JP5541675B2 - 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 recent years, development methods with particularly high resolution and high definition have been demanded, and as one means for satisfying such demands, a reduction in the particle size of toner has been demanded. On the other hand, the printing speed of printers is also increasing, and in addition to the increase in specific surface area associated with the reduction in toner particle size, there is a demand for advanced charge controllability of toner due to the reduction in charging opportunities associated with higher speeds. It became so. In general, when the particle size of the toner becomes small, the charge amount of each toner particle tends to be non-uniform due to the deterioration of fluidity. Therefore, defects such as image defects are likely to occur.

  Furthermore, from the problem of energy saving, it is required to lower the fixing temperature of the toner as much as possible, and the softening point of the resin constituting the toner is being lowered. However, in energy-saving toners, it is not easy to obtain a toner with little deterioration while maintaining chargeability, and various studies have been made in the past.

  Conventionally, studies have been made to stabilize the charge by adding a charge control agent to the toner, to improve the image quality, and to maintain the image quality after a large number of copying operations. Among them, one using a charge control resin is effective, and there is a proposal that it is internally added to the toner (for example, see Patent Document 1). However, although the charge amount improvement by the charge control resin is excellent, the charge control agent does not surely exist on the toner surface. Therefore, the chargeability of individual toners is different, and the overall charge amount distribution may not be uniform.

  Further, there has been proposed an attempt to stabilize the charge by mechanically fixing the resin fine particles containing the charge control unit to the toner base so that the charge control agent is surely present on the toner surface (for example, patents). Reference 2). However, like the external additive, the charge control agent may be peeled off or embedded in the toner particles during the copying operation. Therefore, it is suggested that the charge amount distribution also changes as the toner deteriorates due to embedding or the like, and it has not yet been solved to solve problems such as image defects.

Special registration No. 2694572 JP 2004-318043 A

  Accordingly, an object of the present invention is to provide a toner having a quick charge amount rise and a sharp charge amount distribution.

  Another object of the present invention is to provide a toner that can produce a high-quality image with less toner scattering during transfer and excellent microdot reproducibility.

  Furthermore, an object of the present invention is to provide a toner having both low-temperature fixability and storage stability.

  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.

That is,
(1) forming Chakujushi, a toner having toner particles with an anchored resin fine particles mother particles mother particle arrangement containing a colorant and a wax,
The toner particles have the resin fine particles 0.10% by weight, based on the weight of the base particles,
The resin fine particles, and contains a resin microparticles a made of a resin containing a unit A represented by the following (Equation 1), and a resin fine particle b made of a resin containing a unit B represented by the following (Equation 2) ,
The content of the units A of the resin particles in a is 0 with respect to the resin particles. 10 0 mmol / g or more and 0.800 mmol / g or less ,
Toner, wherein the molar ratio of the content of the said unit A and said unit B in the toner particles is 0.10 or more 10.00 or less.

（式１中、Ｘは、置換基を有していてもよい脂肪族基、または、置換基を有していてもよい芳香族基を示し、Ｒ₁は、水素原子、アルカリ金属原子、炭素数１以上４以下のアルキル基、または、芳香族基を示す。）

(In the formula 1, X is a substituted group aliphatic group which may have a or, represents an aromatic group optionally having a substituent, R ₁ is a hydrogen atom, an alkali metal atom, the carbon having 1 to 4 alkyl group or an aromatic group.)

（式２中、Ｒ₂は、水素原子、または、炭素数１以上４以下のアルキル基もしくはアルコキシ基を示す。）
（２）前記ユニットＡが、フェニルスルホン酸系ユニットである（１）に記載のトナー。
（３）前記トナー粒子が、水系媒体中で生成されたトナー粒子である（１）または（２）に記載のトナー。
（４）前記トナー粒子が、前記樹脂微粒子を前記母粒子の質量に対して１．００質量％以上有する（１）〜（３）に記載のトナー。
であることにより本発明の目的が好適に達成可能となる。

(In the formula 2, R ₂ is a hydrogen atom or an alkyl group or alkoxy group having 1 to 4 carbon atoms.)
(2) the unit A toner according to Ru phenyl sulfonic acid unit der (1).
(3) the toner particles, toner according to Ru Oh toner particles produced in an aqueous medium (1) or (2).
(4) the toner particles, toner according to the resin fine particles to chromatic 1.00 mass% or more with respect to the mass of the base particles (1) to (3).
Therefore, the object of the present invention can be suitably achieved.

  According to the present invention, it is possible to provide a toner having a rapid charge amount rise, a sharp charge amount distribution, less toner scattering and toner scattering during transfer, and high quality image quality. Further, by sufficiently covering the base particles with the resin fine particles of the present invention, it has become possible to achieve a high degree of low-temperature fixability while maintaining the storage stability of the toner.

It is a schematic explanatory drawing of a triboelectric charge amount measuring apparatus. It is explanatory drawing of the pattern image for micro dot reproducibility evaluation.

  The inventors of the present invention exert the above-described effect by the toner in which the resin fine particles a having the unit A represented by the following formula 1 and the resin fine particles b having the unit B represented by the following formula 2 are fixed to the surface of the mother particle. As a result, they have reached the present invention.

（Ｘは置換基を有していてもよい脂肪族基または置換基を有していてもよい芳香族基。Ｒ₁はＨ、アルカリ金属、炭素数１から４のアルキル基または芳香族基を示す。）

(X is an aliphatic group which may have a substituent or an aromatic group which may have a substituent. R ₁ is H, an alkali metal, an alkyl group having 1 to 4 carbon atoms or an aromatic group. Show.)

（Ｒ₂はＨ、炭素数１乃至４のアルキル基、アルコキシ基から選ばれる置換基を示す。）

(R ₂ represents a substituent selected from H, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group.)

  The details are not clear, but they are considered as follows. The toner of the present invention is considered to have at least resin fine particles having a power generation function and resin fine particles having a charge dissipation function fixed on the surface thereof. The power generation function is based on a resin having the structure of unit A represented by Formula 1. On the other hand, the charge dissipation function is based on a resin having the structure of unit B expressed by Formula 2. When the resin fine particles are fixed to the toner surface, it has been found that uniform shell formation can be achieved by using the two kinds of resin fine particles. Although the mechanism is not clear, it is considered that the resin particles are uniformly charged at the time of manufacture and electrostatic repulsion between the particles is difficult to occur, so that they are uniformly attached and excellent in manufacturing stability even in the fixing process. Yes. For this reason, the fixed layer of resin fine particles formed on the surface of the toner particles has the effect that the charge sites are uniformly dispersed and the adhesion is excellent, so that the charge amount rises quickly and has a sharp charge amount distribution. I believe that. That is, even if an excessive charge is generated in the process of frictional charging of the toner, the charge is diffused by the charge dissipation sites that are also present on the surface, and an appropriate surface charge is maintained. By this action, it is considered that the electrostatic cohesiveness between the toners is kept moderate, toner scattering and member contamination at the time of transfer are suppressed, and high-quality image quality excellent in fine dot reproducibility can be obtained.

  Hereinafter, preferred embodiments of the present invention will be described.

  The toner of the present invention has toner particles in which resin fine particles a and resin fine particles b mixed with mother particles serving as nuclei are fixed. It is necessary to fix the fine particles including at least the resin fine particles a and the resin fine particles b to the base particles in a range of 0.10% by mass or more. If the mass of the resin fine particles with respect to the base particles is less than 0.10% by mass, there may be a toner that is not sufficiently fixed and the charge distribution may be nonuniform. Further, when the resin mass of the resin fine particles with respect to the mother particles is fixed at 1.00% by mass or more, it is possible to achieve both low-temperature fixability and storage stability of the toner. Further, as the amount of resin fine particles increases with respect to the mother particles, uniform fixation becomes difficult, and the charge amount distribution may become non-uniform. Therefore, it is preferable that the resin fine particles including the resin fine particles a and the resin fine particles b are fixed to the base particle with an upper limit of 10.0% by mass.

  Further, the content of the unit A contained in the resin fine particles a needs to be 0.010 to 0.800 mmol / g. More preferably, it is 0.100 to 0.800 mmol / g. As a result, the occurrence of image defects due to external additive deterioration can be suppressed, and the stability of the toner can be improved. If the content of the unit A contained in the resin fine particles a is less than 0.010 mmol / g, a sufficient charge amount may not be obtained, and the effect is difficult to obtain. Further, when the content of unit A exceeds 0.800 mmol / g, the water solubility of the resin increases, and there may be a problem in toner production such as difficulty in producing resin fine particles and fixing to the toner.

  The substituent X in the unit A represented by Formula 1 is an aliphatic group or an aromatic group that may have a substituent. When the unit A is an aromatic group such as a phenylsulfonic acid unit, the charging performance of the sulfonic acid group is increased, and it is most preferable that the substituent is present at the ortho position adjacent to the amide group. The content of unit A in the toner can be detected by quantifying the amount of sulfur derived from sulfonic acid groups by elemental analysis. Therefore, the unit A content in the toner is controlled by the charged amount of the unit A-containing resin fine particles.

  On the other hand, the unit B represented by Formula 2 is a unit that mainly exhibits a charge dissipation effect. This is an aromatic unit in which at least a hydroxy group and a carboxyl group are present, and a salicylic acid structure present adjacent to each other is preferred. The other substituent is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group. The content of unit B in the toner is difficult to detect directly from the toner, but the content of unit B in the resin b can be determined by NMR, acid value, hydroxyl value measurement, or the like. The amount of unit B in the resin fine particles is preferably 0.070 to 1.000 mmol / g from the viewpoint of easy production of the resin fine particles. Therefore, the unit B content in the toner is controlled by the charged amount of the unit B-containing resin fine particles.

