JP2010091660A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner that has high temperature fixability and has a high rising speed of electricity charging which lowered when it is left in high humidity. <P>SOLUTION: The toner has toner particles containing at least a binder resin, wax, a coloring agent, and a sulfur-containing polymer. Number (%) of sulfur atoms with respect to the sum of numbers of atoms of respective elements of carbon, oxygen, nitrogen and sulfur detected by surface analysis by the X-ray photoelectron spectroscopy (XPS) of the toner particles is 0.05%-0.74%. The ratio of the number (%) of sulfur atoms to the number (%) of oxygen atoms is 0.050-0.140. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a toner for developing an electrostatic image in an image forming method such as electrophotography and electrostatic printing, or a toner for forming a toner image in a toner jet type image forming method.

  Conventionally, in an image forming method using electrophotography, electrostatic printing, or the like, charged toner particles are configured to develop an electrostatic latent image on a drum by an electrostatic force corresponding to a potential difference on the photosensitive drum. . At this time, the charging of the toner is specifically caused by friction between the toner and the toner or between the toner and the carrier, and further with a regulating blade or the like. For this reason, in addition to the particle size and particle size distribution of the toner, it is essential to control the chargeability.

  In order to control the chargeability of the toner, the triboelectric charging characteristics of the binder resin itself can be used, but the triboelectric charging characteristics of the binder resin generally used for toners are often low, depending on the composition. Control of the charging property is not easy. Therefore, generally, a charge control agent that imparts chargeability is added.

  Conventionally, as a negatively chargeable charge control agent, metal complexes of monoazo dyes, nitrohumic acid and its salts, metal compounds such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid, boron compounds, urea compounds, silicon compounds , Calixarene, sulfonated copper phthalocyanine pigment, chlorinated paraffin and the like. The charge control agents containing these dyes and pigments have a complicated structure, the properties are not constant, and many of them have poor stability, and most of them change their chargeability depending on the environment such as temperature and humidity. In addition, some may be altered by decomposition during heat kneading.

  Furthermore, the charge control agent added to these toners must be present on the toner surface to some extent in order to impart frictional charging ability. As a result, friction between the toners, collision with the carrier, conveyance sleeve or roller, regulating blade, and friction with the photosensitive drum cause these additives to fall off the toner surface, causing contamination of the carrier, developing member, and photosensitive drum. Contamination may occur. As a result, as the number of durable sheets increases, the triboelectric chargeability decreases, and at the same time, deterioration due to contamination progresses, which easily causes problems such as a change in image density and a decrease in image quality. As described above, it can be seen that there are very few charge control agents that can stably provide a toner with sufficient triboelectric chargeability for a long period of time. In addition, in order to apply to a full-color toner, it is preferable that what is added to the toner is colorless, and very few can be put to practical use.

  On the other hand, recent copiers and printers have received various requests such as high image quality, small size and light weight, high speed and high productivity, and energy saving. Development of systems and materials that can achieve energy saving and high reliability is an important technical issue. In order to solve this technical problem, it is indispensable to greatly improve the fixing characteristic ability of the toner, and the ability to be sufficiently fixed on the fixing sheet at a lower temperature (hereinafter referred to as low temperature fixing property). Improvement is necessary. However, in general, when the low-temperature fixing performance is improved, charging control tends to be difficult.

  From the background as described above, studies for achieving both low-temperature fixability and chargeability of toner have been actively conducted. In particular, in recent years, proposals have been made to use a resin having a charge control function as a toner raw material for reasons such as environmental considerations, more stable charging requirements, and manufacturing costs. For example, a toner using a resin containing sulfonic acid group-containing acrylamide as a resin having a charge control function has been proposed (for example, Patent Document 1).

  Patent Document 1 discloses a toner which is a copolymer of a sulfonic acid group-containing acrylamide and a vinyl monomer and has a glass transition point (Tg) of 30 ° C. or higher and 70 ° C. or lower. According to the above invention, the chargeability is excellent, and the glass transition point of the copolymer is 30 ° C. or higher and 70 ° C. or lower, so that the balance between storage stability and fixability is good and environmental dependency is reduced. I can do it.

  However, the present situation is that fogging still tends to occur in an image obtained with a copier or printer left under high humidity. The cause is that the rising speed of the charge that is lowered when left under high humidity is slow, and it is desired to improve their charging performance.

JP 2000-56518 A

  An object of the present invention is to provide a toner that is excellent in low-temperature fixability and has a fast recovery speed of triboelectric charge and a rapid charge rising speed that are reduced when left under high humidity.

  In the toner having toner particles containing at least a binder resin, a wax, a colorant, and a sulfur-containing polymer, the inventors of the present invention have physical properties of the toner having a fast charge rising speed that is reduced when left under high humidity. We studied diligently. As a result, in the toner particles, it was found that there is a close relationship between the constituent elements of the sulfur-containing polymer exhibiting charging properties having excellent environmental characteristics and the constituent elements of the resin forming the outer layer, and the present invention has been achieved.

  The present invention relates to a toner having toner particles containing at least a binder resin, a wax, a colorant, and a sulfur-containing polymer, and carbon detected by surface analysis of the toner particles by an X-ray photoelectron spectroscopy (XPS) method. With respect to the sum of the number of atoms of each element of an atom, oxygen atom, nitrogen atom and sulfur atom, the number% of sulfur atoms with respect to the sum of the number of atoms is 0.05 to 0.74%, and the number of sulfur atoms ( %) / The number of oxygen atoms (%). The present invention relates to a toner having a ratio of 0.050 to 0.140.

  According to the present invention, low-temperature fixability is achieved by highly controlling the presence state of the constituent elements of the sulfur-containing polymer exhibiting excellent charging characteristics with excellent environmental characteristics and the constituent elements of the resin forming the outer layer in the toner particles. Even in the case of having toner, it is possible to provide a toner having a fast charge rising speed which is lowered when left under high humidity.

  The toner of the present invention is a toner having toner particles containing at least a binder resin, a wax, a colorant, and a sulfur-containing polymer, and is detected by a surface analysis of the toner particles by an X-ray photoelectron spectroscopy (XPS) method. The number of sulfur atoms is 0.05 to 0.74% with respect to the sum of the numbers of carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. The above-described effects can be obtained by controlling the ratio of (%) / number of oxygen atoms (%) to 0.050 to 0.140.

  As a reason why the effect of the present invention can be obtained by controlling within this range, the present inventors consider as follows. The sulfur atom on the toner surface is derived from a sulfur-containing polymer containing a sulfonic acid group derivative such as a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester, and serves as a charging site.

  On the other hand, since oxygen atoms on the toner surface are elements with high electronegativity, they exist in a dispersed manner, thereby delocalizing negative charges generated in the toner and leaking charges due to moisture adsorption / desorption. Work as a site. The balance between the amount of sulfur atoms and the amount of oxygen atoms on the toner surface is related to the rising performance of charging, and it is considered that the effect of the present invention is exhibited by controlling this balance.

  In the toner of the present invention, when the number% of sulfur atoms relative to the sum of the number of atoms is less than 0.05, it is difficult to charge the toner particles because the amount of charging sites is small. Further, when the value exceeds 0.74, the amount of charging sites is large, so that the toner is likely to be charged up.

  Further, in the toner of the present invention, when the ratio of the number of sulfur atoms (%) / the number of oxygen atoms (%) is less than 0.050, oxygen atoms with respect to sulfur atoms serving as charging sites. Since it is excessively present, when it is left under high humidity, it is affected by water and the rise of charging is deteriorated.

  On the other hand, when the range of the ratio of the number of sulfur atoms (%) / the number of oxygen atoms (%) is larger than 0.140, since the number of oxygen atoms is smaller than the sulfur atoms on the toner surface, the generated negative Since it is difficult to delocalize the charge, the toner is likely to be charged up.

  The toner of the present invention is capable of highly controlling the existence state of the constituent element of the sulfur polymer containing a sulfonic acid group derivative such as a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester and the constituent element of the resin forming the outer layer. To be achieved.

  The number% of sulfur atoms present on the toner surface is determined by the number of sulfur atoms present in the sulfur-containing polymer and the ratio of the resin that forms the outer layer with the sulfur-containing polymer present on the toner surface.

  For example, in the case of producing toner particles by suspension polymerization in an aqueous medium, a sulfur-containing polymer dissolved in a monomer or a polar resin forming an outer layer has a lower polymerization rate as the polymerization reaction proceeds. Phase separation occurs. At this time, the sulfur-containing polymer and the polar resin forming the outer layer are unevenly distributed on the droplet surface due to the influence of polarity. In this case, the sulfur-containing polymer present on the surface is controlled by controlling the acid value of the sulfur-containing polymer and the acid value of the polar resin that forms the outer layer, and the amount of the polar resin that forms the outer layer with the sulfur-containing polymer. It is possible to adjust the amount.

  On the other hand, the ratio of the number of sulfur atoms (%) / the number of oxygen atoms (%) is the number of sulfur atoms (%) present in the sulfur-containing polymer, the number of oxygen atoms (%), and the polarity that forms the outer layer. It is determined by the number (%) of oxygen atoms present in the resin and the ratio of the sulfur-containing polymer present on the toner surface and the polar resin forming the outer layer. The ratio of the sulfur-containing polymer present on the toner surface to the resin that forms the outer layer is determined by the acid value of the sulfur-containing polymer and the acid value of the resin that forms the outer layer, and the charging of the polar resin that forms the outer layer with the sulfur-containing polymer. Adjustment is possible by controlling the amount.

  Further, in the present invention, a toner having a rapid charge rising speed that is lowered when left under high humidity, the same characteristics in the second half of the durability, and improved toner developability, transferability and fixability. In order to obtain the toner, a capsule toner is preferable.

  This capsule-type toner generally has a structure in which an inner layer is protected by an outer layer. However, when the adhesiveness between the inner layer and the outer layer is weak, if the toner is continuously stressed with continuous output, the outer layer may be peeled off or scraped off, and the surface property of the toner particles may change suddenly.

  And, as the resin that forms the outer layer, it is possible to form the outer layer while ensuring sufficient adhesion to the inner layer when using a resin that has a cyclohexane insoluble content and is easily compatible with the inner layer resin. Thus, it was found that such a rapid change can be suppressed.

  Since cyclohexane has a property of being hardly soluble in a polar solvent, the solubility in a polymer having no polarity is high, but the solubility in a polymer having polarity is low. For this reason, it is considered that a resin having no polarity and a resin having polarity can be separated by dissolving the resin in cyclohexane. That is, the fact that a resin component that is insoluble in cyclohexane in the THF-soluble component means that a polar resin is included.

  In order to increase the compatibility of the inner layer and the outer layer, the binder resin component forming the inner layer and the polar resin forming the outer layer are preferably the same type of resin. In the toner of the present invention, the outer layer The polar resin that forms the polymer is preferably a vinyl polymer.

  When a resin having a polarity that is easily compatible with the binder resin forming the inner layer is used, compatibilization occurs at the interface between the polar resin and the binder resin, and a concentration gradient of the polar resin occurs at the interface. The present inventors are thinking.

  For example, when producing toner particles by suspension polymerization in an aqueous medium, the polar resin dissolved in the monomer progresses in the polymerization reaction, and the solubility in the monomer is reduced, resulting in phase separation. At this time, the polar resin is unevenly distributed on the surface of the droplet due to the influence of the polarity, but since the familiarity between the polar resin and the binder resin component is good, no clear interface is formed between the two components, and the particles It exists with a concentration gradient so that the concentration of the polar resin gradually decreases from the surface toward the inside and the concentration of the binder resin component increases.

  As a result, the adhesion between the inner layer and the outer layer of the toner is increased and the toughness is enhanced, so that the toner is less likely to be destroyed and the developability and transferability of the toner are improved. In addition, when the wax is dissolved in the fixing step, the wax easily moves to the surface of the toner particles quickly, thereby improving the fixability.

  High adhesion between the inner and outer layers of the toner, great toughness against external factors when the toner is pressed, and good bleedability of the wax when the toner is heated The present inventors consider that the fixing property is improved.

  Further, the toner of the present invention preferably has a glass transition temperature (TgA) measured by a differential scanning calorimeter within a range of 40 to 60 ° C. In this case, the adhesion force of the binder resin to the transfer material when the toner is heated and pressurized is improved. Therefore, the low-temperature fixability of the toner can be improved. When TgA is less than 40 ° C., adverse effects on developability and transferability occur, and when TgA exceeds 60 ° C., low-temperature fixability becomes poor. Moreover, the said conditions regarding the said TgA can be satisfy | filled by adjusting the composition ratio etc. of a polymerizable monomer.

  The toner of the present invention preferably has a glass transition temperature (TgB) of 80 to 120 ° C. as measured with a differential scanning calorimeter in the cyclohexane insoluble content in the THF soluble content. As described above, the cyclohexane insoluble component mainly contains a resin having polarity, and the resin having this polarity mainly forms an outer layer. When the glass transition temperature TgB of this component is 80 to 120 ° C., the strength of the outer layer of the toner can be increased, so that the toughness of the toner is improved. As a result, development efficiency can be improved by increasing the stress resistance of the toner during development. Furthermore, since circumferential streaks and toner scattering are reduced, transfer efficiency can be further increased. Further, since the glass transition temperature (TgB) of the toner is affected by the physical properties of the polar resin of the toner raw material, the above-mentioned conditions relating to TgB can be satisfied by adjusting the monomer composition ratio at the time of manufacturing the polar resin. It is.

  The temperature difference (TgB-TgA) between the TgB and the TgA is preferably 25 ° C to 70 ° C. When the temperature difference between TgB and TgA is 25 ° C. to 70 ° C., it is possible to satisfactorily achieve both low temperature fixability and developability of the toner. Further, since the generation of circumferential streaks and toner scattering is reduced, the transfer efficiency can be further increased, and an image with high uniformity can be obtained with respect to images on the same page. Further, even with a transfer material with low smoothness, uniform transfer properties can be obtained.

