JPH0726340B2 - Dye manufacturing method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for coloring an organic material, and more particularly to a method for coloring an organic material which gives a colored product excellent in heat resistance, sharpness, transparency and the like.

(Prior art and its problems) Conventionally, as a method for coloring synthetic fibers such as polyester,
A dyeing method using a disperse dye and a stock solution coloring method using a pigment are widely used.

Dyeing with a disperse dye is for dyeing polyester fibers with a dye having a relatively low molecular weight, and a beautiful colored fiber is provided, but since the molecular weight of the dye is small, heat resistance such as sublimation resistance is low. It is insufficient and causes various problems during heat treatment.

On the other hand, in the case of the stock solution coloring method using a pigment, the heat resistance problem as described above is small, but there is a problem in the dispersibility of the pigment.
There is a problem of nozzle clogging and color development during spinning, and there is a problem that the clarity and transparency of the colored product are insufficient because the pigment does not dissolve in the polyester.

There is no problem if such a sharpness or transparency is obtained by using a dye in the undiluted solution coloring method, but since the temperature during undiluted solution coloring is a high temperature of 200 to 300 ° C or higher, the dye is easily thermally decomposed and the dye The stock solution coloring method is difficult.

The above-mentioned problems are not limited to polyester, and occur similarly in other synthetic resins and synthetic fibers such as polyethylene, polypropylene, polyamide and polycarbonate.

Therefore, an object of the present invention is to provide a method for coloring an organic material, which gives a colored product excellent in heat resistance, sharpness, transparency and the like.

(Means for Solving Problems) The above object is achieved by the present invention described below.

That is, the present invention is characterized by using a quinophthalone dye represented by the following general formula (I) and a dye represented by the following general formula (II) obtained by reacting N-hydroxymethylphthalimide or a derivative thereof. It is a method of coloring an organic material.

(A ring in the above formula is a benzene ring or a naphthalene ring, and R _{1 to} R ₃ are hydrogen atoms, halogen atoms, lower alkyl groups, lower alkoxy groups, phenyl groups, benzoyl groups, acyl groups, nitro groups or amino groups. (Function) The dye represented by the following general formula (I) is conventionally known,
It is called a quinophthalone dye and is widely used as a disperse dye for synthetic fibers such as polyester.

(R ₁ and R ₂ in the formula have the same meanings as described above.) When the above quinophthalone dye is used in a stock solution coloring method for a synthetic resin such as polyester, the high temperature during stock solution coloring causes
It cannot be used due to sublimation or thermal decomposition.

On the other hand, by bonding a phthalimidomethyl group or a group of a derivative thereof to the quinophthalone dye, the heat resistance is remarkably improved, and there is no sublimation or thermal decomposition due to the high temperature at the time of coloring the undiluted solution. Unlike an organic pigment, it dissolves in a synthetic resin that is a material to be colored, so that a colored product that is uniformly beautiful and has excellent sharpness and transparency is provided.

(Preferred Embodiment) The dye of the general formula (II) used in the present invention is obtained by reacting the known quinophthalone dye of the general formula (I) with N-hydroxymethylphthalimide or a derivative thereof.

The quinophthalone dye used is represented by the above general formula (I).
R ₁ and R ₂ are preferably hydrogen atoms, but halogenated quinophthalone dyes obtained by halogenating this are also preferably used, and R ₁ and / or R ₂ is a methyl group, an ethyl group or a propyl group. It may have a lower alkyl group, a lower alkoxy group such as a methoxy group, an ethoxy group and a propoxy group, and a substituent such as a nitro group.

The N-hydroxymethylphthalimide or its derivative reacted with the quinophthalone dye is a known compound obtained by reacting phthalimide or its derivative with formalin, and preferred specific examples thereof include N-hydroxymethylphthalimide and N. -Hydroxymethyl-4-nitrophthalimide, N-hydroxymethyl-3-nitrophthalimide, N-hydroxymethyl-3-hydroxyphthalimide, N-hydroxymethyl-3-chlorophthalimide, N-hydroxymethyl-4-chlorophthalimide, N -Hydroxymethyl-3,6-dichlorophthalimide, N-hydroxymethyl-3,4,5,6-tetrachlorophthalimide, N-hydroxymethyl-3,4,5,6-tetrabromophthalimide, N-hydroxymethyl- 3-amino Talimide, N-hydroxymethyl-4-aminophthalimide, N-hydroxymethyl-3-methoxyphthalimide, N-hydroxymethyl-3-methylphthalimide, N-hydroxymethyl-4-methylphthalimide, N-hydroxymethyl-4,5 -Dibromophthalimide and the like.

