JP5013746B2 - Dye compound and recording ink - Google Patents

Description

  The present invention relates to a dye compound and a recording ink.

  Due to the remarkable development of recording technology in recent years, high-quality color recording and image output have become possible very easily. In particular, the use of digital cameras, scanners, ink jet printers, color laser printers and the like as personal computers and input / output devices has become common. Among the above, the recording apparatus using the ink jet recording method has been rapidly spread because the material cost is low, high speed recording is possible, noise during recording is small, and color recording is easily obtained. Therefore, further development is demanded. That is, it is required that a higher-definition image or document can be output more easily, and an image excellent in color reproduction can be obtained, and this state can be maintained for a long period of time.

  A water-based ink is generally used as the ink-jet ink. Moreover, as a pigment | dye used for the ink for inkjet, both a dye and a pigment can be used. And it is preferable to select suitably the pigment | dye used for an ink from the point of the suitability with respect to an inkjet recording system. For example, in a method called thermal jet method in which bubbling of ink liquid by heat is an energy source for ejecting ink, it is common to use a water-soluble dye as a coloring material for the ink rather than a pigment from the viewpoint of suitability of the ink jet recording method. Is. This is because inks using pigments as coloring materials are excellent in terms of durability of the image after printing, but the ink jet method as described above, such as problems of ink storage stability and irregularities in ejection characteristics This is because it is often difficult to apply to the above. On the other hand, inks containing water-soluble dyes have advantages in ink jetting characteristics and storage stability, but recorded images formed with the inks are generally inferior in image storage stability (ie, weather resistance). There was a problem of inferiority).

On the other hand, various studies have been made for the purpose of solving these problems and enabling image formation satisfying the storage stability while maintaining the color reproducibility and transparency of the image. For example, a method in which a water-soluble dye that gives an image having high fastness to oxidizing gas (NO _x , SO _x , ozone, etc.) in light or air is used as a coloring material for ink-jet ink. However, the water-soluble dyes that have been used so far in the above methods are not sufficient in color tone, and there is a strong demand for the development of pigments with excellent color reproducibility for higher image quality. Yes. Some azo dyes use a special coupler in the production process, and there is a demand for dyes that can be obtained by a simpler method.

  Among those studied so far, there is a proposal for an azopyridone dye as a high-color yellow water-soluble dye compound (see Patent Document 1). Furthermore, as a system with improved weather resistance of this system, a dye having a carboxyl group at the o-position of the diazo component has been proposed as a highly robust dye (see Patent Document 2). However, these dyes are still not sufficient to satisfy all the performances, and images with sufficient water resistance cannot be obtained. Furthermore, for example, the dye disclosed in Patent Document 3 can give an image having high fastness, but an image having a sufficient color tone has not been obtained.

  In addition, as a result of investigations by the present inventors, the compounds described in Patent Document 2 are very wide, and although there are compounds that give images showing good fastness properties, they can exhibit sufficient fastness properties. There was a problem that some compounds were not included. In addition, when the compound described in Patent Document 2 is used as a coloring material for ink, sufficient performance with respect to wet fastness of an image cannot be obtained.

  There is also a proposal for a method for producing a color filter for a color liquid crystal display by an ink jet recording method (see, for example, Patent Document 4). In image formation using a color filter, generally, a color filter having a cell composed of three primary colors of red, blue and green light is colored by a method of observing with a light selectively transmitted through the liquid crystal cell. ing. For this reason, red, blue, and green pigments are used for the ink forming the color filter. In recent years, image quality in liquid crystal display images has been improved, and output devices have become more sophisticated. Therefore, there is a need for green ink that has excellent color development and transparency, better color tone, and high robustness. Yes.

JP 2001-288393 A Special table 2003-510398 gazette Special Table 2002-504613 Japanese Patent Laid-Open No. 7-072325

  Accordingly, an object of the present invention is to provide a dye compound which is excellent in spectral reflection characteristics such as color developability and transparency and has high fastness. Another object of the present invention is to provide a water-based ink that gives an image having a good color tone and excellent storage stability when used as an inkjet ink.

［上記一般式（１）中、Ｘは、−ＣＯＮＨ₂又は−ＳＯ₃Ｍ、Ｙは、−ＣＯＯＭを表す。Ｍは、カウンターイオンを表す。］ The above object is achieved by the present invention described below. That is, the present invention is a dye compound characterized by having a structure represented by the following general formula (1).

[In the general formula (1), X is -CONH ₂ or -SO ₃ M, Y is - represents a COOM. M represents a counter ion. ]

  The pyridone azo dye which is the coloring compound of the present invention is useful as an acidic yellow dye which gives an image having excellent light resistance, high wet fastness and a wide color reproduction range. Further, the coloring compound of the present invention can be effectively used as a coloring material for ink for ink jet recording. Furthermore, since the coloring compound of the present invention is excellent in spectral characteristics such as color developability and transparency, it is useful as a coloring material for ink for forming pixels of a color filter.

  Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. As a result of intensive studies to solve the problems of the prior art described above, the present inventors have found that the dye compound represented by the following general formula (1) is excellent in spectral reflection characteristics such as color developability and transparency, The present invention has been found by finding that it is a dye having high fastness to oxidizing gas in the air. When the dye compound is used to form an aqueous ink, it is possible to provide an ink suitable for ink jet recording having a good color tone. Hereinafter, the following general formula (1) will be described in detail.

［上記一般式（１）中、Ｘは、−ＣＯＮＨ₂又は−ＳＯ₃Ｍ、Ｙは、水素原子又は−ＣＯＯＭを表す。Ｍは、カウンターイオンを表す。］ [Dye Compound Represented by General Formula (1)]

[In the general formula (1), X represents —CONH ₂ or —SO ₃ M, and Y represents a hydrogen atom or —COOM. M represents a counter ion. ]

Y in the general formula (1) is either a carboxyl group (—COOM) or a hydrogen atom, but a carboxyl group with higher water solubility is preferable in consideration of application to ink jet ink. Regarding the substitution position, assuming that the site linked to the azo group is 1 and the binding site of the o-carboxyl group is 2, a compound having a carboxyl group at positions 3 to 5 is preferably used. On the other hand, use of a compound having a bulky substituent at the 6-position is not preferable because light resistance is lowered. Examples of X in the general formula (1) include a carbamoyl group (—CONH ₂ ) and a sulfone group (—SO ₃ M). When Y described above is a hydrogen atom, X is preferably a sulfonic acid in order to ensure the water solubility necessary for the compound.

M in each general formula including general formulas (5) and (6) described later represents a counter ion. Preferred counter ions include the following. That is, a hydrogen atom;
Ions of alkali metals such as lithium, sodium and potassium;
Ammonium, methylammonium, dimethylammonium, trimethylammonium, tetramethylammonium;
Ethylammonium, diethylammonium, triethylammonium, tetraethylammonium;
n-propylammonium, isopropylammonium, diisopropylammonium;
n-butylammonium, tetra-n-butylammonium, isobutylammonium;
Examples include ammonium such as monoethanolammonium, diethanolammonium, and triethanolammonium, or organic ammonium. Of those described above, hydrogen atoms, lithium ions, sodium ions, potassium ions, and ammonium are particularly preferable.
In the formula, M represents “counter ion” because it is considered to dissociate into counter ions when, for example, a water-based ink for inkjet recording is formed using the coloring compound of the present invention. It does not mean to exclude those that are not dissociated. The same applies to the term “representing a counter ion” in other dye compounds.

The dye compound represented by the general formula (1) of the present invention can be synthesized according to a known method. An example of a synthesis scheme is shown below. First, a pyridone compound having the following structure used as a coupler can be synthesized as follows.

For example, methyl cyanoacetate (NC—CH ₂ —COO—CH ₃ ) is first reacted with ethylamine (H ₂ N—C ₂ H ₅ ) to give cyanoacetic acid ethylamide (NC—CH ₂ —CO—NH—C). ₂ H ₅₎ to synthesize.

Next, this is reacted with ethyl acetoacetate (CH ₃ —CO—CH ₂ —COO—C ₂ H ₅ ) to give a pyridone compound (1) [1-N ethyl-3-cyano-4- Methyl-6-hydroxy-2-pyridone] is synthesized.

Furthermore, for example, the target pyridone coupler can be obtained by hydrolyzing the cyano group of this pyridone compound (1) (in Table 2, (3)) according to a conventional method. For example, a pyridone coupler ((2) in Table 2) having —CONH ₂ as the substituent X is obtained. Moreover, the pyridone coupler (X in Table 2, (3)) in which X is a sulfone group can also be synthesized by appropriately selecting the hydrolysis conditions.

  Moreover, as a manufacturing method of the pigment | dye compound of this invention, the following methods are mentioned, for example. First, an aqueous sodium nitrite solution is added to anilines as listed in Table 1 in hydrochloric acid to obtain a diazotized product. Next, the pyridone azo dye can be obtained by adding the diazo compound to a pyridone coupler synthesized by the method as described above and coupling it.

［上記一般式（１）中、Ｘは、−ＣＯＮＨ₂又は−ＳＯ₃Ｍ、Ｙは、水素原子又は−ＣＯＯＭを表す。Ｍは、カウンターイオンを表す。］ By the above method, Exemplified Compounds 1 to 10 having the structure represented by the following general formula (1), wherein X, Y and M in the formula are those shown in Table 3, respectively, were obtained.

[In the general formula (1), X represents —CONH ₂ or —SO ₃ M, and Y represents a hydrogen atom or —COOM. M represents a counter ion. ]

  In addition, the manufacturing method of the compound which has a structure represented by General formula (1) as illustrated above is not limited to an above described manufacturing method. Further, the final product obtained by the reaction as described above is used for the intended purpose by purifying it after treating it according to the post-treatment of a normal organic synthesis reaction.

