JP2012058477A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide toner which has excellent charge retention properties and charge stability, and high developability even when high-speed printing is performed for a long period of time.SOLUTION: In the toner containing at least toner particles manufactured in an aqueous medium and an inorganic fine powder, the toner particles contain at last a binder resin, a colorant and a nonionic surfactant, and the binder resin contains a polyester resin manufactured by using a titanium compound as a catalyst. When the extraction amount of the nonionic surfactant to be extracted from the toner with methanol is represented by A (ppm), and a theoretical specific surface area obtained from the particle size distribution of the toner using a precision particle size distribution measurement device through a pore electrical resistivity method is represented by B (m/g), A/B is within a specific range, the nonionic surfactant includes a polyoxyalkylene structure, and the average addition molar number of oxyalkylene in the polyoxyalkylene structure is within a specific range.

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.
Examples of the toner include improving the low-temperature fixing by using a resin having a low glass transition temperature for the toner particles. Also, such toner is generally advantageous for image gloss.
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 having a melting point into a binder resin of toner is disclosed (for example, see Patent Document 1). Crystalline polyester has a sharp melt property and fluidizes in a temperature range exceeding the melting point, and is thus greatly involved in toner fixing properties. Further, sufficient strength can be obtained at a temperature not exceeding the melting point, and good durability can be found. However, polyester resins need to be improved in order to satisfy the recently required performance in terms of charge stability.
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 surface, the toner hardly adheres to various members.
However, since various performances deteriorate when a surfactant is present in the toner, it is commonly known 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.
Although surfactants in the toner field are generally in the above-described situation, there are several documents focusing on surface nonionic surfactants. 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 charge retention performance.
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 Japanese Patent Laid-Open No. 2002-131977 JP 2008-151950 A Japanese Patent No. 3107062

  The present invention is to provide a toner in view of the above background. That is, an object of the present invention is to provide a toner having excellent charge retention and charge stability and high developability even when high-speed printing is performed for a long period of time.

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 contains a polyester resin produced using a titanium compound as a catalyst, the extraction amount of the nonionic surfactant extracted from the toner by methanol is A (ppm), When the theoretical specific surface area obtained from the particle size distribution of the toner using a precision particle size distribution measuring device by the resistance method is B (m ² / g), the ratio of A to B (A / B) is 1. 0 × ^{10 -4} or more ^{9.0 × 10 -3 (g / m} 2) or less, the nonionic surfactant comprises a polyoxyalkylene structure obtained by addition polymerization of oxyalkylene A toner wherein the average addition mole number of oxyalkylene in the polyoxyalkylene structure is 5 or more and 60 or less.

  According to the present invention, it is possible to provide a toner that is excellent in charge retention and charge stability and has high developability even when high-speed printing is performed for a long period of time.

