JP5649396B2 - Charge control resin and toner containing the charge control resin - Google Patents

Description

  The present invention relates to a positively chargeable charge control resin. The present invention also relates to a toner for developing an electrostatic charge image used in image forming methods such as electrophotography and electrostatic printing.

In recent years, with the development of computers and multimedia, there has been a demand for means for outputting high-definition full-color images in a wide range of fields from offices to homes.
Heavy users demand high durability that does not deteriorate image quality even when a large number of copies or prints are made. On the other hand, in small offices and homes, high-quality images are obtained, and downsizing of the device is required from the viewpoints of space saving, energy saving, and weight reduction. Less), it is necessary to lower the fixing temperature. Considering the above requirements, it is in a situation that cannot be fully addressed without further improvement in toner performance such as low-temperature fixability, high durability, environmental stability, and storage stability.
In recent years, full-color output has increased. In the case of full color, three or four color toners are superimposed to form an image. However, if the color toners of the respective colors are not developed in the same manner, color reproduction is inferior and color unevenness occurs. However, these toners are colored with pigments and dyes, and these have a great influence on development. Further, in a full-color image, fixability and color mixing at the time of fixing are important. In order to achieve the required high speed, a binder resin suitable for low-temperature fixability is selected, but the influence on the developability and durability of the binder resin is also great. One of the effects is a change in charge amount due to the influence of temperature and humidity, and contamination of members such as a developing roller, a charging roller, a regulating blade, and a photosensitive drum. Therefore, there is an urgent need to develop a color toner that has stable chargeability and durability without contamination even when stored for a long time in a wide range of environments.
As one of means for solving such various problems, there is a method of controlling the chargeability of the resin.
As one of the causes of long-term storage stability and charge amount fluctuation of the toner due to temperature and humidity, the charge control agent and charge control resin component ooze out from the surface of the charge control resin component resin or toner binder resin (hereinafter referred to as bleed). It is also referred to as changing the surface properties of the toner. As a means for stabilizing the charging performance of the toner, in the case of a positively charged toner, a toner containing a positively chargeable compound such as an ammonium salt as a positively charged charge control agent is disclosed (see Patent Document 1). However, there are some problems due to changes in image density due to changes in chargeability at high temperatures and member contamination due to toner fusion.
The charge control resin has a glass transition temperature (Tg) of 70 to 100 ° C. as a toner excellent in high temperature storage stability and printing durability in a normal temperature and normal humidity environment during printing or in a high temperature and high humidity environment. A toner using a quaternary ammonium base-containing copolymer is disclosed (see Patent Document 2). However, there are some problems with durability and component contamination in harsh environments.
Furthermore, a polymerized toner is disclosed in which a resin having a polymerizable double bond at the polymer end is used for the toner in order to improve the fixing property (see Patent Document 3). However, the toner has some problems as a toner excellent in environmental stability and development durability.

JP 2003-302787 A JP 2008-191189 A JP 2007-279666 A

  The present invention provides a charge control resin that solves the above problems and a toner containing the charge control resin. More specifically, an object of the present invention is to provide a charge control resin excellent in harsh environment stability and storage stability, and a toner containing the charge control resin.

As a result of intensive studies, the present inventors have found that the above problem can be solved by adopting the following configuration.
That is, the present invention is a charge control resin obtained by polymerizing a polymerizable monomer and a polymerizable charge control resin, wherein the polymerizable charge control resin has a quaternary ammonium base as a functional group. , ends Ri macromonomer der styrene having a double bond, in the measurement of the nuclear magnetic resonance device using a deuterated chloroform solvent, the double bond in 4.6~4.9ppm and 5.0~5.3ppm about charge control resin, characterized in Rukoto to have a peak derived from.
The present invention also relates to a toner having toner particles containing the charge control resin.

  According to the present invention, it is possible to provide a charge control resin excellent in harsh environment stability and storage stability, and a toner containing the charge control resin.

Hereinafter, the present invention will be described in detail.
Charge control resin of the present invention is a charge control resin obtained by polymerizing a polymerizable charge control resin and heavy polymerizable monomers, the polymerizable charge control resin is a quaternary ammonium base functionality possess as a terminal to have a double bond, characterized in that a (hereinafter, also referred to as "having a terminal double bond") styrene macromonomer.
When the polymerizable charge control resin is a macromonomer having a terminal double bond, a charge control resin having a cross-linked structure via the terminal part can be obtained by reacting with the polymerizable monomer. It is considered that the terminal cross-linked structure of the resin having an ammonium base suppresses unevenness due to bleeding or movement of the resin having an ammonium base in a harsh environment. The charge control resin in which bleeding and movement of the resin having an ammonium base are suppressed is excellent in harsh environment stability and storage stability.
Moreover, it is a preferable aspect that a terminal double bond is a styrenic terminal double bond shown in following formula (1). The styrenic terminal double bond has peaks at 4.6 to 4.9 ppm and 5.0 ppm to 5.3 ppm, which are different from the double bond of the styrene monomer, in nuclear magnetic resonance ( ¹ H-NMR) measurement. Have

（Ｒは、第４級アンモニウム塩基を官能基として有するスチレン系重合体又は共重合体）

(R is a styrene polymer or copolymer having a quaternary ammonium base as a functional group)

The polymerizable charge control resin used in the present invention is a styrenic resin having a quaternary ammonium base as a functional group, and is a macromonomer having a double bond at the terminal.
A charge control resin obtained by polymerizing a polymerizable charge control resin having a quaternary ammonium base as a functional group and a polymerizable monomer, compared to a charge control resin having primary, secondary, and tertiary amines, It is hard to be compatible with resin and has excellent surface precipitation. Therefore, a molecular chain having a quaternary ammonium base is likely to appear on the resin surface and has good chargeability. Further, it is immobilized in the vicinity of the resin surface by a cross-linked molecular chain generated from the polymerizable charge control resin. Therefore, even if it has a hydrophilic ammonium salt, bleed and movement hardly occur in a harsh environment, and the charging property is high. Further, when the charge control resin is produced in an aqueous medium, a molecular chain having a quaternary ammonium base is more likely to precipitate on the resin surface. A resin having a quaternary ammonium base has very good positive chargeability.
The kind and content of the quaternary ammonium base can be adjusted by selecting the monomer type having a quaternary ammonium base and the amount added during production.
In addition, the kind and content of ammonium base are liquid chromatograph mass spectrometer (LC / MS), gas chromatograph mass spectrometer (GC / MS), nuclear magnetic resonance analyzer (NMR), infrared spectrometer (IR) ) And a mass spectrometer (MS).

  The styrene resin having the quaternary ammonium base as a functional group preferably contains a repeating unit represented by the following formulas (2) and (3).

［式（２）中、Ｒ_１は水素原子またはメチル基である。］

[In Formula (2), R ₁ is a hydrogen atom or a methyl group. ]

［式（３）中、Ｒ_２は、水素原子又はメチル基を示し、Ｒ_４、Ｒ_５、Ｒ_６は、各々独立してアルキル基、フェニル基、又は炭素数７〜１２のアラルキル基を示し、Ｒ_３は、アルキレン基を示し、Ａは、ハロゲン原子、又は、炭素数１〜６のアルキルスルホン酸残基、ベンゼンスルホン酸残基、若しくはパラトルエンスルホン酸残基を示す。］

[In Formula (3), R ₂ represents a hydrogen atom or a methyl group, and R ₄ , R ₅ , and R ₆ each independently represent an alkyl group, a phenyl group, or an aralkyl group having 7 to 12 carbon atoms. , R ₃ represents an alkylene group, and A represents a halogen atom or an alkylsulfonic acid residue, benzenesulfonic acid residue, or paratoluenesulfonic acid residue having 1 to 6 carbon atoms. ]

  It is more preferable that the styrene resin having the quaternary ammonium base as a functional group contains a repeating unit represented by the above formula (2) and the following formula (4).

［式（４）中、Ｒ_２は水素原子またはメチル基であり、Ｒ_３はアルキレン基であり、Ｒ_４，Ｒ_５及びＲ_６は各々独立してアルキル基である。］

[In Formula (4), R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group, and R ₄ , R ₅ and R ₆ are each independently an alkyl group. ]

In the present specification, the term “lower” means that the number of carbon atoms of the group or compound modified with this word is 10 or less, preferably 5 or less. "Alkyl group" and "alkylene group" are linear, branched or cyclic aliphatic hydrocarbon groups, respectively. Examples of alkyl groups are methyl, ethyl, n- or iso-propyl, n-, sec. -, Iso- or tert-butyl, n-, sec-, iso- or tert-amyl, n-, sec-, iso- or tert-hexyl, n-, sec-, iso- or tert-octyl, n- , Sec-, iso-, tert-nonyl and the like having 1 to 10 carbon atoms are included, and among them, a lower alkyl group is preferable.
Examples of the alkylene group include linear or branched alkylene groups having 2 to 3 carbon atoms such as ethylene and propylene.
When the unit of the formula (2) exceeds 98.0% by mass in the styrene resin having a quaternary ammonium base as a functional group, the positive charge characteristic of the resin itself is lowered, and the toner is used for a positively chargeable toner. The usage will increase. On the other hand, when the amount is less than 60.0% by mass, the compatibility with the binder resin is lowered and the humidity resistance of the toner tends to be deteriorated.
Accordingly, the repeating unit of the general formula (2) is 60.0 to 98.0% by mass, preferably 65.0 to 97.0% by mass based on the mass of the styrene resin having a quaternary ammonium base as a functional group. %, More preferably 70.0 to 95.0% by mass.

  Moreover, a part of repeating unit of the said Formula (2) can be substituted with the repeating unit induced | guided | derived from the (meth) acrylic-acid alkylester shown by following formula (5). Thereby, the compatibility in the resin of the styrene resin which has a quaternary ammonium base as a functional group can further be improved. However, since the positive charging property of the toner tends to be lowered when the amount of the unit is too large, it is 20.0% by mass or less based on the mass of the styrene resin having a quaternary ammonium base as a functional group, preferably 15. It should be 0% by mass or less, more preferably 3.0 to 15.0% by mass.

［式（５）中、Ｒ_７は水素原子またはメチル基であり、Ｒ_８はアルキル基、好ましくはメチル、エチル、ｎ−もしくはｉｓｏ−プロピル、ｎ−もしくはｉｓｏ−ブチル、２−エチルヘキシル基、又は、ヒドロキシエチル、ヒドロキシプロピル基である。］

[In formula (5), R ₇ is a hydrogen atom or a methyl group, R ₈ is an alkyl group, preferably methyl, ethyl, n- or iso-propyl, n- or iso-butyl, 2-ethylhexyl group, or , Hydroxyethyl and hydroxypropyl groups. ]

On the other hand, the repeating unit of the above formula (3) or (4) is a unit derived from an acrylate through a quaternization step by a method described later, and the repeating unit has a quaternary ammonium base as a functional group. 40.0 to 1.0% by mass, preferably 30.0 to 2.0% by mass, and more preferably 25.0 to 3.0% by mass based on the mass of the styrenic resin contained as
Further, in the formation of the repeating unit of the above formula (3) or (4), a part of the starting monomer is left unreacted without being quaternized, or in the form of an intermediate ammonium halide. Even if it is introduced into the resin, there is no problem. Therefore, the styrenic resin having a quaternary ammonium base as a functional group may contain a repeating unit represented by the following formula (6) or (7).

［式（６）及び（７）中、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５及びＲ_６は前記と同じ意味を有し、Ｈａｌはハロゲン原子である。）

[In the formulas (6) and (7), R ₂ , R ₃ , R ₄ , R ₅ and R ₆ have the same meaning as described above, and Hal is a halogen atom. )

However, for example, the presence of the repeating unit of the above formula (6) may cause member contamination. For this reason, the presence of these units of the formula (6) or (7) causes the quaternary ammonium base to be functionalized. Based on the mass of the styrene-based resin that is included, it is 3.5% by mass or less, preferably 2.0% by mass or less, more preferably 1.0% by mass or less.
Examples of the dialkylaminoalkyl (meth) acrylate derived from the repeating unit of the above formula (3) or (4) include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meta) ) Acrylates, di (lower alkyl) aminoethyl (meth) acrylates such as dibutylaminoethyl (meth) acrylate are preferred.
Styrenic resin having a quaternary ammonium base as a functional group starts polymerization of (a) styrene and / or α-methylstyrene, dialkylaminoalkyl (meth) acrylate, and (meth) acrylic acid alkyl ester as necessary Copolymerization in the presence of an agent, and the resulting copolymer is quaternized with a paratoluenesulfonic acid alkyl ester such as methyl paratoluenesulfonate, ethyl paratoluenesulfonate, propyl paratoluenesulfonate, or the like, or (B) Dialkylaminoalkyl (meth) acrylate is quaternized with an alkyl halide such as methyl chloride, methyl bromide, ethyl chloride, ethyl bromide, propyl chloride, propyl bromide, butyl chloride, butyl bromide and the like according to a conventional method. Produced by converting to quaternary ammonium halide, copolymerizing quaternary ammonium halide with styrene and / or α-methylstyrene and (meth) acrylic acid alkyl ester if necessary, and reacting the resulting copolymer with paratoluenesulfonic acid. can do. In general, the former method (a) is preferable because there is no byproduct of hydrogen halide.
Examples of the polymerization initiator that can be used in the copolymerization reaction include azo initiators such as azobisisobutyronitrile, azobisdimethylvaleronitrile, azobis (2,4-dimethyl-4-methoxyvaleronitrile), 2 -Phenylazo (2,4-dimethyl-4-methoxyvaleronitrile) and the like, and these polymerization initiators are usually 0.5% by mass or more and 5.0% by mass or less based on the total mass of the monomer mixture. It is preferable to use within the range.
As the polymerization method, any method such as solution polymerization, suspension polymerization, bulk polymerization and the like can be used, and it is not particularly limited. Control of the weight average molecular weight (Mw) of the obtained polymer is relatively easy, and the operation of reacting the copolymer obtained in the next step with paratoluenesulfonic acid alkyl ester or paratoluenesulfonic acid is easy. It is particularly preferable to use the solution polymerization method for the reasons such as. In addition, as a solvent for the solution polymerization, an organic solvent such as benzene, toluene, xylene, dioxane, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethyl acetate, isopropyl acetate, methyl ethyl ketone, diethyl ketone, isobutyl ketone, or these organic solvents It is preferable to use a mixed solvent of alcohol and lower alcohols such as methanol, ethanol, propanol, isopropanol, and butanol.

