JP4777046B2 - Charge control resin and toner for toner - 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 charging characteristics of the binder resin itself can be used, but the triboelectric charging characteristics of the binder resin generally used for toners are often low, depending on the composition. Control of the charging property is not easy. Therefore, generally, a charge control agent that imparts chargeability is added.

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

  Furthermore, the charge control agent added to these toners must be present on the toner surface to some extent in order to impart frictional charging ability. 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 toner particle size is simply reduced, and the adhesion force (mirror image force, van der Waals force, etc.) of the toner particles to the photoreceptor is larger than the Coulomb force applied to the toner particles in the transfer process. As a result, in addition to the increase in the residual toner, the reduction in the toner diameter is accompanied by a deterioration in fluidity, so that the charge amount of individual toner particles tends to be non-uniform, resulting in fog and toner particles having poor transferability. This is because it increases.

  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. Further, these publications sometimes have problems with 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 charging performance (particularly the initial startup performance) is insufficient when the process speed is increased by a contact one- component development system or the like.

  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 improvement in the stability of the charge amount before and after durability and under high temperature and high humidity. Furthermore, the toners described in these documents have insufficient 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. 2807955 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 to provide a toner having good fixability, excellent charging characteristics, maintaining stable chargeability from the initial stage after printing out a large number of sheets, and further maintaining developability and transferability. It is an object of the present invention to provide a toner capable of obtaining a stable image.

  As a result of intensive studies, the inventors of the present invention can improve the charging performance of the toner and maintain the fixing property and the development / transfer property by including a specific structure having an aryl group in the copolymer. The present inventors have found that the toner resin can be used and completed the present invention.

That is, the present invention relates to the following toner charge control resin (hereinafter referred to merely as "toner resin"), and toner over.
(1) At least 1) Unit A having a structure represented by the following general formula (1),
2) Unit B having a structure represented by the following general formula (2), and 3) Unit C derived from styrene monomer
A charge control resin for toner which is a copolymer comprising
Content based on the number of units of unit A and unit B in the copolymer is the sum of unit A and unit B = 0.2 to 1.5 mmol / g
Because
Unit A: Unit B = 50: 50 to 95: 5
Der is,
Co acid value of the polymer, for toner charge control resin, characterized in 0.1~40.0mgKOH / g der Rukoto.

（式中、Ｂ１は置換基を有していてもよいベンゼン核又はナフタレン核を表し、置換基としては水素原子又はメトキシ基を有する。Ｒ１はメチル基、エチル基又はイソプロピル基を表し、Ａ１はアミド結合又はエステル結合を表す。Ｒ２は水素原子又はメチル基を表す。）

(In the formula, B1 represents an optionally substituted benzene nucleus or naphthalene nucleus, and the substituent has a hydrogen atom or a methoxy group. R1 represents a methyl group, an ethyl group or an isopropyl group, and A1 represents Represents an amide bond or an ester bond, and R2 represents a hydrogen atom or a methyl group.

（式中、Ｂ２は置換基を有していてもよいベンゼン核又はナフタレン核を表し、置換基としては水素原子又はメトキシ基を有する。Ｘ１は水素原子又はナトリウムを表し、Ａ２はアミド結合又はエステル結合を表す。Ｒ８は水素原子又はメチル基を表す。）
（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ことを特徴とするトナー。

(In the formula, B2 represents an optionally substituted benzene nucleus or naphthalene nucleus, the substituent has a hydrogen atom or a methoxy group, X1 represents a hydrogen atom or sodium, and A2 represents an amide bond or ester. R8 represents a hydrogen atom or a methyl group.
(2) A toner comprising toner particles containing at least a binder resin, a colorant, and the charge control resin for toner.

  By using the toner containing the toner resin characterized by the present invention described below, good low-temperature fixability and stable triboelectric chargeability can be obtained, and as a result, developability and transferability are good over a long period of time. And a stable image can be obtained.

  The present inventors have intensively studied the fixing property, charging stability, development / transferability, etc. of the toner, and as a result, at least the unit A having the structure represented by the following general formula (1) and the following general formula (2): By incorporating a copolymer having a unit B having the structure shown below and a unit C derived from an aromatic vinyl monomer as a partial structure (hereinafter sometimes simply referred to as “copolymer”), It has been found that even if an excellent toner is used, a toner having stable charging characteristics and excellent developability can be provided.

（式中、Ｂ１は置換基を有していてもよい芳香族環を表し、置換基としては水素原子、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い。Ｒ１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。）

(In the formula, B1 represents an aromatic ring which may have a substituent, and the substituent represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an aryl group, or an alkoxy group; May form a 5-membered or 6-membered aromatic ring, R1 represents an alkyl group having 1 to 12 carbon atoms or an aryl group, and A1 represents an amide bond, a urethane bond, a urea bond, or an ester. Represents a bond or an ether bond.)

（式中、Ｂ２は置換基を有していてもよい芳香族環を表し、置換基としては水素原子、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い。Ｘ１は水素原子、アルカリ金属イオン、４級アンモニウムイオンを表し、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。）

(In the formula, B2 represents an aromatic ring which may have a substituent, and the substituent represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an aryl group or an alkoxy group, and is adjacent to each other. May form a 5-membered or 6-membered aromatic ring, X1 represents a hydrogen atom, an alkali metal ion, or a quaternary ammonium ion, and A2 represents an amide bond, urethane bond, urea bond, ester. Represents a bond or an ether bond.)

  The most characteristic point of the resin for toner is the unit A having a sulfonate group as a substituent. That is, by using a sulfonic acid ester group with respect to a conventionally proposed resin having a sulfonic acid group, it is possible to improve the charging effect. 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.

  In addition, a characteristic feature of the toner resin is that it also contains a unit B having a sulfonic acid group as a substituent. The copolymer containing only unit A showed a tendency to be charged up by repeating frictional charging, and it was found that the influence under low temperature and low humidity conditions was particularly great. Further, by containing the unit B, the dispersion / localization state in the toner can be arbitrarily controlled, and as a result, the abundance on the toner surface can be controlled.

