JP2011008078A - Electrophotographic toner set - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic toner set excellent in color reproducibility, light resistance and ozone resistance when performing color-mixing of respective color toners.SOLUTION: The electrophotographic toner set including a yellow toner, a magenta toner and a cyan toner contains a zinc phthalocyanine pigment as a colorant in a cyan toner, whereby a hue angle (h) according to an Labcolor system of the cyan toner is 170°≤h≤230° and a hue angle (h) according to the Labcolor system of the magenta toner is 300°≤h≤340°.

Description

  The present invention relates to an electrophotographic toner set having good color reproducibility and durability.

  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 inhibited. 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).

  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 magenta toner and a cyan toner are mixed to form a printed matter. Development of a satisfactory toner set is desired.

  In recent years, the demand for printing images on display devices for image processing on CRT displays and liquid crystal displays, submission with electronic data, personal use, etc. is rapidly expanding. SRGB, which is a typical color space (see, for example, “Multimedia Systems and Equipment-Color Measurement and Management-Part2-1: Color Management-Default RGB Color Space-sRGB” corresponding to IEC 1966-2-2) 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

  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. As a second object of the present invention, there is provided an electrophotographic toner set which has good compatibility with sRGB and has high color reproducibility when printed from a screen of a display device such as a CRT or a liquid crystal display. It is.

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

1. An electrophotographic toner set having at least a yellow toner, a magenta toner, and a cyan toner contains a colorant represented by the following general formula (1) in the cyan toner, and an L ^* a ^* b ^* table of the cyan toner. The hue angle (h) according to the color system is 170 ° ≦ h ≦ 230 °, and the hue angle (h) according to the L ^* a ^* b ^* color system of the magenta toner is 300 ° ≦ h ≦ 340 °. A toner set for electrophotography.

(Wherein X ₁ , X ₂ , X ₃ and X ₄ represent a hydrogen atom, an alkyl group, an alkoxy group or an aryloxy group, and may be the same or different. N represents 1 or 2. )
2. 2. The toner set for electrophotography according to 1 above, wherein the magenta toner contains at least one anthraquinone compound as a colorant.

  3. 2. The toner set for electrophotography according to 1 above, wherein the magenta toner contains at least one azo compound having a heterocyclic ring as a colorant.

  4). 2. The electrophotographic toner set as described in 1 above, wherein the magenta toner contains at least one compound represented by the following general formula (DX-1) as a colorant.

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

  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, the color tone adjustment is good when images on various displays are printed, and the color reproducibility is high.

1 is a schematic diagram illustrating an example of a tandem full-color image forming apparatus capable of two-component development type image formation. 1 is a schematic view of a 4-cycle full-color image forming apparatus capable of image formation by a non-magnetic one-component development system. FIG. 2 is a schematic diagram illustrating an example of a developing device (toner cartridge). FIG. 3 is a schematic diagram illustrating an example of a belt fixing type fixing device using a belt and a heating roller.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have a specific structure represented by the general formula (1) as a cyan colorant, and a hue based on the L ^* a ^* b ^* color system. A cyan toner having an angle (h) of 170 ° ≦ h ≦ 230 °, and an azo compound having a heterocyclic ring as a magenta colorant, an anthraquinone compound, or a specific formula represented by the general formula (DX-1) Containing a magenta toner having a structure and a hue angle (h) according to the L ^* a ^* b ^* color system of 300 ° ≦ h ≦ 340 ° makes the toner manufacturing method a problem Thus, the present invention has led to the invention of a toner set for electrophotography that has a good hue at the time of color mixing, has excellent light resistance and ozone resistance of images, has good color tone adjustment, and has excellent color reproducibility. .

  Hereinafter, the best mode for carrying out the present invention will be described in detail.

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

  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 170 ° to 230 °, preferably 200 ° to 220 ° as a cyan toner single color. Is characteristic.

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 °. Using the a ^* value and b ^* value obtained by the measurement, the hue angle (h) is calculated from h = tan ⁻¹ (b ^* / a ^* ).

  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 to form an image. The colorant may be a dye or a pigment.

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

X ₁ , X ₂ , X ₃ and X ₄ in the general formula (1) are a hydrogen atom, an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, hexyl group, Octyl group, etc.), alkoxy groups (for example, methoxy group, ethoxy group, propoxy group, etc.), and aryloxy groups (for example, phenoxy group, naphthyloxy group, etc.). X ₁ , X ₂ , X ₃ and X ₄ are preferably a hydrogen atom, an alkyl group or an alkoxy group, more preferably a hydrogen atom, a propyl group, an isopropyl group, a propoxy group, an isopropoxy group or an n-butyl group. , T-butyl group, n-butoxy group and t-butoxy group, most preferably a hydrogen atom, t-butyl group and t-butoxy group.

  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 represents a substituent, and all of Rn are the same species at the time of synthesis. May include isomers at the substitution positions (defined as R ₁ : 1 to R ₁₆ : 16)), but these substitution isomers should be distinguished from each other. In many cases, they are regarded as the same derivative. Further, even when isomers are included in the 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) represented by the general formulas (1) and (2) 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.

In the general formula (1), preferred substitution types of X ₁ , X ₂ , X ₃ and X ₄ are preferably β-position substitution type and α, β-position mixed substitution type, and β-position substitution type. Most preferred.

  As the number of substituents, n in the general formula (1) is 1 or 2, respectively.

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 compound represented by the general formula (1) according to the present invention will be shown. However, these are one structure among isomers having different substitution positions described above, and are not limited thereto. Absent.

  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.

  Next, the magenta colorant having a specific structure 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 and an image is formed. The colorant may be a dye or a pigment.

  The magenta toner used in the present invention is characterized by having a hue angle in the range of 300 ° to 340 °, preferably in the range of 310 ° to 330 °, as a single magenta toner.

  The magenta colorant in the present invention is not particularly limited as long as it has the above-mentioned properties, but is preferably an azo compound having a heterocyclic ring, an anthraquinone compound, or a compound represented by the above general formula (DX-1). is there.

  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 (DY1-1).

Formula _{(DY1-1) 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.

The general formula (DY1-1) 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 a group having 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 in the ring. Say. 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, an indazolyl group. 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, azaphena Down based on, 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, a methyl group, an ethyl group, n-propyl group, isopropyl group, t-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 group, 3-butenyl group, 1-methyl-3-propenyl group, 3-pentenyl group, 1-methyl- -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 (eg, methyl Sulfinyl 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, methylaminocarbonyl group, Dimethylamino Sulfonyl 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, benzene) Sulfonamide group etc.), cyano group, alkoxy group (eg 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 (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 -Pyridylami Ureido 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 _one of Ax ₁ or Bx ₁ is an aromatic hydrocarbon group, the other heterocyclic group is preferably a 5-membered ring structure.

  The azo compound represented by the general formula (DY1-1) is more preferably the following general formula (DY1-2).

Formula _{(DY1-2) 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 an aromatic hydrocarbon group or a heterocyclic group containing at least one 5-membered ring or 6-membered ring structure. To express.

Further, the general formula (DY1-2) will be described. In the general formula (DY1-2), 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 heterocyclic group containing at least one 5-membered ring or 6-membered ring structure. Examples of the aromatic hydrocarbon group include the aromatic group represented by Ax ₁ or Bx ₁ described above. Examples of the heterocyclic group having at least one 5-membered ring structure or 6-membered ring structure having the same meaning as the group hydrocarbon group include the 5-membered ring or 6-membered ring represented by Ax ₁ or Bx ₁ described above A group having the same meaning as the example of the heterocyclic group containing at least one structure can be exemplified. Ax ₂ and Bx ₂ may each be further condensed with an aliphatic ring, an aromatic ring or another heterocyclic ring.

Each of Ax ₂ and Bx ₂ may 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 (DY1-1) and General Formula (DY1-2) is more preferably the following General Formula (DY1-3) or General Formula (DY1-4).

Wherein, Ax ₃ represents a thienyl group, a pyrrolyl group, an imidazolyl group, a pyrazolyl group, a thiazolyl group, an isothiazolyl group, a group selected from thiadiazolyl group or benzothiazolyl group.

-CRx ₃ = independently Qx ₁ and Qx ₂ is, - CRx ₄ = a or represents, or either one nitrogen atom and the other represents a -CRx ₃ = or -CRx ₄ =, X is a nitrogen atom or - CRx ₅ = Rx ₁ and Rx ₂ are each independently a hydrogen atom, alkyl, cycloalkyl group, aromatic hydrocarbon group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, Represents an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group;

Gx, Rx ₃ , Rx ₄ and Rx ₅ are each independently a hydrogen atom, halogen atom, alkyl, cycloalkyl group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryl Oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkyl group or aryl group or hetero Amino group substituted with a cyclic group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl and arylsulfonylamino group, aryloxycarbonylamino group, nitro group, Alkyl and arylthio group, an alkyl- or arylsulfonyl group, an alkyl- or arylsulfinyl 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 combine 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.

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.

Qx ₃ and Qx ₄ is, -CRx ₈ each independently =, - CRx ₉ = or represents, or either one nitrogen atom and the other represents a -CRx ₈ = or -CRx ₉ =, Rx ₈ and Rx ₉ Each independently represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an alkylthio group, an alkylsulfonyl group, an alkylsulfinyl group, an alkoxycarbonyl group, a carbamoyl group, an alkoxy group, an aromatic hydrocarbon group, an arylthio group, An arylsulfonyl group, an arylsulfinyl group, an aryloxy group or an acylamino group is represented. Each substituent may be further substituted.

  General formula (DY1-3) and general formula (DY1-4) will be further described.

In the general formula (DY1-3), Ax ₃ 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, preferably a thienyl group, an imidazolyl group, A pyrazolyl group, a thiazolyl group, 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. .

The group substitutable for Ax ₃ is not particularly limited, and examples thereof are the same groups as the examples of the substituent substitutable on the aromatic hydrocarbon group or heterocyclic group represented by Ax ₁ or Bx ₁ described above. 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.

Qx ₁ and Qx ₂ is, -CRx ₃ = independently, - CRx ₄ = a or represents, or either one nitrogen atom and the other represents a -CRx ₃ = or -CRx ₄ =, preferably Qx ₁ and Qx ₂ each -CRx ₃ =, - CRx is ₄ =.

Rx ₁ and Rx ₂ are each independently a hydrogen atom, alkyl, cycloalkyl group, aromatic hydrocarbon group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, aryl It represents a sulfonyl group or a sulfamoyl group, and preferably a hydrogen atom, an alkyl, a cycloalkyl group, an aromatic hydrocarbon group, a heterocyclic group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group. Each group may further have a substituent.

X represents a = nitrogen atom or -CRx _5, preferably nitrogen atom.

Gx, Rx ₃ , Rx ₄ and Rx ₅ are each independently a hydrogen atom, halogen atom, alkyl, cycloalkyl group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryl Oxycarbonyl, acyl, hydroxy, alkoxy, aryloxy, silyloxy, acyloxy, carbamoyloxy, heterocyclic oxy, alkoxycarbonyloxy, aryloxycarbonyloxy, alkyl, aryl or hetero Amino group substituted with a ring group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl and arylsulfonylamino group, aryloxycarbonylamino group, nitro group, al Le and arylthio group, an alkyl- or arylsulfonyl group, an alkyl- or arylsulfinyl 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 combine to form a 5- to 6-membered ring.

In the general formula (DY1-4), 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, preferably a thienyl group, an imidazolyl group, A pyrazolyl group, a thiazolyl group, 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. .

The group substitutable to Ax ₄ is not particularly limited, but examples thereof are the same as those of the above-described examples of the substituent substitutable on the aromatic hydrocarbon group represented by Ax ₁ or Bx ₁ or the heterocyclic group. The 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.

Qx ₃ and Qx ₄ is, -CRx ₈ = independently, - CRx ₉ = or represents, or one nitrogen atom and the other represents a -CRx ₈ = or -CRx ₉ =, one preferably one is a nitrogen atom and the other -CRx ₈ = or -CRx ₉ = a.

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, preferably a hydrogen atom, an alkyl, a cycloalkyl group, an aromatic hydrocarbon group, a heterocyclic group, an acyl group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group. Each group may further have a substituent.

