JP2014186256A - Magenta toner for electrostatic charge image development - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge image development that ensures fixability and blocking resistance, while suppressing dust generated during fixation, and provides excellent image quality, and in particular, to provide a toner for electrostatic charge image development that is excellent in the above performances even being a low-temperature fixing toner.SOLUTION: There is provided a magenta toner containing at least a colorant, a binder resin, and a wax, in which the wax has a specific structure, and the colorant is obtained by appropriately selecting compounds having a specific structure and combining the selected compounds.

Description

  The present invention relates to a magenta toner for developing an electrostatic charge image containing a specific wax and pigment, and in particular, suppresses dust generated at the time of fixing and secures fixability and anti-blocking properties, and can be used for repeated printing over a long period of time. The present invention relates to a magenta toner for developing an electrostatic charge image that retains good charging characteristics and exhibits stable and good image quality.

In an image forming apparatus such as an electrophotographic apparatus or an electrostatic recording apparatus, an electrostatic latent image formed on a photoreceptor is developed with toner. Next, the formed toner image is transferred onto a transfer material such as paper as necessary, and then fixed by heating, pressing, or the like.
In such image forming apparatuses, digital full-color copying machines and digital full-color printers have been put into practical use.

In a digital color copying machine, a color image original is color-separated by blue (B), green (G) and red (R) filters, and then a static image having a dot diameter of 20 to 70 μm corresponding to the original color original. A full-color image is formed by using a subtractive color mixing method using yellow, magenta, cyan, and black toners as an electrostatic latent image.
Conventionally, quinacridone colorants, thioindigo colorants, xanthene colorants, monoazo colorants, perylene colorants, diketopyrrolopyrrole colorants, and the like have been used as colorants for magenta toners.

  For example, Japanese Patent Publication No. 49-46951 proposes a 2,9-dimethylquinacridone pigment, Japanese Patent Publication No. 55-26574 proposes a thioindigo pigment, and Japanese Patent Publication No. 59-57256 discloses A xanthene dye is proposed, a diketopyrrolopyrrole pigment is proposed in Japanese Patent Application Laid-Open No. 2-210459, and an anthraquinone dye is proposed in Japanese Patent Publication No. 55-42383.

  These magenta colorants have good affinity with the binder resin and light resistance, and can provide magenta toners with excellent tribocharging properties and color tone, but they can be printed repeatedly over a long period in copiers and printers. When it did, there existed a difficulty which image degradation will produce. This is due to the deterioration of the charging characteristics, such as the amount of charge changing and the amount of reversely charged toner increasing due to repeated printing, and good charging characteristics are maintained for repeated printing over a long period of time. There is a need for a magenta toner that can provide stable and good image quality.

  Furthermore, with the recent spread of copiers and printers, in addition to the demand for further improvement in image quality, a toner that is particularly excellent in high-speed printing and low-energy fixability has been desired, and the low-temperature fixability of the toner has been increased. Improvements are being attempted. At the same time, environmental standards centered on Europe have been established to deal with the impact on the human body in the office environment, and countermeasures are becoming essential in electrophotographic fixing systems.

In recent years, in particular, it has become essential to obtain the most stringent “Blue Angel” certification, and in electrophotographic fixing systems, substances that are generated during high-temperature fixing and diffused outside the device, specifically sublimation. There is a demand for “dust and organic volatile substances” due to substances and the like to be less than or equal to the regulation values defined in ECMA-328 / RAL-UZ122.
In Japan, the standard values of RAL-UZ122 have been adopted as they were since the re-revision in 2008 as the Eco Mark certification standards for copiers and multifunction machines. It has been demanded.
Low melting point wax is used to fix toner at low temperature.

Japanese Patent Laid-Open No. 06-123999 JP 07-199538 A JP-A-11-249331 JP 11-288124 A JP 2001-209209 A However, since the low melting point wax is easily dissolved and sublimated at a low temperature, it becomes a causative substance of dust and it is difficult to achieve a reduction in the sublimation substance.

On the other hand, although it is possible to reduce sublimation substances by using a wax having a high melting point, low-temperature fixability and glossiness are required as toner performance, and simply selecting a high melting point wax These toner performances are significantly impaired.
In addition, the wax tends to be poorly dispersed in the toner as the melting point becomes higher. For this reason, the chargeability and fluidity of the toner are impaired, and image quality deterioration such as fog is likely to occur.

  In other words, environmental safety and toner performance are in a trade-off relationship, and no one that can meet both requirements has been provided.

  An object of the present invention is to suppress static dust generated at the time of fixing, to secure fixing property and anti-blocking property, to maintain good charging characteristics for repeated printing over a long period of time, and to provide a stable and good image quality. It is to provide a magenta toner for image development.

The present inventor has repeatedly studied to solve the above problems and found that the above problems can be solved by using a specific wax and pigment in combination.
That is, the present invention contains at least a colorant, a binder resin and a wax and is represented by the structural formula (1), and the colorant is represented by the structural formula (2) and / or (3) and the structural formula (4). It is an object of the present invention to provide an electrostatic charge image developing toner characterized by being a compound.

[In Structural Formula (2), R ¹¹ and R ¹² each independently represent H or CH ₃ . ]

[In the structural formula (3), R ¹³ represents CH ₃ or OCH ₃ , R ¹⁴ represents H or Cl, and R ¹⁵ represents OCH ₃ or Cl. ]

[In Structural Formula (4), R ¹⁶ represents Cl or SO ₃ ^— , R ¹⁷ represents H, CH ₃ or Cl, R ¹⁸ represents H or SO ₃ ^— , and any one of R ¹⁶ and R ¹⁸ or the other only SO ₃ ^- represents a. M ²⁺ represents a divalent metal ion. ]

  According to the present invention, electrostatic charge that suppresses dust generated during fixing, secures fixability and anti-blocking properties, maintains good charging characteristics for repeated printing over a long period, and exhibits stable and good image quality. It is to provide a magenta toner for image development.

It is a longitudinal cross-sectional view of the wet bead mill which is an example of the apparatus used in preparation of a coloring agent dispersion liquid. It is the schematic which shows an example of a structure of the dispersion | distribution process used in preparation of a coloring agent dispersion liquid.

The magenta toner for developing an electrostatic charge image of the present invention contains a wax having a specific structure, two or three kinds of pigments and a resin having a specific structure, and, if necessary, a charge control agent, an external additive and the like. You may do it. Hereinafter, “magenta toner for developing an electrostatic image” may be simply abbreviated as “toner” or “magenta toner”.
According to the study of the present inventor, most of the causative substances of dust generated at the time of heat fixing and diffused outside the apparatus are wax components contained in the toner. The heated fixing device that passes when the toner transferred onto the paper is fixed not only dissolves the wax in the toner and exerts a releasing action, but also a part of the toner sublimates to generate “dust”. It has occurred. Therefore, since dust is the result of the physical sublimation phenomenon of the wax component, a method for suppressing the sublimation of the wax itself is required.

  Here, “dust” in the present invention refers to a substance collected by a filter in accordance with a measurement method (RAL-UZ122-2006) certified by Blue Angel Mark and collected on the filter. Therefore, “dust” in the present invention is not limited to solids such as dust, dust, and debris, but refers to all substances other than gas collected on the filter by the measurement method. The “dust” in the present invention includes those dusts that have been emitted from the toner, once converted into a gas or liquid, and collected on the filter as a liquid or solid.

When non-polar wax is used as the wax of the toner, a high release effect is obtained without being familiar with the binder resin, and since it is highly hydrophobic, it is advantageous in terms of environmental resistance, but the intermolecular force is low. Therefore, it may be difficult to suppress dust. In addition, when a method of suppressing the dust by increasing the molecular weight is used, the melting point is increased and the low-temperature fixability may not be achieved.
In addition, in the wet method, since non-polar wax is handled in an aqueous medium, sufficient dispersion stability is required, and the wax incorporated during the production is uniformly dispersed in the toner, and is added to the resin. It must also be well wrapped. That is, nonpolar wax tends to improve toner performance, but it may be difficult to manufacture.

On the other hand, there is a method of suppressing sublimation by increasing the intermolecular force between wax molecules or between a wax and a resin component. A typical example is an ester wax having a polar group, but these have low sublimation even at a relatively low melting point, and are useful for suppressing dust without deteriorating fixing performance. However, the familiarity with the resin and the introduction of polar groups make it possible to manufacture wax relatively easily by preventing the leakage of wax, but at the same time chargeability under high temperature and high humidity and long-term storage stability. Since the toner may be damaged greatly, the toner performance itself may be problematic.
The relationship between the dispersion state of the wax and the charging characteristics of the toner is not always clear, but it is thought that the charging characteristics change due to direct or indirect factors such as differences in toner fluidity due to the difference in the dispersion state of the wax. It is done.

That is, controlling the dispersion state of the wax is an important means for controlling the charging characteristics of the toner.
It is also known that the dispersibility of pigments and waxes in toner varies greatly depending on the type and combination.
For this reason, the optimum combination of pigment and wax can optimize the dispersion state of each, have good charging characteristics, maintain good charging characteristics for long-term repeated printing, and provide stable and good image quality. Magenta toner is expected to be obtained.

The present invention has been completed on the basis of these findings. It suppresses dust generated at the time of fixing, secures fixability and blocking resistance even with a low-temperature fixing toner, and has excellent image quality. A magenta toner for developing a charge image can be provided. Further, by using a specific pigment in combination, it is possible to provide a magenta toner for developing an electrostatic charge image that has excellent charging characteristics, maintains good charging characteristics for repeated printing over a long period of time, and exhibits stable and good image quality.
The wax used in the toner of the present invention is represented by the following structural formula (1).

[In the formula (1), R ¹ represents an alkyl group having 10 or more carbon atoms or an alkoxy group, R ² represents —X—COOR ³ (wherein X represents an alkylene group, and R ³ represents an alkyl group having 10 or more carbon atoms. Or an alkyl group having 10 or more carbon atoms. ]
R ¹ is an alkyl group or an alkoxy group, and R ³ is an alkyl group having 20 or more carbon atoms. Alternatively, R ² is an alkyl group having 10 or more carbon atoms, preferably 16 or more carbon atoms. Particularly preferred is an alkyl group having 20 or more carbon atoms. When R ² is —X—COOR ³ , R ¹ is preferably an alkoxy group (ie, a diester). Specific examples include aliphatic ketones such as di-n-decyl ketone, di-dodecyl ketone, di-n-stearyl ketone, di-n-icosyl ketone, di-n-behenyl ketone, and di-n-tetracosyl ketone. Aliphatic diesters such as dodecyl sebacate, distearyl sebacate and dibehenyl sebacate; aliphatic monoesters such as stearyl laurate, behenyl laurate, stearyl stearate, behenyl stearate, stearyl behenate and behenyl behenate Etc. These mixtures are also suitable, but at this time, it is preferable that the half width of the DSC endothermic peak is 30 ° C. or less.

As a method of adding the wax, a known method can be used.
In the present invention, the amount of wax added is preferably 3 to 30 parts by weight. A more preferred range is 5 to 20 parts by weight, and a most preferred range is 5 to 15 parts by weight.
When the wax content is less than the preferred range, performance such as low-temperature fixability, glossiness, and high-temperature offset property may not be sufficient, and when it exceeds the above range, toner fluidity and charging characteristics deteriorate. There is a case. In addition, there may be a problem that a large amount of dust is generated during fixing. Further, the blocking resistance may not be sufficient, or the apparatus may be contaminated due to leakage of wax from the toner.