  In addition, the effect on the triboelectric charging ability of the unit A and the unit B is that the sulfonic acid ester group or the sulfonic acid (salt) group is present on the aromatic ring as shown in the formulas (1) and (2). It was found that it is more prominent by being. The reason for this is considered to be that the order of the molecular orbitals of the sulfonic acid moiety varies depending on the conjugated system of the aromatic ring by containing a sulfonic acid ester group or a sulfonic acid (salt) group via an aromatic ring. . Therefore, it is considered that the structure of the aromatic ring and the type and location of the substituent are factors that greatly influence the charging characteristics of the sulfonic acid ester group and the sulfonic acid (salt) group. The most preferable structure is not generally determined, but a phenyl group and a naphthyl group are preferable structures.

  Furthermore, as shown in the above formulas (1) and (2), it can be seen that when the aromatic ring is bonded by an amide bond, a urethane bond, a urea bond, an ester bond or an ether bond, it exhibits excellent charging characteristics. It was. Of these, amide bonds, urethane bonds, and urea bonds are particularly excellent. The reason for this is not clear, but it is thought that the conjugated system spreads due to the resonance structure of the amide moiety and that an intramolecular hydrogen bond with the sulfonic acid moiety is formed by the hydrogen atom on the nitrogen atom.

  As shown in the formulas (1) and (2), the aromatic ring may have other substituents, specifically, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an aryl group, It is an alkoxy group, and adjacent groups may form a 5-membered or 6-membered aromatic ring.

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

  In addition to the above description, in consideration of the ease of manufacturing the resin for toner of the present invention and the cost merit, unit A and unit B are represented by the following formulas (3) or (4). It is preferable that it is a structure shown by these.

（式中、Ｒ２は水素原子又はメチル基を表し、Ｒ３〜６は独立に水素原子、水酸基、炭素数１〜４のアルキル基、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、Ｒ７は炭素数１〜４のアルキル基を表す。）

(In the formula, R2 represents a hydrogen atom or a methyl group, R3 to 6 independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group, and the adjacent groups are a 5-membered ring or 6 (It may form a membered aromatic ring, and R7 represents an alkyl group having 1 to 4 carbon atoms.)

（式中、Ｒ８は水素原子又はメチル基を表し、Ｒ９〜１２は独立に水素原子、水酸基、炭素数１〜４のアルキル基、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、Ｘ２は水素原子、アルカリ金属イオン、４級アンモニウムイオンを表す。）

(In the formula, R8 represents a hydrogen atom or a methyl group, R9 to 12 independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group. A membered aromatic ring may be formed, and X2 represents a hydrogen atom, an alkali metal ion, or a quaternary ammonium ion.)

  In addition, a characteristic point of the toner resin is that it contains a unit C derived from an aromatic vinyl monomer. By having the unit C, it becomes easy to control the compatibility with the binder resin. This compatibility control means not only the control of dispersibility / locality in the toner, but also the control of the state of the toner resin at the molecular level. . In other words, the compatibility between the toner resin and the binder resin changes the elasticity of the molecular chain of the toner resin, which affects the orientation of Unit A and Unit B. It was found to be very closely involved in the stability of the charging properties of the polymer itself. This effect is considered to be due to the affinity between the aromatic ring part of unit A and unit B and aromatic unit C.

  The vinyl monomer component that can be used as the aromatic vinyl monomer for forming the unit C is not particularly limited. 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- Examples thereof include styrene such as n-dodecylstyrene and derivatives thereof.

  Next, the content ratio of unit A and unit B in the toner resin of the present invention will be described. First, the content of unit A and unit B contained in the resin cannot be determined unconditionally due to the difference in the structure or the main chain structure of the resin, but the total of unit A and unit B is 0.2. It needs to be in the range of ~ 1.5 mmol / g. When it is less than 0.2 mmol / g, the charging characteristics are insufficient and unstable. On the other hand, when the amount is more than 1.5 mmol / g, it has been found that the dispersibility / locality in the toner is affected and the development / transferability is lowered. For the above reasons, the range of 0.3 to 0.9 mmol / g is more preferable.

Furthermore, the ratio of unit A to unit B is based on the number of units.
Unit A: Unit B = 50: 50 to 95: 5
It is necessary to be. When the ratio of unit A is less than 50:50, the initial charging characteristics are insufficient, and conversely, when it is more than 95: 5, charge-up occurs in the latter half of the durability or under low temperature and low humidity. . For the above reasons, it is necessary that the ratio of unit A and unit B coexist in a specific ratio, but a more preferable range is 60:40 to 85:15.

  In view of adjusting the physical properties of the toner resin of the present invention, it is preferable to have a (meth) acrylic acid ester unit represented by the following formula (5). By having the (meth) acrylic acid ester unit, it is possible to finely adjust the compatibility with the binder resin and the wax, and the glass transition point can be easily adjusted. Moreover, random copolymerizability can be improved and the uniform distribution in the molecule | numerator of the unit A and the unit B is accelerated | stimulated.

（式中、Ｒ１３は水素原子又はメチル基を表し、Ｒ１４は置換基を有していても良い炭化水素基を表し、置換基としてはハロゲン、水酸基、アミノ基からなる群から選ばれる官能基である。）

(In the formula, R13 represents a hydrogen atom or a methyl group, R14 represents a hydrocarbon group which may have a substituent, and the substituent is a functional group selected from the group consisting of a halogen, a hydroxyl group and an amino group. is there.)

  Specific examples of the compound having the above structure include methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylate-n-octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate. Α-methylene fatty acid monocarboxylic acid esters such as 2-hydroxyethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, Propyl acrylate, acrylate-n-octyl, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, 2-hydroxyacrylate Le, can be mentioned acrylic acid esters such as.

  In the toner resin of the present invention, another monomer may be copolymerized 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.

  The method for synthesizing the resin for toner of the present invention is not particularly limited and can be produced by a known method, but can be roughly divided into two types.

  One is a method of copolymerizing at least an aromatic vinyl monomer and a vinyl monomer having a structure represented by the above formulas (1) and (2). The other is a method in which at least an aromatic vinyl monomer and a reactive monomer are copolymerized, and the above formulas (1) and (2) are bonded as side chains or functional groups by a polymer reaction. In these methods, it is possible to form a unit A by forming a copolymer containing only unit B and esterifying sulfonic acid.