Rx ₈ and Rx ₉ are 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 carbonization It represents a hydrogen group, an arylthio group, an arylsulfonyl group, an arylsulfinyl group, an aryloxy group or an acylamino group. Each substituent may be further substituted.

Examples of the group represented by Rx ₁ , Rx ₂ , Gx, Rx ₃ , Rx ₄ , Rx ₅ , Rx ₆ , Rx ₇ , Rx ₈ and Rx ₉ include the aromatic carbon represented by the aforementioned Ax ₁ or Bx ₁ It is synonymous with the example enumerated by the applicable group in the example of the substituent which can be substituted by a hydrogen group or a heterocyclic group.

  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 (DY2-1) or general formula (DY2-2).

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, an aryloxy group. Represents an alkylthio group or an arylthio group, Ry ₄ represents an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group, a heterocyclic group, a halogen atom, an alkoxy group or an aryloxy group, ny1 represents an integer of 0 to 2, 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 (DY2-1), Ry ₆ represents a group having the same meaning as Ry ₄ in the general formula (DY2-1), and ny3 is 0 to 2 Ny4 represents an integer of 0 to 4. Zy represents an amino group or a hydroxyl group.

  General formula (DY2-1) and general formula (DY2-2) are further demonstrated.

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, and examples thereof include the above-described alkyl group, cycloalkyl group, Synonymous with aromatic hydrocarbon group, heterocyclic group, halogen atom, alkoxy group, aryloxy group, alkylthio group or arylthio group, preferably a halogen atom.

Ry ₄ represents an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group, a heterocyclic group, a halogen atom, an alkoxy group or an aryloxy group, ny1 represents an integer of 0 to 2, and 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 (DY2-1), and 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 (DY2-1). 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, the 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 general formula (DX-1) is demonstrated.

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 (DX-1) in the present invention is not particularly limited as long as it is a compound having the above-described magenta colorant properties.

In General Formula (DX-1), 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 the aromatic hydrocarbon group represented by Ax ₁ or Bx ₁ or the heterocyclic group described above. The same group as the example of the substituent which can be substituted 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 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 examples of the branched alkyl group include an iso-propyl group, an iso-butyl group, a sec-butyl group, a t-butyl group, 1 1,3,3-tetramethylbutyl group, iso-pentyl group, t-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 (DX-1), Zd represents a nonmetallic atom group necessary for forming a nitrogen-containing 5- to 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.

  The compound represented by General Formula (DX-1) in the present invention is more preferably the following General Formula (DY3-1), General Formula (DY3-2), or General Formula (DY3-3).

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 Rd12 may be the same or different.

In General Formula (DY3-1), Rd ₁₁ , Rd ₁₂ , md11, and md12 have the same meanings as Rd ₁ , Rd ₂ , md1, and md2 in General Formula (DX-1) described above, respectively.

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, 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 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 General Formula (DY3-2), Rd ₂₁ , Rd ₂₂ , md21, and md22 have the same meanings as Rd ₁ , Rd ₂ , md1, and md2 in General Formula (DX-1) described above, respectively.

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 an alkyl group, an aromatic hydrocarbon group or a heterocyclic group is preferable.

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, 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 from each other, and when md32 is 2 or more, the plurality of Rd32 may be the same or different from each other.

In formula _{(DY3-3), Rd 31, Rd} 32, md31 and md32 are synonymous with each _Rd 1 in general formula _{(DX-1), Rd 2} , md1 and md2.

Rd ₃₃ 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 an alkyl group, an aromatic hydrocarbon group or a heterocyclic group is preferable.

  Examples of the compound represented by the general formula (DX-1) preferably used in the present invention include JP-A-7-84416, JP-A-2004-123899, JP-A-2004-190007, JP-A-2005-2005. No. 2223, No. 2005-60629, No. 2005-126587, No. 2005-146002, No. 2005-146002, No. 2005-146193, No. 2005-154539, Special 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 used in the present invention can be easily produced by a known method.

  Examples of the compounds represented by the general formulas (DY1-1) to (DY1-4) according to the present invention include, for example, JP-A-5-297636, JP-A-8-123089, JP-A-8-123091, Conventionally disclosed in JP-A-8-152745, JP-A-8-166589, JP-A-8-166690, JP-A-2002-371214, JP-A-2003-49099, and JP-A-2005-255868. It can be synthesized with reference to the method of

  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. No. 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-6-152744. No. 3858, JP-A-8-15911, JP-A-7-84416, JP-A-8-123088, and the like can be easily produced by known methods.

  The compound represented by the general formula (DX-1) used in the present invention is disclosed in JP-A-7-84416, JP-A-2004-123899, JP-A-2004-190007, JP-A-2005-2223. 2005-60629, JP 2005-126587, JP 2005-146002, JP 2005-146002, JP 2005-146193, JP 2005-154539, JP 2005. It can be easily produced by a known method with reference to Japanese Patent No. 196018.

  In addition, the magenta colorant used in the present invention includes, for example, the magenta colorant used in the present invention among the pigments described in “CMC Technical Library 180 Functional Pigment Technology” (CMC Publishing Co., Ltd.). A pigment that satisfies the above requirements can also be suitably used.

  The magenta colorant used in 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 (DX-1). It may be used in combination with other magenta colorants.

  The yellow toner used in the present invention preferably has a hue angle in the range of 70 ° to 95 ° as a yellow toner single color, and 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. CI 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.

  The toner according to the present invention is excellent in light resistance and ozone gas resistance by using the toner having the cyan colorant and the toner having the magenta colorant described above, and is wider and more stable than conventional toner images and images using printing inks. Color reproducibility can be expressed.

  In particular, in recent years, there are many cases where an image displayed on a computer screen is printed out, but since the color gamut of conventional color printing is much narrower than the color gamut of a computer display, the image on the display is printed out. A big difference appeared in the hue of.

  However, by using the toner according to the present invention, a printed image closer to the color gamut of the computer display than before can be obtained. Thus, it can be said that the toner according to the present invention greatly contributes to the expansion of the color gamut in the printed image.

(Combination dye)
The toner according to the present invention is obtained by salting out / fusion-bonding composite resin particles and colorant particles described later.

  Examples of the colorant constituting the toner according to the present invention (colorant particles used for salting out / fusion with the composite resin particles) include various inorganic pigments, organic compounds in addition to the above-described cyan colorant and magenta colorant. Examples thereof include pigments and dyes. A conventionally well-known thing can be used as an inorganic pigment. Specific inorganic pigments are exemplified below.

  Examples of the black pigment include carbon black such as furnace black, channel black, acetylene black, thermal black, and lamp black, and magnetic powder such as magnetite and ferrite.

  These inorganic pigments can be used alone or in combination as required. Moreover, the addition amount of a pigment is 2-20 mass% with respect to a polymer, Preferably 3-15 mass% is selected.

  When used as a magnetic toner, the above-mentioned magnetite can be added. In this case, it is preferable to add 20 to 60% by mass in the toner from the viewpoint of imparting predetermined magnetic properties.

  Conventionally known organic pigments and dyes can also be used. Specific organic pigments and dyes are exemplified below.

  Examples of the magenta or red pigment include C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. And CI Pigment Red 222.

  Examples of the pigment for orange or yellow include C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 93, C.I. I. And CI Pigment Yellow 156.

  Examples of the pigment for green or cyan include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 16, C.I. I. Pigment blue 60, C.I. I. And CI Pigment Green 7.

  Examples of the dye include C.I. I. Solvent Red 1, 49, 52, 58, 63, 111, 122, C.I. I. Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162, C.I. I. Solvent Blue 25, 36, 60, 70, 93, 95, etc. can be used, and mixtures thereof can also be used.

  The colorant (colorant particles) constituting the toner according to the present invention may be surface-modified. A conventionally well-known thing can be used as a surface modifier, Specifically, a silane coupling agent, a titanium coupling agent, an aluminum coupling agent etc. can be used preferably. Examples of the silane coupling agent include alkoxysilanes such as methyltrimethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxysilane, and diphenyldimethoxysilane, siloxanes such as hexamethyldisiloxane, γ-chloropropyltrimethoxysilane, vinyltrimethyl. Chlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-ureido Examples thereof include propyltriethoxysilane.

  As the titanium coupling agent, for example, TTS, 9S, 38S, 41B, 46B, 55, 138S, 238S and the like, which are commercially available under the trade name “Plenact” manufactured by Ajinomoto Co., Ltd., a commercial product A-1 manufactured by Nippon Soda Co., Ltd. , B-1, TOT, TST, TAA, TAT, TLA, TOG, TBSTA, A-10, TBT, B-2, B-4, B-7, B-10, TBSTA-400, TTS, TOA-30 , TSDMA, TTAB, TTOP and the like. As an aluminum coupling agent, Ajinomoto "Plenact AL-M" etc. are mentioned, for example.

  The addition amount of these surface modifiers is preferably 0.01 to 20% by mass, and more preferably 0.1 to 5% by mass with respect to the colorant.

  Examples of the method for modifying the surface of the colorant particles include a method in which a surface modifier is added to the dispersion of the colorant particles and this system is heated to react.

  The surface-modified colorant particles are collected by filtration, washed with the same solvent and filtered, and then dried.

  One preferred form of the toner according to the present invention is that the colorant is an oil-soluble dye. Oil-soluble dyes are usually dyes that are soluble in organic solvents that do not have water-soluble groups such as carboxylic acids and sulfonic acids, and are insoluble in water. 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, Valifast Yellow 4120, Variast Yellow 3150, Varifast Yellow 3108, Varifast Yellow 2310N, Varifast R1 304, Valifast R1 304, Valifast R3 , BaliFast Blue 2610, VariFast 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 Il Red RR, Oil Red OG, Oil Red 5B, Oil Pink 312, Oil Blue BOS, Oil Blue 613, Oil Blue 2N, Oil Black BY, Oil Black BS, Oil Black 860, Oil Black 5970Ol Black 5960 5905, Kayset Yellow SF-G, Kayset 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, FS Yellow 1015, FS Magenta 1404, FS Cyan 1522, FS Blue 1504, C.I. 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. I. Solvent 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 made by Mitsui Chemicals, MS Red G, MS Magenta HM-1450H, MS Blue HM-1384, Sumitomo Chemical ES Red 3001, ES Red 3002 ES Red 3003, TS Red 305, ES Yellow 1001, ES Yellow 1002, TS Yellow 118, ES Orange 2001, ES Blue 6001, TS Turq Blue 618, Bayer's MACROLEX Yellow 6G, Ceres Blue 75G MACROLEX Red Viol t R, and the like.

  Disperse dyes can be used as the oil-soluble dye, and are 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, azomethine dyes derived from couplers such as cyclic methylene compounds such as phenol, naphthols, pyrazolones and pyrazolotriazoles, and open-chain methylene compounds, and indoaniline dyes are also preferably used as oil-soluble dyes.

(Colorant content)
In the toner according to the present invention, the content of the colorant represented by the general formula (1) is preferably in the range of 2 to 20% by mass with respect to the resin, and further contains 3 to 15% by mass of the colorant. A sufficient concentration can be obtained, and the protective ability of the colorant by the resin can be expressed.

  In order to improve the storage stability of the colorant, for example, a compound described and cited on pages 10 to 13 of JP-A-8-29934 may be added as an image stabilizer, and is commercially available. Phenol-based, amine-based, sulfur-based and phosphorus-based compounds are also included. For the same purpose, for example, an organic ultraviolet absorbent or an inorganic ultraviolet absorbent may be added as an ultraviolet absorbent.

  Examples of organic ultraviolet absorbers include 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole and 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole. Benzotriazole compounds such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, etc., phenyl salsylate, 4-t-butylphenyl salsylate, 2, Hydroxybenzoate systems such as 5-t-butyl-4-hydroxybenzoic acid n-hexadecyl ester, 2,4-di-t-butylphenyl-3 ', 5'-di-t-butyl-4'-hydroxybenzoate Compounds and the like.

