Toner and method for producing toner

Abstract

The present invention relates to a toner and a method for producing a toner. A toner includes toner particles, the toner particles including a binder resin and a release agent, wherein the binder resin includes a first resin and a second resin; the first resin is a crystalline resin having a melting point (Tp) of 50°C to 90°C; the second resin is a non-crystalline resin; in a cross-section of the toner particle observed through a transmission electron microscope, the cross-section of the toner particle has a matrix-domain structure consisting of a matrix including the first resin and domains including the second resin; the area ratio of the matrix including the first resin to the total area of ​​the cross-section of the toner particle is 35 to 70 area%; and, with the longest direction of each domain being taken as the longitudinal direction, the standard deviation of the angle of the longitudinal direction of the domain is 25° or less.

Description

Technical Field

[0001] The present disclosure relates to a toner used in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and a toner jet method, and also relates to a method for producing the toner. Background Art

[0002] With the recent surge in the number of full-color electrophotographic copiers, the demand for higher printing speeds and greater energy savings is also increasing. To achieve high-speed printing, technologies for faster toner melting during the fixing process have been developed. Technologies for shortening various control times within a job and between jobs to improve productivity have also been studied. As an energy-saving measure, technologies for fixing toner at low temperatures to reduce energy consumption during the fixing process have also been studied.

[0003] Toners containing a rapidly melting crystalline resin as their main component are known to have superior low-temperature fixing properties compared to toners containing amorphous resins as their main component. For example, Japanese Patent Application Publication No. 2014-059489 describes a toner having a domain-matrix structure comprising a matrix composed of a crystalline resin and domains composed of amorphous resins and colorants, with the domain diameter and storage modulus set within predetermined ranges. As a result, a toner having excellent fixing properties, image density, and image gloss can be obtained.

[0004] Furthermore, Japanese Patent Application Publication No. 2014-142632 describes a toner having a domain-matrix structure comprising a matrix composed of a crystalline resin having a predetermined melting point range and domains composed of an amorphous resin. As a result, a toner capable of being fixed with low energy and capable of producing images resistant to external forces such as friction and scratching can be obtained. Summary of the Invention

[0005] The toner described in the aforementioned document has a domain-matrix structure, and a rapidly melting crystalline resin forms the matrix, resulting in excellent fixability at low energy. However, it has been found that under certain conditions, the transfer of the release agent to the image surface during fixation can be insufficient, and the fixation separation performance can deteriorate. The present disclosure aims to provide a toner that achieves both low-temperature fixability and fixation separation performance.

[0006] The present disclosure relates to a toner comprising toner particles.

[0007] Binder resin and release agent, wherein

[0008] The binder resin includes a first resin and a second resin;

[0009] The first resin is a crystalline resin having a melting point Tp of 50° C. to 90° C.;

[0010] The second resin is a non-crystalline resin;

[0011] In a cross section of a toner particle observed by a transmission electron microscope,

[0012] The cross section of the toner particle has a matrix-domain structure composed of a matrix including a first resin and domains including a second resin;

[0013] an area ratio of the matrix in the total area of ​​the cross section of the toner particle of 35 to 70 area %; and

[0014] When the longest direction of each domain is defined as the longitudinal direction, the standard deviation of the angles in the longitudinal directions of the domains is 25° or less.

[0015] The present disclosure can provide a toner that can achieve both low-temperature fixability and fixation separation properties.Further features of the present invention will become apparent from the following description of exemplary embodiments. DETAILED DESCRIPTION

[0016] Unless otherwise indicated, descriptions of numerical ranges such as "from XX to YY" or "XX to YY" in this disclosure include the numerical values ​​at the upper and lower limits of the range. In this disclosure, (meth)acrylate refers to acrylate and / or methacrylate. When describing numerical ranges in stages, the upper and lower limits of each numerical range can be combined arbitrarily. The term "monomer unit" describes the reaction form of a monomer material in a polymer. For example, a carbon-carbon bonded section in the main chain of a polymerized vinyl monomer in a polymer is considered a unit. A vinyl monomer can be represented by the following formula (Z):

[0017]

[0018] In formula (Z), R Z1 represents a hydrogen atom or an alkyl group (preferably C 1-3 alkyl, or more preferably methyl), and R Z2 represents an arbitrary substituent. The crystalline resin is a resin that shows a clear endothermic peak in differential scanning calorimetry (DSC) measurement.

[0019] The present disclosure relates to a toner comprising toner particles.

[0020] Binder resin and release agent, wherein

[0021] The binder resin includes a first resin and a second resin;

[0022] The first resin is a crystalline resin having a melting point Tp of 50° C. to 90° C.;

[0023] The second resin is a non-crystalline resin;

[0024] In a cross section of a toner particle observed by a transmission electron microscope,

[0025] The cross section of the toner particle has a matrix-domain structure composed of a matrix including a first resin and domains including a second resin;

[0026] an area ratio of the matrix in the total area of ​​the cross section of the toner particle of 35 to 70 area %; and

[0027] When the longest direction of each domain is defined as the longitudinal direction, the standard deviation of the angles in the longitudinal directions of the domains is 25° or less.

[0028] As a result of in-depth research by the present inventors, it was found that the above-mentioned problems can be solved by forming a domain-matrix structure consisting of a matrix including a first resin as a crystalline resin having a predetermined melting point and domains including a second resin as a non-crystalline resin, and controlling the area occupied by the first resin in the cross section of the colorant particle and the orientation state of the domain.

[0029] The present inventors speculate that the reasons for solving the above problems are as follows. First, excellent low-temperature fixing properties can be obtained by using a crystalline resin with a melting point Tp of 50°C to 90°C that has excellent rapid melting properties at low energy, and forming a matrix-domain structure consisting of a matrix including a first resin and a domain including a second resin. In the absence of a domain-matrix structure, and in the case where the first resin and the second resin are compatible with each other and form a uniform structure, the fixing separation property tends to decrease. In addition, the rapid melting properties of the crystalline resin are easily lost, and the low-temperature fixing properties are easily reduced. The melting point Tp is preferably 55°C to 70°C.

[0030] At the same time, for good fixing and releasability, it is important that the release agent dispersed in the toner particles migrate to the toner particle surfaces during fixing and become interposed between the toner image surface and the fixing roller. It is believed that in a toner having a matrix-domain structure composed of a matrix including a first resin (a crystalline resin) and domains (a non-crystalline resin), the release agent migrates to the toner particle surfaces during fixing through the matrix including the first resin.

[0031] Therefore, it is believed that when the orientation of the domain including the second resin is irregular, the transfer of the release agent to the surface of the colorant particle is hindered. Therefore, it is believed that by aligning the orientation of the domain including the second resin, the transfer of the release agent to the surface of the colorant particle during fixing can be promoted. As a result of the study, it was found that by setting the standard deviation of the angle in the length direction of the domain to 25° or less, the transfer of the release agent to the surface of the colorant particle can be promoted and good fixing separation can be obtained. The standard deviation of the angle in the length direction of the domain is preferably 22° or less. There is no particular restriction on the lower limit, but it is preferably 1° or more, more preferably 5° or more, and further preferably 10° or more.

