JP5441677B2 - 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.

  Conventionally, in an image forming method using electrophotography, electrostatic printing or the like, it is indispensable to control 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 the negatively chargeable charge control agent, there are metal complex salts of monoazo dyes, metal compounds such as salicylic acid, alkyl salicylic acid, and dialkyl salicylic acid, calixarene, and the like. Many of these charge control agents have a complicated structure, a constant property, and poor stability.

  Furthermore, the charge control agent added to these toners must be present on the toner surface to some extent in order to impart frictional charging ability. As a result, friction between the toners, collision with the carrier, conveyance sleeve or roller, regulating blade, and friction with the photosensitive drum cause these additives to fall off the toner surface, causing contamination of the carrier, developing member, and photosensitive drum. Contamination may occur. As a result, as the number of durable sheets increases, the triboelectric chargeability decreases, and at the same time, deterioration due to contamination progresses, which easily causes problems such as a change in image density and a decrease in image quality.

  From the background as described above, studies for improving the triboelectric charging characteristics of toner have been actively conducted. Particularly, due to environmental considerations, more stable chargeability requirements, manufacturing costs, etc., in recent years, proposals have been made to use a resin having a charge control function (charge control resin) as a charge control agent for toner. . For example, a toner using a resin containing a salicylic acid structure as a charge control resin has been proposed (Patent Document 1). According to this method, it is said that a toner having good charging characteristics can be obtained while improving the sublimability of salicylic acid. However, there is still room for improvement as the speed of copying machines and printers increases. In particular, when the process speed is increased with a contact one-component development system or the like, it has become clear that the charging performance (particularly, the initial charge rising performance) is insufficient. Furthermore, it has been clarified that there is room for improvement in the stability of charging at the time of printing out a large number of sheets and the stability of the charge amount under high temperature and high humidity. For this phenomenon, the toner is required to have a quicker charge that rises to a sufficient charge amount in a short time, and that the charge level is stable from the initial stage to after printing a large number of sheets. There is a need for charge control resins that can be achieved.

Japanese Patent Registration No. 2694572

  The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a toner that has a further rapid charge that rises to a sufficient charge amount in a short period of time and a toner whose charge level is stable from the initial stage to after printing out a large number of sheets.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by the toner of the present invention, and have reached the present invention.

  In order to achieve the object of the present invention, the invention according to the present application provides a toner having toner particles containing at least a binder resin, a colorant, and a charge control agent as the toner. ) And a metal chloride or metal complexed unit of a metal derived from the unit A, and the amount of metal in the polymer is 5 mol% or more based on the unit A It is characterized by being 45 mol% or less.

（式（１）におけるＣＯＯＨとＯＨは隣り合う位置に結合し、Ｒ₁は水素または炭素数１乃至６のアルキル基を表し、Ｒ₂は、水素またはメチル基を表す。）

(COOH and OH in Formula (1) are bonded to adjacent positions, R ₁ represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and R ₂ represents hydrogen or a methyl group.)

  According to the present invention, in a toner having toner particles containing at least a binder resin, a colorant, and a charge control agent, the charge control agent is derived from at least the unit A represented by the formula (1) and the unit A. A copolymer containing a unit made of metal chloride or metal complex with a metal to be produced, and the amount of metal in the polymer is 5 mol% or more and 45 mol% or less with respect to unit A, so that a short time is sufficient. A toner having a triboelectric charging property that rises up to a charge amount and having a stable charge level over time can be obtained.

  Further, in a toner having toner particles containing at least a binder resin, a colorant, and the charge control agent, in a toner using a pigment, in particular, a copper phthalocyanine compound of a cyan colorant as a colorant, the pigment dispersibility as well as the charge stability. Improved toner can be obtained.

It is a figure which shows the structure of the apparatus used for the measurement of the triboelectric charge amount of the developing agent using the toner of this invention.

  The inventors of the present invention provide a copolymer in which the charge control agent includes at least a unit A represented by the formula (1) and a metal chloride or metal complex unit of a metal derived from the unit A, It has been found that when the amount of metal in the polymer is 5 mol% or more and 45 mol% or less with respect to unit A, the above-described effect is exhibited, and the present invention has been achieved.

（式（１）におけるＣＯＯＨとＯＨは隣り合う位置に結合し、Ｒ₁は水素または炭素数１乃至６のアルキル基を表し、Ｒ₂は、水素またはメチル基を表す。）

(COOH and OH in Formula (1) are bonded to adjacent positions, R ₁ represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and R ₂ represents hydrogen or a methyl group.)

Although the mechanism that exerts the effect is not clear, the present inventors have the charging performance of the charge control agent,
(A) Effect of charge generation and charge accumulation (B) Charge dissipation rate, which is considered to contribute to charge uniformity, is considered to be involved.

  In the present invention, it is considered that a unit in which a metal is chlorinated or complexed with the unit A represented by the formula (1) generates an electric charge and has an effect of accumulating the electric charge.

  On the other hand, it is considered that the unit A represented by the formula (1) dissipates the accumulated excess charge and contributes to uniform charge.

  In the present invention, since these two types of units coexist closely at the molecular level, it is considered that the generation of charges and the homogenization of charges occur instantaneously, and the rise of charge is improved.

  In addition, when the amount of metal in the polymer was 5 mol% or more and 45 mol% or less with respect to the unit A, the charging performance was successfully extracted.

  Although the reason for this is not clear, the amount of metal in the polymer with respect to the polymer having the unit A having the salicylic acid derivative is 5 mol% or more and 45 mol% or less with respect to the unit A. This is because the effect of accumulating charges and the effect of charge equalization are controlled at the molecular level.

  When the amount of the metal salt in the polymer is less than 5 mol% with respect to the unit A, the effect of charge generation and charge accumulation is reduced, and it becomes difficult to charge the toner particles. On the other hand, when it exceeds 45 mol%, the effect of uniformizing the charge is reduced, and charge-up is likely to occur.

  Further, in the present invention, it was found that when the charge control agent is used, the pigment, particularly the copper phthalocyanine compound of the cyan colorant, is effective in improving the pigment dispersibility as well as the charge stability. The reason for this is not clear, but the charge control agent of the present invention includes a unit containing at least unit A represented by the formula (1) and a metal chloride or metal complexed unit of a metal derived from unit A. By combining, it is considered that the affinity with the copper phthalocyanine compound is increased, adsorbed by the pigment, and exerts an effect on the dispersibility of the pigment.

  In the present invention, the charge control agent is preferably a copolymer in which the unit A represented by the formula (1) contains 1.00% by mass or more and 40.00% by mass or less in the total mass part. .

  When the unit A represented by the formula (1) is less than 1.00% by mass with respect to the total mass part of the charge control agent, the charge uniformization is delayed, so that the rise of charge as toner particles is delayed. There is a case. On the other hand, when the amount is more than 40.00% by mass, the charging performance may be hindered due to the moisture absorption effect of unit A, and fogging immediately after long-term storage may be deteriorated.