  Examples of inorganic ultraviolet absorbers include titanium oxide, zinc oxide, cerium oxide, iron oxide, barium sulfate, etc., but organic ultraviolet absorbers are preferred, and ultraviolet absorbers have a transmittance of 50%. The wavelength is preferably 350 to 420 nm, more preferably 360 to 400 nm, the ultraviolet blocking ability is weak at a wavelength lower than 350 nm, and the coloring becomes strong at a wavelength higher than 420 nm, which is not preferable. Although there is no restriction | limiting in particular about addition amount, The range of 10-200 mass% is preferable with respect to a pigment | dye, and 50-150 mass% is more preferable. It is also preferable to use these in combination.

(Silanol compound)
The toner used in the present invention preferably contains a silanol compound represented by the following general formula (2).

General formula (2) (R) _m Si (OH) _n
In the formula, R represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group or a siloxy group, m and n each represents an integer of 1 to 3, and m + n = 4. When m is 2 or 3, R may be the same or different.

In the general formula (2), examples of the alkyl group represented by R include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, and an n-octyl group. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthranyl group. Examples of the heterocyclic group include a pyridyl group, a pyrimidyl group, a quinolyl group, a pyrazolyl group, and an imidazolyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, and an n-octoxy group. These may be further substituted by the substituents mentioned for R _{1 to} R ₄ in the general formula (1).

  R is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group, an alkoxy group having 1 to 12 carbon atoms, or a siloxy group. In the case of a siloxy group, it is an oligomer, and more preferably a hydrogen atom or carbon. These are an alkyl group having 1 to 8 carbon atoms and an alkoxy group having 1 to 8 carbon atoms.

  As the silanol compound according to the present invention, those having knowledge in the field can be easily synthesized according to a known method, and can also be obtained as a commercial product. For example, JP-A-63-22759, JP-A-63-316789, JP-A-63-5093, JP-A-3-157388, JP-A-6-256355, JP-A-8-143581 and JP-A-2020390 Publications and the like can be cited as references.

  The specific structure of the general formula (2) according to the present invention is shown below, but the structural isomers depending on the substitution positions of the substituents are only examples, and are not limited thereto.

  The content of the silanol compound represented by the general formula (2) is not particularly limited, but is preferably 100 to 500 ppm, more preferably 100 to 350 ppm with respect to the toner. By setting the content of the silanol compound according to the present invention to 100 ppm or more, the object and effects of the present invention can be exhibited. By setting the content to 500 ppm or less, the toner does not become too soft and the toner storage stability is deteriorated. It is preferable because a reduction in fixing rate or odor does not become a problem.

  The addition amount in the production process of the silanol compound represented by the general formula (2) is preferably 100 to 350 ppm with respect to the toner. By setting the addition amount within this range, the release agent ( The residual amount of the silanol compound in the toner after drying under reduced pressure can be set within the range specified in the present invention, but is not limited thereto.

  As a method for adding the silanol compound represented by the general formula (2) to the toner, for example, in the case of a polymerization method toner including a step of producing a resin by polymerizing the following polymerizable monomer in an aqueous medium. Is preferably a method in which a silanol compound is added at the time of preparing a colorant dispersion, but there may also be a method in which a silanol compound is added to a polymerizable monomer at the time of preparing resin particles. When the production method of the polymerization toner is the following multistage polymerization method, a method of adding at the same time as the addition of the release agent may be mentioned.

  In the present invention, the silanol compound is quantified by a head space type gas chromatograph using a detection method used in a normal gas chromatograph such as an internal standard method. In this method, toner is sealed in an open / close container, heated at the time of thermal fixing of a copying machine, etc., and the container is filled with volatile components, and the gas in the container is quickly injected into the gas chromatograph for volatilization. In addition to measuring the amount of components, MS (mass spectrometry) is also performed.

  Below, the measuring method by a head space gas chromatograph is demonstrated in detail.

1. Sample collection A 0.8 g sample is collected in a 20 ml headspace vial. The sample amount is weighed to 0.01 g (necessary for calculating the area per unit mass). Seal the vial with a septum using a dedicated crimper.

2. Heating the sample Place the sample in a 170 ° C constant temperature bath and heat for 30 minutes.

3. Setting of gas chromatographic separation conditions A column coated with silicon oil SE-30 in a column having an inner diameter of 3 mm and a length of 3 m so as to have a mass ratio of 15% is used as a separation column. The separation column is attached to a gas chromatograph, and He is used as a carrier to flow at 50 ml / min. The temperature of the separation column is set to 40 ° C., and measurement is performed while the temperature is increased to 260 ° C. at 15 ° C./min. Hold for 5 minutes after reaching 260 ° C.

4). Introduction of sample The vial bottle is taken out from the thermostatic chamber, immediately 1 ml of gas generated from the sample is collected with a gas tight syringe, and this is injected into the separation column.

5. Calculation A calibration curve is prepared in advance using the silanol compound used as the internal reference substance, and the concentration of each component is determined.

6). Equipment (1) Headspace conditions Headspace device Hewlett Packard's HP 7694 “Head Space Sampler”
Temperature conditions Transfer line: 200 ° C
Loop temperature: 200 ° C
Sample volume: 0.8 g / 20 ml vial.

(2) GC / MS conditions GC: HP5890 made by Hewlett-Packard
MS: HP5971 manufactured by Hewlett-Packard
Column: HP-624 30m x 0.25mm
Oven temperature: 40 ° C (3min) -15 ° C / min-260 ° C
Measurement mode: SIM.

  The toner according to the present invention preferably has a production method (polymerization method) in which a polymerizable monomer is polymerized in an aqueous medium. This production method comprises polymerizing the polymerizable monomer by a suspension polymerization method to obtain resin particles. Or by emulsion polymerization of the monomer in a liquid (in an aqueous medium) containing the necessary additive emulsion or mini-emulsion polymerization to prepare fine resin particles. After adding the charge controllable resin particles, an organic solvent, an aggregating agent such as a salt, and the like are added, and the resin particles are produced by a method of aggregating and fusing.

<Suspension polymerization method>
As an example of a method for producing a toner according to the present invention, a charge control resin is dissolved in a polymerizable monomer, and various constituent materials such as a colorant, a release agent as necessary, and a polymerization initiator are used. Then, various constituent materials are dissolved or dispersed in the polymerizable monomer using a homogenizer, a sand mill, a sand grinder, an ultrasonic disperser, or the like. The polymerizable monomer in which these various constituent materials are dissolved or dispersed is dispersed in oil droplets of a desired size as a toner in an aqueous medium containing a dispersion stabilizer using a homomixer or a homogenizer. Thereafter, the stirring mechanism is transferred to a reaction device (stirring device) which is a stirring blade described later, and the polymerization reaction is advanced by heating. After completion of the reaction, the dispersion stabilizer is removed, filtered, washed, and dried to prepare the toner of the present invention.

<Emulsion polymerization method>
Further, as another method for producing the toner according to the present invention, a method in which resin particles are prepared by salting out / fusion in an aqueous medium is preferable. The method is not particularly limited, and examples thereof include methods described in JP-A Nos. 5-265252, 6-329947, and 9-15904.

  That is, a method of salting out, agglomerating, and fusing a plurality of fine particles composed of resin particles and a coloring material, or a resin, a coloring agent, and the like, particularly in water using an emulsifier Later, a coagulant with a critical coagulation concentration or higher is added for salting out, and at the same time, the particle size is gradually grown while forming a fused particle by heating and fusing above the glass transition temperature of the formed polymer itself, When the desired particle size is reached, a large amount of water is added to stop particle size growth, and the shape is controlled by smoothing the particle surface while heating and stirring, and the particles are heated and dried in a fluid state while containing water. By doing so, the toner according to the present invention can be formed. Here, a solvent that dissolves infinitely in water, such as alcohol, may be added simultaneously with the flocculant.

  In the toner production method according to the present invention, the composite resin fine particles and the colorant particles formed through the step of polymerizing the polymerizable monomer after dissolving the crystalline substance in the polymerizable monomer are salted out / A method of fusing is preferably used. When the crystalline substance is dissolved in the polymerizable monomer, the crystalline substance may be dissolved and dissolved, or may be melted and dissolved.

  In addition, as a method for producing the toner according to the present invention, a step of salting out / fusion of composite resin fine particles and colorant particles obtained by a multistage polymerization method is preferably used. Here, the multistage polymerization method will be described below.

(Method for producing composite resin particles obtained by multistage polymerization method)
When the multistage polymerization method is used, the toner production method of the present invention is preferably composed of the following steps.

1: Multi-stage polymerization step 2: Salting out / fusion step of salting out / fusing composite resin particles and colorant particles to obtain toner particles 3: Filtering off the toner particles from a dispersion system of toner particles, Filtration / washing step for removing surfactants from toner particles 4: Drying step for drying washed toner particles 5: Step for adding external additive to dried toner particles.

  Hereinafter, each step will be described in detail.

[Multistage polymerization process]
The multi-stage polymerization step is a polymerization method performed for expanding the molecular weight distribution of the resin particles so as to obtain a toner in which offset generation is prevented. That is, in order to form phases having different molecular weight distribution in one resin particle, the polymerization reaction is performed in multiple stages, and the obtained resin particle has a molecular weight gradient from the center of the particle toward the surface layer. It is intended to be formed.

  For example, a method of forming a low molecular weight surface layer by first obtaining a high molecular weight resin particle dispersion and then newly adding a polymerizable monomer and a chain transfer agent is employed.

  In the present invention, it is preferable to employ a multi-stage polymerization method of three-stage polymerization or more from the viewpoint of production stability and crushing strength of the resulting toner. Hereinafter, a two-stage polymerization method and a three-stage polymerization method, which are representative examples of the multistage polymerization method, will be described. In the toner obtained by such a multistage polymerization reaction, the surface layer preferably has a lower molecular weight from the viewpoint of crushing strength.

<Two-stage polymerization method>
The two-stage polymerization method is a method for producing composite resin particles composed of a central portion (core) formed from a high molecular weight resin containing a crystalline substance and an outer layer (shell) formed from a low molecular weight resin. is there.

  This method will be explained in detail. First, a crystalline substance is dissolved in a monomer to prepare a monomer solution, and this monomer solution is dispersed in oil droplets in an aqueous medium (for example, a surfactant aqueous solution). Then, this system is polymerized (first stage polymerization) to prepare a dispersion of high molecular weight resin particles containing a crystalline substance.

  Next, a polymerization initiator and a monomer for obtaining a low molecular weight resin are added to the dispersion of the resin particles, and the monomer is polymerized in the presence of the resin particles (second-stage polymerization). Thus, a coating layer made of a low molecular weight resin (monomer polymer) is formed on the surface of the resin particles.

<Three-stage polymerization method>
The three-stage polymerization method produces composite resin particles composed of a central part (core) formed from a high molecular weight resin, an intermediate layer containing a crystalline substance, and an outer layer (shell) formed from a low molecular weight resin. Is the method. The toner of the present invention exists as the composite resin particles as described above.

  Specifically describing this method, first, a dispersion of resin particles obtained by polymerization treatment (first-stage polymerization) according to a conventional method is added to an aqueous medium (for example, an aqueous solution of a surfactant), and Resin particles (core particles) are obtained by dispersing oil droplets of a monomer solution obtained by dissolving a crystalline substance in a monomer in the aqueous medium and then polymerizing the system (second-stage polymerization). A coating layer (intermediate layer) made of a resin (monomer polymer) containing a crystalline substance is formed on the surface of the surface to prepare a dispersion of composite resin particles (high molecular weight resin-intermediate molecular weight resin).

  Next, a polymerization initiator and a monomer for obtaining a low molecular weight resin are added to the obtained dispersion of composite resin particles, and the monomer is polymerized in the presence of the composite resin particles (third-stage polymerization). ), A coating layer made of a low molecular weight resin (monomer polymer) is formed on the surface of the composite resin particles. In the above method, it is preferable that a crystalline substance can be finely and uniformly dispersed by incorporating an intermediate layer.

  One aspect of the toner production method according to the present invention is that the polymerizable monomer is polymerized in an aqueous medium. That is, when forming resin particles (core particles) or coating layers (intermediate layers) containing a crystalline substance, the crystalline substance is dissolved in the monomer, and the resulting monomer solution is oiled in an aqueous medium. It is a method of obtaining latex particles by dispersing in drops and adding a polymerization initiator to this system for polymerization treatment.

