JP5347757B2 - Toner set for electrophotography - Google Patents

Description

  The present invention relates to an electrophotographic toner set.

  In recent years, the dispersed light is exposed on a photoconductor to form an electrostatic latent image of an original, which is developed with each color toner to obtain a colored copy image, or each color copy image is superimposed. A color copying method for obtaining a full-color copy image has been put into practical use, and color toners such as yellow, magenta, and cyan in which colorants of respective colors are dispersed in a binder resin have been manufactured as color toners used for this.

  As electrophotographic color image forming apparatuses become widespread, their applications have been diversified and demands on image quality have become stricter. When copying images such as general photographs, catalogs, and maps, it is required to reproduce very finely and faithfully up to minute parts, and accordingly, the demand for color vividness is also increasing. It is desired to extend the reproduction range. In recent years, especially in the field of printing, where high-definition is required, the electrophotographic method is required to have high definition equal to or higher than the printing quality.

  Conventionally, known organic pigments and oil-soluble 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 oil-soluble dyes, but are present in a state of being dispersed in the form of particles in the toner, resulting in increased hiding power and transparency. It will decline. 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. In addition, in order to make it possible to visually confirm the color of the toner in the lowermost layer, the lowermost toner in the color-superposed toner is not hidden by the upper layer, and is fixed. In addition, the transparency of the toner is required, and in order to maintain the color reproducibility of the original, the dispersibility of the colorant and the coloring power are required.

  Transparency is improved by, for example, using the flushing method as a method of dispersing the pigment to achieve the pigment dispersion diameter of the order of submicron by primary particles without aggregated secondary particles. Means for improving the charging property, fixing property, and image uniformity by coating the pigment particles with a binder resin and an outer shell resin have been proposed (for example, see Patent Documents 1 and 2).

  However, even in the case of outputting with the toner proposed in these cases, it is still difficult to obtain sufficient hue and transparency in the case of a toner using pigment.

  In color image forming apparatuses, in principle, all color reproduction can be performed by subtractive color mixing using the three primary colors of yellow, magenta, and cyan. However, in reality, the spectrum when a pigment is dispersed in a thermoplastic resin is used. The range of color reproducibility and saturation are reduced by the color mixing characteristics when toners of different colors are superimposed on each other, so there are still many issues remaining to faithfully reproduce the color of the document. Yes.

  As described above, since a full-color image is colored by mixing two or more color toners that are superimposed, it is necessary to obtain a balanced hue. For example, color toners of yellow, magenta, and cyan are used. There has been proposed a color toner set in which the pigments and the contents thereof are appropriately selected (see, for example, Patent Document 3). Also, a method has been proposed in which an image is formed by using a solid color toner (dark toner) in the solid portion and a lighter toner (light toner) in the highlight portion (see, for example, Patent Document 4).

  Furthermore, there is a technique that realizes reproduction of delicate hues by expanding the color gamut using seven color toners including red, blue, and green toners (see, for example, Patent Documents 5 and 6).

  However, even if these methods are used, color reproducibility at the time of color mixing is still insufficient.

  Further, as a unique problem that occurs when toners of different colors are mixed instead of a single color toner, for example, there is a phenomenon that the light resistance of cyan toner deteriorates when magenta toner and cyan toner are mixed. This is because the light energy absorbed by the magenta dye moves to the cyan dye. In general, when a phthalocyanine dye is used as a cyan dye, such a phenomenon hardly occurs because light resistance is high.

  However, since phthalocyanine-based dyes have low ozone resistance, it is difficult to achieve both light resistance and ozone resistance when a cyan toner and other toners are mixed to form a printed matter. Development of a toner set that satisfies the above requirements is desired.

  In recent years, there has been a rapid increase in demand for printing images on display devices for image processing on CRT displays and liquid crystal displays, electronic data submission, personal use, and the like. SRGB, which is a simple color space (for example, “Multimedia Systems and Equipment-Color Measurement and Management-Part2-1: Color Management-Default RGB Color Space-sRGB” can be referred to “IEC” 1966-2-61) Therefore, a toner set having high color reproducibility is demanded.

Japanese Patent Laid-Open No. 9-26673 JP-A-11-160914 JP 2004-126248 A JP 2000-347476 A JP 2004-1108020 A JP 2004-142153 A

  The first object of the present invention is to solve the above-described problems, and is an electrophotographic toner set having good color reproducibility, light resistance, and ozone resistance when each color toner is mixed. The purpose is to provide. The second object of the present invention is to provide an electrophotographic toner that has good compatibility with sRGB, that is, has a wide color reproduction range and high color reproducibility when printed from the screen of a display device such as a CRT or liquid crystal display. Is to provide a set.

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

1. In an electrophotographic toner set including at least a yellow toner, a magenta toner, a cyan toner, and an orange toner, the cyan toner contains a compound represented by the following general formula (1) as a cyan colorant, and L ^* a ^* b ^{* The} hue angle (h) according to the color system is 180 ° ≦ h ≦ 230 °, the orange toner contains an organic dye as an orange colorant, and the hue angle (h) according to the L ^* a ^* b ^* color system ) Is 10 ° ≦ h ≦ 60 °, and a toner set for electrophotography.

(Wherein, A11, A12, A13 and A14 _.R is representative of the aromatic or heterocyclic ring 5-6 membered _11, R _{12, R 13} and _{R 14} are a hydrogen atom or a .o representing a substituent,, p, q and r represent an integer of 1 to 4. M represents Mg, Fe, Co, Ni, Zn, Al, Si, SnX, VX, SiXY, SnXY, AlX, FeX, X or Y represents a hydrogen atom, oxygen Atom, halogen atom, hydroxy group, alkyl group, alkynyl group, alkoxy group, siloxy group, aryl group, aryloxy group, acyloxy group, alkylamino group, arylamino group, alkylthio group, arylthio group are represented.)

  The toner set for electrophotography of the present invention has an excellent effect on the light resistance and ozone resistance of an image, making the hue at the time of color mixing good without causing a problem of the toner production method. In addition, color tone adjustment is good when images on various displays are printed, and the color reproducibility is high.

