JP2012083430A - Charge control resin and toner including the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a charge control resin which is excellent in severe environmental stability and shelf stability under a high-temperature high-humidity environment, and a toner which is excellent in severe environmental stability, shelf stability under a high-temperature high-humidity environment, contamination prevention of members, and development durability and allows formation of a high quality image.SOLUTION: A charge control resin is obtained by polymerizing at least a polymerizable monomer and a polymerizable charge control resin. The polymerizable charge control resin contains an aromatic vinyl monomer unit and a monomer unit including a sulfonic acid group, a sulfonic acid salt group or a sulfonic acid ester group as a constitutional unit and is a macromonomer having a styrene double bond at a terminal. In measurement by a nuclear magnetic resonance apparatus employing a heavy chloroform solvent, the polymerizable charge control resin has a peak derived from the double bond in 4.6-4.9 ppm and 5.0-5.3 ppm and has an acid value of 5.0 mgKOH/g or more and 50.0 mgKOH/g or less.

Description

  The present invention relates to a negatively 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.
Temperature / humidity is one of the causes of fluctuations in long-term storage stability and charge amount of the toner, and 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.
A charge control resin in which a monomer type, a weight average molecular weight (Mw), and a copolymerization ratio are defined in order to control the chargeability of the resin surface is disclosed (see Patent Document 1).
However, in a temperature / humidity fluctuation and harsh environment, the charge control agent resin cannot bleed onto the resin surface or flow on the resin surface, resulting in an environment such as poor chargeability, member contamination, or image density fluctuation due to changes in toner charge amount. Has some challenges to stability.
To improve low-temperature fixability and storage stability, a toner is disclosed that uses a resin having a polymerizable double bond at the polymer terminal (see Patent Document 2).
However, the toner has some problems as a toner excellent in environmental stability, durability, low-temperature fixability, and storage stability that are currently required.
In addition, 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 fixability (see Patent Document 3).
However, the toner has some problems as a toner excellent in environmental stability and development durability.

JP 63-184762 A Japanese Patent Laid-Open No. 03-203746 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, the present invention provides a charge control resin excellent in harsh environment stability and storage stability in a high temperature and high humidity environment, and a toner containing the charge control agent resin.

The present invention is a charge control resin obtained by polymerizing at least a polymerizable monomer and a polymerizable charge control resin, the polymerizable charge control resin comprising an aromatic vinyl monomer unit and a sulfonic acid group A macromonomer containing a monomer unit having a sulfonate group or a sulfonate group as a constituent unit and having a styrenic double bond at the terminal (hereinafter also referred to as “having a styrenic terminal double bond”) Yes, it has peaks derived from double bonds at 4.6 to 4.9 ppm and 5.0 to 5.3 ppm in the measurement of nuclear magnetic resonance apparatus ( ¹ H-NMR) using deuterated chloroform solvent, The present invention relates to a charge control resin having a value of 5.0 mgKOH / g or more and 50.0 mgKOH / g or less.
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 stability in harsh environments and storage stability under a high temperature and high humidity environment, and a toner containing the charge control agent.

FIG. 2 is a schematic configuration diagram illustrating an example of a process cartridge and an image forming apparatus.

Hereinafter, the present invention will be described in detail.
The charge control resin of the present invention is a charge control resin obtained by polymerizing at least a polymerizable monomer and a polymerizable charge control resin, the polymerizable charge control resin comprising an aromatic vinyl monomer unit, and A macromonomer containing a monomer unit having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group (hereinafter also referred to as a sulfonic acid group) as a constituent unit and having a styrenic double bond at the terminal, In the measurement of a nuclear magnetic resonance apparatus ( ¹ H-NMR) using a chloroform solvent, there are peaks derived from double bonds at 4.6 to 4.9 ppm and 5.0 to 5.3 ppm, and the acid value is 5 It is characterized by being not less than 0.0 mgKOH / g and not more than 50.0 mgKOH / g.
Since the polymerizable charge control resin is a macromonomer having a styrenic terminal double bond represented by the following formula (1), the charge control having a crosslinked structure via the terminal part by reacting with the polymerizable monomer A resin can be obtained. It is considered that the cross-linked structure of a resin having a sulfonic acid group or the like suppresses unevenness due to bleeding or movement of the resin having a sulfonic acid group or the like under a severe environment such as high temperature and high humidity. A charge control resin in which bleeding and movement of a resin having a sulfonic acid group or the like are suppressed is excellent in harsh environment stability and storage stability under a high temperature and high humidity environment.
The styrenic terminal double bond of the polymerizable charge control resin 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 ¹ H-NMR measurement. Have. The structure of the polymerizable charge control resin having a styrenic terminal double bond is shown in (1) below.

（Ｒは、芳香族ビニル単量体単位、スルホン酸基、スルホン酸塩基又はスルホン酸エステル基を有する単量体単位、所望によりその他の単量体単位を共重合体の構成単位とする共重合体）

(R is a copolymer having an aromatic vinyl monomer unit, a monomer unit having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group, and, if desired, another monomer unit as a constituent unit of the copolymer. Coalesce)

