JP5541674B2 - 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, in the transfer process, the toner particles adhere to the toner carrier, so-called development carrier or photosensitive drum, due to local charge-up on the surface of the toner, and the adhesion force (mirror power) of the toner particles increases, resulting in problems such as image defects. It becomes easy to do.

  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 are many proposals (for example, see Patent Document 1). Furthermore, there has been proposed an attempt to stabilize charging by mechanically fixing resin fine particles containing a charge control unit to a toner base (for example, see Patent Document 2).

  However, in any case, as the particle size of the toner is reduced, the toner is likely to adhere to the developing roller and the photosensitive drum due to local charge-up of the toner surface, and it has not yet been solved.

Japanese Patent Laid-Open No. 11-184165 JP 2004-318043 A

  Accordingly, an object of the present invention is to provide a toner having a rapid charge amount rise and a sharp charge amount distribution even in a high-speed one-component development system.

  It is another object of the present invention to provide a toner having a low development efficiency and transferability with less toner adhesion to the developer carrying member and the photosensitive drum due to local charge-up on the toner surface.

  Furthermore, an object of the present invention is to provide a high-quality image with good microdot reproducibility even after a large number of copying operations.

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 having adhered particulate mother particles C and the surface of the mother particles C containing colorants and waxes,
The toner particles have 0.05 wt% or more of the particles by weight of the base particles C,
The fine particles contain resin fine particles a containing units A represented by the following ( formula 1 ) ,
The mother particle C contains a resin containing a unit B represented by the following ( formula 2 ) :
The content of the units A of the resin particles in a is not more than 0.010 mmol / g or more 0.800 mmol / g,
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。
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).
Therefore, the object of the present invention can be suitably achieved.

  According to the present invention, it is possible to provide a toner that has a rapid charge amount rise in a high-speed one-component development system, has a sharp charge amount distribution, and can obtain high-quality image quality even after a large number of sheet copying operations. In addition, it is possible to prevent the toner from adhering to the developing carrier and the photosensitive drum due to local charge-up of the toner surface, and to provide a toner with good development efficiency and transferability.

FIG. 6 is a diagram illustrating an example of measurement of toner charge amount rising characteristics. It is explanatory drawing of the pattern image for micro dot reproducibility evaluation.

  The present inventors use the toner having toner particles in which the resin fine particles a having the unit A represented by the following formula 1 are fixed on the surface of the mother particle C containing the resin having the unit B represented by the following formula 2. The inventors have found that the effect is exerted and 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がＨ、炭素数１から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.)

  In general, when the chargeability on the surface of the toner increases, local charge-up may occur. Due to this action, the adhesion force to the developer carrying member and the photosensitive drum increases, thereby causing problems such as a reduction in development efficiency and transferability. This tendency is conspicuous in a large number of images after the copying operation, and it is considered that embedding of an external additive on the toner surface promotes a problem due to charge-up.

  According to the toner of the present invention, those problems are less likely to occur, and high-quality images can be obtained efficiently even after endurance. The details are not clear, but they are considered as follows. The toner of the present invention is considered to be less likely to adhere to the developer carrying member and the photosensitive drum because the charge density on the toner surface is kept moderately low without locally increasing. The toner of the present invention is considered to have at least resin fine particles having a power generation function fixed on its surface. This is due to the resin having the structure of unit A represented by Formula 1. It is considered that the rise of the charge amount is accelerated by the resin fine particles even in a development system with few charging opportunities. In addition, it is considered that the presence of the chargeable substance in the toner can be eliminated and a sharp charge distribution can be obtained by making the toner surface reliably exist. On the other hand, a resin that is considered to have a charge dissipation mechanism is internally added inside the toner. This is due to the resin having the structure of unit B represented by Formula 2. Even if an excessive charge is generated in the process of frictional charging of the toner, it is expected that the charge density penetrates into the toner and diffuses to keep the charge density on the toner surface moderately low. By this action, it is considered that local charge-up due to excessive charges is suppressed, and the adhesion force of toner to the developing carrier and the photosensitive drum is reduced.

