JP5544220B2 - Azo pigment or tautomer thereof, production method thereof, pigment dispersion, coloring composition, ink for inkjet recording, coloring composition for color filter, and color filter - Google Patents

Description

  The present invention relates to an azo pigment or a tautomer thereof, a production method thereof, a pigment dispersion, a coloring composition, an ink for inkjet recording, a coloring composition for a color filter, and a color filter.

  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 mixing method and subtractive color mixing method are used to display or record full color images. The fact is that there are no fast-acting dyes that have absorption characteristics that can satisfy the above conditions and that can withstand various use conditions and environmental conditions, and improvements are 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 other words, the required performance for pigments is wider than dyes that require performance as pigment molecules, and not only the performance as pigment molecules but also the above requirements as a solid (fine particle dispersion) as an aggregate 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.

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.
Patent Document 1 discloses an azo pigment that has excellent color characteristics such as coloring power and hue, and also has excellent durability such as light resistance.

On the other hand, many of the typical organic pigments are polymorphic, and it is known that such pigments take two or more crystalline forms despite having the same chemical composition.
Some organic pigments, such as azo pigments, can obtain finely sized particles by selecting appropriate reaction conditions during synthesis, such as copper phthalocyanine green pigments during synthesis. The very fine and agglomerated particles that are produced are pigmented by particle growth and sizing in the subsequent process, such as copper phthalocyanine blue pigment, coarse and irregular particles that are produced during synthesis are refined in the subsequent process, Some pigments are made by sizing. For example, a diketopyrrolopyrrole pigment is generally synthesized by reacting an oxalic acid diester and an aromatic nitrile in an organic solvent (see, for example, Patent Document 2). The crude diketopyrrolopyrrole pigment is heat treated in water or an organic solvent, and then powdered such as wet milling to make it suitable for use (see, for example, Patent Document 3). C. I. As pigment red 254, α-type and β-type crystal forms are known (for example, see Patent Document 4). Further, C.I. which is an azo pigment. I. Pigment Yellow 181 has several known crystal forms (see, for example, Patent Document 5).

JP 2010-47750 A JP 58-210084 JP-A-5-222314 JP-A-8-48908 US Patent Application Publication No. 2008/0058531

An object of the present invention is to provide an azo compound, an azo pigment, an azo pigment dispersion, and a coloring composition that are excellent in color characteristics such as coloring power, hue, and color reproducibility, and exhibit heat resistance, light resistance, and high contrast. That is.
Furthermore, this invention aims at providing the coloring composition containing this azo pigment.
An object of the present invention is to provide a method for producing an azo pigment that can be produced with high reproducibility and high efficiency while controlling to a specific structural isomerism and crystal polymorphism.
Furthermore, it aims at providing the coloring composition containing the dispersion of this azo pigment.

As a result of intensive studies in view of the above circumstances, the present inventors have found that an azo pigment having a characteristic X-ray diffraction peak at a specific position in the embodiment of the present invention has extremely high color reproducibility, dispersibility, and pigment dispersion stability. It was found to be good and have excellent hue, color reproducibility and tinting strength. In addition, the coloring composition in which the pigment is dispersed has excellent color reproducibility, and can produce an ink for ink jet recording having excellent pigment dispersion stability and ink liquid stability with stable pigment particle diameter over time. I found.
Furthermore, the inventors have found a method for producing an azo pigment capable of producing an azo pigment with high reproducibility and high efficiency while controlling to specific structural isomerism and crystal polymorphism, and have completed the present invention.

That is, the present invention is as follows.
[1]
The Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction has characteristic X-ray diffraction peaks at 6.9 °, 25.8 ° and 27.1 °, and the peak height at 11.9 ° An azo pigment represented by the following formula (1) having a peak height at 10.9 of 0.2 or less, a tautomer, salt, hydrate or solvate thereof.

[2]
A Bragg angle (2θ in CuKα characteristic X-ray diffraction) comprising a step of subjecting a diazonium salt derived from a heterocyclic amine represented by the following formula (2) to a compound represented by the following formula (3) by an azo coupling reaction: ± 0.2 °) has characteristic X-ray diffraction peaks at 6.9 °, 25.8 ° and 27.1 °, with a peak height at 10.9 ° relative to the peak height at 11.9 °. The manufacturing method of the azo pigment represented by following formula (1) which is 0.2 or less, or its tautomer.

[3]
Furthermore, the composition containing the azo pigment represented by the above formula (1) having a water content of 50% by mass or more and 200% by mass or less or a tautomer thereof and water is provided for the post-treatment step [ [2] A process for producing an azo pigment or a tautomer thereof.
[4]
The azo pigment represented by the formula (1) has a Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction of 6.9 °, 11.9 °, 23.8 °, 25.8 °, It has characteristic X-ray diffraction peaks at 26.7 ° and 27.1 °, and the peak height at 10.9 ° is 0.2 or less with respect to the peak height at 11.9 ° [ [2] A process for producing an azo pigment or a tautomer thereof according to [3].
[5]
The azo pigment obtained by the production method according to any one of [2] to [4], a tautomer, salt, hydrate or solvate thereof.
[6]
A pigment dispersion comprising at least one selected from the azo pigments according to [1] or [5], tautomers, salts, hydrates or solvates thereof.
[7]
A coloring composition comprising the pigment dispersion according to [6].
[8]
[7] An ink for ink-jet recording comprising the colored composition according to [7].
[9]
[7] A colored composition for a color filter comprising the colored composition according to [7].
[10]
A color filter manufactured using the coloring composition for a color filter according to [9].

  According to the present invention, there is provided an azo pigment that is excellent in color characteristics such as coloring power, is stable in pigment particle diameter over time, and is excellent in pigment dispersion stability and ink liquid stability. By dispersing the pigment of the present invention in various media, a pigment dispersion having excellent color characteristics, dispersion stability and ink liquid stability can be obtained. The pigment dispersion can be used, for example, in printing inks such as inkjet, color toners for electrophotography, displays such as LCDs and PDPs, color filters used in image sensors such as CCDs, paints, and colored plastics. it can.

2 is an X-ray diffraction pattern of a β-type crystal form pigment (1) synthesized according to Synthesis Example 1. FIG. 2 is an X-ray diffraction pattern of a pigment (D-1) synthesized according to Comparative Synthesis Example 1. FIG.

Hereinafter, the present invention will be described in detail.
The azo pigment of the present invention or a tautomer thereof may be a hydrate, a solvate or a salt thereof.

Hereinafter, the present invention will be described in detail.
The azo pigment of the present invention has characteristic X-ray diffraction peaks at Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction of 6.9 °, 25.8 ° and 27.1 °, and 11 It is an azo pigment represented by the following formula (1) having a peak height at 10.9 ° of 0.2 or less with respect to a peak height at .9 ° or a tautomer thereof.
In the present specification, hereinafter, the Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction have characteristic X-ray diffraction peaks at 6.9 °, 25.8 °, and 27.1 °, An azo pigment represented by the following formula (1) having a peak height at 10.9 ° of 0.2 or less with respect to a peak height at 11.9 ° is referred to as a β-type crystal form azo pigment.

A pigment is a state in which molecules are firmly bonded to each other by cohesive energy due to strong interaction between dye molecules. In order to create this state, it is described in, for example, Journal of Imaging Society of Japan, Vol. 43, page 10 (2004) that van der Waals force between molecules and hydrogen bonding between molecules are necessary.
In order to increase the van der Waals force between molecules, introduction of an aromatic group, a polar group and / or a hetero atom into the molecule can be considered. Moreover, in order to form an intermolecular hydrogen bond, introduction | transduction of the substituent containing the hydrogen atom couple | bonded with the hetero atom to a molecule | numerator and / or introduction | transduction of an electron-donating ring-setting group etc. can be considered. Further, it is considered preferable that the polarity of the whole molecule is high. For this purpose, for example, a shorter chain group such as an alkyl group is preferred, and a smaller molecular weight / azo group value is preferred.
From these viewpoints, the pigment molecule generally preferably contains an amide bond, a sulfonamide bond, an ether bond, a sulfone group, an oxycarbonyl group, an imide group, a carbamoylamino group, a heterocycle, a benzene ring, etc. The compound represented by (1) can easily form an intermolecular interaction of dye molecules due to its specific structure, has low solubility in water or an organic solvent, and can be an azo pigment.
Unlike a dye that dissolves in water or an organic solvent in a molecular dispersion state, the pigment is finely dispersed in the solvent as solid particles such as a molecular assembly.

  In the present invention, the X-ray diffraction measurement of the β-type crystal form azo pigment represented by the above formula (1) is performed in accordance with Japanese Industrial Standard JISK0131 (general rules for X-ray diffraction analysis). (Manufactured by Rigaku Corporation).

