JPH11106671A - Production of delta type indanthron blue pigment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a δtype indanthron blue pigment having a more reddish hue and a higher chroma than those of an a type indanthron blue pigment, a less dichromatic property (a flip-flop property) than that of the a type indanthron blue pigment as a coating material, especially as a mica and aluminum metallic coating material and a weather resistance practically fitting for use, without using a large amount of a reducing agent or an oxidizing agent such as hydrosulfite or hydrogen peroxide. SOLUTION: This method for producing a δ type indanthron blue pigment is to dissolve or disperse a crude indanthron blue with sulfuric acid or an aqueous solution thereof to obtain a solution containing a reduced indanthron blue, then adjusting the concentration of sulfuric acid at 79-86 wt.%, putting the solution into water for obtaining a crude δ type indanthron blue pigment and then treating for making a pigment. It is desirable that the treatment for making the pigment of the δ type indanthron blue pigment is to mix the crude δ type indanthron blue pigment with water and/or an organic solvent and wet pulverizing in the presence of a crushing medium by using a crusher.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a δ-form in which the crystal form is stabilized by adding a metal having a higher ionization tendency than hydrogen before the crystallization step of δ-indanthrone blue by the sulfuric acid method. By producing Indanthrone Blue Coarse Coarse Pigment and subjecting it to pigmentation treatment, it has a reddish and highly chromatic hue compared to α-type Indanthrone Blue pigment. The present invention relates to a process for producing a δ-type indanthrone blue pigment having less dichroism (flip-flop property) than a blue pigment and having practically useful weatherability and crystal stability as a coloring material.

[0002]

2. Description of the Related Art There are four types of indanthrone blue known as α, β, γ and δ crystal types (PB Report 85172). Is said to be the most stable crystal structure (color materials,
43, 1970, P-560) as a coloring material for reddish blue pigments and commercially available. The α-type indanthrone blue pigment currently on the market has a strong dichroism (flip-flop property), and the coating object, especially the object coated with mica and aluminum metallic coating, has an angle of light and an observer. Depending on the position, there is a phenomenon in which reddish color appears to be floating on the surface of the object to be coated (reddishness in a shade), which is not preferred in some cases.

On the other hand, according to a PB report, δ-type indanthrone blue has a grayish blue hue,
Since the crystal form was unstable, it was considered to lack performance as a coloring material, and was not used as a pigment. As a method for obtaining a δ-type crystal of indanthrone blue, a sulfuric acid method is known. So far, we have reduced the water-insoluble indanthrone blue to a water-soluble sodium salt and then rapidly oxidized it. .
4 ゜, 11.2 ゜, 13.0 ゜, 16.7 ゜, 22.5
Obtaining water-insoluble δ-type crystals characterized by having diffraction peaks at ゜, 23.9 ゜ and 27.1 ゜;
The δ-type indanthrone blue pigment obtained by this reduction / rapid oxidation method has a reddish and highly-saturated hue compared to the α-type indanthrone blue pigment. It has been found that it has less dichroism (flip-flop properties) than Ronblue pigment and has weather resistance that can be practically used (WO 96/05255). But,
This reduction / rapid oxidation method involves a large amount of a reducing agent and an oxidizing agent such as hydrosulfite and hydrogen peroxide in the production process, and therefore has a problem in environmental and production safety.

In addition, a conventional method for obtaining δ-type crystals of indanthrone blue, indanthrone blue is stirred and crystallized in a predetermined concentration of sulfuric acid, and taken out in water to form δ-type crystals of indanthrone blue. In the obtained sulfuric acid method, the hue becomes a grayish blue δ-type crystal and cannot be used as a pigment. Also, when a mixture of water and an organic solvent of δ-type indanthrone blue obtained by the sulfuric acid method is finely pulverized using a pulverizer, similar to the reduction / rapid oxidation method,
δ which is redder and has higher chroma than α-type indanthrone blue pigment, and which has less dichroism (flip-flop property) than α-type in paints, especially mica and aluminum metallic paints
A type-indanthrone blue pigment is obtained, but its crystals are unstable, and when a dispersion operation is carried out when forming a coating in the presence of α-type indanthrone blue, δ-type crystals are converted to α-type crystals. And the reddish hue characteristic of the δ-type pigment changes to greenish, and the weather resistance is inferior to those of the α-type pigment and the δ-type pigment obtained by the reduction / rapid oxidation method. Furthermore, it is also known that heating to 200 ° C. in air causes crystal transformation into α-form crystals.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an α-indanthrone blue pigment which has a reddish and highly saturated hue compared to an α-indanthrone blue pigment and which is used in paints, especially mica and aluminum metallic paints. Uses δ-indanthrone blue pigment, which has less dichroism (flip-flop property) and has weather resistance that can withstand practical use, and uses a large amount of reducing agents and oxidizing agents such as hydrosulfite and hydrogen peroxide The aim is to find a manufacturing method that can be manufactured without performing.

[0006]

In order to solve the above-mentioned drawbacks of the prior art, the present inventors have found that the δ-type indanthrone blue pigment obtained by the reduction / rapid oxidation method has good crystal stability and weather resistance. As a result of intensive research, δ
When obtaining a crude indanthrone blue pigment, crude indanthrone blue is dissolved or dispersed in sulfuric acid or an aqueous solution thereof, and one containing reduced indanthrone blue, preferably crude indanthrone blue After dissolving in sulfuric acid or an aqueous solution thereof, a metal having a greater ionization tendency than hydrogen, for example, aluminum, a piece of metal such as zinc or a metal powder is added to reduce a part of the quinone structure of the indanthrone blue crude pigment. A hydroquinone structure was obtained, and then the concentration of sulfuric acid (concentration of sulfuric acid with respect to a total of 100% by weight of sulfuric acid and water, and the same in the following) was adjusted by dilution with water.
After adjusting to 86% by weight, by taking out in water,
Hydrosulfite, a stable δ-type crystal of indanthrone blue crude pigment can be obtained without using a large amount of a reducing agent or an oxidizing agent such as hydrogen peroxide, which is subjected to a pigmentation treatment, for example, with water and / or By performing wet pulverization in the presence of an organic solvent, a δ-type indanthrone blue pigment having excellent crystal stability and weather resistance can be easily obtained. In the diffraction diagram, 2θ ± 0.2 ° is 6.4 °, 11.2
The inventors have found diffraction peaks at {, 13.0}, 16.7, 22.5, 23.9, and 27.1 °, etc., and have completed the present invention.

