JPS6020970A - New metal-free phthalocyanine crystal polymorph and its production method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel crystalline polymorphs of metal-free phthalocyanines.

Phthalocyanine pigments are highly valued for their properties such as high coloring power, beautiful color tone, and excellent heat resistance, chemical resistance, and weather resistance, and have a wide range of applications in the color material industry, and their importance is increasing year by year. It has increased. Among them, metal-free phthalocyanine has a strong yellowish blue color and has a unique hue.In addition to pigments, it is also attracting attention as an organic electronic material, especially for electrophotographic photoreceptors, solar cells, photoelectric conversion materials, etc. It is being considered.

In general, metal-free phthalocyanine has crystal polymorphisms of α type and β type.
Type, β type, and X type are known, and these can be easily distinguished by comparing their X-ray diffraction patterns and/or infrared absorption spectra.

On the other hand, the crystalline polymorphisms of these metal-free phthalocyanines, except for the β type, have poor crystal stability as phthalocyanine pigments and have problems in heat resistance and solvent resistance.

As a result of research on Mukinho phthalocyanine, the present inventors have discovered that the X-ray diffraction pattern and/or infrared absorption spectrum are different from those of conventionally known ones, and that a new unique greenish hue with extremely excellent heat resistance and solvent resistance has been discovered. crystal polymorphism (
Hereinafter, it will be referred to as modified η-type metal-free phthalocyanine in this specification. ), which led to the present invention. In this specification, the modified η-type metal-free phthalocyanine refers to a pure metal-free phthalocyanine and a mixture with other phthalocyanines as will be described later.

The first invention of the present application comprises 100 parts by weight of thermal metal phthalocyanine, and one or two types of metal-free phthalocyanine having a substituent on the benzene nucleus, or a phthalocyanine nitrogen isomer or metal phthalocyanine which may contain a substituent on the benzene nucleus. It is a mixture crystal with 50 parts by weight or less of the above mixture, and the infrared absorption spectrum has four absorption bands with the strongest 753±1 crn-1 between 700 and 760 cm.
A new crystalline polymorph of metal-free metal-free phthalocyanine (modified η-type metal-free phthalocyanine) having two absorption bands of approximately the same intensity between 320 and 1340 crn' (r3297±5 cm-1). The second invention of the present application comprises 100M parts of α-type metal-free phthalocyanine and a metal-free phthalocyanine having a substituent on the benzene nucleus, or a phthalocyanine nitrogen isoconstruct or metal phthalocyanine which may have a substituent on the benzene nucleus. A mixture consisting of 50 M parts or less of one or more types of mixture 30 to 220
℃, preferably 60 to 130℃, the crystal shape is deformed η
The present invention relates to a method for producing a modified η-type metal-free phthalocyanine, which is characterized by stirring for a sufficient time or milling with mechanical strain to convert it into a mold.

In the present invention, infrared spectra and X-ray diffraction diagrams have different ranges depending on the formation of lattice defects or dislocations in the crystal due to differences in manufacturing conditions.

In addition, the Bragg angle 2θ is calculated using a powder X-ray diffractometer.
cur<ak/Nio 1.54 □Kyu tm e cm+
1w.

Table 1 compares the infrared absorption spectra of various crystal forms of metal-free phthalocyanine.
Spectrum of type J, Phys.

Sharp (J. Chem, Vol. 27.3230 (1968).

H, 5harp) OJ: Biuniton (M, Lardo
n) Both of them announced [Spectral characteristics of a new crystal polymorph of metal-free phthalocyanine].
c Characterization of new
polymorph of Metal Free Ph
The infrared absorption spectrum of modified η-type metal-free phthalocyanine is based on actual measurements. In addition, the β type is α
It is omitted because it is a typeless metal phthalocyanine with poor crystallinity and is close to the shapeless type.

Table-1 The units of the numbers in Table 1 are l? The strength of ll+-1' absorption is weak...W1 middle...m, %...S, and as is clear from Table 1, it is 700 to 800 cm-'
The absorption wave number of the modified η-form metal phthalocyanine is α
type, β type, and X type, and fcX type, which has a relatively similar X-ray diffraction pattern.
There is a clear difference in absorption wavenumbers around 10 to 1340 cm-'.

