JP2000141921A - Coloring matter for sublimation type heat-transfer recording - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring matter for post-chelate wherein preservation stabilities such as light-resistance, heat-resistance and moisture-resistance are improved, an ink sheet for which a metal chelate coloring matter and the coloring matter for post-chelate are used, an image forming method, an optical recording medium, and a coloring composition for a color filter. SOLUTION: A coloring matter which is represented by the formula, wherein a reduction potential which can form a chelate with a metal ion-containing compound is in a range from -1,100 to -800 mV (SCE), a chelate coloring matter of the coloring matter and a metal ion-containing compound, an ink sheet having the coloring matter and an image forming method, an optical recording medium using the chelate coloring matter and a coloring composition for a color filter are provided. In the formula, R1, R2 each represent an alkyl group which may be substituted. Also, the group may be one which forms a cycle with R1 and R2 connected. R3, R4, R5, R6 each represent H, an alkyl group and an alkoxy group. A, B each represent a substituent, but, at least either one of A or B is a group which can form a chelate with a metal ion-containing compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cyan dye for post-chelation, which has improved storage stability such as light resistance, heat resistance and moisture resistance, and a chelate dye thereof, and an ink sheet and an image using the dye. The present invention relates to a forming method, an optical recording medium, and a coloring composition for a color filter.

[0002]

2. Description of the Related Art In recent years, with the development of electronic images, there has been an increasing need for color hard copies having good image storability and needs for optical recording media such as CD-Rs having good storability.
However, since color hardcopy is stored in various environments, it is important that image storability such as light resistance, heat resistance, and moisture resistance be excellent. Attempts have been made, but there are still no dyes that can provide sufficient image storability.

Further, with respect to the cyan dye, it is necessary that absorption is small in the yellow and magenta regions in order to obtain good color reproducibility, but the color reproducibility is excellent and the storage stability is also excellent. No pigment has been obtained at present.

[0004] Among dyes used in optical recording media, dyes having appropriate absorption in the near infrared region and excellent storage stability have not been obtained at present.

To obtain a color hard copy, for example,
There are a sublimation thermal transfer method and an ink jet method. In the sublimation thermal transfer method, in order to form an image by heating the image with a thermal head or the like and transferring the sublimable dye to the image receiving layer like an image,
Since the dye can be transferred in proportion to the amount of heat, an image having a rich gradation can be formed. In addition, in the ink jet system, a dye dissolved in a solvent is sprayed as small dots on an image receiving sheet from a nozzle called a head, so that there is an advantage that the type of the image receiving sheet does not have to be selected.

The light fastness, heat resistance,
As a means for improving image storability such as moisture resistance, a method in which a metal chelate-forming dye (post-chelate dye) is reacted with a metal ion-containing compound (metal source) to form a metal chelate dye on an image (post-chelate method) )It has been known. (The thermal transfer method is described in JP-A-59-78893, JP-A-59-10349, JP-A-60-2398, and the like.
Further, regarding the ink jet system, Japanese Patent Application Laid-Open No. 55-5
3591, JP-A-55-150396, JP-A-62-198491, JP-A-62-2524.
No. 84, JP-A-63-299970, JP-A-8-156399, JP-A-9-277693 and the like. ) These post-chelating cyan dyes include, for example,
Azo dyes described in JP-A-4-62094, JP-A-4-82784, and JP-A-7-137467, for example, imidazole azomethine dyes described in JP-A-7-246771 are known. However, the azomethine dyes described above have good image storage stability but have a large side absorption in the yellow region, and thus have a problem in color reproducibility.
The above imidazole azomethine dye has good color reproducibility due to little side absorption in the yellow region, but has storage stability,
In particular, there was a problem in moisture resistance.

With the rapid increase in the amount of information to be recorded in recent years, large-capacity optical recording media have become necessary. Organic optical recording media have been used for these large-capacity optical recording media. In addition, long wavelength absorbing dyes that absorb light in the red to near infrared region are used in organic optical recording media.

Hitherto, cyanine dyes having excellent absorption and reflection characteristics have been used for this purpose among various dyes. However, due to low storage stability such as light resistance, information is lost over time, There was a drawback that writing was not possible. In order to solve such a problem, for example, US Pat.
No. 00, No. 4,050,938, JP-A-60-118748, JP-A-63-199248.
JP-A No. 2-300288 and JP-A-2-300288 disclose a light stabilizer and a light stabilizing method, but have not yet achieved sufficient storage stability. Also, Japanese Unexamined Patent Publication No.
No. 86, Japanese Unexamined Patent Publication No. 2-76884, Japanese Unexamined Patent Publication No.
No. 17701 describes a metal chelate dye having excellent storage stability, but cannot be used for applications such as optical recording media because the absorption wavelength is too long.

An attempt to use a metal chelate obtained by reacting a post chelate with a metal ion-containing compound (metal source) as a chelating dye for an optical recording medium has been disclosed in Japanese Patent Application No. 9-6.
No. 9404, but this was not at a satisfactory level.

[0010] Further, since a color filter is required to have high transparency, a method called a dyeing method of coloring with a dye has been performed. For example, a color filter used in a liquid crystal display device is obtained by applying a photosensitive material to be dyed to a substrate such as glass, performing pattern exposure of one filter color, and washing unexposed portions in a developing process. The operation of dyeing the remaining pattern portion with the dye of the filter color is repeated for all the required filter colors.

This method has a high transmittance due to the use of a dye and has excellent optical characteristics of a color filter, but has limitations in light resistance and heat resistance. Therefore, instead of dyes, organic pigments having excellent light resistance and heat resistance have come to be used, but it has been difficult to obtain optical characteristics like dyes with color filters using pigments. For example, Japanese Patent Application No. 9-69404 has proposed an attempt to use a metal chelate obtained by reacting a post chelate with a metal ion-containing compound (metal source) as a chelating dye for an optical recording medium. Not a level.

[0012]

Accordingly, the first aspect of the present invention is as follows.
An object of the present invention is to provide a dye for post-chelation and a metal chelate dye having improved storage stability such as light resistance, heat resistance and moisture resistance. Further, a second object of the present invention is to provide an ink sheet, an image forming method, an optical recording medium and a coloring composition for a color filter using the dye.

