JP4732137B2 - Charge control resin for toner, toner and method for producing toner particle - Google Patents

Description

  The present invention relates to a toner for developing an electrostatic charge image in an image forming method such as electrophotography or electrostatic printing, or a toner for forming a toner image in a toner jet type image forming method. In particular, the present invention relates to a toner that is used in a fixing method in which a toner image formed with toner is fixed by heating and pressing on a print sheet such as a transfer material.

  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 charge characteristic of the binder resin itself can be used, but generally the binder resin used in the toner often has a low triboelectric charge characteristic, and the chargeability due to its composition. Control 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. Therefore, these additives fall off from the toner surface due to friction between toners, collision with a carrier, friction with a conveying sleeve or roller, a regulation blade, a photosensitive drum, and the like. Contamination of body drums may occur. As a result, as the number of durable sheets increases, the chargeability deteriorates and deterioration due to contamination progresses, causing 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 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 it is preferable that there is no polymerization inhibitory property for use in a polymerized toner. Therefore, if these are taken into consideration, there are very few that can be put into practical use.

  As a process for fixing the toner image, a pressure heating method using a heat roller (hereinafter referred to as a heat roller fixing method), or a heat fixing method (hereinafter referred to as a film) in which a fixing sheet is fixed to a heated body through a fixing film. The fixing method) has been developed.

  In the heat roll or film fixing method, fixing is performed by allowing a toner image on a fixing sheet to pass through the surface of a heat roller or a fixing film while being contacted under pressure by a pressure member that abuts. In this fixing method, the surface of the heat roller or fixing film and the toner image of the fixing sheet are in contact with each other under pressure, so that the thermal efficiency when fusing the toner image on the sheet is extremely high, and quick and good fixing is achieved. It can be carried out.

  In response to various demands for recent electrophotographic devices such as higher image quality, smaller and lighter, higher speed and higher productivity, energy saving, higher reliability, lower cost, and maintenance-free, especially in the fixing process. Development of systems and materials that can achieve even higher speeds, energy savings, and higher reliability is an important technical issue. However, in order to solve these problems with a heat roller or film fixing method, it is essential to significantly improve the fixing characteristics of the toner, which is a material, and it is sufficiently fixed on the fixing sheet at a lower temperature. Improved performance (hereinafter referred to as low-temperature fixing performance) and performance capable of preventing offset, which is a phenomenon that stains the next fixing sheet due to toner contamination adhering to the heating roller or film surface (hereinafter referred to as anti-offset performance) Need to be improved.

  In a heat and pressure fixing toner, a toner containing a wax having a high affinity with a binder resin exhibits good offset resistance and low temperature fixing performance under specific fixing conditions (for example, Patent Documents 1 and 2). reference). However, these toners have a glass transition point and a melt viscosity of the toner that are reduced as the wax is dissolved in the binder resin. In addition to fluidity, chargeability tends to be impaired. In particular, when continuous printing is performed, a significant density drop and image defects are likely to occur. For this reason, there is a long-awaited toner that satisfies development stability performance due to excellent charging performance and has further low-temperature fixing performance.

  By the way, LED and laser beam printers have become the mainstream in the recent market as printer devices, and the direction of technology is higher resolution, that is, the conventional 300, 400 dpi has become 600, 1200 dpi. Accordingly, with this development, higher definition has been demanded. In addition, copiers are also becoming more sophisticated, and therefore are moving toward digitalization. Since this method mainly uses a method of forming an electrostatic latent image with a laser, it is also proceeding in the direction of high resolution, and here again, a high-resolution and high-definition developing method has been required as in the case of a printer. Yes. As one means for satisfying this requirement, the particle size of the toner has been reduced, and a toner having a small particle size within a specific particle size distribution range has been proposed (for example, see Patent Documents 3 to 8).

However, as the toner particle size becomes smaller, stable tribocharging of the toner powder becomes an important technique. In other words, unless the fine individual toner particles have a uniform charge amount, the above-described decrease in image stability is more likely to appear. This is because the particle size of the toner is simply reduced, and the adhesion force of the toner particles to the photoreceptor (compared to the Coulomb force applied to the toner particles in the transfer process) (
In addition to an increase in residual toner, resulting in a decrease in toner diameter and a decrease in fluidity, the charge amount of individual toner particles becomes uneven. This is because toner particles that are easy to fog and have poor transferability increase.

  From the background as described above, studies for improving the charging characteristics 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 because of environmental considerations, more stable charging requirements, manufacturing costs, and the like (for example, Patent Documents). 9, 10).

  According to these documents, a toner having improved chargeability can be obtained. However, when the present inventors examined these toners, when a large number of printouts were made, the toner charged with a reverse polarity gradually increased in the developing device, and so-called reversal fog rapidly deteriorated. It turns out that it has the problem of doing. In these documents, only a binary copolymer composed of styrene and 2-acrylamido-2-methylpropanesulfonic acid is described, but the glass transition temperature of the binary copolymer described is 90. The temperature was higher than or equal to ℃, and there were cases where problems occurred in low-temperature fixability.

  Further, a toner containing a further improved copolymer of sulfonic acid group-containing acrylamide and a vinyl monomer has been proposed (see, for example, Patent Documents 11, 12, and 13). However, even in these documents, the compatibility between the charging performance (particularly the initial rising performance) and the fixing performance is not sufficiently satisfactory.

  There have been some proposals for improving the chargeability of resins having a charge control function (see, for example, Patent Documents 14 and 15). According to these documents, it is possible to obtain a toner having a relatively good rise in chargeability and good dispersion of various additives in the binder resin. However, there is room for further improvement with respect to the chargeability, and it cannot be said that the low-temperature fixability is sufficient. Furthermore, the toners described in these documents may not have sufficient transferability and may cause problems in image quality.

JP-A-8-50367 JP 2001-318484 A Japanese Patent Laid-Open No. 1-112253 JP-A-1-191156 JP-A-2-214156 JP-A-2-284158 Japanese Patent Laid-Open No. 3-181952 JP-A-4-162048 Japanese Patent Publication No.8-12467 Japanese Patent No. 2663016 Japanese Patent Laid-Open No. 11-184165 JP 11-288129 A Japanese Patent Laid-Open No. 2000-56518 Japanese Patent No. 2807795 JP-A-8-30017

  The present invention has been made in view of the above problems. That is, the object of the present invention is a toner having good fixability, excellent charging characteristics, stable development and transferability from the initial stage to after printing out a large number of sheets, and stable images over a long period of time. An object of the present invention is to provide a toner capable of obtaining the toner.

As a result of intensive studies, the present inventors have improved the charging performance of the toner and maintained the fixability and development / transferability by causing the copolymer to have a specific structure having a sulfonate group. The present invention has been completed by finding a charge control resin for toner that can be used.
That is, the present invention relates to the following charge control resin for toner, toner and a method for producing toner particles.
(1) at least one) units A derived from a monomer is Ru represented by the following general formula (4),
2) Unit B having a carboxyl group,
3) a copolymer comprising a unit C derived from an aromatic vinyl monomer, and 4) a unit derived from an acrylate ester or methacrylate ester,
The content ratio of unit A based on the number of units in the copolymer is
Unit A: All units other than Unit A = 1: 99 to 15:85
Because
The content ratio based on the number of units of unit B in the copolymer is:
Unit B: All units other than unit B = 0.05: 99.95 to 8.00: 92.00
I der,
The content ratio of unit C based on the number of units in the copolymer is
Unit C: All units other than unit C = 80.6: 19.4 to 98.0: 2.0
Toner charge control resin, characterized in der Rukoto.

(In the formula, R18 represents a hydrogen atom or a methyl group, and B is represented by the following formula (1) or (2).)

（式中、Ｒ１〜４は独立に水素原子、炭素数１〜１２のアルキル基を表し、Ｒ５はメチル基又はエチル基を表し、Ａ１はアミド結合を表す。）

(In the formula, R1 to 4 independently represent a hydrogen atom and an alkyl group having 1 to 12 carbon atoms, R5 represents a methyl group or an ethyl group, and A1 represents an amide bond.)

（式中、Ｒ６〜９は独立に水素原子、炭素数１〜１２のアルキル基、メトキシ基を表し、Ｒ１０はメチル基を表し、Ａ２はアミド結合を表す。）
（２）少なくとも結着樹脂、着色剤、及び、前記トナー用荷電制御樹脂を含有するトナー粒子を有するトナーであって、
該トナー用荷電制御樹脂の含有量が、前記結着樹脂１００質量部に対して０．１〜２０質量部であることを特徴とするトナー。
（３）トナー用荷電制御樹脂を有する組成物を水系媒体中で分散する工程を有するトナー粒子の製造方法であり、
該トナー粒子は、少なくとも結着樹脂、着色剤及びトナー用荷電制御樹脂を含有し、
該トナー用荷電制御樹脂の含有量が、該結着樹脂１００質量部に対して０．１〜２０質量部であり、
該トナー用荷電制御樹脂が前記トナー用荷電制御樹脂であることを特徴とするトナー粒子の製造方法。

(Wherein R6 to 9 independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a methoxy group, R10 represents a methyl group, and A2 represents an amide bond.)
(2) A toner having toner particles containing at least a binder resin, a colorant, and the charge control resin for toner,
The toner, wherein the content of the charge control resin for toner is 0.1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.
(3) A method for producing toner particles comprising a step of dispersing a composition having a charge control resin for toner in an aqueous medium.
The toner particles contain at least a binder resin, a colorant, and a charge control resin for toner,
The content of the charge control resin for toner is 0.1 to 20 parts by mass with respect to 100 parts by mass of the binder resin,
A method for producing toner particles, wherein the charge control resin for toner is the charge control resin for toner.

By using the toner containing the charge control resin for toner characterized by the present invention described below, good low-temperature fixability and stable triboelectric chargeability can be obtained, and as a result, long-term development and transferability are good. It is possible to obtain a stable image over a wide range.

