JP2009276415A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner, achieving vivid color tone, and having excellent document offsetability and sublimation resistance. <P>SOLUTION: This toner includes resin and a coloring agent, wherein a coloring component of the coloring agent has a structure expressed by a general formula (A). In the above general formula (A), Y is a polymer with a molecular weight Mp of 2000 to 18000. Z indicates an aromatic ring or heterocycle which may have a substitutional group. R<SB>1</SB>, indicates an alkyl group, an aromatic ring or heterocycle, which may have a substitutional group. R<SB>2</SB>, R<SB>3</SB>, and R<SB>4</SB>and R<SB>5</SB>respectively indicate an alkyl group, an alkoxy group, a hydroxyl group or a halogen group which may have a substitutional group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a toner.

The development of color electrophotographic image forming apparatuses such as printers and multifunction peripherals (MFPs) used in offices and the like is intensifying.
As a result of the significant increase in processing speed, these image forming apparatuses have come to be used as applications for printing variable information such as direct mail and fee details as “digital printers”. Since no printing plate is required, it is becoming popular as an alternative to offset printing machines, which were the mainstream of commercial printing. In addition, high-speed machines have a large number of printed sheets, so the rotation rate of consumables such as toner is high, and there are a number of companies entering with differentiated technologies.

  By the way, the standard color adopted in the printing market is called “JAPAN COLOR 2001”. Already, full-color image forming apparatuses conforming to this standard color have been developed by various companies and provided to the market. In the future, as the specifications of digital cameras and display devices become higher, there is an increasing need for faithful color reproduction as displayed even when printing an image displayed on a display.

  A standard called “s-RGB” established by the International Electrotechnical Communication (IEC) is adopted for the color gamut of the display. The color gamut according to this standard was originally achieved by an additive color method using RGB, and “JAPAN” is a color reduction method centering on Y (yellow), M (magenta), C (cyan), and K (black). The color gamut of “COLOR 2001” is much wider. For this reason, the currently used toner cannot faithfully reproduce the color of the image displayed on the display. In particular, there was a need to increase saturation to vividly reproduce secondary colors in the blue and red regions.

  2. Description of the Related Art Conventionally, a technique using a low molecular weight dye as a colorant has been disclosed as a colorant that increases saturation and transparency (see, for example, Patent Document 1). However, since the low molecular weight dye has a high sublimation property, the high-speed machine has a problem of in-machine contamination due to sublimation. This is because the high-speed machine sets the temperature of the fixing heating member to be high for the toner having the same thermal characteristics in consideration of the heat conduction speed, and the number of images passing through the fixing device per unit time is large.

  In addition, as a method for improving the coloring efficiency, a technique has been proposed in which a pigment is used as a colorant and the particle surface of the pigment is processed to be easily incorporated into toner particles (see, for example, Patent Document 2). According to this, by using a pigment dispersant having a radical polymerizable group, it is possible to obtain toner particles having a uniform particle diameter containing a pigment inside the particles. However, in actuality, it can be slightly incorporated into the particles, and further improvement in coloring efficiency is desired.

In addition, in the method of Patent Document 2, the pigment incorporation efficiency at the initial stage of the polymerization reaction is poor, and as a result, the pigment tends to be attached in the vicinity of the surface, and depending on the type of pigment, the environmental characteristics of the toner surface are poor. In some cases, it was difficult to control charging. On the other hand, in order to easily disperse the pigment, the pigment dispersion has a structure in which the phthalocyanine-based molecular skeleton adsorbed on the pigment and the oligomer or polymer that prevents the reaggregation of the pigment and has a dispersion effect are bonded by a covalent bond. A method using an agent has been proposed (see, for example, Patent Document 3).
JP-A-10-123759 Japanese Unexamined Patent Publication No. Heisei 3-200976 JP 2002-226727 A

  On the other hand, low-temperature fixing of toner is being promoted in parallel with the improvement of color reproduction, and when this low-temperature fixing is advanced, this is called document offset, in which part of the image is contaminated between the contacting image surfaces. The problem is an obstacle. In other words, when a color image with a high pixel ratio is printed on both sides, characters and images are contaminated between the image planes, causing image defects during long-term storage, and sometimes adhesion between papers occurs. There is an urgent need to solve such problems.

  However, it is difficult to solve both the document offset problem and the problem of colorant sublimation from toner particles while realizing a vivid color tone by the techniques of Patent Documents 1 to 3 described above.

  An object of the present invention is to provide a toner having excellent document offset and sublimation resistance while realizing a vivid color tone.

上記一般式Ａにおいて、Ｙは分子量Ｍｐが２０００〜１８０００の重合体である。Ｚは置換基を有してもよい芳香環又は複素環を示す。Ｒ_１は置換基を有してもよいアルキル基、芳香環又は複素環を示す。Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５は、それぞれ置換基を有してもよいアルキル基、アルコキシル基、ヒドロキシル基又はハロゲン基を示す。 According to the invention of claim 1,
In a toner containing a resin and a colorant,
A toner in which the coloring component of the colorant has a structure represented by the following general formula A.

In the above general formula A, Y is a polymer having a molecular weight Mp of 2000 to 18000. Z represents an aromatic ring or a heterocyclic ring which may have a substituent. R ₁ represents an alkyl group, an aromatic ring or a heterocyclic ring which may have a substituent. R ₂ , R ₃ , R ₄ and R ₅ each represents an alkyl group, an alkoxyl group, a hydroxyl group or a halogen group which may have a substituent.

  According to the present invention, a vivid color tone can be realized. In addition, it is possible to provide a toner having excellent document offset property, which has less colorant sublimation and less contamination due to sublimation.

"toner"
The toner according to the present invention is composed of particles containing at least a resin and a colorant (hereinafter also referred to as colored particles). A mold release agent, a charge control agent, and an external additive can be added as necessary.

<resin>
Although resin is not specifically limited, The polymer formed by superposing | polymerizing the polymerizable monomer called the following vinylic monomer is mentioned as an example. This polymer comprises a polymer obtained by polymerizing at least one polymerizable monomer as a constituent component, and is a polymer produced by combining these vinyl monomers alone or in combination. .

Specific examples of vinyl polymerizable monomers are shown below.
(1) Styrene or styrene derivatives For example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-phenylstyrene, p- Ethyl styrene, 2,4-dimethyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl Examples include styrene.

(2) Methacrylic acid ester derivatives For example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid Examples include stearyl acid, lauryl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, and the like.

(3) Acrylic acid ester derivatives For example, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, acrylic Examples include stearyl acid, lauryl acrylate, and phenyl acrylate.

(4) Olefin Examples include ethylene, propylene, isobutylene and the like.
(5) Vinyl esters For example, vinyl propionate, vinyl acetate, vinyl benzoate and the like.
(6) Vinyl ethers Examples include vinyl methyl ether and vinyl ethyl ether.

(7) Vinyl ketones Examples include vinyl methyl ketone, vinyl ethyl ketone, and vinyl hexyl ketone.
(8) N-vinyl compounds Examples include N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone and the like.

(9) Others Other examples include vinyl compounds such as vinyl naphthalene and vinyl pyridine, acrylic acid such as acrylonitrile, methacrylonitrile, and acrylamide, and methacrylic acid derivatives.
Further, as the vinyl polymerizable monomer constituting the resin that can be used in the toner according to the present invention, those having an ionic dissociation group shown below can be used. For example, what has functional groups, such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group, in the side chain of a monomer is mentioned. Specifically, those having a carboxyl group include acrylic acid, methacrylic 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 group include styrene sulfonic acid, allyl sulfosuccinic acid, and 2-acrylamido-2-methylpropane sulfonic acid. Examples of the phosphoric acid group include acid phosphooxyethyl methacrylate.

  Moreover, it is also possible to produce a resin having a crosslinked structure by using polyfunctional vinyls as a crosslinking agent. Examples of polyfunctional vinyls include divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neo Examples thereof include pentyl glycol diacrylate.

Examples of resins that can be used in the toner according to the present invention include polyester resins and polyester polyol resins.
As the polyester resin monomer, alcohol and carboxylic acid or carboxylic anhydride, carboxylic acid ester, or the like can be used.
Specifically, for example, as the dihydric alcohol component, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis ( 4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2, Alkylene oxide adducts of bisphenol A such as 2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1 , 2-Propylene glycol, 1,3-propylene glycol, 1,4-butanedio , Neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, hydrogenated bisphenol A and the like.

  Examples of the trivalent or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. Can be mentioned.

  Examples of the carboxylic acid component include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; Examples thereof include succinic acid substituted with 6 to 12 alkyl groups or anhydrides thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, and citraconic acid, or anhydrides thereof.

式中、Ｒ_１１はエチレン基又はプロピレン基を示し、ｘ、ｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値は２〜１０である。 Among them, in particular, a bisphenol derivative represented by the following general formula B1 as a diol component and a carboxylic acid component comprising a divalent or higher carboxylic acid or an acid anhydride thereof or a lower alkyl ester thereof (for example, fumaric acid, maleic acid) A polyester resin obtained by polycondensation of these components using acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, or the like as an acid component is preferable because it imparts good electric resistance to the toner.

In the formula, R ₁₁ represents an ethylene group or a propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10.