[0032] Such effects are achieved when the matrix area ratio relative to the total cross-sectional area of ​​the toner particles is between 35 area% and 70 area%. When the matrix ratio is less than 35 area%, the aforementioned matrix-domain structure is reversed, resulting in a matrix-domain structure composed of a matrix comprising the second resin and domains comprising the first resin, and low-temperature fixability is reduced. Meanwhile, when the matrix ratio exceeds 70 area%, the viscosity of the matrix comprising the molten first resin tends to decrease, and fixation separation tends to decrease during high-temperature fixing.

[0033] Furthermore, the area ratio of the matrix in the total area of ​​the toner particle cross section is preferably 40 area % to 60 area %. As described above, since it is believed that the release agent moves to the toner particle surface through the matrix, when the ratio of the matrix is ​​60% or less, the density of the domains including the second resin becomes high, and the fixing separation property tends to improve. The ratio of the matrix in the total area of ​​the toner particle cross section can be controlled by the loading amounts of the first resin and the second resin.

[0034] The softening temperature Tm of the second resin is preferably at least 10°C higher than the melting point Tp of the first resin. When the softening temperature Tm of the second resin is close to the melting point of the first resin, the viscosity difference between the first and second resins becomes smaller during fixing. Therefore, it is believed that the release agent will also migrate toward the second resin forming the domains, and its transfer to the toner particle surface will be hindered.

[0035] Therefore, to promote transfer of the release agent to the toner particle surface and improve fixation separation, it is conceivable to set the softening temperature (Tm) of the second resin at least 10°C higher than the melting point (Tp) of the first resin. This allows the release agent to easily transfer to the toner particle surface through the matrix comprising the first resin. The softening temperature (Tm) of the second resin can be controlled by factors such as the molecular weight of the amorphous resin contained in the second resin. Increasing the molecular weight can increase the softening temperature (Tm) of the second resin. More preferably, the softening temperature (Tm) of the second resin is between Tp + 20°C and Tp + 50°C.

[0036] In cross-sectional observation of the toner particles, the average length (average major diameter) of the domain in the length direction is preferably 20 nm to 500 nm. When the average major diameter of the domain is 500 nm or less, the second resin is easily melted even when the toner is fixed at low temperatures, and the fixability is improved. At the same time, when fixed at high temperatures, the viscosity of the matrix including the molten first resin is less likely to decrease, and the fixability is improved. In addition, when the average major diameter of the domain is 20 nm or more, the fixability becomes better, the rapid melting property of the crystalline resin is easily manifested, and the low-temperature fixability becomes better. The average length of the domain in the length direction is more preferably 80 nm to 430 nm.

[0037] The average major diameter of the domain can be controlled by the composition of the monomers constituting the crystalline resin, the composition of the monomers constituting the amorphous resin, and the production conditions of the toner particles. Examples of methods for controlling the average major diameter of the domain include the relationship between the SP values ​​of the resins constituting the matrix and the domain, the mixing temperature and screw speed during the melt mixing process, and the stirring speed during the aggregation process. When the SP values ​​of the matrix and the resin of the domain are close to each other, the compatibility between the matrix and the domain is improved, and the average major diameter of the domain tends to be small. In addition, when the screw speed and the stirring speed are increased, the shear force acting on the resin becomes stronger, and the average major diameter of the domain becomes smaller.

[0038] The ratio La / Lb of the domain length La in the longitudinal direction to the maximum length Lb in the direction perpendicular to the longitudinal direction is preferably 8.0 or less, and more preferably 5.5 or less. The lower limit is not particularly limited, but is preferably 1.1 or more, and more preferably 1.5 or more.

[0039] A high La / Lb ratio indicates that the surface area of ​​the domains is wider than that of a sphere of the same volume; that is, the contact area between the matrix and the domains is wider. In other words, this is considered a state in which the matrix comprising the first resin and the domains comprising the second resin are in close contact with each other. When the matrix comprising the first resin and the domains comprising the second resin are functionally separated, a highly effective toner can be obtained. Therefore, by setting the La / Lb ratio to 8.0 or less, the fixing separation properties are further improved. The La / Lb ratio can be controlled by adjusting the SP values ​​of the first resin contained in the matrix and the second resin contained in the domains. By increasing the difference between the two SP values, the La / Lb ratio can be reduced.

[0040] Materials that can be used will be described in detail below.

[0041] <First Resin>

[0042] Binder resin comprises the first resin, and the first resin is a crystalline resin. Known crystalline resin can be used as this crystalline resin. Suitable examples include crystalline vinyl resin, crystalline polyester resin, crystalline polyurethane resin and crystalline polyurea resin. Other examples include ethylene copolymers, such as ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-methacrylic acid copolymer and ethylene-acrylic acid copolymer etc.

[0043] From the viewpoint of low temperature fixability, crystalline vinyl resin and crystalline polyester resin are preferred. In addition, it can be a mixed resin in which vinyl resin and polyester resin are combined. The first resin preferably includes a vinyl resin, more preferably a vinyl resin, and preferably has a first monomer unit represented by the following formula (1). The first resin is preferably a vinyl resin having a monomer unit represented by the following formula (1). Vinyl resin is a polymer or copolymer of a compound including a group having an ethylenically unsaturated bond such as vinyl. Examples of groups with an ethylenically unsaturated bond include vinyl, (meth)allyl, and (meth)acryloyl.

[0044] The content ratio of the first monomer unit in the first resin is preferably 30.0% to 90.0% by mass, and more preferably 45.0% to 75.0% by mass. The weight average molecular weight (Mw) of the first resin is preferably 5,000 to 100,000, and more preferably 15,000 to 50,000.

[0045]

[0046] In formula (1), R Z1 represents a hydrogen atom or a methyl group, and R 1 represents an alkyl group having 18 to 36 carbon atoms. The first monomer unit represented by formula (1) has an alkyl group having 18 to 36 carbon atoms in the side chain and is represented by R 1 The first monomer unit represented by formula (1) is preferably a monomer unit derived from at least one first polymerizable monomer selected from the group consisting of (meth)acrylates having an alkyl group having 18 to 36 carbon atoms.

[0047] Each has C 18-36 Examples of the (meth)acrylates of the alkyl group include 18-36(Meth)acrylates of linear alkyl groups [stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acrylate, dioctadecyl (meth)acrylate, myricyl (meth)acrylate, tridecyl (meth)acrylate, etc.] and groups each having C 18-36 Branched alkyl (meth)acrylates [such as 2-decyltetradecyl (meth)acrylate].

[0048] Among these, from the viewpoint of low-temperature fixing properties, at least one member selected from the group consisting of (meth)acrylates having a linear alkyl group with 18 to 36 carbon atoms is preferred, at least one member selected from the group consisting of (meth)acrylates having a linear alkyl group with 18 to 30 carbon atoms is more preferred, and at least one member selected from the group consisting of linear stearyl (meth)acrylate and behenyl (meth)acrylate is even more preferred. As the monomer forming the first monomer unit, one member may be used alone, or two or more members may be used in combination.

[0049] The SP value (J / cm 3 ) 0.5 When represented by SP1, SP1 is preferably less than 20.00, more preferably 19.00 or less, and further preferably 18.40 or less. The lower limit is not particularly limited, but is preferably 17.00 or more.

[0050] Here, the SP value is an abbreviation of the solubility parameter and is an indicator of solubility. The calculation method thereof will be described later. The unit of the SP value is (J / cm 3 ) 0.5 , but by using 1(cal / cm 3 ) 0.5 =2.045×10 3 (J / cm 3 ) 0.5 , which can be converted to (cal / cm 3 ) 0.5 .

