Toner additive and toner

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]

[0001] The present disclosure relates to an external toner additive and a toner used in an electrophotographic process that uses the external toner additive. [Background technology]

[0002] In recent years, with the widespread use of electrophotographic full-color copiers, there has been an increasing demand for toners used in electrophotography that can handle higher printing speeds, and that are environmentally stable and have a longer lifespan. Conventionally, silica has been widely used as an external additive in toners. Generally, there have been reports of silica obtained by a dry or wet method (sol-gel method) being surface-treated to enhance its hydrophobicity. For example, Patent Document 1 discloses an example in which highly hydrophobic spherical sol-gel silica microparticles are added to toner base particles to improve the charging stability of the toner.

[0003] However, when images are printed in a high-temperature, high-humidity environment for a long period of time, the silica present on the toner surface becomes susceptible to the effects of moisture within the image printing device, which can cause changes in the toner surface condition. This can change the toner's chargeability and result in variations in image density. Furthermore, when the image is then printed in a low-humidity environment or a normal-temperature, normal-humidity environment, the silica present on the toner surface is also affected by the humidity change, resulting in variations in image density. Thus, there is still room for improvement in terms of toner charge stability when the image printing environment changes.

[0004] 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. Patent Document 4 discloses an example of silica in which the number of highly hydrophilic silanol groups has been reduced. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-099582 [Patent Document 2] International Publication No. 2015 / 107961 [Patent Document 3] Japanese Patent Application Publication No. 2018-004949 [Patent Document 4] Japanese Patent Application Laid-Open No. 2008-189545 Summary of the Invention [Problem to be solved by the invention]

[0006] However, it has been found that the techniques of all of the documents are insufficient to suppress changes in the hygroscopicity of the external additives when images are printed in a high-temperature, high-humidity environment or when images are printed under conditions of changing humidity, and therefore there is room for improvement in terms of toner charging stability, image density stability, and environmental stability. The present disclosure provides an external toner additive and a toner that have charging stability and can suppress fluctuations in image density even when images are printed in high-temperature, high-humidity environments or when images are printed under conditions of changing humidity. [Means for solving the problem]

[0007] The present disclosure relates to siloxane bonds and Si-R 1 An external toner additive comprising particles of a silicon polymer having a bond, The external additive for toner 29 In the chart obtained by Si-NMR measurement, the total peak area attributed to the external toner additive is defined as A, and Si-R 1 Bond (the R 1 represents an alkyl group having 1 to 6 carbon atoms. When the peak area attributed to the above group is defined as B, the following formula (1) is satisfied: The external additive for toner 29 In a chart obtained by Si-NMR measurement, when the total peak area attributable to the silicon polymer is SA and the peak area attributable to the T unit structure is S3, the external toner additive satisfies the following formula (2): 0.260≦B / A≦0.450 (1) 0.00≦S3 / SA≦0.50 (2) [Effects of the Invention]

[0008] The present disclosure can provide an external toner additive and a toner that have charging stability and can suppress fluctuations in image density even when images are printed in high-temperature, high-humidity environments or when images are printed under conditions of changing humidity. DETAILED DESCRIPTION OF THE INVENTION

[0009] In the present disclosure, unless otherwise specified, the expressions "XX or more and YY or less" or "XX to YY" representing a numerical range mean a numerical range including the lower and upper limits, which are the endpoints. When a numerical range is described in stages, the upper and lower limits of each numerical range can be combined in any way.

[0010] The present inventors believe the mechanism by which the above-mentioned effects are realized is as follows. Typical sol-gel silica particles that have been used as external toner additives are particles whose main component is a siloxane bond (Si-O-Si). Normally, sol-gel silica particles have silanol groups at their terminals, resulting in residual unreacted silanol groups on the surface and inside of the silica particles. Even if the residual silanol groups are trimethylsilylated by a coupling reaction with a silane compound or the like to improve hydrophobicity, this is insufficient to suppress changes in charging properties during long-term use in a high-temperature, high-humidity environment. As a result of extensive research by the present inventors, it was found that siloxane bonds and Si-R 1 In an external additive containing a silicon polymer having a bond, the Si-R 1 It was found that the above problem can be solved by optimizing the amount of Si (to which alkyl groups are bonded). The mechanism behind this is thought to be that by introducing alkyl groups such as SiCH3 into the external additive particles, the hydrophobicity of the external additive particles themselves is increased, stabilizing the surface charge. As a result, it is speculated that changes in the toner charge amount in high-temperature, high-humidity environments and changes in the toner charge amount due to humidity changes can be suppressed.

[0011] The present disclosure relates to siloxane bonds and Si-R 1 An external toner additive comprising particles of a silicon polymer having a bond, The external additive for toner 29 In the chart obtained by Si-NMR measurement, the total peak area attributed to the external toner additive is defined as A, and the Si-R 1 Bond (the R 1 represents an alkyl group having 1 to 6 carbon atoms. When the peak area attributed to the above group is defined as B, the following formula (1) is satisfied: The external additive for toner 29 In a chart obtained by Si-NMR measurement, when the total peak area attributable to the silicon polymer is SA and the peak area attributable to the T unit structure is S3, the external toner additive satisfies the following formula (2): 0.260≦B / A≦0.450 (1) 0.00≦S3 / SA≦0.50 (2)

[0012] 29 In Si-NMR, peaks are detected in different shift regions depending on the structure of the functional groups bonded to Si in the constituent compounds of the silicon polymer. By identifying the position of each peak using a standard sample, the structure bonded to Si can be identified. Furthermore, the abundance ratio of each constituent compound can be calculated from the obtained peak area. The ratio of the peak area 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 calculated. [ka]

[0013] 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, and even more preferably 1). Furthermore, of the total peak area A, the Si-R 1 The ratio of the peak area B attributed to the bond (B / A) is the ratio of the Si-R1 By satisfying formula (1), the amount of alkyl groups present inside the external additive particles becomes optimal, and the environmental stability and charging stability of the toner can be improved. 0.260≦B / A≦0.450 (1) Si-R 1 In R 1 represents an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3, more preferably 1 or 2, and even more preferably 1).

[0014] If 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 electrostatic stability is not realized. Also, if B / A is more than 0.450, the amount of siloxane bonds present inside the external additive particles is relatively small, and the robustness and stability of the particles are reduced. Preferably, 0.280≦B / A ≦0.450, more preferably 0.300≦B / A ≦0.400, and even more preferably 0.300≦B / A ≦0.330. Within this range, the environmental stability and charging stability of the toner are further improved.

[0015] The method for producing the silicon polymer particles of the external toner additive is not particularly limited, but it is preferable to form the particles through hydrolysis of a silicon compound (silane monomer) by the sol-gel method and a condensation polymerization reaction. Specifically, it is preferable to form the particles by polymerizing a mixture of a bifunctional silane having two siloxane bonds and a tetrafunctional silane having four siloxane bonds through hydrolysis and a condensation polymerization reaction. Silane monomers such as bifunctional silane and tetrafunctional silane will be described later.

[0016] 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 bifunctional silane is preferably 50 mol% to 70 mol%, more preferably 61 mol% to 65 mol%. The proportion of tetrafunctional silane is preferably 30 mol % to 50 mol %, more preferably 35 mol % to 39 mol %.

[0017] The present inventors have found that in the method for producing an external toner additive, the above-mentioned effects can be achieved by adjusting the mixing ratio of the above-mentioned 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.

[0018] For example, methods for increasing B / A include increasing the mixing ratio of bifunctional silane, lowering the temperature during the condensation reaction, shortening the stirring time, lowering the pH of the solution, lowering the temperature during hydrolysis, etc. Methods for decreasing B / A include increasing the mixing ratio of tetrafunctional silane, raising the temperature during the condensation reaction, lengthening the stirring time, raising the pH of the solution, raising the temperature during hydrolysis, etc.

[0019] The toner external additive contains silicon polymer particles having siloxane bonds, and the silicon polymer particles preferably contain 90% by mass or more, more preferably 95% by mass or more of silicon polymer.

[0020] The method for producing silicon polymer particles is not particularly limited, and for example, a silane compound can be added dropwise to water, hydrolyzed and condensed in the presence of a catalyst, and the resulting suspension can be filtered and dried. The particle size can be controlled by the type of catalyst, the compounding ratio, the reaction initiation temperature, the dropwise addition time, etc. Examples of acidic catalysts include hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, and examples of basic catalysts include, but are not limited to, aqueous ammonia, sodium hydroxide, and potassium hydroxide.

[0021] Silicon polymer particles are preferably produced by the following method.Specifically, it is preferable to include the following steps: a first step of obtaining a hydrolyzate of a silicon compound; a second step of mixing the hydrolyzate with an alkaline aqueous medium to cause a polycondensation reaction of the hydrolyzate; and a third step of mixing the polycondensation reaction product with an aqueous solution to form particles.In some cases, a hydrophobic agent may be further added to the spherical silicon polymer particle dispersion to obtain hydrophobic spherical silicon polymer particles.

[0022] In the first step, a silicon compound is contacted with a catalyst 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. Known catalysts can be suitably used. Specific examples of acidic catalysts include acetic acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, while basic catalysts include aqueous ammonia, sodium hydroxide, and potassium hydroxide.

[0023] The amount of catalyst used may be adjusted appropriately depending on the type of silicon compound and catalyst. Preferably, the amount of catalyst used is 1×10 -3 The amount is selected in the range of 1 part by mass to 1 part by mass.

[0024] The amount of catalyst used is 1×10 -3 If the amount of catalyst used is 1 part by mass or more, the reaction will proceed sufficiently. On the other hand, if the amount of catalyst used is 1 part by mass or less, the concentration of impurities remaining in the fine particles will be low, making hydrolysis easier. The amount of water used is preferably 2 to 15 moles per mole of silicon compound. If the amount of water is 2 moles or more, the hydrolysis reaction will proceed sufficiently, and if it is 15 moles or less, productivity will be improved.

