JPH0230345B2 - FUKASAKUKAGOBUTSUOYOBISONOSEIHO - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel addition complex compound with high color stability against heat and a method for producing the same.

Conventionally, many types of monoazo lake pigments are known, and these are effectively used as coloring materials for paints, printing inks, rubbers, synthetic resins, cosmetics, etc., depending on their properties.

Chemical structure below Those with CINo.15880 (CIPigment
Red63) and is a red monoazo lake pigment commonly called Lake Bordeaux 10B.

This Lake Bordeaux 10B is obtained in the form of needles, spheres, or amorphous, exhibits a bluish red color, and has excellent light resistance, oil resistance, solvent resistance, and water resistance, and is used in a wide range of fields such as paints and cosmetics. .

As a result of intensive research to develop new pigment physical properties for the conventional Lake Bordeaux 10B, the present inventors have developed an addition complex compound that has unprecedented properties and pigment physical properties by adding ethylene glycol to Lake Bordeaux 10B. I found it.

That is, if the conventional Lake Bordeaux 10B is heat treated in ethylene glycol, or the sodium salt of Lake Bordeaux 10B is dispersed or dissolved in a solvent containing ethylene glycol, heated, and a calcium salt solution is added dropwise thereto. It was found that small and large plate-like crystals containing many rhombuses were obtained, and because of their plate-like crystals, they exhibited a pearlescent luster in the pigment dispersion and also exhibited high color stability against heat. Ta. Further examination of the crystal structure revealed that the conventional crystal structure was 2θ
Unlike those that have an X-ray diffraction pattern that shows high intensity at 4.5 to 5.0°, those that have been completely processed to become plate-like crystals and those that have been crushed are 2θ
shows no peak between 4.5 and 5.0°, and 2θ is 5.8°, 8.4°,
It was found that the addition complex of the present invention had a completely new crystal structure as it had high intensity peaks at 11.4°, 24.4°, etc.

Regarding addition complex compounds, those consisting of zinc phthalocyanine pigment and solvent molecules such as amines are known (J.Phys.Chem.72.No.7, 1968,
(pp. 2446-2456), Lake, Bordeaux 10B An addition complex compound consisting of a monoazo lake pigment and ethylene glycol has not been reported so far.

The present invention is based on the following chemical structural formula: It is an addition complex compound consisting of the monoazo lake pigment shown by and ethylene glycol.

Furthermore, the present invention provides a method for producing the addition complex compound, in which the sodium salt of the monoazo lake pigment represented by the above chemical structural formula is dispersed or dissolved in a solvent containing ethylene glycol and heated, and a calcium salt solution is added thereto. It is characterized by forming a lake by dripping. Also, Lake Bordeaux
A similar addition complex can be obtained by directly heat-treating 10B in a solvent containing ethylene glycol. However, the former method of lake formation allows a more complete addition complex to be obtained. The solvent used here may be a mixture of ethylene glycol, ethanol, acetone, etc. Heating is carried out at 40-220°C, particularly preferably at 80-140°C.

The addition complex compound of the present invention will be explained in detail.

The fact that the product of the present invention is a complex compound in which the raw material monoazo lake pigment and the solvent are additionally bonded, and that the crystal structure is different from that of the raw material pigment is as follows: liquid chromatography, differential thermal analysis (DTA) ), confirmed by thermal gravimetric analysis (TGA), X-ray diffraction, and other physical properties.

The retention time of a peak appearing in a liquid chromatogram of a solution of this addition complex dissolved in a solvent such as dimethylformamide is the retention time of a peak appearing in a liquid chromatogram of a solution of the raw material Lake Bordeaux 10B dissolved in the same solvent. matches. This shows that the addition complex of the present invention maintains the chemical structure of Lake Bordeaux 10B and the solvent is additionally bonded to it. This is also supported by the fact that the X-ray diffraction pattern of the pigment according to the invention after immersion in water for several days shows that of Lake Bordeaux 10B.

Next, the first section shows the differential thermal analysis of this addition complex.
According to the figure, an endothermic peak appears at around 250°C due to the elimination of ethylene glycol incorporated into the crystal, and an accompanying weight loss can be seen. Also, from this weight loss, it can be seen that one molecule of ethylene glycol is coordinated per molecule of Lake Bordeaux 10B. These results confirm that this new pigment is an addition complex of Lake Bordeaux 10B.

