toner

Abstract

The present invention relates to a toner. Provided is a toner including: toner particles including a binder resin and a wax, and inorganic fine particles on a surface of the toner particles, wherein the binder resin includes resin A; the toner satisfies 2.50 ≤ SPa-SPw ≤ 4.50, wherein SPa (cal / cm 3 ) 0.5 is an SP value of the resin A, and SPw (cal / cm 3 ) 0.5 is an SP value of the wax; the inorganic fine particles include silica fine particles whose surface is treated with silicone oil; the silica fine particles satisfy 0.5 ≤ SPSi ≤ 1.5, wherein SPSi (cal / cm 29 In a Si solid-state NMR measurement, 30 ≤ B ≤ 60 and 4.0 ≤ A / B ≤ 6.0 are satisfied, A is taken as an integral value of a D unit obtained by taking an integral value of a Q unit in a CP / MAS measurement as 100, and B is taken as an integral value of a D unit obtained by taking an integral value of a Q unit in a DD / MAS measurement as 100.

Description

Technical Field

[0001] This disclosure relates to toners used in image forming methods such as electrophotography. Background Technology

[0002] In recent years, there has been a greater demand for energy-efficient printers and copiers. To meet this demand, toners that melt rapidly at lower temperatures, i.e., those with excellent low-temperature fixing properties, are preferred.

[0003] From the viewpoint of achieving toners with excellent low-temperature fixing properties, for example, Japanese Patent Application Publications Nos. 2015-172744 and 2019-086642 propose the use of wax in toners. The addition of wax is for the purpose of imparting plasticity to the binder resin. The viscosity of the toner at melt is reduced due to the mixing of the wax, which melts and liquefies upon heating, with the binder resin, thus obtaining a toner with excellent low-temperature fixing properties. Summary of the Invention

[0004] The problem the invention aims to solve

[0005] The inventors' research reveals that the toner in Japanese Patent Application Publication No. 2015-172744 contains a large amount of wax, and although it has excellent low-temperature fixing properties, it is problematic in terms of color inhomogeneity. Specifically, the binder resin and wax in the toner particles mix with each other during fixing; as a result, uneven crystallization of wax occurs after fixing, resulting in color inhomogeneity in the fixed image.

[0006] To improve the uniformity of color, it is necessary for the wax to crystallize uniformly and rapidly on the surface of the toner particles. According to Japanese Patent Application Publication No. 2019-086642, the toner achieves rapid crystallization by adding a wax nucleating agent in the form of a crystalline material, thus successfully increasing the wax crystallization rate. However, despite promoting crystallization, there is still room for improvement in ensuring uniform wax crystallization; furthermore, there remains a need to address the issue of uneven color.

[0007] This disclosure provides a toner that maintains low-temperature fixing performance while exhibiting excellent chargeability and improved color uniformity in the fixed image.

[0008] This disclosure provides a toner comprising:

[0009] Toner particles containing binder resins and waxes, and

[0010] Inorganic fine particles on the surface of toner particles

[0011] The adhesive resin includes resin A;

[0012] When SPa(cal / cm)3 ) 0.5 Take the SP value of resin A calculated according to the Fedors method, and

[0013] SPw(cal / cm 3 ) 0.5 When taking the SP value of wax calculated according to the Fedors method,

[0014] Spa and SPw satisfy the following equation (1):

[0015] 2.50≤SPa-SPw≤4.50...(1),

[0016] Inorganic fine particles include silica fine particles whose surfaces are treated with silicone oil;

[0017] In fine silica particles 29 In Si solid-state NMR measurements

[0018] When A is taken as the integral value of cell D obtained by setting the integral value of cell Q in the CP / MAS measurement to 100, and

[0019] When B is taken as the integral value of the D element obtained by setting the integral value of the Q element in the DD / MAS measurement to 100,

[0020] A and B satisfy the following equations (2) and (3):

[0021] 30≤B≤60...(2)

[0022] 4.0≤A / B≤6.0...(3).

[0023] This disclosure provides a toner that maintains low-temperature fixing properties while exhibiting excellent chargeability and improved color uniformity in the fixed image.

[0024] Further features of the invention will become apparent from the following description of exemplary embodiments. Detailed Implementation

[0025] Unless otherwise stated, descriptions of numerical ranges such as "from XX to YY" or "XX to YY" refer to a range that includes both the lower and upper limits as endpoints. When describing a numerical range in segments, the upper and lower limits of each range can be combined arbitrarily.

[0026] As described above, in order to improve color uniformity in the fixed image, it is necessary to make the wax crystallize evenly and quickly on the surface of the toner particles during fixing. In this regard, the inventors conceived that if the wax could be made to uniformly seep onto the surface of the toner particles and crystallize quickly on the surface of the toner particles during fixing, color uniformity could be improved, and as a result of diligent research on this method, the aforementioned toner was obtained.

[0027] This disclosure relates to a toner comprising:

[0028] Toner particles containing binder resins and waxes, and

[0029] Inorganic fine particles on the surface of toner particles

[0030] The adhesive resin includes resin A;

[0031] When SPa(cal / cm) 3 ) 0.5 Take the SP value of resin A calculated according to the Fedors method, and

[0032] SPw(cal / cm 3 ) 0.5 When taking the SP value of wax calculated according to the Fedors method,

[0033] Spa and SPw satisfy the following equation (1):

[0034] 2.50≤SPa-SPw≤4.50...(1),

[0035] Inorganic fine particles include silica fine particles whose surfaces are treated with silicone oil;

[0036] In fine silica particles 29 In Si solid-state NMR measurements

[0037] When A is taken as the integral value of cell D obtained by setting the integral value of cell Q in the CP / MAS measurement to 100, and

[0038] When B is taken as the integral value of the D element obtained by setting the integral value of the Q element in the DD / MAS measurement to 100,

[0039] A and B satisfy the following equations (2) and (3):

[0040] 30≤B≤60...(2)

[0041] 4.0≤A / B≤6.0...(3).

[0042] In these studies, the inventors discovered that by adjusting the value obtained by subtracting the wax's SP value from the SP value of resin A (SPa-SPw) to fall within the range of 2.50 to 4.50, the wax uniformly exudes onto the surface of the toner particles during the melting and deformation of the toner particles during fixing. In their studies, the inventors also discovered that by adjusting the value obtained by subtracting the wax's SP value from the SP value of resin A to fall within the range of 2.50 to 4.50, and by further adjusting the characteristics of the silica fine particles, the occurrence of color unevenness in the fixed image was improved. The inventors speculate the reasons for the above are as follows.

[0043] By adjusting SPa-SPw within the aforementioned range, the wax, which uniformly oozes onto the surface of the toner particles during fixing, rapidly adheres to the silicone oil present on the surface of the fine silica particles. This is believed to be because the SP values ​​of the wax and silicone oil are close to each other, thus facilitating their mixing. Next, during cooling after fixing, wax crystallizes as a result of reduced molecular mobility. In this study, if the molecular mobility of the silicone oil is high, the molecular mobility of the wax is not easily reduced, and crystallization is easily hindered. Conversely, if the molecular mobility of the silicone oil is low, the molecular mobility of the wax also tends to decrease, resulting in easier crystallization. Therefore, by adjusting SPa-SPw within the aforementioned range, the wax is uniformly oozed onto the surface of the toner particles during fixing, and as a result, the wax easily adheres to the surface of the silicone oil containing the fine silica particles. Furthermore, the inventors speculate that the occurrence of color unevenness in the fixed image can be improved by utilizing the fact that wax crystallization is improved through a specific silicone oil.

[0044] As mentioned above, the unit of SP value (SPa-SPw) is (cal / cm²) 3 ) 0.5 The value ranges from 2.50 to 4.50.

[0045] When the SPa-SPw value is below 2.50, the wax and resin A tend to mix during fixing, which in turn inhibits the uniform exudation of wax onto the surface of the toner particles, resulting in uneven color. When the SPa-SPw value exceeds 4.50, the wax and resin A tend to separate during fixing, and the wax tends to become integrated. As a result, the uniform exudation of wax onto the surface of the toner particles is inhibited, causing uneven color. When the SPa-SPw value exceeds 4.50, the wax excessively exudes onto the surface of the toner particles, and its charge decreases. The SPa-SPw value is preferably 2.90 to 4.00, more preferably 3.00 to 3.60.

[0046] There are no particular limitations on resin A, as long as it meets the difference in SP values ​​mentioned above. For example, known resins such as polyester resin, vinyl resin, epoxy resin, polyurethane resin, polyamide resin, cellulose resin, and polyether resin, or mixed or composite resins described above, can be used as resin A. The content of resin A in the toner particles is 0.5% by mass or more, and more preferably 3.0% by mass or more. When the content of resin A in the toner particles is within the above range, the wax may diffuse more evenly during fixing, and combined with the aforementioned effects of silicone oil, it can further improve the occurrence of color unevenness. There is no particular upper limit on the content of resin A, but it is preferably 80.0% by mass or less.

[0047] Resin A is preferably a polyester resin. When resin A is a polyester resin, the wax tends to ooze more evenly onto the surface of the toner particles during fixing; therefore, combined with the above-mentioned effects of silicone oil, the occurrence of color unevenness can be further improved.

[0048] Saturated polyester resins, unsaturated polyester resins, or both can be appropriately selected and used as polyester resins. Ordinary polyester resins produced from alcohol and acid components can be used as polyester resins; examples of these two components are listed below. Diol components that can be used in the preparation of polyester resins include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentanediol, 2-ethyl-1,3-hexanediol, cyclohexenedimethanol, butenyl glycol, octenediol, cyclohexenedimethanol, hydrogenated bisphenol A, bisphenols represented by formula (E) and their derivatives, and diols represented by formula (F).

[0049]

[0050] (In formula (E), R represents ethylene or propylene; and x and y are each integers greater than or equal to 0, such that the average value of x+y is between 0 and 10.)

[0051]

[0052] (In formula (F), R' represents any one of (B1) to (B3); and x' and y' are integers greater than or equal to 0, such that the average of x'+y' is between 0 and 10.)

[0053] From the viewpoint of reactivity with polyester resins, it is preferable to use bisphenol of formula (E) or its derivatives, or bisphenol of formula (E) or its derivatives with an average value of x+y of 1 to 4.

[0054] Examples of teratosides or higher alcohols that can be used to prepare polyester resins include glycerol, sorbitol, 1,2,3,6-hexanetetrol, 1,4-dehydrated sorbitol, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene.

