JP5677031B2 - toner - Google Patents

Description

  The present invention relates to a toner used in electrophotography, electrostatic recording, and magnetic recording. Specifically, the present invention relates to an electrostatic charge image developing toner (hereinafter abbreviated as toner) used in an image recording apparatus that can be used in a copying machine, a printer, a facsimile, a plotter, and the like.

The electrophotographic technology used for copiers, printers, facsimiles and the like is continuing to develop, and recent trends are increasingly demanding that high-speed printing is possible, or that miniaturization and energy saving are achieved.
In order to satisfy such requirements, for example, the toner can be improved to a toner that can be fixed at a lower temperature by lowering the glass transition point of the binder resin used in the toner particles or by lowering the molecular weight of the binder resin. Is underway.
As a toner resin material, a polyester resin or a styrene acrylic resin is generally selected from the viewpoint of charging characteristics, resin strength, and color developability. In particular, polyester resins are actively studied because of the wide selectivity of polymerizable monomers and easy resin design.
For example, in order to maintain durability while achieving further low-temperature fixability, a technique for incorporating a crystalline polyester resin having a melting point into a toner binder resin is disclosed (for example, see Patent Document 1). . The crystalline polyester resin has a sharp melt property and fluidizes in a temperature range exceeding the melting point, and thus greatly contributes to the toner fixability. Moreover, sufficient strength is obtained at a temperature not exceeding the melting point, and higher durability image stability can be derived.
However, the polyester resin has not yet satisfied the performance demanded in recent years in terms of charging stability, and has to be improved.
The inventors of the present invention have been studied with a particular focus on durability. In terms of durability, there are often trade-offs with low-temperature fixing means. For example, if the glass transition temperature of the resin is lowered, the resin fluidizes on the lower temperature side, which is advantageous for fixing. This is likely to cause harmful effects. The inventors of the present invention have focused on changing the point of view and deepening means that does not contaminate the member even when the toner is crushed. As a result of various studies, it has been found that when an appropriate amount of a nonionic surfactant is present on the toner surface, the toner hardly adheres to various members.
Until now, it has been commonly known that the presence of a surfactant on the toner surface deteriorates various performances, so that it should be eliminated as much as possible (see, for example, Patent Document 2). In particular, in Patent Document 2, it is said that the nonionic surfactant should be as good as possible. Further, in other documents, for example, when a surfactant is used at the time of toner production, it has been treated as an implicit understanding matter that the surfactant is completely removed by strong washing, regardless of means. It was.
Among the surfactants in the toner field in the situation as described above, there are some documents focusing on nonionic surfactants on the toner surface. For example, by specifying the types of nonionic surfactants and external additives on the surface and the coverage, it is mentioned that a toner having good environmental stability while improving the low-temperature fixability of the toner can be obtained (patent) Reference 3). Further, it has been proposed that a toner having excellent charging characteristics and environmental stability can be obtained by defining residual surfactant and aggregating agent-derived divalent metal ions in the toner (see Patent Document 4). ).
In Patent Document 3, it has been found that the toner can be plasticized by containing a nonionic surfactant, but has some problems in the uniformity of the charge distribution.
In Patent Document 4, a surfactant that is preferably used as an emulsifier is strong in hydrophilicity, or because both an ionic surfactant and a nonionic surfactant are present. There are still some issues in achieving stability.

JP 2008-191260 A JP 2002-131977 A JP 2008-151950 A Japanese Patent No. 3107062

  The present invention is to provide a toner capable of solving the problems described in the background. That is, it is an object of the present invention to provide a toner having excellent charge distribution uniformity and charge stability even when high-speed printing is performed for a long period of time and having high developability.

［構造式（１）中、ａ、ｂ及びｃは整数であって、ａ＞０、ｂ≧４、ｃ＞０、ａ＋ｃ≧４である。］
That is, the present invention is a toner containing at least toner particles produced in an aqueous medium and inorganic fine powder, wherein the toner particles include at least a binder resin, a colorant, and a nonionic surfactant. And the binder resin includes a polyester resin produced using a titanium compound as a catalyst, and the content of the titanium element derived from the polyester resin produced using the titanium compound as a catalyst is 100 ppm or more and 1,000 ppm or less. There, the extraction amount of the nonionic surfactant is extracted with methanol from the toner and a (ppm), determined from the particle size distribution of the toner using the precision particle size distribution measuring apparatus based on a pore electrical resistance method theory when the specific surface area was B ^(m 2 / g), the ratio B of the a (a / B) ^{is, 5.0 × 10 -4 (g /} m 2) or more 4.0 × and at 10 -3 ^{(g /} m ²⁾ or less, the nonionic surfactants contain block copolymers of alkylene glycol represented by the following structural formula (1), the alkylene glycol The present invention relates to a toner having a number average molecular weight measured by gel permeation chromatography of a block copolymer of 1200 or more and 40000 or less.

[In Structural Formula (1), a, b and c are integers, and a> 0, b ≧ 4, c> 0, a + c ≧ 4. ]

  According to the present invention, even when high-speed printing is performed for a long period of time, a toner having excellent charge distribution uniformity and charging stability and high developability can be provided.

Providing a toner having both stable and high developability and durability in various environments is an essential issue in order to satisfy market needs. As a result of intensive studies on the toner for satisfying such required performance, the present inventors have reached the present invention.
That is, it has been found that the above problem can be addressed by adding an appropriate amount of a specific nonionic surfactant to toner particles containing a polyester resin produced using a titanium compound as a catalyst. Although there are many unclear points for the detailed reason, the present inventors consider as follows.
The polyester resin used in the toner of the present invention is a polyester resin produced using a titanium compound as a catalyst. Therefore, in the toner of the present invention, it is considered that polyester-titanium oxide in which fine titanium oxide and polyester are chemically bonded exists as a charge point (storage point) inside the toner. In addition, the presence of the nonionic surfactant of the present invention on the toner surface causes the injection of charge into the polyester-titanium oxide as a charge point. Therefore, the toner can store charges not only on the surface but also inside the toner, so that a large charge amount can be held and stabilized. In addition, since the electric charge exists in the interior as compared with the toner charged only on the surface, the charge amount per one toner particle does not depend only on the surface area but also on the volume, and between the toner particles. The amount of electrification tends to be uniform. In other words, the smaller the toner particle size, the larger the surface area per volume, so the toner charged only on the surface has a large difference in volume charge density for each particle size, but the charge can be stored up to the inside of the toner. As a result, the difference in the volume charge density due to the particle diameter of the toner becomes small.
From the above, the toner of the present invention has a uniform charge amount distribution and can achieve high charge amount stability.
The present invention is described in further detail below.
The polyester resin used in the present invention is produced using a titanium compound as a catalyst. Since the catalyst of the titanium compound used for the production of the polyester resin has higher hydrolyzability than other polycondensation catalysts, it is considered that the polyester resin has a charge point as polyester-titanium oxide. This polyester-titanium oxide is generated when the catalyst of the titanium compound advances hydrolysis while transesterifying with polyester in the course of the polycondensation reaction. Since the catalyst of the titanium compound gradually changes its structure to titanium oxide by hydrolysis by transesterification, it is considered that the titanium compound produced has a titanium compound in the middle of transesterification. It is thought that a part of the polyester and the titanium compound in the middle of transesterification contained in the titanium oxide produced by this hydrolysis are in direct chemical interaction, and this ties the polyester and titanium oxide together. It becomes very finely dispersed polyester-titanium oxide. Further, the proportion of the titanium oxide part and the titanium compound in the middle of transesterification may be present in various ratios depending on the degree of hydrolysis, and is considered to exist as a compound having various resistance values.
It is estimated that when the finely dispersed polyester-titanium oxide accumulates electric charge in the polyester resin, it acts as a charge point, so that the toner resin can be charged to the inside.
However, a conventional toner using a polyester resin produced by simply using a titanium compound as a catalyst as a binder resin cannot store charges at a charge point efficiently and quickly. This is thought to be due to the large resistance difference between the polyester resin and the charge point polyester-titanium oxide. In general, the charge retention is greater as the resistance value is larger, and less as the resistance value is smaller. On the other hand, those having a large resistance value have a slow charge injection and leakage, and those having a small resistance value have a fast charge injection and leakage. That is, as the resistance value is larger, the movement of charges is less likely to occur, and as the resistance value is smaller, the charges are more likely to move. It is estimated that the polyester-titanium oxide in the polyester resin has a considerably smaller resistance value than the polyester resin. Once the polyester-titanium oxide can obtain a charge, it is considered that charge transfer is limited because it is surrounded by a polyester resin having a high resistance value. Therefore, the charge obtained on the toner surface layer cannot move to the polyester-titanium oxide which is a charge point inside the toner resin. Therefore, it is considered that even a toner using a polyester resin produced using a conventional titanium compound as a catalyst could only exhibit the same charging performance as a toner using another polyester resin.
According to the present invention, it is considered that the presence of the nonionic surfactant on the toner surface enables the charge to be stored efficiently and quickly at the charge point.
The nonionic surfactant is considered to be able to diversify the resistance value depending on how the polar site is coordinated with the toner surface layer and the moisture absorption state. It can be considered that a relatively low resistance value can be obtained when the charge amount is low, and a relatively high resistance value can be obtained when the charge amount is high, and the state of charge on the toner surface can be diversified. It is believed that this makes it possible to smoothly inject charges into the toner. Furthermore, since non-ionic surfactants can diversify their resistance values, tunneling phenomenon from the toner surface layer to the fine titanium oxide, which is the charge point inside the polyester resin, can be made to change the energy state of the charge. It is considered that the charge can be moved by the above. Due to this effect, the charge can be stored inside the toner, so that the charging is stable and the distribution uniformity is considered to be extremely excellent.