[0013]

The object of the present invention is to provide: (1) a compound represented by the following general formula (1) wherein a reduction potential capable of forming a chelate with a metal ion-containing compound is between -1100 mV and -800 mV (SCE). The dye represented by (2) The reduction potential is from -1100 mV to -800 mV (S
A chelate dye comprising a chelate of a dye represented by the following general formula (1) and a metal ion-containing compound between CE). (3) The reduction potential is from -1100 mV to -800 mV (S
An ink sheet comprising a dye represented by the following general formula (1) between CE). (4) The ink sheet containing the dye and the image receiving sheet are overlapped, and the dye of the ink sheet is thermally diffused by imagewise heating according to the recording signal, and is reacted with the metal ion-containing compound to form a chelate dye. In the sublimation thermal transfer recording in which an image is formed on an image receiving sheet, the dye is a dye represented by the following general formula (1) having a reduction potential between -1100 mV and -800 mV (SCE). Image forming method. (5) On the transparent substrate, the reduction potential is from -1100 mV-
An optical recording medium comprising at least one light-absorbing layer containing a dye represented by the following general formula (1) and a chelate dye formed of a metal ion-containing compound at a temperature between 800 mV (SCE). (6) The reduction potential is from -1100 mV to -800 mV (S
A coloring composition for a color filter, comprising a dye represented by the following general formula (1) and a chelate dye formed from a metal ion-containing compound, which is present between CE and CE).

[0014]

Embedded image[Wherein, R¹, R^Two Is an optionally substituted alkyl
Represents a group. Also, R¹And R^TwoIs linked to form a ring
There may be. R^Three, R^Four, R^Five, R⁶Is a hydrogen atom,
And an alkoxy group. A and B represent a substituent. Was
However, at least one of A and B is a metal ion
Is a group capable of forming a chelate with a compound containing a compound. ]
Was achieved.

Hereinafter, the present invention will be described in detail.

First, the following general formula (1) wherein the reduction potential capable of forming a chelate with the metal ion-containing compound in the present invention is between -1100 mV and -800 mV (SCE).
(Hereinafter, also referred to as the dye of the present invention) will be described.

[0017]

Embedded image In the general formula (1), A and B each represent a substituent, and either A or B is a group capable of forming a chelate with a metal ion-containing compound (chelate forming group).

As the chelate-forming group, a nitrogen-containing 5-membered ring represented by the following general formula (2) is preferable.

[0019]

Embedded image In the general formula (2), Z _{1 to} Z ₄ represent a nitrogen atom or ≡
Represents C-Rz. Here, Rz represents an electron donating group having a Hammett's rule substituent constant σp value of 0.1 or less or a hydrogen atom having a σp value of 0.1 or less. Preferred Rz include a hydrogen atom, an electron donating alkyl group (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group,
2-ethylhexyl group, ethoxyethyl group, polyethoxyethyl group), electron donating aryl group (for example, phenyl group, m-tolyl group, p-methoxyphenyl group, o
-Butoxyphenyl group, p-dimethylaminophenyl group, mesityl group, m-methyl-p-methoxyphenyl group), electron-donating alkoxy group (for example, methoxy group,
An ethoxy group, a propoxy group, a butoxy group, an ethoxyethoxyethoxy group or the like), an electron-donating aryloxy group (for example, a phenoxy group, an m-methylphenoxy group,
-Methoxyphenoxy group, o-dimethylaminophenoxy group), and an electron-donating substituted amino group (eg, dimethylamino group, diethylamino group) and the like.

In the general formula (1), one of the substituents represented by A and B may be a substituent that is not a chelate-forming group. An electron donating group having a constant σp value of 0 or less is preferable.

Specifically, an electron-donating alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a 2-ethylhexyl group, an ethoxyethyl group,
A polyethoxyethyl group, an electron donating aryl group (for example, phenyl group, m-tolyl group, p-methoxyphenyl group, o-butoxyphenyl group, p-dimethylaminophenyl group, mesityl group, m-methyl- a p-methoxyphenyl group), an electron donating heterocyclic group (for example,
A pyrrole group, an imidazole group, etc.), an electron donating alkoxy group (eg, methoxy group, ethoxy group, propoxy group, butoxy group, ethoxyethoxyethoxy group, etc.), and an electron donating aryloxy group (eg, phenoxy group, m -Methylphenoxy group, p-methoxyphenoxy group, o-dimethylaminophenoxy group, etc.) and substituted electron-donating amino groups (eg, dimethylamino group, diethylamino group, etc.), and phenyl substituted with an electron-donating group. Groups and electron donating heterocyclic groups are preferred.

In the general formula (2), R ¹ and R ² each represent an alkyl group which may be substituted, and the alkyl group mentioned here includes an alkenyl group. Preferred alkyl groups which may be substituted include, for example, methyl group, ethyl group, propyl group, butyl group, hydroxyethyl group,
Examples thereof include a dimethylaminosulfonylethyl group, a methoxyethyl group, and a 2-ethylhexyl group. Examples of the alkenyl group which may be substituted include an ethynyl group, a propenyl group, and a butenyl group. Also, R ¹
And R ² are linked to form a ring, R ¹ and R ²
Examples of the condensed ring formed by include a cycloalkyl group (eg, a cyclohexyl group) and a cycloalkenyl group (eg, a cyclohexenyl group).

In the general formula (2), R ³ , R ⁴ , R ⁵ ,
R ⁶ represents a hydrogen atom, an alkyl group, or an alkoxy group,
The alkyl group referred to herein includes an alkenyl group and a cyclic one. Further, these alkyl groups and alkoxy groups may have a substituent.

Examples of these alkyl groups include a methyl group, an ethyl group, a propyl group, a butyl group, a hydroxyethyl group, a methoxyethyl group, a 2-ethylhexyl group, a cyclohexyl group and a cyclohexenyl group.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a butoxy group, and an ethoxyethoxyethoxy group.

In the present invention, the dye represented by the general formula (1) has a reduction potential of -1100 to -800 mV (SC
E). When the reduction potential is higher than -800 mV, the storage stability, particularly the moisture storage stability, is significantly deteriorated. Compounds having a reduction potential of less than -1100 mV cannot be synthesized within the range of the general formula (1).

