JP2012140586A - Dipyrromethene metal complex compound, colored composition containing the same, ink sheet for thermosensitive transfer recording, color toner, ink for inkjet recording, and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dipyrromethene metal complex compound exhibiting a sharp absorption spectrum peak, and excellent in the fastness and the dissolvability to a solvent.SOLUTION: The dipyrromethene metal complex compound is represented by formula (1) (wherein Rto Reach independently denote a monovalent substituent; M denotes a metal or a metal compound; and X denotes a (un)substituted 2C-3C acyloxy group, a (un)substituted alkylsulfonyloxy group, or the like).

Description

  The present invention relates to a dipyrromethene metal complex compound, a coloring composition containing the dipyrromethene metal complex compound, a thermal transfer recording ink sheet, a color toner, an ink jet recording ink, and a color filter.

Currently, full color recording is the mainstream for image recording, and various colorants (dyes such as dyes and pigments) have been developed. Inkjet recording materials, thermal transfer recording materials, electrophotographic recording materials, transfer It is applied to silver halide photosensitive materials, printing inks, recording pen inks, and the like.
Also, various colorants for forming color filters have been developed in the technical field of recording or reproducing color images on color filters, such as image sensors such as CCDs, liquid crystal displays, and plasma displays.
For recording materials and color filter forming colorants, so-called additive color mixing methods and subtractive color mixing methods are used for recording or reproducing full color images. However, there is no strong colorant that has an absorption characteristic that can realize a preferable color gamut and can withstand various use environments, and improvement is strongly desired.

  For thermal transfer recording, a thermal transfer material in which a layer containing a heat-meltable ink is formed on a support (base film) is heated by a thermal head to melt the ink and recorded on the image receiving material, and a support. There is a system in which a heat-sensitive transfer material on which a dye-donating layer containing a heat-transferable dye is formed is heated by a thermal head to thermally transfer the dye onto the image receiving material. The latter thermal transfer system is easy to gradation recording because the amount of dye transfer can be changed by changing the energy applied to the thermal head, and is particularly advantageous for high-quality full-color recording. However, there are various restrictions on the heat transfer dyes used in this method, and very few satisfy all of the required performance.

  As the performance required above, for example, it has desirable spectral characteristics for color reproduction, is easy to transfer, is robust to light, heat and humidity (light resistance, heat resistance, moisture resistance), various They are robust to chemicals, easy to synthesize, and easy to make thermal transfer recording materials. However, conventional dyes proposed as having favorable spectral characteristics for color reproduction do not have a satisfactory level of spectral characteristics, and further improvements are strongly desired.

  In color copiers and color laser printers, which are electrophotographic recording devices, toners in which a colorant is dispersed in resin particles are generally used. As performance required for color toners, absorption characteristics that can realize a preferable color reproduction range, particularly high transparency (transparency) required when used in an overhead projector (hereinafter referred to as OHP), and usage environment conditions The fastness is mentioned. Although toners in which pigments are dispersed in particles as a colorant have been proposed (see, for example, Patent Documents 1 to 3), these toners are excellent in light resistance, but are insoluble and thus easily aggregate and have transparency. There is a problem in the drop and hue change of the transmitted color. On the other hand, toners using specific dyes as colorants have been proposed (see, for example, Patent Documents 4 to 6). However, these toners have a problem in light resistance, although they are highly transparent and have no hue change.

  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. In the ejection method, liquid is applied by applying pressure with a piezo element. There are a method of ejecting droplets, a method of generating bubbles in ink by heat to eject droplets, a method of using ultrasonic waves, and a method of sucking and ejecting droplets by electrostatic force. As the ink for ink jet recording, water-based ink, oil-based ink, or solid (melted type) ink is used. For the colorant used in such ink for ink jet recording, the solvent has good solubility or dispersibility, high density recording is possible, hue is good, light, heat, environment It is robust against active gases (oxidizing gases such as NOx, SOx, ozone, etc.), has excellent fastness to water and chemicals, has good fixability to image receiving materials and is difficult to bleed, ink It is required to have excellent storage stability, no toxicity, high purity, and availability at low cost. However, it is extremely difficult to search for colorants that meet these requirements at a high level. In particular, there is a strong demand for a colorant that exhibits a good magenta color and is robust to light, humidity, and heat, and in particular, a colorant that exhibits a good magenta color capable of realizing a preferable color reproduction range.

  Since the color filter needs to have high transparency, a method called a dyeing method for coloring with a dye has been performed. For example, a color filter can be manufactured by sequentially repeating a method of forming a pattern by pattern-exposing and developing a photoresist to be dyed and then dyeing with a filter color dye for all filter colors. In addition to the dyeing method, the color filter can be produced by a method using a positive type or negative type resist. Color filters manufactured by these methods have high transmittance due to the use of pigments and excellent optical properties, but have limited light resistance and heat resistance, etc., and have excellent resistance and transparency. A high colorant was desired. Although a method using an organic pigment having excellent light resistance and heat resistance instead of a pigment is widely known, it is difficult to obtain optical characteristics such as a dye with a color filter using a pigment.

  It is desired that the dyes that can be used for each of the above-mentioned purposes have the following properties in common. That is, it has a hue preferable for color reproduction, has an optimum spectral absorption, has fastness such as light resistance, moisture resistance, heat resistance, chemical resistance, and has good solubility in a solvent. Etc.

  On the other hand, Patent Document 7 discloses a dipyrromethene metal complex compound used as a colorant for a color filter. However, Patent Document 7 does not describe the dipyrromethene metal complex compound represented by the general formula (1) of the present invention, and among the dipyrromethene metal complex compounds, the dipyrromethene metal complex compound of the present invention exhibits excellent characteristics. It is not described that it is applied to a coloring composition as a colorant having, and can be usefully used for various applications including color filter applications.

JP 62-157051 A Japanese Patent Laid-Open No. Sho 62-255556 JP-A-6-118715 JP-A-3-276161 JP-A-2-207274 JP-A-2-207273 JP 2008-292970 A

The present invention has been made in view of the above prior art.
That is, an object of the present invention is to provide a dipyrromethene metal complex compound that exhibits a sharp absorption spectrum peak and is excellent in fastness and solubility in a solvent.
Another object of the present invention is to provide a colored composition containing the dipyrromethene metal complex compound, a thermal transfer recording ink sheet, a color toner, an ink jet recording ink, and a color filter.

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

  <1> A dipyrromethene metal complex compound represented by the following general formula (1).

In general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a monovalent substituent, and M represents a metal or a metal compound. X represents a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms, a substituted or unsubstituted alkylsulfonyloxy group, a substituted or unsubstituted arylsulfonyloxy group, or a halogen atom, and n1 and n2 each represents Independently represents an integer of 0 to 5, and n3 and n4 each independently represents an integer of 0 to 3.

  <2> A dipyrromethene metal complex compound represented by the following general formula (2).

In the general formula (2), R ³ and R ⁴ each independently represent a monovalent substituent, and X represents a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms, a substituted or unsubstituted alkylsulfonyloxy group. Represents a substituted or unsubstituted arylsulfonyloxy group, or a halogen atom.

<3> A colored composition containing the dipyrromethene metal complex compound according to <1> or <2>.
<4> A thermal transfer recording ink sheet comprising the dipyrromethene metal complex compound according to <1> or <2>.
<5> A color toner containing the dipyrromethene metal complex compound according to <1> or <2>.
<6> An inkjet recording ink containing the dipyrromethene metal complex compound according to <1> or <2>.
<7> A color filter containing the dipyrromethene metal complex compound according to <1> or <2>.

ADVANTAGE OF THE INVENTION According to this invention, the dipyrromethene metal complex compound which shows a sharp absorption spectrum peak and is excellent in fastness and the solubility with respect to a solvent can be provided.
In addition, according to the present invention, it is possible to provide a coloring composition, a thermal transfer recording ink sheet, a color toner, an inkjet recording ink, and a color filter containing the dipyrromethene metal complex compound.

2 is an absorption spectrum of exemplary compound (1) synthesized in Example 101. 4 is a reflection spectrum of a recorded image by the ink jet recording ink produced in Example 401. FIG. 10 is a transmission spectrum of a color filter produced in Example 501.

  The description of the configuration of the present invention 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.

  In the present specification, the “dipyrromethene skeleton” in the dipyrromethene metal complex compound means a structure represented by the following structural formula. In the present specification, the substitution position of the dipyrromethene skeleton is represented according to the following structural formula.

<Dipyrromethene metal complex compound>
[Dipyrromethene metal complex compound represented by the general formula (1)]
1st this invention is the dipyrromethene metal complex compound represented by following General formula (1). The dipyrromethene metal complex compound has a sharp absorption spectrum peak and good spectral characteristics. The dipyrromethene metal complex compound is excellent in heat resistance, moisture resistance and light resistance and is robust. Furthermore, the dipyrromethene metal complex compound has high solubility in a solvent.

