamide solution) is shown in FIG. Example 3 17 parts of 4-methyl-8-aminoquinaldine and 29 parts of tetrachlorophthalic anhydride were heated in 200 parts of trichlorobenzene, and the reaction was carried out at the boiling point for 2 hours while the generated water was taken out of the system as steam. .

Next, 69 parts of tetrabromophthalic anhydride and 4 parts of zinc chloride were added, the reaction was carried out for 3 hours, and 5 parts of dimethylformamide was added.
0 part was added and further heated for 1 hour. The product was separated at 120°C, washed with 100 parts of dimethylformamide, and finally washed with ethanol and dried to obtain 52 parts of a yellow compound having the following structural formula. Elemental analysis value is C=36.4
5, H=0.96, N=3.02, halogen 51.63
%, calculated value C=36.61, H=0.91, N=3.1
6. Halogen content was 52.10%.

Incidentally, the infrared spectrum of this compound is shown in FIG.

λMax=427 mμ (dimethylformamide solution) Example 4 62 parts of 8-tetrabromphthalimide-4-methylquinaldine and 43 parts of tetrachlorophthalic anhydride were dissolved in 200 parts of diphenyl ether, and the reaction was carried out at the boiling point for 5 hours. After hot evaporation at 120°C, the product was dispersed in 100 parts of dimethylformamide and stirred at 120°C for 6 hours.

After P was removed, the mixture was washed with ethanol to obtain 54 parts of a yellow compound having the following structural formula. Elemental analysis values are C=36.53, H=
1.02, N=3.23, halogen 51.89%, calculated value C=36.61, H=0.91, N=3.16, halogen 52.10%.

The infrared absorption spectrum of this compound is shown in FIG. λMa
x = 425 mμ (dimetino medium adjoining liquid)

[Brief explanation of drawings]

1 and 3 to 5 are infrared absorption spectra of the novel compound of the present invention shown in Examples, and FIG. 2 is a mass spectrum of the compound of the present invention (Example 1).

Claims (1)

[Claims] 1 General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼......[I] [However, X and Y in the formula represent chlorine atoms or bromine atoms] Yellow color represented by organic compound.