  The toner of the present invention preferably has an acid value of 5 to 40 mgKOH / g in the cyclohexane insoluble component in the THF soluble component. When the acid value of the cyclohexane insoluble component is 5 to 40 mgKOH / g, the strength of the outer layer of the toner can be increased. As a result, since the toughness of the toner is improved, the development efficiency can be increased by increasing the stress resistance of the toner. Furthermore, since circumferential streaks and toner scattering are reduced, transfer efficiency can be further increased. In addition, since the acid value of the cyclohexane insoluble component is affected by the acid value of the polar resin of the toner raw material, the conditions regarding the acid value of the cyclohexane insoluble component include the type and amount of monomer used in the polar resin production, etc. It is possible to satisfy by adjusting.

  The toner of the present invention preferably has a penetration film thickness (L) of 0.20 to 0.60 μm at a penetration time of 5 seconds when the UV photocurable composition is penetrated into the toner. In addition, when the UV photocurable composition is infiltrated into the toner, it is preferable that the average infiltration rate (Va) at an infiltration time of 5 seconds to 10 seconds is 0.020 to 0.070 μm / s. Furthermore, the average penetration rate (Vb) at a penetration time of 10 seconds to 15 seconds is preferably larger than the average penetration rate (Va) at a penetration time of 5 seconds to 10 seconds.

  The present inventors believe that the penetration rate of the UV photocurable composition into the resin reflects the mobility of the molecular chain of the resin. That is, it is estimated that the higher the molecular chain mobility of the resin, the higher the penetration rate, and the lower the molecular chain mobility, the lower the penetration rate. A resin having a larger molecular chain mobility and a higher permeation rate is more likely to melt the toner during fixing, and the wax tends to ooze out to the surface. However, such a resin has low stress resistance and heat resistance. On the other hand, a resin having a low molecular chain mobility and a low permeation rate has high stress resistance and heat resistance, but the toner is difficult to melt at the time of fixing, and the wax does not easily leak onto the surface. That is, it is preferable to use a resin having a high penetration speed as the resin forming the toner inner layer, and it is preferable to use a resin having a low penetration speed as the resin forming the toner outer layer.

  The osmotic film thickness (L) at a penetration time of 5 seconds reflects the penetration speed in the vicinity of the toner surface. The average penetration speed (Va) at a penetration time of 5 seconds to 10 seconds and an penetration time of 10 seconds to 15 seconds. The average penetration rate (Vb) is considered as an index representing the penetration rate on the surface side of the toner outer layer and on the inner side of the toner outer layer.

  When the osmotic thickness (L) is within the above range, it means that the outermost layer is strong, and sufficient toner toughness can be obtained. Moreover, the bleeding property of the wax at the time of fixing is improved. Therefore, developability and fixability are improved. Therefore, the storage stability is improved.

  When the average penetration rate (Va) at the penetration time of 5 seconds or more and 10 seconds or less is within the above range, the molecular chain mobility of the resin of the toner outer layer is in the optimum range, and sufficient toner toughness can be obtained. Good wax bleeding at the time of fixing can be obtained. Therefore, development characteristics and fixing characteristics are improved.

  Further, when Va and Vb satisfy the relationship Va <Vb, this means that the resin constituting the toner outer layer exists with a density gradient from the vicinity of the toner surface toward the inside, The adhesion between the toner inner layer and the toner outer layer is increased. Therefore, development characteristics and low-temperature fixability are improved. By setting L, Va, and Vb of the toner within the above range, adhesion between the binder resin mainly existing in the toner inner layer and the polar resin mainly existing in the toner outer layer is improved. Further, the resin constituting the toner outer layer exists with a density gradient from the vicinity of the toner surface layer toward the inside. Therefore, when the toner is stressed by the continuous output, the toner outer layer is hardly peeled off or scraped off. Therefore, high development efficiency, reduction in circumferential streaks, and reduction in toner scattering can be achieved. In addition, from the above characteristics, the toner inner layer is difficult to be exposed even when the toner is continuously stressed by continuous output, so that the toner inner layer can be designed to be sufficiently soft. Furthermore, the absence of an interface between the toner inner layer and the toner outer layer improves the bleedability of the wax during fixing. Therefore, it is possible to achieve good low-temperature fixability and high-temperature wrapping resistance of the transfer material without deteriorating development characteristics and storage stability.

  The present inventors presume that the Tg, the degree of crosslinking, the molecular weight, etc. of the resin act in a complex manner as factors that determine the penetration rate. The conditions relating to L, Va and Vb of the toner can be satisfied by adjusting the composition ratio of the polymerizable monomer and reducing the difference in composition between the binder resin and the polar resin. It is.

  In the toner of the present invention, the sulfur-containing polymer may be represented by the following chemical formula (1)

（式中、Ｂ１は置換基を有していてもよい炭素数１又は２のアルキレン構造もしくは置喚基を有していてもよい芳香族環を表し、アルキレン構造における置換基としては、水酸基、炭素数１乃至１２のアルキル基、アリール基又はアルコキシ基であり、芳香族環における置喚基としては、水酸基、炭素数１乃至１２のアルキル基、アリール基又はアルコキシ基であり、また、隣接する炭素を含めて５員環又は６員環の芳香族環を形成していてもよい。Ｒ１は炭素数１乃至１２のアルキル基、アリール基を表す。）
で示すユニットを含む重合体であることが好ましい。

(In the formula, B1 represents an optionally substituted alkylene group having 1 or 2 carbon atoms or an aromatic ring optionally having a substituent, and the substituent in the alkylene structure includes a hydroxyl group, An alkyl group having 1 to 12 carbon atoms, an aryl group or an alkoxy group, and the anchoring group in the aromatic ring is a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an aryl group or an alkoxy group, and is adjacent thereto. (Including carbon, a 5-membered or 6-membered aromatic ring may be formed. R1 represents an alkyl group having 1 to 12 carbon atoms or an aryl group.)
It is preferable that it is a polymer containing the unit shown by.

  The present inventors investigated the physical properties of a toner having excellent charging stability even after being left in a high-temperature and high-humidity environment, as well as a sulfur-containing polymer exhibiting high charging ability with excellent environmental characteristics. And studied diligently. As a result, it has been clarified that by using a sulfur-containing polymer containing a unit having a sulfonate group represented by the chemical formula (1), the effect of developing the charge is further improved.

  That is, a toner containing a sulfur-containing polymer containing a unit having a sulfonic acid ester group represented by the chemical formula (1) is excellent in the start-up characteristic in frictional charging from the initial stage. The reason for this is not clear, but sulfonic acid ester groups are considered to be more hydrophobic than sulfonic acid groups. For this reason, it is assumed that it is less susceptible to the influence of water molecules in the air, and that the electron withdrawing property functions. In addition, it is considered that there is a difference in the friction mechanism at the molecular level from an anionic state such as sulfonate, and the influence on the electric resistance value of the obtained toner surface cannot be ignored.

  In addition, it has been found that the effect on the triboelectric charging ability is more markedly exhibited by the presence of the sulfonate group on the aromatic ring. The reason for this is considered to be that the order of molecular orbitals of the sulfonic acid moiety varies depending on the conjugated system of the aromatic ring by containing the sulfonic acid ester group via the aromatic ring. Therefore, the structure of the aromatic ring and the type and location of the substituent are considered to be factors that greatly influence the charging characteristics of the sulfonate group. The most preferable structure is not generally determined, but a phenyl group and a naphthyl group are preferable structures.

  As shown in the chemical formula (1), the aromatic ring may have other substituents, specifically, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an aryl group, or an alkoxy group. Moreover, adjacent members may form a 5-membered or 6-membered aromatic ring.

  The structure of the sulfonic acid ester is not particularly limited, but it is not preferable that the structure is so bulky that it may affect the triboelectric charging characteristics. Therefore, the ester structure of the sulfonic acid ester is preferably an alkyl ester having 1 to 12 carbon atoms or an aryl ester, and more preferably an alkyl ester having 1 to 4 carbon atoms.

  In the toner of the present invention, the sulfur-containing polymer is preferably a vinyl polymer from the viewpoints of cost and productivity.

  Below, the material used by this invention is demonstrated.

  Examples of the binder resin that can be used in the present invention include polystyrene; homopolymers of styrene substitution products such as poly-p-chlorostyrene and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-vinyltoluene. Copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene -Vinylmethyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, etc. Styrene copolymer; acrylic tree ; Methacrylic resins; polyvinyl acetate; silicone resins; polyester resins; polyamide resin; furan resins, epoxy resins, xylene resins. These resins are used alone or in combination.

  The comonomer for the styrene monomer of the styrene copolymer includes, for example, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid , Methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, monocarboxylic acids having a double bond such as acrylamide or substituted products thereof; maleic acid, butyl maleate, methyl maleate , Dicarboxylic acids having a double bond such as dimethyl maleate and their substitutes; vinyl esters such as vinyl chloride, vinyl acetate and vinyl benzoate; ethylene-based olefins such as ethylene, propylene and butylene. Fin; vinyl methyl ketone, vinyl ketones such as vinyl hexyl ketone, vinyl methyl ether, vinyl ethyl ether, vinyl ethers such as vinyl isobutyl ether. These vinyl monomers are used alone or in combination of two or more.

  As the polymerizable monomer used when the toner of the present invention is produced by the polymerization method, a vinyl polymerizable monomer capable of radical polymerization is used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. Examples of the monofunctional polymerizable monomer include styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, and 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 Styrene derivatives such as p-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-ethylhexylua Acrylic polymerizable monomers such as 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 Mer: 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, diethyl phosphate ester Methacrylic polymerizable monomers such as methyl methacrylate and dibutyl phosphate ethyl methacrylate; Methylene aliphatic monocarboxylic acid esters; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; And vinyl ethers such as methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  Examples of the polyfunctional polymerizable monomer include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, Propylene glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis (4- (acryloxy-diethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tri Ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene Recall dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4- (methacryloxydiethoxy) phenyl) propane 2,2′-bis (4- (methacryloxy-polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether and the like.

  In the present invention, the above-described monofunctional polymerizable monomers are used alone or in combination of two or more, or the above-mentioned monofunctional polymerizable monomers and polyfunctional polymerizable monomers are used in combination. be able to. The polyfunctional polymerizable monomer can also be used as a crosslinking agent.

  Further, when the toner is produced by the suspension polymerization method, the monomer may be selected so that the glass transition temperature of the binder resin obtained by polymerization is lower than the glass transition temperature required for the toner. preferable. The glass transition temperature of the polar resin that mainly forms the outer layer of the toner is preferably increased so that the glass transition temperature of the obtained toner is within the range specified by the present invention. As a result, it is possible to improve developability, transferability and fixability while maintaining good heat resistance that tends to decrease when the glass transition temperature of the binder resin is set low.

  In the present invention, as described above, as the resin for forming the outer layer, it is preferable to use a resin that is easily compatible with the binder resin and has polarity. Specifically, it is preferable to use a resin having the same composition as the binder resin. In the toner of the present invention, the polar resin forming the outer layer is preferably a vinyl polymer. A resin having physical properties such that the glass transition temperature (TgB) and the acid value are within the above-described ranges is preferable. Specifically, for example, nitrogen-containing monomers such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; nitrile monomers such as acrylonitrile; halogen-containing monomers such as vinyl chloride; acrylic acid and methacrylic acid Unsaturated carboxylic acid such as: unsaturated dibasic acid; unsaturated dibasic acid anhydride; polymer of nitro monomer. In particular, a copolymer having styrene (or a derivative thereof), acrylic acid (or methacrylic acid), and an acrylic ester (or methacrylic ester) as a copolymerization component is preferable. In that case, the amount of residual styrene is preferably 300 ppm or less because the familiarity between the polar resin and the binder resin can be improved.

  The resin having the polarity preferably has a weight average molecular weight Mw measured by GPC of 8,000 to 260,000 and Mw / Mn of 1.05 to 5.00. Moreover, it is preferable that the glass transition temperature Tg calculated | required by differential scanning calorimetry (DSC) is 80 to 120 degreeC. The acid value is preferably 5 to 40 mgKOH / g.

  The content of the resin having polarity is preferably 5 to 50 parts by mass, and preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polymerizable monomer or the binder resin.

  In the present invention, as described above, a polymer containing a sulfonic acid group derivative such as a sulfonic acid, a sulfonic acid salt, or a sulfonic acid ester is used as the sulfur-containing polymer having excellent environmental characteristics and high charging ability. Can do.

  Of these, a sulfur-containing polymer exhibiting excellent charging characteristics and excellent environmental characteristics was also studied. As a result, the sulfur-containing polymer has the following chemical formula (1)

（式中、Ｂ１は置換基を有していてもよい炭素数１又は２のアルキレン構造もしくは置喚基を有していてもよい芳香族環を表し、アルキレン構造における置換基としては、水酸基、炭素数１乃至１２のアルキル基、アリール基又はアルコキシ基であり、芳香族環における置喚基としては、水酸基、炭素数１乃至１２のアルキル基、アリール基又はアルコキシ基であり、また、隣接する炭素を含めて５員環又は６員環の芳香族環を形成していてもよい。Ｒ１は炭素数１乃至１２のアルキル基、アリール基を表す。）
で示されるスルホン酸エステル基を有するユニットを含有する含硫黄重合体を用いることが好ましい。

(In the formula, B1 represents an optionally substituted alkylene group having 1 or 2 carbon atoms or an aromatic ring optionally having a substituent, and the substituent in the alkylene structure includes a hydroxyl group, An alkyl group having 1 to 12 carbon atoms, an aryl group or an alkoxy group, and the anchoring group in the aromatic ring is a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an aryl group or an alkoxy group, and is adjacent thereto. (Including carbon, a 5-membered or 6-membered aromatic ring may be formed. R1 represents an alkyl group having 1 to 12 carbon atoms or an aryl group.)
It is preferable to use a sulfur-containing polymer containing a unit having a sulfonate group represented by the formula:

  As the production of the sulfur-containing polymer containing a unit having a sulfonate group represented by the chemical formula (1), for example, the following synthesis method can be used.