In the general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a monovalent substituent, and M is a metal or a metal compound X represents a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms, a substituted or unsubstituted alkylsulfonyloxy group, a substituted or unsubstituted arylsulfonyloxy group, or a halogen atom, and n1 and n2 are Each independently represents an integer of 0 to 5, and n3 and n4 each independently represents an integer of 0 to 3. When n1 is an integer of 2 or more, R ⁵ of 2 or more may be the same or different. When n2 is an integer of 2 or more, R ⁶ of 2 or more may be the same or different. When n3 is an integer of 2 or more, R ⁷ of 2 or more may be the same or different. When n4 is an integer of 2 or more, R ⁸ of 2 or more may be the same or different.
In the present specification, the amide groups at the 5-position and the 5′-position of the dipyrromethene metal complex compound are described in the keto form in the keto-enol tautomeric equilibrium, but may be in the enol form.

In the dipyrromethene metal complex compound represented by the general formula (1), the 3-position and 3′-position of the dipyrromethene skeleton are substituted or unsubstituted phenyl groups, and the 5-position and 5′-position are 2 A 6-position unsubstituted phenylcarbonylamino group which is substituted at the -position (substituents of R ³ and R ⁴ in the general formula (1)). A dipyrromethene metal complex compound having such a structure has not been known so far.

In the general formula (1), examples of the monovalent substituent represented by R ^{1 to} R ⁸ include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), an alkyl group (preferably having 1 carbon atom). 48, more preferably a linear, branched, or cyclic alkyl group having 1 to 24 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group Hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group), alkenyl group (preferably having 2 carbon atoms) To 48, more preferably an alkenyl group having 2 to 18 carbon atoms, such as vinyl group, allyl group, 3-buten-1-yl group), aryl group (preferably Or an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, such as a phenyl group or a naphthyl group, or a heterocyclic group (preferably having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms). Heterocyclic groups such as 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazole -1-yl group), silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, such as trimethylsilyl group, triethylsilyl group, tributylsilyl group, t-butyldimethylsilyl group) , T-hexyldimethylsilyl group), hydroxy group, cyano group, nitro group, alkoxy group (preferably having 1 to 48 carbon atoms, more preferably carbon 1 to 24 alkoxy groups, for example, methoxy group, ethoxy group, 1-butoxy group, 2-butoxy group, isopropoxy group, t-butoxy group, dodecyloxy group, and cycloalkyloxy group, for example, , A cyclopentyloxy group, a cyclohexyloxy group), an aryloxy group (preferably an aryloxy group having 6 to 48 carbon atoms, more preferably an aryloxy group having 6 to 24 carbon atoms, such as a phenoxy group or a 1-naphthoxy group), heterocyclic oxy A group (preferably a heterocyclic oxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as 1-phenyltetrazol-5-oxy group or 2-tetrahydropyranyloxy group), a silyloxy group (preferably Is a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as trimethylsilyl An oxy group, a t-butyldimethylsilyloxy group, a diphenylmethylsilyloxy group), an acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as an acetoxy group, a pivaloyloxy group, Benzoyloxy group, dodecanoyloxy group), alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, such as ethoxycarbonyloxy group, t-butoxycarbonyloxy group) A cycloalkyloxycarbonyloxy group, for example, a cyclohexyloxycarbonyloxy group), an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms). Base For example, a phenoxycarbonyloxy group), a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as an N, N-dimethylcarbamoyloxy group, N-butyl group). Rucarbamoyloxy group, N-phenylcarbamoyloxy group, N-ethyl-N-phenylcarbamoyloxy group), sulfamoyloxy group (preferably having 1 to 32 carbon atoms, more preferably having 1 to 24 carbon atoms) Group, for example, N, N-diethylsulfamoyloxy group, N-propylsulfamoyloxy group),

An alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, such as a methylsulfonyloxy group, a hexadecylsulfonyloxy group, a cyclohexylsulfonyloxy group), an arylsulfonyloxy A group (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, more preferably an arylsulfonyloxy group having 6 to 24 carbon atoms, such as a phenylsulfonyloxy group), an acyl group (preferably having 1 to 48 carbon atoms, more preferably 1 carbon atom). To 24 acyl groups, for example, formyl group, acetyl group, pivaloyl group, benzoyl group, tetradecanoyl group, cyclohexanoyl group), alkoxycarbonyl group (preferably having 2 to 48 carbon atoms, more preferably 2 carbon atoms). To 24 alkoxycarbonyl groups, for example A xoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, a 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group), an aryloxycarbonyl group (preferably having 7 to 32 carbon atoms, More preferably, it is an aryloxycarbonyl group having 7 to 24 carbon atoms, such as a phenoxycarbonyl group, and a carbamoyl group (preferably a carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as a carbamoyl group. N, N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methylN-phenylcarbamoyl group, N, N-dicyclohexyl A carbamoyl group), an amino group (preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, such as an amino group, a methylamino group, an N, N-dibutylamino group, a tetradecylamino group, 2- An ethylhexylamino group, a cyclohexylamino group), an anilino group (preferably an anilino group having 6 to 32 carbon atoms, more preferably 6 to 24, for example, an anilino group or an N-methylanilino group), a heterocyclic amino group (preferably A heterocyclic amino group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, such as a 4-pyridylamino group), a carbonamido group (preferably a carbonamide group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms). , For example, acetamide group, benzamide group, tetradecanamide group, pivaloylamide group, cyclohexaneamide group) Ureido groups (preferably ureido groups having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as ureido group, N, N-dimethylureido group, N-phenylureido group), imide groups (preferably An imide group having 36 or less carbon atoms, more preferably 24 or less carbon atoms, for example, an N-succinimide group or an N-phthalimide group) or an alkoxycarbonylamino group (preferably having 2 to 48 carbon atoms, more preferably 2 to 2 carbon atoms). 24 alkoxycarbonylamino groups, for example, methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, octadecyloxycarbonylamino group, cyclohexyloxycarbonylamino group), aryloxycarbonylamino group (preferably having a carbon number) 7 to 32, more preferably 7 to 7 carbon atoms 4 aryloxycarbonylamino group, for example, phenoxycarbonylamino group), sulfonamido group (preferably 1-48 carbon atoms, more preferably 1-24 carbon sulfonamido groups, for example, methanesulfonamido group, A butanesulfonamide group, a benzenesulfonamide group, a hexadecanesulfonamide group, a cyclohexanesulfonamide group), a sulfamoylamino group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms). For example, N, N-dipropylsulfamoylamino group, N-ethyl-N-dodecylsulfamoylamino group), azo group (preferably having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms azo group) And, for example, phenylazo group, 3-pyrazolylazo group),

An alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably an alkylthio group having 1 to 24 carbon atoms, for example, methylthio group, ethylthio group, octylthio group, cyclohexylthio group), arylthio group (preferably having 6 to 48 carbon atoms). More preferably, it is an arylthio group having 6 to 24 carbon atoms, such as a phenylthio group, and a heterocyclic thio group (preferably having 1 to 32 carbon atoms, more preferably a heterocyclic thio group having 1 to 18 carbon atoms, 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group), alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, Dodecanesulfinyl group), arylsulfinyl group (preferably having 6 to 32 carbon atoms, more preferably An arylsulfinyl group having 6 to 24 prime atoms, such as a phenylsulfinyl group, an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably an alkylsulfonyl group having 1 to 24 carbon atoms, such as a methylsulfonyl group, ethyl Sulfonyl group, propylsulfonyl group, butylsulfonyl group, isopropylsulfonyl group, 2-ethylhexylsulfonyl group, hexadecylsulfonyl group, octylsulfonyl group, cyclohexylsulfonyl group), arylsulfonyl group (preferably having 6 to 48 carbon atoms, more preferably An arylsulfonyl group having 6 to 24 carbon atoms, for example, a phenylsulfonyl group, 1-naphthylsulfonyl group), a sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, Rufamoyl group, N, N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group), sulfo group, phosphono Group, phosphonyl group (preferably phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as phenoxyphosphonyl group, octyloxyphosphonyl group, phenylphosphonyl group), phosphinoylamino group (Preferably a phosphinoylamino group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as a diethoxyphosphinoylamino group or a dioctyloxyphosphinoylamino group).

  When the above-described monovalent group is a further substitutable group, it may be further substituted with any of the above-described groups. In addition, when it has two or more substituents, those substituents may be the same or different.