The obtained reaction product was identified by performing various analyzes using an apparatus as described below. That is, ¹ H and ¹³ C nuclear magnetic resonance spectroscopy (ECA-400, manufactured by JEOL Ltd.), high performance liquid chromatography (LC-20A, manufactured by Shimadzu Corporation), LC / TOF MS (LC / MSD) TOF, manufactured by Agilent Technologies), UV / Vis spectrophotometer (U-3310 spectrophotometer, manufactured by Hitachi, Ltd.) was used.

  The coloring compound of the present invention has a vivid color tone, and can be used as a coloring material, preferably an image information recording material, due to its spectral characteristics. Specifically, it can be used as a material for inks for printing, paints, or writing instruments, including ink jet recording inks described in detail below. Particularly preferably, it is useful as a coloring material for ink jet recording ink. Hereinafter, the water-based ink for inkjet recording will be described.

[Inkjet ink]
Next, a method for producing a water-based ink containing the coloring compound of the present invention that can be suitably used as an inkjet ink will be described. The dye compound having the structure represented by the general formula (1) can be dissolved or (and) dispersed in an aqueous medium to prepare an ink composition that can be used as a recording ink. Particularly preferred is an aqueous ink using an aqueous medium. When an inkjet ink is used, it is preferable that a pigment compound having a structure represented by the general formula (1) is contained in an amount of 0.2 to 10 parts by mass in 100 parts by mass of the ink.

  Examples of the aqueous medium used for preparing the aqueous ink include water or a mixed medium of water and a water-soluble organic solvent. The water-soluble organic solvent used in this case is not particularly limited as long as it exhibits water solubility, and examples thereof include alcohols, polyhydric alcohols, polyglycols, glycol ethers, nitrogen-containing polar solvents, sulfur-containing polar solvents, and the like. Can be mentioned.

  Preferred recording inks according to an embodiment of the present invention include the following constitutions. An ink containing water, a water-soluble organic solvent, and a dye compound, wherein the dye compound includes the dye compound of the present invention. Further, the ink is characterized in that at least one of the water-soluble organic solvents contained in the ink has a boiling point of 120 ° C. or more, and the content of the water-soluble organic solvent in the ink is 10% by mass or more. To do.

  The water-soluble organic solvent having a boiling point of 120 ° C. or higher in the above is the water-soluble organic solvent content in consideration of maintaining the moisture retention of the ink, improving the solubility of the coloring material, and effectively penetrating the ink into the recording paper. It is preferable that the amount be in the range of 10% by weight to 40% by weight of the total ink. More preferably, it is set as the range of 10 mass% or more and 30 mass% or less. The water content in the ink is preferably in the range of 30% by mass to 95% by mass. In this way, the colorant containing the coloring compound of the present invention has good dispersibility or solubility in the ink, has a viscosity for stable ink ejection when used for inkjet recording, and Ink that does not cause clogging at the nozzle tip can be obtained.

  A surfactant may be added to the ink of the present invention for the purpose of controlling the permeability of the ink. In this case, a chemically synthesized surfactant such as an ionic surfactant, a nonionic surfactant, or a polymer surfactant can be used. In addition, those derived from natural products and those modified with enzymes or the like can also be used. These surfactants can be used alone or in combination, and the total content of the surfactant is preferably 0.5% by mass or more and 20% by mass or less of the whole ink.

  In addition to the above components, when used as an ink, a pH adjuster, a rust inhibitor, a preservative, a fungicide, an antioxidant, an anti-reduction agent, an evaporation accelerator, a chelating agent, if necessary. Various additives such as a water-soluble polymer may be contained.

  As described above, the ink prepared using the coloring compound of the present invention is suitably used for an ink jet recording system in which recording is performed by discharging droplets by the action of thermal energy. The dye compound of the present invention can be applied to other ink jet recording methods, and can also be used for general writing instruments.

(Ink with phthalocyanine dye)
As a recording ink according to another embodiment of the present invention, in addition to the above-described pigment compound (water-soluble azopyridone dye) having a specific structure, the recording ink may be represented by the following general formula (4). An ink containing a phthalocyanine dye is used. Particularly preferred is a recording ink containing a water-soluble azopyridone dye and a phthalocyanine dye in a mass ratio of 3: 1 to 1: 3 and prepared for a green color tone.

（上記一般式（４）中、Ｒ₁乃至Ｒ₄はそれぞれ独立して、水素原子、スルホン基、スルホアミド基、カルボキシル基、ハロゲン原子、ヒドロキシル基、シアノ基、ニトロ基、アミノ基、ホスホノ基、トリフルオロメチル基、直鎖或いは分岐のアルキル基、直鎖或いは分岐のアルコキシ基、置換基を有してもよい、アリール基、フェノキシ基、チオフェノキシ基又はフェニル基及びこれらの塩の何れかを表し、Ｍは、２個の水素原子、２個のＮａ原子、２個のＬｉ原子、２個の金属、或いは３価又は４価の金属誘導体の何れかを表し、且つ、その構造中に少なくとも２つ以上のスルホン基又はその塩を有する。）

(In the general formula (4), R _{1 to} R ₄ are each independently a hydrogen atom, sulfone group, sulfoamide group, carboxyl group, halogen atom, hydroxyl group, cyano group, nitro group, amino group, phosphono group, A trifluoromethyl group, a linear or branched alkyl group, a linear or branched alkoxy group, an aryl group, a phenoxy group, a thiophenoxy group, a phenyl group, or a salt thereof, which may have a substituent. M represents two hydrogen atoms, two Na atoms, two Li atoms, two metals, or a trivalent or tetravalent metal derivative, and at least in the structure thereof 2 or more sulfone groups or salts thereof.