  Moreover, in this invention, it is preferable that the molecular weight of the polymer in the said charge control agent has the weight average molecular weight computed by the gel permeation chromatography (GPC) being 2000 or more and 100000 or less. When the weight average molecular weight is less than 2000, the unit A represented by the formula (1) introduced into the molecule may not be uniformly introduced, and the uniform chargeability may not be maintained. In addition, when the weight average molecular weight is 100,000 or more, dispersion in the toner is deteriorated, and uniform chargeability may not be maintained.

  Further, from the viewpoint of charging characteristics and fixability, the copolymer preferably has a narrow molecular weight distribution. A preferable range of molecular weight distribution is that Mw / Mn is 1.0 or more and 6.0 or less in the weight average molecular weight Mw and the number average molecular weight Mn calculated by gel permeation chromatography. More preferably, it is 1.0 or more and 4.0 or less.

  The main chain structure of the polymer is not particularly limited as long as the unit A having the salicylic acid derivative represented by the formula (1) can be introduced. Examples thereof include vinyl polymers, polyester polymers, polyamide polymers, polyurethane polymers, polyether polymers, and the like. In view of ease of production in producing the charge control agent of the present invention, cost merit, and the like, polyester polymers and vinyl polymers are preferable.

  In the present invention, the metal in the polymer of the charge control agent is selected from the unit A represented by the formula (1) and a metal atom capable of forming a metal salt or metal complex. Preferred metal atoms are divalent, trivalent, and tetravalent metal atoms. As specific examples thereof, aluminum, zinc, chromium, cobalt, nickel, zirconium, titanium, copper and iron are preferable. Among these, aluminum, zinc, chromium and zirconia are more preferable because they have superior environmental characteristics during durability from the stability of the complex structure.

  In the present invention, the charge control agent is preferably a copolymer of a vinyl monomer copolymerizable with the unit A represented by the formula (1). The reason for this is not clear, but the copolymer with the vinyl monomer makes it easy to control the compatibility with the binder resin, particularly in the case of a suspension polymerization toner. This is because dispersibility and delocalization are possible. As a result, it is considered that the charging characteristics of the copolymer itself are stabilized. As a result, the difference in charge amount (environment dependence) under low temperature and low humidity and high temperature and high humidity is reduced.

  Further, in order to exert the effect without impairing the fixing property of the toner, it is necessary to control the glass transition point (Tg) of the charge control agent, but a copolymer with a vinyl monomer is used. This is because control becomes easy.

  The vinyl monomer that can be used is not particularly limited. Specifically, styrene and its derivatives such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene; ethylene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; Vinyl halides such as vinyl, vinylidene chloride, vinyl bromide, vinyl fluoride; vinyl ester acids such as vinyl acetate, vinyl propionate, vinyl benzoate; acrylic acid-n-butyl, acrylic acid-2-ethylhexyl, etc. Acrylic acid esters; Methacrylic acid esters obtained by changing the acrylic acid of the acrylic acid esters to methacrylic acid; Methacrylic acid amino esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; Vinyl methyl ether, vinyl ethyl ether; Vinyl ethers such as: vinyl ketones such as vinyl methyl ketone; N-vinyl compounds such as N-vinyl pyrrole; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide, acrylic acid, methacrylic acid, etc. Can be mentioned.

  It does not specifically limit as a manufacturing method of the charge control agent of this invention, It can manufacture by a well-known method.

  For example, as an example, a polymerizable monomer (formula (2)) is made into a metal salt or metal complex using a metal-imparting agent (for example, aluminum sulfate) and then copolymerized with a copolymerizable polymer. Is the method.

（式（２）におけるＣＯＯＨとＯＨは隣り合う位置に結合し、Ｒ₃は水素または炭素数１乃至６のアルキル基を表し、Ｒ₄は水素またはメチル基を表す。）

(COOH and OH in formula (2) are bonded to adjacent positions, R ₃ represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and R ₄ represents hydrogen or a methyl group.)

  Examples of the polymerizable monomer (formula (2)) in the present invention include 3-vinyl salicylic acid, 4-vinyl salicylic acid, 5-vinyl salicylic acid, 6-vinyl salicylic acid, 3-vinyl-5-isopropylpropylic acid, 3- Examples thereof include vinyl-5-t-butylsalicylic acid, 4-vinyl-6-t-butylsalicylic acid, and 3-isopropenyl-5-t-butylsalicylic acid.

  A metal salt or metal complexation between a polymerizable monomer (formula (2)) and a metal is known by using a polymerizable monomer (formula (2)) with a metal-imparting agent (for example, aluminum sulfate). By this method, a metal salt or a metal complex can be formed to obtain a product.

  Examples of the metal imparting agent that can be used in the present invention include aluminum compounds such as aluminum sulfate and aluminum acetate, chromium compounds such as chromium formate, chromium acetate, chromium sulfate and chromium nitrate, zirconium compounds such as zirconium acetate and zirconium oxychloride, Examples thereof include zinc compounds such as zinc sulfate, zinc acetate, and zinc chloride.

  The ratio of metal salt or metal complexation can be controlled by adjusting the reaction conditions such as pH and temperature during the reaction and adjusting the molar ratio of the polymerizable monomer (formula (2)) and the metal-imparting agent. .

  The charge control agent of the present invention can be obtained by copolymerizing a metal salt or metal complex of the polymerizable monomer (formula (2)) and metal obtained above with a copolymerizable component.

  In the present invention, it is a copolymer comprising at least a unit A represented by the formula (1) and a metal chloride or metal complexed unit of a metal derived from the unit A, and the amount of metal in the polymer is , It is necessary to control the unit A to 5 mol% or more and 45 mol% or less. For this purpose, a metal salt or metal complex of the polymerizable monomer (formula (2)) obtained above and a metal, and a polymerizable monomer (formula (2)) that is not metal salt or metal complex. The present invention can be achieved by controlling the amount of charge).

  In the present invention, when the charge control agent is a copolymer of a vinyl monomer copolymerizable with the unit A represented by the formula (1), the vinyl monomer that can be used is as described above. And vinyl monomers.

  Various polymerization initiators such as peroxide polymerization initiators and azo polymerization initiators can be used as the polymerization initiator. Examples of the peroxide polymerization initiator that can be used include peroxyesters, peroxydicarbonates, dialkyl peroxides, peroxyketals, ketone peroxides, hydroperoxides, and diacyl peroxides. Examples of the inorganic system include persulfate and hydrogen peroxide. Specifically, t-butyl peroxyacetate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-hexyl peroxyacetate, t-hexyl peroxypivalate, t-hexyl peroxyiso Peroxyesters such as butyrate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate; diacyl peroxides such as benzoyl peroxide; peroxydicarbonates such as diisopropyl peroxydicarbonate; 1 , 1-di-t-hexylperoxycyclohexane and other peroxyketals; di-t-butyl peroxide and other dialkyl peroxides; and other examples include t-butyl peroxyallyl monocarbonate and the like. It is. 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, dimethyl-2,2′-azobis (2-methylpropionate), etc. Illustrated.

