JP2009229497A - Electrophotographic toner set - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrophotographic toner set not only superior in color reproducibility in cyan and magenta images but also in a blue image, and superior in light resistance and ozone gas resistance. <P>SOLUTION: In the electrophotographic toner set containing, as a colorant, at least one of azomethine dyes, cyanine dyes, and squarylium dyes in the cyan toner, and containing at least one of magenta colorant of azo compound, an anthraquinone compound having heterocyclic ring, or an anthracene compound in the magenta toner, a hue angle (h) in the L<SP>*</SP>a<SP>*</SP>b<SP>*</SP>color system of the cyan toner is 170°≤h≤230°. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an electrophotographic toner set excellent in color reproducibility, light resistance and ozone gas resistance.

  As disclosed in various electrophotographic methods, an electrostatic latent image of electrostatic charge is generally formed on a photoreceptor containing a photoconductive material by various means, and then the latent image is developed as a powder image with toner. If necessary, the powder image is transferred to paper or the like, and then fixed by heating, pressurization, or solvent vapor.

  In recent years, an electrostatic latent image of an original is formed by exposure with spectral light, and this is developed with each color toner to obtain a colored copy image, or each color copy image is superimposed to obtain a full color copy image. As a color toner used for this, color toners of yellow, magenta, cyan and the like in which pigments and / or dyes of various colors are dispersed in a binder resin are produced.

  The above-mentioned electrophotographic method generally forms an image by the following steps.

  First, an electrostatic latent image is formed on the photosensitive member by irradiating the photosensitive member made of a photoconductive material with optical information corresponding to image information by various methods. Next, the electrostatic latent image formed on the photosensitive member is developed as a toner image with charged toner, and the toner image is transferred to an image recording medium (such as plain paper or an intermediate transfer member) for thermal fixing. An image is fixed on plain paper using an apparatus.

  In the color image forming method using the above-described electrophotographic method, the electrostatic latent image formed on the photoconductor corresponds to image information separated into yellow, magenta, cyan, and black colors, respectively. The toner of the same color as the image information is developed. A color image is formed by repeating this development process four times for each color.

  Conventionally known organic pigments and dyes have been used as colorants used in electrophotographic toners, but each has various drawbacks. For example, organic pigments are generally superior in heat resistance and light resistance compared to dyes, but because they exist in the form of particles dispersed in the toner, the hiding power is increased and transparency is reduced. End up. Further, since the dispersibility of the pigment is generally poor, the transparency is impaired, the saturation is lowered, and the color reproducibility of the image is hindered.

  As a method for eliminating the drawbacks of the pigment, for example, by using a flushing method as a pigment dispersion method, by achieving a pigment dispersion diameter on the order of submicron by primary particles without aggregated secondary particles, transparency is achieved. Means for improving and means for improving chargeability, fixability, and image uniformity by coating pigment particles with a binder resin and an outer shell resin have been proposed. However, even in the case of outputting with the toner proposed in these cases, it is still difficult to obtain sufficient transparency in the case of the toner using pigment.

  In color image forming apparatuses, in principle, all color reproduction can be performed by subtractive color mixing with the three primary colors of yellow, magenta, and cyan. However, in reality, the spectral characteristics when pigments are dispersed in a thermoplastic resin. The range of color reproducibility and saturation are reduced by the color mixing property when toners of different colors are overlapped with each other. Therefore, many problems still remain in faithfully reproducing the color of an original.

  On the other hand, a toner using a dye or a toner in which a dye and a pigment are mixed has been disclosed. Generally, in a toner using a dye, the dye exists in a state of being dissolved in the binder resin of the toner. However, it has a drawback that light resistance and heat resistance are greatly inferior to pigments. Regarding heat resistance, in addition to lowering the density due to decomposition of the dye, when the toner image is fixed by a heat roller, the dye is sublimated and easily contaminated in the machine, and the dye dissolves in the silicone oil used during fixing, Eventually, there was a problem of causing an offset phenomenon by fusing to a heating roll. As a proposal for solving these disadvantages of dyes, for example, means for making light resistance, sublimation and color reproducibility compatible by using a specific anthraquinone dye or chelate dye as magenta toner (for example, Patent Document 1) See). Further, as a highly saturated toner, for example, a toner using a squarylium dye (see, for example, Patent Document 2) has been proposed.

  On the other hand, copper phthalocyanine pigments are well known as colorants for cyan toners, and organic solvent-soluble pigments have also been put into practical use. The light resistance is very high, but the color tone is still satisfactory due to the influence of aggregation and the like. It was not a thing.

  Further, Patent Document 6 describes that when squarylium dye is used as a pulverization type cyan toner coloring matter, the chroma is high, but low light resistance has become a problem. Further, a toner containing an azomethine dye has also been proposed (see, for example, Patent Document 3), but it has been difficult to obtain light resistance and ozone gas resistance.

Therefore, by using a squarylium dye, tetramethine dye, or azomethine dye having a specific structure dispersed in a thermoplastic resin, it has excellent color reproducibility and transparency, as well as excellent heat resistance, chargeability, and offset resistance. Photographic toners have been proposed (see, for example, Patent Documents 4 to 7). However, when a full-color image is formed, light resistance is still insufficient and ozone gas resistance is also insufficient, and it has been found that the hue change of the full-color image after light irradiation and after exposure to ozone gas is remarkable. Improvement was desired.
Japanese Patent No. 3567403 JP 2000-345059 A Japanese Patent No. 3513792 JP 2001-342364 A JP 2007-316591 A JP 2007-328312 A JP 2007-121816 A

  An object of the present invention is to solve the above-described problems, and is an electrophotographic image having excellent color reproducibility of not only a cyan image and a magenta image but also a blue image, and excellent light resistance and ozone gas resistance. It is an object to provide a toner set.

  The above object of the present invention is achieved by the following means.

1. An azo compound or anthraquinone compound containing at least one dye represented by the following general formulas (1) to (5) as a colorant in the cyan toner and having a heterocyclic ring in the magenta toner, or the following general formula (6 In the toner set for electrophotography containing at least one magenta colorant of the compound represented by formula (1), the hue angle (h) of the cyan toner according to the L ^* a ^* b ^* color system is 170 ° ≦ h ≦ An electrophotographic toner set characterized by being 230 °.

[Wherein, Z ¹ represents a 5- or 6-membered heterocyclic group or carbocyclic group which may have a condensed ring, and Z ² represents a 5- or 6-membered heterocyclic ring which may have a condensed ring. Represents a group or an aryl group, and R ¹ and R ² represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, or a sulfonyl group. ]

[Wherein, R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or a substituent, Z ³ represents a 5-membered or 6-membered heterocyclic ring or carbocycle, and Z ⁴ represents 5 or 6 Represents a member heterocycle. ]

[Wherein, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represents a hydrogen atom or a substituent, X ¹ represents a hydroxyl group, a hydroxyl anion, an alkoxy group or an aryloxy group, and m1 and m2 represent 0 Or 1 and Z ⁵ and Z ⁶ each independently represents a 5- or 6-membered heterocyclic ring or carbocyclic ring which may have a condensed ring. ]

[Wherein, X ² represents a hydroxyl group, a hydroxyl anion, an alkoxy group or an aryloxy group, R ¹¹ and R ¹² each independently represents a hydrogen atom or a substituent, and Z ⁷ and Z ⁸ each independently represent a condensed group. It represents a 5- or 6-membered heterocyclic ring or carbocyclic ring which may have a ring. ]

[Wherein, R ^{13 to} R ¹⁵ each represents a hydrogen atom or a substituent, and Z ⁹ and Z ¹⁰ each independently represent a 5- or 6-membered heterocyclic ring or carbocyclic ring which may have a condensed ring, ³ represents —OR ¹⁷ , —NR ¹⁸ R ¹⁹ , R ¹⁷ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, or a carbonyl group, and R ¹⁸ and R ¹⁹ represent a hydrogen atom, an alkyl group, an aryl group, Represents a heterocyclic group, a carbonyl group or a sulfonyl group, and m3 represents 0 or 1; ]

[Wherein, Rd ₁ , Rd ₂ and Rd ₃ each represents a substituent, Zd represents a nonmetallic atom group necessary for forming a nitrogen-containing 5- to 6-membered heterocyclic ring, and md1 is an integer of 0 to 3 Md2 represents an integer of 0 to 4, and md3 represents an integer of 0 to 2, but md1, md2, and md3 do not represent 0 at the same time. When md1 is 2 or more, the plurality of Rd ₁ may be the same or different from each other, when md2 is 2 or more, the plurality of Rd ₂ may be the same or different from each other, and when md3 is 2, the plurality of Rd ₃ are They may be the same or different. ]
2. 2. The electrophotographic toner set as described in 1 above, wherein the hue angle (h) according to the L ^* a ^* b ^* color system indicated by the cyan toner is in the range of 220 to 200.

3. 3. The electrophotographic toner set as described in 1 or 2 above, wherein Z ¹ in the general formula (1) is represented by the following general formulas (7-1) to (7-7).

[Wherein, R ^{20 to} R ³⁹ represent a hydrogen atom or a substituent, L ¹ represents a nitrogen atom or —C (R) ═, and R represents a hydrogen atom or a substituent. * Represents a binding site. ]
4). Z ³ in the general formula (2) is the general formula (7-3), (7-4), (7-5), (7-6), (7-7), or the following general formula (7- 8), or Z ⁴ in the general formula (2) is represented by any one of the general formulas (8-1) to (8-3). Toner set for electrophotography.

[Wherein, R ⁴⁰ and R ⁴¹ each independently represent a hydrogen atom or a substituent, * represents a bonding site, R ^{51 to} R ⁵³ each independently represent a hydrogen atom or a substituent, and n1, n2, n3 Represents an integer of 0 to 2, X ¹¹ and X ¹² represent an oxygen atom, a sulfur atom, — (NR ⁵⁴ ) —, —CR ⁵⁵ R ⁵⁶ —, and R ^{54 to} R ⁵⁶ each independently represent a hydrogen atom or a substituent. And at least one of X ¹¹ and X ¹² represents — (NR ⁵⁴ ) —, and X ¹³ , X ¹⁴ , and X ¹⁵ represent an oxygen atom, a sulfur atom, — (NR ⁵⁷ ) —, —C (R ⁵⁸ R ⁵⁹⁾ - it represents, R ⁵⁷ to R ⁵⁹ represents a hydrogen atom or a substituent, at least one oxygen atom of X ¹³ to X ^15, a sulfur atom or - (NR ⁵⁷⁾ - represents, ** the binding site Represents. ]
5. In the general formula (3), m1 + m2 = 0 or 1, Z ⁵ is represented by the following general formula (9-1), and Z ⁶ in the general formula (3) is represented by the following general formula (9-2). 3. The toner set for electrophotography as described in 1 or 2 above, wherein

[Wherein R ⁶⁰ represents an oxygen atom, a sulfur atom, = (N ⁺ R ⁶² R ⁶³ ), R ⁶² and R ⁶³ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group; ⁶¹ represents a hydroxyl group, an alkoxy group, a thiol group, a thioalkyl group, —NR ⁶⁴ R ⁶⁵ , R ⁶⁴ and R ⁶⁵ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, L ^{11 to} L ¹⁸ each independently represents a nitrogen atom or —C (R ⁶⁶ ) ═, R ⁶⁶ represents a hydrogen atom or a substituent, and ^* 1 and ^* 2 represent a bonding site. ]
6). Z ⁷ in the general formula (4) is represented by the general formulas (8-1) to (8-3), and Z ⁸ in the general formula (4) is represented by the following general formulas (8-4) to (8- The toner set for electrophotography according to 1 or 2 above, which is represented by 6).

[Wherein, R ^{71 to} R ⁷³ each independently represents a substituent, k 1 represents an integer from 0 to 2, k 2 and k 3 represent an integer from 0 to 4, and k 1, k 2 and k 3 are 2 or more. a case, a plurality of R ^71, R ^72, R ⁷³ may be the same or different, may form a fused ring bond to each other is R ^71, R ^72, R ⁷³ which are adjacent to each other, R ⁷⁴ Represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, or a sulfonyl group, and X ¹⁷ , X ¹⁸ , and X ¹⁹ each independently represent an oxygen atom, a sulfur atom, — (NR ⁷⁵ ) —, —C ( R ⁷⁶ R ⁷⁷ ) —, R ^{75 to} R ⁷⁷ each represent a hydrogen atom or a substituent, and ^* 3 represents a binding site. ]
7). Z ⁹ in the general formula (5) is represented by the general formulas (7-1) to (7-8), and Z ¹⁰ is represented by the general formulas (8-1) to (8-3). 3. The toner set for electrophotography as described in 1 or 2 above.

  According to the present invention, an electrophotographic toner set having excellent color reproducibility of not only a cyan image and a magenta image but also a blue image, and excellent light resistance and ozone gas resistance can be obtained.

The electrophotographic toner set of the present invention contains an azo compound containing at least one dye represented by the following general formulas (1) to (5) as a colorant in the cyan toner and having a heterocyclic ring in the magenta toner. A compound, an anthraquinone compound or at least one magenta colorant of the compound represented by the following general formula (6), the hue angle (h) according to L ^* a ^* b ^* color system of the cyan toner is 170 It is characterized in that ° ≦ h ≦ 230 °.

  First, the cyan colorant that can be contained in the cyan toner used in the present invention will be described.

  The cyan colorant is a colorant that can have a cyan color tone when a toner containing the colorant is prepared and an image is formed.

  The cyan toner used in the present invention is represented by the general formulas (1) to (5) as a cyan colorant, and has a hue angle of 230 to 170, preferably 220 to 200, as a cyan toner single color. It is characteristic to show.

The hue of the image is measured on a toner image formed on an arbitrary white (L ^* value is 90 or more and C ^* value is 7 or less) substrate such as paper or plastic sheet. For the measurement, a color meter “SPM50” (manufactured by Gretag Co., Ltd.) is used, and the toner adhesion amount is controlled to adjust the L ^* value of the toner image to be in the range of 40-60. The measurement conditions are a measurement light D50 and a viewing angle of 2 °. Using the a ^* value and b ^* value obtained by measurement, the following formula h = tan ⁻¹ (b * / a *)
From the above, the hue angle (h) is calculated.

  Next, the structure of the cyan colorant contained in the cyan toner that can be used in the present invention will be described.

In the general formula (1), Z ¹ represents a 5- or 6-membered heterocyclic group or carbocyclic group which may have a condensed ring. As the heterocyclic group represented by Z ¹ , furyl group, benzofuranyl group, thienyl group, pyrrolyl group, indolyl group, imidazolyl group, pyrazolyl group, indazolyl group, triazolyl group, thiazolyl group, isothiazolyl group, thiadiazolyl group, benzoimidazolyl group , Oxazolyl group, isoxazolyl group, furazanyl group, benzoxazolyl group, phthalazyl group, pyranyl group, pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group, piperazyl group, triazyl group, thiapyranyl group, xanthenyl group, quinolyl group, quinoxalinyl And groups derived from a group, quinazolinyl group, cinnolinyl group, isoquinolinyl group, acridinyl group, phenazinyl group, carbazolyl group, phenoxazinyl group, perimidinyl group, and azaphenalene group.

Examples of the carbocyclic group represented by Z ¹ include a cyclohexadienyl group and a group derived from cyclohexadienone, cyclohexadienone, and the like. As a ring that can be condensed with these, an aliphatic ring, an aromatic ring, or another heterocyclic ring may be condensed.