On the other hand, the polymerizable charge control resin used in the present invention is a macromonomer having a double bond at the terminal. Here, the production method for introducing a double bond at the terminal is not particularly limited, but a high temperature polymerization method and a terminal modification method can be used. The high temperature polymerization method means that a monomer for obtaining the above repeating unit is polymerized at 150 ° C. or higher. Moreover, it can superpose | polymerize by making high temperature more than the boiling point of a polymerization solvent by superposing | polymerizing under pressure. For example, when pressure high temperature polymerization is performed using xylene as a solvent, the pressure becomes 0.4 MPa at 220 ° C.
Specifically, in a styrene resin having a quaternary ammonium base produced by polymerization at a high temperature of 170 ° C. or higher as a functional group, in a ¹ H-NMR measurement using a deuterated chloroform solvent, 4.6 to Peaks derived from terminal double bonds different from the styrene monomer are observed at 4.9 ppm and 5.0 to 5.3 ppm. That is, for example, a polymerizable charge control resin obtained by using a high temperature polymerization method has a styrenic terminal double bond.
On the other hand, the terminal modification method is a method of introducing a terminal modification monomer having a double bond to an end functional group by addition reaction or condensation reaction.
Specifically, first, a styrene resin having a hydroxyl group and a quaternary ammonium base as functional groups at the terminal is synthesized. Next, a terminal double bond can be introduced by addition reaction of a monomer having a double bond and an isocyanate group with the resin.
These terminal double bonds are crosslinked during the production of the charge control resin. In this way, by introducing a small amount of cross-linked structure in the charge control resin, even if the charge control resin has a hydrophilic ammonium salt, the resin having an ammonium base in a harsh environment can be made uneven by bleeding or moving. And the chargeability of the charge control resin can be maintained high. As a result, the charge control resin in which unevenness due to bleeding and movement of the resin having an ammonium base is suppressed is excellent in harsh environment stability and storage stability.

The repeating unit constituting the styrene resin having the quaternary ammonium base as a functional group is as described above. However, in the present invention, the following monomers are added to such an extent that the effects of the present invention are not affected. Derived repeating units can be used.
Monofunctional polymerizable monomers include β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butyl. Styrene derivatives such as styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene Tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate Acrylic acid esters such as ethyl acrylate and 2-benzoyloxyethyl acrylate; tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate ethyl Methacrylic acid esters such as methacrylate; Methylene aliphatic monocarboxylic acid esters; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and vinyl formate; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether A vinyl ketone such as vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropyl ketone;
As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Diacrylate, polypropylene glycol diacrylate, 2,2′-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4- (methacryloxy-diethoxy) phenyl) propane, Examples include 2,2′-bis (4- (methacryloxypolyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylol methanetoteramethacrylate, divinylbenzene, divinylnaphthalene, and divinyl ether.

The polymerizable charge control resin preferably contains 1.0 to 40.0% by mass of a repeating unit derived from a monomer having a quaternary ammonium base as a functional group, more preferably 2
. It is preferable to contain 0 to 30.0 mass%, more preferably 3.0 to 25.0 mass%. When the amount is less than 3.0% by mass, the effect of adding the polymerizable charge control resin cannot be sufficiently obtained. Cheap.

In the present invention, the ratio of the terminal double bond of the polymerizable charge control resin is preferably 0.10 mol% or more and 20.00 mol% or less. More preferably, it is 2.00 mol% or more and 10.00 mol% or less.
When the ratio of the terminal double bond of the polymerizable charge control resin is 0.10 mol% or more and 20.00 mol% or less, the chargeability and storage stability under a harsh environment are good. When the ratio of the terminal double bond is smaller than 0.10 mol%, the bleeding or movement of the resin having an ammonium base in a harsh environment tends to be poor. On the other hand, when the ratio of the terminal double bond is larger than 20.00 mol%, the chargeability and the low-temperature fixability tend to deteriorate. The ratio of the terminal double bond can be adjusted by the reaction temperature and pressure during the production of the polymerizable charge control resin, the number of terminal functional groups by the terminal modification method, and the amount of the terminal functional group modifying monomer.

The number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble part of the polymerizable charge control resin of the present invention is preferably 500 or more and 3,000 or less. When the number average molecular weight (Mn) of the polymerizable charge control resin is less than 500, there are many components having a low molecular weight, and the storage stability tends to be lowered due to the leaching thereof. Further, when the number average molecular weight (Mn) is larger than 3,000, the low-temperature fixability tends to be lowered. In the present invention, the number average molecular weight (Mn) of the polymerizable charge control resin can be adjusted by the amount of solvent, the solvent species, the reaction temperature, and the amount of initiator at the time of production of the polymerizable charge control resin.
On the other hand, the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) soluble in tetrahydrofuran (THF) of the polymerizable charge control resin of the present invention is 2,000 or more and 50,000 or less. Preferably, it is 2,000 or more and 30,000 or less, more preferably 2,000 or more and 6,000 or less. When the weight average molecular weight (Mw) of the polymerizable charge control resin is smaller than 2,000, there are many components having a small molecular weight, and the storage stability and the charge stability tend to decrease due to leaching from the inside of the resin. is there. On the other hand, when the weight average molecular weight (Mw) is larger than 50,000, the dispersibility of the resin having an ammonium base is deteriorated and the charging stability is likely to be lowered.
In the present invention, the weight average molecular weight (Mw) of the polymerizable charge control resin can be adjusted by the amount of solvent, the solvent species, the reaction temperature, and the amount of initiator at the time of producing the polymerizable charge control resin.
Moreover, it is preferable that the glass transition temperature (Tg) measured with the scanning scanning calorimeter (DSC) of the said polymeric charge control resin is 40 to 100 degreeC. When the glass transition temperature is less than 40 ° C., the strength of the entire charge control resin is lowered, and the charge control resin is easily deteriorated and the charge characteristics are easily lowered during the durability test. Furthermore, the problem that the charging stability is lowered in a high temperature and high humidity environment is likely to occur. On the other hand, if the glass transition temperature exceeds 100 ° C., the problem of poor fixing tends to occur. The glass transition temperature of the polymerizable charge control resin is more preferably 40 to 70 ° C., particularly preferably 40 to 65 ° C., from the viewpoints of low temperature fixability and high gloss image.
The polymerizable charge control resin is used when polymerizing a polymerizable monomer composition containing at least a polymerizable monomer, a colorant, and a polymerizable charge control resin to obtain toner particles in a one-step reaction. be able to. In this case, the toner particles hit the charge control resin in the present invention. The polymerizable charge control resin is preferably 0.1 to 30.0 parts by mass with respect to 100.0 parts by mass of the polymerizable monomer.
Alternatively, a polymerizable monomer composition containing at least a polymerizable monomer and a polymerizable charge control resin may be polymerized to obtain a charge control resin, and then toner particles containing the charge control resin and a colorant may be used. . In this case, the polymerizable charge control resin is preferably used at a ratio of 30.0 to 80.0% by mass in the charge control resin.

The charge control resin of the present invention comprises a monomer composition containing a polymerizable charge control resin having a terminal double bond and a polymerizable monomer, and, if necessary, other additives such as a polymerization initiator. It is prepared by polymerizing a polymerizable monomer.
In the present invention, the charge control resin has a structure in which the polymerizable charge control resin and the polymerizable monomer are polymerized and cross-linked, thereby exhibiting stable charging performance and storage stability even in a harsh environment. It becomes possible. This is because, as described above, the cross-linked structure suppresses unevenness due to bleeding and migration of the resin having an ammonium base, and has a positive effect on the positive chargeability of the ammonium base.
Although the said polymerizable monomer and polymerization initiator are not specifically limited, The monomer and polymerization start which can be used in order to manufacture the styrene resin which has the said quaternary ammonium base as a functional group are mentioned. An agent can be used. Moreover, it does not specifically limit about polymerization conditions, The conditions used normally can be applied. In addition, as a manufacturing method when the charge control resin of the present invention is used as toner particles, a toner particle manufacturing method described later may be appropriately applied.
As the other additives, the following resins can be used in the monomer composition as long as the effects of the present invention are not affected. Homopolymers of styrene such as polystyrene and polyvinyltoluene and substituted products thereof; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene- Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate Copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer , Styrene-butadi Copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene copolymer such as styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, Polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin. It can be used alone or in combination.

In the present invention, the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the tetrahydrofuran-soluble component of the charge control resin is preferably 7,000 or more and 50,000 or less. When the weight average molecular weight (Mw) measured by GPC of the THF-soluble component of the charge control resin is 7,000 or more and 50,000 or less, performance excellent in storage stability and environmental stability is exhibited. When the weight average molecular weight (Mw) measured by GPC of the THF-soluble component of the charge control resin is less than 7,000, the resin having an ammonium base in a high temperature and high humidity environment becomes uneven or charged due to bleed or movement. When it is larger than 50,000, the chargeability in a low temperature and low humidity environment tends to be high.
The weight average molecular weight (Mw) measured by GPC of the THF-soluble component of the charge control resin in the present invention is adjusted by the type of monomer, initiator amount, reaction temperature and reaction time at the time of charge control resin production. Can do.
In the present invention, the number average molecular weight (Mn) measured by GPC of the THF-soluble component of the charge control resin is preferably 1,000 or more and 30,000 or less. When the number average molecular weight (Mn) measured by GPC of the THF-soluble component of the charge control resin is 1,000 or more and 30,000 or less, performance excellent in storage stability and environmental stability is exhibited. When the number average molecular weight (Mn) measured by GPC of the THF-soluble component of the charge control resin is less than 1,000, the resin having an ammonium base in a high temperature and high humidity environment may become uneven due to bleeding or migration. The chargeability tends to decrease, and when it is greater than 30,000, the chargeability tends to be high in a low temperature and low humidity environment.
The number average molecular weight (Mn) measured by GPC of the THF soluble content of the charge control resin in the present invention is adjusted by the type of monomer, initiator amount, reaction temperature, and reaction time at the time of charge control resin production. Can do.
It is preferable that the glass transition temperature (Tg) measured with the scanning scanning calorimeter (DSC) of charge control resin in this invention is 40 to 100 degreeC. More preferably, it is higher than 70 ° C and not higher than 100 ° C, and more preferably 73 ° C to 100 ° C. When the glass transition temperature is less than 40 ° C., the toner tends to be inferior in fluidity and storability and also inferior in transferability. When the glass transition temperature exceeds 100 ° C., the fixability tends to be inferior when the image has a high toner printing rate.
The charge control resin of the present invention preferably contains 0.01 to 20.00% by mass of a repeating unit derived from a monomer having a quaternary ammonium base as a functional group, and 0.05 to 10.00%. More preferably, it is contained in an amount of 0.10 to 7.00% by mass. When the content is less than 0.01% by mass, the effect of adding the charge control resin cannot be sufficiently obtained. When the content exceeds 20.00% by mass, the chargeability increases and the charging stability decreases. Cheap.
The production method of the charge control resin of the present invention includes a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, an ionic polymerization method, and the like, but the suspension polymerization method is preferable from the viewpoint of operability.
Note that the presence and amount of a repeating unit derived from a monomer having a quaternary ammonium base in the toner binder resin and the charge control resin are described with reference to an X-ray fluorescence apparatus, a mass spectrometer, and a capillary electrophoresis method. Etc. can be obtained.
In addition, in obtaining the physical properties as described above, when extraction of a polymer having a quaternary ammonium base as a functional group from a binder resin or the like is required, the extraction method is not particularly limited, and any The method can be used.