That is, the present invention provides (1) a method in which crude indanthrone blue is dissolved or dispersed in sulfuric acid or an aqueous solution thereof and containing reduced indanthrone blue; ８６86% by weight, and then taken out into water to obtain a crude δ-indanthrone blue pigment, which is subjected to a pigmentation treatment.

(2) After dissolving crude indanthrone blue in sulfuric acid or an aqueous solution thereof, a metal having a higher ionization tendency than hydrogen is added to partially reduce the crude indanthrone blue, and then the sulfuric acid concentration is reduced. After adjusting to 79 to 86% by weight, take out into water to obtain a crude δ-type indanthrone blue pigment;

(3) When the crude δ-type indanthrone blue pigment has an X-ray diffraction pattern, 2θ ± 0.2 ° is 6.4 °,
11.2 ゜, 13.0 ゜, 16.7 ゜, 22.5 ゜, 2
(1) or (2), which has a diffraction peak at 3.9 ° and 27.1 °,

(4) The method according to (2) or (3), wherein the metal having a higher ionization tendency than hydrogen is aluminum and / or zinc.

(5) The pigmentation treatment of the δ-type indanthrone blue crude pigment is carried out by mixing the δ-type indanthrone blue coarse pigment with water and / or an organic solvent, and using a crushing device in the presence of a grinding medium. (1), (2), (3) or (4), which is a pigmentation treatment by wet milling

(6) The process according to (5), wherein the organic solvent is at least one organic solvent selected from the group consisting of aliphatic alcohols having 1 to 5 carbon atoms, dimethylformamide and diethylene glycol.

(7) The production method according to the above (5) or (6), wherein the pulverizing medium used in the wet pulverization is beads having a diameter of 0.1 to 2.0 mm or an inorganic pulverized salt.

(8) The production method according to the above (5), (6) or (7), wherein the pulverizing device is a stirred bead mill or a kneader.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The crude indanthrone blue used in the present invention is not particularly limited. Crude obtained by chemical synthesis or commercially available indanthrone blue called base, preferably indanthrone blue Long Blue Coarse Coarse Pigment, for example, DM-LIGHTBLUE KT
(Manufactured by Mitsui Toatsu Dye Co., Ltd.).

The reduced indanthrone blue used in the present invention includes one in which a part or all of the quinone structure of indanthrone blue is reduced to a hydroquinone structure, and the reduction method is not limited. For example, those obtained by reducing a quinone structure of indanthrone blue by adding a metal having a higher ionization tendency to hydrogen to a solution or dispersion of crude indanthrone blue. This reduced indanthrone blue is
Pre-manufactured ones may be used, but crude indanthrone blue is dissolved or dispersed in sulfuric acid or an aqueous solution thereof, and a metal having a higher ionization tendency than hydrogen is added. Those obtained by partial reduction are preferred. The addition of a metal having a higher ionization tendency than hydrogen is preferably 1 to 50 mol, particularly preferably 2 to 15 mol, per 100 mol of crude indanthrone blue.

The metal having a higher ionization tendency than hydrogen used herein includes, for example, metal pieces such as barium, calcium, lanthanum, titanium, beryllium, aluminum, manganese, zinc, gallium, iron, indium, cobalt, nickel and tin. And metal powders. Among them, aluminum and zinc metal pieces or metal powders are preferable, and aluminum metal pieces or metal powders are particularly preferable because they are excellent in environmental and manufacturing safety.

In order to obtain δ-type indanthrone blue pigment by the production method of the present invention, for example, crude indanthrone blue is prepared by adding sulfuric acid or sulfuric acid in a reaction vessel such as a normal pressure reaction vessel or a pressure reaction vessel. Its aqueous solution, preferably a sulfuric acid concentration of 79%
The above sulfuric acid (aqueous solution) is dissolved or dispersed, preferably dissolved by stirring with a rotating blade or the like. Next, reduced indanthrone blue may be added, but preferably, a metal piece or metal powder of a metal whose ionization tendency is larger than hydrogen is gradually added with stirring to dissolve the metal,
Preferably, the entire amount is completely dissolved. Then, by diluting with water while stirring, the total of sulfuric acid and water is reduced to 10%.
After dilution to a sulfuric acid concentration of 79 to 86% by weight, and preferably a sulfuric acid concentration of 79 to 81% by weight,
A mixture of δ-type indanthrone blue and a sulfuric acid solution until the crystallization of the δ-type crystal of indanthrone blue is completed at a temperature of -100 ° C, preferably 40-70 ° C, preferably for 1-5 hours. To manufacture.