[0055] Other alcohol components that can be used to prepare polyester resins include polyols such as oxidized alkenyl ethers of phenolic resins, for example.

[0056] Examples of dicarboxylic acids that can be used to prepare polyester resins include dicarboxylic acids and their derivatives, such as: phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride, and their anhydrides and lower alkyl esters; alkyl dicarboxylic acids, such as succinic acid, adipic acid, sebacic acid, and azelaic acid, and their anhydrides and lower alkyl esters; alkenyl succinic acids or alkyl succinic acids, such as dodecenyl succinic acid and dodecyl succinic acid, and their anhydrides and lower alkyl esters; and unsaturated dicarboxylic acids, such as fumaric acid, maleic acid, citraconic acid, and itaconic acid, and their anhydrides and lower alkyl esters. In this disclosure, from an operability or reactivity point of view, phthalic acid dicarboxylic acids, such as terephthalic acid and isophthalic acid, are preferred.

[0057] Examples of ternary or higher polycarboxylic acid components that can be used in the preparation of polyester resins include, for example: trimellitic acid, pyromellitic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetra(methylenecarboxy)methane, 1,2,7,8-octanetetracarboxylic acid, Empol trimeric acid, and their anhydrides and lower alkyl esters; and tetracarboxylic acids represented by formula (G), their anhydrides and lower alkyl esters, and other polycarboxylic acids and their derivatives. Trimerictic acid is preferred among the aforementioned components in terms of reactivity or ease of adjusting the acid value of the resin.

[0058]

[0059] (In formula (G), X represents an alkylene or alkenylene group; in this text, X is a substituent having 5 to 30 carbon atoms and having one or more side chains each having 3 or more carbon atoms.)

[0060] Other acidic components that can be used to prepare polyester resins include, for example, 1,2,3,4-butanetetracarboxylic acid and benzophenonetetracarboxylic acid, as well as their anhydrides and other polycarboxylic acids.

[0061] From the viewpoint of charge, the SP value (SPa) of resin A is preferably from 10.50 to 12.80, more preferably from 11.00 to 12.60. When the SPPa is within the above range, appropriate moisture adsorption occurs on resin A, and the charge is easily improved.

[0062] To increase SPa, resin A preferably has monomer units represented by formula (A) in its resin structure. By introducing highly hydrophilic units, such as monomer units represented by formula (A), into resin A, the value of SPa increases, and the phase separation from wax can be further improved. As a result, during fixing, it is easier to promote uniform exudation of wax on the surface of the toner particles, which, combined with the action of silicone oil, further improves the occurrence of color unevenness.

[0063] The term monomer unit refers to the form obtained by the reaction of monomeric substances in a polymer. The content ratio (mass%) of monomer units represented by formula (A) in resin A is preferably 0% by mass or more, and more preferably 20% by mass or less.

[0064]

[0065] When a polyester resin having monomer units represented by formula (A) is used as resin A, the resin can be prepared by condensing a dicarboxylic acid or its anhydride with isosorbide represented by formula (H). Specifically, for example, the resin can be prepared by a method involving dehydration condensation, with a composition ratio of residual carboxyl groups, at a reaction temperature of 180 to 260°C in a nitrogen atmosphere.

[0066]

[0067] There is no particular limitation on the weight-average molecular weight (Mw) of resin A, but it is preferably 5,000 to 50,000, and more preferably 8,000 to 20,000.

[0068] There are no particular restrictions on the type of wax, and the following known materials can be used.

[0069] Examples include esters of monohydric alcohols and aliphatic monohydric carboxylic acids, such as betaine, stearate, and palmitate; esters of monohydric carboxylic acids and aliphatic monohydric alcohols, such as dibenzyl sebacate and hexamethylene dibenzyl sebacate; esters of trihydric alcohols and aliphatic monohydric carboxylic acids, such as tribenzyl trihydrate; esters of pentaerythritol tetrastearate and pentaerythritol tetrapalmitate; and esters of hexahydric alcohols, such as dipentaerythritol hexastearate and dipentaerythritol hexapalmitate. Esters of aliphatic monocarboxylic acids, or esters of hexacarboxylic acids and aliphatic monohydric alcohols; such as esters of polyols and aliphatic monocarboxylic acids, or esters of polycarboxylic acids and aliphatic monohydric alcohols; such as natural ester waxes like carnauba wax and rice wax (hereinafter, the above are also referred to as ester waxes); such as petroleum-based waxes and their derivatives, such as paraffin wax, microcrystalline wax and petrolatum; hydrocarbon waxes and their derivatives obtained by the Fischer-Tropsch process; such as polyolefin waxes and their derivatives, such as polyethylene wax and polypropylene wax (hereinafter, the above are also referred to as hydrocarbon waxes); higher fatty alcohols; such as fatty acids like stearic acid and palmitic acid; amide waxes; and low molecular weight crystalline polyesters such as diethylene glycol distearate.

[0070] The wax preferably comprises at least one selected from the group consisting of the aforementioned ester waxes and hydrocarbon waxes; more preferably, it uses one of the aforementioned ester waxes and hydrocarbon waxes. From the viewpoint of low-temperature fixing and durability, the wax content relative to 100 parts by weight of binder resin is preferably 3.0 parts by weight to 25.0 parts by weight, more preferably 10.0 parts by weight to 25.0 parts by weight. The SP value of the wax (SPw) is preferably 7.90 to 9.60, more preferably 7.90 to 9.20, and even more preferably 8.00 to 9.00.

[0071] The inorganic fine particles comprise silica fine particles whose surfaces are treated with silicone oil. That is, the inorganic fine particles comprise silica fine particles, and the silica fine particles are a surface-treated product using silicone oil. In the silica fine particles… 29 In Si solid-state NMR measurements, when A is taken as the integral value of the D cell obtained by setting the integral value of the Q cell in the CP / MAS measurement to 100, and B is taken as the integral value of the D cell obtained by setting the integral value of the Q cell in the DD / MAS measurement to 100, A and B are required to satisfy the following equations (2) and (3):

[0072] 30≤B≤60...(2)

[0073] 4.0≤A / B≤6.0...(3).

[0074] In this paper, A and B in equations (2) and (3) are derived from... 29 Si solid-state NMR calculations.29 In Si solid-state NMR, four types of peaks can be observed, namely the peaks of the M unit (Equation (4)), D unit (Equation (5)), T unit (Equation (6)) and Q unit (Equation (7)) relative to all silicon atoms in the solid sample.

[0075] M-unit: (Ri)(Rj)(Rk)SiO 1 / 2 Equation (4)

[0076] D unit: (Rg)(Rh)Si(O) 1 / 2 Equation (5)

[0077] T-unit: RmSi(O) 1 / 2 Formula (6)

[0078] Q unit: Si(O) 1 / 2 Formula 4 (7)

[0079] (In formulas (4), (5) and (6), Ri, Rj, Rk, Rg, Rh and Rm are each an alkyl group, halogen atom, hydroxyl group, acetoxy group or alkoxy group bonded to silicon, such as a hydrocarbon group having 1 to 6 carbon atoms.)

[0080] exist 29 Two measurement methods are used in Si solid-state NMR measurements: the DD / MAS method and the CP / MAS method. In the DD / MAS method, all silicon atoms in the sample are observed, and information about the silicon atom content is obtained. In the case of measuring silica fine particles by DD / MAS, the Q unit shows peaks originating from the silica fine particles before surface treatment (hereinafter also referred to as silica matrix), and the D unit shows peaks originating from the silicone oil used as a surface treatment agent. That is, B in equation (2), which is the integral value of the D unit obtained by taking the integral value of the Q unit as 100, represents the amount of silicone oil present on the silica fine particles. For example, the greater the amount of silicone oil present on the surface of the silica matrix, the larger the value of B.

[0081] In contrast, in CP / MAS measurements, measurements are performed simultaneously with magnetization via hydrogen atoms present near silicon atoms, thus allowing for high sensitivity observation of silicon atoms near hydrogen atoms. The presence of hydrogen atoms near silicon atoms indicates low molecular mobility in the measured sample. Specifically, the lower the molecular mobility of the measured sample and the larger the sample quantity, the higher the sensitivity for observing silicon atoms. That is, in the case of measuring fine silica particles by CP / MAS, the value of A in equation (3), i.e., the integral value of the D unit obtained by taking the integral value of the Q unit as 100, includes not only information about the amount of silicone oil relative to the silica matrix, but also information about the molecular mobility of the silicone oil. For example, the more low molecular mobility silicone oil present on the surface of the silica matrix, the larger the observed value of A. Therefore, information about the molecular mobility of silicone oil present on the surface of the silica matrix can be appropriately obtained by calculating the standard value A / B obtained by dividing A by B. The larger the value of A / B, the lower the molecular mobility of the silicone oil.

[0082] While maintaining a value of 30 ≤ B, the silica fine particles are thoroughly surface-treated with silicone oil, and because silicone oil is hydrophobic, their charge-carrying capacity is improved in high-temperature and high-humidity environments. On the other hand, while maintaining a value of B ≤ 60, the silica fine particles are easier to break down, and when added externally to toner particles, they are easily and uniformly fixed to the toner particles, thereby improving their charge-carrying capacity. In this paper, B is preferably 35 to 55. Furthermore, B can be controlled based on the amount of silicone oil treatment or the number-average particle size of the silica base material.

[0083] When the A / B ratio is below 4.0, the molecular mobility of the silicone oil present on the surface of the silica-based material is high, and therefore the molecular mobility of the wax is not easily reduced, wax crystallization is hindered, and uneven color occurs. On the other hand, when the A / B ratio exceeds 6.0, the molecular mobility of the silicone oil becomes too low, and therefore the frequency of wax adhesion to the silicone oil decreases. As a result, it becomes difficult to reduce the molecular mobility of the wax, wax crystallization is hindered, and uneven color occurs. In this paper, an A / B ratio of 4.7 to 5.7 is preferred. Furthermore, the A / B ratio can be controlled by modifying the side chains and terminal substituents of the silicone oil, or based on the amount of silicone oil processed.

[0084] Known materials can be used as silica base materials, which are fine silica particles before surface treatment. Examples include fumed silica produced by burning silicon compounds, particularly silicon halides, generally silicon chloride, and usually purified silicon tetrachloride, in an acid-hydrogen flame; wet silica produced from water glass; sol-gel silica particles obtained by the wet method; gel silica particles; aqueous colloidal silica particles; alcohol silica particles; molten silica particles obtained by the fumed method; and deflagration silica particles.

