JP2022113640A - Toner external additive and toner - Google Patents

Abstract

To provide a toner external additive that has charge stability and can suppress variation in image density even when an image is output under a high-temperature and high-humidity environment or under conditions where humidity changes.SOLUTION: Provided is a toner external additive containing silicon polymer particles having a siloxane bond and an Si-R1 bond, the toner external additive satisfying: the following formula (1) where the total peak area attributed to the toner external additive is A and the peak area attributed to the Si-R1 bond (R1 represents an alkyl group having 1 to 6 carbon atoms) is B in a chart obtained by 29Si-NMR measurement of the toner external additive; and the following formula (2) where the total peak area attributed to the silicon polymer is SA and the peak area attributed to a T unit structure is S3 in a chart obtained by 29Si-NMR measurement of the toner external additive. 0.260≤B/A≤0.450 (1) 0.00≤S3/SA≤0.50 (2)SELECTED DRAWING: None

Description

TECHNICAL FIELD The present disclosure relates to an external additive for toner and a toner used in electrophotography using the external additive for toner.

In recent years, with the widespread use of electrophotographic full-color copiers, the demand for toners used in electrophotography to support high-speed printing, environmental stability, and long life has been increasing. Conventionally, silica is widely known as an external additive used in toners. In general, examples have been reported in which silica obtained by a dry process or a wet process (sol-gel method) is subjected to a surface treatment to increase hydrophobicity. For example, in Patent Document 1, there is an example in which highly hydrophobic spherical sol-gel silica fine particles are added to toner base particles to improve charging stability of the toner.

However, when images are output in a high-temperature, high-humidity environment for a long period of time, the silica present on the toner surface becomes susceptible to moisture in the image output device, causing changes in the toner surface condition. There was a case. As a result, the chargeability of the toner changes, resulting in variations in image density. Further, when the toner is transferred to a low humidity environment or a normal temperature and normal humidity environment to output an image, the silica present on the toner surface is also affected by the change in humidity, resulting in variations in image density. Thus, there is still room for improvement in terms of charging stability of toner under different image output environments.

On the other hand, Patent Documents 2 and 3 disclose examples in which polyalkylsilsesquioxane fine particles are added to toner base particles to improve the fluidity and charging stability of the toner. Further, Patent Document 4 provides an example of silica with reduced silanol groups, which are highly hydrophilic.

JP 2007-099582 A WO2015/107961 JP 2018-004949 A JP 2008-189545 A

However, in any of the techniques described in the documents, when an image is output under a high-temperature and high-humidity environment, or when an image is output under conditions where the humidity changes, it is sufficient to suppress the change in the hygroscopicity of the external additive. It turns out not. Therefore, there is room for improvement in terms of toner charging stability, image density stability, and environmental stability.
The present disclosure is an external additive for toner that has charging stability even when an image is output in a high-temperature, high-humidity environment, or when an image is output under conditions where the humidity changes, and is capable of suppressing image density fluctuations. and provide toner.

The present disclosure provides a toner external additive containing particles of a silicon polymer having a siloxane bond and a Si—R ¹ bond,
In the chart obtained by ²⁹ Si-NMR measurement of the toner external additive, A is the total peak area attributed to the toner external additive, and Si—R ¹ bond (the R ¹ has 1 to 1 carbon atoms). Represents the alkyl group of 6.) When the peak area attributed to B, the following formula (1) is satisfied,
In the chart obtained by ²⁹ Si-NMR measurement of the external additive for toner, SA is the total peak area attributed to the silicon polymer, and S3 is the peak area attributed to the T unit structure. It relates to an external additive for toner that satisfies (2).
0.260≦B/A≦0.450 (1)
0.00≦S3/SA≦0.50 (2)

The present disclosure is an external additive for toner that has charging stability even when an image is output in a high-temperature, high-humidity environment, or when an image is output under conditions where the humidity changes, and is capable of suppressing image density fluctuations. and toner can be provided.

In the present disclosure, the descriptions of “XX or more and YY or less” or “XX to YY” representing numerical ranges mean numerical ranges including the lower and upper limits, which are endpoints, unless otherwise specified. When numerical ranges are stated stepwise, the upper and lower limits of each numerical range can be combined arbitrarily.

The inventors of the present invention consider the mechanism by which the above effects are expressed as follows. A typical sol-gel silica particle conventionally used as an external additive for toner is a particle containing a siloxane bond (Si--O--Si) as a main component. Since sol-gel silica particles generally have silanol groups at their ends, there are unreacted residual silanol groups on the surface and inside of the silica particles. Even if the remaining silanol groups are subjected to a coupling reaction with a silane compound or the like to trimethylsilylate and improve the hydrophobicity, it is not sufficient to suppress changes in chargeability in long-term use in a high-temperature, high-humidity environment. rice field.
As a result of intensive studies by the present inventors, in an external additive having a silicon polymer having a siloxane bond and a Si—R ¹ bond, Si—R ¹ (Si to which an alkyl group is bonded) inside the external additive particle It was found that the above problem can be solved by optimizing the abundance of.
Regarding the mechanism, it is believed that the introduction of an alkyl group such as SiCH ₃ into the external additive particles increases the hydrophobicity of the external additive particles themselves and stabilizes the surface charge. As a result, it is assumed that the change in the charge amount of the toner due to the change in the charge amount of the toner in the high-temperature and high-humidity environment and the change in the humidity change can be suppressed.

The present disclosure provides a toner external additive containing particles of a silicon polymer having a siloxane bond and a Si—R ¹ bond,
In the chart obtained by ²⁹ Si-NMR measurement of the toner external additive, A is the total peak area attributed to the toner external additive, and the Si—R ¹ bond (the R ¹ has 1 carbon atom Represents an alkyl group of ~ 6.) When the peak area attributed to B, the following formula (1) is satisfied,
In the chart obtained by ²⁹ Si-NMR measurement of the external additive for toner, SA is the total peak area attributed to the silicon polymer, and S3 is the peak area attributed to the T unit structure. It relates to an external additive for toner that satisfies (2).
0.260≦B/A≦0.450 (1)
0.00≦S3/SA≦0.50 (2)

In ²⁹ Si-NMR, peaks are detected in different shift regions depending on the structure of the functional group that binds to Si in the constituent compound of the silicon polymer. By specifying each peak position using a standard sample, the structure that binds to Si can be specified. Moreover, the abundance ratio of each constituent compound can be calculated from the obtained peak area. The ratio of the peak areas of the M unit structure (S1), D unit structure (S2), T unit structure (S3) and Q unit structure (S4) to the total peak area can be obtained by calculation.

Ra, Rb, Rc, Rd, Re and Rf each independently represent an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3, more preferably 1 or 2, still more preferably 1). Further, the ratio (B/A) of the peak area B attributed to the Si—R ¹ bond to the total peak area A is the abundance ratio of Si—R ¹ inside the external additive particles. By satisfying formula (1), the amount of alkyl groups present inside the external additive particles is optimized, and the environmental stability and charging stability of the toner can be improved.
0.260≦B/A≦0.450 (1)
In Si—R ¹ , R ¹ represents an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3, more preferably 1 or 2, still more preferably 1).

When B/A is less than 0.260, the amount of alkyl groups present inside the external additive particles is too small, and the effect of improving environmental stability and charging stability is not exhibited. On the other hand, when B/A exceeds 0.450, the amount of siloxane bonds present inside the external additive particles is relatively small, resulting in deterioration in robustness and stability of the particles.
Preferably 0.280 ≤ B/A ≤ 0.450, more preferably 0.300 ≤ B/A ≤ 0.400, still more preferably 0.300 ≤ B/A ≤ 0.330 be. Within this range, the environmental stability and charging stability of the toner are further improved.

The method for producing the external additive for toner, which is silicon polymer particles, is not particularly limited, but particles are preferably formed through hydrolysis and polycondensation of a silicon compound (silane monomer) by a sol-gel method. Specifically, particles can be formed by polymerizing a mixture of a bifunctional silane having two siloxane bonds and a tetrafunctional silane having four siloxane bonds through hydrolysis and condensation polymerization. preferable. Silane monomers such as difunctional silanes and tetrafunctional silanes are described below.

That is, the silicon polymer is preferably a condensation polymer of at least one silicon compound selected from the group consisting of bifunctional silanes and at least one silicon compound selected from the group consisting of tetrafunctional silanes. The proportion of difunctional silane is preferably between 50 mol % and 70 mol %, more preferably between 61 mol % and 65 mol %. The proportion of tetrafunctional silane is preferably between 30 mol % and 50 mol %, more preferably between 35 mol % and 39 mol %.

In the method for producing an external additive for a toner, the present inventors adjusted the mixing ratio of the monomers, the solvent temperature during the hydrolysis and condensation reactions, the type of catalyst, the stirring time, the pH of the solution, and the like. It was discovered that the effect of

For example, to increase B/A, increase the mixing ratio of bifunctional silane, lower the temperature during the condensation reaction, shorten the stirring time, lower the pH of the solution, lower the temperature during hydrolysis. and the like. To reduce B/A, increase the mixing ratio of tetrafunctional silane, increase the temperature during the condensation reaction, increase the stirring time, increase the pH of the solution, increase the temperature during hydrolysis, and other methods.

The external additive for toner has silicon polymer particles having siloxane bonds. The particles of silicon polymer preferably contain at least 90% by weight, more preferably at least 95% by weight of silicon polymer.

The method for producing the silicon polymer particles is not particularly limited. For example, the silane compound may be added dropwise to water, hydrolyzed and condensed with a catalyst, and the resulting suspension may be filtered and dried. The particle size can be controlled by the type of catalyst, compounding ratio, reaction initiation temperature, dropping time, and the like. Acidic catalysts include hydrochloric acid, hydrofluoric acid, sulfuric acid and nitric acid, and basic catalysts include aqueous ammonia, sodium hydroxide, potassium hydroxide and the like, but are not limited to these.

Silicon polymer particles are preferably produced by the following method. Specifically, a first step of obtaining a hydrolyzate of a silicon compound, a second step of mixing the hydrolyzate with an alkaline aqueous medium and subjecting the hydrolyzate to a polycondensation reaction, polycondensation It is preferred to include a third step of mixing and granulating the reactants and the aqueous solution. In some cases, a hydrophobizing agent may be added to the spherical silicon polymer particle dispersion to obtain hydrophobized spherical silicon polymer particles.