[0025] The reaction temperature is not particularly limited, and may be carried out at room temperature or under heating, but it is preferable to carry out the reaction at a temperature maintained at 10 to 60°C, since this allows a hydrolysate to be obtained in a short time and the partial condensation reaction of the produced hydrolysate to be suppressed. The reaction time is not particularly limited, and should be determined taking into consideration the reactivity of the silicon compound used, the composition of the reaction solution prepared by mixing the silicon compound, acid, and water, and productivity. It should be selected appropriately taking into consideration.

[0026] In the second step of the method for producing silicon polymer particles, the raw material solution obtained in the first step is mixed with an alkaline aqueous medium to polycondense the particle precursor, thereby obtaining a polycondensation reaction solution. Here, the alkaline aqueous medium is a liquid obtained by mixing an alkaline component, water, and, if necessary, an organic solvent.

[0027] The alkaline component used in the alkaline aqueous medium is one whose aqueous solution is basic and acts as a neutralizer for the catalyst used in step 1 and as a catalyst for the polycondensation reaction in step 2. Examples of such alkaline components include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; ammonia; and organic amines such as monomethylamine and dimethylamine.

[0028] The amount of the alkali component used is an amount that neutralizes the acid and effectively acts as a catalyst for the polycondensation reaction. For example, when ammonia is used as the alkali component, the amount is usually selected in the range of 0.01 mass % or more and 12.5 mass % or less per 100 parts by mass of the mixture of water and the organic solvent.

[0029] In the second step, in order to prepare an alkaline aqueous medium, an organic solvent may be used in addition to the alkaline component and water. 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 preferred.

[0030] Specific examples include 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; ethers such as ethylene glycol monoethyl ether, acetone, diethyl ether, tetrahydrofuran, and diacetone alcohol; and amide compounds such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

[0031] Among the organic solvents listed above, alcohol solvents such as methanol, ethanol, 2-propanol, butanol, etc. are preferred. Furthermore, from the viewpoint of hydrolysis and dehydration condensation reactions, it is more preferred to select as the organic solvent the same alcohol as the alcohol produced by elimination.

[0032] In the third step, the polycondensation reaction product obtained in the second step is mixed with an aqueous solution to form particles. Water (tap water, pure water, etc.) is preferably used as the aqueous solution, but components compatible with water, such as salts, acids, alkalis, organic solvents, surfactants, and water-soluble polymers, may also be added to the water. The temperatures of the polycondensation reaction liquid and the aqueous solution when mixed are not particularly limited, and are preferably selected in the range of 5 to 70°C, taking into consideration the composition, productivity, etc.

[0033] The silicon polymer particles can be recovered by any known method without any particular limitations. For example, floating powder can be scooped out or a filtration method can be used, but filtration is preferred because of its simple operation. The filtration method is not particularly limited, and known devices such as vacuum filtration, centrifugal filtration, and pressure filtration can be selected. The filter paper, filter, filter cloth, etc. used in filtration are not particularly limited as long as they are industrially available, and can be selected appropriately depending on the device used.

[0034] The silicon polymer particles may be surface-treated by known means such as a silane coupling agent or silicone oil to adjust the degree of hydrophobicity.

[0035] The monomers used can be appropriately selected based on their compatibility with the solvent and catalyst, their hydrolysis properties, etc., but tetraethoxysilane is preferred as the tetrafunctional silane, and dimethyldimethoxysilane is preferred as the bifunctional silane.

[0036] The silicon polymer is preferably a condensation polymer of at least one silicon compound selected from the group consisting of silicon compounds having a structure represented by the following formula (2). [ka]

[0037] In formula (2), R 2 , R 3 , R 4 and R 5 R each independently represents 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 (for example, 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)). 2 , R 3 , R 4 and R 5 At least one of the groups is the reactive group. R 2 , R 3 , R 4 and R 5 are preferably each independently an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3, more preferably 1 or 2) or an alkoxy group (preferably having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms).

[0038] To obtain silicon polymer particles, a silicon compound having four reactive groups in one molecule (tetrafunctional silane) of formula (2), R 2 is an alkyl group or a phenyl group, and three reactive groups (R 3 , R 4 , R 5 ), an organosilicon compound (trifunctional silane) having R in formula (2) 2 , R 3 is an alkyl group or a phenyl group, and two reactive groups (R 4 , R 5 ), an organosilicon compound (bifunctional silane) having R in formula (2) 2 , R 3 , R 4 is an alkyl group or a phenyl group, and one reactive group (R 5 ) can be used.

[0039] These reactive groups undergo hydrolysis, addition polymerization, and condensation polymerization to form crosslinked structures, resulting in silicon polymer particles. 3 , R 4 and R 5 The hydrolysis, addition polymerization, and condensation polymerization can be controlled by the reaction temperature, reaction time, reaction solvent, and pH.

[0040] Examples of tetrafunctional silanes include tetramethoxysilane, tetraethoxysilane, and tetraisocyanate silane.

[0041] Examples of 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, Examples of such silane include silane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, and phenyltrihydroxysilane.

[0042] Examples of bifunctional silanes include di-tert-butyldichlorosilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, dibutyldichlorosilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dichlorodecylmethylsilane, dimethoxydecylmethylsilane, diethoxydecylmethylsilane, dichlorodimethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, and diethyldimethoxysilane.

[0043] Examples of monofunctional silanes include t-butyldimethylchlorosilane, t-butyldimethylmethoxysilane, t-butyldimethylethoxysilane, t-butyldiphenylchlorosilane, t-butyldiphenylmethoxysilane, t-butyldiphenylethoxysilane, chlorodimethylphenylsilane, methoxydimethylphenylsilane, ethoxydimethylphenylsilane, chlorotrimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, triethylmethoxysilane, triethylethoxysilane, tripropylmethoxysilane, tributylmethoxysilane, tripentylmethoxysilane, triphenylchlorosilane, triphenylmethoxysilane, and triphenylethoxysilane.

[0044] Silicon polymers contained in external toner additives have siloxane bonds, Si-R 1 Bonds and Si-OR 2It is preferable that the external additive for toner has a bond. 29 In the chart obtained by Si-NMR measurement, the Si-OR contained in the external toner additive 2 When the area of ​​the peak assigned to is defined as C, it is preferable that the following formula (3) is 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.

[0045] Within the above range, the hydrophobic Si-R 1 When the ratio of the amount of hydrophilic silanol groups present is optimized, the charge-up suppression effect is exhibited in a low-humidity environment. That is, this is preferable from the viewpoint of the environmental stability and charge stability of the toner. More preferably, 0.060≦(C / A) / (B / A)≦0.150, and even more preferably, 0.075≦(C / A) / (B / A)≦0.085.

[0046] The (C / A) / (B / A) ratio can be controlled by the selection of silicon compounds, the mixing ratio of silicon compounds, and the hydrolysis and condensation conditions. For example, methods for increasing the (C / A) / (B / A) ratio include increasing the mixing ratio of tetrafunctional silane, lowering the temperature during the condensation reaction, and lowering the temperature during hydrolysis. Methods for decreasing the (C / A) / (B / A) ratio include increasing the mixing ratio of bifunctional silane, increasing the temperature during the condensation reaction, extending the stirring time, increasing the pH of the solution, and increasing the temperature during hydrolysis.

[0047] The number-average particle size of the primary particles of the external toner additive is preferably 0.02 μm to 0.30 μm. When the number-average particle size of the primary particles is within this range, the external additive can be easily coated uniformly on the toner particles. In addition, stress on the toner can be suppressed, which makes it easier to achieve the effect of charge stability.

[0048] When the number average particle size of the primary particles of the external toner additive is 0.02 μm or more, the Even when a large amount of low-density images are output over a long period of time under such a harsh environment, stress on the toner is reduced, and the external additive particles are less likely to be embedded in the toner particle surface. Furthermore, when the number-average particle size is 0.30 μm or less, the external additive particles are less likely to be detached from the toner particle surface. The number-average particle size of the primary particles of the external toner additive is more preferably 0.05 μm to 0.25 μm, and even more preferably 0.08 μm to 0.18 μm.

[0049] The external toner additive preferably has its surface treated with a hydrophobic treatment agent. That is, the external toner additive particles are preferably silicon polymer particles that have been surface-treated with a hydrophobic treatment agent. The hydrophobic treatment agent is not particularly limited, but is preferably an organosilicon compound.

[0050] Examples of such compounds include alkylsilazane compounds such as hexamethyldisilazane, alkylalkoxysilane compounds such as diethyldiethoxysilane, trimethylmethoxysilane, methyltrimethoxysilane, and butyltrimethoxysilane, fluoroalkylsilane compounds such as trifluoropropyltrimethoxysilane, chlorosilane compounds such as dimethyldichlorosilane and trimethylchlorosilane, siloxane compounds such as octamethylcyclotetrasiloxane, silicone oils, and silicone varnishes.

[0051] By subjecting the surface of the external additive particles to hydrophobic treatment, it is possible to further suppress changes in the charge amount of the toner in a high-temperature, high-humidity environment. Among these, it is preferable that the external toner additive is 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 toner additive is surface-treated with an alkylsilazane compound from the viewpoints of environmental stability and charge stability.

[0052] The hydrophobicity of the external toner additive, as measured by methanol titration, is preferably 40% to 80%, more preferably 50% to 60%, and even more preferably 50% to 55%, from the viewpoint of charge stability.

[0053] External additives for toner 29 In the chart obtained by Si-NMR measurement, when the total peak area attributed to the silicon polymer is SA and the peak area attributed to the T unit structure is S3, the ratio of S3 / SA is 0.00≦S3≦0.50. 1 When S3 / SA is 0.00 or less, the ratio of the amount of silanol groups present becomes optimal, and the environmental stability and charging stability of the toner become better. Furthermore, it is preferable that S3 / SA is 0.00 or less, and it is more preferable that S3 / SA is 0.20 or less.