[0085] The inorganic fine particles include silica fine particles; the silica fine particles are a surface-treated product, wherein the silica fine particles before surface treatment are treated with silicone oil; the number-average particle size of the primary particles of the silica fine particles before surface treatment is preferably 5 nm to 35 nm, and more preferably 5 nm to 30 nm. Within the above range, the toner can be sufficiently endowed with high fluidity and high charge. Within the above range, the values ​​of B and A / B are also easily adjusted.

[0086] Examples of silicone oils (surface treatment agents) include, for example, dimethyl silicone oil (a polysiloxane with methyl side chains and ends), or modified silicone oils in which functional groups such as hydrogen atoms, phenyl, methanol, hydroxyl, carboxyl or epoxy groups are substituted for the side chains or ends of the molecular chains of dimethyl silicone oil.

[0087] The inorganic fine particles include silica fine particles; the silica fine particles are surface-treated products in which the silica fine particles before surface treatment are surface-treated with silicone oil; the amount of silicone oil used is preferably 15.0 to 40.0 parts by weight, more preferably 23.0 to 35.0 parts by weight, relative to 100 parts by weight of the silica fine particles before surface treatment. When the amount is 15.0 parts by weight or more, the silica fine particles are sufficiently surface-treated with silicone oil, and thus, because silicone oil is hydrophobic, the charge-carrying capacity in high temperature and high humidity environments is improved. On the other hand, when the amount is 40.0 parts by weight or less, the silica fine particles are easier to break, and when the silica fine particles are added externally to the toner particles, they are easily and uniformly fixed to the toner particles, and the charge-carrying capacity is easily improved.

[0088] Furthermore, the silicone oil preferably includes a modified silicone oil. When the silicone oil includes a modified silicone oil, the modified silicone oil adheres firmly to the surface of the fine silica particles (i.e., the silica base material) before surface treatment, resulting in a reduction in the molecular mobility of the silicone oil. Therefore, during fixing, wax easily crystallizes from the modified silicone oil, and combined with the aforementioned uniform exudation effect of the wax, it facilitates the improvement of uneven color distribution.

[0089] Furthermore, the silicone oil preferably comprises a modified silicone oil represented by formula (B). This modified silicone oil is a silicone oil having reactive groups at the ends (one or both ends) of the molecular chain of dimethyl silicone oil. The modified silicone oil with reactive groups at the ends of the molecular chain forms chemical bonds with silanol groups on the surface of the silica base material at the ends of the molecular chain, resulting in a tendency to reduce the molecular mobility of the silicone oil. Consequently, wax crystallization is easily promoted, and this, combined with the aforementioned uniform exudation effect of the wax, makes it easier to improve the occurrence of color unevenness.

[0090]

[0091] (where R is in the formula) 1 It can be a methanol group, hydroxyl group, epoxy group, carboxyl group, alkyl group, or hydrogen atom; R 2 The alkyl group is a methanol group, a hydroxyl group, an epoxy group, a carboxyl group, or a hydrogen atom; m is an integer from 30 to 200 (more preferably from 40 to 100); and each alkyl group in the side chain of formula (B) is optionally substituted with a methanol group, a hydroxyl group, an epoxy group, a carboxyl group, or a hydrogen atom.

[0092] The silicone oil preferably comprises a modified silicone oil represented by formula (C). The modified silicone oil represented by formula (C) is a modified silicone oil having hydroxyl groups at both ends of its molecular chain. The hydroxyl groups present at the ends of the molecular chain of the modified silicone oil form strong siloxane bonds with the silanol groups on the surface of the silica base material. As a result, the molecular mobility of the silicone oil tends to decrease. Therefore, wax crystallization is facilitated, and this, combined with the aforementioned uniform exudation effect of the wax, makes it easier to improve the occurrence of color unevenness.

[0093]

[0094] (Where, p is an integer from 30 to 200 (more preferably from 40 to 100).)

[0095] Furthermore, the silicone oil preferably further comprises polydimethylsiloxane represented by formula (D). When the silicone oil comprises polydimethylsiloxane represented by formula (D) and the above-mentioned modified silicone oil, the silica fine particles are sufficiently hydrophobic, and the charge-carrying capacity is easily improved. The values ​​of B and A / B are also easily adjusted within the aforementioned ranges. The amount of polydimethylsiloxane represented by formula (D) is preferably 12.0 to 35.0 parts by weight, more preferably 12.0 to 27.0 parts by weight, relative to 100 parts by weight of silica fine particles before surface treatment.

[0096]

[0097] (Where, n is an integer from 30 to 200 (more preferably from 40 to 100).)

[0098] The amount of modified silicone oil used in the treatment is preferably 0.2 to 15.0 parts by weight, more preferably 1.0 to 13.0 parts by weight, relative to 100 parts by weight of silica particles before surface treatment. By specifying the amount of modified silicone oil within the above-mentioned ranges, the values ​​of B and A / B can be easily adjusted within the above-mentioned ranges. The content of silica particles treated with silicone oil on the surface is preferably 0.2 to 15.0 parts by weight, more preferably 0.5 to 13.0 parts by weight, relative to 100 parts by weight of toner particles.

[0099] Surface treatment of silica-based materials with silicone oil can be performed using known wet or dry methods. By using these methods, surface treatment can be performed while dispersing the silica-based material, resulting in a mechanically appropriate aggregate diameter for the fine silica particles. In surface treatment with silicone oil, the aforementioned silicone oil can be used alone or in multiple forms. In cases where multiple forms are used, a treatment step 1 with a first treatment agent can be performed, wherein the silica-based material is treated with a first silicone oil, followed by a treatment step 2 with a second treatment agent, wherein the silica-based material is treated with a second silicone oil. If multiple treatment steps are present, the values ​​of B and A / B can be adjusted more precisely within the aforementioned ranges.

[0100] Known resins can be used as adhesive resins. For example, homopolymers of styrene and their substituted products, such as polystyrene and polyvinyltoluene, can be used; styrene-propylene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-methyl acrylate copolymers, styrene-ethyl acrylate copolymers, styrene-butyl acrylate copolymers, styrene-octyl acrylate copolymers, styrene-dimethylaminoethyl acrylate copolymers, styrene-methyl methacrylate copolymers, styrene-ethyl methacrylate copolymers, styrene-butyl methacrylate copolymers, styrene-vinylmethyl ether copolymers, styrene-vinylethyl ether copolymers, styrene-vinylmethyl ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-maleic acid copolymers, and styrene-maleic acid ester copolymers can be used; as well as polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resins, polyester resins, polyamide resins, epoxy resins, and polyacrylic acid resins; the above can be used alone or in combination of several. For example, in terms of developing and fixing properties, styrene-acrylate resins, represented by styrene-butyl acrylate and polyester resins, are particularly preferred.

[0101] Examples of polymerizable monomers constituting the above-mentioned styrene-acrylic resins include the following. Examples of styrene-based polymerizable monomers include styrene; α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and p-methoxystyrene.

[0102] Examples of acrylic polymerizable monomers include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, and cyclohexyl acrylate.

[0103] Examples of methacrylic polymerizable monomers include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, and n-octyl methacrylate. There are no particular restrictions on the production methods of styrene-acrylic resins, and known methods can be used.

[0104] Examples of polymerizable monomers that form the above-mentioned polyester resins include those listed below. Examples of polyester resins include condensations of polycarboxylic acids and polyols. In this document, commercially available products or synthetic products may be used as polyester resins.

[0105] Examples of polycarboxylic acids include aliphatic dicarboxylic acids (e.g., oxalic acid, malonic acid, maleic acid, fumaric acid, citracic acid, itaconic acid, glutaric acid, succinic acid, alkenylsuccinic acid, adipic acid, sebacic acid), alicyclic dicarboxylic acids (e.g., cyclohexanedicarboxylic acid), aromatic dicarboxylic acids (e.g., terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid), and their anhydrides and lower alkyl esters (e.g., having 1 to 5 carbon atoms). Preferred polycarboxylic acids among those described above are, for example, aromatic dicarboxylic acids.

[0106] Trivalent or higher carboxylic acids having cross-linked or branched structures can be used in combination with dicarboxylic acids as the aforementioned polycarboxylic acids. Examples of trivalent or higher carboxylic acids include trimellitic acid, pyromellitic acid, their anhydrides, and their lower alkyl esters (e.g., having 1 to 5 carbon atoms). Polycarboxylic acids can be used alone or in combination of two or more forms.

[0107] Examples of polyols include aliphatic diols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, and neopentyl glycol), alicyclic diols (e.g., cyclohexanediol, cyclohexanediol, and hydrogenated bisphenol A), and aromatic diols (e.g., ethylene oxide adducts of bisphenol A and propylene oxide adducts of bisphenol A). Preferred polyols among those described above include aromatic diols and alicyclic diols, with aromatic diols being more preferred.

[0108] As polyols, polyols with a crosslinked or branched structure, consisting of three or more ternary components, can be used in combination with diols. Examples of polyols with three or more ternary components include glycerol, trimethylolpropane, and pentaerythritol. Polyols can be used alone or in combination of two or more forms. There are no particular restrictions on the production method of polyester resins, and known methods can be used. Adhesive resins can also be used in combination with other known resins.

[0109] The toner particles may further comprise colorants. Examples of colorants include the following organic pigments, organic dyes, and inorganic pigments. Examples of yellow pigments include monoazo compounds, diazo compounds, condensed azo compounds, isoindolineone compounds, isoindoline compounds, benzimidazolone compounds, anthrone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specific examples include CI Pigment Yellows 74, 93, 95, 109, 111, 128, 155, 174, 180, and 185.

[0110] Examples of magenta pigments include monoazo compounds, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic lake dye compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, CI pigments Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, and CI pigment Violet 19.

[0111] Examples of cyan pigments include copper phthalocyanine compounds and their derivatives, anthraquinone compounds, and basic dye lake compounds. Specifically, CI Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and 66.

[0112] Examples of black pigments include carbon black, aniline black, non-magnetic ferrites, and magnetite. Pigments that are tinted to black using the aforementioned yellow, magenta, and cyan pigments can also be used.

[0113] The toner disclosed herein can be made into a magnetic toner by introducing a magnetic material therein. In this case, the magnetic material can also be used as a coloring agent. Examples of magnetic materials include iron oxides, such as magnetite, hematite, and ferrite; and metals such as iron, aluminum, copper, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium, as well as alloys and mixtures thereof.

