JPS58183757A - Novel crystal polymorphism of nonmetallic phthalocyanine and preparation thereof - Google Patents

Abstract

NEW MATERIAL:A crystal polymorphism of nonmetallic phthalocyanine having an X-ray diffraction pattern exhibiting characteristic lines at 7.6, 9.2, 16.8, 17.4, 20.4 and 20.9 Bragg angles (2theta+ or -0.2 deg.). USE:A blue pigment having improved crystallinity, brightness, and heat and solvent resistance, etc. PROCESS:alpha-Type nonmetallic phthalocyanine is milled at 50-180 deg.C, preferably 60-130 deg.C, for a time sufficient to transform the crystallographic form under stirring or a mechanical stress.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel crystalline polymorphs of thermometallic phthalocyanides.

Phthalocyanine pigments are highly valued for their properties such as high coloring power, beautiful color tone, and excellent heat resistance, chemical resistance, and light resistance. It is increasing year by year (indicated by -).Among them, metal-free phthalonanine has a strong yellowish blue color and has a unique hue.

In general, metal-free phthalocyanine has crystal polymorphisms of α type and β type.
Type, γ 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, crystal polymorphs of these metal-free phthalocyanines (J phthalocyanine pigments except for the β type) have poor crystal stability and problems in heat resistance and solvent resistance.

As a result of research on metal-free phthalocyanine, the present inventors have discovered that the X-ray diffraction pattern and/or infrared absorption spectrum are different from any previously known ones, and that they have a novel and unique greenish hue with extremely excellent heat resistance and solvent resistance. crystal polymorphism (
The present invention was based on the knowledge that there is a τ-type metal-free phthalonanine (referred to hereinafter as τ-type metal-free phthalonanine).

In other words, the invention in Box 1 of the present application is based on the plastic angle (2θ±02
degree) is 7.6.9.2.16.8, l 7.4.20.
τ having an X-ray diffraction pattern showing strong lines at 4 and 209
Regarding type metal-free phthalocyanine, the invention of No. 02 of the present application is to prepare α-type metal-free phthalocyanine from X to 180°C.
tj-, < refers to a manufacturing method in which milling is performed at 60 to 130° C. with stirring or mechanical strain for a sufficient time to exhibit the τ type.

In the present invention Q, X-ray diffraction and infrared spectra exhibit a range depending on the formation of lattice defects or dislocations in the crystal due to differences in manufacturing conditions. Moreover, the black angle 2θ is powder X,
This was measured using a W diffractometer with CuK"+/N' of 1,541 KA.

1 to 4 are X-ray diffraction patterns of α-type, β-type, X-type and τ-type crystals of metal-free phthalo/anine, respectively. The X-ray diffraction diagram of X-type metal-free phthalo/anine was taken from Japanese Patent Publication No. Sho 44-14106, "Production method of X-type metal-free phthalocyanine."

Note that the τ type is an α type metal-free phthalo-7-anine with poor crystallinity and is almost amorphous, so it is omitted from the drawings.

Comparing the X-ray diffraction diagram angles of the τ-type metal-free phthalocyanine according to the present invention with those of other crystal forms, the τ-type has angles of 201 and 20. A clear diffraction 3 line appears near g, and 2 o
Diffraction lines of length, 2 o, and H are not observed. Deformed, τ type (1
A strong and sharp diffraction pattern comparable to the β-type was obtained.
It can be seen that it has stable and good crystallinity, which is incomparable to the α, γ, and X types, which have poor crystallinity.

Further, it can be clearly distinguished from other crystal forms from the measurement of the infrared absorption spectrum of τ-type metal-free phthalocyanine &1 according to the present invention.

Table 1 compares the infrared absorption spectra of various crystal forms of metal-free phthalonanine.
.

Chem, Vol 127.3230 (1968) by Sharp (J.

-71 し Y'- H, 5harp) O, J: Bi = = half-graduation (M, L1!r
[Spectral characteristics of a new crystal polymorph of metal-free phthalocyanine (5pectrosc)]
opicCharacterizationofn
ew polymorph of Metal Fre
The infrared absorption spectrum of τ-type metal-free phthalonanine is based on the actual measurement.

Weak W1 Intermediate... m1 Strong... Represented as S Ll
sh stands for Njorda.

As is clear from Table 1, the absorption wavenumber of the τ-type metal-free phthalocyanine at 700 to 800 crn is different from that of the α-type, β-type, and X-type, and is relatively low in the X-ray diffraction pattern. The absorption wave number near 3300 is significantly different from the τ type.

