JP2007009106A - Azomethine dye and metal complex dye, and color toner and ink for inkjet using those - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an azomethine dye and a metal complex dye each having sharp optical absorption and high molar extinction coefficient and excellent in stability to heat, light and humidity, and a color toner and ink for inkjet utilizing those. <P>SOLUTION: The azomethine dye is represented by general formula 1 [wherein Y is a substituent satisfying the formula 0.2≤σp≤0.9; Z<SB>1</SB>and Z<SB>2</SB>are each -CR1= or -N=; L is a group represented by general formula 1a or 1b (wherein R1 is a hydroxy group, an aryloxy group, an amino group, a mercapto group or an alkylthio group; Rb is a substituent; p is an integer of 0-4; B is a nonmetal atom group required for forming a heterocycle together with -CR1=); X is an unsubstituted or substituted alkylamino group; R is a substituted or unsubstituted alkyl group; R1 is a hydrogen atom or a substituent; n is an integer of ≥0]. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an azomethine dye, a metal complex dye, and a color toner and an inkjet ink containing them.

  Dyes known as dyes and pigments are widely used in various applications such as fiber dyeing materials, resin and paint colorants, photography, printing, copiers, image forming materials in printers, and light absorbing materials for color filters. It's being used. In recent years, various image forming dyes for color hardcopy using ink jet, electrophotography, silver salt photography, thermal transfer, etc. have been proposed, and with the progress of electronic imaging, dyes for solid imaging tubes, color liquid crystal television filter dyes and semiconductors. The demand for dyes for optical recording media using lasers is increasing, and the field of use of dyes is expanding. It is desired that the above dyes have the following properties in common.

  That is, having a hue preferable for color reproduction, having an optimum spectral absorption characteristic, good image fastness such as light resistance, heat resistance, moisture resistance, chemical resistance, a large molar extinction coefficient, etc. Is mentioned.

  Azomethine dyes are conventionally used as image forming dyes for silver halide color photographic light-sensitive materials using a subtractive color method by mixing three colors of yellow, magenta, and cyan. These dyes are disclosed and proposed as image forming dyes for color hard copy (for example, see Patent Documents 1 to 6). However, these dyes have not yet obtained sufficient image fastness. Moreover, although the metal complex pigment | dye excellent in light resistance is described (for example, refer patent documents 7-9), it is used for uses, such as a pigment | dye for image formation, because a molar absorption coefficient is small and a specific absorption wavelength. Is disadvantageous, and development of a dye having the above properties is desired.

  In color copiers and color laser printers using an electrophotographic method, generally, a toner in which a colorant is dispersed in resin particles, a toner in which a colorant is attached to the resin particle surface, or the like is used. As performance required for color toners, absorption characteristics capable of realizing a preferable color gamut, particularly high transparency (transparency), which is a problem when used in Overhead Projector (hereinafter referred to as OHP), and environmental conditions to be used Various fastnesses are mentioned below.

  Toners in which pigments are dispersed in particles as colorants are disclosed in JP-A-62-157051 and JP-A-6-118715. These toners are excellent in light resistance but are insoluble. Therefore, it is easy to agglomerate, and a decrease in transparency and a change in the hue of the transmitted color are problematic. On the other hand, toners using dyes as colorants are disclosed in JP-A-2-207274, JP-A-2-207273, JP-A-3-276161, JP-A-7-209912, JP-A-8-123085, and JP-A-2002-371214. Although disclosed in the official gazette, these toners have high transparency and no hue change, but have a problem in light resistance.

  The dyes used in ink jet recording inks have high solubility in solvents, high density recording, good hue, and fastness to light, heat, air, water and chemicals. In addition, it is required to have good fixability with respect to an image receiving material and to prevent bleeding, to be excellent in storage stability as an ink, to be non-toxic, to have high purity, and to be available at low cost. However, it is extremely difficult to search for pigments that meet these requirements at a high level. In particular, there is a strong demand for a pigment having a good hue and excellent light fastness.

Japanese Patent Application Laid-Open Nos. 61-36362 and 2-212566 disclose ink jet recording inks for the purpose of achieving both hue and light fastness. However, the dye used in each publication has insufficient solubility in water when used as a water-soluble ink.
JP-A-59-184339, pages 7-9 JP 10-145281 A, pages 10-13 JP-A-2-3450, pages 3-4 JP-A-4-359968 JP-A-7-166084 Japanese Patent Laid-Open No. 10-264541 Japanese Patent Laid-Open No. 2-76884 JP-A-9-131973 JP-A-9-143382

  An object of the present invention is to provide azomethine dyes, metal complex dyes, color toners using them, and inks for inkjets, which have sharp spectral absorption, a high molar extinction coefficient, and excellent stability to heat, light, and humidity. It is.

  The above object of the present invention has been achieved by the following constitution.

(Claim 1)
An azomethine dye represented by the following general formula 1.

(In the formula, Y represents a substituent of 0.2 ≦ σp ≦ 0.9, Z ₁ and Z ₂ represent —CR ₁ = or —N =, and L is represented by the following general formulas 1a and 1b. X represents an unsubstituted or substituted alkylamino group, R represents a substituted or unsubstituted alkyl group, R ₁ represents a hydrogen atom or a substituent, and n represents an integer of 0 or more. )

(In the formula, Rl represents a hydroxyl group, an alkoxy group, an aryloxy group, an amino group, a mercapto group, an alkylthio group or an arylthio group, Rb represents a substituent, p represents an integer of 0 to 4, and B represents -CRl. Represents a group of non-metallic atoms necessary to form a heterocyclic ring together with =.)
(Claim 2)
Y in the general formula 1 is selected from an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a cyano group, and a perfluoroalkyl group. Item 2. The azomethine dye according to Item 1.

