JP2018123190A - Azomethine zinc complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel yellow pigment having an unconventional hue.SOLUTION: The present invention provides an azomethine zinc complex represented by the formula (I) (where, Xand Xindependently represent a hydrogen atom, a halogen atom or an alkoxy group).SELECTED DRAWING: None

Description

  The present invention relates to a novel azomethine zinc complex.

  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).

Japanese Patent Publication No.59-5625

  Currently, colored compositions are used in various fields. Specific applications include printing inks, paints, resin colorants, fiber colorants, information recording colorants (for color filters, toners, ink jets, etc.). Colorant to be used). Colors used in coloring compositions are mainly divided into pigments and dyes. The required properties include color characteristics (coloring power, sharpness) and resistance (weather resistance, light resistance, heat resistance, solvent resistance). )and so on. Usually, unlike a dye that develops color in a molecular state, a pigment develops from a particle state (aggregates of primary particles). For this reason, pigments are generally superior in resistance compared to dyes, but are often inferior in coloring power and sharpness. From such a background, pigments with high coloring power and high saturation are demanded. Of these, organic pigments, which have been dominant in terms of coloring power, are particularly attracting attention.

  Among these organic pigments, many new pigments have been actively developed so far, for example, yellow pigments have the second largest number of registered color indexes after red pigments. As yellow organic pigments in practical use, for example, C.I. I. Pigment Yellow 3, 12 and 74, etc., 74, 83, 109 and 110 etc. are used for paint applications, and 138 and 150 etc. are used for color filters.

Here, the color filter includes 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 of the green pixel portion. As the yellow pigment used in such a color filter, the above-mentioned two types (138 and 150) are mainly used from the viewpoint of transmission waveform and fastness.
However, C. is the most used among yellow pigments. I. Pigment Yellow 138 has poor coloring power, and is not practical in color standards requiring high color reproducibility, which has been increasingly demanded 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 150 is not sufficient in terms of luminance and coloring power, and hue variations are limited.
Under such circumstances, the expansion of the hue of the yellow pigment is an urgent issue in color filter applications.

  As a result of intensive studies in view of such a situation, the present inventors have found that a compound represented by the following formula (I) has a hue that has not existed before and completed the present invention. That is, the present invention provides the following formula (I):

(In formula (I), X ¹ and X ² each independently represent a hydrogen atom, a halogen atom or an alkoxy group) and an azomethine zinc complex represented by the following (sometimes 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 a conventional yellow pigment 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. Among them, a chlorine atom or a bromine atom is preferable, and a chlorine atom is more preferable.

  As the alkoxy group in the above formula (I), methoxy, ethoxy, propyloxy, i-propyloxy, butyloxy, i-butyloxy, s-butyloxy, t-butyloxy, pentyloxy, 1-methylbutyloxy, 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-dimethylbutylo 1-ethylbutyloxy, 2-ethylbutyloxy, 1,1,2-trimethylpropyloxy, 1,2,2-trimethylpropyloxy, 1-ethyl-1-methylpropyloxy, 1-ethyl-2- And methylpropyloxy. Especially, a C1-C8 thing is mentioned as a suitable example.

  The 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 embodiment of the production method of the compound of the present invention will be described. However, the present invention is not limited to these.

The compound of the present invention comprises 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 represents a hydrogen atom, a halogen atom or an alkoxy group), and zinc acetate is added to the obtained reaction solution, followed by further reaction.

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 a solvent, these 1 type (s) or 2 or more types can be selected suitably.

  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.

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

  Zinc acetate may be a hydrate or an anhydride. Moreover, you may use it in a solid state and you may use what was melt | dissolved in the solvent. Since the reaction can proceed efficiently, it is preferable to use zinc acetate dissolved in a solvent. Here, as a 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 applicable to various uses. For example, it can be used as a colorant for a wide range of uses such as printing ink, paint, colored plastic, toner, inkjet ink, light-shielding member for display, and seed coloring.

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

  The compound of the present invention exhibits properties as an organic pigment, and may be more suitably used by subjecting the pigment particles to a finer size, such as by salt milling treatment. Such processing may be performed by a known and conventional 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. These should be appropriately selected according to the use as described above, and the compound of the present invention may be used alone or in combination of two or more depending on the use.

As the colorant that can be used in combination, any of known pigments, dyes and the like may be used.
Depending on the application, azo, disazo, azomethine, anthraquinone, quinophthalone, quinacridone, diketopyrrolopyrrole, dioxazine, benzimidazolone, phthalocyanine, isoindoline, isoindolinone, perylene pigment And xanthene, azo, disazo, anthraquinone, quinophthalone, triarylmethane, methine, phthalocyanine, and rhodamine dyes.