The τ-type metal-free phthalocyanine according to the present invention is produced in the following manner. That is, 100 parts by weight of α-type gold-free maple lid O talonanine is stirred or mechanically strained at a temperature of 180°C to 180°C, preferably 60 to 130°C, for a time sufficient to convert the crystals. Metal-free phthalocyanine having a τ-type crystal form is produced by milling.

The α-type phthalocyanine used in the present invention is the [phthalocyanine compound J (Mo5e
r and Thomas ” Phthalocya
Those obtained by known methods such as nine compounds and other suitable methods are used. For example, hot metal phthalocyanine can be demetallized by acid such as sulfuric acid, such as lithium phthalocyanine, sodium phthalocyanine, calcium phthalocyanine, magnesium phthalocyanine, etc. Those made directly from nitrile, aminoiminoisoindolenine or alcoiminoisoindolenine 7 are used.

The metal-free phthalocyanine obtained by the already well-known method is desirably dissolved in sulfuric acid at 5°C or below, or converted into a sulfate salt, and then poured into water or ice water to re-precipitate. A type 1α metal-free phthalocyanine is obtained. It is preferable to use the α-type free phthalo-7-anine treated in this way in a dry state (however, a water paste form can also be used. As a dispersion medium for stirring and kneading, pigments are usually used. It may be used for dispersion, emulsification, etc., such as glass beads, steel beads, alumina balls, and flint stones.

], or L 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 not necessarily required.

If a solvent is required during stirring, kneading, or grinding, it may be liquid at the temperature during stirring and kneading, such as alcoholic solvents, such as glycerin, ethylene glycol,
Dietylenoglycol also refers to polyethylene glycol - from the group of solvents such as cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ketone solvents, and ester ketone solvents. It is preferable to select one or more types.

Typical devices used in the crystal transition process include general stirring devices such as homomixers,
There are dispersers, agitators, stirrers or kneaders, Banbury mixers, ball mills, sand mills, attritors, etc.

The temperature range in the crystal transition step of the present invention is 08 to 180°C, preferably 60 to 130°C.Also, it is also effective to use crystal nuclei as in the normal crystal transition step. ]j method.

The rate of crystal transition to the τ type largely depends on the efficiency of stirring, the strength of mechanical force, the particle size of the raw material, and the temperature profile, but kinetic analysis is very complex and does not meet the intent of the present invention. It's not the place to do it.

In the present invention, after the completion of the crystal transition step, it is possible to add a long-lasting step that provides clear coloring and strong coloring power simply by removing auxiliary agents, organic solvents, etc. using a conventional purification method and drying.

The particles of the τ-type metal-free 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, unexpectedly, this τ-type metal-free phthalocyanine has a clearer hue and greater coloring power than other crystalline metal-free phthalonanine pigments obtained by conventional methods, and has improved heat resistance and solvent resistance. It is. That is,
The τ-type metal-free phthalo/anine according to the present invention has a stable crystal form when burned in many commonly used solvents, and can be used for various purposes. For example, when τ-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, and even when boiled in toluene at 100°C for more than 3 hours, crystalline forms remain No metastasis is seen. Also,
It also has excellent heat resistance, with no crystalline transformation observed even when left in air at 150°C for 50 hours or more.

The present invention differs from the prior art in that it mills phthalocyanine under a specific temperature with simple stirring or mechanical strain without any special purification treatment, resulting in stable, bright, and strong coloring with excellent crystallinity. The feature is that τ-type phthalocyanine, which is a new crystal form with excellent heat resistance and solvent resistance, can be obtained.

Reference examples and examples are shown below. Example Chubu is 14.5 parts of aminoiminoindolenine by weight and 5 parts of trichlorobenzene.
Heated at 200°C for 2 hours in 0 parts, and after reaction, the solvent was removed by steam distillation. The residue was purified with a 2% aqueous hydrochloric acid solution, followed by a 2% aqueous sodium hydroxide solution, thoroughly washed with water, and dried to obtain 8.8 parts of metal-free phthalocyanine (70% yield). The thermometallic phthalocyanine thus obtained has a β-type crystal form. The transition from β type to α type is produced by the following operation. 98% sulfuric acid 1 below 10℃
In 0 parts, 1 part of β-type metal-free phthalocyanine is dissolved little by little, and the mixture is stirred for about 2 hours while maintaining the temperature below 5°C. Subsequently, the sulfuric acid solution was poured into 200 parts of ice water, and the precipitated crystals were filtered. When the crystals are washed with distilled water using a strainer that leaves no acid remaining and dried once, 0.95 parts of α-type metal-free phthalocyanine is obtained.

