JP5125549B2 - Color toner for electrophotography - Google Patents

Description

  The present invention relates to a color toner for electrophotography using a heat roller type fixing method.

  As disclosed in various electrophotographic methods, it is generally necessary to form an electrostatic latent image of electrostatic charge on a photoreceptor containing a photoconductive material by various means, and then develop the latent image as a powder image with toner. The powder image is transferred to paper or the like according to the above, and then fixed by heating, pressing, solvent vapor, light, or the like.

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

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

  First, an electrostatic latent image is formed on the photoconductor by irradiating light information corresponding to image information on the photoconductor composed of a photoconductive material by various methods. Next, the electrostatic latent image formed on the photoreceptor is developed as a toner image with charged toner, and the toner image is transferred to an image recording medium (such as plain paper or an intermediate transfer member). Let it settle. A color image is formed by repeating this development process four times for each color (yellow, magenta, cyan, black).

  Specifically, the fixing method is a method of fixing an image on plain paper using a heat fixing device (heat roller method) and light-to-heat conversion with an infrared absorber contained in the toner by irradiating light such as a xenon light source. There is a flash fixing method in which fixing is performed (see Patent Document 6). In addition to the flash fixing method, invisible information is embedded as additional data separately from the visible image (because it does not contain a colorant) with a toner containing an infrared absorber, thereby protecting copyright, preventing unauthorized copying, and preventing counterfeiting. In recent years, the spread of color electrophotography and its field of use, such as the intended toner (see Patent Document 7), have been expanding.

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

  As a method of eliminating the disadvantages of the pigment, for example, by using a flushing method as a pigment dispersion method, the transparency of the pigment is improved by achieving a pigment dispersion diameter on the order of submicron with primary particles without aggregated secondary particles. And 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 (see Patent Document 1). However, even in the case of outputting with the toner proposed in these cases, it is still difficult to obtain sufficient transparency in the case of the toner using pigment.

  On the other hand, a toner using a dye (see Patent Document 2), a toner mixed with a dye and a pigment, and the like have been disclosed. Generally, in a toner using a dye, the dye is dissolved in the binder resin of the toner. Since it exists in a state, it has excellent transparency, saturation and the like, but has a drawback that light resistance and heat resistance are greatly inferior to pigments. Regarding heat resistance, in addition to the decrease in density due to the decomposition of the dye, when the toner image is fixed by a heat roller, the dye is sublimated and easily causes internal contamination, and the dye dissolves in the silicone oil used for fixing. Finally, there was a problem of causing an offset phenomenon by fusing to a heating roll. As a proposal to eliminate these disadvantages of dyes, for example, means for making light resistance, sublimation and color reproducibility compatible by using a specific anthraquinone dye or chelate dye as magenta toner (see Patent Document 3) An encapsulated toner in which a core containing a polymer resin and a color dye is coated with a polymer (see Patent Document 4), and a toner with high saturation, for example, a toner using a squarylium dye (see Patent Document 5). Although proposed, these squarylium dyes have not yet been satisfactory in terms of storage stability (especially thermal stability).

In addition, even when the toner is output using the toners proposed in these cases, it is still difficult to obtain sufficient heat resistance (sublimation) and light resistance in the case of a toner using a dye. Development is desired.
JP-A-11-160914 JP-A-5-11504 Japanese Patent No. 3567403 Japanese Patent Laid-Open No. 5-72792 JP 2000-345059 A JP 2005-99419 A JP 2005-227370 A

  The present invention has been made to solve the above-described problems, and its object is to provide color toners for electrophotography (hereinafter referred to as color toners or simply toners) that are excellent in transparency, color reproducibility, and light resistance. (Also referred to as).

The electrophotographic color toner of the present invention is characterized in that colored fine particles comprising an oil-soluble dye having a specific structure and an infrared absorber are dispersed in a thermoplastic resin (hereinafter also referred to as a binder resin). That is, the above object of the present invention is achieved by the following means.
1.
In the color toner for electrophotography used in the electrophotography using the heat roller fixing method,
An electrophotographic color toner comprising an oil-soluble dye represented by any one of the following general formulas (1) to (4) and an infrared absorbent represented by the following general formula (5) .

[Wherein, Q ₁ and Q ₂ represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring, and may be further condensed or have a substituent. L _{1 to} L ₁₀ each represents a substituted or unsubstituted methine group, and R ₁ and R ₂ each represent a substituent. m1, m2, n1, and n2 each represents 0 or 1. ]

[Wherein, R ₁₁ , R ₁₂ , R ₁₉ and R ₂₀ each represent a substituent, and R ₁₃ and R ₁₄ each represent a hydrogen atom or a substituent. R ₁₅ represents ═N ⁺ (R ₁₆ ) R ₁₇ or ═O ⁺ R ₁₈ , and R ₁₆ , R ₁₇ and R ₁₈ each represent a hydrogen atom or a substituent. p1 and p2 each represent an integer of 0 to 3. When p1 or p2 is 2 or 3, a plurality of R ₁₁ or R ₁₂ may be the same or different. ]

[Wherein R ₂₁ and R ₂₃ each represent a hydrogen atom or a substituent, R ₂₂ represents —N (R ₂₄ ) R ₂₅ or —OR ₂₆ , and A ₂₁ and A ₂₂ each represent —C (R ₂₇ ) = Or -N =, X ₂₁ represents an atomic group necessary for forming a 5- or 6-membered aromatic ring or heterocyclic ring, and Z ₂₁ represents a 5- or 6-membered group containing at least one nitrogen atom. It represents an atomic group necessary for forming a heterocyclic ring, may have a substituent, and may further form a condensed ring. R _{24 to} R ₂₇ each represents a hydrogen atom or a substituent. q represents an integer of 0 to 3, and when q is 2 or more, the plurality of R ₂₁ may be the same or different. L ₂₁ represents a single bond or a divalent linking group, L ₂₂ , L ₂₃ and L ₂₄ represent a methine group which may have a substituent, and n ₂₁ represents 0 or 1. ]

[Wherein R ₃₁ and R ₃₃ each represent a hydrogen atom or a substituent, and Z ₃₁ represents an atomic group necessary for forming a 5- or 6-membered heterocyclic ring containing at least one nitrogen atom, It may have a group and may further form a condensed ring, and Q ₃₁ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. It may have a group. L ₃₁ , L ₃₂ , L ₃₄ and L ₃₅ each represents an optionally substituted methine group, L ₃₃ represents a single bond or a divalent linking group, and R ₃₂ represents a substituent. n31 represents 1 or 2, and n32 represents 0 or 1. r represents an integer of 0 to 2, and when r is 2, a plurality of R ₃₁ may be the same or different . ]

[Wherein, R ₅₁ , R ₅₂ , R ₆₁ , R ₆₂ , R ₇₁ , R ₇₂ , R ₈₁ and R ₈₂ each represent a hydrogen atom, an aliphatic group or an aromatic group, and R ₄₀ , R ₅₃ , R ₆₃ , R ₇₃ and R ₈₃ each represent a substituent, n40, n41, n42, n43 and n44 each represent an integer of 0 to 4, and n45 represents 1 or 2. X represents a monovalent or divalent anion, and the product of the valence of X and n45 is 2. ]
2.
2. The general formula (5), wherein X is a perchlorate ion, a carboxylate ion, a sulfonate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, or a hexafluoroantimonate ion. Color toner for electrophotography.
3.
In the general formula (5), X is ClO ₄ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , CF ₃ SO ₂ N ^— SO ₂ CF ₃ , C ₂ F ₅ CON ^— SO ₂ CF ₃ , (CF ^{_{3 SO 2) 3 C -,}} CF 3 SO 3 - electrophotographic color toner according to the item 1, characterized by being represented by.
4).
4. The color toner for electrophotography according to any one of items 1 to 3, wherein the oil-soluble dye is a methine dye or a squarylium dye.
5.
5. The electrophotographic color toner according to any one of items 1 to 4, wherein the electrophotographic color toner is a polymerized toner.
6).
6. The color toner for electrophotography according to any one of 1 to 5, wherein the oil-soluble dye has a light absorption peak in a wavelength range of 600 to 700 nm.

  According to the present invention, an electrophotographic color toner having excellent transparency, color reproducibility, and light resistance can be provided.