(Claim 3)
_2. The azomethine dye according to claim 1, wherein Z _{2 in the} general formula is —CR ₁ ═ (R ₁ represents a hydrogen atom or a substituent).

(Claim 4)
Azomethine dyes represented by the following general formulas 2 to 4.

(Wherein Y represents a substituent of 0.2 ≦ σp ≦ 0.9, Z ₁ and Z ₂ represent —CR ₁ ═ or —N═, R ₁ represents a hydrogen atom or a substituent, X Represents an unsubstituted or substituted alkylamino group, R represents a substituted or unsubstituted alkyl group, and n represents an integer of 0 or more, Ra and Rb represent groups represented by the above general formulas 1a and 1b. Rc and Rd represent a group represented by the general formulas 1a and 1b or a monovalent organic group, and at least one of Rc and Rd represents a group represented by the general formulas 1a and 1b.)
(Claim 5)
A metal complex dye represented by the following general formula 5.

(In the formula, Y represents a substituent of 0.2 ≦ σp ≦ 0.9, Z ₁ and Z ₂ represent —CR ₁ = or —N =, and L is represented by the general formulas 1a and 1b. X represents an unsubstituted or substituted alkylamino group, R represents a substituted or unsubstituted alkyl group, M represents a metal atom or a salt thereof, and R ₁ represents a hydrogen atom or a substituent. , N represents an integer of 0 or more, and m represents an integer.)
(Claim 6)
Y in the general formula 5 is selected from an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a cyano group, and a perfluoroalkyl group. Item 6. The metal complex dye according to Item 5.

(Claim 7)
The metal complex dye according to claim 5, wherein Z ₂ in the general formula 5 is —CR ₁ = (R ₁ represents a hydrogen atom or a substituent).

(Claim 8)
6. The metal complex dye according to claim 5, wherein M in the general formula 5 is a metal atom selected from Ni, Cu, Co, Cr, Zn, Fe, Pd, and Pt or a salt thereof.

(Claim 9)
Metal complex dyes represented by the following general formulas 6-8.

Wherein Y represents a substituent of 0.2 ≦ σp ≦ 0.9, Z ₁ and Z ₂ represent —CR ₁ ═ or —N═, and X represents an unsubstituted or substituted alkylamino group. R represents a substituted or unsubstituted alkyl group, M represents a metal atom or a salt thereof, R ₁ represents a hydrogen atom or a substituent, n represents an integer of 0 or more, and m represents an integer. Ra and Rb represent groups represented by the general formulas 1a and 1b, Rc and Rd represent groups represented by the general formulas 1a and 1b or monovalent organic groups, and at least one of Rc and Rd is general. Represents a group represented by Formulas 1a and 1b.)
(Claim 10)
The metal complex dye according to claim 9, wherein M in the general formulas 6 to 8 is a metal atom selected from Ni, Cu, Co, Cr, Zn, Fe, Pd, and Pt or a salt thereof.

(Claim 11)
A color toner comprising the azomethine dye according to any one of claims 1 to 4.

(Claim 12)
A color toner comprising the metal complex dye according to claim 5.

(Claim 13)
An inkjet ink comprising the azomethine dye according to any one of claims 1 to 4.

(Claim 14)
An ink-jet ink comprising the metal complex dye according to any one of claims 5 to 10.

  According to the present invention, azomethine dyes and metal complex dyes having sharp spectral absorption, high molar extinction coefficient, and excellent stability to heat, light, and humidity can be obtained, and color reproducibility and light resistance can be obtained using them. An excellent color toner and ink-jet ink can be provided.

  Hereinafter, the present invention will be described in more detail.

  In the present invention, σp represents an electronic parameter. Med. Chem. 16, 1207 (1973) and J.A. Med. Chem. 20, 304 (1977).

  In general formula 1, Y represents a substituent of 0.2 ≦ σp ≦ 0.9, preferably 0.3 ≦ σp ≦ 0.8, and more preferably 0.4 ≦ σp ≦ 0.7. To express. When σp <0.2, the absorption wavelength becomes broad, which is not preferable. When σp> 0.9, dyeing during production is not preferable because of low yield. Specific examples of the substituent include an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a cyano group, and a perfluoroalkyl group.

  L represents a group represented by the general formulas 1a and 1b. Examples of the group that forms a heterocyclic ring together with -CRl = represented by the general formula 1a include a pyrrolyl group, an imidazolyl group, an isothiazolyl group, an isoxazolyl group, a pyrazolyl group, Examples include a pyrazinyl group, a triazolyl group, a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a 3H-indolyl group, a 1H-indazolyl group, a purinyl group, an isoquinolyl group, a quinolyl group, a phthalazinyl group, a naphthyridinyl group, a quinosalinyl group, and a quinazolinyl group.

  Rl is a hydroxyl group, an alkoxy group (eg, methoxy, ethoxy, butoxy, etc.), an aryloxy group, an amino group (eg, methylamino, diethylamino, methoxyethylamino, etc.), a mercapto group, an alkylthio group (eg, methylthio, ethylthio, octylthio). Etc.) and an arylthio group (for example, phenylthio, p-tolylthio and the like). These heterocycles may further have a substituent. Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom), an alkyl group (for example, methyl, ethyl, butyl, pentyl, 2- Methoxyethyl, trifluoromethyl, 2-ethylhexyl, etc.), aryl groups (eg, phenyl, p-tolyl, naphthyl, etc.), acyl groups (eg, acetyl, propionyl, benzoyl, etc.), alkoxy groups (eg, methoxy, ethoxy, Butoxy etc.), aryloxy groups (eg phenoxy, naphthoxy etc.), alkoxycarbonyl groups (eg methoxycarbonyl, i-propoxycarbonyl etc.), acyloxy groups (eg acetyloxy, ethylcarbonyloxy etc.), alkylthio groups (eg , Methylthio, ethylthio, octylthio ), Arylthio groups (eg, phenylthio, p-tolylthio, etc.), amino groups (eg, methylamino, diethylamino, methoxyethylamino, etc.), cyano groups, nitro groups, heterocyclic groups (eg, pyridyl, pyrazolyl, imidazolyl, furyl) , Thienyl, etc.).