The charge control resin of the present invention is obtained by polymerizing at least a polymerizable monomer and a polymerizable charge control resin.
The polymerizable charge control resin contains an aromatic vinyl monomer unit and a monomer unit having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group as a constituent unit, and has a styrenic double bond at the terminal. It is a macromonomer having.
Polymerizability The sulfonic acid group and the like are negatively chargeable, and by having the functional group, negative chargeability under high humidity becomes good. The mass ratio [A: B] of the aromatic vinyl monomer unit [A] and the monomer unit [B] having a sulfonic acid group or the like is preferably 70:30 to 98: 2, and 85: More preferably, it is 15-95: 5. Further, the content of other monomer units as desired is in a range that does not affect the effects of the present invention.
The type of sulfonic acid group or the like or the content of the monomer unit having a sulfonic acid group or the like is adjusted by selecting the monomer type and the addition amount shown below. Presence / absence of sulfonic acid group and the like and content of monomer unit having sulfonic acid group and the like are determined by liquid chromatograph mass spectrometer (LC / MS), gas chromatograph mass spectrometer (GC / MS), nuclear magnetic resonance analyzer. (NMR), infrared spectrometer (IR), mass spectrometer (MS).
Examples of the monomer having a sulfonic acid group include sulfones such as styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2-methacrylamide-2-methylpropane sulfonic acid, vinyl sulfonic acid, and methacryl sulfonic acid. Examples thereof include vinyl monomers having an acid group or the like, or maleic acid amide derivatives, maleimide derivatives, and styrene derivatives having the following structural formula (2). Preferred is a vinyl monomer having a sulfonic acid group or the like, more preferred is (meth) acrylamide having a sulfonic acid group or the like, and further preferred is an acrylamide having a sulfonic acid group and / or a sulfonic acid group. is there. (Meth) acrylamide means methacrylamide or acrylamide.
Acrylamide having a sulfonic acid group and / or a sulfonic acid group has good chargeability under high temperature and high humidity. In the case other than acrylamide having a sulfonic acid group and / or a sulfonic acid group, the chargeability at high temperature and high humidity tends to decrease. The presence or absence and content of acrylamide having a sulfonic acid group and / or a sulfonic acid group can be determined by liquid chromatography / mass spectrometry (LC / MS), gas chromatography / mass spectrometry (GC / MS), nuclear magnetic resonance analyzer (NMR). ), An infrared spectrometer (IR), and a mass spectrometer (MS).

As the aromatic vinyl monomer and other monomers as desired, polymerizable monomers as exemplified below can be used.
Monofunctional polymerizable monomers include styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p -Styrene derivatives such as phenylstyrene; 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 Acrylates such as methyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; , 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, diethyl phosphate ethyl methacrylate Methacrylic acid esters such as dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether, vinyl ethyl ether, vinyl And vinyl ethers such as isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and 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.
Of these, styrene and styrene derivatives are preferred as the aromatic vinyl monomer, and (meth) acrylic acid ester is preferred as the other monomer.

The method for producing the polymerizable charge control resin having a styrenic terminal double bond is not particularly limited, and for example, a high temperature polymerization method can be used. The high temperature polymerization method means that the monomer 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 polymerization solvent, the pressure becomes 0.4 MPa at 220 ° C.
The following are mentioned as a polymerization initiator used. 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. In particular, a peroxide-based polymerization initiator is preferable because a hydrogen abstraction reaction easily occurs. 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.
For example, in a styrene copolymer having a sulfonic acid group and the like produced by polymerization at a high temperature of 170 ° C. or higher, 4.6 to 4 in ¹ H-NMR measurement using a deuterated chloroform solvent.
. Peaks derived from terminal double bonds different from the styrene monomer are observed at 9 ppm and 5.0 to 5.3 ppm. That is, the polymerizable charge control resin obtained by the above production method has a styrenic terminal double bond, and the terminal double bond is crosslinked during the production of the charge control resin. Thus, by introducing a certain cross-linked structure into the charge control resin, it is possible to suppress unevenness due to bleeding or movement of the resin having a sulfonic acid group or the like under a severe environment such as high temperature and high humidity. Further, it is considered that the cross-linked structure has a good influence on the negative chargeability such as a sulfonic acid group related to chargeability.

The acid value of the polymerizable charge control resin is 5.0 mgKOH / g or more and 50.0 mgKOH / g or less. When the acid value of the polymerizable charge control resin is 5.0 mgKOH / g or more and 50.0 mgKOH / g or less, performance excellent in severe environmental stability can be obtained. The acid value is preferably 10.0 mgKOH / g or more and 40.0 mgKOH / g or less, more preferably 10.0 mgKOH / g or more and 25.0 mgKOH / g or less. When the acid value is smaller than 5.0 mgKOH / g, the chargeability is lowered under high humidity. On the other hand, when the acid value is larger than 50.0 mgKOH / g, severe environmental stability is deteriorated under low humidity.
The acid value of the polymerizable charge control resin can be adjusted by selecting the type and amount of the functional group in the polymerizable charge control resin.
The ratio of the styrenic terminal double bond of the polymerizable charge control resin is preferably 0.10 mol% or more and 20.00 mol% or less, and more preferably 2.00 mol% or more and 10.00 mol% or less. When the ratio of the styrenic terminal double bond of the polymerizable charge control resin is 0.10 mol% or more and 20.00 mol% or less, the chargeability in a harsh environment and the storage stability in a high-temperature and high-humidity environment are good. When it is less than 0.10 mol%, bleeding and movement of a resin having a sulfonic acid group or the like in a harsh environment tend to deteriorate. If it is greater than 20.00 mol%, the chargeability and the low-temperature fixability tend to deteriorate.
The ratio of the styrenic terminal double bond of the polymerizable charge control resin can be adjusted by the polymerization reaction temperature during the production of the polymerizable charge control resin and the pressure during the polymerization reaction.
The number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of the above-mentioned polymerizable charge control resin in tetrahydrofuran (THF) 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) can be adjusted by the amount of solvent, the solvent species, the polymerization reaction temperature, and the amount of polymerization initiator during the production of the polymerizable charge control resin.
On the other hand, the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the above-mentioned polymerizable charge control resin in tetrahydrofuran (THF) is preferably 2,000 or more and 50,000 or less. 2,000 to 30,000, more preferably 2,000 to 6,000. 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 storability from the inside of the resin and charge stability in a high-humidity environment due to leaching from the inside of the resin. Tend to decrease. In addition, when the weight average molecular weight (Mw) is larger than 50,000, the charge amount is likely to decrease. In the present invention, the weight average molecular weight (Mw) of the polymerizable charge control resin can be adjusted by the solvent amount, the solvent species, the polymerization reaction temperature, and the polymerization initiator amount at the time of producing the polymerizable charge control resin.
The glass transition temperature (Tg) of the polymerizable charge control resin measured by a differential scanning calorimeter (DSC) is preferably 40 to 100 ° C. When the glass transition temperature is less than 40 ° C., the strength of the entire toner particles is lowered, and transferability and development characteristics are liable to be lowered during a durability test of a large number of sheets. Furthermore, there is a problem that the toner particles aggregate in a high temperature and high humidity environment and storage stability is lowered. On the other hand, if the glass transition temperature exceeds 100 ° C., the problem of poor fixing tends to occur. On the other hand, 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. May be. In this case, the resin component constituting the toner particles corresponds to the charge control resin of the present invention. The polymerizable charge control resin is preferably used in an amount of 0.1 to 30.0 parts by mass with respect to 100.0 parts by mass of the polymerizable monomer.
Further, a polymerizable monomer composition containing at least a polymerizable monomer and a polymerizable charge control resin is polymerized to obtain a charge control resin, and then toner particles containing at least the charge control resin and a colorant. You may get In this case, the polymerizable charge control resin is preferably used in an amount of 30.0 to 80.0% by mass in the charge control resin.