Next, the amount of the nonionic surfactant per unit surface area of the toner necessary for exhibiting the above effect will be described. The condition can be obtained from the extraction amount of the nonionic surfactant extracted from the toner with methanol and the theoretical specific surface area obtained from the particle size distribution of the toner. Specifically, the extraction amount of the nonionic surfactant extracted from the toner with methanol is defined as A (ppm), and it is obtained from the particle size distribution of the toner using a precise particle size distribution measuring apparatus by the pore electrical resistance method. When the theoretical specific surface area is B (m ² / g), the ratio of A to B (A / B) is 5.0 × 10 ⁻⁵ or more and 9.0 × 10 ⁻³ (g / m ² ) or less. It is.
This is an approximation of the amount of the surfactant present on the toner surface and expresses the amount of the surfactant necessary in the present invention. When (A / B) is within the above range, the uniformity of charge distribution and the charge stability, which are the objects of the present invention, can be obtained. In the present invention, since the amount of the nonionic surfactant on the toner surface is discussed, the extraction of the nonionic surfactant hardly causes the resin toner to swell or penetrate into the toner. Methanol with strong hydrophilicity was used. Details of the extraction conditions and the like will be described later.
That (A / B) is 5.0 × 10 ⁻⁵ (g / m ² ) or more is a lower limit condition for achieving both uniformity and stability of charging of the toner required by the present invention. On the other hand, if (A / B) is smaller than 5.0 × 10 ⁻⁵ (g / m ² ), the charge leakage property is weakened, so that the toner is easily overcharged, leading to a decrease in charging stability.
On the other hand, if (A / B) is greater than 9.0 × 10 ⁻³ (g / m ² ), the amount of nonionic surfactant per unit surface area of the toner is large, and charge leakage is too strong. In particular, it is also an area where the amount of charge is likely to decrease due to moisture absorption in a high humidity environment. When the total charge amount is greatly reduced, the distribution of the charge amount becomes a region where the zero component and the reverse polarity component increase. In addition, since the leakage property is higher than the charge injection, the distribution of the charge amount is difficult to be made uniform. Furthermore, even when a sufficient amount of charge is obtained, the charge leaks rapidly, so that the charge amount becomes extremely low when the interval is increased after continuous printing, leading to a significant decrease in transfer efficiency.
In addition, the presence of an appropriate amount or more of a nonionic surfactant on the toner surface may cause the toners to aggregate during storage via the presence of the nonionic surfactant. Therefore, (A / B) being 9.0 × 10 ⁻³ (g / m ² ) or less is an upper limit condition that can achieve both uniformity and stability of charging of the toner required by the present invention.
The preferable condition of (A / B) in the present invention is that (A / B) is 5.0 × 10 ⁻⁴ or more and 4.0 × 10 ⁻³ (g / m ² ) or less. By being in this range, the toner charge amount distribution required by the present invention and the charge amount stability can be more suitably obtained.

As a result of the investigation, the nonionic surfactant contains an alkylene glycol block copolymer, and the number average molecular weight (Mn) measured by gel permeation chromatography of the alkylene glycol block copolymer is 1200 or more. It was found that the effect of the present invention can be exhibited when the amount is 40000 or less. The number average molecular weight (Mn) of the block copolymer is preferably 2000 or more and 30000 or less, and the effect of the present invention is more stably exhibited when the number is within the range. More preferably, it is 3000 or more and 18000 or less.
In the block copolymer of alkylene glycol, each block of the block copolymer is obtained by polymerizing a monomer such as oxyethylene or oxypropylene. Hydrophilicity and hydrophobicity can be controlled by the number of moles of monomer added in this block and the monomer structure. In particular, in an aqueous medium, the hydrophilicity increases as the oxyethylene chain length of ethylene glycol increases, and the hydrophobicity tends to increase as the propylene oxide chain length of propylene glycol increases. However, if it is not in an aqueous medium, if there is a spatial degree of freedom in any block body, many orientation states can be taken, and the resistance value as a molecule is diversified.
In addition, since the orientation state varies depending on the molecular size of the nonionic surfactant, the effect of the present invention is exhibited when the number average molecular weight is 1200 or more. On the other hand, when the molecular size of the nonionic surfactant increases, self-aggregation starts in the molecule. When self-aggregation becomes strong, the degree of orientation is limited because the degree of spatial freedom is lost, and the diversification of resistance values is lost. Therefore, if the number average molecular weight is 40,000 or less, the effect of the present invention is exhibited. Moreover, even if a number average molecular weight is 40000 or less, when it is larger than 30000, solubility will fall remarkably. Therefore, a sufficient amount cannot be contained in the toner unless the addition amount is increased compared to the case where the number average molecular weight is 30000 or less.
In addition, the block state of the alkylene glycol existing at both ends of the block copolymer has a high degree of freedom, so the orientation state is likely to be diversified. From this, it is considered that a block copolymer in which ethylene glycol block polymers having a small number of carbon atoms are present at both ends is preferable for obtaining the effects of the present invention.
Therefore, the block copolymer of alkylene glycol in the present invention is preferably an ethylene oxide adduct of polypropylene glycol (PPG) represented by the following structural formula (1).

[構造式中、ａ、ｂ及びｃは整数であって、ａ＞０、ｂ≧４、ｃ＞０、ａ＋ｃ≧４]

[Wherein a, b and c are integers, a> 0, b ≧ 4, c> 0, a + c ≧ 4]

On the contrary, when the both ends are block polymers of propylene oxide, the methyl group can become a steric hindrance, and therefore the orientation state tends to be limited.
Therefore, the structural formula (1) is an ethylene oxide adduct of polypropylene glycol represented by the following structural formula (2), and the number average molecular weight (Mn) of the polypropylene glycol represented by the structural formula (2) is 1000 or more. It is preferable that it is 3600 or less.

[式中、ｂは整数であって、４≦ｂ≦１００]

[Wherein b is an integer and 4 ≦ b ≦ 100]

“B” indicating the number of moles of propylene oxide added in the structural formulas (1) and (2) is preferably 4 or more and 100 or less, and more preferably 10 or more and 80 or less.
On the other hand, “a + c” indicating the total number of added moles of ethylene oxide in the structural formula (1) is preferably 4 or more, more preferably 10 or more and 1000 or less, and more preferably 30 or more and 300 or less. Further preferred.
Compared with other alkylene oxides, the ethylene oxide part in the composition represented by the structural formula (1) tends to be very hydrophilic and tends to be highly hygroscopic in a high humidity environment. Therefore, as described above, if the number average molecular weight of propylene glycol is 1000 or more, it is considered that the moisture adsorption amount in a high humidity environment can be controlled to be small in order to develop sufficient hydrophobicity. In addition, if the number average molecular weight of propylene glycol is 3600 or less, the size of the hydrophobic portion is appropriate, so that the block polymers of ethylene oxide at both ends can interact with each other in the molecule, and thus various alignment states can be obtained. Possible. As a result, charge injection to the charge point is more likely to occur, the charge amount distribution is more uniform, and the stability is also increased.

