JP2012093486A - Toner, method for manufacturing toner, and method for forming image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner simultaneously achieving low-temperature fixability and image stability, a method for manufacturing a toner, and a method for forming an image.SOLUTION: A toner containing at least a resin and a colorant includes: a resin phase 1 that contains a polyfunctional radical polymerizable component; and a resin phase 2 that contains a crosslinked polymer including a structural moiety represented by the following general formula (1). In the above general formula (1), [Rrepresents a hydrogen atom or a chlorine atom, and Rrepresents a hydrogen atom, a chlorine atom, or a methoxy group].

Description

  The present invention relates to a toner, a toner manufacturing method, and an image forming method.

  In recent years, from the viewpoint of global warming prevention, energy saving has been studied in various fields, and efforts have been made to use low energy, such as power saving during standby, in information devices such as image forming apparatuses. On the other hand, studies have been made to lower the fixing temperature in the fixing process that consumes the most energy. Therefore, in order to improve low-temperature fixing, a technique for changing the physical properties of the resin (low Tg, low Tsp) is employed.

JP-A-4-186368

However, although the above-described technique achieves low-temperature fixability, image stability after fixing (document offset) is deteriorated, and a technique is required to achieve both low-temperature fixability and image stability. Therefore, in order to improve the image stability, in Patent Document 1, a thermosetting resin is externally added to the toner to cause the polyester binder resin to undergo a curing reaction. However, there is a demand for low-energy fixing, a demand for screen printing, use of coated paper with poor toner penetration at the time of fixing, a demand for fixing with fixed image halftone, etc. for their high image quality, etc. There are various stress demands, and it is difficult to obtain both a document offset (image loss) at the time of low-temperature fixing and to achieve both characteristics only by such a technique.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a toner, a toner manufacturing method, and an image forming method capable of achieving both low-temperature fixability and image stability.

〔上記一般式（１）において、Ｒ¹ は水素原子または塩素原子、Ｒ² は水素原子、塩素原子またはメトキシ基である。〕 According to the invention of claim 1, in a toner containing at least a resin and a colorant,
Provided is a toner comprising a resin phase 1 containing a polyfunctional radical polymerizable compound and a resin phase 2 containing a crosslinked polymer having a structural moiety represented by the following general formula (1). Is done.

[In the above general formula (1), R ¹ is a hydrogen atom or a chlorine atom, and R ² is a hydrogen atom, a chlorine atom or a methoxy group. ]

  According to a second aspect of the present invention, there is provided the toner according to the first aspect, wherein the polyfunctional radical polymerizable compound is a polyfunctional acrylate / methacrylate compound.

According to invention of Claim 3, the said polyfunctional radically polymerizable compound is 0.3 to 1 time mole equivalent content of the polymeric triarylimidazole compound represented by following General formula (3), It is characterized by the above-mentioned. A toner according to claim 1 or 2 is provided.

〔上記一般式（３）において、Ｒ¹ は水素原子または塩素原子、Ｒ² は水素原子、塩素原子またはメトキシ基、Ｒ³ は水素原子またはメチル基であり、Ｌ¹ は、単結合または２価の有機基である。〕

〔上記一般式（４）において、Ｒ¹ は水素原子または塩素原子、Ｒ² は水素原子、塩素原子またはメトキシ基、Ｒ³ は水素原子またはメチル基であり、Ｌ¹ およびＬ² は、単結合または２価の有機基であって、Ｌ¹ およびＬ² は、互いに同一であっても異なっていてもよい。〕 According to a fourth aspect of the present invention, there is provided a toner production method for producing the toner according to any one of the first to third aspects,
A polymerizable triarylimidazole compound represented by the following general formula (4) is bonded to the polymerizable triarylimidazole compound represented by the following general formula (4) by bonding the imidazole rings of the triarylimidazole group. There is provided a method for producing a toner, characterized in that after a monomer compound is obtained, a step of obtaining a crosslinked polymer by polymerizing the polymerizable triarylimidazole dimer compound is performed.

[In the above general formula (3), R ¹ is a hydrogen atom or a chlorine atom, R ² is a hydrogen atom, a chlorine atom or a methoxy group, R ³ is a hydrogen atom or a methyl group, and L ¹ is a single bond or a divalent group. Is an organic group. ]

[In the above general formula (4), R ¹ is a hydrogen atom or a chlorine atom, R ² is a hydrogen atom, a chlorine atom or a methoxy group, R ³ is a hydrogen atom or a methyl group, and L ¹ and L ² are single bonds or a divalent organic group, L ¹ and L ² may being the same or different. ]

  According to the invention of claim 5, the polymerization treatment is performed in a state in which a polymerization treatment liquid obtained by dissolving or dispersing the polymerizable triarylimidazole dimer compound in an organic solvent is dispersed in an aqueous medium. A method for producing a toner according to claim 4 is provided.

〔上記一般式（３）において、Ｒ¹ は水素原子または塩素原子、Ｒ² は水素原子、塩素原子またはメトキシ基、Ｒ³ は水素原子またはメチル基であり、Ｌ¹ は、単結合または２価の有機基である。〕

〔上記一般式（５）において、Ｒ¹ は水素原子または塩素原子、Ｒ² は水素原子、塩素原子またはメトキシ基、Ｒ³ は水素原子またはメチル基であり、Ｌ¹ は、単結合または２価の有機基である。また、ｎは、繰り返し数である。〕 According to the invention of claim 6, there is provided a method for producing the toner of claim 1.
After polymerizing a polymerizable triarylimidazole compound represented by the following general formula (3) to obtain a triarylimidazole group-containing prepolymer having a structural unit represented by the following general formula (5), the triarylimidazole is obtained. There is provided a method for producing a toner, which comprises a step of obtaining a crosslinked polymer by performing a crosslinking treatment for bonding between imidazole rings of groups.

[In the above general formula (3), R ¹ is a hydrogen atom or a chlorine atom, R ² is a hydrogen atom, a chlorine atom or a methoxy group, R ³ is a hydrogen atom or a methyl group, and L ¹ is a single bond or a divalent group. Is an organic group. ]

[In the general formula (5), R ¹ is a hydrogen atom or a chlorine atom, R ² is a hydrogen atom, a chlorine atom or a methoxy group, R ³ is a hydrogen atom or a methyl group, and L ¹ is a single bond or a divalent group. Is an organic group. N is the number of repetitions. ]

  According to the invention of claim 7, the polymerization treatment is performed in a state where the polymerization treatment liquid containing the polymerizable triarylimidazole compound is dispersed in an aqueous medium. A toner manufacturing method is provided.

According to the invention of claim 8, the method includes a step of fixing the image forming support on which a toner image is formed with toner containing at least a resin and a colorant by passing between the heating roller and the pressure roller. In the image forming method,
The toner has a resin phase 1 containing a polyfunctional radically polymerizable compound and a resin phase 2 containing a crosslinked polymer having a divalent crosslinking group represented by the following general formula (1). There is provided an image forming method characterized in that a radical polymerization reaction occurs between the resin layer 1 and the resin layer 2 by fixing heat.

According to the present invention, the toner has a resin phase 1 containing a polyfunctional radically polymerizable compound and a resin phase 2 containing a cross-linked polymer having a structural portion represented by the general formula (1). Therefore, since the crosslinked polymer having the triphenylimidazole structure represented by the general formula (1) causes decrosslinking by pressure and heat during fixing, low temperature fixing can be achieved.
Further, the crosslinked polymer that has undergone decrosslinking generates radicals. Then, the generated radicals react with the polyfunctional radical polymerizable compound to form a crosslinked structure, so that the image stability after fixing is improved. Therefore, both low temperature fixing and image stability can be achieved.

〔上記一般式（１）において、Ｒ¹ は水素原子または塩素原子、Ｒ² は水素原子、塩素原子またはメトキシ基である。〕 Hereinafter, the present invention will be specifically described.
The toner of the present invention includes a resin phase 1 containing a polyfunctional radically polymerizable compound and a resin phase 2 containing a crosslinked polymer having a structural site (divalent crosslinking group) represented by the following general formula (1). Have

[In the above general formula (1), R ¹ is a hydrogen atom or a chlorine atom, and R ² is a hydrogen atom, a chlorine atom or a methoxy group. ]

[Polyfunctional radical polymerizable compound]
A polyfunctional radically polymerizable compound is a compound having two or more vinyl groups at the end of the compound. Examples of the polyfunctional radical polymerizable compound include polyfunctional acrylate / methacrylate compounds in addition to divinylbenzene.
Examples of the bifunctional acrylate compound include 2-hydroxy-3-acryloyloxypropyl methacrylate, polyethylene glycol diacrylate, propoxylated ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A diacrylate, 9,9-bis [4- (2 -Acryloyloxyethoxy) phenyl] fluorene, propoxylated bisphenol A diacrylate, tricyclodecane dimethanol diacrylate, 1,10-decanediol diacrylate, 1,9-nonanediol diacrylate, 1,6-hexanediol diacrylate 1,4-butanediol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, polytetra Chi glycol diacrylate, tetraethylene glycol diacrylate, etc. 2-n-butyl-2-ethyl-1,3-propanediol diacrylate.
Examples of polyfunctional acrylate compounds include ethoxylated isocyanuric acid triacrylate, ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate, pentaerythritol triacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, ethoxylated penta Examples include erythritol tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol polyacrylate, and dipentaerythritol hexaacrylate.
Bifunctional methacrylate compounds include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, ethoxylated bisphenol A dimethacrylate, tricyclodecane dimethanol dimethacrylate, 1,10-decanediol dimethacrylate. 1,9-nonanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, ethoxylated polypropylene glycol dimethacrylate, glycerin dimethacrylate, polypropylene glycol dimethacrylate and the like.
Examples of the polyfunctional methacrylate compound include trimethylolpropane trimethacrylate.
The addition amount of the polyfunctional radically polymerizable compound is preferably 0.3 to 1 times that of the vinyl-triphenylimidazole compound added to the toner. If it is 0.3 mol or less, the progress of the crosslinking reaction is insufficient, and the desired image stability cannot be obtained. Further, when it is added in an amount of 1 mol or more, a large amount of unreacted polyfunctional radical polymerizable monomer is present and oozes out to the surface of the image, causing deterioration of image characteristics such as gloss.

[Divalent cross-linking group (specific cross-linking group)]
In the general formula (1), R ¹ is a hydrogen atom or a chlorine atom, preferably a hydrogen atom. When R ¹ in a specific bridging group is a chlorine atom, the group R ¹ is preferably bonded to the para position with respect to the imidazole ring.
In the general formula (1), R ² is a hydrogen atom, a chlorine atom or a methoxy group, preferably a hydrogen atom. When R ² in the specific bridging group is a chlorine atom, the group R ² may be bonded to any of the ortho, meta, and para positions with respect to the imidazole ring. When R ² is a methoxy group, the group R ² is preferably bonded to the ortho position with respect to the imidazole ring.