  Among the above, it is particularly preferable to use a copper phthalocyanine compound in which M is copper. As the copper phthalocyanine compound, anything including existing ones can be used, but particularly preferred are compounds represented by the following general formulas (5) and (6). This is because these compounds are particularly excellent in fastness and color development and have a great effect when mixed with the water-soluble azopyridone dye of the present invention described above. Regarding the use of the copper phthalocyanine compound, for example, it can be selected from the phthalocyanine compounds represented by the following general formulas (5) and (6) and used alone or in combination of two or more.

（上記一般式（５）中、ｌ＝０乃至２、ｍ＝１乃至３、ｎ＝１乃至３、但し、ｌ＋ｍ＋ｎ＝３乃至４、置換基の置換位置は、４若しくは４’位を表し、Ｍは、カウンターイオンであり、Ｒ₁及びＲ₂は、それぞれ独立に、水素原子、スルホン基、カルボキシル基を表し（但し、Ｒ₁及びＲ₂は、同時に水素原子となる場合を除く。）、Ｙは、塩素原子、ヒドロキシル基、アミノ基、モノ又はジアルキルアミノ基を表す。）

(In the general formula (5), l = 0 to 2, m = 1 to 3, n = 1 to 3, provided that l + m + n = 3 to 4, and the substitution position of the substituent represents the 4 or 4 ′ position, M is a counter ion, R ₁ and R ₂ each independently represent a hydrogen atom, a sulfone group, or a carboxyl group (provided that R ₁ and R ₂ are simultaneously hydrogen atoms); Y represents a chlorine atom, a hydroxyl group, an amino group, a mono- or dialkylamino group.)

  In the general formula (5), the following Exemplified Compound 11 is the most suitable compound because of its balance between color development and environmental gas resistance.

（上記例示化合物１１中、ｌ＝０乃至２、ｍ＝１乃至３、ｎ＝１乃至３、但し、ｌ＋ｍ＋ｎ＝３乃至４、置換基の置換位置は、４若しくは４’位を表す。）

(In the above exemplified compound 11, l = 0 to 2, m = 1 to 3, n = 1 to 3, provided that l + m + n = 3 to 4, and the substitution position of the substituent represents the 4 or 4 ′ position.)

（上記一般式（６）中、Ｍはスルホン酸基のカウンターイオンを表す。） A copper phthalocyanine compound having a structure of the following general formula (6) is also suitable.

(In the general formula (6), M represents a counter ion of a sulfonic acid group.)

Specific examples of the compound represented by the general formula (6) are shown below, but the phthalocyanine compound used in the present invention is not limited to the following examples.

(Ink containing film-forming component)
In addition to the above-described components, the recording ink according to an embodiment of the present invention is further formed into a film so that the film can be formed by irradiating heat, light, or both after application of the ink. Examples thereof include inks containing components. Suitable coating components that can be used at this time include the following. For example, at least one or several kinds of acrylic monomers or copolymers having acrylic monomer units, vinyl monomers or copolymers having vinyl monomer units. Furthermore, a recording ink containing at least one of the above acrylic monomer units represented by the following general formula (7) as a film-forming component is preferable.

（上記一般式（７）中、Ｒ₁は、水素原子又はメチル基を表し、Ｒ₂は、水素原子又はアルキル基を示す。）

(In the general formula (7), R ₁ represents a hydrogen atom or a methyl group, and R ₂ represents a hydrogen atom or an alkyl group.)

  An ink jet recording method according to an embodiment of the present invention is characterized in that ink jet recording is performed using the recording ink having the above-described configuration prepared for ink jet recording.

  The color filter manufacturing method according to an embodiment of the present invention includes, for example, a method of forming a pattern by an ink jet recording method using the ink in a form containing the above-described film forming component. More specifically, the following method is mentioned. For example, a method of forming a pattern by applying red, blue and green inks that are the three primary colors of light to an ink receiving layer of a transparent substrate having an ink receiving layer by an ink jet method, and providing a transparent protective film on the pattern surface There is. In addition, there is a method including a pixel forming step in which an ink droplet is attached to a predetermined position on a light-transmitting substrate having ink repellency, and then the attached ink is cured to form a colored pixel.

  Next, a recording apparatus that can be used in the ink jet recording method of the present invention will be described. As a recording apparatus suitable for recording using the ink of the present invention, the thermal or mechanical energy corresponding to the recording signal is added to the ink in the chamber of the recording head having the ink storage portion in which these inks are stored. And an apparatus for generating ink droplets by the energy.