  Examples of the trivalent or higher polyvalent carboxylic acid component for forming a polyester resin having a crosslinking site include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2, Examples include 4-naphthalenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, and anhydrides and ester compounds thereof.

上記式Ｂ２において、Ｒ_１２、Ｒ_１３は水素原子、メチル基、エチル基又はフェニル基であり、Ｒ_１２とＲ_１３とで同一でも異なっていてもよい。

上記式Ｂ３において、Ｒ_１４、Ｒ_１５は水素原子、メチル基、エチル基又はフェニル基であり、ｎは０以上の整数である。Ｒ_１４とＲ_１５は同一でもよいし、異なっていてもよい。 Moreover, as a polyester polyol resin, the bisphenol (b1) represented by the following general formula B2, the bisphenol type epoxy resin (b2) represented by the following general formula B3, a polyhydric alcohol (b3), and the said polyvalent At least one selected from a reaction product (b4) of an alcohol and an acid anhydride, a compound (b5) containing in the molecule at least one active hydrogen group that reacts with an epoxy group, and, if necessary, cross-linking The agent (b6) is used as a main raw material and is obtained by reacting these main raw materials.

In the formula B2, R ₁₂ and R ₁₃ are a hydrogen atom, a methyl group, an ethyl group, or a phenyl group, and R ₁₂ and R ₁₃ may be the same or different.

In the above formula B3, R ₁₄ and R ₁₅ are a hydrogen atom, a methyl group, an ethyl group or a phenyl group, and n is an integer of 0 or more. R ₁₄ and R ₁₅ may be the same or different.

Specific examples of the bisphenols (b1) represented by the general formula B2 include 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A), bis (4-hydroxyphenyl) methane (commonly known as bisphenol F), 1,1-bis (4-hydroxyphenyl) ethane (commonly called bisphenol AD), 1-phenyl-1,1-bis (4-hydroxyphenyl) methane, 1-phenyl-1,1-bis (4-hydroxyphenyl) Ethane and the like can be mentioned.
These bisphenols may be used individually by 1 type, and may be used in combination of 2 or more type.

  As the bisphenol type epoxy resin (b2) represented by the general formula B3, for example, a so-called one-step epoxy resin produced from the bisphenols (b1) represented by the general formula B2 and epichlorohydrin, or a one-step method. A two-stage epoxy resin which is a polyaddition reaction product of an epoxy resin and a bisphenol (b1) is mentioned (“New Epoxy Resin” edited by Hiroshi Kakiuchi, Shosodo, 1985, p30).

上記一般式Ｂ４において、Ｒ_１６、Ｒ_１７はエチレン基又はプロピレン基であり、ｐ、ｑは１以上の整数、ｐ＋ｑは２〜１０である。Ｒ_１６とＲ_１７は同一でもよいし異なるものでもよい。 Examples of the polyhydric alcohols (b3) that are one of the main raw materials include dihydric alcohols such as aromatic diols, aliphatic diols, and alicyclic diols, and trivalent or tetravalent alcohols.
Examples of the aromatic diol include compounds represented by the following general formula B4.

In the general formula B4, R ₁₆ and R ₁₇ are an ethylene group or a propylene group, p and q are integers of 1 or more, and p + q is 2 to 10. R ₁₆ and R ₁₇ may be the same or different.

  Specific examples of such aromatic diols include polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene- (2.0) -2,2-bis. (4-hydroxyphenyl) propane, polyoxypropylene (1.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (1.1) -2,2-bis (4-hydroxyphenyl) ) Propane, polyoxypropylene- (2.2) -polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (6) -2,2-bis ( 4-hydroxyphenyl) propane, polyoxypropylene- (3.3) -2,2-bis (4-hydroxyphenyl) propane and the like. In the present invention, p-xylylene glycol and m-xylylene glycol can also be used as the aromatic diol.

Examples of the aliphatic diol include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, tetramethylene glycol, pentamethylene glycol, neopentyl glycol and the like.
Examples of the alicyclic diol include dihydroxymethylcyclohexane and hydrogenated bisphenol A.

  Examples of the trivalent or tetravalent alcohol include 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, tripentaerythritol, 1,2,4-butane taking all, trimethylolethane, Examples include trimethylolpropane and 1,3,5-trihydroxymethylbenzene.

  As for the reaction product (b4) of polyhydric alcohol and acid anhydride which is one of the main raw materials, examples of the acid anhydride used for the reaction with polyhydric alcohol include phthalic anhydride, trimellitic anhydride, Pyromellitic anhydride, ethylene glycol bis trimellitate, glycerol trislimitate, maleic anhydride, tetrahydrophthalic anhydride, methyltentrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methyl Butenyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, methylcyclohexene dicarboxylic acid anhydride, alkylstyrene-maleic anhydride copolymer, chlorendic anhydride, Polya It can be given line anhydride.

  The reaction between the polyhydric alcohol and the acid anhydride can be usually carried out at 80 ° C. to 150 ° C. for 1 to 8 hours in the presence of a catalyst. The reaction between the polyhydric alcohol and the acid anhydride may be performed simultaneously with the polyaddition reaction in the production of the resin preferably used in the present invention described later, or may be performed before the polyaddition reaction. Since the acid anhydride acts as a crosslinking agent and in some cases gelation may occur, it is preferably performed before the polyaddition reaction. Examples of the catalyst used in this reaction include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkali metal alcoholates such as sodium methylate, N, N-dimethylbenzylamine, triethylamine, pyridine and the like. Tertiary amines, quaternary ammonium salts such as tetramethylammonium chloride and benzyltriethylammonium chloride, organophosphorus compounds such as triphenylphosphine and triethylphosphine, alkali metal salts such as lithium chloride and lithium bromide, trifluoride Examples include Lewis acids such as boron, aluminum chloride, tin tetrachloride, tin octylate, and zinc benzoate. The amount used is usually 1 to 1000 ppm, preferably 5 to 500 ppm based on the amount of product. In this reaction, a solvent may or may not be used. When a solvent is used, aromatic hydrocarbons such as toluene, xylene and ethylbenzene, and ketones such as methyl isobutyl ketone and methyl ethyl ketone are preferred.

The compound (b5) having at least one active hydrogen group that reacts with an epoxy group, which is one of the main raw materials, in the molecule is a monovalent phenol, a secondary amine, or a monovalent carboxylic acid.
Examples of the monovalent phenols include phenol, cresol, isopropylphenol, octylphenol, nonylphenol, dodecylphenol, xylenol, P-cumylphenol, α-naphthol, β-naphthol, and the like.

  Secondary amines include, for example, diethylamine, dipropylamine, dibutylamine, dipentylamine, didodecylamine, distearylamine, diethanolamine, diallylamine and other aliphatic secondary amines, N-methylaniline, N-methyltoluidine, N -Aromatic ring-containing secondary amines such as methylnitroaniline, diphenylamine, ditolylamine, benzyldimethylamine and the like.

  Examples of monovalent carboxylic acids include aliphatic carboxylic acids such as propionic acid, butyric acid, caproic acid, caprylic acid, pelargonic acid, stearic acid, benzoic acid, toluic acid, α-naphthoic acid, β-naphthoic acid, and phenylacetic acid. And aromatic ring-containing monovalent carboxylic acids.

  Moreover, as a crosslinking agent (b6) used as needed, polyamines, such as an aromatic polyamine and an aliphatic polyamine, an acid anhydride, a trivalent or more phenolic compound, a trivalent or more epoxy resin, etc. are used, for example. . Examples of polyamines include diethylenetriamine, triethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, trimethylhexamethylenediamine, diethylaminopropylamine, metaxylylenediamine, metaphenylenediamine, diaminodiphenylmethane, and diaminodiphenylsulfone. Can be mentioned.

上記一般式Ａにおいて、Ｙは分子量Ｍｐが２０００〜１８０００の重合体である。Ｚは置換基を有してもよい芳香環又は複素環を示す。Ｒ_１は置換基を有してもよいアルキル基、芳香環又は複素環を示す。Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５は、それぞれ置換基を有してもよいアルキル基、アルコキシル基、ヒドロキシル基又はハロゲン基を示す。Ｒ_１、Ｒ_２において有してもよい置換基としては、ハロゲン基、メトキシ基又はヒドロキシ基が挙げられる。 <Colorant>
In the toner according to the present invention, the colorant contains a compound represented by the following general formula A.

In the above general formula A, Y is a polymer having a molecular weight Mp of 2000 to 18000. Z represents an aromatic ring or a heterocyclic ring which may have a substituent. R ₁ represents an alkyl group, an aromatic ring or a heterocyclic ring which may have a substituent. R ₂ , R ₃ , R ₄ and R ₅ each represents an alkyl group, an alkoxyl group, a hydroxyl group or a halogen group which may have a substituent. Examples of the substituent that R _{1 and} R ₂ may have include a halogen group, a methoxy group, and a hydroxy group.

The compound represented by the general formula A is a polymer-bound dye obtained by bonding a polymer and a dye component.
When the polymer represented by Y in the general formula A is prepared by radical polymerization, a monomer that becomes the structure of Y by polymerization is copolymerized with styrene, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, etc. May be. The copolymerization ratio is preferably 30 to 90% of the monomer to which the dye is bonded. The polymer represented by Y may be polyester, polyurethane, polyurea, or polyamide. Preference is given to polyester polyols.

