TW201229037A - Dipyrromethene metal complex compound and coloring composition, ink sheet, toner, ink and filter including the compound - Google Patents

Abstract

This invention provides a dipyrromethene which showing sharp absorption spectrum peak and excellent in stability and soluability to solvent.

Description

201229037 VI. Description of the Invention: [Technical Profile of the Invention] The present invention relates to a bis(pyrrolidinium metal) metal complex compound, and a coloring composition containing the same product of the dipyrromethene metal compound compound, thermal transfer printing An ink sheet for recording, a color toner, an ink for inkjet recording, and a color filter. [Prior Art] At present, the mainstream of image recording is recorded in full color, and various coloring agents (dyes such as dyes and pigments) have been developed, and are used for recording materials of inkjet methods and recording materials of thermal transfer printing methods. , electrophotographic recording materials, transfer type silver halide photosensitive materials, printing inks, inks for stylus pens, and the like. In addition, in the technical field of recording or reproducing a color image in an image pickup device such as a charge-coupled device (CCD) and a liquid crystal display or a plasma display equal to a color filter, various color filter formations have also been developed. Coloring agent. In the coloring agent for forming a recording material or a color filter, a two-primary coloring agent of a so-called additive color mixing method or a subtractive color mixing method is used for recording or reproducing a full color image. However, the actual situation is that there is no stable coloring agent having an absorption property which can realize a preferable color reproduction region, and can withstand various use environments, and improvement is strongly desired. The thermal transfer recording is performed by heating a scale transfer material having a layer containing finely melted ink formed on a support body (base film) by a thermal head, so that the oil is recorded and recorded in image reception. On the material; and using the 201229037 thermal head to heat the thermal transfer material on which the pigment-providing layer containing the heat transfer pigment is formed on the support body, and the pigment is thermally diffused and transferred to the image receiving. The latter thermal transfer method can change the amount of transfer of the dye by changing the amount applied to the thermal head, so gray scale recording is easier, and it is particularly advantageous for high-quality full-color recording. However, there are various restrictions on the heat transfer pigment used in this method, and there are few heat transfer pigments satisfying all the required properties. As the desired properties, for example, it has better spectral characteristics in color reproduction, is easy to transfer, is stable to light or heat or humidity (light resistance, heat resistance, moisture resistance), and is stable to various chemicals. It is easy to synthesize and easy to produce recording materials for thermal transfer. However, the conventional dye which has been proposed to have better spectral characteristics in terms of color reproduction does not have a satisfactory degree of spectral characteristics, and further improvement is strongly desired. In a color copying machine or a color laser printer as an electrophotographic recording machine, an ink which is obtained by dispersing a coloring agent in resin particles is generally widely used. As the performance required for the color toner, absorption characteristics which can realize a preferable color reproduction region can be cited, and in particular, high transmission in the case of use in an overhead projector (hereinafter referred to as OHP (Overhead Practor)) Sex (transparency) and stability under ambient conditions. In the industry, it has been proposed to disperse a pigment as a coloring agent in a particle (for example, refer to Patent Document 专利 to Patent Document 3). Such a toner is excellent in H property, but is insoluble, so that it is easily aggregated and transparent. The problem of a decrease in sex or a change in the color tone through the color. On the other hand, there has been proposed a toner in which a specific coloring matter is used as a coloring agent (for example, see Patent Document 4 to Patent No. 201229037 J. 6). This type of toner _ transparency is highly audible, but there is a problem. The inkjet § recording method is rapidly popularized because of low material cost, high-speed recording, low mouth sound during recording, and (4) color recording, and it is not secret. In the fascia recording method, there is a continuous method for continuously squeezing the liquid droplets, and an on-demand manner for the image information to be judged to fly the droplets, and the ejection method has a pressure applied by the piezoelectric element to make the liquid shi In the method, a method in which bubbles are generated in the ink to eject the liquid droplets, a method in which the ultrasonic waves are used, and a method in which the liquid droplets are ejected by the electrostatic force is sucked. Further, as the ink for ink jet recording, an aqueous ink, an oil H ink, and a spheroidal (melt type) ink can be used. For the ink for inkjet recording, the coloring agent is required to be soluble or dispersible. Good, consistent enthalpy concentration record, good color tone, stable activity for light, enthalpy, active gas in the environment (NOx, broken, ozone, etc.), stable, excellent stability to water or medicine, for image reception The material has good fixability and is not easily bleed out, and is excellent in preservability of the ink, non-toxic, high in purity, and further inexpensive. However, it is extremely difficult to search for colorants that meet these requirements at a high level. In particular, it is desirable to have a good magenta color, a toner for light, a degree of thermal stability, and a coloring agent which can achieve a better color reproduction region and exhibit a good magenta color is strongly desired. Since the color light-receiving sheet requires south transparency, a method called dyeing using a dye for coloring has been carried out. For example, a pattern which is formed by patterning and dyeing a dyed photoresist in a pattern and then dyeing with a filter of a colored color is sequentially repeated for all of the color, 201229037 Color filter. In addition to the dyeing method, a color filter can also be produced by using a positive or negative etchant. Since the color filter produced by these methods has a high transmittance and excellent optical characteristics, the color filter is excellent in light resistance and heat resistance, and it is expected to have a variety of impurities and high permeability. Among them, a method in which an organic pigment excellent in light resistance or heat resistance is used in place of a pigment is widely known, but a color-based light sheet using a pigment is difficult to obtain optical properties such as dye. It is desirable that the dyes usable for the respective uses have the following properties in common. For example, it has a preferable color tone for color reproduction, and has excellent light absorption, good stability such as 14 um heat resistance and Wei Xue, and good solubility in a solvent. The patent document 7 discloses that it is used as a coloring agent in the color patent document 7 'the description of the methyl metal-doped compound from the genus lanthanum without the present invention, and the two-transformed sub-analog is excellent. Japanese Patent Application Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 4] Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. [7] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. That is, an object of the present invention is to provide a dipyrrolidinium conjugate compound which exhibits a sharp absorption spectrum peak' and is excellent in stability and solubility in a solvent. Further, it is an object of the present invention to provide a second one. A coloring composition of a pyrene methyl metal-miscible compound, an ink sheet for thermal transfer recording, a color toner, an ink for inkjet recording, and a color filter. As a result of repeated efforts by the inventors of the present invention, it has been found that the above problems are achieved by the following constitution. The specific means for achieving the problem are as follows. A two-degree ratio*» respective methylene metal-coordinated compound represented by the following formula (1). General formula (1)

7 £ 201229037

Do not independently represent a -valent substituent, M represents a metal or metal compound, and X represents a substituted filament substituted by a substituted $2~3 _, an unsubstituted alkylsulfonyloxy group, substituted or unsubstituted The substituted aryl sulfonium oxy group or the halogen atoms 'nl and (10) independently represent the number of 〇~5, and n3 and n4 each independently represent an integer of 〇~3. <2> A dipyrrolidino-based metal complex compound represented by the following formula (2). General formula (2)

In the formula (2), R3 and R4 each independently represent a monovalent substituent, and X represents a substituted or unsubstituted decyloxy group having 2 to 3 carbon atoms, a substituted or unsubstituted alkyl group. A decyloxy group, a substituted or unsubstituted aryl group, a decyloxy group, or a halogen atom. &lt;3&gt; A coloring composition comprising the bis-pyromethylene metal complex compound according to the above &lt;1&gt; or &lt;2&gt;. (2012) The ink sheet for thermal transfer recording containing the dipyrromethene-based metal-coordinate compound according to the above <1> or <2>. &lt;5&gt; A color toner containing the dipyrromethene metal complex compound according to the above &lt;1&gt; into &lt;2&gt;. &lt;6&gt; An ink for inkjet recording containing the dipyrromethene-based metal-substituted compound according to the above &lt;1:&gt; or &lt;2&gt;. &lt;7&gt; A color filter containing a methylene metal-substituted compound of a σ ratio p according to the above &lt;1&gt; or &lt;2 &gt; EFFECT OF THE INVENTION According to the present invention, it is possible to provide a dipyrrolidinium-based metal-coordinate compound which exhibits a sharp absorption spectrum peak and is excellent in stability and solubility in a solvent. Further, according to the present invention, there is provided a colored composition containing the dipyrromethene metal complex compound, an ink sheet for thermal transfer recording, a color toner, an ink for inkjet recording, and a color filter. . [Embodiment] The description of the configuration of the present invention described below is based on the description of a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In addition, the numerical range represented by "~" in this specification is the range which shows the numerical value of the before and after the "~. In the present specification, the "dipyrrolethylene skeleton" in the dipyrromethene metal-substituted compound means a structure represented by the following structural formula. In the present specification, the substitution position of the dipyrromethene skeleton is expressed by the following structural formula. 201229037 [Chemical 3] Substitution position of dipyrromethene skeleton • '.· · I : meso

&lt;Dipyrromethene metal complex compound &gt; [dipyrrolidino-based metal complex compound represented by the general formula (1)] The first invention of the present invention is represented by the following general formula (1) A dipyrromethene-based metal complex compound. The dipyrromethene metal complex compound exhibits a sharp absorption spectrum peak and has good spectral characteristics. Further, the diterpene 11 each of the fluorene-based metal-doped compounds has excellent heat, acidity, and wealth, and is stable. Further, the dipyrromethene-based metal-doped compound has high solubility in a solvent. [Chemical 4] 201229037. Formula (1)

In the above formula (1), R1, R2, R3, R4, R5, R6, R7 and R8 each independently represent a monovalent substituent, M represents a metal or a metal compound, and X represents a substituted or unsubstituted group. a nonyloxy 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 represented An integer of 0 to 5, n3 and n4 each independently represent an integer of 0 to 3. When nl is an integer of 2 or more, two or more R5's may be the same or different. When n2 is an integer of 2 or more, two or more R6's may be the same or different. When n3 is an integer of 2 or more, two or more R7's may be the same or different. When n4 is an integer of 2 or more, two or more R8s may be the same or different. In the present specification, the 5-amino group and the 5'-position guanamine group of the dipyrromethene-based metal-substituted compound are described by a keto form in a keto-enol tautomeric equilibrium, but may be an enol type. . The dipyrromethene-based metal represented by the above formula (1) is a compound of the compound: 2012 20120. The 2, and 3, and the positions of the benzene rt methylene skeleton are substituted or not taken. And the 5, · position is a phenyl group amino group which is substituted at the 2 position (R3 dif group in the formula (1)) J.6. unsubstituted phenyl. The monomethylene methylene metal complex compound of such a chemosystem has not been described in the general formula (1) as described in the above, and as the r1 to r8, for example, "atomic (10) gas original ΐ") Preferably, the number of stones is from 1 to 48, more preferably a C24, chain, branched or cyclic alkyl group, such as methyl, ethyl, propyl,

Butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, decyl, hexamethyl, cyclopropyl, cyclopentyl, cyclohexyl, ^, 1-adamantyl), alkenyl (preferably having 2 to 48 L carbon atoms of 2 to 18, such as ethylene, propyl, 3, butyl, aryl (preferably having a carbon number of 6 to 48, more preferably an aryl group having a carbon number of 6 to 24, such as a phenyl group or a naphthyl group, or a heterocyclic group (preferably having a carbon number of n, more preferably a stone = 1 to 18). For example, 2_nonyl, 4♦, 2, Nanwu is 2-based, 1·singyl, 2·benzoinyl, phenyl, babi &amp;, benzotriazol-1-yl) , a mercaptoalkyl group (preferably having a carbon number of 3 to 38, more preferably a methyl group of 3 to 18, such as trimethylmethylpropenyl, triethyl = alkyl, tributyl sulfonium, uncle Butyl bismuthyl fluorite, dimercapto ruthenium, perylene, cyano, nitro, alkoxy (preferably double ^ 1 to 48, more preferably carbon i~24) Alkoxy group, such as methoxy, oxy, 1-butoxy, 2-butoxy, isopropoxy, tert-butoxy, decyloxy, and, if , for example, cyclopentyloxy, jujube 12 201229037,,), money base (preferably having a carbon number of 6 to 48, more preferably a carbon material of 6 to 24, r to m such as a phenoxy group, a 1 base), a heterocyclic oxy group (preferably having a carbon number of 'the more preferred carbon number is a heterocyclic oxy group of 18, such as r phenyl tetraspora: a child's oxy group), and a ferrocene group (preferably having a carbon number of 1 to 32, more alkoxy groups, such as trimethyl-Weiyl, tert-butyl bis-di- "di-t-methyl-methyl oxetyloxy", ethoxylated (preferably having a carbon number of 2 (four) a 2 to 24 decyloxy group, for example, an ethoxycarbonyl group, a p-pentyloxy group, a 4-methyl hydrazine, a small-nano and a hydrazine having a carbon number of 2 to 48, a more carbon number; 2: an alkoxy group a carbonyloxy group (preferably ethoxy-Ml is a methoxyl group, for example, an oxy group is oxygen), and if a ring is alkoxy group is 7 to 32, more preferably, f oxy oxime (more) Preferred carboxy oxy), ammonia oxime A (for example, phenyl is 1 to 24 carbamomethoxy group, for example: 48 more preferred stone butyl carbamethyleneoxy group, „ „ ,-Methyl cyanamide, N_ Xenon A) &amp; Γ 虱 虱 醯 ,, N-ethyl-N-phenylpyrazine The oxy-oxyl group (preferably carbonaceous N-based urethane-branched bristles, such as N, N-di^), preferably having a carbon number of 1 sulfonyloxy group, ethyl acetohydroxy , Ν-propyl ketone continued to brew oxy (preferably carbon carbonyl group, such as methyl _. ^ better carbon number is 1 ~ 24 oxy), aryl simple group (: = Γ Γ oxy The number of aryl bismuth oximes with a good number of 6 to 24 is 6 to 32, more base (preferably having a carbon number of 丨~48, f彳 such as a sulfonyloxy group), a fluorenyl group, and a A thiol group with a number of 1 to 24, such as -methyl (10) group, stupid county, fourteen base, 13 201229037 cyclohexyl), alkoxylate (better carbon number 2 to 48) 2 to 24 thief silk base, oxy county, ethoxy, number is octadecyloxycarbonyl, cyclohexyloxycarbonyl, 2,6•di-tert-butyl:, decaoxyl), silk base 7~ 3 ^, cyclohexyl 7~24 aryloxy county 'such as phenoxy group', ammonia batch, several horses: = two 48, more preferably a carbon number of 1 to 24 of methotrexate, brewing base, N,N-diethylcarbazone, N_ethyl^methyl N,N-dibutylcarbamoyl, N-propylcarbamyl, ν·=bristyl, hydrazine, hydrazine- A terminal phenyl carbamoyl group, called dicyclohexylaminomethyl: methyl methoxy (preferably &amp; number 32 or less, more preferably carbon number 24 to: ammonia: ammonia hydrazine, hydrazine: hydrazine - dibutyl Amino group, tetradecylaminopyrene-ethylhexyl group, % hexyl group minus), anilino group (preferably having a carbon number of 6 to 2, more preferably 6 to 24, an anilino group such as an anilino group or a fluorenyl group) Amine cyclic amino group (preferably having a carbon number of 32, more preferably 18 _ ring group, for example, 4 to 1 amino group), phenylamine (preferably having a carbon number of 2 to 48, more preferably 2 to 24) A benzoguanamine group such as an acetamino group, a benzylamino group, a tetradecylamino group, a tridecylamino group, a cyclohexaneguanidino group, a urea group (preferably having a carbon number of 1 to 1) 32, better carbon number! Urea group of ～24, such as urea group, hydrazine, hydrazine dimethyl ureido group, fluorenyl phenyl ureido group, quinone imine group (preferably having a carbon number of 5% or less, more preferably having a carbon number of 24 or less) Amino group, for example, Νττ醯imino group, Ν-o-phenylene carbamide group, alkoxycarbonylamino group (preferably having a carbon number of 2 to 48', more preferably an alkoxy group having a carbon number of 2 to 24 Carbonylamino group, such as decyloxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, octadecyloxyamino, cyclohexyloxycarbonylamino, aryloxycarbonylamino (comparable to 201229037) The number is 7 to 32, more preferably the carbon number is 7~2 - phenoxy-silylamino), and the continuation of the amine group (preferably: charcoal base, benzoic acid, ten-shaped gas, continuous hydrazine amino group (better carbon) The number is 丨~48 = fine _ base), and the hydrazine amino group, for example, N,N-dipropyl carbite yellow ammonia, ammonia = 24 ammonia, azo (amino), azo (preferably carbon number) ^~^ More sulphur-based (preferably carbon number is 2::1=base), sulphur-based, such as methylthio, ethene, xin-g two, 1~24, its 妒 妒 铋 铋 K丞 octylthio, hexyl thiol), aromatic access group (preferably the number of pessimles is 6 to 48, more preferably a carbon number of 6 to 24, or a heterocyclic thio group (preferably having a carbon number of 32, more preferably: = a heterocyclic thio group of -18) For example, 2-stup and 嗟 硫 硫 、, (5) 3 is 1 phenyl tetrathenethio), sulfite series (preferably carbon number is 卜 ^ ^ Γ 基 亚 W, such as twelve burning Aji) Ϊ 亚 硫 ( 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳The number is the base of the 24, such as the base, the ethyl thiol group, the propyl thiol group, the butyl group, the base, the 2, the ethyl hexyl turn, the ten base, the continuation = 黄 己 基 ) ) 、 、 、 、 芳 芳 芳 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 较佳 较佳 较佳 ( 较佳 较佳 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Base (preferably having a carbon number of 32 or less, more preferably a carbon number of 1 gamma, such as 4 sister base, yt-dipropylammonyl group, = 15 201229037-based dodecylsulfonyl group, N_ethyl·n-stupylsulfonyl, N-cyclohexylaminosulphonyl), sulfo, phosphonic acid, phosphonium (preferably carbon number)~ 32, more preferably a fluorenyl group having a carbon number of 1 to 24, such as a phenoxyphosphonium fluorenyl group, a octylphosphonium fluorenyl group, a phosphinyl fluorenyl group, or a phosphinyl fluorenyl group (preferably a carbon number horse) to 32 Preferred are phosphinylamino groups of i to 24, such as diethoxyphosphinylamino, dioctyloxyphosphinylamino. When the monovalent group is a group which can be further substituted, it may be further substituted by any one of the groups. Further, when # has more than two substituents, these substituents may be the same or different. Hr2 in the above formula (1) is independently independent, and preferably a substituted or unsubstituted alkoxy group having a carbon number of 3 Å, a substituted or 2 generations having a carbon number of 1 to 3 G a substituted or substituted aryl group having a carbon number of 6 to 1 Å, a substituted or unsubstituted alkyl group having 1 to=, substituted or unsubstituted An aryl carbamoyl group having a carbon number of 7 = or a cyano group, more preferably a substituted or unsubstituted number of 6 to 3 fluorene, a substituted or unsubstituted carbon number 萁1 a mercapto group, a substituted or unsubstituted phenyl group of 2: particularly preferably an unsubstituted alkoxycarbonyl group having a carbon number of 6 to 30, and a R3 and RV in the formula (1) An independent, and more representative, decyl group having a carbon number of 1 to 3 G, substituted or unsubstituted 3 其, decyl, substituted or unsubstituted alkoxy group having a carbon number of 1 to 1 , substituted or unsubstituted carbon number of 6~(7), substituted or unsubstituted amino, or (tetra), more preferably 16 201229037 or unsubstituted alkyl having 1 to 12 carbon atoms Substituted or unsubstituted phenyl, 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 an unsubstituted carbon number of 1 to 2 The alkyl group, the unsubstituted carbon number is an alkoxy group of 丨~12, or a chlorine atom. In the above formula (1), hydrazine, octagonal hydrazine, J-led, and preferably substituted or unsubstituted alkyl group having a carbon number of fluorene-substituted or substituted or substituted carbon The aryl group, the substituted or unsubstituted heterocyclic group having 6 to 10, the substituted or unsubstituted alkoxy group having a carbon number of 丨~ buckle, and the substituted or unsubstituted carbon number of 6~ The ω, the substituted or unsubstituted carbon number is 1 to 3 fluorenyl, the substituted filament has a carbon number of 6 to 1 〇, the substituted or unsubstituted carbon number a 2 to 30 fluorenyl group, a 'disubstituted or unsubstituted alkoxycarbonyl group having a carbon number of 2 to 3 Å, a substituted or unmodified carbon number of 1 to 30 yl groups, substituted or The carbon number of the undead is methacrylate, substituted or unsubstituted. The amino group of G~3G, cyano group, halogen atom, secret group, fluorenyl group, phosphonic acid group is more preferably substituted or not. The substituted carbon number is 1~daily __green, substituted silk substituted, unsubstituted or unsubstituted phenoxy, : substituted "stupid! ^ Generation of alkylthio having 1 to 18 carbon atoms, substituted or not a, substituted or unsubstituted carbon having a carbon number of 2 to 18: generation or non-i algebra of 2 to 18 Carboxyl, unsubstituted carbon 3 2 18 fluorenyl, substituted or horse 118 "Kata, substituted or unsubstituted 17 201229037 f number G ~ 18 amino, cyano, (four) , gas secret, county, county, or phosphonic acid group, the second base, unsubstituted phenyl, unsubstituted two ==:1 oxime county, no number; In the general formula (1) of the vehicle base, (four) sub, gas atom, _ sub, ^, winter nl盍,,,; μ from the community ▲ 4 cruel R5 can be bonded to each other to form 5 members, 6 members or 7 The number of the members = the phase = the ring formed, for example, the benzene ring and the ring of the ring of the ring of the ring are singular rings, which can be difficult to sculpt. When η2, η3, and ^ clothing are =: adjacent to adjacent A's &amp; adjacent two are also 5 members and another 6 Ϊ ί : R7 is adjacent, R3 and R7 can be bonded to each other to form a member 6 or 7 . As the formed ring, for example, ?_' is preferably the same as described above when benzene ring R is adjacent to R. Further, when the ring of the five members, the six members, and the seven members formed is a group which can be substituted, it may be substituted with any one of the substituents of the valence, and when two or more substituents are used. When replaced, these same can also be different. In the general formula (1), n1 and n2 are divided into Q~, preferably 〇~3, more preferably 0~2, and particularly preferably (UiU. In the formula (1), n3&amp; N4 is independently 〇~3, preferably 0~2, and particularly preferably (^戈). Nomura number, 18 201229037 In the above formula (1), 'as a metal or a metal compound represented by Μ, as long as it is A metal atom or a metal compound which can form a complex, which may be any, including a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride.

Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni,

Co, Fe, B, etc., in addition to Alcl3, InCl3, FeCl2

Metal vapors such as TiCl2, SnCl2, SiCl2, GeCl2, metal oxides such as Ti〇 and VO, and metal hydroxides such as Si(OH)2. From the viewpoints of stability, spectral characteristics, heat resistance, light resistance, and manufacturing 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, pt, pd, &amp;, Ni, Co, B or VO ' is particularly preferably Zn. In the above formula (1), X represents a substituted or unsubstituted carboxy group having 2 to 3 carbon atoms, a substituted silane group, a substituted or unsubstituted aryl group. The methoxy group, or _ primogen h χ is preferably a substituted or unaged Wei 2~3(tetra)oxy group, a county or unsubstituted thioloxy group having a carbon number of 1 to 3 G, substituted or The unsubstituted carbon number of the aryl sulfoxide having a carbon number of 6 to 30, or the gas atom is preferably a substituted or unsubstituted carbon number of 2 to 3, and the unsubstituted carbon number is 丄~ The aryl group of 18, which is an unsubstituted aryl group having a carbon number of 6 to 2, is particularly preferably a substituted or unsubstituted ethoxy group having 2 to 3 carbon atoms. The substituent represented by R~R, Μ, χ in the di-transmethylene metal-coupling compound represented by the above formula (1) is preferably at least one of these substituents. The substituent is the preferred group, and the most preferred substituent i is a preferred form of the two-fold compound represented by the above formula (1). That is, the base metal is combined: in the above formula (1), the group 疋 and R2 in the following formula are exemplified as or not A; and the substituted aryl group having a carbon number of 6 to 10 continued: The substituted or unsubstituted carbon number is 〜~3〇 or the unsubstituted aryl group with a carbon number of 7~u “醯::; the atmosphere ^ and the substituted or unsubstituted carbon number are 1~30 =:==~:::: aryloxy group, substituted or ung 6 to 10 aryloxy group, substituted or unsubstituted amino group, or dinary number 1: 2 and R: each independently substituted Or unsubstituted carbon aryl i, by: metabox, substituted or unsubstituted carbon number 6^10 = unsubstituted heterocyclic group, substituted or unsubstituted 10 The number of carbons substituted by the fluorene reduction and the peak substitution is 6~. The substituted or unsubstituted carbon number of the thiol red substituted or unsubstituted arylthio group having a carbon number of 6~1〇 Substituting 20 201229037 Two child-substituted thiol groups having a carbon number of 2 to 30, substituted or unsubstituted alkyl group having 2, a substituted or unsubstituted alkyl group (tetra) Base, substituted or unsubstituted carbon number is 1~ The methotrexate, substituted or unsubstituted carbon number is G~3Q amino group, cyano group, atomic, green, hetero, county, or squaric acid group, nl 1 n2, n3 and n4 are each independently 0~ 3, Μ is Fe, zn, Mg, si, pt, pd, M〇, Mn C〇'Ti〇, B or v〇, X is a substituted or unsubstituted fluorenyl group having 2 to 3 carbon atoms The substituted or unsubstituted carbon number is 1 to 3 G decyloxy, substituted or unsubstituted arylheterooxy group having a carbon number of 6 to 3 G, or a gas atom. A more preferred form of the dipyrromethene metal bismuth chelate represented by the above formula. #, the more preferred form is the following group s. In the above formula (1), an R and R is a substituted or unsubstituted alkane having a carbon number of ό~30, and the cyclized, unsubstituted or unsubstituted carbon number is a 12-substituted phenyl sulfonium group. The base or the cyano group, R3 and R4 are all substituted, unsubstituted or unsubstituted phenyl groups substituted by the silk, substituted by the substituted filaments, having a carbon number of 1 to 12 Silk-based, substituted or unsubstituted phenoxy, or bromine , R5 and R6 are both substituted or unsubstituted carbon atoms, substituted phenyl substituted, substituted filaments with a carbon number of 1 to 18, and heterogeneous Or untreated base group, substituted 21 201229037 or unsubstituted alkylthio group having 1 to 18 carbon atoms, substituted or unsubstituted phenylthio group, substituted or unsubstituted carbon number 2~ 18 fluorenyl, substituted or unsubstituted alkoxycarbonyl group having 2 to 18 carbon atoms, substituted or unsubstituted alkylsulfonyl group having a carbon number of from 18 to 18, substituted or unsubstituted a carbamoyl group having 1 to 18 carbon atoms, a substituted or unsubstituted amino group having 0 to 18 carbon atoms, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, a carboxyl group, a sulfo group, or a phosphine. The acid group, R and R8 are each a substituted or unsubstituted alkyl group having a decano group of 18 to 18, a substituted or unsubstituted phenyl group, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms. An oxy group, a substituted or unsubstituted phenoxy group, a substituted or substituted carbon atom having an alkyl group of 丨~18, a substituted or unsubstituted phenylthio group, substituted An unsubstituted fluorenyl group having a carbon number of 2 to 18, a substituted or unsubstituted wei 2 to 18 filament group, a substituted or unsubstituted aryl group having a carbon number of 1 to 18 The substituted or unsubstituted amino-methyl group having a carbon number of 1 to 18, substituted by a substituted filament, having an amino group of 〇 18, a cyano group, a fluorine atom, a gas atom, a desert atom, a thiol group, and a slow Base, contiguous, or phosphonic acid group, nl and n2 are both 〇~2' n3 and n4 are 〇~2, Μ is Fe, Zn, Mg, Si, Pt, pd, Cu, Nic〇VO, ^ X Is a substituted or unsubstituted fluorenyloxy group having 2 to 3 carbon atoms, an alkylsulfonyloxy group having no number of 18, or an unsubstituted arylsulfonyl having 6 to 12 carbon atoms. Oxygen. The dimethylene metal 22 represented by the above formula (1) is shown below. 201229037. The most surface (4) of the compound. That is, the best position is a combination in which R and R are each an unsubstituted alkoxy group having a carbon number of 6 to 3 Å or a cyano group, R and R4 is an unsubstituted carbon group having a carbon number of 12, an unsubstituted alkoxy group having a carbon number of 1 to 12, or a gas atom, and R5 and R6 are each an unsubstituted carbon number of 丨~12. Alkyl, unsubstituted, stupid, unsubstituted, dipyridyl 2 oxy, unsubstituted fluorenyl group having 2 to 12 unsubstituted, unsubstituted alkoxy group having 2 to 18 carbon atoms The base, the unsubstituted carbon number is an alkylsulfonyl group of 丨~12, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, or a carboxyl group, and R, R8 are unsubstituted carbon numbers of 1 to 12 Alkyl, unsubstituted phenyl, unsubstituted carbon number is 12 oxy, unsubstituted fluorenyl group having 2 to 12 carbon atoms, unsubstituted carbon oxide having 2 to 18 carbon atoms The base, the unsubstituted carbon number is an alkylsulfonyl group of 丨~12, a fluorine atom, a chlorine atom, a bromine atom, a thiol group, or a thiol group, and nl and n2 are both 〇 or 卜 n3 and n4 are 〇 or dip is Zn, X is substituted or unsubstituted The number 2 or 3 acyl group; or, dipyrromethene Yue fund the preferred form is represented by the following general formula (2) compound represented by the genus malocclusion. [Dipyrrolidino-based metal-substituted compound represented by the general formula (2)] The dipyrrolidino-based metal represented by the above formula (1) is a compound of 23, 201229037 The compound represented by the formula (2) is more excellent in solubility in an organic solvent, a miscibility of a methylene metal, and a stability of a domain, and is a heat-resistant formula. (2)

In the formula (2), R3 &amp; R4 is a substituent, and X represents a substituted or unsubstituted: f represents a fluorenyloxy group of a sirolimus or a fluorene substituted or nuclear substituted The base record is transferred to the base or better. ▲4 substituted silk in the above formula (2), r3, r^d, AA R3 &gt; p4 „ v ^ and X are respectively the same as R, R and X in the formula (1: The preferred embodiment is the same. The preferred embodiment of the di-transalkylene group represented by the above formula (2) is shown below. The preferred embodiment is the following group s. And _R and R4 are each independently substituted or unsubstituted alkyl having 碳~邛, substituted or unsubstituted 6~1〇 aryl, substituted or unsubstituted carbon The number of 1 to 3G cyanooxy group, the substituted carbon substituted carbon 24 201229037 number is 芳10 aryloxy, substituted or unsubstituted amino, or dentate atom, ^ X is substituted or not Substituted octagonal carbon having 2 to 3 carbon atoms, substituted or unsubstituted oxime having a number of gorges of 1 to 30, substituted or unsubstituted aryl having a carbon number of 6 to 30 Further, the oxy group or the chlorine atom is used. Here, R3 and R4 are preferably the same substituents. The following is a description of the diπ-pyrylene sulfhydryl metal-substituted compound represented by the above formula (2). Good form. That is, A more preferred form is a combination wherein, in the formula (2), R3 and R4 are each independently a substituted or unsubstituted alkyl group having a carbon number of i to 12, substituted or unsubstituted benzene. a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, a substituted or unsubstituted phenoxy group, a chlorine atom or a desert atom, wherein X is substituted or unsubstituted. 2 to 3 of an anthraceneoxy group, an unsubstituted alkylsulfonyloxy group having 1 to 18 carbon atoms, or an unsubstituted arylsulfonyloxy group having 6 to 12 carbon atoms. "The same substituent as R4. The preferred form of the diterpenoidyl metal-substituted compound represented by the above formula (2) is shown below. That is, the most preferable form is the following combination: In the above formula (2), R3 and R4 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, and X is The substituted or unsubstituted fluorenyl group having 2 to 3 carbon atoms. Here, 'preferably R3 and R4 are the same substituents. 25 201229037 The following shows the dipyridyl represented by the above formula (1) Specific examples of the fluorenylene-based metal-substituted compound are not limited to these specific examples. Further, R1()1, R102, R103, M1 and X101 in Tables 1 to 4 represent the following formula ( a substituent in 3). (Chemical Formula 6) Formula (3)

