JP2782809B2 - Method for producing oxytitanium phthalocyanine - Google Patents

Description

The present invention relates to oxytitanium phthalocyanine (hereinafter referred to as TIP).
More specifically, the present invention relates to a method for producing a TIOPC crystal using dichlorotitanium phthalocyanine or dibromotitanium phthalocyanine as a raw material.

(Prior Art) Phthalocyanines are useful compounds for coloring paints, printing inks and resins, or as electronic materials, and have recently been actively used as materials for electrophotographic photoreceptors.

As a result of various studies on the method for producing TiOPc, the present inventor found that the X-ray diffraction spectrum showed a Bragg angle (2θ).
± 0.2 ゜) TiO ゜ with major diffraction peaks at 9.3 ゜, 10.6 ゜, 13.2 ゜, 15.2 ゜, 20.8 ゜, 26.3 ゜ (hereinafter abbreviated as A-type TioPC) and 7.6 ゜, 10.2 ゜, 22.3 ゜, 25.3 ゜, TiOPc having a main diffraction peak at 28.6 ゜ (hereinafter abbreviated as B-type TiOPc), and further, a TiOPc having a main diffraction peak at 7.0 ゜, 15.6 ゜, 23.4 ゜, and 25.6 ゜ (hereinafter abbreviated as C-type TiOPc) The existence of crystal forms was confirmed, and their production methods were proposed (JP-A-62-256865, JP-A-62-256867, and JP-A-63-56867).
-366 publication).

In the above production method, it is necessary to delicately control the rate of temperature rise during the reaction between orthophthalodinitrile and titanium tetrachloride, the overtemperature after the reaction, and the like.
Seed crystal forms tended to be mixed.

According to JP-A-61-217050, dichlorotitanium phthalocyanine (hereinafter abbreviated as TiCl ₂ Pc) is heated together with concentrated ammonia water, washed with acetone, and washed with acetone.
Although OPc is obtained, there is a disadvantage that the operation is complicated and the crystal form tends to be a mixture of the A type and the B type.

As (INVENTION Problems to be Solved) described above, the conventional method to obtain a TiOPc by hydrolyzing TiCl ₂ P _C produced in the condensation reaction with ortho-phthalodinitrile and titanium tetrachloride with water or Anmoniya Water in there, but not only the aforementioned drawbacks, the following equation operations complicated TiCl ₂ P _C It takes a long time for the hydrolysis, low crystallinity of the resulting TiOP _C, the enclosing problems etc. requires treatment with more N- methylpyrrolidone or acetone.

The present inventor has such a problem to solve, and, A-type, made intensive studies to develop a selective preparation of B-type and C-type TiOP _C crystal.

(Means for Solving the Problems) As a result, TiOP _C crystals from Surprisingly TiCl ₂ P _C or dibromo phthalocyanine (hereinafter TiBr abbreviated as ₂ P _C), conventionally known hydrolysis methods other than And found a method for obtaining the compound extremely easily, and arrived at the present invention.

That is, the gist of the present invention is that TiCl2Pc or TiBr2Pc is
Alkyl lactams, aromatic nitro compounds, halogenated phenols, aromatic ring-containing acid amides, nitrogen-containing cyclic ethers, aromatic amines, aliphatic aldehydes, aromatic aldehydes, aliphatic ketones, aromatics Ketones, lactones, lactams, acid amides, substituted phenols and nitriles, N-ethylaniline, contacting with an organic solvent selected from the group consisting of dimethyl sulfoxide, a method for producing a TiOPc crystal, Exist. Thus, with this configuration, TiOPc can be obtained very easily,
Also, by selecting the type of organic solvent, A type, B type and C type
Type TiOPc crystals can be selectively produced. Further, other crystal forms of TiOPc, which are often recognized in the conventional method, are not mixed and have a sufficiently high crystallinity, so that they can be practically used as they are. However, if necessary, water, methanol, acetone, N-methylpyrrolidone can be used. , Dimethylsulfoxide, N, N-dimethylformamide and the like.

(Operation) Hereinafter, the present invention will be described in detail.

Examples of the organic solvent used in the present invention include N-alkyllactams, aromatic nitro compounds, halogenated phenols, aromatic amides, nitrogen-containing cyclic ethers, aromatic amines, aliphatic aldehydes, It can be arbitrarily selected from aromatic aldehydes, aliphatic ketones, aromatic ketones, lactones, lactams, acid amides, substituted phenolic acids and nitriles, N-ethylaniline, and dimethyl sulfoxide. Also, if the organic solvent is liquid at the time of contact, it does not matter whether it is liquid or solid at normal temperature. When a high melting point organic solvent is used, the operability is improved by melting or incorporation of an inert low melting point ether, ester, hydrocarbon or the like, usually up to about 80%, preferably up to 70%. You can also.

