JP2009242757A - Colored composition, ink for ink-jet recording, and pigment compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored composition which does not contain a heavy metal and is excellent in optical solidity. <P>SOLUTION: The colored composition comprises a medium and a pigment compound represented by general formula (1). In the formula, R<SP>1</SP>, R<SP>2</SP>, A<SP>1</SP>and A<SP>2</SP>independently from each other represent a hydrogen atom or a mono-valent substituent group. X<SP>1</SP>and X<SP>2</SP>independently from each other represent a hetero atom which may have a substituent group. Y represents a group of atoms required for forming a 4-7 membered hetero ring Q, together with the carbon atoms to which Y is bonded. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a coloring composition containing a merocyanine dye compound, an ink jet recording ink, and a dye compound.

  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. Further, a color filter is used for recording and reproducing a color image on an image pickup device such as a CCD in a photographing apparatus and on an LCD or PDP in a display. In these color image recording materials and color filters, three primary colors (dyes and pigments) of the so-called additive color mixture method and subtractive color mixture method are used to display or record full color images. In fact, there is no fast-acting dye that has absorption characteristics that can realize the above-mentioned conditions and can withstand various use conditions and environmental conditions, and improvement is strongly desired.

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, pigment-dispersed ink, or solid (melting 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 a good yellow hue, high solubility or dispersibility, fastness to light, humidity and heat, and in particular, fastness to light.

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. However, conventional specific dye compounds (see, for example, Patent Documents 3 and 4) that have been proposed as having spectral characteristics favorable for color reproduction and being robust to light and heat are not satisfactory, and are further improved. Is strongly desired.

  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, but it has been difficult to obtain optical characteristics like a dye with a color filter using the pigment.

The dyes and pigments used in each of the above applications must have the following properties in common. That is, it has preferable absorption characteristics in terms of color reproducibility, fastness under environmental conditions to be used, for example, light resistance, heat resistance, good resistance to oxidizing gases such as ozone, and the like. In addition, when the pigment is a pigment, it is substantially insoluble in water and organic solvents and has good chemical fastness, and even when used as particles, the preferred absorption characteristics in the molecular dispersion state are impaired. It is also necessary to have properties such as absence. The required characteristics can be controlled by the strength of intermolecular interaction, but it is difficult to achieve both because they are in a trade-off relationship.
In addition, when using the pigment, in addition to having a particle size and a particle shape necessary for expressing the desired transparency, fastness under the environmental conditions used, such as light resistance, heat resistance, Good resistance to oxidative gases such as ozone, and other chemical fastness to organic solvents and sulfurous acid gas. Disperse even fine particles in the medium used, and stable dispersion. , Etc. are also required. In particular, there is a strong demand for pigments that have a good yellow hue, have high coloring power among light, wet heat, and active gases in the environment, and are fast to light.

  In other words, the required performance for pigments is more diverse than dyes that require performance as pigment molecules, and not only the performance as pigment molecules, but also the above requirements as solids (fine particle dispersions) as aggregates of pigment molecules All performance needs to be satisfied. As a result, the group of compounds that can be used as pigments is extremely limited compared to dyes, and even if high-performance dyes are derived into pigments, there are only a few that can satisfy the required performance as fine particle dispersions. It cannot be developed. This is confirmed by the fact that the number of pigments registered in the color index is less than 1/10 of the number of dyes.

  Azo pigments are widely used in printing inks, ink-jet inks, electrophotographic materials, and the like because they are excellent in hue and coloring power, which are color characteristics. Of these, the most typically used yellow azo pigments are diarylide pigments. Examples of diarylide pigments include C.I. I. Pigment Yellow 12, 13 and 17 and the like. However, since diarylide pigments are very inferior in fastness, especially light resistance, when the printed matter is exposed to light, the pigment is decomposed and discolored, which is not suitable for long-term storage of the printed matter.

  On the other hand, condensed polycyclic pigments are generally excellent in light fastness and heat resistance, and are therefore used in resin coloring, color filters, inkjet inks, and the like. Representative examples include phthalocyanine pigments (for example, CI Pigment Blue 15: 3, CI Pigment Green 7), quinacridone pigments (for example, CI Pigment Violet 19, CI Pigment, etc.). Red 122 etc.), diketopyrrolopyrrole pigments (eg CI Pigment Red 254 etc.), anthraquinone pigments (eg CI Pigment Red 177 etc.). However, condensed polycyclic pigments have disadvantages that they are inferior in coloring power and dispersibility or have a high halogen content, which is a concern for safety.

  When expressing a full color using a subtractive color mixing method of three colors of yellow, magenta, and cyan, or four colors added with black, if a pigment with poor fastness is used for one color, the gray of the printed matter If the balance is changed and a pigment having poor color characteristics is used, the color reproducibility at the time of printing is lowered. Therefore, in order to obtain a printed matter that maintains high color reproducibility for a long period of time, a pigment dispersion having both color characteristics and fastness is desired.

On the other hand, compounds represented by the following chemical formulas (S-1) to (S-5) are known as heterocyclic compounds containing two sulfur atoms (for example, Patent Document 1 and Non-Patent Documents 1 to 3). reference).
Moreover, the compound represented by following Chemical formula (S-6) is known as an electron donor molecule of a charge transfer complex (for example, refer nonpatent literature 4). Furthermore, compounds represented by the following chemical formulas (S-7) to (S-8) are known as sensitizing dyes for photosensitive compositions (see, for example, Patent Document 2).

JP 2007-256494 A JP 2002-116540 A JP-A-53-67524 JP 59-78895 A Journal of the Chemical Society, Perkin Trans. I, 1975, 1277 Bullet of the Chemical Society of Japan (Bull. Chem. Soc. Jpn.) 1978, Vol. Journal of the Chemical Society Chemical Communications (J. Chem. Soc., Chem. Commun.) 1994, page 1431 Journal of the Chemical Society Chemical Communications (J. Chem. Soc., Chem. Commun.) 1994, page 899

However, the compounds described in Patent Document 1 or Non-Patent Documents 1 to 3 only absorb ultraviolet light or visible light having a very short wavelength in the solution. Further, the compound described in Non-Patent Document 4 is a compound intended as an electron donor molecule of a charge transfer complex, and is not a compound intended for use as a colored compound.
Further, the compound described in Patent Document 2 has been studied as a sensitizing dye in a photosensitive composition, and is intended to absorb only visible light having a very short wavelength in consideration of workability under safelight conditions. It was what it was.

As described above, none of the compounds represented by the chemical formulas (S-1) to (S-8) was intended to be used as a colored compound. Furthermore, there is no indication or suggestion about a coloring composition in which the above-mentioned known condensed polycyclic compounds mentioned above are used in a finely dispersed state in a medium, and the fine particle state of these compounds Nothing is known about the stability and solvent resistance in
An object of the present invention is to provide a coloring composition excellent in light fastness that does not contain a heavy metal, and an ink for ink jet recording containing the coloring composition. Another object of the present invention is to provide a dye compound having excellent spectral characteristics with sharp absorption.

As a result of intensive studies, the present inventors have found that the above problems can be achieved by the following configuration. Specific means for solving the above problems are as follows.

<1> A colored composition comprising a medium and a dye compound represented by the following general formula (1).

(In the formula, R ¹ , R ² , A ¹ and A ² each independently represent a hydrogen atom or a monovalent substituent. X ¹ and X ² each independently have a substituent. And Y represents a group of atoms necessary to form a 4-7 membered heterocycle Q together with the carbon atom to which Y is bonded.

<2> The coloring composition according to <1>, wherein the coloring compound represented by the general formula (1) is dispersed in the medium.
<3> The heterocycle Q in the general formula (1) is represented by any one of the following general formulas (2) to (7), or a tautomer thereof. The coloring composition as described in <2>.

(In the formula, R ²¹ and R ²² each independently represent a hydrogen atom or a monovalent substituent. R ²³ , R ²⁴ and R ²⁵ may each independently have a substituent. When R ²³ has a substituent, the substituent may be bonded to R ²¹ or R ²² to form a ring, and when R ²⁴ has a substituent, the substituent is R And may form a ring by bonding to ^{22. When} R ²⁵ has a substituent, the substituent may bond to R ²¹ to form a ring)

(In the formula, R ³¹ , R ³² and R ³⁴ each independently represent a hydrogen atom or a monovalent substituent. R ³³ and R ³⁵ may each independently have a substituent. Represents a hetero atom, and when R ³³ has a substituent, the substituent may be bonded to R ³¹ or R ³² to form a ring, and when R ³⁵ has a substituent, the substituent is R ^31. To form a ring)

(In the formula, R ⁴¹ and R ⁴⁴ each independently represent a hydrogen atom or a monovalent substituent. R ⁴³ and R ⁴⁵ each independently represent a hetero atom which may have a substituent. When at least one of R ⁴³ and R ⁴⁵ has a substituent, the substituent may combine with R ⁴¹ to form a ring)

(Wherein R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent substituent, and R ⁵¹ and R ⁵² may be bonded to each other to form a ring. R ⁵³ , and R ⁵⁴ represents a hetero atom which may have a substituent independently of each other, and when R ⁵³ has a substituent, the substituent may combine with R ⁵² to form a ring. ^{When 54} has a substituent, the substituent may combine with R ⁵¹ to form a ring)

^{(Wherein, R 62,} and ^{R 64} are the ^{.R 63} represents a hydrogen atom or a monovalent substituent independently of one another, ^{.R 63} representing the hetero atom which may have a substituent is a substituent The substituent may combine with R ⁶² to form a ring)

(Z ⁷¹ and Z ⁷² each independently represent —N═ or —C (R ⁷⁵ ) ═. R ⁷³ , R ⁷⁴ , and R ⁷⁵ each independently represent a hydrogen atom or a monovalent substituent. Represents

<4> At least one of R ²⁴ and R ²⁵ in the general formula (2), R ^{35 in} the general formula (3), R ⁴⁵ in the general formula (4), and R ⁵³ in the general formula (5) And at least one of R ⁵⁴ represents an oxygen atom, respectively, wherein the coloring composition according to <3>.
<5> At least one of R ²¹ in the general formula (2), R ^{31 in} the general formula (3), R ⁴¹ in the general formula (4), and R ⁵¹ and R ⁵² in the general formula (5). Each represents a hydrogen atom, The colored composition as described in <3> or <4> above.

<6> The colored composition according to any one of <1> to <5>, wherein X ¹ and X ² in the general formula (1) each represent a sulfur atom.
<7> In the general formula (1), R ¹ and R ² are each independently a hydrogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a cyano group, or a halogen atom. The coloring composition according to any one of> to <6>.
<8> A ¹ and A ² in the general formula (1) are each independently a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an acyloxy group, an aryloxy group, a carbamoyloxy group, an alkylcarbamoyloxy group, The colored composition according to any one of <1> to <7>, which is an arylcarbamoyloxy group, a cyano group, a carbamoyl group, a halogen atom, or a nitro group.
<9> The colored composition according to any one of <1> to <8>, further including a dispersant.

<10> An ink for inkjet recording, comprising the colored composition according to any one of <1> to <9>.
<11> A thermal transfer ink sheet comprising the colored composition according to any one of <1> to <9>.
<12> A color filter comprising the colored composition according to any one of <1> to <9>.
<13> A dye compound represented by the following general formula (8).

(In the general formula (8), R ⁸¹ and R ⁸² each independently represent a hydrogen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted acyl group, substituted or unsubstituted R ⁸³ , R ⁸⁴ represents a substituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group. , R ⁸⁵ and R ⁸⁶ each independently represents a hydrogen atom or a monovalent substituent.)
<14> A dye compound represented by the following general formula (9).

(In the general formula (9), R ⁹¹ , R ⁹² , R ⁹³ , R ⁹⁴ , R ⁹⁵ , R ⁹⁶ and R ⁹⁷ each independently represent a hydrogen atom or a monovalent substituent)
<15> A dye compound represented by the following general formula (10).

(In the general formula (10), X ¹⁰¹ and X ¹⁰² each independently represent -N = or -C (R ¹⁰⁷ ) =, and R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ And R ¹⁰⁷ each independently represents a hydrogen atom or a monovalent substituent)

<16> A colored composition containing the dye compound according to any one of <13> to <15>.
<17> An ink jet recording ink containing the coloring compound according to any one of <13> to <15>.
<18> A thermal transfer ink sheet containing the dye compound according to any one of <13> to <15>.
<19> A color filter containing the dye compound according to any one of <13> to <15>

  ADVANTAGE OF THE INVENTION According to this invention, the ink for inkjet recording containing the coloring composition excellent in the light fastness which does not contain a heavy metal, and this coloring composition can be provided. Furthermore, according to the present invention, it is possible to provide a dye compound having excellent spectral characteristics with sharp absorption.

In the following, the coloring composition of the present invention, the dye compound used therein, the ink jet ink, the ink sheet for thermal transfer material, the color filter, the novel dye compound used therein, and the like will be described in detail.
The description of the constituent elements described below may be made 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.
The coloring composition of the present invention contains at least one medium and at least one dye compound represented by the following general formula (1), and has an absorption in a wavelength region of 400 to 700 nm. To do.

<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 coloring composition of the present invention includes at least one dye compound represented by the following general formula (1). By including the coloring compound represented by the following general formula (1), a colored composition excellent in light fastness that does not contain a heavy metal can be formed.

In general formula (1), R ¹ , R ² , A ¹ and A ² each independently represent a hydrogen atom or a monovalent substituent.
Examples of the substituent represented by R ¹ , R ² , A ¹ and A ² (hereinafter sometimes referred to as “substituent in the present invention”) include a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, Alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxy group, nitro group, carboxy group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy Group, aryloxycarbonyloxy group, amino group (including anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto Group, alkylthio group Arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, imide group, phosphino group, phosphinyl group, A phosphinyloxy group, a phosphinylamino group, a silyl group, etc. can be mentioned.

  In the substituents exemplified above, the substituent having a hydrogen atom may be further substituted with the substituent exemplified above after the hydrogen atom has been removed. Examples of such a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group. More specifically, examples include a methylsulfonylaminocarbonyl group, a p-methylphenylsulfonylaminocarbonyl group, an acetylaminosulfonyl group, and a benzoylaminosulfonyl group.

