JPH01153758A - Copper phthalocyanine having novel crystal type - Google Patents

Abstract

NEW MATERIAL:A compound exhibiting a strong peak at 2theta=6.8 deg. and weak peaks at 2theta=9.9 deg., 15.7 deg., 26.6 deg. and 27.4 deg. on X-ray diffraction diagram obtained by using CuKalpha ray (lambda=1.542Angstrom ). USE:Useful as a blue organic pigment for the colorant of ink, paint, resin, etc. PREPARATION:Phthalic anhydride is made to react with a urea compound and a compound of formula I-VI in an organic solvent.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention is applicable to inks, paints,
It relates to copper phthalocyanine, which is used as a coloring agent for resins, etc.

<Prior art> Regarding the crystalline form of copper phthalocyanine, there are many homogeneous winter forms, such as the α type, which has a reddish hue and is unstable to heat and solvents, and the well-known β type, which has a greenish hue and is stable. It is widely used in the color material industry and other fields due to its characteristics (color tone, fastness).

Other copper phthalocyanines include the γ type, which is similar to the α type (Industrial Chemistry Magazine, Vol. 70, No. 4, p. 499 (196
7)) δ type with reddish hue and needle-like particles
12836), the δ type which has a reddish hue and high tinting power and is unstable in solvents (Japanese Patent Publication No. 40-2780), the π type with excellent photosensitivity used in electrophotography (Japanese Patent Publication No. 48-725). Type X (Japanese Patent Publication No. 46-42512), Type β (Japanese Patent Publication No. 52-842), which has a bright reddish hue and is unstable to solvents.
31 Publication), and the β type (USP 3050721), which has a reddish hue and is stable against solvents at high concentrations, are also known, but their fields of application are extremely limited and they are not very important industrially. do not have. These X-ray diffraction lines containing a large amount of copper phthalocyanine are introduced in "Dye to Yakuhin", Vol. 23, No. 10, p. 210 (1978).

<Problems to be solved by the invention> In general, the α type has a reddish hue and has excellent light resistance and chemical resistance, but its crystal form changes to the β type when exposed to heat or organic solvents, so it becomes discolored at high temperatures. It cannot be used as is for resin applications that require high temperatures, paints that use large amounts of organic solvents, solvent-based inks, etc.
Water-based paints and inks that do not use vinyl chloride resin or organic solvents that are colored at relatively low temperatures, such as:
It is used only for PRC (pigment printing), etc.

On the other hand, the β type is stable against heat and solvents and can be used for various purposes, but it has a greenish hue and cannot meet the requirements for a reddish tone.

Furthermore, other crystal forms are as follows: 1) The manufacturing method is special and there are economical problems, making it difficult to implement industrially.

2) It cannot be said that it can be used for general purposes because it has insufficient performance compared to the α and β types. For these reasons, there is currently no copper phthalocyanine known that has a reddish hue, is stable against heat and solvents, and is economically viable for a variety of applications. .

<Means for Solving the Problems> As a result of various studies to eliminate these problems of conventional copper phthalocyanine, the present inventors found that copper phthalocyanine having a specific new crystal type has a reddish hue and is resistant to heat and heat. The present invention was completed based on the discovery that it is extremely stable against solvents and can be used for various purposes.

That is, the present invention has a strong peak at 2θ=6.8 degrees, 2θ-9, 9 degrees, 15.7 degrees, 26. 6 degrees and 27
．． The present invention provides a new crystalline type of useful copper phthalocyanine having a weak peak at 4 degrees.

FIG. 1 shows an X-ray diffraction diagram of the novel crystalline copper phthalocyanine of the present invention. It is easy to see from the figure that the new crystal form of the present invention is different from the conventional crystal form, but for a more detailed comparison, the diffraction angle (2θ) of the α type whose X-ray diffraction diagram waveform is relatively similar to that of the present invention. A comparison is shown in Table 1. Incidentally, FIG. 2 shows a conventional α-type X-ray diffraction diagram.

Table 1 shows that when comparing the new crystal form and the α type, the new crystal form has only one strong peak of 6.8 and no 2θ=7.2;
There is a clear difference in that there is no weak peak at 2θ-16,2 seen in the α type.

The novel crystalline copper phthalocyanine pigment of the present invention is typically Wy
It can be easily obtained by adding a compound represented by the following formula when reacting phthalic anhydride and a urea compound copper source in an organic solvent, which is called the ler method, and the obtained product can be pigmented with sulfuric acid or mechanically There is no need for pigmentation, which is usually applied to α-type and β-type products, such as pigmentation by mechanical grinding, and an economically superior product can be obtained.