  The molar ratio of the content of the unit B used in the present invention to the unit A in the toner particles needs to be 0.10 or more and 10.00 or less. When the molar ratio between the unit B and the unit A is less than 0.10, the amount of the unit B having a charge dissipation mechanism is reduced, so that a sufficient charge amount can be obtained. However, it is difficult to uniformly adhere to the toner, and it is not possible to maintain proper electrostatic aggregation between the toners due to non-uniform charge distribution. Therefore, toner scattering may occur during transfer. In addition, when the molar ratio of the unit amount exceeds 10.00, the amount of unit A having the power generation mechanism is small, so that a sufficient rise in charge amount cannot be obtained.

  A known resin composition can be used for the composition of the resin fine particles a having the unit A and the resin fine particles b having the unit B. Specific examples include vinyl polymerization resins such as styrene acrylic resins, and condensation polymerization resins such as polyesters and polyethers. The content of each unit A and unit B can be controlled by a known method.

  The vinyl polymerization resin can be prepared by using those containing unit A or unit B as vinyl monomers and copolymerizing them with other vinyl monomers. At that time, it is possible to adjust the contents of unit A and unit B by the copolymerization ratio of the vinyl monomer. However, when the radical polymerization reaction rate of the monomer having the structure of unit A or unit B is greatly different from that of the other monomer, the concentration of the reaction system is reduced by dropping each monomer during the reaction. It is preferable to devise a uniform composition by adjusting the ratio.

  As the vinyl monomer having the structure of unit A, known monomers can be used, and specific examples thereof include the following. 2- (meth) acrylamide-2-methylpropanesulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid methyl, 2- (meth) acrylamide-2-methylpropanesulfonic acid ethyl, 2- (meth) acrylamide Benzene sulfonic acid, methyl 2- (meth) acrylamide benzene sulfonate, ethyl 2- (meth) acrylamide benzene sulfonate, 2- (meth) acrylamide-5-methoxybenzene sulfonic acid, 2- (meth) acrylamide-5-methoxy (Meth) acrylamide alkylsulfonic acids such as methyl benzenesulfonate, ethyl 2- (meth) acrylamide-5-methoxybenzenesulfonate and esters thereof.

  The production example of the vinyl monomer having the structure of unit A is specifically shown below.

<Monomer 4A>
Into a reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 788 g of 2-amino-5-methoxybenzenesulfonic acid, 642 g of triethylamine and 4 L of tetrahydrofuran are charged, and 352 g of methacrylic acid chloride is dropped at 15 ° C. over 15 minutes. did. The mixture was stirred for 6 hours while maintaining at 5 ° C. or lower. While maintaining the temperature at 5 ° C. or lower, 800 ml of concentrated hydrochloric acid and 12.8 L of water were added to the reaction mixture for liquid separation, and the organic layer was washed with 6.4 L of 2% hydrochloric acid and then washed with 6.4 L of water three times. . The obtained solution was concentrated under reduced pressure to obtain crystals. The obtained crystals were charged into a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, and 1680 g of trimethyl orthoformate and 1.5 g of p-benzoquinone were charged and reacted at 80 ° C. for 10 hours. The reaction mixture was cooled and concentrated under reduced pressure. The precipitated crystals were filtered, added to 5 L of water, dispersed and washed, filtered, and washed twice with 2.5 L of water. The obtained crystals were air-dried at 30 ° C. and purified by column chromatography (silica gel 5 kg, mobile phase hexane / ethyl acetate = 1/1) to obtain 383 g of monomer 4M represented by formula 3. It was.

<Monomer 4B>
Into a reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 856 g of 2-nitrobenzenesulfonyl chloride and 7 L of methanol were charged, and a mixed solution of 745 g of 28% sodium methylate and 600 ml of methanol was added dropwise at 10 ° C. or less over 45 minutes. did. Thereafter, the mixture was kept at 10 ° C. and stirred for 50 minutes. The reaction mixture was acidified by adding 1.6 kg of 0.1N hydrochloric acid, and further 3 L of water was added to precipitate crystals. The crystals were filtered, washed with 2 L of water, and then dried under reduced pressure at 30 ° C. for 10 hours to obtain 702 g of 2-nitrobenzenesulfonic acid methyl ester.

A reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube was charged with 688 g of 2-nitrobenzenesulfonic acid methyl ester, 4.7 L of acetic acid, and 2.18 kg of SnCl.H ₂ O, and cooled to 10 ° C. or lower. Under stirring, hydrochloric acid gas was blown for 4 hours. Then, it was made to stir at 10 degrees C or less for 10 hours. To the reaction mixture, 8.4 L of chloroform was added and neutralized with a 20% aqueous NaOH solution while maintaining the temperature at 10 ° C. or lower. Further, 56 L of water was added for liquid separation. The aqueous phase was extracted with 4 L of chloroform, the chloroform layers were combined, washed twice with 4 L of water, and separated. After drying over anhydrous magnesium sulfate, filtration was performed to obtain a chloroform solution of 2-aminobenzenesulfonic acid methyl ester. The obtained solution was charged into a reaction vessel equipped with a stirrer, a thermometer and a nitrogen introduction tube together with 950 g of diethylaniline, and 287 g of acrylic acid chloride was added dropwise at 5 ° C. or lower over 15 minutes. The mixture was stirred for 6 hours while maintaining at 5 ° C. or lower. The reaction mixture was separated by adding 800 ml of concentrated hydrochloric acid and 12.8 L of water, and the organic layer was divided into 6.4 L of 2% hydrochloric acid, 6.4 L of water, 6.4 L of 3% aqueous sodium hydrogen carbonate solution, and 6.4 L of water. Washed in order. The extract was dried over anhydrous magnesium sulfate, filtered, and dried under reduced pressure at 30 ° C. to obtain 796 g of crystals. This was purified by column chromatography (silica gel 5 kg, mobile phase hexane / ethyl acetate = 2/1) to obtain 406 g of monomer 4B represented by formula 4.

<Monomer 4C>
In the production of the monomer 5A, 352 g of the monomer 4C represented by the formula 5 was obtained in the same manner except that 726 g of p-toluidine-2-sulfonic acid was used instead of 2-amino-5-methoxybenzenesulfonic acid. Obtained.

<Monomer 4D>
Into a reaction vessel equipped with a stirrer, condenser, thermometer, and nitrogen introduction tube, was charged 1500 g of 2-acrylamido-2-methylpropanesulfonic acid, 2060 g of trimethylorthoformate, and 1.5 g of p-benzoquinone, and at 80 ° C. for 5 hours. Reacted. The reaction mixture was cooled and concentrated under reduced pressure. The precipitated crystals were filtered, added to 5 L of water, dispersed and washed, filtered, and washed twice with 2.5 L of water. The obtained crystals were air-dried at 30 ° C., then dispersed and washed with 4 L of hexane, and filtered. The obtained crystals were dried at 30 ° C. under reduced pressure to obtain 1063 g of monomer 4D represented by formula 6.

<Monomer 4E>
As the monomer 4E, 2-acrylamido-2-methylpropanesulfonic acid represented by the formula 7 was used.

<Monomer 4F>
As the monomer 4F, 2-methacrylamide-5-methoxybenzenesulfonic acid represented by the formula 8 was used.

<Monomer 4G>
As the monomer 4G, 2-acrylamidobenzenesulfonic acid represented by the formula 9 was used.

  In addition, esterification of a sulfonic acid group can be performed after preparing a sulfonic acid-containing resin. As a method for esterifying the sulfonic acid in the resin, 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, and a method using an orthoformate. Among them, the method using the orthoformate ester is most excellent as the esterification method of the present invention. According to this method, esterification of sulfonic acid can be easily performed by reacting an orthoformate having a desired alkyl group with a sulfonic acid-containing resin under relatively mild conditions. The rate of esterification can be easily controlled by the reaction temperature, reaction time, amount of orthoformate, and amount of solvent. Specific examples of the orthoformate ester include the following. 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.

  Moreover, in this invention, although a well-known thing can be used as a vinyl monomer which has the structure of unit B, the following can be illustrated specifically. 3-vinylsalicylic acid, 4-vinylsalicylic acid, 5-vinylsalicylic acid, 6-vinylsalicylic acid, 3-vinyl-5-isopropylsalicylic acid, 3-vinyl-5-t-butylsalicylic acid, 4-vinyl-6-t-butylsalicylic acid 3-isopropenyl-5-tert-butylsalicylic acid.

  The production example of the vinyl monomer having the structure of unit B is specifically shown below.

<Monomer 5A>
Monomer 5A represented by Formula 10 was produced using the method described in JP-A-63-270060, Journal of Polymer Science: Polymer Chemistry Edition 18, 2755 (1980).

<Monomer 5B>
Monomer 5B represented by Formula 11 was produced using the method described in JP-A No. 62-187429.

<Monomer 5C>
Monomer 5C represented by Formula 12 was produced using the method described in JP-A-63-270060, Journal of Polymer Science: Polymer Chemistry Edition 18, 2755 (1980).

<Monomer 5D>
Monomer 5D represented by Formula 13 was produced using the method described in Bioorganic & Medicinal Chemistry, 15 (15), 5207 (2007).