[0114] These pigments can be hydrophobically treated using known methods. Furthermore, these pigments can be used alone or in mixtures, and can also be used in a solid solution state. Various dyes conventionally known as colorants can be used with the pigments. The pigment content is preferably 1.0 to 20.0 parts by weight relative to 100.0 parts by weight of binder resin.

[0115] Toner particles may further contain charge control agents. Conventionally known charge control agents can be used without particular limitation. Charge control agents include negative charge control agents that control the toner to a negative charge and positive charge control agents that control the toner to a positive charge. Specific examples of negative charge control agents include metal complexes of aromatic carboxylic acids, represented by salicylic acid, alkyl salicylic acid, dialkyl salicylic acid, naphthic acid, and dicarboxylic acids; polymers or copolymers having sulfonic acid groups, sulfonate groups, or sulfonate groups; metal salts or metal complexes of azo dyes or azo pigments; and boron compounds, silicon compounds, and calixarenes. Examples of positive charge control agents include quaternary ammonium salts, polymer compounds having quaternary ammonium salts in their side chains, guanidine compounds, aniline black compounds, and imidazole compounds. Examples of polymers or copolymers having sulfonic acid groups, sulfonate groups, or sulfonate groups include homopolymers of sulfonic acid-containing vinyl monomers, represented by styrene sulfonic acid, 2-acrylamide-2-methylpropane sulfonic acid, 2-methacrylamide-2-methylpropane sulfonic acid, vinyl sulfonic acid, and methacrylic acid sulfonic acids; and copolymers of the aforementioned sulfonic acid-containing vinyl monomers with the vinyl monomers shown in the examples of the adhesive resin portion. The amount of charge control agent added is preferably from 0.01 parts by weight to 20.0 parts by weight relative to 100.0 parts by weight of adhesive resin.

[0116] In addition to the aforementioned silica fine particles, the following inorganic fine particles can be used in combination as inorganic fine particles: titanium dioxide, carbon black and fluorinated carbon, metal oxides (e.g., strontium titanate, cerium oxide, aluminum oxide, magnesium oxide and chromium oxide); nitrides (e.g., silicon nitride), metal salts (e.g., calcium sulfate, barium sulfate, calcium carbonate); and metal salts of fatty acids (e.g., zinc stearate and calcium stearate). The inorganic fine particles can be hydrophobically treated to improve the flowability of the toner and to make the charge of the toner particles more uniform. Furthermore, regarding the aforementioned modified silicone oil, examples of hydrophobic treatment agents for inorganic fine particles include unmodified silicone varnishes, various modified silicone varnishes, unmodified silicone oils, silane compounds, silane coupling agents, and other organosilicon compounds and organotitanium compounds. These treatment agents can be used alone or in combination with each other. The content of inorganic fine particles relative to 100 parts by weight of colorant particles is preferably from 0.2 parts by weight to 15.0 parts by weight, more preferably from 0.5 parts by weight to 13.0 parts by weight.

[0117] Toner particles can be produced using either a dry production method (e.g., mixing and pulverizing) or a wet production method (e.g., emulsion polymerization or suspension polymerization). In the case of production using the mixing and pulverizing method, for example, a binder resin and wax containing resin A, and materials such as colorants and charge control agents as needed, are thoroughly mixed in a mixer such as a Henschel mixer or a ball mill. Subsequently, the toner material can be dispersed or melted by melt mixing using a heated mixer such as a heated roller, mixer, or extruder, then solidified by cooling, pulverized, and subsequently graded, and surface-treated as needed, to obtain toner particles. The grading and surface treatment can be performed sequentially, one before the other. Preferably, for production efficiency, a multi-stage classifier is used in the grading step.

[0118] In the emulsion aggregation method, an aqueous dispersion of fine particles made of the constituent materials of the toner particles with a sufficiently small target particle size is prepared in advance, and the fine particles are aggregated in an aqueous medium until the given toner particle size is reached. Then, the resin is heated to undergo melt adhesion, thereby producing the toner.

[0119] Specifically, in the emulsion aggregation method, toner particles are produced by a dispersion step of producing a fine particle dispersion made of the constituent material of the toner particles, an aggregation step of aggregating the fine particles made of the constituent material of the toner particles and controlling the particle size until it reaches the toner particle size, a fusion step of initiating the molten adhesion of the resin contained in the obtained aggregated particles, and a subsequent cooling step.

[0120] Suspension polymerization involves uniformly dissolving or dispersing polymerizable monomers, a binder resin including resin A, and waxes (and, as needed, colorants, polymerization initiators, crosslinking agents, charge control agents, and other additives) to obtain a polymerizable monomer composition. Subsequently, while the polymerization reaction is proceeding simultaneously, the polymerizable monomer composition is dispersed in a continuous phase (e.g., an aqueous phase) containing a dispersant using a suitable mixer to obtain toner particles with a desired particle size. The individual toner particles obtained according to this suspension polymerization method (hereinafter also referred to as "polymerizable toner particles") uniformly have a generally spherical toner particle shape; therefore, the distribution of charge is relatively uniform, and the result can be expected to improve image quality.

[0121] Examples of polymerizable monomers used in the production of polymeric toner granules to form polymerizable monomer compositions include: styrene-based monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and p-ethylstyrene; acrylates such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate; methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate; and other monomers such as acrylonitrile, methacrylonitrile, and acrylamide. These monomers can be used alone or in mixtures thereof. From the viewpoint of the developing properties and durability of toners, among the aforementioned monomers, styrene itself, or a mixture thereof with other monomers, is preferred.

[0122] The polymerization initiator used in the above-mentioned production by suspension polymerization preferably has a half-life of 0.5 to 30 hours during the polymerization reaction. When the polymerization reaction is carried out using 0.5 to 20 parts by mass of polymerization initiator relative to 100 parts by mass of polymerizable monomer, a polymer with a maximum molecular weight between 5,000 and 50,000 is obtained, and the toner particles are given the desired strength and suitable melt characteristics.

[0123] Examples of polymerization initiators include the following: azo or diazo polymerization initiators such as 2,2'-azobis-(2,4-dimethylpentanonitrile), 2,2'-azobisisobutanonitrile, 1,1'-azobis(cyclohexane-1-carboxynitrile), 2,2'-azobis-4-methoxy-2,4-dimethylpentanonitrile, and azobisisobutanonitrile; and peroxidation polymerization initiators such as benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl percarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, tert-butyl peroxide-2-ethylhexanoate, and tert-butyl peroxypentanoate.

[0124] Toner particles can be produced by suspension polymerization with the addition of a crosslinking agent. The viscosity of the toner particles at 120°C can be increased by adding a crosslinking agent. The preferred amount of crosslinking agent is 0.001 to 15 parts by weight relative to 100 parts by weight of polymerizable monomer.

[0125] Examples of crosslinking agents mainly include compounds having two or more polymerizable double bonds, such as aromatic divinyl compounds like divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds, such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate; divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone; and compounds having three or more vinyl groups. These can be used alone or as a mixture of two or more.

[0126] To produce toner particles via suspension polymerization, the aforementioned toner composition and other compositions are typically added appropriately, and uniformly dissolved or dispersed using a dispersant such as a homogenizer, ball mill, or ultrasonic disperser to obtain a polymerizable monomer composition, which is then suspended in an aqueous medium containing a dispersant. By using a high-speed disperser such as a high-speed mixer or ultrasonic disperser, the desired toner particle diameter is obtained in a single step, resulting in sharper toner particles. Regarding the timing of the polymerization initiator addition, the polymerization initiator can be added to the polymerizable monomer simultaneously with other additives, or it can be mixed immediately before suspension in the aqueous medium. Alternatively, the polymerization initiator, dissolved in the polymerizable monomer or solvent, can be added immediately after granulation or before the polymerization reaction begins. After granulation, the particle state can be maintained using a conventional mixer to ensure sufficient agitation and prevent particle floating and settling.

[0127] Known surfactants or organic / inorganic dispersants can be used as dispersants to produce toner particles. Inorganic dispersants are preferred because they do not readily produce harmful ultrafine powders, and their steric hindrance provides dispersion stability. Consequently, they do not easily lose their stability even when the reaction temperature changes, and they are easily washed away without adversely affecting the toner particles. Examples of inorganic dispersants include inorganic compounds such as polyvalent metal salts of phosphoric acid, such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and hydroxyapatite; carbonates such as calcium carbonate and magnesium carbonate; inorganic salts such as calcium metasilicate, calcium sulfate, and barium sulfate; and inorganic compounds such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

[0128] Preferably, the inorganic dispersant is used in an amount of 0.2 to 20 parts by weight relative to 100 parts by weight of the polymerizable monomer. The dispersant can be used alone; alternatively, two or more can be used in combination. Furthermore, 0.001 to 0.1 parts by weight of a surfactant can be used in combination.

[0129] When using such inorganic dispersants, the dispersant can be used as is, or it can be used by producing inorganic dispersant particles in an aqueous medium to obtain finer particles. For example, when using tricalcium phosphate, water-insoluble calcium phosphate can be produced by mixing an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high-speed stirring, and a finer and more uniform dispersion can be obtained. Although water-soluble sodium chloride salts are produced as byproducts, the presence of water-soluble salts in an aqueous medium is more convenient because the dissolution of polymerizable monomers in water is inhibited in this case, and it is less likely to produce ultrafine particles of toners obtained by emulsification polymerization.

[0130] Examples of surfactants include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium lauryl sulfate, sodium stearate, and potassium stearate.

[0131] In the polymerization step of polymerizable monomers, the polymerization temperature is set above 40°C, typically between 50 and 90°C.

[0132] The toner particles are obtained by filtering, washing, and drying the polymer particles according to known methods. The toner of this disclosure can be obtained by externally adding and mixing inorganic fine particles containing silica fine particles surface-treated with silicone oil to the toner particles, thereby causing adhesion to the surface of the toner particles. Furthermore, a classification step may be included in the production process (before mixing the inorganic fine powder) to remove coarse or fine powder from the toner particles.

[0133] Known methods can be used as the above mixing method. In this paper, the Henschel mixer is an example of a suitable apparatus.

[0134] The method for measuring the physical properties of the toner disclosed herein will be described next.

[0135] (Measurement of the melting point of wax)

[0136] The melting point of the wax was measured using a Q2000 differential scanning calorimeter according to ASTM D3418-82. The temperature of the instrument's detection unit was calibrated based on the melting points of indium and zinc, and the heat of dissolution was calibrated based on the heat of indium. Specifically, 1.0 mg of wax was accurately weighed and placed on an aluminum pan, using an empty aluminum pan as a reference. Measurements were then performed over a temperature range of 30 to 200 °C at a heating rate of 10 °C / min. During the measurement, the sample was heated to 200 °C in a single step at a heating rate of 10 °C / min, then cooled to 30 °C at a cooling rate of 10 °C / min, and then reheated. The peak temperature (in °C) of the maximum endothermic peak of the DSC curve within the temperature range of 30 to 200 °C during this second heating process was taken as the melting point of the wax in the DSC measurement.

