toner

Abstract

To provide a toner that is excellent in low temperature fixability and hot offset resistance.SOLUTION: A toner particle contains, as a resin component, a crystalline vinyl resin having a unit (a) represented by the formula (1). The resin component contains the unit (a) in an amount of 15.0 mass% or more and 40.0 mass% or less relative to the mass of the resin component. The content of the unit (a) in a component separated by gradient LC analysis of an acetonitrile / chloroform eluted component of chloroform soluble matter W of the toner particles and the storage elastic modulus at 100°C have specific relationships.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to toner.

Background Art

[0002] Conventionally, in electrophotographic apparatuses, energy saving has been considered a major technical issue, and significant reduction of the amount of heat applied to a fixing device has been studied. In toner, there is an increasing need for so-called "low-temperature fixability" that enables fixing at low energy.

[0003] As a method for enabling fixing at low temperature, Patent Document 1 describes a toner to which a plasticizer is added. The plasticizer has an effect of accelerating the softening rate of the binder resin while maintaining the glass transition temperature (Tg) of the toner, and can improve the low-temperature fixability. However, since the toner softens through the step of plasticizing the binder resin after the plasticizer melts, there is a limit to the melting rate of the toner, and further improvement in low-temperature fixability is desired.

[0004] Therefore, a method of using a crystalline resin as the binder resin has been studied. An amorphous resin generally used as a binder resin for toner does not show a distinct endothermic peak in differential scanning calorimetry (DSC) measurement, but when the toner contains a crystalline resin component, an endothermic peak (melting point) appears in the DSC measurement.

[0005] A crystalline resin has properties such that the molecular chains are regularly arranged and it hardly softens at temperatures lower than the melting point. Further, when the melting point is exceeded, the crystals rapidly melt, accompanied by a rapid decrease in viscosity. Such a crystalline resin excellent in sharp meltability has attracted attention as a material useful for improving the low-temperature fixability of toner.

[0006] Examples of the crystalline resin include toners using a crystalline vinyl resin having a long-chain alkyl group in the side chain within the molecule. Generally, the crystalline vinyl resin has a structure in which a long-chain alkyl group as a side chain is bonded to the main chain, and the long-chain alkyl groups in the side chains crystallize to form a crystalline resin.

[0007] Patent Document 2 describes a toner using a crystalline vinyl resin obtained by copolymerizing a polymerizable monomer having a long-chain alkyl group and an amorphous polymerizable monomer having a different SP value as a toner using a crystalline vinyl resin.

[0008] However, the crystalline vinyl resin has problems such as a tendency for the viscosity to decrease at high temperatures and a tendency for hot offset to occur. As a countermeasure, Patent Document 3 describes a toner in which, in addition to the crystalline vinyl resin, a domain matrix structure containing an amorphous resin is formed.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0010] However, it has been found that toners using a combination of a crystalline vinyl resin and an amorphous resin are likely to experience a decrease in gloss during fixing. During fixing, the crystalline vinyl resin melts and rapidly decreases in viscosity. On the other hand, the amorphous resin is not in a molten state or has a slow rate of viscosity decrease even when melted, resulting in relatively high-viscosity and low-viscosity portions inside the toner. As a result, hot offset is likely to occur, causing minute irregularities on the surface of the fixed image and a decrease in gloss. This phenomenon has been found to occur significantly in systems with low-temperature fixing and high-speed printing where differences in the molten state of each resin are likely to occur.

[0011] The present disclosure is directed to providing a toner excellent in low-temperature fixability and hot offset resistance.

Means for Solving the Problems

[0012] The present disclosure is a toner having toner particles containing a resin component, wherein the toner particles contain, as the resin component, a crystalline vinyl resin having a unit (a) represented by the following formula (1),

[0013]

Chemical formula

[0014] R in the formula (1) 1 represents a hydrogen atom or a methyl group, and n represents an integer of 15 to 35, the resin component contains the unit (a) in an amount of 15.0% by mass or more and 40.0% by mass or less based on the mass of the resin component, performing Soxhlet extraction of the toner particles using chloroform, removing components having a molecular weight of 2000 or less from the chloroform-soluble matter obtained by extraction for 18 hours by recycled HPLC, and using the resulting chloroform-soluble matter as chloroform-soluble matter W, Using acetonitrile as a poor solvent and chloroform as a good solvent with respect to the chloroform-soluble content W, linearly changing from a mobile phase of 100% by volume of acetonitrile to a mobile phase of 100% by volume of chloroform, when the eluted components were analyzed by gradient LC analysis, In a graph where the horizontal axis is the ratio (% by volume) of chloroform in the mobile phase and the vertical axis is the signal intensity (μA) of the eluted component detected using a charged particle detector, there are a plurality of maxima, Among the plurality of maxima, the maximum with the smaller ratio of chloroform in the mobile phase among the maximum with the largest intensity and the maximum with the second largest intensity is defined as maximum PA, The maximum with the larger ratio of chloroform in the mobile phase is defined as maximum PB, The minimum with the smallest intensity existing between the maximum PA and the maximum PB is defined as minimum BAB, The ratio of chloroform of the minimum BAB is VAB% by volume (where 20.0 < VAB < 95.0), The component with a ratio of chloroform in the mobile phase of 20.0% by volume or more and less than VAB% by volume is defined as component A, When the component with a ratio of chloroform in the mobile phase of VAB% by volume or more and 95.0% by volume or less is defined as component B, The resin component contains the component B in an amount of 40.0% by mass or more and 80.0% by mass or less based on the mass of the resin component, The content of the unit (a) in the chloroform-soluble content W is WC% by mass, When the content of the unit (a) in the component B is WB% by mass, WC and WB satisfy the following formula (2), WB / WC≧0.70 (2) When the storage elastic modulus of the toner particles at 100°C is G’(T) and the storage elastic modulus of the component B at 100°C is G’(B), G’(T) and G’(B) satisfy the following formulas (3) and (4), 5.0×10 3 Pa≦G’(T)≦1.0×10 5 Pa (3) 2.0×10 3 Pa ≤ G’(T) - G‘(B) ≤ 6.0×10 3 Pa (4) It relates to a toner characterized by the above.

Effect of the Invention

[0015] According to the present disclosure, a toner excellent in low-temperature fixability and hot offset resistance can be provided.

Mode for Carrying Out the Invention

[0016] In the present disclosure, the description of "XX or more and YY or less" or "XX to YY" representing a numerical range means a numerical range including the lower limit and the upper limit which are the endpoints, unless otherwise specified. When the numerical ranges are described stepwise, the upper and lower limits of each numerical range can be arbitrarily combined.

[0017] “(Meth)acrylate” means acrylate and / or methacrylate.

[0018] “Monomer unit” refers to the reacted form of the monomer substance in the polymer. For example, in the main chain where the polymerizable monomer in the polymer has polymerized, one section of the carbon-carbon bond is regarded as one unit. The polymerizable monomer can be represented by, for example, the following formula (C).

[0019]

Chemical Formula

[0020] In the above 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 a monovalent group.

[0021] “Crystalline resin” refers to a resin that shows a distinct endothermic peak in differential scanning calorimetry (DSC) measurement.

[0022] The inventors of the present invention have found that the above problems can be solved by appropriately controlling the viscoelasticity of the resin component containing a large amount of crystalline vinyl resin among the resin components in the toner particles and the viscoelasticity of the toner particles (the entire toner particles).

[0023] The toner according to the present disclosure is a toner having toner particles containing a resin component, wherein the toner particles contain, as the resin component, a crystalline vinyl resin having a unit (a) represented by the following formula (1),

[0024]

Chemical formula

[0025] R in the formula (1) 1 represents a hydrogen atom or a methyl group, and n represents an integer of 15 to 35, the resin component contains the unit (a) in an amount of 15.0% by mass or more and 40.0% by mass or less based on the mass of the resin component, the Soxhlet extraction of the toner particles is performed using chloroform, and the components having a molecular weight of 2000 or less are removed from the chloroform-soluble components obtained by extraction for 18 hours by recycled HPLC to obtain chloroform-soluble components W, when gradient LC analysis is performed on the eluted components using acetonitrile as a poor solvent and chloroform as a good solvent for the chloroform-soluble components W, and linearly changing from a mobile phase of 100% by volume of acetonitrile to a mobile phase of 100% by volume of chloroform, with the horizontal axis representing the ratio (volume%) of chloroform in the mobile phase, in a graph with the vertical axis representing the signal intensity (μA) of the eluted components detected using a charged particle detector, a plurality of maxima exist, among the plurality of maxima, the maximum value with the smaller ratio of chloroform in the mobile phase among the maximum value with the largest intensity and the maximum value with the second largest intensity is defined as the maximum value PA, The maximum value with a larger proportion of chloroform in the mobile phase is defined as the maximum value PB, and the minimum value with the lowest intensity existing between the maximum value PA and the maximum value PB is defined as the minimum value BAB. The proportion of chloroform in the minimum value BAB is VAB volume % (where 20.0 < VAB < 95.0). The component with a chloroform proportion in the mobile phase of 20.0 volume % or more and less than VAB volume % is defined as component A. When the component with a chloroform proportion in the mobile phase of VAB volume % or more and 95.0 volume % or less is defined as component B, the resin component contains 40.0 mass % or more and 80.0 mass % or less of the component B based on the mass of the resin component. The content of the unit (a) in the chloroform-soluble content W is WC mass %. When the content of the unit (a) in the component B is WB mass %, WC and WB satisfy the following formula (2). WB / WC ≧ 0.70 (2) The storage elastic modulus of the toner particles at 100 °C is G’(T). When the storage elastic modulus of the component B at 100 °C is G’(B), G’(T) and G’(B) satisfy the following formulas (3) and (4). 5.0×10 3 Pa ≦ G’(T) ≦ 1.0×10 5 Pa (3) 2.0×10 3 Pa ≦ G’(T) - G‘(B) ≦ 6.0×10 3 Pa (4) It is characterized by the above.