  Due to the above-described action, even in a high-speed one-component developing system with few charging opportunities, a toner having a sharp charge distribution and a sharp charge distribution can be obtained. Further, the toner of the present invention has a surface charge density that does not become excessive locally, so that the coatability of the toner to the developing portion carrier becomes uniform, and the developing bias is uniformly applied, so that the developing efficiency increases. Furthermore, when the toner is transferred to the photosensitive drum, the transfer current is easily received uniformly, so that transferability is improved. Even when the external additive is in a deteriorated state in a large number of copies, the toner of the present invention has a good balance between the development efficiency and the transfer efficiency, and a high-quality image such as a fine dot can be obtained. Can do.

  The toner of the present invention has toner particles in which resin fine particles a are fixed to base particles C serving as nuclei. It is necessary to fix the fine particles including the resin fine particles a to the base particles C in a range of 0.05% by mass or more. If the mass ratio of the resin fine particles a to the mother particles is less than 0.05% by mass, adhesion between the toners becomes nonuniform and the charge distribution may become nonuniform. In addition, when the amount of fine resin particles is very large with respect to the base particle C, uniform fixation may be difficult, and the charge amount distribution may be non-uniform. Therefore, the resin fine particles including the resin fine particles a are preferably fixed to the base particle C with the upper limit being 10.0% by mass.

  Further, the content of the unit A contained in the resin fine particles a needs to be 0.010 mmol / g or more and 0.800 mmol / g or less. More preferably, it is 0.100 mmol / g or more and 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 is less than 0.010 mmol / g, a sufficient charge amount may not be obtained, and the above 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 quantified by NMR, acid value, OH value measurement, or the like. The amount of unit B in the resin b is preferably 0.070 to 1.000 mmol / g from the viewpoint of easy production of resin fine particles. Therefore, the unit B content in the toner is controlled by the charged amount of the unit B-containing resin. This unit may be present dispersed in the mother particle C, but preferably present in the vicinity of the surface of the mother particle C to exhibit the effect of the present invention. An example of a production method for causing the unit B to be concentrated near the surface of the mother particle C is a method of producing the mother particle C in an aqueous medium. The unit B is considered to easily move to the vicinity of the toner surface during production because the functional group itself has a high polarity.

  The molar ratio of the content of unit B to unit A used in the present invention 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 the charge dissipation mechanism is reduced, so that a sufficient charge amount can be obtained, but the local charge-up that is the effect of the present invention is achieved. Can not be suppressed. Therefore, the transfer efficiency may be further deteriorated in a low temperature and low humidity environment. 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.

  As the composition of the (co) polymer having the unit B and the resin fine particles a having the unit A, a known resin composition can be used. 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 then purified by column chromatography (silica gel 5 kg, mobile phase hexane / ethyl acetate = 1/1) to obtain 383 g of the monomer 4M represented by the formula (4A). Got.

<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 the formula (4B).

<Monomer 4C>
Monomer 4C represented by the formula (4C) is produced in the same manner as in the production of monomer 5A, except that 726 g of p-toluidine-2-sulfonic acid is used instead of 2-amino-5-methoxybenzenesulfonic acid. 352g was 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 the formula (4D).

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

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

<Monomer 4G>
As the monomer 4G, 2-acrylamidobenzenesulfonic acid represented by the formula (4G) 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-t-butylsalicylic acid.

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

<Monomer 5A>
The monomer 5A represented by the formula (5A) was produced using the method described in JP-A No. 63-270060, Journal of Polymer Science: Polymer Chemistry Edition 18, 2755 (1980).

<Monomer 5B>
Monomer 5B represented by the formula (5B) was produced using the method described in JP-A-62-1874429.