The charge control resin of the present invention is a monomer composition containing a polymerizable charge control resin having a styrenic terminal double bond and a polymerizable monomer, and, if necessary, other additives such as a polymerization initiator. It is manufactured by preparing a product and polymerizing a polymerizable monomer.
Although the said polymerizable monomer is not specifically limited, In the said polymeric charge control resin, the monomer illustrated as an aromatic vinyl monomer and the other monomer depending on necessity can be used. As the polymerization initiator, those exemplified in the polymerizable charge control resin can be used. The polymerization conditions are not particularly limited, and usually used conditions 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. These 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 content of the charge control resin is 7,000 or more and 50,000 or less, it is excellent in harsh environment stability and storage stability under high temperature and high humidity environment. Performance. When the weight average molecular weight (Mw) is smaller than 7,000, the bleeding and movement of the resin having a sulfonic acid group or the like in a high temperature and high humidity environment tend to deteriorate, and the chargeability tends to be low. On the other hand, when the weight average molecular weight (Mw) is larger than 50,000, the chargeability and the low-temperature fixability tend to be lowered.
The said weight average molecular weight (Mw) can be adjusted with the kind of monomer at the time of charge control resin manufacture, the amount of polymerization initiators, polymerization reaction temperature, and reaction time.
The glass transition temperature (Tg) of the charge control resin is preferably 40 to 100 ° C. More preferably, it is higher than 70 ° C and not higher than 100 ° C, and more preferably 73 to 100 ° C. When the glass transition temperature is less than 40 ° C., the fluidity and storability of the toner are inferior, and the transferability is also inferior. When the glass transition temperature exceeds 100 ° C., the fixability at the time of an image having a high toner printing rate is deteriorated.
The charge control resin preferably contains 0.01 to 20.00% by mass of a unit derived from a monomer having a sulfonic acid group or the like, more preferably 0.05 to 10.00% by mass, More preferably, the content is 0.10 to 7.00% by mass. When the amount is less than 0.01% by mass, the effect of the polymerizable charge control resin cannot be sufficiently obtained, and when it exceeds 20.00% by mass, the chargeability and the fixability tend to deteriorate.
The production method of the charge control resin includes a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, an ionic polymerization method, etc., but the solution polymerization method is preferable from the viewpoint of operability.
The charge control resin has a structure represented by the following formula. The counter ions are preferably hydrogen ions, sodium ions, potassium ions, calcium ions, and ammonium ions, and more preferably hydrogen ions.
X (SO ₃ ⁻ ) _n · _m Y ^{k +}
(In the formula, X represents a polymer site, Y ⁺ represents a counter ion, k is a valence of the counter ion, m and n are integers, and n = k × m.)

  In the toner of the present invention, the content of the monomer unit having a sulfonic acid group or the like is preferably 0.001 to 5.000 parts by mass, and 0.005 to 2 parts per 100.000 parts by mass of the binder resin. The amount is more preferably 0.000 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 a sulfonic acid group or the like 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. Since the toner contains the charge control resin of the present invention, the toner exhibits excellent performance in harsh environment stability, storage stability in a high temperature and high humidity environment, member contamination, and development durability. In contrast, a charge control resin produced without using a polymerizable charge control resin is particularly deteriorated in harsh environment stability and storage stability under a high temperature and high humidity environment. That is, when the toner contains the charge control resin of the present invention, the toner exhibits stable charging performance even in a harsh environment, and the storage stability, suppression of member contamination, and development durability in a high temperature and high humidity environment are improved. .
This is because the charge control resin of the present invention has a cross-linked structure as described above, and this cross-linked structure is caused by bleeding or movement of a resin having a sulfonic acid group or the like under a severe environment such as high temperature and high humidity. This is considered to be because non-uniformity is suppressed, and the cross-linked structure has a good influence on negative chargeability such as a sulfonic acid group related to chargeability.
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) is preferable because it 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. 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 a sulfonic acid group or the like 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 pulverized at the interface of the charge control resin, the charge control resin is likely to be further pulverized at the interface, the chargeability is deteriorated, and the sulfonic acid group in a harsh environment It is difficult to suppress unevenness due to bleeding or movement of the resin having the above.
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 high temperature and high humidity environment tends to be good. In the case where the charge control resin of the present invention is not used, it is difficult to suppress unevenness due to bleeding or movement of a resin having a sulfonic acid group or the like 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 high-temperature and high-humidity environment because the toner particles are formed with the charge control resin deposited in the vicinity of the toner surface. In the case where the charge control resin of the present invention is not used, it is difficult to suppress unevenness due to bleeding or movement of a resin having a sulfonic acid group or the like 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. Next, a polymerizable monomer composition containing at least the charge control resin, the colorant, and the polymerizable monomer is suspended and granulated in an aqueous medium, and the polymerizable monomer is polymerized to form a toner. This is an embodiment of obtaining particles. 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 a sulfonic acid group or the like in a harsh environment is suppressed.