  X represents an unsubstituted or substituted alkylamino group, and examples of the substituent include an aryl group (eg, phenyl, p-tolyl, naphthyl, etc.), an acyl group (eg, acetyl, propionyl, benzoyl, etc.), an alkoxy group ( For example, methoxy, ethoxy, butoxy, etc.), alkoxycarbonyl groups (eg, methoxycarbonyl, i-propoxycarbonyl, etc.), acyloxy groups (eg, acetyloxy, ethylcarbonyloxy, etc.), alkylthio groups (eg, methylthio, ethylthio, octylthio) Etc.), arylthio groups (eg, phenylthio, p-tolylthio, etc.), amino groups (eg, methylamino, diethylamino, etc.), cyano groups, nitro groups, hydroxyl groups, carboxyl groups, sulfonic acid groups, sulfonamido groups (eg, Methanesulfo Amide, ethanesulfonamide, etc.), acylamino groups (eg acetylamino, benzoylamino, etc.), carbamoyl groups (methylcarbamoyl group, phenylcarbamoyl etc.), sulfamoyl groups (eg methylsulfamoyl, phenylsulfamoyl etc.) Can be mentioned.

  R represents a substituted or unsubstituted alkyl group, and examples of the substituent of the substituted alkyl group include an aryl group (eg, phenyl, p-tolyl, naphthyl, etc.), an acyl group (eg, acetyl, propionyl, benzoyl, etc.), alkoxy Groups (eg, methoxy, ethoxy, butoxy, etc.), alkoxycarbonyl groups (eg, methoxycarbonyl, i-propoxycarbonyl, etc.), acyloxy groups (eg, acetyloxy, ethylcarbonyloxy, etc.), alkylthio groups (eg, methylthio, ethylthio, etc.) , Octylthio, etc.), arylthio groups (eg, phenylthio, p-tolylthio, etc.), amino groups (eg, methylamino, diethylamino, etc.), cyano groups, nitro groups, hydroxyl groups, carboxyl groups, sulfonic acid groups, sulfonamido groups ( For example, methane Luphonamide, ethanesulfonamide, etc.), acylamino groups (eg acetylamino, benzoylamino etc.), carbamoyl groups (methylcarbamoyl group, phenylcarbamoyl etc.), sulfamoyl groups (eg methylsulfamoyl, phenylsulfamoyl etc.) Can be mentioned.

R ₁ represents a hydrogen atom or a substituent, and examples of the substituent include an alkyl group (for example, methyl, ethyl, butyl, pentyl, 2-methoxyethyl, trifluoromethyl, 2-ethylhexyl, etc.), an aryl group (for example, phenyl, p-tolyl, naphthyl etc.), acyl group (eg acetyl, propionyl, benzoyl etc.), alkoxy group (eg methoxy, ethoxy, butoxy etc.), aryloxy group (eg phenoxy, naphthoxy etc.), alkoxycarbonyl group (eg For example, methoxycarbonyl, i-propoxycarbonyl etc.), acyloxy group (eg acetyloxy, ethylcarbonyloxy etc.), alkylthio group (eg methylthio, ethylthio, octylthio etc.), arylthio group (eg phenylthio, p-tolylthio etc.) ) Amino group (e.g. methylamino, diethylamino, etc.), a cyano group and a nitro group.

  In the general formula 1b, examples of the substituent represented by Rb include a halogen atom (for example, a fluorine atom, a chlorine atom, etc.), an alkyl group (for example, methyl, ethyl, butyl, pentyl, 2-methoxyethyl, trifluoromethyl, 2-ethylhexyl etc.), aryl groups (eg phenyl, p-tolyl, naphthyl etc.), acyl groups (eg acetyl, propionyl, benzoyl etc.), alkoxy groups (eg methoxy, ethoxy, butoxy etc.), aryloxy groups (Eg, phenoxy, naphthoxy, etc.), alkoxycarbonyl groups (eg, methoxycarbonyl, i-propoxycarbonyl, etc.), acyloxy groups (eg, acetyloxy, ethylcarbonyloxy, etc.), alkylthio groups (eg, methylthio, ethylthio, octylthio, etc.) ), Arylchi Groups (eg, phenylthio, p-tolylthio, etc.), amino groups (eg, methylamino, diethylamino, methoxyethylamino, etc.), cyano groups, nitro groups, heterocyclic groups (eg, pyridyl, pyrazolyl, imidazolyl, furyl, thienyl, etc.) ) And the like.

  In the metal complex dyes represented by the general formulas 5 to 8, the metal represented by M is selected from metal atoms of Group VIII, Group Ib, Group IIb, Group IIIa, Group IVa, Group Va, Group VIa, Group VIIa. Preferably a divalent transition metal. Specific examples include divalent metals such as Ni, Cu, Co, Cr, Zn, Fe, Pd, and Pt, more preferably Ni, Cu, Co, Cr, and Zn, and particularly preferably Ni. . Among metal salts, examples of the inorganic metal salt include perchlorate, halogen salt, sulfate, boron fluoride salt, strontium fluoride salt, hexafluorophosphate, and the like. The metal organic salt or metal complex may be any organic group that can neutralize metal ions. For example, fatty acids, aromatic carboxylic acids, alkyl sulfonic acids, aryl sulfonic acids, phenols, acetylacetones, dithiocarboxylic acids, tetra Examples thereof include phenyl boron.