As a result of intensive studies to solve the above-described problems, the present inventors have a specific structure represented by the general formula (1) as a cyan colorant, and an L ^* a ^* b ^* color system (CIELAB color). A cyan toner characterized by a hue angle (h) of 180 ° ≦ h ≦ 230 ° and an organic dye as an orange colorant, and a hue based on the L ^* a ^* b ^* color system By including an orange toner having an angle (h) of 10 ° ≦ h ≦ 60 °, the hue at the time of color mixing is improved without causing a problem with the toner manufacturing method, and further, the light resistance and resistance of the image are improved. The inventors have invented an electrophotographic toner set excellent in ozone.

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

  The cyan toner used in the present invention is represented by the general formula (1) as a cyan colorant, and has a hue angle of 180 ° to 230 °, preferably 200 ° to 220 ° as a cyan toner single color. Is characteristic.

  The orange toner used in the present invention is characterized by containing an organic dye as an orange colorant and having a hue angle of 10 ° to 60 °, preferably 20 ° to 50 ° as a single color. .

The hue of the image is measured with 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) is used, and the toner adhesion amount and the like are 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 °. The hue angle (h) is calculated from h = tan ⁻¹ (b ^* / a ^* ) using the a ^* value and b ^* value obtained by the measurement.

  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 an electrophotographic toner containing the colorant is prepared and an image is formed. The colorant may be a dye or a pigment.

  The compound represented by the general formula (1) will be described.

  A11, A12, A13 and A14 in the general formula (1) represent a 5- to 6-membered aromatic ring or heterocyclic ring. Specifically, examples of the aromatic ring include a ring forming phenyl, naphthyl, fluorenyl and the like. Heterocycles include furyl, benzofuranyl, thienyl, pyrrolyl, indolyl, imidazolyl, pyrazolyl, indazolyl, triazolyl, thiazolyl, isothiazolyl, thiadiazolyl, benzoimidazolyl, oxazolyl, isoxazolyl, furazanyl, benzoxazolyl, phthalazyl, pyranyl, pyridyl, Pyridazyl, pyrimidyl, pyrazyl, piperazyl, triazyl, thiapyranyl, xanthenyl, quinolyl, quinoxalinyl, quinazolinyl, cinnolinyl, isoquinolinyl, acridinyl, phenazinyl, carbazolyl Phenoxazinyl, perimidinyl, mention may be made of a ring to form a Azafenaren like. These may be condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring.

  The 5- or 6-membered aromatic ring or heterocycle represented by A11, A12, A13 or A14 preferably forms a 6-membered ring, more preferably phenyl, pyridyl, pyridazyl, pyrimidyl or pyrazyl, and phenyl or pyridyl is Most preferred.

In the general formula (1), R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ represent a hydrogen atom or a substituent, and the substituent is not particularly limited. For example, an alkyl group (for example, a methyl group, Ethyl group, n-propyl group, isopropyl group, t-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, trifluoromethyl group, cyclopentyl group, cyclohexyl group, etc.), aromatic Aromatic hydrocarbon group (also referred to as aryl group) (eg, phenyl group, naphthyl group, etc.), acylamino group (eg, acetylamino group, benzoylamino group, etc.), alkylthio group (eg, methylthio group, ethylthio group, etc.), arylthio Groups (also referred to as thioaryl groups. For example, phenylthio groups, naphthylthio groups, etc.), alkenyl groups (for example, vinyl groups, 2- Lopenyl group, 3-butenyl group, 1-methyl-3-propenyl group, 3-pentenyl group, 1-methyl-3-butenyl group, 4-hexenyl group, cyclohexenyl group, etc.), halogen atom (fluorine atom, chlorine atom) , Bromine atom, iodine atom), alkynyl group (for example, propargyl group), heterocyclic group (for example, pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group) Group), arylsulfonyl group (eg phenylsulfonyl group, naphthylsulfonyl group etc.), alkylsulfinyl group (eg methylsulfinyl group etc.), arylsulfinyl group (eg phenylsulfinyl group etc.), phosphono group, acyl group ( For example, acetyl group, pivaloyl group, benzoyl group ), Carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, butylaminocarbonyl group, cyclohexylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), sulfamoyl group (for example, amino group) Sulfonyl 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 (eg, methanesulfonamide group, benzenesulfonamide group, etc.), cyano group, alkoxy group ( For example, methoxy group, ethoxy group, propoxy group, etc.), aryloxy group (eg, phenoxy 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 (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, etc.) , Anilino group (eg, phenylamino group, chlorophenylamino group, toluidino group, anisidino group, naphthylamino group, 2-pyridylamino group, etc.), imide group, ureido group (eg, methylureido group, ethylureido group, pentylureido group) , Cyclohexylureido group, octi Ureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido 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, etc. Each group is mentioned.

R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ are preferably a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryl group, an aryloxy group or an acyl group, more preferably a hydrogen atom, A halogen atom, an alkyl group, an alkoxy group, an aryl group, and an aryloxy group are preferred, and a hydrogen atom alkyl group is most preferred.

If R _{11, R 12, R 13} and _{R 14} there are a plurality each of the plurality of _{R 11,} R _{12, R 13} and _{R 14} may each be the same or different.

  o, p, q, and r represent the integer of 0-4.

  M represents Mg, Fe, Co, Ni, Zn, Al, Si, Sn, VX, SiXY, SnXY, AlX, and FeX. More preferred are Mg, Fe, Co, Ni, Zn and SiXY, and most preferred are Zn and SiXY.

X or Y is a hydrogen atom, oxygen atom, halogen atom, hydroxy group, alkyl group, alkynyl group, alkoxy group, siloxy group, aryl group, aryloxy group, acyloxy group, alkylamino group, arylamino group, alkylthio group, arylthio group Represents a group. Preferably it represents an oxygen atom, a halogen atom, a hydroxy group, an alkoxy group, a siloxy group, an aryloxy group or an acyloxy group, more preferably a halogen atom, a hydroxy group, an alkoxy group, a siloxy group or an aryloxy group. Examples of these include the corresponding examples in the description of the substituents represented by R ₁₁ , R ₁₂ , R ₁₃ and R ₁₄ in the above general formula (1).

  As for the preferred combination of substituents of the compound represented by the general formula (1), a compound in which at least one of various substituents is the preferred group is preferred, and more various substituents are preferred groups. Certain compounds are more preferred, and compounds in which all substituents are the preferred groups are most preferred.