Among the above-described polymerization methods, the suspension polymerization method is particularly preferable as the toner production method of the present invention. Hereinafter, explanation is added regarding the suspension polymerization method.
In the suspension polymerization method, a polymerizable monomer composition containing at least a polymerizable monomer, a colorant, and a polymerizable charge control resin is suspended in an aqueous medium, and a solution of the polymerizable monomer composition is obtained. In this method, toner particles are produced through at least a granulation step for producing droplets and a polymerization step for polymerizing a polymerizable monomer and a 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 reactive functional group for the purpose of improving the viscosity change of the toner at a high temperature. Examples of the reactive functional group include a double bond, an isocyanate group, an epoxy group, an amino group, a carboxylic acid group, and a hydroxyl group.
The low molecular weight resin is intended to improve low-temperature fixability and blocking resistance, and its weight average molecular weight (Mw) measured by GPC of its THF soluble content is 2,000 to 6,000. Preferably there is.
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 polycondensates such as polyamides, or addition polymers such as polyethers and polyimines.
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 polyhydric alcohol and a polyvalent carboxylic acid by a known production method. Among the monomers constituting the polyester resin, as the polyhydric alcohol, ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, diethylene glycol, 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 (I) And diols represented by the following general formula (II). 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（Ｉ）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 (I), 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, the polyvalent carboxylic acids include naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, succinic acid, adipic acid, sebacin Dicarboxylic acids such as 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; .
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 according to 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. For polymerization, conventional polymerization catalysts such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide and the like can be used. Further, the polymerization temperature and the amount of catalyst are not particularly limited, and may be arbitrarily selected as necessary.
The polyester resin is preferably 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 more 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, It is more preferable to contain thru | or 40 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. Moreover, when producing | generating vinyl modified polyester resin, the reactive group which couple | bonds a vinyl polymer and polyester is polyester resin, a vinyl polymer, the monomer which comprises 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) After forming a vinyl polymer, it is a method of forming a vinyl-modified polyester resin while polymerizing polyester in the presence thereof. 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 for producing a vinyl-modified polyester resin 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 esters; vinyl esters such as 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, lauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate. These polymerization initiators are preferably added in an amount of 0.500 to 25.000% 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. Examples of the crosslinkable monomer include the following. 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 preferred addition amount is 0.001 to 15,000 mass% of the polymerizable monomer.
The binder resin of 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.
Further, in the present invention, when preparing an aqueous medium using a hardly water-soluble inorganic dispersion stabilizer, the amount of these dispersion stabilizers used is 0.2 with respect to 100.0 parts by mass of the polymerizable monomer. It is preferable that it is thru | or 2.0 mass parts. 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.
Petroleum wax such as paraffin wax, microcrystalline wax, 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 (the derivatives include oxides, block copolymers with vinyl monomers, and graft modified products). Furthermore, 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.
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 2.0 to 30.0% by mass of wax in the toner particles. When the amount is less than 2.0% by mass, the high-temperature offset resistance is lowered, and further, the image on the back surface may exhibit an offset phenomenon when fixing a double-sided image. When the amount is more than 30.0% by mass, toner particles are easily 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 examples thereof include the following known ones.
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. Examples include isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. 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 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 that are toned to 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.
The content of the colorant is preferably 3.0 to 15.0 parts by mass with respect to 100.0 parts by mass of the binder resin or polymerizable monomer.

