JP6957883B2 - Azomethin zinc complex - Google Patents

Description

The present invention relates to novel azomethine zinc complexes.

Patent Document 1 discloses an azomethine zinc complex having a certain structure. However, Patent Document 1 does not disclose the compound of the present invention represented by the following formula (I).

Special Publication No. 59-5625

Currently, coloring compositions are used in various fields, and specific applications include printing inks, paints, colorants for resins, colorants for fibers, and color materials for information recording (color filters, toners, inkjets, etc.). Color material used) and the like. Dyes used in coloring compositions are mainly classified into pigments and dyes, and the performance required for them is color characteristics (coloring power, sharpness) and resistance (weather resistance, light resistance, heat resistance, solvent resistance). )and so on. Unlike dyes, which usually develop color in the molecular state, pigments develop color from the particle state (aggregates of primary particles). Therefore, pigments are generally superior to dyes in resistance, but are often inferior in coloring power and sharpness. Against this background, pigments with high coloring power and high saturation are required. Among them, organic pigments, which are considered to be superior in terms of coloring power, are attracting particular attention.

Among these organic pigments, many new pigments have been actively developed so far, such as the number of registered yellow pigments is the second largest after red pigments. As a yellow organic pigment that has been put into practical use, for example, in printing ink applications, C.I. I. Pigment Yellow 3, 12, 74, etc. are used, 74, 83, 109, 110, etc. are used for paint applications, and 138, 150, etc. are used for color filter applications.

Here, the color filter is composed of a red pixel portion (R), a green pixel portion (G), and a blue pixel portion (B), and the yellow pigment is often used for toning the green pixel portion. As the yellow pigment used in such a color filter, the above two types (138 and 150) are mainly used from the viewpoint of transmission waveform and fastness.
However, C.I. I. Pigment Yellow 138 has poor coloring power and is not practical in a color standard that requires high color reproducibility, which has been increasing in demand in recent years. Therefore, in the color standard of high color reproducibility, C.I. I. Pigment Yellow 150 is used as the current yellow pigment, but it cannot be said that the pigment yellow 150 is sufficient in terms of brightness and coloring power, and the hue variation is limited.
Under such circumstances, the hue expansion of yellow pigments is an urgent issue in color filter applications.

As a result of diligent studies in view of such a situation, the present inventors have found that the compound represented by the following formula (I) has an unprecedented hue, and have completed the present invention. That is, the present invention has the following formula (I):

(In the formula (I), X ¹ and X ² each independently represent a hydrogen atom, a halogen atom or an alkoxy group), and the azomethine zinc complex (hereinafter, may be referred to as “the compound of the present invention”). ..

The compound of the present invention has an unprecedented color. In particular, the present invention can represent a color gamut that cannot be represented by conventional yellow pigments when used as a coloring composition for a color filter.

Examples of the halogen atom in the above formula (I) include fluorine, chlorine, bromine and iodine atoms, and among them, the chlorine atom or the bromine atom is preferable, and the chlorine atom is more preferable.

Examples of the alkoxy group in the above formula (I) include methoxy, ethoxy, propyloxy, i-propyloxy, butyloxy, i-butyloxy, s-butyloxy, t-butyloxy, pentyloxy, 1-methylbutyloxy and 2-methyl. Butyloxy, 3-methylbutyloxy, 1,1-dimethylpropyloxy, 1,2-dimethylpropyloxy, 2,2-dimethylpropyloxy, 1-ethylpropyloxy, hexyloxy, 1-methylpentyloxy, 2- Methylpentyloxy, 3-methylpentyloxy, 4-methylpentyloxy, 1,1-dimethylbutyloxy, 1,2-dimethylbutyloxy, 1,3-dimethylbutyloxy, 2,2-dimethylbutyloxy, 2, 3-Dimethylbutyloxy, 3,3-dimethylbutyloxy, 1-ethylbutyloxy, 2-ethylbutyloxy, 1,1,2-trimethylpropyloxy, 1,2,2-trimethylpropyloxy, 1-ethyl- Examples thereof include 1-methylpropyloxy and 1-ethyl-2-methylpropyloxy. Among them, those having 1 to 8 carbon atoms can be mentioned as a preferable example.

