Toner and toner manufacturing method

Abstract

To provide a toner that is excellent in heat-resistant storage property and low temperature fixability especially at a light pressure, and satisfies transfer properties at high temperature and high humidity.SOLUTION: A toner has a toner particles containing a binder resin. The binder resin contains a unit (a) represented by the following formula (1), and a unit (b) represented by the following formula (2). In measurement of a surface of the toner particle by time-of-flight secondary ion mass spectrometry TOF-SIMS, when an ion count derived from the unit (a) to the total ion count in a mass-to-charge ratio of 0.5-1850 is defined as Ia1, and an ion count derived from a nitrile group of the unit (b) as Ib1, the Ia1 and the Ib1 satisfy specific formulas.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to toners for developing electrostatic images used in imaging processes such as electrophotography and electrostatic printing. [Background technology]

[0002] In recent years, there has been an increasing demand for smaller copiers and printers with lower energy consumption, and efforts are being made to achieve this by lowering the fixing temperature of the fixing unit. Toners are therefore required to have low-temperature fixability, which allows fixing at lower temperatures. As an example of improving low-temperature fixability, the use of a crystalline material as a binder resin has been proposed. For example, the use of a crystalline vinyl resin as a binder resin has been considered. Crystalline vinyl resins have the property that they hardly soften up to their melting point due to the regular arrangement of side chains within their molecules. Furthermore, once the melting point is reached, the crystals rapidly melt, resulting in a rapid drop in viscosity. For this reason, they have attracted attention as a material that combines excellent sharp melting properties with low-temperature fixability and heat-resistant storage stability. Typically, crystalline vinyl resins have long-chain alkyl groups as side chains in the main chain, and become crystalline when the long-chain alkyl groups on the side chains crystallize with each other. One example of miniaturizing copiers and printers is the miniaturization of the fixing devices attached to the main body. Among fixing devices, film fixing is preferred because it allows for easy simplification of the heat source and device configuration. However, film fixing generally requires a small amount of heat and uses light pressure, making it difficult for sufficient heat to be transferred to the toner, making it difficult for the toner to melt. As a result, insufficient toner melting can lead to image defects such as color transfer when the image is rubbed due to isolated toner particles on the fixed image. Therefore, if the melt viscosity of the toner can be reduced near the toner particle surface, toner particles will fuse together and form a network during fixing, thereby suppressing the above-mentioned image defects. In particular, for light-pressure fixing devices, fixing through a network of toner surface melting is important, so it is preferable to control the presence of crystalline resin near the toner particle surface. Patent Document 1 proposes a toner that uses a crystalline vinyl resin obtained by copolymerizing a polymerizable monomer having a long-chain alkyl group with an amorphous polymerizable monomer having a different SP value, which is said to achieve both low-temperature fixability and heat-resistant storage stability. Patent Document 2 proposes a core-shell toner having a core containing a crystalline vinyl resin and an amorphous shell, thereby achieving both low-temperature fixability, chargeability, and heat-resistant storage stability. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2020-173414 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-130243 Summary of the Invention [Problem to be solved by the invention]

[0004] However, while Patent Document 1 satisfies low-temperature fixability and heat-resistant storage stability, when the toner is continuously used under high temperature and humidity conditions, localized heat is applied to the toner, causing parts of the toner particle surface to melt and increasing adhesion to various components of the device. This can lead to poor transferability. Patent Document 2 has a core-shell structure, but the crystalline vinyl resin near the toner particle surface, which is partially compatible with the shell layer, also melts, which can also lead to poor transferability. Furthermore, if the shell layer becomes thick, there is a risk that low-temperature fixability, especially at light pressure, will deteriorate. In view of the above, an object of the present invention is to provide a toner that is excellent in heat-resistant storage stability, low-temperature fixability especially at low pressure, and transferability under high temperature and high humidity conditions. [Means for solving the problem]

[0005] The present invention provides a toner having toner particles containing a binder resin, The binder resin contains a unit (a) represented by the following formula (1) and a unit (b) represented by the following formula (2):

[0006] [ka] (In formula (1), R1 represents a hydrogen atom or a methyl group, L1 represents a single bond or a divalent linking group, and m represents an integer of 15 or more and 35 or less.)

[0007] [ka] (In formula (2), R2 represents a hydrogen atom or a methyl group.)

[0008] In the surface measurement of the toner particles by time-of-flight secondary ion mass spectrometry TOF-SIMS, The following partial structure (a-1) of the unit (a) for the total ion count in the mass-to-charge ratio range of 0.5 to 1850:

[0009] [ka] (In (a-1), L1 and m are the same as in formula (1) above.) When the ion count derived from the unit (b) is Ia1 and the ion count derived from the nitrile group of the unit (b) is Ib1, Ia1 and Ib1 can be expressed by the following formulas (3) and (4): Ia1≦0.0050 Formula (3) 0.100≦Ib1 Formula (4) Fulfilling The toner has a complex elastic modulus G at 70°C * (70) is 3.0 × 10 4 Pa or more 5.0×10 6 The present invention relates to a toner characterized by having a viscosity of 100 Pa or less.

[0010] The present invention also provides a method for producing a toner having toner particles containing a binder resin, comprising the steps of: The method includes a step of forming particles of a polymerizable monomer composition containing a polymerizable monomer in an aqueous medium, and a polymerization step of polymerizing the polymerizable monomer contained in the particles with an oil-soluble polymerization initiator to obtain toner particles, the polymerizable monomer composition contains a first polymerizable monomer and a second polymerizable monomer different from the first polymerizable monomer; The first polymerizable monomer is represented by the following formula (A), and the second polymerizable monomer is represented by the following formula (B): The toner manufacturing method is characterized in that in the polymerization step, a water-soluble polymerization initiator is added separately from the oil-soluble polymerization initiator when the polymerization conversion rate of the first polymerizable monomer is 30.0% by mass or more and the polymerization conversion rate of the second polymerizable monomer is 90.0% by mass or less.

[0011] [ka] (In formula (A), R1 represents a hydrogen atom or a methyl group, L1 represents a single bond or a divalent linking group, and m represents an integer of 15 or more and 35 or less.)

[0012] [ka] (In formula (B), R2 represents a hydrogen atom or a methyl group.) [Effects of the Invention]

[0013] According to the present invention, it is possible to provide a toner that is excellent in low-temperature fixability and heat-resistant storage stability, and further has excellent transferability under high-temperature and high-humidity conditions. DETAILED DESCRIPTION OF THE INVENTION

[0014] In the present disclosure, unless otherwise specified, the expressions "XX or more and YY or less" and "XX to YY" representing a numerical range mean a numerical range including the endpoints, that is, the lower limit and the upper limit.

[0015] The (meth)acrylic acid ester means an acrylic acid ester and / or a methacrylic acid ester.

[0016] When numerical ranges are stated in stages, the upper and lower limits of each numerical range can be combined in any way.

[0017] A "unit" refers to the reacted form of a monomer substance in a polymer. For example, one section of carbon-carbon bond in the main chain formed by polymerizing a polymerizable monomer in a polymer is considered to be one unit. A polymerizable monomer can be represented by the following formula (C):

[0018] [ka] [In formula (C), R A represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group), and R B represents an optional substituent.]

[0019] A crystalline resin is a resin that shows a clear endothermic peak in a differential scanning calorimeter (DSC) measurement.

[0020] [Characteristics of the toner of the present invention] As mentioned above, when a crystalline vinyl resin is used as a binder resin, if a large amount of the crystalline vinyl resin is exposed on the toner particle surface, frictional heat between the toner particle and the device components melts a portion of the toner particle surface, increasing the adhesion to each component. This results in poor transferability. On the other hand, if a thick shell layer made of an amorphous resin is used to suppress melting of the toner particle surface, low-temperature fixability at light pressure is impaired. Therefore, after extensive research, the inventors have found that the above problem can be solved without making the shell layer excessively thick by appropriately arranging the units (a) and (b) described below on the outermost surface of the toner particles.

[0021] The present invention is characterized by controlling the composition of the toner particle surface. The depth direction of the toner particle surface was analyzed using time-of-flight secondary ion mass spectrometry (TOF-SIMS), and the toner particle structure was identified based on the intensity of the secondary ions obtained for the toner particles.

[0022] TOF-SIMS irradiates a high-speed ion beam (primary ions) onto the sample surface in a high vacuum and collects secondary ions that are expelled from the sample surface due to the sputtering phenomenon, allowing stable observation of secondary ions in an area up to about 1 μm from the sample surface. The toner particle structure can be observed using the depth profiling function of TOF-SIMS. In this case, the primary ion beam scans a square area, typically measuring 100 to several hundred μm on a side, which corresponds to the area of ​​several hundred toner particles.

[0023] This method primarily measures the composition near the surface of toner particles, and by etching the toner particles in the depth direction, the composition of the toner particles can be measured. High-resolution depth profiles can be obtained particularly for shallow regions, specifically regions up to 0.025 μm deep from the toner particle surface, and the structure of the toner particles can be identified by analyzing the depth profile of secondary ions corresponding to the compositional components of the toner particles. Details of the method for measuring secondary ions on the surface of toner particles using time-of-flight secondary ion mass spectrometry (TOF-SIMS) are described below.

[0024] The present inventors believe that the mechanism by which the effects of the present invention are exhibited is as follows.

[0025] The toner of the present invention contains a unit (a) represented by the following formula (1) and a unit (b) represented by the following formula (2) in the binder resin.

[0026] [ka] (In formula (1), R1 represents a hydrogen atom or a methyl group, L1 represents a single bond or a divalent linking group, and m represents an integer of 15 or more and 35 or less.)

[0027] [ka] (In formula (2), R2 represents a hydrogen atom or a methyl group.) The unit (a) has the following partial structure (a-1):

[0028] [ka] (In (a-1), L1 and m are the same as in formula (1) above.) This indicates that the unit (b) has a long-chain alkyl group as shown in the figure, and by exhibiting crystallinity, it improves low-temperature fixability. On the other hand, unit (b) has high heat resistance, and its presence on the toner particle surface suppresses melting of the toner particle surface, thereby suppressing an increase in adhesion to various components. The inventors also believe that the nitrile group in unit (b) exhibits a strong induction effect, resulting in uniform charging of the toner surface. As a result, localized aggregation does not occur between toner particles, and the load on the toner from components is dispersed, further suppressing melting of the toner particle surface and improving transferability.

[0029] These effects are also due to the complex elastic modulus G of the toner at 70°C. * This can only be achieved by appropriately controlling (70). The effects of the present invention cannot be obtained by simply controlling the arrangement of units (a) and (b) on the surface of a toner particle, because it is not possible to control the melting properties of the entire toner particle.