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 in order to satisfy such required performance, the present inventors have reached the present invention.
That is, the present inventors have found that the above problem can be addressed by incorporating a specific amount of a specific nonionic surfactant into a toner using 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.
First, the polyester resin used in the present invention is produced using a titanium compound as a catalyst. The titanium compound catalyst used in the production of the polyester resin has higher hydrolyzability than other polycondensation catalysts. For this reason, the catalyst of the titanium compound is hydrolyzed during the course of the polycondensation reaction, thereby changing to a titanium oxide structure. This titanium compound-derived titanium oxide is considered to be extremely finely dispersed in the polyester resin.
Moreover, the catalyst of a titanium compound advances hydrolysis, transesterifying with polyester. Therefore, when the structure is changed to titanium oxide by hydrolysis, there is a possibility that a part of the titanium oxide and the polyester resin are directly chemically interacted and exist as polyester-titanium oxide. Further, it is considered that the catalyst of the titanium compound does not change the structure to titanium oxide at a time, but gradually expands the domain of the titanium oxide structure. From this, it is considered that the domain of the titanium compound existing as a catalyst and the domain of titanium oxide exist in a mixed state. And, it is considered that extremely minute titanium oxide or polyester-titanium oxide present in the polyester resin can take various resistance values depending on the particle diameter, the size of the domain of the titanium oxide structure, and the like. Therefore, when finely dispersed titanium oxide or polyester-titanium oxide accumulates electric charge in the polyester resin, it acts as a charge point (electric storage point). Therefore, it can be charged up to the inside of the binder resin constituting the toner, and it is considered that the charge can be stably maintained higher than usual.
However, simply using a polyester resin produced by using a titanium compound as a catalyst for the binder resin of the toner, the charge cannot be stored efficiently and quickly at the charge point. This is believed to be due to the large resistance difference between the polyester resin and the fine titanium oxide that is the charge point. In general, the larger the resistance value, the more charges are retained, and the smaller the resistance value, the smaller the charges are retained. 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 fine titanium oxide in the polyester resin has a considerably smaller resistance value than the polyester. Once fine titanium oxide can obtain a charge, it is considered that charge transfer is limited because it is surrounded by high resistance polyester. Therefore, the electric charge obtained on the toner surface layer cannot move to fine 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. This effect allows charge to be stored inside the toner, so that charging is stable and charge retention is 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 1.0 × 10 ⁻⁴ 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 in the above range, the charge retention and 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 1.0 × 10 ⁻⁴ (g / m ² ) or more is a lower limit condition for obtaining the effect of suppressing the adhesion of the toner to the member required by the present invention. On the other hand, if (A / B) is smaller than 1.0 × 10 ⁻⁴ (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. For this reason, since the amount of leakage exceeds the amount of injected charge, the charge rising property becomes extremely poor. Furthermore, even when the charge is sufficiently obtained, the charge leaks rapidly, so that the charge becomes extremely low and an image detrimental effect such as fogging occurs when an interval is provided after continuous printing.
Furthermore, since an appropriate amount or more of a nonionic surfactant is present on the toner surface, there is a possibility that the toner aggregates during storage through 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 the effect of suppressing adhesion of the toner to the member and the environmental stability of charging.
A more preferable condition of (A / B) in the present invention is that (A / B) is 3.0 × 10 ⁻⁴ or more and 5.0 × 10 ⁻³ (g / m ² ) or less. More preferably, it is 5.0 × 10 ⁻⁴ or more and 2.0 × 10 ⁻³ (g / m ² ) or less. By being in this range, the charge rising property and charge retention property of the toner required by the present invention can be obtained more suitably.

The nonionic surfactant used in the present invention includes a polyoxyalkylene structure obtained by addition polymerization of oxyalkylene, and the average addition mole number of oxyalkylene in the polyoxyalkylene structure is 5 or more and 60 or less. . The average added mole number is preferably 5 or more and 45 or less, and more preferably 8 or more and 18 or less.
A result suggesting that oxyalkylene has a very great effect of suppressing the adhesion of the toner to the member has been obtained. However, since it has hydrophilicity, it tends to absorb moisture in a high-humidity environment, and there is a strong tendency for attenuation of charging to become extremely large. That is, it means that there is a big problem in charge retention. Therefore, it has been said that there has been an adverse effect on electrophotographic characteristics so far, and has not received much attention in an attempt to eliminate it as much as possible.
The present invention makes it possible to achieve both rising characteristics of charge and charge retention by the tunnel effect to fine titanium oxide, which is manifested by diversification of the orientation state of oxyalkylene. When the average added mole number of the oxyalkylene is less than 5, the number of orientation states is insufficient, and a sufficient tunnel effect cannot be caused. For this reason, charge stability is lowered because charge leakage is insufficient. Particularly in a low-temperature and low-humidity environment, the charge amount increases and the image density decreases as the durable output progresses.
On the other hand, when the average number of added moles of oxyalkylene is more than 60, a low-level orientation state is likely to occur, so that it is difficult to achieve a level necessary to cause a tunnel effect. In addition, since the resistance value is low, the charge leakage property is extremely high. Furthermore, since the hygroscopicity is increased, both charge retention and riseability are extremely deteriorated in a high temperature and high humidity environment. Such a toner has particularly low charging stability and causes problems such as fogging in a high temperature and high humidity environment.

The nonionic surfactant is preferably a polyoxyalkylene alkyl ether, a polyoxyalkylene alkyl ester, or a polyoxyalkylene alkyl phenyl ether, and more preferably represented by the following formula (1) or formula (2). It is a compound.
Here, the polyoxyalkylene structure is preferably a polyoxyalkylene structure obtained by addition polymerization of ethylene oxide and / or propylene oxide (that is, ethylene oxide, propylene oxide, or ethylene oxide and propylene oxide). . Therefore, the nonionic surfactant is more preferably a polyoxyalkylene alkyl ether represented by the following formula (3).