Examples of the 5- or 6-membered heterocyclic group optionally having a condensed ring represented by Z ² include the same heterocyclic groups as Z ¹ . Examples of the aryl group represented by Z ² include a phenyl group and a naphthyl group. Examples of the ring condensable with these include the same rings as the ring condensable with Z1.

The groups represented by Z ¹ and Z ² may further have a substituent, and examples of the substituent include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group). Group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group), alkenyl group (for example, vinyl group, allyl group), alkynyl group (for example, , Ethynyl group, propargyl group), aryl group (for example, phenyl group, naphthyl group), heterocyclic group (for example, furyl group, thienyl group, pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group, triazyl group, imidazolyl group, Pyrazolyl group, thiazolyl group, benzimidazolyl group, benzoxazolyl group, quinazolyl group, lid Zyl group, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group), cyclo Alkoxy groups (for example, cyclopentyloxy group, cyclohexyloxy group), aryloxy groups (for example, phenoxy group, naphthyloxy group), alkylthio groups (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group) , Dodecylthio group), cycloalkylthio group (for example, cyclopentylthio group, cyclohexylthio group), arylthio group (for example, phenylthio group, naphthylthio group), alkoxycarbonyl group (for example, methyloxy group) Rubonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group), aryloxycarbonyl group (for example, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl) Group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylamino Sulfonyl group), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbo group) Group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octyl) Carbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group), acylamino group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, trifluoromethylcarbonylamino group, phenyl Sulfonylamino group, naphthylcarbonylamino group), sulfonylamino group (for example, methylsulfonylamino group, ethylsulfonylamino group, hexylsulfonylamino group, decylsulfonylamino group, phenylsulfonylamino group), carbamoyl group (for example, aminocarbonyl group) , Methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylamino Carbonyl group, 2-pyridylaminocarbonyl group), ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclo Hexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2- Ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group) , Dodecylsulfonyl group), arylsulfonyl group (for example, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group), a Group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino group, 2-pyridylamino group), cyano group, Nitro group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom), alkyl halide (for example, methyl fluoride group, trifluoromethyl group, chloromethyl group, trichloromethyl group, perfluoropropyl group) It is done.

R ¹ and R ² each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and may have a substituent, and the substituent can be substituted with the aforementioned Z ¹ or Z ^2. The same group as a group is mentioned, You may have a substituent further. R ¹ and R ² are preferably a hydrogen atom, an alkyl group, or an aryl group.

In the general formula (1), Z ¹ is preferably a structure of the general formulas (7-1) to (7-7).

In the general formulas (7-1) to (7-7), R ^{20 to} R ³⁹ each represents a hydrogen atom or a substituent, and the substituent is the same group as the group that can be substituted for Z ¹ and Z ² described above. And may have the same substituent. Note that * represents a binding site.

R ^{20 to} R ²⁶ are preferably a hydrogen atom, an alkyl group, a halogen atom, a cyano group, a nitro group, a hydroxyl group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, a carbamoyl group, or a sulfamoyl group.

R ²⁷ and R ²⁸ are preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, a carbamoyl group, an acylamino group, or a sulfonylamino group.

R ^{29 to} R ³¹ are preferably hydrogen atom, alkyl group, aryl group, heterocyclic group, alkoxycarbonyl group, acyl group, acylamino group, sulfamoyl group, sulfonylamino group, carbamoyl group, halogenated methyl group, nitro group, cyano group It is a group.

R ^{32 to} R ³⁹ are preferably an aryl group, a heterocyclic group, an alkoxycarbonyl group, a sulfamoyl group, a sulfonyl group, a carbamoyl group, a halogenated methyl group, a nitro group, or a cyano group.

L ¹ represents a nitrogen atom or —C (R) ═, R represents a hydrogen atom or a substituent, and examples of the substituent include the same groups as R ^{20 to} R ²⁶ .

In the general formula (1), Z ² is preferably an aryl group, a pyridyl group, a pyrazyl group, a pyrimidyl group, a pyridazyl group, an imidazolyl group, or a thienyl group, more preferably an aryl group or a pyridyl group.

  Next, the general formula (2) will be described in detail.

R ^{3 to} R ⁶ each independently represents a hydrogen atom or a substituent, and examples of the substituent include an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, a hydroxyl group, an alkoxy group, an acylamino group, a carbamoyl group, and an alkylsulfonyl. Represents a group, an arylsulfonyl group, a halogen atom, or a halogenated alkyl group. R ^{3 to} R ⁶ are preferably a hydrogen atom, an alkyl group, an alkoxycarbonyl group, an alkoxy group, an alkylsulfonyl group, a halogen atom, or a halogenated alkyl group, and more preferably a hydrogen atom.

Z ³ represents a 5-membered or 6-membered heterocyclic ring or carbocyclic ring, may have a substituent, and a plurality of adjacent substituents may be bonded to each other to form a condensed ring. Are preferably groups represented by the general formulas (7-3) to (7-7) and (7-8).

In the general formula (7-8), R ⁴⁰ and R ⁴¹ each independently represent a hydrogen atom or a substituent, and the substituent represents an alkyl group, an aryl group, and * represents a bonding site.

Examples of the substituent represented by R ⁴⁰ include a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, amino group, alkylthio group, arylthio group, alkoxy group. Group, aryloxy group, ureido group, alkoxycarbonylamino group, carbamoyl group, carboxyl group or alkoxycarbonyl group, halogenated alkyl group, preferably alkyl group (especially methyl group, t-butyl group), aryl group, A carbamoyl group, an alkoxycarbonyl group, and a halogenated alkyl group.

R ⁴¹ is preferably a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group or a halogenated alkyl group, more preferably an alkyl group, an aryl group or a heteroaryl group.

Z ⁴ represents a 5- or 6-membered heterocyclic ring, may have a substituent, and may have a condensed ring. Examples of the substituent include the same substituents as those that can be substituted for Z ¹ and Z ² .

Z ⁴ is preferably represented by the general formulas (8-1) to (8-3). R ⁵¹ , R ⁵² and R ⁵³ each independently represent a hydrogen atom or a substituent, preferably a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkyl group, a thioaryl group, an amino group, An alkylamino group, a dialkylamino group, and an anilino group, more preferably a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, and a thioalkyl group.

  n1, n2, and n3 represent an integer of 0 to 2, and when n1, n2, and n3 are each 2 or more, they may be bonded to each other to form an aromatic ring or a heterocyclic ring.

X ¹¹ and X ^{12 each} represents an oxygen atom, a sulfur atom, — (NR ⁵⁴ ) — or —CR ⁵⁵ R ⁵⁶ —, and at least one of X ¹¹ and X ¹² represents — (NR ⁵⁴ ) —.

R ^{54 to} R ⁵⁶ each independently represents a hydrogen atom or a substituent, and examples of the substituent include the same groups as those that can be substituted for Z ¹ and Z ^2, and may further have a substituent. . R ⁵⁴ is preferably an alkyl group, R ⁵⁵ and R ⁵⁶ are preferably at least one of R ⁵⁵ and R ⁵⁶ , and more preferably both R ⁵⁵ and R ⁵⁶ are alkyl groups.

More preferably, at least one of X ¹¹ and X ¹² is — (NR ⁵⁴ ) —, and the other is a sulfur atom or —CR ⁵⁵ R ⁵⁶ —.

X ¹³ , X ¹⁴ and X ^{15 each} represents an oxygen atom, a sulfur atom, — (NR ⁵⁷ ) — or —C (R ⁵⁸ R ⁵⁹ ) —, R ^{57 to} R ⁵⁹ each represent a hydrogen atom or a substituent, and X ¹³ at least one oxygen atom to X ^15, a sulfur atom or - (NR ⁵⁷⁾ - represents, ** indicates the binding site.

R ⁵⁷ has the same meaning as R ^54, R ^58, R ⁵⁹ has the same meaning as R ^55, R ^56.

Next, general formula (3) will be described. In the general formula (3), R ^{7 to} R ¹⁰ each independently represent a hydrogen atom or a substituent, and the substituent is synonymous with R ^{3 to} R ⁶ in the general formula (2).

X ¹ represents a hydroxyl group, a hydroxyl anion, an alkoxy group or an aryloxy group, preferably a hydroxyl group or a hydroxyl anion.

  m1 and m2 represent 0 or 1, preferably m1 + m2 = 0 or 1, and more preferably m1 = m2 = 0.

Z ⁵ and Z ⁶ each independently represents a 5- or 6-membered heterocyclic ring or carbocyclic ring which may have a condensed ring.

Examples of the 5- or 6-membered heterocyclic group represented by Z ⁵ include groups derived from pyrrole, pyrazole, imidazole, triazole, oxazole, thiazole, isoxazole, isothiazole, oxadiazole, thiadiazole, pyrimidinedione, etc. Is mentioned. Examples of the carbocycle include cyclopentadiene, cyclohexadiene-4-one, naphthalen-4-one and the like. These may have the above-described substituents, and examples of the substituent include the same groups as those described above for Z1 and Z2, and a plurality of adjacent substituents are bonded together to form a condensed ring. May be formed. Z ⁵ is preferably the aforementioned general formula (9-1).

In the formula, R ⁶⁰ represents an oxygen atom, a sulfur atom, ═N ⁺ (R ⁶² R ⁶³ ), and R ⁶² and R ⁶³ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, preferably An alkyl group and an aryl group;

L ^{11 to} L ¹⁴ each independently represents a nitrogen atom or —C (R ⁶⁶ ) ═, and R ⁶⁶ represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an aryl group, a heterocyclic group, a halogen atom, a hydroxyl group, an amino group, a sulfonylamino group, an acylamino group, an alkoxy group, an aryloxy group, a halogenated methyl group, a cyano group, a nitro group, and an alkyl group. Examples thereof include an oxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfonyl group, and a sulfamoyl group. R ⁶⁶ is preferably a hydrogen atom, alkyl group, halogen atom, hydroxyl group, amino group, sulfonylamino group, acylamino group, alkoxy group, halogenated methyl group, cyano group or alkyloxycarbonyl group, more preferably a hydrogen atom. An alkyl group, a halogen atom, a hydroxyl group, a sulfonylamino group, an acylamino group, and an alkoxy group.

Preferably, among L ^{11 to} L ^14, the number of nitrogen atoms is 0 or 1.

Examples of the 5- or 6-membered heterocyclic group represented by Z ⁶ include pyrrole, pyrazole, imidazole, triazole, oxazole, thiazole, isoxazole, isothiazole, oxadiazole, thiadiazole, and pyrimidinedione groups. . Examples of the carbocycle include cyclopentadiene, benzene, and naphthalene groups.

These may have the above-described substituents, and examples of the substituent include the same groups as those described above for Z ¹ and Z ² , and a plurality of adjacent substituents may be bonded together. A condensed ring may be formed. Z ⁶ is preferably the aforementioned general formula (9-2).

R ⁶¹ represents a hydroxyl group, an alkoxy group, a thiol group, a thioalkyl group, a ^{-NR 64 R 65, * 1,} * 2 denotes the binding site.

R ⁶⁴ and R ⁶⁵ each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, preferably an alkyl group or an aryl group.

L < ¹⁵ > -L < ¹⁸ > is synonymous with L < ¹¹ > -L < ¹⁴ > in Z < ⁵ >, Preferably the nitrogen atom is 0 or 1 among L < ¹⁵ > -L < ¹⁸ >.

In the general formula (4), X ² represents a hydroxyl group, a hydroxyl anion, an alkoxy group or an aryloxy group, preferably a hydroxyl group or a hydroxyl anion.

R ¹¹ and R ¹² each independently represents a hydrogen atom or a substituent. Examples of the substituent include the same groups as those described above for Z ¹ and Z ^2, and may further have the same substituent. R ¹¹ and R ¹² are preferably a hydrogen atom, an alkyl group, an alkoxycarbonyl group, a halogen atom, or a halogenated alkyl group, and more preferably a hydrogen atom.

Z ⁷ and Z ⁸ each independently represents a 5- or 6-membered heterocyclic ring or carbocyclic ring which may have a condensed ring.

Specific examples of Z ⁷ include the same groups as Z ⁵ , which may further have a substituent, and examples of the substituent include the same groups as the groups that can be substituted for Z ¹ and Z ² described above. Is mentioned. Z ⁷ is preferably general formulas (8-1) to (8-3), and more preferably general formula (8-1).

Examples of Z ⁸ include the same groups as Z ⁶ in the general formula (3), preferably the general formulas (8-4) to (8-6). R ^{71 to} R ⁷³ each independently represent a substituent, and examples of the substituent include the same groups as those described above for Z ¹ and Z ^2, and may further have a substituent.

k1 represents an integer from 0 to 2, and k2 and k3 represent integers from 0 to 4. When k1, k2, and k3 are 2 or more, a plurality of R ⁷¹ , R ⁷² , and R ⁷³ may be the same or different, and adjacent R ⁷¹ , R ⁷² , and R ⁷³ are bonded to each other to form a condensed ring. You may do it.

R ⁷⁴ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, or a sulfonyl group, and may further have a substituent. Preferably R ⁷⁴ is an alkyl group.

X ¹⁷ , X ¹⁸ and X ¹⁹ each independently represent an oxygen atom, a sulfur atom, — (NR ⁷⁵ ) — or —C (R ⁷⁶ R ⁷⁷ ) —. R ^{75 to} R ⁷⁷ represent a hydrogen atom or a substituent, R ⁷⁵ has the same meaning as R ⁵⁴ , and R ⁷⁶ and R ⁷⁷ have the same meanings as R ⁵⁵ and R ⁵⁶ . ^* 3 represents a binding site.

Z ⁸ is more preferably general formulas (8-4) to (8-6).

In General formula (5), R < ¹³ > -R < ¹⁵ > represents a hydrogen atom or a substituent, and is specifically synonymous with R < ⁷ > -R < ¹⁰ > in General formula (3).

Z ⁹ and Z ¹⁰ each independently represents a 5- or 6-membered heterocyclic ring or carbocyclic ring which may have a condensed ring, and the heterocyclic ring or carbocyclic ring is the same as Z ⁵ in formula (3) A ring is mentioned. Z ⁹ and Z ¹⁰ may have a substituent and may have a condensed ring. Examples of the substituent include the same substituents as those which can be substituted for Z ¹ and Z ² described above.

Preferably, Z ⁹ is the general formulas (7-1) to (7-8), and Z ¹⁰ is the general formulas (8-1) to (8-3).

X ³ represents —OR ¹⁷ or —NR ¹⁸ R ¹⁹ . R ¹⁷ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group or a carbonyl group, preferably a hydrogen atom or an alkyl group. R ¹⁸ and R ^{19 each} represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a carbonyl group or a sulfonyl group, preferably a hydrogen atom, an alkyl group, a carbonyl group or a sulfonyl group.

  m3 is represented by 0 or 1, and is preferably 1.

  Although the specific example of the pigment | dye represented by the said General formula (1)-(5) which can be used for this invention below is shown, the pigment | dye used for this invention is not limited to the following example. In addition, when there are tautomers and positional isomers, they are described only by one kind of description method, but are not limited to the tautomers and positional isomers, and a plurality of tautomers or positions are also described. Also included are mixtures of isomers.

  The dye of the present invention can be easily produced by a known method.

  The compounds represented by the general formulas (1) to (5) according to the present invention are, for example, Japanese Patent No. 3513792, Japanese Patent Application Laid-Open No. 2001-342364, Japanese Patent Application Laid-Open No. 2001-334755, Japanese Patent Application Laid-Open No. 2007-121816. Japanese Patent No. 3567403, Japanese Patent Laid-Open No. 2001-159832, Japanese Patent Laid-Open No. 2007-328312, Japanese Patent Laid-Open No. 2000-345059, Japanese Patent Laid-Open No. 2007-316591, etc. It can be easily synthesized.