In the toner of the present invention, the content of the monomer unit having a quaternary ammonium base as a functional group is preferably 0.001 to 5.000 parts by mass per 100.000 parts by mass of the binder resin. The amount is more preferably 0.005 to 2.000 parts by mass, and still more preferably 0.010 to 1.500 parts by mass. In the toner binder resin, the presence and content of a monomer unit having an ammonium base as a functional group can be determined by a fluorescent X-ray apparatus or a mass spectrometer.
The toner of the present invention is a toner having toner particles containing the charge control resin of the present invention. When the toner contains the charge control resin of the present invention, stable charging performance, storage stability, and durability are improved even in a harsh environment. This is because, as described above, the cross-linked structure suppresses unevenness due to bleeding and migration of the resin having an ammonium base, and has a positive effect on the positive chargeability of the ammonium base.
A method for producing the toner of the present invention is not particularly limited, but a method for producing a toner directly in a medium such as a suspension polymerization method, an interfacial polymerization method, a dissolution suspension method and a dispersion polymerization method (hereinafter also referred to as a polymerization method). Can be suitably exemplified. The toner obtained by this polymerization method (hereinafter also referred to as “polymerized toner”) has high transferability because the shape of individual toner particles is almost spherical and the distribution of charge amount is relatively uniform.
Hereinafter, specific embodiments in which the charge control resin of the present invention is contained in the toner particles will be described, but the invention is not limited thereto.
First, a polymerizable monomer composition containing at least a polymerizable monomer, a colorant, and a polymerizable charge control resin is suspended and granulated in an aqueous medium, and then the polymerizable monomer and the polymerization are polymerized. In this embodiment, toner particles are obtained by polymerizing the neutral charge control resin. Since the toner having the toner particles is polymerized in a state where the charge control resin component is deposited in the vicinity of the toner surface, the chargeability in a severe environment is particularly good. Moreover, since it has a crosslinked structure, unevenness due to bleeding or movement of a resin having an ammonium base in a harsh environment is suppressed. In this embodiment, the charge control resin of the present invention is toner particles.
The second is an embodiment in which at least a binder resin, the charge control resin of the present invention, and a colorant are melt-kneaded and pulverized to obtain toner particles. The toner having the toner particles is easily pulverized at the interface of the charge control resin, and since the charge control resin is fixed at the interface, the development durability and the chargeability are improved. When the charge control resin of the present invention is not used, when it is pulverized at the interface of the charge control resin, there is a high possibility of further pulverization at the interface, and the chargeability tends to deteriorate.
Thirdly, the organic phase dispersion prepared by dissolving at least the binder resin, the charge control resin of the present invention and the colorant in an organic solvent is suspended and granulated in an aqueous medium, and then the organic solvent is removed. Thus, toner particles are obtained. The toner having the toner particles is preferable because the toner particles are formed in a state where the charge control resin component is deposited in the vicinity of the toner surface, and the chargeability in a severe environment tends to be good. When the charge control resin of the present invention is not used, it is difficult to maintain chargeability in a harsh environment.
A fourth aspect is an embodiment in which at least binder resin particles, particles containing the charge control resin of the present invention, and colorant particles are aggregated in an aqueous medium and associated to obtain toner particles. The toner having the toner particles has good chargeability in a harsh environment because the toner particles are formed with the charge control resin deposited in the vicinity of the toner surface. When the charge control resin of the present invention is not used, it is difficult to maintain chargeability in a harsh environment.
Fifth, a polymerizable monomer composition containing at least a polymerizable monomer and a polymerizable charge control resin is suspended and granulated in an aqueous medium, and the polymerizable monomer and the polymerizable charge control resin are then granulated. To obtain a charge control resin, and then suspend and granulate the polymerizable monomer composition containing at least the charge control resin, the colorant, and the polymerizable monomer in an aqueous medium, and polymerize. In this embodiment, toner particles are obtained by polymerizing the polymerizable monomer. The toner having the toner particles is polymerized in a state where the charge control resin component is deposited in the vicinity of the toner surface, so that the chargeability in a high temperature and high humidity environment is particularly good. Moreover, since it has a crosslinked structure, unevenness due to bleeding or movement of a resin having an ammonium base in a harsh environment is suppressed.

As the method for producing the toner of the present invention, among the above-described production methods, the suspension polymerization method is particularly preferable. Hereinafter, the suspension polymerization method will be described as an example to add description.
In the suspension polymerization method, a polymerizable monomer composition containing at least a polymerizable monomer, a polymerizable charge control resin and a colorant is suspended in an aqueous medium, and droplets of the polymerizable monomer composition are suspended. The toner particles are produced by at least a granulating step for producing a polymer and a polymerization step for polymerizing the polymerizable monomer and the polymerizable charge control resin in the droplets. If necessary, a wax, a polar resin, and a low molecular weight resin can be added to the polymerizable monomer composition. Further, after the polymerization step is completed, the produced particles are washed and collected by filtration and dried to obtain toner particles. The temperature may be raised in the latter half of the polymerization step. Furthermore, in order to remove the unreacted polymerizable monomer or by-product, it is possible to partially distill off the dispersion medium from the reaction system in the latter half of the polymerization step or after the completion of the polymerization step.
In the toner of the present invention, the resin component may have a polymerizable functional group for the purpose of improving the viscosity change of the toner at high temperature. Examples of the polymerizable functional group include a double bond, an isocyanate group, an epoxy group, an amino group, a carboxylic acid group, and a hydroxyl group.
The polar resin is intended to improve toner particle shape, material dispersibility, fixability, or image characteristics. For example, hydrophilic functions such as amino groups, carboxylic acid groups, hydroxyl groups, sulfonic acid groups, glycidyl groups, and nitrile groups cannot be used because monomers are water-soluble and dissolve in aqueous suspension to cause emulsion polymerization. When it is desired to introduce a monomer component containing a group into toner particles, a random copolymer of these and a vinyl compound such as styrene or ethylene, a block copolymer, a copolymer such as a graft copolymer, a polyester, and It can be used in the form of a polycondensate such as polyamide or an addition polymer such as polyether and polyimine.
The toner particles may have a core part and a shell part. The toner particles have a shell portion so as to cover the core portion. By adopting such a structure, it becomes easy to prevent poor charging and blocking in each environment due to deposition of the core portion on the toner surface. It is also possible to adopt a mode in which a surface layer portion having a contrast different from that of the shell portion exists on the surface of the shell portion. The presence of this surface layer portion can improve environmental stability, durability, and blocking resistance.
The material constituting the surface layer portion preferably has a molecular chain polar structure. In the present invention, the molecular chain polar structure refers to a molecular structure having a number of δ ⁺ or δ ⁻ electron density states at atoms in the molecule.
Resin molecules are composed of a plurality of types of atoms, and the constituent atoms have inherent electronegativity, and the values differ greatly depending on the atoms. Due to this difference in electronegativity, electrons are localized in the molecule. In this localization, the state changes depending on the type, number, and bonding mode of the atoms to be configured, and the polarity of the molecular chain changes.
What is preferable as the molecular chain polar structure is, for example, a bond structure formed by condensation polymerization or addition polymerization. Specifically, ester bond (—COO—), ether bond (—O—), amide bond (—CONH—), imine bond (—NH—), urethane bond (—NHCOO—), urea bond (—NHCONH) -).
For example, in an ether chain (—CH ₂ —O—CH ₂ —) or the like, electrons on the carbon atom are slightly deficient (δ ⁺ ), electrons on the oxygen atom are slightly excessive (δ ⁻ ), and oxygen The bond angle with the atom as the apex is in a state. Thus, if there are many polarized molecular chains, the polarity of the molecule, that is, the resin will increase, and if there are few polarized molecular chains, it will decrease. In general, molecules composed of hydrocarbons have low polarity.
When the surface layer portion has a molecular chain polar structure, charging stability is improved. In addition, when toner particles are generated in a polar solvent such as an aqueous or hydrophilic medium, the surface layer portion having a molecular chain polar structure is more uniformly formed in the vicinity of the toner surface. Improves charging stability in low humidity environments and durability during high-speed printing.
From the above viewpoint, the toner of the present invention preferably contains a polyester resin.
Examples of suitable materials for the surface layer include polyester resins and derivatives thereof.
The polyester resin can be produced from a polyvalent alcohol and a polyvalent carboxylic acid by a known production method. Among the monomers constituting the polyester resin, polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, diethylene glycol, and dipropylene glycol. , Triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2,2,4-trimethylpentane-1,3-diol, hydrogenated bisphenol A, represented by the following general formula (A) And diols represented by the following general formula (B). These polyhydric alcohols may be used alone or in a mixed state. However, it is not limited to these, and other trivalent or higher alcohols can be used as the crosslinking component.

［一般式（Ａ）中、Ｒはエチレン基又はプロピレン基であり、ｘ及びｙはそれぞれ１以上の整数であり、且つｘ＋ｙの平均値は２〜１０である。］

[In general formula (A), R is an ethylene group or a propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2-10. ]

Among the monomers constituting the polyester resin, polyvalent carboxylic acids include naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, succinic acid, adipic acid, Dicarboxylic acids such as sebacic acid and azelaic acid; dicarboxylic anhydrides such as phthalic anhydride and maleic anhydride; and lower alkyl esters of dicarboxylic acids such as dimethyl terephthalate, dimethyl maleate and dimethyl adipate; it can.
The polyester resin may be cross-linked by using the following trivalent or higher carboxylic acid. Examples of crosslinking components include trimellitic acid, tri-n-ethyl 1,2,4-tricarboxylate, tri-n-butyl 1,2,4-tricarboxylate, and tri-n-hexyl 1,2,4-tricarboxylate. 1,2,4-benzenetricarboxylic acid triisobutyl, 1,2,4-benzenetricarboxylic acid tri-n-octyl, 1,2,4-benzenetricarboxylic acid tri-2-ethylhexyl and tricarboxylic acid lower alkyl ester Can be used. However, it is not limited to these, and other trivalent or higher carboxylic acids or trivalent or higher carboxylic acid lower alkyl esters can be used as the crosslinking component.
Moreover, you may use monovalent carboxylic acid and monovalent alcohol. For example, benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, dodecanoic acid, stearic acid, etc. One or more of n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, lauryl alcohol, 2-ethylhexanol, decanol, cyclohexanol, benzyl alcohol, dodecyl alcohol, etc. A monofunctional monomer or the like can be added.
The polyester resin can be produced by a normal polyester synthesis method. For example, an esterification reaction or a transesterification reaction between a polyvalent carboxylic acid and a polyhydric alcohol, followed by a polycondensation reaction in accordance with a conventional method by introducing a low-boiling polyhydric alcohol under reduced pressure or introducing nitrogen gas. Get. In the esterification or transesterification reaction, an ordinary esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate, magnesium acetate, or the like can be used as necessary. Regarding polymerization, known polymerization catalysts such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, and germanium dioxide can be used. Further, the polymerization temperature and the amount of catalyst are not particularly limited, and may be arbitrarily selected as necessary.
It is also a preferred embodiment that the polyester resin is a vinyl-modified polyester resin modified with a vinyl monomer.
The vinyl-modified polyester resin has a structure in which a polyester and a vinyl polymer are bonded to each other, the internal protection performance is given by a polyester skeleton, and the charging stability can be improved by a vinyl polymer unit.
The vinyl-modified polyester resin is preferably a resin in which a vinyl polymer obtained by addition polymerization of an aromatic vinyl monomer and a (meth) acrylic acid ester monomer and a polyester are chemically bonded.
Further, the vinyl-modified polyester resin is contained in the ester exchange reaction between the hydroxyl group contained in the polyester and the (meth) acrylic acid ester contained in the vinyl polymer, the hydroxyl group contained in the polyester and the vinyl polymer. It can be produced by an ester reaction with a carboxy group. The vinyl-modified polyester resin preferably contains 1 to 60% by mass of a vinyl monomer as a monomer component constituting the resin, more preferably 10 to 50% by mass, and further 15 to 40% by mass. When the content is less than 1% by mass, the charging performance may be inferior, and when it exceeds 60% by mass, the fixing performance may be inferior.
As a particularly preferable polyester or vinyl-modified polyester resin, it is preferable to contain bisphenol A and / or linear alkyldiol as an alcohol constituting the resin in an amount of less than 50 mol% with respect to 100 mol% of the total alcohol. Moreover, it is preferable to contain 50 mol% or more of linear aryl dicarboxylic acid and / or linear alkyl dicarboxylic acid as carboxylic acid in 100 mol% of all carboxylic acids.
Examples of vinyl monomers that can be used to produce the vinyl-modified polyester resin include vinyl polymerizable monomers copolymerizable with styrene. Examples of such vinyl polymerizable monomers include the vinyl polymerizable monomers described below.
In the case of producing a vinyl-modified polyester resin, a polymerizable group for bonding the vinyl polymer and the polyester is a polyester resin, a vinyl polymer, a monomer constituting the polyester, and a vinyl polymerizable monomer. It is preferable to contain in at least any one of these. Examples of monomers that can react with the vinyl polymer among the monomers constituting the polyester resin include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Examples of the monomer constituting the vinyl polymer include those having a carboxy group or a hydroxy group, and acrylic acid or methacrylic acid esters.
As a manufacturing method of the said vinyl modified polyester resin, the manufacturing method shown to the following (1)-(4) can be mentioned, for example.
(1) A method of forming a vinyl-modified polyester resin while polymerizing a polyester in the presence of a vinyl-based polymer. An organic solvent can be appropriately used.
(2) A method for producing a vinyl-modified polyester resin by forming a polyester and then polymerizing a vinyl-based polymerizable monomer in the presence of the polyester.
(3) By forming a vinyl polymer and polyester and then adding a vinyl polymerizable monomer and / or a monomer constituting the polyester (alcohol, carboxylic acid, etc.) in the presence of these polymers. This is a method for producing a vinyl-modified polyester resin. Also in this case, an organic solvent can be appropriately used.
(4) A method in which a vinyl-modified polyester resin is produced by forming a vinyl polymer and a polyester and then bonding them together by an ester bond or an amide bond. Also in this case, an organic solvent can be appropriately used.
In the production methods (1) to (4), the reaction may be performed in the presence of a low softening point compound. Among the production methods (1) to (4), the production method (2) is particularly preferable because the molecular weight control of the vinyl polymer unit is easy.
Further, a vinyl-modified polyester resin having a block type in which a vinyl polymer is bonded to a polyester terminal by introducing a vinyl group only at the terminal of the polyester unit and polymerizing a vinyl monomer by the production method of (2) above. Is particularly preferable from the viewpoint of low-temperature fixability and charging stability.