  As yellow pigments that can be used in combination with the compounds of the present invention, C.I. I. Pigment Yellow 3, 12 and 74, etc., for paint applications 74, 83, 109 and 110, etc., for color filters, 83, 129, 138, 139, 150, Examples thereof include quinophthalone pigments described in Nos. 185, 231 and 5817028.

  In particular, when the compound of the present invention is used for forming a green pixel portion in color filter applications, for example, C.I. I. Pigment Green 1, 2, 4, 4, 7, 10, 13, 14, 14, 17, 17, 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 weight of the yellow pigment per 100 parts by weight of the green pigment. It is.

Moreover, when using this invention compound for green pixel part formation, this invention compound and a blue pigment can also be used together. 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 aluminum phthalocyanine derivative include compounds represented by the following general formula (3-1).

(In formula (3-1), R represents 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 represents a binding site.)

  As said halogen atom in R in above-described formula (3-1), a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example. Among these, the halogen atom in R is preferably a chlorine atom or a bromine atom.

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

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

  Preferred examples of the formula (3-1) include, for example, hydroxyaluminum phthalocyanine, chloroaluminum phthalocyanine, bromoaluminum phthalocyanine, a compound represented by the following formula (3-1-1), and the following formula (3-1-2) ), A compound represented by the following formula (3-1-3), and the like.

  Furthermore, this invention compound can also be used together with a red pigment for red pixel part formation in a color filter use. Examples of red pigments include C.I. I. Pigment red 177, 254, and the like.

  When the present invention is used for forming the pattern of the green pixel portion of the color filter, a known method can be employed. 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 applied onto a transparent substrate such as glass by a spin coating method, a roll coating method, an ink jet method, etc. There is a method called photolithography in which the coating film is subjected to pattern exposure with ultraviolet rays through a photomask, and then an unexposed portion is washed with a solvent or the like to obtain a green pattern. The same applies to the case where the present invention is used for forming the pattern of the red pixel portion of the color filter.

  In addition, a color filter may be manufactured by forming a pattern of the pixel portion by an electrodeposition method, a transfer method, a micellar electrolysis method, or a PVED (Photovoltaic Electrodeposition) method.

  In order to prepare the photosensitive composition for color filters, 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 is generally used in which a dispersion is prepared using a pigment, an organic solvent, and a dispersant as required, and then a photosensitive resin or the like is added thereto.

  As a pigment here, when obtaining a green pixel part, what pigment-ized this invention compound and the above-mentioned green pigment and blue pigment can be used. Similarly, when a red pixel portion is obtained, a pigment obtained by compounding the compound of the present invention and the red pigment described above can be used.

  Examples of the dispersant used as needed include, for example, DISPERBYK (registered trade name) 130, 161, 162, 163, 170, LPN-6919, LPN-21116, Efka 46 of BASF, Fuka 47 etc. are mentioned. In addition, a revenig rigging agent, a coupling agent, a cationic surfactant, and the like can be used together.

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

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

  In the case of a green pixel application, the above color filter pigment composition is 10 parts by mass of the azomethine zinc complex of the present invention, and in the case of a green pixel application, 200 parts by mass or less of a green pigment and / or 200 parts by mass or less of a blue pigment. The mixture is appropriately set and mixed. In the case of a red pixel application, 200 parts by mass or less of a red pigment is mixed. In addition, you may mix another yellow pigment as needed.

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

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

  The thus prepared photosensitive composition for a color filter pixel portion is subjected to pattern exposure with ultraviolet rays through a photomask, and then a color filter is prepared by washing an unexposed portion with an organic solvent or alkaline water. Can do.

EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not limited by this. In Examples and Comparative Examples, “part” and “%” are based on mass unless otherwise specified.
The measurement methods used in the examples are as follows.
(1) Molecular weight measurement About 5 mg of a sample was dispersed in 1 ml of THF to prepare a solution, and this was performed using GC / TOFMS JMS-T100GC, manufactured by JEOL Ltd.
(2) UV-vis spectrum measurement A sample was dissolved in 50 mL of DMSO and further diluted with DMSO to prepare a solution, which was measured using a spectrophotometer U3900 manufactured by Hitachi.