[0030] In the toner of the present invention, in a surface measurement of the toner particles by time-of-flight secondary ion mass spectrometry TOF-SIMS, when the ion count derived from the partial structure (a-1) of the unit (a) relative to the total ion count at a mass-to-charge ratio of 0.5 to 1850 is defined as Ia1 and the ion count derived from the nitrile group of the unit (b) is defined as Ib1, Ia1 and Ib1 satisfy the following formulas (3) and (4): Ia1≦0.0050 Formula (3) 0.100≦Ib1 Formula (4) Meet the following.

[0031] By making Ia1 0.0050 or less and Ib1 0.100 or less, melting of the toner particle surface is suppressed, local aggregation does not occur between toner particles, and the load that the toner receives from members can be dispersed.

[0032] If Ia1 exceeds 0.0050, the presence of the unit (a) on the toner particle surface becomes excessive, and the effect of suppressing melting of the toner particle surface during continuous use cannot be obtained, resulting in deterioration of transferability. Preferably, Ia1 is 0.0001 or more and 0.0030 or less.

[0033] If Ib1 is less than 0.100, the heat resistance of the toner particle surface becomes insufficient, and the toner particle surface melts. Ib1 is expressed by the following formula (5): 0.150≦Ib1≦0.400 Formula (5) It is preferable that the following is satisfied.

[0034] Furthermore, the toner of the present invention has a complex modulus G * (70) is 3.0 × 10 4 Pa or more 5.0×10 6 Pa or less. Complex modulus of elasticity G * When (70) is within the above range, melting from the surface of the toner particles to the entire toner is not inhibited during fixing, and low-temperature fixing properties are improved.

[0035] Complex modulus of elasticity G * (70) is 5.0 × 10 6 If the modulus of elasticity exceeds 100 Pa, the toner will not melt sufficiently during fixing, resulting in poor low-temperature fixing properties. * (70) is 3.0 × 10 4 If the pressure is less than Pa, the toner melts excessively during fixing, resulting in poor high-temperature offset resistance.

[0036] In addition, in the elasticity measurement of the toner, the complex elastic modulus G * (100) is 1.0 × 10 3 It is preferable that the viscosity is at least 100 Pa. By setting the viscosity within the above range, excessive melting during fixing can be suppressed, and high-temperature offset resistance can be improved.

[0037] In addition, in the surface measurement of toner particles by time-of-flight secondary ion mass spectrometry (TOF-SIMS), when the ion count derived from unit (a) of the toner particles at a depth of 25 nm from the outermost surface of the toner particles normalized with polymethyl methacrylate resin is Ia2, and the ion count derived from the nitrile group of unit (b) of the toner particles is Ib2, it is preferable to satisfy the following formulas (6) and (7). 20 < Ib1 / Ia1 < 500 Formula (6) 0.10 < (Ib2 / Ia2) / (Ib1 / Ia1) < 3.00 Formula (7)

[0038] Ib1 / Ia1 represents the ratio of unit (b) to unit (a) on the outermost surface of the toner particles. By being within the above range, the chargeability on the outermost surface of the toner particles becomes uniform, and the fogging suppression is improved. More preferably, Ib1 / Ia1 is 50 or more and 400 or less.

[0039] (Ib2 / Ia2) / (Ib1 / Ia1) represents the change in the ratio of unit (b) to unit (a) in the range of 25 nm depth from the outermost surface of the toner particles. By being within the above range, the melt viscosity near the surface of the toner particles can be lowered, and the low-temperature fixing property is improved. More preferably, (Ib2 / Ia2) / (Ib1 / Ia1) is 0.20 or more and 1.00 or less.

[0040] Furthermore, in the surface measurement of the toner particles by time-of-flight secondary ion mass spectrometry (TOF-SIMS), when the ion count derived from the sulfonic acid group with respect to the total ion count at a mass-to-charge ratio of 0.5 to 1850 is Ic1, it is preferable that Ic1 satisfies 0.005 or more and 0.050 or less. The presence of a specific amount of nitrile groups and sulfonic acid groups with a strong inductive effect on the surface of the toner particles increases the uniformity of chargeability between the toner particles and further improves the transferability. More preferably, it is 0.010 or more and 0.040 or less.

[0041] [Composition Materials of Toner] [Binder Resin] The toner of the present invention contains, as a binder resin, a unit (a) represented by the following formula (1) and a unit (b) represented by the following formula (2).

[0042] [ka] (In formula (1), R1 represents a hydrogen atom or a methyl group, L1 represents a single bond or a divalent linking group, and m represents an integer of 15 or more and 35 or less.)

[0043] [ka] (In formula (2), R2 represents a hydrogen atom or a methyl group.)

[0044] When m in formula (1) is less than 15, the crystallinity tends to be insufficient, and the heat-resistant storage stability is impaired.

[0045] Methods for introducing the unit (a) into the binder resin include a method in which a monomer such as an α-olefin, a β-olefin, a (meth)acrylic acid ester, or an N-alkylacrylamide having a long alkyl chain is subjected to vinyl polymerization.

[0046] Among these, it is preferable that the unit (a) in the binder resin represented by the formula (1) is a unit represented by the following formula (8), because it is easy to control the physical properties of the binder resin, such as the SP value and the melting point.

[0047] [ka] (In formula (8), R1 represents a hydrogen atom or a methyl group, and m represents an integer of 15 or more and 35 or less.)

[0048] As a method for introducing the unit represented by formula (8), a method in which a (meth)acrylic acid ester is subjected to vinyl polymerization as exemplified below can be mentioned.

[0049] Specific examples of such monomers include stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acrylate, octacosa (meth)acrylate, myricyl (meth)acrylate, dodriaconta (meth)acrylate, and 2-decyltetradecyl (meth)acrylate.

[0050] The monomer having the unit (a) may be used alone or in combination of two or more kinds.

[0051] The proportion of the unit (a) in the binder resin is preferably 40.0% by mass or more and 80.0% by mass or less. By setting the proportion within this range, both the sharp melting property and the heat-resistant storage stability of the binder resin can be achieved. It is more preferably 40.0% by mass or more and 70.0% by mass or less, and even more preferably 40.0% by mass or more and 60.0% by mass or less.

[0052] As a method for introducing the unit (b) into the binder resin, a method in which acrylonitrile or methacrylonitrile is subjected to vinyl polymerization can be mentioned.

[0053] The content of the monomer unit (b) in the binder resin is preferably 5.0% by mass or more and 40.0% by mass or less, and more preferably 20.0% by mass or more and 35.0% by mass or less.

[0054] The binder resin may contain other units in addition to the units (a) and (b). Methods for introducing other units include polymerizing the above-exemplified monomers with other vinyl monomers.

[0055] Other vinyl monomers include the following:

[0056] (meth)acrylic acid esters such as styrene, α-methylstyrene, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0057] Monomers having a urea group: for example, monomers obtained by reacting an amine having from 3 to 22 carbon atoms [primary amines (normal butylamine, t-butylamine, propylamine, isopropylamine, etc.), secondary amines (di-normal ethylamine, di-normal propylamine, di-normal butylamine, etc.), aniline, cycloxylamine, etc.] with an isocyanate having from 2 to 30 carbon atoms and having an ethylenically unsaturated bond by a known method.

[0058] Monomers having a carboxy group; for example, methacrylic acid, acrylic acid, and 2-carboxyethyl (meth)acrylate.

[0059] Monomers having a hydroxy group; for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.

[0060] Monomers having an amide group: for example, acrylamide, a monomer obtained by reacting an amine having 1 to 30 carbon atoms with a carboxylic acid having 2 to 30 carbon atoms and an ethylenically unsaturated bond (such as acrylic acid or methacrylic acid) by a known method.

[0061] Monomers having a urethane group: For example, alcohols having 2 to 22 carbon atoms and having an ethylenically unsaturated bond (e.g., 2-hydroxyethyl methacrylate, vinyl alcohol, etc.) and isocyanates having 1 to 30 carbon atoms [monoisocyanate compounds (benzenesulfonyl isocyanate, tosyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, butyl isocyanate, hexyl isocyanate, t-butyl isocyanate, cyclohexyl isocyanate, octyl Isocyanates, 2-ethylhexyl isocyanate, dodecyl isocyanate, adamantyl isocyanate, 2,6-dimethylphenyl isocyanate, 3,5-dimethylphenyl isocyanate, and 2,6-dipropylphenyl isocyanate, etc.), aliphatic diisocyanate compounds (trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, etc.) ester, dodecamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate, etc.), alicyclic diisocyanate compounds (1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated tetramethylxylylene diisocyanate, etc.), and and an aromatic diisocyanate compound (phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, xylylene diisocyanate, etc.), by a known method, and Alcohols with 1 to 26 carbon atoms (methanol, ethanol, propanol, isopropyl alcohol, butanol, t-butyl alcohol, pentanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, undecyl alcohol, lauryl alcohol, dodecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetanol, heptadecanol, stearyl alcohol, isostearyl alcohol, elaidyl alcohol, oleyl alcohol, linoleyl alcohol, linoleyl alcohol) Monomers obtained by reacting, by a known method, an isocyanate having 2 to 30 carbon atoms and having an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl (meth)acrylate, 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl (meth)acrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate, 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate, etc.).

[0062] Vinyl esters: vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl pivalate, vinyl octylate.

[0063] Among these, it is preferable to use styrene, methyl (meth)acrylate, and t-butyl (meth)acrylate.

[0064] The toner of the present invention may contain resin components other than the binder resin for various purposes. Examples of resins that can be used include vinyl resins, polyesters, polyurethanes, and epoxy resins that do not fall under the category of binder resins.

[0065] Examples of polymerizable monomers constituting vinyl resins that do not fall under the category of binder resins include those constituting units (a) and (b) among those mentioned above. Two or more types may be used in combination as needed.

[0066] Polyesters can be obtained by a polycondensation reaction between a divalent or higher polycarboxylic acid and a polyhydric alcohol.

[0067] Examples of polycarboxylic acids include the following compounds:

[0068] Dibasic acids such as succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, malonic acid, and dodecenylsuccinic acid, and their anhydrides or lower alkyl esters, and aliphatic unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, and citraconic acid. 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, and their anhydrides or lower alkyl esters. These may be used alone or in combination of two or more.