In the first step, a silicon compound and a catalyst are brought into contact with each other by stirring, mixing, or the like in an aqueous solution in which an acidic or alkaline substance serving as a catalyst is dissolved in water. A known catalyst can be suitably used as the catalyst. Specifically, acidic catalysts include acetic acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, and basic catalysts include aqueous ammonia, sodium hydroxide, potassium hydroxide, and the like.

The amount of catalyst to be used may be appropriately adjusted depending on the type of silicon compound and catalyst. Preferably, it is selected in the range of 1×10 ⁻³ to 1 part by mass with respect to 100 parts by mass of water used for hydrolyzing the silicon compound.

If the amount of catalyst used is 1×10 ⁻³ parts by mass or more, the reaction proceeds sufficiently. On the other hand, when the amount of the catalyst used is 1 part by mass or less, the concentration of impurities remaining in the fine particles becomes low, and hydrolysis is facilitated. The amount of water used is preferably 2 to 15 mol per 1 mol of the silicon compound. When the amount of water is 2 mol or more, the hydrolysis reaction proceeds sufficiently, and when it is 15 mol or less, productivity improves.

The reaction temperature is not particularly limited, and it may be carried out at room temperature or in a heated state, but it is kept at 10 to 60 ° C. because the hydrolyzate can be obtained in a short time and the partial condensation reaction of the produced hydrolyzate can be suppressed. It is preferable to carry out the reaction in such a state. The reaction time is not particularly limited, and may be appropriately selected in consideration of the reactivity of the silicon compound used, the composition of the reaction solution prepared by mixing the silicon compound, acid and water, and the productivity.

In the method for producing silicon polymer particles, in the second step, the raw material solution obtained in the first step and an alkaline aqueous medium are mixed to cause a polycondensation reaction of the particle precursors. Thus, a polycondensation reaction liquid is obtained. Here, the alkaline aqueous medium is a liquid obtained by mixing an alkaline component, water, and, if necessary, an organic solvent or the like.

The alkaline component used in the alkaline aqueous medium is one whose aqueous solution exhibits basicity, and acts as a neutralizing agent for the catalyst used in the first step and as a catalyst for the polycondensation reaction in the second step. It is something to do. Examples of such alkali components include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonia; and organic amines such as monomethylamine and dimethylamine.

The amount of the alkaline component used is an amount that neutralizes the acid and acts effectively as a catalyst for the polycondensation reaction. Therefore, it is usually selected in the range of 0.01% by mass or more and 12.5% by mass or less.

In the second step, in addition to the alkaline component and water, an organic solvent may be used to prepare the alkaline aqueous medium. The organic solvent is not particularly limited as long as it is compatible with water, but an organic solvent that dissolves 10 g or more of water per 100 g at room temperature and normal pressure is suitable.

Specifically, alcohols such as methanol, ethanol, n-propanol, 2-propanol and butanol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane and hexanetriol; ethylene glycol monoethyl ether, ethers such as acetone, diethyl ether, tetrahydrofuran and diacetone alcohol; amide compounds such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone;

Among the organic solvents listed above, alcoholic solvents such as methanol, ethanol, 2-propanol and butanol are preferred. Furthermore, from the viewpoint of hydrolysis and dehydration condensation reaction, it is more preferable to select the same alcohol as the alcohol to be eliminated as the organic solvent.

In the third step, the polycondensation reaction product obtained in the second step is mixed with an aqueous solution to form particles. As the aqueous solution, water (tap water, pure water, etc.) can be suitably used. Further may be added. The temperature of the polycondensation reaction solution and the aqueous solution when mixed is not particularly limited, and a range of 5 to 70° C. is preferably selected in consideration of their composition, productivity and the like.

As a method for recovering the silicon polymer particles, any known method can be used without particular limitation. For example, the floating powder can be scooped out, and a filtering method may be employed, but the filtering method is preferable because of the simple operation. The filtration method is not particularly limited, and a known device such as vacuum filtration, centrifugal filtration, pressure filtration, or the like may be selected. Filter papers, filters, filter cloths, and the like used for filtration are not particularly limited as long as they are industrially available, and may be appropriately selected according to the device to be used.

The silicon polymer particles may be surface-treated with a known means such as a silane coupling agent or silicone oil to adjust the degree of hydrophobicity.

The monomer to be used can be appropriately selected depending on compatibility with the solvent and catalyst, hydrolyzability, etc., but tetraethoxysilane is preferable as the tetrafunctional silane. Dimethyldimethoxysilane is preferred as the bifunctional silane.

The silicon polymer is preferably a polycondensation product of at least one silicon compound selected from the group consisting of silicon compounds having a structure represented by the following formula (2).

In formula (2), R ² , R ³ , R ⁴ and R ⁵ are each independently an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3, more preferably 1 or 2), a phenyl group, or a reactive group (eg, a halogen atom, a hydroxy group, an acetoxy group, or an alkoxy group (preferably having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms)). At least one of R ² , R ³ , R ⁴ and R ⁵ is the reactive group.
R ² , R ³ , R ⁴ and R ⁵ are each independently an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3, more preferably 1 or 2), or (preferably 1 to 6, more preferably an alkoxy group having 1 to 3 carbon atoms.

To obtain silicon polymer particles, a silicon compound (tetrafunctional silane) having four reactive groups in one molecule of formula (2), R ² in formula (2) being an alkyl group or a phenyl group, , an organosilicon compound (trifunctional silane) having three reactive groups (R ³ , R ⁴ , R ⁵ ), R ² and R ³ in formula (2) are alkyl groups or phenyl groups, and two Organosilicon compounds (bifunctional silanes) having reactive groups (R ⁴ , R ⁵ ), R ² , R ³ and R ⁴ in formula (2) are alkyl groups or phenyl groups, and one reactive group ( R ⁵ ) can be used (monofunctional silanes).

These reactive groups undergo hydrolysis, addition polymerization, and condensation polymerization to form a crosslinked structure, and silicon polymer particles can be obtained. Hydrolysis, addition polymerization and condensation polymerization of R ³ , R ⁴ and R ⁵ can be controlled by reaction temperature, reaction time, reaction solvent and pH.

Tetrafunctional silanes include tetramethoxysilane, tetraethoxysilane, tetraisocyanatosilane, and the like.

Trifunctional silanes include methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane. , methyldiethoxychlorosilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, methyldiethoxyhydroxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane , propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyl triethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenyltrihydroxysilane and the like.

Difunctional silanes include di-tert-butyldichlorosilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, dibutyldichlorosilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dichlorodecylmethylsilane, dimethoxydecylmethylsilane, diethoxydecylmethylsilane, dichlorodimethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, diethyldimethoxysilane and the like.

Monofunctional silanes include t-butyldimethylchlorosilane, t-butyldimethylmethoxysilane, t-butyldimethylethoxysilane, t-butyldiphenylchlorosilane, t-butyldiphenylmethoxysilane, t-butyldiphenylethoxysilane, chlorodimethylphenyl silane, methoxydimethylphenylsilane, ethoxydimethylphenylsilane, chlorotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, triethylmethoxysilane, triethylethoxysilane, tripropylmethoxysilane, tributylmethoxysilane, tripentylmethoxysilane, triphenylchlorosilane, triphenylmethoxysilane, triphenylethoxysilane, and the like.

The silicon polymer contained in the toner external additive preferably has a siloxane bond, a Si--R ¹ bond and a Si--OR ² bond. Then, in the chart obtained by ²⁹ Si-NMR measurement of the external additive for toner, when C is the area of the peak attributed to Si-OR ² contained in the external additive for toner, the following formula (3) is obtained. is preferably satisfied.
0.050≦(C/A)/(B/A)≦0.180 (3)
R ² represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom.

Within the above range, the abundance ratio of hydrophobic Si—R ¹ and hydrophilic silanol groups inside the external additive particles is optimal, and the effect of suppressing charge build-up in a low-humidity environment is exhibited. That is, it is preferable from the viewpoint of the environmental stability and charging stability of the toner. More preferably, 0.060≦(C/A)/(B/A)≦0.150, and still more preferably 0.075≦(C/A)/(B/A)≦0.085.

(C/A)/(B/A) can be controlled by the selection of the silicon compound, the mixing ratio of the silicon compound, hydrolysis and condensation conditions. For example, to increase (C/A)/(B/A), methods such as increasing the mixing ratio of tetrafunctional silane, lowering the temperature during the condensation reaction, lowering the temperature during the hydrolysis, etc. is mentioned. To reduce (C/A)/(B/A), increase the mixing ratio of bifunctional silane, increase the temperature during the condensation reaction, increase the stirring time, increase the pH of the solution, and add water. A method of raising the temperature at the time of decomposition can be mentioned.

The number average particle diameter of the primary particles of the external additive for toner is preferably 0.02 μm to 0.30 μm. When the number average particle diameter of the primary particles is within the above range, the toner particles are easily coated with the external additive uniformly. In addition, since the stress to the toner can be suppressed, the effect of charging stability can be easily obtained.

When the number average particle diameter of the primary particles of the external additive for toner is 0.02 μm or more, it is difficult to output a large amount of images with low print density over a long period of time in a severe environment such as a high-temperature and high-humidity environment. Even if there is, since the stress on the toner is reduced, the external additive particles are less likely to be embedded in the toner particle surface. Further, when the number average particle diameter is 0.30 μm or less, the external additive particles are less likely to detach from the toner particle surfaces. The number average particle diameter of the primary particles of the external additive for toner is more preferably 0.05 μm to 0.25 μm, still more preferably 0.08 μm to 0.18 μm.

The surface of the external additive for toner is preferably treated with a hydrophobizing agent. That is, the toner external additive particles are preferably silicon polymer particles surface-treated with a hydrophobizing agent. Although the hydrophobizing agent is not particularly limited, it is preferably an organic silicon compound.

For example, alkylsilazane compounds such as hexamethyldisilazane; alkylalkoxysilane compounds such as diethyldiethoxysilane, trimethylmethoxysilane, methyltrimethoxysilane, butyltrimethoxysilane; fluorosilanes such as trifluoropropyltrimethoxysilane; Examples include alkylsilane compounds, chlorosilane compounds such as dimethyldichlorosilane and trimethylchlorosilane, siloxane compounds such as octamethylcyclotetrasiloxane, silicone oil, and silicone varnish.