Next, the mixture is taken out into water and filtered with a filter such as a filter press or a centrifugal filter, and then deflocculated, washed and filtered until the filtrate is near neutral. Rinsing with hot water or water to obtain a wet cake of δ-type indanthrone blue coarse pigment, and if necessary, drying the wet cake with a dryer or the like to obtain a δ-type indanthrone blue coarse pigment powder. To manufacture. Here, as a method of taking out the mixture into water, a method of throwing into a large amount of water, for example, 2 to 20 times by weight of the mixture, preferably 3 to 10 times by weight, is generally used. It may be. Δ of the crude indanthrone blue pigment thus obtained
In the X-ray diffraction pattern, the type crystal has 2θ ± 0.2 ° of 6.
4 ゜, 11.2 ゜, 13.0 ゜, 16.7 ゜, 22.5
It has diffraction peaks at {, 23.9} and 27.1 °.

Further, the obtained δ-type indanthrone blue coarse pigment powder or its wet cake is subjected to a pigmentation treatment. The pigmentation treatment method is not particularly limited as long as the pigmentation can be performed while maintaining the δ-type crystal, and is not particularly limited. The δ-type indanthrone blue coarse pigment powder or the wet cake thereof is mixed with water and / or an organic solvent. A pigmentation method of mixing, adjusting the pH to 6 to 8 as necessary, and wet-pulverizing the mixture using a pulverizer in the presence of a pulverizing medium is preferred.

The organic solvent used here may be any solvent which does not convert the δ-type crystals of the δ-type indanthrone blue crude pigment, such as aliphatic alcohols, aromatic hydrocarbons, dimethylformamide, dimethylsulfoxide, tetrahydrofuran and the like. Is mentioned.

Examples of the aliphatic alcohol include:
Methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, diethylene glycol, and the like.Examples of aromatic hydrocarbons include benzene,
Examples include toluene, o-xylene, m-xylene, p-xylene, and ethylbenzene. Among them, aliphatic alcohols having 1 to 5 carbon atoms and dimethylformamide are preferred, and isobutyl alcohol and isopropyl alcohol are particularly preferred.

As a pigmentation method by wet pulverization, for example, a diameter of 0.1 to 2.0 mm, preferably 0.2 to 2.0 mm
In the presence of 0.5 mm grinding media, preferably ceramic, glass or steel beads, particularly preferably abrasion resistant zirconia beads, batch or continuous grinding equipment, such as a bead mill, The δ-type indanthrone blue coarse pigment powder or its wet cake is finely pulverized by a sand grinder, a ball mill, a kneader, or the like, and the obtained finely pulverized product is filtered by a filter, for example, a filter press, a centrifugal filter or the like. , Then separation,
Water washing, hot water washing, drying method, inorganic crushed salt, for example,
Using a kneader in the presence of sodium chloride, finely pulverize the δ-type indanthrone blue pigment powder or its wet cake, pulverize the obtained finely pulverized product into water, hot water or the like, and use a filter, for example, a filter. A method characterized by separating δ-type indanthrone blue by filtration with a press, a centrifugal separation type or the like, followed by washing with hot water and water, and drying by a drier. As the pulverizer used here, a stirring type bead mill and a kneader are preferable.

The δ-type indanthrone blue pigment obtained by the production method of the present invention can be used as a paint, for example, an acrylic melamine paint, an acrylic urethane paint, a melamine alkyd paint, etc. Similar to the indanthrone blue pigments, the reddish blue paints, which are more saturated and luxurious than the α-indanthrone blue pigments, especially mica and aluminum metallic paints,
Dichroism (Flip-
(Flop property) and a crystal type stability and weather resistance that can withstand practical use. The δ-type indanthrone blue pigment obtained by the production method of the present invention is also suitable for uses such as printing inks, resin colorants, and color filters in addition to these paints.

The pigment dispersion is obtained by dispersing the δ-indanthrone blue pigment obtained by the production method of the present invention together with a dispersion medium or the like using a known disperser.

Examples of the dispersion medium include resins and solvents used for dispersions such as paints, plastics, printing inks and color toners.
Acrylic resin, urethane resin, polyester resin, amide resin, melamine resin, ether resin, fluorine resin, vinyl chloride resin, polystyrene, ABS resin, AS resin,
Polyolefin resins such as polyethylene and polypropylene, polyacetal resins, resins such as polycarbonate resins; water, aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as mineral spirits,
Examples include, but are not limited to, alcohol-based solvents such as methanol and ethanol, ester-based solvents such as ethyl acetate, ketone-based solvents such as methyl ethyl ketone, and ether-based solvents such as ethylene glycol.

Further, if necessary, various auxiliary materials and stabilizers such as a dispersing wetting agent, an anti-skinning agent, an ultraviolet absorber and an antioxidant may be used.

The ratio of the δ-type indanthrone blue pigment in the pigment dispersion is preferably 90% by weight or less,
A range of 1 to 50% by weight is particularly preferred. The remainder is a dispersion medium.

Since the dispersion conditions vary depending on the dispersion medium and the disperser, the dispersion temperature and dispersion time are not limited, but the dispersion temperature is from room temperature to 240 ° C., preferably from room temperature to 150 ° C., and the dispersion time is within 120 hours, preferably Within 5 hours.

These pigment dispersions are mixed with other additives, pigments and dyes, if necessary, and prepared and used in final paints, printing inks, plastics, color toners, recording agents and the like.

As a disperser for dispersing the δ-type indanthrone blue pigment in these pigment dispersions, known dispersers such as a disper, a homomixer, a bead mill, a ball mill, a two-roll, a three-roll, and a pressure kneader can be used. But are not limited to these.