In the present invention, R ¹ and R ² are each a hydrogen atom or an alkyl group having 1 to 9 carbon atoms (for example, methyl, ethyl, etc.) from the viewpoint of optical properties and various fastnesses of the dye compound represented by the general formula (1). N-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, etc.), carbon number 5 9 cycloalkyl groups (cyclopentyl, cyclohexyl, etc.), C 6-10 aryl groups (eg, phenyl, 4-t-butylphenyl, etc.), C 3-9 heterocyclic groups (eg, imidazolyl, pyrazolyl, Triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, etc.), an acyl group having 2 to 9 carbon atoms (for example, acetyl) 3-phenylpropanoyl, benzoyl and the like), an alkoxy group having 1 to 9 carbon atoms (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-methylsulfonylethoxy, etc.), an aryloxy group having 6 to 9 carbon atoms (for example, Phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbonylphenoxy, 3-methoxycarbonylphenyloxy and the like, a heterocyclic oxy group having 3 to 9 carbon atoms (for example, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy, etc.), C2-C9 acyloxy groups (eg acetoxy, propionyloxy, 2-ethylhexanoyloxy etc.), hydroxy groups, halogen atoms (eg , Fluorine atom, chlorine atom, bromine atom, etc.), nitro group, cyano Group, amino group, alkylamino group having 1 to 9 carbon atoms (for example, methylamino, butylamino, diethylamino, methylbutylamino, etc.), arylamino group having 6 to 9 carbon atoms (for example, phenylamino, 2-chloroanilino, etc.) ), A C3-C9 heterocyclic amino group, a C1-C9 alkoxycarbonyl group (e.g., methoxycarbonyl, butyloxycarbonyl, etc.), a C6-C9 aryloxycarbonyl group (e.g., phenoxycarbonyl, etc.) ), A carbamoyl group, and a substituent selected from the group consisting of sulfamoyl groups, preferably a hydrogen atom, a hydroxy group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a nitro group, a cyano group Group, an alkoxy group having 1 to 9 carbon atoms (for example, methoxy, ethoxy, 2-methoxy Ethoxy, 2-methylsulfonylethoxy, etc.), and an acyloxy group having 2 to 9 carbon atoms (for example, acetoxy, propionyloxy, 2-ethylhexanoyloxy, etc.) More preferably, a hydrogen atom, a hydroxy group, a halogen atom (for example, fluorine atom, chlorine atom, bromine atom), a cyano group, an alkoxy group having 1 to 9 carbon atoms (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-methyl) More preferably a substituent selected from the group consisting of an acyloxy group having 2 to 9 carbon atoms (for example, acetoxy, propionyloxy, 2-ethylhexanoyloxy, etc.), and a fluorine atom. , Chlorine atom, cyano group, acetoxy group, methoxy group, or ethoxy group There is further preferable.

In the present invention, A ¹ and A ² are each a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, or 6 to 6 carbon atoms from the viewpoint of optical properties and various fastnesses of the dye compound represented by the general formula (1). 10 aryl groups, C3-C9 heterocyclic groups, C2-C9 acyl groups, C1-C9 alkoxy groups, C6-C9 aryloxy groups, C3-C9 hetero Ring oxy group, acyloxy group having 2 to 9 carbon atoms, hydroxy group, halogen atom, nitro group, cyano group, amino group, alkylamino group having 1 to 9 carbon atoms, arylamino group having 6 to 9 carbon atoms, carbon number A heterocyclic amino group having 3 to 9 carbon atoms, an alkoxycarbonyl group having 2 to 9 carbon atoms, an aryloxycarbonyl group having 7 to 9 carbon atoms, a carbamoyl group, a carbamoyloxy group, an alkylcarbamoyloxy group having 2 to 10 carbon atoms, and a carbon number It is preferably any substituent selected from the group consisting of ˜11 arylcarbamoyloxy groups and sulfamoyl groups, a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an aryl group having 6 to 10 carbon atoms, carbon Any substituent selected from the group consisting of an alkoxy group having 1 to 9 carbon atoms, an aryloxy group having 6 to 9 carbon atoms, an acyloxy group having 2 to 9 carbon atoms, a halogen atom, a nitro group, a cyano group, and a sulfamoyl group And more preferably a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom or a cyano group, and even more preferably a hydrogen atom.

In the general formula (1), adjacent ones of R ¹ , R ² , A ¹ , and A ² may be bonded to each other to form a ring. However, this ring is a 5-membered heterocycle, and a hetero atom (for example, a nitrogen atom, an oxygen atom, a sulfur atom) is directly attached to the benzene ring to which R ¹ , R ² , A ¹ , and A ² are bonded. Except when combined.
The ring formed by adjacent ones of R ¹ , R ² , A ¹ , and A ² is a 4- to 7-membered ring from the viewpoint of thermodynamic stability of the dye compound represented by the general formula (1). It is preferably a 5-membered ring, more preferably a 6-membered ring. When this ring is a 6-membered ring, it may be an aliphatic ring or an aromatic ring, but is more preferably an aromatic ring.

The ring formed by the adjacent ones of R ¹ , R ² , A ¹ , and A ² may further have a substituent. Examples of such substituents are the same as the above-mentioned examples of “substituents in the present invention”.

Although the preferable specific example of the combination of R < ¹ >, R < ² >, A < ¹ > and A < ² > in the said General formula (1) is shown in following Table 1 and Table 2, this invention is not limited to these. Note that wavy line in the Table indicates the binding site to X ¹ and X ² in the general formula (1).

In the general formula (1) in the present invention, X ¹ and X ² represent a hetero atom which may have a substituent. Examples of such heteroatoms include boron atoms, nitrogen atoms, oxygen atoms, silicon atoms, phosphorus atoms, sulfur atoms, and selenium atoms. From the viewpoint of optical properties and various fastnesses of the dye compound represented by the general formula (1), a nitrogen atom, an oxygen atom or a sulfur atom which is an electron donating atom having an unshared electron pair is preferable, and a sulfur atom Is particularly preferred. Among these heteroatoms, a heteroatom (for example, a boron atom, a nitrogen atom, a silicon atom, or a phosphorus atom) that can form three or more covalent bonds may have a substituent. Examples of the substituent on the hetero atom in this case are the same as the above-described example of the “substituent in the present invention”.

Favorable examples of 5-membered heterocyclic ring containing X ¹ and X ² in the general formula (1) are shown in the following Table 3, the present invention is not limited thereto. In addition, the wavy line in a table | surface shows the coupling | bond part to the heterocyclic ring Q in the said General formula (1).

  In the general formula (1) in the present invention, Y represents an atomic group necessary for forming a 4- to 7-membered heterocyclic ring Q together with the carbon atom to which Y itself is bonded.

The heterocycle Q in the present invention is not particularly limited as long as it is a 4 to 7 member containing at least one heteroatom, and may be an aliphatic heterocycle or an aromatic heterocycle. Further, the heterocycle Q may be further condensed with another ring.
Although the preferable specific example of the ring Q in this invention is shown in following Table 4 and Table 5, this invention is not limited to these. Note that wavy line in the Table indicates the binding site on the heterocycle containing X ¹ and X ² in the general formula (1).

  The heterocyclic ring Q in the present invention is preferably a heterocyclic ring containing a nitrogen atom from the viewpoints of optical properties and various fastnesses of the dye compound represented by the general formula (1). From the viewpoint of thermodynamic stability of the dye compound represented by formula (5), a 5- to 6-membered ring is more preferable, and any one of the following general formulas (2) to (7) or a tautomer thereof More preferably, it is more preferably represented by any one of the following general formulas (3) to (7) or a tautomer thereof, and the following general formula (6) or a tautomer thereof: It is particularly preferred that

R ²¹ and R ²² in the general formula (2) each independently represent a hydrogen atom or a monovalent substituent. Examples of the substituent represented by R ²¹ and R ²² are the same as those in the above-mentioned “substituent in the present invention”.

In the present invention, as R ²¹ and R ²² , from the viewpoint of optical properties and various fastnesses of the dye compound represented by the general formula (1), a hydrogen atom, an alkyl group having 1 to 9 carbon atoms (for example, methyl, Ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), carbon number 6-10 aryl groups (for example, phenyl, 4-t-butylphenyl), C3-C9 heterocyclic groups (for example, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2 -Benzothiazolyl), acyl group having 2 to 9 carbon atoms (for example, acetyl, 3-phenylpropanoyl, benzoyl), 1 carbon atom Any one of the substituents selected from the group consisting of 9 alkoxycarbonyl groups (for example, methoxycarbonyl, butyloxycarbonyl), aryloxycarbonyl groups having 6 to 9 carbon atoms (for example, phenoxycarbonyl), carbamoyl groups, and sulfamoyl groups And preferably a hydrogen atom or an alkyl group having 1 to 9 carbon atoms (for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, 2-ethylhexyl). , 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), an aryl group having 6 to 10 carbon atoms (for example, phenyl, 4-t-butylphenyl), a hydrogen atom, methyl Group, ethyl group, and phenyl group are more preferable, and a hydrogen atom is Preferred.

R ²³ , R ²⁴ and R ²⁵ each independently represent a hetero atom which may have a substituent.
Specific examples of such a hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a selenium atom from the viewpoint of optical properties and various fastnesses of the dye compound represented by the general formula (1). Is preferably a heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom. Moreover, it is preferable that at least one of R ²⁴ and R ²⁵ is an oxygen atom.
Moreover, when the hetero atom represented by R ²³ , R ²⁴ , and R ²⁵ has a substituent, examples of the substituent on the hetero atom are the same as those in the above-mentioned “substituent in the present invention”.

Further, when R ²³ has a substituent, the substituent may be bonded to R ²¹ or R ²² to form a ring, and when R ²⁴ has a substituent, the substituent is bonded to R ^22. A ring may be formed, and when R ²⁵ has a substituent, the substituent may be bonded to R ²¹ to form a ring.

R ³¹ , R ³² and R ³⁴ in the general formula (3) each independently represent a hydrogen atom or a monovalent substituent.

Examples of the substituent represented by R ³¹ are the same as the examples of the “substituent in the present invention”.
In the present invention, R ³¹ is specifically a hydrogen atom or an alkyl group having 1 to 9 carbon atoms (for example, methyl) from the viewpoint of optical properties and various fastnesses of the dye compound represented by the general formula (1). , Ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), carbon An aryl group having 6 to 10 carbon atoms (for example, phenyl, 4-t-butylphenyl), a heterocyclic group having 3 to 9 carbon atoms (for example, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), acyl group having 2 to 9 carbon atoms (for example, acetyl, 3-phenylpropanoyl, benzoyl), 1 to 9 carbon atoms Any substituent selected from the group consisting of an alkoxycarbonyl group (for example, methoxycarbonyl, butyloxycarbonyl), an aryloxycarbonyl group having 6 to 9 carbon atoms (for example, phenoxycarbonyl), a carbamoyl group, and a sulfamoyl group. It is preferably a hydrogen atom, an alkyl group having 1 to 9 carbon atoms (for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), an aryl group having 6 to 10 carbon atoms (for example, phenyl, 4-t-butylphenyl), more preferably a hydrogen atom, a methyl group , An ethyl group and a phenyl group are more preferable, and a hydrogen atom is particularly Masui.

Examples of the substituent represented by R ³² are the same as the examples of the “substituent in the present invention”.
As R ³² in the present invention, specifically, from the viewpoint of optical properties and various fastnesses of the dye compound represented by the general formula (1), specifically, a hydrogen atom, an aryl group having 6 to 10 carbon atoms (for example, Phenyl, 4-t-butylphenyl), a heterocyclic group having 3 to 9 carbon atoms (for example, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), 2 to 4 carbon atoms Acyl groups (for example, acetyl, 3-phenylpropanoyl, benzoyl), nitro groups, cyano groups, alkoxycarbonyl groups having 1 to 4 carbon atoms, aryloxycarbonyl groups having 6 to 9 carbon atoms (for example, methoxycarbonyl, ethoxy Carbonyl, butyloxycarbonyl), a carbamoyl group, and any substituent selected from the group consisting of sulfamoyl groups It is preferable that a hydrogen atom, a cyano group, an acetyl group, and a carbamoyl group are particularly preferable.

Examples of the substituent represented by R ³⁴ are the same as the above-described examples of the “substituent in the present invention”.
In the present invention, R ³⁴ is specifically a hydrogen atom or an alkyl group having 1 to 9 carbon atoms (for example, methyl) from the viewpoint of optical properties and various fastnesses of the dye compound represented by the general formula (1). , Ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), carbon An aryl group having 6 to 10 carbon atoms (for example, phenyl, 4-t-butylphenyl) and an alkoxy group having 1 to 9 carbon atoms (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-methylsulfonylethoxy) are preferable. Particularly preferred are a hydrogen atom, a methyl group, an ethyl group, a methoxy group, and an ethoxy group.

R ³³ and R ³⁵ each independently represent a hetero atom which may have a substituent.
Specific examples of such a hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a selenium atom from the viewpoint of optical properties and various fastnesses of the dye compound represented by the general formula (1). Is preferably a heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom. R ³⁵ is particularly preferably an oxygen atom.
Examples of the substituent on the hetero atom are the same as those in the above-mentioned “substituent in the present invention”.

Further, when R ³³ has a substituent, the substituent may be bonded to R ³¹ or R ³² to form a ring. When R ³⁵ has a substituent, the substituent may be bonded to R ³¹ to form a ring.

R ⁴¹ and R ⁴⁴ in the general formula (4) each independently represent a hydrogen atom or a monovalent substituent.