The oxidation potential and reduction potential referred to in the present invention are B
This was measured by Oster Young square wave voltammetry using a 100B / W apparatus manufactured by AS Corporation. The measurement is
The dye sample was dissolved in a dry acetonitrile solvent containing 0.1 mol / L of tetrabutylammonium perchlorate as a supporting electrolyte at a concentration of approximately 10 ^-4 to 10 ^-3 mol / L, and after degassing through nitrogen gas, A silver / silver nitrate electrode was used as a reference electrode, a fine platinum electrode was used as a working electrode, and a platinum wire was used as a counter electrode. All the obtained values are values obtained by correcting the value of ferrocene measured at the same time as 400 mV (vs SCE).

Hereinafter, the dye of the present invention will be exemplified, but the dye of the present invention is not limited thereto.

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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The metal ion-containing compound used in the chelate dye formed from the dye of the present invention will be described.

The metal ion-containing compounds used in these chelate dyes include inorganic or organic salts of metal ions and metal chelates.

Examples of the metal in the metal ion-containing compound include monovalent and polyvalent metals belonging to Groups 1 to 8 of the periodic table. Among them, Al, Co, Cr, Cu, F
e, Mg, Mn, Mo, Ni, Sn, Ti and Zn are preferred, and Ni, Cu, Cr, Co and Zn are particularly preferred. Specific examples of the metal ion-containing compound (hereinafter, also referred to as a metal source) include Ni ²⁺ , Cu ²⁺ ,
Cr ²⁺ , Co ²⁺ and Zn ²⁺ and an aliphatic salt such as acetic acid or stearic acid, or a salt of an aromatic carboxylic acid such as benzoic acid or salicylic acid, or Cl ⁻ ion, Br ⁻ ion, B
Salts with inorganic ions such as F ^- ₄ ion, ClO ^- ₄ ion and SO ^- ₄ ion are exemplified.

The metal ion-containing compound used in the present invention
In particular, a complex represented by the following general formula (17) is particularly preferred.
Can be used. General formula (17) [M (Q₁)_l(Q _Two)_m(Q_Three)_n]^{p +}(Y^-)_p [Wherein, M represents a metal ion;₁, Q_Two, Q_ThreeAre each
A coordination compound capable of coordinating with a metal ion represented by M
And Y represents an organic anion group. l is 1, 2 or 3
M represents 1, 2 or 0, and n represents 1 or
Represents 0, and p represents 0, 1 or 2. In the general formula (17), a metal ion represented by M
The Ni²⁺, Cu²⁺, Cr²⁺, Co²⁺And Zn²⁺Is good
Good.

The coordination compounds represented by Q ₁ , Q ₂ and Q ₃ may be the same or different. Examples of these coordination compounds include the coordination compounds described in Chelate Chemistry (5) (Nankodo).

Specific examples of the organic anion group represented by Y include a tetraphenylboron anion and an alkylbenzenesulfonic acid anion.

1 represents an integer of 1, 2 or 3, m represents 1, 2 or 0, and n represents 1 or 0, which is a tetradentate of the complex represented by the general formula (17). Coordination
It is determined by hexadentate coordination or by the number of Q ₁ , Q ₂ , Q ₃ ligands.

P represents 0, 1 or 2. P is 0 when the coordination compound represented by Q is an anionic compound and the anionic compound represented by Q and the metal cation represented by M are electrically neutralized. .

The anionic compound is preferably a compound represented by the following general formula (18).

[0044]

Embedded image [Wherein, R ³¹ and R ³³ each represent an alkyl group, an aryl group or a heterocyclic group which may be the same or different,
R ³² represents an alkyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, or a hydrogen atom. The metal chelate compound may be formed by mixing the dye (post-chelate dye) of the present invention and a metal ion-containing compound in a solvent. Further, the coating solution of the post-chelating dye and the solution of the metal ion-containing compound may be separately prepared and mixed, or may be formed by applying these solutions repeatedly. Alternatively, the metal chelate dye may be isolated by reacting the post chelate dye with the metal ion-containing compound in advance.

Next, the ink sheet and the image forming method of the present invention will be described.

The image forming method of the present invention is an image forming method for forming an image by a sublimation type thermal transfer recording system using a post-chelating dye and a metal ion-containing compound.

In the sublimation type thermal transfer recording system, a thermal transfer layer of an ink sheet containing a dye or a metal chelate compound thereof is superimposed on an image receiving material, and heat corresponding to image information is applied to the ink sheet to thereby provide a dye or the present invention. An image by the metal chelate compound is formed on the image receiving material. The dye of the present invention can be used in the above-described sublimation type thermal transfer recording system.

In the image forming method of the present invention, the above-described reduction potential is from -1100 mV to -800 mV (SCE).
An ink sheet containing a heat-diffusible dye represented by the following general formula (1) (hereinafter, sometimes referred to as the dye of the present invention) and an image-receiving sheet are superimposed on each other to form an image corresponding to a recording signal. By such heating, the dye thermally diffused from the ink sheet is reacted with the metal ion-containing compound to form a chelate dye, thereby forming an image on the image receiving sheet.

After the image is formed as described above, the image-receiving material on which the image has been formed may be heated once more in order to improve the fixing property of the image.

The ink sheet containing the heat-diffusible dye used in the image forming method of the present invention may be constituted, for example, by providing a heat-sensitive transfer layer containing the dye of the present invention or its metal chelate compound on a support. it can.

In the above ink sheet, the thermal transfer layer is prepared by dissolving the dye of the present invention in a solvent or dispersing it as fine particles together with a binder, for example, to prepare an ink liquid, and applying the ink liquid on a support. And by appropriately drying.

The thickness of the thermal transfer layer is 0.1 to 1 in terms of dry film thickness.
0 μm is preferred.

As the binder used for the ink liquid, acrylic resin, methacrylic resin, polyvinyl chloride, poly (vinyl chloride-vinyl acetate copolymer), polystyrene,
Polystyrene-acrylic copolymer, polycarbonate,
Solvent-soluble polymers such as polysulfone, polyethersulfone, polyvinyl butyral, polyvinyl acetal, nitrocellulose, and ethyl cellulose, and polymer copolymers are preferred.

These binders can be used alone or in combination of two or more. In addition to being used by dissolving in an organic solvent, the binder can be used by dispersing it in a latex form in a solvent. The amount of the binder used is preferably 0.1 to ²⁰ g per 1 m ² of the support.

