JPS6213989B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula () (In the formula, R ₁ and R ₂ are each a hydrogen atom,
Represents any one of a halogen atom, a lower alkyl group, and a lower alkoxy group. However, R ₁ , R ₂
cannot be hydrogen at the same time. ) is related to a novel azomethine pigment. The compounds represented by the general formula () are useful pigments colored in various colors depending on the types of substituents R ₁ and R ₂ in the formula. For example, as shown in the examples below,
When R ₁ and R ₂ each contain a hydrogen atom, a chlorine atom, a methyl group, or a methoxy group, the pigment exhibits a very clear reddish-yellow to yellow color. A compound represented by the general formula () is a compound represented by the formula () For 2 moles of 3-imino-4,5,6,7-tetrachloroisoindolin-1-one represented by the general formula () (In the formula, R ₁ and R ₂ have the same meanings as in the general formula ().)
Obtained by reaction in an inert solvent. 3-imino-4,5,6, represented by the formula ()
7-tetrachloroisoindolin-1-one is
Obtained by hydrolyzing tetrachlorophthalonitrile in an acetone-water mixed solvent using ammonia and hydrogen peroxide as catalysts. In addition, the above-mentioned tetrachlorophthalonitrile is, for example,
According to the method described in No. 36-5716, phthalonitrile is obtained by subjecting it to a gas phase chlorination reaction using activated carbon as a catalyst. Various diisocyanate compounds represented by the general formula () can be considered depending on the types of R ₁ and R ₂ , and the R ₁ and R ₂ of the compound represented by the general formula () are as follows _. and synthesized as _R2 . Specific examples of the isocyanate compound include 3,3'-dichloro-4,4'-diphenylmethane diisocyanate (R ₁ :Cl, R ₂ :H), 3,
3'-dimethyl-4,4'-diphenylmethane diisocyanate (R ₁ : CH ₃ , R ₂ : H), 3,3'-methoxy-4,4'-diphenylmethane diisocyanate (R ₁ : OCH ₃ , R ₂ :H), 3,3'-diethyl-
4,4'-diphenylmethane diisocyanate (R ₁ : CH ₂ CH ₃ , R ₂ : H), 2,2'-dichloro-
4,4'-diphenylmethane diisocyanate (R ₁ :H, R ₂ :Cl), 2,2'-dimethyl-4,4'-
Diphenylmethane diisocyanate (R ₁ :H,
R ₂ : CH ₃ ), 2,2'-dimethoxy-4,4'-diphenyl diisocyanate (R ₁ : H, R ₂ :
OCH ₃ ), 2,2′,5,5′-tetrachloro-4,
4′-diphenylmethane diisocyanate (R ₁ :
Cl, R ₂ :Cl), 2,2',5,5'-tetramethyl-
4,4'-diphenylmethane diisocyanate (R ₁ : CH ₃ , R ₂ : CH ₃ ), 2,2'-dimethyl-5,
5'-dichloro-4,4'-diphenylmethane diisocyanate (R ₁ : Cl, R ₂ : CH ₃ ), 2,2',5,
Examples include 5'-tetramethoxy-4,4'-diphenylmethane diisocyanate (R ₁ :OCH ₃ , R ₂ :OCH ₃ ). The reaction for producing the compound represented by the general formula () is carried out in an inert solvent, and examples of reaction solvents that can be used include chlorobenzene, O-dichlorobenzene, nitrobenzene,
Examples include benzene, toluene, dioxane, acetonitrile, dibutyl ether, methyl ethyl ketone, anisole, and the like. The reaction solvent is preferably used in an amount that allows the reaction to be carried out physically well, and usually the 3-imino-
4,5,6,7-tetrachloroisoindoline-
A suitable amount is 5 to 30 times the weight of 1-one. Various reaction temperatures should be applied depending on the reactivity of the raw material compounds used, but usually 50 -
250°C is preferred. The compound represented by the general formula () can be sufficiently used as a pigment as it is, but by further pulverizing or grinding it, the pigment performance such as coloring power can be significantly improved. The compound of the present invention can be identified by its infrared absorption spectrum showing characteristic absorption derived from urea bonds around 1510 cm ^-1 and 1670 cm ^-1 and by structural analysis using nuclear magnetic resonance spectroscopy. Examples will be described below. Example 1 10.0 g of 3-imino-4,5,6,7-tetrachloroisoindolin-1-one and 5.62 g of 3,3'-dichloro-4,4'-diphenylmethane diisocyanate, and an inert solvent Put 200g of O-dichlorobenzene into a flask and heat at 175℃ for 6 hours.
Allowed time to react. Next, the reaction solution was filtered, and the solid material was washed with N,N-dimethylformamide, acetone, and water, and then dried at 120°C. As a result, 13.7 g of a yellow pigment was obtained (yield: 88%). Structural analysis using infrared absorption spectroscopy and nuclear magnetic resonance spectroscopy and elemental analysis revealed that this pigment was a compound represented by the following structural formula. The infrared absorption spectrum of this compound is shown in the drawing. The device used for the measurement was IR-G manufactured by JASCO Corporation.
It was a model infrared spectrophotometer, and the measurement method was the KBr method. Next, the elemental analysis values of this compound are shown. C H N O Cl Calculated value (%) 41.9 1.4 9.5 7.2 40.0 Actual value (%) 41.9 1.5 9.8 7.0 39.8 This pigment exhibits a very bright yellow color and has excellent solvent resistance, chemical resistance, weather resistance, and coloring strength. It has excellent properties and can be used as a coloring agent in paints or printing inks using known methods. Furthermore, the colored product colored in this manner has extremely excellent weather resistance, heat resistance, chemical resistance, and migration resistance. Example 2 10.0 g of 3-imino-4,5,6,7-tetrachloroisoindolin-1-one and 4.89 g of 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, and an inert solvent Put 200g of O-dichlorobenzene into a flask and heat at 120℃ for 6 hours.
Allowed time to react. The reaction product was then treated in the same manner as in Example 1 to obtain 13.3 g of a reddish-yellow pigment (yield: 89%). As a result of the same structural analysis as in Example 1, this pigment was found to be a compound having the following structural formula. Next, the elemental analysis values of this compound are shown. C H N O Cl Calculated value (%) 46.8 2.1 9.9 7.6 33.6 Actual value (%) 46.7 2.0 10.1 7.9 33.3 This pigment exhibits a very bright reddish-yellow color and has the same pigment performance as the pigment of Example 1. It has physical properties. Example 3 10.0 g of 3-imino-4,5,6,7-tetrachloroisoindolin-1-one and 5.46 g of 3,3'-dimethoxy-4,4'-diphenylmethane diisocyanate, further inert solvent 200 g of O-dichlorobenzene was placed in a flask and reacted at 100°C for 6 hours. The reaction product was then prepared in Example 1.
14.2 g of reddish-yellow pigment (yield 92
%) was obtained. As a result of structural analysis in the same manner as in Example 1, it was found that this compound had the following structural formula. Next, the elemental analysis values of this compound are shown. C H N O Cl Calculated value (%) 45.1 2.1 9.6 10.9 32.3 Actual value (%) 45.5 2.0 9.8 10.6 32.1 This pigment exhibits a very bright reddish-yellow color and has the same pigment performance as the pigment of Example 1. It has physical properties. Examples 4 to 10 By the same method as in Example 1, the pigments shown in the table below could be produced. The structures of these compounds are shown by the general formula () above, where R ₁ and
Only R ₂ is different. Moreover, the pigment performance of these compounds was equivalent to that of the compound of Example 1.