  The aqueous medium used in the present invention refers to a medium comprising 50 to 100% by mass of water and 0 to 50% by mass of a water-soluble organic solvent. Examples of the water-soluble organic solvent include methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, tetrahydrofuran, and the like, and an alcohol-based organic solvent that does not dissolve the obtained resin is preferable.

  As a suitable polymerization method for forming resin particles or a coating layer containing a crystalline substance, the crystalline substance is a monomer in an aqueous medium in which a surfactant having a concentration equal to or lower than the critical micelle concentration is dissolved. The monomer solution dissolved in is dispersed in oil droplets using mechanical energy to prepare a dispersion, and a water-soluble polymerization initiator is added to the resulting dispersion to cause radical polymerization in the oil droplets. A method (hereinafter referred to as “mini-emulsion method” in the present invention), and the effects of the present invention can be exhibited more preferably. In the above method, an oil-soluble polymerization initiator may be used instead of the water-soluble polymerization initiator or together with the water-soluble polymerization initiator.

  According to the mini-emulsion method that mechanically forms oil droplets, unlike the usual emulsion polymerization method, there is little detachment of the crystalline substance dissolved in the oil phase, and it is sufficient in the resin particles or coating layer to be formed. Any amount of crystalline material can be introduced.

  Here, the disperser for dispersing oil droplets by mechanical energy is not particularly limited. For example, a stirring device “CLEARMIX” (M Technique (Equation Technique) equipped with a rotor that rotates at high speed is used. Co., Ltd.), ultrasonic disperser, mechanical homogenizer, manton gorin, pressure homogenizer, and the like. Moreover, as a dispersed particle diameter, 10-1000 nm is preferable, More preferably, it is 50-1000 nm, Most preferably, it is 30-300 nm.

  By giving a distribution to the dispersed particle diameter, the phase separation structure of the crystalline substance in the toner particles, that is, the ferret horizontal diameter, the shape factor, and the coefficient of variation thereof may be controlled.

  In addition, as other polymerization methods for forming resin particles or a coating layer containing a crystalline substance, known methods such as an emulsion polymerization method, a suspension polymerization method, and a seed polymerization method can be employed. These polymerization methods can also be employed to obtain resin particles (core particles) or coating layers constituting the composite resin particles that do not contain a crystalline substance.

  The particle diameter of the composite resin particles obtained in this polymerization step may be in the range of 10 to 1000 nm in terms of mass average particle diameter measured using an electrophoretic light scattering photometer “ELS-800” (manufactured by Otsuka Electronics). preferable.

  Moreover, it is preferable that the glass transition temperature (Tg) of a composite resin particle exists in the range of 48-74 degreeC, More preferably, it is 52-64 degreeC. The softening point of the composite resin particles is preferably in the range of 95 to 140 ° C.

  The toner according to the present invention is obtained by fusing resin particles on the surface of the resin and colored particles by a salting-out / fusing method to form a resin layer. This will be described below.

[Salting out / fusion process]
This salting-out / fusion step is carried out by salting out / bonding the composite resin particles and the colorant particles obtained in the multi-stage polymerization step (to cause salting-out and fusion at the same time) to form an irregular shape ( This is a step of obtaining non-spherical toner particles.

  In the present invention, salting out / fusion means that salting out (aggregation of particles) and fusion (disappearance of the interface between particles) occur at the same time or salting out and fusion occur at the same time. In order to perform salting-out and fusion at the same time, it is preferable to agglomerate particles (composite resin particles, colorant particles) under a temperature condition higher than the glass transition temperature (Tg) of the resin constituting the composite resin particles. .

  In this salting-out / fusion step, internal additive particles such as charge control agents (fine particles having a number average primary particle size of about 10 to 1000 nm) may be salted out / fused together with the composite resin particles and the colorant particles. Good. Further, the colorant particles may be surface-modified, and conventionally known ones can be used as the surface modifier.

[Aging process]
The aging step is a step that follows the salting out / fusion step, and the temperature is kept near the melting point of the crystalline substance, preferably the melting point ± 20 ° C., and the stirring is continued at a constant strength even after the resin particles are fused. In this step, the crystalline substance is phase-separated. In this step, it is possible to control the ferret horizontal diameter, shape factor, and variation coefficient of the crystalline material.

  Moreover, in this invention, it is preferable that the total value of the bivalent (trivalent) metal element used for a coagulant | flocculant and the monovalent | monohydric metal element added as an aggregation terminator mentioned later is 350-35000 ppm.

  The residual amount of metal ions in the toner can be measured by using a fluorescent X-ray analyzer “System 3270” (manufactured by Rigaku Denki Kogyo Co., Ltd.) and using a metal species of a metal salt used as a flocculant (for example, calcium chloride). It can be determined by measuring the intensity of the fluorescent X-ray emitted from the derived calcium or the like.

  As a specific measurement method, a plurality of toners having a known content ratio of the flocculant metal salt are prepared, each toner 5g is pelletized, the content ratio (mass ppm) of the flocculant metal salt, and the metal species of the metal salt The relationship (calibration curve) with the fluorescent X-ray intensity (peak intensity) is measured. Next, the toner (sample) whose content of the flocculant metal salt is to be measured is similarly pelletized, and the fluorescent X-ray intensity from the metal species of the flocculant metal salt is measured, and the content, that is, “metal ions in the toner” The “residual amount” can be determined.

[Filtering and washing process]
In this filtration / washing step, a filtration treatment for filtering the toner particles from the toner particle dispersion obtained in the above step, and a surfactant or salt from the filtered toner particles (cake-like aggregate). A cleaning process for removing deposits such as a depositing agent is performed. Here, the filtration method is not particularly limited, such as a centrifugal separation method, a vacuum filtration method using Nutsche or the like, a filtration method using a filter press or the like.

[Drying process]
This step is a step of drying the washed toner particles, but in the present invention, a step of drying under reduced pressure is preferred.

  Examples of the vacuum dryer used in this step include, but are not limited to, a vacuum spray dryer, a vacuum freeze dryer, and a vacuum dryer. Specifically, it is preferable to use a stationary shelf dryer, a movable shelf dryer, a fluidized bed dryer, a rotary dryer, a stirring dryer, or the like that can be decompressed.

  The conditions for drying under reduced pressure may be any temperature as long as the drying temperature is equal to or lower than the Tg of the resin used in the toner, and the degree of reduced pressure, the drying time, and the like are not particularly limited and can be set as appropriate.

  In addition, when the toner particles subjected to the drying under reduced pressure are aggregated with a weak interparticle attractive force, the aggregate may be crushed. Here, as the crushing treatment apparatus, a mechanical crushing apparatus such as a jet mill, a Henschel mixer, a coffee mill, or a food processor can be used.

  The toner according to the present invention forms composite resin particles in the absence of a colorant, adds a dispersion of colorant particles to the dispersion of the composite resin particles, and salting out the composite resin particles and the colorant particles. It is preferably prepared by fusing.

  Thus, the polymerization reaction for obtaining the composite resin particles is not inhibited by preparing the composite resin particles in a system in which no colorant is present. Therefore, according to the toner of the present invention, the excellent offset resistance is not impaired, and the fixing device is not contaminated or the image is not stained due to the accumulation of toner.

  In addition, as a result of the polymerization reaction for obtaining the composite resin particles being reliably performed, no monomer or oligomer remains in the obtained toner particles, and the heat fixing step of the image forming method using the toner In this case, no off-flavor is generated.

  Further, since the surface characteristics of the obtained toner particles are uniform and the charge amount distribution is sharp, an image having excellent sharpness can be formed over a long period of time. According to such a toner having a uniform composition, molecular weight, and surface characteristics between toner particles, an image forming method including a fixing process using a contact heating method maintains good adhesion (high fixing strength) to an image support. However, it is possible to improve the offset resistance and the anti-winding property, and an image having an appropriate gloss can be obtained.

  Next, each component used in the toner manufacturing process will be described in detail.

(Polymerizable monomer)
As a polymerizable monomer for producing the resin (binder) used in the present invention, a hydrophobic monomer is an essential constituent, and a crosslinkable monomer is used as necessary. Further, as described below, it is desirable to contain at least one monomer having an acidic polar group or a monomer having a basic polar group.

(1) Hydrophobic monomer The hydrophobic monomer constituting the monomer component is not particularly limited, and conventionally known monomers can be used. Moreover, it can be used combining 1 type (s) or 2 or more types so that the required characteristic may be satisfy | filled.

  Specifically, monovinyl aromatic monomers, (meth) acrylic acid ester monomers, vinyl ester monomers, vinyl ether monomers, monoolefin monomers, diolefin monomers , Halogenated olefin monomers and the like can be used.

  Examples of vinyl aromatic monomers include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-methoxy styrene, p-phenyl styrene, p-chloro styrene, p-ethyl styrene, p. -N-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, 2, Examples thereof include styrene monomers such as 4-dimethylstyrene and 3,4-dichlorostyrene and derivatives thereof.

  Examples of acrylic monomers include acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, methyl methacrylate, methacrylic acid. Examples include butyl acid, hexyl methacrylate, 2-ethylhexyl methacrylate, ethyl β-hydroxyacrylate, propyl γ-aminoacrylate, stearyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like.

  Examples of vinyl ester monomers include vinyl acetate, vinyl propionate, and vinyl benzoate.

  Examples of the vinyl ether monomer include vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl phenyl ether and the like.

  Examples of the monoolefin monomer include ethylene, propylene, isobutylene, 1-butene, 1-pentene, 4-methyl-1-pentene and the like.

  Examples of the diolefin monomer include butadiene, isoprene, chloroprene and the like.

(2) Crosslinkable monomer A crosslinkable monomer may be added to improve the properties of the resin particles. Examples of the crosslinkable monomer include those having two or more unsaturated bonds such as divinylbenzene, divinylnaphthalene, divinyl ether, diethylene glycol methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and diallyl phthalate.

(3) Monomer having an acidic polar group Monomers having an acidic polar group include (a) an α, β-ethylenically unsaturated compound having a carboxyl group (—COOH) and (b) a sulfone group (— Mention may be made of α, β-ethylenically unsaturated compounds having SO ₃ H).

  Examples of the α, β-ethylenically unsaturated compound (a) having a —COO group include acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, cinnamic acid, maleic acid monobutyl ester, maleic acid. Examples thereof include acid monooctyl esters and metal salts thereof such as Na and Zn.

Examples of the α, β-ethylenically unsaturated compound having a —SO ₃ H group in (b) include sulfonated styrene, its Na salt, allylsulfosuccinic acid, octyl allylsulfosuccinate, and its Na salt. it can.

(4) Monomer having a basic polar group As the monomer having a basic polar group, (i) 1 to 12 carbon atoms having an amine group or a quaternary ammonium group, preferably 2 to 8, particularly preferably 2. (Meth) acrylic acid esters of aliphatic alcohols, (ii) (meth) acrylic acid amides or (meth) acrylic acid amides optionally monosubstituted or disubstituted with alkyl groups of 1 to 18 carbon atoms on N, (iii) And vinyl compounds substituted with a heterocyclic group having N as a ring member, and (iv) N, N-diallyl-alkylamine or a quaternary ammonium salt thereof.

  Among them, the (i) aliphatic alcohol (meth) acrylic acid ester having an amine group or a quaternary ammonium group is preferable as a monomer having a basic polar group.

  Examples of (i) amine (meth) acrylic esters of aliphatic alcohols having an amine group or quaternary ammonium group include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, the above four compounds Quaternary ammonium salts, 3-dimethylaminophenyl acrylate, 2-hydroxy-3-methacryloxypropyltrimethylammonium salt, and the like.

  (Ii) (Meth) acrylic acid amide or optionally mono- or dialkyl-substituted (meth) acrylic acid amide on N includes acrylamide, N-butylacrylamide, N, N-dibutylacrylamide, piperidylacrylamide, methacrylamide N-butylmethacrylamide, N, N-dimethylacrylamide, N-octadecylacrylamide and the like.