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

<Monomer 5D>
The monomer 5D represented by the formula (5D) 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; an alkyl group having 6 to 12 carbon atoms 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 C that can be used in the present invention will be described below.

  As a means for producing the mother particle C of the present invention, a known method can be used. 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. .

  In the kneading and pulverization method, the binder resin, the colorant and / or the magnetic material, the (co) polymer having the unit B, and / or other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill. The mother particles C can be prepared by melt-kneading using a heat kneader such as a kneader or an extruder, cooling and solidifying the kneaded product, pulverizing the solidified product, and classifying the pulverized product.

  In the suspension polymerization method, the (co) polymer having unit B is dissolved or finely dispersed in a polymerizable monomer together with other necessary components, suspended and granulated in an aqueous medium, and then contained in droplets. The monomer particles C can be produced by polymerizing the monomer.

  In the dissolution suspension method, the (co) polymer having unit B is dissolved or dispersed in an organic solvent together with other necessary components, suspended and granulated in an aqueous medium, and then the organic solvent contained in the droplets is removed. By removing, the mother particle C can be produced.

  In the emulsion aggregation method, the (co) polymer having unit B is finely dispersed in an aqueous medium by a method such as phase inversion emulsification, mixed with fine particles of other necessary components, and the zeta potential of those in the aqueous medium. The mother particles C can be produced by agglomeration to the toner particle diameter by control.

  The mother particle C of the present invention contains at least a binder resin, a colorant and a release agent.

  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.

  As a polymerization initiator that can be used when copolymerizing the polymerizable monomer component described above, various substances such as a peroxide polymerization initiator and an azo polymerization initiator can be used. 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 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. Examples of the crosslinking agent used in this case 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 0.1 mass part or more and 60 mass parts or less in total with respect to 100 mass parts of binder resin, Preferably it is 0.5 mass part or more and 50 mass parts The following are appropriate.

  In order to improve the offset property to the fixing device at the time of fixing the toner, 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. The release agent that can be used in the toner of the present invention is not particularly limited, and known ones can be used. For example, aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, and paraffin wax; waxes based on fatty acid esters such as carnauba wax, sazol wax, and montanic acid ester wax; behenic acid monoglyceride Examples thereof include partially esterified products of fatty acids and polyhydric alcohols; methyl ester compounds having hydroxyl groups obtained by hydrogenating vegetable oils and fats.

  The molecular weight distribution of the release agent used in the present invention is preferably such that the main peak is in the region of molecular weight of 400 or more and 2400 or less, more preferably in the region of 430 or more and 2000 or less, and imparts favorable thermal characteristics to the toner. can do.

  Moreover, as addition amount of a mold release agent, it is preferable that content with respect to binder resin is 2.5 to 15.0 mass parts in total, Furthermore, 3.0 to 10.0 mass parts is preferable. The following is more preferable. If the amount of the release agent added is less than 2.5 parts by mass, oilless fixing becomes difficult. If the amount exceeds 15.0 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 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 present invention, known methods can be used as the method for producing the resin fine particles a.

  For example, the following methods are specifically 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 method for preparing the resin fine particles a is not particularly limited, and is prepared by emulsion polymerization, or by dissolving or melting the resin in a solvent to liquefy it, and suspending or phase inversion emulsifying it in an aqueous medium. The method of doing is mentioned. At this time, a known surfactant or dispersant can be used, or the resin forming the resin fine particles a can have self-emulsifying properties.

  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 the emulsion polymerization method is an addition polymerization monomer that generates the unit A having a sulfonic acid substituent represented by Formula 1. Good. 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 forming the resin fine particles a is preferably formed by copolymerizing a monomer that forms 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, a known method can be used as a method for fixing the resin fine particles a to the base particles C.

  For example, there is a method of applying mechanical stress by mixing base particles C and fine particles including resin fine particles a. Further, there is a method in which fine particles containing resin fine particles a are added and fixed in an aqueous medium containing the mother particles C. 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 the resin fine particles a on the surface of the base particle C uniformly and firmly.