  The inventors of the present invention have made extensive studies on toner fixing properties, charging stability, development / transfer properties, and the like. As a result, at least a unit A having a structure represented by the following formula (1) or (2) or (3) is used. By including a copolymer contained as a partial structure (hereinafter, sometimes simply referred to as “copolymer”), a toner with excellent charging properties and stable charging characteristics even with a toner having excellent fixing properties. It has been found that can be provided.

（式中、Ｒ１〜４は独立に水素原子、水酸基、炭素数１〜１２のアルキル基、アリール基、アルコキシ基を表し、Ｒ５は炭素数１〜１２のアルキル基、アリール基を表し、Ａ１はアミド結合、ウレタン結合、ウレア結合、エステル結合、エーテル結合を表す。）

(Wherein R1 to 4 independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an aryl group or an alkoxy group, R5 represents an alkyl group having 1 to 12 carbon atoms or an aryl group, and A1 represents (Represents an amide bond, urethane bond, urea bond, ester bond, or ether bond.)

（式中、Ｒ６〜９は独立に水素原子、水酸基、炭素数１〜１２のアルキル基、アリール基、アルコキシ基を表し、また、隣接する同士が５員環又は６員環の芳香族環を形成していてもよく、Ｒ１０は炭素数１〜１２のアルキル基、アリール基を表し、Ａ２はアミド結合、ウレタン結合、ウレア結合、エステル結合、エーテル結合を表す。）

(Wherein R6 to 9 independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an aryl group, or an alkoxy group, and adjacent to each other represent a 5-membered or 6-membered aromatic ring. R10 represents an alkyl group having 1 to 12 carbon atoms or an aryl group, and A2 represents an amide bond, a urethane bond, a urea bond, an ester bond, or an ether bond.

（式中、Ｒ１１〜１６は独立に水素原子、水酸基、炭素数１〜１２のアルキル基、アリール基、アルコキシ基を表し、また、隣接する同士が５員環又は６員環の芳香族環を形成していてもよく、Ｒ１０は炭素数１〜１２のアルキル基、アリール基を表し、Ａ３はアミド結合、ウレタン結合、ウレア結合、エステル結合、エーテル結合を表す。）

(Wherein R11 to 16 independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an aryl group, or an alkoxy group, and adjacent to each other represent a 5-membered or 6-membered aromatic ring. R10 represents an alkyl group having 1 to 12 carbon atoms or an aryl group, and A3 represents an amide bond, a urethane bond, a urea bond, an ester bond, or an ether bond.

  The most characteristic point of the copolymer is that it has a sulfonate group as shown in the formula (1), (2) or (3). That is, it is possible to improve the charging effect by having a sulfonic acid ester group with respect to a conventionally proposed resin having a sulfonic acid group. As a result, the toner containing this resin is excellent in the start-up characteristic in the frictional charging from the initial stage. The reason for this is not clear, but it is presumed that the sulfonic acid ester group has higher hydrophobicity than the sulfonic acid group, and the electron withdrawing property functions without being affected by water molecules in the air. Further, 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. Further, in a toner produced by a production method having a granulation step in an aqueous medium, a resin having a sulfonic acid group or a sulfonic acid group may affect the granulation property. In some cases, however, the resin having a sulfonic acid ester group significantly reduces the influence on the granulation property. On the other hand, it has been found that when there are too many units A having a sulfonic acid ester group, the toner developability and transferability may be impaired. For this reason, the charge imparting effect is exhibited when the unit A is present at a specific ratio.

  In addition, a characteristic point of the copolymer is that it contains a unit B having a carboxyl group. In the method of producing toner particles under the condition that the copolymer of the present invention is previously contained in the process of producing toner particles and the copolymer is localized on the surface of the toner particles to be produced, In order to localize the copolymer on the surface of the toner particles, it has been found that it is important to give an acid value to the copolymer.

  Furthermore, although the reason is not clear, the copolymer containing the unit B having a carboxyl group can not only localize on the surface of the toner particles, but also stabilizes the toner containing the toner particles before and after endurance of frictional charging. It has been found that the property can be improved. In addition, the carboxyl group in the unit B containing a carboxyl group may be a carboxylate anion.

  In addition, a characteristic point of the copolymer is that it has a unit C derived from an aromatic vinyl monomer. When the copolymer as described above is localized in the vicinity of the toner surface, when the glass transition point of the copolymer is low, the storage stability of the toner is deteriorated to cause a blocking phenomenon, particularly in a high temperature environment. There is a risk of causing fusion to the inside of the developing unit and the developing member, and further, toners may be fused to cause a decrease in fluidity. In addition, it is essential to control the compatibility with the binder resin. As a result of intensive studies by the present inventor, having the unit C derived from the aromatic vinyl monomer makes it possible to control the compatibility of the toner with the binder resin without hindering the charging effect of the units A and B. Furthermore, it has been found that the glass transition point of the resin can be designed within a suitable range. In addition, the molecular weight can be easily controlled while maintaining the random copolymerizability, and the uneven distribution of the units A in the molecule can be prevented. For the reasons described above, the charging characteristics can be stabilized without impairing the fixability of the resulting toner.

Next, the content ratio of each unit in the copolymer will be described. In the present invention, the unit A represented by the general formula (1) is based on the number of units (molar basis) with respect to other units (all other than the unit A) forming the copolymer,
Unit A: All units other than unit A = 1: 99 to 15:85
It is more preferable that it is 3: 97-12: 88. If the number of units A is too small, the chargeability may be insufficient. Conversely, if the number of units A is too large, the development / transferability may be deteriorated. In addition, in this invention, a unit is a structural unit derived from the monomer which is used for superposition | polymerization of a copolymer and comprises a copolymer.

In the copolymer, unit B is based on the number of units (molar basis) with respect to other units (all except unit B) forming the copolymer,
Unit B: All units other than unit B = 0.05: 99.95 to 8.00: 92.00
And more preferably 0.5: 99.5 to 6.0: 94.0. When the proportion of unit B is less than 0.05, the amount of the copolymer present on the toner surface may be insufficient, or the chargeability may not be stable after the endurance. On the contrary, when the ratio of the unit B is more than 8.00: 92.00, the dispersion state of the copolymer in the toner is affected, or the chargeability of the toner is the environment (temperature / humidity). May be affected by change. For the above reasons, it is preferable that the units B coexist at the specific ratio.

Furthermore, when the proportion of the unit C derived from the aromatic vinyl monomer is too small, the Tg of the resin may be lowered, and the storage stability and durability stability of the toner may be lowered. In some cases, the solubility is significantly deteriorated and the amount of the resin existing in the vicinity of the toner surface is extremely reduced (or increased), and the effect of containing the resin is not sufficiently exhibited. Therefore, unit C is based on the number of units (molar basis) with respect to other units (all except unit C) forming the copolymer.
Unit C: All units other than unit C = 30.0: 70.0 to 98.0: 2.0
It is particularly preferable to satisfy 50.0: 50.0 to 98.0: 2.0.

  The method for synthesizing the copolymer is not particularly limited, but as a preferred method, a monomer component containing at least a monomer represented by the following general formula (4), a monomer having a carboxyl group, and an aromatic vinyl monomer is copolymerized. It is a method to do.

（式中、Ｒ１８は水素原子又はメチル基を表し、Ｂは下記式（５）又は（６）又は（７）で表される。）

(In the formula, R18 represents a hydrogen atom or a methyl group, and B is represented by the following formula (5) or (6) or (7).)

（式中、Ｒ１９〜２２は独立に水素原子、水酸基、炭素数１〜１２のアルキル基、アリール基、アルコキシ基を表し、Ｒ２３は炭素数１〜１２のアルキル基、アリール基を表し、Ａ４はアミド結合、ウレタン結合、ウレア結合、エステル結合、エーテル結合を表す。）

(In the formula, R19 to 22 independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an aryl group or an alkoxy group, R23 represents an alkyl group having 1 to 12 carbon atoms or an aryl group, and A4 represents (Represents an amide bond, urethane bond, urea bond, ester bond, or ether bond.)

（式中、Ｒ２４〜２７は独立に水素原子、水酸基、炭素数１〜１２のアルキル基、アリール基、アルコキシ基を表し、また、隣接する同士が５員環又は６員環の芳香族環を形成していてもよく、Ｒ２８は炭素数１〜１２のアルキル基、アリール基を表し、Ａ５はアミド結合、ウレタン結合、ウレア結合、エステル結合、エーテル結合を表す。）

(In the formula, R24 to 27 each independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an aryl group, or an alkoxy group, and adjacent to each other represent a 5-membered or 6-membered aromatic ring. R28 represents an alkyl group having 1 to 12 carbon atoms or an aryl group, and A5 represents an amide bond, a urethane bond, a urea bond, an ester bond or an ether bond.

（式中、Ｒ２９〜３４は独立に水素原子、水酸基、炭素数１〜１２のアルキル基、アリール基、アルコキシ基を表し、また、隣接する同士が５員環又は６員環の芳香族環を形成していてもよく、Ｒ３５は炭素数１〜１２のアルキル基、アリール基を表し、Ａ６はアミド結合、ウレタン結合、ウレア結合、エステル結合、エーテル結合を表す。）

(In the formula, R29 to 34 each independently represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an aryl group, or an alkoxy group, and adjacent to each other are 5-membered or 6-membered aromatic rings. R35 may represent an alkyl group having 1 to 12 carbon atoms or an aryl group, and A6 represents an amide bond, urethane bond, urea bond, ester bond or ether bond.)

  A known method can be used as a method for synthesizing the monomer represented by the above formula (4). For example, a method in which an amine or alcohol having the structure of the above formula (5) or (6) or (7) is combined with a reactive acrylate or the like (for example, acrylic acid chloride, methacrylic anhydride, isocyanate oxyethyl methacrylate, or the like). is there.

