JP2008088198A - Dye compound, colored composition, ink sheet for heat-sensitive transfer recording, heat-sensitive transfer recording method, color toner, inkjet ink and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new azomethine dye or azo dye having spectral characteristics of a sharp absorption waveform. <P>SOLUTION: The dye compound is represented by general formula (1) (Q is an atomic group necessary for having an absorption at least in one region of a visible light region and a near infrared region; R<SP>1</SP>is a hydrogen atom or a substituent group; R<SP>2</SP>and R<SP>3</SP>are each a substituent group and may be mutually bonded to form a ring structure). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a specific novel coloring compound, a coloring composition containing the coloring compound, a thermal transfer recording ink sheet, a thermal transfer recording method, a color toner, an inkjet ink, and a color filter.

Technical background

In recent years, a material for forming a color image has been mainly used as an image recording material, and specifically, an ink jet recording material, a thermal transfer recording material, an electrophotographic recording material, a transfer halogen. Silver halide photosensitive materials, printing inks, recording pens and the like are actively used. In addition, a color filter is used to record and reproduce a color image in an imaging device such as a CCD in a photographing apparatus and in an LCD or PDP in a display.
In color image recording materials and color filters, three primary colorants (pigments and pigments) of the so-called additive color mixing method and subtractive color mixing method are used to reproduce or record full color images. However, there is no solid colorant that has an absorption characteristic that can realize a preferable color gamut and can withstand various use conditions, and improvement is strongly desired.

  In thermal transfer recording, a thermal transfer material in which a heat-meltable ink layer is formed on a support (base film) is heated by a thermal head, the ink is melted and recorded on an image receiving material, and on the support. There is a method in which a heat-sensitive transfer material having a dye-donating layer containing a heat-transferable dye is heated by a thermal head to thermally transfer the dye onto the image receiving material. The latter thermal transfer system can change the transfer amount of the dye by changing the energy applied to the thermal head, so that gradation recording is easy and is particularly advantageous for high-color full-color recording. However, the heat transfer dyes used in this method have various limitations, and very few satisfy all the required performance.

The required performance includes, for example, favorable spectral characteristics for color reproduction, easy transfer, fastness to light and heat, fastness to various chemicals, and easy synthesis. It is easy to make a recording material for thermal transfer. In particular, when used as a thermal transfer ink, excellent spectral characteristics in color reproduction and transfer performance are required.
However, it is very difficult to satisfy these requirements simultaneously. Various specific dyes have been proposed as dyes that have favorable spectral characteristics for color reproduction and are fast to light and heat (see, for example, Patent Documents 1 to 6), but are not satisfactory, and further improvements are strong. It is desired.

  In color copiers and color laser printers that use electrophotography, toners in which a colorant is dispersed in resin particles are generally used. As performance required for color toners, absorption characteristics that can realize a preferable color gamut, particularly high transparency (transparency) required when used in an overhead projector (hereinafter referred to as OHP), and the environment in which it is used Various fastness conditions are mentioned. Although toners in which pigments are dispersed in particles as a colorant have been proposed (see, for example, Patent Documents 7 to 9), these toners are excellent in light resistance, but are insoluble and thus easily aggregate and decrease in transparency. And there is a problem with the hue change of the transmitted color. On the other hand, toners using specific dyes as colorants have also been proposed (see, for example, Patent Documents 10 to 12). However, these toners are conversely high in transparency and have no hue change, but have a problem in light resistance. .

The ink jet recording method is rapidly spreading and further developing because of its low material cost, high speed recording, low noise during recording, and easy color recording.
Inkjet recording methods include a continuous method in which droplets are continuously ejected and an on-demand method in which droplets are ejected in accordance with image information signals. There are a method of discharging bubbles, a method of generating bubbles in the ink by heat and discharging droplets, a method of using ultrasonic waves, and a method of sucking and discharging droplets by electrostatic force. As the ink for ink jet recording, water-based ink, oil-based ink, or solid (melted type) ink is used.
For the colorant used in such ink for ink jet recording, the solvent has good solubility or dispersibility, high density recording is possible, hue is good, light, heat, environment It is robust against active gases (oxidizing gases such as NOx, SOx, ozone, etc.), has excellent fastness to water and chemicals, has good fixability to image receiving materials, and is difficult to bleed, ink It is required to have excellent storage stability, no toxicity, high purity, and availability at low cost. However, it is extremely difficult to search for colorants that meet these requirements at a high level. In particular, it is strongly desired to have high solubility and fastness to light, humidity, and heat, and in particular, to be fastness to light.

  Since color filters are required to have high transparency, a method called a dyeing method in which coloring is performed using a dye has been performed. For example, a color filter can be produced by sequentially repeating a method of forming a pattern by pattern exposure and development of a dyeable photoresist and then dyeing with a filter color dye for all filter colors. In addition to the dyeing method, a color filter can be produced by a method using a positive resist. The color filter produced by these methods has a high transmittance and excellent optical characteristics because it uses a dye, but has limitations in light resistance, heat resistance, and the like. For this reason, the coloring agent which was excellent in various tolerances and high in transparency was desired. On the other hand, a method using an organic pigment having excellent light resistance and heat resistance in place of a dye is widely known. However, it is difficult to obtain optical characteristics like a dye with a color filter using the pigment.

The dyes that can be used for each of the above-mentioned applications are desired to have the following properties in common. That is, it has a hue preferable for color reproduction, an optimum spectral absorption, fastness such as light resistance, moisture resistance and chemical resistance, and high solubility.
For use in thermal transfer recording, a dye having a specific aminothiazole skeleton has been proposed (see, for example, Patent Documents 6, 13, 14, and 15). However, these dyes have problems in spectral characteristics.
JP-A-63-205288 JP-A-64-63194 Japanese Patent No. 3013137 JP-A-62-294593 JP-A-6-1227091 Japanese Patent No. 3001991 JP 62-157051 A Japanese Patent Laid-Open No. Sho 62-255556 JP-A-6-118715 JP-A-3-276161 JP-A-2-207274 JP-A-2-207273 JP-A-3-93862 JP-A-4-338592 JP 2001-271003 A

  An object of the present invention is to provide a novel azomethine dye or azo dye having spectral characteristics with a sharp absorption waveform. Furthermore, another object of the present invention is to provide a thermal transfer recording ink sheet and a thermal transfer recording method which satisfy all of excellent color reproducibility, image storage stability and transfer sensitivity in a print sample. Furthermore, it is providing the color toner using this pigment | dye, the ink for inkjets, and a color filter.

  As a result of intensive studies, the present inventors have found that the above problems can be achieved by the following configuration.

(1) A dye compound represented by the following general formula (1).

（一般式（１）において、Ｑは前記一般式（１）で表される化合物が可視域または近赤外域の少なくとも一方に吸収を持つために必要な原子団を表し、Ｒ¹は水素原子または置換基を表し、Ｒ²およびＲ³は各々独立に置換基を表し、互いに結合して環構造を形成してもよい。）

(In General Formula (1), Q represents an atomic group necessary for the compound represented by General Formula (1) to have absorption in at least one of the visible region and the near infrared region, and R ¹ represents a hydrogen atom or Represents a substituent, and R ² and R ³ each independently represent a substituent, and may be bonded to each other to form a ring structure.

(2) In the general formula (1), Q is = C (Ra) (Rb) or = N-Rc (Ra and Rb each independently represents a hydrogen atom or a substituent, and Rc represents a heterocyclic group) The coloring matter compound according to (1), wherein

(3) The dye according to (1) or (2), wherein in the general formula (1), Q is represented by any one of the following general formulas (A-1) to (A-47): Compound.

(In the general formulas (A-1) to (A-47), R ⁴ and R ^{7 to} R ⁵³ each independently represents a substituent. R ⁵ and R ⁶ each independently represents an electron-withdrawing substituent. A represents an integer of 0 to 3, b represents an integer of 0 to 2, and c and d each independently represents an integer of 0 to 4. Here, * represents a nitrogen of aminothiazole in the general formula (1). (Shows the site of bonding to an atom through a double bond.)

(4) In the said General formula (1), Q is represented by the said General formula (A-3), The pigment | dye compound as described in (3) characterized by the above-mentioned.
(5) In the general formula (1), Q is represented by the general formula (A-29), (A-30), (A-42), (A-43) or (A-44). (3) The dye compound according to (3)

(6) A coloring composition comprising the dye compound according to any one of (1) to (5).
(7) An ink sheet for thermal transfer recording, comprising the dye compound according to any one of (1) to (5).
(8) A thermal transfer recording method comprising forming an image on an image receiving material having an ink receiving layer containing a polymer on a support using the thermal transfer recording ink sheet described in (7).

(9) A color toner comprising the dye compound according to any one of (1) to (5).
(10) An ink-jet ink comprising the dye compound according to any one of (1) to (5).
(11) A color filter comprising the dye compound according to any one of (1) to (5).

  According to the present invention, a novel dye compound having a sharp absorption spectrum and excellent spectral characteristics can be provided, and a thermal transfer ink sheet and a thermal transfer recording method containing the dye can be provided. Ink sheet for thermal transfer material that has excellent solubility in solvents, can reduce the work load and environmental burden of ink sheet preparation, and satisfies all of excellent color reproducibility, image preservation, and transfer sensitivity in printed samples. A thermal transfer recording method can be provided. Furthermore, a color toner, an ink jet ink and a color filter using the coloring matter can be provided.

In the following, the ink sheet for thermal transfer material, color toner, ink jet ink and color filter of the present invention and the azomethine dye compound or azo dye compound used therefor (hereinafter also simply referred to as azomethine dye, azo dye or dye of the present invention) This will be described in detail.
The description of the constituent elements described below is based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Dye Compound Represented by General Formula (1)]
First, the dye compound represented by the general formula (1) of the present invention will be described in detail.
The dye compound represented by the general formula (1) is a dye characterized by having a thiazole skeleton having a substituted amino group at the azomethine site or the ortho position of the azo group.
A dye having this specific structure has never been known.
This dye has a sharper absorption spectrum and excellent spectral characteristics than a dye having a thiazole skeleton such as a hydrogen atom or an alkyl group at the ortho position of the azomethine moiety or azo group. This is considered to be due to the fact that hydrogen on the amino group at the ortho position can be bonded to the azomethine moiety or the nitrogen atom of the azo group to form a specific and stable three-dimensional structure.
It is considered that a dye having spectral characteristics based on such a structure can be suitably used for a thermal transfer recording ink sheet and other ink liquids.

