JPS6019780B2 - New phthalide derivatives, their production methods, and methods for coloring organic materials. - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula (wherein R represents a 1,4-phenylene group, a 4,4'-biphenylene group, or a 4,4''-terphenylene group, which may contain a methyl group or a methoxy group, A, and represent a phenyl group which may contain a halogen atom or a methyl group, and represent a hydrogen atom or a phenyl group, respectively.

Also, A, and A2, A2 and A3, or A3 and A4,
It also includes the case where they are combined to form a benzene ring or a naphthylene group. ), as well as its preparation and use as a coloring agent. Conventionally, many organic colorants for organic materials have been known, and among them, isoindolinone compounds, flavanthrone compounds, and azo compounds are known as yellow ones. However, these yellow organic colorants have
There are problems in that there are few satisfactory light fastness and other properties, and the manufacturing method is complicated and expensive. The inventors of the present invention have conducted intensive studies with the aim of obtaining a new coloring agent that has performance comparable to existing organic colorants in terms of light resistance and heat resistance, and is extremely easy to manufacture. The present invention was completed based on the knowledge that the compound represented by formula (1) satisfactorily achieves this objective. The present invention is based on the general formula (where A, A2, A3, and A4 are the same as above).

) and a phthalic anhydride derivative represented by the general formula ratio N-R-NH2 (m) (in the formula, R
is the same as above. ) in a weakly basic organic solvent, and then treated with a dehydrating agent. Examples of the phthalic anhydride derivative represented by the general formula (b) include 3.
6-diphenyl phthalic anhydride, 3-phenyl-6-P-
Chlorophenyl phthalic anhydride, 31P-chlorophenyl-61P-methylphenyl phthalic anhydride, 3-phenyl-6-P-bromophenyl phthalic anhydride, 3, 4, 5
・6-tetraphenyl phthalic anhydride, 3,6-diphenyl-4,5-di-P-chlorophenyl phthalic anhydride, 3
・6-di-P-chlorophenyl-4,5-diphenyl phthalic anhydride, halogen substituted product of 3,4,5,6-tetraphenyl phthalic anhydride, 3,6-diphenyl-4,5-benzo phthalic anhydride, or Halogen substituted product of the phenyl group, 7,10-diphenylfluoranthene-8,9
-dicarboxylic acid anhydride or its nuclear halide, 3,4,5,6-dibenzophthalic anhydride, etc.

Synthesis methods for these phthalic anhydride derivatives are known, and for example, phenyl-substituted phthalic anhydride derivatives can be obtained as shown in Table 1.

Table 1 In the formulas, X, Y, X' and Y represent hydrogen atoms or halogen atoms.

Further, dibenzophthalic anhydride can be obtained as follows. Further, examples of aromatic diamine derivatives represented by the general formula (m) include 1,4-phenylenediamine, 2-methyl-1,4-phenylenediamine, and 2-methoxy 1,4-phenylenediamine.
4-phenylenediamine, benzidine, 0-tolidine,
Examples include ○-dianisidine and 4,4″-diaminoterphenyl.

The ratio of the above-mentioned phthalic anhydride derivative and aromatic diamine used in the reaction is most appropriately 2 mol to a slight excess of 2 mol to 1 mol of the aromatic diamine derivative.

In order to react the phthalic anhydride derivative and the aromatic diamine derivative, a weakly basic organic solvent with high solubility is used as the reaction solvent, examples of which include dimethylformamide, dimethylacetamide, N-methylpyrrolidone, Examples include hexamethylphosphamide. The amount of these organic solvents to be used is preferably in the range of 3 to 2 ps of the total amount of the reactants, that is, the sum of the weights of the phthalic anhydride derivative and the aromatic diamine derivative used. Further, as the dehydrating agent, phosphorus trichloride, phosphorus oxychloride, thionyl chloride, phosgene, etc. are suitable. The amount of these dehydrating agents used is 0.5 to 1 mole of phthalic anhydride derivative.
Advantageously, the amount is 4 mol. In carrying out the reaction for producing the compound represented by the general formula (1), first the phthalic anhydride derivative represented by the general formula (b), the aromatic diamine derivative represented by the general formula (m), and the above-mentioned weak A basic organic solvent is mixed and allowed to stand for an appropriate period of time to carry out the condensation reaction. This reaction depends on the type of phthalic anhydride derivative and the type of aromatic diamine (
Particularly when there is a substituent at the ortho position of the amino group) heating is required to around 100 o'clock, but of course at room temperature (20 qo)
In some cases, there may be a sufficient reaction in the vicinity. The reaction time is preferably 30 minutes or more, for example 1 to 2 hours. After this condensation reaction, the above-mentioned dehydrating agent is added dropwise to the reaction solution, and the cyclization reaction is carried out by continuing the mixing.