  In General Formulas 2 to 4, Ra and Rb are groups represented by General Formulas 1a and 1b, Rc and Rd represent groups represented by General Formulas 1a and 1b or monovalent organic groups, and Rc and At least one of Rd represents a group represented by the general formulas 1a and 1b. Examples of the monovalent organic group include a halogen atom (for example, a fluorine atom, a chlorine atom), an alkyl group (for example, methyl, ethyl, butyl, pentyl, 2-methoxyethyl, trifluoromethyl, 2-ethylhexyl, etc.). , Aryl groups (eg, phenyl, p-tolyl, naphthyl, etc.), acyl groups (eg, acetyl, propionyl, benzoyl, etc.), alkoxy groups (eg, methoxy, ethoxy, butoxy, etc.), aryloxy groups (eg, phenoxy, Naphthoxy, etc.), alkoxycarbonyl groups (eg, methoxycarbonyl, i-propoxycarbonyl, etc.), acyloxy groups (eg, acetyloxy, ethylcarbonyloxy, etc.), carbamoyl groups (eg, methylcarbamoyl, ethylcarbamoyl, butylcarbamoyl, phenylcalyl) Moyl etc.), sulfamoyl groups (eg sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl etc.), alkylthio groups (eg methylthio, ethylthio, octylthio etc.), arylthio groups (eg phenylthio, p- Tolylthio etc.), amino group (eg amino, methylamino, diethylamino, methoxyethylamino etc.), acylamino group (eg acetylamino, chloroacetylamino, propionylamino, benzoylamino, trifluoroacetylamino etc.), alkylureido group (Eg, methylureido, ethylureido, methoxyethylureido, dimethylureido, etc.), arylureido groups (eg, phenylureido etc.), alkylsulfonamide groups (eg, methanes) Honamide, ethanesulfonamide, butanesulfonamide, trifluoromethylsulfonamide, 2,2,2-trifluoroethylsulfonamide, etc.), arylsulfonamide groups (for example, phenylsulfonamide, tolylsulfonamide, etc.), alkylaminosulfonyl Amino group (eg, methylaminosulfonylamino, ethylaminosulfonylamino, etc.), arylaminosulfonylamino group (eg, phenylaminosulfonylamino, etc.), hydroxyl group, cyano group, nitro group, heterocyclic group (eg, pyridyl, pyrazolyl) Imidazolyl, furyl, thienyl, etc.).

  The metal complex dye of the present invention is only required to form a complex between the dye represented by formulas 1 to 4 and a metal ion. Preferably, the dye serving as a ligand has at least two coordination sites. And a metal complex dye in which both of the coordination sites are nitrogen atoms. In particular, metal complex dyes represented by general formulas 5 to 8 are preferably used.

  In the following, typical specific examples of the azomethine dye and the metal complex azomethine dye of the present invention are listed, but the present invention is not limited thereto.

Next, the metal ion-containing compound will be described. Examples of the metal ion-containing compound include inorganic or organic salts and metal complexes of metal ions, and among them, salts and complexes of organic acids are preferable. The metal constituting the metal ion-containing compound is selected from metal atoms of Group VIII, Group Ib, Group IIb, Group IIIa, Group IVa, Group Va, Group VIa, Group VIIa, preferably a divalent transition metal. is there. More preferred are divalent metals such as Ni, Cu, Co, Cr, Zn, Fe, Pd, and Pt, and particularly preferred are Ni, Cu, Co, Cr, and Zn. Specific examples include Ni ²⁺ , Cu ²⁺ , Cr ²⁺ , Co ²⁺ and Zn ²⁺ and a salt of an aliphatic acid such as acetic acid or stearic acid, or an aromatic carboxylic acid such as benzoic acid or salicylic acid. Examples include salts. Moreover, the complex represented by the following formula can be particularly preferably used.

[Me (Q ₁ ) _l (Q ₂ ) _m (Q ₃ ) _n ] (Y ⁻ ) _p
However, in the formula, Me represents a metal ion, preferably Ni ²⁺ , Cu ²⁺ , Cr ²⁺ , Co ²⁺ and Zn ²⁺ . Q ₁ , Q ₂ , and Q ₃ each represent a coordination compound capable of coordination with a metal ion represented by Me, and may be the same or different from each other. These coordination compounds can be selected, for example, from the coordination compounds described in “Chelate Science (5)” (Nanedo). Y ^- is represents an organic anion group, specifically can tetraphenylboron anion and alkylbenzene sulfonate anion is exemplified. l, m and n each independently represents an integer of 0 to 3, which is determined depending on whether the complex is tetradentate or hexadentate, or the coordination of Q ₁ , Q ₂ and Q ₃ Determined by the number of children. p represents 1 or 2.

  Furthermore, a metal complex represented by the following formula (when l, m, n = 0) is preferably used.

Me ²⁺ (Y ^-) ₂
In the formula, Me ²⁺ represents a divalent transition metal ion. Y ⁻ represents a coordination compound capable of forming a complex with a divalent metal ion.

  As the binder resin for a color toner of the present invention, all commonly used binders can be used. Examples thereof include styrene resin, acrylic resin, styrene / acrylic resin, and polyester resin.

  In the present invention, inorganic fine powder and organic fine particles may be externally added to the color toner for the purpose of improving fluidity and controlling charging. 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 have a number average primary particle size of preferably 10 to 500 nm, and more preferably 0.1 to 20% by mass in the toner.

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

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

  As the carrier, either an uncoated carrier composed only of magnetic material particles such as iron and ferrite, or 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 the carrier is preferably 30 to 150 μm in terms of volume average particle size.