  Examples of the vinyl compound substituted with a heterocyclic group having N as a ring member in (iii) include vinylpyridine, vinylpyrrolidone, vinyl-N-methylpyridinium chloride, vinyl-N-ethylpyridinium chloride and the like.

  Examples of (iv) N, N-diallyl-alkylamine include N, N-diallylmethylammonium chloride and N, N-diallylethylammonium chloride.

(Polymerization initiator)
The radical polymerization initiator used in the present invention can be appropriately used as long as it is water-soluble. For example, persulfates (for example, potassium persulfate, ammonium persulfate, etc.), azo compounds (for example, 4,4′-azobis-4-cyanovaleric acid and its salts, 2,2′-azobis (2-amidinopropane) Salt), peroxide compounds and the like. Furthermore, the radical polymerization initiator can be combined with a reducing agent as necessary to form a redox initiator. Use of a redox initiator is preferred because the polymerization activity is increased, the polymerization temperature can be lowered, and the polymerization time can be shortened.

  As the polymerization temperature, any temperature may be selected as long as it is equal to or higher than the lowest radical generation temperature of the polymerization initiator. For example, a range of 50 ° C. to 90 ° C. is used. However, it is also possible to perform polymerization at room temperature or higher by using a polymerization initiator that starts at room temperature, for example, a combination of hydrogen peroxide-reducing agent (such as ascorbic acid).

(Surfactant)
In particular, in order to perform miniemulsion polymerization using the above-described polymerizable monomer, it is preferable to disperse oil droplets in an aqueous medium using a surfactant. The surfactant that can be used in this case is not particularly limited, and the following ionic surfactants can be given as examples of suitable compounds.

  Examples of the ionic surfactant include sulfonate (sodium dodecylbenzenesulfonate, sodium arylalkylpolyethersulfonate, 3,3-disulfonediphenylurea-4,4-diazo-bis-amino-8-naphthol- 6-sulfonate sodium, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-6-sulfonate sodium, etc.) , Sulfate salts (sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, etc.), fatty acid salts (sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, stearyl Potassium, calcium oleate and the like).

  Nonionic surfactants can also be used. Specifically, for example, polyethylene oxide, polypropylene oxide, a combination of polypropylene oxide and polyethylene oxide, ester of polyethylene glycol and higher fatty acid, alkylphenol polyethylene oxide, ester of higher fatty acid and polyethylene glycol, ester of higher fatty acid and polypropylene oxide, And sorbitan esters.

  In the present invention, these surfactants are mainly used as an emulsifier during emulsion polymerization, but may be used for other steps or for other purposes.

(Molecular weight distribution of resin particles and toner)
The toner according to the present invention preferably has a peak or shoulder at 100,000 to 1,000,000 and 1,000 to 50,000, and further has a peak or shoulder of 100,000 to 1,000,000. 25,000-150,000 and 1,000-50,000 are more preferred.

  The molecular weight of the resin particles is both a high molecular weight component having a peak or shoulder in the region of 100,000 to 1,000,000 and a low molecular weight component having a peak or shoulder in the region of 1,000 to less than 50,000. A resin containing at least is preferable. More preferably, an intermediate molecular weight resin having a peak or shoulder at a peak molecular weight of 15,000 to 100,000 is preferably used.

  The molecular weight measurement method of the toner or resin is preferably measured by GPC (gel permeation chromatography) using THF (tetrahydrofuran) as a solvent. That is, 1.0 ml of THF is added to 0.5 to 5 mg of a measurement sample, more specifically 1 mg, and the mixture is stirred at room temperature using a magnetic stirrer or the like and sufficiently dissolved. Subsequently, after processing with a membrane filter having a pore size of 0.45 to 0.50 μm, the solution is injected into GPC. The measurement conditions of GPC are measured by stabilizing the column at 40 ° C., flowing THF at a flow rate of 1.0 ml / min, and injecting about 100 μl of a sample having a concentration of 1 mg / ml.

  The column is preferably used in combination with a commercially available polystyrene gel column. For example, combinations of Shodex GPC KF-801, 802, 803, 804, 805, 806, and 807 manufactured by Showa Denko, and combinations of TSKgel G1000H, G2000H, G3000H, G4000H, G5000H, G6000H, G7000H, and TSKguard column manufactured by Tosoh, etc. Can be mentioned.

  As a detector, a refractive index detector (IR detector) or a UV detector may be used. In the measurement of the molecular weight of a sample, the molecular weight distribution of the sample is calculated using a calibration curve created using monodisperse polystyrene standard particles. About 10 points may be used as polystyrene for preparing a calibration curve.

(Flocculant)
The flocculant used in the present invention is preferably selected from metal salts.

  Examples of the metal salt include monovalent metals such as alkali metal salts such as sodium, potassium and lithium, divalent metals such as alkaline earth metal salts such as calcium and magnesium, and divalent metals such as manganese and copper. Examples of the metal salt include trivalent metal salts such as iron and aluminum.

  Specific examples of these metal salts are shown below. Specific examples of the monovalent metal salt include sodium chloride, potassium chloride, lithium chloride, and divalent metal salts such as calcium chloride, zinc chloride, copper sulfate, magnesium sulfate, and manganese sulfate. Examples of the trivalent metal salt include aluminum chloride and iron chloride. These are appropriately selected according to the purpose. In general, the divalent metal salt has a smaller critical aggregation concentration (coagulation value or coagulation point) than the monovalent metal salt, and the trivalent metal salt has a smaller critical aggregation concentration.

  The critical flocculation concentration referred to in the present invention is an index related to the stability of the dispersion in the aqueous dispersion, and indicates the concentration at which flocculation occurs when a flocculant is added. This critical coagulation concentration varies greatly depending on the latex itself and the dispersant. For example, it is described in Seizo Okamura et al., Polymer Chemistry 17,601 (1960), etc., and the value can be known by following these descriptions. As another method, a desired salt is added to the target particle dispersion at different concentrations, the ζ potential of the dispersion is measured, and the salt concentration at the point where the ζ potential starts to change is defined as the critical aggregation concentration. It is also possible to do.

  In the present invention, the polymer fine particle dispersion is treated with a metal salt so as to have a concentration equal to or higher than the critical aggregation concentration. At this time, as a matter of course, whether the metal salt is added directly or as an aqueous solution is arbitrarily selected according to the purpose. When added as an aqueous solution, the added metal salt must be equal to or higher than the critical aggregation concentration of the polymer particles with respect to the volume of the polymer particle dispersion and the total volume of the metal salt aqueous solution.

  The concentration of the metal salt as a flocculant in the present invention may be not less than the critical aggregation concentration, but is preferably 1.2 times or more, more preferably 1.5 times or more the critical aggregation concentration.

(Release agent)
The toner used in the present invention is preferably a toner obtained by fusing resin particles containing a release agent in an aqueous medium. Thus, the resin particles in which the release agent is encapsulated in the resin particles are salted out / fused in the aqueous medium with the colorant particles, whereby a toner in which the release agent is finely dispersed can be obtained.

  In the toner according to the present invention, low molecular weight polypropylene (number average molecular weight = 1500 to 9000), low molecular weight polyethylene, and the like are preferable as the release agent, and ester compounds represented by the following formula are particularly preferable.

R ^1- (OCO-R ² ) _n
In the formula, n is an integer of 1 to 4, preferably 2 to 4, more preferably 3 to 4, particularly preferably 4. R ¹ and R ² each represents a hydrocarbon group that may have a substituent. R ¹ has 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 2 to 5 carbon atoms. R ² has 1 to 40 carbon atoms, preferably 16 to 30 carbon atoms, and more preferably 18 to 26 carbon atoms.

  Next, the example of a typical compound is shown below.

  The amount of the compound added is 1 to 30% by mass, preferably 2 to 20% by mass, and more preferably 3 to 15% by mass with respect to the whole toner.

  The toner according to the present invention is preferably prepared by encapsulating the release agent in resin particles by a mini-emulsion polymerization method, and salting out and fusing together with the toner particles.

(Charge control agent)
In addition to the colorant and the release agent, a material that can impart various functions as a toner material can be added to the toner. Specific examples include charge control agents. These components can be added simultaneously with the resin particles and the colorant particles in the salting out / fusion step described above, and can be added by various methods such as a method included in the toner and a method of adding to the resin particles themselves.

  As the charge control agent, various known ones that can be dispersed in water can be used. Specific examples include nigrosine dyes, naphthenic acid or higher fatty acid metal salts, alkoxylated amines, quaternary ammonium salt compounds, azo metal complexes, salicylic acid metal salts or metal complexes thereof.

(External additive)
To the toner according to the present invention, so-called external additives can be added and used for the purpose of improving fluidity and improving cleaning properties. These external additives are not particularly limited, and various inorganic fine particles, organic fine particles and lubricants can be used.

  Examples of inorganic fine particles that can be used as an external additive include conventionally known fine particles. Specifically, silica fine particles, titanium fine particles, alumina fine particles and the like can be preferably used. These inorganic fine particles are preferably hydrophobic.

  Specific examples of the silica fine particles include commercially available products R-805, R-976, R-974, R-972, R-812, R-809 manufactured by Nippon Aerosil Co., Ltd., and HVK-2150 manufactured by Hoechst Co., Ltd. , H-200, commercially available products TS-720, TS-530, TS-610, H-5, MS-5 manufactured by Cabot Corporation.

  Specific examples of the titanium fine particles include, for example, commercial products T-805 and T-604 manufactured by Nippon Aerosil Co., Ltd., and commercial products MT-100S, MT-100B, MT-500BS, and MT-600 manufactured by Teika Co., Ltd. , MT-600SS, JA-1, commercial products manufactured by Fuji Titanium Co., Ltd. TA-300SI, TA-500, TAF-130, TAF-510, TAF-510T, commercial products IT-S manufactured by Idemitsu Kosan Co., Ltd. IT-OA, IT-OB, IT-OC and the like.

  Specific examples of the alumina fine particles include commercial products RFY-C and C-604 manufactured by Nippon Aerosil Co., Ltd., and commercial products TTO-55 manufactured by Ishihara Sangyo Co., Ltd.

  Examples of the organic fine particles that can be used as the external additive include spherical fine particles having a number average primary particle diameter of about 10 to 2000 nm. Examples of the constituent material of the organic fine particles include polystyrene, polymethyl methacrylate, and styrene-methyl methacrylate copolymer.

  Examples of the lubricant that can be used as an external additive include metal salts of higher fatty acids. Specific examples of the metal salts of such higher fatty acids include zinc stearate, aluminum stearate, copper stearate, magnesium stearate, calcium stearate, and the like; zinc oleate, manganese oleate, iron oleate, olein Oleic acid metal salts such as acid copper and magnesium oleate; palmitate metal salts such as zinc palmitate, copper palmitate, magnesium palmitate and calcium palmitate; linoleic acid metal salts such as zinc linoleate and calcium linoleate; ricinol Examples include ricinoleic acid metal salts such as zinc acid and calcium ricinoleate.

  The addition amount of the external additive is preferably about 0.1 to 5% by mass with respect to the toner.

<External additive addition process>
This step is a step of adding an external additive to the dried toner particles.

  Examples of the apparatus used for adding the external additive include various known mixing apparatuses such as a Turbuler mixer, a Henschel mixer, a Nauter mixer, and a V-type mixer.

(Toner particles)
The particle diameter of the toner according to the present invention is preferably 3 to 10 μm in terms of number average particle diameter, and more preferably 3 to 8 μm. This particle size can be controlled by the concentration of the flocculant (salting-out agent), the amount of organic solvent added, the fusing time, and the polymer composition in the toner production method.

  When the number average particle diameter is 3 to 10 μm, toner particles having high adhesion force that fly and adhere to the heating member and generate offset in the fixing process are reduced, and transfer efficiency is increased and halftone The image quality is improved, and the image quality of fine lines and dots is improved.

  The number average particle diameter of the toner can be measured using a Coulter Counter TA-II, Coulter Multisizer, SLAD 1100 (a laser diffraction particle diameter measuring apparatus manufactured by Shimadzu Corporation) or the like.