When the wax in the toner is in the above range, both “suppression of dust generated during fixing” and “coexistence of low-temperature fixing property and blocking resistance” can be achieved.
One type of wax may be used in the present invention, or a plurality of waxes may be mixed.
The pigment used in the present invention is a combination of the structural formula (2) and / or (3) and the structural formula (4).

[In Structural Formula (2), R ¹¹ and R ¹² each independently represent H or CH ₃ . ]

[In the structural formula (3), R ¹³ represents CH ₃ or OCH ₃ , R ¹⁴ represents H or Cl, and R ¹⁵ represents OCH ₃ or Cl. ]

[In Structural Formula (4), R ¹⁶ represents Cl or SO ₃ ^— , R ¹⁷ represents H, CH ₃ or Cl, R ¹⁸ represents H or SO ₃ ^— , and any one of R ¹⁶ and R ¹⁸ or the other only SO ₃ ^- represents a. M ²⁺ represents a divalent metal ion. ]
The compounds of structural formulas (2) and (3) can be used in any ratio, but the sum of the compounds of structural formulas (2) and (3) and the compound of structural formula (4) are 95: 5 to 5: A range of 95 is preferred. More preferably, it is 95: 5 to 50:50, and most preferably 95: 5 to 60:40.

If the content of the compounds of the structural formulas (2) and (3) is too large, the change in the charge amount during repeated printing is large, causing deterioration in image quality. On the other hand, if the content of the compound of the structural formula (4) is too large, the image quality is deteriorated due to deterioration of charging characteristics under high temperature and high humidity.
Further, the addition amount of the pigment is preferably 3 to 20 parts by weight. More preferably, it is 3 to 15 parts by weight, and most preferably 3 to 10 parts by weight.

The magenta toner of the present invention preferably has a core / shell structure. The core / shell structure can be prepared by a known method, but the emulsion polymerization aggregation method or its modified method is most preferable.
When using the emulsion polymerization agglomeration method or a modified method thereof, the compounding method of the wax includes a method of pre-dispersing in the resin in the resin particle dispersion, and a method of emulsifying the wax to obtain a dispersion, and a colorant dispersion, a resin particle dispersion There is a method of agglomerating and fusing together with a raw material dispersion.

  As the former method, a method using so-called seed emulsion polymerization in which wax is added as a seed during emulsion polymerization, a method using so-called mini-emulsion polymerization in which emulsion polymerization is performed in a state where wax is dissolved or finely dispersed in a monomer, vinyl A method of dispersing a wax in a resin particle in a resin particle dispersion by emulsifying the resin after a wax is previously dispersed in a binder resin such as a resin or a polyester resin by kneading or the like can be used.

Further, as the latter, there is a method in which wax is emulsified and dispersed by a known method and agglomerated and fused together with a raw material dispersion such as a colorant dispersion or a resin particle dispersion. At this time, the hydrocarbon wax and the ester wax may be used by being melt-mixed in advance or may be separately dispersed and used, but it is more preferable to use them after being melt-mixed in advance.
Among these, the former method, that is, a method in which the wax is previously dispersed in the resin particles of the resin particle dispersion is preferable from the viewpoint that the wax can be uniformly dispersed.

The emulsion polymerization agglomeration method is to prepare a resin particle dispersion, a colorant dispersion, etc., which are dispersions of polymer primary particles obtained by emulsion polymerization, and prepare a wax dispersion if necessary. In this method, the toner base particles are obtained by dispersing these in an aqueous medium and performing heating or the like, followed by an aggregation step and a ripening step of fusing the particles.
In emulsion polymerization, wax or the like can be contained in polymer primary particles (resin particles in a resin particle dispersion) by seed emulsion polymerization or miniemulsion polymerization.

A modification of the emulsion polymerization aggregation method is a resin particle dispersion wherein a vinyl resin, a polyester resin or the like polymerized in advance by a known method is emulsified by a known method to obtain a resin particle dispersion, at least a colorant dispersion. And a method of obtaining toner base particles through a process of aggregating and fusing the resin particle dispersion.
In a modification of the emulsion polymerization aggregation method, a toner can be produced in the same manner as the emulsion polymerization aggregation method except that a raw material such as wax can be dispersed in the resin in advance.

In the present invention, as the binder resin contained in the toner and the resin constituting the resin particles in the resin particle dispersion, resins conventionally used as the binder resin for the toner can be appropriately used.
For example, among the binder resins, monomers used for the vinyl resin include the following.

Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene , Pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, etc. Styrene derivatives of ethylene; ethylenically unsaturated monoolefins such as ethylene, propylene, putylene, isobutylene; unsaturated polyenes such as butadiene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; vinyl acetate , Vinyl esters such as vinyl propionate and vinyl benzoate, Methyl acrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, behenyl methacrylate, phenyl methacrylate, Methacrylic acid esters such as dimethylaminoethyl methacrylate and dimethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, behenyl acrylate, phenyl acrylate, 2-chloroethyl acrylate, dimethylaminoethyl acrylate, dimethyl acrylate Acrylic esters such as Noethyl; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole N-vinyl compounds such as N-vinylindole and N-vinylpyrrolidone; vinyl naphthalenes; and acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide.

These vinyl monomers are used alone or as two or more copolymers, but are not limited thereto.
Among these, a combination of vinyl monomers forming a styrene copolymer, a styrene-acrylic copolymer, and a styrene-methacrylic copolymer is preferable.
Furthermore, it is preferable that a monomer having two or more polymerizable double bonds is mainly used as the crosslinkable monomer.

  Examples of such compounds include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, and 1,5-pentanediol. Diacrylates linked by alkyl chains such as diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, etc .; dimethacrylates in which the acrylate of the above compound is replaced by methacrylate; diethylene glycol diacrylate, triethylene glycol diacrylate Diacrylates linked with alkyl chains containing ether linkages such as acrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, dipropylene glycol diacrylate, etc. Acrylates; dimethacrylates in which the acrylate of the above compound is replaced by methacrylate; polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2- Aromatic groups such as bis (hydroxyphenyl) propane diacrylate; dimethacrylate in which the acrylate of the above compound is replaced by methacrylate; polyester-type diacrylate compounds, pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane tri Acrylate, tetramethylol methane tetraacrylate, oligoester acrylate; acrylate of the above compound replaced with methacrylate; triallyl cyanurate; triallyl trimellite DOO; Although the like can be exemplified, but the invention is not limited thereto.

From the viewpoint of fixability and offset resistance, those that are preferably used include aromatic divinyl compounds and diacrylate compounds linked by a chain containing an aromatic group or an ether bond.
These crosslinking agents are preferably used in an amount of 0 to 5% by mass, particularly preferably 0.03 to 3% by mass, relative to 100% by mass of other monomer components.
These binder resins may be formed into a resin particle dispersion by emulsion polymerization, or may be polymerized by a known method and then emulsified and dispersed by a known method to obtain a resin particle dispersion.

Among the binder resins, as the polyester resin, a polyester resin obtained by condensing a polyvalent carboxylic acid component and a polyhydric alcohol component can be used.
Among the polyvalent carboxylic acid components, examples of the divalent carboxylic acid component include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, oxalic acid, and succinic acid. Acid, glutaric acid, adipic acid, pemelic acid, azelinic acid, sebacic acid, azelaic acid, malonic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12 -Dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4, 4'-biphenyldicarboxylic acid, n-dodecenyl succinic acid, isododecenyl succinate Examples include succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, isooctenyl succinic acid, n-octyl succinic acid, isooctyl succinic acid, anhydrides or lower alkyl esters of these acids, etc. It is not limited to.

  Among the polyhydric alcohol components, examples of the divalent alcohol component include polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene (3,3) -2,2 -Bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) Bisphenol A alkylene oxide adducts such as propane, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol 1,4-butenediol, 1,5-pentanedio 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polytetramethylene glycol , Bisphenol A, hydrogenated bisphenol A and the like, but are not limited thereto.

As the crosslinking agent, a trivalent or higher carboxylic acid component and / or a trivalent or higher alcohol component is used.
Examples of the trivalent or higher carboxylic acid component include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, and 1,2 , 4-Naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4- Examples include cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, embol dimer acid, acid anhydrides thereof, and lower alkyl esters.

  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, trimetroleethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. However, it is not limited to these.

The trivalent or higher carboxylic acid component and / or the trivalent or higher alcohol component used as the crosslinking agent is preferably 0 to 10% by mass, particularly preferably 0.03 to 5% by mass with respect to 100% by mass of the monomer component. % Used.
These resins are polymerized by a known method, then emulsified and dispersed by a known method, and used as a resin particle dispersion.

A crystalline resin can also be used.
Examples of the crystalline resin include those obtained by copolymerizing long-chain alkyl acrylates such as stearyl acrylate and behenyl acrylate and long-chain alkyl methacrylates alone or with other vinyl monomers. However, it is not limited to these.

These resins may be formed into a resin particle dispersion by emulsion polymerization, or may be polymerized by a known method and then emulsified and dispersed by a known method to obtain a resin particle dispersion.
In the polyester resin, as the polyvalent carboxylic acid component, for example, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10 -Decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradidecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18 -Octadecanedicarboxylic acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, or the like, or acid anhydrides or lower alkyl esters thereof are used. For example, ethylene glycol, 1,3-propanediol, 1,4-butanedio 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecane Diols, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol and the like are used, but are not limited thereto. is not.

These resins are polymerized by a known method, then emulsified and dispersed, and used as a resin particle dispersion.
In the present invention, it is preferable to use one or more types of crosslinked resin particle dispersions and, if necessary, one or more types of non-crosslinked resin particle dispersions. It is particularly preferable that the resin particle dispersion is a particle dispersion of a crosslinked resin and a non-crosslinked resin. That is, it is particularly preferable to use one or more types of crosslinked resin particle dispersions and one or more types of non-crosslinked resin particle dispersions in combination.

  For example, a plurality of types of crosslinked resin dispersions having different monomer compositions may be used, and a plurality of types of non-crosslinked resin particle dispersions having different monomer compositions may be used in combination as necessary. Moreover, you may use the crosslinked resin particle dispersion which has 2 or more types of different crosslinking degree as a crosslinked resin particle dispersion. Furthermore, one or more types of crosslinked resin particle dispersions having different molecular weights or molecular weight distributions and one or more types of non-crosslinked resin particle dispersions having different molecular weights or molecular weight distributions may be used.

  Although the THF-insoluble content is determined by the ratio of the crosslinked resin and the non-crosslinked resin, the THF-insoluble content in the toner is preferably 10% by mass or more, more preferably 15% by mass or more based on the whole toner, It is particularly preferably 20% by mass or more. Further, the upper limit is preferably 40% by mass or less, more preferably 35% by mass or less, and particularly preferably 30% by mass or less. If the THF-insoluble content in the toner is small, a hot offset phenomenon tends to occur, and if the THF-insoluble content is large, the low-temperature fixability and gloss may be impaired.

  The resin design may be such that the tetrahydrofuran (THF) insoluble content of the resin component in the toner is preferably 3 to 35% by mass, more preferably 5 to 30% by mass, and particularly preferably 10 to 20% by mass. preferable. When the THF-insoluble content of the resin component in the toner is small, a hot offset phenomenon tends to occur, and when the THF-insoluble content is large, the low-temperature fixability and gloss may be impaired.

The weight-average molecular weight of the toner soluble matter in THF as measured by gel permeation chromatography (GPC) is preferably 30,000 to 100,000, and the molecular weight peak is 10,000 to 60,000. It is more preferable. More preferably, the weight average molecular weight is 30,000 to 80,000, and the molecular weight peak is particularly preferably 10,000 to 50,000.