ｋ、ｌ、ｍ、ｎは有る程度の分布を持つが、そのピーク値でｋ、ｌ、ｍ、ｎを示すと、式Ａ１において、ｋ＝２０、ｍ＝３０、ｎ＝３であり、式Ａ２においては、ｊ＝４５、ｋ＝３０、ｍ＝３５、ｎ＝３である。 The following formulas A1 and A2 are specific examples of polymer-bound dyes.

k, l, m, and n have a certain degree of distribution. When k, l, m, and n are indicated by their peak values, k = 20, m = 30, and n = 3 in equation A1, In A2, j = 45, k = 30, m = 35, and n = 3.

The compound represented by the general formula A can be synthesized, for example, by the following method.
First, p-nitrostyrene, styrene, n-butyl acrylate and the like are emulsion-polymerized to obtain a nitro polymer. As the polymerization-related drug, those generally used for emulsion polymerization can be used. Next, this nitro polymer is catalytically reduced to give an amino polymer. For the catalytic reduction, a general catalyst such as Pd—C can be used. Next, this amino polymer is diazotized with sodium nitrite to obtain a diazonium salt. At this time, the diazonium salt may become unstable depending on the counter anion. Therefore, for stabilization, it is replaced with a counter anion such as phosphorus hexafluoride or boron tetrafluoride and used for the next reaction in a water-containing state. Next, after coupling the obtained diazonium salt and a coupling agent which is a pigment component, the compound represented by the general formula A is obtained by separating and drying.

Here, as a coupling agent, the thing of following formula D1-D23 is mentioned. In the following formulas D1 to D23, the structure excluding X corresponds to Z represented by the general formula A.

上記式において、Ｒ_１は一般式Ａで示すＲ_１に該当する。 In the above formulas D1 to D23, X is represented by the following formula.

In the above formula, R ₁ corresponds to R ₁ represented by the general formula A.

  As another method of bonding the polymer represented by Y and a coupling agent, there is a method of reacting an isocyanate group-containing coupling agent with a polyester polyol having a hydroxyl group in a side chain. As another method, a method of polycondensation of a trivalent or higher alcohol or a trivalent or higher carboxylic acid to form a side chain having a substituent capable of ester bond to the polymer and co-condensation with the coupling agent moiety Is mentioned.

  By using a colorant containing a polymer-bound dye represented by the general formula A for the toner, a toner free from contamination due to document offset or sublimation can be produced. This is probably because the dye component in the toner particles is fixed to the toner by selecting the structure of the general formula A in which the low molecular weight dye is bonded to the polymer, and the dispersibility of the dye in the toner is good. Thus, it is assumed that the sublimation property and the document offset property are improved.

The molecular weight Mp is measured as follows. First, a measurement sample is added to tetrahydrofuran so that the concentration becomes 1 (mg / ml), and the mixture is dispersed for 5 minutes using an ultrasonic disperser at room temperature to be dissolved. Subsequently, after processing with a membrane filter having a pore size of 0.2 μm, 10 μl of a sample solution is injected into GPC (gel permeation chromatograph). The measurement conditions for GPC are as follows.
Apparatus: HLC-8220 (manufactured by Tosoh Corporation)
Column: TSKguardcolmn + TSKgelSuperHZM-M3 (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Solvent: Tetrahydrofuran Flow rate: 0.2 (ml / min)
Detector: Refractive index detector In the measurement of the molecular weight of a sample, the molecular weight distribution of the sample is calculated using a calibration curve measured using monodisperse polystyrene standard particles. And the peak top molecular weight Mp is calculated | required from the position of the peak vertex of the drawn molecular weight distribution.

<Release agent>
Examples of the release agent that can be used in the toner according to the present invention include known waxes as shown below.
(1) Polyolefin wax Examples include polyethylene wax and polypropylene wax.

(2) Long-chain hydrocarbon wax Examples include paraffin wax and sazol wax.
(3) Dialkyl ketone-based wax Examples include distearyl ketone.
(4) Amide wax Examples include ethylenediamine dibehenyl amide and trimellitic acid tristearyl amide.

(5) Ester wax Carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetramyristate, pentaerythritol tetrastearate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tri Examples include behenate, 1,18-octadecanediol distearate, tristearyl trimellitic acid, distearyl maleate 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 a stable toner image can be formed without causing a cold offset or the like even when fixing at a low temperature. Further, the wax content in the toner is preferably 1% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.

<External additive>
By adding the external additive, the fluidity and chargeability of the toner are improved, and the cleaning property is improved. The type of external additive is not particularly limited, and examples thereof include inorganic fine particles, organic fine particles, and lubricants.

  As the inorganic fine particles, known ones having an average primary particle size of about 4 to 800 nm 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 commercially available products R-805, R-976, R-974, R-972, R-812, R-809 manufactured by Nippon Aerosil Co., Ltd., HVK-2150 manufactured by Hoechst, H- 200, commercial products TS-720, TS-530, TS-610, H-5, MS-5 and the like manufactured by Cabot Corporation.
As titania fine particles, for example, commercially available products T-805 and T-604 manufactured by Nippon Aerosil Co., Ltd., commercially available products MT-100S, MT-100B, MT-500BS, MT-600, MT-600SS, and JA-1 manufactured by Teika Corporation. Commercial products TA-300SI, TA-500, TAF-130, TAF-510, TAF-510T manufactured by Fuji Titanium Co., Ltd. Commercial products IT-S, IT-OA, IT-OB, IT-OC manufactured by Idemitsu Kosan Co., Ltd. Etc.
Examples of the alumina fine particles include commercial products RFY-C and C-604 manufactured by Nippon Aerosil Co., Ltd., and commercial products TTO-55 manufactured by Ishihara Sangyo Co., Ltd.

  As the organic fine particles, spherical 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.

  In order to further improve the cleaning property and transfer property, a lubricant can be used. Examples of the lubricant include metal salts of higher fatty acids, such as zinc stearate, aluminum, copper, magnesium, calcium and other salts, zinc oleate, manganese, iron, copper, magnesium and other salts, zinc palmitate, Examples thereof include salts such as copper, magnesium and calcium, zinc linoleic acid, salts such as calcium, and salts such as zinc ricinoleic acid and calcium.

  The addition amount of these external additives is preferably 0.1 to 10.0% by mass with respect to the whole toner. Examples of the method for adding the external additive include a method using various known mixing apparatuses such as a Turbuler mixer, a Henschel mixer, a Nauter mixer, and a V-type mixer.

Next, the particle diameter of the toner according to the present invention will be described.
The toner according to the present invention preferably has a volume-based median diameter (D50v) of 3 μm or more and 8 μm or less. The toner according to the present invention has one of the problems of faithfully reproducing the color of a photographic image. By setting the volume-based median diameter within this range, for example, 1200 dpi (dpi; 1 inch (2.54 cm)) Can be reproduced faithfully. Thereby, even when printing a photographic image, the dot image constituting the photographic image is miniaturized, and a high-definition photographic image equal to or higher than the printed image is obtained. In particular, in the printing field called on-demand printing, where orders for printing are made at the level of hundreds to thousands, even if high-definition photographic images are included in the order, high-quality printed materials can be delivered to the user quickly. it can.

The volume-based median diameter (D50v) of the toner can be measured and calculated using an apparatus 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 (for example, a surfactant solution in which a neutral detergent containing a surfactant component was diluted 10-fold for the purpose of toner dispersion). Then, ultrasonic dispersion is performed for 1 minute to prepare a toner dispersion. This toner dispersion is poured into a beaker containing ISOTON II (manufactured by Beckman Coulter, Inc.) in a sample stand with a pipette until the measured concentration becomes 5 to 10%, and measurement is performed with a measuring instrument count set to 2500. The aperture diameter of the multisizer 3 is 50 μm.

The toner according to the present invention preferably has a coefficient of variation (CV value) in the volume-based particle size distribution of 2% to 21%, more preferably 5% to 15%.
The coefficient of variation (CV value) in the volume-based particle size distribution indicates the degree of dispersion in the particle size distribution of the toner particles on the volume basis and is defined by the following equation.
CV value (%) = (standard deviation in number particle size distribution) / (median diameter (D50v) in number particle size distribution) × 100

  The smaller this CV value, the sharper the particle size distribution, and the larger the toner particle size. That is, toners with uniform sizes can be obtained, and fine dots and fine lines required for an image can be reproduced with higher accuracy.

  The toner according to the present invention preferably has a softening point temperature (Tsp) of 70 ° C. or higher and 130 ° C. or lower, and more preferably 70 ° C. or higher and 110 ° C. or lower. By setting the softening point of the toner within this range, it is possible to fix the toner image at a temperature lower than the conventional one, and it is possible to form an environment-friendly image with reduced power consumption. The colorant used in the toner according to the present invention has a stable property that the spectrum does not change even under the influence of heat. However, by setting the softening point in the above range, the toner can be used during fixing. Since the thickness of the formed toner image is stabilized due to thermal deformation, it is preferable in terms of expressing more vivid and stable color reproducibility.