  In the present invention, a Coulter multisizer is used, and an interface (manufactured by Nikkaki Co., Ltd.) for outputting a particle size distribution and a personal computer are connected. The aperture in the Coulter Multisizer was 100 μm, and the toner volume distribution of 2 μm or more (for example, 2 to 40 μm) was measured to calculate the particle size distribution and average particle size.

<Preferable shape factor range of toner particles>
The shape factor of the toner according to the present invention is 1.0 to 1.6, 65% by number or more, preferably 1.2 to 1.6, 65% by number or more, particularly preferably 1.2 to 1. .6 is 70% by number or more.

  The shape factor of the toner according to the present invention is represented by the following formula and indicates the degree of roundness of the toner particles.

Shape factor = ((maximum diameter / 2) ² × π) / projection area Here, the maximum diameter is the distance between the parallel lines when the projected image of toner particles on a plane is sandwiched between two parallel lines. This is the maximum particle width. The projected area refers to the area of the projected image of the toner particles on the plane. In the present invention, this shape factor is obtained by taking a photograph in which toner particles are enlarged 2000 times with a scanning electron microscope, and then using “SCANNING IMAGE ANALYZER” (manufactured by JEOL) based on this photograph. It was measured by performing an analysis. At this time, the shape factor of the present invention was measured by the above formula using 100 toner particles.

  As the toner according to the present invention, when the particle size of the toner particles is D (μm), the horizontal axis is the natural logarithm lnD and the horizontal axis is divided into a plurality of classes at intervals of 0.23. Is a sum (M) of the relative frequency (m1) of the toner particles included in the most frequent class and the relative frequency (m2) of the toner particles included in the most frequent class after the most frequent class. The toner is preferably 70% or more.

  When the sum (M) of the relative frequency (m1) and the relative frequency (m2) is 70% or more, the dispersion of the particle size distribution of the toner particles becomes narrow. Therefore, selective development can be performed by using the toner in the image forming process. Can be reliably suppressed.

  In the present invention, the histogram showing the particle size distribution based on the number is a natural logarithm lnD (D: particle size of individual toner particles) having a plurality of classes (0 to 0.23: 0.23) at intervals of 0.23. 0.46: 0.46-0.69: 0.69-0.92: 0.92-1.15: 1.15-1.38: 1.38-1.61: 1.61-1. 84: 1.84 to 2.07: 2.07 to 2.30: 2.30 to 2.53: 2.53 to 2.76, and so on). This histogram was created by transferring the particle size data of the sample measured by the Coulter Multisizer to the computer via the I / O unit according to the following conditions and using the particle size distribution analysis program in the computer. is there.

〔Measurement condition〕
1: Aperture: 100 μm
2: Sample preparation method: electrolytic solution [ISOTON R-11 (manufactured by Coulter Scientific Japan)] A suitable amount of a surfactant (neutral detergent) is added to 50 to 100 ml and stirred, and 10 to 20 mg of a measurement sample is added thereto. . This system is prepared by dispersing for 1 minute with an ultrasonic disperser.

  The toner according to the present invention preferably has a median diameter (D50v) on a volume basis of 3 μm or more and 8 μm or less. By setting the volume-based median diameter in the above range, for example, it is possible to faithfully reproduce a very minute dot image at a level of 1200 dpi (dpi; number of dots per inch (2.54 cm)).

  The toner according to the present invention is one of the problems to be able to faithfully reproduce the color of a photographic image. By making the volume-based median diameter a small diameter level in the above range, a photographic image can be formed. The dot image to be reduced is miniaturized, and a high-definition photographic image equivalent to or better than the printed image is obtained. In particular, in a printing field called “on-demand printing” where a print order is received at a level of several hundred to several thousand copies, high-quality prints containing high-definition photographic images can be quickly delivered to the user.

  The volume-based median diameter (D50v diameter) of toner can be measured and calculated using a device in which a computer system for data processing is connected to Multisizer 3 (manufactured by Beckman Coulter).

  As a measurement procedure, 0.02 g of toner was mixed with 20 ml of a surfactant solution (for example, a surfactant solution obtained by diluting a neutral detergent containing a surfactant component 10 times with pure water for the purpose of dispersing the toner). Then, ultrasonic dispersion is performed for 1 minute to prepare a toner dispersion. This toner dispersion is poured into a beaker containing ISOTON II (manufactured by Beckman Coulter) in a sample stand with a pipette until the measured concentration reaches 5 to 10%, and the measurement is performed by setting the measuring machine count to 2500. . The aperture size of the multisizer 3 is 50 μm.

  The toner according to the present invention preferably has a coefficient of variation (CV value) in the volume-based particle size distribution of 2% to 21%, more preferably 5% to 15%. The coefficient of variation (CV value) in the volume-based particle size distribution represents the degree of dispersion in the particle size distribution of the toner particles on the volume basis, and is defined by the following equation.

CV value (%) = (standard deviation in number particle size distribution) / (median diameter (D50v) in number particle size distribution) × 100
The smaller the CV value, the sharper the particle size distribution, and the larger the toner particle size. In other words, since toners having a uniform size can be obtained, it is possible to reproduce a fine dot image and fine lines required for digital image formation with higher accuracy. Further, when printing a photographic image, it is possible to create a high-quality photographic image at an image level produced with printing ink or higher by using small-diameter toner having a uniform size.

  The toner according to the present invention preferably has a softening point temperature (Tsp) of 70 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower. The colorant used in the toner according to the present invention has a stable property that the spectrum does not change even under the influence of heat. However, by setting the softening point within the above range, The influence of the applied heat can be further reduced. Therefore, since image formation can be performed without imposing a burden on the colorant, it is expected that a wider and more stable color reproducibility is expressed.

  In addition, by setting the softening point of the toner within the above range, the toner image can be fixed at a temperature lower than that of the prior art, and environmentally friendly image formation with reduced power consumption can be realized.

The softening point of the toner can be controlled by, for example, the following methods alone or in combination. That is,
(1) Adjusting the type and composition ratio of monomers used for resin formation (2) Adjusting the molecular weight of the resin according to the type and addition amount of the chain transfer agent (3) Adjusting the type and addition amount of wax and the like.

Further, the method for measuring the softening point temperature of the toner is specifically a “flow tester CFT-500 (manufactured by Shimadzu Corporation)”, which is formed into a columnar shape with a height of 10 mm and heated at a temperature rising rate of 6 ° C./min. While applying a pressure of 1.96 × 10 ⁶ Pa from the plunger while pushing from a nozzle having a diameter of 1 mm and a length of 1 mm, a curve between the plunger drop amount and temperature of the flow tester (softening flow curve) The temperature at which the gas first flows out is the melting start temperature, and the temperature for the drop amount of 5 mm is the softening point temperature.

  Next, a toner manufacturing method according to the present invention will be described.

  The toner according to the present invention includes at least a resin, a colorant represented by the general formula (1), and particles containing a silanol compound represented by the general formula (2) (hereinafter also referred to as colored particles). Is. The colored particles constituting the toner according to the present invention are not particularly limited, and can be produced by a conventional toner production method.

  That is, a so-called polymerized toner in which a toner is produced through a kneading, pulverizing, and classification process, a toner manufacturing method by a so-called pulverizing method, or a polymerizable monomer is polymerized and particles are formed while simultaneously controlling the shape and size. The production method (for example, emulsion polymerization method, suspension polymerization method, polyester elongation method, etc.) can be applied.

  When the toner according to the present invention is produced by a pulverization method, it is preferable to produce the toner while maintaining the temperature of the kneaded material at 130 ° C. or lower. This is because if the temperature applied to the kneaded product exceeds 130 ° C., the colorant aggregation state in the kneaded product changes due to the action of heat applied to the kneaded product, and the uniform aggregated state may not be maintained. Because there is. If variation occurs in the aggregated state, the produced toner may vary in color tone, which may cause color turbidity.

(Developer)
The toner according to the present invention may be used as a one-component developer or a two-component developer.

  When used as a one-component developer, a non-magnetic one-component developer or a magnetic one-component developer containing about 0.1 to 0.5 μm of magnetic particles in the toner can be used. be able to.

  Further, it can be mixed with a carrier and used as a two-component developer. In this case, conventionally known materials such as metals such as iron, ferrite and magnetite, and alloys of these metals with metals such as aluminum and lead can be used as the magnetic particles of the carrier. Ferrite particles are particularly preferable. The magnetic particles preferably have a volume average particle diameter of 15 to 100 μm, more preferably 25 to 80 μm.

  The volume average particle diameter of the carrier can be typically measured by a laser diffraction type particle size distribution measuring apparatus “HELOS” (manufactured by SYMPATEC) equipped with a wet disperser.

  The carrier is preferably a carrier in which magnetic particles are further 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, silicone resin, ester resin, or fluorine-containing polymer resin is used. In addition, the resin for constituting the resin-dispersed carrier is not particularly limited, and a known resin can be used. For example, a styrene-acrylic resin, a polyester resin, a fluorine resin, a phenol resin, or the like is used. be able to.

  Next, an image forming method using the toner according to the present invention will be described. First, an image forming method when the toner according to the present invention is used as a two-component developer will be described.

  FIG. 1 is a schematic view showing an example of an image forming apparatus that can be used when a toner according to the present invention is used as a two-component developer.

  In FIG. 1, 1Y, 1M, 1C and 1K are photoreceptors, 4Y, 4M, 4C and 4K are developing devices, 5Y, 5M, 5C and 5K are primary transfer rolls as primary transfer means, and 5A is a secondary transfer. Secondary transfer rolls as means, 6Y, 6M, 6C and 6K are cleaning devices, 7 is an intermediate transfer member unit, 24 is a heat roll type fixing device, and 70 is an intermediate transfer member.

  This image forming apparatus is called a tandem color image forming apparatus, and includes a plurality of sets of image forming units 10Y, 10M, 10C, and 10K, an endless belt-shaped intermediate transfer body unit 7 as a transfer unit, and a recording member P. An endless belt-shaped sheet feeding / conveying means 21 and a heat roll type fixing device 24 as a fixing means. A document image reading device SC is disposed on the upper part of the main body A of the image forming apparatus.

  As one of the different color toner images formed on each photoconductor, an image forming unit 10Y that forms a yellow image includes a drum-shaped photoconductor 1Y as a first photoconductor, and a periphery of the photoconductor 1Y. A charging unit 2Y, an exposure unit 3Y, a developing unit 4Y, a primary transfer roll 5Y as a primary transfer unit, and a cleaning unit 6Y.

  An image forming unit 10M that forms a magenta image as another different color toner image is disposed around a drum-shaped photoconductor 1M as a first photoconductor, and the photoconductor 1M. A charging unit 2M, an exposure unit 3M, a developing unit 4M, a primary transfer roll 5M as a primary transfer unit, and a cleaning unit 6M.

  In addition, an image forming unit 10C that forms a cyan image as one of other different color toner images is disposed around the photoconductor 1C as a drum-type photoconductor 1C as a first photoconductor. The charging unit 2C, the exposure unit 3C, the developing unit 4C, the primary transfer roll 5C as the primary transfer unit, and the cleaning unit 6C are provided.

  Further, an image forming unit 10K that forms a black image as one of other different color toner images is disposed around a drum-shaped photosensitive member 1K as a first photosensitive member, and the photosensitive member 1K. It has a charging means 2K, an exposure means 3K, a developing means 4K, a primary transfer roll 5K as a primary transfer means, and a cleaning means 6K.

  The endless belt-like intermediate transfer body unit 7 has an endless belt-like intermediate transfer body 70 as an intermediate transfer endless belt-like second image carrier that is wound around a plurality of rolls and is rotatably supported.

  Each color image formed by the image forming units 10Y, 10M, 10C, and 10K is sequentially transferred onto the rotating endless belt-shaped intermediate transfer body 70 by the primary transfer rolls 5Y, 5M, 5C, and 5K, and is combined. A colored image is formed. A recording member P such as a sheet as a transfer material accommodated in the sheet feeding cassette 20 is fed by the sheet feeding / conveying means 21, passes through a plurality of intermediate rolls 22 A, 22 B, 22 C, 22 D, and a registration roll 23, and is secondary. A color image is transferred onto the recording member P at a time by being conveyed to a secondary transfer roll 5A as a transfer means. The recording member P to which the color image has been transferred is fixed by the heat roll type fixing device 24, is sandwiched by the paper discharge roll 25, and is placed on the paper discharge tray 26 outside the apparatus.