  When the pigment is in a single crystal form, the molecules become dense and the interaction between molecules 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. The azo pigment represented by the formula (1) and its tautomer have Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction of 6.9 °, 25.8 ° and 27.1 °. It has a characteristic X-ray diffraction peak, the peak height at 10.9 ° is 0.2 or less with respect to the peak height at 11.9 °, and there is no clear X-ray diffraction peak at 10.9 ° A single crystal form is preferred. Furthermore, it is more preferable that the crystal form has X-ray diffraction peaks characteristic at 6.9 °, 11.9 °, 23.8 °, 25.8 °, 26.7 ° and 27.1 °.

The β-type crystal form azo pigment which is a single crystal form can be obtained by the production method of the present invention described later.
As azo pigments represented by the formula (1) other than β-type crystal form azo pigments, Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction are 6.9 °, 21.5 ° and 27.3. An azo pigment represented by the formula (1) having a characteristic X-ray diffraction peak at ° (hereinafter referred to as an α-type crystal form azo pigment) and a mixture of an α-type crystal form azo pigment and a β-type crystal form azo pigment be able to. The α-type crystal form azo pigment has a bright red hue. On the other hand, a mixture of an α-type crystal form azo pigment and a β-type crystal form azo pigment has excellent dispersibility.

When the height of the peak at 11.9 ° of the Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction is 1, the peak height at 10.9 ° is 0.2 or less. From the standpoint that the hue is less susceptible to yellowing.
Therefore, the peak height at 20.0 ° of the Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction is 0 to 0.2 when the peak height at 27.2 ° is 1. It is preferably 0, more preferably 0 to 0.1, and most preferably 0 to 0.05.

  The length in the major axis direction when the primary particles of the β-type crystal form azo pigment represented by the above formula (1) 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 10 μm or less, and particularly preferably 0.03 μm or more and 0.5 μm or less.

  When the primary particles are observed with a transmission microscope, the length in the major axis direction is 0.01 μm or more, so that the fastness to light and ozone, and the dispersibility in the case of a pigment dispersion are more reliably ensured. It can be expressed. On the other hand, when the length in the major axis direction is 30 μm or less, when dispersed to a desired volume average particle diameter, it is difficult to be in an overdispersed state and agglomeration hardly occurs, so that the storage stability of the pigment dispersion is improved. It can be expressed more reliably.

  If the length in the major axis direction of the primary particles is within the above range, the pigment particles exhibit high fastness to light and ozone, and the pigment dispersion is excellent in storage stability and preferable.

  As described above, the azo pigment of the present invention has a specific structure and has a characteristic X-ray diffraction peak at a specific position, so that the color characteristics such as coloring power, hue, and color reproducibility are improved. It exhibits excellent characteristics and also exhibits excellent characteristics in fastness (particularly solvent resistance).

The present invention includes within its scope tautomers of the azo pigments represented by the formula (1). Formula (1) is shown in the form of an ultimate structural formula among several tautomers that can be taken in terms of chemical structure, but may be a tautomer other than the described structure, You may use as a mixture containing the tautomer.
For example, the pigment represented by the formula (1) may be an azo-hydrazone tautomer represented by the following formula (1 ′).
The present invention includes in its scope a compound represented by the following formula (1 ′), which is a tautomer of the azo pigment represented by the formula (1).

  The ratio of azo and hydrazone can be easily grasped semi-quantitatively by solid-state NMR measurement or Raman absorption measurement. Although azo and hydrazone exhibit good performance, it is preferable that the ratio of hydrazone is large from the viewpoint of hue. The hydrazone is preferably 50% or more, more preferably 80% or more, and most preferably 90% or more.

  In particular, the Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction has characteristic X-ray diffraction peaks at 6.9 °, 25.8 ° and 27.1 °, and the peak height at 11.9 ° The β-type crystal form azo pigment represented by the formula (1) whose peak height at 10.9 ° is 0.2 or less is characterized by good absorption characteristics of red dyes, and is used for photo and CF applications. It is suitable for the field where color reproducibility is required.

[Method for producing azo pigment or tautomer thereof]
The method for producing an azo pigment or a tautomer thereof according to the present invention comprises a azo coupling of a diazonium salt derived from a heterocyclic amine represented by the following formula (2) and a compound represented by the following formula (3). It is a manufacturing method of the azo pigment or its tautomer represented by following formula (1) including the process made to react. This production method has characteristic X-ray diffraction peaks at Bragg angles (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction of 6.9 °, 25.8 ° and 27.1 °, and 11.9 The azo pigment (β-type crystal form azo pigment) represented by formula (1) having a peak height at 10.9 ° of 0.2 or less with respect to the peak height at ° is highly reproducible. It is a method that can be manufactured efficiently. The azo pigment represented by the formula (1) has a Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction of 6.9 °, 11.9 °, 23.8 °, 25.8 °, 26 It is preferable to have characteristic X-ray diffraction peaks at .7 ° and 27.1 °.

  The preparation of the diazonium salt and the coupling reaction between the diazonium salt and the compound represented by the formula (3) can be carried out by a conventional method.

  The diazonium salt preparation of the heterocyclic amine represented by the 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.) Conventional diazonium salt preparation methods using nitrosonium ion sources such as nitrous acid, nitrite or nitrosylsulfuric acid are applicable.

  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 phosphoric acid is particularly preferable.

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

Examples of preferred nitrosonium ion sources include nitrites, nitrites, nitrosylsulfuric acid and the like. Among these, sodium nitrite, potassium nitrite, isoamyl nitrite, and nitrosylsulfuric acid (for example, ONHSO ₄ sulfuric acid solution) are preferable. In particular, by using sodium nitrite, a diazonium salt can be prepared stably and efficiently. At this time, an appropriate amount of a trap agent (for example, urea) for trapping an excessive amount of substance (for example, nitrosonium ion) derived from sodium nitrite may be added to the reaction medium. Generation of impurities due to an excessive amount of material can be suppressed.

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

  In the present invention, the heterocyclic amine of the formula (2) may be in a state where it is dispersed in a solvent, or may be in the state of a solution depending on the type of diazo component. It is preferable that

  The amount of the 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 with respect to the heterocyclic amine of formula (2). .50 equivalents are preferred.

  The reaction temperature is preferably −15 ° C. to 40 ° C., more preferably −10 ° C. to 35 ° C., and still more preferably −5 ° C. to 30 ° C. If it is less than -15 ° C, the reaction rate is remarkably slow and the time required for the synthesis becomes remarkably long, which is not economical, and it is preferable to synthesize at a high temperature exceeding 40 ° C 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.

  Although the compound represented by Formula (3) can be obtained as a commercial product, it can be produced by a method according to the description in JP-A-2008-13472.

[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 to decompose the diazonium salt. It can be suppressed and efficiently derived into an azo pigment.

  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 Examples thereof include diol organic solvents such as glycol and 1,3-propanediol, ether organic solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol diethyl ether, tetrahydrofuran, dioxane, acetonitrile, and the like. These solvents 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.

  A preferable example of the reaction medium is a polar aprotic solvent. 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 of the above formula (3) may or may not be completely dissolved in the solvent.

  The reaction medium exemplified above may contain an acid-containing reaction medium used for deriving the heterocyclic amine represented by the formula (2) to a diazonium salt.

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

  In the present invention, the compound represented by the formula (3) may be either dispersed in a solvent or dissolved.

  The amount of the compound represented by the formula (3) is preferably 0.5 to 5 equivalents, more preferably 0.6 to 3 equivalents, particularly 0.6 to 1.5 equivalents with respect to the diazonium salt. Preferably there is.

  The reaction temperature is preferably -30 ° C to 30 ° C, more preferably -20 ° C to 20 ° C, and still more preferably -10 ° C to 10 ° 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 250 minutes, and still more preferably 30 minutes to 200 minutes.

  In the method for synthesizing the azo pigment or the tautomer thereof according to 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 purified. Can be served without.

  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 synthesizing the azo pigment of the present invention or a tautomer thereof will be described in detail.

  The method for producing an azo pigment or a tautomer thereof according to the present invention comprises coupling 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). In the reaction, it is preferable to carry out a coupling reaction after dissolving the compound of the formula (3) in an organic solvent.

  The diazoniumation reaction of the heterocyclic amine represented by the above formula (2) can be performed, for example, in an acidic solvent such as sulfuric acid, phosphoric acid, and acetic acid, with a reagent such as sodium nitrite and nitrosylsulfuric acid at a temperature of 30 ° C. or less for 10 minutes to The reaction can be carried out for about 6 hours. 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.

  As a method for producing the azo pigment, it is preferable to use, for example, the method of the present invention in which the compound represented by the above formula (3) is once dissolved in an organic solvent and then subjected to a coupling reaction. Examples of the organic solvent that can be used at this time include alcohol solvents, ketone solvents, and polar aprotic 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. Examples of polar aprotic solvents include acetone and methyl ethyl ketone exemplified as ketone solvents, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea Acetonitrile and the like are preferable, and N, N-dimethylacetamide is particularly preferable among them.