  That is, in order to obtain the toner surface fixing uniformity, the resin fine particle a 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 the individual fine particles, and there is concern about the presence of the unit A contained in the fine particles. In this case, 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 resin fine particle a particle diameter can satisfy the above range by adjusting the granulation conditions at the time of fine particle production. 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 a particle diameter measuring 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).

  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 14 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 ・ 68.0 parts of styrene 15.0 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.

  100 parts of THF was put into a 1 L tall beaker, and 60 parts of resin PA-1 was added little by little with stirring to dissolve. 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, it was confirmed that the obtained resin PA-1 contained unit A derived from 0.591 mmol / g sulfonic acid. The particle diameter was 74 nm. Table 1 summarizes the physical properties of the resin fine particles PA-1.

[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.
・ Methyl 2-methacrylamide-2-methylbenzenesulfonate 22.0 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-2 was confirmed to contain unit A derived from 0.752 mmol / g sulfonic acid. The particle diameter was 73 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.
・ Methyl 2-methacrylamide-5-methylbenzenesulfonate 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-3 contained unit A derived from 0.105 mmol / g sulfonic acid. The particle diameter was 75 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.
・ Methyl 2-methacrylamide-5-methylbenzenesulfonate 0.5 part ・ 84.5 parts of styrene ・ 15.0 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, it was confirmed that the obtained resin PA-4 contained unit A derived from 0.018 mmol / g sulfonic acid. The particle diameter was 69 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.
-7.0 parts of 2-acrylamido-2-methylpropanesulfonic acid-77.0 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, it was confirmed that the obtained resin PA-5 contained unit A derived from 0.332 mmol / g sulfonic acid. The particle diameter was 73 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-acrylamide-2-methylpropanesulfonic acid 3.0 parts styrene 82.0 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-6 was confirmed to contain unit A derived from 0.145 mmol / g sulfonic acid. The particle diameter was 72 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.
-2-acrylamido-2-methylpropanesulfonic acid 17.0 parts-Styrene 67.0 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, it was confirmed that the obtained resin PA-7 contained unit A derived from 0.748 mmol / g sulfonic acid. The particle diameter was 69 nm.

[Synthesis Example 8 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-8.
・ Methyl 2-acrylamido-2-methylpropanesulfonate 11.0 parts ・ Styrene 73.0 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, it was confirmed that the obtained resin PA-8 contained unit A derived from 0.489 mmol / g sulfonic acid. The particle diameter was 65 nm.

[Synthesis Example 9 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-9.
-2-methacrylamido-5-methylbenzenesulfonic acid 10.0 parts-Styrene 74.0 parts-2-ethylhexyl acrylate 16.0 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-9 was confirmed to contain unit A derived from 0.364 mmol / g sulfonic acid. The particle diameter was 68 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.
・ Methyl 2-methacrylamide-5-methoxybenzenesulfonate 14.0 parts ・ Styrene 76.0 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-10 was confirmed to contain unit A derived from 0.484 mmol / g sulfonic acid. The particle diameter was 81 nm.

[Synthesis Example 11 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 20 parts of 4-aminobenzenesulfonic acid were put into 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-11 contained unit A derived from 0.517 mmol / g sulfonic acid. The particle diameter was 79 nm.

[Synthesis Example 12 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,
20.0 parts methyl 2-methacrylamide-5-methoxybenzenesulfonate 80.0 parts styrene 1.5 parts dimethyl-2,2′-azobis (2-methylpropionate) The solution 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-12.