The above-mentioned “THF soluble matter of toner” includes THF soluble components such as the above-mentioned wax and a resin having a sulfonic acid group and / or a sulfonic acid salt described later.
The resin particle dispersion, the colorant dispersion, and, if necessary, the wax dispersion are separately prepared as emulsified dispersions, and are contained in the toner by aggregation and fusion.
Furthermore, a core / shell structure can be obtained by using one or more types of resin particle dispersions as a core and one or more types of resin particle dispersions as a shell.

The core resin particle dispersion preferably contains at least one kind of crosslinked resin particle dispersion.
The shell preferably contains at least one non-crosslinked resin particle dispersion.
The resin component that forms the shell is preferably 0.5 to 40% by mass, particularly preferably 1 to 20% by mass, based on the total resin component.

The content of the non-crosslinked resin particles is preferably 0.1 to 30% by mass, and more preferably 3 to 25% by mass with respect to the entire resin particles.
In the present invention, by designing the wax, the crosslinked resin and the non-crosslinked resin as described above, excellent low-temperature fixability, high glossiness, excellent offset resistance and blocking resistance, and dust is suppressed. Toner can be obtained.

By using a combination of crosslinked resin particles and non-crosslinked resin particles, a toner having a better balance in terms of low-temperature fixability, glossiness, offset resistance, blocking resistance, and dust suppression than using crosslinked resin particles alone is obtained. be able to.
This seems to be because in the emulsion polymerization aggregation method and its modified method, the crosslinked resin particles and the non-crosslinked resin particles are not completely compatible with each other and are in an appropriate phase separation state.

The non-crosslinked resin particles are preferably present as close to the toner surface as possible. For this reason, when designing a core / shell structure, it is preferable to contain many non-crosslinked resin components in a shell part.
In this invention, it is preferable to contain resin which has a sulfonic acid group and / or a sulfonate. By containing these resins, the chargeability can be improved, and thereby high image quality of the toner can be realized. In addition, it has excellent environmental characteristics and can provide stable image quality even for long-term repeated live action, and in combination with the wax in the present invention, while suppressing dust generated during fixing, It is possible to provide a toner for developing an electrostatic charge image that ensures blocking resistance and is excellent in image quality.

  The resin having a sulfonic acid group and / or a sulfonate is not particularly limited, and examples thereof include monomers having a sulfonic acid group and / or a sulfonate represented by the following structural formula (5) or the following structural formula (6). Examples thereof include resins obtained by copolymerizing other vinyl monomers that can be copolymerized.

[In the structural formula (5), R ³ represents H or CH ₃ , R ⁴ represents C ₂ H ₄ or C ₃ H ₆ , and M ¹ is selected from the group consisting of H, Na, K and NH _4. Represents one type. ]

[In the structural formula (6), R ⁵ represents H or CH ₃ , R ⁶ represents C ₂ H ₄ or C ₃ H ₆ , M ² represents Ca or Mg, p is 1 or 2, q is 2-p. ]
Although the copolymerization ratio of the monomer having a sulfonic acid group and / or sulfonate represented by the structural formula (5) or the structural formula (6) with other vinyl monomers copolymerizable is not particularly limited, The monomers having a sulfonic acid group and / or a sulfonate are preferably 1% by mass or more and 30% by mass or less based on the entire resin.

  If the copolymerization ratio of monomers having sulfonic acid groups and / or sulfonates is too small, it may be difficult to accumulate a sufficient amount of charge in the resulting toner, and the toner may scatter and be unusable. . On the other hand, if the amount is too large, the electric resistance value of the resulting toner will be low, the stability over time of the change in charge amount will be poor, the compatibility with the binder will be poor, and the transparency may be impaired.

  When the “resin having sulfonic acid and / or sulfonate” is used in combination with the above-described combination of waxes in the present invention, the gloss can be increased while maintaining a favorable fixing temperature range. When using a resin with few crosslinking components in an attempt to increase gloss, the high-temperature offset property decreases. However, when the above-mentioned “resin having sulfonic acid and / or sulfonate” is used in combination, it increases gloss while maintaining a good fixing temperature range. Is possible.

  Specific examples of monomers having a sulfonic acid group and / or a sulfonate represented by the above structural formula (5) that can be used in the present invention include, for example, sulfoethylacrylic acid, sulfoethylmethacrylic acid, sulfoethyl Sodium acrylate, sulfoethyl methacrylate, ammonium sulfoethyl acrylate, ammonium sulfoethyl methacrylate, potassium sulfoethyl acrylate, potassium sulfoethyl methacrylate, potassium sulfopropyl acrylate, potassium sulfopropyl methacrylate, etc. Specific examples of monomers represented by the structural formula (6) include, for example, calcium sulfoethyl acrylate, calcium sulfoethyl methacrylate, magnesium sulfoethyl acrylate, sulfoethyl methacrylate Neshiumu and the like, these monomers singly or can be used in combination of two or more thereof.

  Among the monomers having a sulfonic acid group and / or a sulfonate salt exemplified above, the reason is that it is easy to copolymerize and a copolymer having a softness that is preferable as a component of an electrophotographic toner is easily obtained. And at least one selected from the group consisting of sodium sulfoethyl acrylate, sodium sulfoethyl methacrylate, ammonium sulfoethyl acrylate, ammonium sulfoethyl methacrylate, potassium sulfopropyl acrylate and potassium sulfopropyl methacrylate Is preferred.

  Other vinyl monomers that can be used as a copolymer component with monomers having the sulfonic acid group and / or sulfonate are not particularly limited, and may be those having a polymerizable unsaturated bond. Any of them can be used. Specific examples include styrene, o, m, p-chlorostyrene, α-methylstyrene, vinyltoluene, (meth) acrylic acid, maleic acid, itaconic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (Meth) acrylic acid propyl, (meth) acrylic acid butyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid amyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid lauryl, (meth) acrylic acid Examples include stearyl, (meth) acrylic acid behenyl, acrylamide, vinyl chloride, vinyl acetate, etc. Among these vinyl monomers, at least one selected from the group consisting of styrene and (meth) acrylic acid alkyl esters is used. It is preferable that the (meth) acrylic acid alkyl ester is It is preferable to use with an atom number 1 to 18 alkyl groups (meth) acrylic acid alkyl ester.

  In the present invention, as the above sulfoalkyl (meth) acrylic acid monomer, at least one selected from the group consisting of ammonium sulfoethyl methacrylate, sodium sulfoethyl methacrylate and potassium sulfopropyl methacrylate is used. A copolymer obtained by copolymerizing at least one selected from the group consisting of styrene and (meth) acrylic acid alkyl ester as a system monomer is well compatible in a transparent state in a binder, and is at high temperature and high humidity. This is preferable because the toner characteristics can be stabilized even under such a severe environment.

These resins having a sulfonic acid group and / or a sulfonate may be formed into a resin particle dispersion by emulsion polymerization, or are polymerized by a known method and then emulsified and dispersed by a known method. It is good.
Moreover, the addition amount is preferably 0.1 to 20% by mass, and particularly preferably 1 to 10% by mass. If the added amount is small, the effect of charge control is reduced, and if it is too large, the charge amount may be lowered or the charge amount distribution may be deteriorated.

The addition method may be included in the entire toner particles together with other resin particle dispersions, or may be added alone or together with other resin particle dispersions as a shell and contained in the vicinity of the toner surface. The effect can be exhibited in a smaller amount by incorporating it into.
Furthermore, by using a non-crosslinked resin having a sulfonic acid group and / or a sulfonate, the low-temperature fixability and the gloss can be improved as well as the chargeability. If low-temperature fixability and gloss can be improved, it will be easier to secure a balance between dust suppression and low-temperature fixability and blocking resistance during fixing, and a synergistic effect with the wax described above will be achieved, resulting in excellent electrostatic charge. An image developing toner can be provided.

In the case of using a non-crosslinked resin having a sulfonic acid group and / or a sulfonate, the weight average molecular weight is preferably 10,000 to 50,000, more preferably, in the gel permeation chromatography (GPC) measurement of THF-soluble matter. It is desirable that it is 15,000-40,000. A non-crosslinked resin having a sulfonic acid group and / or a sulfonate salt can provide a toner having an excellent balance of low-temperature fixability / gloss and offset / blocking resistance as compared with non-crosslinked resin particles not containing these. This is presumed to be because non-crosslinked resin particles containing sulfonic acid groups and / or sulfonates form a network due to loose interaction different from the covalently crosslinked structure.

By incorporating a non-crosslinked resin having a sulfonic acid group and / or a sulfonic acid salt in the vicinity of the toner surface, the effect of improving low-temperature fixability and gloss can be exhibited in a small amount.
When preparing a resin particle dispersion by emulsion polymerization in the present invention, for example, as a monomer, a polymerizable monomer having an acidic group (hereinafter sometimes simply referred to as “acidic monomer”), A polymerizable monomer having a basic group (hereinafter sometimes simply referred to as “basic monomer”), a polymerizable monomer having neither an acidic group nor a basic group (hereinafter referred to as “other monomers”). Any of the polymerizable monomers (sometimes abbreviated as “monomer”) can be used.

In the emulsion polymerization step, the polymerizable monomer is usually polymerized in an aqueous medium in the presence of an emulsifier. At this time, when supplying the polymerizable monomer to the reaction system, each monomer is added separately. Alternatively, a plurality of types of monomers may be mixed in advance and added simultaneously. Further, the monomer may be added as it is, or may be added as an emulsified liquid previously mixed and adjusted with water or an emulsifier.
As the acidic monomer, a polymerizable monomer having a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, cinnamic acid, a polymerizable monomer having a sulfonic acid group such as sulfonated styrene, Examples thereof include polymerizable monomers having a sulfonamide group such as vinylbenzenesulfonamide. Examples of the basic monomer include aromatic vinyl compounds having an amino group such as aminostyrene, nitrogen-containing heterocyclic-containing polymerizable monomers such as vinylpyridine and vinylpyrrolidone, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, etc. And (meth) acrylic acid ester having an amino group. These acidic monomers and basic monomers may be used alone or in combination as a mixture, or may exist as a salt with a counter ion. Among these, it is preferable to use an acidic monomer, more preferably acrylic acid and / or methacrylic acid.

The total amount of the acidic monomer and the basic monomer in 100 parts by mass of the total polymerizable monomers constituting the binder resin is preferably 0.05 parts by mass or more, more preferably 0.5 parts by mass. As mentioned above, More preferably, it is 1 mass part or more, Preferably it is 10 mass parts or less, More preferably, it is 5 mass parts or less.
As the other polymerizable monomer, the known vinyl monomers mentioned above can be used, and they may be used alone or in combination.

Further, when the binder resin is a cross-linked resin, the above-mentioned polymerizable monomer and the above-mentioned polyfunctional monomer can be used alone or in combination.
In the emulsion polymerization of the present invention, a known polymerization initiator can be used as necessary, and the polymerization initiators can be used alone or in combination of two or more. For example, persulfates such as potassium persulfate, sodium persulfate, ammonium persulfate, and the like, and redox initiators combining these persulfates as a component with a reducing agent such as acidic sodium sulfite, hydrogen peroxide, 4,4 Water-soluble polymerization initiators such as' -azobiscyanovaleric acid, t-butyl hydroperoxide, cumene hydropeoxide, etc., and these water-soluble polymerization initiators as a component combined with a reducing agent such as ferrous salt Redox initiator systems, benzoyl peroxide, 2,2′-azobis-isobutyronitrile, and the like are used. These polymerization initiators may be added to the polymerization system before, simultaneously with the addition of the monomer, or after the addition, and these addition methods may be combined as necessary.

