JPH03250060A - Method for producing oxytitanium phthalocyanine - Google Patents

Abstract

PURPOSE:To prepare type I oxytitanium phthalocyanite with a high purity by milling an aq. oxytitanium phthalocyanine paste in a solvent contg. a satd. hydrocarbon solvent. CONSTITUTION:Type I oxytitanium phthalocyanine of the formula (wherein X1 to X4 are each Cl or Br; and (n), (m), (l) and (k) are each 0-4), having strong peaks at Bragg angles (2theta+ or -0.2 deg.) of 9.0 deg., 14.2 deg., 23.9 deg. and 27.1 deg. in the CuKalpha characteristic X ray diffraction pattern, is prepd. by milling an aq. oxytitanium phthalocyanine paste contg. 15-45wt.% solid and obtd. by acid pasting in 5-40 pts.wt. (based on 1 pt.wt. oxytitanium phthalocyanine) solvent contg. a 5-12C aliph. satd. hydrocarbon solvent optionally having a methyl group at the 2-position (e.g. n-pentane) in the presence of a dispersion medium, such as glass beads or steel beads, at 80 deg.C, or lower for at least 1hr.

Description

[Detailed description of the invention]

[0001]

[Industrial application field]

The present invention relates to a method for producing oxytitanium phthalocyanine crystals, and more specifically, the Bragg angle (2θ±0.2°) in Cukα characteristic X-ray diffraction is 9.0° 14°2°.
■ Has strong peaks at 23.9° and 27.1°
The present invention relates to a method for producing type oxytitanium phthalocyanine crystals. [0003]

[Conventional technology]

In addition to conventional uses such as coloring paints, inks, and resins, phthalocyanine pigments are also used as catalysts, electrophotographic photoreceptors, solar cells,
It has attracted attention as an electronic material used in sensors, etc., and has come to be widely used. [0003] Among phthalocyanine pigments, oxytitanium phthalocyanine is known to have very excellent properties as an electrophotographic material. Properties vary depending on the crystal form of oxytitanium phthalocyanine, and various types of crystal forms can be obtained depending on subtle differences in the manufacturing conditions of oxytitanium phthalocyanine. [0004] For example, Japanese Patent Application Laid-Open No. 59-49544 (USP 4,4
44,861) JP-A-59-166959,
Japanese Patent Application Publication No. 61-239248 (USP 4,728.
592) Japanese Unexamined Patent Publication No. 62-67094 (USP4
, 664,997) JP-A-63-366, JP-A-63-116158, JP-A-63-198067
Oxytitanium phthalocyanine having different crystal forms produced under various production conditions is described in JP-A-64-17066 and the like. [0005] However, since these crystal forms are usually obtained as a mixture, there has been a problem with the stability of the product. [0006] Therefore, a manufacturing method capable of obtaining pure crystalline oxytitanium phthalocyanine has been desired, and many attempts have been made to date. For example, JP-A-63-3
No. 64, JP-A-63-365, JP-A-63-
37163, JP-A-63-57670, JP-A-63-80263, etc., A-type and C-type
A method of manufacturing a type crystal is described. [0007] On the other hand, the Bragg angle (2θ
±0.2°) is 9.014.2° Crystalline oxytitanium phthalocyanine with strong peaks at 23.9° and 27.1°, so-called type 1 oxytitanium phthalocyanine, has extremely excellent properties as an electrophotographic material. It is described in the specification of Japanese Patent Application No. 189200/1999. Type (3) oxytitanium phthalocyanine can be easily produced in the laboratory by the production method described in the same specification, but when further industrial usefulness is taken into consideration, the selection of the solvent is not fully satisfactory. [0008] For example, ether-based solvents used in milling processes are flammable and have the risk of explosion due to the formation of peroxides, and monoterpene-based solvents are difficult to use for general purposes; Since paraffin has a high viscosity, it takes a long time to process and is difficult to handle. [0009] (Problems to be Solved by the Invention) An object of the present invention is to provide a method for producing pure type 3 oxytitanium phthalocyanine. The object of the present invention is to provide a method for producing type 2 oxytitanium phthalocyanine that can be easily mass-produced. [0011]

[Means to solve the problem]