  FIG. 2 shows an example of an ink jet recording apparatus incorporating this head. In FIG. 2, reference numeral 61 denotes a blade as a wiping member, one end of which is held by a blade holding member to become a fixed end and form a cantilever. The blade 61 is disposed at a position adjacent to the recording area by the recording head, and in the case of the example shown in FIG. 2, the blade 61 is held in a form protruding in the moving path of the recording head. Reference numeral 62 denotes a cap, which is disposed at a home position adjacent to the blade 61 and moves in a direction perpendicular to the moving direction of the recording head so as to come into contact with the ejection surface and perform capping. Further, reference numeral 63 in FIG. 2 denotes an ink absorber provided adjacent to the blade 61 and, like the blade 61, is held in a form protruding in the moving path of the recording head.

  The blade 61, the cap 62, and the absorber 63 constitute a discharge recovery portion 64, and the blade 61 and the absorber 63 remove moisture, dust, dust, and the like from the ink discharge port surface. Reference numeral 65 denotes a recording head that has discharge energy generation means and performs recording by discharging ink onto a recording medium facing the discharge port surface on which the discharge ports are arranged. Reference numeral 66 denotes a recording head 65 on which the recording head 65 is mounted. It is a carriage for performing the movement. The carriage 66 is slidably engaged with the guide shaft 67, and a part of the carriage 66 is connected to a belt 69 driven by a motor 68. Accordingly, the carriage 66 can move along the guide shaft 67, and the recording area by the recording head 65 and its adjacent area can be moved.

  Reference numeral 51 denotes a paper feed unit for inserting a recording medium, and 52 denotes a paper feed roller driven by a motor (not shown). With these configurations, the recording medium is fed to a position facing the ejection port surface of the recording head, and is discharged to a paper discharge portion provided with a paper discharge roller 53 as recording progresses.

  In the above configuration, when the recording head 65 returns to the home position due to the end of recording or the like, the cap 62 of the ejection recovery unit 64 is retracted from the moving path of the recording head 65, but the blade 61 protrudes into the moving path. As a result, the ejection port surface of the recording head 65 is wiped. When the cap 62 is in contact with the ejection surface of the recording head 65 to perform capping, the cap 62 moves so as to protrude into the moving path of the recording head.

  When the recording head 65 moves from the home position to the recording start position, the cap 62 and the blade 61 are at the same position as that at the time of wiping described above. As a result, even in this movement, the ejection port surface of the recording head 65 is wiped. The above-mentioned movement of the recording head to the home position is performed not only at the end of recording or at the time of recovery of ejection, but also to the home position adjacent to the recording area at a predetermined interval while the recording head moves the recording area for recording. In accordance with this movement, the wiping is performed.

  FIG. 3 is a cross-sectional view showing an example of an ink cartridge 45 containing ink supplied to the head via an ink supply member, for example, a tube. Here, reference numeral 40 denotes an ink container, for example, an ink bag, in which supply ink is stored, and a rubber plug 42 is provided at the tip thereof. By inserting a needle (not shown) into the stopper 42, the ink in the ink bag 40 can be supplied to the head. An ink absorber 44 receives waste ink.

  The ink jet recording apparatus used in the present invention is not limited to the one in which the head and the ink cartridge as described above are separated, and an apparatus in which they are integrated as shown in FIG. 4 is also preferably used. In FIG. 4, reference numeral 70 denotes a recording unit, in which an ink containing portion containing ink, for example, an ink absorber is housed, and a head portion in which the ink in the ink absorber has a plurality of orifices. 71 is ejected as ink droplets. Reference numeral 72 denotes an atmosphere communication port for communicating the inside of the recording unit with the atmosphere. The recording unit 70 is used in place of the recording head 65 shown in FIG. 2, and is detachable from the carriage 66.

  FIG. 5 shows an example of an ink jet cartridge that can be mounted on the above-described ink jet recording apparatus. The cartridge 1012 in this example is of a serial type, and the main part is composed of an ink jet recording head 100 and a liquid tank 1001 for containing a liquid such as ink. The inkjet recording head 100 is formed with a number of ejection ports 832 for ejecting liquid, and liquid such as ink is supplied from the liquid tank 1001 to a common liquid chamber of the liquid ejection head 100 via a liquid supply passage (not shown). It has come to be guided. A cartridge 1012 shown in FIG. 5 integrally forms an ink jet recording head 100 and a liquid tank 1001 so that liquid can be supplied into the liquid tank 1001 as necessary. A structure in which a liquid tank 1001 is connected to 100 in a replaceable manner may be adopted.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. In the text, “parts” and “%” represent “parts by mass” and “mass%”, respectively, unless otherwise specified. Moreover, the remainder means the remainder which made the whole 100% and deducted each component.