  As a result of quantitative determination of sulfur atoms by elemental analysis, the obtained resin PA-12 was confirmed to contain unit A derived from 0.466 mmol / g sulfonic acid. The particle diameter was 66 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.
・ Methyl 2-methacrylamide-5-methoxybenzenesulfonate 0.1 parts ・ Styrene 86.9 parts ・ N-butyl acrylate 13.0 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 0.004 mmol / g sulfonic acid. The particle diameter was 68 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.
・ Methyl 2-methacrylamide-5-methoxybenzenesulfonate 30.0 parts ・ Styrene 60.0 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-14 was confirmed to contain unit A derived from 0.998 mmol / g sulfonic acid. The particle diameter was 85 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-74.0 parts of styrene-16.0 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 the acid value measurement, the obtained resin PB-1 was confirmed to contain unit B derived from 0.589 mmol / g of salicylic acid. 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-tertiary butyl-5-vinylsalicylic acid 1.5 parts styrene 82.5 parts 2-ethylhexyl acrylate 16.0 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 0.055 mmol / g of salicylic acid.

[Synthesis example 3 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-3.
3-tert-butyl-5-vinylsalicylic acid 13.0 parts styrene 71.0 parts 2-ethylhexyl acrylate 16.0 parts dimethyl-2,2'-azobis (2-methylpropionate) 5.0 Part

  As a result of acid value measurement, the obtained resin PB-3 was confirmed to contain unit B derived from 0.578 mmol / g of salicylic acid.

[Synthesis example 4 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 12 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-4 was confirmed to contain unit B derived from 0.647 mmol / g salicylic acid.

[Synthesis example 5 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-5.

  As a result of acid value measurement, the obtained resin PB-5 was confirmed to contain unit B derived from 0.476 mmol / g of salicylic acid.

  Subsequently, toners A to Y 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-Resin PB-1 4.0 parts After the above material was well premixed in a container, it was kept at 20 ° C or lower. The mixture was dispersed with a bead mill for about 4 hours to prepare a pigment dispersion paste.

Preparation of toner particles:
390 parts of a 0.1 mol / liter-Na ₃ PO ₄ aqueous solution was added to 1150 parts of ion-exchanged water, heated to 60 ° C., and then 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, 4.0 parts of the PA-1 resin fine particle dispersion is solidly added to the obtained dispersion of the base particle C and the solid content of 100 parts. 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 6.5 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 charge amount rise characteristic>
The toner charge amount rising characteristics of the present invention were evaluated as follows. The drum unit of the process cartridge of the Canon laser beam printer LBP5500 is removed and 50 g of the obtained toner is filled. A cartridge is set on an idle rotating jig formed so that the developing roller rotates, and a surface potential probe is arranged on the developing roller. While monitoring the surface potential, the developing roller is rotated at a rotational speed of 250 rpm. The surface potential can monitor the change in the coat state of the toner in proportion to the toner amount and the charge amount on the developing roller. The obtained data is shown in FIG. 1, for example. Evaluation of the rising property of the toner charge amount was performed as follows. That is, the ratio (V10 / V30) of the absolute value of the potential (V30) after 30 seconds to the surface potential (V10) after 10 seconds was taken, and ranking was performed according to the following criteria.
A rank: 0.75 ≦ V10 / V30
B rank: 0.65 ≦ V10 / V30 <0.75
C rank: 0.55 ≦ V10 / V30 <0.65
D rank: V10 / V30 <0.55

<Image quality evaluation after copying many sheets>
Evaluation of image quality after copying a large number of toner charge amounts of the present invention was performed as follows.

(Evaluation-1: Fine dot reproducibility)
The cartridge used for the evaluation of the rising of the charge amount is continuously idled and is temporarily stopped for 2 minutes from the initial stage. In order to evaluate the image quality at this time, the removed drum unit was attached again. Then, it was mounted on the LBP 5500, and an image of an isolated dot pattern with a small diameter (45 μm) as shown in FIG. Subsequently, the drum unit is removed again, and the idling of the developing unit is continued for 4 hours. Images at this time were evaluated in the same manner as in the initial stage, and ranked according to the following criteria.
A: 2 or less defects / 100 B: 3-5 defects / 100 defects C: 6-10 defects / 100 defects D: 11 defects / 100 defects / 100