[0137] (Measurement of weight-average particle size (D4) and number-average particle size (D1) of toner (granules) or silica-based materials)

[0138] The weight-average particle size (D4) and number-average particle size (D1) of the toner (or toner particles) were measured using a precision particle size distribution measuring device, the "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman-Coulter Inc.), based on pore resistance and equipped with a 100 μm orifice, and dedicated software, "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman-Coulter Inc.), for setting measurement conditions and analyzing measurement data. The measurement data were analyzed and calculated. The electrolyte aqueous solution used for measurement could be prepared by dissolving premium sodium chloride in ion-exchanged water to a concentration of approximately 1% by mass. For example, "ISOTON II" (manufactured by Beckman-Coulter Inc.) could be used. The dedicated software was set up as follows before measurement and analysis.

[0139] In the "Change Standard Measurement Method (SOM) Screen" of the dedicated software, set the total count in the control mode to 50,000 particles, the number of measurement cycles to 1, and the Kd value to the value obtained using "Standard Particle 10.0 μm" (manufactured by Beckman-Coulter Inc.). The threshold and noise level are automatically set by pressing the "Threshold / Noise Level Measurement Button". Additionally, set the current to 1600 μA, the gain to 2, and the electrolyte solution to ISOTON II, and check the "Flush the measuring tube after measurement" option. In the "Set Pulse to Particle Size Conversion Screen" of the dedicated software, set the element spacing to logarithmic particle size, the number of particle size elements to 256, and the particle size range to 2 μm to 60 μm. The specific measurement method is as follows.

[0140] (1) Place approximately 200 ml of electrolyte solution into a 250 mL glass round-bottom beaker provided with the Multisizer 3. Place the beaker on the sample stage and stir counterclockwise with a stir bar at 24 seconds / revolution. Then, remove dirt and air bubbles from the mouthpiece using the "mouthpiece rinse" function of the dedicated software.

[0141] (2) Place about 30 ml of electrolyte aqueous solution into a 100 mL flat-bottomed glass beaker made of glass, and add about 0.3 ml of a 10% by mass aqueous solution of "Contaminone N" (a neutral detergent for cleaning precision measuring instruments with a pH of 7, consisting of nonionic surfactants, anionic surfactants, and organic detergent builders, prepared by diluting three times the mass of the solution with ion-exchanged water) as a dispersant.

[0142] (3) Place the predetermined amount of ion-exchanged water into a water tank equipped with an "Ultrasonic Dispersion System Tetora150" (manufactured by Nikkaki Bios Co., Ltd.) with two oscillators with an oscillation frequency of 50kHz and a phase offset of 180° and a power output of 120W, and add about 2ml of Contaminone N to the water tank.

[0143] (4) Place the beaker from (2) into the beaker fixing hole of the ultrasonic disperser and start the ultrasonic disperser. Adjust the height of the beaker to maximize the surface resonance of the electrolyte solution in the beaker.

[0144] (5) While irradiating the electrolyte solution in the beaker of (4) with ultrasound, add approximately 10 mg of toner (or toner granules) little by little to the electrolyte solution and disperse it. Then, continue the ultrasonic dispersion process for another 60 seconds. During ultrasonic dispersion, adjust the water temperature in the bath appropriately to 10°C to 40°C.

[0145] (6) Using a pipette, drop the electrolyte aqueous solution in (5) in which the colorant is dispersed into the round-bottom beaker in (1) mounted on the sample stage, and adjust the measurement concentration to about 5%. Then perform the measurement until the number of particles measured reaches 50,000.

[0146] (7) Analyze the measurement data using the dedicated software provided with the equipment, and calculate the weight-average particle size (D4) and the number-average particle size (D1). When setting the chart / volume % in the dedicated software, the "arithmetic diameter" on the analysis / volume statistics (arithmetic mean) screen is the weight-average particle size (D4). When setting the chart / number % in the dedicated software, the "arithmetic diameter" on the analysis / number statistics (arithmetic mean) screen is the number-average particle size (D1).

[0147] (Methods for measuring the molecular weight of wax and resin A)

[0148] The molecular weights of wax and resin A were measured by gel permeation chromatography (GPC) as follows.

[0149] First, dissolve the sample in tetrahydrofuran (THF) at room temperature. Then, filter the obtained solution with a solvent-resistant membrane filter "Maeshori Disc" with a pore size of 0.2 μm (manufactured by Tosoh Corporation) to obtain a sample solution. Adjust the sample solution so that the concentration of the soluble component in THF is 0.8% by mass. This sample solution is used for measurement under the following conditions.

[0150] Equipment: High-speed GPC device "HLC-8220GPC" (manufactured by Tosoh Corporation)

[0151] Column: LF-604, double column

[0152] Eluent: THF

[0153] Flow rate: 0.6 ml / min

[0154] Oven temperature: 40 °C

[0155] Sample injection volume: 0.020 ml

[0156] To calculate the molecular weight of each sample, a molecular weight calibration curve created using standard polystyrene resins (trade names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000 or A-500", Tosoh Corporation) is used.

[0157] <Method for Measuring SP Value> <The

[0158] According to the commonly used Fedors method, the SP value used in the present invention is calculated based on the types and proportions of the monomers constituting each resin. The evaporation energy (Δei) (cal / mol) and molar volume (Δvi) (cm 3 / mol) are calculated from the table given in "Polym. Eng. Sci., 0.5 0.5 14(2), 147-154(1974)", and (ΣΔei / ΣΔvi) 3 is taken as the SP value (cal / cm 0.5 )

[0159] <Method for Calculating B and A / B by Si Solid-State NMR Measurement of Silica Fine Particles> 29 ​

[0160] After the silica fine particles are separated from the toner surface, the silica fine particles are then processed. 29 Si solid-state NMR measurements will be described next. The method for separating fine silica particles from the toner surface will also be described. 29 Si solid-state NMR measurement method.

[0161] <Methods for separating fine silica particles from the surface of toners>

[0162] When fine silica particles separated from the surface of a toner are used as a measurement sample, the fine silica particles are separated from the toner through the following steps.

[0163] A total of 160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) was added to 100 mL of deionized water and dissolved in a water bath to prepare a sucrose concentrate. A dispersion was prepared by placing a total of 31 g of the sucrose concentrate and 6 mL of Contaminone N (a 10% by mass aqueous solution of a neutral detergent for cleaning precision measuring instruments, consisting of nonionic surfactants, anionic surfactants, and organic detergent builders, with a pH of 7, manufactured by Wako Pure Chemical Industries) into a centrifuge tube. 1 g of toner was added to the dispersion, and the toner clumps were loosened using a spatula or similar tool.

[0164] Centrifuge tubes were placed in a "KM Shaker" (model: V.SX) manufactured by Iwaki Sangyo Co., Ltd., and shaken for 20 minutes at 350 vibrations per minute. After shaking, the solution was transferred to a glass tube (50 mL) for oscillating the rotor and centrifuged at 3500 rpm for 30 minutes.

[0165] In the centrifuged glass tube, the toner particles are present on the top layer, and the fine silica particles are present on the lower aqueous solution side. The lower aqueous solution is collected, and centrifugation is repeated as needed. After thorough separation, the dispersion is dried, and the fine silica particles are collected.

[0166] Next, the silica fine particles recovered from the toner particles were measured under the conditions shown below. 29 Si solid-state NMR measurement.

[0167] < 29 Measurement conditions for Si-NMR (solid-state) >

[0168] solid state 29 The DD / MAS measurement conditions for Si-NMR (solid-state) are as follows.

[0169] Device: JNM-ECX5002 (JEOL RESONANCE Co., Ltd.)

[0170] Temperature: Room temperature

[0171] Measurement method: DD / MAS method 29 Si, 45°

[0172] Sample tube: Zirconia

[0173] Sample: Filled into the test tube in powder form.

[0174] Sample rotation speed: 10kHz

[0175] Relaxation delay: 180s

[0176] Scan count: 2000 scans

[0177] solid state 29 The CP / MAS measurement conditions for Si-NMR (solid-state) are as follows.

[0178] Device: JNM-ECX5002 (JEOL RESONANCE Co., Ltd.)

[0179] Temperature: Room temperature

[0180] Measurement method: CP / MAS method 29 Si, 45°

[0181] Sample tube: Zirconia

[0182] Sample: Filled into the test tube in powder form.

[0183] Sample rotation speed: 10kHz

[0184] Relaxation delay: 5s

[0185] Scan count: 15,000 scans

[0186] Following the above measurements, peak separation of various silane components with different substituents and different bonding groups in silica fine particles was performed by fitting the curves to the following M, D, T, and Q units.

[0187] M-unit: (Ri)(Rj)(Rk)SiO 1 / 2 Equation (4)

[0188] D unit: (Rg)(Rh)Si(O) 1 / 2 Equation (5)

[0189] T-unit: RmSi(O)1 / 2 Formula (6)

[0190] Q unit: Si(O) 1 / 2 Formula 4 (7)

[0191] (In formulas (4), (5) and (6), Ri, Rj, Rk, Rg, Rh and Rm each represent an alkyl group, halogen atom, hydroxyl group, acetoxy group or alkoxy group having 1 to 6 carbon atoms, bonded to silicon atoms.)

[0192] After peak separation, the values ​​of B and A / B are calculated, where A is the integral value of the D unit obtained by setting the integral value of the Q unit in the CP / MAS measurement to 100, and B is the integral value of the D unit obtained by setting the integral value of the Q unit in the DD / MAS measurement to 100.

[0193] Example

[0194] The present disclosure will now be described in more detail with reference to production examples and embodiments, but these embodiments are not intended to limit the present disclosure in any way. As used in the embodiments, the term "parts" in all cases refers to parts by mass.

[0195] <Production of Magnetic Materials>

[0196] (Production of magnetic iron oxides)

[0197] An aqueous solution containing ferrous hydroxide is prepared by mixing 1.00 to 1.10 equivalents of caustic soda solution relative to iron, 0.15% by mass of P₂O₅ relative to iron (calculated as phosphorus), and 0.50% by mass of SiO₂ relative to iron (calculated as silicon) into an aqueous solution of ferrous sulfate. The pH of the aqueous solution is set to 8.0, and an oxidation reaction is carried out at 85°C while air is blown into the aqueous solution to prepare a slurry with seed crystals.