  Hereinafter, the present invention will be described in more detail. First, materials constituting the color toner of the present invention will be described.

<Compound represented by formula (1)>
In the general formula (1), Q ₁ and Q ₂ represent an atomic group necessary for forming a 5-membered or 6-membered nitrogen-containing heterocycle and may be condensed or have a substituent. L _{1 to} L ₁₀ each represents an unsubstituted or substituted methine group, and R ₁ and R ₂ each represent a substituent. m1, m2, n1, and n2 each represents 0 or 1;

Preferred examples of the heterocyclic ring formed by Q ₁ and Q ₂ include benzothiazole, benzoxazole, benzoselenazole, benzotelrazole, 2-quinoline, 4-quinoline, benzimidazole, thiazoline, indolenine, oxadiazole. , Thiazole, imidazole nucleus, etc. In addition to the benzene ring, examples of the condensed ring include a pyridine ring, a thiophene ring, and the like. More preferred are benzothiazole, benzoxazole, benzimidazole, benzoselenazole, 2- (Or 4-) quinoline and indolenine nucleus, particularly preferably benzothiazole, benzoxazole, 2- (or 4-) quinoline and indolenine nucleus.

  As substituents on these rings, carboxyl group, phosphono group, sulfo group, halogen atom (fluorine, chlorine, bromine, iodine), cyano group, alkoxy group (methoxy, ethoxy, i-propoxy, methoxyethoxy, etc.), aryl Oxy groups (phenoxy, etc.), alkyl groups (methyl, ethyl, t-butyl, cyclopropyl, cyclohexyl, trifluoromethyl, methoxyethyl, allyl, benzyl, etc.), alkylthio groups (methylthio, ethylthio, etc.), alkenyl groups ( Vinyl, 1-propenyl, etc.), aryl groups (phenyl, thienyl, toluyl, chlorophenyl, etc.) and the like are mentioned, preferably a halogen atom, an alkyl group, an alkoxy group, and a hydrogen atom is also preferred.

L _{1 to} L ₁₀ each represents a methine group which may have a substituent, and the substituent includes a substituted or unsubstituted alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 1 carbon atoms). 7 methyl, ethyl, propyl, i-propyl, cyclopropyl, butyl, 2-carboxyethyl, benzyl and the like, a substituted or unsubstituted aryl group (preferably having 6 to 10 carbon atoms, more preferably 6 to 8 carbon atoms). , Phenyl, toluyl, chlorophenyl, o-carboxyphenyl, etc.), heterocyclic groups (pyridyl, thienyl, furanyl, pyridyl, barbituric acid, etc.), halogen atoms (chlorine, bromine, etc.), alkoxy groups (methoxy, ethoxy, etc.) An amino group (preferably having 1 to 12 carbon atoms, more preferably 6 to 12, diphenylamino, methylphenylamino, 4-acetylpiperazi 1-yl, etc.), etc. oxo group. These substituents on the methine group may be linked to each other to form a ring such as cyclopentene, cyclohexene, squarylium ring, etc., or may form a ring with an auxiliary color group. An alkyl group and a halogen atom are preferred, but an unsubstituted methine group is particularly preferred.

The substituents represented by R ₁ and R ₂ are each preferably an aromatic group or an aliphatic group that may have a substituent, and the aromatic group preferably has 1 to 16 carbon atoms, more preferably Is 5 or 6. The number of carbon atoms of the aliphatic group is preferably 1 to 18, more preferably 4 to 18, but the total number of carbon atoms of R ₁ and R ₂ is more preferably 17 or more. Examples of the unsubstituted aliphatic group and aromatic group include groups such as methyl, ethyl, propyl, butyl, octyl, decyl, i-hexadecyl, phenyl, and naphthyl.

The substituent that Q ₁ and Q ₂ may have is not particularly limited as long as it can be substituted, but an alkyl group (methyl, ethyl, propyl, isopropyl, t-butyl, pentyl, hexyl, octyl, Dodecyl, tridecyl, tetradecyl, pentadecyl, trifluoromethyl, etc.), cycloalkyl groups (cyclopentyl, cyclohexyl, etc.), alkenyl groups (vinyl, allyl, etc.), alkynyl groups (ethynyl, propargyl, etc.), aryl groups (phenyl, naphthyl, etc.) , Heterocyclic groups (furyl, thienyl, pyridyl, pyridazyl, pyrimidyl, pyrazyl, triazyl, imidazolyl, pyrazolyl, thiazolyl, benzoimidazolyl, benzoxazolyl, quinazolyl, phthalazyl, pyrrolidyl, imidazolidyl, morpholyl, oxazolidyl), alcohol Xy group (methoxy, ethoxy, propyloxy, pentyloxy, hexyloxy, octyloxy, dodecyloxy, etc.), cycloalkoxy group (cyclopentyloxy, cyclohexyloxy, etc.), aryloxy group (phenoxy, naphthyloxy, etc.), alkylthio group ( Methylthio, ethylthio, propylthio, pentylthio, hexylthio, octylthio, dodecylthio, etc., cycloalkylthio groups (cyclopentylthio, cyclohexylthio, etc.), arylthio groups (phenylthio, naphthylthio, etc.), alkoxycarbonyl groups (methyloxycarbonyl, ethyloxycarbonyl, butyl) Oxycarbonyl, octyloxycarbonyl, dodecyloxycarbonyl, etc.), aryloxycarbonyl groups (phenyloxycarbonyl, Tiloxycarbonyl, etc.), sulfamoyl groups (aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, butylaminosulfonyl, hexylaminosulfonyl, cyclohexylaminosulfonyl, octylaminosulfonyl, dodecylaminosulfonyl, phenylaminosulfonyl, naphthylaminosulfonyl, 2- Pyridylaminosulfonyl, etc.), acyl groups (acetyl, ethylcarbonyl, propylcarbonyl, pentylcarbonyl, cyclohexylcarbonyl, octylcarbonyl, 2-ethylhexylcarbonyl, dodecylcarbonyl, phenylcarbonyl, naphthylcarbonyl, pyridylcarbonyl, etc.), acyloxy groups (acetyloxy, Ethylcarbonyloxy, butylcarbonyloxy, octylcarbo Ruoxy, dodecylcarbonyloxy, phenylcarbonyloxy, etc.), amide groups (methylcarbonylamino, ethylcarbonylamino, dimethylcarbonylamino, propylcarbonylamino, pentylcarbonylamino, cyclohexylcarbonylamino, 2-ethylhexylcarbonylamino, octylcarbonylamino, dodecyl Carbonylamino, phenylcarbonylamino, naphthylcarbonylamino, etc.), carbamoyl group (aminocarbonyl, methylaminocarbonyl, dimethylaminocarbonyl, propylaminocarbonyl, pentylaminocarbonyl, cyclohexylaminocarbonyl, octylaminocarbonyl, 2-ethylhexylaminocarbonyl, dodecyl) Aminocarbonyl, phenylaminocarbonyl, naphthy Ureidocarbonyl (2-pyridylaminocarbonyl, etc.), ureido group (methylureido, ethylureido, pentylureido, cyclohexylureido, octylureido, dodecylureido, phenylureido, naphthylureido, 2-pyridylaminoureido, etc.), sulfinyl group (methylsulfinyl) , Ethylsulfinyl, butylsulfinyl, cyclohexylsulfinyl, 2-ethylhexylsulfinyl, dodecylsulfinyl, phenylsulfinyl, naphthylsulfinyl, 2-pyridylsulfinyl, etc.), alkylsulfonyl groups (methylsulfonyl, ethylsulfonyl, butylsulfonyl, cyclohexylsulfonyl, 2-ethylhexyl) Sulfonyl, dodecylsulfonyl, etc.), arylsulfonyl groups (phenylsulfuryl) Nyl, naphthylsulfonyl, 2-pyridylsulfonyl, etc.), amino group (amino, ethylamino, dimethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, naphthylamino, 2-pyridylamino, etc.), cyano group , A nitro group, a halogen atom (fluorine, chlorine, bromine, etc.) and the like. These may be further substituted by the same substituent.