[0054] External additives for toner 29 In a chart obtained by Si-NMR measurement, when the total peak area attributable to the silicon polymer is SA, the peak area attributable to the Q unit structure is S4, the peak area attributable to the T unit structure is S3, and the peak area attributable to the D unit structure is S2, it is preferable that the following formulas (I) to (III) are satisfied. 0.20≦S4 / SA≦0.60 (I) 0.00≦S3 / SA≦0.50 (II) 0.20≦S2 / SA≦0.70 (III)

[0055] If the above formulae (I) to (III) are satisfied, when the toner is subjected to stress from members such as the carrier, it is possible to prevent the external additive particles from being embedded in the surface of the toner particles and the external additive particles themselves from being destroyed.

[0056] Furthermore, it is more preferable that 0.30≦S4 / SA≦0.50, 0≦S3 / SA≦0.10, and 0.50≦S2 / SA≦0.70. When the above ranges are satisfied, the Si-R such as Si-CH3 inside the external additive particles can be easily obtained. 1When the ratio of the amount of silanol groups present is set to be optimal, it 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 the selection of silicon compounds, the mixing ratio of the silicon compounds, and the hydrolysis and condensation conditions.

[0057] External additives for toner 29 The ratio of the peak area attributable to siloxane bonds to the total peak area attributable to silicon polymers calculated from a chart obtained by Si-NMR measurement is preferably 60.0% to 85.0%, and more preferably 63.0% to 68.0%. Within the above range, the Si-R such as Si-CH3 inside the external additive particles can be easily obtained. 1 This is preferable because the ratio of the amount of siloxane bonds present becomes optimal and charging properties are improved in a high-humidity environment. The above area ratio can be controlled by the selection of the silicon compound, the mixing ratio of the silicon compound, and the hydrolysis and condensation conditions.

[0058] The average circularity of the external toner additive is preferably 0.85 to 0.95 from the viewpoint of the durability and charging stability of the toner, and more preferably 0.88 to 0.93. The average circularity can be controlled by the mixing ratio of the above-mentioned monomers and the condensation conditions.

[0059] The toner has toner particles containing a binder resin and an external toner additive, and the external toner additive is the above-mentioned external toner additive. The content of the external toner additive in the toner is preferably 0.1 to 20.0 parts by mass per 100 parts by mass of toner particles from the viewpoint of charge stability. 0.5 to 15.0 parts by mass is more preferable, and 1.0 to 10.0 parts by mass is even more preferable.

[0060] When the content of the external toner additive is 0.1 parts by mass or more, stress on the toner can be suppressed, and durability and charging stability can be improved, even when a large amount of low-density images are output over a long period of time in a harsh environment such as a high-temperature, high-humidity environment. Furthermore, when the content of the external toner additive is 20.0 parts by mass or less, filming of the external additive particles on the carrier or photosensitive material can be suppressed, even when a high-density image is output over a long period of time.

[0061] <Binder resin> The binder resin used in the toner is not particularly limited, and the following polymers can be used: homopolymers of styrene and its substituted derivatives, such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, and styrene-acrylonitrile-indene copolymer; polyvinyl chloride, phenolic resin, natural resin-modified phenolic resin, natural resin-modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral resin, terpene resin, coumarone-indene resin, and petroleum-based resin. Among these, polyester resin is preferred from the viewpoint of durability and charging stability.

[0062] In addition, it is preferable that the acid value of the polyester resin is 0.5 mgKOH / g to 40 mgKOH / g from the viewpoint of environmental stability and charging stability. 1 The acid value is preferably 1 mgKOH / g to 20 mgKOH / g. and more preferably 1 mgKOH / g to 15 mgKOH / g.

[0063] <Coloring agent> A colorant may be used in the toner particles. Examples of the colorant include the following: Black colorants include carbon black, and those toned to black using a yellow colorant, a magenta colorant, and a cyan colorant. As the colorant, a pigment may be used alone, but it is more preferable to use a dye and a pigment in combination to improve the clarity from the viewpoint of the image quality of a full-color image.

[0064] Examples of pigments for magenta toner include CI 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; CI Pigment Violet 19; CI Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

[0065] Dyes for magenta toner include solvent dyes such as CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, and 121; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21, and 27; and CI Disperse Violet 1; and basic dyes such as CI Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, and 40; and CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28.

[0066] Examples of pigments for cyan toners include CI Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, and 17; CI Vat Blue 6; CI Acid Blue 45; and copper phthalocyanine pigments with one to five phthalimidomethyl groups substituted on the phthalocyanine skeleton. Examples of dyes for cyan toners include CI Solvent Blue 70.

[0067] Examples of yellow toner pigments include CI 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, and 185; and CI Vat Yellow 1, 3, and 20. An example of a yellow toner dye is CI Solvent Yellow 162. The content of the colorant is preferably 0.1 to 30 parts by weight per 100 parts by weight of the binder resin.

[0068] <Wax> The toner particles may contain wax, for example: 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; waxes containing fatty acid esters as the main component such as carnauba wax; and partially or completely deoxidized fatty acid esters such as deoxidized carnauba wax.

[0069] Further examples include saturated straight-chain fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassidic acid, eleostearic acid, and parinaric acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; polyhydric alcohols such as sorbitol; esters of fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid with alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, and hexyl alcohol. Examples of suitable binder resins include saturated fatty acid bisamides such as m-xylene bisstearamide; unsaturated fatty acid amides such as ethylene bisoleamide, hexamethylene bisoleamide, N,N'-dioleyl adipamide, and N,N'-dioleyl sebacate; aromatic bisamides such as m-xylene bisstearamide and N,N'-distearyl isophthalamide; fatty acid metal salts (commonly known as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene or acrylic acid; partial esters of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; and hydroxyl-containing methyl ester compounds obtained by hydrogenating vegetable oils. The wax content is preferably 2.0 to 30.0 parts by mass per 100 parts by mass of the binder resin.

[0070] <Charge control agent> The toner particles may contain a charge control agent as needed. Known charge control agents can be used, but particularly preferred are metal compounds of aromatic carboxylic acids, which are colorless, can charge the toner quickly, and can stably maintain a constant charge amount.

[0071] Examples of negative charge control agents include metal salicylate compounds, metal naphthoate compounds, metal dicarboxylate compounds, polymeric compounds having sulfonic acid or carboxylic acid on the side chain, polymeric compounds having sulfonate salts or sulfonate esters on the side chain, polymeric compounds having carboxylate salts or carboxylate esters on the side chain, boron compounds, urea compounds, silicon compounds, and calixarenes.

[0072] Examples of positive charge control agents include quaternary ammonium salts, polymeric compounds having the quaternary ammonium salts in their side chains, guanidine compounds, and imidazole compounds. The charge control agent may be added internally or externally to the toner particles. The amount of charge control agent added is preferably 0.2 to 10 parts by mass per 100 parts by mass of the binder resin.

[0073] <Inorganic fine particles> In addition to the external toner additives described above, the toner may contain other inorganic fine particles as needed. 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 contained as an external additive, inorganic fine particles such as silica fine particles, titanium oxide fine particles, and aluminum oxide fine particles are preferred. The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

[0074] As an external additive to improve fluidity, 2 / g or more 400m 2 In order to simultaneously improve the flowability and stabilize the durability, inorganic fine particles having a specific surface area within the above range may be used in combination with the external toner additive.

[0075] The inorganic fine particles are preferably used in an amount of 0.1 to 10.0 parts by mass per 100 parts by mass of toner particles. When the above range is satisfied, the effect of charge stability is easily obtained. The content of the external toner additive is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, and even more preferably 90 to 100% by mass, of the total amount of external additives.

[0076] <Developer> The toner can be used as a one-component developer, but in order to further improve dot reproducibility and to provide stable images over a long period of time, it can also be mixed with a magnetic carrier and used as a two-component developer. That is, it is preferable that the toner is the above-mentioned toner, which is a two-component developer containing a toner and a magnetic carrier.

[0077] Examples of magnetic carriers that can be used include commonly known ones such as iron oxide, unoxidized iron powder; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth elements, alloy particles thereof, and oxide particles thereof; magnetic materials such as ferrite; and magnetic material-dispersed resin carriers (so-called resin carriers) containing a magnetic material and a binder resin that holds the magnetic material in a dispersed state. The mixing ratio of the magnetic carrier and the toner is preferably such that the toner concentration in the two-component developer is 2% by mass or more and 15% by mass or less, more preferably 4% by mass or more and 13% by mass or less.

[0078] <Method of manufacturing toner particles> The method for producing toner particles is not particularly limited, and known production methods such as suspension polymerization, emulsion aggregation, melt kneading, dissolution suspension, etc. The obtained toner particles can be mixed with the above-mentioned external additive for toner and, if necessary, other external additives to obtain a toner.

[0079] To mix the toner particles and external additives, a mixing device such as a double cone mixer, a V-type mixer, a drum mixer, a super mixer, a Henschel mixer, a Nauta mixer, a Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.), or a Nobilta (manufactured by Hosokawa Micron Corporation) can be used.

[0080] The methods for measuring various physical properties are explained below. <Separation of external additive particles and toner particles from toner> Physical properties can also be measured using external additives separated from toner using the following method. 200 g of sucrose (Kishida Chemical) is added to 100 mL of ion-exchanged water and dissolved in a hot water bath to prepare a sucrose concentrate. 31 g of the sucrose concentrate and 6 mL of Contaminon N (a 10% by weight aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) are placed in a centrifuge tube to prepare a dispersion. 1 g of toner is added to this dispersion, and any clumps of toner are broken up using a spatula or similar tool.

[0081] The centrifuge tube is shaken for 20 minutes in a shaker (Iwaki Sangyo KM Shaker (model: V.SX)) at 350 strokes per minute. After shaking, the solution is transferred to a glass tube (50 mL) for a swing-out rotor and centrifuged at 3500 rpm for 30 minutes.