As a more specific synthesis method, a method for synthesizing a copolymer containing the structures of the above formulas (3) and (4) is exemplified. (A) An aromatic vinyl monomer and a monomer represented by the following formula (7) Method of copolymerizing and then esterifying sulfonic acid in the copolymer

（式中、Ｒ１９は水素原子又はメチル基を表し、Ｒ２０〜２３は独立に水素原子、水酸基、炭素数１〜４のアルキル基、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、Ｘ４は水素原子、アルカリ金属イオン、４級アンモニウムイオンを表す。）
（Ｂ）芳香族ビニルモノマー及び（メタ）アクリル酸等のカルボン酸含有モノマーとを共重合させ、さらに共重合体中のカルボン酸と下記一般式（６）のアミンを縮合させ、その後に共重合体中のスルホン酸をエステル化する方法

(In the formula, R19 represents a hydrogen atom or a methyl group, R20 to 23 independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group. A membered aromatic ring may be formed, and X4 represents a hydrogen atom, an alkali metal ion, or a quaternary ammonium ion.)
(B) An aromatic vinyl monomer and a carboxylic acid-containing monomer such as (meth) acrylic acid are copolymerized, and the carboxylic acid in the copolymer is condensed with an amine of the following general formula (6). Method for esterifying sulfonic acid in coalescence

（式中、Ｒ１５〜１８は独立に水素原子、水酸基、炭素数１〜１２のアルキル基、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、Ｘ３は水素原子、アルカリ金属イオン、４級アンモニウムイオンを表す。）
を挙げることができる。他にも、ウレタン結合やウレア結合を利用した高分子架橋反応を利用した合成方法も利用できる。

(In the formula, R15 to 18 independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, and an alkoxy group, and adjacent groups form a 5-membered or 6-membered aromatic ring. X3 represents a hydrogen atom, an alkali metal ion, or a quaternary ammonium ion.)
Can be mentioned. In addition, a synthesis method using a polymer crosslinking reaction using a urethane bond or a urea bond can also be used.

  As a method of condensing the carboxyl group in the resin with the amine by the method (B), a known method can be used. Specific examples include a method of reacting with triphenyl phosphite in an organic base.

  As a method of esterifying the sulfonic acid in the resin as in the methods (A) and (B), a known method can be used. Specific examples include a method of reacting with an alcohol after chlorination of sulfonic acid, a method using a methyl esterifying agent such as dimethyl sulfate, trimethylsilyldiazomethane, and trimethyl phosphate, a method using an orthoformate, and the like. Among them, the method using the orthoformate ester is most excellent as the esterification method of the present invention. According to this method, by reacting an orthoformate having a desired alkyl group with a sulfonic acid-containing resin under relatively mild conditions, the sulfonic acid can be easily esterified, and the reaction temperature and reaction time are reduced. The ratio of esterification can be easily controlled by the amount of orthoformate, the amount of solvent, and the like.

  The orthoformate used in the present invention specifically includes trimethyl orthoformate, triethyl orthoformate, tri-n-propyl orthoformate, tri-iso-propyl orthoformate, tri-n-butyl orthoformate. , Tri-sec-butyl orthoformate, tri-tert-butyl orthoformate, and mixtures thereof.

  As a method for synthesizing the monomer represented by the formula (7), a known method can be used. For example, the amine represented by the formula (6) is amidated with a reactive acrylate or the like (for example, acrylic acid chloride or methacrylic anhydride).

  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, when the molecular weight of the copolymer is too small, the charging characteristics of the unit A and the unit B may be adversely affected in addition to easily contaminating members such as a sleeve and a carrier. 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.

By the copolymer molecular weight and molecular weight distribution Gerupami et chromatography (GPC), but are intended to be calculated in terms of polystyrene, as in the copolymer of the present invention, is one containing a sulfonic acid group Since the column elution rate also depends on the amount of sulfonic acid groups, the accurate molecular weight and molecular weight distribution are not measured. Therefore, it is necessary to prepare a material in which the sulfonic acid group is capped beforehand. Methyl esterification is preferred for capping, and commercially available methyl esterifying agents can be used. Specifically, a method of treating with trimethylsilyldiazomethane can be mentioned.

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

Each resin sample is added to THF (tetrahydrofuran), and the solution which has been allowed 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 resin for toner in order to exert the effect without impairing the fixing property of the toner, and Tg measured by a differential scanning calorimeter (DSC). Is preferably in the range of 45 ° C to 110 ° C. A more preferable range is 50 ° C to 90 ° C.

  In order to cope with the toner production method, to improve compatibility with the binder resin, and to localize the toner resin in the vicinity of the toner surface when producing toner particles in an aqueous medium, the toner resin is used. May have a specific acid value. However, when the acid value is too high, the charging characteristics of the aryl group may be hindered, and furthermore, the chargeability of the toner may be influenced by changes in the environment (temperature / humidity), which is not preferable. A preferable acid value range of the resin for toner is 0.1 to 40.0 mgKOH / g, and more preferably 2.0 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 toner resin, 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 molecular weight distribution of the binder resin of the toner of the present invention is not particularly limited, but the peak molecular weight calculated by GPC of the resin component soluble in THF is preferably in the range of 3000 to 80000. If it is less than 3000, there may be a problem in chargeability. If it is more than 80000, it is 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 fixing properties, the temperature of the melting peak (endothermic peak) of the wax seen at the time of temperature rise is important in the DSC curve of the toner measured by a 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 as described above, in the DSC curve of a preferable toner, the temperature range of the endothermic 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, and even if the charging characteristics are improved by the features of the present invention, the fluidity of the toner may be reduced, leading to a decrease in image characteristics. is there.

  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. Furthermore, as a result, the triboelectric charging efficiency is lowered, so that even when the toner resin of the present invention is used, toner scattering and fogging occur 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.

  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 colorant is added 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 the increase in the surface area of the entire toner, the fluidity and stirring properties as powders are reduced, so that fog and transferability tend to decrease even when the toner resin of the present invention is used, In addition to shaving and fusion, non-uniformity in the image tends to occur. Further, when the weight average particle diameter of the toner exceeds 9.0 μm, the characters and the line image are likely to be scattered, and it becomes difficult to obtain a 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. The high average circularity synergizes with the effect of the resin for toner of the present invention, promotes uniform chargeability, and is extremely excellent in transferability. This is because the contact area between the toner particles and the photoconductor is small, the adhesion force of the toner particles to the photoconductor due to the mirror image force, van der Waals force, etc. is reduced. This is thought to be because excessive charging is suppressed.

