JPS5815561A - Preparation of addition complex compound of brilliant carmine 6b - Google Patents

Abstract

PURPOSE:To prepare the title compd. with excellent color tone stability under heat, by dispersing or dissolving a specified monoazo lake pigment in a solvent which contain polyhydric alcohol, and adding a solution of a Ca salt dropwise to it under heating. CONSTITUTION:Brilliant Carmine 6B monoazo lake pigment of formulaIis dispersed or dissolved in a solvent which contains a polyhydric alcohol (e.g. ethylene glycol), followed by heating to 40-220 deg.C. Then a solution of a Ca salt (e.g. CaCl2) in an identical or different solvent is added dropwise for formation of the title compd. of formula II in plate crystals having red color and pearly luster. EFFECT:The compd. has improved thermal stability, for it contains no water of crystallization which comes off at 70-80 deg.C but contains high-boiling polyhydric alcohol in the crystal. USE:Coating, cosmetic, printing ink, etc.

Description

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

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

Red 57:1), generally called brilliant carmine 6B, and is one of the typical red monoazo lake pigments.

Brilliant Carmine 6E is obtained in the form of needles, spheres, or amorphous, exhibits a bluish red color, and has excellent light resistance, heat resistance, oil resistance, solvent resistance, and water resistance, and is used in a wide range of fields such as paints and cosmetics. ing.

This pigment is polymorphic and has α-type and β-type crystal structures, and it has been found that this crystal transition is based on the desorption of crystal water (“Coloring Materials Association Journal”, Vol. 2, (1965), pp. 52-56). That is, when the β-form is placed under humidified conditions, it takes in crystal water and transforms into the α-form, and the color tone changes from bluish red to yellowish red. When this α-form is heated to 80° C. or higher, water of crystallization is eliminated and it easily transforms into the β-form.

As described above, by heating the α-type to 80° C. or higher or humidifying the β-type, the crystal structure changes, and the color tone changes accordingly. In addition, α type is Ouk, L radiation 20 is 46°, 93°, 11D0.207°, 23
It has an X-ray diffraction pattern showing peaks at 4°, 254°, but the β type has peaks at 20°, 549°, 150°, and 183°.
There is no difference in the peaks at 185°, 21.4°, 260°, and 2730°.

Generally, to obtain Brilliant Carmine 6B, the thorium salt is dispersed in water and heated, rosin or extender pigment is added thereto, and an aqueous calcium salt solution is added dropwise.

The present inventors conducted intensive research to develop new pigment physical properties for the conventional Brilliant Carmine 6B, and as a result, the sodium salt of Brilliant Carmine 6B was dispersed or dissolved in a specific solvent, and the result was that the sodium salt of Brilliant Carmine 6B was dispersed or dissolved in a specific solvent and heated. However, it was discovered that when a calcium salt solution is added dropwise, an addition complex compound having unprecedented properties and pigment physical properties can be obtained.

The crystals obtained in this way are basically plate-shaped crystals containing many rhomboid or hexagonal crystals.
It was also found that it exhibits high color stability against heat.

Further examination of the crystal structure revealed that the conventional one was 0.
20 shows high intensity at 45-50° in uKa radiation
Unlike those that have a line diffraction pattern, those that have been completely processed into plate crystals and those that have been crushed do not show a peak at 2θ of 45 to 50°, and 2θ is the type of processing solvent. It was also found that the addition complex of the present invention has a highly intense peak in the range of 8° to 11°, and therefore has a completely new crystal structure.

Regarding addition complex compounds, those consisting of zinc phthalocyanine pigments and solvent molecules such as amines are known (J, Phys, Ohem, 72.! 7, 1).
'968, pp. 2446-2456), an addition complex compound consisting of a brilliant cardin 6B monoazo lake pigment and a solvent polyhydric alcohol has not been reported so far.