  On the other hand, in the case of a condensation polymerization resin, it is common to synthesize a substituent of unit A or unit B using a reactive group contained in the resin after the resin is produced. For example, when a carboxyl group is present in the resin, there is a method in which the unit is subjected to addition reaction by dehydration condensation reaction using an amine compound having unit A or B. As the compound having the unit A or B, a method of reacting with an amino group or a hydroxy group in a resin using an epoxy group addition product or an acid halide can be used. At that time, the addition amount of the units A and B can be adjusted by the introduction amount of the reactive group of each resin and the charge amount of the compound having the unit.

  A known method can be used as a method for introducing a reactive group in preparing the resin. For example, in the case of polyester, a carboxyl group or a hydroxy group present at the end of the resin may be used as it is. In order to further increase the reactive group, there is a method of leaving uncondensed carboxylic acid by using a trifunctional carboxylic acid as a polyester monomer.

  As other units constituting the resin containing the units A and B of the present invention, known units can be used. Specific examples include vinyl polymers, resins having a polyester structure, and hybrid resins in which they are combined. As the unit constituting the vinyl polymer, a known radical polymerizable monomer can be used. Specific examples include the following. Styrene such as styrene and α-methylstyrene and derivatives thereof; vinyl esters such as vinyl acetate; methyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid (Meth) acrylic acid esters such as 2-hydroxyethyl; vinyl ethers such as vinyl methyl ether; unsaturated dibasic acids such as maleic acid or anhydrides thereof.

  The following are mentioned as a polyhydric alcohol component which comprises resin containing a polyester structure. Specific examples of the dihydric alcohol component include the following. Alkylene oxide of bisphenol A such as polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane Adducts: diols such as ethylene glycol, 1,4-butanediol and neopentyl glycol.

  Examples of the trivalent or higher alcohol component include the following. 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.

  Examples of the polyvalent carboxylic acid component include the following. Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or their anhydrides; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or their anhydrides; Substituted succinic acids or anhydrides thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof.

  As a method for hybridizing the polyester resin with a vinyl monomer, a known method can be used. Specifically, a method of producing a hybrid resin by performing vinyl modification of polyester with a peroxide-based initiator or graft-modifying a polyester resin having an unsaturated group. The method of adding a radically polymerizable compound using the carboxyl group and hydroxyl group which exist in the terminal of polyester can be mentioned. As the vinyl monomer that can be used for hybridization of the polyester resin in the present invention, known monomers can be used, and the above-described vinyl monomers can be exemplified.

  Next, a method for producing mother particles that can be used in the present invention will be described below.

  A known method can be used as a means for producing the mother particles of the present invention. Specific examples include kneading and pulverizing methods, suspension polymerization methods, dissolution suspension methods, and emulsion aggregation methods. Further, in order to more appropriately express the effects of the present invention, a suspension polymerization method, a dissolution suspension method, and an emulsion aggregation method in which a toner is prepared in an aqueous medium can be mentioned. Among these, the suspension polymerization method is more preferable. .

  Below, the preparation method of the mother particle by suspension polymerization method is demonstrated concretely. A polymerizable monomer composition containing at least a polymerizable monomer, a colorant and a release agent is added to an aqueous medium, and the polymerizable monomer composition is granulated in the aqueous medium to form a polymerizable monomer. It is preferably obtained by forming particles of a monomer composition and polymerizing a polymerizable monomer contained in the particles of the polymerizable monomer composition.

  The specific production method will be explained. First, at least a colorant and a release agent are added to the polymerizable monomer that is the main constituent material of the mother particles, and a disperser such as a homogenizer, a ball mill, a colloid mill, or an ultrasonic disperser. To prepare a polymerizable monomer composition in which these are uniformly dissolved or dispersed. At this time, in the polymerizable monomer composition, a polyfunctional monomer, a chain transfer agent, a charge control agent, a plasticizer, and other additives (for example, a pigment dispersant, Release agent dispersant) can be added as appropriate. Next, the polymerizable monomer composition is put into an aqueous medium containing a dispersion stabilizer prepared in advance and suspended using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser. , Granulate. The polymerization initiator may be mixed with other additives when preparing the polymerizable monomer composition, or may be mixed into the polymerizable monomer composition just before being suspended in the aqueous medium. Good. Moreover, it can also be added in the state melt | dissolved in the polymerizable monomer or other solvent as needed during granulation or after granulation completion, ie, just before starting a polymerization reaction. In the polymerization reaction, the granulated suspension is heated to a temperature of 50 to 90 ° C., the particles of the polymerizable monomer composition in the suspension maintain the particle state, and the particles are suspended and settled. It is carried out with stirring so that it does not occur.

  The said polymerization initiator decomposes | disassembles easily by heating and produces | generates a free radical (radical). The generated radical is added to the unsaturated bond of the polymerizable monomer to newly generate an adduct radical. The generated adduct radical is further added to the unsaturated bond of the polymerizable monomer. By repeating such an addition reaction in a chained manner, the polymerization reaction proceeds, and mother particles having a binder resin derived from the polymerizable monomer as a main constituent material are formed.

  Distillation may be carried out using a known method such as reduced pressure or elevated temperature after the latter half of the polymerization reaction or after the completion of the polymerization reaction. By performing the distillation step, the remaining unreacted polymerizable monomer can be removed.

  Here, the following are mentioned as a polymerizable monomer for forming the binder resin which is the main constituent material of the mother particles.

  Styrene; Styrenic monomers such as α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene; methyl acrylate, ethyl acrylate, n-butyl acrylate, acrylic acid Acrylates such as isobutyl, n-propyl acrylate; methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate; acrylamide.

  Among these polymerizable monomers, it is preferable to use a mixture of styrene or a styrene-based monomer and another polymerizable monomer from the viewpoint of developing characteristics and durability of the toner. The mixing ratio of these polymerizable monomers may be appropriately selected in consideration of the desired glass transition temperature of the mother particles.

  The polymerization initiator used in the production of the mother particles is not particularly limited, and a known peroxide polymerization initiator or azo polymerization initiator can be used.

  Examples of peroxide polymerization initiators include the following. 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; Peroxyketals such as 1,1-di-t-hexylperoxycyclohexane; dialkyl peroxides such as di-t-butyl peroxide; other examples include t-butyl peroxyallyl monocarbonate It is below. 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.

  In the production of the mother particles, a chain transfer agent can be used for the purpose of adjusting the molecular weight. Examples of the chain transfer agent include the following. alkyl mercaptans such as n-pentyl mercaptan, isopentyl mercaptan, 2-methylbutyl mercaptan, n-hexyl mercaptan, n-heptyl mercaptan; alkyl esters of thioglycolic acid; alkyl esters of mercaptopropionic acid; α-methyl Styrene dimer.

  These chain transfer agents are not necessarily used, but a preferable addition amount when used is 0.05 to 3.00 parts by mass with respect to 100.00 parts by mass of the polymerizable monomer. is there.

  In the production of the mother particles, a small amount of a polyfunctional monomer can be used in combination for the purpose of improving the high temperature offset resistance. The high temperature offset is a phenomenon in which a part of the toner melted at the time of fixing adheres to the surface of the above-described heat roller or fixing film, which contaminates the subsequent fixing sheet. As the polyfunctional monomer, a compound having two or more polymerizable double bonds is mainly used. Aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylate esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate and 1,3-butanediol dimethacrylate; divinylaniline, divinyl ether and divinyl Divinyl compounds such as sulfide and divinyl sulfone; compounds having three or more vinyl groups. These polyfunctional monomers are not necessarily used, but the preferred addition amount when used is 0.01 parts by mass or more and 1.00 parts by mass with respect to 100.00 parts by mass of the polymerizable monomer. It is as follows.

  In the production of the mother particles, a known surfactant, organic dispersant, or inorganic dispersant can be used as a dispersion stabilizer added to the aqueous medium. Among these, inorganic dispersants can be suitably used because they are less likely to produce ultrafine powder, are less likely to lose stability even when the polymerization temperature is changed, are easy to wash and do not adversely affect the toner. Examples of such inorganic dispersants include the following. Polyvalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate and zinc phosphate; carbonates such as calcium carbonate and magnesium carbonate; inorganic salts such as calcium metasuccinate, calcium sulfate and barium sulfate; Inorganic oxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, silica, bentonite and alumina.

  When these inorganic dispersants are used, they may be used as they are in an aqueous medium, but in order to obtain finer particles, they are prepared and used in an aqueous medium using a compound capable of generating inorganic dispersant particles. You can also For example, in the case of tricalcium phosphate, sodium phosphate aqueous solution and calcium chloride aqueous solution can be mixed under high-speed stirring to produce water-insoluble tricalcium phosphate, which enables more uniform and fine dispersion. Become. These inorganic dispersants can be almost completely removed by adding an acid or an alkali after the polymerization and dissolving.

  Further, these inorganic dispersants are desirably used alone in an amount of 0.20 parts by mass or more and 20.00 parts by mass or less based on 100.00 parts by mass of the polymerizable monomer. You may use together 0.001 mass part or more and 0.100.00 mass part or less surfactant. Examples of the surfactant include the following. Sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium stearate, potassium stearate.

