JP2018204019A - Aniline black particle, resin composition using aniline black particle, aqueous dispersion, and solvent-based dispersoid - Google Patents

Abstract

To provide an aniline black particle excellent in blackness, capable of expressing free color tone blacks, and capable of bluish black, purplish black and jet-black, which are hard to be expressed in prior art, high in heat resistance, high in volume resistivity value, and excellent in dispersibility.SOLUTION: There is provided an aniline black particle having content of a chromatic color pigment with average particle diameter of primary particles of 0.01 to 0.2 μm of 1 to 60 pts.wt. based on 100 pts.wt. of an aniline black basic skeleton, and volume resistivity of 10to 10Ω cm.SELECTED DRAWING: None

Description

  The present invention can express black of any hue, has excellent blackness, can be expressed in blue, purple, and jet black, which was difficult to express in the past, and is volume-specific. The present invention provides aniline black having a high resistance value, high heat resistance, and excellent dispersibility.

  The present invention also provides aniline black that is excellent in dispersibility in hydrophobic media such as resins and organic solvents and has excellent blackness.

  In addition, the present invention is colored by the aniline black, has excellent dispersibility, excellent blackness, high heat resistance, and can express black with a free hue, and can be expressed in bluish black, purple, which has been difficult to express in the past. It is possible to express even black of taste and jet black, and provides a resin composition, an aqueous dispersion, and a solvent dispersion that are excellent in blackness. In the present invention, aniline black particles may be simply abbreviated as aniline black.

  Aniline black is a black pigment obtained by oxidative polymerization of an aromatic amine such as aniline, and has a basic skeleton of aniline black by an N-phenyldibenzoparaazine polymer represented by Chemical Formula 1.

(In the chemical formula 1, it is said that n = 1 to 3. X represents an acid group such as a hydroxyl group and chlorine.)
The above acid group refers to a portion obtained by removing one or more hydrogen atoms or salts from various organic acids, inorganic acids, or salts thereof, and functions as a counter ion of N ^+. . Organic acids are formic acid, acetic acid, benzoic acid, benzene sulfonic acid, paratoluene sulfonic acid, citric acid, oxalic acid, adipic acid, etc., and inorganic acids are hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, boric acid, fluoric acid, etc. Hydrochloric acid, perchloric acid and the like.

  Aniline black exhibits various black expressions such as greenish black, blackish black, reddish black, and bluish black that cannot be expressed with carbon black, making use of its features, paint, printing ink, paint, Used in various applications such as poster colors, plastics, and thermal transfer inks. In addition, since the structure contains many polar groups such as amino groups and diazine structures, it has extremely hydrophilic characteristics and has been used mainly in aqueous media. Conventionally, a method using dichromate has been considered optimal as an oxidizing agent used in the production of aniline black. Since dichromate is a very strong oxidant, it generates sufficient oxidative condensation. In addition, chromium ions and some of the copper ions used as catalysts coordinate with the aromatic amine condensate, forming a strong network between molecules and absorbing light of various wavelengths uniformly. Therefore, aniline black prepared using this exhibits extremely high blackness.

  However, chromium ion contained in dichromate is a pollutant that is extremely harmful to the human body (currently chromium contained in aniline black synthesized with dichromic acid is coordinated to the pigment and harmful hexavalent Although chromium is not included and safety is recognized), copper ions derived from the copper salt used as a catalyst are also harmful substances. Accordingly, there is a demand for a product that does not use these harmful substances at the time of manufacture and has no fear of mixing these harmful substances. With these achievements, it can also be used for direct skin contact applications such as eyebrow pencils, eyebrow powders, eyebrow mascaras, eye shadows, compact powders, foundations, lipsticks, and nail enamels that have been avoided. The possibility comes out.

  Conventionally, a production method (Patent Document 1) characterized in that aniline is made into an aqueous solution of acid and oxidized with persulfate, which does not contain toxic substances such as chromium and copper, hydrogen peroxide and its decomposition catalyst There is known a production method (Patent Document 2 and Patent Document 3) in which aniline is oxidized using an OH radical generated as a oxidizing agent using a metal or a metal salt that can be formed.

  In addition, as a π-conjugated polymer having a high blackness and a highly controlled particle diameter, a black pigment obtained by oxidative polymerization with an oxidizing agent in the presence of a water-soluble polymer compound, a transition metal compound and a protonic acid ( Patent document 4) is known.

  Furthermore, by simultaneously dropping the catalyst and the oxidant during the oxidative polymerization process, the decomposition rate of the oxidant is arbitrarily controlled, aniline black having a small primary particle axial ratio (Patent Document 5), and aniline during the oxidative polymerization process. An aniline black (Patent Document 6) containing a sulfone group by a copolymerization reaction between a sulfonyl compound and sulfonyl compound is known.

  On the other hand, most black colorants such as non-magnetic developer for electrophotography and black matrix for liquid crystal are inexpensive, excellent in coloring power, excellent in blackness, and excellent in heat resistance. In recent years, there has been a demand for higher image quality of electrophotographic images and higher light blocking ratio of the black matrix, and higher density such as increasing the amount of colorant added has been studied. However, since carbon black is difficult to disperse in the binder resin and has a low volume resistivity, the former case still has the problem that the charging performance of the developer is hindered (charge holding ability is reduced). In the latter case, it is difficult to impart dispersion stability of carbon black in a dispersion such as an organic solvent, resulting in poor fluidity and a low volume resistivity as a resist thin film.

  In general, aniline black is known to have a higher volume resistivity value than inorganic black pigments such as carbon black, and application of aniline black is being studied to overcome the aforementioned problems. As a black colorant for a non-magnetic developer for electrophotography, application as a developer excellent in charge retention performance with little charge leakage even at high temperatures and high humidity is being studied. (Patent Document 7, Patent Document 8, Patent Document 9)

JP 2001-261989 A Japanese Patent Laid-Open No. 10-245497 JP 2000-72974 A JP-A-9-31353 JP 2012-153744 A JP 2012-153745 A JP 2010-19970 A JP 2005-195893 A JP 2001-106938 A

As mentioned above, aniline black, which does not contain harmful substances such as chromium and copper, has excellent blackness, and has a high volume resistivity, is used for conventional applications such as paints and printing inks, as well as electrophotography. It has come to be used in applications such as non-magnetic developer for liquid crystal and black matrix for liquid crystal. In addition, along with the expansion of such needs, it has become necessary to make exquisite color adjustments according to the purpose in the black category. For example, there are various demands of manufacturers such as jet black, black black, blue black, green black, purple black, and red black. In particular, bluish black and purple black, which are difficult to express with conventional black pigments such as carbon black and aniline black, are highly demanded because of their high-class feeling. There is also a demand for jet black that requires strict color adjustment.
In order to adjust various colors, complementary colors are generally performed by simply adding and mixing dyes and pigments. However, when the dye is added, the effect is small even if it is added in a large amount. In addition, the addition of a pigment has a great effect on the hue, but a decrease in blackness, a change in volume specific resistance, and a decrease in dispersibility due to mixing of different kinds of particles occur.
Therefore, while having the characteristics such as non-chrome, high blackness, and high volume resistivity as described above, it is possible to freely express black in hues according to the application and purpose, and bluish black and purple that were difficult to express in the past Although aniline black that can be expressed in black and jet black and has excellent dispersibility is desired, such aniline black has not yet been obtained.
Moreover, in addition to the advantages of aniline black such as bluish black expression and high volume resistivity, further improvements in blackness and heat resistance are expected, but such aniline black has not yet been obtained. Absent.
In addition to the advantages of aniline black such as bluish black expression and high volume resistivity, aniline has excellent dispersibility in hydrophobic media such as resins and organic solvents, which was also a problem with carbon black, and has high blackness. Black is expected, but such aniline black has not yet been obtained.

That is, although the thing of the above-mentioned patent document 1 is bluish black as shown in the after-mentioned comparative example 1-3, it cannot be said that blackness is enough and fine adjustment of a hue is impossible. Furthermore, the volume resistivity value is 2 × 10 ⁵ Ω · cm, which is relatively low resistance. Furthermore, it is difficult to say that the heat resistance is sufficient. Furthermore, dispersibility is inferior.

  Those described in Patent Documents 2 and 3 described above are reddish black as described in Comparative Example 1-4, and it is difficult to say that the blackness is sufficient, and fine adjustment of the hue is impossible. Furthermore, it is difficult to say that the heat resistance is sufficient. Furthermore, dispersibility is inferior.

The thing described in the above-mentioned patent document 4 is green black as shown in the following comparative examples 1-5, it is hard to say that blackness is enough, and the fine adjustment of a hue is impossible. Furthermore, the volume resistivity value is 4 × 10 ⁴ Ω · cm, which is relatively low resistance. Furthermore, it is difficult to say that the heat resistance is sufficient. Further, the dispersibility is inferior.

  The thing of the above-mentioned patent documents 5 and 6 has sufficient blackness, as shown in the following comparative examples 1-1 and 1-2, respectively. However, Patent Document 5 expresses blackish black and Patent Document 6 expresses reddish black, and further adjustment of the hue is impossible. Dispersibility in a medium having high hydrophobicity is poor.

Therefore, the present invention can express black of any hue, and can be expressed in bluish black, purple black, and jet black, which was difficult to express in the past, has excellent blackness, high heat resistance, and volume-specific An object of the present invention is to provide aniline black particles having a high resistance value and excellent dispersibility. In addition, it is possible to express black with a free hue colored with the aniline black, and it is possible to express blue black, purple black, jet black which was difficult to express in the past, excellent dispersibility, excellent blackness, It is a technical object to provide a resin composition having high heat resistance, an aqueous dispersion, and a solvent dispersion.
In addition, the present invention provides aniline black having a high degree of hydrophobicity and excellent blackness, as well as excellent dispersibility in hydrophobic media such as resins and organic solvents colored with the aniline black. It is a technical problem to provide an excellent resin composition and a solvent-based dispersion.

  The technical problems include the following first invention 1-1 to 1-10, second invention 2-1 to 2-8, third invention 3-1 to 3-9, and fourth invention. 4-1 to 4-8.

  The first invention is aniline black particles containing at least one kind of acidic dye. (Invention 1-1)

  In the first invention, the acid dye contained is at least one or more functional groups selected from aromatic sulfonic acid, aromatic carboxylic acid, phenol, aromatic phosphoric acid, aromatic boric acid, and thiophenol, Or it is the aniline black particle | grains of this invention 1-1 which have the functional group of those salts. (Invention 1-2)

  The first invention is the aniline black particles according to the invention 1-1 or 1-2, wherein the acidic dye contained has any skeleton of triphenylmethane, xanthene, indigo, naphtholazo, anthraquinone, or phthalocyanine. It is. (Invention 1-3)

  Moreover, 1st invention is the aniline black particle in any one of this invention 1-1 to 1-3 which contains 1-30 weight part of acidic dyes with respect to 100 weight part of aniline black basic skeleton. (Invention 1-4)

The first invention, volume resistivity, aniline black particles according to any one of the present invention 1-1 to 1-4 which is a ^{1.0 × 10 6 ~1.0 × 10 10} Ω · cm is there. (Invention 1-5)

  Moreover, 1st invention is the aniline black particle | grains in any one of this invention 1-1 to 1-5 whose average particle diameter of a primary particle is the range of 0.05-1.0 micrometer. (Invention 1-6)

  Moreover, 1st invention is the aniline black particle | grains in any one of this invention 1-1 to 1-6 whose powder pH is 4.0-9.0. (Invention 1-7)

  The first invention is a resin composition comprising the aniline black particles according to any one of the inventions 1-1 to 1-7. (Invention 1-8)

  The first invention is an aqueous dispersion comprising the aniline black particles according to any one of the inventions 1-1 to 1-7. (Invention 1-9)

  Moreover, 1st invention is a solvent dispersion which contains the aniline black particle | grains in any one of this invention 1-1 to 1-7. (Invention 1-10)

The second invention is an aniline black containing 1 to 60 parts by weight of carbon black with respect to 100 parts by weight of aniline black basic skeleton, and the volume resistivity of the aniline black is 10 ⁶ to 10 ¹⁰ Ω · cm. Aniline black particles characterized by (Invention 2-1)

  Moreover, 2nd invention is the aniline black particle | grains of this invention 2-1 whose average particle diameter of the primary particle | grains of carbon black contained is 0.01-0.1 micrometer. (Invention 2-2)

  Moreover, 2nd invention is the aniline black particle | grains as described in this invention 2-1 or 2-2 whose sulfur content is 0.2 weight%-10.0 weight%. (Invention 2-3)

  Moreover, 2nd invention is the aniline black particle | grains in any one of this invention 2-1 to 2-3 whose average particle diameter of a primary particle is 0.05-1.0 micrometer. (Invention 2-4)

  Moreover, 2nd invention is aniline black particle | grains in any one of this invention 2-1 to 2-4 whose powder pH is 4.0-9.0. (Invention 2-5)

  The second invention is a resin composition comprising the aniline black particles according to any one of the inventions 2-1 to 2-5. (Invention 2-6)

  The second invention is an aqueous dispersion comprising the aniline black particles according to any one of the inventions 2-1 to 2-5. (Invention 2-7)

  The second invention is a solvent-based dispersion comprising the aniline black particles according to any one of the inventions 2-1 to 2-5. (Invention 2-8)

A third invention is an aniline black containing 1 to 60 parts by weight of a chromatic color pigment based on 100 parts by weight of an aniline black basic skeleton, and the volume resistivity of the aniline black is 10 ⁶ to 10 ¹⁰ Ω · cm. This is an aniline black particle. (Invention 3-1)

  Moreover, 3rd invention is the aniline black particle | grains of this invention 3-1 whose average particle diameter of the primary particle of the chromatic pigment contained is 0.01-0.2 micrometer. (Invention 3-2)

  Moreover, 3rd invention is the aniline black particle | grains in any one of this invention 3-1 or 3-2 whose average particle diameter of a primary particle is 0.05-1.0 micrometer. (Invention 3-3)

  Moreover, 3rd invention is the aniline black particle | grains in any one of this invention 3-1 to 3-3 whose volume average particle size distribution is a single peak. (Invention 3-4)

  Moreover, 3rd invention is aniline black particle | grains as described in this invention 3-1 to 3-4 whose sulfur content is 0.2 weight%-10.0 weight%. (Invention 3-5)

  Moreover, 3rd invention is the aniline black particle | grains in any one of this invention 3-1 to 3-5 whose powder pH is 4.0-9.0. (Invention 3-6)

  Moreover, 3rd invention is a resin composition which comprises the aniline black particle | grains in any one of this invention 3-1 to 3-6. (Invention 3-7)

  The third invention is an aqueous dispersion comprising the aniline black particles according to any one of the inventions 3-1 to 3-6. (Invention 3-8)

  Moreover, 3rd invention is a solvent dispersion which contains the aniline black particle | grains in any one of this invention 3-1 to 3-6. (Invention 3-9)

  4th invention is the aniline black particle | grains whose hydrophobicity by a powder wettability test is 5-80 volume%. (Invention 4-1)

  Moreover, 4th invention is aniline black particle | grains of this invention 4-1 in which 0.1-60.0 weight% of 1 or more processing agents chosen from the alkylamine, the vinyl alkyl ketone, the fatty acid, and the silane exist. It is. (Invention 4-2)

  Moreover, 4th invention is aniline black particle | grains as described in this invention 4-1 or 4-2 whose sulfur content is 0.2 weight%-10.0 weight%. (Invention 4-3)

  Moreover, 4th invention is the aniline black particle | grains in any one of this invention 4-1 to 4-3 whose average particle diameter of a primary particle is 0.05-1.0 micrometer. (Invention 4-4)

  Moreover, 4th invention is aniline black particle | grains in any one of this invention 4-1 to 4-4 whose powder pH is 4.0-9.0. (Invention 4-5)

A fourth aspect of the present invention is at aniline black particles according to any one of the present invention 4-1 to 4-5 in which the volume resistivity is ^{1.0 × 10 6 ~1.0 × 10 10} Ω · cm is there. (Invention 4-6)

  A fourth invention is a resin composition comprising the aniline black particles according to any one of the inventions 4-1 to 4-6. (Invention 4-7)

  The fourth invention is a solvent-based dispersion comprising the aniline black particles according to any one of the inventions 4-1 to 4-6. (Invention 4-8)

  The aniline black particles according to the first invention can express black of any hue, and can be expressed even in bluish black, purple black, and jet black that were difficult to express in the past. It is excellent as an aniline black particle having excellent volume resistivity.

