JP2010235936A - Yellow pigment dispersion, ink for inkjet recording, cartridge for inkjet recording, method for inkjet recording, inkjet recording device, and inkjet recorded matter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide: a yellow pigment dispersion giving a recorded matter excellent in hue, optical density, light fastness and ozone gas fastness; ink for inkjet recording; a cartridge for inkjet recording; and a method for inkjet recording; as well as an inkjet recorded matter excellent in hue, optical density, light fastness and ozone gas fastness. <P>SOLUTION: The yellow pigment dispersion includes at least one azo pigment of formula (1) or a tautomer thereof, and at least one selected from C.I. pigment yellows 1, 2, 3, 12, 13, 14, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 120, 128, 138, 139, 150, 151, 154, 155, 180, 185, and 213. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a yellow pigment dispersion, an ink for ink jet recording, a cartridge for ink jet recording, an ink jet recording method, an ink jet recording apparatus, and an ink jet recorded material.

  In recent years, a material for forming a color image has been mainly used as an image recording material, and specifically, an ink jet recording material, a thermal transfer recording material, an electrophotographic recording material, a transfer halogen. Silver halide photosensitive materials, printing inks, recording pens, and the like are actively used. Further, a color filter is used for recording and reproducing a color image on an image pickup device such as a CCD in a photographing apparatus and on an LCD or PDP in a display. In these color image recording materials and color filters, three primary colors (dyes and pigments) of the so-called additive color mixture method and subtractive color mixture method are used to display or record full color images. The fact is that there is no fast-acting dye that has absorption characteristics that can realize the above-mentioned conditions and can withstand various use conditions and environmental conditions, and improvement is strongly desired.

The dyes and pigments used in each of the above applications must have the following properties in common. That is, it has preferable absorption characteristics in terms of color reproducibility, fastness under environmental conditions to be used, for example, light resistance, heat resistance, good resistance to oxidizing gases such as ozone, and the like. In addition, when the pigment is a pigment, it is further substantially insoluble in water and organic solvents and has good chemical fastness, and even when used as particles, the preferred absorption characteristics in the molecular dispersion state are impaired. It is also necessary to have properties such as absence. The required characteristics can be controlled by the strength of intermolecular interaction, but it is difficult to achieve both because they are in a trade-off relationship.
In addition, when using the pigment, in addition to having a particle size and a particle shape necessary for expressing the desired transparency, fastness under the environmental conditions used, such as light resistance, heat resistance, Good resistance to oxidative gases such as ozone, and other chemical fastness to organic solvents and sulfurous acid gas. Disperse even fine particles in the medium used, and stable dispersion. , Etc. are also required. In particular, there is a strong demand for pigments that have a good hue, have high coloring power among light, wet heat, and active gases in the environment, and are fast to light.

  In other words, the required performance for pigments is more diverse than dyes that require performance as pigment molecules, and not only the performance as pigment molecules, but also the above requirements as solids (fine particle dispersions) as aggregates of pigment molecules All performance needs to be satisfied. As a result, the group of compounds that can be used as pigments is extremely limited compared to dyes, and even if high-performance dyes are derived into pigments, there are only a few that can satisfy the required performance as fine particle dispersions. It cannot be developed. This is confirmed by the fact that the number of pigments registered in the color index is less than 1/10 of the number of dyes.

  Azo pigments are widely used in printing inks, ink-jet inks, electrophotographic materials and the like because they are excellent in hue and coloring power, which are color characteristics. Of these, the most typically used azo pigments are yellow diarylide pigments and red naphthol azo pigments. Examples of diarylide pigments include C.I. I. Pigment Yellow 12, 13 and 17 and the like. Examples of naphthol azo pigments include C.I. I. Pigment Red 208, 242 and the like. However, these pigments are extremely inferior in fastness, particularly light resistance, and are therefore not suitable for long-term storage of printed matter because the pigment is decomposed and faded when the printed matter is exposed to light.

  In order to improve such defects, azo pigments having improved fastness by increasing the molecular weight or introducing a group having a strong intermolecular interaction are also disclosed (for example, Patent Documents 1 to 3). 3). However, even in the improved pigment, for example, the pigment described in Patent Document 1 has improved light resistance, but is still insufficient. For example, the pigment described in Patent Documents 2 and 3 has a green hue. There was a drawback that coloring power was lowered by taste and color characteristics were inferior.

  Further, Patent Documents 4 to 5 disclose dyes having absorption characteristics excellent in color reproducibility and sufficient fastness. However, since all of the specific compounds described in the patent document dissolve in water or an organic solvent, the chemical fastness is not sufficient.

  When expressing a full color using a subtractive color mixing method with three colors of yellow, magenta and cyan, or even four colors with black added, if a pigment with only one color is inferior in color fastness, If the balance is changed and a pigment having poor color characteristics is used, the color reproducibility at the time of printing is lowered. Therefore, in order to obtain a printed matter that maintains a high color reproducibility for a long period of time, a pigment and a pigment dispersion having both color characteristics and fastness are desired.

JP-A-56-38354 US Pat. No. 2,936,306 Japanese Patent Laid-Open No. 11-1000051 JP 2005-213357 A Japanese Patent Laid-Open No. 2003-246942

The present invention provides a yellow pigment dispersion, an ink jet recording ink, an ink jet recording cartridge, an ink jet recording method, and an ink jet recording apparatus capable of obtaining a recorded matter excellent in hue, coloring power, light fastness and ozone gas fastness. The purpose is to do.
Another object of the present invention is to provide an ink-jet recorded matter excellent in hue, tinting strength, light fastness and ozone gas fastness.

  As a result of intensive studies in view of the above circumstances, the present inventors have bonded a pyrazole ring having a specific substituent and another pyrazole ring having a different substituent through an azo group to form a dye mother nucleus, and The bisazo pigment formed by linking two of these dye nuclei via a nitrogen-containing heterocycle or a pigment dispersion of a tautomer thereof has found excellent color characteristics and fastness. It was.

That is, the present invention is as follows.
[1]
At least one azo pigment or tautomer represented by the following formula (1):
C. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 120, 128, 138, 139, 150, A yellow pigment dispersion comprising a colorant containing at least one selected from the group consisting of 151, 154, 155, 180, 185, and 213.

[2]
The above azo pigment or tautomer has characteristic X-ray diffraction peaks with Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction of 7.6 °, 25.6 °, and 27.7 °. The yellow pigment dispersion according to [1] having

[3]
The yellow pigment dispersion according to [1] or [2], wherein the azo pigment or tautomer is contained in an amount of 10% by mass or more based on the total pigment solid content in the yellow pigment dispersion.

[4]
The yellow pigment dispersion according to any one of [1] to [3], further comprising a dispersant in an amount of 10 to 140% by mass based on the colorant.

[5]
The yellow pigment dispersion according to any one of [1] to [4], further comprising a high-boiling organic solvent in an amount of 0.1 to 30% by mass relative to the total amount of the yellow pigment dispersion.

[6]
The yellow pigment dispersion according to any one of [1] to [5], further comprising a penetration accelerator in an amount of 1 to 20% by mass based on the total amount of the yellow pigment dispersion.

[7]
Ink for inkjet recording containing the yellow pigment dispersion as described in any one of [1] to [6].

[8]
An ink jet recording cartridge comprising the ink for ink jet recording according to [7].

[9]
The inkjet recording method which forms an image using the ink for inkjet recording as described in [7].

[10]
An ink jet recording apparatus for forming an image using the ink for ink jet recording according to [7].

[11]
[7] An ink-jet recorded matter formed by forming an image using the ink for ink-jet recording described in [7].

According to the yellow pigment dispersion, the ink for ink jet recording, the ink jet recording method, the ink jet recording method and the ink jet recording apparatus of the present invention, it is possible to obtain a recorded matter excellent in hue, coloring power, light fastness and ozone gas fastness. it can.
Moreover, according to the inkjet recorded matter of the present invention, an inkjet recorded matter excellent in coloring power, light fastness and ozone gas fastness can be obtained.
The yellow pigment dispersion of the present invention is used as a colored product excellent in light fastness, for example, in printing ink such as inkjet, color toner for electrophotography, display such as LCD and PDP, and image sensor such as CCD. Can be used for color filters, paints, colored plastics and the like.

2 is an X-ray diffraction pattern of an azo pigment (1) synthesized according to Synthesis Example 1. FIG.

Hereinafter, the present invention will be described in detail.
The yellow pigment dispersion of the present invention comprises at least one azo pigment represented by the following formula (1) or a tautomer (hereinafter sometimes simply referred to as an azo pigment represented by the formula (1)). , C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 120, 128, 138, 139, 150, At least one selected from the group consisting of 151, 154, 155, 180, 185 and 213 (hereinafter sometimes simply referred to as “A group yellow pigment” or “yellow pigment (A)”). .

The yellow pigment dispersion preferably contains 10 mass% or more of the azo pigment represented by the formula (1) with respect to the total pigment solid content in the yellow pigment dispersion, and contains 30 mass% to 100 mass%. More preferably, 55 mass% to 95 mass% is further included, and 70 mass% to 85 mass% is particularly preferable.
Components other than the azo pigment represented by the formula (1) contained in the yellow pigment dispersion of the present invention include tautomers, crystal polymorphs, salts, and water of the azo pigment represented by the formula (1). A Japanese thing etc. can be mentioned.

  The content of the yellow pigment of Group A is preferably 0.1% by mass or more and less than 99% by mass with respect to the total pigment solid content of the yellow pigment dispersion of the present invention, and is 1% by mass or more and less than 70% by mass. More preferably, it is more preferably 5% by mass or more and less than 45% by mass, and most preferably 15% by mass or more and less than 30% by mass.

  The yellow pigment dispersion of the present invention contains the azo pigment represented by the formula (1) (azo pigment (1)) and the yellow pigment of group A (yellow pigment (A)), so that the hue and tinting strength are increased. The light fastness and ozone gas fastness can be excellent.

  The ratio of the content of the azo pigment (1) and the yellow pigment (A) in the yellow pigment dispersion is preferably as follows: azo pigment (1) / yellow pigment (A) = 5/95 (mass% / mass%) to 95/5 (mass% / mass%), more preferably 20/80 (mass% / mass%) to 80/20 (mass% / mass%), particularly preferably 40/60. (Mass% / mass%) to 60/40 (mass% / mass%).

  In addition, the yellow pigment dispersion of the present invention contains the azo pigment (1) and the yellow pigment (A) in the above range, so that when the yellow pigment dispersion is used for an ink jet recording ink or the like, Further, the coloring power, light fastness and ozone gas fastness can be improved.

  The azo pigment (1) has characteristic X-ray diffraction peaks at a Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction of 7.6 °, 25.6 °, and 27.7 °. An azo pigment represented by the formula (1) (hereinafter referred to as α-type crystal form azo pigment), Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction is 7.0 °, 26.4 °, 27 An azo pigment represented by the above formula (1) having a characteristic X-ray diffraction peak at 3 ° (hereinafter referred to as β-type crystal form azo pigment) and a Bragg angle in CuKα characteristic X-ray diffraction (2θ ± 0.2 °) Is an azo pigment represented by the above formula (1) (hereinafter referred to as γ-type crystal form azo pigment) having characteristic X-ray diffraction peaks at 6.4 °, 26.4 °, and 27.2 °. .

The azo pigment represented by the formula (1) has characteristic X-rays with Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction of 7.6 °, 25.6 °, and 27.7 °. An α-type crystal form azo pigment having a diffraction peak is preferable, and the hue, coloring power, light fastness, and ozone gas fastness can be further improved.
The X-ray diffraction measurement of the present invention can be performed with a powder X-ray diffraction measurement apparatus RINT2500 (manufactured by Rigaku Corporation) in accordance with Japanese Industrial Standard JISK0131 (general rules for X-ray diffraction analysis).

  In the present invention, the means for obtaining the azo pigment represented by the above formula (1) includes a diazonium salt derived from a heterocyclic amine (diazo component) represented by the following formula (2), and the following formula (3): Examples thereof include a method of controlling and obtaining reaction conditions (solvent species, pH value, reaction temperature, reaction time, etc.) by a method in which the compound (coupling component) represented is subjected to an azo coupling reaction.

  In the case of a single crystal form, the molecules become dense and the intermolecular interaction becomes strong. As a result, the solvent resistance, thermal stability, light resistance, gas resistance and printing density are increased, and the color reproduction range is further expanded.

  Therefore, the azo pigment represented by the above formula (1) has characteristic Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction of 7.6 °, 25.6 ° and 27.7 °. Crystal forms having X-ray diffraction peaks are preferred, and crystal forms having characteristic X-ray diffraction peaks at 7.6 °, 13.5 °, 25.6 ° and 27.7 ° are more preferred. Among them, a crystal form having characteristic X-ray diffraction peaks at 7.6 °, 13.5 °, 15.9 °, 16.9 °, 25.6 ° and 27.7 ° is most preferable.