  In the general formula (1), the imidazole ring in the specific cross-linking group is a polymer to be bonded to the end of the specific cross-linking group with respect to the benzene ring serving as a bond at the end of the specific cross-linking group. The chain is preferably bonded to the meta position.

上記一般式（２）において、Ｌ¹およびＬ^２は、各々、単結合または２価の有機基である。
基Ｌ¹および基Ｌ^２を構成する２価の有機基としては、例えば−Ｃ（＝Ｏ）−ＮＨ−、−Ｃ（＝Ｏ）Ｏ−、−ＮＨ（Ｃ＝Ｏ）ＮＨ−および−ＮＨＣ（＝Ｏ）Ｏ−などが挙げられる。
また、上記一般式（２）において、Ｒ^３は水素原子またはメチル基である。 [Crosslinked polymer]
Specifically, the crosslinked polymer crosslinked by the specific crosslinking group as described above may contain a structural unit represented by the following general formula (2).

In the general formula (2), L ¹ and L ² are each a single bond or a divalent organic group.
Examples of the divalent organic group constituting the group L ¹ and the group L ² include —C (═O) —NH—, —C (═O) O—, —NH (C═O) NH— and —NHC. (= O) O- and the like.
In the general formula (2), R ³ is a hydrogen atom or a methyl group.

  Moreover, in the said General formula (2), m and n are repeating numbers, respectively, and are specifically the integers of 1-100, for example.

The molecular weight of such a crosslinked polymer has a peak molecular weight from a molecular weight distribution based on a styrene-converted molecular weight measured by gel permeation chromatography (GPC) in a state where a bond between imidazole rings is cleaved by applying pressure. It is preferably 3,500 to 20,000, more preferably 10,000 to 20,000.
The peak molecular weight is a molecular weight corresponding to the elution time of the peak top in the molecular weight distribution. When there are a plurality of molecular weight peaks, the molecular weight corresponds to the elution time of the peak top having the largest peak area ratio.

Specifically, the molecular weight of the cross-linked polymer was determined using a device “HLC-8220” (manufactured by Tosoh Corporation) and a column “TSKguardcolumn + TSKgelSuperHZM-M3 series” (manufactured by Tosoh Corporation) while maintaining the column temperature at 40 ° C. Tetrahydrofuran (THF) as a solvent is allowed to flow at a flow rate of 0.35 ml / min, and the measurement sample (the toner obtained by subjecting the toner to the following cross-linking cleavage treatment) is treated under a dissolution condition in which treatment is performed for 5 minutes using an ultrasonic disperser at room temperature. The sample solution was dissolved in tetrahydrofuran to 1 mg / ml and then processed with a membrane filter having a pore size of 0.2 μm, and 10 μL of this sample solution was injected into the apparatus together with the above carrier solvent, and the refractive index detector (RI detector) is used to detect the molecular weight distribution of the measurement sample It is intended to be measured.
Cross-linking cleavage treatment: At room temperature, 30 g of the measurement sample toner is put in an automatic agate mortar (AMM-140D / KN3324014 manufactured by Tech Jam Co., Ltd.), and pressure is applied for 10 minutes under the condition of a rotation speed of a negative pestle of 100 rpm.

Moreover, it is preferable that the glass transition point of a crosslinked polymer is 45-100 degreeC, More preferably, it is 50-65 degreeC.
When the glass transition point of the crosslinked polymer is 45 ° C. or higher, the obtained toner can have sufficient heat-resistant storage property. On the other hand, when the glass transition point of the crosslinked polymer is higher than 100 ° C., the phenomenon of lowering the glass transition point does not proceed sufficiently even by the cleavage of the bond between the imidazole rings due to the application of pressure, and as a result, a sufficiently low temperature There is a possibility that the fixing property cannot be obtained.

  The glass transition point of the crosslinked polymer is measured using a differential scanning calorimeter “Diamond DSC” (manufactured by PerkinElmer). Specifically, 4.50 mg of toner is sealed in an aluminum pan “PARTNO.BO14-3016”, which is set in a sample holder of “Diamond DSC”, and an empty aluminum pan is used for reference measurement. Heat-cool-Heat temperature control was performed under the measurement conditions of a measurement temperature of 0 to 200 ° C., a temperature increase rate of 10 ° C./min, and a temperature decrease rate of 10 ° C./min. Data on Heat is acquired, and the glass transition point is the intersection of the baseline extension before the rise of the first endothermic peak and the tangent line indicating the maximum slope between the rise of the first endothermic peak and the peak apex. As shown. 1st. The heat was raised at 200 ° C. for 5 minutes.

The degree of crosslinking, which is the proportion of bonds between the imidazole rings of the triarylimidazole group in the crosslinked polymer, is preferably 1-20%, more preferably 2-8%, particularly preferably 5% in the crosslinked polymer. is there.
When the degree of cross-linking in the cross-linked polymer is less than 1%, the effects of the present invention are hardly exhibited, and specifically, heat-resistant storage stability and particle strength may be reduced. On the other hand, when the degree of crosslinking in the crosslinked polymer exceeds 20%, the low-temperature fixability may be insufficient.

  The degree of crosslinking in the crosslinked polymer can be controlled by the mixing ratio of the polymerizable triarylimidazole compound, that is, the copolymer ratio.

The crosslinked polymer as described above can be used as it is as a binder resin for a toner, but various known resins other than the crosslinked polymer (hereinafter also referred to as “other toner resins”) can be used. A mixture of these can also be used as the binder resin.
The content of the crosslinked polymer in the binder resin constituting the toner particles is preferably 20% by mass or more.

  The toner particles constituting the toner of the present invention may further contain a colorant, a charge control agent, a magnetic powder, a release agent, and the like as desired.

[Colorant]
When the toner particles are configured to contain a colorant, organic or inorganic pigments of various colors as exemplified below can be used as the colorant.
That is, as a colorant for black toner, carbon black, magnetic material, iron / titanium composite oxide black, etc. can be used. As carbon black, channel black, furnace black, acetylene black, thermal black, lamp Black and the like can be mentioned, and examples of the magnetic material include ferrite and magnetite.
As a colorant for yellow toner, C.I. I. Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162, etc., and C.I. I. Pigment Yellow 14, 17, 74, 93, 94, 138, 155, 180, 185, etc. can be used, and mixtures thereof can also be used.
As a colorant for magenta toner, C.I. I. Solvent Red 1, 49, 52, 58, 63, 111, 122, etc. I. Pigment Red 5, 48: 1, 53: 1, 57: 1, 122, 139, 144, 149, 166, 177, 178, 222, etc. can be used. Mixtures of these can also be used.
As a colorant for cyan toner, C.I. I. Solvent Blue 25, 36, 60, 70, 93, 95, etc. I. Pigment Blue 1, 7, 15, 15, 60, 62, 66, 76, etc. can be used, and a mixture thereof can also be used.

  The content ratio of the colorant is preferably 0.5 to 20% by mass in the toner particles, and more preferably 2 to 10% by mass.

[Magnetic powder]
When the toner particles are configured to contain magnetic powder, for example, magnetite, γ-hematite, or various ferrites can be used as the magnetic powder.
The content ratio of the magnetic powder is preferably 10 to 500% by mass in the toner particles, and more preferably 20 to 200% by mass.

[Charge control agent]
Further, in the case where the toner particles are configured to contain a charge control agent, the charge control agent is not particularly limited as long as it is a substance that can give positive or negative charge by frictional charging, and there are various known ones. Can be used. Specifically, as the positive charge control agent, for example, a nigrosine dye such as “Nigrosine Base EX” (manufactured by Orient Chemical Industries), “quaternary ammonium salt P-51” (manufactured by Orient Chemical Industries), “ Quaternary ammonium salts such as “Copy Charge PX VP435” (manufactured by Hoechst Japan), alkoxylated amines, alkylamides, molybdate chelate pigments, and imidazole compounds such as “PLZ1001” (manufactured by Shikoku Kasei Kogyo) Examples of the negative charge control agent include “Bontron S-22” (manufactured by Orient Chemical Industries), “Bontron S-34” (manufactured by Orient Chemical Industries), and “Bontron E-81” (Orient Chemical Industries). Manufactured by Co., Ltd.), "Bontron E-84" (manufactured by Orient Chemical Industry Co., Ltd.), "Spiron Black TRH" Metal complexes such as (Hodogaya Chemical Industries, Ltd.), thioindigo pigments, quaternary ammonium salts such as “Copy Charge NX VP434” (Hoechst Japan), “Bontron E-89” (Orient Chemical Industries) And boron compounds such as “LR147” (manufactured by Nippon Carlit), fluorine compounds such as magnesium fluoride and carbon fluoride, and the like. In addition to the metal complexes used as negative charge control agents, oxycarboxylic acid metal complexes, dicarboxylic acid metal complexes, amino acid metal complexes, diketone metal complexes, diamine metal complexes, azo group-containing benzene-benzene derivatives Those having various structures such as a skeletal metal body and an azo group-containing benzene-naphthalene derivative skeleton metal complex can be used.
As described above, the toner particles are configured to contain the charge control agent, whereby the chargeability of the toner is improved.

  The content ratio of the charge control agent is preferably 0.01 to 30% by mass in the toner particles, and more preferably 0.1 to 10% by mass.

〔Release agent〕
Further, when the toner particles are configured to contain a release agent, various known waxes can be used as the release agent. As the wax, it is particularly preferable to use a polyolefin-based wax such as low molecular weight polypropylene, polyethylene, or oxidized polypropylene or polyethylene.

  The content of the release agent is preferably 0.1 to 30% by mass in the toner particles, and more preferably 1 to 10% by mass.

[Other toner resins]
In addition, when the toner particles are produced by an emulsion association method as described later, examples of polymerizable monomers for obtaining other toner resins include styrene; methyl methacrylate, ethyl methacrylate, and n-butyl methacrylate. , Isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, etc. Methacrylic acid ester derivatives; methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, n-octyl acrylate, acrylic acid 2 Acrylic ester derivatives such as ethylhexyl, stearyl acrylate, lauryl acrylate, and phenyl acrylate; olefins such as ethylene, propylene, and isobutylene; vinyl simple substances such as acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide A polymer can be mentioned. These vinyl monomers can be used alone or in combination of two or more.

  Moreover, it is preferable to use combining what has an ionic dissociation group as a polymerizable monomer. The polymerizable monomer having an ionic dissociation group has, for example, a substituent such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group as a constituent group, and specifically includes acrylic acid, methacrylic acid, maleic acid. Acid, itaconic acid, cinnamic acid, fumaric acid and the like can be mentioned.

[Toner Production Method]
A method for producing the toner of the present invention containing the polyfunctional radical polymerizable compound as described above and a crosslinked polymer will be described.
The toner manufacturing method according to the present invention includes the following steps (1) to (5).