ΗΝ Μ ΝΗ

26 201229037 [Table i] Exemplary compound R'01 R102 R,03' X'0' M1 1 t-Bu , —Ο^-Ο-ΛΛ-Μβ ~o Me ~ζ) —OC-Me S Zn 2 t- Bu ^ , βΚ • ^o Me 七-OC-Et 0 Zn 3 t-Bu Me OH -OC Human Me 0 Zn 4 t:Bu —Ο-ΟΗ^Λ-Μβ Me -b —Cl 2n 5 t-Bu — C _0.·^^ )-Me -o Me -b —Br Zn 6 t-Bu —^~^~~ j〉~Me Me 〇—Me s Zn 7 t-Bu —C-0—^ \—Me ° t-Bif^ Me 0 -o-^-a &amp; Zn 8 t-Bu , —C-0-(^-Wle o Me 〇^*e Zn 9 t-Bu —C-0-/~~VMe t-Bu ~o Me -b -fO Zn 10 t-Bu _ir_° \Z)^Me -o Me -3⁄4 o — _0'l_O_Me 0 Zn 27 201229037 [Table 2] Exemplary compound R101 R102 R103 X101 M1 11 t- Bu l*DU —O^Q-Me 0 Zn 12 t-Bu t-Bu F3Q —〇-Q-Me 0 Zn 13 t-Bu t-Bu Me —CH,a m. eO-fJ-Me 0 Zn 14 t-Bu t-Bu7 —^^-NHAc —〇-Q-Me 0 Zn 15 t-Bu \Z/Me t-Bu ~8 —〇-Q-Me 0 Zn 16 t-Bu §_〇O~Me t-Bu Me(D -b MeQ - OQ-Me 0 Zn 17 t-Bu t-Bu 广MeO C〇2Et - Ο-ζ-Μβ 0 Zn 18 t-Bu -ς-Ο-ΛΛ-Me t-Bu -^^-0 Me MeO O'Me —〇-Q-Me 〇Zn 19 t-Bu, t-Bi/ MeO H3C NHAc 七一 O-fJ-Me 0 Zn 20 -C N -o Mev ~v^~Me -^Ο*〇-Μβ 0 Zn 28 201229037 [Table 3] Exemplary compound R101 R102 R103 X1. 1 M1 21 A C〇2Me —O:0-Me 0 Zn 22. -C02Et HO —Ο-ζ-Me 0 Zn 23 Me -CO^Me -o h3chn —OQ-Me 0 Zn 24 PH3 -co2^Me -8 —OC-Me 0 Zn 25&quot; A CONhl2 o Me Me —ο-ς- Μβ 0 Zn 26 -CONHEt -o —Ο-ζ^-Me 0 Zn 27 o -bF —0 兮Me 〇Zn 2δ —S〇2Me o MeG OMe —0 —Q—Me 0 Zn 29 o Cl a —O- ^-Me 0 Zn 3〇O -Q Me^ a C|2 a 29 201229037 [Table 4] Exemplary compound R101 R102 R103 X101 M1 31 A CONHAc o Q HInTj302H -Cl Ni 32 t-Bu -ς-Ο-ty- Me t-Bu o Q % -C! Co 33 t-Bu t-Bu factory o P -3⁄4 -Cl Fe 34 t-Bg. t-Bu o ~F -Gt Cu 35 t-Bu 〇t-Bu Guang- Q Me. -og-cH3 0 Zn 36 t-Bu^ -g-0-/~VMe 〇t-Bu Guang Ma -〇-Μθ -〇-q-ch3 0 Zn 37 t-Bu -ς-ο-/ ~Λ-Μθ t-Bu广〇-o -Og-CHa 0 Zn 38 t-Bu υ t-Bu factory~o M€i —Cl 2n 39 t-Bu -C-〇-〇&quot;Me 0 t- BiJ -o Me -0-C-CH3 0 Zn Among the exemplified compounds, the exemplified compound (1) to the exemplified compound (10) are also represented by the above formula (2) Specific examples of the dipyrrolidino group metal-substituted compound. 201229037 „ The dipyrromethene metal-doped compound represented by the above formula (1) can be referred to the specification of U.S. Patent No. 4,774,339, the specification of U.S. Patent No. 5,433,896, and the Japanese Patent Laid-Open Publication No. Hei. Japanese Patent Laid-Open Publication No. 2002-155〇52, Japanese Patent No. 3614586, Australian Journal of Chemistry 1965, 11, 1835~1845 (Aust. J. Chem, 1965, 11, 1835~1845), J Η. Borg et al., Heteroatomic Chemistry, Vol.l, No. 5, 389 (1990) (J. H, Boger et al, Heteroatom Chemistry, Vol_l, No. 5, 389 (1990)), Japanese Patent The maximum absorption wavelength Xmax of the dipyrromethene metal compound represented by the above formula (1) is synthesized by the description of the paragraph 〇l3i to the paragraph 〇157 of JP-A-2008-292970. The maximum absorption wavelength Xmax of the bis-α-methylene methylene metal-doped compound represented by the above formula (2) is preferably in the range of 500 nm to 620 nm, more preferably in the range of 520 nm to 600 nm, which is particularly preferable. It is in the range of 530 nm to 580 nm. Furthermore, the maximum absorption wavelength λ Μχ is using spectrophotometry. UV-2400PC (manufactured by Shimadzu Corporation). The dipyrromethene-based metal-doped compound of the present invention is preferably used as a magenta in the three primary colors in the use of a color image forming material. The ruthenium-based metal-doping compound is preferably used as, for example, a bright-line truncation in the use of a color ray-reel material (blocking the yoke wavelength of 1064 nm as a Yttrium Aluminum Garnet (YAG) laser 2 The use of double-wavelength 532 nm light), or the color-correction use of the long-wavelength end of the red filter, and the short-wavelength end of the blue light-sensitive sheet 31 201229037 Color correction use. &lt;Coloring composition> Bu Yi Ben Mao Ming The second invention is a coloring group containing a binary ratio = methyl gold compound represented by the above formula (1). The color composition of the material is a, a, ', and a photosensitive transfer ink. Sheet, ink for inkjet recording, color ink, color light film, pen for notes, colored plastic, other ink liquid, etc. The colored composition of the present invention is particularly preferably used as a thermal transfer recording ink Tablet inkjet δ self-employed oil In the following, a thermal transfer recording ink sheet containing the dipyrromethene compound represented by the above formula (1), and an oily ink for inkjet recording, The % color toner and the color filter are described in detail. <Ink sheet for thermal transfer recording> The ink sheet for thermal transfer recording of the present invention usually has a phase structure provided on a support body, and a coloring matter thereof The feedstock containing the general-purpose sheet can be produced by dissolving the =, - Γ 一 亚 a methylene metal-misc compound and a binder - in a solvent towel, or a granule , _ will correct the Wei green on the dragon, appropriate: color division by the general formula (1) two = base metal error. In addition to the compound, it is also possible to use other pigment coloring ink sheets simultaneously. When it is used for the full-z recording material, it is preferable to contain a cyan ink sheet which can form a heat-diffusing cyan pigment which can form a blue 32 201229037 color image, and can be formed. ? The magenta ink sheet of the heat-diffusing magenta dye of the work color image and the yellow ink sheet containing the heat-diffusing yellow pigment of the yellow image are sequentially formed on the support. Further, an ink sheet containing a color image forming material may be formed as needed. ", as the cyan ink sheet, for example, a cyan ink sheet described in Japanese Patent Laid-Open No. Hei No. 103-477477 or Japanese Patent Laid-Open No. Hei No. 194----- The yellow ink sheet described in Japanese Patent No. 4468907 or the like is used. As the magenta ink sheet, the present invention comprising the compound of the formula (1), which is called a methylene metal compound, is used. The thermal transfer printing ink sheet is used for the thermal transfer printing. # (Support) The support of the printing ink 4 can be appropriately selected as the support for the support for the ink sheet. For example, 曰 can be preferably used. The material described in the paragraph No. of the Kaikai No. 7-137466. The thickness of the branch _ is preferably 2 μm to 3 〇 μηη. (Pigment providing layer): for the transfer printing ink sheet The pigment provides a thickening of the layer: it is required to be (five) heat ten, which is hindered by the heating material, which is represented by the general formula, which is represented by the formula, or the other pigmentation diagram. There are no special types. For example, 'Japanese patents can be cited. In the case of the solvent for forming a dye supply layer, a previously known solvent can be appropriately selected, and a Japanese patent can be preferably used. The solvent described in the example of the Unexamined Patent Publication No. 7466. The pigment in the dye-providing layer, and the bismuth-based metal ruthenium compound represented by the formula (1) is preferably 〇.〇3 g/m2. ~i 〇g/m2, more 〇] coffee 2~μ 咖. In addition, the thickness of the pigment supply layer is preferably 〇.2μιη~5 is called 'better than 0.4 μπι~2 μιη. (functional layer) sensitive The ink sheet for transfer recording may have a layer other than the dye supply layer as long as it does not excessively inhibit the inside of the present invention. 歹 '少伽 can have an intermediate between the branch body and the dye supply layer. The layer may also be a side surface of the branch opposite to the dye supply layer (hereinafter also referred to as "back = square Γ: surface layer. As the intermediate layer, for example, an undercoat layer may be used, or: The dipyrromethene eutectic represented by the general formula (1): It is known that a ^ is used as the old surface layer, and for example, a weather resistant layer and a moon layer can be cited, so that it is possible to prevent the thermal head from sticking to the ink sheet. ... (The thermal transfer recording method) The ink sheet for transfer recording is used in combination with a heating mechanism such as a thermal transfer recording head and an image receiving material. That is, the sensor/head ===force square= special_(4) image recording signal has heat from the heat The portion of the passivation 5 is transferred to the image receiving material and fixed, thereby being recorded in Figure t 34 201229037. The image receiving material usually has a configuration in which a polymer-containing ink absorbing layer is provided on the support. For the configuration of the image-receiving material or the material to be used, for example, the constitution or the material used in the paragraph No. 0056 to Paragraph No. 0074 of the Japanese Patent Laid-Open No. Hei 7-137466 can be preferably used. &lt;Color toner&gt; + The color toner of the invention contains the dipyrromethene metal complex compound represented by the above formula (i). As the color toner for introducing a specific sulfhydryl-based metal-based compound represented by the above formula (1), it is possible to use all the binders generally used in toner applications. Resin. = styrene resin, acrylic resin, styrene/propylene 2 resin, polylysate, etc. are mentioned. In order to improve the secret function of the secret fluid, it is also possible to externally add inorganic fine powder and organic micro- _ can be preferably used to treat the surface with a coupling agent or the like. 2 = fine particles, titanium dioxide fine particles. Further, these fine particles are preferably fine particles having a particle diameter of 1 Gnm to 5 GG nm, and further, 0.1 mass% / 〇 to 20 mass% is added to the toner. Two of the five release agents were used as the color ink. With Zhao, it is a kind of H-knife, polystyrene, ethylene-acrylic copolymer, etc. 1. Add 1 mass 〇 / 〇 ~ 5 quality 〇 / / add powder to the toner, charge control :. , can be used as needed. For example, four can be cited: ί is a colorless charge control, a charge control agent for a salt structure, a charge control agent having a hydrocarbon structure of a cup aryl 35 201229037, and the like. Or the only one of the resin packs containing the surface of the iron particles: the average particle diameter of the average particle size is preferably 3 G μπι 15 15 μm i i = the image forming method using the color toner, and there is no special Restriction: after:: Γΐ the following method: forming a color map on the photoreceptor to transfer an image to form an image; or transferring an inter-image transfer body or the like formed on the photoreceptor, in the intermediate transfer body After the color image is formed, the silk image is transferred onto the paper image forming member. &lt;Inkjet recording ink&gt; The ink for inkjet recording of the present invention contains a -biloline methyl metal-coordinated compound represented by the above formula (丨). The ink for inkjet recording can be produced by dissolving and dispersing a methylene metal represented by the above formula (1), and dispersing and/or dispersing it in a lipophilic medium or an aqueous medium. Good use of aqueous media. The ink for inkjet recording contains a dye compound (except for the dipyrromethene metal complex compound represented by the above formula (1)), which is excellent in not only spectral characteristics or stability, but also excellent in solubility. Therefore, it is suitable as an ink for inkjet recording. (Additive) The ink for inkjet recording contains other additives as needed insofar as the effect of the present invention is not impaired. As other additives, for example, an anti-drying agent (wetting agent), an anti-fading agent, an emulsion stabilizer, an infiltration 36 201229037, a facial absorbent, a preservative, an antifungal agent, a pH adjuster, a table adjuster, and an elimination agent are mentioned. Foaming agents, viscosity modifiers, dispersing agents, and fractions: often known as two additives. These various additives are preferably used to prevent the ink from being dried by the ink of the ink jet recording ink as the anti-drying agent, preferably having a lower vapor pressure than the anti-drying agent. The water solubility of water. Specific examples are exemplified by ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol, thiodiglycol, dithiodiglycol, and 2-methyldecapropanediol, 1,2,6-hexyl Polyols such as triol, acetylene glycol derivatives, glycerol, trishydroxypropyl propyl alcohol, etc., such as ethylene glycol monodecyl (or ethyl) ether, diethylene glycol monodecyl (or B) Lower alkyl ethers of polyols such as ether, triethylene glycol monoethyl (or butyl) ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dioxan-2- a heterocyclic compound such as an imidazolidinone or an N-ethylmorpholine; a sulfur-containing compound such as sulfolane, dimercaptosulfonium or 3-sulfolenesulfone; or a polyfunctional compound 'urea derivative such as di-propanol or diethanolamine. Among these, a polyhydric alcohol such as glycerin or diethylene glycol is more preferred. Further, the anti-drying agent may be used singly or in combination of two or more. It is preferred to contain 1 〇 mass 0 / 〜 to 50% by mass of these anti-drying agents in the ink. The penetration enhancer is preferably used for the purpose of better penetrating the ink for inkjet recording into paper. As the permeation enhancer, ethanol, isopropanol, butanol, di(tri)ethylene glycol mono-, 1,2-hexanediol, etc., can be used. If the ink contains 5 mass of active surfactant, the amount of penetration of these penetration-promoting papers (through-printing), which usually has a sufficient effect, produces a bleed of the print, and the ultraviolet absorber is For promotion. For the purpose of using the ultraviolet ray absorbing agent, the singularity of the second singularity of the singularity of the singularity of the singularity of the singularity of the smear The cinnamic acid-based compound described in the publication of the Japanese Patent Publication No. __6, the Japanese Patent Special Kaiping 4 Marriage, the Suihua No. 427 Bulletin, the Japanese Special ==Special _ Kaiping Patent Special Open No. = + Day == The bulletin, 曰本铼八报曰本本特表平8-501291 ctllt * ^search Disclosure (Yayan Jiu Phi Road) No.24239, the compound or the laughing system, benzodiazepine absorbs ultraviolet light to emit firefly Light compound 'The anti-fading agent is used for the purpose of improving the preservation of an image. As the anti-fading agent, various organic and metal complex type toners can be used. As an organic anti-coloring agent', there are p-phenylene _, alkoxy 38 201229037. Phenols, dialkoxyphenols, phenols, anilines, amines, confluences, chromans, alkoxy Examples of the metal complexes such as anilines and heterocyclic rings include nickel complexes and rhodium complexes. More specifically, Research Disclosure No. 17643, items VII to J of Research VII, Research Disclosure No. 15162, 650 pages of Research Disclosure No. 18716, 527 pages of Research Disclosure Νο·36544, Research Disclosure 872 pages of No.307105, Research Disclosure

