JP2019112624A - Aniline black particles, and resin composition, aqueous dispersion body and non-aqueous dispersion body using the aniline black particles - Google Patents

Abstract

To provide aniline black particles providing aniline black which has a small content of chromium, suppresses bleeding, is excellent in blackness and has high volume resistivity value, a resin composition which is colored by the aniline black, suppresses bleeding, is excellent in blackness and is excellent in dispersibility, and an aqueous dispersion body and a non-aqueous dispersion body which are colored by the aniline black, are excellent in blackness, and are excellent in dispersibility.SOLUTION: There are provided aniline black particles that have an average particle diameter of primary particles of 0.05-1.0 μm and have bleeding resistance, in which contents of an aniline tetramer and an aniline trimer are 1-50 ppm respectively; and a resin composition, an aqueous dispersion body or a non-aqueous dispersion body containing the aniline black particles.SELECTED DRAWING: None

Description

  The present invention provides an aniline black particle in which the bleeding of the phenomenon in which a coloring component is eluted in a medium such as a resin is suppressed.

  The present invention also provides a resin composition, an aqueous dispersion, and a non-aqueous dispersion colored by the aniline black particles and in which bleeding is suppressed.

  Aniline black has been used as a black pigment since it emits characteristic black color and is hardly soluble in dispersion media such as aqueous and non-aqueous systems. Aniline black is a kind of polyaniline obtained by oxidative polymerization of an aromatic amine such as aniline, and it is said that the basic skeleton of the N-phenyl dibenzo paraazine polymer shown in Chemical formula 1 is composed as a main component . In addition, linear polyaniline such as emeraldine polymerized at the p-position of aniline is green to purple and is mainly used as an organic conductor.

In Chemical Formula 1, n represents the degree of polymerization, and X represents a hydroxyl group or an acid group such as chlorine. The acid group of Chemical Formula 1 is to be the N ⁺ counter anion of aniline black and is composed of various organic acids and inorganic acids. Representative organic acids are formic acid, acetic acid and the like, and representative inorganic acids are hydrochloric acid, nitric acid, sulfuric acid and the like.

  Conventionally, aniline black has a bluish black color that can not be expressed by carbon black, and is used for various applications such as paints, printing inks, paints, poster colors, plastics, thermal transfer inks, etc., taking advantage of its features (Patent Document 1) ~ 3). Heretofore, as an oxidizing agent used for producing aniline black, a method using dichromate is considered to be optimum. Here, since dichromate is an extremely strong oxidizing agent, sufficient oxidative condensation is generated from starting materials such as aniline. Furthermore, since a chromium oxide derived from dichromic acid is coordinated to the aniline black main chain skeleton, it forms a strong intramolecular or intermolecular network and exhibits high robustness.

  However, chromium contained in bichromate can be a very harmful pollutant to the human body. (Currently, chromium oxide contained in aniline black synthesized with dichromic acid coordinates to the pigment, and harmful hexavalent chromium is not included and safety has been recognized.) Therefore, these chromiums are manufactured at the time of production. There is a need for aniline black which is not used and has no risk of being mixed. Safety has been achieved from the viewpoint of manufacturing and quality, and eye cosmetics such as eyebrow pencils, eyebrow powder, eyebrow powder, eyebrow powder, eye shadow, compact powder, foundation, lipstick, nail enamel etc. There is also the possibility of development for applications that directly touch the skin.

  In recent years, as a method for producing chromium-free aniline black, aniline is made into an aqueous solution of acid and oxidized with a persulfate salt (patent document 4) or hydrogen peroxide and its decomposition catalyst There is known a production method (Patent Documents 5 and 6) in which aniline is oxidized using an available metal or metal salt and an OH radical generated as an oxidizing agent.

  In addition, as a π-conjugated polymer with high degree of blackness and highly controlled particle size, oxidation polymerization of starting materials such as aniline with an oxidizing agent in the presence of a water-soluble polymer compound, a transition metal compound, and a protonic acid The black pigment (patent document 7) obtained by this is known.

  Furthermore, by simultaneously dropping the catalyst and the oxidizing agent in the oxidation polymerization process, the decomposition rate of the oxidizing agent is arbitrarily controlled to reduce the axial ratio of the primary particles aniline black (Patent Document 8), aniline in the oxidation polymerization process Aniline black (Patent Document 9) containing a sulfone group is known as a result of the copolymerization reaction of the compound and a sulfonyl compound.

  On the other hand, carbon blacks, which are mostly inexpensive, have excellent blackness, and have excellent heat resistance, are generally used as black colorants such as nonmagnetic developers for electrophotography and black matrices for liquid crystals. In recent years, it has been required to improve the image quality of electrophotographic images and to increase the light blocking ratio of the black matrix, and studies are being conducted to increase the density by, for example, increasing the amount of the colorant added. However, carbon black is difficult to disperse in a binder resin, and its volume resistivity is low. Therefore, when carbon black is used as a nonmagnetic black phenomenon agent, there remains a problem that the chargeability of the developer is inhibited (the charge retention ability is lowered). On the other hand, when carbon black is used as a black matrix, it is difficult to impart dispersion stability of the carbon black in the dispersion, so that the fluidity becomes worse, and the problem that the volume resistance value as a resist thin film also decreases remains.

  In general, aniline black is known to have a higher volume specific resistance value than inorganic black pigments such as carbon black, and application studies of aniline black are being conducted in order to overcome the problems described above. As a black coloring agent of a nonmagnetic developer for electrophotography, application as a developer excellent in charge retention performance with little leakage of charge even at high temperature and high humidity is examined (Patent Documents 10 to 12).

  In the conventional chromium-rich aniline black, chromium oxide ions are coordinated as acid groups. Therefore, even low molecular weight aniline polymers (aniline tetramer and aniline trimer) of the dye component contained in aniline black are insolubilized by coordination of chromium oxide ions, and elution to the medium is small, ie, It may function as bleed-inhibited aniline black. On the other hand, in the case of aniline black having a low content of chromium oxide ions, the low molecular weight aniline polymer contained in the aniline black may be partially eluted in a medium such as a resin or a non-aqueous solvent. That is, a defect called bleed may often occur due to the presence of aniline tetramer or aniline trimer. There is also an attempt to mix a montmorillonite-based clay mineral with aniline black so that a bleeding component is adsorbed to the montmorillonite-based clay mineral (Patent Document 2).

Japanese Patent Application Laid-Open No. 11-140349 Unexamined-Japanese-Patent No. 10-212428 Japanese Patent Application Publication No. 2002-371219 Unexamined-Japanese-Patent No. 2001-261989 Unexamined-Japanese-Patent No. 10-245497 gazette Unexamined-Japanese-Patent No. 2000-72974 JP-A-9-31353 JP 2012-153744 A JP 2012-153745 A Unexamined-Japanese-Patent No. 2010-19970 Japanese Patent Application Laid-Open No. 2005-195693 Unexamined-Japanese-Patent No. 2001-106938

  As described above, aniline black, which has a low chromium content, excellent blackness, reduced bleeding, and high volume resistivity, is used for electrophotography in addition to applications such as conventional paints and printing inks. It has been developed for applications such as non-magnetic developers for use, black matrices for liquid crystals, and cosmetics. Therefore, aniline black in which bleeding is suppressed is desired while having the above-mentioned characteristics such as low chromium content, high blackness, and high volume resistivity. However, aniline black satisfying such properties has not been obtained yet, probably because of the high quality required.

  That is, in the aniline black described in the above-mentioned patent document 1, an additive is required for bleeding suppression, and it becomes impossible to show sufficient blackness. Moreover, in the aniline black of the above-mentioned patent documents 1-12, there is no description regarding the content of the low molecular weight aniline polymer for bleed suppression, and it can not be said that bleed suppression was able to be performed by aniline black alone.