In the general formula (1), R ¹ and R ² are preferably each independently, preferably a substituted or unsubstituted alkoxycarbonyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted alkylsulfonyl having 1 to 30 carbon atoms. Group, substituted or unsubstituted arylsulfonyl group having 6 to 10 carbon atoms, substituted or unsubstituted alkylcarbamoyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbamoyl group having 7 to 11 carbon atoms, or cyano group And more preferably a substituted or unsubstituted alkoxycarbonyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylsulfonyl group having 1 to 12 carbon atoms, a substituted or unsubstituted phenylsulfonyl group, or a cyano group. In particular, an unsubstituted alkoxycarbonyl group having 6 to 30 carbon atoms or a cyano group is preferable.

In the general formula (1), R ³ and R ⁴ are preferably each independently, preferably a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms, a substituted or unsubstituted amino group, or a halogen atom, more preferably substituted or unsubstituted. A substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted phenoxy group, a chlorine atom, or a bromine atom; Particularly preferably, they are an unsubstituted alkyl group having 1 to 12 carbon atoms, an unsubstituted alkoxy group having 1 to 12 carbon atoms, or a chlorine atom.

In the general formula (1), R ⁵ , R ⁶ , R ⁷ and R ⁸ are preferably each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number 6. -10 aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms, substituted or unsubstituted carbon An alkylthio group having 1 to 30 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 10 carbon atoms, a substituted or unsubstituted acyl group having 2 to 30 carbon atoms, and a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms Substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, substituted or unsubstituted aryl group having 0 to 30 carbon atoms. Group, a cyano group, a halogen atom, a hydroxy group, a carboxy group, a sulfo group, or a phosphono group, more preferably a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted phenyl group, Substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms, substituted or unsubstituted phenoxy group, substituted or unsubstituted alkylthio group having 1 to 18 carbon atoms, substituted or unsubstituted phenylthio group, substituted or unsubstituted carbon An acyl group having 2 to 18 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 18 carbon atoms, a substituted or unsubstituted alkylsulfonyl group having 1 to 18 carbon atoms, and a substituted or unsubstituted carbamoyl group having 1 to 18 carbon atoms Group, substituted or unsubstituted amino group having 0 to 18 carbon atoms, cyano group, fluorine atom, chlorine atom, bromine atom, hydride A xy group, a carboxy group, a sulfo group, or a phosphono group, particularly preferably an unsubstituted alkyl group having 1 to 12 carbon atoms, an unsubstituted phenyl group, an unsubstituted alkoxy group having 1 to 12 carbon atoms, A substituted acyl group having 2 to 12 carbon atoms, an unsubstituted alkoxycarbonyl group having 2 to 18 carbon atoms, an unsubstituted alkylsulfonyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, a hydroxy group, or It is a carboxy group.

In Formula (1), when n1 is an integer of 2 or more, 5 membered by bonding R ⁵ adjacent to each other, they may form a 6- or 7-membered ring. In addition, as a ring formed, a benzene ring, a naphthalene ring, a pyridine ring, a furan ring, a thiophene ring is mentioned, for example, Preferably a benzene ring is mentioned. When n2, n3 and n4 are each an integer of 2 or more, the same applies to adjacent R ⁶ , adjacent R ⁷ and adjacent R ⁸ .
When R ³ and R ⁷ are adjacent to each other, R ³ and R ⁷ may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring. Examples of the ring formed include a benzene ring, a naphthalene ring, a pyridine ring, a furan ring, and a thiophene ring, and preferably a benzene ring. The same applies to the case where R ⁴ and R ⁸ are adjacent to each other.
In addition, when the formed 5-membered, 6-membered and 7-membered rings are further substitutable groups, they may be substituted with any of the aforementioned monovalent substituents. When substituted with a substituent, these substituents may be the same or different.

In the general formula (1), n1 and n2 are each independently an integer of 0 to 5, preferably 0 to 3, more preferably 0 to 2, particularly preferably 0 or 1. .
In the general formula (1), n3 and n4 are each independently an integer of 0 to 3, preferably 0 to 2, and particularly preferably 0 or 1.

In the general formula (1), the metal or metal compound represented by M may be any metal atom or metal compound capable of forming a complex, and may be any divalent metal atom or divalent metal. Oxides, divalent metal hydroxides, or divalent metal chlorides are included. For example, in addition to Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, etc., AlCl ₃ , InCl ₃ , FeCl ₂ , TiCl ₂ , SnCl ₂ Further, metal chlorides such as SiCl ₂ and GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ are also included.
From the viewpoint of the stability, spectral characteristics, heat resistance, light resistance, and production suitability of the complex, the metal or metal compound represented by M is preferably Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn. Cu, Ni, Co, TiO, B, or VO, more preferably Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO, and particularly preferably Zn. It is.

  In the general formula (1), X represents a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms, a substituted or unsubstituted alkylsulfonyloxy group, a substituted or unsubstituted arylsulfonyloxy group, or a halogen atom. . X is preferably a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms, a substituted or unsubstituted alkylsulfonyloxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyloxy group having 6 to 30 carbon atoms. Or a chlorine atom, more preferably a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms, an unsubstituted alkylsulfonyloxy group having 1 to 18 carbon atoms, or an unsubstituted aryl having 6 to 12 carbon atoms. A sulfonyloxy group, particularly preferably a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms.

In the dipyrromethene metal complex compound represented by the general formula (1), a preferable combination of the substituents represented by R ^{1 to} R ⁸ , M, and X is that at least one of these substituents is the preferred group. More preferably, more substituents are the preferred groups, and most preferably all substituents are the preferred groups.

Preferred embodiments of the dipyrromethene metal complex compound represented by the general formula (1) are shown below. That is, in the general formula (1),
R ¹ and R ² are each independently a substituted or unsubstituted alkoxycarbonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number 6 to 6 10 arylsulfonyl groups, substituted or unsubstituted alkylcarbamoyl groups having 1 to 30 carbon atoms, substituted or unsubstituted arylcarbamoyl groups having 7 to 11 carbon atoms, or cyano groups,
R ³ and R ⁴ are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms. A substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms, a substituted or unsubstituted amino group, or a halogen atom,
R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a substituted or unsubstituted group. Heterocyclic group, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms, substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, substituted or unsubstituted A substituted arylthio group having 6 to 10 carbon atoms, a substituted or unsubstituted acyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon number 1 to 30 Alkylsulfonyl group, substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, substituted or unsubstituted amino group having 0 to 30 carbon atoms, cyano group, halogen atom, Dorokishi group, a carboxy group, a sulfo group, or a phosphono group,
n1, n2, n3 and n4 are each independently 0 to 3,
M is Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B, or VO;
X is a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms, a substituted or unsubstituted alkylsulfonyloxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyloxy group having 6 to 30 carbon atoms, or A combination that is a chlorine atom.

The more preferable aspect of the dipyrromethene metal complex compound represented by the said General formula (1) is shown below. That is, in the general formula (1),
R ¹ and R ² are both substituted or unsubstituted alkoxycarbonyl groups having 6 to 30 carbon atoms, substituted or unsubstituted alkylsulfonyl groups having 1 to 12 carbon atoms, substituted or unsubstituted phenylsulfonyl groups, or cyano groups. And
R ³ and R ⁴ are both substituted or unsubstituted alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted phenyl groups, substituted or unsubstituted alkoxy groups having 1 to 12 carbon atoms, substituted or unsubstituted phenoxy. A group, a chlorine atom, or a bromine atom,
R ⁵ and R ⁶ are both substituted or unsubstituted alkyl groups having 1 to 18 carbon atoms, substituted or unsubstituted phenyl groups, substituted or unsubstituted alkoxy groups having 1 to 18 carbon atoms, substituted or unsubstituted phenoxy. Group, substituted or unsubstituted alkylthio group having 1 to 18 carbon atoms, substituted or unsubstituted phenylthio group, substituted or unsubstituted acyl group having 2 to 18 carbon atoms, substituted or unsubstituted alkoxy group having 2 to 18 carbon atoms Carbonyl group, substituted or unsubstituted alkylsulfonyl group having 1 to 18 carbon atoms, substituted or unsubstituted carbamoyl group having 1 to 18 carbon atoms, substituted or unsubstituted amino group having 0 to 18 carbon atoms, cyano group, fluorine An atom, a chlorine atom, a bromine atom, a hydroxy group, a carboxy group, a sulfo group, or a phosphono group,
R ⁷ and R ⁸ are both substituted or unsubstituted alkyl groups having 1 to 18 carbon atoms, substituted or unsubstituted phenyl groups, substituted or unsubstituted alkoxy groups having 1 to 18 carbon atoms, substituted or unsubstituted phenoxy. Group, substituted or unsubstituted alkylthio group having 1 to 18 carbon atoms, substituted or unsubstituted phenylthio group, substituted or unsubstituted acyl group having 2 to 18 carbon atoms, substituted or unsubstituted alkoxy group having 2 to 18 carbon atoms Carbonyl group, substituted or unsubstituted alkylsulfonyl group having 1 to 18 carbon atoms, substituted or unsubstituted carbamoyl group having 1 to 18 carbon atoms, substituted or unsubstituted amino group having 0 to 18 carbon atoms, cyano group, fluorine An atom, a chlorine atom, a bromine atom, a hydroxy group, a carboxy group, a sulfo group, or a phosphono group,
n1 and n2 are both 0-2, n3 and n4 are both 0-2,
M is Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO;
A combination in which X is a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms, an unsubstituted alkylsulfonyloxy group having 1 to 18 carbon atoms, or an unsubstituted arylsulfonyloxy group having 6 to 12 carbon atoms. .