In this case, the reaction temperature may be around room temperature, and the reaction time may be about 2 hours. By carrying out the cyclization reaction in this manner, the generated target product is precipitated.

This is strained and washed with a reaction solvent, then treated with a large amount of hot water to remove impurities, strained, and washed with water. A novel phthalide derivative represented by the general formula (1) can be obtained by washing with methanol or the like if necessary and drying. The compound of general formula (1) thus obtained is a fine powder having a hue ranging from yellow to light yellow,
Its melting point is above 300° C., slightly soluble in aromatic hydrocarbons, chlorinated hydrocarbons or nitrated hydrocarbons, and insoluble in water. The compound represented by the general formula (1) of the present invention is an organic material, such as a synthetic or semi-synthetic organic polymer material, such as a polyolefin type, polystyrene or a copolymer thereof, a resin type, a polymethacrylic type, a polyester Acrylic type, polyvinyl chloride type, polychloride pinylidene type, polyamide type, polycarbonate type, urea or melamine-formaldehyde type, sulfonamide resin type, polyester type, alkyd resin or its modified product,
It can be applied as a coloring agent to organic polymeric materials such as cellulose ether type or cellulose ester type. In the present invention, in order to color the above organic material using the compound represented by the general formula (1), for example, these organic materials and the compound represented by the general formula (1) are blended and mixed. Do it by doing this.

If necessary, cross-wire heating. This makes it possible, for example, to color paints. Further, by molding using a common processing method such as compression molding, injection molding, calender molding, or extrusion molding, it is possible to color molded products such as films, sheets, pipes, etc. In the above coloring method,
The amount of the compound of the present invention can be changed depending on the hue, color density, etc. of the intended colored product, but in the case of resin molded products, it is 0.01 to 2%. W. A range of R (0W.R means per weight of resin) is suitable. In addition, when used as a coloring agent in paints, it accounts for 0.1 to 20% of the solid components of paints.
(weight) is appropriate. The compound represented by the general formula (1) has good compatibility with the organic material, but in order to further improve this compatibility, a lubricant or other suitable dispersing agent is added to form a fine powder before use. It's also good to do. It is also possible to obtain a colored organic material by blending the compound represented by formula (1) into a liquid monomer or prepolymer and then polymerizing and curing the compound.

It can also be used as a coloring component of ink, and can be used in a wide range of applications as a colorant. Next, Table 2 illustrates the hue of the melamine-alkyd resin coating obtained by using the compound represented by the general formula (1) of the present invention as a colorant.

The coating was produced under the following conditions (parts are by weight).

A mixture of 70 parts of modified phthalkyd resin 133-60 (manufactured by Hitachi Chemical Co., Ltd., Solventsha) and 3 parts of melamine resin Ruban-2 E-60 (manufactured by Mitsui Toatsu Co., Ltd., Solventsha) was prepared. Take 95 parts of this mixture, mix with 5 parts of the coloring agent of the present invention (represented by compound numbers 1 to 21) and 45 parts of a mixed solvent of 8 xylene and 2 n-butanol, and mix at room temperature. Add the weight of glass grade granules and stir at 160 pm for 6 minutes. Separate the glass grains and apply the resulting paint to a paper or metal slope in a layer of 40# thick.
Bake for 30 minutes at qo. In addition, the general formula (1
) The structure of the phthalide derivative represented by the following formula (wherein A is an o-phenylene group and R is the same as above).

) represents the hue of the film when A and R were variously changed. Moreover, regarding the compounds of compound numbers 1 to 21,
Infrared absorption spectrum diagrams of each were taken using the KBr tablet method and are shown in Figures 1 to 21.

The vertical axis of the scale values in each drawing is the transmittance (Perc).
ent transmission), the lower horizontal axis is the wave number (
Wavenumber, skin-1), the upper machine axis is the wavelength (W
Represents the avelength ratio (mountain surface).