The softening point of the toner can be controlled by, for example, the following methods (1) to (3) alone or in combination.
(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 measurement of the softening point of the toner can be performed using “Flow Tester TFT-500 (manufactured by Shimadzu Corporation)”. First, a measurement sample is formed into a columnar shape having a height of 10 mm and set on a flow tester TFT-500. Then, a pressure of 1.96 × 10 6 Pa is applied from the plunger while heating at a heating rate of 6 ° C./min, and the mixture is pushed out from a nozzle having a diameter of 1 mm and a length of 1 mm. As a result, a curve (softening flow curve) between the plunger descending amount and temperature of the flow tester is drawn, and the temperature that flows out first is the melting start temperature, and the temperature for the descending amount of 5 mm is the softening point temperature.

<Method for producing toner>
The toner according to the present invention can be produced by a conventional toner production method. Conventional toner manufacturing methods include kneading, pulverization, and classification steps, as well as polymerizing polymerizable monomers and simultaneously forming toner particles while controlling the shape and size. It can be produced by applying a polymerization toner production method (for example, an emulsion association method, a suspension polymerization method, a polyester stretching method, etc.). The toner may be composed of a core and a shell, and the toner may be encapsulated.

For example, in the case of a toner manufacturing method using a pulverization method, the following steps are included.
(1) Synthesis of polymer-bound dyes (2) Kneading and crushing of materials constituting the toner (resins, colorants including synthesized products of polymer-bound dyes, release agents, external additives, etc.) When the toner according to the present invention is produced, the colorant dispersibility can be prepared by maintaining the temperature of the kneaded product at a discharge portion, that is, before the kneaded product is cooled, in a state where it is maintained at a temperature equal to or higher than the softening point of the resin. From the viewpoint of increasing

In the case of a toner production method by an emulsion association method, the following steps are included.
(1) Synthesis of polymer-bound dye (2) Preparation of dispersion of colorant containing synthesized product of polymer-bound dye (3) Polymerization of resin particles (4) Salting out / fusion of resin particles and colorant particles (5) Filtration and washing (6) External treatment

  From the viewpoint of enhancing the dispersibility of the colorant, in the emulsion association method and suspension polymerization method, after the colorant of the present invention is dissolved or dispersed in the polymerizable monomer, the polymerizable monomer in an aqueous medium is used. In the dissolution suspension method and the polyester elongation method, it is preferable to provide a step of polymerizing the body. By providing a step of dissolving the colorant of the present invention in a resin solution such as methyl ethyl ketone, the colorant of the present invention is added to the toner particles. Can be introduced.

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

  When used as a non-magnetic one-component developer, the toner is charged by sliding and pressing the charging member and the developing roller surface during image formation. Image formation by the non-magnetic one-component development method can simplify the structure of the developing device, and thus has an advantage that the entire image forming device can be made compact. Therefore, when the toner according to the present invention is used as a non-magnetic one-component developer, it is possible to perform full color printing which is compact and excellent in color reproducibility even in a working environment where space is limited.

When used as a two-component developer, full-color printing at high speed is possible using a tandem image forming apparatus described later. Further, by selecting a resin or wax constituting the toner, full color printing corresponding to so-called low-temperature fixing, in which the paper temperature at the time of fixing is about 100 ° C., is possible.
A well-known carrier can be used as a carrier which is a magnetic particle used when used as a two-component developer. Examples thereof include metals such as iron, ferrite, and magnetite, and alloys of these metals with metals such as aluminum and lead. 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.

<Image forming method>
An image forming method and an image forming apparatus using the toner according to the present invention will be described.
First, an image forming method and an image forming apparatus when the toner according to the present invention is used as a two-component developer will be described with reference to FIG. FIG. 1 shows an example of an image forming apparatus 11 that forms an image using the toner according to the present invention. The image forming apparatus 11 is called a tandem type color image forming apparatus.

As shown in FIG. 1, an image reading device 21 is provided on the upper part of the main body of the image forming apparatus 11.
The image forming apparatus 11 includes units uY, uM, uC, and uK that perform exposure and development for each color of Y, M, C, and K toners. The units uY, uM, uC, and uK include an exposure device u1, a developing device u2, a photoconductor u3, a charging unit u4, a cleaning unit u5, and a primary transfer roller u6, respectively. The primary transfer roller u6 is in pressure contact with the photoreceptor u3.

  Further, the image forming apparatus 11 includes an intermediate transfer unit 22, a secondary transfer roller 23, a fixing device 24, and a paper feeding unit 25. The intermediate transfer unit 22 includes an intermediate belt 2a wound by a plurality of rolls and rotatably supported, and a cleaning unit 2b. The secondary transfer roller 23 is pressed against the intermediate belt 2a.

  At the time of image formation, when the photosensitive member u3 is charged by the charging unit u4, exposure is performed by the exposure device u1, and an electrostatic latent image based on an image signal is formed on the photosensitive member u3. Next, development is performed by the developing device u2, and when toner is deposited on the photoreceptor u3 to form a toner image, the toner image is transferred to the intermediate belt 2a by the rotation of the photoreceptor u3 and the action of the primary transfer roller u6. Transcribed above. The exposure, development, and transfer processes are sequentially repeated by the units uY, uM, uC, and uK for each color in accordance with the rotation of the intermediate belt 2a, thereby superimposing the toner images of the respective colors on the intermediate belt 2a. An image is formed.

  On the other hand, when the paper is transported from the paper supply unit 25 and the paper is transported to the position of the secondary transfer roller 23, the secondary transfer roller 23 acts to collect color images from the intermediate belt 2a onto the paper. Transcribed. Thereafter, when the sheet is conveyed to the fixing device 24 and the color image is fixed and fixed on the sheet by pressurization and heating, the sheet is finally discharged to a tray provided outside. In this way, when the image formation is completed, the toner remaining on the photoconductor u3 and the intermediate belt 2a is removed by the cleaning units u5 and 22.

Next, an image forming method and an image forming apparatus when the toner according to the present invention is used as a nonmagnetic one-component developer will be described with reference to FIG.
FIG. 2 is an example of a color image forming apparatus 12 using a nonmagnetic one-component developer.
As shown in FIG. 2, the image forming apparatus 12 includes a charging brush 61 and a cleaning unit 63 that uniformly charge the surface of the photoconductor 62 to a predetermined potential around the photoconductor 62 that is rotationally driven.

  The exposure apparatus 3 is a laser scanning optical system including a laser diode, a polygon mirror, and an fθ optical element. When an image signal of each color of Y, M, C, and K is transferred from a host computer (not shown), the exposure device 3 outputs a laser beam based on the image signal and is uniformly charged by the charging brush 61. The surface 62 is scanned and exposed to form an electrostatic latent image on the photoreceptor 62.

  Further, the image forming apparatus 12 includes four developing devices 4Y, 4M, 4C, and 4K that accommodate non-magnetic one-component toners of Y, M, C, and K colors around the support shaft 43, respectively. Yes. Each time an electrostatic latent image of each color is formed on the photoconductor 62 by the exposure device 3, the developing devices 4Y, 4M, 4C, and 4K that contain the corresponding color toners are positioned so as to face the photoconductor 62. The developing devices 4Y, 4M, 4C, and 4K are driven to rotate about the support shaft 43. Each of the developing devices 4Y, 4M, 4C, and 4K guided to the position facing the photoconductor 62 performs development by attaching toner of each color onto the charged photoconductor 62.

  An intermediate transfer unit 7 having an intermediate belt 71 and a cleaning unit 74, a primary transfer roller 5, and a secondary transfer roller 73 are provided on the downstream side in the rotation direction of the photoconductor 62. The intermediate belt 71 rotates in synchronization with the photoconductor 62. Since the primary transfer roller 5 is pressed toward the photoconductor 62, the intermediate belt 71 comes into contact with the photoconductor 62 at the portion pressed by the primary transfer roller 5, and the toner image formed on the photoconductor 62. Is transferred to the intermediate belt 71. By repeating the above exposure, development, and transfer for each color image, a color image is formed on the intermediate belt 71 by superimposing the toner images for each color.

  On the other hand, the sheet is conveyed from the sheet feeding unit 64 to the position of the secondary transfer roller 73. The secondary transfer roller 73 is provided to face the support roller 72 that supports the intermediate belt 71, and the sheet is conveyed between the two rollers. Therefore, the toner image on the intermediate belt 71 is pressed and transferred onto the sheet. Is done. The sheet onto which the toner image has been transferred is conveyed to the fixing device 8 by the conveying unit 65, and the toner image is fixed. When the fixing is completed, the sheet is discharged to the outside of the image forming apparatus 12. Thereafter, the toner remaining on the photoreceptor 62 and the intermediate belt 71 is removed by the cleaning units 63 and 74.

  In the image forming apparatus 12 shown in FIG. 2, the developing devices 4Y, 4M, 4C, and 4K (hereinafter collectively referred to as the developing device 4) are configured to be replaceable. Such a replaceable developing device 4 is called a toner cartridge. The developing device 4 provided in the form of a toner cartridge supplies the developer stored therein when loaded in a predetermined position in the image forming apparatus 12. When there is no developer to be supplied, the developing devices 4Y, 4M, 4C, and 4K can be removed and replaced with a new developing device 4.