[0069] Examples of polyhydric alcohols include the following compounds:

[0070] Alkylene glycols (ethylene glycol, 1,2-propylene glycol, and 1,3-propylene glycol); alkylene ether glycols (polyethylene glycol and polypropylene glycol); alicyclic diols (1,4-cyclohexanedimethanol); bisphenols (bisphenol A); and alkylene oxide (ethylene oxide and propylene oxide) adducts of alicyclic diols. The alkyl moieties of the alkylene glycols and alkylene ether glycols may be linear or branched. In the present invention, branched alkylene glycols are also preferably used. Further examples include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol. These may be used alone or in combination of two or more.

[0071] For the purpose of adjusting the acid value or hydroxyl value, monovalent acids such as acetic acid and benzoic acid, and monovalent alcohols such as cyclohexanol and benzyl alcohol can also be used as needed.

[0072] The method for producing the polyester is not particularly limited, but examples thereof include transesterification and direct polycondensation.

[0073] Polyurethane is obtained by the reaction of a diol component and a diisocyanate component.

[0074] Examples of diisocyanate components include the following: aromatic diisocyanates having 6 to 20 carbon atoms (excluding carbon atoms in NCO groups, the same applies below), aliphatic diisocyanates having 2 to 18 carbon atoms, alicyclic diisocyanates having 4 to 15 carbon atoms, modified products of these diisocyanates (modified products containing a urethane group, a carbodiimide group, an allophanate group, a urea group, a biuret group, a uretdione group, a uretoimine group, an isocyanurate group, or an oxazolidone group; hereinafter, also referred to as "modified diisocyanates"), and mixtures of two or more of these.

[0075] Aromatic diisocyanates include m- and / or p-xylylene diisocyanate (XDI) and α,α,α',α'-tetramethylxylylene diisocyanate.

[0076] Additionally, examples of aliphatic diisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), and dodecamethylene diisocyanate.

[0077] Examples of alicyclic diisocyanates include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate, cyclohexylene diisocyanate, and methylcyclohexylene diisocyanate.

[0078] Among these, aromatic diisocyanates having 6 to 15 carbon atoms, aliphatic diisocyanates having 4 to 12 carbon atoms, and alicyclic diisocyanates having 4 to 15 carbon atoms are preferred, and XDI, IPDI, and HDI are particularly preferred.

[0079] In addition to the diisocyanate component, a tri- or higher isocyanate compound can also be used.

[0080] As the diol component that can be used in the polyurethane, the same dihydric alcohols that can be used in the polyester described above can be used.

[0081] The toner of the present invention preferably has a weight average molecular weight (Mw) of tetrahydrofuran (THF) soluble matter measured by gel permeation chromatography (GPC) of 10,000 or more and 200,000 or less. The lower limit is more preferably 30,000 or more, and even more preferably 50,000 or more. The upper limit is more preferably 180,000 or less. When Mw is within the above range, the durability of the toner is likely to be improved.

[0082] <Release agent> The toner may contain a release agent. The release agent is preferably at least one selected from the group consisting of hydrocarbon waxes and ester waxes. By using a hydrocarbon wax and / or an ester wax, effective release properties can be easily ensured. The hydrocarbon wax is not particularly limited, but examples thereof include the following.

[0083] Aliphatic hydrocarbon waxes: low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymer, Fischer-Tropsch wax, or waxes obtained by oxidizing or adding an acid to these.

[0084] The ester wax may be either a natural ester wax or a synthetic ester wax, as long as it has at least one ester bond in one molecule. The ester wax is not particularly limited, but examples thereof include the following:

[0085] Esters of monohydric alcohols and monocarboxylic acids, such as behenyl behenate, stearyl stearate, and palmityl palmitate; Esters of dicarboxylic acids and monoalcohols, such as dibehenyl sebacate; Esters of dihydric alcohols and monocarboxylic acids, such as ethylene glycol distearate and hexanediol dibehenate; Esters of trihydric alcohols and monocarboxylic acids, such as glycerin tribehenate; Esters of tetrahydric alcohols and monocarboxylic acids, such as pentaerythritol tetrastearate and pentaerythritol tetrapalmitate; Esters of hexahydric alcohols and monocarboxylic acids, such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate, and dipentaerythritol hexabehenate; Esters of polyfunctional alcohols and monocarboxylic acids, such as polyglycerin behenate; natural ester waxes, such as carnauba wax and rice wax; Of these, esters of hexahydric alcohols and monocarboxylic acids such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate, and dipentaerythritol hexabehenate are preferred.

[0086] The release agent may be a hydrocarbon wax or an ester wax, or may be a combination of a hydrocarbon wax and an ester wax, or may be a mixture of two or more of each, but it is preferable to use a hydrocarbon wax alone or two or more of each, and it is more preferable that the release agent is a hydrocarbon wax.

[0087] The content of the release agent in the toner particles is preferably 1.0% by mass or more and 30.0% by mass or less, and more preferably 2.0% by mass or more and 25.0% by mass or less. When the content of the release agent in the toner particles is in the above range, releasability during fixing is easily ensured.

[0088] The melting point of the release agent is preferably 60° C. or higher and 120° C. or lower. When the melting point of the release agent is within the above range, the release agent melts and easily seeps onto the surface of the toner particles during fixing, and the release property is easily exhibited. A melting point of 70° C. or higher and 100° C. or lower is more preferable.

[0089] <Coloring agent> The toner may contain a colorant. Examples of the colorant include known organic pigments, organic dyes, inorganic pigments, carbon black as a black colorant, magnetic particles, etc. In addition, colorants that have been conventionally used in toners may also be used.

[0090] Examples of yellow colorants include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, CI Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, and 180 are preferably used.

[0091] Examples of magenta colorants include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specific examples of suitable magenta colorants include CI Pigment Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, and 254.

[0092] Examples of cyan colorants include copper phthalocyanine compounds and their derivatives, anthraquinone compounds, and basic dye lake compounds. Specific examples of suitable colorants include CI Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and 66. Colorants are selected based on hue angle, saturation, brightness, lightfastness, transparency for overhead projectors, and dispersibility in toner.

[0093] The content of the colorant is preferably 1.0 to 20.0 parts by mass relative to 100.0 parts by mass of the binder resin. When magnetic particles are used as the colorant, the content is preferably 40.0 to 150.0 parts by mass relative to 100.0 parts by mass of the binder resin.

[0094] <Charge control agent> If necessary, a charge control agent may be contained in the toner particles. Alternatively, the charge control agent may be added externally to the toner particles. By incorporating a charge control agent, the charge characteristics can be stabilized, and the optimal triboelectric charge amount can be controlled according to the development system. Known charge control agents can be used, and charge control agents that have a high charging speed and can stably maintain a constant charge amount are particularly preferred.

[0095] Examples of charge control agents that control the toner to be negatively charged include the following: organic metal compounds and chelate compounds are effective, and examples thereof include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds.

[0096] Examples of compounds that control the toner to a positive charge include nigrosine, quaternary ammonium salts, metal salts of higher fatty acids, diorgano tin borates, guanidine compounds, and imidazole compounds.

[0097] The content of the charge control agent is preferably 0.01 parts by mass or more and 20.0 parts by mass or less, and more preferably 0.5 parts by mass or more and 10.0 parts by mass or less, relative to 100.0 parts by mass of the toner particles.

[0098] <External additives> The toner particles may be used as they are, or may be used as a toner by mixing an external additive, etc., as needed, and adhering it to the surface of the toner particles. The external additive may be an inorganic fine particle selected from the group consisting of silica fine particles, alumina fine particles, and titania fine particles, or a composite oxide thereof. Examples of the composite oxide may include silica aluminum fine particles and strontium titanate fine particles.

[0099] The content of the external additive is preferably 0.01 parts by mass or more and 8.0 parts by mass or less, and more preferably 0.1 parts by mass or more and 4.0 parts by mass or less, relative to 100 parts by mass of the toner particles.

[0100] [Toner manufacturing method] Next, the toner manufacturing method will be described in detail. The toner particles may be manufactured by any conventionally known method, such as a suspension polymerization method, an emulsion aggregation method, a solution suspension method, or a pulverization method, as long as the toner particles are manufactured within the scope of the present invention. Among these, the suspension polymerization method is preferred because it is easy to satisfy the above formulas (1) and (2).

[0101] <Toner manufacturing method using suspension polymerization method> (Dispersion process) Polymerizable monomers for forming the binder resin and various materials such as colorants, if necessary, are mixed, and a disperser is used to melt, dissolve, or disperse the mixture to prepare a raw material dispersion. Furthermore, waxes, charge control agents, viscosity-adjusting solvents, and other additives, as listed in the materials section, can be added to the raw material dispersion as needed. As the viscosity-adjusting solvent, any known solvent can be used without particular limitation, as long as it can well dissolve and disperse the above materials and has low solubility in water. Examples of the solvent include toluene, xylene, and ethyl acetate. Examples of the disperser include a homogenizer, a ball mill, a colloid mill, and an ultrasonic disperser.

[0102] (granulation process) The raw material dispersion is added to a previously prepared aqueous medium, and a suspension is prepared using a dispersing machine such as a high-speed stirrer or an ultrasonic dispersing machine. The aqueous medium preferably contains a dispersion stabilizer for adjusting particle size and suppressing aggregation. As the dispersion stabilizer, any conventionally known dispersion stabilizer can be used without any particular limitation.

[0103] Examples of inorganic dispersion stabilizers include phosphates such as hydroxyapatite, tricalcium phosphate, dicalcium phosphate, magnesium phosphate, aluminum phosphate, and zinc phosphate; carbonates such as calcium carbonate and magnesium carbonate; metal hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide; sulfates such as calcium sulfate and barium sulfate, calcium metasilicate, bentonite, silica, and alumina.

[0104] Examples of organic dispersion stabilizers include polyvinyl alcohol, gelatin, methyl cellulose, methylhydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and its salts, and starch.

[0105] Among these, inorganic dispersion stabilizers are preferred because they have a strong aggregation-inhibiting effect due to their large charge polarization and strong adsorption to the oil phase. Hydroxyapatite, tricalcium phosphate, and dicalcium phosphate are even more preferred because they can be easily removed by adjusting the pH.

[0106] (Polymerization process) Toner particles are obtained by polymerizing the polymerizable monomer in the suspension. The polymerization initiator may be mixed with other additives when preparing the raw material dispersion, or may be mixed into the raw material dispersion immediately before suspending it in an aqueous medium. Alternatively, the polymerization initiator may be added in a dissolved state in the polymerizable monomer or another solvent, as needed, during or after the granulation process, i.e., immediately before starting the polymerization process, or during the polymerization process. After the polymerizable monomer is polymerized to obtain a polymer, a solvent removal treatment is performed by heating or reducing pressure as needed, to obtain an aqueous dispersion of toner particles.