The toner of the present invention is a toner containing at least toner particles produced in an aqueous medium and inorganic fine powder, and the toner particles include at least a binder resin, a colorant, and a nonionic surfactant. contains. The binder resin includes a polyester resin produced using a titanium compound as a catalyst.
In the present invention, as described above, the effect is exhibited when titanium oxide derived from the titanium compound in the toner using the polyester resin produced using the titanium compound as a catalyst contributes as a charge point. For this reason, the content of titanium element derived from the polyester resin produced using a titanium compound as a catalyst in the toner is preferably 30 ppm or more and 3,000 ppm or less, and more preferably 100 ppm or more and 1000 ppm or less.
If the content of the titanium element is 30 ppm or more, a sufficient charge point can be obtained to exhibit the charge retention, and if it is 3,000 ppm or less, it has excellent charging stability because it has an appropriate charge leakage property. There is no overcharging.
Next, the titanium compound as the catalyst will be described. The titanium compound is preferably alkoxy titanium or a titanium chelate compound.
Specific examples of the alkoxy titanium include the following. Tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, tetrapentyloxytitanium, tetrahexyloxytitanium, tetraheptyloxytitanium, tetraoctyloxytitanium, tetranonyloxytitanium, tetradecyloxytitanium.
Of these, tetrabutoxy titanium, tetrahexyloxy titanium, and tetraoctyloxy titanium are preferable.
As said titanium chelate compound, it is preferable that a ligand is either diol, dicarboxylic acid, and oxycarboxylic acid. Among these, the ligand is particularly preferably an aliphatic diol, dicarboxylic acid, or oxycarboxylic acid.
Specific ligands include 1,2-ethanediol, 1,2-propanediol, and 1,3-propanediol for the diol. Examples of the dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and maleic acid. Examples of the oxycarboxylic acid include glycolic acid, lactic acid, hydroxyacrylic acid, α-oxybutyric acid, glyceric acid, tartronic acid, malic acid, tartaric acid, and citric acid. In particular, it is preferable to have a dicarboxylic acid as a ligand. Further, the titanium chelate compound may be a hydrate.
The counter cation of the titanium chelate compound is preferably an alkali metal. Examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium. Among these, lithium, sodium, and potassium are preferable, and sodium and potassium are particularly preferable. Two or more of these titanium chelate compounds are used in combination and used as a catalyst is also a good form of the present invention.
If it is said alkoxy titanium or a titanium chelate compound, the effect of this invention will be acquired favorably. This is considered because the catalyst of the titanium compound has optimum reactivity and hydrolyzability for obtaining an effect.
The amount of the titanium compound used as the catalyst is preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the polyester resin monomer composition. By setting it as the said usage-amount, the said titanium compound favorable to express the effect of this invention can be produced | generated in a polyester resin.
As described above, the toner particles used in the present invention contain at least a polyester resin produced using a titanium compound as a catalyst. That is, you may use together the polyester resin manufactured without using a titanium compound as a catalyst, and other resin as a binder resin.
The content of the polyester resin produced using a titanium compound as a catalyst is preferably 1% by mass or more and 100% by mass or less with respect to the entire binder resin constituting the toner particles.
Examples of the polyester resin produced using a titanium compound as a catalyst in the present invention include conventionally known polyester resins, and may be either an amorphous polyester resin or a crystalline polyester resin. Here, the crystalline polyester resin refers to a polyester resin having an endothermic peak at the time of temperature increase and an exothermic peak at the time of temperature decrease in differential scanning calorimetry (DSC) measurement. This exothermic peak is taken as the melting point of the crystalline polyester resin. Here, the DSC measurement is performed according to “ASTM D 3417-99”. The amorphous polyester resin means a polyester resin other than the crystalline polyester resin.
These polyester resins can be manufactured according to the synthesis method of a normal polyester resin. For example, a desired polyester resin can be obtained by subjecting a carboxylic acid monomer and an alcohol monomer to an esterification reaction or transesterification reaction, and then subjecting it to a polycondensation reaction under reduced pressure or by introducing nitrogen gas according to a conventional method. Can be obtained.
The weight average molecular weight (Mw) measured using gel permeation chromatography (GPC) of the amorphous polyester resin and the crystalline polyester resin used in the toner of the present invention is 2,000 to 20,000. It is preferably 2,000 to 15,000. When the weight average molecular weight of the amorphous polyester resin and the crystalline polyester resin is less than 2,000, not only the compatibility with the binder resin is likely to occur during the production of the toner, it is difficult to obtain the intended effect of the present invention. It tends to deteriorate the storage stability and durability of the toner.
On the other hand, when the weight average molecular weight of the amorphous polyester resin and the crystalline polyester resin is larger than 20,000, it is difficult to obtain good dispersibility, and further, the response to heat is lowered (it takes time to melt). ) And low temperature fixability tends to decrease.
The weight average molecular weight of the polyester resin is determined by the GPC method. As a specific measurement procedure, 0.03 g of the polyester resin to be measured is dispersed and dissolved in 10 ml of o-dichlorobenzene. The obtained solution is shaken with a shaker at 135 ° C. for 24 hours, and then the solution is filtered with a 0.2 μm filter. The obtained filtrate is used as a sample and measured under the following analysis conditions.
[Analysis conditions]
Separation column: Shodex (TSK GMHHR-H HT20) × 2
Column temperature: 135 ° C
Mobile phase solvent: o-dichlorobenzene mobile phase flow rate: 1.0 ml / min.
Sample concentration: about 0.3%
Injection volume: 300 μl
Detector: Differential refractive index detector Shodex RI-71
Further, in calculating the molecular weight of the sample, a molecular weight calibration curve prepared with a standard polystyrene resin is used. As standard polystyrene resin, Tosoh Corporation 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 are used.

The amorphous polyester resin can be obtained by a reaction between a divalent or higher polyvalent carboxylic acid and a polyhydric alcohol.
Examples of polycarboxylic acids include terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, naphthalenedicarboxylic acid, and other aromatic carboxylic acids, maleic anhydride, fumaric acid, succinic acid, alkenyl Examples thereof include aliphatic carboxylic acids such as succinic anhydride and adipic acid, and alicyclic carboxylic acids such as cyclohexanedicarboxylic acid. These polyvalent carboxylic acids can be used alone or in combination. Among these polyvalent carboxylic acids, it is preferable to use aromatic carboxylic acids, and in order to ensure good fixability, trivalent or higher carboxylic acids (trimellitic acid and its isomers) that can form a crosslinked structure or a branched structure are preferable. It is preferable to use an acid anhydride or the like in combination.
Among polyhydric alcohols, examples of dihydric alcohols include aromatic alcohols such as polyoxyethylenated bisphenol A and polyoxypropylenated bisphenol A; 1,4-cyclohexanedimethanol and the like. Examples of polyhydric alcohols having three or more valences among polyhydric alcohols include aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2, Contains aliphatic alcohols such as 4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, etc. It is.
The ratio (molar basis) of the acid component to the total amount of the acid component and the alcohol component in these monomer compositions is preferably 40 mol% to 60 mol%.
Furthermore, the amorphous polyester resin may contain a monovalent carboxylic acid. Examples of monovalent carboxylic acids include benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid Monocarboxylic acids such as dodecanoic acid and stearic acid.
Here, in the esterification or transesterification reaction or the polycondensation reaction, all monomers are charged together to increase the strength of the obtained polyester resin, or 2 to reduce the low molecular weight component of the obtained polyester resin. After first reacting the valent monomer, a trivalent or higher valent monomer can be added and reacted.

The crystalline polyester resin can be obtained by a reaction between a divalent or higher polyvalent carboxylic acid and a diol. Among them, a polyester resin mainly composed of an aliphatic diol and an aliphatic dicarboxylic acid is preferable because of its high crystallinity.
In particular, in the present invention, a polyester resin containing an aliphatic diol having 2 to 22 carbon atoms and an aliphatic dicarboxylic acid having 2 to 22 carbon atoms as main components is preferable. Here, “containing as a main component” means that 50 mol% or more (preferably 70 mol% or more) of the monomer composition is the above aliphatic dicarboxylic acid or aliphatic diol. By making the main component of the monomer composition a combination of an aliphatic diol having 2 to 22 carbon atoms and an aliphatic dicarboxylic acid having 2 to 22 carbon atoms, the order of the molecular arrangement of the resulting crystalline polyester resin can be adjusted. Therefore, it is considered that the crystallinity can be increased.
The ratio (molar basis) of the acid component to the total amount of the acid component and diol component in the monomer composition is preferably 40 mol% to 60 mol%.
The aliphatic diol having 2 to 22 carbon atoms (more preferably 2 to 12 carbon atoms) is not particularly limited, but is preferably a chain (more preferably linear) aliphatic diol. Examples of chain aliphatic diols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,4-butadiene. Examples include glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, neopentyl glycol and the like. Among these, linear aliphatic α, ω-diols such as ethylene glycol, diethylene glycol and 1,4-butanediol are particularly preferred.
Further, as described above, among the diol components, preferably 50% by mass or more, more preferably 70% by mass or more is selected from aliphatic diols having 2 to 22 carbon atoms.
In addition, a polyhydric alcohol monomer other than the aliphatic diol can be used to the extent that the characteristics of the crystalline polyester resin in the present invention are not impaired. Examples of the dihydric alcohol monomer among the polyhydric alcohol monomers include aromatic alcohols such as polyoxyethylenated bisphenol A and polyoxypropylenated bisphenol A; 1,4-cyclohexanedimethanol and the like. . Examples of the trihydric or higher polyhydric alcohol monomer among the polyhydric alcohol monomers include aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; pentaerythritol, dipentaerythritol, tritriol. Pentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, etc. Of aliphatic alcohols.
Furthermore, you may use a monovalent alcohol to such an extent that the characteristic of the crystalline polyester resin in this invention is not impaired. Examples of the monohydric alcohol include 1 such as n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, lauryl alcohol, 2-ethylhexanol, decanol, cyclohexanol, benzyl alcohol, dodecyl alcohol and the like. Functional monomers and the like are included.
On the other hand, the aliphatic dicarboxylic acid having 2 to 22 carbon atoms (more preferably 4 to 14 carbon atoms) is not particularly limited, but is preferably a linear (more preferably linear) aliphatic dicarboxylic acid. . Specific examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, Undecanedicarboxylic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, and itaconic acid, and acid anhydrides thereof are included.
Alternatively, the lower alkyl ester can be hydrolyzed and used as the aliphatic dicarboxylic acid.
As described above, among the carboxylic acid components, preferably 50% by mass or more, more preferably 70% by mass or more is selected from aliphatic dicarboxylic acids having 2 to 22 carbon atoms.
Furthermore, polyvalent carboxylic acids other than aliphatic dicarboxylic acids having 2 to 22 carbon atoms may be included. Examples of divalent carboxylic acids among other polyvalent carboxylic acid monomers include: aromatic carboxylic acids such as isophthalic acid and terephthalic acid; n-dodecyl succinic acid, aliphatic carboxylic acid of n-dodecenyl succinic acid; cyclohexane Alicyclic carboxylic acids such as dicarboxylic acids are included, and these acid anhydrides are also included. Further, the lower alkyl ester may be hydrolyzed and used as a divalent carboxylic acid.
Examples of other polyvalent carboxylic acids among other polyvalent carboxylic acid monomers include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid. Acids, aromatic carboxylic acids such as 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2 -Aliphatic carboxylic acids such as methyl-2-methylenecarboxypropane and the like, and these acid anhydrides are also included. Further, the lower alkyl ester may be hydrolyzed and used as a polyvalent carboxylic acid.
Furthermore, you may contain monovalent carboxylic acid to such an extent that the characteristic of the crystalline polyester resin in this invention is not impaired. Examples of monovalent carboxylic acids include benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid Monocarboxylic acids such as dodecanoic acid and stearic acid.
In the esterification or transesterification reaction or polycondensation reaction, all the monomers are charged together to increase the strength of the resulting polyester resin, or divalent to reduce the low molecular weight component of the resulting polyester resin. After the monomer is first reacted, a trivalent or higher monomer can be added and reacted.