Hydrophobization treatment of the surfaces of the external additive particles can further suppress changes in the charge amount of the toner under high-temperature and high-humidity environments. Among these, the toner external additive is preferably surface-treated with at least one compound selected from the group consisting of alkylsilazane compounds, alkylalkoxysilane compounds, chlorosilane compounds, siloxane compounds and silicone oils. Furthermore, it is more preferable that the external additive for toner is surface-treated with an alkylsilazane compound from the viewpoint of environmental stability and charge stability.

The degree of hydrophobicity of the external additive for toner by the methanol titration method is preferably 40% to 80%, more preferably 50% to 60%, still more preferably 50% to 55%, from the viewpoint of charging stability. be.

In the chart obtained in the ²⁹ Si-NMR measurement of the external additive for toner, when SA is the total peak area attributed to the silicon polymer and S3 is the peak area attributed to the T unit structure, 0.00. ≦S3/SA≦0.50. Within the above range, the abundance ratio of Si—R ¹ inside the external additive particles and the silanol group is optimal, and the environmental stability and charging stability of the toner are improved. Furthermore, it is preferable that 0.00≦S3/SA≦0.40, and more preferably 0.00≦S3/SA≦0.20.

In the chart obtained by ²⁹ Si-NMR measurement of the external additive for toner, SA is the total peak area attributed to the silicon polymer, S4 is the peak area attributed to the Q unit structure, and S4 is the peak area attributed to the T unit structure. When the peak area attributed to the D unit structure is S3 and the peak area attributed to the D unit structure is S2, the following formulas (I) to (III) are preferably satisfied.
0.20≦S4/SA≦0.60 (I)
0.00≦S3/SA≦0.50 (II)
0.20≦S2/SA≦0.70 (III)

When the above formulas (I) to (III) are satisfied, when the toner receives stress from a member such as a carrier, it is possible to suppress the embedding of the external additive particles in the toner particle surface and the destruction of the external additive particles themselves. .

More preferably, 0.30≦S4/SA≦0.50, 0≦S3/SA≦0.10, and 0.50≦S2/SA≦0.70. Within this range, the abundance ratio of Si--R ¹ such as Si--CH ₃ inside the external additive particles and the silanol group is optimal, which is more preferable from the viewpoint of the environmental stability and charging stability of the toner. S4/SA, S3/SA and S2/SA can be controlled by selection of silicon compound, mixing ratio of silicon compound, hydrolysis and condensation conditions.

The ratio of the peak area attributed to the siloxane bond to the total peak area attributed to the silicon polymer calculated from the chart obtained by measuring the ²⁹ Si-NMR of the external additive for toner is 60.0% to 85%. 0%, preferably 63.0% to 68.0%. Within the above range, the abundance ratio of Si--R ¹ such as Si--CH ₃ inside the external additive particles and the siloxane bond is optimal, which is preferable because the chargeability is improved in a high-humidity environment. The area ratio can be controlled by selection of the silicon compound, mixing ratio of the silicon compound, hydrolysis and condensation conditions.

The average circularity of the external additive for toner is preferably 0.85 to 0.95 from the viewpoint of durability stability and charging stability of the toner. It is more preferably 0.88 to 0.93. The average circularity can be controlled by the mixing ratio of the monomers and condensation conditions.

The toner has toner particles containing a binder resin and an external additive for toner, and the external additive for toner is the external additive for toner. The content of the toner external additive in the toner is preferably 0.1 to 20.0 parts by mass with respect to 100 parts by mass of toner particles from the viewpoint of charging stability. 0.5 parts by mass to 15.0 parts by mass is more preferable, and 1.0 parts by mass to 10.0 parts by mass is even more preferable.

When the content of the external additive for toner is 0.1 parts by mass or more, even when a large amount of images with low print density are output over a long period of time in a harsh environment such as a high-temperature and high-humidity environment. , the stress applied to the toner can be suppressed, and durability stability and charging stability are improved. Further, when the content of the external additive for toner is 20.0 parts by mass or less, filming of the external additive particles on the carrier or photosensitive member is prevented even when an image with high print density is output for a long time. can be suppressed.

<Binder resin>
The binder resin used in the toner is not particularly limited, and the following polymers and the like can be used. Homopolymers of styrene and substituted products thereof such as polystyrene, poly-p-chlorostyrene and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene - acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-methyl chloromethacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether Styrenic copolymers such as copolymers, styrene-vinyl methyl ketone copolymers, styrene-acrylonitrile-indene copolymers; polyvinyl chloride, phenolic resin, natural resin-modified phenolic resin, natural resin-modified maleic acid resin, acrylic resins, methacrylic resins, polyvinyl acetates, silicone resins, polyester resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral resins, terpene resins, cumarone-indene resins, petroleum-based resins, and the like. Among them, polyester resins are preferable from the viewpoint of durability stability and charging stability.

Also, the acid value of the polyester resin is preferably 0.5 mgKOH/g to 40 mgKOH/g from the viewpoint of environmental stability and charge stability. The functional group that produces an acid value in the polyester resin interacts with Si--R ¹ in the external additive to further improve the toner chargeability in a high-humidity environment. The acid value is more preferably 1 mgKOH/g to 20 mgKOH/g, still more preferably 1 mgKOH/g to 15 mgKOH/g.

<Colorant>
A colorant may be used in the toner particles. Colorants include the following. Black colorants include those toned black using carbon black; yellow colorants, magenta colorants and cyan colorants. A pigment may be used alone as a coloring agent, but it is more preferable to use a dye and a pigment in combination to improve the definition from the viewpoint of image quality of a full-color image.

Examples of magenta toner pigments include the following. C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48:2, 48:3, 48:4, 49, 50, 51, 52, 53, 54, 55, 57:1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; I. Pigment Violet 19; C.I. I. Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

Dyes for magenta toner include the following. C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; C.I. I. disperse thread 9;C. I. Solvent Violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; C.I. I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

Examples of cyan toner pigments include the following. C. I. Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, 17; C.I. I. Bat Blue 6; C.I. I. Acid Blue 45, a copper phthalocyanine pigment having a phthalocyanine skeleton substituted with 1 to 5 phthalimidomethyl groups. As dyes for cyan toners, C.I. I. There is Solvent Blue 70.

Examples of yellow toner pigments include the following. C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; I. Bat Yellow 1, 3, 20. As a yellow toner dye, C.I. I. There is Solvent Yellow 162. The content of the colorant is preferably 0.1 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin.

<Wax>
Wax may be used for the toner particles. Examples of wax include the following. Hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; Polymers; waxes containing fatty acid ester as a main component such as carnauba wax; partially or wholly deoxidized fatty acid esters such as deoxidized carnauba wax.

Furthermore, the following are mentioned. saturated straight chain fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid and parinaric acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, saturated alcohols such as ceryl alcohol and mericyl alcohol; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid and montanic acid; esters with alcohols such as carnauvyl alcohol, ceryl alcohol, and melisyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylene bis stearic acid amide, ethylene biscaprine Saturated fatty acid bisamides such as acid amides, ethylenebislauric acid amide, and hexamethylenebisstearic acid amide; Unsaturated fatty acid amides such as N' dioleyl sebacamide; Aromatic bisamides such as m-xylene bisstearic acid amide and N,N' distearyl isophthalic acid amide; Calcium stearate, calcium laurate, stearin Fatty acid metal salts such as zinc acid and magnesium stearate (generally referred to as metallic soaps); Waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid partial esters of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; methyl ester compounds having a hydroxy group obtained by hydrogenation of vegetable oils and fats. The wax content is preferably 2.0 parts by mass to 30.0 parts by mass with respect to 100 parts by mass of the binder resin.

<Charge control agent>
The toner particles may optionally contain a charge control agent. As the charge control agent, known ones can be used, but a metal compound of an aromatic carboxylic acid which is colorless, has a high charging speed of the toner, and can stably maintain a constant charge amount is particularly preferable.

Negative charge control agents include metal salicylate compounds, metal naphthoate compounds, metal dicarboxylic acid compounds, polymeric compounds having sulfonic acid or carboxylic acid side chains, and sulfonate or sulfonate ester side chain compounds. Polymeric compounds, polymeric compounds having carboxylates or carboxylic acid esters in side chains, boron compounds, urea compounds, silicon compounds, and calixarene can be mentioned.

Examples of the positive charge control agent include quaternary ammonium salts, polymeric compounds having the quaternary ammonium salts in side chains, guanidine compounds, and imidazole compounds. The charge control agent may be added internally or externally to the toner particles. The amount of the charge control agent to be added is preferably 0.2 parts by mass to 10 parts by mass with respect to 100 parts by mass of the binder resin.

<Inorganic fine particles>
The toner may optionally contain other inorganic fine particles in addition to the external additive for toner described above. The inorganic fine particles may be internally added to the toner particles, or may be mixed with the toner particles as an external additive. When it is contained as an external additive, inorganic fine particles such as silica fine particles, titanium oxide fine particles, and aluminum oxide fine particles are preferable. The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil or a mixture thereof.

As an external additive for improving fluidity, inorganic fine particles having a specific surface area of 50 m ² /g or more and 400 m ² /g or less are preferable. In order to improve fluidity and stabilize durability, inorganic fine particles having a specific surface area within the above range may be used in combination with the external additive for toner.

The inorganic fine particles are preferably used in an amount of 0.1 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the toner particles. When the above range is satisfied, the effect of charging stability is likely to be obtained. The content of the external additive for toner described above is preferably 50% by mass to 100% by mass, more preferably 80% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass of the total external additive. .

<Developer>
The toner can be used as a one-component developer, but in order to further improve dot reproducibility and to supply stable images over a long period of time, it can be mixed with a magnetic carrier and used as a two-component developer. can also be used. That is, it is a two-component developer containing a toner and a magnetic carrier, and the toner is preferably the above toner.

Magnetic carriers include, for example, iron oxide, unoxidized iron powder; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earths; Oxide particles; magnetic substances such as ferrite; magnetic substance-dispersed resin carriers (so-called resin carriers) containing magnetic substances and a binder resin that holds the magnetic substances in a dispersed state; As for the mixing ratio of the magnetic carrier and the toner, the toner concentration in the two-component developer is preferably 2% by mass or more and 15% by mass or less, more preferably 4% by mass or more and 13% by mass or less.

<Method for producing toner particles>
The method for producing toner particles is not particularly limited, and known production methods such as suspension polymerization, emulsion aggregation, melt-kneading, and dissolution suspension can be employed. A toner can be obtained by mixing the obtained toner particles with the above external additive for toner and, if necessary, other external additives.