  The length in the major axis direction when the primary particles of the azo pigment represented by the above formula (1) described above are observed with a transmission microscope is preferably 0.01 μm or more and 30 μm or less. The thickness is more preferably 0.02 μm or more and 30 μm or less, and particularly preferably 0.03 μm or more and 2 μm or less.

  When the length of the major axis when the primary particles are observed with a transmission microscope is 0.01 μm or more, the fastness to light and ozone, and the dispersibility when used as a pigment dispersion are more reliable. Can be expressed. On the other hand, when the particle size is 30 μm or less, it is difficult to be in an overdispersed state (a form in which primary particles are destroyed) when dispersed to have a desired volume average particle diameter, and the active surface is not easily exposed on the surface of pigment particles. Therefore, aggregation is difficult to occur, so that the storage stability of the pigment dispersion can be expressed more reliably.

  By controlling the size of the primary particles within the above range, pigment particles form a strong and stable three-dimensional network with strong intramolecular and intermolecular interactions, and light, heat, humidity, and oxidative properties. A colored product using a pigment dispersion exhibiting high fastness to gas is preferred because of its excellent storage stability.

  For measurement of the volume average particle size of the pigment dispersion of the present invention, a Nanotrac UPA particle size analyzer (UPA-EX150; manufactured by Nikkiso Co., Ltd.) can be used. The measurement can be performed, for example, by placing 3 ml of pigment dispersion in a measurement cell and according to a predetermined measurement method. As parameters input at the time of measurement, the ink viscosity is used as the viscosity, and the pigment density is used as the density of the dispersed particles.

  The average volume particle diameter (Mv) of the azo pigment dispersion represented by the above formula (1) is preferably 0.01 μm or more and 30 μm or less, more preferably 0.02 μm or more and 30 μm or less, and 0.03 μm. The thickness is particularly preferably 20 μm or less and most preferably 30 nm or more and 150 nm or less.

  If it is in the above range, the print density of the printed matter is high, the stability of the dispersion is increased, the color reproducibility of the mixed color portion such as red and green is improved, the transparency is high, and when printing with an inkjet or the like. It is preferable because nozzle clogging is less likely to occur. Further, it is preferable from the viewpoint that aggregation of the pigment dispersion hardly occurs and stability with time of the dispersion becomes high.

  In order to make the volume average particle diameter of the pigment dispersion of the present invention in the above range, it can be easily adjusted by combining the pigment dispersion conditions described later for convenience.

  In the following equation (2), the Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction have characteristic X-ray diffraction peaks at 7.6 °, 25.6 °, and 27.7 °. The method for producing an azo pigment composition containing at least one azo pigment or tautomer represented will be described in detail.

  The production method of the azo pigment composition represented by the following formula (1) is represented by the diazonium salt derived from the heterocyclic amine (diazo component) represented by the following formula (2) and the following formula (3). A step of subjecting the compound (coupling component) to an azo coupling reaction.

[Diazonium salt preparation step of heterocyclic amine]
Preparation of a heterocyclic amine (diazo component) represented by the above formula (2) to a diazonium salt and a coupling reaction between the diazonium salt and the compound represented by the above formula (3) (coupling component) are carried out by conventional methods. Can be implemented.

  The diazonium salt preparation of the heterocyclic amine represented by the above formula (2) is prepared in a reaction medium containing an acid (for example, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc.). A conventional diazonium salt preparation method using a nitrosonium ion source such as nitrous acid, nitrite or nitrosylsulfuric acid can be applied.

  Examples of more preferred acids include the case where acetic acid, propionic acid, methanesulfonic acid, phosphoric acid and sulfuric acid are used alone or in combination, among which phosphoric acid or a combined system of acetic acid and sulfuric acid, acetic acid and propion A combined system of acid, a combined system of acetic acid, propionic acid and sulfuric acid is more preferable, and a combined system of acetic acid and propionic acid and a combined system of acetic acid, propionic acid and sulfuric acid are particularly preferable.

  Preferable examples of the reaction medium (solvent) include organic acids and inorganic acids, and phosphoric acid, sulfuric acid, acetic acid, propionic acid, and methanesulfonic acid are particularly preferable. Among these, acetic acid and / or propionic acid are preferable.

Examples of preferred nitrosonium ion sources include nitrites, nitrites, nitrosylsulfuric acid and the like. Among them, sodium nitrite, potassium nitrite, isoamyl nitrite, nitrosylsulfuric acid (e.g., ONHSO ₄ sulfuric acid solution) are preferred, isoamyl nitrite, nitrosylsulfuric acid (e.g., 40% to 50% by weight ONHSO ₄ sulfuric acid solution) Among these, the use of nitrosylsulfuric acid in the above-mentioned preferable acid-containing reaction medium can prepare a diazonium salt stably and efficiently.

  0.5-50 mass times is preferable, as for the usage-amount of the solvent with respect to the diazo component of Formula (2), More preferably, it is 1-20 mass times, and 3-15 mass times is especially preferable.

  In the present invention, the diazo component of the formula (2) may be in a state of being dispersed in a solvent, or may be in a solution state depending on the kind of the diazo component.

  The amount of nitrosonium ion source used is preferably 0.95 to 5.0 equivalents, more preferably 1.00 to 3.00 equivalents, particularly 1.00 to 1.10 equivalents, relative to the diazo component. Is preferred.

  The reaction temperature is preferably −15 ° C. to 40 ° C., more preferably −5 ° C. to 35 ° C., and still more preferably −0 ° C. to 30 ° C. Less than −10 ° C. is not economical because the reaction rate is remarkably slow and the time required for the synthesis is remarkably increased. In addition, when synthesizing at a high temperature exceeding 40 ° C., the amount of by-products increases, which is preferable. Absent.

  The reaction time is preferably 30 minutes to 300 minutes, more preferably 30 minutes to 200 minutes, and still more preferably 30 minutes to 150 minutes.

[Coupling reaction process]
The step of coupling reaction can be carried out in an acidic reaction medium to a basic reaction medium, but the azo pigment of the present invention is preferably carried out in an acidic to neutral reaction medium, particularly in an acidic reaction medium. It is possible to efficiently induce the azo pigment by suppressing the decomposition of the diazonium salt.

  As a preferable example of the reaction medium (solvent), an organic acid, an inorganic acid, or an organic solvent can be used, but an organic solvent is particularly preferable, and a solvent that does not cause a liquid separation phenomenon during the reaction and presents a uniform solution with the solvent. preferable. For example, alcoholic organic solvents such as methanol, ethanol, propanol, isopropanol, butanol, t-butyl alcohol, amyl alcohol, ketone organic solvents such as acetone, methyl ethyl ketone, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene Diol-based organic solvents such as glycol and 1,3-propanediol, ether-based organic solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol diethyl ether, tetrahydrofuran, dioxane, acetonitrile, and the like. May be a mixture of two or more.

  Preferably, the organic solvent has a polarity parameter (ET) value of 40 or more. Among them, a glycol solvent having two or more hydroxyl groups in a solvent molecule, an alcohol solvent having 3 or less carbon atoms, a ketone solvent having a total carbon number of 5 or less, preferably an alcohol having 2 or less carbon atoms. Solvents (for example, methanol, ethylene glycol) and ketone solvents having a total carbon number of 4 or less (for example, acetone, methyl ethyl ketone) are preferable. These mixed solvents are also included.

  The amount of the solvent used is preferably 1 to 100 times, more preferably 1 to 50 times, more preferably 2 to 30 times the amount of the coupling component represented by the above formula (3).

  In the present invention, the coupling component represented by the formula (3) may be in a state of being dispersed in a solvent, or may be in a state of a solution depending on the type of the coupling component.

  The amount of the coupling component used is preferably 0.95 to 5.0 equivalents, more preferably 1.00 to 3.00 equivalents, particularly 1.00 to 1.50, based on the azo coupling site. It is preferable that it is equivalent.

  The reaction temperature is preferably -30 ° C to 30 ° C, more preferably -15 ° C to 10 ° C, and further preferably -10 ° C to 5 ° C. Less than −30 ° C. is not economical because the reaction rate is remarkably slow and the time required for synthesis becomes remarkably long. In addition, synthesis at a high temperature exceeding 30 ° C. is preferable because the amount of by-products increases. Absent.

  The reaction time is preferably 30 minutes to 300 minutes, more preferably 30 minutes to 200 minutes, and still more preferably 30 minutes to 150 minutes.

  In the method for producing an azo pigment composition of the present invention, the product (crude azo pigment) obtained by these reactions is treated according to a post-treatment method of a normal organic synthesis reaction and then purified or used without purification. be able to.

  That is, for example, the product liberated from the reaction system can be used without being purified, or can be purified by recrystallization, salt formation, etc., alone or in combination.

  After completion of the reaction, the reaction solvent is distilled off, or it is poured into water or ice without being distilled off, and the liberated product is extracted with neutralization or without neutralization, or extracted with an organic solvent / aqueous solution. It can also be used after purification or refining by recrystallization, crystallization, salt formation or the like, either alone or in combination.

  The method for producing the azo pigment composition of the present invention will be described in more detail.

  The method for producing an azo pigment composition of the present invention includes a coupling reaction between a diazonium compound obtained by diazonium-izing a heterocyclic amine represented by the above formula (2) and a compound represented by the above formula (3). A coupling reaction is performed after the compound represented by the formula (3) is dissolved in an organic solvent.

  The diazonium salt preparation reaction of the heterocyclic amine represented by the above formula (2) is carried out at a temperature of 15 ° C. or less with a reagent such as sodium nitrite and nitrosylsulfuric acid in an acidic solvent such as sulfuric acid, phosphoric acid and acetic acid. The reaction can be carried out for about 6 minutes to 6 minutes. The coupling reaction can be performed by reacting the diazonium salt obtained by the above-described method with the compound represented by the above formula (3) at 40 ° C. or less, preferably 15 ° C. or less for about 10 minutes to 12 hours. preferable.

  The tautomerism and / or crystal polymorphism described above can be controlled by the production conditions during the coupling reaction. Pigment composition mainly composed of crystals of formula (1) (α-type crystal form azo pigments) having characteristic X-ray diffraction peaks at 7.6 °, 25.6 ° and 27.7 ° which are more preferable forms As a method for producing a product, for example, it is preferable to use the method of the present invention in which a compound represented by the above formula (3) is once dissolved in an organic solvent and then a coupling reaction is performed. Examples of the organic solvent that can be used at this time include alcohol solvents and ketone solvents. As examples of the alcohol solvent, methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol and the like are preferable, and methanol is particularly preferable among them. As an example of the ketone solvent, acetone, methyl ethyl ketone, cyclohexanone and the like are preferable, and acetone is particularly preferable among them.

  Another method for producing an azo pigment composition of the present invention is a coupling reaction between a diazonium compound obtained by diazonium-izing a heterocyclic amine represented by the above formula (2) and a compound represented by the above formula (3). The coupling reaction is performed in the presence of a polar aprotic solvent.

  Even when the coupling reaction is carried out in the presence of a polar aprotic solvent, crystals of the formula (1) having the characteristic X-ray diffraction peaks at 7.6 °, 25.6 ° and 27.7 ° (form α It is possible to efficiently produce a pigment composition mainly composed of a crystal form azo pigment). Examples of polar aprotic solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, acetone, methyl ethyl ketone, acetonitrile, and mixed solvents thereof. Etc. Among these solvents, acetone, methyl ethyl ketone, N, N-dimethylacetamide, and acetonitrile are particularly preferable. When these solvents are used, the compound represented by the above formula (2) may or may not be completely dissolved in the solvent.

  The compound obtained by the above production method may or may not be adjusted to pH by adding a base as a purification step depending on the use. When adjusting pH, 4-10 are preferable for pH. Among these, pH is more preferably 5-8, and particularly preferably 5.5-7.5.

  If the pH is 10 or less, it is preferable from the viewpoint of ensuring a hue of constant quality without causing discoloration and fading from the viewpoint of hue and without increasing redness. When the pH is 4 or more, for example, when used as an inkjet recording ink, it is preferable because problems such as corrosion of the nozzle hardly occur.

By the above production method, the compound represented by the above formula (1) is obtained as a crude azo pigment (crude).
The present invention also relates to an azo pigment composition produced by the above production method.

[Post-treatment process]
In the manufacturing method of this invention, it is preferable to include the process of performing a post-process. As a method of this post-treatment step, for example, solvent particle milling process such as solvent salt milling, salt milling, dry milling, solvent milling, acid pasting, pigment heat control process, solvent heating treatment, etc., resin, surfactant and dispersion And a surface treatment step using an agent.