[0026] The toner according to the present disclosure is a toner having toner particles containing a resin component, and the toner particles contain, as the resin component, a crystalline vinyl resin having a unit (a) represented by the following formula (1).

[0027]

Chemical formula

[0028] In the above formula (1), R 1 represents a hydrogen atom or a methyl group, and n represents an integer of 15 to 35.

[0029] The unit (a) represents a unit having a long-chain alkyl group. By having the unit (a), a crystalline vinyl resin is obtained. When n in the formula (1) is 15 to 35, the crystallinity of the crystalline vinyl resin is likely to be exhibited. n is preferably an integer of 17 to 29.

[0030] The resin component according to the present disclosure contains the unit (a) in an amount of 15.0% by mass or more and 40.0% by mass or less based on the mass of the resin component. When the unit (a) is within the above range, the crystal amount of the toner becomes appropriate, and good low-temperature fixability is obtained. If it is less than 15.0% by mass, the crystal amount in the toner is small, so the low-temperature fixability deteriorates. If it is more than 40.0% by mass, the crystal amount in the toner (in the toner particles) becomes too large, and the melt viscosity of the toner during fixing becomes too low, resulting in a decrease in hot offset resistance. The preferable range of the unit (a) in the resin component is 20.0% by mass or more and 35.0% by mass or less.

[0031] Gradient LC analysis will be described. Gradient LC analysis is performed as follows unless otherwise specified.

[0032] As a sample, chloroform-soluble component W is used, which is obtained by removing components with a molecular weight of 2000 or less by recycled HPLC from the soluble components obtained by Soxhlet extraction of toner particles using a chloroform solvent for 18 hours. For the chloroform-soluble components extracted from the toner particles, acetonitrile is used as a poor solvent and chloroform is used as a good solvent, and the mobile phase composition is linearly changed from 100% by volume of acetonitrile to 100% by volume of chloroform. The eluted components when changed in this way are subjected to gradient LC analysis.

[0033] As a result, a graph is obtained with the horizontal axis being the proportion (volume %) of chloroform in the mobile phase and the vertical axis being the signal intensity (μA) of the eluted component detected using a charged particle detector. Acetonitrile is a highly polar solvent, and initially, components with high polarity are eluted. As the proportion of chloroform increases, components with lower polarity are gradually eluted. Therefore, in this analysis, separation according to the polarity in the chloroform-soluble component W can be achieved. In the toner according to the present disclosure, there are a plurality of maxima in the above analysis. Among the plurality of maxima, the maximum with the lowest intensity and the second-highest intensity, the maximum with the lower proportion of chloroform in the mobile phase, that is, the relatively higher-polarity maximum, is defined as maximum PA. Also, the maximum with the higher proportion of chloroform in the mobile phase, that is, the relatively lower-polarity maximum, is defined as maximum PB. Further, the minimum with the lowest intensity existing between the maximum PA and the maximum PB is defined as minimum BAB, and the proportion of chloroform at the minimum BAB is VAB volume % (where 20.0 < VAB < 95.0). Components with a chloroform proportion in the mobile phase of 20.0 volume % or more and less than VAB volume % are defined as component A, and components with a chloroform proportion in the mobile phase of VAB volume % or more and 95.0 volume % or less are defined as component B.

[0034] The resin component according to the present disclosure contains 40.0 mass % or more and 80.0 mass % or less of the component B based on the mass of the resin component. Also, when the content of the unit (a) in the chloroform-soluble component W is WC mass % and the content of the unit (a) in the component B is WB mass %, WC and WB satisfy the following formula (2).

[0035] WB / WC ≧ 0.70 (2) Since the unit (a) has a long-chain alkyl group, its polarity is relatively low. Therefore, satisfying the formula (2) means that component A and component B can be clearly separated, and it means that the unit (a) showing crystallinity in component B, that is, most of the crystalline vinyl resin, is present.

[0036] Also, the fact that the component B is contained in an amount of 40.0% by mass or more and 80.0% by mass or less based on the mass of the resin component means that an appropriate amount of the crystalline component is present, thereby obtaining good low-temperature fixability. If it is less than 40.0% by mass, the amount of the component exhibiting crystallinity becomes too small, so the low-temperature fixability deteriorates. If it is more than 80.0% by mass, the amount of the component exhibiting crystallinity becomes too large, so the hot offset resistance decreases. The preferable range of the component B in the resin component is 50.0% by mass or more and 75.0% by mass or less, and more preferably 55.0% by mass or more and 70.0% by mass or less. The content of the component B in the resin component can be adjusted by the content of the crystalline vinyl resin in the resin component, the content of the unit (a) of the crystalline vinyl resin, etc.

[0037] When the storage elastic modulus of the toner particles at 100 °C is G'(T), the toner according to the present disclosure satisfies the following formula (3).

[0038] 5.0×10 3 Pa ≦ G'(T) ≦ 1.0×10 5 Pa (3) The storage elastic modulus at 100 °C represents the viscosity after melting of the toner particles. Since G'(T) is within the above range, the penetration of the toner particles into the paper and the release from the fixing film can be effectively achieved, and the low-temperature fixability becomes good. If G'(T) is less than 5.0×10 3 Pa, the viscosity after melting of the toner particles is too small, so toner transfer to the fixing member (such as a fixing film) during fixing is likely to occur, and the hot offset resistance decreases. If it is more than 1.0×10 5 Pa, the viscosity after melting of the toner particles is too large, so the penetration of the toner particles into the paper during fixing is unlikely to occur, and the low-temperature fixability deteriorates. The preferable range of G'(T) is 8.0×10 3 Pa or more and 8.0×10 4 Pa or less, and more preferably 9.0×10 3 Pa or more and 5.0×10 4It is below Pa. G’(T) can be adjusted by the content of the unit (a) in the resin component in the toner particles, the molecular weight of the resin component, the content of component B, and the like.

[0039] Regarding the toner particles according to the present disclosure, when the storage elastic modulus of the component B at 100°C is defined as G’(B), the following formula (4) is satisfied.

[0040] 2.0×10 3 Pa ≦ G’(T) - G‘(B) ≦ 6.0×10 3 Pa (4) As described above, most of the unit (a) that exhibits crystallinity in the resin component is present in the component B. Therefore, the storage elastic modulus of the component B at 100°C is relatively lower than that of the toner particles. On the other hand, if there is a component in the toner particles with a large difference in the storage elastic modulus at 100°C, relatively high-viscosity and low-viscosity parts will occur inside the toner particles during fixing, resulting in minute irregularities on the surface of the fixed image and a decrease in gloss. This phenomenon occurs prominently in systems of low-temperature fixing and high-speed printing where differences in the molten state of each resin are likely to occur.

[0041] By satisfying the formula (4), the difference in the relative storage elastic modulus is within an appropriate range, so high gloss can be achieved even during high-speed low-temperature fixing.

[0042] If G’(T) - G‘(B) is smaller than 2.0×10 3 Pa, penetration into the paper during fixing becomes difficult, and the rub resistance of the fixed image decreases. If G’(T) - G‘(B) is larger than 6.0×10 3 Pa, the gloss during high-speed low-temperature fixing decreases.

[0043] G’(T) - G‘(B) can be adjusted by the content of the crystalline vinyl resin that occupies most of the component B, the ratio of the unit (a) in the crystalline vinyl resin, the molecular weight of the crystalline vinyl resin, and the like.

[0044] The component B according to the present disclosure will be described.