FIGS. 1 to 5 are X-ray diffraction patterns of α-type, β-type, X-type, and two modified η-hair crystals of metal-free phthalocyanine, respectively. The X-ray diffraction diagram of the X-type metal-free phthalocyanine was taken from Japanese Patent Publication No. 14106/1988 [Method for producing X-type metal-free phthalocyanine]. Two patterns are shown for the modified η type, but this is because the infrared absorption spectra are the same depending on the manufacturing conditions, but the X-ray diffraction patterns are different at high Bragg angles. . Since these have the same infrared absorption spectra, this difference is thought to be due to the directionality of crystal plane growth, and both can be considered to be modified η type.

Comparing the X-ray diffraction diagram angles of the modified η-type metal-free 7-talocyanine according to the present invention with those of other crystal forms, there are clear differences between the α-type and β-type and the relatively similar X-type. The diffraction patterns are completely different at high Bragg angles of 20.0 or more. 20, 3.20.8.2 for modified η type
1.4 and 27.4 Furthermore, clear diffraction lines appear near 22.1 and 28.5, while in the X type, 20.3.20.8.21.4.27.4 and 28 ．．
The diffraction line No. 5 does not appear. In addition, the modified η type has a strong and sharp diffraction pattern that is comparable to the β type, and it is incomparable to the α, β, γ, and X types, which have poor crystallinity, and has stable and good crystallinity. I understand that you have it.

The α-type 7-thalocyanine used in producing the modified η-type metal phthalocyanine according to the present invention and metal-free phthalocyanine containing a substituent on the benzene nucleus; Alternatively, metal phthalocyanines can be used as described in Moser and Torts [Phthalocyanine Compounds J (Mo5er and
Thomas''' Phthalocyanine C
Examples of metal-free phthalocyanines include metal phthalocyanines that can be demetalized with acids such as sulfuric acid, e.g. lithium phthalocyanine,
By acid treatment of metal phthalocyanines containing sodium phthalocyanine, calcium phthalocyanine, magnesium phthalocyanine, etc., -F, phthalodinitrile, and aminoiminoisoindolenine can also be produced directly from haalkoxyiminoindolenine. used. The metal-free phthalocyanine obtained by this already well-known method is preferably dissolved in sulfuric acid at 5°C or below or made into a sulfate salt, and then poured into water or ice water and reprecipitated or hydrolyzed to obtain α-type metal-free phthalocyanine. Phthalocyanine is obtained. At this time, if an inorganic pigment dissolved or dispersed in sulfuric acid or a reprecipitation solution is used, an α-type metal-free phthalocyanine containing an inorganic pigment can be obtained. The inorganic pigment may be any water-insoluble powder used as a hue filler, such as titanium white, zinc white, white carbon, calcium carbonate, etc., and may be used in the form of powder in a variety of ways. Examples include metal powder, alumina, iron oxide powder, and kaolin. The α-type metal-free phthalocyanine containing this inorganic pigment is much easier to grind during pigmentation than that containing no inorganic pigment, and is easier to form into fine particles, which is effective in saving labor and energy.

The α-type metal-free phthalocyanine subjected to such treatment is preferably used in a dry state, or may be used in the form of a water paste. In addition, phthalonanine nitrogen isoforms include various novolfins, such as copper tetrapyridinovolphyrazine in which one or more of the benzene nuclei of phthalocyanine are replaced with all quinoline nuclei, and metal phthalocyanines include copper, di-, Examples include various materials such as kel, cobalt, zinc, tin, and aluminum.

1. Examples of substituents include amide groups, nitro groups, alkyl groups, alkoxy groups, cyan groups, mercapto groups, halogen atoms, and sulfonic acid groups, carboxylic acid groups or their metal salts, ammonium salts, and amines. A relatively simple example is salt. Furthermore, a benzene-nuclear dialkyl group, a carboxylic acid group or a metal salt thereof,
Comparatively simple examples include ammonium salts and amine salts. Furthermore, various substituents can be introduced via a benzene nucleus, a dialkylene group, a sulfonyl group, a carbonyl group, an imino group, etc., and these are conventionally known in the technical field of phthalocyanine pigments as aggregation inhibitors or crystal conversion inhibitors. (e.g. USP
3973981, 4.088507), or an unknown one.

Known methods for introducing each substituent will be omitted.

In addition, those that are not known are described in the Examples as reference examples.