The most preferred embodiment of the dipyrromethene metal complex compound represented by the general formula (1) is shown below. That is, in the general formula (1),
R ¹ and R ² are both unsubstituted C6-C30 alkoxycarbonyl groups or cyano groups,
R ³ and R ⁴ are both an unsubstituted alkyl group having 1 to 12 carbon atoms, an unsubstituted alkoxy group having 1 to 12 carbon atoms, or a chlorine atom,
R ⁵ and R ⁶ are both an unsubstituted alkyl group having 1 to 12 carbon atoms, an unsubstituted phenyl group, an unsubstituted alkoxy group having 1 to 12 carbon atoms, an unsubstituted acyl group having 2 to 12 carbon atoms, An unsubstituted alkoxycarbonyl group having 2 to 18 carbon atoms, an unsubstituted alkylsulfonyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, a hydroxy group, or a carboxy group;
R ⁷ and R ⁸ are both an unsubstituted alkyl group having 1 to 12 carbon atoms, an unsubstituted phenyl group, an unsubstituted alkoxy group having 1 to 12 carbon atoms, an unsubstituted acyl group having 2 to 12 carbon atoms, An unsubstituted alkoxycarbonyl group having 2 to 18 carbon atoms, an unsubstituted alkylsulfonyl group having 1 to 12 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, a hydroxy group, or a carboxy group;
n1 and n2 are both 0 or 1, n3 and n4 are both 0 or 1,
M is Zn;
A combination in which X is a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms,
It is a dipyrromethene metal complex compound represented by the following general formula (2).

[Dipyrromethene metal complex compound represented by general formula (2)]
Among the dipyrromethene metal complex compounds represented by the general formula (1), the dipyrromethene metal complex compound represented by the following general formula (2) is soluble in organic solvents, easy to synthesize, stable against heat and alkali. It is superior in terms of sex.

In the general formula (2), R ³ and R ⁴ each independently represent a monovalent substituent, and X represents a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms, a substituted or unsubstituted alkylsulfonyloxy. Represents a group, a substituted or unsubstituted arylsulfonyloxy group, or a halogen atom.

Wherein ^R 3 in the general formula (2), ^{R 4} and X are the same as ^R 3, ^{R 4} and X in the general formula (1), and preferred examples are also the same.

Preferred embodiments of the dipyrromethene metal complex compound represented by the general formula (2) are shown below. That is, in the general formula (2),
R ³ and R ⁴ are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms. A substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms, a substituted or unsubstituted amino group, or a halogen atom,
X is a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms, a substituted or unsubstituted alkylsulfonyloxy group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyloxy group having 6 to 30 carbon atoms, or A combination that is a chlorine atom. Here, R ³ and R ⁴ are preferably the same substituent.

The more preferable aspect of the dipyrromethene metal complex compound represented by the said General formula (2) is shown below. That is, in the general formula (2),
R ³ and R ⁴ are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted group. A substituted phenoxy group, a chlorine atom, or a bromine atom,
A combination in which X is a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms, an unsubstituted alkylsulfonyloxy group having 1 to 18 carbon atoms, or an unsubstituted arylsulfonyloxy group having 6 to 12 carbon atoms. . Here, R ³ and R ⁴ are preferably the same substituent.

The most preferred embodiment of the dipyrromethene metal complex compound represented by the general formula (2) is shown below. That is, in the general formula (2),
R ³ and R ⁴ are each independently an unsubstituted alkyl group having 1 to 12 carbon atoms, an unsubstituted alkoxy group having 1 to 12 carbon atoms, or a chlorine atom,
A combination in which X is a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms. Here, R ³ and R ⁴ are preferably the same substituent.

Specific examples of the dipyrromethene metal complex compound represented by the general formula (1) are shown below, but the present invention is not limited thereto. In Tables 1 to 4, R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , M ¹ and X ¹⁰¹ represent a substituent in the following general formula (3).

  Among the exemplary compounds, exemplary compounds (1) to (10) are also specific examples of the dipyrromethene metal complex compound represented by the general formula (2).

  The dipyrromethene metal complex compound represented by the general formula (1) is disclosed in U.S. Pat. Nos. 4,774,339, 5,433,896, JP-A-2001-240761, and 2002-155052. Publication, Japanese Patent No. 3614586, Aust. J. et al. Chem, 1965, 11, 1835-1845, J. Am. H. Boger et al, Heteroatom Chemistry, Vol. 1, no. 5, 389 (1990), Japanese Patent Application Laid-Open No. 2008-292970, paragraph numbers 0131 to 1157.

  The maximum absorption wavelength λmax of the dipyrromethene metal complex compound represented by the general formula (1) and the maximum absorption wavelength λmax of the dipyrromethene metal complex compound represented by the general formula (2) are preferably in the range of 500 to 620 nm. More preferably, it is the range of 520-600 nm, Most preferably, it is the range of 530-580 nm. The maximum absorption wavelength λmax is measured by a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation).

The dipyrromethene metal complex compound of the present invention is preferably used as a magenta color among the three primary colors in color image forming material applications.
The dipyrromethene metal complex compound of the present invention is used for color filter materials, for example, for bright line cutting (for blocking 532 nm light, which is a second harmonic of the YAG laser oscillation wavelength 1064 nm), and for color correction at the long wavelength end of a red filter. It is preferably used as a color correction application at the short wavelength end of a blue filter.

<Coloring composition>
2nd this invention is a coloring composition containing the dipyrromethene metal complex compound represented by the said General formula (1). The colored composition refers to a thermal transfer recording ink sheet, an inkjet recording ink, a color toner, a color filter, a writing pen, a colored plastic, and other ink liquids. The colored composition of the present invention can be suitably applied particularly as a thermal transfer recording ink sheet, an ink jet recording ink, a color toner, and a color filter.
Hereinafter, the thermal transfer recording ink sheet, the inkjet recording ink, the color toner, and the color filter containing the dipyrromethene metal complex compound represented by the general formula (1) will be described in detail.

<Ink sheet for thermal transfer recording>
The ink sheet for thermal transfer recording of the present invention generally has a structure in which a dye-donating layer is formed on a support, and the dipyrromethene metal complex compound represented by the general formula (1) in the dye-donating layer. Containing. The ink sheet for thermal transfer recording is prepared by dissolving the dipyrromethene metal complex 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 the ink liquid on a support and drying it appropriately to form a dye-donating layer. In addition to the dipyrromethene metal complex compound represented by the general formula (1), other dye compounds may be used simultaneously.

In order to apply the thermal transfer recording ink sheet of the present invention 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 being formed 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 the cyan ink sheet, for example, those described in JP-A-3-103477 and JP-A-3-150194 can be preferably used. As the yellow ink sheet, for example, those described in Japanese Patent No. 4468907 can be preferably used. As the magenta ink sheet, the thermal transfer recording ink sheet of the present invention containing the dipyrromethene metal complex compound represented by the general formula (1) is 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 dipyrromethene metal complex compound represented by the general formula (1) and other dye compounds are used. The type is not particularly limited as long as it does not prevent the transfer to the image receiving material. For example, what was 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 dipyrromethene metal complex compound represented by the general formula in the dye-donor layer (1) is preferably from 0.03 to 1.0 g / ^{m 2,} more preferably 0.1 to 0.6 g / ^{m 2} . 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 ink sheet for thermal transfer recording may have a layer other than the dye-donating layer as long as the effect of the present invention is not excessively inhibited. For example, an intermediate layer may be provided between the support and the dye-donating layer, or a back layer may be provided on the support surface opposite to the dye-donating layer (hereinafter also referred to as “back surface”). There may be. As the intermediate layer, for example, an undercoat layer, a diffusion preventing layer (hydrophilic barrier layer) for preventing diffusion of the dipyrromethene metal complex compound represented by the general formula (1) and other dye compounds toward the support. Can be mentioned. 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 from the thermal head to the ink sheet in accordance with the image recording signal, and the dipyrromethene metal complex compound represented by the general formula (1) and other dye compounds in the portion where the thermal energy is applied to the image receiving material. A thermal transfer recording method characterized in that image recording is performed by shifting and fixing. The image receiving material usually has a structure in which an ink receiving layer containing a polymer is provided on a support. As the configuration and materials used of the image receiving material, for example, those described in paragraph numbers 0056 to 0074 of JP-A-7-137466 can be preferably used.