(Evaluation-2: Evaluation of transferability by leaving in a low-temperature and low-humidity environment)
The evaluation toner is put in a cartridge and left in a low temperature and low humidity environment chamber (16 ° C., 15%) overnight (12 hours). For the transferability, an evaluation machine similar to Evaluation-1 was used to develop and transfer the image before and after the 4-hour idling, and the toner amount (per unit area) before transfer on the photoreceptor and the toner amount on the transfer material ( Per unit area) was measured and determined by the following equation. The evaluation criteria are as follows.
Transfer rate (%) = (toner amount on transfer material) / (toner amount before transfer on photoconductor) × 100
A: 90% or more B: 88% or more and less than 90% C: 86% or more and less than 88% D: less than 86%

  When the toner was evaluated based on the above evaluation methods and standards, the toner A of this example was excellent in charge rising characteristics and ranked A. In addition, in the image after idling for 4 hours, fine dots were reproduced well compared with the initial value, and the A rank was obtained. Furthermore, the transferability evaluation after leaving in a low-temperature and low-humidity environment was also more efficient than the initial transfer and was ranked A. All the evaluation results are shown in Table 3.

[Example 2]
The amount of PB-2 used to prepare the pigment dispersion paste of Example 1 was 1.00 part, the resin fine particle dispersion to be fixed was PA-2, and the amount of fixation was 0.08 part (solid content). A toner was prepared in the same manner as in Example 1 except that Toner B was obtained.

Example 3
The amount of PB-1 used for preparing the pigment dispersion paste of Example 1 was 0.80 part, the fine resin particle dispersion to be fixed was PA-1, and the fixed amount was 3.00 parts (solid content). A toner was prepared in the same manner as in Example 1 except that Toner C was obtained.

Example 4
The amount of PB-1 used in the preparation of the pigment dispersion paste of Example 1 was 25.0 parts, the fine resin particle dispersion to be fixed was PA-1, and the fixed amount was 3.00 parts (solid content). A toner was prepared in the same manner as in Example 1 except that Toner D was obtained.

Example 5
The amount of PB-1 used for preparing the pigment dispersion paste of Example 1 was 1.00 part, the resin fine particle dispersion to be fixed was PA-3, and the amount of fixation was 3.00 parts (solid content). A toner was prepared in the same manner as in Example 1 except that Toner E was obtained.

Example 6
The amount of PB-1 used to prepare the pigment dispersion paste of Example 1 was 1.00 part, the resin fine particle dispersion to be fixed was PA-4, and the amount of fixation was 4.00 parts (solid content). A toner was prepared in the same manner as in Example 1 except that Toner F was obtained.

Example 7
The amount of PB-1 used for preparing the pigment dispersion paste of Example 1 was 10.0 parts, the resin fine particle dispersion to be fixed was PA-2, and the amount of fixing was 5.00 parts (solid content). A toner was prepared in the same manner as in Example 1 except that Toner G was obtained.

Example 8
The materials used for preparing the pigment dispersion paste of Example 1 were changed as follows. In addition, the amount of the pigment paste added to the monomer mixture was 47.5 parts, the resin fine particle dispersion to be fixed was PA-5, and the fixing amount was 5.00 parts (solid content). A toner was prepared in the same manner as in Example 1 to obtain a toner H.
-Styrene monomer 80.0 parts-Cu phthalocyanine (Pigment Blue 15: 3) 13.0 parts-Resin PB-1 3.0 parts

Example 9
The amount of PB-1 used in the preparation of the pigment dispersion paste of Example 8 was changed to 0.50 part, the fine resin particle dispersion to be fixed was PA-5, and the fixed amount was 5.00 parts (solid content) A toner was prepared in the same manner as in Example 1 except that the toner I was obtained.