  If necessary, two or more of these polymerization initiators can be used simultaneously. The amount of the polymerization initiator used at this time is preferably 0.1 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. 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.

  On the other hand, the charge control agent of the present invention can be a polymer having a polyester structure, has a polyester structure formed by polycondensation of at least a polyhydric alcohol component and a polyvalent carboxylic acid component, and at least A copolymer comprising a unit A represented by the formula (1) and a metal chloride or metal complex unit of a metal derived from the unit A, wherein the amount of metal in the polymer is 5 mol% or more and 45 mol% or less are contained. In this case, a hybrid resin modified with a vinyl monomer can be used as the resin having a polyester structure.

  A known method can be used to adjust the vinyl modification ratio in the hybrid resin. Specifically, an arbitrary modification ratio can be adjusted by changing the charged amount ratio of the polyester resin component to be used and the vinyl monomer component.

  The following are mentioned as a polyhydric alcohol component which comprises resin containing the said polyester structure. Specifically, for example, as the dihydric alcohol component, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis ( 4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2 -Alkylene oxide adducts of bisphenol A such as bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, Opentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A And hydrogenated bisphenol A.

  Examples of the trivalent or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. Can be mentioned.

  Examples of the polyvalent carboxylic acid component include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; And succinic acid substituted with an alkyl group having 6 to 12 carbon atoms or an anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof; and the like.

  Among them, in particular, a carboxylic acid component (for example, fumaric acid, maleic acid, maleic anhydride, phthalate, which includes a bisphenol derivative as a diol component and a divalent or higher carboxylic acid or an acid anhydride thereof, or a lower alkyl ester thereof) A polyester resin obtained by polycondensation of these with an acid component such as acid, terephthalic acid, trimellitic acid, pyromellitic acid or the like can be preferably used.

  As a method for hybridizing the polyester resin with a vinyl monomer, a known method can be used. Specific examples include a method in which a polyester is vinyl-modified with a peroxide-based initiator or a polyester resin having an unsaturated group is graft-modified to produce a hybrid resin.

  Moreover, as a vinyl monomer which can be used for hybridization of a polyester resin in the present invention, the above-described vinyl monomers can be used.

  In the present invention, it is a copolymer comprising at least a unit A represented by the formula (1) and a metal chloride or metal complexed unit of a metal derived from the unit A, and the amount of metal in the polymer is , It is necessary to control the unit A to 5 mol% or more and 45 mol% or less. For this purpose, a metal salt or metal complex of the polymerizable monomer (formula (2)) obtained above and a metal, and a polymerizable monomer (formula (2)) that is not metal salt or metal complex. The present invention can be achieved by controlling the amount of charge).

  In the present invention, a known method can be used as a method for adjusting the weight average molecular weight of the polymer. Specifically, in the polyester resin, it can be arbitrarily adjusted depending on the charging ratio of the acid component and the alcohol component and the polymerization time. In addition, in the hybrid resin, in addition to adjusting the molecular weight of the polyester component, it is possible to adjust the molecular weight of the vinyl-modified unit. Specifically, it can be arbitrarily adjusted by the radical initiator amount, the polymerization temperature, etc. in the vinyl modification reaction step.

  In the toner of the present invention, the content of the charge control agent is not particularly limited, but is preferably 0.1 parts by mass or more and 20.0 parts by mass or less, more preferably 0 with respect to 100 parts by mass of the binder resin. .3 parts by mass or more and 10.0 parts by mass or less. When the content is less than 0.1 parts by mass, the content is too small, and thus the effect of improving the triboelectric charging characteristics may not be sufficiently exhibited. If the amount exceeds 20.0 parts by mass, the dispersibility of the charge control agent in the toner particles may deteriorate.

  In the toner of the present invention, the binder resin used 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 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, and if it is more than 80000, it is difficult to achieve low-temperature fixing.

  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 a 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 at the time of fixing, and the anti-offset performance can be remarkably improved. Furthermore, the low-temperature fixability can be improved by accelerating the melting of the toner at the time of fixing. In the DSC curve of the toner, it is preferable to use a wax having a peak temperature range of 45 ° C. or higher and 130 ° C. or lower when the temperature is increased. More preferably, the wax is 50 ° C. or higher and 110 ° C. or lower, more preferably 50 ° C. or higher and 90 ° C. or lower.

  The wax used in the toner of the present invention preferably has a content in the range of 0.5 to 30.0 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 30.0 parts by mass, the long-term storage stability may deteriorate. In addition, the dispersibility of other toner materials deteriorates, and the amount of wax present in the vicinity of the toner surface increases. Even if the charging characteristics are improved by the features of the present invention, the fluidity of the toner is reduced. Doing so may lead to degradation of image characteristics.

  The wax that can be used in the toner of the present invention may be selected from those having an endothermic peak in the above range. Specific examples include, but are not limited to, petroleum waxes such as paraffin wax, microcrystalline wax, petrolatum and derivatives thereof, montan wax and derivatives thereof, hydrocarbon waxes and derivatives thereof according to Fischer-Tropsch method, and polyethylene. Polyolefin wax and derivatives thereof, natural wax such as carnauba wax and candelilla wax and derivatives thereof, and the derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. Furthermore, fatty acids such as higher aliphatic alcohols, stearic acid and palmitic acid, or compounds thereof, acid amide waxes, ester waxes, ketones, hydrogenated castor oil and derivatives thereof, plant waxes, animal waxes and 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, the storage stability of the toner is deteriorated, which may cause a blocking phenomenon. Further, in a high temperature environment, the toner may be fused into the developing device, and the toners may be fused to cause a decrease in fluidity. Furthermore, as a result, the frictional charging efficiency is lowered, and even when the charge control resin of the present invention is used, toner scattering and fogging may 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 ° C. or higher and 70 ° C. or lower, more preferably in the range of 50 ° C. or higher and 70 ° C. or lower.

  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 74, 93, 94, 95, 109, 111, 128, 138, 151, 155, 174, 180, and 185 are preferably used. Examples of the dye system include C.I. l. Solvent Yellow 93, 162, and 163 are listed.