  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.

  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 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 the toner resin can be effectively localized in the vicinity of the toner particle surface in the step of granulating in an aqueous medium (granulation step). Each suspension method will be described below.

  In the method for producing toner particles by the polymer dissolution (melting) suspension method, first, a binder resin, a toner resin and a colorant are dissolved and mixed or dispersed in an organic medium, or the resin is melted by heat. The toner resin 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 binding, 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. As a result, the organic solvent can be completely removed and toner particles can be obtained.

  In the method for producing toner particles by the suspension polymerization method, 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 resin for toner 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. Finely disperse to the toner particle size (granulation step). Then, the monomer composition finely dispersed in the polymerization step is subjected to a polymerization reaction by light or heat, whereby toner particles can be obtained.

  The organic medium that can be used in the polymer dissolution (melting) suspension method is determined according to the toner binder resin, 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, and those listed as monomers that can be used in the method for producing the resin for toner are used.

  The dispersion medium that can be used in the production method is determined based on the solubility of the binder resin, organic medium, monomer, and toner resin in the dispersion medium, but is preferably an aqueous medium. Examples of water-based dispersion media that can be used 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, 3 -Alcohols such as pentanol, octyl alcohol, benzyl alcohol, cyclohexanol; ether alcohols such as methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, diethylene glycol monobutyl ether, and other water-soluble ones such as acetone, Ketones such as methyl ethyl ketone and methyl isobutyl ketone; Estes such as ethyl acetate, butyl acetate, 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; nitropropene, nitrobenzene, dimethylamine, monoethanolamine, pyridine, dimethylsulfoxide, dimethylformamide Selected from sulfur and nitrogen-containing organic compounds, etc., and water or alcohols are particularly preferred. 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 listed as starting materials that can be used in the method for producing the resin for toner 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 exceeds 5.0 parts by mass, 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 also 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.

Moreover, the analytical instruments used in the examples are as follows.
FT-IR spectrum AVATAR360FT-IR manufactured by Nicolet
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)

Production Examples of Toner Resins Toner resins J1 to J6 were synthesized by the following method.

Production of resin J1 for toner < Production of raw material copolymer>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube, 50 parts of methanol and 200 parts of tetrahydrofuran were charged and refluxed under a nitrogen stream.

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

<Monomer composition, mixing ratio>
-90.0 parts of styrene-10.0 parts of acrylic acid In addition to this monomer mixture, 3.0 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was further mixed, and the reaction vessel The solution was added dropwise 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 styrene acrylic acid copolymer.

<Introduction of unit B ... condensation reaction>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer and a nitrogen introduction tube, 100 parts of the obtained styrene acrylic acid copolymer and 114 parts of 2-aminobenzenesulfonic acid are added, and 380 parts of pyridine are added and stirred. After that, 410 parts of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 500 parts of ethanol. The obtained polymer was washed twice with 200 parts of 1N hydrochloric acid, then washed twice with 200 parts of water, and dried under reduced pressure. As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from the carboxylic acid decreased, and a new peak derived from the amide bond was confirmed at 1658 cm ⁻¹ . In addition, from the result of ¹ H-NMR, it was confirmed that the peak derived from the phenyl group of 2-aminobenzenesulfonic acid was shifted.

<Introduction of unit A: esterification of sulfonic acid>
Furthermore, 400 parts of trimethyl orthoformate was charged in a reaction vessel equipped with a cooling tube, a stirrer, a thermometer and a nitrogen introduction tube and heated to 80 ° C. To this, 100 parts of the polymer obtained was added in 5 minutes and then stirred for 15 hours. Thereafter, the reaction mixture was added dropwise to 9000 parts of hexane with stirring. The resin was deposited and allowed to stand for a while. The supernatant was removed by decantation, and 500 parts of chloroform was added to the residue and dissolved. This was dropped into 7500 parts of hexane under stirring, precipitated and precipitated, the supernatant was removed by decantation, and the residue was dried under reduced pressure. This was washed with 300 parts of methanol and further with 300 parts of water. This was dried under reduced pressure to obtain toner resin J1.

Production of resin J2 for toner < Production of raw material copolymer>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer and a nitrogen introduction tube, 67 parts of methanol, 50 parts of toluene and 83 parts of methyl ethyl ketone were charged and refluxed under a nitrogen stream.

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

<Monomer composition, mixing ratio>
・ Styrene 72.0 parts ・ N-butyl acrylate 20.0 parts ・ Acrylic acid 8.0 parts In addition to this monomer mixture, 2,2′-azobis (2,4-dimethylvaleronitrile) was added as a polymerization initiator. .5 parts 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 styrene acrylic acid copolymer.

<Introduction of unit B ... condensation reaction>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer and a nitrogen introduction tube, 100 parts of the obtained styrene acrylic acid copolymer and 114 parts of 4-methoxyaniline-2-sulfonic acid were placed, and 380 parts of pyridine were added. In addition, after stirring, 350 parts of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 500 parts of ethanol. The obtained polymer was washed twice with 200 parts of 1N hydrochloric acid, then washed twice with 200 parts of water, and dried under reduced pressure. As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from the carboxylic acid decreased, and a new peak derived from the amide bond was confirmed at 1658 cm ⁻¹ . In addition, from the result of ¹ H-NMR, it was confirmed that the peak derived from the methoxy group of 4-methoxyaniline-2-sulfonic acid was shifted.

<Introduction of unit A: esterification of sulfonic acid>
Furthermore, 800 parts of trimethyl orthoformate was charged in a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube, and heated to 80 ° C. To this, 100 parts of the polymer obtained was added in 5 minutes and then stirred for 15 hours. Thereafter, the reaction mixture was added dropwise to 9000 parts of hexane with stirring. The resin was deposited and allowed to stand for a while. The supernatant was removed by decantation, and 500 parts of chloroform was added to the residue and dissolved. This was dropped into 7500 parts of hexane under stirring, precipitated and precipitated, the supernatant was removed by decantation, and the residue was dried under reduced pressure. This was washed with 300 parts of methanol and further with 300 parts of water. This was dried under reduced pressure to obtain resin J2 for toner.