Examples of the substituent represented by R ⁴¹ are the same as the examples of the “substituent in the present invention”.
In the present invention, R ⁴¹ is specifically a hydrogen atom or an alkyl group having 1 to 9 carbon atoms (for example, methyl) from the viewpoint of optical properties and various fastnesses of the dye compound represented by the general formula (1). , Ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), carbon An aryl group having 6 to 10 carbon atoms (for example, phenyl, 4-t-butylphenyl), a heterocyclic group having 3 to 9 carbon atoms (for example, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), acyl group having 2 to 9 carbon atoms (for example, acetyl, 3-phenylpropanoyl, benzoyl), 1 to 9 carbon atoms Any substituent selected from the group consisting of an alkoxycarbonyl group (for example, methoxycarbonyl, butyloxycarbonyl), an aryloxycarbonyl group having 6 to 9 carbon atoms (for example, phenoxycarbonyl), a carbamoyl group, and a sulfamoyl group. It is preferably a hydrogen atom, an alkyl group having 1 to 9 carbon atoms (for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), or an aryl group having 6 to 10 carbon atoms (for example, phenyl, 4-t-butylphenyl), preferably a hydrogen atom, a methyl group More preferably an ethyl group or a phenyl group, It is particularly preferred.

Examples of the substituent represented by R ⁴⁴ are the same as the examples of the “substituent in the present invention”.
In the present invention, R ⁴⁴ is specifically a hydrogen atom or an alkyl group having 1 to 9 carbon atoms (for example, methyl) from the viewpoint of optical properties and various fastnesses of the dye compound represented by the general formula (1). , Ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), carbon An aryl group having 6 to 10 carbon atoms (for example, phenyl, 4-t-butylphenyl) or an alkoxy group having 1 to 9 carbon atoms (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-methylsulfonylethoxy) is preferable. A hydrogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group is particularly preferable.

R ⁴³ and R ⁴⁵ each independently represent a hetero atom which may have a substituent.
Specific examples of such a hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a selenium atom from the viewpoint of optical properties and various fastnesses of the dye compound represented by the general formula (1). Is preferably a heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom. R ⁴⁵ is particularly preferably an oxygen atom.
Examples of the substituent on the hetero atom are the same as those in the above-mentioned “substituent in the present invention”.

Further, when at least one of R ⁴³ and R ⁴⁵ has a substituent, the substituent may be bonded to R ⁴¹ to form a ring.

R ⁵¹ and R ⁵² in the general formula (5) each independently represent a hydrogen atom or a monovalent substituent. Examples of the substituent represented by R ⁵¹ and R ⁵² are the same as those of the above-mentioned “substituent in the present invention”.

In the present invention, R ⁵¹ and R ⁵² are specifically a hydrogen atom, an alkyl having 1 to 9 carbon atoms from the viewpoint of optical properties and fastness of the dye compound represented by the general formula (1). Groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, Cyclopentyl), aryl groups having 6 to 10 carbon atoms (for example, phenyl, 4-t-butylphenyl), heterocyclic groups having 3 to 9 carbon atoms (for example, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), acyl group having 2 to 9 carbon atoms (for example, acetyl, 3-phenylpropanoyl, benzoyl) , An alkoxycarbonyl group having 1 to 9 carbon atoms (for example, methoxycarbonyl, butyloxycarbonyl), an aryloxycarbonyl group having 6 to 9 carbon atoms (for example, phenoxycarbonyl), a carbamoyl group, and a sulfamoyl group. It is preferably any one of the substituents, more preferably an aryl group having 6 to 10 carbon atoms (for example, phenyl or 4-t-butylphenyl), and further preferably a phenyl group.

R ⁵³ and R ⁵⁴ each independently represent a hetero atom which may have a substituent.
Specific examples of such a hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a selenium atom from the viewpoint of optical properties and various fastnesses of the dye compound represented by the general formula (1). Is preferably a heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom. Moreover, it is particularly preferable that at least one of R ⁵³ and R ⁵⁴ is an oxygen atom.
Examples of the substituent on the hetero atom are the same as those in the above-mentioned “substituent in the present invention”.

In addition, when R ⁵³ has a substituent, the substituent may be bonded to R ⁵² to form a ring, and when R ⁵⁴ has a substituent, the substituent is bonded to R ⁵¹ to form a ring. May be.

R ⁶² and R ⁶⁴ in the general formula (6) each independently represent a hydrogen atom or a monovalent substituent.
Examples of the substituent represented by R ⁶² are the same as those of the above-mentioned “substituent in the present invention”.

In the present invention, R ⁶² is specifically a hydrogen atom or an alkyl group having 1 to 9 carbon atoms (for example, methyl) from the viewpoint of optical properties and various fastnesses of the dye compound represented by the general formula (1). , Ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), carbon An aryl group having 6 to 10 carbon atoms (for example, phenyl, 4-t-butylphenyl), a heterocyclic group having 3 to 9 carbon atoms (for example, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), acyl group having 2 to 9 carbon atoms (for example, acetyl, 3-phenylpropanoyl, benzoyl), 1 to 9 carbon atoms Any substituent selected from the group consisting of an alkoxycarbonyl group (for example, methoxycarbonyl, butyloxycarbonyl), an aryloxycarbonyl group having 6 to 9 carbon atoms (for example, phenoxycarbonyl), a carbamoyl group, and a sulfamoyl group. It is preferably a hydrogen atom, an alkyl group having 1 to 9 carbon atoms (for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl) or an aryl group having 6 to 10 carbon atoms (for example, phenyl, 4-t-butylphenyl) is more preferable. More preferably a group, an ethyl group or a phenyl group, water Atom is particularly preferred.

Examples of the substituent represented by R ⁶⁴ are the same as the examples of the “substituent in the present invention”.
In the present invention, R ⁶⁴ is specifically a hydrogen atom or an alkyl group having 1 to 9 carbon atoms (for example, methyl) from the viewpoint of optical properties and various fastnesses of the dye compound represented by the general formula (1). , Ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), carbon An aryl group having 6 to 10 carbon atoms (for example, phenyl, 4-t-butylphenyl), an alkoxy group having 1 to 9 carbon atoms (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-methylsulfonylethoxy), 1 carbon atom Is preferably a carbamoyl group having 9 to 9 carbon atoms, or an acylamino group having 2 to 9 carbon atoms, a hydrogen atom, a methyl group, an ethyl group, a methoxy group Or an ethoxy group is particularly preferred.

R ⁶³ represents a hetero atom which may have a substituent.
Specific examples of such a hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a selenium atom from the viewpoint of optical properties and various fastnesses of the dye compound represented by the general formula (1). Is preferably a heteroatom selected from the group consisting of an oxygen atom, a nitrogen atom, and a sulfur atom. R ⁶³ is particularly preferably an oxygen atom.
Examples of the substituent on the hetero atom are the same as those in the above-mentioned “substituent in the present invention”.

Further, when R ⁶³ has a substituent, the substituent may be bonded to R ⁶² to form a ring.

Z ⁷¹ and Z ⁷² in the general formula (7) each independently represent N═ or —C (R ⁷⁵ ) ═.

R ⁷³ , R ⁷⁴ , and R ⁷⁵ each independently represent a hydrogen atom or a monovalent substituent. Examples of the substituent represented by R ⁷³ , R ⁷⁴ , and R ⁷⁵ are the same as those in the above-mentioned “substituent in the present invention”.
In the present invention, as R ⁷³ and R ⁷⁴ , specifically, from the viewpoint of optical properties and various fastnesses of the dye compound represented by the general formula (1), an aryl group having 6 to 10 carbon atoms (for example, Phenyl, 4-t-butylphenyl), a heterocyclic group having 3 to 9 carbon atoms (for example, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), 2 to 4 carbon atoms Acyl groups (for example, acetyl, 3-phenylpropanoyl, benzoyl), nitro groups, cyano groups, alkoxycarbonyl groups having 1 to 4 carbon atoms, aryloxycarbonyl groups having 6 to 9 carbon atoms (for example, methoxycarbonyl, ethoxy Carbonyl, butyloxycarbonyl), carbamoyl groups, and arylcarbamoyl groups (eg, N-phenylcarbamoyl) N- (2-methoxyphenyl) carbamoyl) is preferably any substituent selected from the group consisting of phenyl, acetyl, nitro, cyano, alkoxycarbonyl, or carbamoyl. Are more preferable, and a cyano group, a methoxycarbonyl group, an ethoxycarbonyl group, or a (2,6-di (t-butyl) -4-methylcyclohexyl) oxycarbonyl group is particularly preferable.

In the present invention, R ⁷⁵ is specifically a hydrogen atom or an alkyl group having 1 to 9 carbon atoms (for example, methyl) from the viewpoint of optical properties and various fastnesses of the dye compound represented by the general formula (1). , Ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl), carbon An aryl group having 6 to 10 carbon atoms (for example, phenyl, 4-t-butylphenyl), a heterocyclic group having 3 to 9 carbon atoms (for example, imidazolyl, pyrazolyl, triazolyl, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), acyl group having 2 to 9 carbon atoms (for example, acetyl, 3-phenylpropanoyl, benzoyl), 1 to 9 carbon atoms Any substituent selected from the group consisting of an alkoxycarbonyl group (for example, methoxycarbonyl, butyloxycarbonyl), an aryloxycarbonyl group having 6 to 9 carbon atoms (for example, phenoxycarbonyl), a carbamoyl group, and a sulfamoyl group. It is preferably a hydrogen atom, an alkyl group having 1 to 9 carbon atoms (for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl) or an aryl group having 6 to 10 carbon atoms (for example, phenyl, 4-t-butylphenyl) is more preferable. A group, ethyl group or phenyl group is particularly preferred.

In the dye compound represented by the general formula (1) in the present invention, the substituents represented by R ¹ , R ² , A ¹ , and A ² and the substituent in Q generally improve various fastnesses of the pigment. It is also preferable that the substituent is a known substituent, specifically, for example, a substituent having an amide bond, particularly a benzimidazolone or quinoxalinedione structure.

In the present invention, from the viewpoint of optical properties and various fastnesses of the dye compound represented by the general formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkoxy group having 1 to 6 carbon atoms, An acyloxy group having 2 to 9 carbon atoms, a hydroxy group, a halogen atom, a cyano group, an amino group, a monoalkylamino group having 1 to 9 carbon atoms, an alkoxycarbonyl group having 1 to 9 carbon atoms, a sulfamoyl group, or a carbamoyl group. , A ¹ and A ² are a hydrogen atom, alkyl group, aryl group, alkoxy group, acyloxy group, aryloxy group, carbamoyloxy group, alkylcarbamoyloxy group, arylcarbamoyloxy group, cyano group, carbamoyl group, halogen atom, or a nitro group, or a heterocyclic ring Q is a 5-6 membered, X ¹ and X ² is nitrogen atom, an oxygen atom, or a sulfate It is preferable that the atom.

More preferably, R ¹ and R ² are each independently a hydrogen atom, an alkoxy group having 1 to 6 carbon atoms, an acyloxy group having 2 to 9 carbon atoms, a hydroxy group, a cyano group, or a halogen atom, and A ¹ And A ² is a hydrogen atom or a halogen atom, the ring Q is any one of the general formulas (2) to (7), or a tautomer thereof, and X ¹ and X ² are sulfur atoms. .

More preferably, R ¹ and R ² are a methoxy group, an ethoxy group, an acetoxy group, a hydroxy group, A ¹ and A ² are hydrogen atoms, and ring Q is represented by formula (6) or a tautomer thereof. And X ¹ and X ² are sulfur atoms.

Particularly preferably, R ¹ and R ² are a methoxy group or an acetoxy group, A ¹ and A ² are hydrogen atoms, the ring Q is the general formula (6), and the general formula (6) A compound in which R ⁶³ is an oxygen atom, R ⁶⁴ is an alkyl group, an alkoxy group, a carbamoyl group, or an acylamino group, and X ¹ and X ² are sulfur atoms.

  The dye compound represented by the general formula (1) in the present invention can take a tautomer depending on the structure and the environment in which it is placed. Although described in this specification in one of the representative forms, tautomers different from those described in the present specification are also included in the compounds of the present invention.

  The dye compound represented by the general formula (1) can be a cation or anion with an appropriate counter ion depending on the structure and the environment in which it is placed. In this specification, hydrogen ions are used as counter cations and hydroxide ions are used as counter anions as typical counter ions. However, compounds having other counter ions are also included in the compounds of the present invention. There may be one type of counter ion, or a plurality of types having an arbitrary ratio.

The dye compound represented by the general formula (1) can be a geometric isomer when the positions of R ¹ and R ² , X ¹ and X ^2, or A ¹ and A ² are different from each other. Further, when the heterocyclic ring Q has an asymmetric substituent, that is, when the heterocyclic ring Q in the general formula (1) is not C2 symmetric by an axis including a double bond, a geometric isomer centered on the double bond Can exist. Even if only one of the geometric isomers is described in the present specification, other geometric isomers are also included in the compound of the present invention. In addition, even when a geometric isomer mixture is obtained in the process of synthesis or purification, only the typical structure is described in this specification. In the case of a geometric isomer mixture, the abundance ratio may be any ratio.

The dye compound represented by the general formula (1) may contain an isotope (for example, ² H, ³ H, ¹³ C, ¹⁵ N, ¹⁷ O, ¹⁸ O, etc.).

[Dye Compound Represented by General Formula (8)]
Next, the dye compound represented by the following general formula (8) of the present invention will be described in detail. The dye compound represented by the general formula (8) is included in the dye compound represented by the general formula (1). The dye compound represented by the general formula (8) is a compound having a 1,3-benzodithiolane-2-ylidenepyrazolidinedione skeleton, and these are classified into merocyanine dyes (here, merocyanine dyes). The dye is defined, for example, by Shin Okawara, Ken Matsuoka, Tsuneaki Hirashima, Kojiro Kitao, “Functional Pigment” Kodansha Scientific Co., 1992, p. 52). A dye having such a skeleton (for example, in Japanese Patent No. 25552550, wherein R ⁸¹ and R ⁸² are ethyl groups and R ⁸⁴ is a t-butyl group in the general formula (8)) is used in, for example, an increase in a photosensitive composition. Although known as a dye-sensitive dye, its usefulness as a colorant has not been reported. This only known compound was studied as a sensitizing dye in the photosensitive composition and was intended to absorb only visible light with a very short wavelength in consideration of workability under safelight conditions. Therefore, only a light yellow color was exhibited, and it was impossible to imagine that the skeletal compound showed excellent performance as a colorant.
The present inventors pay attention to 1,3-benzodithiolane-2-ylidene-3,5-pyrazolidinedione compounds, and repeat the synthesis and evaluation in detail. It has been found that the benzodithiolane-2-ylidene-3,5-pyrazolidinedione compound exhibits particularly excellent performance as a yellow colorant.