  The resin composition colored with the aniline black particles according to the first invention is suitable as a resin composition because it is excellent in dispersion and blackness. In addition, the aqueous dispersion and the solvent-based dispersion colored with the aniline black particles according to the present invention are excellent in dispersibility and can express black of a free hue, and are conventionally difficult to express bluish black, purple It can also be expressed in black of taste or jet black, and is excellent in blackness, and therefore suitable as various dispersions.

  The aniline black particles according to the second invention are suitable as aniline black particles having the advantages of carbon black such as high blackness and heat resistance in addition to the advantages of aniline black particles such as bluish black expression and high volume resistivity. It is.

  The resin composition colored with the aniline black particles according to the second invention is suitable as a resin composition because it has excellent dispersibility and excellent blackness. In addition, the aqueous dispersion and the solvent-based dispersion colored with particles of aniline black according to the present invention are suitable as various dispersions because of excellent dispersibility and excellent blackness.

  The aniline black particles according to the third invention are suitable as aniline black particles that can express black of a free hue, have excellent blackness, have a high volume resistivity, and have excellent dispersibility.

  The resin composition colored with the aniline black particles according to the third invention can express black having a free hue, and is suitable as a resin composition excellent in blackness and dispersibility. In addition, the aqueous dispersion and the solvent-based dispersion colored with the aniline black particles according to the present invention can express black having a free hue, and are suitable as various dispersions excellent in blackness and dispersibility. .

  Since the aniline black particles according to the fourth invention have a high degree of hydrophobicity, the aniline black particles have excellent dispersibility in hydrophobic media such as resins and organic solvents, and are suitable as aniline black particles with excellent blackness.

  The resin composition colored with the aniline black particles according to the fourth invention is suitable as a resin composition because it has excellent dispersibility and excellent blackness. The solvent-based dispersion colored with the aniline black particles according to the present invention is suitable as a solvent-based dispersion because of its excellent dispersibility and excellent blackness.

  The configuration of the present invention will be described in more detail as follows. In the present invention, the aniline black particles in the first to fourth inventions may be simply abbreviated as aniline black.

  First, aniline black particles according to the first invention will be described.

  The aniline black particles according to the first invention include at least one kind of acidic dye. This acid dye is insolubilized by being included as part of the acid group of aniline black, and is further included in layers in the entanglement of the polymer of aniline black due to interactions such as π-π stacking with aniline black. Therefore, it is estimated that it becomes difficult to dissolve in water or a solvent.

  The acidic dye contained in the aniline black particles according to the first invention preferably has one or more functional groups selected from aromatic sulfonic acid, aromatic carboxylic acid, and phenol, or a functional group of a salt thereof. . Or you may have a functional group of aromatic phosphoric acid, aromatic boric acid, thiophenol, or those salts. It is estimated that the functional group of these acidic dyes becomes a direct acid group.

  The acidic dye contained in the aniline black particles according to the first invention is preferably one having a skeleton of triphenylmethane, xanthene, phthalocyanine, indigo, anthraquinone, or naphtholazo. Since these skeletons have a planar structure and are similar in size to the N-phenyldibenzoparaazine skeleton of aniline black, interactions such as π-π stacking are likely to occur, and the aniline black polymer It is estimated that it becomes easy to be included in the entanglement in layers. For example, (example of triphenylmethane) C.I. I. Acid Blue 1, 9, 90, 93, 119, C.I. I. Acid Violet 17, C.I. I. Food Blue 5, C.I. I. Food Green 3, phenolphthalein, etc. (example of xanthene) C.I. I. Acid Red 51, 52, 92, 93, 94, rhodamine B, rhodamine 123, fluorescein, etc. (example of phthalocyanine) C.I. I. Direct Blue 86, 199, C.I. I. Reactive Blue 15, etc. (example of anthraquinone) C.I. I. Acid Blue 25, 40, 43, 62, 129, C.I. I. Acid Green 25, 41, C.I. I. Acid Violet 42, 43, C.I. I. Acid Black 48, C.I. I. Reactive Blue 19, etc. (example of naphtholazo) C.I. I. Acid Red 1, 13, 14, 18, 27, 32, 42, 88, 138, C.I. I. Acid Orange 7, 19, C.I. I. Acid Violet 14, C.I. I. Acid Blue 92, 113, C.I. I. Acid Black 1, 26, C.I. I. Acid Yellow 65, C.I. I. Modern Black 9, 11, C.I. I. Modern Blue 13, C.I. I. Food Yellow3, C.I. I. Food Red 3, 7, 9, 40, C.I. I. Food Black 1 etc. are mentioned.

  Among the acid dyes contained in the aniline black particles according to the first invention, those having a function, for example, those that emit fluorescence (rhodamine B, rhodamine 123, fluorescein, etc.), the color changes depending on pH, heat, etc. There are also things (phenolphthalein etc.), and they may be included to give a function.

  The amount of the acid dye contained in the aniline black particles according to the first invention preferably includes 1 to 30 parts by weight of the acid dye with respect to 100 parts by weight of the aniline black basic skeleton. When the amount is less than 1 part by weight, the effect of the acid dye is dilute. When the amount exceeds 30 parts by weight, the amount of the acid dye exceeds the amount contained as the acid group of aniline black, and the liberated acid dye may be dissolved in a medium such as resin, water, or solvent. A more preferred amount is 1 to 25 parts by weight. A more preferred amount is 3 to 20 parts by weight.

  The acidic dye contained in the aniline black particles according to the first invention is contained in aniline black by adjusting the kind and amount thereof in order to express the target hue, blackness and function. A plurality of acidic dyes may be mixed and included. Also, aniline black containing different acid dyes can be mixed and used. Furthermore, the aniline black according to the present invention can be used by mixing with an existing pigment such as carbon black.

  The aniline black particles according to the first invention may further contain a sulfur-containing compound used in the aniline black particles according to the second invention described later. The aniline black particles according to the first invention may further contain carbon black used in the aniline black particles according to the second invention described later. The aniline black particles according to the first invention may further contain a chromatic pigment used in the aniline black particles according to the third invention described later, that is, the exemplified inorganic pigment and organic pigment. The aniline black particles according to the first invention may be further subjected to a hydrophobization treatment performed with the aniline black particles according to the fourth invention described later, and may have a specified degree of hydrophobicity.

  Next, aniline black particles according to the second invention will be described.

  The aniline black particles according to the second invention contain 1 to 60 parts by weight of carbon black with respect to 100 parts by weight of the aniline black basic skeleton. If the carbon black is less than 1 part by weight, the effect of including carbon black is dilute. When carbon black exceeds 60 parts by weight, the volume resistivity value becomes low. A more preferable carbon black content is 5 to 50 parts by weight.

  The aniline black particles according to the second invention are preferably in a state in which dispersed carbon black is coated with a polymer aniline black. By encapsulating carbon black in a dispersed state, it can have a bluish black expression and high volume resistivity, and can have high blackness and heat resistance.

  The average particle size of the primary particles of carbon black contained in the aniline black particles according to the second invention is preferably 0.01 to 0.1 μm. When the average particle size of the carbon black primary particle is smaller than 0.01 μm, it is difficult to disperse in the aniline black particle, and when it is larger than 0.1 μm, it protrudes to the surface of the aniline black particle and the volume resistivity value is remarkably lowered. To do.

  The carbon black contained in the aniline black particles according to the second invention is not particularly limited, and any of furnace black, lamp black, channel black, acetylene black, and thermal black can be used. Further, depending on the purpose, a plurality of types of carbon black may be mixed and included in aniline black. Further, aniline black containing different carbon blacks can be mixed and used. Furthermore, the aniline black particles according to the second invention can be used by mixing with existing pigments such as carbon black.

  The aniline black particles according to the second invention may contain inorganic pigments, organic pigments, resins and the like other than carbon black in a dispersed state or a dissolved state, or may be simply added. Examples include inorganic pigments such as iron titanate, cobalt black, manganese black, iron copper chromite black, manganese ferrite black, iron cobalt black, copper chromite black, molybdenum sulfide, iron oxide, perylene black, phthalocyanine, quinacridone, monoazo yellow, etc. Examples include organic pigments, resins such as polystyrene, polyethylene, and polyester. As the inorganic pigment and the organic pigment, inorganic pigments and organic pigments exemplified as chromatic pigments used in aniline black particles according to the third invention described later can also be used.

  The aniline black particles according to the first invention may be used together with carbon black to form the aniline black particles according to the second invention. Furthermore, the hydrophobization process performed with the aniline black particle which concerns on 4th invention mentioned later may be performed, and you may have the hydrophobization degree prescribed | regulated.

  Next, aniline black particles according to the third invention will be described.

  The aniline black particles according to the third invention contain 1 to 60 parts by weight of the chromatic pigment with respect to 100 parts by weight of the aniline black basic skeleton. When the chromatic color pigment is less than 1 part by weight, the effect of including the chromatic color pigment is dilute. When the chromatic pigment exceeds 60 parts by weight, the volume specific resistance value becomes low. A more preferable content of the chromatic pigment is 5 to 50 parts by weight.

  The pigment contained in the aniline black particles according to the third invention is not particularly limited, but chromatic pigments other than black and white are preferable, and any of inorganic pigments and organic pigments can be used. Further, depending on the purpose, a plurality of types of chromatic pigments may be mixed and included in aniline black. Further, aniline black containing different chromatic pigments can be mixed and used. Furthermore, the aniline black according to the third invention can be mixed with an existing dye and used.

  The inorganic pigment is not particularly limited, but iron oxide, barium yellow, strontium chromate, yellow lead, cadmium zinc yellow, cobalt yellow, titanium yellow, brown, molybdate orange, cobalt blue, ultramarine blue, cerulean Examples include blue, zirconium vanadium blue, and chromium oxide. Specifically, C.I. I. Pigment Yellow 31, 32, 34, 35, 35: 1, 36, 37, 37: 1, 40, 41, 42, 43, 48, 53, 118, 119, 157, 158, 159, 160, 161, 162, 163 , 164, 184, 189, Pigment Orange 20, 21, 23, 75, 78, C.I. I. Pigment Red 101, 102, 104105, 106, 107, 108, 108: 1, 113, 230, 231, 232, 233, 235, 235, 275, C.I. I. Pigment Violet 14, 15, 16, 47, 49, C.I. I. Pigment Blue 27, 28, 29, 33, 35, 36, 71, 72, 73, 74, C.I. I. Pigment Green 17, 18, 19, 21, 23, 26, 50, C.I. I. Pigment Brown 6, 7, 11, 24, 29, 31, 33, 34, 35, 37, 39, 40, 43, 44, 45, C.I. I. Pigment Metal 1, 2, 4, 5, 6, pearl pigment, daylight fluorescent pigment, inorganic fluorescent pigment, and the like.

  The organic pigment is not particularly limited, and examples thereof include indigo, phthalocyanine blue, phthalocyanine green, naphthol red, diketopyrrolopyrrole, quinacridone, monoazo yellow, and disazo yellow. Specifically, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 18, 24, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 115, 116, 117, 120, 126, 127, 128, 138, 139, 147 , 150,151,152,153,154,155,156,166,167,168,169,170,172,173,174,175,176,180,181,182,183,185,188,191,193 , 194, 198, 199, 202, 203, C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 22, 24, 34, 36, 38, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 71, 72, 73 74, 77, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 48: 1, 48: 2. 48: 3, 48: 4, 49: 1, 49; 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 57, 57: 1, 58: 4, 60 63: 1, 63: 2, 64: 1, 68, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 112, 114, 122, 123, 144 , 146,147,149,150,151,166,168,169,170,171,172,173,174,175,176,177,178,179,181,184,185,187,188,190,191 , 193, 194, 200, 202, 206, 2 7, 208, 209, 210, 214, 216, 220, 221, 224, 242, 243, 245, 247, 251, 253, 254, 255, 256, 257, 258, 260, 264, 266, 267, 268, 269, 270, 272, 273, 274, 275, C.I. I. Pigment Violet 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 50, C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 24, 25, 56, 60, 61, 62, 63 66, C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 12, 15, 36, C.I. I. Pigment Brown 1, 22, 23, 25, 27, and the like.

  The aniline black particles according to the third invention are preferably in a state in which a dispersed chromatic pigment is coated with a polymer aniline black. By including the chromatic pigment in the dispersed state, the aniline black having high blackness and high volume resistivity is obtained while effectively reflecting the hue of the pigment.

  The average particle diameter of the primary particles of the chromatic pigment contained in the aniline black particles according to the third invention is preferably 0.01 to 0.2 μm. When the average particle size of the primary particles of the pigment is smaller than 0.01 μm, it is difficult to disperse in the aniline black particles, and when it is larger than 0.2 μm, it protrudes to the surface of the aniline black particles and the volume resistivity value is remarkably lowered. There is a case.

  The aniline black particles according to the third invention may contain a resin other than the chromatic pigment in a dispersed state or a dissolved state, or may be simply added. Examples thereof include resins such as polystyrene, polyethylene, and polyester.

  Next, aniline black particles according to the fourth invention will be described.

  The aniline black particles according to the fourth invention have a degree of hydrophobicity of 5 to 80% by volume by a powder wettability test. When the degree of hydrophobicity is within the above range, even a highly hydrophobic resin or organic solvent can be easily dispersed. When the degree of hydrophobicity is less than 5% by volume, the hydrophilicity is too strong and difficult to disperse in the resin or organic solvent. On the other hand, when the degree of hydrophobicity is 80% by volume or more, the surface of the aniline black particles is difficult to wet with the resin or organic solvent, and dispersion becomes difficult. The degree of hydrophobicity is preferably 8 to 75% by volume, more preferably 7 to 70% by volume.

  The degree of hydrophobicity by the powder wettability test is determined by allowing sample powder to float in pure water and continuously supplying a water-soluble organic solvent with high wettability while stirring to allow the sample powder to wet and settle. The intensity was measured, the transmitted light intensity and the concentration of the water-soluble organic solvent were plotted, and the concentration of the water-soluble organic solvent when the transmitted light intensity reached 50% was defined as the degree of hydrophobicity. It is determined that the higher the degree of hydrophobicity, the higher the hydrophobicity of the powder.

  Although it does not specifically limit as a water-soluble organic solvent, Alcohol, a ketone, etc. are used. For example, methanol, ethanol, isopropanol, acetone and the like can be mentioned, and one or more may be combined.

  The above-mentioned range can be achieved for the degree of hydrophobicity by adjusting the type of treatment agent, the amount of treatment agent added, and the type and amount of sulfur-containing compounds present as acid groups of aniline black.