Manufacture of toner resin J3 < Manufacture of raw material copolymer>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube, 50 parts of methanol and 200 parts of tetrahydrofuran were charged and refluxed under a nitrogen stream.

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

<Monomer composition, mixing ratio>
-Styrene 84.0 parts-2-ethylhexyl acrylate 10.0 parts-Acrylic acid 6.0 parts In addition to this monomer mixture, 2,2'-azobis (2,4-dimethylvaleronitrile) is added as a polymerization initiator. 0.0 part was mixed, and it was dripped at the said reaction container, stirring, and hold | 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 styrene acrylic acid copolymer.

<Introduction of unit B ... condensation reaction>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer and a nitrogen introduction tube, 100 parts of the obtained styrene acrylic acid copolymer and 94 parts of 2-amino-1-naphthalenesulfonic acid were added, and 380 parts of pyridine were added. After addition and stirring, 265 parts of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 500 parts of ethanol. The obtained polymer was washed twice with 200 parts of 1N hydrochloric acid, then washed twice with 200 parts of water, and dried under reduced pressure. As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from the carboxylic acid decreased, and a new peak derived from the amide bond was confirmed at 1658 cm ⁻¹ . In addition, from the result of ¹ H-NMR, it was confirmed that the peak derived from the phenyl group of 2-amino-1-naphthalenesulfonic acid was shifted.

<Introduction of unit A: esterification of sulfonic acid>
Further, 800 parts of triethyl orthoformate was charged in a reaction vessel equipped with a cooling pipe, a stirrer, a thermometer, and a nitrogen introduction pipe and heated to 80 ° C. To this, 100 parts of the polymer obtained was added in 5 minutes and then stirred for 15 hours. Thereafter, the reaction mixture was added dropwise to 9000 parts of hexane with stirring. The resin was deposited and allowed to stand for a while. The supernatant was removed by decantation, and 500 parts of chloroform was added to the residue and dissolved. This was dropped into 7500 parts of hexane under stirring, precipitated and precipitated, the supernatant was removed by decantation, and the residue was dried under reduced pressure. This was washed with 300 parts of methanol and further with 300 parts of water. This was dried under reduced pressure to obtain toner resin J3.

<Production of Toner Resin J4>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer and a nitrogen introduction tube, 20 parts of methanol and 100 parts of tetrahydrofuran were charged and refluxed under a nitrogen stream.

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

<Monomer composition, mixing ratio>
-Styrene 72.3 parts-N-butyl acrylate 20.0 parts-2-acrylamido-benzenesulfonic acid methyl ester 4.5 parts-2-acrylamido-benzenesulfonic acid sodium 3.2 parts To this monomer mixture, methanol 20 And 60 parts of tetrahydrofuran were mixed, and 3.0 parts of perbutyl PV (manufactured by Nippon Oil & Fats Co., Ltd.) was mixed as a polymerization initiator, 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 toner resin J4.

Manufacture of toner resin J5 < Manufacture of raw material copolymer>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube, 50 parts of methanol and 200 parts of tetrahydrofuran were charged and refluxed under a nitrogen stream.

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

<Monomer composition, mixing ratio>
-Styrene 85.0 parts-Acrylic acid 15.0 parts Further mixed with 3.0 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator in the monomer mixture, the reaction vessel The solution was added dropwise 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 styrene acrylic acid copolymer.

<Introduction of unit B ... condensation reaction>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer and a nitrogen introduction tube, 100 parts of the obtained styrene acrylic acid copolymer and 182 parts of 4-aminobenzenesulfonic acid are added, and 380 parts of pyridine are added and stirred. After that, 600 parts of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 500 parts of ethanol. The obtained polymer was washed twice with 200 parts of 1N hydrochloric acid, then washed twice with 200 parts of water, and dried under reduced pressure. As a result of IR measurement, the peak at 1695 cm ⁻¹ derived from the carboxylic acid decreased, and a new peak derived from the amide bond was confirmed at 1658 cm ⁻¹ . In addition, from the result of ¹ H-NMR, it was confirmed that the peak derived from the phenyl group of 4-aminobenzenesulfonic acid was shifted.

<Introduction of unit A: esterification of sulfonic acid>
Further, 1200 parts of tri (isopropyl) orthoformate was charged into a reaction vessel equipped with a cooling pipe, a stirrer, a thermometer, and a nitrogen introduction pipe and heated to 80 ° C. To this, 100 parts of the polymer obtained was added in 5 minutes and then stirred for 15 hours. Thereafter, the reaction mixture was added dropwise to 9000 parts of hexane with stirring. The resin was deposited and allowed to stand for a while. The supernatant was removed by decantation, and 500 parts of chloroform was added to the residue and dissolved. This was dropped into 7500 parts of hexane under stirring, precipitated and precipitated, the supernatant was removed by decantation, and the residue was dried under reduced pressure. This was washed with 300 parts of methanol and further with 300 parts of water. This was dried under reduced pressure to obtain toner resin J5.

<Manufacture of Toner Resin J6>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer and a nitrogen introduction tube, 20 parts of methanol and 100 parts of tetrahydrofuran were charged and refluxed under a nitrogen stream.
Next, the following monomers were mixed to prepare a monomer mixture.

<Monomer composition, mixing ratio>
Styrene 65.0 parts n-butyl acrylate 10.0 parts Monomer of the following general formula 25.0 parts

  To this monomer mixture, 20 parts of methanol and 60 parts of tetrahydrofuran are mixed, and 3.0 parts of perbutyl PV (manufactured by Nippon Oil & Fats Co., Ltd.) is further mixed as a polymerization initiator and added dropwise to the reaction vessel while stirring. Held for hours. Thereafter, distillation was performed to distill off the solvent, followed by drying at 50 ° C. under reduced pressure.