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

  The ink-jet ink containing the coloring matter of the present invention can be used in various ink-jet recording liquids such as water-based ink jet recording liquid, oil-based ink jet recording liquid, and solid (phase change) ink jet recording liquid.

  The water-based inkjet recording liquid generally uses water and a water-soluble organic solvent as a solvent in addition to the dye of the present invention. Examples of water-soluble organic solvents include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.), 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, etc.), polyhydric alcohol ether (E.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethyl Glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl Ether, propylene glycol monophenyl ether, etc.), amines (eg ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, tri Tylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocyclics (eg, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides (eg dimethyl sulfoxide etc.), sulfones (eg sulfolane) Etc.), urea, acetonitrile, acetone and the like.

  In the water-based ink jet recording liquid as described above, the dye can be used as it is if it is soluble in the solvent system. On the other hand, when it is an insoluble solid as it is, the dye of the present invention can be applied to various dispersing machines (for example, a ball mill, a sand mill, an attritor, a roll mill, an agitator mill, a Henschel mixer, a colloid mill, an ultrasonic homogenizer, a pearl mill, a jet mill, Or the like, or after dissolving the dye in a soluble organic solvent, it can be dispersed in the solvent system together with a polymer dispersant or a surfactant. Furthermore, in the case of an insoluble liquid or a semi-molten material as it is, it can be dissolved in an organic solvent as it is or in a soluble state and can be dispersed in the solvent system together with a polymer dispersant or a surfactant. Specific methods for adjusting such an aqueous ink jet recording liquid are disclosed in, for example, JP-A Nos. 5-148436, 5-295212, 7-97541, 7-82515, and 7-118584. Reference may be made to the method described.

  The oil-based inkjet recording liquid uses an organic solvent as a solvent in addition to the dye of the present invention. Examples of the solvent for the oil-based ink jet recording liquid include alcohols (eg, pentanol, heptanol, octanol, phenylethyl alcohol, phenylpropyl alcohol, in addition to those exemplified as the water-soluble organic solvent in the water-based ink jet recording liquid. Furfuryl alcohol, anil alcohol, etc.), esters (eg, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, propylene glycol diacetate, ethyl acetate, amyl acetate, benzyl acetate, phenylethyl acetate, phenoxy acetate Ethyl, ethyl phenylacetate, benzyl propionate, ethyl benzoate, butyl benzoate, butyl laurate, isopropyl myristate, Triethyl phosphate, tributyl phosphate, diethyl phthalate, dibutyl phthalate, diethyl malonate, dipropyl malonate, diethyl diethyl malonate, diethyl succinate, dibutyl succinate, diethyl glutarate, diethyl adipate, dipropyl adipate, adipine Dibutyl acid, di (2-methoxyethyl) adipate, diethyl sebacate, diethyl maleate, dibutyl maleate, dioctyl maleate, diethyl fumarate, dioctyl fumarate, cinnamic acid-3-hexenyl, etc.), ethers ( For example, butyl phenyl ether, benzyl ethyl ether, hexyl ether, etc.), ketones (eg, benzyl methyl ketone, benzyl acetone, diacetone alcohol, cyclohexanone, etc.), hydrocarbons (eg, petroleum ether, Oil benzyl, tetralin, decalin, t-amyl benzene, dimethyl naphthalene, etc.), amides (e.g., N, N-diethyldodecanamide, etc.).

  In the oil-based ink jet recording liquid as described above, the dye can be used as it is dissolved, or can be used after being dispersed or dissolved in combination with a resinous dispersant or a binder.

  For specific methods for preparing such oil-based inkjet recording liquids, the methods described in JP-A-3-231975 and JP-T-5-508883 can be referred to.

  In addition to the dye of the present invention, the solid (phase change) ink jet recording liquid uses a phase change solvent that is solid at room temperature as a solvent and is in a molten liquid state when the ink is heated and jetted.

  Such phase change solvents include natural waxes (eg, beeswax, carnauba wax, rice wax, wood wax, jojoba oil, whale wax, candelilla wax, lanolin, montan wax, ozokerite, ceresin, paraffin wax, microwax. Crystallin wax, petrolactam, etc.), polyethylene wax derivatives, chlorinated hydrocarbons, organic acids (eg palmitic acid, stearic acid, behenic acid, tiglic acid, 2-acetonaphthone behenic acid, 12-hydroxystearic acid, dihydroxystearic acid) Acid), organic acid esters (for example, esters of the above-mentioned organic acids with alcohols such as glycerin, diethylene glycol, and ethylene glycol), alcohols (for example, dodecanol, tetradecanol, hexadecanol, eicosano) , Docosanol, tetracosanol, hexacosanol, octacosanol, dodecenol, myricyl alcohol, tetrasenol, hexadecenol, eicosenol, docosenol, pinene glycol, hinokiol, butynediol, nonanediol, isophthalyl alcohol, mesythelin, teleaphthalyl alcohol , Hexanediol, decanediol, dodecanediol, tetradecandiol, hexadecanediol, docosandiol, tetracosanediol, tvneol, phenylglycerin, eicosanediol, octanediol, phenylpropylene glycol, bisphenol A, paraalphacumylphenol Etc.), ketones (eg benzoylacetone, diacetobenzene, benzophenone, tricho Non, heptacosanone, heptatriacontanone, hentriacontanone, heptatriacontanone, stearone, laurone, dianisole, etc.), amides (eg oleic amide, lauric amide, stearic amide, ricinoleic amide, palmitic amide , Tetrahydrofuranic acid amide, erucic acid amide, myristic acid amide, 12-hydroxystearic acid amide, N-stearyl erucic acid amide, N-oleyl stearic acid amide, N, N'-ethylenebislauric acid amide, N, N'- Ethylene bis stearic acid amide, N, N'-ethylene bis oleic acid amide, N, N'-methylene bis stearic acid amide, N, N'-ethylene bis behenic acid amide, N, N'-xylylene bis stearic acid amide , N, N'-Buchi Lenbis stearic acid amide, N, N′-dioleyl adipic acid amide, N, N′-distearyl adipic acid amide, N, N′-dioleyl sebacic acid amide, N, N′-cysteallyl sebacic acid amide, Like N, N'-distearyl terephthalamide, N, N'-distearylisophthalamide, phenacetin, toluamide, acetamide, oleic acid dimer / ethylenediamine / stearic acid (1: 2: 2 molar ratio) A reaction product of dimer acid, diamine and fatty acid such as tetraamide), sulfonamide (eg, paratoluenesulfonamide, ethylbenzenesulfonamide, butylbenzenesulfonamide, etc.), silicones (eg, silicone SH6018 (Toray Silicone), Silicone KR215, 216, 220 (Shin-Etsu Corn), etc.), coumarones (for example, Escron G-90 (Nippon Chemical Co., Ltd.)), cholesterol fatty acid esters (for example, stearic acid cholesterol, palmitic acid cholesterol, myristic acid cholesterol, behenic acid cholesterol, lauric acid cholesterol, melisin) Acid cholesterol, etc.), saccharide fatty acid esters (for example, sucrose stearate, saccharose palmitate, saccharose behenate, saccharose laurate, saccharose melicinate, lactose stearate, lactose palmitate, lactose myristate, lactose behenate, lactose laurate) , Lactose melicinate, etc.).