In the present invention, a conventionally known polyester resin produced without using a titanium compound catalyst can be used in combination.
Here, in order to obtain a polyester resin efficiently, it is preferable to add a catalyst. Specifically, the catalyst other than the titanium compound can be carried out using a normal esterification catalyst or transesterification catalyst such as sulfuric acid, dibutyltin oxide, manganese acetate, and magnesium acetate.
Moreover, as resin other than polyester resin used for binder resin, a conventionally well-known thermoplastic resin etc. are mentioned, for example.
Specifically, homopolymers or copolymers (styrene-based resins) of styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, n-butyl acrylate,
Homopolymers or copolymers of vinyl esters such as lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate and the like having vinyl groups Homopolymers or copolymers of vinyl nitriles such as acrylonitrile and methacrylonitrile (vinyl resins); homopolymers or copolymers of vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether (vinyl resins); Homopolymers or copolymers of vinyl ketones such as vinyl methyl ketone and vinyl isopropenyl ketone (vinyl resins); Homopolymers or copolymers of olefins such as ethylene, propylene, butadiene and isoprene (olefin resins) ; Epoxy resin, polyurethane resin , Polyamide resins, cellulose resins, non-vinyl condensation resin of polyether resin and the like, and the like graft polymer of these non-vinyl condensation resin and a vinyl monomer and the like. These resins may be used alone or in combination of two or more.
Among these resins, vinyl resins are preferable. Further, a styrene-acrylic resin with a small change in charge amount of the toner in a high temperature and high humidity or low temperature and low humidity environment is more preferable.
In the case of vinyl resin, it is advantageous in that the resin particle dispersion can be easily prepared by emulsion polymerization or seed polymerization. Examples of vinyl monomers for producing vinyl resins include vinyl polymer acids such as acrylic acid, methacrylic acid, maleic acid, cinnamic acid, fumaric acid, vinyl sulfonic acid, ethyleneimine, vinyl pyridine, and vinyl amine. And monomers used as raw materials for vinyl polymer bases. Among these vinyl monomers, vinyl polymer acids are more preferable in terms of ease of formation reaction of vinyl resins, and specifically, acrylic acid, methacrylic acid, maleic acid, cinnamic acid, fumaric acid, etc. A dissociable vinyl monomer having a carboxyl group as a dissociation group is particularly preferred from the viewpoint of controlling the degree of polymerization and the glass transition temperature. Furthermore, at this time, in order to adjust the molecular weight, a chain transfer agent, a crosslinking agent, or the like can be used in combination.
The chain transfer agent is not particularly limited, and mercaptans such as octyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, halogen compounds such as carbon tetrabromide, disulfides and the like are used.
As the cross-linking agent, one having two or more unsaturated bonds such as divinylbenzene, divinylnaphthalene, divinyl ether, diethylene glycol methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, hexanediol diacrylate, diallyl phthalate, etc. should be used. In particular, divinylbenzene is preferably used.
In the present invention, the radical polymerization initiator can be appropriately used as long as it is water-soluble. For example, persulfates (potassium persulfate, ammonium persulfate, etc.), azo compounds [4,4′-azobis-4-cyanovaleric acid and its salts, 2,2′-azobis (2-amidinopropane) salts, etc.], Examples thereof include peroxide compounds such as hydrogen oxide and benzoyl peroxide.
Furthermore, the radical polymerization initiator can be combined with a reducing agent as necessary to form a redox initiator. By using a redox initiator, the polymerization activity is increased, the polymerization temperature can be lowered, and the polymerization time can be further shortened.
The polymerization temperature may be any temperature as long as it is equal to or higher than the minimum radical generation temperature of the polymerization initiator. Further, polymerization can be performed at a temperature equal to or higher than the boiling point of the dispersion (usually an aqueous medium) under pressurized conditions.
Surfactants that can be used for polymerization include sulfonates (sodium dodecylbenzenesulfonate, sodium arylalkylpolyethersulfonate, 3,3-disulfonediphenylurea-4,4-diazo-bis-amino-8- Sodium naphthol-6-sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-6-sulfonate Sulfate ester salts (sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, etc.), fatty acid salts (sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate) , Potassium stearate, calcium oleate), and the like.

  The toner particles used in the present invention contain a colorant. Examples of the colorant include phthalocyanine pigments, monoazo pigments, bisazo pigments, quinacridone pigments, and the like. Specific examples thereof include, for example, carbon black, chrome yellow, hansa yellow, benzidine yellow, slen yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brillianthamine 3B, brillianthamine. 6B, DuPont Oil Red, Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C, Rose Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Phthalocyanine Green, Malachite Green Oxalate, etc. Various pigments: acridine, xanthene, azo, benzoquinone, azine, anthraquinone, dioxane Various dyes such as gin, thiazine, azomethine, indico, thioindico, phthalocyanine, aniline black, polymethine, triphenylmethane, diphenylmethane, thiazine, thiazole, and xanthene; . These colorants may be used alone or in combination of two or more.

The toner particles used in the present invention preferably contain a release agent in order to improve the fixing performance. As a mold release agent, the melting point is preferably 150 ° C. or less, more preferably 45 ° C. to 130 ° C., from the viewpoint of achieving both durability and mold release properties.
For example, low molecular weight polyolefins such as polyethylene, silicones having a melting point (softening point) upon heating; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide, and ester waxes such as stearyl stearate Plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil, animal waxes such as beeswax, montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, etc. And particles such as mineral / petroleum wax; and modified products thereof. Of these, ester wax is preferably used from the viewpoints of stability when it is used as a release agent particle dispersion, environmental resistance when it is made into a toner, image stability, and the like.
As an optimal mold release agent that can achieve a good balance between low temperature fixability and durability by matching with the physical properties of the binder resin used in the present invention, a low melting point ester wax having a melting point of 45 ° C. or higher and 75 ° C. or lower. Is particularly preferred. In order to widen the latitude of the fixable temperature, a function can be suitably imparted by using a high melting point wax having a melting point higher than 70 ° C. and not higher than 130 ° C. in addition to the low melting point wax.
In the present invention, a charge control agent can be added to further improve the charging characteristics. Examples of the charge control agent include particles of a quaternary ammonium salt compound, a nigrosine compound, a compound made of a complex such as aluminum, iron, chromium, zinc, and zirconium. The charge control agent particles in the present invention are preferably those that are difficult to dissolve in water from the viewpoints of controlling ionic strength that affects the stability during aggregation and fusion and recycling wastewater.

The toner of the present invention exhibits the effect by having a nonionic surfactant on the toner particle surface. The nonionic surfactant can be retained on the toner surface by adding a nonionic surfactant to the toner particle dispersion and adhering it, or by using a nonionic surfactant in a highly volatile solvent such as methanol. A method of spraying and mixing with a spray after dispersing is used. However, the nonionic surfactant is preferably present as uniformly as possible on the toner surface. For this purpose, it is preferable to disperse and adhere the toner particles to a solution obtained by dissolving a nonionic surfactant in water or an aqueous methanol solution.
The timing of addition of the nonionic surfactant may be such that the nonionic surfactant is added to the binder resin dispersion, the colorant dispersion, the release agent dispersion, etc. before toner particle granulation. . However, from the viewpoint of environmental stability of the charge amount, it is preferable that the toner particles are after granulation. This is because, by adding a nonionic surfactant before granulation of toner particles, the environmental stability of the toner charge amount is reduced when the nonionic surfactant is contained even inside the toner particles. It is because it tends to do. The reason is presumed that when the nonionic surfactant is present in the resin constituting the toner in a state of absorbing water, the charge is likely to leak from the toner in a high humidity environment.
Further, as the solid-liquid separation method of the toner particles, any known method such as filtration, centrifugation, decantation, etc. may be used. Also, any cleaning method may be used, but a method of cleaning the obtained toner particle cake using a vacuum belt filter is preferable. By using this method, it is possible to easily control the content of the nonionic surfactant on the surface of the toner particles. In this method, a toner particle cake is obtained without using a nonionic surfactant, and then washed with a nonionic surfactant solution or a nonionic surfactant dispersion having a desired concentration. In addition, the amount of nonionic surfactant present on the toner surface can be easily controlled.