It is clear from the X-ray diffraction pattern that the novel monoazo lake pigment of the present invention has a new crystal structure different from the conventional Lake Bordeaux 10B.
In other words, according to Figure 2, which shows the X-ray diffraction pattern of conventional Lake Bordeaux 10B due to CuKα radiation, 2θ is
It has peaks at 4.6°, 9.3°, 10.8°, 11.6°, and 158°, but in Figure 3, which shows the X-ray diffraction pattern by CuKα radiation of the product obtained by the present invention, 2θ is approximately
It has peaks at 5.8°, 8.4°, 11.4°, and 24.4°.

As is clear from the above, the X-ray diffraction pattern obtained with the present invention is different from that of the conventional rake pattern.
It is a new pigment with a new crystal structure different from Bordeaux 10B.

As described above, the novel monoazo lake pigment addition complex compound obtained by the present invention is a different substance from the conventional Lake Bordeaux 10B, but it has basic physical properties such as light resistance and oil resistance, and color tone. There is no difference between the two. However, the pigment of the present invention has further improved color stability against heat,
Moreover, the particle shape is different from that of the conventional Lake Bordeaux 10B, and the plate-shaped crystals are obtained, and these plate-shaped crystals can produce a pearlescent luster in a pigment dispersion. It is clear from differential thermal analysis that the pigments of the invention have high thermal stability. Figure 4 shows the conventional differential thermal analysis of Lake Bordeaux 10B.
As shown in the figure, in the case of pigments manufactured in ethylene glycol, no peaks appear until around 250℃, and unlike the conventional Lake Bordeaux 10B, there is no change in color tone at 140℃, and even at 250℃ It is completely thermally stable up to ℃. Therefore, such pigments are used in paints, printing inks, and other applications that require color stability.
It can be suitably used in fields such as rubber, synthetic resins, paint, and cosmetics.

The reason for this characteristic is that, unlike the conventional Lake Bordeaux 10B, which incorporates water into its crystals, the pigment according to the present invention incorporates ethylene glycol, which has a higher boiling point than water, into its crystals. Therefore, it is thought that the water of crystallization that is desorbed at 140°C and 210°C is not retained, and furthermore, the temperature at which ethylene glycol in the crystal is desorbed is higher than that of water, resulting in improved thermal stability. . In addition,
This characteristic is the same for both plate-shaped crystals and amorphous powder obtained by crushing them.

The pigment of the present invention is suitably used as a color-stable red colorant in the fields of paints and synthetic resins that require heat resistance.

In addition, the pigment of the present invention is obtained in the form of plate-like crystals, and since these plate-like crystals impart a pearlescent luster to the pigment dispersion, they can be used in applications requiring pearlescent luster, such as nail paints and lipsticks in the decorative field and cosmetics. It can be used effectively.

Normally, in order to give a colored liquid a pearlescent luster, a pearling agent such as ichthyosa, titanium-mica, or aluminum metal powder is dispersed in addition to the pigment to give it a pearlescent luster, but the plate-shaped crystal pigment of the present invention When used, the pigment itself serves as both a coloring agent and a pearling agent, so there is no need to use a pearling agent, and the pigment alone provides a beautiful red colored product with pearlescent luster.

The above thermal stability and pigment physical properties are different from those of conventional lakes and pigments.
This cannot be obtained with Bordeaux 10B, and in this respect, the pigment of the present invention can be said to be extremely useful industrially.

Next, the manufacturing method of the present invention will be explained.

First, the first method is the lake formation method, in which the sodium salt of Lake Bordeaux 10B is dispersed or dissolved in a solvent containing ethylene glycol and heated, and then a calcium salt is dissolved in the same or a different solvent, and this calcium salt is dissolved or dissolved in a solvent containing ethylene glycol. Add salt and make a lake.

Calcium salts used here include chlorides, sulfides, sulfates, phosphates, acetates, borates, carbonates, and hydroxides, but considering its solubility in solvents, calcium chloride is particularly preferred. If stirred at this time, plate-shaped crystals of about 10 to 20 microns will be obtained, and if not stirred, large diamond-shaped plate crystals of about 50 microns will be obtained.

The second method is a heat treatment method, in which Lake Bordeaux 10B itself is used as a raw material and heat treatment is performed in a solvent containing ethylene glycol. However, the first raking method yields a more complete plate-like addition complex.

Figure 5 shows the X-ray diffraction pattern of CuKα obtained by heat treatment, and Figure 6 shows the differential thermal analysis results. 2θ is approximately 5.2°, 10.4°,
The peaks at 15.7° and 25.0° overlap.