  Among the methods for producing the azo pigment or the tautomer thereof described above, the heterocyclic amine represented by the formula (2) is used by using a solution in which the heterocyclic amine is dissolved in phosphoric acid. Preparing a solution of a diazonium salt derived from a cyclic amine, and then mixing the solution of the diazonium salt with a solution of the compound represented by the formula (3) dissolved in N, N-dimethylacetamide. It is particularly preferable to carry out the azo coupling reaction.

  In addition, in the said preferable form, in addition to N, N- dimethylacetamide, the reaction medium of a coupling reaction process is an acid containing reaction medium used by diazotization of the heterocyclic amine represented by Formula (2). It is in a state containing phosphoric acid.

  The phosphoric acid used to derive the heterocyclic amine represented by the formula (2) into a diazonium salt functions as an acid and a reaction medium in the above-described acid-containing reaction medium.

  The compound obtained by the above production method can be subjected to a purification step depending on the application. The purification step may or may not adjust the pH by adding a base. 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 pH is 10 or less, a hue does not increase yellowishness and it is preferable from a viewpoint of a hue. When the pH is 4 or more, for example, when used as an ink for ink jet recording, problems such as corroding the nozzle hardly occur, which is preferable.

[Post-treatment process]
The compound represented by the formula (1) of the present invention is preferably subjected to a solvent heating treatment as a post-treatment step. Thereby, a β-type crystal form azo pigment can be obtained with high purity.

In the present invention, the post-treatment step preferably includes a solvent heat treatment using a solvent having an SP value of 7.0 to 14.0. Since the pigment is dissolved by this solvent heating treatment, the impurities incorporated in the pigment can be removed.
As a solvent used for the solvent heat treatment, a solvent having an SP value of 7.0 to 14.0 is preferably used, an SP value of 9.0 to 13.0 is more preferable, and ethyl acetate, dibutyl phthalate, acetone, isopropyl are used. Alcohol, acetonitrile, acetic acid, N, N-dimethylacetamide and N, N-dimethylformamide are more preferred, and acetone, acetonitrile, N, N-dimethylacetamide and N, N-dimethylformamide are most preferred.

The amount of the solvent used for the solvent heat treatment varies depending on the type of the solvent, but is preferably 1 to 100 times by weight, more preferably 5 to 70 times by weight, and 5 to 30 times by weight of the compound represented by the formula (1). Is particularly preferred.
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.

  The above-described tautomerism and crystal polymorphism can be controlled by the production conditions during the post-treatment. Examples of post-treatment methods include solvent salt milling, salt milling, dry milling, solvent milling, pigment particle control step by grinding treatment such as acid pasting, solvent heating treatment, resin, surfactant and dispersant. The surface treatment process by etc. is mentioned.

  The tautomerism and / or crystal polymorphism described above can be controlled by the production conditions during the post-treatment. Examples of post-treatment methods include solvent salt milling, salt milling, dry milling, solvent milling, pigment particle control step by grinding treatment such as acid pasting, solvent heating treatment, resin, surfactant and dispersant. The surface treatment process by etc. is mentioned.

  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.

[Post-treatment process in the presence of water]
In another embodiment of the present invention, a composition containing an azo pigment represented by the above formula (1) having a water content of 50% by mass or more and 200% by mass or less or a tautomer thereof and water is used as a post-treatment step. It is preferable to provide. That is, the formula (1) is preferably subjected to a post-treatment step in the presence of water. Thereby, the β-type crystal form azo pigment can be produced with higher reproducibility and higher efficiency. The water content is obtained by placing 100 mg of the pigment to be measured on an aluminum dish and subtracting the mass (g) of the pigment that has been allowed to stand overnight at 80 ° C. to dryness from the total mass (100 mg) of the pigment before drying. The value (difference) can be determined by calculating the ratio (mass%) in the total mass (100 mg) of the pigment before drying.
As the post-treatment step, it is preferable to perform the solvent heating treatment described above.
The compound represented by the formula (1) subjected to the solvent heat treatment is a compound in the presence of water in which the powder obtained by filtration or the like is neutralized after the azo coupling reaction and the filtration step is performed. preferable.

  The water content of the compound represented by formula (1) when the post-treatment step is performed in the presence of water is preferably 20% by mass or more and 400% by mass or less, and 50% by mass or more and 200% by mass or less. Is more preferable, and it is particularly preferably 100% by mass or more and 200% by mass or less. When the water content is 20% by mass or more, a β-type crystal form azo pigment that does not contain an α-type crystal form azo pigment can be easily obtained. On the other hand, when the water content is 400% by mass or less, β-type crystals Crystals can be arranged to form azo pigments.

  The present invention also relates to a β-type crystal form azo pigment produced by the above production method, a tautomer, salt, hydrate or solvate thereof.

[Pigment dispersion]
The pigment dispersion of the present invention is characterized by containing the above β-type crystal form azo pigment or a tautomer thereof, or the azo pigment obtained by the production method of the present invention or a tautomer thereof. Thereby, it can be set as the pigment dispersion excellent in chromatic characteristics, durability, and dispersion stability.

  The 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 Polyhydric 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 a water-soluble resin that dissolves in water, a water-dispersible resin that disperses in water, a colloidal dispersion resin, or a mixture thereof. Specific examples of the aqueous resin include acrylic, styrene-acrylic, polyester, polyamide, polyurethane, and fluorine resins.

  When the aqueous pigment dispersion in the present invention contains an aqueous resin, the content is not particularly limited. For example, it can be 0 to 100% by mass with respect to the pigment.

  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.

  When the aqueous pigment dispersion in the present invention contains a surfactant, the content is not particularly limited. For example, it can be 0 to 100% by mass with respect to the pigment.

  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 fatty acid Examples include esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, fluorine-based materials, and silicon-based materials.

  The non-aqueous pigment dispersion of the present invention is obtained by dispersing the pigment represented by the formula (1) in a non-aqueous vehicle. Resins used in non-aqueous vehicles are, for example, petroleum resins, casein, shellac, rosin modified maleic resin, rosin modified phenolic resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber, chlorinated rubber, oxidized rubber, 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.

  In the present invention, the volume average particle diameter of the pigment is preferably 10 nm or more and 250 nm or less. The volume average particle diameter of the pigment particles refers to the particle diameter of the pigment itself or the particle diameter to which the additive has adhered when an additive such as a dispersant is attached to the pigment. In the present invention, a nanotrac UPA particle size analyzer (UPA-EX150; manufactured by Nikkiso Co., Ltd.) can be 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 putting 3 ml of the pigment dispersion in a measuring cell. 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.

  A more preferable volume average particle diameter is 20 nm or more and 250 nm or less, and further preferably 30 nm or more and 230 nm or less. When the number average particle size of the particles in the pigment dispersion is less than 20 nm, there are cases where the storage stability cannot be ensured, whereas when it exceeds 250 nm, the optical density may be lowered.

  The concentration of the pigment contained in the pigment dispersion of the present invention is preferably in the range of 1 to 35% by mass, and more preferably in the range of 2 to 25% by mass. 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.

  The pigment dispersion of the present invention can be obtained by dispersing the above azo pigment and an 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.

  Applications of the azo pigments of the present invention include image recording materials for forming images, particularly color images. Specifically, the ink-jet recording materials described in detail below, thermal recording materials, Pressure recording material, recording material using an electrophotographic method, transfer type silver halide photosensitive material, printing ink, recording pen, etc., preferably an ink jet recording material, a thermal recording material, a recording material using an electrophotographic method, More preferred are ink jet recording materials.

  Further, the present invention can be applied to a solid-state imaging 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 staining solution for dyeing various fibers.

  The azo pigment of the present invention is used by adjusting physical properties such as solvent resistance, dispersibility, and heat mobility suitable for the application with a substituent. Further, the azo pigment of the present invention can be used in an emulsified dispersion state or further in a solid dispersion state depending on the system used.

[Coloring composition]
The colored composition of the present invention means a colored composition containing the above-described azo pigment or a tautomer thereof, or the above-described pigment dispersion. The coloring composition of the present invention can contain a medium, but when a solvent is used as the medium, it is particularly suitable as an ink for inkjet recording. The coloring composition of the present invention can be produced by using a lipophilic medium or an aqueous medium as a medium and dispersing the azo pigment of the present invention in the medium. Preferably, an aqueous medium is used. The coloring composition of the present invention includes an ink composition excluding a medium. The coloring composition of the present invention may contain other additives as necessary 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-soluble ink. In the case of oil-soluble ink, 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.

[Ink for inkjet recording]
Next, the ink for inkjet recording of the present invention will be described.
The pigment dispersion described above is used for the inkjet recording ink of the present invention (hereinafter sometimes referred to as “ink”). 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 of the present invention is preferably in the range of 1 to 100% by mass in consideration of the hue, color density, saturation, transparency and the like of the image formed on the recording medium. The range of mass% is particularly preferable, and the range of 3 to 10 mass% is most preferable among them.

  The pigment of the present invention is preferably contained in an amount of 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass in 100 parts by mass of the ink of the present invention. It is more preferable to contain 10 parts by mass. Further, in the ink of the present invention, other pigments may be used in combination with the pigment of the present invention. When two or more kinds of pigments are used in combination, the total content of the pigments is preferably within the above range.