  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 part by mass or more and 20.0 parts by mass or less based on 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 preferably a surface-modified magnetic material. When used in a polymerization method toner produced by a production method such as a polymer dissolution suspension method or a suspension polymerization method, a toner subjected to a hydrophobic treatment with a surface modifier which is a substance that does not inhibit polymerization is preferable. 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 0.1 μm or more and about 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 characteristics when applied with 796 kA / m (10 k Oersted) are coercive force (Hc) of 1.59 kA / m or more, 23.9 kA / m or less (20 Oersted or more, 300 Oersted or less), saturation magnetization (σs) 50 Am ² / kg As described above, a magnetic material having 200 Am ² / kg or less, residual magnetization (σr) of ² Am ² / kg or more and 20 Am ² / kg or less is preferable.

  In the toner of the present invention, in order to develop finer latent image dots faithfully in order to improve the image quality, the weight average particle diameter (D4) of the toner is 3.0 μm or more and 9.0 μm or less. Preferably, it is 4.0 μm or more and 6.5 μm or less.

  In the toner of the present invention, other charge control agents can be contained in order to assist the triboelectric charging characteristics. 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, dicarboxylic acid; sulfonic acid, carboxylic acid in the side chain For example, boron compound; urea compound; silicon compound; 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. In particular,
(A) 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 (B) ) A method for producing toner particles by an interfacial polymerization method such as a microcapsule production method (C) A method for producing toner particles by a coacervation method (D) Japanese Patent Laid-Open Nos. 62-106473 and 63-186253 A method of obtaining toner particles by an associative polymerization method for aggregating at least one kind of fine particles as disclosed in the official gazette to obtain particles having a desired particle size (E) Toner particles by a dispersion polymerization method characterized by monodispersion Method of manufacturing (F) A method of obtaining toner particles by dissolving a necessary resin in a water-insoluble organic solvent and then forming a toner in water using a polymer dissolution (melting) suspension method (G) an emulsion dispersion method (H) A toner component is kneaded and uniformly dispersed using a pressure kneader, an extruder, a media disperser, etc., and then cooled, and the kneaded product is allowed to collide with a target under a mechanical or jet stream to obtain a desired value. A pulverization method in which toner particles are produced by finely pulverizing the toner to a toner particle size and then making a particle size distribution through a classification process. (I) Further, the toner obtained by the pulverization method is spheroidized by heating in a solvent, etc. Examples thereof include a method for obtaining particles.

  Among them, the effect of the present invention is particularly remarkable when toner particles are produced by a suspension polymerization method. Although the reason for this is not clear, it is considered that the charge control agent can be effectively present in the vicinity of the toner particle surface in the step of granulating in an aqueous medium (granulation step).

  In the method for producing toner particles by the suspension polymerization method, first, a colorant is uniformly dissolved and mixed or dispersed in the polymerizable monomer constituting the 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. A polymerizable monomer composition is prepared by uniformly dissolving, mixing, or dispersing this together with a polymerizable monomer, a charge control resin, a polymerization initiator, a wax, and other additives as necessary, using a stirrer or the like. . The polymerizable monomer composition thus obtained is added to a dispersion medium (preferably an aqueous medium) containing a dispersion stabilizer, and a high-speed dispersion such as a high-speed stirrer or an ultrasonic disperser is used as a stirrer. Using a machine, finely disperse to the toner particle size (granulation step). Thereby, particles of the polymerizable monomer composition are formed. In the polymerization step, the polymerizable monomer contained in the particles of the polymerizable monomer composition is polymerized by light or heat to obtain toner particles.

  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.

  As the polymerizable monomer that can be suitably used in the suspension polymerization method, a vinyl monomer that can be used in the charge control agent of the present invention can be used in the same manner.

  The dispersion medium that can be used in the production method is determined based on the solubility in the dispersion medium such as the charge control agent, the binder resin, the organic medium, and the polymerizable monomer of the present invention. Those are preferred. What can be used as an aqueous dispersion medium is, for example, water; alcohols such as methyl alcohol, ethyl alcohol, modified ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, sec-butyl alcohol; methyl cellosolve , Cellosolve, isopropyl cellosolve, butyl cellosolve, ether alcohols such as diethylene glycol monobutyl ether, and other water-soluble ones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc .; esters such as ethyl acetate; ethyl ether Selected from ethers such as ethylene glycol; acetals such as methylal and diethyl acetal; acids such as formic acid, acetic acid and propionic acid, etc. And particularly preferably an alcohol. Two or more of these solvents can be mixed and used. The concentration of the liquid mixture or the polysynthetic monomer composition with respect to the dispersion medium is preferably 1% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 65% by mass or less 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 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the liquid mixture or the polymerizable monomer composition.

  As the polymerization initiator used in the toner of the present invention using the suspension polymerization method, a polymerization initiator that can be used in the charge control agent of the present invention can be used in the same manner. It is preferable that the usage-amount of the polymerization initiator used in this case is 0.1 to 20.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  Further, when a toner is produced by a suspension polymerization method, a known crosslinking agent may be added. A preferable addition amount is 0.001 part by mass or more and 15.000 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.

  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.

  In the inorganic fine powder in the present invention, the number average particle diameter (D1) of the primary particles is preferably 4 nm or more and 80 nm or less.

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 amount of the inorganic fine powder having a primary particle number average particle diameter (D1) of 4 nm or more and 80 nm or less is preferably 0.1 parts by mass or more and less than 5.0 parts by mass with respect to 100 parts by mass of the toner particles. . If the addition amount is less than 0.1 parts by mass, the effect is not sufficient, and if it is 5.0 parts by mass or more, the fixability may be deteriorated.

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

  The toner of the present invention can be mixed with a magnetic 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 characteristics of charging are important, the effect is more remarkably exhibited.

  When the toner of the present invention is used in a two-component developer, examples of the magnetic carrier include surface oxidized or unoxidized metals such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earths. Particles, alloy particles thereof, oxide particles, ferrites and the like that are finely divided can be used. Further, a magnetic fine particle dispersed resin carrier in which magnetic fine particles are dispersed in a resin can also be used.

  The surface of the magnetic carrier particles is preferably coated with a resin, and the coating method includes a method of adhering a coating solution prepared by dissolving or suspending a coating material such as a resin in a solvent to the surface of the magnetic carrier core particles, Conventionally known methods such as a method of mixing magnetic carrier core particles and a coating material with powder 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% by mass or more and 30% by mass or less (preferably 0.5% by mass or more and 20% by mass or less) with respect to the carrier core particles. The average particle size of these carriers is preferably 10 μm or more and 100 μm or less, and more preferably 20 μm or more and 70 μm or less.

  When a two-component developer is prepared by mixing the toner of the present invention and a magnetic carrier, the mixing ratio is 2% by mass or more and 15% by mass or less, preferably 4% by mass or more and 13% as the toner concentration in the developer. Good results are usually obtained when the content is less than or equal to mass%. 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.

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

1. Molecular Weight Distribution of Polymer The molecular weight distribution of the polymer was measured by gel permeation chromatography (GPC) as follows.