In the general formula (8), R ⁸¹ and R ⁸² each independently represent a hydrogen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted acyl group, a substituted or unsubstituted group It represents an alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group.

In the general formula (8), R ⁸³ , R ⁸⁴ , R ⁸⁵ , and R ⁸⁶ each independently represent a hydrogen atom or a monovalent substituent. The monovalent substituent is not particularly limited, but representative examples include halogen atoms, aliphatic groups [saturated aliphatic groups (alkyl groups, cycloalkyl groups, bicycloalkyl groups, bridged cyclic saturated hydrocarbon groups or spiro A cyclic saturated aliphatic group including a saturated hydrocarbon 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 cyclo An alkenyl 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 (preferably a phenyl optionally having a substituent) Group), a heterocyclic group (preferably a 5- to 8-membered ring containing an oxygen atom, a sulfur atom or a nitrogen atom as a ring-constituting atom, which is an alicyclic ring, an aromatic ring or a heterocyclic ring. Cyano group, aliphatic oxy group (typically alkoxy group), aryloxy group, acyloxy group, carbamoyloxy group, aliphatic oxycarbonyloxy group (typically alkoxycarbonyloxy group), Aryloxycarbonyloxy group, amino group [including aliphatic amino group (typically alkylamino group), anilino group and heterocyclic amino group], acylamino group, aminocarbonylamino group, aliphatic oxycarbonylamino group (typically alkoxy Carbonylamino group), aryloxycarbonylamino group, sulfamoylamino group, aliphatic (typically alkyl) or arylsulfonylamino group, aliphatic thio group (typically alkylthio group), arylthio group, sulfamoyl group, aliphatic ( representative Alkyl) or arylsulfinyl group, aliphatic (typically alkyl) or arylsulfonyl group, acyl group, aryloxycarbonyl group, aliphatic oxycarbonyl group (typically alkoxycarbonyl group), carbamoyl group, aryl or heterocyclic azo Groups, imide groups, aliphatic oxysulfonyl groups (typically alkoxysulfonyl groups), aryloxysulfonyl groups, hydroxyl groups, nitro groups, carboxyl groups, and sulfo groups. The monovalent substituents mentioned in the above).

R ⁸¹ and R ⁸² are each independently preferably a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted acyl group having 2 to 30 carbon atoms, A substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, more preferably a substituted or unsubstituted phenyl group, substituted or unsubstituted hetero A cyclic group, a substituted or unsubstituted acyl group having 2 to 20 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, or a substituted or unsubstituted alkylsulfonyl group having 1 to 20 carbon atoms, Particularly preferably, an unsubstituted phenyl group, a pyridyl group, a substituted or unsubstituted acyl group having 2 to 10 carbon atoms, a substituted or unsubstituted group An alkoxycarbonyl group or a substituted or unsubstituted alkylsulfonyl group having 1 to 10 carbon atoms, from 2 to 10 carbon atoms.

R ⁸³ and R ⁸⁶ are each independently preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon group. An aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted acyloxy group having 2 to 30 carbon atoms, a hydroxyl group, or a halogen atom, more preferably a hydrogen atom, a substituted or unsubstituted alkoxy having 1 to 20 carbon atoms. Group, a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, or a substituted or unsubstituted acyloxy group having 2 to 20 carbon atoms, particularly preferably a hydrogen atom, or a substituted or unsubstituted carbon atom having 1 to 2 carbon atoms. 18 alkoxy groups.

R ⁸⁴ and R ⁸⁵ are each independently preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a halogen atom, or a cyano group. And more preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and particularly preferably a hydrogen atom.

  Regarding the preferred combination of substituents in the dye compound represented by the general formula (8) of the present invention, a compound in which at least one of these substituents is the above preferred group is preferred, and more various substituents are the above. A compound that is a preferred group is more preferred, and a compound in which all substituents are the preferred groups is most preferred.

In the preferred combination of substituents in the dye compound represented by the general formula (8) of the present invention, R ⁸¹ and R ⁸² are each independently substituted or unsubstituted aryl groups having 6 to 10 carbon atoms, substituted or unsubstituted. A substituted or unsubstituted acyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms. R ⁸³ is a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, or a substituted or unsubstituted acyloxy group having 2 to 30 carbon atoms, and R ⁸⁴ is a hydrogen atom, or a substituted or unsubstituted carbon number. 1 to 30 alkyl ^group, a ^{R 85} is a hydrogen ^{atom, R 86} is a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms or if substituted, Is an unsubstituted acyloxy group having 2 to 30 carbon atoms.

More preferable combinations are as follows: R ⁸¹ and R ⁸² are each independently substituted or unsubstituted phenyl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted acyl group having 2 to 20 carbon atoms, substituted or unsubstituted Or a substituted or unsubstituted alkylsulfonyl group having 1 to 20 carbon atoms, and R ⁸³ is a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted group. A substituted acyloxy group having 2 to 20 carbon atoms, R ⁸⁴ is a hydrogen atom, R ⁸⁵ is a hydrogen atom, R ⁸⁶ is a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted group. The combination is a substituted acyloxy group having 2 to 20 carbon atoms.

Particularly preferred combinations are those in which R ⁸¹ and R ⁸² are an unsubstituted phenyl group, an unsubstituted pyridyl group, a substituted or unsubstituted acyl group having 2 to 18 carbon atoms, a substituted or unsubstituted alkoxycarbonyl having 2 to 18 carbon atoms. A substituted or unsubstituted alkylsulfonyl group having 1 to 18 carbon atoms, R ⁸³ is a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, R ⁸⁴ is a hydrogen atom, and R ⁸⁵ is A combination that is a hydrogen atom and R ⁸⁶ is a substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms.

[Dye Compound Represented by General Formula (9)]
Next, the dye compound represented by the following general formula (9) of the present invention will be described in detail. The dye compound represented by the general formula (9) is included in the dye compound represented by the general formula (1). The dye compound represented by the general formula (9) is classified into a merocyanine dye in which 1,3-benzodithiolane is a basic heterocyclic ring and 6-hydroxy-2-pyridone is an acidic heterocyclic ring (here, (The basic heterocyclic ring and the acidic heterocyclic ring are defined, for example, by James, “The Theory of the Photographic Process”, 4th edition, McMillan Publishing Company, 1977, page 197.) . However, a dye compound having a skeleton composed of such an acidic heterocyclic ring and a basic heterocyclic ring has never been known so far.

In the general formula (9), R ⁹¹ , R ⁹² , R ⁹³ , R ⁹⁴ , R ⁹⁵ , R ⁹⁶ and R ⁹⁷ each independently represent a hydrogen atom or a monovalent substituent. The monovalent substituent is not particularly limited, but representative examples include halogen atoms, aliphatic groups [saturated aliphatic groups (alkyl groups, cycloalkyl groups, bicycloalkyl groups, bridged cyclic saturated hydrocarbon groups or spiro A cyclic saturated aliphatic group including a saturated hydrocarbon 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 cyclo An alkenyl 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 (preferably a phenyl optionally having a substituent) Group), a heterocyclic group (preferably a 5- to 8-membered ring containing an oxygen atom, a sulfur atom or a nitrogen atom as a ring-constituting atom, which is an alicyclic ring, an aromatic ring or a heterocyclic ring. Cyano group, aliphatic oxy group (typically alkoxy group), aryloxy group, acyloxy group, carbamoyloxy group, aliphatic oxycarbonyloxy group (typically alkoxycarbonyloxy group), Aryloxycarbonyloxy group, amino group [including aliphatic amino group (typically alkylamino group), anilino group and heterocyclic amino group], acylamino group, aminocarbonylamino group, aliphatic oxycarbonylamino group (typically alkoxy Carbonylamino group), aryloxycarbonylamino group, sulfamoylamino group, aliphatic (typically alkyl) or arylsulfonylamino group, aliphatic thio group (typically alkylthio group), arylthio group, sulfamoyl group, aliphatic ( representative Alkyl) or arylsulfinyl group, aliphatic (typically alkyl) or arylsulfonyl group, acyl group, aryloxycarbonyl group, aliphatic oxycarbonyl group (typically alkoxycarbonyl group), carbamoyl group, aryl or heterocyclic azo Groups, imide groups, aliphatic oxysulfonyl groups (typically alkoxysulfonyl groups), aryloxysulfonyl groups, hydroxyl groups, nitro groups, carboxyl groups, and sulfo groups. And may have a monovalent substituent).

R ⁹¹ is preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, more preferably a hydrogen atom, or substituted or unsubstituted. A substituted alkyl group having 1 to 20 carbon atoms, particularly preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 18 carbon atoms.

R ⁹² is preferably a hydrogen atom, a cyano group, a nitro group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted acyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms. Group, or a substituted or unsubstituted aryloxy group having 7 to 30 carbon atoms, more preferably a hydrogen atom, a cyano group, or a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, particularly preferably. It is a cyano group.

R ⁹³ is preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, more preferably a hydrogen atom, or substituted or unsubstituted. A substituted alkyl group having 1 to 20 carbon atoms, particularly preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 18 carbon atoms.

R ⁹⁴ and R ⁹⁷ are each independently preferably a hydrogen atom, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, and more A hydrogen atom or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms is preferable, and a hydrogen atom or an unsubstituted alkoxy group having 1 to 18 carbon atoms is particularly preferable.

R ⁹⁵ and R ⁹⁶ are each independently preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a halogen atom, or cyano. Group, more preferably a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and particularly preferably a hydrogen atom.

  Regarding the preferred combination of substituents in the dye compound represented by the general formula (9) of the present invention, a compound in which at least one of these substituents is the above preferred group is preferred, and more various substituents are the above. A compound that is a preferred group is more preferred, and a compound in which all substituents are the preferred groups is most preferred.

In the preferred combination of substituents in the dye compound represented by the general formula (9) of the present invention, R ⁹¹ is a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and R ⁹² is a cyano group. Or a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, R ⁹³ is a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, and R ⁹⁴ is substituted or unsubstituted. An alkoxy group having 1 to 30 carbon atoms, or a substituted or unsubstituted acyloxy group having 2 to 30 carbon atoms, R ⁹⁵ is a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, R ⁹⁶ is a hydrogen atom, R ⁹⁷ is a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, or a substituted or unsubstituted acyloxy group having 2 to 30 carbon atoms Is a combination.

A more preferred combination is that R ⁹¹ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, R ⁹² is a cyano group, or a substituted or unsubstituted alkoxycarbonyl group having 2 to 20 carbon atoms, and R ⁹³ Is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, R ⁹⁴ is a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted carbon group having 2 to 20 carbon atoms. An acyloxy group, R ⁹⁵ is a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, R ⁹⁶ is a hydrogen atom, and R ⁹⁷ is a substituted or unsubstituted carbon atom having 1 to 20 carbon atoms. A combination which is an alkoxy group or a substituted or unsubstituted acyloxy group having 2 to 20 carbon atoms.

A particularly preferred combination is that R ⁹¹ is an unsubstituted alkyl group having 1 to 8 carbon atoms, R ⁹² is a cyano group, R ⁹³ is a hydrogen atom, or an unsubstituted alkyl group having 1 to 8 carbon atoms. R ⁹⁴ is a substituted or unsubstituted alkoxy group having 1 to 8 carbon atoms or a substituted or unsubstituted acyloxy group having 2 to 8 carbon atoms, R ⁹⁵ is a hydrogen atom, R ⁹⁶ is a hydrogen atom, ⁹⁷ is a combination in which ⁹⁷ is an unsubstituted alkoxy group having 1 to 8 carbon atoms or an unsubstituted acyloxy group having 2 to 8 carbon atoms.

[Dye Compound Represented by General Formula (10)]
Next, the dye compound represented by the following general formula (10) of the present invention will be described in detail. The dye compound represented by the general formula (10) is included in the dye compound represented by the general formula (1). The compound represented by the general formula (10) is classified into merocyanine dyes in which 1,3-benzodithiolane is a basic heterocyclic ring and, for example, pyrrolotriazole is an acidic heterocyclic ring. However, a dye compound having a skeleton composed of such an acidic heterocyclic ring and a basic heterocyclic ring has never been known so far.

In the general formula (10), X ¹⁰¹ and X ¹⁰² each independently represent —N═ or —C (R ¹⁰⁷ ) ═.

In the general formula (10), R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ and R ¹⁰⁷ each independently represent a hydrogen atom or a monovalent substituent. The monovalent substituent is not particularly limited, but representative examples include halogen atoms, aliphatic groups [saturated aliphatic groups (alkyl groups, cycloalkyl groups, bicycloalkyl groups, bridged cyclic saturated hydrocarbon groups or spiro A cyclic saturated aliphatic group including a saturated hydrocarbon 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 cyclo An alkenyl 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 (preferably a phenyl optionally having a substituent) Group), a heterocyclic group (preferably a 5- to 8-membered ring containing an oxygen atom, sulfur atom or nitrogen atom as a ring-constituting atom, and an alicyclic ring, aromatic ring or heterocyclic ring. May be condensed), cyano group, aliphatic oxy group (typically alkoxy group), aryloxy group, acyloxy group, carbamoyloxy group, aliphatic oxycarbonyloxy group (typically alkoxycarbonyloxy group), aryl Oxycarbonyloxy group, amino group [including aliphatic amino group (typically alkylamino group), anilino group and heterocyclic amino group], acylamino group, aminocarbonylamino group, aliphatic oxycarbonylamino group (typically alkoxycarbonyl) Amino group), aryloxycarbonylamino group, sulfamoylamino group, aliphatic (typically alkyl) or arylsulfonylamino group, aliphatic thio group (typically alkylthio group), arylthio group, sulfamoyl group, aliphatic (typical) When Alkyl) or arylsulfinyl group, aliphatic (typically alkyl) or arylsulfonyl group, acyl group, aryloxycarbonyl group, aliphatic oxycarbonyl group (typically alkoxycarbonyl group), carbamoyl group, aryl or heterocyclic azo group , Imide groups, aliphatic oxysulfonyl groups (typically alkoxysulfonyl groups), aryloxysulfonyl groups, hydroxyl groups, nitro groups, carboxyl groups, and sulfo groups. The monovalent substituents mentioned above may be present.