  Among these, alkyl groups, aryl groups, heterocyclic groups, alkoxy groups, sulfamoyl groups, ureido groups, amino groups, amide groups, acyl groups, alkoxycarbonyl groups, carbamoyl groups, cyano groups, halogen atoms and the like are preferable. Are more preferably an alkyl group, an aryl group, an alkoxy group, a carbamoyl group, a cyano group, an amide group, or a halogen atom.

  m1, m2, n1 and n2 each represent 0 or 1, but m1 and n1 are preferably 0 for ease of synthesis, and m2 and n2 are 0 from the point of the absorption waveform of the dye. Although it is preferable, it is not limited in terms of adjusting the absorption wavelength.

<Compound represented by formula (2)>
In the general formula (2), R ₁₁ , R ₁₂ , R ₁₉ and R ₂₀ each represent a substituent, and R ₁₃ and R ₁₄ each represent a hydrogen atom or a substituent. R ₁₅ represents ═N ⁺ (R ₁₆ ) R ₁₇ or ═O ⁺ R ₁₈ , and R ₁₆ , R ₁₇ and R ₁₈ each represent a hydrogen atom or a substituent. p1 and p2 each represent an integer of 0 to 3. When p1 or p2 is 2 or 3, a plurality of R ₁₁ or R ₁₂ may be the same or different.

The substituent represented by R ₁₉ and R ₂₀ is not particularly limited as long as it can be substituted, but is synonymous with the substituent that Q ₁ and Q ₂ in General Formula (1) may have.

Among the above substituents, a halogen atom, an alkyl group, an aryl group, an acyl group, an alkoxy group, an acylamino group, a sulfonylamino group, an alkylsulfonyl group, a hydroxyl group, and the like are preferable, and a hydroxyl group, an acylamino group, and a sulfonylamino are more preferable. It is a group. R ₁₉ and R ₂₀ may be the same or different. p1 and p2 each represent an integer of 0 to 3, and in the case of 2 or more, the plurality of R ₁₁ and R ₁₂ may be the same or different. P1 and p2 may be the same or different. p1 and p2 are each preferably 0 or 1.

Examples of the substituent represented by R ₁₃ and R ₁₄ include an alkyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, an acyloxy group, a carbamoyl group and the like, and further the substituents exemplified for the aforementioned R ₁₁ and R _12. It may have the same substituent as the group. R ₁₃ and R ₁₄ may be the same or different. R ₁₃ and R ₁₄ are preferably a hydrogen atom, an alkyl group, an aryl group, an acyl group, or a sulfonyl group, and more preferably an alkyl group or an aryl group.

R ₁₅ represents ═N ⁺ (R ₁₆ ) R ₁₇ or ═O ⁺ R ₁₈ , where R _{16 to} R ₁₈ each represents a hydrogen atom or a substituent.

R ₁₆ and R ₁₇ have the same meanings as R ₁₃ and R ₁₄ , respectively, preferably a hydrogen atom, an alkyl group, an aryl group, an acyl group, and a sulfonyl group, and more preferably an alkyl group and an aryl group. The combination of R ₁₃ and R _{14 and} the combination of R ₁₆ and R ₁₇ may be the same or different.

Examples of the substituent represented by R ₁₈ include an alkyl group, a carbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkylcarbonylamino group, an arylcarbonylamino group, and the like, which are further represented by the aforementioned R ₁₁ and R ₁₂ . A group similar to the above-described substituents may be substituted. R ₁₈ is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.

R < ₁₃ > -R < ₁₅ > is synonymous with R < ₃ > -R < ₅ > in the said General formula (1).

<Compound represented by formula (3)>
In the general formula (3), R ₂₁ and R ₂₃ each represent a hydrogen atom or a substituent, R ₂₂ represents —N (R ₂₄ ) R ₂₅ or —OR ₂₆ , and A ₂₁ and A _{22 each} represent —C (R ₂₇ ) ═ or —N═, X ₂₁ represents an atomic group necessary for forming a 5- or 6-membered aromatic ring or heterocyclic ring, and Z ₂₁ represents 5 or at least one nitrogen atom. It represents an atomic group necessary for forming a 6-membered heterocyclic ring, may have a substituent, and may further form a condensed ring. R _{24 to} R ₂₇ each represents a hydrogen atom or a substituent. q represents an integer of 0 to 3, and when q is 2 or more, the plurality of R ₂₁ may be the same or different. L ₂₁ represents a single bond or a divalent linking group, L ₂₂ , L ₂₃ and L ₂₄ each represents a methine group which may have a substituent, and n ₂₁ represents 0 or 1.

The substituent represented by R ₂₁ and R ₂₃ is not particularly limited as long as it can be substituted, and has the same meaning as the substituent R ₁ in the general formula (1). R ₂₁ is preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, a carbamoyl group, an alkoxycarbonyl group, an amide group, etc., more preferably an alkyl group, an aryl group, a heterocyclic group, or a carbamoyl group. Group, an alkoxycarbonyl group. R ₂₃ preferably includes an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an acylamino group, a sulfonamide group, and more preferably an alkyl group, an alkoxy group, and an acylamino group.

-N (R ₂₄ ) R ₂₅ or -OR ₂₆ represented by R ₂₂ is preferably -N (R ₂₄ ) R ₂₅ from the viewpoint of ε (molar extinction coefficient), but -OR from the viewpoint of wavelength adjustment. _{26 is} also preferred. R _{24 to} R ₂₆ each represents a hydrogen atom or a substituent, and examples of the substituent include those similar to R ₂₁ , preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group. More preferred are a hydrogen atom, an alkyl group, an aryl group, and an acyl group.

A ₂₁ and A ₂₂ each represent —C (R ₂₇ ) ═ or —N═, and preferably —C (R ₂₇ ) ═. R ₂₇ is a hydrogen atom or a substituent, and the substituent is synonymous with R ₂₁ . A hydrogen atom, a halogen atom, an alkoxycarbonyl group and the like are preferable, and a hydrogen atom is most preferable.

Examples of the 5- or 6-membered aromatic ring or heterocyclic ring represented by X ₂₁ include benzene, naphthalene, pyridine, pyrazine, furan, thiophene, imidazole, thiazole ring, etc., preferably benzene, pyridine, thiophene ring It is.

The 5- or 6-membered heterocyclic ring containing at least one nitrogen atom represented by Z ₂₁ is derived from pyridine, pyrimidine, quinoline, pyrazole, imidazole, pyrrole, pyrazolidine ring (pyrazolidine-3,5-dione, etc.), etc. And a ring may be formed, and a condensed ring may be further formed, and the following structures (a) to (f) are preferable.

<Structure represented by (a) and (b)>
The substituent represented by R ³¹ , R ³² , R ⁴¹ and R ⁴² has the same meaning as the group represented by R ₂₁ in the general formula (3), but R ³¹ and R ⁴¹ are each a hydrogen atom, Alkyl group, alkenyl group, aryl group, heterocyclic group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, amino group, alkylthio group, arylthio group, alkoxy group, aryloxy group, ureido group, alkoxycarbonylamino group, A carbamoyl group, a carboxyl group or an alkoxycarbonyl group, preferably an alkyl group, a carboxyl group, an alkoxyl group or a carbamoyl group, more preferably an alkyl group (especially methyl, t-butyl, trifluoromethyl) or a carbamoyl group. , An alkoxycarbonyl group.

R ³² and R ⁴² have the same meaning as the group represented by R ₂₃ in the general formula (3), and the same applies to the preferred groups.

A part of the linking group or ring structure having 1 or 2 carbon atoms represented by L ³¹ and L ⁴¹ has the same meaning as the group represented by L ₂₁ in the general formula (3), and the same applies to the preferred groups. It is.

<Structure represented by (c) and (d)>
The substituent represented by R ⁵¹ , R ⁵² , R ⁵³ , R ⁶¹ and R ⁶² has the same meaning as the group represented by R ₂₁ in the general formula (3), but R ⁵¹ represents a hydrogen atom or an alkyl group. , Aryl group, heterocyclic group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group, sulfamoyl group, alkylsulfonyl group or arylsulfonyl group, more preferably aryl group, heterocyclic group, carbamoyl. Group, alkoxycarbonyl group and cyano group.