[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 form a solution, and then refluxed for 4 hours. . After returning to room temperature, 8.78 parts of zinc acetate was dissolved in 39.6 parts of methanol, and this solution was added and stirred for 2 hours. The yellow precipitate produced by the reaction was collected by filtration, and the resulting cake was washed with 158.4 parts of methanol to obtain 5.8 parts of an azomethine zinc complex (a) having the following structure. m / z = 359

Synthesis Example 1-2
1-amino-2-naphthol hydrochloride 5.85 parts, salicylaldehyde 3.66 parts, and methanol 142.5 parts were mixed and stirred to form a solution, and then refluxed for 4 hours. After returning to room temperature, 6.58 parts of zinc acetate was dissolved in 39.6 parts of methanol, and this solution was added and stirred for 2 hours. The yellow precipitate produced by the reaction was collected by filtration, and the obtained cake was washed with 158.4 parts of methanol to obtain 5.2 parts of an 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 form a solution, and then refluxed for 4 hours. . After returning to room temperature, 8.78 parts of zinc acetate was dissolved in 39.6 parts of methanol, and this solution was added and stirred for 2 hours. The yellow precipitate produced by the reaction was collected by filtration, and the obtained cake was washed with 158.4 parts of methanol to obtain 5.8 parts of an azomethine zinc complex (c) having the following structure. m / z = 355

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

Synthesis Example 1-5
1-Amino-8-methoxy-2-naphthol (5.68 parts), salicylaldehyde (3.66 parts), and methanol (142.5 parts) were mixed and stirred to form a solution, and then refluxed for 4 hours. After returning to room temperature, 6.58 parts of zinc acetate was dissolved in 39.6 parts of methanol, and this solution was added and stirred for 2 hours. The yellow precipitate produced by the reaction was collected by filtration, and the obtained cake was washed with 158.4 parts of methanol to obtain 5.5 parts of an 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 mixed solution. The solution was added. Thereafter, 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 resulting product was stirred in 625 parts of water, and 71.5 parts of zinc (II) sulfate and 75 parts of 28% ammonium hydroxide were added thereto. The mixture was stirred for 2 hours and the yellow precipitate produced by the reaction was collected 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-described 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 were used in BYK-LPN21116 (solid content: 40%) 1.063. Part, Unidic ZL-295 (solid content: 40%) 2.36 parts, propylene glycol monomethyl ether acetate 13.74 parts and zircon beads having a particle size of 0.3 to 0.4 mm, and 2 with a paint shaker After time dispersion, a colored composition 1 was obtained. Color filter evaluation composition 1 was obtained by adding 0.813 parts of Unidic ZL-295 to 2.0 parts of the obtained colored composition and mixing with a paint shaker. This evaluation composition 1 was applied to soda glass. The glass substrate for evaluation was produced so that film thickness might differ by changing the rotation speed of a spin coater when apply | coating. The produced glass substrate for evaluation was dried at 90 ° C. for 3 minutes, and chromaticity (x, y) in a 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. 1. 636 parts of Pigment Green 58 (manufactured by FASTOGEN GREEN A110 DIC Corporation), 0.744 parts of the azomethine complex (b) obtained in Production Example 2, 1.063 parts of BYK-LPN21116 (solid content: 40%) 2 hours on a paint shaker using zircon beads having 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 Dispersion was performed to obtain a colored composition 2. 2.0 parts of the obtained colored composition and 0.813 parts of Unidic ZL-295 were added and mixed with a paint shaker to obtain a composition 2 for color filter evaluation. Using this evaluation composition 2 in the same manner as in Test Example 2, the chromaticity (x, y) in a C light source was measured. 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 the azomethine complex (f) 0.744 parts obtained in Production Example 2 are used in 1.063 parts of BYK-LPN21116 (solid content: 40%). 2 hours on a paint shaker using zircon beads having 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 Dispersion was performed to obtain a colored composition 3. 2.0 parts of the obtained colored composition and 0.813 parts of Unidic ZL-295 were added and mixed with a paint shaker to obtain a composition 3 for color filter evaluation. Using this evaluation composition 3 in the same manner as in Test Example 2, the chromaticity (x, y) in a C light source was measured. 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, in Test Example 3, the x value was about 0.02 points smaller than that of Comparative Test Example 1, and a completely different bluish hue from that of Comparative Test Example 1 was exhibited.

Claims (4)

The following formula (I):

(In formula (I), X ¹ and X ² each independently represents a hydrogen atom, a halogen atom or an alkoxy group). The coloring agent containing the azomethine zinc complex of Claim 1. A coloring composition containing at least the azomethine zinc complex according to claim 1. A color filter comprising the azomethine zinc complex according to claim 1 in a pixel portion.