(1) Step of preparing a polyfunctional radical polymerizable compound-containing resin dispersion In this step, a polyester resin, a styrene acrylic resin, or a polyfunctional radical polymerizable compound is dissolved in a solvent such as ethyl acetate and dispersed in an aqueous medium. After emulsifying and dispersing using a machine and removing the solvent, a polyfunctional radical polymerizable compound-containing resin dispersion is prepared.

(2) Step of producing resin particle dispersion containing crosslinked polymer The crosslinked polymer can be produced by passing through the following two steps (I) and (II).
(I) A polymerizable triarylimidazole compound represented by the following general formula (3) is used to perform a bonding treatment for bonding the imidazole rings of the triarylimidazole group, thereby being represented by the following general formula (4). Step (II) of obtaining a crosslinked polymer by polymerizing the polymerizable triarylimidazole dimer compound after obtaining the polymerizable triarylimidazole dimer compound represented by the following general formula (3) After polymerizing a polymerizable triarylimidazole compound to obtain a triarylimidazole group-containing prepolymer having a structural unit represented by the following general formula (5), crosslinking treatment for bonding between imidazole rings of the triarylimidazole group Step of obtaining a crosslinked polymer by performing

[Method through step (I)]
In the general formula (3), R ¹ is a hydrogen atom or a chlorine atom, preferably a hydrogen atom. When R ¹ in the polymerizable triarylimidazole compound represented by the general formula (3) is a chlorine atom, the group R ¹ is preferably bonded to the para position with respect to the imidazole ring. According to the polymerizable triarylimidazole compound in which the group R ¹ composed of a chlorine atom is bonded to the para position with respect to the imidazole ring, it is easy to form a cross-linking bond between the imidazole rings.
In the general formula (3), R ² is a hydrogen atom, a chlorine atom or a methoxy group, preferably a hydrogen atom. When R ² in the polymerizable triarylimidazole compound represented by the general formula (3) is a chlorine atom, the group R ² is bonded to any of the ortho, meta, and para positions with respect to the imidazole ring. May be. When R ² is a methoxy group, the group R ² is preferably bonded to the ortho position with respect to the imidazole ring.
In the general formula (3), the imidazole ring in the triaryl imidazole groups, in the triaryl imidazole group, the benzene ring to be bonded in succession groups L ^1, meta to the group L ¹ It is preferable that they are bonded. According to the polymerizable triarylimidazole compound in which the imidazole ring is to be bonded continuously to the group L ¹ in the triarylimidazole group, the imidazole ring is bonded to the meta position relative to the group L ¹ . It is easy to form a cross-linking bond.

In the general formula (3), L ¹ is a single bond or a divalent organic group.
Examples of the divalent organic group constituting the group L ¹ include —C (═O) —NH—, —C (═O) O—, —NH (C═O) NH— and —NHC (═O). O- etc. are mentioned.
Further, in the above general formula (3), R ³ is a hydrogen atom or a methyl group.

Examples of the polymerizable triarylimidazole compound represented by the general formula (3) include those represented by the following [Exemplary Compound 1] to [Exemplary Compound 9].

The coupling treatment in the step (I) can be performed by adding an oxidizing agent to the polymerizable triarylimidazole compound. Examples of the oxidizing agent include potassium ferricyanide, potassium permanganate, potassium chlorate, potassium bromate, and sodium bromate. Of these, potassium ferricyanide is particularly preferably used.
The treatment temperature can be 5 to 15 ° C., and the treatment time can be 2 to 8 hours.

In the general formula (4), R ¹ , R ² and R ³ are the same as R ¹ , R ² and R ³ in the general formula (3). In the general formula (4), L ¹ and L ² are the same as L ¹ in the general formula (3).

  The polymerizable triarylimidazole dimer compound represented by the general formula (4) is, for example, the following formula (4-1) which is a dimer of the triarylimidazole compound represented by [Exemplary Compound 1]. ) Can be mentioned.

  In the method for producing the toner through the step (I), a method in which the polymerization treatment is performed in an aqueous medium is preferable, and a so-called suspension polymerization method, emulsion polymerization method, and emulsion association method can be used. By using such a method, it is possible to obtain a toner that remains sufficiently without cleavage of a bond related to crosslinking. In addition, in a toner manufactured by a so-called pulverization method, there is a possibility that a bond related to crosslinking may be broken by an external force such as kneading during the manufacturing process.

Specifically, the polymerization treatment is performed in a state where a polymerization treatment liquid obtained by dissolving or dispersing a polymerizable triarylimidazole dimer compound in an organic solvent is dispersed or suspended in an aqueous medium.
When the suspension polymerization method or the emulsion polymerization method is adopted, the resin particle dispersion containing the obtained polymer particles is directly mixed with the polyfunctional radical polymerizable compound-containing resin dispersion for aggregation and fusion. In the case of employing the emulsion association method, the obtained polymer particles are further mixed with other toner resin fine particles and a polyfunctional radical polymerizable compound-containing resin dispersion to be aggregated and fused. Toner particles can be obtained.

  In the present invention, the “aqueous medium” refers to a material whose main component (50% by mass or more) is water. Examples of components other than water include organic solvents that dissolve in water, such as methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran. Among these, alcohol-based organic solvents such as methanol, ethanol, isopropanol, and butanol, which are organic solvents that do not dissolve the resin, are particularly preferable.

In the polymerization treatment, it is preferable to copolymerize with a copolymerizable monomer copolymerizable with the polymerizable triarylimidazole dimer compound, thereby obtaining a crosslinked polymer.
Examples of the monomer for copolymerization include (meth) acrylic acid, (meth) acrylic acid ester, and styrene. In particular, butyl acrylate and 2-ethylhexyl acrylate are preferably used.
In this way, according to the crosslinked polymer synthesized through copolymerization with the copolymerization monomer, the fixability of the obtained toner can be easily controlled.

  The copolymerization ratio of the polymerizable triarylimidazole dimer compound and the copolymerization monomer is 1:99 to 20:80 in terms of the molar ratio of the polymerizable triarylimidazole dimer compound: copolymerization monomer. preferable.

[Method through step (II)]
In the general formula (5), R ^1, R ^2, and R ³ are the same as R ^1, R ² and R ³ in the general formula (3). When R ¹ in the triarylimidazole group-containing prepolymer represented by the general formula (5) is a chlorine atom, the group R ¹ is preferably bonded to the para position with respect to the imidazole ring. According to the triarylimidazole group-containing prepolymer in which the group R ¹ composed of a chlorine atom is bonded to the para position with respect to the imidazole ring, it is easy to form a cross-linked bond between the imidazole rings. Further, when R ² in the triarylimidazole group-containing prepolymer represented by the general formula (5) is a chlorine atom, the group R ² is in any of the ortho, meta, and para positions with respect to the imidazole ring. It may be combined. When R ² is a methoxy group, the group R ² is preferably bonded to the ortho position with respect to the imidazole ring.

In the above general formula (5), the imidazole ring of the triarylimidazole group is in the meta position with respect to the group L ^{1 with} respect to the benzene ring to be continuously bonded to the group L ¹ in the triarylimidazole group. It is preferable that they are bonded. In an imidazole ring triaryl imidazole group, the benzene ring to be bonded in succession groups L ^1, according to the triaryl imidazole group containing prepolymer which is bonded in a meta position with respect to group L ^1, imidazole ring It is easy to form a crosslink between them.
In the general formula (5), L ¹ is the same as L ¹ in the general formula (3). Furthermore, in the said General formula (5), n is a repeating number, and is an integer of 1-100 specifically, for example.

  Also in the method for producing the toner through the step (II), a method in which the polymerization treatment is performed in an aqueous medium is preferable, and a so-called suspension polymerization method, emulsion polymerization method, and emulsion association method can be used. By using such a method, it is possible to obtain a toner that remains sufficiently without cleavage of a bond related to crosslinking. In addition, in a toner manufactured by a so-called pulverization method, there is a possibility that a bond related to crosslinking may be broken by an external force such as kneading during the manufacturing process.

  In the case of passing through the step (II), the polymerization treatment is performed in a state where a polymerization treatment liquid containing a polymerizable triarylimidazole compound is dispersed or suspended or emulsified in an aqueous medium. When the suspension polymerization method or the emulsion polymerization method is employed, the resulting polymer particles are subjected to a crosslinking treatment, mixed with a polyfunctional radical polymerizable compound-containing resin dispersion, and then aggregated and fused to form toner particles. When the obtained emulsion association method is employed, the polymer particles obtained are subjected to a crosslinking treatment, and further mixed with other toner resin fine particles and a polyfunctional radical polymerizable compound-containing resin dispersion, Toner particles are obtained by fusing and associating.

Also in the polymerization treatment in the step (II), it is preferable to copolymerize with a copolymerizable monomer copolymerizable with the polymerizable triarylimidazole compound, thereby obtaining a crosslinked polymer.
Examples of the polymerizable triarylimidazole compound for copolymerization include the same monomers as the copolymerization monomer used in the method through the step (I).
Thus, according to the crosslinked polymer synthesized by copolymerization, the fixability of the obtained toner can be easily controlled.

  The copolymerization ratio between the polymerizable triarylimidazole compound and the copolymerization monomer is preferably 2:99 to 40:80 in terms of a molar ratio of polymerizable triarylimidazole compound: copolymerization monomer.

The crosslinking treatment in the step (II) can be performed by adding an oxidizing agent to the triarylimidazole group-containing prepolymer. As an oxidizing agent, the same thing as what is used in the process of (I) can be mentioned.
The treatment temperature can be 5 to 15 ° C., and the treatment time can be 2 to 8 hours.

(3) Aggregation / fusion process Aqueous medium in which the resin particle dispersion containing the cross-linked polymer obtained in (2) and the polyfunctional radical polymerizable compound-containing resin dispersion obtained in (1) are mixed. By adding an aggregating agent and adjusting the temperature, the particles are aggregated and fused to form toner particles.
When the cross-linked polymer-containing resin particle dispersion is obtained by an emulsion polymerization method or an emulsion association method, a colorant particle dispersion or a release agent particle dispersion is added in advance to start the aggregation reaction. Add the functional radical polymerizable compound-containing resin dispersion.
The toner particles constituting the toner of the present invention may have a core-shell structure comprising core particles and a shell layer covering the outer peripheral surface of the core particles. In such core / shell toner particles, the shell layer preferably contains the radical polymerizable compound.
The toner particles having a core / shell structure preferably have a form in which the shell layer completely covers the core particles. If the material component constituting the core particles is not exuded to the outside, the shell layer is cracked. Etc. may be formed and a part of the core particle may be exposed.
When a charge control agent and / or magnetic powder is contained, these are preferably contained in the shell layer.
Further, when a colorant and / or a release agent are contained, these are preferably contained as material components constituting the core particles, but may also be contained in the shell layer.
The core particles of the toner particles having the core / shell structure can contain various known resins, and preferably contain, for example, a styrene-acrylic resin.
Examples of the resin to be contained in the core particle include those obtained by polymerizing the following vinyl monomers.
Examples of vinyl monomers include styrene; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, Methacrylic acid ester derivatives such as stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-acrylate -Derivation of acrylate esters such as butyl, isobutyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, phenyl acrylate, etc. , Ethylene, propylene, olefins such as isobutylene; acrylonitrile, methacrylonitrile, acrylic acid or methacrylic acid derivatives such as acrylamide. These vinyl monomers can be used alone or in combination of two or more.