[0045] As described above, most of the crystalline vinyl resin is present in Component B.

[0046] Component B preferably contains 25.0% by mass or more and 50.0% by mass or less of the unit (a) based on the mass of Component B. By being within this range, it becomes easier to make the content of the unit (a) in the toner particles fall within an appropriate range, and it becomes easier to balance low-temperature fixability and hot offset resistance. Preferably, it is 30.0% by mass or more and 45.0% by mass or less.

[0047] Component B preferably has a weight average molecular weight (Mw) of the tetrahydrofuran (THF) soluble component measured by gel permeation chromatography (GPC) of 30,000 or more and 200,000 or less. By Mw being within this range, it becomes easier to make G’(T) - G‘(B) fall within an appropriate range. The preferable range of Mw is 40,000 or more and 180,000 or less, and more preferably 60,000 or more and 150,000 or less.

[0048] The crystalline vinyl resin according to the present disclosure will be described.

[0049] As described above, the crystalline vinyl resin is a component in which most of it is present in Component B.

[0050] The crystalline vinyl resin contains the unit (a). As a method for introducing the unit (a), for example, there is a method of polymerizing the following (meth)acrylic acid esters. For example, stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, cerinyl (meth)acrylate, octacosyl (meth)acrylate, myricyl (meth)acrylate, dotriacontyl (meth)acrylate, 2-decyltetradecyl (meth)acrylate, and the like can be mentioned.

[0051] The crystalline vinyl resin may contain only one kind of the unit (a) or may contain two or more kinds of the unit (a).

[0052] The content ratio of the unit (a) in the crystalline vinyl resin is preferably 40.0% by mass or more and 90.0% by mass or less, more preferably 45.0% by mass or more and 85.0% by mass or less, and still more preferably 50.0% by mass or more and 80.0% by mass or less. When it is within this range, the balance between low-temperature fixability and hot offset resistance is excellent.

[0053] In addition to the unit (a), the crystalline vinyl resin may have other units. As a method for introducing other units into the crystalline vinyl resin, for example, there is a method of polymerizing the (meth)acrylic acid ester and another vinyl monomer.

[0054] Examples of other vinyl monomers include the following.

[0055] Styrene, α-methylstyrene, (meth)acrylic acid methyl esters such as (meth)acrylic acid methyl, (meth)acrylic acid ethyl, (meth)acrylic acid -n-butyl, (meth)acrylic acid -t-butyl, (meth)acrylic acid -2-ethylhexyl.

[0056] Monomers having a urea group: for example, amines having 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, cyclohexylamine, etc.] and ethylenically unsaturated isocyanates having 2 to 30 carbon atoms reacted by a known method, and the like.

[0057] Monomers having a carboxy group; for example, methacrylic acid, acrylic acid, (meth)acrylic acid -2-carboxyethyl.

[0058] Monomers having a hydroxy group; for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.

[0059] Monomers having an amide group; for example, acrylamide, monomers obtained by reacting an amine having 1 to 30 carbon atoms with a carboxylic acid having 2 to 30 carbon atoms having an ethylenically unsaturated bond (such as acrylic acid and methacrylic acid) by a known method.

[0060] Monomers having a lactam structure; N-vinyl-2-pyrrolidone.

[0061] Among these, monomers having a lactam structure are preferred, monomers having a 5-membered lactam structure are preferred, and N-vinyl-2-pyrrolidone is more preferred. By containing units having a lactam structure, the affinity between the crystalline vinyl resin and paper is improved, and the rubbing resistance of the fixed image is easily improved.

[0062] The content ratio of the unit having a lactam structure in the crystalline vinyl resin is preferably 2.0% by mass or more and 15.0% by mass or less.

[0063] For the crystalline vinyl resin, after synthesizing a crystalline vinyl resin by copolymerizing a (meth)acrylate ester for introducing the unit (a) and other vinyl monomers, it is also possible to further react other vinyl monomers by a hydrogen abstraction reaction. The hydrogen abstraction reaction is a reaction that generates radicals by abstracting hydrogen atoms bonded to carbon atoms, and other vinyl monomers can be further reacted from the generated radicals. Thereby, the unit (a) in the crystalline vinyl resin can form a more aggregated state in the molecule, and the crystallinity can be easily increased. Also, it becomes easier to satisfy the formula (4).

[0064] The crystalline vinyl resin preferably has a weight average molecular weight (Mw) of the tetrahydrofuran (THF) soluble content measured by gel permeation chromatography (GPC) of 30,000 or more and 200,000 or less. When Mw is within this range, it becomes easier to set G’(T) - G‘(B) within an appropriate range. The preferred range of Mw is 40,000 or more and 180,000 or less, more preferably 60,000 or more and 150,000 or less.

[0065] The content of the crystalline vinyl resin in the toner particles according to the present disclosure is preferably 30.0% by mass or more and 80.0% by mass or less based on the mass of the toner particles. By being within this range, an appropriate amount of the crystalline component of the toner particles is likely to be present, and it becomes easier to achieve both low-temperature fixability and hot offset resistance. More preferably, it is 40.0% by mass or more and 75.0% by mass or less, and still more preferably 50.0% by mass or more and 70.0% by mass or less.

[0066] The toner particles according to the present disclosure preferably have a melting point derived from the crystalline vinyl resin in differential scanning calorimetry (DSC) measurement of 50°C or more and 80°C or less. When the melting point derived from the crystalline vinyl resin is within the above range, it becomes easier to improve low-temperature fixability. The preferred range of the melting point is 55°C or more and 75°C or less, and the more preferred range is 57°C or more and 70°C or less.

[0067] Component A according to the present disclosure will be described.

[0068] Component A is a component with higher polarity than Component B. Since most of the crystalline vinyl resin is present in Component B, most of the other resin components are present in Component A. Examples of the other resin components include amorphous resins.

[0069] It is preferable that the resin component contains the component A in an amount of 10.0% by mass or more and 60.0% by mass or less based on the mass of the resin component. By being within the above range, an appropriate amount of the component having crystallinity of the toner particles is likely to exist, and it becomes easier to achieve both low-temperature fixability and hot offset resistance. More preferably, it is 15.0% by mass or more and 55.0% by mass or less, and still more preferably, it is 20.0% by mass or more and 50.0% by mass or less.

[0070] It is preferable that the component A has a weight average molecular weight (Mw) of the tetrahydrofuran (THF) soluble component measured by gel permeation chromatography (GPC) of 20,000 or more and 200,000 or less. More preferably, it is 25,000 or more and 150,000 or less.

[0071] Examples of the amorphous resin include vinyl resins, polyester resins, polyurethane resins, epoxy resins, etc., but vinyl resins and polyester resins are preferable.

[0072] When the amorphous resin is a vinyl resin, the vinyl monomers usable for the crystalline vinyl resin can be used. The (meth)acrylate ester for introducing the unit (a) can also be used as long as the amorphous resin does not exhibit crystallinity.

[0073] In addition, so-called crosslinking agents having a plurality of vinyl groups per monomer can also be used. Examples of the crosslinking agent include the following. Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis(4-(acryloxydiethoxy)phenyl)propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis(4-(methacryloxydiethoxy)phenyl)propane, 2,2'-bis(4-(methacryloxypolyethoxy)phenyl)propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether, 4,4'-divinylbiphenyl.

[0074] When the amorphous resin is a polyester resin, a polyester resin obtainable by the reaction of a polyvalent carboxylic acid having a valence of 2 or more and a polyhydric alcohol can be used.

[0075] Examples of the polyvalent carboxylic acid include the following. Dibasic acids such as succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, malonic acid, dodecenyl succinic acid, and anhydrides or lower alkyl esters thereof, 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 anhydrides or lower alkyl esters thereof. These may be used alone or in combination of two or more.

[0076] Examples of the polyhydric alcohol include the following. 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); 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. Further, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, etc. These may be used alone or in combination of two or more.

[0077] For the purpose of adjusting the acid value and 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 necessary.

[0078] As a method for producing the polyester resin, for example, the transesterification method or the direct polycondensation method can be used alone or in combination.

[0079] The resin component according to the present disclosure contains a chloroform-insoluble component, and the content of the chloroform-insoluble component is preferably 3.0% by mass or more and 15.0% by mass or less based on the mass of the resin component. By being within this range, it becomes easier to effectively impart elasticity to the toner, and it becomes easier to achieve both low-temperature fixability and hot offset resistance.

[0080] The toner particles according to the present disclosure may have a core-shell structure having core particles having a resin and a shell covering the core particles. From the viewpoint of charge stability, the resin forming the shell is preferably a vinyl resin or a polyester resin. More preferably, it is an amorphous polyester resin. The shell does not necessarily have to cover the entire core, and there may be a portion where the core is exposed. As the vinyl resin and polyester resin constituting the shell, the vinyl resin and polyester resin that can be used for the above-described component A and component B can be used.