In the general formula (1), R ¹ represents a hydrogen atom or a substituent. The substituent is not particularly limited, but as a typical example, an aliphatic group [saturated aliphatic group (an alkyl group, a cycloalkyl group, a bicycloalkyl group, a bridged cyclic saturated hydrocarbon group or a cyclic structure containing a spiro saturated hydrocarbon group) A saturated aliphatic group), an unsaturated aliphatic group (a chain unsaturated aliphatic group having a double bond or a triple bond, such as an alkenyl group or an alkenyl group, or a cycloalkenyl group, a bicycloalkenyl group, A cyclic unsaturated aliphatic group including a bridged cyclic unsaturated hydrocarbon group or a spiro unsaturated hydrocarbon group)], an aryl group, a heterocyclic group (preferably the ring-constituting atom is an oxygen atom, sulfur atom or nitrogen) 5- to 8-membered ring containing atoms, which may be condensed with an alicyclic ring, an aromatic ring or a heterocyclic ring), a cyano group, an aliphatic oxy group (typically an alkoxy group), an aryloxy group Acyloxy group, carbamoyloxy group, aliphatic oxycarbonyloxy group (typically alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group [amino group, aliphatic amino group (typically alkylamino group), anilino group and heterocyclic ring Including amino groups], acylamino groups, aminocarbonylamino groups, aliphatic oxycarbonylamino groups (typically alkoxycarbonylamino groups), aryloxycarbonylamino groups, sulfamoylamino groups, aliphatic (typically alkyl) or aryl Sulfonylamino group, aliphatic thio group (typically alkylthio group), arylthio group, sulfamoyl group, aliphatic (typically alkyl) or arylsulfinyl group, aliphatic (typically alkyl) or Sulfonyl group, acyl group, aryloxycarbonyl group, aliphatic oxycarbonyl group (typically alkoxycarbonyl group), carbamoyl group, aryl or heterocyclic azo group, imide group, aliphatic oxysulfonyl group (typically alkoxysulfonyl group), Examples thereof include an aryloxysulfonyl group, a halogen atom, a hydroxyl group, a nitro group, a carboxyl group, and a sulfo group, and each group may further have a substituent (for example, the substituent described in the above R ¹ ). .
These substituents are further described below.

R ¹ is preferably a substituted or unsubstituted aliphatic group (more preferably an alkyl group, an alkenyl group, a cycloalkyl group or a cycloalkenyl group), a substituted or unsubstituted aryl group (more preferably a substituent). A substituted or unsubstituted heterocyclic group, a substituted or unsubstituted acyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted aliphatic oxycarbonyl group (more preferably an alkyloxycarbonyl group, An alkenyloxycarbonyl group, a cycloalkyloxycarbonyl group or a cycloalkenyloxycarbonyl group), a substituted or unsubstituted sulfamoyl group or a substituted or unsubstituted aliphatic oxysulfonyl group (more preferably an alkoxysulfonyl group, an alkenoxysulfonyl group, Cycloalkoxysulfoni Is a group or a cycloalkyl alkenoxy sulfonyl group). R ¹ is more preferably an unsubstituted alkyl group having 1 to 6 carbon atoms, an unsubstituted phenyl group, an unsubstituted acyl group, an unsubstituted carbamoyl group, an unsubstituted alkoxycarbonyl group, an unsubstituted sulfamoyl group, or An unsubstituted alkoxysulfonyl group. R ¹ is most preferably an unsubstituted acyl group, an unsubstituted carbamoyl group, or an unsubstituted alkoxycarbonyl group.

In the general formula (1), R ² and R ³ each independently represent a substituent. The substituents for R ² and R ³ are not particularly limited, but the substituents listed for R ¹ are preferred, and each of these groups may further have a substituent as in R ¹ .
R ^{2 and} R ³ are preferably each independently a substituted or unsubstituted aliphatic group (more preferably an alkyl group, an alkenyl group, a cycloalkyl group or a cycloalkenyl group, still more preferably an alkyl group), a substituted or unsubstituted group. A substituted aryl group (more preferably a phenyl group which may have a substituent), a substituted or unsubstituted heterocyclic group, more preferably an unsubstituted alkyl group having 1 to 4 carbon atoms, and most preferably Is a methyl group, an ethyl group, an n-propyl group or an isopropyl group.
R ² and R ³ may combine with each other to form a ring structure. The ring structure is preferably a 5- to 8-membered ring structure, and more preferably a 5- to 6-membered ring structure. Specific examples of the ring structure constituted by R ² , R ³ and the nitrogen atom to which they are bonded include pyrrolidine ring, pyrazolidine ring, imidazolidine ring, piperidine ring, piperazine ring, pyrazodiline ring, morpholine ring, pyrrolidine ring, A piperidine ring and a morpholine ring are preferred.

  In the general formula (1), Q represents an atomic group necessary for the dye represented by the general formula (1) to have absorption in at least one of the visible region and the near infrared region. Here, the visible region refers to a region having a wavelength of 400 to 780 nm, and the near infrared region refers to a region having a wavelength of 780 to 2000 nm. Further, the atomic group necessary for having such absorption includes an atomic group constituting a partial structure corresponding to Q in the dye of the general formula (1) having absorption in at least one of the visible region and the near infrared region. Are all included.

Here, Q is preferably a group that forms a conjugated system through the nitrogen atom and carbon atom of aminothiazole and the nitrogen atom bonded to aminothiazole, and is a group that draws π electrons in aminothiazole to the Q side. It is preferable.
More preferably, Q has a structure represented by ═C (Ra) (Rb) or ═N—Rc. Here, Ra and Rb each independently represent a hydrogen atom or a substituent, and examples of the substituent include the substituents described for R ¹ . Here, at least one of Ra and Rb is preferably an electron-withdrawing group. The electron-withdrawing group is one having a positive Hammett σ _p value. For example, among the substituents mentioned for R ¹ , a cyano group, an acyloxy group, a carbamoyloxy group, an aliphatic oxy group. Carbonyloxy group (typically alkoxycarbonyloxy group, aryloxycarbonyloxy group, sulfamoylamino group, aliphatic (typically alkyl) or arylsulfonylamino group, sulfamoyl group, aliphatic (typically alkyl) or arylsulfinyl group , Aliphatic (typically alkyl) or arylsulfonyl group, acyl group, aryloxycarbonyl group, aliphatic oxycarbonyl group (typically alkoxycarbonyl group), carbamoyl group, imide group, aliphatic oxysulfonyl group (typically alkoxysulfonyl) Group), a Examples include a reeloxysulfonyl group, a halogen atom, a nitro group, a carboxylate group, a sulfonate group, and an aliphatic group substituted with an electron withdrawing group such as a heterocyclic group, a trifluoromethyl group, or a pentafluorophenyl group. Or an aryl group is mentioned.

Here, Hammett's substituent constant σ _p value will be further described.
The Hammett rule is an empirical rule proposed by LP Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives, which is widely accepted today. Substituent constants obtained by Hammett's rule include σ _p and σ _m values, and these values can be found in many general books. For example, in JADean's `` Lange's Handbook of Chemistry '' 12th edition, 1979 (Mc Graw-Hill), “Chemical domain” extra number 122, 96-103, 1979 (Nankodo). In the present specification, each substituent is limited or explained by Hammett's substituent constant σ _p, but this is limited only to a substituent having a known value found in the above-mentioned book. It does not mean that, even if the value is unknown, it also includes substituents that would be included within that range when measured according to Hammett's rule. In addition, the general formula of the present invention includes those that are not benzene derivatives, but the σ _p value is used as a scale indicating the electronic effect of the substituent regardless of the substitution position. In this specification, the σ _p value is used in this sense.

The electron withdrawing group represents a functional group having Hammett's substituent constant σ _p value of 0 or more. The electron withdrawing group preferably has a σ _p value of 0.30 or more, more preferably 0.45 or more, and particularly preferably 0.60 or more. The upper limit of σ _p is preferably 1.0 or less. Examples of electron withdrawing groups having a σ _p value of 0.60 or more include nitro group, cyano group, methanesulfonyl group, trifluoromethanesulfonyl group, trifluoroacetyl group, dimethylaminosulfonyl group, sulfamoyl group, and the like. Examples of the electron withdrawing group having a σ _p value of 0.45 or more include an alkoxycarbonyl group, an acyl group, and a carboxy group. Examples of the electron withdrawing group having a σ _p value of 0.30 or more include a sulfo group. Group and carbamoyl group. More preferred are a cyano group, a carboxyl group, an alkoxycarbonyl group, and a carbamoyl group, still more preferred are a cyano group, an alkoxycarbonyl group, and a carbamoyl group, and most preferred are a cyano group and a carbamoyl group.

  When Q is = C (Ra) (Rb), Ra and Rb may be bonded to each other to form a ring, and the ring includes a heterocycle (preferably an oxygen atom, a sulfur atom or a nitrogen atom at least One ring-constituting atom, which is a 5- or 6-membered ring, and further a heterocyclic ring to which a benzene ring or a 5- to 6-membered heterocyclic ring may be condensed, more preferably an unsaturated heterocyclic ring ) Or an alicyclic ring (preferably a 6-membered alicyclic ring on which the above-mentioned hetero ring or benzene ring may be condensed, and more preferably an unsaturated alicyclic ring other than an aromatic ring). The heterocycle formed by combining Ra and Rb with each other is preferably a 5-membered ring, more preferably one having at least one nitrogen atom as a ring-constituting atom, and preferably a heterocycle (preferably a 5- to 6-membered at least one ring). A heterocyclic ring condensed with an unsaturated heterocyclic ring having a nitrogen atom as a ring constituent atom is more preferred. Moreover, when forming an alicyclic ring, the ring which has a 6-membered quinoid structure is more preferable.

Rc represents a heterocyclic group, preferably an oxygen atom, a sulfur atom or a nitrogen atom is at least one ring constituent atom, and is a 5- or 6-membered ring, and further a benzene ring or a 5- to 6-membered heterocyclic ring Is a heterocyclic group which may be condensed, more preferably the unsaturated heterocyclic group described above, and most preferably an aromatic heterocyclic group. Here, the aromatic heterocyclic group means a group in which the number of conjugated π electrons on the ring is 4n + 2 (n is a non-negative integer).
The heterocyclic group in Rc is preferably a 5-membered aromatic heterocyclic group, and more preferably has a nitrogen atom as one of the ring constituent atoms.