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

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

2. Determination of amount of metal in monomer and polymer The amount of metal in the monomer and polymer is determined by fluorescent X-rays. The measurement of fluorescent X-rays conforms to JIS K 0119-1969, and is specifically as follows.

  As a measuring device, a wavelength dispersion type fluorescent X-ray analyzer “Axios” (manufactured by PANalytical) and attached dedicated software “SuperQ ver. 4.0F” (manufactured by PANalytical) for setting measurement conditions and analyzing measurement data ) Is used. Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 27 mm, and the measurement time is 10 seconds. Further, when measuring a light element, it is detected by a proportional counter (PC), and when measuring a heavy element, it is detected by a scintillation counter (SC).

  As a measurement sample, 4 g of the polymer was put in a dedicated aluminum ring for press and leveled, and a tablet-forming compressor “BRE-32” (manufactured by Maekawa Test Instruments Co., Ltd.) was used. Pellets that have been pressed for 2 seconds and formed into a thickness of 2 mm and a diameter of 39 mm are used.

  The measurement is performed under the above conditions, the element is identified based on the obtained X-ray peak position, and the concentration is calculated from the count rate (unit: cps) which is the number of X-ray photons per unit time.

  Using this measurement result and a calibration curve prepared in advance for the metal element to be quantified, the metal element is quantified.

3. Acid value of polymer The acid value is the number of mg of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. The acid value in the present invention is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.

(I) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95 vol%), and ion exchange water is added to make 100 ml to obtain a phenolphthalein solution.

  7 g of special grade potassium hydroxide is dissolved in 5 ml of water, and ethyl alcohol (95 vol%) is added to make 1 l. In order not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 ml of 0.1 mol / l hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxide required for neutralization. Determined from the amount of potassium solution. As the 0.1 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

(Ii) Operation main test;
2.0 g of the measurement sample is precisely weighed into a 200 ml Erlenmeyer flask, and 100 ml of a mixed solution of toluene / ethanol (3: 1) is added and dissolved over 1 hour. Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of the titration is when the light red color of the indicator lasts for 30 seconds.

Blank test;
Titration is performed in the same manner as described above, except that no sample is used (that is, only a mixed solution of toluene / ethanol (3: 1) is used).

(Iii) The acid value is calculated by substituting the obtained result into the following equation.
A = [(C−B) × f × 5.61] / S

  Here, A: acid value (mgKOH / g), B: addition amount (ml) of a potassium hydroxide solution in a blank test, C: addition amount (ml) of a potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g).

4). Hydroxyl value of polymer The hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated. The hydroxyl value in the present invention is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.

(1) Preparation of reagent 25 g of special grade acetic anhydride is placed in a 100 ml volumetric flask, pyridine is added to make a total volume of 100 ml, and shaken sufficiently to obtain an acetylating reagent. The obtained acetylating reagent is stored in a brown bottle so as not to come into contact with moisture, carbon dioxide gas and the like.

  Dissolve 1.0 g of phenolphthalein in 90 ml of ethyl alcohol (95 vol%) and add ion exchange water to make 100 ml to obtain a phenolphthalein solution.

  Dissolve 35 g of special grade potassium hydroxide in 20 ml of water and add ethyl alcohol (95 vol%) to make 1 liter. In order not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 ml of 0.5 mol / l hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxide required for neutralization. Determined from the amount of potassium solution. As the 0.5 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

(2) Operation (A) Main test 1.0 g of a measurement sample is precisely weighed in a 200 ml round bottom flask, and 5.0 ml of the acetylating reagent is accurately added to this using a whole pipette. At this time, if the sample is difficult to dissolve in the acetylating reagent, a small amount of special grade toluene is added and dissolved.

  Place a small funnel in the mouth of the flask and immerse 1 cm of the bottom of the flask in a 97 ° C. glycerin bath and heat. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, it is preferable to cover the base of the neck of the flask with a cardboard having a round hole.

  After 1 hour, the flask is removed from the glycerin bath and allowed to cool. After standing to cool, 1 ml of water is added from the funnel and shaken to hydrolyze acetic anhydride. The flask is again heated in the glycerin bath for 10 minutes for further complete hydrolysis. After cooling, wash the funnel and flask walls with 5 ml of ethyl alcohol.

  Add several drops of the phenolphthalein solution as an indicator and titrate with the potassium hydroxide solution. The end point of the titration is when the light red color of the indicator lasts for 30 seconds.

(B) Blank test Titration similar to the above operation is performed except that the measurement sample is not used.

(3) Substituting the obtained results into the following formula to calculate the hydroxyl value.
A = [{(BC) × 28.05 × f} / S] + D

  Here, A: hydroxyl value (mg KOH / g), B: addition amount (ml) of potassium hydroxide solution in blank test, C: addition amount (ml) of potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g), D: acid value (mgKOH / g) of the measurement sample.

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

6). Glass transition temperature of polymer and toner The glass transition temperature of the polymer and toner in the present invention was measured using a differential operation calorimeter (DSC measuring device).

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

7). Measurement of particle diameter of resin fine particles The number average particle diameter of the resin fine particles in the present invention can be determined by the following method.
Using a Microtrac particle size distribution measuring apparatus HRA (X-100) (manufactured by Nikkiso Co., Ltd.), measurement was performed with a range setting from 0.001 μm to 10 μm, and the number average particle diameter was determined.

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

  As the electrolytic aqueous solution used for the measurement, a solution obtained by dissolving special grade sodium chloride in ion-exchanged water to a concentration of 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, the dedicated software was set as follows.

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

  In the “pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

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

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. “Part” means “part by mass”.

  The salicylic acid derivative-based monomer represented by the formula (2) used in the present invention can be produced by a known method.

<Preparation Example 1>
The monomer 2A represented by the formula (2A) was produced using the method described in JP-A-63-270060, Journal of Polymer Science: Polymer Chemistry Edition 18, 2755 (1980).

<Preparation Example 2>
The monomer 2B represented by the formula (2B) was produced by using the method described in JP-A-62-1874429.

<Preparation Example 3>
The monomer 2C represented by the formula (2C) was produced using the method described in JP-A 63-270060, Journal of Polymer Science: Polymer Chemistry Edition 18, 2755 (1980).

<Preparation Example 4>
The monomer 2D represented by the formula (2D) was produced using the method described in Bioorganic & Medicinal Chemistry, 15 (15), 5207 (2007).

<Preparation Example 5>
An aqueous solution of 0.5 mol of NaOH and 0.4 mol of the monomer 2A produced in Preparation Example 1 were mixed and dissolved by heating. This solution was mixed with a 0.1 mol aqueous solution of aluminum sulfate, heated and stirred, and then collected by filtration under conditions from neutral to weak alkali. The collected white precipitate was washed with water until the washing water became neutral, and then dried to obtain monomer 3A containing monomer 2A and containing aluminum as a metal salt or metal complex. About the obtained monomer 3A containing aluminum, aluminum was quantified by the fluorescent X ray, and it was confirmed that 7.60% is contained. From the obtained results, it was confirmed that the monomer 3A contains 50 mol% of aluminum with respect to the monomer 2A.