  The compound represented by the above formula (1) of the present invention is preferably subjected to solvent heat treatment and / or solvent salt milling as a post-treatment step. For example, an azo pigment having a desired crystal form can be produced by refluxing in an organic solvent excluding water.

  Examples of the solvent used in the solvent heat treatment include water, aromatic hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as chlorobenzene and o-dichlorobenzene, and alcohols such as isopropanol and isobutanol. Examples include solvents, polar aprotic organic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, acetone, methyl ethyl ketone, and acetonitrile, glacial acetic acid, pyridine, and mixtures thereof. It is done. An inorganic or organic acid or base may be further added to the solvents mentioned above.

  The temperature of the solvent heat treatment varies depending on the desired primary particle diameter of the pigment, but is preferably 40 to 150 ° C, more preferably 60 to 100 ° C. The treatment time is preferably 30 minutes to 24 hours.

  As solvent salt milling, for example, a crude azo pigment, an inorganic salt, and an organic solvent that does not dissolve the crude azo pigment are charged into a kneader and kneaded and ground therein. As the inorganic salt, a water-soluble inorganic salt can be preferably used. For example, an inorganic salt such as sodium chloride, potassium chloride, sodium sulfate is preferably used. Moreover, it is more preferable to use an inorganic salt having an average particle size of 0.5 to 50 μm. The amount of the inorganic salt used is preferably 3 to 20 times by mass, more preferably 5 to 15 times by mass with respect to the crude azo pigment. As the organic solvent, a water-soluble organic solvent can be suitably used, and the solvent easily evaporates due to a temperature rise during kneading, so that a high boiling point solvent is preferable from the viewpoint of safety. Examples of such organic solvents include diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, diethylene glycol Propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene Glycol or mixtures thereof. The amount of the water-soluble organic solvent used is preferably 0.1 to 5 times by mass with respect to the crude azo pigment. The kneading temperature is preferably 20 to 130 ° C, particularly preferably 40 to 110 ° C. As a kneader, for example, a kneader or a mix muller can be used.

  In the present invention, a β-type crystal form azo pigment or an acquisition means for an azo pigment composition containing a γ-type crystal form azo pigment includes a diazonium salt derived from a heterocyclic amine represented by the above formula (2), The method of controlling by the reaction conditions (a solvent seed | species, pH value, reaction temperature, reaction time, etc.) of the process of making an azo coupling reaction with the compound represented by the said Formula (3) is mentioned. Furthermore, the azo pigment obtained in the above step can be easily obtained under the conditions (solvent type, pH value, reaction temperature, reaction time, etc.) when further treating in the subsequent step.

As described above, the yellow pigment dispersion of the present invention contains a group A yellow pigment in addition to the azo pigment represented by the formula (1).
From the viewpoint of hue, image fastness and pigment dispersibility, this group A yellow pigment is a C.I. I. Pigment Yellow 74, 110, 120, 128, 138, 139, 150, 155, 185, 213 is preferably at least one selected from the group consisting of C.I. I. It is more preferable that it is at least one selected from the group consisting of CI Pigment Yellow 74, 128, 155, 138, 139, 185 and 213. I. Most preferred is at least one selected from the group consisting of CI Pigment Yellow 74, 128, 155, 185 and 213.

  The yellow pigment dispersion of the present invention may be aqueous or non-aqueous, but is preferably an aqueous pigment dispersion. As the aqueous liquid in which the pigment is dispersed in the aqueous pigment dispersion of the present invention, a mixture containing water as a main component and optionally adding a hydrophilic organic solvent can be used. Examples of the hydrophilic organic solvent include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol and other alcohols, ethylene glycol, diethylene glycol , Other alcohols such as triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, ethylene glycol butyl ether, diethylene glycol mono Chill ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate triethylene glycol monoethyl ether, ethylene glycol monophenyl ether Glycol derivatives such as ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine Such as amine, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1 , 3-dimethyl-2-imidazolidinone, acetonitrile, acetone and the like.

  Further, the aqueous pigment dispersion of the present invention may contain an aqueous resin. Examples of the aqueous resin include water-soluble resins that dissolve in water, water-dispersible resins that disperse in water, colloidal dispersion resins, and mixtures thereof. Specific examples of the aqueous resin include acrylic, styrene-acrylic, polyester, polyamide, polyurethane, and fluorine resins.

  In addition, surfactants and dispersants may be used to improve pigment dispersion and image quality. Examples of the surfactant include anionic, nonionic, cationic and amphoteric surfactants. Any surfactant may be used, but anionic or nonionic surfactants may be used. It is preferable to use it. Examples of anionic surfactants include fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl diaryl ether disulfonates, alkyl phosphates, and polyoxyethylene alkyls. Examples thereof include ether sulfate, polyoxyethylene alkylaryl ether sulfate, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester salt, glycerol borate fatty acid ester, polyoxyethylene glycerol fatty acid ester and the like.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin Examples include fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, fluorine-based resins, and silicon-based materials.

  As the dispersant, a commercially available dispersant containing a polymer such as vinyl polymer, modified polyurethane, salt of polyaminoamide and acid ester, modified polyethyleneimine, modified polyallylamine, or a base can be used.

Only one type of dispersant may be added to the yellow pigment dispersion, or two or more types may be used in combination. The content of the dispersant in the yellow pigment dispersion is preferably 10% by mass to 150% by mass, more preferably 10% by mass to 100% by mass, and more preferably 30% by mass to 80% by mass with respect to the total pigment solid content. % Is most preferred.
Further, in the yellow pigment dispersion, the dispersant is preferably included at 10 to 140% by mass, more preferably 20 to 80% by mass, and more preferably 30 to 55% by mass with respect to the colorant. This is particularly preferable from the viewpoints of the stability of the dispersion over time, the ejection properties of the ink jet ink, the print density, the color reproducibility of the print, and the like.

  The non-aqueous pigment dispersion is obtained by dispersing the yellow pigment of formula (1) and group A in a non-aqueous vehicle. Resins used in non-aqueous vehicles include, for example, petroleum resins, casein, shellac, rosin-modified maleic resin, rosin-modified phenolic resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber, chlorinated rubber, oxidized rubber, and hydrochloric acid rubber. , Phenolic resin, alkyd resin, polyester resin, unsaturated polyester resin, amino resin, epoxy resin, vinyl resin, vinyl chloride, vinyl chloride-vinyl acetate copolymer, acrylic resin, methacrylic resin, polyurethane resin, silicone resin, fluorine resin , Drying oil, synthetic drying oil, styrene / maleic acid resin, styrene / acrylic resin, polyamide resin, polyimide resin, benzoguanamine resin, melamine resin, urea resin chlorinated polypropylene, butyral resin, vinylidene chloride resin and the like. A photocurable resin may be used as the non-aqueous vehicle.

  Examples of the solvent used in the non-aqueous vehicle include aromatic solvents such as toluene, xylene, and methoxybenzene, and acetates such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Solvents, propionate solvents such as ethoxyethyl propionate, alcohol solvents such as methanol and ethanol, ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone solvents, aliphatic hydrocarbon solvents such as hexane, N, N-dimethylformamide, γ-butyrolactam, N Methyl-2-pyrrolidone, aniline, nitrogen compound-based solvent such as pyridine, a lactone-based solvents such as γ- butyrolactone, carbamic acid esters such as a mixture of 48:52 of methyl carbamate and ethyl carbamate acid.

The yellow pigment dispersion of the present invention preferably further contains a high boiling point organic solvent in an amount of 0.1 to 30% by mass based on the total amount of the yellow pigment dispersion. More preferably, it is 0.5-20 mass%, More preferably, it is 1.0-20 mass%.
The high-boiling organic solvent is an organic solvent having a boiling point of 150 ° C. or higher, and preferably 170 ° C. or higher. Examples thereof include high-boiling organic solvents described in JP-A Nos. 2001-262018, 2001-240763, 2001-335734, and 2002-80772. Among these, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, propylene glycol, butylene glycol, 1,2,6-hexanetriol, thioglycol, 1,2-hexanediol, glycerin, trimethylolethane, trimethyl Polyhydric alcohols such as methylolpropane, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol Polyvalent alcohol such as monobutyl ether Alkyl ethers, urea, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, more preferably propylene glycol, 1,2-hexanediol, glycerin, tri Methylolpropane, triethylene glycol monobutyl ether, and 2-pyrrolidone.

  The yellow pigment dispersion of the present invention can be obtained by dispersing the azo pigment and the aqueous or non-aqueous medium using a dispersing device. Dispersing devices include simple stirrer, impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, bead mill, attritor, roll mill, jet mill, paint shaker, agitator mill, etc.), ultrasonic method Further, a high-pressure emulsification dispersion system (high-pressure homogenizer; specific commercially available devices such as gorin homogenizer, microfluidizer, DeBEE2000, etc.) can be used.

  In the present invention, the volume average particle diameter of the pigment dispersion is preferably 0.01 μm to 0.2 μm. The volume average particle size of the pigment dispersion is the size of the pigment dispersion particles formed from the pigment and the pigment dispersant, or an additive such as a synergist (pigment derivative) attached to the pigment and the pigment dispersion. The particle size in the dispersion to which the additive has adhered. In the present invention, a Nanotrac UPA particle size analyzer (UPA-EX150; manufactured by Nikkiso Co., Ltd.) was used as a measuring device for the volume average particle diameter of the pigment. The measurement was performed according to a predetermined measuring method by placing 3 ml of the pigment dispersion in a measuring cell. As parameters to be input at the time of measurement, the ink viscosity was used as the viscosity, and the pigment density was used as the density of the dispersed particles.

  A more preferable volume average particle size is 20 nm or more and 200 nm or less, more preferably 30 nm or more and 180 nm or less, and most preferably 30 nm or more and 150 nm or less. When the volume average particle diameter of the particles in the pigment dispersion is less than 20 nm, there are cases where the storage stability cannot be ensured, while when it exceeds 250 nm, the optical density may be lowered.

  The concentration of the total pigment contained in the yellow pigment dispersion of the present invention is preferably in the range of 1 to 35% by mass, more preferably in the range of 2 to 25% by mass, and further 2 to 20% by mass. It is preferable that it is a range, and it is especially preferable that it is the range of 5-20 mass% among these. If the density is less than 1% by mass, sufficient image density may not be obtained when the pigment dispersion is used alone as the ink. If the concentration exceeds 35% by mass, the dispersion stability may decrease.

  Applications of the yellow pigment dispersion of the present invention include image recording materials for forming images, particularly color images, and specifically, thermal recording materials including ink jet recording materials described in detail below. , Pressure-sensitive recording materials, recording materials using electrophotography, transfer-type silver halide photosensitive materials, printing inks, recording pens, etc., preferably ink-jet recording materials, thermal recording materials, recording materials using electrophotography Yes, more preferably an ink jet recording material.

  The present invention can also be applied to a solid-state image pickup device such as a CCD, a color filter for recording / reproducing a color image used in a display such as an LCD or PDP, and a dyeing solution for dyeing various fibers.

  The yellow pigment dispersion of the present invention can be used in an emulsified dispersion state or further in a solid dispersion state depending on the system used.

  The yellow pigment dispersion of the present invention contains the azo pigment represented by the above formula (1) and the yellow pigment of group A as colorants. The yellow pigment dispersion of the present invention can contain a medium, but is particularly suitable as an ink for ink jet recording when a solvent is used as the medium. The coloring composition of the present invention can be produced by using a lipophilic medium or an aqueous medium as a medium and dispersing a colorant in the medium. Preferably, an aqueous medium is used. The yellow pigment dispersion of the present invention may contain other additives as required within a range that does not impair the effects of the present invention. Other additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, Known additives (described in JP-A No. 2003-306623) such as a foaming agent, a viscosity modifier, a dispersant, a dispersion stabilizer, a rust inhibitor, and a chelating agent can be used. These various additives are directly added to the ink liquid in the case of water-based ink. In the case of oil-based inks, it is common to add to the dispersion after preparation of the azo pigment dispersion, but it may be added to the oil phase or water phase at the time of preparation.

The penetration enhancer is preferably used for the purpose of allowing the ink for inkjet to penetrate better into paper. Examples of the penetration enhancer include alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, and nonionic surfactants. it can. If these are contained in the ink in an amount of 1 to 30% by mass, they usually have a sufficient effect, and it is preferable to use them in a range of addition amounts that do not cause printing bleeding and paper loss (print through).
The yellow pigment dispersion of the present invention preferably contains 1 to 20% by mass of a penetration enhancer based on the total amount of the yellow pigment dispersion. More preferably, it is contained at 1 to 15% by mass, and further preferably at 3 to 10% by mass.