<Color toner>
The color toner of the present invention contains the dipyrromethene metal complex compound represented by the general formula (1). As the binder resin for a color toner into which the dipyrromethene metal complex compound represented by the general formula (1) is introduced, all binders generally used for toners can be used. For example, a styrene resin, an acrylic resin, a styrene / acrylic resin, a polyester resin, and the like can be given. For the purpose of imparting fluidity improvement or charge control to the toner, inorganic fine powder or organic fine particles may be externally added. Silica fine particles and titania fine particles whose surface is treated with an alkyl group-containing coupling agent or the like are preferably used. These particles preferably have a number average primary particle size of 10 to 500 nm, and more preferably 0.1 to 20% by mass in the toner.

  As the release agent used for the color toner, any release agent conventionally used for toner can be used. Specific examples include olefins such as low molecular weight polypropylene, low molecular weight polyethylene, and ethylene-propylene copolymer, microcrystalline wax, carnauba wax, sazole wax, and paraffin wax. These addition amounts are preferably 1 to 5% by mass in the toner.

  The charge control agent used in the color toner may be added as necessary, but is preferably colorless from the viewpoint of color development. Examples thereof include those having a quaternary ammonium salt structure and those having a calixarene structure.

  As the carrier used for the color toner, any of an uncoated carrier composed only of magnetic material particles such as iron and ferrite and a resin-coated carrier whose magnetic material particle surface is coated with a resin or the like may be used. The average particle size of this carrier is preferably 30 to 150 μm in terms of volume average particle size.

  The image forming method to which the color toner is applied is not particularly limited. For example, a method of forming an image by repeatedly forming a color image on a photoconductor to form an image, or a photoconductor formed on the photoconductor. For example, the image may be transferred sequentially to an intermediate transfer member and the like, and a color image may be formed on the intermediate transfer member and then transferred to an image forming member such as paper to form a color image.

<Ink for inkjet recording>
The ink for inkjet recording of the present invention contains the dipyrromethene metal complex compound represented by the general formula (1). The inkjet recording ink can be prepared by dissolving and / or dispersing the dipyrromethene metal complex compound represented by the general formula (1) in an oleophilic medium or an aqueous medium. Use.
Since the ink for inkjet recording contains a pigment compound (dipyrromethene metal complex compound represented by the general formula (1)) that is excellent in spectral characteristics and fastness, and also has excellent solubility, It is suitable as an inkjet recording ink.

(Additive)
The ink for ink jet recording contains other additives as necessary within a range that does not impair the effects of the present invention. Other additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, Well-known additives, such as a foaming agent, a viscosity modifier, a dispersing agent, a dispersion stabilizer, a rust preventive agent, a chelating agent, are mentioned. These various additives are generally added to the dispersion after the preparation of the dye compound dispersion, but may be added to the oil phase or the aqueous phase at the time of preparation.

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

  The penetration enhancer is preferably used for the purpose of allowing the ink for inkjet recording to penetrate better into paper. Examples of the penetration enhancer include alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, and nonionic surfactants. it can. If these are contained in the ink in an amount of 5 to 30% by mass, they usually have a sufficient effect, and it is preferable to use them in a range of addition amounts that do not cause printing bleeding and paper loss (print through).

  The ultraviolet absorber is used for the purpose of improving image storage stability. Examples of the ultraviolet absorber include benzotriazoles described in JP-A Nos. 58-185677, 61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Compounds, benzophenone compounds described in JP-A-46-2784, JP-A-5-194443, US Pat. No. 3,214,463, etc., JP-B-48-30492, 56 -21141, JP-A-10-88106, etc., cinnamic acid compounds, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, and JP-A-10-182621. Triazine compounds described in JP-A-8-501291 and the like, Research Disclosure No. Compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based and benzoxazole-based compounds, so-called fluorescent brighteners, can also be used.

  The anti-fading agent is used for the purpose of improving image storage stability. As the anti-fading agent, various organic and metal complex anti-fading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like. More specifically, Research Disclosure No. No. 17643, No. VII, I to J, ibid. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. It is possible to use the compounds described in the patent literature cited in 15162, or the compounds contained in the general formulas and compound examples of representative compounds described on pages 127 to 137 of JP-A-62-215272. it can.

  Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. These are preferably used in the ink in an amount of 0.02 to 1.00% by mass.

  The neutralizer (organic base, inorganic alkali) can be used as the pH adjuster. For the purpose of improving the storage stability of the ink for ink jet recording, the pH adjuster is preferably added so that the ink for ink jet recording has a pH of 6 to 10, and more preferably added to have a pH of 7 to 10. preferable.

  Examples of the surface tension adjusting agent include nonionic, cationic and anionic surfactants. The surface tension of the ink for inkjet recording of the present invention is preferably 20 to 60 mN / m, and more preferably 25 to 45 mN / m. Further, the viscosity of the inkjet recording ink of the present invention is preferably 30 mPa · s or less, and more preferably 20 mPa · s or less.

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

  As the antifoaming agent, fluorine-based and silicone-based compounds, chelating agents represented by EDTA, and the like can be used as necessary.

(Method for preparing ink for inkjet recording)
When the dipyrromethene metal complex compound represented by the general formula (1) is dispersed in an aqueous medium, each of JP-A Nos. 11-286637, 2001-240763, 2001-262039, and 2001-247788 As described in the publication, colored fine particles containing a dipyrromethene metal complex compound and an oil-soluble polymer are dispersed in an aqueous medium, or Japanese Patent Application Laid-Open Nos. 2001-262018, 2001-240763, 2001-335734, 2002. As described in each publication of -80772, it is preferable to disperse a dipyrromethene metal complex compound dissolved in a high boiling point organic solvent in an aqueous medium. Specific methods for dispersing the dipyrromethene metal complex compound represented by the general formula (1) in an aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additives, and the amounts used thereof are disclosed in the above-mentioned patent document. Those described in (1) can be preferably used. Alternatively, the dipyrromethene metal complex compound may be dispersed in a fine particle state as a solid. At the time of dispersion, a dispersant or a surfactant can be used.

  Examples of the dispersing device include a stirrer, an impeller stirring device, an in-line stirring device, a mill (for example, a colloid mill, a ball mill, a sand mill, an attritor, a roll mill, and an agitator mill), an ultrasonic stirring device, and a high-pressure emulsifying dispersion device (high-pressure homogenizer; As a specific commercial apparatus, a gorin homogenizer, a microfluidizer, DeBEE2000 (manufactured by BEE International Co., Ltd.) and the like can be used. Regarding the method for preparing the ink for ink jet recording, in addition to the aforementioned patent documents, JP-A-5-148436, JP-A-5-295212, JP-A-7-97541, JP-A-7-82515, JP-A-7-118584, Details are described in JP-A-11-286637 and JP-A-2001-271003, and can be applied to the present invention.

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

<Color filter>
The color filter of the present invention contains the dipyrromethene metal complex compound represented by the general formula (1). The color filter has a high transmittance by containing the dipyrromethene metal complex compound.

As a method for forming the color filter, a pattern is first formed with a photoresist and then dyed, or Japanese Patent Application Laid-Open Nos. 4-163552, 4-128703, 4-175653, 2008-. As disclosed in publications such as No. 292970, there is a method of forming a pattern with a photoresist added with a colorant.
As a method used when introducing the dipyrromethene metal complex compound represented by the general formula (1) into a color filter, any of these methods may be used. No. 6-35182, that is, a positive resist composition containing a thermosetting resin, a quinonediazide compound, a crosslinking agent, a colorant and a solvent is applied on a substrate and then exposed through a mask. A method of forming a color filter comprising 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 is preferable. In addition, the method described in JP-A-2008-292970, that is, after applying a negative resist composition containing a polymerizable compound, a polymerization initiator, a developing resin, a colorant and a solvent on a substrate, There is also a method for forming a color filter comprising exposing through a mask, developing the exposed portion to form a negative resist pattern, exposing the entire positive resist pattern, and then curing the exposed negative resist pattern. preferable. In addition, a black matrix can be formed according to a conventional method, and an RGB primary color system or YMC complementary color system color filter can be obtained.

  Regarding the thermosetting resin, quinonediazide compound, crosslinking agent, polymerizable compound, polymerization initiator, developing resin, and solvent used in this case, and those used, those described in the above publications are preferably used. Can do.

  Hereinafter, the present invention will be described in more detail 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. Accordingly, the scope of the present invention should not be construed as being limited by the specific examples shown below.