Next, the toner of the present invention will be described in detail.
The toner particles used in the present invention are not particularly limited as long as they are produced in an aqueous medium.
Specific examples of the method for producing toner particles in an aqueous medium include an emulsion aggregation method, a dissolution suspension method, and a suspension polymerization method. Among them, the titanium compound in the polyester resin and the nonionic surface activity are mentioned. The emulsion aggregation method is also preferred in order to allow the agent to interact uniformly. Specifically, the toner particles used in the invention of the present application are binder resin particles, colorant particles, and binder resin particles, colorant particles, and an aqueous medium containing at least release agent particles as necessary. In addition, toner particles obtained by forming aggregated particles containing at least release agent particles and the like as necessary and then fusing the aggregated particles by heating are preferable.
Regarding the toner obtained by the melt-kneading and pulverizing method, after the toner particles are produced by the melt-kneading and pulverizing method using the polyester resin produced by using the constitution of the present invention, that is, the titanium compound as a catalyst, the non-ion described above When the surface treatment was carried out with the surfactant, the effect of the present invention was not obtained. It is presumed that this is because when the polyester resin is melt-kneaded at high temperature and non-aqueous, the dehydration reaction proceeds in the polyester resin and the bond between the polyester and titanium oxide is broken.
Hereinafter, a method for producing toner particles using the emulsion aggregation method will be exemplified and described in detail, but the production method is not limited to the method.

(Dispersion preparation process)
For example, the binder resin particle dispersion is prepared as follows. That is, the resin in the binder resin particle is a homopolymer or copolymer of a vinyl monomer such as the ester having a vinyl group, the vinyl nitrile, the vinyl ether, or the vinyl ketone (vinyl resin). ), The vinyl monomer is subjected to emulsion polymerization or seed polymerization in an ionic surfactant to form a vinyl monomer homopolymer or copolymer (vinyl resin). A dispersion is prepared by dispersing resin particles in an ionic surfactant.
When the resin in the binder resin particles is a resin other than the homopolymer or copolymer of the vinyl monomer, the resin is added to an aqueous medium in which an ionic surfactant or a polymer electrolyte is dissolved. Mix. Thereafter, this solution is heated to a melting point or a softening point or higher and dissolved, and resin particles other than vinyl resin are dispersed in the ionic surfactant using a dispersing machine having a strong shearing force such as a homogenizer. A dispersion is prepared.
The dispersion means is not particularly limited, and examples thereof include known dispersion apparatuses such as a rotary shear type homogenizer and a ball mill having a medium, a sand mill, and a dyno mill.
The number average particle diameter of the binder resin particles is usually 1 μm or less, preferably 0.01 to 1.00 μm. When the number average particle size exceeds 1.00 μm, the particle size distribution of the finally obtained toner is broadened, free particles are generated, and performance and reliability are liable to be lowered. On the other hand, when the number average particle diameter is within the above range, there are no disadvantages, and the uneven distribution among the toners is reduced, the dispersion in the toner is improved, and the variation in performance and reliability is advantageous. .
The colorant particle dispersion is obtained by dispersing at least colorant particles in a dispersant. The number average particle diameter of the colorant particles is preferably 0.5 μm or less, and more preferably 0.2 μm or less. When the number average particle diameter exceeds 0.5 μm, irregular reflection of visible light cannot be prevented, and when coarse particles are present, coloring power, color reproducibility, and OHP permeability are adversely affected, and agglomeration described later. In the process, the binder resin particles and the colorant particles are not aggregated, or even when aggregated, they may be detached at the time of fusion, which is not preferable in that the quality of the obtained toner may be deteriorated. On the other hand, when the number average particle diameter is within the above range, it is advantageous in that the above disadvantages are eliminated, uneven distribution between toners is reduced, dispersion in the toner is improved, and variations in performance and reliability are reduced. is there.
The release agent particle dispersion is obtained by dispersing at least release agent particles in a dispersant. The number average particle size of the release agent particles is preferably 2.0 μm or less, and more preferably 1.0 μm or less. When the number average particle diameter exceeds 2.0 μm, the content of the release agent tends to occur between the toner particles, which adversely affects the stability of the image over a long period of time. On the other hand, when the number average particle diameter is within the above range, uneven distribution among toners is reduced, dispersion in the toner is improved, and variations in performance and reliability are reduced.
The combination of the colorant particles and the binder resin particles, and the combination of the colorant particles and the binder resin particles and the release agent particles used as necessary are not particularly limited and may be used depending on the purpose. Can be selected freely.
In addition to the binder resin particle dispersion, the colorant particle dispersion, and the release agent particle dispersion used as necessary, a particle dispersion obtained by dispersing appropriately selected particles in a dispersant. Furthermore, you may mix.
The particles contained in the particle dispersion are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include internal additive particles, charge control agent particles, inorganic particles, and abrasive particles. In the present invention, these particles may be dispersed in the binder resin particle dispersion or the colorant particle dispersion.
The number average particle diameter of the charge control agent particles is usually 1 μm or less, preferably 0.01 to 1.00 μm. When the number average particle size exceeds 1.00 μm, the particle size distribution of the finally obtained toner is widened, and the performance and reliability are likely to be lowered. On the other hand, when the number average particle diameter is within the above range, there are no disadvantages, and the uneven distribution among the toners is reduced, the dispersion in the toner is improved, and the variation in performance and reliability is advantageous. .
Examples of the dispersant contained in the binder resin particle dispersion, the colorant particle dispersion, the release agent fine dispersion, the particle dispersion, and the like include an aqueous medium containing a polar surfactant. It is done. Examples of the aqueous medium include water such as distilled water and ion exchange water, and alcohols. These may be used individually by 1 type and may use 2 or more types together. The content of the polar surfactant cannot be generally defined and can be appropriately selected according to the purpose.
Examples of the polar surfactant include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type Is mentioned. Specific examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate and the like. Specific examples of the cationic surfactant include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like. These may be used individually by 1 type and may use 2 or more types together.
In the present invention, these polar surfactants and nonpolar surfactants can be used in combination. Examples of the nonpolar surfactant include nonionic surfactants such as polyethylene glycol, alkylphenol ethylene oxide adducts, and polyhydric alcohols.
The content of the colorant particles is preferably 1 to 10 parts by mass with respect to 100 parts by mass of the binder resin in the aggregated particle dispersion when the aggregated particles are formed.
The content of the releasing agent particles is about 1 to 25 parts by mass with respect to 100 parts by mass of the binder resin in the aggregated particle dispersion when the aggregated particles are formed, and 5 to 20 parts by mass. Is preferred. When the content is less than 5 parts by mass, it is difficult to obtain a sufficient release effect and the low-temperature fixability tends to be poor. On the other hand, if the content of the release agent exceeds 20 parts by mass, the amount of the release agent present on the surface or the amount of precipitation increases with the endurance deterioration of the toner, so that the fog characteristic tends to be lowered. Moreover, when the said content is larger than 20 mass parts, a particle size distribution may spread depending on the kind of mold release agent, and a characteristic may deteriorate. In this case, for example, when the resin particles are produced, the above problem can be solved by performing seed polymerization on the release agent.
Furthermore, in order to control the chargeability of the obtained toner in more detail, the charge control particles and the binder resin particles may be added after the aggregated particles are formed.
The particle size measurement of the binder resin particles, the colorant particle dispersion, the release agent fine dispersion, the particle dispersion, and the like was performed using a laser diffraction / scattering particle size distribution measuring apparatus LA-920 manufactured by Horiba. I went.

(Aggregation process)
The aggregating step for forming the agglomerated particles includes the binder resin particles, the colorant particles, and the binder resin particles, the colorant particles, and, if necessary, in an aqueous medium containing at least the binder resin particles and the release agent particles as necessary. This is a step of forming aggregated particles including at least release agent particles.
The agglomerated particles can be formed in the aqueous medium by, for example, adding and mixing a pH adjusting agent, an aggregating agent, and a stabilizer in the aqueous medium, and appropriately adding temperature, mechanical power, and the like.
Examples of the pH adjuster include alkalis such as ammonia and sodium hydroxide, and acids such as nitric acid and citric acid. Examples of the flocculant include monovalent metal salts such as sodium and potassium; divalent metal salts such as calcium and magnesium; trivalent metal salts such as iron and aluminum; and alcohols such as methanol, ethanol and propanol. It is done.
Examples of the stabilizer mainly include the polar surfactant itself or an aqueous medium containing the same. For example, when the polar surfactant contained in each particle dispersion is anionic, a cationic one can be selected as the stabilizer.
The addition / mixing of the flocculant and the like is preferably performed at a temperature not higher than the glass transition temperature of the resin contained in the aqueous medium. When mixing is performed under this temperature condition, aggregation proceeds in a stable state. Mixing can be performed using, for example, a known mixing device, a homogenizer, a mixer and the like.
In the aggregation step, the second binder resin particles are adhered to the surface of the aggregated particles using the binder resin particle dispersion containing the second binder resin particles to form a coating layer (shell layer). By doing so, it is possible to obtain aggregated particles having a core / shell structure in which a shell layer is formed on the surface of the core aggregated particles. Note that the second binder resin particles used at this time may be the same as or different from the binder resin particles constituting the core aggregated particles. The aggregating step may be repeatedly performed in multiple steps.

(Aging process)
The aging step is a step of heating and fusing the obtained aggregated particles. Before entering the ripening step, the pH adjuster, the polar surfactant, the nonpolar surfactant, and the like can be appropriately added in order to prevent fusion between toner particles.
The heating temperature may be the glass transition temperature of the resin contained in the aggregated particles (the glass transition temperature of the resin having the highest glass transition temperature when there are two or more types of resin) or the decomposition temperature of the resin. Therefore, the temperature of the heating varies depending on the type of resin of the binder resin particles and cannot be generally defined. However, generally, the glass transition temperature of the resin contained in the aggregated particles is 140 ° C. is there. In addition, the said heating can be performed using a publicly known heating apparatus and instrument.
As the fusing time, a short time is sufficient if the heating temperature is high, and a long time is necessary if the heating temperature is low. That is, the fusion time depends on the temperature of heating and cannot be defined in general, but is generally 30 minutes to 10 hours.
The toner particles obtained through the above steps can be solid-liquid separated according to a known method, the toner particles can be recovered, and then washed, dried, and the like under appropriate conditions.