The toner of the present invention can contain a charge control agent. A well-known thing can be used as a charge control agent. 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.
Organometallic compounds and chelate compounds are effective as charge control agents for controlling the toner to be negatively charged. Monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids And dicarboxylic acid-based metal compounds. Others include aromatic oxycarboxylic acids, aromatic mono and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenols. Further examples include urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarene, and resin charge control agents.
The toner of the present invention can contain these charge control agents singly or in combination of two or more. Among these charge control agents, metal-containing salicylic acid compounds are preferable, and the metal is particularly preferably aluminum or zirconium. The most preferred charge control agent is an aluminum 3,5-di-tert-butylsalicylate compound. The addition amount of the charge control agent 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 preferably contains toner particles and inorganic fine powder for the purpose of imparting various properties. The inorganic fine powder is preferably added to the toner particles as an external additive. The 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 inorganic fine powder, the following are used, for example.
(1) Fluidity imparting agent: alumina, titanium oxide, silica, carbon black, and carbon fluoride.
(2) Abrasive: strontium titanate, cerium oxide, alumina, magnesium oxide, chromium oxide, nitride (for example, silicon nitride), metal salt (for example, calcium sulfate, barium sulfate, calcium carbonate).
(3) Lubricant: Zinc stearate, calcium stearate.
(4) Charge controllable particles: tin oxide, titanium oxide, zinc oxide, silica, alumina, carbon black.
These inorganic fine powders are more preferably hydrophobized from the viewpoint of adjusting the chargeability of the toner and improving the characteristics under a high humidity environment. When the inorganic fine powder added to the toner absorbs moisture, the chargeability as the toner is lowered, and the developability and transferability are easily lowered.
Treatment agents for hydrophobic treatment of inorganic fine powders include 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 as or after the hydrophobic treatment with the coupling agent. Hydrophobized inorganic fine powder treated with silicone oil can maintain a high toner charge amount even under a high humidity environment, and can reduce selective developability.
The addition amount of the inorganic fine powder is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 3.5 parts by mass with respect to 100.0 parts by mass of the toner particles. These inorganic fine powders may be used alone or in combination.
The BET specific surface area of the inorganic fine powder is preferably 10 m ² / g or more and 450 m ² / g or less. Here, the BET specific surface area of the 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 1,000 Pa · s or more and 40,000 Pa · s or less, the toner has excellent low-temperature fixability. On the other hand, the toner containing the charge control resin of the present invention has a sulfonic acid group bleed on the toner surface or a sulfonic acid group on the toner surface. The flow of the resin can be prevented. The viscosity at 100 ° C. is more preferably 2,000 Pa · s or more and 20,000 Pa · s or less. 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. In addition, with use over a long period of time, the inorganic fine powder added as an external additive is embedded 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 addition, the said 100 degreeC viscosity can be adjusted with the addition amount of low molecular weight resin, the monomer seed | species at the time of binder resin manufacture, the amount of polymerization initiators, polymerization reaction temperature, and reaction time.
The value of 100 ° C. viscosity of the toner measured by a constant load extrusion type capillary rheometer can be determined 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 diameter (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 5.0 to 7.0 μm. More preferably.
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), put into a cylindrical filter paper (for example, No. 86R manufactured by Toyo Filter Paper), passed through a Soxhlet extractor, extracted with 200 ml of THF as a solvent for 20 hours, and soluble components extracted by the solvent are extracted. After concentration, vacuum dry at 40 ° C. for several hours and weigh the amount of THF soluble (W2 g). The weight of a component other than a resin component such as a pigment in the toner (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 10,000 to 80. , 000 is preferable, and 10,000 to 60,000 is more preferable. When the weight average molecular weight (Mw) of the toner is less than 10,000, the blocking resistance and durability are likely to deteriorate, and when it exceeds 80,000, 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 weight average molecular weight (Mw) of the low molecular resin, the polymerization reaction temperature at the time of toner production, the polymerization time, the polymerization initiator amount, and the chain transfer agent amount. And the amount of the crosslinking agent can be adjusted.
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: 5 to 100 is preferable, and 5 to 30 is more preferable. 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 is a circularity from 0.40 to 1.00, 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 measuring acid value of resin>
The acid value is the number of mg of potassium hydroxide necessary to neutralize the acid contained in 1.0 g of the sample. The acid value of the resin is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.
(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95 vol%), and ion exchanged water is added to make 100 ml to obtain a phenolphthalein solution.
7 g of special grade potassium hydroxide is dissolved in 5 ml of water, and ethyl alcohol (95 vol%) is added to make 1 l. In order not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 ml of 0.1 mol / l hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxide required for neutralization. Determined from the amount of potassium solution. As the 0.1 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.
(2) Operation (A) Main test 2.0 g of the pulverized sample is precisely weighed into a 200 ml Erlenmeyer flask, and 100 ml of a mixed solution of toluene / ethanol (3: 1) is added and dissolved over 5 hours. Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.
(B) Blank test Titration is performed in the same manner as described above, except that no sample is used (that is, only a mixed solution of toluene / ethanol (3: 1) is used).
(3) The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (ml) of a potassium hydroxide solution in a blank test, C: addition amount (ml) of a potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g).

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 as a solvent, 50 parts by mass of 2-propanol, and 94.0 parts by mass of styrene as a monomer Then, 6.6 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid was added and heated under pressure until the reaction temperature reached 195 ° C. while stirring. The pressure at this time was 0.4 atm. 2,2′-azobisisobutyronitrile 0.8 which is a polymerization initiator
A solution diluted with 20 parts by mass of 2-propanol was added dropwise 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 polymerizable charge control resin thus obtained has a Tg of about 83 ° C., a main peak molecular weight (Mp) of 2,900, a number average molecular weight (Mn) of 2,100, and a weight average molecular weight (Mw) of 3,100. The acid value was 22.1 mgKOH / g. In ¹ H-NMR (EX-400: 400 MHz manufactured by JEOL Ltd.), peaks derived from terminal double bonds were observed at 4.7 ppm and 5.1 ppm. The ratio of double bonds was 2.50 mol%. The obtained resin is referred to as “polymerizable charge control resin 1”.

<Production example of polymerizable charge control resin 2>
In the production example of the polymerizable charge control resin 1, in the same manner as in the production example of the polymerizable charge control resin 1, except that 6.6 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid was changed to 1.8 parts by mass. A polymerizable charge control resin 2 was obtained.
<Production Example of Polymerizable Charge Control Resin 3>
In the production example of the polymerizable charge control resin 1, in the same manner as in the production example of the polymerizable charge control resin 1, except that 6.6 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid was changed to 14.8 parts by mass. A polymerizable charge control resin 3 was obtained.
<Production Example of Polymerizable Charge Control Resin 4>
In the production example of the polymerizable charge control resin 1, except that 6.6 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid was changed to 5.4 parts by mass of styrene sulfonate, In the same manner, a polymerizable charge control resin 4 was obtained.
<Production Example of Polymerizable Charge Control Resin 5>
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 2.0 parts by mass. Thus, a polymerizable charge control resin 5 was obtained.
<Production example of polymerizable charge control resin 6>
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 6 was obtained.
<Production Example of Polymerizable Charge Control Resin 7>
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 0.5 part by mass. Thus, a polymerizable charge control resin 7 was obtained.
<Production example of polymerizable charge control resin 8>
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 8 was obtained.
<Production Example of Polymerizable Charge Control Resin 9>
In the production example of the polymerizable charge control resin 1, the polymerizable charge control resin is the same as the production example of the polymerizable charge control resin 1 except that the reaction temperature is changed from 195 ° C. to 170 ° C. and 0.4 Mpa to 0.1 Mpa. 9 was obtained.
<Production Example of Polymerizable Charge Control Resin 10>
In the production example of the polymerizable charge control resin 1, the polymerizable charge control resin is the same as the production example of the polymerizable charge control resin 1 except that the reaction temperature is changed from 195 ° C. to 220 ° C. and 0.4 Mpa to 0.5 Mpa. 10 was obtained.
<Production Example of Polymerizable Charge Control Resin 11>
In the production example of the polymerizable charge control resin 1, the polymerizable charge control resin is the same as the production example of the polymerizable charge control resin 1 except that the reaction temperature is changed from 195 ° C. to 162 ° C. and 0.4 Mpa to 0.1 Mpa. 11 was obtained.
<Production example of polymerizable charge control resin 12>
In the production example of the polymerizable charge control resin 1, in the same manner as in the production example of the polymerizable charge control resin 1, except that the reaction temperature was changed from 195 ° C. to 230 ° C. and 0.4 Mpa to 0.5 Mpa. 12 was obtained.