<Example 101>
[Synthesis of Exemplary Compound (1)]
The exemplified compound (1) described above, which is a dipyrromethene metal complex compound represented by the general formula (1), was synthesized by the method described below.

-Synthesis of Intermediate A-
Intermediate A having the following structural formula was synthesized by the method described in US Patent Application Publication No. 2008/0076044.

-Synthesis of Intermediate B-
690 ml of acetonitrile was added to 225.8 g (0.55 mol) of intermediate A, and the mixture was stirred under ice cooling. To this solution, 93.5 g (0.61 mol) of o-toluoyl chloride was added dropwise. Thereafter, 52.2 g (0.66 mol) of pyridine was added dropwise, and the mixture was stirred for 1 hour under ice cooling and 2 hours at room temperature. After completion of the reaction, the precipitated solid was filtered, and the filtrate was washed with acetonitrile and dried. In this manner, 229 g (yield 79%) of Intermediate B having the following structural formula was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are δ: 11.04 (d, 2H), 7.64 (d, 1H), 7.45 to 7.23 (m, 8H), 6.37. (D, 1H), 5.86 (s, 1H), 2.60 (s, 3H), 1.27 to 1.12 (m, 3H), 1.06 to 0.92 (m, 2H) 0 .84 (s, 18H), 0.70 (d, 3H), 0.63 to 0.47 (m, 2H).

-Synthesis of Intermediate C-
In 420 ml of acetic anhydride, 222.1 g (0.42 mol) of Intermediate B and 31.1 g (0.21 mol) of triethyl orthoformate were added and stirred at room temperature. To this solution, 630 ml of trifluoroacetic acid was added dropwise and stirred at room temperature for 3 hours. After completion of the reaction, the reaction solution was poured into a solution obtained by adding 940 g of sodium bicarbonate to 6400 ml of water, extracted with 3200 ml of ethyl acetate, and then neutralized with a saturated aqueous solution of sodium bicarbonate. After drying over sodium sulfate, the mixture was filtered, and the filtrate was concentrated under reduced pressure. To the obtained solid, 2600 ml of methanol was added, and the mixture was heated and stirred at 60 ° C. for 1 hour, then filtered while hot, washed again with methanol, and the obtained solid was dried. In this way, 170.3 g (yield 76%) of Intermediate C having the following structural formula was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are δ: 11.10 (s, 2H), 7.72 (d, 2H), 7.39 to 7.13 (m, 16H), 6.12. (S, 1H), 5.85 (s, 2H), 2.70 (s, 6H), 1.29 to 1.08 (m, 6H), 1.02 to 0.92 (m, 4H) 0 .80 (s, 36H), 0.64 (d, 6H), 0.44 to 0.31 (m, 4H).

-Synthesis of Exemplified Compound (1)-
Intermediate C (3.1 g, 2.9 mmol) was added to tetrahydrofuran (22 ml), and the mixture was stirred at room temperature. To this solution, methanol (22 ml) was added 0.70 g (3.2 mmol) of zinc acetate dihydrate. Added and stirred for 3 hours. The reaction solution was concentrated using a rotary evaporator, and the resulting residue was added to 80 ml of methanol and stirred at 60 ° C. for 1 hour. Subsequently, filtration was performed, and the residue was dried. In this way, 2.34 g (yield 67%) of Exemplary Compound (1) was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: σ 11.6 (s, 2H), 7.73 (d, 2H), 7.4 to 7.1 (16H), 6.4 (s 1H), 5.8 (s, 2H), 2.8 (s, 6H), 2.0 (s, 3H), 1.3-1.1 (m, 6H), 1.05-0. They were 95 (m, 4H), 0.85 (s, 36H), 0.7 (d, 6H), and 0.6 to 0.25 (m, 4H).

−Evaluation of maximum absorption wavelength−
Exemplified compound (1) was dissolved in the measurement solvent described in Table 5 below (concentration 1 × 10 ⁻⁶ mol / L), and the absorption spectrum was measured (optical path length 10 mm). Table 5 below shows the maximum absorption wavelength of the absorption spectrum of the exemplary compound (1).

<Examples 102 to 110>
[Synthesis of Exemplified Compounds (2) to (10)]
The above-described exemplary compounds (2) to (10) according to Examples 102 to 110 were synthesized by a method according to Example 101. In addition, the dipyrromethene metal complex compound represented by the general formula (1) other than the exemplary compounds (2) to (10) can also be synthesized by a method according to Example 101 from a chemical standpoint.

−Evaluation of maximum absorption wavelength−
Exemplified compounds (2) to (10) were dissolved in the measurement solvents described in Table 5 below (concentration: 1 × 10 ⁻⁶ mol / L), and absorption spectra were measured (optical path length: 10 mm). Table 5 below shows the maximum absorption wavelengths of the absorption spectra of the exemplary compounds (2) to (10).

<Example 111>
[Synthesis of Exemplified Compound (36)]
The exemplified compound (36) described above, which is a dipyrromethene metal complex compound represented by the general formula (1), was synthesized by the method described below.

-Synthesis of Intermediate D-
To 165.2 g (1.1 mol) of 2,4-dimethylbenzoic acid, 200 ml of dimethylacetamide and 300 ml of acetonitrile were added and stirred under ice cooling. To this solution, 130.9 g (1.1 mol) of thionyl chloride was added dropwise, and the mixture was stirred for 30 minutes under ice-cooling and then at room temperature for 1 hour to obtain a reaction solution A. Subsequently, 800 ml of dimethylacetamide was added to 410.6 g (1 mol) of the intermediate A and stirred under ice cooling. To this solution, the previously prepared reaction solution A was added dropwise, and after completion of the addition, the solution was returned to room temperature and stirred for 2 hours. After completion of the reaction, the reaction solution was poured into 6 L of water, the precipitated solid was filtered, and the residue was washed with water and acetonitrile and dried. In this way, 510.8 g (yield 94%) of Intermediate D having the following structural formula was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are δ: 11.04 (d, 2H), 7.57 (d, 1H), 7.38 to 7.12 (m, 7H), 6.36. (S, 1H), 5.87 (s, 1H), 2.58 (s, 3H), 2.39 (s, 3H), 1.27 to 1.12 (m, 3H), 1.04 to It was 0.97 (m, 2H) 0.84 (s, 18H), 0.71 (d, 3H), 0.63 to 0.47 (m, 2H).

-Synthesis of Intermediate E-
In 60 ml of acetic anhydride, 27.14 g (0.05 mol) of Intermediate D and 3.71 g (0.025 mol) of triethyl orthoformate were added and stirred at room temperature. To this solution, 75 ml of trifluoroacetic acid was added dropwise and stirred at room temperature for 2 hours. After completion of the reaction, the reaction solution was poured into a solution obtained by adding 112 g of sodium bicarbonate to 200 ml of ethyl acetate and 750 ml of water, and stirred at room temperature for 2 hours. Subsequently, the precipitated solid was filtered, and the filtrate was washed with ethyl acetate and dried. In this way, 14.8 g (yield 54%) of Intermediate E having the following structural formula was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 11.14 (s, 2H), 7.67 (d, 2H), 7.31 to 7.12 (m, 14H), 6.12 (S, 1H), 5.87 (s, 2H), 2.71 (s, 6H), 2.40 (s, 6H), 1.28 to 1.12 (m, 6H), 1.01 It was 0.96 (m, 4H) 0.82 (s, 36H), 0.66 (d, 6H), 0.45 to 0.33 (m, 4H).

-Synthesis of Exemplified Compound (36)-
4.93 g (4.5 mmol) of Intermediate E was added to 30 ml of tetrahydrofuran and stirred at room temperature. Subsequently, 1.09 g (4.95 mmol) of zinc acetate dihydrate was added and stirred for 1 hour. Subsequently, 100 ml of methanol was added to the liquid and further stirred for 2 hours. After completion of the reaction, the precipitated solid was filtered, and the filtrate was washed with methanol and dried. In this way, 4.8 g (88%) of the exemplified compound (36) was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are δ: 11.59 (s, 2H), 7.65 (d, 2H), 7.28 to 7.12 (m, 14H), 6.30. (S, 1H), 5.86 (s, 2H), 2.69 (s, 6H), 2.38 (s, 6H), 1.97 (s, 3H), 1.26 to 1.15 ( m, 6H), 0.99-0.94 (m, 4H), 0.83 (s, 18H), 0.76 (s, 18H), 0.65 (d, 6H), 0.55-0 .43 (m, 2H), 0.32 to 0.20 (m, 2H).

−Evaluation of maximum absorption wavelength−
The exemplified compound (36) was dissolved in the measurement solvent described in Table 5 below (concentration: 1 × 10 ⁻⁶ mol / L), and the absorption spectrum was measured (optical path length: 10 mm). Table 5 below shows the maximum absorption wavelength of the absorption spectrum of the exemplified compound (36).