X ¹⁰¹ is preferably -N =. X ¹⁰² is preferably -C (R ⁷ ) =.

R ¹⁰¹ is preferably a cyano group, a substituted or unsubstituted alkoxycarbonyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, more preferably a cyano group or a substituted group. Or it is an unsubstituted C1-C20 alkoxycarbonyl group, Most preferably, it is a substituted or unsubstituted C1-C18 alkoxycarbonyl group.

R ¹⁰² is preferably a cyano group, a substituted or unsubstituted alkoxycarbonyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, more preferably a cyano group or a substituted group. Or it is an unsubstituted C1-C20 alkoxycarbonyl group, Most preferably, it is a cyano group.

R ¹⁰³ and R ¹⁰⁶ are each independently preferably a hydrogen atom, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and more A hydrogen atom or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms is preferable, and a hydrogen atom or an unsubstituted alkoxy group having 1 to 18 carbon atoms is particularly preferable.

R ¹⁰⁴ and R ¹⁰⁵ are each independently preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a halogen atom, or cyano. Group, more preferably a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and particularly preferably a hydrogen atom.

R ¹⁰⁷ is preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, more preferably a substituted or unsubstituted carbon group having 6 to 20 carbon atoms. And particularly preferably a phenyl group having a substituent.

  Regarding the preferred combination of substituents in the dye compound represented by the general formula (10) of the present invention, a compound in which at least one of these substituents is the above preferred group is preferred, and more various substituents are the above. A compound that is a preferred group is more preferred, and a compound in which all substituents are the preferred groups is most preferred.

In a preferred combination of substituents in the dye compound represented by the general formula (10) of the present invention, X ¹⁰¹ is —N═, X ¹⁰² is ═C (R ¹⁰⁷ ) —, R ¹⁰¹ is a cyano group, Or a substituted or unsubstituted alkoxycarbonyl group having 1 to 30 carbon atoms, R ¹⁰² is a cyano group, or a substituted or unsubstituted alkoxycarbonyl group having 1 to 30 carbon atoms, and R ¹⁰³ is a hydrogen atom, substituted or unsubstituted A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms or a substituted or unsubstituted acyloxy group having 2 to 30 carbon atoms, and R ¹⁰⁴ is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms. R ¹⁰⁵ is a hydrogen atom, R ¹⁰⁶ is a hydrogen atom, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, or a substituted or unsubstituted carbon. It is a combination of a prime number 2-30 acyloxy group and R ¹⁰⁷ is a substituted or unsubstituted phenyl group.

A more preferable combination is that X ¹⁰¹ is —N═, X ¹⁰² is ═C (R ¹⁰⁷ ) —, and R ¹⁰¹ is a cyano group or a substituted or unsubstituted alkoxycarbonyl group having 1 to 20 carbon atoms. R ¹⁰² is a cyano group, or a substituted or unsubstituted alkoxycarbonyl group having 1 to 20 carbon atoms, and R ¹⁰³ is a hydrogen atom, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted group. An acyloxy group having 2 to 20 carbon atoms, R ¹⁰⁴ is a hydrogen atom, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, R ¹⁰⁵ is a hydrogen atom, and R ¹⁰⁶ is a hydrogen atom, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms or a substituted or unsubstituted acyloxy group having 2 to 20 carbon ^{atoms,, R 107} is a substituted or Is an unsubstituted phenyl group.

A particularly preferred combination is that X ¹⁰¹ is —N═, X ¹⁰² is ═C (R ¹⁰⁷ ) —, R ¹⁰¹ is a substituted or unsubstituted alkoxycarbonyl group having 1 to 18 carbon atoms, and R ¹⁰² is A cyano group, R ¹⁰³ is a hydrogen atom, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted acyloxy group having 2 to 10 carbon atoms, R ¹⁰⁴ is a hydrogen atom, R ¹⁰⁵ is a hydrogen atom, R ¹⁰⁶ is a hydrogen atom, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, or a substituted or unsubstituted acyloxy group having 2 to 10 carbon atoms, and R ¹⁰⁷ is substituted phenyl. A combination that is a group.

  Specific examples of the dye compound represented by the general formula (1) in the present invention include the compounds (1-1) to (1-17), the compounds (2-1) to (2-16), the compound (3- 1) to (3-21), compounds (4-1) to (4-8), compounds (5-1) to (5-10), compounds (6-1) to (6-20), compound ( Although 7-1)-(7-2) are shown below, this invention is not limited to these.

  In the compounds exemplified above, the compounds (5-1), (5-2), (5-6), and (5-8) to (5-10) are the dye compounds represented by the general formula (8). It is also an example. In the compounds exemplified above, the compounds (3-1) to (3-10), (3-15) and (3-16) are also examples of the dye compound represented by the general formula (9). In the compounds exemplified above, the compound (7-2) is also an example of the dye compound represented by the general formula (10).

The dye compound of the present invention is preferably used as yellow or orange among the three primary colors.
The maximum absorption wavelength of the dye compound of the present invention is preferably in the range of 380 to 480 nm, more preferably in the range of 390 to 450 nm.
The dye compound represented by the general formula (1) of the present invention can be synthesized by a conventionally known method or according thereto. Specifically, for example, a method of obtaining a compound (2-1) by reacting a heterocyclic dithiocarboxylic acid and benzoquinone as shown in the following reaction scheme, a benzodithiol having a nitrogen leaving group or a sulfur leaving group, and an electron It can be synthesized by a method of obtaining compounds (3-5) and (5-6) by reacting abundant heterocycles.

<Coloring composition>
The coloring composition of the present invention contains at least one medium and at least one dye compound represented by the general formula (1). The dye compound represented by the general formula (1) may be dissolved or dispersed in the medium. The colored composition in the present specification refers to a pigment dispersion, ink for ink jet recording, ink sheet for thermal transfer recording, color filter, writing pen, colored plastic, and other ink liquids.
The colored composition of the present invention can be effectively used particularly as an ink for inkjet recording, an ink sheet for thermal transfer recording, and a color filter.
In the colored composition of the present invention, the dye compound represented by the general formula (1) may be a colorless compound or a chromatic compound, but from the viewpoint of light fastness of the colored composition, The dye compound represented by the general formula (1) is preferably a chromatic compound. In addition, the coloring composition of this invention can be further colored with the dye or pigment added to a medium.

  In the colored composition of the present invention, the dye compound represented by the general formula (1) is preferably uniformly dissolved in the medium or dispersed and contained in the medium from the viewpoint of handleability. From the viewpoint of diversity of combination with the medium and light fastness, it is more preferable that the medium is dispersed in the medium. Here, the pigment compound represented by the general formula (1) is dispersed in the medium. The pigment compound represented by the general formula (1) is in a fine particle state and is suspended or suspended in the medium. It means being in a state.

  Although the coloring compound represented by the above general formula (1) is obtained as a crude pigment by the above production method, when used as the colored dispersion composition of the present invention, it is desirable to perform post-treatment. Examples of post-processing methods include, for example, solvent particle milling process such as solvent salt milling, salt milling, dry milling, solvent milling, acid pasting, solvent heat treatment, etc., resin, surfactant and dispersant. The surface treatment process by etc. is mentioned.

  The dye compound represented by the general formula (1) of the present invention is preferably subjected to a solvent heating treatment as a post-treatment. Examples of the solvent used in the solvent heat treatment include water, aromatic hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as chlorobenzene and o-dichlorobenzene, and alcohols such as isopropanol and isobutanol. Examples thereof include solvents, polar aprotic organic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone, glacial acetic acid, pyridine, and mixtures thereof. It is preferable to adjust the average particle diameter of the pigment to 0.01 μm to 1 μm by these post-treatments.

The dye compound represented by the general formula (1) by the above operation gives a regular crystal, which can be recognized from, for example, an X-ray diffraction diagram. As described in “Basics of X-ray Crystallography” (1973, Maruzen), according to Scherrer's formula, the full wave height half-width of the peak of the X-ray diffraction diagram (hereinafter referred to as half-width) Is inversely proportional to the average grain size.
In the present invention, it is preferable that the half-width of the maximum peak in the X-ray diffraction pattern of the solid is 0.40 ° or less in the previous stage in which the coloring compound represented by the general formula (1) is used as the coloring composition. More preferably, it is 0.30 ° or less. By forming large crystals, the fastness of the coloring composition is improved, and the dispersion stability is improved by reducing the active surface.
In the case where the maximum peak in the X-ray diffraction diagram is composed of a plurality of adjacent peaks, it can be determined from another appropriate single peak.

The coloring composition of the present invention includes at least one medium, and the medium may be an aqueous medium or a non-aqueous medium. From the viewpoint of ease of handling and environmental safety, A water-based coloring composition containing an aqueous medium is preferable.
In the colored composition of the present invention, as an aqueous medium for dispersing the pigment, a mixture containing water as a main component and optionally adding at least one hydrophilic organic solvent can be used.

  Examples of the hydrophilic organic solvent include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, and benzyl alcohol; ethylene glycol, diethylene glycol , Polyhydric alcohols such as triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol; ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, ethylene glycol butyl ether, diethylene glycol mono Chill 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 monoethyl ether, ethylene glycol monophenyl ether Glycol derivatives such as: ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine Amines such as 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 and the like can be mentioned.

  The aqueous coloring composition (pigment dispersion) in the present invention may further contain an aqueous resin. Examples of the aqueous resin include a water-soluble resin that dissolves in water, a water-dispersible resin that disperses in water, a colloidal dispersion resin, or a mixture thereof. Specific examples of the aqueous resin include acrylic, styrene-acrylic, polyester, polyamide, polyurethane, and fluorine resins.

  The coloring composition of the present invention preferably further includes at least one of a surfactant and a dispersant, and more preferably further includes at least one of a dispersant. By further including a surfactant and a dispersant, the dispersibility of the dye compound represented by the general formula (1) and the quality of the image formed using the colored composition can be improved.

The dispersant in the present invention is not particularly limited as long as it is a compound capable of dispersing the dye compound represented by the general formula (1) in a medium. For example, the dispersant described in “Pigment Dispersion Technology, Surface Treatment, Usage of Dispersant and Evaluation of Dispersibility (published by Technical Information Society 1999)” and the like can be suitably used in the present invention. In the present invention, from the viewpoint of dispersion stability, a surfactant or a hydrophilic polymer is preferable.
The content of the dispersant in the coloring composition is not particularly limited as long as the dye compound represented by the general formula (1) can be dispersed in the medium. For example, it can be 0.1-200 mass% with respect to the pigment | dye compound represented by General formula (1), and it is 1-100 mass% from a viewpoint of dispersion stability and the quality control of a coloring composition. Is preferable, and it is more preferable that it is 2-50 mass%.

  Examples of the surfactant include anionic, nonionic, cationic and amphoteric surfactants. Any surfactant may be used, but an anionic or nonionic surfactant is used. Is preferred.

  Examples of the anionic surfactant include fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl diaryl ether disulfonates, alkyl phosphates, and polyoxyethylene alkyls. Examples thereof include ether sulfate, polyoxyethylene alkyl aryl ether sulfate, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester salt, glycerol borate fatty acid ester, polyoxyethylene glycerol fatty acid ester and the like.

  Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, Examples thereof include glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, fluorine-based surfactant, and silicon-based surfactant.

  The non-aqueous coloring composition in the present invention is obtained by dispersing the dye compound represented by the general formula (1) in a non-aqueous vehicle (non-aqueous medium). Resins used in non-aqueous vehicles are, for example, petroleum resins, casein, shellac, rosin modified maleic resin, rosin modified phenolic resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber, chlorinated rubber, oxidized rubber, hydrochloric acid rubber , Phenolic resin, alkyd resin, polyester resin, unsaturated polyester resin, amino resin, epoxy resin, vinyl resin, vinyl chloride, vinyl chloride-vinyl acetate copolymer, acrylic resin, methacrylic resin, polyurethane resin, silicone resin, fluorine resin , Drying oil, synthetic drying oil, styrene / maleic acid resin, styrene / acrylic resin, polyamide resin, polyimide resin, benzoguanamine resin, melamine resin, urea resin chlorinated polypropylene, butyral resin, vinylidene chloride resin and the like. A photocurable resin may be used as the non-aqueous vehicle.

  Examples of the solvent used in the non-aqueous vehicle include aromatic solvents such as toluene, xylene, and methoxybenzene; acetates such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Propionate solvents such as ethoxyethyl propionate; Alcohol solvents such as methanol and ethanol; Ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether; Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone solvents; aliphatic hydrocarbon solvents such as hexane; N, N-dimethylformamide, γ-butyrolactam, N Lactone-based solvents γ- butyrolactone; methyl-2-pyrrolidone, aniline, nitrogen compound-based solvent such as pyridine carbamate esters such as a mixture of 48:52 of methyl carbamate and ethyl carbamate acid.

  The colored composition of the present invention can be obtained by dispersing the coloring compound represented by the general formula (1) and an aqueous or non-aqueous medium using a dispersing device. Examples of the dispersing device that can be used include a ball mill, a sand mill, a bead mill, a roll mill, a jet mill, a paint shaker, an attritor, an ultrasonic disperser, and a disper.

In the colored composition of the present invention, when the dye compound represented by the general formula (1) is contained as a pigment, the volume average particle diameter of the pigment particles is preferably 10 nm or more and 250 nm or less. The volume average particle diameter of the pigment particles refers to the particle diameter of the pigment itself or the particle diameter in a state where the additive is attached when an additive such as a dispersant is attached to the colorant.
The volume average particle diameter of the pigment particles in the present invention is measured using a Nanotrac UPA particle size analyzer (UPA-EX150; manufactured by Nikkiso Co., Ltd.). The volume average particle diameter of the pigment particles is measured by placing 3 ml of the pigment dispersion in a measurement cell and according to a predetermined measurement method. As parameters input at the time of measurement, the viscosity of the pigment dispersion is used as the viscosity, and the density of the pigment is used as the density of the dispersed particles.