[0032]

EXAMPLES Next, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following, unless otherwise noted
“Parts” and “%” are “parts by weight” and “% by weight”, respectively.
Represents

Example 1 Indanthrone Blue Coarse Coarse Pigment (DM-LIGHT BLUE KT;) was placed in a glass-lined reaction vessel charged with 90000 parts of 98% sulfuric acid.
12400 parts (Mitsui Toatsu Dye Co., Ltd.) were gradually added with stirring to dissolve, and 10,000 parts of 98% sulfuric acid was further added while washing the indanthrone blue adhering to the reaction vessel wall. After stirring for 60 minutes, 49.6 parts of aluminum powder (manufactured by Kokusan Chemical Co., Ltd., reagent first grade) was added, and the mixture was stirred and dissolved for 2 hours. Then, 24000 parts of water was gradually added, and an indanthrone blue suspension having a sulfuric acid concentration of 80% (weight ratio of indanthrone blue / 80% aqueous sulfuric acid = 1/1).
10) was obtained.

The obtained suspension was stirred at 60 to 70 ° C. for 2 hours to convert the crystal form from α-form to δ-form. Then, this suspension was stirred with a rubber-lined stirring charged with 682,000 parts of water. After taking out into a tank and stirring for 30 minutes, it was filtered by a filter press and washed with water until the filtrate became neutral, to obtain a wet cake of δ-type indanthrone blue crude pigment (solid content: 46.5%). .

3225.8 parts (solid content: 1500 parts) of a wet cake of the obtained δ-type indanthrone blue crude pigment
Was dispersed in 11774.2 parts of water, and the pH was adjusted to 7 by adding a 48% aqueous sodium hydroxide solution to obtain 15,000 parts of a suspension before wet milling.

Next, the obtained suspension before wet pulverization is
Stirring type bead mill (Dry Swerke PM-DCP)
-3; manufactured by Dry Swerke Co., Ltd.), the peripheral speed of the stirrer is 11.7 m / sec, the power density is 20 to 25 kW, the crushing space is 1 liter, the pressure is 0.5 to 1.0 bar, and the diameter is 0.25.
mm of Micro Haica Z250 zirconia beads (manufactured by Showa Shell Sekiyu KK) 35 kg, suspension wet grinding treatment amount 7.2-9.4 kg / hour, suspension wet grinding temperature 39-
The process of wet pulverization under the condition of 54 ° C. is repeated four times to obtain δ
After obtaining an aqueous suspension of the type Indanthrone Blue pigment, the solution was filtered, washed with water, dried and powdered to obtain a δ-type Indanthrone Blue pigment.

Example 2 Indanthrone Blue Coarse Coarse Pigment (DM-LIGHT BLUE KT;) was placed in a glass-lined reaction vessel charged with 90000 parts of 98% sulfuric acid.
12400 parts (Mitsui Toatsu Dye Co., Ltd.) were gradually added with stirring to dissolve, and 10,000 parts of 98% sulfuric acid was further added while washing the indanthrone blue adhering to the reaction vessel wall. After stirring for 60 minutes, 49.6 parts of aluminum powder (manufactured by Kokusan Chemical Co., Ltd., first grade reagent) was added, and the mixture was stirred for 2 hours. Then, 14000 parts of water was gradually added to obtain an indanthrone blue suspension having a sulfuric acid concentration of 86% (weight ratio of indanthrone blue / 86% sulfuric acid = 1 / 9.2).

Next, a wet cake of δ-type indanthrone blue crude pigment (solid content: 36.9%) was obtained in the same manner as in Example 1 except that this suspension was used.

4065.0 parts of a wet cake of the obtained δ type indanthrone blue crude pigment (1500 parts of solid content)
Was dispersed in 10935.0 parts of water, and the pH was adjusted to 7 to obtain 15,000 parts of a suspension before wet pulverization.

Next, except that this suspension before wet pulverization was used, wet pulverization, filtration, washing with water, drying and pulverization were carried out in the same manner as in Example 1 to obtain a δ-type indanthrone blue pigment. .

Example 3 Wet cake 3225.8 of the crude δ-type indanthrone blue pigment obtained in Example 1
Part (solid content: 1500 parts) was dispersed in 11774.2 parts of water, the pH was adjusted to 6, and the suspension before wet pulverization was 1500.
0 parts were obtained.

Next, the obtained suspension before wet pulverization is
Stirring type bead mill (Dry Swerke PM-DCP)
-3; manufactured by Dry Swerke Co., Ltd.), the peripheral speed of the stirrer is 16.7 m / sec, the power density is 20 to 25 kW, the crushing space is 1 liter, the pressure is 0.5 to 1.0 bar, and the diameter is 0.20.
mm of Micro Haica Z200 zirconia beads (manufactured by Showa Shell Sekiyu KK) 35 kg, suspension wet grinding treatment amount 7.2-9.4 kg / hour, suspension wet grinding temperature 39-
The process of wet pulverization under the condition of 54 ° C. is repeated four times to obtain δ
After obtaining an aqueous suspension of type Indanthrone blue pigment, the solution was filtered, washed with water, dried, and powdered to obtain a δ-type indanthrone blue pigment.

(Comparative Example 1) Indanthrone blue coarse pigment (DM-LIGHT BLUE KT;) was placed in a glass-lined reaction vessel charged with 90000 parts of 98% sulfuric acid.
12400 parts (Mitsui Toatsu Dye Co., Ltd.) were gradually added with stirring to dissolve, and 10,000 parts of 98% sulfuric acid was further added while washing the indanthrone blue adhering to the reaction vessel wall. After stirring for 60 minutes, 24,000 parts of water was gradually added, and an indanthrone blue suspension having a sulfuric acid concentration of 80% (weight ratio of indanthrone blue / 80% sulfuric acid = 1/1).
0) was obtained.

A wet cake of δ-type indanthrone blue crude pigment (solid content% by weight: 37.3%) was obtained in the same manner as in Example 1 except that this suspension was used.

4021.4 parts of a wet cake of the obtained δ type indanthrone blue crude pigment (solid content: 1500 parts)
Was dispersed in 10978.6 parts of water, and the pH was adjusted to 7 to obtain 15,000 parts of a suspension before wet pulverization.