  In order to improve the offset resistance to the fixing device during toner fixing, it is common to apply oil to the fixing device or introduce a release agent such as wax in the toner in advance. Also in the toner of the present invention, a release agent may be contained in the toner. Examples of the release agent used in the toner of the present invention include the following. Petroleum wax such as paraffin wax, microcrystalline wax, petrolatum and derivatives thereof; montan wax and derivatives thereof; hydrocarbon wax and derivatives thereof according to Fischer-Tropsch method; polyolefin wax and derivatives thereof typified by polyethylene; carnauba wax and candelilla Natural waxes such as waxes and derivatives thereof. Derivatives include block copolymers with oxides and vinyl monomers, and graft modified products. Furthermore, higher fatty alcohols, fatty acids such as stearic acid and palmitic acid, or compounds thereof, acid amide waxes, ester waxes, ketones, plant waxes and animal waxes can also be used. Among these release agents, paraffin wax that is more easily included in the mother particles in the suspension polymerization method is particularly preferable. The amount of the release agent added is preferably 2.50 parts by mass or more and 15.00 parts by mass or less, more preferably 3.00 parts by mass or more, with respect to 100.00 parts by mass of the binder resin. The amount is more preferably 10.00 parts by mass or less. If the addition amount of the release agent is less than 2.50 parts by mass, oilless fixing becomes difficult. If the addition amount exceeds 15.00 parts by mass, the amount of the release agent in the toner is too large. A large amount exists on the surface, which may hinder desired charging characteristics, which is not preferable.

  In the mother particle of the present invention, a binder resin may be added to the polymerizable monomer composition described above. As the binder resin that can be used in the present invention, known resins can be used, and vinyl resins such as styrene-acrylic resins, polyester resins, or hybrid resins obtained by bonding them can be used. For example, the following can be exemplified. Styrene resin, (meth) acrylic resin, styrene- (meth) acrylic resin, polyethylene resin, polyethylene-vinyl acetate resin, vinyl acetate resin, polybutadiene resin, phenol resin, polyurethane resin, polybutyral resin, polyester resin, , A hybrid resin in which these resins are arbitrarily combined. Among them, a styrene resin, a (meth) acrylic resin, a styrene- (meth) acrylic resin, a polyester resin, and a hybrid resin in which a styrene- (meth) acrylic resin and a polyester resin are combined are desirably used in terms of toner characteristics.

  As the polyester resin, a polyester resin that is usually produced using a polyhydric alcohol and a carboxylic acid, a carboxylic acid anhydride, or a carboxylic acid ester as raw material monomers can be used. Specifically, the same polyhydric alcohol component and polyvalent carboxylic acid component as the above-described polyester resin can be used. Among these, polyester resins obtained by condensation polymerization of the following components are particularly preferable. The diol component is a bisphenol derivative. As the acid component, a carboxylic acid composed of a divalent or higher carboxylic acid or an acid anhydride thereof; a lower alkyl ester such as fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid component.

  On the other hand, as a hybrid resin, specifically, a polyester unit and a vinyl polymer unit obtained by polymerizing a monomer having a carboxylic acid ester group such as (meth) acrylic acid ester are combined by a transesterification reaction. Is. Preferably, a graft copolymer (or block copolymer) in which a vinyl polymer is a trunk polymer and a polyester unit is a branch polymer is used. As the vinyl monomer for producing the vinyl (co) polymer and the vinyl (co) polymer unit, the same vinyl monomers as those exemplified above can be used. .

  In the toner of the present invention, the vinyl polymer or vinyl polymer unit used for the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. In this case, examples of the crosslinking agent used include the following. Aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; di (meth) linked by alkyl chains such as ethylene glycol di (meth) acrylate, 1,6 hexanediol di (meth) acrylate and neopentylglycol di (meth) acrylate ) Acrylate compounds; di (meth) acrylate compounds linked by an alkyl chain containing an ether bond such as diethylene glycol di (meth) acrylate and polyethylene glycol # 400 di (meth) acrylate; polyoxyethylene (2) -2, In a chain containing an aromatic group and an ether bond such as 2-bis (4-hydroxyphenyl) propane di (meth) acrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane di (meth) acrylate Tied di Meth) acrylate compounds. The following can be illustrated as a polyfunctional crosslinking agent. Pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, oligoester (meth) acrylate, triallyl cyanurate, triallyl trimellitate.

The toner of the present invention may be either magnetic toner or non-magnetic toner. When used as a magnetic toner, a magnetic material is used as the colorant, and the following magnetic materials are preferably used. Iron oxide including magnetite, maghemite, ferrite, or other metal oxides; metals such as Fe, Co, Ni, or these metals and Al, Co, Cu, Pb, Mg, Ni, Sn, Alloys with metals such as Zn, Sb, Ca, Mn, Se, Ti, and mixtures thereof. Iron trioxide (Fe ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), iron oxide zinc (ZnFe ₂ O ₄ ), copper iron oxide (CuFe ₂ O ₄ ), iron oxide neodymium (NdFe ₂ O) ₃ ), iron barium oxide (BaFe ₁₂ O ₁₉ ), iron magnesium oxide (MgFe ₂ O ₄ ), iron manganese oxide (MnFe ₂ O ₄ ). The magnetic materials described above are used alone or in combination of two or more. A magnetic material particularly suitable for the purposes of the present invention is a fine powder of iron trioxide or γ-iron trioxide.

These magnetic materials have an average particle size of 0.1 μm or more and 2 μm or less, preferably 0.1 μm or more and 0.3 μm. The magnetic characteristics when 795.8 kA / m (10 K Oersted) is applied are as follows: the coercive force (Hc) is 1.6 kA / m to 12 kA / m (20 Oersted to 150 Oersted), and the saturation magnetization (σr) is 5 Am ² / kg. It is 200 Am < ² > / kg or less, preferably 50 Am < ² > / kg or more and 100 Am < ² > / kg or less. Residual magnetization (.sigma.r) is, 2Am ² / kg or more 20 Am ² / kg or less being preferred.

  The magnetic material may be used in an amount of 10 to 200 parts by mass, preferably 20 to 150 parts by mass with respect to 100 parts by mass of the binder resin.

  On the other hand, as a colorant for use as a non-magnetic toner, a known colorant such as various conventionally known dyes and pigments can be used.

  For example, as magenta coloring pigments, for example, C.I. I. Pigment red 3, 5, 17, 22, 23, 38, 41, 112, 122, 123, 146, 149, 178, 179, 190, 202, C.I. I. Pigment Violet 19, 23. Such a pigment may be used alone, or a dye and a pigment may be used in combination.

  Examples of the color pigment for cyan include C.I. I. Pigment Blue 15, 15: 1, 15: 3 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.

  Examples of the color pigment for yellow include C.I. I. Pigment yellow 1, 3, 12, 13, 14, 55, 73, 74, 83, 93, 94, 95, 97, 98, 109, 110, 154, 155, 166, 180, 185.

  As the black colorant, for example, carbon black, aniline black, acetylene black, titanium black, and those that are toned in black using the yellow / magenta / cyan colorant described above can be used.

  In addition, although the usage-amount of a coloring agent changes with kinds of coloring agent, it is 0.10 mass part or more and 60.00 mass part or less in total with respect to 100.00 mass part of binder resin, Preferably it is 0.50 mass part. The amount of 50.00 parts by mass or less is appropriate.

  In the toner of the present invention, an organometallic compound may be used in combination with the resin of the present invention. For example, the metal compound of the aromatic oxycarboxylic acid derivative shown below is mentioned.

M ₂ in the above formula is a divalent metal atom, and Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Pb ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Zn ²⁺ , Cu ²⁺ Is mentioned. M ₃ is a trivalent metal atom, and examples thereof include Al ³⁺ , Cr ³⁺ , Fe ³⁺ , and Ni ³⁺ . M ₄ is a tetravalent metal atom, and examples thereof include Zr ⁴⁺ , Hf ⁴⁺ , Mn ⁴⁺ , and Co ⁴⁺ . Among these metal atoms, Al ³⁺ , Fe ³⁺ , Cr ³⁺ , Zr ⁴⁺ , Hf ⁴⁺ and Zn ²⁺ are ^preferable .

In the formula, R ₁ to R ₄ represent the same or different groups, and are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, —OH, —NH ₂ , —NH ( _{CH 3), - N (CH} 3) 2, -OCH 3, -O (C 2 H 5), - shows a COOH or -CONH _2. Preferable R ₁ includes a hydroxyl group, an amino group, and a methoxy group, and among them, a hydroxyl group is preferable.

  In the kneading and pulverizing method, the binder resin, the colorant and / or the magnetic material, and other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill. Mother particles can be produced by melt-kneading using a heat kneader such as a kneader or extruder, cooling and solidifying the kneaded product, pulverizing the solidified product, and classifying the pulverized product.

  In the dissolution suspension method, mother particles can be prepared by dissolving or dispersing together with necessary components in an organic solvent, suspending and granulating in an aqueous medium, and then removing the organic solvent contained in the droplets. .

  In the emulsion aggregation method, fine particles of necessary components are mixed, and the toner particles are aggregated in an aqueous medium by controlling their zeta potential to produce mother particles.

  In the present invention, a known method can be used as a method for producing the resin fine particles a or the resin fine particles b.

  For example, when the unit A is specifically used, the following method may be mentioned. Examples include a method of synthesizing a resin containing the unit A having a sulfonic acid-based substituent and emulsifying it in an aqueous medium to obtain fine particles. By producing fine particles in an aqueous medium, uniform fine particles having a small particle size and a narrow particle size distribution can be obtained, which is a preferred embodiment. The resin fine particles b are the same as the resin fine particles a except that the unit B having a salicylic acid-based substituent is used.

  The method for preparing the resin fine particles is not particularly limited, and is prepared by emulsion polymerization or liquefaction by dissolving or melting the resin in a solvent and suspending or phase inversion emulsification in an aqueous medium. A method is mentioned. At this time, known surfactants and dispersants can be used, and the resin forming the resin fine particles can be made self-emulsifying.

  The solvent that can be used when preparing the fine particles by dissolving the resin in a solvent is not particularly limited.

  Hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as methylene chloride, chloroform and dichloroethane; ester solvents such as methyl acetate, ethyl acetate, butyl acetate and isopropyl acetate; ether solvents such as diethyl ether; Ketone solvents such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexane; alcohol solvents such as methanol, ethanol and butanol.

  The polymerizable monomer that can be used when the resin fine particles a are produced by an emulsion polymerization method may be an addition polymerization monomer that generates a unit A having a sulfonic acid substituent represented by Formula 1. That's fine. Specifically, the following monomers are mentioned. 2-acrylamido-2-methylpropanesulfonic acid methyl ester, 2-acrylamido-phenylsulfonic acid methyl ester, 2-acrylamido-5-methoxyphenylsulfonic acid methyl ester, 2-methacrylamido-5-methoxyphenylsulfonic acid ethyl ester, 2-Methacrylamide-naphthylsulfonic acid methyl ester.

  The vinyl polymer that forms the resin fine particles is preferably formed by copolymerizing a monomer that generates the unit A having a sulfonic acid-based substituent represented by Formula 1 and other monomers. As the monomer to be copolymerized, the same monomers as those described above and enumerated can be used.

  In the present invention, known methods can be used as the method for fixing the resin fine particles to the mother particles. For example, there is a method of applying mechanical stress by mixing mother particles and fine particles including at least resin fine particles a and resin fine particles b. Further, there is a method in which fine particles containing at least resin fine particles a and resin fine particles b are added and fixed in an aqueous medium containing mother particles. At that time, a strong fixing state can be obtained by controlling the temperature, pH, time, and changing the conditions for adding the electrolyte flocculant as necessary.

  In the present invention, the following configuration is important in order to fix the fine particles having at least the resin fine particles a and the resin fine particles b uniformly and firmly on the surface of the mother particles.

  That is, in order to obtain the toner surface fixing uniformity, the resin fine particle diameter is preferably 10 to 150 nm. A method for measuring the particle diameter of the resin fine particles will be described later. The smaller the resin fine particle a particle diameter, the easier it is to obtain film uniformity. However, if the particle diameter is less than 10 nm, the composition distribution tends to occur in individual fine particles, and there is a concern about variation in the unit amount of unit A or unit B contained in the fine particles. In the fixing step of the mother particles, the yield may be lowered, which is not preferable. When the particle diameter is larger than 150 nm, the toner surface after fixing may be uneven, and image characteristics may be deteriorated due to the release of these fine particles. The particle diameter is preferably 30 to 120 nm, more preferably 40 to 80 nm.

  The particle diameter of the resin fine particles a or the resin fine particles b can satisfy the above range by adjusting the granulation conditions at the time of producing the fine particles. Specifically, the solid-liquid ratio in the aqueous medium, the pH of the aqueous medium, the stirring speed, and the like can be mentioned.

The produced toner particles can be further mixed with the fluidity improver and the toner particles by a mixing machine such as a Henschel mixer to obtain a toner having the fluidity improver on the surface of the toner particles. As the fluidity improver, the fluidity can be increased by adding the toner particles externally before and after the addition. For example, fluororesin powder such as vinylidene fluoride fine powder, polytetrafluoroethylene fine powder; silica fine powder by wet production method, silica fine powder such as silica fine powder by dry production method, these silica fine powders as silane coupling agent, Examples thereof include a treated silica fine powder subjected to a surface treatment with a treating agent such as a titanium coupling agent and silicone oil; a titanium oxide fine powder; an alumina fine powder, a treated titanium oxide fine powder, and a treated alumina oxide fine powder. A fluidity improver having a specific surface area of 30 m ² / g or more, preferably 50 m ² / g or more, gives good results by nitrogen adsorption measured by the BET method. The fluidity improver is used in an amount of 0.01 to 8.0 parts by weight, preferably 0.1 to 4.0 parts by weight, based on 100 parts by weight of the toner particles.

  In the present invention, the weight average particle diameter (D4) of the toner is 3.0 μm or more and 10.0 μm or less, preferably 4.0 μm or more and 9.0 μm or less. When the weight average particle diameter (D4) of the toner is less than 3.0 μm, it becomes difficult to achieve charging stabilization when applied to an electrophotographic development system, and fogging occurs in continuous development operation (endurance operation) of a large number of sheets. And toner scattering is likely to occur. When the weight average particle diameter (D4) of the toner exceeds 10.0 μm, the reproducibility of the halftone portion is greatly lowered, and the obtained image becomes a gritty image, which is not preferable.

  The measurement method used in the present invention will be described below.

<Molecular weight of resin>
The molecular weight and molecular weight distribution of the charge control resin of the present invention are calculated in terms of polystyrene by gel permeation chromatography (GPC). Among the resins of the present invention, those containing a sulfonic acid group cannot accurately measure the molecular weight and molecular weight distribution because the column elution rate depends on the amount of the sulfonic acid group. Therefore, it is necessary to prepare a material in which the sulfonic acid group is capped beforehand. Methyl esterification is preferable for capping, and a commercially available methyl esterifying agent can be used. Specifically, a method of treating with trimethylsilyldiazomethane can be mentioned.

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

The resin was added to THF (tetrahydrofuran) and allowed to stand at room temperature for 24 hours. The solution was filtered through a solvent-resistant membrane filter “Mysholy disk” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. Measure under the following conditions. In addition, sample preparation adjusts the quantity of THF so that the density | concentration of resin may be about 0.8 mass%. If the resin does not dissolve or is difficult to dissolve in THF, a basic solvent such as DMF (N, N-dimethylformamide) can be used.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran or DMF when resin is difficult to dissolve 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, a molecular weight calibration curve prepared using a standard polystyrene resin column listed below is used. Specifically, for example, Tosoh Corporation 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 ".

<Resin acid value>
The acid value of the resin in the present invention is determined by the following method.

  The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value of the binder resin is measured according to JIS K 0070-1966. Specifically, it is measured according to the following procedure.

(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95 vol%), and ion 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 to avoid contact with carbon dioxide, etc., it is placed in an alkali-resistant container and allowed to stand for 3 days, followed by filtration to obtain a “potassium hydroxide solution”. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The orientation is performed according to JIS K 0070-1996.

(2) Operation (A) Main test 2.0 g of the pulverized binder resin sample is precisely weighed into a 200 ml Erlenmeyer flask, and 100 ml of a mixed solution of toluene / ethanol (2: 1) is added and dissolved over 5 hours. . Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of the titration is when the light red color of the indicator lasts for 30 seconds.
(B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).

(3) The acid value is calculated by substituting the obtained result into the following formula.
A = [(BC) × 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).

<Composition analysis>
The structure of the produced resin was determined using the following apparatus.
[FT-IR spectrum]
NICOLET AVATAR360FT-IR
[ 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)

<Resin fine particle diameter measurement method>
The particle size of the present invention was measured under the following measurement conditions using a Zetasizer Nano-ZS (manufactured by MALVERN).

<Measurement conditions>
Cell: quartz glass cell Dispersant: Water (Dispersant RI: 1.330)
・ Temperature: 25 ° C
・ Material RI: 1.60
・ Result Calculation: General Purpose
The sample was prepared by diluting an aqueous dispersion of resin fine particles to be measured so that the solid-liquid ratio was 0.20 to 0.30% by mass.

<Measuring method of weight average particle diameter (D4) and number average particle diameter (D1) of toner>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are 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 is performed with 25,000 effective measurement channels.

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

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

  On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.

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

The specific measurement method is as follows.
(1) In a glass 250 ml round bottom beaker for exclusive use of Multisizer 3, 200 ml of the electrolytic aqueous solution is placed and set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) Put 30 ml of the aqueous electrolytic solution into 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.
(3) An ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikkaki Bios Co., Ltd.) having an electrical output of 120 W is prepared by incorporating two oscillators having an oscillation frequency of 50 kHz with the phases shifted by 180 degrees. Into the water tank of the ultrasonic disperser, 3.3 l of ion-exchanged water is added, and 2 ml of Contaminone N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker (1) installed in the sample stand, the electrolyte aqueous solution (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to 5%. Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) 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 the number% is set, the “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).

<Measurement of triboelectric charge amount of toner (two-component method)>
For the measurement of the amount of charge, 50 g of each developer was collected, left in a room temperature and normal humidity environment (23 ° C./60%) for 3 days and nights, then placed in a 50 cc plastic container and shaken 200 times over 1 minute. Measurement was performed using the apparatus shown in FIG. 0.5 g of a two-component developer whose frictional charge is to be measured is placed in a metal measuring container 2 having a 500 mesh screen 3 at the bottom, and a metal lid 4 is formed. At this time, the mass of the entire measurement container 2 is weighed and is defined as W1 (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, suction is sufficiently performed, preferably for 2 minutes, and the toner is removed by suction. 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 (μC / g) of the toner is calculated as follows.
Triboelectric charge (μC / g) = (C × V) / (W1−W2)

  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.

  PA resins 1 to 10 and PB resins 1 to 5 were synthesized by the following method.

[Synthesis Example 1 of PA resin]
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of xylene was charged and refluxed under a nitrogen stream.

next,
・ Methyl 2-methacrylamide-5-methoxybenzenesulfonate 17.0 parts ・ 67.0 parts of styrene ・ 16.0 parts of 2-ethylhexyl acrylate ・ Dimethyl-2,2′-azobis (2-methylpropionate) 5 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 40 ° C. under reduced pressure to obtain Resin PA-1.

  The obtained resin PA-1 was micronized by the following procedure to prepare a dispersion of resin microparticles a.