Preferred examples of the polymerizable monomer in the suspension polymerization method include the following vinyl polymerizable monomers. Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- Styrene derivatives such as n-hexyl styrene, pn-octyl, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene; methyl acrylate, ethyl Acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl Acrylic polymerizable monomers such as acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n- Propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethylphos Fate ethyl methacrylate, dibutyl phosphate ethyl Methacrylic polymerizable monomers such as acrylate; methylene aliphatic monocarboxylic acid esters; vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether, vinyl Vinyl ethers such as ethyl ether and vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.
The shell part is preferably composed of a vinyl polymer formed from these vinyl polymerizable monomers and an added resin. Among these vinyl polymers, a styrene polymer, a styrene-acrylic copolymer, or a styrene-methacrylic copolymer is preferable from the viewpoint of efficiently covering the wax mainly forming the inside or the central portion.
Moreover, the following are mentioned as a polymerization initiator used in the case of superposition | polymerization. 2,2′-azobis- (2,4-divaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis Azo or diazo polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyloxy carbonate, cumene hydroperoxide, 2,4-dichloro Peroxide polymerization initiators such as benzoyl peroxide and lauroyl peroxide. These polymerization initiators are preferably added in an amount of 0.5 to 20.0% by mass relative to the polymerizable monomer, and may be used alone or in combination.
In order to control the molecular weight of the binder resin constituting the toner particles, a chain transfer agent may be added during the polymerization. A preferred addition amount is 0.001 to 15,000 mass% of the polymerizable monomer.
On the other hand, in order to control the molecular weight of the binder resin constituting the toner particles, a crosslinking agent may be added during the polymerization. The following are mentioned as a crosslinkable monomer. Divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 -Hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene Glycol diacrylate, polyester-type diacrylate (MANDA Nippon Kayaku), and the above acrylates replaced with methacrylate of.
The following are mentioned as a polyfunctional crosslinking monomer. Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and methacrylate thereof, 2,2-bis (4-methacryloxy-polyethoxyphenyl) propane, diacrylphthalate, Triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diaryl chlorendate. A preferable addition amount is 0.001 to 15.000 mass% with respect to the polymerizable monomer.
The binder resin constituting the toner particles is preferably a vinyl resin. The vinyl resin is produced by polymerization of the vinyl polymerizable monomer described above. Vinyl resin is excellent in environmental stability.

When the medium used in the polymerization is an aqueous medium, the following can be used as the dispersion stabilizer for the particles of the polymerizable monomer composition. Tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina . Examples of the organic dispersant include the following. Polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt, starch.
Commercially available nonionic, anionic and cationic surfactants can also be used. Examples of such surfactants include the following. Sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate.
In the present invention, when an aqueous medium is prepared using a hardly water-soluble inorganic dispersion stabilizer, the amount of these dispersion stabilizers used is 0.2 to 2 with respect to 100 parts by mass of the polymerizable monomer. 0.0 part by mass is preferable. In the present invention, it is preferable to prepare an aqueous medium using 300 to 3,000 parts by mass of water with respect to 100 parts by mass of the polymerizable monomer composition.
In the present invention, when preparing an aqueous medium in which the above poorly water-soluble inorganic dispersant is dispersed, a commercially available dispersion stabilizer may be used as it is. In order to obtain a dispersion stabilizer having a fine and uniform particle size, a poorly water-soluble inorganic dispersant may be produced in a liquid medium such as water under high-speed stirring. For example, when tricalcium phosphate is used as a dispersion stabilizer, a preferred dispersion stabilizer can be obtained by mixing sodium phosphate aqueous solution and calcium chloride aqueous solution under high speed stirring to form fine particles of tricalcium phosphate. Can do.

The toner of the present invention preferably contains a wax. The wax that can be used is not particularly limited, and examples thereof include the following. Paraffin wax, microcrystalline wax, petroleum wax such as petrolatum and derivatives thereof, montan wax and derivatives thereof, hydrocarbon wax and derivatives thereof according to Fischer-Tropsch method, polyolefin wax and derivatives thereof such as polyethylene and polypropylene, carnauba wax, candelilla Natural waxes such as waxes and derivatives thereof. Derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. In addition, fatty acids such as higher aliphatic alcohols, stearic acid and palmitic acid, or compounds thereof, acid amide waxes, ester waxes, ketones, hydrogenated castor oil and derivatives thereof, plant waxes, animal waxes, and silicone resins. Can be used.
In recent years, the need for full-color double-sided images has increased, and when a double-sided image is formed, the toner image on the transfer material first formed on the front surface is also used when the next image is formed on the back surface. There is a possibility of passing again through the heating section. In that case, it is necessary to sufficiently consider the high-temperature offset resistance of the fixed image of the toner. Specifically, it is preferable to add 2 to 30% by mass of wax in the toner particles. When the content is less than 2% by mass, the high temperature offset resistance is lowered, and further, the image on the back surface may show an offset phenomenon when fixing a double-sided image. When the amount is more than 30% by mass, toner particles are likely to be coalesced during granulation in the production by the polymerization method, and those having a wide particle size distribution are likely to be generated.

The colorant used in the toner of the present invention is not particularly limited, and known ones shown below can be used.
Examples of yellow pigments include yellow iron oxide, navel yellow, naphthol yellow S, hansa yellow G, hansa yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, and tartrazine lake. Isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specific examples include the following. C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 168, C.I. I. Pigment Yellow 180.
Examples of the orange pigment include the following. Permanent orange GTR, pyrazolone orange, Vulcan orange, benzidine orange G, indanthrene brilliant orange RK, indanthrene brilliant orange GK.
Red pigments include Bengala, Permanent Red 4R, Resol Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red C, Lake D, Brilliant Carmine 6B, Brilliant Carmine 3B, Eoxin Lake, Rhodamine Lake B, Alizarin Lake, etc. Examples thereof include azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specific examples include the following. C. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 23, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 166, C.I. I. Pigment red 169, C.I. I. Pigment red 177, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment Red 254.
Blue pigments include alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, first sky blue, indanthrene blue BG and other copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dyes Examples include lake compounds. Specific examples include the following. C. I. Pigment blue 1, C.I. I. Pigment blue 7, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. Pigment Blue 66.
Examples of purple pigments include fast violet B and methyl violet lake.
Examples of the green pigment include Pigment Green B, Malachite Green Lake, and Final Yellow Green G. Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.
Examples of the black pigment include carbon black, aniline black, non-magnetic ferrite, magnetite, the above-described yellow colorant, red colorant, and blue colorant, and those that are toned in black. These colorants can be used alone or in combination, and further in a solid solution state.
Further, depending on the toner production method, it is necessary to pay attention to the polymerization inhibiting property and the dispersion medium transferability of the colorant. If necessary, the surface may be modified by subjecting the colorant to a surface treatment with a substance that does not inhibit polymerization. In particular, since dyes and carbon black often have polymerization inhibiting properties, care must be taken when using them.
A preferable method for treating the dye includes a method in which a polymerizable monomer is previously polymerized in the presence of the dye and the obtained colored polymer is added to the polymerizable monomer composition. Moreover, about carbon black, you may process with the substance (for example, organosiloxane etc.) which reacts with the surface functional group of carbon black besides the process similar to the said dye.
In addition, it is preferable that content of a coloring agent is 3.0 thru | or 15.0 mass parts with respect to 100 mass parts of binder resin or a polymerizable monomer.

In the toner of the present invention, a charge control agent can be used at the time of toner production. Known charge control agents can be used. In particular, a charge control agent that has a high charging speed and can stably maintain a constant charge amount is preferable. Further, when the toner particles are produced by a direct polymerization method, a charge control agent having a low polymerization inhibition property and substantially free from a solubilized product in an aqueous medium is particularly preferable. Examples of the charge control agent include nigrosine dyes, quaternary ammonium salts, triphenylmethane compounds, and the like. Among these, a triphenylmethane compound is particularly preferable. The toner of the present invention can contain these charge control agents alone or in combination of two or more.
The addition amount of these charge control agents is preferably 0.01 to 10.00 parts by mass with respect to 100 parts by mass of the binder resin or polymerizable monomer.

The toner of the present invention can be obtained by externally adding various organic or inorganic fine powders to toner particles for the purpose of imparting various properties. The organic or inorganic fine powder preferably has a particle size of 1/10 or less of the weight average particle size of the toner particles in view of durability when added to the toner particles.
As organic or inorganic fine powder, the following are used, for example.
(1) Fluidity imparting agent: silica, alumina, titanium oxide, carbon black, and carbon fluoride.
(2) Abrasive: metal oxide (for example, strontium titanate, cerium oxide, alumina, magnesium oxide, chromium oxide), nitride (for example, silicon nitride), carbide (for example, silicon carbide), metal salt (for example, calcium sulfate, sulfuric acid) Barium, calcium carbonate).
(3) Lubricant: fluororesin powder (for example, vinylidene fluoride, polytetrafluoroethylene), fatty acid metal salt (for example, zinc stearate, calcium stearate).
(4) Charge controllable particles: metal oxide (for example, tin oxide, titanium oxide, zinc oxide, silica, alumina), carbon black.
The organic or inorganic fine powder treats the surface of the toner particles in order to improve the fluidity of the toner and to make the charge of the toner particles uniform. By using hydrophobic treatment of organic or inorganic fine powder, it is possible to adjust the chargeability of the toner and improve the properties in a high humidity environment. Use hydrophobic organic or inorganic fine powder. Is preferred. When the organic or inorganic fine powder added to the toner absorbs moisture, the chargeability as the toner is lowered, and the developability and transferability are easily lowered.
As the treatment agent for hydrophobic treatment of organic or inorganic fine powder, unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, An organic titanium compound is mentioned. These treatment agents may be used alone or in combination.
Among these, inorganic fine powder treated with silicone oil is preferable. More preferably, the inorganic fine powder is treated with silicone oil at the same time or after the hydrophobic treatment with the coupling agent. Hydrophobized inorganic fine powder treated with silicone oil is good for maintaining a high charge amount of toner even in a high humidity environment and reducing selective developability.
The addition amount of these organic or inorganic fine powders is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 3.5 parts by mass with respect to 100 parts by mass of the toner particles. These organic or inorganic fine powders may be used alone or in combination.
Here, the BET specific surface area of the organic or inorganic fine powder is preferably 10 m ² / g or more and 450 m ² / g or less.
The specific surface area BET of the organic or inorganic fine powder can be determined by a low temperature gas adsorption method by a dynamic constant pressure method according to the BET method (preferably the BET multipoint method). For example, by using a specific surface area measuring device “Gemini 2375 Ver. 5.0” (manufactured by Shimadzu Corporation), nitrogen gas is adsorbed on the sample surface, and measurement is performed using the BET multipoint method. m ² / g) can be calculated.

The toner of the present invention preferably has a viscosity at 100 ° C. measured by a constant load extrusion type capillary rheometer of 1,000 Pa · s or more and 40,000 Pa · s or less. When the viscosity at 100 ° C. is 1000 to 40,000 Pa · s, the toner has excellent low-temperature fixability. On the other hand, the toner containing the charge control resin of the present invention prevents bleeding of the resin having an ammonium base to the toner surface and the flow of the charge control resin on the toner surface even if the toner is advantageous for low-temperature fixing. it can. The viscosity at 100 ° C. is more preferably 2,000 Pa · s to 20,000 Pa · s. When the viscosity at 100 ° C. is less than 1,000 Pa · s, the gloss tends to decrease due to the penetration of the toner into the transfer material. Further, with use over a long period of time, inorganic fine powder or the like added as an external additive is buried in the surface of the toner particles, or the toner particles are deformed and the triboelectric charge characteristics are likely to be non-uniform. On the other hand, when the viscosity at 100 ° C. is larger than 40,000 Pa · s, the toner cannot be sufficiently deformed during the fixing process in high-speed and low-temperature printing, and the toner image is peeled off when the surface of the fixed image is rubbed. Cheap. In the present invention, the viscosity at 100 ° C. can be adjusted by the addition amount of the low molecular weight resin, the monomer species at the time of producing the binder resin, the initiator amount, the reaction temperature and the reaction time.
The value of the viscosity at 100 ° C. measured by the capillary rheometer of the constant load extrusion method of toner can be obtained by the following method.
As an apparatus, for example, a flow tester CFT-500D (manufactured by Shimadzu Corporation) is used, and measurement is performed under the following conditions.
Sample: About 1.0 g of toner is weighed and molded using a pressure molding machine for 1 minute at a load of 100 kg / cm ² to obtain a sample.
-Die hole diameter: 1.0 mm
-Die length: 1.0 mm
・ Cylinder pressure: 9.807 × 10 ⁵ (Pa)
・ Measurement mode: Temperature rising method ・ Temperature rising speed: 4.0 ° C./min
By the above method, the viscosity (Pa · s) of the toner at 50 to 200 ° C. is measured to obtain the viscosity (Pa · s) at 100 ° C. The value is defined as a viscosity at 100 ° C. measured with a capillary rheometer of a toner constant load extrusion method.