<Example of production of non-polymerizable charge control resin 1>
In a reaction vessel equipped with a reflux tube, a stirrer, a thermometer, a nitrogen introduction tube, a dropping device, and a decompression device, 255 parts by mass of methanol as a solvent, 145 parts by mass of 2-butanone and 100 parts by mass of 2-propanol, as a monomer 88 parts by mass of styrene, 6.2 parts by mass of 2-ethylhexyl acrylate, and 6.6 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid were added and heated under reflux at normal pressure. A solution prepared by diluting 0.8 part by mass of 2,2′-azobisisobutyronitrile as a polymerization initiator with 20 parts by mass of 2-butanone was added dropwise 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-butanone was added dropwise over 30 minutes, and further stirred for 5 hours under reflux at normal pressure to polymerize. Ended.
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 methyl ethyl ketone in methanol for reprecipitation. 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 polymerizable charge control resin thus obtained has a Tg of about 83 ° C., a main peak molecular weight (Mp) of 19,400, a number average molecular weight (Mn) of 12,900, and a weight average molecular weight (Mw) of 21,000. The acid value was 20.2 mgKOH / g. Further, ¹ H-NMR (EX-400: 400MH manufactured by JEOL Ltd.
In z), no peak derived from the terminal double bond was observed. The obtained resin is designated as non-polymerizable charge control resin 1.

(Example of production of polyester resin (1))
・ Terephthalic acid: 11.1 mol ・ Bisphenol A-propylene oxide 2-mol adduct (PO-BPA): 10.2 mol
The above monomers are 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 the pressure is reduced to 190 ° C. according to a conventional method while reducing the pressure in a nitrogen atmosphere. The polyester resin 1 was obtained by reacting until Tg reached 70 ° C. Weight average molecular weight (Mw) is 10,600, number average molecular weight (Mn)
Was 3,340 and the acid value was 20.4 mgKOH / g.

(Production example of styrene resin (1))
A reactor equipped with a dropping funnel, a Liebig cooler, a nitrogen-filled tube (nitrogen flow rate 100 ml / min) and a stirrer was charged with 610 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 resulting styrene resin had a weight average molecular weight (Mw) of 8,300 and a Tg of 61 ° C. This is 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 2.2 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 resin had a weight average molecular weight (Mw) of 432,000 and a Tg of 64 ° C. This is designated as styrene resin (2).

(Production example of charge control resin 1 and toner particles 1)
In a four-necked vessel, 720 parts by weight of ion-exchanged water, 970 parts by weight of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution, and 15.0 parts by weight of a 1.0 mole aqueous HCl solution are added, and a high-speed stirring device TK is added. -Hold at 60 ° C with stirring at 12,000 rpm using a homomixer. To this, 100 parts by mass of a 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 control agent 1 (3,5-di -Aluminum compound of tert-butylsalicylic acid)
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.]
10.0 parts by mass 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate 9 serving 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 0.0 part by mass (toluene solution 50%) was added was put into an aqueous dispersion medium, and granulated for 5 minutes while maintaining the rotation 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 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 polymer particle slurry 1. Dilute hydrochloric acid was added to the container containing the polymer particle slurry 1 to remove the dispersion stabilizer. Further, the polymer particles 1 having a weight average particle diameter of 5.7 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 example of charge control resins 2 to 12 and toner particles 2 to 12)
In the manufacture example of the charge control resin 1, the charge control resins 2 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 2 to 12. . The charge control resins 2 to 12 are toner particles 2 to 12. Table 1 shows the physical properties of each charge control resin, each polymerizable charge control resin used, and each toner particle.