[0081] The toner particles may contain wax. The wax is at least one selected from the group consisting of hydrocarbon waxes and ester waxes. By using a hydrocarbon wax and / or an ester wax, it becomes easier to ensure effective releasability.

[0082] Examples of the hydrocarbon wax include the following.

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

[0084] The ester wax only needs to have at least one ester bond in one molecule, and either natural ester wax or synthetic ester wax may be used.

[0085] Examples of the ester wax include the following.

[0086] 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 glyceryl 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 polyglyceryl behenate; natural ester waxes such as carnauba wax and rice wax; Among these, ester waxes that are esters of alcohols with 4 to 8 valences and aliphatic monocarboxylic acids, or ester waxes that are esters of carboxylic acids with 4 to 8 valences and aliphatic monoalcohols are preferred. When these waxes are included, the compatibility with the crystalline vinyl resin during fixing is reduced, making it easier to improve the releasability during low-temperature fixing and enhancing the low-temperature fixing property.

[0087] Also, esters of tetrahydric alcohols and monocarboxylic acids such as pentaerythritol tetrastearate, pentaerythritol tetrapalmitate, and pentaerythritol tetrabehenate, esters of hexahydric alcohols and monocarboxylic acids such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate, and dipentaerythritol hexabehenate, and esters of octahydric alcohols and monocarboxylic acids such as tripentaerythritol octastearate, tripentaerythritol octapalmitate, and tripentaerythritol octabehenate are more preferred.

[0088] The wax content in the toner particles is preferably 1.0% by mass or more and 30.0% by mass or less, more preferably 2.0% by mass or more and 25.0% by mass or less. When the wax content in the toner particles is within the above range, the releasability during fixing is easily ensured.

[0089] The melting point of the wax is preferably 60°C or more and 120°C or less. When the melting point of the wax is within the above range, it easily melts during fixing and oozes out onto the surface of the toner particles, and the wax is easily exerted. More preferably, it is 70°C or more and 100°C or less.

[0090] The toner particles 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 conventionally used in toners may also be used.

[0091] Examples of the colorant for yellow include the following. Condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, allylamide compounds. Among these, C.I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, 180 are preferably used.

[0092] Examples of the colorant for magenta include the following. Condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds. Among these, C.I. 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, 254 are preferably used.

[0093] Examples of cyan colorants include the following: copper phthalocyanine compounds and their derivatives, anthraquinone compounds, and basic dye lake compounds. Among these, C.I. Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and 66 are preferably used.

[0094] The colorant is selected in terms of hue angle, chroma, lightness, lightfastness, OHP transparency, and dispersibility in the toner.

[0095] The content of the colorant in the toner particles is preferably 1.0 part by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the toner particles. When magnetic particles are used as the colorant, the content is preferably 40.0 parts by mass or more and 150.0 parts by mass or less with respect to 100.0 parts by mass of the toner particles.

[0096] The toner particles may contain a charge control agent. Alternatively, the charge control agent may be externally added to the toner particles. By using a charge control agent, the charge characteristics can be stabilized and the optimum triboelectric charge amount can be controlled according to the development system.

[0097] As the charge control agent, a charge control agent with a fast charging speed and the ability to stably maintain a certain charge amount is preferred.

[0098] Examples of charge control agents for controlling the toner to be negatively chargeable include the following: organometallic compounds and chelate compounds are effective, and monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds are included.

[0099] Examples of charge control agents for controlling the toner to be positively chargeable include the following: nigrosine, quaternary ammonium salts, metal salts of higher fatty acids, diorganotin borates, guanidine compounds, and imidazole compounds.

[0100] The content of the charge control agent in the toner particles is preferably 0.01 part by mass or more and 20.0 parts by mass or less, more preferably 0.5 part by mass or more and 10.0 parts by mass or less with respect to 100.0 parts by mass of the toner particles.

[0101] The toner particles may be used as toner as they are, or may be used as toner by mixing external additives or the like and attaching them to the surface of the toner particles if necessary.

[0102] Examples of the external additive include inorganic fine particles selected from the group consisting of silica fine particles, alumina fine particles, and titania fine particles, or composite oxides thereof. Examples of the composite oxide include silica-aluminum fine particles and strontium titanate fine particles.

[0103] The content of the external additive is preferably 0.01 part by mass or more and 8.0 parts by mass or less, more preferably 0.1 part by mass or more and 4.0 parts by mass or less with respect to 100 parts by mass of the toner particles.

[0104] The toner particles according to the present disclosure can be manufactured by methods such as a suspension polymerization method, an emulsion aggregation method, a dissolution suspension method, and a pulverization method. It is preferable to manufacture by the suspension polymerization method.

[0105] The suspension polymerization method will be described in detail.

[0106] For example, a synthetic crystalline vinyl resin is added to a mixture of each polymerizable monomer. If necessary, other materials such as a colorant, a wax, and a charge control agent are added and uniformly dissolved or dispersed to prepare a polymerizable monomer composition.

[0107] Thereafter, the polymerizable monomer composition is dispersed in an aqueous medium using a stirrer or the like to prepare suspension particles of the polymerizable monomer composition. Thereafter, the polymerizable monomer contained in the particles is polymerized by an initiator or the like to obtain toner particles. By utilizing a hydrogen abstraction reaction during this polymerization reaction, a certain amount of each polymerizable monomer reacts with the previously polymerized crystalline vinyl resin, making it easier to control the crystalline vinyl resin to desired physical properties.

[0108] After the completion of the polymerization, the toner particles are filtered, washed, and dried, and an external additive is added as necessary to obtain toner.

[0109] Examples of the polymerization initiator include azo-based or diazo-based 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; peroxide-based polymerization initiators such as benzoyl peroxide, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxy octoate, t-butyl peroxy neodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide. A peroxide-based polymerization initiator, which easily causes a hydrogen abstraction reaction, is preferably used. Among these, initiators such as t-butyl peroxy 2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxy octoate, and t-butyl peroxy neodecanoate are more preferably used.

[0110] The temperature of the polymerization reaction is preferably 15°C or higher and 25°C or lower with respect to the 10-hour half-life temperature of the initiator. Within this range, the hydrogen abstraction reaction occurs moderately, and it becomes easier to control the crystalline vinyl resin to the desired physical properties.

[0111] Also, a chain transfer agent and / or a polymerization inhibitor may be used.

[0112] The aqueous medium may contain an inorganic and / or organic dispersion stabilizer.

[0113] 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.

[0114] Examples of organic dispersion stabilizers include polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium carboxymethylcellulose, polyacrylic acid and its salts, and starch.

[0115] When using an inorganic compound as the dispersion stabilizer, a commercially available product may be used as it is, or the inorganic compound may be generated in an aqueous medium for use in order to obtain finer particles.

[0116] For example, in the case of calcium phosphate such as hydroxyapatite or tricalcium phosphate, it is advisable to mix an aqueous phosphate solution and an aqueous calcium salt solution under high agitation.

[0117] The aqueous medium may contain a surfactant. Examples of surfactants include anionic surfactants such as sodium dodecylbenzenesulfate and sodium oleate; cationic surfactants; amphoteric surfactants; and nonionic surfactants.

[0118] The calculation methods and measurement methods for various physical properties of the toner and toner materials will be described below.

[0119] <Separation of toner particles from toner> By the following method, the toner particles obtained by separating the toner particles and the external additive can be used for each analysis.

[0120] Add 160 g of sucrose (manufactured by Kinoshita Chemical Co., Ltd.) to 100 mL of ion-exchanged water and dissolve it while stirring with hot water to prepare a sucrose aqueous solution. Put 31 g of the sucrose aqueous solution and 6 mL of Contaminon N (a 10% by mass aqueous solution of a neutral detergent for precision measuring instrument cleaning with pH 7, composed of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Fujifilm Wako Pure Chemical Corporation) into a centrifuge tube to prepare a dispersion. Add 1 g of toner to this dispersion and loosen the toner clumps with a spatula or the like.

[0121] Set the centrifuge tube on "KM Shaker" (model: V.SX) manufactured by Iwaki Sangyo Co., Ltd. and shake it for 20 minutes under the condition of 350 reciprocations per minute. After shaking, transfer the solution to a glass tube (50 mL) for a swinging rotor and centrifuge it at 3500 rpm for 30 minutes using a centrifuge.

[0122] In the glass tube after centrifugation, toner particles exist in the uppermost layer, and external additives such as silica fine particles exist on the aqueous solution side of the lower layer. Collect the toner particles in the upper layer, filter them, wash them with running water using 2 L of ion-exchanged water warmed to 40°C, and take out the washed toner particles.