The phthalocyanine compound represented by the following general formula (A-1) inevitably has a substituent R _n (n = 1 to 16, R is a substituent, and all of R _n is May include isomers at the substitution positions (defined as R ₁ : 1 to R ₁₆ : 16) of the same type of substituents, but these substitution position isomers may be distinguished from each other. In many cases, they are regarded as the same derivative. In addition, when an isomer is included in a substituent, they are often regarded as the same phthalocyanine compound without distinguishing them.

The case where the structures of the phthalocyanine compounds in this specification are different from each other is explained by the general formula (A-1). When the constituent atomic species are different for the substituent R _n (n = 1 to 16), the number of substituents is Either it is different or the substitution position is different.

  Derivatives having different structures (particularly substitution positions) of the phthalocyanine compound represented by the general formula (1) are classified into the following three types and defined.

(1) β-position substitution type: (phthalocyanine compound having a specific substituent at the 2 and / or 3 position, 6 and / or 7 position, 10 and / or 11 position, 14 and / or 15 position)
(2) α-position substitution type: (phthalocyanine compound having a specific substituent at the 1 and / or 4 position, 5 and / or 8 position, 9 and / or 12 position, 13 and / or 16 position)
(3) α, β-position mixed substitution type: (phthalocyanine compound having a specific substituent without regularity at positions 1 to 16).

  In the present specification, when a derivative of a phthalocyanine compound having a different structure (especially a substitution position) is described, the β-position substitution type, α-position substitution type, and α, β-position mixed substitution type are used.

As preferred substitution types of R ₁₁ , R ₁₂ , R ₁₃ and R _{14 in} the general formula (1), β-position substitution type and α, β-position mixed substitution type are preferred, and β-position substitution type is most preferred. preferable.

The phthalocyanine compound having a substituent at the β-position is usually a compound represented by the following general formulas (a) -1 to (a) -4. These four kinds of compounds are isomers having different substitution positions of R _{1 to} R ₄ .

  The compounds represented by the general formulas (a) -1 to (a) -4 are β-position substituted (2 and / or 3, 6 and or 7 position, 10 and or 11 position, 14 and 15 position) A phthalocyanine compound having a specific substituent in the α-position substitution type and the α, β-position mixed substitution type, which are completely different in structure (substitution position).

  Hereinafter, specific examples of the phthalocyanine ring structure according to the present invention will be shown. However, these are one of the isomers having different substitution positions described above, and the phthalocyanine ring structure of the compound according to the present invention is not limited thereto. Not a thing.

  Specific examples of the compound represented by the general formula (1) according to the present invention are shown below.

  Examples of the phthalocyanine compound used in the present invention include “Phthalocyanine—Chemistry and Function” (P. 1-62), C.I. C. Leznoff-A. B. P. Lever co-authored by VCH and published in 'Phthalogicanes-Properties and Applications' (P. 1-54), etc., can be synthesized by combining quoted or similar methods.

The orange toner suitably used in the present invention preferably has a hue angle (h) of 10 ° to 60 °, more preferably 20 ° to 50 °, as a single color of the toner, according to the L ^* a ^* b ^* color system. . The organic colorant used as the orange colorant of the orange toner used in the present invention is not particularly limited as long as it is a single color toner and has the above-described hue angle, and any dye or pigment can be suitably used. Depending on the purpose, the user may appropriately mix a plurality of colorants and adjust the hue angle within an appropriate range for use.

  Next, specific examples of the colorant for orange toner include the following.

  C. I. Pigment orange 36, C.I. I. Pigment orange 43, C.I. I. Pigment orange 2, C.I. I. Pigment orange 5, C.I. I. Pigment orange 22, C.I. I. Pigment orange 24, C.I. I. Pigment orange 148, C.I. I. Pigment orange 38, C.I. I. Pigment orange 17, C.I. I. Pigment orange 62, C.I. I. Pigment orange 15, C.I. I. Pigment orange 16, C.I. I. Pigment orange 44, C.I. I. Pigment orange 13, C.I. I. Pigment orange 34, C.I. I. Pigment orange 61, C.I. I. Pigment orange 66, C.I. I. Pigment orange 69, C.I. I. Pigment orange 65, C.I. I. Pigment Orange 68.

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

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

In the magenta toner suitably used in the present invention, the hue angle (h) according to the L ^* a ^* b ^* color system is preferably 300 ° to 330 °, more preferably 310 ° to 330 ° as a single toner color. .

  Specific examples of the colorant for magenta toner include the following.

  C. I. Pigment red 48: 2, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 58: 2, C.I. I. Pigment red 200, C.I. I. Pigment red 7, C.I. I. Pigment red 8, C.I. I. Pigment red 13, C.I. I. Pigment red 23, C.I. I. Pigment red 223, C.I. I. Pigment red 212, C.I. I. Pigment red 213, C.I. I. Pigment red 222, C.I. I. Pigment red 238, C.I. I. Pigment red 245, C.I. I. Pigment red 49: 2, C.I. I. Pigment red 175, C.I. I. Pigment red 144, C.I. I. Pigment red 214, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 190, C.I. I. Pigment red 224, C.I. I. Pigment red 202, C.I. I. Pigment red 88, C.I. I. Pigment Red 181.

  As the yellow toner used in the present invention, a conventionally known yellow toner can be used, and an optimal toner may be selected according to the use and purpose of the user. In order to effectively use the present invention, the hue angle of the yellow toner is preferably in the range of 70 ° to 95 °, more preferably in the range of 80 ° to 90 °.

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

  Examples of yellow colorants for yellow toner include C.I. I. Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162, etc. I. Pigment Yellow 14, 17, 74, 94, 138, 155, 180, 185, and the like, and mixtures thereof can also be used. In particular, C.I. I. Solvent Yellow 162, C.I. I. Pigment Yellow 74, 93, 138, and 180 are preferable.

  In the present invention, other dyes may be used in combination, and generally known dyes can be used as the dyes used together, but in the present invention, the dyes are preferably oil-soluble dyes. Oil-soluble dyes are usually dyes that are soluble in organic solvents that do not have a water-soluble group such as carboxylic acid and sulfonic acid and are insoluble in water. However, oil-soluble dyes are formed by salting water-soluble dyes with long-chain bases. Also included are dyes that exhibit solubility. For example, acid dyes, direct dyes, and salt-forming dyes of reactive dyes and long chain amines are known.