  The cyan colorant of the present invention may be used alone from among the dyes represented by the general formulas (1) to (5) or may be arbitrarily used in combination of two or more.

  In addition to the general formulas (1) to (5), any cyan colorant can be used in combination with the cyan toner used in the present invention. For example, an aryl or heteryl azo dye having a phenol, naphthol, aniline or the like as a coupler component; for example, a cyan dye that can be used in the present invention having a hetero ring such as phenol, naphthol, or pyrrolotriazole as a coupler component Azomethine dyes or methine dyes not applicable to the above; polymethine dyes such as cyanine dyes, oxonol dyes, merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes; phthalocyanine dyes; anthraquinone dyes; indigo thioindigo And dyes.

  Next, the magenta colorant used in the present invention will be described.

  The magenta colorant is a colorant that can have a magenta color tone when an electrophotographic toner containing the colorant is prepared and an image is formed. The colorant may be a dye or a pigment.

  The azo compound having a heterocyclic ring in the present invention has the above-mentioned magenta colorant property, and is present in either or both of azo groups which are divalent substituents represented by the form -N = N-. It is a compound having a heterocyclic ring and is represented by the following general formula (10).

General formula (10)
Ax ₁ −N = N−Bx ₁
In the formula, Ax ₁ and Bx ₁ each independently represents an aromatic hydrocarbon group or a heterocyclic group. However, either Ax ₁ or Bx ₁ is a heterocyclic group.

General formula (10) will be further described. Examples of the aromatic hydrocarbon group represented by Ax ₁ or Bx ₁ include a phenyl group, a naphthyl group, a fluorenyl group, and the like. The heterocyclic group represented by Ax ₁ or Bx ₁ has one or more rings, and the ring has an element such as an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom, or a tellurium atom in addition to a carbon atom. Refers to the group. The heterocyclic group represented by Ax ₁ or Bx ₁ preferably has at least one or more 5-membered or 6-membered ring structures.

  Examples of the heterocyclic group having at least one 5-membered or 6-membered ring structure include a furyl group, a benzofuranyl group, a thienyl group, a pyrrolyl group, an indolyl group, an imidazolyl group, a pyrazolyl group, Indazolyl group, triazolyl group, thiazolyl group, isothiazolyl group, thiadiazolyl group, benzoimidazolyl group, oxazolyl group, isoxazolyl group, furazanyl group, benzoxazolyl group, phthalazyl group, pyranyl group, pyridyl group, pyridazyl group, pyrimidyl group, pyrazyl group , Piperazyl group, triazyl group, thiapyranyl group, xanthenyl group, quinolyl group, quinoxalinyl group, quinazolinyl group, cinnolinyl group, isoquinolinyl group, acridinyl group, phenazinyl group, carbazolyl group, phenoxazinyl group, perimidinyl group, azaph Naren group, and the like can be given. These may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring.

The aromatic hydrocarbon group or heterocyclic group represented by Ax ₁ or Bx ₁ may further have a substituent. Although there is no restriction | limiting in particular as a substituent, For example, alkyl group (For example, methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-octyl group) , N-dodecyl group, trifluoromethyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aromatic hydrocarbon group (also referred to as aryl group) (eg, phenyl group, naphthyl group, etc.), acylamino Groups (for example, acetylamino group, benzoylamino group, etc.), alkylthio groups (for example, methylthio group, ethylthio group, etc.), arylthio groups (for example, phenylthio group, naphthylthio group, etc.), alkenyl groups (for example, vinyl group, 2- Propenyl, 3-butenyl, 1-methyl-3-propenyl, 3-pentenyl, 1-methyl Ru-3-butenyl group, 4-hexenyl group, cyclohexenyl group, etc.), halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), alkynyl group (eg, propargyl group etc.), heterocyclic group (eg, Pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, etc.), alkylsulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group, etc.), arylsulfonyl group (eg, phenylsulfonyl group, naphthylsulfonyl group, etc.), alkylsulfinyl group ( For example, methylsulfinyl group etc.), arylsulfinyl group (eg phenylsulfinyl group etc.), phosphono group, acyl group (eg acetyl group, pivaloyl group, benzoyl group etc.), carbamoyl group (eg aminocarbonyl group, methylamino) Carbonyl group, dimethyl Minocarbonyl group, butylaminocarbonyl group, cyclohexylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group) Hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), sulfonamide group (for example, methanesulfonamide group, Benzenesulfonamido group, etc.), cyano group, alkoxy group (eg methoxy group, ethoxy group, propoxy group etc.), aryloxy group (eg phenoxy group) Si group, naphthyloxy group, etc.), heterocyclic oxy group, siloxy group, acyloxy group (eg, acetyloxy group, benzoyloxy group, etc.), sulfonic acid group, sulfonic acid salt, aminocarbonyloxy group, amino group (eg, Amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, etc.), anilino group (for example, phenylamino group, chlorophenylamino group, toluidino group, anisidino group) , Naphthylamino group, 2-pyridylamino group, etc.), imide group, ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido) Group, 2-pyrid Aminoureido group etc.), alkoxycarbonylamino group (eg methoxycarbonylamino group, phenoxycarbonylamino group etc.), alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl etc.), aryloxycarbonyl group (eg , Phenoxycarbonyl group, etc.), heterocyclic thio group, thioureido group, carboxyl group, carboxylic acid salt, hydroxy group, mercapto group, nitro group and the like. When a plurality of substituents can be substituted on the aromatic hydrocarbon group or heterocyclic group represented by Ax ₁ or Bx ₁ , each substituent may be the same or different.

Either Ax ₁ or Bx ₁ is a heterocyclic group, but both may be heterocyclic groups. When either Ax ₁ or Bx ₁ is an aromatic hydrocarbon group, the other heterocyclic group preferably has a 5-membered ring structure.

  The azo compound represented by the general formula (10) is more preferably the following general formula (11).

Formula (11)
Ax ₂ -N = N-Bx ₂
In the formula, Ax ₂ represents a heterocyclic 5-membered ring group containing at least one nitrogen atom or sulfur atom, and Bx ₂ represents a heterocycle containing at least one aromatic hydrocarbon group or 5-membered ring or 6-membered ring structure. Represents a group.

Further explanation will be given. In the general formula (11), Ax ₂ represents a 5-membered heterocyclic group containing at least one nitrogen atom or sulfur atom. Examples of such a heterocyclic group include thienyl group, pyrrolyl group, indolyl group, An imidazolyl group, a pyrazolyl group, an indazolyl group, a triazolyl group, a thiazolyl group, an isothiazolyl group, a thiadiazolyl group, a benzoimidazolyl group, an oxazolyl group, an isoxazolyl group, a furazanyl group, a benzoxazolyl group, and the like can be given. Bx ₂ represents an aromatic hydrocarbon group or a hetero group containing at least one 5-membered ring or 6-membered ring structure. Examples of the aromatic hydrocarbon group include the aromatic represented by Ax ₁ or Bx ₁ described above. Examples of the hetero group containing at least one 5-membered ring or 6-membered ring structure having the same meaning as the example of the hydrocarbon group are the 5-membered or 6-membered ring structure represented by Ax ₁ or Bx ₁ described above. And groups having the same meanings as the examples of the heterocyclic group containing at least one or more. Ax ₂ and Bx ₂ may each be further condensed with an aliphatic ring, an aromatic ring, or another heterocyclic ring.

Ax ₂ and Bx ₂ may each have a substituent, and examples of the substituent include a substituent that can be substituted with the aromatic hydrocarbon group or heterocyclic group represented by Ax ₁ or Bx ₁ described above. The group which is synonymous with the example of group can be mentioned. When a plurality of substituents can be substituted on Ax ₂ and Bx ₂ , each substituent may be the same or different.

  The azo compound represented by general formula (10) and general formula (11) is more preferably the following general formula (12) or general formula (13).

In the formula, Ax ₃ represents a thienyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, a thiadiazolyl group, or a benzothiazolyl group, and Qx ₁ and Qx ₂ are each independently -CRx ₃ =, or represents -CRx ₄ =, or either one nitrogen atom and the other represents a -CRx ₃ = or -CRx ₄ =, X represents a = nitrogen atom or -CRx _5, Rx ₁ and Rx ₂ are each independently And represents a hydrogen atom, alkyl, cycloalkyl group, aromatic hydrocarbon group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or sulfamoyl group, _{gx, Rx 3, Rx 4,} Rx 5 are each independently a hydrogen atom, c Gen atom, alkyl, cycloalkyl group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group , Acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group substituted with alkyl group, aryl group or heterocyclic group, acylamino group, ureido group, sulfamoylamino Group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl and arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkyl and arylthio group, alkyl and arylsulfonyl group Alkyl or aryl sulfinyl group, a sulfamoyl group, a sulfo group, or a heterocyclic thio group. Each group may be further substituted. Rx ₁ and Rx ₂ , or Rx ₁ and Rx ₄ may be bonded to form a 5- to 6-membered ring.

In the formula, Ax ₄ represents a group selected from a thienyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, a thiadiazolyl group, or a benzothiazolyl group, and Rx ₆ and Rx ₇ each independently represent a hydrogen atom, an aliphatic group Represents a group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, and each group further has a substituent. May be. Qx ₃ and Qx ₄ -CRx each independently ₈ =, - CRx ₉ = or represents, or either one nitrogen atom and the other represents a -CRx ₈ = or -CRx ₉ =, Rx ₈ and Rx ₉ is Each independently a hydrogen atom, halogen atom, cyano group, alkyl group, cycloalkyl group, alkylthio group, alkylsulfonyl group, alkylsulfinyl group, alkoxycarbonyl group, carbamoyl group, alkoxy group, aromatic hydrocarbon group, arylthio group, aryl A sulfonyl group, an arylsulfinyl group, an aryloxy group or an acylamino group is represented. Each substituent may be further substituted.

  General formula (12) and general formula (13) are further demonstrated.

Ax ₃ and Ax ₄ represent a thienyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, a thiadiazolyl group, or a benzothiazolyl group, preferably a thienyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, or An isothiazolyl group, a thiadiazolyl group or a benzothiazolyl group, which may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring, and may further have a substituent. There are no particular restrictions on the groups that can be substituted for Ax ₃ and Ax ₄ , but examples include substituents that can be substituted on the aromatic hydrocarbon group or heterocyclic group represented by Ax ₁ or Bx ₁ described above. A synonymous group can be mentioned. As the group capable of substituting for Ax ₃ and Ax ₄ , an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a nitro group, a cyano group are preferable. Group, carboxy group, halogen atom, alkoxy group, aryloxy group, acylamino group, alkylsulfonyl group, arylsulfonyl group, aminosulfonyl group, aminocarbonyl group, alkylaminosulfonyl group, alkylaminocarbonyl group, amino group, anilino group, Examples thereof include a hydroxy group and a sulfamoyl group. When a plurality of substituents can be substituted on Ax ₃ and Ax ₄ , each substituent may be the same or different.

Rx ₆ and Rx ₇ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or sulfamoyl. Represents a group, and each group may further have a substituent. Preferable substituents represented by Rx ₆ and Rx ₇ include a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group.

Examples of groups represented by Rx ₁ , Rx ₂ , Gx, Rx ₃ , Rx ₄ , Rx ₅ , Rx ₈ and Rx ₉ include the aromatic hydrocarbon group or heterocyclic group represented by Ax ₁ or Bx ₁ described above. It is synonymous with the example enumerated by the applicable group in the example of a substituent which can be substituted.

  The anthraquinone compound in the present invention is not particularly limited as long as it is an anthraquinone compound having the above-described magenta colorant properties.

  The anthraquinone compound in the present invention is more preferably the following general formula (14) or general formula (15).

In the formula, Ry ₁ and Ry ₂ each independently represents an alkyl group or a cycloalkyl group, and Ry ₃ represents an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group, a heterocyclic group, a halogen atom, an alkoxy group, or an aryloxy group. or an alkylthio group or an arylthio group, Ry ₄ represents an alkyl group or a cycloalkyl group or an aromatic hydrocarbon group or heterocyclic group, or a halogen atom or an alkoxy group or an aryloxy group, an integer from 0 to 2 ny1, ny2 represents an integer of 0 to 4.

In the formula, Ry ₅ represents a group having the same meaning as Ry ₃ in the general formula (14), Ry6 represents a group having the same meaning as Ry ₄ in the general formula (14), ny3 represents an integer of 0 to 2, ny4 Represents an integer of 0 to 4. Zy represents an amino group or a hydroxyl group.

General formula (14) and general formula (15) will be further described. Ry ₁ and Ry ₂ each independently represents an alkyl group or a cycloalkyl group, and examples thereof have the same meaning as the alkyl group or cycloalkyl group described above. Ry ₃ represents an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group, a heterocyclic group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group, for example, the above-described alkyl group, cycloalkyl group, or It is synonymous with an aromatic hydrocarbon group, a heterocyclic group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group or an arylthio group, and preferably a halogen atom. Ry ₄ represents an alkyl group or a cycloalkyl group or an aromatic hydrocarbon group or heterocyclic group, or a halogen atom or an alkoxy group or an aryloxy group, ny1 represents an integer of 0 to 2, when ny1 is 2, a plurality of Ry ₃ may be the same or different, and is preferably 1. ny2 represents an integer of 0 to 4. When ny2 is 2 to 4, a plurality of Ry ₄ may be the same or different, and is preferably 0 or 1. Ry ₅ represents a group having the same meaning as Ry ₃ in formula (14), and is preferably an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group. Ry ₆ represents a group having the same meaning as Ry ₄ in formula (14). ny3 represents an integer of 0 to 2, and when ny3 is 2, a plurality of Ry ₅ may be the same or different, and is preferably 1. ny4 represents an integer of 0 to 4. When ny4 is 2 to 4, a plurality of Ry ₆ may be the same or different, and preferably 0 or 1.

  Examples of the anthraquinone compound suitably used in the present invention include JP-A-9-502470, JP-A-7-43948, JP-A-2006-154363, JP-A-8-314189, JP-A-5-173369, and JP-A-5-173369. JP-A-5-257321, JP-A-6-59509, JP-A-6-59511, JP-A-6-59512, JP-A-6-148939, JP-A-7-209912, JP-A-8-152744, JP-A-6 No. 3858, JP-A-8-15911, JP-A-7-84416, JP-A-8-123088 and the like.

  Next, the compound represented by the general formula (6) will be described.

In the formula, Rd ₁ , Rd ₂ and Rd ₃ each represent a substituent, Zd represents a group of nonmetallic atoms necessary to form a nitrogen-containing 5- to 6-membered heterocyclic ring, md1 represents an integer of 0 to 3 Md2 represents an integer of 0 to 4, and md3 represents an integer of 0 to 2, but md1, md2, and md3 do not represent 0 at the same time. When md1 is 2 or more, the plurality of Rd ₁ may be the same or different from each other, when md2 is 2 or more, the plurality of Rd ₂ may be the same or different from each other, and when md3 is 2, the plurality of Rd ₃ are They may be the same or different.

  The compound represented by the general formula (6) in the present invention is not particularly limited as long as it is a compound having the above-described magenta colorant properties.

