JPS6012373B2 - Yellow organic compound, its production method, and colored composition containing the same - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel yellow compound, its production method, and its use as a polymeric colorant. More specifically, the present invention relates to a quinophthalone-based yellow compound suitable as a beam pigment, which has particularly excellent light resistance, heat resistance, and migration resistance. Conventionally, many compounds have been known as quinophthalone compounds, but compounds suitable as beam pigments, particularly those having excellent heat resistance and light resistance, are not well known. The present inventors found that when a certain specific compound is reacted, the formula [1] [wherein R represents a lower alkyl group or a lower alkoxy group, × represents a halogen atom, and Y represents two carbonyl groups] Represents a phenylene group or naphthylene group (these groups may be substituted with a nonionized substituent such as a halogen atom) bonded at the ortho position or the perpendicular position, and rings A and B are substituted with a halogen atom. may have been done. A novel compound represented by the following formula was obtained, and it was discovered that this compound has excellent heat resistance and light resistance, and is suitable as a beam pigment, and the present invention was achieved. That is, the present invention is based on the general formula [1] [wherein R represents a lower alkyl group or a lower alkoxy group, X represents a halogen atom, and Y is bonded to two carbonyl groups at the ortho position or the perpendicular position. represents a phenylene group or a naphthylene group (these groups may be substituted with a nonionizable substituent such as a halogen atom), and rings A and B may be substituted with a halogen atom. ], a method for producing the same, and a colored composition containing the same. The compound represented by the general formula [1] of the present invention has the following tautomeric structures, but the compound represented by the general formula [1] in the present invention has all of these structural formulas [11a
], [1], and [11b]. One of the characteristics of the novel yellow compound according to the present invention is its migration resistance when used as a pigment for coloring plastics. For example, the novel compound of the present invention having the following structural formula [V] (
(See Example 1) has a migration resistance of grade 5 on a gray scale, whereas the compound represented by the following structural formula [V'] has a migration resistance of grade 2, and the migration resistance of the compound represented by the following structural formula [V'] is grade 2. The group has the effect of dramatically improving migration resistance. The general formula used as a starting material in the present invention [
Specific examples of compounds represented by m] include 5-amino-8-methyl-quinaldine, 5-amino-8-ethyl-
Examples thereof include quinaldine, 5-amino-8-methoxyquinaldine, and the like. Specific examples of compounds represented by Y(COOH)2 include phthalic acid, monochlorophthalic acid, dichlorophthalic acid, tetrachlorophthalic acid, monopromophthalic acid, dibromophthalic acid, tetrabromophthalic acid, and 1,8-naphthalic acid. , 3- or 4-chloro-1,8-naphthalic acid, 3- or 4-chloro-1,8-naphthalic acid, naphthalene-2.
3-dicarboxylic acid, dibromnaphthalene-2,3-dicarboxylic acid, tetrab. Examples include munaphthalene-2,3-dicarboxylic acid and naphthalene-112-dicarboxylic acid. Therefore, examples of the compound represented by Y(CO)20 include acid anhydrides corresponding to the dicarboxylic acids mentioned above. Yellow organic compound of the present invention Aminoquinaldines represented by the above general formula [m] and general formula [W], that is, Y(COO
A compound represented by H)2 or Y(C02)○ is heated and condensed to obtain an imidized quinaldine derivative represented by the general formula [B], and then a tetrahalogenated phthalic acid such as tetrachlorophthalic acid, tetrabromophthalic acid, or It is produced by heating and reacting with those acid anhydrides. When Y(COOH)2 represents tetrachlorophthalic acid or tetrabromophthalic acid and a compound represented by the following general formula [W] is synthesized, [wherein R and X are the same as above]. ] The aminoquinaldine derivative represented by the general formula [m] and two molecules of tetrahalogenated phthalic acid or its anhydride can be condensed at once. In addition, dicarboxylic acid Y(COOH)2 or its anhydride Y(C
O) Even if the tetrahalogenated phthalic acid or its anhydride used in the second stage condensation is different from 20, there may be a compound in the middle.