  The monomer having a carboxyl group is not particularly limited, and specific examples include acrylic acid, methacrylic acid, maleic acid, vinyl acetate and the like, and acrylic acid and methacrylic acid are particularly preferable. . Specific examples of the aromatic vinyl monomer include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-methoxy styrene, p-phenyl styrene, p-chloro styrene, 3,4-distyrene. Chlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, Examples thereof include styrene such as pn-decyl styrene and pn-dodecyl styrene, and derivatives thereof. In particular, styrene is most commonly used.

  In order to control the physical properties of the copolymer according to the toner performance and the toner production method, it is preferable to copolymerize a monomer ((meth) acrylic acid ester) represented by the following formula (8). When the copolymer has a (meth) acrylic acid ester unit, the compatibility with the binder resin and the wax can be finely adjusted, and the glass transition point can be easily adjusted. In addition, the solubility in a solvent can be improved, and further, random copolymerization can be further enhanced, and the uniform distribution of sulfonic acid ester units in the molecule is promoted.

As the mixing ratio of these monomers, if the content ratio of unit C is considered,
Monomer represented by formula (8): Aromatic vinyl monomer = 99.1: 0.1-40.0: 60.0
Is preferred.

（式中、Ｒ３６は水素原子又はメチル基を表し、Ｒ３７は置換基を有していても良い炭素数１〜２０のアルキル基を表し、置換基としては水酸基、メトキシ基、エトキシ基、アセチル基、アミノ基である。）

(In the formula, R36 represents a hydrogen atom or a methyl group, R37 represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, and the substituent includes a hydroxyl group, a methoxy group, an ethoxy group, and an acetyl group. An amino group.)

  Specific examples of the compound having the structure of the above formula (8) include methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid-n-octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid. Α-methylene fatty acid monocarboxylic acid esters such as stearyl, phenyl methacrylate, 2-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate , Isobutyl acrylate, propyl acrylate, -n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, 2-acrylate Rokishiechiru, may be mentioned acrylic acid esters such as.

  In consideration of solubility in a solvent, compatibility with a binder resin, compatibility with waxes, and the like, the copolymer resin may be copolymerized with another monomer as a constituent component. Monomers that may be copolymerized can be arbitrarily selected from known ones. Specific examples include ethylene unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene; unsaturated polyenes such as butadiene and isoprene, Vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; N-vinyl compounds such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone Vinyl naphthalenes; acrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide.

  Various polymerization initiators such as peroxide polymerization initiators and azo polymerization initiators can be used as the polymerization initiator that can be used when copolymerizing the monomer components as described above.

  Examples of the peroxide polymerization initiator that can be used include peroxyesters, peroxydicarbonates, dialkyl peroxides, peroxyketals, ketone peroxides, hydroperoxides, diacyl peroxides, and inorganic ones. Examples of the system include persulfate and hydrogen peroxide. Specifically, t-butyl peroxyacetate, t-butyl peroxylaurate, t-butyl peroxypivalate, t-butyl peroxy- 2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxyneodecanoate, t-hexylperoxyacetate, t-hexylperoxylaurate, t-hexylperoxypivalate, t -Hexylperoxy-2-ethylhexanoate, t- Xylperoxyisobutyrate, t-hexylperoxyneodecanoate, t-butylperoxybenzoate, α, α'-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1, 1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate Ate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate , T-butyl peroxyisopropyl monocarbonate, t-butyl -Oxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxy-m-toluoylbenzoate, bis (t-butylperoxy) Oxy) isophthalate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, 2,5-dimethyl-2,5-bis (m-toluoylperoxy) Peroxyesters such as hexane; diacyl peroxides such as benzoyl peroxide, lauroyl peroxide, and isobutyryl peroxide; peroxydicarbons such as diisopropyl peroxydicarbonate and bis (4-t-butylcyclohexyl) peroxydicarbonate Ne 1,1-di-t-butylperoxycyclohexane, 1,1-di-t-hexylperoxycyclohexane, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, , 2-di-t-butylperoxybutane and other peroxyketals; di-t-butyl peroxide, dicumyl peroxide and t-butylcumyl peroxide and other dialkyl peroxides; A monocarbonate etc. are mentioned. Examples of the azo polymerization initiator that can be used include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane- 1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile and the like.

  If necessary, two or more of these polymerization initiators can be used simultaneously.

  It is preferable that the usage-amount of the polymerization initiator used in this case is 0.1-20 mass parts with respect to 100 mass parts of monomers.

  As the polymerization method, any method such as solution polymerization, suspension polymerization, emulsion polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization and the like can be used, and it is not particularly limited.

  In the present invention, if the molecular weight of the copolymer is too small, in addition to easily contaminating members such as a sleeve and a carrier, the charging characteristics of the sulfonic acid unit and the sulfonic acid ester unit may be adversely affected. . On the other hand, when the molecular weight is too large, not only the fixability of the toner may be impaired, but also the presence state of the copolymer in the toner may not be stable, and uniform charging characteristics may not be exhibited. From the above viewpoint, the molecular weight of the copolymer is preferably 2000 to 200000 in weight average molecular weight calculated by gel permeation chromatography. As a more preferable range, the weight average molecular weight is 5,000 to 100,000.

  Further, from the viewpoint of charging characteristics and fixability, the copolymer preferably has a narrow molecular weight distribution. The preferred molecular weight distribution ranges from 1.0 to 6.0 in terms of weight average molecular weight Mw and number average molecular weight Mn calculated by gel permeation chromatography (GPC), more preferably 1. 0 to 4.0.

  Measurement of molecular weight by GPC may be performed as follows.

A solution obtained by adding the copolymer to THF (tetrahydrofuran) and allowing to stand at room temperature for 24 hours is filtered through a solvent-resistant membrane filter having a pore diameter of 0.2 μm to obtain a sample solution, which is measured under the following conditions. In addition, sample preparation adjusts the quantity of THF so that the density | concentration of a copolymer may be 0.4-0.6 mass%.
Apparatus: High-speed GPC HLC8120 GPC (manufactured by Tosoh Corporation)
Column: Shodex KF-801, 802, 803, 804,
Seven series of 805, 806, 807 (made by Showa Denko KK)
Eluent: Tetrahydrofuran Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml

  In calculating the molecular weight of the sample, standard polystyrene resin (TSO standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F- manufactured by Tosoh Corporation) was used. 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500).

  As described above, it is preferable to control the glass transition point (Tg) of the copolymer in order to exert the effect without impairing the toner fixing property, and Tg measured by a differential scanning calorimeter (DSC). Is preferably in the range of 45 ° C to 90 ° C. A more preferable range is 50 ° C to 85 ° C.

  In order to cope with the toner production method, to improve the compatibility with the binder resin, and to localize the copolymer in the vicinity of the toner surface when producing toner particles in an aqueous medium, the copolymer is used. Preferably has a specific acid value. However, when the acid value is too high, the charging characteristics of the unit A may be hindered. A preferable acid value range of the copolymer is 3.0 to 40.0 mgKOH / g, and more preferably 5.0 to 30.0 mgKOH / g.

  In addition, the acid value in this invention is calculated | required with the following method.

Basic operation is based on JIS K-0070.
1) Weigh accurately 0.5 to 2.0 g of pulverized sample. The weight at this time is W (g).
2) Put the sample in a 300 ml beaker, and add 150 ml of a toluene / ethanol (4/1) mixture to dissolve.
3) Perform titration using a 0.1 mol / l ethanol solution of KOH using a potentiometric titrator (for example, a potentiometric titrator AT-400 (winworkstation) manufactured by Kyoto Electronics Co., Ltd.) and an ABP-410 electric burette. Automatic titration using can be used.)
4) The amount of KOH solution used at this time is S (ml). At the same time, a blank is measured, and the amount of KOH used at this time is defined as B (ml).
5) Calculate the acid value according to the following formula. f is a factor of KOH.
Acid value (mgKOH / g) = {(SB) × f × 5.61} / W

  The toner of the present invention exhibits the effect by containing the copolymer, but the content is not particularly limited. A preferred range is 0.1 to 20 parts by mass, and more preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the binder resin.

  There is no restriction | limiting in particular as binder resin used in this invention. For example, styrene resin, acrylic resin, styrene-acrylic resin, polyethylene resin, polyethylene-vinyl acetate resin, vinyl acetate resin, polybutadiene resin, phenol resin, polyurethane resin, polybutyral resin, polyester resin, and the like can be given. Among these, styrenic resins, acrylic resins, styrene-acrylic resins, polyester resins, and the like are desirable in terms of toner characteristics.

  The peak molecular weight calculated by GPC of the resin component soluble in THF of the toner of the present invention is preferably in the range of 3000 to 80000, and if it is smaller than 3000, there may be a problem in chargeability, and it is larger than 80000. It becomes difficult to fix at low temperature. The method for measuring the peak molecular weight is the same as the method for measuring the molecular weight of the resin.

  The toner of the present invention preferably contains a wax. By including a wax in the toner, it is possible to obtain a toner excellent in fixability that can obtain a fixed image having excellent low-temperature fixability and offset resistance and excellent surface smoothness.

  When the wax is contained in the toner, the melted wax acts as a release agent between the transfer material and the fixing member due to the surface tension, and not only significantly improves the anti-offset performance. The low-temperature fixability can be improved by accelerating the melting of the toner at the time of fixing. In order to effectively exhibit such a wax action in the toner, the melting point of the wax is very important. That is, in the toner having excellent fixability, the melting peak temperature seen at the time of temperature rise is important in the toner DSC curve measured by the differential scanning calorimeter. When the temperature of the melting peak is too high, the releasing action at low temperature is not exhibited, and not only sufficient offset resistance is not obtained, but also low temperature fixing performance cannot be expected. On the other hand, if it is too low, the melt viscosity of the toner will be too low, so that the releasing action on the high temperature side will not be exhibited, sufficient offset resistance will not be obtained, Even sticking is caused. For the reasons described above, in the preferable toner DSC curve, the temperature range of the melting peak observed at the time of temperature rise is 45 ° C to 130 ° C, more preferably 50 ° C to 110 ° C, and further preferably 50 ° C to 110 ° C. 90 ° C.