Example 10
The amount of PB-1 used for the preparation of the pigment dispersion paste of Example 8 was changed to 30.0 parts, the resin fine particle dispersion to be fixed was PA-5, and the amount of fixation was 6.00 parts (solid content) A toner was prepared in the same manner as in Example 1 except that the toner J was obtained.

Example 11
The amount of PB-1 used in the preparation of the pigment dispersion paste of Example 8 was changed to 1.00 part, the fine resin particle dispersion to be fixed was PA-6, and the fixed amount was 5.00 parts (solid content) A toner was prepared in the same manner as in Example 1 except that the toner K was obtained.

Example 12
The amount of PB-1 used for the preparation of the pigment dispersion paste of Example 8 was changed to 10.0 parts, the resin fine particle dispersion to be fixed was PA-7, and the amount of fixation was 5.00 parts (solid content) A toner was prepared in the same manner as in Example 1 except that the toner L was obtained.

Example 13
The materials used for preparing the pigment dispersion paste of Example 1 were changed as follows. Further, an example except that the amount of pigment paste added to the monomer mixture was 47.5 parts, the fine resin particle dispersion to be fixed was PA-8, and the fixed amount was 3.00 parts (solid content). Toner M was obtained in the same manner as in Example 1.
-Styrene monomer 80.0 parts-Carbon black 15.0 parts-Resin PB-1 2.00 parts

Example 14
The material used for preparation of the pigment dispersion paste of Example 1 was changed as follows, and the resin fine particle dispersion to be fixed was PA-9, and the amount of fixation was 5.00 parts (solid content). In the same manner, a toner was prepared to obtain a toner N.
・ Styrene monomer 80.0 parts ・ Quinacridone (Pigment Violet 19) 13.0 parts ・ Resin PB-3 3.0 parts

Example 15
The material used for the preparation of the pigment dispersion paste of Example 1 was changed to the following, Example 1 except that the resin fine particle dispersion to be fixed was PA-10, and the fixing amount was 3.00 parts (solid content). In the same manner, a toner was prepared to obtain a toner O.
-Styrene monomer 80.0 parts-Cu phthalocyanine (Pigment Blue 15: 3) 13.0 parts-Resin PB-4 3.0 parts

Example 16
<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-Resin PB-4 20.0 parts-Cu phthalocyanine (Pigment Blue 15: 3) 5.0 parts-Paraffin wax (HNP-7: manufactured by Nippon Seiki Co., Ltd.) 3.0 parts The toner material is sufficiently premixed with a Henschel mixer (Mitsui Miike Chemical Co., Ltd.), melt-kneaded with a twin-screw extruder, cooled, and then coarsened to a particle size of about 1 to 2 mm using a hammer mill. Next, the mixture was pulverized with an air jet type pulverizer, and the obtained pulverized product was classified with a multi-division classifier to obtain mother particles.

  Next, 100 parts of the mother particles obtained in an aqueous solution in which 2.0 parts of the anionic surfactant Neogen SC (Daiichi Kogyo Seiyaku Co., Ltd.) was dissolved in 200 parts of ion-exchanged water were added with stirring. A particle dispersion was prepared. Further, a resin fine particle dispersion of PA-11 is gradually added to a solid content equivalent to 5.00 parts. 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. Toner P was obtained by externally adding hydrophobic silica to the obtained toner particles in the same manner as in Example 1.

Example 17
The toner was changed in the same manner as in Example 12 except that the PB resin of Example 12 was changed to PB-5, 18.0 parts, and the resin fine particle dispersion to be fixed was PA-12, 5.00 parts (solid content). The toner Q was produced.

