JP2941955B2 - Method for producing oxytitanium phthalocyanine - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing oxytitanium phthalocyanine crystals, and more particularly, to CuKα
The present invention relates to a method for producing type I oxytitanium phthalocyanine having strong peaks at 9.0 °, 14.2 °, 23.9 ° and 27.1 ° in Bragg angles (2θ ± 0.2 °) in characteristic X-ray diffraction.

[0002]

2. Description of the Related Art Phthalocyanine-based pigments have attracted attention as electronic materials used in catalysts, electrophotographic photoreceptors, solar cells, sensors, and the like, in addition to conventional applications such as coloring of paints, inks, and resins. Became.

[0003] Among phthalocyanine pigments, it is known that oxytitanium phthalocyanine has extremely excellent properties as an electrophotographic material. The characteristics vary depending on the crystal form of oxytitanium phthalocyanine, and various kinds of crystal forms can be obtained depending on subtle differences in the production conditions of oxytitanium phthalocyanine.

For example, JP-A-59-49544 (US Pat. No. 4,444,861) and JP-A-59-1669.
No. 59, JP-A-61-239248 (USP
4,728,592), JP-A-62-67094 (US Pat. No. 4,664,997), JP-A-63-366, JP-A-63-116158, and JP-A-63-116158.
JP-A-198067 and JP-A-64-17066 disclose oxytitanium phthalocyanines having different crystal forms produced under various production conditions.

However, since these crystal forms are usually obtained as a mixture, there is a problem in product stability.

[0006] Therefore, a production method capable of obtaining pure crystalline oxytitanium phthalocyanine has been desired, and many attempts have been made in the past. For example, JP-A-63-364, JP-A-63-365,
JP-A-63-37163, JP-A-63-5767
No. 0, JP-A-63-80263 and the like describe a method for producing A-type and C-type crystals.

On the other hand, in the CuKα characteristic X-ray diffraction, the Bragg angles (2θ ± 0.2 °) of 9.0 °, 14.2 °, 2 °
Japanese Patent Application No. 1-189200 discloses that the so-called I-type oxytitanium phthalocyanine of the crystalline form having strong peaks at 3.9 ° and 27.1 ° has extremely excellent properties as an electrophotographic material. It is described in. Although the type I oxytitanium phthalocyanine is easily produced in the laboratory by the production method described in the specification, it is not sufficiently satisfactory in selecting a solvent in view of further industrial utility. Was.

[0008] For example, ether solvents used for milling treatment have flammability, and there is a danger of explosion due to generation of peroxide. Monoterpene solvents are solvents which are difficult to use for general purposes. Paraffin has a high viscosity, and therefore requires a long processing time and is difficult to handle.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing pure type I oxytitanium phthalocyanine.

Another object of the present invention is to provide a method suitable for industrialization,
An object of the present invention is to provide a method for producing type I oxytitanium phthalocyanine which can be easily mass-produced.

[0011]

That is, the present invention relates to a solvent containing oxytitanium phthalocyanine as a raw material containing a saturated hydrocarbon solvent (excluding liquid paraffin).
Characteristic X characterized by milling with
9.0 of the Bragg angle (2θ ± 0.2 °) in X-ray diffraction
This is a method for producing oxytitanium phthalocyanine having strong peaks at °, 14.2 °, 23.9 ° and 27.1 °.

The X-ray diffraction (using CuKα characteristic X-ray) pattern of the type I oxytitanium phthalocyanine crystal obtained by the present invention has a Bragg angle (2θ ± 2) as shown in FIG.
(0.2 °) at 9.0 °, 14.2 °, 23.9 ° and 27.1 °. The peak is
The top four points with the highest peak intensities are taken and are the main peaks.

Here, the structure of oxytitanium phthalocyanine is

[0014]

[Outside]

Is represented by

Here, X ₁ , X ₂ , X ₃ and X ₄ represent Cl or Br, and n, m, l and k are integers of 0-4.

The oxytitanium phthalocyanine used as a raw material in the present invention includes a Bragg angle (2θ ± 2) in CuKα characteristic X-ray diffraction as shown in FIG.
0.2 °), so-called M-type oxytitanium phthalocyanine having major peaks at 7.2 °, 14.2 °, 24.0 ° and 27.2 °, and C as shown in FIG.
Bragg angle in uKα characteristic X-ray diffraction (2θ ± 0.2
So-called Mc-type oxytitanium phthalocyanine having main peaks at 7.1 °, 10.3 ° and 27.3 ° in (°). Since milling treatment of either M-type oxytitanium phthalocyanine or Mc-type oxytitanium phthalocyanine can similarly obtain an I-type oxytitanium phthalocyanine crystal, there is no problem even if a mixture of both is used as oxytitanium phthalocyanine used as a raw material.