The resin contained in the core particles preferably has a glass transition point in the range of 10 to 46 ° C.
A toner having core particles containing a resin having a glass transition point in the above range can provide sufficient low-temperature fixability.
The glass transition point of the resin contained in the core particle is measured by the same method as described above using the measurement sample as the resin contained in the core particle.

  As a method for producing such a toner having a core / shell structure, for example, an emulsion association method is used to form a shell layer in a dispersion of core particles produced by an appropriate method in an aqueous medium. Fine particles (for example, radical polymerizable compound-containing resin) are added, and the fine particles (for example, radical polymerizable compound-containing resin) related to the shell layer are aggregated and fused on the surface of the core particles to cover the surface of the core particles. It can be obtained by forming a shell layer.

(4) Washing / drying step The toner particles are filtered off from the aqueous medium, and unnecessary substances such as surfactants are removed from the toner particles by the washing treatment, and the washed toner particles are dried (5) external addition. Agent Addition Step An external additive is added to the dried toner particles.

[Particle size of toner particles]
The particle diameter of the toner particles constituting the toner as described above is preferably 4 to 10 μm, and more preferably 6 to 9 μm, for example, on a volume basis median diameter.
When the volume-based median diameter is in the above range, the transfer efficiency is increased, the image quality of halftone is improved, and the image quality of fine lines and dots is improved.

  The volume-based median diameter of toner particles is measured and calculated using a measuring device in which a computer system for data processing (Beckman Coulter, Inc.) is connected to “Coulter Multisizer TA-III” (Beckman Coulter, Inc.). Is. Specifically, 0.02 g of toner is added to 20 mL of a surfactant solution (for example, a surfactant solution in which a neutral detergent containing a surfactant component is diluted 10-fold with pure water for the purpose of dispersing the toner). Then, ultrasonic dispersion was performed for 1 minute to prepare a toner dispersion, and this toner dispersion was placed in a beaker containing “ISOTON II” (manufactured by Beckman Coulter) in a sample stand. Pipette until the indicated concentration is between 5% and 10%. Here, a reproducible measurement value can be obtained by setting the concentration range. In the measurement apparatus, the measurement particle count is 25000, the aperture diameter is 50 μm, the frequency value is calculated by dividing the measurement range of 1 to 30 μm into 256, and the volume integrated fraction is 50 % Particle diameter was defined as the volume-based median diameter.

[Average circularity of toner particles]
The toner of the present invention preferably has an average circularity represented by the above formula (T) of 0.930 to 1.000 for the individual toner particles constituting the toner from the viewpoint of improving transfer efficiency. More preferably, it is 0.950-0.995.
Formula (T): Average circularity = circumference of circle determined from equivalent circle diameter / perimeter of particle projection image

(External additive)
The above toner particles can constitute the toner of the present invention as they are, but in order to improve fluidity, chargeability, cleaning properties, etc., a fluidizing agent that is a so-called post-treatment agent is added to the toner particles. An external additive such as a cleaning aid may be added to constitute the toner of the present invention.

As the post-treatment agent, for example, inorganic oxide fine particles composed of silica fine particles, alumina fine particles, titanium oxide fine particles, etc., inorganic stearate compound fine particles such as aluminum stearate fine particles, zinc stearate fine particles, or strontium titanate, titanium Inorganic titanic acid compound fine particles such as zinc acid are listed. These can be used individually by 1 type or in combination of 2 or more types.
These inorganic fine particles are preferably subjected to surface treatment with a silane coupling agent, a titanium coupling agent, a higher fatty acid, silicone oil or the like in order to improve heat-resistant storage stability and environmental stability.

  The total amount of these various external additives added is 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the toner. In addition, various external additives may be used in combination.

(Developer)
The toner of the present invention can be used as a magnetic or non-magnetic one-component developer, but may be mixed with a carrier and used as a two-component developer. When the toner of the present invention is used as a two-component developer, the carrier is made of a conventionally known material such as a metal such as iron, ferrite, or magnetite, or an alloy of such a metal with a metal such as aluminum or lead. Magnetic particles can be used, and ferrite particles are particularly preferable. Further, as the carrier, a coat carrier in which the surface of the magnetic particles is coated with a coating agent such as a resin, a binder type carrier in which a magnetic fine powder is dispersed in a binder resin, or the like may be used.
The coating resin constituting the coat carrier is not particularly limited, and examples thereof include olefin resins, styrene resins, styrene-acrylic resins, silicone resins, ester resins, and fluorine resins. Moreover, it does not specifically limit as resin which comprises a resin dispersion type carrier, A well-known thing can be used, For example, a styrene-acrylic-type resin, a polyester resin, a fluororesin, a phenol resin etc. can be used.

  The volume-based median diameter of the carrier is preferably 20 to 100 μm, and more preferably 20 to 60 μm. The volume-based median diameter of the carrier can be typically measured by a laser diffraction particle size distribution measuring apparatus “HELOS” (manufactured by SYMPATEC) equipped with a wet disperser.

(Image forming method)
The toner of the present invention can be suitably used in an image forming method including a fixing step by a heat and pressure fixing method capable of applying pressure and heating. Particularly, it is suitable for an image forming method in which fixing is performed at a relatively low fixing temperature in which the fixing temperature in the fixing step is 80 to 110 ° C., preferably 80 to 95 ° C. at the surface temperature of the heating member in the fixing nip portion. Can be used for
Further, it can be suitably used for a high-speed fixing image forming method in which the fixing linear velocity is 5 to 600 mm / sec.
In this image forming method, specifically, the toner as described above is used, for example, an electrostatic latent image formed on a photoreceptor is developed to obtain a toner image, and this toner image is used as an image support. Then, the toner image transferred onto the image support is fixed on the image support by a fixing process using a thermal pressure fixing method, whereby a printed matter on which a visible image is formed is obtained.

  The application of pressure and heating in the fixing step are preferably simultaneous, and the pressure may be applied first and then heated.

The pressure to be applied to the toner particles constituting the toner image transferred onto the image support is, for example, (i) a contact load between the heating roller and the pressure roller in a heat roller type fixing device described later. May be a pressure at which is 40 to 350N. Further, for example, in a later-described (ii) film heating type fixing device, the surface pressure of the fixing belt with respect to the image support may be any pressure that is 9 × 10 ^{3 to} 5 × 10 ⁵ N / m ² .

  As the fixing device of the heat and pressure fixing method in the image forming method using the toner of the present invention, various known devices can be employed. Hereinafter, a heat roller type fixing device and a film heating type fixing device will be described as the thermal pressure fixing device.

(I) Heat roller type fixing device Generally, a heat roller type fixing device is provided with a roller pair of a heating roller and a pressure roller in contact with the heating roller, and the pressure applied between the heating roller and the pressure roller. When the pressure roller is deformed, a so-called fixing nip portion is formed in the deformed portion.

In general, the heating roller includes a metal core made of a hollow metal roller made of aluminum or the like and a heat source made of a halogen lamp or the like disposed therein, the metal core is heated by the heat source, and the outer peripheral surface of the heating roller is The temperature is adjusted by controlling energization to the heat source so as to be maintained at a predetermined fixing temperature.
In particular, when used as a fixing device of an image forming apparatus that forms a full-color image that requires a capability of sufficiently melting and mixing a toner image composed of a maximum of four toner layers, a core metal is used as a heating roller. It is preferable to use a material having a high heat capacity and a rubber elastic layer for uniformly melting the toner image on the outer peripheral surface of the metal core.

The pressure roller has an elastic layer made of a soft rubber such as urethane rubber or silicon rubber.
As the pressure roller, for example, a metal core made of a hollow metal roller made of aluminum or the like and having an elastic layer formed on the outer peripheral surface of the metal core may be used.
Furthermore, when the pressure roller is configured to have a metal core, a heat source such as a halogen lamp is disposed inside the pressure roller, and the metal core is heated by the heat source. Alternatively, the temperature may be adjusted by controlling the power supply to the heat source so that the outer peripheral surface of the heat source is maintained at a predetermined fixing temperature.

  As these heating rollers and / or pressure rollers, as the outermost layer, a mold release made of a fluororesin such as polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) or the like is used. It is preferable to use a layer formed. The thickness of the release layer can be approximately 10 to 30 μm.

  In such a heat roller type fixing device, the roller pair is rotated and the image support to form a visible image is sandwiched and conveyed in the fixing nip portion, whereby the heating by the heating roller and the pressure in the fixing nip portion are reduced. Thus, an unfixed toner image is fixed on the image support.

(Ii) Film heating type fixing device Generally, a film heating type fixing device is made of, for example, a heating body made of a ceramic heater, a pressure roller, and a heat resistant film between the heating body and the pressure roller. The fixing film is sandwiched, and the pressure roller is deformed by the pressure applied between the heating body and the pressure roller, so that a so-called fixing nip portion is formed in the deformed portion. .

  As the fixing film, a heat-resistant film made of polyimide or the like, a sheet or a belt is used, and the heat-resistant film, sheet or belt made of polyimide or the like is used as a film substrate, and tetrafluoro is formed on the film substrate. A release layer made of a fluororesin such as ethylene (PTFE) or tetrafluoroethylene-perfluoroalkyl ether copolymer (PFA) may be formed, and further, a film substrate and a release layer Between the two, an elastic layer made of rubber or the like may be provided.

In such a film heating type fixing device, an image support carrying an unfixed toner image is nipped and conveyed together with the fixing film between a fixing film forming a fixing nip portion and a pressure roller. Thus, heating by the heating body through the fixing film and application of pressure at the fixing nip portion are performed, whereby an unfixed toner image is fixed on the image support.
According to such a film heating type fixing device, the heating body only needs to be energized to generate heat at a predetermined fixing temperature only during image formation. Quick start performance with a short waiting time until image formation can be performed is obtained, power consumption during standby of the image forming apparatus is extremely small, and power saving can be achieved.

(Image support)
Examples of the image support used in the image forming method using the toner of the present invention include thin paper to heavy paper, coated paper such as fine paper, art paper or coated paper, and commercially available Japanese paper. Various types of paper such as postcard paper, plastic film for OHP, and cloth can be cited, but the invention is not limited to these.