  In a 1 L tall beaker, 100 parts of THF was added, and 60 parts of resin PA-1 was gradually added and dissolved while stirring. Thereto was added 1.50 parts of dimethylaminoethanol and mixed well. While continuing gentle stirring, 180 parts of distilled water was added dropwise over 30 minutes, and then THF was distilled off with an evaporator to obtain a fine particle dispersion of PA-1. As a result of quantitative determination of sulfur atoms by elemental analysis, the obtained resin PA-1 was confirmed to contain unit A derived from 0.583 mmol / g sulfonic acid. The particle diameter was 67 nm. Table 1 summarizes the physical properties of the resin fine particles a.

[Synthesis Example 2 of PA resin]
Resin PA was synthesized in the same manner as in Synthesis Example 1 except that the following materials were used to obtain Resin PA-2.
2 methyl methyl 2-methacrylamide-5-methoxybenzenesulfonate 63.0 parts styrene 15.0 parts 2-ethylhexyl acrylate dimethyl-2,2′-azobis (2-methylpropionate) 5 .0 part

  As a result of quantitative determination of sulfur atoms by elemental analysis, the obtained resin PA-2 was confirmed to contain unit A derived from 0.751 mmol / g sulfonic acid. The particle diameter was 71 nm.

[Synthesis Example 3 of PA resin]
Resin PA was synthesized in the same manner as in Synthesis Example 1 except that the following materials were used to obtain Resin PA-3.
・ 2-Acrylamido-2-methylpropanesulfonic acid 10.0 parts ・ Styrene 74.0 parts ・ 2-Ethylhexyl acrylate 16.0 parts ・ Dimethyl-2,2′-azobis (2-methylpropionate) 5.0 Part

  As a result of quantitative determination of sulfur atoms by elemental analysis, the obtained resin PA-3 was confirmed to contain unit A derived from 0.472 mmol / g sulfonic acid. The particle diameter was 64 nm.

[Synthesis Example 4 of PA resin]
Resin PA was synthesized in the same manner as in Synthesis Example 1 except that the following materials were used to obtain Resin PA-4.
・ 2-acrylamido-2-methylpropanesulfonic acid 16.0 parts ・ styrene 69.0 parts ・ 2-ethylhexyl acrylate 15.0 parts ・ dimethyl-2,2′-azobis (2-methylpropionate) 5.0 Part

  As a result of quantitative determination of sulfur atoms by elemental analysis, the obtained resin PA-4 was confirmed to contain unit A derived from 0.763 mmol / g sulfonic acid. The particle diameter was 77 nm.

[Synthesis Example 5 of PA resin]
Resin PA was synthesized in the same manner as in Synthesis Example 1 except that the following materials were used to obtain Resin PA-5.
・ Methyl 2-acrylamido-2-methylpropanesulfonate 10.0 parts ・ Styrene 74.0 parts ・ 2-ethylhexyl acrylate 16.0 parts ・ Dimethyl-2,2′-azobis (2-methylpropionate) 5. 0 copies

  As a result of quantitative determination of sulfur atoms by elemental analysis, the obtained resin PA-5 was confirmed to contain unit A derived from 0.447 mmol / g sulfonic acid. The particle diameter was 71 nm.

[Synthesis Example 6 of PA resin]
Resin PA was synthesized in the same manner as in Synthesis Example 1 except that the following materials were used to obtain Resin PA-6.
• 2-methacrylamide-5-methoxybenzenesulfonic acid 15.0 parts • Styrene 70.0 parts • 2-ethylhexyl acrylate 15.0 parts • Dimethyl-2,2′-azobis (2-methylpropionate) 0 copies

  As a result of quantitative determination of sulfur atoms by elemental analysis, the obtained resin PA-6 was confirmed to contain unit A derived from 0.539 mmol / g sulfonic acid. The particle diameter was 63 nm.

[Synthesis Example 7 of PA resin]
Resin PA was synthesized in the same manner as in Synthesis Example 1 except that the following materials were used to obtain Resin PA-7.
・ Methyl 2-methacrylamide-5-methoxybenzenesulfonate 15.0 parts ・ Styrene 75.0 parts ・ N-butyl acrylate 10.0 parts ・ Dimethyl-2,2′-azobis (2-methylpropionate) 5 .0 part

  As a result of quantitative determination of sulfur atoms by elemental analysis, the obtained resin PA-7 was confirmed to contain unit A derived from 0.495 mmol / g sulfonic acid. The particle diameter was 69 nm.

[Synthesis Example 8 of PA resin]
Preparation of polyester P-1:
・ Add 67.8 parts of bisphenol A, 2.2 mol of propylene oxide, 23.2 parts of terephthalic acid, 9.0 parts of trimellitic anhydride, 0.005 part of dibutyltin oxide in a four-necked flask, and add a thermometer. The polyester resin P-1 was obtained by attaching a stirring bar, a condenser, and a nitrogen introduction tube and reacting at 220 ° C. for 5 hours in a nitrogen atmosphere.

Next, 80 parts of polyester resin P-1 and 11 parts of 4-aminobenzenesulfonic acid were placed in a reaction vessel equipped with a cooling pipe, a stirrer, a thermometer and a nitrogen introduction pipe, and 270 parts of pyridine were added and stirred. Thereafter, 96 parts of triphenyl phosphite was added, and the mixture was heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 360 parts of ethanol. The polymer obtained was washed twice with 140 parts of 1N hydrochloric acid, then washed twice with 140 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, the peak derived from the aromatic ring of 4-aminobenzenesulfonic acid was shifted. As a result of quantitative determination of sulfur atoms by elemental analysis, it was confirmed that the obtained resin PA-8 contained unit A derived from 0.526 mmol / g sulfonic acid. The particle diameter was 76 nm.

[Synthesis Example 9 of PA resin]
Preparation of polyester P-2:
・ Bisphenol A ・ Propylene oxide 2.2 mol adduct 70.0 parts ・ Terephthalic acid 28.0 parts ・ Fumaric acid 3.0 parts ・ Dibutyltin oxide 0.005 parts are put into a four-necked flask, thermometer, stirring A polyester resin P-2 was obtained by attaching a rod, a condenser, and a nitrogen introducing tube and reacting at 220 ° C. for 5 hours in a nitrogen atmosphere.

  In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of xylene was charged and refluxed under a nitrogen stream. Thereto, 70 parts of the previously produced resin P-2 was added and dissolved.

next,
・ Methyl 2-methacrylamide-5-methoxybenzenesulfonate 15.0 parts ・ 13.5 parts of styrene ・ 1.5 parts of dimethyl-2,2′-azobis (2-methylpropionate) The mixture was added dropwise to the container with stirring and held for 10 hours. Thereafter, distillation was performed to distill off the solvent, followed by drying at 40 ° C. under reduced pressure to obtain Resin PA-9.

  As a result of quantitative determination of sulfur atoms by elemental analysis, the obtained resin PA-9 was confirmed to contain unit A derived from 0.475 mmol / g sulfonic acid. The particle diameter was 86 nm.

[Synthesis Example 10 of PA resin]
Resin PA was synthesized in the same manner as in Synthesis Example 1 except that the following materials were used to obtain Resin PA-10.
-0.09 part 2-acrylamido-2-methylpropanesulfonic acid-83.9 parts styrene-16.0 parts 2-ethylhexyl acrylate-Dimethyl-2,2'-azobis (2-methylpropionate) 5.0 Part

  As a result of quantitative determination of sulfur atoms by elemental analysis, the obtained resin PA-10 was confirmed to contain unit A derived from 0.004 mmol / g sulfonic acid. The particle diameter was 89 nm.

[Synthesis Example 11 of PA resin]
Resin PA was synthesized in the same manner as in Synthesis Example 1 except that the following materials were used to obtain Resin PA-11.
-2-acrylamido-2-methylpropanesulfonic acid 20.0 parts-Styrene 65.0 parts-2-ethylhexyl acrylate 15.0 parts-Dimethyl-2,2'-azobis (2-methylpropionate) 5.0 Part

  As a result of quantitative determination of sulfur atoms by elemental analysis, the obtained resin PA-11 was confirmed to contain unit A derived from 0.943 mmol / g sulfonic acid. The particle diameter was 64 nm.

[Synthesis Example 12 of PA resin]
Resin PA was synthesized in the same manner as in Synthesis Example 1 except that the following materials were used to obtain Resin PA-12.
・ Methyl 2-methacrylamide-5-methoxybenzenesulfonate 3.0 parts ・ Styrene 82.0 parts ・ 2-ethylhexyl acrylate 15.0 parts ・ Dimethyl-2,2′-azobis (2-methylpropionate) 5 .0 part

  As a result of quantitative determination of sulfur atoms by elemental analysis, it was confirmed that the obtained resin PA-12 contained unit A derived from 0.105 mmol / g sulfonic acid. The particle diameter was 73 nm.

[Synthesis Example 13 of PA resin]
Resin PA was synthesized in the same manner as in Synthesis Example 1 except that the following materials were used to obtain Resin PA-13.
-2-acrylamido-2-methylpropanesulfonic acid 3.0 parts-Styrene 82.0 parts-2-ethylhexyl acrylate 15.0 parts-Dimethyl-2,2'-azobis (2-methylpropionate) 5.0 Part

  As a result of quantitative determination of sulfur atoms by elemental analysis, the obtained resin PA-13 was confirmed to contain unit A derived from 0.145 mmol / g sulfonic acid. The particle diameter was 75 nm.