<Example 112>
[Synthesis of Exemplary Compound (35)]
The exemplified compound (35) described above, which is a dipyrromethene metal complex compound represented by the general formula (1), was synthesized by the method described below.

-Synthesis of Intermediate F-
1L of toluene was added to 184.77 g (0.45 mol) of Intermediate A obtained by the method described in US Patent Application Publication No. 2008/0076044, and 40 g (0.27 mol) of triethyl orthoformate, and the mixture was cooled under ice cooling. Stir. To this solution, 21.62 g (0.225 mol) of methanesulfonic acid was added dropwise, and then heated and stirred at 90 ° C. for 8 hours. After completion of the reaction, the solvent was distilled off, and the precipitated solid was washed with methanol and dried. In this way, 152.3 g (yield 73%) of Intermediate F having the following structural formula was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 11.63 (br, 2H), 7.48 (br, 4H), 7.30 to 7.02 (m, 5H), 7.02 ˜6.99 (m, 5H), 5.84 (s, 2H), 5.73 (s, 1H), 3.00 (s, 3H), 1.25 to 1.19 (m, 6H), They were 0.99-0.95 (m, 4H) 0.78 (s, 36H), 0.64 (d, 6H), 0.35-0.28 (m, 4H).

-Synthesis of Intermediate G-
To 30 g (0.2 mol) of 2,5-dimethylbenzoic acid were added 100 ml of toluene and 1.46 g (0.02 mol) of dimethylformamide, and the mixture was stirred at room temperature. To this solution, 23.8 g (0.2 mol) of thionyl chloride was added dropwise and stirred at 50 ° C. for 1 hour to obtain a reaction solution B. Subsequently, 100 ml of toluene and 23.2 g (0.025 mol) of Intermediate F were added to 216 g of 25% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature. To this solution, the previously prepared reaction solution B was added dropwise and stirred at room temperature for 10 hours. After completion of the reaction, the aqueous layer was removed, and the reaction solution was washed with 200 ml of 10% aqueous sodium hydroxide solution three times, and then washed once with 200 ml of 5% aqueous acetic acid. Subsequently, 200 ml of methanol was added to this solution and stirred for 2 hours, and then the precipitated solid was filtered and dried. In this way, 19.4 g (yield 71%) of Intermediate G having the following structural formula was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 11.05 (s, 2H), 7.53 (s, 2H), 7.30 to 7.13 (m, 14H), 6.12. (S, 1H), 5.86 (s, 2H), 2.62 (s, 6H), 2.36 (s, 6H), 1.25 to 1.18 (m, 6H), 0.99 to They were 0.95 (m, 4H), 0.79 (s, 36H), 0.63 (d, 6H), and 0.43 to 0.31 (m, 4H).

-Synthesis of Exemplified Compound (35)-
11.0 g (0.01 mol) of Intermediate G was added to 50 g of tetrahydrofuran and stirred at 50 ° C., followed by addition of 2.42 g (0.011 mol) of zinc acetate dihydrate and stirring at 50 ° C. for 1 hour. Subsequently, 200 ml of methanol was added to the solution, and the mixture was returned to room temperature and stirred for 2 hours. After completion of the reaction, the precipitated solid was filtered, and the filtrate was washed with methanol and dried. Thus, 9.0g (yield 74%) of exemplary compound (35) was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 11.57 (s, 2H), 7.53 (s, 2H), 7.28 to 7.17 (m, 14H), 6.32. (S, 1H), 5.88 (s, 2H), 2.65 (s, 6H), 2.38 (s, 6H), 1.99 (s, 3H), 1.25 to 1.18 ( m, 6H), 0.99 to 0.95 (m, 4H) 0.81 (d, 36H), 0.65 (d, 6H), 0.48 to 0.21 (m, 4H) .

−Evaluation of maximum absorption wavelength−
The exemplified compound (35) was dissolved in the measurement solvent described in Table 5 below (concentration 1 × 10 ⁻⁶ mol / L), and the absorption spectrum was measured (optical path length 10 mm). Table 5 below shows the maximum absorption wavelength of the absorption spectrum of the exemplified compound (35).

<Example 113>
[Synthesis of Exemplary Compound (37)]
The exemplified compound (37) described above, which is a dipyrromethene metal complex compound represented by the general formula (1), was synthesized by the method described below.

-Synthesis of Intermediate H-
To 30 g (0.2 mol) of 2,3-dimethylbenzoic acid were added 100 ml of toluene and 1.46 g (0.02 mol) of dimethylformamide, and the mixture was stirred at room temperature. To this solution, 23.8 g (0.2 mol) of thionyl chloride was added dropwise and stirred at 50 ° C. for 1 hour to obtain a reaction solution C. Subsequently, 100 ml of toluene and 23.2 g (0.025 mol) of Intermediate F obtained in Example 112 were added to 216 g of 25% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature. To this solution, the previously prepared reaction solution C was added dropwise and stirred at room temperature for 10 hours. After completion of the reaction, the aqueous layer was removed, and the reaction solution was washed with 200 ml of 10% aqueous sodium hydroxide solution three times, and then washed once with 200 ml of 5% aqueous acetic acid. Subsequently, 200 ml of methanol was added to this solution and stirred for 2 hours, and then the precipitated solid was filtered and dried. In this way, 15.9 g (yield 58%) of intermediate H having the following structural formula was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are as follows: δ: 10.94 (s, 2H), 7.50 (s, 2H), 7.31 to 7.13 (m, 14H), 6.13. (S, 1H), 5.83 (s, 2H), 2.52 (s, 6H), 2.33 (s, 6H), 1.26 to 1.18 (m, 6H), 0.98 to They were 0.94 (m, 4H), 0.79 (s, 36H), 0.63 (d, 6H), and 0.43 to 0.31 (m, 4H).

-Synthesis of Exemplified Compound (37)-
16.4 g (0.015 mol) of Intermediate H was added to 55 g of tetrahydrofuran, and the mixture was stirred at 50 ° C. Subsequently, 3.62 g (0.0165 mol) of zinc acetate dihydrate was added, and the mixture was stirred at 50 ° C for 1 hour. Subsequently, 120 ml of methanol was added to the solution, and the mixture was returned to room temperature and stirred for 2 hours. After completion of the reaction, the precipitated solid was filtered, and the filtrate was washed with methanol and dried. In this manner, 7.2 g (yield 39%) of Exemplary Compound (37) was obtained.
The details of ¹ H-NMR (CDCl ₃ ) are δ: 11.50 (s, 2H), 7.53 (s, 2H), 7.31 to 7.14 (m, 14H), 6.34. (S, 1H), 5.85 (s, 2H), 2.56 (s, 6H), 2.35 (s, 6H), 2.02 (s, 3H), 1.29 to 1.19 ( m, 6H), 0.99 to 0.95 (m, 4H) 0.80 (d, 36H), 0.65 (d, 6H), 0.48 to 0.21 (m, 4H) .

−Evaluation of maximum absorption wavelength−
The exemplified compound (37) was dissolved in the measurement solvent described in Table 5 below (concentration: 1 × 10 ⁻⁶ mol / L), and the absorption spectrum was measured (optical path length: 10 mm). Table 5 below shows the maximum absorption wavelength of the absorption spectrum of the exemplified compound (37).

<Example 114>
[Synthesis of Exemplary Compound (39)]
The aforementioned exemplified compound (39), which is the dipyrromethene metal complex compound represented by the general formula (1), was synthesized by a method according to Example 111 in which the exemplified compound (36) was synthesized.

−Evaluation of maximum absorption wavelength−
The exemplified compound (39) was dissolved in the measurement solvent described in Table 5 below (concentration: 1 × 10 ⁻⁶ mol / L), and the absorption spectrum was measured (optical path length: 10 mm). Table 5 below shows the maximum absorption wavelength of the absorption spectrum of the exemplified compound (39).

  Moreover, the absorption spectrum of exemplary compound (1) is shown in FIG. As is apparent from the absorption spectrum shown in FIG. 1, the dipyrromethene metal complex compound of the present invention exhibits a sharp absorption spectrum peak.

<Example 201>
[Preparation of thermal transfer recording ink sheet]
Using a 6.0 μm thick polyester film (trade name Lumirror, manufactured by Toray Industries, Inc.) with a heat-resistant slip treatment applied to the back using a thermosetting acrylic resin (thickness 1 μm), the front side of the film A coating composition for forming a dye-donating layer having the following composition containing the exemplified compound (1) obtained in Example 101 was applied by wire bar coating to a thickness of 1 μm when dried, and the thermal transfer of Example 201 was performed. A recording ink sheet was prepared.