In the present invention, the mixing ratio of α-type metal-free phthalocyanine and metal-free phthalocyanine having a substituent on the benzene nucleus, or a phthalocyanine nitrogen isomer or metal phthalocyanine which may have a substituent on the benzene nucleus is 1001
It is sufficient if it is 50 (weight ratio) or more, but preferably I O
O/30 to 10010.1 (fi amount ratio). If the ratio exceeds this ratio, the modified η-type phthalocyanine obtained tends to bleed, reducing its suitability as a pigment.

In the present invention, in order to mix in the above-mentioned ratio, it is possible to simply mix the α-type metal-free phthalocyanine,
Mixing may be performed prior to dosing. The method of stirring or milling the mixture thus mixed may be the one normally used for dispersing, emulsifying, mixing, etc. of pigments, and examples of dispersion media for stirring and mixing include glass beads, steel beads, alumina balls, etc. One example is flint stone. However, distributed media is not necessarily required. As the grinding aid, those commonly used as grinding aids for pigments may be used, and examples thereof include common salt, bicarbonate of soda, and sulfur salt. However, this grinding aid is also not absolutely necessary.

If a solvent is required during stirring, mixing, or grinding, it may be liquid at the temperature during stirring, mixing, or grinding, such as alcoholic solvents, such as glycerin, ethylene glycol,
It is preferable to select one or more from the group of diethylene glycol or polyethylene glycol and calhitol bath agents, ethylene glycol monomethyl ether, ethylene glycol heptanoethyl ether-based selonlube solvents, ketone solvents, ester ketone solvents, and the like.

Typical devices used in the crystal transition process include general stirring devices, homomixers,
Disperser, agitator, stirrer or kneader, Banbury mixer, ball mill, sand mill,
There are attritors, etc.

The temperature range in the crystal transition step of the present invention is 30 to 220
℃, preferably from 60 to 30℃, within the temperature range z'' It is also an effective method to use crystal nuclei as in the transition process.

The rate of crystal transition to the deformed η-type largely depends on the efficiency of stirring, the strength of mechanical force, the particle size of the raw material, and the temperature, but kinetic analysis is very complicated, and the present invention That's not what I intended.

In the present invention, after the crystal transition process is completed, auxiliary agents and organic solvents are removed by a normal purification method, and a pigment with excellent heat resistance and solvent resistance, which is clear and has high coloring power, can be obtained simply by drying. However, it is also possible to add a normal surface treatment process using a surfactant or resin.

The particles of the modified η-type metal phthalocyanine according to the present invention are extremely soft and can be easily dispersed in a color vehicle, and especially when used as a paint, there is no decrease in coloring power or thickening during storage. Additionally, when two or more types of pigments are mixed, the degree of the pigment decreases or the pigment suitability changes, but this deformation η
Metallic phthalocyanine has a clearer hue and greater coloring power than other crystalline metal-free phthalocyanine pigments obtained by conventional methods, allows subtle hue adjustment without degrading saturation, and is heat resistant and solvent resistant. The improvement in performance is unexpected. That is, the modified η-type metal phthalocyanine according to the present invention has a stable crystal form in many commonly used solvents, and can be used for various purposes. For example, when a modified η-type phthalocyanine is boiled for 3 hours or more at the boiling points of acetone, THF, and ethyl acetate, no change in crystal form occurs. In particular, it is extremely stable against aromatic solvents that easily transform solvent unstable forms such as α-type phthalocyanine into β-type, for example in toluene at 100°C.
Even when boiled for more than 3 hours, no change in crystal form is observed. Furthermore, it has excellent heat resistance, and no change in crystal form is observed even when it is left in air at 200° C. for 50 hours or more.

Furthermore, the modified η-type metal-free phthalonanine according to the present invention is
Subtle hue adjustment is possible by changing the type and amount of various derivatives used in combination with the metal-free phthalocyanine. For example, when the absorption spectrum of the modified type I metal-free phthalocyanine obtained in Examples 1-d and 2-a dispersed in a dioxane solution is measured as shown in Figure 6, the changes in the spectrum can be understood. Good morning.

The present invention differs from the prior art in that it mills 7-thalocyanine with simple stirring or mechanical strain at special temperatures without any special purification treatment, resulting in a safe, bright and colorful product with excellent crystallinity. The method is characterized in that a modified L-type metal-free phthalocyanine, which is a new crystalline form with excellent heat resistance and solvent resistance, has a high coloring power, allows subtle hue adjustment without deterioration of color, and is characterized by the ability to obtain a modified type I metal-free phthalocyanine.