Looking at the differential thermal analysis in Figure 6, in addition to 250℃, 220℃
An endothermic peak was observed near °C, indicating that the addition complex was not completely formed into a plate-like addition complex.

In either method, the solvent contains something other than ethylene glycol, such as methanol,
Appropriate amounts of alcohols such as ethanol and other organic solvents may be included, but water is less than 1/4 of the total weight in the case of the lake forming method, and less than 1/10 in the case of the heat treatment method. This is desirable.

Heating temperature is 40° to 220°C, preferably 80° to 140°C
It is. The heating temperature is related to the rate of formation of plate crystals, and generally, the higher the heating temperature, the faster the rate of formation.

Note that the higher the pure pigment concentration of the raw material Lake Bordeaux 10B, the faster the production rate.

Example 1 4 parts of sodium salt of Lake Bordeaux 10B are dispersed in 750 parts of ethylene glycol and completely dissolved at 120°C. A solution of 2 parts of calcium chloride (dihydrate) dissolved in 200 parts of ethylene glycol is added dropwise thereto over 30 minutes with or without stirring.
After 4 hours of dropping and keeping at 120°C, the mixture was washed with filtrate and ethanol, and dried at 80°C for 1 hour to obtain 3.5 parts of diamond-shaped plate crystals with pearlescent luster.

When the obtained pigment was observed under a microscope, many diamond-shaped plate crystals were observed. (Figure 7) This thing is
The diffraction angle 2θ due to CuKα radiation is approximately 5.8°, 8.4°,
An X-ray diffraction pattern with peaks at 11.4° and 24.4° was obtained. When observed with the naked eye, a liquid obtained by dispersing this pigment in a nitrified cotton lacquer exhibited a beautiful red color with a pearlescent luster.

In addition, when differential thermal analysis was performed on the obtained pigment, as shown in Figure 1, there was an endothermic peak at about 250°C, and a corresponding weight loss was observed.
As seen in the traditional Lake Bordeaux 10B
Endothermic peaks at 140°C and 210°C and accompanying weight loss were not observed. According to this, the obtained pigment first releases ethylene glycol in the crystal around 250℃, causing a change in crystal structure, and at 140℃, the crystal structure is much more thermally stable than the conventional Lake Bordeaux 10B. It can be seen that it is.

Example 2 20 parts of Lake Bordeaux 10B were mixed with 1000 parts of ethylene glycol, and heat treatment was continued at 120°C for 8 hours. After treatment, filter, wash with ethanol, and store at 80°C.
After drying for 1 hour, 18 parts of the same red pigment as in Example 1 was obtained.

[Brief explanation of drawings]

FIG. 1 shows differential thermal analysis (DTA) and gravimetric thermal analysis (TGA) of a lake-Bordeaux 10B addition complex obtained by lake formation in ethylene glycol. FIG. 2 shows the X-ray diffraction patterns of the conventional Lake Bordeaux 10B, and FIG. 3 shows the X-ray diffraction patterns of the addition complex obtained by the lake forming method of the present invention, measured with CuKα radiation. FIG. 4 is a diagram of a conventional differential thermogravimetric analysis of Lake Bordeaux 10B. Figure 5 shows the addition complex of Lake Bordeaux 10B obtained by heat treatment.
This is an X-ray diffraction pattern measured with CuKα radiation, and FIG. 6 is a diagram of its differential thermal and gravithermal analysis.
FIG. 7 is a micrograph of an addition complex produced by the lake forming method of the present invention.

Claims (1)

[Claims] 1. The following chemical structural formula (A) An addition complex compound consisting of a monoazo lake pigment and ethylene glycol. 2 The following chemical structural formula (B) A monoazo lake pigment represented by the chemical structural formula (A) below and ethylene glycol, characterized in that the monoazo dye represented by is dispersed or dissolved in a solvent containing ethylene glycol, heated, and a calcium salt solution is added dropwise. Method for producing addition complex compounds. 3. The manufacturing method according to claim 2, wherein the heating temperature is 40° to 200°C. 4 The following chemical structural formula (A) A method for producing an addition complex compound consisting of a monoazo lake pigment represented by the above chemical structural formula (A) and ethylene glycol, which comprises heat-treating the monoazo lake pigment represented by the formula (A) in a solvent containing ethylene glycol. 5. The manufacturing method according to claim 4, wherein the heating temperature is 40° to 200°C.