[Ink for inkjet recording]
The ink for inkjet recording of the present invention (hereinafter sometimes referred to as “ink”) uses the yellow pigment dispersion described above. Preferably, it is prepared by mixing a water-soluble solvent, water and the like. However, if there is no particular problem, the pigment dispersion of the present invention may be used as it is.

  The content ratio of the pigment dispersion in the ink is preferably in the range of 1 to 100% by mass, and preferably 3 to 20% by mass in consideration of the hue, color density, saturation, transparency, etc. of the image formed on the recording medium. The range is particularly preferable, and the range of 3 to 10% by mass is most preferable among them.

  The pigment used in the present invention (that is, the azo pigment represented by the formula (1) and the yellow pigment of the group A) is contained in an amount of 0.1 to 20 parts by mass in 100 parts by mass of the ink. More preferably, it is contained in an amount of 0.2 to 10 parts by weight, more preferably 1 to 10 parts by weight, and most preferably 3.0 to 8.0 parts by weight. . In addition to the pigment used in the present invention, other pigments may be used in combination in the ink of the present invention. When other pigments are further used in combination, the total content of the pigments is preferably within the above range.

  The ink can be used not only for forming a single color image but also for forming a full color image. In order to form a full color image, a magenta color ink, a cyan color ink, and a yellow color ink can be used, and a black color ink may be further used to adjust the color tone.

  As the water-soluble solvent used in the ink, polyhydric alcohols, polyhydric alcohol derivatives, nitrogen-containing solvents, alcohols, sulfur-containing solvents and the like are used.

  Specific examples of polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2-hexanediol, 1,5-pentanediol, 1,2,6-hexanetriol, glycerin. Etc.

  Examples of the polyhydric alcohol derivatives include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, triethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, and dipropylene. Examples include glycol monobutyl ether and diglycerin ethylene oxide adducts.

  Examples of the nitrogen-containing solvent include pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, and triethanolamine. Examples of alcohols include alcohols such as ethanol, isopropyl alcohol, butyl alcohol, and benzyl alcohol. Examples of the solvent include thiodiethanol, thiodiglycerol, sulfolane, dimethyl sulfoxide and the like. In addition, propylene carbonate, ethylene carbonate, or the like can be used.

  The water-soluble solvent used in the present invention may be used alone or in combination of two or more. The content of the water-soluble solvent is 1% by mass or more and 60% by mass or less, preferably 5% by mass or more and 40% by mass or less of the entire ink. When the amount of the water-soluble solvent in the ink is less than 1% by mass, a sufficient optical density may not be obtained. Conversely, when the amount is more than 60% by mass, the viscosity of the liquid increases. In some cases, the ejection characteristics of the ink liquid become unstable.

  The preferred physical properties of the ink in the present invention are as follows. The surface tension of the ink is preferably 20 mN / m or more and 60 mN / m or less. More preferably, it is 20 mN or more and 45 mN / m or less, More preferably, it is 25 mN / m or more and 35 mN / m or less. If the surface tension is less than 20 mN / m, liquid may overflow on the nozzle surface of the recording head, and printing may not be performed normally. On the other hand, if it exceeds 60 mN / m, the permeability to the recording medium after printing may be slow, and the drying time may be slow. The surface tension was measured under the environment of 23 ° C. and 55% RH using a Wilhelmy surface tension meter as described above.

  The viscosity of the ink is preferably from 1.2 mPa · s to 8.0 mPa · s, more preferably from 1.5 mPa · s to less than 6.0 mPa · s, still more preferably from 1.8 mPa · s to 4. It is less than 5 mPa · s. When the viscosity is greater than 8.0 mPa · s, the dischargeability may be reduced. On the other hand, when it is smaller than 1.2 mPa · s, the long-term jetting property may deteriorate.

The viscosity (including those described later) was measured using a rotational viscometer Rheomat 115 (manufactured by Contraves) at 23 ° C. and a shear rate of 1400 s ⁻¹ .

  In addition to the components described above, water is added to the ink in the range of the above-described preferable surface tension and viscosity. The amount of water added is not particularly limited, but is preferably 10% by mass to 99% by mass, and more preferably 30% by mass to 80% by mass with respect to the entire ink.

  Furthermore, if necessary, for the purpose of controlling properties such as improvement in ejection properties, cellulose derivatives such as polyethyleneimine, polyamines, polyvinylpyrrolidone, polyethylene glycol, ethylcellulose, carboxymethylcellulose, polysaccharides and derivatives thereof, other water-soluble polymers, acrylics Polymer emulsion, polyurethane emulsion, polymer emulsion such as hydrophilic latex, hydrophilic polymer gel, cyclodextrin, macrocyclic amines, dendrimers, crown ethers, urea and derivatives thereof, acetamide, silicone surfactant, fluorine-based A surfactant or the like can be used.

  In order to adjust conductivity and pH, compounds of alkali metals such as potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide, triethanolamine, diethanolamine, ethanolamine, 2-amino-2-methyl Nitrogen-containing compounds such as -1-propanol, alkaline earth metal compounds such as calcium hydroxide, acids such as sulfuric acid, hydrochloric acid and nitric acid, strong acid and weak alkali salts such as ammonium sulfate, and the like can be used.

  In addition, a pH buffer, an antioxidant, a fungicide, a viscosity modifier, a conductive agent, an ultraviolet absorber, and the like can be added as necessary.

[Inkjet recording method, ink cartridge for inkjet recording, inkjet recording apparatus and inkjet recorded matter]
The ink jet recording method is a method of forming an image on the surface of a recording medium by using ink for ink jet recording and ejecting ink from the recording head of the ink jet recording apparatus to the surface of the recording medium in accordance with a recording signal.
Here, the ink jet recording apparatus is provided with a recording head that uses ink for ink jet recording and ejects ink (treatment liquid if necessary) onto the surface of the recording medium. By ejecting the ink from the recording head onto the surface of the recording medium, an image is obtained. Is a device for forming The ink jet recording apparatus supplies an ink cartridge for ink jet recording (hereinafter sometimes referred to as “ink cartridge”) that can supply ink to the recording head and is detachable from the main body of the ink jet recording apparatus. You may have. In this case, ink is stored in the ink cartridge for ink jet recording.

As the ink jet recording apparatus, a normal ink jet recording apparatus having a printing method capable of using ink for ink jet recording can be used. In addition to this, a heater for controlling the drying of the ink as necessary is provided. It may be mounted, or may be equipped with an intermediate transfer mechanism, and a mechanism for discharging (printing) ink and processing liquid onto the intermediate and then transferring it to a recording medium such as paper.
Further, an ink cartridge for ink jet recording is detachable from an ink jet recording apparatus provided with a recording head, and can be used as long as it has a configuration capable of supplying ink to the recording head while attached to the ink jet recording apparatus. A known ink cartridge can be used.

  The ink jet recording method (apparatus) preferably employs a thermal ink jet recording method or a piezo ink jet recording method from the viewpoint of the effect of improving bleeding and intercolor bleeding. In the case of the thermal ink jet recording method, the ink is heated at the time of ejection and has a low viscosity, but the viscosity rapidly increases because the temperature of the ink is lowered on the recording medium. For this reason, there is an effect of improving bleeding and intercolor bleeding. On the other hand, in the case of the piezo ink jet method, it is possible to discharge a high-viscosity liquid, and the high-viscosity liquid can suppress spreading in the paper surface direction on the recording medium. There is an improvement effect on intercolor bleeding.

  In the ink jet recording method (apparatus), replenishment (supply) of ink to the recording head is preferably performed from an ink cartridge filled with ink liquid (including a treatment liquid tank if necessary). The ink cartridge is preferably of a cartridge type that can be attached to and detached from the apparatus main body, and ink can be easily replenished by replacing the ink cartridge of this cartridge type.

  The ink jet recorded matter of the present invention is formed by forming an image using the above-described ink jet recording ink of the present invention. Here, the image formation can be suitably obtained by adopting an ink jet recording method using the above-described ink jet recording apparatus.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples at all. In the examples, “parts” represents parts by mass.

  The X-ray diffraction of the pigment composition of the present invention is measured using CuKα rays with a powder X-ray diffraction measurement apparatus RINT2500 (manufactured by Rigaku Corporation) in accordance with Japanese Industrial Standard JISK0131 (general rules for X-ray diffraction analysis). The test was performed under the following conditions.

Measuring instrument used: Automatic X-ray diffractometer RINT2500 manufactured by Rigaku
X-ray wound ball: Cu
Tube voltage: 55KV
Tube current: 280 mA
Scanning method: 2θ / θ scan Scanning speed: 6 deg. / Min.
Sampling interval: 0.100 deg.
Start angle (2θ): 5 deg.
Stop angle (2θ): 55 deg.
Divergence slit: 2 deg.
Scattering slit: 2 deg.
Resiping slit: 0.6mm
Using vertical goniometer

  [Synthesis Example 1] Synthesis of azo pigment composition (1)

  A synthesis scheme of the azo pigment (1) is shown below.

(1) Synthesis of intermediate (a) 29.7 g (0.3 mol) of methyl cyanoacetate, 42.4 g (0.4 mol) of trimethyl orthoformate, 20.4 g (0.2 mol) of acetic anhydride, p- Toluenesulfonic acid 0.5 g was added and heated to 110 ° C. (external temperature), and the mixture was stirred for 20 hours while distilling off low-boiling components generated from the reaction system. The reaction solution was concentrated under reduced pressure, and then purified on a silica gel column to obtain 14.1 g of the intermediate (a) (yellow powder, yield 30%). The NMR measurement result of the obtained intermediate (a) is as follows.
¹ H-NMR (300 MHz, CDCl ₃ ) 7.96 (s, 1H), 4.15 (s, 3H), 3.81 (s, 3H)

(2) Synthesis of Intermediate (b) 150 mL of isopropanol was added to 7.4 mL (141 mmol) of methyl hydrazine and cooled to 15 ° C. (internal temperature), and 7.0 g (49. 6 mmol) was gradually added, and the mixture was heated to 50 ° C. and stirred for 1 hour and 40 minutes. The reaction solution was concentrated under reduced pressure, and then purified on a silica gel column to obtain 10.5 g of the intermediate (b) (white powder, yield 50%). The NMR measurement result of the obtained intermediate (b) is as follows.
¹ H-NMR (300 MHz, CDCl ₃ ) 7.60 (s, 1H), 4.95 (brs, 2H), 3.80 (s, 3H), 3.60 (s, 3H)

(3) Synthesis of Intermediate (c) 298 mL of methanol was added to 387 mL (7.98 mol) of hydrazine monohydrate and cooled to 10 ° C. (internal temperature), and 149 g of 4,6-dichloropyrimidine was added to this mixed solution ( 1.00 mol) was gradually added (internal temperature 20 ° C. or lower), the ice bath was removed, the temperature was raised to room temperature, and the mixture was stirred at the same temperature for 30 minutes. Thereafter, the mixture was further heated to raise the internal temperature to 60 ° C. and stirred at the same temperature for 5 hours. After completion of the reaction, 750 mL of water was added, and the mixture was cooled with ice and cooled to an internal temperature of 8 ° C. The precipitated crystals were collected by filtration, washed with water, and washed with isopropanol. It dried at room temperature for 36 hours, and obtained the said intermediate body (c) by 119g (white powder, yield 84.5%). The NMR measurement result of the obtained intermediate (c) is as follows.
¹ H-NMR (300 MHz, d-DMSO) 7.80 (s, 1H), 7.52 (s, 2H), 5.98 (s, 1H), 4.13 (s, 4H)

(4) Synthesis of Intermediate (d) To 50 g (357 mmol) of Intermediate (c), 128 mL of water was added and stirred at room temperature. To this suspension, 98.2 g (785 mmol) of pivaloylacetonitrile was added, and 12M hydrochloric acid was added dropwise at the same temperature to pH 3, and then heated until the internal temperature reached 50 ° C. For 6 hours. After completion of the reaction, the solution was neutralized by adding 8N aqueous potassium hydroxide solution to pH 6.4. The mixture was cooled with ice and cooled to an internal temperature of 10 ° C., and the precipitated crystals were collected by filtration and washed with water. The obtained crystal was dried at 60 ° C. under reduced pressure, and 30 mL of toluene was added to the obtained crude product, and heated to 60 ° C. for dissolution. The obtained solution was allowed to stand at room temperature for 12 hours, and the precipitated crystals were collected by filtration, washed with cooled toluene and dried at 60 ° C. under reduced pressure, and 87.7 g of the intermediate (d) (white powder) Yield 69.3%). The NMR measurement result of the obtained intermediate (d) is as follows.
¹ H-NMR (300 MHz, d-DMSO) 8.74 (s, 1H), 7.99 (s, 1H), 6.87 (s, 4H), 5.35 (s, 2H), 1.24 (s, 18H)

(5) Synthesis of azo pigment (1)

  In a mixed solution of 55 mL of acetic acid and 37 mL of propionic acid, 9.2 g of intermediate (b) was dissolved at room temperature. The inner temperature was cooled to -3 ° C by cooling with ice, and a 40 mass% sulfuric acid solution of nitrosylsulfuric acid was added dropwise over 10 minutes at an inner temperature of -3 ° C to 4 ° C. After stirring for 1 hour at an internal temperature of 4 ° C., 0.2 g of urea was added, and then the internal temperature was cooled to −3 ° C. and further stirred for 10 minutes to obtain a diazonium salt solution. Separately, 10 g of intermediate (d) was completely dissolved in 150 mL of acetone, then the internal temperature was cooled to 17 ° C., and added to the above diazonium salt solution over 25 minutes within the range of the internal temperature of −3 ° C. to 3 ° C. . After completion of the addition, the mixture was stirred at 3 ° C. for 30 minutes, then the ice bath was removed and the temperature was raised to room temperature over 30 minutes. After stirring at room temperature for 30 minutes, the obtained crystals were separated by filtration, washed with 150 mL of acetone, and further washed with 100 mL of water. The obtained crystals were suspended in 400 mL of water without drying, and an 8N aqueous potassium hydroxide solution was added to adjust the pH to 5.7. After stirring at room temperature for 20 minutes, the obtained crystals were separated by filtration, thoroughly washed with water, and then washed with 80 mL of acetone. The obtained crystal was dried at room temperature for 12 hours.