  When Q is = C (Ra) (Rb) or = N-Rc, the former is a group that forms an azomethine dye compound, and the latter is a group that forms an azo dye compound, but in the former, Ra And Rb form a ring (preferably the above-mentioned heterocycle).

Describing Q more specifically, Q is preferably any one of the general formulas (A-1) to (A-47).
Below, each group of general formula (A-1)-(A-47) is demonstrated.
For convenience of explanation, in the following explanation, the term “alkyl” is used as a representative of the “aliphatic” moiety. For example, an aliphatic group is described as an alkyl group and an aliphatic oxy group as an alkoxy group.
The term “aliphatic” is represented by an aliphatic group in R ¹ , for example, in the case of an aliphatic group, a saturated aliphatic group (an alkyl group, a cycloalkyl group, a bicycloalkyl group, a bridged cyclic saturated hydrocarbon group) Or a cyclic saturated aliphatic group containing a spiro saturated hydrocarbon group), or an unsaturated aliphatic group (a chain unsaturated aliphatic group having a double bond or triple bond, such as an alkenyl group or an alkenyl group) Or a cyclounsaturated aliphatic group including a cycloalkenyl group, a bicycloalkenyl group, a bridged cyclic unsaturated hydrocarbon group, or a spiro unsaturated hydrocarbon group), and having an aliphatic moiety (For example, an aliphatic oxy group and the like) are used in the same meaning.
Here, among “aliphatic”, preferred are “alkyl”, “alkenyl”, “cycloalkyl”, and “cycloalkenyl”, and more preferred are “alkyl”, “alkenyl”, and “cycloalkyl”. More preferably “alkyl” or “alkenyl”, and most preferably “alkyl”.

On the other hand, the “aryl” in the “aryl” moiety is preferably “phenyl optionally having substituent (s)”. Examples of the substituent include the substituents exemplified as the substituent that may be substituted by the substituent of R ¹ .
Furthermore, the “heterocycle” in the “heterocycle” moiety is similarly “having at least an oxygen atom, a sulfur atom or a nitrogen atom as a ring-constituting atom, a 5- to 6-membered ring, an alicyclic ring, an aromatic ring or a heterocyclic ring. And a heterocyclic ring which may be condensed with is preferable.
Further, unless otherwise specified, each group described below may be further substituted with a substituent, and examples of the substituent include the substituents exemplified as the substituent which the substituent of R ¹ may substitute. Groups.
Below, each general formula is demonstrated. In the following description of the general formula, those described as the substituents that R ^{4 to} R ⁵³ can take are those exemplified as preferred substituents.

In (A-1), R ⁴ represents an alkyl group, an aryl group, a heterocyclic group, or an alkoxy group. Among the R ⁴ groups, tert-butyl group, 1-ethylcyclopropyl group, 1-methylcyclopropyl group, 1-benzylcyclopropyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted indolin-1-yl Group or a substituted or unsubstituted indol-3-yl group is preferred. In (A-1), R ⁵ represents a carbamoyl group or a cyano group. Among the R ^{5 s} , an N-arylcarbamoyl group or a cyano group is preferable.

In (A-2), R ⁶ represents an aryl group or a heterocyclic group. Among the R ⁶ , a substituted or unsubstituted phenyl group, a substituted or unsubstituted heterocyclic group is preferable, and a thiazol-2-yl group, a benzothiazol-2-yl group, an oxazol-2-yl group, and a benzoxazole- 2-yl group, 1,2,4-oxadiazol-3 (or 5) -yl group, 1,3,4-oxadiazol-2 (or 5) -yl group, 1,2,4-thiadiazole -3 (or 5) -yl group, 1,3,4-thiadiazol-2 (or 5) -yl group, pyrazol-3-yl group, indazol-3-yl group, 1,2,4-triazole-3 A -yl group, a 2-pyridyl group, a 2-pyrimidinyl group, a 2-pyrazinyl group, a quinazolin-2-yl group, or a quinazolin-4-yl group is more preferable. In (A-2), R ⁵ represents a carbamoyl group or a cyano group. Of the R ⁵ , a cyano group is preferable.

In (A-3), R ⁷ represents an alkyl group, aryl group, heterocyclic group, acylamino group, amino group, alkoxy group, aryloxy group, alkylthio group, arylthio group, aminocarbonylamino group, or alkoxycarbonylamino group. Represents. Among the R ⁷ , an alkyl group, an acylamino group, an amino group, an aminocarbonylamino group, or an alkoxycarbonylamino group is preferable, and an acylamino group or an N-arylamino group is more preferable. In (A-3), R ⁸ represents an alkyl group, an aryl group, or a heterocyclic group. Among R ⁸ , an aryl group or a heterocyclic group is preferable, and an aryl group is more preferable.

In (A-4) and (A-5), R ⁹ and R ¹⁰ are each independently a hydrogen atom, alkyl group, aryl group, heterocyclic group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, An amino group, an alkylthio group, an arylthio group, an alkoxy group, an aryloxy group, an aminocarbonylamino group, or an alkoxycarbonylamino group is represented. Among the R ^{9 s} , an alkyl group, an aryl group, an alkoxy group, or an aryloxy group is preferable, and a methyl group, a tert-butyl group, or a substituted or unsubstituted phenyl group is more preferable. Among these, an alkyl group or an aryl group is preferable.

In (A-6) and (A-7), R ⁹ represents a group having the same meaning as R ⁹ . Among the R ^{9 s} , an alkyl group, an aryl group, an alkoxy group, or an aryloxy group is preferable. In (A-6) and (A-7), R ¹¹ , R ¹² , and R ¹³ are each independently a hydrogen atom, alkyl group, aryl group, heterocyclic group, acylamino group, alkyl or arylsulfonylamino group Represents an amino group, an alkylthio group, an arylthio group, an alkoxy group, an aryloxy group, an aminocarbonylamino group, an alkoxycarbonylamino group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group. Of the R ¹¹ , R ¹² , and R ¹³ , a hydrogen atom, an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group is preferable.

In (A-8), R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acylamino group, an alkyl or arylsulfonylamino group, an amino group, an alkylthio group, an arylthio group, An alkoxy group, an aryloxy group, an aminocarbonylamino group, an alkoxycarbonylamino group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group is represented. Among the R ¹⁴ and R ¹⁵ , a hydrogen atom, an alkyl group, or an aryl group is preferable.

In (A-9), (A-10), (A-11), and (A-12), R ¹⁶ represents an alkyl group, an aryl group, or a heterocyclic group. Among these, an alkyl group or an aryl group is preferable. In (A-9), (A-10), and (A-11), R ¹⁷ represents a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a silyl group, an acylamino group, an alkyl or arylsulfonylamino group, amino Represents a group, an aminocarbonylamino group, an alkylthio group, an arylthio group, an alkoxy group, or an alkoxycarbonylamino group. Among the R ¹⁷ , a halogen atom, an alkyl group, or an acylamino group is preferable. In (A-12), R ¹⁸ represents a hydrogen atom or an alkyl group. Among the R ^{18 s} , a hydrogen atom, a methyl group, or an ethyl group is preferable. In (A-9), (A-10), (A-11) and (A-12), a represents an integer of 0 to 3, b represents an integer of 0 to 2, and c represents 0 to 4 Represents an integer. Among the a, 1 or 2 is preferable, among b, 1 or 2 is preferable, and among c, an integer of 0 to 2 is preferable. When a, b, or c is plural, a plurality of R ¹⁷ may be the same as or different from each other. In (A-12), R ¹⁹ represents a hydrogen atom or an alkyl group. Among the R ^{19 s} , a hydrogen atom, a methyl group, or an ethyl group is preferable.

In (A-13), R ²⁰ represents a carbamoyl group, an alkoxycarbonyl group, a cyano group, a sulfamoyl group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, or an alkyl or arylsulfonylamino group. Of the R ²⁰ , a carbamoyl group, a sulfamoyl group, or an acylamino group is preferable. In (A-13), R ²¹ represents a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an acylamino group, an alkyl or arylsulfonylamino group, an amino group, an alkylthio group, an arylthio group, an alkoxy group, an aryloxy group, An aminocarbonylamino group or an alkoxycarbonylamino group is represented. Among the R ^{21 s} , an acylamino group, an alkyl or arylsulfonylamino group, an aminocarbonylamino group, or an alkoxycarbonylamino group is preferable. In (A-13), d represents an integer of 0 to 4. Of the d, 0 or 1 is preferable. When d is plural, the plural R ²¹ may be the same as or different from each other.

In (A-14), R ²¹ and d represent the same meaning as described above. Among the R ²¹ , a halogen atom, an alkyl group, or an aryl group is preferable, and among the d, an integer of 0 to 2 is preferable. In (A-14), R ²⁴ and R ²⁵ represent a group having the same meaning as R ²¹ . Of the R ²⁴ and R ²⁵ , a halogen atom, an alkyl group, or an aryl group is preferable. In (A-14), R ²² and R ²³ represent a cyano group, a sulfamoyl group, an alkyl or arylsulfonyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group. Of the R ²² and R ²³ , a cyano group is preferable.

In (A-15), R ²¹ and d represent the same meaning as described above. Among the R ²¹ , a halogen atom, an alkyl group, or an aryl group is preferable, and an integer of 0 to 2 is preferable among the d. In (A-15), R ²⁶ and R ²⁷ represent a cyano group, a sulfamoyl group, an alkyl or arylsulfonyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group. Of the R ²⁶ and R ²⁷ , a cyano group is preferable.

In (A-16), R ²⁸ , R ²⁹ and R ³⁰ are each independently a hydrogen atom, alkyl group, aryl group, heterocyclic group, acylamino group, alkyl or arylsulfonylamino group, amino group, alkylthio group. Represents an arylthio group, an alkoxy group, an aryloxy group, an aminocarbonylamino group, or an alkoxycarbonylamino group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group.

In (A-17), R ³¹ and R ³² are each independently a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acylamino group, an alkyl or arylsulfonylamino group, an amino group, an alkylthio group, an arylthio group, Represents an alkoxy group, an aryloxy group, an aminocarbonylamino group, an alkoxycarbonylamino group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group; Among each of R ³¹ and R ³² , a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acylamino group, an alkylsulfonylamino group, and an arylsulfonylamino group are preferable.