<Introduction of unit A: esterification of sulfonic acid>
Furthermore, 800 parts of trimethyl orthoformate was charged in a reaction vessel equipped with a cooling pipe, a stirrer, a thermometer and a nitrogen introduction pipe and heated to 40 ° C. To this, 100 parts of the polymer obtained was added in 5 minutes and then stirred for 2 hours. Thereafter, the reaction mixture was added dropwise to 9000 parts of hexane with stirring. The resin was deposited and allowed to stand for a while. The supernatant was removed by decantation, and 500 parts of chloroform was added to the residue and dissolved. This was dropped into 7500 parts of hexane under stirring, precipitated and precipitated, the supernatant was removed by decantation, and the residue was dried under reduced pressure. This was washed with 300 parts of methanol and further with 300 parts of water. This was dried under reduced pressure to obtain a resin J6 for toner.

  Resins H1 to H5 for comparative examples were synthesized by the method shown below.

  In the production example of the resin J1 for the toner, the resin H1 for the comparative example was obtained by changing the step of introducing the unit A (esterification of the sulfonic acid) as follows.

<Introducing unit A>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube, 400 parts of trimethyl orthoformate was charged and heated to 40 ° C. To this, 100 parts of a styrene acrylic acid copolymer was added in 5 minutes, and then stirred for 30 minutes. Thereafter, the reaction mixture was added dropwise to 9000 parts of hexane with stirring. The resin was deposited and allowed to stand for a while. The supernatant was removed by decantation, and 500 parts of chloroform was added to the residue and dissolved. This was dropped into 7500 parts of hexane under stirring, precipitated and precipitated, the supernatant was removed by decantation, and the residue was dried under reduced pressure. This was washed with 300 parts of methanol and further with 300 parts of water. This was dried under reduced pressure to obtain Comparative Example Resin H1.

  In the production example of the resin J1 for the toner, the resin H2 for the comparative example was obtained by changing the step of introducing the unit A (esterification of the sulfonic acid) as follows.

<Introducing unit A>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube, 100 parts of a styrene acrylic acid copolymer, 3500 parts of chloroform, and 800 parts of methanol were added and dissolved, and cooled to 0 ° C. To this was added 75 parts of a 2 mol / liter trimethylsilyldiazomethane-hexane solution (manufactured by Aldrich) and stirred for 4 hours. Thereafter, distillation was performed to distill off the solvent.

  Furthermore, 2500 parts of toluene and 1000 parts of methyl ethyl ketone were added to redissolve the polymer, and the solvent was distilled off by distillation. This re-dissolution / distillation operation was repeated three times and dried at 50 ° C. under reduced pressure. The obtained solid was pulverized to obtain a comparative resin H2.

  In the production example of the resin J4 for toner, the resin H3 for comparative example was obtained by changing the monomer composition (mixing ratio) as follows.

<Monomer composition, mixing ratio>
-Styrene 77.6 parts-n-butyl acrylate 20.0 parts-2-acrylamido-benzenesulfonic acid methyl ester 1.4 parts-2-acrylamido-benzenesulfonic acid sodium 1.0 part In preparation example of resin J4 for toner The resin composition H4 for Comparative Example was obtained by changing the monomer composition (mixing ratio) as follows.

<Monomer composition, mixing ratio>
-Styrene 40.0 parts-n-butyl acrylate 20.0 parts-2-acrylamido-benzenesulfonic acid methyl ester 23.5 parts-2-acrylamido-benzenesulfonic acid sodium salt 16.5 parts In the preparation example of resin J4 for toner The resin composition H5 for Comparative Example was obtained by changing the monomer composition (mixing ratio) as follows.

<Monomer composition, mixing ratio>
・ Methyl methacrylate 72.3 parts ・ n-butyl acrylate 20.0 parts ・ 2-acrylamido-benzenesulfonic acid methyl ester 4.5 parts ・ 2-acrylamido-benzenesulfonic acid sodium 3.2 parts Resins S1 to S6 prepared above And for the resins H1 to H5 for Comparative Examples, the structure and content (mmol / g) of unit A and unit B calculated from the results of ¹ H-NMR and ¹³ C-NMR and elemental analysis and the content of unit C ( mol%) is shown in Table 1, and the results of measuring the acid value, molecular weight, and Tg by the above-described method are shown in Table 2.

Toner Production Examples Toners 1 to 6 of the present invention were produced by the following method.

<Manufacture of toner 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 42.0 parts n-Butyl acrylate 18.0 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 10 mg KOH / g, Mw 16000)
・ Toner resin J1 1.5 parts

  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. The mixture was stirred at 10000 rpm for 20 minutes using a CLEARMIX at 60 ° C. in a nitrogen atmosphere to granulate the monomer composition. 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.

<Manufacture of toner 2>
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.

Preparation of toner particles:
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-38.0 parts of styrene monomer-22.0 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 10 mg KOH / g, Mw 16000)
・ Toner resin J2 1.5 parts

  These were heated to 60 ° C., dissolved and dispersed to obtain a monomer mixture. Further, while maintaining the temperature at 60 ° C., 5 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was added and dissolved as a polymerization initiator to prepare a monomer composition.

The monomer composition was charged into the dispersion medium. The mixture was stirred at 10000 rpm for 20 minutes using a CLEARMIX at 60 ° C. in a nitrogen atmosphere to granulate the monomer composition. 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, a toner 2 was obtained by externally adding hydrophobic silica fine powder to toner particles in the same manner as in Toner Production Example 1.

<Manufacture of toner 3>
Toner 3 was obtained in the same manner as in the production example of toner 1 except that 3.0 parts of toner resin J3 was used instead of 1.5 parts of toner resin J1.

<Manufacture of toner 4>
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.)
-Toner resin J1 5.0 parts-Ethyl acetate 100.0 parts After the above materials are well premixed in a container, the mixture is dispersed in a bead mill for about 4 hours while keeping it 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 container 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, a toner 4 was obtained by externally adding hydrophobic silica fine powder to toner particles in the same manner as in Toner Production Example 1.

<Manufacture of toner 5>
Toner 5 was obtained in the same manner as in the production example of toner 4, except that 10.0 parts of toner resin J4 was used instead of 5.0 parts of toner resin J1.