The weight average particle size (D4) of the toner of the present invention is preferably 4.0 to 9.0 μm, more preferably 5.0 to 8.0 μm, and still more preferably 5.0 to 7.0 μm. It is.
The glass transition temperature (Tg) of the toner of the present invention is preferably 40 to 100 ° C., more preferably 40 to 80 ° C., and further preferably 45 to 70 ° C. When the glass transition temperature is less than 40 ° C., the blocking resistance of the toner decreases. When the glass transition temperature exceeds 100 ° C., the low temperature offset resistance of the toner and the transparency of the transmitted image of the overhead projector film are lowered.
The content of insoluble content of tetrahydrofuran (THF) in the toner of the present invention is preferably less than 16.0% by mass with respect to the toner components other than the toner colorant and inorganic fine powder. More preferably, it is 0.0 mass% or more and less than 10.0 mass%, More preferably, it is 0.0 mass% or more and less than 5.0 mass%. When it is larger than 16.0% by mass, the low-temperature fixability tends to be lowered.
The content of the THF-insoluble matter in the toner means the mass ratio of the ultra-high polymer component (substantially crosslinked polymer) that has become insoluble in the THF solvent. In the present invention, the content of the THF-insoluble matter in the toner is a value measured as follows.
1.0 g of toner is weighed (W1 g), placed in a cylindrical filter paper (for example, No. 86R manufactured by Toyo Filter Paper), subjected to a Soxhlet extractor, extracted for 20 hours using 200 ml of THF as a solvent, and soluble components extracted by the solvent are extracted. After concentration, vacuum drying is performed at 40 ° C. for several hours, and the amount of THF-soluble resin component is weighed (W2 g). The weight of a component other than the resin component such as a pigment in the toner is (W3 g). The THF-insoluble content is obtained from the following formula.
Content (mass%) of THF insoluble matter = (W1− (W3 + W2)) / (W1−W3) × 100
The content of the toner insoluble matter in the toner can be adjusted by the degree of polymerization and the degree of crosslinking of the binder resin.
In the present invention, the weight average molecular weight (hereinafter also referred to as toner weight average molecular weight) (Mw) measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble content of the toner is 7,000 to 50. , 000 is preferable. If the weight average molecular weight (Mw) of the toner is less than 7,000, the blocking resistance and durability are likely to deteriorate, and if it exceeds 50,000, it becomes difficult to obtain a low-temperature fixability and a high gloss image. In the present invention, the weight average molecular weight (Mw) of the toner includes the addition amount and the weight average molecular weight (Mw) of the low molecular resin, the reaction temperature, the reaction time, the initiator amount, the chain transfer agent amount, and the crosslinking amount at the time of toner production. It can be adjusted by the amount of the agent.
In the present invention, the ratio [Mw / Mn] of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble part of the toner is: It is preferably 5 to 100, more preferably 5 to 30. When [Mw / Mn] is less than 5, the fixable temperature range is narrow, and when it exceeds 100, the low-temperature fixability tends to decrease.

A method for measuring and evaluating physical properties relating to the toner of the present invention will be described below.
<Method of measuring weight average molecular weight (Mw), number average molecular weight (Mn) and main peak molecular weight (Mp) of toner and various resins>
The weight average molecular weight (Mw), number average molecular weight (Mn), and main peak molecular weight (Mp) of the toner and various resins are measured under the following conditions using gel permeation chromatography (GPC).
[Measurement condition]
Column (made by Showa Denko KK): Shodex GPC KF-801, KF-802, KF-803, KF-804, KF-805, KF-806, KF-807 (diameter 8.0 mm, length 30 cm) 7 stations, eluent: tetrahydrofuran (THF)
・ Temperature: 40 ℃
・ Flow rate: 0.6ml / min
・ Detector: RI
Sample concentration and amount: 10 μl of 0.1% by mass sample
[Sample preparation]
0.04 g of a measurement target (toner, various resins) was dispersed and dissolved in 20 ml of tetrahydrofuran, allowed to stand for 24 hours, and filtered with a 0.2 μm filter [Mysholy disk H-25-2 (manufactured by Tosoh Corporation)]. The filtrate is used as a sample.
The calibration curve uses a molecular weight calibration curve created with a monodisperse polystyrene standard sample. As standard polystyrene samples for preparing calibration curves, TSK standard polystyrenes F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F- manufactured by Tosoh Corporation 4, F-2, F-1, A-5000, A-2500, A-1000, and A-500 are used. At this time, at least about 10 standard polystyrene samples are used.
In creating the molecular weight distribution of GPC, the chromatogram rises from the baseline on the high molecular weight side and starts measurement from the starting point, and the molecular weight is measured up to about 400 on the low molecular weight side.

<Method for Measuring Glass Transition Temperature (Tg) of Toner and Various Resins>
The glass transition temperature (Tg) of the toner and various resins is measured according to the following procedure using a differential scanning calorimeter (DSC) M-DSC (trade name: Q1000, manufactured by TA Instruments). Weigh precisely 6 mg of the sample (toner, various resins) to be measured. This is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rising rate of 1 ° C./min and normal temperature and humidity in a measurement temperature range of 20 to 200 ° C. Measurement is performed at a modulation amplitude of ± 0.5 ° C. and a frequency of 1 / min. The glass transition temperature (Tg: ° C.) is calculated from the obtained reversing heat flow curve. Tg is obtained as Tg (° C.) as the center value of the intersection of the baseline before and after endotherm and the tangent of the curve due to endotherm.

<Method for Measuring Weight Average Particle Size (D4) and Number Average Particle Size (D1) of Toner>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are measured with a fine particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, Beckman 2) Effective measurement channel number 25,000 using “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter) Measure in the channel, analyze the measurement data, and calculate.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.
Prior to measurement and analysis, the dedicated software is set as follows.
In the “Standard measurement method (SOM) change screen” of the dedicated software, set the total count in the control mode to 50000 particles, the number of measurements is 1 and the Kd value is “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked.
In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm or more and 60 μm or less.
The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
(2) About 30 ml of the electrolytic aqueous solution is put in a glass 100 ml flat bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder pH 7 precision measurement is used as a dispersant therein. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing a vessel (made by Wako Pure Chemical Industries, Ltd.) 3 times with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and is placed in a water tank of an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) with an electrical output of 120 W. A predetermined amount of ion-exchanged water is put, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. When the graph / volume% is set with the dedicated software, the “average diameter” on the analysis / volume statistics (arithmetic average) screen is the weight average particle size (D4), and the graph / number% is set with the dedicated software. The “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).

<Measuring method of average circularity of toner>
The average circularity of the toner is measured using “FPIA-3000 type” (manufactured by Sysmex Corporation), which is a flow type particle image analyzer, under the measurement / analysis conditions at the time of calibration work.
A suitable amount of a surfactant, preferably an alkylbenzene sulfonate, is added to 20 ml of ion-exchanged water, and then 0.02 g of a measurement sample is added. A desktop ultrasonic cleaner with an oscillation frequency of 50 kHz and an electric output of 150 watts. Dispersion treatment is performed for 2 minutes using a disperser (for example, “VS-150” (manufactured by Vervo Creer, etc.) to obtain a dispersion for measurement, and the temperature of the dispersion is 10 ° C. or more and 40 ° C. or less. Cool as appropriate.
The flow type particle image analyzer equipped with a standard objective lens (10 ×) is used for measurement, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) is used as the sheath liquid. The dispersion prepared in accordance with the above procedure is introduced into the flow type particle image analyzer, 3000 toner particles are measured in the total count mode in the HPF measurement mode, and the binarization threshold at the time of particle analysis is 85%. The analysis particle diameter is limited to a circle equivalent diameter of 1.98 μm or more and 19.92 μm or less, and the average circularity of the toner particles is obtained.
In measurement, automatic focus adjustment is performed using standard latex particles (for example, Duke Scientific 5100A diluted with ion-exchanged water) before the start of measurement. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.
In the circularity distribution of the toner, when the mode circularity is 0.98 to 1.00, it means that most of the toner particles have a shape close to a true sphere. The decrease in the adhesion force of the toner to the photoreceptor due to the mirror image force, van der Waals force, etc. becomes more remarkable, and the transfer efficiency becomes very high, which is preferable.
Here, the mode circularity means that the circularity from 0.40 to 1.00 is 0.40 or more and less than 0.41, 0.41 or more and less than 0.42,... Or more and less than 1.00 and It is divided into 61 every 0.01 as 1.00, and the measured circularity of each particle is assigned to each divided range, and the circularity of the divided range where the frequency value is maximum in the circularity frequency distribution is said.

<Measurement method of ¹ H-NMR (nuclear magnetic resonance) spectrum>
[Method for confirming the presence of styrenic terminal double bonds and measuring the ratio of styrenic terminal double bonds]
Measure under the following conditions.
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Data points: 32768
Frequency range: 10500Hz
Integration count: 10000 times Measurement temperature: 60 ° C
Sample: 50 mg of a measurement sample is put into a sample tube having a diameter of 5 mm, CDCl ₃ is added as a solvent, and this is dissolved in a constant temperature bath at 60 ° C. to prepare.
(Methylene group derived from the double bond by the ¹ H-NMR measurement _{(CH 2 = C (C 6} H 5) -) qualitative and quantitative) of
^{It is} determined from a signal of 4.6 to 4.9 ppm hydrogen (corresponding to 1H each) and a peak of 5.0 to 5.3 ppm hydrogen (corresponding to 1H each) in the ¹ H-NMR spectrum.
With styrenic terminal double bonds: peaks at 4.6 to 4.9 ppm and 5.0 to 5.3 ppm Without styrenic terminal double bonds: between 4.6 to 4.9 ppm and 5.0 to 5.3 ppm No peak The signal intensity Sd per 1H of the terminal double bond was determined by comparing the signal of 4.6 to 4.9 ppm hydrogen (corresponding to 1H each) and 5.0 to 5.3 ppm of hydrogen (1H each) in the ¹ H-NMR spectrum. Equivalent) signal half-value {(S _4.6-4.9 ) + (S _5.0-5.3 )} / 2. Let S be the signal intensity per 1H other than the terminal double bond. The signal intensity S _all per 1 H other than the terminal double bond is determined from the average number of protons H per molecule. The ratio (mol%) of the styrenic terminal double bond is determined from the following formula.
S = S _all / H
Styrene terminal double bond ratio (mol%) = Sd / S × 100
[Method for confirming the presence of terminal double bonds and measuring the ratio of terminal double bonds]
Measure under the following conditions.
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Data points: 32768
Frequency range: 10500Hz
Integration count: 10000 times Measurement temperature: 60 ° C
Sample: 50 mg of a measurement sample is put into a sample tube having a diameter of 5 mm, CDCl ₃ is added as a solvent, and this is dissolved in a constant temperature bath at 60 ° C. to prepare.
(Qualitative and quantitative determination of vinyl group (CH ₂ = RR′-) derived from terminal double bond by ¹ H-NMR measurement)
^{It is} determined from a signal of hydrogen of methylene group (corresponding to 1H each) in ¹ H-NMR spectrum.
With terminal double bond: With peak of double bond methylene group Without terminal double bond: Without peak of double bond methylene group Signal intensity Sd per 1H of terminal double bond, ¹ H-NMR spectrum The half value {( _Smethylene )} / 2 of the signal intensity ( _Smethylene ) of hydrogen of the methylene group (corresponding to 1H each) in Let S be the signal intensity per 1H other than the terminal double bond. The signal intensity S _all per 1 H other than the terminal double bond is determined from the average number of protons H per molecule. The ratio (mol%) of the terminal double bond is determined from the following formula.
S = S _all / H
Terminal double bond ratio (mol%) = Sd / S × 100

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the examples. In addition, the part in the following mixing | blending shows a mass part unless there is particular description.
A production example of the polymerizable charge control resin used in the present invention will be described.
<Production example of polymerizable charge control resin 1>
In a pressurizable reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube, a dropping device and a decompression device, 450 parts by mass of xylene, 92.0 parts by mass of styrene, 5.0 parts by mass of n-butyl acrylate and methacrylic acid 1.1 parts by mass of dimethylaminoethyl acid was added and heated under pressure while stirring until the reaction temperature reached 195 ° C. The pressure at this time was 0.40 atm. A solution obtained by diluting 0.8 parts by mass of 2,2′-azobisisobutyronitrile as a polymerization initiator with 20 parts by mass of 2-propanol was dropped over 30 minutes, and stirring was continued for 5 hours. Further, a solution obtained by diluting 1.2 parts by mass of 2,2′-azobisisobutyronitrile with 20 parts by mass of 2-propanol was added dropwise over 30 minutes, and further stirred for 5 hours at 195 ° C. and 0.4 MPa. The high temperature pressure polymerization was terminated.
The obtained solution polymer was cooled, 3.5 parts by mass of toluene, 5.0 parts by mass of ethanol, and 1.3 parts by mass of methyl paratoluenesulfonate were added, and salt formation was performed with stirring at 70 ° C. for 5 hours. After doing so, the contents were cooled.
Next, the polymer obtained after the polymerization solvent was distilled off under reduced pressure was coarsely pulverized to 100 μm or less by a cutter mill equipped with a 150 mesh screen, and further finely pulverized by a jet mill. The fine powder was classified with a 250 mesh sieve to obtain particles of 60 μm or less. Next, methyl ethyl ketone was added to dissolve the particles so as to have a concentration of 10%, and the resulting solution was gradually poured into 20 times the amount of methanol of xylene to reprecipitate. The resulting precipitate was washed with one-half the amount of methanol used for reprecipitation, and the filtered particles were vacuum dried at 35 ° C. for 48 hours.
Furthermore, methyl ethyl ketone was added and redissolved so that the particles after the vacuum drying had a concentration of 10%, and the obtained solution was gradually poured into n-hexane 20 times the amount of methyl ethyl ketone and reprecipitated. The obtained precipitate was washed with half the amount of n-hexane used for reprecipitation, and the filtered particles were vacuum dried at 35 ° C. for 48 hours. The obtained resin was designated as a polymerizable charge control resin 1. The polymerizable charge control resin thus obtained has a Tg of about 75 ° C., a main peak molecular weight (Mp) of 3,700, a number average molecular weight (Mn) of 1,600, and a weight average molecular weight (Mw) of 3,100. Met. Further, ¹ H-NMR (EX-400: 400MH manufactured by JEOL Ltd.
In z), peaks derived from terminal double bonds were observed at 4.7 ppm and 5.1 ppm. The ratio of double bonds was 2.54 mol%.