In (A-18) to (A-20), R ³³ and R ³⁴ represent a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a sulfamoyl group, an alkanesulfonyl group, an arenesulfonyl group, or a nitro group. To express. Among the R ³³ , a carbamoyl group, an alkoxycarbonyl group, or a cyano group is preferable, and a cyano group is more preferable. Among the R ³⁴ , a carbamoyl group, an alkoxycarbonyl group, a cyano group, or an alkyl or arylsulfonyl group is preferable, and an alkoxycarbonyl group is more preferable. In (A-18) to (A-20), R ³⁵ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Among R ³⁵ , an alkyl group or an aryl group is preferable, and an aryl group is more preferable. In (A-20), R ³⁶ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Among R ³⁶ , an alkyl group or an aryl group is preferable, and an aryl group is more preferable.

In (A-21) to (A-26), R ³⁷ and R ³⁸ are an alkyl group, an aryl group, a heterocyclic group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a cyano group, a sulfamoyl group, and an alkanesulfonyl group. Represents an arenesulfonyl group or a nitro group. Among the R ^{37 s} , an aryl group, a heterocyclic group, a carbamoyl group, an alkoxycarbonyl group, and a cyano group are preferable. Among the R ³⁸ , a carbamoyl group, an alkoxycarbonyl group, a cyano group, a sulfamoyl group, an alkylsulfonyl group, or an arylsulfonyl group is preferable. In (A-21) to (A-26), R ³⁹ , R ⁴⁰ and R ⁴¹ are a hydrogen atom, alkyl group, aryl group, heterocyclic group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, alkyl Alternatively, an arylsulfonylamino group, a halogen atom, an amino group, an alkylthio group, an arylthio group, an alkoxy group, or an aryloxy group is represented. Among the R ³⁹ , R ⁴⁰ , and R ⁴¹ , a hydrogen atom, an alkyl group, an acylamino group, a halogen atom, an amino group, an alkylthio group, or an arylthio group is preferable.

In (A-27), R ⁴² represents an amino group, an alkylthio group, an arylthio group, an alkoxy group or an aryloxy group. Among the R ⁴² , an N-arylamino group is preferable. In (A-27), R ⁴³ , R ⁴⁴ and R ⁴⁵ each independently represent a hydrogen atom, a cyano group, a sulfamoyl group, an alkyl or arylsulfonyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group. Of each of R ⁴³ , R ⁴⁴ and R ⁴⁵ , a hydrogen atom or a cyano group is preferable.

In (A-28), R ⁴⁶ and R ⁴⁷ each independently represent a hydrogen atom, a perfluoroalkyl group, a cyano group, a nitro group, a sulfamoyl group, an alkyl or arylsulfonyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group. Represents an alkylthio group or an arylthio group. Among each of R ⁴⁶ and R ⁴⁷ , a hydrogen atom, a perfluoroalkyl group, a cyano group, a nitro group, an alkyl or arylsulfonyl group, an alkylthio group, or an arylthio group is preferable. In (A-28), R ⁴⁸ represents an alkyl group, an aryl group, a heterocyclic group, a sulfamoyl group, an alkyl or arylsulfonyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group. Among the R ⁴⁸ , an aryl group or a heterocyclic group is preferable.

In (A-29), R ⁴⁹ is preferably a hydrogen atom, or a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or an acyl group. More preferred are a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group. R ⁵⁰ and R ⁵¹ are each independently preferably a hydrogen atom, or a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, substituted Or an unsubstituted acyl group, a cyano group, a carbamoyl group, or an alkoxycarbonyl group. More preferred are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and a cyano group.

In (A-30), R ⁴⁹ is preferably a hydrogen atom, or a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or an acyl group. More preferred are a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group. R ⁵⁰ and R ⁵¹ are each independently preferably a hydrogen atom, or a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, substituted Or an unsubstituted acyl group, a cyano group, a carbamoyl group, or an alkoxycarbonyl group. More preferred are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and a cyano group.

In (A-31) to (A-41) and (A-45) to (A-52), R ¹¹ and R ⁴⁹ are preferably a hydrogen atom, or a substituted or unsubstituted alkyl group, substituted or unsubstituted. An aryl group, a substituted or unsubstituted heterocyclic group. More preferred are a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group. R ⁵⁰ , R ⁵¹ , R ⁵² and R ⁵³ are each independently preferably a hydrogen atom, or a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, substituted or unsubstituted A heterocyclic group, a substituted or unsubstituted acyl group, a cyano group, a carbamoyl group, and an alkoxycarbonyl group. More preferred are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and a cyano group.

In (A-42), R ⁵⁰ and R ⁵¹ are preferably each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, substituted or unsubstituted A substituted heterocyclic group, a substituted or unsubstituted acyl group, a cyano group, a carbamoyl group, and an alkoxycarbonyl group. More preferred are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and a cyano group. Most preferably, they are a substituted or unsubstituted alkyl group and a cyano group.

In (A-43), R ⁵⁰ is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, A substituted or unsubstituted acyl group, a cyano group, a carbamoyl group, and an alkoxycarbonyl group; More preferred are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and a cyano group. Most preferably, they are a substituted or unsubstituted alkyl group and a cyano group.

In (A-44), R ⁵⁰ is preferably a hydrogen atom, or a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, A substituted or unsubstituted acyl group, a cyano group, a carbamoyl group, and an alkoxycarbonyl group; More preferred are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and a cyano group. Most preferably, they are a substituted or unsubstituted alkyl group and a cyano group.

Among the above general formulas, Q is more preferably the above general formulas (A-3), (A-29), (A-30), (A-42), (A-43), (A- 44).
Regarding a preferable combination of substituents (a combination of R ¹ , R ² , R ³ , and Q) of the dye compound represented by the general formula (1), a compound in which at least one of these substituents is the above-mentioned preferable group. More preferred are compounds in which more various substituents are the preferred groups, and most preferred are compounds in which all substituents are the preferred groups.

A preferred combination of substituents of the dye represented by the general formula (1) is that R ¹ is a substituted or unsubstituted acyl group, R ² is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and R ³ is substituted. Or an unsubstituted alkyl group having 1 to 4 carbon atoms, Q is (A-3), (A-29), (A-30), (A-42), (A-43) or (A-44) It is group represented by these. A more preferable combination of substituents of the dye compound represented by the general formula (1) is that R ¹ is an acyl group, R ² is an unsubstituted alkyl group, R ³ is an unsubstituted alkyl group, and Q is (A-3 ) Or (A-42).

  Among the dye compounds represented by the general formula (1), particularly preferred dye compounds include compounds represented by the following general formulas (B-1) to (B-6).

In the general formula (B-1) ~ (B -6), R 1, R 2 and R ³ each independently have the same meaning as R ^1, R ^2, R ³ in the general formula (1), the preferred range Is the same. R ⁷ and R ^{8 in} (B-1) are each independently synonymous with R ⁷ and R ^{8 in} formula (A-3), and the preferred range is also the same. R ^49, R ⁵⁰ and R ⁵¹ in the general formula (B-2) has the same meaning as R ^49, R ^50, R ⁵¹ each said general formula independently (A-29). R ⁵⁰ and R ⁵¹ of the formula (B-3) has the same meaning as R ^50, R ⁵¹ in the general formula (A-30), and the preferred range is also the same. R ^{50 in} formula (B-4) has the same meaning as R ^{50 in} formula (A-42), and the preferred range is also the same. R ^{50 in} formula (B-5) has the same definition as R ^{50 in} formula (A-43), and the preferred range is also the same. R ^{50 in} formula (B-6) has the same definition as R ^{50 in} formula (A-44), and the preferred range is also the same.
The most preferred dye compound of the present invention is the dye compound represented by the above general formula (B-1) or (B-4), and those having the above-mentioned preferred ranges are particularly preferred.

The substituents used in the present invention (substituents in each group or substituents that each group may substitute) will be described in more detail below.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a chlorine atom and a bromine atom are preferable, and a chlorine atom is particularly preferable.
The aliphatic group is a linear, branched, or cyclic aliphatic group. As described above, the saturated aliphatic group includes an alkyl group, a cycloalkyl group, and a bicycloalkyl group, and has a substituent. May be. These carbon numbers are preferably 1-30. Examples include methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, benzyl and 2-ethylhexyl. Can do. Here, the cycloalkyl group includes a substituted or unsubstituted cycloalkyl group. The substituted or unsubstituted cycloalkyl group is preferably a cycloalkyl group having 3 to 30 carbon atoms. Examples include a cyclohexyl group, a cyclopentyl group, and a 4-n-dodecylcyclohexyl group. Examples of the bicycloalkyl group include a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. Examples include a bicyclo [1.2.2] heptan-2-yl group and a bicyclo [2.2.2] octan-3-yl group. Further, it includes a tricyclo structure having many ring structures.

  The unsaturated aliphatic group is a linear, branched or cyclic unsaturated aliphatic group, and includes an alkenyl group, a cycloalkenyl group, a bicycloalkenyl group, and an alkynyl group. The alkenyl group represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group. As the alkenyl group, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms is preferable. Examples include vinyl group, allyl group, prenyl group, geranyl group, and oleyl group. The cycloalkenyl group is preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms. Examples include a 2-cyclopenten-1-yl group and a 2-cyclohexen-1-yl group. The bicycloalkenyl group includes a substituted or unsubstituted bicycloalkenyl group. The bicycloalkenyl group is preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group in which one hydrogen atom of a bicycloalkene having one double bond is removed. Examples include a bicyclo [2.2.1] hept-2-en-1-yl group and a bicyclo [2.2.2] oct-2-en-4-yl group. The alkynyl group is preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, and examples thereof include an ethynyl group and a propargyl group.

The aryl group is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, and an o-hexadecanoylaminophenyl group. The phenyl group which may have a substituent is preferable.
The heterocyclic group is a monovalent group obtained by removing one hydrogen atom from a substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and they may be further condensed. These heterocyclic groups are preferably 5- or 6-membered heterocyclic groups, and the hetero atoms of the ring structure are preferably oxygen atoms, sulfur atoms and nitrogen atoms. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. The heterocyclic ring in the heterocyclic group includes pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, quinazoline ring, cinnoline ring, phthalazine ring, quinoxaline ring, pyrrole ring, indole ring, furan ring Benzofuran ring, thiophene ring, benzothiophene ring, pyrazole ring, imidazole ring, benzimidazole ring, triazole ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, isothiazole ring, benzisothiazole ring, thiadiazole ring, Examples include isoxazole ring, benzisoxazole ring, pyrrolidine ring, piperidine ring, piperazine ring, imidazolidine ring and thiazoline ring.
The aliphatic oxy group (typically an alkoxy group) includes a substituted or unsubstituted aliphatic oxy group (typically an alkoxy group), and preferably has 1 to 30 carbon atoms. Examples thereof include a methoxy group, an ethoxy group, an isopropoxy group, an n-octyloxy group, a methoxyethoxy group, a hydroxyethoxy group, and a 3-carboxypropoxy group.
The aryloxy group is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms. Examples of the aryloxy group include phenoxy group, 2-methylphenoxy group, 4-tert-butylphenoxy group, 3-nitrophenoxy group, 2-tetradecanoylaminophenoxy group and the like. Preferably, it is a phenyloxy group that may have a substituent.