[0051] The first resin preferably has a second monomer unit that is different from the first monomer unit and is at least one selected from the group consisting of monomer units represented by the following formulae (2) and (3). In addition, the SP value of the second monomer unit is represented by SP2 (J / cm 3 ) 0.5 When , it is preferable to satisfy the following relational expression (4). It is more preferable to satisfy the following relational expression (4'). The upper limit of SP2 is not particularly limited, but is preferably 30.00 or less.

[0052] 21.00(J / cm 3 ) 0.5 ≤SP2 (4)

[0053] 25.00(J / cm 3 ) 0.5 ≤SP2 (4')

[0054] When the SP2 of the second monomer unit satisfies formula (4), the second monomer unit becomes highly polar, and a polarity difference occurs between the first and second monomer units. Due to this polarity difference, crystallization of the first monomer unit is promoted, resulting in excellent low-temperature fixing properties. Specifically, the first monomer unit is introduced into the crystalline resin and aggregates to generate crystallinity.

[0055] Generally, when other monomer units are introduced, the crystallization of the first monomer unit is hindered, making it difficult to achieve the crystallinity of a crystalline resin. However, it is believed that by setting the SP1 of the first monomer unit and the SP2 of the second monomer unit within the above range, the first monomer unit and the second monomer unit can form a clear phase separation state in the first resin without being compatible with each other, and the melting point can be easily maintained without reducing crystallinity.

[0056]

[0057] (In formula (2), X represents a single bond or an alkylene group having 1 to 6 carbon atoms.

[0058] R 3 = -C≡N,

[0059] -C(=O)NHR 10 (R 10 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms),

[0060] hydroxyl groups,

[0061] -COOR 31 (R 31 represents a hydrogen atom, an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms, or a hydroxyalkyl group having 1 to 6 (preferably 1 to 4) carbon atoms),

[0062] -NH-C(=O)-N(R 33 )2(two R 33 independently represents a hydrogen atom or an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms),

[0063] -COO(CH2)2NHCOOR 34 (R 34 represents an alkyl group having 1 to 4 carbon atoms), or

[0064] -COO(CH2)2-NH-C(=O)-N(R 35 )2(two R 35 Each independently represents a hydrogen atom or an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms.

[0065] R 4 represents a hydrogen atom or a methyl group.)

[0066]

[0067] (In formula (3), R 5 represents an alkyl group having 1 to 4 carbon atoms, and R 6 represents a hydrogen atom or a methyl group.)

[0068] Specific examples of the second polymerizable monomer forming the second monomer unit include the polymerizable monomers listed below: Preferably, a polymerizable monomer capable of forming a monomer unit represented by formula (2) or (3) is used.

[0069] Monomers having a nitrile group; for example, acrylonitrile, methacrylonitrile, and the like.

[0070] Monomers having a hydroxyl group; for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and the like.

[0071] Monomers having an amide group; for example, acrylamide and monomers obtained by reacting an amine having 1 to 30 carbon atoms and a carboxylic acid having 2 to 30 carbon atoms and having an ethylenically unsaturated bond (acrylic acid, methacrylic acid, etc.) by a known method.

[0072] A monomer having a urea group; for example, a monomer obtained by reacting an amine having 3 to 22 carbon atoms [primary amines (n-butylamine, tert-butylamine, propylamine, and isopropylamine, etc.), secondary amines (di-n-ethylamine, di-n-propylamine, and di-n-butylamine, etc.), aniline, and epoxidized amines, etc.] with an isocyanate having 2 to 30 carbon atoms and having an ethylenically unsaturated bond by a known method.

[0073] Monomers having a carboxyl group; for example, methacrylic acid, acrylic acid, and 2-carboxyethyl (meth)acrylate.

[0074] Among these, monomers having a nitrile group, an amide group, a hydroxyl group, or a urea group are preferably used. More preferably, monomers having an ethylenically unsaturated bond and at least one functional group selected from the group consisting of a nitrile group, an amide group, a hydroxyl group, and a urea group are used. Acrylonitrile and methacrylonitrile are particularly preferred.

[0075] In addition, vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl decanoate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl pivalate, and vinyl octanoate are also preferably used as the second monomer unit. Among them, vinyl esters are non-conjugated monomers that tend to maintain appropriate reactivity with the first polymerizable monomer and easily improve the crystallinity of the polymer. Therefore, vinyl monomers are preferred from the viewpoint of low-temperature fixability.

[0076] The content ratio of the second monomer unit in the first resin is preferably 5.0% by mass to 40.0% by mass, and more preferably 7.0% by mass to 30.0% by mass.

[0077] The first resin may include a third monomer unit obtained by polymerizing a third polymerizable monomer that is not included in the above formula (4) (i.e., different from the first polymerizable monomer and the second polymerizable monomer) within a range that does not impair the mass ratio of the first monomer unit to the second monomer unit. As the third polymerizable monomer, a monomer that does not satisfy the above formula (4) may be used among the monomers exemplified as the second polymerizable monomer.

[0078] For example, the following monomers can also be used. For example, styrene and o-methylstyrene and their derivatives, and (meth)acrylates such as methyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Among them, from the perspective of charge diffusion, the third polymerizable monomer is preferably styrene. The content ratio of the third monomer unit in the first resin is preferably 5.0% to 50.0% by mass, and more preferably 10.0% to 35.0% by mass.

[0079] <Second Resin>

[0080] The binder resin includes a second resin, and the second resin is a non-crystalline resin. As the second resin forming the domain, known non-crystalline resins can be used, and polyester resins, styrene acrylic resins, or mixed resins thereof are preferred from the perspectives of low-temperature fixability and fixation separation properties. As the styrene acrylic resin, styrene acrylic resins commonly used in toners can be preferably used.

[0081] The second resin preferably includes a styrene acrylic resin, and more preferably a styrene acrylic resin. The styrene acrylic resin is preferably a copolymer of a styrene monomer and a (meth) acrylic monomer. The weight average molecular weight (Mw) of the second resin is preferably 10,000 to 100,000, and more preferably 20,000 to 60,000.

[0082] Examples of styrene monomers include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, and p-phenylstyrene. These styrene monomers can be used alone or in combination of two or more.

[0083] Examples of the (meth)acrylic acid monomer include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, dimethyl phosphate, ethyl (meth)acrylate, diethyl phosphate, ethyl (meth)acrylate, dibutyl phosphate, ethyl (meth)acrylate, 2-benzoyloxyethyl (meth)acrylate, (meth)acrylonitrile, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid, and maleic acid. These (meth)acrylic acid monomers can be used alone or in combination of two or more.

[0084] As the polyester resin, polyester resins commonly used for toners can be preferably used. Monomers used in the polyester resin include polyols (divalent or trivalent or higher alcohols), polycarboxylic acids (divalent or trivalent or higher carboxylic acids), and anhydrides or lower alkyl esters thereof.

[0085] Examples of polyols include the following. Examples of diols include the following bisphenol derivatives. Polyoxypropylene-(2.2)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene-(3.3)-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene-(2.0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene-(2.0)-polyoxyethylene-(2.0)-2,2-bis(4-hydroxyphenyl)-propane, and polyoxypropylene-(6)-2,2-bis(4-hydroxyphenyl)propane.