R ⁵² is preferably a hydrogen atom, a halogen atom, an alkyl group, an acylamino group, an alkoxycarbonyl group, an amino group, an alkylthio group, an arylthio group or the like, and more preferably a hydrogen atom, a halogen atom, an alkyl group, or an acylamino group.

R ⁶¹ is a hydrogen atom, alkyl group, aryl group, heterocyclic group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, amino group, alkylthio group, arylthio group, alkoxyl group, aryloxy group, ureido group, alkoxy group. A carbonylamino group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, and the like are preferable, and a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acylamino group, and an alkoxy group are more preferable.

R ⁵³ and R ⁶² each have the same meaning as the group represented by R ₂₁ in the general formula (3), and the same applies to the preferred groups.

L ⁵¹ and L ⁶¹ each represent a linking group having 1 or 2 carbon atoms or a part of the ring structure, but are the same as the group represented by L ₂₁ in the general formula (3), and the same applies to the preferred groups. It is.

<Structure represented by (e) and (f)>
Examples of the substituent represented by ^{R 71, R 72, R 73} , R 81, R 82 and R ^83, but is synonymous with the groups represented by R ₂₁ in the general formula (3), R ⁷¹ and R ⁷² is preferably a hydrogen atom, alkyl group, aryl group, heterocyclic group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, carboxyl group, cyano group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group or nitro group, More preferred are an alkoxycarbonyl group and a cyano group.

R ⁸¹ is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an amino group, an alkylthio group, an arylthio group, an alkoxyl group, an aryloxy group, a ureido group, an alkoxycarbonyl An amino group, an acyl group, an alkoxycarbonyl group or a carbamoyl group is preferable, and a hydrogen atom, an alkyl group, an aryl group, an acyl group, an acylamino group, an alkoxycarbonyl group or a carbamoyl group is more preferable.

R ⁸² has the same meaning as the group represented by R ₃₁ in the general formula (3), and the same applies to the preferred groups.

R ⁷³ and R ⁸³ have the same meaning as the group represented by R ₂₃ in the general formula (3), and the same applies to the preferred groups.

A part of the linking group having 1 or 2 carbon atoms or the ring structure represented by L ⁷¹ and L ⁸¹ has the same meaning as the group represented by L ₂₁ in the general formula (3), and the preferred group is also synonymous. It is.

In the general formula (3), R ₂₃ is a chelatable group or a group substituted by a chelatable group (substituted or unsubstituted methylene group, ethylene group, ethyne group or aromatic group, heterocyclic group). It is also preferable. The chelatable group represents a substituent containing an atom having an unshared electron pair, and specifically includes a heterocyclic group, a hydroxyl group, a carbonyl group, an oxycarbonyl group, a carbamoyl group, an alkoxy group, and a heterocyclic oxy group. , Carbonyloxy group, urethane group, sulfonyloxy group, amino group, imino group, sulfonylamino group, sulfamoylamino group, acylamino group, ureido group, sulfonyl group, sulfamoyl group, alkylthio group, arylthio group, and heterocyclic thio Groups and the like. Preferred substituents include hydroxyl group, carbonyl group, oxycarbonyl group, carbamoyl group, alkoxy group, carbonyloxy group, urethane group, sulfonyloxy group, amino group, imino group, sulfonylamino group, acylamino group, ureido group, alkylthio group. Group, arylthio group, and more preferable substituents include hydroxyl group, carbonyl group, carbamoyl group, alkoxy group, sulfonylamino group, acylamino group and the like.

L ₂₁ represents a single bond or a divalent linking group, and L ₂₂ , L ₂₃ and L ₂₄ represent a methine group which may have a substituent, and the methine group represents L _{1 to} L in the general formula (1). Substituents that are synonymous with ₁₀ and may have are alkyl groups and halogen atoms, but unsubstituted methine groups are more preferred.

<Compound represented by formula (4)>
In the general formula (4), R ₃₁ and R ₃₃ each represent a hydrogen atom or a substituent, and Z ₃₁ represents an atomic group necessary for forming a 5- or 6-membered heterocyclic ring containing at least one nitrogen atom. Q ₃₁ represents an atomic group necessary for forming a 5-membered or 6-membered nitrogen-containing heterocycle, and may be further condensed. Or may have a substituent. L ₃₁ , L ₃₂ , L ₃₄ and L ₃₅ each represents an optionally substituted methine group, L ₃₃ represents a single bond or a divalent linking group, and R ₃₂ represents a substituent. n31 represents 1 or 2, and n32 represents 0 or 1. r represents an integer of 0 to 2, and when r is 2, a plurality of R ₃₁ may be the same or different.

The substituent represented by R ₃₁ and R ₃₃ is not particularly limited as long as it can be substituted, and has the same meaning as the substituent in formula (1). R ₃₁ has the same meaning as R ₂₁ in formula (3), and the same applies to the preferred substituents. R ₃₃ has the same meaning as R ₂₃ in formula (3), and the same applies to the preferred substituents.

The 5- or 6-membered heterocyclic ring containing at least one nitrogen atom represented by Z ₃₁ is the same as Z ₂₁ in the general formula (3), preferably in the general formulas (a) to (f). The structure represented is mentioned.

L ₃₁ , L ₃₂ , L ₃₄ and L ₃₅ are synonymous with L _{1 to} L ₈ in the general formula (1), and the substituent which may be present is preferably an alkyl group or a halogen atom, but is not substituted. A methine group is more preferred. L ₃₃ has the same meaning as L ₂₁ in formula (3).

Q ₃₁ has the same meaning as Q ₁ in formula (1), preferably benzothiazole, benzoxazole, benzimidazole, benzoselenazole, 2- (or 4-) quinoline, indolenine nucleus, particularly preferably benzo Thiazole, benzoxazole, 2- (or 4-) quinoline, indolenine nucleus.

R ₃₂ has the same meaning as R ₁ in formula (1), and is preferably an aromatic group or an aliphatic group that may have a substituent, and the number of carbon atoms of the aromatic group is preferably Is 1-16, more preferably 5 or 6. The number of carbon atoms in the aliphatic group is preferably 1-18, more preferably 4-18. Examples of the unsubstituted aliphatic group and aromatic group include groups such as methyl, ethyl, propyl, butyl, octyl, decyl, i-hexadecyl, phenyl, and naphthyl.

  Specific examples of the dyes represented by the general formulas (1) to (4) are shown below, but the present invention is not limited thereto. In these specific examples, when a tautomer exists, the tautomer is described by only one kind of description method, but is not limited to the tautomer, and includes a mixture of a plurality of tautomers.

<Compound represented by formula (5)>
R ₅₁ , R ₅₂ , R ₆₁ , R ₆₂ , R ₇₁ , R ₇₂ , R ₈₁ and R ₈₂ each represents a hydrogen atom, an aliphatic group or an aromatic group, preferably a hydrogen atom, an alkyl group or an alkenyl group. An alkynyl group and an aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and 6 to 6 carbon atoms. 20 aryl groups. More preferably, they are an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms, and particularly preferably an alkyl group having 1 to 8 carbon atoms and a carbon atom. An aryl group having 6 to 8 carbon atoms, most preferably an alkyl group having 2 to 6 carbon atoms. R ₅₁ , R ₅₂ , R ₆₁ , R ₆₂ , R ₇₁ , R ₇₂ , R ₈₁ and R ₈₂ are preferably all the same.

R ₄₀ , R ₅₃ , R ₆₃ , R ₇₃ and R ₈₃ each represent a substituent, preferably a halogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, cyano group, hydroxyl group, carboxyl group, alkoxy group Group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfo group Famoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryl Alkoxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, an imido group, a phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, a silyl group. More preferably, a halogen atom, alkyl group, alkenyl group, aryl group, cyano group, hydroxyl group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, amino group, alkylthio group, arylthio group, imide group, silyl group More preferred are a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a silyloxy group, and an amino group, and particularly preferred is an alkyl group. It is also preferred that all of R ₄₀ , R ₅₃ , R ₆₃ , R ₇₃ and R ₈₃ are the same.
n40, n41, n42, n43 and n44 represent 0 to 4, preferably 0 to 3, more preferably 0 to 2, still more preferably 0 or 1, and most preferably 0.