  Then, this invention makes it a technical subject to provide low content of chromium and low content of low molecular weight aniline polymer aniline black. In addition, it is intended to provide a resin composition which is colored by the aniline black, suppresses bleeding, is excellent in blackness, and is excellent in dispersibility. In addition, it is an object of the present invention to provide aqueous and non-aqueous dispersions colored by the aniline black, excellent in blackness, and excellent in dispersibility.

  The above technical problems can be achieved by the present invention as follows.

  That is, according to the present invention, in the bleed-resistant aniline black particles in which the average particle diameter of the primary particles is 0.05 to 1.0 μm, the content of the aniline tetramer and the aniline trimer is 1 to 10, respectively. It is an aniline black particle characterized by being 50 ppm. (Invention 1)

  The present invention is also the aniline black particle according to the present invention 1, wherein the mass-to-charge ratio m / z value is 379 to 381 in the measurement of the aniline tetramer by liquid chromatography mass spectrometry (LC / MS). . (Invention 2)

  Further, the present invention is the liquid chromatograph mass spectrometry (LC / MS) according to the present invention 1 or 2, wherein the mass-to-charge ratio m / z value is 290 to 292 in the measurement of the aniline trimer by LC / MS. Aniline black particles. (Invention 3).

  Moreover, this invention is aniline black particle | grains in any one of this invention 1-3 whose sulfur content is 0.01 to 0.19 weight%. (Invention 4)

  Moreover, this invention is aniline black particle | grains in any one of this invention 1-4 whose powder pH is 2.0-9.0. (Invention 5)

Moreover, this invention is aniline black particle | grains in any one of this invention 1-5 whose volume specific resistance value is 10 < ⁶ > -10 < ¹⁰ > ohm * cm. (Invention 6)

The present invention is also a resin composition comprising the aniline black particles according to any of the present inventions 1 to 6. (Invention 7)

The present invention is also an aqueous dispersion comprising the aniline black particles according to any of the present inventions 1 to 6. (Invention 8)

The present invention is also a non-aqueous dispersion comprising the aniline black particles according to any of the present inventions 1 to 6. (Invention 9)

  The aniline black according to the present invention is suitable as an aniline black having a very low chromium content, suppressed bleeding, excellent in blackness, and high in volume resistivity.

  The resin composition colored with aniline black according to the present invention is suitable as a resin composition which has suppressed bleeding, is excellent in blackness, and is excellent in dispersibility.

  The aqueous and non-aqueous dispersions colored with aniline black according to the present invention are suitable as aqueous and non-aqueous dispersions excellent in blackness and excellent in dispersibility.

It is a spectrum by the Fourier-transform infrared spectrophotometer (FT-IR) of aniline black obtained in Example 1 of this invention. It is a chromatograph chart of UV-vis (wavelength: 258 nm) detection by liquid chromatography mass spectrometry of aniline black obtained in Example 1 of the present invention. It is a chromatograph chart of UV-vis (wavelength: 258 nm) detection by liquid chromatography mass spectrometry of aniline black obtained by comparative example 1 of the present invention.

  The configuration of the present invention will be described in more detail as follows.

  First, the aniline black particles according to the present invention will be described. In addition, aniline black particles may be described simply as aniline black throughout this specification.

  The aniline black according to the present invention has a chromium content of 1000 ppm or less. When the content of chromium exceeds 1000 ppm, it is necessary to contain chromium in aniline black using a chromium-containing compound as a raw material in the production of aniline black. The use of chromium-containing compounds is not a safe process, and high chromium content aniline black is not a safe product. Preferably, the content of chromium is 900 ppm or less, more preferably 800 ppm or less. Ideally it is preferred not to contain chromium. The chromium contained in aniline black also includes chromium which is inevitably mixed, such as an elution component of piping at the time of aniline black production.

  The average particle size of primary particles of aniline black according to the present invention is in the range of 0.05 μm to 1.0 μm. When the average particle size of primary particles of aniline black is less than 0.05 μm, the transparency is increased and the coloring power is reduced, so the obtained blackness is inferior. In addition, when the average particle size of the primary particles exceeds 1.0 μm, it is difficult to use as a black pigment because the coloring power is low. The preferred primary particles have an average particle size of 0.10 to 0.85 μm.

Aniline black according to the present invention has bleed resistance. Specifically, after preparation of the aniline black-containing resin composition according to the present invention, it is preferable that the bleed color difference ΔE ^* is 3.0 or less in a bleed test with vinyl chloride described later. Bleeding is a phenomenon in which a coloring component is eluted in a medium such as a resin, and causes problems such as bleeding of a coloring matter and color transfer. Therefore, the suppression of bleeding can mean the case where ΔE ^* is 3.0 or less in the bleeding test of the resin composition. When ΔE ^* is more than 3.0, even if only a slight amount of dissolution of the coloring component into the medium such as a resin, the coloring due to bleeding can be visually identified. More preferably, ΔE ^* is 1.5 or less, and more preferably, ΔE ^* is 1.0 or less. The detection limit ΔE ^* is 0.01.

  The cause of bleeding of aniline black according to the present invention is expected to be a low molecular weight aniline polymer of a dye component contained in a small amount in aniline black. In particular, since the basic structure of the N-phenyldibenzoparaazine in Formula 1 exhibits chromogenicity, it is expected that the aniline trimer having at least the basic structure or more is the cause of bleeding. As a result of intensive studies by the present inventors, when aniline black in which bleeding occurred was extracted with a solvent, dye components of aniline tetramer and aniline trimer were extracted. It was discovered that there was a correlation between the amount of aniline tetramer extracted and the amount of aniline trimer and the frequency of bleed, and aniline black with reduced amounts of these was developed, leading to the present invention. The aniline pentamer or more does not extract into the solvent or the resin, so the aniline pentamer or more behaves as a pigment and is considered to have no correlation with bleeding.

The aniline tetramer contained in aniline black according to the present invention is presumed to be aminophenylamino-N-phenyldibenzoparaazine (molecular weight M = 363). Mass-to-charge ratio m / z value by positive ion detection mass spectrum by electrospray method in LC / MS is a state where addition ion is bound to molecular weight detected by conditions, hydrogen ion addition [M + H] ⁺ = 364, ammonium ion addition [M + NH ₄ ] ⁺ = 380, sodium ion addition [M + Na] ⁺ = 386, potassium ion addition [M + K] ⁺ = 402, or a mixture of two or more. Moreover, even if the error on an apparatus is considered, the mass to charge ratio m / z detected as an aniline tetramer is 363 to 403.

The aniline trimer contained in aniline black according to the present invention is presumed to be amino-N-phenyldibenzoparaazine (molecular weight M = 272). Similar to the identification of the aniline tetramer, the mass-to-charge ratio m / z value is the state in which the addition ion is bound to the molecular weight detected by the conditions, hydrogen ion addition [M + H] ⁺ = 273, ammonium ion addition [M + NH ₄ ] ⁺ = 289, sodium ion addition [M + Na] ⁺ = 295, potassium ion addition [M + K] ⁺ = 311, or a plurality of mixtures are detected. Moreover, even if the error on an apparatus is considered, the mass-to-charge ratio m / z value detected as an aniline trimer is 272-312.

  Aniline black according to the present invention contains 1 to 50 ppm of aniline tetramer and aniline trimer, respectively. As mentioned above, aniline tetramer and aniline trimer can be main causes of bleeding. These low molecular weight aniline polymers are yellow to red dye components, and when each exceeds 50 ppm, the phenomenon that the dye components are eluted in a dispersion medium such as a resin is observed as bleeding. It was difficult to produce aniline tetramer and aniline black having less than 1 ppm of aniline trimer. Preferably, the contents of aniline tetramer and aniline trimer are each in the range of 2 to 45 ppm. More preferably, it is in the range of 3 to 40 ppm, respectively.