The obtained crystals were suspended in 580 mL of acetone and then stirred for 30 minutes under reflux. Then, it cooled to room temperature over 10 minutes, the obtained crystal | crystallization was separated by filtration, and it was made to dry at room temperature for 5 hours, and 17.1g of azo pigments (1) were obtained. Yield 88.5%.
When the obtained azo pigment (1) was visually observed with a transmission microscope (manufactured by JEOL Ltd .: JEM-1010 electron microscope), the length of the primary particles in the major axis direction was about 15 μm. It was.
When the X-ray diffraction of the azo pigment (1) was measured under the above-mentioned conditions, the characteristic X in the Bragg angles (2θ ± 0.2 °) of 7.6 °, 25.6 ° and 27.7 ° was obtained. A line diffraction peak was shown. A CuKα characteristic X-ray diffraction diagram is shown in FIG.

[Synthesis Example 2] Synthesis of vinyl polymer solution (1) The components of the following monomer composition were mixed so that the total amount was 100 parts by mass, and 2,2'-azobis (2,4-dimethylvaleronitrile was further used as a polymerization initiator. ) 1 part by mass was added, and nitrogen gas substitution was sufficiently performed to obtain a synthetic mixed solution.

Phenoxyethyl methacrylate 54.9 parts by weight Methyl methacrylate 35 parts by weight Methacrylic acid 10 parts by weight 2-Mercaptoethanol 0.1 parts by weight

  Next, 100 parts by mass of methyl ethyl ketone was heated to 75 ° C. with stirring in a nitrogen atmosphere. The synthetic mixture was added dropwise over 3 hours at 75 ° C. with stirring. The reaction was further continued at 75 ° C. with stirring for 5 hours. Thereafter, the reaction product was naturally cooled to 25 ° C. and then diluted by adding methyl ethyl ketone so that the solid content was 50%, to obtain a vinyl polymer solution (1) having an average molecular weight of 41,000.

Example 1 Preparation of Pigment Dispersion 1 2.25 parts by mass of azo pigment (1) synthesized in Synthesis Example 1 and C.I. I. 145 parts by weight of Pigment Yellow 74 (Iralite YELLOW GO manufactured by Ciba Specialty), 0.5 parts by weight of sodium oleate, 5 parts by weight of glycerin, and 42 parts by weight of water are mixed, and zirconia beads 100 having a diameter of 0.1 mm are mixed. Dispersion was performed at 300 rpm for 3 hours using a planetary ball mill together with the mass part. After completion of the dispersion, the zirconia beads were separated to obtain a yellow pigment dispersion 1 (volume average particle size; Mv≈68 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).

Example 2 Preparation of Pigment Dispersion 2 2.0 parts by mass of the azo pigment (1) synthesized in Synthesis Example 1 was obtained. I. 0.5 parts by weight of Pigment Yellow 74 (Iralite YELLOW GO manufactured by Ciba Specialty), 0.5 parts by weight of sodium oleate, 5 parts by weight of glycerin, and 42 parts by weight of water are mixed, and zirconia beads 100 having a diameter of 0.1 mm are mixed. Dispersion was performed at 300 rpm for 3 hours using a planetary ball mill together with the mass part. After completion of the dispersion, the zirconia beads were separated to obtain a yellow pigment dispersion 2 (volume average particle diameter; Mv≈73 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).

Example 3 Production of Pigment Dispersion 3 1.5 parts by mass of the azo pigment (1) synthesized in Synthesis Example 1 and C.I. I. Pigment Yellow 74 (Iralite YELLOW GO manufactured by Ciba Specialty Inc.) 1.0 part by mass, 0.5 part by mass of sodium oleate, 5 parts by mass of glycerin, and 42 parts by mass of water are mixed, and zirconia beads 100 having a diameter of 0.1 mm are mixed. Dispersion was performed at 300 rpm for 3 hours using a planetary ball mill together with the mass part. After the completion of dispersion, zirconia beads were separated to obtain yellow pigment dispersion 3 (volume average particle diameter; Mv≈77 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).

Example 4 Preparation of Pigment Dispersion 4 The azo pigment (1) synthesized in Synthesis Example 1 was added in an amount of 1.25 parts by mass, C.I. I. 145 parts by weight of Pigment Yellow 74 (Iralite YELLOW GO manufactured by Ciba Specialty), 0.5 parts by weight of sodium oleate, 5 parts by weight of glycerin, and 42 parts by weight of water are mixed, and zirconia beads 100 having a diameter of 0.1 mm are mixed. Dispersion was performed at 300 rpm for 3 hours using a planetary ball mill together with the mass part. After the completion of dispersion, zirconia beads were separated to obtain yellow pigment dispersion 4 (volume average particle diameter; Mv≈78 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).

Example 5 Production of Pigment Dispersion 5 2.25 parts by mass of the azo pigment (1) synthesized in Synthesis Example 1 and C.I. I. 0.25 parts by mass of Pigment Yellow 155 (INKJET YELLOW 4G VP2532 manufactured by Clariant), 0.5 parts by mass of sodium oleate, 5 parts by mass of glycerin, and 42 parts by mass of water were mixed to give zirconia beads 100 having a diameter of 0.1 mm. Dispersion was performed at 300 rpm for 2 hours using a planetary ball mill together with the mass part. After completion of the dispersion, zirconia beads were separated to obtain a yellow pigment dispersion 5 (volume average particle diameter; Mv≈70 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).

Example 6 Preparation of Pigment Dispersion 6 The azo pigment (1) synthesized in Synthesis Example 1 was added in an amount of 2.0 parts by mass, C.I. I. Pigment Yellow 155 (INKJET YELLOW 4G VP2532 manufactured by Clariant) 0.5 parts by mass, 0.5 parts by mass of sodium oleate, 5 parts by mass of glycerin, and 42 parts by mass of water are mixed, and zirconia beads 100 having a diameter of 0.1 mm are mixed. Dispersion was performed at 300 rpm for 3 hours using a planetary ball mill together with the mass part. After completion of the dispersion, the zirconia beads were separated to obtain a yellow pigment dispersion 6 (volume average particle diameter; Mv≈75 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).

Example 7 Production of Pigment Dispersion 7 1.5 parts by mass of azo pigment (1) synthesized in Synthesis Example 1 I. Pigment Yellow 155 (Clariant INKJET YELLOW 4G VP2532) 1.0 part by mass, sodium oleate 0.5 part by mass, glycerin 5 part by mass, and water 42 parts by mass are mixed, and zirconia beads 100 having a diameter of 0.1 mm are mixed. Dispersion was performed at 300 rpm for 3 hours using a planetary ball mill together with the mass part. After completion of the dispersion, zirconia beads were separated to obtain a yellow pigment dispersion 7 (volume average particle diameter; Mv≈79 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).

Example 8 Production of Pigment Dispersion 8 The azo pigment (1) synthesized in Synthesis Example 1 was added in an amount of 1.25 parts by mass, C.I. I. 1.25 parts by mass of Pigment Yellow 155 (INKJET YELLOW 4G VP2532 manufactured by Clariant), 0.5 parts by mass of sodium oleate, 5 parts by mass of glycerin, and 42 parts by mass of water were mixed to give zirconia beads 100 having a diameter of 0.1 mm. Dispersion was performed at 300 rpm for 3 hours using a planetary ball mill together with the mass part. After completion of the dispersion, the zirconia beads were separated to obtain a yellow pigment dispersion 8 (volume average particle diameter; Mv≈78 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).

Example 9 Production of Pigment Dispersion 9 2.25 parts by mass of the azo pigment (1) synthesized in Synthesis Example 1 and C.I. I. Pigment Yellow 110 (IRGAZIN YELLOW 2RLT manufactured by Ciba Specialty Co., Ltd.) 0.25 parts by mass, sodium oleate 0.5 parts by mass, glycerin 5 parts by mass, and water 42 parts by mass are mixed, and zirconia beads 100 having a diameter of 0.1 mm are mixed. Dispersion was performed at 300 rpm for 3 hours using a planetary ball mill together with the mass part. After completion of the dispersion, zirconia beads were separated to obtain a yellow pigment dispersion 9 (volume average particle size; Mv≈76 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).

Example 10 Production of Pigment Dispersion 10 2.25 parts by mass of the azo pigment (1) synthesized in Synthesis Example 1 and C.I. I. 0.25 parts by mass of Pigment Yellow 128 (CROMOPHTAL YELLOW 8GN manufactured by Ciba Specialty), 0.5 parts by mass of sodium oleate, 5 parts by mass of glycerin, and 42 parts by mass of water are mixed, and zirconia beads 100 having a diameter of 0.1 mm are mixed. Dispersion was performed at 300 rpm for 3 hours using a planetary ball mill together with the mass part. After completion of the dispersion, the zirconia beads were separated to obtain a yellow pigment dispersion 10 (volume average particle diameter; Mv≈79 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).

Example 11 Production of Pigment Dispersion 11 2.25 parts by mass of azo pigment (1) synthesized in Synthesis Example 1 was obtained. I. Pigment Yellow 138 (PASFIOTL L YELLOW 0960 HD manufactured by BASF) was mixed with 0.25 parts by mass, sodium oleate 0.5 parts by mass, glycerin 5 parts by mass, and water 42 parts by mass, and zirconia beads having a diameter of 0.1 mm. Dispersion was performed at 300 rpm for 3 hours using a planetary ball mill together with 100 parts by mass. After completion of the dispersion, the zirconia beads were separated to obtain a yellow pigment dispersion 11 (volume average particle diameter; Mv≈76 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).

Example 12 Production of Pigment Dispersion 12 2.25 parts by mass of the azo pigment (1) synthesized in Synthesis Example 1 and C.I. I. 0.25 parts by mass of Pigment Yellow 139 (PALIOTOL D YELLOW 1891 manufactured by BASF), 0.5 parts by mass of sodium oleate, 5 parts by mass of glycerin, and 42 parts by mass of water are mixed, and zirconia beads 100 having a diameter of 0.1 mm are mixed. Dispersion was performed at 300 rpm for 3 hours using a planetary ball mill together with the mass part. After completion of the dispersion, the zirconia beads were separated to obtain a yellow pigment dispersion 12 (volume average particle diameter; Mv≈78 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).

Example 13 Production of Pigment Dispersion 13 2.25 parts by mass of azo pigment (1) synthesized in Synthesis Example 1 and C.I. I. Pigment Yellow 150 (CROMOPHTAL YELLOW LA2 manufactured by Ciba Specialty Co., Ltd.) 0.25 parts by mass, sodium oleate 0.5 parts by mass, glycerin 5 parts by mass, and water 42 parts by mass are mixed, and zirconia beads 100 having a diameter of 0.1 mm are mixed. Dispersion was performed at 300 rpm for 3 hours using a planetary ball mill together with the mass part. After completion of the dispersion, the zirconia beads were separated to obtain a yellow pigment dispersion 13 (volume average particle diameter; Mv≈65 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).