  The treating agent for aniline black particles according to the fourth invention is preferably one or more treating agents selected from alkylamines, vinyl alkyl ketones, fatty acids, and silanes. Alkylamine, fatty acid, etc. are deposited on the surface without reaction, or are present on the surface by adsorption. Vinyl alkyl ketone, silane, and the like are covalently bonded to the surface through Michael addition reaction, dehydration reaction, and the like.

  The amount of the treatment agent for aniline black particles according to the fourth invention is preferably 0.1 to 60.0% by weight. When the amount of the treatment agent is less than 0.1% by weight, the degree of hydrophobicity is 0%. When the amount of the treatment agent is 60.0% by weight or more, the treatment agent itself tends to interfere with dispersion because the treatment agent is too much. The amount of the treatment agent is more preferably 0.2 to 50.0% by weight, still more preferably 0.5 to 48.0% by weight.

  Alkylamines include methylamine, ethylamine, propylamine, butylamine hexylamine, octylamine (caprylamine), decylamine, dodecylamine (laurylamine), tetradecylamine (myristylamine), hexadecylamine, octadecylamine, stearylamine , Oleylamine, coconut amine, beef tallow amine, distearylamine, dimethyl coconutamine, dimethyloctylamine, dimethyldecylamine, dimethylsilyllaurylamine, dimethylmyristylamine, dimethylpalmitylamine, dimethylstearylamine, dimethylbehenylamine, dilaurylmonomethyl Amine, trioctylamine, cured beef tallow propylene diamine, tallow propylene diamine, etc. It may be those together.

  Examples of the vinyl alkyl ketone include vinyl methyl ketone, vinyl ethyl ketone, vinyl propyl ketone, vinyl pentyl ketone, vinyl hexyl ketone, 2-cyclohexen-1-one, and vinyl phenyl ketone. Good.

  Examples of fatty acids include butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, stearic acid, oleic acid, vacenoic acid, linol Acid, linolenic acid, eleostearic acid, arachidic acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid and the like may be mentioned, and one or more may be combined.

  Silanes include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, dimethyldiethoxysilane, trimethyltrimethoxysilane, triethylethoxysilane, hexyltrimethoxysilane, and hexyltriethoxysilane. , Decyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, triphenylethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxy Rumethyldiethoxysilane, 3-glycidpropylpropyltriethoxysilane, p-styrylmethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3 -Methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane 3-aminopropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane N- (vinylbenzyl) -2-aminoethyl-3-aminoethyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (Triethoxypropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, alkoxysilane oligomer, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, hexamethyldisilazane, hexaphenyldisilazane, and the like. It may be a dish.

  The treatment agent for aniline black particles according to the fourth aspect of the present invention is present by adjusting the type and amount in order to express the target hue and blackness. A plurality of treatment agents may be mixed and present. Further, aniline black containing different treatment agents can be mixed and used. Furthermore, the aniline black particles according to the fourth invention can be used by mixing with existing pigments such as carbon black.

  Next, features common to the aniline black particles according to the first to fourth inventions will be described.

The sulfur content contained in the aniline black particles according to the first to fourth inventions is preferably 0.2 to 10.0% by weight. The origin of sulfur content is due to the sulfur-containing compound contained in part of the acid group of aniline black. The sulfur-containing compound is added in the synthesis stage of aniline black, and is combined with an aromatic amine such as aniline or a part of the salt of the aromatic amine as an acid group to form a micelle in water.
In the aniline black particles according to the second and third inventions, carbon black (aniline black particles according to the second invention) and chromatic pigment (aniline black particles according to the third invention) are dispersed using this aqueous solution. In the micelle, the carbon black and the chromatic pigment are dispersed in an incorporated state (emulsified state). Then, when an oxidizing agent is added as it is, polymerization is performed in an emulsified state, and the aniline black particles according to the second and third inventions become aniline black particles containing carbon black and a chromatic pigment. Further, it is presumed that the sulfur-containing compound remaining as an acid group contributes to improving the dispersibility of the aniline black particles. A more preferable sulfur content is 0.2 to 6.0% by weight.
In the aniline black particles according to the fourth invention, after the above-described oxidative polymerization, when the above-described treatment agent is surface-treated, the aniline black particles according to the fourth invention are obtained. This sulfur-containing compound is presumed to greatly contribute to particle shape control and surface properties. When there is no sulfur-containing compound, the degree of hydrophobicity is low even when a large amount of the treatment agent is treated, and it may be difficult to disperse in a resin or organic solvent. Further, when there is no sulfur-containing compound, even if a large amount of treatment agent is treated to increase the degree of hydrophobicity, it is difficult to disperse in a resin or an organic solvent. A more preferable sulfur content is 0.2 to 8.0% by weight, and still more preferably 0.3 to 6.0% by weight.

Examples of the sulfur-containing compound include aromatic sulfonic acid, aliphatic sulfonic acid, aromatic thiol, and aliphatic thiol. These sulfur-containing compounds act as a part of the emulsifier as described above, and in the aniline black particles according to the second invention, carbon black is included in the dispersed state in the aniline black. In such aniline black particles, it becomes a factor that chromatic pigments are included in aniline black in a dispersed state.
In the aniline black particles according to the fourth aspect of the invention, the shape control and surface properties of the particles are improved, and the processing agent is present or reacts efficiently. In addition, it is presumed that the sulfur-containing compound exists as an acid group in aniline black and contributes to ease of dispersion by lowering the interfacial tension between aniline black particles.
Examples of sulfur-containing compounds include benzenesulfonic acid, paratoluenesulfonic acid, dodecylbenzenesulfonic acid, methyl sulfate, ethyl sulfate, propyl sulfate, butyl sulfate, pentyl sulfate, hexyl sulfate, heptyl sulfate, octyl sulfate, decyl sulfate, dodecyl. Examples include sulfuric acid, thiophenol, and dodecyl thiol.

  As the sulfur-containing compound, an acid dye having color developability may be used. As the acid dye, the acid dye described and exemplified in the aniline black particles according to the first invention can be used. The aniline black particles according to the first and fourth inventions may be used together with carbon black or a chromatic pigment.

  Some sulfur-containing compounds have a function, for example, those that emit fluorescence such as sulforhodamine B and sulfofluorescene, and the color changes by external stimuli such as thermochromism, photochromism, electrochromism, solvatochromism There are also things, etc., and they may be included to give functions.

The hue of aniline black according to the first to fourth inventions refers to the a * value and the b * value in the color index measured by the evaluation method described later. Saturation refers to the c * value.
The blackness of aniline black according to the first invention uses the lightness L * value as an index, and being excellent in blackness means that the L * value is 12.0 or less among the measured values. When the L * value exceeds 12.0, it is difficult to say that the blackness is excellent. A more preferred L * value is 11.5 or less, still more preferably 5 to 11.0.
The blackness of aniline black according to the second invention uses the lightness L * value as an index, and being excellent in blackness means that the L * value is less than 14.0 among the measured values. When the L * value is 14.0 or more, it is difficult to say that the blackness is excellent. A more preferred L * value is less than 12.0.
The blackness of the aniline black according to the third invention uses the lightness L * value as an index, and being excellent in blackness means a case where the L * value is less than 15.0 among the measured values. When the L * value is 15.0 or more, it is difficult to say that the blackness is excellent. A more preferred L * value is less than 14.0.
The blackness of aniline black according to the fourth invention uses the lightness L * value as an index, and being excellent in blackness means that the L * value is less than 14.0 among the measured values. When the L * value is 14.0 or more, it is difficult to say that the blackness is excellent. A more preferable L * value is 12.0 or less.
The a * value, b * value, and c * value vary depending on the purpose, and are controlled by the particle size, shape, polymerization degree, and type and amount of acidic dye contained in aniline black. When expressed as normal black, the a * value is preferably -20 to 20, the b * value is preferably -20 to 20, and the c * value is preferably 0 to 28, but is controlled according to the purpose. Should not be limited to this value.

  The color of the aniline black according to the first to fourth inventions is a jet black, blackish black, bluish black, greenish, depending on the a * value, b * value, and c * value, which will be described later. This is expressed in specific color expressions such as black, purple black, and red black. Moreover, what emitted the fluorescent color by irradiating a black light was described as fluorescence.

  The heat resistance of the aniline black according to the first to fourth inventions is evaluated by the color reduction rate due to heat, which is measured by a measurement method described later. This is because the heat resistance is not required to be reduced in the production stage when used in an electrophotographic non-magnetic developer or a liquid crystal black matrix. “Excellent heat resistance” means that the color reduction rate due to heat is less than 30%. When the color reduction rate due to heat is 30% or more, it is difficult to say that the material has heat resistance. A more preferable heat reduction rate is less than 20%.

  Examples of the aromatic amine used in the aniline black according to the first to fourth inventions include aromatic amines such as aniline, methylaniline, ethylaniline, toluidine, and aminonaphthalene, and nitrogen-containing heterocyclic compounds such as pyrrole and pyridine. These may contain a combination of one or more of them, or may be copolymerized.

  In order to improve the properties such as dispersibility and color developability, the aniline black according to the first to fourth inventions includes an aromatic compound other than an aromatic amine, a heterocyclic compound, a fragment thereof, It may contain what combined 2 or more, and may be copolymerized. Aromatic compounds include aromatics such as benzene, toluene, xylene and naphthalene, aromatic acids such as phenol, benzenesulfonic acid, paratoluenesulfonic acid and benzoic acid, and heterocyclic compounds such as furan, thiophene and quinone. Can be mentioned.

  The aniline black according to the first to fourth inventions may contain an acid group other than the acid dye and an acid group other than the sulfur-containing compound. The acid group refers to a portion obtained by removing one or more hydrogen atoms from various inorganic acid and organic acid molecules, and functions as an N + counter ion. Organic acids are formic acid, acetic acid, benzoic acid, benzenesulfonic acid, paratoluenesulfonic acid, citric acid, oxalic acid, adipic acid, phenol, etc., and inorganic acids are hydroxyl, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, Examples thereof include boric acid, hydrofluoric acid, and perchloric acid.

  The aniline black according to the first to third inventions may be subjected to a surface treatment in order to improve dispersibility, color developability and the like. The surface treatment material is not particularly limited, but surfactants such as alkyl alcohols, fatty acids and alkylamines, polymers such as acrylic resins, polyester resins and urethane resins, silane coupling agents, and organic silicon such as silanes. Examples include organic surface treatment agents such as compounds, inorganic surface treatment agents such as inorganic fine particles such as silica, alumina and titanium oxide, and organic and inorganic surface treatment agents such as rosin-calcium and rosin-magnesium, or two of them. What was processed with what was combined above is also good. That is, the aniline black according to the fourth invention may be applied to the first to third inventions.

The volume resistivity of the aniline black particles according to the first to fourth inventions is preferably 1.0 × 10 ^{6 to} 1.0 × 10 ¹⁰ Ω · cm. When the volume resistivity value is less than 10 ⁶ Ω · cm, the high volume resistivity characteristic of aniline black is lost, and the volume resistivity value when used as a resin composition is also relatively low resistance. This is not preferable because it is difficult to adapt to non-magnetic developer for electrophotography and black matrix use.
A more preferable volume specific resistance value of the aniline black particles according to the first invention is 1.0 × 10 ^{7 to} 1.0 × 10 ¹⁰ Ω · cm, and even more preferably 1.5 × 10 ^{7 to} 5.0 × 10. ⁹ Ω · cm.
In the aniline black particles according to the second invention, the volume resistivity of carbon black is usually about 10 ⁻² to 10 ¹ Ω · cm, and the volume resistivity decreases when exposed to a small amount on the surface of the substance. End up. When the carbon black is coated with the polymer aniline black in a dispersed state, the aniline black according to the second invention has a high volume resistivity. A more preferable volume resistivity value is 10 ⁶ to 10 ⁹ Ω · cm.
In the aniline black particles according to the third invention, some chromatic pigments have extremely low volume resistivity. For example, the volume specific resistance value of iron oxide is usually about 10 ¹ to 10 ² Ω · cm, and the volume specific resistance value becomes low if it is exposed even on a small amount on the surface of the substance. When the chromatic pigment is coated with the polymer aniline black in a dispersed state, the aniline black according to the third invention has a high volume resistivity. A more preferable volume resistivity value is 10 ⁶ to 10 ⁹ Ω · cm.
A more preferable volume specific resistance value of aniline black according to the fourth invention is 1.0 × 10 ^{7 to} 1.0 × 10 ¹⁰ Ω · cm, and even more preferably 1.5 × 10 ^{7 to} 5.0 × 10 ^9. Ω · cm.

  The average particle diameter of the primary particles of aniline black according to the first to fourth inventions is preferably in the range of 0.05 μm to 1.0 μm. When the average particle size of the primary particles is less than 0.05 μm, the dispersion is difficult and the blackness is inferior. Moreover, since the coloring power is low when the average particle diameter of the primary particles exceeds 1.0 μm, the blackness is inferior. A more preferable average particle diameter of primary particles is 0.10 to 0.85 μm.

  The powder pH of the aniline black according to the first to fourth inventions is preferably in the range of 4.0 to 9.0. When the powder pH is less than 4.0, a stronger acid may be contained as an acid group, and an acid dye may not be contained in aniline black. When the powder pH exceeds 9.0, the acid dye as an acid group may be dissociated and dissolved in a medium such as water. A more preferable powder pH is 4.5 to 8.5, and still more preferably 5.0 to 8.0.

  Next, a method for producing aniline black particles according to the first to fourth inventions will be described.

  The aniline black particles according to the first invention are prepared by dissolving aniline, an aniline acid salt, an aromatic amine, an aromatic amine acid salt or a mixture thereof in water, After adjusting to pH, an acidic dye is added and dissolved to make an acidic aqueous solution. To this, a metal or metal salt that can be a decomposition catalyst for the oxidant is added to form a mixed solution. While stirring the mixed solution, the oxidant is added dropwise and subjected to oxidative polymerization to obtain crude aniline black. Next, the aniline black particles according to the first invention can be obtained by neutralizing the crude aniline black with an alkali agent, performing filtration, washing with water and drying, followed by pulverization. The metal or metal salt that can serve as a decomposition catalyst may be dropped simultaneously with the oxidizing agent after making it into a uniform aqueous solution in advance.

  In the production stage of the aniline black particles according to the first invention, an aniline, an aniline acid salt aromatic amine, an aromatic acid acid salt, or a part of a mixture thereof and an acid dye are contained in water. An electrostatic interaction occurs, and an acid dye salt is formed in the reaction solution. Since it acts as a pseudo emulsifier to form micelles and undergoes oxidative polymerization therein, it is presumed to be a pseudo emulsion polymerization. Therefore, it is presumed that the acid dye is closely contained in the polymer of aniline black and hardly dissolves in the resin, water or solvent.

  The aniline black particles according to the second invention are obtained by dispersing or dissolving an aniline acid salt, an aromatic amine, an aromatic amine acid salt, or a mixture thereof in water. After adjusting to a predetermined pH, a sulfur-containing compound is added to make an acidic aqueous solution. Carbon black is added to this acidic aqueous solution and a dispersion operation is performed to obtain a dispersion. While stirring the dispersion, a metal or a metal salt that can become a decomposition catalyst for the oxidant is added. Then, an oxidizing agent is added dropwise with stirring, and oxidative polymerization is performed to obtain crude aniline black. Next, the crude aniline black is neutralized with an alkali agent, filtered, washed with water, dried, and then pulverized to obtain the aniline black according to the present invention. The metal or metal salt that can serve as a decomposition catalyst may be dropped simultaneously with the oxidizing agent after making it into a uniform aqueous solution in advance.