  The mass-to-charge ratio m / z value of the aniline tetramer of aniline black according to the present invention is preferably 379 to 381 in liquid chromatography mass spectrometry (LC / MS). Under the synthesis conditions of aniline black according to the present invention, although various values of the mass to charge ratio m / z value of the aniline tetramer can be taken, the mass to charge ratio m / z value detectable as a coloring component is 379 to 381. there were. Preferably, it is 379.2 to 380.8.

  The mass-to-charge ratio m / z value of the aniline trimer of aniline black according to the present invention is preferably 290 to 292 by liquid chromatography-mass spectrometry (LC / MS). Under the synthesis conditions of aniline black according to the present invention, although various values of the mass to charge ratio m / z value of the aniline trimer can be taken, the mass to charge ratio m / z value detectable as a coloring component is 290 to 292 there were. Preferably, it is 290.2 to 291.8.

  The sulfur content of aniline black according to the present invention is preferably 0.01 to 0.19% by weight. The sulfur-containing origin of the obtained aniline black is an acid such as sulfuric acid used to dissolve aniline in water, a persulfate such as ammonium persulfate used as an oxidizing agent, or iron sulfate used as an oxidation catalyst, etc. It is due to the addition of sulfur-containing compounds frequently used in black synthesis. It is inferred that an aromatic amine such as aniline or a part of a salt of an aromatic amine is linked as an acid group, embedded in the structure of aniline black, and remaining. It is also possible to use an industrial water containing a slight amount of sulfur component as water, or to leave a sulfur component in aniline black by contamination or the like. Although the residual sulfur itself is not directly related to bleeding, by reducing these sulfur components as much as possible, it is possible to reduce by-products that can be the main cause of bleeding such as aniline tetramer and aniline trimer I tended to That is, when the sulfur content of aniline black exceeds 0.19% by weight, bleeding tends to occur. On the other hand, the content of less than 0.01% by weight was below the detection limit. The more preferable sulfur content is 0.02 to 0.18% by weight. An even more preferable sulfur content is 0.03 to 0.16% by weight.

  The powder pH of aniline black according to the present invention is measured by the evaluation method described later, and the range of 2.0 to 9.0 is preferable. When the powder pH is less than 2.0, aniline tetramer and aniline trimer ionize in the medium as a cationic salt and liberate more to facilitate bleeding. On the other hand, when the powder pH exceeds 9.0, the aniline tetramer and the aniline trimer ionize in the medium as an anion salt and are more liberated to easily promote bleeding. More preferable powder pH is 2.5-7.0. Furthermore, more preferable pH is 3.0-6.0.

The volume resistivity of the aniline black according to the present invention is preferably 10 ⁶ to 10 ¹⁰ Ω · cm. A more preferable volume specific resistance value is 10 ⁶ to 8 × 10 ⁹ Ω · cm. If it is less than 10 ⁵ Ω · cm, differentiation from highly conductive carbon black is difficult, and it is difficult to manufacture one exceeding 10 ¹⁰ Ω · cm. An even more preferable volume resistivity is 5 × 10 ^{6 to} 5 × 10 ⁹ Ω · cm.

The hue of aniline black according to the present invention refers to L ^* , a ^* , b ^* values among the coloration indexes measured by the evaluation method described later. The degree of blackness uses lightness L ^* as an index, and being excellent in blackness refers to the case where L ^* is 15.0 or less among the measured values. When L ^* exceeds 15.0, it is difficult to say that the blackness is excellent. More preferable L ^* value is 12.0 or less. Further, the a ^* value and the b ^* value vary depending on the purpose, and are controlled by the reaction specification of aniline black, specifically, the particle size, the shape, and the kind and amount of the contained acid groups. When expressed as normal black, the a ^* and b ^* values are preferably -20 to 20, respectively, but should be controlled according to the purpose, and are not limited to these values.

The aniline black according to the present invention may contain various acid groups. The acid group refers to a moiety obtained by removing one or more hydrogen atoms from molecules of various inorganic acids and organic acids, and refers to one that acts as a counter ion of N ⁺ . Organic acids are formic acid, acetic acid, benzoic acid, citric acid, oxalic acid, adipic acid, phenol and the like, and inorganic acids are hydroxyl group, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, boric acid, hydrofluoric acid, peroxy acid Chloric acid and the like can be mentioned. However, from the viewpoint of the aniline black residual sulfur component, it is preferable not to use sulfuric acid as much as possible.

  Aniline black according to the present invention has an aromatic compound other than an aromatic amine, a heterocyclic compound, a fragment thereof, or two or more of them in the structure in order to improve properties such as dispersibility and color development. They may be combined or copolymerized. As the aromatic compounds, aromatic compounds such as benzene, toluene, xylene and naphthalene; aromatic acids such as phenol, benzenesulfonic acid, p-toluenesulfonic acid and benzoic acid; and heterocyclic compounds such as furan, thiophene and quinone It can be mentioned. However, it is preferable not to use benzenesulfonic acid, p-toluenesulfonic acid and thiophene as much as possible from the viewpoint of aniline black residual sulfur component.

  The aniline black according to the present invention may be further subjected to surface treatment in order to improve the dispersibility, color development and the like. The surface treatment material is not particularly limited, but surfactants such as alkyl alcohol, fatty acid and alkyl amine, polymers such as acrylic resin, polyester resin and urethane resin, silane coupling agents, organic silicon such as silane Organic surface treatment agents such as compounds, inorganic surface treatment agents such as inorganic particles such as silica, alumina and titanium oxide, organic inorganic surface treatment agents such as rosin-calcium, rosin-magnesium, etc. or two of them What was processed by the thing combined above is also good.

  Next, the process for producing aniline black in the present invention will be described. The present invention is not limited to this.

  In the method for producing aniline black in the present invention, aniline is preferably the main component as an aromatic amine as a starting material. That is, aromatic amines such as methyl aniline, ethyl aniline, toluidine and aminonaphthalene, and nitrogen-containing heterocyclic compounds such as pyrrole and pyridine. Alternatively, two or more of them may be combined or copolymerized.

  In the method for producing aniline black according to the present invention, either aniline, an acid salt of aniline, an aromatic amine or an acid salt of an aromatic amine, or a mixture thereof is dispersed or dissolved in water and then dissolved in an acid. After adjusting to a predetermined pH, an acidic aqueous solution is obtained. A catalyst is added to this acidic aqueous solution, an oxidizing agent is added dropwise while stirring to oxidize and polymerize, neutralized with an alkali agent, filtered, washed with water and dried, and then crushed and aniline according to the present invention You can get black.

In the production step of aniline black in the present invention, the amounts of by-produced aniline tetramer and aniline trimer are each suppressed in the range of 1 to 50 ppm, and have bleed resistance. For example, the bleed color difference ΔE ^* is preferably 3.0 or less. This leads to aniline black in the present invention. In order to adjust the amounts of by-produced aniline tetramer and aniline trimer within the above-mentioned range and to have bleed resistance, it is preferable to carry out the reaction so as to satisfy the following conditions. In particular, since there is a close relationship between the content of sulfur and the amounts of aniline tetramer and aniline trimer, the raw materials should be selected and reacted so as to control the sulfur content within a predetermined range. Is preferred.

  Examples of the acid 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, alone or as a mixture. You may use it. The acid is preferably 0.5 to 3.0 equivalents relative to aniline. If it is less than 0.5 equivalent, aniline can not be converted to an acid salt, and the reaction is difficult to proceed. If it exceeds 3.0 equivalents, bleeding may occur. More preferably, it is 1.0 equivalent to 2.0 equivalents. In terms of parts by weight, for example, 17 to 117 parts by weight is preferable as 35% hydrochloric acid with respect to 30 parts by weight of aniline. More preferably, it is 33 to 67 parts by weight. However, from the viewpoint of the aniline black residual sulfur component, it is preferable not to use sulfuric acid as much as possible.