The compound described in the patent document cited in No. 15162, or the formula and the compound example of the representative compound described in pages 127 to 137 of JP-A-62-215272. Compounds included. Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyrithione _1 _ oxide, ethyl p-hydroxybenzoate, benzopyrene isothiophene and its Salt and so on. It is preferred to use 0.02% by mass to i.oo in the ink for these anti-indicators.

As the pH adjuster, the neutralizing agent (organic domain, inorganic domain) can be used. In order to improve the storage stability of the ink for inkjet recording, it is preferred to add the pH adjuster in such a manner that the pH of the ink for ink jet recording reaches 6 to ' to better adjust the pH of the ink for inkjet recording. The pH adjuster was added in such a manner that it reached 7 to 1 Torr. As the surface tension adjusting agent, a nonionic, cationic or anionic surfactant can be mentioned. Further, the surface tension of the ink for inkjet recording of the present invention is preferably from 20 mN/m to 60 mN/m, more preferably from 25 mN/m to 45 mN/m. Further, the ink for inkjet recording of the present invention The viscosity is preferably 3〇39 201229037 mPa.s or less 'more preferably 2〇mPa.s or less. As examples of the surfactant, preferred are fatty acid salts, alkyl sulfates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, dialkylsulfosuccinates, alkyl phosphates, An anionic surfactant such as a naphthalenesulfonic acid formaldehyde condensate or a polyfluorene vinyl alkyl sulfate salt, or a polyoxyethylene alkyl ether, a polyoxyethylene alkyl allyl ether, a polyoxyethylene fatty acid ester, or a sorbitan A nonionic surfactant such as a fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, a polyoxyethylene alkylamine, a glycerin fatty acid ester, or an oxyethylene oxypropylene block copolymer. Further, SURFYNOLS (trade name, manufactured by Air PiOducts & Chemicals), which is an acetylene-based polyoxyethylene oxide surfactant, is preferably used. Further, an amine oxide type amphoteric surfactant such as N,N_, fluorenyl-hydrazine-alkylamine oxide or the like is also preferable. Further, as a surfactant, it is also possible to use a surfactant as described in Japanese Patent Laid-Open No. 59-157636, pages 37 to 38, Research Disclosure No. 308119 (1989). As the antifoaming agent, a fluorine-based or organic stone-based compound or a chelating agent represented by ethylenediaminetetraacetic acid (Ethylene Diamine (3) such as Acid, EDTA) may be used as needed. (Preparation method of ink for inkjet recording) When the dipyrromethene metal-coordinated CT article represented by the above formula (1) is dispersed in an aqueous medium, it is preferably as disclosed in Japanese Patent Laid-Open No. 11-286637, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2, No. Hei. No. Hei. No. Hei. The fluorene-based metal-miscing compound and the oil 201229037 The colored particles of the soluble polymer are dispersed in the aqueous medium t, or as described in Japanese Patent Laid-Open No. 2001-262018, Japanese Patent Application Laid-Open No. Hei No. Hei. Dispersing a diterpene methylene metal complex compound dissolved in a high-boiling organic solvent in an aqueous medium as described in each of Japanese Patent Laid-Open Publication No. Hei. No. 2002-80772 . Specific method for dispersing a dipyrromethene metal compound represented by the above formula (aqueous group) in an aqueous medium, oil-soluble polymer, high-boiling organic compound, additive, and their use amount The divalent methylene metal compound may be dispersed in a fine state in a solid state, or a dispersing agent or a surfactant may be used in the dispersion. For the dispersing device's use of age H or impeller equipment, online search for skirts, grinding machines (such as colloid mills, ball mills, sand mills, grinding machines, grinding machines, mixing mills, etc.), ultrasonically Drop device, high-pressure emulsification and dispersing device (high-pressure homogenizer; Gaulin as a specific commercially available device, micro-fluid homogenizer, DeBEE2000 (BEE International), etc.). Preparation method for ink for nozzle ink recording In addition to the above-mentioned special documents, Japanese Patent Laid-Open No. Hei 5-148436, Japanese Patent No. Hei 5-295312, Japanese Patent Laid-Open No. Hei 7-97541, Japanese Patent, Kaiping No. 7-82515 It is also described in detail in each of the publications of Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Water is used as a domain, and a mixture of water-miscible organic _ can be used for rooting. Examples of the water-miscible organic solvent 201229037 include: alcohol (for example, methanol, ethanol, s-alcohol, diethylene glycol) , triethyl 4-tetrapropyl, propanol, dipropylene glycol, polyprene-alcohol, propylene glycol, hexanol, isobutanol, sec-butanol, tert-butanol, = n-propanol, butanol), polyols (such as B Dioxin, knowing, enzymatic, cyclohexanol, stupyl alcohol, butanediol, p, polyalcohol, thiodiglycol), diol street ♦ guangguang = glycol monoterpene ether, ethylene glycol monoethyl ether Ethylene glycol monobutyl ether II (eg: early methyl ether, diethylene glycol monobutyl hydrazine, propylene glycol monomethyl test, internal 222 τ 乙 知 early methyl ether, ethylene glycol diacetic acid shovel ethyl alcohol early methyl ether Acetic acid vinegar, triethylene glycol monomethyl ether, triethyl?:, ethylene glycol monophenyl (4), amine (such as ethanolamine, diethanolamine, three B =, - mercapto monoethanolamine, hydrazine ethyl diethanolamine, morpholine, N-ethyl, = diamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethyl' internal diamine And other polar solvents (such as guanamine, hydrazine, hydrazine-dimercaptocarboxamide ~ ν, ν-dimethylacetamide, dimethyl sulfoxide, cyclobutyl hydrazine, 2 - pyrrolidine hydrazine, hydrazine -Methyl-2·°pyrrolidone, fluorenyl-vinyl-2-pyrrolidone, 2-oxazole-sintered, 乜3·didecyl-2-imidazolidinone, acetonitrile, acetone). Further, the water-miscible organic solvent may be used in combination of two or more kinds. ° &lt;Color filter&gt; The color filter of the present invention contains the two-π-pyroya represented by the above formula (1) Sulfhydryl metal is a compound. Since the color filter contains the dipyrromethene-based metal-miscible compound, the transmittance is high. As a method of forming the color filter, there is a method of first forming a pattern by using a photoresist and then performing dyeing; or, for example, Japanese Patent Laid-Open No. Hei 4-146052, Japanese Patent Laid-Open No. Hei 4-128703 42 201229037 j. The photo-resistance of the 歼 各 各 4 4 _ _ _ _ _ _ _ _ _ _ _ _ _ _ 4 008 008 008 008 008 008 来 来 来 来 来 来 来 来 来 来 来 来 来 来 来 来 来 来 来 来 来 来The method used in the case of the second dimethylene metal erbium 2 nd film can be used in the method described in Japanese Patent Laid-Open No. Hei. Second, = the color of the color, the formation method: the composition containing the thermosetting tree diterpenoid compound, cross-stitching, coloring agent and dissolved positive anti-| composition on the substrate, through the Wei cover for exposure The exposure is nine. P is subjected to development _ into a positive _ pattern, and the positive anti-reagent pattern of Ranlin is subjected to full exposure, which in turn hardens the exposed positive resist pattern. In addition, a method of forming a color filter including the following steps: a method of forming a color filter containing a polymerizable compound, a polymerization initiator, and a developing resin, is also preferred as described in Japanese Laid-Open Patent Publication No. 2,829,297. After the negative anti-money agent shattered by the coloring agent and the solvent is applied onto the substrate, the exposure portion is exposed to develop the exposed portion to form a 贞-type anti-rice pattern: and then the 贞-type secret case is prepared. Saki is fully exposed, which in turn hardens the exposed negative resist pattern. Further, a black matrix is formed according to a conventional method, whereby an RGB primary color system or a YMC complementary color system color filter can be obtained. A thermosetting resin, a diazonium compound, a crosslinking agent, a polymerizable compound, and a polymerization initiator used at this time. The developer, the solvent, and the amount thereof to be used can be preferably used as described in each of the above publications. 43 201229037 [Examples] Fen: The present invention will be more specifically described by way of a synthesis example and an example. The following materials, usage, ratio, processing contents, and handling of the stems and the contents of the stems are the appropriate ones, and can be changed as appropriate. Therefore, the fcilii of the enthalpy = should not be spoofed by the specific example shown by the town. &lt;Example 101&gt; [Synthesis of exemplified compound (1)] The above-described exemplification of the dipyrromethene metal-doped compound represented by the above formula (1) was synthesized by the method described below. Compound (1). - Synthesis of Intermediate A - Intermediate A of the following structural formula was synthesized by the method described in the specification of U.S. Patent Application Publication No. 2008/0076044. [Chemistry 7]