(Production example of charge control resin 13 and toner particles 13)
In the production example of the charge control resin 1, except that 9.0 parts by mass of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (toluene solution 50%) was changed to 14.0 parts by mass The charge control resin 13 was obtained in the same manner as in the manufacture example of the charge control resin 1. The charge control resin 13 was used as toner particles 13. Table 2 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 14 and toner particles 14)
In the production example of the charge control resin 1, except that 9.0 parts by mass of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (toluene solution 50%) was changed to 15.0 parts by mass The charge control resin 14 was obtained in the same manner as in the manufacture example of the charge control resin 1. The charge control resin 14 was changed to toner particles 14. Table 2 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 15 and toner particles 15)
In the production example of the charge control resin 1, except that 9.0 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 15 was obtained in the same manner as in the manufacture example of the charge control resin 1. The charge control resin 15 was used as toner particles 15. Table 2 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 16 and toner particles 16)
In the production example of the charge control resin 1, except that 9.0 parts by mass of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (toluene solution 50%) was changed to 6.0 parts by mass The charge control resin 16 was obtained in the same manner as in the manufacture example of the charge control resin 1. The charge control resin 16 was used as toner particles 16. Table 2 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 17 and toner particles 17)
Styrene resin (1) 60 parts by weight Styrene resin (2) 40 parts by weight Methacrylic acid 1.0 part by weight Copper phthalocyanine pigment 6.5 parts by weight Negative charge control agent 1 (3,5-di-tert-butylsalicylic acid Aluminum compound)
0.5 parts by mass Polymerizable charge control resin 1 1.0 part by mass Wax [Fischer-Tropsch wax, endothermic main peak temperature 78 ° 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 By pulverization and classification using an air classifier, the weight average particle size is 5.1 μm.
m charge control resin 17 was obtained. The charge control resin 17 was used as toner particles 17. Table 2 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 18 and toner particles 18)
[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 (1), endothermic main peak temperature 78.2 ° C.] 12 parts by mass, and 15,000 rpm using a TK homomixer at 55 ° C. 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, dried, and then classified by air to obtain the charge control resin 18. The charge control resin 18 was used as toner particles 18. Table 2 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 19 and toner particles 19)
[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 7.0 parts by weight of nonionic surfactant Nonipol 400 (trade name, manufactured by Toho Chemical Co., Ltd.) and 10.5 parts by weight of anionic surfactant Neogen SC (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Then, 50 parts by mass of ion-exchanged water in which 4.5 parts by mass of ammonium persulfate was dissolved was added while being dispersed and emulsified in a flask dissolved in 550.0 parts by mass of ion-exchanged water and slowly mixed for 10 minutes. Replacement was performed. 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 mixing slowly for 50 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.
[Production of release agent dispersion]
Paraffin wax HNP0190 (melting point: 85 ° C. Nippon Seiwa) 200 parts by weight Anionic surfactant Neogen SC (Daiichi Kogyo Seiyaku Co., Ltd.) 10 parts by weight Deionized water 780 parts by weight The above materials are heated to 95 ° C. The mixture was emulsified with a homogenizer at a discharge pressure of 560 × 10 ⁵ N / m ² and then 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 19)
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, the mixture was filtered and sufficiently washed with ion exchange water to obtain a charge control resin 19. The charge control resin 19 was used as toner particles 19. Table 2 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 20 and toner particles 20)
In the production example of the charge control resin 1, 70.0 parts by mass of styrene was 20.3 parts by mass, 30.0 parts by mass of n-butyl acrylate was 8.7 parts by mass, and 1.0 part by mass of the polymerizable charge control resin 1 was 71. The charge control resin 20 was obtained in the same manner as in the manufacture example of the charge control resin 1 except that the content was changed to 0.0 parts by mass. The charge control resin 20 was used as toner particles 20. Table 2 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 21 and toner particles 21)
In the manufacture example of the charge control resin 1, the charge control resin 21 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 1. The charge control resin 21 was used as toner particles 21. Table 2 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 production example of the charge control resin 17, the polymerizable charge control resin 1 is replaced with the non-polymerizable charge control resin 1.
The charge control resin 22 was obtained in the same manner as in the manufacture example of the charge control resin 17 except that the charge control resin 17 was changed. The charge control resin 22 was used as toner particles 22. Table 2 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 18, the charge control resin 23 was obtained in the same manner as the manufacture example of the charge control resin 18 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 2 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 24 and toner particles 24)
In the manufacture example of the charge control resin 19, the charge control resin 24 was obtained in the same manner as the manufacture example of the charge control resin 19 except that the polymerizable charge control resin 1 was changed to the non-polymerizable charge control resin 1. The charge control resin 24 was used as toner particles 24. Table 2 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 production example of the charge control resin 1, the polymerizable charge control resin 1 is replaced with non-polymerizable charge control resin 1, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate 9.0 parts by mass, 3 parts. A charge control resin 25 was obtained in the same manner as in the manufacture example of the charge control resin 1 except that the content was changed to 0.0 parts by mass. The charge control resin 25 was used as toner particles 25. Table 2 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 a four-necked vessel, 720 parts by weight of ion-exchanged water, 980 parts by weight of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution, and 15.0 parts by weight of an aqueous 1.0 mol HCl solution are added, and a high-speed stirring device TK is added. -Hold at 60 ° C with stirring at 12,000 rpm using a homomixer. To this, 100 parts by mass of a 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 49.4 parts by mass n-butyl acrylate 0.6 parts by mass Polymerizable charge control resin 1 50.0 parts by mass Polymerization initiator in monomer mixture A obtained by dispersing the above monomer mixture for 3 hours with an attritor A monomer composition to which 12.0 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 polymer particle slurry A. Dilute hydrochloric acid was added to the container containing the polymer particle slurry A to remove the dispersion stabilizer. Further, filtration, washing, and drying were performed to obtain charge control resin 26 resin particles having a weight average particle diameter of 5.6 μm. Table 2 shows the physical properties of the charge control resin 26 and the polymerizable charge control resin 1 used.
(Production Example of Toner Particle 26)
In a four-necked vessel, 720 parts by weight of ion-exchanged water, 970 parts by weight of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution, and 15.0 parts by weight of a 1.0 mole aqueous HCl solution are added, and a high-speed stirring device TK is added. -Hold at 60 ° C with stirring at 12,000 rpm using a homomixer. To this, 100 parts by mass of a 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 control agent 1 (3,5-di -Aluminum compound of tert-butylsalicylic acid)
0.5 parts by mass Charge control resin 26 5.0 parts by mass Wax [Fischer-Tropsch wax, endothermic main peak temperature 78.2 ° C.]
10.0 parts by mass 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate 9 as a polymerization initiator in the monomer mixture B in which the monomer mixture was dispersed for 3 hours with an attritor The monomer composition to which 0.0 part by mass (toluene solution 50%) was added was put into an aqueous dispersion medium, and granulated for 5 minutes while maintaining the rotation 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 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 polymer particle slurry B. Dilute hydrochloric acid was added to the container containing the polymer particle slurry B to remove the dispersion stabilizer. Further, the toner particles 26 having a weight average particle diameter of 5.7 μm were obtained by filtration, washing and drying. The physical properties of the toner particles 26 are shown in Table 2.