<Manufacture of toner 6>
Production of resin dispersion:
Styrene 370 parts n-Butyl acrylate 30 parts Acrylic acid 6 parts Dodecanethiol 24 parts 4 Carbon bromide 4 parts Mixing and dissolving the above nonionic surfactant Nonipol 400 6 parts, anionic surfactant Neogen SC 10 parts Dispersed and emulsified in a flask dissolved in 550 parts of ion-exchanged water, slowly mixed for 10 minutes, and then charged with 50 parts of ion-exchanged water in which 4 parts of ammonium persulfate had been dissolved, was purged with nitrogen. After that, the flask was heated with an oil bath while stirring until the content reached 70 ° C., and emulsion polymerization was continued for 5 hours. As a result, a resin dispersion having a center diameter of 155 nm, a glass transition point of 59 ° C., and Mw of 12000 was obtained.

Production of resin J5 dispersion for toner:
40 parts of resin J5 for toner is added to 360 parts of ion-exchanged water, heated to 90 ° C., adjusted to pH = 7 with 5% aqueous ammonia, and added with 0.8 part of 10% aqueous dodecylbenzenesulfonic acid solution. Using Turrax T-50 (manufactured by IKA), the mixture was stirred at 8000 rpm to prepare a dispersion of resin J5 for toner having a center diameter of 200 nm.

Preparation of blue pigment dispersion:
The following compositions were mixed and dissolved, and dispersed by homogenizer (IKA Ultra Tarrax) and ultrasonic irradiation to obtain a blue pigment dispersion having a central particle size of 150 nm.
Cyan pigment C.I. I. Pigment Blue 15: 3 50 parts (copper phthalocyanine manufactured by Dainippon Ink)
・ Anionic surfactant Neogen SC 5 parts ・ Ion-exchanged water 200 parts

Preparation of release agent dispersion:
The following composition was mixed, heated to 97 ° C., and then dispersed with IKA Ultra Turrax T50. Thereafter, the dispersion was dispersed with a gorin homogenizer (manufactured by Kyowa Shoji Co., Ltd.) and treated 20 times under the conditions of 105 ° C. and 550 kg / cm ² to obtain a release agent dispersion having a center diameter of 190 nm.
Aliphatic wax 100 parts (Mw 1850, Mw / Mn 1.27, melting point 78.6 ° C.)
・ Anionic surfactant Neogen SC 5 parts ・ Ion-exchanged water 300 parts

Toner particle production:
Resin dispersion 200 parts Colorant dispersion 30 parts Release agent dispersion 30 parts Sanizol B50 1.5 parts The above mixture was mixed and dispersed in a round stainless steel flask with Ultra Turrax T50, and the flask was then heated with an oil bath for heating. Heat to 48 ° C. with stirring. After maintaining at 48 ° C. for 30 minutes, observation with an optical microscope confirmed that aggregated particles of about 5 μm were formed. To this, 60 parts of the toner resin S3 dispersion was slowly added, and the temperature of the heating oil bath was raised and held at 50 ° C. for 1 hour. When observed with an optical microscope, it was confirmed that aggregated particles of about 5.6 μm were formed. Then, after adding 3 parts of neogen SC here, the stainless steel flask was sealed, and it heated to 105 degreeC, continuing stirring using a magnetic seal, and hold | maintained for 3 hours. After cooling, it was filtered, washed thoroughly with ion exchange 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 Toner Production Example 1, hydrophobic silica fine powder was externally added to the toner particles to obtain toner 6.

  Toners 7 to 11 for comparative examples were produced by the following method.

<Manufacture of toner 7>
Toner 7 was obtained in the same manner as in the production method of toner 1 except that resin H1 for comparative example was used instead of resin J1 for toner.

<Manufacture of toner 8>
Toner 8 was obtained in the same manner as in the production method of Toner 1 except that Comparative Example Resin H2 was used instead of Toner Resin J1.

<Manufacture of toner 9>
A toner 9 was obtained in the same manner as the production method of the toner 5 except that the resin H3 for comparative example was used instead of the resin J4 for toner.

<Manufacture of Toner 10>
Toner 10 was obtained in the same manner as in the production method of toner 5 except that resin H4 for comparative example was used instead of resin J4 for toner.

<Manufacture of toner 11>
A toner 11 was obtained in the same manner as the production method of the toner 1 except that the comparative resin H5 was used instead of the toner resin J1.

  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.

  Further, the image formation evaluation was performed as follows for the toners 1 to 11 of the above examples and comparative examples. The results are shown in Table 4.

Image printing test method Using a commercially available full-color laser beam printer (LBP-5500, manufactured by Canon), remove the product toner from the commercially available cartridge, and fill each cartridge with 200 g of toner to clean the interior by air blow. A drawing test was conducted. The test contents were 8000 sheets continuous print test under normal temperature and humidity environment (23.5 ° C, 60% RH), and 2000 sheets continuous print test under low temperature and low humidity environment (15 ° C, 10% RH). It was. During the print test, the first to fifth sheets were initially treated, the 7996 to 8000 sheets were endured, and the 1996 to 2000 sheets were subjected to severe endurance in a low-temperature and low-humidity environment. The concentration was measured and the average value was determined. In this test, the printing speed was set to A4 horizontal 17 sheets / minute (75 g / m ² A4 plain paper), and an original chart having a printing ratio of 2% with respect to the paper area was used. In addition, a halftone image having an image density of about 0.7 was output after 8000 sheets were endured and 2000 sheets were endured in a low-temperature and low-humidity environment, and the fineness and uniformity were visually evaluated.

The criteria for visual evaluation of a halftone image are as follows.
A: Very good and very fine and fine B: No problem in practical use Slight spots are observed C: Practical problem is likely to occur D: Has a blur on the image D: Difficult Conspicuous shading Bad image occurs

  As is apparent from the results shown in Table 4, the toners 1 to 6 of the examples according to the present invention have good charging characteristics from the beginning in the image output test, and can be maintained even after printing out 8,000 sheets. Was confirmed. Furthermore, it was confirmed that high charging characteristics were maintained even after 2000 sheets were printed out under low temperature and low humidity. As a result, the image density and the halftone image quality were stable at a satisfactory level throughout the durability.