Example 14 Production of Pigment Dispersion 14 2.25 parts by mass of azo pigment (1) synthesized in Synthesis Example 1 and C.I. I. Pigment Yellow 185 (PASFIOTL YELLOW D1155 manufactured by BASF) was mixed with 0.25 parts by mass, 0.5 parts by mass of sodium oleate, 5 parts by mass of glycerin, and 42 parts by mass of water, and 100 parts by mass of zirconia beads having a diameter of 0.1 mm. Using a planetary ball mill together with the part, dispersion was performed at 300 rpm for 3 hours. After completion of the dispersion, zirconia beads were separated to obtain a yellow pigment dispersion 14 (volume average particle diameter; Mv≈71 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).

Example 15 Production of Pigment Dispersion 15 2.25 parts by mass of the azo pigment (1) synthesized in Synthesis Example 1 and C.I. I. 0.25 parts by mass of Pigment Yellow 213 (Hostaper Yellow H5G manufactured by Clariant), 0.5 parts by mass of sodium oleate, 5 parts by mass of glycerin, and 42 parts by mass of water were mixed, and 100 parts by mass of zirconia beads having a diameter of 0.1 mm. Using a planetary ball mill together with the part, dispersion was performed at 300 rpm for 3 hours. After completion of the dispersion, the zirconia beads were separated to obtain a yellow pigment dispersion 15 (volume average particle diameter; Mv≈66 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).

Comparative Example 1 Preparation of Comparative Pigment Dispersion 1 2.25 parts by mass of azo pigment (1) used in Example 1 and C.I. I. A total of 2.5 parts by mass of C.I. I. Pigment Yellow 74 (Iralite YELLOW GO manufactured by Ciba Specialty) was replaced with 2.5 parts by mass in the same manner as in Example 1 except that the dispersion time was 100 nm or less (volume average particle size (Mv) of the pigment dispersion). Volume average particle diameter; Mv≈68 nm: Measurement was carried out until it was measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd., and a yellow comparative pigment dispersion 1 was obtained.

Comparative Example 2 Preparation of Comparative Pigment Dispersion 2 2.25 parts by mass of azo pigment (1) used in Example 5 and C.I. I. A total of 2.5 parts by mass of C.I. I. Pigment Yellow 155 (Clariant INKJET YELLOW 4G VP2532) was replaced with 2.5 parts by mass in the same manner as in Example 5 except that the dispersion time was 100 nm or less (volume volume average particle size (Mv) of the pigment dispersion). Average particle size: Mv≈38 nm: Measurement was carried out until measurement was performed using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd., to obtain a yellow comparative pigment dispersion 2.

[Comparative Example 3] Preparation of Comparative Pigment Dispersion 3 2.25 parts by mass of azo pigment (1) used in Example 9 and C.I. I. A total of 2.5 parts by mass of C.I. I. Pigment yellow 110 (IRGAZIN YELLOW 2RLT manufactured by Ciba Specialty) was replaced with 2.5 parts by mass in the same manner as in Example 9, and the volume average particle diameter (Mv) of the pigment dispersion was 100 nm or less (volume). Average particle diameter: Mv≈55 nm: Measurement was carried out until it was measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd., and a yellow comparative pigment dispersion 3 was obtained.

[Comparative Example 4] Preparation of Comparative Pigment Dispersion 4 2.25 parts by mass of azo pigment (1) used in Example 10 and C.I. I. A total of 2.5 parts by mass of C.I. I. Pigment Yellow 128 (CROMOPHTAL YELLOW 8GN manufactured by Ciba Specialty) was replaced with 2.5 parts by mass in the same manner as in Example 10, but the volume average particle size (Mv) of the pigment dispersion was 100 nm or less (volume). Average particle diameter: 50 Mv≈nm: Measurement was carried out until it was measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd., and a yellow comparative pigment dispersion 4 was obtained.

[Comparative Example 5] Preparation of Comparative Pigment Dispersion 5 2.25 parts by mass of azo pigment (1) used in Example 11 and C.I. I. A total of 2.5 parts by mass of 0.25 parts by mass of CI Pigment Yellow 138; I. Pigment Yellow 138 (BASF PALIOTOL L YELLOW 0960 HD) was replaced with 2.5 parts by mass in the same manner as in Example 11 except that the dispersion time was 100 nm or less (volume average particle size (Mv) of the pigment dispersion). Volume average particle diameter; Mv≈78 nm: Measurement was carried out until it was measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd., and a yellow comparative pigment dispersion 5 was obtained.

Comparative Example 6 Preparation of Comparative Pigment Dispersion 6 2.25 parts by mass of azo pigment (1) used in Example 12 and C.I. I. A total of 2.5 parts by mass of C.I. I. Pigment Yellow 139 (BASF PALIOTOL D YELLOW 1891) was replaced with 2.5 parts by mass in the same manner as in Example 12 except that the dispersion time was 100 nm or less (volume average particle size (Mv) of the pigment dispersion). Average particle diameter; Mv≈51 nm: Measurement was carried out until measurement was performed using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd., thereby obtaining a yellow comparative pigment dispersion 6.

Comparative Example 7 Preparation of Comparative Pigment Dispersion 7 2.25 parts by mass of azo pigment (1) used in Example 13 and C.I. I. A total of 2.5 parts by mass of C.I. I. Pigment Yellow 150 (CROMOPHTAL YELLOW LA2 manufactured by Ciba Specialty) was replaced with 2.5 parts by mass in the same manner as in Example 13, and the volume average particle size (Mv) of the pigment dispersion was 100 nm or less (volume). Average particle diameter; Mv67≈nm: Measurement was performed until measurement was performed using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd., to obtain a yellow comparative pigment dispersion 7.

[Comparative Example 8] Preparation of Comparative Pigment Dispersion 8 2.25 parts by mass of azo pigment (1) used in Example 14 and C.I. I. A total of 2.5 parts by mass of C.I. I. Pigment Yellow 185 (BASF PALIOTOL YELLOW D1155) was replaced with 2.5 parts by mass in the same manner as in Example 14 except that the dispersion time was 100 nm or less (volume average). Particle diameter; Mv70≈nm: measured until it was measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd., to obtain a yellow comparative pigment dispersion 8.

[Comparative Example 9] Preparation of Comparative Pigment Dispersion 9 2.25 parts by mass of azo pigment (1) used in Example 15 and C.I. I. A total of 2.5 parts by mass of C.I. I. Pigment Yellow 213 (Clariant Hostaper Yellow H5G) was replaced with 2.5 parts by mass in the same manner as in Example 15 except that the dispersion time was 100 nm or less (volume average). Particle diameter; Mv≈44 nm: Measurement was performed until measurement was performed using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd., and a yellow comparative pigment dispersion 9 was obtained.

[Comparative Example 10] Preparation of Comparative Pigment Dispersion 10 2.25 parts by mass of azo pigment (1) used in Example 1 and C.I. I. The same procedure as in Example 1 was conducted except that 2.5 parts by mass of 0.25 parts by mass of Pigment Yellow 74 was replaced with 2.5 parts by mass of the compound represented by the following formula (DYE-1). However, it was dissolved and could not be dispersed.

<Dispersibility>
Mix 2.5 parts by weight of pigment, 0.5 parts by weight of sodium oleate, 5 parts by weight of glycerin and 42 parts by weight of water, and rotate at 300 rpm using a planetary ball mill with 100 parts by weight of zirconia beads having a diameter of 0.1 mm. As a result of measuring the particle size of the dispersion at the point where the dispersion was performed for 3 hours, X indicates that coarse particles of 100 nm or more are confirmed, XX indicates that the particles cannot be dispersed, and ○ indicates that almost no particles are confirmed. Inventive pigment dispersions 1-15 and comparative pigment dispersions 1-10 were evaluated. The results are shown in Table-1.

<Dispersion stability>
The pigment dispersions obtained in Examples 1 to 15 and Comparative Examples 1 to 10 were allowed to stand at room temperature for 4 weeks. As a result, the case where the precipitate was visually confirmed was rated as x, and the case where the precipitate was not confirmed was marked as ◯. The results are shown in Table-1.

<Evaluation of coloring power>
The pigment dispersions obtained in Examples 1 to 15 and Comparative Examples 1 to 9 are No. 3 was applied to a photomat paper manufactured by Epson. The image density of the obtained coated material was measured using a reflection densitometer (X-Rite 938 manufactured by X-Rite), and “coloring power (OD: Optical Density)” was evaluated according to the following criteria. The case where the OD was 1.4 or more was rated ◎, the case where the OD was 1.2 or more and less than 1.4, and the case where it was less than 1.2, ×. The results are shown in Table-1.

<Hue evaluation>
Regarding the hue, ◎ (good) if the chromaticity of the coated material obtained above is visually green and large vividness, ◯ if either one does not apply, and one that does not apply either Evaluation was performed as x (defect). The results are shown in Table-1.

<Light fastness evaluation>
A coated product having an image density of 1.0 used for hue evaluation was prepared, xenon light (99000 lux; in the presence of a TAC filter) was irradiated for 14 days using a fade meter, and the image density before and after the xenon irradiation was measured using a reflection densitometer. ◎ when the residual ratio of dye [(concentration after irradiation / concentration before irradiation) × 100%] is 90% or more, ○ when it is 80% or more and less than 90%, and when it is 60% or more and less than 80%. (Triangle | delta) and the case of less than 60% were set to x, and the pigment dispersions 1-15 and the comparative pigment dispersions 1-9 were evaluated. The results are shown in Table-1.

<Ozone gas fastness evaluation>
Create a coating with an image density of 1.0 used for hue evaluation, expose the ozone concentration to 5.0 ppm at 25 ° C and 50% humidity for 28 days, measure the image density before and after exposure to ozone gas using a reflection densitometer, Dye residual ratio [(post-irradiation density / pre-irradiation density) × 100%] is 90% or more, ◎, 80% to less than 90%, ７０, 70% to less than 80%, △, 70% The pigment dispersions 1 to 15 and the comparative pigment dispersions 1 to 9 were evaluated with x being less than x. The results are shown in Table-1.
For example, “(1) / PY-74 = 9/1” in the table represents azo pigment (1) and C.I. I. This means that CI Pigment Yellow 74 was used at a mass ratio of 9: 1.

[Example 16] Preparation of yellow pigment ink liquid 1 The yellow pigment dispersion 1 obtained in Example 1 was 5% by mass in solid content, 10% by mass glycerin, 5% by mass 2-pyrrolidone, 1,2-hexane. 2% by mass of diol, 2% by mass of triethylene glycol monobutyl ether, 0.5% by mass of propylene glycol, 1% by mass of Surfynol 465 (nonionic surfactant manufactured by Air Products), 74.5% by mass of ion-exchanged water Each component was added so that the resulting mixture was filtered with a 20 ml syringe equipped with a 1.2 μm filter (acetylcellulose membrane, outer diameter: 25 mm, manufactured by Fuji Film Co., Ltd.), and coarse particles The yellow pigment ink liquid 1 was obtained by removing.

[Example 17] Preparation of yellow pigment ink liquid 2 A yellow pigment ink liquid was prepared in the same manner as in Example 16 except that the pigment dispersion 2 obtained in Example 2 was used instead of the yellow pigment dispersion 1. 2 was obtained.

[Example 18] Preparation of yellow pigment ink liquid 3 A yellow pigment ink liquid was prepared in the same manner as in Example 16 except that the pigment dispersion 3 obtained in Example 3 was used instead of the yellow pigment dispersion 1. 3 was obtained.

[Example 19] Preparation of yellow pigment ink liquid 4 A yellow pigment ink liquid was prepared in the same manner as in Example 16 except that the pigment dispersion 4 obtained in Example 4 was used instead of the yellow pigment dispersion 1. 4 was obtained.

[Example 20] Preparation of yellow pigment ink liquid 5 A yellow pigment ink liquid was prepared in the same manner as in Example 16 except that the pigment dispersion 5 obtained in Example 5 was used instead of the yellow pigment dispersion 1. 5 was obtained.

[Example 21] Preparation of yellow pigment ink liquid 6 A yellow pigment ink liquid was prepared in the same manner as in Example 16 except that the pigment dispersion 6 obtained in Example 6 was used instead of the yellow pigment dispersion 1. 6 was obtained.

[Example 22] Preparation of yellow pigment ink liquid Yellow pigment ink liquid was prepared in the same manner as in Example 16 except that the pigment dispersion 7 obtained in Example 7 was used instead of the yellow pigment dispersion 1. 7 was obtained.

[Example 23] Preparation of yellow pigment ink liquid Yellow pigment ink liquid was prepared in the same manner as in Example 16 except that the pigment dispersion 8 obtained in Example 8 was used in place of the yellow pigment dispersion 1. 8 was obtained.

[Example 24] Preparation of yellow pigment ink liquid 9 A yellow pigment ink liquid was prepared in the same manner as in Example 16 except that the pigment dispersion 9 obtained in Example 9 was used instead of the yellow pigment dispersion 1. 9 was obtained.