FIG. 3A shows an external appearance of the replaceable developing device 4, and FIG. 3B shows a cross-sectional configuration.
As shown in FIG. 3B, the developing device 4 is provided with a buffer chamber 42 adjacent to the developing roller 41 and a hopper 43 adjacent to the buffer chamber 42.

  The developing roller 41 has a conductive cylindrical base and an elastic layer formed on the outer periphery of the base using a material having high hardness such as silicone rubber. Further, a supply roller 46 is pressed against the developing roller 41. The supply roller is driven to rotate in the same direction as the developing roller 41 (counterclockwise fragrance in the drawing) 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.

  A blade 44 is disposed in the buffer chamber 42 so as to be in pressure contact with the developing roller 41. The blade 44 regulates the charge amount and adhesion amount of the toner on the developing roller 41. Furthermore, an auxiliary blade 45 can be provided on the downstream side of the blade 44 with respect to the rotation direction of the developing roller 41 as a member that assists in regulating the charge amount and adhesion amount of the toner on the developing roller 41.

  The hopper 43 contains toner T as a one-component developer. The hopper 43 is provided with a rotating body 431 for stirring the toner T. A film-like transport blade is attached to the rotating body 431, and the rotating body 431 rotates in the direction of the arrow shown in FIG. By conveyance, the toner T is supplied to the buffer chamber 42 via a passage 433 provided in a partition wall separating the hopper 43 and the buffer chamber 42. As the rotating body 431 rotates, the conveying blade is bent while conveying the toner T in the forward direction of the conveying blade, and when the conveying blade reaches the left end of the passage 433, the conveying blade returns to a straight state. Yes. In this way, the toner T can be supplied to the passage 433 by forming the conveying blade so that the shape returns straight after passing through the curved state.

  The passage 433 is provided with a valve for closing the passage 433. This valve is a film-like member, and one end is fixed to the upper side of the right side of the passage 433 of the partition wall. When the toner T is supplied from the hopper 43 to the passage 433, the valve T is pushed to the right by the pressing force of the toner T. A passage 433 is connected to. As a result, the toner T is supplied into the buffer chamber 42.

  A regulating member 432 is attached to the other end of the valve. The regulating member 432 and the supply roller 46 are arranged so as to form a slight gap even when the valve closes the passage 433. The regulating member 432 adjusts the amount of toner accumulated at the bottom of the buffer chamber 42 so that the toner T collected from the developing roller 41 to the supply roller 46 does not drop to the bottom of the buffer chamber 42 in a large amount. It is formed.

  When developing in the image forming apparatus 12, the developing roller 41 in the developing apparatus 4 is driven to rotate in the direction of the arrow shown in FIG. 3B, and the toner T in the buffer chamber 42 is supplied onto the developing roller 41 by the rotation of the supply roller 46. The The toner T supplied onto the developing roller 41 is charged and thinned by the blade 44 and the auxiliary blade 45, and then conveyed to a region facing the photoconductor 62, where the electrostatic latent image on the photoconductor 62 is developed. To be served. The toner T 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.

Next, the fixing device 8 will be described with reference to FIG.
The toner according to the present invention does not change the crystal structure of the colored azimuth in the toner at the heating temperature of the conventional fixing device, 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. For this reason, attention is also paid to reducing energy consumption in the fixing process, and so-called low-temperature fixing technology for fixing a toner image at a temperature lower than the current fixing temperature is employed.

  Therefore, when the toner according to the present invention is a toner compatible with low-temperature fixing, the surface temperature of the heating member in the fixing device 8 is preferably set to less than 200 ° C., and the surface temperature of the heating member is set to less than 180 ° C. Is more preferable. Under this set temperature, it is required to efficiently supply heat supplied from the heating member to the paper, and a fixing method called a belt fixing using a heat-resistant belt as either the heating member or the pressure member. Is preferred.

FIG. 4 is a view showing an example of a belt fixing type fixing device 8.
As shown in FIG. 4, the fixing device 8 is a type using a belt and a heating roller to ensure a nip width. The fixing device 8 mainly includes a fixing roller 81, a seamless belt 82, a pressure pad 821, and a lubricant supply member 85. Prepare.

  The fixing roller 81 is formed by forming a heat-resistant elastic body layer 81b and a release layer (heat-resistant resin layer) 81c around a metal core (cylindrical core) 81a, and a heating source is provided inside the core 81a. As a halogen lamp 83. The surface temperature of the fixing roller 81 is measured by the temperature sensor 84, and the halogen lamp 83 is feedback-controlled by a temperature controller (not shown) based on the measurement signal so that the surface of the fixing roller 81 is adjusted to maintain a constant temperature.

  The seamless belt 82 is in contact with the fixing roller 81 so as to be wound at a predetermined angle, thereby forming a nip portion. Inside the seamless belt 82, a pressure pad 821 having a low friction layer on its surface is disposed in a state of being pressed against the fixing roller 81 via the seamless belt 82. The pressure pad 821 includes a pressure pad 821a having a strong nip pressure and a pressure pad 821b having a weak nip pressure, and is held by a holder 821c made of metal or the like. A belt traveling guide is attached to the holder 821c so that the seamless belt 82 slides and rotates smoothly. The belt traveling guide is preferably a member having a low coefficient of friction because it rubs against the inner surface of the seamless belt 82, and a member having low thermal conductivity so that heat is not easily removed from the seamless belt 82. A specific example of such a material is polyimide.

  In addition, as the paper on which image formation is performed using the toner according to the present invention, in addition to coated paper such as plain paper and high-quality paper, art paper and coated paper from thin paper to thick paper, commercially available Japanese paper and Various paper such as postcard paper, plastic film for OHP, cloth and the like can be exemplified, but the invention is not limited to these.

  Examples of the present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In addition, although Examples 1 to 17 will be described, the toners according to these Examples and the developers using the toners are denoted by numbers 1 to 17. In addition, toners according to the comparative examples 1 to 3 are represented as comparative toners H1 to H3, and a developer using the comparative toners H1 to H3 is represented as developers H1 to H3.

<< Production of Toner according to Example >>
<Synthesis of polymer-bound dye>
First, a polymer-bound dye used for a colorant was synthesized. At this time, as shown in Tables 1 to 3, the polymer-bound dyes of Examples 1 to 17 were synthesized by changing the main materials used for the synthesis.

Hereinafter, a method for synthesizing a polymer-bound dye will be described as an example.
Polymerization step: First, 1.5 parts by mass of sodium lauryl sulfate is dissolved in 3000 parts by mass of distilled water. Thereafter, the mixture is heated to an internal temperature of 80 ° C. under a nitrogen stream, and an aqueous potassium persulfate solution (a solution obtained by dissolving 10.3 parts by mass of potassium persulfate in 200 parts by mass of distilled water) is added. Next, a solution in which 350 parts by mass of p-nitrostyrene, 350 parts by mass of methyl methacrylate, and 14 parts by mass of n-octyl mercaptan are well mixed is dropped into this solution over 1 hour. Thereafter, the internal temperature was raised to 90 ° C., and stirring was continued for 1 hour, followed by cooling to obtain a copolymer latex serving as a base polymer for the polymer-bound dye. The molecular weight Mp determined by gel permeation chromatography was 15300.

Reduction step: To this liquid, 50 parts by mass of a palladium carbon (Pd—C) catalyst is added, and hydrogen gas is passed through with stirring. After stirring for 24 hours, the palladium carbon catalyst was removed to obtain an amino compound.
Diazotization step: Next, the palladium carbon (Pd-C) catalyst was removed by decantation, and the resulting liquid was cooled with ice under a sodium nitrite aqueous solution (180 parts by mass of sodium nitrite to 1800 parts by mass of distilled water). Slowly add the dissolved one). After stirring this liquid for 1 hour, what dissolved 435 mass parts of sodium hexafluorophosphate in 2000 mass parts of distilled water is added, and also stirring is continued. After stirring for 1 hour, the liquid was filtered to obtain a wet diazo compound. This diazo compound was stored in a refrigerator in a wet state and used for the next reaction within 24 hours.

Coupling step: Next, 370 parts by mass of a coupling agent (coupling agent represented by Formula D1) and a reagent that serves as a catalyst for the coupling reaction are placed in 3000 parts by mass of dimethylformamide and stirred under ice cooling. The diazo compound was added to 2000 parts by mass of dimethylformamide and stirred under ice-cooling, and was gradually added with care so as not to generate heat suddenly to obtain an orange colored product. . Centrifugation and decantation were repeated and purified, and then thoroughly dried to obtain 950 parts by mass of the polymer-bound dye according to Example 1.
About the polymer coupling | bonding pigment | dye which concerns on Examples 2-17, main raw materials, such as a coupling agent, were changed as shown in the said Table 1-Table 3, and it synthesize | combined by the method similar to having mentioned above. In Examples 6 to 10, as shown in Table 2, the catalyst used in the reduction step is changed to a PS-PEG (polystyrene-polyethylene glycol) -fixed Pd complex catalyst.