[0086] Examples of other polyols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, sorbitol, 1,2,3,6-hexanetetraol, 1,4-sorbitol, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylglycerol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trimethylolbenzene. These polyols can be used alone or in combination of two or more.

[0087] The example of polycarboxylic acid comprises the following.The example of dicarboxylic acid comprises toxilic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenylsuccinic acid, isododecenylsuccinic acid, n-dodecylsuccinic acid, isododecylsuccinic acid, n-octenylsuccinic acid, n-octylsuccinic acid, isooctenylsuccinic acid, isooctylsuccinic acid, the acid anhydrides of these acids and their lower alkyl esters. Among them, preferably use toxilic acid, fumaric acid, terephthalic acid, and n-dodecenylsuccinic acid.

[0088] Examples of trivalent or higher carboxylic acids, their anhydrides, or their lower alkyl esters include the following: 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetrakis(methylenecarboxy)methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, Empol trimer acid, their anhydrides, or their lower alkyl esters.

[0089] Among them, 1,2,4-benzenetricarboxylic acid (trimellitic acid) or its anhydride derivatives are preferably used due to low cost and ease of reaction control. These polycarboxylic acids can be used alone or in combination of two or more.

[0090] <Other resins>

[0091] For the purpose of improving pigment dispersibility, the binder resin may include a third resin in addition to the first resin and the second resin to the extent that the effect of the present disclosure is not impaired. Examples of such resins include the following. Polyvinyl chloride, phenolic resin, natural resin-modified phenolic resin, natural resin-modified maleic acid resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone-indene resin, and petroleum resin.

[0092] <Release Agent>

[0093] The toner includes a release agent. The release agent can be selected and used from an optimal combination of the first resin and the second resin. It is believed that during fixing, the release agent migrates through the first resin to the surface of the toner particles. Therefore, the melting point of the release agent is preferably between the melting point Tp of the first resin and the softening temperature Tm of the second resin. Wax is a synonym for release agent.

[0094] Examples of release agents (waxes) include the following: hydrocarbon waxes such as microcrystalline wax, paraffin wax and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax and block copolymers thereof; waxes mainly composed of fatty acid esters such as carnauba wax; and waxes composed of partially or completely deoxygenated fatty acid esters such as deoxygenated carnauba wax.

[0095] Other examples include the following: saturated straight-chain fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and stearidonic acid; saturated alcohols such as stearyl alcohol, aralkyl alcohols, behenyl alcohol, lignoceryl alcohol, wax alcohol, and melissyl alcohol; polyols such as sorbitol; esters of fatty acids such as palmitic acid, stearic acid, behenyl alcohol, and montanic acid with alcohols such as stearyl alcohol, aralkyl alcohols, behenyl alcohol, lignoceryl alcohol, wax alcohol, and melissyl alcohol; fatty acid amides such as linoleamide, oleamide, and lauric acid amide; and fatty acid amides such as methylenebisstearamide, ethylenebiscapric acid amide, ethylenebislauric acid amide, and hexamethylenebisstearamide. Saturated fatty acid bisamides; unsaturated fatty acid amides such as ethylenebisoleamide, hexamethylenebisoleamide, N,N'-dioleyl adipamide and N,N'-dioleyl sebacamide; aromatic bisamides such as m-xylene bisstearamide and N,N'-distearylisophthalamide; fatty metal salts (commonly known as metal soaps) such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate; waxes obtained by grafting vinyl monomers such as styrene and acrylic acid onto aliphatic hydrocarbon waxes; partial esterification products of polyols and fatty acids such as monoglyceride of behenic acid; and methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable oils and fats.

[0096] The release agent preferably includes a hydrocarbon wax, and the content of the wax is preferably 2.0 to 30.0 parts by mass relative to 100 parts by mass of the binder resin.

[0097] <Colorant>

[0098] The toner particles may further include a colorant. Examples of the colorant include the following.

[0099] Examples of black colorants include carbon black and black colorants obtained by blending yellow, magenta, and cyan colorants. Pigments can be used alone as colorants, but from the viewpoint of image quality of full-color images, it is desirable to combine dyes and pigments to improve clarity.

[0100] Examples of pigments for magenta toners include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48:2, 48:3, 48:4, 49, 50, 51, 52, 53, 54, 55, 57:1, 58, 60, 63, 64, 68, 81:1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, and 282; CI Pigment Violet 19; and CI Vat Red 1, 2, 10, 13, 15, 23, 29, and 35.

[0101] Examples of dyes used for magenta toners include CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, and 121; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21, 27; oil-soluble dyes such as CI Disperse Violet 1, and CI Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, and 40, and basic dyes such as CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28.

[0102] Examples of pigments for cyan toners include CI Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, and 17; CI Vat Blue 6; and CI Acid Blue 45 and copper phthalocyanine pigments having 1 to 5 phthalimidomethyl substituents in the phthalocyanine skeleton. Examples of dyes for cyan toners include CI Solvent Blue 70.

[0103] Examples of pigments for yellow toners include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, and 185; and CI Vat Yellow 1, 3, and 20. Examples of dyes for yellow toners include CI Solvent Yellow 162.

[0104] These colorants can be used alone or in mixtures, and can even be used in the form of solid solutions. The colorant is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner. The content of the colorant is preferably 0.1 to 30.0 parts by mass relative to 100 parts by mass of the binder resin.

[0105] <Charge Control Agent>

[0106] Toner particles may contain a charge control agent as needed. By blending a charge control agent, the charge characteristics can be stabilized, and the optimal triboelectric charge amount can be controlled according to the development system. While any known charge control agent can be used, metal compounds of aromatic carboxylic acids are particularly preferred because they are colorless, have a high toner charging speed, and can stably maintain a constant charge amount.

[0107] Examples of the negative charge control agent include metal compounds of salicylic acid, metal compounds of benzoic acid, metal compounds of dicarboxylic acids, polymer compounds having sulfonic acid or carboxylic acid in the side chain, polymer compounds having sulfonates or sulfonated products in the side chain, polymer compounds having carboxylates or carboxylated products in the side chain, boron compounds, urea compounds, silicon compounds, and calixarenes.

[0108] The charge control agent may be added to the toner particles internally or externally.The content of the charge control agent is preferably 0.2 parts by mass to 10.0 parts by mass, and more preferably 0.5 parts by mass to 10.0 parts by mass relative to 100 parts by mass of the binder resin.

[0109] <Inorganic fine particles>

[0110] As needed, the toner may include inorganic fine particles. The inorganic fine particles may be added internally to the toner particles or may be mixed with the toner as an external additive. Examples of inorganic fine particles include fine particles such as silica fine particles, titanium oxide fine particles, aluminum oxide fine particles, and composite oxide fine particles thereof. Among the inorganic fine particles, silica fine particles and titanium oxide fine particles are preferred for improving fluidity and uniformizing charge. The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

[0111] From the viewpoint of improving fluidity, the specific surface area of ​​the inorganic fine particles as the external additive is preferably 50 m 2 / g to 400m 2 / g. In addition, from the viewpoint of improving durable stability, the specific surface area of ​​the inorganic fine particles as the external additive is preferably 10 m 2 / g to 50m 2 Inorganic fine particles having a specific surface area within the above range may be used in combination to achieve both improved fluidity and durable stability.

[0112] The content of the external additive is preferably 0.1 parts by mass to 10.0 parts by mass relative to 100 parts by mass of the toner particles. A known mixer such as a Henschel mixer can be used to mix the toner particles and the external additive.