  According to the toner of the present invention as described above, a cross-linked polymer is contained, and the cross-linked polymer has a characteristic of decrosslinking by cleaving a bond between imidazole rings of a triarylimidazole group by application of pressure. Therefore, by applying pressure, the glass transition point is changed to a lower one. By applying pressure and heating, the state of sufficient elasticity of the toner is lowered even at a low heating temperature. Is obtained early, and as a result, sufficient low-temperature fixability is obtained. On the other hand, in the state before the pressure is applied, the specific crosslinked polymer has heat-resistant storage stability because the micro Brownian motion due to heat is suppressed. In addition, according to such a toner, a sufficiently reduced state of the elastic modulus of the crosslinked polymer due to the application of pressure can be obtained at an early stage, so that sufficient high-speed fixability can also be obtained.

  In addition, in the present invention, since the resin phase 1 containing a polyfunctional radical polymerizable compound is included in addition to the resin phase 2 containing the crosslinked polymer, the crosslinked polymer causing decrosslinking is generated. The radical and the polyfunctional radical polymerizable compound react to form a crosslinked structure. Therefore, the image stability after fixing is improved. Therefore, both low temperature fixing and image stability can be achieved.

  The toner embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment, and various modifications can be made.

1. Resin synthesis (polyester resin synthesis)
(Polyvalent carboxylic acid monomer)
Terephthalic acid: 36 parts by mass Isophthalic acid: 5.2 parts by mass (polyhydric alcohol monomer)
2,2-bis (4-hydroxyphenyl) propanepropylene oxide 2-mole adduct: 76 parts by mass 2,2-bis (4-hydroxyphenyl) propaneethylene oxide 2-mole adduct: 24 parts by mass Stirrer, nitrogen inlet tube The polyvalent carboxylic acid monomer and the polyhydric alcohol component are charged into a reaction vessel equipped with a temperature sensor and a rectifying tower, and the temperature is raised to 190 ° C. over 1 hour, and the reaction system is uniformly stirred. Then, the catalyst Ti (OBu) ₄ (0.003% by mass with respect to the total amount of the polyvalent carboxylic acid monomer) was added.
Furthermore, 6 hours were required from the same temperature while distilling off the generated water, the temperature was raised to 240 ° C., and the dehydration condensation reaction was continued at 240 ° C. for another 6 hours to carry out polymerization to obtain a polyester resin. When the molecular weight of the obtained polyester resin was measured by GPC, it was a number average molecular weight of 3100 (HLC-8 120GPC manufactured by Tosoh Corporation, converted in terms of styrene standard substance). Moreover, as a result of measuring the thermal characteristics of the resin obtained with a differential scanning calorimeter (Diamond DSC manufactured by PerkinElmer: temperature rising rate: 10 ° C./min), Tg was 62 ° C.

[Synthesis example of styrene acrylic resin]
600 parts by mass of water was charged in a reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube, and a nitrogen introducing device, and the internal temperature was raised to 70 ° C. while stirring at a stirring speed of 230 rpm under a nitrogen stream. 119 parts by mass of styrene, 33 parts by mass of n-butyl acrylate, 8 parts by mass of methacrylic acid, 4.5 parts by mass of n-octyl mercaptan were added thereto, and 3 parts by mass of a polymerization initiator (potassium persulfate; KPS) was ionized. An aqueous solution dissolved in 40 parts by mass of exchange water was added, and the system was heated and stirred at 70 ° C. for 10 hours to prepare resin particles.
The weight average molecular weight (Mw) of the resin particles was 13200. The number average particle diameter of the composite resin particles constituting the resin particles was 221 nm, and the glass transition temperature (Tg) was 55.4 ° C.
Methanol and hydrochloric acid were added to the resin particles to precipitate the resin component, followed by filtration and drying to obtain a styrene acrylic resin.

2. Synthesis of polyfunctional radical polymerizable compound-containing particle dispersion [Synthesis Example 1 of polyfunctional radical polymerizable compound-containing particle dispersion]
400 parts by weight of “polyester resin” and 8.3 parts by weight of polyfunctional radical polymerizable compound divinylbenzene are added to 1700 parts by weight of ethyl acetate, and the mixture is heated to 70 ° C. and dissolved and mixed to obtain “resin solution 1”. It was. Separately, 2000 parts by weight of ion-exchanged water and 4.8 parts by weight of sodium dodecyl sulfate were stirred and dispersed to prepare “Aqueous Phase 1” to be a continuous phase. In this “water phase 1”, “oil phase 1” is added while stirring with “TK Homomixer Mark II2.5” (manufactured by PRIMIX Co., Ltd.), and by adjusting the rotation speed of stirring, “oil droplet 1” is added. Prepared. Thereafter, the solution was distilled off under reduced pressure at 50 ° C. to remove ethyl acetate, and a polyfunctional radical polymerizable compound-containing particle dispersion 1 having a volume-based median diameter of 180 nm was obtained.

[Synthesis Example 2 of polyfunctional radical polymerizable compound-containing particle dispersion]
Charge 1700 parts by weight of toluene with 400 parts by weight of “styrene acrylic resin” and 8.3 parts by weight of divinylbenzene, a polyfunctional radical polymerizable compound, and heat up to 70 ° C. to dissolve and mix to obtain “resin solution 2”. It was. Separately, 2,000 parts by weight of ion-exchanged water and 4.8 parts by weight of sodium dodecyl sulfate were stirred and dispersed to prepare “Aqueous Phase 2” to be a continuous phase. In this “water phase 2”, “oil phase 2” is added while stirring with “TK homomixer Mark II2.5” (manufactured by PRIMIX Co., Ltd.), and “oil droplet 2” is adjusted by adjusting the stirring speed. Prepared. Thereafter, the toluene was removed under reduced pressure at 50 ° C. to obtain a polyfunctional radical polymerizable compound-containing particle dispersion 2 having a volume-based median diameter of 200 nm.

[Synthesis example 3 of polyfunctional radical polymerizable compound-containing particle dispersion]
Example of synthesis of polyfunctional radical polymerizable compound-containing particle dispersion, except that 70.6 parts by weight of polyethylene glycol diacrylate was used instead of 8.3 parts by weight of divinylbenzene in Synthesis Example 1 of polyfunctional radical polymerizable compound-containing particle dispersion 1 and a polyfunctional radical polymerizable compound-containing particle dispersion 3 having a volume-based median diameter of 200 nm was obtained.

[Polyfunctional radical polymerizable compound-containing particle dispersion synthesis example 4]
Example of synthesis of polyfunctional radical polymerizable compound-containing particle dispersion, except that 70.6 parts by weight of polyethylene glycol diacrylate was used instead of 8.3 parts by weight of divinylbenzene in Synthesis Example 2 of polyfunctional radical polymerizable compound-containing particle dispersion 2 and a polyfunctional radical polymerizable compound-containing particle dispersion 4 having a volume-based median diameter of 220 nm was obtained.

[Polyfunctional radical polymerizable compound-containing particle dispersion synthesis example 5]
Synthesis of polyfunctional radical polymerizable compound-containing particle dispersion, except that 72.4 parts by weight of polyethylene glycol dimethacrylate was used instead of 8.3 parts by weight of divinylbenzene in Synthesis Example 1 of particle dispersion containing polyfunctional radical polymerizable compound Synthesis was performed in the same manner as in Example 1 to obtain a polyfunctional radical polymerizable compound-containing particle dispersion 5 having a volume-based median diameter of 220 nm.

[Polyfunctional radical polymerizable compound-containing particle dispersion synthesis example 6]
Synthesis of polyfunctional radical polymerizable compound-containing particle dispersion, except that 72.4 parts by weight of polyethylene glycol dimethacrylate was used instead of 8.3 parts by weight of divinylbenzene in Synthesis Example 2 of particle dispersion containing polyfunctional radical polymerizable compound Synthesis was conducted in the same manner as in Example 2 to obtain a polyfunctional radical polymerizable compound-containing particle dispersion 6 having a volume-based median diameter of 230 nm.

[Synthesis Example 7 of polyfunctional radically polymerizable compound-containing particle dispersion]
Polyfunctional radical polymerizable compound-containing particle dispersion synthesis example except that 22.4 parts by weight of pentaerythritol tetraacrylate was used instead of 8.3 parts by weight of divinylbenzene in Synthesis example 1 of particle dispersion containing polyfunctional radical polymerizable compound 1 and a polyfunctional radical polymerizable compound-containing particle dispersion 7 having a volume-based median diameter of 250 nm was obtained.

[Synthesis example 8 of polyfunctional radical polymerizable compound-containing particle dispersion]
Polyfunctional radical polymerizable compound-containing particle dispersion synthesis example, except that 22.4 parts by weight of pentaerythritol tetraacrylate was used instead of 8.3 parts by weight of divinylbenzene in Synthesis example 2 of particle dispersion containing polyfunctional radical polymerizable compound 2 and a polyfunctional radical polymerizable compound-containing particle dispersion 8 having a volume-based median diameter of 260 nm was obtained.

[Polyfunctional radical polymerizable compound-containing particle dispersion synthesis example 9]
A polyfunctional radical polymerizable compound-containing particle dispersion synthesis example 1 was synthesized in the same manner as in the polyfunctional radical polymerizable compound-containing particle dispersion synthesis example 1 except that the polyfunctional radical polymerizable compound was not added, and the volume-based median diameter was 200 nm. The polyfunctional radically polymerizable compound-containing particle dispersion 9 was obtained.

[Polyfunctional Radical Polymerizable Compound-Containing Particle Dispersion Synthesis Example 10]
A polyfunctional radical polymerizable compound-containing particle dispersion synthesis example 2 was synthesized in the same manner as in the polyfunctional radical polymerizable compound-containing particle dispersion synthesis example 2 except that no polyfunctional radical polymerizable compound was added, and the volume-based median diameter was 210 nm. The polyfunctional radically polymerizable compound-containing particle dispersion 10 was obtained.

3. Synthesis example of vinyl triphenylimidazole compound [Synthesis example 1 of vinyl-triphenylimidazole compound]
In the reaction vessel,
Benzoin (2-hydroxy-1,2-diphenylethanone) 1609 parts by weight 3-vinylbenzaldehyde 1002 parts by weight Ammonium acetate 5838 parts by weight Boron tetrafluoride 1603 parts by weight, and heated to 100 ° C., Stirring was continued for 1.5 hours. After completion of the reaction, the reaction mixture was diluted with water, and the resulting solid was filtered, washed repeatedly with water, dried, and then subjected to silica gel column chromatography with a mixed solvent of hexane / ethyl acetate (mass ratio 9: 1). After purification by using, recrystallization with a mixed solvent of methanol / dichloroethane (mass ratio 9: 1) gave the vinyl-triphenylimidazole compound [1] represented by the exemplified compound 1.