The relationship between the type of the organic solvent used and the crystal form of the TiOPc to be formed is approximately as shown in Tables 1 and 2 below, but there are, of course, exceptions.

In addition, 2,5-xylenol is given as one that gives C-type TiOPc.

Of course, organic solvents other than the above also include N-alkyl lactams, aromatic nitro compounds, halogenated phenols,
Aromatic ring-containing acid amides, nitrogen-containing cyclic ethers, aromatic amines, aliphatic aldehydes, aromatic aldehydes,
Any aliphatic ketones, aromatic ketones, lactones, lactams, acid amides, substituted phenolic acids and nitriles can be used.

The temperature at which TiCl ₂ Pc or TiBr ₂ Pc is brought into contact with the organic solvent can be arbitrarily selected, but is preferably in the range of 50 to 200 ° C. Since the higher the temperature, the higher the rate of formation of TiOPc, it is advantageous to use an organic solvent having a high boiling point.

The contact time between TiCl ₂ Pc or TiBr ₂ Pc and the organic solvent is determined by the type and amount of the organic solvent and the temperature, but is usually 1 to 3 hours at 130 ° C.

There is no particular limitation on the use ratio of TiCl ₂ Pc or TiBr ₂ Pc to the organic solvent, but a range of 1: 5 to 100 is preferable in consideration of contact efficiency, operability, and the like. If the amount of the organic solvent used is too low, the contact efficiency becomes poor, and the generation rate of the TiOPc crystal decreases.

The method of contacting TiCl ₂ Pc or TiBr ₂ Pc with the organic solvent is not particularly limited, but a method of contacting and mixing both in a stirring tank is preferable. In addition, a method of flowing an organic solvent through a column filled with TiCl ₂ Pc or TiBr ₂ Pc can also be adopted. In short, a method in which both are brought into contact with each other may be used.

(Effects of the Invention) As described above in detail, the present invention provides a novel method for producing a TiOPc crystal, and a TiOPc crystal having a specific crystal form can be selectively obtained extremely easily as compared with the conventional method. Therefore, it is extremely advantageous for production on an industrial scale.

(Examples) Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

Synthesis Example of TiCl ₂ Pc In a two-reaction flask equipped with a thermometer, a stirrer, and a reflux condenser, 184 g (0.718 mol) of orthophthalodinitrile and α
-200 ml of chloronaphthalene was charged, 40 ml (0.364 mol) of titanium tetrachloride was added with stirring, and the mixture was heated to 200 ° C and reacted for 5 hours. After cooling the reaction solution to 120 ° C, the mixture was heated, and the obtained crude cake of TiCl ₂ Pc was washed with α-chloronaphthalene at 120 ° C.
After washing with 1000 ml, 224 g of a blue wet cake of pure TiCl ₂ Pc was obtained.

 Elemental analysis values (dry product) were as follows.

C H N Cl calculated value% 60.88 2.55 17.75 11.23 Found% 60.66 2.37 17.68 11.08 Example 1 thermometer, stirrer, a 200ml flask equipped with a reflux condenser and a wet cake 11.2g of TiCl ₂ P _C N-methylpyrrolidone 150m
l, heat to 140 ° C and stir for 2 hours, then 80 ° C
The resulting cake was washed with methanol and dried to obtain 7.2 g of blue powder of A-type TiOPc. 70% yield
(Vs. orthophthalodinitrile).

The powder X-ray diffraction spectrum of the obtained TiOPc is shown in FIG.

Examples 2 to 26 and Comparative Examples 1 to 3 The results of experiments conducted in the same manner as in Example 1 except that the kind of the organic solvent and the processing conditions were changed are shown in the following table.

FIGS. 2 and 3 show the powder X-ray diffraction spectra of the TiOPc obtained in Examples 2 and 3, respectively.

[Brief description of the drawings]

FIG. 1 is a powder X-ray diffraction spectrum of the A-type TiOPc obtained in Example 1, and FIG. 2 is a B-type TiPc obtained in Example 2.
3 is a powder X-ray diffraction spectrum of OPc. FIG. 3 is a powder X-ray diffraction spectrum of the C-type TiOPc obtained in Example 3.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C09B 67/12 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. Dichlorotitanium phthalocyanine or dibromotitanium phthalocyanine is converted to N-alkyl lactams, aromatic nitro compounds, halogenated phenols, aromatic ring-containing acid amides, nitrogen-containing cyclic ethers, aromatic amines, aliphatic amines Organics selected from the group consisting of aldehydes, aromatic aldehydes, aliphatic ketones, aromatic ketones, lactones, lactams, acid amides, substituted phenols and nitriles, N-ethylaniline, dimethyl sulfoxide A method for producing an oxytitanium phthalocyanine crystal, which is brought into contact with a solvent.