Mixing of the toner particles and the external additive can be performed by a double-con mixer, V-type mixer, drum-type mixer, super mixer, Henschel mixer, Nauta mixer, Mechanohybrid (manufactured by Nippon Coke Kogyo Co., Ltd.), Nobilta (manufactured by Hosokawa Micron Co., Ltd.), etc. can be used.

Methods for measuring various physical properties are described below.
<Separation of External Additive Particles and Toner Particles from Toner>
Each physical property can also be measured using an external additive separated from the toner by the following method. 200 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water and dissolved in a hot water bath to prepare a concentrated sucrose solution. 31 g of the concentrated sucrose solution and 6 mL of contaminon N (a 10% by mass aqueous solution of a neutral detergent for washing precision measuring instruments at pH 7 consisting of a nonionic surfactant, an anionic surfactant, and an organic builder in a centrifugation tube) , manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a dispersion. 1 g of toner is added to this dispersion, and clumps of toner are loosened with a spatula or the like.

The tube for centrifugation is shaken for 20 minutes with a shaker ("KM Shaker" (model: V.SX) manufactured by Iwaki Sangyo Co., Ltd.) at 350 reciprocations per minute. After shaking, the solution is replaced in a swing rotor glass tube (50 mL), and centrifuged at 3500 rpm for 30 minutes in a centrifuge.

In the glass tube after centrifugation, the toner exists in the uppermost layer, and the external additive for toner exists in the aqueous solution side of the lower layer. The aqueous solution of the lower layer is collected and centrifuged to separate the sucrose and the external toner additive, and the external toner additive is collected. If necessary, the centrifugal separation is repeated, and after sufficient separation, the dispersion is dried and the external additive for toner is collected. When a plurality of toner external additives are added, a centrifugal separation method or the like can be used to sort out the toner external additives.

<Method for Measuring Number Average Particle Diameter of Primary Particles of External Additive Particles for Toner>
The number average particle size of the primary particles of the external additive for toner is obtained by measurement by a centrifugal sedimentation method. Specifically, 0.01 g of dried external additive particles is put into a 25 ml glass vial, and 0.2 g of a 5% triton solution and 19.8 g of RO water are added to prepare a solution. Next, a probe of an ultrasonic disperser (the tip of the tip is immersed in the above solution and ultrasonically dispersed for 15 minutes at an output of 20 W to obtain a dispersion. Subsequently, using this dispersion, CPS Instruments
The number average particle diameter of the primary particles is measured using a centrifugal sedimentation particle size distribution analyzer DC24000 manufactured by the company. The rotation speed of the disk is set to 18000 rpm and the true density is set to 1.3 g/cm ³ . Prior to measurement, the instrument is calibrated using polyvinyl chloride particles with an average particle size of 0.476 μm.

<Method for measuring acid value of resin>
The acid value is mg of potassium hydroxide required to neutralize acid components such as free fatty acid and resin acid contained in 1 g of sample. Acid value is measured as follows according to JIS-K0070-1992.

(1) Reagent 1.0 g of phenolphthalein is dissolved in 90 mL of ethyl alcohol (95% by volume), and ion-exchanged water is added to make 100 mL to obtain a phenolphthalein solution.
Dissolve 7 g of special grade potassium hydroxide in 5 mL of water, and add ethyl alcohol (95% by volume) to make 1 L. The solution is placed in an alkali-resistant container so as not to come in contact with carbon dioxide gas, etc., and left for 3 days, then filtered to obtain a potassium hydroxide solution. The resulting potassium hydroxide solution is stored in an alkali-resistant container. The potassium hydroxide solution factor was obtained by taking 25 mL of 0.1 mol/L hydrochloric acid in an Erlenmeyer flask, adding a few drops of the phenolphthalein solution, titrating with the potassium hydroxide solution, and determining the potassium hydroxide required for neutralization. Determined from the amount of solution. The 0.1 mol/L hydrochloric acid used is prepared according to JIS K 8001-1998.

(2) Operation (A) Main Test 2.0 g of the pulverized sample is precisely weighed in a 200 mL Erlenmeyer flask, 100 mL of a mixed solution of toluene/ethanol (2:1) is added, and dissolved over 5 hours. A few drops of the phenolphthalein solution are then added as an indicator, and the potassium hydroxide solution is used for titration. The end point of titration is when the light red color of the indicator continues for about 30 seconds.
(B) Blank test Titration is performed in the same manner as described above except that no sample is used (that is, only a mixed solution of toluene/ethanol (2:1) is used).
(3) Calculate the acid value by substituting the obtained result into the following formula.
A = [(CB) x f x 5.61]/S
Here, A: acid value (mgKOH / g), B: added amount of potassium hydroxide solution for blank test (mL), C: added amount of potassium hydroxide solution for main test (mL), f: potassium hydroxide Solution factor, S: mass of sample (g).

<Measurement of Acid Value of Polyester Resin from Toner>
As a method for measuring the acid value of the polyester resin in the toner, the following method can be used. The polyester resin is separated from the toner by the following method, and the acid value is measured. The toner is dissolved in tetrahydrofuran (THF), and the solvent is distilled off from the obtained soluble matter under reduced pressure to obtain the tetrahydrofuran (THF) soluble matter of the toner. A tetrahydrofuran (THF) soluble component of the obtained toner is dissolved in chloroform to prepare a sample solution having a concentration of 25 mg/ml. 3.5 ml of the obtained sample solution is injected into the following apparatus, and resin components having a molecular weight of 2000 or more are fractionated under the following conditions.
Preparative GPC device: Preparative HPLC LC-980 type manufactured by Nippon Analytical Industry Co., Ltd. Preparative column: JAIGEL 3H, JAIGEL 5H (manufactured by Nippon Analytical Industry Co., Ltd.)
Eluent: chloroform Flow rate: 3.5 ml/min
After separating the resin-derived high molecular weight component, the solvent is distilled off under reduced pressure, and the residue is dried in an atmosphere of 90° C. under reduced pressure for 24 hours. The above operation is repeated until about 2.0 g of the resin component is obtained. Using the obtained sample, the acid value is measured according to the procedure described above.

<Method for Measuring Weight Average Particle Diameter (D4) of Toner Particles>
The weight-average particle diameter (D4) of the toner particles was measured using a precision 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. Using the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter) for setting conditions and analyzing measurement data, the number of effective measurement channels is 25,000. is analyzed and calculated.
As the electrolytic aqueous solution used for measurement, a solution obtained by dissolving special grade sodium chloride in ion-exchanged water to a concentration of about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter, Inc.) can be used. Before performing measurement and analysis, the dedicated software is set as follows.

In the "change standard measurement method (SOM) screen" of the dedicated software, set the total count number in control mode to 50000 particles, set the number of measurements to 1, and set the Kd value to "standard particle 10.0 μm" (Beckman Coulter (manufactured by Co., Ltd.) is used to set the value obtained. By pressing the threshold/noise level measurement button, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check the flash of aperture tube after measurement. In the "pulse-to-particle size conversion setting screen" of the dedicated software, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm or more and 60 μm or less. A specific measuring method is as follows.

(1) About 200 ml of the electrolytic aqueous solution is placed in a 250 ml round-bottom glass beaker exclusively for Multisizer 3, set on a sample stand, and stirred with a stirrer rod counterclockwise at 24 rotations/second. Then, remove the dirt and air bubbles inside the aperture tube using the dedicated software's "Flush Aperture Tube" function.
(2) About 30 ml of the electrolytic aqueous solution is placed in a 100 ml flat-bottomed glass beaker, and "Contaminon N" (a nonionic surfactant, an anionic surfactant, and an organic builder consisting of an organic builder) is used as a dispersing agent in the beaker. About 0.3 ml of a diluent obtained by diluting a 10% by mass aqueous solution of a neutral detergent for washing ware (manufactured by Wako Pure Chemical Industries, Ltd.) with ion-exchanged water three times by mass is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in with a phase shift of 180 degrees, and an ultrasonic disperser with an electrical output of 120 W "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios) in a water tank. A predetermined amount of ion-exchanged water is put into the water tank, and about 2 ml of the contaminon 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. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.
(5) About 10 mg of toner particles are added little by little to the aqueous electrolytic solution in the beaker of (4) while the aqueous electrolytic solution is being irradiated with ultrasonic waves, and dispersed. Then, the ultrasonic dispersion treatment is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water in the water tank is appropriately adjusted to 10°C or higher and 40°C or lower.
(6) The electrolytic aqueous solution of (5) above, in which the toner is dispersed, is dropped into the round-bottomed beaker of (1) above set in the sample stand, and adjusted so that the measured concentration is about 5%. . The measurement is continued until the number of measured particles reaches 50,000.
(7) Analyze the measurement data with the dedicated software attached to the apparatus, and calculate the weight average particle size (D4). The weight average particle diameter (D4) is the "average diameter" on the analysis/volume statistics (arithmetic mean) screen when graph/vol% is set using dedicated software.

<Method for Measuring Average Circularity of External Additive Particles for Toner, Toner Particles, and Toner>
The average circularity is used as a simple method of quantitatively expressing the shape of particles. Particles with equivalent circle diameters in the range of 0.01 μm to 400 μm are measured using a flow-type particle image analyzer FPIA-3000 manufactured by Sysmex Corporation, and the circularity of the measured particles is determined by the following formula. The average circularity is defined as the sum of the circularities divided by the total number of particles. Note that the number of particles to be measured is 5000 particles.
Circularity a = L0/L
(In the formula, L0 indicates the perimeter of a circle having the same projected area as the particle image, and L is the particle projection image when image processing is performed with an image processing resolution of 512 × 512 (pixels of 0.3 μm × 0.3 μm). indicates the perimeter of

<Method for Measuring Hydrophobicity of External Additive for Toner>
The degree of hydrophobicity of the external additive particles for toner is calculated by a methanol titration method. Specifically, it is measured by the following procedure. 0.5 g of external toner additive particles are added to 50 ml of RO water, and methanol is added dropwise from a burette while stirring the mixed liquid until the entire amount of the external additive for toner is wetted.

Whether or not the entire amount has been wetted is determined by whether or not the external toner additive floating on the surface of the water is completely submerged and suspended in the liquid. At this time, the volume percentage value of methanol with respect to the total amount of the mixed liquid and the dropped methanol at the end of dropping is defined as the degree of hydrophobicity. Higher hydrophobicity values indicate higher hydrophobicity.