1. A method for producing an addition complex compound consisting of a monoazo lake pigment and a polyhydric alcohol represented by 1, wherein the monoazo dye according to 1 is dispersed or dissolved in a solvent containing a polyhydric alcohol and heated, and the same or a different solvent is added thereto. This method is characterized by dissolving a calcium salt in water and adding this calcium salt solution. In other words, the pigment is laked in a solvent system containing polyhydric alcohol instead of the conventional aqueous solution.The solvents used here include ethylene glycol,
12-propylene glycol, glycerin, or those containing one or two of these are preferred, and in some cases, ethanol, acetone, etc. may be further mixed therewith. Of these, water is preferably 1/4 or less of the total weight. Also, the calcium salts used here include chlorides, sulfides, sulfates, phosphates, acetates, and oxalates. , carbonates, hydroxides, etc. are used. Considering its solubility in the solvent JP-A-58-15561(3), calcium chloride is particularly preferred.

, the heating temperature is 40 to 220°C, particularly preferably 80°C.
Perform at ~140°C.

Stirring may or may not be performed during the reaction.

When stirred, the plate-like crystals produced are small, and when there is no stirring, they become large.

Further, the calcium salt solution may be added dropwise or may be added all at once.If added all at once, it will take longer to form, but large plate-shaped crystals will be obtained.

Furthermore, the sodium salt may be completely dissolved in the solvent or may be in a dispersed state, but complete dissolution produces clearer plate-like crystals.

The obtained pigment is post-treated by conventional means such as aging, washing with ethanol, drying, etc., and is obtained as a powder.

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

The present invention is a complex compound in which a monoazo lake pigment and a solvent are additionally bonded, and the crystal structure is different from conventional pigments that do not have such addition.・Liquid chromatography and differential thermal analysis are as follows. (DTA), gravithermal analysis (TGA), elemental analysis, 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 same as the retention time of a peak appearing in a liquid chromatogram of a solution of conventional brilliant carmine 6B dissolved in the same solvent. Match. This shows that the addition complex of the present invention maintains the chemical structure of brilliant carmine 6B and the solvent is additionally bonded to it.

The above fact is also supported by the fact that the X-ray diffraction pattern of the pigment according to the present invention after immersing it in water for several days shows the α form of brilliant carmine 6B.

Next, according to Figure 1, which shows the differential thermal analysis of pigments produced in ethylene glyfur, an endothermic peak due to the elimination of ethylene glyfur incorporated into the crystals appears at around 225°C, and the weight increases accordingly. A decrease is seen. Furthermore, it can be seen from this weight loss that one molecule of ethylene glycol is coordinated per molecule of brilliant cardin 6E. Furthermore, the fact that ethylene glycol is not simply physically adsorbed to brilliant carmine 6B but is incorporated into the crystal shows that differential thermal analysis of the surface of the generated addition complex with ethylene glycol still attached (
This is clear from Fig. 2).

That is, when comparing Figure 2 with Figure 1, apart from the peak around 225°C, a new endothermic peak around 136°C due to the desorption of ethylene glycol adhering to the surface was observed. It can be confirmed that the nearby peak is the removal of ethylene glycol incorporated into the crystal. These results show that this new slB material is an addition complex compound of brilliant carmine 6B.

Further, the elemental analysis values of the ethylene glycol addition complex obtained according to the present invention are 0:49.30%, H:3.
80%, N: 5.83%, S: 7.08%, C
a: 8.29%, and the calculated value assuming that one molecule of ethylene glycol is added to brilliant carmine 6B is 0: 49.38%, H: 3. '73%N:
5. '76%, S: 6.59%, Oa: 8.24%
The analytical values l are in good agreement.

(Left below) It is clear from the X-ray diffraction pattern that the new moazo lake pigment of the present invention has a new crystal structure different from that of the conventional brilliant carmine 6B. That is, according to FIGS. 3 and 4, which show the X-ray diffraction patterns of α type and β type of conventional brilliant carmine 6B due to Cukek radiation, α
The 2θ of the mold is 46°, 93°, 11.0°, 20.7°,
It has a peak at 234°, 25.4', and the β type has aθ of 49°, 1500.183°, 18.5°, 214°,
It has peaks at #≠, 260°, and 273°. Among those obtained according to the present invention, CuK6 produced in ethylene glycol. In Figure 5, which shows the X-ray diffraction pattern due to radiation, 2θ is approximately 82°, 99°, ]32°, ]
]58°22f3°, has a peak at 2400.