  Although not limited to the following, for example, Variast Yellow 4120, Varifast Yellow 3150, Varifast Yellow 3108, Varifast Yellow 2310N, Varifast R1 304, Valifast R3, 304 , BaliFast Blue 2610, Valifast Blue 2606, VariFast Blue 1603, Oil Yellow GG-S, Oil Yellow 3G, Oil Yellow 129, Oil Yellow 107, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105, Oil Yellow 105 l Red RR, Oil Red OG, Oil Red 5B, Oil Pin 312, Oil Blue BOS, Oil Blue 613, Oil Blue 2N, Oil Black BY, Oil Black BS, Oil Black 860, Oil Black 5970Oil Black 5960 5905, Kayset Yellow SF-G, Kayase Yellow K-CL, Kayase Yellow GN, Kayase Yellow A-G, Kayset Yellow 2G, Kayset Red SF-4G, Kayase Red Kad SetK-4 -BR, Kayset Magenta 312, Kay set Blue K-FL, Arimoto Chemical Industry Co., Ltd. of FS Yellow 1015, FS Magenta 1404, FS Cyan 1522, FS Blue 1504, C. I. Solvent Yellow 88, 83, 82, 79, 56, 29, 19, 16, 14, 04, 03, 02, 01, C.I. I. Solvent Red 84: 1, C.I. I. Solvent Red 84, 218, 132, 73, 72, 51, 43, 27, 24, 18, 01, C.I. I. Solvent Blue 70, 67, 44, 40, 35, 11, 02, 01, C.I. ISolent Black 43, 70, 34, 29, 27, 22, 7, 3, C.I. I. Solvent Violet 3, C.I. I. Solvent Green 3 and 7, Plast Yellow DY352, Plast Red 8375, MS Yellow HD-180 manufactured by Mitsui Chemicals, MS Red G, MS Magenta HM-1450H, MS Blue HM-1384, ES Red 3001, manufactured by Sumitomo Chemical 3002, ES Red 3003, TS Red 305, ES Yellow 1001, ES Yellow 1002, TS Yellow 118, ES Orange 2001, ES Blue 600, TS Turnq Blue 618, Bayer's MACROLEX Yellow Elu 6G, CerS GN, MACROLEX Red Vio et R, and the like.

  A disperse dye can be used as the oil-soluble dye, and is not limited to the following, but examples thereof include C.I. I. Disperse Yellow 5, 42, 54, 64, 79, 82, 83, 93, 99, 100, 119, 122, 124, 126, 160, 184: 1, 186, 198, 199, 204, 224 and 237; C . I. Disperse Orange 13, 29, 31: 1, 33, 49, 54, 55, 66, 73, 118, 119 and 163; C.I. I. Disperse Red 54, 60, 72, 73, 86, 88, 91, 92, 93, 111, 126, 127, 134, 135, 143, 145, 152, 153, 154, 159, 164, 167: 1, 177 , 181, 204, 206, 207, 221, 239, 240, 258, 277, 278, 283, 311, 323, 343, 348, 356 and 362; I. Disperse violet 33; C.I. I. Disperse Blue 56, 60, 73, 87, 113, 128, 143, 148, 154, 158, 165, 165: 1, 165: 2, 176, 183, 185, 197, 198, 201, 214, 224, 225 257, 266, 267, 287, 354, 358, 365 and 368 and C.I. I. Disperse Green 6: 1 and 9 etc. are mentioned.

  In addition, as the oil-soluble dye, cyclic methylene compounds such as phenol, naphthols, pyrazolone and pyrazolotriazole, couplers such as open-chain methylene compounds, p-diaminopyridines, azomethine dyes, indoaniline dyes and the like are also preferably used.

  The number average primary particle diameter of these colorants in a dispersed state in the toner varies depending on the type, but is preferably about 10 to 200 nm. The addition amount of these colorants is 1 to 10% by mass, preferably 2 to 8% by mass in the toner. When the amount is less than 1% by mass, the coloring power of the toner may be insufficient. When the amount exceeds 10% by mass, the colorant is liberated or adhered to the carrier, which may affect the chargeability. .

(Addition to toner)
Any method can be used as an addition form to the toner. For example, dissolution in a binder resin, impregnation, addition of a dye other than the binder resin as a solid dispersion, and addition of a polymer to the dye solid dispersion A form in which a high-boiling oil or the like is mixed can be considered.

  As a preferable addition form, a solid dispersion having a particle diameter of 10 nm to less than 1 μm is preferable from the viewpoint of stability. Furthermore, a monodispersed solid dispersion having a particle diameter of 10 nm to less than 100 nm is preferable from the viewpoint of color reproducibility because light scattering can be suppressed and concealing particles can be eliminated.

  Further, since the solid dispersion is not dissolved, diffusibility and bleeding are suppressed, and the light resistance and heat resistance of the dye are improved. It is also effective to prevent agglomeration and control the particle size by mixing a polymer and a high-boiling oil agent to form a solid dispersion, and it is preferable to add as necessary. Further, coating with another polymer to form a core / shell can also be used to enhance manufacturing stability and storage stability. The toner can be applied to both a polymerized toner and a pulverized toner, but is more suitable for a polymerized toner because of the processability of the toner and the ease of adding a dye.

(Production method of particles)
A preferred method for producing a solid dispersion in the present invention will be described.

  In the present invention, the dye solid dispersion is obtained by, for example, a submerged drying method in which a dye is dissolved (or dispersed) in a water-immiscible organic solvent such as ethyl acetate or toluene, emulsified and dispersed in water, and then the organic solvent is removed. Can be obtained.

  Further, when the dye can be dispersed in a solid state, the solid dye may be emulsified and dispersed in water to which a surfactant is added, instead of the above-described drying method in liquid. The emulsifying disperser is not limited, and for example, an ultrasonic disperser, a high-speed stirring disperser, or the like is used.

(Surfactant)
Although it does not restrict | limit especially as an emulsifier, a dispersing agent, and a surface tension regulator in this invention, Surfactant of cationic type, anionic type, amphoteric type, and nonionic type can be used.

  As the emulsifier or dispersant, anionic or nonionic surfactants are particularly preferable. It is also possible to use both active agents together to satisfy various conditions.