Examples of the organic solvent include alcohols (eg, ethanol, propanol), cellosolves (eg, methylcellosolve), aromatics (eg, toluene, xylene), esters (eg, acetate), ketones (Eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, dioxane) and the like can be used.

The support used for the ink sheet may be any as long as it has good dimensional stability and can withstand heating of a thermal head or the like used for recording. Examples thereof include thin paper such as condenser paper and glassine paper, and polyethylene. A heat-resistant plastic film such as terephthalate, polyamide, or polycarbonate is preferably used. The thickness of the support is preferably 2 to 30 μm. The support is preferably provided with an undercoat layer for the purpose of improving adhesion, preventing transfer of dye to the support, and preventing dyeing. Further, a slipping layer may be provided on the back surface of the support (the side opposite to the side on which the thermal transfer layer is provided) for the purpose of preventing the thermal head or the like from sticking to the support.

The ink sheet of the present invention may be formed on a heat-sensitive transfer layer or on a support on which a heat-sensitive transfer layer is coated, for the purpose of using an image-receiving material having no image-receiving layer, such as plain paper. And a heat-fusible layer containing a heat-fusible compound as described in JP-A-59-106997. As the heat-fusible compound, 65
A colorless or white compound that melts at a temperature of about 150 ° C. is preferably used. For example, waxes such as carnauba wax, beeswax, candeline wax, microcrystalline wax, and polyethylene wax are preferably used.

Incidentally, these heat-meltable layers include, for example,
Polymers such as polyvinylpyrrolidone, polyvinylbutyral, polyester, and vinyl acetate may be contained.

In the full-color image recording, a cyan heat-sensitive transfer layer containing a heat-diffusible cyan dye capable of forming a cyan image and a magenta heat-sensitive transfer containing a heat-diffusible magenta dye capable of forming a magenta image are used. A layer and a yellow heat-sensitive transfer layer containing a heat-diffusable yellow dye capable of forming a yellow image, and three layers of a heat-sensitive transfer layer containing a black image-forming substance, if necessary, are further provided with four layers. It can be carried out by using ink sheets which are sequentially arranged and applied on the same upper surface.

In the image forming method of the present invention, after the heat-sensitive transfer layer of the ink sheet and the image receiving material are overlaid,
Applying heat according to image information to the ink sheet, transferring the dye of the present invention onto the image receiving material, and forming an image with the metal chelate dye formed by the reaction between the transferred dye of the present invention and the metal ion-containing compound on the image receiving material. May be formed on top,
Also, after superimposing the ink sheet and the image receiving material,
Heat corresponding to the image information may be applied to the thermal transfer recording material, and an image may be formed on the image receiving material by a metal chelate dye formed by a reaction between the thermally diffused dye of the present invention and the metal ion-containing compound.

In the image forming method of the present invention, the metal ion-containing compound may be present in the image receiving material, or may be present in a heat-meltable layer or the like provided on the ink sheet.

Examples of the metal ion-containing compound used in the image forming method of the present invention include inorganic or organic salts of metal ions and metal chelates. Among them, salts and complexes of organic acids are preferred.

Examples of the metal in the metal ion-containing compound include monovalent and polyvalent metals belonging to Groups 1 to 8 of the periodic table. Among them, Al, Co, Cr, Cu, F
e, Mg, Mn, Mo, Ni, Sn, Ti and Zn are preferred, and Ni, Cu, Cr, Co and Zn are particularly preferred. Specific examples of the metal ion-containing compound (metal source) include Ni ²⁺ , Cu ²⁺ , Cr ²⁺ , Co ²⁺ and Zn ²⁺
And aliphatic salts such as acetic acid and stearic acid; and salts of aromatic carboxylic acids such as benzoic acid and salicylic acid.

As the metal ion-containing compound used in the present invention, the complex represented by the general formula (17) described above is also preferably used.

The metal source is usually 0.5 to 20 g /
It is preferably used m ^2, and the more preferable for use in 1 to 15 g / m ^2.

As the image receiving sheet, for example, paper, a plastic film, or a paper-plastic film composite generally used as the image receiving sheet can be used.

When the image receiving sheet comprises a support and an image receiving layer, examples of the image receiving layer include polyester resin, polyvinyl chloride resin, vinyl chloride and other monomers (for example,
One or two or more polymer layers such as a copolymer resin with vinyl acetate), polyvinyl butyral, polyvinyl pyrrolidone, and polycarbonate can be used.

The image-receiving sheet may be provided with a protective layer on the image-receiving layer for the purpose of preventing fusion, and an intermediate layer between the support and the image-receiving layer for the purpose of adhesion, heat insulation or cushioning effect. May be provided.

Next, the optical recording medium of the present invention will be described.

The optical recording medium according to the present invention comprises:
The reduction potential described above is from -1100 mV to -800 m
At least one light-absorbing layer containing a dye (dye of the present invention) represented by the general formula (1) between V (SCE) and a chelate dye formed of a metal ion-containing compound is provided.

Examples of the metal ion-containing compound used in the chelate dye include inorganic or organic salts of metal ions and metal complexes.

Examples of the metal in the metal ion-containing compound include monovalent and polyvalent metals belonging to Groups 1 to 8 of the periodic table. Among them, Al, Co, Cr, Cu, F
e, Mg, Mn, Mo, Ni, Sn, Ti and Zn are preferred, and Ni, Cu, Cr, Co and Zn are particularly preferred. Specific examples of the metal ion-containing compound (hereinafter, also referred to as a metal source) include Ni ²⁺ , Cu ²⁺ , C 2
r ²⁺ , Co ²⁺ and Zn ²⁺ and salts of aliphatic acids such as acetic acid and stearic acid, or salts of aromatic carboxylic acids such as benzoic acid and salicylic acid, or Cl ⁻ ions, Br ⁻ ions and BF
^- ₄ ion, ClO ^- ₄ ion, SO ^- ₄ and salts with inorganic ions such as ions. Further, the complex represented by the general formula (17) described above is also preferably used.