(External addition process)
In the present invention, an inorganic fine powder generally known as an external additive is added to the toner particle surface. As the inorganic fine powder used in the present invention, known inorganic fine particles are used, and in order to improve charging stability, developability, fluidity, and cleaning properties, it is preferable that the silica particles have been subjected to hydrophobic treatment. .
The above-mentioned hydrophobized silica particles are silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane coupling agents, silane coupling agents having a functional group, for the purpose of hydrophobicity and chargeability control, etc. In addition, it is desirable to treat with a treating agent such as an organic silicon compound or an organic titanium compound, or in combination with various treating agents.
For example, silane coupling agents typically include dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, hexamethyldisilazane, allylphenyldichlorosilane, benzyldimethylchlorosilane, vinyltriethoxysilane, γ- Examples thereof include methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, divinylchlorosilane and the like. In addition, a well-known method can be used for the processing method containing the addition amount of a processing agent.
The total amount of the inorganic fine powder is preferably 1.0 to 5.0 parts by mass with respect to 100 parts by mass of the toner particles. More preferably, it is 1.0 to 2.5 parts by mass.

Hereafter, the measuring method of the various physical-property values concerning this invention is demonstrated.
<Measurement of theoretical specific surface area (B) obtained from particle size distribution of toner and measurement of weight average particle size (D4) of toner>
The theoretical specific surface area (B) and the weight average particle diameter (D4) of the toner determined from the particle size distribution of the toner are calculated as follows. In addition, about the measurement of the said theoretical specific surface area (B) and a weight average particle diameter (D4), the process to (6) mentioned later is common by each.
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 is set as follows.
On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) 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) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, 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) About 30 ml of the electrolytic aqueous solution is put 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. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikkaki Bios) with an electrical output of 120 W is prepared. A predetermined amount of ion-exchanged water is placed in a water tank of an ultrasonic disperser, and about 2 ml of the contamination 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, about 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 of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Measurement is performed until the number of measured particles reaches 50,000.
Thereafter, the process proceeds to (7-1) in the case of measurement of the theoretical specific surface area (B), and proceeds to (7-2) in the case of the weight average particle diameter (D4).
(7-1) The measurement data is analyzed with the dedicated software attached to the apparatus, and the theoretical specific surface area is calculated as described later. First, the result of the next 16 channels is calculated on the “analysis / number statistical value (arithmetic mean)” screen when the graph / number% is set in the dedicated software. Specifically, in the measurement result of the particle size distribution (number statistic value) of the measured toner sample, it is divided into the following 16 channels and the number% of the particle diameters in each range range is calculated.

Number CH range DIF%
1 1.587-2.000 μm N ₁
2 2.000 to 2.520 μm N ₂
3 2.520-3.175 μm N ₃
4 3.175 to 4.000 μm N ₄
5 4.000-5.040 μm N ₅
6 5.040-6.350 μm N ₆
7 6.350-8.000 μm N ₇
8 8.000-10.079 μm N ₈
9 10.079-12.699 μm N ₉
10 12.699-16.000 μm N ₁₀
11 16.000-20.159 μm N ₁₁
12 20.159-25.398 μm N ₁₂
13 25.398-32.000 μm N ₁₃
14 32.000-40.317 μm N ₁₄
15 40.317-50.797 μm N ₁₅
16 50.797 to 64.000 μm N ₁₆

Next, it is assumed that the particles in the range of each range are true spherical particles having a particle size just in the middle of each range and a specific gravity of 1.00 (g / cm ³ ) (for example, 1.587 to 2.000 μm). All particles in the range are assumed to be 1.7935 μm). Then, the theoretical specific surface area (m ² / g) of the measured toner is calculated from the surface area and volume per particle of each range of particles and the number% of the particles of each range.
That is, assuming that the radius of the particle diameter in the middle of a certain range is Rn (m) and the number% of the range is Nn (number%), the calculation is performed for all the corresponding ranges. (B) is calculated as follows.
Theoretical specific surface area B (m ² / g)
= {Σ (4πRn ² × Nn)} / [Σ {(4/3) πRn ³ × Nn × 1.00 × 10 ⁻⁶ }]
(N = 1-16)

(7-2) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the “analysis / volume statistics (arithmetic average)” screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

<Measurement of Extraction Amount of Nonionic Surfactant Extracted from Toner Surface>
The extraction amount of the nonionic surfactant extracted from the toner surface is determined as follows using ¹ H-NMR (nuclear magnetic resonance) measurement.
First, 50 mL of methanol and 5 g of toner are precisely weighed and mixed well in a sample bottle, and then ultra-high with a tabletop ultrasonic cleaner (trade name “B2510J-MTH”, manufactured by Branson) with an oscillation frequency of 42 kHz and an electrical output of 125 W. Irradiate with sound waves for 30 minutes. Thereafter, filtration is performed using a solvent-resistant membrane filter “Maeshori Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm. After removing methanol from the filtrate by an evaporator, the filtrate is dissolved with 10 mg of trichlorosilane (TMS) in deuterated chloroform (1% TMS) and analyzed by ¹ H-NMR.
Extraction amount A of nonionic surfactant extracted from the toner surface using a TMS intensity standard calibration curve obtained using the same surfactant as the surfactant already contained in the toner (Ppm) is calculated. The calibration curve is prepared from the TMS intensity and the peak intensity ratio derived from hydrogen of 3.0 ppm to 5.0 ppm oxyalkylene group.
The measurement apparatus and measurement conditions are as follows.
Apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Frequency range: 10500Hz
Integration count: 1024 times Measurement temperature: 40 ° C

<Calculation of number average molecular weight (Mn) of block polymer or copolymer of alkylene glycol in nonionic surfactant>
The number average molecular weight (Mn) of the block copolymer of alkylene glycol in the nonionic surfactant in the present invention is measured by gel permeation chromatography (GPC) as follows.
First, a nonionic surfactant (alkylene glycol block copolymer) is dissolved in tetrahydrofuran (THF) over 24 hours at room temperature. The obtained solution is filtered through a solvent-resistant membrane filter “Maescho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml
In calculating the molecular weight of the sample, standard polystyrene resin (trade names “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used.

<Measurement of titanium element content in toner>
The titanium element content is measured using a wavelength dispersive X-ray fluorescence analyzer.
The measurement of fluorescent X-rays conforms to JIS K 0119-1969, and is specifically as follows.
As a measuring device, a wavelength dispersion type fluorescent X-ray analyzer “Axios” (manufactured by PANalytical) and attached dedicated software “SuperQ ver. 4.0F” (manufactured by PANalytical) for setting measurement conditions and analyzing measurement data ) Is used. Here, rhodium (Rh) is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 27 mm, and the measurement time is 10 seconds. Further, when measuring a light element, it is detected by a proportional counter (PC), and when measuring a heavy element, it is detected by a scintillation counter (SC).
As a measurement sample, about 4 g of toner is put in a dedicated aluminum ring for press and leveled, and a tablet-forming compressor “BRE-32” (manufactured by Maekawa Test Instruments Co., Ltd.) is used for 60 seconds at 20 MPa. Pellets that are pressed and molded to a thickness of about 2 mm and a diameter of about 39 mm are used.
The measurement is performed under the above conditions, the element is identified based on the obtained X-ray peak position, and the concentration is calculated from the count rate (unit: cps) which is the number of X-ray photons per unit time.
On the other hand, titanium dioxide (TiO ₂ ) fine powder is added to 100 parts by mass of toner particles so as to be 0.10 parts by mass, and sufficiently mixed using a coffee mill. Similarly, fine particles of titanium dioxide are mixed with toner particles so as to be 0.20 parts by mass and 0.50 parts by mass, respectively, and these are used as samples for a calibration curve.
For each sample, a pellet for a calibration curve was prepared as described above using a tablet molding compressor, and when LiF200 was used for a spectroscopic crystal, a diffraction angle (2θ) = 86.11 ° was observed. The counting rate (unit: cps) of Ti-Kα rays is measured. At this time, the acceleration voltage and the current value of the X-ray generator are 40 kV and 60 mA, respectively. A calibration curve of a linear function is obtained with the X-ray count rate obtained on the vertical axis and the added amount of TiO ₂ in each calibration curve sample on the horizontal axis.
Next, the toner to be analyzed is formed into pellets as described above using a tablet molding compressor, and the counting rate of the Ti-Kα ray is measured. Then, the titanium element content in the toner is determined from the calibration curve.

Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples as long as the gist thereof is not exceeded. In addition, all the parts and% of an Example and a comparative example are mass references | standards unless there is particular notice.
<Method for Producing Nonionic Surfactant 1>
6.0 parts by mass of 5,10,15,20-tetraphenylporphyrin (TPP) was placed in a flask equipped with a three-way cock, and after the inside of the container was replaced with dry nitrogen, 245 parts by mass of dichloromethane was added and dissolved. To this solution, 35.0 parts by mass of a 5.0% by mass diethylaluminum chloride solution in a hexane solvent was added and reacted at room temperature for 5 hours. The reaction mixture was subjected to solvent removal under reduced pressure to obtain 5,10,15,20-tetraphenylporphyrin (TPP) aluminum chloride catalyst.
1.0 part by mass of the TPP aluminum chloride catalyst and 2.0 parts by mass of methanol were dissolved in 50 parts by mass of dichloromethane, the inside of the container was replaced with dry nitrogen, and the mixture was cooled in a liquid nitrogen bath. To this, 120 parts by mass of purified propylene oxide was introduced by a trap-to-trap method. The reaction was performed at room temperature for 60 hours under a nitrogen atmosphere. Here, when a part of the reaction product was taken out and the molecular weight was measured by GPC, the number average molecular weight (Mn) was 2000. 700 parts by mass of purified ethylene oxide was further introduced into the reaction product by a trap-to-trap method, and reacted at room temperature for 120 hours under nitrogen. 300 parts by mass of methanol was added to complete the polymerization reaction. Next, 3.0 parts by mass of activated carbon was added and stirred for 3 hours to adsorb the catalyst in the mixed solution to the activated carbon. Then, the activated carbon which adsorb | sucked the catalyst was removed by filtration, the solvent was removed under reduced pressure, and the nonionic surfactant 1 was obtained. A part of the obtained nonionic surfactant 1 was dissolved in tetrahydrofuran, GPC measurement was performed, and the molecular weight distribution was measured. The number average molecular weight (Mn) was 15000.

<Method for Producing Nonionic Surfactants 2-9>
Nonionic surfactants 2 to 9 were produced in the same manner as the production method of nonionic surfactant 1 except that the type and amount of alkylene oxide used were changed as shown in Table 1.

<Method for producing polyester resin 1>
A reactor equipped with a stirrer, a thermometer, and an outflow cooler is 20 parts by mass of propylene oxide modified bisphenol A (2 mol adduct), 80 parts by mass of propylene oxide modified bisphenol A (3 mol adduct), and 20 masses of terephthalic acid. Part, 20 parts by mass of isophthalic acid and 0.50 parts by mass of tetrabutoxytitanium were added, and an esterification reaction was carried out at 190 ° C. Thereafter, 1 part by mass of trimellitic anhydride (TMA) was added, the temperature was raised to 220 ° C., the pressure inside the system was gradually reduced, and a polycondensation reaction was performed at 150 Pa to obtain polyester resin 1. The polyester resin 1 is shown in Table 2.

<Method for producing polyester resins 2 to 8>
In the production method of polyester resin 1, polyester resins 2 to 8 were obtained in the same manner as polyester resin 1 except that the kind and amount of raw material monomer used and the kind and amount of polycondensation catalyst were changed. The obtained polyester resins 2 to 8 are shown in Table 2.

<Method for producing polyester resin 9>
100 parts by mass of polyester resin 7 and 0.2 parts by mass of titanium oxide were melt-kneaded to obtain polyester resin 9. The obtained polyester resin 9 is shown in Table 2.

(Preparation of polyester resin particle dispersion 1)
-Polyester resin 1 200 parts by mass-Ion-exchanged water 500 parts by mass The above materials are put in a stainless steel container, heated and melted to 95 ° C in a warm bath, and 7800 rpm is sufficient using a homogenizer (IKA: Ultra Turrax T50). While stirring, add 0.1N sodium bicarbonate to increase the pH above 7.0. Thereafter, a mixed solution of 3 parts by mass of sodium dodecylbenzenesulfonate and 297 parts by mass of ion-exchanged water was gradually added dropwise and emulsified and dispersed to obtain a polyester resin particle dispersion 1. When the particle size distribution of the polyester resin particle dispersion 1 was measured using a particle size measuring device (LA-920, manufactured by Horiba, Ltd.), the number average particle size of the polyester resin particle dispersion 1 contained was 0.25 μm. In addition, coarse particles exceeding 1 μm were not observed.

(Preparation of polyester resin particle dispersions 2 to 9)
In the preparation of the polyester resin particle dispersion 1, polyester resin particle dispersions 2 to 9 are obtained in the same manner as the preparation of the crystalline polyester resin particle dispersion 1 except that the polyester resin 1 is changed to polyester resins 2 to 9. It was.
When the particle size distributions of the polyester resin particle dispersions 2 to 9 were measured using a particle size measuring device (LA-920, manufactured by Horiba, Ltd.), the number average particle sizes of the polyester resin particle dispersions 2 to 8 included were respectively They were 0.27 μm, 0.31 μm, 0.24 μm, 0.26 μm, 0.21 μm, 0.21 μm, 0.23 μm, and 0.30 μm, and no coarse particles exceeding 1 μm were observed.

(Preparation of release agent particle dispersion)
・ Ion-exchanged water 500 parts by mass ・ Releasing agent (ester compound mainly composed of behenyl behenate) 250 parts by mass (Unistar M-2222SL, manufactured by NOF Corporation)
Put the above materials in a stainless steel container, heat and melt to 95 ° C. in a warm bath, add 0.1N sodium hydrogen carbonate with sufficient stirring at 7800 rpm using a homogenizer (IKA: Ultra Tarrax T50) to adjust the pH. Make it larger than 7.0. Thereafter, a mixed solution of 5 parts by mass of sodium dodecylbenzenesulfonate and 245 parts by mass of ion-exchanged water was gradually added dropwise to carry out emulsification dispersion. When the particle size distribution of the release agent particles contained in this release agent particle dispersion was measured using a particle size measuring device (LA-920, manufactured by Horiba, Ltd.), the number average particle size of the release agent particles contained was , 0.35 μm, and coarse particles exceeding 1 μm were not observed.

(Preparation of colorant particle dispersion)
・ C. I. Pigment Blue 15: 3 100 parts by mass, sodium dodecylbenzenesulfonate 5 parts by mass, ion-exchanged water 400 parts by mass or more were mixed and dispersed using a sand grinder mill. When the particle size distribution of the colorant particles contained in this colorant particle dispersion was measured using a particle size measuring device (LA-920, manufactured by Horiba, Ltd.), the number average particle size of the colorant particles contained was 0.00. No coarse particles of 2 μm or more than 1 μm were observed.

<Production Example of Toner 1>
・ Polyester resin particle dispersion 1 425 parts by mass (equivalent to 85 parts by mass of polyester resin)
・ Polyester resin particle dispersion 2 75 parts by mass (equivalent to 15 parts by mass of polyester resin)
-Colorant particle dispersion 50 parts by weight-Release agent particle dispersion 40 parts by weight-Sodium dodecylbenzenesulfonate 5 parts by weight Polyester resin particle dispersion 1, polyester in a reactor (volume 1 liter flask, anchor blade with baffle) The resin particle dispersion 2, the release agent particle dispersion, and sodium dodecylbenzenesulfonate are charged and mixed uniformly. On the other hand, the colorant particle dispersion is uniformly mixed in a 500 mL beaker, and this is gradually added to the reactor while stirring to obtain a mixed dispersion. While stirring the obtained mixed dispersion, 0.5 part by mass of an aluminum sulfate aqueous solution as a solid content was dropped (aggregation step).
After completion of the dropwise addition, the system was replaced with nitrogen, and the system was maintained at 50 ° C. for 1 hour and further at 55 ° C. for 1 hour.
Thereafter, the temperature was raised and maintained at 90 ° C. for 30 minutes (thermal fusion process). Thereafter, the temperature was lowered to 63 ° C. and then held for 3 hours (aging process). The reaction at this time was performed in a nitrogen atmosphere. After completion of the predetermined time, cooling was performed until the temperature reached room temperature at a rate of 0.5 ° C. per minute.
After cooling, the reaction product was subjected to solid-liquid separation with a 10 L pressure filter under a pressure of 0.4 MPa to obtain a toner cake. Thereafter, ion-exchanged water was added to the pressure filter until the water became full, and washing was performed at a pressure of 0.4 Mpa. Further, the same washing was carried out for a total of 3 washings. This toner cake was dispersed in 1 L of a 50/50 mixed solvent of methanol / water in which 0.15 parts by mass of nonionic surfactant 1 was dissolved to obtain a surface-treated toner particle dispersion.
The toner particle dispersion was poured into a pressure filter, and 5 L of ion exchange water was further added. After solid-liquid separation under a pressure of 0.4 MPa, fluidized bed drying was performed at 45 ° C. to obtain toner particles.
Toner 100 was obtained by stirring and mixing 100 parts by mass of the toner particles with 1.0 part by mass of hydrophobized silica having a BET specific surface area of 50 (m ² / g). The obtained toner 1 is shown in Tables 3 and 4.

<Production Examples of Toner 2 to 12 and Toner 16 to 21>
In the production example of the toner 1, the toner 2 is the same as the toner 1 except that the type and amount of the polyester resin particle dispersion used and the type and amount of the nonionic surfactant are changed as shown in Table 3. To 12 and toners 16 to 21 were obtained. The obtained toners 2 to 12 and toners 16 to 21 are shown in Tables 3 and 4.