[0113] <Developer>

[0114] Although the toner can be used as a one-component developer, it is more preferable to use it as a two-component developer by being mixed with a magnetic carrier because stable images can be obtained over a long period of time.

[0115] Examples of magnetic carriers include generally known materials such as iron powder having an oxidized surface, unoxidized iron powder, metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese and rare earth and alloys thereof, magnetic bodies such as ferrite, and magnetic body-dispersion resin carriers (so-called resin carriers) comprising a magnetic body and a binder resin for maintaining the magnetic body in a dispersed state, and the like.

[0116] In the case where the colorant is mixed with a magnetic carrier and used as a two-component developer, good results are generally obtained when the mixing ratio of the carrier as the colorant concentration in the two-component developer is preferably from 2.0 mass % to 15.0 mass %, and more preferably from 4.0 mass % to 13.0 mass %.

[0117] <Toner Manufacturing Method>

[0118] The method for producing the toner is not particularly limited, and a known method can be used. A melt-kneading and pulverizing method is preferred. The melt-kneading and pulverizing method includes, for example, a melt-kneading step of melt-kneading a composition including a binder resin and a release agent to obtain a melt-kneaded product, a cooling and solidifying step of cooling and solidifying the melt-kneaded product to obtain a cooled solidified product, and a pulverizing step of pulverizing the cooled solidified product to obtain a pulverized product.

[0119] In the case of the above production method, it is easy to apply shear stress to the melt-kneaded product immediately after the formation of the matrix-domain structure composed of the matrix including the first resin and the domains including the second resin. For example, when a twin-screw kneader is used in the melt-kneading step, a mechanism for applying shear stress to the discharged melt-kneaded product can be provided.

[0120] As a mechanism for applying shear stress to the melt-kneaded product, when the melt-kneaded product is cooled and solidified, cooling after rolling or rolling while cooling can be used. As a method for cooling after rolling, a method of rolling with a pressure roller and then cooling with a steel strip cooler can be used. As a method of rolling while cooling, a method of simultaneously cooling and rolling with a pressure roller having a cooling mechanism can be used. Rolling makes it easy to align the orientation of the domains and maintain this state by cooling. That is, as a method for producing toner, when the melt-kneaded product is cooled and solidified, it is preferably rolled while cooling.

[0121] In addition, it is preferred to use the first resin and the second resin in a combination as follows: wherein when a melt-kneaded product obtained by melt-kneading the first resin and the second resin at 150°C is observed at 150°C, the first resin and the second resin are incompatible. By using a combination of resins that are incompatible at high temperatures, it becomes easier to apply shear stress and align the orientation of the domains. The observation of the melt-kneaded product at 150°C is specifically carried out as follows. The melt-kneaded product obtained by melt-kneading a mixture of the first resin and the second resin at 150°C with a twin-screw mixer is heated to 150°C on a hot plate and observed. During the observation, when the melt-kneaded product is opaque, it is determined that the two resins are incompatible with each other.

[0122] Hereinafter, the production steps of the toner in the melt-kneading and pulverization method will be described.

[0123] <Raw Material Mixing Step>

[0124] In the raw material mixing step, as materials constituting the toner particles, for example, a binder resin, a release agent, and, as needed, other components such as a colorant and a charge control agent are weighed in predetermined amounts and blended. Examples of the mixing apparatus include a double cone mixer, a V-type mixer, a drum mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a Mechanohybrid (manufactured by Nippon Coke Industries, Ltd.).

[0125] <Melt-kneading step>

[0126] Next, the mixed material is melt-mixed so that releasing agent etc. are dispersed in the binder resin.In the melt-mixing step, the batch type mixers such as pressure mixer or Banbury mixer can be used, or continuous mixer, and due to the advantage of continuous production, single screw or twin screw extruder have become main flow.Its example comprises KTK type twin screw extruder (by Kobe Steel, Ltd. manufacture), TEM type twin screw extruder (by Toshiba Machine Co., Ltd. manufacture), PCM mixer (by Ikegai Iron Works Co., Ltd. manufacture), twin screw extruder (by Kabushiki Kaisha KCK manufacture), co-mixer (by Buss AG manufacture) and Kneedex (by Nippon Coke Industries Co., Ltd. manufacture) etc.In addition, the resin combination obtained by melt-mixing can be rolled with two rollers etc., and cooled with water etc. in cooling step.

[0127] Especially, preferably after melt mixing, resin combination is rolled, and immediately thereafter resin combination is cooled rapidly, because it becomes easy to control the degree of orientation of domain within the above-mentioned specific range.The example of suitable method comprises with biaxial roller or drum, the resin combination after melt mixing is rolled and then with the method for steel belt cooler (manufactured by Nippon SteelConveyor Co., Ltd.) cooling, and with the method for rolling while such as with the press roller of cooling mechanism and drum cooling of the inside with drum flaker (manufactured by Nippon Coke Co., Ltd.).In preferred method, the resin combination is rolled while the resin combination after melt mixing is cooled by press roller and drum provided with cooling mechanism inside.

[0128] In order to control the orientation of the domain, the melt-mixed resin composition preferably has a high cooling rate when cooled to below the melting point Tp of the first resin, and the time until the melt-mixed resin composition is cooled to below the melting point Tp of the first resin is preferably short. The time from melting until the melt-mixed resin composition is rolled and cooled to reach below the melting point Tp of the first resin is preferably within 30 seconds, more preferably within 20 seconds, and further preferably within 15 seconds. The cooling rate from rolling to reaching below the melting point Tp of the first resin is preferably 3°C / second to 50°C / second, more preferably 4°C / second to 30°C / second, and even more preferably 5°C / second to 12°C / second. The dispersion state of the first resin and the second resin, and the average major diameter of the domain, etc. can be controlled by the mixing temperature of the melt mixing step, and the speed of the screw, etc.

[0129] <Crushing Step>

[0130] Then, the cooled product of the resin composition is pulverized to a desired particle size in a pulverization step. In the pulverization step, after coarse pulverization using a pulverizer such as a crusher, a hammer mill, or a feather mill, fine pulverization is further performed using, for example, a Cryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), a super rotor (manufactured by Nisshin Engineering Co., Ltd.), a turbo mill (manufactured by Turbo Industries Co., Ltd.), or an air jet system.

[0131] <Grading steps>

[0132] Thereafter, classification is performed as needed using a classifier or a mesh screen such as an inertial classification type elbow nozzle (manufactured by Nittetsu Mining Co., Ltd.), a centrifugal classification type Turboplex (manufactured by Hosokawa Micron Corporation), a TSP separator (manufactured by Hosokawa Micron Corporation), and a Faculty (manufactured by Hosokawa Micron Corporation).

[0133] <External addition steps>

[0134] The toner particles obtained can be used as a toner as they are. As needed, the toner particle surface can be externally treated with an external additive to obtain a toner. As a method for externally adding an external additive, a predetermined amount of a classified toner and various known external additives are blended and then stirred and mixed by using a mixing device such as a double cone mixer, a V-type mixer, a drum mixer, a super mixer, a Henschel mixer, a Nauta mixer, a Mechanohybrid (manufactured by Nippon Coke Industries, Ltd.), and a Nobilta (manufactured by Hosokawa Micron Corporation) as an external mixer.