  Wide range of chemical formula (2)

で示すユニットを含む重合体と、下記化学式（３）

A polymer containing a unit represented by the following chemical formula (3)

（式中、Ｂ１は置換基を有していてもよい炭素数１又は２のアルキレン構造もしくは置喚基を有していてもよい芳香族環を表し、アルキレン構造における置換基としては、水酸基、炭素数１〜１２のアルキル基、アリール基又はアルコキシ基であり、芳香族環における置喚基としては、水酸基、炭素数１〜１２のアルキル基、アリール基又はアルコキシ基であり、また、隣接する炭素を含めて５員環又は６員環の芳香族環を形成していてもよい。）
で示すスルホン酸基を含有するアミン化合物の少なくとも１種とを、縮合剤を用いて、反応させてアミド結合を形成し、下記化学式（４）

(In the formula, B1 represents an optionally substituted alkylene group having 1 or 2 carbon atoms or an aromatic ring optionally having a substituent, and the substituent in the alkylene structure includes a hydroxyl group, It is a C1-C12 alkyl group, an aryl group, or an alkoxy group, and as an anchoring group in an aromatic ring, it is a hydroxyl group, a C1-C12 alkyl group, an aryl group, or an alkoxy group, and is adjacent. (It may form a 5-membered or 6-membered aromatic ring including carbon.)
Is reacted with at least one amine compound containing a sulfonic acid group represented by the formula (4) to form an amide bond.

（式中、Ｂ１は置換基を有していてもよい炭素数１又は２のアルキレン構造もしくは置喚基を有していてもよい芳香族環を表し、アルキレン構造における置換基としては、水酸基、炭素数１乃至１２のアルキル基、アリール基又はアルコキシ基であり、芳香族環における置喚基としては、水酸基、炭素数１乃至１２のアルキル基、アリール基又はアルコキシ基を表し、また、隣接する炭素を含めて５員環又は６員環の芳香族環を形成していてもよい。）
で示すユニットを含む重合体を製造する工程と；

(In the formula, B1 represents an optionally substituted alkylene group having 1 or 2 carbon atoms or an aromatic ring optionally having a substituent, and the substituent in the alkylene structure includes a hydroxyl group, An alkyl group having 1 to 12 carbon atoms, an aryl group or an alkoxy group, and the anchoring group in the aromatic ring represents a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an aryl group or an alkoxy group, and is adjacent to each other. (It may form a 5-membered or 6-membered aromatic ring including carbon.)
Producing a polymer comprising a unit represented by:

A step of esterifying the polymer containing the unit represented by the chemical formula (4) using an esterifying agent to produce a polymer containing the unit represented by the chemical formula (1);
Can be manufactured.

  The polymer containing the unit represented by the chemical formula (2) is applicable to vinyl polymers, ester polymers, ether polymers, amide polymers, urethane polymers, and urea polymers. The molecular weight of the polymer applicable to the present invention is in the range of 1,000 to 1,000,000 in terms of number average molecular weight. When the number average molecular weight is less than 1000, the composition distribution in the polymer becomes wide, which is not preferable. Moreover, when the number average molecular weight is larger than 1,000,000, it is generally not preferable because it is difficult to dissolve in a solvent during the reaction.

  When the polymer is a vinyl polymer, examples of the unit having a carboxyl group represented by the chemical formula (2) include acrylic acid and methacrylic acid. The polymer in this case may be a homopolymer or a copolymer. When the vinyl polymer containing a unit having a carboxyl group represented by the chemical formula (2) is a copolymer, it is preferably a copolymer with the following vinyl monomer. Specifically, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, p Styrene and its derivatives such as n-dodecylstyrene; ethylene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl acetate , Vinyl ester acids such as vinyl propionate and vinyl benzoate; methacryl Methyl, ethyl methacrylate, propyl methacrylate, methacrylate-n-butyl, isobutyl methacrylate, methacrylate-n-octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethyl methacrylate Α-methylene aliphatic monocarboxylic acid esters such as aminoethyl, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, acrylic acid-n-butyl, acrylic acid-isobutyl, acrylic acid-propyl, acrylic acid-n-octyl, Acrylic esters such as dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl methyl ether, vinyl ethyl ether Vinyl ethers such as vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone. Compounds; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide.

  The compound represented by the chemical formula (3) includes 2-aminoethanesulfonic acid (sometimes called taurine), 2-amino-2-methylpropanesulfonic acid and p-aminobenzenesulfonic acid (also called another name). Sometimes referred to as sulfanilic acid), m-aminobenzenesulfonic acid, o-aminobenzenesulfonic acid, m-toluidine-4-sulfonic acid, p-toluidine-2-sulfonic acid, 4-methoxyaniline-2-sulfonic acid O-anisidine-5-sulfonic acid, p-anisidine-3-sulfonic acid, 2,4-dimethylaniline-6-sulfonic acid, 3,4-dimethylaniline-5-sulfonic acid, 4-isopropylaniline-6- Aminobenzenesulfonic acid derivatives of sulfonic acid, 1-naphthylamine-4-sulfonic acid, 1-naphthyl Min-5-sulfonic acid, 1-naphthylamine-6-sulfonic acid, 1-naphthylamine-7-sulfonic acid, 1-naphthylamine-8-sulfonic acid, 2-naphthylamine-1-sulfonic acid, 2-naphthylamine-5-sulfone Examples thereof include naphthylamine sulfonic acid derivatives such as acids.

  A polymer containing a unit represented by the chemical formula (2) and at least one amine compound represented by the chemical formula (3) containing a sulfonic acid group can be produced using a condensing agent. As the condensing agent, a phosphoric acid condensing agent or the like can be used, and a phosphite ester condensing agent is preferably used. As the phosphites used at this time, triphenyl phosphite is preferably used. The amount of the condensing agent to be used is in a range of 0.1 times mol or more, preferably 1 time mol or more with respect to the compound represented by the chemical formula (2). Further, the condensing agent itself can be used as a reaction solvent.

  The amine compound represented by the chemical formula (3) used in this method is used in an amount of 0.1 to 50.0 times mol, preferably 1.0 mol, based on the unit represented by the chemical formula (2) used as a starting material. It is the range of thru | or 20.0 times mole. During the reaction, a solvent can be used as necessary. As the solvent to be used, pyridine is preferably used. The reaction time is, for example, in the range of 1 to 48 hours. The isolation of the reaction mixture is not particularly limited, but it can be purified by reprecipitation, column chromatography or the like.

  The polymer containing the unit represented by the chemical formula (4) produced by the above method can be subsequently transferred to a step of esterifying sulfonic acid using an esterifying agent. Through the esterification reaction, a polymer containing the unit represented by the chemical formula (1) can be produced. As a method for esterifying the sulfonic acid, a known method can be used. Specific examples include a method of reacting with an alcohol after chlorination of sulfonic acid, a method using a methyl esterifying agent such as dimethyl sulfate, trimethylsilyldiazomethane, and trimethyl phosphate, a method using an orthoformate, and the like. In particular, in the production of a polymer containing a unit represented by the chemical formula (1), a method using an orthoformate is preferable. According to this method, an orthoformate having a desired alkyl group and a polymer having a sulfonic acid group containing a unit represented by the chemical formula (4) can be reacted under relatively mild conditions. Specific examples of the orthoformate ester include trimethyl orthoformate (sometimes called trimethyl orthoformate), triethyl orthoformate (sometimes called triethyl orthoformate), tri-n-formate. -Propyl (sometimes called tri-n-propyl orthoformate), tri-iso-propyl orthoformate (sometimes called tri-iso-propyl orthoformate), tri-orthoformate -N-butyl (also referred to as tri-n-butyl orthoformate), tri-sec-butyl orthoformate (also referred to as tri-sec-butyl orthoformate), orthogi Tri-tert-butyl acid (also known as tri-t Sometimes called rt- butyl orthoformate there) and the like. These can be selected according to the desired sulfonate ester. The esterifying agent may be used alone or in combination. The amount of the esterifying agent used is preferably in the range of 1.0 to 500-fold molar amount with respect to the unit represented by the chemical formula (4), although it depends on the desired proportion of sulfonic acid.

  The reaction temperature in the esterification by the above method is not particularly limited, but is usually carried out in the range of 0 ° C. to the boiling temperature of the esterifying agent. The reaction time is usually in the range of 1 to 48 hours, preferably in the range of 1 to 24 hours. The isolation of the reaction mixture is not particularly limited, but the remaining esterifying agent and its decomposition product contained in the reaction mixture can be removed, for example, by distillation. Subsequently, the residue can be purified by reprecipitation in a solvent in which the product is poorly soluble.

  The sulfur-containing polymer is preferably contained in an amount of 0.5 to 2.5 parts by mass with respect to 100 parts by mass of the polymerizable monomer or binder resin. The number of sulfur atoms relative to the sum of the number of atoms relative to the sum of the number of atoms of carbon, oxygen, nitrogen and sulfur atoms detected by surface analysis of toner particles by X-ray photoelectron spectroscopy (XPS) %, And the ratio of the number of sulfur atoms (%) to the number of oxygen atoms (%) is within the range, and the constituent elements on the toner surface of the resin that forms the outer layer and the sulfur-containing polymer are taken into consideration. It can satisfy | fill by adjusting the preparation amount of the polymerizable monomer, polar resin, sulfur-containing polymer at the time of manufacture.

  The toner of the present invention may contain a charge control agent in order to further stabilize the charging characteristics. Known charge control agents can be used. Further, when the toner is produced by a direct polymerization method, a charge control agent having a low polymerization inhibitory property and substantially free of a soluble component in an aqueous dispersion medium is particularly preferable. Specific compounds include, as negative charge control agents, for example, metal compounds of aromatic carboxylic acids such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid and dicarboxylic acid; metal salts or metal complexes of azo dyes or azo pigments Boron compound; silicon compound; calixarene. Examples of the positive charge control agent include a quaternary ammonium salt; a polymer compound having the quaternary ammonium salt in the side chain; a guanidine compound; a nigrosine compound; and an imidazole compound.

  The amount of these charge control agents used is preferably in the range of 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the binder resin, when added internally. In addition, when externally added, the amount is preferably 0.005 to 1.0 part by mass, more preferably 0.01 to 0.3 part by mass with respect to 100 parts by mass of the toner particles.

  Examples of the wax that can be used in the present invention 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 wax and polypropylene wax; carnauba wax; Natural wax such as candelilla wax and its derivatives. Examples of the derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. Furthermore, the following are mentioned. Higher fatty alcohols; fatty acids such as stearic acid and palmitic acid; acid amide waxes; ester waxes; hardened castor oil and its derivatives; plant waxes; Among these, ester wax or hydrocarbon wax is preferable from the viewpoint of excellent releasability. More preferably, when 50 to 95% by mass of a compound having the same total carbon number is contained in the wax, good developability is easily obtained and the effects of the present invention are easily exhibited.

  The wax is preferably contained in an amount of 1 to 40 parts by mass with respect to 100 parts by mass of the binder resin. More preferably, it is 3 to 25 parts by mass. When the wax content is in the above range, moderate wax bleeding is obtained at the time of fixing, and the occurrence of winding of the transfer material around the transfer member can be suppressed even when the temperature becomes high. Further, even when stress is applied to the toner during development or transfer, the exposure of the wax to the toner surface is small, and uniform chargeability of each toner can be obtained.

  As the black colorant used in the present invention, carbon black, a magnetic material, and a toned color of each color using the following yellow / magenta / cyan colorant are used. In particular, since dyes and carbon black have many polymerization-inhibiting properties, care must be taken when using them.

  Examples of the yellow colorant used in the present invention include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, for example, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 128, 129, 138, 147, 150, 151, 154, 155, 168, 180, 185, 214 and the like.

  Examples of the magenta colorant used in the present invention include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, for example, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. And CI Pigment Bio Red 19.

  Examples of the cyan colorant used in the present invention include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like. Specifically, for example, C.I. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66, and the like.

  These colorants can be used alone or in a mixture or in a solid solution state. The colorant is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner. The addition amount of the colorant is preferably in the range of 1 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer or binder resin.

  Furthermore, the toner of the present invention can be made into a magnetic toner by containing a magnetic material as a colorant. In this case, the magnetic material can also serve as a colorant. Examples of magnetic materials include iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel, or aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, and metals of these metals. Examples thereof include alloys of metals such as cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof.

  The magnetic body is more preferably a surface-modified magnetic body. When a magnetic toner is prepared by a polymerization method, it is preferable to apply a hydrophobic treatment with a surface modifier, which is a substance that does not inhibit polymerization. Examples of such surface modifiers include silane coupling agents and titanium coupling agents.

  These magnetic materials have a number average particle diameter of 0.1 to 2 μm, preferably 0.1 to 0.5 μm. The amount to be contained in the toner particles is 20 to 200 parts by mass with respect to 100 parts by mass of the polymerizable monomer or binder resin, and particularly preferably 40 to 150 parts by mass with respect to 100 parts by mass of the binder resin.

  The toner of the present invention is preferably produced in an aqueous medium. Examples of a method for producing toner particles in an aqueous medium include the following methods. An emulsion aggregation method in which an emulsion composed of essential toner components is agglomerated in an aqueous medium; the essential toner components are dissolved in an organic solvent, granulated in an aqueous medium, and then the organic solvent is volatilized. Grain method: Dispersing a polymerizable monomer in which toner essential components are dispersed in an aqueous medium, granulating it, and then polymerizing it by suspension polymerization method or emulsion polymerization method; after suspension polymerization or emulsion polymerization, seed polymerization is performed. A method of using an outer layer on a toner by using a microcapsule method represented by interfacial polycondensation or drying in liquid.