Next, except that this suspension before wet milling was used, wet milling, filtration, washing with water, drying and powdering were performed in the same manner as in Example 1 to obtain a δ-type indanthrone blue pigment. .

(Comparative Example 2) The suspension before wet pulverization obtained in Comparative Example 1 was stirred with a bead mill (Dry Swerke P).
M-DCP-3; manufactured by Dry Swerke Co., Ltd.), the peripheral speed of the stirrer is 16.7 m / sec, and the power density is 20 to 25 kW /
1 liter space for pulverization, 0.5-1.0 bar pressure, 0.20 mm diameter, microfiller Z200 zirconia beads (manufactured by Showa Shell Sekiyu KK) 35 kg, suspension wet pulverization processing amount 8.3-10.4 kg / The process of wet milling under the conditions of suspension wet milling temperature of 39 to 54 ° C. for 8 hours is repeated eight times to obtain an aqueous suspension of the δ-type indanthrone blue pigment each time, followed by filtration and washing with water And dried and powdered to obtain a δ-type indanthrone blue pigment.

Example 4 Dried product of wet cake of crude δ-indanthrone blue pigment obtained in Example 1 15
00 parts were peptized and dispersed in 13500 parts of isobutanol to obtain 15,000 parts of a suspension before wet pulverization.

Next, an isobutanol suspension of δ-type indanthrone blue pigment was obtained by wet milling in the same manner as in Example 1 except that the suspension before wet milling was used. After 15,000 parts of water was added to the butanol suspension, isobutanol was distilled off azeotropically to replace the suspension with an aqueous suspension to obtain an aqueous suspension. This aqueous suspension was filtered, washed with water, dried, and powdered to obtain a δ-type indanthrone blue pigment.

(Example 5) Dry product 32 of wet cake of crude pigment of δ-type indanthrone blue obtained in Example 1
25.8 parts were peptized and dispersed in 111774.2 parts of isopropyl alcohol to obtain 15,000 parts of a suspension before wet pulverization.

Next, a wet crushing was carried out in the same manner as in Example 1 except that the suspension before wet crushing was used to obtain an isopropyl alcohol-based suspension of a δ-type indanthrone blue pigment. 15 water in alcoholic suspension
After adding 000 parts, isopropyl alcohol was distilled off azeotropically, and the suspension was replaced with an aqueous suspension to obtain an aqueous suspension. This aqueous suspension was filtered, washed with water, dried, and powdered to obtain a δ-type indanthrone blue pigment.

Example 6 Wet cake 3225.8 of the crude δ-indanthrone blue pigment obtained in Example 1
4050.0 parts of dimethylformamide and 772 of water
The mixture was peptized and dispersed in a mixed solution consisting of 4.2 parts to obtain 15,000 parts of a suspension before wet pulverization.

Next, the obtained suspension before wet pulverization is
Stirring type bead mill (Dry Swerke PM-DCP)
-3; manufactured by Dry Swerke Co., Ltd.), the peripheral speed of the stirrer is 11.7 m / sec, the power density is 20 to 25 kW, the crushing space is 1 liter, the pressure is 0.5 to 1.0 bar, and the diameter is 0.25.
mm of Micro Haica Z250 zirconia beads (manufactured by Showa Shell Sekiyu KK) 35 kg, suspension wet grinding treatment amount 7.2-9.4 kg / hour, suspension wet grinding temperature 39-
The step of wet pulverization at 54 ° C. is repeated twice to obtain δ
After obtaining a dimethylformamide-based suspension of the indanthrone blue pigment, filtration, washing with water, drying, and powdering were performed to obtain a δ-indanthrone blue pigment.

(Example 7) Dry product 33 of wet cake of crude pigment of δ-type indanthrone blue obtained in Example 1
0.0 parts, 2970.0 parts of sodium chloride and 500 parts of diethylene glycol were pulverized by a kneader at 80 ° C. for 6 hours to obtain a pigment mixture. The obtained pigment mixture was dispersed in 10,000 parts of water, stirred at 80 ° C. for 1 hour, filtered, washed with hot water, dried, and powdered to obtain a δ-type indanthrone blue pigment.

Comparative Example 3 Dried product of wet cake of δ-type indanthrone blue crude pigment obtained in Comparative Example 1
00 parts were peptized and dispersed in 13500 parts of isobutanol to obtain 15,000 parts of a suspension before wet pulverization.

Next, an isobutanol suspension of δ-type indanthrone blue pigment was obtained by wet milling in the same manner as in Example 1 except that the suspension before wet milling was used. After 15,000 parts of water was added to the butanol suspension, isobutanol was distilled off azeotropically to replace the suspension with an aqueous suspension to obtain an aqueous suspension. This aqueous suspension was filtered, washed with water, dried, and powdered to obtain a δ-type indanthrone blue pigment.

Comparative Example 4 1800 parts of water was weighed and placed in a reaction vessel, and the temperature was raised to 60 ° C. while stirring. Next, 163.2 parts of a 48% by weight sodium hydroxide solution and 56.4 parts of hydrosulfite were added, and 36.0 parts of indanthrone blue coarse coarse pigment (DM-LIGHT BLUEKT; manufactured by Mitsui Toatsu Dye Co., Ltd.) were further added. In addition, a reduction reaction was performed by stirring at 60 ° C. for 15 minutes to obtain a reduced liquid.

Further, 1200 parts of water and 30 parts
75.0 parts of a 2% aqueous hydrogen peroxide solution and weigh them with stirring.
The solution was kept at 0 ° C. to obtain an oxidizing solution.