[Synthesis Example 2 of Vinyl-Triphenylimidazole Compound]
In the reaction vessel,
Benzoin (2-hydroxy-1,2-diphenylethanone) 1609 parts by mass p-hydroxybenzaldehyde 850 parts by mass Ammonium acetate 5838 parts by mass Boron tetrafluoride 1603 parts by mass, and a mixture at 100 ° C for 1.5 hours Stirring was continued. After completion of the reaction, it is diluted with 0.1N aqueous sodium hydroxide solution, and the resulting solid is filtered, washed repeatedly with water, dried, and then mixed with a mixed solvent of hexane / ethyl acetate (mass ratio 9: 1). After purification using silica gel column chromatography, Compound 1 was obtained by recrystallization from a mixed solvent of methanol / dichloroethane (mass ratio 9: 1).
Subsequently, 1000 parts by mass of Compound 1 12500 parts by mass of tetrahydrofuran, 400 parts by mass of triethylamine were added to the reactor, 330 parts by mass of acryloyl chloride was added dropwise, and stirring was continued at 5 ° C. for 20 hours. After completion of the reaction, the obtained solid was filtered, repeatedly washed with methylo / water (weight ratio 1: 1), and recrystallized with acetone, whereby the vinyl-triphenylimidazole compound represented by the above exemplary compound 3 was obtained. [2] was obtained.

4). Suspension polymerization particle synthesis example [Suspension polymerization particle synthesis example 1]
To 900 parts by mass of ion-exchanged water heated to 60 ° C., 2.3 parts by mass of tricalcium phosphate is added and stirred at 10,000 rpm using a TK homomixer Mark II2.5 type (manufactured by Primics Co., Ltd.). A medium was prepared.
on the other hand,
Vinyl-triphenylimidazole compound [1] 10 parts by mass Styrene 118.4 parts by mass n-butyl acrylate 50.6 parts by mass Cyan colorant (CI Pigment Blue 15.3) 13 parts by mass of “Attritor” (Mitsui Miike Kako Co., Ltd.) is uniformly dispersed and mixed, heated to 60 ° C., and ester wax mainly composed of behenyl behenate (maximum endothermic peak in DSC measurement: 72 ° C.) 32 mass A polymerizable monomer composition was prepared by adding 4 parts by mass of a polymerization initiator lauroyl peroxide (10 hour half-life temperature: 62 ° C.).
The polymerizable monomer composition was put into the above aqueous medium, and granulated by stirring at 10,000 rpm for 7 minutes with a TK homomixer at a temperature of 60 ° C. in an N ₂ atmosphere.
Next, the mixture was reacted at a temperature of 60 ° C. for 6 hours while stirring with a paddle stirring blade, and then the liquid temperature was set to 80 ° C. and stirring was further continued for 4 hours to obtain a suspension.
After completion of the reaction, the suspension was cooled to 10 ° C. at a cooling rate of −5 ° C./min. The obtained suspension polymerization particles had a particle size of 6.1 μm and an average circularity of 0.96.
Thereafter, 5 parts by mass of a 1% aqueous potassium ferricyanide solution was added, and the mixture was further stirred at 10,000 rpm for 1 minute, and then reacted at a temperature of 10 ° C. for 6 hours while stirring with a paddle stirring blade to obtain a suspension.

[Synthesis Example 2 of Suspension Polymerized Particles] (Vinyl-Triphenylimidazole Dimer Compound)
Vinyl-triphenylimidazole compound [1] 617 parts by mass Ethanol 80 parts by mass Tetrahydrofuran (THF) To a solution consisting of 100 parts by mass, 340 parts by mass of a 1% aqueous potassium ferricyanide solution was added and stirred at a temperature of 10 ° C. with a paddle stirring blade. For 2 hours. Thereafter, the solvent (ethanol and tetrahydrofuran) was distilled off to obtain a vinyl-triphenylimidazole dimer compound which is a dimer compound of the vinyl-triphenylimidazole compound [1].
On the other hand, 2.3 parts by mass of tricalcium phosphate is added to 900 parts by mass of ion-exchanged water heated to 60 ° C., and the mixture is stirred at 10,000 rpm using a TK homomixer Mark II2.5 type (manufactured by PRIMIX Corporation). An aqueous medium was prepared.
Also,
Vinyl-triphenylimidazole dimer compound 10 parts by mass Styrene 118.4 parts by mass n-Butyl acrylate 50.6 parts by mass Cyan colorant (CI Pigment Blue 15.3) 13 parts by mass of “Attritor” (Mitsui Miike Kako Co., Ltd.) is uniformly dispersed and mixed, heated to 60 ° C., and ester wax mainly composed of behenyl behenate (maximum endothermic peak in DSC measurement: 72 ° C.) 32 mass A polymerizable monomer composition was prepared by adding 4 parts by mass of a polymerization initiator lauroyl peroxide (10 hour half-life temperature: 62 ° C.).
The polymerizable monomer composition was put into the above aqueous medium, and granulated by stirring at 10,000 rpm for 7 minutes with a TK homomixer at a temperature of 60 ° C. in an N ₂ atmosphere.
Next, the mixture was reacted at a temperature of 60 ° C. for 6 hours while stirring with a paddle stirring blade, and then the liquid temperature was set to 80 ° C. and stirring was further continued for 4 hours to obtain a suspension. The obtained suspension polymerization particles had a particle size of 6.2 μm and an average circularity of 0.93.

5). Emulsion polymerization particle synthesis example [Emulsion polymerization particle synthesis example 1]
(1) Preparation Step of Resin Fine Particle Dispersion Vinyl-Triphenylimidazole Compound [1] 18 parts by mass Styrene 207 parts by mass Butyl acrylate 91 parts by mass Acrylic acid 6 parts by mass Tertiary decyl mercaptan 24 parts by mass were mixed and dissolved. In a water-based medium in which 6 parts by mass of polyoxyethylene lauryl ether “E-700” (manufactured by Nippon Emulsion Co., Ltd.) and 10 parts by mass of sodium n-dodecylbenzenesulfonate were dissolved in 550 parts by mass of ion-exchanged water, The mixture was dispersed therein, dispersed, emulsified, and slowly mixed for 10 minutes, and then 50 parts by mass of ion-exchanged water in which 4 parts by mass of potassium persulfate was dissolved was added to perform nitrogen substitution.
Next, while stirring the inside of the flask with an oil bath until the content reached 70 ° C., emulsion polymerization was continued for 5 hours to obtain an emulsion.
Thereafter, the resin particle dispersion is cooled to 10 ° C. at a cooling rate of −5 ° C./min, 5 parts by mass of 1% potassium ferricyanide aqueous solution is added, and the mixture is reacted at a temperature of 10 ° C. for 6 hours to disperse the resin fine particles [1]. Thus obtained emulsion polymerized particles 1 were obtained.
Emulsion polymerized particles 1 had a volume-based median diameter of 140 nm.
Further, since the emulsion polymer particles 1 formed a crosslinked structure, they were substantially insoluble in tetrahydrofuran.

[Synthesis Example 2 of Emulsion Polymerized Particles]
Instead of 16 parts by mass of the vinyl-triphenylimidazole compound [1] in [Synthesis Example 1 of Emulsion Polymerized Particles], 16 parts by mass of the vinyl-triphenylimidazole dimer compound was used, and “−5 ° C./min. The resin particle dispersion was cooled to 10 ° C. at a cooling rate of 5% by weight, and 5 parts by weight of 1% potassium ferricyanide aqueous solution was added and reacted at a temperature of 10 ° C. for 6 hours. Emulsion polymerized particles 2 in which was dispersed were prepared. Emulsion polymerized particles 2 had a volume-based median diameter of 160 nm.
Further, since the emulsion polymer particles 2 formed a crosslinked structure, they were substantially insoluble in tetrahydrofuran.

[Synthesis Example 3 of Emulsion Polymerized Particles]
In the same manner as in [Emulsion polymerized particle synthesis example 1], except that 16 parts by mass of the vinyl-triphenylimidazole compound [1] was used instead of 16 parts by mass of the resin particles [1] 3] dispersed therein was prepared. Emulsion polymerized particles 3 had a volume-based median diameter of 130 nm.
Further, since the emulsion polymer particles 3 formed a bridge structure, they were substantially insoluble in tetrahydrofuran.

[Synthesis Example 4 of Emulsion Polymerized Particles]
In the same manner as in [Emulsion polymerized particle synthesis example 2], except that 16 parts by mass of the vinyl-triphenylimidazole compound [1] was used instead of 16 parts by mass of the resin fine particles [1] Emulsion polymerized particles 4 in which [4] was dispersed were prepared. The emulsion polymer particles 4 had a volume-based median diameter of 150 nm.
Further, since the emulsion polymerized particles 4 formed a crosslinked structure, they were substantially insoluble in tetrahydrofuran.

6). Toner Production [Toner Production Example 1]
1800 parts by weight of the suspension obtained in Synthesis Example 1 of suspension polymerized particles, 1 part by weight of polyoxyethylene lauryl ether “E-700” (manufactured by Nippon Emulsion Co., Ltd.), 1000 parts by weight of pure water were thermometer, cooling tube Then, it was put into a separable flask provided with a nitrogen introducing device and a stirring device. Next, an aqueous solution in which 10 parts by mass of magnesium chloride hexahydrate was dissolved in 10 parts by mass of ion-exchanged water was added, and then the temperature in the system was raised to 70 ° C. Next, 767 parts by weight of a polyfunctional radical polymerizable compound-containing resin dispersion 3 for forming a toner shell layer was added. When the shell layer was formed on the toner surface, 10 parts by mass of ethylenediaminetetraacetic acid was added. The temperature was raised to 80 ° C. and left for 1 hour, and then cooled to 30 ° C. at 6 ° C./min to complete the reaction. Toner particles 1 having a toner particle size of 6.5 μm and an average circularity of 0.97 were obtained.
Next, the produced toner particle dispersion was subjected to solid-liquid separation with a basket-type centrifuge “MARK III type” (model number 60 × 40) (manufactured by Matsumoto Kikai Kogyo Co., Ltd.) to form a toner wet cake. Thereafter, the toner washing and solid-liquid separation were repeated until the electric conductivity of the filtrate reached 15 μS / cm or less.
Subsequently, the wet cake was transferred to an airflow dryer “flash jet dryer” (manufactured by Seishin Enterprise Co., Ltd.), and dried until the water content reached 0.5% by mass. The drying process was performed by blowing an air current of 40 ° C. and 20% RH. The dried toner was allowed to cool to 24 ° C., and 1.0 part by mass of hydrophobic silica was mixed with 100 parts by mass of the toner using a Henschel mixer. The peripheral speed of the rotary blade was 24 m / s, and the mixture was mixed for 20 minutes, and then passed through a 400 MESH sieve. The obtained toner is referred to as “toner particles 1”.
1% by mass of hydrophobic silica particles are added to the toner particles 1 obtained, and the mixture is mixed for 20 minutes using a Henschel mixer at a peripheral speed of a rotating blade of 24 m / s. The external additive was added by passing it through to obtain “Toner 1”.