Such a method for producing the compound of the present invention is not particularly limited, and can be produced by appropriately using a conventionally known method. Hereinafter, one aspect of the method for producing the compound of the present invention will be described. However, the present invention is not limited thereto.

The compound of the present invention is a compound represented by the following formula (II) (in the formula (II), X ¹ represents a hydrogen atom, a halogen atom or an alkoxy group) in the presence of a solvent, and the following formula (III) (formula). In (III), X ² can be obtained by reacting with a compound represented by (representing a hydrogen atom, a halogen atom or an alkoxy group), adding zinc acetate to the obtained reaction solution, and further reacting.

The solvent may be any solvent as long as it is inert to the reaction, and examples thereof include ethers such as diethyl ether, dioxane, tetrahydrofuran and dimethoxyethane; alcohols such as methanol and ethanol.
As the solvent, one or more of these can be appropriately selected.

The reaction temperature can be 25 ° C. to 65 ° C., preferably 40 ° C. to 65 ° C., and the reaction time can be 1 hour to 4 hours, preferably 3 hours to 4 hours.

After completion of the reaction, the target product obtained by the above reaction can be isolated and purified by known and commonly used operations such as filtration, extraction and washing.

Zinc acetate may be hydrated or anhydrous. Further, it may be used in a solid state, or a substance dissolved in a solvent may be used. Since the reaction can proceed efficiently, it is preferable to use zinc acetate dissolved in a solvent. Here, as the solvent used for dissolving zinc acetate, a solvent generally known as a solvent for refluxing can be used, and methanol or the like can be used.

The compound of the present invention is considered to be applicable to various uses. For example, it can be used as a colorant for a wide range of applications such as printing inks, paints, colored plastics, toners, ink jet inks, light-shielding members for displays, and seed coloring.

The compound of the present invention may be used alone, or two or more kinds of compounds may be appropriately selected and used in combination.

The compound of the present invention exhibits properties as an organic pigment, and may be used more preferably by making the pigment particles finer by a salt milling treatment or the like. Such a process may be performed by a known and commonly used method.

The compound of the present invention may be used in combination with a coloring material such as an organic pigment, an organic dye, or an organic pigment derivative other than the compound of the present invention for the purpose of toning or the like. These should be appropriately selected according to the above-mentioned uses, and depending on the use, the compound of the present invention may be used alone, or two or more kinds may be used in combination as appropriate.

The color material that can be used in combination may be any known pigment, dye, or the like.
Depending on the application, azo, disazo, azomethine, anthraquinone, quinophthalone, quinacridone, diketopyrrolopyrrole, dioxazine, benzimidazolone, phthalocyanine, isoindoline, isoindolinone, perylene pigments , And xanthene-based, azo-based, disazo-based, anthraquinone-based, quinophthalone-based, triarylmethane-based, methine-based, phthalocyanine-based, and rhodamine-based dyes.

Examples of the yellow pigment that can be used in combination with the compound of the present invention include C.I. I. Pigment Yellow 3, 12, 74, etc., 74, 83, 109, 110, etc. for paint applications, 83, 129, 138, 139, 150, 150, etc. for color filter applications. Examples thereof include the quinophthalone pigments described in 185, 231 and Patent No. 5817028.

In particular, when the compound of the present invention is used for forming a green pixel portion in a color filter application, for example, C.I. I. Pigment Green 1, 2, 4, 4, 7, 8, 10, 13, 14, 14, 15, 17, 18, 18, 19, 26, 36, 45, 48, It can be used in combination with green pigments such as 50, 51, 54, 55, 58, 59, 62, and 63, but is not limited thereto. When the compound of the present invention is used for forming a green pixel portion in a color filter application, the combined ratio of the green pigment and the yellow pigment of the present invention is, for example, 10 to 100 parts by mass of the yellow pigment per 100 parts by mass of the green pigment. Is.