Reference examples and examples are shown below. For example, the middle section indicates the M section.

Reference Example 1 Aminoimimeindolenine 14.5 parts 't) i Heated in 50 parts of dichlorobenzene at 200°C for 2 hours. After the reaction, the solvent was removed by steam distillation, followed by dihydrochloric acid aqueous solution. After purification with a 2% aqueous sodium hydroxide solution, the product was thoroughly washed with water and dried to obtain 8.8 parts of metal-free phthalocyanine (yield: 70%). Do it like this×
The obtained metal-free phthalocyanine has a β-type crystal form. The transition from β type to α type is produced by the following operation. 1
One part of β-type metal-free phthalocyanine is gradually dissolved in 10 parts of 98-thiosulfuric acid at 0° C. or lower, and the mixture is stirred for about 2 hours while maintaining the temperature at 5° C. or lower. Subsequently, the sulfuric acid solution is poured into 200 parts of ice water, and the precipitated crystals are filtered. The crystals are washed with distilled water until no alcohol remains and are dried to obtain 0.95 parts of α-type metal-free phthalocyanine.

Example 11 100 parts of pure metal phthalocyanine and 10 parts of each derivative shown in Table 2 obtained in the same manner as Reference Example 2.3 described later were dissolved in ice-cooled 98 thiosulfuric acid, precipitated on fire, and then boiled. A homogeneous mixture of both is obtained by filtering, washing with water, and drying. 100 parts of this mixture, 400 parts of ground common salt and 100 parts of polyethylene glycol were placed in a kneader, and
Milled for 8 hours at °C. After taking it out, it was purified with a 2% dilute sulfuric acid aqueous solution, filtered, washed with water, and dried to obtain clear greenish blue crystals.

This crystal was a modified η-type metal-free phthalocyanine having the X-ray diffraction pattern shown in FIG. 4 and the infrared absorption spectrum shown in Table 1.

Table 2 (CuPC is copper phthalocyanine residual fund, and the number outside parentheses indicates the average number of substitutions based on analysis.) Reference example 2 15 parts of copper phthalocyanine, trichlorbe, 50 parts of copper phthalocyanine
A mixture of 0 parts of acetyl chloride, 25 parts of acetyl chloride, and 70 parts of aluminum chloride was stirred at 60 to 80°C for 8 hours,
Thereafter, it was poured into water, and the solid fraction was filtered, washed with water, and dried to obtain a compound represented by the following formula.

CuPc(-COCH2(,t)t3 Various phthalocyanine derivatives were obtained by reacting CuPc(-COCH2(,t)t3) with amines by a known method.

Reference Example 3 The various phthalocyanine derivatives obtained in Reference Example 2 were reduced by a known method to obtain the general formula (where R1 and R2 are a hydrogen atom, an alkyl group, an aryl group, a hetero group'-! or a nitrogen atom and ll+ , R2 may form a heterocycle.) A phthalocyanine derivative represented by the following formula is obtained. For example, to reduce the phthalocyanine derivatives shown in the table below,
6 parts of potassium hydroxide is dissolved in 80 parts of diethylene glycol, 6 parts of the above-mentioned phthalocyanine derivative is pulverized sufficiently finely and added thereto, 10 parts of hydrazine hydrate is gradually added, and the mixture is refluxed for about 10 hours. The resulting deep blue slurry was poured into water through a spout, washed with water, and dried.

Example 2 Metal-free phthalocyanine was dissolved in ice-cooled 98% sulfuric acid,
α-type metal-free phthalosinine is obtained by precipitating it in water at 20° C. or lower, filtering it, washing with alkali, washing with water, and drying. 100 parts of this α-type metal-free phthalocyanine, 10 parts each of the hot metal phthalocyanine shown in Table 3 which was halogenated by a conventional method.
M, food [2 oo parts and polyethylene glycol 100
100 to 120 of the crystals had the X-ray diffraction pattern shown in FIG. 5 and were a modified η-type metal-free phthalocyanine exhibiting the infrared absorption spectrum shown in Table 1.

Table 3 However, Table 3ct-Pc shows thermometallic phthalocyanine derivatives.

Example 3 Metal-free phthalocyanine, copper phthalocyanine (hereinafter referred to as cu-Pc), and nickel phthalocyanine (hereinafter referred to as N i-P, c), which were chlorosulfonated by a conventional method.
was reacted with various amines to form phthalocyanine derivatives shown in Table 4.