  On the other hand, in the toner 7 of the comparative example, the initial charging characteristics showed a relatively low value and the image density was low. In the toner 8, although the initial charging characteristics were good, it was confirmed that it was slightly higher after printing out 8000 sheets, and was significantly increased after printing out 2000 sheets under low temperature and low humidity. As the charge amount increases, the halftone image is also blurred, and the uniformity of the image quality is impaired. In addition, it can be seen that the toner 9 has a low initial charge amount and poor charge rising characteristics. Although the charge amount increased with durability, it showed a high charge amount under low temperature and low humidity. As a result, the initial image density was low, and spots were confirmed in the halftone image quality under low temperature and low humidity. The toner 10 showed very high charging characteristics from beginning to end, and spots were confirmed in the halftone image. Further, the image density was low throughout. This is because the transfer efficiency is low. In the toner 11, the image density and the halftone image level were low throughout. This is because the transfer efficiency is low and the developability deteriorates. Furthermore, charge-up under low temperature and low humidity was confirmed.

<Evaluation of two-component developer>
Two-component development is performed by mixing the toners 1 to 6 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 toner with low charge rise characteristics, fogging occurs in the white background portion in the initial (1 to 10 sheets) output image, and disturbance of the line image due to toner scattering is observed, but when the toners 1 to 6 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 8,000 A4 images having an image area ratio of 7% are continuously observed, the image density is stable as in the initial state, and the reproducibility of fogging and fine lines is initial. The same level was maintained. Further, when the same A4 image was observed after the endurance of 2,000 sheets in the low temperature and low humidity environment (15 ° C., 10% RH) as described above, the image density was stable as in the initial stage, and the fog and fine lines were The reproducibility was also at a level that had no practical problems.

<Manufacture of toners 12 and 13>
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)
-Toner resin J1 15.0 parts-Magnetic iron oxide (average particle size 0.18 [mu] m) 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.

  Toner 13 was obtained in the same manner as in the production example of toner 12, except that 30 parts of toner resin J6 was used instead of 15 parts of toner resin J1.

  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), 8000 sheets were imaged, 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. Also, the charge amount was maintained at −28.0 μC / g−30.0 μC / g from the initial stage to after the endurance, indicating good stability. Furthermore, 2000 images were printed under a low temperature and low humidity environment (15 ° C., 10% RH), and when the toner charge amount on the toner carrier was measured simultaneously with the image density, both of the image densities were maintained at 1.45 or more. It was confirmed that the charge amount was maintained at −35.0 μC / g or less. From the above results, it was confirmed that the toners 12 and 13 of the present invention are practically excellent.

Claims (13)

At least 1) a unit A having a structure represented by the following general formula (1):
2) Unit B having a structure represented by the following general formula (2), and 3) Unit C derived from styrene monomer
A charge control resin for toner which is a copolymer comprising
Content based on the number of units of unit A and unit B in the copolymer is the sum of unit A and unit B = 0.2 to 1.5 mmol / g
Because
Unit A: Unit B = 50: 50 to 95: 5
And
A charge control resin for toner, wherein the copolymer has an acid value of 0.1 to 40.0 mgKOH / g.

(In the formula, B1 represents an optionally substituted benzene nucleus or naphthalene nucleus, and the substituent has a hydrogen atom or a methoxy group. R1 represents a methyl group, an ethyl group or an isopropyl group, and A1 represents Represents an amide bond or an ester bond, and R2 represents a hydrogen atom or a methyl group.

(In the formula, B2 represents an optionally substituted benzene nucleus or naphthalene nucleus, the substituent has a hydrogen atom or a methoxy group, X1 represents a hydrogen atom or sodium, and A2 represents an amide bond or ester. R8 represents a hydrogen atom or a methyl group. The charge control resin for toner according to claim 1, wherein the unit A is represented by the following general formula (3), and the unit B is represented by the following general formula (4).

(Wherein R2 represents a hydrogen atom or a methyl group, R3 to 6 independently represent a hydrogen atom or a methoxy group, and R7 represents a methyl group, an ethyl group or an isopropyl group.)

(In the formula, R8 represents a hydrogen atom or a methyl group, R9 to 12 independently represent a hydrogen atom or a methoxy group, and X2 represents a hydrogen atom or sodium.) The charge control resin for toner according to claim 1, wherein the copolymer further includes a unit represented by the following general formula (5).

(In the formula, R13 represents a hydrogen atom or a methyl group, R14 represents a hydrocarbon group which may have a substituent, and the substituent is a functional group selected from the group consisting of a halogen, a hydroxyl group and an amino group. is there.) The toner charge control resin condenses at least a part of a carboxyl group of a copolymer obtained by copolymerizing styrene and a vinyl monomer having a carboxyl group with an amine represented by the following formula (6). The toner for toner according to any one of claims 1 to 3, which is a copolymer obtained by esterifying a part of a sulfonic acid group or a sulfonic acid group of the copolymer obtained in the above. Charge control resin.

(In formula, R15-18 represents a hydrogen atom or a methoxy group independently, and X3 represents a hydrogen atom or sodium.)   The charge control resin for toner is formed by condensing at least a part of the carboxyl group of the copolymer obtained by copolymerizing styrene and a vinyl monomer having a carboxyl group with the amine represented by the formula (6). 5. The copolymer obtained by esterifying a part of the sulfonic acid group or sulfonate group of the copolymer obtained by using an orthoformate ester, according to claim 4. Charge control resin for toner.   6. 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.   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 any one of 1 to 6.   The charge control for toner according to any one of claims 1 to 7, wherein the copolymer has a glass transition point in a range of 45 to 110 ° C in a DSC curve measured by a differential scanning calorimeter. resin. A toner having toner particles containing at least a binder resin, a colorant, and a charge control resin for toner,
The charge control resin for toner is the charge control resin for toner according to any one of claims 1 to 8, and the content of the charge control resin for toner is 0.1 relative to 100 parts by mass of the binder resin. A toner characterized in that it is ˜20 parts by mass.   10. The toner according to claim 9, wherein the toner contains a wax and has an endothermic peak in a range of 45 to 130 ° C. when the temperature is increased in a DSC curve of the toner measured by a differential scanning calorimeter. toner.   11. The toner according to claim 9, wherein the toner has a glass transition point in a range of 45 to 70 ° C. in a DSC curve of the toner measured by a differential scanning calorimeter.   The toner according to claim 9, wherein the toner has a weight average particle diameter (D4) of 3.0 to 9.0 μm.   9. The toner particles according to claim 9, wherein the toner particles are formed by a production method including a step of dispersing the composition having the charge control resin for toner according to any one of claims 1 to 8 in an aqueous medium. The toner according to any one of 12 above.