It is not necessary to isolate [0], but first Y(
A second reaction can be carried out by carrying out imidization with COOH)2 or Y(CO)20 and subsequently adding tetrahalogenated phthalic acid or its anhydride. The above two condensation reactions in the present invention can be carried out in the presence or absence of a solvent. When the reaction is carried out in the presence of a solvent, the solvent to be used is an organic solvent that is non-trivalent to the reaction, such as nitrobenzene, orthodichlorobenzene, trichlorobenzeso, trimethylbenzene, decalin, tetralin, diphenyl ether, chlornaphthalene. , N-methylpyrrolidone, etc. are used. The amount used may be 1 to 2 times the weight of the reactant, and a larger amount of solvent may be used, but from the viewpoint of solvent recovery after the reaction, it is preferably 2 to 1 times the cloud weight.
Furthermore, the ratio of the aminoquinaldine represented by the above general formula [m] and Y(COOH)2 or Y(CO)20 may be within any range, but the following condensation reaction may be carried out without isolating the product m]. If this is to be carried out continuously, it is better to have a ratio close to 1:1 molar. Also general formula

The proportion of the imidized quinaldine derivative represented by [0] and the tetrahalogenated phthalic acid or its anhydride may be within any range, but it is usually 0.
．． It may be in the range of 3 to 3. The reaction can be carried out at a temperature range of 100 to 30 qo, preferably 150 to 270 qo.
is within the range of The synthesis of compound [b] by imidization of compound [m] proceeds easily by simply heating the raw material mixture at an appropriate temperature in the presence or absence of the above-mentioned solvent. It is preferable to remove the water generated at this time from the system. On the other hand, the compound [
Since the condensation reaction between [0] and tetrahalogenated phthalic acid or its anhydride is slower than the above-mentioned imidization reaction, the reaction temperature should be raised, or to make it more effective, a catalyst such as zinc chloride or aluminum chloride should be added. . After reacting in this way, to remove the target yellow quinophthalone compound from the reaction mixture, cool the reaction mixture, separate the precipitate, and wash it with dimethylformamide, dimethylacetamide, methanol, ethanol, or acetone. Bye. Alternatively, the above-mentioned solvent may be added to the reaction mixture before the reaction mixture is cooled and processed. If further purification is required, washing and recrystallization may be carried out using a solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, Q-chlornaphthalene, or the like. Alternatively, after cooling the reaction mixture, methanol, ethanol, dimethylformamide, etc. may be added to separate the precipitate. The quinophthalone-based yellow compound thus obtained can be further used after being made into a pigment by a conventional pigmentation method, as the case requires. The novel compound of the present invention produced by the method detailed above has excellent heat resistance, light resistance, migration resistance, and color tone, and is extremely useful as a coloring agent for polymeric materials. Polymer materials colored using the compounds of the present invention include:
Polyolefins such as polyethylene and polypropylene,
Polystyrene, polyester, polycarbonate,
A spots, polyacrylonitrile type, polyacrylate type,
Polyvinyl chloride-based, polyacetal-based, amino resin-based,
Materials include cellulose acetate, epoxy resin, and polyamide. When coloring a polymeric material using the compound [1] of the present invention, the polymeric material blended with the compound [1] is heated and kneaded, and then molded using a conventional method such as compression molding, injection molding, or calendar molding. Molded products such as films, sheets, fibers, pipes, and pellets can be colored yellow depending on the processing method, and a new compound represented by the general formula [1] can be added to liquid monomers and prepolymers to polymerize and harden them. It can also be colored using a cast molding method. 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 the general formula [1] with a polymeric material used in printing inks, it can also be used as a coloring agent for inks. The novel compound of the present invention exhibits excellent heat resistance, light resistance, migration resistance, and solvent resistance in the above-mentioned coloring method, colors polymeric materials in vivid yellow, and has excellent coloring effects. Next, examples will be shown. Note that "parts" in the examples are "parts by weight." Example 1 172 parts of 5-amino-8-methylquinaldine, 715 parts of tetrachlorophthalic anhydride, and 40 parts of anhydrous zinc chloride were mixed with 1.