  Among these, the suspension polymerization method is particularly preferable in that a toner satisfying the provisions of the present invention can be easily obtained. In this suspension polymerization method, a wax, a colorant, and a sulfur-containing polymer (in addition, a polymerization initiator, a crosslinking agent, a charge control agent, a polar resin, and other additives as required) are uniformly added to the polymerizable monomer. The polymerizable monomer composition is dissolved or dispersed in Thereafter, the polymerizable monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer using a suitable stirrer, and a polymerization reaction is performed to obtain toner particles having a desired particle size. Moreover, it is preferable to control the amount of dissolved oxygen in the reaction vessel for the purpose of allowing the polymerization reaction to proceed efficiently. If there is little dissolved oxygen, the polymerization reaction will be more efficient. As a result, generation of low molecular weight components that adversely affect developability and transferability can be suppressed, and excellent high development efficiency, high transfer efficiency, and uniformity can be obtained. After the polymerization, the toner particles are filtered, washed and dried by a known method, and if necessary, a fluidity improver is mixed and adhered to the surface to obtain the toner of the present invention.

  When the toner is produced by this suspension polymerization method, since the individual toner particle shapes are substantially spherical, the charge amount distribution is relatively uniform and a toner having satisfactory development characteristics can be easily obtained. Further, it is possible to obtain a toner that is low in dependence on external additives and maintains high transferability.

  Examples of the polymerizable monomer for producing a toner by the suspension polymerization method include the monofunctional polymerizable monomer and the polyfunctional polymerizable monomer.

  As the crosslinking agent, a compound having two or more polymerizable double bonds is mainly used. Specifically, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate; Examples include divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone; compounds having three or more vinyl groups, and the like. These can be used alone or as a mixture. A preferable addition amount is 0.001 to 15 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  As the polymerization initiator, an oil-soluble initiator and / or a water-soluble initiator is used. Preferably, the half-life at the reaction temperature during the polymerization reaction is 0.5 to 30 hours. When the polymerization reaction is carried out at an addition amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer, a polymer having a maximum between 10,000 and 100,000 is usually obtained. A toner having strength and melting characteristics can be obtained.

  As polymerization initiators, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), Azo or diazo polymerization initiators such as 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide, t-butylperoxy 2-ethylhexano Ate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoylper Peroxide polymerization such as oxide and lauroyl peroxide It can be exemplified initiator like. Particularly preferred is a polymerization initiator that produces an ether compound as described below upon decomposition during the polymerization reaction.

  The toner of the present invention preferably contains a compound represented by the following structural formula (5) or (6).

（式中、Ｒ₂乃至Ｒ₁₂は、炭素数１乃至６のアルキル基であり、より好ましくは、炭素数１乃至４のアルキル基である。）

(In the formula, R _{2 to} R ₁₂ are each an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.)

  Since the above compound is excellent in compatibility with the binder resin, when it is contained in the toner, it is dispersed in a nearly uniform state. Since the oxygen atom is an element having a high electronegativity, it exists in a dispersed manner, thereby delocalizing the negative charge generated in the toner. For this reason, the negative charge of the toner can be stabilized by containing an ether compound. The effect of containing the ether compound is particularly remarkable when the toner of the present invention is a negative triboelectrically chargeable toner. In addition, it has the effect of suppressing charge-up even in the case of positive frictional charging.

  The ether compound has tertiary carbon and has a bulky structure. Since the functional group centered on tertiary carbon functions as a steric hindrance, it is hardly affected by water and charge leakage is suppressed. However, since the carbon bonded to the oxygen atom rotates, the functional group that can become steric hindrance can move, and the water molecule involved in the leakage of triboelectric charge is a small molecule. Must not. As a result, the functional group centered on tertiary carbon functions as an appropriate steric hindrance and appropriately blocks water molecules. Therefore, the toner containing the ether compound can obtain good chargeability even in a high humidity environment or a low humidity environment. In particular, when the polar resin and the ether compound are used in combination, the charge stabilizing effect can be exhibited even in the outer layer resin, and the chargeability can be improved more favorably. Accordingly, the toner coat uniformity on the toner carrier and the transfer efficiency, which are the effects of the present invention, can be maintained at a high level, the toner transfer uniformity within the same page, and the toner to the transfer material with low smoothness. Is excellent in that it is easily transferred uniformly.

  The ether compound is preferably contained in the toner in the range of 5 to 1,000 ppm. More preferably, it is 10 to 800 ppm. More preferably, it is 10 to 500 ppm. As the ether compound, an ether compound having another structure may be included as long as the compound having the above structure is a main component. The content at that time is the total amount of the ether compounds contained. When the content of the ether compound in the toner is within the above range, a good triboelectric charge amount can be obtained, and uniform toner charge can be obtained. Further, the toner coating uniformity on the toner carrier and the transfer efficiency can be maintained high, the toner transfer uniformity within the same page can be obtained, and even if the transfer material has low smoothness, Can be transferred uniformly.

  The ether compound may be added and contained as a prescription during the production of the toner particles, but it can also be produced in the polymerization vessel from the decomposition product of the polymerization initiator.

  Examples of the structure of the ether compound include the following structures.

  When the toner is produced by the suspension polymerization method, a known chain transfer agent, polymerization inhibitor, etc. can be further added and used in order to control the polymerization degree of the polymerizable monomer.

  In addition, although the mechanism is not clear, when toluene or xylene is added to the monomer to produce a polymerized toner, the solubility of the polar resin in the monomer is improved and the outer layer is formed by precipitation. Since the stability of the is increased, the effect of the present invention is easily exhibited. The addition amount of toluene or xylene is preferably 0.5 to 5.0 parts by mass with respect to 100 parts by mass of the monomer.

  A dispersion stabilizer can also be added to the aqueous medium. Examples of inorganic compounds that can be used as a dispersion stabilizer include calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, Examples thereof include barium sulfate, bentonite, silica, and alumina. Examples of the organic compound include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt, polyacrylic acid and its salt, starch and the like. These dispersion stabilizers are preferably used in an amount of 0.2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  Further, 0.001 to 0.1 parts by mass of a surfactant may be used for fine dispersion of these dispersion stabilizers. This is to promote the intended action of the dispersion stabilizer. Specific examples include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate and the like.

  When an inorganic compound is used as the dispersion stabilizer, a commercially available one may be used as it is, but in order to obtain finer particles, the inorganic compound may be generated and used in an aqueous medium. For example, in the case of calcium phosphate, a sodium phosphate aqueous solution and a calcium chloride aqueous solution may be mixed under high stirring.

  Furthermore, in the toner of the present invention, a fluidity improver may be externally added to the toner particles for the purpose of improving the fluidity of the toner particles. Examples of the fluidity improver include fluorine resin powder such as vinylidene fluoride fine powder, polytetrafluoroethylene fine powder; fatty acid metal salt such as zinc stearate, calcium stearate, lead stearate; titanium oxide powder, aluminum oxide Examples thereof include powders, metal oxides such as zinc oxide powder, or powders obtained by hydrophobizing the metal oxides; and silica fine powders such as wet process silica and dry process silica. It is more preferable to subject these fine powders to a surface treatment with a treatment agent such as a silane coupling agent, a titanium coupling agent, or silicone oil. The fluidity improver is preferably used in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass of the toner particles.

  Next, an example of an image forming method using the toner of the present invention will be described with reference to FIGS.

  FIG. 4 shows the configuration of the image forming apparatus (contact single component development system) used in this embodiment. The image forming apparatus is a tandem type color LBP (color laser printer LBP-2510, manufactured by Canon Inc.).

  In FIG. 4, reference numeral 101 (101a to 101d) denotes a drum-type electrophotographic photosensitive member (hereinafter referred to as a photosensitive drum) as an electrostatic latent image carrier that rotates at a predetermined process speed in the direction indicated by an arrow (counterclockwise). It is. The photosensitive drums 101a, 101b, 101c, and 101d sequentially share the yellow (Y) component, magenta (M) component, cyan (C) component, and black (Bk) component of the color image. These photosensitive drums 101a to 101d are rotationally driven by a drum motor (DC servo motor) (not shown). An independent drive source may be provided for each of the photosensitive drums 101a to 101d. The rotational drive of the drum motor is controlled by a DSP (digital signal processor) (not shown), and other control is performed by a CPU (not shown).

  The electrostatic adsorption transport belt 109a is stretched around a driving roller 109b, fixed rollers 109c and 109e, and a tension roller 109d, and is rotationally driven by the driving roller 109b in the direction of the arrow in the drawing, thereby transferring the material S (recording medium S). Adsorb and transport.

  Hereinafter, yellow (Y) of the four colors will be described as an example.

  The photosensitive drum 101a is uniformly charged to a predetermined polarity and potential by the primary charging means 102a during its rotation. Then, the photosensitive drum 101a is exposed by a laser beam exposure means (hereinafter referred to as a scanner) 103a, and an electrostatic latent image is formed on the photosensitive drum 101a.

  Next, the electrostatic latent image is developed by the developing unit 104a, and a toner image is formed on the photosensitive drum 101a. Similar steps are performed for the other three colors (magenta (B), cyan (C), and black (Bk)).

  Next, at the nip portion between the photosensitive drums 101a to 101d and the electrostatic adsorption conveyance belt 109a, the toner images of four colors are sequentially transferred to the recording medium S conveyed after adjusting the timing by the paper feed roller 108b and the registration roller 108c. Is done.

  In addition, after the toner image is transferred to the recording medium S, the photosensitive drums 101a to 101d are cleaned of residual deposits such as transfer residual toner by the cleaning units 106a, 106b, 106c, and 106d.

  The recording medium S on which the toner images are transferred from the four photosensitive drums 101a to 101d is separated from the surface of the electrostatic attraction / conveyance belt 109a by the driving roller 109b and sent to the fixing device 110. Then, after the toner image is fixed on the recording medium S in the fixing device 110, the toner image is discharged to the discharge tray 113 by the discharge roller 110c.

  Next, a specific example of an image forming method using the nonmagnetic one-component contact development method will be described with reference to an enlarged view of the developing unit (FIG. 3). In FIG. 3, the developing unit 13 is located in a developer container 23 containing a non-magnetic toner 17 as a one-component developer, and an opening extending in the longitudinal direction in the developer container 23, and carries an electrostatic latent image. A body (photosensitive drum) 10 and a toner carrier 14 disposed opposite to each other are provided. The toner 17 is transported to the toner carrier by the toner transport member 25.

  The developing unit 13 develops the electrostatic latent image on the electrostatic latent image carrier 10 to form a toner image. The electrostatic latent image carrier contact charging member 11 is in contact with the electrostatic latent image carrier 10. The bias of the electrostatic latent image carrier contact charging member 11 is applied by a power source 12.

  The toner carrying member 14 is provided sideways with the substantially half right circumferential surface shown in the drawing exposed in the developer container 23 and the left half circumferential surface exposed outside the developer container 23 at the opening.

  The surface exposed to the outside of the developer container 23 is in contact with the electrostatic latent image carrier 10 located on the left side of the developing unit 13 as shown in FIG.

  The peripheral speed of the electrostatic latent image carrier 10 is 50 to 170 mm / s, and the toner carrier 14 is 1 to 2 times the peripheral speed of the electrostatic latent image carrier 10 in the direction of arrow B. Rotate.

  At the upper position of the toner carrier 14, a metal plate such as SUS, a rubber material such as urethane or silicone, a metal thin plate of SUS or phosphor bronze having spring elasticity is used as a base, and the contact surface side to the toner carrier 14 A restricting member 16 having a rubber material adhered thereto is supported by a restricting member support sheet metal 24.

  The regulating member 16 is provided so that the vicinity of the free end side tip is brought into contact with the outer peripheral surface of the toner carrying member 14 by surface contact. The counter direction is located upstream of the rotation direction of the body 14. As an example of the regulating member 16, a plate-like urethane rubber having a thickness of 1.0 mm is bonded to the regulating member support sheet metal 24, and the contact pressure (linear pressure) with respect to the toner carrier 14 is appropriately set. is there. The contact pressure is preferably 20 to 300 N / m. The measurement of the contact pressure is converted from a value obtained by inserting three thin metal plates having a known friction coefficient into the contact portion and pulling out the central one with only a spring. The regulating member 16 having a rubber material adhered to the abutting surface side is preferable in terms of adhesion to the toner and can suppress the fusion and fixing of the toner to the regulating member in long-term use. Further, the restricting member 16 can be in contact with the toner carrier 14 by edge contact with which the tip is in contact. In the case of edge contact, it is more preferable in terms of toner layer regulation to set the contact angle of the regulating member 16 with respect to the tangent of the toner carrying body at the contact point with the toner carrying body to be 40 degrees or less.

  The toner supply roller 15 (15a is a shaft of the toner supply roller) is in contact with the contact portion of the regulating member 16 with the surface of the toner carrier 14 on the upstream side in the rotation direction of the toner carrier 14 and is rotatably supported. Has been. The contact width of the toner supply roller 15 with respect to the toner carrier 14 is preferably 1 to 8 mm, and it is preferable that the toner carrier 14 has a relative speed at the contact portion.

  The toner carrying member charging roller 29 is an elastic body such as NBR or silicone rubber, and is attached to the suppression member 30. The contact load of the toner carrying member charging roller 29 on the toner carrying member 14 by the suppressing member 30 is set to 0.49 to 4.9N. The toner layer on the toner carrier 14 is finely packed and uniformly coated by the contact of the charging roller 29 for the toner carrier. The longitudinal positional relationship between the regulating member 16 and the toner carrying member charging roller 29 is arranged so that the toner carrying body charging roller 29 can reliably cover the entire contact area of the regulating member 16 on the toner carrying member 14. Is preferred.

  Further, for driving the toner carrying member charging roller 29, a driven or the same peripheral speed is indispensable between the toner carrying member 14 and the peripheral speed difference between the toner carrying member charging roller 29 and the toner carrying member 14. If it occurs, the toner coat becomes non-uniform and unevenness occurs on the image, which is not preferable.