  Examples of the anionic surfactant include higher fatty acid salts such as sodium oleate; alkyl aryl sulfonates such as sodium dodecylbenzene sulfonate; alkyl sulfate salts such as sodium lauryl sulfate; Polyoxyethylene alkyl ether sulfate salts such as sodium ethylene lauryl ether sulfate; for example, polyoxyethylene alkyl aryl ether sulfate salts such as sodium polyoxyethylene nonylphenyl ether sulfate; sodium monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate, poly And alkyl sulfosuccinic acid ester salts such as sodium oxyethylene lauryl sulfosuccinate and derivatives thereof. In addition, for example, the dispersants Demol SNB, MS, N, SSL, ST, and P (trade names) manufactured by Kao Corporation are also included.

  Moreover, the following water-soluble resins can be used as the polymer surfactant. As the water-soluble resin, styrene-acrylic acid-acrylic acid alkyl ester copolymer, styrene-acrylic acid copolymer, styrene-maleic acid-acrylic acid alkyl ester copolymer, styrene-maleic acid copolymer are preferably used. Polymer, styrene-methacrylic acid-acrylic acid alkyl ester copolymer, styrene-methacrylic acid copolymer, styrene-maleic acid half ester copolymer, vinyl naphthalene-acrylic acid copolymer, vinyl naphthalene-maleic acid copolymer Etc. Other examples of the polymer surfactant include Jonkrill, an acrylic-styrene resin (Johnson).

  In addition, compounds having both a monomer group and a surfactant component known as reactive emulsifiers are also useful because of their low dye solubility and high emulsifying ability.

  Examples of reactive emulsifiers include “Ramtel S-120”, “Ramtel S-120A”, “Ramtel S-180”, “Ramtel S-180A” manufactured by Kao, and “Eleminol JS-2” manufactured by Sanyo Chemical Industries. ”, NE series such as“ Adekaria Soap NE-10 ”,“ Adekaria Soap NE-20 ”,“ Adekaria Soap NE-30 ”manufactured by Asahi Denka Kogyo,“ Adekaria Soap SE-10N ”,“ Adekaria ” SE series such as “SOPE SE-20N” and “ADEKA rear soap SE-30N”, “AQUALON RN-10”, “AQUALON RN-20”, “AQUALON RN-30”, “AQUALON RN-” manufactured by Daiichi Kogyo Seiyaku RN series such as “50”, “AQUALON HS-05”, “AQUALON HS-10”, “AQUALON HS-2” ”,“ Aqualon HS-30 ”and other HS series, or Aqualon BC series,“ Aqualon KH-05 ”,“ Aquaron KH-10 ”,“ Aquaron HS-05 ”,“ Aquaron HS ”manufactured by Daiichi Kogyo Seiyaku Co., Ltd. -10 ”,“ Adekaria Soap SE Series ”(Asahi Denka Kogyo),“ Aqualon HS Series ”(Daiichi Kogyo Seiyaku),“ Latemul S Series ”(Kao),“ Eleminol JS Series ”(Sanyo Chemical Industries) Manufactured).

  Examples of nonionic surfactants include polyoxyethylene octyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether; for example, polyoxyethylene alkyl phenyl ethers such as polyoxyethylene nonylphenyl ether; Sorbitan higher fatty acid esters such as sorbitan monolaurate, sorbitan monostearate and sorbitan trioleate; for example, polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate; for example, polyoxyethylene monolaurate Polyoxyethylene higher fatty acid esters such as polyoxyethylene monostearate; for example, oleic acid monoglyceride, stearic acid monoglyceride, etc. Glycerine higher fatty acid esters; e.g., polyoxyethylene - polyoxypropylene - block copolymers; and the like can be given.

  Examples of amphoteric surfactants include carboxybetaine type, sulfobetaine type, aminocarboxylate, imidazolinium betaine, and the like. Examples of cationic surfactants include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalco. Examples thereof include nium salts, benzethonium chloride, pyridinium salts, and imidazolinium salts.

  When using these surfactants, they can be used singly or in combination of two or more, and should be used by adding them in the range of 0.001 to 1.0 mass% with respect to the solid dispersion. Can do.

(polymer)
When the polymer (resin) is contained in the dispersion in the present invention, the weight average molecular weight is less than 40,000, particularly 500 or more and less than 40,000 for at least one, forming fine particles, It is preferable in terms of excellent dispersion stability and image transparency.

  In the present invention, generally known resins can be used, for example, (meth) acrylate resins, polyester resins, polyamide resins, polyimide resins, polystyrene resins, polyepoxy resins, polyester resins. , Amino resins, fluorine resins, phenol resins, polyurethane resins, polyethylene resins, polyvinyl chloride resins, polyvinyl alcohol resins, polyether resins, polyether ketone resins, polyphenylene sulfide resins, polycarbonate resins Aramid resin and the like can be mentioned, but preferred resins are those obtained by radical polymerization of polymers containing acetal groups, especially polyvinyl butyral, polyvinyl acetal, and vinyl monomers having a polymerizable ethylenically unsaturated double bond. Polymers are preferred.

  Specific monomers used in the vinyl monomer radical copolymer include vinyl acetate, methyl acrylate, ethyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, Dodecyl acrylate, octadecyl acrylate, 2-phenoxyethyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, dodecyl methacrylate, methacryl Octadecyl acid, cyclohexyl methacrylate, stearyl methacrylate, benzyl methacrylate, glycidyl methacrylate, phenyl methacrylate, styrene, α-methylstyrene, acrylonitrile, etc. DOO acetoxyethyl methacrylate, glycidyl methacrylate of soybean oil fatty acid modified products: include (Blenmer G-FA manufactured by NOF Corporation) and the like.

(composition)
In the present invention, the solid dispersion contains a pigment, and optionally a polymer and a high boiling oil agent. When adding a polymer and a high boiling oil agent, 30 to 70 mass% of the polymer and the high boiling oil agent are preferable.

(Particle size)
The dye solid dispersion in the present invention preferably has a volume-based median diameter in the range of 10 to 200 nm, more preferably 10 to 100 nm, and particularly preferably 10 to 50 nm. When the volume-based median diameter is 10 nm or less, since the surface area per unit volume becomes very large, the stability of the solid dispersion 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.