The mixture was reacted in 200 parts of 2,4-trichlorobenzene at the boiling point for 3 hours under reflux, and then 50 liters of dimethylformamide was added and the mixture was heated under reflux at the boiling point for 1 hour. After furnace separation at 120 qo, the yellow reaction product was washed with 100 g of dimethylformamide, further washed with ethanol, and dried to obtain a yellow compound 59 represented by the following structural formula.
I got 7 copies. The maximum absorption in the visible absorption spectrum in dimethylformamide solution was 42 cm and 44 cm. The infrared absorption spectrum is -CO-N at 172 & Pig-1 and 1782 Skin-1.
-Absorption of CO-, 1625 arc-1, 1685 skin-1-
Absorption of CO-C-CO- was observed. C27 is 04N
The elemental analysis values for 2CI8 were as shown in the table below. Two parts of this compound and 30 parts of di-(2-ethylhexyl)-phthalate were mixed with 70 parts of polyvinyl chloride resin, and then kneaded with two rolls at 155 to 160 millimeters to obtain a bright yellow sheet. This colored sheet was placed between two white vinyl chloride sheets and left for 2 hours under a load of 80 mm and 9' kg, and a migration resistance test was conducted, and the result was grade 5 on the gray scale. When the same test was conducted on compound [V'], the result was grade 2. Example 2 172 parts of 5-amino-8-methyl-quinaldine, 148 parts of phthalic anhydride, and 80 parts of 112,4-trichlorobenzene
Anchorage was added and the mixture was reacted under reflux for 2 hours at the boiling point, then cooled, and the precipitated crystals were filtered out, washed with benzene, and dried to obtain 257 parts of 8-methyl-5-phthalimidoquinaldine. To this were added 365 parts of tetrachlorophthalic anhydride, 2000 parts of trichlorobenzene, and 4 parts of anhydrous zinc chloride, and the mixture was heated and reacted under reflux for 3 hours. 50 parts of dimethylformamide was added and the mixture was heated under reflux for 1 hour. A similar treatment was carried out to obtain compound 39, represented by the following structural formula.The maximum absorption in the visible spectrum in dimethylformamide solution was 41
He was 44 years old. 172 in infrared absorption spectrum
There was absorption of -CO-N-CO- in 5-1, 1780 skin-1, and absorption of -CO-C-CO- in 162&next-1, 1 Chomatsu-1. Elemental analysis value (%) is C=57.44,
H=2.10N=5.01, CI=24.37, calculated value (%) is C=56.87, H=2.12, N=4.91
, CI=24.87. 1.5 parts of this compound was blended with 100% polyethylene resin and mixed and extruded using a melt extruder at 23 mm to obtain pellets colored yellow. This pellet was injection molded under the conditions shown in Table 1 below to obtain a molded plate. At this time, no difference in color tone was observed depending on the injection conditions. Table 1 Injection molding conditions When this molded plate was irradiated with light using a weather meter and a light resistance test was conducted, it was judged to be grade 6 or higher on a pull scale. Example 3 The reaction and treatment were carried out in the same manner as in Example 1 using tetrabromo phthalic anhydride 116 base instead of tetrachlorophthalic anhydride to obtain 936 parts of a yellow compound having the following structural formula. The visible spectrum maximum absorption in dimethylformamide solution was 42 skin, 44 rule kite. 1 in infrared absorption spectrum
732 arc-1, 1778 stream-1 absorbs -CO-N-CO, 1630-1, 1690-1 absorbs -CO-C-
Absorption of CO was observed. Elemental analysis values (%): C = 30.56, H: 0.79 N
:2.51, Br=59.01, calculated value (%) is C=
30.48, H=0.67, N=2.63, Br=60
．． It was 11. This compound 0. The mixture was blended with 20 parts of polystyrene resin and mixed and extruded using a melt extruder at 23 parts to obtain a pellet colored yellow. This pellet was injection molded under the conditions shown in Table 2 below to obtain a molded plate. At this time, no difference in color tone was observed depending on the injection conditions. Table 2 Example of injection molding conditions 4 172 parts of 5-amino/-8-methyl-quinaldine and 464 parts of tetrabromine hydrothermal phthalic acid were mixed with 20 parts of trichlorobenzene.
