JPS629143B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel and useful phthalocyanine compounds and phthalocyanine pigments, and methods for producing them. Phthalocyanine compounds have been studied in various directions since Linstead's research, and in particular, countless studies have been conducted, including the development of new compounds for copper phthalocyanine and methods for producing new copper phthalocyanine pigments. However, research on metal phthalocyanines other than copper phthalocyanine as new compounds and pigments has been limited to US Pat. No. 3,094,535, US Pat. While researching various metal phthalocyanines, the present inventor discovered a new and useful metal phthalocyanine that had not been previously described in the literature, leading to the present invention. That is, the present invention provides the general formula (In the formula, M represents germanium, aluminum, gallium, or indium. _{R 1} is

[Formula] is shown. R ₂ and R ₃ each represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a nitro group, a sulfone group, or a halogen atom. n is
Indicates 1 or 2. However, M is aluminum,
In the case of gallium, n indicates 1. ), pigments using the compounds, and methods for producing these. The novel phthalocyanine compound according to the present invention is
General formula () (In the formula, M is germanium, aluminum,
Indicates gallium and indium. X represents a halogen atom, and n represents 1 or 2. However, when M is aluminum or gallium, n represents 1. )
Halogenated metal phthalocyanine represented by and general formula ()

[Formula] (wherein, R ₂ and R ₃ represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a nitro group, a sulfone group, and a halogen atom, respectively.) A method of reacting at ~90℃, or a method of reacting a halogenated metal phthalocyanine represented by the general formula () with the general formula ()

[Formula] (In the formula, R ₂ and R ₃ are each a hydrogen atom and a carbon number of 1
~18 alkyl groups, nitro groups, sulfone groups, and halogen atoms. ) and can be obtained by a method of heating reaction with sulfuric acid. The halogenated metal phthalocyanine represented by the general formula () related to the present invention can be obtained by a conventionally known method, and the phthalodinitrile and the metal halide are not involved in the reaction of nitrobenzene, trichlorobenzene, etc. A method of heating reaction in the presence or absence of a solvent, a method of heating a metal halide with phthalic acid or phthalimide and urea, or a method of heating ammonium molybdate with a metal halide (so-called solid phase method), It can be easily obtained by a method conducted in an active reaction solvent (so-called liquid phase method). As the aromatic sulfonic acid represented by the general formula () related to the present invention, xylene sulfonic acid, toluenesulfonic acid, dodecylbenzenesulfonic acid, nitrobenzenesulfonic acid, chlorobenzenesulfonic acid, etc. can be used. In addition, when the aromatic sulfonic acid represented by the above general formula () is not used directly, the general formula ()

An aromatic compound represented by the formula (wherein R ₂ and R ₃ are the same as above), such as xylene, toluene, dodecylbenzene, nitrobenzene, and chlorobenzene, and sulfuric acid are used. These range from 0°C to 90°C, preferably from 30°C to 60°C.
By reacting for 2 to 6 hours, the novel metal phthalocyanine related to the present invention can be obtained. In addition, the obtained metal phthalocyanine compound is
Suitability as a pigment, i.e. weather resistance, heat resistance,
It has good acid resistance and alkali resistance, and can be used as it is or after being made into a pigment for use in paints and printing inks. Furthermore, by adding 2 parts by weight or more of the pigment according to the present invention to 100 parts by weight of the copper phthalocyanine pigment, it is effective to improve the coating suitability of the copper phthalocyanine pigment (for example, improving flocculation properties and thickening properties). It turns out that there is. The present invention will be explained in more detail below using Examples. Reference example 1 300g of trichlorobenzene and 64g of phthalodinitrile in a 500ml 4-necked flask equipped with a condenser.
(0.5mol), germanium tetrachloride 26.8g
(0.125mol) and heat while stirring.
Reflux for 6 hours. Cool, filter, xylene,
Wash with acetone, then warm water, and dry. The elemental analysis value of this thing is

[Table] The parent peak according to the mass spectrum is 656,
The molecular weight was consistent with that of dichlorogermanium phthalocyanine. This infrared absorption spectrum is shown in FIG. 1, and the visible absorption spectrum is shown in FIG. Reference example 2 64 phthalodinitrile in a 500ml 4-necked flask
g (0.5mol), aluminum chloride 16.7g
(0.125mol) and heat while stirring.
The initial reaction occurs at 250°C, and the reaction occurs quite vigorously at 300°C, releasing hydrochloric acid gas. The reaction was continued at the same temperature for 2 hours, and the reactant was dissolved in 0.5% hydrochloric acid solution.
After heating with water, filtering, and washing with warm water,
Heat with 1% alkaline water and wash with filtered and warm water. The analytical value of the dried product is