[0123] <Separation and Measurement of the Content Ratio of Chloroform-Insoluble Components in Component A, Component B, and Resin from Toner Particles> Precisely weigh 1.5 g of toner particles (W1 [g]) and put them into a pre-precise weighed cylindrical filter paper (product name: No. 86R, size 28×100 mm, manufactured by Advantec Toyo Co., Ltd.) and set it in a Soxhlet extractor. Extract with 200 mL of chloroform as a solvent for 18 hours, and perform the extraction at a reflux rate such that the extraction cycle of the solvent is about once every 5 minutes.

[0124] After extraction is completed, take out the cylindrical filter paper, air-dry it, and then vacuum-dry it at 40 °C for 8 hours. Weigh the mass of the cylindrical filter paper containing the extraction residue, and subtract the mass of the cylindrical filter paper to calculate the mass (W3 [g]) of the extraction residue (chloroform-insoluble matter). Also, when recovering the chloroform-soluble matter (W2 [g]), it can be recovered by sufficiently distilling off the chloroform from the soluble matter in chloroform using an evaporator.

[0125] Next, determine the content (W4 [g]) of the resin component in the chloroform-insoluble matter by the following procedure.

[0126] Precisely weigh (Wa’ [g]) 2 g of the chloroform-insoluble matter of toner particles into a pre-weighed 30 mL magnetic crucible.

[0127] Place the magnetic crucible in an electric furnace, heat it at approximately 900 °C for 3 hours, let it cool in the electric furnace, then let it cool in a desiccator at room temperature for 1 hour or more, weigh the mass of the crucible containing the calcined residual ash, and subtract the mass of the crucible to calculate the calcined residual ash (Wb’ [g]).

[0128] Then, calculate the mass (W5 [g]) of the calcined residual ash in the sample W1 [g] using the following formula.

[0129] W5 = W1 × (Wb’ / Wa’) Next, calculate the mass (W4 [g]) of resin C, which is the resin component excluding the calcined residual ash in the chloroform-insoluble matter of the toner particles, using the following formula.

[0130] W4 = W1 - W5 In addition, when the toner particles contain wax, it is necessary to separate the resin and the wax. The separation of the resin and the wax is carried out by recycling HPLC, considering components with a molecular weight of 2000 or less as wax and separating them. The measurement method is shown below. First, the chloroform-soluble component is separated by the method described above and dissolved in chloroform. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Microlidisk" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. Note that the sample solution is adjusted so that the concentration of the components soluble in chloroform is 1.0% by mass. Using this sample solution, measurements are carried out under the following conditions.

[0131] · Apparatus: LC-Sakura NEXT (manufactured by Nippon Analytical Industry Co., Ltd.) · Column: JAIGEL2H, 4H (manufactured by Nippon Analytical Industry Co., Ltd.) · Eluent: Chloroform · Flow rate: 10.0 mL / min · Oven temperature: 40.0 °C · Sample injection volume: 1.0 mL When calculating the molecular weight of the sample, a molecular weight calibration curve prepared using a standard polystyrene resin (for example, trade names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation) is used.

[0132] From the molecular weight curve thus obtained, the components with a molecular weight of 2000 or less are repeatedly fractionated to separate the resin component (W) and the wax component (Wd) in the chloroform-soluble component of the toner. Then, the content (W6 [g]) of the resin component in the chloroform-soluble component (W2) in the toner particles W1 [g] is calculated by the following formula.

[0133] W2 = W1 - W3 W6 = W2 × (Wc / (W + Wd)) × W1 × 0.01 The separation of component A and component B from the toner particles uses the resin component (W) in the chloroform-soluble portion of the toner particles described above as a sample. The sample was adjusted with chloroform so that the sample concentration was 1.0% by mass, and the solution filtered through a 0.45 μm PTFE filter was used for measurement. The gradient polymer LC measurement conditions are shown below.

[0134] Apparatus: UlTIMATE3000 (manufactured by Thermo Fisher Scientific) Mobile phase: A Chloroform (HPLC), B Acetonitrile (HPLC) Gradient: 2 minutes (A / B = 0 / 100) → 25 minutes (A / B = 100 / 0) (Note that the gradient of the change in the mobile phase was made linear) Flow rate: 1.0 mL / min Injection: 1.0% by mass × 20 μL Column: Tosoh TSKgel ODS (diameter 4.6 mm × length 150 mm × 5 μm) Column temperature: 40 °C Detector: Corona charged particle detector (Corona-CAD) (manufactured by Thermo Fisher Scientific) Regarding the graph of time-signal intensity (μA) obtained in the measurement, the time is converted to the proportion of chloroform (volume %). Then, among the observed maxima, the maximum with the largest signal intensity and the second largest maximum are selected. Among these two maxima, the maximum with the smaller proportion of chloroform in the mobile phase is designated as PA, and the maximum with the larger proportion of chloroform in the mobile phase is designated as PB. Furthermore, the minimum with the smallest intensity existing between PA and PB is designated as BAB, and the proportion of chloroform of BAB is designated as VAB (volume %).

[0135] Thereafter, the above measurement is repeated 50 times. Then, the region where the ratio of the mobile phase is 20.0% by volume or more and less than VAB% by volume is fractionated as the acetonitrile / chloroform solution of component A, and the region where the ratio is VAB% by volume or more and 95.0% or less is fractionated as the acetonitrile / chloroform solution of component B. By sufficiently distilling off the acetonitrile / chloroform with an evaporator, component A (We [g]) and component B (Wf [g]) are taken out respectively.

[0136] Then, the content (W7 [g]) of component A and the content (W8 [g]) of component B in the chloroform-soluble component (W2) in the toner particles W1 [g] are calculated respectively by the following formula.

[0137] W7 = W6 × We / (1.484 × 1.0 × 0.01 × 20 × 0.001 × 50) W8 = W7 × Wf / (1.484 × 1.0 × 0.01 × 20 × 0.001 × 50) The content ratio (W9 [mass%]) of component A, the content ratio (W10 [mass%]) of component B, and the content ratio (W11 [mass%]) of the chloroform-insoluble component of the resin component in the present disclosure are calculated by the following formula.

[0138] W9 = W7 / (W6 + W4) W10 = W8 / (W6 + W4) W11 = W4 / (W6 + W4) <Measurement Method of Resin Component, Chloroform-Soluble Component W, and Content Ratio of Unit (a) in Component B> The measurement of the resin component, the chloroform-soluble component W, and the content ratio of the unit (a) in component B is 1 performed by 1H-NMR under the following conditions.

[0139] Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measuring frequency: 400 MHz Pulse condition: 5.0 μs Frequency range: 10500 Hz Number of integrations: 64 times Measuring temperature: 30 °C Sample: Prepared as follows Place 50 mg of the measurement sample into 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 to prepare the sample.

[0140] The obtained 1 Analyze the 1H-NMR chart to identify the structure of each unit. Here, as an example, the measurement of the content ratio of unit (a) in component B will be described. The obtained 1 In the 1H-NMR chart, select a peak independent of the peaks attributed to the components of other units from among the peaks attributed to the components of unit (a), and calculate the integral value S1 of this peak. Similarly, calculate the integral value for each of the other units contained in the resin.

[0141] When the units constituting component B are unit (a) and one other unit, the content ratio of unit (a) is determined as follows using the integral value S1 and the integral value S2 of the peak of the other unit. Here, n1 and n2 are the number of hydrogens in the components to which the peaks focused on for each site are attributed.

[0142] Content ratio of unit (a) (mol%) = {(S1 / n1) / ((S1 / n1)+(S2 / n2))}×100 Even when there are two or more other units, the content ratio of unit (a) can be calculated in the same manner (using S3···Sx, n3···nx).

[0143] When a monomer containing no hydrogen atom in the components other than the vinyl group is used, 13 Use 13C-NMR to measure the nuclei 13 as 13C and perform the measurement in single pulse mode, 1 and it can be calculated in the same manner as with 1H-NMR. Multiply the ratio (mol%) of each unit calculated by the above method by the molecular weight of each unit to convert the content ratio of each unit to mass%.

[0144] <Measurement of Storage Elastic Modulus of Toner Particles and Component B at 100 °C> The measurement of the storage elastic modulus was carried out using an MCR302 (manufactured by Anton Paar). The method for measuring the storage elastic modulus of toner particles at 100 °C is shown below.

[0145] 120 mg of toner particles were weighed and molded at 20 kN for 1 minute using a tablet molding machine to obtain a disk-shaped sample with a diameter of 8 mm.

[0146] Using the obtained sample, the sample was set on the measurement jig under the following conditions.