<Production example of polymerizable charge control resin 2>
In the production example of the polymerizable charge control resin 1, 95.0 parts by mass of styrene is 95.0 parts by mass, 5.0 parts by mass of n-butyl acrylate is 3.1 parts by mass, and dimethylaminoethyl methacrylate is 1.1 parts by mass. The polymerizable charge control resin 2 was obtained in the same manner as in the production of the polymerizable charge control resin 1 except that 0.8 part by mass and 1.3 parts by mass of methyl paratoluenesulfonate were changed to 1.0 part by mass. <Production Example of Polymerizable Charge Control Resin 3>
In the production example of the polymerizable charge control resin 1, 97.8 parts by mass of styrene is 67.8 parts by mass, 5.0 parts by mass of n-butyl acrylate is 0.1 parts by mass, and dimethylaminoethyl methacrylate is 1.1 parts by mass. The polymerizable charge control resin 3 was obtained in the same manner as in the production of the polymerizable charge control resin 1 except that 12.6 parts by mass and 1.3 parts by mass of methyl paratoluenesulfonate were changed to 16.1 parts by mass.
<Production Example of Polymerizable Charge Control Resin 4>
In the production example of the polymerizable charge control resin 1, 92.0 parts by mass of styrene is 66.5 parts by mass, 5.0 parts by mass of n-butyl acrylate is 0.2 parts by mass, and dimethylaminoethyl methacrylate is 1.1 parts by mass. The polymerizable charge control resin 4 was obtained in the same manner as in the production of the polymerizable charge control resin 1 except that 13.6 parts by mass and 1.3 parts by mass of methyl paratoluenesulfonate were changed to 16.1 parts by mass.
<Production Example of Polymerizable Charge Control Resin 5>
A polymerizable charge control resin 5 was obtained in the same manner as the polymerizable charge control resin 1 except that the reaction temperature was changed from 195 ° C. to 170 ° C. and 0.40 atm to 0.12 atm in the production example of the polymerizable charge control resin 1.
<Production example of polymerizable charge control resin 6>
A polymerizable charge control resin 6 was obtained in the same manner as the polymerizable charge control resin 1 except that the reaction temperature was changed from 195 ° C. to 220 ° C. and 0.40 atm to 0.50 atm in the production example of the polymerizable charge control resin 1.
<Production Example of Polymerizable Charge Control Resin 7>
A polymerizable charge control resin 7 was obtained in the same manner as in the polymerizable charge control resin 1 except that the reaction temperature was changed from 195 ° C. to 165 ° C. and 0.40 atm to 0.10 atm in the production example of the polymerizable charge control resin 1.
<Production example of polymerizable charge control resin 8>
A polymerizable charge control resin 8 was obtained in the same manner as the polymerizable charge control resin 1 except that the reaction temperature was changed from 195 ° C. to 230 ° C. and 0.40 atm to 0.55 atm in the production example of the polymerizable charge control resin 1.
<Production Example of Polymerizable Charge Control Resin 9>
In the production example of the polymerizable charge control resin 1, the same procedure as in the production example of the polymerizable charge control resin 1 except that 0.8 part by mass of 2,2′-azobisisobutyronitrile was changed to 2.2 parts by mass. Thus, a polymerizable charge control resin 9 was obtained.
<Production Example of Polymerizable Charge Control Resin 10>
In the production example of the polymerizable charge control resin 1, the same procedure as in the production example of the polymerizable charge control resin 1 except that 0.8 part by mass of 2,2′-azobisisobutyronitrile was changed to 1.9 parts by mass. Thus, a polymerizable charge control resin 10 was obtained.
<Production Example of Polymerizable Charge Control Resin 11>
In the production example of the polymerizable charge control resin 1, the same procedure as in the production example of the polymerizable charge control resin 1 except that 0.8 part by mass of 2,2′-azobisisobutyronitrile was changed to 0.6 part by mass. Thus, a polymerizable charge control resin 11 was obtained.
<Production example of polymerizable charge control resin 12>
In the production example of the polymerizable charge control resin 1, the same procedure as in the production example of the polymerizable charge control resin 1 except that 0.8 part by mass of 2,2′-azobisisobutyronitrile was changed to 0.4 part by mass. Thus, a polymerizable charge control resin 12 was obtained.

<Production Example of Polymerizable Charge Control Resin 13>
In a pressurizable reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, a dropping device and a decompression device, 1050 parts by mass of xylene, 92.0 parts by mass of styrene, 5.0 parts by mass of n-butyl acrylate, 2 -1.0 part by mass of hydroxyethylmethyl methacrylate and 3.0 parts by mass of dimethylaminoethylbenzyl chloride methacrylate were added and heated while stirring until the reaction temperature reached 120 ° C. A solution obtained by diluting 0.8 parts by mass of 2,2′-azobisisobutyronitrile as a polymerization initiator with 20 parts by mass of 2-propanol was dropped over 30 minutes, and stirring was continued for 5 hours. Further, a solution obtained by diluting 1.2 parts by mass of 2,2′-azobisisobutyronitrile with 20 parts by mass of 2-propanol was added dropwise over 30 minutes, and further stirred for 5 hours to complete the polymerization at 120 ° C. . Next, the polymerization solvent was distilled off under reduced pressure and then dried to obtain a resin A.
Next, 80 parts by mass of resin A and 4 parts by mass of isocyanate ethyl methacrylate were added to 50 parts by mass of xylene and heated at 40 ° C. for up to 4 hours. Further, the pressure was reduced while heating, and the solvent was removed to obtain a charge control resin 13 having a terminal double bond.

<Production Example of Polymerizable Charge Control Resin 14>
In a pressurizable reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet tube, a dropping device and a decompression device, 450 parts by mass of xylene, 92.4 parts by mass of styrene, 5.2 parts by mass of n-butyl acrylate and methacryl 2.4 parts by mass of dimethylaminoethylbenzyl chloride was added and heated under pressure until the reaction temperature reached 195 ° C. with stirring. The pressure at this time was 0.40 atm. A solution obtained by diluting 0.8 parts by mass of 2,2′-azobisisobutyronitrile as a polymerization initiator with 20 parts by mass of 2-propanol was dropped over 30 minutes, and stirring was continued for 5 hours. Further, a solution obtained by diluting 1.2 parts by mass of 2,2′-azobisisobutyronitrile with 20 parts by mass of 2-propanol was added dropwise over 30 minutes, and further stirred for 5 hours at 195 ° C. and 0.4 MPa. The high temperature pressure polymerization was terminated.
Next, the polymer obtained after the polymerization solvent was distilled off under reduced pressure was coarsely pulverized to 100 μm or less by a cutter mill equipped with a 150 mesh screen, and further finely pulverized by a jet mill. The fine powder was classified with a 250 mesh sieve to obtain particles of 60 μm or less. Next, methyl ethyl ketone was added to dissolve the particles so as to have a concentration of 10%, and the resulting solution was gradually poured into 20 times the amount of methanol of xylene to reprecipitate. The resulting precipitate was washed with one-half the amount of methanol used for reprecipitation, and the filtered particles were vacuum dried at 35 ° C. for 48 hours.
Furthermore, methyl ethyl ketone was added and redissolved so that the particles after the vacuum drying had a concentration of 10%, and the obtained solution was gradually poured into n-hexane 20 times the amount of methyl ethyl ketone and reprecipitated. The obtained precipitate was washed with half the amount of n-hexane used for reprecipitation, and the filtered particles were vacuum dried at 35 ° C. for 48 hours. The obtained resin was designated as a polymerizable charge control resin 14. The polymerizable charge control resin thus obtained has a Tg of about 75 ° C., a main peak molecular weight (Mp) of 3,900, a number average molecular weight (Mn) of 1,400, and a weight average molecular weight (Mw) of 3,400. Met. Further, ¹ H-NMR (EX-400: 400M manufactured by JEOL Ltd.
Hz), peaks derived from terminal double bonds were observed at 4.7 ppm and 5.1 ppm. The proportion of double bonds was 2.59 mol%.

<Example of production of non-polymerizable charge control resin 1>
In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, a dropping device and a decompression device, 450 parts by mass of xylene, 92.0 parts by mass of styrene, 5.0 parts by mass of n-butyl acrylate and dimethylaminoethyl methacrylate 3.0 parts by mass of benzyl chloride was added and heated with stirring until the reaction temperature reached 120 ° C. A solution obtained by diluting 0.8 parts by mass of 2,2′-azobisisobutyronitrile as a polymerization initiator with 20 parts by mass of 2-propanol was dropped over 30 minutes, and stirring was continued for 5 hours. Further, a solution obtained by diluting 1.2 parts by mass of 2,2′-azobisisobutyronitrile with 20 parts by mass of 2-propanol was added dropwise over 30 minutes, and further stirred for 5 hours to complete the polymerization at 120 ° C. .
Next, the polymer obtained after the polymerization solvent was distilled off under reduced pressure was coarsely pulverized to 100 μm or less by a cutter mill equipped with a 150 mesh screen, and further finely pulverized by a jet mill. The fine powder was classified with a 250 mesh sieve to obtain particles of 60 μm or less. Next, methyl ethyl ketone was added to dissolve the particles so as to have a concentration of 10%, and the resulting solution was gradually poured into 20 times the amount of methanol of xylene to reprecipitate. The resulting precipitate was washed with one-half the amount of methanol used for reprecipitation, and the filtered particles were vacuum dried at 35 ° C. for 48 hours.
Furthermore, methyl ethyl ketone was added and redissolved so that the particles after the vacuum drying had a concentration of 10%, and the obtained solution was gradually poured into n-hexane 20 times the amount of methyl ethyl ketone and reprecipitated. The obtained precipitate was washed with half the amount of n-hexane used for reprecipitation, and the filtered particles were vacuum dried at 35 ° C. for 48 hours. The obtained resin was designated as non-polymerizable charge control resin 1. The non-polymerizable charge control resin thus obtained has a Tg of about 79 ° C., a main peak molecular weight (Mp) of 18,000, a number average molecular weight (Mn) of 8,920, and a weight average molecular weight (Mw) of 22, 000. Further, ¹ H-NMR (EX-400: 4 manufactured by JEOL Ltd.)
00 MHz), no peak derived from the terminal double bond was observed.

<Example of production of non-polymerizable charge control resin 2>
Non-polymerization was carried out in the same manner as in the production example of non-polymerizable charge control resin 1 except that 3.0 parts by mass of dimethylaminoethylbenzyl chloride methacrylate was changed to 0.0 parts by mass in the production example of non-polymerizable charge control resin 1. Neutral charge control resin 2 was obtained.

<Example of production of polyester resin (1)>
-Terephthalic acid: 11.2 mol-Bisphenol A-propylene oxide 2-mol adduct (PO-BPA): 10.7 mol
The above monomer is charged into an autoclave together with an esterification catalyst, and a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device and a stirring device are attached to the autoclave and 195 ° C. according to a conventional method while decompressing in a nitrogen atmosphere. The polyester resin 1 was obtained by carrying out the reaction until Tg reached 74 ° C. The weight average molecular weight (Mw) was 11,700, and the number average molecular weight (Mn) was 3,670.

<Production Example of Styrenic Resin (1)>
A reactor equipped with a dropping funnel, a Liebig cooler, a nitrogen-filled tube (nitrogen flow rate 80 ml / min) and a stirrer was charged with 600 parts by mass of xylene and heated to 140 ° C. A mixture of 100 parts by mass of a styrene monomer, 1.2 parts by mass of a polymerizable charge control resin 1 and 8.0 parts by mass of di-tert-butyl peroxide was charged into a dropping funnel, and the mixture was added to xylene at 140 ° C. for 1.5 hours. And dropped at normal pressure. Further, the reaction was carried out for 2 hours under reflux of xylene (137 ° C. to 145 ° C.) to complete solution polymerization, and xylene was removed. The obtained styrene-based resin had a weight average molecular weight (Mw) of 8,600 and Tg of 62 ° C. This was designated as styrene resin (1).
<Production example of styrene resin (2)>
A mixture of 20 parts by mass of xylene, 80 parts by mass of styrene, 20 parts by mass of n-butyl acrylate and 2.4 parts by mass of di-tert-butyl peroxide as an initiator was charged into a reactor equipped with a Liebig cooler and a stirrer. Polymerization was carried out at a temperature of 100 ° C. for 24 hours. Thereafter, xylene was removed to obtain a styrene resin (2). The obtained styrene-based resin had a weight average molecular weight (Mw) of 458,000 and Tg of 65 ° C. This was designated as styrene resin (2).