[0107] The polymerization initiator may be any known polymerization initiator without any particular limitation. Specific examples include hydrogen peroxide, acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propionyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, lauroyl peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, pertriphenylacetic acid tert-hydroperoxide, tert-butyl performate, tert-butyl peracetate, and tert-butyl perbenzoate. peroxide polymerization initiators such as benzoyl peroxide, tert-butyl perphenylacetate, tert-butyl permethoxyacetate, tert-butyl per-N-(3-toluyl)palmitate, tert-butylbenzoyl peroxide, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxyisobutylate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide; Azo or diazo polymerization initiators such as 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, and azobisisobutyronitrile.

[0108] The concentration of the polymerization initiator is preferably in the range of 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the polymerizable monomer. The type of the polymerization initiator varies slightly depending on the polymerization method, but is used alone or in combination, taking into account the 10-hour half-life temperature.

[0109] When a highly hydrophilic amorphous resin is added to the raw material dispersion, the amorphous resin migrates to the surface of the toner particles during the granulation process and polymerization process, forming a shell layer.

[0110] (filtration process, washing process, drying process, classification process, external addition process) Toner particles are obtained by a filtration process in which solids are obtained from an aqueous dispersion of toner particles by solid-liquid separation, followed by a washing process, a drying process, and a classification process for particle size adjustment as needed. The toner particles may be used as they are as toner. If necessary, toner can also be obtained by mixing and adhering the toner particles with external additives such as inorganic fine powders using a mixer.

[0111] In the suspension polymerization method, in order to easily satisfy the above formulas (3) and (4), the toner particles are preferably produced by the following method.

[0112] That is, a method for producing a toner having toner particles containing a binder resin, The method includes a step of forming particles of a polymerizable monomer composition containing a polymerizable monomer in an aqueous medium, and a polymerization step of polymerizing the polymerizable monomer contained in the particles with an oil-soluble polymerization initiator to obtain toner particles, the polymerizable monomer composition contains a first polymerizable monomer and a second polymerizable monomer different from the first polymerizable monomer; The first polymerizable monomer is represented by the following formula (A), and the second polymerizable monomer is represented by the following formula (B): The polymerization step is characterized in that a water-soluble polymerization initiator is added separately from the oil-soluble polymerization initiator when the polymerization conversion rate of the first polymerizable monomer is 30.0 mass% or more and the polymerization conversion rate of the second polymerizable monomer is 90.0 mass% or less.

[0113] [ka] (In formula (A), R1 represents a hydrogen atom or a methyl group, L1 represents a single bond or a divalent linking group, and m represents an integer of 15 or more and 35 or less.)

[0114] [ka] (In formula (B), R2 represents a hydrogen atom or a methyl group.)

[0115] By employing the above-described production method, it is possible to produce a binder resin in which the amounts of the first polymerizable monomer and the second polymerizable monomer are biased to some extent, and therefore the above formulas (3) and (4) can be satisfied.

[0116] The first polymerizable monomer represented by formula (A) forms a monomer unit (a) represented by formula (1). The second polymerizable monomer represented by formula (B) forms a monomer unit (b) represented by formula (2).

[0117] Examples of the oil-soluble polymerization initiator include pigment dispersants such as 2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), and 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile; and peroxide initiators such as acetylcyclohexylsulfonyl peroxide, diisopropyl peroxycarbonate, decanonyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide, acetyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butylperoxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t-butyl peroxypivalate, and cumene hydroperoxide. Two or more oil-soluble polymerization initiators may be used.

[0118] Examples of the water-soluble polymerization initiator include ammonium persulfate, potassium persulfate, 2,2'-azobis(N,N'-dimethyleneisobutyromidine) hydrochloride, 2,2'-azobis(2-aminodinopropane) hydrochloride, azobis(isobutylamidine) hydrochloride, 2,2'-azobisisobutyronitrile sodium sulfonate, ferrous sulfate, and hydrogen peroxide.

[0119] In particular, ammonium persulfate, potassium persulfate, and ferrous sulfate are preferred because they can easily satisfy the Ic1 value of 0.005 or more and 0.050 or less.

[0120] Furthermore, in the polymerization step, when the polymerization conversion rate of the first polymerizable monomer is 30.0% by mass or more and the polymerization conversion rate of the second polymerizable monomer is 90.0% by mass or less, adding a water-soluble polymerization initiator causes the second polymerizable monomer dissolved in the aqueous phase to polymerize on the surface of the toner particles, thereby causing localization of unit (b), which is preferable.

[0121] [Method for measuring physical properties of toner] The calculation and measurement methods for various physical properties of the toner and toner materials are described below.

[0122] <Monomer analysis of resin components such as binder resins> The types of monomers of resin components such as binder resins are analyzed by using a pyrolysis GC / MS device to analyze samples of each resin component separated from the toner under the following conditions. Measuring device: "Voyager" (product name, manufactured by Thermo Electron) Pyrolysis temperature: 600℃ Column: HP-1 (15 m x 0.25 mm x 0.25 μm) Inlet: 300℃, Split: 20.0 Injection volume: 1.2mL / min Temperature rise: 50℃ (4 min) - 300℃ (20℃ / min)

[0123] <Measurement of secondary ions on toner particle surfaces using time-of-flight secondary ion mass spectrometry TOF-SIMS> The depth profile of ions derived from the resin that makes up the surface of toner particles was measured using a TOF-SIMS (TRIFTIV) manufactured by ULVAC-PHI, Inc. The conditions were as follows:

[0124] [Sample Preparation] An indium plate is placed on the sample holder and toner particles are allowed to adhere to it. If the toner particles move on the sample holder, the indium plate can be placed on the sample holder and coated with carbon paste, after which the toner particles can be fixed. When using a fixing aid such as carbon paste or a silicon wafer, the background is measured under the same conditions without toner particles and converted.

[0125] [Sputtering conditions] Sputter ion species: argon cluster ions ((Arn)+, n = approx. 2000) Accelerating voltage: 10 kV Current value: 8.5nA Sputtering area: 600 x 600 μm 2 Sputtering time: 2 sec / cycle Sputtering rate: 1 nm / sec The sputtering rate was calculated by sputtering a polymethyl methacrylate resin to a film thickness of 300 nm under the above sputtering conditions, calculating the time required to complete sputtering to a film thickness of 300 nm, and then normalizing the calculation.

[0126] [Analysis conditions] Primary ion species: gold ions (Au+) Acceleration voltage: 30 keV Current value: 2pA Analysis area: 300×300μm 2 Number of pixels: 64 x 64 pixels Analysis time: 4sec / cycle Repetition frequency: 8.2kHz Charge neutralization: ON Secondary ion polarity: Positive Secondary ion mass-to-charge ratio (m / z) range: 0.5 to 1850

[0127] [Calculation of Ia1] After identifying the monomer species of the binder resin by the above-described monomer analysis, the intensity ratio of the ion count originating from the partial structure (a-1) of the unit (a) to the ion count originating from all resins including the binder resin in the secondary ion mass-to-charge ratio range of 0.5 to 1850 on the outermost surface of the toner particle is defined as Ia1.

[0128] [Calculation of Ib1] After identifying the monomer species of the binder resin by the above-described monomer analysis, the intensity ratio of the ion count with a secondary ion mass-to-charge ratio of 26 derived from the nitrile group of the unit (b) to the ion count derived from all resins including the binder resin in the secondary ion mass-to-charge ratio range of 0.5 to 1850 on the outermost surface of the toner particle is defined as Ib1.

[0129] [Calculation of Ia2] At a depth of 25 nm from the outermost surface of a toner particle normalized by the above-mentioned polymethyl methacrylate resin, the intensity ratio of the ion count originating from the partial structure (a-1) of the unit (a) to the ion count originating from all resins including the binder resin in a secondary ion mass-to-charge ratio range of 0.5 to 1850 is defined as Ia2.

[0130] [Calculation of Ib2] At a depth of 25 nm from the outermost surface of a toner particle normalized by the above-mentioned polymethyl methacrylate resin, the intensity ratio of the ion count having a secondary ion mass-to-charge ratio of 26 derived from the nitrile group of the unit (b) to the ion count derived from all resins including the binder resin in the secondary ion mass-to-charge ratio range of 0.5 to 1850 is defined as Ib2.

[0131] [Calculation of Ic1] After identifying the monomer species of the binder resin by the above-described monomer analysis, Ic1 is defined as the intensity ratio of the ion count at a secondary ion mass-to-charge ratio of 80 derived from sulfonic acid groups to the ion count derived from all resins including the binder resin in the secondary ion mass-to-charge ratio range of 0.5 to 1850 on the outermost surface of the toner particle.

[0132] (Isolation of Toner Particles from Toner) The above measurement can also be carried out using toner particles isolated from a toner in the following manner.

[0133] Add 160 g of sucrose (Kishida Chemical) to 100 mL of ion-exchanged water and dissolve in a hot water bath to prepare a sucrose concentrate. Add 31 g of the sucrose concentrate and 6 mL of Contaminon N (a 10% by weight aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of nonionic surfactants, anionic surfactants, and organic builders, manufactured by Wako Pure Chemical Industries, Ltd.) to a centrifuge tube (50 mL). Add 1.0 g of toner and break up any clumps with a spatula. Shake the centrifuge tube at 300 strokes per minute (spm) for 20 minutes using a shaker (AS-1N, AS ONE Corporation). After shaking, transfer the solution to a 50 mL glass tube for a swing-out rotor and separate it in a centrifuge (H-9R, Kokusan Corporation) at 3500 rpm for 30 minutes.

[0134] This operation separates the toner particles from the external additives. Visually confirm that the toner particles and aqueous solution have been sufficiently separated, and collect the toner particles that have separated to the top layer with a spatula or similar. The collected toner particles are filtered through a vacuum filter and then dried in a dryer for at least one hour to obtain a sample for measurement. This operation is repeated multiple times to ensure the required amount.

[0135] <Method for measuring the content ratio of various monomer units in binder resin> The content ratio of various monomer units in the binder resin is measured as follows: 1 H-NMR was performed under the following conditions. ·Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measurement frequency: 400MHz Pulse condition: 5.0μs Frequency range: 10500Hz Number of times: 64 ·Measurement temperature: 30℃ · Sample: Place 50 mg of the measurement sample in a sample tube with an inner diameter of 5 mm, add deuterated chloroform (CDCl3) as a solvent, and dissolve it in a constant temperature bath at 40°C.

[0136] obtained 1 From the H-NMR chart, a peak that is independent of the peaks attributable to the constituent elements of the monomer unit (a) is selected from the peaks attributable to the constituent elements of the other monomer units, and the integral value S1 of this peak is calculated. Similarly, a peak that is independent of the peaks attributable to the constituent elements of the monomer unit (b) is selected from the peaks attributable to the constituent elements of the other monomer units, and the integral value S2 of this peak is calculated.