[Synthesis Example 14 of PA resin]
Resin PA was synthesized in the same manner as in Synthesis Example 1 except that the following materials were used to obtain Resin PA-14.
-0.1 part of 2-acrylamido-2-methylpropanesulfonic acid-82.6 parts of styrene-16.0 parts of 2-ethylhexyl acrylate-dimethyl-2,2'-azobis (2-methylpropionate) 5.0 Part

  As a result of quantitative determination of sulfur atoms by elemental analysis, the obtained resin PA-14 was confirmed to contain unit A derived from 0.014 mmol / g sulfonic acid. The particle diameter was 68 nm.

[Synthesis Example 1 of PB resin]
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of xylene was charged and refluxed under a nitrogen stream.

next,
-10.0 parts of 5-vinyl salicylic acid-75.0 parts of styrene-15.0 parts of 2-ethylhexyl acrylate-5.0 parts of dimethyl-2,2'-azobis (2-methylpropionate) The reaction vessel was added dropwise with stirring and held for 10 hours. Thereafter, distillation was performed to distill off the solvent, followed by drying at 40 ° C. under reduced pressure to obtain Resin PB-1.

  As a result of acid value measurement, the obtained resin PB-1 was confirmed to contain unit B derived from 0.572 mmol / g of salicylic acid. The particle diameter was 65 nm. The physical properties of the resin are summarized in Table 1.

[Synthesis example 2 of PB resin]
Resin PB was synthesized in the same manner as in Synthesis Example 1 except that the following materials were used to obtain Resin PB-2.
3-tert-butyl-5-vinylsalicylic acid 13.0 parts styrene 72.0 parts 2-ethylhexyl acrylate 15.0 parts dimethyl-2,2'-azobis (2-methylpropionate) 5.0 Part

  As a result of acid value measurement, the obtained resin PB-2 was confirmed to contain unit B derived from 0.580 mmol / g of salicylic acid. The particle diameter was 62 nm.

[Synthesis example 3 of PB resin]
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer and a nitrogen introduction tube, 88 parts of polyester resin P-1 and 10 parts of 4-aminosalicylic acid were added, and 270 parts of pyridine were added and stirred. 96 parts of triphenyl acid was added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 360 parts of ethanol. The polymer obtained was washed twice with 140 parts of 1N hydrochloric acid, then washed twice with 140 parts of water and dried under reduced pressure. As a result of acid value measurement, the obtained resin PB-3 was confirmed to contain unit B derived from 0.639 mmol / g of salicylic acid. The particle diameter was 73 nm.

[Synthesis example 4 of PB resin]
Preparation of polyester P-3:
・ Bisphenol A ・ Propylene oxide 2.2 mol adduct 70.0 parts ・ Terephthalic acid 26.0 parts ・ Fumaric acid 4.0 parts ・ Dibutyltin oxide 0.005 parts are put into a four-necked flask, thermometer, stirring A polyester resin P-3 was obtained by attaching a rod, a condenser, and a nitrogen introducing tube and reacting at 220 ° C. for 5 hours in a nitrogen atmosphere.

  In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of xylene was charged and refluxed under a nitrogen stream. Thereto, 70 parts of the previously prepared resin P-3 was added and dissolved.

next,
-8.1 parts of 5-vinyl salicylic acid-18.9 parts of styrene-3.0 parts of n-butyl acrylate-1.5 parts of dimethyl-2,2'-azobis (2-methylpropionate) The reaction vessel was added dropwise with stirring and held for 10 hours. Thereafter, distillation was performed to distill off the solvent, followed by drying at 40 ° C. under reduced pressure to obtain Resin PB-4.

  As a result of acid value measurement, the obtained resin PB-4 was confirmed to contain unit B derived from 0.482 mmol / g of salicylic acid. The particle diameter was 79 nm.

[Synthesis example 5 of PB resin]
Resin PB was synthesized in the same manner as in Synthesis Example 1 except that the following materials were used to obtain Resin PB-5.
-1.25 parts of 5-vinyl salicylic acid-83.8 parts of styrene-15.0 parts of 2-ethylhexyl acrylate-5.0 parts of dimethyl-2,2'-azobis (2-methylpropionate)

  As a result of acid value measurement, the obtained resin PB-5 was confirmed to contain unit B derived from 0.059 mmol / g of salicylic acid. The particle diameter was 61 nm.

  Subsequently, toners A to Z of the present invention were produced by the following method.

[Example 1]
Preparation of pigment dispersion paste:
・ Styrene monomer 80.0 parts ・ Cu phthalocyanine (Pigment Blue 15: 3) 13.0 parts After premixing the above materials well in a container, the mixture was dispersed in a bead mill for 4 hours while keeping it at 20 ° C. or less, and pigment. A dispersion paste was prepared.

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 stirred at 13,000 rpm using Creamix (M Technique). . 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 13 mg KOH / g, Mw 14500)
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 13000 rpm for 15 minutes using Claremix 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.

  Subsequently, 2.5 parts of PA-1 resin fine particle dispersion and 2 parts of PB-1 resin fine particle dispersion were used as solids with respect to 100 parts of the obtained mother particle dispersion and solids of 2 parts. Add 7 parts slowly. Thereto was added dropwise 0.1M hydrochloric acid while taking care that the pH in the system gradually changed, and the pH was adjusted to 1.5. Furthermore, the internal temperature was raised to 62 ° C. with a heating oil bath and held for 2 hours. The obtained dispersion was filtered, washed with water, and dried to obtain toner particles.

The obtained toner particles are classified, and the toner is obtained by externally adding hydrophobic silica by the following operation. That is, after treating the surface with hexamethyldisilazane, 1.0 part of hydrophobic silica fine powder 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 was added to 100 parts of toner particles and Henschel. Mix and externally add with a mixer (Mitsui Miike Chemical Co., Ltd.). The obtained toner A had a weight average particle diameter (D4) of 6.8 μm. Hereinafter, physical properties of the obtained toner are shown in Table 2.

  The toner A produced as described above was evaluated by the following evaluation methods and evaluation criteria. The results are shown in Table 3.

<Evaluation of toner scattering>
A two-component developer for toner to be evaluated is put in a developing device and set in an idle rotator. Place A4 paper around the sleeve of the developing unit, rotate it for 3 minutes, and evaluate the scattering state of the toner falling on the paper with an optical microscope (VHX-200 KEYENC) according to the following conditions. It was. At a magnification of 500 times, 10 fields of an area of 100 μm square were observed arbitrarily, the number of toners in the area was counted, and an average value per 100 μm square was evaluated.
(Evaluation criteria)
A: 0.0 or more and less than 2.0 B: 2.0 or more and less than 5.0 C: 5.0 or more and less than 10.0 D: 10.0 or more

<Reproducibility of minute dots>
Image quality evaluation was performed with a color copier CLC5500 (manufactured by Canon) in a normal temperature and humidity environment (23 ° C./60%) using the developing unit used for toner scattering evaluation. In order to evaluate the image quality at this time, an image of an isolated dot pattern having a small diameter (45 μm) as shown in FIG. 2 was printed out, and the dot reproducibility was evaluated. .
(Evaluation criteria)
A: 2 or less defects / 100 B: 3 to 5 defects / 100 defects C: 6 to 10 defects / 100 defects D: 11 defects or more / 100 defects

<Evaluation of rising of triboelectric charge>
450g of each two-component developer is allowed to stand for 7 days under high temperature and high humidity (30 ℃ / 80%), and then left for another 3 days under normal temperature and humidity (23 ℃ / 60%) to reset the triboelectric charge due to initial mixing. did. The images were evaluated in a normal temperature and humidity environment (23 ° C./60%) with a color copier CLC5500 modified (manufactured by Canon). The CLC5500 increased the process speed to the normal 135%. Each developer was charged into the developing unit, 50 solid A4 images were output without preliminary rotation, and the reflectance of the solid white portion of the image was measured. Further, the reflectance of the unused paper was measured and subtracted from the reflectance of the solid white portion of the image to obtain the fog density. The reflectance was measured with TC-6DS (manufactured by Tokyo Denshoku).
(Evaluation criteria)
A: Within 10 sheets, fog density is less than 1.0% B: 11 to 20 sheets, fog density is less than 1.0% C: 21 to 30 sheets, fog density is less than 1.0% D: 31 The fog density is 1.0% or more on the sheet.

<Storage stability evaluation>
10 g of toner is weighed into a 100 ml capacity polycup and placed in a thermostatic chamber with an internal temperature of 50 ° C. and a room adjusted to 25 ° C. and left for 7 days. Thereafter, the fluidity of the toner when the polycup was gently taken out and rotated slowly was compared between the toner left at 50 ° C. and the toner left at 25 ° C., and evaluated visually. Judgment criteria are as follows.
(Evaluation criteria)
A: The fluidity of the toner left at 50 ° C. is equivalent to that of the toner left at 25 ° C.
B: Although the fluidity of the toner standing at 50 ° C. is slightly inferior to that of the toner standing at 25 ° C., the fluidity gradually recovers as the polycup rotates.
C: The toner left standing at 50 ° C. shows agglomerated and fused lump.
D: Toner left at 50 ° C. does not flow

  When the toner was evaluated based on the evaluation methods and criteria as described above, the toner A of this example was excellent in charge rising characteristics, and was ranked A in terms of toner scattering. In addition, the image also reproduced fine dots well and was ranked A. Furthermore, regarding the storage stability, the evaluation was A rank. All the evaluation results are shown in Table 3.

[Example 2]
The toner is the same as in Example 1 except that the resin PA-1 is 0.80 part (solid content) and the resin PB-1 is 0.90 part (solid content) of the fixed amount of the resin fine particle dispersion to be fixed. The toner B was produced.