[0135] <Evaluation of Domain-Matrix Structure by Cross-Section Observation of Toner>

[0136] First, a slice was prepared as a reference sample for the presence ratio. First, the first resin (crystalline resin) was thoroughly dispersed in a visible light-curable resin (Aronix LCR Series D800) and cured by exposure to short-wavelength light. The resulting cured resin was sliced ​​using an ultramicrotome equipped with a diamond knife to prepare 250 nm sample slices. Samples of the second resin (amorphous resin) were prepared in the same manner.

[0137] The first resin and the second resin were mixed at a ratio of 30 / 70 and 70 / 30, and melt-kneaded to prepare a kneaded mixture. Similarly, these were dispersed in a visible light curable resin and cut to prepare a sample slice.

[0138] Next, these reference samples were observed in cross section by TEM-EDX using a transmission electron microscope (JEOL Ltd., JEM-2800 electron microscope), and element mapping was performed by EDX. The mapped elements were carbon, oxygen, and nitrogen. The mapping conditions were as follows.

[0139] Accelerating voltage: 200 kV

[0140] Electron beam exposure size: 1.5nm

[0141] Time limit: 600 seconds

[0142] Stagnation period: 20 to 30

[0143] Mapping resolution: 256×256

[0144] (Oxygen intensity / carbon intensity) and (nitrogen intensity / carbon intensity) were calculated based on the spectral intensity of each element (average within a 10 nm square area), and a calibration curve was created for the mass ratio of the first and second resins. When the monomer units of the first resin contain nitrogen, the (nitrogen intensity / carbon intensity) calibration curve was used for subsequent measurements.

[0145] Next, the toner samples were analyzed. First, the toner was fully dispersed in a visible light-curable resin (Aronix LCR Series D800) and cured by exposure to short-wavelength light. The resulting cured resin was cut using an ultramicrotome equipped with a diamond knife to prepare 250 nm sample slices. The cut samples were then observed using a TEM-EDX transmission electron microscope (JEOL Ltd., JEM-2800 electron microscope). Cross-sectional images of the toner particles were obtained, and elemental mapping was performed using EDX. The mapped elements were carbon, oxygen, and nitrogen.

[0146] The toner particle cross-sections for observation are selected as follows. First, the cross-sectional area of ​​the toner particle is determined from the cross-sectional image, and the diameter of a circle having the same area as the cross-sectional area (equivalent circle diameter) is determined. Observation is limited to toner particle cross-sectional images in which the absolute value of the difference between the equivalent circle diameter and the weight-average particle size (D4) is within the range of 1.0 μm. For domains confirmed in the observed image, (oxygen element intensity / carbon element intensity) and / or (nitrogen element intensity / carbon element intensity) are calculated based on the spectral intensity of each element (average of 10 nm squares), and the ratio of the first and second resins is calculated based on comparison with the calibration curve. Domains in which the ratio of the second resin is at least 80% are considered to be domains in the present disclosure.

[0147] When the proportion of toner particle cross-sections forming a matrix-domain structure in the toner particle cross-section is 80% or more by number, the toner particle cross-section is determined to have a matrix-domain structure. A matrix-domain structure is a state in which domains, a discontinuous phase, are dispersed within a matrix, a continuous phase. Here, when 90% by area or more of the area of ​​the first resin or the area occupied by the second resin in the toner particle cross-section exists as a continuous region, the first resin or the second resin is determined to be a continuous phase.

[0148] After identifying domains confirmed by image observation, binarization processing is performed. By analyzing the binarized image, the domain long diameter La, the angle along the domain's lengthwise direction, and the maximum length Lb perpendicular to the domain's long diameter La, present in the toner particle's cross-sectional image, are determined. Measurements are taken at 10 points on each toner particle, and the arithmetic mean of the domain long diameters La for these 10 toner particles is defined as the average long diameter (μm) of the domains. The domain's lengthwise direction is the longest direction of the domain. That is, it is the direction of the line segment that forms the long diameter La.

[0149] At the same time, the standard deviation of the angles in the longitudinal direction of the domains is calculated by the following method. First, an arbitrary reference axis (the vertical axis or horizontal axis of the SEM photograph) is set, and the value of the angle formed by the reference axis and the longitudinal direction of each domain is measured in 10 domains in one toner particle. This is the angle in the longitudinal direction of the domain. The average value of the angles in the longitudinal direction of the 10 domains measured for each toner particle is obtained, and the angle obtained by subtracting the average value from the measured value is determined. This operation is performed for 10 toner particles, and the standard deviation is calculated based on the 100 angle data, and the result is used as the standard deviation of the angles in the longitudinal direction of the domains. In addition, the value of La / Lb is calculated for each domain, and the arithmetic mean of the 100 domains is defined as the La / Lb of the toner particle.

[0150] Meanwhile, for the domain area, the total area is obtained by summing the areas of all domains present in the cross-sectional image of one toner particle, and the total area is represented by S1. The total area of ​​the domains of 100 toner particles is calculated (i.e., S1+S2…+S100), and the arithmetic mean of the 100 particles is defined as the "domain area."

[0151] To determine the domain area of ​​a toner particle cross section, the total cross-sectional area of ​​the toner particles (for 100 toner particles) obtained from the toner cross-sectional image was used, and the arithmetic mean thereof was calculated as the "total area of ​​toner particle cross sections." Furthermore, the "total area of ​​toner particle cross sections" minus the "domain area" was defined as the "matrix area." The "matrix area" / "total area of ​​toner particle cross sections" × 100 was defined as the matrix area ratio (matrix area ratio (%)) in the total area of ​​the toner particle cross sections. The image processing software "ImageJ" was used for binarization processing and calculation of the average major diameter of the domains and the standard deviation of the angles in the longitudinal direction of the domains.

[0152] In the image processing software, the major diameter La can be selected via Analyze menu>Analyze Particles>Fit Ellipse>Major. The maximum length Lb can be selected via Analyze menu>Analyze Particles>Fit Ellipse>Minor, and the angle along the length can be selected via Analyze menu>Analyze Particles>Fit Ellipse>Ma Angle.

[0153] <Method of Separating Materials from Toner>

[0154] Each material contained in the toner can be separated from the toner using the difference in solubility of each material in the solvent.

[0155] First separation: The toner is dissolved in methyl ethyl ketone (MEK) at 23° C., and the soluble component (second resin) is separated from the insoluble components (first resin, releasing agent, colorant, inorganic fine particles, etc.).

[0156] Second separation: The insoluble components (first resin, releasing agent, colorant, inorganic fine particles, etc.) obtained in the first separation are dissolved in MEK at 100°C, and the soluble components (first resin, releasing agent) are separated from the insoluble components (colorant, inorganic fine particles, etc.).

[0157] Third separation: The soluble component (first resin, releasing agent) obtained in the second separation was dissolved in chloroform at 23° C., and separated into a soluble component (first resin) and an insoluble component (releasing agent).

[0158] (Including the case of the third resin)

[0159] First separation: The toner is dissolved in methyl ethyl ketone (MEK) at 23° C., and soluble components (second resin, third resin) are separated from insoluble components (first resin, releasing agent, colorant, inorganic fine particles, etc.).

[0160] Second separation: The soluble components (second resin, third resin) obtained in the first separation were dissolved in toluene at 23° C., and separated into a soluble component (third resin) and an insoluble component (second resin).