[0137] Furthermore, when a third and a fourth monomer unit are contained, a peak that is independent of the peaks that are attributed to the constituent elements of the third and fourth monomer units is selected from the peaks that are attributed to the constituent elements of the other monomer units, and the integral values ​​S3 and S4 of this peak are calculated.

[0138] The content of the monomer unit (a) is determined using the above integral values ​​S1, S2, S3, and S4 as follows: where n1, n2, n3, and n4 are the numbers of hydrogen atoms in the constituent elements to which the peaks of interest for each site belong.

[0139] Content of monomer unit (a) (mol%)= {(S1 / n1) / ((S1 / n1)+(S2 / n2)+(S3 / n3)+(S4 / n4))}×100 Similarly, the proportions of the monomer unit (b), the third monomer unit, and the fourth monomer unit are determined as follows.

[0140] Content of monomer unit (b) (mol%)= {(S2 / n2) / ((S1 / n1)+(S2 / n2)+(S3 / n3)+(S4 / n4))}×100 Content of third monomer unit (mol%)= {(S3 / n3) / ((S1 / n1)+(S2 / n2)+(S3 / n3)+(S4 / n4))}×100 Content of fourth monomer unit (mol%)= {(S4 / n4) / ((S1 / n1)+(S2 / n2)+(S3 / n3)+(S4 / n4))}×100

[0141] In addition, when a polymerizable monomer that does not contain a hydrogen atom in any component other than the vinyl group is used in the binder resin, 13 Measured nuclei using C-NMR 13 C, and measurements were taken in single pulse mode. 1 The same calculation is performed by H-NMR. Furthermore, when the toner is manufactured by suspension polymerization, the peaks of the release agent and shell resin may overlap, and independent peaks may not be observed. This may make it impossible to calculate the content ratio of each unit in the binder resin. In such cases, a binder resin ' can be manufactured by performing a similar suspension polymerization without using a release agent or other resin, and the binder resin ' can be considered as the binder resin for analysis.

[0142] <Method for measuring polymerization conversion rate of polymerizable monomer> The polymerization conversion rate of the polymerizable monomer is measured using gas chromatography (GC) as follows: 500 mg of toner particle dispersion is precisely weighed and placed in a sample bottle. 10 g of precisely weighed acetone is added to this, and the bottle is capped. The mixture is then mixed thoroughly and irradiated with ultrasonic waves for 30 minutes using a tabletop ultrasonic cleaner (product name "B2510J-MTH" manufactured by Branson) with an oscillation frequency of 42 kHz and an electrical output of 125 W. The mixture is then filtered using a solvent-resistant membrane filter "Myshoridisc" (manufactured by Tosoh Corporation) with a pore diameter of 0.2 μm, and 2 μL of the filtrate is analyzed by gas chromatography. GC:HP 6890GC Column: HP INNOWax (200 μm x 0.40 μm x 25 m) Carrier gas: He (constant pressure mode: 20 psi) Oven: (1) Hold at 50°C for 10 minutes, (2) Heat to 200°C at 10°C / min, (3) Hold at 200°C for 5 minutes Injection port: 200°C, pulsed splitless mode (20→40 psi, until 0.5 min) Split ratio: 5.0:1.0 Detector: 250℃ (FID)

[0143] Then, the "residual amount" of the remaining polymerizable monomer is calculated using a calibration curve prepared in advance using the polymerizable monomer used. Thereafter, the polymerization conversion rate (mass%) of the polymerizable monomer is determined according to the following formula. Polymerization conversion rate (mass%) = 100×(1-(remaining amount of polymerizable monomer) / (total amount of polymerizable monomer used))

[0144] Furthermore, in the case of polymerizable monomers that cannot be detected by gas chromatography (such as behenyl acrylate), the polymerization conversion rate is measured using gel permeation chromatography (GPC) as follows: First, approximately 500 mg of the toner particle dispersion during polymerization is precisely weighed and placed in a sample bottle. This is then dissolved in approximately 10 g of precisely weighed tetrahydrofuran (THF). The resulting solution is then filtered through a solvent-resistant membrane filter "Myshoridisc" (manufactured by Tosoh Corporation) with a pore diameter of 0.2 μm to obtain a sample solution. This sample solution is used for measurements under the following conditions: Apparatus: HLC8120 GPC (detector: RI) (Tosoh Corporation) Column: Shodex KF-801, 802, 803, 804, 805, 806, 807 (7 columns, manufactured by Showa Denko Co., Ltd.) Eluent: tetrahydrofuran (THF) ·Flow rate: 1.0ml / min Oven temperature: 40.0℃ Sample injection volume: 0.10 ml

[0145] Then, the "residual amount" of the remaining polymerizable monomer is calculated using a calibration curve prepared in advance using the polymerizable monomer used. Thereafter, the polymerization conversion rate (mass%) of the polymerizable monomer is determined according to the following formula. The measurement device and measurement conditions are the same as those used in the method for measuring the molecular weight of the resin. Polymerization conversion rate (mass%) = 100×(1-(remaining amount of polymerizable monomer) / (total amount of polymerizable monomer used))

[0146] <Method for measuring the complex elastic modulus of toner> The measuring device used is a rotating plate type rheometer "ARES" (manufactured by TA INSTRUMENTS).

[0147] The measurement sample is prepared by press-molding the toner into a disk shape with a diameter of 25 mm and a thickness of 2.0±0.3 mm using a tablet press in an environment of 25° C.

[0148] The sample is mounted on a parallel plate and heated from room temperature (25°C) to 110°C over 15 minutes. After the sample is shaped, it is cooled to the viscoelasticity measurement starting temperature, and the measurement is started to measure the complex viscosity. At this time, the measurement sample is set so that the initial normal force is 0.

[0149] Furthermore, as described below, in subsequent measurements, the influence of normal force can be cancelled by turning on the auto tension adjustment (Auto Tension Adjustment).

[0150] The measurement is carried out under the following conditions: (1) Use parallel plates with a diameter of 25 mm. (2) The frequency is 6.28 rad / sec (1.0 Hz). (3) The initial applied strain (Strain) is set to 1.0%. (4) Measurement is performed at a temperature ramp rate of 2.0°C / min between 40°C and 100°C. The measurement is performed under the following automatic adjustment mode settings: Measurement is performed in automatic strain adjustment mode (Auto Strain). (5) Set the maximum applied strain to 40.0%. (6) Set the maximum torque (Max Allowed Torque) to 150.0 g·cm and the minimum torque (Min Allowed Torque) to 0.2 g·cm. (7) Set the strain adjustment to 20.0% of the current strain. The measurement is performed in the auto tension adjustment mode. (8) Set Auto Tension Direction to Compression. (9) Set the initial static force to 10.0 g and the auto tension sensitivity to 40.0 g. (10) The operating condition of the auto tension is a sample modulus of 1.0 × 10 3 Pa or more.

[0151] <Measurement of weight average particle size (D4) of toner> Toner particle size can be measured by the pore electrical resistance method. For example, it can be measured and calculated using the Coulter Counter Multisizer 3 and the accompanying dedicated software Beckman Coulter Multisizer 3 Version 3.51 (manufactured by Beckman Coulter, Inc.).

[0152] A precision particle size distribution measuring device using the pore electrical resistance method (product name: Coulter Counter Multisizer 3) and dedicated software (product name: Beckman Coulter Multisizer 3 Version 3.51, manufactured by Beckman Coulter, Inc.) is used. An aperture diameter of 100 μm is used, and measurements are made with an effective number of 25,000 measurement channels, and the measurement data is analyzed and calculated.

[0153] The aqueous electrolyte solution used for the measurement is prepared by dissolving special grade sodium chloride in ion-exchanged water to a concentration of approximately 1% by mass, such as ISOTON II (trade name) manufactured by Beckman Coulter.

[0154] Before carrying out the measurements and analysis, the dedicated software is set up as follows.

[0155] In the "Change Standard Measurement Method (SOM) screen" of the dedicated software, set the total count in control mode to 50,000 particles, the number of measurements to 1, and the Kd value obtained using standard particles (10.0 μm, manufactured by Beckman Coulter). Press the threshold / noise level measurement button to automatically set the threshold and noise level. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II (trade name), and check the option to flush the aperture tube after measurement.

[0156] In the dedicated software's "Pulse to particle size conversion setting screen," set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm or more and 60 μm or less.

[0157] The specific measurement method is as follows. (1) Pour approximately 200 mL of the electrolyte solution into a 250 mL round-bottom glass beaker made specifically for the Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 revolutions per second. Then, use the "aperture tube flush" function of the dedicated software to remove any dirt and air bubbles from inside the aperture tube. (2) Approximately 30 mL of the aqueous electrolyte solution is placed in a 100 mL flat-bottom glass beaker, and approximately 0.3 mL of a diluted solution prepared by diluting Contaminon N (trade name) (a 10% aqueous solution of a neutral detergent for cleaning precision measuring instruments, manufactured by Wako Pure Chemical Industries, Ltd.) three times by mass with ion-exchanged water is added. (3) A predetermined amount of ion-exchanged water and approximately 2 mL of Contaminon N (trade name) are added to the water tank of an ultrasonic disperser (trade name: Ultrasonic Dispersion System Tetora150, manufactured by Nikkaki Bios Co., Ltd.) that has two oscillators with an oscillation frequency of 50 kHz built in with a phase shift of 180 degrees and an electrical output of 120 W. (4) Set the beaker (2) in the beaker fixing hole of the ultrasonic disperser, operate the ultrasonic disperser, and adjust the height of the beaker so that the resonance state of the liquid surface of the electrolytic solution in the beaker is maximized. (5) While the electrolyte solution in the beaker in (4) is irradiated with ultrasonic waves, approximately 10 mg of toner is added little by little to the electrolyte solution and dispersed. The ultrasonic dispersion process is then continued for another 60 seconds. During the ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be between 10°C and 40°C. (6) Using a pipette, add the electrolytic solution (5) containing dispersed toner particles to the round-bottom beaker (1) placed in the sample stand, and adjust the measurement concentration to approximately 5%. Then, measure the number of particles measured until it reaches 50,000. (7) The measurement data is analyzed using the dedicated software provided with the device, and the weight-average particle size (D4) is calculated. Note that when the dedicated software is set to Graph / Volume %, the "Average diameter" on the Analysis / Volume Statistics (Arithmetic Mean) screen is the weight-average particle size (D4). [Example]

[0158] The present invention will be described in more detail below with reference to examples, but these examples are not intended to limit the scope of the present invention. In the following formulations, parts are by weight unless otherwise specified.