  The ink of the present invention can be used not only for monochromatic image formation but also for full color image formation. 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.

  Furthermore, in the ink of the present invention, other pigments can be used simultaneously in addition to the azo pigment of the present invention. Examples of yellow pigments that can be applied include C.I. I. P. Y. 74, C.I. I. P. Y. 128, C.I. I. P. Y. 155, C.I. I. P. Y. 213, and magenta pigments that can be applied include C.I. I. P. V. 19, C.I. I. P. R. 122, and examples of applicable cyan pigments include C.I. I. P. B. 15: 3, C.I. I. P. B. 15: 4 can be mentioned, and apart from these, any one can be used. Applicable black materials include disazo, trisazo, and tetraazo pigments, as well as carbon black dispersions.

  As the water-soluble solvent used in the ink jet recording ink of the present invention, 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, 1,5-pentanediol, 1,2,6-hexanetriol, and glycerin.

  Examples of the polyhydric alcohol derivative include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diglycerin. And 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.

Preferred physical properties of the ink for ink jet recording of 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 ejection improvement, 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 its derivatives, 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.

[Coloring composition for color filter]
The coloring composition for a color filter of the present invention contains the above-described pigment composition of the present invention, but preferably further contains a polymerizable compound and a solvent.
Moreover, when manufacturing the coloring composition for color filters of this invention, the azo pigment obtained by making it above may be mix | blended as it is, or the pigment dispersion disperse | distributed in the solvent may be mix | blended. An azo pigment is preferably a pigment dispersion because it has excellent color characteristics, durability and dispersion stability, light resistance and weather resistance.

  The amount of the organic pigment used in the color filter coloring composition of the present invention is preferably 0.01 to 2 parts by mass, and 0.1 to 1 part by mass with respect to 1 part by mass of the polymerizable compound. Particularly preferred.

(Polymerizable compound)
The polymerizable compound may be appropriately selected in consideration of the production process of the color filter. Examples of the polymerizable compound include a photosensitive compound and / or a thermosetting compound, and the photosensitive compound is particularly preferable.

The photosensitive compound is preferably selected from at least one of a photopolymerizable resin, a photopolymerizable monomer and a photopolymerizable oligomer and having an ethylenically unsaturated bond. What is necessary is just to include what becomes resin in the state which hardened | cured in the coloring composition for color filters, and includes the case where only the component which is not resin-ized is contained in the uncured state.
Examples of the photopolymerizable compound, photopolymerizable monomer, and photopolymerizable oligomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and ethylene glycol di (meth). Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) Acrylate, bisphenol A type epoxy di (meth) acrylate, bisphenol F type epoxy di (meth) acrylate, bisphenol fluorene type epoxy di (meth) acrylate Rate (meth) acrylic acid esters such as and the like. Also, vinyl resins such as acrylic acid (co) polymer, (meth) acrylic acid (co) polymer, maleic acid (co) polymer, polyethylene oxide, polyvinylpyrrolidone, polyamide, polyurethane, polyether, polyester, etc. Resins having an ethylenic double bond in the side chain can also be mentioned. These may be used alone or in combination of two or more. The compounding quantity of a polymeric compound is 20-95 mass% in the total solid in a composition for color filters, Preferably the range of 40-80 mass% is good.

  The blending ratio of the polymerizable compound is preferably 40 to 95% by mass, more preferably 50 to 90% by mass, based on the total solid content in the color filter composition. In the composition, other resins and the like can be blended as necessary. In this case, it is desirable that the total amount of the other resins falls within the above range. The total solid content means a component that remains as a solid content after drying and curing, does not include a solvent, and includes a monomer.

(Photopolymerization initiator)
When a photosensitive compound is used as the polymerizable compound, a photopolymerization initiator is used together with the monomer and / or oligomer of the photosensitive compound. Examples of the photopolymerization initiator include one or more selected from compounds such as benzophenone derivatives, acetophenone derivatives, benzoin derivatives, benzoin ether derivatives, thioxanthone derivatives, anthraquinone derivatives, naphthoquinone derivatives, and triazine derivatives. A known photosensitizer may be used together with these photopolymerization initiators.

Examples of the thermosetting resin include melamine resin, urea resin, alkyd resin, epoxy resin, phenol resin, and cyclopentadiene resin.
In the present specification and claims, “photosensitive resin” and “thermosetting resin” include not only a cured resin but also a polymerizable monomer and / or oligomer.

  In addition to the photosensitive resin and / or thermosetting resin, as other polymerizable compound, a binder resin having an acidic group and a resin generally used for inks such as an acrylic resin and a urethane resin may be used. Good.

〔solvent〕
The pigment dispersion may be aqueous or non-aqueous, but differs depending on the method of producing the color filter. For example, the photolithography method is preferably non-aqueous, and the inkjet method may be either.
Examples of the solvent used in the coloring composition of the present invention include fatty acid esters such as ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, and the like. Ketones; aromatics such as benzene, toluene, xylene; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol; ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol , Dipropylene glycol, tripropylene glycol, polypropylene glycol, trimethylene glycol Glycerin; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and other alkylene glycol monoalkyl ethers; triethylene Alkylene glycol dialkyl ethers such as glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether; ethers such as tetrahydrofuran, dioxane, diethylene glycol diethyl ether; monoethanolamine, diethanol Alkanolamines such as amine and triethanolamine; N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc. Nitrogen-containing polar organic solvent; water and the like.

  Among these solvents, those which are water-soluble may be mixed with water and used as an aqueous medium. Moreover, you may mix and use 2 or more types chosen from said solvent except water, and may use it as an oil-based medium.

  It is preferable that the coloring composition for color filters in the present invention further contains one or more dispersants selected from surfactants, silicone additives, silane coupling agents, and titanium coupling agents. Two or more of these dispersants may be used in combination.

Specific examples of the dispersant will be described below.
The surfactant is not particularly limited as long as it has a surface active action, and examples thereof include cationic, anionic, nonionic, and amphoteric surfactants. Specific examples thereof include alkanes. Sulfonate, linear alkylbenzene sulfonate, branched alkylbenzene sulfonate, alkyl naphthalene sulfonate, naphthalene sulfonate formaldehyde condensate, alkyl sulfate, polyoxyethylene alkyl ether sulfate, alkyl phosphate, poly Anionic surfactants such as oxyethylene alkyl ether phosphates and aliphatic monocarboxylates; cationic surfactants such as alkylamine salts and quaternary amine salts; glycerin fatty acid esters, sorbitan fatty acid esters, Polyoxyethylene alkyl ether, polyoxy Nonionic surfactants such as ethylene alkylphenyl ether, polyethylene glycol fatty acid esters, and polyoxyethylene sorbitan fatty acid esters; amphoteric surfactants such as alkylbetaines; any of cationic, anionic, nonionic, or amphoteric Examples thereof may include a high molecular weight surfactant.

  Specific examples of the silicone-based additive include polyalkylsiloxane, polyalkylphenylsiloxane, polyorganosiloxane, polydimethylsiloxane, polyorganosiloxane polyether copolymer, polyfluorosiloxane, and organosilane. These silicone additives may be used in combination of two or more.

  Specific examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-glycidoxy. Propyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, Methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane n- butyl trimethoxysilane, isobutyl trimethoxysilane, trimethyl methoxysilane, hydroxypropyl Ritori silane, n- hexadecyl trimethoxysilane, and the like n- octadecyl trimethoxysilane.

  Specific examples of the titanium coupling agent include isopropyl tri (N-aminoethylaminoethyl) titanate and dibutoxybistriethanolamine titanate.

  Although the usage-amount of said dispersing agent is based also on the kind of dispersing agent to be used, it is preferable to use 0.1-100 mass parts with respect to 100 mass parts of organic pigments, and 0.5-80 mass parts is used. Is particularly preferred.

  The method for using the dispersant is not particularly limited, and may be a known method for preparing a coloring composition for photolithography.

  The present invention also provides a color filter obtained using the above-described coloring composition for a color filter. The color filter exhibits high contrast and good light transmission. Specifically, at a wavelength of 650 nm, the light transmittance is preferably 85% or more, more preferably 90% or more.

  In order to produce the color filter of the present invention, any known method may be used, and preferred examples include a photolithography method and an ink jet method. Hereinafter, the photolithography method and the inkjet method will be described in detail.

1) Photolithographic method When a color filter is formed by a photolithography method, a photosensitive resin is used as the polymerizable compound of the coloring composition for a color filter of the present invention. The photosensitive resin is blended in the coloring composition together with the photopolymerization initiator as a monomer and / or oligomer, and is cured by light irradiation to form a film on the transparent substrate.

  As the photosensitive resin, a polymer or copolymer of a polymerizable monomer having one or more ethylenic double bonds in the molecule is preferably used.