1. In Figure 6, which shows the X-ray diffraction pattern of the product produced in 2-propylene glycol, 2θ is approximately 80°, 94°,
Peaks appear at 11.4°, 151O1227°, and 231°. In addition, in FIG. 7 showing the xi diffraction pattern of the product produced in glycerin, the 2θ is about 810.
．． It has peaks at positions corresponding to 95°, 14o0.232°, 242°, and 258°. As is clear from the above, the X-ray diffraction pattern of the pigment obtained in the present invention is completely different from that of the conventional α and β types, and it is a pigment with a new crystal structure different from that of brilliant carmine 6B. 0 As mentioned above, the addition complex compound of the new moazo lake pigment obtained by the present invention is a different substance from the conventional brilliant carmine 6B, but it has basic physical properties such as light resistance and oil resistance, and color tone. There is no difference in terms. However, the pigment of the present invention has much improved color stability against heat, and is moreover
The particle shape is different from that of B, and 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 8 shows the differential thermal analysis of conventional brilliant carmine 6B, which shows 70~
The endothermic peak at 80°C is due to the detachment of weakly bound crystal water, which causes a crystal transition from α type to β type and changes in color tone.Furthermore, at around 200°C, strongly bound crystal water is released. It takes on a blackish flavor.

As shown in Figure 9, in the case of the pigment produced in 1,2-propylene glycol, no peak appears around 250'C, and the pigment changes from the α type to the β type, like the conventional brilliant carmine 6B. There is no change in color tone due to the transition.

That is, it is completely thermally stable up to 250°C.

Therefore, such pigments can be suitably used in fields where color stability is required, such as paints, printing inks, rubbers, synthetic resins, paints, and cosmetics.

The reason for this characteristic is that, unlike conventional brilliant carmine 6B, which incorporates water into its crystals, the pigment according to the present invention incorporates polyhydric alcohol, which has a boiling point higher than water, into its crystals. , 70~
It is thought that this is because the water of crystallization that is eliminated at 80° C. is not retained, and furthermore, the temperature at which the polyhydric alcohol in the crystal is eliminated is higher than that of water, resulting in improved thermal stability. Note that this feature is the same for both plate-shaped crystals and amorphous powder obtained by pulverizing them.

In the addition complex compound of the present invention, solvent molecules are incorporated into the crystal as described above, but in this case, the amount of solvent molecules incorporated varies depending on the type of solvent and manufacturing conditions, and the raw material of the solvent molecules is The quantity ratio to pigment is usually in the range 0.05-2. The polyhydric alcohol incorporated may be one species or two or more species.

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.

Furthermore, the manufactured 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 burl luster, such as heavy-duty paints and lipsticks in the decorative field and cosmetics. It can be used effectively.

Normally, in order to give a pearlescent luster to a coloring liquid, a pearlescent luster is dispersed in addition to the pigment, such as fish scale flakes, titanium-mica, or aluminum metal powder, to give the pearlescent luster. When used, the pigment itself serves as both a coloring agent and a burl agent, so there is no need to use a burl agent, and the pigment alone provides a beautiful red-colored colored product with pearlescent luster.

The above-mentioned thermal stability and pigment physical properties cannot be obtained with the conventional Antocarmine 6B, and in this respect it can be said that the pigment of the present invention is extremely useful industrially.

The present invention will be explained in more detail with reference to Examples.
The present invention is not limited thereby.

Example 1 5 parts of the sodium salt of Brilliant Carmine 6B are mixed with 700 parts of ethylene glycol and heated to 120°C.

A solution of calcium chloride (dihydrate) Z51 dissolved in 300 parts of ethylene glycol was added dropwise over 1 hour, kept at 120°C for another 3 hours, filtered, washed with ethanol, and heated at 80°C for 2 hours. After drying for an hour, 4 parts of red pigment were obtained.

When the obtained pigment was observed under a microscope (100x magnification), many type 1 plate-shaped crystals were observed (Figure 30).
The diffraction angle 2θ due to uKd radiation is approximately 82°, 99°, 1
An X-ray diffraction pattern with peaks at 3.2°, 15.8°, 2Z6°, and 240° was given. When observed with the naked eye, the liquid obtained by dispersing this pigment in nitrified cotton gave a beautiful red color with a pearlescent luster.