[Comparative Example 1]
The material used for preparation of the pigment dispersion paste of Example 1 was changed to the following, Example 1 except that the resin fine particle dispersion to be fixed was PA-8, and the fixing amount was 6.70 parts (solid content). In the same manner, a toner was produced to obtain a toner R.
-Styrene monomer 80.0 parts-Cu phthalocyanine (Pigment Blue 15: 3) 13.0 parts-Resin PB-3 0.25 parts

[Comparative Example 2]
In Comparative Example 1, the charge amount of the material PB-3 used for preparing the pigment dispersion paste was changed to 35.0 parts, the resin fine particle dispersion to be fixed was PA-8, and the fixation amount was 3.50 parts (solid A toner was prepared in the same manner as in Comparative Example 1 except that the toner S was obtained.

[Comparative Example 3]
In Comparative Example 1, the resin fine particle dispersion to be fixed is PB-2, the charging amount is changed to 2.00 parts, the resin fine particle dispersion to be fixed is PA-8, and the fixation amount is 0.03 parts (solid content). A toner was prepared in the same manner as in Comparative Example 1 except that the toner T was obtained.

[Comparative Example 4]
The material used for preparation of the pigment dispersion paste of Example 1 was changed as follows, and the resin fine particle dispersion to be fixed was PA-13, and the amount of fixation was 2.00 parts (solid content). In the same manner, a toner was prepared to obtain a toner U.
-Styrene monomer 80.0 parts-Cu phthalocyanine (Pigment Blue 15: 3) 13.0 parts-Resin PB-1 0.10 parts

[Comparative Example 5]
The material used for preparation of the pigment dispersion paste of Example 1 was changed to the following, and the resin fine particle dispersion to be fixed was PA-14, and the amount of fixation was 5.00 parts (solid content). In the same manner, a toner was prepared to obtain a toner V.
-Styrene monomer 80.0 parts-Cu phthalocyanine (Pigment Blue 15: 3) 13.0 parts-Resin PB-4 10.0 parts

[Comparative Example 6]
The material used for the preparation of the pigment dispersion paste of Example 1 was changed to the following, except that the resin fine particle dispersion to be fixed was PA-10, and the fixing amount was 3.00 parts (solid content). A toner was prepared in the same manner as in Example 1, and Toner W was obtained.
-Styrene monomer 80.0 parts-Cu phthalocyanine (Pigment Blue 15: 3) 13.0 parts

[Comparative Example 7]
In preparation of the pigment dispersion paste of Example 1, the material was changed to the following to obtain a pigment paste.

-Styrene monomer 80.0 parts-Cu phthalocyanine (Pigment Blue 15: 3) 13.0 parts-Resin PB-1 3.0 parts After the above material was well premixed in a container, it was kept at 20 ° C or lower. The mixture was dispersed with a bead mill for about 4 hours to prepare a pigment dispersion paste.

Preparation of toner particles:
390 parts of a 0.1 mol / liter-Na ₃ PO ₄ aqueous solution was added to 1150 parts of ion-exchanged water, heated to 60 ° C., and then 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.

After cooling to room temperature, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ and filtered, washed with water, and dried to obtain toner particles. The obtained toner particles were classified, and hydrophobic silica was externally added in the same manner as in Example 1 to obtain toner X.

[Comparative Example 8]
In Comparative Example 1, the resin fine particle dispersion to be fixed is PB-2, the charging amount is changed to 0.01 part, the resin fine particle dispersion to be fixed is PA-13, and the fixation amount is 0.01 part (solid content). A toner was prepared in the same manner as in Comparative Example 1 except that the toner Y was obtained.

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

  As a result, in Examples 1 to 17, it was found that both the charge rising property and the image stability were good. However, the toners of the comparative examples are not compatible with each other.

Claims (2)

A toner having toner particles having mother particles C containing a binder resin, a colorant and a wax, and fine particles fixed to the surfaces of the mother particles C,
The toner particles have 0.05 wt% or more of the particles by weight of the base particles C,
The fine particles contain resin fine particles a containing units A represented by the following ( formula 1 ) ,
The mother particle C contains a resin containing a unit B represented by the following ( formula 2 ) :
The content of the units A of the resin particles in a is not more than 0.010 mmol / g or more 0.800 mmol / g,
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.

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