[0082] After centrifugation, the toner is present in the top layer in the glass tube, and the external toner additive is present in the lower aqueous solution. The lower aqueous solution is sampled and centrifuged to separate the sucrose and the external toner additive, and the external toner additive is collected. If necessary, centrifugation is repeated to separate the sucrose and the external toner additive thoroughly, and then the dispersion is dried and the external toner additive is collected. When multiple external toner additives are added, the external toner additives are separated by centrifugation or the like. can be selected.

[0083] <Method for measuring the number average particle size of primary particles of external toner additive particles> The number-average particle size of the primary particles of the external toner additive is determined by centrifugal sedimentation. Specifically, 0.01 g of dried external additive particles is placed in a 25 ml glass vial, and a solution is prepared by adding 0.2 g of 5% Triton solution and 19.8 g of RO water. Next, the tip of the probe (inner tip) of the ultrasonic disperser is immersed in the solution, and ultrasonic dispersion is performed at an output of 20 W for 15 minutes to obtain a dispersion. This dispersion is then used to measure the particle size of the external toner additive using a CPS Instruments The number average particle size of primary particles was measured using a centrifugal sedimentation particle size distribution analyzer DC24000 manufactured by Epson Corporation. The disk rotation speed was set to 18,000 rpm, and the true density was 1.3 g / cm. 3 Before measurement, the instrument is calibrated using polyvinyl chloride particles with an average particle size of 0.476 μm.

[0084] <Method for measuring the acid value of resin> The acid value is the number of milligrams of potassium hydroxide required to neutralize the acid components, such as free fatty acids and resin acids, contained in 1 g of sample. The acid value is measured as follows in accordance with JIS-K0070-1992.

[0085] (1) Reagents Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume), and add ion-exchanged water 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. Place in an alkali-resistant container to avoid contact with carbon dioxide and leave for 3 days, then filter to obtain potassium hydroxide solution. Store the resulting potassium hydroxide solution in an alkali-resistant container. The potassium hydroxide solution factor is determined by placing 25 mL of 0.1 mol / L hydrochloric acid in an Erlenmeyer flask, adding several drops of the phenolphthalein solution, and titrating with the potassium hydroxide solution to determine the amount of potassium hydroxide solution required for neutralization. The 0.1 mol / L hydrochloric acid used is prepared in accordance with JIS K 8001-1998.

[0086] (2) Operation (A) Main test 2.0 g of the crushed sample was accurately weighed into a 200 mL Erlenmeyer flask, and 100 mL of a toluene / ethanol (2:1) mixture was added and allowed to dissolve for 5 hours. Next, several drops of the phenolphthalein solution were added as an indicator, and the solution was titrated with the potassium hydroxide solution. The endpoint of the titration was determined when the indicator's light red color persisted for approximately 30 seconds. (B) Blank test The titration is carried out in the same manner as above, except that no sample is used (i.e., only the toluene / ethanol (2:1) mixed solution is used). (3) The obtained results are substituted into the following formula to calculate the acid value. A=[(CB)×f×5.61] / S where A is the acid value (mgKOH / g), B is the amount of potassium hydroxide solution added for the blank test (mL), C is the amount of potassium hydroxide solution added for the main test (mL), f is the factor of the potassium hydroxide solution, and S is the mass of the sample (g).

[0087] <Measurement of the acid value of polyester resin from toner> The acid value of the polyester resin in the toner can be measured by the following method. 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 removed from the obtained soluble matter by distillation under reduced pressure to obtain the tetrahydrofuran (THF) soluble component of the toner. The obtained tetrahydrofuran (THF) soluble component of the toner is dissolved in chloroform to prepare a sample solution with a concentration of 25 mg / ml. 3.5 ml of the obtained sample solution is poured into the following apparatus, and a sample of a polymer having a molecular weight of 2000 or less is measured under the following conditions. The upper part is separated as the resin component. Preparative GPC device: Preparative HPLC LC-980 model manufactured by Japan Analytical Industry Co., Ltd. Preparative columns: JAIGEL 3H, JAIGEL 5H (manufactured by Japan Analytical Industry Co., Ltd.) Eluent: chloroform Flow rate: 3.5ml / min After separating the high molecular weight component derived from the resin, the solvent is distilled off under reduced pressure and the mixture is dried under reduced pressure at 90°C for 24 hours. The above procedure is repeated until about 2.0 g of the resin component is obtained. The acid value of the obtained sample is measured according to the procedure described above.

[0088] <Method for measuring weight average particle size (D4) of toner particles> The weight-average particle size (D4) of the toner particles is measured with an effective number of 25,000 measurement channels using a precision particle size distribution measuring device equipped with a 100 μm aperture tube and using the narrow-pore electrical resistance method, the Coulter Counter Multisizer 3 (registered trademark, manufactured by Beckman Coulter, Inc.), and the accompanying dedicated software for setting measurement conditions and analyzing measurement data, the Beckman Coulter Multisizer 3 Version 3.51 (manufactured by Beckman Coulter, Inc.), and the measurement data is analyzed and calculated. The aqueous electrolyte solution used for the measurement is prepared by dissolving special-grade sodium chloride in ion-exchanged water to a concentration of approximately 1% by mass, such as "ISOTON II" (manufactured by Beckman Coulter). Before performing the measurement and analysis, the dedicated software is set up as follows:

[0089] In the dedicated software's "Change Standard Measurement Method (SOM) Screen," set the total count in control mode to 50,000 particles, the number of measurements to 1, and the Kd value to the value obtained using a "Standard Particle 10.0 μm" (Beckman Coulter). Press the threshold / noise level measurement button to automatically set the threshold and noise level. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check the "Flush aperture tube after measurement" box. In the dedicated software's "Pulse to Particle Size Conversion Setting Screen," set the bin spacing 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. The specific measurement method is as follows.

[0090] (1) Pour approximately 200 ml of the electrolyte solution into a 250 ml round-bottom glass beaker made specifically for the Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 revolutions per second. Then, use the "aperture tube flush" function of the dedicated software to remove any dirt and air bubbles from inside the aperture tube. (2) Approximately 30 ml of the above-mentioned aqueous electrolyte solution is placed in a 100 ml flat-bottom glass beaker, and approximately 0.3 ml of a dilution obtained by diluting "Contaminon N" (a 10% by weight aqueous solution of a neutral detergent for cleaning precision measuring instruments, pH 7, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) three times by weight with ion-exchanged water is added as a dispersant. (3) A predetermined amount of ion-exchanged water is placed in the water tank of an ultrasonic disperser, "Ultrasonic Dispersion System Tetora150" (manufactured by Nikkaki Bios Co., Ltd.), which has two built-in oscillators with an oscillation frequency of 50 kHz and a phase difference of 180 degrees and an electrical output of 120 W, and approximately 2 ml of the Contaminon N is added to this water tank. (4) Set the beaker (2) in the beaker fixing hole of the ultrasonic disperser, operate the ultrasonic disperser, and adjust the height of the beaker so that the resonance state of the liquid surface of the electrolytic solution in the beaker is maximized. (5) While ultrasonic waves are irradiated to the electrolyte solution in the beaker in (4), approximately 10 mg of toner particles are added little by little to the electrolyte solution and dispersed. The ultrasonic dispersion process is then continued for another 60 seconds. During the ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be between 10°C and 40°C. (6) Using a pipette, transfer the solution to the round-bottom beaker (1) placed in the sample stand. The electrolytic solution (5) in which the toner particles are dispersed is dropped to adjust the measurement concentration to about 5%. Then, measurement is continued until the number of particles measured reaches 50,000. (7) The measurement data is analyzed using the dedicated software provided with the device, and the weight-average particle size (D4) is calculated. Note that when the dedicated software is set to Graph / Volume %, the "Average diameter" on the Analysis / Volume Statistics (Arithmetic Mean) screen is the weight-average particle size (D4).

[0091] <Method for measuring average circularity of toner external additive particles, toner particles, and toner> The average circularity is used as a simple method to quantitatively express the shape of particles. Using a Sysmex flow particle image analyzer FPIA-3000, particles with equivalent circle diameters in the range of 0.01 μm to 400 μm were measured, and the circularity of the measured particles was calculated using the following formula. The average circularity was defined as the sum of the circularities of the measured particles divided by the total number of particles. The number of measured particles was 5,000. Circularity a=L0 / L (In the formula, L0 represents the perimeter of a circle having the same projected area as the particle image, and L represents the perimeter of the particle projected image when image-processed at a 512 x 512 image processing resolution (0.3 μm x 0.3 μm pixels).)

[0092] <Method for measuring the hydrophobicity of external toner additives> The hydrophobicity of the toner external additive particles is calculated by the methanol titration method. Specifically, it is measured as follows: 0.5 g of the toner external additive particles is added to 50 ml of RO water, and methanol is added dropwise from a burette while stirring the mixture until the entire amount of the toner external additive is wetted.

[0093] Whether or not the entire amount is wetted is determined by whether or not all of the external toner additives floating on the water surface are submerged and suspended in the liquid. At this time, the volume percentage of methanol relative to the total volume of the mixed liquid and the dropped methanol at the end of the dropping is taken as the hydrophobicity. A higher value of the hydrophobicity indicates higher hydrophobicity.

[0094] <Solid 29 Method for measuring the abundance ratios of constituent compounds of external toner additives, B / A and (C / A) / (B / A) by Si-NMR solid 29In Si-NMR, peaks are detected in different shift regions depending on the structure of the functional group that bonds to Si in the constituent compounds of the toner additive. By identifying the position of each peak using a standard sample, the structure that bonds to Si can be identified. Furthermore, the abundance ratio of each constituent compound can be calculated from the obtained peak area. The ratio of the peak area of ​​the Q unit structure, T unit structure, and D unit structure to the total peak area can be calculated.