  Examples of the oxidizing agent include ammonium persulfate, sodium persulfate, persulfates such as potassium persulfate, hydrogen peroxide, oxygen and the like, which may be used alone or as a mixture. The amount of the oxidizing agent used is preferably 0.1 to 10 equivalents relative to aniline. If the amount is less than 0.1 equivalent, the oxidizing agent is insufficient and the reaction to aniline black is difficult. If it exceeds 10 equivalents, bleeding may occur due to the low molecular weight aniline polymer obtained. More preferably, it is 0.5-5 equivalents. When converted to parts by weight, for example, 12 to 1200 parts by weight as 9% hydrogen peroxide water is preferable to 30 parts by weight of aniline. More preferably, it is 60 to 600 parts by weight. Moreover, it is preferable to add an oxidizing agent gradually with respect to the reaction solution. The addition of the oxidizing agent for 10 minutes to 10 hours, preferably 5 hours to 10 hours, makes it possible to control the oxidation polymerization rate of the starting aromatic amine. Due to the control, it is also possible to control the particle size of the resulting aniline black particles. However, from the viewpoint of the aniline black residual sulfur component, it is preferable not to use the persulfate as much as possible.

  As a metal or metal salt which can be a catalyst, iron, ferric chloride, ferric nitrate, ferric sulfate, ferrous chloride, ferrous nitrate, ferrous sulfate, iron-EDTA chelate, chloride Platinum, gold chloride or silver nitrate may, for example, be used alone or as a mixture. The amount of the catalyst used is usually preferably 0.1 to 10 mol% with respect to the oxidizing agent. If it is less than 0.1 mol%, the reaction is difficult to progress. If it exceeds 10% by mole, bleeding may occur. More preferably, it is 0.2-5 mol%. In terms of parts by weight, for example, 0.2 to 21 parts by weight as ferric chloride hexahydrate is preferable to 300 parts by weight of 9% hydrogen peroxide water. More preferably, it is 0.4 to 11 parts by weight. Moreover, it is preferable not to contain chromium. However, from the viewpoint of the aniline black residual sulfur component, it is preferable not to use ferric sulfate and ferrous sulfate as much as possible.

  In order to advance the reaction to aniline black in a more preferable direction, a surfactant, a water-soluble polymer or the like may be added to the reaction solution. By adding these, the oxidative polymerization reaction of aniline turns from solution polymerization to emulsion polymerization, which makes it difficult to form a low molecular weight aniline polymer. As surfactant, for example, nonionic surfactant such as polyoxyethylene alkyl ether, anionic surfactant such as polyoxyethylene alkyl ether carboxylate, as water soluble polymer, water soluble acrylic, polyethylene glycol, polyvinyl pyrrolidone And polyvinyl alcohol. The addition of these to carry out the oxidative polymerization of aniline suppresses the bleeding component of the resulting aniline black, though the reason is not clear. The addition amount is preferably 1 to 10% by weight with respect to aniline. More preferably, it is 2 to 8% by weight.

  The reaction temperature is preferably 10 to 35 ° C. More preferably, 10 to 30 ° C. is preferable. When the reaction temperature exceeds 35 ° C., a large amount of aniline tetramer and aniline trimer are generated, and there is a concern that bleeding may occur due to the resulting aniline. If it is less than 10 ° C., there is a concern that the oxidative polymerization reaction will not proceed. The reaction solution is preferably stirred usually for 10 minutes to 10 hours, preferably for 20 minutes to 7 hours, as the reaction initiation time immediately after the addition of the oxidizing agent.

  Since aniline black immediately after the completion of the reaction is strongly acidic, it is preferable to adjust the pH to a range of 2.0 to 9.0 with an alkali agent. Furthermore, preferably, the pH is adjusted in the range of 3.0 to 6.0. If necessary, heating and stirring may be performed at 20 to 95 ° C. for 30 minutes to 4 hours before and after the pH adjustment.

  The alkali agent 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, carbonates such as sodium carbonate, and ammonia. Examples of organic compounds include trialkanolamines such as triethanolamine and triisopropanolamine. can give.

  After neutralization with an alkaline agent, filtration, washing with water and drying in the usual manner give the aniline black according to the present invention.

  Next, the resin composition according to the present invention will be described.

  The resin composition according to the present invention comprises aniline black according to the present invention, a well-known thermoplastic resin, and, if necessary, additives such as a lubricant, a plasticizer, an antioxidant, a UV absorber, various stabilizers and the like. Ru.

  The compounding ratio of aniline black in the resin composition according to the present invention can be used in the range of 0.01 to 200 parts by weight with respect to 100 parts by weight of the constituent substrate, and in consideration of handling of the resin composition, The amount is preferably 0.05 to 100 parts by weight, more preferably 0.1 to 50 parts by weight. Here, the parts by weight of the constituent base material refer to the total parts by weight of the above-mentioned aniline black, a known thermoplastic resin, and various additives.

  The amount of various additives may be 50% by weight or less based on the total of aniline black and the thermoplastic resin. If the content of the additive exceeds 50% by weight, molding of the resulting resin becomes difficult.

The lightness L ^* value of the resin composition according to the present invention is a coloration index measured by the evaluation method described later, as in the evaluation method of aniline black. The term "excellent blackness" means the case where the L ^* value is 15.0 or less. When the L ^* value exceeds 15.0, it is difficult to say that the blackness is excellent. More preferable L ^* value is 12.0 or less. Moreover, the result of the visual observation of dispersibility is the range of level 3-5 among the evaluation methods mentioned later, and is excellent in dispersibility.

The bleed of the resin composition according to the present invention is evaluated by the bleed test as described in the above aniline black bleed according to the present invention. As described above, ΔE ^* is preferably 3.0 or less, more preferably ΔE ^* is 1.5 or less, and more preferably 1.0 or less.

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

  The resin composition according to the present invention is obtained by kneading aniline black and varnish, etc. to form a toner, and then adding a strong shearing action under heating with the kneader or extruder with the toner and resin to obtain aniline in the resin. After the black is dispersed uniformly, it is molded and manufactured into a shape according to the purpose.

  Next, the aqueous dispersion according to the present invention will be described.

  The aqueous dispersion according to the present invention includes various additives such as aniline black according to the present invention, water, and optionally an extender pigment, an aqueous solvent, a surfactant, a pigment dispersant, a resin, a pH adjuster, an antifoamer, etc. Is formulated and configured.

  The compounding ratio of aniline black in the aqueous dispersion according to the present invention 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 base material. Preferably, it is 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight. Here, the parts by weight of the dispersion-constituting base material refer to the total parts by weight of the aniline black, water, and various additives described above.

  As the resin, a water-soluble alkyd resin, a water-soluble melamine resin, a water-soluble acrylic resin, or a water-soluble urethane emulsion resin which is usually used can be used.

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

  As an antifoamer, a well-known antifoamer can be used. For example, NOPCO 8034 (trade name), SN deformer 477 (trade name), SN deformer 5013 (trade name), SN deformer 247 (trade name), SN deformer 382 (trade name) (all of which are made by San Nopco), anti-home 08 (trade name), Emulgen 903 (trade name) (all of which are made by Kao) and the like.

  The viscosity of the aqueous dispersion according to the present invention is 20.0 mPa · s or less. More preferably, it is 15.0 mPa · s or less. When the viscosity exceeds 20 mPa · s, the degree of blackness is poor. The lower limit value of the viscosity is about 1.0 mPa · s.

  The storage stability of the aqueous dispersion according to the present invention is ± 30% or less in the viscosity change rate measured by the evaluation method described later. More preferably, it is ± 10% or less, still more preferably ± 5% or less.