Table 2 Table 2 (continued) Table 2 (continued) Table 2 (continued) As seen in Table 2, the hue of the compound represented by general formula (1) is greatly influenced by the structure of the phthalide derivative. .

As a coloring agent, this phthalide derivative has excellent light resistance and heat resistance, and can withstand conditions of 180 pm and 3 pm when mixed with, for example, melamine-phthalkyd side fat baking paint. The light resistance of the coated coating was also good, and no browning was observed when irradiated with a Carbon Arc Fade Meter 10 or the like. It also has good migration resistance and can be heated to 150°C for 30 minutes.
Migration due to heating is not observed. It shows good fastness to various types of resistance required for other pigments. Furthermore, when used for coloring polyolefin resins, etc., the heat resistance, light resistance, migration resistance, and other fastness properties are good. Other general properties required of pigments are good. Next, the method of synthesis and use thereof will be explained in more detail with reference to Examples.

In the text, parts mean parts by weight.

Example 1 Synthesis of 1,4-phenylene-bis-tetraphenyliminophthalide (compound number-7 in Table 2) Add 5.4 parts of paraphenylenediamine as a powder to 20 Ikarito dimethylformamide and stir well to dissolve. do.

When 45.2 grams of tetraphenyl phthalic anhydride powder is added and stirred at room temperature, a weak heat is generated and the mixture dissolves, and white crystals eventually precipitate. (70-80q depending on the case)
It may be added to o. ) After stirring with water at room temperature, 25 parts of phosphorus trichloride was added dropwise to the mixture in 3 dishes, then the mixture was stirred at room temperature, and the yellow precipitate formed was strained and washed with a small amount of dimethylformamide to remove the cake. The mixture was thoroughly squeezed, mixed with a large amount of hot water, strained again, washed with water, and dried to obtain the desired compound in almost quantitative yield. Other compounds listed in the second list were also synthesized using the same machine.

In the case of compounds having o-substituted amines such as o-tolidine as a structural factor, the reaction between phthalic anhydride derivatives and diamines is
It has been advantageous to carry out the reaction at temperatures up to 100 qo water. Example 2 2 parts of the compound No. 4 in Table 2 was mixed with 1000 parts of PoIJ propylene resin pellets (Mitsui Noblen JHG), kneaded in a cylinder heated to 21000, and injection molded to give a bright yellow color. I got a colored plate.

This kneading was carried out for 15 minutes at 270°C to obtain a plate having exactly the same color tone as that produced by injection molding at 210°C. Place these plates in a carbon arc feed meter.
No browning was observed after irradiation for 0 field hours. The same machine was colored using compounds listed in Table 2 other than Compound No. 4, and good results were obtained. Example 3 Table 2 Compound No. 13
0.5 parts of the compound, 5 parts of rutile titanium oxide and AB
Mix 1000 parts of S resin and use an extruder to
It was extruded and made into a colored pellet at 0 to 220 oo.

This pellet was injection molded from a 23,000 heated cylinder to yield a tan plate. This plate showed good lightfastness and bleed resistance. Using compounds listed in Table 2 other than Compound No. 13, A-mo resin was colored in the same manner as described above, and good results were obtained. Example 4 0.5 part of compound No. 10 in Table 2 was mixed with 1000 parts of polystyrene resin pellets (Tobolex 525-51, manufactured by Toyo Polystyrene ■), kneaded in a cylinder heated to 18000 °C, and injection molded. A plate colored yellow was obtained.

The fastness of this plate was good. Compound number 10
Polystyrene resin could be colored in the same manner as above using the other compounds listed in Table 2, and good results were obtained. Example 5 0.1 part of the compound No. 1 in Table 2 was kneaded with a mixture consisting of 5 parts of polyvinyl chloride and 5 parts of dioctyl phthalate at 15 and 0 for 10 minutes, and then at 160
It was pressed for 5 minutes between metal plates kept at ℃ to form a sheet with a thickness of 5 ribs.

The obtained sheet exhibited a yellow color with good fastness. Using the same machine, polyvinyl chloride was colored using compounds listed in Table 2 other than Compound No. 1, and good results were obtained. Example 6 Two parts of fine powder of the compound No. 7 in Table 2 was mixed with a xylene-butanol (4:1) solution containing 7 ethylene glycol esters of acrylic acid-methacrylic acid copolymer and thoroughly dispersed. Ta.