Furthermore, a known chain transfer agent can be used as necessary. Specific examples of the chain transfer agent include t-dodecyl mercaptan, 2-mercaptoethanol, diisopropyl xanthogen, carbon tetrachloride, trichlorobromomethane, and the like. The chain transfer agent may be used alone or in combination of two or more, and is used in an amount of 0 to 5% by mass based on the polymerizable monomer.
Moreover, a well-known suspension stabilizer can be used as needed. Specific examples of the suspension stabilizer include calcium phosphate, magnesium phosphate calcium hydroxide, magnesium hydroxide and the like. These may be used alone or in combination of two or more, and may be used in an amount of 1 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the polymerizable monomer.

Both the polymerization initiator and the suspension stabilizer may be added to the polymerization system at any time before, simultaneously with, or after the addition of the polymerizable monomer. You may combine.
In addition, a pH adjuster, a polymerization degree adjuster, an antifoaming agent, and the like can be appropriately added to the reaction system.

In the present invention, when the binder resin is polymerized by emulsion polymerization, known emulsifiers can be used, but one kind selected from a cationic surfactant, an anionic surfactant and a nonionic surfactant Alternatively, two or more emulsifiers can be used in combination.
Examples of the cationic surfactant include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl ammonium bromide, and examples of the anionic surfactant include And fatty acid soap such as sodium stearate and sodium dodecanoate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate and the like. Nonionic surfactants include, for example, polyoxyethylene dodecyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monooleate ether, monodecanoyl sucrose, etc. Is mentioned.

  In this invention, it is preferable that the usage-amount of an emulsifier is used by 0.1 to 10 mass parts with respect to 100 mass parts of polymerizable monomers. These emulsifiers can be used as protective colloids, for example, one or two or more of partially or completely saponified polyvinyl alcohols such as polyvinyl alcohol and cellulose derivatives such as hydroxyethyl cellulose.

  In the present invention, the volume average particle size of the polymer primary particles obtained by emulsion polymerization is usually 0.02 μm or more, preferably 0.05 μm or more, more preferably 0.1 μm or more, and usually 1 μm or less, preferably 0. 0.8 μm or less, more preferably 0.5 μm or less. If the particle size is too small, it may be difficult to control the aggregation rate in the aggregation process. If it is too large, the particle size of the toner particles obtained by aggregation tends to be large, and a toner having the target particle size is obtained. May be difficult.

  The blending of the colorant in the emulsion polymerization aggregation method is usually performed in an aggregation step. A dispersion of polymer primary particles and a dispersion of colorant particles are mixed to form a mixed dispersion, which is then aggregated to form a particle aggregate. The colorant is preferably used in the state of being dispersed in water in the presence of an emulsifier, and the volume average particle size of the colorant particles is 0.01 or more, more preferably 0.05 μm or more, and more preferably 2 μm or less. 1 μm or less.

When a charge control agent is used in the present invention, any known one can be used alone or in combination. For example, as a positively chargeable charge control agent, a quaternary ammonium salt, a basic / electron-donating agent can be used. Examples of negative charge control agents include metal chelates, metal salts of organic acids, metal-containing dyes, nigrosine dyes, amide group-containing compounds, phenol compounds, naphthol compounds and their metal salts, urethane bond-containing compounds , Acidic or electron withdrawing organic substances.

  It is preferable to use a charge control agent that is colorless or light in color and does not impair the color tone of the toner. Metal salts with chromium, zinc, aluminum, etc., metal complexes, metal salts of benzylic acid, metal complexes, amide compounds, phenol compounds, naphthol compounds, phenolamide compounds, 4,4′-methylenebis [2- [N- ( Hydroxynaphthalene compounds such as 4-chlorophenyl) amido] -3-hydroxynaphthalene] are preferred.

  In the present invention, when the charge control agent is contained in the toner using the emulsion polymerization aggregation method, the charge control agent is added together with the polymerizable monomer or the like during the emulsion polymerization, or the charge control agent is The dispersion liquid dispersed in is added in the agglomeration step together with the polymer primary particles and the colorant, or is added after the polymer primary particles and the colorant are agglomerated to almost the target particle size. Can be blended. Among these, it is preferable to disperse the charge control agent in water by a known method and add it as a dispersion having a volume average particle size of 0.01 μm or more and 3 μm or less to the aggregation step.

  In the emulsion polymerization aggregation method, the aggregation is usually carried out in a tank equipped with a stirrer, but there are a heating method, a method of adding an electrolyte, and a method of combining them. When polymer primary particles are agglomerated with stirring to obtain particle aggregates of the desired size, the particle size of the particle aggregates is controlled based on the balance between the agglomeration force between the particles and the shearing force due to agitation. However, the cohesive force can be increased by heating or adding an electrolyte.

In the present invention, the electrolyte in the case of performing aggregation by adding an electrolyte may be either an organic salt or an inorganic salt. Specifically, NaCl, KCl, LiCl, Na ₂ SO ₄ , K ₂ SO ₄ , Li ₂ SO ₄ , MgCl ₂ , CaCl ₂ , MgSO ₄ , CaSO ₄ , ZnSO ₄ , Al ₂ (SO ₄ ) ₃ , Fe ₂ (SO ₄ ) ₃ , CH ₃ COONa, C ₆ H ₅ SO ₃ Na, etc. It is done. Of these, inorganic salts having a divalent or higher polyvalent metal cation are preferred.

  In the present invention, the amount of electrolyte added varies depending on the type of electrolyte, target particle size, etc., but is preferably 0.05 parts by mass or more, and 0.1 parts by mass with respect to 100 parts by mass of the solid component of the mixed dispersion. Part or more is more preferable. Further, it is preferably 25 parts by mass or less, more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less. If the amount added is too small, the progress of the agglomeration reaction will be slow, and there will be problems such as a fine powder of 1 μm or less remaining after the agglomeration reaction or the average particle size of the obtained particle aggregate will not reach the target particle size. In some cases, if the amount is larger than the above range, rapid agglomeration tends to occur and it becomes difficult to control the particle size, and the obtained agglomerated particles may cause problems such as inclusion of coarse powder or irregular shapes. .

The aggregation temperature in the case of performing aggregation by adding an electrolyte is preferably 20 ° C. or higher, particularly preferably 30 ° C. or higher. Moreover, 70 degrees C or less is preferable and 60 degrees C or less is especially preferable.
The aggregation temperature in the case of performing aggregation only by heating without using an electrolyte is preferably (Tg-20) ° C. or higher, and more preferably (Tg-10) ° C. or higher, where Tg is the glass transition temperature of the polymer primary particles. . Moreover, Tg or less is preferable and (Tg-5) degree C or less is preferable.

The time required for agglomeration is optimized depending on the shape of the apparatus and the processing scale, but in order for the toner particle size to reach the target particle size, it is usually held at the predetermined temperature for at least 30 minutes. desirable. The temperature rise until reaching the predetermined temperature may be raised at a constant rate, or may be raised stepwise.
If necessary, particles having resin fine particles attached or fixed thereto may be formed on the surface of the particle aggregate after the above-described aggregation treatment. By attaching or fixing resin fine particles whose properties are controlled to the surface of the particle aggregate, the chargeability and heat resistance of the obtained toner may be improved, and the effect of the present invention can be further enhanced. .

  When resin fine particles having a glass transition temperature higher than the glass transition temperature of the polymer primary particles are used as the resin fine particles, it is preferable because blocking resistance can be further improved without impairing fixability. The volume average particle size of the resin fine particles is preferably 0.02 μm or more, and more preferably 0.05 μm or more. Moreover, 1 micrometer or less, Furthermore 0.6 micrometer or less are preferable. As the resin fine particles, those obtained by emulsion polymerization of monomers similar to the polymerizable monomers used for the above-described polymer primary particles can be used.

The resin fine particles are usually used as a dispersion dispersed in water or a liquid mainly composed of water using a surfactant. However, when a charge control agent is added after the aggregation treatment, charge control is performed on the dispersion containing particle aggregates. It is preferable to add resin fine particles after adding the agent.
In order to increase the stability of the particle aggregate obtained in the aggregation step, it is preferable to perform fusion in the aggregated particles in the aging step after the aggregation step. The temperature of the ripening step is preferably not less than Tg of the polymer primary particles, more preferably not less than 5 ° C higher than Tg, and preferably not more than 80 ° C higher than Tg, more preferably not less than 50 ° C higher than Tg. It is as follows. The time required for the ripening step varies depending on the shape of the target toner, but is usually 0.1 to 10 hours, preferably 0.5 to 5 hours after reaching the glass transition temperature or higher of the polymer primary particles. It is desirable to do.

  In addition, it is preferable to add a surfactant or raise the pH value after the aggregation process, preferably before the aging process or at a stage during the aging process. As the surfactant used here, one or more emulsifiers can be selected from the emulsifiers that can be used when producing the polymer primary particles. In particular, the emulsifiers used when producing the polymer primary particles. It is preferable to use the same. Although the addition amount in the case of adding surfactant is not limited, Preferably it is 0.1 mass part or more with respect to 100 mass parts of solid components of a mixed dispersion liquid, More preferably, it is 1 mass part or more, More preferably, it is 3 masses. It is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less. After the aggregation process, before the completion of the ripening process, by adding a surfactant or raising the pH value, it is possible to suppress aggregation of the particle aggregates aggregated in the aggregation process, In some cases, the generation of coarse particles can be suppressed.

  By heat treatment in the aging step, the polymer primary particles in the aggregate are fused and integrated, and the toner particle shape as the aggregate becomes close to a spherical shape. The particle aggregate before the aging step is considered to be an aggregate due to electrostatic or physical aggregation of the polymer primary particles, but after the aging step, the polymer primary particles constituting the particle aggregate are fused to each other. In addition, the shape of the toner particles can be made nearly spherical. According to such an aging process, by controlling the temperature and time of the aging process, the primary shape of the polymer primary particles is agglomerated, a potato type with advanced fusion, and a spherical shape with further fusion For example, various shapes of toner can be manufactured according to the purpose.

The toner mother particles are subjected to a step of filtering and washing the toner mother particles from a dispersion containing the toner mother particles and a dispersion medium using a centrifuge.
In the step of filtering and washing, for example, the toner base particle collecting property, clogging resistance, cake forming property, water permeability, simplicity when replacing the filter cloth, and the like are required. It is not easy to satisfy these required characteristics at the same time. In particular, toner base particles obtained by a wet method are particles having a small particle size, and it is difficult to satisfy them simultaneously.

  Further, in the toner base particle dispersion (slurry) processed in the step of filtering and washing, it is derived not only from the toner base particles but also from raw materials, surfactants, additives, etc. used in each manufacturing process. Since impurities such as various by-products and contaminants are present, when effective filtration and washing that appropriately removes these impurities in the filtration and washing process is not performed, the finally obtained electrostatic charge image developing toner Performance will be poor. That is, toner obtained from toner base particles from which impurities are not properly removed tends to be inferior in terms of storage stability, and when image formation is performed, the image is fogged. Temperature and humidity changes during image formation Image quality changes such as image density, toner scattering in the image forming apparatus, and images with a constant image quality cannot be obtained when used for a long period of time. Become. Therefore, filtration cleaning that can sufficiently remove impurities is desired.