  The wax used in the toner of the present invention preferably has a content in the range of 0.5 to 30 parts by mass with respect to 100 parts by mass of the binder resin. If the content is less than 0.5 parts by mass, the effect of improving the offset resistance described above is not sufficient, and if it exceeds 30 parts by mass, the long-term storage stability is lowered and the dispersibility of other toner materials is poor. In addition, the amount of wax present in the vicinity of the toner surface increases, which may lead to a case where the charging characteristics which are the characteristics of the present invention are hindered, a decrease in toner fluidity, and a decrease in image characteristics.

  The wax that can be used in the toner of the present invention is not particularly limited as long as it is selected from those having a melting peak in the above-mentioned range. Specifically, paraffin wax, microcrystalline wax, Petroleum and other petroleum waxes and derivatives thereof, montan wax and derivatives thereof, hydrocarbon waxes and derivatives thereof by Fischer-Tropsch method, polyolefin waxes and derivatives thereof typified by polyethylene, natural waxes and derivatives thereof such as carnauba wax and candelilla wax Derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. Furthermore, fatty acids such as higher aliphatic alcohols, stearic acid and palmitic acid, or compounds thereof, acid amide waxes, ester waxes, ketones, hydrogenated castor oil and derivatives thereof, plant waxes, animal waxes and the like can be mentioned.

  As described above, when a toner having excellent fixing properties is used, it is preferable to control the glass transition point of the toner. That is, when the glass transition point of the toner is too high, low temperature fixing performance cannot be obtained. However, although the melting temperature is lowered by lowering the glass transition point of the toner, if the temperature is too low, not only the storage stability of the toner may be deteriorated and a blocking phenomenon may be caused. As a result, the toner is fused in the developing unit, the toners are fused, and the fluidity is lowered. Further, as a result, the charging performance is lowered, and thus toner scattering and fogging are generated during development. For the above reasons, the glass transition point obtained from the DSC curve of the toner is preferably in the range of 45 to 70 ° C, more preferably in the range of 50 to 70 ° C.

  In the present invention, the melting peak of the wax, the softening point temperature of the toner, and the glass transition point can be measured using, for example, a differential scanning calorimetry (DSC) apparatus (manufactured by M-DSC TA Instruments). As a measuring method, about 6 mg of a sample is precisely weighed on an aluminum pan, an empty aluminum pan is used as a reference pan, and measurement is performed in a nitrogen atmosphere with a modulation amplitude of ± 0.6 ° C. and a frequency of 1 / min. The glass transition point is determined by the midpoint method from the reversing heat flow curve during temperature rise. A melting peak is calculated | required from the heat flow curve obtained by the said measurement.

  In the toner of the present invention, other charge control agents can be contained in order to assist the triboelectric charge characteristics, but it is preferable not to contain them. Specifically, as the charge control agent that can be contained, the negative control agent includes, for example, metal compounds such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, and dicarboxylic acid; sulfonic acid and carboxylic acid in the side chain. Preferred are a polymer compound having boron, a boron compound, a urea compound, a silicon compound, and calixarene. Examples of the positive control agent include a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, and an imidazole compound.

  The toner of the present invention contains a colorant. As the black colorant, carbon black, a magnetic material, and a color toned to black using a yellow / magenta / cyan colorant shown below are used.

  As the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complex methine compounds, and allylamide compounds are used as pigments. Specifically, C.I. I. Pigment Yellow 3, 7, 10, 12, 13, 14, 15, 17, 23, 24, 60, 62, 74, 75, 83, 93, 94, 95, 99, 100, 101, 104, 108, 109, 110 111,117,123,128,129,138,139,147,148,150,166,168,169,177,179,180,181,183,185,191: 1,191,192,193,199 Are preferably used. Examples of the dye system include C.I. l. solvent Yellow 33, 56, 79, 82, 93, 112, 162, 163, C.I. I. disperse Yellow 42.64.2011.211.

  As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, 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, 254, C.I. I. Pigment Bio Red 19 is particularly preferable.

  As the cyan colorant, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, and 66 are particularly preferably used.

  These colorants can be used alone or in combination and further in the form of a solid solution. The colorant of the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. The coloring agent is used in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

  Furthermore, the toner of the present invention contains a magnetic material and can be used as a magnetic toner. In this case, the magnetic material can also serve as a colorant. In the present invention, the magnetic material includes iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel, or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, and beryllium. , Bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, alloys with metals such as vanadium, and mixtures thereof.

  The magnetic material used in the present invention is more preferably a surface-modified magnetic material, and when used in a polymerization method toner produced by a production method such as a polymer dissolution suspension method or suspension polymerization method, Those subjected to a hydrophobizing treatment with a surface modifier, which is a substance without inhibition, are preferred. Examples of such surface modifiers include silane coupling agents and titanium coupling agents.

  These magnetic materials preferably have an average particle size of 2 μm or less, preferably about 0.1 to 0.5 μm. The amount to be contained in the toner is 20 to 200 parts by mass, particularly preferably 40 to 150 parts by mass with respect to 100 parts by mass of the binder resin.

  Magnetic properties when 796 kA / m (10 k Oersted) is applied are coercive force (Hc) of 1.59 to 23.9 kA / m (20 to 300 Oersted), saturation magnetization (σs) of 50 to 200 emu / g, residual magnetization (σr) A magnetic body of 2 to 20 emu / g is preferable.

  In the toner of the present invention, the toner preferably has a weight average particle diameter of 3.0 to 9.0 μm in order to faithfully develop finer latent image dots in order to improve image quality. More preferably, it is -6.5 micrometers. In a toner having a weight average particle diameter of less than 3.0 μm, the transfer residual toner on the photoconductor increases due to a decrease in transfer efficiency, and it becomes difficult to suppress photoconductor scraping and toner fusion. Furthermore, in addition to an increase in the surface area of the entire toner, the fluidity and agitation as a powder decrease, so there is a tendency for fogging and transferability to decrease. Etc. are likely to occur. When the weight average particle diameter of the toner exceeds 9.0 μm, the characters and line images are likely to be scattered, and it becomes difficult to obtain high resolution, and the dot reproducibility tends to be lowered.

  The weight average particle diameter and particle size distribution of the toner can be measured by various methods such as Coulter Counter TA-II type or Coulter Multisizer (manufactured by Coulter Inc.). In the present invention, a Coulter Multisizer (manufactured by Coulter) is connected to an interface (manufactured by Nikkiki) that outputs a number distribution and volume distribution, and a PC 9801 personal computer (manufactured by NEC). Use to prepare 1% NaCl aqueous solution. For example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, 0.1 to 5 ml of a surfactant, preferably alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolyte in which the sample is suspended is dispersed for about 1 to 3 minutes using an ultrasonic disperser, and the volume distribution is determined by measuring the volume and number of toner particles of 2 μm or more using the 100 μm aperture as the aperture by the Coulter Multisizer. And the number distribution are calculated, and the weight average particle diameter (D4) is measured therefrom.

  The average circularity of the toner of the present invention is preferably 0.955 or more. Particularly preferably, the average circularity is 0.970 or more. A toner having a high average circularity is very excellent in transferability. This is presumably because the contact area between the toner particles and the photoconductor is small, and the adhesion force of the toner particles to the photoconductor due to mirror image force, van der Waals force, or the like is reduced.

  The average circularity in the present invention is used as a simple method for quantitatively expressing the shape of particles. In the present invention, a flow type particle image measuring apparatus “FPIA-3000 type” (manufactured by Sysmex Corporation) is used. Measurement is performed, the circularity of the measured particle is obtained by the following equation, and the value obtained by dividing the total circularity of all the particles measured by the total equation as defined by the following equation is defined as the average circularity.

  In addition, “FPIA-3000”, which is a measuring apparatus used in the present invention, calculates the circularity of each particle, and then calculates the average circularity, and the circularity is 0.400 depending on the obtained circularity. 61 in the range of 1.000 at intervals of 0.010, such as 0.400 or more and less than 0.410, 0.410 or more and less than 0.420, ..., 0.990 or more and less than 1.000, and 1.000. A calculation method is used in which the average circularity is calculated using the center value and the frequency of the dividing points. However, there is very little error between the average circularity value calculated by this calculation method and the average circularity value calculated by the above-described calculation formula that directly uses the circularity of each particle, and is virtually ignored. In the present invention, using the concept of the calculation formula that directly uses the circularity of each particle described above for reasons of handling data such as a short calculation time and simplification of the calculation formula, You may use such a calculation method changed partially.

  As a specific measurement method, an appropriate amount of a surfactant, preferably an alkyl benzene sulfonate, is added to 20 ml of ion-exchanged water, and then 0.02 g of a measurement sample is added, and an oscillation frequency of 50 kHz and an electric output of 150 W is added. Dispersion treatment was carried out for 2 minutes using a desktop type ultrasonic cleaner / disperser (for example, “VS-150” (manufactured by VervoCrea Co., Ltd.)) to obtain a dispersion for measurement. It cools suitably so that it may become 10 to 40 degreeC.

  For the measurement, the flow type particle image measuring apparatus equipped with a standard objective lens (10 times) was used, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion prepared in accordance with the above procedure is introduced into the flow type particle image measuring apparatus, 3000 toner particles are measured in the total count mode, and the analysis particle diameter is set to a circle equivalent diameter of 2.00 μm or more and 200.00 μm or less. The average circularity of the toner particles was determined.