  As these photosensitive resins (polymerizable monomers), acrylic acid esters and methacrylic acid esters are particularly preferable. Specifically, methyl acrylate, methyl methacrylate, butyl methacrylate, butyl acrylate, pentaerythritol tetraacrylate, pentaerythritol tetra Methacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, glycerol diacrylate, glycerol dimethacrylate, 1,4-butanediol Diacrylate, 1,4-butanediol dimethacrylate, vinyl Phenol A diacrylate, and bisphenol A dimethacrylate.

  In the case of using the photolithography method, a binder resin having an acidic group is used in addition to the above-described photosensitive resin in the coloring composition for a color filter of the present invention. Examples of the binder resin having an acidic group include resins having a carboxyl group, a hydroxyl group, a sulfonic acid group, and the like, and a binder resin having a carboxyl group and / or a hydroxyl group is preferable.

  Examples of the binder resin having an acidic group include monomers having an ethylenic double bond selected from acrylic esters, methacrylic esters, styrene, vinyl acetate, vinyl chloride, N-vinylpyrrolidone, acrylamide, and the like. , Acrylic acid, methacrylic acid, p-styrene carboxylic acid, p-styrene sulfonic acid, p-hydroxystyrene, maleic anhydride and the like, and a monomer having an ethylenic double bond having an acidic group Polymers are preferably used.

  The binder resin having an acidic group is preferably used in an amount of 0.5 to 4 parts by mass, particularly preferably 1 to 3 parts by mass with respect to 1 part by mass of the photosensitive resin (polymerizable monomer).

  Solvents used in the coloring composition for photolithography include fatty acid esters, ketones, aromatics, alcohols, glycols, glycerin, alkylene glycol monoalkyl ethers, alkylene glycol dialkyl ethers, ethers, and One or more oily media selected from nitrogen-containing polar organic solvents can be mentioned.

  The amount of these solvents used is preferably 3 to 30 times, and particularly preferably 4 to 15 times, the total mass of components other than the solvent in the colored composition.

  In addition to the above-described components, the coloring composition for the photolithography method in the present invention, if necessary, wetting agent, anti-fading agent, emulsion stabilizer, ultraviolet absorber, preservative, antifungal agent, pH adjustment And known additives (described in JP-A-2003-306623) such as an agent, a surface tension modifier, an antifoaming agent, a viscosity modifier, a dispersion stabilizer, a rust inhibitor, and a chelating agent. These various additives may be added to the oil phase or the aqueous phase at the time of preparation.

  The coloring composition for a color filter of the present invention includes the above-described pigment composition of the present invention, a polymerizable compound, a solvent, and other various additives such as a bead mill, a ball mill, a sand mill, a two-roll mill, a three-roll mill, and a homogenizer. It can be prepared by a method including a step of uniformly mixing and dispersing using a device such as a kneader or a shaker and a step of adjusting the viscosity using the solvent or the like.

  As a method for forming a color filter on a display substrate using the coloring composition for a color filter of the present invention, a known photolithography method may be used. For example, the step of uniformly applying the colored composition of the present invention onto a display substrate by a known method such as a printing method, a spray method, a bar coating method, a roll coating method, or a spin coating method, and removing the solvent in the ink by heating. The color filter can be obtained by a method including a step of exposing the color filter pattern on the display substrate using a high-pressure mercury lamp, an alkali developing step, a cleaning step, and a baking step.

2) Inkjet method When a color filter is formed using an inkjet method, the polymerizable compound of the coloring composition for a color filter of the present invention is not particularly limited as long as it is conventionally used for an inkjet ink. Any of them may be used. A monomer of a photosensitive resin and / or a thermosetting resin is preferably used.

  Examples of these photosensitive resins include acrylic resins, methacrylic resins, and epoxy resins, and acrylic resins and methacrylic resins are preferably used. Acrylic resins and methacrylic resins are photopolymerizable monomers selected from acrylic esters, methacrylic esters, urethane acrylates, urethane methacrylates, acrylic amides, methacrylic amides, alkyl acrylates, benzyl methacrylates, benzyl acrylates, aminoalkyl methacrylates, and the like. A combination of a monomer and a photopolymerization initiator selected from compounds such as a benzophenone derivative, an acetophenone derivative, a benzoin derivative, a benzoin ether derivative, a thioxanthone derivative, an anthraquinone derivative, a naphthoquinone derivative, and a triazine derivative is preferable. In addition to the above photopolymerizable monomer, a photopolymerizable monomer having a hydrophilic group such as acrylic acid, methacrylic acid, maleic acid, and vinyl acetate may be added.

  Examples of the thermosetting resin include melamine resin, urea resin, alkyd resin, epoxy resin, phenol resin, and cyclopentadiene resin.

  When the inkjet method is used, the solvent used for the coloring composition may be an oily medium or an aqueous medium, but an aqueous medium is more preferably used. As the aqueous medium, water or a mixed solvent of water and a water-soluble organic solvent is used, and a mixed solvent of water and a water-soluble organic solvent is preferable. Moreover, it is desirable to use what was deionized.

  Although the oil-based medium used in said coloring composition is not specifically limited, For example, what was mentioned as a solvent for coloring compositions used for the photolithographic method etc. can be used.

  The solvent used in the aqueous medium is selected from alcohols, ketones, ethers, glycols, glycerin, alkylene glycol monoalkyl ethers, alkylene glycol dialkyl ethers, alkanolamines, and nitrogen-containing polar organic solvents. And those having water solubility. These water-soluble organic solvents may be used alone or in combination of two or more.

  The amount of these solvents used is not particularly limited, but the amount used may be appropriately adjusted so that the viscosity of the colored composition is 20 mPa · s or less, preferably 10 mPa · s or less at room temperature.

  The colored composition of the present invention can be prepared by a method including a step of dispersing and mixing components in the same manner as the colored composition for photolithography. If necessary, a dispersing agent may be added at the time of dispersion as in the case of the photolithography method.

  In addition to the above-described components, the coloring composition according to the present invention may include a wetting agent, an antifading agent, an emulsion stabilizer, an ultraviolet absorber, an antiseptic, an antifungal agent, a pH adjuster, and a surface tension adjuster. Various known additives such as an agent, an antifoaming agent, a viscosity modifier, and a dispersion stabilizer may be included.

  A method for forming a color filter using the colored composition obtained as described above is not particularly limited as long as it is a method for forming a color filter by a known inkjet method. For example, a step of forming a predetermined color filter pattern in the form of droplets on a display substrate, a step of drying the color filter pattern, and a heat treatment or light irradiation or both are performed to cure and form a film on the color filter pattern on the substrate. A color filter can be formed by a method including steps.

  Although the photolithography method and the ink jet method have been described above, the color filter of the present invention may be obtained by other methods.

Even when a color filter forming method other than the above (for example, various printing methods such as an offset printing method) is used, the colored composition contains the polymerizable compound and the solvent described above, and is represented by the formula (1). As long as the compound is used as a colorant, both the color filter coloring composition and the obtained color filter are included in the scope of the present invention.
For example, the components such as the polymerizable compound, the solvent, and the additive, and the formulation at the time of forming the color filter may be selected according to conventional examples, and are not limited to those described in the description of the photolithography method and the inkjet method described above.

  The color filter of the present invention obtained as described above forms pixels together with G (green) and B (blue) color filter patterns by a known method. Such a filter can provide a liquid crystal display that can display a clear image with very high transparency, excellent spectral characteristics, and a small depolarization effect.

  As a method for forming a color filter, a pattern is first formed with a photoresist and then dyed, or disclosed in JP-A-4-163552, JP-A-4-128703, and JP-A-4-175653. As described above, there is a method of forming a pattern with a photoresist added with a dye. Any of these methods may be used as a method for introducing the pigment composition of the present invention into a color filter. Preferred methods include JP-A-4-175533 and JP-A-6-35182. And a positive resist composition comprising a thermosetting resin, a quinonediazide compound, a cross-linking agent, the pigment composition of the present invention and a solvent, and exposure through a mask after coating on the substrate. And developing the exposed portion to form a positive resist pattern, exposing the entire surface of the positive resist pattern, and then curing the exposed positive resist pattern. it can. In addition, a black matrix is formed according to a conventional method, and an RGB primary color system or Y, M, C complementary color system color filter can be obtained. In the case of a color filter, the amount of the organic pigment used in the pigment composition of the present invention is not limited, but is preferably 0.1 to 50% by mass.

  Regarding the thermosetting resin, quinonediazide compound, crosslinking agent, and solvent used in this case, and those used, those described in the above-mentioned patent documents can be preferably used.

  EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited to these examples. Hereinafter, “parts” means parts by mass.

  The X-ray diffraction measurement of the β-type crystal form azo pigment uses CuKα rays with a powder X-ray diffraction measurement device RINT2500 (manufactured by Rigaku Corporation) according to Japanese Industrial Standards JISK0131 (general rules for X-ray diffraction analysis) The test was conducted under the following conditions.