The hue of the aqueous dispersion according to the present invention indicates the L ^* value, the a ^* value, and the b ^* value among the coloration indexes measured by the evaluation method described later, as in the evaluation method of aniline black. Outstanding blackness refers to the case where the L ^* value is 15.0 or less among the measured values. More preferable L ^* value is 12.0 or less. Further, the a ^* value and the b ^* value vary depending on the purpose, and are controlled by the particle size, the shape, the polymerization degree of aniline black, and the kind and amount of the contained acid group. When expressed as ordinary 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.

  For the dispersibility of the aqueous dispersion according to the present invention, the glossiness with a gloss meter according to the evaluation method described later can be used. The higher the gloss value, the better the dispersibility of the dispersion. For example, a gloss of 45 ° can be measured, and a preferred value is 13 or more.

  Next, the method for producing the aqueous dispersion according to the present invention will be described.

  The aqueous dispersion according to the present invention is mixed with aniline black, water and additives, and is dispersed using a media disperser such as a bead mill, or a medialess disperser such as a CLARE MIX, FILMIX, and an ultrasonic homogenizer. It is manufactured after being post-treated such as filtration. In order to enhance dispersion stability, it may be manufactured by self-dispersion treatment or microcapsule treatment.

  Next, the non-aqueous dispersion according to the present invention will be described.

  The non-aqueous dispersion according to the present invention comprises an aniline black according to the present invention, a resin, a solvent, and optionally an extender, a drying accelerator, a surfactant, a curing accelerator, an auxiliary agent, etc. .

  The blending ratio of aniline black in the non-aqueous dispersion according to the present invention 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 base material, considering handling of the dispersion For example, it is preferably 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight.

  As the resin, an acrylic resin, an alkyd resin, a polyester resin, a polyurethane resin, an epoxy resin, a phenol resin, a melamine resin, an amino resin and the like which are usually used can be used.

  As the solvent, toluene, xylene, tetrahydrofuran, ethyl acetate, butyl acetate, methyl acetate, methyl isobutyl ketone, butyl cellosolve, ethyl cellosolve, butyl alcohol, propylene glycol monomethyl ether acetate, aliphatic hydrocarbon etc. may be used as the solvent. it can.

  The viscosity of the non-aqueous dispersion according to the present invention is preferably 20.0 mPa · s or less, more preferably 17.0 mPa · s or less, similarly to the viscosity of the aqueous dispersion. When it exceeds 20 mPa · s, the dispersibility is poor and the blackness is poor. The lower limit value of the viscosity of the non-aqueous dispersion is about 2.0 mPa · s.

  The storage stability evaluation of the non-aqueous dispersion according to the present invention is, similarly to the viscosity of the aqueous dispersion, preferably ± 30% or less, more preferably ± 10% or less in viscosity change rate measured by an evaluation method described later. Still more preferably, it is ± 5% or less.

The hue of the non-aqueous dispersion according to the present invention indicates the L ^* value, the a ^* value, and the b ^* value among the coloration indexes measured by the evaluation method described later, as in the evaluation method of aniline black. Outstanding blackness refers to the case where the L ^* value is 15.0 or less among the measured values. More preferable L ^* value is 12.0 or less. Further, the a ^* value and the b ^* value vary depending on the purpose, and are controlled by the particle size, the shape, the polymerization degree of aniline black, and the kind and amount of the contained acid group. When expressed as ordinary 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.

  For the dispersibility of the non-aqueous dispersion according to the present invention, the glossiness with a gloss meter according to the evaluation method described later can be used. Similar to the method of evaluating the dispersibility of the aqueous dispersion, for example, the glossiness of 45 ° can be measured, and the preferable value is 15 or more.

  Next, the method for producing the non-aqueous dispersion according to the present invention will be described.

  The non-aqueous dispersion according to the present invention is prepared by mixing aniline black, a solvent, an additive, and a resin, and using a media disperser such as a bead mill, or a medialess disperser such as a clear mix, film mix, and ultrasonic homogenizer. It is dispersed and manufactured by post-treatment such as filtration. In order to enhance dispersion stability, it may be manufactured by self-dispersion treatment or microcapsule treatment.

<Function>
The aniline black according to the present invention has a chromium content of 3 to 1000 ppm, and is prepared while identifying and quantifying the main cause substance of the generated bleed and the expected low molecular weight aniline polymer and controlling their amount low. Aniline black. It is believed that bleeding is less likely to occur due to the low amount of predicted aniline tetramer and aniline trimer. The bleeding agents have mass-to-charge m / z values of 379 to 381, and 290 to 292 in the mass spectrum, which are considered to correspond to aniline tetramer and aniline trimer, respectively. These are by-produced in the polymerization process of aniline and are difficult to be dissolved in water, so they are difficult to remove in the production stage. These dissolve relatively well in non-aqueous solvents and resins, and turn yellow to red to cause bleeding. Aniline monomer and dimer are not detected because they are water soluble and can be easily removed in the water washing process. Since no more than aniline pentamer has been detected, it is considered that it does not dissolve in non-aqueous solvents and resins. In order to control the content of the main cause of the bleeding, the amount of the residual sulfur compound of aniline black was limited. As a result, aniline black having a significantly reduced content of the main cause of bleeding was obtained. Although the details are not clear, since this sulfur component is a relatively large molecule, when it is bound to the amino group of aniline as a sulfate or sulfonate, the steric structure of the reaction site such as the ortho or para position of the aniline aromatic ring It is considered to be a hindrance and to inhibit the oxidative polymerization of aniline. That is, it has a polymerization degree such as a low molecular weight aniline polymer having a mass to charge ratio m / z value of 379 to 381 in the mass spectrum and a low molecular weight aniline polymer having a mass to charge ratio m / z value of 290 to 292 in the mass spectrum It is believed that low dye components form and tend to remain in aniline black.

Representative embodiments of the present invention are as follows.
<Evaluation of Aniline Black, Resin Composition, and Dispersion>

  Elemental components contained in aniline black according to the present invention were measured by fluorescent X-ray ZSXPrimus II (manufactured by RIGAKU), and the amounts of chromium and sulfur contained were quantified. The chromium content of aniline black obtained in each of Examples 1 to 5 and Comparative Examples 1 to 5 was 500 ppm or less.

The characterization of aniline black according to the present invention by FT-IR was performed by scanning 4000 to 400 cm ⁻¹ by the KBr method using an infrared spectrophotometer NICOLET iS5 (manufactured by Thermo Scientific).

The molecular weight of aniline black according to the present invention is a weight-average molecular weight measured by GPC (Gel Permeation Chromatography) method using a high performance liquid chromatograph, SEC (Size-exclusion chromatography) column with 10 mg of sample dissolved in dimethylformamide. It is a value. The measurement conditions are shown below.
High-performance liquid chromatograph: LaChrom Elite (manufactured by Hitachi High-Tech Science)
Detector: RI
SEC column: TSKgel α-3000 (manufactured by Tosoh Corporation)
Standard sample: STANDARD SM-105 (molecular weight range: 1.3 × 10 ^{3 to} 3.0 × 10 ⁶ ) (manufactured by Showa Denko)
Eluent: Dimethylformamide flow rate containing 10 mM lithium bromide: 0.5 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 20 μl

Qualification and quantification of the low molecular weight aniline polymer contained in aniline black according to the present invention were performed as follows. Here, it is assumed that the low molecular weight aniline polymer is completely dissolved in acetonitrile. First, 20 mg of particle powder is weighed, immersed in 500 μL of acetonitrile, irradiated with ultrasonic waves for 30 minutes, and filtered. The components contained in the acetonitrile are subjected to high-performance liquid chromatograph, 2-phase linear of reverse phase chromatography. It separated and quantified by the gradient method. The measurement conditions are shown below.
High-performance liquid chromatograph :: LaChrom Elite (made by Hitachi High-Tech Science)
Detector: UV-vis (258 nm)
Reversed phase chromatography column: TSKgel ODS-100z (4.6 mm ID × 15 cm) (manufactured by Tosoh Corporation)
Elution method: 2-component linear gradient (linear gradient elution)
Eluent 1: 0.1% aqueous solution of trifluoroacetic acid Eluent 2: acetonitrile Flow rate: 1.0 ml ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 20 μl
However, as a program, the combination of (eluent 1 and eluant 2) is (100%, 0%), (0%, 100%) when the outflow time is 0 minutes, 30 minutes and 40 minutes, respectively. It was set to be (0%, 100%). In addition, the mass spectrum of each chromatographic peak was measured with a Hitachi 5610 mass detector (manufactured by Hitachi High-Tech Science) (electrospray method, positive ion mode). Furthermore, the UV-visible absorption spectrum of the chromatographic peak was measured with a double beam spectrophotometer UH5300 (manufactured by Hitachi High-Tech Science).