  The toner carrier charging roller 29 is biased by a power source 27 between the toner carrier 14 and the electrostatic latent image carrier 10 in a direct current (27 in FIG. 3). The magnetic toner 17 is given a charge by a discharge from a charging roller 29 for toner carrier.

  The bias of the charging roller 29 for the toner carrier is a bias equal to or higher than the discharge start voltage having the same polarity as that of the nonmagnetic toner, and is set so that a potential difference of 1000 to 2000 V is generated with respect to the toner carrier 14.

  After being charged by the toner carrying member charging roller 29, the toner layer formed on the toner carrying member 14 is uniformly transported to the developing unit which is opposite to the electrostatic latent image carrying member 10. Is done.

  In this developing unit, the toner layer formed on the toner carrier 14 is thinned by a DC bias applied between the toner carrier 14 and the electrostatic latent image carrier 10 by the power source 27 shown in FIG. The electrostatic latent image on the electrostatic latent image carrier 10 is developed to form a toner image.

  The measuring method of each physical property value is described below.

(1) The total number of carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms present on the toner particle surface, and the sulfur atom number% relative to the sum of the atoms and the toner particle surface. Ratio of the number of sulfur atoms (%) / the number of oxygen atoms (%) with respect to the sum of the number of atoms of each element of carbon atom, oxygen atom, nitrogen atom and sulfur atom The carbon atom present on the toner particle surface in the present invention , Oxygen atom, nitrogen atom and sulfur atom, the number of sulfur atoms with respect to the sum of the number of atoms, and the carbon atom, oxygen atom, nitrogen atom and sulfur atom present on the toner particle surface The ratio of the number of sulfur atoms (%) / the number of oxygen atoms (%) with respect to the sum of the number of atoms of each element can be calculated by performing surface composition analysis by ESCA (X-ray photoelectron spectroscopy).

The ESCA apparatus and measurement conditions in the present invention are shown below.
Equipment used: 1600S type X-ray photoelectron spectrometer manufactured by PHI (Physical Electronics Industries, Inc.) Measurement conditions: X-ray source MgKα (400 W)
Spectral region: 800 μmφ

In the present invention, the abundance of each element was quantified based on a peak having a peak top at the following energy.
Carbon element: 160 to 172 eV
Oxygen element: 528 to 538 eV
Nitrogen element: 398 to 402 eV
Sulfur element: 280 to 290 eV

  In the present invention, the surface atomic concentration of the toner particles is calculated from the measured peak intensity of each element using a relative sensitivity factor provided by PHI.

  As a measurement sample, toner is used. When an external additive is added to the toner, the toner is washed with a solvent that does not dissolve the toner, such as isopropanol, and the measurement is performed after removing the external additive. Do.

(2) Content of cyclohexane insoluble matter in tetrahydrofuran soluble matter of toner The content of cyclohexane insoluble matter in the tetrahydrofuran soluble matter of toner in the present invention can be determined according to the following procedure.

  The toner and THF were mixed at a concentration of 450 mg / ml, and the mixture was thoroughly shaken at room temperature for 10 hours until the samples were not united. The THF and the sample were mixed well, and then allowed to stand for 7 days. Thereafter, the lysate is separated into a supernatant and a sediment by centrifuging at 15000 rpm for 60 minutes in a 10 ° C. environment using a cooling high-speed centrifuge (for example, H-9R (manufactured by Kokusan)). The supernatant was collected. Further, the supernatant was reduced by 50% while bubbling the supernatant with nitrogen gas to prepare a concentrated solution. Thereafter, 5 ml of the concentrated solution was added to 100 ml of cyclohexane to produce an insoluble matter.

Thereafter, the liquid in which insoluble matter is generated is centrifuged for 60 minutes at 15000 rpm in a 10 ° C. environment using a cooling high-speed centrifuge (for example, H-9R (manufactured by Kokusan Co., Ltd.)). It was separated into (cyclohexane insoluble matter) and the supernatant was removed. The precipitate after removal was allowed to stand at room temperature for 24 hours, and then the solvent was removed in a vacuum dryer (40 ° C.) for 24 hours, and the components that were insoluble in cyclohexane were collected. The content of the cyclohexane insoluble component in the THF soluble component of the toner can be obtained from the following formula.
Content (% by mass) of cyclohexane insoluble matter in THF soluble matter for toner
= {(Cyclohexane insoluble matter in THF soluble matter) / toner mass} × 100

(3) Glass transition temperature (TgA) of toner and glass transition temperature (TgB) of cyclohexane insoluble in the tetrahydrofuran solubles of toner
In the present invention, the glass transition temperature (TgA) of the toner and the glass transition temperature (TgB) of the cyclohexane insoluble component in the tetrahydrofuran soluble component of the toner can be measured using a differential operation calorimeter (DSC measuring apparatus).

  The differential scanning calorimeter was measured using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments) according to ASTM D3418-82 as follows. The measurement sample was precisely weighed 2 to 5 mg, preferably 3 mg. It was placed in an aluminum pan and an empty aluminum pan was used as a control. After maintaining the equilibrium at 20 ° C. for 5 minutes, the measurement was performed at a temperature increase rate of 1 ° C./min with a modulation of 1.0 ° C./min in the measurement range of 20 to 140 ° C. In the present invention, the glass transition temperature was determined by the midpoint method.

(4) Acid value of cyclohexane insoluble component in tetrahydrofuran soluble component of toner and acid value of polar resin and sulfur-containing resin The acid value is the number of mg of potassium hydroxide necessary to neutralize the acid contained in 1 g of the sample. It is. The acid value of the cyclohexane insoluble component in the tetrahydrofuran soluble component of the toner in the present invention is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.

(I) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95 vol%), and ion exchange 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.

(Ii) Operation main test;
2.0 g of the measurement 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 1 hour. 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.

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).

(Iii) The acid value is calculated by substituting the obtained result into the following equation.
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).

(5) Weight average particle diameter (D4) and number average particle diameter (D1) of the toner
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner in the present invention were calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement was performed with 25,000 effective measurement channels.

  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 was set as follows.

  On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter The value obtained using the product was set. The threshold value and the noise level were automatically set by pressing the “threshold / noise level measurement button”. Further, the current was set to 1600 μA, the gain was set to 2, the electrolyte was set to ISOTON II, and the “aperture tube flush after measurement” was 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 to 60 μm.

The specific measurement method is as follows.
(I) About 200 ml of the electrolytic solution was placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod was stirred counterclockwise at 24 rotations / second. The dirt and air bubbles in the aperture tube were removed using the “aperture flush” function of the dedicated software.
(Ii) About 30 ml of the electrolytic aqueous solution was placed in a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting the solution with ion exchange water about 3 times by mass.
(Iii) Two oscillators with an oscillation frequency of 50 kHz were incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios) with an electrical output of 120 W was prepared. About 3.3 liters of ion-exchanged water was placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N was added to the water tank.
(Iv) The beaker of (ii) was set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser was operated. Then, the height position of the beaker was adjusted so that the resonance state of the liquid surface of the electrolytic aqueous solution in the beaker was maximized.
(V) In the state where the electrolytic aqueous solution in the beaker of (iv) was irradiated with ultrasonic waves, about 10 mg of toner was added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion treatment was further continued for 60 seconds. In the ultrasonic dispersion, the water temperature in the water tank was appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(Vi) To the round bottom beaker (i) installed in the sample stand, the electrolyte solution (v) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . The measurement was performed until the number of measured particles reached 50,000.
(Vii) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. The “average diameter” on the “analysis / volume statistics (arithmetic average)” screen when the graph / volume% is set in the dedicated software is the weight average particle size (D4). When “number%” was set, the “average diameter” on the “analysis / number statistics (arithmetic average)” screen was the number average particle diameter (D1).

(6) Molecular weight distribution of polar resin and sulfur-containing polymer The molecular weight distribution of the polar resin and sulfur-containing polymer was measured by gel permeation chromatography (GPC) as follows.

First, a measurement sample is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. The obtained solution is filtered through a solvent-resistant membrane filter “Maescho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml

  In calculating the molecular weight of the measurement sample, standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F -10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 "manufactured by Tosoh Corporation) were used.

(7) Penetration film thickness L (μm) at a permeation time of 5 seconds, average permeation speed Va (μm / s) at a permeation time of 5 seconds to 10 seconds, and a permeation time when the UV photocurable composition is permeated Average penetration speed Vb (μm / s) in 10 seconds or more and 15 seconds or less
UV photocurable composition Luxtrax D-800 (tri (ethylene glycol) dimethacrylate) and a composition comprising acrylic modified urethane oligomer combined with hexamethylene diisocyanate, OH group-containing methacrylate and bisphenol A propylene oxide adduct ; Toagosei Co., Ltd.) was put into a cylindrical container with a diameter of 1 mm, and the toner to be measured was put from above, and the UV photocurable composition was infiltrated for 5 seconds. Thereafter, for example, a sample is placed at a distance of 3.0 ± 0.1 cm from the irradiation part of the irradiator LS-800 (manufactured by JEOL Datum Co., Ltd.), irradiated with UV light at an output of 150 W for 30 seconds, and the UV photocurability The composition was cured in toner. The toner after penetration and curing of the UV photocurable composition was made into a toner slice having a thickness of 50 to 100 nm using, for example, ULTRACUT UCT (manufactured by Leica Microsystems). Note that when the slice was created, it was a slice at the center of the toner particles. The toner slice was observed using, for example, a field emission scanning electron microscope S-4800 (manufactured by Hitachi High-Tech Co., Ltd.) to obtain a transmission electron image (STEM image) of the toner slice.

The penetration film thickness of the UV photocurable composition in the transmission electron image was L. The permeation film thickness (La) of each particle is Lx as the permeation film thickness of the UV photocurable composition in the major axis direction in the toner slice, and Ly as the permeation film thickness of the UV photocurable composition in the minor axis direction. When
La = (Lx + Ly) / 2
Defined.

  In order to eliminate measurement errors as much as possible, toner particles having a toner number average particle diameter D1 of ± 0.2 μm were selected and the osmotic film thickness was measured. For measurement, 100 particles satisfying the above conditions are selected and measured, and the osmotic thickness La of each particle obtained as a measurement result is obtained by removing the remaining 80 particles excluding 10 from the maximum value and the minimum value. It was used as data, and the osmotic film thickness L at a osmosis time of 5 seconds was determined as an arithmetic average value of the 80 samples.

Similarly, a section was prepared for a toner impregnated with the UV photocurable composition for 10 seconds. As in the case of the osmotic film thickness L, the osmotic film thickness of 100 toner particles is measured, and the remaining 80 values obtained by removing 10 from the maximum value and the minimum value are used as data. The arithmetic mean value was defined as L _{10 for} the osmotic film thickness when the osmosis time was 10 seconds. At this time, the average penetration speed Va at the penetration time of 5 seconds or more and 10 seconds or less is Va = (L ₁₀ −L) / 5.
Defined.

Similarly, a section was prepared for a toner impregnated with a UV photocurable composition for 15 seconds. As in the case of the osmotic film thickness L, the osmotic film thickness of 100 toner particles is measured, and the remaining 80 values obtained by removing 10 from the maximum value and the minimum value are used as data. The arithmetic average value was defined as L _{15 for} the osmotic film thickness when the osmosis time was 15 seconds. At this time, the average penetration speed Vb at the penetration time of 10 seconds or more and 15 seconds or less is Vb = (L ₁₅ −L ₁₀ ) / 5.
Defined.

  FIG. 2 shows an image of the relationship between the osmotic film thickness and the osmotic time at this time. Incidentally, the osmotic film thickness at a permeation time of 0 second is obtained in the same manner as the measurement of the osmotic film thickness L, using a sample when irradiated with UV light immediately after the toner is put into the UV photocurable composition. The osmotic film thickness. The reason why the osmotic film thickness is not 0 μm at the permeation time of 0 second is that the UV light curable composition permeates while being cured by irradiation with UV light. In this case, “penetration time of 5 seconds”, “penetration time of 10 seconds”, and “penetration time of 15 seconds” are specified, but strictly speaking, in addition to the specified times, UV light is irradiated to UV light. The time until the curable composition is cured is included in the actual penetration time.

(8) Structural analysis of polar resin and sulfur-containing polymer The structure of the polar resin and sulfur-containing polymer was determined using a nuclear magnetic resonance apparatus ( ¹ H-NMR, ¹³ C-NMR) and an FT-IR spectrum. . The apparatus used is described below.
(I) ¹ H-NMR, ¹³ C-NMR
FT-NMR JNM-EX400 manufactured by JEOL (solvent: heavy chloroform)
(Ii) FT-IR spectrum AVATAR360FT-IR manufactured by Nicolet

  The present invention will be specifically described with reference to the following examples. This does not limit the invention in any way.

<Example of production of sulfur-containing polymer>
Preparation example 1 of sulfur-containing polymer (production of sulfur-containing polymer 1)
Styrene-acrylic acid copolymer 100 parts by mass (copolymerization ratio: 93.0: 7.0, Mw = 16600, Mw / Mn = 3.6, acid value = 40.2 mgKOH / g)
4-Methoxyaniline-2-sulfonic acid 18 parts by weight Pyridine 375 parts by weight Triphenyl phosphite 27 parts by weight In the reaction vessel equipped with a cooling tube, a stirrer, a thermometer and a nitrogen introduction tube, the above styrene-acrylic acid 100 parts by weight of copolymer was added. Next, 18 parts by mass of 4-methoxyaniline-2-sulfonic acid was added, 375 parts by mass of pyridine was added and stirred, and then 27 parts of triphenyl phosphite was added and heated at 120 ° C. for 6 hours.