Next, the entire amount of the reducing solution was injected into the stirring oxidizing solution by omitting a pump for 4 minutes, and a rapid oxidation reaction was performed. After further stirring for 1 hour, the mixture was filtered and washed with water until the filtrate became neutral. After drying the obtained δ-type indanthrone blue wet cake, pulverized,
A δ-indanthrone blue pigment produced by a reduction / rapid oxidation method was obtained.

(Test Example 1) << Hue comparison test with melamine alkyd paint >> δ-indanthrone blue pigment obtained in Examples 1 to 7 and Comparative Examples 1-4 and commercially available α-indanthrone blue pigment ( Monolite Blue 3R; manufactured by Zeneca Corporation; hereinafter, abbreviated as “α-type pigment 1”) in an amount of 2.0 g; 1026 Clear (Kansai Paint) 1
6.0 g, baking thinner No. 10.0 g of 3 mm (manufactured by Kansai Paint Co., Ltd.) and 80 g of 3 mmφ glass beads were placed in a 100 ml polyethylene bottle and dispersed with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 2 hours. 50.0 g of 1026 clear was added, and the mixture was further dispersed for 10 minutes with a paint conditioner to obtain a melamine alkyd primary color paint.

Each of 6.0 g of the obtained primary color paint and Amirac No. 1531 white (Kansai Paint Co., Ltd.)
10.0 g was placed in a polyethylene cup and mixed uniformly to obtain a melamine alkyd light-colored paint.

Each of the obtained melamine alkyd light-colored paints was applied and spread on an art paper using a 6 mil (152 μm) applicator, and allowed to stand for 1 hour.
And baked for 20 minutes in a dryer.

The color of these coatings was measured using an ACS-1400STC spectrophotometer (manufactured by ACS, USA), and the hue of the indanthrone blue pigment was compared based on lightness L *, hue angle h and chroma C *.

[0064]

[Table 1]

The δ-type indanthrone blue pigments obtained in Examples 1 to 3 have a larger hue angle h and a reddish hue than Comparative Examples 1 and 2, and were obtained in Examples 4 to 7. The hue angle h of the δ-type indanthrone blue pigment was larger than that of Comparative Example 3, and the hue was reddish. In addition, these Examples 1 to
Each of the δ-indanthrone blue pigments obtained in 7 has a red hue equivalent to or higher than that of the δ-indanthrone blue pigment produced by the reduction / rapid oxidation method of Comparative Example 4, and is commercially available. The hue angle h was larger than that of the α-type indanthrone blue pigment, and the hue was reddish. The δ-type indanthrone blue pigments obtained in Examples 1 to 7 were found to be pigments having extremely excellent performance as a coloring material.

(Test Example 2) << Crystal stability comparison test with melamine alkyd paint >> In the same manner as in Test Example 1, δ-type indanthrone blue pigments obtained in Examples 1 to 7 and Comparative Examples 1 to 4 α-type pigment 1
(Monolite Blue 3R; manufactured by Zeneca) was used to obtain a melamine alkyd primary color paint in the same manner as in Test Example 1.

Each of 3.0 g of the primary color paint obtained by using the δ-type indanthrone blue pigment obtained in Examples 1 to 7 and Comparative Examples 1 to 4 and the primary color paint 3 obtained by using the α-type pigment 1 .0
g and Amirac No. 10.03 g of 1531 white (manufactured by Kansai Paint Co., Ltd.) was placed in a polyethylene cup and mixed uniformly to obtain a light-colored paint (A).

1.0 g of each of the δ-type indanthrone blue pigment and α-type pigment 1 obtained in Examples 1 to 7 and Comparative Examples 1 to 4, and Amirac No. 1026 Clear (manufactured by Kansai Paint Co., Ltd.) 16.0 g, and baked thinner 3
After putting 10.0 g (manufactured by Kansai Paint Co., Ltd.) and 80 g of 3 mmφ glass beads into a polyethylene bottle having a capacity of 100 ml and dispersing them for 2 hours with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.), Amirac No. 50.0 g of 1026 clear was added, and the mixture was further dispersed for 10 minutes with a paint conditioner to obtain a melamine alkyd mixed primary color paint of δ-type indanthrone blue pigment and α-type indanthrone blue pigment.

6.0 g of each of the obtained mixed primary color paints
And Amirac No. 10.03 g of 1531 white (manufactured by Kansai Paint Co., Ltd.) was placed in a polyethylene cup and mixed uniformly to obtain a mixed light-colored paint (B).

The light-colored paint (A) and the mixed light-colored paint (B) obtained above were each coated on an art paper by 6 mil (1 mil).
(52 μm) and spread for 1 minute, and then baked in a dryer at 140 ° C. for 20 minutes to dry.

The color of these coatings was measured using an ACS-1400STC spectrophotometer (manufactured by ACS, USA), and the difference in the hue of the mixed light-colored paint (B) with respect to the hue of the light-colored paint (A) was determined by ΔL * ( Difference in lightness L *), ΔH * (difference in hue angle h)
And the ΔC * (difference in chroma C *) and the color difference ΔE * to evaluate the crystal stability in the dispersion of δ-indanthrone blue pigment in the presence of α-type indanthrone blue pigment did.

[0072]

[Table 2]

Here, when ΔH * becomes negative, the hue becomes green due to the mixture and dispersion with the α-type indanthrone blue pigment, indicating that the δ-type indanthrone blue pigment undergoes crystal transformation. Is shown. That is,
The closer the ΔH * is to zero, the better the crystal stability is.
It is a type indanthrone blue pigment.

The δ-type indanthrone blue pigments obtained in Examples 1 to 7 have ΔH * closer to zero and reddish than the δ-type indanthrone blue pigments obtained in Comparative Examples 1 to 3. Is maintained, that is, the crystal form is stable, the hue change (ΔE *) is small, and the crystal form stability is the same as that of the δ-type in Comparative Example 4 obtained by the reduction / rapid oxidation method. It was found to be as good as or better than Dunthrone Blue pigment.