  In the measurement, automatic focus adjustment is performed using standard latex particles (for example, Duke Scientific 5200A diluted with ion-exchanged water) before the measurement is started. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.

  In the embodiment of the present application, a flow type particle image measuring apparatus, which has been calibrated by Sysmex Corporation and has been issued a calibration certificate issued by Sysmex Corporation, has an analysis particle diameter of 2.00 μm. The measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that it was limited to 200.00 μm or less.

  The “circularity” in the present invention is an index of the degree of unevenness of toner particles, and indicates 1.000 when the toner is perfectly spherical, and the circularity becomes smaller as the toner shape becomes more complicated.

  In general, the toner having an irregular shape has low charging uniformity at the convex or concave portions of the toner, and further, since it is irregular, the contact area between the electrostatic latent image carrier and the toner increases. As a result, the toner adhesion becomes high, resulting in an increase in the residual toner.

  The method for producing the toner of the present invention is not particularly limited, and a known production method is used. Specifically, a method for directly producing toner particles using the suspension polymerization method described in JP-B-36-10231, JP-A-59-53856, and JP-A-59-61842. A method of producing toner particles by an interfacial polymerization method such as a microcapsule production method; toner formation by a coacervation method; as disclosed in JP-A-62-106473 and JP-A-63-186253 A method of obtaining toner particles by an associative polymerization method in which at least one kind of fine particles are aggregated to obtain particles having a desired particle size; a method of producing toner particles by a dispersion polymerization method characterized by monodispersion; a water-insoluble organic solvent Polymer dissolution (melting) suspension method in which necessary resins are dissolved and then converted into toner in water; method of obtaining toner particles by emulsion dispersion method; and pressure kneader and extruder The toner component is kneaded and uniformly dispersed using a printer or a media disperser, and then cooled, and the kneaded product is collided with a target under a mechanical or jet stream to finely pulverize to a desired toner particle size. Further, a pulverization method in which the particle size distribution is sharpened through a classification step to produce toner particles; a method in which the toner obtained by the pulverization method is spheroidized by heating or the like in a solvent to obtain toner particles.

  However, the effect of the present invention appears more remarkably in the polymer dissolution (melting) suspension method or suspension polymerization method. The reason is that in the step of granulating in an aqueous medium (granulation step), the copolymer can be effectively localized near the surface of the toner particles. Each suspension method will be described below.

  In the method of producing toner particles by the polymer dissolution (melting) suspension method, first, a binder resin, a copolymer, and a colorant are dissolved and mixed or dispersed in an organic medium, or the resin is melted by heat. The copolymer and the colorant are dissolved and mixed or dispersed. Furthermore, together with wax and other additives as required, the mixture is uniformly dissolved and mixed or dispersed by a stirrer or the like to prepare a liquid mixture for toner formation. In that case, you may add what knead | mixed the colorant, wax, and another additive beforehand. The liquid mixture thus obtained is added to a dispersion medium (preferably an aqueous medium) containing a dispersion stabilizer, and a toner is prepared using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser as a stirrer. Disperse and suspend to the particle size (granulation step). When an organic solvent is used to dissolve the binder, the organic solvent is removed by heating or reduced pressure, and a solvent such as methanol, ethanol, 1-propanol, t-butyl alcohol, or acetone is added. By removing the organic solvent completely, toner particles can be obtained.

  In the method for producing toner particles by suspension polymerization, first, a colorant is uniformly dissolved and mixed or dispersed in a polymerizable monomer constituting a binder resin by a stirrer or the like. In particular, when the colorant is a pigment, it is preferably treated with a disperser to obtain a pigment dispersion paste. This is uniformly dissolved and mixed or dispersed by a stirrer or the like together with a polymerizable monomer, a copolymer and a polymerization initiator, and further, a wax and other additives as required to prepare a monomer composition. The monomer composition thus obtained is added to a dispersion medium (preferably an aqueous medium) containing a dispersion stabilizer, and a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser is used as a stirrer. Then, it is finely dispersed to the toner particle diameter (granulation step). Then, the monomer composition finely dispersed in the polymerization step is polymerized by light or heat to obtain toner particles.

  The organic medium that can be used in the polymer dissolution (melting) suspension method is determined according to the toner binder and is not particularly limited. Specifically, ether alcohols such as methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, diethylene glycol, monobutyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; ethyl acetate, butyl acetate, ethyl propionate, cellosolve acetate, etc. Esters; hydrocarbons such as hexane, octane, petroleum ether, cyclohexane, benzene, toluene, xylene; halogenated hydrocarbons such as trichloroethylene, dichloromethane, chloroform; ethers such as ethyl ether, dimethyl glycol, trioxane tetrahydrofuran; Acetals such as methylal and diethyl acetal; containing sulfur and nitrogen such as nitropropene, nitrobenzene and dimethyl sulfoxide Selected from compounds, and the like.

  As a method of dispersing the pigment composition in the organic medium, a known method can be used. For example, if necessary, a resin and a pigment dispersant are dissolved in an organic medium, and the pigment powder is gradually added while being stirred, so that the solvent is sufficiently blended. Further, by applying mechanical shearing force with a dispersing machine such as a ball mill, paint shaker, dissolver, attritor, sand mill, or high speed mill, the pigment can be stably finely dispersed, that is, dispersed into uniform fine particles.

  The resin as the binder resin used in the polymer dissolution (melting) suspension method is not particularly limited. For example, styrene resin, acrylic resin, styrene-acrylic resin, polyethylene resin, polyethylene-vinyl acetate resin, vinyl acetate resin, polybutadiene resin, phenol resin, polyurethane resin, polybutyral resin, polyester resin, and the like can be given. Among these, styrenic resins, acrylic resins, styrene-acrylic resins, polyester resins, and the like are desirable in terms of toner characteristics.

  The polymerizable monomer that can be suitably used in the suspension polymerization method is an addition polymerization monomer or a condensation polymerization monomer. Preferably, it is an addition polymerization 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 such as n-dodecylstyrene and derivatives thereof; Ethylene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; Unsaturated polyenes such as butadiene and isoprene; Vinyl chloride, vinylidene chloride, vinyl bromide and vinyl iodide Vinyl halides such as vinyl acetate, vinyl propionate, benzoic acid Vinyl esters such as Nyl; methyl methacrylate, ethyl methacrylate, propyl methacrylate, -n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate Α-methylene fatty acid monocarboxylic acid esters such as diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, acrylic acid-n-butyl, acrylic acid isobutyl, propyl acrylate, acrylic acid-n-octyl, dodecyl acrylate Acrylates such as 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, etc .; vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl Examples thereof include vinyl ethers such as tilether; N-vinyl compounds such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone; vinyl naphthalenes; acrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide.

  The dispersion medium that can be used in the above production method is determined based on the solubility of the binder resin, organic medium, monomer and copolymer in the dispersion medium, but is preferably an aqueous medium. Examples of the aqueous dispersion medium include water; methyl alcohol, ethyl alcohol, modified ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, sec-butyl alcohol, tert-amyl alcohol, and 3-pentanol. , Alcohols such as octyl alcohol, benzyl alcohol, cyclohexanol; ether alcohols such as methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, diethylene glycol monobutyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; ethyl acetate, butyl acetate , Esters such as ethyl propionate and cellosolve acetate; ethers such as ethyl ether and ethylene glycol Acetals such as methylal and diethyl acetal; acids such as formic acid, acetic acid, and propionic acid; selected from sulfur and nitrogen-containing organic compounds such as nitropropene, nitrobenzene, dimethylamine, monoethanolamine, pyridine, dimethyl sulfoxide, and dimethylformamide However, water or alcohols is particularly preferable. Two or more of these solvents can be mixed and used. The concentration of the liquid mixture or the monomer composition with respect to the dispersion medium is preferably 1 to 80% by mass, more preferably 10 to 65% by mass with respect to the dispersion medium.

  As a dispersion stabilizer that can be used when an aqueous dispersion medium is used, known ones can be used. Specific examples include inorganic compounds such as calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate. , Bentonite, silica, alumina and the like. As the organic compound, polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and its salt, starch and the like can be dispersed in an aqueous phase. The concentration of the dispersion stabilizer is preferably 0.2 to 20 parts by mass with respect to 100 parts by mass of the liquid mixture or the monomer composition.

  Examples of the polymerization initiator used in the toner of the present invention using the suspension polymerization method include known polymerization initiators. Specifically, those enumerated in the method for producing the copolymer are used.

  Further, examples of the chain transfer agent used when the toner is produced by the suspension polymerization method include known chain transfer agents.

  The toner of the present invention preferably has an inorganic fine powder on the surface of toner particles.

  The inorganic fine powder is added to and mixed with toner particles to improve the fluidity of the toner and make the charge uniform, and the added inorganic fine powder exists in a state of being uniformly attached to the surface of the toner particles.

  The inorganic fine powder in the present invention preferably has a number average primary particle size of 4 to 80 nm. When the number average primary particle size of the inorganic fine powder is larger than 80 nm, or when the inorganic fine powder of 80 nm or less is not added, good toner fluidity cannot be obtained, and charging is imparted to the toner particles. Are likely to be non-uniform, and problems such as increased fog, decreased image density, and toner scattering may be unavoidable. When the number average primary particle size of the inorganic fine powder is smaller than 4 nm, the agglomeration of the inorganic fine powder is strengthened. And image defects due to development of the aggregate, damage to the image carrier or development carrier, and the like. In order to make the charge distribution of the toner particles more uniform, the number average primary particle size of the inorganic fine powder is more preferably 6 to 35 nm.

  In the present invention, the number average primary particle size of the inorganic fine powder is measured by a photograph of the toner magnified by a scanning electron microscope, and further by an elemental analysis means such as XMA attached to the scanning electron microscope. Measure 100 or more primary particles of inorganic fine powder adhering to or releasing from the toner particle surface while comparing the photograph of the toner mapped with the elements contained in the body, and obtain the number average particle size. Can be obtained.