Intermediate A

44 201229037 - Synthesis of Intermediate B - To the intermediate A225.8 g (0.55 m〇1) and lion was cooled in an ice bath. Sakizaki nitrile, ml, chlorine 93.5g (〇.61 mol). After that, add it dropwise. Mix 5'22, methamphetamine and mix for 1 hour under ice-cooling, _ 626^ at room temperature. After the completion of the reaction, the precipitated solid was filtered, and then the filtrate was washed with acetonitrile and dried. Thus, an intermediate body 229 229 g of the following structural formula was obtained (yield: 79%). Furthermore, the details of W-NMRX CDC13) 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), 1.27~1.12 (m, 3H), 1.06~0.92 (m, 2H), 0.84 (s, 18Η), 0.70 (d, 3Η), 0.63~0.47 (m, 2Η). Intermediate 8

Me 45 201229037 - Synthesis of intermediate c - Add intermediate B222.lg (0.42m〇l), triethyl orthoformate 31.1 g (0.21 mol) to 42 〇ml of acetic anhydride, and mix at room temperature . To the solution was added dropwise a solution of trifluoroacetic acid, and stirred at room temperature for 3 hours. After the completion of the reaction, the reaction solution was poured into a solution of 940 g of sodium hydrogencarbonate added to 6400 ml of water, and extracted with 3,200 ml of ethyl acetate. Then, it was neutralized with a saturated aqueous solution of sodium hydrogencarbonate. After drying with sodium sulfate, filtration was carried out, and the filtrate was concentrated under reduced pressure. To the obtained solid, 2600 m of decyl alcohol was added, and the mixture was heated and stirred at 60 ° C for 1 hour. Then, 'filtered in a hot state, and then washed again with f-fermentation, and the solid obtained was obtained. Dry it. Thus, the intermediate C 170.3 g (yield 76%) was obtained. Furthermore, the details of ' ^-NMRC CDCb ) are δ: 1 ij 〇 (5, 7.72 (d, 2H), 7.39~7.13 (m, 16H), 6.12 (s, 1H), 5 85 (5, 20〇) 2·7〇(s,6Η),1,29~1·08 (m,6Η),1.02~ο.% (m,4 lean),〇.8 (s,36H),〇.64 (d, 6H), 〇44~〇31 (m, 4Ii). [Chem. 9] 46 201229037 Intermediate c

- Synthesis of the exemplified compound (1) - To a solution of 22 ml of tetrahydrofuran, an intermediate C 3.1 g (2.9 mmol), and stirred at room temperature, and then added to the solution, zinc acetate dihydrate 0.7 〇 8 (3.2 111111) 〇 1) A solution obtained by adding to methanol 221111 and stirring for 3 hours. The reaction liquid was concentrated by a rotary evaporator, and the obtained residue was added to 80 ml of decyl alcohol at 6 Torr. Spoiled underarm for 1 hour. Then, the crucible was carried out and the filtrate was dried. Thus, the exemplified compound (1) 2.34 g (yield 67%) was obtained. Furthermore, the details of iH-NMRC CDC1S) are δ: σ 11.6 (s, 2H), 7.73 (d, 2H), 7.4-7.1 (16H), 6.4 (s, 1H), 5.8 (s, 2H), 2.8 (s, 6H), 2.0 (s, 3H), 1.3 to 1.1 (m, 6H), 1.05 to 0.95 (m, 4H), 0.85 (s, 36H), 0, 7 (d, 6H), 0.6~ 0.25 (m, 4H). - Evaluation of Maximum Absorption Wavelength - The exemplary compound (1) was dissolved in the measurement solvent described in Table 5 below (agronomic degree: lxl〇-6m〇l/L), and the absorption spectrum was measured (the optical path length was 10 mm). ). The maximum absorption wave of the absorption spectrum of the exemplified compound (1) 201229037 is shown in Table 5 below. <Example 102 to Example 11〇&gt; [Synthesis of exemplified compound (2) to exemplified compound (10)] The exemplified compound (2) to the exemplified compound described above were synthesized by the method of Example 101. 1〇). Further, from the viewpoint of chemistry, the dipyrromethene-based metal-doped compound represented by the above formula (1) other than the exemplified compound (2) to the exemplified compound (1 〇) may be passed in accordance with The method of Example 1〇1 was synthesized. —Evaluation of the maximum absorption wavelength— The exemplary compound (2) to the exemplary compound (10) were each dissolved in the measurement solvent described in Table 5 below (concentration: lxl〇-6 m〇l/L), and the absorption spectrum was measured. The optical path length is 10 mm). The maximum absorption wavelengths of the absorption spectra of the exemplified compound (2) to the exemplified compound (10) are shown in Table 5 below. &lt;Example 111&gt; [Synthesis of exemplified compound (36)] The above-exemplified compound which is a dipyrromethene metal complex compound represented by the above formula (丨) is synthesized by the method described below. (3 6 ). - Synthesis of intermediate D - Add dimethylacetamide 2 〇〇m acetonitrile 300 m to 65.2 g (1.丨m〇1) of 2,4-dimethylbenzoate and cool in ice bath Under the mixing. To the solution, ruthenium chloride 13Q.9 g (丨丨-) was added dropwise, and the mixture was stirred for 3 G minutes in an ice bath, and then stirred at room temperature for 丨 hours, thereby obtaining the anti-48 201229037 solution A . Then, to 410.6 g (1 mol) of the intermediate A, dimercaptoacetamide 800 m was added and stirred under ice cooling. To the solution, the previously prepared reaction liquid A was added dropwise, and after completion of the dropwise addition, it 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, and the precipitated solid was filtered, and the filtrate was washed with water and acetonitrile, and dried. Thus, Intermediate D 510.8 g of the following structural formula was obtained (yield 94%). Furthermore, the details of iH-NMRC CDC13) are δ: 11.04 (d, 2H), 7.57 (d, 1H), 7.38 to 7.12 (m, 7H), 6.36 (s, 1H), 5.87 (s, (1), 2.58 (s, 3H), 2. ~0.47 (m, 2H). [化10]

Intermediate D

- Synthesis of Intermediate E - To a solution of 60 ml of acetic anhydride, intermediate D 27.14 g (0.05 mol) and triethyl orthoformate 3.71 g (0.025 mol) were added and stirred at room temperature. 49 201229037 To this solution, 75 m 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 hydrogencarbonate to 200 ml of ethyl acetate and 750 ml of water, and the mixture was stirred at room temperature for 2 hours. Then, the precipitated solid was allowed to pass, and then the filtrate was washed with acetoacetate and dried. Thus, Intermediate E 14.8 g of the following formula was obtained (yield 54%). Furthermore, the details of 'iH-NMRCCDCl3) are δ: n 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),1.28~1.12 (m,6H), 1.01 to 0.96 (m,4H),0.82 (s,36H),0.66 (d,6H),0.45~0.33 (m, 4H). [化11]