Ｒ：アルキル基
ＡＯ：オキシアルキレン
ｎ：平均付加モル数

R: alkyl group AO: oxyalkylene n: average number of added moles

Ｒ：アルキル基

R: alkyl group

In the above formulas (1) to (3), R is preferably an alkyl group having 1 to 60 carbon atoms, and more preferably an alkyl group having 5 to 30 carbon atoms.
In the above formula (3), r represents the total number of moles added of oxyethylene groups, and s represents the total number of moles added of oxypropylene groups. The nonionic surfactant used in the present invention may have a structure in which blocks of polyoxyethylene and polyoxypropylene are alternately present, in which case r and s are the sum of the added moles of each block. To express. Here, the average added mole number n is obtained by n = r + s, and is preferably within the above-mentioned range. Also, either r or s may be 0.

  In the case of the above-described nonionic surfactant, the alkyl group site functions as a hydrophobic portion, so that the hygroscopicity can be lowered as compared with other surfactants, and excessive charging leakage can be suppressed. In addition, since the polyoxyalkylene moiety is present appropriately, the charge can be sufficiently transferred into the toner by a tunnel effect.

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.
As described above, in the present invention, the titanium oxide derived from the titanium compound present in the polyester resin produced using the titanium compound as a catalyst contained in the binder resin constituting the toner particles contributes as a charge point. The effect is expressed. Therefore, in the present invention, the content of the titanium element derived from the polyester resin produced using the titanium compound in the toner as a catalyst is preferably 30 ppm to 3,000 ppm, and more preferably 100 ppm to 1000 ppm. More preferred.
If the content of the titanium element is 30 ppm or more, a sufficient charge point can be obtained to exhibit charge retention, and if it is 3,000 ppm or less, it has excellent charge 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 titanium chelate.
Specific examples of the alkoxy titanium include the following. Tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, tetrapentyloxytitanium, tetrahexyloxytitanium, tetraheptyloxytitanium, tetraoctyloxytitanium, tetranonyloxytitanium, tetradecyloxytitanium.
Of these, tetrabutyl polytitanate, tetrahexyl polytitanate, and tetraoctyl polytitanate are preferable.
As said titanium chelate, 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 examples of the diol include 1,2-ethanediol, 1,2-propanediol, and 1,3-propanediol. 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 may be a hydrate.
The counter cation of the titanium chelate 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. These titanium chelates may be used in combination of two or more and used as a catalyst.
If it is said alkoxy titanium or titanium chelate, 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 any of amorphous polyester and / or crystalline polyester. Here, the crystalline polyester means a polyester 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. Here, the DSC measurement is performed according to “ASTM D 3417-99”. Amorphous polyester refers to polyester other than crystalline polyester.
These polyester resins can be produced according to a normal polyester synthesis method. 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.
Amorphous polyester can be obtained by the reaction of 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. Of these polyvalent carboxylic acids, it is preferable to use aromatic carboxylic acids, and in order to take a crosslinked structure or a branched structure in order to ensure good fixability, tricarboxylic or higher carboxylic acids (trimerits) It is preferable to use an acid or an acid anhydride thereof in combination.
Examples of dihydric alcohols among polyhydric alcohols include aromatic alcohols such as polyoxyethylenated bisphenol A and polyoxypropylenated bisphenol A; 1,4-cyclohexanedimethanol and the like. Examples of polyhydric alcohol monomers having a valence of 3 or more among polyhydric alcohols include aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; pentaerythritol, dipentaerythritol, tripentaerythritol, 1 , 2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and other aliphatic alcohols Etc. are included.
The ratio (molar basis) between the acid component and the alcohol component of these monomer compositions is preferably acid component: alcohol component = 60: 40 to 40:60.
Furthermore, the amorphous polyester 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 the monomers are charged at once in order to increase the strength of the obtained polyester, or divalent in order to reduce the low molecular weight component of the obtained polyester. These monomers can be reacted first, and then a trivalent or higher monomer can be added and reacted.
The number average molecular weight of the amorphous polyester measured using gel permeation chromatography (GPC) is preferably 2,000 to 10,000, and more preferably 2,000 to 6,000. If the number average molecular weight of the amorphous polyester is less than 2,000, it is easy to cause compatibility with other resins contained in the binder resin during the production of toner particles, and it is difficult to obtain the intended effect of the present invention. In other words, the storage stability and durability of the toner are liable to be reduced.
On the other hand, when the number average molecular weight of the amorphous polyester is larger than 10,000, it is difficult to obtain good dispersibility, and further, the responsiveness to heat is likely to decrease (it takes time to melt, etc.), Low temperature fixability tends to decrease.