The reaction between the quinophthalone dye and N-hydroxymethylphthalimide can be performed by dehydration condensation of both,
Although any method capable of dehydration condensation is effective, a particularly preferable method is to dissolve both in concentrated sulfuric acid (eg, 95 to 99%) and react at a temperature of about 10 to 100 ° C for 1 to 24 hours. The desired dye, which is represented by the general formula (II), is obtained (for details, refer to the reference example described later).

The reaction between the two is preferably carried out at a ratio of 1 to 3 mol of N-hydroxymethylphthalimide or its derivative per mol of quinophthalone dye, and especially 0.8 mol of N-hydroxymethylphthalimide or its derivative per mol of quinophthalone dye.
By reacting 1 to 1.5 mol of the quinophthalone dye with 1 mol of N-hydroxymethylphthalimide or a derivative thereof, a product obtained by reacting 1 mol of the quinophthalone dye with 1 mol of the product is obtained.

Although the bonding position of the N-hydroxymethylphthalimide group or its derivative group is not clearly confirmed, it is highly possible that it is bonded to the ortho position of the hydroxyl group of the quinophthalone dye.

It is a yellowish powder of the dye represented by the general formula (II) obtained as described above, has a maximum absorption wavelength between 440 and 450 nm, and has sufficient thermal stability against temperatures up to about 300 ° C. have.

Typical examples of organic substances colored by the dye represented by the general formula (II) are thermoplastic synthetic resins such as polyester resin, polyamide resin, polypropylene resin, polyethylene resin, polystyrene resin, polyvinyl chloride resin and polycarbonate resin. Is. Particularly, the polyester resin which is made into fiber is most suitable. Of course, in the present invention,
Not limited to these resins, it is possible to color other organic substances such as paints, printing inks and oils.

The coloring method is not particularly limited, but a preferred method is a stock solution coloring method. This stock solution coloring method uses resin pellets containing the dye represented by the general formula (II) per 100 parts by weight of the resin.
It is a method of adding 0.01 to 1 part by weight, melt-kneading the mixture, and extrusion-molding, injection-molding, melt-spinning, and a method of adding the above-mentioned dye to a resin-forming monomer to perform polymerization and coloring. Other known methods can be used as well.

(Effect) According to the present invention as described above, a colored product having excellent heat resistance, sharpness, transparency and the like can be easily provided.

(Example) Next, the present invention will be described more specifically with reference to Examples and Examples. In the text, parts and% are based on weight unless otherwise specified.

Reference Example 1 28.9 parts of 3'-hydroxy-quinophthalone was added to 98% sulfuric acid 580
Dissolve in parts with stirring at a temperature of 20 to 25 ° C. Add 18.6 parts of N-hydroxymethylphthalimide to this
Stir for 24 hours at a temperature of 20-25 ° C. Then, the reaction product was gradually added to 6,000 parts of ice water at a temperature of 10 ° C or lower, the precipitated crystals were filtered, washed with water to neutrality, and then dried at 90 ° C to obtain 42.6 parts of a novel yellow dye represented by the following formula. can get. The thermal decomposition point of this dye is 290 ° C, and the maximum absorption wavelength is 443 nm. Further, this dye colors a synthetic resin such as polyester in a bright yellow color to give a colored product having excellent heat resistance, sharpness and transparency.

Reference example 2 28.9 parts of 3'-hydroxy-quinophthalone was added to 98% sulfuric acid 580
Dissolve in parts with stirring at a temperature of 25-30 ° C. To this was added 33.1 parts of N-hydroxymethyl-3,4,5,6-tetrachlorophthalimide and the mixture was stirred at a temperature of 25 to 30 ° C for 24 hours. Then, the reaction product was gradually added to 6,000 parts of ice water at a temperature of 10 ° C or lower, and the precipitated crystals were filtered, washed with water to neutrality, and dried at 90 ° C to obtain 55.7 parts of a novel yellow dye represented by the following formula. can get. The thermal decomposition point of this dye is 320 ° C., and the maximum absorption wavelength is 444 nm.