Example 1 10 parts of α-type metal-free phthalocyanine, 20 parts of a grinding aid, and 8 parts of a solvent were placed in a kneader, and 60 to 12
Milled at 0°C for 7-15 hours. In this case, kneading at a high temperature tends to show a β-type crystal form and also makes it easier to decompose.

After confirming the transition to the τ form using an X-ray diffraction diagram, the product was taken out from the container, and the grinding aid and solvent were removed with L1 water and methanol, and then purified with a 2% dilute sulfuric acid water bath, filtered, washed with water, After drying, clear greenish blue crystals were obtained. This crystal was found to be τ-type phthalocyanine by X-ray diffraction and infrared spectroscopy.

Table 2 Example 2 10 parts of α-type metal-free phthalocyanine, 100 parts of grinding aid,
300 parts of the solvent was placed in a container and stirred at 100°C to 130°C under the recipe and conditions shown in Table 3.

Thereafter, processing and analysis similar to those in Example 1 were carried out to obtain τ-type gold-free maple phthalocyanini/.

Table 3 10 parts of α-type metal-free phthalocyanine, 100 parts of grinding aid,
300 parts of the solvent was placed in a sand mill according to the recipe shown in the table, and mixed at a temperature of 100°±20°C for 15 to 25 hours. Confirm the conversion of the crystal in the same manner as in Example 1. Take out 11,
Washing, filtration, drying and analysis (all results were τ
type metal-free phthalonanine was produced.

Table 4

[Brief explanation of the drawing]

FIGS. 1 to 4 are X-ray diffraction patterns of α-type, β-type, τ-type, and τ-type metal-free phthalonanine, respectively. 9b 25 2o +S
+o 5 Procedural amendments (voluntary) 111 cases were displayed by the Commissioner of the Japan Patent Office in the evening of Showa and February 2009 > (Japan Patent Application No. 16191)
Relationship to Case No. 5 Patent Applicant 5 Supplement 11.0 Contents Contents of the Amendment (1) The "Scope of Claims" is corrected as shown in the attached sheet. (2) The [Detailed Description of the Invention J] column of the specification is corrected as follows. ■) Line 3 of page 3 of the specification, “Blank” is replaced by “Bragg”
I am corrected. 42) In the third page of the specification, in the line, "strong" is corrected to "characteristic." 3) Line 3 of page 3 of the specification, replace “blank” with “Bragg”
I am corrected. 4) Page 5 of the specification, lines 1 to 3, “Seems to be X-shaped”
can not see. ” to “20°4.20.
Diffraction line 9 does not appear. ” he corrected. 5) Delete "r100 parts by weight" on page 7, line 6 of the specification. 6) Insert the following sentence on page 8, line 9 of the specification path, after "is obtained." [At this time, inorganic impurities such as sulfuric acid and sand in the water may be mixed in, but this does not interfere with obtaining α-type crystals. 7) On page 11, line 13 of the specification, "special" is corrected to "special." Claims [1, Bragg angle (2θ±0.2 degrees) is 7.6, 9.
A novel metal-free phthalocyanine crystal polymorph having an X-ray diffraction pattern showing renal rays at 2° 16.8, 17.4, 20.4 and 20.9. = 1 2, the infrared absorption spectrum has four absorption bands with the strongest one being 751±23-1 between 700 and 760 cm. A novel metal-free phthalocyanine crystal polymorph according to claim 1, which has two absorption bands of approximately the same intensity between 1320 and 1340 cm-1 and a characteristic absorption at 328B±3 cm-1. . 3. α-type metal-free phthalocyanine at 50-180°C. Preferably, milling is carried out at 60 to 130°C with stirring or mechanical strain for a time sufficient to convert the crystal form.The Bragg angle (2θ±0.2 degrees) is 7.6.9.2, 16. A method for producing a novel metal-free phthalocyanine crystal polymorph having an X-ray diffraction diagram showing characteristic lines at .8, 17.4°, 20.4 and 20.9. ”

Claims (1)

[Claims] 1. The braking angle (2θ±0.2 degrees) is 7.6.92.
X showing strong lines at 168.174.204 and 209
A novel metal-free phthalonanine crystal polymorph with a line diffraction pattern. 2 Infrared absorption surface is between 700 and 760 m'i
The four absorption bands that are strongest at 751±2m are
Between ~1340m and 2 approximately the same strength phthalonanine G crystal polymorph. 3 α-type metal-free phthalocyanine - 180℃, good 4
Black angle (2θ±02 degrees) is 76.9.2.16.8. .17.4.20.4 and 2
A method for producing a novel metal-free phthalocyanine crystal polymorph having an X-ray diffraction pattern showing a strong line at 0.9.