[0159] Example 1 [Toner production by suspension polymerization method] (Production of Toner Particles 1) Methacrylonitrile (polymerizable monomer B; equivalent to formula (B)) 30.0 parts Styrene 13.0 parts Ethyl methacrylate 7.0 parts Aluminum di-t-butyl salicylate 1.0 parts Colorant: Pigment Blue 15:3 6.5 parts The mixture was placed in an attritor (manufactured by Nippon Coke Corporation) and dispersed at 200 rpm for 2 hours using zirconia beads with a diameter of 5 mm to obtain a raw material dispersion.

[0160] Meanwhile, 735.0 parts of ion-exchanged water and 16.0 parts of trisodium phosphate (12-hydrate) were added to a container equipped with a high-speed stirring device, a homomixer (manufactured by Primix Corporation), and a thermometer, and the temperature was raised to 60°C while stirring at 12,000 rpm. An aqueous calcium chloride solution prepared by dissolving 9.0 parts of calcium chloride (dihydrate) in 65.0 parts of ion-exchanged water was added thereto, and the mixture was stirred at 12,000 rpm for 30 minutes while maintaining the temperature at 60°C. 10% hydrochloric acid was added thereto to adjust the pH to 6.0, and an aqueous medium in which an inorganic dispersion stabilizer containing hydroxyapatite was dispersed in water was obtained.

[0161] Next, the raw material dispersion liquid was transferred to a container equipped with a stirrer and a thermometer, and the temperature was raised to 60°C while stirring at 100 rpm. Behenyl acrylate (polymerizable monomer A; equivalent to formula (A)) 50.0 parts Release agent 1 10.0 parts (Release agent 1: DP18 (dipentaerythritol stearate ester wax, melting point 79°C, manufactured by Nippon Seiro Co., Ltd.) After stirring at 100 rpm for 30 minutes while maintaining the temperature at 60°C, 7.0 parts of t-butyl peroxypivalate (NOF Corp.: Perbutyl PV) as oil-soluble polymerization initiator 1 and 1.0 part of t-butyl peroxyisobutyrate (Arkema Yoshitomi Co., Ltd.: L80) as oil-soluble polymerization initiator 2 were added and stirred for another minute, and then poured into the aqueous medium being stirred at 12,000 rpm with the high-speed stirrer. Stirring was continued at 12,000 rpm with the high-speed stirrer while maintaining the temperature at 60°C for 20 minutes to obtain a granulation liquid.

[0162] The granulation liquid was transferred to a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube, and the temperature was raised to 70 ° C. under a nitrogen atmosphere while stirring at 150 rpm. The first-stage polymerization reaction was carried out at 150 rpm. The polymerization conversion rates were measured in advance during the reaction. When the polymerization conversion rate of polymerizable monomer A reached 50.0% by mass and the polymerization conversion rate of polymerizable monomer B reached 80.0% by mass, 1.0 parts of potassium persulfate (KPS) was added as a water-soluble polymerization initiator. The retention time for the first-stage polymerization reaction was 5 hours.

[0163] The temperature was then raised to 90°C, and a second polymerization reaction was carried out for 4 hours while maintaining the temperature at 90°C. The temperature was then further raised to 99°C, and a third polymerization reaction was carried out for 3 hours while maintaining the temperature at 99°C, thereby obtaining a toner particle dispersion.

[0164] The resulting toner particle dispersion was cooled to 45°C while stirring at 150 rpm, and then heat-treated for 5 hours while maintaining the temperature at 45°C. Subsequently, while continuing to stir, dilute hydrochloric acid was added until the pH reached 1.5 to dissolve the dispersion stabilizer. The solid content was filtered, thoroughly washed with ion-exchanged water, and then vacuum-dried at 30°C for 24 hours to obtain toner particles 1.

[0165] (Preparation of Toner 1) For the above toner particles, 1:100.0 parts, silica fine particles (hydrophobicized with hexamethyldisilazane, number average particle diameter of primary particles: 10 nm, BET specific surface area: 170 m) were added as an external additive. 22.0 parts of the toner powder (1.0 parts / g) was added and mixed at 3,000 rpm for 15 minutes using a Henschel mixer (manufactured by Nippon Coke Co.), to obtain Toner 1. The physical properties of Toner 1 obtained are shown in Tables 2 and 3.

[0166] <Examples 2 to 3, 5 to 16> Toner particles 2 to 3 and 5 to 16 were obtained in the same manner as in Example 1, except that the types and amounts of polymerizable monomers used, the types and amounts of oil-soluble polymerization initiators and water-soluble polymerization initiators used, and polymerization conditions were changed as shown in Tables 1-1 and 1-2.

[0167] Furthermore, external addition was carried out in the same manner as in Example 1 to obtain toners 2 to 3 and 5 to 16. The physical properties of the toners are shown in Tables 2 and 3.

[0168] Example 4 [Toner production by suspension polymerization method] (Production of Toner Particles 4) Methacrylonitrile (polymerizable monomer B; equivalent to formula (B)) 30.0 parts Styrene 13.0 parts Ethyl methacrylate 7.0 parts Aluminum di-t-butyl salicylate 1.0 parts Colorant: Pigment Blue 15:3 6.5 parts The mixture was placed in an attritor (manufactured by Nippon Coke Corporation) and dispersed at 200 rpm for 2 hours using zirconia beads with a diameter of 5 mm to obtain a raw material dispersion.

[0169] Meanwhile, 735.0 parts of ion-exchanged water and 16.0 parts of trisodium phosphate (12-hydrate) were added to a container equipped with a high-speed stirring device, a homomixer (manufactured by Primix Corporation), and a thermometer, and the temperature was raised to 60°C while stirring at 12,000 rpm. An aqueous calcium chloride solution prepared by dissolving 9.0 parts of calcium chloride (dihydrate) in 65.0 parts of ion-exchanged water was added thereto, and the mixture was stirred at 12,000 rpm for 30 minutes while maintaining the temperature at 60°C. 10% hydrochloric acid was added thereto to adjust the pH to 6.0, and an aqueous medium in which an inorganic dispersion stabilizer containing hydroxyapatite was dispersed in water was obtained.

[0170] Next, the raw material dispersion liquid was transferred to a container equipped with a stirrer and a thermometer, and the temperature was raised to 60°C while stirring at 100 rpm. Behenyl acrylate (polymerizable monomer A; equivalent to formula (A)) 50.0 parts Release agent 1 10.0 parts (Release agent 1: DP18 (dipentaerythritol stearate ester wax, melting point 79°C, manufactured by Nippon Seiro Co., Ltd.) After stirring at 100 rpm for 30 minutes while maintaining the temperature at 60°C, 7.0 parts of t-butyl peroxypivalate (NOF Corp.: Perbutyl PV) as oil-soluble polymerization initiator 1 and 1.0 part of t-butyl peroxyisobutyrate (Arkema Yoshitomi Co., Ltd.: L80) as oil-soluble polymerization initiator 2 were added and stirred for another minute, and then poured into the aqueous medium being stirred at 12,000 rpm with the high-speed stirrer. Stirring was continued at 12,000 rpm with the high-speed stirrer while maintaining the temperature at 60°C for 20 minutes to obtain a granulation liquid.

[0171] The granulation liquid was transferred to a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube. The temperature was raised to 70°C while stirring at 150 rpm under a nitrogen atmosphere, and the first-stage polymerization reaction was carried out at 150 rpm. After stirring for 2 hours, 2.0 parts of methacrylonitrile were added and stirred for 5 minutes. The polymerization conversion rates were measured during the reaction. When the polymerization conversion rate of polymerizable monomer A reached 50.0% by mass and the polymerization conversion rate of polymerizable monomer B reached 75.0% by mass, 1.0 parts of potassium persulfate (KPS) was added as a water-soluble polymerization initiator. The retention time for the first-stage polymerization reaction was 5 hours in total.

[0172] The temperature was then raised to 90°C, and a second polymerization reaction was carried out for 4 hours while maintaining the temperature at 90°C. The temperature was then further raised to 99°C, and a third polymerization reaction was carried out for 3 hours while maintaining the temperature at 99°C, thereby obtaining a toner particle dispersion.

[0173] The resulting toner particle dispersion was cooled to 45°C while stirring at 150 rpm, and then heat-treated for 5 hours while maintaining the temperature at 45°C. Subsequently, while continuing to stir, dilute hydrochloric acid was added until the pH reached 1.5 to dissolve the dispersion stabilizer. The solid content was filtered, thoroughly washed with ion-exchanged water, and then vacuum-dried at 30°C for 24 hours to obtain toner particles 4.

[0174] (Preparation of Toner 4) For the above toner particles, 1:100.0 parts, silica fine particles (hydrophobicized with hexamethyldisilazane, number average particle diameter of primary particles: 10 nm, BET specific surface area: 170 m) were added as an external additive. 2 2.0 parts of the toner powder (1.0 parts / g) was added and mixed at 3,000 rpm for 15 minutes using a Henschel mixer (manufactured by Nippon Coke Co.), to obtain Toner 4. The physical properties of Toner 4 obtained are shown in Tables 2 and 3.

[0175] <Comparative Examples 1 and 2> Toner particles 17 and 18 were obtained in the same manner as in Example 1, except that the types and amounts of polymerizable monomers used, the types and amounts of oil-soluble polymerization initiators and water-soluble polymerization initiators used, and polymerization conditions were changed as shown in Tables 1-1 and 1-2.

[0176] Furthermore, external addition was carried out in the same manner as in Example 1 to obtain toners 17 and 18. The physical properties of the toners are shown in Tables 2 and 3.

[0177] <Comparative Example 3> (Production of amorphous resin 1) The following materials were added to an autoclave equipped with a pressure reducing device, a water separating device, a nitrogen gas introducing device, a temperature measuring device and a stirring device. Terephthalic acid 32.3 parts (50.0 mol%) Bisphenol A-propylene oxide 2 mole adduct 67.7 parts (50.0 mole%) Potassium titanium oxalate (catalyst) 0.02 parts Subsequently, the reaction was carried out under a nitrogen atmosphere at normal pressure at 220°C until the desired molecular weight was reached, to obtain amorphous resin 1. The weight average molecular weight of amorphous resin 1 was 15,200, and the glass transition temperature was 70°C.

[0178] [Toner production by suspension polymerization method] (Production of toner particles 19) Methacrylonitrile (polymerizable monomer B; equivalent to formula (B)) 30.0 parts Styrene 13.0 parts Ethyl methacrylate 7.0 parts Aluminum di-t-butyl salicylate 1.0 parts Colorant: Pigment Blue 15:3 6.5 parts The mixture was placed in an attritor (manufactured by Nippon Coke Corporation) and dispersed at 200 rpm for 2 hours using zirconia beads with a diameter of 5 mm to obtain a raw material dispersion.