<Method for measuring B/A and (C/A)/(B/A) abundance ratio of constituent compounds of external additive for toner by solid ²⁹ Si-NMR>
In solid-state ²⁹ Si-NMR, peaks are detected in different shift regions depending on the structure of the functional group bonded to Si of the constituent compound of the external additive for toner. By specifying each peak position using a standard sample, the structure that binds to Si can be specified. Moreover, the abundance ratio of each constituent compound can be calculated from the obtained peak area. The ratio of the peak areas of the Q unit structure, the T unit structure, and the D unit structure to the total peak area can be obtained by calculation.

Specific measurement conditions for solid-state ²⁹ Si-NMR are as follows.
Equipment: JNM-ECX5002 (JEOL RESONANCE)
Temperature: Room temperature Measurement method: DDMAS method ²⁹ Si 45°
Sample tube: Zirconia 3.2 mmφ
Sample: filled in a powder state in a test tube Sample rotation speed: 10 kHz
relaxation delay: 180s
Scan: 2000

After the measurement, a plurality of silane components having different substituents and bonding groups in the sample or external additive for toner were peak-separated into the following M unit structure, D unit structure, T unit structure, and Q unit structure by curve fitting. and calculate the peak area for each.
Curve fitting is performed using EXcalibur for Windows (registered trademark) version 4.2 (EX series) of software for JNM-EX400 manufactured by JEOL. Click "1D Pro" from the menu icon to read the measurement data. Next, select "Curve fitting function" from "Command" on the menu bar to perform curve fitting. Curve fitting is performed for each component so that the difference (composite peak difference) between the composite peak obtained by combining the peaks obtained by curve fitting and the peak of the measurement result is minimized.
M unit structure: (Ra) (Rb) (Rc) SiO _1/2 (S1)
D unit structure: (Rd)(Re)Si(O _1/2 ) ₂ (S2)
T unit structure: RfSi(O _1/2 ) ₃ (S3)
Q unit structure: Si(O _1/2 ) ₄ (S4)
(S1+S2+S3+S4)=SA.

Ra, Rb, Rc, Rd, Re, and Rf in the formulas (S1), (S2), and (S3) are silicon-bonded organic groups such as hydrocarbon groups having 1 to 6 carbon atoms (e.g., alkyl group), indicating a halogen atom. If it is necessary to confirm the structure in more detail, the measurement results of ¹³ C-NMR and ¹ H-NMR may be identified together with the measurement results of ²⁹ Si-NMR. S2/SA, S3/SA and S4/SA are calculated from SA, S2, S3 and S4 thus obtained.

(B/A calculation method)
From the chart obtained by solid-state ²⁹ Si-NMR, the peak area of (Si-R ¹ ) in each unit structure at the following positions is calculated. R ¹ is as described above and represents an alkyl group having 1 to 6 carbon atoms.
The peak area of the Q4 unit structure having (Si—R ¹ ) is S44, the peak area of the Q3 unit structure having (Si—R ¹ ) is S43, and the peak area of the Q2 unit structure having (Si—R ¹ ) is S42. , (Si—R ¹ ), the peak area of the Q1 unit structure is S41.
The peak area of the T3 unit structure having (Si—R ¹ ) is S33, the peak area of the T2 unit structure having (Si—R ¹ ) is S32, and the peak area of the T1 unit structure having (Si—R ¹ ) is S31. and
Let S22 be the peak area of the D2 unit structure having (Si—R ¹ ), and S21 be the peak area of the D1 unit structure having (Si—R ¹ ).
Let S11 be the peak area of the M1 unit structure having (Si—R ¹ ).

At this time, the peak area ratio of Si—R ¹ in each unit structure is calculated as follows.
Peak area ratio QB of Si—R ¹ attributed to Q unit structure = (S44/S4) × 0 + (S43/S4) × 0 + (S42/S4) × 0 + (S41/S4) × 0
Peak area ratio TB of Si—R ¹ attributed to the T unit structure = (S33/S3) × 1/4 + (S32/S3) × 1/4 + (S31/S3) × 1/4
Peak area ratio DB of Si—R ¹ attributed to D unit structure = (S22/S2) × 1/2 + (S21/S2) × 1/2
Peak area ratio MB of Si—R ¹ attributed to the M unit structure MB=S11/S1×3/4

The constituent units of the silicon polymer are classified into M units (monofunctional), D units (bifunctional), T units (trifunctional), and Q units (tetrafunctional) according to the number of functional groups. be. In the present disclosure, the degree of condensation in each unit is distinguished by the number of bridging oxygens, such as D1 unit, D2 unit, T1 unit, T2 unit, T3 unit, and the like. That is, a number following an alphabet such as D or T indicates the number of bridging oxygens forming a siloxane bond. For example, a T3 unit indicates that all three functional groups are condensed and participate in a siloxane bond. Also, the T2 unit shows that two of the three functional groups are condensed and participate in the siloxane bond, and one functional group is not condensed.

Q unit structure Q4: -105 ppm to -115 ppm
Q3: -95 ppm to -104 ppm
Q2: -85 ppm to -94 ppm
Q1: -75 ppm to -84 ppm
T unit structure T3: -60 ppm to -70 ppm
T2: -50 ppm to -59 ppm
T1: -40 ppm to -49 ppm
D unit structure D2: -15 ppm to -25 ppm
D1: -10ppm to 14-ppm
M unit structure M1: -5 ppm to -9 ppm
From the above formula, B/A=QB+TB+DB+MB is calculated.

(How to calculate C/A and (C/A)/(B/A))
From the chart obtained by solid-state ²⁹ Si-NMR, the peak area of the unreacted group (Si-OR ² ) in each unit structure at the following positions is calculated. R ² represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom.
The peak area of the Q4 unit structure having an unreacted group (Si—OR ² ) is S44, the peak area of the Q3 unit structure having an unreacted group (Si—OR ² ) is S43, and the unreacted group (Si—OR ² ) is Let S42 be the peak area of the Q2 unit structure having Si, and let S41 be the peak area of the Q1 unit structure having an unreacted group (Si—OR ² ).
The peak area of the T3 unit structure having an unreacted group (Si—OR ² ) is S33, the peak area of the T2 unit structure having an unreacted group (Si—OR ² ) is S32, and the unreacted group (Si—OR ² ) is Let S31 be the peak area of the T1 unit structure.
Let S22 be the peak area of the D2 unit structure having an unreacted group (Si—OR ² ), and S21 be the peak area of the D1 unit structure having an unreacted group (Si—OR ² ).
Let S11 be the peak area of the M1 unit structure having an unreacted group (Si—OR ² ).

At this time, the peak area ratio of Si—OR ² in each unit structure is calculated as follows.
Peak area ratio QC of Si—OR ² attributed to the Q unit structure = (S44/S4) × 0 + (S43/S4) × 1/4 + (S42/S4) × 1/2 + (S41/S4) × 3/ 4,
Peak area ratio TC of Si—OR ² attributed to the T unit structure = (S33/S3) × 0 + (S32/S3) × 1/4 + (S31/S3) × 1/2,
The peak area ratio DC of Si—OR ² attributed to the D unit structure = (S22/S2) × 0 + (S21/S2) × 1/4,
Peak area ratio of Si—OR ² attributed to M unit structure MC=S11/S1×0

Q unit structure Q4: -105 ppm to -115 ppm
Q3: -95 ppm to -104 ppm
Q2: -85 ppm to -94 ppm
Q1: -75 ppm to -84 ppm
T unit structure T3: -60 ppm to -70 ppm
T2: -50 ppm to -59 ppm
T1: -40 ppm to -49 ppm
D unit structure D2: -15 ppm to -25 ppm
D1: -10ppm to 14-ppm
M unit structure M1: -5 ppm to -9 ppm
From the above formula, C/A=QC+TC+DC+MC is calculated. Also, (C/A)/(B/A) is calculated from B/A calculated above.

(Proportion of peak area attributed to siloxane bond)
From the chart obtained by solid-state ²⁹ Si-NMR, the ratio of the peak area attributed to siloxane bonds to the total peak area attributed to the silicon polymer is calculated by the following method.
p44 the peak area attributed to the Q4 unit structure having a siloxane bond, p43 the peak area attributed to the Q3 unit structure having a siloxane bond, p42 the peak area attributed to the Q2 unit structure having a siloxane bond, the siloxane bond Let p41 be the peak area attributed to the Q1 unit structure.
The peak area attributed to the T3 unit structure having a siloxane bond is p33, the peak area attributed to the T2 unit structure having a siloxane bond is p32, and the peak area attributed to the T1 unit structure having a siloxane bond is p31.
Let p22 be the peak area attributed to the D2 unit structure having a siloxane bond, and p21 be the peak area attributed to the D1 unit structure having a siloxane bond.
Let p11 be the peak area attributed to the M1 unit structure having a siloxane bond.

At this time, the peak area ratio attributed to the siloxane bond in each unit structure is calculated as follows.
Peak area ratio of siloxane bonds attributed to the Q unit structure Qp = (p44/S4) + (p43/S4) × 3/4 + (p42/S4) × 1/2 + (p41/S4) × 1/4
Peak area ratio of siloxane bond attributed to T unit structure Tp = (p33/S3) × 3/4 + (p32/S3) × 1/2 + (p31/S3) × 1/4
Peak area ratio Dp of siloxane bond attributed to D unit structure = (p22/S2) x 1/2 + (p21/S2) x 1/2
Peak area ratio Mp of siloxane bond attributed to M unit structure Mp = p11/S1 × 1/4
From the above, the area ratio of peaks attributed to siloxane bonds=Qp+Tp+Dp+Mp is calculated.

<Method for measuring surface treatment agent of external additive for toner>
The surface treatment agent of the toner external additive is analyzed by pyrolysis GC-MS (gas chromatography mass spectrometry). Specifically, the measurement conditions are as follows.
Apparatus: GC6890A (manufactured by Agilent), thermal decomposition apparatus (manufactured by Nippon Analytical Industry)
Column: HP-5ms 30m
Thermal decomposition temperature: 590°C
By specifying each peak position of the profile obtained by the measurement using a standard sample, the surface treatment agent of the external additive for toner is specified.

The present invention will be specifically described by way of examples shown below. However, these do not limit the present invention at all. Unless otherwise specified, "parts" in the following prescriptions are all based on mass.