[0198] Next, an aqueous solution of ferrous sulfate is added to the slurry in an amount of 0.90 to 1.20 equivalents relative to the initial alkali amount (sodium component of caustic soda), and the slurry is then maintained at pH 7.6 and an oxidation reaction is carried out while blowing air to obtain a slurry containing magnetic iron oxides.

[0199] (Production of silane compounds)

[0200] Here, 30 parts of isobutyltrimethoxysilane were added dropwise to 70 parts of ion-exchanged water while stirring. The resulting aqueous solution was then maintained at pH 9.0 and a temperature of 45°C, and dispersed using a dispersing blade at a circumferential speed of 0.46 m / s for 120 minutes to allow for hydrolysis and condensation reactions. After adjusting the pH of the aqueous solution to 9.0, it was immediately cooled to 10°C to stop the hydrolysis and condensation reactions. An aqueous solution containing a silane compound was thus obtained.

[0201] (Production of magnetic materials)

[0202] Then, the solution containing 4.7 parts of silane compound relative to 100 parts of the aforementioned magnetic iron oxide was added to the slurry containing the magnetic iron oxide, and the mixture was dispersed using a needle mill. Simultaneously, the pH was maintained at 9.0 and the temperature at 55°C, and the product was dispersed for 60 minutes to perform a hydrophobication treatment of the magnetic material. The dispersion was then filtered using a filter press and washed with plenty of water. Furthermore, the particles obtained by drying at 120°C for 2 hours were crushed and passed through a sieve with a mesh size of 100 μm to obtain a magnetic material with a number average particle size of 230 nm.

[0203] <Production of Fine Silica Particles 1>

[0204] Here, 100 parts of fumed silica (silica-based material; spherical, Evonik Japan Co., Ltd.) with the number-average particle size given in Table (1) were placed in a reaction vessel and diluted to obtain a solution. Under stirring and nitrogen purging, 15 parts of treatment agent 1 (average repeatability unit n = 60) in 100 parts of hexane as given in Table (1) were added; then the whole mixture was stirred at 300°C for 120 minutes. The obtained silica fine particles were then crushed using a needle-type depolymerization device to obtain silica fine particles 1.

[0205] <Production of fine silica particles 2-8 and 11>

[0206] Except that the fractions of fumed silica having the number-average particle size as given in Table (1) are used relative to 100 parts of the fractions of treatment agent 1 and treatment agent 2 shown in Table (1), the fine silica particles 2-8 and 11 are produced in the same manner as in the fine silica particles 1.

[0207] <Production of Silica Fine Particles 9 and 10>

[0208] Except for the use of treatment agent 1, which is of the type and part number shown in Table (1) relative to 100 parts of fumed silica having the number average particle size as given in Table (1), silica fine particles 9 and 10 are produced in the same manner as silica fine particles 1.

[0209] [Table 1]

[0210]

[0211] In the table, the R values ​​of treatment agents 1 and 2 are... 1 and R 2 R represents the modified silicone oil represented by formula (B). 1 and R 2 The parts of treatment agents 1 and 2 here refer to the treatment parts of treatment agents 1 and 2 relative to 100 parts of silica base material (i.e., fine silica particles before surface treatment). The n values ​​of treatment agents 1 and 2 represent the values ​​of m in the modified silicone oil as expressed by formula (B).

[0212] <Production of Resin A1>

[0213] A total of 100 parts of a mixture, consisting of raw material monomers other than trimellitic anhydride and 0.52 parts of di(2-ethylhexanoate)tin as a catalyst, were added to a polymerization tank equipped with a nitrogen inlet line, a dehydration line, and a stirrer, as shown in Table 2. Next, the atmosphere in the polymerization tank was replaced with a nitrogen atmosphere, and a polycondensation reaction was carried out at 200°C for 6 hours. Then, after raising the temperature to 210°C, trimellitic anhydride was added, the pressure in the polymerization tank was reduced to 40 kPa, and a further polycondensation reaction was carried out. Table 2 shows the acid value, weight-average molecular weight (Mw), and SP value (SPa) of the obtained resin. This resin is referred to as Resin A1.

[0214] <Production of Resins A2 to A10>

[0215] Resins A2 through A10 were produced using the same procedures as for resin A1, with the input amounts of the starting monomers given in Table 2 below. Sampling and measurements were then performed sequentially, and the polymerization reaction was stopped once the desired molecular weight was reached. The product was then removed from the polymerization tank. The physical properties of the obtained resins are given in Table 2 below. In the production of resin A9, a 3-molar adduct of bisphenol A in propylene oxide and a 2-molar adduct of bisphenol A in ethylene oxide were used as the BPA in a molar ratio of 45.0 to 44.2. In the production of resin A10, a 3-molar adduct of bisphenol A in propylene oxide and a 2-molar adduct of bisphenol A in ethylene oxide were used as the BPA in a molar ratio of 29.8 to 33.0. When the BPA was not specified, a 3-molar adduct of bisphenol A in propylene oxide was used.

[0216] [Table 2]

[0217]

[0218] In the table, the isosorbide item in the physical properties of resin represents the percentage (by mass) of monomer units obtained from the polymerization of isosorbide represented by formula (A) in resin A.

[0219] The abbreviations in the table are as follows:

[0220] TPA: Terephthalic acid

[0221] IPA: Isophthalic acid

[0222] TMA: Trimeric trioxide

[0223] BPA: Propylene oxide adduct or ethylene oxide adduct of bisphenol A (details as described above).

[0224] EG: Ethylene glycol

[0225] <Wax 1-7>

[0226] The waxes listed in Table 3 below are used here. Table 3 below shows the SP value (SPw) and melting point of waxes 1-7.

[0227] [Table 3]

[0228] Wax 1 benzyl stearate 8.60 68.0 Wax 2 Dipentaerythritol hexamyristicin 9.07 68.0 Wax 3 Polyolefin wax 8.01 72.0 Wax 4 Glycol distearate 8.85 65.0 Wax 5 Fe-Torwax 8.11 78.0 Wax 6 Di-shamianite sebacic acid 8.77 73.3 Wax 7 Paraffin HNP9 8.11 75.0

[0229] Production of Toner Granules 1

[0230] Here, 850 parts of a 0.1 mol / L Na3PO4 aqueous solution were added to a container equipped with a CLEARMIX (MTechnique Co. Ltd.) high-speed stirrer, and the solution was heated to 60°C while stirring at a circular speed of 33 m / s. Then, 68 parts of a 1.0 mol / L CaCl2 aqueous solution were added to prepare an aqueous medium containing a small amount of the slightly water-soluble dispersant Ca3(PO4)2.

[0231] Alternatively, a solution is prepared by mixing and dissolving the following materials using a propeller-type mixer. To mix the materials, the mixer speed is set to 100 rpm.

[0232] -Styrene: 75.0 parts

[0233] - n-Butyl acrylate: 25.0 parts

[0234] - Resin A1: 13.0 parts

[0235] -Magnetic material: 90.0 parts

[0236] - Wax 1: 18.0 parts

[0237] - Iron complex of monoazo dyes (T-77: Hodogaya Chemical Co., Ltd.): 1.0 part

[0238] -1,6-Hexanediol diacrylate: 0.5 parts

[0239] Subsequently, the mixed solution was heated to 60°C and stirred using a TK homogenizer (Primix Corporation (formerly Tokushu Kika Kogyo Co., Ltd.)) at a speed of 9000 rpm to dissolve and disperse the solid portion.

[0240] Then, 10.0 parts of tert-butyl peroxyisopropyl monocarbonate (NOFCorporation, trade name: Perbutyl I) as a polymerization initiator were added and dissolved in the mixed solution to prepare a polymerizable monomer composition. Next, the polymerizable monomer composition was added to the above-mentioned aqueous medium, and the whole mixture was heated to a temperature of 60°C, followed by granulation for 15 minutes while rotating CLEARMIX at a circumferential speed of 33 m / s.

[0241] The product was then transferred to a propeller mixer and reacted at 70°C for 5 hours while stirring at 100 rpm / min. The temperature was then raised to 85°C and reacted for an additional 4 hours to produce magnetic toner particles. Once polymerization was complete, the suspension was cooled to room temperature. After cooling, hydrochloric acid was added to lower the pH to below 2.0, thereby dissolving the inorganic fine particles. After several washes with water, the product was dried at 40°C for 72 hours using a dryer, and then classified using a multi-stage classifier based on the wall adhesion effect to produce toner particles 1.

[0242] <Production of toner granules 2 to 14, 16, 17, 19 to 23, and 25 to 28>

[0243] Except for using the materials and quantities given in Table 4, toner particles 2 to 14, 16, 17, 19 to 23 and 25 to 28 are produced in the same manner as in the production method of toner particles 1.

[0244] Production of Toner Granules 15

[0245] Here, 2.3 parts of tricalcium phosphate were added to 900 parts of ion-exchange water heated to 60°C, and stirred at 10,000 rpm using a TK homogenizer (Tokushu Kika Kogyo Co., Ltd.) to obtain an aqueous medium.

[0246] The following materials were uniformly dissolved and mixed using a propeller-type mixer at 100 rpm to prepare a resin-containing monomer.

[0247] -45.0 parts of styrene

[0248] - 25.0 parts of n-butyl acrylate

[0249] - Resin A9 4.0 parts

[0250] -1,6-Hexanediol diacrylate: 0.5 parts

[0251] The following materials were dispersed using a grinder (Mitsui Miike Engineering Corporation) to obtain monomers containing fine-grained colorants.

[0252] - 30.0 parts of styrene

[0253] -CI Pigment Blue 15:3 7.4 parts

[0254] - Charge control agent (Bontron E-88 (Orient Chemical Industries Co., Ltd.)) 1.0 part

[0255] - Wax 7: Paraffin HNP9 (Nippon Seiro Co., Ltd.) 5.0 parts

[0256] Next, the monomers containing fine-grained colorants and resin-containing monomers were uniformly mixed to obtain a polymerizable monomer composition; then, the polymerizable monomer composition was heated to 60°C. Next, the polymerizable monomer composition was added to an aqueous medium, and the mixture was stirred at 10,000 rpm using a TK homogenizer (Tokushu Kika Kogyo Co., Ltd.) to obtain granules of the polymerizable monomer composition. Then, 10.0 parts of tert-butyl peroxypentanoate as a polymerization initiator were added, and granulation was continued for 10 minutes.