Table 4 Each of the above phthalocyanine derivatives was treated with metal-free phthalocyanine in the same manner as in Example 1 to obtain a greenish blue pigment having similar modified η-type crystals.

Example 4 Copper phthalocyanine is chloromethylated and reacted with various amines to obtain the phthalocyanine derivatives shown in Table 5.

These derivatives were produced by methods known in the art, such as Japanese Patent Publication No. 32-5083.

Example 1 using various phthalocyanine derivatives shown in Table 5
By treating with phthalocyanine in the same manner as in Example 1, results similar to those in Example 1 are obtained.

Table 5 Example 5 Copper tetrapyridinoborohydrazine was synthesized by a known method.

100 parts of metal-free phthalocyanine and 5 parts of the above copper tetrapyridinoporphyrazine were dissolved in concentrated sulfuric acid, poured into water, filtered, washed with water, and dried to obtain a homogeneous and fine mixture.

Put 100 parts of this mixture, 500 parts of common salt and 100 parts of diethylene glycol into an attritor,
The product was ground for 8 hours at 0.degree. C., and post-treated in the same manner as in Example 1 to obtain a metal-free phthalocyanine having a modified η-type packed crystal form with clear color and high tinting power.

Example 6 100 parts of phthalocyanine and 20 parts of kelphthalocyanine
Dissolve part of the mixture in concentrated sulfuric acid, pour into water, filter through the mouth, wash with water, and dry to obtain a homogeneous and fine mixture. 100 parts of this mixture, 1,000 parts of steel balls, and 500 parts of polyethylene glycol were placed in a pot and ground at 100°C for 40 hours. A phthalocyanine having the modified η-type packed crystal form shown below was obtained. .

[Brief explanation of drawings]

Figures 1 to 5 are two types of X-ray diffraction patterns of α-type, β-type, FIG. 3 is an absorption spectrum diagram of the modified η-type metal-free thalocyanine. Patent applicant Toyo Ink Manufacturing Co., Ltd. 1 Meo, 2.1 2θ 7G opening 1], VGO-20970 (8) 2/ Hari-1 2 tough t■゛4 exhibition (IyIK) Continued from page 1■ Applicant: Hitachi, Ltd. 5-1 Marunouchi, Chiyoda-ku, Tokyo

Claims (4)

[Claims] (1) 100 parts by weight of metal-free phthalocyanine and one or more types of metal-free phthalocyanine having a substituent on the benzene nucleus, a phthalocyanine nitrogen isomer or metal phthalocyanine which may have a substituent on the benzene nucleus It is a mixture crystal with 50 parts by weight or less, and the infrared absorption spectrum is between 700 and 760.
' is the strongest four absorption bands from 1320 to 1340c
Two absorption bands of almost equal strength between rn 'z, 329
A novel metal-free phthalocyanine polymorph with a characteristic absorption at 7±5 m-1. (2) Bragg angle (2θ±0.2 degrees) is 7.5.9.
1.16.8.17.3.2o, 3.2o, 8.21.
The novel metal-free phthalocyanine crystal polymorph according to claim 1, which has an X-ray diffraction pattern showing strong peaks at 4 and 27.4. (3) Bragg angle (2θ±0.2 degrees) is 7.5.9.
1116.8, l 7.3.20.3.20.8.21
．． 4.22.1. The novel metal-free phthalocyanine crystal polymorph according to claim 1, which has an X-ray diffraction pattern showing strong peaks at 27.4 and 28.5. (4) Mixture of the following (A) and (B) at 30 to 220
The infrared absorption hypervector is 70°C, preferably 60 to 130°C, with stirring or mechanical strain for a time sufficient to convert the crystal form.
753±crn-1 is the strongest four absorption bands between 0 and 760 cm', and 2 absorption bands between 1320 and 1340 crn'.
A method for producing a new crystalline polymorph of metal-free phthalocyanine having a characteristic absorption in the absorption band k of approximately the same intensity as that of 3297±5 crn''. (A) - 100 parts by weight of α-type metal-free ntthalocyanine. B) 50 parts by weight or less of a metal-free phthalocyanine having a substituent on the benzene nucleus, a phthalocyanine nitrogen isomer or a mixture of two or more metal phthalocyanines which may have a substituent on the benzene nucleus.