<Production Example of Charge Control Resin 1 and Toner Particle 1>
In a four-necked vessel, 700 parts by mass of ion-exchanged water, 970 parts by mass of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution, and 15.0 parts by mass of a 1.0 mol aqueous HCl solution were added, and a high-speed stirring device TK was added. -Hold at 60 ° C with stirring at 12,000 rpm using a homomixer. To this, 110 parts by mass of 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .
Styrene monomer 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Copper phthalocyanine pigment (Pigment Blue 15: 3) 6.50 parts by mass Polyester resin (1) 5 parts by mass Charge represented by the following formula (8) Control agent 1 (ammonium salt) 0.5 parts by mass

Polymerizable charge control resin 1 1.0 part by mass Wax [Fischer-Tropsch wax, endothermic main peak temperature 78.2 ° C.]
10 parts by mass 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate 11.0 as a polymerization initiator in the monomer mixture 1 obtained by dispersing the monomer mixture for 3 hours with an attritor The monomer composition to which part by mass (toluene solution 50%) was added was put into an aqueous dispersion medium, and granulated for 5 minutes while maintaining the rotational speed of the high-speed stirring device at 12,000 rpm. Thereafter, the high-speed stirrer was changed to a propeller stirrer, the internal temperature was raised to 70 ° C., and the reaction was allowed to proceed for 5 hours with slow stirring. Next, the temperature inside the container was raised to 80 ° C. and maintained for 3 hours, and then gradually cooled to 30 ° C. at a cooling rate of 1 ° C. per minute to obtain a polymer slurry 1. Dilute hydrochloric acid was added to the container containing the polymer slurry 1 to remove the dispersion stabilizer. Further, the polymer particles 1 having a weight average particle diameter of 5.6 μm, that is, the charge control resin 1 were obtained by filtration, washing and drying. The charge control resin 1 was toner particles 1. Table 1 shows the physical properties of the charge control resin 1, the polymerizable charge control resin 1 and the toner particles 1 used.
<Production Examples of Charge Control Resins 2 to 4 and Toner Particles 2 to 4>
In the manufacture example of the charge control resin 1, the charge control resins 2 to 4 were obtained in the same manner as the manufacture example of the charge control resin 1 except that the polymerizable charge control resin 1 was changed to the polymerizable charge control resins 2 to 4. . The charge control resins 2 to 4 are toner particles 2 to 4. Table 1 shows the physical properties of each charge control resin, the polymerizable charge control resin used, and each toner particle.
<Production Example of Charge Control Resin 5 and Toner Particles 5>
In the production example of the charge control resin 1, except that 11.0 parts by mass of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (toluene solution 50%) was changed to 18.0 parts by mass The charge control resin 5 was obtained in the same manner as in the production example of the charge control resin 1. The charge control resin 5 was used as toner particles 5. Table 1 shows the physical properties of the charge control resin, the polymerizable charge control resin used, and the toner particles.
<Production Example of Charge Control Resin 6 and Toner Particle 6>
In the production example of the charge control resin 1, except that 11.0 parts by mass of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (toluene solution 50%) was changed to 8.0 parts by mass The charge control resin 6 was obtained in the same manner as in the manufacture example of the charge control resin 1. The charge control resin 6 was used as toner particles 6. Table 1 shows the physical properties of the charge control resin, the polymerizable charge control resin used, and the toner particles.
<Production Example of Charge Control Resin 7 and Toner Particle 7>
In the production example of the charge control resin 1, except that 11.0 parts by mass of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (toluene solution 50%) was changed to 19.0 parts by mass The charge control resin 7 was obtained in the same manner as in the manufacture example of the charge control resin 1. The charge control resin 7 was used as toner particles 7. Table 1 shows the physical properties of the charge control resin, the polymerizable charge control resin used, and the toner particles.
<Production Example of Charge Control Resin 8 and Toner Particle 8>
In the production example of the charge control resin 1, except that 11.0 parts by mass of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (toluene solution 50%) was changed to 7.0 parts by mass The charge control resin 8 was obtained in the same manner as in the manufacture example of the charge control resin 1. The charge control resin 8 was used as toner particles 8. Table 1 shows the physical properties of the charge control resin, the polymerizable charge control resin used, and the toner particles.
<Production Examples of Charge Control Resins 9 to 12 and Toner Particles 9 to 12>
In the manufacture example of the charge control resin 1, the charge control resins 9 to 12 were obtained in the same manner as the charge control resin 1 except that the polymerizable charge control resin 1 was changed to the polymerizable charge control resins 5 to 8. . The charge control resins 9 to 12 are toner particles 9 to 12. Table 1 shows the physical properties of each charge control resin, the polymerizable charge control resin used, and each toner particle.
<Production Example of Charge Control Resin 13 and Toner Particles 13>
Styrene resin (1) 60 parts by mass Styrene resin (2) 40 parts by mass Copper phthalocyanine pigment 6.5 parts by mass Charge control agent 1 (ammonium salt) represented by the above formula (8) 0.5 parts by mass Polymerization Charge control resin 1 1.0 part by weight wax [Fischer-Tropsch wax, endothermic main peak temperature 78.2 ° C.]
10 parts by mass After mixing the above materials with a Henschel mixer, melt kneading with a twin-screw kneading extruder at 135 ° C., cooling the kneaded product, coarsely pulverizing with a cutter mill, using a fine pulverizer using a jet stream The charge control resin 13 having a weight average particle size of 5.6 μm was obtained by pulverization and further classification using an air classifier. The charge control resin 13 was used as toner particles 13. The physical properties of the charge control resin, the polymerizable charge control resin used and the toner particles are shown in Table 2.
<Production Example of Charge Control Resin 14 and Toner Particles 14>
[Synthesis of toner binder]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 660 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 100 parts by mass of bisphenol A propylene oxide 2 mol adduct, 290 parts by mass of terephthalic acid and dibutyltin oxide 2 .7 parts by mass, react at normal pressure of 210 ° C. for 11 hours, further react for 7.0 hours at a reduced pressure of 10 to 15 mmHg, then cool to 190 ° C., and add 30 parts by mass of phthalic anhydride to this. In addition, it reacted for 2 hours. Subsequently, 300 parts by mass of styrene, 2.0 parts by mass of 2,2′-azobisisobutyronitrile and 5.0 parts by mass of the polymerizable charge control resin 1 were added dropwise over 30 minutes. The reaction was continued for 2 hours. The mixture was cooled to 80 ° C. and reacted with 180 parts by mass of isophorone diisocyanate in ethyl acetate for 2 hours to obtain an isocyanate-containing prepolymer (1). Next, 265 parts by mass of prepolymer (1) and 15 parts by mass of isophoronediamine were reacted at 55 ° C. for 2 hours to obtain a urea-modified polyester (1) having a weight average molecular weight (Mw) of 66,000. 625 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 100 parts by mass of bisphenol A propylene oxide 2 mol adduct, 140 parts by mass of terephthalic acid and 140 parts by mass of isophthalic acid for 4.5 hours at 230 ° C. under normal pressure. Polycondensation was carried out, followed by reaction at a reduced pressure of 10 to 15 mmHg for 5.5 hours to obtain unmodified polyester (a) having a peak molecular weight (Mp) of 6,600. 250 parts by mass of urea-modified polyester (1) and 750 parts by mass of unmodified polyester (a) were dissolved and mixed in 2,000 parts by mass of tetrahydrofuran solvent to obtain a tetrahydrofuran solution of toner binder (1).
240 parts by mass of a tetrahydrofuran solution of the toner binder (1); I. Pigment Blue 15: 3 pigment 5.5 parts by mass, wax [Fischer-Tropsch wax, endothermic main peak temperature 78.2 ° C.] 12 parts by mass, charge control agent 1 (ammonium salt) 0 represented by the above formula (8) .5 parts by mass was added and stirred at 12000 rpm at 55 ° C. using a TK homomixer, and uniformly dissolved and dispersed. In a beaker, 710 parts by mass of ion-exchanged water, 295 parts by mass of hydroxyapatite suspension (Superite 10 manufactured by Nippon Chemical Industry Co., Ltd.) and 0.20 parts by mass of sodium dodecylbenzenesulfonate were uniformly dissolved. Next, the temperature was raised to 55 ° C., and the toner material solution was added and stirred for 10 minutes while stirring at 12,000 rpm with a TK homomixer. Next, this mixed solution was transferred to a Kolben equipped with a stirrer and a thermometer, heated to 98 ° C. to remove the solvent, filtered, washed and dried, and then subjected to air classification to obtain a charge control resin 14. The charge control resin 14 was used as toner particles 14. The physical properties of the charge control resin, the polymerizable charge control resin used and the toner particles are shown in Table 2.
<Production Example of Charge Control Resin 15 and Toner Particles 15>
[Preparation of resin fine particle dispersion 1]
Styrene 360 parts by mass n-butyl acrylate 40 parts by mass Acrylic acid 7 parts by mass Dodecanethiol 25 parts by mass Carbon tetrabromide 2.5 parts by mass Polymerizable charge control resin 1 1.0 part by mass Charge control agent 1 (ammonium salt) 0.5 part by mass The above-mentioned materials mixed and dissolved were mixed with nonionic surfactant Nonipol 400 (trade name, manufactured by Toho Chemical Co., Ltd.) 7.0 parts by mass and anion Surfactant Neogen SC (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 10.5 parts by mass, dissolved in 550.0 parts by mass of ion-exchanged water is dispersed and emulsified in a flask and slowly mixed for 10 minutes. Then, 50 parts by mass of ion exchange water in which 4.5 parts by mass of ammonium persulfate was dissolved was added to perform nitrogen substitution. Then, the flask was heated with an oil bath while stirring until the contents reached 70 ° C., and emulsion polymerization was continued for 5 hours. As a result, an anionic resin fine particle dispersion 1 having a center diameter of 135 nm, a glass transition temperature of 54 ° C., and a weight average molecular weight (Mw) of 11,200 was obtained.
[Preparation of resin fine particle dispersion 2]
Styrene 280 parts by mass n-butyl acrylate 120 parts by mass Acrylic acid 7.0 parts by mass A mixture of the above materials was dissolved in a nonionic surfactant Nonipol 400 (trade name, manufactured by Toho Chemical Co., Ltd.) 7.0 10 parts by mass and 12.0 parts by mass of anionic surfactant Neogen SC (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) dissolved in 550.0 parts by mass of ion-exchanged water were dispersed and emulsified in a flask. While slowly mixing for 5 minutes, 50 parts by mass of ion-exchanged water in which 3.5 parts by mass of ammonium persulfate was dissolved was added to perform nitrogen substitution. Then, the flask was heated with an oil bath while stirring until the contents reached 70 ° C., and emulsion polymerization was continued for 5 hours. As a result, an anionic resin fine particle dispersion 2 having a center diameter of 112 nm, a glass transition temperature of 54 ° C., and a weight average molecular weight (Mw) of 500,000 was obtained.
[Preparation of colorant dispersion]
Copper phthalocyanine pigment PV FAST BLUE (BASF) 20 parts by mass Anionic surfactant Neogen SC 2.6 parts by mass Ion-exchanged water 80 parts by mass The above materials are mixed and an ultrasonic cleaner W-113 manufactured by Honda Electronics Co., Ltd. Was dispersed for 10 minutes at an oscillation frequency of 28 kHz to obtain a colorant dispersion. When the particle size distribution of this sample was measured with a particle size measuring device LA-700 manufactured by Horiba, Ltd., the volume average particle size was 145 nm and coarse particles of 1 μm were not observed.
[Preparation of release agent dispersion]
Paraffin wax HNP0190 (melting point 85 ° C. Nippon Seiwa) 200 parts by weight Anionic surfactant Neogen SC 10 parts by weight Ion-exchanged water 780 parts by weight The above material is heated to 95 ° C. and 560 × 10 ⁵ N / m with a gorin homogenizer. After emulsification at a discharge pressure of ² , the mixture was rapidly cooled to obtain a release agent dispersion. When this sample was measured with a particle size measuring apparatus LA-700 manufactured by Horiba, Ltd., the volume average particle diameter was 128 nm, and coarse particles of 0.8 μm or more were 5% or less.
[Manufacture of charge control resin 15]
Resin fine particle dispersion 1 220 parts by weight Resin fine particle dispersion 2 30 parts by weight Colorant dispersion 30 parts by weight Release agent dispersion 30 parts by weight SANISOL B50 (generic name manufactured by Kao Corporation) 1.4 parts by weight The mixture was placed in a round stainless steel flask, mixed and dispersed with Ultra Turrax T50, and then heated to 50 ° C. while stirring the flask in an oil bath for heating. After holding at 50 ° C. for 1 hour, 3.2 parts by weight of the anionic surfactant Neogen SC (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added, the stainless steel flask was sealed, and a magnetic seal was used. While stirring, the mixture was heated to 105 ° C. and held for 3 hours. After cooling, it was filtered and sufficiently washed with ion exchange water to obtain a charge control resin 15. The charge control resin 15 was used as toner particles 15. The physical properties of the charge control resin, the polymerizable charge control resin used and the toner particles are shown in Table 2.
(Production example of charge control resins 16 to 19 and toner particles 16 to 19)
In the manufacture example of the charge control resin 1, the charge control resins 16 to 19 were obtained in the same manner as the manufacture example of the charge control resin 1 except that the polymerizable charge control resin 1 was changed to the polymerizable charge control resins 9 to 12. . The charge control resins 16 to 19 are toner particles 16 to 19. Table 2 shows the physical properties of the charge control resin, polymerizable charge control resin, and toner particles.
<Production Example of Charge Control Resin 20 and Toner Particle 20>
In the production example of the charge control resin 1, 11.0 parts by mass of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (toluene solution 50%) was changed to 8.5 parts by mass. A charge control resin 20 was obtained in the same manner as in the production example of the charge control resin 1 except that the control resin 1 was changed to the non-polymerizable charge control resin 1. The charge control resin 20 was used as toner particles 20. Table 3 shows the physical properties of the charge control resin, the non-polymerizable charge control resin used, and the toner particles.
<Production Example of Charge Control Resin 21 and Toner Particles 21>
In the manufacture example of the charge control resin 13, the charge control resin 21 was obtained in the same manner as in the manufacture example of the charge control resin 13 except that the polymerizable charge control resin 1 was changed to the non-polymerizable charge control resin 1. The charge control resin 21 was used as toner particles 21. Table 3 shows the physical properties of the charge control resin, the non-polymerizable charge control resin used, and the toner particles.
<Production Example of Charge Control Resin 22 and Toner Particles 22>
In the manufacture example of the charge control resin 14, the charge control resin 22 was obtained in the same manner as in the manufacture example of the charge control resin 14 except that the polymerizable charge control resin 1 was changed to the non-polymerizable charge control resin 1. The charge control resin 22 was used as toner particles 22. Table 3 shows the physical properties of the charge control resin, the non-polymerizable charge control resin used, and the toner particles.
<Production Example of Charge Control Resin 23 and Toner Particles 23>
In the manufacture example of the charge control resin 15, the charge control resin 23 was obtained in the same manner as in the manufacture example of the charge control resin 15 except that the polymerizable charge control resin 1 was changed to the non-polymerizable charge control resin 1. The charge control resin 23 was used as toner particles 23. Table 3 shows the physical properties of the charge control resin, the non-polymerizable charge control resin used, and the toner particles.
<Example of Production of Charge Control Resin 24 and Toner Particles 24>
In the production example of the charge control resin 1, the polymerizable charge control resin 1 is replaced with the non-polymerizable charge control resin 1 by 11.0 parts by mass of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate ( The charge control resin 24 was obtained in the same manner as in the production example of the charge control resin 1 except that the toluene solution (50%) was changed to 6.0 parts by mass. The charge control resin 24 was used as toner particles 24. Table 3 shows the physical properties of the charge control resin, the non-polymerizable charge control resin used, and the toner particles.
(Production example of charge control resin 25 and toner particles 25)
In the manufacture example of the charge control resin 1, the charge control resin 25 was obtained in the same manner as in the manufacture example of the charge control resin 1 except that the polymerizable charge control resin 1 was changed to the non-polymerizable charge control resin 2. The charge control resin 25 was used as toner particles 25. Table 3 shows the physical properties of the charge control resin, the non-polymerizable charge control resin used, and the toner particles.
<Production Example of Charge Control Resin 26 and Toner Particles 26>
In the manufacture example of the charge control resin 1, the charge control resin 26 was obtained in the same manner as in the manufacture example of the charge control resin 1 except that the polymerizable charge control resin 1 was changed to the polymerizable charge control resin 13. The charge control resin 26 was used as toner particles 26. Table 3 shows the physical properties of the charge control resin, the polymerizable charge control resin used, and the toner particles.
<Production Example of Charge Control Resin 27 and Toner Particles 27>
In the manufacture example of the charge control resin 1, the charge control resin 27 was obtained in the same manner as in the manufacture example of the charge control resin 1 except that the polymerizable charge control resin 1 was changed to the polymerizable charge control resin 14. The charge control resin 27 was used as toner particles 27. Table 3 shows the physical properties of the charge control resin, the polymerizable charge control resin used, and the toner particles.
<Production Example of Charge Control Resin 28 and Toner Particles 28>
(Production example of charge control resin 28)
In a four-necked vessel, 700 parts by mass of ion-exchanged water, 980 parts by mass of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution, and 15.0 parts by mass of a 1.0 mol aqueous HCl solution were added, and a high-speed stirring device TK was added. -Hold at 60 ° C with stirring at 12,000 rpm using a homomixer. To this, 110 parts by mass of 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .
Styrene monomer 49.6 parts by weight n-butyl acrylate 0.4 part by weight Polymerizable charge control resin 1 50.0 parts by weight Polymerization initiator in monomer mixture A obtained by dispersing the above monomer mixture for 3 hours with an attritor A monomer composition to which 15.0 parts by mass of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (toluene solution 50%) is added is introduced into an aqueous dispersion medium, and high speed Granulation was carried out for 5 minutes while maintaining the rotational speed of the stirring device at 12,000 rpm. Thereafter, the high-speed stirrer was changed to a propeller stirrer, the internal temperature was raised to 70 ° C., and the reaction was allowed to proceed for 5 hours with slow stirring. Next, the temperature in the container was raised to 80 ° C. and maintained for 3 hours, and then gradually cooled to 30 ° C. at a cooling rate of 1 ° C. per minute to obtain a polymer slurry A. Dilute hydrochloric acid was added to the container containing the polymer slurry A to remove the dispersion stabilizer. Further, filtration, washing, and drying were performed to obtain polymer particles 28 having a weight average particle diameter of 6.2 μm, that is, charge control resin 28.
(Example of production of toner particles 28)
In a four-necked vessel, 700 parts by mass of ion-exchanged water, 970 parts by mass of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution, and 15.0 parts by mass of a 1.0 mol aqueous HCl solution were added, and a high-speed stirring device TK was added. -Hold at 60 ° C with stirring at 12,000 rpm using a homomixer. To this, 110 parts by mass of 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .
Styrene monomer 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Copper phthalocyanine pigment (Pigment Blue 15: 3) 6.50 parts by mass Polyester resin (1) 5 parts by mass Charge represented by the following formula (8) Control agent 1 (ammonium salt) 0.5 parts by mass