Measuring instrument: Automatic X-ray diffractometer RINT2500 manufactured by Rigaku
X-ray tube: 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.
Receiving slit: 0.6mm
Using vertical goniometer

[Synthesis Example 1]
The β-type crystal form azo pigment represented by the formula (1) was synthesized by the following route.

Synthesis of β-type crystal form azo pigment 20 g of the compound represented by the formula (2) was added to 200 ml of phosphoric acid to completely dissolve at room temperature, this solution was ice-cooled and kept at −5 ° C., and sodium nitrite 8 0.0 g was added, and the mixture was stirred for 40 minutes. Thereafter, 3.3 g of sodium nitrite was added, and the mixture was further stirred for 20 minutes. To this reaction solution, 1.5 g of urea was added to obtain a diazonium salt solution. This diazonium salt solution was dropped into a solution prepared by dissolving 21 g of the compound represented by the formula (3) in N, N-dimethylacetamide (DMAc) (400 ml) over 80 minutes while maintaining at 5 to 10 ° C. The resulting solution was stirred for 2 hours while maintaining at 5 to 10 ° C., and then 240 ml of methanol was added and further stirred for 10 minutes. The precipitated crystals were separated by filtration and washed with 300 ml of methanol. The crystals were neutralized by adding 500 ml of water and 50 ml of saturated sodium bicarbonate without drying. The precipitated crystals were separated by filtration and washed with 300 ml of water. The obtained crystal and water-containing composition (water content 61 mass%) was suspended in 400 mL of DMAc without drying, and then stirred at 80 ° C. for 60 minutes and then cooled to room temperature over 2 hours. The crystals were separated by filtration and dried at room temperature for 24 hours and in a vacuum desiccator at 50 ° C. for 10 hours to obtain 26.2 g of β-type crystal form azo pigment (D-2). Yield 80%.
When the X-ray diffraction of the obtained β-type crystal form azo pigment was measured under the above conditions, the Bragg angle (2θ ± 0.2 °) was 7.1 °, 11.7 °, 20.0 ° and 27. It showed a characteristic X-ray diffraction peak at 1 °. The peak height at 10.9 relative to the peak height at 11.9 ° was 0.2 or less. A CuKα characteristic X-ray diffraction diagram is shown in FIG.

[Example 1] Preparation of pigment dispersion 1 2.5 parts of the β-type crystal form azo pigment synthesized in Synthesis Example 1 were mixed with 0.5 part of sodium oleate, 5 parts of glycerin and 42 parts of water, and the diameter was 0. Using a planetary ball mill with 100 parts of 1 mm zirconia beads, dispersion was performed at 300 rpm for 6 hours. After completion of the dispersion, the zirconia beads were separated to obtain a red pigment dispersion 1 (volume average particle diameter; Mv≈82 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.).

[Comparative Synthesis Example 1]
The azo pigment (D-1) represented by the formula (1) was synthesized by the following route.

1.0 g of the compound (2) was dissolved in 10 ml of phosphoric acid (Wako Pure Chemical Industries, Ltd .; reagent special purity 85%, the same applies hereinafter). This solution was ice-cooled and kept at −5 to 0 ° C., 0.38 g of sodium nitrite was added and stirred for 1 hour to obtain a diazonium salt solution. Separately, 25 ml of acetonitrile was added to 1.30 g of compound (3), and the above diazonium salt solution was added at 8 ° C. or lower with stirring. Upon completion of the addition, the ice bath was removed and the mixture was further stirred for 3 hours. 50 ml of acetonitrile was added to the reaction solution, and the mixture was stirred for 30 minutes. The precipitated crystals were separated by filtration and washed with 30 ml of acetonitrile. The crystals were added to 100 ml of water without drying, and a solution of 0.5 g of sodium bicarbonate dissolved in 30 ml of water was added, followed by stirring at 20 to 25 ° C. for 30 minutes. The precipitated crystals were separated by filtration, and further thoroughly washed with water. The obtained crystals were added to 50 ml of dimethylacetamide without drying and heated and stirred at 100 ° C. for 30 minutes. The mixture was stirred at room temperature for 30 minutes, and the precipitated crystals were filtered and washed with 30 ml of dimethylacetamide. The obtained crystals were added to 50 ml of dimethylacetamide without drying, 25 ml of water was gradually added dropwise, stirred at 80 ° C. for 1 hour, and further stirred at room temperature for 30 minutes. The precipitated crystals were filtered and washed with 20 ml of dimethylacetamide / water = 2/1 and 20 ml of methanol. The obtained crystal was dried to obtain 1.2 g of (D-1) represented by the formula (1). Yield 52%.
The obtained azo pigment (D-1) was analyzed using CuKα characteristic X-ray diffraction, and the peak intensity of 10.9 ° characteristic of the α-type crystal form azo pigment was characteristic of the α-type crystal form azo pigment. By dividing by the sum of the peak intensity of 10.9 ° and the peak intensity of 11.9 ° characteristic of the β-type crystal form azo pigment, the azo pigment (D-1) is represented by the α type represented by the formula (1) It was found to be a mixture of 74% crystal form azo pigment and 26% β type crystal form azo pigment represented by the formula (1) (a mixture of α type crystal and β type crystal). A CuKα characteristic X-ray diffraction pattern of the azo pigment (D-1) is shown in FIG.

[Comparative Example 1] Preparation of Comparative Pigment Dispersion 1 Comparison of red color was conducted in the same manner as in Example 1 except that the azo pigment (D-1) was used instead of the β-type crystal form azo pigment used in Example 1. A pigment dispersion 1 was obtained.

Comparative Example 2 Preparation of Comparative Pigment Dispersion 2 In place of the β-type crystal form azo pigment used in Example 1, C.I. I. A red comparative pigment dispersion 2 was obtained in the same manner as in Example 1 except that CI Pigment Red 254 (B-CF manufactured by Ciba Specialty) was used.

(Evaluation)
<Evaluation of coloring power>
Each pigment dispersion obtained above was designated as No. No. 3 bar coater was applied to a photo mat paper <pigment only> manufactured by Seiko Epson Corporation. 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 results are shown in Table 1.
◎: OD value is 1.6 or more ○: OD value is 1.4 or more and less than 1.6 △: OD value is 1.2 or more and less than 1.4 ×: OD value is less than 1.2

<Solvent resistance evaluation>
Regarding solvent resistance, the β-type crystal form azo pigment represented by the formula (1) used in Pigment Dispersion 1 (Example 1) and the azo pigment (D) used in Comparative Pigment Dispersion 1 (Comparative Example 1) -1) and C.I. used in Comparative Pigment Dispersion 2 (Comparative Example 2). I. For each of Pigment Red 254, 10 mg of the pigment was suspended in 50 mL of N-methylpyrrolidone, and when it was heated at an internal temperature of 60 ° C. for 10 minutes, x was completely dissolved, and ○ was not completely dissolved. did.

<Hue evaluation>
In the reflection spectrum of the coated product having an OD value of 1.0 by the method used in the evaluation of the coloring power described above, the following three visual criteria were used.
(1) Not yellowish (2) Not bluish (3) Judged to be vivid.
◎: When all are satisfied ○: When two are satisfied △: When one is satisfied ×: When all are not satisfied

<Light resistance evaluation>
The coated product having an image density of 1.0 used for evaluating the coloring power was irradiated with xenon light (170000 lux .; in the presence of a cut filter of 325 nm or less) for 30 days using a fade meter, and the image density before and after the xenon irradiation was measured as the reflection density. It was measured using a meter and evaluated as a dye residual ratio [(post-irradiation density / pre-irradiation density) × 100%]. The results are shown in Table 1.

As is apparent from the results in Table 1, the β-form crystal form pigment of the present invention exhibits high solvent resistance and is particularly excellent in coloring power and hue when made into a pigment dispersion.
Therefore, the pigment dispersion using the pigment of the present invention can be suitably used, for example, for printing ink such as inkjet.

[Example 2]
The polymer dispersant represented by Dispersant 10 described on page 22 of International Publication No. WO06 / 064193 was neutralized with an aqueous potassium hydroxide solution. 30 parts by mass of the β-type crystal form azo pigment synthesized in Synthesis Example 1 and 95 parts by mass of ion-exchanged water are added to 75 parts by mass of the aqueous dispersant solution (solid content concentration: 20% by mass), and the mixture is stirred with a disper. Mix and coarsely disperse with wings. 600 parts by mass of zirconia beads were added to the mixed and roughly dispersed liquid, and this was dispersed with a disperser (sand grinder mill) for 4 hours, and then separated into beads and a dispersion. While stirring the resulting mixture, 2 parts by mass of polyethylene glycol diglycidyl ether (Denacol EX-821 manufactured by Nagase Kasei Kogyo Co., Ltd.) was slowly added at 25 ° C., and the mixture was stirred at 50 ° C. for 6 hours. Furthermore, impurities were removed using an ultrafiltration membrane having a fractional molecular number of 300K, and this was attached to a filter having a pore size of 5 μm (acetylcellulose membrane, outer diameter: 25 mm, manufactured by Fuji Film Co., Ltd.). By filtering with a syringe and removing coarse particles, a pigment dispersion 2 (particle size 80 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.) was obtained.