In the general formula (6), Rd ₁ , Rd ₂ and Rd ₃ each represent a substituent. The substituents represented by Rd ₁ , Rd ₂ and Rd ₃ are not particularly limited, but examples of the substituent include substitution with the above-described aromatic hydrocarbon group or heterocyclic group represented by Ax ₁ or Bx _1. The group which is synonymous with the example of a possible substituent can be mentioned. These substituents may be further substituted with the same substituent. At least one of Rd ₁ , Rd ₂ and Rd ₃ is substituted with a linear alkyl group having 8 to 30 carbon atoms, and at least one of Rd ₁ , Rd ₂ and Rd ₃ is a branched alkyl group. Substituted with a group. Examples of the linear alkyl group having 8 to 30 carbon atoms include n-octyl group, n-dodecyl group, n-pentadecyl group, n-octadecyl group, and n-eicosyl group. The linear alkyl group having 8 to 30 carbon atoms may have a substituent, and the substituent is a group other than the alkyl group and the cycloalkyl group in the substituents represented by Rd ₁ and Rd _2. The same group can be mentioned. The straight chain alkyl group having 8 to 30 carbon atoms preferably has no substituent. A linear alkyl group having 10 to 20 carbon atoms is preferable, and a linear alkyl group having 12 to 18 carbon atoms is more preferable. The branched alkyl group means an alkyl group having a secondary or tertiary carbon atom, and the branched alkyl group includes an iso-propyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, 1 , 1,3,3-tetramethylbutyl group, iso-pentyl group, tert-pentyl group, 2-ethylhexyl group, iso-pentadecyl group, iso-heptadecyl group and the like. The branched alkyl group may have a substituent, and examples of the substituent include the same groups as the substituents represented by Rd ₁ and Rd ₂ . Rd ₁ is preferably a halogen atom, an alkoxy group, an aryloxy group, an anilino group, an alkylamino group, an acylamino group, or a sulfonamide group.

  In General formula (6), Zd represents a nonmetallic atom group required in order to form a nitrogen-containing 5-6 membered heterocyclic ring. Examples of the heterocyclic ring formed by Zd include a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, and a pyridone ring. As the heterocyclic ring formed by Zd, a pyridine ring, a pyrimidine ring and a pyridone ring are preferable.

In the general formula (6), md1 represents an integer of 0 to 3, md1 multiple Rd ₁ when 2 or more may be the same or different from each other. As for md1, 1-2 are preferable. md2 represents an integer of 0 to 4, and when md2 is 2 or more, a plurality of Rd ₂ may be the same or different from each other. md2 is preferably 0. md3 represents an integer of 0 to 2, and when md3 is 2, a plurality of Rd ₃ may be the same or different from each other. As for md3, 1-2 are preferable. In the general formula (6), md1, md2, and md3 do not represent 0 at the same time.

  The compound represented by the general formula (6) in the present invention is more preferably the following general formula (6-1), general formula (6-2), or general formula (6-3).

In the formula, Rd ₁₁ and Rd ₁₂ each represent a substituent, Rd ₁₃ and Rd ₁₄ each represent a hydrogen atom or a substituent, Zd ₁ represents a hydrogen atom, an alkyl group, an aromatic hydrocarbon group or a heterocyclic group, md11 represents an integer of 0 to 2, and md12 represents an integer of 0 to 4. When md11 is 2, the plurality of Rd ₁₁ may be the same or different, and when md12 is 2 or more, the plurality of Rd ₁₂ may be the same or different.

In the general formula (6-1), Rd ₁₁ , Rd ₁₂ , md11 and md12 are respectively synonymous with Rd ₁ , Rd ₂ , md1 and md2 in the general formula (6) described above.

Rd ₁₃ and Rd ₁₄ each represent a hydrogen atom or a substituent. Examples of the substituent include the same groups as the substituents represented by Rd ₁ and Rd ₂ . These substituents may be further substituted with the same substituent. Rd ₁₃ is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group. Rd ₁₄ is preferably a hydrogen atom, a heterocyclic group, an acyl group, a carbamoyl group, a cyano group, an alkoxycarbonyl group, or an aryloxycarbonyl group. Zd ₁ represents a hydrogen atom, an alkyl group, an aromatic hydrocarbon group or a heterocyclic group, and is preferably an alkyl group, an aromatic hydrocarbon group or a heterocyclic group.

In the formula, Rd ₂₁ and Rd ₂₂ each represent a substituent, Rd ₂₃ and Rd ₂₄ each represent a hydrogen atom or a substituent, Zd ₂ represents a hydrogen atom, an alkyl group, an aromatic hydrocarbon group or a heterocyclic group, md21 represents an integer of 0 to 2, and md22 represents an integer of 0 to 4. When md21 is 2, the plurality of Rd ₂₁ may be the same or different, and when md22 is 2 or more, the plurality of Rd ₂₂ may be the same or different.

In the general formula (6-2), Rd ₂₁ , Rd ₂₂ , md21 and md22 are respectively synonymous with Rd ₁ , Rd ₂ , md1 and md2 in the general formula (6) described above.

Rd ₂₃ and Rd ₂₄ each represent a hydrogen atom or a substituent. Examples of the substituent include the same groups as the substituents represented by Rd ₁ and Rd ₂ . These substituents may be further substituted with the same substituent. Rd ₂₃ is preferably a hydrogen atom, an alkyl group, an aryl group, an amino group, or an anilino group. Rd ₂₄ is preferably a hydrogen atom, a heterocyclic group, an acyl group, a carbamoyl group, a cyano group, an alkoxycarbonyl group, or an aryloxycarbonyl group. Zd ₂ represents a hydrogen atom, an alkyl group, an aromatic hydrocarbon group or a heterocyclic group, and is preferably an alkyl group, an aromatic hydrocarbon group or a heterocyclic group.

In the formula, Rd ₃₁ and Rd ₃₂ each represent a substituent, Rd ₃₃ represents a hydrogen atom or a substituent, Zd ₃ represents a hydrogen atom or an alkyl group, an aromatic hydrocarbon group or a heterocyclic group, and md31 represents 0 Integer 32 is represented, md32 represents the integer of 0-4. When md31 is 2, the plurality of Rd ₃₁ may be the same or different, and when md32 is 2 or more, the plurality of Rd ₃₂ may be the same or different.

In the general formula (6-3), Rd ₃₁ , Rd ₃₂ , md31 and md32 are respectively synonymous with Rd ₁ , Rd ₂ , md1 and md2 in the general formula (6).

Rd ₃₃ each represents a hydrogen atom or a substituent. Examples of the substituent include the same groups as the substituents represented by Rd ₁ and Rd ₂ . These substituents may be further substituted with the same substituent. Rd ₃₃ is preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably an aryl group. Zd ₂ represents a hydrogen atom, an alkyl group, an aromatic hydrocarbon group or a heterocyclic group, and is preferably an alkyl group, an aromatic hydrocarbon group or a heterocyclic group.

  Examples of the compound represented by the general formula (6) preferably used in the present invention include JP-A-7-84416, JP-A-2004-123899, JP-A-2004-190007, and JP-A-2005-2223. JP, 2005-60629, JP 2005-126587, JP 2005-146002, JP 2005-146002, JP 2005-146193, JP 2005-154539, Examples thereof include compounds described in Kaikai 2005-196018.

  Specific examples of the magenta colorant of the present invention are shown below, but the present invention is not limited thereto.

  The magenta colorant of the present invention can be easily produced by a known method.

  The compounds represented by the general formulas (10) to (13) according to the present invention are, for example, JP-A-5-297636, JP-A-8-123089, JP-A-8-123091, JP-A-8- No. 152745, JP-A-8-166589, JP-A-8-166690, JP-A-2002-371214, JP-A-2003-49099, JP-A-2005-255868, and the like. It can be synthesized with reference.

  Examples of the anthraquinone compound used in the present invention include JP-A-9-502470, JP-A-7-43948, JP-A-2006-154363, JP-A-8-314189, JP-A-5-173369, and JP-A-5-257321. JP-A-6-59509, JP-A-6-59511, JP-A-6-59512, JP-A-6-148939, JP-A-7-209912, JP-A-8-152744, JP-A-6-3858. These can be easily produced by known methods with reference to JP-A-8-15911, JP-A-7-84416, JP-A-8-123088 and the like.

  The compounds represented by the general formula (6) used in the present invention are disclosed in JP-A-7-84416, JP-A-2004-123899, JP-A-2004-190007, JP-A-2005-2223, and JP-A-2005-2223. JP 2005-60629 A, JP 2005-126587 A, JP 2005-146002 A, JP 2005-146002 A, JP 2005-146193 A, JP 2005-154539 A, JP 2005-196018 A. It can be easily produced by a known method with reference to the gazette.

  In addition, as the magenta colorant of the present invention, for example, among the pigments described in “CMC Technical Library 180 Functional Pigment Technology” (CMC Publishing Co., Ltd.), the requirements for the magenta colorant of the present invention are as follows. A filling pigment or the like can also be suitably used.

  The magenta colorant of the present invention may be used in combination of any two or more of azo compounds having an heterocyclic ring, anthraquinone compounds or compounds represented by the general formula (6).

  As the magenta toner used in the present invention, any magenta colorant can be used in addition to the azo compound having a heterocyclic ring, the anthraquinone compound, and the dye represented by the general formula (6). For example, aryl azo dyes having phenols, naphthols, anilines, etc. as coupler components; for example, azomethine dyes or methine dyes having pyrazolones, pyrazolotriazoles, etc. as coupler components; for example arylidene dyes, styryl dyes, merocyanine dyes, cyanine dyes Methine dyes such as oxonol dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone, etc. A ring dye etc. can be mentioned.

  In the color toner set of the present invention, in order to form a full-color image, in addition to the above-described cyan toner and magenta toner, yellow toner can be used together. Further, black toner may be used to further adjust the color tone.

  As the yellow toner that can be used in the toner set of the present invention, any yellow colorant can be used. Examples of yellow dyes include aryl or heteroaryl azo dyes having phenols, naphthols, anilines, heterocycles such as pyrazolone and pyridone, and open-chain active methylene compounds as coupling components (hereinafter referred to as coupler components) For example, azomethine dyes having open-chain active methylene compounds as coupler components; for example, methine dyes such as benzylidene dyes and monomethine oxonol dyes; for example, quinone dyes such as naphthoquinone dyes and anthraquinone dyes, etc. Examples of other dye species include quinophthalone dyes, nitro / nitroso dyes, acridine dyes, acridinone dyes, and the like.

  Examples of the black toner that can be used in the toner set of the present invention include carbon black dispersions as well as disazo, trisazo, and tetraazo dyes as black materials.

  Also, pigments can be preferably used in combination with the cyan, magenta, yellow, and black toners that can be used in the toner set of the present invention. Examples of the pigment include pigments described in “CMC Technical Library 180 Functional Pigment Technology” (CMC Publishing Co., Ltd.), but the present invention is not limited thereto.

  Furthermore, a compound containing a metal ion may be added to each colorant used in the toner set of the present invention for the purpose of improving the fastness of the dye.

  The metal ion is selected from metal atoms of Group VIII, Group Ib, Group IIb, Group IIIa, Group IVa, Group Va, Group Vaa, Group VIIa, and is preferably a divalent transition metal ion. Specific examples include divalent metal ions of Ni, Cu, Co, Cr, Zn, Fe, Pd, and Pt, more preferably divalent metal ions of Cu, Co, and Zn, and particularly preferably. It is a divalent metal ion of Cu.

Counter ions of metal ions include enolate (acetylacetonate, hexafluoroacetylacetonate), halogen ion (fluoride, chloride, bromide, iodide, etc.), hydroxide ion, sulfite ion, sulfate ion, alkylsulfonate ion, aryl sulfonate ion, nitrate ion, nitrite ion, carbonate ion, perchlorate ion, alkylcarboxylic acid ion, aryl carboxylate ion, tetraalkyl borate, Sarishineto, ^{benzoate, PF6 -, BF4 -, SbF6} - anions include such Preferably an enolate anion.

(Dye dispersion method)
The color toner that can be used in the toner set of the present invention is obtained by directly dispersing a pigment dispersion in a binder resin or mixing a colored fine particle dispersion, and further using a desired additive described later, It can be produced by other known methods such as a pulverization method, suspension polymerization method, emulsion polymerization method, emulsion dispersion granulation method, encapsulation method and the like. Among these production methods, the emulsion polymerization method is preferred from the viewpoints of production cost and production stability in consideration of the reduction in the toner particle size accompanying the increase in image quality. In the emulsion polymerization method, a thermoplastic resin emulsion produced by emulsion polymerization is mixed with a dispersion of other toner particle components such as a dye solid dispersion, and the repulsive force of the particle surface generated by pH adjustment and aggregation by addition of an electrolyte. Toner particles are produced by slowly agglomerating while balancing the force, associating while controlling the particle size and particle size distribution, and simultaneously performing heating and stirring to control the fusion and shape between the fine particles.

  The toner used in the toner set of the present invention preferably contains a dye as colored fine particles in a latex resin. In order to incorporate a dye in the latex resin as colored fine particles, for example, the dye or the dye and the resin are emulsified and dispersed in water, or the dye or the dye and the resin are immiscible with water such as ethyl acetate and toluene. A colored fine particle dispersion is obtained by a method of dissolving (or dispersing) in an organic solvent, emulsifying and dispersing in water, and then removing the organic solvent. The obtained colored fine particle dispersion can be obtained by agglomerating with a (thermoplastic) latex resin. Although an emulsification disperser is not limited, an ultrasonic disperser, a high-speed stirring disperser, etc. are used, for example.

  The resin that dissolves (or disperses) together with the dye is not particularly limited as long as it has a composition different from that of the thermoplastic resin. For example, a (meth) acrylate resin, a polyester resin, a polyamide resin, a polyimide resin, or a polystyrene resin. Resin, Polyepoxy resin, Polyester resin, Amino resin, Fluorine resin, Phenol resin, Polyurethane resin, Polyethylene resin, Polyvinyl chloride resin, Polyvinyl alcohol resin, Polyether resin, Polyether ketone Resin, polyphenylene sulfide resin, polycarbonate resin, aramid resin, etc., preferably (meth) acrylate resin, polystyrene resin, polyethylene resin, polyvinyl chloride resin, polyvinyl alcohol resin, etc. Ethylenic Resin obtained by polymerizing the unsaturated double bond is preferred. Most preferred are (meth) acrylate resins and polystyrene resins.

  The solid dispersion of the dye is preferably a small particle having a particle diameter of 10 nm to 100 nm, and more preferably a small particle having a particle diameter of 10 nm to 80 nm. When the solid dispersion has a small particle size and monodispersion, light scattering is suppressed, and concealing particles that block light can be eliminated. These effects improve the transparency of the toner in a single color and can greatly improve the saturation with respect to the amount of the dye attached.

  On the other hand, it can also be obtained by agglomerating a colored fine particle dispersion obtained by mixing a pigment solid with a surfactant and atomizing with a medium type stirrer with a (thermoplastic) latex resin.

(Preparation method of colored fine particles)
Next, a method for producing colored fine particles, which is one of the preferred embodiments according to the present invention, will be described.

  The colored fine particles according to the present invention can be obtained by the above-described dye dispersion method. When the resin is further added and coated with an outer shell resin (shell), the colored fine particles have a polymerizable unsaturated double bond. Is added, and emulsion polymerization is carried out in the presence of an activator, and colored particles having a core-shell structure can be obtained by depositing on the core surface simultaneously with the polymerization. Alternatively, for example, an aqueous dispersion of resin fine particles is formed in advance by emulsion polymerization, an organic solvent solution in which a dye is dissolved is mixed in the aqueous dispersion of resin fine particles, and then the resin fine particles are impregnated with the dye, and then the coloring is performed. It can be obtained by various methods such as a method of forming a shell using fine particles as a core.