[0095] solid 29 The specific conditions for Si-NMR measurement are as follows: Equipment: JNM-ECX5002 (JEOL RESONANCE) Temperature: room temperature Measurement method: DDMAS method 29 Si 45° Sample tube: zirconia 3.2 mm diameter Sample: Filled in powder form into a test tube Sample rotation speed: 10kHz Relaxation delay: 180s Scan:2000

[0096] After the measurement, the peaks of a plurality of silane components of the sample or external toner additive, which have different substituents and bonding groups, are separated into the following M unit structure, D unit structure, T unit structure, and Q unit structure by curve fitting, and the peak area of ​​each is calculated. Curve fitting is performed using EXcalibur for Windows (registered trademark) version 4.2 (EX series), software for the JNM-EX400 manufactured by JEOL Ltd. Click "1D Pro" from the menu icon to load 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 curve fitting and the peak of the measurement results 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) Let (S1+S2+S3+S4)=SA.

[0097] In the formulas (S1), (S2), and (S3), Ra, Rb, Rc, Rd, Re, and Rf represent silicon-bonded organic groups such as hydrocarbon groups having 1 to 6 carbon atoms (e.g., alkyl groups), and halogen atoms. 29 Along with the Si-NMR measurement results 13 C-NMR and 1 The results of H-NMR may also be used for identification. S2 / SA, S3 / SA, and S4 / SA are calculated from SA, S2, S3, and S4 thus determined.

[0098] (Calculation method for B / A) solid 29 From the chart obtained by Si-NMR, the (Si-R 1 ) and calculate the peak area of ​​R 1 is as described above and represents an alkyl group having 1 to 6 carbon atoms. (Si-R 1 ) is the peak area of ​​the Q4 unit structure having S44, (Si-R 1 ) is the peak area of ​​the Q3 unit structure having S43, (Si-R 1 ) is the peak area of ​​the Q2 unit structure having S42, (Si-R 1 The peak area of ​​the Q1 unit structure having the formula (II) is designated as S41. (Si-R 1 ) is the peak area of ​​the T3 unit structure having S33, (Si-R 1 ) is the peak area of ​​the T2 unit structure having S32, (Si-R 1 The peak area of ​​the T1 unit structure having the formula (II) is designated as S31. (Si-R 1) is the peak area of ​​the D2 unit structure having S22, (Si-R 1 The peak area of ​​the D1 unit structure having the formula (II) is defined as S21. (Si-R 1 The peak area of ​​the M1 unit structure having the formula (I) is designated as S11.

[0099] At this time, the Si-R in each unit structure is as follows: 1 The peak area ratio is calculated. Si-R assigned to Q unit structure 1 Peak area ratio QB = (S44 / S4) × 0 + (S43 / S4) × 0 + (S42 / S4) × 0 + (S41 / S4) × 0 Si-R assigned to T unit structure 1 Peak area ratio TB = (S33 / S3) × 1 / 4 + (S32 / S3) × 1 / 4 + (S31 / S3) × 1 / 4 Si-R assigned to D unit structure 1 Peak area ratio DB = (S22 / S2) × 1 / 2 + (S21 / S2) × 1 / 2 Si-R assigned to M unit structure 1 Peak area ratio MB = S11 / S1 × 3 / 4

[0100] The constituent units of silicon polymers are classified into M units (monofunctional), D units (difunctional), T units (trifunctional), and Q units (tetrafunctional) according to the number of functional groups. In this disclosure, the degree of condensation in each unit is distinguished by the number of bridging oxygens, and they are classified as D1 units, D2 units, T1 units, T2 units, T3 units, etc. In other words, the number following the letter D or T indicates the number of bridging oxygens that form the siloxane bond. For example, a T3 unit indicates that all three functional groups are condensed and involved in the siloxane bond. A T2 unit indicates that two of the three functional groups are condensed and involved in the siloxane bond, and one functional group is not condensed. Indicates that.

[0101] 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: -10 ppm to 14 ppm M unit structure M1: -5 ppm to -9 ppm Using the above formula, calculate B / A=QB+TB+DB+MB.

[0102] (Calculation method for C / A and (C / A) / (B / A)) solid 29 From the chart obtained by Si-NMR, the unreacted groups (Si-OR 2 ) and calculate the peak area of ​​R 2 represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom. Unreacted group (Si-OR 2 The peak area of ​​the Q4 unit structure having the unreacted group (Si-OR 2 The peak area of ​​the Q3 unit structure having the unreacted group (Si-OR 2 The peak area of ​​the Q2 unit structure having the unreacted group (Si-OR 2 The peak area of ​​the Q1 unit structure having the formula (II) is designated as S41. Unreacted group (Si-OR 2 The peak area of ​​the T3 unit structure having unreacted groups (Si-OR 2 The peak area of ​​the T2 unit structure having the unreacted group (Si-OR 2 The peak area of ​​the T1 unit structure having the formula (II) is designated as S31. Unreacted group (Si-OR 2 The peak area of ​​the D2 unit structure having the unreacted group (Si-OR 2 The peak area of ​​the D1 unit structure having the formula (II) is defined as S21. Unreacted group (Si-OR 2The peak area of ​​the M1 unit structure having the formula (I) is designated as S11.

[0103] At this time, the Si-OR in each unit structure is as follows: 2 The peak area ratio is calculated. Si-OR assigned to Q unit structure 2 Peak area ratio QC = (S44 / S4) × 0 + (S43 / S4) × 1 / 4 + (S42 / S4) × 1 / 2 + (S41 / S4) × 3 / 4, Si-OR assigned to T unit structure 2 Peak area ratio TC = (S33 / S3) × 0 + (S32 / S3) × 1 / 4 + (S31 / S3) × 1 / 2, Si-OR assigned to D unit structure 2 Peak area ratio DC = (S22 / S2) × 0 + (S21 / S2) × 1 / 4, Si-OR assigned to M unit structure 2 Peak area ratio MC = S11 / S1 × 0

[0104] 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: -10 ppm to 14 ppm M unit structure M1: -5 ppm to -9 ppm From the above formula, calculate C / A = QC + TC + DC + MC. Also, calculate (C / A) / (B / A) from the B / A calculated above.

[0105] (Percentage of peak area attributed to siloxane bonds) solid 29From the chart obtained by Si-NMR, the ratio of the peak area attributable to siloxane bonds to the total peak area attributable to silicon polymers is calculated using the following method. The peak area assigned to the Q4 unit structure having a siloxane bond is designated p44, the peak area assigned to the Q3 unit structure having a siloxane bond is designated p43, the peak area assigned to the Q2 unit structure having a siloxane bond is designated p42, and the peak area assigned to the Q1 unit structure having a siloxane bond is designated p41. The peak area assigned to the T3 unit structure having a siloxane bond is designated p33, the peak area assigned to the T2 unit structure having a siloxane bond is designated p32, and the peak area assigned to the T1 unit structure having a siloxane bond is designated p31. The peak area attributed to the D2 unit structure having a siloxane bond is designated p22, and the peak area attributed to the D1 unit structure having a siloxane bond is designated p21. The peak area assigned to the M1 unit structure having a siloxane bond is designated as p11.

[0106] At this time, the peak area ratio attributable to the siloxane bond in each unit structure is calculated as follows. Peak area ratio of siloxane bonds attributed to Q unit structure Qp = (p44 / S4) + (p43 / S4) × 3 / 4 + (p42 / S4) × 1 / 2 + (p41 / S4) × 1 / 4 Peak area ratio of siloxane bonds attributed to T unit structure Tp = (p33 / S3) × 3 / 4 + (p32 / S3) × 1 / 2 + (p31 / S3) × 1 / 4 Peak area ratio of siloxane bonds attributed to D unit structure Dp = (p22 / S2) × 1 / 2 + (p21 / S2) × 1 / 2 Peak area ratio of siloxane bonds attributed to M unit structure Mp=p11 / S1×1 / 4 From the above, the area ratio of the peaks attributable to siloxane bonds is calculated as Qp+Tp+Dp+Mp.

[0107] <Method for measuring surface treatment agents in external toner additives> The surface treatment agent of the external toner additive is analyzed by pyrolysis GC-MS (gas chromatography mass spectrometry). The specific measurement conditions are as follows. Equipment: GC6890A (Agilent), pyrolysis equipment (Japan Analytical Industry Co., Ltd.) Column: HP-5ms 30m Thermal decomposition temperature: 590℃ The surface treatment agent of the external toner additive is identified by identifying the position of each peak in the profile obtained by the measurement using a standard sample. [Example]

[0108] The present invention will be described in more detail with reference to the following examples, which, however, are not intended to limit the scope of the present invention. Unless otherwise specified, the "parts" in the following formulations are all by mass. Hereinafter, Examples 17 to 19, 22, 23, 26 and 27 will be referred to as Reference Examples 17 to 19, 22, 23, 26 and 27, respectively.

[0109] <Production Example of Toner Additive Particles 1> 1. Hydrolysis process 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.

[0110] 2. Polycondensation process An alkaline aqueous medium was prepared by adding 68.8 g of RO water, 340.0 g of methanol, and 2.0 g of 25% aqueous ammonia to a 1000 ml beaker and stirring at 30°C. The raw material solution obtained in step 1, Hydrolysis, was added dropwise to this alkaline aqueous medium over 1 minute. After the raw material solution was added dropwise, the mixture was stirred for 1.5 hours while maintaining the temperature at 30°C to allow the polycondensation reaction to proceed, yielding a polycondensation reaction liquid.

[0111] 3.Particleization process 1000g of RO water was placed in a 2000ml beaker, and the polycondensation reaction liquid obtained in 2. Polycondensation Step was added dropwise over 10 minutes while stirring at 25°C. The polycondensation reaction liquid immediately became cloudy upon mixing with the water, yielding a dispersion containing silicon polymer particles with siloxane bonds.