Intermediate E

- Synthesis of the exemplified compound (36) - Intermediate E4 93 g (45 mm 〇1) was added to 30 ml of tetrahydrofuran, and stirred at room temperature, followed by the addition of acetic acid dihydrate 9 g (4 95 mmol). Stir for 1 hour. Then, methanol i〇〇ml was added to the solution, and 50 201229037 was further stirred for 2 hours. After the completion of the reaction, the precipitated solid was filtered, and then the mash was washed with decyl alcohol and dried. Thus, 4.8 g (88%) of the exemplified compound (36) was obtained. Furthermore, the details of 'iH-NMRCCDCb) are δ: 11.59 (s, 2H), 7.65 (d, 2Η), 7.28~7.12 (m, 14Η), 6.30 (s, 1Η), 5.86 (s, 2Η), 2.69 (s,6H), 2.38 (s,6H),1_97 (s,3H), 1.26~1.15 (m, 6H), 0.99~0.94 (m,4H),0.83 (s,18H),0.76 (s, 18H), 0.65 (d, 6H), 0.55 to 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: lxl 〇 6 m 〇 l / L), and the absorption spectrum was measured (the optical path length was 10 mm). . The maximum absorption wavelength of the absorption spectrum of the exemplified compound (36) is shown in Table 5 below. &lt;Example 112&gt; [Synthesis of exemplified compound (35)] The above-described synthesis of a dipyrromethene-based metal-doped compound represented by the above formula (丨) was carried out by the method described below. An exemplified compound (35). - Synthesis of Intermediate F - 184.77 g (0.45 福) of intermediate ^, ^ decanoic acid triacetate 40 obtained by the method described in the description of U.S. Patent Application Publication No. 2008/〇〇76〇44 Toluene i L was added to g (0.27 mol) and scrambled under ice cooling. To the solution, decanoic acid η &amp; milk _) was added dropwise and heated under stirring at 90 ° for 8 hours. After the reaction is completed, the solvent of 51 201229037 is left, and the precipitated 111 body is washed with # and dried. Thus, the intermediate F i52.3 g of the following structural formula was obtained (yield 73%). Furthermore, the details of iH-NMRCCDC1:!) are: U.63, such as 9fr) 7.48 (br, 4H), 7.30~7.02 (m, 5H), 7.02~6.99 (m, 5H) 3 5 84 (s , 2H), 5.73 (s, 1H), 3.00 (s, 3H), 1.25~1.19 (edge, 6H), ' 〇99 ～0.95 (m, 4H), 0.78 (s, 36H), 0.64 (d, 6H) ), 〇.35~〇28 (9) 4H). Melon ‘[12]

Intermediate F

• Synthesis of intermediate G - Add 1 〇〇ml of 2,5-dimethylbenzoic acid to 30 g (0.2 mol) and 1.46 g of dimercaptoamine (〇.〇2 mol) ' The mixing was carried out at room temperature. To the solution, 23.8 g (0.2 mol) of sulfinium chloride was added dropwise, and the mixture was stirred at 50 C for 1 hour, whereby a reaction liquid b was obtained. Then, 10 mM of toluene and 23.2 g (0.025 mol) of the intermediate f were added to 216 g of a 25% aqueous sodium hydroxide solution, and stirred at room temperature. The previously prepared reaction liquid B was added dropwise to the solution, and stirred at room temperature for 1 hour. End of reaction 52 201229037 After the removal of the aqueous layer, the reaction solution was washed 3 times with 2 〇〇 ml of a 1% aqueous sodium hydroxide solution, and then washed once with 200 ml of 5% acetic acid water. Then, 200 ml of methanol was added to the solution, and after stirring for 2 hours, the precipitated solid was filtered and dried. Thus, an intermediate G of 19.4 g of the following structural formula was obtained (yield 71%). Furthermore, the details of 'kNMRC CDC13' are δ: 11 .〇5 (s, 2H), 7.53 (s, 2Η), 7.30 to 7.13 (m, 14Η), 6.12 (s, 1Η), 5.86 (s, 2Η) ), 2.62 (s, 6H), 2.36 (s, 6H), 1.25~1.18 (m, 6H), 0.99~0.95 (m, 4H), 0.79 (s, 36H), 0.63 (d, 6H), 0.43~ 0.31 (m, 4H). [Chem. 13]

Intermediate G

- Synthesis of the exemplified compound (35) _ Adding the intermediate G11 〇g to 四 四 南 〇 〇〇 〇〇 〇〇 〇〇 〇〇 中间体 中间体 中间体 中间体 中间体 中间体 中间体 中间体 中间体 中间体 中间体 中间体 中间体 中间体 中间体 中间体 中间体 中间体 中间体 中间体 中间体 中间体 中间体 中间体 中间体 中间体 中间体 中间体 中间体 中间体 中间体 中间体Then, methanol was added to the solution, and the mixture was returned to room temperature for 2 hours. After the reaction was completed, the solid precipitated in ^53 201229037 was filtered, and then the filtrate was washed with methanol and dried. Illustrative compound (35 ) 9 〇g (yield^

Further 7.53 (s 2.65 (s 0.99 〜 (m, 4H). • Evaluation of the maximum absorption wavelength - The exemplified compound (35) was dissolved in the measurement/combination described in Table 5 below (concentration: 1x10 mol/L) 'And the absorption spectrum (optical path length: 10 mm) was measured. The maximum absorption wavelength of the absorption spectrum of the exemplified compound (35) is shown in the following Table 5. <Example 113> [Synthesis of the exemplified compound (37)] The above-exemplified exemplified compound (37) which is a dipyrromethene metal complex compound represented by the above formula (丨) is synthesized by the method described. - Synthesis of intermediate oxime - to 2, 5 To 100 g of dimethylbenzoic acid (〇2 m〇i), 100 ml of toluene and 1.46 g of dimethylformamide (〇.〇2 mol) were added, and the mixture was stirred at room temperature. 23.8 g (0.2 mol) of sulfite gas was added dropwise, and stirred at 50 ° C for 1 hour, thereby obtaining a reaction liquid c. Then, 100 ml of toluene was added to 216 g of a 25% aqueous sodium hydroxide solution, and Example 112 Intermediate F23.2g (0.025 mol) obtained in the middle, and stirred at room temperature. 54 201229037 To the solution, the previously prepared The solution c should be stirred at room temperature for ίο. After the reaction is completed, the aqueous layer is removed, and the reaction solution is washed 3 times with 200 ml of a 1% by weight aqueous sodium hydroxide solution, followed by washing with 5% acetic acid water, for example, 1 Then, 200 ml of sterol was added to the solution, and after stirring for 2 hours, the precipitated solid was filtered and dried. Thus, an intermediate of the following structural formula was obtained, 15.9 § (yield 58%) &quot; Furthermore, the details of ^H-NMRCCDCl3) are 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 0.94 (m, 4H), 0.79 (s, 36H), 0.63 (d, 6H), 0.43~0.31 (m, 4H) [Chemical 14] Intermediate Η

- Synthesis of exemplified compound (37) - Add intermediate Η 16.4 g (0.015 mol) to 55 g of tetrahydrofuran, and stir at 50 ° C, followed by the addition of acetic acid dihydrate 3.62 g (0.0165 mol), and Stir at 50 ° C for 1 hour. Then, 120 ml of decyl alcohol was added to the solution, and the mixture was returned to room temperature, followed by stirring for 2 hours. After the reaction is completed 55 201229037, the precipitated solid is filtered, and the filtrate is washed with methanol and dried. Thus, the exemplified compound (37) was obtained in an amount of 7 2 g (yield 39%). Furthermore, the details of Wnmr( cdci3 ) are the heart] 5n (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), 1.29~1.19 (m, '6 0.99~0_95 (m, 4H), 0.80 (d, 36H), 0.65 (d, 6H), 0.48~〇.2i' (m, 4H) e - Evaluation of the maximum absorption wavelength - The exemplary compound (37) was dissolved in the measurement solvent described in Table 5 below (concentration: lxlO·6 mol) /L) 'and the absorption spectrum (optical path length: 10 mm) was measured. The maximum absorption wavelength of the absorption spectrum of the exemplified compound (37) is shown in the following Table 5. <Example 114> [Synthesis of the exemplified compound (39) The above-exemplified exemplary compound (39) is synthesized by the method of the synthesis example exemplified compound (36), which is represented by the above formula (1); each of the fluorenylene-based metal-substituted compounds. ° - Evaluation of the maximum absorption wavelength - The exemplified compound (39) was dissolved in the measurement solvent described in Table 5 below (concentration: lxl (T6 mol/L)' and the absorption spectrum (optical path length: 10 mm) was measured. Will be instantiated The maximum absorption wavelength of the absorption spectrum of (39) is shown in the following Table 5. [Table 5] 56 201229037 Exemplary absorption maximum wavelength of the compound [nm] Determination of solvent 1 561 Tetrahydrogen 0 2 2 561 Tetranitrogen 3 561 Hydroquinone 'South 4 561 Tetrahydrogen Fu Fur 5 560 Tetrahydrogen Fu Fu 6 560 Four nitrogen bites 7 561 Tetrahydrogen Fuchuan 8 561 — Tetrahydrogen Fushou domain 9 561 Tetrahydrogen. Fu shout 10 561 ^ _ Tetrahydrofuran __ ethyl acetate 35 559 36 560 ethyl acetate 37 557 Acetate B S 39 560 ____ Acetic acid B S In addition, Figure 1 shows the absorption spectrum of the exemplified compound (1). As is clear from the absorption spectrum, the dipyrrolidinium-based metal-doped compound of the present invention exhibits a sharp absorption spectrum peak. <Example 201> [Production of thermal-sensitive recording ink sheet] A thermosetting acrylic resin ( A film having a thickness of 6.0 μm and having a thickness of 6.0 μm (manufactured by Lumirror's Toray Co., Ltd.) is used as a support, and then coated by a wire bar to dry. The way the thickness reaches 1 will be included in Example 101. The following dye composition Exemplified compound (1) obtained by providing a coating layer forming composition is coated on a surface side of the membrane, thereby producing 201 examples of thermal transfer recording ink sheet. "Paint supply layer forming coating composition" 57 201229037 „) 5.5 ft# . Polyethylene butyl hydrazine 4·5 parts by mass (trade name S-LECBX·Bushui Chemicals f (share) manufacturing • Methyl succinct /甲笨(川[v/v]) Q〇Quality price-Preparation of thermal transfer recording image · The thermal transfer obtained in the above manner is obtained in such a manner that the dye supply layer is in contact with the image receiving layer The ink sheet for printing is superimposed on the ASK2GGG image receiving material manufactured by Fuji (4) (share). From the back side of the pigment supply material, the power of the thermal head is 〇25 w/point and the pulse width is The ink is printed under the condition of 0.15 milliseconds to 15 sec. and the dot density is 6 dots per liter, so that the magenta pigment is image-printed on the image receiving layer of the image receiving material, and as a result, no transfer is obtained. A clear thermal recording image was recorded. - Example 301, Comparative Example 301 &gt; [Production of Color Toner] The exemplified compound (2) obtained in Example 102 was damaged by a ball mill, and ink was obtained. Powder resin (styrene-acrylic acid ester copolymer; trade name HymerTB-lOOOF, Sanyohua (manufactured by Seisaku Co., Ltd.) 1 part by mass of mixed pulverization, heated to 150 C, and subjected to smelting and mixing, cooled, coarsely pulverized using a hammer mill, and then finely pulverized by a jet mill. The particles of 1 μm to 20 μm were selected to prepare the color toner of Example 301. Further, the carrier iron powder (trade name EFV250/400, Japan Iron Powder (share) was made with respect to 1 part by mass of the color toner. Manufactured) 900 parts by mass of 58 201229037 uniformly mixed 'to thereby produce the developer of Example 301. In Example 301 'Replace the exemplified compound (2) with CI Pigment Red 122 (trade name Cromophtal Jet Magenta DMQ, Ciba Specialty The color toner and developer of Comparative Example 301 were produced in the same manner as in Example 301 except that the developer of Example 301 and Comparative Example 301 was passed through a dry plain paper electrophotographic copying machine (trade name NP_5〇). 〇〇, Canon (share) manufacturing) to make a copy. Using a spectrodensitometer (trade name x_Rite939, manufactured by X-Rite, Inc.), the copy sample is subjected to spectrophotometry. The results are shown in Table 6. [Table 6]