  The average particle diameter of primary particles of aniline black according to the present invention was determined by measuring the specific surface area BET value, and from the value, the spherical conversion value was calculated according to Equation 1, and the average particle diameter of primary particles was obtained. here. Ρ represented by the number 1 is the true density of particles, which was regarded as the true density of aniline black (1.36 g / mL). Further, the specific surface area BET value was measured by the BET method using nitrogen. The apparatus used Monosorb MS-21 (made by QUANTA CHROME).

<Equation 1>
Average particle size of primary particles of aniline black [μm] = 6 / (BET value × ρ)

  For powder pH value, weigh 5 g of the sample in a 300 ml Erlenmeyer flask, add 100 ml of boiled pure water, heat and maintain the boiled state for about 5 minutes, then stopper it and allow it to cool to room temperature. The corresponding water was added, the mixture was again stoppered, shaken for 1 minute, and allowed to stand for 5 minutes, and then the pH of the supernatant obtained was measured according to JIS Z8802-7, and the obtained value was used as the powder pH value. .

First, 0.5 g of particle powder is weighed, and pressure molding is performed at a pressure of 1.372 × 10 ⁷ Pa (140 kg / cm ² ) using a KBr tablet molding machine (manufactured by Shimadzu Corporation). A cylindrical sample to be measured was produced. The sample to be measured was set between stainless steel electrodes, and a voltage of 15 V was applied by an electrical resistance measuring device (model 4329A manufactured by Yokogahoku Tanso Electric Co., Ltd.) to measure a resistance value R (Ω). Next, measure the area A (cm ² ) and thickness t ₀ (cm) of the upper surface of the sample to be measured (cylindrical), insert the respective measured values into the following equation 2, and measure the volume resistivity (Ω · cm). Asked for).

<Equation 2>
Volume specific resistance (Ω · cm) = R × (A / t ₀ )

The bleed of aniline black according to the present invention was colored with a black resin composition colored with prepared aniline black and titanium oxide as shown in Examples 6 to 10 and Comparative Examples 6 to 10 described later. The white resin composition was laminated, heated, and conducted by a bleed test to evaluate the color transfer to the white resin composition. Specifically, a resin composition prepared in an example described later and a white resin composition (not colored with aniline black) prepared in a similar operation are superimposed, sandwiched between glass plates and fixed. The mixture was heated at 110 ° C. for 2 hours and allowed to return to room temperature. Thereafter, each composition is peeled off, and the hue of the white resin composition before and after heating is determined according to JIS Z8729 using a spectrocolorimeter X-Rite 939 (manufactured by X-Rite), and the coloration index L ^* value, The a ^* value and the b ^* value were measured, respectively, and the amounts of change in coloration index before and after heating were taken as ΔL ^* , Δa ^* , and Δb ^* , respectively. The color difference ΔE ^* was calculated by substituting the obtained variation of the coloration index into the following equation 3.

<Equation 3>
ΔE ^* = {(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² } ^1/2

With regard to the hue and lightness (blackness) of aniline black according to the present invention, as shown in Examples 11 to 20 and Comparative Examples 11 to 20 described later, first, an aqueous system containing aniline black prepared, and The aqueous dispersions were each coated on a glass plate using a bar coater with a WET film thickness of 24 μm and dried to prepare a coating (film thickness: about 6 μm). With respect to the coating film, using a spectrocolorimeter X-Rite 939 (manufactured by X-Rite), the coloration index L ^* value, the a ^* value and the b ^* value are shown as measured values in accordance with JIS Z8729.

The determination of the degree of blackness of aniline black according to the present invention was evaluated in the following four stages by the value of L ^* of the obtained coating film.
:: L ^* is 10.0 or less ○: L ^* is more than 10.0 and 12.0 or less △: L ^* is more than 12.0 and 15.0 or less ×: L ^* is 15 More than .0

  About the glossiness of the obtained coating film, the glossiness of 45 degrees was measured and calculated | required using gloss meter UGV-5D (made by Suga Test Instruments). The higher the gloss value of the aqueous dispersion according to the present invention and the coating of the non-aqueous dispersion, the better the dispersibility of the dispersion.

Regarding the lightness L ^* value of the resin composition according to the present invention, the resin sheets produced in Examples 6 to 10 and Comparative Examples 6 to 10 described later were compared with a spectrocolorimeter X-Rite 939 (manufactured by X-Rite). The L ^* value was measured in accordance with JIS Z8729.

The determination of the degree of blackness of the resin composition according to the present invention was evaluated in the following four stages by the value of L ^{* in} the same manner as the determination of the degree of blackness of aniline black.
:: L ^* is 10.0 or less ○: L ^* is more than 10.0 and 12.0 or less △: L ^* is more than 12.0 and 15.0 or less ×: L ^* is 15 More than .0

As shown in Examples 6 to 10 and Comparative Examples 6 to 10 described later, the dispersibility of the resin composition according to the present invention is visually determined by the number of undispersed aggregated particles on the surface of the obtained resin composition. And rated it on a scale of 5. Level 5 indicates that the dispersion is the best.
Level 5: No dispersion is observed.
Level 1 to 4 per 1 cm ² are recognized.
There are 5-9 per level 3: 1 cm ² .
There are 10-49 per level 2: 1 cm ² .
Level: 50 or more per 1 cm ² .

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

The storage stability evaluation of the aqueous dispersion according to the present invention and the non-aqueous dispersion is carried out using an E-type viscometer TV-30 (manufactured by Toki Sangyo Co., Ltd.) with initial viscosity and temporal viscosity after 1 week at 25 ° C. Measured. The viscosity change rate from this initial viscosity (V ₁ ) to the temporal viscosity (V ₂ ) was calculated by the following equation 4 and evaluated in the following three steps.

<Equation 4>
Viscosity change rate (%) = (V _2- V ₁ ) / V ₁ × 100

○: Viscosity change rate is ± 10% or less Δ: Viscosity change rate exceeds ± 10% ± 30% or less ×: Viscosity change rate exceeds 30%

<Production of aniline black>
Example 1
In 50.4 parts by weight of 35% hydrochloric acid (17.6 parts by weight as hydrochloric acid) and 1050 parts by weight of water, 30 parts by weight of aniline is added, and 1.2 parts by weight of polyvinylpyrrolidone (Daiichi Kogyo Seiyaku Pitzcoal K-30) The mixture was added and stirred to form an acidic aqueous solution. The pH of this acidic aqueous solution was 1.2. Thereafter, while stirring and mixing at a liquid temperature of 25 ° C., an aqueous solution of 1.74 parts by weight of ferric chloride hexahydrate dissolved in 33 parts by weight of water is added, and 300 parts by weight of 9% hydrogen peroxide water 27 parts by weight of hydrogen oxide was added dropwise while stirring for 7 hours. The temperature reached by the reaction was 30.degree. After completion of the dropwise addition, the mixture was further stirred at room temperature for 12 hours. Thereafter, the mixture was stirred at 50 ° C. for 2 hours, 10% sodium hydroxide was added to adjust the pH to 4.0, filtered, washed with water, and the paste was dried at 80 ° C. and crushed to obtain a black pigment . When the infrared absorption spectrum of this black pigment was measured, as shown in FIG. 1, it was almost identical to the FT-IR spectrum of aniline listed in SDBS of the organic compound. That is, the stretching vibration of the amino group to 3230cm ^-1, 3050cm ^-1, CH stretching vibration derived from aromatic to ^{2950cm -1, 1580cm -1, 1500cm -1} , C = C stretching vibration of aromatic confirmation to 1450 cm ^-1 Were found to be compounds composed of aminobenzene (= aniline). The weight average molecular weight was about 10,000 and was found to be polyaniline. Moreover, since it was visually black, it was identified as aniline black (name: aniline black-1).