  In the production stage of the aniline black particles according to the second invention, either aniline, an aniline acid salt aromatic amine, or an aromatic acid acid salt in water, or a part of a mixture thereof and a sulfur-containing compound Causes electrostatic interaction and becomes a sulfur-containing compound salt in the reaction solution. It becomes a micelle in the water. When carbon black was added thereto and dispersed, carbon black and aniline, aniline acid aromatic amine, or aromatic amine acid salt were incorporated into the micelle. Disperse (emulsify). Since it is oxidatively polymerized, it is presumed to be a pseudo emulsion polymerization. Therefore, it is presumed that carbon black becomes aniline black particles incorporated in the polymer of aniline black in a dispersed state.

  As the sulfur-containing compound and carbon black, one or more of the sulfur-containing compound and carbon black may be used.

  The carbon black is dispersed using a media disperser such as a bead mill or a medialess disperser such as CLEARMIX, FILMIX, or an ultrasonic homogenizer.

  The aniline black particles according to the third invention are obtained by dispersing or dissolving aniline, an aniline acid salt, an aromatic amine, an aromatic amine acid salt, or a mixture thereof in water. After adjusting to a predetermined pH, add a sulfur-containing compound to make an acidic aqueous solution. A chromatic pigment is added to this acidic aqueous solution, and a dispersion operation is performed to obtain a dispersion. While stirring the dispersion, a metal or a metal salt that can become a decomposition catalyst for the oxidant is added. Then, an oxidizing agent is added dropwise with stirring, and oxidative polymerization is performed to obtain crude aniline black. Next, the crude aniline black is neutralized with an alkali agent, filtered, washed with water, dried, and then pulverized to obtain the aniline black according to the present invention. The metal or metal salt that can serve as a decomposition catalyst may be dropped simultaneously with the oxidizing agent after making it into a uniform aqueous solution in advance.

  In the production stage of the aniline black particles according to the third invention, in water, either aniline, an aniline acid salt aromatic amine, or an aromatic acid acid salt, or a part of a mixture thereof and a sulfur-containing compound Causes electrostatic interaction and becomes a sulfur-containing compound salt in the reaction solution. It becomes a micelle in the water. When a chromatic pigment is added thereto and dispersion operation is performed, the pigment and aniline, an aniline acid salt aromatic amine, or one or more of the aromatic amine acid salts are incorporated in the micelle. Disperse (emulsify). Since it is oxidatively polymerized, it is presumed to be a pseudo emulsion polymerization. Therefore, it is presumed that the pigment becomes aniline black particles incorporated in the polymer of aniline black in a dispersed state.

  As the sulfur-containing compound, one or more of the various sulfur compounds may be used.

  As the pigment, one or more of the chromatic pigments may be used.

  The chromatic color pigment is dispersed using a media dispersing machine such as a bead mill or a medialess dispersing machine such as CLEARMIX, FILMIX, or an ultrasonic homogenizer.

  The aniline black particles according to the fourth invention are prepared by dispersing or dissolving aniline, an aniline acid salt, an aromatic amine, an aromatic amine acid salt, or a mixture thereof in water. After adjusting to a predetermined pH, add a sulfur-containing compound to make an acidic aqueous solution. While stirring this aqueous solution, a metal or metal salt that can be a decomposition catalyst for the oxidizing agent is added. And an oxidizing agent is dripped, stirring, and it is obtained by oxidative polymerization. Then, a treatment agent such as alkylamine is added to this and diffused to the surface. Thereafter, the pH is readjusted again to fix or react the treatment agent on the surface. Then, after filtering, washing with water, and drying, it can grind | pulverize and the aniline black particle | grains based on this invention can be obtained. The metal or metal salt that can serve as a decomposition catalyst may be dropped simultaneously with the oxidizing agent after making it into a uniform aqueous solution in advance.

  As the sulfur-containing compound, one or more of the various sulfur compounds may be used.

  As the treatment agent, one or more of the various treatment agents may be used.

  Examples of the acid used for pH adjustment used in the production of the aniline black particles according to the first to fourth inventions include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, tetrafluoroboric acid, perchloric acid, periodic acid, Formic acid, acetic acid, citric acid, oxalic acid, adipic acid and the like may be mentioned, and these may be used alone or as a mixture. The concentration of the acidic aqueous solution is usually 0.1 to 20%, preferably about 0.2 to 15%, although it depends on the type of acid.

  Examples of the oxidizing agent used in the production of the aniline black particles according to the first to fourth inventions include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate, hydrogen peroxide, oxygen, and the like. It may be used as a mixture. The usage-amount of an oxidizing agent is 0.1-10 mol with respect to 1 mol of anilines, Preferably it is 0.5-5 mol. Further, it is preferable to gradually add the oxidizing agent to the reaction solution. Addition usually takes 10 minutes to 10 hours, preferably 20 minutes to 5 hours, so that the oxidative polymerization rate can be controlled, which is preferable in terms of particle size control.

  Examples of the metal or metal salt that can be a decomposition catalyst for the oxidant used in the production of the aniline black particles according to the first to fourth inventions include iron, ferric chloride, ferric nitrate, ferric sulfate, and ferric chloride. Examples thereof include ferrous iron, ferrous nitrate, ferrous sulfate, iron-EDTA chelate, platinum chloride, gold chloride and silver nitrate, and these may be used alone or as a mixture. The amount of the catalyst used is usually about 0.01 to 1 mol, preferably about 0.02 to 0.5 mol, per 1 mol of aniline. Moreover, it is preferable to add gradually the metal or metal salt which can become a decomposition catalyst of an oxidizing agent with respect to the reaction solution. It is more preferable to add the decomposition catalyst for the oxidant and the oxidant at the same time because the decomposition rate of the oxidant can be more easily controlled. An oxidative polymerization reaction proceeds by adding an oxidizing agent and a metal or a metal salt that can be a decomposition catalyst of the oxidizing agent to the reaction solution.

  Although the reaction temperature in the manufacturing method of the aniline black particle which concerns on 1st-4th invention is not specifically limited, Usually, you may make it react at 10-70 degreeC, Preferably it is 20-60 degreeC. Moreover, after adding an oxidizing agent, it is preferable to stir the reaction solution normally for 10 minutes to 10 hours, preferably for 20 minutes to 5 hours.

  Since the crude aniline black obtained by the method for producing aniline black particles according to the first invention is strongly acidic, the pH is adjusted to a range of 5 to 10 with an acid agent or an alkali agent. Preferably the pH is adjusted in the range of 5-8. If necessary, the mixture may be heated and stirred at 20 to 95 ° C. for 30 minutes to 1 hour.

  Since the crude aniline black obtained by the method for producing aniline black particles according to the second to fourth inventions is strongly acidic, the pH is adjusted within the range of 4.0 to 9.0 with an acid agent or an alkali agent. Adjusted. Preferably, the pH is adjusted in the range of 5.0 to 8.0. If necessary, the mixture may be heated and stirred at 20 to 95 ° C. for 30 minutes to 1 hour.

  The acid agent used in the production of the aniline black particles according to the first to fourth inventions may be either an inorganic compound or an organic compound. Examples of the inorganic compound include inorganic acids such as hydrochloric acid and sulfuric acid, and examples of the organic compound include organic acids such as acetic acid, citric acid, and adipic acid.

  The alkali agent used in the method for producing aniline black particles according to the first to fourth inventions may be either an inorganic compound or an organic compound. Examples of inorganic compounds include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and carbonates such as sodium carbonate, and examples of organic compounds include trialkanolamines such as triethanolamine and triisopropanolamine. .

  In the method for producing aniline black particles according to the first to fourth inventions, the pH of the aniline black particles is adjusted by neutralization with an alkali agent, and then filtered, washed with water and dried according to a conventional method. Is obtained.

  Next, the resin composition according to the first to fourth inventions will be described.

  The resin compositions according to the first to fourth inventions are aniline black particles according to the first to fourth inventions, known thermoplastic resins, and if necessary, lubricants, plasticizers, antioxidants, ultraviolet absorbers, various stabilizers. Additives such as are blended and configured.

  The blending ratio of the aniline black particles in the resin compositions according to the first to fourth inventions can be used in the range of 0.01 to 200 parts by weight with respect to 100 parts by weight of the constituent base material. Is preferably 0.05 to 100 parts by weight, more preferably 0.1 to 50 parts by weight.

  The amount of the additive may be 50% by weight or less with respect to the total of the aniline black particles and the thermoplastic resin. When the content of the additive exceeds 50% by weight, the moldability is lowered.

  The lightness L * value of the resin composition according to the first aspect of the invention is such that the L * value of the color index measured by an evaluation method described later is 12.0 or less, which is black compared to the case where a known aniline black is used. It is excellent. Furthermore, the L * value is preferably 11.5 or less. Moreover, the result of the visual observation of a dispersibility is the range of 3-4 among the evaluation methods mentioned later.

  The lightness L * value of the resin composition according to the second invention is a color index measured by an evaluation method described later. Blackness refers to the lightness L * value as an index, and excellent blackness refers to a case where the L * value is less than 14.0. When the L * value is 14.0 or more, it is difficult to say that the blackness is excellent. A more preferred L * value is less than 12.0. Moreover, the result of the visual observation of a dispersibility is the range of 3-5 among the evaluation methods mentioned later.

  The lightness L * value of the resin composition according to the third invention is a color index measured by an evaluation method described later. Blackness uses lightness L * value as an index, and being excellent in blackness means that the L * value is less than 15.0. When the L * value is 15.0 or more, it is difficult to say that the blackness is excellent. A more preferred L * value is less than 14.0. Moreover, the result of the visual observation of a dispersibility is the range of 3-5 among the evaluation methods mentioned later.

  The lightness L * value of the resin composition according to the fourth invention is a color index measured by an evaluation method described later. Blackness refers to the lightness L * value as an index, and excellent blackness refers to a case where the L * value is less than 14.0. When the L * value is 14.0 or more, it is difficult to say that the blackness is excellent. A more preferred L * value is less than 12.0. Moreover, the result of the visual observation of a dispersibility is the range of 3-5 among the evaluation methods mentioned later.

  The heat resistance of the resin compositions according to the first to fourth inventions is evaluated by the color reduction rate due to heat, which is measured by a measurement method described later. This is because the heat resistance is not required to be reduced in the production stage when used in an electrophotographic non-magnetic developer or a liquid crystal black matrix. “Excellent heat resistance” means that the color reduction rate due to heat is less than 30%. When the color reduction rate due to heat is 30% or more, it is difficult to say that the material has heat resistance. A more preferable heat reduction rate is less than 20%.

  Next, a method for producing the resin composition according to the present invention will be described.

  The resin composition according to the present invention thoroughly mixes the aniline black particles and the resin beforehand, and then applies a strong shearing action under heating using a kneader or an extruder to break up the aggregates of the aniline black particles. After the aniline black particles are uniformly dispersed in the resin, the resin is molded into a shape suitable for the purpose.

  Next, the aqueous dispersion according to the first to third inventions will be described.

  The aqueous dispersions according to the first to third inventions are aniline black particles according to the first to third inventions, water, if necessary, extender pigments, aqueous solvents, surfactants, pigment dispersants, resins, pH adjusters. An antifoaming agent is blended and configured.

  The mixing ratio of the aniline black particles in the aqueous dispersions according to the first to third inventions can be used in the range of 0.1 to 200 parts by weight with respect to 100 parts by weight of the dispersion-constituting substrate. Is preferably 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight.

  As the resin, commonly used water-soluble alkyd resins, water-soluble melamine resins, water-soluble acrylic resins, and water-soluble urethane emulsion resins can be used.

  As the solvent, alcohol such as butyl alcohol, glycerin, butyl cellosolve and the like can be used.

  As an antifoaming agent, a well-known antifoaming agent can be used. For example, Nopco 8034 (product name), SN deformer 477 (product name), SN deformer 5013 (product name), SN deformer 247 (product name), SN deformer 382 (product name) (all of which are manufactured by San Nopco Corporation), Antihome 08 (trade name), Emulgen 903 (trade name) (all of which are manufactured by Kao Corporation).

  The viscosity of the aqueous dispersion according to the first to third inventions is preferably 20.0 mPa · s or less, more preferably 15.0 mPa · s or less. When the viscosity exceeds 20 mPa · s, the blackness is inferior. The lower limit of the viscosity is about 1.0 mPa · s.

  The storage stability evaluation of the aqueous dispersions according to the first to third inventions is preferably less than ± 10%, more preferably ± 6% or less, and even more preferably ± in the viscosity change rate measured by the evaluation method described later. 5% or less.

The hue of the aqueous dispersion according to the second invention refers to the L * value, a * value, and b * value of the color index measured by the evaluation method described later. Blackness uses lightness L * value as an index, and being excellent in blackness means that the L * value is less than 14.0 among the measured values. When the L * value is 14.0 or more, it is difficult to say that the blackness is excellent. A more preferred L * value is less than 12.0.
The hue of the aqueous dispersion according to the third invention refers to an L * value, an a * value, and a b * value among the color index measured by an evaluation method described later. Saturation refers to c *. Blackness uses the lightness L * value as an index, and being excellent in blackness means that the L * value is less than 15.0 among the measured values. When the L * value is 15.0 or more, it is difficult to say that the blackness is excellent. A more preferred L * value is less than 14.0.
The a * value and the b * value vary depending on the purpose, and are controlled by the particle size, shape, polymerization degree, and type and amount of acid groups contained in the aniline black particles. When expressed as normal black, the a * value is preferably -20 to 20, and the b * value is preferably -20 to 20, but should be controlled according to the purpose and is limited to this value. is not.

  The colors of the aqueous dispersions according to the second and third inventions are jet black, blackish black, bluish black, greenish according to the notation method to be described later based on the a * value, b * value, and c * value. It is written in specific color expressions such as black, purple black, and reddish black.

  The heat resistance of the aqueous dispersions according to the first to third inventions is evaluated by the color reduction rate due to heat, measured by a measurement method described later. This is because the heat resistance is not required to be reduced in the production stage when used in an electrophotographic non-magnetic developer or a liquid crystal black matrix. “Excellent heat resistance” means that the color reduction rate due to heat is less than 30%. When the color reduction rate due to heat is 30% or more, it is difficult to say that the material has heat resistance. A more preferable heat reduction rate is less than 20%.

  Next, the manufacturing method of the aqueous dispersion which concerns on 1st-3rd invention is described.

  The aqueous dispersions according to the first to third inventions are prepared by mixing aniline black particles, water and additives, and media dispersers such as bead mills, or medialess dispersers such as CLEARMIX, FILMIX, and ultrasonic homogenizers. It is dispersed by using and manufactured by post-treatment such as filtration. In order to improve the dispersion stability, it may be produced by a self-dispersion process or a microcapsule process.

  Next, the solvent dispersion according to the first to fourth inventions will be described.

  The solvent-based dispersions according to the first to fourth inventions are the aniline black particles, resins, solvents, as necessary, extender pigments, drying accelerators, surfactants, curing accelerators, assistants according to the first to fourth inventions. Agents are blended and configured.

  The blending ratio of the aniline black particles in the solvent-based dispersion according to the first to fourth inventions can be used in the range of 0.1 to 200 parts by weight with respect to 100 parts by weight of the dispersion-constituting substrate. Considering handling, it is preferably 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight.

  As the resin, commonly used acrylic resins, alkyd resins, polyester resins, polyurethane resins, epoxy resins, phenol resins, melamine resins, amino resins, and the like can be used.