(Test Example 3) << Weather resistance comparison test with acrylic melamine paint >> (Adjustment of primary color enamel) δ-type indanthrone blue pigment and α-type pigment obtained in Examples 1 to 7 and Comparative Examples 1 to 4 1. Commercially available α-type indanthrone blue pigment (Paliogen)
Blue L-6480; manufactured by BASF, hereinafter abbreviated as “α-type pigment 2” and commercially available α-type indanthrone blue pigment (Fastogen Super Blue 60)
70S; Dainippon Ink and Chemicals, hereinafter abbreviated as “α-type pigment 3”), 11.25 g each, and Acridic 47-712 (Dainippon Ink and Chemicals) 37.5.
g and a mixed solvent (weight ratio of xylene / n-butanol =
75/25) 43.75 g and 3 mmφ glass beads 1
50 g was placed in a polyethylene bottle having a capacity of 250 ml, dispersed with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 2 hours, and then Acridic 47-712 57.
5 g and 25.0 g of Super Beckamine L-117-60 (manufactured by Dainippon Ink and Chemicals, Inc.) were added, and the mixture was further dispersed with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 10 minutes to obtain an acrylic melamine primary color enamel. .

(Adjustment of Aluminum Enamel) Alpaste 7
620NS (manufactured by Toyo Aluminum Co., Ltd.), 40.5 g, Acrydik 47-712 (manufactured by Dainippon Ink and Chemicals, Inc.), 342.0 g, and Super Beckamine L-117-
60 (manufactured by Dainippon Ink and Chemicals, Inc.) and a mixed solvent (xylene / n-butanol weight ratio = 75/2)
5) 157.5 g was mixed in a stainless steel cup to obtain an aluminum enamel.

(Coating of acrylic melamine paint) 35.0 g of each of the acrylic melamine primary color enamels obtained above.
And 35.0 g of aluminum enamel and a mixed solvent (weight ratio of Solvesso # 100 / xylene / ethyl acetate / n-butanol = 40/30/20/10) were mixed in a plastic cup, and each mixed with 5 : 5 An aluminum acrylic melamine paint enamel was obtained.

Each of the obtained 5: 5 aluminum acrylic melamine paint enamels is applied to a painting robot (Softboy S).
B41-110R-0GA1; manufactured by Takubo Engineering Co., Ltd.) and applied to a 70 × 150 mm intermediate coated water-sharpened aluminum plate surface so that the dried coating film has a thickness of about 20 μm. Nippon Ink Chemical Industry Co., Ltd.) 59.6% and Super Beckamine L-
117-60 (manufactured by Dainippon Ink and Chemicals, Inc.) 21.3%
Solvesso # 100; 17.2% and n-butanol; 1.9%, a clear paint was applied by a coating robot so that the dried film had a thickness of about 25 μm, and was left for one day. Then, it was baked in a dryer at 140 ° C. for 23 minutes and dried to obtain a sample plate for an exposure test.

(Accelerated exposure test of acrylic melamine paint)
Each of the obtained test plates for an exposure test was subjected to an accelerated exposure test for 288 hours in a dew cycle (irradiation-dark-condensation) using an eye super UV tester (manufactured by Iwasaki Electric Co., Ltd.). The hue of the sample plate before and after the exposure is ACS-1400ST
The color was measured using a C spectrophotometer (manufactured by ACS, USA) to obtain a color difference ΔE * due to accelerated exposure.

[0080]

[Table 3]

The smaller the ΔE * obtained as described above, the smaller the change in hue due to accelerated exposure, indicating that the weather resistance required for automotive paint applications and the like is excellent. I have.

The δ-type indanthrone blue pigments obtained in Examples 1 to 7, particularly Example 1, have a smaller ΔE * than the δ-type indanthrone blue pigments obtained in Comparative Examples 1 to 3, Δ-type indanthrone blue pigment with improved weather resistance. Further, α-type pigment 1 which is an α-type indanthrone blue pigment which is commercially available and used for applications such as automotive paints
3) has the same or better weather resistance as
It has been clarified that the δ-type indanthrone blue pigment obtained by the production method of the present invention is a high-performance pigment that can withstand applications such as automotive paints requiring high weather resistance.

(Test Example 4) << Evaluation Test of Dichroism with Acrylic Melamine Paint >> Each of the δ-type indanthrone blue pigment and the α-type pigment 1 (Monolite Blue 3R; manufactured by Zeneca) obtained in Example 1 was used. The sample plate for the exposure test obtained in Test Example 3 was used as a gonio-spectrophotometer GONIO-SPECTOROPH.
OTOMETERS GSP-1 (manufactured by Murakami Color Research Laboratory), incident angle: fixed at 45 °, light receiving angle range: -75
The hue angle h with respect to the light receiving angles of 30 ° and −75 ° was measured and compared with a light source of ゜ to 75 ° and a D65 light source.

[0084]

[Table 4]

The δ-type indanthrone blue pigment obtained in Example 1 has a higher chroma C * and a smaller change in the hue angle h with respect to the change in the light receiving angle than the commercially available α-type indanthrone blue pigment. It is clear that the pigment is a good pigment for applications such as metallic paints for automobiles having little dichroism.

(Test Example 5) << Hue Comparison Test of Lithographic Ink >> (Preparation of Dark Ink) Examples 1, 2, 3,
Comparative Example 1, Comparative Example 4, and α-type pigment 1 (Monolit
e Blue 3R; manufactured by Zeneca Corporation)
And MG-63 varnish (Dainippon Ink and Chemicals)
Using a Hoover Mahler, 1.5 g was dispersed three times by repeating a load of 150 lbs and 100 rotations, thereby producing dark inks.