  The outer shell resin that forms the shell is not particularly limited. For example, poly (meth) acrylate resin, polyester resin, polyamide resin, polyimide resin, polystyrene resin, polyepoxy resin, polyester resin, Amino resin, fluorine resin, phenol resin, polyurethane resin, polyethylene resin, polyvinyl chloride resin, polyvinyl alcohol resin, polyarylate resin, polyether resin, polyether ketone resin, polyphenylene sulfide resin Polycarbonate resins, aramid resins, and the like are mentioned, and poly (meth) acrylate resins are preferable from the viewpoint of combination with toner binder resin (thermoplastic resin).

  As a method for forming the shell, there is a method in which a resin dissolved in an organic solvent is gradually dropped, and the resin is adsorbed on the surface of the colored fine particle core simultaneously with the precipitation. A method in which a colored fine particle is formed, a monomer having a polymerizable unsaturated double bond is added, emulsion polymerization is performed in the presence of an activator, and a shell is formed by depositing on the core surface simultaneously with the polymerization is preferable.

(Reactive emulsifier)
The reactive emulsifier preferably used in the present invention may be any of anionic and nonionic reactive emulsifiers, but compounds having the following A, B or C substituents are preferred.

A: a linear alkyl group, a branched alkyl group, or a substituted or unsubstituted aromatic group having a total carbon number of 6 or more B: a nonionic substituent or anionic substituent that exhibits surface activity C: A polymerizable group capable of radical polymerization.

  Examples of the linear alkyl group described in the section A include a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, and the like, and examples of the branched alkyl group include a 2-ethylhexyl group, Examples of the aromatic group include a phenyl group, a nonylphenyl group, and a naphthyl group.

  Examples of the nonionic substituent or anionic substituent that expresses the emulsifying ability (surfactant ability) described in Item B include polyethylene oxide, polypropylene oxide, polyalkylene oxide of a copolymer thereof, and the like. Specific examples of the anionic substituent include carboxylic acid, phosphoric acid, sulfonic acid, and salts thereof. Moreover, what substituted the above-mentioned anionic group at the terminal of alkylene oxide is one of the specific examples of an anionic group. The substituent represented by the item B is preferably an anionic group, and more preferably a terminal terminal is a salt.

  The radically polymerizable group described in the item C is a group that undergoes polymerization or crosslinking reaction by radically active species. For example, a vinyl group having an ethylenically unsaturated bond, an allyl group, a 1-propenyl group, an isotopic group, Examples include propenyl group, acrylic group, methacryl group, maleimide group, acrylamide group, styryl group and the like.

  As the reactive emulsifier used in the present invention, compounds represented by the following general formulas (A) to (C) are preferable.

In the general formula (A), R ₁ represents a linear alkyl group having 6 to 20 carbon atoms, a branched alkyl group, or a substituted or unsubstituted aromatic group. For example, heptyl, octyl, nonyl, Examples include linear alkyl groups such as decyl and dodecyl groups, branched alkyl groups such as 2-ethylhexyl group, and aromatic groups such as phenyl, nonylphenyl, and naphthyl groups.

R ₂ represents a substituent having a polymerizable group capable of radical polymerization, and examples thereof include (meth) acrylic and maleimide groups which are ethylenically unsaturated bonds described in the above section C. Y ₂₁ represents a sulfonic acid, a carboxylic acid, or a salt thereof.

  The compound represented by the general formula (A) can be synthesized by a person skilled in the art by a known method. Further, it can be easily obtained from commercial products, for example, “Ramtel S-120”, “Ramtel S-120A”, “Ramtel S-180”, “Ramtel S-180A” manufactured by Kao Corporation, Sanyo Chemical An example is “Eleminol JS-2” manufactured by Kogyo Co., Ltd.

In the general formula (B), R ₃ has the same meaning as R ₁ in the general formula (A), R ₄ has the same meaning as R ₂ in formula (A). Y ₂₂ represents a hydrogen atom, a sulfonic acid, a carboxylic acid, or a salt thereof. AO represents an alkylene oxide.

  The compound represented by the general formula (B) can be synthesized by a person skilled in the art by a known method. Also, it can be easily obtained from commercial products, for example, NE series such as “Adekaria Soap NE-10”, “Adekaria Soap NE-20”, “Adekaria Soap NE-30” manufactured by Asahi Denka Kogyo Co., Ltd. SE series such as “Adekaria soap SE-10N”, “Adekaria soap SE-20N”, “Adekaria soap SE-20N”, “Aqualon RN-10”, “Aquaron RN-” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. RN series such as “20”, “AQUALON RN-30”, “AQUALON RN-50”, “AQUALON HS-05”, “AQUALON HS-10”, “AQUALON HS-20”, “AQUALON HS-30”, etc. Examples include the HS series or the Aqualon BC series.

In the general formula (C), R ₅ has the same meaning as R _{1 in the} general formula (A), R ₆ has the same meaning as R _{2 in the} general formula (A), and Y ₃₂ represents the general formula (A ) has the same meaning as Y ₂₁ of, AO has the same meaning as AO in the general formula (B).

  The compound represented by the general formula (C) can be synthesized by a person skilled in the art by a known method. Moreover, it can obtain easily from a commercial item, for example, "AQUALON KH-05", "AQUALON KH-10", "AQUALON KH-20", etc. by Dai-ichi Kogyo Seiyaku Co., Ltd. can be mentioned.

  In the general formulas (B) and (C), the average degree of polymerization n of the alkylene oxide chain (AO) is preferably 1 to 10, for example, “AQUALON KH-05” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. , “AQUALON KH-10”, “AQUALON HS-05”, “AQUALON HS-10”, and the like.

  In the present invention, the reactive emulsifier is preferably anionic. For example, the above-mentioned “Adekaria soap SE series” (Asahi Denka Kogyo Co., Ltd.), “Aqualon HS series” (Daiichi Kogyo Seiyaku Co., Ltd.) , “Latemul S series” (manufactured by Kao Corporation), “Eleminol JS series” (manufactured by Sanyo Chemical Industries), and the like.

  In the present invention, these reactive emulsifiers are generally used in an amount of 0.1 to 80 parts by weight, preferably 1 to 70 parts by weight, per 100 parts by weight in total of the resin forming the colored fine particles used in the present invention. Particularly preferably, 10 to 60 parts by mass are used.

(Surfactant)
When emulsifying the colored fine particles used in the present invention, a normal anionic emulsifier (surfactant) and / or a nonionic emulsifier (surfactant) can be used as necessary.

  Examples of the normal nonionic emulsifier include, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether, polyoxyethylene alkyl phenyl ethers such as polyoxyethylene nonylphenyl ether, and sorbitan monolaurate. Sorbitan higher fatty acid esters such as sorbitan monostearate and sorbitan trioleate, polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene monolaurate, polyoxyethylene monostearate, etc. Higher fatty acid esters of glycerin such as polyoxyethylene higher fatty acid esters, oleic acid monoglyceride, stearic acid monoglyceride Class, polyoxyethylene - polyoxypropylene - and the like block copolymer.

  Examples of the normal anionic emulsifier include higher fatty acid salts such as sodium oleate, alkylaryl sulfonates such as sodium dodecylbenzene sulfonate, alkyl sulfates such as sodium lauryl sulfate, and polyethoxyethylene lauryl ether. Polyoxyethylene alkyl ether sulfates such as sodium sulfate, polyoxyethylene alkylaryl ether sulfates such as sodium polyoxyethylene nonylphenyl ether sulfate, sodium monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate, polyoxyethylene lauryl sulfosuccinic acid Examples thereof include alkylsulfosuccinic acid ester salts such as sodium and derivatives thereof.

(Additive)
In the electrophotographic toner of the present invention, additives such as an antioxidant and an ultraviolet absorber can be preferably used for improving light resistance and heat resistance.

  The antioxidant can be used without limitation as long as it is a compound that improves light resistance. Among them, useful antioxidants include phenol ether compounds, hindered amine compounds, phosphorus compounds, sulfur compounds, heat resistance, and the like. Examples thereof include a processing stabilizer and an oxygen scavenger, and among these, phenol ether is particularly preferably used.

  As the ultraviolet absorber, those which are excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less from the viewpoint of storage stability of the toner and have little absorption of visible light having a wavelength of 400 nm or more from the viewpoint of color reproducibility of the toner image are preferable.

  Examples of the ultraviolet absorber used in the present invention include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, triazine compounds, and the like. However, benzophenone compounds, less colored benzotriazole compounds, and triazine compounds are preferable. Further, ultraviolet absorbers described in JP-A Nos. 10-182621 and 8-337574, and polymer ultraviolet absorbers described in JP-A Nos. 6-148430 and 2003-113317 may be used.

(Particle size)
The colored fine particles in the present invention preferably have a volume-based median diameter in the range of 10 to 100 nm, more preferably 10 to 50 nm. When the volume-based median diameter is 10 nm or less, the surface area per unit volume becomes very large, so that the stability of the colored fine particles tends to deteriorate and the storage stability tends to deteriorate. When the particle size exceeds 100 nm, the saturation per unit color material amount in the toner is lowered. The volume-based median diameter can be determined by using a dynamic light scattering method, a laser diffraction method, a centrifugal sedimentation method, an FFF method, an electrical detector method, and the like. In the present invention, the microtrack UPA-150 ( It is preferable to obtain by a dynamic light scattering method using Nikkiso Co., Ltd.

(Thermoplastic resin)
The thermoplastic resin (binder resin) contained in the toner of the present invention is preferably a thermoplastic resin having high adhesion to colored fine particles, and particularly preferably a solvent-soluble one. Further, if the polymer precursor is solvent-soluble, a curable resin that forms a three-dimensional structure can also be used. As the thermoplastic resin, those generally used as a binder resin for a toner are used without particular limitation. For example, styrene resins, acrylic resins such as alkyl acrylates and alkyl methacrylates, and styrene acrylic copolymer resins. Polyester resin, silicon resin, olefin resin, amide resin, epoxy resin, etc. are preferably used, but in order to improve transparency and color reproducibility of superimposed images, transparency is high and melting characteristics are high. Resins with low viscosity and high sharp melt properties are required. As the binder resin having such characteristics, styrene resins, acrylic resins, and polyester resins are suitable.

  As the binder resin, the number average molecular weight (Mn) is 3000 to 6000, preferably 3500 to 5500, and the ratio Mw / Mn of the mass average molecular weight (Mw) to the number average molecular weight (Mn) is 2 to 6, preferably 2. It is desirable to use a resin having a glass transition point of 0.5 to 5.5, a glass transition point of 50 to 70 ° C, preferably 55 to 70 ° C, and a softening temperature of 90 to 110 ° C, preferably 90 to 105 ° C.

  When the number average molecular weight of the binder resin is smaller than 3000, the image portion is peeled off when a full-color solid image is folded, and image defect occurs (folded fixing property is deteriorated). The meltability is lowered and the fixing strength is lowered. Further, if Mw / Mn is less than 2, high temperature offset is likely to occur, and if it is greater than 6, sharp melt characteristics at the time of fixing are lowered, and toner translucency and color mixing at the time of full color image formation are lowered. End up.

  Further, if the glass transition point is lower than 50 ° C., the heat resistance of the toner becomes insufficient, and toner aggregation tends to occur during storage. Color mixing at the time of image formation is reduced. Further, when the softening temperature is lower than 90 ° C., high temperature offset tends to occur. When the softening temperature is higher than 110 ° C., fixing strength, translucency, color mixing property, and gloss of a full color image are deteriorated.

(toner)
In the toner of the present invention, a known charge control agent, offset preventive agent, and the like can be used in addition to the above thermoplastic resin and colored fine particles.

  The charge control agent is not particularly limited. As the negative charge control agent used in the color toner, a colorless, white, or light color charge control agent that does not adversely affect the color tone and translucency of the color toner can be used. For example, a zinc or chromium metal complex of a salicylic acid derivative , Calixarene compounds, organoboron compounds, fluorine-containing quaternary ammonium salt compounds and the like are preferably used. Examples of the salicylic acid metal complex include those described in JP-A Nos. 53-127726 and 62-145255, and examples of calixarene compounds include those described in JP-A No. 2-201378. As the organic boron compound, for example, those described in JP-A-2-221967 can be used, and as the organic boron compound, for example, those described in JP-A-3-1162 can be used.

  When such a charge control agent is used, it is desirable to use 0.1 to 10 parts by mass, preferably 0.5 to 5.0 parts by mass with respect to 100 parts by mass of the thermoplastic resin (binder resin).

  There are no particular restrictions on the anti-offset agent. For example, polyethylene wax, oxidized polyethylene wax, polypropylene wax, oxidized polypropylene wax, carnauba wax, sazol wax, rice wax, candelilla wax, jojoba oil wax, honey Wax wax or the like can be used. The added amount of such wax is 0.5 to 5 parts by mass, preferably 1 to 3 parts by mass with respect to 100 parts by mass of the thermoplastic resin (binder resin). This is because if the addition amount is less than 0.5 parts by mass, the effect of the addition is insufficient, and if it exceeds 5 parts by mass, the translucency and color reproducibility deteriorate.

  The toner of the present invention uses the above-described thermoplastic resin (binder resin), colored fine particles and other desired additives, kneading / pulverizing method, suspension polymerization method, emulsion polymerization method, emulsion dispersion granulation method, capsule It can manufacture by other well-known methods, such as chemical conversion method. Among these production methods, the emulsion polymerization method is preferred from the viewpoints of production cost and production stability in consideration of the reduction in toner particle size accompanying the improvement in image quality.

  In the emulsion polymerization method, a thermoplastic resin emulsion produced by emulsion polymerization is mixed with a dispersion of toner particle components such as other colored fine particles, and the balance between the repulsive force of the particle surface generated by pH adjustment and the cohesive force due to the addition of an electrolyte. The toner particles are produced by slowly agglomerating while taking particles, and performing association while controlling the particle diameter and particle size distribution, and at the same time, fusing and shape control between the fine particles by heating and stirring. The toner particles according to the present invention preferably have a volume average particle diameter of 4 to 10 μm, preferably 6 to 9 μm, from the viewpoint of high-definition image reproducibility.

  In the toner of the present invention, a post-treatment agent can be added and mixed from the viewpoint of imparting toner fluidity and improving cleaning properties, and is not particularly limited. Examples of such post-treatment agents include inorganic oxide fine particles such as silica fine particles, alumina fine particles, and titania fine particles, inorganic stearate compound fine particles such as aluminum stearate fine particles and zinc stearate fine particles, and strontium titanate and titanium. Inorganic titanate compound fine particles such as zinc oxide can be used, and it is possible to use single or different additives in combination. These fine particles are preferably used after being surface-treated with a silane coupling agent, a titanium coupling agent, a higher fatty acid, silicon oil, etc. from the viewpoint of environmental stability and heat-resistant storage stability, and the amount added is 100 parts by mass of the toner. On the other hand, it is desirable to use 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass.

  The toner of the present invention can be used as a two-component developing toner used by mixing with a carrier, or as a one-component developing toner that does not use a carrier.

  As the carrier used in combination with the toner of the present invention, conventionally known carriers for two-component development can be used. For example, a carrier made of magnetic particles such as iron or ferrite, such magnetic A resin-coated carrier obtained by coating body particles with a resin, or a binder-type carrier obtained by dispersing magnetic fine powder in a binder resin can be used. Among these carriers, it is possible to use a resin-coated carrier using a silicone resin, a copolymer resin (graft resin) of an organopolysiloxane and a vinyl monomer or a polyester resin as a coating resin, such as toner spent. From the viewpoint, a carrier coated with a resin obtained by reacting an isocyanate with a copolymer resin of an organopolysiloxane and a vinyl monomer is particularly preferable from the viewpoint of durability, environmental stability, and spent resistance. . As the vinyl monomer, it is necessary to use a monomer having a substituent such as a hydroxyl group reactive with isocyanate. In addition, it is preferable to use a carrier having a volume average particle size of 20 to 100 μm, preferably 20 to 60 μm from the viewpoint of ensuring high image quality and preventing carrier fogging.