  The phase change temperature in the solid-liquid phase change of the solid ink is preferably 60 ° C. or higher, and more preferably 80 to 150 ° C.

  In the solid ink jet recording liquid as described above, the dye of the present invention can be used as it is by dissolving it in a heated molten solvent, or it can be used by dispersing or dissolving it together with a resinous dispersant or binder. You can also.

  For a specific method for preparing such a solid ink jet recording liquid, methods described in JP-A-5-186723 and JP-A-7-70490 can be referred to.

The above-described water-based, oil-based, and solid ink jet recording liquids have a flying viscosity of preferably 4 × 10 ⁻² Pa · s or less, and more preferably 3 × 10 ⁻² Pa · s or less. .

The inkjet ink of the present invention preferably has a surface tension of 2 × 10 ⁻⁴ N / cm or more, more preferably 3 × 10 ⁻⁴ to 80 × 10 ⁻⁴ N / cm, as the surface tension at the time of flight.

  The coloring matter of the present invention is preferably used in the range of 0.1 to 25% by mass of the total ink liquid amount, and more preferably in the range of 0.5 to 10% by mass.

  In the inkjet ink of the present invention, the viscosity adjusting agent, the surface tension adjusting agent, the ratio according to the purpose of improving the ejection stability, the compatibility with the print head and the ink cartridge, the storage stability, the image storage stability, and other various performances. Resistance adjusting agents, film forming agents, dispersants, surfactants, UV absorbers, antioxidants, fading inhibitors, antifungal agents, rust inhibitors, and the like can also be added.

  The ink-jet ink of the present invention is not particularly limited with respect to the recording method used, but can be preferably used as an ink for an on-demand ink-jet printer. As an on-demand type, an electro-mechanical conversion type (for example, a single cavity type, a double cavity type, a bender type, a piston type, a shear mode type, a shared wall type, etc.), an electro-thermal conversion type (for example, a thermal type) Specific examples include an ink jet type, a bubble jet (registered trademark) type, an electrostatic suction type (for example, an electric field control type, a slit jet type, etc.), and a discharge type (for example, a spark jet type). it can.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples.

Example 1
[Synthesis of Exemplified Compound 1]

  (B) 1.6 g (0.00592 mol) was suspended in 20 ml of ethyl acetate. An aqueous solution in which 1.8 g (0.0169 mol) of sodium carbonate was dissolved in 5 ml of water was added thereto, followed by stirring until complete dissolution. (A) 0.4 g (0.00186 mol) was dissolved in 1 ml of water and added. While maintaining the temperature at 40 ° C., an aqueous solution prepared by dissolving 0.9 g (0.00378 mol) of sodium persulfate and 0.8 g (0.00754 mol) of sodium carbonate in 2 ml of water was slowly added dropwise and stirred for 1 hour. This was repeated 4 times. After completion of the reaction, the aqueous layer was removed and the ethyl acetate layer was washed with warm water. The residue obtained by removing the solvent under reduced pressure was separated and purified by column chromatography using ethyl acetate / toluene as a developing solvent. The obtained dye was recrystallized from acetonitrile to obtain 1.4 g (yield 55%) of (1). The structure was confirmed by NMR spectrum and Mass spectrum.

Example 2
Table 1 shows molar extinction coefficients of the azomethine dyes and metal complex azomethine dyes of the present invention in acetone (the metal complex dye was determined per molecule of the constituting dye).

  The absorption of the azomethine dye and metal complex dye of the present invention is sharp and exhibits a high molar extinction coefficient.

Example 3
On the synthetic paper (product name: YUPO FPG-150, manufactured by Oji Yuka Co., Ltd.) having a thickness of 150 μm, the following reagents are mixed to prepare a coating solution, which is coated with a wet film thickness of 65 μm and dried. And the sample which coated the layer containing the metal complex pigment | dye of this invention was produced. A comparative sample was prepared in the same manner as described above except that the comparative dye was used.