  On the other hand, after the color image is transferred to the recording member P by the secondary transfer roll 5A, the residual toner is removed from the endless belt-shaped intermediate transfer body 70 from which the recording member P is separated by the curvature by the cleaning means 6A.

  During the image forming process, the primary transfer roll 5K is always in pressure contact with the photoreceptor 1K. The other primary transfer rolls 5Y, 5M, and 5C are in pressure contact with the corresponding photoreceptors 1Y, 1M, and 1C, respectively, only during color image formation.

  The secondary transfer roll 5A comes into pressure contact with the endless belt-shaped intermediate transfer body 70 only when the recording member P passes through the secondary transfer roll 5A and secondary transfer is performed.

  Further, the housing 8 can be pulled out from the apparatus main body A through the support rails 82L and 82R. The housing 8 includes image forming units 10Y, 10M, 10C, and 10K, and an endless belt-shaped intermediate transfer body unit 7.

  The image forming units 10Y, 10M, 10C, and 10K are arranged in tandem in the vertical direction. An endless belt-shaped intermediate transfer body unit 7 is disposed on the left side of the photoreceptors 1Y, 1M, 1C, and 1K in the figure. The endless belt-shaped intermediate transfer body unit 7 includes an endless belt-shaped intermediate transfer body 70 that can be rotated by winding rolls 71, 72, 73, 74, and 76, primary transfer rolls 5Y, 5M, 5C, and 5K, and a cleaning unit. 6A.

  The image forming units 10Y, 10M, 10C, and 10K and the endless belt-shaped intermediate transfer body unit 7 are integrally pulled out from the main body A by the drawer operation of the housing 8.

  In this way, toner images are formed on the photoreceptors 1Y, 1M, 1C, and 1K by charging, exposure, and development, and the toner images of the respective colors are superimposed on the endless belt-shaped intermediate transfer body 70, and are collectively applied to the recording member P. The image is transferred and fixed by the fixing device 24 by pressing and heating. The photoreceptors 1Y, 1M, 1C, and 1K after transferring the toner image to the recording member P are cleaned with the cleaning device 6A to remove the toner remaining on the photoreceptor, and then the above-described charging, exposure, and development cycle. The next image formation is performed.

  Next, an image forming method when the toner according to the present invention is used as a non-magnetic one-component developer will be described. FIG. 2 is an example of a full-color image forming apparatus that uses a non-magnetic one-component developer. An image forming apparatus 100 shown in FIG. 2 is a typical image forming apparatus in which the above-described developing device 20 can be mounted. 2 includes a charging brush 2 for uniformly charging the surface of the photosensitive drum 1 to a predetermined potential around a rotating electrostatic latent image carrier (hereinafter also referred to as a photosensitive drum) 1, and a photosensitive member. A cleaner 6 for removing residual toner on the drum 1 is provided.

  The laser scanning optical system 3 scans and exposes the photosensitive drum 1 uniformly charged by the charging brush 2 to form an electrostatic latent image on the photosensitive drum 1. The laser scanning optical system 3 includes a laser diode, a polygon mirror, and an fθ optical element, and print data for each of yellow, magenta, cyan, and black is transferred from the host computer to the control unit. Based on the print data for each color, a laser beam is sequentially output, and the photosensitive drum 1 is scanned and exposed to form an electrostatic latent image for each color.

  The developing device unit 40 that accommodates the developing device 4 supplies toner of each color to the photosensitive drum 1 on which the electrostatic latent image is formed to perform development. The developing device unit 40 is provided with four developing devices 4Y, 4M, 4C, and 4Bk each containing non-magnetic one-component toners of yellow, magenta, cyan, and black around the support shaft 33. Rotating to the center, each developing device 4 is guided to a position facing the photosensitive drum 1.

  The developing device unit 40 rotates around the support shaft 33 each time an electrostatic latent image of each color is formed on the photosensitive drum 1 by the laser scanning optical system 3, and stores the corresponding color toner. 4 is guided to a position facing the photosensitive drum 1. Then, each of the developing devices 4Y, 4M, 4C, and 4Bk sequentially supplies each charged color toner to the photosensitive drum 1 for development.

  In the image forming apparatus of FIG. 2, an endless intermediate transfer belt 7 is provided downstream of the developing device unit 40 in the rotation direction of the photosensitive drum 1, and is driven to rotate in synchronization with the photosensitive drum 1. The intermediate transfer belt 7 comes into contact with the photosensitive drum 1 at a portion pressed by the primary transfer roller 5 and transfers a toner image formed on the photosensitive drum 1. Further, a secondary transfer roller 73 is rotatably provided so as to face the support roller 72 that supports the intermediate transfer belt 7, and on the intermediate transfer belt 7 at a portion where the support roller 72 and the secondary transfer roller 73 face each other. The toner image is pressed and transferred onto a recording material P such as recording paper.

  A cleaner 8 for removing residual toner on the intermediate transfer belt 7 is provided between the full-color developing device unit 40 and the intermediate transfer belt 7 so as to be able to contact with and separate from the intermediate transfer belt 7.

  The paper feeding means 60 that guides the recording material P to the intermediate transfer belt 7 includes a paper feeding tray 61 that houses the recording material P, and a paper feeding roller 62 that feeds the recording material P stored in the paper feeding tray 61 one by one. It is composed of a timing roller 63 for feeding the fed recording material P to the secondary transfer site.

  The recording material P to which the toner image has been pressed and transferred is conveyed to the fixing device 24 by a conveying means 66 constituted by an air suction belt or the like, and the toner image transferred by the fixing device 24 is fixed on the recording material P. After fixing, the recording material P is transported through the vertical transport path 80 and discharged onto the upper surface of the apparatus main body 100.

  The image forming apparatus shown in FIG. 2 is one in which a replaceable developing device 4 is loaded to form an image. The developing device 4 shown in FIG. 3A is usually called a toner cartridge, and stores a predetermined amount of toner inside a part where components such as a developing roller are arranged. The developing device supplied in the form of a toner cartridge is loaded at a predetermined position in the image forming apparatus, and then the developer stored therein is supplied to the photosensitive drum for development, and a predetermined number of images are formed and developed. When the agent runs out, it is removed from the apparatus and a new toner cartridge is loaded.

  FIG. 3B is a schematic diagram illustrating an example of a cross-sectional configuration of the developing device 4. Hereinafter, the developing device 4 is also referred to as a toner cartridge 4. The toner cartridge 4 has a buffer chamber 42 adjacent to the developing roller 41 and a hopper 43 adjacent to the buffer chamber 42.

  The developing roller 41 has a conductive cylindrical base and an elastic layer formed on the outer periphery of the base using a material having high hardness such as silicone rubber.

  In the buffer chamber 42, a blade 44, which is a toner regulating member, is disposed in pressure contact with the developing roller 41. The blade 44 regulates the charge amount and adhesion amount of toner on the developing roller 41. It is also possible to further provide an auxiliary blade 45 for assisting regulation of the toner charge amount and adhesion amount on the developing roller 41 on the downstream side of the blade 41 with respect to the rotation direction of the developing roller 41.

  A supply roller 46 is pressed against the developing roller 41. The supply roller 46 is driven to rotate in the same direction as the developing roller 41 (counterclockwise direction in the drawing) by a motor (not shown). The supply roller 46 has a conductive cylindrical substrate and a foam layer formed of urethane foam or the like on the outer periphery of the substrate.

  The hopper 43 contains toner T as a one-component developer. The hopper 43 is provided with a rotating body 47 for stirring the toner. A film-like conveying blade is attached to the rotating body 47, and the toner is conveyed by the rotation of the rotating body 47 in the arrow direction. The toner conveyed by the conveying blades is supplied to the buffer chamber 42 through a passage 44 provided in a partition wall that separates the hopper 43 and the buffer chamber 42.

  The shape of the conveying blade is bent while conveying the toner in front of the rotation direction of the blade as the rotating body 47 rotates, and returns to a straight state when the left end of the passage 48 is reached. In this way, the blades return the toner to the passage 48 by returning the shape straight after passing through the curved state.

  The passage 48 is provided with a valve 321 for closing the passage 48. This valve is a film-like member, one end of which is fixed to the upper right side surface of the passageway 48 of the partition wall. When toner is supplied from the hopper 43 to the passageway 48, the passageway 48 is opened by being pushed rightward by the pressing force from the toner. It is like that. As a result, toner is supplied into the buffer chamber 42.

  Further, a regulating member 322 is attached to the other end of the valve 321. The regulating member 322 and the supply roller 46 are arranged so as to form a slight gap even when the valve 321 closes the passage 48. The regulating member 322 adjusts so that the amount of toner accumulated at the bottom of the buffer chamber 42 does not become excessive, so that a large amount of toner collected from the developing roller 41 to the supply roller 46 does not fall to the bottom of the buffer chamber 42. Adjusted.

  In the toner cartridge 4, the developing roller 41 is rotated in the direction of the arrow during image formation, and the toner in the buffer chamber 42 is supplied onto the developing roller 41 by the rotation of the supply roller 46. The toner supplied onto the developing roller 41 is charged and thinned by a blade 44 and an auxiliary blade 45 and then transported to a region facing the image carrier to develop an electrostatic latent image on the image carrier. Provided. The toner that has not been used for development returns to the buffer chamber 42 as the developing roller 41 rotates, and is scraped and collected from the developing roller 41 by the supply roller 46.

  The toner according to the present invention does not change the crystal structure of the colorant in the toner at the heating temperature at the time of fixing in the prior art, and a toner image having stable color reproducibility can be obtained with a known fixing device. can get. By the way, in recent years, there is a movement to reduce the energy consumption of the image forming apparatus from the viewpoint of consideration for the global environment. Among them, the reduction of energy consumption in the fixing process has attracted attention, and so-called low-temperature fixing technology that fixes a toner image at a temperature lower than the current fixing temperature has been adopted.

  That is, when the toner according to the present invention is a toner compatible with low-temperature fixing, the surface temperature of the heating member in the fixing device is preferably set to less than 140 ° C., and the surface temperature of the heating member is set to less than 130 ° C. Is more preferable.

  Under the set temperature, it is required to efficiently supply the heat supplied from the heating member to the transfer sheet, and so-called belt fixing using a heat-resistant belt for either the heating member or the pressure member. A fixing method is preferred.

  FIG. 4 shows an example of a belt fixing type fixing device (a type using a belt and a heating roller) capable of fixing the toner according to the present invention.

  The fixing device 24 shown in FIG. 4 is a type that uses a belt and a heating roller to secure a nip width, and is pressed against the fixing roller 240 via the fixing roller 240, the seamless belt 241, and the seamless belt 241. The pressure pad (pressure member) 242a, the pressure pad (pressure member) 242b, and the lubricant supply member 243 constitute main parts.

  The fixing roller 240 is formed of a heat-resistant elastic layer 240b and a release layer (heat-resistant resin layer) 240c around a metal core (cylindrical metal core) 240a, and a heat source is provided inside the core 240a. A halogen lamp 244 is arranged.

  The surface temperature of the fixing roller 240 is measured by the temperature sensor 245, and the halogen lamp 244 is feedback-controlled by a temperature controller (not shown) based on the measurement signal so that the surface of the fixing roller 240 is adjusted to a constant temperature. The seamless belt 241 contacts the fixing roller 240 so as to be wound at a predetermined angle, thereby forming a nip portion.

  Inside the seamless belt 241, a pressure pad 242 having a low friction layer on its surface is disposed in a state of being pressed against the fixing roller 240 via the seamless belt 241. The pressure pad 242 is provided with a pressure pad 242a to which a strong nip pressure is applied and a pressure pad 242b to which a weak nip pressure is applied, and is held by a holder 242c made of metal or the like.

  A belt traveling guide is attached to the holder 242c so that the seamless belt 241 slides and rotates smoothly. The belt running guide is preferably a member having a low coefficient of friction because it rubs against the inner surface of the seamless belt 241, and a member having low heat conduction is preferable so that heat is not easily removed from the seamless belt 241. In addition, as a specific example of the material of the seamless belt 241, a polyimide is mentioned, for example.