Example 3
The toner is the same as in Example 1 except that the resin PA-1 is 1.50 parts (solid content) and the resin PB-1 is 0.50 parts (solid content) of the fixed amount of the resin fine particle dispersion to be fixed. The toner C was produced.

Example 4
The toner is the same as in Example 1 except that the resin PA-1 is 0.50 part (solid content) and the resin PB-1 is 4.00 part (solid content) out of the fixed amount of the resin fine particle dispersion to be fixed. The toner D was produced.

Example 5
The toner was prepared in the same manner as in Example 1 except that the resin PA-12 was 3.00 parts (solid content) and the resin PB-1 was 2.00 parts (solid content) of the fixed amount of the resin fine particle dispersion to be fixed. The toner E was produced.

Example 6
The toner is the same as in Example 1 except that the resin PA-2 is 2.50 parts (solid content) and the resin PB-1 is 3.50 parts (solid content) of the fixed amount of the resin fine particle dispersion to be fixed. The toner F was produced.

[ Reference Example 7]
The toner is the same as in Example 1 except that the resin PA-14 is 6.00 parts (solid content) and the resin PB-1 is 0.50 parts (solid content) of the fixed amount of the resin fine particle dispersion to be fixed. The toner G was produced.

Example 8
The toner is the same as in Example 1 except that the resin PA-1 is 0.60 part (solid content) and the resin PB-1 is 0.50 part (solid content) of the fixed amount of the resin fine particle dispersion to be fixed. The toner H was produced.

Example 9
The toner was prepared in the same manner as in Example 1 except that the amount of resin fine particle dispersion to be fixed was 2.50 parts (solid content) of resin PA-3 and 2.50 parts (solid content) of resin PB-1. The toner I was produced.

Example 10
In the same manner as in Example 1 except that the resin PA-3 is 3.50 parts (solid content) and the resin PB-1 is 1.00 parts (solid content) of the fixed amount of the resin fine particle dispersion to be fixed. The toner J was produced.

Example 11
In the same manner as in Example 1, except that the resin PA-3 was 1.00 parts (solid content) and the resin PB-1 was 7.00 parts (solid content) out of the fixed amount of the resin fine particle dispersion to be fixed. The toner K was produced.

Example 12
The toner was prepared in the same manner as in Example 1 except that the resin PA-13 was 3.00 parts (solid content) and the resin PB-1 was 2.00 parts (solid content) of the fixed amount of the resin fine particle dispersion to be fixed. The toner L was produced.

Example 13
In the same manner as in Example 1 except that the amount of resin fine particle dispersion to be fixed is 2.50 parts (solid content) of resin PA-4 and 3.50 parts (solid content) of resin PB-1. The toner M was produced.

Example 14
The materials used for preparing the pigment dispersion paste of Example 1 were changed as follows. Further, the amount of the pigment paste added to the monomer mixture is 47.5 parts, the fine resin particle dispersions to be fixed are PA-5 and PB-1, and the fixed amounts are 2.50 parts and 2.50 parts, respectively. A toner N was obtained in the same manner as in Example 1 except that (solid content) was used.
・ Styrene monomer 80.0 parts ・ Carbon black 15.0 parts

Example 15
The material used for preparation of the pigment dispersion paste of Example 1 was changed as follows, and the resin fine particle dispersions to be fixed were PA-6 and PB-2, and the fixing amounts were 2.50 parts and 2.50 parts ( Toner O was obtained in the same manner as in Example 1 except that the solid content was changed.
・ Styrene monomer 80.0 parts ・ Quinacridone (Pigment Violet 19) 13.0 parts

Example 16
The material used for the preparation of the pigment dispersion paste of Example 1 was changed as follows, and the resin fine particle dispersions to be fixed were PA-7 and PB-3, and the fixing amounts were 2.50 parts and 2.50 parts, respectively ( Toner P was obtained in the same manner as in Example 1 except that the solid content was changed.
-Styrene monomer 80.0 parts-Cu phthalocyanine (Pigment Blue 15: 3) 13.0 parts

Example 17
The toner particles were fixed in the same manner as in Example 1 except that the resin fine particle dispersions to be fixed in Example 1 were PA-7 and PB-3, and the fixing amounts were 0.90 parts and 0.30 parts (solid content), respectively. The toner Q was produced.

Example 18
<Example of binder resin production>
-Bisphenol A-Propylene oxide 2.2 mol adduct 50.0 parts-Bisphenol A-Ethylene oxide 2.2 mol adduct 20.0 parts-Terephthalic acid 10.0 parts-Trimellitic anhydride 8.0 parts-Fumar Put 12.0 parts of acid and 0.005 part of dibutyltin oxide into a four-necked flask, attach a thermometer, stir bar, condenser, and nitrogen inlet tube, and react at 220 ° C. for 5 hours in a nitrogen atmosphere. Resin P-4 was obtained. The molecular weight of the obtained resin was Mw = 22,500 and Mn = 3600.

next,
-Resin P-4 100.0 parts-Cu phthalocyanine (Pigment Blue 15: 3) 5.0 parts-Paraffin wax (HNP-7: manufactured by Nippon Seiki Co., Ltd.) 3.0 parts Henschel mixer (Mitsui Mitsui) After sufficiently premixed with Kako Koki Co., Ltd., melt-kneaded with a twin-screw extruder, cooled, and coarsely pulverized to a particle size of about 1 to 2 mm using a hammer mill. The resulting finely pulverized product was classified with a multi-division classifier to obtain mother particles.

  Next, using a Henschel mixer, 100 parts of the base particles, resin fine particle dispersion PA-8: 0.60 parts and PB-3: 0.50 parts are mixed and dried in a fluidized bed dryer, and the fine particles are mixed. Thus, toner particles having adhered thereto were obtained. The toner particles were put into a hybridizer type I (manufactured by Nara Machinery Co., Ltd.) and treated at 7000 rpm for 5 minutes to fix resin fine particles. The toner particles subjected to the above treatment were externally added in the same manner as in Example 1 to obtain toner R.

Example 19
The toner fine particle dispersion to be fixed in Example 17 is PA-9 and PB-4, and the amounts of fixing are 0.60 parts and 0.50 parts (solid content), respectively. The toner S was produced.

Example 20
The toner fine particle dispersion to be fixed in Example 17 is PA-3 and PB-1, and the fixing amounts are 0.60 parts and 0.50 parts (solid content), respectively. A toner T was produced.

[Comparative Example 1]
The toner fine particle dispersion to be fixed in Example 1 was PA-3 and PB-1, and the fixing amounts were 8.00 parts and 0.25 parts (solid content), respectively. The toner U was produced.

[Comparative Example 2]
In Comparative Example 1, the toner fine particle dispersion to be fixed is PA-3 and PB-1, and the fixing amounts are 0.50 parts and 6.00 parts (solid content), respectively. And Toner V was obtained.

[Comparative Example 3]
In the same manner as in Comparative Example 1, except that the resin fine particle dispersions to be fixed in Comparative Example 1 were PA-3 and PB-5, and the fixing amounts were 0.03 parts and 0.03 parts (solid content), respectively. The toner W was produced.

[Comparative Example 4]
In the same manner as in Comparative Example 1, except that the fixed resin fine particle dispersions of Comparative Example 1 are PA-10 and PB-1, and the fixed amounts are 2.50 parts and 2.50 parts (solid content), respectively. The toner X was produced.

[Comparative Example 5]
In the same manner as in Comparative Example 1, except that the resin fine particle dispersions to be fixed in Comparative Example 1 are PA-11 and PB-1, and the fixing amounts are 2.50 parts and 4.00 parts (solid content), respectively. The toner Y was produced.

[Comparative Example 6]
The toner fine particle dispersion liquid of Comparative Example 1 is PA-10 and PB-5, and the amount of fixing is 0.02 part and 0.03 part (solid content), respectively. The toner Z was produced.

  The evaluation results of the above toner are shown in Table 3.

  As a result, it was found that in Examples 1 to 20, toner scattering was suppressed, and both the rising property of charging and the stability of the image in the minute dots were good. Furthermore, it was found that the storage stability was good when the amount ratio of units A and B in the resin fine particles was appropriate and the fixing amount was 1.00% by mass or more. However, the toners of the comparative examples are not compatible with each other.

Claims (4)

Binding Chakujushi, a toner having toner particles with an anchored resin fine particles mother particles mother particle arrangement containing a colorant and a wax,
The toner particles have the resin fine particles 0.10% by weight, based on the weight of the base particles,
The resin fine particles, and contains a resin microparticles a made of a resin containing a unit A represented by the following (Equation 1), and a resin fine particle b made of a resin containing a unit B represented by the following (Equation 2) ,
The content of the units A of the resin particles in a is 0 with respect to the resin particles. 10 0 mmol / g or more and 0.800 mmol / g or less ,
Toner, wherein the molar ratio of the content of the said unit A and said unit B in the toner particles is 0.10 or more 10.00 or less.

(In the formula 1, X is a substituted group aliphatic group which may have a or, represents an aromatic group optionally having a substituent, R ₁ is a hydrogen atom, an alkali metal atom, the carbon having 1 to 4 alkyl group or an aromatic group.)

(In the formula 2, R ₂ is a hydrogen atom or an alkyl group or alkoxy group having 1 to 4 carbon atoms.) The unit A toner according to 請 Motomeko 1 Ru phenyl sulfonic acid units der. The toner particles The toner according to Oh Ru claim 1 or 2 in the toner particles produced in an aqueous medium. The toner particles The toner according to any one of claims 1 to 3 Yes 1.00 mass% or more of the resin fine particles relative to the weight of the base particles.

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