3.0 parts by mass of charge control resin 28 [Fischer-Tropsch wax, endothermic main peak temperature 78.2 ° C.]
10 parts by mass 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate 11.0 which is a polymerization initiator in the monomer mixture B obtained by dispersing the above monomer mixture with an attritor for 3 hours The monomer composition to which part by mass (toluene solution 50%) was added was put into an aqueous dispersion medium, and granulated for 5 minutes while maintaining the rotational speed of the high-speed stirrer at 12,000 rpm. Thereafter, the high-speed stirrer was changed to a propeller stirrer, the internal temperature was raised to 70 ° C., and the reaction was allowed to proceed for 5 hours with slow stirring. Next, the temperature inside the container was raised to 80 ° C. and maintained for 3 hours, and then gradually cooled to 30 ° C. at a cooling rate of 1 ° C. per minute to obtain a polymer slurry B. Dilute hydrochloric acid was added to the container containing the polymer slurry B to remove the dispersion stabilizer. Further, the toner particles 28 having a weight average particle diameter of 5.8 μm were obtained by filtration, washing and drying. Table 3 shows the physical properties of the charge control resin 28 and the toner particles 28.

<Production Example of Toner 1>
The toner particles 1 100 parts by weight, specific surface area by BET method of 210 m ² / g, specific surface area by aminosilane 4 Hydrophobic silica 1.2 parts by weight having hydrophobicized surface mass% and the BET method ^70m 2 / Toner 1 is obtained by mixing 0.15 parts by mass of aluminum oxide (g) with a Henschel mixer (Mitsui Mining Co., Ltd.).
<Production Example of Toners 2 to 28>
In the toner 1 production example, toners 2 to 28 were obtained in the same manner as in the toner 1 production example except that the toner particles 1 were changed to toner particles 2 to 28.

<Example 1>
A toner cartridge of laser printer (manufactured by Brother Industries) HL-5380DN was used, and 130 g of toner 1 was loaded. And it was left to stand under each environment of low temperature and low humidity (10 ° C./15% RH), normal temperature and normal humidity (25 ° C./50% RH), and high temperature and high humidity (32.0 ° C./85% RH) for 24 hours. After leaving for 24 hours in each environment, images with a printing ratio of 1.0% are printed out to 10,000 sheets, and the initial and solid image density and fog at the time of 10,000 sheets output are 10,000.
Filming and development streaks during sheet output were evaluated.
In addition, a toner cartridge of HL-5380DN, a laser printer (Brother Kogyo Co., Ltd.) was used, and 130 g of toner 1 was loaded and left for 148 hours in a harsh environment (40 ° C./95%). Then, after leaving it in high temperature and high humidity (32.0 ° C./85% RH) for 24 hours, it prints out an image with a printing ratio of 1.0% up to 10,000 sheets to obtain the initial solid image density and fog. Filming and development streaks were evaluated when 10,000 sheets were output. The results are shown in Table 4, Table 5, Table 6, and Table 7.

<Evaluation of toner triboelectric charge>
The triboelectric charge amount of the toner 1 was determined by the following method. Toner 1 and a standard carrier for positively charged polarity toner (trade name: P-01, manufactured by The Imaging Society of Japan) were left in the environment shown below for the time shown below. 24 hours at low temperature and low humidity (10 ° C./15% RH), 24 hours at normal temperature and normal humidity (25 ° C./50% RH), 24 hours at high temperature and high humidity (32.0 ° C./85% RH), (° C / 95%) for 148 hours and then at high temperature and high humidity (32.0 ° C / 85% RH) for 24 hours. After leaving, the toner 1 and a standard carrier for positively charged polarity toner (trade name: P-01, manufactured by the Imaging Society of Japan) are mixed for 120 seconds using a turbula mixer in each environment so that the mass of the toner 1 is 5% by mass. A developer was prepared. Within 1 minute after mixing the obtained developer, put it in a metal container equipped with a conductive screen with an opening of 20 μm at the bottom at normal temperature and humidity (25 ° C./50% RH). The mass difference between before and after and the potential accumulated in the capacitor connected to the container were measured. At this time, the suction pressure was 4.0 kPa. Using the mass difference, the stored potential, and the capacitance of the capacitor, the triboelectric charge amount of the toner was calculated from the following formula.
The standard carrier for positively charged polarity toner (trade name: P-01, manufactured by Japan Imaging Society) used for measurement passes through 250 mesh, and the one remaining on 350 mesh is 70% by mass or more. To do.
Q (mC / kg) = C ′ × V / (W1-W2)
Q: Toner triboelectric charge amount C ′ (μF): Capacitor capacity V (volt): Potential accumulated in the capacitor W1-W2 (g): Mass difference before and after suction

<Evaluation of image density>
Regarding the image density, the image density of the fixed image portion of the output image was measured using a Macbeth densitometer (RD-914; manufactured by Macbeth Co.) equipped with an SPI auxiliary filter, and evaluated according to the following criteria.
A: 1.40 or more B: 1.30 to 1.39
C: 1.20 to 1.29
D: 1.10 to 1.19
E: 1.00 to 1.09
F: 0.99 or less

<Evaluation of development lines>
The development streak was evaluated according to the following criteria from a halftone image (toner applied amount 0.25 mg / cm ² ) obtained after printing 10,000 sheets.
A: A vertical streak in the paper discharge direction, which appears as a development streak, is not seen on the developing roller or the halftone image. There is no problem in practical use.
B: Although there are one or two circumferential thin stripes at both ends of the developing roller, no vertical stripe in the paper discharge direction, which appears as a developing stripe, is seen on the halftone image. There is no problem in practical use.
C: Although there are 3 to 5 thin circumferential streaks at both ends of the developing roller, no vertical streak in the paper discharge direction, which appears as a developing streak, is seen on the halftone image. However, there is no practical problem at the level that can be erased by image processing.
D: There are 6 to 20 fine circumferential streaks at both ends of the developing roller, and several fine developing streaks can be seen on the halftone image. It cannot be erased even with image processing.
E: 20 or more development streaks are observed on the developing roller and the image of the halftone portion, and cannot be erased even by image processing.

<Evaluation of low temperature fixability (low temperature offset end temperature)>
The fixing unit of the Canon laser beam printer LBP5500 is modified so that the fixing temperature can be adjusted, and an unfixed toner image with a toner load of 0.5 mg / cm ^{2 at} a process speed of 230 mm / sec is received by a modified fixing device. Then, heat and pressure were applied without oil to form a fixed image on the image receiving paper.
The fixing property is Kimwipe [S-200 (Crecia)], and the fixed image is rubbed 10 times with a load of 75 g / cm ² , and the temperature at which the density reduction rate before and after the rub is less than 5% is finished at the low temperature offset. It was temperature. Evaluation was carried out at room temperature and normal humidity (25 ° C./50% RH).

<Evaluation of fog>
The fog density (%) is calculated from the difference between the whiteness of the white portion of the printed image and the whiteness of the transfer paper measured by “Reflectometer” (manufactured by Tokyo Denshoku Co., Ltd.), and the image fog is evaluated according to the following criteria. did.
A: Very good (less than 1.0%)
B: Good (1.0% or more, less than 2.5%)
C: Practical use possible (2.5% or more, less than 4.0%)
D: Not practical (4.0% or more and less than 5.5%)
E: Not practical (5.5% or more and less than 7.0%)
F: Not practical (7.0% or more)

<Filming>
Filming was evaluated for the degree of contamination of the developing roller after the solid white image was printed. The evaluation criteria are shown below.
A: The surface state of the developing roller is extremely uniform.
B: Although the surface state of the developing roller is uniform, a ripple pattern can be seen in a very small part.
C: A ripple pattern is seen on a part of the surface of the developing roller.
D: A ripple pattern appears on the entire surface of the developing roller.
E: Ripples on the surface of the developing roller grow and some irregularities are clearly seen.
F: Unevenness on the surface of the developing roller spreads over the entire surface and is clearly understood.

<Examples 2 to 22>
The same evaluation as in Example 1 was performed except that the toner 1 of Example 1 was changed to toners 2 to 19 and toners 26 to 28. The results are shown in Table 4, Table 5, Table 6, and Table 7.
<Comparative Examples 1 to 6>
The same evaluation as in Example 1 was performed except that the toner 1 of Example 1 was changed to toners 20 to 25. The results are shown in Table 4, Table 5, Table 6, and Table 7.

Claims (6)

A charge control resin obtained by polymerizing a polymerizable monomer and a polymerizable charge control resin,
The polymerizable charge control resin has a quaternary ammonium salt as a functional group, ends Ri macromonomer der styrene having a double bond, in the measurement of the nuclear magnetic resonance device using a deuterated chloroform solvent, charge control resin, characterized in Rukoto that the 4.6~4.9ppm and 5.0~5.3ppm having a peak derived from the double bond. The polymerizable charge control resin, the proportion of terminal double bonds, charge control resin according to claim 1 or less than 0.10mol% 20.00mol%. 3. The charge control resin according to claim 1, wherein the polymerizable charge control resin has a weight average molecular weight (Mw) measured by gel permeation chromatography of a tetrahydrofuran-soluble content of the polymerizable charge control resin from 2,000 to 50,000. . The weight average molecular weight measured by gel permeation chromatography of tetrahydrofuran-soluble matter of the charge control resin (Mw) is, according to any one of claims 1 to 3, 7,000 to 50,000 Charge control resin. A toner having toner particles containing a charge control resin,
Toner wherein the charge control resin is a charge control resin according to any one of claims 1-4. The toner, 100 ° C. viscosity measured by capillary rheometer of constant-load extrusion method, toner according to claim 5 or less 1,000 Pa · s or more 40,000 Pa · s.