【table】

【table】 [Brief explanation of the drawing]

The figure is an infrared absorption spectrum of the compound of Example 1.

Claims (1)

[Claims] 1. General formula (In the formula, R ₁ and R ₂ are each a hydrogen atom,
Represents any one of a halogen atom, a lower alkyl group, and a lower alkoxy group. However, R ₁ , R ₂
cannot be hydrogen at the same time. ) A novel azomethine pigment. 2. Claim 1, wherein R ₁ and R ₂ are each a hydrogen atom, a chlorine atom, a methyl group, or a methoxy group (however, R ₁ and R ₂ are not hydrogen at the same time) pigment. 3. The pigment according to claim ₁ , wherein R 1 is a chlorine atom and R ₂ is a hydrogen atom. 4. The pigment according to claim 1, wherein R ₁ is a methyl group and R ₂ is a hydrogen atom. 5. The pigment according to claim 1, wherein R ₁ is a methoxy group and R ₂ is a hydrogen atom. 6. The pigment according to claim ₁ , wherein R 1 is a hydrogen atom and R ₂ is a chlorine atom. 7. The pigment according to claim _{1, wherein R 1} is a hydrogen atom and R ₂ is a methyl group. 8. The pigment according to claim ₁ , wherein R 1 is a hydrogen atom and R ₂ is a methoxy group. 9. The pigment according to claim ₁ , wherein R 1 is a chlorine atom and R ₂ is a chlorine atom. 10. The pigment according to claim ₁ , wherein R 1 is a methyl group and R ₂ is a methyl group. 11. The pigment according to claim ₁ , wherein R 1 is a chlorine atom and R ₂ is a methyl group. 12. The pigment according to claim ₁ , wherein R 1 is a methoxy group and R ₂ is a methoxy group.