Example 25 Preparation of Yellow Pigment Ink Liquid 10 A yellow pigment ink liquid was prepared in the same manner as in Example 16 except that the pigment dispersion 10 obtained in Example 10 was used instead of the yellow pigment dispersion 1. 10 was obtained.

Example 26 Preparation of Yellow Pigment Ink Liquid 11 A yellow pigment ink liquid was prepared in the same manner as in Example 16 except that the pigment dispersion 11 obtained in Example 11 was used instead of the yellow pigment dispersion 1. 11 was obtained.

[Example 27] Preparation of yellow pigment ink liquid Yellow pigment ink liquid was prepared in the same manner as in Example 16 except that the pigment dispersion 12 obtained in Example 12 was used in place of the yellow pigment dispersion 1. 12 was obtained.

[Example 28] Preparation of yellow pigment ink liquid Yellow pigment ink liquid was prepared in the same manner as in Example 16 except that the pigment dispersion 13 obtained in Example 13 was used instead of the yellow pigment dispersion 1. 13 was obtained.

[Example 29] Preparation of yellow pigment ink liquid Yellow pigment ink liquid was prepared in the same manner as in Example 16 except that the pigment dispersion 14 obtained in Example 14 was used instead of the yellow pigment dispersion 1. 14 was obtained.

[Example 30] Preparation of yellow pigment ink liquid 15 A yellow pigment ink liquid was prepared in the same manner as in Example 16 except that the pigment dispersion 15 obtained in Example 15 was used instead of the yellow pigment dispersion 1. 15 was obtained.

[Comparative Example 11] Preparation of Comparative Yellow Pigment Ink Liquid 1 Comparative yellow as in Example 16 except that the comparative pigment dispersion 1 obtained in Comparative Example 1 was used in place of the yellow pigment dispersion 1. A pigment ink liquid 1 was obtained.

[Comparative Example 12] Preparation of Comparative Yellow Pigment Ink Liquid 2 Comparative yellow as in Example 16 except that the comparative pigment dispersion 2 obtained in Comparative Example 2 was used in place of the yellow pigment dispersion 1. A pigment ink liquid 2 was obtained.

[Comparative Example 13] Preparation of Comparative Yellow Pigment Ink Liquid 3 Comparative yellow as in Example 16 except that the comparative pigment dispersion 4 obtained in Comparative Example 4 was used in place of the yellow pigment dispersion 1. A pigment ink liquid 3 was obtained.

Example 31
The yellow pigment ink liquids of Examples 16 to 30 and Comparative Examples 11 to 13 were filled in a yellow ink liquid cartridge of an ink jet printer PX-V630 manufactured by Seiko Epson Corporation, and the image receiving paper was manufactured by Seiko Epson Corporation. Photographic paper Crispier <high gloss>, color setting: no color correction, print quality: a single color image pattern of yellow with the density changed stepwise so that the OD value of yellow is 0.7 to 1.8 A printed matter was obtained by printing. The recorded material was evaluated for hue, printing characteristics, image fastness (light resistance and ozone gas resistance) and image quality.

[Hue test method]
The reflection density of each recorded matter of Example 31 in which a yellow single-color image pattern having a stepwise change in density was printed with an ink jet printer was measured using a spectrophotometer GRETAG SPM-50 (manufactured by GRETAG).
Measurement conditions were light source D50, no light source filter, white standard was absolute white, viewing angle was 2 °, and L * value, a * value, and b * value defined by CIE were obtained. Evaluation was made based on the following criteria.

[Criteria]
Evaluation A: When a * = 0, when b * ≧ 95 and b * = 95, a * ≦ −5,
When -5 ≦ a * ≦ 0 and b * ≦ 30 and 60 ≦ b * ≦ 95, a * ≦ −10
Evaluation ○: Applicable to any one of the conditions of evaluation ◎ Evaluation ×: Applicable to any of the conditions of evaluation ◎

[Evaluation of coloring power]
The above yellow pigment ink liquid is loaded into a yellow ink liquid cartridge of an ink jet printer PX-V630 manufactured by Seiko Epson Corporation, and the image receiving sheet is color set to Seiko Epson Co., Ltd. photographic paper Krispia <high gloss>: color No correction, print quality: A yellow solid print pattern is created with a photo, and a single color density of 2.0 ≦ ODmax is ◎, 1.8 ≦ ODmax <2.0 is ○, 1.5 ≦ ODmax < A value of 1.8 was evaluated as x.

[Light fastness test method]
Using a weather meter (manufactured by Atlas), the image was irradiated with xenon light (99,000 lux) for 14 days. The OD value of a single color (yellow) recorded in each recorded matter of Example 31 was measured using a reflection densitometer (X-Rite 310TR) at every elapse of a certain period from the start of irradiation. The reflection density was measured at three points of 0.7, 1.0, and 1.8.
From the obtained results, the residual optical density (ROD) was determined using the following formula: ROD (%) = (D / D ₀ ) × 100. (In the formula, D represents the OD value after the exposure test, and D ₀ represents the OD value before the exposure test.)
Furthermore, based on the result of the above test, the light resistance of the image recorded on the recorded material was evaluated using the following criteria.

(Criteria)
Evaluation A: ROD 14 days after the start of the test is 85% or more at any concentration.
Evaluation (circle): ROD 14 days after the start of a test has the density | concentration of any one point less than 85%.
Evaluation Δ: ROD 14 days after the start of the test, the concentration at any two points is less than 85%.
Evaluation x: ROD 14 days after the start of the test is less than 85% at all concentrations.
In this test, a recorded matter with little decrease in ROD even when exposed to light for a long time is excellent.
The obtained results are shown in Table 2-1 as “light fastness”.

[Ozone gas fastness test method]
The recorded material was exposed to ozone gas for 28 days under the condition that the ozone gas concentration was set to 5 ppm (25 ° C .; 50% RH). The ozone gas concentration was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS. The OD value of a single color (yellow) recorded on photographic paper Krispia <High Gloss> manufactured by Seiko Epson Corporation was measured using a reflection densitometer (X-Rite 310TR) after a certain period from the start of exposure. . The reflection density was measured at three points of 0.7, 1.0, and 1.8.
From the obtained results, the residual optical density (ROD) was determined using the following formula: ROD (%) = (D / D ₀ ) × 100. (In the formula, D represents the OD value after the exposure test, and D ₀ represents the OD value before the exposure test.)
Furthermore, based on the result of the above test, the ozone resistance of the image recorded on the recorded material was evaluated using the following criteria.

(Criteria)
Evaluation A: ROD after 28 days from the start of the test is 85% or more at any concentration.
Evaluation ○: ROD after 28 days from the start of the test, the concentration at any one point is less than 85%.
Evaluation Δ: ROD after 28 days from the start of the test, the concentration at any two points is less than 85%.
Evaluation x: ROD after 28 days from the start of the test is less than 85% at all concentrations.
In this test, a recorded material with little decrease in ROD is excellent even when exposed to ozone for a long time.
The obtained results are shown in Table 2-1 as “Ozone gas fastness”.

[Example 32]
The yellow pigment ink liquids of Examples 16 to 30 and Comparative Examples 11 to 13 were filled in a yellow ink liquid cartridge of an ink jet printer PX-V630 manufactured by Seiko Epson Corporation, and the image receiving paper was a normal one manufactured by Xerox Corporation. Color (color correction: no color correction) on paper (4024), print quality: photo prints and records a yellow single-color image pattern whose density changes stepwise so that the OD value of yellow is 0.3 to 1.0. I got a thing. The recorded material was evaluated for hue, printing characteristics, image fastness (light resistance and ozone gas resistance) and image quality.

[Light fastness test method]
Using a weather meter (manufactured by Atlas), the image was irradiated with xenon light (99,000 lux) for 14 days. The OD value of a single color (yellow) recorded on each recorded matter of Example 32 was measured using a reflection densitometer (X-Rite 310TR) after a certain period of time from the start of irradiation. The reflection density was measured at three points of 0.5, 0.8 and 1.0.
From the obtained results, the residual optical density (ROD) was determined using the following formula: ROD (%) = (D / D ₀ ) × 100. (In the formula, D represents the OD value after the exposure test, and D ₀ represents the OD value before the exposure test.)
Furthermore, based on the result of the above test, the light fastness of the image recorded on the recorded material was evaluated using the following criteria.

(Criteria)
Evaluation A: ROD 14 days after the start of the test is 85% or more at any concentration.
Evaluation (circle): ROD 14 days after the start of a test has the density | concentration of any one point less than 85%.
Evaluation Δ: ROD 14 days after the start of the test, the concentration at any two points is less than 85%.
Evaluation x: ROD 14 days after the start of the test is less than 85% at all concentrations.
In this test, a recorded matter with little decrease in ROD even when exposed to light for a long time is excellent.
The obtained results are shown in Table 2-2 as “light fastness”.

[Ozone gas fastness test method]
The recorded matter was exposed to ozone gas for 14 days under the condition that the ozone gas concentration was set to 5 ppm (25 ° C .; 50% RH). The ozone gas concentration was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS. The OD value of a single color (yellow) recorded on Xerox Co., Ltd. plain paper <4024> was measured using a reflection densitometer (X-Rite 310TR) after a certain period of time from the start of exposure. The reflection density was measured at three points of 0.5, 0.8 and 1.0.
From the obtained results, the residual optical density (ROD) was determined using the following formula: ROD (%) = (D / D ₀ ) × 100. (In the formula, D represents the OD value after the exposure test, and D ₀ represents the OD value before the exposure test.)
Furthermore, based on the result of the above test, the ozone gas fastness of the image recorded on the recorded material was evaluated using the following criteria.

(Criteria)
Evaluation A: ROD 14 days after the start of the test is 85% or more at any concentration.
Evaluation (circle): ROD 14 days after the start of a test has the density | concentration of any one point less than 85%.
Evaluation Δ: ROD 14 days after the start of the test, the concentration at any two points is less than 85%.
Evaluation x: ROD 14 days after the start of the test is less than 85% at all concentrations.
In this test, a recorded material with little decrease in ROD is excellent even when exposed to ozone for a long time.
The obtained results are shown in Table 2-2 as “Ozone gas fastness”.

[Example 41]
(Preparation of aqueous dispersion of pigment-containing polymer vinyl polymer particles)
The polymer vinyl polymer solution (1) obtained in Synthesis Example 2 having a solid content of 50% was neutralized by adding a 5 mol / L sodium hydroxide aqueous solution to 10 parts by mass. In addition, the alkali amount which completely neutralizes methacrylic acid or acrylic acid of a high molecular vinyl polymer was added. 9.5 parts by mass of the azo pigment (1) synthesized in Synthesis Example 1 and C.I. I. 0.5 parts by weight of Pigment Yellow 74 (Iralite YELLOW GO manufactured by Ciba Specialty) was added and kneaded in a roll mill for 4 hours. The kneaded product was dispersed in 100 parts by mass of ion-exchanged water. The organic solvent was completely removed from the obtained dispersion at 55 ° C. under reduced pressure, and further concentrated by removing water to obtain an aqueous dispersion of pigment-containing vinyl polymer particles having a solid content concentration of 15% by mass. .

(Preparation of self-dispersing polymer fine particles)
Into a 2 liter three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube, 350.0 g of methyl ethyl ketone was charged and heated to 75 ° C. While maintaining the temperature in the reaction vessel at 75 ° C., 162.0 g of phenoxyethyl acrylate, 180.0 g of methyl methacrylate, 18.0 g of acrylic acid, 70 g of methyl ethyl ketone, and polymerization initiator “V-601” (manufactured by Wako Pure Chemical Industries, Ltd.) ) A mixed solution consisting of 1.44 g was added dropwise at a constant speed so that the addition was completed in 2 hours. After completion of the dropwise addition, a solution consisting of 0.72 g of “V-601” and 36.0 g of methyl ethyl ketone was added and stirred at 75 ° C. for 2 hours, and then a solution consisting of 0.72 g of “V-601” and 36.0 g of isopropanol was added. After stirring at 75 ° C. for 2 hours, the temperature was raised to 85 ° C., and stirring was further continued for 2 hours. The mass average molecular weight (Mw) of the obtained copolymer was 64000 (calculated in terms of polystyrene by gel permeation chromatography (GPC), the columns used were TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (manufactured by Tosoh Corporation)), The acid value was 38.9 (mgKOH / g).
Next, 668.3 g of the above mixed solution at room temperature was weighed, 388.3 g of isopropanol and 145.7 ml of 1 mol / L NaOH aqueous solution were added, and then the temperature in the reaction vessel was raised to 80 ° C. Next, 720.1 g of distilled water was added dropwise at a rate of 20 ml / min to disperse in water. Thereafter, the temperature in the reaction vessel was maintained at 80 ° C. for 2 hours, 85 ° C. for 2 hours, and 90 ° C. for 2 hours under atmospheric pressure, and then the reaction vessel was depressurized, and isopropanol, methyl ethyl ketone, and distilled water totaled 913. 7 g was distilled off to obtain an aqueous dispersion (emulsion) of self-dispersing polymer fine particles (B-01) having a solid content concentration of 28.0%.