  On the other hand, the particle size distribution also affects the saturation. The particle size distribution was defined as CV value as follows. A cumulative curve is obtained by setting the total particle size measurement value to 100%, and when the particle size at which the cumulative curve is 16%, 50%, 84% is d16, d50, d84, CV value = (d84−d16) × 100 / (2 × d50). The CV value is preferably 100 or less, more preferably 50 or less, and even more preferably 30 or less.

  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, etc. In the present invention, the microtrack UPA-150 is used. It is preferable to obtain the dynamic light scattering method using (Nikkiso Co., Ltd.).

(toner)
In the present invention, a known charge control agent, offset preventive agent and the like can be used in addition to the following binder resin and pigment solid dispersion. 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. , 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 No. 53-127726 and JP-A No. 62-145255, and examples of the calixarene compound include, for example, JP-A No. 2-201378. As the organic boron compound, 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. is there. 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 binder 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 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.

  In the present invention, the above-mentioned binder resin, pigment solid dispersion and other desired additives are used, kneading / pulverizing method, suspension polymerization method, emulsion polymerization method, emulsion dispersion granulation method, encapsulation method, etc. It can be produced by other known methods. 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, the binder resin emulsion produced by emulsion polymerization is mixed with a dispersion of toner particle components such as other pigment solid dispersions, and the repulsive force on the particle surface generated by pH adjustment and aggregation by addition of electrolyte Toner particles are produced by slowly agglomerating while maintaining a balance of forces, and performing aggregation while controlling the particle size and particle size distribution, and simultaneously performing heating and stirring to control fusion and shape between the fine particles.

  The toner particles according to the present invention preferably have a volume-based median diameter of 4 to 10 μm, preferably 6 to 9 μm, from the viewpoint of high-definition image reproducibility.

  In the present invention, from the viewpoint of imparting toner fluidity and improving cleaning properties, a post-treatment agent can be added and mixed, 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 desirably used after being surface-treated with a silane coupling agent, a titanium coupling agent, a higher fatty acid, silicone oil, etc. from the viewpoint of environmental stability and heat-resistant storage stability, and the addition amount is 100 parts by mass of toner. 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass is used.

  As the toner in the present invention, a two-component developing toner used by mixing with a carrier or a one-component developing toner not using a carrier can be used.

  As the carrier to be used, those conventionally known as two-component developing carriers can be used. For example, a carrier made of magnetic particles such as iron or ferrite, and such magnetic particles are coated with a resin. Or a binder-type carrier obtained by dispersing magnetic fine powder in a binder resin.

  Among these carriers, a silicone resin, a copolymer resin (graft resin) of an organopolysiloxane and a vinyl monomer, or a resin-coated carrier using a polyester resin can be used 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-based median diameter of 20 to 100 μm, preferably 20 to 60 μm from the viewpoint of ensuring high image quality and preventing carrier fogging.

(Binder resin)
In the present invention, the binder resin contained in the toner is preferably a thermoplastic resin having high adhesion to the solid dispersion, and particularly preferably a solvent-soluble one. Further, if the polymer precursor is soluble in a solvent, a curable resin that forms a three-dimensional structure can also be used.

  As the binder resin, those generally used as a binder resin for toner are used without any particular limitation. For example, styrene resins, acrylic resins such as alkyl acrylates and alkyl methacrylates, and styrene acrylic copolymer resins are used. 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. Moreover, these resins can be mixed and used, and a polymer in which an addition polymerization type resin and a polycondensation type resin are combined via acrylic acid or the like can also be used.

  As a composite resin, (i) by performing a transesterification reaction between a vinyl resin component obtained by polymerizing a monomer component having a carboxylic acid ester group such as an acrylic ester or a methacrylic ester and a polyester resin component. (Ii) formed by an esterification reaction between a vinyl resin component obtained by polymerizing a monomer component having a carboxylic acid group such as acrylic acid or methacrylic acid and a polyester component, (iii) And) formed by polymerizing a vinyl monomer in the presence of an unsaturated polyester resin component polymerized using a monomer having an unsaturated bond such as fumaric acid.

  Furthermore, a modified polymer obtained by reacting a functional group present in the terminal of the resin or in the monomer with a compound having activity in the functional group can also be used.

  The modified polymer contains a polymer having a site capable of reacting with a compound having an active hydrogen group in an organic solvent, and is obtained by reacting with a compound having an active hydrogen group when granulated in an aqueous medium. The polymer having a site capable of reacting with a compound having a hydrogen group is preferably an isocyanate group-containing polyester prepolymer, and the compound having an active hydrogen group is preferably an amine, a ketimine compound, an oxazoline compound, or the like.

  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 weight 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 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. Two or more polymers having different number average molecular weights can be used in combination.

  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.

(Image forming method)
Next, an image forming method using the electrophotographic toner set 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 according to 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 photosensitive member on which the first and second images are formed is uniformly charged, exposed according to the third image, and subjected to the third development to form a third toner image on the photosensitive member. . Further, the photoconductor on which the first, second, and third images are formed is uniformly charged, exposed according to the fourth image, and developed for the fourth time, and the fourth toner image is formed on the photoconductor. To form.

  For example, a full color toner image is formed on the photosensitive member 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. Further, as described above, the non-contact development method is preferable as the development method for forming a superimposed color image on the image forming body and transferring the images collectively.

  The volume-based median 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-based median 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, an olefin resin, a styrene resin, a styrene / acrylic resin, a silicone resin, an ester resin, a fluorine-containing polymer resin, or the like 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 the image formation in which development, transfer, and fixing are performed using the toner set for electrophotography of the present invention, the state of transfer to fixing will be described. The toner used in the present invention transferred onto the transfer material is fixed. Even after that, the pigment solid dispersion does not disintegrate and adheres to the paper surface.

  In the present invention, since the solid dispersion is dispersed in the toner particles as described above, the dye is not released (migrated) to the surface of the toner particle even though the toner particle contains the dye. (1) Low charge amount, (2) Large difference in charge amount between high temperature and high humidity and low temperature and low humidity (environment dependence), (3) Colorant type, for example, As in full-color image recording, it is possible to wipe away variations in the charge amount of each color toner when using pigments of cyan, magenta, yellow, and black.