Further, when the compound of the present invention is used for forming a green pixel portion, the compound of the present invention and a blue pigment can be used in combination. Examples of the blue pigment include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, aluminum phthalocyanine derivatives and the like.
Here, examples of the above-mentioned aluminum phthalocyanine derivative include compounds represented by the following general formula (3-1).

(In the formula (3-1), R is a halogen atom, a hydroxy group, or a group represented by the following general formula (3-2).)

(In formula (3-2), X is a direct bond or an oxygen atom. Ar is a phenyl group or a naphthyl group. In the formula, an asterisk indicates a binding site.)

Examples of the halogen atom in R in the above formula (3-1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Above all, the halogen atom in R is preferably a chlorine atom or a bromine atom.

In the formula (3-1), R is preferably a chlorine atom, a bromine atom, a hydroxy group, or a group represented by the above general formula (3-2).

In formula (3-2), X is preferably an oxygen atom.

Among the formulas (3-1), for example, hydroxyaluminum phthalocyanine, chloroaluminum phthalocyanine, bromoaluminum phthalocyanine, compounds represented by the following formula (3-1-1), and the following formula (3-1-2) are preferable. ), A compound represented by the following formula (3-1-3), and the like.

Further, the compound of the present invention can also be used in combination with a red pigment for forming a red pixel portion in a color filter application. Examples of the red pigment include C.I. I. Pigment Red 177, Pigment Red 254 and the like.

When the present invention is used for forming a pattern of a green pixel portion of a color filter, a known method can be adopted. Typically, a photosensitive composition for a color filter containing the compound of the present invention and a photosensitive resin as essential components can be obtained.

As a method for producing a color filter, for example, the compound of the present invention is dispersed in a dispersion medium made of a photosensitive resin, and then coated on a transparent substrate such as glass by a spin coating method, a roll coating method, an inkjet method, or the like. An example is a method called photolithography in which the coated film is subjected to pattern exposure with ultraviolet rays via a photomask, and then the unexposed portion is washed with a solvent or the like to obtain a green pattern. The same applies when the present invention is used for forming a pattern of a red pixel portion of a color filter.

In addition, a color filter may be manufactured by forming a pattern of pixel portions by an electrodeposition method, a transfer method, a micelle electrolysis method, or a PVED (Photovoltaic Electrolysis) method.

To prepare a photosensitive composition for a color filter, for example, a pigment, a photosensitive resin, a photopolymerization initiator, and an organic solvent that dissolves the resin are mixed as essential components. As a manufacturing method thereof, a method of preparing a dispersion liquid by using a pigment, an organic solvent and, if necessary, a dispersant, and then adding a photosensitive resin or the like to the dispersion liquid is generally used.

As the pigment here, when a green pixel portion is obtained, a pigmented compound of the present invention and the above-mentioned green pigment or blue pigment can be used. Similarly, when the red pixel portion is obtained, a pigmented compound of the present invention and the above-mentioned red pigment can be used.

Dispersants used as needed include, for example, DISPERBYK (registered trademark name) 130, 161 and 162, 163, 170, LPN-6919, LPN-21116 of BASF, and Fuka 46 of BASF. Fuka 47 and the like can be mentioned. In addition, a leven rig agent, a coupling agent, a cationic surfactant and the like can also be used together.

Examples of the organic solvent include aromatic solvents such as toluene, xylene and methoxybenzene, acetate solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, and ethoxyethyl propionate. Propionate solvent, alcohol solvent such as methanol and ethanol, ether solvent such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether and diethylene glycol dimethyl ether, ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, fat such as hexane. Group hydrocarbon solvents, nitrogen compound solvents such as N, N-dimethylformamide, γ-butyrolactam, N-methyl-2-pyrrolidone, aniline, pyridine, lactone solvents such as γ-butyrolactone, methyl carbamate and carbamate There are carbamate esters such as a 48:52 mixture of ethyls and the like. As the organic solvent, water-soluble polar solvents such as propionate-based, alcohol-based, ether-based, ketone-based, nitrogen compound-based, and lactone-based solvents are particularly suitable.