  Usable solvents include commonly used toluene, xylene, tetrahydrofuran, ethyl acetate, butyl acetate, methyl acetate, methyl isobutyl ketone, butyl cellosolve, ethyl cellosolve, butyl alcohol, propylene glycol monomethyl ether acetate, aliphatic hydrocarbons, etc. it can.

  The viscosity of the solvent-based dispersion according to the first to fourth inventions is preferably 20.0 mPa · s or less, more preferably 17.0 mPa · s or less. If it exceeds 20 mPa · s, the dispersibility is poor and the blackness is poor. The lower limit of the viscosity of the solvent-based dispersion is about 2.0 mPa · s.

  The storage stability evaluation of the solvent-based dispersion according to the first to fourth inventions is preferably less than ± 10%, more preferably ± 6% or less, even more preferably ±± 10% in viscosity change rate measured by an evaluation method described later. 5% or less.

The hue of the solvent-based dispersion according to the second and fourth inventions refers to the L * value, a * value, and b * value among the color index measured by the evaluation method described later. Blackness uses lightness L * value as an index, and being excellent in blackness means that the L * value is less than 14.0 among the measured values. When the L * value is 14.0 or more, it is difficult to say that the blackness is excellent. A more preferred L * value is less than 12.0.
The hue of the solvent-based dispersion according to the third invention indicates an L * value, an a * value, and a b * value among the color index measured by an evaluation method described later. Saturation refers to c *. Blackness uses the lightness L * value as an index, and being excellent in blackness means that the L * value is less than 15.0 among the measured values. When the L * value is 15.0 or more, it is difficult to say that the blackness is excellent. A more preferred L * value is less than 14.0.
In any of the inventions, the a * value and b * value vary depending on the purpose, and are controlled by the particle size, shape, polymerization degree, and type and amount of acid groups contained in the aniline black particles. When expressed as normal black, the a * value is preferably -20 to 20, and the b * value is preferably -20 to 20, but should be controlled according to the purpose and is limited to this value. is not.

  The colors of the solvent-based dispersions according to the first to fourth inventions are jet black, blackish black, blackish blue, green, depending on the a * value, b * value, and c * value, as described later. It is expressed in specific color expressions such as taste black, purple black, and red black.

  The heat resistance of the solvent-based dispersion according to the first to fourth inventions is evaluated by the color reduction rate due to heat, measured by a measurement method described later. This is because the heat resistance is not required to be reduced in the production stage when used in an electrophotographic non-magnetic developer or a liquid crystal black matrix. “Excellent heat resistance” means that the color reduction rate due to heat is less than 30%. When the color reduction rate due to heat is 30% or more, it is difficult to say that the material has heat resistance. A more preferable heat reduction rate is less than 20%.

  Next, a method for producing a solvent-based dispersion according to the first to fourth inventions will be described.

  The solvent-based dispersions according to the first to fourth inventions are prepared by mixing aniline black particles, a solvent, an additive, and a resin, and a media dispersion machine such as a bead mill, or a medialess machine such as a clear mix, a fill mix, and an ultrasonic homogenizer. It is dispersed by using a disperser and is subjected to post-treatment such as filtration. In order to improve the dispersion stability, it may be produced by a self-dispersion process or a microcapsule process.

<Action>
In the first invention, the aniline black particles containing at least one or more types of acidic dyes are added with color development and color expression derived from the acid dye component in addition to the original color development and black expression of aniline black. Therefore, it was found that free black expression is possible. The contained acid dye is insolubilized by being included as part of the acid group of aniline black, and is further included in layers between the entanglement of the polymer of aniline black due to interactions such as π-π stacking with aniline black. Therefore, it is estimated that it is difficult to dissolve in resin, water or solvent.

An aniline black particle comprising 1 to 60 parts by weight of carbon black in the second invention based on 100 parts by weight of the aniline black basic skeleton, wherein the volume resistivity of the aniline black particle is 10 ⁶ to 10 ¹⁰ Ω · cm. The aniline black particles are characterized in that the carbon black contained is present in the polymer formed by aniline black and is not exposed to the surface. Realized resistance value. Furthermore, since the aniline black particles according to the present invention contain carbon black having high blackness and high heat resistance, the black aniline black particles have higher blackness and higher heat resistance than conventional aniline black.

An aniline black particle comprising 1 to 60 parts by weight of the chromatic pigment according to the third invention based on 100 parts by weight of the aniline black basic skeleton, wherein the volume resistivity of the aniline black is 10 ⁶ to 10 ¹⁰ Ω · cm. The aniline black particles, which are characterized by their pigment components, can express black of any hue, and the chromatic pigments contained are present in the polymer formed by aniline black and are not exposed to the surface. Despite containing coloring pigments, it has excellent blackness and high volume resistivity.

  The aniline black particles having a hydrophobization degree of 5 to 80% by volume according to the powder wettability test according to the fourth invention are easily dispersed in a hydrophobic medium such as a resin or an organic solvent that cannot be achieved by the conventional aniline black. It is suitable as aniline black particles having characteristics, excellent blackness, and high volume resistivity.

  A typical embodiment of the present invention is as follows. In the following Examples and Comparative Examples, Examples 1-1 to 1-20 and Comparative Examples 1-1 to 1-20 are examples relating to the first invention, and Examples 2-1 to 2-20 and Comparative Examples 2-1 to 2-20 are examples relating to the second invention, Examples 3-1 to 3-32 and Comparative Examples 3-1 to 3-20 are examples relating to the third invention, Examples 4-1 to 4-15 and Comparative Examples 4-1 to 4-15 are examples relating to the fourth invention. The evaluation method is shown below.

For the volume resistivity, first, 0.5 g of the particle powder is measured, and pressure molding is performed at a pressure of 1.372 × 107 Pa (140 Kg / cm ² ) using a KBr tablet molding machine (Shimadzu Corporation). A cylindrical sample to be measured was prepared. This sample to be measured was set between stainless steel electrodes, and a resistance value R (Ω) was measured by applying a voltage of 15 V with an electric resistance measuring device (model 4329A manufactured by Yokogawa Hokushin Electric Co., Ltd.). Next, the area A (cm ² ) and the thickness t0 (cm) of the upper surface of the sample to be measured (cylindrical) are measured, and each measured value is inserted into the following equation 1 to determine the volume resistivity (Ω · cm). Asked.
<Equation 1>
Volume resistivity (Ω · cm) = R × (A / t0)

  The average particle size of the primary particles is the particle size of 350 primary particles shown in the micrographs by scanning electron microscope (manufactured by Hitachi High-Technologies) or transmission electron microscope JEM-1200EX II (manufactured by JASCO), respectively. Measured and shown as the average value.

  The pH value of the powder was measured by weighing 5 g of a sample into a 300 ml Erlenmeyer flask, adding 100 ml of boiled pure water, heating and holding the boiled state for about 5 minutes, then plugging it and letting it cool to room temperature. After adding water corresponding to the above, plugging again, shaking for 1 minute, allowing to stand for 5 minutes, the pH of the obtained supernatant was measured according to JIS Z8802-7, and the obtained value was determined as the powder pH value. did.

  The degree of hydrophobicity by the powder wettability test was determined using a powder wettability tester WET-101P (manufactured by RHESCA) which is a dedicated machine. First, 1.0 g of sample powder was weighed, suspended in pure water contained in a 200 mL beaker, and while the solution was stirred at 400 rpm, methanol sufficiently deaerated with an ultrasonic cleaner was continuously added therein. It was supplied at 2 ml / min. Then, when the powder is wetted and settled, the transmitted light intensity is measured using laser light (780 nm), the transmitted light intensity and the methanol concentration are plotted, and the methanol when the transmitted light intensity reaches 50%. The concentration was recorded as the degree of hydrophobicity.

  The sulfur content and the quantification of the carbon content were determined by measuring the sulfur content and the carbon content using a Horiba metal carbon / sulfur analyzer EMIA-2200 (manufactured by Horiba Seisakusho).

The hue, lightness (blackness), and saturation of the aniline black particles according to the present invention were applied by applying the dispersions prepared in Examples and Comparative Examples, which will be described later, on cast coated paper using a bar coater having a WET film thickness of 24 μm. A piece (coating thickness: about 6 μm) was prepared, and for the coated piece, a colorimetric index L * value, a * value according to JIS Z8729 using a spectrocolorimeter X-Rite 939 (manufactured by X-Rite) , B * values are shown as measured values. The c * value was calculated by the following formula 2.
<Equation 2>
c * = ((a *) 2+ (b *) 2) 1/2

The determination of the blackness in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-5 was evaluated according to the following four stages according to the value of L *.
◎: L * is less than 11 ○: L * is 11 or more and less than 12 △: L * is 12 or more and less than 15 ×: L * is 15 or more

The determination of the blackness of aniline black particles in Examples 2-1 to 2-5 and Comparative Examples 2-1 to 2-5 was evaluated based on the value of L * in the following four stages.
◎: L * is less than 10.0 ○: L * is 10.0 or more and less than 12.0 △: L * is 12.0 or more and less than 14.0 ×: L * is 14.0 or more Things

The determination of the blackness of aniline black in Examples 3-1 to 3-8 and Comparative Examples 3-1 to 3-5 was evaluated according to the following four levels according to the value of L *.
◎: L * is less than 10.0 ○: L * is 10.0 or more and less than 12.0 △: L * is 12.0 or more and less than 15.0 ×: L * is 15.0 or more Things

The determination of the blackness of aniline black in Examples 4-1 to 4-5 and Comparative Examples 4-1 to 4-5 was evaluated according to the following four levels according to the value of L *.
◎: L * is less than 10.0 ○: L * is 10.0 or more and less than 12.0 △: L * is 12.0 or more and less than 14.0 ×: L * is 14.0 or more Things

The heat resistance of aniline black according to the present invention is obtained by applying a coating dispersion (coating film thickness: about 1 μm) obtained by applying the solvent-based dispersion prepared in Examples described later on a glass plate using a bar coater having a WET film thickness of 6 μm. After preparing and drying at 120 degreeC for 30 minutes, it heated at 250 degreeC for 2 hours in the gear oven. And about this application | coating piece, OD value (OD1) before a heating and OD value (OD2) after a heating are measured using the spectrocolorimeter X-Rite939 (product made from X-Rite), and by the following formula 2, it depends on heat The color reduction rate (%) was calculated.
<Equation 2>
Color reduction rate due to heat (%) = (OD1-OD2) / OD1 × 100

The determination of heat resistance was evaluated according to the following four stages according to the value of the color reduction rate due to heat.
◎: The color reduction rate due to heat is less than 10% ○: The color reduction rate due to heat is 10% or more and less than 20% △: The color reduction rate due to heat is 20% or more and less than 30% ×: The color reduction rate due to heat is 30 % Or more

  The color of aniline black according to the present invention is described in the following six types according to a * value, b * value, and c * value. Moreover, what emitted fluorescent color when irradiated with black light (UVmax = 365 nm) was described as fluorescence.

Jet black black: a * and b * are both 0.0 Black black: c * <1.0 Blue black: −20 ≦ a * <0 and −20 ≦ b * <0 And 1.0 ≦ c * ≦ 28 Greenish black: −20 ≦ a * <0 and 0 ≦ b * ≦ 20 and 1.0 ≦ c * ≦ 28 Purple black: 0 ≦ a * ≦ 20 and −20 ≦ b * <0 and 1.0 ≦ c * ≦ 28 Reddish black: 0 ≦ a * ≦ 20 and 0 ≦ b * ≦ 20 and 1.0 ≦ c * ≦ 28

  Examples 1-6 to 1-10 and Comparative Examples 1-6 to 1-10, Examples 2-6 to 2-10 and Comparative Examples 2-6 to 2-10, Examples 3-9 to 3-16 and About the lightness L * value of the resin composition in Comparative Examples 3-6 to 3-10, a spectrophotometer X-Rite 939 (manufactured by X-Rite) was used for the resin plates prepared in Examples and Comparative Examples described later. In accordance with JIS Z8729, L * values are shown as measured values.

The determination of the blackness of the resin compositions in Examples 1-6 to 1-10 and Comparative Examples 1-6 to 1-10 was evaluated according to the following four levels according to the value of L *.
◎: L * is less than 11 ○: L * is 11 or more and less than 12 △: L * is 12 or more and less than 15 ×: L * is 15 or more

The determination of the blackness of the resin compositions in Examples 2-6 to 2-10 and Comparative Examples 2-6 to 2-10 was evaluated according to the following four levels depending on the value of L *.
◎: L * is less than 10.0 ○: L * is 10.0 or more and less than 12.0 △: L * is 12.0 or more and less than 14.0 ×: L * is 14.0 or more Things

The determination of the blackness of the resin composition in Examples 3-9 to 3-16 and Comparative Example 3-6f3-10 was evaluated according to the following four levels according to the value of L *.
◎: L * is less than 10.0 ○: L * is 10.0 or more and less than 12.0 △: L * is 12.0 or more and less than 15.0 ×: L * is 15.0 or more Things

  For the lightness L * values of the resin compositions in Examples 4-6 to 4-10 and Comparative Examples 4-6 to 4-10, 3.0 g of the resin compositions prepared in Examples and Comparative Examples described later were weighed. A coating piece (coating thickness: about 6 μm) was prepared by immersing in 6.0 g of tetrahydrofuran and coated on cast-coated paper using a bar coater with a WET film thickness of 24 μm. The color index L * value was shown as a value measured according to JIS Z8729 using X-Rite 939 (manufactured by X-Rite).

The determination of the blackness of the resin compositions in Examples 4-6 to 4-10 and Comparative Examples 4-6 to 4-10 was evaluated according to the following four stages according to the value of L *.
◎: L * is less than 10.0 ○: L * is 10.0 or more and less than 12.0 △: L * is 12.0 or more and less than 14.0 ×: L * is 14.0 or more Things

Examples 1-6 to 1-10 and Comparative Examples 1-6 to 1-10, Examples 2-6 to 2-10 and Comparative Examples 2-6 to 2-10, Examples 3-9 to 3-16 and The dispersion state of the resin composition in Comparative Examples 3-6 to 3-10 was evaluated in five stages by visually determining the number of undispersed aggregated particles on the surface of the obtained resin composition. 5 indicates the best dispersion state.
5: Undispersed material is not recognized.
1 to 4 pieces are recognized per 4: 1 cm ² .
3 to 9 per 1 cm ² are recognized.
2 to 10-49 are observed per 1 cm ² .
50 or more are recognized per 1 cm ² .

  In Examples 4-6 to 4-10 and Comparative Examples 4-6 to 4-10, the dispersibility of the aniline black particles in the resin is such that the resin composition described later has a dispersibility of 3 or more, and that of 2 △ and 1 were judged as x.

  The dispersibility of aniline black in organic solvents in Examples 4-6 to 4-10 and Comparative Examples 4-6 to 4-10 is such that the viscosity of the solvent-based dispersion described later is 10 mP · s or less and the storage stability is ○ ○, the viscosity is more than 10 mP · s and less than 20 mP · s and the storage stability is ○, or the viscosity is less than 10 mP · s and the storage stability is Δ, and the others X.

The dispersibility of the resin compositions in Examples 4-6 to 4-10 and Comparative Examples 4-6 to 4-10 was obtained by dispersing a resin composition having the composition described later in an epoxy monomer at the following composition at 60 ° C., 24 Curing was allowed to stand for hours to produce pellets.
(Epoxy resin embedding)
Resin composition 1mg
Epoxy resin embedding agent Quetol-812 for electron microscope 3.0g
(Manufactured by Nissin EM)
DDSA (curing agent) 1.0 g
(Manufactured by Nissin EM)
MNA (curing agent) 2.0g
(Manufactured by Nissin EM)
DMP-30 (polymerization accelerator) 0.01 g
(Manufactured by Nissin EM)
Then, this pellet was sliced into a film thickness of 2 μm with this RMC ultramicrotome MT2C (Keiwa Corporation), and this was observed with a transmission electron microscope and evaluated in the following four stages.
4: Undispersed material is not recognized.
3: 1 to 10 undispersed materials are observed per 100 μm ² .
2: 10 to 49 undispersed materials are observed per 100 μm ² .
1: 50 or more non-dispersed materials are observed per 100 μm ² .