[Table] The parent peak according to the mass spectrum is 575,
The molecular weight was consistent with that of chloroaluminum phthalocyanine. (Figures 2 and 13) Reference example 3 64 phthalodinitrile in a 500ml 4-necked flask
g (0.5 mol) and potassium chloride 22 g (0.125 mol), and heat while stirring. 280℃ to 300℃
The reaction takes place with the rapid release of hydrochloric acid gas.
React at the same temperature for 1 hour, and reduce the reactant to 0.5%.
Heating with 1 part of hydrochloric acid water, washing with filtrated and warm water, then heating with 1 part of 0.2% alkaline water,
Wash with warm water. The analytical value of the dried material is

[Table] The parent peak according to the mass spectrum is 617,
The molecular weight was consistent with that of chlorogallium phthalocyanine. (Figures 3 and 14) Example 1 200 g of 98% sulfuric acid, 20 g of xylene, and 20 g of dichlorogermanium phthalocyanine obtained in Reference Example 1 were stirred and reacted at 40 to 50°C for 4 hours in a 300 ml four-necked flask. Afterwards, pour into water 2 to wash the precipitate, and then dry. 28.5 g of dixylene sulfonyl germanium phthalocyanine was obtained. C% H% Ge% Analytical value 59.85 3.60 7.70 Calculated value 60.33 3.59 7.60 (Fig. 4, Fig. 15) Example 2 In a 300 ml four-necked flask, 200 g of 98% sulfuric acid, 20 g of xylene, the sample obtained in Reference Example 2 After stirring 20 g of chloroaluminum phthalocyanine at 40 to 50°C for 4 hours, it is poured into water 2, and the precipitate is washed with water and dried. 23.9 g of xylene sulfonyl aluminum phthalocyanine was obtained. C% H% Al% Analytical value 66.54 3.30 3.82 Calculated value 66.29 3.48 3.72 The parent peak of this mass spectrum is:
725, which matched the molecular weight of xylene sulfonylaluminum phthalocyanine. (Fig. 5, Fig. 16) Examples 3 to 15 As shown in Table 1, the products shown in Table 1 were obtained by changing the raw materials and reaction conditions. Note that infrared absorption spectra and visible absorption spectra of Reference Examples and Examples are shown in the drawings. The infrared absorption spectrum is based on the KBr method (tablet method). (Infrared analyzer Model IRA-1 manufactured by JASCO Corporation) The visible absorption spectrum was measured using dimethylformamide as a solvent and a spectrophotometer MPS manufactured by Shimadzu Corporation.
-Measured using a 50L model. In addition, the mass spectrum was measured using a mass spectrometer LKD9000 manufactured by Shimadzu Corporation.

【table】

[Table] Table 2 also shows the results of a pigment suitability test conducted on the compounds obtained in Reference Examples and Examples according to the pigment test method according to JISK-5101.

【table】 [Brief explanation of the drawing]

FIGS. 1 to 3 are infrared absorption spectrum diagrams of reference examples. FIGS. 12 to 14 are visible absorption spectra of reference examples. FIG. 4 to FIG. 11 are infrared absorption spectrum diagrams of Examples. FIG. 15 to FIG. 22 are visible absorption spectrum diagrams of Examples.

Claims (1)

[Claims] 1. General formula (In the formula, M represents germanium, aluminum, gallium, or indium. _{R 1} is
[Formula] is shown. R ₂ and R ₃ each represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a nitro group, a sulfone group, or a halogen atom. n is
Indicates 1 or 2. However, M is aluminum,
In the case of gallium, n indicates 1. ) phthalocyanine compound. 2 General formula (In the formula, M represents germanium, aluminum, gallium, or indium. _{R 1} is
[Formula] is shown. R ₂ and R ₃ each represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a nitro group, a sulfone group, or a halogen atom. n is
Indicates 1 or 2. However, M is aluminum,
In the case of gallium, n indicates 1. ) Phthalocyanine pigments. 3 General formula (In the formula, M represents germanium, aluminum, gallium, or indium. X represents a halogen atom, and when M is aluminum or gallium, n
indicates 1. ) and a halogenated metal phthalocyanine represented by the general formula [Formula] (where R ₂ and R ₃ represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a nitro group, a sulfone group, and a halogen atom, respectively.) with the compound shown in 0~
General formula characterized by reaction at 90℃ (In the formula, M represents germanium, aluminum, gallium, or indium. R ₁ represents [Formula]. R ₂ and R ₃ are each a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a nitro group, a sulfone group, A method for producing a phthalocyanine compound (represents a halogen atom; n represents 1 or 2; however, when M is aluminum or gallium, n represents 1).