(Image forming method)
Next, an image forming method using the toner of the present invention will be described.

  In the present invention, the image forming method is not particularly limited. For example, a method of forming a plurality of images on the photoconductor and transferring them in a batch, a method of sequentially transferring the images formed on the photoconductor to a transfer belt, etc. are not particularly limited, but more preferably a plurality of images on the photoconductor In this method, an image is formed and transferred in a batch.

  In this method, the photosensitive member is uniformly charged and exposed in accordance with the first image, and then the first development is performed to form a first toner image on the photosensitive member. Next, the photoconductor on which the first image is formed is uniformly charged, and exposure according to the second image is given, and the second development is performed to form a second toner image on the photoconductor. Further, the photoconductor on which the first and second images are formed is uniformly charged, exposure according to the third image is performed, the third development is performed, and a third toner image is formed on the photoconductor Let Further, the photosensitive member on which the first, second, and third images are formed is uniformly charged to give exposure according to the fourth image, and the fourth development is performed, and the fourth toner image is formed on the photosensitive member. To form.

  For example, a full-color toner image is formed on the photoreceptor by developing the first time with yellow, the second time with magenta, the third time with cyan, and the fourth time with black toner. Thereafter, the image formed on the photoreceptor is collectively transferred to an image support such as paper, and further fixed on the image support to form an image.

  In this method, the images formed on the photoconductor are collectively transferred to paper or the like to form an image. Therefore, unlike the so-called intermediate transfer method, the number of times of transfer that causes image disturbance is one. The image quality can be improved by using only once.

  As a method for developing on the photoreceptor, non-contact development is preferable because a plurality of developments are necessary. In addition, a method in which an alternating electric field is applied during development is also a preferable method. In addition, as described above, the non-contact development method is preferable as a development method in which a superimposed color image is formed on an image forming body and batch transfer is performed.

  The volume average particle diameter of the carrier that can be used as the two-component developer is 15 to 100 μm, more preferably 25 to 60 μm. The volume average particle diameter of the carrier can be typically measured by a laser diffraction particle size distribution measuring apparatus “HELOS” (manufactured by SYMPATEC) equipped with a wet disperser.

  The carrier is preferably coated with a resin, or a so-called resin dispersion type carrier in which magnetic particles are dispersed in a resin. The resin composition for coating is not particularly limited, and for example, olefin resin, styrene resin, styrene / acrylic resin, silicon resin, ester resin, or fluorine-containing polymer resin is used. The resin for constituting the resin-dispersed carrier is not particularly limited, and known resins can be used. For example, styrene / acrylic resin, polyester resin, fluorine resin, phenol resin, etc. are used. Can do.

  As a suitable fixing method used in the present invention, a so-called contact heating method can be exemplified. In particular, typical examples of the contact heating method include a heat roll fixing method and a pressure heating fixing method in which fixing is performed by a rotating pressure member including a fixedly arranged heating body.

(image)
In image formation in which development, transfer, and fixing are performed using the toner of the present invention, the state from transfer to fixing is such that the colored fine particles collapse even after the toner of the present invention transferred onto the transfer material is fixed. In other words, it is in a state of adhering to the paper surface in a state of being dispersed in the toner particles.

  In the present invention, by dispersing the colored fine particles in the toner particles as described above, even though the toner particles contain a high concentration of the dye, the dye does not release (transfer) to the surface of the toner particle. This is a problem of the toner in which the pigment obtained by dispersing or dissolving the pigment in the thermoplastic resin (toner binder resin) as it is is exposed on the surface of the toner particles as in the prior art.

1. Low charge,
2. Large difference in charge between high temperature and high humidity and low temperature and low humidity (environment-dependent)
3. It is possible to eliminate the variation in the charge amount of each color toner in the case of using pigments of cyan, magenta, yellow, and black as in the type of colorant, for example, full color image recording.

  In addition, when heat-fixing to a transfer material, the dye that is the colorant does not migrate out of the colored fine particles (exposure to the surface of the colored fine particles), so heat-fixing that is a problem in toners using general dyes There will be no dye sublimation or oil contamination.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

1. 1. Preparation of toner 1-1. Preparation of toners 1 and 2 (toner by kneading and pulverization method) The following toner components were put into a Henschel mixer (manufactured by Mitsui Miike Mining Co., Ltd.), and the peripheral speed of the stirring blade was set to 25 m / second and mixed for 5 minutes. .

100 parts by mass of polyester resin (bisphenol A-ethylene oxide adduct, terephthalic acid, trimellitic acid condensate weight average molecular weight 20,000)
Dye 1-17 2 parts by weight Release agent (pentaerythritol tetrastearate) 6 parts by weight Charge control agent (boron dibenzylate) 1 part by weight The mixture was kneaded with a twin-screw extrusion kneader and then coarsely pulverized with a hammer mill Thereafter, the mixture was pulverized by a turbo mill pulverizer (manufactured by Turbo Kogyo Co., Ltd.), and further finely classified by an airflow classifier utilizing the Coanda effect, thereby obtaining colored particles having a volume-based median diameter of 5.5 μm.

  Next, the following external additives were added to the colored particles, and external addition processing was performed with a Henschel mixer (manufactured by Mitsui Miike Mining Co., Ltd.) to prepare “Toner 1”.

Silica treated with hexamethylsilazane (average primary particle size: 12 nm) 0.6 parts by mass Titanium dioxide treated with n-octylsilane (average primary particle size: 24 nm) 0.8 parts by mass Was performed under conditions of a peripheral speed of 35 m / sec, a processing temperature of 35 ° C., and a processing time of 15 minutes.

  Further, “Toner 2” was prepared in the same procedure except that “Dye 1-17” was changed to “Dye M-1” in the preparation of “Toner 1”.

1-2. Preparation of Toner 3-29 and Comparative Toner 1-7 (Toner by Emulsion Association Method) (1) Preparation of “Colorant Fine Particle Dispersion 1” 11.5 parts by mass of sodium n-dodecyl sulfate was added to 160 parts by mass of ion-exchanged water. The solution was added, dissolved and stirred to prepare an aqueous surfactant solution. In this surfactant aqueous solution, 2 parts by weight of “Dye 1-17” is gradually added, and dispersion treatment is performed using “Clearmix W Motion CLM-0.8 (manufactured by M Technique Co., Ltd.)”. Colorant fine particle dispersion 1 ”was prepared.

  “Colorant fine particle 1” in “Colorant fine particle dispersion 1” had a volume-based median diameter of 98 nm. The volume-based median diameter is measured using “MICROTRAC UPA-150 (manufactured by HONEYWELL)” under the following measurement conditions.

Sample refractive index 1.59
Sample specific gravity 1.05 (in terms of spherical particles)
Solvent refractive index 1.33
Solvent viscosity 0.797 (30 ° C), 1.002 (20 ° C)
0-point adjustment Ion-exchanged water was added to the measurement cell for preparation.

(2) Production of “resin particle 1 for core part” “Resin particle 1 for core part” having a multilayer structure was produced through first-stage polymerization, second-stage polymerization and third-stage polymerization shown below.

(A) First-stage polymerization 4 parts by mass of an anionic surfactant shown below (Structural Formula 1) together with 3040 parts by mass of ion-exchanged water are charged into a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introduction device. Then, a surfactant aqueous solution was prepared.

(Structural Formula 1) C ₁₀ H ₂₁ (OCH ₂ CH ₂ ) ₂ SO ₃ Na
A polymerization initiator solution in which 10 parts by mass of potassium persulfate (KPS) was dissolved in 400 parts by mass of ion-exchanged water was added to the surfactant aqueous solution, and the temperature was raised to 75 ° C. The resulting monomer mixture was dropped into the reaction vessel over 1 hour.

Styrene 532 parts by mass n-butyl acrylate 200 parts by mass Methacrylic acid 68 parts by mass n-octyl mercaptan 16.4 parts by mass After the above monomer mixture is added dropwise, the system is heated and stirred at 75 ° C. for 2 hours. Polymerization (first stage polymerization) was performed to prepare resin particles. This resin particle is referred to as “resin particle A1”. The “resin particle A1” produced by the first stage polymerization had a weight average molecular weight of 16,500.

(B) Second-stage polymerization A monomer mixed solution composed of the following compounds was charged into a flask equipped with a stirrer, and then paraffin wax “HNP-57 (manufactured by Nippon Wax Co., Ltd.)” 93 as a release agent. .8 parts by mass was added and dissolved by heating to 90 ° C. In this way, a monomer solution was prepared.

Styrene 101.1 parts by weight n-butyl acrylate 62.2 parts by weight Methacrylic acid 12.3 parts by weight n-octyl mercaptan 1.75 parts by weight On the other hand, 3 parts by weight of the anionic surfactant is dissolved in 1560 parts by weight of ion-exchanged water. An aqueous surfactant solution was prepared and heated to 98 ° C. A mechanical type having a circulation path after adding 32.8 parts by mass (in terms of solid content) of the “resin particles A1” to the surfactant aqueous solution, and further adding the monomer solution containing the paraffin wax. It was mixed and dispersed for 8 hours with a disperser “CLEAMIX (M Technique Co., Ltd.)”. An emulsified particle dispersion containing emulsified particles having a dispersed particle size of 340 nm was prepared by the mixing and dispersing.

  Next, a polymerization initiator solution in which 6 parts by mass of potassium persulfate is dissolved in 200 parts by mass of ion-exchanged water is added to the emulsified particle dispersion, and the system is polymerized by heating and stirring at 98 ° C. for 12 hours. (Second stage polymerization) was performed to prepare resin particles. This resin particle is referred to as “resin particle A2”. The “resin particle A2” produced by the second stage polymerization had a weight average molecular weight of 23,000.

(C) Third-stage polymerization A polymerization initiator solution in which 5.45 parts by mass of potassium persulfate is dissolved in 220 parts by mass of ion-exchanged water is added to the “resin particles A2” obtained by the second-stage polymerization. Under a temperature condition of 80 ° C., a monomer mixed solution composed of the following compounds was added dropwise over 1 hour.

Styrene 293.8 parts by mass n-butyl acrylate 154.1 parts by mass n-octyl mercaptan 7.08 parts by mass After completion of the dropwise addition, the mixture was heated and stirred for 2 hours to perform polymerization (third stage polymerization). It cooled to 28 degreeC and produced "resin particle 1 for core parts." Prepared by third stage polymerization. The “core part resin particles 1” had a weight average molecular weight of 26,800.

(3) Production of “resin particles for shell” Polymerization was carried out in the same manner except that the monomer mixture used in the first stage polymerization in the production of “resin particles for core 1” was changed to the following. Reaction and post-reaction treatment were performed to produce “shell resin particles 1”.

Styrene 624 parts by weight 2-ethylhexyl acrylate 120 parts by weight Methacrylic acid 56 parts by weight n-octyl mercaptan 16.4 parts by weight (4) Preparation of “Toner 3” “Toner 3” was prepared by the following procedure.

(A) Formation of core part In a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device,
Resin particle for core part 420.7 parts by mass (solid content conversion)
900 parts by mass of ion-exchanged water 200 parts by mass of the colorant particle dispersion 1 were added and stirred. After adjusting the temperature in the reaction vessel to 30 ° C., a 5 mol / liter aqueous sodium hydroxide solution was added to adjust the pH to 8-11.

  Next, an aqueous solution obtained by dissolving 2 parts by mass of magnesium chloride hexahydrate in 1000 parts by mass of ion-exchanged water was added at 30 ° C. over 10 minutes with stirring. After standing for 3 minutes, the heating was started, and the system was heated to 65 ° C. over 60 minutes to associate the particles. In this state, the particle size of the associated particles was measured using “Multisizer 3 (manufactured by Coulter)”. When the volume-based median diameter of the associated particles reached 5.5 μm, 40.2 parts by mass of sodium chloride was ion-exchanged. The association was stopped by adding an aqueous solution dissolved in 1000 parts by mass of water.

  After termination of the association, the core temperature 1 was further produced by continuing the fusion by heating and stirring for 1 hour at a liquid temperature of 70 ° C. as an aging treatment.

  The average circularity of the “core part 1” was measured by “FPIA 2000 (manufactured by Systex)” and found to be 0.912.

(B) Formation of Shell Next, 96 parts by mass of “Shell Resin Particle 1” is added at 65 ° C., and 2 parts by mass of magnesium chloride hexahydrate is added to 1000 parts by mass of ion-exchanged water. After the dissolved aqueous solution was added over 10 minutes, the temperature was raised to 70 ° C. and stirring was performed for 1 hour. In this way, after the “shell resin particles 1” were fused to the surface of the “core part 1”, an aging treatment was performed at 75 ° C. for 20 minutes to form a shell.

  Thereafter, an aqueous solution in which 40.2 parts by mass of sodium chloride was dissolved in 1000 parts by mass of ion-exchanged water was added to stop shell formation. Further, the colored particles generated by cooling to 30 ° C. at a rate of 8 ° C./min are filtered, washed repeatedly with ion exchange water at 45 ° C., and then dried with warm air at 40 ° C. “Colored particles 3” having a shell were produced.

(C) External Addition Treatment The following external additives were added to the produced “colored particles 3”, and external addition treatment was performed with a Henschel mixer (manufactured by Mitsui Miike Mining Co., Ltd.) to produce “Toner 3”.

Hexamethylsilazane-treated silica (average primary particle size 12 nm) 0.6 parts by mass n-octylsilane-treated titanium dioxide (average primary particle size 24 nm)
0.8 parts by mass The external addition treatment by the Henschel mixer was performed under the conditions of a peripheral speed of the stirring blade of 35 m / second, a treatment temperature of 35 ° C., and a treatment time of 15 minutes.

(5) Preparation of “Toners 4 to 29” and “Comparative Toners 1 to 7” In the preparation of “Toner 3”, “Dye 1-17” was changed to various colorants shown in Table 1, and the same procedure was followed. “Toners 4 to 29” and “Comparative toners 1 to 7” were prepared.

1-3. Example of Preparation of “Toner 30, 31” (Composite Polyester Toner) <Preparation of Polycondensation Resin 1>
Dodecylbenzenesulfonic acid 9.0 parts by mass 1,9-nonanediol 200 parts by mass dodecanedioic acid 287.5 parts by mass styrene 500 parts by mass at 90 ° C./1.013×10 ⁵ Pa for 5 hours while flowing nitrogen, then The temperature was changed to 110 ° C./1.013×10 ⁵ Pa, and the mixture was oligomerized by heating and stirring for 2 hours while flowing water out of the system. To this, 200 parts by mass of styrene was added, and a cooling pipe was attached so that the distilled styrene returned to the reactor. Thereafter, the reaction was carried out at 80 ° C./1 atm for 10 hours to obtain a viscous liquid (polycondensation resin 1-containing liquid). A portion of the obtained polyester was air-dried for analysis, and then dried with hot air at 60 ° C. to sufficiently remove styrene and subjected to analysis. The weight average molecular weight was 25,000. As a result of differential thermal analysis of the polyester, the melting point was 70.3 ° C.

<Preparation of resin particle dispersion (1)>
[Preparation of oil phase 1]
Liquid containing polycondensation resin 1 70 parts by weight Acrylic acid 1.5 parts by weight Dodecanethiol 1.5 parts by weight Stearyl methacrylate 1.5 parts by weight Styrene 21.6 parts by weight The above composition was weighed and heated at 120 ° C. to obtain a uniform oil Phase 1 was prepared. The amount of styrene added was adjusted so that the mass ratio of the polycondensation resin 1 to the total addition polymerizable monomer was 65% by mass.