As shown in Table 6, it is understood that the color toner using the dipyrromethene-based metal-based compound of the present invention has a higher absolute value of a and b* than the pigmented red 12 cedar toner used as a pigment. A wide color and privacy can be realized &lt;Example 401&gt; [Production of Inkjet Recording Ink] The exemplified compound obtained in Example 1〇3 was made 5.63 g and dioctyl-succinyl-sodium 7 at 7 〇C. 4 g is dissolved in a high boiling organic agent (S-2) 422 g, a high point organic solvent (s_u) &amp; vinegar a 5 〇: '''''''' - Face-to-face &quot; Add 5 〇〇ml of deionized water to the solution to prepare a coarse dispersion of water in the form of water 59 201229037. Further, the high boiling organic solvent (S - 2 ) and the high boiling organic solvent (s _ i j ) are compounds of the following structural formula. [化15]

(S-11)

O-P

Me

3 Secondly, under the pressure of 60 MPa, "Working", I ~ kiss Τ · 〇 · U Λ 月 月 仍 # 佩 佩 贝 贝 贝 贝 贝 贝 MIC MIC MIC MIC MIC MIC MIC MIC MIC MIC MIC MIC MIC MIC MIC MIC MIC MIC MIC MIC MIC MIC MIC MIC MIC MIC MIC MIC MIC MIC MIC MIC MIC The emulsified product of _ _ _ _ _ _ (4) is desolvated until the acetic acid B, the fine emulsion obtained in the formula t, disappears. To the gas product and chemistry of the above-mentioned party g, SURFYNOL 465 (trade name, ^ ethylene glycol 140 g, glycerol 5 〇 &amp; Chemicals) 7 (Air Products inkjet recording ink. §, Deionized water 900 ml to obtain the inkjet recording oil repeatedly PM-G800, Seiko Epson (into the inkjet printer (trade name inkjet printer will record the image in I made) cartridge In the ink recording medium (trade name: 20120293, photo final processing, manufactured by Fujifilm Co., Ltd.), Fig. 2 shows a reflection spectrum of a recorded image of the ink for inkjet recording which is deleted by the example. As is clear from the reflection spectrum shown in Fig. 2, it is understood that the ink for inkjet recording of the present invention exhibits a sharp absorption spectrum peak and exhibits excellent properties as an ink for inkjet recording. &lt;Example 501&gt; Preparation of the film] - Preparation of a positive anti-surname agent composition - A non-phenolic novolac resin obtained from a mixture of hydrazine/p-phenol/formaldehyde (reaction molar ratio == 5/5/7.5, polystyrene The converted mass average molecular star is 4300) 3.4 quality Quantitative parts, o-diazepine naphthoquinone-5-sulfonate (average 2 hydroxyl groups esterified) 1.8 parts by mass, hexamethoxy hydroxy hydroxylated melamine 0.8 parts by mass using a compound of the following structural formula 20 parts by mass of lactic acid ethenylate and the exemplified compound (1) 1 obtained in Example 101 were mixed to obtain a positive-type anti-money composition. [Chem. 16] 201229037

Phenol compound OH

- Production of Color Filter - After the obtained positive resist composition was spin-coated on a glass substrate, the solvent was evaporated. Then, the germanium wafer is exposed through a mask to decompose the diazonium compound. Thereafter, heating was performed at 100 ° C, and then the exposed portion was removed by an alkaline sheet, and a positive coloring pattern having a resolution of 〇 8 μm was obtained. After the full-color exposure of the positive coloring pattern, 22 〇. 〇下加=〇 minutes to obtain the magenta monochrome color filter of the example 501. The exposure is made by using the i-ray exposure stepper HITACHILD-5010-i (trade name, manufactured by the company), NA = 〇.4〇). The other two are using SOH) or S0PD_B (all manufactured under the trade name (shares)). And the chemical-evaluation - the solubility of the pigment compound and the color smear The evaluation results are shown in the following Table 7. (Solubility) 62 201229037 The solubility of the composition of the positive anti-money agent in ethyl lactate was visually observed, and the residue was evaluated as △. The evaluation of the section was carried out. The total dissolved one was evaluated as 〇. When the insoluble one was evaluated as X, the pigment compound was ◦, and a part was used, and the third order (color change in the heating step) was visually observed to produce a filter. The heating step of the light sheet changes before and after 'will Zhike Qianhua commented on the occasion, and the money discoloration was judged as △, and the apparent discoloration was evaluated as X, and evaluated in three stages. Bei (color filter surface) Λ Made by visual observation The surface of the color filter was evaluated as 〇, and a part of the turbidity was evaluated as Δ, and a person who was turbid (or precipitated) was evaluated as X, and evaluated in three stages (transmission spectrum). Figure 3 shows the transmission spectrum of the color filter &gt;} of Example 501. As is clear from the transmission spectrum shown in Figure 3, the color filter of Example 501 exhibited a sharp absorption spectrum peak. In addition, the color filter of Example 501 The light sheet showed good light transmittance. <Example 502 to Example 509, Comparative Example 501 to Comparative Example 503> The exemplified compound (1) of Example 501 was replaced with the exemplified compound (2) to the exemplified compound (5) described above. A positive type was produced in the same manner as in Example 501 except that the compound (35) to the exemplified compound (37) and the exemplified compound (39) and the comparative coloring matter (1) to the comparative coloring matter (3) were exemplified. Resist composition and fabrication Color suddenly light sheet. Further carry out the same evaluation as in Example 501 The evaluation results are shown in Table record below 7 ° 63 201229037

Comparative pigment (2)

[Chemical π] Comparative Pigment (1) [Chem. 18] [Chem. 19] 64 201229037 Comparative Pigment (3)

[Table 7] ___ Solubility of Pigment Compound for Ethyl Lactate Color Change Caused by Heating Step Surface Example of Color Filter 501 Illustrative Compound (1) 〇〇 Example 5 〇 2 Illustrative Compound (2) 〇 〇Example 503 exemplified compound (3) 〇〇〇 Example 504 exemplified compound (4) 〇〇〇 Example 505 exemplified compound (5) 〇〇〇 Example 506 exemplified compound (35) 〇〇〇 Example 507 exemplified compound (36) 〇〇 Example 508 Example Compound (37 &gt; 〇〇〇 Example 509 Illustrative Compound (39) 〇〇〇 Comparative Example 501 Comparative Pigment (1) Δ Δ X Comparative Example 502 Comparative Pigment (2) 〇Δ 〇 Comparative Example 503 Comparative dye (3) 〇〇Δ As is clear from Table 7, it is understood that the dipyrromethene metal-doped compound of the present invention is excellent in solubility in a solvent. It is understood that the dipyrromethene metal complex of the present invention is used. Compound 65 201229037 Example 501 to Example 509 have less color change in the heating step when producing a color light sheet, and the surface of the produced color filter INDUSTRIAL APPLICABILITY The present invention provides a dipyrromethene metal complex compound which exhibits a sharp absorption spectrum peak, is excellent in stability and solubility in a solvent, and contains the dipyrromethene. Further, according to the present invention, an ink sheet for thermal transfer recording, a color toner, an ink for ink recording, and a color transfer can be provided. The present invention is expected to be used for High-quality recording of high-quality materials, etc., and high industrial applicability. [Simplified description of the drawings] Figure 1 is the utilization of the absorbing light 2::::1 of the exemplified compound (1) synthesized in Example 101. The reflection spectrum of the recorded image of the ink for inkjet recording. Fig. 3 is a transmission spectrum of the color (four) light sheet which is referred to in [Example 501].

Claims (1)

201229037 VII. Patent application scope: 1. A dipyrrolidinium metal complex compound represented by the following general formula (1): [Chemical Formula 1] General formula (1) In the formula (1), R1, R2, R3, R4, R5, R6, R7 and R8 each independently represent a monovalent substituent, Μ represents a metal or a metal compound, and X represents a substituted or unsubstituted carbon number. a 2 to 3 decyloxy group, a substituted or unsubstituted alkylsulfonyloxy group, a substituted or unsubstituted arylsulfonyloxy group, or a halogen atom, n1 and η2 each independently represent 0~ An integer of 5, η3 and η4 each independently represent an integer of 0 to 3. 2. A dipyrrolidino-based metal complex compound represented by the following formula (2): [Chemical 2] 67 201229037 Formula (2) In the formula (2), R3 and R4 each independently represent a monovalent substituent, and f is an unsubstituted or unsubstituted decyloxy group having 2 to 3 carbon atoms, substituted or unsubstituted filamentous oxygen. The aryl group or the halogen atom of the aryl group. 3. A coloring composition comprising a dipyrromethene metal complex compound as described in claim 2 or 2. An ink sheet for thermal transfer recording comprising a dipyrromethene metal complex compound as described in the first or second aspect of the patent application. 5. A color toner comprising a dipyrromethene metal complex compound as described in claim 1 or 2. 6. An ink for inkjet recording comprising a dipyrylene methylene metal complex compound as described in claim 1 or 2. 7. A color filter comprising the diterpene methylene metal complex compound as described in claim 1 or 2. 68