That is, the present invention is characterized in that a water paste of oxytitanium phthalocyanine is milled with a solvent containing a saturated hydrocarbon solvent. 14.2
This is a method for producing oxytitanium phthalocyanine having strong peaks at 239° and 27.1°. [0013] As shown in FIG. 1, the X-ray diffraction (using Cukα characteristic X-ray) pattern of the ■-type oxytitanium phthalocyanine crystal obtained by the present invention has a Bragg angle (2θ±02°) of 9.0° 14.2 ° 23.9° and 27,1
It shows a strong peak at the position of °. The above peaks are obtained by selecting the top four points with the highest peak intensities, and are the main peaks. [0013] Here, the structure of oxytitanium phthalocyanine is [00
14]

[Outside]

It is expressed as [0015] However, Xl, X2, X3, and X4 represent CI or Br, and n, m, and l are integers of O to 4. [0016] When a water paste of oxytitanium phthalocyanine is used in the present invention, a water paste obtained by a normal acid pacing method is preferably used. This water paste only needs to contain water uniformly, and the preferred solid content is 15 to 45% by weight. Further, the crystal form of oxytitanium phthalocyanine used in this water paste is not particularly limited. The oxytitanium phthalocyanine contained in the water paste is subjected to kami acid pacing treatment to form various slightly amorphous crystalline or amorphous forms depending on the conditions such as the amount of sulfuric acid used in the acid pacing treatment, the amount of water, and the treatment temperature. Any amorphous, semi-amorphous, crystalline form, or mixtures thereof, may be used. [0017] The saturated hydrocarbon solvent used as a dispersion medium for milling includes an aliphatic saturated hydrocarbon solvent having 5 to 12 carbon atoms in the main chain, which may have a methyl group at the 2-position;
For example, n-pentane, n-hexane, n-octane, n-
-decane, n--dodecane, 2-methylpentane, 2
-Aliphatic saturated hydrocarbon solvents such as methyloctane are preferred. Further, a mixed solvent can be used as long as the above-mentioned solvent is the main component, and for example, solvents such as ligroin and petroleum benzene can also be used. [0018] The amount of dispersion solvent used can be selected arbitrarily, preferably 5 to 4 parts by weight per 1 part by weight of oxytitanium phthalocyanine.
0 parts by weight. If the amount of solvent is less than this, the viscosity after treatment will be high, making uniform treatment difficult. Moreover, if the amount is larger than this, the throughput per unit volume will be reduced, resulting in poor productivity. [0019] As the dispersion media used in the milling process in the present invention, commonly available media such as glass beads, still beads, and alumina beads may be used. [0020] The treatment time is preferably 1 hour or more, particularly 5 hours to 30 hours.
time is preferable. If the treatment time is less than 1 hour, complete crystal conversion may not occur, and if it exceeds 30 hours, productivity cannot be said to be good. [0021] Further, the treatment temperature is not particularly limited, but is preferably 80° C. or lower from the viewpoint of stability of the force plate crystal. [0023]Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. [0023] Example 1 Japanese Patent Application Laid-Open No. 61-239248 (USP 4,728,
Oxytitanium phthalocyanine crystals, generally referred to as type B, were obtained according to the production example disclosed in No. 592). 2.0kg of this Bg crystal was added to 60kg of concentrated sulfuric acid.
The mixture was slowly added and dissolved at a temperature below 0.degree. C., and then dropped into 600 kg of ice water over 2 hours. The obtained pigment was filtered and thoroughly washed with water to obtain a water paste of oxytitanium phthalocyanine (hereinafter referred to as water paste ①). Note that the solid content of this water paste was 20%. [0024] A portion of this water paste was dried and subjected to X-ray diffraction measurement. The obtained diffraction pattern is shown in FIG. [0025] Water paste ■5. Add 20kg of n-hexane to Okg, and milling with 1mmφ glass beads for 20 minutes.
℃ for 20 hours. A solid content was taken out from this dispersion, thoroughly washed with n-hexane, and dried to obtain a -type oxytitanium phthalocyanine crystal. Yield: 0.9 kg. [0026] An X-ray diffraction diagram of the obtained oxytitanium phthalocyanine is shown in FIG. [0027] Examples 2 to 10 Oxytitanium phthalocyanine was obtained in the same manner as in Example 1, except that the treatment solvent, treatment time, and treatment temperature were changed as shown in Table 1. The results are shown in Table 1. [0028]