<Production Example of Toner 13>
500 parts by mass of 0.1 M Na ₃ PO ₄ aqueous solution is added to 720 parts by mass of ion-exchanged water and heated to 60 ° C., and then 72 parts by mass of 1.0 M CaCl ₂ aqueous solution is added to contain a dispersion stabilizer. An aqueous medium was obtained.
-Styrene 70 mass parts-N-butyl acrylate 20 mass parts-Polyester resin 2 10 mass parts-C.I. I. Pigment Blue 15: 3 10 parts by mass The above formulation was uniformly dispersed and mixed using an attritor (Mitsui Miike Chemical Co., Ltd.) to obtain a monomer composition. The monomer composition was heated to 60 ° C., 10 parts by weight of a release agent (behenyl behenate) was added, mixed and dissolved, and then a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile). ) 5.5 parts by mass were dissolved.
The monomer composition was put into the aqueous medium and stirred at 12,000 rpm using a TK homomixer in a nitrogen atmosphere at 60 ° C. for granulation. Thereafter, the reaction was carried out at 70 ° C. for 5 hours while stirring with a paddle stirring blade, then the temperature was raised to 90 ° C. and the mixture was stirred as it was for 2 hours. After completion of the reaction, the suspension was cooled and washed with acid by adding hydrochloric acid.
The reaction product was subjected to solid-liquid separation with a 10 L pressure filter under a pressure of 0.4 MPa to obtain a toner cake. Thereafter, ion-exchanged water was added to the pressure filter until the water became full, and washing was performed at a pressure of 0.4 Mpa. Further, the same washing was carried out for a total of 3 washings. This toner cake was dispersed in 1 L of a 50/50 mixed solvent of methanol / water in which 0.10 parts by mass of nonionic surfactant 1 was dissolved to obtain a surface-treated toner particle dispersion.
The toner particle dispersion was poured into a pressure filter, and 5 L of ion exchange water was further added. Thereafter, individual liquid separation was performed under a pressure of 0.4 MPa, and fluidized bed drying was performed at 45 ° C. to obtain toner particles.
For 100 parts by mass of the toner particles, 1.0 part by mass of hydrophobized silica having a BET specific surface area value of 300 (m ² / g) and hydrophobization having a BET specific surface area value of 50 (m ² / g) Toner 13 was obtained by stirring and mixing with 0.5 part by mass of the treated silica. The obtained toner 13 is shown in Tables 3 and 4.

<Production Example of Toner 14 and Toner 15>
In the production example of the toner 13, the toner 14 is the same as the toner 13 except that the type and amount of the polyester resin particle dispersion used and the type and amount of the nonionic surfactant are changed as shown in Table 3. And Toner 15 was obtained. The obtained toners 14 and 15 are shown in Tables 3 and 4.

<Method for Manufacturing Toner 22>
Polyester resin 5 30 parts by mass Hybrid resin 70 parts by mass (styrene, 2-ethylhexyl acrylate, α-methylstyrene, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxy Ethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, succinic acid, trimellitic anhydride, fumaric acid (mass ratio; 20: 10: 7: 30: 30: 10: 5: 3: 15) The weight average molecular weight (Mw) is 38000, the number average molecular weight (Mn) is 22000, Tg is 60 ° C.)
-Copper phthalocyanine pigment (CI Pigment Blue 15: 3) 4 parts by mass-Paraffin wax (maximum endothermic peak 67 ° C) 5 parts by mass After thoroughly mixing the materials of the above formulation with a Henschel mixer, set the temperature at 130 ° C It knead | mixed with the prepared biaxial kneader. The obtained kneaded product was cooled and coarsely pulverized to 2 mm or less with a hammer mill to obtain a coarsely pulverized product.
The obtained coarsely pulverized product was internally pulverized to a weight average particle size of 100 μm using ACM10 manufactured by Hosokawa Micron Co., Ltd. And pulverized. Thereafter, the resulting finely pulverized product was subjected to coarse particle classification using a turboplex 100ATP manufactured by Hosokawa Micron Corporation to obtain toner particles.
The toner particles were dispersed in 1 L of a 50/50 mixed solvent of methanol / water in which 0.10 parts by mass of the nonionic surfactant 1 was dissolved to obtain a surface-treated toner particle dispersion.
This toner particle dispersion was poured into a pressure filter, and 5 L of ion exchange water was further added. Thereafter, individual liquid separation was performed under a pressure of 0.4 MPa, and fluidized bed drying was performed at 45 ° C. to obtain toner particles.
For 100 parts by mass of the toner particles, 1.0 part by mass of hydrophobized silica having a BET specific surface area value of 300 (m ² / g) and hydrophobization having a BET specific surface area value of 50 (m ² / g) Toner 22 was obtained by stirring and mixing with 0.5 part by mass of the treated silica. The obtained toner 22 is shown in Tables 3 and 4.

<Image evaluation>
In the present invention, image evaluation was performed by partially modifying a commercially available color laser printer HP Color LaserJet 3525dn (manufactured by HP). In the modification, the process speed was changed to 240 mm / sec. The cartridge was filled with the toner (200 g). The image output cartridge was mounted on the cyan station, and a dummy cartridge was mounted on the other, and image evaluation was performed.
For image evaluation, images with a printing rate of 1% are output continuously in each environment under high temperature and high humidity (HH: 30 ° C, 80% RH) and low temperature and low humidity (LL: 15 ° C, 10% RH). And after outputting 1000 sheets and 15000 sheets.
As the transfer material, XEROX 4024 paper (manufactured by XEROX, 75 g / m ² ) of LETTER size was used.

<Evaluation of transfer efficiency>
After outputting 15000 sheets, an image having a solid image was output after being left for 48 hours. As a measuring apparatus, “REFLECTMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku Co., Ltd.) was used.
The transfer residual toner on the photoconductor after the transfer of the solid image was removed by taping with a Mylar tape. After that, the tape that has not been taped with the tape is a LETTER-sized XEROX
It affixed on 4200 paper (The product made by XEROX, 75 g / m < ² >). The transfer efficiency (%) (= Dr (%) − Ds (%)) was calculated from the difference between the reflectivity Ds (%) of the tape and the reflectivity Dr (%) of the tape attached without taping. A yellow filter was used as the filter. A, B, and C are levels that do not cause a problem in use, but D is a level that causes a problem in use, and some other countermeasure is required.
A: Less than 1.0% B: 1.0% or more and less than 2.0% C: 2.0% or more and less than 3.0% D: 3.0% or more

<Concentration stability>
After outputting 1000 sheets and 15000 sheets, a sample image in which 20 mm square solid black images were printed at the four corners and the center of the paper surface was output, and the average density of the five points was measured. Evaluation was made according to the following criteria from the difference (= D (15000) −D (1000)) between the average density D (1000) after printing 1000 sheets and the average density D (15000) after printing 15000 sheets. A, B, and C are levels that do not cause a problem in use, but D is a level that causes a problem in use, and some other countermeasure is required.
The image density was measured by using a “Macbeth reflection densitometer RD918” (manufactured by Macbeth Co., Ltd.) to measure the relative density with respect to an image of a white background portion having a document density of 0.00.
A: Less than 0.05 B: 0.05 or more and less than 0.10 C: 0.10 or more and less than 0.15 D: 0.15 or more

[Example 1]
Evaluation was performed using toner 1. As a result, good results were obtained for each item. The evaluation results are shown in Table 5.

[Examples 2 to 15]
Evaluation was performed in the same manner as in Example 1 using toners 2 to 15. In either case, the results were satisfactory for practical use. Table 5 shows the evaluation results of the toners 2 to 15.
Examples 2-12 and 14-15 are referred to as Reference Examples 2-12 and 14-15, respectively.

[Comparative Examples 1 to 7]
Evaluation was performed in the same manner as in Example 1 using toners 16 to 22. The toners 16 and 17 were at a level where transfer efficiency in a high-temperature and high-humidity environment was particularly poor and could not be used practically. Further, the density stability of toner 19 under high-temperature and high-humidity environment and toners 18 and 20 to 22 were low in low-temperature and low-humidity levels, so that they could not be used practically. Table 5 shows the evaluation results of the toners 16 to 22.

Claims (5)

A toner containing toner particles produced in an aqueous medium and inorganic fine particles,
The toner particles contain a binder resin, a colorant and a nonionic surfactant;
The binder resin includes a polyester resin produced using a titanium compound as a catalyst, and the content of titanium element derived from the polyester resin produced using the titanium compound as a catalyst is 100 ppm or more and 1,000 ppm or less,
The theoretical specific surface area determined from the particle size distribution of the toner using a precise particle size distribution measuring device by pore electrical resistance method, where A (ppm) is the amount of the nonionic surfactant extracted from the toner with methanol. When B is B (m ² / g), the value of the ratio of A to B (A / B) is 5.0 × 10 ⁻⁴ (g / m ² ) or more and 4.0 × 10 ^−3. (G / m ² ) or less,
The nonionic surfactant contains an alkylene glycol block copolymer represented by the following structural formula (1) , and the number average molecular weight measured by gel permeation chromatography of the alkylene glycol block copolymer is A toner having a viscosity of 1200 or more and 40000 or less.

[In Structural Formula (1), a, b and c are integers, and a> 0, b ≧ 4, c> 0, a + c ≧ 4. ] 2. The toner according to claim 1, wherein the content of titanium element derived from the polyester resin in the toner is 180 ppm or more and 300 ppm or less. The block copolymer of alkylene glycol represented by the structural formula (1) is an ethylene oxide adduct of polypropylene glycol represented by the following structural formula (2), and is an polypropylene oxide represented by the following structural formula (2). the toner according to claim 1 or 2 a number average molecular weight, characterized in that it is 1000 or more 3600 or less.

[Wherein b is an integer and 4 ≦ b ≦ 100] The ratio (A / B) is 6.3 × 10 ^-4 (G / m ² ) Above 8.4 × 10 ^-4 (G / m ² The toner according to any one of claims 1 to 3, wherein: The toner according to claim 1, wherein the toner particles are produced by an emulsion aggregation method.