<Preparation Example 6>
A 0.3 mol NaOH aqueous solution and 0.3 mol of the monomer 2A produced in Preparation Example 1 were mixed and dissolved by heating. This solution was mixed with a 0.1 molar aqueous solution of aluminum sulfate and stirred under heating. The solution was adjusted from neutral to weakly alkaline and collected by filtration. The collected white precipitate was washed with heated washing water and then dried to obtain monomer 3B containing monomer 2A and containing aluminum as a metal salt or metal complex. About the obtained monomer 3A containing aluminum, aluminum was quantified by fluorescent X-rays and it was confirmed that it contained 9.90%. From the obtained result, it was confirmed that the monomer 3B contains 67 mol% of aluminum with respect to the monomer 2A.

<Preparation Example 7>
An aqueous solution of 0.5 mol of NaOH and 0.4 mol of the monomer 2B produced in Preparation Example 2 were mixed and dissolved by heating. This solution was mixed with a 0.1 mol aqueous solution of aluminum sulfate, heated and stirred, and then collected by filtration under conditions from neutral to weak alkali. The collected white precipitate was washed with water until the washing water became neutral, and then dried to obtain monomer 3C containing monomer 2B and containing aluminum as a metal salt or metal complex. About the obtained monomer 3C containing aluminum, aluminum was quantified by fluorescent X-ray and it was confirmed that 5.80% was contained. From the obtained results, it was confirmed that the monomer 3C contains 50 mol% of aluminum with respect to the monomer 2B.

<Preparation Example 8>
A 0.3 mol NaOH aqueous solution and 0.3 mol of the monomer 2B produced in Preparation Example 1 were mixed and dissolved by heating. This solution was mixed with a 0.1 molar aqueous solution of aluminum sulfate and stirred under heating. The solution was adjusted from neutral to weakly alkaline and collected by filtration. The collected white precipitate was washed with heated washing water and dried to obtain monomer 3D containing monomer 2B and containing aluminum as a metal salt or metal complex. About the obtained monomer 3D containing aluminum, aluminum was quantified by the fluorescent X ray, and it was confirmed that 7.60% is contained. From the obtained result, it was confirmed that the monomer 3D contains 67 mol% of aluminum with respect to the monomer 2B.

<Preparation Example 9>
0.4 mol of the NaOH 0.4 mol aqueous solution and the monomer 2C produced in Preparation Example 3 were mixed and dissolved by heating. This solution was mixed with a 0.1 mol aqueous solution of chromium sulfate and heated and stirred, and then the solution was adjusted to neutral and collected by filtration. The collected white precipitate was washed with water until the washing water became neutral, and then dried to obtain monomer 3E containing monomer 2C and containing chromium as a metal salt or metal complex. About the obtained monomer 3E containing chromium, chromium was quantified by fluorescent X-rays, and it was confirmed that 13.70% was contained. From the obtained result, it was confirmed that the monomer 3E contains 50 mol% of chromium with respect to the monomer 2C.

<Preparation Example 10>
A 0.2 mol aqueous solution of NaOH and 0.2 mol of the monomer 2D produced in Preparation Example 4 were mixed and dissolved by heating. This solution was mixed with a 0.1 molar aqueous solution of zinc chloride and stirred under heating, and the solution was adjusted from neutral to weakly alkaline and collected by filtration. The collected white precipitate was washed with heated washing water and dried to obtain monomer 3F containing monomer 2D and containing zinc as a metal salt or metal complex. The obtained zinc-containing monomer 3F was quantified by fluorescent X-ray and was confirmed to contain 16.60%. From the obtained result, it was confirmed that the monomer 3F contains 50 mol% of zinc with respect to the monomer 2D.

<Preparation Example 11>
To a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 60.00 parts of toluene was charged and refluxed under a nitrogen stream.

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

<Monomer composition, mixing ratio>
-7.45 parts of monomer 2A prepared in Preparation Example 1. 7.45 parts of monomer 3A containing aluminum prepared in Preparation Example 5-85.10 parts of styrene-60.00 parts of toluene

  To this monomer mixture, 6.60 parts of t-butylperoxyisopropyl monocarbonate (75% hydrocarbon solvent diluted product) was further mixed as a polymerization initiator and added dropwise to the reaction vessel over 30 minutes. . The mixture was stirred at 110 ° C. for 4 hours, and cooled to room temperature after completion of the reaction. The obtained polymer-containing composition was added dropwise to a mixed solution of 1400 parts of methanol and 10 parts of acetone over 10 minutes with stirring to precipitate and crystallize the resin composition. The obtained resin composition was filtered and rinsed twice with 200 parts of methanol. The obtained resin powder was dried at 60 ° C. under reduced pressure for 10 hours to obtain a polymer 1.

<Preparation Examples 12 to 28, Comparative Preparation Examples 29 to 33>
Polymers 2 to 23 were obtained in the same manner as in Preparation Example 11 except that the monomer composition, the mixing ratio, and the polymerization initiator amount were changed as shown in Table 1.

  The composition ratio, yield and molecular weight of the polymers 1 to 23 obtained in Preparation Examples 11 to 28 are shown in Table 2. The composition ratio in the polymer was as follows.

  In addition, about the unit shown by Formula (1) in a table | surface, it is the structure of the following description.

<Preparation Example 34>
Propylene glycol 90.0 parts, terephthalic acid 104.8 parts, trimellitic acid 5 parts, adipic acid 10.0 parts, maleic anhydride in a reactor equipped with a condenser, stirrer, thermometer and nitrogen inlet 24.0 parts and 2.0 parts of tetrastearyl titanate as a condensation catalyst were added and reacted at 230 ° C. for 6 hours while distilling off water produced under a nitrogen stream. Subsequently, it was made to react under reduced pressure of 5-20 mmHg for 8 hours, and the unsaturated polyester resin 1 was obtained. This unsaturated polyester resin 1 had an acid value of 36.2, a hydroxyl value of 10.1, Mn of 2400, and Mw of 4600.