Per 100 parts by mass of the pigment composition for a color filter of the present invention, 300 to 1000 parts by mass of an organic solvent and, if necessary, 100 parts by mass or less of a dispersant are stirred and dispersed so as to be uniform to obtain a dispersion liquid. be able to. Next, in this dispersion, 3 to 20 parts by mass of a photosensitive resin per 100 parts by mass of the dispersion, 0.05 to 3 parts by mass of a photopolymerization initiator per 1 part by mass of the photosensitive resin, and, if necessary, further organic. A photosensitive composition for a color filter pixel portion can be obtained by adding a solvent and stirring and dispersing the mixture so as to be uniform.

The above pigment composition for a color filter includes, in the case of green pixel use, 10 parts by mass of the azomethine zinc complex of the present invention, and in the case of green pixel use, 200 parts by mass or less of green pigment and / and 200 parts by mass or less of blue pigment. It is a mixture that is appropriately set and mixed, or in the case of a red pixel application, a red pigment of 200 parts by mass or less is mixed. In addition, other yellow pigments may be mixed if necessary.

Examples of the photosensitive resin that can be used at this time include thermoplastic resins such as urethane resin, acrylic resin, polyamic acid resin, polyimide resin, styrene maleic acid resin, and styrene maleic anhydride resin. Bifunctional monomers such as 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (acryloxyethoxy) bisphenol A, 3-methylpentanediol diacrylate, etc. Examples thereof include photopolymerizable monomers such as polyfunctional monomers such as trimethylolpropane triacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and the like.

Examples of the photopolymerization initiator include acetophenone, benzophenone, benzyldimethylketanol, benzoyl peroxide, 2-chlorothioxanthone, 1,3-bis (4'-azidobenzal) -2-propane, and 1,3-bis (4'). -Azidobenzal) -2-Propane-2'-sulfonic acid, 4,4'-diazidostilbene-2,2'-disulfonic acid and the like.

The photosensitive composition for the pixel portion of the color filter thus prepared is subjected to pattern exposure with ultraviolet rays through a photo mask, and then the unexposed portion is washed with an organic solvent, alkaline water, or the like to prepare a color filter. Can be done.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Unless otherwise specified in Examples and Comparative Examples, "parts" and "%" are based on mass.
The measurement method used in the examples is as follows.
(1) Molecular Weight Measurement A solution was prepared by dispersing about 5 mg of a sample in 1 ml of THF, and the solution was prepared using GC / TOFMS JMS-T100GC, manufactured by JEOL Ltd.
(2) UV-vis spectrum measurement A sample was dissolved in 50 mL of DMSO, further diluted with DMSO to prepare a solution, and the spectrophotometer U3900 manufactured by Hitachi, Ltd. was used.

[Synthesis example]
Synthesis Example 1-1
6.37 parts of 1-amino-2-naphthol hydrochloride, 6.26 parts of 4-chloro-2-hydroxybenzaldehyde, and 142.5 parts of methanol were mixed and stirred to prepare a solution, and then reflux was performed for 4 hours. .. After returning to room temperature, 8.78 parts of zinc acetate was dissolved in 39.6 parts of methanol, this solution was added, and the mixture was stirred for 2 hours. The yellow precipitate produced by the reaction was recovered by filtration, and the obtained cake was washed with 158.4 parts of methanol to obtain 5.8 parts of the azomethine zinc complex (a) having the following structure. m / z = 359