The recording layer having a metal chelate compound may be formed by mixing a post-chelate dye and a metal ion-containing compound in a coating solution and then coating the mixture. The coating solution of the ion-containing compound may be separately prepared and formed by applying multiple layers when applying, or the post-chelating dye and the metal ion-containing compound may be reacted in advance to isolate the metal chelating dye. After that, it may be dissolved in a coating solution and applied.

The transparent substrate constituting the optical recording medium of the present invention is a substrate which is substantially transparent (having a transmittance of 80% or more) in a wavelength region (for example, 600 to 900 nm) of a laser beam used for recording / reproducing. Say.

When the optical recording medium of the present invention is used as a normal compact disc, the thickness is 1.2 mm.
A circular base having a diameter of about 80 to 120 mm is used. Examples of the material constituting the base include transparent resins such as polymethyl methacrylate resin, acrylic resin, polycarbonate resin, epoxy resin, polysulfone resin, and methylpentene polymer, and glass.

An oxygen barrier coating may be formed on the outer surface, inner surface, and inner / outer peripheral surface of the substrate, if necessary. It is preferable that a tracking groove is formed.

The light absorbing layer using the dye of the present invention has a preferable extinction coefficient k in the wavelength region of laser light as a light absorbing layer of an optical recording medium. Therefore, it also has a suitable reflectance.

If the extinction coefficient k of the light absorbing layer in the wavelength region of the laser beam is excessively large, the reflectivity is reduced, and reproduction with reflected light cannot be performed sufficiently well. If it is too small, it becomes difficult to perform recording with normal recording power. The preferred range of the extinction coefficient k is 0.01 to 0.1.

The refractive index n (the real part of the complex refractive index) of the light absorbing layer in the wavelength region of the laser light is preferably 1.8 to 4.0.

The light absorbing layer may contain other types of dye compounds, various resins, surfactants, antistatic agents, dispersants, antioxidants, crosslinking agents, and the like.

The light absorbing layer may be formed on one surface of the substrate, or may be formed on both surfaces of the substrate.
In addition, the thickness of the light absorbing layer is usually 500 to 300.
0 Å is preferred.

The method for forming the light absorbing layer on the substrate is not particularly limited, and examples thereof include spin coating, dipping coating, spray coating, blade coating, roller coating, bead coating, and the like. Meyer coating method,
Various methods such as a curtain coating method can be used.

Examples of the solvent used for forming the light absorbing layer include ketone solvents such as cyclohexanone, ester solvents such as butyl acetate, ether solvents such as ethyl cellosolve, alcohol solvents, and aromatic solvents such as toluene. Solvents, alkyl halide solvents and the like.

A reflection layer may be formed on the light absorption layer. The reflection layer is made of, for example, Au, Al-Mg alloy, Al
-It can be formed by means of vapor deposition, sputtering, or the like, using a metal having high reflectivity such as a Ni alloy, Ag, Pt, and Cu. Preferably, the thickness of the reflective layer is at least 500 angstroms.

A protective film made of, for example, an ultraviolet curable resin may be formed on the reflective layer. The thickness of the protective film is about 0.1 to 100 μm, and its hardness is
The pencil hardness at 25 ° C. is preferably H to 8H.

An adhesive layer may be provided between the light absorbing layer and the reflecting layer to make them adhere to each other. It is desirable that the thickness of the adhesive layer be 10 to 300 Å.

As the light source for recording and reproducing the optical recording medium of the present invention, a solid laser, a gas laser, a dye laser,
Although a semiconductor laser is used, a semiconductor laser is preferable from the viewpoint of low cost, small size, low power consumption, and the like. Since the light absorbing layer of the optical recording medium of the present invention has particularly high recording sensitivity, a semiconductor laser of 600 nm to 800 nm is suitable.

Next, the coloring composition for a color filter of the present invention will be described.

The coloring composition for a color filter of the present invention has a reduction potential of from -1100 mV to -80 as described above.
It contains a dye (dye of the present invention) represented by the general formula (1) between 0 mV (SCE) and a chelate dye formed with a metal ion-containing compound.

Examples of the metal ion-containing compound used in the chelate dye include an inorganic or organic salt of a metal ion and a metal complex.

Examples of the metal in the metal ion-containing compound include monovalent and polyvalent metals belonging to Groups 1 to 8 of the periodic table. Among them, Al, Co, Cr, Cu, F
e, Mg, Mn, Mo, Ni, Sn, Ti and Zn are preferred, and Ni, Cu, Cr, Co and Zn are particularly preferred. Specific examples of the metal ion-containing compound (hereinafter, also referred to as a metal source) include Ni ²⁺ , Cu ²⁺ , C 2
r ²⁺ , Co ²⁺ and Zn ²⁺ and salts of aliphatic acids such as acetic acid and stearic acid, or salts of aromatic carboxylic acids such as benzoic acid and salicylic acid, or Cl ⁻ ions, Br ⁻ ions and BF
^- ₄ ion, ClO ^- ₄ ion, SO ^- ₄ and salts with inorganic ions such as ions. Further, the complex represented by the general formula (17) described above is also preferably used.

The coloring composition for a color filter can be obtained, for example, by adding a chelating dye to a resin varnish.

In order to contain the chelate dye in the resin varnish, the dye of the present invention and the metal ion-containing compound may be mixed and dissolved in a resin varnish together with a solvent, or the dye of the present invention and the metal ion-containing compound may be mixed. After the compound is added to the resin varnish, it may be dispersed and contained, or the chelate dye formed by reacting the dye of the present invention and the metal ion-containing compound in advance is isolated and then dissolved in the resin varnish. Alternatively, they may be dispersed.

As the resin varnish, a varnish used in a conventionally known coloring composition for a color filter is used. As the dispersion medium, a solvent or an aqueous medium suitable for the resin varnish is used. Also, if necessary,
Conventionally known additives, for example, a dispersing aid, a smoothing agent, a cohesion agent and the like are added and used.

The weight ratio of the chelate dye to the binder in the varnish was 5 parts per 100 parts of the binder.
Parts to 500 parts is preferred.

As the resin varnish, either a photosensitive resin varnish or a non-photosensitive resin varnish can be used.
Examples of the photosensitive resin varnish include, for example, a UV curable ink and a photosensitive resin varnish used for an electron beam curable ink. Examples of the non-photosensitive resin varnish include letterpress ink, planographic ink, and intaglio. Gravure ink,
Varnishes used for printing inks such as stencil screen inks, varnishes used for electrodeposition coating, varnishes used for developers of electronic printing and electrostatic printing, varnishes used for thermal transfer ribbons, and the like can be given.