On the other hand, the crystalline polyester can be obtained by the reaction of a divalent or higher polyvalent carboxylic acid and a diol. Among these, a polyester mainly composed of an aliphatic diol and an aliphatic dicarboxylic acid is preferable because of high crystallinity.
In particular, in the present invention, a polyester 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. When the main component of the monomer composition is 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 is improved. Therefore, it is considered that the crystallinity can be increased.
The ratio (molar basis) between the acid component and the alcohol component of the monomer composition is preferably acid component: alcohol component = 60: 40 to 40:60.
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 glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, neopentyl glycol, etc. Is included. Among these, linear aliphatic α, ω-diols such as ethylene glycol, diethylene glycol and 1,4-butanediol are particularly preferred.
In addition, a polyhydric alcohol monomer other than the aliphatic diol can be used to the extent that the characteristics of the crystalline polyester 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, monovalent alcohol may be used to such an extent that the characteristics of the crystalline polyester are not impaired. Examples of monohydric alcohols include monofunctional groups such as n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, lauryl alcohol, 2-ethylhexanol, decanol, cyclohexanol, benzyl alcohol, and dodecyl alcohol. Sex 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. Here, the lower alkyl ester can be hydrolyzed and used as an aliphatic dicarboxylic acid.
Moreover, polyvalent carboxylic acid other than C2-C22 aliphatic dicarboxylic acid 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; aliphatic carboxylic acids such as n-dodecyl succinic acid and n-dodecenyl succinic acid; Alicyclic carboxylic acids such as cyclohexanedicarboxylic acid are included, and these acid anhydrides are also included. Here, the lower alkyl ester may be hydrolyzed and used as a divalent carboxylic acid.
Among other polyvalent carboxylic acid monomers, examples of trivalent or higher polyvalent carboxylic acids include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, Aromatic carboxylic acids such as 1,2,4-naphthalenetricarboxylic acid and pyromellitic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl Aliphatic carboxylic acids such as 2-methylenecarboxypropane and the like, and these acid anhydrides are also included. Here, 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 crystalline polyester 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.
Here, in the esterification or transesterification reaction or the polycondensation reaction, in order to increase the strength of the polyester obtained, all monomers are charged at once, or to reduce the low molecular weight component of the polyester component obtained, 2 After first reacting the valent monomer, a trivalent or higher valent monomer can be added and reacted.
The number average molecular weight of the crystalline polyester measured using gel permeation chromatography (GPC) is preferably 2,000 to 10,000, and more preferably 2,000 to 6,000. When the number average molecular weight of the crystalline polyester is less than 2,000, not only the compatibility with other resins contained in the binder resin is likely to occur during the production of the toner particles, and it is difficult to obtain the intended effect of the present invention. , Toner storage stability and durability are likely to be lowered.
On the other hand, if the number average molecular weight of the crystalline polyester is larger than 10,000, it is difficult to obtain good dispersibility, and further, the response to heat is likely to be lowered (it takes time to melt) and the low temperature. The fixability tends to be lowered.

The number average molecular weight of the polyester is determined by the GPC method. As a specific measurement procedure, 0.03 g of the polyester 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.