The technique of the present invention realizes filtration and cleaning satisfying each of these required characteristics.
To the toner of the present invention, an external additive can be added as necessary to improve the fluidity and charge control of the toner. Examples of such an external additive include various inorganic or organic fine particles. It can be appropriately selected and used.
Examples of inorganic fine particles include silicon carbide, boron carbide, titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, tantalum carbide, niobium carbide, tungsten carbide, chromium carbide, molybdenum carbide, calcium carbide, and other carbides, boron nitride, titanium nitride. , Various nitrides such as zirconium nitride, various borides such as zirconium boride, various oxides such as titanium oxide, calcium oxide, magnesium oxide, zinc oxide, copper oxide, aluminum oxide, cerium oxide, silica, colloidal silica, titanium Various titanate compounds such as calcium oxide, magnesium titanate and strontium titanate, phosphate compounds such as calcium phosphate, sulfides such as molybdenum disulfide, fluorides such as magnesium fluoride and fluorocarbon, aluminum stearate, stearin Calcium, zinc stearate, can be used various metal soaps such as magnesium stearate, talc, bentonite, various carbon black or conductive carbon black, magnetite, ferrite or the like. As the organic fine particles, fine particles such as styrene resin, acrylic resin, epoxy resin, and melamine resin can be used.

  Among these external additives, silica, titanium oxide, alumina, zinc oxide, various carbon blacks, conductive carbon blacks, and the like are preferably used. In addition, the external additive, the surface of the inorganic or organic fine particles, silane coupling agent, titanate coupling agent, silicone oil, modified silicone oil, silicone varnish, fluorine silane coupling agent, fluorine silicone oil, What has been subjected to surface treatment such as hydrophobization by a treating agent such as a coupling agent having an amino group or a quaternary ammonium base can also be used. Two or more kinds of the treatment agents can be used in combination.

The external additive preferably has an average particle size of 0.001 μm or more, more preferably 0.005 μm or more. Moreover, 3 micrometers or less are preferable, More preferably, it is 1 micrometer. Also, a plurality of types having different particle sizes can be blended. The average particle diameter of the external additive can be determined by observation with an electron microscope.
In addition, the external additive can be used in combination of two or more different types, can be used in combination with those that have not been surface-treated and those that have been surface-treated, A positively chargeable one and a negatively chargeable one can be used in appropriate combination.

The content of the external additive in the present invention is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, preferably 5 parts by mass or less, more preferably 100 parts by mass of the toner particles. Is 3 parts by mass or less.
Examples of the method for adding the external additive include a method using a high-speed stirrer such as a Henschel mixer, a method using an apparatus capable of applying a compressive shear stress, and the like.

Further, inorganic fine powders such as magnetite, ferrite, cerium oxide, strontium titanate, and conductive titania can be added. The amount of these additives used may be appropriately selected depending on the desired performance, and is usually preferably 0.05 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the toner particles.
The toner for developing an electrostatic charge image of the present invention preferably has a volume median diameter (Dv50) of 7 μm or less, more preferably 6.5 μm or less, and particularly preferably 6 μm or less. Moreover, it is preferable that it is 4 micrometers or more, and it is especially preferable that it is 4.5 micrometers or more. If the volume median diameter (Dv50) is too large, it may not be suitable for high-resolution image formation. In addition, toner consumption during continuous shooting may increase, or toner deterioration such as burying of external additives may easily occur. On the other hand, if it is too small, the wax tends to be liberated during production, and as a result, the chargeability and fluidity of the toner may be deteriorated and handling as a powder may be difficult.

Since ester wax has good compatibility with the resin for toner, there are cases where storage stability is deteriorated and charging characteristics are deteriorated. This tendency was remarkable in a high temperature and high humidity environment.
However, in the present invention, by using a colorant having a specific structure, this defect can be solved, and a toner having a small amount of free wax and good wax dispersibility can be obtained. Further, it is excellent in storage stability and chargeability, and a toner excellent in these performances can be obtained not only at normal temperature / normal humidity but also at high temperature / high humidity and low temperature / low humidity.

As a result, it is possible to provide a toner for developing an electrostatic image having excellent image quality while ensuring the fixing property and blocking resistance while suppressing the generation of dust during fixing.
A value (Dv50 / Dn50) obtained by dividing the volume median diameter (Dv50) of the toner by the number median diameter (Dn50) is referred to as “particle size distribution”, and the “particle size distribution” is preferably close to 1, and 1.1 or less. Preferably, 1.09 or less is more preferable. Since the electrostatic charge image developing toner has a sharper particle size distribution, the chargeability between the particles tends to be uniform. Therefore, the particle size distribution (Dv50) of the electrostatic image developing toner for achieving high image quality and high speed. / Dn50) is preferably in the above range.

On the other hand, in order to sharpen the particle size distribution, it is important that the wax is uniformly dispersed in the toner resin and that no free wax is generated during production.
In order to achieve high speed, it is necessary that the toner melts in a short time and is resistant to heat generated by high-speed stirring in the developing machine. In order to satisfy these contradictory performances, it is important that the wax is uniformly dispersed in the toner resin and that no free wax is generated during production.

In the present invention, an electrostatic charge image developing toner having excellent image quality with a sharp particle size distribution while ensuring fixing property and blocking resistance, while suppressing dust generated during fixing, depending on the type and mixing ratio of the wax described above. Can be provided.
The volume median diameter (Dv50) and the number median diameter (Dn50) are measured and defined by the methods described in the examples.

In addition, the shape of the toner for developing an electrostatic charge image is preferably as close to a sphere as possible. In the scattergram based on the number-of-circle-based equivalent diameter-circularity scattergram measured by the flow type particle image measuring device, the average circularity is preferably Is 0.95 or more, more preferably 0.96 or more, and particularly preferably 0.97 or more. The closer to a sphere, the less the amount of charge is localized in the particles and the developability tends to be uniform. On the other hand, a perfect spherical toner is a toner in the cleaning process on the photoreceptor in electrostatic charge image development. The average circularity is preferably 0.995 or less, and more preferably 0.990 or less. Further, the circularity standard deviation is preferably less than 0.10, and more preferably less than 0.05.

  “Average circularity” and “circularity standard deviation” are defined as values obtained by measuring by the method described in the Examples and measuring in such a manner. The “average circularity” and “circularity standard deviation” of the toner for developing an electrostatic charge image are equal to the “average circularity” and “circularity standard deviation” of the toner base particles before external addition. Further, the toner base particles were measured, and they were defined as “average circularity” and “circularity standard deviation” of the electrostatic image developing toner, respectively.

  The electrostatic image developing magenta toner obtained by the production method of the present invention is used in the form of a two-component developer using the toner together with a carrier, or a magnetic or non-magnetic one-component developer using no carrier. Also good. When used as a two-component developer, the carrier may be a magnetic substance such as iron powder, magnetite powder, ferrite powder or the like, or a known material such as a resin-coated surface or a magnetic carrier. As the coating resin of the resin coating carrier, generally known styrene resin, acrylic resin, styrene acrylic copolymer resin, silicone resin, modified silicone resin, fluororesin, or a mixture thereof can be used.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. Hereinafter, “part” means “part by mass”, and “%” simply means “% by mass” in terms of concentration and the like.
Measurement Example The particle size, circularity, electrical conductivity, wax carbon number, and the like were measured as follows.

<Measurement method and definition of volume average diameter (Mv)>
The volume average diameter (Mv) of the particles having a volume average diameter (Mv) of less than 1 μm is a model Microtrac Nanotrac 150 (hereinafter abbreviated as “Nanotrack”) manufactured by Nikkiso Co., Ltd. and its analysis software Microtrac Particle Analyzer Ver10.1. .2-019EE, using ion-exchanged water with an electric conductivity of 0.5 μS / cm as a solvent, solvent refractive index: 1.333, measurement time: 600 seconds, number of measurements: 1 It was measured by the method described in the document. Other setting conditions were particle refractive index: 1.59, transparency: transmission, shape: true sphere, density: 1.04.

<Measurement method and definition of volume median diameter of wax dispersion>
Measurement was performed using Partica LA-950V2 (hereinafter abbreviated as “LA950”) manufactured by HORIBA, Ltd., which is a laser diffraction scattering type particle size distribution measuring apparatus capable of high-speed measurement. The end point particle size for determining the end point during wax emulsification was set as the median diameter.
The solvent used was ion-exchanged water having an electric conductivity of 0.5 μS / cm, and the measurement was performed by adjusting the sample amount in a concentration range of solvent refractive index: 1.333 and visible light transmittance of 70% to 90%.

<Measurement method and definition of volume median diameter (Dv50) and number median diameter (Dn50)>
The toner finally obtained through the external addition process was subjected to the following pre-measurement treatment.
That is, in a cylindrical polyethylene (PE) beaker having an inner diameter of 47 mm and a height of 51 mm, 0.100 g of toner using a spatula and 20% by weight DBS aqueous solution using a syringe (Daiichi Kogyo Seiyaku Co., Ltd., Neogen S-) 20A) (hereinafter abbreviated as “20% DBS aqueous solution”) was added in an amount of 0.15 g. At this time, toner and a 20% DBS aqueous solution were added only to the bottom of the beaker so that the toner would not scatter on the edges of the beaker.

Next, the mixture was stirred for 3 minutes using a spatula until the toner and 20% DBS aqueous solution became a paste. At this time, the toner was prevented from being scattered on the edge of the beaker.
Subsequently, 30 g of dispersion medium Isoton II was added, and the mixture was stirred for 2 minutes using a spatula to obtain a uniform solution as a whole. Next, a fluororesin-coated rotor having a length of 31 mm and a diameter of 6 mm was placed in a beaker and dispersed using a stirrer at 400 rpm for 20 minutes. At this time, macroscopic particles visually observed at the gas-liquid interface and the edge of the beaker were dropped into the beaker at a rate of once every 3 minutes so as to form a uniform dispersion. Subsequently, this was filtered through a mesh having an opening of 63 μm, and the obtained filtrate was designated as “toner dispersion”.

Regarding the measurement of the particle diameter during the production process of the toner base particles, the filtrate obtained by filtering the agglomerated slurry with a 63 μm mesh was used as the “slurry liquid”.
The median diameter (Dv50 and Dn50) of the particles is Bocman Coulter's Multisizer III (aperture diameter 100 μm) (hereinafter abbreviated as “Multisizer”), the dispersion medium is Isoton II, and the above-mentioned The “toner dispersion liquid” or “slurry liquid” was diluted to a dispersoid concentration of 0.03% by mass, and KD was used with Multisizer III analysis software.
The value was measured as 118.5.

  The measurement particle diameter range is from 2.00 to 64.00 μm, and this range is discretized into 256 divisions so as to be equally spaced on a logarithmic scale, and those calculated based on the statistical values on the basis of the volume are “ The volume median diameter (Dv50) ”and the value calculated based on the statistical value on the basis of the number were referred to as“ number median diameter (Dn50) ”.

<Measurement method and definition of toner particle size distribution>
The volume median diameter (Dv50) was divided by the number median diameter (Dn50) to obtain Dv50 / Dn50 as the “particle size distribution”.
<Measuring method and definition of average circularity and circularity standard deviation of toner>
The “average circularity” in the present invention was measured as follows and defined as follows.
That is, the toner is dispersed in a dispersion medium (Isoton II, manufactured by Beckman Coulter, Inc.) so as to be in the range of 5720-7140 particles / μL, and the toner is obtained using a flow-type particle image analyzer (manufactured by Sysmex Corporation, FPIA 3000). The number-based circle equivalent diameter-circularity scattergram was measured under the following apparatus conditions, and the value was defined as the “average circularity” of the toner. In the present invention, the same measurement was performed three times at different locations, and an arithmetic average value of three “average circularity” was adopted as the “average circularity”.
・ Mode: HPF
-HPF analysis amount: 0.35 μL
-Number of HPF detected: 8,000-10,000 The following are measured by the above device and automatically calculated and displayed in the above device, but "roundness" is defined by the following formula The

[Circularity] = [Perimeter of a circle with the same area as the projected particle area] / [Perimeter of projected particle image]
Then, the number of HPF detected is 8,000 to 10,000, and the arithmetic average (arithmetic mean) of the circularity of each particle is displayed on the apparatus as “average circularity”.
The standard deviation of 8,000 to 10,000 circularities measured as described above is defined as “circularity standard deviation”.