<Effects of the Invention> The new crystalline copper phthalocyanine pigment of the present invention has a more reddish tone than the β type and is stable against heat and organic solvents, so it can be used in water-based paints where the conventional α type has been used. It can be used for resin applications that are colored at high temperatures, which cannot be used with other types of water-based ink PRC, or for paints and inks that use large amounts of organic solvents. Furthermore, the new crystalline copper phthalocyanine pigment of the present invention is economically superior as described above, and can be used in various applications such as inks, paints, and resins. The present invention can be said to be revolutionary in that it solves various problems with conventional copper phthalocyanine pigments.

<Example> Examples are given below. In the examples, parts and % are based on weight. Further, the specific surface area value was determined by the N2 gas phase adsorption method using the BET method. X-ray diffraction is XD-5A (CDP'-51)
(manufactured by Bokuji Seisakusho, X-ray diffractometer), λ=1.
Measurements were carried out using 5428 Cukα radiation.

Example-1 (Synthesis of new crystalline copper phthalocyanine) Phthalic anhydride 5
92 parts of urea, 960 parts of urea, 105 parts of cuprous chloride, 80 parts of titanium tetrachloride, and 18 parts of 3.4.5.6-tetrahydrophthalimide were added to 4500 parts of sulfolane, and 180 parts of urea was added under stirring.
The temperature was raised to ~190°C and heated at the same temperature for 5 hours. Next, the mixture was cooled to 100°C, and 5000 parts of warm water previously kept at 60°C was added. Next, the reaction mass is filtered, and after the filtration is completed, it is washed with 5000 parts of 80°C warm water. Thereafter, the wet cake taken out was added to 10,000 parts of 5% hydrochloric acid, stirred at 60°C for 1 hour, and then filtered. Then,
By washing with 10,000 parts of 80° C. hot water and drying, 570 parts of the desired copper phthalocyanine were obtained. The purity of the obtained compound was 94%, and the specific surface area was 70 m'/g. The X-ray diffraction pattern was as shown in FIG.

(Performance of new crystalline copper phthalocyanine) The performance of the new crystalline copper phthalocyanine, which was synthesized and has not been converted into a pigment, was compared with conventionally known α-type and β-type commercially available copper phthalocyanine pigments.

■Performance with PP resin Dumiman Noble l/N AH661V (Dumiman Chemical) 100
After mixing 0.5 parts of Part Tie2R-615 (Ishiraya Sangyo) with a mixer, kneading it at 220℃ and pelletizing it, molding it with a 3.5oz injection molding machine at 220-300℃, changing the color and heat resistance. The gender was evaluated. The results are shown in Table-2.

The new crystalline copper phthalocyanine pigment has better heat resistance than the α type, and more surprisingly, it shows better heat resistance than the β type, and its hue is more reddish than the β type.

■Crystal type change in organic solvent Table 3 shows the crystal type changes in organic solvents.

As shown in the table above, the synthesized product of the present invention is stable in organic solvents and no change in crystal type is observed. What is even more surprising is that while particle growth was observed in the commercially available β and α forms, this was not observed in the new crystal form, indicating that it is extremely stable.

Example 2 The performance of the synthetic product obtained in Example 1 with a solvent-based melamine alkyd paint was evaluated.

A paint with a pigment content of 5% was prepared using primary color paint Near Mirak 1000 Clear and thinner (Kansai Paint).

Light color paint: A primary color paint and Amylac 1000 White (Kansai Paint) were mixed to make a paint with pigment/Ti02=1/10. The results are shown in Table 4.

Table 4 *α-type 11B-2 changes in crystal type when it is made into a paint.
causing particle growth.

The synthetic product of Example 1 of the present invention has a reddish hue with higher concentration than the β type, and is suitable for solvent-based paints.

The synthetic product of Example 1 of the present invention shows no change in crystal type or particle growth, unlike the (IIB-2) α type, even in the solvent-based melamine alkyd paint, and (GN-C-2)
Compared to the β type, it has a reddish hue and is highly concentrated.

Example 3 A novel crystalline copper phthalocyanine was obtained in the same manner using the compounds shown in Table 4 instead of the additives used in the synthesis of Example 1.

[Brief explanation of the drawing]

FIG. 1 shows an X-ray diffraction pattern of the novel crystalline copper phthalocyanine of the present invention. FIG. 2 shows an X-ray diffraction diagram of a crystalline form of conventional α-type copper phthalocyanine.

Claims (1)

[Claims] In the X-ray diffraction diagram using Cukα radiation (λ = 1.542 Å), there is a strong peak at 2θ = 6.8 degrees and a strong peak at 2θ = 9.
A new crystal type copper phthalocyanine having weak peaks at 9 degrees, 15.7 degrees, 26.6 degrees and 27.4 degrees.