(Preparation of Light Ink) 0.11 g of the obtained dark ink and titanium white (R-550, manufactured by Ishihara Sangyo Co., Ltd.)
1.5 g and a varnish of 1.1 g were dispersed by using a Hoover Mahler at a load of 150 pounds and repeating 100 rotations twice to prepare a light-colored ink.

(Evaluation of Hue of Lithographic Ink) Examples 1 and 2 were obtained by spreading a light-color ink on a spread paper having a black belt with a spatula.
The hue of the δ-type indanthrone blue pigment obtained in Example 3 and the hue of Comparative Example 1, Comparative Example 4 and α-type pigment 1 were visually compared.

The hue of the δ-type indanthrone blue pigment obtained in each of Examples 1, 2 and 3 is redder than that of Comparative Example 1, Comparative Example 4 and α-type pigment 1. The coloring power was also found to be excellent.

(Test Example 6) << Comparison of Weathering Resistance with Resin Coloring >> 0.5 g of the δ-indanthrone blue pigment obtained in Example 1 and Comparative Example 1 was mixed with polypropylene (Mitsubishi Noblen MA-4). ) 1000g and Taipaque R-68
0 (titanium oxide manufactured by Ishihara Sangyo Co., Ltd.) 3.2 g and aluminum stearate 1.3 g were mixed, and molding temperature 22
Injection molding was performed at 0 ° C. to obtain a weather-resistant test piece.

The obtained test piece was subjected to a dew cycle (irradiation-irradiation) using an eye super UV tester (manufactured by Iwasaki Electric Co., Ltd.).
(Dark-condensation) for an accelerated exposure test of 288 hours. The hue of the sample plate before and after exposure was measured with an ACS-1400STC spectrophotometer (ACS, USA) to obtain a color difference ΔE * due to accelerated exposure.

The test piece using the δ-type indanthrone blue pigment obtained in Comparative Example 1 had a color difference ΔE * before and after accelerated exposure of 1.
On the other hand, ΔE * of the test piece using the δ-type indanthrone blue pigment obtained in Example 1 was very small at 0.8, whereas the ΔE * of the test piece obtained in Example 1 was 0.8. Dunthrone blue pigment showed high weather resistance.

Test Example 7 << Evaluation Method of Color Filter >> In a glass container, 2.0 g of the δ-indanthrone blue pigment obtained in Example 1 and an ultraviolet-curable acrylic resin (Unidick S5-122: Dainippon Ink and Chemicals, Inc.)
4.0 g of 2-butoxy-1-propanol 94.0
g and 300 g of 0.4 mm zirconia beads,
The mixture was dispersed for 2 hours using a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) to prepare a coating solution.

The obtained coating solution was applied to a spin coater (1H-
Using a 3D type (manufactured by Mikasa Co., Ltd.), it was applied onto a glass plate (7059: manufactured by Corning) to obtain a colored glass plate usable as an optical element. The application condition is 10 at 200 rpm.
Seconds, then 30 seconds at 2000 rpm.

The obtained colored glass plate was judged to be usable as a color filter because of its good transparency and clearness.

[0096]

According to the process for producing δ-type indanthrone blue pigment of the present invention, it is possible to use industrial materials without using hydrosulfite or hydrogen peroxide, which poses environmental and operational safety problems. It can be manufactured in a special way. Moreover, the δ-type indanthrone blue pigment obtained by the production method of the present invention has a more stable crystal form than the δ-type indanthrone blue crystal obtained by the conventional sulfuric acid method, and can be used as a paint, a printing ink or a resin colorant. In applications such as color filters and the like, the pigment has a hue that is redder and has higher saturation than the α-type indanthrone blue pigment, and is also excellent in weather resistance.

Claims (8)

[Claims] 1. A crude indanthrone blue dissolved or dispersed in sulfuric acid or an aqueous solution thereof and containing reduced indanthrone blue, and then the sulfuric acid concentration was adjusted to 79 to 86% by weight. Thereafter, the mixture is taken out into water to obtain a crude δ-indanthrone blue pigment, which is subjected to a pigmentation treatment. 2. After dissolving crude indanthrone blue in sulfuric acid or an aqueous solution thereof, a portion of the crude indanthrone blue is reduced by adding a metal having a higher ionization tendency than hydrogen, and then the sulfuric acid concentration is reduced to 79%. The production method according to claim 1, wherein the pigment is adjusted to ~ 86% by weight and taken out in water to obtain a crude δ-type indanthrone blue pigment. 3. The crude δ-indanthrone blue pigment is
In the line diffraction diagram, 2θ ± 0.2 ° is 6.4 °, and 11.
2 ゜, 13.0 ゜, 16.7 ゜, 22.5 ゜, 23.9
3. The production method according to claim 1, wherein the compound has diffraction peaks at {and 27.1}. 4. A metal having an ionization tendency greater than that of hydrogen is aluminum and / or zinc.
The manufacturing method as described. 5. The pigmentation treatment of the crude δ-indanthrone blue pigment is carried out by mixing the crude δ-indanthrone blue pigment with water and / or an organic solvent and using a grinding device in the presence of a grinding medium. 5. The production method according to claim 1, wherein the pigmentation treatment is performed by wet pulverization. 6. The method according to claim 5, wherein the organic solvent is at least one organic solvent selected from the group consisting of aliphatic alcohols having 1 to 5 carbon atoms, dimethylformamide and diethylene glycol. 7. The production method according to claim 5, wherein the pulverization medium used in the wet pulverization is beads having a diameter of 0.1 to 2.0 mm or an inorganic pulverized salt. 8. The production method according to claim 5, wherein the crushing device is a stirring type bead mill or a kneader.