In the present invention, the same measurement was performed three times at different locations, and an arithmetic average value of three “circularity standard deviations” was adopted as the “circularity standard deviation”.
<Measurement method and definition of insoluble content of tetrahydrofuran (THF)>
1 g of a sample is added to 50 g of tetrahydrofuran, dissolved by standing at 25 ° C. for 24 hours, filtered using 10 g of Celite, the solvent of the filtrate is distilled off to determine the amount of tetrahydrofuran (THF) soluble, and the amount of sample charged ( By subtracting from 1 g), “tetrahydrofuran (THF) insoluble matter (mass%)” was calculated.
As a sample, it is applied to a toner, a resin in a resin particle dispersion, and the like.

<Method for measuring weight average molecular weight and molecular weight peak>
The THF soluble content of toner and polymer primary particles (resin particles) was measured by gel permeation chromatography (GPC) under the following conditions.
Apparatus: GPC apparatus HLC-8020 manufactured by Tosoh Corporation
Column: Polymer Laboratory, PL-gel Mixed-B 10μ
Solvent: tetrahydrofuran (THF)
Sample concentration: 0.1% by mass
Calibration Curve Preparation: Standard Polystyrene As the THF soluble content of the toner, the “tetrahydrofuran (THF) soluble content” obtained by the above “Method for measuring tetrahydrofuran (THF) insoluble content” was used.
Further, the THF soluble content of the polymer primary particles (resin particles) is obtained by adding 1 g of the polymer primary particles (resin particles) to 50 g of THF and allowing to stand at 25 ° C. for 24 hours, followed by filtration and evaporation of the solvent. Prepared.

Example 1
<Preparation of wax dispersion W1>
Behenyl behenate 30.0 parts, 20% DBS aqueous solution 2.8 parts, demineralized water 67.3 parts, heated to 100 ° C., homogenizer with pressurized circulation line (manufactured by Gorin, LAB 60-10TBS type) Was used for primary circulation emulsification under a pressure of 10 MPa.

The particle diameter was measured every few minutes with LA950, and when the median diameter decreased to around 500 nm, the pressure condition was further increased to 25 MPa, followed by secondary circulation emulsification. A wax dispersion W1 was prepared by dispersing until the median diameter became 230 nm or less.
The volume median diameter of the wax dispersion was 200 nm.
<Preparation of wax dispersion W2>
A wax dispersion W2 was prepared in the same manner as the wax dispersion W1 except that distearyl ketone was used.

The volume median diameter of the wax dispersion was 220 nm.
<Preparation of wax dispersion W3>
A wax dispersion W3 was prepared in the same manner as the wax dispersion W1, except that HNP-11 (Nippon Seiwa Co., Ltd.) was used.
The volume median diameter of the wax dispersion was 230 nm.

<Preparation of colorant dispersion>
In a container of a stirrer equipped with a propeller blade, 20 parts of a pigment in which R in the structural formula (1) is CH3, a nonionic surfactant (manufactured by Kao Corporation, 1204 parts of Emulgen (20 parts relative to the pigment), conductivity 76 parts of ion-exchanged water of 2 μS / cm was added and predispersed to obtain a pigment premix solution.

The volume median diameter Dv1 of the particles in the dispersion after the premix was about 90 μm.
The premix solution was used as a raw material slurry and supplied to a wet bead mill equipped with a rotating screen (bead separation mesh separator) as shown in FIG. 1, and circulated and dispersed in the configuration shown in FIG. The inner diameter of the stator is 120 mmφ, the separator diameter is 60 mmφ,
As dispersion media, zirconia beads having a diameter of 100 μm (0.1 mm) (true density of 6.0 g / cm ³ ) were used. The effective internal volume of the stator is about 0.5 L, and the media filling volume is 0.35 L, so the media filling rate is 70%.

The premix slurry was supplied from the supply port at a supply speed of about 54 L / hr by a non-pulsating metering pump with the rotor rotating speed kept constant (the peripheral speed at the rotor tip was about 7 m / sec). During the operation, cooling water of about 10 ° C. was circulated from the jacket to obtain a colorant dispersion C1 having a volume median diameter Dv1 of 0.15 μm. Similarly, colorant dispersions C1 to C10 shown in Table 2 were obtained.
In addition, a pigment in which R ¹¹ in the structural formula (2) is CH ₃ and a pigment in which R ¹⁶ in the structural formula (4) is Cl, R ¹⁷ is CH ₃ , R ¹⁸ is SO _3- , and M ²⁺ is Sr. A pigment mixed in a ratio of 7: 3 was similarly submerged in water to obtain a colorant dispersion C11 having a volume median diameter Dv1 of 0.16 μm.

<Measurement Method and Definition of Volume Median Diameter Dv1 of Colorant Premix Liquid and Colorant Dispersion>
The volume median diameter Dv1 (μm) is as follows using an ultrafine particle size distribution measuring apparatus (manufactured by Nikkiso Co., Ltd., UPA-EX150, hereinafter abbreviated as “UPA”) using a dynamic light scattering method. It is defined as measured by the following settings.
Measurement upper limit: 6.54 μm
Measurement lower limit: 0.0008 μm
Number of channels: 52
Measurement time: 100 seconds Particle permeability: Absorption Particle refractive index: N / A (not applicable)
Particle shape: non-spherical density: 1 (g / cm ³ )
Dispersion medium type: WATER
Dispersion medium refractive index: 1.333
At the time of measurement, the colorant dispersion is diluted with pure water so that the sample concentration index is in the range of 0.01 to 0.1, and the measurement is performed with a sample that has been subjected to dispersion treatment with an ultrasonic cleaner or the like.

  In the present invention, the volume median diameter Dv1 (μm) is obtained by accumulating the above volume particle size distribution results from the small particle diameter side to obtain a volume cumulative distribution (curve), and measuring it as a particle diameter at a point of 50% by volume. It is what is done.

<Preparation of polymer primary particle dispersion D1>
A reactor equipped with a stirring device (three blades), a heating / cooling device, a concentrating device, and each raw material / auxiliary charging device was charged with 36.3 parts of wax dispersion W1 and 218 parts of demineralized water while stirring. The temperature was raised to 90 ° C. under a nitrogen stream.
Thereafter, the mixture of the following “polymerizable monomers and the like” and “emulsifier aqueous solution” was added to the solution over 5 hours while continuing to stir the liquid. The time at which this mixture was started to be dropped was designated as “polymerization start”, and the following “initiator aqueous solution” was added over 4.5 hours from 30 minutes after the start of polymerization. The agent aqueous solution ”was added over 2 hours, and the internal temperature was maintained at 90 ° C. for 1 hour while continuing stirring.

[Polymerizable monomers, etc.]
Styrene: 76.8 parts Butyl acrylate: 23.2 parts Acrylic acid: 1.5 parts Hexanediol diacrylate: 0.7 parts Dodecyl mercaptan: 4.0 parts [Emulsifier aqueous solution]
20% DBS aqueous solution: 1.0 part Demineralized water: 67.1 parts

[Initiator aqueous solution]
8% by mass aqueous hydrogen peroxide solution: 20.0 parts 8% by mass L (+)-ascorbic acid aqueous solution: 20.0 parts [Additional initiator aqueous solution]
8% by mass L (+)-ascorbic acid aqueous solution: 14.2 parts Cooled after completion of the polymerization reaction, to obtain a milky white primary polymer particle dispersion E1.
The volume average diameter (Mv) measured using Nanotrac was 260 nm, and the solid content concentration was 22.5% by mass.
The weight average molecular weight Mw by GPC measurement was 67000.

<Preparation of polymer primary particle dispersion D2>
A reactor equipped with a stirring device (three blades), a heating / cooling device, a concentrating device, and each raw material / auxiliary charging device was charged with 36.3 parts of wax dispersion W2 and 218 parts of demineralized water while stirring. The temperature was raised to 90 ° C. under a nitrogen stream.
Thereafter, the mixture of the following “polymerizable monomers and the like” and “emulsifier aqueous solution” was added to the solution over 5 hours while continuing to stir the liquid. The time at which this mixture was started to be dropped was designated as “polymerization start”, and the following “initiator aqueous solution” was added over 4.5 hours from 30 minutes after the start of polymerization. The agent aqueous solution ”was added over 2 hours, and the internal temperature was maintained at 90 ° C. for 1 hour while continuing stirring.

[Polymerizable monomers, etc.]
Styrene: 76.8 parts Butyl acrylate: 23.2 parts Acrylic acid: 1.5 parts Hexanediol diacrylate: 0.7 parts Trichlorobromomethane: 1.0 part [Emulsifier aqueous solution]
20% DBS aqueous solution: 1.0 part Demineralized water: 67.1 parts

[Initiator aqueous solution]
8% by mass aqueous hydrogen peroxide solution: 15.5 parts 8% by mass L (+)-ascorbic acid aqueous solution: 15.5 parts [Additional initiator aqueous solution]
8% by mass L (+)-ascorbic acid aqueous solution: 14.2 parts Cooled after completion of the polymerization reaction, to obtain a milky white primary polymer particle dispersion E2.
The volume average diameter (Mv) measured using Nanotrac was 255 nm, and the solid content concentration was 22.7% by mass.
The weight average molecular weight Mw by GPC measurement was 75000.

<Preparation of polymer primary particle dispersion D3>
A polymer primary particle dispersion D3 was obtained in the same manner as the polymer primary particle dispersion D1, except that the wax dispersion W3 was used.
The volume average diameter (Mv) measured using Nanotrac was 270 nm, and the solid content concentration was 22.1% by mass.
The weight average molecular weight Mw by GPC measurement was 77000.

<Manufacture of toner mother particles E1>
By using the following components, toner base particles F1 were produced by carrying out the following aggregation process (core material aggregation process / shell coating process) / rounding process.
Polymer primary particle dispersion D1 100 parts colorant dispersion C1 as solid content 4.0 parts colorant dispersion C8 as colorant solids 1.0 part 20% DBS aqueous solution as colorant solids 6 parts as solid content ○ Core material agglomeration step Polymer primary particle dispersion D1 in a mixer (volume 1000 L, inner diameter 850 mm) equipped with a stirrer (double helical blade), heating / cooling device, and each raw material / auxiliary charging device Was mixed uniformly at an internal temperature of 10 ° C. for 10 minutes. Then at an internal temperature of 10 ° C., allowed to stir at 101Rpm, a 5 wt% aqueous solution of potassium sulfate _from continuously added over 1 minute 0.12 parts as K 2 SO _4, and colorant dispersion C1 coloring The agent dispersion C8 was continuously added over 5 minutes and mixed uniformly at an internal temperature of 10 ° C.