For the heat resistance of the resin composition according to the present invention, the resin composition prepared in Examples described later was pulverized at 12000 rpm using an ultracentrifugal pulverizer ZM200 (manufactured by Lecce), of which 3.0 g was propylene glycol 1 -Monomethyl ether 2-acetate was immersed in 6.0 g, and this was coated on a glass plate using a bar coater having a WET film thickness of 6 μm (coating thickness: about 1 μm), and 30 minutes at 120 ° C. And dried in a gear oven at 250 ° C. for 2 hours. And about this application | coating piece, OD value (OD1) before a heating and OD value (OD2) after a heating are measured using the spectrocolorimeter X-Rite939 (product made from X-Rite), and by the following formula 3, it depends on heat The color reduction rate (%) was calculated.
<Equation 3>
Color reduction rate due to heat (%) = (OD1-OD2) / OD1 × 100

The determination of heat resistance was evaluated according to the following four stages according to the value of the color reduction rate due to heat.
◎: The color reduction rate due to heat is less than 10% ○: The color reduction rate due to heat is 10% or more and less than 20% △: The color reduction rate due to heat is 20% or more and less than 30% ×: The color reduction rate due to heat is 30 % Or more

  The viscosity of the aqueous dispersion and the solvent dispersion according to the present invention was measured using an E-type viscometer TV-30 (manufactured by Toki Sangyo Co., Ltd.).

  The storage stability evaluation of the aqueous dispersion and the solvent dispersion according to the present invention was performed using an E-type viscometer TV-30 (manufactured by Toki Sangyo Co., Ltd.) for the initial viscosity and the time-lapse viscosity after 1 week at 25 ° C. Measured. The viscosity change rate from the initial viscosity (V1) to the time-dependent viscosity (V2) was calculated by the following formula 3, and evaluated in the following three stages.

<Equation 3>
Viscosity change rate (%) = (V2−V1) / V1 × 100

○: Viscosity change rate is less than ± 10% Δ: Viscosity change rate is ± 10% or more and less than ± 30% ×: Viscosity change rate is 30% or more

Regarding the hue, lightness (blackness), and saturation of the coating film of the aqueous dispersion according to the present invention and the solvent dispersion, the dispersion was applied onto cascoat paper using a bar coater having a WET film thickness of 24 μm. A coated piece (coating thickness: about 6 μm) was prepared, and the coated piece was subjected to colorimetric index L * value, a * according to JIS Z8729 using a spectrocolorimeter X-Rite 939 (manufactured by X-Rite). Value and b * value are shown as measured values. Moreover, c * was calculated by the following formula 4.
<Equation 4>
c * = ((a *) ² + (b *) ² ) ^1/2

The determination of the blackness of the coating films of the aqueous dispersion and the solvent-based dispersion in Examples 1-12 to 1-20 and Comparative Examples 1-11 to 1-20 was made in the following four stages depending on the value of L *. evaluated.
◎: L * is less than 11 ○: L * is 11 or more and less than 12 △: L * is 12 or more and less than 15 ×: L * is 15 or more

The determination of the blackness of the coating films of the aqueous dispersions and the solvent dispersions in Examples 2-12 to 2-28 and Comparative Examples 2-11 to 2-20 was made in the following four stages depending on the value of L *. evaluated.
◎: L * is less than 10.0 ○: L * is 10.0 or more and less than 12.0 △: L * is 12.0 or more and less than 14.0 ×: L * is 14.0 or more Things

The determination of the blackness of the coating film of the aqueous dispersion and the solvent-based dispersion in Examples 3-17 to 3-32 and Comparative Examples 3-11 to 3-20 was performed in the following four stages depending on the value of L *. evaluated.
◎: L * is less than 10.0 ○: L * is 10.0 or more and less than 12.0 △: L * is 12.0 or more and less than 15.0 ×: L * is 15.0 or more Things

The determination of the blackness of the coating film of the solvent-based dispersion in Examples 4-11 to 4-15 and Comparative Examples 4-11 to 4-15 was evaluated according to the following four levels depending on the value of L *.
◎: L * is less than 10.0 ○: L * is 10.0 or more and less than 12.0 △: L * is 12.0 or more and less than 14.0 ×: L * is 14.0 or more Things

  The color of the coating film of the aqueous dispersion and the solvent dispersion according to the present invention was described in the following six types according to the a * value, b * value, and c * value. Moreover, what emitted fluorescent color when irradiated with black light (UVmax = 365 nm) was described as fluorescence.

Jet black black: a * and b * are both 0.0 Black black: c * <1.0 Blue black: −20 ≦ a * <0 and −20 ≦ b * <0 And 1.0 ≦ c * ≦ 28 Greenish black: −20 ≦ a * <0 and 0 ≦ b * ≦ 20 and 1.0 ≦ c * ≦ 28 Purple black: 0 ≦ a * ≦ 20 and −20 ≦ b * <0 and 1.0 ≦ c * ≦ 28 Reddish black: 0 ≦ a * ≦ 20 and 0 ≦ b * ≦ 20 and 1.0 ≦ c * ≦ 28

  About the glossiness of the coating film of the aqueous dispersion which concerns on this invention, and a solvent dispersion, the coating piece apply | coated using the bar coater was used for the gloss meter UGV-5D (made by Suga Test Instruments Co., Ltd.). It was determined by measuring a glossiness of 45 °. The higher the gloss value, the better the dispersibility of the dispersion.

The heat resistance of the aqueous dispersion and the solvent dispersion according to the present invention was determined by applying a dispersion prepared in Examples described later on a glass plate using a bar coater having a WET film thickness of 6 μm (coating film) (Thickness: about 1 μm) was prepared, dried at 120 ° C. for 30 minutes, and then heated in a gear oven at 250 ° C. for 2 hours. And about this application | coating piece, OD value (OD1) before a heating and OD value (OD2) after a heating are measured using the spectrocolorimeter X-Rite939 (product made from X-Rite), and by the following number 5, The color reduction rate (%) was calculated.
<Equation 5>
Color reduction rate due to heat (%) = (OD1-OD2) / OD1 × 100

The determination of heat resistance was evaluated according to the following four stages according to the value of the color reduction rate due to heat.
◎: The color reduction rate due to heat is less than 10% ○: The color reduction rate due to heat is 10% or more and less than 20% △: The color reduction rate due to heat is 20% or more and less than 30% ×: The color reduction rate due to heat is 30 % Or more

The following Examples 1-1 to 1-20 and Comparative Examples 1-1 to 1-20 are examples relating to the first invention.
<Manufacture of aniline black>
Example 1-1
To 15.8 g (0.11 mol) of 71% sulfuric acid, 31.8 g (0.32 mol) of 35% hydrochloric acid and 2500 ml of water, 30 g (0.32 mol) of aniline was added. I. Acid Red 52 0.9 g was added and dissolved. Then, while stirring and mixing at a liquid temperature of 60 ° C., an aqueous solution prepared by dissolving 4.6 g (0.036 mol) of ferric chloride in 70 ml of water and 78.0 g (0.69 mol) of 30% hydrogen peroxide over 2 hours. Then, the mixture was stirred and mixed at a liquid temperature of 60 ° C. for 1 hour to complete the reaction. After completion of the reaction, the reaction solution was filtered and washed with water. The resulting cake was redispersed with 1000 ml of water and stirred for 24 hours. Thereafter, the mixture was neutralized with 10% caustic soda to pH 8.0, and after the pH was stabilized, it was filtered and washed with water. The paste was dried at 60 ° C. to obtain aniline black. (Aniline black 1-1)
The aniline black 1-6 of Comparative Example 1 prepared under the same conditions except that it does not contain an acid dye is slightly blackish with a * = 0.1, b * = 0.7 and blackish black. doing. On the other hand, the aniline black 1-1 of the present example was prepared by intentionally adjusting a * = 0.0 and b * = 0.0 by selecting and including the kind and amount of the acid dye. It can express the black color of jet black according to the goal.

Examples 1-2 to 1-5:
An aniline black whose color was intentionally adjusted was obtained in the same manner as in Example 1-1 except that the type and amount of the acid dye and the reaction conditions were variously changed. As target colors, Example 1-2 is bluish black, Example 1-3 is bluish black, Example 1-4 is purple black, and Example 1-5 is purple black + fluorescence. It is.

  The production conditions in these examples are shown in Table 1-1, and various characteristics of the obtained aniline black are shown in Table 1-2.

Comparative example 1-1 (follow-up experiment of Example 1 of JP2012-153744A):
To 15.8 g (0.11 mol) of 71% sulfuric acid, 31.8 g (0.32 mol) of 35% hydrochloric acid and 2500 ml of water, 30 g (0.32 mol) of aniline was added and stirred and mixed at a liquid temperature of 60 ° C. An aqueous solution obtained by dissolving 4.6 g (0.0363 mol) of ferric iron in 70 ml of water and 78.0 g (0.69 mol) of 30% hydrogen peroxide were added dropwise over 2 hours, and then stirred and mixed at a liquid temperature of 60 ° C. for 1 hour. To complete the reaction. After completion of the reaction, the reaction solution was filtered and washed with water. The resulting cake was redispersed with 1000 ml of water and stirred for 24 hours. Thereafter, the mixture was neutralized with 10% caustic soda to pH 9.5. After the pH was stabilized, the mixture was filtered and washed with water, and the paste was dried at 60 ° C. to obtain aniline black. (Aniline black 1-6)

Comparative example 1-2 (follow-up experiment of Example 1 of JP2012-153745A):
To 33.8 g (0.33 mol) of 35% hydrochloric acid and 1250 ml of water, 30 g (0.32 mol) of aniline was added, and 15.0 g (0.086 mol) of 4-hydroxybenzenesulfonic acid was added while stirring and mixing at a liquid temperature of 60 ° C. After adding and dissolving uniformly, an aqueous solution in which 4.6 g (0.036 mol) of ferrous chloride was dissolved in 70 ml of water, 78.0 g (0.69 mol) of 30% hydrogen peroxide was dropped over 2 hours, Thereafter, the mixture was stirred and mixed at a liquid temperature of 60 ° C. for 1 hour to complete the reaction. After completion of the reaction, the reaction solution was filtered and washed with water. The resulting cake was redispersed with 1000 ml of water and stirred for 24 hours. Thereafter, the mixture was neutralized with 10% caustic soda to pH 6.5. After the pH was stabilized, the mixture was filtered and washed with water, and the paste was dried at 60 ° C. to obtain aniline black. (Aniline black 1-7)

Comparative Example 1-3 (Follow-up experiment of Example 5 of JP 2001-261989 A):
30 g (0.32 mol) of aniline was dissolved in 600 ml (0.31 mol) of a 5.1% aqueous sulfuric acid solution, and 7.8 g (0.029 mol) of ferric chloride hexahydrate was added thereto at once, and the mixture was heated at 40 ° C. A solution prepared by dissolving 144 g (0.63 mol) of ammonium persulfate in 600 ml of water was added dropwise over 15 minutes, and then heated to 70 to 75 ° C. and stirred for 1 hour. After the reaction, insoluble matters were collected by filtration and washed with water. The obtained cake was reslurried in 900 ml of water, adjusted to pH 7 with a 10% aqueous sodium hydroxide solution, and then heated and stirred at 90 ° C. for 30 minutes. The insoluble material was collected by filtration, washed with water, and dried to obtain aniline black. (Aniline black 1-8)

Comparative Example 1-4 (Follow-up experiment of Example 1 of JP-A-2000-72974):
To 18.0 g (0.11 mol) of 62% sulfuric acid, 31.8 g (0.32 mol) of 35% hydrochloric acid and 300 ml of water, 30 g (0.32 mol) of aniline was added and dissolved by stirring, and then 13.2 g of ferrous sulfate. (0.087 mol) dissolved in 60 ml of water is added all at once. While stirring and mixing at a liquid temperature of 15 ° C., 90.0 g (0.79 mol) of 30% hydrogen peroxide was added over 4 hours, and then stirred and mixed at a liquid temperature of 15 ° C. for 4 hours to complete the reaction. After completion of the reaction, the reaction solution was filtered and washed with water. The cake obtained was redispersed with 960 ml of water, neutralized with 10% caustic soda to PH7, and after PH was stabilized, filtered and washed, and the paste was washed at 60 ° C. Drying gave aniline black. (Aniline black 1-9)

Comparative Example 1-5 (Additional test of Example 4 of JP-A-9-31353):
540 parts of ion-exchanged water, 30 parts of 4-methylbenzenesulfonic acid (0.17 mol), 15 parts of ferric sulfate at a concentration of 1% (0.0004 mol), pre-dissolved sodium polyisoprenesulfonate (molecular weight = 3 10) 350% of a 10% strength aqueous solution was charged into a reaction vessel, stirred well, and then charged with 33.8 g (0.33 mol) of 35% hydrochloric acid and 30 g (0.32 mol) of aniline. While maintaining the reaction temperature at 20 ° C., 360 parts of 5% hydrogen peroxide solution was continuously added over 2 hours, stirred for another 2 hours, filtered, washed with water, and the paste was dried at 60 ° C. Aniline black was obtained. (Unlin Black 1-10)

  The production conditions of these comparative examples are shown in Table 1, and the characteristics of the obtained aniline black are shown in Table 2.

    As described above, the aniline black particles of the first invention can express black with a hue according to the purpose, and can also be expressed in bluish black, purple black, and jet black that were difficult to express in the past. It is clear that it is possible, has excellent blackness, and has a high volume resistivity.

<Manufacture of resin composition>
Example 1-6:
Weigh 1.5 g of aniline black 1-1 particles obtained in Example 1-1 and 48.5 g of polyvinyl chloride resin powder 103EP8D (manufactured by Nippon Zeon Co., Ltd.), put them in a 100 cc poly beaker and use a spatula. Mixed powder was obtained by mixing. 0.5 g of calcium stearate is added to and mixed with the obtained mixed powder, the clearance of the hot roll heated to 160 ° C. is set to 0.2 mm, and the resin composition is kneaded into the roll little by little. After the kneading was continued until they were integrated, the resin composition was peeled off from the roll. Next, the resin composition is sandwiched between surface-polished stainless steel plates, placed in a hot press heated to 180 ° C., and press molded at a pressure of 1 ton / cm ² to obtain a resin composition having a thickness of 1 mm. It was.
The dispersion state of the obtained resin composition was 5, the L * value was 7.9, and the blackness was ◎.

Examples 1-7 to 1-10, Comparative Examples 1-6 to 1-10:
A resin composition was obtained in the same manner as in Example 6 except that the type of aniline black particles was changed.

    Various characteristics of the resin composition obtained at this time are shown in Table 1-3.

    As described above, it is obvious that the resin composition of the first invention is excellent in the dispersed state and excellent in blackness.