The acyloxy group is preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms. Examples of the acyloxy group include formyloxy group, acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group and the like.
The carbamoyloxy group is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms. Examples of carbamoyloxy groups include N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn-octyl A carbamoyloxy group can be exemplified.
The aliphatic oxycarbonyloxy group (typically an alkoxycarbonyloxy group) preferably has 2 to 30 carbon atoms and may have a substituent. Examples thereof include a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a tert-butoxycarbonyloxy group, and an n-octylcarbonyloxy group.
The aryloxycarbonyloxy group is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms. Examples of the aryloxycarbonyloxy group include a phenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, and a pn-hexadecyloxyphenoxycarbonyloxy group. Preferable is a phenoxycarbonyloxy group which may have a substituent.

The amino group includes an amino group, an aliphatic amino group (typically an alkylamino group), an arylamino group, and a heterocyclic amino group. The amino group is preferably a substituted or unsubstituted aliphatic amino group having 1 to 30 carbon atoms (typically an alkylamino group) or a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms. Examples of amino groups include, for example, amino group, methylamino group, dimethylamino group, anilino group, N-methyl-anilino group, diphenylamino group, hydroxyethylamino group, carboxyethylamino group, sulfoethylamino group, 3,5-Dicarboxyanilino group, 4-quinolylamino group and the like can be mentioned.
The acylamino group is preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms. Examples of the acylamino group include formylamino group, acetylamino group, pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group, and the like.
The aminocarbonylamino group is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms. Examples of the aminocarbonylamino group include carbamoylamino group, N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, morpholinocarbonylamino group and the like. The term “amino” in this group has the same meaning as “amino” in the aforementioned amino group.

The aliphatic oxycarbonylamino group (typically an alkoxycarbonylamino group) preferably has 2 to 30 carbon atoms and may have a substituent. Examples thereof include a methoxycarbonylamino group, an ethoxycarbonylamino group, a tert-butoxycarbonylamino group, an n-octadecyloxycarbonylamino group, and an N-methyl-methoxycarbonylamino group.
The aryloxycarbonylamino group is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms. Examples of the aryloxycarbonylamino group include phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxycarbonylamino group, and the like. The phenyloxycarbonylamino group which may have a substituent is preferable.
The sulfamoylamino group is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms. Examples of the sulfamoylamino group include a sulfamoylamino group, an N, N-dimethylaminosulfonylamino group, and an Nn-octylaminosulfonylamino group.
An aliphatic (typically alkyl) or arylsulfonylamino group is a substituted or unsubstituted aliphatic sulfonylamino group having 1 to 30 carbon atoms (typically an alkylsulfonylamino group), a substituted or unsubstituted group having 6 to 30 carbon atoms. An arylsulfonylamino group (preferably a phenylsulfonylamino group which may have a substituent) is preferable. Examples thereof include a methylsulfonylamino group, a butylsulfonylamino group, a phenylsulfonylamino group, a 2,3,5-trichlorophenylsulfonylamino group, and a p-methylphenylsulfonylamino group.

The aliphatic thio group (typically an alkylthio group) is preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms. Examples of the alkylthio group include a methylthio group, an ethylthio group, and an n-hexadecylthio group.
The sulfamoyl group is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms. Examples of the sulfamoyl group include N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N-benzoylsulfa group. A moyl group, an N- (N′-phenylcarbamoyl) sulfamoyl) group, and the like.
The aliphatic (typically alkyl) or arylsulfinyl group is a substituted or unsubstituted aliphatic sulfinyl group having 1 to 30 carbon atoms (typically an alkylsulfinyl group), a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms (preferably Is preferably a phenylsulfinyl group which may have a substituent. Examples thereof include a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group, and a p-methylphenylsulfinyl group.
The aliphatic (typically alkyl) or arylsulfonyl group is a substituted or unsubstituted aliphatic sulfonyl group having 1 to 30 carbon atoms (typically an alkylsulfonyl group), a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms (preferably Is preferably a phenylsulfonyl group which may have a substituent. For example, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-toluenesulfonyl group and the like can be mentioned.

The acyl group is a formyl group, a substituted or unsubstituted aliphatic carbonyl group having 2 to 30 carbon atoms (typically an alkylcarbonyl group), a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms (preferably a substituent). An optionally substituted phenylcarbonyl group), and a heterocyclic carbonyl group bonded to the carbonyl group at a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms is preferable. Examples thereof include acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl group and the like.
The aryloxycarbonyl group is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms. Examples of the aryloxycarbonyl group include phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p-tert-butylphenoxycarbonyl group and the like. A phenyloxycarbonyl group which may have a substituent is preferable.
The aliphatic oxycarbonyl group (typically an alkoxycarbonyl group) preferably has 2 to 30 carbon atoms and may have a substituent. Examples thereof include methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl group and the like.
The carbamoyl group is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms. Examples of the carbamoyl group include carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl group and the like.
Examples of the aryl or heterocyclic azo group include phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo group, and the like.
Examples of the imide group include an N-succinimide group and an N-phthalimide group.
In addition to these, there are a hydroxyl group, a cyano group, a nitro group, a sulfo group, and a carboxyl group.
Each of these groups may further have the above-described substituent, and examples of such a substituent include the above-described substituent.

The molecular weight of the dye compound represented by the general formula (1) is preferably 500 or less, and more preferably 450 or less, from the viewpoint of thermal diffusibility.
The dye compound represented by the general formula (1) is preferably used as a magenta or yellow color among the three primary colors. Moreover, the maximum absorption wavelength of the dye compound represented by the general formula (1) is preferably in the range of 400 to 570 nm, and more preferably in the range of 410 to 450 nm or 510 to 550 nm.
Specific examples of the dye compound represented by the general formula (1) are shown below, but the range of the dye compound represented by the general formula (1) that can be used in the present invention is limited by these exemplary compounds. Is not to be interpreted.

  Among the dye compounds represented by the general formula (1), the azomethine dye is an intermediate defined by Q according to the general synthesis method described in the literature (3rd edition Experimental Chemistry Course, page 1413, etc.) ( 3) and the following intermediate (2) can be easily synthesized by, for example, dehydrating condensation reaction according to the following reaction scheme. A detailed synthesis method will be specifically described in Examples.

In the above reaction scheme 1, R ^1, R ² and R ³ have the same meaning as R ^1, R ^2, R ³ corresponding in formula (1). Q is a group in which a double bond is replaced with a hydrogen atom or a substituent in Q = in the general formula (1).
Raw material A can be synthesized by the synthesis method described in J. Chem. Soc. Perkin. Trans. 1, 12, 3243 (1990).
As raw material B, bromoacetonitrile is commercially available from Aldrich and can be purchased (catalog number 242489-25G, etc.).
The intermediate 1 can be easily synthesized from the raw material A and the raw material B according to the heterocyclic synthesis method described in Heterocycles, Vol. 45, No. 5, 875 (1997).
Intermediate 2 is obtained from intermediate 1 according to the heterocylation amination method described in Heterocycles, Vol. 45, No. 5, page 875 (1997), or the acylation method described in the 3rd edition, New Experimental Chemistry Course, page 2555. It can be easily synthesized.
The intermediate 3 can be easily synthesized according to the method described in the 4th edition, Experimental Chemistry Course, Volume 20, page 405 and the like.

  On the other hand, the azo dye of the dye compound represented by the general formula (1) is obtained from the heterocyclic amino compound defined by Q according to the general synthesis method described in the literature (3rd edition Experimental Chemistry Course, page 1525, etc.). The obtained diazonium salt (intermediate (3)) and intermediate (2) can be easily synthesized by diazo coupling.

R ¹ , R ² , R ³ and Q in Reaction Scheme 2 are the same as in Reaction Scheme 1. The raw materials A and B and intermediates 1 and 2 can also be synthesized or purchased as described in Reaction Scheme 1.

(Coloring composition)
The coloring composition of this invention contains the pigment | dye of this invention represented by General formula (1), It is characterized by the above-mentioned. The coloring composition of the present invention includes a writing pen, colored plastic, other ink liquid, thermal transfer recording ink sheet, thermal transfer recording, color toner, inkjet ink, color filter and the like. In particular, it can be effectively used as an ink sheet for thermal transfer recording, thermal transfer recording, color toner, inkjet ink, and color filter.

[Ink sheet for thermal transfer recording]
The thermal transfer recording ink sheet of the present invention is characterized by containing the dye compound represented by the general formula (1). The thermal transfer recording ink sheet generally has a structure in which a dye-donating layer is formed on a support, and the dye-donating layer contains the dye compound represented by the general formula (1). The ink sheet for thermal transfer recording of the present invention prepares an ink liquid by dissolving the dye compound represented by the general formula (1) in a solvent together with a binder, or by dispersing in fine particles in a solvent, It can be produced by coating an ink liquid on a support and drying it appropriately to form a dye-donating layer.
As the support for the thermal transfer recording ink sheet of the present invention, any conventionally used support for an ink sheet can be appropriately selected and used. For example, the material described in paragraph No. 0050 of JP-A-7-137466 can be preferably used. The thickness of the support is preferably 2 to 30 μm.