[0112] 4. Hydrophobization process 27.1 g of hexamethyldisilazane as a hydrophobizing agent was added to the dispersion containing the silicon polymer particles having siloxane bonds obtained in the granulation step, and the mixture was stirred at 60°C for 2.5 hours. After leaving the mixture to stand for 5 minutes, the powder that settled to the bottom of the solution was collected by suction filtration and dried under reduced pressure at 120°C for 24 hours to obtain external toner additive particles 1. The number average particle size of the primary particles of the obtained external toner additive particles 1 was 0.12 μm. The physical properties of external toner additive particles 1 are shown in Table 1.

[0113] <Production Example of Toner Additive Particles 2> Except for changing the amount of hexamethyldisilazane used in the hydrophobization step to 16.3 g, the same procedure as in the production example of external toner additive particles 1 was carried out to obtain external toner additive particles 2. The physical properties of the obtained external toner additive particles 2 are shown in Table 1.

[0114] <Production Example of Toner Additive Particles 3> Except for changing the amount of hexamethyldisilazane used in the hydrophobization step to 37.9 g, the same procedure as in the production example of external toner additive particles 1 was carried out to obtain external toner additive particles 3. The physical properties of the obtained external toner additive particles 3 are shown in Table 1.

[0115] <Production Example of Toner Additive Particles 4> Except for changing the stirring temperature in the hydrolysis step to 50°C and changing the amount of 25% aqueous ammonia used in 2. Polycondensation step to 1.5 g, the same procedure as in Production Example 1 for Toner External Additive Particles 1 was repeated to obtain Toner External Additive Particles 4. The physical properties of the obtained Toner External Additive Particles 4 are shown in Table 1.

[0116] <Production Example of Toner Additive Particles 5> Except for changing the stirring temperature in the hydrolysis step to 40°C and changing the amount of 25% aqueous ammonia used in the polycondensation step to 2.3 g, the same procedure as in the production example for external toner additive particles 1 was carried out to obtain external toner additive particles 5. The physical properties of the obtained external toner additive particles 5 are shown in Table 1.

[0117] <Production Example of Toner Additive Particles 6> Except for changing the stirring temperature in the hydrolysis step to 50°C and changing the RO water, methanol, and 25% aqueous ammonia to 98.8 g, 310.0 g, and 1.5 g, respectively, used in the polycondensation step, the same procedure as in the production example for toner external additive particles 1 was repeated to obtain toner external additive particles 6. The physical properties of the obtained toner external additive particles 6 are shown in Table 1.

[0118] <Production Example of Toner Additive Particles 7> Except for changing the stirring temperature in the hydrolysis step to 40°C and changing the amounts of RO water, methanol, and 2.5g of 25% aqueous ammonia used in the polycondensation step to 58.8g, the procedure was the same as in the production example for toner external additive particles 1, to obtain toner external additive particles 7. The physical properties of the obtained toner external additive particles 7 are shown in Table 1.

[0119] <Production Example of Toner Additive Particles 8> In the polycondensation step, the stirring time of the mixed solution after the dropwise addition of the raw material solution was changed to 1.0 hour, and the same procedure as in the production example of external toner additive particles 1 was repeated to obtain external toner additive particles 8. The physical properties of the obtained external toner additive particles 8 are shown in Table 1.

[0120] <Production Example of Toner Additive Particles 9> In the polycondensation step, the stirring time of the mixed solution after the dropwise addition of the raw material solution was changed to 2.0 hours, and the same procedure as in the production example of the toner external additive particles 1 was repeated to obtain the toner external additive particles 9. The physical properties of the obtained toner external additive particles 9 are shown in Table 1.

[0121] <Production Example of Toner Additive Particles 10> Except for changing the stirring time in the hydrolysis step to 1.0 hour and the stirring time of the mixed solution after dropwise addition of the raw material solution in the polycondensation step to 1.0 hour, the same procedure as in the production example for toner external additive particles 1 was carried out to obtain toner external additive particles 10. The physical properties of the obtained toner external additive particles 10 are shown in Table 1.

[0122] <Production Example of Toner Additive Particles 11> Except for changing the stirring time in the hydrolysis step to 2.0 hours and the stirring time of the mixed solution after dropwise addition of the raw material solution in the polycondensation step to 2.0 hours, the same procedure as in the production example of external toner additive particles 1 was carried out to obtain external toner additive particles 11. The physical properties of the obtained external toner additive particles 11 are shown in Table 1.

[0123] <Production Example of Toner Additive Particles 12> In the hydrophobizing step, the hydrophobizing agent used was changed to octamethylcyclotetrasiloxane, and the same procedure as in the production example of the toner external additive particle 1 was repeated to obtain the toner external additive particle 12. The physical properties of the obtained toner external additive particle 12 are shown in Table 1.

[0124] <Production Example of Toner Additive Particles 13> In the hydrophobizing step, the hydrophobizing agent used was changed to chlorotrimethylsilane, and the same procedure as in the production example of the toner external additive particle 1 was repeated to obtain the toner external additive particle 13. The physical properties of the obtained toner external additive particle 13 are shown in Table 1.

[0125] <Production Example of Toner Additive Particles 14> In the hydrophobizing step, the hydrophobizing agent used was changed to trifluoropropyltrimethoxysilane, and the same procedure as in the production example of the toner external additive particle 1 was repeated to obtain the toner external additive particle 14. The physical properties of the obtained toner external additive particle 14 are shown in Table 1.

[0126] <Production Example of Toner Additive Particles 15> In the hydrophobizing step, the hydrophobizing agent used was changed to dimethyl silicone oil, and the same procedure as in the production example of the toner external additive particles 1 was repeated to obtain the toner external additive particles 15. The physical properties of the obtained toner external additive particles 15 are shown in Table 1.

[0127] <Production Example of Toner Additive Particles 16> Except for not adding a hydrophobizing agent in the hydrophobizing step, the same procedure as in the production example of the toner external additive particles 1 was carried out to obtain the toner external additive particles 16. The physical properties of the obtained toner external additive particles 16 are shown in Table 1.

[0128] <Production Example of Toner Additive Particles 17> In the hydrolysis step, the amount of tetraethoxysilane was changed to 30.1 g and the amount of dimethyldimethoxysilane was changed to 24.3 g, and the same procedure as in the production example of external toner additive particles 1 was carried out to obtain external toner additive particles 17. The physical properties of the obtained external toner additive particles 17 are shown in Table 1.

[0129] <Production Example of Toner Additive Particles 18> In the hydrolysis step, the amount of tetraethoxysilane was changed to 23.5 g and the amount of dimethyldimethoxysilane was changed to 30.9 g, and the same procedure as in the production example of external toner additive particles 1 was carried out to obtain external toner additive particles 18. The physical properties of the obtained external toner additive particles 18 are shown in Table 1.

[0130] <Production Example of Toner Additive Particles 19> In the hydrolysis step, the amount of tetraethoxysilane was changed to 33.8 g and the amount of dimethyldimethoxysilane was changed to 20.6 g, and the same procedure as in the production example of external toner additive particles 1 was carried out to obtain external toner additive particles 19. The physical properties of the obtained external toner additive particles 19 are shown in Table 1.

[0131] <Production Example of Toner Additive Particles 20> Toner external additive particles 20 were obtained in the same manner as in the production example for toner external additive particles 1, 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 mixed solution after dropwise addition of the raw material solution was changed to 2.5 hours. The physical properties of the obtained toner external additive particles 20 are shown in Table 1.

[0132] <Production Example of Toner Additive Particles 21> Except for changing the stirring temperature to 35°C and the stirring time to 1.0 hour in the hydrolysis step, and changing the stirring time of the mixed solution after dropwise addition of the raw material solution to 1.0 hour in the polycondensation step, the same procedure as in the production example for toner external additive particles 1 was carried out to obtain toner external additive particles 21. The physical properties of the obtained toner external additive particles 21 are shown in Table 1.

[0133] <Production Example of Toner Additive Particles 22> In the hydrolysis step, the amounts of tetraethoxysilane and dimethyldimethoxysilane were changed to 16.9 g and 18.6 g, respectively, and 18.9 g of trimethoxymethylsilane was added, and the stirring temperature was changed to 30° C. and the stirring time to 0.5 hours, respectively. Except for this, external toner additive particles 22 were obtained in the same manner as in the production example for external toner additive particles 1. The physical properties of the obtained external toner additive particles 22 are shown in Table 1.

[0134] <Production Example of Toner Additive Particles 23> In the hydrolysis step, the amount of tetraethoxysilane was changed to 22.1 g, the amount of dimethyldimethoxysilane was changed to 21.6 g, and 10.7 g of trimethylsilanol was added. Except for this, the procedure was the same as in the production example of external toner additive particles 1 to obtain external toner additive particles 23. The physical properties of the obtained external toner additive particles 23 are shown in Table 1.

[0135] <Production Example of Toner Additive Particles 24> In the hydrolysis step, tetraethoxysilane was not added, and 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 to 0.5 hours, but the same procedure as in the production example of external toner additive particles 1 was repeated to obtain external toner additive particles 24. The physical properties of the obtained external toner additive particles 24 are shown in Table 1.

[0136] <Production Example of Toner Additive Particles 25> External toner additive particles 25 were obtained in the same manner as in the production example for external toner additive particles 18, except that in the hydrolysis step, the stirring temperature was changed to 50°C and the stirring time to 1.0 hour, and in the polycondensation step, the stirring time of the mixed solution after dropwise addition of the raw material solution was changed to 1.0 hour. The physical properties of the obtained external toner additive particles 25 are shown in Table 1.