[Toner Production Example 2]
Toner as in Toner Production Example 1, except that 767 parts by weight of polyfunctional radical polymerizable compound-containing resin dispersion 3 used in Toner Production Example 1 was changed to 767 parts by weight of polyfunctional radical polymerizable compound-containing resin dispersion 4 Manufactured. Toner particles 2 having a toner particle size of 6.4 μm and an average circularity of 0.96 were obtained.

[Toner Production Example 3]
Except for changing 1800 parts by weight of the suspension obtained in Synthesis Example 1 of the suspension polymerization particles used in Toner Production Example 1 to 1800 parts by weight of the suspension obtained in Synthesis Example 2 of the suspension polymerization particles, A toner was produced in the same manner as in Toner Production Example 1. Toner particles 3 having a toner particle size of 6.6 μm and an average circularity of 0.96 were obtained.

[Toner Production Example 4]
(Preparation process of colorant fine particle dispersion)
6 parts by mass of a nonionic surfactant “E-700” (Japan Emulsion Co., Ltd.) is stirred and dissolved in 200 parts by mass of ion-exchanged water, and a cyan pigment (CI Pigment Blue) is used as a colorant while continuing stirring. 15.3) 50 parts by mass were gradually added, and then dispersed for 10 minutes with a homogenizer “Ultra Turrax” (manufactured by IKA) to prepare a colorant fine particle dispersion in which colorant fine particles were dispersed. . When the particle diameter of the colorant fine particles in this colorant fine particle dispersion was measured using “MICROTRAC UPA 150” (manufactured by Nikkiso Co., Ltd.), the volume-based median diameter was 180 nm.
(Process for preparing release agent fine particle dispersion)
6 parts by mass of a nonionic surfactant “E-700” (Japan Emulsion Co., Ltd.) is stirred and dissolved in 200 parts by mass of ion-exchanged water, and paraffin wax “HNP-0190” ( (Nippon Seiki Co., Ltd.) 50 parts by mass was added, heated to 95 ° C., and then dispersed with a homogenizer “Ultra Turrax T50” (IKA) for 10 minutes to disperse the release agent fine particles. A release agent fine particle dispersion was prepared. The particle diameter of the release agent fine particles in this release agent fine particle dispersion was measured using “MICROTRAC UPA 150” (manufactured by Nikkiso Co., Ltd.), and the volume-based median diameter was 250 nm.
(Toner preparation process)
Emulsion polymerized particles 1 272 parts by mass (in terms of solid content), ion exchange water 2200 parts by mass, colorant particle dispersion 98 parts by mass, release agent fine particle dispersion 243 parts by mass, thermometer, cooling tube, nitrogen introducing device, It put into a separable flask provided with a stirrer. Furthermore, the pH in which the aqueous sodium hydroxide solution (25% by mass) was added was adjusted to 10 while maintaining the temperature in the system at 30 ° C.
Next, an aqueous solution in which 54.3 parts by mass of magnesium chloride hexahydrate is dissolved in 54.3 parts by mass of ion-exchanged water is added, and then the temperature in the system is raised to 60 ° C. to obtain resin particles. And the aggregation reaction of the colorant particles was started.
After starting agglutination, it is a regular sampling, using a particle size distribution measuring apparatus "COULTER Multisizer 3" (manufactured by Beckman Coulter, Inc.), the median diameter (D ₅₀₎ in volume-based particle to 6.0μm Then, 857 parts by weight of a polyfunctional radical polymerizable compound-containing resin dispersion 1 forming a toner shell layer was added. When the shell layer was formed on the toner surface, 20.1 parts by mass of ethylenediaminetetraacetic acid was added. The circularity of the toner particles at this time was 0.92.
The temperature was raised to 80 ° C., and when the circularity of the toner particles reached 0.96, the reaction was completed by cooling to 30 ° C. at 6 ° C./min. Toner particles 4 having a toner particle size of 6.6 μm and an average circularity of 0.96 were obtained.
Next, the produced toner particle dispersion was subjected to solid-liquid separation with a basket-type centrifuge “MARK III type” (model number 60 × 40) (manufactured by Matsumoto Kikai Kogyo Co., Ltd.) to form a toner wet cake. Thereafter, the toner washing and solid-liquid separation were repeated until the electric conductivity of the filtrate reached 15 μS / cm or less.
Subsequently, the wet cake was transferred to an airflow dryer “flash jet dryer” (manufactured by Seishin Enterprise Co., Ltd.), and dried until the water content reached 0.5% by mass. The drying process was performed by blowing an air current of 40 ° C. and 20% RH. The dried toner was allowed to cool to 24 ° C., and 1.0 part by mass of hydrophobic silica was mixed with 100 parts by mass of the toner using a Henschel mixer. The peripheral speed of the rotary blade was 24 m / s, and the mixture was mixed for 20 minutes, and then passed through a 400 MESH sieve. The obtained toner is referred to as “toner particles 4”.
1% by mass of hydrophobic silica particles are added to the obtained toner particles 4 and mixed for 20 minutes using a Henschel mixer at a peripheral speed of a rotating blade of 24 m / s. The external additive was added by passing it through to obtain “Toner 4”.

[Toner Production Example 5]
Example of toner production, except that 857 parts by weight of the polyfunctional radical polymerizable compound-containing resin dispersion 1 forming the toner shell layer of toner production example 4 is changed to 857 parts by weight of the polyfunctional radical polymerizable compound-containing resin dispersion 2 A toner was produced in the same manner as in Example 4. Toner particles 5 having a toner particle size of 6.5 μm and an average circularity of 0.96 were obtained.

[Toner Production Example 6]
Toner production example, except that 857 parts by weight of the polyfunctional radical polymerizable compound-containing resin dispersion liquid 1 forming the toner shell layer of toner production example 4 is changed to 767 parts by weight of the polyfunctional radical polymerizable compound-containing resin dispersion liquid 3 A toner was produced in the same manner as in Example 4. Toner particles 6 having a toner particle diameter of 6.7 μm and an average circularity of 0.97 were obtained.

[Toner Production Example 7]
Toner production example, except that 857 parts by weight of the polyfunctional radical polymerizable compound-containing resin dispersion 1 forming the shell layer of the toner of Production Example 4 is changed to 767 parts by weight of the polyfunctional radical polymerizable compound-containing resin dispersion 4 A toner was produced in the same manner as in Example 4. Toner particles 7 having a toner particle size of 6.6 μm and an average circularity of 0.97 were obtained.

[Toner Production Example 8]
Toner production example, except that 857 parts by weight of the polyfunctional radical polymerizable compound-containing resin dispersion 1 forming the shell layer of the toner of Production Example 4 is changed to 763 parts by weight of the polyfunctional radical polymerizable compound-containing resin dispersion 5. A toner was produced in the same manner as in Example 4. Toner particles 8 having a toner particle size of 6.5 μm and an average circularity of 0.96 were obtained.

[Toner Production Example 9]
Toner production example, except that 857 parts by weight of the polyfunctional radical polymerizable compound-containing resin dispersion 1 forming the toner shell layer of toner production example 4 is changed to 763 parts by weight of the polyfunctional radical polymerizable compound-containing resin dispersion 6 A toner was produced in the same manner as in Example 4. Toner particles 9 having a toner particle size of 6.4 μm and an average circularity of 0.96 were obtained.

[Toner Production Example 10]
Toner production example except that 857 parts by weight of the polyfunctional radical polymerizable compound-containing resin dispersion 1 forming the shell layer of the toner of Production Example 4 is changed to 838 parts by weight of the polyfunctional radical polymerizable compound-containing resin dispersion 7 A toner was produced in the same manner as in Example 4. Toner particles 10 having a toner particle size of 6.6 μm and an average circularity of 0.97 were obtained.

[Toner Production Example 11]
Toner production example, except that 857 parts by weight of the polyfunctional radical polymerizable compound-containing resin dispersion 1 forming the toner shell layer of toner production example 4 is changed to 838 parts by weight of the polyfunctional radical polymerizable compound-containing resin dispersion 8 A toner was produced in the same manner as in Example 4. Toner particles 11 having a toner particle size of 6.5 μm and an average circularity of 0.96 were obtained.

[Toner Production Example 12]
A toner was produced in the same manner as in Toner Production Example 4 except that 272 parts by mass (in terms of solid content) of Emulsion Polymerized Particle 1 in Toner Production Example 4 was changed to 272 parts by mass (in terms of solid content). Toner particles 12 having a toner particle size of 6.6 μm and an average circularity of 0.96 were obtained.

[Toner Production Example 13]
The colorant fine particle dispersion preparation step and the release agent fine particle dispersion preparation step of Toner Production Example 4 were performed in the same manner.
(Toner preparation process)
Emulsion polymerized particles 1 272 parts by mass (in terms of solid content), ion exchange water 2200 parts by mass, colorant particle dispersion 98 parts by mass, release agent fine particle dispersion 243 parts by mass, thermometer, cooling tube, nitrogen introducing device, It put into a separable flask provided with a stirrer. Furthermore, the pH in which the aqueous sodium hydroxide solution (25% by mass) was added was adjusted to 10 while maintaining the temperature in the system at 30 ° C.
Next, an aqueous solution in which 54.3 parts by mass of magnesium chloride hexahydrate is dissolved in 54.3 parts by mass of ion-exchanged water is added, and then the temperature in the system is raised to 60 ° C. to obtain resin particles. And the aggregation reaction of the colorant particles was started.
Sampling is periodically performed after the start of the agglutination reaction, and using a particle size distribution measuring device “Coulter Multisizer 3” (manufactured by Beckman Coulter, Inc.), the median diameter (D ₅₀ ) on the volume basis of the particles is set to 3.0 μm. At that time, 767 parts by weight of a polyfunctional radical polymerizable compound-containing resin dispersion 3 was added. When the median diameter (D ₅₀ ) on the volume basis of the particles became 6.5 μm, 20.1 parts by mass of ethylenediaminetetraacetic acid was added. The circularity of the toner particles at this time was 0.93.
The temperature was raised to 80 ° C., and when the circularity of the toner particles reached 0.96, the reaction was completed by cooling to 30 ° C. at 6 ° C./min. Toner particles 9 having a toner particle size of 6.4 μm and an average circularity of 0.96 were obtained.
Next, the produced toner particle dispersion was subjected to solid-liquid separation with a basket-type centrifuge “MARK III type” (model number 60 × 40) (manufactured by Matsumoto Kikai Kogyo Co., Ltd.) to form a toner wet cake. Thereafter, the toner washing and solid-liquid separation were repeated until the electric conductivity of the filtrate reached 15 μS / cm or less.
Subsequently, the wet cake was transferred to an airflow dryer “flash jet dryer” (manufactured by Seishin Enterprise Co., Ltd.), and dried until the water content reached 0.5% by mass. The drying process was performed by blowing an air current of 40 ° C. and 20% RH. The dried toner was allowed to cool to 24 ° C., and 1.0 part by mass of hydrophobic silica was mixed with 100 parts by mass of the toner using a Henschel mixer. The peripheral speed of the rotary blade was 24 m / s, and the mixture was mixed for 20 minutes, and then passed through a 400 MESH sieve. The obtained toner is referred to as “toner particles 13”.
1% by mass of hydrophobic silica particles is added to the toner particles 13 obtained, and mixed using a Henschel mixer for 20 minutes under the condition of a peripheral speed of the rotary blade of 24 m / s. The external additive was added by passing it through to obtain “Toner 13”.