[Preparation of aqueous phase 1]
Ion-exchanged water 200 parts by mass Dodecylbenzenesulfonic acid 1.6 parts by mass Dodecylbenzenesulfonic acid was dissolved in ion-exchanged water heated to 80 ° C. to prepare an aqueous phase 1, and 15 was obtained using a homogenizer (IKA Corporation, Ultra Turrax). After emulsifying for minutes, the oil phase 1 was added and further emulsified at 8,000 rpm for 10 minutes. Furthermore, using a nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.), 5 passes were dispersed at a discharge speed of 60 (discharge pressure 49.43 MPa) to obtain an emulsion. The volume average particle diameter of the droplet was 0.5 μm. The emulsion was put into a 1 liter reactor equipped with a stirrer, and 1.6 parts by mass of ammonium persulfate dissolved in 10 parts by mass of ion-exchanged water was added, and polymerization was performed in a nitrogen atmosphere for 6 hours. A stable resin particle dispersion having a median diameter of 0.4 μm was obtained. A small amount of the obtained dispersion was taken and the physical properties of the composite polymer were measured.

Weight average molecular weight of addition polymerization type resin by GPC 15,000
Weight average molecular weight of polyester by GPC 28,000
Melting point of polyester 71 ℃
The polymer obtained as described above was confirmed to be a composite particle of polyester-addition polymerization resin. Ion exchange water was added to the obtained resin particle dispersion to adjust the solid content to 20% to obtain a resin particle dispersion (1).

  The resin particles in the resin particle dispersion (1) have an overall ratio of particles having a median diameter of 0.03 μm or less or 5.0 μm or more (hereinafter also referred to as “large / small particle total ratio”) of 6.1%. Met.

  Further, when the stability of the resin particle dispersion (1) was examined, no aggregates were observed and the dispersion was in a stable state (）).

<Preparation of Colorant Particle Dispersion (1)>
Dye 1-57 50 parts by weight Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R) 5 parts by weight Ion-exchanged water 200 parts by weight According to the above composition, the components were mixed and dissolved, and a homogenizer (manufactured by IKA, Ultra-Turrax) was dispersed for 5 minutes and ultrasonic bath for 10 minutes to obtain a cyan colorant particle dispersion (1) having a median diameter (median diameter) of 240 nm and a solid content of 21.5%.

<Preparation of Colorant Particle Dispersion (2)>
Dye M-29 50 parts by weight Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R) 5 parts by weight Ion-exchanged water 200 parts by weight According to the above composition, the components were mixed and dissolved, and a homogenizer (manufactured by IKA, Ultra-Turrax) was dispersed for 5 minutes using an ultrasonic bath to obtain a magenta colorant particle dispersion (2) having a median diameter (median diameter) of 240 nm and a solid content of 21.5%.

<Preparation of release agent particle dispersion>
Paraffin wax (Nippon Seiwa Co., Ltd., HNP9; melting point 70 ° C.) 50 parts by mass Anionic surfactant (Dow Fax manufactured by Dow Chemical Co.) 5 parts by weight Ion-exchanged water 200 parts by weight And then sufficiently dispersed with a homogenizer (IKA, Ultra Turrax T50), and then dispersed with a pressure discharge type homogenizer (Gorin homogenizer, Gorin), with a center diameter (median diameter) of 180 nm and a solid content. A 21.5% release agent particle dispersion was obtained.

<Preparation of Toner 30>
Resin particle dispersion (1) 210 parts by mass (42 parts by mass of resin particles)
Colorant particle dispersion (1) 40 parts by mass (8.6 parts by mass of pigment)
Release agent particle dispersion 40 parts by mass (release agent 8.6 parts by mass)
0.15 parts by mass of polyaluminum chloride 300 parts by mass of ion-exchanged water In accordance with the above composition, the components were thoroughly mixed and dispersed in a round stainless steel flask with a homogenizer (manufactured by IKA, Ultra Turrax T50), and then heated oil The flask was heated to 40 ° C. while stirring the flask with a bath, and held at 40 ° C. for 60 minutes, and then 105 parts by mass (21 parts by mass of resin particles) of the resin particle dispersion (1) was added and gently stirred.

  Thereafter, the pH in the system was adjusted to 6.0 with a 0.5 mol / liter aqueous sodium hydroxide solution, and then heated to 85 ° C. while stirring was continued. During the temperature rise to 85 ° C, the pH in the system usually drops to 5.0 or less, but here, an aqueous sodium hydroxide solution is added dropwise to keep the pH from dropping to 5.5 or less. did.

  After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then solid-liquid separated by Nutsche suction filtration. Then, it was redispersed in 3 liters of ion exchange water at 40 ° C., and stirred and washed at 300 rpm for 15 minutes. This washing operation was repeated 5 times, and solid-liquid separation was performed by Nutsche suction filtration, followed by vacuum drying for 12 hours to obtain toner 30.

<Preparation of Toner 31>
Further, a toner 31 was obtained in the same manner as the toner 30 except that the colorant particle dispersion (1) was changed to the colorant particle dispersion (2).

1-4. Preparation example of “Toners 32 and 33” (modified polymer toner)
(Production of aqueous medium)
In a reaction vessel in which a stir bar and a thermometer are set, 683 parts by mass of water, 11 parts by mass of sodium salt of an ethylene oxide adduct sulfate (“Eleminol RS-30”; manufactured by Sanyo Chemical Industries Ltd.), 80 styrene 1 part by weight, 83 parts by weight of methacrylic acid, 110 parts by weight of butyl acrylate, 12 parts by weight of butyl thioglycolate, and 1 part by weight of ammonium persulfate were stirred for 15 minutes at 400 rpm, and the white emulsion was Obtained. The emulsion was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Next, 30 parts by mass of a 1% by mass ammonium persulfate aqueous solution was added to the reaction solution, and aged for 5 hours at 75 ° C., and a vinyl resin (styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate sodium salt co-polymerized. An aqueous dispersion (hereinafter referred to as “fine particle dispersion 1”) was prepared. The obtained “fine particle dispersion 1” had a volume average particle size of 120 nm as measured with a laser diffraction particle size distribution analyzer (“LA-920”; manufactured by Shimadzu Corporation). Further, a part of the obtained “fine particle dispersion 1” was dried to isolate the resin component. The glass transition temperature (Tg) of the resin was 42 ° C., and the weight average molecular weight (Mw) was 30,000. Then, 990 parts by mass of water, 83 parts by mass of the above-mentioned “fine particle dispersion 1”, 37 parts by mass of a 48.5% by mass aqueous solution of sodium dodecyl diphenyl ether disulfonate (“Eleminol MON-7”; manufactured by Sanyo Chemical Industries, Ltd.), and 90 parts by mass of ethyl acetate was mixed and stirred to prepare a milky white liquid (hereinafter referred to as “aqueous phase”).

(Synthesis of polyester (1))
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 229 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 529 parts by mass of bisphenol A propylene oxide 3 mol adduct, 208 parts by mass of terephthalic acid, 46 adipic acid 46 Part by mass and 2 parts by mass of dibutyltin oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure. Next, after reacting the reaction solution under reduced pressure of 1.33 × 10 ^{3 to} 2.00 × 10 ³ Pa for 5 hours, 45 parts by mass of trimellitic anhydride was added to the reaction vessel, Reaction was performed at 180 ° C. for 2 hours to synthesize polyester (1). The obtained polyester (1) had a number average molecular weight (Mn) of 2,500, a weight average molecular weight (Mw) of 6,500, a glass transition temperature (Tg) of 43 ° C., and an acid value of 25.

(Synthesis of prepolymer (1))
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 81 parts by mass of bisphenol A propylene oxide 2 mol adduct, 283 parts by mass of terephthalic acid, trimellitic anhydride 22 parts by mass of acid and 2 parts by mass of dibutyltin oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure. Then, under a reduced pressure of ^{1.33 × 10 3 ~2.00 × 10 3} Pa, and reacted for 5 hours to synthesize an intermediate polyester.

  The resulting intermediate polyester has a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 9,500, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51. Then, 1410 parts by mass of the “intermediate polyester”, 89 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate were charged in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and the mixture was charged at 100 ° C. for 5 hours. The prepolymer (1) was synthesized by reaction. The free isocyanate content of the obtained prepolymer (1) was 1.53% by mass.

(Synthesis of ketimine)
In a reaction vessel in which a stir bar and a thermometer were set, 170 parts by mass of isophoronediamine and 75 parts by mass of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound. The amine value of the obtained ketimine compound was 418.
(Emulsification / Dispersion)
In a tank, 170 parts of 35% carnauba wax ethyl acetate dispersion, 267 parts by weight of the prepolymer (1), 2.9 parts by weight of the ketimine compound, 31 parts by weight of dye 5-23, 546 parts by weight of polyester (1), After charging 1165 parts of ethyl acetate and mixing for 10 minutes at 5,000 rpm using a TK homomixer (made by Tokushu Kika), 3350 parts by mass of the aqueous phase was added to the reaction vessel, and the TK homomixer was added. The mixture was mixed for 20 minutes at a rotational speed of 13,000 rpm to perform urea formation and emulsification / dispersion to prepare an emulsified slurry. Next, the emulsified slurry was charged into a reaction vessel equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours. Thereafter, the emulsified slurry was aged at 45 ° C. for 4 hours. The obtained emulsified slurry had a volume average particle diameter measured by Multisizer II (manufactured by Coulter Counter) of 5.7 μm and a number average particle diameter of 5.4 μm.

(Washing and drying)
After 100 parts by mass of the emulsified slurry after aging was filtered under reduced pressure, 100 parts by mass of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at a rotation speed of 5,000 rpm), and then filtered. . 100 mass parts of 10 mass% sodium hydroxide aqueous solution was added to the filter cake obtained here, and it mixed by TK type homomixer (30 minutes at the rotation speed of 5,000 rpm), Then, it filtered under reduced pressure. 100 mass parts of 10 mass% hydrochloric acid was added to the filter cake obtained here, and it mixed with TK type homomixer (10 minutes at the rotation speed of 5,000 rpm), and then filtered. An operation of adding 300 parts by mass of ion-exchanged water to the obtained filter cake, mixing with a TK homomixer (10 minutes at a rotation speed of 5,000 rpm), and then filtering was performed twice. " The final filter cake obtained here was dried at 45 ° C. for 48 hours with a circulating drier, pulverized with an opening mixer, and then sieved with a mesh of 44 μm to obtain toner particles (1).

  Next, 100 parts of the obtained toner particles (1) and 0.25 part of a charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) were charged into a Q-type mixer (manufactured by Mitsui Mining Co., Ltd.), and the peripheral speed of the turbine blades Was set to 50 m / sec and mixed. In this case, the mixing operation was performed for 2 minutes, 5 cycles of 1 minute pause, and the total treatment time was 10 minutes.

  Further, 0.5 part of hydrophobic silica (H2000, manufactured by Clariant Japan) was added and mixed. In this case, the mixing operation was performed at a peripheral speed of 15 m / sec and 30 seconds of mixing for 1 minute and resting for 5 cycles.

  Thus, toner 32 was obtained.

  A toner 33 was obtained in the same manner except that the dye was changed from the dye 5-23 to the dye M-73.

1-5. Preparation example of “toners 34 and 35” (toner using aromatic carboxylic acid titanium compound)
<Synthesis of low molecular weight resin component (1)>
A glass 4-liter four-necked flask equipped with a thermometer, a stirring bar, a condenser and a nitrogen inlet tube was placed in the oil bath. This was filled with the following composition.

Xylene 500 parts Styrene 60 parts Methyl methacrylate 40 parts 1,1'-Azobis (cyclohexane-1-carbonitrile) 10 parts While stirring this flask at 150 rpm with a stirrer, the temperature of the oil bath is raised to 70-80 ° C. The polymerization was carried out by adjusting stepwise and reacting for 10 hours.

  After the reaction, the solvent was removed from the content obtained by an evaporator, and the resulting product was precipitated in methanol to purify the low molecular resin. When the molecular weight of the obtained low molecular weight resin (1) was measured, it was 3200 in Mw.

<Preparation of polyester resin>
[Synthesis of aromatic carboxylic acid titanium compounds]
65.3 parts of isophthalic acid and 18.0 parts of ethylene glycol were mixed in a glass 4-liter four-necked flask equipped with a thermometer, a stirring bar, a condenser and a nitrogen introduction tube and placed in a mantle heater, and the temperature was 100 ° C. And then depressurized and dehydrated. Thereafter, after cooling to 50 ° C., 17.2 parts of titanium tetramethoxide was added under a nitrogen atmosphere. Thereafter, the pressure was reduced, and methanol as a reaction product was distilled off to obtain an aromatic carboxylic acid titanium compound (1).

[Polyester resin synthesis]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 694 parts of bisphenol A propylene oxide 2-mole adduct, 303 parts of terephthalic acid and 1 part of titanium aromatic carboxylate compound (1) were placed at 230 ° C. The reaction was carried out for 12 hours while distilling off the water produced under a nitrogen stream. Next, the reaction was carried out under a reduced pressure of 6.7 × 10 ^{2 to} 2.7 × 10 ³ Pa. When the acid value reached 1, the mixture was cooled to 180 ° C., added with 27 parts of trimellitic anhydride, and sealed at normal pressure. And reacted for 1 hour. Thereafter, it was taken out to obtain a polyester resin (1).

The polyester resin (1) was a light yellowish brown resin, had a glass transition temperature Tg of 68 ° C., a peak molecular weight of 9,500, and a ratio of the peak molecular weight to Tg of 140 (° C.) ⁻¹ . The acid value was 12 mgKOH / g, and the hydroxyl value was 17 mgKOH / g.

<Preparation of Toner 34>
A polymerization toner was prepared in an aqueous medium by the following procedure.

  3 parts of magnesium phosphate was added to 900 g of ion-exchanged water heated to 60 ° C., and stirred at 10,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to prepare an aqueous medium.

  Further, the following formulation was put into a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), heated to 60 ° C., and then stirred at 9,000 rpm for dissolution and dispersion.

Styrene 64 parts n-butyl acrylate 16 parts Low molecular weight resin (1) 20 parts Ester wax (pentaerythritol stearate, acid value 4) 8 parts Dye 3-9 8 parts Benzyl acid boron complex (Nippon Carlit: LR-147) 2 Part Polyester resin (1) 10 parts (Polycondensation product of propylene oxide modified bisphenol A and isophthalic acid, Tg = 65 ° C., Mw = 10000, Mn = 6000)
15 parts of stearyl stearate wax (DSC main peak 60 ° C.) 15 parts of this, 2.5 parts of polymerization initiator 1,1′-azobis (cyclohexane-1-carbonitrile) is dissolved to prepare a polymerizable monomer composition. did.

  The polymerizable monomer composition was charged into the aqueous medium, and the mixture was granulated by stirring at 8,000 rpm using a TK homomixer at 60 ° C. in a nitrogen atmosphere.

  Then, the temperature was raised to 70 ° C. over 2 hours while stirring by transferring to a propeller type stirring device, and further 4 hours later, the temperature was raised to 80 ° C. at a rate of temperature rise of 40 ° C./Hr and reacted at 80 ° C. for 5 hours Went. Thereafter, the styrene monomer was removed by distillation to complete the reaction. After the completion of the polymerization reaction, the slurry containing the particles was cooled, washed with an amount of water 10 times that of the slurry, filtered and dried, and then the particle diameter was adjusted by classification to obtain toner particles 1.