[0161] Third separation: The insoluble components (first resin, releasing agent, colorant, inorganic fine particles, etc.) obtained in the first separation were dissolved in MEK at 100°C and separated into soluble components (first resin, releasing agent) and insoluble components (colorant, inorganic fine particles, etc.).

[0162] Fourth separation: The soluble component (first resin, releasing agent) obtained in the third separation was dissolved in chloroform at 23° C., and separated into a soluble component (first resin) and an insoluble component (releasing agent).

[0163] (Measurement of Contents of First Resin and Second Resin in Binder Resin in Toner)

[0164] The masses of the soluble component and the insoluble component obtained in the above separation step are measured to calculate the contents of the first resin and the second resin in the binder resin in the toner.

[0165] In addition, one can use, for example 1Known methods such as H-NMR are used to specify the structure of the first resin separated from the toner and the like.

[0166] <Calculation method of SP value>

[0167] The SP value is determined as follows according to the calculation method proposed by Fedors. For atoms or atomic groups in the molecular structure of each polymerizable monomer, the evaporation energy (Δei) (cal / mol) and molar volume (Δvi) (cm 3 / mol) are determined from the table described in "Polym. Eng. Sci., 14(2), 147-154(1974)", and (4.184×ΣΔei / ΣΔvi) 0.5 is regarded as the SP value (J / cm 3 ) 0.5 .

[0168] For atoms or atomic groups in the molecular structure of the same polymerizable monomer having a double bond broken by polymerization, the SP value of the monomer unit is calculated by a similar method.

[0169] <Method for measuring the weight-average molecular weight (Mw) of a resin or the like using gel permeation chromatography (GPC)>

[0170] For example, the weight-average molecular weight (Mw) of the tetrahydrofuran (THF)-soluble component of a resin is measured by gel permeation chromatography (GPC) as follows.

[0171] First, a sample such as a resin is dissolved in tetrahydrofuran (THF) over a 24-hour period at room temperature. The resulting solution is filtered through a solvent-resistant membrane filter (Maishori Disk, Tosoh Corp.) with a pore size of 0.2 μm to obtain a sample solution. The concentration of the THF-soluble component in the sample solution is adjusted to about 0.8 mass%. The sample solution is used for measurement under the following conditions.

[0172] System: HLC8120 GPC (Detector: RI) (Tosoh Corp.)

[0173] Columns: Shodex KF-801, 802, 803, 804, 805, 806, 807 (total 7) (Showa Denko)

[0174] Eluent: Tetrahydrofuran (THF)

[0175] Flow rate: 1.0 mL / min

[0176] Oven temperature: 40.0 °C

[0177] Sample injection volume: 0.10 mL

[0178] The molecular weight of the sample was calculated using a molecular weight calibration curve prepared using standard polystyrene resins (trade names: TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500, Tosoh Corp.).

[0179] <Method for measuring the melting point, endothermic peak, and endothermic amount of resins, etc.>

[0180] The melting point, endothermic peak, and endothermic amount of the resin and the like are measured using DSC Q1000 (manufactured by TA Instruments) under the following conditions.

[0181] Heating rate: 10℃ / min

[0182] Measurement start temperature: 20°C

[0183] Measurement end temperature: 180℃

[0184] The melting points of indium and zinc were used for temperature calibration of the device's detection section, and the heat of solution of indium was used for calorific value calibration. Specifically, 5 mg of sample was accurately weighed into an aluminum pan and subjected to differential scanning calorimetry. An empty silver pan was used as a reference. The peak temperature of the maximum endothermic peak during the first temperature increase was considered the melting point. If multiple peaks were present, the maximum endothermic peak was the peak with the highest endothermic value. Furthermore, the endothermic value of the maximum endothermic peak was determined.

[0185] <Method for measuring the softening temperature (Tm) of the resin>

[0186] The softening temperature of the resin was measured using a constant-load extrusion capillary rheometer (Shimadzu Corporation, CFT-500D Flowtester flow characteristics evaluation device) according to the attached manual. With this device, the temperature of a measurement sample contained in a cylinder is raised to melt the sample while a fixed load is applied to the measurement sample from above by a piston. The molten measurement sample is then extruded through a die at the bottom of the cylinder, and a flow curve showing the relationship between temperature and piston descent during this process can be obtained. The "melting temperature by the 1 / 2 method" described in the manual attached to the CFT-500D Flowtester flow characteristics evaluation device was taken as the softening temperature.

[0187] The melting temperature by the 1 / 2 method is calculated as follows.

[0188] Half the difference between the amount of piston descent at the end of outflow (outflow end point, designated as "Smax") and the amount of piston descent at the start of outflow (lowest point, designated as "Smin") is determined and taken as X (X = (Smax - Smin) / 2). The temperature at which the piston descent in the flow curve is the sum of X and Smin is the melting temperature determined by the 1 / 2 method.

[0189] For the measurement sample, about 1.0 g of the resin was compression molded at about 10 MPa for about 60 seconds at 25° C. using a desktop compression molding machine (eg, NPa System Co., Ltd., NT-100H) to obtain a cylindrical sample with a diameter of about 8 mm.

[0190] Perform specific measurement operations according to the device manual.

[0191] The measurement conditions of CFT-500D are as follows.

[0192] Test mode: heating method

[0193] Starting temperature: 50℃

[0194] Reach temperature: 200℃

[0195] Measuring interval: 1.0℃

[0196] Heating rate: 4.0℃ / min

[0197] Piston cross-sectional area: 1.000cm 2

[0198] Test load (piston load): 10.0kgf / cm 2 (0.9807MPa)

[0199] Warm-up time: 300 seconds

[0200] Die hole diameter: 1.0mm

[0201] Mold length: 1.0mm

[0202] <Method for measuring weight-average particle size (D4) of toner particles>

[0203] Using a Multisizer (registered trademark) 3 CoulterCounter precision particle size distribution analyzer (Beckman Coulter, Inc.) based on the pore resistance method and equipped with a 100 μm aperture, and the accompanying dedicated Beckman Coulter Multisizer 3 Version 3.51 software (Beckman Coulter, Inc.) for setting measurement conditions and analyzing measurement data, 25,000 effective measurement channels were measured, and the measurement data were analyzed to calculate the weight-average particle size (D4) of the toner particles (or toner). The electrolyte aqueous solution used in the measurement can be a solution obtained by dissolving special grade sodium chloride in ion exchange water to a concentration of about 1% by mass, such as ISOTON II (Beckman Coulter, Inc.). Prior to measurement and analysis, the dedicated software settings were performed as follows.

[0204] 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 to the value obtained using "Standard Particles 10.0 μm" (Beckman Coulter, Inc.). The threshold and noise level were automatically set by pressing the "Threshold / Noise Level Measurement Button." The current was set to 1600 μA, the gain to 2, and the electrolyte solution to ISOTON II, with the post-measurement nozzle flush selected. In the "Set Pulse to Size Conversion" screen of the dedicated software, the element interval was set to logarithmic particle size, the particle size elements to 256, and the particle size range to 2 μm to 60 μm.

[0205] The specific measurement method is as follows.

[0206] (1) Add approximately 200 ml of electrolyte aqueous solution to a 250 mL round-bottom beaker dedicated to the Multisizer 3. Place the beaker on the sample stage and stir counterclockwise with a stirring rod at a speed of 24 seconds per revolution. Then, use the "Bore Rinse" function in the dedicated software to preliminarily remove dirt and bubbles from the bore.