Synthesis Example 1-2
5.85 parts of 1-amino-2-naphthol hydrochloride, 3.66 parts of salicylaldehyde, and 142.5 parts of methanol were mixed and stirred to prepare a solution, and then reflux was carried out for 4 hours. After returning to room temperature, 6.58 parts of zinc acetate was dissolved in 39.6 parts of methanol, this solution was added, and the mixture was stirred for 2 hours. The yellow precipitate produced by the reaction was recovered by filtration, and the obtained cake was washed with 158.4 parts of methanol to obtain 5.2 parts of the azomethine zinc complex (b) having the following structure. m / z = 325

Synthesis Example 1-3
6.37 parts of 1-amino-2-naphthol hydrochloride, 6.09 parts of 4-methoxy-2-hydroxybenzaldehyde, and 142.5 parts of methanol were mixed and stirred to prepare a solution, and then reflux was performed for 4 hours. .. After returning to room temperature, 8.78 parts of zinc acetate was dissolved in 39.6 parts of methanol, this solution was added, and the mixture was stirred for 2 hours. The yellow precipitate produced by the reaction was recovered by filtration, and the obtained cake was washed with 158.4 parts of methanol to obtain 5.8 parts of the azomethine zinc complex (c) having the following structure. m / z = 355

Synthesis Example 1-4
5.79 parts of 1-amino-8-chloro-2-naphthol, 3.66 parts of salicylaldehyde, and 142.5 parts of methanol were mixed and stirred to prepare a solution, and then reflux was carried out for 4 hours. After returning to room temperature, 6.58 parts of zinc acetate was dissolved in 39.6 parts of methanol, this solution was added, and the mixture was stirred for 2 hours. The yellow precipitate produced by the reaction was recovered by filtration, and the obtained cake was washed with 158.4 parts of methanol to obtain 5.6 parts of the azomethine zinc complex (d) having the following structure. m / z = 359

Synthesis Example 1-5
5.68 parts of 1-amino-8-methoxy-2-naphthol, 3.66 parts of salicylaldehyde, and 142.5 parts of methanol were mixed and stirred to prepare a solution, and then reflux was carried out for 4 hours. After returning to room temperature, 6.58 parts of zinc acetate was dissolved in 39.6 parts of methanol, this solution was added, and the mixture was stirred for 2 hours. The yellow precipitate produced by the reaction was recovered by filtration, and the obtained cake was washed with 158.4 parts of methanol to obtain 5.5 parts of the azomethine zinc complex (e) having the following structure. m / z = 355

Synthesis Example 2 (Synthesis of Comparative Compound)
44.3 parts of 2-hydroxy-1-naphthaldehyde, 27.3 parts of 2-aminophenol, and 1000 parts of water are mixed and stirred, and 41.4 parts of 25% caustic soda is diluted with 100 parts of water in the mixture. The solution was added. Then, 38.6 parts of sodium bisulfite was added, the temperature was raised to 90 ° C., and the mixture was stirred as it was for 15 minutes. After cooling, it was filtered and washed with 2200 parts of water. The obtained product was stirred in 625 parts of water, to which 71.5 parts of zinc (II) sulfate and 75 parts of 28% ammonium hydroxide were added. The mixed solution was stirred for 2 hours, and the yellow precipitate formed by the reaction was recovered by filtration. The obtained cake was washed with 4000 parts of water to obtain 78.7 parts of an azomethine zinc complex (f) having the following structure.

Test Example 1 (Measurement of maximum absorption wavelength of azomethine zinc complex synthesized in Synthesis Examples 1 to 4)
The maximum absorption wavelength of the azomethine zinc complex synthesized in Synthesis Examples 1 to 4 was measured according to the above-mentioned UV-vis spectrum measurement method. The results are shown in Table 1.