Aqueous dispersion of pigment-containing vinyl polymer particles 25 parts by mass Glycerin 5 parts by mass Diethylene glycol 5 parts by mass Triethylene glycol monobutyl ether 5 parts by mass Polyoxypropylene glyceryl ether 10 parts by mass Dipropylene glycol 5 parts by mass Triethanolamine 1 part by mass Olphine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.) 1 part by mass Aqueous dispersion of self-dispersing polymer fine particles (B-01) 15 parts by mass Ion-exchanged water 28 parts by mass The above was mixed to obtain a yellow pigment ink composition 21 .
When the pH of the ink composition was measured with a pH meter-WM-50EG manufactured by Toa DKK Corporation, the pH was 8.5.

[Example 42]
9.5 parts by mass of the azo pigment (1) used in Example 41 and C.I. I. Pigment Yellow 74 (Iralite YELLOW GO, manufactured by Ciba Specialty) 0.5 parts by weight of azo pigment (1) and C.I. I. A yellow pigment ink composition 22 was obtained in the same manner as in Example 41 except that 1 part by mass of Pigment Yellow 74 (Iralite YELLOW GO manufactured by Ciba Specialty) was used.

[Example 43]
C. used in Example 41 I. Pigment Yellow 74 (Iralite YELLOW GO manufactured by Ciba Specialty) 0.5 parts by mass, C.I. I. A yellow pigment ink composition 23 was obtained in the same manner as in Example 41 except that 0.5 parts by mass of Pigment Yellow 155 (INKJET YELLOW 4G VP2532 manufactured by Clariant) was used.

[Example 44]
C. used in Example 41 I. Pigment Yellow 74 (Iralite YELLOW GO manufactured by Ciba Specialty) 0.5 parts by mass, C.I. I. A yellow pigment ink composition 24 was obtained in the same manner as in Example 41 except that 0.5 part by mass of Pigment Yellow 110 (IRGAZIN YELLOW 2RLT manufactured by Ciba Specialty) was used.

[Example 45]
C. used in Example 41 I. Pigment Yellow 74 (Iralite YELLOW GO manufactured by Ciba Specialty) 0.5 parts by mass, C.I. I. A yellow pigment ink composition 25 was obtained in the same manner as in Example 41 except that 0.5 parts by mass of Pigment Yellow 128 (CROMOPHTAL YELLOW 8GN manufactured by Ciba Specialty) was used.

[Example 46]
C. used in Example 41 I. Pigment Yellow 74 (Iralite YELLOW GO manufactured by Ciba Specialty) 0.5 parts by mass, C.I. I. A yellow pigment ink composition 26 was obtained in the same manner as in Example 41 except that 0.5 parts by mass of Pigment Yellow 138 (PALIOTOL L YELLOW 0960 HD manufactured by BASF) was used.

[Example 47]
C. used in Example 41 I. Pigment Yellow 74 (Iralite YELLOW GO manufactured by Ciba Specialty) 0.5 parts by mass, C.I. I. A yellow pigment ink composition 27 was obtained in the same manner as in Example 41 except that 0.5 part by mass of Pigment Yellow 139 (PALIOTOL D YELLOW 1891 manufactured by BASF) was used.

[Example 48]
C. used in Example 41 I. Pigment Yellow 74 (Iralite YELLOW GO manufactured by Ciba Specialty) 0.5 parts by mass, C.I. I. A yellow pigment ink composition 28 was obtained in the same manner as in Example 41 except that 0.5 part by mass of Pigment Yellow 150 (CROMOPHTAL YELLOW LA2 manufactured by Ciba Specialty) was used.

[Example 49]
C. used in Example 41 I. Pigment Yellow 74 (Iralite YELLOW GO manufactured by Ciba Specialty) 0.5 parts by mass, C.I. I. A yellow pigment ink composition 29 was obtained in the same manner as in Example 41 except that 0.5 part by mass of Pigment Yellow 185 (PALIOTOL YELLOW D1155 manufactured by BASF) was used.

[Example 50]
C. used in Example 41 I. Pigment Yellow 74 (Iralite YELLOW GO manufactured by Ciba Specialty) 0.5 parts by mass, C.I. I. A yellow pigment ink composition 30 was obtained in the same manner as in Example 41 except that 0.5 part by mass of Pigment Yellow 213 (Hostaper Yellow H5G manufactured by Clariant) was used.

[Comparative Example 21]
9.5 parts by weight of the azo pigment (1) used in Example 41 and C.I. I. Pigment Yellow 74 (Iralite YELLOW GO, manufactured by Ciba Specialty) I. A comparative yellow ink composition 21 was obtained in the same manner as in Example 41 except that 10 parts by mass of Pigment Yellow 74 (Iralite YELLOW GO manufactured by Ciba Specialty) was used.

[Comparative Example 22]
9.5 parts by weight of the azo pigment (1) used in Example 41 and C.I. I. Pigment Yellow 74 (Iralite YELLOW GO, manufactured by Ciba Specialty) I. A comparative yellow ink composition 22 was obtained in the same manner as in Example 41 except that 10 parts by mass of Pigment Yellow 155 (INKJET YELLOW 4G VP2532 manufactured by Clariant) was used.

[Comparative Example 23]
9.5 parts by weight of the azo pigment (1) used in Example 41 and C.I. I. Pigment Yellow 74 (Iralite YELLOW GO, manufactured by Ciba Specialty) I. A comparative yellow ink composition 23 was obtained in the same manner as in Example 41 except that 10 parts by weight of Pigment Yellow 128 (CROMOPHTAL YELLOW 8GN manufactured by Ciba Specialty) was used.

[Example 51]
The yellow pigment ink liquids of Examples 41 to 50 and Comparative Examples 21, 22, and 23 were loaded into a yellow ink liquid cartridge of an ink jet printer PX-V630 manufactured by Seiko Epson Corporation, and the image receiving sheet was Seiko Epson Corporation. Company photo paper Krispia <High Gloss> Color setting: No color correction, Print quality: Yellow single color image pattern with density changed stepwise so that the OD value of yellow is 0.7-1.8 in the photo Were printed to obtain recorded materials. The hue, printing characteristics and image fastness of the recorded matter were evaluated.

[Hue test method]
The reflection density of each recorded matter of Example 51 obtained by printing a yellow single-color image pattern whose density changed stepwise was measured using a spectrophotometer GRETAG SPM-50 (manufactured by GRETAG).
Measurement conditions were light source D50, no light source filter, white standard was absolute white, viewing angle was 2 °, and L * value, a * value, and b * value defined by CIE were obtained. Evaluation was made based on the following criteria, and the results are shown in Table 3.

[Criteria]
Evaluation ◎: When a * = 0, b * ≧ 95 and b * = 95 a * ≦ −5
When b * ≦ 30 and 60 ≦ b * ≦ 95 when −5 ≦ a * ≦ 0, a * ≦ −10
Evaluation ○: Applicable to one of the conditions under evaluation ◎ Applicable △: Applicable to none of the conditions under evaluation ◎

[Evaluation of coloring power]
The yellow pigment ink liquids of Examples 41 to 50 and Comparative Examples 21, 22, and 23 were loaded into a yellow ink liquid cartridge of an ink jet printer PX-V630 manufactured by Seiko Epson Corporation, and the image receiving sheet was Seiko Epson Corporation. Photographic paper Krispia <High Gloss> Color setting: No color correction, Print quality: Create a solid yellow print pattern with photo, and a single color density of 2.0 ≦ ODmax ◎, 1.8 ≦ ODmax < 2.0 was evaluated as ◯, 1.5 ≦ ODmax <1.8 was evaluated as Δ, and ODmax <1.5 was evaluated as ×. The obtained results are shown as “coloring power” in Table 3.

[Light fastness test method]
Using a weather meter (manufactured by Atlas), the images of each recorded matter of Example 51 were irradiated with xenon light (100,000 lux) for 42 days. The OD value of the color (yellow) recorded on each recorded matter was measured using a reflection densitometer (X-Rite 310TR) at every elapse of a certain period from the start of irradiation. The reflection density was measured at three points of 0.7, 1.0, and 1.8.
From the obtained results, the residual optical density (ROD) was determined using the following formula: ROD (%) = (D / D ₀ ) × 100. (In the formula, D represents the OD value after the exposure test, and D ₀ represents the OD value before the exposure test.)
Furthermore, based on the results of the above test, the light fastness of the color (yellow) recorded on the recorded material was evaluated based on the following criteria using the following criteria.
[Criteria]
Evaluation A: ROD after 42 days from the start of the test is 85% or more at any concentration.
Evaluation ○: ROD 42 days after the start of the test, the concentration at any one point is less than 85%.
Evaluation Δ: ROD 42 days after the start of the test, the concentration at any two points is less than 85%.
Evaluation x: ROD 42 days after the start of the test is less than 85% at all concentrations.
In this test, a recorded matter with little decrease in ROD even when exposed to light for a long time is excellent. The obtained results are shown in Table 3 as “light fastness”.

[Ozone gas fastness test method]
Each recorded matter of Example 51 was exposed to ozone gas for 28 days under the condition that the ozone gas concentration was set to 5 ppm (25 ° C .; 50% RH). The ozone gas concentration was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS. The OD value of the color (yellow) recorded on each printed matter was measured using a reflection densitometer (X-Rite 310TR) at every elapse of a certain period from the start of exposure. The reflection density was measured at three points of 0.7, 1.0, and 1.8.
Next the results obtained formula: ROD (%) = determine the optical density retention (ROD) with _{(D / D 0) × 100} . (In the formula, D represents the OD value after the exposure test, and D ₀ represents the OD value before the exposure test.)

Furthermore, based on the results of the above test, the following criteria were used to evaluate the ozone fastness of the color (yellow) recorded on the recorded matter based on the following criteria.
[Criteria]
Evaluation A: ROD after 28 days from the start of the test is 85% or more at any concentration.
Evaluation ○: ROD after 28 days from the start of the test, the concentration at any one point is less than 85%.
Evaluation Δ: ROD after 28 days from the start of the test, the concentration at any two points is less than 85%.
Evaluation x: ROD after 28 days from the start of the test is less than 85% at all concentrations.

  In this test, a recorded material with little decrease in ROD is excellent even when exposed to ozone for a long time. The obtained results are shown in Table 3 as “ozone gas fastness”.

From these results, the yellow pigment dispersion of the present invention is easily dispersible, the pigment dispersion has good stability, excellent hue as yellow, high coloring power, light resistance and ozone gas resistance It was also found to be excellent.
Therefore, the yellow pigment dispersion of the present invention includes, for example, printing inks such as inkjet, color toners for electrophotography, displays such as LCDs and PDPs, and color filters, paints, and colored plastics used in image pickup devices such as CCDs. Etc. can be used suitably.

Claims (11)

At least one azo pigment or tautomer represented by the following formula (1):
C. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 73, 74, 75, 83, 93, 95, 97, 98, 109, 110, 114, 120, 128, 138, 139, 150, A yellow pigment dispersion comprising a colorant containing at least one selected from the group consisting of 151, 154, 155, 180, 185, and 213.

  The azo pigment or tautomer has characteristic X-ray diffraction peaks with Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction of 7.6 °, 25.6 °, and 27.7 °. The yellow pigment dispersion according to claim 1, comprising:   The yellow pigment dispersion according to claim 1 or 2, wherein the azo pigment or tautomer is contained in an amount of 10% by mass or more based on the total pigment solid content in the yellow pigment dispersion.   Furthermore, the yellow pigment dispersion of any one of Claims 1-3 which contains a dispersing agent at 10-140 mass% with respect to the said coloring agent.   The yellow pigment dispersion according to any one of claims 1 to 4, further comprising a high-boiling organic solvent in an amount of 0.1 to 30% by mass relative to the total amount of the yellow pigment dispersion.   Furthermore, the yellow pigment dispersion of any one of Claims 1-5 which contains a penetration enhancer in 1-20 mass% with respect to the whole quantity of a yellow pigment dispersion.   An ink for inkjet recording, comprising the yellow pigment dispersion according to any one of claims 1 to 6.   An ink jet recording cartridge comprising the ink for ink jet recording according to claim 7.   An ink jet recording method for forming an image using the ink for ink jet recording according to claim 7.   An ink jet recording apparatus for forming an image using the ink for ink jet recording according to claim 7.   An ink-jet recorded matter formed by forming an image using the ink for ink-jet recording according to claim 7.

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