  In addition, when heat fixing to a transfer material, there is no transfer of the colorant dye outside the dye solid dispersion (exposure to the surface of the dye solid dispersion). Thus, there is no dye sublimation or oil contamination during heat fixing.

  Next, typical embodiments of the present invention will be specifically described, but the present invention is not limited thereto.

Example 1
(Manufacture of latex 1)
In a 5000 ml separable flask equipped with a stirrer, a temperature sensor, a condenser, and a nitrogen introducing device, 7.08 g of an anionic active agent (sodium dodecylbenzenesulfonate: SDS) was dissolved in ion-exchanged water (2760 g) in advance. Add the solution. The internal temperature was raised to 80 ° C. while stirring at a stirring speed of 230 rpm under a nitrogen stream. On the other hand, 72.0 g of the formula (1) as a release agent is added to a monomer composed of 115.1 g of styrene, 42.0 g of n-butyl acrylate, and 10.9 g of methacrylic acid, and heated to 80 ° C. to dissolve the monomer solution. Was made.

  Here, the above heated solution was mixed and dispersed by a mechanical disperser having a circulation path to produce emulsified particles having a uniform dispersed particle size. Next, a solution in which 0.90 g of a polymerization initiator (potassium persulfate: KPS) was dissolved in 200 g of ion-exchanged water was added, and the particles were heated and stirred at 80 ° C. for 3 hours to produce latex particles.

  Subsequently, a solution obtained by dissolving 8.00 g of a polymerization initiator (KPS) in 240 ml of ion-exchanged water was added, and after 15 minutes, 383.6 g of styrene, 140.0 g of n-butyl acrylate, 36 mg of methacrylic acid, 36 ° C. .4 g and a 13.7 g mixture of t-dodecyl mercaptan was added dropwise over 120 minutes. After completion of dropping, the mixture was heated and stirred for 60 minutes, and then cooled to 40 ° C. to obtain latex particles. This latex particle is referred to as “Latex 1”.

<< Production of Toner 1 >>
12 g of sodium n-dodecyl sulfate is dissolved in 175 ml of ion-exchanged water with stirring. 25 g of Example Compound c-1 was gradually added to this liquid with stirring, and then dispersed using CLEARMIX. As a result of measuring the particle diameter of the dispersion using an electrophoretic light scattering photometer ELS-800 manufactured by Otsuka Electronics, the weight average particle diameter was 122 nm. This dispersion is referred to as “colorant dispersion 1”.

  Latex 1, 1250 g, ion-exchanged water 2000 ml, and colorant dispersion 1 are put into a 5 L four-necked flask equipped with a temperature sensor, a cooling tube, a nitrogen introducing device, and a stirring device and stirred. After adjusting to 30 degreeC, 5 mol / L sodium hydroxide aqueous solution was added to this solution, and pH was adjusted to 10.0. Subsequently, an aqueous solution in which 52.6 g of magnesium chloride hexahydrate was dissolved in 72 ml of ion-exchanged water was added at 30 ° C. for 5 minutes with stirring. Then, after standing for 1 minute, temperature increase is started, and the liquid temperature is increased to 90 ° C. in 6 minutes (temperature increase rate = 10 ° C./min).

  In this state, the particle size was measured with a Coulter Counter TA-II. When the volume average particle size reached 6.5 μm, an aqueous solution in which 115 g of sodium chloride was dissolved in 700 ml of ion-exchanged water was added to stop particle growth. The mixture is further stirred for 6 hours at a liquid temperature of 90 ° C. ± 2 ° C. to cause salting out / fusion. Then, it cooled to 30 degreeC on the conditions of 6 degreeC / min, hydrochloric acid was added, pH was adjusted to 2.0, and stirring was stopped. The produced colored particles were filtered, washed repeatedly with ion-exchanged water, and then dried with hot air at 40 ° C. to obtain colored particles. The colored particles obtained as described above are referred to as “colored particles 1”.

  Subsequently, 1% by mass of hydrophobic silica (number average primary particle size = 12 nm, hydrophobicity = 68) and hydrophobic titanium oxide (number average primary particle size = 20 nm, hydrophobicity = 63) are added to the colored particles 1. The toner 1 was obtained by mixing with a Henschel mixer.

<< Production of Toners 2 to 27 >>
Exemplified Compound c-1 was converted to Exemplified Compound c-2, c-9, c-10, c-11, c-17, c-18, c-19, c-23, c-26, c-29, c -34, c-35, c-37, c-38, c-43, c-46, c-50, c-51, c-52, and C.I. I. Pigment orange 36, C.I. I. Pigment orange 17, C.I. I. Pigment orange 61, C.I. I. Pigment red 122, C.I. I. Pigment red 48: 1, C.I. I. Pigment yellow 74, C.I. I. Toners 2 to 27 were produced in the same manner as in the toner 1 except that the pigment yellow 75 was used.

<< Production of Toners 28-30 >>
Toners 28 to 30 were produced in the same manner as in the toner 1 except that the exemplary compound c-1 was changed to the comparative color material 1, the comparative color material 2, and the comparative color material 3.

<< Production of Toner 31 >>
Instead of “Colorant Dispersion 1” described above, “Colorant Dispersion 21” and “Colorant Dispersion 24” are mixed at a ratio of 2: 1 to the same volume as “Colorant Dispersion 1”. Toner 31 was produced in the same manner as toner 1 except that the colorant dispersion liquid 31 was changed.

<< Production of Toner 32 >>
Instead of “Colorant Dispersion Liquid 1” described above, “Colorant Dispersion Liquid 21 (Colorant Dispersion Liquid in which Colorant Dispersion 1 was replaced with CI Pigment Orange 36 instead of Exemplary Compound c-1)” And “colorant dispersion 24 (colorant dispersion in which color pigment dispersion 1 is replaced with CI pigment red 122 instead of exemplary compound c-1”) at a ratio of 2: 3. Toner 32 was prepared in the same manner as Toner 1 except that the colorant dispersion liquid 32 was mixed so as to have the same volume as “1”.

<< Production of Toner 33 >>
Instead of “Colorant Dispersion 1” described above, “Colorant Dispersion 21” and “Colorant Dispersion 24” are mixed at a ratio of 1: 8 so as to have the same volume as “Colorant Dispersion 1”. The toner 33 was produced in the same manner as the toner 1 except that the “colorant dispersion liquid 33” was changed.