<Crushing and dispersion of polymer-bound dye>
The previously obtained polymer-bound dye was well pulverized with a Henschel mixer.
Next, 100 parts by mass of Emar E-27C (manufactured by Kao Corporation) was dissolved in 3000 parts by mass of distilled water, and 380 parts of pulverized polymer-bound dye was added and stirred well. After stirring, it was dispersed to 200 nm (D50v) with an SC mill (Mitsui Mining Co., Ltd.). This dispersion is used as a dispersion of polymer dye for the production of toner.

In Examples 2-17, a polymer is obtained with the monomers 1-4 shown in Table 1 using the chain transfer agent and the polymerization initiator shown in Table 1 in the polymerization step. The molecular weight Mp of the obtained polymer is as shown in Table 1. In Table 1, MMA; methyl methacrylate, ST: styrene, BA; n-butyl acrylate, AA; acrylic acid, MAA; methacrylic acid, IA; itaconic acid, NOM; n-octyl mercaptan, NOMP; β-mercapto Propionic acid-n-octyl ester, TDM; t-dodecyl mercaptan, TOM: t-octyl mercaptan, KPS; potassium persulfate, APS; ammonium persulfate, SPS; sodium persulfate. In addition, Table 2 shows the catalysts used in the reduction steps of Examples 2 to 17, the parts by mass of sodium nitrite used in the diazotization step, and the substituted salts. In the coupling step, a coupling reaction was carried out by changing the coupling agent as shown in Table 3. The R _{1 to} R ₅ in the general formula A of the polymer-bound dye obtained by the coupling reaction, the yield and color of the polymer-bound dye are as shown in Table 3. In addition,

<Production of toner>
(1) Preparation of Toner 1 (Toner by Kneading and Crushing Method) The following materials were put into a Henschel mixer (manufactured by Mitsui Miike Mining Co., Ltd.), and the peripheral speed of the stirring blade was set to 25 m / second and mixed for 5 minutes.
Polyester resin (bisphenol A-ethylene oxide adduct, terephthalic acid, trimellitic acid condensate, weight average molecular weight 20000): 100 parts by mass Polymer-bound dye (according to Example 1): 5 parts by weight Release agent ( Pentaerythritol tetrastearate): 6 parts by mass Charge control agent (boron dibenzylate): 1 part by mass

In addition, the said polyester resin can be prepared with the following methods, for example.
First, 3.6 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 1. 6 mol, 1.7 mol of terephthalic acid, 0.1 mol of trimellitic anhydride, 2.4 mol of fumaric acid, and 0.12 g of dibutyltin oxide were placed in a 4-liter four-necked flask made of glass. A thermometer, a stirring rod, a condenser, and a nitrogen introducing tube were attached to the flask and placed in a mantle heater. The mixture is reacted at 215 ° C. for 5 hours under a nitrogen atmosphere to obtain a polyester resin (Tm = 95 ° C.). The molecular weight Mp of this polyester resin was 12000.

Moreover, when using polyester polyol resin instead of polyester resin, it can prepare with the following method.
Polyoxypropylene- (1,1) -2,2-bis (4-hydroxyphenyl) propane (Mitsui Toatsu Chemical Co., Ltd.) was added to a 500 ml separable flask equipped with a stirrer, thermometer, nitrogen inlet and reflux tube. Manufactured, KB-280, OH number: 291 KOH mg / g) 33.9 g, phthalic anhydride 26.1 g, and xylene 15 g were charged and stirred at an internal temperature of 80 ° C. until the system became uniform. Next, after adding 30 mg of benzyldimethylamine (BDMA) as a catalyst, the temperature was raised to 130 ° C. and reacted for 4 hours.
After cooling the reaction mixture to 50 ° C. or lower, 41.3 g of bisphenol A, 127.6 g of bisphenol A type liquid epoxy resin (Epomic R140P, epoxy equivalent 188 g / eq, manufactured by Mitsui Petrochemical Co., Ltd.), bisphenol A type solid epoxy resin (Mitsui Oil) Chemical Co., Epoxy R309, epoxy equivalent 2750 g / eq) 48 g, benzoic acid 19.7 g, stearic acid 3.5 g were charged, and tetramethylammonium chloride 50% aqueous solution 0.12 g was added at 80 ° C. After reacting at 160 ° C. for 1 hour, the reflux tube was replaced with a vacuum distillation apparatus, and xylene and water were distilled off while gradually increasing the degree of vacuum. After 1 hour, the degree of vacuum reached 1333 Pa (10 mmHg). After further stirring for 1 hour, the pressure in the reaction system is returned to normal pressure, and stirring is continued for 7 hours to obtain a polyester polyol resin.

  The mixture obtained by the mixing process is kneaded with a twin-screw extrusion kneader, coarsely pulverized with a hammer mill, then pulverized with a turbo mill pulverizer (manufactured by Turbo Kogyo Co., Ltd.), and further finely divided with an air classifier using the Coanda effect. By performing the classification treatment, colored particles having a volume-based median diameter of 5.5 μm were obtained.

Next, the following external additive was added to the colored particles, and the mixture was charged with a Henschel mixer (manufactured by Mitsui Miike Mining Co., Ltd.) and subjected to external addition treatment, whereby Toner 1 according to Example 1 was produced. In the external addition treatment, mixing is performed under conditions of a peripheral speed of 35 m / second of a stirring blade of a Henschel mixer, 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 parts by mass Titanium dioxide treated with n-octylsilane (average primary particle size 24 nm): 0.8 parts by mass

(2) Preparation of toner 2 (toner by emulsion association method; introduction method at the time of association) i) Preparation of colorant particle dispersion 11.5 parts by weight of sodium n-dodecyl sulfate was added to 160 parts by weight of ion-exchanged water and dissolved. The aqueous surfactant solution was prepared by stirring. In this surfactant aqueous solution, 5 parts by mass of the polymer binding dye according to Example 2 was gradually added, and dispersion treatment was performed using Clearmix W Motion CLM-0.8 (manufactured by MTechnic Co., Ltd.). A colorant particle dispersion was prepared.

The colorant particles in the colorant particle dispersion had a volume-based median diameter (D50v) 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: Prepared by adding ion-exchanged water to the measurement cell

ii) Preparation of core resin particles Core resin particles having a multilayer structure were prepared through the following first-stage polymerization, second-stage polymerization, and third-stage polymerization.
a) First-stage polymerization An anionic surfactant 4 having a structural formula of C ₁₀ H ₁₂ (OCH ₂ CH ₂ ) ₂ SO ₃ Na in a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device. Part by mass was added together with 3040 parts by mass of ion-exchanged water to prepare a surfactant aqueous solution.

A polymerization initiator solution in which 10 parts by mass of potassium persulfate (KPS) was dissolved in 400 parts by mass of ion-exchanged water was added to the surfactant aqueous solution, and the temperature was raised to 75 ° C. The monomer mixture was dropped into the reaction vessel over 1 hour.
Styrene: 532 parts by mass n-butyl acrylate: 200 parts by mass Methacrylic acid: 68 parts by mass n-octyl mercaptan: 16.4 parts by mass After dropwise addition of the monomer mixture, the diameter is heated at 75 ° C. for 2 hours. Then, polymerization was performed by stirring (this is referred to as first-stage polymerization) to produce resin particles J1.

b) Second stage polymerization Into a flask equipped with a stirrer, a monomer mixture composed of the following materials was charged, followed by 93.8 parts by mass of paraffin wax HNP-57 (manufactured by Nippon Wax Co., Ltd.) as a release agent. Was added and dissolved by heating to 90 ° C. to prepare a monomer solution.
Styrene: 101.1 parts by weight n-butyl acrylate: 62.2 parts by weight Methacrylic acid: 12.3 parts by weight n-octyl mercaptan: 1.75 parts by weight

  On the other hand, a surfactant aqueous solution in which 3 parts by mass of the anionic surfactant was dissolved in 1560 parts by mass of ion-exchanged water was prepared and heated to 90 ° C. A mechanical disperser having a circulation path after adding 132.8 parts by mass of the resin particles J (value converted to solid content) and further adding a monomer solution containing the paraffin wax to the aqueous surfactant solution. The mixture was mixed and dispersed for 8 hours using Claremix (M Technique Co., Ltd.). Thereby, an emulsified particle dispersion containing emulsified particles having a dispersed particle size of 340 nm (D50v) was prepared.