  Moreover, the sulfur content of this aniline black-1 was 0.05 weight%. In Comparative Examples 1 to 5 described later, bleeding occurred, and a sulfur compound such as sulfuric acid was contained under the reaction conditions, and the sulfur content was 0.2% by weight or more, respectively. From this, it can be seen that the reaction conditions for increasing the sulfur content are likely to be correlated with bleed.

Moreover, since the BET value was 15.8 m < ² > / g, when the average particle diameter of the primary particle of aniline black-1 was converted by several 1, it was 0.28 micrometer. The powder pH was 3.6.

Moreover, the volume specific resistance value of aniline black-1 was 2 × 10 ⁹ Ω · cm. The volume specific resistance value of carbon black which has been often used conventionally 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-1 is high.

  In addition, the components contained in aniline black-1 were extracted into acetonitrile, and qualitatively and quantitatively determined by high performance liquid chromatograph. As shown in FIG. 2, two characteristic chromatographs having an outflow time of 22 minutes and 23 minutes. A peak was observed. A chromatographic peak area-content calibration curve prepared using an aniline hydrochloride diluted solution was prepared, and the respective contents were calculated to be 12 ppm and 30 ppm from the respective chromatographic peak areas. Moreover, when the ultraviolet visible absorption spectrum of the chromatographic peak was measured, it was a coloring component which has absorption in the visible region of 367 nm and 382 nm, respectively. Therefore, substances derived from these peaks can be said to be the main cause of bleeding. Furthermore, the mass-to-charge ratio m / z calculated from the mass spectrum of each chromatographic peak was 380, 291. These are considered to correspond approximately to aniline tetramer and aniline trimer. However, these contents were kept low compared to the explanation of FIG. 3 of Comparative Example 1. Therefore, the bleed of the resin composition (Example 6) using aniline black-1 mentioned later was suppressed.

Examples 2 to 5
Aniline black according to the present invention was obtained in the same manner as in Example 1 except that the types and amounts of additives and reaction conditions were variously changed (names: aniline black-2 to 5). In addition, Example 5 (aniline black-5) is an aniline-pyrrole copolymer.

  The manufacturing conditions in these examples are shown in Table 1, and the various properties of the obtained aniline black are shown in Table 2.

Comparative Example 1
Referring to Example 1 of JP 2012-153744 A, 15.8 parts by weight of 71% sulfuric acid (11.2 parts by weight as sulfuric acid) and 31.8 parts by weight of 35% hydrochloric acid (17.6 parts by weight as hydrochloric acid) And 30 parts by weight of aniline in water and 2500 parts by weight of water, and an aqueous solution of 30 parts by weight of an aqueous solution of 4.6 parts by weight of ferric chloride hexahydrate dissolved in 70 parts by weight of water while stirring and mixing at a liquid temperature of 60 ° C. 78.0 parts by weight of hydrogen oxide (23.4 parts by weight as hydrogen peroxide) was added dropwise over 2 hours, and the mixture was 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, and the obtained cake was redispersed using 1000 parts by weight of water and stirred for 24 hours. Thereafter, the mixture was neutralized with 10% caustic soda to pH 9.5, and after the pH was stabilized, it was filtered and washed with water, and the paste was dried at 60 ° C. to obtain aniline black (aniline black-6).

  Moreover, when the component contained in aniline black-6 was extracted to acetonitrile and it quantified and quantified with the high performance liquid chromatograph, as shown in FIG. 3, two characteristic chromatographs of 22 minutes and 23 minutes of outflow time are shown. A peak was observed. A chromatographic peak area-content calibration curve prepared using an aniline hydrochloride diluted solution was prepared, and the respective contents were calculated to be 65 ppm and 100 ppm from the respective chromatographic peak areas. Moreover, when the ultraviolet visible absorption spectrum of the chromatography peak was measured, it was a coloring component which has absorption in 367 nm and 382 nm, respectively. Furthermore, the mass-to-charge ratio m / z calculated from the mass spectrum of each chromatographic peak was 380, 291. This corresponded to aniline tetramer and aniline trimer. Because the content of these low molecular weight aniline polymers is high, bleeding of the resin composition to be described later occurred strongly (Comparative Example 6).

Comparative example 2
Referring to Example 1 of JP 2012-153745 A, 30 parts by weight of aniline is added to 33.8 parts by weight of 35% hydrochloric acid (11.8 parts by weight as hydrochloric acid) and 1250 parts by weight of water, and the liquid temperature is 60 ° C. While stirring and mixing, 15.0 parts by weight of 4-hydroxybenzenesulfonic acid was added and uniformly dissolved. Then, an aqueous solution of 4.6 parts by weight of ferrous chloride hexahydrate dissolved in 70 parts by weight of water, 78.0 parts by weight of 30% hydrogen peroxide (23.4 parts by weight as hydrogen peroxide) is applied over 2 hours The reaction mixture was 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, and the obtained cake was redispersed using 1000 parts by weight of water and stirred for 24 hours. Thereafter, the mixture was neutralized to pH 6.5 with a 10% aqueous sodium hydroxide solution, and after the pH was stabilized, it was filtered and washed with water, and the paste was dried at 60 ° C. to obtain aniline black (aniline black-7). Bleeding of the resin composition described later occurred strongly.

Comparative example 3
30 parts by weight of aniline is dissolved in 600 parts by weight of a 5.1% aqueous solution of sulfuric acid (30.6 parts by weight as sulfuric acid) with reference to Example 5 of JP-A 2001-261989, and ferric chloride 6 water is dissolved therein After 7.8 parts by weight of the hydrate was added in one portion and a solution of 144 parts by weight of ammonium persulfate dissolved in 600 parts by weight of water was dropped over 15 minutes at 40 ° C., the mixture was heated to 70 to 75 ° C. and stirred for 1 hour. After the reaction, insolubles were collected by filtration, washed with water, and the obtained cake was reslurried in 900 parts by weight 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 insolubles were collected by filtration, washed with water and dried to obtain aniline black (aniline black-8). Bleeding of the resin composition described later occurred strongly.

Comparative example 4
Referring to Example 1 of JP-A-2000-72974, 18.0 parts by weight of 62% sulfuric acid (11.2 parts by weight as sulfuric acid) and 31.8 parts by weight of 35% hydrochloric acid (11.2 parts by weight as hydrochloric acid) 30 parts by weight of aniline is added to 300 parts by weight of water and stirred and dissolved, and then 13.2 parts by weight of ferrous sulfate dissolved in 60 parts by weight of water is added at once. While stirring and mixing at a liquid temperature of 15 ° C., 90.0 parts by weight of 30% hydrogen peroxide (27 parts by weight as hydrogen peroxide) is added in 4 hours, and then stirring and mixing are performed at a liquid temperature of 15 ° C. for 4 hours Perform and complete the reaction. After completion of the reaction, the reaction solution was filtered and washed with water, and the obtained cake was redispersed using 960 parts by weight of water. Thereafter, the mixture was neutralized with 10% caustic soda to pH 7, and after the pH was stabilized, it was filtered and washed with water, and the paste was dried at 60 ° C. to obtain aniline black (aniline black-9). Bleeding of the resin composition described later occurred strongly.