(Production example of toner 1)
To 100 parts by mass of toner particles 1, the specific surface area according to the BET method is 200 m ² / g, the silica treated with 4% by mass of hexamethyldisilazane and 3% by mass of dimethyl silicone oil and 0.15 parts by mass of silica. Toner 1 is obtained by mixing 80 m ² / g of titanium oxide treated with 3% by mass of hexamethyldisilazane with a Henschel mixer (Mitsui Mining Co., Ltd.).
(Production example of toners 2 to 26)
In the toner 1 production example, toners 2 to 26 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 26.

<Example 1>
A toner cartridge of a tandem Canon laser beam printer LBP5500 having the configuration shown in FIG. 1 was used, and 220 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 (32.5 ° C./85% RH) for 24 hours. After leaving for 24 hours in each environment, print out an image with a printing ratio of 1.0% up to 18,500 sheets, solid image density and fog at the initial and 18,500 sheets output, and at 18,500 sheets output Filming and development streaks were evaluated.
Further, a toner cartridge of a tandem Canon laser beam printer LBP5500 having the configuration shown in FIG. 1 was used, 220 g of toner 1 was loaded, and left in a harsh environment (40 ° C./95%) for 148 hours. After that, after leaving it in high temperature and high humidity (32.5 ° C./85% RH) for 24 hours, it prints out an image with a printing ratio of 1.0% up to 18,500 sheets, and the initial solid image density and fogging. Evaluation of filming and development streaks when 18,500 sheets were output. The results are shown in Table 3, Table 4, Table 5, and Table 6.

<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 negatively charged polarity toner (trade name: N-01, manufactured by the Japan Imaging Society) were left in the environment shown below for the following time. 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 (32.5 ° C./85% RH), (C / 95%) after 148 hours, high temperature and high humidity (32.5 ° C./85% RH) for 24 hours.
After leaving, the toner 1 and a standard carrier for negatively charged polarity toner (trade name: N-01, manufactured by the Japan Imaging Society) are 120 using a turbula mixer in each environment so that the mass of the toner 1 is 6.0% by mass. The developer was prepared by mixing for 2 seconds. Within 1 minute after mixing the developer obtained, 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 are measured. At this time, the suction pressure is set to 4.0 kPa. Using the mass difference, the stored potential, and the capacitance of the capacitor, the triboelectric charge amount of the toner is calculated from the following equation.
The standard carrier for negatively charged polarity toner (trade name: N-01, manufactured by Japan Imaging Society) used for measurement passes through 250 mesh, and the one remaining on the 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 18,500 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)>
A toner fixing amount of 0.5 mg / cm ² at a process speed of 240 mm / sec by a modified fixing device in which a fixing unit of a laser beam printer LBP5500 manufactured by Canon in the tandem system having the configuration shown in FIG. The unfixed toner image was heated and pressed without oil on the image receiving paper 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: Less than 1.0% B: 1.0% or more, less than 2.5% C: 2.5% or more, less than 4.0% D: 4.0% or more, less than 5.5% E: 5. 5% or more, less than 7.0% F: 7.0% or more

<Filming evaluation>
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 20>
The same evaluation as in Example 1 was performed except that the toner 1 of Example 1 was changed to toners 2 to 20. The results are shown in Table 3, Table 4, Table 5, and Table 6.
<Comparative Examples 1 to 5>
Evaluation similar to Example 1 was performed except that the toner 1 of Example 1 was changed to toners 21 to 25. The results are shown in Table 3, Table 4, Table 5, and Table 6.

Reference Signs List 5 photosensitive drum, 6 developing roller, 7 toner supply roller, 8 toner, 9 regulating blade, 10 developing device, 11 laser beam, 12 charging device, 13 cleaning device, 14 cleaning charging device, 15 fixing device, 16 driving roller, 17 Transfer roller, 18 Bias power supply, 19 Tension roller, 20 Transfer conveyance belt, 21 Drive roller, 22 Paper, 23 Paper feed roller, 24 Adsorption roller

Claims (7)

A charge control resin obtained by polymerizing at least a polymerizable monomer and a polymerizable charge control resin,
The polymerizable charge control resin contains an aromatic vinyl monomer unit and a monomer unit having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group as a constituent unit, and a styrenic double bond at the terminal. In the measurement of a nuclear magnetic resonance apparatus ( ¹ H-NMR) using a deuterated chloroform solvent, peaks derived from double bonds at 4.6 to 4.9 ppm and 5.0 to 5.3 ppm A charge control resin characterized by having an acid value of 5.0 mgKOH / g or more and 50.0 mgKOH / g or less.   The charge control resin according to claim 1, wherein the monomer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group is acrylamide having a sulfonic acid and / or a sulfonic acid group.   The charge control resin according to claim 1 or 2, wherein a ratio of the styrenic double bond in the polymerizable charge control resin is 0.10 mol% or more and 20.00 mol% or less.   The weight average molecular weight (Mw) measured by gel permeation chromatography of the tetrahydrofuran-soluble content of the polymerizable charge control resin is 2,000 or more and 50,000 or less, The charge control resin according to any one of the above.   5. The weight average molecular weight (Mw) measured by gel permeation chromatography of the tetrahydrofuran-soluble component of the charge control resin is 7,000 or more and 50,000 or less. The charge control resin according to Item 1.   A toner having toner particles containing a charge control resin, wherein the charge control resin is the charge control resin according to any one of claims 1 to 5.   The toner according to claim 6, wherein the toner 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.

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