[Comparative Example 3]
A comparative pigment dispersion 3 was obtained in the same manner as in Example 2 except that the azo pigment (D-1) was used instead of the β-type crystal form azo pigment used in Example 2.

Example 3
5% by mass of the pigment dispersion 2 obtained in Example 2, 10% by mass of glycerin, 5% by mass of 2-pyrrolidone, 2% by mass of 1,2-hexanediol, 2% by mass of triethylene glycol monobutyl ether, Each component was added so that it might become 0.5 mass% of propylene glycol, and 75.5 mass% of ion-exchange water, and the obtained liquid mixture was filtered with a 1 μm pore size filter (acetylcellulose membrane, outer diameter: 25 mm, Fujifilm Corporation). The pigment ink liquid 3 of the present invention was obtained by filtering with a syringe having a capacity of 20 ml equipped with a) and removing coarse particles.

[Comparative Example 4]
A comparative pigment ink liquid 4 was obtained in the same manner as in Example 3 except that the comparative pigment dispersion 3 obtained in Comparative Example 3 was used instead of the pigment dispersion 2 obtained in Example 2.

  In Table 2, “Ejection stability”, “Light fastness”, “Heat fastness”, “Ozone fastness”, “Metal gloss”, and “Ink liquid stability” are the same for each ink. ) Installed in a magenta ink liquid cartridge of an ink jet printer PX-V630 manufactured by the company, PX-V630 pigment ink liquid was used for the other color inks, and the image receiving sheet was a photographic paper <glossy> manufactured by Seiko Epson Corporation. In addition, the photographic paper Krispia <High Gloss> manufactured by Seiko Epson Co., Ltd. recommends the recommended mode and prints a monochrome image pattern with clear and stepwise density changes, as well as blue, red, and gray image patterns. And image robustness were evaluated. Evaluations other than metallic luster were performed in a single color.

  The following evaluation was performed on Example 3 (Pigment Ink Liquid 3) and Comparative Example 4 (Comparative Pigment Ink Liquid 4). The results are shown in Table 2.

(Evaluation experiment)
1) About discharge stability, after setting a cartridge in a printer and confirming the protrusion of the ink from all the nozzles, 20 sheets of A4 were output and evaluated according to the following criteria.
A: No printing disturbance from the start to the end of printing B: Output with a printing disorder occurs C: There is a printing disturbance from the start to the end of printing

2) For image storage stability, the following evaluation was performed using a print sample.
[1] Light fastness is measured by measuring the image density Ci immediately after printing with a Photographic Densitometer 310 (X-rite 310) manufactured by X-Rite, and then using xmason light (100,000 lux) on the image for 14 days using a weather meter manufactured by Atlas. After the irradiation, the image density Cf was measured again, and the image remaining rate Cf / Ci × 100 was obtained and evaluated.
The image afterimage rate is evaluated at three points of reflection density of 1, 1.5 and 2. A is the case where the image remaining rate is 80% or more at any density, and B is the case where 1 or 2 points is less than 80%. The case where the concentration was less than 80% at all concentrations was defined as C.
[2] For heat fastness, the density before and after storing the print sample for 7 days under conditions of 80 ° C. and 60% RH was measured with a reflection densitometer X-rite 310, and the image residual ratio was determined and evaluated. . The image afterimage rate is evaluated at three points of reflection density of 1, 1.5 and 2, and A is the case where the image remaining rate is 95% or more at any density, and B is the case where 1 or 2 points is less than 95%. , C was defined as less than 95% at all concentrations.
[3] With regard to ozone resistance (ozone fastness), the sample was left in a box where the ozone gas concentration was set to 5 ppm (25 ° C .; 50%) for 14 days, and the image density before and after being left under ozone gas was measured using a reflection densitometer X- It measured using Rite310 and evaluated as image residual ratio. The reflection density was measured at three points of 1, 1.5 and 2.0. The ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS. The evaluation was made in three stages, with A as the case where the image remaining ratio was 80% or higher at any density, as B when the 1 or 2 points were less than 80%, and C when the density was less than 70% at all densities.
3) Presence or absence of occurrence of metallic luster: Magenta, blue, and red solid printed portions were visually observed with reflected light and evaluated.
The case where the metallic luster was not visible was evaluated as “◯”, and the case where the metallic luster was visible was evaluated as “x”.
4) Ink liquid stability: After aging the pigment ink liquids of Examples and Comparative Examples at 60 ° C. for 10 days, the evaluation was made with “◯” indicating no change in the particle diameter in the pigment ink liquid and “X” indicating that there was a change in the particle diameter. did. The results are shown in Table 2 below.

From the results in Table 2, it was found that the pigment ink liquid using the pigment of the present invention was excellent in ejection property and fastness, suppressed the occurrence of metallic luster, and excellent in pigment ink liquid stability.
As is apparent from the results in Table 2, it can be seen that the system using the ink liquid of the present invention is excellent in all performance. In particular, the light fastness, ozone fastness and ink liquid stability are superior to the comparative examples.

Example 4
An image of the pigment ink liquid 3 produced in Example 3 was printed on “inksai”, an inkjet paper photo glossy paper manufactured by Fuji Film Co., Ltd., using PX-V630 manufactured by Epson Corporation. Similar results were obtained when similar evaluations were performed.
As is apparent from the results of Tables 1 and 2, Pigment Dispersions 1 and 2 and the pigment ink liquid 3 using the pigment of the present invention are excellent in color tone and exhibit high coloring power and light resistance.
Therefore, the pigment dispersion using the pigment of the present invention can be suitably used, for example, for printing ink such as inkjet.

Example 201
[Production of color filters by photolithography]
The β-type crystal form azo pigment synthesized in Synthesis Example 1 was used. The material shown below was put into a 70 cc mayonnaise bottle, and this was shaken for 6 hours with a shaking disperser (DAS200 manufactured by LAU) to separate zirconia beads, whereby a pigment dispersion 201 was obtained.

Example 202
The following materials were added to the pigment dispersion 201, and the mixture was further shaken for 30 minutes with the above shaker disperser to prepare a color filter coloring composition 202 for photolithography.

Example 203
The color filter coloring composition 202 obtained in Example 202 was placed on a slide glass with a bar coater Rod No. 10 and then dried in an oven at 80 ° C. for 5 minutes to obtain an ink coating film.
The above-mentioned coating film was exposed by irradiating under a condition of 200 mJ / cm ² using a high-pressure mercury lamp after appropriately masking a part of the coating film. Thereafter, development was performed at 25 ° C. using a 0.5% aqueous sodium carbonate solution, followed by drying in an oven at 220 ° C. for 20 minutes to produce a color filter 203. The light transmittance of this color filter was measured using a spectrophotometer (manufactured by Hitachi, Ltd., U-3310). Moreover, the wavelength with the minimum transmittance | permeability of the obtained color filter 203 was calculated | required between wavelengths 540-610 nm. The results are shown in Table 5.

Example 204
In Example 201, 0.5 g of a surfactant (BIG Chemie Co., Ltd. pigment wetting dispersant BYK-161) was further added as a dispersant to 0.6 g of the β-type crystal form azo pigment to perform dispersion. Except for the above, the same operation as in Examples 201 to 203 was performed, and a color filter 204 having the same performance as that of the color filter 203 was obtained.

[Comparative Examples 201-203]
Instead of the β-type crystal form azo pigment used in Example 201, azo pigment (D-1), C.I. I. Pigment Red 254 (CI Pigment Red 254 (PR 254): IRGAPHORE DPP RED, manufactured by Ciba Specialty Chemicals) and a compound represented by the following formula [I] were used in Examples 201 to 201, respectively. Comparative color filters 201 to 203 were prepared in exactly the same manner as in 204.

  The light transmittance of the obtained color filter was measured, and the minimum wavelength of the light transmittance, the light transmittance of 650 nm, and the light transmittance of 540 nm were obtained. The results are shown in Table 5.

  The color filters 203 and 204 prepared using the coloring composition for a color filter of the present invention containing a β-type crystal form azo pigment as a colorant have a sharply rising transmittance curve and are transmitted in a region of 650 to 750 nm. The rate was high and an excellent transmittance curve was exhibited. Furthermore, the color filter of Comparative Example 201 has a portion with a high transmittance at 540 nm.

  In addition, the color filter prepared using the coloring composition for a color filter of the present invention has a very low transmittance of blue light of 350 to 400 nm as compared with the color filters obtained in Comparative Examples 202 and 203. In other words, it is possible to display red with high color purity.

  That is, the coloring composition for a color filter of the present invention has a Bragg angle (2θ ± 0.2 °) in CuKβ characteristic X-ray diffraction of 6.9 °, 25.8 among the azo pigments represented by the formula (1). By selecting the one with characteristic X-ray diffraction peaks at ° and 27.1 ° and having a peak height at 10.9 of 0.2 or less relative to the peak height at 11.9 °, It is useful in that red having an optimum hue can be obtained according to the light source wavelength of the light, and as a result, color reproducibility is improved.