"Dye-donating layer-forming coating composition"
Exemplified compound (1) 5.5 parts by mass Polyvinyl butyral resin 4.5 parts by mass (trade name S-REC BX-1, manufactured by Sekisui Chemical Co., Ltd.)
・ 90 parts by mass of methyl ethyl ketone / toluene (1/1 [v / v])

-Preparation of thermal transfer recording image-
The ink sheet for thermal transfer recording obtained as described above and the image receiving material for ASK2000 manufactured by Fuji Film Co., Ltd. are superposed so that the dye-donating layer and the image-receiving layer are in contact with each other, from the back side of the dye-donating material. Using a thermal head, printing is performed under the conditions of thermal head output of 0.25 W / dot, pulse width of 0.15 to 15 milliseconds, dot density of 6 dots / mm, and a magenta dye is applied to the image receiving layer of the image receiving material. When dyed in the form of an image, a clear heat-sensitive transfer recorded image without transfer unevenness was obtained.

<Example 301, comparative example 301>
[Production of color toner]
A ball mill containing 3 parts by mass of the exemplary compound (2) obtained in Example 102 and 100 parts by mass of a toner resin (styrene-acrylic acid ester copolymer; trade name Hymer TB-1000F, manufactured by Sanyo Chemical Co., Ltd.) After mixing and grinding, the mixture was melt-mixed by heating to 150 ° C., cooled and coarsely pulverized using a hammer mill, and then finely pulverized by an air jet fine pulverizer. Classification was performed to select particles having a size of 1 to 20 μm, and the color toner of Example 301 was obtained.
Further, 900 parts by mass of carrier iron powder (trade name: EFV250 / 400, manufactured by Nippon Iron Powder Co., Ltd.) was uniformly mixed with 10 parts by mass of the color toner to obtain a developer of Example 301.

  In Example 301, Exemplified Compound (2) was converted to C.I. I. A color toner and developer of Comparative Example 301 were prepared in the same manner as in Example 301 except that Pigment Red 122 (trade name Chromophthaljet Magenta DMQ, manufactured by Ciba Specialty Chemicals) was used.

  Using the developers of Example 301 and Comparative Example 301, copying was performed with a dry plain paper electrophotographic copying machine (trade name NP-5000, manufactured by Canon Inc.). Table 6 shows the results of spectral colorimetry using a spectral densitometer (trade name: X-Rite 939, manufactured by X-Rite) for the copy sample.

As shown in Table 6, the color toner using the dipyrromethene metal complex compound of the present invention has a high absolute value of a ^* and b ^* and a wide color compared to the color toner using Pigment Red 122, which is a general-purpose pigment. It was found that the reproduction range was feasible.

<Example 401>
[Preparation of ink for inkjet recording]
5.63 g of the exemplary compound (3) obtained in Example 103 and 7.04 g of sodium dioctyl sulfosuccinate, 4.22 g of the high boiling organic solvent (S-2), and the high boiling organic solvent (S-11) 5 It was dissolved at 70 ° C. in a mixed solvent of .63 g and 50 ml of ethyl acetate. 500 ml of deionized water was added to this solution while stirring with a magnetic stirrer to prepare an oil-in-water type coarse particle dispersion.
In addition, the high boiling point organic solvents (S-2) and (S-11) are compounds having the following structural formula.

  Next, the coarse particle dispersion is micronized by passing it through a microfluidizer (MICROFLUIDEX Inc.) five times at a pressure of 60 MPa, and the resulting emulsion is odor of ethyl acetate on a rotary evaporator. The solvent was removed until there was no more. To the fine emulsion thus obtained, 140 g of diethylene glycol, 50 g of glycerin, 7 g of SURFYNOL 465 (trade name, manufactured by Air Products & Chemicals) and 900 ml of deionized water were added to obtain an ink for inkjet recording of Example 401.

  The above ink for ink jet recording is packed in a cartridge of an ink jet printer (trade name: PM-G800, manufactured by Seiko Epson Corp.), and the recording medium for ink jet (product name: Photographic Finishing Pro, manufactured by Fuji Photo Film Co., Ltd.) ) Was recorded.

  FIG. 2 shows a reflection spectrum of a recorded image by the ink jet recording ink of Example 401. As apparent from the reflection spectrum shown in FIG. 2, the ink for ink jet recording of the present invention showed a sharp absorption spectrum peak, and was found to exhibit excellent properties as an ink for ink jet recording.

<Example 501>
[Production of color filter]
-Preparation of positive resist composition-
A cresol novolak resin (reaction molar ratio = 5/5 / 7.5, polystyrene-equivalent mass average molecular weight 4300) obtained from m-cresol / p-cresol / formaldehyde mixture, 3.4 parts by mass, using a phenol compound of the following structural formula O-naphthoquinonediazide-5-sulfonic acid ester (average of two hydroxyl groups esterified) 1.8 parts by mass, hexamethoxymethylolated melamine 0.8 parts by mass, ethyl lactate 20 parts by mass, and 1 part by mass of the exemplary compound (1) obtained in Example 101 was mixed to obtain a positive resist composition.

-Fabrication of color filter-
The obtained positive resist composition was spin-coated on a glass substrate, and then the solvent was evaporated. Next, the silicon wafer was exposed through a mask to decompose the quinonediazide compound. Thereafter, heating was performed at 100 ° C., and then the exposed portion was removed by alkali development to obtain a positive colored pattern having a resolution of 0.8 μm. After the entire surface was exposed, it was heated at 220 ° C. for 30 minutes to obtain a magenta single color filter of Example 501. 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.).

-Evaluation-
The solubility of the dye compound and the properties of the color filter were evaluated by the following methods. The evaluation results are shown in Table 7 below.

(Solubility)
The solubility of the dye compound in ethyl lactate at the time of preparing the positive resist composition was visually observed, and evaluated in three stages: ○ that completely dissolved, Δ that partially remained undissolved, and × that did not dissolve.

(Color change in the heating process)
The color change before and after the heating process at the time of producing the color filter was visually observed and evaluated in three stages: ◯ for substantially unchanged, Δ for slightly discolored, and x for apparently discolored.

(Color filter surface)
The surface of the produced color filter was visually observed and evaluated in three stages: ◯ for uniform, Δ for some haze, and x for clear haze (or precipitation).

(Transmission spectrum)
FIG. 3 shows the transmission spectrum of the color filter of Example 501. As is apparent from the transmission spectrum shown in FIG. 3, the color filter of Example 501 showed a sharp absorption spectrum peak. In addition, the color filter of Example 501 showed good light transmittance.

<Examples 502-509, Comparative Examples 501-503>
The exemplified compound (1) of Example 501 was replaced with the exemplified compounds (2) to (5), (35) to (37) and (39) described above and the following comparative dyes (1) to (3). A positive resist composition was produced in the same manner as in Example 501, except that a color filter was produced. Further, the same evaluation as in Example 501 was performed. The evaluation results are shown in Table 7 below.

As is apparent from Table 7, it can be seen that the dipyrromethene metal complex compound of the present invention is excellent in solubility in a solvent.
It can be seen that in Examples 501 to 509 using the dipyrromethene metal complex compound of the present invention, the color change in the heating process during the production of the color filter is small, and the surface shape of the produced color filter is good.

  ADVANTAGE OF THE INVENTION According to this invention, the coloring composition containing the dipyrromethene metal complex compound which shows a sharp absorption spectrum peak, is excellent in fastness and the solubility with respect to a solvent, and the said dipyrromethene metal complex compound can be provided. In addition, according to the present invention, it is possible to provide a thermal transfer recording ink sheet, a color toner, an ink jet recording ink, and a color filter. The present invention is expected to be used for high-quality full-color recording and the like, and has high industrial applicability.

Claims (7)

A dipyrromethene metal complex compound represented by the following general formula (1).

[In General Formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represents a monovalent substituent, and M is a metal or a metal compound X represents a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms, a substituted or unsubstituted alkylsulfonyloxy group, a substituted or unsubstituted arylsulfonyloxy group, or a halogen atom, and n1 and n2 are Each independently represents an integer of 0 to 5, and n3 and n4 each independently represents an integer of 0 to 3. ] A dipyrromethene metal complex compound represented by the following general formula (2).

[In General Formula (2), R ³ and R ⁴ each independently represent a monovalent substituent, and X represents a substituted or unsubstituted acyloxy group having 2 to 3 carbon atoms, a substituted or unsubstituted alkylsulfonyloxy. Represents a group, a substituted or unsubstituted arylsulfonyloxy group, or a halogen atom. ]   The coloring composition containing the dipyrromethene metal complex compound of Claim 1 or Claim 2.   An ink sheet for thermal transfer recording, comprising the dipyrromethene metal complex compound according to claim 1.   A color toner containing the dipyrromethene metal complex compound according to claim 1.   An ink for ink jet recording comprising the dipyrromethene metal complex compound according to claim 1.   A color filter containing the dipyrromethene metal complex compound according to claim 1.