[0137] <Production Example of Toner Additive Particles 26> External toner additive particles 26 were obtained in the same manner as in the production example for external toner additive particles 18, except that in the hydrolysis step, the amount of tetraethoxysilane was changed to 22.1 g and the amount of dimethyldimethoxysilane to 32.3 g, the stirring temperature was changed to 50°C, the stirring time was changed to 1.0 hour, and in the condensation polymerization step, the stirring time of the mixed solution after dropwise addition of the raw material solution was changed to 1.0 hour. The physical properties of the obtained external toner additive particles 26 are shown in Table 1.

[0138] <Production Example of Toner Additive Particles 27> External toner additive particles 27 were obtained in the same manner as in the production example for external toner additive particles 1, except that in the hydrolysis step, tetraethoxysilane and dimethyldimethoxysilane were not added, but 54.4 g of trimethoxymethylsilane was added instead, and the stirring temperature was changed to 30°C and the stirring time to 0.5 hours. The physical properties of the obtained external toner additive particles 27 are shown in Table 1.

[0139] <Production Example of Toner Additive Particles 28> External toner additive particles 28 were obtained in the same manner as in the production example of external toner additive particles 27, except that trimethoxymethylsilane was changed to 50.6 g and 3.8 g of tetraethoxysilane was added. The physical properties of the obtained external toner additive particles 28 are shown in Table 1.

[0140] <Production Example of Toner Additive Particles 29> In the hydrolysis step, the amounts of tetraethoxysilane and dimethyldimethoxysilane were changed to 30.1 g and 8.2 g, respectively, and 16.1 g of trimethoxymethylsilane was added, and the stirring temperature was changed to 30° C. and the stirring time to 0.5 hours, respectively. Except for this, the same procedure as in Production Example of External Toner Additive Particles 1 was repeated to obtain External Toner Additive Particles 29. The physical properties of the obtained External Toner Additive Particles 29 are shown in Table 1.

[0141] <Production Example of Toner Additive Particles 30> In the hydrolysis step, the amounts of tetraethoxysilane and dimethyldimethoxysilane were changed to 15.4 g and 8.2 g, respectively, and 30.8 g of trimethoxymethylsilane was added, and the stirring temperature was changed to 30° C. and the stirring time to 0.5 hours, respectively. Except for this, external toner additive particles 30 were obtained in the same manner as in the production example for external toner additive particles 1. The physical properties of the obtained external toner additive particles 30 are shown in Table 1.

[0142] <Production Example of Toner Additive Particles 31> A 2000 ml beaker was charged with 124.0 g of ethanol, 24.0 g of RO water, and 10.0 g of 28% aqueous ammonia. The solution was adjusted to 70°C, and 232.0 g of tetraethoxysilane and 84.0 g of 5.4% aqueous ammonia were added dropwise over 0.5 hours with stirring. After the addition was complete, stirring was continued for another 0.5 hours to allow hydrolysis to occur, yielding a dispersion of silicon polymer particles having siloxane bonds.

[0143] To the dispersion of silicon polymer particles having siloxane bonds obtained in the above step, 95.0 g of hexamethyldisilazane was added at room temperature, and the dispersion was then heated to 50-60°C and stirred for 3.0 hours. The powder in the dispersion was collected by suction filtration and dried under reduced pressure at 120°C for 24 hours to obtain a toner. Thus, toner external additive particles 31 were obtained. Table 1 shows the physical properties of the obtained toner external additive particles 31.

[0144] <Production Example of Toner Additive Particles 32> External toner additive particles 32 were obtained in the same manner as in the production example of external toner additive particles 31, except that tetraethoxysilane was changed to 208.8 g and 23.2 g of trimethoxymethylsilane was added in the production example of external toner additive particles 31. The physical properties of the obtained external toner additive particles 32 are shown in Table 1. [Table 1] In the table, Si-O-Si% represents the percentage of siloxane in the total peak area attributed to silicon polymers. The particle size is the number average particle size of the primary particles, and the circularity is the average circularity.

[0145] <Production Example of Polyester Resin A1> Polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane 76.9 parts (0.167 mole parts) Terephthalic acid (TPA) 25.0 parts (0.145 mole parts) Adipic acid 8.0 parts (0.054 moles) Titanium tetrabutoxide 0.5 parts The above materials were placed in a 4-liter, four-necked glass flask, fitted with a thermometer, stirrer, condenser, and nitrogen inlet tube, and placed in a mantle heater. The atmosphere in the flask was then purged with nitrogen gas, and the temperature was gradually raised with stirring. The mixture was allowed to react for 4 hours at 200°C while stirring (first reaction step). Then, 1.2 parts (0.006 moles) of trimellitic anhydride (TMA) was added, and the mixture was allowed to react for 1 hour at 180°C (second reaction step), yielding polyester resin A1. The acid value of this polyester resin A1 was 5 mgKOH / g.

[0146] <Production Example of Polyester Resin A2> Polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane 71.3 parts (0.155 mole parts) Terephthalic acid 24.1 parts (0.145 mole parts) Titanium tetrabutoxide 0.6 parts The above materials were placed in a 4-liter, four-necked glass flask, fitted with a thermometer, stirring rod, condenser, and nitrogen inlet tube, and placed in a mantle heater. The atmosphere in the flask was then purged with nitrogen gas, and the temperature was gradually raised with stirring. The mixture was allowed to react for 2 hours at 200°C while stirring. Subsequently, 5.8 parts (0.030 moles) of trimellitic anhydride was added, and the mixture was allowed to react for 10 hours at 180°C, yielding polyester resin A2. The acid value of this polyester resin A2 was 10 mgKOH / g.

[0147] <Production example of polyester resin A3> Polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane 73.4 parts (0.186 mole parts) Terephthalic acid (TPA) 11.6 parts (0.070 mole parts) Adipic acid 6.8 parts (0.047 moles) 0.5 parts tin di(2-ethylhexyl)ate The above materials were placed in a 4-liter, four-necked glass flask, fitted with a thermometer, stirrer, condenser, and nitrogen inlet tube, and placed in a mantle heater. The atmosphere in the flask was then purged with nitrogen gas, and the temperature was gradually raised with stirring. The mixture was allowed to react for 2 hours at 200°C while stirring. 8.2 parts (0.039 moles) of trimellitic anhydride (TMA) was then added, and the mixture was allowed to react for 15 hours at 160°C, yielding Polyester Resin A3. The acid value of this Polyester Resin A3 was 20 mgKOH / g.

[0148] <Production example of polyester resin A4> Polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane 76.9 parts (0.167 mole parts) Terephthalic acid (TPA) 24.1 parts (0.140 mole parts) Titanium tetrabutoxide 0.5 parts The above materials were placed in a 4-liter, four-necked glass flask, and a thermometer, stirring rod, condenser, and nitrogen inlet tube were attached. The flask was then placed in a mantle heater. The atmosphere inside the flask was then replaced with nitrogen gas, and the temperature was gradually raised with stirring. The mixture was allowed to react for 4 hours at 200°C while stirring. After that, 5.3 parts (0.024 moles) of trimellitic anhydride (TMA) was added, and the resulting mixture was stirred for 1 hour. The reaction was carried out at 80° C. for 1 hour to obtain Polyester Resin A4, which had an acid value of 25 mg KOH / g.

[0149] <Production Example of Toner Particle 1> Polyester resin A1 70.0 parts Polyester resin A2 30.0 parts Fischer-Tropsch wax (maximum endothermic peak temperature 78°C) 5.0 parts CI Pigment Blue 15:3 5.0 parts 0.1 parts of 3,5-di-t-butylsalicylic acid aluminum compound The raw materials shown in the above recipe were mixed in a Henschel mixer (FM-75, manufactured by Nippon Coke and Engineering Co., Ltd.) at a rotation speed of 20 s -1After mixing for 5 minutes, the mixture was kneaded in a twin-screw kneader (PCM-30, manufactured by Ikegai Corporation) set at 125°C and 300 rpm. The resulting mixture was cooled and coarsely crushed to a diameter of 1 mm or less using a hammer mill. The resulting coarsely crushed material was then finely crushed in a mechanical crusher (T-250, manufactured by Freund Turbo Corporation).

[0150] Further, classification was carried out using a rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) to obtain toner particles 1. The operating conditions of the rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) were a classification rotor rotation speed of 50.0 s -1 The resulting toner particles 1 had a weight average particle size (D4) of 5.9 μm.

[0151] <Production Example of Toner Particle 2> Toner particles 2 were obtained in the same manner as in the production example of toner particles 1, except that polyester resin A1 in the production example of toner particles 1 was changed to polyester resin A3. The obtained toner particles 2 had a weight average particle size (D4) of 5.9 μm.

[0152] <Production Example of Toner Particle 3> Toner particles 3 were obtained in the same manner as in the production example of toner particles 1, except that polyester resin A1 in the production example of toner particles 1 was changed to polyester resin A4. The obtained toner particles 3 had a weight average particle size (D4) of 5.9 μm.

[0153] <Toner 1 manufacturing example> 100 parts of toner particles 6.0 parts of external additive particles for toner 1 The above materials were mixed in a Henschel mixer FM-10C (Mitsui Miike Chemical Engineering Co., Ltd.) at a rotation speed of 30 s -1 The mixture was mixed for 10 minutes, and a toner 1 was obtained.

[0154] <Production Examples of Toners 2 to 34> Toners 2 to 34 were obtained by carrying out the same production procedure as in the production example of Toner 1, except that the toner particles and external toner additives were changed to those shown in Table 2. [Table 2] In the table, the amount added is the number of parts per 100 parts of toner particles.

[0155] <Carrier 1 manufacturing example> Number average particle size: 0.30 μm, magnetization strength: 65 Am under a magnetic field of 1000 / 4π (kA / m) 2 / kg) of magnetite 1 Number average particle size: 0.50 μm, magnetization strength: 65 Am under a magnetic field of 1000 / 4π (kA / m) 2 / kg) magnetite2 To 100 parts of each of the above materials, 4.0 parts of a silane compound (3-(2-aminoethylaminopropyl)trimethoxysilane) was added, and the mixture was mixed and stirred at high speed in a container at 100° C. or higher to treat each of the fine particles.