[0147] Name of measurement jig: Measuringplate PP08 / SD:8mm sandblasted Setting conditions: 80 °C 0.1 N Next, viscoelasticity measurement was carried out under the following conditions.

[0148] Frequency: 1 Hz Normal force: 100 mN Applied strain: Changing from 0.5% to 7.0% at 0.22% / min The temperature was raised from 70 °C to 130 °C at 2 °C / min and measured for 30 minutes. The sampling pitch at this time was 1 point / 0.5 min.

[0149] In the above measurement, the value of the storage elastic modulus (Pa) at 100 °C calculated was taken as the storage elastic modulus G’(T) of the toner particles at 100 °C. Similarly, the value of the storage elastic modulus at 100 °C when component B was used as the sample was taken as the storage elastic modulus G’(B).

[0150] <Method for Measuring Molecular Weight (Weight-Average Molecular Weight Mw) of Component B> The molecular weight (weight-average molecular weight Mw) of the THF-soluble fraction of component B is measured by gel permeation chromatography (GPC) as follows.

[0151] First, at room temperature over 24 hours, dissolve Component B in tetrahydrofuran (THF). Filter the resulting solution through a solvent-resistant membrane filter "Micron Disc" with a pore size of 0.2 μm (manufactured by Tosoh Corporation) to obtain a sample solution. Note that the sample solution is adjusted so that the concentration of the components soluble in THF is 0.8% by mass. Measure under the following conditions using this sample solution.

[0152] · Apparatus: HLC8120 GPC (Detector: RI) (manufactured by Tosoh Corporation) · Column: 7-connected Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Resonac Co., Ltd.) · Eluent: Tetrahydrofuran (THF) · Flow rate: 1.0 mL / min · Oven temperature: 40.0 °C · Sample injection volume: 0.10 mL When calculating the molecular weight (weight average molecular weight Mw) of the sample, use the molecular weight calibration curve prepared using a standard polystyrene resin (for example, trade names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation).

Example

[0153] Hereinafter, it will be specifically described by way of examples. In the following formulations, "parts" are "parts by mass" on a mass basis unless otherwise specified.

[0154] (Preparation of Resin A1) Add the following materials into an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device.

[0155] · Terephthalic acid 25.3 parts · Bisphenol A-propylene oxide 2-mol adduct 74.7 parts · Potassium titanium oxalate (catalyst) 0.02 parts Subsequently, under a nitrogen atmosphere, the reaction was carried out at 220 °C for 5 hours under normal pressure and at 220 °C for 3 hours under reduced pressure. After cooling, it was pulverized to obtain Resin A1. The weight-average molecular weight (Mw) of Resin A1 was 10,280.

[0156] (Preparation of Resin A2) 50.0 parts of xylene was charged into an autoclave, replaced with nitrogen, and then heated to 185 °C with stirring under a sealed state. Here, a mixed solution of 79.0 parts of styrene, 17.0 parts of n-butyl acrylate, 3.1 parts of divinylbenzene, 0.9 part of acrylic acid, 1.0 part of di-tert-butyl peroxide and 20.0 parts of xylene was continuously dropped and polymerized over 3 hours while controlling the temperature inside the autoclave at 185 °C. Further, it was kept at the same temperature for 1 hour to complete the polymerization, and the solvent was removed to obtain Resin A2. The weight-average molecular weight (Mw) of Resin A2 was 60,000.

[0157] (Preparation of Resin B1) Under a nitrogen atmosphere, the following materials were charged into a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube.

[0158] · 100.0 parts of toluene · 100.0 parts of monomer composition (The monomer composition is a mixture of the following monomers in the following proportions) · 60.0 parts of behenyl acrylate · 20.0 parts of styrene · 10.0 parts of methacrylonitrile · 10.0 parts of N-vinyl-2-pyrrolidone · 0.5 part by mass of polymerization initiator t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) While stirring the above materials in a reaction vessel at 200 rpm, heat to 70 °C and carry out a polymerization reaction for 12 hours to obtain a solution in which the polymer in the monomer composition is dissolved in toluene. Subsequently, after cooling the solution to 25 °C, the solution was poured into 1000.0 parts of methanol while stirring to precipitate the methanol-insoluble matter. The obtained methanol-insoluble matter was separated by filtration, further washed with methanol, and then vacuum dried at 40 °C for 24 hours to obtain Resin B1. The physical properties of Resin B1 are shown in Table 1.

[0159] (Preparation of Resins B2 - B6) In the preparation of Resin B1, crystalline Resins B2 - B6 were prepared in the same manner except that the addition amount of the monomer composition was changed as shown in Table 1. The physical properties of Resins B2 - B6 are shown in Table 1.

[0160]

Table 1

[0161] <Example 1> [Manufacture of Toner by Suspension Polymerization Method] (Manufacture of Toner Particles 1) A mixture of the following materials was prepared.

[0162] · Styrene 45.0 parts · n-Butyl acrylate 15.0 parts · Pigment Blue 15:3 (colorant) 6.5 parts The above mixture was put into an attritor (manufactured by Nippon Coke & Engineering Co., Ltd.) and dispersed at 200 rpm for 2 hours using zirconia beads with a diameter of 5 mm to obtain a raw material dispersion.

[0163] To a container equipped with a high-speed stirring device, a homomixer (manufactured by Primix Corporation), and a thermometer, 735.0 parts of ion-exchanged water and 16.0 parts of trisodium phosphate (dodecahydrate) were added, 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, thereby obtaining an aqueous medium in which an inorganic dispersion stabilizer containing hydroxyapatite was dispersed in water.

[0164] Subsequently, the raw material dispersion was transferred to a container equipped with a stirring device and a thermometer, and the temperature was raised to 60°C while stirring at 100 rpm. Then, the following materials · 4.0 parts of Resin A1 · 35.0 parts of Resin B1 · 9.0 parts of DP18 (dipentaerythritol stearate wax, melting point 79°C, manufactured by Nisshin Oillio Group, Ltd.) · 0.1 part of HDDA (hexanediol diacrylate) were added, and the mixture was stirred at 100 rpm for 30 minutes while maintaining the temperature at 60°C. Then, 8.0 parts of t-butyl peroxy pivalate (manufactured by NOF Corporation: Perbutyl PV) as a polymerization initiator was added, and the mixture was stirred for another 1 minute. Thereafter, it was added to the aqueous medium being stirred at 12,000 rpm by the high-speed stirring device. Stirring was continued at 12,000 rpm for 20 minutes by the high-speed stirring device while maintaining the temperature at 60°C to obtain a granulation liquid.

[0165] 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 76°C while stirring at 150 rpm under a nitrogen atmosphere. A polymerization reaction was carried out at 150 rpm for 6 hours while maintaining the temperature at 76°C to obtain a toner particle dispersion.

[0166] The obtained 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. Thereafter, while maintaining the stirring, dilute hydrochloric acid was added until the pH reached 1.5 to dissolve the dispersion stabilizer. The solid content was filtered off, thoroughly washed with ion-exchanged water, and then vacuum-dried at 30°C for 24 hours to obtain toner particles 1.

[0167] (Preparation of Toner 1) To 98.0 parts of the toner particles 1, 2.0 parts of silica fine particles (hydrophobically treated with hexamethyldisilazane, number average particle diameter of primary particles: 10 nm, BET specific surface area: 170 m 2 / g) were added, and using a Henschel mixer (manufactured by Nippon Coke & Engineering Co., Ltd.), they were mixed at 3000 rpm for 15 minutes to obtain toner 1. The physical properties, etc. of the obtained toner 1 are shown in Table 3.

[0168] <Examples 2 to 23> In Example 1, except that the types and amounts of polymerizable monomers used, the amount of polymerization initiator added, the types and amounts of release agents, other additives, reaction temperature, and reaction time were changed as shown in Table 2, toner particles 2 to 23 were obtained in the same manner.

[0169] Furthermore, external addition was performed in the same manner as in Example 1 to obtain toners 2 to 23. The physical properties of the toners are shown in Table 3.

[0170] <Comparative Examples 1 to 6> In Example 1, except that the types and amounts of polymerizable monomers used, the amount of polymerization initiator added, the types and amounts of release agents, other additives, reaction temperature, and reaction time were changed as shown in Table 2, comparative toner particles 1 to 6 were obtained in the same manner.

[0171] Furthermore, external addition was performed in the same manner as in Example 1 to obtain comparative toners 1 to 6. The physical properties of the toners are shown in Table 3.

[0172] <Comparative Example 7> (Manufacture of Comparative Toner Particles 7) A mixture consisting of the following materials was prepared.