The binder resin that can be used in the dye-donating layer of the ink sheet for thermal transfer recording of the present invention is particularly high as long as it has high heat resistance and does not prevent the dye compound from moving to the image receiving material when heated. The type is not limited. For example, what is described in paragraph number 0049 of JP-A-7-137466 can be given as a preferred example. As the solvent for forming the dye-donating layer, a conventionally known solvent can be appropriately selected and used, and those described in Examples of JP-A-7-137466 can be preferably used.
The content of the dye compound represented by the general formula (1) in the dye-donor layer is preferably ^{0.03~1.0g / m 2, 0.1~0.6g / m} 2 is more preferable. Further, the thickness of the dye-donating layer is preferably 0.2 to 5 μm, and more preferably 0.4 to 2 μm.
The ink sheet for thermal transfer recording of the present invention may have a layer other than the dye-donating layer as long as the effect of the present invention is not excessively inhibited. For example, it may have an intermediate layer between the support and the dye-donating layer, or it may have a back layer on the support surface opposite to the dye-donating layer (hereinafter also referred to as “back surface”). There may be. Examples of the intermediate layer include an undercoat layer and a diffusion prevention layer (hydrophilic barrier layer) for preventing diffusion of the dye in the direction of the support. Examples of the back layer include a heat resistant slip layer, and can prevent adhesion of the thermal head to the ink sheet.

In order to apply the present invention to a thermal transfer recording material capable of recording a full color image, a cyan ink sheet containing a heat diffusible cyan dye capable of forming a cyan image, and a heat diffusibility capable of forming a magenta image. It is preferable that a magenta ink sheet containing a magenta dye and a yellow ink sheet containing a heat-diffusible yellow dye capable of forming a yellow image are sequentially coated on a support. In addition, an ink sheet containing a black image forming substance may be further formed as necessary.
As a cyan ink sheet containing a heat-diffusible cyan dye capable of forming a cyan image, for example, those described in JP-A-3-103477 and JP-A-3-150194 are preferably used. it can. When providing a yellow ink sheet according to the present invention, as a magenta ink sheet containing a heat-diffusible magenta dye capable of forming a magenta image, for example, those described in JP-A-5-286268 are preferable. Can be used. In the case of providing a magenta ink sheet according to the present invention, as a yellow ink sheet containing a heat diffusible yellow dye capable of forming a yellow image, for example, those described in JP-A 1-222592 are preferably used. Can be used.

[Thermal transfer recording]
When performing thermal transfer recording using the ink sheet for thermal transfer recording of the present invention, a heating means such as a thermal head and an image receiving material are used in combination. In other words, thermal energy is applied from the thermal head to the ink sheet in accordance with the image recording signal, and the dye in the portion to which the thermal energy is applied moves to the image receiving material and is fixed, thereby recording an image. The image receiving material usually has a structure in which an ink receiving layer containing a polymer is provided on a support. As the configuration and materials used of the image receiving material, for example, those described in paragraph numbers 0056 to 0074 of JP-A-7-137466 can be preferably used.

[Color toner]
The color toner of the present invention contains the coloring compound represented by the general formula (1). As the binder resin for a color toner into which the dye compound (preferably an azo dye compound) represented by the general formula (1) of the present invention is introduced, all binders generally used for toners can be used. For example, a styrene resin, an acrylic resin, a styrene / acrylic resin, a polyester resin, and the like can be given. For the purpose of imparting fluidity improvement or charge control to the toner, inorganic fine powder or organic fine particles may be externally added. Silica fine particles and titania fine particles whose surface is treated with an alkyl group-containing coupling agent or the like are preferably used. These particles preferably have a number average primary particle size of 10 to 500 nm, and more preferably 0.1 to 20% by mass in the toner.
As the release agent, any release agent conventionally used for toners can be used. Specific examples include olefins such as low molecular weight polypropylene, low molecular weight polyethylene, and ethylene-propylene copolymer, microcrystalline wax, carnauba wax, sazol wax, and paraffin wax. These addition amounts are preferably 1 to 5% by mass in the toner.

The charge control agent may be added as necessary, but is preferably colorless from the viewpoint of color development. Examples thereof include those having a quaternary ammonium salt structure and those having a calixarene structure.
As the carrier, either an uncoated carrier composed only of magnetic material particles such as iron or ferrite, or a resin-coated carrier whose surface is coated with a resin or the like may be used. The average particle size of this carrier is preferably 30 to 150 μm in terms of volume average particle size.
The image forming method to which the toner of the present invention is applied is not particularly limited. For example, a method of forming a color image by repeatedly performing transfer after forming a color image on the photoconductor or forming on the photoconductor Examples include a method of sequentially transferring the formed image to an intermediate transfer member or the like, forming a color image on the intermediate transfer member or the like, and then transferring the image to an image forming member such as paper to form a color image.

[Ink-jet ink]
The inkjet ink according to the present invention is characterized by containing the coloring compound represented by the general formula (1). The ink of the present invention can be prepared by dissolving and / or dispersing the coloring compound represented by the general formula (1) in an oleophilic medium or an aqueous medium. Preferably, an aqueous medium is used. is there. Since the ink of the present invention contains a pigment excellent in spectral characteristics and fastness as described above, it can be suitably used as an ink for ink jet recording. If necessary, other additives are contained within a range that does not impair the effects of the present invention. Other additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, Well-known additives, such as a foaming agent, a viscosity modifier, a dispersing agent, a dispersion stabilizer, a rust preventive agent, a chelating agent, are mentioned. These various additives are generally added to the dispersion after the preparation of the pigment dispersion, but may be added to the oil phase or the aqueous phase at the time of preparation.

The anti-drying agent is preferably used for the purpose of preventing clogging due to drying of the ink-jet ink at the ink jet port of the nozzle used in the ink-jet recording method.
The anti-drying agent is preferably a water-soluble organic solvent having a vapor pressure lower than that of water. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin. Polyhydric alcohols typified by trimethylolpropane, etc., lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocycles such as N-ethylmorpholine, sulfolane, dimethylsulfoxy , Sulfur-containing compounds such as 3-sulfolene, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred. Moreover, said anti-drying agent may be used independently and may be used together 2 or more types. These drying inhibitors are preferably contained in the ink in an amount of 10 to 50% by mass.

The penetration enhancer is preferably used for the purpose of allowing ink jet ink to penetrate better into paper. Examples of the penetration enhancer include alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, and nonionic surfactants. it can. If these are contained in the ink in an amount of 5 to 30% by mass, they usually have a sufficient effect, and it is preferable to use them in a range of addition amounts that do not cause printing bleeding and paper loss (print through).
The ultraviolet absorber is used for the purpose of improving image storage stability. Examples of the ultraviolet absorber include benzotriazoles described in JP-A Nos. 58-185677, 61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Compounds, benzophenone compounds described in JP-A-46-2784, JP-A-5-194443, US Pat. No. 3,214,463, etc., JP-B-48-30492, 56 -21141, JP-A-10-88106, etc., cinnamic acid compounds, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, and JP-A-10-182621. Triazine compounds described in JP-A-8-501291 and the like, Research Disclosure No. Compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based and benzoxazole-based compounds, so-called fluorescent brighteners, can also be used.

The anti-fading agent is used for the purpose of improving image storage stability. As the anti-fading agent, various organic and metal complex anti-fading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like. More specifically, Research Disclosure No. No. 17643, Nos. VII to I, J; 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544 at page 527, ibid. 307105, page 872, ibid. Compounds described in the patent literature cited in 15162 and compounds represented by the general formulas and compound examples of representative compounds described on pages 127 to 137 of JP-A-62-215272 can be used. .
Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. These are preferably used in the ink in an amount of 0.02 to 1.00% by mass.

The neutralizer (organic base, inorganic alkali) can be used as the pH adjuster. For the purpose of improving the storage stability of the inkjet ink, the pH adjuster is preferably added so that the inkjet ink has a pH of 6 to 10, and more preferably added to have a pH of 7 to 10.
Examples of the surface tension adjusting agent include nonionic, cationic and anionic surfactants. In addition, as for the surface tension of the inkjet ink containing the coloring composition of this invention, 20-60 mN / m is preferable. Furthermore, 25-45 mN / m is preferable. The viscosity of the inkjet ink of the present invention is preferably 30 mPa · s or less. Furthermore, it is more preferable to adjust to 20 mPa · s or less.

  Examples of surfactants include fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl sulfates. Anionic surfactants such as ester salts, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester Nonionic surfactants such as oxyethyleneoxypropylene block copolymers are preferred. Further, SURFYNOLS (trade name, manufactured by AirProducts & Chemicals) which is an acetylene-based polyoxyethylene oxide surfactant is also preferably used. An amine oxide type amphoteric surfactant such as N, N-dimethyl-N-alkylamine oxide is also preferred. Furthermore, pages (37) to (38) of JP-A-59-157636, Research Disclosure No. The surfactants described in 308119 (1989) can also be used.

As the antifoaming agent, fluorine-based, silicone-based compounds, chelating agents represented by EDTA, and the like can be used as necessary.
In the case where the dye compound represented by the general formula (1) is dispersed in an aqueous medium, JP-A-11-286637, JP-A-2001-246763, JP-A-2001-262039, and JP-A-2001-247788 are disclosed. As described, colored fine particles containing a compound and an oil-soluble polymer are dispersed in an aqueous medium, or JP-A Nos. 2001-262018, 2001-240763, 2001-335734, 2002-808072. It is preferable to disperse | distribute the pigment | dye compound represented by General formula (1) melt | dissolved in the high boiling point organic solvent in an aqueous medium as described in above. Specific methods for dispersing the dye compound represented by the general formula (1) in an aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additives, and the amounts used thereof are described in the aforementioned patent document. Can be preferably used. Alternatively, the bisazo compound may be dispersed in a fine particle state as a solid. At the time of dispersion, a dispersant or a surfactant can be used.

  Dispersing devices include simple stirrer, impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.), ultrasonic method, high-pressure emulsification dispersion method (high-pressure homogenizer) Specific examples of commercially available devices include gorin homogenizers, microfluidizers, DeBEE2000 (manufactured by BEE International), and the like. Regarding the method for preparing the ink for ink jet recording, in addition to the above-mentioned patent documents, JP-A Nos. 5-148436, 5-295212, 7-97541, 7-82515, 7-118584, Details are described in JP-A-11-286637 and JP-A-2001-271003, and can also be used for preparing the ink for ink jet recording of the present invention.

  As the aqueous medium, a mixture containing water as a main component and optionally adding a water-miscible organic solvent can be used. Examples of the water miscible organic solvent include alcohols (eg, methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), Polyhydric alcohols (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl Ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether , Triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amine (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetri) Min, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl) 2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone). In addition, the said water miscible organic solvent may use 2 or more types together.