[0156] Phenol: 10% by weight Formaldehyde solution: 6% by mass (40% by mass of formaldehyde, 10% by mass of methanol, 50% by mass of water) Magnetite treated with the above silane compound 1:58 mass% Magnetite treated with the above silane compound 2: 26 mass%

[0157] 100 parts of the above material, 5 parts of a 28% by weight aqueous ammonia solution, and 20 parts of water were placed in a flask, and the mixture was heated to 85°C over 30 minutes and maintained at that temperature while stirring and mixing. The polymerization reaction was carried out for 3 hours, resulting in hardening of the resulting phenolic resin. The hardened phenolic resin was then cooled to 30°C, and water was added. The supernatant was removed, and the precipitate was washed with water and air-dried. This was then dried under reduced pressure (5 mmHg or less) at 60°C to obtain magnetic material-dispersed spherical carrier 1. The volume-based 50% particle size (D50) was 34.2 μm.

[0158] <Manufacturing example of two-component developer 1> To 92.0 parts of Carrier 1, 8.0 parts of Toner 1 were added and mixed in a V-type mixer (V-20, manufactured by Seishin Enterprises) to obtain Two-Component Developer 1.

[0159] <Production Examples of Two-Component Developers 2 to 34> Two-component developers 2 to 34 were obtained by carrying out the same production procedure as in the production example of two-component developer 1, except that the toner was changed as shown in Table 3. [Table 3]

[0160] <Toner evaluation method> (1) Measurement of image density changes The image forming apparatus was a Canon full-color copier, imagePress C800, and the above two-component developer was placed in the cyan developer of the image forming apparatus, and the above toner was placed in the cyan toner container, and the evaluation described below was carried out. The modification was to remove the mechanism for discharging excess magnetic carrier from the developer. The evaluation paper was plain paper GF-C081 (A4, basis weight 81.4 g / m 2 (sold by Canon Marketing Japan Inc.) was used.

[0161] The amount of toner on the paper in a FFh image (solid image) is 0.45 mg / cm 2 The settings were adjusted so that the result was as follows: FFh is the hexadecimal representation of 256 gradations, with 00h being the first gradation of 256 gradations (white background) and FF being the 256th gradation of 256 gradations (solid area). First, an image output test of 1,000 sheets was conducted at an image ratio of 1%. During the continuous printing of 1,000 sheets, the sheets were printed under the same development and transfer conditions (without calibration) as the first sheet.

[0162] After that, an image output test of 1,000 sheets was conducted at an image ratio of 80%. During the continuous printing of 1,000 sheets, the sheets were printed under the same development and transfer conditions (without calibration) as the first sheet. The image density of the 1,000th sheet printed at an image ratio of 1% was taken as the initial density, and the density of the 1,000th image printed at an image ratio of 80% was measured and evaluated.

[0163] The above tests were carried out under normal temperature and humidity conditions (N / N; temperature 25°C, relative humidity 55%), high temperature and humidity conditions (H / H; temperature 30°C, relative humidity 80%), and normal temperature and humidity conditions (N / L; temperature 23°C, relative humidity 5%). Using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite), the initial density and the density of the 1,000th image printed at an image ratio of 80% were measured, and the difference Δ was used to rank the images according to the following criteria. (Evaluation standard: 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

[0164] (2) Evaluation method for fogging on non-image areas (white areas) after durability test As an image forming device, Canon's full-color copier imageRUNNER ADVA Using a modified NCE C5255 machine, two-component developer 1 was injected into the cyan station developer. 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, and the evaluation paper was GFC-081 plain copy paper (A4, basis weight 81.4 g / m 2 (Sold by Canon Marketing Japan Inc.) In each environment, a 1cm x 1cm FFh ​​image was printed in the center of an A4 sheet of paper, and after printing 50,000 sheets, fogging in the white area was measured.

[0165] The reflectance Dr (%) of the evaluation paper before image output was measured using a reflectometer (Tokyo Denshoku Co., Ltd.'s "REFLECTOMETER MODEL TC-6DS"). After durability testing (50,001 sheets), the reflectance Ds (%) of the 00H image area (white area) was measured. The 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

[0166] (3) Evaluation method for charging stability Toner on the electrostatic latent image carrier is collected by suction using a metal cylindrical tube and a cylindrical filter. The amount of triboelectric charge of the toner was calculated from the above equation. Specifically, the amount of triboelectric charge of the toner on the electrostatic latent image carrier was measured using a Faraday cage. A Faraday cage is a coaxial double cylinder, with the inner and outer cylinders insulated. If a charged body with a charge Q is placed inside this inner cylinder, electrostatic induction will create the same effect as if a metal cylinder with a charge Q were present. This induced charge was measured using an electrometer (Kesley 6517A, manufactured by Kesley), and the amount of charge Q (mC) divided by the toner mass M (kg) in the inner cylinder (Q / M) was determined as the amount of triboelectric charge of the toner. Toner triboelectric charge (mC / kg) = Q / M Evaluation image: A 2cm x 5cm FFh ​​image placed in the center of an A4 sheet of paper

[0167] First, the evaluation image was formed on the electrostatic latent image carrier. Before the image was transferred to the intermediate transfer member, the rotation of the electrostatic latent image carrier was stopped, and the toner on the electrostatic latent image carrier was suction-collected using a metal cylindrical tube and a cylindrical filter, and the [initial Q / M] was measured. Subsequently, the developer was left in the evaluation machine for two weeks in N / N, H / H, and N / L environments with the developer still inside. The same procedures were then performed as before the storage, and the charge amount Q / M (mC / kg) per unit mass on the electrostatic latent image carrier after storage was measured. From the initial Q / M per unit mass on the electrostatic latent image carrier and the Q / M per unit mass on the electrostatic latent image carrier after storage, the rate of change in Q / M after storage was calculated as ([initial Q / M] - [Q / M after storage in each environment]) × 100 / [initial Q / M], and the evaluation was evaluated according to the following criteria: (Evaluation Criteria) A: Change rate is less than 2% B: Change rate is 2% or more but less than 5% C: Change rate is 5% or more but less than 10% D: Change rate is 10% or more but less than 15% E: Change rate is 15% or more

[0168] <Evaluation Results of Examples 1 to 27> The evaluation results of Examples 1 to 27 are shown in Table 4.

[0169] <Evaluation Results of Comparative Examples 1 to 7> The evaluation results of Comparative Examples 1 to 7 are shown in Table 4. [Table 4]

[0170] <Production example of toners 35 to 39> Toners 35 to 39 were obtained by carrying out the same production procedure as in the production example of Toner 1, except that the toner particles and external toner additives were changed to those shown in Table 5. [Table 5]

[0171] <Manufacturing examples of two-component developers 35 to 39> Two-component developers 35 to 39 were obtained by carrying out production 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. [Table 6]

[0172] <Evaluation Results of Examples 28 to 32> The evaluation results of Examples 28 to 32 are shown in Table 7. [Table 7]

Claims

1. Siloxane bond and Si—R １ An external toner additive comprising particles of a silicon polymer having a bond, The external additive for toner ２９ In the chart obtained by Si-NMR measurement, the total peak area attributed to the external toner additive is designated as A, and Si-R １ Bond (the R １ represents an alkyl group having 1 to 6 carbon atoms. When the peak area attributed to the above group is defined as B, the following formula (1) is satisfied: The external additive for toner ２９ In a chart obtained by Si-NMR measurement, when the total peak area attributable to the silicon polymer is SA and the peak area attributable to the T unit structure is S3, the following formula (2) is satisfied: The silicon polymer is a condensation polymer of a bifunctional silane and a tetrafunctional silane, wherein the proportion of the bifunctional silane is 61 to 65 mol % and the proportion of the tetrafunctional silane is 35 to 39 mol %. 0.260≦B / A≦0.450 (1) 0.00≦S3 / SA≦0.50 (2)

2. The silicon polymer is １ Bond and Si—OR ２ having a bond, The external additive for toner ２９ In the chart obtained by Si-NMR measurement, the Si—OR contained in the external additive for toner ２ 2. The external toner additive according to claim 1, wherein the following formula (3) is satisfied when C is the peak area attributable to the bond: 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. 3. The external toner additive according to claim 1, wherein the number average particle size of the primary particles of the external toner additive is 0.02 μm to 0.30 μm.

4. The external toner additive according to any one of claims 1 to 3, wherein the external toner additive is surface-treated with at least one compound selected from the group consisting of alkylsilazane compounds, alkylalkoxysilane compounds, chlorosilane compounds, siloxane compounds, and silicone oils.

5. 5. The external toner additive according to claim 1, wherein the average circularity of the external toner additive is 0.85 to 0.

95.

6. The external additive for toner ２９ The external toner additive according to any one of claims 1 to 5, wherein the ratio of the peak area attributable to the siloxane bond to the total peak area attributable to the silicon polymer, calculated from a chart obtained by Si-NMR measurement, is 60.0% to 85.0%.

7. The external additive for toner ２９ 7. The external toner additive according to claim 1, wherein, in a chart obtained by Si-NMR measurement, when the total peak area attributable to the silicon polymer is SA, the peak area attributable to the Q unit structure is S4, the peak area attributable to the T unit structure is S3, and the peak area attributable to the D unit structure is S2, the following formulae (I) to (III) are satisfied: 0.20≦S4 / SA≦0.60...(I) 0.00≦S3 / SA≦0.50...(II) 0.20≦S2 / SA≦0.70...(III)

8. 8. The external toner additive according to claim 1, wherein the degree of hydrophobicity of the external toner additive as measured by methanol titration method is 50% to 60%.

9. A toner having toner particles and an external toner additive, the toner particles contain a binder resin, A toner, wherein the external toner additive is the external toner additive according to any one of claims 1 to 8.

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