As the inorganic fine powder used in the present invention, an inorganic fine powder selected from silica, alumina, titania or a double oxide thereof can be used. Examples of the double oxide include aluminum silicate fine powder and strontium titanate fine powder. Further, as the silicic acid fine powder, both a so-called dry method produced by vapor phase oxidation of silicon halide or dry silica called fumed silica, and so-called wet silica produced from water glass or the like can be used. is there. Dry silica is preferred because it has few silanol groups on the surface and inside of the silicate fine powder and little production residue such as Na ₂ O, SO ₃ ^2- . In dry silica, it is also possible to obtain composite fine powders of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride and titanium chloride together with silicon halogen compounds in the production process. They are also included.

  The addition amount of the inorganic fine powder having a number average primary particle size of 4 to 80 nm is preferably 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the toner particles. If the addition amount is less than 0.1 parts by mass, the effect is not sufficient, and if it is 5.0 parts by mass or more, the fixability may be deteriorated.

  The inorganic fine powder in the present invention is added to improve the fluidity of the toner and to make the charge of the toner particles uniform. The adjustment of the charge amount of the toner and the environmental stability by a treatment such as a hydrophobic treatment of the inorganic fine powder. It is also a preferable form to provide a function such as improvement.

  When the inorganic fine powder added to the toner absorbs moisture, the charge amount of the toner particles is remarkably reduced, and the toner is easily scattered.

  Hydrophobic treatments for hydrophobizing inorganic fine powder include silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, and organic titanium compounds. You may process an agent individually or in combination.

  Among them, those treated with the above silicone oil are preferable, and more preferably, when the inorganic fine powder is treated with the silicone oil at the same time or after the hydrophobic treatment, the magnetic toner particles are used even in a high humidity environment. It is sufficient to keep the charge amount of the toner particles high and prevent toner scattering.

The toner of the present invention has a primary particle size of more than 30 nm (preferably a specific surface area of less than 50 m ² / g), more preferably a primary particle size of 50 nm or more (preferably a specific surface area) for the purpose of improving cleaning properties. It is also a preferable form to add inorganic particles or organic particles close to a sphere having a particle size of less than 30 m ² / g). Specifically, for example, spherical silica particles, spherical polymethylsilsesquioxane particles, spherical resin particles and the like are preferably used.

  Further, the toner used in the present invention may further contain other additives, for example, a lubricant powder such as Teflon (registered trademark) powder, zinc stearate powder, polyvinylidene fluoride powder, or the like within a range that does not substantially adversely affect the toner. Development of abrasives such as cerium oxide powder, silicon carbide powder, strontium titanate powder, fluidity-imparting agents such as titanium oxide powder and aluminum oxide powder, anti-caking agent, and organic and / or inorganic fine particles of opposite polarity A small amount can be used as a property improver. These additives can also be used after hydrophobizing the surface.

  In addition, the toner of the present invention can be mixed with a carrier and used as a two-component developer, or can be used as a one-component developer composed only of toner. In particular, when it is used as a non-magnetic one-component developer in which the rising property of charging is important, the effect is more remarkably exhibited.

  When the toner of the present invention is used for a two-component developer, the toner is used by mixing with a magnetic carrier. Examples of magnetic carriers include surface oxidized or unoxidized iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, rare earth metal particles, alloy particles thereof, oxide particles, ferrite and the like. Although fine particles can be used, the charging characteristics of the present invention can be more preferably achieved by using a magnetic fine particle dispersed resin carrier in which magnetic fine particles are dispersed in a resin.

  The coated carrier obtained by coating the surface of the magnetic carrier particles with a resin is particularly preferable in a developing method in which an AC bias is applied to the developing sleeve. Coating methods include a method in which a coating solution prepared by dissolving or suspending a coating material such as a resin in a solvent is adhered to the surface of the magnetic carrier core particles, and a method in which the magnetic carrier core particles and the coating material are mixed with powder. A conventionally known method can be applied.

  Examples of the coating material on the surface of the magnetic carrier core particles include silicone resin, polyester resin, styrene resin, acrylic resin, polyamide, polyvinyl butyral, and aminoacrylate resin. These are used alone or in plural. The treatment amount of the coating material is preferably 0.1 to 30% by mass (preferably 0.5 to 20% by mass) with respect to the carrier core particles. The average particle size of these carriers is preferably 10 to 100 μm, more preferably 20 to 70 μm.

  When a two-component developer is prepared by mixing the toner of the present invention and a magnetic carrier, the mixing ratio is usually 2 to 15% by mass, preferably 4 to 13% by mass as the toner concentration in the developer. Good results are obtained. If the toner concentration is less than 2% by mass, the image density tends to decrease, and if it exceeds 15% by mass, fogging or in-machine scattering tends to occur.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. All parts used in the examples indicate parts by mass.

Production Example of Sulfonic Acid Ester Group-Containing Copolymer A sulfonic acid ester group-containing copolymer A was synthesized by the following method.

<Production of copolymer A>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of xylene was charged and refluxed under a nitrogen stream.

  Next, the following monomers were mixed to prepare a monomer mixture.

<Monomer composition, mixing ratio>
-Methyl ester of 2-acrylamido-2-methylpropanesulfonic acid 8.0 parts-75.0 parts of styrene-4.0 parts of acrylic acid-13.0 parts of 2-ethylhexyl acrylate In addition to this monomer mixture, as a polymerization initiator 1.0 part of azobisisobutyronitrile was mixed and added dropwise to the reaction vessel with stirring, and held for 10 hours. Thereafter, distillation was performed to distill off the solvent, followed by drying at 50 ° C. under reduced pressure. The obtained solid was pulverized to obtain a copolymer A.

<Production of copolymer B>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of tetrahydrofuran was charged and refluxed under a nitrogen stream.

  Next, the following monomers were mixed to prepare a monomer mixture.

<Monomer composition, mixing ratio>
-2-acrylamido-2-methylpropanesulfonic acid ethyl ester 15.0 parts-Styrene 70.0 parts-Acrylic acid 2.0 parts-2-Ethylhexyl acrylate 13.0 parts 3.0 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was mixed, added dropwise to the reaction vessel with stirring, and held for 10 hours. Thereafter, distillation was performed to distill off the solvent, followed by drying at 50 ° C. under reduced pressure. The obtained solid was pulverized to obtain a copolymer B.

<Production of copolymer C>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of tetrahydrofuran was charged and refluxed under a nitrogen stream.

  Next, the following monomers were mixed to prepare a monomer mixture.

<Monomer composition, mixing ratio>
2-acrylamide-benzenesulfonic acid methyl ester 15.0 parts styrene 73.0 parts methacrylic acid 2.0 parts n-butyl acrylate 10.0 parts In addition to this monomer mixture, 2,2 as a polymerization initiator 1.0 part of '-azobis (2,4-dimethylvaleronitrile) was mixed, dropped into the reaction vessel with stirring, and maintained for 10 hours. Thereafter, distillation was performed to distill off the solvent, followed by drying at 50 ° C. under reduced pressure. The obtained solid was pulverized to obtain a copolymer C.

<Production of copolymer D>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of xylene was charged and refluxed under a nitrogen stream.

  Next, the following monomers were mixed to prepare a monomer mixture.

<Monomer composition, mixing ratio>
・ 2-Methacrylamide-5-methoxy-benzenesulfonic acid methyl ester
10.0 parts styrene 78.0 parts methacrylic acid 2.0 parts n-butyl acrylate 10.0 parts In addition to this monomer mixture, perbutyl I (manufactured by NOF Corporation) 5.0 as a polymerization initiator. Partly mixed, dropped into the reaction vessel with stirring, and held for 10 hours. Thereafter, distillation was performed to distill off the solvent, followed by drying at 50 ° C. under reduced pressure. The obtained solid was pulverized to obtain a copolymer D.

<Manufacture of copolymer E>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of xylene was charged and refluxed under a nitrogen stream.

  Next, the following monomers were mixed to prepare a monomer mixture.

<Monomer composition, mixing ratio>
・ 2-Methacrylamide-5-methoxy-benzenesulfonic acid methyl ester
20.0 parts · Styrene 69.0 parts · Methacrylic acid 1.0 part · n-Butyl acrylate 10.0 parts Perbutyl I (manufactured by Nippon Oil & Fats Co., Ltd.) 5.0 as a polymerization initiator was further added to this monomer mixture. Partly mixed, dropped into the reaction vessel with stirring, and held for 10 hours. Thereafter, distillation was performed to distill off the solvent, followed by drying at 50 ° C. under reduced pressure. The obtained solid was pulverized to obtain a copolymer E.

<Production of copolymer F>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of xylene was charged and refluxed under a nitrogen stream.

  Next, the following monomers were mixed to prepare a monomer mixture.

<Monomer composition, mixing ratio>
・ 2-acrylamide-2-methylpropanesulfonic acid methyl ester 35.0 parts ・ Styrene 48.0 parts ・ Acrylic acid 4.0 parts ・ 2-ethylhexyl acrylate 13.0 parts In addition to this monomer mixture, as a polymerization initiator 1.0 part of azobisisobutyronitrile was mixed and added dropwise to the reaction vessel with stirring, and held for 10 hours. Thereafter, distillation was performed to distill off the solvent, followed by drying at 50 ° C. under reduced pressure. The obtained solid was pulverized to obtain a copolymer F.

<Production of copolymer G>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of tetrahydrofuran was charged and refluxed under a nitrogen stream.

  Next, the following monomers were mixed to prepare a monomer mixture.