[Example 1]
(Synthesis of Exemplified Compound 4 below)

1) Synthesis of pyridone coupler <Synthesis of 1- (N-ethyl) -3-carbamoyl-4-methyl-6-hydroxy-2-pyridone coupler>
Using 9.2 g of 1-ethyl-3-cyano-4-methyl-6-hydroxy-2-pyridone obtained as described above, this was stirred at a temperature of 20 ° C. with stirring in 31 g of 96% concentrated sulfuric acid. It took 1 hour below and added. Subsequently, it heated up at 60 to 65 degreeC, and reacted at the same temperature for 30 hours. This was cooled and discharged into 270 g of ice water. This solution was stirred at 5 ° C. to 10 ° C. for 5 hours, filtered, washed with cold water, and dried at 60 ° C. The dried crystals were purified by recrystallization from ethanol and vacuum-dried at 60 ° C. to obtain 9.8 g of the pyridone coupler described above as white crystals.

2) Synthesis of azo compound 13.2 g of 2-aminoterophical acid (2,5-dicarboxyaniline) (manufactured by Tokyo Chemical Industry) was dissolved in 100 g of ion-exchanged water. Next, the solution was cooled in a bath and kept at 5 ° C. or lower, and 20 g of concentrated hydrochloric acid was added. Further, 18.4 g of sodium nitrite was added, and the reaction mixture was stirred at 10 ° C. or lower for 30 minutes. Thereafter, sulfamic acid (0.4 g) was added to decompose excess nitrous acid to obtain a diazonium salt solution (diazotized product).

11 g of the previously prepared pyridone coupler was dissolved in 100 ml of water, and then adjusted to pH 8 with 1N sodium hydroxide solution. To this solution, the diazonium salt solution prepared above was dropped and reacted for 3 hours. The yellow solution was then acidified with concentrated hydrochloric acid until the pH was 1, and the resulting precipitate was collected by filtration. The obtained precipitate was washed with cold water, then dispersed in 200 g of water, 2N sodium hydroxide solution was added to adjust the pH to 8 and dissolved. Finally, the product is dialyzed to remove inorganic compounds, filtered through a 0.45 μm filter, concentrated by an evaporator, acetone is added, and the resulting precipitate is vacuum-dried at 60 ° C. as a yellow powder as described above. The exemplified compound 4 having a structure was obtained. The structure of the obtained compound was confirmed by ¹ H-NMR spectrum, ¹³ C-NMR spectrum and mass spectrum.

[Analysis results of the exemplified compound (4)]
[1] Results of ¹ H-NMR (400 MHz, D ₂ O, room temperature) (FIG. 1):
δ [ppm] = 0.89 (1H, s), 2.22 (1H, s), 2.57 (1H, s), 3.46 (1H, br s), 7.44 (1H, d) 7.72 (1H, d), 8.18 (1H, s)

[2] Results of ¹³ C-NMR (100 MHz, DMSO-d ₆ , room temperature):
δ [ppm] = 13.13, 14.33, 33.72, 115.30, 123.52, 124.10, 125.26, 127.78, 131.82, 134.76, 142.97, 144 .32, 158.82, 160.98, 166.65, 167.46, 168.66

[3] Results of mass spectrometry (ESI-TOF):
m / z = 409.08 (M-2H + Na) ⁻ , 387.09 (M−H) ⁻ , 193.04 (M−2H) ²⁻

[4] HPLC results:
Purity = 96.7 area%, retention time 10.6 minutes (0.1 mM TFA solution-MeOH)

[5] Results of UV / Vis spectroscopic analysis:
λ _max = 427 nm (solvent: H ₂ O in room temperature)

[Example 2]
(Synthesis of Exemplified Compound 8 below)

1) Synthesis of pyridone coupler <Synthesis of 1- (N-ethyl) -3-sulfonyl-4-methyl-6-hydroxy-2-pyridone>
1-ethyl-3-cyano-4-methyl-6-hydroxy-2-pyridone obtained as described above was reacted in 10 g, 90 g of 2% fuming sulfuric acid at 20 ° C. to 25 ° C. for 15 hours. It was. After the reaction, it was cooled and discharged into 100 g of ice water. This solution was stirred at 5 ° C. to 10 ° C. for 5 hours, filtered, washed with cold water, and dried at 60 ° C. The dried crystal was purified by recrystallization from ethanol and vacuum dried at 60 ° C. to obtain 4.6 g of the above pyridone coupler (the following structure) as a white crystal.

1- (N-ethyl) -3-sulfonyl-4-methyl-6-hydroxy-2-pyridone obtained above was used as the pyridone coupler, and anthranilic acid was used as a starting material for the diazo component (diazotized product). In the same manner as in Example 1, Example Compound 8 having the structure described above was synthesized. The structure of the dye compound was confirmed by ¹ H-NMR spectrum, ¹³ C-NMR spectrum, and mass spectrum (see below).
Mass spectrometry (ESI-TOF) results:
m / z = 380.09 (M−H) ⁻ , 189.54 (M−2H) ²⁻
The absorption maximum wavelength of the aqueous solution was 429 nm.

[Examples 3 and 4]
(Synthesis of Exemplified Compounds 6 and 5 in Table 3)
When neutralizing the dye synthesized in Example 1, Li salt and ammonium salt were obtained by using lithium hydroxide and aqueous ammonia, respectively, instead of using sodium hydroxide. Subsequent purification was performed in the same manner as in Example 1 to obtain the following exemplified compounds 6 and 5.