(Coating solution composition)
100 mg of metal complex dye of the present invention, comparisons 3 and 4 (described in Table 2)
Polyvinyl butyral resin (S-LEC BX-1: Sekisui Chemical Co., Ltd.) 4.0 g
Methyl ethyl ketone 25g
Tetrahydrofuran 25g
The sample according to the present invention and the comparative sample were measured by the following methods, and the fastness (light resistance, heat resistance, moisture resistance) of the metal complex dye and the comparative dye was evaluated. The results are shown in Table 2.

(Light resistance)
The obtained dye image was irradiated with light with a xenon fade meter for 72 hours, the light density was expressed as (D1 / D0) × 100, where D0 was the density before light irradiation and D1 was the light density after light irradiation. Sex was evaluated.

(Heat-resistant)
The obtained dye image was stored under conditions of 77 ° C. and 10% RH for 7 days, the dye residual ratio represented by (D2 / D0) × 100, where D0 is the concentration before the start of storage and D2 is the concentration after storage. %) Was evaluated for heat resistance.

(Moisture resistance)
The obtained dye image was stored for 7 days under the conditions of 40 ° C. and 80% RH, the dye residual ratio (%) represented by (D3 / D0) × 100, where D0 is the concentration before the start of storage and D3 is the concentration after storage. The moisture resistance was evaluated.

  As is apparent from Table 2, the metal complex dye of the present invention is a dye excellent in light fastness, heat resistance, and moisture fastness of image fastness.

Example 4
<Manufacture of color toner: grinding method>
100 parts of a polyester resin, 8 parts of the compound shown in Table 3, and 3 parts of polypropylene were mixed, kneaded, pulverized and classified to obtain a powder having an average particle size of 8.5 μm. Further, 100 parts of this powder and 1.0 part of silica fine particles (particle diameter 12 nm, hydrophobization degree 60) were mixed with a Henschel mixer to obtain a color toner.

<Manufacture of color toner: polymerization method>
By adding 20 g of the compound shown in Table 3 to an aqueous solution obtained by dissolving 5 g of sodium dodecyl sulfate in 200 ml of pure water, stirring and applying ultrasonic waves, an aqueous dispersion of the colorant and a low molecular weight polypropylene (number average molecular weight) = 3200) was preliminarily prepared by emulsifying in water such that the solid concentration was 30% by mass with a surfactant while applying heat.

  60 g of a low molecular weight polypropylene emulsified dispersion is mixed with the dispersion of the above colorant, and further 220 g of styrene monomer, 40 g of n-butyl acrylate monomer, 12 g of methacrylic acid monomer, and 5.4 g of t-dodecyl mercaptan as a chain transfer agent. After adding 2000 ml of neat pure water, emulsion polymerization was carried out by maintaining at 70 ° C. for 3 hours while stirring under a nitrogen stream.

  To 1000 ml of the resulting dispersion of the colorant-containing resin fine particles, sodium hydroxide was added to adjust the pH to 7.0, 270 ml of a 2.7 mol% aqueous potassium chloride solution was added, 160 ml of isopropyl alcohol, and 9.0 g of polyoxyethylene octylphenyl ether having an average degree of polymerization of ethylene oxide of 10 was dissolved in 67 ml of pure water and added, and the reaction was carried out with stirring at 75 ° C. for 6 hours.

  The obtained reaction solution is filtered, washed with water, further dried and pulverized to obtain colored particles, and 1.0 part of the colored particles and silica fine particles (particle diameter 12 nm, hydrophobization degree 60) are mixed with a Henschel mixer. A color toner was obtained.

  To 10 parts of the toner, 900 parts of carrier iron powder (trade name: EFV250 / 400, manufactured by Nippon Iron Powder) were uniformly mixed to obtain a developer. Similarly, a sample was prepared in the same manner except that 3 parts by mass of the compound shown in Table 3 was used. Using these developers, copying was performed with a dry plain paper electrophotographic copying machine (trade name: NP-5000, manufactured by Canon Inc.).

The evaluation test was carried out by the following method by producing a reflection image (an image on paper) and a transmission image (an OHP image) on paper and OHP by the above image forming method using the developer using the above color toner, respectively. did. The toner adhesion amount was evaluated in the range of 0.7 ± 0.05 (mg / cm ² ).

  About the obtained image, hue, light fastness, and transparency were evaluated. The hue was visually evaluated in three stages: best, good and poor.

Hue is the best: ○
Good hue: △
Bad hue: x.

  Regarding the light fastness, after measuring the image density Ci immediately after recording, the image was irradiated with xenon light (85,000 lux) for 5 days using a weather meter (Atlas C.165), and the image was again displayed. The density Cf was measured, and the dye residual ratio ({(Ci−Cf) / Ci} × 100%) was calculated from the difference in image density before and after the xenon light irradiation and evaluated. The image density was measured using a reflection densitometer (X-Rite 310TR).

Dye residual ratio is 90% or more: ○
Dye remaining ratio is 80 to 89%: Δ
Dye remaining rate is less than 80%: x.

  The transparency of the OHP image was evaluated by the following method. The visible spectral transmittance of an image is measured with a “330 type self-recording spectrophotometer” manufactured by Hitachi, Ltd., using an OHP sheet on which toner is not supported as a reference, the spectral transmittance at 650 nm is obtained, and the transparency of the OHP image is measured. It was.

Spectral transmittance is 80% or more: ○
Spectral transmittance is 70 to 79%: Δ
Spectral transmittance is less than 70%: x.

  The above results are shown in Table 3.

  As is apparent from Table 3, since the faithful color reproduction and high OHP quality are exhibited by using the color toner of the present invention, the color toner of the present invention is suitable for use as a full color toner. Furthermore, since the light resistance is good, it is possible to provide an image that can be stored for a long time.