  X represents a monovalent or divalent anion, and n45 represents 1 or 2, but the product of the valence of X and n45 is 2. X is preferably perchlorate ion, carboxylate ion, sulfonate ion, hexafluorophosphate ion, tetrafluoroborate ion or hexafluoroantimonate ion, more preferably perchlorate ion, sulfonate ion, hexafluorophosphate. Ions, tetrafluoroborate ions or hexafluoroantimonate ions, more preferably sulfonate ions, hexafluorophosphate ions, tetrafluoroborate ions or hexafluoroantimonate ions, particularly preferably hexafluorophosphate ions, Tetrafluoroborate ion or hexafluoroantimonate ion.

In order to produce these dimonium dyes, the corresponding phenylenediamine compound is oxidized with Cu ²⁺ (Japanese Patent Publication No. 59-40825, Japanese Patent Laid-Open No. 63-51462), or is oxidized with Fe ³⁺ (Japanese Unexamined Patent Publication No. Hei. 2-311447, JP-A-11-315054), a method utilizing an oxidation reaction with a solid catalyst (JP-A-5-98243), a method of oxidizing with peroxodisulfate (JP-A-2003-55643), hexafluoro Methods such as oxidation with silver antimonate (Journal of Dispersion Science and Technology, 23, 555 (2002)) and electrical oxidation (Japanese Patent Laid-Open No. 61-246391) are known. It can be easily synthesized by the methods described in these or methods based thereon.

  Although the specific example of the infrared absorber represented by General formula (5) below is shown, this invention is not limited to these.

  In the toner according to the present invention, the amount of the infrared absorber represented by the general formula (5) is not particularly limited, but is preferably in the range of 10 to 200% by mass, and 50 to 150% by mass with respect to the dye. More preferred.

  The toner according to the present invention can express a wider and more stable color reproducibility than conventional toner images and images using printing inks by using the above-described colorant and infrared absorber, and image storage is possible. The properties (light resistance, heat and humidity resistance) were also improved. In particular, in recent years, there are many cases where the image displayed on the computer screen is printed out, but since the color gamut of conventional color printing is much narrower than the color gamut of the computer display, the image on the display and the printed output There was a big difference in the shades.

  However, by using the toner of 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 of the present invention greatly contributes to the expansion of the color gamut in a printed image.

<Combination dye>
The oil-soluble dyes represented by the general formulas (1) to (4) according to the present invention may be used alone or in combination with other pigments, and commonly used dyes are used as the dyes used together. Can be used. One preferred form is that the combined dye is an oil-soluble dye.

  Oil-soluble dyes are usually dyes that do not have water-soluble groups such as carboxylic acids and sulfonic acids, are soluble in organic solvents, and are insoluble in water, but salt water-soluble dyes with long-chain bases. Also included are dyes that exhibit oil 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, Varifast Yellow 4120, 3150, 3108, 2310N, 1101 manufactured by Orient Chemical Industry Co., Ltd .; Variifast Red 3320, 3304, 1306; Varifast Blue 2610, 2606, 1603; Oil Yellow GG-S, 3G, 129, 107, 105; Oil Scallet 308; Oil Red RR, OG, 5B; Oil Pin 312; Oil Blue BOS, 613, 2N; Oil Black BY, BS, 860, 5970, 5906, 5905; Nippon Kayaku Co., Ltd. Kayset Yellow SF-G, K-CL, GN, AG, 2G; Kayset Red SF-4G, K-BL, A-BR; Nta 312; Kayase Blue K-FL; FS Yellow 1015 manufactured by Arimoto Chemical Industry; FS Magenta 1404; FS Cyan 1522; FS Blue 1504; I. Solvent Yellow 88, 83, 82, 79, 56, 29, 19, 16, 14, 04, 03, 02, 01; C.I. I. Solvent Red 84: 1, 84, 218, 132, 73, 72, 51, 43, 27, 24, 18, 01; I. Solvent Blue 70, 67, 44, 40, 35, 11, 02, 01; C.I. I. Solvent Black 43, 70, 34, 29, 27, 22, 7, 3; I. Solvent Violet 3; C.I. I. Solvent Green 3 and 7; Plast Yellow DY352; Plast Red 8375; MS Yellow HD-180 manufactured by Mitsui Chemicals; MS Red G; MS Msgenta HM-1450H; MS Blue HM-1384; ES Red 3001, 3002, manufactured by Sumitomo Chemical Co., Ltd. 3003; TS Red 305; ES Yellow 1001, 1002; TS Yellow 118; ES Orange 2001; ES Blue 6001; TS Turq Blue 618; Bayer's MACROLel Yellow RO 6G; R etc. are mentioned.

  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.

  In the toner of the present invention, the content of the colorant is preferably in the range of 2 to 20% by mass with respect to the resin, and when the colorant is contained in the range of 3 to 15% by mass, a more sufficient concentration can be obtained. The protective ability of the colorant 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. Examples of such compounds include amine, amine, sulfur and phosphorus compounds. For the same purpose, for example, an organic or inorganic ultraviolet absorber may be added as the ultraviolet absorber.

  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, benzophenone compounds such as 2-hydroxy-4-octyloxybenzophenone, phenyl salsylate, 4-t-butylphenyl salsylate, 2,5- hydroxybenzoate compounds such as t-butyl-4-hydroxybenzoic acid hexadecyl ester, 2,4-di-t-butylphenyl-3 ', 5'-di-t-butyl-4'-hydroxybenzoate Can be mentioned.

  Examples of inorganic ultraviolet absorbers include titanium oxide, zinc oxide, cerium oxide, iron oxide, and barium sulfate. Organic ultraviolet absorbers are preferred, and ultraviolet absorbers include 50% transmittance. The wavelength at is preferably 350 to 420 nm, more preferably 360 to 400 nm. By being in this range, the ultraviolet blocking ability is sufficient, and the effect of little coloring is exhibited. 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.

  Next, the particle diameter of the toner according to the present invention will be described.

  The toner of the present invention preferably has a median diameter (D50v) on a volume basis of 3 to 8 μm. By setting the volume-based median diameter in the above range, it is possible to faithfully reproduce a very small dot image having a level of 1,200 dpi (dpi is the number of dots per inch, that is, 2.54 cm), for example.

  One of the problems with toner is to make it possible to faithfully reproduce the color of a photographic image. By setting the volume-based median diameter to a small diameter level within the above range, the dot image constituting the photographic image can be changed. High-definition photographic images equivalent to or better than printed images can be 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 of the 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 conditioned with 20 ml of a surfactant solution (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). Thereafter, 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 measuring machine count is set to 2,500. To measure. Note that the aperture size of the multisizer 3 is 50 μm.

  The toner of 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 CV value represents the degree of dispersion in the particle size distribution of toner particles on a 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 created with printing ink or higher by using small-diameter toners of uniform size.

  The toner preferably has a softening point temperature (Tsp) of 70 to 110 ° C, more preferably 70 to 100 ° C. The colorant used in the toner of the present invention has a stable property that the spectrum does not change even under the influence of heat, but is added to the toner during fixing by setting the softening point in the above range. The influence of 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. Further, 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 the environment-friendly image formation in which the power consumption is reduced 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) The type and composition ratio of monomers used for resin formation are adjusted.
(2) The molecular weight of the resin is adjusted according to the type and amount of chain transfer agent.
(3) Adjust the type and amount of wax.

The toner softening point temperature is specifically measured by using a flow tester CFT-500 (manufactured by Shimadzu Corporation), forming a cylindrical shape with a height of 10 mm, and heating at a heating rate of 6 ° C./min. While applying a pressure of 1.96 × 10 ⁶ Pa from the plunger and pushing it out from a nozzle with a diameter of 1 mm and a length of 1 mm, the curve between the plunger drop amount of the flow tester and the temperature (softening flow curve) The temperature that flows out first is the melting start temperature, and the temperature for the drop of 5 mm is the softening point temperature.

<Toner production method>
Next, a toner manufacturing method according to the present invention will be described.

  The toner of the present invention is composed of particles containing at least a resin and a colorant (hereinafter also referred to as colored particles). The colored particles constituting the toner are not particularly limited and can be produced by a conventional toner production method. That is, a toner manufacturing method by a so-called pulverization method in which a toner is prepared through a kneading, pulverization, and classification process, or a so-called polymerized toner in which a polymerizable monomer is polymerized and particles are formed while controlling the shape and size at the same time. It can be produced by applying a production method (emulsion polymerization method, suspension polymerization method, polyester elongation method, etc.).