The saturated hydrocarbon-based solvent used as a dispersion medium for milling may have a methyl group at the 2-position, and may have an aliphatic saturated hydrocarbon-based solvent having 5 to 12 carbon atoms in the main chain. For example, n-pentane, n-hexane, n-
Aliphatic saturated hydrocarbon solvents such as octane, n-decane, n-dodecane, 2-methylpentane and 2-methyloctane are preferred. Further, a mixed solvent containing the above-mentioned solvent as a main component can be used, and for example, a solvent such as ligroin and petroleum benzine can also be used. However, liquid paraffin is excluded.

The amount of the dispersing solvent used can be arbitrarily selected.
Preferably, it is selected from the range of 5 to 40 parts by weight per 1 part by weight of oxytitanium phthalocyanine. If the amount of the solvent is less than this, the viscosity of the processing liquid increases, so that uniform processing is difficult. On the other hand, if the amount is larger than this, the throughput per unit volume is reduced, and the productivity is poor.

As the dispersion medium used in the milling treatment in the present invention, any commonly used medium such as glass beads, still beads and alumina beads may be used.

The treatment time is preferably at least 1 hour, particularly preferably 5 to 30 hours. If the processing time is less than 1 hour, the crystal conversion may not be completely performed, and if it exceeds 30 hours, the productivity cannot be said to be good.

The processing temperature is not particularly limited.
The temperature is preferably 80 ° C. or lower from the viewpoint of stability of the crystal.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

Example 1 Low crystalline oxytitanium phthalocyanine M type 2.0K
To 40 g, 40 kg of n-bexane was added, and a milling treatment was performed at room temperature for 15 hours together with 1 mmφ glass beads. Solids were taken out of the dispersion, washed thoroughly with methanol and then with ion-exchanged water, and dried to obtain type I oxytitanium phthalocyanine crystals. Yield 1.9 kg.

Examples 2 to 13 and Comparative Examples 1 to 10 Tables 1 and 2 show the results of treatment in the same manner as in Example 1 except that the crystal form of the raw material oxytitanium phthalocyanine, the treatment solvent and the treatment time were changed. .

The B type used as a raw material described in Table 2,
A-type oxytitanium phthalocyanine crystals are disclosed in, for example, JP-A-61-239248 (US Pat. No. 4,728,
592), JP-A-62-67094 (USP 4,
664, 997). The respective X-ray diffraction diagrams are shown in FIGS.

[0026] Incidentally, the X-ray diffraction measurement in Examples and Comparative Examples of the present invention was performed using MAC Science Co., automatic X-ray diffractometer MXP ^18.

[0027]

【table】

[0028]

【table】

[0029]

As described above, according to the manufacturing method of the present invention, the Bragg angles (2θ ± 0.2 °) of 9.0 °, 14.2 °, and 23 ° in the CuKα characteristic X-ray diffraction. 9
Oxytitanium phthalocyanine having strong peaks at ° and 27.1 ° can be obtained purely and simply.

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction diagram of oxytitanium phthalocyanine obtained in Example 1.

FIG. 2 is an X-ray diffraction diagram of M-type oxytitanium phthalocyanine used in Examples.

FIG. 3 is an X-ray diffraction diagram of Mc-type oxytitanium phthalocyanine used in Examples.

FIG. 4 is an X-ray diffraction diagram of B-type oxytitanium phthalocyanine used in Comparative Example.

FIG. 5 is an X-ray diffraction diagram of A-type oxytitanium phthalocyanine used in a comparative example.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hideyuki Takai 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (56) References JP-A-3-128973 (JP, A) (58) Survey ⁶ (Int. Cl. ⁶ , DB name) C09B 67/50 G03G 5/06 371 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] 1. A Bragg angle (2θ) in CuKα characteristic X-ray diffraction, wherein oxytitanium phthalocyanine as a raw material is milled with a solvent containing a saturated hydrocarbon solvent (excluding liquid paraffin).
± 0.2 °), which has strong peaks at 9.0 °, 14.2 °, 23.9 ° and 27.1 °. 2. The method for producing oxytitanium phthalocyanine according to claim 1, wherein the main chain of the saturated hydrocarbon solvent has 5 to 12 carbon atoms. 3. The method for producing oxytitanium phthalocyanine according to claim 1, wherein the saturated hydrocarbon solvent has a methyl group at the 2-position. 4. The oxytitanium phthalocyanine as a raw material has a Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction of 7.2 °, 14.2 °, 24.
The method for producing oxytitanium phthalocyanine according to any one of claims 1 to 3, wherein the oxytitanium phthalocyanine has strong peaks at 0 ° and 27.2 °. 5. The oxytitanium phthalocyanine as a raw material has a Bragg angle (2θ ± 0.2 °) of 7.1 °, 10.3 ° and 2 ° in CuKα characteristic X-ray diffraction.
The method for producing oxytitanium phthalocyanine according to any one of claims 1 to 3, wherein the oxytitanium phthalocyanine has a strong peak at 7.3 °.