The reaction was carried out under heating and reflux for 2 hours in the
- 532 parts of tetrapromophthalimidoquinaldine were obtained. To this were added 36 parts of tetrachlorophthalic anhydride and 200 parts of Q-chlornaphthalene, and the mixture was allowed to react under reflux for 2 hours.
The product was dispersed in 100 parts of Q-chlornaphthalene suitable for a hot furnace at 120 qo, washed with a heating lamp, heated in a hot furnace, washed with ethyl alcohol, and then dried to obtain the following structural formula. 671 parts of a yellow compound was obtained. The maximum absorption in the visible absorption spectrum in dimethylformamide solution is 421n “4
It was 4. According to the infrared absorption spectrum, 1732 Ka-1, 1780
Absorption of -CO-N-C○m in Ka-1, 1630 arc-1,
Absorption of -CO-C-CO- was observed in 1690ka-1. Elemental analysis values (%) are C: 36.49, H = 0.9, N = 3.04, halogen = 51.60, calculated values (%)
C=36.61, H=0.91, N=3.16, and halogen=52.10. Three parts of this compound was blended with polycarbonate resin 200 mm and melt-extruded at 260 to 265 oC to obtain a yellow colored pellet. The molded plate obtained by injection molding this pellet at a cylinder temperature of 28,000 showed no discoloration or fading when irradiated with light from a weather meter, and was grade 6 or higher on the blue scale. Example 5 188 parts of 5-amino-8-methoxyquinaldine and 715 parts of tetrachlorophthalic anhydride were reacted under reflux for 5 hours at the boiling point in 200 parts of Q-chlornaphthalene, and then 50 parts of dimethylformamide was added for another 1 hour. I was closely accompanied. After furnace separation at 120qC, dimethylformamide 100
The mixture was washed with a base layer, and finally washed with ethanol and dried to obtain 3 parts of a yellow compound having the following structural formula. The maximum absorption in the visible absorption spectrum is 42 and 44 (
dimethylformamide solution). Infrared absorption spectrum: 173 hyphen-1, 1775 arc-1
-CO-N-CO- absorption, 1635 arc-1, 169
Absorption of -CO-C-CO-1 was observed in Skin-1. Elemental analysis values (%) are C=45.24, H=1.09, N=3
．． 83, CI = plaque. 40, calculated value (%) is C=44.7
9, H=1.11, N=3.87, CI=39.18. 0.5 part of this compound was added and mixed with 500 parts of prepolymerized methyl methacrylate syrup, and this colored syrup was poured into a glass cell and polymerized at 50 to 70 qo for 6 hours, then for 100 to 120 qo for 3 hours, and then cooled and peeled off. A robust colored polymethyl methacrylate resin plate was obtained.
Example 6 94 parts of 5-amino-8-methoxy-quinaldine, 118
9 parts of mono-naphthalene dicarboxylic anhydride are reacted under reflux for 2 hours at the medium boiling point of 100 parts of Q-chloronaphthalene, and then 215 parts of tetrachlorophthalic anhydride is added and the reaction is further continued for 3 hours. 25 bales of dimethylformamide were added and refluxed for an additional hour. The yellow compound obtained by furnace separation at 120°C was washed with 50 parts of dimethylformamide, then washed with acetone, and dried to obtain compound 2 represented by the following structural formula.
Obtained 28 copies. The maximum absorption of the visible absorption spectrum in the dimethylformamide solution was 421n skin and 444 nm. Infrared absorption spectrum: 1700-1, 1715-1
-CO-N-CO- absorption, 163 ratio Ne-1, 168
&Yen-1 had absorption of -CO-C-CO-. Elemental analysis values (%) are C=58.69, H=2.24, N=4.