Furthermore, when differential thermal analysis was performed on the obtained pigment, as shown in Figure 1, there was an endothermic peak at approximately 225°C, and a corresponding weight loss was observed. 70~80° as seen in
No endothermic peak at C and accompanying weight loss were observed. According to this, the obtained pigment is 225°
It can be seen that it is much more thermally stable than conventional brilliant carmine 6B, which first releases ethylene glycol in the crystal around C and changes its crystal structure at 70 to 80'C.

Example 2 Brilliant Carmine 6B as in Example 1
10 parts of the sodium salt of This thing, 12-
The mixture was mixed with 700 parts of propylene glycol, and when the temperature reached 40°C, 300 parts of 12-propylene glycol in which 5 parts of calcium acetate had been dissolved was added dropwise over 1 hour with stirring, and stirring was continued for 5 hours. After the treatment, 7 parts of a red pigment was obtained in the same manner as in Example 1. Microscopic observation revealed that many plate crystals were produced. This one is Ou
20 in Klφ radiation is approximately 80°, 94°, 114°,
An X-ray diffraction pattern with peaks at 15.1° and latitudes 22.7' and 23.1' was given. In differential thermal analysis (Figure 9), 25
It showed an endothermic peak near 0° and a corresponding weight loss. According to this result, the temperature of the obtained pigment is about 250°C.
It can be seen that it is stable until

Example 3 Seven parts of a red pigment were obtained in exactly the same manner as in Example 2 except that glycerin was used instead of 12-propylene glycol. This item is au xi$ radiation te 2i (approximately 8
An X-ray diffraction pattern was given with camellia 1 peaks at 1°, 950.14.00.232°, and 242°.

Example 4 As in Example], 5 parts of the sodium salt of Brilliant Carmine 6B is dispersed in a mixed solvent of 500 parts of ethylene glycol and 100 parts of ethanol, and heated to 100°C.

A solution prepared by dissolving 25 parts of calcium chloride (dihydrate) in 100 parts of ethylene glycol and 1 part of ethanol was added dropwise over 1 hour and kept at 100"C for an additional 3 hours. Then, plate-like crystals similar to those in Example] were formed. Obtained.

Example 5 10 parts of the sodium salt of Brilliant Carmine 6B is dispersed in a mixed solvent of 300 parts of ethylene glycol and 500 parts of 2-propylene glycol and heated to 120'C.

A solution prepared by dissolving 5 parts of calcium chloride (dihydrate) in a mixed solvent of ethylene glycol blade and 8 parts of 2-propylene glycol was added dropwise to the solution over 2 hours, and then 120 minutes for another 5 hours.
Keep at °C. As a result, plate-shaped crystals to which co-2-propylene glycol was added as in Example 2 were obtained.

(Margin below)

[Brief explanation of drawings]

Figure 1 shows differential thermal analysis (DTA) and gravimetric thermal analysis (T
GA), and FIG. 2 is a differential thermal analysis diagram of a pigment with ethylene glycol adhered to the surface of the cleaning plate. FIG. 3 is an X-ray diffraction pattern of the d-type of brilliant carmine 6B measured with 0uKj radiation, and cylinder shape 4 is an X-ray diffraction pattern of its β-type. Figure 5 is an X-ray diffraction diagram of 0uKd radiation of a pigment prepared from brilliant carmine 6B in ethylene glycol, and Figures 6 and 7 are ft, 2-propylene glycol and glycerin pigments, respectively. This is an X-ray diffraction pattern of the pigment produced in this process. FIG. 8 is a diagram of differential thermal analysis and gravimetric analysis of a conventional brilliant carmine 6B type, and FIG. 9 is a diagram of differential thermal analysis and gravimetric thermal analysis of a pigment treated with 12-propylene glycol. Figure 3 is a micrograph (100x magnification) of a pigment prepared in ethylene glycol.

Claims (1)

[Claims] The calcium salt mo/azo pigment of (A) obtained by dispersing or dissolving the monoazo dye represented by in a polyhydric alcohol-containing solvent, heating it, and dropping a calcium salt solution thereto. Method for producing brilliant cardin 6B addition complex compound consisting of
12-Propylene glycol, glycerin, or a mixture thereof. (3) The manufacturing method according to claim (1), wherein the heating is performed at a temperature of no O to 220'O.