[Heat resistance evaluation]
A heat resistance test was conducted using the color filters obtained in Example 203, Example 204, and Comparative Examples 201 to 203.
<Heat resistance test method>
The color filter was exposed at 250 ° C. for 300 minutes in the atmosphere, and the color difference (ΔE ^* _ab ) before and after that was measured with a spectrophotometer (Macbeth Colorey-3000 manufactured by Sakata Inx Corporation). Evaluation was made according to the following criteria, and these results are shown in Table 6.
<Criteria>
○: ΔE * ab <1.0
Δ1.0 ≦ ΔE * ab <1.1
×: 1.1 ≦ ΔE * ab

  The color filters of Examples 203 and 204 prepared using the color filter coloring composition of the present invention containing a β-type crystal form azo pigment as a colorant are compared with those using the color filters of Comparative Examples 201 to 203. The heat resistance was equivalent or better.

(Light resistance evaluation)
The color filters obtained in Example 203, Example 204, and Comparative Examples 201 to 203 were irradiated with xenon light (170000 lux .; Suga test machine in the presence of a cut filter of 325 nm or less) using a fade meter for 40 days. The color difference before and after (ΔE ^* _ab ) was measured with a spectrophotometer (Macbeth Colorey-3000 manufactured by Sakata Inx Corporation). Evaluation was made according to the following criteria, and these results are shown in Table 7.
<Criteria>
○: ΔE * ab ≦ 3.0
Δ: 3.0 <ΔE * ab ≦ 6.0
X: 6.0 <ΔE * ab

  The color filters of Examples 203 and 204 prepared using the coloring composition for a color filter of the present invention containing the azo compound represented by the formula (1) as the colorant used the color filters of Comparative Examples 201 to 203. Compared to those, the light resistance was equivalent or better.

(Contrast evaluation)
The contrast of the color filter obtained in Examples 203 and 204 and Comparative Examples 203 and 204 was measured using a contrast tester CT-1 manufactured by Aisaka Electric Co., Ltd. In the evaluation, contrast ≧ 23000 is indicated by ○, 23000> contrast ≧ 18000 is indicated by Δ, and 18000> contrast is indicated by ×, and the results are shown in Table 8.

  The color filters 203 and 204 of Examples 203 and 204 prepared using the coloring composition for a color filter of the present invention containing a β-type crystal form azo pigment as a colorant are compared with those using the pigment of Comparative Example 203. Showed excellent contrast.

Example 301
<Preparation of Green pigment dispersion>
-Preparation of Green pigment dispersion P1-
As a pigment, C.I. I. Pigment Green 36 and C.I. I. 12.6 parts of a 100/55 (mass ratio) mixture with Pigment Yellow 139, 5.2 parts of a dispersing agent, BYK2001 (Disperbyk: manufactured by BYK Corporation, solid content concentration: 45.1% by mass), and dispersion A mixed solution consisting of 2.7 parts of benzyl methacrylate / methacrylic acid copolymer (acid value 134 mgKOH / g, Mw = 30,000) as a resin and 78.3 parts of propylene glycol monomethyl ether acetate as a solvent was obtained by a bead mill. Green pigment dispersion P1 was prepared by mixing and dispersing for 15 hours.

<Preparation of Red pigment dispersion>
-Preparation of Red pigment dispersion P2-
Β-type crystal form azo pigments and C.I. I. 12.1 parts of 100/45 (mass ratio) mixture with Pigment Yellow 139, and 10.4 parts of BYK2001 (Disperbyk: BYK Corporation (solid content concentration: 45.1% by mass)) as a dispersing agent A mixed solution consisting of 3.8 parts of benzyl methacrylate / methacrylic acid copolymer (acid value 134 mgKOH / g, Mw = 30,000) as resin and 73.7 parts of propylene glycol monomethyl ether acetate as solvent was By mixing and dispersing for 15 hours, a Red pigment dispersion P2 was prepared.

<Preparation of Blue Pigment Dispersion>
-Preparation of Blue pigment dispersion P3-
As a pigment, C.I. I. Pigment blue 15: 6 and C.I. I. 14 parts of a 100/25 (mass ratio) mixture with CI Pigment Violet 23, 4.7 parts of BYK2001 (Disperbyk: BYK Corporation (solid content concentration: 45.1% by mass)) as a dispersant, and a dispersion resin A mixed solution composed of 3.5 parts of a benzyl methacrylate / methacrylic acid copolymer (acid value 134 mgKOH / g, Mw = 30,000) and 77.8 parts of propylene glycol monomethyl ether acetate as a solvent was mixed with a bead mill for 15 hours. Blue pigment dispersion P3 was prepared by mixing and dispersing.

<Preparation of Green Colored Photosensitive Composition (Coating Solution) A-1>
Using the above-mentioned Green pigment dispersion P1, a colored photosensitive composition A-1 was prepared by mixing and stirring so as to have the following composition.

<Preparation of Red colored photosensitive composition (coating liquid) B-1>
Using the above-mentioned Red pigment dispersion P2, the photosensitive composition B-1 was prepared by mixing and stirring so as to have the following composition.

<Preparation of Blue colored photosensitive composition (coating liquid) C-1>
Using the above-mentioned Blue pigment dispersion P3, the photosensitive composition C-1 was prepared by mixing and stirring so as to have the following composition.

The green colored photosensitive composition A-1 prepared above was applied onto an 8-inch device-formed silicon wafer previously sprayed with hexamethyldisilazane to form a photocurable coating film. Then, heat treatment (pre-baking) was performed for 180 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 1.0 μm. Then, using an i-line stepper exposure apparatus FPA-3000i5 + (Canon (Ltd.)), it was irradiated in 50~1000mJ / cm ² through 1.0μm square Bayer pattern mask at a wavelength of 365nm (50mJ / cm ² The amount of exposure changes in steps). Then, the silicon wafer on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type; manufactured by Chemitronics), and CD-2000 (Fuji Film Electronics). Paddle development was performed at 23 ° C. for 180 seconds using a 40% diluted solution (manufactured by Materials Co., Ltd.) to form a colored pattern on the silicon wafer.

A silicon wafer on which a colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer is rotated at a rotation speed of 50 rpm by a rotating device, and pure water is ejected from above the rotation center from a jet nozzle. And then rinsed and then spray dried.
Next, it was heated on a hot plate at 200 ° C. for 5 minutes to obtain a color filter on which a pattern was formed.

Furthermore, by repeating the same process as Green except that the red colored photosensitive composition B-1 and the Blue photosensitive composition C-1 are used and the exposure pattern is exposed through a 1.0 μm square island pattern mask, A color filter 301 formed with an RGB pattern was formed.
It was confirmed that when a camera module was created using a device in which the color filter 301 was formed, it had good spectral characteristics.

Claims (10)

The Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction has characteristic X-ray diffraction peaks at 6.9 °, 25.8 ° and 27.1 °, and the peak height at 11.9 ° An azo pigment represented by the following formula (1) having a peak height at 10.9 of 0.2 or less, a tautomer, salt, hydrate or solvate thereof.

A Bragg angle (2θ in CuKα characteristic X-ray diffraction) comprising a step of subjecting a diazonium salt derived from a heterocyclic amine represented by the following formula (2) to a compound represented by the following formula (3) by an azo coupling reaction: ± 0.2 °) has characteristic X-ray diffraction peaks at 6.9 °, 25.8 ° and 27.1 °, with a peak height at 10.9 ° relative to the peak height at 11.9 °. The manufacturing method of the azo pigment represented by following formula (1) which is 0.2 or less, or its tautomer.

  Furthermore, the composition containing the azo pigment represented by the formula (1) having a water content of 50% by mass or more and 200% by mass or less or a tautomer thereof and water is provided for the post-treatment step. Item 3. A process for producing an azo pigment or a tautomer thereof according to Item 2.   The azo pigment represented by the formula (1) has a Bragg angle (2θ ± 0.2 °) in CuKα characteristic X-ray diffraction of 6.9 °, 11.9 °, 23.8 °, 25.8 °, It has characteristic X-ray diffraction peaks at 26.7 ° and 27.1 °, and the peak height at 10.9 ° is 0.2 or less with respect to the peak height at 11.9 °. Item 4. A method for producing an azo pigment or a tautomer thereof according to Item 2 or 3.   The azo pigment obtained by the manufacturing method according to any one of claims 2 to 4, a tautomer, salt, hydrate or solvate thereof.   A pigment dispersion comprising at least one selected from the azo pigments according to claim 1 or 5, tautomers, salts, hydrates or solvates thereof.   A coloring composition comprising the pigment dispersion according to claim 6.   An ink for inkjet recording, comprising the colored composition according to claim 7.   A coloring composition for a color filter, comprising the coloring composition according to claim 7.   A color filter produced using the coloring composition for a color filter according to claim 9.

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