36, CI co21.84 calculated value (%) is C=58.52
, H=2.22, N=4.40 CI=22.29. 1 part of this compound, 6 parts of calcium carbonate powder, 4 parts of zinc stearate, 25 parts of styrene monomer, and 35 parts of finely powdered polystyrene were mixed in a ball mill, and 30 parts of glass fiber
Bobe, 240 parts of isophthalic acid type unsaturated polyester, and 1 dollar of calcium hydroxide were mixed, and a polymerization initiator was added to the mixture.
When heated and molded at 0:00 o'clock, a reinforced polyester molded product colored bright yellow was obtained. Example 7 1.8-Naphthalene dicarboxylic anhydride cutter 1.
Example 6 using 2-naphthalene dicarboxylic anhydride
In the same manner as above, 132 parts of a yellow compound having the following structural formula was obtained. The maximum absorption in the visible spectrum was 421 nm, which was the 44 rule skin. Infrared absorption spectrum: 1730 kyo-1, 1780 kyo-1
, absorption of -CO-N-CO-, 1633 Ne-1, 16
There was absorption of -CO-C-CO- in 90-1. Elemental analysis values (%) are C=58.69, H=2.20N
=4.44, CI=22.07, calculated value (%) is C=5
8.52, H=2.22, N=4.4ri CI=pine. 29
It is. 18 parts of this compound and 282 parts of a commercially available clear (melamiso-alkyd paint) were milled in a pot mill for 4 hours, diluted with thinner, sprayed on a tin plate, left for 15 minutes, and then brazed at 130°C for about minutes to create a clear color. A yellow painted board was obtained. Examples 8 to 14 Examples of characteristic absorption spectra of infrared absorption spectra and visible absorption spectra of various yellow organic compounds synthesized according to Example 6 from various aminoquinaldine derivatives and acid anhydrides are shown in the table below.

Claims (1)

[Claims] 1 General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼ [However, in the formula, R represents a lower alkyl group or lower alkoxy group, X represents a halogen atom, and Y represents two Represents a phenylene group or naphthylene group (these groups may be substituted with a nonionized substituent such as a halogen atom) bonded to a carbonyl group at the ortho or peri position, and rings A and B are halogen May be substituted with an atom. ] A yellow organic compound represented by 2 General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, in the formula, R represents a lower alkyl group or a lower alkoxy group, and Y is bonded to two carbonyl groups at the ortho or peri position. phenylene group or naphthylene group (
These groups may be substituted with nonionizable substituents such as halogen atoms. ), and rings A and B may be substituted with a halogen atom. ] An imidized quinaldine derivative represented by
General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, in the formula, R represents a lower alkyl group or a lower alkoxy group. , X represents a halogen atom, Y is a phenylene group or a naphthylene group bonded to two carbonyl groups at the ortho or peri position (these groups are substituted with a nonionizable substituent such as a halogen atom) ), and rings A and B may be substituted with a halogen atom. ] A method for producing a yellow organic compound represented by 3 General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. Represents a phenylene group or naphthylene group (these groups may be substituted with a nonionized substituent such as a halogen atom) bonded at the peri-position, and rings A and B are substituted with a halogen atom. Good too. ] When producing the yellow organic compound represented by the general formula [III] ▲ there are mathematical formulas, chemical formulas, tables, etc. Same as the definition of B. ] and the aminoquinaldine derivative represented by the general formula [I
V〕▲Mathematical formulas, chemical formulas, tables, etc.▼[However, in the formula Y
is the same as the definition of Y in formula [I] above. ] by reacting with a compound represented by the general formula [II]▲
There are mathematical formulas, chemical formulas, tables, etc.▼ [However, in the formula, R, rings A, B, and Y are R in the above formula [I],
Same as the definitions of rings A, B and Y. ], and then condensing the same with tetrahalogenated phthalic acid or its anhydride under heating. 4 General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, in the formula, R represents a lower alkyl group or lower alkoxy group, X represents a halogen atom, and Y represents two carbonyl groups and the ortho position or Represents a phenylene group or naphthylene group (these groups may be substituted with a nonionized substituent such as a halogen atom) bonded at the peri-position, and rings A and B are substituted with a halogen atom. Good too. ] A colored polymeric material composition containing a yellow organic compound represented by the following as a coloring component.