Thereafter, 0.3 part by weight of an aqueous solution of 0.5% by mass of aluminum sulfate was continuously added over 30 minutes, and the internal temperature was raised to 48.0 ° C. over 70 minutes while maintaining the rotation speed at 101 rpm ( 0.5 ° C./min). Subsequently, after raising the temperature by 1 ° C. every 30 minutes (0.03 ° C./min), the temperature was maintained at 54.0 ° C., the volume median diameter was measured using a multisizer, and grown to 5.5 μm.
○ Circularization process Subsequently, a mixed aqueous solution of 20% DBS aqueous solution (6 parts as solids) and 0.04 part of water was added over 30 minutes with the same rotation speed, and the temperature was raised to 90 ° C. The temperature was raised by 1 ° C. every 30 minutes, raised to 95 ° C., and heating and stirring were continued under these conditions until the average circularity became 0.968 over 2.5 hours. Thereafter, the mixture was cooled to 20 ° C. over 50 minutes to obtain a slurry of toner base particles E1.

At this time, the volume median diameter of the particles was 5.7 μm, the number median diameter was 5.3 μm, the distribution Dv50 / Dn50 was 1.08, the average circularity was 0.968, and the circularity standard deviation was 0.014. It was.
○ Washing and drying process Using a wet electromagnetic sieve shaker (AS200 / Lecche Co., Ltd.) equipped with a sieve with a mesh size of 24μm, the resulting slurry is filtered for the purpose of removing coarse particles and equipped with a stirrer Once stored in the tank. Thereafter, this slurry was subjected to a horizontal centrifuge (HZ40Si type / Mitsubishi Chemical Corporation) equipped with a filter cloth (polyester TR815C, Nakao filter industry / thickness 0.3 mm / air permeability 48 (cc / cm ² / min)). Then, centrifugal dehydration washing was performed under the condition of acceleration 800G.

When ion-exchanged water having an electric conductivity of 1 μS / cm was added at a rate not to overflow from the rim at about 50 times the amount of slurry solids, the electric conductivity of the filtrate was 2 μS / cm. Finally, water was thoroughly shaken off, and the cake was recovered with a scraping device.
The obtained cake was spread on a stainless steel bat so as to have a height of 20 mm, and dried in a blow dryer set at 40 ° C. for 48 hours to obtain toner mother particles E1.

<Manufacture of developing toner F1: external addition process>
To the toner base particle F1 obtained 2500g, 50g of Clariant H05TD silica and 15g H30TD silica as external additives are mixed, mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developing toner F1. Got.
<Manufacture of toner mother particles E2>
Polymer primary particle dispersion D2 Toner base particles E2 were obtained in the same manner as F1, except that the 100 parts component was changed to the above as the solid content.

The volume median diameter (Dv) was 5.9 μm, the number median diameter (Dn) was 5.4 μm, Dv50 / Dn50 was 1.09, the average circularity was 0.972, and the circularity standard deviation was 0.012. It was.
<Manufacture of developing toner F2: external addition process>
The toner base particle F2 (2,500 g) obtained is mixed with 50 g of Clariant H05TD silica and 15 g of H30TD silica (external additive), mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developing toner F2 Got.

<Manufacture of toner mother particles E3>
Colorant Dispersion C1 Toner base particle E3 was obtained in the same manner as E1, except that 1.0 part of the colorant solid was changed to 4.0 parts as the colorant solid.
Volume median diameter (Dv) is 5.6 μm, number median diameter (Dn) is 5.2 μm, Dv50 / Dn.
50 was 1.08, the average circularity was 0.971, and the circularity standard deviation was 0.011.

<Manufacture of developing toner F3: external addition process>
The toner base particle E3 (2,500 g) was mixed with 50 g of Clariant H05TD silica and 15 g H30TD silica (external additive), mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developed toner F3. Got.
<Manufacture of toner mother particle E4>
Polymer primary particle dispersion D2 100 parts colorant dispersion C1 as solid content 4.0 parts colorant dispersion C9 as colorant solid content E1 except that 1.0 part component was changed to the above as colorant solid content Similarly, toner base particles E4 were obtained.

Volume median diameter (Dv) was 5.9 μm, number median diameter (Dn) was 5.5 μm, Dv50 / Dn50 was 1.07, average circularity was 0.967, and circularity standard deviation was 0.011. It was.
<Manufacture of developing toner F4: external addition process>
The toner base particle E4 2500 obtained is mixed with 50 g of Clariant H05TD silica and 15 g H30TD silica as an external additive, mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developing toner F4 Got.

<Manufacture of toner mother particles E5>
Colorant Dispersion C1 Toner base particle E5 was obtained in the same manner as E1, except that 2.4 parts colorant dispersion C10 as the colorant solids and 1.6 parts component as the colorant solids were changed as described above.
The volume median diameter (Dv) was 5.9 μm, the number median diameter (Dn) was 5.4 μm, Dv50 / Dn50 was 1.09, the average circularity was 0.975, and the circularity standard deviation was 0.012. It was.

<Manufacture of developing toner F5: external addition process>
The toner base particle E5 (2,500 g) was mixed with 50 g of Clariant H05TD silica and 15 g H30TD silica (external additive), mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developed toner F5. Got.
<Production of toner base particles E6>
Polymer primary particle dispersion D2 80 parts colorant dispersion C1 as solids 2.4 parts colorant dispersion C2 as colorant solids 0.4 parts colorant dispersion C9 as colorant solids As colorant solids The polymer primary particle dispersion D2 was charged into a mixer as 1.2 parts in the same manner as in E1, and aggregation was performed in the same manner as in E1.

Furthermore, when the internal temperature was 54.0 ° C. and the volume-median system (Dv50) was 5.2 μm, 20 parts of polymer primary particle dispersion D2 was added as a solid material as a shell material, and held at that temperature for 60 minutes. .
Thereafter, toner mother particles E6 were obtained by rounding, washing and drying in the same manner as in E1.
Volume median diameter (Dv) was 5.7 μm, number median diameter (Dn) was 5.3 μm, Dv50 / Dn50 was 1.08, average circularity was 0.971, and circularity standard deviation was 0.016. It was.

<Manufacture of developing toner F6: external addition process>
The toner base particle E6 (2,500 g) was mixed with 50 g of Clariant H05TD silica and 15 g H30TD silica (external additive), mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developed toner F6. Got.

<Manufacture of toner mother particle E7>
Polymer Primary Particle Dispersion D1 95 parts colorant dispersion C3 as solids 3.6 parts colorant dispersion C10 as colorants solids 0.4 parts as colorant solids in the blender as in E1 The primary particle dispersion D1 was charged, and aggregation was performed in the same manner as in E1.

Furthermore, when the internal temperature was 54.0 ° C. and the volume-median system (Dv50) was 5.4 μm, 5 parts of the polymer primary particle dispersion D2 was added as a solid material as a shell material and held at that temperature for 60 minutes. .
Thereafter, toner mother particles E7 were obtained by rounding, washing and drying in the same manner as in E1.
Volume median diameter (Dv) was 5.6 μm, number median diameter (Dn) was 5.2 μm, Dv50 / Dn50 was 1.08, average circularity was 0.973, and circularity standard deviation was 0.012. It was.

<Manufacture of developing toner F7: external addition process>
To the toner base particle E7 obtained, 50 g of H05TD silica manufactured by Clariant and 15 g of H30TD silica manufactured by Clariant are mixed as an external additive, mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developing toner F7. Got.
<Production of toner mother particles E8>
Colorant dispersion C4 Toner base particle E8 was obtained in the same manner as E4, except that 3.6 parts of colorant dispersion C8 was used as the colorant solid, and 0.4 part of the component was changed as described above.
The volume median diameter (Dv) was 5.6 μm, the number median diameter (Dn) was 5.2 μm, Dv50 / Dn50 was 1.08, the average circularity was 0.971, and the circularity standard deviation was 0.014. It was.

<Manufacture of developing toner F8: external addition process>
To the toner base particle E8 obtained, 50 g of H05TD silica manufactured by Clariant and 15 g of H30TD silica manufactured by Clariant are mixed as external additives, mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developing toner F8. Got.

<Manufacture of toner mother particles E9>
Colorant Dispersion C1 Colorant Solids 2.2 parts Colorant Dispersion C4 Colorant Solids 0.6 Part Colorant Dispersion C10 Colorant Solids Except for changing 1.2 parts to the above In the same manner as in E1, toner mother particles E9 were obtained.

The volume median diameter (Dv) was 5.6 μm, the number median diameter (Dn) was 5.2 μm, Dv50 / Dn50 was 1.08, the average circularity was 0.971, and the circularity standard deviation was 0.012. It was.
<Manufacture of developing toner F9: external addition process>
To 2500 g of the obtained toner base particle E9, 50 g of H05TD silica manufactured by Clariant Co., Ltd. and 15 g of H30TD silica manufactured by the same company are mixed as external additives, mixed with a Henschel mixer (Mitsui Mine Co., Ltd.), sieved with 150 mesh, and developing toner E9. Got.

<Manufacture of toner mother particle E10>
Colorant dispersion C11 Toner base particles E10 were obtained in the same manner as E1, except that the 7.0 parts component was changed to the above as the colorant solid content.
Volume median diameter (Dv) was 5.7 μm, number median diameter (Dn) was 5.3 μm, Dv50 / Dn50 was 1.08, average circularity was 0.966, and circularity standard deviation was 0.017. It was.

<Manufacture of developing toner F10: external addition process>
To 2500 g of the obtained toner base particle E10, 50 g of H05TD silica manufactured by Clariant Co., Ltd. and 15 g of H30TD silica manufactured by the same company are mixed as external additives, mixed with a Henschel mixer (Mitsui Mine Co., Ltd.), sieved with 150 mesh, and developing toner F10. Got.
<Manufacture of toner mother particles E11>
Colorant dispersion C1 Toner base particles E11 were obtained in the same manner as in E1, except that the 5.0 parts component was changed to the above as the solid content of the colorant.
The volume median diameter (Dv) was 5.6 μm, the number median diameter (Dn) was 5.2 μm, Dv50 / Dn50 was 1.08, the average circularity was 0.971, and the circularity standard deviation was 0.012. It was.

<Manufacture of developing toner F11: external addition process>
To 2500 g of the obtained toner base particle E11, 50 g of H05TD silica manufactured by Clariant Co., Ltd. and 15 g of H30TD silica manufactured by the same company are mixed as external additives, mixed with a Henschel mixer (Mitsui Mine Co., Ltd.), sieved with 150 mesh, and developing toner F11. Got.

<Manufacture of toner mother particle E12>
Colorant dispersion C3 Toner base particles E12 were obtained in the same manner as in E2, except that the 4.0 parts component was changed to the above as the colorant solid content.
Volume median diameter (Dv) was 5.9 μm, number median diameter (Dn) was 5.4 μm, Dv50 / Dn50 was 1.09, average circularity was 0.973, and circularity standard deviation was 0.018. It was.

<Manufacture of developing toner F12: external addition process>
To 2500 g of the obtained toner base particle E12, 50 g of H05TD silica manufactured by Clariant Co., Ltd. and 15 g of H30TD silica manufactured by the company are mixed as external additives, mixed with a Henschel mixer (Mitsui Mine Co., Ltd.), sieved with 150 mesh, and developing toner F12. Got.

<Manufacture of toner mother particles E13>
Colorant dispersion C4 Toner base particles E13 were obtained in the same manner as in E1, except that the 4.0 parts component was changed to the above as the colorant solid content.
Volume median diameter (Dv) was 6.0 μm, number median diameter (Dn) was 5.5 μm, Dv50 / Dn50 was 1.09, average circularity was 0.969, and circularity standard deviation was 0.014. It was.

<Manufacture of developing toner F13: external addition process>
The toner base particle E13 (2,500 g) was mixed with 50 g of Clariant H05TD silica and 15 g H30TD silica (external additive), mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developing toner F13. Got.