[0179] Meanwhile, 735.0 parts of ion-exchanged water and 16.0 parts of trisodium phosphate (12-hydrate) were added to a container equipped with a high-speed stirring device, a homomixer (manufactured by Primix Corporation), and a thermometer, and the temperature was raised to 60°C while stirring at 12,000 rpm. An aqueous calcium chloride solution prepared by dissolving 9.0 parts of calcium chloride (dihydrate) in 65.0 parts of ion-exchanged water was added thereto, and the mixture was stirred at 12,000 rpm for 30 minutes while maintaining the temperature at 60°C. 10% hydrochloric acid was added thereto to adjust the pH to 6.0, and an aqueous medium in which an inorganic dispersion stabilizer containing hydroxyapatite was dispersed in water was obtained.

[0180] Next, the raw material dispersion liquid was transferred to a container equipped with a stirrer and a thermometer, and the temperature was raised to 60°C while stirring at 100 rpm. Behenyl acrylate (polymerizable monomer A; equivalent to formula (A)) 50.0 parts Release agent 1 10.0 parts (Release agent 1: DP18 (dipentaerythritol stearate ester wax, melting point 79°C, manufactured by Nippon Seiro Co., Ltd.) Amorphous resin 1 5.0 parts The mixture was added and stirred at 100 rpm for 30 minutes while maintaining the temperature at 60°C, and then 7.0 parts of t-butyl peroxypivalate (Perbutyl PV, manufactured by NOF Corporation) was added as an oil-soluble polymerization initiator and stirred for another minute, after which the mixture was poured into the aqueous medium being stirred at 12,000 rpm by the high-speed stirring device.

[0181] While maintaining the temperature at 60°C, stirring was continued at 12,000 rpm for 20 minutes using the high-speed stirring device to obtain a granulation liquid.

[0182] The granulation liquid was transferred to a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube, and the temperature was raised to 70°C while stirring at 150 rpm under a nitrogen atmosphere, and a first-stage polymerization reaction was carried out at 150 rpm. The first-stage polymerization reaction was held for 5 hours. The temperature was then raised to 90°C, and a second polymerization reaction was carried out for 4 hours while maintaining the temperature at 90°C. The temperature was then further raised to 99°C, and a third polymerization reaction was carried out for 3 hours while maintaining the temperature at 99°C, thereby obtaining a toner particle dispersion.

[0183] The resulting toner particle dispersion was cooled to 45°C while stirring at 150 rpm, and then heat-treated for 5 hours while maintaining the temperature at 45°C. Subsequently, while continuing to stir, dilute hydrochloric acid was added until the pH reached 1.5 to dissolve the dispersion stabilizer. The solid content was filtered, thoroughly washed with ion-exchanged water, and then vacuum-dried at 30°C for 24 hours to obtain toner particles 19.

[0184] (Preparation of Toner 19) For 100.0 parts of the above toner particles, silica fine particles (hydrophobicized with hexamethyldisilazane, number average particle size of primary particles: 10 nm, BET specific surface area: 170 m) were added as an external additive. 2 The mixture was mixed at 3000 rpm for 15 minutes using a Henschel mixer (manufactured by Nippon Coke Co.) to obtain Toner 19. The physical properties of Toner 19 obtained are shown in Tables 2 and 3.

[0185] <Comparative Example 4> [Toner production by emulsion aggregation method] (Preparation of Resin Particle Dispersion 1) Styrene 280.0 parts Methacrylonitrile 220.0 parts Stearyl acrylate 500.0 parts Dodecyl mercaptan 6.0 parts Decanediol acrylate 4.0 parts The above ingredients were mixed and dissolved, and the resulting solution was dispersed and emulsified in a flask with 20.0 parts of the anionic surfactant Newlex Paste H (NOF Corporation) dissolved in 1,300.0 parts of ion-exchanged water. While stirring for 10 minutes, 200.0 parts of ion-exchanged water containing 20.0 parts of ammonium persulfate was added, and the atmosphere was replaced with nitrogen. The contents were then heated to 70°C and emulsion polymerization was carried out for 6 hours. The reaction solution was then cooled to room temperature to produce Resin Particle Dispersion 1.

[0186] (Preparation of Resin Particle Dispersion 2) Styrene 280.0 parts Methacrylonitrile 220.0 parts Stearyl acrylate 500.0 parts Acrylic acid 20.0 parts Dodecyl mercaptan 12.0 parts Decanediol acrylate 4.0 parts The above ingredients were mixed and dissolved, and the resulting solution was dispersed and emulsified in a flask with 20.0 parts of the anionic surfactant Newlex Paste H (NOF Corporation) dissolved in 1,300.0 parts of ion-exchanged water. While stirring for 10 minutes, 200.0 parts of ion-exchanged water containing 20.0 parts of ammonium persulfate was added, and the atmosphere was replaced with nitrogen. The contents were then heated to 70°C and emulsion polymerization was carried out for 6 hours. The reaction solution was then cooled to room temperature to produce resin particle dispersion 2.

[0187] (Preparation of Colorant Dispersion) Phthalocyanine pigment: 250 parts (PV FAST BLUE, manufactured by Dainichi Seika Chemicals Co., Ltd.) Anionic surfactant: 20 parts (Dai-ichi Kogyo Seiyaku Co., Ltd.: Neogen RK) Ion-exchanged water: 730 parts The above ingredients were mixed and dissolved, and then dispersed using a homogenizer (Ultra Turrax manufactured by IKA) to obtain a colorant dispersion.

[0188] (Preparation of Release Agent Particle Dispersion) -Preparation of release agent particle dispersion- Polyethylene wax: 400 parts (Toyo Petrolite: Polywax 725) Anionic surfactant: 20 parts (Nyu-Rex R manufactured by Nippon Oil & Fats Co., Ltd.) Ion-exchanged water: 580 parts The above ingredients were mixed and dissolved, and then dispersed using a homogenizer (Ultra Turrax, manufactured by IKA Corporation), and then dispersed using a pressure discharge homogenizer to prepare a release agent particle dispersion liquid in which release agent particles (polyethylene wax) were dispersed.

[0189] (Preparation of Shell Resin Particle Dispersion) The following materials were placed in a reaction vessel equipped with a reflux condenser, a stirrer, and a nitrogen inlet tube under a nitrogen atmosphere. Toluene 100.0 parts Styrene (St) 84.5 parts n-Butyl acrylate (BA) 11.3 parts Methyl methacrylate (MMA) 2.5 parts Methacrylic acid (MAA) 1.7 parts t-Butyl peroxypivalate 3.0 parts The contents of the vessel were stirred at 200 rpm, heated to 70°C, and stirred for 10 hours. The contents were then heated to 100°C and polymerized for 6 hours. The solvent was then distilled off to obtain Shell Resin 1. Shell Resin 1 had a Tg of 71°C, an SP value of 9.9, and a peak molecular weight (Mp) of 15,000.

[0190] The following raw materials were placed in a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen inlet tube, and were dissolved by heating to a temperature of 80°C. Shell Resin 1 100.0 parts Methyl ethyl ketone 45.0 parts Tetrahydrofuran 45.0 parts Diethylaminoethanol 1.0 parts Next, 300.0 parts of 80°C ion-exchanged water was slowly added under stirring to effect phase inversion emulsification, and the resulting aqueous dispersion was then transferred to a distillation apparatus and distilled until the distillate temperature reached 100°C.

[0191] After cooling, ion-exchanged water was added to the obtained aqueous dispersion to adjust the shell resin concentration in the dispersion to 20%, which was designated as Shell Resin Dispersion A. A portion of Shell Resin Dispersion 1 was sampled and the volume-based median diameter (D50) was measured, which was 480 nm.

[0192] (Production of toner particles 20) Resin particle dispersion 1 900.0 parts Resin particle dispersion 2 225.0 parts Colorant particle dispersion 100.0 parts Release agent particle dispersion 63.0 parts Aluminum sulfate 5.0 parts (Wako Pure Chemical Industries, Ltd.) Ion-exchanged water 1000.0 parts The above was placed in a round stainless steel flask, adjusted to pH 2.0, dispersed using a homogenizer (IKA Ultra Turrax T50), and then heated to 64°C with stirring in a heating oil bath. After holding at 61°C for 3 hours, observation with an optical microscope confirmed the formation of aggregated particles with an average particle size of approximately 5.0 μm. After further heating and stirring at 61°C for 4 hours, observation with an optical microscope confirmed the formation of aggregated particles with an average particle size of approximately 5.4 μm.

[0193] Ion-exchanged water was added to the obtained dispersion to adjust the resin concentration in the dispersion to 20%, thereby preparing a core particle dispersion.

[0194] To 500.0 parts of the core particle dispersion (100.0 parts solids), 6 parts of a 10% aqueous solution of polyaluminum chloride were added dropwise, and then 50 parts of shell resin dispersion 1 (10.0 parts solids) were added to adjust the pH to 4, followed by stirring for 30 minutes. The suspension was heated to 71°C and stirred for an additional 3 hours. The suspension was then filtered, thoroughly washed with ion-exchanged water, and dried in a vacuum dryer to obtain toner particles 20.

[0195] (Preparation of Toner 20) For 100.0 parts of the above toner particles, silica fine particles (hydrophobicized with hexamethyldisilazane, number average particle diameter of primary particles: 10 nm, BET specific surface area: 170 m) were added as an external additive. 2 2.0 parts of the toner powder (1.0 parts / g) was added and mixed at 3000 rpm for 15 minutes using a Henschel mixer (manufactured by Nippon Coke Co.), to obtain toner 20. The physical properties of the toner 20 obtained are shown in Tables 2 and 3.

[0196] [Table 1-1]

[0197] [Table 1-2]

[0198] [Table 2]

[0199] [Table 3]

[0200] [Toner evaluation method] Toners 1 to 16 according to Examples 1 to 16 and toners 17 to 20 according to Comparative Examples 1 to 4 were evaluated by the following methods. The evaluation results are shown in Table 4. Table 4 also shows the weight average particle size (D4) of each toner.

[0201] <1> Low temperature fixability For the evaluation of low-temperature fixability, a laser beam printer, HP LaserJet Enterprise 600 M603, manufactured by Hewlett-Packard Co., was prepared with the film fixing unit removed. The removed fixing unit was also modified so that the temperature could be set arbitrarily and the process speed was set to 400 mm / sec.