Reference Example 3 28.9 parts of 3'-hydroxy-quinophthalone and N as raw materials
-Hydroxymethyl-4-nitrophthalimide (23.3 parts), 98% sulfuric acid (580 parts) as a solvent, and the same treatment as in Reference Example 1 except that the novel yellow dye 46.8 shown below was used.
Part is obtained. The thermal decomposition point of this dye is 285 ° C, and the maximum absorption wavelength is 442 nm.

Reference Example 4 28.9 parts of 3'-hydroxy-quinophthalone and N as raw materials
-Hydroxymethyl-4-methylphthalimide (20.1 parts), 98% sulfuric acid (580 parts) as a solvent and the same treatment as in Reference Example 1 except that the novel yellow dye 4 represented by the following formula:
3.9 copies will be obtained. The thermal decomposition point of this dye is 305 ℃,
The maximum absorption wavelength is 446mn.

Reference Example 5 The dyes shown in Table 1 below were obtained in the same manner as in Reference Examples 1 to 4 except that the raw materials shown in Table 1 below were used.

Example 1 A sheet prepared by kneading 0.5 parts of the dye of Reference Example 1 and 1.0 part of Pansolve H was mixed with 50 parts of polyvinyl chloride resin compound and roll-kneaded with a 6-inch roll at 155 to 160 ° C. for 3 minutes. Was formed, and this sheet was press-molded at a temperature of 170 ° C. and a pressure of 50 kg to a thickness of 5 mm, and was colored transparent pure yellow.

Example 2 A finely pulverized product of the dye of Reference Example 2 (5 parts) was mixed with 1,000 parts of polyethylene and injection-molded at 250 ° C. The molded product was transparent and uniformly colored yellow.

Example 3 10 parts of the dye of Reference Example 3, 1 part of a dispersant and 89 parts of ethylene glycol were ground with a ball mill, and 15 parts of this ground product was transesterified from 1 mol of dimethyl terephthalate and 2 mol of ethylene glycol. The product was added to 100 parts and heat-polymerized under reduced pressure at about 280 ° C. for 4 hours to obtain a uniformly and beautifully colored yellow polyester. When this colored polyester was spun according to a conventional method, a spinning nozzle was not clogged at all, and a polyester fiber excellent in transparency and sharpness was obtained. This fiber bundle was sandwiched between two white polyester sheets and heat-treated at 120 ° C. under a pressure of 20 kg for 2 hours, but no dye transfer to the white polyester sheet was observed.

Example 4 1 part of the dye of Reference Example 4 and 200 parts of polyethylene terephthalate resin pellets were mixed, and 3 denier fiber was spun with a residence time of 8 minutes in a dry spinning device at a temperature of 290 to 300 ° C. No polyester was clogged and a polyester fiber excellent in transparency and sharpness was obtained. Insert this fiber bundle between two white polyester sheets 12
When heat-treated at 0 ° C. under a pressure of 20 kg for 2 hours, transfer of the dye to the white polyester sheet was not observed.

The dyes of the other reference examples also give colored products excellent in heat resistance, sharpness and transparency as in Examples 1 to 4.

Claims (4)

[Claims] 1. A dye represented by the following general formula (II) which is obtained by reacting a quinophthalone dye represented by the following general formula (I) with N-hydroxymethylphthalimide or a derivative thereof. How to color organic materials. (A ring in the above formula is a benzene ring or a naphthalene ring, and R _{1 to} R ₃ are hydrogen atoms, halogen atoms, lower alkyl groups, lower alkoxy groups, phenyl groups, benzoyl groups, acyl groups, nitro groups or amino groups. It is.) 2. The method for coloring an organic material according to claim 1, wherein the organic material is a thermoplastic synthetic resin. 3. The method for coloring an organic material according to claim 1, wherein the dye represented by the general formula (II) and the synthetic resin are melt-kneaded. 4. The method for coloring an organic material according to claim 1, wherein the organic material is a polyester resin.