<Manufacture of toner mother particles E14>
Colorant dispersion C5 Toner base particles E14 were obtained in the same manner as E4, except that the 4.0 parts component was changed to the above as the colorant solid content.
Volume median diameter (Dv) was 5.8 μm, number median diameter (Dn) was 5.4 μm, Dv50 / Dn50 was 1.07, average circularity was 0.970, and circularity standard deviation was 0.011. It was.

<Manufacture of developing toner F14: external addition process>
To 2500 g of the obtained toner base particles E14, 50 g of Clariant H05TD silica and 15 g of H30TD silica manufactured as external additives are mixed, mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developing toner F14. Got.

<Manufacture of toner mother particle E15>
Colorant dispersion C6 Toner base particles E15 were obtained in the same manner as E9, except that the 4.0 parts component was changed to the above as the colorant solid content.
The volume median diameter (Dv) was 6.1 μm, the number median diameter (Dn) was 5.6 μm, Dv50 / Dn50 was 1.09, the average circularity was 0.968, and the circularity standard deviation was 0.015. It was.

<Manufacture of developing toner F15: external addition process>
To the toner base particle E15 thus obtained, 50 g of Clariant H05TD silica and 15 g H30TD silica manufactured as external additives are mixed, mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developing toner F15. Got.

<Manufacture of toner mother particles E16>
Colorant dispersion C7 Toner base particles E16 were obtained in the same manner as E2, except that the 4.0 parts component was changed to the above as the colorant solid content.
The volume median diameter (Dv) was 5.8 μm, the number median diameter (Dn) was 5.2 μm, Dv50 / Dn50 was 1.12, the average circularity was 0.973, and the circularity standard deviation was 0.019. It was.

<Manufacture of developing toner F16: external addition process>
To 2500 g of the obtained toner base particles E16, 50 g of Clariant H05TD silica and 15 g of H30TD silica manufactured as external additives are mixed, mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developing toner F16. Got.

<Manufacture of toner mother particle E17>
Colorant dispersion C8 Toner base particles E17 were obtained in the same manner as E2, except that the 4.0 parts component was changed to the above as the colorant solid content.
Volume median diameter (Dv) was 6.0 μm, number median diameter (Dn) was 5.2 μm, Dv50 / Dn50 was 1.15, average circularity was 0.971, and circularity standard deviation was 0.012. It was.

<Manufacture of developing toner F17: external addition process>
To 2500 g of the obtained toner base particles E17, 50 g of Clariant H05TD silica and 15 g of H30TD silica manufactured as external additives are mixed, mixed with a Henschel mixer (Mitsui Mine), sieved with 150 mesh, and developing toner F17. Got.

<Manufacture of toner mother particles E18>
Wax dispersion liquid W3 Toner base particles E18 were obtained in the same manner as in E1, except that the 7-part component was changed to the above as the solid content.
Volume median diameter (Dv) was 5.8 μm, number median diameter (Dn) was 5.1 μm, Dv50 / Dn50 was 1.14, average circularity was 0.972, and circularity standard deviation was 0.014. It was.

<Manufacture of developing toner F18: external addition process>
To 2500 g of the obtained toner base particle E18, 50 g of H05TD silica manufactured by Clariant Co., Ltd. and 15 g of H30TD silica manufactured by the same company are mixed as external additives, mixed with a Henschel mixer (manufactured by Mitsui Mine), sieved with 150 mesh, and developing toner F18. Got.
Evaluation example of developing toner G27 by sieving with mesh

<Fixing test>
<< Measurement method and definition of fixing temperature range >>
When recording paper carrying an unfixed toner image is prepared, the surface temperature of the heating roller is changed from 100 ° C. to 215 ° C. in increments of 5 ° C., conveyed to the fixing nip, and discharged at a speed of 150 mm / sec. The fixing state of was observed.

A temperature region in which toner on the heating roller or paper wrapping does not occur at the time of fixing and the toner on the recording paper after fixing is sufficiently adhered to the recording paper is defined as a “fixing temperature region”. The heating roller of the fixing machine has a release layer made of PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), and was evaluated without application of silicone oil. The “fixing temperature region” was determined according to the following criteria.
A (Good): Offset occurs at a fixing temperature of + 50 ° C. or higher.
○ (Practical use possible): Offset occurs at a fixing temperature of + 40 ° C. or higher and lower than 50 ° C.
Δ (insufficient): Offset occurs at a fixing temperature of + 30 ° C. or higher and lower than 40 ° C.
X (Unusable): Offset at a fixing temperature of less than + 30 ° C.

<< Measurement method and definition of low-temperature fixability >>
Further, in the above measurement method, the actual image test was performed with the roller temperature set at 130 ° C., the obtained fixed image was rubbed under a certain load, the density drop before and after rubbing was visually compared, and the following criteria were used. The “low temperature fixability” was determined.
◎ (Good): No decrease in concentration ○ (Practical use possible): Slight decrease in concentration is observed Δ (Inadequate): Concentration decrease is conspicuous × (Unusable): Almost peeled off

<Measurement method and definition of toner cohesion>
The toner cohesiveness was confirmed by a vibration sieve measurement method using a three-stage mesh.
Using a powder tester manufactured by Hosokawa Micron Co., Ltd., three types of sieves are stacked and fixed, and a sample is placed on the shaking table.
The measurement conditions are as follows.
Mesh opening (top): 250 μm (60 mesh)
Mesh opening (medium): 150 μm (100 mesh)
Mesh opening (bottom): 75 μm (200 mesh)
Swing scale: 1.0mm
Sampling amount: 2.0 g
Vibration time: 90 seconds After measurement, the degree of aggregation was determined from the following calculation.
(Weight of powder remaining in upper mesh / amount of sample collected) × 100
(Weight of powder remaining in middle mesh / sample collection amount) × 100 × 0.6
(Weight of powder remaining in lower mesh / sample collection amount) × 100 × 0.2
The total of the above three calculated values is defined as the degree of aggregation (%).

The determination of “toner aggregation” is as follows.
○ (Practical use possible): Aggregation degree is less than 10% Δ (Insufficient): Aggregation degree is 10% or more and less than 20% x (Unusable): Aggregation degree is 20% or more <Definition and measurement method of blocking resistance>
10 g of toner is put into a cylindrical container having an inner diameter of 3 cm and a height of 6 cm, and a load of 20 g is put on it and left in an environment of 50 ° C. and 40% RH for 24 hours. Then, the toner is taken out of the container and the load is applied from above. The degree of solidification of the toner was confirmed by applying, and “blocking resistance” was determined according to the following criteria.
◎ (Good): Even if no load is applied, it collapses and does not solidify.
○ (Practical use possible): Solidified but collapsed with a load of less than 50 g.
Δ (insufficient): solidified and collapsed with a load of 50 g or more and less than 200 g.
X (Unusable): It is consolidated and does not collapse unless a load of 200 g or more is applied.

<Dust generation measurement method and definition>
Put all four development toners into the cartridge of the color page printer ML9600PS (Oki Data Co., Ltd.) and write “Dust” in RAL-UZ122-2006 according to the measurement method (RAL-UZ122-2006) certified by Blue Angel Mark. The “dissipation rate (mg / h) described in RAL-UZ122-2006” was determined from the mass measurement of the substance collected on the filter.

The “emission rate (mg / h) described in RAL-UZ122-2006” was defined as the “dust generation amount (mg / h)” of the present invention. The definition of “dust” is as described above, and is not limited to “dust”.
As described above, the substance derived from wax is actually dominant.
Specifically, after the blanking measurement was performed by baking the emission test chamber (VOC-010 / Volume 1000L / Espec Corp.) in advance, the printer and the dust measurement filter were installed, and the tank was for 60 minutes. After waiting for the temperature and humidity to be within the specified value (23 ± 2 ° C / 50 ± 5%), the printer is operated by remote control and at the same time, suction from the filter is started, and the specified number of sheets is printed for 2 hours. Suction collection was performed until later. Note that VE110-7, Version 2006-06-01 (RAL-UZ122 / RALC00.PDF) was used as the print pattern.

The emission rate (mg / h), that is, “dust generation amount (mg / h)” was obtained from the following equation.
(1) Dust mass after temperature / humidity correction m _St (mg)
= ( _{M MF bruto} -m _{MF tara} ) + (m _RF1 -m _RF2 )
m _{MF tara} : Mass of measurement filter with stable mass before dust sampling (mg)
m _{MF bruto} : Mass of measurement filter with stable mass after dust sampling (mg)
m _RF1 : Mass of reference filter before test (mg)
m _RF2 : Mass of the reference filter after the test (mg)
(2) _Emission rate EF _uSt (mg / h)
= (M _St × n × V × t _o ) / (V _S × t _p )
n: Number of ventilations (h ^-1 )
t _o : Total sampling time (min)
t _p : Printing time (min)
V: chamber volume (m ³ )
V _S : volume of air sucked through the filter (m ³ )

<Repeated printing evaluation method>
Printing was repeated using Microline 9600 manufactured by Oki Data Co., Ltd., and the initial image and image quality evaluation after printing 30,000 sheets were performed as follows.
A: Image defects including image density and fog are hardly observed.
○: A fine image defect is recognized, but there is no major problem.
Δ: An image defect is recognized but within an allowable limit.
X: An unacceptable image defect is recognized.

Claims (6)

At least a colorant, a binder resin, and a wax, wherein the wax is represented by Structural Formula (1), and the colorant is a compound of Structural Formula (2) and / or (3) and Structural Formula (4) A magenta toner for developing an electrostatic charge image.

[In the formula (1), R ¹ represents an alkyl group or alkoxy group having 10 or more carbon atoms, R ² represents —X—COOR ³ (where X represents an alkylene group, and R ³ represents an alkyl group having 10 or more carbon atoms. Or an alkyl group having 10 or more carbon atoms. ]

[In Structural Formula (2), R ¹¹ and R ¹² each independently represent H or CH ₃ . ]

[In the structural formula (3), R ¹³ represents CH ₃ or OCH ₃ , R ¹⁴ represents H or Cl, and R ¹⁵ represents OCH ₃ or Cl. ]

[In Structural Formula (4), R ¹⁶ represents Cl or SO ₃ ^— , R ¹⁷ represents H, CH ₃ or Cl, R ¹⁸ represents H or SO ₃ ^— , and any one of R ¹⁶ and R ¹⁸ or the other only SO ₃ ^- represents a. M ²⁺ represents a divalent metal ion. ]   The magenta toner for developing an electrostatic charge image according to claim 1, wherein the toner has a core / shell structure.   3. The magenta toner for developing an electrostatic charge image according to claim 1, wherein the crosslinked resin is a core and the non-crosslinked resin is a shell.   The weight average molecular weight in gel permeation chromatography of tetrahydrofuran-soluble matter is 30,000 to 100,000, and the molecular weight peak is 20,000 to 60,000. 4. The magenta toner for developing an electrostatic charge image according to any one of 3 above. The volume median diameter (Dv50) is 4 μm or more and 7 μm or less, and the particle size distribution Dv / Dn50 represented by the ratio of the volume median diameter to the number median diameter (Dn50) is 1.1 or less. The magenta toner for developing an electrostatic charge image according to claim 1.   In the toner-based circle equivalent diameter-circularity scattergram measured by the flow type particle image measuring apparatus, the average circularity is 0.950 to 0.990 and the circularity standard deviation is less than 0.05. The magenta toner for developing an electrostatic charge image according to any one of claims 1 to 5.

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