[Comparative Examples 1-3]
Each comparative dye compound was synthesized in the same manner as in Example 1 except that anilines having the functional groups shown in Table 4 were used as starting materials for the diazo component (diazotized product). The structures of the obtained comparative compounds 1 to 3 of each comparative example are shown.

<Evaluation>
[Ink formula 1]
・ Dye 5%
・ Glycerin 5%
・ Ethylene glycol 5%
・ Isopropyl alcohol 2%
・ Urea 5%
・ Acetylenol EH (Kawaken Fine Chemicals) 0.8%
・ Ion exchange water remaining

  Based on the above ink formulation 1, an ink liquid was prepared using any one of the above exemplary compounds 4 to 6, 8 and comparative compounds 1 to 3 as a dye. These inks were respectively filled in ink cartridges of a bubble jet (registered trademark) printer PIXUS950i manufactured by Canon Inc. Then, with the above inkjet printer, a 2 cm square solid image was printed on Canon glossy professional photo paper (PR-101 paper) and Canon plain paper PPC paper to create a recorded matter. . Next, the obtained recorded matter was naturally dried for 24 hours to obtain a recorded matter to be tested.

[Color tone]
Each recorded matter on photographic glossy paper obtained by the above method was measured for optical density and chromaticity (L ^* , a ^* , b ^* ) in the L ^* a ^* b ^* color system with a reflection densitometer Spectrolino (manufactured by GretagMacbeth). It was measured. The saturation was calculated by the following formula based on the measured value of the color characteristic.
Saturation (c ^* ) = √ {(a ^* ) ² + (b ^* ) ² }

The evaluation criteria are as follows. That is, it was determined that a high-quality recorded material could be obtained if L ^* was 90 or more when c ^* = 80. The results obtained are shown in Table 5.
A: L ^* ≧ 92
○: 92> L ^* ≧ 90
X: L ^* <90

[Light resistance]
The obtained recorded matter was put into a xenon test apparatus (AtlasCi4000, manufactured by Suga Test Instruments Co., Ltd.), and the conditions were (illuminance: 0.39 W / m ² @ 340 nm, temperature: 50 ° C., relative humidity: 70%). , 50 hr exposure. The reflection density of the printed matter was measured before and after the test. From the initial yellow image density M ₀ and the yellow image density M _f after exposure, the yellow density remaining rate ({M _f / M ₀ } × 100 [%]) was calculated. The results obtained are shown in Table 5.

The evaluation criteria are as follows.
A: Yellow density remaining rate of 80% or more B: Yellow density remaining rate of 50% or more and less than 80% X: Yellow density remaining rate of 50% or less

[Ozone resistance]
Each recorded matter obtained was subjected to an ozone weather meter [OMS-H (trade name), manufactured by Suga Test Instruments Co., Ltd.] in an atmosphere having an ozone concentration of 3 ppm, a temperature of 40 ° C., and a relative humidity of 55% for 2 hours. Exposed. The reflection density of the recorded matter was measured before and after the test. The evaluation criteria are the same as in the case of the above light resistance evaluation. The evaluation results are shown in Table 5.

[Wet resistance]
Each of the inks of Examples 1 to 4 and Comparative Examples 1 to 3 was used, and 50 single dots were independently printed on the recording medium to obtain printed matter. The obtained printed matter was allowed to stand at room temperature and humidity for 12 hours, and then the printed matter was allowed to stand in an environment of 80% RH at 30 ° C. for 2 weeks. The printed matter held in this way under high temperature and high humidity was visually compared before and after storage for the dot diameter on the recording medium, evaluated for wet resistance, and evaluated according to the following criteria. The evaluation results are shown in Table 5.
◎: Excellent ○: Good ×: Inferior

  As shown in Table 5, it was found that the recorded matter obtained by the ink liquid of the example using the coloring compound of the present invention had good color tone, light resistance, ozone resistance and wet resistance. . From this, it was confirmed that it is useful as a coloring agent for yellow ink for inkjet.

[Examples 5 to 8]
[Ink formula 2]
・ Dyes (types and contents shown in Table 6)
・ Glycerin 5%
・ Ethylene glycol 5%
・ Isopropyl alcohol 2%
・ Urea 5%
・ Acetylenol EH (Kawaken Fine Chemicals) 0.8%
・ Ion exchange water remaining

Using the dye set described in Table 6, ink of ink formulation 2 was prepared. All were good green tone inks. The obtained green inks were evaluated in the same manner as the inks of Examples 1 to 4 and Comparative Examples 1 to 3. However, the color tone was evaluated by L ^* when c ^* = 70, and it was determined that a high-quality printed matter could be obtained if L ^* was 60 or more. The evaluation results are shown in Table 7.

(Evaluation criteria for color tone)
A: L ^* ≧ 70
○: 70> L ^* ≧ 60
X: L ^* <60

  As shown in Table 7, the recorded matter obtained with the green ink liquid of Examples using the coloring compound of the present invention was good in all of color tone, light resistance, ozone resistance and wet resistance. From this, it was confirmed that the ink of the present invention is useful as a colorant for an inkjet green ink.