Test Example 2 (Measurement of chromaticity of azomethine zinc complex (a))
C. I. Pigment Green 58 (manufactured by FASTOGEN GREEN A110 DIC Corporation) 1.736 parts and 0.744 parts of the azomethine zinc complex (a) obtained in Synthesis Example 1 by BYK-LPN21116 (solid content: 40%) 1.063 2 parts with a paint shaker using zircon beads with a particle size of 0.3 to 0.4 mm together with 2.36 parts of Unidic ZL-295 (solid content: 40%) and 13.74 parts of propylene glycol monomethyl ether acetate. After time dispersion, coloring composition 1 was obtained. To 2.0 parts of the obtained coloring composition, 0.813 parts of Unidic ZL-295 was added and mixed with a paint shaker to obtain a color filter evaluation composition 1. This evaluation composition 1 was applied to soda glass. When coating, the evaluation glass substrate was prepared so that the film thickness was different by changing the rotation speed of the spin coater. The prepared glass substrate for evaluation was dried at 90 ° C. for 3 minutes, and the chromaticity (x, y) in the C light source was measured. The chromaticity was measured with CM-3500d manufactured by Konica Minolta.
(X, y) = (0.320, 0.490)

Test Example 3 (Measurement of chromaticity of azomethine zinc complex (b))
C. I. Pigment Green 58 (manufactured by FASTOGEN GREEN A110 DIC Corporation) 1.736 parts and 0.744 parts of the azomethine complex (b) obtained in Production Example 2 by BYK-LPN21116 (solid content: 40%) 1.063 parts , Unidic ZL-295 (solid content: 40%) 2.36 parts, propylene glycol monomethyl ether acetate 13.74 parts and zircon beads with a particle size of 0.3 to 0.4 mm for 2 hours in a paint shaker. The mixture was dispersed to obtain a coloring composition 2. 2.0 parts of the obtained coloring composition and 0.813 parts of Unidic ZL-295 were added and mixed with a paint shaker to obtain an evaluation composition 2 for a color filter. The chromaticity (x, y) of this evaluation composition 2 in a C light source was measured using the same method as in Test Example 2. The chromaticity was measured with CM-3500d manufactured by Konica Minolta.
(X, y) = (0.304, 0.490)

Comparative Test Example 1 (Measurement of chromaticity of azomethine zinc complex (f))
C. I. Pigment Green 58 (manufactured by FASTOGEN GREEN A110 DIC Corporation) 1.736 parts and 0.744 parts of the azomethine complex (f) obtained in Production Example 2 by BYK-LPN21116 (solid content: 40%) 1.063 parts , Unidic ZL-295 (solid content: 40%) 2.36 parts, propylene glycol monomethyl ether acetate 13.74 parts and zircon beads with a particle size of 0.3 to 0.4 mm for 2 hours in a paint shaker. The mixture was dispersed to obtain a coloring composition 3. 2.0 parts of the obtained coloring composition and 0.813 parts of Unidic ZL-295 were added and mixed with a paint shaker to obtain an evaluation composition 3 for a color filter. The chromaticity (x, y) of this evaluation composition 3 in a C light source was measured using the same method as in Test Example 2. The chromaticity was measured with CM-3500d manufactured by Konica Minolta.

The results of Test Examples 1 and 2 and Comparative Test Example 1 are summarized in Table 2.

It can be seen that the azomethine zinc complexes of Test Example 2 and Test Example 3 have a smaller x value than Comparative Test Example 1 and exhibit a bluish hue different from that of Comparative Test Example 1. In particular, Test Example 3 had an x value of about 0.02 points smaller than that of Comparative Test Example 1 and exhibited a bluish hue completely different from that of Comparative Test Example 1.

Claims (5)

The following formula (I') :

(I')
Table in (formula (in I '), X ¹ and X ² indicates each independently a hydrogen atom, a halogen atom or an alkoxy group, at least one of X ¹ and X ² is a halogen atom or an alkoxy group) Azomethin zinc complex to be made. The colorant containing the azomethine zinc complex according to claim 1. A coloring composition containing at least the zinc azomethine complex according to claim 1. A color filter having the azomethine zinc complex according to claim 1 in a pixel portion. The following formula (I):

(I)
(In formula (I), X ¹ And X ² Is a pigment for a color filter containing an azomethine-zinc complex represented by (representing a hydrogen atom, a halogen atom or an alkoxy group) independently.