Examples of the photosensitive resin varnish include a photosensitive cyclized rubber resin, a photosensitive phenol resin, a photosensitive polymethacrylate resin, a photosensitive polyamide resin, a photosensitive polyimide resin, and an unsaturated polyester resin. Resin,
Resin varnishes using polyester acrylate-based resins, polyepoxy acrylate-based resins, polyurethane acrylate-based resins, polyether acrylate-based resins, polyol acrylate-based resins, and the like, and further, a resin varnish to which a monomer is added as a reactive diluent Is mentioned. The photosensitive resin varnish can be obtained by adding a photopolymerization initiator such as benzoin ether or benzophenone to the above varnish, and performing a briquetting method by a conventionally known method.

When a thermal polymerization initiator is used instead of the photopolymerization initiator, a varnish of a thermopolymerizable resin can be obtained.

When the coloring composition for a color filter using the above-mentioned photosensitive resin varnish is used, the color filter is prepared by coating the coloring composition for a color filter on a transparent substrate in a conventional manner and curing the composition. Can be made. In addition, a color filter formed with a specific pattern is formed by spin-coating a coloring composition for a color filter on a transparent substrate, coating the entire surface using a low-speed rotation coater, a roll coater, a knife coater, or various printing methods. Perform full-scale printing or partial printing slightly larger than the pattern using, after pre-drying, using a mask with a specific pattern, for example, exposure and baking using an ultra-high pressure mercury lamp, then perform development and washing, if necessary By performing post-baking, a color filter having a filter layer formed in a specific pattern can be manufactured.

Examples of the non-photosensitive resin varnish include cellulose acetate resins, nitrocellulose resins, styrene (co) polymers, polyvinyl butyral resins, amino alkyd resins, polyester resins, and amino resin modified resins. Polyester resin, polyurethane resin, acrylic polyol urethane resin, soluble polyamide resin, soluble polyimide resin, soluble polyamideimide resin, soluble polyesterimide resin, casein, hydroxyethylcellulose, styrene-maleic ester copolymer Water-soluble salts, water-soluble salts of (meth) acrylate (co) polymers, water-soluble aminoalkyd resins, water-soluble aminopolyester resins,
A resin varnish using a water-soluble polyamide-based resin alone or in combination may be used.

When a coloring composition for a color filter using the above non-photosensitive coloring composition is used, the coloring composition for the color filter is applied on a transparent substrate by a conventional method and dried. It can be manufactured by the following. Also, a color filter formed with a specific pattern, a coloring composition for a color filter on a transparent substrate, for example, using a printing ink for a color filter,
For example, a letterpress printing method, a lithographic printing method, an intaglio gravure printing method, a method of directly printing a colored pattern on a substrate by a stencil screen printing method, or the like, a substrate by electrodeposition coating using an aqueous electrodeposition coating composition for a color filter. It can be manufactured by a method of forming a colored pattern, a method of forming a colored pattern on a substrate using an electronic printing method or an electrostatic printing method. Further, it can be produced by a method in which a colored pattern is once formed on a transferable substrate by the above method or the like, and then transferred to a transparent substrate. Subsequently, baking, polishing for smoothing the surface, and top coating for protecting the surface can be performed as necessary according to a conventional method.

When a color filter used in a liquid crystal display device or the like is obtained, a black matrix may be formed according to a conventional method.

[0103]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. Example 1 << Synthesis of Exemplified Dye (1) >>

[0104]

Embedded image

First step: 4.56 g (0.03 mol) of amidine (intermediate 1) and 2.29 g (0.01 mol) of p-methoxy-α-bromoacetophenone were dissolved in 30 ml of ethyl acetate. 5
Heated to reflux for an hour. After removing the formed precipitate, the mixture was concentrated, and separated and purified by column chromatography to obtain 2.12 g of Intermediate 2 as colorless crystals. Second step 1.41 g (0.005 mol) of the intermediate 2 was dissolved in 20 ml of methanol, and 4.0 g of triethylamine was obtained.
1.15 g (0.0065 mol) of CD-2 are added.
Under ice-cooling, a 10 ml aqueous solution of 3.4 g (0.015 mol) of ammonium persulfate is added dropwise. The resulting precipitate was collected by filtration and washed with methanol to obtain 1.26 g of a green dye. [Yield 55%, λmax 619 nm, ε53300
(acetone)〕

Example 2 << PC Sublimation Type Thermal Transfer Recording >> -Preparation of Ink- The following raw materials were mixed to obtain an ink of a uniform solution containing the dye according to the present invention. The solubility of the dye is good,
Ink suitability was also good.

Illustrative dye (l) 0.72 g polyvinyl acetoacetal resin (KY-24, manufactured by Denki Kagaku Kogyo) 1.08 g methyl ethyl ketone 26.4 ml toluene 1.6 ml

-Preparation of Ink Sheets 101 to 112- The above ink was applied on a 4.5 μm-thick polyethylene terephthalate base using a wire bar and dried so that the application amount after drying was 2.3 g / m ^2. Then, an ink sheet-1 having a heat-sensitive transfer layer formed on a polyethylene phthalate film was produced. A nitrocellulose layer containing a silicon-modified urethane resin (SP-2105, manufactured by Dainichi Seika) is provided on the back surface of the polyethylene terephthalate base as a sticking preventing layer.

Ink sheets 102 to 112 were produced in the same manner as in the ink sheet 101 except that the dyes shown in Table 1 were used instead of the exemplary dye (l).

-Preparation of Image Receiving Sheet 1- A coating solution having the following composition was dried on a support (polyethylene layer on one side containing white pigment (TiO ₂ ) and a bluing agent) on both sides of paper laminated with polyethylene. The later application amount is 7.
The resultant was coated and dried so as to be 2 g, and an image receiving sheet 1 was produced.