  After completion of the reaction, it was recovered by reprecipitation in 500 parts by mass of ethanol. The obtained polymer was washed twice with 200 parts by mass of 1N hydrochloric acid, then washed twice with 200 parts by mass of water, and dried under reduced pressure, whereby the sulfonic acid unit represented by the chemical formula (11) was obtained. A containing polymer was obtained.

  Next, 100 parts by mass of the polymer obtained above was added to a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube. 760 parts by mass of trimethyl orthoformate was charged, and the mixture was heated and stirred at 80 ° C. for 8 hours. After completion of the reaction, the reaction mixture was cooled to 50 ° C., and excess trimethyl orthoformate and its decomposition product were distilled off by distillation under reduced pressure. The residue was dropped into a mixed solvent of 1500 parts by mass of isopropanol and 500 parts by mass of water. After stirring for a while, the mixture was allowed to stand to precipitate and precipitate the resin. After removing the supernatant by decantation, 200 parts by mass of acetone was added to the residue and dissolved. This solution was dropped into a mixed solvent of 1500 parts by mass of isopropanol and 500 parts by mass of water. After stirring for a while, precipitation and precipitation occurred. The supernatant was removed by decantation. The obtained residue was dried under reduced pressure to obtain sulfur-containing polymer 1.

The obtained sulfur-containing polymer 1 was subjected to molecular weight measurement by the method described above, and was Mw = 16600 and Mw / Mn = 3.7. Also, composition analysis of the resulting sulfur-containing polymers, using ^{1 H-NMR, 13 C-} NMR, was measured by the aforementioned methods. As a result, it was confirmed that the polymer was a sulfur-containing polymer containing 6 mol% of the sulfonic acid methyl unit represented by the chemical formula (12) and 1 mol% of the sulfonic acid unit represented by the chemical formula (11).

Preparation example 2 of sulfur-containing polymer (production of sulfur-containing polymer 2)
Styrene-acrylic acid copolymer 100 parts by mass (copolymerization ratio: 90.0: 10.0, Mw = 1800, Mw / Mn = 2.6, acid value = 48.7 mgKOH / g)
4-Methoxyaniline-2-sulfonic acid 21 parts by mass Pyridine 375 parts by mass Triphenyl phosphite 32 parts by mass In the reaction vessel equipped with a cooling tube, a stirrer, a thermometer and a nitrogen introduction tube, the above styrene-acrylic acid 100 parts by weight of copolymer was added. Next, 21 parts by mass of 4-methoxyaniline-2-sulfonic acid was added, 375 parts by mass of pyridine was added and stirred, and then 32 parts by mass of triphenyl phosphite was added and heated at 120 ° C. for 6 hours.

  After completion of the reaction, it was recovered by reprecipitation in 500 parts by mass of ethanol. The obtained polymer was washed twice with 200 parts by mass of 1N hydrochloric acid, then washed twice with 200 parts by mass of water, and dried under reduced pressure, whereby the sulfonic acid unit represented by the chemical formula (11) was obtained. A containing polymer was obtained.

  Next, 100 parts by mass of the polymer obtained above was added to a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube. 921 parts by mass of trimethylorthoformate was charged and stirred with heating at 80 ° C. for 8 hours. After completion of the reaction, the reaction mixture was cooled to 50 ° C., and excess trimethyl orthoformate and its decomposition product were distilled off by distillation under reduced pressure. The residue was dropped into a mixed solvent of 1500 parts by mass of isopropanol and 500 parts by mass of water. After stirring for a while, the mixture was allowed to stand to precipitate and precipitate the resin. After removing the supernatant by decantation, 200 parts by mass of acetone was added to the residue and dissolved. This solution was dropped into a mixed solvent of 1500 parts by mass of isopropanol and 500 parts by mass of water. After stirring for a while, precipitation and precipitation occurred. The supernatant was removed by decantation. The obtained residue was dried under reduced pressure to obtain sulfur-containing polymer 2.

The obtained sulfur-containing polymer 2 was subjected to molecular weight measurement by the method described above, and was Mw = 11900 and Mw / Mn = 2.8. Also, composition analysis of the resulting sulfur-containing polymers, using ^{1 H-NMR, 13 C-} NMR, was measured by the aforementioned methods. As a result, it was confirmed to be a sulfur-containing polymer containing 9 mol% of a sulfonic acid methyl unit represented by the chemical formula (12) and 1 mol% of a sulfonic acid unit represented by the chemical formula (11).

Preparation example 3 of sulfur-containing polymer (production of sulfur-containing polymer 3)
Styrene-acrylic acid copolymer 100 parts by mass (copolymerization ratio: 95.0: 5.0, Mw = 11700, Mw / Mn = 3.5, acid value = 26.7 mgKOH / g)
4-Methoxyaniline-2-sulfonic acid 12 parts by mass Pyridine 375 parts by mass Triphenyl phosphite 18 parts by mass In the reaction vessel equipped with a cooling tube, a stirrer, a thermometer and a nitrogen introduction tube, the above styrene-acrylic acid 100 parts by weight of copolymer was added. Next, 12 parts by mass of 4-methoxyaniline-2-sulfonic acid was added, 375 parts by mass of pyridine was added and stirred, 18 parts by mass of triphenyl phosphite was added, and the mixture was heated at 120 ° C. for 6 hours.

  After completion of the reaction, it was recovered by reprecipitation in 500 parts by mass of ethanol. The obtained polymer was washed twice with 200 parts by mass of 1N hydrochloric acid, then washed twice with 200 parts by mass of water, and dried under reduced pressure, whereby the sulfonic acid unit represented by the chemical formula (11) was obtained. A containing polymer was obtained.

  Next, 100 parts by mass of the polymer obtained above was added to a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube. 505 parts by mass of trimethylorthoformate was charged, and heated and stirred at 80 ° C. for 8 hours. After completion of the reaction, the reaction mixture was cooled to 50 ° C., and excess trimethyl orthoformate and its decomposition product were distilled off by distillation under reduced pressure. The residue was dropped into a mixed solvent of 1500 parts by mass of isopropanol and 500 parts by mass of water. After stirring for a while, the mixture was allowed to stand to precipitate and precipitate the resin. After removing the supernatant by decantation, 200 parts by mass of acetone was added to the residue and dissolved. This solution was dropped into a mixed solvent of 1500 parts by mass of isopropanol and 500 parts by mass of water. After stirring for a while, precipitation and precipitation occurred. The supernatant was removed by decantation. The obtained residue was dried under reduced pressure to obtain sulfur-containing polymer 3.

The obtained sulfur-containing polymer 3 was subjected to molecular weight measurement by the method described above, and was Mw = 11900 and Mw / Mn = 2.8. Also, composition analysis of the resulting sulfur-containing polymers, using ^{1 H-NMR, 13 C-} NMR, was measured by the aforementioned methods. As a result, it was confirmed that the polymer was a sulfur-containing polymer containing 4 mol% of the sulfonic acid methyl unit represented by the chemical formula (12) and 1 mol% of the sulfonic acid unit represented by the chemical formula (11).

Preparation example 4 of sulfur-containing polymer (production of sulfur-containing polymer 4)
Styrene-acrylic acid copolymer 100 parts by mass (copolymerization ratio: 93.0: 7.0, Mw = 16600, Mw / Mn = 3.6, acid value = 40.2 mgKOH / g)
2-Aminobenzenesulfonic acid 15 parts by mass Pyridine 375 parts by mass Triphenyl phosphite 27 parts by mass In Preparation Example 1 of the sulfur-containing polymer, 18 parts by mass of 4-methoxyaniline-2-sulfonic acid was added to 2-aminobenzenesulfonic acid. The sulfur-containing polymer 4 was obtained by performing the method similar to the preparation example 1 except changing to 15 mass parts.

The obtained sulfur-containing polymer 4 was subjected to molecular weight measurement by the method described above, and Mw: 16700 and Mw / Mn = 3.4. Moreover, the composition analysis of the obtained sulfur-containing polymer 4 was measured by the method as described above using ¹ H-NMR and ¹³ C-NMR. As a result, it was confirmed that the polymer contained 6 mol% of the sulfonic acid methyl unit represented by the chemical formula (13) and 1 mol% of the sulfonic acid unit represented by the chemical formula (14).

Preparation example 5 of sulfur-containing polymer (production of sulfur-containing polymer 5)
Styrene-methacrylic acid-butyl acrylate copolymer 100 parts by mass (copolymerization ratio: 77.0: 7.0: 16.0, Mw = 13500, Mw / Mn = 2.9, acid value = 36.4 mgKOH / g)
p-Toluidine-2-sulfonic acid 15 parts by weight Pyridine 375 parts by weight Triphenyl phosphite 24 parts by weight In the reaction vessel equipped with a cooling tube, a stirrer, a thermometer and a nitrogen introduction tube, the above styrene-methacrylic acid- 100 parts by weight of butyl acrylate copolymer was added. Next, 15 parts by mass of p-toluidine-2-sulfonic acid was added, 375 parts by mass of pyridine was added and stirred, 24 parts by mass of triphenyl phosphite was added, and the mixture was heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 500 parts by mass of ethanol. The obtained polymer was washed twice with 200 parts by mass of 1N hydrochloric acid, then washed twice with 200 parts by mass of water, and dried under reduced pressure, so that the sulfonic acid unit represented by the chemical formula (15) was obtained. A containing polymer was obtained.

  Next, 100 parts of the polymer obtained above was added to a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube. 688 parts by mass of trimethyl orthoformate was charged, and the mixture was stirred with heating at 80 ° C. for 8 hours. After completion of the reaction, the reaction mixture was cooled to 50 ° C., and excess trimethyl orthoformate and its decomposition product were distilled off by distillation under reduced pressure. The residue was dropped into a mixed solvent of 1500 parts by mass of isopropanol and 500 parts by mass of water. After stirring for a while, the mixture was allowed to stand to precipitate and precipitate the resin. After removing the supernatant by decantation, 200 parts by mass of acetone was added to the residue and dissolved. This solution was dropped into a mixed solvent of 1500 parts by mass of isopropanol and 500 parts by mass of water. After stirring for a while, precipitation and precipitation occurred. The supernatant was removed by decantation. The obtained residue was dried under reduced pressure to obtain sulfur-containing polymer 5.

The obtained sulfur-containing polymer 5 was subjected to molecular weight measurement by the method described above, and Mw: 12800 and Mw / Mn = 2.9. Moreover, the composition analysis of the obtained sulfur-containing polymer 5 measured using the method of the said description using < ¹ > H-NMR and < ¹³ > C-NMR. As a result, it was confirmed to be a sulfur-containing polymer containing 5 mol% of a sulfonic acid methyl unit represented by the chemical formula (16) and 1 mol% of a sulfonic acid unit represented by the chemical formula (15).

Preparation Example 6 of Sulfur-Containing Polymer (Production of Sulfur-Containing Polymer 6)
Styrene-methacrylic acid copolymer 100 parts by mass (copolymerization ratio: 93.3: 6.7, Mw = 13100, Mw / Mn = 2.7, acid value = 37.5 mgKOH / g)
2-Amino-1-naphthalenesulfonic acid 18 parts by weight Pyridine 375 parts by weight Triphenyl phosphite 25 parts by weight In the reaction vessel equipped with a cooling tube, a stirrer, a thermometer and a nitrogen introduction tube, the above styrene-methacrylic acid 100 parts by weight of copolymer was added. Next, 18 parts by mass of 2-amino-1-naphthalenesulfonic acid was added, 375 parts by mass of pyridine was added and stirred, and then 25 parts by mass of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 500 parts by mass of ethanol. The obtained polymer was washed twice with 200 parts by mass of 1N hydrochloric acid, then washed twice with 200 parts by mass of water, and dried under reduced pressure, so that the sulfonic acid unit represented by the chemical formula (17) was obtained. A containing polymer was obtained.

  Next, 100 parts by mass of the polymer obtained above was added to a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube. 710 parts by mass of trimethylorthoformate was charged, and heated and stirred at 80 ° C. for 8 hours. After completion of the reaction, the reaction mixture was cooled to 50 ° C., and excess trimethyl orthoformate and its decomposition product were distilled off by distillation under reduced pressure. The residue was dropped into a mixed solvent of 1500 parts by mass of isopropanol and 500 parts by mass of water. After stirring for a while, the mixture was allowed to stand to precipitate and precipitate the resin. After removing the supernatant by decantation, 200 parts by mass of acetone was added to the residue and dissolved. This solution was dropped into a mixed solvent of 1500 parts by mass of isopropanol and 500 parts by mass of water. After stirring for a while, precipitation and precipitation occurred. The supernatant was removed by decantation. The obtained residue was dried under reduced pressure to obtain sulfur-containing polymer 6.

The obtained sulfur-containing polymer 6 was subjected to molecular weight measurement by the method described above, and Mw: 13300 and Mw / Mn = 2.8. Also, composition analysis of the sulfur-containing polymer 6 obtained are used ^{1 H-NMR, 13 C-} NMR, it was measured by the aforementioned methods. As a result, it was confirmed to be a sulfur-containing polymer containing 5 mol% of a sulfonic acid methyl unit represented by the chemical formula (18) and 1 mol% of a sulfonic acid unit represented by the chemical formula (17).

Preparation example 7 of sulfur-containing polymer (production of sulfur-containing polymer 7)
Styrene 100 parts by mass o-methyl styrenesulfonate 10 parts by mass 2,2′-azobisisobutyronitrile 1.3 parts by mass dimethylformamide 110 parts by mass Reaction with cooling tube, stirrer, thermometer and nitrogen introduction tube Styrene, methyl o-styrenesulfonate, and 2,2′-azobisisobutyronitrile were added to the tank, dissolved in dimethylformamide, and then polymerized at 70 ° C. for 5 hours in a nitrogen atmosphere. After completion of the reaction, it was recovered by reprecipitation in 500 parts by mass of methanol. The obtained polymer was washed twice with 500 parts by mass of water and dried under reduced pressure to obtain a sulfur-containing polymer 7 containing a methyl sulfonate unit represented by the chemical formula (19).