【table】

Table Example 11 2.0 kg of B-type oxytitanium phthalocyanine used in Example 1 was slowly added to and dissolved in 60 kg of concentrated sulfuric acid at 5° C. or below, and then added dropwise to 800 kg of water at 25° C. over 1 hour. The obtained pigment was separated by filtration and thoroughly washed with water to obtain a water paste of oxytitanium phthalocyanine (hereinafter referred to as water paste ①). Note that the solid content of this water paste was 24%. [0029] A portion of this water paste was dried and subjected to X-ray diffraction measurement. The obtained diffraction diagram 1 is shown [0030] 20 kg of n-hexane was added to 4.2 kg of water paste ■, and milled with 1 mmφ glass beads for 20 minutes.
℃ for 20 hours. A solid content was taken out from this dispersion, thoroughly washed with n-hexane, and dried to obtain a -type oxytitanium phthalocyanine crystal. Yield: 0.9 kg. [0031] Examples 12 to 18 Oxytitanium phthalocyanine was obtained in the same manner as in Example 11, except that the treatment solvent, treatment time, and treatment temperature were changed as shown in Table 2. The results are shown in Table 1. [0033]

【table】

Table 2 Example 19 Japanese Unexamined Patent Publication No. 62-67094 (USP 4,664,9
97), 2.0 kg of A-type oxytitanium phthalocyanine obtained according to the production example disclosed in
．． Slowly add and dissolve in 0kg at 30℃ or below,
It was dropped into 800 kg of water at 30° C. over 30 minutes. The obtained pigment was filtered and thoroughly washed with water to obtain a water paste of oxytitanium phthalocyanine (hereinafter referred to as water paste ①). Note that the solid content of this water paste was 22%. [0033] A portion of this water paste was dried and subjected to X-ray diffraction measurement. The obtained diffraction pattern is shown in FIG. [0034] 20 kg of n-hexane was added to 4.5 kg of water paste ■, and milled with 1 mm diameter glass beads for 20 minutes.
℃ for 20 hours. A solid content was taken out from this dispersion, thoroughly washed with n-hexane, and dried to obtain a -type oxytitanium phthalocyanine crystal. Yield: 0.9 kg. [0035] Examples 20 to 26 Oxytitanium phthalocyanine was obtained in the same manner as in Example 19, except that the treatment solvent, treatment time, and treatment temperature were changed as shown in Table 3. The results are shown in Table 3. [0036]

【table】

Table Comparative Examples 1 to 14 Oxytitanium phthalocyanine was obtained in the same manner as in Example 1, except that the water paste (1), treatment solvent, treatment time, and treatment temperature were changed as shown in Table 4. The results are shown in Table 4. [0037] The X-ray diffraction measurements in the examples and comparative examples of the present invention were carried out by Massi Scien [0038]

【table】

Table [0039] [Effects of the invention] As explained above, according to the production method of the present invention, CuK
Bragg angle (2θ±0.2
°) is 9,0° 1442° 23.9° and 2
Oxytitanium phthalocyanine having a strong peak at 7.1° can be obtained purely and easily.

[Brief explanation of drawings]

[Figure 1] An X-ray diffraction diagram of a dried product of water paste (■) used in Examples.

[Figure 2] An X-ray diffraction diagram of a dried product of water paste (■) used in Examples.

[Figure 3] An X-ray diffraction diagram of a dried product of water paste (■) used in Examples.

FIG. 4 is an X-ray diffraction diagram of the ■-type oxytitanium phthalocyanine obtained in Example 1.

FIG. 5 is an X-ray diffraction diagram of type B oxytitanium phthalocyanine used in Examples and Comparative Examples.

FIG. 6 is an X-ray diffraction diagram of A-type oxytitanium phthalocyanine used in Examples and Comparative Examples.

[Claim 2] drawing

[Figure 1]

[Figure 2]

[Figure 3]

[Figure 4]

[Figure 5]

[Figure 6]

Claims (4)

[Claims] 1. A water paste of oxytitanium phthalocyanine is milled with a solvent containing a saturated hydrocarbon solvent, and the Bragg angle (2θ±0.2°) in Cukα characteristic X-ray diffraction is 9. 0°, 14.2
°, 23. A method for producing oxytitanium phthalocyanine having strong peaks at 9° and 27.1°. 2. The saturated hydrocarbon solvent has 5 carbon atoms in its main chain.
12. The method for producing oxytitanium phthalocyanine according to claim 1. 3. The method for producing oxytitanium phthalocyanine according to claim 1 or 2, wherein the saturated hydrocarbon solvent has a methyl group at the 2-position. 4. The method for producing oxytitanium phthalocyanine according to claim 1, wherein the water paste of oxytitanium phthalocyanine is a water paste obtained by an acid pacing method.