  When the toner of the present invention is produced by a pulverization method, it is preferable to produce the toner while maintaining the temperature of the kneaded product at 130 ° C. or lower. This is because the uniform aggregation state of the colorant in the kneaded product can be maintained by maintaining the temperature applied to the kneaded product at 130 ° C. or lower. If variation occurs in the aggregated state, there is a concern that it may cause color turbidity.

  Next, the resin, wax and the like constituting the toner according to the present invention will be described with specific examples.

  First, the resin that can be used in the toner of the present invention is not particularly limited, but a polymer formed by polymerizing a polymerizable monomer called a vinyl monomer described below is representative. It is. The polymer constituting the resin that can be used in the present invention is a polymer obtained by polymerizing at least one polymerizable monomer, and these vinyl monomers are used alone. Or it is the polymer produced combining multiple types.

Specific examples of vinyl polymerizable monomers are shown below.
(1) Styrene or styrene derivatives Styrene, o- (m-, p-) methylstyrene, α-methylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-phenylstyrene, p-ethylstyrene, 2, 4-dimethyl styrene, pt-butyl styrene, p-hexyl styrene, p-octyl styrene, p-nonyl styrene, p-decyl styrene, p-dodecyl styrene and the like.
(2) Methacrylic acid ester derivatives Methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacrylic acid-i-propyl, methacrylic acid-i-butyl, methacrylic acid-t-butyl, octyl methacrylate, methacrylic acid-2-ethylhexyl , Stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, and the like.
(3) Acrylic acid ester derivatives Methyl acrylate, ethyl acrylate, acrylate-i-propyl, butyl acrylate, acrylate-t-butyl, acrylate-i-butyl, octyl acrylate, -2-ethylhexyl acrylate , Stearyl acrylate, lauryl acrylate, phenyl acrylate and the like.
(4) Olefins Ethylene, propylene, i-butylene and the like.
(5) Vinyl esters Vinyl propionate, vinyl acetate, vinyl benzoate and the like.
(6) Vinyl ethers Vinyl methyl ether, vinyl ethyl ether and the like.
(7) Vinyl ketones Vinyl methyl ketone, vinyl ethyl ketone, vinyl hexyl ketone and the like.
(8) N-vinyl compounds N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone and the like.
(9) Others Vinyl compounds such as vinyl naphthalene and vinyl pyridine, acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide, etc. Also, vinyl-based polymerization that constitutes a resin that can be used in the toner according to the present invention As the ionic monomer, those having an ionic dissociation group shown below can be used. Examples thereof include those having a functional group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group in the side chain of the monomer. Specific examples include the following.

  First, those having a carboxyl group include (meth) acrylic acid, maleic acid, itaconic acid, cinnamic acid, fumaric acid, maleic acid monoalkyl ester, itaconic acid monoalkyl ester, and the like. Examples of those having a sulfonic acid group include styrenesulfonic acid, allylsulfosuccinic acid, 2-acrylamido-2-methylpropanesulfonic acid, and examples of those having a phosphoric acid group include acid phosphooxyethyl methacrylate. .

  Moreover, it is also possible to produce a resin having a crosslinked structure by using the following polyfunctional vinyls. Specific examples of polyfunctional vinyls are shown below.

  Divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, and the like.

Next, examples of the wax that can be used in the toner according to the present invention include the following known waxes.
(1) Polyolefin wax Polyethylene wax, polypropylene wax, and the like.
(2) Long chain hydrocarbon wax Paraffin wax, sazol wax and the like.
(3) Dialkyl ketone waxes such as distearyl ketone.
(4) Ester wax Carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetramyristate, pentaerythritol tetrastearate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tri Behenate, 1,18-octadecanediol distearate, tristearyl trimellitic acid, distearyl maleate and the like.
(5) Amide wax Ethylenediamine dibehenyl amide, trimellitic acid tristearyl amide and the like.

  The melting point of the wax is usually 40 to 125 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. By setting the melting point within the above range, the heat-resistant storage stability of the toner is ensured, and stable toner image formation can be performed without causing cold offset or the like even when fixing at a low temperature.

  The wax content in the toner is preferably 1 to 30% by mass, more preferably 5 to 20% by mass.

  The toner of the present invention can be produced by adding particles such as inorganic fine particles and organic fine particles having a number average primary particle size of 4 to 800 nm as external additives (referred to as external additives) in the production process. is there.

  By adding the external additive, the fluidity and chargeability of the toner are improved, and the cleaning property is improved. The type of the external additive is not particularly limited, and examples thereof include the following inorganic or organic fine particles and slip agents.

  As the inorganic fine particles, conventionally known fine particles can be used. For example, silica, titania, alumina, strontium titanate fine particles and the like are preferable. Moreover, what hydrophobized these inorganic fine particles as needed can also be used.

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

  Examples of titania fine particles include T-805 and T-604 manufactured by Nippon Aerosil Co., Ltd .; MT-100S, MT-100B, MT-500BS, MT-600, MT-600SS, and JA-1 manufactured by Teica; Fuji Titanium Co., Ltd. TA-300SI, TA-500, TAF-130, TAF-510, TAF-510T made by Idemitsu Kosan Co., Ltd. IT-S, IT-OA, IT-OB, IT-OC, etc. are mentioned.

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

  As the organic fine particles, spherical organic fine particles having a number average primary particle diameter of about 10 to 2000 nm can be used. Specifically, homopolymers such as styrene and methyl methacrylate, and copolymers thereof can be used.

  Further, a slip agent can be used to further improve the cleaning property and transfer property, and examples thereof include the following higher fatty acid metal salts. That is, zinc stearate, aluminum, copper, magnesium, calcium salt, oleic zinc, manganese, iron, copper, magnesium salt, palmitic acid zinc, copper, magnesium, calcium salt, linoleic acid Zinc, calcium salt, ricinoleic acid zinc, calcium salt, etc.

  The addition amount of these external additives and lubricants is preferably 0.1 to 10.0% by mass with respect to the total amount of toner. Examples of methods for adding external additives and lubricants include methods using various known mixing devices such as a turbuler mixer, a Henschel mixer, a nauter mixer, and a V-type mixer.

  The toner of the present invention can be used as a two-component developer composed of a carrier and a toner, or as a non-magnetic one-component developer composed only of a toner.

  When the toner of the present invention is used as a two-component developer, a full-color print can be created at a high speed using, for example, a tandem image forming apparatus described later. In addition, by selecting the resin or wax constituting the toner, it is possible to create a so-called full-color print compatible with low-temperature fixing, in which the paper temperature during fixing is about 100 ° C.

  Carriers that are magnetic particles used when used as a two-component developer are 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. Among these, ferrite particles are preferable. The carrier has a volume average particle size of preferably 15 to 100 μm, more preferably 25 to 80 μm.

  When the toner is used as a non-magnetic one-component developer that forms an image without using a carrier, the toner is slid and pressed against the charging member and the developing roller surface during image formation. The image formation by the non-magnetic one-component development method can simplify the structure of the developing device, and has an advantage that the entire image forming device can be made compact. Therefore, when the toner of the present invention is used as a non-magnetic one-component developer, a full-color print can be created with a compact color printer, and a full-color print having excellent color reproducibility can be created even in a space-limited work environment. Is possible.

<Image formation>
Next, an image forming method using the toner of 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 above 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 another different color toner image is arranged around a drum-shaped photoconductor 1C as a first photoconductor, and around the photoconductor 1C. 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, as one of other different color toner images, an image forming unit 10K for forming a black image 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 is pressed against the endless belt-shaped intermediate transfer body 70 only when the recording member P passes through the secondary transfer roll 5A and the secondary transfer is performed.

  Further, the casing 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 of the present invention is used as a nonmagnetic one-component developer will be described. FIG. 2 shows 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 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 and the like 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 rotationally driven in the same direction as the developing roller 41 (counterclockwise direction in the figure) by a motor (not shown). The supply roller 46 has a conductive cylindrical base and a foam layer formed of urethane foam or the like on the outer periphery of the base.