In order to obtain polyester efficiently, it is preferable to add a catalyst. Specifically, the catalyst other than the titanium compound can be used in combination with an ordinary esterification catalyst or transesterification catalyst such as sulfuric acid, dibutyltin oxide, manganese acetate, and magnesium acetate.
Examples of the resin other than the polyester resin include conventionally known thermoplastic resins. Specifically, homopolymers or copolymers of styrenes such as styrene, parachlorostyrene, α-methylstyrene (styrene resin); methyl acrylate, n-butyl acrylate, lauryl acrylate, acrylic acid 2 -Ethylhexyl, methyl methacrylate, n-propyl methacrylate, lauryl methacrylate, homopolymers or copolymers of vinyl groups such as 2-ethylhexyl methacrylate (vinyl resin); acrylonitrile, methacrylonitrile, etc. Homopolymers or copolymers of vinyl nitriles (vinyl resins); Homopolymers or copolymers of vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether (vinyl resins); Vinyl methyl ketone, vinyl isopropenyl Homopolymers or copolymers of vinyl ketones such as ketones Polymer (vinyl resin); homopolymer or copolymer of olefins such as ethylene, propylene, butadiene and isoprene (olefin resin); non-epoxy resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, etc. Examples thereof include vinyl condensation resins and graft polymers of these non-vinyl condensation resins and vinyl monomers. 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 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. And then spraying and mixing with a spray. 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 adding the nonionic surfactant is preferably after toner particle granulation, and if it is after toner particle granulation, more excellent performance was exhibited. A nonionic surfactant may be added to the binder resin dispersion, colored resin dispersion and wax resin dispersion before toner particle granulation, but there is a slight deterioration in the environmental stability of the charge amount. It was. This is presumed to be a result of the nonionic surfactant being contained even inside the toner particles by adding the nonionic surfactant before the toner particles are granulated. Specifically, it is presumed that the nonionic surfactant is present inside the resin in a water-absorbed state, and 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. In a toner manufactured using a medium other than an aqueous medium such as a kneading and pulverizing method, the dehydration reaction proceeds because of high temperature and non-aqueous. Therefore, the polyester-titanium oxide in the polyester resin loses its function as a charge point due to the dehydration reaction.
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 surfactant are mentioned. The emulsion aggregation method is also preferred in order to allow them 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.
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, when the resin in the binder resin particles is a homopolymer or copolymer (vinyl resin) of vinyl monomers such as esters having vinyl groups, vinyl nitriles, vinyl ethers, vinyl ketones. Makes resin particles made of homopolymers or copolymers of vinyl monomers (vinyl resins) ionic by conducting emulsion polymerization or seed polymerization of vinyl monomers in an ionic surfactant. A dispersion obtained by dispersing in a surfactant is prepared.
When the resin in the binder resin particles is a resin other than a homopolymer or copolymer of a vinyl monomer, the resin is mixed in an aqueous medium in which an ionic surfactant or a polymer electrolyte is dissolved. . Thereafter, the solution is heated to a melting point or a softening point or higher and dissolved, and using a dispersing device having a strong shearing force such as a homogenizer, resin particles other than the vinyl resin are dispersed in the ionic surfactant. 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, a sand mill, and a dyno mill having media.
The average particle size of the binder resin particles is usually 1 μm or less, preferably 0.01 to 1.00 μm. When the 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 average particle diameter is within the above range, there are no disadvantages, and the uneven distribution between 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 fine particles in a dispersant. 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 average particle diameter of the colorant particles is preferably 0.5 μm or less, and more preferably 0.2 μm or less. When the 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. The binder resin particles and the colorant particles are not agglomerated, or even if agglomerated, they may be detached at the time of fusion, which is not preferable in that the quality of the obtained toner may deteriorate. On the other hand, when the 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 release agent particle dispersion is obtained by dispersing at least release agent fine particles in a dispersant.
As the mold release agent, those having a melting point of 150 ° C. or lower are used, and those having a melting point of preferably 45 ° C. to 130 ° C. can satisfy 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. An example of an optimum release agent that can achieve a good balance between low-temperature fixability and durability by matching with the physical properties of the binder resin is a low melting point ester wax having a melting point of 45 ° C. or higher and 75 ° C. or lower. Further, in order to widen the latitude of the fixable temperature, in addition to the low melting point wax, a high melting point wax having a melting point higher than 70 ° C. and not higher than 130 ° C. can be used to impart a function suitably.
The 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 average particle diameter exceeds 2.0 μm, the toner content tends to be generated between the toners, which adversely affects the stability of the image over a long period of time. On the other hand, when the average particle diameter is within the above range, uneven distribution between toners is reduced, dispersion in the toner is improved, and variations in performance and reliability are reduced.
There is no restriction | limiting in particular as a combination of a colorant particle, a binder resin particle, and a mold release agent particle, According to the objective, it can select suitably suitably.