<Production Example of External Additive Particle 1 for Toner>
1. Hydrolysis Step A 200 ml beaker was charged with 43.2 g of RO water and 0.008 g of acetic acid as a catalyst, and stirred at 45°C. 27.2 g of tetraethoxysilane and 27.2 g of dimethyldimethoxysilane were added thereto and stirred for 1.5 hours to obtain a raw material solution.

2. Condensation Polymerization Step 68.8 g of RO water, 340.0 g of methanol and 2.0 g of 25% aqueous ammonia were placed in a 1000 ml beaker and stirred at 30° C. to prepare an alkaline aqueous medium. In this alkaline aqueous medium, 1. The raw material solution obtained in the hydrolysis step was added dropwise over 1 minute. The mixed solution after dropping the raw material solution was stirred for 1.5 hours while being kept at 30° C. to proceed the polycondensation reaction and obtain a polycondensation reaction solution.

3. Particulation step 1000 g of RO water was put into a 2000 ml beaker, and the mixture was stirred at 25°C. The polycondensation reaction liquid obtained in the polycondensation step was added dropwise over 10 minutes. As soon as the polycondensation reaction liquid was mixed with water, it became cloudy and a dispersion liquid containing silicon polymer particles having siloxane bonds was obtained.

4. Hydrophobizing step 3. 27.1 g of hexamethyldisilazane as a hydrophobizing agent was added to the dispersion liquid containing silicon polymer particles having siloxane bonds obtained in the granulating step, and the mixture was stirred at 60° C. for 2.5 hours. After allowing to stand for 5 minutes, the powder precipitated at the bottom of the solution was collected by suction filtration and dried under reduced pressure at 120° C. for 24 hours to obtain external additive particles 1 for toner. The number average particle diameter of the primary particles of the obtained external additive particles 1 for toner was 0.12 μm. Table 1 shows the physical properties of the external additive particles 1 for toner.

<Production Example of External Additive Particle 2 for Toner>
External toner additive particles 2 were obtained in the same manner as in the production example of external additive particles 1 for toner, except that 16.3 g of hexamethyldisilazane was used in the hydrophobization step. Table 1 shows the physical properties of the obtained external additive particles 2 for toner.

<Production Example of External Additive Particles 3 for Toner>
External toner additive particles 3 were obtained in the same manner as in the production example of external additive particles 1 for toner, except that 37.9 g of hexamethyldisilazane used in the hydrophobization step was changed. Table 1 shows the physical properties of the obtained external additive particles 3 for toner.

<Production Example of External Additive Particles 4 for Toner>
In the hydrolysis step, the stirring temperature was changed to 50°C;2. Toner external additive particles 4 were obtained in the same manner as in the production example of toner external additive particles 1 except that the 25% aqueous ammonia used in the polycondensation step was changed to 1.5 g. Table 1 shows the physical properties of the obtained external additive particles 4 for toner.

<Production Example of External Additive Particles 5 for Toner>
In the hydrolysis step, the stirring temperature was changed to 40° C., and the amount of 25% aqueous ammonia used in the polycondensation step was changed to 2.3 g. External additive particles 5 were obtained. Table 1 shows the physical properties of the obtained external additive particles 5 for toner.

<Production Example of External Additive Particles 6 for Toner>
In the hydrolysis step, the stirring temperature was changed to 50° C., and the RO water used in the polycondensation step was changed to 98.8 g, methanol to 310.0 g, and 25% ammonia water to 1.5 g. External additive particles 6 for toner were obtained in the same manner as in the production example of additive particles 1 . Table 1 shows the physical properties of the obtained external additive particles 6 for toner.

<Production Example of External Additive Particles 7 for Toner>
In the hydrolysis step, the stirring temperature was changed to 40° C., and the amount of RO water used in the polycondensation step was changed to 58.8 g, methanol to 350.0 g, and 25% ammonia water to 2.5 g. External additive particles 7 for toner were obtained in the same manner as in the production example of additive particles 1 . Table 1 shows the physical properties of the obtained external additive particles 7 for toner.

<Production Example of External Additive Particles 8 for Toner>
External additive particles 8 for toner were obtained in the same manner as in Production Example of External Additive Particles 1 for Toner, except that in the polycondensation step, the stirring time of the mixture after dropping the raw material solution was changed to 1.0 hour. rice field. Table 1 shows the physical properties of the obtained external additive particles 8 for toner.

<Production Example of External Additive Particles 9 for Toner>
External additive particles 9 for toner were obtained in the same manner as in Production Example of External Additive Particles 1 for Toner, except that in the polycondensation step, the stirring time of the mixture after dropping the raw material solution was changed to 2.0 hours. rice field. Table 1 shows the physical properties of the obtained external additive particles 9 for toner.

<Production Example of External Additive Particles 10 for Toner>
Manufacture of External Additive Particles 1 for Toner Except for changing the stirring time to 1.0 hour in the hydrolysis step and changing the stirring time to 1.0 hour for the mixed solution after dropping the raw material solution in the polycondensation step. External additive particles 10 for toner were obtained in the same manner as in Examples. Table 1 shows the physical properties of the obtained external additive particles 10 for toner.

<Production Example of External Additive Particles 11 for Toner>
Manufacture of External Additive Particles 1 for Toner Except for changing the stirring time to 2.0 hours in the hydrolysis step and changing the stirring time to 2.0 hours for the mixed solution after dropping the raw material solution in the polycondensation step. External additive particles 11 for toner were obtained in the same manner as in Examples. Table 1 shows the physical properties of the obtained external additive particles 11 for toner.

<Production Example of External Additive Particles 12 for Toner>
Toner external additive particles 12 were obtained in the same manner as in the production example of toner external additive particles 1 except that the hydrophobizing agent used in the hydrophobization step was changed to octamethylcyclotetrasiloxane. Table 1 shows the physical properties of the obtained external additive particles 12 for toner.

<Production Example of External Additive Particles 13 for Toner>
Toner external additive particles 13 were obtained in the same manner as in the production example of toner external additive particles 1 except that the hydrophobizing agent used in the hydrophobizing step was changed to chlorotrimethylsilane. Table 1 shows the physical properties of the obtained external additive particles 13 for toner.

<Production Example of External Additive Particles 14 for Toner>
Toner external additive particles 14 were obtained in the same manner as in the production example of toner external additive particles 1 except that the hydrophobizing agent used in the hydrophobizing step was changed to trifluoropropyltrimethoxysilane. Table 1 shows the physical properties of the obtained external additive particles 14 for toner.

<Production Example of External Additive Particles 15 for Toner>
Toner external additive particles 15 were obtained in the same manner as in the production example of toner external additive particles 1 except that the hydrophobizing agent used in the hydrophobizing step was changed to dimethylsilicone oil. Table 1 shows the physical properties of the obtained external additive particles 15 for toner.

<Production Example of External Additive Particles 16 for Toner>
Toner external additive particles 16 were obtained in the same manner as in the production example of toner external additive particles 1 except that no hydrophobizing agent was added in the hydrophobizing step. Table 1 shows the physical properties of the obtained external additive particles 16 for toner.

<Production Example of External Additive Particles 17 for Toner>
External toner additive particles 17 were obtained in the same manner as in Production Example of External Toner Additive Particles 1, except that 30.1 g of tetraethoxysilane and 24.3 g of dimethyldimethoxysilane were used in the hydrolysis step. rice field. Table 1 shows the physical properties of the obtained external additive particles 17 for toner.

<Production Example of External Additive Particles 18 for Toner>
External toner additive particles 18 were obtained in the same manner as in Production Example of External Toner Additive Particles 1, except that 23.5 g of tetraethoxysilane and 30.9 g of dimethyldimethoxysilane were used in the hydrolysis step. rice field. Table 1 shows the physical properties of the obtained external additive particles 18 for toner.

<Production Example of External Additive Particles 19 for Toner>
External toner additive particles 19 were obtained in the same manner as in Production Example of external toner additive particles 1, except that 33.8 g of tetraethoxysilane and 20.6 g of dimethyldimethoxysilane were used in the hydrolysis step. rice field. Table 1 shows the physical properties of the obtained external additive particles 19 for toner.

<Production Example of External Additive Particles 20 for Toner>
Manufacture of External Additive Particles 1 for Toner except that in the hydrolysis step, the stirring time was changed to 2.0 hours, and in the polycondensation step, the stirring time of the mixture after dropping the raw material solution was changed to 2.5 hours. External additive particles 20 for toner were obtained in the same manner as in the example. Table 1 shows the physical properties of the obtained external additive particles 20 for toner.

<Production Example of External Additive Particles 21 for Toner>
In the hydrolysis step, the stirring temperature was changed to 35° C. and the stirring time was changed to 1.0 hour. External additive particles 21 for toner were obtained in the same manner as in the production example of additive particles 1 . Table 1 shows the physical properties of the obtained external additive particles 21 for toner.

<Production Example of External Additive Particles 22 for Toner>
In the hydrolysis step, 16.9 g of tetraethoxysilane and 18.6 g of dimethyldimethoxysilane were added, 18.9 g of trimethoxymethylsilane was added, the stirring temperature was 30°C, and the stirring time was 0.5 hours. External additive particles 22 for toner were obtained in the same manner as in Production Example of External Additive Particles 1 for Toner, except for changing to . Table 1 shows the physical properties of the obtained external additive particles 22 for toner.

<Production Example of External Additive Particles 23 for Toner>
In the hydrolysis step, 22.1 g of tetraethoxysilane and 21.6 g of dimethyldimethoxysilane were used, and 10.7 g of trimethylsilanol was added. Thus, external additive particles 23 for toner were obtained. Table 1 shows the physical properties of the obtained external additive particles 23 for toner.

<Production Example of External Additive Particles 24 for Toner>
In the hydrolysis step, tetraethoxysilane was not added, instead 45.2 g of trimethoxymethylsilane and 9.2 g of dimethyldimethoxysilane were added, and the stirring temperature was changed to 30°C and the stirring time was changed to 0.5 hours. External additive particles 24 for toner were obtained in the same manner as in Production Example of External Additive Particles 1 for toner except for the above. Table 1 shows the physical properties of the obtained external additive particles 24 for toner.

<Production Example of External Additive Particles 25 for Toner>
In the manufacturing example of the external additive particles 18 for toner, in the hydrolysis step, the stirring temperature is set to 50° C. and the stirring time is set to 1.0 hour, and in the polycondensation step, the mixed solution after dropping the raw material solution is stirred for 1 hour. Toner external additive particles 25 were obtained in the same manner as in Production Example of toner external additive particles 18, except that the time was changed to 0.0 hours. Table 1 shows the physical properties of the obtained external additive particles 25 for toner.