  The more preferable volume average particle diameter of the pigment particles in the present invention is 10 nm or more and 250 nm or less, and more preferably 15 nm or more and 230 nm or less. By setting the number volume average particle diameter of the particles in the pigment dispersion to 10 nm or more, the storage stability of the colored composition is improved. On the other hand, the optical density of a coloring composition can be made high by setting it as 250 nm or less.

  The content of the coloring compound (pigment) represented by the general formula (1) contained in the colored composition of the present invention is preferably in the range of 1 to 35% by mass, and in the range of 2 to 25% by mass. It is more preferable. By setting the content to 1% or more, a sufficient image density can be obtained even when the colored composition is used alone as an ink. On the other hand, it can suppress that the dispersion stability of a pigment falls because a content rate shall be 35 mass% or less.

  Applications of the colored composition of the present invention include image recording materials for forming images, particularly color images. Specifically, ink-jet recording inks described in detail below, heat-sensitive recording materials, pressure-sensitive recording materials, recording materials using electrophotographic methods, transfer-type silver halide photosensitive materials, printing inks, recording pens, etc. Can be mentioned. Preferred are inkjet recording inks, thermal recording materials, and recording materials using an electrophotographic method, and more preferred are inkjet recording inks.

  The colored composition of the present invention can also be applied to a solid-state imaging device such as a CCD, a color filter for recording / reproducing a color image used in a display such as an LCD or PDP, and a dyeing solution for dyeing various fibers. .

[Ink for inkjet recording]
Next, the ink for ink jet recording (ink jet recording material) of the present invention will be described.
The ink for inkjet recording of the present invention (hereinafter sometimes referred to as “ink”) includes at least one of the above-described colored composition (pigment dispersion), preferably a water-soluble solvent, It can further comprise water and the like. Further, the pigment dispersion of the present invention may be used as it is.

  The content of the pigment dispersion in the ink of the present invention is preferably in the range of 1 to 100% by mass from the viewpoint of the hue, color density, saturation, transparency, etc. of the image formed on the recording medium, and 3 to 20 The range of mass% is particularly preferable, and the range of 3 to 10 mass% is most preferable among them.

In 100 parts by mass of the ink of the present invention, the pigment compound (pigment) represented by the general formula (1) is preferably contained in an amount of 0.1 to 20 parts by mass, and 0.2 to 10 parts by mass. It is more preferable to contain it by mass part or less, and it is further more preferable to contain 1-10 mass parts.
In addition to the dye compound (pigment) represented by the general formula (1), other pigments may be used in combination with the ink of the present invention. When two or more kinds of pigments are used in combination, the total content of the pigments is preferably in the above range.

  The ink of the present invention can be used not only for monochromatic image formation but also for full color image formation. In order to form a full color image, a magenta color ink, a cyan color ink, and a yellow color ink can be used, and a black color ink may be further used to adjust the color tone.

  Furthermore, in the ink of the present invention, another pigment can be used at the same time in addition to the coloring compound (pigment) represented by the general formula (1). Applicable yellow pigments (eg CI PY-74, CI PY-128, CI PY-155, CI PY-213), applicable magenta pigments (eg CI PV-19, CI PR-122) Any applicable cyan pigment (for example, CI PB-15: 3, CI PB-15: 4) should be used. Can do. Further, examples of applicable black materials include disazo, trisazo, and tetraazo pigments, as well as carbon black dispersions.

As the water-soluble solvent used in the ink jet recording ink of the present invention, polyhydric alcohols, polyhydric alcohol derivatives, nitrogen-containing solvents, alcohols, sulfur-containing solvents and the like are used.
Specific examples of polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,5-pentanediol, 1,2,6-hexanetriol, and glycerin.

  Examples of the polyhydric alcohol derivative include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diglycerin. And ethylene oxide adducts.

  Examples of the nitrogen-containing solvent include pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, and triethanolamine. Examples of alcohols include alcohols such as ethanol, isopropyl alcohol, butyl alcohol, and benzyl alcohol. Examples of the solvent include thiodiethanol, thiodiglycerol, sulfolane, dimethyl sulfoxide and the like. In addition, propylene carbonate, ethylene carbonate, or the like can be used.

  The water-soluble solvent used in the present invention may be used alone or in combination of two or more. The content of the water-soluble solvent is 1% by mass or more and 60% by mass or less, preferably 5% by mass or more and 40% by mass or less of the entire ink. By setting the content of the water-soluble solvent in the ink to 1% by mass or more, a sufficient optical density can be obtained. On the other hand, when the content is 60% by mass or less, an increase in the viscosity of the ink can be suppressed, and the stability of the ejection characteristics of the ink can be improved.

Preferred physical properties of the ink for ink jet recording of the present invention are as follows.
The surface tension of the ink is preferably 20 mN / m or more and 60 mN / m or less. More preferably, it is 20 mN or more and 45 mN / m or less, More preferably, it is 25 mN / m or more and 35 mN / m or less. By setting the surface tension to 20 mN / m or more, liquid overflow to the nozzle surface of the recording head can be suppressed. On the other hand, by setting it to 60 mN / m or less, the permeability to the recording medium after printing can be improved, and the drying time is shortened.
The surface tension is a value measured using a Wilhelmy surface tension meter in an environment of 23 ° C. and 55% RH.

The viscosity of the ink is preferably from 1.2 mPa · s to 8.0 mPa · s, more preferably from 1.5 mPa · s to less than 6.0 mPa · s, still more preferably from 1.8 mPa · s to 4. It is less than 5 mPa · s. By setting the viscosity to 8.0 mPa · s or less, the discharge property is improved. On the other hand, long-term jetting property becomes favorable by setting it as 1.2 mPa * s or more.
The above-mentioned viscosity (including those described later) was measured using a rotational viscometer Rheomat 115 (manufactured by Contraves) at 23 ° C. and a shear rate of 1400 s ⁻¹ .

  In addition to the components described above, water is added to the ink in the range of the above-described preferable surface tension and viscosity. The amount of water added is not particularly limited, but is preferably 10% by mass to 99% by mass, and more preferably 30% by mass to 80% by mass with respect to the entire ink.

  Furthermore, the ink for inkjet recording of the present invention, if necessary, for the purpose of controlling properties such as improvement of ejection properties, polyethylene derivatives, polyamines, polyvinyl pyrrolidone, polyethylene glycol, ethyl cellulose, carboxymethyl cellulose and other cellulose derivatives, polysaccharides And other derivatives thereof, other water-soluble polymers, acrylic polymer emulsions, polyurethane emulsions, polymer emulsions such as hydrophilic latex, hydrophilic polymer gels, cyclodextrins, macrocyclic amines, dendrimers, crown ethers, urea and derivatives thereof, Acetamide, silicone surfactants, fluorine surfactants, and the like can be used.

In order to adjust conductivity and pH, compounds of alkali metals such as potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide, triethanolamine, diethanolamine, ethanolamine, 2-amino-2-methyl Nitrogen-containing compounds such as -1-propanol, alkaline earth metal compounds such as calcium hydroxide, acids such as sulfuric acid, hydrochloric acid and nitric acid, strong acid and weak alkali salts such as ammonium sulfate, and the like can be used.
Furthermore, a pH buffer, an antioxidant, an antifungal agent, a viscosity modifier, a conductive agent, an ultraviolet absorber, and the like can be added as necessary.

The ink for ink jet recording of the present invention can be used in an image forming method using an ink jet recording method. As the ink jet recording method, a known method can be applied without particular limitation.
The ink jet recording method supplies energy to ink for ink jet recording, and images on known image receiving materials such as plain paper, resin-coated paper, ink jet special paper, film, electrophotographic co-paper, fabric, glass, metal, ceramics, etc. Is formed.
Further, there is no limitation on the ink jet recording method, and a known method, for example, a charge control method that ejects ink using electrostatic attraction, a drop-on-demand method (pressure pulse method) that uses the vibration pressure of a piezo element, An acoustic ink jet method in which an electrical signal is converted into an acoustic beam and ink is irradiated and ink is ejected by using radiation pressure, and a thermal ink jet method in which ink is heated to form bubbles and the generated pressure is used is used. be able to.

[Ink sheet for thermal transfer recording]
The thermal transfer recording ink sheet of the present invention is characterized by containing at least one 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. In addition to the dye compound represented by the general formula (1), other dye compounds may be used simultaneously.

In order to apply the thermal transfer recording ink sheet to a thermal transfer recording material capable of full color image recording, a cyan ink sheet containing a heat-diffusible cyan dye capable of forming a cyan image, and a magenta image are formed. It is preferable that a magenta ink sheet containing a heat-diffusible magenta dye capable of forming a yellow image 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. As a magenta ink sheet containing a heat-diffusible magenta dye capable of forming a magenta image, for example, those described in JP-A-2-123166 can be preferably used. As a yellow ink sheet containing a heat diffusible yellow dye capable of forming a yellow image, for example, those described in JP-A-1-225559 can be preferably used.

(Support)
As the support for the thermal transfer recording ink sheet, 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.

(Dye-donating layer)
The binder resin that can be used in the dye-donating layer of the thermal transfer recording ink sheet has high heat resistance, and when heated, the dye compound represented by the general formula (1) and other dye compounds are image receiving materials. The type is not particularly limited as long as it does not hinder the transition. 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.

(Functional layer)
The thermal transfer recording ink sheet may have a layer other than the dye-donating layer as long as it does not excessively impair the effects of the present invention. 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 compound represented by the general formula (1) and other dye compounds toward the support. Can do. Examples of the back layer include a heat resistant slip layer, and can prevent adhesion of the thermal head to the ink sheet.

[Thermal transfer recording method]
When performing thermal transfer recording using the thermal transfer recording ink sheet, a heating means such as a thermal head and an image receiving material are used in combination. That is, thermal energy is applied to the ink sheet from the thermal head in accordance with the image recording signal, and the dye compound represented by the general formula (1) and other dye compounds in the portion to which the thermal energy is applied migrate to the image receiving material and are fixed. The thermal transfer recording method is characterized in that image recording is performed as a result. 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 filter〕
The color filter in the present invention includes at least one dye compound represented by the general formula (1). 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.
Moreover, 5-80 mass% is preferable with respect to the total mass of a filter layer, and, as for content of the pigment | dye compound represented by General formula (1) contained in a color filter, 10-60 mass% is more preferable. In addition, the smaller the volume average particle diameter of the dye compound represented by the general formula (1) contained in the color filter, the better the transmittance of the color filter. On the other hand, considering the ease of handling, it is 10 to 100 nm. Is preferable, and 10 to 50 nm is more preferable.

The features of the present invention will be described more specifically with reference to synthesis examples and 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. Unless otherwise specified, “part” and “%” are based on mass.

Example 1
The compounds (2-1), (2-3), (2-4), (2-6), (3-5), (3-9), (5-9), ( 6-1), (6-2), (6-3), (6-13), (6-14), (6-15), (6-16), and (7-2) were synthesized, respectively. .

[Synthesis Example 1]

Compound (a) was synthesized according to J. Org. Chem. 69, 2164-2177 (2004).
1.31 g of compound (a) and 0.77 g of barbituric acid were suspended in 40 mL of dimethyl sulfoxide and stirred at 80 ° C. for 30 minutes. 40 mL of water was added to the obtained uniform solution, and the deposited precipitate was separated by filtration. The obtained solid was washed with water and dried to obtain 1.03 g of compound (2-1) (yellow crystals).
¹ H-NMR (DMSO-d ₆ ): 6.8 (s, 2H), 10.3 (s, 2H), 11.2 (s, 2H)
Infrared absorption spectrum (cm ⁻¹ ): 3423 (br), 3176 (br), 3023 (br), 2831 (br), 1711 (s), 1632 (s), 1443 (s)

[Synthesis Example 2]
0.62 g of the compound (2-1) was suspended in 20 mL of tetrahydrofuran, and 0.42 mL of acetic anhydride and 0.61 mL of triethylamine were sequentially added. The mixture was heated to reflux for 2.5 hours. The obtained heterogeneous reaction mixture was cooled to room temperature, and the deposited precipitate was filtered off. The obtained solid was washed with tetrahydrofuran and dried to obtain 0.54 g of compound (2-3) (pale yellow crystals).
¹ H-NMR (DMSO-d ₆ ): 2.4 (s, 6H), 7.5 (s, 2H), 11.4 (s, 2H)
Infrared absorption spectrum (cm ⁻¹ ): 3431 (br), 3184 (br), 3037 (br), 2840 (w), 1774 (m), 1727 (m), 1645 (m), 1452 (s), 1184 (m)

[Synthesis Example 3]

1.31 g of compound (a) and 0.86 g of thiobarbituric acid were suspended in 20 mL of dimethyl sulfoxide and stirred at 60 ° C. for 30 minutes. 20 mL of water was added to the obtained uniform solution, and the deposited precipitate was separated by filtration. The obtained solid was washed with water and dried to obtain 1.32 g of compound (2-4) (yellow crystals).
¹ H-NMR (DMSO-d ₆ ): 6.8 (s, 2H), 10.4 (s, 2H), 12.4 (s, 2H)
Infrared absorption spectrum (cm ^-1 ): 3400-3500 (s, br), 3132 (s, br), 1639 (s), 1429 (s), 1149 (s), 1005 (m)

[Synthesis Example 4]
0.65 g of the compound (2-4) was suspended in 20 mL of tetrahydrofuran, and 0.42 mL of acetic anhydride and 0.61 mL of triethylamine were sequentially added. The mixture was heated to reflux for 2.5 hours. The obtained homogeneous solution was cooled to room temperature, and the deposited precipitate was filtered off. The obtained solid was washed with tetrahydrofuran and dried to obtain 0.45 g of compound (2-6) (yellow crystals).
¹ H-NMR (DMSO-d ₆ ): 2.4 (s, 6H), 7.5 (s, 2H), 12.6 (s, 2H)
Infrared absorption spectrum (cm ⁻¹ ): 3432 (br), 3000-3120 (br), 1774 (s), 1632 (s), 1457 (s), 1184 (s)

[Synthesis Example 5]