  As a result of measuring the particle diameters of the dispersion liquids of the above-described toners 2 to 33 by the same method as that of the toner 1, the particle diameters of the dispersion liquids of the toners 2 to 33 are approximately in the range of 120 to 123 nm in terms of weight average particle diameter. It was confirmed.

<Production of developer for live-action test>
Each of the above toners 1 to 33 was mixed with a ferrite carrier having a volume average particle diameter of 60 μm coated with a silicone resin to prepare developers 1 to 33 having a toner concentration of 6%.

<Image formation>
An actual image was evaluated using a color copying machine (KL-2010: manufactured by Konica Minolta) as an image forming apparatus.

  As the fixing machine, a commonly used hot roll fixing type was used. Specifically, the surface of a cored bar (inner diameter = 40 mm, wall thickness = 1.0 mm, total width = 310 mm) made of an aluminum alloy with a heater built in the center is coated with tetrafluoroethylene-perfluoroalkyl vinyl ether. A heated roller is formed by coating with a 120 μm thick tube of coalescence (PFA), and the surface of a cylindrical core made of iron (inner diameter = 40 mm, wall thickness = 2.0 mm) is made of sponge silicone rubber (Asker C A pressure roller was formed by coating with a hardness of 48 and a thickness of 2 mm, and the heating roller and the pressure roller were brought into contact with a load of 150 N to form a 5.8 mm wide nip.

  Using this fixing device, the linear velocity of printing was set to 480 mm / sec. Note that a web type supply system impregnated with polydiphenyl silicone (having a viscosity of 10 Pa · s at 20 ° C.) was used as a cleaning mechanism of the fixing device. The fixing temperature was controlled by the surface temperature of the heating roller (set temperature 175 ° C.). The amount of silicone oil applied was 0.1 mg / A4.

<Image evaluation>
Reflective images (images on paper) were respectively produced on paper using the above-described image forming apparatus with the toner set using the color toner of the present invention, and evaluated by the following methods. The toner adhesion amount was evaluated in the range of 0.7 ± 0.05 (mg / cm ² ).

(Hue evaluation)
About the hue, it visually evaluated by ten test subjects using the created image, and the evaluation was performed with a maximum of 10 points. The average score of 10 people was A to 10-9, the average score of 10 to 9 was B, the average score of 10 to 8 was C, and less than 7 was D. A and B were at a level that could withstand practical use.

(Color gamut evaluation)
Using each of the solid image portions of yellow / magenta / cyan and R / G / B, the color gamut was measured to confirm the area expansion. The area is compared with the color gamut of the Japan color for printing as 100. An enlargement of 10% or more was designated as A, an enlargement of 10% to 10% was designated as B, a less than 5% was designated as C, and an unexpanded was designated as D.

(Hue angle)
The a ^* and b ^* values of the cyan toner were measured using a color meter “SPM50” (manufactured by Gretag), the hue angle was determined from these values, and evaluated according to the following criteria.

A toner in which the hue angle of the cyan toner is in the range of 200 ° ≦ h ≦ 220 ° is A
A toner in which the hue angle of the cyan toner is in the range of 180 ° ≦ h <200 ° and 220 ° <h ≦ 230 ° is B
C is a toner in which the hue angle of the cyan toner is in the range of 180 °> h and h> 230 °.

The a ^* and b ^* values of the orange toner were measured using a color meter “SPM50” (manufactured by Gretag), the hue angle was determined from these values, and evaluated according to the following criteria.

A toner whose hue angle of orange toner is in the range of 20 ° ≦ h ≦ 50 ° is A
Toners whose hue angle of orange toner is in the range of 10 ° ≦ h <20 ° and 50 ° <h ≦ 60 ° are B
C is a toner in which the hue angle of the orange toner is in the range of 10 °> h and h> 60 °.

<Image preservation>
(Light resistance)
The image fixed on the paper was irradiated with a xenon fade meter for 7 days, and the hue change of the mixed color image before and after the irradiation was evaluated. Hue change was visually observed by 10 test subjects, and evaluation was performed with a maximum of 10 points. The average score of 10 people was A to 10-9, the average score of 10 to 9 was B, the average score of 10 to 8 was C, and less than 7 was D. A and B were at a level that could withstand practical use.

(Ozone resistance)
Under the condition that the ozone gas concentration was set to 5 ppm (25 ° C .; 60% RH), the mixed color image was exposed to ozone gas for 7 days. Hue changes were evaluated for the mixed color images before and after exposure. Hue change was visually observed by 10 test subjects, and evaluation was performed with a maximum of 10 points. The average score of 10 people was A to 10-9, the average score of 10 to 9 was B, the average score of 10 to 8 was C, and less than 7 was D.

  Table 1 shows the ranks A, B, and C of the hue angle of cyan toner, and Table 2 shows the ranks A, B, and C of the hue angle of orange toner. Table 3 shows the toner set. Table 4 shows the evaluation results of the toner set.

  As is apparent from Table 4, it can be seen that the electrophotographic toner set of the present invention has good color reproducibility, light resistance and ozone resistance when the color toners are mixed, and the color reproduction range is further expanded. .

Claims (1)

In an electrophotographic toner set including at least a yellow toner, a magenta toner, a cyan toner, and an orange toner, the cyan toner contains a compound represented by the following general formula (1) as a cyan colorant, and L ^* a ^* b ^{* The} hue angle (h) according to the color system is 180 ° ≦ h ≦ 230 °, the orange toner contains an organic dye as an orange colorant, and the hue angle (h) according to the L ^* a ^* b ^* color system ) Is 10 ° ≦ h ≦ 60 °, and a toner set for electrophotography.

(Wherein, A11, A12, A13 and A14 _.R is representative of the aromatic or heterocyclic ring 5-6 membered _11, R _{12, R 13} and _{R 14} are a hydrogen atom or a .o representing a substituent,, p, q and r represent an integer of 1 to 4. M represents Mg, Fe, Co, Ni, Zn, Al, Si, SnX, VX, SiXY, SnXY, AlX, FeX, X or Y represents a hydrogen atom, oxygen Atom, halogen atom, hydroxy group, alkyl group, alkynyl group, alkoxy group, siloxy group, aryl group, aryloxy group, acyloxy group, alkylamino group, arylamino group, alkylthio group, arylthio group are represented.)