<Monomer composition, mixing ratio>
2-acrylamide-benzenesulfonic acid methyl ester 15.0 parts styrene 75.0 parts n-butyl acrylate 10.0 parts In addition to this monomer mixture, 2,2'-azobis (2,4 -Dimethylvaleronitrile) was mixed with 1.0 part, dropped into the reaction vessel with stirring, and held for 10 hours. Thereafter, distillation was performed to distill off the solvent, followed by drying at 50 ° C. under reduced pressure. The obtained solid was pulverized to obtain a copolymer G.

<Production of copolymer H>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of tetrahydrofuran was charged and refluxed under a nitrogen stream.

  Next, the following monomers were mixed to prepare a monomer mixture.

<Monomer composition, mixing ratio>
2-acrylamide-benzenesulfonic acid methyl ester 15.0 parts styrene 67.0 parts methacrylic acid 8.0 parts n-butyl acrylate 10.0 parts In addition to this monomer mixture, 2,2 as a polymerization initiator 1.0 part of '-azobis (2,4-dimethylvaleronitrile) was mixed, dropped into the reaction vessel with stirring, and maintained for 10 hours. Thereafter, distillation was performed to distill off the solvent, followed by drying at 50 ° C. under reduced pressure. The obtained solid was pulverized to obtain a copolymer H.

<Production of Copolymer I>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of tetrahydrofuran was charged and refluxed under a nitrogen stream.

  Next, the following monomers were mixed to prepare a monomer mixture.

<Monomer composition, mixing ratio>
・ 2-acrylamide-benzenesulfonic acid methyl ester 15.0 parts ・ methyl methacrylate 73.0 parts ・ methacrylic acid 2.0 parts ・ n-butyl acrylate 10.0 parts In addition to this monomer mixture, 1.0 part of 2′-azobis (2,4-dimethylvaleronitrile) was mixed, dropped into the reaction vessel while stirring, and held for 10 hours. Thereafter, distillation was performed to distill off the solvent, followed by drying at 50 ° C. under reduced pressure. The obtained solid was pulverized to obtain a copolymer I.

For the copolymers A to I produced above, Table 1 shows the mixing ratio of each monomer and the composition ratio calculated from the results of ¹ H-NMR and ¹³ C-NMR and elemental analysis in mol%. Table 2 shows the results of measuring the molecular weight, Tg, and acid value by the method described above.
¹ H-NMR, ¹³ C-NMR
FT-NMR JNM-EX400 manufactured by JEOL (solvent: heavy chloroform)
Elemental analysis Elemental analyzer EA-1108 manufactured by Carlo Elba (calculates C, O, S and N amounts)

Example 1
Preparation of pigment dispersion paste:
・ Styrene monomer 80 parts ・ Cu phthalocyanine (Pigment Blue 15: 3) 13 parts After pre-mixing the above materials well in a container, disperse the mixture in a bead mill for about 4 hours while keeping it at 20 ° C. or lower. Produced.

Preparation of toner particles:
390 parts of 0.1 mol / liter-Na ₃ PO ₄ aqueous solution was added to 1150 parts of ion-exchanged water, heated to 60 ° C., and then stirred at 11,000 rpm using CLEAMIX (M Technique). did. To this was added 58 parts of a 1.0 mol / liter-CaCl ₂ aqueous solution to obtain a dispersion medium containing Ca ₃ (PO ₄ ) ₂ .
- the pigment dispersed paste 46.5 parts Styrene monomer 38.0 parts n-Butyl acrylate 22.0 parts Ester wax 13.0 parts (main component _{C 19 H 39 COOC 20 H 41} , mp 68.6 ° C.)
Saturated polyester resin 5.0 parts (terephthalic acid-propylene oxide modified bisphenol A copolymer, acid value 15 mg KOH / g, Mw 18000)
-Copolymer A 1.0 part

These were heated to 60 ° C., dissolved and dispersed to obtain a monomer mixture. Further, while maintaining the temperature at 60 ° C., 3.0 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was added and dissolved to prepare a monomer composition. The monomer composition was charged into the dispersion medium prepared in the 2-liter flask of the homomixer. The monomer composition was granulated by stirring at 60 ° C. for 20 minutes at 10,000 rpm using a TK homomixer in a nitrogen atmosphere. Thereafter, the mixture was reacted at 60 ° C. for 5 hours while stirring with a paddle stirring blade, and then stirred at 80 ° C. for 5 hours to complete the polymerization. After cooling to room temperature, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ and filtered, washed with water, and dried to obtain toner particles. Further, the obtained toner particles were classified, and 2 to 10 μm was selected to prepare toner particles.

Toner preparation:
Hydrophobic silica fine powder 1 having a number average primary particle size of 9 nm and a BET specific surface area of 180 m ² / g treated with silicone oil after treating the surface with 100 parts of the obtained toner particles with hexamethyldisilazane. Parts were mixed and externally added with a Henschel mixer (Mitsui Miike Chemical Co., Ltd.) to obtain toner 1.

Example 2
Toner 2 was obtained in the same manner as in Example 1, except that 1.5 parts of copolymer B was used instead of 1.0 part of copolymer A.

Example 3
Toner 3 was obtained in the same manner as in Example 1, except that 1.5 parts of copolymer C was used instead of 1.0 part of copolymer A.

Example 4
Preparation of pigment dispersion paste:
-Styrene monomer 80 parts-Carbon black 13 parts After the above material was well premixed in a container, it was dispersed in a bead mill for about 4 hours while keeping it at 20 ° C or lower to prepare a pigment dispersion paste.

350 parts of 0.1 mol / liter-Na ₃ PO ₄ aqueous solution was added to 1200 parts of ion-exchanged water, heated to 60 ° C., and then stirred at 11,000 rpm using CLEARMIX (M Technique Co., Ltd.). did. To this, 52 parts of a 1.0 mol / liter-CaCl ₂ aqueous solution was added to obtain a dispersion medium containing Ca ₃ (PO ₄ ) ₂ .
-46.5 parts of the above pigment dispersion paste-35.0 parts of styrene monomer-25.0 parts of n-butyl acrylate-10.0 parts of aliphatic wax (Mw 1850, Mw / Mn 1.27, melting point 78.6 ° C)
Saturated polyester resin 5.0 parts (terephthalic acid-propylene oxide modified bisphenol A copolymer, acid value 15 mg KOH / g, Mw 18000)
-Copolymer D 1.5 parts These were heated to 60 ° C, dissolved and dispersed to obtain a monomer mixture. Further, while maintaining at 60 ° C., 5 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was added as a polymerization initiator and dissolved to prepare a monomer composition.

The monomer composition was charged into the dispersion medium prepared in the 2-liter flask of the homomixer. The monomer composition was granulated by stirring at 60 ° C. for 20 minutes at 10,000 rpm using a TK homomixer in a nitrogen atmosphere. Thereafter, the mixture was reacted at 60 ° C. for 5 hours while stirring with a paddle stirring blade, and then stirred at 80 ° C. for 5 hours to complete the polymerization. After cooling to room temperature, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ and filtered, washed with water, and dried to obtain toner particles. Further, the obtained toner particles were classified, and 2 to 10 μm was selected to prepare toner particles. Further, in the same manner as in Example 1, a toner 4 was obtained by externally adding hydrophobic silica fine powder to toner particles.

Example 5
Toner 5 was obtained in the same manner as in Example 4, except that 3.0 parts of copolymer E was used instead of 1.5 parts of copolymer D.

Example 6
Preparation of toner composition mixture:
Copolymerized polyester resin of bisphenol A propylene oxide adduct / bisphenol A ethylene oxide adduct / terephthalic acid derivative (Tg 62 ° C., softening point 102 ° C., Mw 21000) 100.0 parts Cu phthalocyanine (Pigment Blue 15: 3) 0 parts, aliphatic wax 8.0 parts (Mw 1850, Mw / Mn 1.27, melting point 78.6 ° C.)
-Copolymer A 1.0 part-Ethyl acetate 100.0 parts After the above material was well premixed in a container, it was dispersed in a bead mill for about 4 hours while maintaining the temperature at 20 ° C or lower, and a toner composition mixed solution Was made.

Preparation of toner particles:
Into 240 parts of ion-exchanged water, 78 parts of 0.1 mol / liter-Na ₃ PO ₄ aqueous solution was added, heated to 60 ° C., and then stirred at 11,000 rpm using CLEAMIX (M Technique Co., Ltd.). did. To this, 12 parts of a 1.0 mol / liter-CaCl ₂ aqueous solution was added to obtain a dispersion medium containing Ca ₃ (PO ₄ ) ₂ . Furthermore, 1.0 part of carboxymethylcellulose (trade name: Cellogen BS-H, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added and stirred for 10 minutes.

While the dispersion medium prepared in the homomixer flask was adjusted to 30 ° C. and stirred, 180 parts of the toner composition mixed solution adjusted to 30 ° C. was added, stirred for 1 minute, and then stopped. A toner composition dispersion suspension was obtained. The obtained toner composition dispersion suspension was stirred at a constant temperature of 40 ° C., and the gas phase on the suspension surface was forcibly renewed by a local exhaust device and kept for 17 hours to remove the solvent. After cooling to room temperature, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ and filtered, washed with water, and dried to obtain toner particles. Further, the obtained toner particles were classified, and 2 to 10 μm was selected to prepare toner particles. Further, in the same manner as in Example 1, a toner 6 was obtained by externally adding hydrophobic silica fine powder to toner particles.

Example 7
Toner 7 was obtained in the same manner as in Example 6 except that 1.5 parts of copolymer D was used instead of 1.0 part of copolymer A.

Comparative Example 1
A toner 8 was obtained in the same manner as in Example 1 except that the copolymer F was used instead of the copolymer A.

Comparative Example 2
A toner 9 was obtained in the same manner as in Example 3, except that the copolymer G was used instead of the copolymer C.

Comparative Example 3
A toner 10 was obtained in the same manner as in Example 3, except that 0.5 part of copolymer H was used instead of 1.5 parts of copolymer C.