The obtained sulfur-containing polymer 7 was subjected to molecular weight measurement by the method described above, and Mw: 11900 and Mw / Mn = 2.6. Also, composition analysis of the sulfur-containing polymer 6 obtained are used ^{1 H-NMR, 13 C-} NMR, it was measured by the aforementioned methods. As a result, it was confirmed to be a sulfur-containing polymer containing 9 mol% of a methyl sulfonate unit represented by the chemical formula (19).

<Example 1>
A toner was manufactured according to the following procedure.

  To 1300 parts by mass of ion-exchanged water heated to 60 ° C., 9 parts by mass of tricalcium phosphate and 11 parts by mass of 10% hydrochloric acid are added, and 10,000 using a TK homomixer (manufactured by Special Machine Industries). The mixture was stirred at rotation / minute to prepare an aqueous medium having a pH of 5.2.

Further, the following materials were dissolved at 100 rpm with a propeller type stirring device to prepare a solution.
-Styrene 70.0 parts by mass-n-Butyl acrylate 30.0 parts by mass-Toluene 2.5 parts by mass-Sulfur-containing polymer 1 1.5 parts by mass-Polar resin 1: styrene-methacrylic acid-methyl methacrylate 20.0 parts by mass of polymer (copolymerization ratio (mass basis) = 95.6: 1.7: 2.7, Mw = 68000, Tg = 102 ° C., acid value = 12.0 mgKOH / g, Mw / Mn = 2.1)

Next, C. I. Pigment Blue 15: 3 7.0 parts by mass / Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass / 0.05 parts by mass of di-t-butyl ether, and then a mixed solution Was heated to 60 ° C., and then stirred and dissolved and dispersed at 9,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.).

  In this, 8.0 parts by mass of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition. The polymerizable monomer composition was put into the aqueous medium, and the mixture was granulated by stirring at 60 ° C. at 10,000 rpm for 30 minutes using a TK homomixer.

  Thereafter, the mixture was transferred to a propeller type stirring device and stirred at 100 revolutions / minute, reacted at 70 ° C. for 5 hours at 0.50% or less of dissolved oxygen in a nitrogen atmosphere, and then heated to 80 ° C. Reaction was performed for 5 hours to produce toner particles. After the completion of the polymerization reaction, the slurry containing the particles was cooled, washed with an amount of water 10 times that of the slurry, filtered and dried, and then the particle diameter was adjusted by classification to obtain cyan toner particles.

Hydrophobic silica fine powder (primary particles treated with a fluidity improver (dimethylsilicone oil (20% by mass)) and charged with the same polarity (negative polarity) as the toner particles with respect to 100 parts by mass of the cyan toner particles (Diameter: 10 nm, BET specific surface area: 170 m ^{2 /} g)) 2.0 parts by mass were externally added and mixed at 3000 rpm for 15 minutes using a Henschel mixer (Mitsui Miike) to obtain cyan toner 1. . The physical properties of the obtained cyan toner 1 are shown in Table 1.

<Example 2>
Styrene 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Toluene 2.5 parts by mass Sulfur-containing polymer 2 1.5 parts by mass Polar resin 1 20.0 parts by mass I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 2 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Example 3>
-Styrene 70.0 parts by mass-n-butyl acrylate 30.0 parts by mass-Toluene 2.5 parts by mass-Sulfur-containing polymer 3 0.5 parts by mass-Polar resin 1 20.0 parts by mass-C.I. I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 3 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Example 4>
Styrene 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Toluene 2.5 parts by mass Sulfur-containing polymer 5 1.5 parts by mass Polar resin 1 20.0 parts by mass I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 4 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Example 5>
Styrene 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Toluene 2.5 parts by mass Sulfur-containing polymer 4 1.5 parts by mass Polar resin 1 20.0 parts by mass I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 5 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Example 6>
Styrene 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Toluene 2.5 parts by mass Sulfur-containing polymer 6 1.5 parts by mass Polar resin 1 20.0 parts by mass I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 6 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Example 7>
-Styrene 70.0 parts-N-butyl acrylate 30.0 parts-Toluene 2.5 parts-Sulfur polymer 1 1.5 parts-Polar resin 2: Styrene-methacrylic acid-methyl methacrylate 20.0 parts by mass of polymer (copolymer ratio: 91.6: 5.7: 2.7, Mw = 68000, Mw / Mn = 2.1, Tg = 102 ° C., acid value = 40.0 mgKOH / g )
・ C. I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 7 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Example 8>
Styrene 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Toluene 2.5 parts by mass Sulfur-containing polymer 1 1.5 parts by mass Polar resin 3: styrene-methacrylic acid-methyl methacrylate 20.0 parts by mass of polymer (copolymer ratio: 96.6: 0.7: 2.7, Mw = 68000, Mw / Mn = 2.1, Tg = 102 ° C., acid value = 5.0 mgKOH / g )
・ C. I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 8 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Example 9>
Styrene 75.0 parts by mass n-butyl acrylate 25.0 parts by mass Toluene 2.5 parts by mass Sulfur-containing polymer 1 2.0 parts by mass Polar resin 4: styrene-methacrylic acid-methyl methacrylate 20.0 parts by mass of polymer (copolymer ratio: 95.6: 1.7: 2.7, Mw = 24,000, Mw / Mn = 2.1, Tg = 102 ° C., acid value = 12.0 mgKOH / g )
・ C. I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 9 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Example 10>
Styrene 68.0 parts by mass n-butyl acrylate 32.0 parts by mass Toluene 2.5 parts by mass Sulfur-containing polymer 1 1.5 parts by mass Polar resin 1 5.0 parts by mass I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 10 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Example 11>
-Styrene 72.5 parts by mass-n-butyl acrylate 27.5 parts by mass-Toluene 2.5 parts by mass-Sulfur-containing polymer 1 1.5 parts by mass-Polar resin 5: Styrene-n-butyl acrylate-methacrylic acid -Methyl methacrylate copolymer 20.0 parts by mass (copolymerization ratio = 83.6: 12.0: 1.7: 2.7, Mw = 68000, Tg = 80 ° C., acid value = 12.0 mgKOH / g , Mw / Mn = 2.1)
・ C. I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 11 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Example 12>
Styrene 66.5 parts by mass n-butyl acrylate 33.5 parts by mass Toluene 2.5 parts by mass Sulfur-containing polymer 2 1.5 parts by mass Polar resin 6: Styrene-α-methylstyrene-methacrylic acid Methyl methacrylate copolymer 20.0 parts by mass (copolymerization ratio = 65.6: 30.0: 1.7: 2.7, Mw = 43000, Tg = 120 ° C., acid value = 12.0 mgKOH / g, Mw / Mn = 2.1)
・ C. I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 12 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Example 13>
Styrene 72.5 parts by mass n-butyl acrylate 27.5 parts by mass Toluene 2.5 parts by mass The above sulfur-containing polymer 4 1.5 parts by mass Polar resin 7: Styrene-n-butyl acrylate-methacrylic acid -Methyl methacrylate copolymer 20.0 parts by mass (copolymerization ratio = 80.6: 15.0: 1.7: 2.7, Mw = 68000, Tg = 70 ° C., acid value = 12.0 mgKOH / g , Mw / Mn = 2.2)
・ C. I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 13 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Example 14>
Styrene 66.5 parts by mass n-butyl acrylate 33.5 parts by mass Toluene 2.5 parts by mass The above sulfur-containing polymer 2 1.5 parts by mass Polar resin 8: Styrene-α-methylstyrene-methacrylic acid Methyl methacrylate copolymer 20.0 parts by mass (copolymerization ratio = 60.6: 35.0: 1.7: 2.7, Mw = 44000, Tg = 130 ° C., acid value = 12.0 mgKOH / g, Mw / Mn = 2.2)
・ C. I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 14 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Example 15>
Styrene 77.0 parts by mass n-butyl acrylate 23.0 parts by mass Toluene 2.5 parts by mass Sulfur-containing polymer 1 1.5 parts by mass Polar resin 1 20.0 parts by mass I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 15 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Example 16>
Styrene 77.0 parts by mass n-butyl acrylate 23.0 parts by mass Toluene 2.5 parts by mass The above sulfur-containing polymer 4 2.0 parts by mass The polar resin 1 20.0 parts by mass I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 16 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Example 17>
Toner was produced in the same manner as in Example 1 except that 9.0 parts by mass of tricalcium phosphate was changed to 30.0 parts by mass and the formulation was changed as follows.
Styrene 77.0 parts by mass n-butyl acrylate 23.0 parts by mass Toluene 2.5 parts by mass The above sulfur-containing polymer 1 2.0 parts by mass Polar resin 9: Styrene-methyl methacrylate copolymer 20 0.0 part by mass (copolymerization ratio (mass basis) = 97.3: 2.7, Mw = 68000, Tg = 102 ° C., acid value = 0 mgKOH / g, Mw / Mn = 2.2)
・ C. I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 17 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Example 18>
Styrene 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Toluene 2.5 parts by mass Sulfur-containing polymer 1 1.5 parts by mass Polar resin 10: styrene-methacrylic acid-methyl methacrylate Polymer
20.0 parts by mass (copolymer ratio: 91.0: 6.3: 2.7, Mw = 230,000, Mw / Mn = 3.1, Tg = 102 ° C., acid value = 45.0 mgKOH / g)
・ C. I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 18 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Example 19>
Styrene 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Toluene 2.5 parts by mass The above sulfur-containing polymer 1 1.5 parts by mass Polar resin 11: Styrene-α-methylstyrene-methacrylic acid Methyl methacrylate copolymer 20.0 parts by mass (copolymerization ratio = 56.0: 35.0: 6.3: 2.7, Mw = 43000, Tg = 130 ° C., acid value = 45.0 mgKOH / g, Mw / Mn = 2.2)
・ C. I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 19 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Example 20>
Styrene 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Toluene 2.5 parts by mass The above sulfur-containing polymer 1 0.7 parts by mass Polar resin 12: styrene-methacrylic acid-methyl methacrylate Polymer
20.0 parts by mass (copolymerization ratio = 95.6: 1.7: 2.7, Mw = 10000, Tg = 102 ° C., acid value = 12.0 mgKOH / g, Mw / Mn = 2.0)
・ C. I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 20 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Example 21>
Styrene 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Toluene 2.5 parts by mass The above sulfur-containing polymer 1 0.7 parts by mass Polar resin 13: styrene-methacrylic acid-methyl methacrylate Polymer
20.0 parts by mass (copolymerization ratio = 95.6: 1.7: 2.7, Mw = 250,000, Tg = 102 ° C., acid value = 12.0 mgKOH / g, Mw / Mn = 2.8)
・ C. I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 21 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Example 22>
Styrene 58.0 parts by mass n-butyl acrylate 42.0 parts by mass Toluene 2.5 parts by mass Sulfur-containing polymer 7 1.5 parts by mass Polar resin 12 20.0 parts by mass I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 22 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Example 23>
Styrene 66.5 parts by mass n-butyl acrylate 33.5 parts by mass Toluene 2.5 parts by mass Sulfur-containing polymer 7 1.5 parts by mass Polar resin 14 20.0 parts by mass I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 23 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Comparative Example 1>
Styrene 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Toluene 2.5 parts by mass The above sulfur-containing polymer 1 3.0 parts by mass The polar resin 1 20.0 parts by mass I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 24 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Comparative example 2>
-Styrene 70.0 parts by mass-n-butyl acrylate 30.0 parts by mass-Toluene 2.5 parts by mass-Sulfur-containing polymer 2 3.0 parts by mass-Polar resin 1 20.0 parts by mass-C.I. I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 25 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Comparative Example 3>
Styrene 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Toluene 2.5 parts by mass Sulfur-containing polymer 1 0.1 parts by mass Polar resin 1 20.0 parts by mass I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 26 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Comparative example 4>
Styrene 70.0 parts by mass n-butyl acrylate 30.0 parts by mass Toluene 2.5 parts by mass Sulfur-containing polymer 3 0.2 parts by mass Polar resin 1 20.0 parts by mass I. Pigment Blue 15: 3 7.0 parts by mass, wax: WEP-3 (melting point 73 ° C .; manufactured by NOF Corporation) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis ( 2,4-dimethylvaleronitrile) 8.0 parts by mass Cyan toner 27 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Comparative Example 5>
-Styrene 77.0 mass parts-N-butyl acrylate 30.0 mass parts-Toluene 2.5 mass parts-The sulfur-containing polymer 1 0.3 mass parts-The polar resin 13 20.0 mass parts-C.I. I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 28 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Comparative Example 6>
Styrene 62.0 parts by mass n-butyl acrylate 38.0 parts by mass Toluene 2.5 parts by mass Sulfur-containing polymer 4 2.5 parts by mass Polar resin 1 20.0 parts by mass I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 29 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Comparative Example 7>
Toner was produced in the same manner as in Example 1 except that 9.0 parts by mass of tricalcium phosphate was changed to 30.0 parts by mass and the formulation was changed as follows.
* Styrene 70.0 mass parts * N-butyl acrylate 30.0 mass parts * Toluene 2.5 mass parts * Said sulfur-containing polymer 7 1.5 mass parts * Said polar resin 9 20.0 mass parts * C.I. I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 30 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

<Comparative Example 8>
-Styrene 66.5 mass parts-N-butyl acrylate 33.5 mass parts-Toluene 2.5 mass parts-The above sulfur-containing polymer 1 2.5 mass parts-The polar resin 14 20.0 mass parts-C.I. I. Pigment Blue 15: 3 7.0 parts by mass, Wax: HNP-10 (melting point 75 ° C .; manufactured by Nippon Seiki Co., Ltd.) 10.0 parts by mass, di-t-butyl ether 0.05 parts by mass, 2,2′-azobis (2,4-Dimethylvaleronitrile) 8.0 parts by mass Cyan toner 31 was obtained in the same manner as in Example 1 except that the formulation was changed to the above materials and addition amounts. Table 1 shows the physical properties of the cyan toner.