[0257] The product was then transferred to a propeller mixer and reacted at 75°C for 5 hours while stirring at 100 rpm / min. The temperature was then raised to 85°C and reacted for another 5 hours. Once polymerization was complete, the product was cooled to room temperature (25°C), hydrochloric acid was added to dissolve the calcium phosphate, and the product was filtered and washed with water to obtain moist colored granules. The moist colored granules were dried at 40°C for 72 hours to obtain toner granules 15.

[0258] Production of Toner Granules 18

[0259] (Preparation of resin particle dispersion)

[0260] [Preparation of resin particle dispersion (1)]

[0261] -Terephthalic acid: 30 parts

[0262] - Fumaric acid: 70 parts

[0263] - Bisphenol A ethylene oxide 2-molar adduct: 5 parts

[0264] - Bisphenol A propylene oxide 3-molar adduct: 95 parts

[0265] The above materials were added to a 5L flask equipped with a stirrer, nitrogen inlet pipe, temperature sensor, and distillation column. The temperature was raised to 210°C over 1 hour, followed by the addition of 1 part tetraethoxytitanium per 100 parts of the above materials. While distilling off the generated water, the temperature was raised to 230°C over 0.5 hours, and the dehydration condensation reaction was continued at this temperature for 1 hour, followed by cooling of the reaction product. A polyester resin with a weight-average molecular weight of 18,500, an acid value of 14 mg KOH / g, and a glass transition temperature of 59°C was synthesized in this manner.

[0266] Then, 40 parts of ethyl acetate and 25 parts of 2-butanol were added to a container equipped with a temperature control device and a nitrogen purging device to prepare a mixed solvent. Subsequently, 100 parts of the above-mentioned polyester resin were gradually added to and dissolved in the mixed solvent. Then, 10% by mass ammonia solution (resin acid value in 3 times the molar equivalent) was added and stirred for 30 minutes.

[0267] Next, the inside of the container was purged with dry nitrogen to maintain the temperature at 40°C, and 400 parts of deionized water were added dropwise at a rate of 2 parts / minute while stirring the mixture to initiate emulsification. After the addition was complete, the emulsion was allowed to return to room temperature (20°C to 25°C) and bubbled with dry nitrogen for 48 hours while stirring, thereby reducing the amounts of ethyl acetate and 2-butanol to below 1,000 ppm and obtaining a resin particle dispersion in which resin particles with a number average particle size of 200 nm were dispersed. Deionized water was added to the resin particle dispersion to adjust the amount of solids to 20% by mass, and resin particle dispersion (1) was obtained.

[0268] [Preparation of resin particle dispersion (2)]

[0269] Except that resin A1 is used instead of polyester resin here, resin particle dispersion (2) is obtained as in the preparation of resin particle dispersion 1.

[0270] (Preparation of colorant particle dispersion)

[0271] [Preparation of colorant particle dispersion]

[0272] - Cyan pigment, CI Pigment Blue 15:3 (Copper Phthalocyanine, DIC Corporation, Trade Name: FASTOGEN BLUELA 5380): 70 parts

[0273] - Anionic surfactant (Dai-ichi Kogyo Seiyaku Co., Ltd., Neogen RK): 5 parts

[0274] - Ion-exchanged water: 200 parts

[0275] The above materials were mixed and dispersed for 10 minutes using a homogenizer (Ultra-Turrax T50 from IKA-Werke GmbH & Co. KG). Ion-exchanged water was added to make the amount of solid component in the dispersion 20% by mass, so as to obtain a colorant particle dispersion (1) in which colorant particles with a number average particle size of 190 nm are dispersed.

[0276] (Preparation of release agent particle dispersion)

[0277] [Preparation of release agent particulate dispersion (1)]

[0278] - Wax 1: 100 parts

[0279] - Anionic surfactant (Dai-ichi Kogyo Seiyaku Co., Ltd., Neogen RK): 1 part

[0280] - Ion-exchanged water: 350 parts

[0281] The above materials were mixed, heated to 100°C, and dispersed using a homogenizer (Ultra-Turrax T50 from IKA-Werke GmbH & Co. KG), and then dispersed using a Manton-Gaulin high-pressure homogenizer (SPX Flow Technology Systems, Inc.) to obtain a release agent particle dispersion (20% by mass) containing release agent particles with a number average particle size of 200 nm.

[0282] (Production of colorant granules)

[0283] [Preparation of toner particles (1)]

[0284] Prepare the following apparatus, wherein a round stainless steel flask and container A are connected to each other by means of a pipe pump A, which supplies liquid held in container A to the flask; and containers A and B are connected to each other by means of a pipe pump B, which supplies liquid held in container B to container A. Use this apparatus to perform the following operations.

[0285] - Resin particle dispersion (1): 500 parts

[0286] -Colorant particle dispersion (1): 40 parts

[0287] - Anionic surfactant (Tayca Power, trademark, BN2070M, sodium dodecylbenzenesulfonate): 2 parts

[0288] The above materials were placed in a round stainless steel flask, and 0.1N nitric acid was added to adjust the pH to 3.5. Then, 30 parts of a 10% by mass aqueous solution of polyaluminum chloride in nitric acid were added. Next, the mixture was homogenized at 30°C using a homogenizer (IKA-Werke GmbH & Co. KG Ultra-Turrax T50). Subsequently, the aggregated particles were grown in a heated oil bath while the temperature was increased at a rate of 1°C / 30 minutes.

[0289] Simultaneously, 50 parts of resin particle dispersion (2) were placed in container A in the form of a polyester bottle, and 25 parts of release agent particle dispersion (1) were similarly placed in container B. Next, the feed rate of pipeline pump A was set to 0.70 parts / min and the feed rate of pipeline pump B was set to 0.14 parts / min. Then, during the formation of aggregated particles, starting from the point when the temperature inside the round stainless steel flask reached 37.0°C, pipeline pumps A and B were driven to begin supplying the dispersions. As a result, during the formation of aggregated particles, a mixed dispersion containing resin particles and release agent particles was supplied from container A to the round stainless steel flask, while the concentration of release agent particles gradually increased.

[0290] After the dispersion is supplied to the flask, the temperature is maintained for 30 minutes from the point when the temperature inside the flask reaches 48°C to induce the formation of secondary aggregated particles.

[0291] Subsequently, 50 parts of resin particle dispersion (2) were slowly added and maintained for 1 hour. Then, 0.1N sodium hydroxide aqueous solution was added to adjust the pH to 8.5. The temperature was then raised to 85°C while continuing to stir and maintained for 5 hours. The whole mixture was then cooled to 20°C at a rate of 20°C / min.

[0292] The above dispersion was filtered, thoroughly washed with deionized water, and dried to obtain toner particles 18.

[0293] Production of Toner Granules 24

[0294] Here, 850 parts of a 0.1 mol / L Na3PO4 aqueous solution were added to a container equipped with a CLEARMIX (MTechnique Co. Ltd.) high-speed stirrer, and the solution was heated to 60°C while stirring at a circular speed of 33 m / s. Then, 68 parts of a 1.0 mol / L CaCl2 aqueous solution were added to prepare an aqueous medium containing a small amount of the slightly water-soluble dispersant Ca3(PO4)2. The solution was then prepared by mixing and dissolving the following materials using a propeller-type stirrer. To mix the materials, the stirrer speed was set to 100 r / min.

[0295] -Styrene: 75.0 parts

[0296] - n-Butyl acrylate: 25.0 parts

[0297] -Magnetic material: 90.0 parts

[0298] - Wax 3: 18.0 parts

[0299] - Iron complex of monoazo dyes (T-77: Hodogaya Chemical Co., Ltd.): 1.0 part

[0300] -1,6-Hexanediol diacrylate: 0.5 parts

[0301] Subsequently, the resulting mixed solution was heated to 60°C and stirred using a TK homogenizer (Primix Corporation (formerly Tokushu Kika Kogyo Co., Ltd.)) at a speed of 9000 rpm to dissolve and disperse the solid portion.

[0302] Then, a polymerizable monomer composition was prepared by adding 10.0 parts of tert-butyl peroxypentanoate as a polymerization initiator and dissolving tert-butyl peroxypentanoate in the mixed solution. Next, the polymerizable monomer composition was added to the above-mentioned aqueous medium, and the whole mixture was heated to a temperature of 60°C. Then, granulation was carried out for 15 minutes while rotating CLEARMIX at a circumferential speed of 33 m / s.

[0303] The product was then transferred to a propeller mixer and reacted at 70°C for 5 hours while stirring at 100 rpm / min. The temperature was then raised to 85°C and reacted for another 4 hours to produce magnetic toner particles. Once polymerization was complete, the suspension was cooled to room temperature. After cooling, hydrochloric acid was added to lower the pH to below 2.0, thereby dissolving the inorganic fine particles. After several washes with water, the product was dried at 40°C for 72 hours using a dryer, and then classified using a multi-stage classifier based on the wall adhesion effect to produce toner particles 24. Table 4 illustrates the physical properties of each toner particle.

[0304] [Table 4]

[0305]

[0306] <Production of Toner 1>

[0307] Externally mix toner particles 1 (100.0 parts) and silica fine particles 7 (1.0 parts) using FM10C (Nippon Coke & Engineering Co., Ltd.).

[0308] The external addition conditions included an input of 1.8 kg of toner particles, a rotation speed of 3600 rpm, and an external addition time of 30 minutes. Subsequently, toner 1 was obtained by sieving through a 200 μm mesh.

[0309] <Production of Toners 2 to 25 and Comparative Toners 1 to 10>

[0310] Except for the changes in toner particles and silica fine particles shown in the table below, toners 2 to 25 and comparative toners 1 to 10 are obtained using the same method as in the production of toner 1.

[0311] [Table 5]

[0312]

[0313] In the table, the content of resin A is the content (mass %) in the toner particles.

[0314] (Evaluation of toners)

[0315] Toners 1 to 25 and comparison toners 1 to 10 were evaluated using the following method. A modified color laser printer (LBP-712Ci, Canon Inc.) with a processing speed of 300 mm / s was used in the evaluation. The toner contained in the cyan cartridge of the printer was removed, and the cartridge was filled with 150g each of toners 18 and 25. Furthermore, the toner contained in the black cartridge was removed, and the cartridge was filled with 150g each of toners 1 to 17, 19 to 24, and comparison toners 1 to 10. Subsequently, the cartridges were installed in the printer station, and the following evaluation was performed.