  Next, a polymerization initiator solution in which 6 parts by mass of potassium persulfate was dissolved in 200 parts by mass of ion-exchanged water was added to the obtained emulsified particle dispersion, and polymerization was performed by heating and stirring at 88 ° C. for 12 hours. Was referred to as second-stage polymerization) to prepare resin particles J2. The weight average molecular weight of the resin particles J2 was 23000.

c) Third-stage polymerization To the resin particles J2 obtained by the second-stage polymerization, a polymerization initiator solution in which 45 parts by mass of potassium persulfate was dissolved in 220 parts by mass of ion-exchanged water was added, Under a temperature condition, a monomer mixed solution composed of the following materials was dropped over 1 hour.
Styrene: 293.8 parts by mass n-butyl acrylate: 154.1 parts by mass n-octyl mercaptan: 7.08 parts by mass After completion of dropping, the mixture is heated and stirred for 2 hours to perform polymerization (this is called third-stage polymerization). After completion of the polymerization, cooling to 28 ° C. produced core resin particles. The core resin particles had a weight average molecular weight of 26800.

iii) Production of resin particles for shell The above resin for cores, except that the monomer mixture used in the first stage polymerization in the production of the resin particles for core was changed to a monomer mixture comprising the following materials: The polymerization reaction and the treatment after the reaction were performed in the same manner as the preparation of the particles, and the shell resin particles were prepared.
Styrene: 624 parts by mass 2-ethylhexyl acrylate: 120 parts by mass Methacrylic acid: 56 parts by mass n-octyl mercaptan: 16.4 parts by mass

iv) Preparation of Toner 2 Toner 2 according to Example 2 was prepared according to the following procedure.
a) Formation of core The following materials were charged and stirred in a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device. After adjusting the temperature in the reaction vessel to 30 ° C., a 5 mol / liter aqueous sodium hydroxide solution was added to adjust the pH to 8-11.
Resin particles for core: 420.7 parts by mass (solid content conversion)
Ion exchange water: 900 parts by weight Colorant particle dispersion: 200 parts by weight

Subsequently, an aqueous solution in which 2 parts by mass of magnesium chloride hexahydrate was dissolved in 1000 parts by mass of ion-exchanged water was added to the adjustment liquid at 30 ° C. over 10 minutes while stirring. After standing for 3 minutes, the temperature was raised and the temperature was raised to 85 ° C. over 60 minutes to associate the core resin particles with the colorant particles. In this state, the particle size of the associated particles was measured using Multisizer 3 (manufactured by Coulter, Inc.). When the volume-based median diameter of the associated particles reached 5.5 μm, 40.2 parts by mass of sodium chloride was added to ion-exchanged water. The association was stopped by adding an aqueous solution dissolved in 1000 parts by mass.
After the association was stopped, as a further aging treatment, the liquid temperature was set to 90 ° C., and the mixture was heated and stirred for 1 hour to continue the fusion, thereby forming a core. It was 0.895 when the average circularity of the core was measured by FPIA2000 (manufactured by Systex).

b) Formation of Shell Next, the liquid in which the association has been stopped is brought to 65 ° C., and 96 parts by mass of resin particles for shells are added. Further, 2 parts by mass of magnesium chloride hexahydrate is added to 1000 parts by mass of ion-exchanged water. Add dissolved aqueous solution over 10 minutes. Then, after heating up to 70 degreeC and stirring for 1 hour and fusing the resin particle for shells on the surface of a core, the aging process was performed at 90 degreeC for 20 minutes, and the shell was formed.

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

c) External Addition Treatment The following external additives were added to the produced toner particles, and the resulting mixture was added to a Henschel mixer (manufactured by Mitsui Miike Mining Co., Ltd.) and subjected to external addition treatment, whereby toner 2 according to Example 2 was obtained. In the external addition treatment, mixing is performed under conditions of a peripheral speed of 35 m / second of a stirring blade of a Henschel mixer, 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 parts by mass Titanium dioxide treated with n-octylsilane (average primary particle size 24 nm): 0.8 parts by mass

(3) Preparation of Toners 3-14 Toners 3-14 were prepared in the same procedure as in the preparation of Toner 2, except that the polymer-bound dye was changed to that according to Examples 3-14. The average circularity of the core measured for the toners according to Examples 3 to 14 is shown in Table 4.

(4) Preparation of Toner 15 (Toner by Emulsion Association Method: Introduction Method During Polymerization) i) Preparation of Dye-Containing Core Resin Particles Multi-layer structure through first-stage polymerization, second-stage polymerization and third-stage polymerization shown below Core resin particles having the following were produced.
a) First-stage polymerization An anionic surfactant 4 having a structural formula of C ₁₀ H ₁₂ (OCH ₂ CH ₂ ) ₂ SO ₃ Na in a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device. A mass part was added together with 3000 parts by mass of ion-exchanged water to prepare an aqueous surfactant solution.

A polymerization initiator solution in which 10 parts by mass of potassium persulfate (KPS) was dissolved in 700 parts by mass 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 by mass n-butyl acrylate: 200 parts by mass Methacrylic acid: 68 parts by mass n-octyl mercaptan: 16.4 parts by mass After dropwise addition of the monomer mixture, the diameter is heated at 75 ° C. for 2 hours. Then, polymerization (first stage polymerization) was carried out by stirring to produce resin particles J3.

b) Second-stage polymerization Into a flask equipped with a stirrer, a monomer mixture composed of the following materials was charged, followed by 72.8 parts by weight of paraffin wax HNP-57 (manufactured by Nippon Wax Co., Ltd.) as a release agent. Further, 40 parts by mass of the polymer-bound dye according to Example 15 was added, and the mixture was heated to 90 ° C. and dissolved to prepare a monomer solution.
Styrene: 100.0 parts by mass n-butyl acrylate: 60.2 parts by mass Methacrylic acid: 8.5 parts by mass n-octyl mercaptan: 1.50 parts by mass

  On the other hand, an aqueous surfactant solution in which 3 parts by mass of the anionic surfactant was dissolved in 1500 parts by mass of ion-exchanged water was prepared and heated to 98 ° C. A machine having a circulation path after adding 30.5 parts by mass (value converted to solid content) of the resin particles J3, and further adding a monomer solution containing the paraffin wax to the aqueous surfactant solution. It was mixed and dispersed for 8 hours using a Clairemix (manufactured by M Technique). Thus, an emulsified particle dispersion containing emulsified particles having a dispersed particle size of 375 nm (D50v) was prepared.

Next, a polymerization initiator solution in which 6 parts by mass of potassium persulfate was dissolved in 200 parts by mass of ion-exchanged water was added to the obtained emulsified particle dispersion, and polymerization was performed by heating and stirring at 92 ° C. for 12 hours. The resin particles J4 prepared by performing two-stage polymerization) had a weight average molecular weight of 23,000.

c) Third-stage polymerization To the resin particles J4 obtained by the second-stage polymerization, a polymerization initiator solution in which 5.45 parts by mass of potassium persulfate was dissolved in 220 parts by mass of ion-exchanged water was added, Under a temperature condition, a monomer mixed solution composed of the following materials was dropped over 1 hour.
Styrene: 300.0 parts by mass n-butyl acrylate: 150.0 parts by mass n-octyl mercaptan: 5.08 parts by mass After completion of the dropwise addition, the mixture is heated and stirred for 2 hours to perform polymerization (third stage polymerization). After the completion, it was cooled to 28 ° C. to produce core resin particles. The core resin particles had a weight average molecular weight of 27000.

ii) Preparation of resin particles for shell The resin for cores described above except that the monomer mixture used in the first stage polymerization in the preparation of the core resin particles was changed to a monomer mixture consisting of the following materials: The polymerization reaction and the treatment after the reaction were performed in the same manner as the preparation of the particles, and the shell resin particles were prepared.
Styrene: 605 parts by mass 2-ethylhexyl acrylate: 110 parts by mass Methacrylic acid: 50 parts by mass n-octyl mercaptan: 12.0 parts by mass

iii) Preparation of Toner 15 Toner 15 according to Example 15 was prepared according to the following procedure.
a) Formation of core The following materials were charged and stirred in a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introducing device. After adjusting the temperature in the reaction vessel to 30 ° C., the pH was adjusted to 10 by adding a 5 mol / l aqueous sodium hydroxide solution.
Resin particles for core: 300.0 parts by mass (solid content conversion)
Ion exchange water: 1000 parts by mass

Next, an aqueous solution in which 2 parts by mass of magnesium chloride hexahydrate was dissolved in 1000 parts by mass of ion-exchanged water was added to the preparation solution at 30 ° C. over 10 minutes while stirring. After standing for 3 minutes, the temperature was raised and the temperature was raised to 85 ° C. over 60 minutes to associate the core resin particles containing the colorant. In this state, the particle size of the associated particles was measured using Multisizer 3 (manufactured by Coulter), and when the volume-based median diameter (D50v) of the associated particles became 5.5 μm, 40.2 parts by mass of sodium chloride was added. The association was stopped by adding an aqueous solution dissolved in 1000 parts by mass of ion-exchanged water.
After the association was stopped, as a further aging treatment, the liquid temperature was set to 90 ° C., and the mixture was heated and stirred for 1 hour to continue the fusion, thereby forming a core. It was 0.912 when the average circularity of the core was measured with FPIA2100 (manufactured by Systex).

b) Formation of the shell Next, the liquid in which the association was stopped was brought to 85 ° C., 96 parts by mass of resin particles for the shell were added, and 2 parts by mass of magnesium chloride hexahydrate was dissolved in 1000 parts by mass of ion-exchanged water. The aqueous solution is added over 10 minutes. Thereafter, the temperature was raised to 90 ° C., and the mixture was stirred for 1 hour to fuse the resin particles for the shell to the surface of the core, followed by aging treatment at 75 ° C. for 20 minutes to form a shell.

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

c) External Addition Treatment The following external additives were added to the produced toner particles, and the mixture was added to a Henschel mixer (manufactured by Mitsui Miike Mining Co., Ltd.) and subjected to external addition treatment, whereby toner 15 according to Example 15 was obtained. In the external addition treatment, mixing is performed under conditions of a peripheral speed of 35 m / second of a stirring blade of a Henschel mixer, 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 parts by mass Titanium dioxide treated with n-octylsilane (average primary particle size 24 nm): 0.8 parts by mass

(4) Preparation of Toners 16 and 17 Toners 16 and 17 were prepared in the same procedure except that the polymer-bound dye was changed to that in Examples 16 and 17 in the preparation of toner 15.