2.62 g of compound (a) and 1.54 g of 3-cyano-2,6-dihydroxypyridine (b) were suspended in 50 mL of dimethyl sulfoxide and stirred at room temperature for 2 hours. The resulting homogeneous solution was stirred at 80 ° C. for 2 hours. After cooling, 100 mL of diluted hydrochloric acid (1 N) was added, and the deposited precipitate was filtered off. The obtained solid was washed with water and dried to obtain 2.0 g of compound (3-5) (yellow-orange crystal).
¹ H-NMR (DMSO-d ₆ ): 6.9 (s, 2H), 8.7 (s, 1H), 10.5 (s, 1H), 10.6 (s, 1H), 11.8 (s, 1H)
Infrared absorption spectrum (cm ⁻¹ ): 3000-3500 (br), 2224 (m), 1659 (s), 1568 (s), 1417 (s), 1286 (s)

[Synthesis Example 6]
0.90 g of compound (3-5) and 1.66 g of potassium carbonate were suspended in 20 mL of dimethylacetamide under a nitrogen atmosphere, and 0.64 mL of iodoethane was added. The mixture was stirred at 60 ° C. for 7 hours. After cooling, the precipitate was filtered off. The obtained solid was poured into water, heated and stirred, filtered again, and dried to obtain 0.90 g of compound (3-9) (orange crystals).
¹ H-NMR (CDCl ₃ ): 1.3 (t, 3H), 1.5 (t, 6H), 4.1-4.3 (m, 6H), 6.9 (s, 2H), 8.2 (s, 1H)
Infrared absorption spectrum (cm ⁻¹ ): 3300-3600 (br), 1978 (w), 2222 (m), 1670 (m), 1624 (s), 1572 (s), 1431 (s), 1294 (s )

[Synthesis Example 7]

3.27 g of compound (a) and 2.77 g of 1,2-diphenylpyrazolidine-3,5-dione were suspended in 20 mL of dimethyl sulfoxide and stirred at 80 ° C. for 1 hour. After cooling, 10 mL of 1N aqueous hydrochloric acid was added, and the deposited precipitate was filtered off. The obtained solid was washed with water and dried to obtain 2.2 g of compound (5-9) (yellow-orange crystal).
¹ H-NMR (DMSO-d ₆ ): 6.9 (s, 2H), 7.2 (t, 2H), 7.3-7.5 (m, 8H), 10.5 (s, 2H)
Infrared absorption spectrum (cm ^-1 ): 3000-3500 (br), 1503 (s), 1362 (m)

[Synthesis Example 8]

3.27 g of compound (a) and 3.13 g of compound (c) were dissolved in 50 mL of acetic acid and 5 mL of pyridine and heated to reflux for 9 hours. After cooling to room temperature, the precipitated solid was filtered off. It was washed with water and dried to obtain 2.30 g of compound (6-1) (light yellow crystals).
¹ H-NMR (DMSO-d ₆ ): 3.2 (s, 3H), 6.8 (s, 2H), 7.2 (t, 1H), 7.4 (t, 2H), 8.0 (d, 2H), 10.3 (s, 1H), 10.4 (s, 1H)
Infrared absorption spectrum (cm ⁻¹ ): 3000-3500 (br), 1630 (m), 1595 (m), 1497 (s), 1338 (m)

[Synthesis Example 9]
0.71 g of the compound (6-1) was suspended in 20 mL of tetrahydrofuran, and 0.42 mL of acetic anhydride and 0.61 mL of triethylamine were sequentially added. This was heated to reflux for 2 hours, the precipitated solid was filtered off, washed with tetrahydrofuran, and dried to obtain 0.71 g of compound (6-2) (yellow crystals).
¹ H-NMR (DMSO-d ₆ ): 2.1 (s, 3H), 2.4 (s, 3H), 2.4 (s, 3H), 7.2 (t, 1H), 7.4 (t, 2H), 7.5 (s, 2H), 7.9 (d, 2H)
Infrared absorption spectrum (cm ⁻¹ ): 3350-3550 (br), 1774 (s), 1657 (m), 1527 (s), 1497 (s), 1180 (s)

[Synthesis Example 10]
0.71 g of the compound (6-1) and 0.83 g of potassium carbonate were suspended in 20 mL of dimethylacetamide under a nitrogen atmosphere. 0.56 mL of iodomethane was added and stirred at room temperature for 9 hours. The precipitated solid was filtered off and washed with dimethylacetamide and then water. Drying gave 0.50 g of compound (6-3) (yellow crystals).
¹ H-NMR (TFA-d): 3.0 (s, 3H), 4.1 (s, 6H), 7.3 (s, 2H), 7.5-7.7 (m, 5H)
Infrared absorption spectrum (cm ^-1 ): 3300-3600 (br), 1662 (m), 1525 (s), 1489 (s), 1335 (m), 1259 (m)

[Synthesis Example 11]

3.27 g of compound (a) and 1.40 g of compound (d) were suspended in 50 mL of dimethyl sulfoxide, and this was stirred at 80 ° C. for 1.5 hours. After cooling to room temperature, 200 mL of water was added, and the precipitated solid was filtered off. After washing with water, it was dried to obtain 3.10 g of compound (6-13) (pale yellow crystals).
¹ H-NMR (DMSO-d ₆ ): 2.6 (s, 3H), 2.6 (s, 3H), 6.8 (s, 2H), 10.5 (br, 2H)
Infrared absorption spectrum (cm ^-1 ): 2500-3600 (br), 1701 (m), 1606 (m), 1545 (s), 1498 (s), 1471 (s), 1423 (s), 1330 (s )

[Synthesis Example 12]
0.96 g of the compound (6-13) was suspended in 20 mL of tetrahydrofuran, and 0.85 mL of acetic anhydride and 1.7 mL of triethylamine were sequentially added. This was heated to reflux for 9 hours, cooled to room temperature, and 20 mL of water was added. The precipitated solid was collected by filtration, washed with water, and dried to obtain 0.47 g of compound (6-14) (pale yellow crystals).
¹ H-NMR (CDCl ₃ ): 2.6 (s, 6H), 2.6 (s, 3H), 2.7 (s, 3H), 7.4 (s, 2H)
Infrared absorption spectrum (cm ^-1 ): 3300-3600 (br), 1768 (s), 1558 (s), 1510 (m), 1468 (m), 1427 (m), 1369 (m), 1330 (m ), 1190 (s)

[Synthesis Example 13]
0.48 g of the compound (6-13) and 0.55 g of potassium carbonate were suspended in 15 mL of dimethylacetamide under a nitrogen atmosphere. 0.25 mL of iodomethane was added and stirred at room temperature for 6.5 hours. 30 mL of water was added, and the precipitated solid was filtered off and washed with water. Drying gave 0.25 g of compound (6-15) (dark yellow crystals).
¹ H-NMR (CDCl ₃ ): 2.6 (s, 3H), 2.6 (s, 3H), 3.9 (s, 3H), 4.0 (s, 3H), 6.9 (s, 2H)
Infrared absorption spectrum (cm ⁻¹ ): 3300-3600 (br), 2937 (br, m), 1722 (m), 1554 (s), 1485 (s), 1327 (s), 1263 (s), 1055 (m)

[Synthesis Example 14]
0.48 g of the compound (6-13) and 0.55 g of potassium carbonate were suspended in 15 mL of dimethylacetamide under a nitrogen atmosphere. 0.50 mL of iodoethane was added and stirred at 60 ° C. for 3 hours. 30 mL of water was added, and the precipitated solid was filtered off and washed with water. Drying gave 0.40 g of compound (6-16) (dark yellow crystals).
¹ H-NMR (CDCl ₃ ): 1.4-1.6 (m, 6H), 2.6 (s, 3H), 2.6 (s, 3H), 3.9-4.1 (m, 4H), 6.9 (s, 2H)
Infrared absorption spectrum (cm ^-1 ): 3300-3600 (br), 1551 (s), 1327 (s), 1265 (s), 1055 (m)

[Synthesis Example 15]

0.92 g of compound (e) and 0.53 ml of dimethyl sulfate were mixed and reacted at 120 ° C. for 4 hours. After cooling to room temperature, 10 ml of acetic acid, 2.58 g of compound (f) and 1 ml of pyridine were added and reacted at 100 ° C. for 4 hours. After cooling to room temperature, 30 ml of methanol was added and the resulting solid was filtered off. It was washed with acetone and dried to obtain 3 g of compound (7-2) (red crystals).
¹ H-NMR (TFA-d): 1.1 (s, 18H), 1.3 (brs, 4H), 1.6 (s, 9H), 1.7 (m, 2H), 1.8-1.9 (m, 3H), 2.1 (m , 1H), 6.5 (s, 1H), 7.9 (d, 2H), 8.1 (m, 2H), 8.4 (d, 2H), 8.6 (m, 2H)
MS: m / z 666 (M ^<+> ).

(Example 2-1)
0.40 g of the compound (6-2) obtained above was suspended in 8 ml of a 1: 1 mixture of N, N-dimethylacetamide and water and stirred at 100 ° C. for 3 hours. This suspension was filtered while hot, and the solid on the filter paper was washed with water and methanol, and then dried to obtain 0.40 g of a yellow solid. This solid is characterized by the following diffraction angle 2θ in a powder X-ray diffraction pattern (measured using Rigaku RINT 2000, Inc., the same applies hereinafter) by CuKα ray irradiation.
High intensity: 24.6 ° (half width 0.24 °), medium intensity: 5.9 °, 7.6 °, 9.7 °, 11.4 °, 12.9 °, 15.4 °, 18 0.0 °, 19.1 °, 21.9 °, 25.5 °, 27.1 °

(Example 2-2)
The same operation as in Example 2-1 was performed, except that 0.40 g of the compound (2-3) was used instead of the compound (6-2) in Example 2-1. 0.40 g of solid was obtained. This solid is characterized by the following diffraction angle 2θ in the powder X-ray diffraction diagram (CuKα ray irradiation).
High intensity: 8.3 ° (half-value width 0.30 °), medium intensity: 9.0 °, 11.7 °, 25.0 °, 27.0 °

(Example 2-3)
The procedure of Example 2-1 was repeated except that 0.40 g of the compound (2-6) was used instead of the compound (6-2) in Example 2-1. 0.40 g of solid was obtained. This solid is characterized by the following diffraction angle 2θ in the powder X-ray diffraction diagram (CuKα ray irradiation).
High intensity: 8.0 ° (half width 0.31 °), 24.4 ° (half width 0.49 °), 26.7 ° (half width 0.52 °), medium strength: 8.8 ° 11.8 °

(Example 2-4)
The procedure of Example 2-1 was repeated except that 0.40 g of the compound (3-9) was used instead of the compound (6-2) in Example 2-1. 0.40 g of solid was obtained. This solid is characterized by the following diffraction angle 2θ in the powder X-ray diffraction diagram (CuKα ray irradiation).
High intensity: 9.0 ° (half width 0.23 °), medium intensity: 7.1 °, 25.6 °, 27.6 °

(Example 2-5)
The procedure of Example 2-1 was repeated except that 0.40 g of the compound (6-16) was used instead of the compound (6-2) in Example 2-1. 0.40 g of solid was obtained. This solid is characterized by the following diffraction angle 2θ in the powder X-ray diffraction diagram (CuKα ray irradiation).
High intensity: 8.5 ° (half width 0.27 °), 24.9 ° (half width 0.34 °), medium strength: 15.1 °, 25.9 °

(Example 2-6)
The same operation as in Example 2-1 was performed, except that 0.40 g of the compound (6-14) was used instead of the compound (6-2) in Example 2-1. 0.40 g of solid was obtained. This solid is characterized by the following diffraction angle 2θ in the powder X-ray diffraction diagram (CuKα ray irradiation).
High strength: 8.8 ° (half-value width 0.29 °), medium strength: 12.0 °, 24.1 °

(Example 2-7)
The procedure of Example 2-1 was repeated except that 0.40 g of the compound (6-15) was used instead of the compound (6-2) in Example 2-1. 0.40 g of solid was obtained. This solid is characterized by the following diffraction angle 2θ in the powder X-ray diffraction diagram (CuKα ray irradiation).
High intensity: 9.1 ° (half width 0.29 °), medium intensity: 24.9 °, 26.1 °

(Example 2-8)
A yellow solid was obtained in the same manner as in Example 2-1, except that 0.40 g of the compound (6-3) was used instead of the compound (6-2) in Example 2-1. 0.40 g was obtained. This solid is characterized by the following diffraction angle 2θ in the powder X-ray diffraction diagram (CuKα ray irradiation).
High strength: 7.5 ° (half-width 0.22 °), Medium strength: 9.6 °, 15.0 °, 25.9 °

(Example 2-9)
The procedure of Example 2-1 was repeated except that 0.40 g of the compound (5-9) was used instead of the compound (6-2) in Example 2-1. 0.40 g of solid was obtained. This solid is characterized by the following diffraction angle 2θ in the powder X-ray diffraction diagram (CuKα ray irradiation).
High intensity: 6.0 ° (half width 0.33 °), medium intensity: 13.7 °, 25.2 °

(Comparative Example 2-A)
Instead of compound (6-2) in Example 2-1, C.I. I. Pigment Yellow 128 (Chrofthal (registered trademark) Yellow 8GN manufactured by Ciba Specialty Chemicals Co., Ltd.) was used except that 0.40 g was used. As a result, 0.40 g of a yellow solid was obtained. was gotten. This solid is characterized by the following diffraction angle 2θ in the powder X-ray diffraction diagram (CuKα ray irradiation).
High intensity: 6.4 ° (half width 0.48 °), medium intensity: 23.1 °, 25.9 °, 26.7 °

  In the solid powder X-ray diffractograms obtained in accordance with Examples (2-1) to (2-8) and Comparative Example (2-A), the half widths of the peaks having the highest diffraction intensity are summarized in Table 6 below. It was.

  From Table 6, it can be seen that the pigment obtained from the compound of the present invention is composed of crystals having excellent crystallinity and a large particle size.

-Solvent resistance evaluation-
The solvent resistance of a solution obtained by adding 0.05 part of the pigment obtained above to 200 parts of the organic solvent shown in Table 7 and allowing to stand at room temperature for 24 hours was evaluated. Evaluation criteria are C in which the compound of the example or comparative example is completely dissolved in the organic solvent, B is insoluble in the filtrate although the insoluble matter remains without being completely dissolved, and B is insoluble. Was left and the filtrate was not colored. As the organic solvent, four types of methanol, acetone, ethyl acetate, and xylene were used.
In addition, a similar evaluation was made on C.I. I. Pigment Yellow 74 (Irgalite (registered trademark) Yellow GO manufactured by Ciba Specialty Chemicals) was also used. The evaluation results are shown in Table 7 below.