  Next, 200 parts of toluene and 100 parts of the unsaturated polyester resin 2 were charged into a reaction vessel equipped with a cooling pipe, a stirrer, a thermometer, and a nitrogen introduction pipe, and stirred at 50 ° C. in a nitrogen stream.

next,
-2.00 parts of monomer 2A prepared in Preparation Example 1-8.00 parts of monomer 3A containing aluminum prepared in Preparation Example 5-40.00 parts of styrene-50.00 parts of toluene

To this monomer mixed solution, 3.50 parts of t-butylperoxyisopropyl monocarbonate (75% hydrocarbon solvent diluted product) was further mixed as a polymerization initiator and added dropwise to the reaction vessel over 30 minutes. . The mixture was stirred at 110 ° C. for 3 hours and cooled to room temperature. The obtained polymer-containing composition was added dropwise to a mixed solution of 2800 parts of methanol and 20 parts of acetone over 10 minutes with stirring to precipitate and crystallize the resin composition. The obtained resin composition was filtered and rinsed twice with 300 parts of methanol. The obtained resin powder was dried at 60 ° C. under reduced pressure for 10 hours to obtain a polymer 24. From the result of ¹ H-NMR, the obtained polymer was confirmed to contain 6.2% by mass of the unit represented by the formula (1A). Moreover, the amount of aluminum was quantified by fluorescent X-rays, and it was confirmed that 20.0 mol% of aluminum was contained with respect to the formula (1A). The polymer had Mn of 4200 and Mw of 6800.

Example of toner production:
<Example 1>
Preparation of pigment dispersion paste <Feed ratio>
-80 parts of styrene-C.I. I. Pigment Blue 15: 3 13 parts After the above material was well premixed in a container, it was dispersed in a bead mill for 4 hours while keeping it at 20 ° C. or lower to prepare a pigment dispersion paste.

Preparation of toner particles 390 parts of a 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 11000 rpm using CLEARMIX (M Technique). Was stirred. To this, 58 parts of 1.0 mol / liter-CaCl ₂ aqueous solution was added to obtain a dispersion containing Ca ₃ (PO ₄ ) ₂ .

<Feed ratio>
-46.0 parts of the above pigment dispersion paste-42.0 parts of styrene-18.0 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 mgK OH / g, Mw: 16000)
-Polymer 1 prepared in Preparation Example 11 2.0 parts

  These were heated to 60 ° C., melted and dispersed to obtain a monomer mixture. Furthermore, while maintaining the temperature at 60 ° C., 5.0 parts of 2,2-azobis (2,4-dimethylvaleronitrile) was added as a polymerization initiator and dissolved to prepare a monomer composition.

The monomer composition was charged into the dispersion medium. 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 to select 2 μm or more and less than 10 μm to prepare toner particles 1.

Preparation of Toner 100 parts of the obtained toner particles A were treated with hexamethyldisilazane, and then treated with silicone oil. The number average primary particle size was 9 nm, and the BET specific surface area was 180 m ² / g. Toner 1 was obtained by mixing and externally adding 1 part of silica fine powder with a Henschel mixer (Mitsui Miike Chemical Co., Ltd.).

<Examples 2 to 16>
Toners 2 to 16 were obtained in the same manner as in Example 1 except that instead of the polymer 1, the polymers 2 to 16 obtained in Preparation Examples 12 to 26 were respectively changed.

<Example 17>
Preparation of pigment dispersion paste (preparation ratio)
-80 parts of styrene-13 parts of carbon black The above materials were well premixed in a container, and then dispersed in a bead mill for 4 hours while being kept at 20 ° C or lower to prepare a pigment dispersion paste.

Preparation of toner particles 350 parts of a 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 used with Claremix (manufactured by M Technique). Stir at 000 rpm. 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 .

- the pigment dispersed paste 46.0 parts Styrene 39.0 parts n-Butyl acrylate 22.0 parts Ester wax 13.0 parts (main component _{C 19 H 39 COOC 20 H 41} , mp 68.6 ° C.)
Saturated polyester resin 5.0 parts (terephthalic acid-propylene oxide modified bisphenol A copolymer, acid value 10 mgK OH / g, Mw 16000)
-Polymer 17 obtained in Preparation Example 27 2.0 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 to select 2 μm or more and less than 10 μm to prepare toner particles 17. Further, in the same manner as in Example 1, the toner 17 was obtained by externally adding hydrophobic silica fine powder to the toner particles 17.

<Example 18>
In Example 1, polymer 18 obtained in Preparation Example 28 was used instead of polymer 1, and C.I. I. Pigment Blue 15: 3 instead of C.I. I. A toner 18 was obtained in the same manner as in Example 1 except that it was changed to CI Pigment Bio Red 19.

<Example 19>
In Example 1, a toner 19 was obtained in the same manner as in Example 1 except that the polymer 24 obtained in Preparation Example 29 was used instead of the polymer 1.

<Example 20>
Preparation of binder resin (preparation ratio)
Bisphenol A / propylene oxide 2.2 mol adduct 1206 parts Bisphenol A / ethylene oxide 2.2 mol adduct 475 parts terephthalic acid 249 parts trimellitic anhydride 192 parts fumaric acid 290 parts dibutyltin oxide 0.1 parts made of glass The flask was placed in a 4-liter four-necked flask, and a thermometer, a stir bar, a condenser, and a nitrogen inlet tube were attached and placed in a mantle heater. Under a nitrogen atmosphere, reaction was carried out at 220 ° C. for 5 hours to obtain a polyester resin.

Preparation of toner particles (preparation ratio)
-100.0 parts of the above polyester resin-C.I. I. Pigment Blue 15: 3 5.0 parts, Aliphatic wax 3.0 parts (Mw 1850, Mw / Mn 1.27, melting point 78.6 ° C.)
-After sufficiently premixing 2.0 parts of the polymer 1 obtained in Preparation Example 11 with a Henschel mixer (Mitsui Miike Chemical Co., Ltd.), melt-kneading with a twin-screw extruder, cooling, hammer mill And then finely pulverized with an air jet fine pulverizer, and the resulting finely pulverized product was classified with a multi-division classifier to obtain toner particles 20. Further, in the same manner as in Example 1, the toner 20 was obtained by externally adding hydrophobic silica fine powder to the toner particles 20.

<Comparative Examples 1 to 5>
In Example 1, toners 21 to 25 of the comparative examples were prepared in the same manner as in Example 1 except that the polymers 19 to 23 obtained in Preparation Examples 29 to 33 of the comparative examples were used instead of the polymer 1. Got.

  The weight average diameter (D4) and DSC measurement result (Tg) of the obtained toner are shown in the table.

  Toners 1 to 25 obtained here and ferrite carrier F813-300 (manufactured by Powdertech) were mixed so as to have a toner concentration of 6.0% by weight to obtain a two-component developer.

  The obtained toner and two-component developer were evaluated as follows.

Toner charge rise characteristics and environmental dependency evaluation:
For the measurement of the charge amount, 50 g of each two-component developer is fractionated, and the room temperature and humidity environment (23 ° C./60% Rh), the low temperature and low humidity environment (15 ° C./15% Rh), and the high temperature and high humidity environment (30 ° C.). / 80% Rh) for 4 days, put in a 50cc plastic container, shake 30 times for 15 seconds, and 180 times for 1 minute 30 seconds. Measurement was performed using an apparatus. The evaluation was made by measuring the absolute value of the triboelectric charge amount at each shaking frequency and judging according to the following criteria. The results are shown in Table 7.