[Example 9]
(Create color filter)
A recording ink is prepared with an ink formulation 3 containing a film-forming component that is formed by irradiation with heat, light, or both, and the resulting ink is used as follows. A color filter was prepared. An acrylic copolymer was used as the film forming component. The acrylic copolymer has the following mass composition of monomers. That is, a composition comprising 20 parts of N-methylolacrylamide, 10 parts of N, N-dimethylaminoethyl methacrylate, 25 parts of methyl methacrylate, 40 parts of 2-hydroxyethyl methacrylate, and 5 parts of acrylic acid was used.

[Ink formula 3]
-Dye (Dye set of mixing ratio used in Example 7)
・ Acrylic copolymer of the above mass composition 10.0%
・ Ethylene glycol (boiling point 197.9 ° C) 36.0%
・ Ethyl alcohol (boiling point 78 ° C) 6.0%
・ Water 43.0%

  First, a black pigment resist CK-S171B manufactured by Fuji Hunt Co., Ltd. was applied on a glass substrate by a spin coating method, and then a black matrix having a thickness of 1.0 μm was formed on the substrate by exposure, development, and heat treatment. .

  Subsequently, using the curable ink prepared based on the said ink prescription 3, the ink was discharged from the opening part with the inkjet printer, and the pattern was formed. Next, the ink was formed into a film by heat treatment at 230 ° C. for 30 minutes to form a color filter for a liquid crystal element.

<Evaluation method>
(Evaluation 1: Adhesion)
First, the color filter was washed for 5 minutes in a water bath using an ultrasonic cleaner with an output of 100 W (35 kHz). Subsequently, it observed visually and evaluated the adhesiveness of the washing | cleaning part in the following three grades.
A: Good adhesion (no peeling in the central 100 pixels)
B: Slightly inferior in adhesion (peeling in the central 100 pixels is 5 pixels or less)
C: Adhesiveness is inferior (peeling in the central 100 pixels is more than 6 pixels)

(Evaluation 2: Dullness of colored portion)
A specific cell of the above color filter was spectroscopically measured, immersed in warm pure water at 60 ° C. for 10 minutes, and dried on a 120 ° C. hot plate for 1 minute. The same cell was subjected to spectroscopic measurement, and the rate of decrease in absorbance from the absorbance at the initial absorption maximum wavelength was evaluated as follows.
A: Less than 1% decrease in absorbance at colored portion B: Less than 1% to less than 3% absorbance at colored portion C: Not less than 3% decrease in absorbance at colored portion

(Evaluation 3: Heat resistance)
The above color filter was allowed to stand in an oven at 250 ° C. for 1 hour, and the magnitude of fading color was calculated as ΔE determined by CIE and evaluated according to the following criteria.
A: ΔE is 3 or less B: ΔE exceeds 3 and 10 or less C: ΔE is greater than 10

(Evaluation 4: Discharge stability)
The green ink prepared above was loaded into an inkjet printer (trade name BJ-10V manufactured by Canon), and 300 character patterns were printed on A4 paper. The 300th printed A4 paper was visually observed and evaluated according to the following criteria.
A: No problem at all B: Some blurring occurred C: Almost no discharge

  Evaluation of the color filter prepared in Example 9 is as shown in Table 8 below, and can be suitably used. In addition, in each evaluation, it was judged that the thing more than B determination could endure use, and the thing of A determination was judged to be used especially suitably.

D in ₂ O of the exemplary compound 4 according to the present invention, it is a graph showing a ¹ H-NMR spectrum at room temperature, at 400 MHz. It is a perspective view which shows an example of an inkjet recording device. It is a longitudinal cross-sectional view of an ink cartridge. It is a perspective view of a recording unit. It is a schematic perspective view showing an example of an ink jet cartridge provided with a liquid discharge head.

Claims (8)

A coloring compound having a structure represented by the following general formula (1).

[In the general formula (1), X is -CONH ₂ or -SO ₃ M, Y is - represents a COOM. M represents a counter ion. ] A coloring composition comprising a coloring compound having a structure represented by the following general formula (2).

In [the formula (2), Y is - represents a COOM. M represents a counter ion. ] A coloring composition comprising a coloring compound having a structure represented by the following general formula (3).

In [the formula (3), Y is - represents a COOM. M represents a counter ion. ]   A recording ink comprising water, a water-soluble organic solvent, and a dye compound, wherein the dye compound comprises the dye compound according to any one of claims 1 to 3, and the water-soluble organic solvent contained in the ink. At least one of them has a boiling point of 120 ° C. or higher, and the content of the water-soluble organic solvent in the ink is 10% by mass or more.   The recording ink according to claim 4, further comprising a phthalocyanine dye and prepared for a green color tone.   The recording ink according to claim 4 or 5, further comprising a film-forming component that is formed by irradiation with heat, light, or both.   An ink jet recording method using the recording ink according to any one of claims 4 to 6.   A method for producing a color filter, comprising a step of forming a plurality of colored pixels using the recording ink according to claim 6.

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