[0202] Using the above printer, under normal temperature and humidity conditions (temperature 23.5°C, humidity 60% RH), the toner amount per unit area is 0.5 mg / cm 2 An unfixed image was then prepared. The unfixed image was then passed through the above-mentioned fixing device adjusted to 130°C. The recording medium was "Prober Bond Paper" (105 g / m 2 The resulting fixed image was fixed at 4.9 kPa (50 g / cm 2 The image was rubbed five times with Silbon paper under a load of 1000 kJ / cm2, and the image density was evaluated based on the decrease (%) in image density before and after rubbing. A: The reduction rate of image density is less than 5.0%. B: The rate of decrease in image density is 5.0% or more and less than 10.0%. C: The rate of decrease in image density is 10.0% or more and less than 15.0%. D: The reduction rate of image density is 15.0% or more.

[0203] <2> High temperature offset resistance The fixing temperature was increased from 130°C in increments of 10°C, and the highest temperature at which no hot offset was observed was defined as the maximum fixing temperature, and the difference between 130°C and the minimum fixing temperature was defined as the fixable range. The evaluation criteria for the fixable range were as follows: A: The temperature at which hot offset does not occur is the low temperature starting point temperature + 60°C or more. B: The temperature at which hot offset does not occur is the temperature at the low temperature starting point +50°C or more but less than +60°C. C: The temperature at which hot offset does not occur is higher than the temperature at the low temperature starting point +40°C and lower than +50°C. D: The temperature at which hot offset does not occur is the temperature at the low temperature starting point +30°C or more and less than +40°C It is full. E: Hot offset occurs in the temperature range below the low temperature starting point +30°C.

[0204] <3> Heat resistant storage stability To evaluate the stability during storage, heat resistance storage stability was evaluated. 5 g of toner was placed in a 100 ml resin cup and left for 3 days in an environment of a temperature of 52.5°C and a humidity of 70 RH%, after which the cohesion of the toner was measured as follows and evaluated according to the following criteria.

[0205] The measurement device used was a "Powder Tester" (Hosokawa Micron Corporation) with a digital display vibrometer "Digivro MODEL 1332A" (Showa Sokki Co., Ltd.) connected to the side of the vibration table. A sieve with a mesh size of 38 μm (400 mesh), a sieve with a mesh size of 75 μm (200 mesh), and a sieve with a mesh size of 150 μm (100 mesh) were placed on top of each other on the vibration table of the powder tester from the bottom up. Measurements were carried out in an environment of 23°C and 60% RH as follows. (1) The vibration amplitude of the vibration table was adjusted in advance so that the displacement value on the digital display vibrometer would be 0.60 mm (peak-to-peak). (2) The toner that had been left for 10 days as described above was then left in advance in an environment of 23°C and 60% RH for 24 hours, and 5.00 g of the toner was precisely weighed out and gently placed on the top sieve with 150 μm openings. (3) After the sieves were vibrated for 15 seconds, the mass of the toner remaining on each sieve was measured, and the degree of cohesion was calculated according to the following formula. Cohesion degree (%) = {(mass of sample on 150 μm sieve (g)) / 5.00 (g)} × 100 + {(Sample mass (g) on ​​75 μm mesh sieve) / 5.00 (g)} x 100 x 0.6 + {(Sample mass (g) on ​​38 μm mesh sieve) / 5.00 (g)} x 100 x 0.2

[0206] [Evaluation criteria] A: Cohesion level is less than 10.0% B: Cohesion degree is 10.0% or more and less than 15.0% C: Cohesion degree is 15.0% or more and less than 20.0% D: Cohesion degree is 20.0% or more

[0207] <4> Transferability evaluation after endurance use in a high temperature and humidity environment The image forming apparatus used was a commercially available laser printer, the LBP-712Ci (Canon), equipped with an intermediate transfer belt as an intermediate transfer member. The secondary transfer bias was made variable, and the printer was modified to have a process speed of 240 mm / sec. A commercially available process cartridge, the 040H (cyan) toner cartridge (Canon), was used. The product toner was removed from the cartridge, which was then cleaned with an air blower, and 150 g of the toner to be evaluated was then refilled.

[0208] The yellow, magenta and black cartridges were inserted into each of the yellow, magenta and black stations, with the product toner removed and the remaining toner amount detection mechanism disabled, and the evaluation was carried out.

[0209] The above process cartridge, the modified laser printer, and evaluation paper (GFC081 (Canon) A4: 81.4 g / m 2 ) was left standing in a high temperature and high humidity environment (32.5°C / 80% RH, hereinafter referred to as H / H environment) for 48 hours.

[0210] In a H / H environment, 20,000 images with a print ratio of 0.5% were printed continuously on evaluation paper.

[0211] The secondary transfer bias of the modified laser printer was set to a potential that was 200 V less than the normal potential, and a full solid image was output in a hand-held environment. The device was stopped during transfer from the intermediate transfer body to the paper, and the toner amount M1 (mg / cm) on the intermediate transfer body before the transfer process was measured. 2 ) and the amount of toner on the intermediate transfer body after the transfer process M2 (mg / cm 2 From the obtained toner amount, the transfer efficiency (%) was calculated as [(M1-M2) / M1] x 100.

[0212] The transferability was evaluated according to the following evaluation criteria. The better the transferability, the better the transfer efficiency. This makes it possible to faithfully transfer the toner image on the drum onto paper, resulting in a high-quality image.

[0213] (Evaluation criteria for transferability) A: Shows a transfer efficiency of 95% or more. B: Shows a transfer efficiency of 90% or more. C: Shows a transfer efficiency of 85% or more. D: Shows transfer efficiency of less than 85%.

[0214] <5> Charge Stability Using the LBP-712Ci printer, 5,000 images with a printing rate of 1% were printed out in a high-temperature, high-humidity environment (temperature 32.5°C, humidity 80%RH). After leaving the printer for 3 days, one image with a white background was printed out. The reflectance of the resulting image was measured using a reflection densitometer (Reflectometer Model TC-6DS, manufactured by Tokyo Denshoku Co., Ltd.). An amber filter was used for the measurement.

[0215] The worst value Ds (%) of the reflectance of the white background and Dr (%) of the reflectance of the transfer material before image formation were taken as Dr-Ds, and the fogging was evaluated according to the following criteria.

[0216] [Evaluation criteria] A: Fog is less than 1.0% B: Fog is 1.0% or more and less than 3.0% C: Fog is 3.0% or more and less than 5.0% D: Fog is 5.0% or more

[0217] [Table 4]

Claims

1. A toner having toner particles containing a binder resin, The binder resin contains a unit (a) represented by the following formula (1) and a unit (b) represented by the following formula (2): 【Chemistry 1】 (In formula (1), R 1 represents a hydrogen atom or a methyl group, L 1 represents a single bond or a divalent linking group, and m represents an integer of 15 or more and 35 or less. 【Chemistry 2】 (In formula (2), R 2 represents a hydrogen atom or a methyl group. In surface measurement of the toner particles by time-of-flight secondary ion mass spectrometry TOF-SIMS, the following partial structure (a-1) of the unit (a) is obtained with respect to the total ion count at a mass-to-charge ratio of 0.5 to 1850: 【Transformation 3】 ((a-1), L 1 and m are the same as in formula (1) above. When the ion count derived from the unit (b) is Ia1 and the ion count derived from the nitrile group of the unit (b) is Ib1, Ia1 and Ib1 can be expressed by the following formulas (3) and (4): Ia1≦0.0050 Formula (3) 0.100≦Ib1 Formula (4) Fulfilling The toner has a complex elastic modulus G at 70° C. * (70) is 3.0 × 10 4 Pa or more 5.0×10 6 The toner is characterized in that the viscosity is 0.01 Pa or less.

2. 2. The toner according to claim 1, wherein the toner particles satisfy the following formula (5) in time-of-flight secondary ion mass spectrometry TOF-SIMS: 0.150≦Ib1≦0.400 Formula (5)

3. In the elasticity measurement of the toner, the complex elastic modulus G * (100) is 1.0 x 10 3 3. The toner according to claim 1, wherein the viscosity is 100 Pa or more.

4. 3. The toner according to claim 1 or 2, wherein, in surface measurement of the toner particles by time-of-flight secondary ion mass spectrometry TOF-SIMS, when the ion count derived from the unit (a) of the toner particles relative to the total ion count at a mass-to-charge ratio of 0.5 to 1850 at a depth of 25 nm from the outermost surface of the toner particles normalized with polymethyl methacrylate resin is Ia2 and the ion count derived from the nitrile group of the unit (b) of the toner particles is Ib2, the following formulas (6) and (7) are satisfied: 20<Ib1 / Ia1<500 Formula (6) 0.10<(Ib2 / Ia2) / (Ib1 / Ia1)<3.00 Formula (7)

5. 3. The toner according to claim 1, wherein the binder resin contains the unit (a) represented by the formula (1) in an amount of 40.0% by mass or more and 80.0% by mass or less.

6. 3. The toner according to claim 1, wherein the unit (a) represented by the formula (1) in the binder resin is a unit represented by the following formula (8): 【Chemistry 4】 (In formula (8), R 1 represents a hydrogen atom or a methyl group, and m represents an integer of 15 or more and 35 or less.

7. 3. The toner according to claim 1, wherein, in a surface measurement of the toner particles by time-of-flight secondary ion mass spectrometry TOF-SIMS, when the ion count derived from sulfonic acid groups relative to the total ion count at a mass-to-charge ratio of 0.5 to 1850 is defined as Ic1, the Ic1 satisfies 0.005 or more and 0.050 or less.

8. A method for producing a toner having toner particles containing a binder resin, comprising: The method includes a step of forming particles of a polymerizable monomer composition containing a polymerizable monomer in an aqueous medium, and a polymerization step of polymerizing the polymerizable monomer contained in the particles with an oil-soluble polymerization initiator to obtain toner particles, the polymerizable monomer composition contains a first polymerizable monomer and a second polymerizable monomer different from the first polymerizable monomer; The first polymerizable monomer is represented by the following formula (A), and the second polymerizable monomer is represented by the following formula (B): a method for producing a toner, wherein in the polymerization step, a water-soluble polymerization initiator is added separately from the oil-soluble polymerization initiator when the polymerization conversion rate of the first polymerizable monomer is 30.0% by mass or more and the polymerization conversion rate of the second polymerizable monomer is 90.0% by mass or less. 【Transformation 5】 (In formula (A), R 1 represents a hydrogen atom or a methyl group, L 1 represents a single bond or a divalent linking group, and m represents an integer of 15 or more and 35 or less. 【Transformation 6】 (In formula (B), R 2 represents a hydrogen atom or a methyl group.

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