In addition to the binder resin particle dispersion, the colorant particle dispersion, and the release agent particle dispersion, a particle dispersion obtained by dispersing appropriately selected particles in the dispersant may be further mixed.
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 a binder resin particle dispersion or a colorant particle dispersion.
Examples of the charge control agent particles include particles such as quaternary ammonium salt compounds, nigrosine compounds, compounds composed of complexes of aluminum, iron, chromium, zinc, zirconium, and the like. The charge control agent particles are preferably made of materials that are difficult to dissolve in water from the viewpoint of controlling ionic strength that affects the stability during aggregation and fusion and recycling wastewater.
The average particle size of the above-mentioned particles is usually 1 μm or less, and preferably 0.01 to 1.00 μm. When the average particle size exceeds 1.00 μm, the particle size distribution of the finally obtained toner is widened, and performance and reliability are likely to be lowered. On the other hand, when the average particle diameter is within the above range, there are no disadvantages, and the uneven distribution between 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. 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. Can be 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 binder resin particles in 100 parts by mass of the binder resin particle dispersion is preferably 5 to 60 parts by mass. The content of the binder resin particles in 100 parts by mass of the aggregated particle dispersion when the aggregated particles are formed is preferably 50 parts by mass or less.
The content of the colorant particles is preferably about 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 release agent particles is about 1 to 25 parts by mass and about 5 to 20 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. Is preferred. When the content is less than 5 parts by mass, a sufficient release effect cannot be obtained and the low-temperature fixability tends to be inferior. On the other hand, when 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 deteriorate. Moreover, when content is larger than 20 mass parts, depending on the kind of mold release agent, a particle size distribution may spread 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.
Further, in order to control the chargeability of the obtained toner, the charge control particles and the binder resin particles may be added after the aggregated particles are formed.
The particle size of the colorant particle dispersion, release agent particle dispersion, particle dispersion and the like was measured using a laser diffraction / scattering particle size distribution analyzer LA-920 manufactured by Horiba. The average particle diameter is a volume-based 50% particle diameter (median diameter).

(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 adding, for example, a pH adjusting agent, an aggregating agent, and a stabilizer to the aqueous medium and mixing them, 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 a plurality of 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, polar surfactant, nonpolar surfactant and the like can be appropriately added to prevent fusion between the 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. Accordingly, the heating temperature varies depending on the type of resin of the binder resin particles and cannot be generally defined, but is generally the glass transition temperature of the resin contained in the aggregated particles to 140 ° C. In addition, heating can be performed using a publicly known heating device / apparatus.
As the fusion time, a short time is sufficient if the heating temperature is high, and a long time is required 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 external additive used in the present invention, known inorganic fine particles or resin particles are used. However, the external additive is a silica fine powder hydrophobized to improve charging stability, developability, fluidity, and cleaning properties. Is preferred. Hydrophobized silica fine powder includes silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane coupling agents, silane coupling agents having functional groups, other organic silicon compounds, organic titanium compounds, etc. It is desirable to be treated with a treatment agent. Typical examples of silane coupling agents include dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, hexamethyldisilazane, allylphenyldichlorosilane, benzyldimethylchlorosilane, vinyltriethoxysilane, and γ-methacryloxy. Examples thereof include propyltrimethoxysilane, 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.

Hereinafter, the measurement methods for various physical properties according to the present invention will be described.
<Measurement of theoretical specific surface area (B) determined 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 Nikka Ki Bios) having 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 per particle of each range and the number% of the particles in 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 in a sample bottle and mixed well, and then ultra-cleaned with a desktop 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). The calibration curve is prepared from the TMS intensity and the peak intensity ratio derived from hydrogen of the oxyalkylene group near 3.0 to 5.0 ppm. 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 average addition mole number of polyoxyalkylene chain in nonionic surfactant>
In the present invention, the average number of added moles of the polyoxyalkylene chain in the nonionic surfactant is measured by gel permeation chromatography (GPC) as follows.
First, the polyoxyalkylene used for the production of the nonionic surfactant 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.
The measured average molecular weight is divided by the unit molecular weight of the alkylene constituting the polyoxyalkylene chain, and the value obtained by rounding down the decimal point is defined as the average added mole number.

<Measurement of content of titanium element in toner or resin>
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 or resin is put in a dedicated press aluminum ring, and is flattened. Using a tablet molding compressor “BRE-32” (manufactured by Maekawa Test Instruments Co., Ltd.) , And pressurizing for 60 seconds and using pellets molded to a thickness of about 2 mm and a diameter of about 39 mm. 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 or resin so as to be 0.10 parts by mass, and sufficiently mixed using a coffee mill. Similarly, titanium dioxide fine powder is mixed with a toner or a resin 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 or resin to be analyzed is pelletized as described above using a tablet molding compressor, and the counting rate of the Ti-Kα ray is measured. Then, the content of titanium element in the toner or resin 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 polyoxyalkylene 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 wt% 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. The TPP aluminum chloride catalyst was dissolved in 1.2 parts by mass and 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, 0.90 part by mass of a 20: 1 mixture of purified ethylene oxide and purified propylene oxide was introduced by a trap-to-trap method. After reacting at room temperature for 80 hours under nitrogen, 300 parts by mass of methanol was added to terminate 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. Thereafter, the activated carbon adsorbing the catalyst was removed by filtration, and the solvent was removed under reduced pressure to obtain polyoxyalkylene 1. A part of the obtained polyoxyalkylene 1 was dissolved in tetrahydrofuran, GPC was measured, and molecular weight distribution was measured. Table 1 shows the average number of added moles of the resulting polyoxyalkylene 1 alkylene oxide.