<Production Example of External Additive Particles 26 for Toner>
In the production example of external additive particles 18 for toner, in the hydrolysis step, 22.1 g of tetraethoxysilane and 32.3 g of dimethyldimethoxysilane were used, the stirring temperature was 50° C., and the stirring time was 1.0 hour. Then, in the polycondensation step, the toner external additive particles 26 were obtained in the same manner as in the production example of the toner external additive particles 18, except that the stirring time of the mixture after dropping the raw material solution was changed to 1.0 hour. got Table 1 shows the physical properties of the obtained external additive particles 26 for toner.

<Production Example of External Additive Particles 27 for Toner>
In the hydrolysis step, tetraethoxysilane and dimethyldimethoxysilane were not added, 54.4 g of trimethoxymethylsilane was added instead, the stirring temperature was changed to 30 ° C., and the stirring time was changed to 0.5 hours. External additive particles 27 for toner were obtained in the same manner as in Production Example of External Additive Particles 1 for Toner. Table 1 shows the physical properties of the obtained external additive particles 27 for toner.

<Production Example of External Additive Particles 28 for Toner>
In the production example of external additive particles 27 for toner, the same procedure as in production example of external additive particles 27 for toner was carried out, except that the amount of trimethoxymethylsilane was changed to 50.6 g and 3.8 g of tetraethoxysilane was added. External additive particles 28 for toner were obtained. Table 1 shows the physical properties of the obtained external additive particles 28 for toner.

<Production Example of External Additive Particles 29 for Toner>
In the hydrolysis step, 30.1 g of tetraethoxysilane and 8.2 g of dimethyldimethoxysilane were added, 16.1 g of trimethoxymethylsilane was added, the stirring temperature was 30° C., and the stirring time was 0.5 hours. Toner external additive particles 29 were obtained in the same manner as in the production example of external additive particles 1 for toner except for changing to . Table 1 shows the physical properties of the obtained external additive particles 29 for toner.

<Production Example of External Additive Particles 30 for Toner>
In the hydrolysis step, 15.4 g of tetraethoxysilane and 8.2 g of dimethyldimethoxysilane were added, 30.8 g of trimethoxymethylsilane was added, the stirring temperature was 30° C., and the stirring time was 0.5 hours. Toner external additive particles 30 were obtained in the same manner as in the production example of external additive particles 1 for toner except for changing to . Table 1 shows the physical properties of the obtained external additive particles 30 for toner.

<Production Example of External Additive Particles 31 for Toner>
124.0 g of ethanol, 24.0 g of RO water, and 10.0 g of 28% ammonia water are added to a 2000 ml beaker, the solution is adjusted to 70° C., and 232.0 g of tetraethoxysilane and 232.0 g of tetraethoxysilane are stirred while stirring. 84.0 g of 5.4% aqueous ammonia was added dropwise over 0.5 hours. After the dropwise addition was completed, hydrolysis was continued for 0.5 hour to obtain a dispersion of silicon polymer particles having siloxane bonds.

After adding 95.0 g of hexamethyldisilazane at room temperature to the dispersion of silicon polymer particles having siloxane bonds obtained in the above step, the dispersion is heated to 50 to 60° C. and stirred for 3.0 hours. Then, the powder in the dispersion liquid was collected by suction filtration and dried under reduced pressure at 120° C. for 24 hours to obtain external additive particles 31 for toner. Table 1 shows the physical properties of the obtained external additive particles 31 for toner.

表中、Ｓｉ－Ｏ－Ｓｉ％は、ケイ素重合体に帰属される全ピーク面積のうちシロキサン
結合に帰属されるピーク面積の割合である。また、粒径は一次粒子の個数平均粒径であり、円形度は平均円形度である。 <Production Example of External Additive Particles 32 for Toner>
In Production Example of External Additive Particles 31 for Toner, the same procedure as in Production Example of External Additive Particles 31 for Toner was carried out, except that 208.8 g of tetraethoxysilane and 23.2 g of trimethoxymethylsilane were added. External additive particles 32 for toner were obtained. Table 1 shows the physical properties of the obtained external additive particles 32 for toner.

In the table, Si--O--Si % is the ratio of the peak area attributed to siloxane bonds to the total peak area attributed to silicon polymer. The particle size is the number average particle size of primary particles, and the circularity is the average circularity.

<Production example of polyester resin A1>
・Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane
76.9 parts (0.167 mole part)
- Terephthalic acid (TPA) 25.0 parts (0.145 mol part)
- Adipic acid 8.0 parts (0.054 mol part)
- Titanium tetrabutoxide 0.5 parts The above materials were placed in a 4-liter glass flask with four necks, equipped with a thermometer, a stirring bar, a condenser and a nitrogen inlet tube, and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200°C. (First reaction step) After that, 1.2 parts (0.006 mol part) of trimellitic anhydride (TMA) was added and reacted at 180°C for 1 hour (second reaction step) to obtain polyester resin A1. . The acid value of this polyester resin A1 was 5 mgKOH/g.

<Production example of polyester resin A2>
・Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane
71.3 parts (0.155 mole part)
- Terephthalic acid 24.1 parts (0.145 mol part)
- Titanium tetrabutoxide 0.6 part The above materials were placed in a 4-liter four-necked glass flask, equipped with a thermometer, a stirring bar, a condenser and a nitrogen inlet tube, and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2 hours while stirring at a temperature of 200°C. Thereafter, 5.8 parts (0.030 mol part) of trimellitic anhydride was added and reacted at 180° C. for 10 hours to obtain polyester resin A2. The acid value of this polyester resin A2 was 10 mgKOH/g.

<Production example of polyester resin A3>
・Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane
73.4 parts (0.186 mole part)
- Terephthalic acid (TPA) 11.6 parts (0.070 mol part)
- Adipic acid 6.8 parts (0.047 mol part)
Di(2-ethylhexylic acid) tin 0.5 part The above materials were placed in a 4-liter four-necked glass flask, equipped with a thermometer, a stirring bar, a condenser and a nitrogen inlet tube, and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2 hours while stirring at a temperature of 200°C. Thereafter, trimellitic anhydride (TMA): 8.2 parts (0.039 mol part) was added and reacted at 160° C. for 15 hours to obtain polyester resin A3. The acid value of this polyester resin A3 was 20 mgKOH/g.

<Production example of polyester resin A4>
・Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane
76.9 parts (0.167 mole part)
- Terephthalic acid (TPA) 24.1 parts (0.140 mol part)
- Titanium tetrabutoxide 0.5 parts The above materials were placed in a 4-liter glass flask with four necks, equipped with a thermometer, a stirring bar, a condenser and a nitrogen inlet tube, and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200°C. After that, 5.3 parts (0.024 mole parts) of trimellitic anhydride (TMA) are added,
A reaction was carried out at 80° C. for 1 hour to obtain a polyester resin A4. The acid value of this polyester resin A4 was 25 mgKOH/g.

<Production Example of Toner Particle 1>
- 70.0 parts of polyester resin A1 - 30.0 parts of polyester resin A2 - 5.0 parts of Fischer-Tropsch wax (maximum endothermic peak temperature of 78°C) - C.I. I. Pigment Blue 15: 3 5.0 parts 3,5-di-t-butylsalicylic acid aluminum compound 0.1 parts Henschel mixer (FM-75 type, manufactured by Nippon Coke Industry Co., Ltd.) After mixing at a rotation speed of 20 s ⁻¹ and a rotation time of 5 minutes, it was kneaded with a twin-screw kneader (PCM-30 type, manufactured by Ikegai Co., Ltd.) set at a temperature of 125° C. and a rotation speed of 300 rpm. The resulting kneaded product was cooled and coarsely pulverized with a hammer mill to a diameter of 1 mm or less to obtain a coarsely pulverized product. The coarsely crushed material obtained was finely pulverized with a mechanical pulverizer (T-250, manufactured by Freund Turbo Co., Ltd.).

Further, classification was performed using a rotary classifier (200 TSP, manufactured by Hosokawa Micron Corporation), and toner particles 1 were obtained. As for the operating conditions of a rotary classifier (200 TSP, manufactured by Hosokawa Micron Corporation), classification was performed at a classification rotor speed of 50.0 s ⁻¹ . The obtained toner particles 1 had a weight average particle size (D4) of 5.9 μm.

<Production Example of Toner Particles 2>
Toner Particle 2 was obtained in the same manner as in Toner Particle 1 Production Example, except that Polyester Resin A1 was changed to Polyester Resin A3. The obtained toner particles 2 had a weight average particle size (D4) of 5.9 μm.

<Production Example of Toner Particles 3>
Toner Particles 3 were obtained in the same manner as in Production Example of Toner Particles 1, except that Polyester Resin A1 in Production Example of Toner Particles 1 was changed to Polyester Resin A4. The obtained toner particles 3 had a weight average particle diameter (D4) of 5.9 μm.

<Production Example of Toner 1>
・Toner particles 1 100 parts ・Toner external additive particles 1 6.0 parts The above materials are mixed in a Henschel mixer FM-10C (manufactured by Mitsui Miike Kakoki Co., Ltd.) at a rotation speed of 30 s ⁻¹ for a rotation time of 10 minutes to obtain a toner. got 1.

表中、添加量は、トナー粒子１００部に対する部数である。 <Manufacturing Examples of Toners 2 to 34>
Toners 2 to 34 were produced in the same manner as in Toner 1 Production Example except that the toner particles and external additives for toner were changed to those shown in Table 2.

In the table, the amount added is the number of parts per 100 parts of the toner particles.

<Manufacturing example of carrier 1>
・Magnetite 1 having a number average particle diameter of 0.30 μm and a magnetization strength of 65 Am ² /kg under a magnetic field of 1000/4π (kA/m)
・Magnetite 2 with a number-average particle size of 0.50 μm and a magnetization strength of 65 Am ² /kg under a magnetic field of 1000/4π (kA/m)
Add 4.0 parts of a silane compound (3-(2-aminoethylaminopropyl)trimethoxysilane) to 100 parts of each of the above materials, mix and stir at high speed in a container at 100 ° C. or higher, and separate each fine particle. processed.