<Production of aqueous dispersion>
Example 1-11:
In a 140 ml glass bottle, 7.50 g of the aniline black powder obtained in Example 1 was used, and the aqueous dispersion composition was blended at the following ratio, and mixed and dispersed with a paint shaker for 60 minutes together with 50 g of 1.5 mmφ glass beads to obtain an aqueous dispersion. Prepared.
Aniline black 7.50 parts by weight,
2.50 parts by weight of anionic surfactant
(Hitenol NF-08: manufactured by Daiichi Kogyo Seiyaku)
10.00 parts by weight of a styrene-acrylic copolymer,
(JONCRYL63J: manufactured by BASF)
0.50 part by weight of antifoaming agent,
(Envelope Gem AD-01: Nissin Chemical Industry)
31.00 parts by weight of water.

    The viscosity of the obtained aqueous dispersion was 13.8 mPa · s. The storage stability was ○. From the above, the dispersibility is good. Further, the glossiness was 20%, and the coating film had an L * value of 8.6, an a * value of 0.0, and a b * value of 0.0, and jet black could be expressed as intended.

Examples 1-12 to 1-15, Comparative Examples 1-11 to 1-15:
An aqueous dispersion was obtained in the same manner as in Example 1-11 except that the types of aniline black particles were variously changed. As target colors, Example 1-12 is bluish black, Example 1-13 is bluish black, Example 1-14 is purple black, and Example 1-15 is purple black + fluorescence. It is.

    Various characteristics of the aqueous dispersion obtained at this time are shown in Table 1-4.

As described above, the aqueous dispersion of the first invention is excellent in dispersibility, can express black with a hue according to the target, and has been conventionally difficult to express blue, purple, and jet black. However, it can be expressed, and it is clear that it has excellent blackness.

<Production of solvent-based dispersion>
Example 1-16:
In a 140 ml glass bottle, use 7.50 g of the aniline black 1-1 powder obtained in Example 1-1, mix the solvent-based dispersion composition at the following ratio, and mix for 60 minutes with 50 g of 1.5 mmφ glass beads in a paint shaker. A solvent dispersion was prepared by dispersion.
Aniline black 1-1 7.50 parts by weight,
2.00 parts by weight of a polymeric dispersant,
(PB822: Ajinomoto Fine Techno)
Styrene-acrylic copolymer 3.00 parts by weight,
(JONCRYL680: manufactured by BASF)
Propylene glycol 1-monomethyl ether 2-acetate
37.50 parts by weight.

  The solvent viscosity thus obtained was 15.1 mPa · s. The storage stability was ○. From the above, the dispersibility is good. Further, the glossiness was 20%, the coating film had an L * value of 8.9, an a * value of 0.0, and a b * value of 0.0, and jet black was able to be expressed as intended.

Examples 1-17 to 1-20, Comparative Examples 1-16 to 1-20:
A solvent-based dispersion was obtained in the same manner as in Example 1-16 except that the type of aniline black was variously changed. As target colors, Example 1-17 is bluish black, Example 1-18 is bluish black, Example 1-19 is purple black, and Example 1-20 is purple black + fluorescence. It is.

  Various characteristics of the solvent-based dispersion obtained at this time are shown in Table 1-5.

  As described above, the solvent-based dispersion of the first invention is excellent in dispersibility, can express black with a hue according to the target, and has a bluish black, purple black, or jet black that has been difficult to express in the past. It is possible to express even in black, and it is clear that the blackness is excellent.

The following Examples 2-1 to 2-20 and Comparative Examples 2-1 to 2-20 are examples relating to the second invention.
<Manufacture of aniline black>
Example 2-1
30 g (0.32 mol) of aniline was added to 31.8 g (0.32 mol) of 35% hydrochloric acid and 2500 ml of water, and 10.4 g (0.032 mol) of sodium dodecylbenzenesulfonate was added to obtain an acidic aqueous solution. To this liquid, 3.0 g of carbon black (REGAL 330R, average particle size of primary particles: 0.025 μm, manufactured by Cabot) was added, and dispersion operation was performed using CLEARMIX (manufactured by M Technique). Then, while stirring and mixing at a liquid temperature of 60 ° C., an aqueous solution prepared by dissolving 4.6 g (0.036 mol) of ferric chloride in 70 ml of water and 78.0 g (0.69 mol) of 30% hydrogen peroxide over 2 hours. Thereafter, the mixture was stirred and mixed (ripened) for 1 hour at a liquid temperature of 60 ° C. to complete the reaction. After completion of the reaction, the reaction solution was filtered and washed with water. The resulting cake was redispersed with 1000 ml of water and stirred for 24 hours. Thereafter, the mixture was neutralized with 10% caustic soda to pH 8.0, and after the pH was stabilized, the mixture was filtered and washed with water. The paste was dried at 60 ° C. to obtain aniline black (aniline black 2-1).

  In order to quantify the amount of carbon black contained in aniline black 2-1, aniline black 2-1 and 1.00 g were weighed and 10 mL of N-methylpyrrolidone was added to dissolve aniline black. Thereafter, the mixture was filtered, washed with N-methylpyrrolidone and pure water, and dried to obtain 0.09 g of black particles. From the infrared absorption spectrum measurement of this black particle (Shimadzu FT-IR8300: manufactured by Shimadzu Corporation) and the determination of the carbon content, it was identified as carbon black. That is, it became clear that the aniline black 2-1 contained 10 parts by weight of carbon black with respect to 100 parts by weight of the aniline black basic skeleton. The average particle size of the primary particles of the carbon black was 0.025 μm.

The volume resistivity value of aniline black 2-1 was 2 × 10 ⁸ Ω · cm. When 10% by weight of carbon black was mixed with the non-chrome aniline black (volume resistivity: 6 × 10 ⁹ Ω · cm) shown in Comparative Example 1, the volume resistivity was measured to be 2 × 10 ³ Ω · cm. Even if it is a small amount, if carbon black is simply mixed, the volume resistivity value will drop dramatically. It is presumed that the volume resistivity value of aniline black 2-1 does not decrease because carbon black is coated with aniline black.

The aniline black 2-1 had a sulfur content of 1.5% by weight. The origin of the sulfur component is due to the added dodecylbenzenesulfonic acid, and this dodecylbenzenesulfonic acid is presumed to be part of aniline black as an acid group. When this reaction is carried out without adding dodecylbenzene, mixed particles in which carbon black and aniline black exist separately are obtained. The mixed particles have a volume resistivity value of 2 × 10 ³ Ω · cm, which matches the value of the mixture of aniline black and carbon black described above. As described above, a sulfur-containing compound such as dodecylbenzenesulfonic acid effectively acts on the composite of aniline black and carbon black.

Examples 2-2 to 2-5:
Aniline black according to the present invention was obtained in the same manner as in Example 2-1, except that the type and amount of carbon black and the reaction conditions were variously changed.

  Production conditions in these examples are shown in Table 2-1, and various characteristics of the obtained aniline black are shown in Table 2-2.

Comparative example 2-1 (follow-up experiment of Example 1 of JP 2012-153744 A):
Aniline black was obtained by the same operation as Comparative Example 1-1 (aniline black 2-6).

Comparative Example 2-2 (Additional Experiment of Example 1 of JP2012-153745):
Aniline black was obtained by the same operation as Comparative Example 1-2 (aniline black 2-7).

Comparative Example 2-3 (Follow-up experiment of Example 5 of JP 2001-261989 A):
Aniline black was obtained by the same operation as in Comparative Example 1-3 (aniline black 2-8).

Comparative Example 2-4 (Follow-up experiment of Example 1 of JP 2000-72974 A):
Aniline black was obtained by the same operation as Comparative Example 1-4 (aniline black 2-9).

Comparative Example 2-5 (follow-up experiment of Example 4 of JP-A-9-31353):
Aniline black was obtained by the same operation as Comparative Example 1-5 (aniline black 2-10).

  The production conditions of these comparative examples are shown in Table 2-1, and the characteristics of the obtained aniline black are shown in Table 2-2.

  As described above, it is clear that the aniline black particles according to the second invention are aniline black having excellent blackness, high volume resistivity, and high heat resistance.

<Manufacture of resin composition>
Example 2-6:
1.5 parts by weight of aniline black 2-1 particles obtained in Example 2-1 and 48.5 parts by weight of a styrene-acrylic copolymer JONCRYL680 (manufactured by BASF) were weighed and mixed to obtain a mixed powder. Add 0.5 parts by weight of calcium stearate to the obtained mixed powder, mix, set the clearance of the hot roll heated to 160 ° C. to 0.2 mm, and knead the mixed powder into the roll little by little. After the kneading was continued until the products were integrated, the resin composition was peeled from the roll. Next, the resin composition is sandwiched between surface-polished stainless steel plates, placed in a hot press heated to 180 ° C., and press molded at a pressure of 1 ton / cm ² to obtain a resin composition having a thickness of 1 mm. It was.
The resulting resin composition had a dispersibility of 5, an L * value of 7.5, and a blackness of ◎.
Furthermore, the color reduction rate due to heat was 12%, and the heat resistance was good.

Examples 2-7 to 2-10, Comparative Examples 2-6 to 2-10:
A resin composition was obtained in the same manner as in Example 2-6 except that the type of aniline black was changed.

  Various characteristics of the resin composition obtained at this time are shown in Table 2-3.

  As described above, it is obvious that the resin composition of the second invention is excellent in dispersibility, excellent in blackness, and high in heat resistance.

<Production of aqueous dispersion>
Example 2-11:
Using the aniline black 2-1 obtained in Example 2-1, the aqueous dispersion composition was blended at the following ratio, and mixed and dispersed for 60 minutes with a paint shaker together with 50 parts by weight of 1.5 mmφ glass beads to prepare an aqueous dispersion. .
Aniline black 2-1 7.50 parts by weight,
2.50 parts by weight of anionic surfactant
(Hitenol NF-08: manufactured by Daiichi Kogyo Seiyaku)
10.00 parts by weight of a styrene-acrylic copolymer,
(JONCRYL63J: manufactured by BASF)
0.50 part by weight of antifoaming agent,
(Envelope Gem AD-01: Nissin Chemical Industry)
31.00 parts by weight of water.
The viscosity of the obtained aqueous dispersion was 7.5 mPa · s. The storage stability was ○. From the above, the dispersibility is good. The glossiness was 19%, the L * value was 8.2, the a * value was −0.3, the b * value was −0.1, and the blackness was ◎. Furthermore, the color reduction rate due to heat was 14%, and the heat resistance was good.

Examples 2-12 to 2-15, Comparative Examples 2-11 to 2-15:
An aqueous dispersion was obtained in the same manner as in Example 2-11 except that the type of aniline black was variously changed.

  Various characteristics of the aqueous dispersion obtained at this time are shown in Table 2-4.

  As described above, it is clear that the aqueous dispersion of the second invention is excellent in dispersibility such as storage stability and gloss, and excellent in blackness and heat resistance.

<Production of solvent-based dispersion>
Example 2-16:
Using the aniline black 2-1 obtained in Example 1, the solvent-based dispersion composition was blended at the following ratio, and mixed and dispersed with a paint shaker for 60 minutes together with 50 parts by weight of 1.5 mmφ glass beads to prepare a solvent-based dispersion. .
Aniline black 2-1 7.50 parts by weight,
2.00 parts by weight of a polymeric dispersant,
(PB822: Ajinomoto Fine Techno)
Styrene-acrylic copolymer 3.00 parts by weight,
(JONCRYL680: manufactured by BASF)
Propylene glycol 1-monomethyl ether 2-acetate
37.50 parts by weight.
The solvent viscosity thus obtained was 8.0 mPa · s. The storage stability was ○. From the above, the dispersibility is good. Further, the glossiness was 20%, the coating film had an L * value of 7.5, an a * value of -0.2, a b * value of -0.1, and a blackness of ◎. Furthermore, the color reduction rate due to heat was 15%, and the heat resistance was good.

Examples 2-17 to 2-20, Comparative Examples 2-16 to 2-20:
A solvent-based dispersion was obtained in the same manner as in Example 2-16 except that the kind of aniline black was variously changed.

  Various characteristics of the solvent-based dispersion obtained at this time are shown in Table 2-5.

  As described above, it is clear that the solvent-based dispersion of the second invention is excellent in dispersibility such as storage stability and glossiness, and excellent in blackness and heat resistance.

The following Examples 3-1 to 3-28 and Comparative Examples 3-1 to 3-20 are examples relating to the third invention.
<Manufacture of aniline black>
Example 3-1:
30 parts by weight of aniline was added to 15.8 parts by weight of 71% sulfuric acid, 31.8 parts by weight of 35% hydrochloric acid and 2500 parts by weight of water, and 9.1 parts by weight of sodium dodecylbenzenesulfonate was added to prepare an acidic aqueous solution. To this solution, 3.0 parts by weight of phthalocyanine (CI Pigment Blue 15: 3) (HOSTAPERM BLUE B4G, average particle size of primary particles 0.1 μm, made by Clariant) was added, and Claremix (M Technique) was used. The dispersion operation was performed. Then, while stirring and mixing at a liquid temperature of 60 ° C., an aqueous solution in which 4.0 parts by weight of ferric chloride hexahydrate was dissolved in 70 parts by weight of water and 73.0 parts by weight of 35% hydrogen peroxide solution were taken over 2 hours. Then, the mixture was stirred and mixed (ripened) for 1 hour at a liquid temperature of 60 ° C. to complete the reaction. After completion of the reaction, the reaction solution was filtered and washed with water. The cake obtained was redispersed with 1000 parts by weight of water and stirred for 24 hours. Thereafter, the solution was neutralized to pH 8.0 with a 10% aqueous sodium hydroxide solution. After the pH was stabilized, the mixture was filtered, washed with water, and the paste was dried at 60 ° C. to obtain aniline black (aniline black 3-1).
The aniline black 3-9 of Comparative Example 3-1 prepared under the same conditions except that it does not contain phthalocyanine and sodium dodecylbenzenesulfonate was a * = 0.1, b * = 0.7 and blackish black It has a slight reddishness. In contrast, the aniline black 3-1 of this example was prepared by intentionally adjusting a * = 0.0 and b * = 0.0 by selecting and including the type and amount of pigment. It is able to express jet black as planned.

  In order to quantify the amount of phthalocyanine contained in aniline black 3-1, 1.00 part by weight of aniline black 3-1 was weighed and 10 parts by weight of N-methylpyrrolidone was added to dissolve aniline black. Thereafter, the mixture was filtered, washed with N-methylpyrrolidone and pure water, and dried to obtain 0.09 parts by weight of cyan particles. From the infrared absorption spectrum measurement of this cyan particle (Shimadzu FT-IR8300: manufactured by Shimadzu Corporation), it was identified to be the same as the phthalocyanine used as a raw material. That is, it became clear that aniline black 3-1 contained 10 parts by weight of phthalocyanine with respect to 100 parts by weight of aniline black basic skeleton. The average particle size of the primary particles of the phthalocyanine was 0.10 μm.

Further, the volume resistivity value of aniline black 3-1 was 2 × 10 ⁹ Ω · cm. The volume specific resistance value of carbon black, which has been conventionally used as a black pigment, is about 1 × 10 ⁻² Ω · cm, and it can be said that the volume specific resistance value of aniline black 3-1 is high.

  The aniline black 3-1 had a sulfur content of 1.5% by weight. While the sulfuric acid was contained under the reaction conditions of Comparative Example 3-1, the sulfur content of aniline black 3-9 was 0.1% by weight, so the origin of the sulfur component of aniline black 3-1 was added. It can be presumed to be due to dodecylbenzenesulfonic acid. Furthermore, considering that dodecylbenzenesulfonic acid remains even after neutralization of sodium hydroxide, this dodecylbenzenesulfonic acid is considered to be chemically strongly bound to aniline black. That is, it is presumed that it is part of aniline black as an acid group. When this reaction is carried out without adding dodecylbenzenesulfonic acid, mixed particles in which phthalocyanine and aniline black exist separately are obtained, which is clearly mottled. As described above, a sulfur-containing compound such as dodecylbenzenesulfonic acid effectively acts on the composite of aniline black and phthalocyanine.