〔Color filter〕
The color filter of this invention contains the pigment | dye compound represented by the said General formula (1), It is characterized by the above-mentioned. As a method for forming a color filter, a pattern is first formed with a photoresist and then dyed, or disclosed in JP-A-4-163552, JP-A-4-128703, JP-A-4-17553, and the like. As described above, there is a method of forming a pattern with a photoresist added with a colorant. Any of these methods may be used as a method used for introducing the dye compound represented by the general formula (1) of the present invention into a color filter, and a preferable method is disclosed in JP-A-4-175754. After applying a positive resist composition comprising a thermosetting resin, a quinonediazide compound, a cross-linking agent, a colorant and a solvent onto a substrate, the method described in JP-A-6-35182 and JP-A-6-35182. A method for forming a color filter comprising exposing through a mask, developing the exposed portion to form a positive resist pattern, exposing the entire surface of the positive resist pattern, and then curing the exposed positive resist pattern Can be mentioned. Further, a black matrix is formed according to a conventional method, and an RGB primary color system or Y.I. M.M. A C-complementary color filter can be obtained.

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

Hereinafter, the present invention will be described in more detail with reference to examples.
The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

Example 1 Synthesis and Evaluation of Dye [1]
<Synthesis of Exemplary Compound (2)>

Here, Ph represents a phenyl group (—C ₆ H ₅ ), Et represents an ethyl group (—C ₂ H ₅ ), and t-Bu represents a t-butyl group (—C (CH ₃ ) ₃ ).

(Synthesis of Intermediate (2c))
To 50 g (380 mmol) of ethyl isothiocyanatoformate (manufactured by Wako Pure Chemical Industries, Ltd.) was added 440 mL of hexane. This was cooled to 0 ° C. or less, and 27.8 g (380 mmol) of diethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise. The reaction solution was concentrated under reduced pressure, 200 mL of hydrochloric acid was added, and the mixture was heated to reflux for 3 hours. The reaction mixture was neutralized with sodium hydroxide and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, and filtered. Hexane was slowly added dropwise to the organic layer concentrated under reduced pressure to obtain an intermediate (2c). Yield 29.42 g (58% yield).

(Synthesis of Intermediate (2d))
To the intermediate (2c), 6.61 g (0.050 mol), chloroacetonitrile (manufactured by Aldrich) (0.055 mol) was added 40 mL of ethanol, and the mixture was heated to reflux. After 1 hour, the reaction was concentrated. Further, ethyl acetate was added and the precipitated crystals were filtered to obtain an intermediate (2d). 8.8 g (yield 85%).

(Synthesis of Intermediate (2e))
To 5.19 g (0.025 mol) of intermediate (2d), 25 mL of dimethylacetamide and 7.0 mL of triethylamine were added and cooled to 0 ° C., and 3.15 g of pivaloyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise. After 3 hours, water was added and the mixture was extracted with ethyl acetate. The extract was washed with water and saturated brine, and dried over magnesium sulfate. After filtration, the filtrate was concentrated and purified by silica gel column chromatography to obtain intermediate (2e). Yield 3.92 g (61% yield).

(Synthesis of Intermediate (2f))
14.5 g (0.10 mol) of phenylhydrazine hydrochloride (manufactured by Aldrich) and 21.0 g (0.10 mol) of diethyl sodium oxalate acetate (manufactured by Tokyo Chemical Industry) were added to 150 mL of acetic acid and stirred at 90 ° C. for 2 hours. After cooling to 0 ° C., the produced crystals were filtered and washed with water to obtain an intermediate (2f). Yield 11.6 g (yield 50%).

(Synthesis of Intermediate (2g))
Intermediate (2f) was added to 27.9 g (0.12 mol) and 300 mL of 28% aqueous ammonium hydroxide, and the mixture was heated to reflux at 80 ° C. After 12 hours, the solution was neutralized with hydrochloric acid and poured into an ice bath, and the purified crystals were filtered. After washing with water and drying, an intermediate (2 g) was obtained. Yield 17.0 g (70% yield).

(Synthesis of Intermediate (2h))
Intermediate (2 g) (40.6 g, 0.20 mol) was added to 300 mL of acetonitrile and cooled to 0 ° C. A mixed solution of phosphorus oxychloride (70 mL) -DMF (200 mL) was slowly added, and the mixture was stirred at 15 ° C. or lower. After 1 hour, the reaction solution was added to an ice bath, and the generated crystals were filtered. The obtained crystals were dissolved in ethyl acetate and recrystallized by adding hexane. The obtained crystal was washed with hexane and dried to obtain an intermediate (2h). Yield 16.6 g (45% yield).

(Synthesis of Intermediate (2i))
To intermediate (2h) (3.49 g, 18.85 mmol), 40 mL of acetic acid, 10 mL of hydrochloric acid and 10 mL of water were added and cooled to 0 ° C. with an ice bath. Sodium nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) (1.30 g, 18.85 mmol) was slowly added, followed by stirring for 1 hour. The produced crystal was filtered and washed with water to obtain an intermediate (2i). Yield 2.8 g (70% yield).

(Synthesis of Exemplary Compound (2))
50 mL of methanol was added to 2.57 g (12.0 mmol) of intermediate (2a) and intermediate (2i) (2.54 g, 10.0 mmol), and the mixture was stirred at room temperature. After 2 hours, the produced crystals were filtered and washed with methanol to obtain Exemplified Compound (2). Yield 2.92 g (6.47 mmol), 65% yield.

<Synthesis of Comparative Control Dye (A)>
The following comparative control dye (A) was synthesized according to the above synthesis method of the exemplary compound (2). The comparative control dye (A) is similar in structure to the compound 7 of Patent Document 14 (JP-A-4-338592) and the compound D-11 of Patent Document 15 (JP-A-2001-271003).

<Evaluation of absorption characteristics>
The absorption characteristics of the exemplary compound (2) obtained in Example 1 and the comparative control dye (A) were evaluated. Absorption characteristics were normalized to 1.0 for the maximum absorption wavelength and the half width (abs. Of the maximum absorption wavelength) of the absorption spectrum in an ethyl acetate solution (concentration 1 × 10 ⁻⁶ mol / L, optical path length 10 mm). The Abs.
The results of evaluation are shown in Table 1 below together with ¹ H-NMR data.

As is apparent from Table 1 above, all of the dyes exhibit a magenta color, but the exemplified compound (2) which is the dye compound of the present invention is bonded to the thiazole ring in the comparative dye (A) − C (CH ₃ ) _{3 is changed} to —NHC (═O) —C (CH ₃ ) ₃ . The exemplary compound (2) has a hydrogen atom on the nitrogen atom of the amide group, and as a result, it can be seen that the half width is significantly narrower than that of the comparative control dye (A). That is, it was confirmed that the dye compound of the present invention had a nitrogen atom group (—NHR ¹ ) having a hydrogen atom at the ortho position, and thus the absorption was sharp and exhibited favorable spectral characteristics for color reproduction.

Example 2: Synthesis and evaluation of dye [2]
<Synthesis of Exemplary Compound (7)>

(Synthesis of Intermediate (7a))
3-Amino-2-cyano-4,4-dimethyl-2-pentenenitrile (29.8 g, 0.20 mol) was dissolved in 120 mL of methanol, and 101.2 g of 20% ammonium sulfide was gradually added at room temperature. The mixture was warmed to 50 ° C. and stirred. After 5 hours, the mixture was extracted with ethyl acetate, washed with water and saturated brine, and concentrated under reduced pressure. 150 mL of methanol was added to the concentrated solution, cooled in an ice bath, 56 mL of 30% aqueous hydrogen peroxide was gradually added, and the mixture was stirred for 2 hours. 450 mL of water was added dropwise, and the generated crystals were filtered. Washing with water and drying gave intermediate (7a). Yield 33.4 g (92% yield).

(Synthesis of Exemplary Compound (7))
Intermediate (7a) (1.09 g, 0.006 mol) was dissolved in 10 mL of 85% phosphoric acid and cooled to an internal temperature of 0 ° C. Sodium nitrite 0.48 g (0.007 mol) was added in portions, stirred at an internal temperature of 0-5 ° C. for 30 minutes, and then 1.27 g (0.005 mol) of intermediate (2e) was added. The mixture was stirred at an internal temperature of 0 to 5 ° C. for 30 minutes and then at room temperature for 1 hour. Water was added to the reaction solution, and the precipitated crystals were filtered off. The crystal was purified by silica gel chromatography (developing solvent: ethyl acetate / hexane = 1/2) to obtain Illustrative Compound (7). Yield 1.30 g (58% yield).

<Synthesis of Exemplified Compounds (8) and (9) and Comparative Control Dye (B)>
Exemplified Compound (8), Exemplified Compound (9), and Comparative Control Dye (B) were synthesized according to the synthesis method of Exemplified Compound (7). The comparative dye (B) is similar in structure to the compound 76 of Patent Document 6 (Japanese Patent No. 3001991).

<Evaluation of absorption characteristics>
The absorption characteristics of the exemplary compounds (7) to (9) and the comparative control dye (B) were evaluated by the same method as in Example 1.
The evaluation results are shown in Table 2 below together with ¹ H-NMR data.

As is clear from Table 2 above, all are magenta dyes.
Exemplified compounds of the present invention (7) is obtained by changing the -Bu-t attached to the thiazole ring of the comparative dye (B) to -NH (= O) -C (CH 3) 3. It can be seen that the exemplary compound (7) has a hydrogen atom on the nitrogen atom of the amide group, and as a result, the half-value width is significantly narrower than that of the comparative control dye (B).
In addition, Exemplified Compounds (8) and (9) having —NH (═O) —C (CH ₃ ) ₃ at the same position as Exemplified Compound (7) also have a narrow half-value width and exhibit favorable spectral characteristics for color reproduction. It was confirmed.

Example 3: Synthesis and evaluation of dye [3]
<Synthesis of Exemplary Compound (1)>
The exemplified compound (1) was synthesized according to the synthesis method of the exemplified compound (2) of Example 1. ¹ H-NMR of the obtained exemplary compound (1) was as follows.
¹ H-NMR (in CDCl ₃ ) 9.24 (s), 4.43 (q, J = 7.2Hz, 2H), 3.86 (q, J = 7.2Hz, 2H), 3.60 (q, J = 7.2Hz), 2.57 ( s, 3H), 1.60-1.59 (m, 9H), 1.44 (t, J = 7.2 Hz, 3H), 1.39-1.32 (m, 6H)

<Evaluation of absorption characteristics>
The absorption characteristics of the exemplified compound (1) were evaluated by the same method as in Example 1.
The maximum absorption wavelength was 543.0 nm, and the half width was 87.8 nm.