<Method for producing polyoxyalkylene 2-6>
Polyoxyalkylenes 2 to 6 were produced in the same manner as in the production method of polyoxyalkylene 1 except that the type and amount of alkylene oxide used were changed as shown in Table 1. Table 1 shows the average number of added moles of the resulting polyoxyalkylene 2-6 alkylene oxide.

For polyoxyalkylenes 7-11, the following raw materials were used.
Polyoxyalkylene 7 Tetraethylene glycol polyoxyalkylene 8 manufactured by Tokyo Chemical Industry Co., Ltd. Pentaethylene glycol polyoxyalkylene 9 manufactured by Tokyo Chemical Industry Co., Ltd. Octaethylene glycol polyoxyalkylene 10 manufactured by Tokyo Chemical Industry Co., Ltd. Polyerylene glycol (PEG) manufactured by Sanyo Chemical Co., Ltd. ―2000)
Polyoxyalkylene 11 Polyerylene glycol (PEG-4000) manufactured by Sanyo Chemical Industries
N)
Table 1 shows the average number of added moles of alkylene oxide of polyoxyalkylenes 7 to 11.

<Method for Producing Nonionic Surfactant 1>
In a three-necked flask equipped with a reflux condenser and a stirrer, 9.3 parts by mass of polyoxyalkylene 1 was reacted with 0.15 parts by mass of metallic sodium while heating and stirring. A mixture of 1.5 parts by mass of n-chlorododecane and 50 parts by mass of hexane was gradually added thereto and reacted at 120 ° C. for 3 hours. After cooling the reaction solution, the reaction solution is neutralized with a large amount of acetone, the reaction by-product sodium chloride is precipitated, filtered, and purified by molecular distillation to obtain the nonionic surfactant 1. It was. The obtained nonionic surfactant 1 is shown in Table 2.
<Method for Producing Nonionic Surfactants 2-12>
In the production method of the nonionic surfactant 1, the same kind as that of the nonionic surfactant 1 except that the kind and amount of polyoxyalkylene used and the kind and amount of the reagent for constituting the alkyl chain were changed. The nonionic surfactant 2-12 was obtained by the method. It shows in Table 2 about the obtained nonionic surfactant 2-12.
<Nonionic surfactant 13>
As the nonionic surfactant 13, polyoxyethylene nonylphenyl ether (average added mole number 10) manufactured by Tokyo Chemical Industry Co., Ltd. was used.

<Method for producing polyester resin 1>
A reaction apparatus equipped with a stirrer, a thermometer, and an outflow cooler was added with 20 parts by mass of propylene oxide modified bisphenol A (2 mol adduct), propylene oxide modified bisphenol A (3
Mole adduct) 80 parts by mass, 20 parts by mass of terephthalic acid, 20 parts by mass of isophthalic acid and 0.30 parts by mass of tetrabutoxytitanium were added, and an esterification reaction was performed at 190 ° C. Thereafter, 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 a polyester resin 1. The polyester resin 1 is shown in Table 3.
<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 3.
<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 3.

ＴＰＡ：テレフタル酸
ＩＰＡ：イソフタル酸
ＴＭＡ：無水トリメリット酸

TPA: terephthalic acid IPA: isophthalic acid TMA: trimellitic anhydride

(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 particles contained in the polyester resin particle dispersion 1 was measured using a particle size measuring device (LA-920, manufactured by Horiba, Ltd.), the average particle size of the polyester resin particles contained was 0.00. Coarse particles of 25 μm and exceeding 1 μm were not observed.
(Preparation of polyester resin particle dispersions 2 to 8)
In preparing the polyester resin particle dispersion 1, polyester resin particle dispersions 2 to 8 were obtained in the same manner as the preparation of the polyester resin particle dispersion 1, except that the polyester resin 1 was changed to the polyester resins 2 to 8. When the particle size distribution of the polyester resin particles contained in the polyester resin particle dispersions 2 to 8 was measured using a particle size measuring device (LA-920, manufactured by Horiba, Ltd.), the average particle size of the polyester resin particles contained was respectively The particle sizes were 0.27 μm, 0.31 μm, 0.24 μm, 0.26 μm, 0.21 μm, 0.21 μm, and 0.23 μm, and no coarse particles exceeding 1 μm were observed.