  To 100 parts of the toner particles, 1.5 parts of silica (R972 manufactured by Aerosil Co., Ltd.) was mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.) to obtain toner 34.

<Preparation of Toner 35>
Toner 35 was obtained in the same manner except that the dye was changed from "Dye 3-9" to "Dye M-45".

1-6. Preparation of black toner BK-1 (dispersion of colorant)
90 g of sodium dodecyl sulfate was dissolved in 1600 ml of ion-exchanged water with stirring. While stirring this solution, 400.0 g of carbon black (Regal 330R: manufactured by Cabot) was gradually added, and then dispersed using a mechanical disperser CLEARMIX (manufactured by M Technique Co., Ltd.). A dispersion of colorant particles was prepared. The particle diameter of the colorant particles in this dispersion was measured using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics Co., Ltd.) and found to be 110 nm.

(Aggregation / fusion) Meeting Latex for core 2L
670 g of ion exchange water
Colorant dispersion 400g
The above was put into a 5 L reaction vessel equipped with a temperature sensor, a cooling pipe, a nitrogen introducing device, and a stirring device, and the liquid temperature was adjusted to 30 ° C. Then, a 5N aqueous sodium hydroxide solution was added to this solution to adjust the pH. Was adjusted to 10.

  Next, an aqueous solution in which 60 g of magnesium chloride hexahydrate was dissolved in 60 ml of ion-exchanged water was added over 10 minutes at 30 ° C. with stirring. After standing for 3 minutes, the temperature was raised and the system was heated to 99 ° C. over 60 minutes to grow the particle size and carry out an association reaction. In this state, the particle size of the associated particles was measured with Coulter Multisizer III, and when the volume average median diameter reached 5 μm, an aqueous solution in which 8.5 g of sodium chloride was dissolved in 35 ml of ion-exchanged water was added to form particles. Stopped growth.

  Further, 530 g of the shell latex was added, and the heating and stirring were continued for 4 hours to fuse the latex 2L to the surface of the aggregated particles of the core latex 1. Here, 17 g of sodium chloride was added to stop particle growth, and then the mixture was superheated at 97 ° C. for fusing the latex for the shell. When the desired circularity was reached, the mixture was cooled to 30 ° C., hydrochloric acid was added to adjust the pH to 4.0, and stirring was stopped.

  Thereafter, “toner BK-1” was prepared by the same external addition process as “toner 3”.

1-7. Preparation of Yellow Toner Y-1 Toner 1 Legal 330R was converted to C.I. I. “Toner Y-1” was prepared in the same manner as Black Toner BK-1, except that it was changed to Pigment Yellow 185.

1-8. Preparation of “Developers 1-35”, “Comparative Developers 1-7”, “Developer BK-1”, “Developer Y-1” “Toners 1-35” and “Comparative Toners 1-7” ”,“ Toner Y-1 ”and“ Black Toner BK-1 ”were mixed with a ferrite carrier having a volume average particle diameter of 60 μm coated with a silicone resin, and“ Developers 1 to 35 ”having a toner concentration of 6%. “Comparative developers 1 to 7”, “Developer BK-1”, and “Developer Y-1” were prepared.

<Evaluation of toner>
The evaluation was performed on each of cyan, magenta, yellow, and black produced on a commercially available composite printer “bizhub Pro C500 (manufactured by Konica Minolta Business Technologies, Inc.)” corresponding to the two-component development type image forming apparatus of FIG. Developer was charged.

  Further, the belt fixing type fixing device shown in FIG. 4 was mounted on the printer for evaluation. Various conditions such as the surface material and surface temperature of the heating roller in the belt fixing type fixing device described above were set as follows.

Fixing speed: 230mm / sec
Heat roller surface material: Polytetrafluoroethylene (PTFE)
Heating roller surface temperature: 125 ° C
In the evaluation, the toner prepared above was loaded in the evaluation apparatus in order, and the toner set No. shown in Table 3 under the environment of normal temperature and normal humidity (20 ° C., 55% RH). 1-3, yellow, magenta, cyan, black and green, red, blue, and gray color patterns of monochromatic and mixed colors whose density is changed stepwise so that the density is 0.7 to 1.8. The output image was evaluated on plain paper copier paper having an L ^* value of 94.5 and a C ^* value of 3.4.

(Hue angle of cyan toner)
Using a colorimeter “SPM50” (manufactured by Gretag), the portion of the cyan single color L ^* value of 40-60 is measured with the measurement light D50 and the viewing angle of 2 °. The L ^* value, a ^* value of the unfixed image The b ^* value was measured, and the hue angle (h) was calculated according to the above formula, and evaluated in four stages as follows.

A: Hue angle (h) is in the range of 220 ≧ h ≧ 200 B: Hue angle (h) is in the range of 225 ≧ h> 220 or 200> h ≧ 180 C: Hue angle (h) is 230 ≧ h> 225 or 180> h ≧ 170. D: Hue angle (h) is in a range of h> 230 or h <170 (color reproduction of magenta toner)
The color reproducibility of the magenta image pattern was visually evaluated in five stages by 10 subjects. The total of 10 people was 45 or more as A, 39-44 as B, 33-38 as C, and 32 or less as D.

(Light resistance evaluation of cyan and magenta toners)
Immediately after recording the produced cyan or magenta image, and after the image was subjected to a 14-day exposure test using a “Xenon Long Life Weather Meter” (Xenon Arc Lamp, 70000 Lux, 24.0 ° C.) manufactured by Suga Test Instruments Co., Ltd. Was measured by Macbeth Color-Eye 7000, and the value of (density after light irradiation) / (density before light irradiation) was evaluated as the dye residual ratio of cyan or magenta in the following four stages.

A: Dye remaining ratio is 0.95 or more A: Dye remaining ratio is 0.90 or more and less than 0.95 B: Dye remaining ratio is 0.80 or more and less than 0.90 Δ: Dye remaining ratio is 0.70 or more and 0 Less than 80 x: Dye residual ratio is less than 0.70 [Ozone resistance test method]
Each color and mixed images were exposed to ozone gas for 7 days under the condition that the ozone gas concentration was set to 5 ppm (25 ° C .; 60% RH). The ozone gas concentration was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS. After a certain period of time from the start of exposure, the dye remaining rate of the cyan dye in each color and the mixed color image was measured using Macbeth Color-Eye 7000. The reflection density was measured at three points of 0.7, 1.0 and 1.8. From the obtained results, the dye residual ratio was obtained using the following formula: dye residual ratio (%) = (concentration before exposure / concentration before exposure) × 100%, and recorded on the recorded matter using the following criteria. The ozone resistance of cyan and magenta colors was ranked 5-1.

  5: ROD after 7 days from the start of the test is 85% or more at any concentration.

  4: The ROD after 7 days from the start of the test is such that the concentration at any one point is less than 85%.

  3: The ROD after 7 days from the start of the test is such that the concentration at any two points is less than 85%.

  2: The ROD after 7 days from the start of the test is such that the concentration at any two points is less than 80%.

  1: ROD 7 days after the start of the test is less than 75% at all concentrations.

  Table 1 shows the evaluation results of the hue angle, light resistance, and ozone gas resistance of the cyan image, and Table 2 shows the evaluation results of the color reproducibility, light resistance, and ozone gas resistance of the magenta image.

(Evaluation of blue image pattern)
<Blue reproducibility>
The color reproducibility of the produced blue image pattern was visually evaluated on a five-point scale by 10 persons. In the evaluation method, blue reproducibility was visually evaluated in 5 stages by 10 subjects.

  The total of 10 people was 45 or more as A, 39-44 as B, 33-38 as C, and 32 or less as D.

<Hue change after light irradiation of blue image>
The light resistance of the blue image before and after the light irradiation was evaluated under the same light irradiation conditions as those for evaluating the cyan and magenta images. In the evaluation method, the blue reproducibility of the sample after the light irradiation was visually evaluated in 5 stages by 10 subjects. The total of 10 people was 45 or more as A, 39-44 as B, 33-38 as C, and 32 or less as D.

<Ozone gas resistance evaluation>
Similarly to cyan and magenta single colors, an ozone exposure test was performed on blue images under the same conditions. As an evaluation method, a blue hue change before and after exposure to ozone was visually observed by 10 test subjects, and an evaluation was made on a 5-point scale. The total of 10 people was 45 or more as A, 39-44 as B, 33-38 as C, and 32 or less as D.

  Table 3 shows the evaluation results of the blue image.

  As shown in Table 3, by combining the cyan toner and the magenta toner used in the color toner set of the present invention, a blue image better than imagined from the color reproducibility, light resistance, and ozone resistance of cyan or magenta toner alone. Color reproducibility was obtained, and it was also clarified that there was little hue change due to light irradiation and ozone exposure.

Claims (7)

An azo compound or anthraquinone compound containing at least one dye represented by the following general formulas (1) to (5) as a colorant in the cyan toner and having a heterocyclic ring in the magenta toner, or the following general formula (6 In the toner set for electrophotography containing at least one magenta colorant of the compound represented by formula (1), the hue angle (h) of the cyan toner according to the L ^* a ^* b ^* color system is 170 ° ≦ h ≦ An electrophotographic toner set characterized by being 230 °.

[Wherein, Z ¹ represents a 5- or 6-membered heterocyclic group or carbocyclic group which may have a condensed ring, and Z ² represents a 5- or 6-membered heterocyclic ring which may have a condensed ring. Represents a group or an aryl group, and R ¹ and R ² represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, or a sulfonyl group. ]

[Wherein, R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or a substituent, Z ³ represents a 5-membered or 6-membered heterocyclic ring or carbocycle, and Z ⁴ represents 5 or 6 Represents a member heterocycle. ]

[Wherein, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represents a hydrogen atom or a substituent, X ¹ represents a hydroxyl group, a hydroxyl anion, an alkoxy group or an aryloxy group, and m1 and m2 represent 0 Or 1 and Z ⁵ and Z ⁶ each independently represents a 5- or 6-membered heterocyclic ring or carbocyclic ring which may have a condensed ring. ]

[Wherein, X ² represents a hydroxyl group, a hydroxyl anion, an alkoxy group or an aryloxy group, R ¹¹ and R ¹² each independently represents a hydrogen atom or a substituent, and Z ⁷ and Z ⁸ each independently represent a condensed group. It represents a 5- or 6-membered heterocyclic ring or carbocyclic ring which may have a ring. ]

[Wherein, R ^{13 to} R ¹⁵ each represents a hydrogen atom or a substituent, and Z ⁹ and Z ¹⁰ each independently represent a 5- or 6-membered heterocyclic ring or carbocyclic ring which may have a condensed ring, ³ represents —OR ¹⁷ , —NR ¹⁸ R ¹⁹ , R ¹⁷ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, or a carbonyl group, and R ¹⁸ and R ¹⁹ represent a hydrogen atom, an alkyl group, an aryl group, Represents a heterocyclic group, a carbonyl group or a sulfonyl group, and m3 represents 0 or 1; ]

[Wherein, Rd ₁ , Rd ₂ and Rd ₃ each represents a substituent, Zd represents a nonmetallic atom group necessary for forming a nitrogen-containing 5- to 6-membered heterocyclic ring, and md1 is an integer of 0 to 3 Md2 represents an integer of 0 to 4, and md3 represents an integer of 0 to 2, but md1, md2, and md3 do not represent 0 at the same time. When md1 is 2 or more, the plurality of Rd ₁ may be the same or different from each other, when md2 is 2 or more, the plurality of Rd ₂ may be the same or different from each other, and when md3 is 2, the plurality of Rd ₃ are They may be the same or different. ] 2. The toner set for electrophotography according to claim 1, wherein a hue angle (h) according to L ^* a ^* b ^* color system indicated by cyan toner is in a range of 220 to 200. The electrophotographic toner set according to claim 1, wherein Z ¹ in the general formula (1) is represented by the following general formulas (7-1) to (7-7).

[Wherein, R ^{20 to} R ³⁹ represent a hydrogen atom or a substituent, L ¹ represents a nitrogen atom or —C (R) ═, and R represents a hydrogen atom or a substituent. * Represents a binding site. ] Z ³ in the general formula (2) is the general formula (7-3), (7-4), (7-5), (7-6), (7-7), or the following general formula (7- 8), and Z ⁴ in formula (2) is represented by any one of formulas (8-1) to (8-3). Toner set for electrophotography.

[Wherein, R ⁴⁰ and R ⁴¹ each independently represent a hydrogen atom or a substituent, * represents a bonding site, R ^{51 to} R ⁵³ each independently represent a hydrogen atom or a substituent, and n1, n2, n3 Represents an integer of 0 to 2, X ¹¹ and X ¹² represent an oxygen atom, a sulfur atom, — (NR ⁵⁴ ) —, —CR ⁵⁵ R ⁵⁶ —, and R ^{54 to} R ⁵⁶ each independently represent a hydrogen atom or a substituent. And at least one of X ¹¹ and X ¹² represents — (NR ⁵⁴ ) —, and X ¹³ , X ¹⁴ , and X ¹⁵ represent an oxygen atom, a sulfur atom, — (NR ⁵⁷ ) —, —C (R ⁵⁸ R ⁵⁹⁾ - it represents, R ⁵⁷ to R ⁵⁹ represents a hydrogen atom or a substituent, at least one oxygen atom of X ¹³ to X ^15, a sulfur atom or - (NR ⁵⁷⁾ - represents, ** the binding site Represents. ] In the general formula (3), m1 + m2 = 0 or 1, Z ⁵ is represented by the following general formula (9-1), and Z ⁶ in the general formula (3) is represented by the following general formula (9-2). The toner set for electrophotography according to claim 1, wherein the toner set is represented by:

[Wherein R ⁶⁰ represents an oxygen atom, a sulfur atom, = (N ⁺ R ⁶² R ⁶³ ), R ⁶² and R ⁶³ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group; ⁶¹ represents a hydroxyl group, an alkoxy group, a thiol group, a thioalkyl group, —NR ⁶⁴ R ⁶⁵ , R ⁶⁴ and R ⁶⁵ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, L ^{11 to} L ¹⁸ each independently represents a nitrogen atom or —C (R ⁶⁶ ) ═, R ⁶⁶ represents a hydrogen atom or a substituent, and ^* 1 and ^* 2 represent a bonding site. ] Z ⁷ in the general formula (4) is represented by the general formulas (8-1) to (8-3), and Z ⁸ in the general formula (4) is represented by the following general formulas (8-4) to (8- The toner set for electrophotography according to claim 1, wherein the toner set is represented by 6).

[Wherein, R ^{71 to} R ⁷³ each independently represents a substituent, k 1 represents an integer from 0 to 2, k 2 and k 3 represent an integer from 0 to 4, and k 1, k 2 and k 3 are 2 or more. a case, a plurality of R ^71, R ^72, R ⁷³ may be the same or different, may form a fused ring bond to each other is R ^71, R ^72, R ⁷³ which are adjacent to each other, R ⁷⁴ Represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, or a sulfonyl group, and X ¹⁷ , X ¹⁸ , and X ¹⁹ each independently represent an oxygen atom, a sulfur atom, — (NR ⁷⁵ ) —, —C ( R ⁷⁶ R ⁷⁷ ) —, R ^{75 to} R ⁷⁷ each represent a hydrogen atom or a substituent, and ^* 3 represents a binding site. ] Z ⁹ in the general formula (5) is represented by the general formulas (7-1) to (7-8), and Z ¹⁰ is represented by the general formulas (8-1) to (8-3). The toner set for electrophotography according to claim 1, wherein the toner set is an electrophotographic toner set.