To this is added a solution of xylesophtanol (4:1) containing 2 parts of butylated methylol melamine and 1 part of cellulose acetate butyrate and mixed well. Further 2.
Add 2 parts of aluminum pigment (non-IJ-fing type) and paint it on a metal plate to form a film with a thickness of 25 cm,
After baking for 0 minutes, a clear greenish-yellow film was obtained. The yellow color of this film was excellent in resistance to erosion and other various fastnesses.
Using short oil type modified phthalkyd resin instead of acrylic acid ester, using titanium dioxide instead of aluminum pigment,
A similar yellow opaque film was obtained.

In addition, a lacquer consisting of nitrocellulose-dioctyl phthalate alkyd resin (dry at room temperature or
00 short time drying) A yellow film with good fastness was obtained in the same manner. Good colored films were obtained in the same manner using compounds listed in Table 2 other than Compound No. 7.

Example 7 5% of a powdered compound of Compound No. 2 in Table 2 was added to a rosin maleic acid-modified polyester resin, thoroughly kneaded with boiling oil and a solvent to form a printing ink, and this was printed on a suitable substrate. A yellow print with good fastness was obtained.

A printing ink prepared in the same manner using a long oil alkyd resin or a modified phenolic resin in place of the maleic acid-modified polyester gave a bright yellow printed surface when printed on a metal surface. A second compound other than compound number 2
Printed matter with good fastness was obtained in the same manner using the compounds shown in the table. Example 8 5 parts of the compound No. 6 in Table 2 was added to Oresta-Q-60.
2 (Mitsui Tosho acrylic polyol, non-volatile content 50%)
4 parts and appropriate amount of solvent (xylene-butyl nitrate, 4 parts
:1) and thoroughly mixed and dispersed.

4.8 parts of Desmodyur N-75 (manufactured by Bayer, diazocyanate compound) was mixed with this, and the mixture was applied onto a suitable surface and left to dry at room temperature for a long time to obtain a yellow coating film with good fastness. A yellow coating film with good fastness was obtained in the same manner using compounds listed in Table 2 other than Compound No. 6.

[Brief explanation of the drawing]

1 to 21 show infrared absorption spectrum diagrams corresponding to compounds 1 to 21 shown in Table 2 of the specification, respectively. Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 Figure 12 Figure 13 Figure 14 Figure 15 Figure 16 Figure 17 Figure 18 Figure 19 Figure 20 Figure 21

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is a 1,4-phenylene group, 4,4'-biphenylene group, or Represents a 4,4″-terphenylene group, A_
1 and A_4 represent a phenyl group that may contain a halogen atom or a methyl group, and A_2 and A_3
each represents a hydrogen atom or a phenyl group. Also, A_1 and A_2 and A_3 or A_3 and A_4
This also includes the case where these are combined to form a benzene ring or a naphthylene group. ) A novel phthalide derivative represented by 2 General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, A_1 and A_4 represent a phenyl group that may contain a halogen atom or a methyl group, and A_2
and A_3 each represent a hydrogen atom or a phenyl group. Also, A_1 and A_2, A_2 and A_3 or A_3
and A_4 may be combined to form a benzene ring or a naphthylene group. ) and a phthalic anhydride derivative represented by the general formula H_2N-R-NH_
2 (III) (In the formula, R represents a 1,4-phenylene group, a 4,4'-biphenyl group, or a 4,4''-terphenylene group, which may contain a methyl group or a methoxy group.) A general formula that is characterized by condensing aromatic diamine with a weakly basic solvent and then treating with a dehydrating agent ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R, A_1, A_2, A_3 , and A_4 are the same as above.) A method for producing a novel phthalide derivative.
3 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R is a 1,4-phenylene group, 4,4'-biphenylene group, or 4,4''-terphenylene group, which may contain a methyl group or a methoxy group. Represents the base, A_
1 and A_4 represent a phenyl group that may contain a halogen atom or a methyl group, and A_2 and A_3
each represents a hydrogen atom or a phenyl group. Also, A_1 and A_2, A_2 and A_3 or A_3
and A_4 may be combined to form a benzene ring or a naphthylene group. ) A method for coloring organic materials, characterized by using a novel phthalide derivative represented by