Examples 3-2 to 3-8:
An aniline black according to the present invention was obtained in the same manner as in Example 3-1, except that the kind and amount of the pigment and the reaction conditions were variously changed.

  Production conditions in these examples are shown in Table 3-1, and various characteristics of the obtained aniline black are shown in Table 3-2.

Comparative example 3-1 (follow-up experiment of Example 1 of JP2012-153744A):
Aniline black was obtained by the same operation as Comparative Example 1-1 (aniline black 3-9).

Comparative Example 3-2 (Follow-up experiment of Example 1 of JP2012-153745A):
Aniline black was obtained in the same manner as in Comparative Example 1-2 (aniline black 3-10).

Comparative Example 3-3 (Additional Experiment of Example 5 of JP-A-2001-261989):
Aniline black was obtained by the same operation as in Comparative Example 1-3 (aniline black 3-11).

Comparative Example 3-4 (Follow-up experiment of Example 1 of JP 2000-72974 A):
Aniline black was obtained by the same operation as in Comparative Example 1-4 (aniline black 3-12).

Comparative Example 3-5 (Additional test of Example 4 of JP-A-9-31353):
Aniline black was obtained in the same manner as in Comparative Example 1-5 (Anlin Black 3-13).

  The production conditions of these comparative examples are shown in Table 3-1, and the characteristics of the obtained aniline black are shown in Table 3-2.

  As described above, it is clear that the aniline black according to the third invention is an aniline black that can express black having a hue according to various purposes, has excellent blackness, and has a high volume resistivity.

<Manufacture of resin composition>
Example 3-9:
1.5 parts by weight of aniline black 3-1 particles obtained in Example 3-1 and 48.5 parts by weight of styrene-acrylic copolymer JONCRYL680 (manufactured by BASF) were weighed and mixed to obtain a mixed powder. Add 0.5 parts by weight of calcium stearate to the obtained mixed powder, mix, set the clearance of the hot roll heated to 160 ° C. to 0.2 mm, and knead the mixed powder into the roll little by little. After the kneading was continued until the products were integrated, the resin composition was peeled from the roll. Next, the resin composition is sandwiched between surface-polished stainless steel plates, placed in a hot press heated to 180 ° C., and press molded at a pressure of 1 ton / cm ² to obtain a resin composition having a thickness of 1 mm. It was.
The resulting resin composition had a dispersibility of 5, an L * value of 7.5, and a blackness of ◎.

Examples 3-10 to 3-16, Comparative Examples 3-6 to 3-10:
A resin composition was obtained in the same manner as in Example 3-9 except that the type of aniline black was changed.

  Various characteristics of the resin composition obtained at this time are shown in Table 3-3.

  As described above, it is clear that the resin composition of the present invention has excellent dispersibility and excellent blackness.

<Production of aqueous dispersion>
Example 3-17
Using the aniline black 3-1 particles obtained in Example 3-1, the aqueous dispersion composition was blended at the following ratio, and mixed and dispersed in a paint shaker for 60 minutes together with 50 parts by weight of 1.5 mmφ glass beads to prepare an aqueous dispersion. did.
Aniline black 3-1 particles 7.50 parts by weight,
2.50 parts by weight of anionic surfactant
(Hitenol NF-08: manufactured by Daiichi Kogyo Seiyaku)
10.00 parts by weight of a styrene-acrylic copolymer,
(JONCRYL63J: manufactured by BASF)
0.50 part by weight of antifoaming agent,
(Envelope Gem AD-01: Nissin Chemical Industry)
31.00 parts by weight of water.
The viscosity of the obtained aqueous dispersion was 7.5 mPa · s. The storage stability was ○. From the above, the dispersibility is good. The glossiness was 19%, the L * value was 8.2, the a * value was 0.0, the b * value was 0.0, the blackness was 度, and jet black could be expressed.

Examples 3-18 to 3-24, Comparative Examples 3-11 to 3-15:
An aqueous dispersion was obtained in the same manner as in Example 3-17 except that the kind of aniline black was variously changed.

  Various characteristics of the aqueous dispersion obtained at this time are shown in Table 3-4.

  As described above, it is clear that the aqueous dispersion of the third invention can express black with a hue according to various purposes, has excellent dispersibility such as storage stability and glossiness, and excellent blackness.

<Production of solvent-based dispersion>
Example 3-25
Using the aniline black 3-1 particles obtained in Example 3-1, the solvent-based dispersion composition was blended at the following ratio, and mixed and dispersed in a paint shaker for 60 minutes together with 50 parts by weight of 1.5 mmφ glass beads. Was prepared.
Aniline black 3-1 particles 7.50 parts by weight,
2.00 parts by weight of a polymeric dispersant,
(PB822: Ajinomoto Fine Techno)
Styrene-acrylic copolymer 3.00 parts by weight,
(JONCRYL680: manufactured by BASF)
Propylene glycol 1-monomethyl ether 2-acetate
37.50 parts by weight.
The solvent viscosity thus obtained was 8.0 mPa · s. The storage stability was ○. From the above, the dispersibility is good. Further, the glossiness was 20%, and the coating film had an L * value of 7.5, an a * value of 0.0, and a b * value of 0.0, and jet black could be expressed. The blackness was ◎.

Examples 3-26 to 3-32 and Comparative Examples 3-16 to 3-20:
A solvent dispersion was obtained in the same manner as in Example 3-16 except that the type of aniline black was variously changed.

  Various characteristics of the solvent-based dispersion obtained at this time are shown in Table 3-5.

  As described above, it is clear that the solvent-based dispersion according to the third aspect of the invention can express black having a hue according to various purposes, is excellent in storage stability, dispersibility such as glossiness, and is excellent in blackness. .

The following Examples 4-1 to 4-15 and Comparative Examples 4-1 to 4-15 are examples relating to the fourth invention.
<Manufacture of aniline black>
Example 4-1
30 g (0.32 mol) of aniline was added to 31.8 g (0.32 mol) of 35% hydrochloric acid and 2500 ml of water, and 10.4 g (0.032 mol) of sodium dodecylbenzenesulfonate was added to obtain an acidic aqueous solution. Then, while stirring and mixing at a liquid temperature of 60 ° C., an aqueous solution prepared by dissolving 4.6 g (0.036 mol) of ferric chloride in 70 ml of water and 78.0 g (0.69 mol) of 30% hydrogen peroxide over 2 hours. Then, the mixture was stirred and mixed at a liquid temperature of 60 ° C. for 1 hour to complete the reaction. After completion of the reaction, the reaction solution was filtered and washed with water. The resulting cake was redispersed with 1000 ml of water and stirred for 24 hours. Thereafter, 1.5 g of laurylamine was dissolved in an appropriate amount of 1N aqueous hydrochloric acid solution, and the mixture was stirred for 1 hour. Thereafter, the solution was neutralized with a 10% aqueous sodium hydroxide solution to pH 8.0, and after the pH was stabilized, the mixture was filtered and washed with water. The paste was dried at 60 ° C. to obtain aniline black. (Aniline black 4-1)

  The degree of hydrophobicity of aniline black 4-1 was 10% by volume. The hydrophobicity of aniline black in the comparative example is all 0% by volume, which indicates that the surface treatment functions effectively for hydrophobicity.

  In order to quantify the amount of the treating agent contained in aniline black 4-1, 1.0 g of aniline black 4-1 was weighed, 10 mL of 1N hydrochloric acid was added, and the mixture was stirred for 1 hour. Thereafter, the mixture was filtered, and 1N sodium hydroxide was added to the filtrate, thereby causing precipitation. This precipitate was filtered and dried to obtain 0.05 g of a solid content. From the infrared absorption spectrum measurement of this solid (Shimadzu FT-IR8300: manufactured by Shimadzu Corporation) and the quantification of the carbon content, it was identified as laurylamine. That is, it was revealed that aniline black 4-1 has 5.0% by weight of laurylamine on the surface.

  The aniline black 4-1 had a sulfur content of 1.6% by weight. The origin of the sulfur component is due to the added dodecylbenzenesulfonic acid, and this dodecylbenzenesulfonic acid is presumed to be part of aniline black as an acid group. When this reaction is carried out without adding dodecylbenzenesulfonic acid, aniline black 4-1 seemingly unchanged particles are obtained, but the sulfur content is 0.1% by weight and the degree of hydrophobicity is 1.5%. The volume was as low as%, and the dispersibility in resins and organic solvents was low. As described above, a sulfur-containing compound such as dodecylbenzenesulfonic acid effectively acts on the surface treatment of aniline black.

Examples 4-2 to 4-5:
Aniline black according to the present invention was obtained in the same manner as in Example 4-1, except that the type and amount of the treating agent and the reaction conditions were variously changed.

  Production conditions in these examples are shown in Table 4-1, and various characteristics of the obtained aniline black are shown in Table 4-2.

Comparative Example 4-1 (Follow-up experiment of Example 1 of JP2012-153744A):
Aniline black was obtained by the same operation as Comparative Example 1-1 (aniline black 4-6).

Comparative example 4-2 (follow-up experiment of Example 1 of JP2012-153745A):
Aniline black was obtained by the same operation as Comparative Example 1-2 (aniline black 4-7).

Comparative Example 4-3 (follow-up experiment of Example 5 of JP-A-2001-261989):
Aniline black was obtained by the same operation as Comparative Example 1-3 (aniline black 4-8).

Comparative Example 4-4 (Follow-up experiment of Example 1 of JP 2000-72974 A):
Aniline black was obtained by the same operation as Comparative Example 1-4 (aniline black 4-9).

Comparative Example 4-5 (follow-up experiment of Example 4 of JP-A-9-31353):
Aniline black was obtained in the same manner as in Comparative Example 1-5 (Anlin Black 4-10).

  The production conditions of these comparative examples are shown in Table 4-1, and the characteristics of the obtained aniline black are shown in Table 4-2.

  In all of the aniline blacks of the examples, the dispersibility in the resin was “◯” and the dispersibility in the organic solvent was also “◯”. On the other hand, all the aniline blacks of the comparative examples had “x” dispersibility in the resin and “x” in the organic solvent. As described above, the aniline black according to the fourth invention is clearly aniline black having excellent dispersibility in hydrophobic media such as resins and organic solvents, excellent blackness, and high volume resistivity. is there.

<Manufacture of resin composition>
Example 4-6:
24.0 g of aniline black 4-1 particles obtained in Example 4-1 and 36.0 g of polyester resin DIACRON ER561 (manufactured by Mitsubishi Rayon) were weighed and ground in a sample mill. This was kneaded at 120 ° C. and 25 rpm for 10 minutes in a Laboplast mill (manufactured by Toyo Seiki), taken out, and then cooled to room temperature. Then, it grind | pulverized at 12000 rpm using the ultra centrifugal crusher ZM200 (made by Lecce), and obtained the resin composition.
The obtained resin composition had a dispersibility of 5, an L * value of 8.0, and a blackness of ◎.

Examples 4-7 to 4-10, comparative examples 4-6 to 4-10:
A resin composition was obtained in the same manner as in Example 4-6 except that the type of aniline black was changed.

  Various characteristics of the resin composition obtained at this time are shown in Table 4-3.

  As described above, it is obvious that the resin composition of the fourth invention is excellent in dispersibility and excellent in blackness.

<Production of solvent-based dispersion>
Example 4-11:
Using the aniline black 4-1 obtained in Example 1, the solvent-based dispersion composition was blended in the following proportions and mixed and dispersed with a paint shaker for 60 minutes together with 50 g of 1.5 mmφ glass beads to prepare a solvent-based dispersion.
Aniline black 7.50 parts by weight,
2.00 parts by weight of a polymeric dispersant,
(PB822: Ajinomoto Fine Techno)
Styrene-acrylic copolymer 3.00 parts by weight,
(JONCRYL611: manufactured by BASF)
Propylene glycol 1-monomethyl ether 2-acetate
37.50 parts by weight.
The solvent viscosity thus obtained was 8.2 mPa · s. The storage stability was ○. From the above, the dispersibility is good. Further, the glossiness was 21%, and the coating film had an L * value of 8.0, an a * value of −0.5, and a b * value of −0.4.

Examples 4-12 to 4-15, Comparative Examples 4-11 to 15:
A solvent-based dispersion was obtained in the same manner as in Example 11 except that the type of aniline black was variously changed.

  Various characteristics of the solvent-based dispersion obtained at this time are shown in Table 4-4.

  As described above, it is clear that the solvent-based dispersion of the fourth invention is excellent in dispersibility such as storage stability and glossiness and excellent in blackness.

  The aniline black according to the present invention does not contain harmful substances such as chromium, and can be freely expressed in black according to the purpose and purpose. However, since it has a high blackness and a high volume resistivity, it can be used in the field of electronic equipment such as a non-magnetic developer for electrophotography, a charge control agent for toner, and a colorant for black matrix, It is suitable for various uses such as cosmetics such as eyebrow pencil, eyebrow powder, eyebrow mascara, eye shadow, compact powder, foundation, lipstick, nail enamel, paint, printing ink, and ink jet ink. In addition, the resin composition, the aqueous dispersion, and the solvent dispersion containing the aniline black can be freely expressed in black according to the purpose and purpose. , Purple black, jet black, can be expressed, high blackness, excellent dispersibility, high volume resistivity, high heat resistance, so non-magnetic developer for electrophotography, for toner Fields such as electronic devices such as charge control agents and colorants for black matrix, eyebrow pencils, eyebrow powders, eyebrow mascaras, eye shadows, compact powders, foundations, lipsticks, nail enamels and other cosmetics, paints and printing inks It is suitable for various uses such as inkjet ink.

Claims (9)

The content of the chromatic pigment having an average primary particle size of 0.01 to 0.2 μm is 1 to 60 parts by weight with respect to 100 parts by weight of the aniline black basic skeleton, and the volume resistivity is 10 ⁶ to 10. Aniline black particles of ¹⁰ Ω · cm.   The aniline black particles according to claim 1, wherein the average particle size of the primary particles is in the range of 0.05 to 1.0 µm.   The aniline black particles according to claim 1 or 2, wherein the powder has a pH of 4.0 to 9.0.   The aniline black particles according to claim 1, wherein the dispersed chromatic pigment is coated with a polymer aniline black.   The aniline black particles according to claim 1 or 4, wherein the dispersed chromatic pigment is encapsulated with a polymer aniline black.   A resin composition comprising the aniline black particles according to claim 1.   An aqueous dispersion comprising the aniline black particles according to any one of claims 1 to 5.   A solvent-based dispersion comprising the aniline black particles according to claim 1.   The method for producing aniline black particles according to any one of claims 1 to 5, wherein aniline, aniline acid salt, aromatic amine, or aromatic amine acid salt, or a mixture thereof is used. After dispersing or dissolving in water and adjusting to a predetermined pH with an acid, the first step of adding a sulfur-containing compound to make an acidic aqueous solution, adding a chromatic pigment to the acidic aqueous solution, Performing a second step of making a dispersion, a third step of adding a metal or a metal salt that can be a decomposition catalyst of the oxidant while stirring the dispersion, dropping an oxidant while stirring, oxidative polymerization, A fourth step of obtaining crude aniline black, a method of producing aniline black particles, comprising a fifth step of neutralizing the obtained crude aniline black with an alkaline agent, filtering, washing with water, drying and then pulverizing.