[0173] · 30.0 parts of methyl methacrylonitrile · 13.0 parts of styrene · 7.0 parts of ethyl methacrylate · 1.0 part of aluminum di-t-butyl salicylate · 6.5 parts of colorant Pigment Blue 15:3 The above mixture was put into an attritor (manufactured by Nippon Coke & Engineering Co., Ltd.), and using zirconia beads with a diameter of 5 mm, it was dispersed at 200 rpm for 2 hours to obtain a raw material dispersion. On the other hand, 735.0 parts of ion-exchanged water and 16.0 parts of trisodium phosphate (dodecahydrate) were added to a container equipped with a high-speed stirring device homomixer (manufactured by Primix Corporation) and a thermometer, and the temperature was raised to 60 °C while stirring at 12,000 rpm. Then, an aqueous calcium chloride solution in which 9.0 parts of calcium chloride (dihydrate) was dissolved in 65.0 parts of ion-exchanged water was added, and it was stirred at 12,000 rpm for 30 minutes while maintaining 60 °C. Then, 10% hydrochloric acid was added 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.

[0174] Subsequently, the raw material dispersion was transferred to a container equipped with a stirring device and a thermometer, and the temperature was raised to 60 °C while stirring at 100 rpm. Then, the following materials · 50.0 parts of behenyl acrylate · 10.0 parts of DP18 were added and stirred at 100 rpm for 30 minutes while maintaining 60 °C. Then, 7.0 parts of t-butyl peroxy pivalate (manufactured by NOF Corporation: Perbutyl PV) and 1.0 part of t-butyl peroxyisobutyrate (manufactured by Arkema Kishimoto Co., Ltd.: L80) were added as polymerization initiators and stirred for another 1 minute. Then, it was put into the aqueous medium being stirred at 12,000 rpm by the above high-speed stirring device. Stirring was continued at 12,000 rpm for 20 minutes by the above high-speed stirring device while maintaining 60 °C to obtain a granulation liquid.

[0175] Transfer the granulation liquid to a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube. While stirring at 150 rpm under a nitrogen atmosphere, heat the mixture to 70°C and carry out the first-stage polymerization reaction at 150 rpm for 5 hours. Then, heat the mixture to 90°C and carry out the second-stage polymerization reaction at 90°C for 5 hours to obtain a toner particle dispersion liquid.

[0176] After cooling the obtained toner particle dispersion liquid to 45°C while stirring at 150 rpm, heat treatment was carried out for 5 hours while maintaining the temperature at 45°C. Then, while maintaining stirring, dilute hydrochloric acid was added until the pH reached 1.5 to dissolve the dispersion stabilizer. The solid content was filtered off, washed thoroughly with ion-exchanged water, and then vacuum dried at 30°C for 24 hours to obtain comparative toner particles 7. Further, external addition was carried out in the same manner as in Example 1 to obtain comparative toner 7. The physical properties of the obtained comparative toner 7 are shown in Table 3.

[0177] <Comparative Example 8> (Production Example of Comparative Toner Particles 8) Mix the following materials, · 40 parts of Resin A2 · 60 parts of Resin B6 Supply the mixture to a twin-screw kneader (manufactured by Kurimoto Iron Works, S5KRC kneader) at a rate of 1 kg / h, and at the same time supply 4.0 parts of t-butylperoxyisopropyl monocarbonate as a radical reaction initiator at a rate of 0.1 kg / h. Kneading and extrusion were carried out at 160°C for 5 minutes at 100 rpm to carry out the reaction. Further, nitrogen was supplied from the vent port to carry out mixing while removing the organic solvent. By cooling the kneaded product obtained by kneading, comparative resin 8 was obtained. Measurement using gel permeation chromatography (GPC) confirmed that Resin A2 and Resin B6 had partially reacted and the weight average molecular weight had increased. The content of the reacted resin in comparative resin 8 was 5% by mass.

[0178] The following materials · 100 parts of Comparative Resin 8 · 5.0 parts of hydrocarbon wax (Fisher-Tropsch wax; DSC: peak temperature of the maximum endothermic peak 90°C) · 6.5 parts of C.I. Pigment Blue 15:3 Using a Henschel mixer (Model FM-75, manufactured by Nippon Coke & Engineering Co., Ltd.), the mixture was rotated at 20 s -1 for 5 minutes. Then, using a twin-screw kneader (Model PCM-30, manufactured by Ikegai Corporation), the mixture was kneaded at a screw rotation speed of 250 rpm and a discharge temperature of 130 °C with the temperature set at 130 °C. The obtained kneaded material was cooled and coarsely pulverized to 1 mm or less using a hammer mill to obtain a coarsely pulverized material. The obtained coarsely pulverized material was finely pulverized using a mechanical pulverizer (Model T-250, manufactured by Freund Turbo Co., Ltd.).

[0179] Furthermore, classification was performed using a Faculity F-300 (manufactured by Hosokawa Micron Corporation) to obtain comparative toner particles 8 with a weight average particle diameter of approximately 6.0 μm. The operating conditions were a classification rotor rotation speed of 130 s -1 and a dispersion rotor rotation speed of 120 s -1 .

[0180] The following materials · 100 parts of comparative toner particles 8 · 0.5 part of hydrophobized silica fine particles with a number average particle diameter of primary particles of 15 nm · 1.0 part of hydrophobized silica fine particles with a number average particle diameter of primary particles of 80 nm were mixed using a Henschel mixer Model FM-10C (manufactured by the Chemical Machinery Division of Nippon Coke & Engineering Co., Ltd.) at a rotation speed of 30 s -1 for 10 minutes to obtain comparative toner 8. The physical properties of the obtained comparative toner 8 are shown in Table 3.

[0181]

Table 2-1

[0182]

Table 2-2

[0183]

Table 3-1

[0184] [Table 3-2]

[0185] <Toner Evaluation Method> The following evaluations were performed on the toners of Examples 1 to 23 and Comparative Examples 1 to 8, respectively.

[0186] <1> Low-temperature Fixing Property A process cartridge filled with toner (a process cartridge for a laser beam printer (LBP-712Ci, manufactured by Canon Inc.)) was left standing at 25°C and a humidity of 40% RH for 48 hours. Using a modified machine that was modified based on the laser beam printer (LBP-712Ci, manufactured by Canon Inc.) so that it could operate even with the fuser removed, an unfixed image with an image pattern in which 9-point square images of 10 mm × 10 mm were evenly arranged over the entire transfer paper was output. The toner loading on the transfer paper was set to 0.80 mg / cm 2 and the fixing start temperature was evaluated. The transfer paper used was A4 paper (Prova Bond paper: 105 g / m 2 , manufactured by Fox River).

[0187] For the fuser, the fuser of a laser beam printer (LBP-712Ci, manufactured by Canon Inc.) was removed externally, and an external fuser modified to operate outside the laser beam printer was used. The external fuser was heated with the fixing temperature increased in 5°C increments from 90°C, and fixing was performed under the condition of a process speed of 360 mm / s.

[0188] The fixed image was visually inspected, and the low-temperature fixing property was evaluated with the lowest temperature at which cold offset did not occur as the fixing start temperature. The evaluation results are shown in Table 4.

[0189] <2> Adhesion to Paper (Scratch Resistance of Fixed Image) Using the same method as the evaluation of <1> above, a fixed image was printed. The fixing temperature was set to a temperature 5°C higher than the fixing start temperature. A soft tissue paper (DASPER, manufactured by Otsu Sangyo Co., Ltd.) was placed over the image area of the obtained fixed image, and the image area was rubbed 5 times back and forth while applying a load of 4.9 kPa from above the tissue paper. The image density before and after rubbing was measured respectively, and the reduction rate ΔD(%) of the image density was calculated by the following formula. This ΔD(%) was used as an index of rub resistance.

[0190] ΔD(%) = {(image density before rubbing - image density after rubbing) / image density before rubbing} × 100 The image density was measured with a color reflection densitometer (Color reflection densitometer X-Rite 404A, manufactured by X-Rite). The evaluation results are shown in Table 4.

[0191] <3> Hot offset resistance Under the same conditions as the evaluation of <1> above, the highest temperature at which no hot offset was observed was defined as the maximum fixing temperature, and the difference between the maximum fixing temperature and the minimum fixing temperature was defined as the fixable region. The evaluation criteria for the fixable region are as follows.

[0192] <4> Gloss evaluation Using the fixed image at the fixing start temperature in the evaluation of <1> above, the gloss value was measured using a handy gloss meter PG-1 (manufactured by Nippon Denshoku Industries Co., Ltd.). The measurement conditions were set such that the light projection angle and the light reception angle were both 75°, all the image patterns arranged in a 9-point array were measured, and the average value was evaluated. The evaluation results are shown in Table 4. C.O. in the table means cold offset, and H.O. means hot offset.