Comparative Example 4
A toner 11 was obtained in the same manner as in Example 3 except that the copolymer I was used instead of the copolymer C.

  With respect to the above toners 1 to 11, the volume average particle diameter and the circularity were measured by the above-described method, and the DSC was further measured. The results are shown in Table 3.

  As shown in Table 3, in the toners 8 to 11 of Comparative Examples 1 to 4, the average particle diameter was slightly larger. In particular, in Comparative Examples 1 and 4, many coarse particles considered to be due to low solubility of the copolymers F and I in the monomer solution were observed. In Comparative Example 3, both coarse powder and fine powder were large and the particle size was very broad, and many agglomerates were confirmed.

  Further, the fixability test and the image output evaluation were performed for the toners 1 to 11 of Examples 1 to 7 and Comparative Examples 1 to 4 as follows. The results are shown in Table 4.

Fixability test method Each toner and a ferrite carrier (volume average particle size 42 μm) surface-coated with a silicone resin were mixed to a toner concentration of 6% by mass to prepare a two-component developer. An unfixed toner image (0.6 mg / cm ² ) was formed on a transfer paper (80 g / m ² ) by using a commercially available full-color digital copying machine (CLC700, manufactured by Canon). A fixing unit removed from a commercially available full-color laser beam printer (LBP-2040, manufactured by Canon) was modified so that the fixing temperature could be adjusted, and a fixing test of an unfixed image was performed using the fixing unit. Under normal temperature and normal humidity (23.5 ° C., 60% RH), the process speed is set to 180 mm / s, and the toner image is changed at each temperature while changing the set temperature every 5 ° C. within the range of 120 ° C. to 220 ° C. Was fixed. A fixed image at a temperature equal to or higher than the temperature at which low temperature offset is no longer observed is rubbed with sylbon paper lacking a load of 50 g / cm ² , and the fixing temperature at which the density reduction rate before and after rubbing is 5% or less The starting point was the point where the gross value was the maximum, and the end point on the high temperature side. When a high temperature offset or image receiving paper wrapping occurred, the same temperature as above was set as the high temperature end point.

  The gloss of the fixed image was measured using a gloss measuring device Micro-Tri-Gloss (manufactured by Gardner) at a measurement angle of 60 °.

Image printing test method Using a commercially available full-color laser beam printer (LBP-2040, manufactured by Canon), replenishing toner as needed, at room temperature and normal humidity (23.5 ° C., 60% RH), 5000 images were printed at a printing speed of 16 sheets / minute (A4 size paper) in the single color mode, and the toner charge amount on the toner carrier was measured simultaneously with the image density. Further, the toner carrier was removed after 5,000 images were printed, the toner was wiped off, and the surface contamination state was observed with a microscope, and the determination was made according to the following criteria.
A: No particular contamination is observed B: Some deposits or fusion products are seen C: Significant deposits or fusion products are seen

  As is apparent from the results shown in Table 4, Examples 1 to 7 according to the present invention (Toners 1 to 7) showed good results in offset resistance and low-temperature fixability in the fixing test, such as winding. Also, it was found that it has a sufficient fixing temperature range. Also, in the image output test, it was confirmed that it had good charging characteristics from the beginning and could be maintained after printing out 5000 sheets. As a result, the image density was stable at a good value throughout the durability. Further, no contamination on the surface of the toner carrier was observed.

  On the other hand, the toner of Comparative Example 1 (Toner 8) showed good results in the fixing test, but a decrease in charge amount and image density after durability was observed. It was speculated that this was caused by the contamination on the surface of the toner carrying member, which was considered to be the fusion of toner. In addition, the toner 9 of Comparative Example 2 showed good results in the fixing test, but the initial charge amount was low in the image output test (slow start-up characteristics) and the initial image density was low. It became. On the contrary, in the toner 10 of Comparative Example 3, the charge amount after durability was low, and the image density after durability was low. In the toner 11 of Comparative Example 4, winding occurred at 175 ° C. in the fixing test. Also, in the image output test, both the charge amount and the image density are low, and a large amount of fine powder of 0.1 to 2.0 μm adheres to the surface of the toner carrier, along with contamination that appears to be the fusion of the toner. It was.

<Evaluation of two-component developer>
Two-component development by mixing the toners 1 to 7 obtained above and a magnetic fine particle dispersed resin carrier (average particle size 35 μm) surface-coated with a silicone resin so that the toner concentration is 7.0% by mass, respectively. An agent was prepared. Each 450g of the two-component developer prepared was left for 7 days under high temperature and high humidity (30 ° C / 80%), then left for another 3 days under normal temperature and normal humidity (23 ° C / 60%) to reset the charge due to initial mixing. did. These were loaded into a developing unit of a color copying machine CLC-5100 (manufactured by Canon), and A4 image output with an image area ratio of 25% was performed without preliminary rotation. In the case of toner with low charge rise characteristics, fogging occurs on the white background in the initial (1 to 10 sheets) output image, and disturbance of the line image due to toner scattering is observed, but when toners 1 to 7 of the present invention are used An image excellent in fine line reproducibility without fogging was obtained. Further, when observing A4 images similar to the above after 5,000 A4 images having an image area ratio of 7% were continuously observed, the image density was stable as in the initial state, and the reproducibility of fogging and fine lines was initial. The same level was maintained.

Example 8
A mixture of the following materials was thoroughly mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.), and then a twin-screw kneader (PCM-30 type, Ikegai Iron Works Co., Ltd.) set at a temperature of 130 ° C. Kneaded).
Styrene-butyl acrylate-divinylbenzene copolymer 85.0 parts (Tg 58 ° C., Mn 8000, Mw 120,000)
Resin A for toner 15.0 parts Magnetic iron oxide (average particle size 0.18 μm) 100.0 parts Polymethine wax 5.0 parts (Mw: 1850, Mw / Mn: 1.27, melting point: 78.6 ℃)
The obtained kneaded material was cooled, coarsely pulverized to 1 mm or less with a hammer mill, and then finely pulverized with an air jet type pulverizer. The resulting finely pulverized product was classified to obtain toner particles. Further, in the same manner as in the production example of the toner 1, the toner 12 was obtained by externally adding hydrophobic silica fine powder to the toner particles.

  The toner 12 thus obtained had a volume average particle size of 6.85 μm, an average circularity of 0.962, and a DSC of Tg of 57.6 ° C. and a melting main peak of 74.0 ° C.

Example 9
Toner 13 was obtained in the same manner as in the production example of toner 12 except that 30 parts of toner resin C was used instead of 15 parts of toner resin A.

  The obtained toner 13 had a volume average particle size of 6.88 μm, an average circularity of 0.964, a TSC of 57.4 ° C., and a melting main peak of 74.2 ° C. in DSC.

Image printing test method Using a commercially available full-color laser beam printer (LBP-930, manufactured by Canon Inc.), replenishing toner as necessary, under normal temperature and normal humidity (23.5 ° C., 60% RH), 5000 images were printed, and the toner charge amount on the toner carrier was measured simultaneously with the image density.

  As a result, the toners 12 and 13 were both stable at an image density of 1.47 to 1.50 from the initial stage to after the endurance, and good images were obtained. In addition, the charge amount was also maintained at −25.0 μC / g to −30.0 μC / g from the initial stage to after the endurance, indicating good stability. From the above results, it was confirmed that the toners 12 and 13 of the present invention are practically excellent.

Claims (7)

At least 1) units A derived from a monomer is Ru represented by the following general formula (4),
2) Unit B having a carboxyl group,
3) a copolymer comprising a unit C derived from an aromatic vinyl monomer, and 4) a unit derived from an acrylate ester or methacrylate ester,
The content ratio of unit A based on the number of units in the copolymer is
Unit A: All units other than Unit A = 1: 99 to 15:85
Because
The content ratio based on the number of units of unit B in the copolymer is:
Unit B: All units other than unit B = 0.05: 99.95 to 8.00: 92.00
I der,
The content ratio of unit C based on the number of units in the copolymer is
Unit C: All units other than unit C = 80.6: 19.4 to 98.0: 2.0
Toner charge control resin, characterized in der Rukoto.

(In the formula, R18 represents a hydrogen atom or a methyl group, and B is represented by the following formula (1) or (2).)

(In the formula, R1 to 4 independently represent a hydrogen atom and an alkyl group having 1 to 12 carbon atoms, R5 represents a methyl group or an ethyl group, and A1 represents an amide bond.)

(Wherein R6 to 9 independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and a methoxy group, R10 represents a methyl group, and A2 represents an amide bond.)   2. The charge control resin for toner according to claim 1, wherein the copolymer has a weight average molecular weight calculated by gel permeation chromatography in the range of 2000 to 200000. 3.   The weight average molecular weight (Mw) and number average molecular weight (Mn) calculated by gel permeation chromatography of the copolymer are such that Mw / Mn is in the range of 1.0 to 6.0. The charge control resin for toner according to 1 or 2.   The charge for toner according to any one of claims 1 to 3, wherein the copolymer has a glass transition point in a range of 45 ° C to 90 ° C in a DSC curve measured by a differential scanning calorimeter. Control resin.   The charge control resin for toner according to claim 1, wherein the copolymer has an acid value of 3.0 to 40.0 mg KOH / g. A toner having toner particles containing at least a binder resin, a colorant, and the charge control resin for toner according to claim 1,
The toner, wherein the content of the charge control resin for toner is 0.1 to 20 parts by mass with respect to 100 parts by mass of the binder resin. A method for producing toner particles comprising a step of dispersing a composition having a charge control resin for toner in an aqueous medium,
The toner particles contain at least a binder resin, a colorant, and a charge control resin for toner,
The content of the charge control resin for toner is 0.1 to 20 parts by mass with respect to 100 parts by mass of the binder resin,
6. A method for producing toner particles, wherein the charge control resin for toner is the charge control resin for toner according to any one of claims 1 to 5.