<Charging rising characteristics>
Compared to the absolute value of triboelectric charge of 180 times shaking under low temperature and low humidity and high temperature and high humidity, the absolute value of triboelectric charge amount of 30 times shaking is A rank: 90% or more and 100%
B rank: 80% or more and less than 90% C rank: 70% or more and less than 80% D rank: less than 70%

<Environment dependency>
Difference in triboelectric charge amount between low temperature and low humidity and high temperature and high humidity when shaken 180 times A rank: 0 or more and less than 15 μC / g B rank: 15 or more and less than 20 μC / g C rank: 20 or more and less than 30 μC / g D Rank: 30μC or more

(Measurement method of charge amount)
A metal measuring vessel 2 having a 500 mesh screen 3 at the bottom is charged with 0.5 g of a developer for measuring the triboelectric charge amount, and a metal lid 4 is placed thereon. The total mass of the measurement container 2 at this time is weighed and is defined as Wl (g). Next, in the suction device 1 (at least the portion in contact with the measurement container 2) is suctioned from the suction port 7 and the air volume control valve 6 is adjusted to set the pressure of the vacuum gauge 5 to 250 mmAq. In this state, the toner is removed by suction for 2 minutes. The potential of the electrometer 9 at this time is set to V (volt). Here, 8 is a capacitor, and the capacity is C (μF). The mass of the entire measurement container after the suction is weighed and is defined as W2 (g). The triboelectric charge amount (mC / kg) of the toner is calculated as follows.
Frictional charge (mC / kg) = (C × V) / (W1-W2)

As a result, it was found that the toners of Examples 1 to 20 according to the present invention are superior to the toner of Comparative Examples 1 to 5 with respect to the rising characteristics of charging and environmental dependency.
With respect to the toners of Examples 1 to 20 and Comparative Examples 1 to 5, image output evaluation was performed as follows.

Image evaluation:
Using a modified machine (process speed: 220 mm / sec) of a full color laser beam printer LBP-5300 (manufactured by Canon Inc.) as an evaluation machine, 23 ° C./60% Rh (under normal temperature and normal humidity) and 30 ° C./80% Rh ( The image was evaluated in a high-temperature and high-humidity environment. In the evaluation, an image output cartridge filled with 150 g of each toner was mounted on a cyan station, and a dummy cartridge was mounted on the other, and image evaluation was performed in a normal temperature and normal humidity environment and a high temperature and high humidity environment. In the image evaluation, the image output cartridge was left in each environment for 4 days and then carried out.

In the image output test, the image density and fog were measured and the average value was obtained with the first to fifth sheets as the initial 1, the 45th to the 50th sheets as the initial 2, the 11995 to the 12,000th sheets after endurance. . In this test, A4 plain paper of 75 g / m ² was used, and an original chart with an image area ratio of 2% was continuously output. The results are shown in Table 5.

(Image density)
For image density measurement, a Macbeth reflection densitometer RD918 (manufactured by Macbeth) was used to measure a relative density with respect to a printout image of a white background portion having an original density of 0.00, and evaluation was performed according to the following criteria.
A rank: 1.40 or more B rank: 1.30 or more, less than 1.40 C rank: 1.20 or more, less than 1.30 D rank: less than 1.20

(Fog measurement)
The fog is measured using a REFECTOMETER MODEL TC-6DS (manufactured by Tokyo Denshoku Co., Ltd.) and calculated from the following formula. As the value is smaller, the fog is suppressed.

Fog (Reflectance) (%) = [Reflectance of standard paper (%)] − [Reflection of non-image part of sample]
rate(%)〕

Evaluation was made according to the following criteria.
A rank: 0.6% or less B rank: exceeding 0.6%, 1.2% or less C rank: exceeding 1.2%, 1.8% or less D rank: exceeding 1.8%

  As a result, with the toners of Examples 1 to 20 according to the present invention, good image results were obtained in both image density and fog in a normal temperature and normal humidity environment and a high temperature and high humidity environment.

  On the other hand, in the toners of Comparative Examples 6 to 10, image defects occurred in both the normal temperature and normal humidity environment and the high temperature and high humidity environment.

Pigment dispersibility evaluation:
The toners of Examples 1 to 16 and Comparative Example 1 that are toners using a cyan colorant copper phthalocyanine compound were evaluated for pigment dispersibility.

  When the cross section of the toner 1 obtained in Example 1 was observed with a transmission electron microscope (TEM) by the dyeing ultrathin section method, it was divided into a resin part mainly composed of styrene-acrylic resin and a central part mainly composed of wax. The capsule structure was confirmed. Further, it was confirmed that about 50 nm of pigment particles were uniformly finely dispersed in the styrene-acrylic resin layer.

For toners 2 to 16 and 21, the pigment dispersibility was evaluated in the same manner as described above, and the following evaluation criteria were used. The results are shown in Table 6.
Rank A: Present in a state where pigment particles of about 50 nm are uniformly dispersed B Rank: Present in a state where many pigments are uniformly dispersed, Rank C: State in which most of the pigment is aggregated Present

  As a result, it was confirmed that the toner particles of Examples 1 to 16 according to the present invention are more effective in pigment dispersion than Comparative Example 1.

DESCRIPTION OF SYMBOLS 1 Suction machine 2 Measurement container 3 Screen 4 Lid 5 Vacuum gauge 6 Air volume control valve 7 Suction port 8 Condenser 9 Electrometer

Claims (4)

In a toner having toner particles containing at least a binder resin, a colorant, and a charge control agent, the charge control agent is a metal of at least a unit A represented by the formula (1) and a metal derived from the unit A A toner comprising a unit containing a chlorinated or metal complexed unit, wherein the amount of metal in the polymer is 5 mol% or more and 45 mol% or less with respect to unit A.

(COOH and OH in Formula (1) are bonded to adjacent positions, R ₁ represents hydrogen or an alkyl group having 1 to 6 carbon atoms, and R ₂ represents hydrogen or a methyl group.)   The toner according to claim 1, wherein the metal in the polymer of the charge control agent is a metal selected from the group consisting of aluminum, zinc, chromium, and zirconium.   The toner according to claim 1, wherein the polymer of the charge control agent is a copolymer of a vinyl monomer copolymerizable with the unit A.   The toner adds a polymerizable monomer composition containing at least a polymerizable monomer, a colorant, and the charge control agent to an aqueous medium, and granulates the polymerizable monomer composition in the aqueous medium. A toner having toner particles obtained by forming particles of the polymerizable monomer composition and polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition. The toner according to any one of claims 1 to 3, wherein:

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