  The hopper 43 contains toner T which is 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 the forward 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.

  A restricting 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 of 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. It is done. 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. Of these, the reduction of energy consumption in the fixing process has attracted attention, and so-called low-temperature fixing technology for fixing a toner image at a temperature lower than the current fixing temperature has been adopted.

  That is, when the toner of 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 as either the heating member or the pressure member. The 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 cannot be taken away from the seamless belt 241. A specific example of the material of the seamless belt 241 is, for example, polyimide.

  The toner image formed with the toner of 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 high-quality paper from thin paper to thick paper, coated printing paper such as art paper and coated paper, commercially available Japanese paper and postcard paper, OHP plastic film, cloth, etc. Although not limited to these, it is not limited to these.

Hereinafter, although an example is given and an embodiment of the present invention is explained concretely, the present invention is not limited to this. Unless otherwise specified, “part” in the examples represents “part by mass” and “%” represents “mass%”.
1. Preparation of toners 1 to 26 1-1. Preparation of toners 1 to 5 (toner by kneading and pulverization method) The following toner components were charged 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. .

Polyester resin (bisphenol A-ethylene oxide adduct / terephthalic acid / trimellitic acid condensate, weight average molecular weight 20,000) 100 parts Colorant 2 parts Infrared absorber 2 parts Release agent (pentaerythritol tetrastearate) 6 parts Charge control agent (boron dibenzylate) 1 part The mixture was kneaded with a twin-screw extrusion kneader, then coarsely pulverized with a hammer mill, then pulverized with a turbo mill pulverizer (manufactured by Turbo Kogyo Co., Ltd.), and the Coanda effect was further utilized. By performing fine powder classification with an airflow classifier, colored particles having a volume-based 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 (described above) to prepare toners 1 to 5. This external addition treatment was performed under the conditions of a stirring blade peripheral speed of 35 m / second, a treatment temperature of 35 ° C., and a treatment time of 15 minutes.

Silica treated with hexamethylsilazane (average primary particle size 12 nm) 0.6 part Titanium dioxide treated with octylsilane (average primary particle size 24 nm) 0.8 part Table 1 shows the types of colorants and infrared absorbers To do.
1-2. Preparation of Toners 2 to 26 (Toner by Emulsion Association Method) (1) Preparation of Colorant Fine Particle Dispersion 1 11.5 parts of sodium dodecyl sulfate was added to 160 parts of ion-exchanged water, dissolved and stirred, and an aqueous surfactant solution. Was prepared. In this surfactant aqueous solution, 2 parts of each of the colorant and infrared absorber shown in Table 1 are gradually added, and dispersion treatment is performed using Clearmix W Motion CLM-0.8 (M Technique Co., Ltd.). Thus, a colorant fine particle dispersion 1 was prepared.

  The colorant fine particles 1 in the 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)
Zero-point adjustment Ion-exchanged water was added to the measurement cell for adjustment.
(2) Preparation of core part resin particles 1 Core part resin particles 1 having a multilayer structure were prepared through the following first-stage polymerization, second-stage polymerization, and third-stage polymerization.
(A) First-stage polymerization 4 parts of the anionic surfactant (S-1) shown below are charged together with 3,040 parts of ion-exchanged water into a reaction vessel equipped with a stirrer, temperature sensor, cooling pipe, and nitrogen introducing device. Then, a surfactant aqueous solution was prepared.

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

Styrene 532 parts Butyl acrylate 200 parts Methacrylic acid 68 parts Octyl mercaptan 16.4 parts After the dropwise addition of the above monomer mixture, the system was polymerized by heating and stirring at 75 ° C for 2 hours (first stage polymerization). ) To prepare resin particles. Let this resin particle be resin particle A1. The weight average molecular weight (Mw) of this resin particle A1 was 16,500.
(B) Second-stage polymerization A monomer mixed solution having the following composition was charged into a flask equipped with a stirrer, and then paraffin wax (HNP-57: manufactured by Nippon Wax Co., Ltd.) as a mold release agent. 8 parts were added and dissolved by heating to 90 ° C. In this way, a monomer solution was prepared.

Styrene 101.1 parts Butyl acrylate 62.2 parts Methacrylic acid 12.3 parts Octyl mercaptan 1.75 parts On the other hand, an aqueous surfactant solution was prepared by dissolving 3 parts of S-1 in 1,560 parts of ion-exchanged water. And heated to 98 ° C. After adding 32.8 parts (in terms of solid content) of the resin particles A1 to the surfactant aqueous solution, and further adding a monomer solution containing the paraffin wax, a mechanical disperser CLEARMIX having a circulation path is added. (Mtechnic Co., Ltd.) mixed and dispersed for 8 hours. An emulsified particle dispersion containing emulsified particles having a dispersed particle size of 340 nm was prepared by the mixing and dispersing.

Next, a polymerization initiator solution in which 6 parts of potassium persulfate is dissolved in 200 parts of ion-exchanged water is added to this 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. Let this resin particle be resin particle A2. Mw of this resin particle A2 was 23,000.
(C) Third-stage polymerization A polymerization initiator solution prepared by dissolving 5.45 parts of potassium persulfate in 220 parts of ion-exchanged water is added to the resin particles A2 obtained by the second-stage polymerization, and the temperature is 80 ° C. Under the conditions, a monomer mixture having the following composition was dropped over 1 hour.

Styrene 293.8 parts Butyl acrylate 154.1 parts Octyl mercaptan 7.08 parts After completion of dropping, the mixture is heated and stirred for 2 hours to conduct polymerization (third stage polymerization), and after completion of the polymerization, cooled to 28 ° C. Thus, the core part resin particles 1 were produced. The Mw of the core part resin particles 1 was 26,800.
(3) Preparation of resin particles for shell The polymerization reaction and after the reaction were the same except that the monomer mixture used in the first stage polymerization in the preparation of the resin particles 1 for the core was changed to the following: The resin particle 1 for shells was produced by performing the above process.

Styrene 624 parts 2-Ethylhexyl acrylate 120 parts Methacrylic acid 56 parts Octyl mercaptan 16.4 parts (4) Preparation of toners 6 to 26 Toners 2 to 26 were prepared according to the following procedure.
(A) Formation of core part A reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device was charged with a mixture having the following composition. After adjusting the temperature in the reaction vessel to 30 ° C., a 5 mol / L sodium hydroxide aqueous solution was added to adjust the pH to 8-11.

Resin particle for core part 420.7 parts (solid content conversion)
900 parts of ion-exchanged water 200 parts of colorant particle dispersion 1 Then, an aqueous solution prepared by dissolving 2 parts of magnesium chloride hexahydrate in 1,000 parts 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 of sodium chloride was added to ion-exchanged water 1, The aqueous solution dissolved in 000 parts was added to stop the association.

After the association was stopped, the core part 1 was produced by continuing the fusion by further heating and stirring for 1 hour at a liquid temperature of 70 ° C. as an aging treatment. It was 0.912 when the average circularity of the core part 1 was measured by FPIA2000 (made by Systex).
(B) Formation of Shell Next, an aqueous solution in which 96 parts of resin particles 1 for shells were added at a temperature of 65 ° C. and 2 parts of magnesium chloride hexahydrate was dissolved in 1,000 parts of ion-exchanged water was added. After addition 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 obtained by dissolving 40.2 parts of sodium chloride in 1,000 parts 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 hot air at 40 ° C. Colored particles 2 having a shell were produced.
(C) External Addition Treatment The following external additives were added to the produced colored particles 2 and external addition treatment was performed with a Henschel mixer (manufactured by Mitsui Miike Mining Co., Ltd.) to prepare toners 6 to 26.

Hexamethylsilazane-treated silica (average primary particle size: 12 nm) 0.6 part Octylsilane-treated titanium dioxide (average primary particle size: 24 nm) 0.8 part / Second, treatment temperature 35 ° C., treatment time 15 minutes.