  The cyan toners 1 to 31 thus obtained were mixed with a magnetic fine particle dispersed resin carrier (number average particle size 35 μm) surface-coated with a silicone resin so that the toner concentration was 7.0% by mass. Component developer was used.

  The cyan toners 1 to 31 described above were evaluated as follows.

<Evaluation of triboelectric charge amount of toner>
The triboelectric charge is measured by separating 50 g of the two-component developer, leaving it in a high temperature and high humidity environment (30 ° C., 80% RH) for 3 days, placing it in a 50 cc plastic container, 360 times over 3 minutes. Each was shaken, left in a high-temperature and high-humidity environment (30 ° C., 80% RH) for 3 days, shaken 30 times over 15 seconds, and shaken 300 times over 2 minutes 30 seconds, respectively. Measurement was performed using an apparatus. The evaluation was made by measuring the absolute value of the triboelectric charge amount at each shaking frequency and judging according to the following criteria. The results are shown in Table 2.
Rank A: The absolute value of the triboelectric charge after 30 times of shaking is 90% or more and 100% of the absolute value of the triboelectric charge after 30 times of shaking.
Rank B: Absolute value of triboelectric charge amount of 30 times shaking is 80% or more and less than 90% with respect to absolute value of triboelectric charge amount of 300 times of shaking C Rank: Absolute value of triboelectric charge amount of 300 times shaking On the other hand, the absolute value of the triboelectric charge amount of 30 times shaking is 70% or more and less than 80%. D rank: The absolute value of the triboelectric charge amount of 30 times shaking is 70% with respect to the absolute value of the triboelectric charge amount of 300 times shaking. %Less than

(Measurement method of triboelectric charge)
About 0.5 g of a developer for measuring the triboelectric charge amount is placed in a metal measuring container 2 having a 500 mesh screen 3 at the bottom, and a metal lid 4 is formed. The total mass of the measurement container 2 at this time is weighed and is defined as Wl (g). Next, in the suction device 1 (at least the portion in contact with the measurement container 2) is suctioned from the suction port 7 and the air volume control valve 6 is adjusted to set the pressure of the vacuum gauge 5 to 250 mmAq. In this state, the toner is removed by suction for 2 minutes.

The potential of the electrometer 9 at this time is set to V (volt). Here, 8 is a capacitor, and the capacity is C (μF). The mass of the entire measurement container after the suction is weighed and is defined as W2 (g). The triboelectric charge amount (mC / kg) of the toner is calculated as follows.
Frictional charge (mC / kg) = (C × V) / (W1-W2)

  As a result, it was found that in Examples 1 to 23 according to the present invention, the rising rate of charge decreased when left under high humidity as compared with Comparative Examples 1 to 8.

<Evaluation of toner durability>
(I) Evaluation was performed using the image forming apparatus of the contact one-component developing system shown in FIG. The developing unit was charged with 100 g of the toner and left in a high temperature and high humidity environment (30 ° C./80% RH) for 10 days. At this time, the transfer paper was also left in the same manner. Then, after being left for 1 day in a normal humidity and normal humidity environment (23 ° C., 60% RH), the density detection is corrected in a normal temperature and normal humidity environment (23 ° C., 60% RH), and the printing ratio is 1%. The continuous output was performed up to 3000 sheets in the chart. Then, it was left to stand for 10 days in a high temperature and high humidity environment (30 ° C./80% RH). At this time, the transfer paper was also left in the same manner. Then, after being left for 1 day in a normal humidity and normal humidity environment (23 ° C., 60% RH), the density detection is corrected in a normal temperature and normal humidity environment (23 ° C., 60% RH), and the printing ratio is 1%. In the chart, continuous output was performed up to 20 sheets (3020 total output sheets).

  As for the total number of output sheets, development efficiency after output of 3020 sheets, circumferential streaks and toner scattering, toner coat uniformity, transfer efficiency, uniformity within the same page, and transfer uniformity were confirmed.

i) When measuring the development efficiency, after 3020 sheets are output, the main body power is forcibly turned off while outputting the entire solid image (toner loading amount 0.55 mg / cm ² ), and the toner before development on the toner carrier The mass per unit area of the toner developed on the photosensitive drum was measured, and the development efficiency was calculated by the following equation.
Development efficiency (%) = (amount of toner developed on photosensitive drum / amount of toner on toner carrier) × 100

Evaluation conforms to the following judgments A, B, C, and D.
A: The development efficiency was 95% or more.
B: The development efficiency was 88% or more and less than 95%.
C: The development efficiency was 80% or more and less than 88%.
D: The development efficiency was less than 80%.

ii) Evaluation of circumferential streaks and toner scattering was made by outputting 3020 solid whole area images (toner loading 0.55 mg / cm ² ), then disassembling the developing container and visually observing the surface and edges of the toner carrier. I went. The criteria are shown below.
A: After output of 3020 sheets, it is caused by circumferential streaks due to foreign matter pinching between the toner regulating member and the toner carrying member due to toner destruction or fusion, or foreign matter pinching between the toner carrying member and the toner end seal. No toner scattering occurred.
B: After output of 3020 sheets, some toner scattering due to foreign matter sandwiched between the toner carrier and the toner end seal is observed.
C: After outputting 3020 sheets, toner scattering is slightly observed, and 1 to 4 circumferential streaks are also observed at the end.
D: After 3020 sheets are output, toner scattering is observed, and five or more circumferential streaks are also observed.

iii) When confirming toner coat uniformity, after 3020 sheets of half-tone entire area image (toner loading amount of 0.20 mg / cm ² ) are output, the main body power is forcibly turned off and the dots on the developed photosensitive drum The reproducibility was confirmed. Evaluation was performed while visually observing an image magnified 100 times with an optical microscope. The criteria are shown below.
A: Even after 3020 sheets were output, the dot reproducibility was excellent.
B: There was some disturbance after 3020 sheets were output.
C: Disturbance was large after 3020 sheets were output.

iv) When measuring the transfer efficiency, after outputting 3020 solid whole area images (toner loading amount of 0.55 mg / cm ² ), the main body power is forcibly turned off, the toner before transfer on the photosensitive drum, and the transfer material The mass per unit area of the toner transferred to the toner was measured, and the transfer efficiency was calculated by the following equation.
Transfer efficiency (%) = (amount of toner transferred to transfer material / amount of toner on photosensitive drum) × 100

The transfer efficiency is evaluated according to the following judgments A, B, C, and D.
A: The development efficiency was 90% or more.
B: The development efficiency was 83% or more and less than 90%.
C: The development efficiency was 75% or more and less than 83%.
D: The development efficiency was less than 75%.

v) When confirming the uniformity of the image in the same page, the half-tone entire image (toner applied amount 0.20 mg / cm ² ) and the solid entire image (toner applied amount 0.55 mg / cm ² ) are stored in Xerox 4024 ( 75 g / cm ² ) and evaluated. The criteria are shown below.
A: Even after 3020 sheets were output, the uniformity of images in the same page was excellent for both halftone and solid.
B: After 3020 sheets were output, the uniformity of images in the same page was slightly inferior in a halftone image.
C: After 3020 sheets were output, the uniformity of images in the same page was inferior for both halftone and solid.

vi) When confirming the transfer uniformity, the entire halftone image with a toner loading of 0.20 mg / cm ² is transferred to Xerox 4024 paper (75 g / cm ² ) and Fox River Bond paper (90 / cm ² ). And evaluated. The criteria are shown below.
A: Even after 3020 sheets were output, good transfer uniformity was exhibited on both Xerox 4024 paper and Fox River Bond paper.
B: After 3020 sheets were output, the transfer uniformity was slightly inferior on Fox River Bond paper.
C: After 3020 sheets were output, the transfer uniformity was greatly inferior on Fox River Bond paper.

(II) Evaluation of low-temperature fixability / high-temperature wrapping property In the image forming apparatus of the contact one-component development system shown in FIG. 4, the developer is filled with 85 g of the toner described in the examples and comparative examples, Leave it in a humid environment (30 ° C, 80% RH) for 10 days, then leave it in a room temperature and normal humidity environment (23 ° C, 60% RH) for 2 hours, and then transfer a 10 mm x 10 mm square image to the entire transfer paper. An image pattern in which 9 points were evenly arranged on the paper was formed on Fox River Bond paper (90 / cm ² ), and an unfixed image was output. In this case, the applied amount of toner was a monochromatic halftone image of 0.2 mg / cm ² .

  The temperature can be controlled, the oil application function is not provided, and the fixing speed is 150 mm / sec by using an external fixing device that performs fixing by passing through a nip portion composed of a heat roller and a pressure roller having a diameter of 40 mm. The unfixed image was fixed. In this case, as the roller material, a fluorine material was used for both the upper part and the lower part, and the nip width was 6 mm.

Also, the determination of fixing start is made by rubbing the fixed image (including the image offset at a low temperature) with a load of 50 g / cm ² with Sylbon paper [Lenz Cleaning Paper “dasper (R)” (Ozu Paper Co. Ltd)]. Went by. The temperature at which the density reduction rate after rubbing becomes less than 20% was set as a temperature for evaluating “low temperature fixability”.

  Further, the winding property at high temperature was confirmed visually. The maximum temperature at which paper could be passed without winding was taken as the temperature for evaluating “high temperature winding property”.

  As a result, in Examples 1 to 23 according to the present invention, compared to Comparative Examples 1 to 8, the rising speed of charging decreased when left under high humidity, and further, development efficiency after endurance and streak in the circumferential direction were increased. In addition, it was found that toner scattering, toner coat uniformity, transfer efficiency, uniformity within the same page, transfer uniformity are excellent, and low-temperature fixability can also be achieved.

It is a figure which shows the structure of the apparatus used for the measurement of the triboelectric charge amount of the developing agent using the toner of this invention. It is a figure which shows the penetration time-penetration film thickness curve at the time of UV photocurable composition osmosis | permeation of a toner, and L, Va, Vb. It is an enlarged view of the developing unit of the electrophotographic apparatus. 1 is a diagram illustrating a configuration of an image forming apparatus using a contact one-component developing system.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Suction machine 2 Measuring container 3 Screen 4 Lid 5 Vacuum gauge 6 Air volume control valve 7 Suction port 8 Condenser 9 Electrometer 10 Photosensitive drum 11 Electrostatic latent image carrier contact charging member 12 Power supply 13 Development unit 14 Toner carrier 15 Toner supply Roller 16 Restriction member 17 Non-magnetic toner 23 Developer container 24 Restriction member support sheet metal 25 Toner transport member 27 Bias 101 (101a to 101d) Drum type electrophotographic photosensitive member (photosensitive drum)
102 (102a to 102d) Primary charging means 103 (103a to 103d) Laser beam exposure means (scanner)
104 (104a to 104d) Developing section 106 (106a to 106d) Cleaning means 108b Paper feed roller 108c Registration roller 109a Electrostatic adsorption transport belt 109b Drive roller 109c Fixed roller 109d Tension roller 109e Fixed roller 110 Fixing device 110c Discharge roller 113 Discharge tray S transfer material (recording medium)

Claims (6)

  A toner having toner particles containing at least a binder resin, a wax, a colorant, and a sulfur-containing polymer, and carbon atoms and oxygen atoms detected by surface analysis of the toner particles by an X-ray photoelectron spectroscopy (XPS) method , The number% of sulfur atoms is 0.05 to 0.74% with respect to the sum of the number of atoms of each element of nitrogen atom and sulfur atom, and the number of sulfur atoms (%) / oxygen A toner having a ratio of the number (%) of atoms of 0.050 to 0.140. The toner has a glass transition temperature (TgA) measured by a differential scanning calorimeter of 40 to 60 ° C., and the cyclohexane insoluble content in the tetrahydrofuran (THF) soluble content of the toner is:
i) The glass transition temperature (TgB) measured by a differential scanning calorimeter is 80 to 120 ° C.,
ii) The acid value is 5 to 40 mgKOH / g, and the glass transition temperature (TgA) and the glass transition temperature (TgB) are represented by the following formula (1)
(Formula 1) 25 ° C. ≦ (TgB−TgA) ≦ 70 ° C.
And
The toner according to claim 1, wherein the toner has toner particles containing a polar resin, and the polar resin is a vinyl polymer containing a cyclohexane insoluble matter. When the UV photocurable composition is infiltrated into the toner, the osmotic film thickness at an osmosis time of 5 seconds is L (μm), and the average osmotic speed is Va (μm / s) in the range of an osmosis time of 5 seconds to 10 seconds. ), Where the average penetration speed in the range of 10 seconds to 15 seconds is Vb (μm / s), L, Va, Vb are represented by the following formulas (2) to (4):
Formula (2) 0.20 <= L <= 0.60
Formula (3) 0.02 ≦ Va ≦ 0.07
Formula (4) Va <Vb
The toner according to claim 1, wherein the toner satisfies the following condition.   The toner particles are obtained by granulating a polymerizable monomer composition containing at least the polymerizable monomer, the wax, the colorant, and the sulfur-containing polymer in an aqueous medium, The toner according to claim 1, wherein the toner particles are produced by polymerization. The sulfur-containing polymer has the following chemical formula (1)

(In the formula, B1 represents an optionally substituted alkylene group having 1 or 2 carbon atoms or an aromatic ring optionally having a substituent, and the substituent in the alkylene structure includes a hydroxyl group, It is a C1-C12 alkyl group, an aryl group, or an alkoxy group, and as an anchoring group in an aromatic ring, it is a hydroxyl group, a C1-C12 alkyl group, an aryl group, or an alkoxy group, and is adjacent. (Including carbon, a 5-membered or 6-membered aromatic ring may be formed. R1 represents an alkyl group having 1 to 12 carbon atoms or an aryl group.)
5. The toner according to claim 1, wherein the toner comprises a unit represented by the formula:   The toner according to claim 5, wherein the sulfur-containing polymer is a vinyl polymer.

Images