  The toner image formed with the toner according to the present invention is finally transferred onto the transfer material P, and fixed on the transfer material by a fixing process to form an image. The transfer material P used for the image formation is a support for holding a toner image, and is usually called an image support, a recording material, or transfer paper.

  Specifically, various transfer materials such as plain paper and fine paper from thin paper to thick paper, coated printing paper such as art paper and coated paper, commercially available Japanese paper and postcard paper, plastic film for OHP, cloth, etc. However, it is not limited to these.

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

Example 1
[Production of toner]
<< Production of Toner 1 (Kneading / Crushing Method) >>
The following toner composition was 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)
Exemplified compound 1-1 6 parts by mass Silanol compound (Exemplary compound (2) -2) 0.05 part by weight Release agent (pentaerythritol tetrastearate) 6 parts by mass Charge control agent (boron dibenzylate) 1 part by mass After kneading with a twin-screw extrusion kneader, then coarsely pulverizing with a hammer mill, pulverizing with a turbo mill pulverizer (manufactured by Turbo Kogyo), and further performing fine powder classification with an airflow classifier utilizing the Coanda effect, Colored particles having a reference median diameter of 5.5 μm were obtained.

  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.

<< Production of Toner 2 (Kneading / Crushing Method) >>
Toner 2 was produced in the same manner as Toner 1 except that Exemplified Compound 1-1 was changed to Exemplified Compound DYM-1.

<< Production of Toner 3 (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, and dissolved and stirred to prepare an aqueous surfactant solution. In this surfactant aqueous solution, Illustrative Compound 1-1, 6 parts by mass and Silanol Compound (Exemplary Compound (2) -2) and 0.05 part by mass are gradually added as a colorant, and “Clearmix W Motion CLM” is added. -0.8 "(manufactured by M Technique) was used for dispersion treatment to prepare" Colorant fine particle dispersion 1 ".

  “Colorant fine particle 1” in “Colorant fine particle dispersion 1” had a volume-based median diameter of 98 nm. The volume-based median diameter was 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 In a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introduction device, 4 parts by mass of an anionic surfactant shown below (Structural Formula 1) together with 3040 parts by mass of ion-exchanged water 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 weight n-butyl acrylate 200 parts by weight Methacrylic acid 68 parts by weight n-octyl mercaptan 16.4 parts by weight After the above monomer mixture was added dropwise, the system was heated and stirred at 75 ° C. for 2 hours. Thus, 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)” as a mold release agent. 8 parts by mass was added and heated to 90 ° C. to dissolve. 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. After adding 32.8 parts by mass (in terms of solid content) of the above-mentioned “resin particles A1” to this surfactant aqueous solution, and further adding the monomer solution containing the paraffin wax, mechanical dispersion having a circulation path It was mixed and dispersed for 8 hours using a “CLEAMIX (M-Technic)” machine. By the mixing and dispersion, an emulsified particle dispersion containing emulsified particles having a dispersed particle size of 340 nm was prepared.

  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 this system is heated and stirred at 98 ° C. for 12 hours. Polymerization (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 dropping, the mixture is heated and stirred for 2 hours to perform polymerization (third stage polymerization), and after completion of polymerization. Then, it was cooled to 28 ° C. to produce “core part resin particles 1”. The “core part resin particles 1” produced by the third stage polymerization 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 The following was put into a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device, and stirred.

Resin particle for core part 420.7 parts by mass (solid content conversion)
900 parts by mass of ion-exchanged water 1 200 parts by mass of colorant particle dispersion 1 After adjusting the temperature in the reaction vessel to 30 ° C., a 5 mol / L aqueous sodium hydroxide solution was added to adjust the pH to 8 to 11.

  Next, an aqueous solution in which 2 parts by mass of magnesium chloride hexahydrate was dissolved in 1000 parts by mass of ion-exchanged water was added over 10 minutes at 30 ° C. 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 added to ion-exchanged water. The association was stopped by adding an aqueous solution dissolved in 1000 parts by mass.

  After the association was stopped, as the aging treatment, the liquid temperature was set to 70 ° C., and the mixture was heated and stirred for 1 hour to continue the fusion, thereby producing “core part 1”.

  The average circularity of the “core part 1” was measured by “FPIA2000 (manufactured by Systex)” and found to be 0.912.

(B) Formation of shell Next, the above-mentioned liquid is brought to 65 ° C., and 96 parts by mass of “shell resin particles 1” is added, and further 2 parts by mass of magnesium chloride hexahydrate is dissolved in 1000 parts by mass of ion-exchanged water. After the added 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 portion 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 produced 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 the following characteristics were prepared.

(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”.

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.

<< Production of Toners 4 to 26 (Emulsion Association Method) >>
In the production of “Toner 3”, Exemplified Compound 1-1 is converted to Exemplified Compound 1-2, 1-4, 1-5, 1-7, 1-9, 1-15, 1-17, 1-19, 1- 20, 1-23, 1-25, 1-27, 1-28, 1-33, 1-36 and exemplary compounds DYM-1, DYM-18, DYM-22, DYM-29, DYM-46, DYM Toners 3 to 18 and Toners 19 to 26 were produced in the same manner as Toner 3 except that they were changed to -50, DYM-64, and DYM-73.

<< Production of Toners 27 to 30 and 31 (Emulsion Association Method) >>
Toners 27 to 30 and 31 were prepared in the same manner as in the production of “Toner 3”, except that Comparative Compounds 1 to 4 and 5 were used instead of Example Compound 1-1.

(Preparation of developer)
The above “toners 1 to 31” were mixed with a silicone carrier-coated ferrite carrier having a volume average particle diameter of 60 μm to prepare “developers 1 to 31” having a toner concentration of 6%.

[Evaluation]
Evaluation was performed by loading a developing device with each developer into a commercially available composite printer “bizhub Pro C500 (manufactured by Konica Minolta Business Technologies, Inc.)” corresponding to the two-component developing type image forming apparatus of FIG. I went.

  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 as follows.

Fixing speed: 230mm / sec
Heat roller surface material: Polytetrafluoroethylene (PTFE)
Heat roller surface temperature: 125 ° C.

  In the evaluation, the toner prepared above was loaded in the evaluation device in order, and the following items were evaluated in an environment of normal temperature and normal humidity (20 ° C., 55% RH).

  The print is performed in an environment of normal temperature and humidity (25 ° C., 55% RH), each of a halftone image having an image density of 0.4, a solid white image, a solid black image having an image density of 0.8, and a fine line image. / 4 A4 size printing was performed.

<Hue angle>
Measure the a ^* and b ^* values of cyan and magenta toners using a color meter “SPM50” (manufactured by Gretag) using a single color image on a copy sheet, determine the hue angle from those values, and evaluate according to the following criteria did.

(Cyan toner hue angle)
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 185 ° ≦ h <200 ° and 220 ° <h ≦ 225 ° is B
A toner whose hue angle of cyan toner is in the range of 170 ° ≦ h <185 °, 225 ° <h ≦ 230 ° is C
The toner in which the hue angle of the cyan toner is in the range of 170 °> h and h> 230 ° is D.

(Magenta toner hue angle)
A toner whose hue angle of magenta toner is in the range of 310 ° ≦ h ≦ 330 ° is A
A toner whose hue angle of magenta toner is in the range of 305 ° ≦ h <310 ° and 330 ° <h ≦ 335 ° is B
A toner whose hue angle of magenta toner is in the range of 300 ° ≦ h <305 °, 335 ° <h ≦ 340 ° is C
The toner in which the hue angle of the magenta toner is in the range of 300 °> h and h> 340 ° is D.

  Tables 1 and 2 show the evaluation results of the hue angle of the cyan toner and the magenta toner according to the above ranking.

<Color reproducibility>
The color reproducibility of the mixed color image on the copy paper was evaluated according to the following evaluation criteria by visual evaluation with 10 monitors. The toner adhesion amount was evaluated in the range of 0.7 ± 0.05 (mg / cm ² ).

A: Excellent color reproducibility (bright color)
○: Excellent color reproducibility △: Slight color contamination, but at a level that is practically acceptable (slightly turbid color)
X: Color contamination is large and there is a problem in image quality (appears blue or cloudy blue).

<Light resistance>
The mixed color image on the copy paper is irradiated with a xenon fade meter for 7 days, and the residual ratio of the dye in the portion near density 1 before irradiation ({(density before irradiation−density after irradiation) / density before irradiation} × 100%) Was evaluated according to the following evaluation criteria. The mixed color image was evaluated based on the hue change and the residual ratio of the magenta dye. 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 10 to 9 points, the average score of 10 people was 9 to 8 points, the average score of 10 people was 8 to 7 points, and the less than 7 points was rated as x.

(Dye remaining rate)
5: Residual density is 90% or more 4: Residual density is less than 90-80% 3: Residual density is less than 60-70% 2: Residual density is less than 70-60% 1: Residual density is less than 60% Image density is reflected It measured using the densitometer (X-Rite310TR).

<Ozone resistance>
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. The dye residual ratio of the cyan dye of each color and the mixed color image was measured using a reflection densitometer (X-Rite 310TR) after a certain period of time from the start of exposure.

The reflection density was measured at three points of 0.7, 1.0, and 1.8. From the obtained results, the dye residual ratio (R _OD (%)) = {(concentration before exposure−concentration after exposure) / concentration before exposure} × 100% was determined. Further, based on the results of the above test, the ozone resistance of each color recorded on the recorded material was ranked 5 to 1 using the following criteria.

5: _ROD after 7 days from the start of the test is 85% or more at any concentration 4: _ROD after 7 days from the start of the test, the concentration at any one point is less than 85% 3: 7 days after the start of the test The _ROD of any two points is less than 85% 2: The _ROD after 7 days from the start of the test is less than 80% of any 2 points 1: The _ROD after 7 days from the start of the test Less than 75% at all concentrations.

  Moreover, about the color-mixed image, the hue change before and behind ozone exposure was visually observed by 10 test subjects, and evaluation was performed on a 10-point scale. The average score of 10 people was 10 to 9 points, the average score of 10 people was 9 to 8 points, the average score of 10 people was 8 to 7 points, and the less than 7 points was rated as x.

  Table 3 shows the evaluation results of color reproducibility, light resistance, and ozone resistance for the mixed color image.

  As is clear from Tables 1 and 2, since the toner set using the cyan colorant and the magenta colorant exhibits an excellent hue angle, the color toner of the present invention is suitable for use as a full color toner. Furthermore, as shown in Table 3, since the color reproducibility, light resistance, and ozone resistance when mixed colors are used, the color reproducibility of the monitor image is high, and an image that can be stored for a long time is provided. Is possible.

1 Photoconductor (Photoconductor drum)
4 Development device (toner cartridge)
6 Cleaning Device 7 Intermediate Transfer Belt 10 Image Forming Unit 24 Fixing Device 240 Heating Roller 241 Pressure Belt (Seamless Belt)
P Transfer material (recording material)

Claims (4)

An electrophotographic toner set having at least a yellow toner, a magenta toner, and a cyan toner contains a colorant represented by the following general formula (1) in the cyan toner, and an L ^* a ^* b ^* table of the cyan toner. The hue angle (h) according to the color system is 170 ° ≦ h ≦ 230 °, and the hue angle (h) according to the L ^* a ^* b ^* color system of the magenta toner is 300 ° ≦ h ≦ 340 °. A toner set for electrophotography.

(Wherein X ₁ , X ₂ , X ₃ and X ₄ represent a hydrogen atom, an alkyl group, an alkoxy group or an aryloxy group, and may be the same or different. N represents 1 or 2. )   2. The toner set for electrophotography according to claim 1, wherein the magenta toner contains at least one anthraquinone compound as a colorant.   2. The electrophotographic toner set according to claim 1, wherein the magenta toner contains at least one azo compound having a heterocyclic ring as a colorant. The toner set for electrophotography according to claim 1, wherein the magenta toner contains at least one compound represented by the following general formula (DX-1) as a colorant.

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

Images