[Toner Production Example 14]
A toner is produced in the same manner as in Toner Production Example 4, except that 767 parts by weight of the polyfunctional radical polymerizable compound-containing resin dispersion 3 in Toner Production Example 13 is changed to 767 parts by weight of the polyfunctional radical polymerizable compound-containing resin dispersion 4 did. Toner particles 14 having a toner particle size of 6.5 μm and an average circularity of 0.96 were obtained.

[Comparative toner production example 1]
Similar to Toner Production Example 1 except that 767 parts by weight of the polyfunctional radical polymerizable compound-containing resin dispersion 3 of the toner used in Toner Production Example 1 was changed to 767 parts by weight of the polyfunctional radical polymerizable compound-containing resin dispersion 9 Toner was manufactured. Comparative toner particles 1 having a toner particle size of 6.5 μm and an average circularity of 0.96 were obtained.

[Comparative toner production example 2]
Example of toner production, except that 767 parts by weight of the polyfunctional radical polymerizable compound-containing resin dispersion 1 forming the shell layer of the toner of toner production example 4 is changed to 767 parts by weight of the polyfunctional radical polymerizable compound-containing resin dispersion 9 A toner was produced in the same manner as in Example 3. Comparative toner particles 2 having a toner particle size of 6.4 μm and an average circularity of 0.96 were obtained.

[Comparative Toner Production Example 3]
Example of toner production, except that 767 parts by weight of polyfunctional radical polymerizable compound-containing resin dispersion 1 forming the shell layer of toner of toner production example 4 is changed to 767 parts by weight of polyfunctional radical polymerizable compound-containing resin dispersion 10 A toner was produced in the same manner as in Example 3. Comparative toner particles 3 having a toner particle size of 6.6 μm and an average circularity of 0.97 were obtained.

[Comparative Toner Production Example 4]
A toner is produced in the same manner as in Toner Production Example 13, except that 767 parts by weight of the polyfunctional radical polymerizable compound-containing resin dispersion 3 in Toner Production Example 13 is changed to 767 parts by weight of the polyfunctional radical polymerizable compound-containing resin dispersion 9. did. Comparative toner particles 4 having a toner particle size of 6.5 μm and an average circularity of 0.96 were obtained.

[Comparative Toner Production Example 5]
A toner is produced in the same manner as in Toner Production Example 13, except that 767 parts by weight of the polyfunctional radical polymerizable compound-containing resin dispersion 3 in Toner Production Example 13 is changed to 767 parts by weight of the polyfunctional radical polymerizable compound-containing resin dispersion 10. did. Comparative toner particles 5 having a toner particle size of 6.7 μm and an average circularity of 0.96 were obtained.

7). Preparation of two-component developer Ferrite particles (volume-based median diameter: 50 μm (manufactured by Powdertech)) and methyl methacrylate-cyclohexyl methacrylate copolymer resin (volume-based median diameter of primary particles: 85 nm) 4 The mass part is put into a horizontal stirring blade type high-speed stirring device, and the stirring blade is mixed at a peripheral speed of 8 m / s and a temperature of 30 ° C. for 15 minutes, and then heated to 120 ° C. and stirring is continued for 4 hours. did. Then, it cooled and the resin-coated carrier was produced by removing the fragment of methyl methacrylate-cyclohexyl methacrylate copolymer resin using a 200 mesh sieve.
The resin-coated carrier is mixed with each of the toners [1] to [14] and the comparative toners [1] to [5] so that the concentration of the toner becomes 7% by mass, and a two-component developer. [1] to [14] and comparative two-component developers [1] to [5] were prepared.

8). Evaluation The following evaluation items (1) and (2) were evaluated using the two-component developers [1] to [14] and the comparative two-component developers [1] to [5]. The results are shown in Table 1 below.
(1) Low-temperature fixability A commercially available multifunction machine “bizhub PRO C6500” (manufactured by Konica Minolta Business Technologies) is used as an image forming apparatus, and developers (1) to (5) are used as developers in this apparatus, respectively. In addition, the comparative developer (1) and the comparative developer (2) are mounted, and the surface temperature of the fixing heating member in the fixing means of the heat roll fixing method is changed in increments of 5 ° C. in the range of 80 to 150 ° C., At each temperature, in a normal temperature and normal humidity environment (temperature 20 ° C., humidity 50% RH), an image is formed using a paper weighing 350 g as an image support, and a solid image with an image density of 0.8 is visible. Got as. Thereafter, the fixing solid image is folded using a folding machine, air of 0.35 MPa is blown onto the fixing solid image, the crease state is evaluated in five stages with reference to a limit sample, and the fixing temperature of rank 3 is set as the lower limit fixing temperature. did.
Rank 5: No peeling at all folds, Rank 4: Peeling according to some folds, Rank 3:
There is thin linear peeling according to the crease, Rank 2: thick peeling according to the fold, Rank 1: large peeling in the image.
If the minimum fixing temperature indicating Rank 3 level is 130 ° C. or lower, sufficient low-temperature fixing property is exhibited.

(2) Evaluation of document offset resistance As an image forming apparatus, a “bizhub PRO C6500” (manufactured by Konica Minolta Business Technologies) loaded with a dedicated finisher “FS-608” (manufactured by Konica Minolta Business Technologies) Used, an automatic product creation test of 20 copies of saddle stitch printing (5 copies per copy) was repeated 50 times. In this automatic product creation test, the pixel rate per page was set to 50%, and paper having a basis weight of 64 g was used as the image forming support (transfer paper).
After naturally cooling the created saddle stitch print to room temperature, all the pages of the saddle stitch print were visually confirmed and evaluated according to the criteria shown below with the page having the largest image defect degree of the visible image. . In this evaluation standard, rank 3 and rank 4 are acceptable levels.
Rank 1:
Image defects such as white spots occur in the image area, and clear image transfer occurs in the non-image area, and the document offset resistance is extremely poor.
Rank 2:
There is a problem in practical use, for example, when the edge of the paper is cut while the paper alignment is disturbed and the image is tilted on some pages, or there is uneven glossiness as a trace of image adhesion in some parts of the image area. The resulting image loss and image transfer occur, and the document offset resistance is poor.
Rank 3:
Although there is a crisp sound when turning pages where image parts overlap each other, there is no image loss or image transfer that would cause practical problems in normal use of image and non-image parts, and document offset resistance Good properties.
Rank 4:
The image portion and the non-image portion have no image loss and no image transfer, and the document offset resistance is very good.

  From the results shown in Table 1, it can be seen that the toners [1] to [14] are excellent in low-temperature fixability and image stability (document offset resistance) as compared with the comparative toners [1] to [5]. it is obvious.

Claims (8)

In a toner containing at least a resin and a colorant,
The toner having a resin phase 1 containing a polyfunctional radical polymerizable compound and a resin phase 2 containing a crosslinked polymer having a structural moiety represented by the following general formula (1).

[In the above general formula (1), R ¹ is a hydrogen atom or a chlorine atom, and R ² is a hydrogen atom, a chlorine atom or a methoxy group. ]   The toner according to claim 1, wherein the polyfunctional radical polymerizable compound is a polyfunctional acrylate / methacrylate compound. The polyfunctional radically polymerizable compound is contained in an amount of 0.3 to 1 times the molar equivalent of the polymerizable triarylimidazole compound represented by the following general formula (3). The toner described in 1.

A toner production method for producing the toner according to claim 1,
A polymerizable triarylimidazole compound represented by the following general formula (4) is bonded to the polymerizable triarylimidazole compound represented by the following general formula (4) by bonding the imidazole rings of the triarylimidazole group. A method for producing a toner, comprising: obtaining a crosslinked compound by polymerizing the polymerizable triarylimidazole dimer compound after obtaining the monomer compound.

[In the above general formula (3), R ¹ is a hydrogen atom or a chlorine atom, R ² is a hydrogen atom, a chlorine atom or a methoxy group, R ³ is a hydrogen atom or a methyl group, and L ¹ is a single bond or a divalent group. Is an organic group. ]

[In the above general formula (4), R ¹ is a hydrogen atom or a chlorine atom, R ² is a hydrogen atom, a chlorine atom or a methoxy group, R ³ is a hydrogen atom or a methyl group, and L ¹ and L ² are single bonds or a divalent organic group, L ¹ and L ² may being the same or different. ]   The said polymerization process is performed in the state which disperse | distributed in the aqueous medium the polymerization process liquid formed by melt | dissolving or disperse | distributing the said polymerizable triarylimidazole dimer compound in the organic solvent. A method for producing the toner according to the description. A method for producing the toner according to claim 1, comprising:
After polymerizing a polymerizable triarylimidazole compound represented by the following general formula (3) to obtain a triarylimidazole group-containing prepolymer having a structural unit represented by the following general formula (5), the triarylimidazole is obtained. A method for producing a toner, comprising a step of obtaining a crosslinked polymer by performing a crosslinking treatment for bonding between imidazole rings of a group.

[In the above general formula (3), R ¹ is a hydrogen atom or a chlorine atom, R ² is a hydrogen atom, a chlorine atom or a methoxy group, R ³ is a hydrogen atom or a methyl group, and L ¹ is a single bond or a divalent group. Is an organic group. ]

[In the general formula (5), R ¹ is a hydrogen atom or a chlorine atom, R ² is a hydrogen atom, a chlorine atom or a methoxy group, R ³ is a hydrogen atom or a methyl group, and L ¹ is a single bond or a divalent group. Is an organic group. N is the number of repetitions. ]   The toner production method according to claim 6, wherein the polymerization treatment is performed in a state where a polymerization treatment liquid containing the polymerizable triarylimidazole compound is dispersed in an aqueous medium. In an image forming method including a step of fixing an image forming support formed with a toner containing at least a resin and a colorant by passing between a heating roller and a pressure roller.
The toner has a resin phase 1 containing a polyfunctional radically polymerizable compound and a resin phase 2 containing a crosslinked polymer having a divalent crosslinking group represented by the following general formula (1). An image forming method, wherein the resin layer 1 and the resin layer 2 cause a radical polymerization reaction by fixing heat.