Metal ion-containing compound (I-1) 4.0 g polyvinyl butyral resin (BX-1, manufactured by Sekisui Chemical Co., Ltd.) 6.0 g modified polyester silicon 0.3 g methyl ethyl ketone 60 ml cyclohexanone 15 ml

[0112]

Embedded image

-Thermal transfer recording method-The obtained ink sheet and the image receiving sheet are overlapped, and a thermal printer is used to record an image by applying a thermal head from the back side of the ink sheet to obtain images 101 to 11 having excellent gradation.
2 was obtained. After recording, the maximum density of the image, the sensitivity of the recording material, and the image storability were evaluated according to the following. Table 1 shows the obtained results.

<Evaluation of maximum density> X-Rite310T
The maximum reflection density (usually, the portion where the application time was the maximum) of the image was measured by R, and the maximum density was evaluated.

<Evaluation of Sensitivity> The applied energy when the density of the image formed by the ink sheet and the image receiving sheet was 1.0 was determined. Table 1 shows relative applied energies when the applied energy when the density of an image formed by the ink sheet 101 and the image receiving sheet 1 becomes 1.0 is 1.

<Evaluation of Image Preservation> The obtained image was irradiated with light for 5 days with a xenon fade meter to prepare an evaluation sample of light resistance.

The obtained image was taken at 50 ° C. and 80 RH%.
Was stored for 7 days in a constant temperature and humidity condition to prepare an evaluation sample for moisture resistance storage stability.

X-Rite was evaluated for each evaluation sample.
The image density was measured by 310TR, and the dye remaining ratio was determined as follows.

Dye residual rate = (D / D ₀ ) × 100 where D ₀ is the density before light irradiation or storage, and D is the density after light irradiation or storage.

[0120]

[Table 1]

[0121]

Embedded image

As is clear from the results shown in Table 1, it is found that the use of the dye of the present invention can provide an image having good image storability (light storage stability, moisture storage stability).

Similar results were obtained when other exemplified dyes were used in place of the dyes shown in Table 1. Example 3 << Laser-to-heat conversion PC sublimation type thermal transfer recording >> -Preparation of ink sheet 201- Using a 6 μm polyethylene terephthalate film (manufactured by Toray Industries, Inc.) as a support, forming an ink layer of the following composition on the surface thereof The coating liquid for application was applied by a wire bar coating method so as to have a dried film thickness of 1 μm and dried to form an ink layer, thereby producing an ink sheet 201. In addition, on the back surface of the polyethylene terephthalate film, a nitrocellulose layer containing a silicon-modified urethane resin (SP-2105, manufactured by Dainichi Seika Co., Ltd.) was provided as a backing layer.

Ink layer forming coating liquid Exemplified dye (1) 5 parts Nitrocellulose (Celnova BTH1 / 2 manufactured by Asahi Kasei Corporation) 3 parts Light-to-heat conversion material (IR-1) 2 parts Methyl ethyl ketone 80 parts Cyclohexanone 10 parts

-Preparation of Image Receiving Sheet 2- A receiving layer having the following composition was formed on a 100 μm thick white polyester film (W400, manufactured by Diafoil Co., Ltd.) obtained by biaxially stretching a mixture of a white pigment and a polyester resin. The coating liquid for application was applied by a wire bar coating method so as to have a thickness of 5 μm after drying, and dried to obtain an image receiving sheet 2.

Coating Liquid for Forming Receptive Layer Metal Ion-Containing Compound (I-1) 5.0 parts Polyvinyl chloride resin (TK-300, manufactured by Shin-Etsu Chemical Co., Ltd.) 9.5 parts Polyester modified silicone resin 0.5 part (Manufactured by Shin-Etsu Chemical Co., Ltd .: X-24-8300) Methyl ethyl ketone 60 parts Dioxane 20 parts Cyclohexanone 10 parts The ink sheet 201 and the image receiving sheet 2 are overlapped, and a semiconductor laser (manufactured by Sharp Corporation: (LT090MD / MF, wavelength 0.83 μm, maximum optical output 100 mW), and a laser pattern was irradiated under the following conditions to record a 5 cm × 5 cm patch pattern.

Irradiation energy density: 1.8 mJ / mm ² Single laser beam spot diameter: 16.0 μm Scanning pitch: 10.0 μm Next, the ink sheet 201 and the image receiving sheet 2 were peeled off. The formed image was exposed with an infrared flash lamp to complete the decoloring reaction of the photothermal conversion material on the image. As a result, a clear image without color turbidity was obtained.

Ink sheets 202 to 212 were produced in the same manner as in ink sheet 201 except that the dyes shown in Table 2 were used instead of the exemplary dye (l).

The obtained images were evaluated in the same manner as in the evaluation of the image storability of Example 2 to evaluate the light storability and the moisture storability. Table 2 shows the obtained results.

[0130]

[Table 2]

As is evident from the results in Table 2, it is found that the use of the dye of the present invention can provide an image having good image storability (light storage stability, moisture storage stability).

Similar results were obtained when other exemplified dyes were used in place of the dyes shown in Table 2.

Example 4 << Chelate Dye-Containing Optical Recording Medium >> (a) Production of Optical Recording Medium On a 5 inch diameter grooved polycarbonate substrate, the exemplary dye (2) and the metal ion-containing compound I-1 were fluorinated with alcohol. The light-absorbing layer is formed by applying the liquid mixed therein, and then a reflective layer (Au, thickness of 1000 angstrom) and a protective film (ultraviolet curable resin, thickness of 5 μm) are sequentially formed according to a conventional method. Optical recording medium 301
Was prepared.

The optical recording medium 30 except that the dye shown in Table 3 was used instead of the exemplary dye (2) and the metal ion-containing compound shown in Table 3 was used instead of the metal ion-containing compound I-1.
Optical recording media 302 to 307 were produced in the same manner as in No. 1.

(B) Evaluation of Optical Recording Medium The reflectance of the manufactured optical recording media 301 to 307 was measured and found to be all 70% or more. Optical recording medium 3
Information was recorded by changing the power from 01 to 307 with a 780 nm semiconductor laser, and then reproduction was performed with a 0.8 mW semiconductor laser to determine the number of reproductions. Also,
After performing light irradiation at 70,000 lux for 30 hours using a xenon fade meter, the number of reproductions was obtained in the same manner as described above. Table 3 shows the obtained results.

[0136]

[Table 3] Metal ion supply compound I-2 NaBF ₄

As is clear from the results in Table 3, the optical recording medium of the present invention was able to perform good recording / reproduction satisfying the CD standard. In particular, stable recording with excellent light resistance
Has reproduction characteristics.