  From Table 7, it can be seen that the compound contained in the colored composition of the present invention has low solubility in organic solvents and is excellent in organic solvent resistance.

(Example 3-1)
-Preparation of aqueous coloring dispersion composition-
In a zirconia container with a total content of 12 ml,
-0.25 g of the solid of the compound (6-2) obtained according to Example 2-1 above,
・ 0.05 g of sodium oleate
・ 0.50 g of glycerin,
-4.20 g of deionized water,
Was put together with 10 g of zirconia beads having a diameter of 0.1 mm and pulverized using a planetary ball mill (Fritsch Japan Co., Ltd., P-7 type) (rotation speed: 300 rpm, pulverization time: 3 hours). After completion of the pulverization, the beads were separated from the mixture in the container by decantation to obtain a pigment dispersion composition (coloring composition) containing 5.0% of the compound (6-2) in a fine particle state.
When this colored composition was diluted 30 times with deionized water and measured by a dynamic light scattering method (Nikkiso Co., Ltd. Microtrac UPA-150), the volume average particle size of the contained fine particles was 70 nm. .

(Example 3-2)
In Example 3-1, the solid of the compound (3-9) obtained according to Example 2-4 was used instead of the solid of the compound (6-2) obtained according to Example 2-1. Except for the above, the same operation as in Example 3-1 was performed. As a result, a pigment dispersion composition containing 5.0% of the compound (3-9) in a fine particle state was obtained. The volume average particle diameter of the contained fine particles was 20 nm.

(Example 3-3)
In Example 4-1, the solid of the compound (6-16) obtained according to Example 2-7 was used instead of the solid of the compound (6-2) obtained according to Example 2-1. Except for the above, the same operation as in Example 3-1 was performed. As a result, a pigment dispersion composition containing 5.0% of the compound (6-16) in a fine particle state was obtained. The volume average particle diameter of the contained fine particles was 49 nm.

(Example 3-4)
In Example 3-1, the solid of the compound (6-14) obtained according to Example 2-5 was used instead of the solid of the compound (6-2) obtained according to Example 2-1. Except for the above, the same operation as in Example 3-1 was performed. As a result, a pigment dispersion composition containing 5.0% of the compound (6-14) in a fine particle state was obtained. The volume average particle diameter of the contained fine particles was 47 nm.

(Example 3-5)
In Example 3-1, the solid of the compound (6-3) obtained according to Example 2-8 was used instead of the solid of the compound (6-2) obtained according to Example 2-1. Except for the above, the same operation as in Example 3-1 was performed. As a result, a pigment dispersion composition containing 5.0% of the compound (6-3) in a fine particle state was obtained. The volume average particle diameter of the contained fine particles was 38 nm.

(Example 3-6)
In Example 3-1, the solid of the compound (5-9) obtained according to Example 2-9 was used instead of the solid of the compound (6-2) obtained according to Example 2-1. Except for the above, the same operation as in Example 3-1 was performed. As a result, a pigment dispersion composition containing 5.0% of the compound (5-9) in a fine particle state was obtained. The volume average particle diameter of the contained fine particles was 88 nm.

(Comparative Example 3-A)
In Example 3-1, instead of the solid of the compound (6-2) obtained according to Example 2-1, C.I. I. Pigment Yellow 128 (Crofthal (registered trademark) Yellow 8GN manufactured by Ciba Specialty Chemicals) was used except that Pigment Yellow 128 was used, and 5.0% C.I. I. A pigment dispersion composition containing Pigment Yellow 128 in a fine particle state was obtained. The volume average particle diameter of the contained fine particles was 304 nm.

  Table 8 below summarizes the volume average particle diameters of the fine particles contained in the colored dispersion compositions obtained according to the above Examples (3-1) to (3-6) and Comparative Example (3-A).

  From Table 8, it can be seen that in the colored composition of the present invention, the pigment particles easily take a fine particle dispersed state.

-Light fastness-
When the colored composition containing the compound (6-2) obtained according to Example 3-1 was measured using a reflection type spectrocolorimeter (XRite 938), the optical density of the coating was 1 The coated material was prepared by applying the ink to an inkjet paper (Epson Co., Ltd. photomat paper) using a bar coater.
Similarly, the coloring composition obtained according to Examples 3-2 to 3-6 and C.I. I. A colored composition coated material containing Pigment Yellow 74 (Irgalite (registered trademark) Yellow GO manufactured by Ciba Specialty Chemicals) was prepared.
Next, using a xenon fading tester, each coated material was irradiated with xenon light (170,000 lux, transmitted through a 325 nm filter) for 2 weeks. The optical density after irradiation was measured, and the remaining rate relative to the optical density before irradiation was calculated to evaluate the light fastness. The results are shown in Table 9 below.

  From Table 9, it can be seen that the coating formed using the colored composition of the present invention has excellent light fastness, although it does not contain a heavy metal that is concerned about safety.

Example 4
<Preparation of inkjet ink>
In a zirconia container with a total content of 12 ml,
-0.50 g of the solid of the compound (3-9) obtained according to the above Example 2-4;
・ 0.10 g of sodium oleate,
-4.40 g of deionized water,
Was put together with 10 g of zirconia beads having a diameter of 0.1 mm and pulverized using a planetary ball mill (Fritsch Japan Co., Ltd., P-7 type) (rotation speed: 300 rpm, pulverization time: 3 hours). After completion of the pulverization, the beads were separated from the mixture in the container by decantation, whereby a pigment dispersion composition containing 10% of the compound (3-9) in a fine particle state was obtained.
Using the pigment dispersion composition (coloring composition) thus obtained, an ink for inkjet recording having the following ink composition (containing 5% of the compound (3-9)) was produced.

~ Ink composition ~
10% pigment dispersion composition 50 parts Glycerol 10 parts 2-pyrrolidone 5 parts 1,2-hexanediol 2 parts Triethylene glycol monobutyl ether 2 parts Propylene glycol 0.5 parts Deionized water 30.5 Part

The ink-jet ink thus obtained was refilled into a cartridge of an ink-jet printer (PX-V600, trade name, manufactured by Seiko Epson Corporation), and inkjet paper painting mat finishing (trade name, manufactured by Fuji Photo Film Co., Ltd.) was performed on the same machine. ) Were recorded solid images.
The reflection spectrum of the obtained image is shown in FIG. It can be seen from FIG. 1 that an image formed with the ink jet recording ink of the present invention has excellent spectral characteristics with sharp absorption. That is, it was found that the inkjet recording ink of the present invention exhibits excellent properties.

Example 5
<Preparation of thermal transfer recording ink sheet>
Using a 6.0 μm thick polyester film (Lumirror, trade name, manufactured by Toray Industries, Inc.) with a heat-resistant slip treatment applied to the back surface by thermosetting acrylic resin (thickness 1 μm) on the front side of the film The coating composition for forming a dye-donating layer having the following composition containing the compound (6-7) obtained in the same manner as in Synthesis Example 8 was applied and formed by wire bar coating so that the thickness when dried was 1 μm. The ink sheet for thermal transfer recording of Example 7 was produced.

-Coating composition for forming dye-donating layer-
Compound (6-7) 5.5 parts Polyvinyl butyral resin 4.5 parts (ESREC BX-1, trade name, manufactured by Sekisui Chemical Co., Ltd.)
90 parts of methyl ethyl ketone / toluene (1/1)

  The thermal transfer recording ink sheet obtained above and the image receiving material for ASK2000 manufactured by FUJIFILM Corporation are superposed so that the dye donating layer and the image receiving layer are in contact with each other, and a thermal head is attached from the back side of the dye donating material. Used, printing is performed under the conditions of an output of a thermal head of 0.25 W / dot, a pulse width of 0.15 to 15 milliseconds, and a dot density of 6 dots / mm. When dyed, a clear thermal transfer recorded image without transfer unevenness was obtained. That is, it was found that the ink sheet exhibits excellent properties as a thermal transfer ink sheet.

Example 6
<Production of color filter>
(Preparation of positive resist composition)
Using 3.4 parts of cresol novolak resin (polystyrene equivalent weight 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 According to 1.8 parts of o-naphthoquinonediazide-5-sulfonic acid ester produced (average of two hydroxyl groups are esterified), 0.8 part of hexamethoxymethylolated melamine, 20 parts of ethyl lactate, and Synthesis Example 15 One part of the obtained compound (7-2) was mixed to obtain a positive resist composition.

(Production of color filter)
After the positive resist composition obtained above was spin coated on a silicon wafer, 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 an orange complementary color filter. The exposure was performed using 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.).
It was found that the obtained color filter had excellent spectral characteristics with sharp absorption and light transmission, and exhibited excellent properties as a color filter.

  According to the present invention, a colored composition containing no metal can be provided. In addition, according to the present invention, it is also possible to provide an inkjet recording ink, a thermal transfer ink sheet, a thermal transfer recording method, and a color filter. Therefore, the present invention is expected to be effectively used for high-quality full-color recording and the like, and has high industrial applicability.

It is a reflection spectrum of an inkjet recording image.

Claims (13)

The coloring composition containing a medium and the pigment | dye compound represented by following General formula (1).

(In the formula, R ¹ , R ² , A ¹ and A ² each independently represent a hydrogen atom or a monovalent substituent. X ¹ and X ² each independently have a substituent. And Y represents a group of atoms necessary to form a 4-7 membered heterocycle Q together with the carbon atom to which Y is bonded.   The coloring composition according to claim 1, wherein the coloring compound represented by the general formula (1) is dispersed in the medium. The heterocycle Q in the general formula (1) is represented by any one of the following general formulas (2) to (7) or a tautomer thereof. The coloring composition as described.

(In the formula, R ²¹ and R ²² each independently represent a hydrogen atom or a monovalent substituent. R ²³ , R ²⁴ and R ²⁵ may each independently have a substituent. When R ²³ has a substituent, the substituent may be bonded to R ²¹ or R ²² to form a ring, and when R ²⁴ has a substituent, the substituent is R And may form a ring by bonding to ^{22. When} R ²⁵ has a substituent, the substituent may bond to R ²¹ to form a ring)

(In the formula, R ³¹ , R ³² and R ³⁴ each independently represent a hydrogen atom or a monovalent substituent. R ³³ and R ³⁵ may each independently have a substituent. Represents a hetero atom, and when R ³³ has a substituent, the substituent may be bonded to R ³¹ or R ³² to form a ring, and when R ³⁵ has a substituent, the substituent is R ^31. To form a ring)

(In the formula, R ⁴¹ and R ⁴⁴ each independently represent a hydrogen atom or a monovalent substituent. R ⁴³ and R ⁴⁵ each independently represent a hetero atom which may have a substituent. When at least one of R ⁴³ and R ⁴⁵ has a substituent, the substituent may combine with R ⁴¹ to form a ring)

(Wherein R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent substituent, and R ⁵¹ and R ⁵² may be bonded to each other to form a ring. R ⁵³ , and R ⁵⁴ represents a hetero atom which may have a substituent independently of each other, and when R ⁵³ has a substituent, the substituent may combine with R ⁵² to form a ring. ^{When 54} has a substituent, the substituent may combine with R ⁵¹ to form a ring)

^{(Wherein, R 62,} and ^{R 64} are the ^{.R 63} represents a hydrogen atom or a monovalent substituent independently of one another, ^{.R 63} representing the hetero atom which may have a substituent is a substituent The substituent may combine with R ⁶² to form a ring)

(Z ⁷¹ and Z ⁷² each independently represent —N═ or —C (R ⁷⁵ ) ═. R ⁷³ , R ⁷⁴ , and R ⁷⁵ each independently represent a hydrogen atom or a monovalent substituent. Represents At least one of R ²⁴ and R ²⁵ in the general formula (2), R ^{35 in} the general formula (3), R ⁴⁵ in the general formula (4), and R ⁵³ and R ⁵⁴ in the general formula (5). The coloring composition according to claim 3, wherein at least one of each represents an oxygen atom. At least one of R ²¹ in the general formula (2), R ^{31 in} the general formula (3), R ⁴¹ in the general formula (4), and R ⁵¹ and R ⁵² in the general formula (5) is The coloring composition according to claim 3, wherein the coloring composition represents a hydrogen atom. 6. The coloring composition according to claim 1, wherein X ¹ and X ² in the general formula (1) each represent a sulfur atom. R ¹ and R ² in the general formula (1) are each independently a hydrogen atom, a hydroxy group, an alkoxy group, an acyloxy group, a cyano group, or a halogen atom. 7. The coloring composition according to any one of 6 above. A ¹ and A ² in the general formula (1) are each independently a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an acyloxy group, an aryloxy group, a carbamoyloxy group, an alkylcarbamoyloxy group, or an arylcarbamoyloxy group. The coloring composition according to claim 1, wherein the coloring composition is a group, a cyano group, a carbamoyl group, a halogen atom, or a nitro group.   The coloring composition according to any one of claims 1 to 8, further comprising a dispersant.   An ink for inkjet recording comprising the colored composition according to any one of claims 1 to 9. A dye compound represented by the following general formula (8).

(In the general formula (8), R ⁸¹ and R ⁸² each independently represent a hydrogen atom, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted acyl group, substituted or unsubstituted R ⁸³ , R ⁸⁴ represents a substituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group. , R ⁸⁵ , and R ⁸⁶ each independently represents a hydrogen atom or a monovalent substituent) A dye compound represented by the following general formula (9).

(In the general formula (9), R ⁹¹ , R ⁹² , R ⁹³ , R ⁹⁴ , R ⁹⁵ , R ⁹⁶ and R ⁹⁷ each independently represent a hydrogen atom or a monovalent substituent) A dye compound represented by the following general formula (10).

(In the general formula (10), X ¹⁰¹ and X ¹⁰² each independently represent -N = or -C (R ¹⁰⁷ ) =, and R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ And R ¹⁰⁷ each independently represents a hydrogen atom or a monovalent substituent)

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