Comparative example 5
Referring to Example 4 of JP-A-9-31353, 540 parts by weight of ion-exchanged water, 30 parts by weight of p-toluenesulfonic acid, and 15 parts by weight of ferric sulfate at 1% concentration (0. 15 parts by weight), 350 parts by weight of a 10% aqueous solution of sodium polyisoprene sulfonate (molecular weight = 30,000) dissolved in advance are charged into a reaction vessel, well stirred, and then 33.8 parts by weight of 35% hydrochloric acid 11.8 parts by weight of hydrochloric acid and 30 parts by weight of aniline were charged. While maintaining the reaction temperature at 20 ° C., 360 parts by weight of 5% hydrogen peroxide water (18 parts by weight as hydrogen peroxide water) are continuously added over 2 hours, and after stirring for 2 hours, filtration After washing with water, the paste was dried at 60 ° C. to obtain aniline black (Anrin Black -10). Aniline black-10 had a low volume resistivity (4 × 10 ⁴ Ωcm) because polyisoprene sulfonic acid was bonded as a counter anion. Bleeding of the resin composition described later occurred strongly.

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

  As described above, it is apparent that the aniline black according to the present invention is an aniline black having a low sulfur content, a low content of aniline tetramer and an aniline trimer, and a high volume resistivity. is there.

<Production of Resin Composition>
Example 6
0.5 parts by weight of Aniline Black-1 obtained in Example 1 and 1.5 parts by weight of No. 4 varnish were kneaded at a load of 150 lb and 100 rotations × 3 times with a Huber-Maller to obtain a toner. 0.8 parts by weight of this toner is weighed, 40 parts by weight of a transparent vinyl chloride compound (glass transition temperature: 67 ° C.) is added, the mixture is heated for 5 minutes at 160 ° C. with a heating two roll, and 180 ° C. with a heating press. A sheet of 6 cm long × 3.5 cm wide × 1 mm thick was prepared by applying a pressure of 5 kg / cm ² to obtain a resin composition.

The level of dispersibility of the obtained resin composition was 5, and the dispersibility was high. The L ^* value was as low as 7.5, and the blackness was ◎.

The white resin composition used in the bleed test was prepared by kneading 40 parts by weight of a vinyl chloride white compound (5 wt% of titanium oxide) with a heating two-roll roller at 160 ° C. for 5 minutes, and using a heating press at 180 ° C. and a pressure of 5 kg. A sheet of 6 cm in length × 3.5 cm in width × 1 mm in thickness was prepared by applying 1 cm ² / cm ² to obtain a white resin composition. As a result of bleed determination, ΔE ^* was 1 or less.

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

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

  As described above, it was clear that the aniline black of the present invention has suppressed bleeding, and the obtained resin composition has excellent dispersibility by visual observation and is excellent in the blackness of the coloration index. Aniline black-8 was hard to be dispersed in the resin, the level of dispersion was low, the lightness was high, and the degree of blackness was low.

<Manufacture of aqueous dispersion>
Example 11
Using the aniline black-1 obtained in Example 1, the aqueous dispersion composition was blended in the following proportions, and mixed with 50 parts by weight of 1.5 mmφ glass beads for 60 minutes with a paint shaker to prepare an aqueous dispersion.
Aniline black-1 7.50 parts by weight
Anionic surfactant 2.50 parts by weight,
(Hitenor NF-08: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
10.00 parts by weight of styrene-acrylic copolymer,
(JONCRYL 63J: made by BASF)
0.50 parts by weight of antifoam agent,
(Envirogem AD-01: made by Nisshin Chemical Industry Co., Ltd.)
31.00 parts by weight of water.
The viscosity of the obtained aqueous dispersion was 7.5 mPa · s. Storage stability was ○. Further, the glossiness of the coating film obtained from the aqueous dispersion was 19%, and the dispersibility of the aqueous dispersion was good. The L ^* value of the coating film was 8.2, the a ^* value was -0.3, the b ^* value was -0.1, and the blackness was ◎.

Examples 12-15, comparative examples 11-15
An aqueous dispersion was obtained in the same manner as in Example 11 except that the type of aniline black used was variously changed.

  Various properties of the aqueous dispersion obtained at this time are shown in Table 4.

  As described above, it is apparent that the aniline black of the present invention is excellent in blackness, and the obtained aqueous dispersion is excellent in storage stability by viscosity measurement, dispersion by glossiness of a coating film, and excellent in blackness. is there.

<Production of non-aqueous dispersion>
Example 16
Using the aniline black-1 obtained in Example 1, the non-aqueous dispersion composition was blended in the following proportions 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 a non-aqueous dispersion.
Aniline black-1 7.50 parts by weight
2.00 parts by weight of a polymeric dispersant,
(PB 822: made by Ajinomoto Fine Techno Co., Ltd.)
3.00 parts by weight of styrene-acrylic copolymer,
(JONCRYL 680: made by BASF)
Propylene glycol 1-monomethyl ether 2-acetate 37.50 parts by weight.
The viscosity of the obtained non-aqueous dispersion was 8.0 mPa · s. The storage stability was ○, and the gloss of the coating was 20%. From the above, the dispersibility of the dispersion was good. In addition, the L ^* value was 7.5, the a ^* value was -0.2, the b ^* value was -0.1, and the blackness was 。.

Examples 17 to 20, Comparative Examples 16 to 20
A non-aqueous dispersion was obtained in the same manner as in Example 16 except that the type of aniline black used was variously changed.

  Various properties of the non-aqueous dispersion obtained at this time are shown in Table 5.

  As described above, the aniline black of the present invention is excellent in blackness, and the obtained non-aqueous dispersion, like the aqueous dispersion, is excellent in dispersibility such as storage stability and gloss, and excellent in blackness it is obvious.

Aniline black according to the present invention has a low chromium content, suppresses bleeding, is excellent in blackness, and has a high volume specific resistance, and thus electronic devices such as nonmagnetic developers for electrophotography, colorants for black matrix, etc. It is suitable for various applications such as eyebrow pencils, eyebrow powders, eyebrow powders, eye shadows, compact powders, foundations, lipsticks, nail enamels, cosmetics such as paints, paints, printing inks, and inkjet inks. In the resin composition containing the aniline black, or in the aqueous dispersion or the non-aqueous dispersion containing the aniline black, bleeding is suppressed, the dispersibility is excellent, and the blackness is high. It is suitable as the said use.

Claims (9)

The bleed-resistant aniline black particles having an average primary particle diameter of 0.05 to 1.0 μm are characterized in that the contents of aniline tetramer and aniline trimer are 1 to 50 ppm, respectively. Aniline black particles. The aniline black particle according to claim 1, wherein the mass to charge ratio m / z value is 379 to 381 in the measurement of the aniline tetramer by liquid chromatography mass spectrometry (LC / MS). The aniline black particle according to claim 1 or 2, wherein the mass to charge ratio m / z value is 290 to 292 in the measurement of the aniline trimer by liquid chromatography-mass spectrometry (LC / MS). The aniline black particles according to any one of claims 1 to 3, wherein the sulfur content is 0.01 to 0.19% by weight. The aniline black particles according to any one of claims 1 to 4, wherein the powder pH is 2.0 to 9.0. The aniline black particle according to any one of claims 1 to 5, which has a volume resistivity of 10 ⁶ to 10 ¹⁰ Ω · cm. A resin composition comprising the aniline black particles according to any one of claims 1 to 6. An aqueous dispersion comprising the aniline black particles according to any one of claims 1 to 6. A non-aqueous dispersion comprising the aniline black particles according to any one of claims 1 to 6.