<< Production of Toner according to Comparative Example >>
(1) Preparation of Comparative Toner H1 Comparative toner H1 according to Comparative Example 1 was prepared in the same procedure except that the polymer-binding dye according to Example 2 was changed to the low molecular color material G1 in the preparation of Toner 2. Produced.
The low molecular color material G1 has a structure obtained by removing Y of the polymer portion from the structure of the polymer-bound dye according to Example 1. In order to prepare the low molecular color material G1, in the production process of the polymer-bound dye according to Example 1, an amino form of p-nitrostyrene is obtained in the reduction process without passing through the polymerization process, and the diazotization process, cup What is necessary is just to pass through a ring process.

(2) Preparation of Comparative Toner H2 Comparative toner H2 according to Comparative Example 2 was prepared in the same procedure except that the polymer-bound dye according to Example 2 was changed to the low molecular color material G2 in the preparation of toner 2. Produced. The low molecular color material G1 has a structure obtained by removing Y of the polymer portion from the structure of the polymer-bound dye according to Example 2. In order to prepare the low molecular weight colorant G2, in the production process of the polymer-bound dye according to Example 2, an amino form of p-nitrostyrene is obtained in the reduction step without passing through the polymerization step, and the diazotization step, cup What is necessary is just to pass through a ring process.

(3) Preparation of Comparative Toner H3 Comparative toner H3 according to Comparative Example 3 was prepared in the same procedure except that the polymer-binding dye according to Example 2 was changed to the low molecular color material G3 in the preparation of Toner 2. Produced. The low molecular color material G3 has a structure obtained by removing Y of the polymer portion from the structure of the polymer-bound dye according to Example 3. In order to prepare the low molecular weight colorant G3, in the production process of the polymer-bound dye according to Example 3, an amino form of p-nitrostyrene was obtained in the reduction step without passing through the polymerization step, and the diazotization step, cup What is necessary is just to pass through a ring process.

<Production of developer>
Each of the toners 1 to 17 and the comparative toners H1 to H3 produced above is mixed with a ferrite carrier having a volume average particle diameter of 60 μm coated with a silicone resin, and the developer 1 to 17 having a toner concentration of 6% and comparative development Agents H1-H3 were prepared.

《Evaluation experiment》
(1) Evaluation of document offset property Evaluation images were printed on both sides with a commercially available full-color high-speed multifunction device (c6500; manufactured by Konica Minolta Business Technologies). The evaluation image is obtained by printing 6.0-point alphabets for 36 lines on the yellow background with the adjusted developers 1 to 17 and comparative developers H1 to H3. This evaluation image is printed on both sides using A4 size glossy paper, and printing is continuously performed for 50 sheets of paper (that is, 100 pages are printed).

The printed matter of 50 sheets printed on both sides was stacked and placed on a marble table, and a weight was placed so that a pressure equivalent to 19.6 kPa (200 g / cm ² ) was applied to the stacked portion. In this state, after being left for 3 days in an environment of a temperature of 30 ° C. and a humidity of 60% RH, the degree of image loss on the superimposed toner images was evaluated according to the following criteria.
Excellent: Image defect due to toner transfer or slight sticking between toner images is not seen, and there is no problem of image loss. Good: A crisp sound was heard when separating the printed materials one by one. However, there is no image defect and there is no problem of image loss. Practical use: When the printed materials in a stacked state are separated one by one, some gloss unevenness is observed on the toner image, but there is no image defect. Level at which it can be determined that there is almost no image defect. Bad: Character image transfer is recognized on the area where the character image was not originally output on the yellow background, and the contact toner is also discolored due to the image transfer on the character image. Among the above-mentioned evaluations of good, good, practical use, and failure, those with good, good, practical use were accepted.

(2) Sublimation property of toner 1.0 g of toner is spread on an aluminum foil petri dish, and the upper surface of the petri dish is covered with white paper. After heating the petri dish for 30 minutes with a hot plate heated to 200 ° C., the color change of the paper due to colorant sublimation was visually evaluated. The evaluation criteria are as follows.
○: No color change △: Small color change ×: Clear color change

(3) In-machine contamination property 100,000 sheets were printed by the above-mentioned evaluation machine, and the contamination state in the fixing device due to the sublimation of the colorant was visually evaluated. The evaluation criteria are as follows.
○: No contamination is observed Δ: Slight adhesion of the sublimated colorant is observed on the member near the fixing roller ×: Clear adhesion of the sublimated colorant is observed on a part of the fixing device member

(4) Toner scattering property (charging characteristics)
After 100,000 sheets were printed by the evaluation machine, the developing device was taken out and set in an idle rotating machine. A4 paper was placed around the sleeve of the developing device, and was rotated idly for 60 minutes, and the weight of the toner dropped on the paper was measured. The measured values were ranked and evaluated according to the following criteria. Note that the peripheral rotational speed of the sleeve of the developing device was 620 mm / second.
Rank 1: Less than 3 mg Rank 2: 3 mg or more but less than 6 mg Rank 3: 6 mg or more but less than 9 mg Rank 4: 9 mg or more but less than 12 mg Rank 5: 12 mg or more but less than 15 mg Rank 6: 15 mg or more Ranks 1 to 3 are acceptable.

(5) Transparency An image was formed on the OHT sheet, and the transparency of the image was evaluated. First, the visible spectral transmittance of an image was measured with a 330-type self-recording spectrophotometer (manufactured by Hitachi, Ltd.) using an OHT sheet on which toner is not carried as a reference, and the spectral transmittance at 650 nm was obtained. A scale. The greater the numerical value of the obtained spectral transmittance, the better the transparency. Here, it was judged that if it was 65% or more, it had good transparency. The evaluation image is printed under the condition that the toner adhesion amount is 4 g / m ² .

The evaluation results are shown in Table 5.

  As shown in Table 5, all of the toners 1 to 17 according to the examples are excellent in document offset property, and also have good results with respect to sublimation and contamination due to sublimation. This is probably because, by selecting the structure of the general formula A in which a low molecular weight dye is bonded to the polymer as the dye used for the colorant, the fixing of the dye in the toner particles is ensured and the dispersion to the whole toner is prevented. This is thought to be due to the improvement. On the other hand, the toners H1 to H3 according to the comparative examples are all poor in document offset property and have low evaluation of sublimation, and thus it is understood that contamination in the fixing device has occurred. This is presumably because the low molecular weight dye is used as it is without being bound to the polymer, so that the fixing of the dye on the toner particles is weak.

  In addition, the toners 1 to 17 according to the examples have good results that the evaluation value of the scattering / charging characteristics is 6.1 mg even if the evaluation value of the scattering / charging characteristics is large, which is considerably lower than the acceptable rank of 9 mg due to the improvement of the sublimation property. The toners H1 to H3 according to the comparative examples are all 13.0 g or more and cannot reach the pass rank.

Further, in the evaluation of transparency, most of the toners 1 to 17 according to the examples exceed 80 (%), and a vivid and transparent color development is possible.
In addition, as shown in Table 3, the synthesized products of the polymer-bound dyes synthesized in the examples exhibit various colors among the same orange colors such as orange, citrus color, and Yamabuki. That is, in the toner according to the present invention, the color tone can be selected by the combination of the coupling agent and the base (coupling reaction with the diazonium salt), and stable color reproducibility can be realized with a wider color tone than conventional. It becomes possible. In particular, in recent years, there are many cases in which images displayed on a display are printed, but the color gamut of conventional color printing is much narrower than the color gamut on the display, so the color of the image on the display and the printed image is different. There was a big difference. However, by using the toner according to the present invention, it is possible to obtain a print image closer to the color gamut of the display than before. Thus, it can be said that the toner according to the present invention greatly contributes to the expansion of the color gamut in the toner image.

1 is an example of an image forming apparatus capable of image formation by a two-component development system. 1 is an example of an image forming apparatus capable of image formation using a non-magnetic one-component development system. FIG. 4 is a diagram illustrating an example of a developing device (toner cartridge). FIG. 3 is an internal cross-sectional view of a developing device (toner cartridge). It is an example of a fixing device of a belt fixing system using a belt and a heating roller.

Explanation of symbols

11 Image forming device (two-component development system)
u2 developing device 24 fixing device 12 image forming device (non-magnetic one-component developing system)
4Y, 4M, 4C, 4K Developing device 41 Developing roller

Claims (1)

In a toner containing a resin and a colorant,
A toner in which the coloring component of the colorant has a structure represented by the following general formula A.

In the above general formula A, Y is a polymer having a molecular weight Mp of 2000 to 18000. Z represents an aromatic ring or a heterocyclic ring which may have a substituent. R ₁ represents an alkyl group, an aromatic ring or a heterocyclic ring which may have a substituent. R ₂ , R ₃ , R ₄ and R ₅ each represents an alkyl group, an alkoxyl group, a hydroxyl group or a halogen group which may have a substituent.

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