The types of colorants and infrared absorbers are listed in Table 1.
1-4. Preparation of Developers 1 to 26 Each of the toners 2 to 5 and 7 to 25 of the present invention and the comparative toners 1, 6 and 26 are mixed with a ferrite carrier having a volume average particle diameter of 60 μm coated with a silicone resin, and the toner concentration 6% developer 1-26 was prepared.
2. Performance Evaluation With respect to each of the developers 1 to 26 obtained as described above, a digital copying machine Konica 7075 (manufactured by Konica Corporation) in which the configuration of the fixing device is changed as described below is used in a normal temperature / humidity environment ( A real photograph test was performed on paper at 25 ° C. and RH 55%), and color reproducibility, light resistance, and heat and humidity resistance were evaluated. Development conditions are as shown below.

(Development conditions)
Photoconductor surface potential: -700V
DC bias: -500V
Dsd (distance between the photoconductor and the developing sleeve): 600 μm
Developer layer regulation: Magnetic H-Cut system Developer layer thickness: 700 μm
Developing sleeve diameter: 40 mm.

(Fixer)
As the fixing device, a heat roll fixing type was used. More specifically, a tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (with a cylindrical shape (inner diameter = 40 mm, wall thickness = 1.0 mm, total width = 310 mm)) made of an aluminum alloy with a built-in heater at the center is provided. A heating roller is formed by coating with a PFA) tube having a thickness of 120 μm, and the surface of a cylindrical metal core made of iron (inner diameter = 40 mm, wall thickness = 2.0 mm) is made of sponge silicone rubber (Asker C hardness 48 The pressure roller was configured by coating with a thickness of 2 mm), and the heating roller and the pressure roller were brought into contact with each other with a load of 150 N to form a 5.8 mm wide nip.

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

《Color reproducibility》
The color reproducibility of the single-color image on the copy paper was evaluated according to the following evaluation criteria by visual evaluation using 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 (the impression is close to blue or cloudy blue. In the case of a magenta image, the impression is close to red or vermilion)

《Light resistance》
For light resistance, after measuring the image density Ci immediately after recording, the image was irradiated with xenon light (70,000 lux) for 14 days using a weather meter (Atlas C.165), and the image density Cf was again measured. The dye residual ratio ({(Ci-Cf) / Ci} × 100%) was calculated and evaluated from the difference in image density before and after irradiation with xenon light. The image density was measured using a reflection densitometer (X-Rite 310TR).

A: Dye remaining ratio is 98% or more A: Dye remaining ratio is 95 to 98%
○: Dye remaining rate is less than 90 to 95% Δ: Dye remaining rate is less than 80 to less than 90% ×: Dye remaining rate is less than 80%.

《Heat resistance》
For heat and humidity resistance, the image density Ci immediately after recording was measured, stored for 14 days under the conditions of 50 ° C. and 80% RH, and then the image density Cf was measured again. ({(Ci−Cf) / Ci} × 100%) was calculated and evaluated. The image density was measured using a reflection densitometer (X-Rite 310TR). In addition, the color change was observed visually.

A: Dye remaining ratio is 95% or more A: Dye remaining ratio is 90 to 95%
○: Dye remaining ratio is less than 80 to 90% Δ: Dye remaining ratio is less than 80%, and the color appears slightly cloudy visually: D: Dye remaining ratio is less than 80%, and the color appears cloudy visually.

  Apart from these performances, toner consumption was also measured.

<Toner consumption>
Using each toner, 2,000 A4 size monochrome images with a pixel rate of 6% are printed, and the amount of toner consumed per printed sheet is calculated and evaluated from the amount of toner consumed when creating the print. Went. A toner having a toner consumption per print of less than 16 mg / sheet was regarded as acceptable.

  The results are also shown in Table 1.

As shown in Table 1, the developers 2 to 5 and 7 to 24 using the toner corresponding to the toner of the present invention are all good in each evaluation item, and the effects of the present invention are exhibited. It was confirmed. On the other hand, in Comparative Examples 1, 6 and 26 using toners other than the present invention, the results obtained in the present invention were not obtained for the above evaluation items, and it was confirmed that the effects of the present invention were not exhibited. . Further, the dyes represented by the general formulas (1) to (4) are better than the dye A-1.

1 is a schematic diagram illustrating an example of a tandem full-color image forming apparatus capable of image formation by a two-component development system. 1 is a schematic diagram of a four-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.

Explanation of symbols

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 (6)

In the color toner for electrophotography used in the electrophotography using the heat roller fixing method,
An electrophotographic color toner comprising an oil-soluble dye represented by any one of the following general formulas (1) to (4) and an infrared absorbent represented by the following general formula (5) .

[Wherein, Q ₁ and Q ₂ represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring, and may be further condensed or have a substituent. L _{1 to} L ₁₀ each represents a substituted or unsubstituted methine group, and R ₁ and R ₂ each represent a substituent. m1, m2, n1, and n2 each represents 0 or 1. ]

[Wherein, R ₁₁ , R ₁₂ , R ₁₉ and R ₂₀ each represent a substituent, and R ₁₃ and R ₁₄ each represent a hydrogen atom or a substituent. R ₁₅ represents ═N ⁺ (R ₁₆ ) R ₁₇ or ═O ⁺ R ₁₈ , and R ₁₆ , R ₁₇ and R ₁₈ each represent a hydrogen atom or a substituent. p1 and p2 each represent an integer of 0 to 3. When p1 or p2 is 2 or 3, a plurality of R ₁₁ or R ₁₂ may be the same or different. ]

[Wherein R ₂₁ and R ₂₃ each represent a hydrogen atom or a substituent, R ₂₂ represents —N (R ₂₄ ) R ₂₅ or —OR ₂₆ , and A ₂₁ and A ₂₂ each represent —C (R ₂₇ ) = Or -N =, X ₂₁ represents an atomic group necessary for forming a 5- or 6-membered aromatic ring or heterocyclic ring, and Z ₂₁ represents a 5- or 6-membered group containing at least one nitrogen atom. It represents an atomic group necessary for forming a heterocyclic ring, may have a substituent, and may further form a condensed ring. R _{24 to} R ₂₇ each represents a hydrogen atom or a substituent. q represents an integer of 0 to 3, and when q is 2 or more, the plurality of R ₂₁ may be the same or different. L ₂₁ represents a single bond or a divalent linking group, L ₂₂ , L ₂₃ and L ₂₄ represent a methine group which may have a substituent, and n ₂₁ represents 0 or 1. ]

[Wherein R ₃₁ and R ₃₃ each represent a hydrogen atom or a substituent, and Z ₃₁ represents an atomic group necessary for forming a 5- or 6-membered heterocyclic ring containing at least one nitrogen atom, It may have a group and may further form a condensed ring, and Q ₃₁ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. It may have a group. L ₃₁ , L ₃₂ , L ₃₄ and L ₃₅ each represents an optionally substituted methine group, L ₃₃ represents a single bond or a divalent linking group, and R ₃₂ represents a substituent. n31 represents 1 or 2, and n32 represents 0 or 1. r represents an integer of 0 to 2, and when r is 2, a plurality of R ₃₁ may be the same or different. ]

[Wherein, R ₅₁ , R ₅₂ , R ₆₁ , R ₆₂ , R ₇₁ , R ₇₂ , R ₈₁ and R ₈₂ each represent a hydrogen atom, an aliphatic group or an aromatic group, and R ₄₀ , R ₅₃ , R ₆₃ , R ₇₃ and R ₈₃ each represent a substituent, n40, n41, n42, n43 and n44 each represent an integer of 0 to 4, and n45 represents 1 or 2. X represents a monovalent or divalent anion, and the product of the valence of X and n45 is 2. ] 2. The general formula (5), wherein X is a perchlorate ion, a carboxylate ion, a sulfonate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, or a hexafluoroantimonate ion. Color toner for electrophotography. In the general formula (5), X is ClO. ₄ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , CF ₃ SO ₂ N ⁻ SO ₂ CF ₃ , C ₂ F ₅ CON ⁻ SO ₂ CF ₃ , (CF ₃ SO ₂ ) ₃ C ⁻ , CF ₃ SO ₃ ⁻ The color toner for electrophotography according to claim 1, which is represented by: The color toner for electrophotography according to any one of claims 1 to 3, wherein the oil-soluble dye is a methine dye or a squarylium dye.   The color toner for electrophotography according to claim 1, wherein the color toner for electrophotography is a polymerized toner.   6. The color toner for electrophotography according to claim 1, wherein the oil-soluble dye has a light absorption peak in a wavelength range of 600 to 700 nm.

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