Example 5
A metal complex dye (C1) was prepared in an ink composition I-1 having the composition described below according to a conventional method, and the same as that of I-1 except that the copper phthalocyanine compound C described below was used as a cyan dye. Ink composition I-2 having the following composition was prepared:

(Composition of ink composition I-1)
Metal complex dye (C1) 1.4% by mass
Diethylene glycol 19% by mass
9% by mass of triethylene glycol monobutyl ether
Surfactant Surfynol 465 (produced by Air Products and Chemicals Inc.) 0.6% by mass
Ion-exchanged water 70% by mass

  Using the prepared ink compositions I-1 and I-2, a sample recorded on a dedicated inkjet paper (PM photo paper: manufactured by Seiko Epson Corporation) by an inkjet printer PM800C (manufactured by Seiko Epson Corporation) is prepared, When the color tone was visually evaluated, the sample obtained using the ink composition I-1 containing the coloring matter of the present invention showed a bright cyan color, but was obtained using the ink composition I-2. The sample was slightly less saturated and the color tone was close to blue. Similar results were obtained when QP paper (manufactured by Konica Minolta) was used as the recording medium instead of PM photographic paper. Further, ink compositions I-3, I-4, I-5, I prepared using metal complex dyes (C6), (C15), (C21), and (C26) instead of the metal complex dye (C1). -6, and the ink composition I-7 prepared by using the compound obtained by mixing and concentrating the exemplified compound (71) and the following metal ion-containing compound in acetone at a ratio of 1: 5 in place of the metal complex dye Similar results were obtained when visual evaluation of the color tone of the sample recorded on the recording paper with an ink jet printer was performed in the same manner as the ink compositions I-1 and I-2. As described above, by using the inkjet ink using the coloring matter of the present invention, a recorded image having excellent color tone can be obtained.

Claims (14)

An azomethine dye represented by the following general formula 1.

(In the formula, Y represents a substituent of 0.2 ≦ σp ≦ 0.9, Z ₁ and Z ₂ represent —CR ₁ = or —N =, and L is represented by the following general formulas 1a and 1b. X represents an unsubstituted or substituted alkylamino group, R represents a substituted or unsubstituted alkyl group, R ₁ represents a hydrogen atom or a substituent, and n represents an integer of 0 or more. )

(In the formula, Rl represents a hydroxyl group, an alkoxy group, an aryloxy group, an amino group, a mercapto group, an alkylthio group or an arylthio group, Rb represents a substituent, p represents an integer of 0 to 4, and B represents -CRl. Represents a group of non-metallic atoms necessary to form a heterocyclic ring together with =.) Y in the general formula 1 is selected from an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a cyano group, and a perfluoroalkyl group. Item 2. The azomethine dye according to Item 1. _2. The azomethine dye according to claim 1, wherein Z _{2 in the} general formula is —CR ₁ ═ (R ₁ represents a hydrogen atom or a substituent). Azomethine dyes represented by the following general formulas 2 to 4.

(Wherein Y represents a substituent of 0.2 ≦ σp ≦ 0.9, Z ₁ and Z ₂ represent —CR ₁ ═ or —N═, R ₁ represents a hydrogen atom or a substituent, X Represents an unsubstituted or substituted alkylamino group, R represents a substituted or unsubstituted alkyl group, and n represents an integer of 0 or more, Ra and Rb represent groups represented by the above general formulas 1a and 1b. Rc and Rd represent a group represented by the general formulas 1a and 1b or a monovalent organic group, and at least one of Rc and Rd represents a group represented by the general formulas 1a and 1b.) A metal complex dye represented by the following general formula 5.

(In the formula, Y represents a substituent of 0.2 ≦ σp ≦ 0.9, Z ₁ and Z ₂ represent —CR ₁ = or —N =, and L is represented by the general formulas 1a and 1b. X represents an unsubstituted or substituted alkylamino group, R represents a substituted or unsubstituted alkyl group, M represents a metal atom or a salt thereof, and R ₁ represents a hydrogen atom or a substituent. , N represents an integer of 0 or more, and m represents an integer.) Y in the general formula 5 is selected from an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a cyano group, and a perfluoroalkyl group. Item 6. The metal complex dye according to Item 5. The metal complex dye according to claim 5, wherein Z ₂ in the general formula 5 is —CR ₁ = (R ₁ represents a hydrogen atom or a substituent). 6. The metal complex dye according to claim 5, wherein M in the general formula 5 is a metal atom selected from Ni, Cu, Co, Cr, Zn, Fe, Pd, and Pt or a salt thereof. Metal complex dyes represented by the following general formulas 6-8.

Wherein Y represents a substituent of 0.2 ≦ σp ≦ 0.9, Z ₁ and Z ₂ represent —CR ₁ ═ or —N═, and X represents an unsubstituted or substituted alkylamino group. R represents a substituted or unsubstituted alkyl group, M represents a metal atom or a salt thereof, R ₁ represents a hydrogen atom or a substituent, n represents an integer of 0 or more, and m represents an integer. Ra and Rb represent groups represented by the general formulas 1a and 1b, Rc and Rd represent groups represented by the general formulas 1a and 1b or monovalent organic groups, and at least one of Rc and Rd is general. Represents a group represented by Formulas 1a and 1b.) The metal complex dye according to claim 9, wherein M in the general formulas 6 to 8 is a metal atom selected from Ni, Cu, Co, Cr, Zn, Fe, Pd, and Pt or a salt thereof. A color toner comprising the azomethine dye according to any one of claims 1 to 4. A color toner comprising the metal complex dye according to claim 5. An inkjet ink comprising the azomethine dye according to any one of claims 1 to 4. An ink-jet ink comprising the metal complex dye according to any one of claims 5 to 10.