[0193]

Table 4

[0194] The present disclosure relates to the following configuration.

[0195] (Configuration 1) A toner having toner particles containing a resin component, wherein the toner particles contain, as the resin component, a crystalline vinyl resin having a unit (a) represented by the following formula (1), the resin component contains the unit (a) in an amount of 15.0% by mass or more and 40.0% by mass or less based on the mass of the resin component,

[0196] [Chemical formula]

[0197] R in the formula (1) 1 represents a hydrogen atom or a methyl group, and n represents an integer of 15 to 35, performing Soxhlet extraction of the toner particles using chloroform, removing components having a molecular weight of 2000 or less from the chloroform-soluble matter obtained by extraction for 18 hours by recycled HPLC, and using the resulting chloroform-soluble matter as chloroform-soluble matter W, when using acetonitrile as a poor solvent and chloroform as a good solvent for the chloroform-soluble matter W, linearly changing from a mobile phase of 100% by volume of acetonitrile to a mobile phase of 100% by volume of chloroform, and performing gradient LC analysis on the eluted components, in a graph with the horizontal axis representing the ratio (volume%) of chloroform in the mobile phase and the vertical axis representing the signal intensity (μA) of the eluted components detected using a charged particle detector, there are a plurality of maxima, among the plurality of maxima, when the maximum having the highest intensity and the maximum having the second highest intensity are considered, the maximum with the smaller ratio of chloroform in the mobile phase is defined as maximum value PA, the maximum with the larger ratio of chloroform in the mobile phase is defined as maximum value PB, the minimum value with the lowest intensity existing between the maximum value PA and the maximum value PB is defined as minimum value BAB, the ratio of chloroform of the minimum value BAB is defined as VAB volume% (where 20.0 < VAB < 95.0), the components with a ratio of chloroform in the mobile phase of 20.0 volume% or more and less than VAB volume% are defined as component A, and the components with a ratio of chloroform in the mobile phase of VAB volume% or more and 95.0 volume% or less are defined as component B, The resin component contains the component B in an amount of 40.0% by mass or more and 80.0% by mass or less based on the mass of the resin component. When the content of the unit (a) in the chloroform-soluble content W is WC% by mass and the content of the unit (a) in the component B is WB% by mass, WC and WB satisfy the following formula (2): WB / WC ≧ 0.70 (2) When the storage elastic modulus of the toner particles at 100°C is G’(T) and the storage elastic modulus of the component B at 100°C is G’(B), G’(T) and G’(B) satisfy the following formulas (3) and (4): 5.0×10 3 Pa ≦ G’(T) ≦ 1.0×10 5 Pa (3) 2.0×10 3 Pa ≦ G’(T) - G‘(B) ≦ 6.0×10 3 Pa (4) A toner characterized by the above.

[0198] (Configuration 2) The toner according to Configuration 1, wherein the component B contains the unit (a) in an amount of 25.0% by mass or more and 50.0% by mass or less based on the mass of the component B.

[0199] (Configuration 3) The toner according to Configuration 1 or 2, wherein the weight average molecular weight (Mw) of the component B is 30,000 or more and 200,000 or less.

[0200] (Configuration 4) The toner according to any one of Configurations 1 to 3, wherein the resin component contains the component A in an amount of 10.0% by mass or more and 60.0% by mass or less based on the mass of the resin component.

[0201] (Configuration 5) The toner according to any one of Configurations 1 to 4, wherein the resin component contains a chloroform-insoluble content in an amount of 3.0% by mass or more and 15.0% by mass or less based on the mass of the resin component.

[0202] (Configuration 6) The toner particles contain wax, The wax is at least one selected from the group consisting of esters of alcohols having 4 to 8 valences and aliphatic monocarboxylic acids, and ester waxes of carboxylic acids having 4 to 8 valences and aliphatic monoalcohols. The toner according to any one of Configurations 1 to 5.

[0203] (Configuration 7) The toner particles have a core-shell structure having a core containing the crystalline vinyl resin and a shell containing an amorphous resin. The toner according to any one of Configurations 1 to 6.

[0204] (Configuration 8) Component B has a lactam structure. The toner according to any one of Configurations 1 to 7.

[0205] (Configuration 9) The lactam structure contains a unit having a 5-membered lactam structure. The toner according to Configuration 8.

[0206] (Configuration 10) The crystalline vinyl resin contains a crystalline vinyl resin obtained by polymerizing a vinyl monomer containing a (meth)acrylate ester for introducing the unit (a) and then reacting another vinyl monomer by a hydrogen abstraction reaction. The toner according to any one of Configurations 1 to 9.

Claims

1. A toner having toner particles containing a resin component, wherein the toner particles contain, as the resin component, a crystalline vinyl resin having a unit (a) represented by the following formula (1), the resin component contains the unit (a) in an amount of 15.0% by mass or more and 40.0% by mass or less based on the mass of the resin component, 【Chemical 1】 R in the formula (1) above １ represents a hydrogen atom or a methyl group, and n represents an integer of 15 to 35, performing Soxhlet extraction of the toner particles using chloroform, removing components having a molecular weight of 2000 or less by recycled HPLC from the chloroform-soluble matter obtained by extraction for 18 hours, and using the resulting chloroform-soluble matter as chloroform-soluble matter W, when using acetonitrile as a poor solvent and chloroform as a good solvent for the chloroform-soluble matter W, linearly changing from a mobile phase of 100% by volume of acetonitrile to a mobile phase of 100% by volume of chloroform, and performing gradient LC analysis on the eluted components, in a graph with the horizontal axis representing the proportion (volume%) of chloroform in the mobile phase and the vertical axis representing the signal intensity (μA) of the eluted components detected using a charged particle detector, there are a plurality of maxima, among the plurality of maxima, the maximum with the smallest proportion of chloroform in the mobile phase among the maximum with the largest intensity and the maximum with the second largest intensity is defined as maximum value PA, the maximum with the largest proportion of chloroform in the mobile phase is defined as maximum value PB, the minimum value with the smallest intensity existing between the maximum value PA and the maximum value PB is defined as minimum value BAB, the proportion of chloroform of the minimum value BAB is defined as VAB volume% (where 20.0 < VAB < 95.0), components with a proportion of chloroform in the mobile phase of 20.0% by volume or more and less than VAB volume% are defined as component A, and components with a proportion of chloroform in the mobile phase of VAB volume% or more and 95.0% by volume or less are defined as component B, the resin component contains the component B in an amount of 40.0% by mass or more and 80.0% by mass or less based on the mass of the resin component, when the content of the unit (a) in the chloroform-soluble matter W is WC mass% and the content of the unit (a) in the component B is WB mass%, WC and WB satisfy the following formula (2), WB / WC ≧ 0.70 (2) when the storage elastic modulus of the toner particles at 100°C is G'(T) and the storage elastic modulus of the component B at 100°C is G'(B), G'(T) and G'(B) satisfy the following formulas (3) and (4), 5.0×10 ３ Pa ≤ G’(T) ≤ 1.0×10 ５ Pa (3) 2.0×10 ３ Pa ≤ G'(T) - G'(B) ≤ 6.0×10 ３ Pa (4) a toner characterized by the above.

2. The toner according to claim 1, wherein the component B contains the unit (a) in an amount of 25.0% by mass or more and 50.0% by mass or less based on the mass of the component B.

3. The toner according to claim 1 or 2, wherein the weight average molecular weight (Mw) of the component B is 30,000 or more and 200,000 or less.

4. The toner according to claim 1 or 2, wherein the resin component contains the component A in an amount of 10.0% by mass or more and 60.0% by mass or less based on the mass of the resin component.

5. The toner according to claim 1 or 2, wherein the resin component contains chloroform-insoluble matter in an amount of 3.0% by mass or more and 15.0% by mass or less based on the mass of the resin component.

6. The toner particles contain wax, The toner according to claim 1 or 2, wherein the wax is at least one selected from the group consisting of esters of tetravalent or higher to octavalent alcohols and aliphatic monocarboxylic acids, and ester waxes of tetravalent or higher to octavalent carboxylic acids and aliphatic monoalcohols.

7. The toner according to claim 1 or 2, wherein the toner particles have a core-shell structure having a core containing the crystalline vinyl resin and a shell containing an amorphous resin.

8. The toner according to claim 1 or 2, wherein the component B has a lactam structure.

9. The toner according to claim 8, wherein the lactam structure contains a unit having a 5-membered lactam structure.

10. The toner according to claim 1 or 2, wherein the crystalline vinyl resin contains a crystalline vinyl resin obtained by polymerizing a vinyl monomer containing a (meth)acrylate for introducing the unit (a) and then reacting another vinyl monomer by a hydrogen abstraction reaction.

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