(Preparation of release agent particle dispersion)
・ Ion exchange water 500 parts by mass
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 average particle size of the release agent particles contained was: Coarse particles of 0.35 μm and 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 measurement device (LA-920, manufactured by Horiba, Ltd.), the average particle size of the colorant particles contained was 0.2 μm. In addition, coarse particles exceeding 1 μm were not observed.

<Production Example of Toner 1>
・ Polyester particle dispersion 1 425 parts by mass (equivalent to 85 parts by mass of polyester resin)
・ Polyester 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 particle dispersion 1, polyester particles in a reactor (volume 1 liter flask, anchor blade with baffle) Dispersion liquid 2, release agent particle dispersion liquid and sodium dodecylbenzenesulfonate are charged and mixed uniformly. On the other hand, the colorant particle dispersion is gradually added to the reactor 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). 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 2.0 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. 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 4 and 5.
<Production Examples of Toner 2 to 12 and Toner 16 to 21>
In the production example of the toner 1, except that the type and amount of the polyester particle dispersion used and the type and amount of the nonionic surfactant are changed, the toners 2 to 12 and the toners 16 to 21 are added in the same manner as the toner 1. Obtained. The obtained toners 2 to 12 and toners 16 to 21 are shown in Tables 4 and 5.

<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 (an ester compound mainly composed of behenyl behenate) was added, mixed and dissolved, and then a polymerization initiator 2,2′-azobis (2 , 4-dimethylvaleronitrile) was dissolved in 5.5 parts by mass.
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 2.0 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. To 100 parts by mass of the toner particles, 1.0 part by mass of hydrophobic silica having a BET specific surface area of 50 (m ² / g) was stirred and mixed to obtain toner 13. The obtained toner 13 is shown in Tables 4 and 5.
<Method for Producing Toner 14 and Toner 15>
In the toner 13 production example, toner 14 and toner 15 were obtained in the same manner as toner 13 except that the type and amount of the polyester particle dispersion used and the amount of the nonionic surfactant were changed. The obtained toners 14 and 15 are shown in Tables 4 and 5.

<Image evaluation>
The 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 fog>
After outputting 15000 sheets, an image having a white background portion 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 fog value is determined by calculating the fog density (%) (= Dr (%) from the difference between the whiteness (reflectance Ds (%)) of the white background portion of the printout image and the whiteness (average reflectance Dr (%)) of the transfer region. ) -Ds (%)). 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 1.00 C: 1.00 or more and less than 1.50 D: 1.50 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 6.
[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 6 shows the evaluation results of the toners 2 to 15.
[Comparative Examples 1 to 6]
Evaluation was performed in the same manner as in Example 1 using toners 16 to 21. The toners 16, 17 and 21 were all at a level where fogging in a high temperature and high humidity environment was particularly bad and could not be used practically. Further, the density stability of toner 18 under high-temperature and high-humidity environment and toner 19 and 20 under low-temperature and low-humidity conditions were particularly poor and could not be used practically. Table 6 shows the evaluation results of the toners 16 to 21.

Claims (4)

A toner containing at least toner particles produced in an aqueous medium and inorganic fine powder,
The toner particles contain at least a binder resin, a colorant, and a nonionic surfactant,
The binder resin includes a polyester resin produced using a titanium compound as a catalyst,
The theoretical specific surface area determined from the particle size distribution of the toner using a fine particle size distribution measuring device by the pore electrical resistance method, where A (ppm) is the extraction amount of the nonionic surfactant extracted from the toner with methanol. Is B (m ² / g), the ratio of A to B (A / B) is 1.0 × 10 ⁻⁴ or more and 9.0 × 10 ⁻³ (g / m ² ) or less. ,
The nonionic surfactant includes a polyoxyalkylene structure obtained by addition polymerization of oxyalkylene, and an average addition mole number of oxyalkylene in the polyoxyalkylene structure is 5 or more and 60 or less. toner.   2. The toner according to claim 1, wherein a content of a titanium element derived from the polyester resin in the toner is 30 ppm or more and 3,000 ppm or less.   The toner according to claim 1, wherein the nonionic surfactant is a polyoxyalkylene alkyl ether or a polyoxyalkylene alkyl ester.   The toner according to claim 1, wherein the toner particles are produced by emulsion aggregation.