  Exemplified compounds other than the compounds synthesized in Examples 1 to 3 can also be synthesized according to Examples 1 to 3 and Heterocycles, Vol. 45, No. 5, 1997, 875-888 (synthesis of alkylaminothiazole).

Example 4: Preparation and evaluation of thermal transfer recording ink sheet < Preparation of thermal transfer recording ink sheet>
A 6.0 μm thick polyester film (Lumirror, trade name, manufactured by Toray Industries, Inc.) with heat-resistant slip treatment applied to the back side with a thermosetting acrylic resin (thickness 1 μm) on the back side is used. The following dye-donating layer-forming coating composition was applied and formed by wire bar coating so that the thickness when dried was 1 μm, to prepare ink sheet 1 for thermal transfer recording.

(Coating composition for forming dye-donating layer)
Illustrative compound (1) 5.5 parts by mass Polyvinyl butyral resin 4.5 parts by mass (S-REC BX-1, trade name, manufactured by Sekisui Chemical Co., Ltd.)
90 parts by mass of methyl ethyl ketone / toluene (1/1)

  Next, an ink sheet was produced in which the exemplified compound (1) was changed to the exemplified compounds (2), (7), (8), (9), and the comparative dyes (A) and (B), respectively. At this time, it was confirmed that each dye compound of the present invention has no problem in solubility.

<Production of image receiving material>
Synthetic paper (YUPO FPG200, trade name, manufactured by YUPO Corporation, thickness 200 μm) is used as a support, and a white intermediate layer-forming coating composition and a receiving layer-forming coating composition having the following composition are placed on one side in this order. Application was performed by a coater. The amount of each coating was such that the white intermediate layer was 1.0 g / m ² and the receiving layer was 4.0 g / m ² during drying, and the drying was performed at 110 ° C. for 30 seconds.

(White intermediate layer forming coating composition)
Polyester resin (Byron 200, trade name, manufactured by Toyobo Co., Ltd.) 10 parts by weight Optical brightener (Uvitex OB, trade name, manufactured by Ciba Geigy) 1 part by weight Titanium oxide 30 parts by weight Methyl ethyl ketone / toluene (1/1) 90 parts by mass

(Coating composition for receiving layer formation)
100 parts by weight of vinyl chloride-vinyl acetate resin (Solvine A, trade name, manufactured by Nissin Chemical Industry Co., Ltd.)
Amino-modified silicone 5 parts by mass (X22-3050C, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)
Epoxy-modified silicone 5 parts by mass (X22-300E, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.)
Methyl ethyl ketone / toluene (= 1/1) 400 parts by mass Benzotriazole UV absorber 5 parts by mass (Tinuvin 900, trade name, manufactured by Ciba Specialty Chemicals)

<Image recording and evaluation>
Each ink sheet manufactured above and the image receiving material are superposed so that the dye-donating layer and the image-receiving layer are in contact with each other, and a thermal head is used from the back side of the dye-donating material, and the output of the thermal head is 0.25 W / dot. When printing was performed under the conditions of a pulse width of 0.15 to 15 milliseconds and a dot density of 6 dots / mm, and a magenta color dye was imagewise dyed on the image receiving layer of the image receiving material, the dye compound of the present invention was used. All of the ink sheets were able to record a clear image without uneven transfer, as compared with the ink sheet of the corresponding comparative dye.

Example 5: Preparation and evaluation of color toner < Preparation of color toner>
3 parts by mass of the above exemplified compound (7), 100 parts by mass of a resin for toner [styrene-acrylic acid ester copolymer; Hymer TB-1000F (trade name, manufactured by Sanyo Chemical Co., Ltd.)] are mixed and ground by a ball mill, and then 150 parts. The mixture was melt-mixed by heating to ° C, and after cooling, coarsely pulverized using a hammer mill, and then finely pulverized by an air jet type pulverizer. Further, classification was performed to select particles having a size of 1 to 20 μm to obtain toner. To 10 parts by mass of each of these toners, 900 parts by mass of carrier iron powder (EFV250 / 400, trade name, manufactured by Nippon Iron Powder Co., Ltd.) was uniformly mixed to obtain a developer.
Further, each developer was prepared in the same manner except that equimolar amounts of Exemplified Compound (8), (9) and Comparative Control Dye (B) were used instead of Exemplified Compound (7).

<Evaluation>
When each of the developers thus obtained was copied with a dry plain paper electrophotographic copying machine [NP-5000, trade name, manufactured by Canon Inc.], a developer using the dye compound of the present invention was used. As compared with the developer using the comparative dye (B), it was found that all of them have excellent spectral characteristics and show excellent properties as a toner.

Example 6: Preparation and evaluation of inkjet ink < Preparation of inkjet ink>
5.63 g of the exemplified compound (1), 7.04 g of sodium dioctylsulfosuccinate, 4.22 g of the following high boiling organic solvent (S-2), 5.63 g of the following high boiling organic solvent (S-11) and 50 ml of ethyl acetate. It was dissolved in at 70 ° C. 500 ml of deionized water was added to this solution while stirring with a magnetic stirrer to prepare an oil-in-water type coarse particle dispersion.
Next, the coarse particle dispersion is micronized by passing it through a microfluidizer (manufactured by MICROFLUIDEX INC) five times at a pressure of 60 MPa, and the resulting emulsion is odor of ethyl acetate using a rotary evaporator. The solvent was removed until there was no more.
Ink jet ink was prepared by adding 140 g of diethylene glycol, 50 g of glycerin, 7 g of SURFYNOL 465 (trade name, manufactured by AirProducts & Chemicals) and 900 ml of deionized water to the fine emulsion of the hydrophobic dye thus obtained.
Similarly, instead of Exemplified Compound (1), Exemplified Compound (2), (7), (8), (9), Comparative Control Dyes (A) and (B) were used in equimolar amounts. In the same manner, each ink-jet ink was prepared.

<Evaluation>
Each obtained ink liquid is packed in a cartridge of an ink jet printer (PM-G800, trade name, manufactured by Seiko Epson Corporation), and ink jet paper painting photo finishing Pro (trade name, manufactured by Fuji Photo Film Co., Ltd.) on the same machine. ) Was recorded. As a result, any of the inks using the dye compound of the present invention has superior spectral characteristics as compared with inks using the corresponding comparative dyes, and has excellent properties as an inkjet ink. I found out.

Example 7: Production and evaluation of color filter < Production of color filter>
(Preparation of positive resist composition)
Using 3.4 parts by mass of a cresol novolak resin (polystyrene-converted mass average molecular weight 4300) obtained from a mixture of m-cresol / p-cresol / formaldehyde (reaction molar ratio = 5/5 / 7.5), a phenol compound of the following formula O-naphthoquinonediazide-5-sulfonic acid ester (average of two hydroxyl groups are esterified) 1.8 parts by mass, hexamethoxymethylolated melamine 0.8 parts by mass, ethyl lactate 20 parts by mass, and A positive resist composition was obtained by mixing 1 part by mass of the exemplified compound (1).

(Production of color filter)
The obtained positive resist composition was spin-coated on a silicon wafer, and then the solvent was evaporated. Next, the silicon wafer was exposed through a mask to decompose the quinonediazide compound. Thereafter, heating was performed at 100 ° C., and then the exposed portion was removed by alkali development to obtain a positive colored pattern having a resolution of 0.8 μm. After the entire surface was exposed, it was heated at 150 ° C. for 15 minutes to obtain a magenta complementary color filter. The exposure was performed with an i-line exposure stepper HITACHI LD-5010-i (trade name, manufactured by Hitachi, Ltd., NA = 0.40). The developer used was SOPD or SOPD-B (both trade names, manufactured by Sumitomo Chemical Co., Ltd.).
Similarly, each of Exemplified Compound (1) was similarly replaced except that Exemplified Compound (2), (7), (8), (9), and Comparative Control Dyes (A) and (B) were replaced by equimolar amounts. A color filter was produced.

<Evaluation>
Any color filter using the dye compound of the present invention has excellent spectral characteristics and light transmission properties as compared with a color filter using a corresponding comparative dye, and exhibits excellent properties as a color filter. It was confirmed.

  According to the present invention, a novel dye compound having excellent spectral characteristics and high fastness with sharp absorption, and excellent solubility, a colored composition containing the same, and excellent storage stability containing the dye An ink sheet for thermal transfer recording and a thermal transfer recording method are provided. In addition, a color toner, an ink jet ink and a color filter containing the coloring matter are provided. Therefore, the present invention is expected to be effectively used for high-quality full-color recording and the like, and has high industrial applicability.

Claims (11)

A dye compound represented by the following general formula (1).

(In General Formula (1), Q represents an atomic group necessary for the compound represented by General Formula (1) to have absorption in at least one of the visible region and the near infrared region, and R ¹ represents a hydrogen atom or Represents a substituent, and R ² and R ³ each independently represent a substituent, and may be bonded to each other to form a ring structure.   In the general formula (1), Q is = C (Ra) (Rb) or = N-Rc (Ra and Rb each independently represents a hydrogen atom or a substituent, and Rc represents a heterocyclic group). The coloring matter compound according to claim 1 characterized by things. The dye compound according to claim 1 or 2, wherein in the general formula (1), Q is represented by any one of the following general formulas (A-1) to (A-47).

(In the general formulas (A-1) to (A-47), R ⁴ and R ^{7 to} R ⁵³ each independently represents a substituent. R ⁵ and R ⁶ each independently represents an electron-withdrawing substituent. A represents an integer of 0 to 3, b represents an integer of 0 to 2, and c and d each independently represents an integer of 0 to 4. Here, * represents a nitrogen of aminothiazole in the general formula (1). (Shows the site of bonding to an atom through a double bond.)   The dye compound according to claim 3, wherein in the general formula (1), Q is represented by the general formula (A-3).   In the general formula (1), Q is represented by the general formula (A-29), (A-30), (A-42), (A-43) or (A-44). The dye compound according to claim 3.   The coloring composition characterized by including the pigment | dye compound of any one of Claims 1-5.   An ink sheet for thermal transfer recording, comprising the dye compound according to any one of claims 1 to 5.   A thermal transfer recording method comprising forming an image on an image receiving material having an ink receiving layer containing a polymer on a support, using the thermal transfer recording ink sheet according to claim 7.   A color toner comprising the dye compound according to claim 1.   An ink-jet ink comprising the dye compound according to any one of claims 1 to 5.   A color filter comprising the dye compound according to claim 1.