・Phenol: 10% by mass
Formaldehyde solution: 6% by mass (40% by mass formaldehyde, 10% by mass methanol, 50% by mass water)
・ Magnetite treated with the above silane compound 1: 58% by mass
・ Magnetite 2 treated with the above silane compound: 26% by mass

100 parts of the above materials, 5 parts of a 28% by mass aqueous ammonia solution, and 20 parts of water are placed in a flask, heated to 85° C. for 30 minutes while stirring and mixing, and polymerized for 3 hours to form a phenolic resin. was cured. Thereafter, the hardened phenol resin was cooled to 30° C., water was added, the supernatant was removed, and the precipitate was washed with water and then air-dried. Then, this was dried at a temperature of 60° C. under reduced pressure (5 mmHg or less) to obtain a magnetic material-dispersed spherical carrier 1 . The volume-based 50% particle size (D50) was 34.2 μm.

<Production example of two-component developer 1>
Two-component developer 1 was obtained by adding 8.0 parts of toner 1 to 92.0 parts of carrier 1 and mixing them with a V-type mixer (V-20, manufactured by Seishin Enterprise Co., Ltd.).

<Production Examples of Two-Component Developers 2 to 34>
Two-component developers 2 to 34 were obtained in the same manner as in the production example of two-component developer 1, except that the toner was changed as shown in Table 3.

<Toner evaluation method>
(1) Measurement of Image Density Change Using a full-color copier imagePress C800 manufactured by Canon as an image forming apparatus, the two-component developer is placed in a cyan developer of the image forming apparatus, and the toner is added to a cyan toner container. It was put in and evaluated later. The modified point is to remove the mechanism for discharging the magnetic carrier, which has become excessive inside the developing device, from the developing device. Plain paper GF-C081 (A4, basis weight 81.4 g/m ² , marketed by Canon Marketing Japan Inc.) was used as evaluation paper.

Adjustment was made so that the amount of toner on the paper in the FFh image (solid image) was 0.45 mg/cm ² . FFh is a value representing 256 gradations in hexadecimal, where 00h is the first gradation of 256 gradations (white background) and FF is the 256th gradation of 256 gradations (solid portion). . First, an image output test was performed on 1,000 sheets with an image ratio of 1%. While 1,000 sheets were continuously passed, the sheets were passed under the same developing conditions and transfer conditions (without calibration) as those for the first sheet.

After that, an image output test was performed on 1,000 sheets with an image ratio of 80%. While 1,000 sheets were continuously passed, the sheets were passed under the same developing conditions and transfer conditions (without calibration) as those for the first sheet. The image density of the 1,000th sheet printed with an image ratio of 1% was defined as the initial density, and the density of the image on the 1,000th sheet printed with an image ratio of 80% was measured and evaluated.

The above test was performed under normal temperature and normal humidity environment (N / N; temperature 25 ° C., relative humidity 55%), high temperature and high humidity environment (H / H; temperature 30 ° C., relative humidity 80%) and normal temperature and low humidity environment (N /L; temperature 23° C., relative humidity 5%). Using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite), the density of the 1,000th image in printing with an initial density and an image ratio of 80% is measured, and the difference Δ is used. were ranked according to the following criteria.
(Evaluation criteria: image density difference Δ)
A: Less than 0.02 B: 0.02 or more and less than 0.05 C: 0.05 or more and less than 0.10 D: 0.10 or more and less than 0.15 E: 0.15 or more

(2) Method for evaluating fogging in non-image areas (white background areas) after running As an image forming apparatus, Canon's full-color copier imageRUNNER ADVA was used.
Using a modified machine of NCE C5255, two-component developer 1 was put into the developing device of the cyan station and evaluated. Adjustment was made so that the amount of toner on the paper in the FFh image (solid image) was 0.45 mg/cm ² . The evaluation environment was N/N, H/H, and N/L environments, and the evaluation paper was plain copy paper GFC-081 (A4, basis weight 81.4 g/ ^m2 , sold by Canon Marketing Japan Inc.). Using. In each environment, an FFh image of 1 cm×1 cm was printed in the center of A4 paper, and the fogging of the white background portion was measured after 50,000 sheets were output.

The reflectance Dr (%) of the evaluation paper before image reproduction was measured by a reflectometer ("REFECTOMETER MODEL TC-6DS" manufactured by Tokyo Denshoku Co., Ltd.). After the endurance (50001st sheet), the reflectance Ds (%) of the 00H image portion (white background portion) was measured. Fog (%) was calculated from the obtained Dr and Ds using the following formula.
Fog (%) = Dr (%) - Ds (%)
The evaluation results were ranked according to the following criteria.
(Evaluation criteria fog (%))
A: Less than 1.0% B: 1.0% or more and less than 1.5% C: 1.5% or more and less than 2.0% D: 2.0% or more and less than 2.5% E: 2.5% or more

(3) Evaluation Method of Charging Stability The triboelectrification amount of the toner was calculated by collecting the toner on the electrostatic latent image carrier by suction using a metal cylindrical tube and a cylindrical filter. Specifically, the triboelectric charge amount of the toner on the electrostatic latent image bearing member was measured by a Faraday-Cage. A Faraday cage is a coaxial double cylinder in which the inner and outer cylinders are insulated. If a charged body with an electric charge of Q is placed in this inner cylinder, it will be as if a metal cylinder with an electric charge of Q exists due to electrostatic induction. The amount of this induced charge was measured with an electrometer (Kesley 6517A, manufactured by Kessley). Quantity.
Triboelectric charge amount of toner (mC/kg)=Q/M
Evaluation image: A 2 cm x 5 cm image of FFh is placed in the center of A4 paper

First, the evaluation image is formed on an electrostatic latent image carrier, and before being transferred to an intermediate transfer member, the rotation of the electrostatic latent image carrier is stopped, and the toner on the electrostatic latent image carrier is transferred to a metal. It was collected by suction using a cylindrical tube and a cylindrical filter, and [initial Q/M] was measured. Subsequently, after leaving the developing device in the evaluation machine for two weeks in N/N, H/H and N/L environments, the same operation as before leaving was performed, and the electrostatic latent image bearing member after leaving. The charge amount Q/M (mC/kg) per unit mass was measured. From the Q/M per unit mass on the initial electrostatic latent image carrier and the Q/M per unit mass on the electrostatic latent image carrier after standing, the rate of change in Q/M after standing ( [Initial Q/M]-[Q/M after being left in each environment])×100/[Initial Q/M] was calculated and judged according to the following criteria. (Evaluation criteria)
A: The rate of change is less than 2% B: The rate of change is 2% or more and less than 5% C: The rate of change is 5% or more and less than 10% D: The rate of change is 10% or more and less than 15% E: The rate of change is 15% or more

<Evaluation results of Examples 1 to 27>
Table 4 shows the evaluation results of Examples 1 to 27.

<Evaluation results of Comparative Examples 1 to 7>
Table 4 shows the evaluation results of Comparative Examples 1 to 7.

<Manufacturing Examples of Toners 35 to 39>
Toners 35 to 39 were produced in the same manner as in Toner 1 Production Example, except that the toner particles and external additives for toner were changed to those shown in Table 5.

<Production Examples of Two-Component Developers 35 to 39>
Two-component developers 35 to 39 were obtained in the same manner as in the production example of two-component developer 1, except that the toner was changed as shown in Table 6.

<Evaluation results of Examples 28 to 32>
Table 7 shows the evaluation results of Examples 28 to 32.

Claims (10)

An external additive for toner containing silicon polymer particles having a siloxane bond and a Si—R ¹ bond,
In the chart obtained by ²⁹ Si-NMR measurement of the toner external additive, A is the total peak area attributed to the toner external additive, and Si—R ¹ bond (the R ¹ has 1 to 1 carbon atoms). represents the alkyl group of 6.) When the peak area attributed to B, the following formula (1) is satisfied,
In the chart obtained by ²⁹ Si-NMR measurement of the external additive for toner, SA is the total peak area attributed to the silicon polymer, and S3 is the peak area attributed to the T unit structure. An external additive for a toner that satisfies (2).
0.260≦B/A≦0.450 (1)
0.00≦S3/SA≦0.50 (2) the silicon polymer has the siloxane bond, the Si—R ¹ bond and the Si—OR ² bond;
In the chart obtained by ²⁹ Si-NMR measurement of the external additive for toner, when C is the peak area attributed to the Si-OR ² bond contained in the external additive for toner, the following formula (3) is obtained. The external additive for toner according to claim 1, which satisfies:
0.050≦(C/A)/(B/A)≦0.180 (3)
(The R ² represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom.) 3. The external additive for toner according to claim 1, wherein the primary particles of the external additive for toner have a number average particle size of 0.02 μm to 0.30 μm. 4. The toner external additive according to any one of claims 1 to 3, wherein the surface is treated with at least one compound selected from the group consisting of alkylsilazane compounds, alkylalkoxysilane compounds, chlorosilane compounds, siloxane compounds and silicone oils. An external additive for toner according to the above item. The external additive for toner according to any one of claims 1 to 4, wherein the external additive for toner has an average circularity of 0.85 to 0.95. The ratio of the peak area attributed to the siloxane bond to the total peak area attributed to the silicon polymer calculated from the chart obtained by ²⁹ Si-NMR measurement of the external additive for toner is 60.0. % to 85.0%, the external additive for toner according to any one of claims 1 to 5. In the chart obtained by ²⁹ Si-NMR measurement of the external additive for toner, SA is the total peak area attributed to the silicon polymer, S4 is the peak area attributed to the Q unit structure, and S4 is the peak area attributed to the T unit structure. The external toner according to any one of claims 1 to 6, which satisfies the following formulas (I) to (III), where S3 is the peak area assigned to the D unit structure and S2 is the peak area attributed to the D unit structure. additives.
0.20≦S4/SA≦0.60 (I)
0.00≦S3/SA≦0.50 (II)
0.20≦S2/SA≦0.70 (III) Claims 1 to 7, wherein said silicon polymer is a polycondensation product of at least one silicon compound selected from the group consisting of difunctional silanes and at least one silicon compound selected from the group consisting of tetrafunctional silanes. The external additive for toner according to any one of . The external additive for toner according to any one of claims 1 to 8, wherein the external additive for toner has a degree of hydrophobicity of 50% to 60% by a methanol titration method. A toner having toner particles and an external additive for toner,
The toner particles contain a binder resin,
A toner, wherein the toner external additive is the toner external additive according to any one of claims 1 to 9.