On the other hand, in the optical recording media 305 and 306 using the comparative compound A, the reflectivity with respect to the laser reproduction light decreases after light irradiation, and reproduction failure occurs, and a sufficient number of reproductions cannot be obtained. Was. In addition, when only the comparative compound C was used, a phenomenon was observed in which recording could not be performed after light exposure.

Similar results were obtained when other exemplified dyes were used in place of the dyes shown in Table 4.

[0140]

Embedded image

Example 5 << Chelate Dye-Containing Color Filter >> A photosensitive coating agent for a blue (B) color filter was prepared by using the following components. The photosensitive polyimide resin varnish used was a photosensitive polyimide resin varnish containing a photosensitizer. -Photosensitive coating agent component for color filter- Exemplary dye (1) 5 parts Metal ion-containing compound (I-1) 15 parts Photosensitive polyimide resin varnish 50 parts N-methyl-2-pyrrolidone 40 parts

The glass plate which had been treated with the silane coupling agent was set on a spin coater.
The photosensitive coating agent for a blue (B) color filter was spin-coated under the conditions of 2000 seconds and then 2000 rpm for 5 seconds. Next, prebaking was performed at 80 ° C. for 15 minutes, a photomask having a mosaic pattern was brought into close contact, and exposure was performed using an ultrahigh pressure mercury lamp at a light amount of 900 mJ / cm ² . Next, development and washing were performed using a dedicated developer and a dedicated rinse to form a color filter having a blue mosaic pattern on a glass plate.

The color filter obtained above has excellent properties such as light fastness and moisture fastness, and also has excellent properties of light transmission, and also has excellent properties as a color filter for a liquid crystal color display. Had.

Similar results were obtained when other exemplified compounds were used in place of the exemplified compound (1).

[0145]

As described above, the dye of the present invention can obtain a chelate dye excellent in fastness such as light fastness and moisture fastness, and the chelate dye obtained from the dye of the present invention has fastness such as light fastness and moisture fastness. The diffusion transfer image, the optical recording medium, and the color filter using the chelate dye are also excellent in fastness such as light fastness and moisture fastness.

 ──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Motoaki Sugino 1 Sakuracho, Hino-shi, Tokyo Konica Corporation F-term (reference) 2H048 AA05 BA02 BA29 BA30 CA04 2H111 AA09 AA27 BA03 BA39 BA44 CA03 CA33 EA04 EA12 EA25 FB42

Claims (6)

[Claims] 1. Forming a chelate with a metal ion-containing compound
Possible reduction potential is from -1100 mV to -800 mV (S
A dye represented by the following general formula (1) between CE) Embedded image[Wherein, R¹, R^Two Is an optionally substituted alkyl
Represents a group. Also, R¹And R^TwoIs linked to form a ring
There may be. R^Three, R^Four, R^Five, R⁶Is a hydrogen atom,
And an alkoxy group. A and B represent a substituent. Was
However, at least one of A and B is a metal ion
Is a group capable of forming a chelate with a compound containing a compound. ] 2. The reduction potential is from -1100 mV to -800.
mV (SCE), represented by the following general formula (1)
Consisting of a chelate of a dye and a metal ion-containing compound
A chelating dye characterized by the following. Embedded image[Wherein, R¹, R^Two Is an optionally substituted alkyl
Represents a group. Also, R¹And R^TwoIs linked to form a ring
There may be. R^Three, R^Four, R^Five, R⁶Is a hydrogen atom,
And an alkoxy group. A and B represent a substituent. Was
However, at least one of A and B is a metal ion
Is a group capable of forming a chelate with a compound containing a compound. ] 3. The reduction potential is from -1100 mV to -800.
mV (SCE), represented by the following general formula (1)
An ink sheet comprising a dye. Embedded image[Wherein, R¹, R^Two Is an optionally substituted alkyl
Represents a group. Also, R¹And R^TwoIs linked to form a ring
There may be. R^Three, R^Four, R^Five, R⁶Is a hydrogen atom,
And an alkoxy group. A and B represent a substituent. Was
However, at least one of A and B is a metal ion
Is a group capable of forming a chelate with a compound containing a compound. ] 4. An ink sheet containing a dye and an image receiving sheet.
By heating the images according to the recording signal
Thermal diffusion of the dye on the ink sheet and metal ions
Reacts with the compound to form a chelate dye,
In sublimation type thermal transfer recording formed on an image receiving sheet, color
Element has a reduction potential of -1100 mV to -800 mV (S
CE), a dye represented by the following general formula (1):
An image forming method. Embedded image[Wherein, R¹, R^Two Is an optionally substituted alkyl
Represents a group. Also, R¹And R^TwoIs linked to form a ring
There may be. R^Three, R^Four, R^Five, R⁶Is a hydrogen atom,
And an alkoxy group. A and B represent a substituent. Was
However, at least one of A and B is a metal ion
Is a group capable of forming a chelate with a compound containing a compound. ] 5. The transparent substrate has a reduction potential of −1100 m.
The following general formula between -V and -800 mV (SCE)
Formed by the dye represented by (1) and a metal ion-containing compound
At least one light absorbing layer containing a modified chelate dye
An optical recording medium comprising: Embedded image[Wherein, R¹, R^Two Is an optionally substituted alkyl
Represents a group. Also, R¹And R^TwoIs linked to form a ring
There may be. R^Three, R^Four, R^Five, R⁶Is a hydrogen atom,
And an alkoxy group. A and B represent a substituent. Was
However, at least one of A and B is a metal ion
Is a group capable of forming a chelate with a compound containing a compound. ] 6. The reduction potential is from -1100 mV to -800.
mV (SCE), represented by the following general formula (1)
Chelate dye formed with dye and metal ion-containing compound
Coloring set for color filters, characterized by containing
Adult. Embedded image[Wherein, R¹, R^Two Is an optionally substituted alkyl
Represents a group. Also, R¹And R^TwoIs linked to form a ring
There may be. R^Three, R^Four, R^Five, R⁶Is a hydrogen atom,
And an alkoxy group. A and B represent a substituent. Was
However, at least one of A and B is a metal ion
Is a group capable of forming a chelate with a compound containing a compound. ]