[0316] (Evaluation of uneven color)

[0317] Under normal temperature and humidity (temperature 23℃, humidity 60%RH), on coated paper (OS coated paper, Fuji Xerox Co., Ltd., basis weight 127g / m³) 2 ) Create solid 5cm×5cm images with 100% cyan toner and 100% black toner on the image, and continuously output 100 of each image.

[0318] When using black toners 1 to 17 and 19 to 24, and comparison toners 1 to 10, the a* and b* values ​​(in the CIE 1976 L*a*b* color system) of the 100th image were measured at 30 random points using a reflectance spectrophotometer (trade name: Xrite-939, X-Rite Inc.). The color difference ΔE between the two points whose measurements are furthest apart was calculated and used as an indicator of color non-uniformity. The color difference ΔE is calculated according to the following expression, where the a* value of one of the two points is... 1 and b* 1 Let a* and b* be the values ​​of another point, respectively. 2 and b* 2 These are respectively used as the a* value and the b* value.

[0319] ΔE=((a* 1 -a* 2 ) 2 +(b* 1 -b* 2 ) 2 ) 0.5

[0320] When using toners 18 and 25 as cyan toners, the L*, a*, and b* values ​​(in the CIE 1976 L*a*b* color system) of the 100th image were measured at 30 random points using a reflectance spectrophotometer (trade name: Xrite-939, X-Rite Inc.). The color difference ΔE between the two points whose measurements are furthest apart was calculated and used as an indicator of color non-uniformity. The color difference ΔE is calculated according to the following expression, where the L* of one of the two points is... 1 a* 1 and b* 1 Let L*, a*, and b* be the values ​​respectively, and let L* be the value of another point. 2 a* 2 and b* 2 These are respectively used as L* value, a* value, and b* value.

[0321] ΔE=((L* 1 -L* 2 ) 2 +(a* 1 -a* 2 ) 2 +(b* 1 -b* 2 ) 2 ) 0.5

[0322] If the value is below 2.0, the above-mentioned ΔE values ​​are good, and it is more preferable to be below 1.0.

[0323] (Evaluation of fogging in high temperature and high humidity environments)

[0324] In a high-temperature and high-humidity environment (temperature 30°C, humidity 80% RH), a printout test of 16,000 sheets was conducted by repeatedly printing horizontal lines at a percentage of 0.2%, with output paused every two intervals. After the test, the images were left to stand for 48 hours, and then blank images were printed again. The reflectance (%) of the non-image portions of the obtained images was then measured using a "REFLECTOMETER MODEL TC-6DS" (Tokyo Denshoku Co., Ltd.). The obtained reflectance was evaluated according to the following criteria by subtracting the obtained reflectance (%) from the reflectance (%) of unused printout paper (standard paper) measured in the same manner. A smaller value indicates greater suppression of image fogging and better electrophoresis. Glossy paper (HP Brochure Paper 200g, Glossy, HP Inc., 200g / m²) was used. 2 Evaluation is based on the glossy paper model. Grades of C and above are considered good.

[0325] (Evaluation Criteria)

[0326] A: Less than 0.5%

[0327] B: 0.5% or more but less than 1.5%

[0328] C: 1.5% or more but less than 3.0%

[0329] D: 3.0% or more

[0330] (Evaluation of low-temperature fixing performance)

[0331] The following evaluations were conducted using toners 1 to 25 and comparison toners 1 to 10.

[0332] The evaluation was conducted under normal temperature and humidity conditions (temperature 23℃, humidity 50%RH). The fixing medium used was FOXRIVER BOND paper (110g / m²). 2 By using a medium with a relatively uneven surface and made of heavy paper, blank spots are easily generated, thus allowing for a rigorous evaluation of low-temperature fixing performance. As the fixing unit cools to room temperature (25°C), 100 solid black prints are continuously printed, and the average number of blank spots in the solid black images of 95 to 100 prints is measured. As a result of continuous solid black printing, heat from the fixing unit is lost to the medium, leading to a state where sufficient heat cannot be maintained, resulting in a rigorous evaluation of the toner's low-temperature fixing performance. When the toner's fixing performance is insufficient, an image with so-called blank spots, where unfixed toner appears as blank, is output. The evaluation results are assessed by visually observing the average number of blank spots appearing in the output image, for example, using a microscope providing magnification of 10x or higher. Fewer blank spots indicate better low-temperature fixing performance of the toner. In this evaluation, fixing performance is evaluated based on the temperature of the fixing unit with fewer than 10 blank spots. The lower this temperature, the better the low-temperature fixing performance of the toner.

[0333] [Table 6]

[0334] Example 1 Toner 1 0.5 A(0.2) 160 Example 2 Toner 2 1.7 C(2.7) 160 Example 3 Toner 3 1.5 C(2.7) 160 Example 4 Toner 4 1.8 B(1.0) 160 Example 5 Toner 5 1.7 A(0.2) 159 Example 6 Toner 6 0.5 A(0.4) 160 Example 7 Toner 7 0.7 B(0.9) 161 Example 8 Toner 8 1.4 B(1.4) 160 Example 9 Toner 9 1.8 C(1.9) 162 Example 10 Toner 10 1.4 A(0.3) 164 Example 11 Toner 11 0.8 A(0.3) 164 Example 12 Toner 12 0.3 A(0.4) 162 Example 13 Toner 13 0.1 A(0.4) 162 Example 14 Toner 14 0.1 A(0.4) 160 Example 15 Toner 15 0.7 A(0.3) 160 Example 16 Toner 16 0.5 A(0.3) 160 Example 17 Toner 17 0.7 A(0.4) 162 Example 18 Toner 18 0.6 A(0.3) 167 Example 19 Toner 19 0.8 A(0.4) 164 Example 20 Toner 20 1.3 B(1.4) 164 Example 21 Toner 21 0.8 A(0.4) 169 Example 22 Toner 22 1.1 A(0.4) 164 Example 23 Toner 23 0.8 C(1.9) 152 Example 24 Toner 24 1.0 C(2.8) 150 Example 25 Toner 25 1.1 A(0.4) 160 Comparative Example 1 Comparison of toners 1 2.7 A(0.3) 160 Comparative Example 2 Comparison of colorants 2 2.3 D(3.1) 160 Comparative Example 3 Comparison of colorants 3 2.1 D(3.0) 160 Comparative Example 4 Comparison of colorants 4 2.7 B(0.8) 160 Comparative Example 5 Compare colorants 5 2.5 B(0.9) 160 Comparative Example 6 Comparison of colorants 6 2.2 B(1.1) 160 Comparative Example 7 Compare toner 7 2.4 B(1.3) 160 Comparative Example 8 Comparison of colorants 8 2.1 D(3.0) 160 Comparative Example 9 Comparison of colorants 9 3.1 B(0.8) 160 Comparative Example 10 Compare toner 10 3.5 B(0.6) 160

[0335] While the invention has been described with reference to exemplary embodiments, it should be understood that this disclosure is not limited to the disclosed exemplary embodiments. The scope of the appended claims should be interpreted in the broadest possible sense to cover all such modifications and equivalent structures and functions.

Claims

1. A toner, characterized in that, It includes Toner particles containing binder resins and waxes, and Inorganic fine particles on the surface of the toner particles The adhesive resin comprises resin A; When SPa(cal / cm) 3 ) 0.5 Take the SP value of resin A calculated according to the Fedors method, and SPw(cal / cm 3 ) 0.5 When the SP value of the wax is taken as calculated according to the Fedors method, The Spa and the SPw satisfy the following equation (1): 2.50≤SPa-SPw≤4.50... (1), The inorganic fine particles comprise silica fine particles whose surface is treated with silicone oil. The fine silica particles 29 In Si solid-state NMR measurements When A is taken as the integral value of cell D obtained by setting the integral value of cell Q in the CP / MAS measurement to 100, and When B is taken as the integral value of the D element obtained by setting the integral value of the Q element in the DD / MAS measurement to 100, A and B satisfy the following equations (2) and (3): 30≤B≤60... (2) 4.0≤A / B≤6.0... (3), The content of the silica fine particles treated with silicone oil on the surface is 0.2 to 15.0 parts by weight relative to 100 parts by weight of the toner particles.

2. The colorant according to claim 1, wherein the resin A is a polyester resin.

3. The toner according to claim 1 or 2, wherein the content of resin A in the toner particles is 0.5% by mass or more.

4. The toner according to claim 1 or 2, wherein the SPa satisfies the following formula (4): 10.50≤SPa≤12.80... (4).

5. The toner according to claim 1 or 2, wherein the SPw satisfies the following formula (5): 7.90≤SPw≤9.60... (5).

6. The toner according to claim 5, wherein the SPw satisfies the following formula (6): 7.90≤SPw≤9.20... (6).

7. The toner according to claim 1 or 2, The inorganic fine particles include the silica fine particles. The silica fine particles are a surface-treated product obtained by treating the silica fine particles before surface treatment with the silicone oil, and The amount of silicone oil treated is 15.0 to 40.0 parts by weight relative to 100 parts by weight of the fine silica particles before surface treatment.

8. The toner according to claim 1 or 2, wherein the resin A has a monomer unit represented by the following formula (A): 。 9. The toner according to claim 1 or 2, wherein the silicone oil comprises a modified silicone oil.

10. The toner according to claim 1 or 2, wherein the silicone oil comprises a modified silicone oil represented by formula (B): In the formula, R 1 It can be a methanol group, hydroxyl group, epoxy group, carboxyl group, alkyl group, or hydrogen atom; R 2 The alkyl group is a methanol group, hydroxyl group, epoxy group, carboxyl group or hydrogen atom; m is an integer from 30 to 200; and each alkyl group in the side chain of formula (B) is optionally replaced by a methanol group, hydroxyl group, epoxy group, carboxyl group or hydrogen atom.

11. The toner according to claim 10, wherein the modified silicone oil represented by formula (B) is a modified silicone oil represented by formula (C): In the formula, p is an integer from 30 to 200.

12. The toner according to claim 9, wherein the silicone oil further comprises a polydimethylsiloxane represented by formula (D): In the formula, n is an integer from 30 to 200.

13. The toner according to claim 1 or 2, The inorganic fine particles include the silica fine particles; The silica fine particles are a surface treatment product obtained by treating the silica fine particles before surface treatment with the silicone oil on the surface; and The number average particle size of the primary particles of the silica fine particles before surface treatment is 5 to 35 nm.

14. The colorant according to claim 1 or 2, wherein the number average particle size of the primary particles of the silica fine particles before surface treatment is 5 to 30 nm.

Images