[0207] (2) 30 ml of the same electrolyte aqueous solution was placed in a 100 mL flat-bottom glass beaker, and about 0.3 ml of a dilution solution obtained by diluting three times the mass of "Contaminon N" (a 10 mass % aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments comprising a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries) with ion-exchanged water was added.

[0208] (3) A specific amount of ion-exchanged water was placed in a water tank of an ultrasonic disperser (Ultrasonic Dispersion System Tetora 150, Nikkaki Bios) having a power output of 120 W and equipped with two oscillators having an oscillation frequency of 50 kHz and a phase shift of 180° from each other, and about 2 ml of Contaminon N was added to the water tank.

[0209] (4) Place the beaker in (2) above in the beaker fixing hole of the ultrasonic disperser and start the ultrasonic disperser. Adjust the vertical position of the beaker so that the liquid surface resonance state of the electrolyte aqueous solution in the beaker is maximized.

[0210] (5) The electrolyte aqueous solution in the beaker of (4) is exposed to ultrasonic waves, and approximately 10 mg of the toner (particles) is added little by little to the electrolyte aqueous solution and dispersed. Then, ultrasonic dispersion is continued for another 60 seconds. During ultrasonic dispersion, the water temperature in the tank is appropriately adjusted to 10°C to 40°C.

[0211] (6) The electrolyte aqueous solution in which the toner (particles) is dispersed in (5) is added dropwise to the round-bottom flask set on the sample stand in (1) using a pipette and adjusted to a measurement concentration of about 5%. Measurement is then performed until the number of particles measured reaches 50,000.

[0212] (7) Analyze the measurement data using the dedicated software included with the device and calculate the weight-average particle size (D4). When the graph / volume % is set in the dedicated software, the "Average Diameter" on the "Analysis / Volume Statistics (Arithmetic Mean)" screen is the weight-average particle size (D4). Example

[0213] The basic structure and features of the present invention have been described above, but the invention of the present application will be described in detail below based on examples. However, the present invention is not limited thereto. Unless otherwise specified, parts and % are based on mass.

[0214] <Production Example of First Resin 1 (Crystalline Resin 1)>

[0215] -Solvent: 100.0 parts of toluene

[0216] - 100.0 parts of monomer composition

[0217] (The monomer composition is a mixture of the following behenyl acrylate, acrylonitrile and styrene in the proportions shown below).

[0218] (Behenyl acrylate 60.0 parts)

[0219] (10.0 parts of acrylonitrile)

[0220] (27.5 parts of styrene)

[0221] - 0.5 parts of polymerization initiator

[0222] [tert-Butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV)]

[0223] Under a nitrogen atmosphere, the above materials are placed in a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube. While stirring at 200 rpm, the interior of the reaction vessel is heated to 70 ° C, and polymerization reaction is carried out for 12 hours to obtain a solution in which the polymer of the monomer composition is dissolved in toluene. Subsequently, after the temperature of the solution is reduced to 25 ° C, the solution is poured into 1000.0 parts of methanol while stirring to precipitate the methanol insoluble matter. The obtained methanol insoluble matter is filtered out, further washed with methanol, and then vacuum dried at 40 ° C for 24 hours. Thereby obtaining the first resin 1 (crystalline resin 1). The weight average molecular weight (Mw) of the first resin 1 (crystalline resin 1) is 34,000, and the melting point (Tp) is 61 ° C.

[0224] When the first resin 1 (crystalline resin 1) was analyzed by NMR, it was found that the first resin included 60.0 parts of monomer units derived from behenyl acrylate, 10.0 parts of monomer units derived from acrylonitrile, and 27.5 parts of monomer units derived from styrene in a mass ratio. In addition, the SP value (unit: (J / cm)) of the crystalline resin 1 was calculated. 3 ) 0.5 ).

[0225] <Production Example of First Resins 2 to 9 (Crystalline Resins 2 to 9)>

[0226] First resins 2 to 9 (crystalline resins 2 to 9) were obtained by conducting reactions in the same manner as in the production example of the first resin 1 (crystalline resin 1) except that each monomer and mass fraction were changed as shown in Table 1.

[0227] [Table 1]

[0228]

[0229] The abbreviations in Table 1 are as follows. The values ​​in parentheses are SP values ​​(J / cm 3 ) 0.5 .

[0230] BEA: Behenyl acrylate (SP value: 18.3)

[0231] SA: Stearyl acrylate (SP value: 18.4)

[0232] MYA: Myristyl acrylate (SP value: 18.1)

[0233] GEA: tetratriacontyl acrylate (SP value: 18.0)

[0234] AN: Acrylonitrile (SP value: 29.4)

[0235] AA: Acrylic acid (SP value: 28.7)

[0236] MN: Methacrylonitrile (SP value: 27.5)

[0237] St: Styrene (SP value: 20.1)

[0238] <Production Example of First Resin 10 (Crystalline Resin 10)>

[0239] -1,12-Dodecanediol: 46.5 parts

[0240] - Dodecanedioic acid: 53.3 parts

[0241] -2-Ethylhexanoate tin: 0.5 parts

[0242] The above materials were weighed into a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen inlet tube, and a thermocouple. After purging the interior of the flask with nitrogen, the temperature was gradually increased while stirring, and the reaction was carried out at a temperature of 140°C while stirring for 3 hours. Next, the pressure in the reaction vessel was reduced to 8.3 kPa, and the reaction was carried out while maintaining the temperature at 200°C for 4 hours. Then, the interior of the reaction vessel was depressurized to below 5 kPa, and the reaction was carried out at 200°C for 3 hours, thereby obtaining crystalline resin 10.

[0243] <Production Example of Second Resin 1 (Amorphous Resin 1)>

[0244] A total of 50.0 parts of xylene was placed in an autoclave, which was subsequently purged with nitrogen and then heated to 185°C in a sealed state under stirring. While the temperature inside the autoclave was controlled at 185°C, a mixed solution of 80.7 parts of styrene, 17.8 parts of n-butyl acrylate, 1.1 parts of divinylbenzene, 0.5 parts of acrylic acid, 1.5 parts of di-tert-butyl peroxide, and 20.0 parts of xylene was continuously added dropwise for 3 hours to perform polymerization. Further, the polymerization was completed by maintaining the same temperature for 1 hour, and the solvent was removed to obtain a second resin 1 (amorphous resin 1). The weight average molecular weight (Mw) of the second resin 1 (amorphous resin 1) was 40,000, and the softening temperature (Tm) was 100°C.

[0245] <Production Example of Second Resin 2 (Amorphous Resin 2)>

[0246] Second resin 2 (non-crystalline resin 2) was obtained by reacting in the same manner as in the production example of second resin 1 (non-crystalline resin 1), except that the amount of di-tert-butyl peroxide was changed from 1.5 parts to 4.0 parts. The weight average molecular weight (Mw) of second resin 2 (non-crystalline resin 2) was 15,000, and the softening temperature (Tm) was 70°C.

[0247] <Production Example of Second Resin 3 (Amorphous Resin 3)>

[0248] Second resin 3 (non-crystalline resin 3) was obtained by reacting in the same manner as in the production example of second resin 1 (non-crystalline resin 1), except that the amount of di-tert-butyl peroxide was changed from 1.5 parts to 5.0 parts. The weight average molecular weight (Mw) of second resin 3 (non-crystalline resin 3) was 10,000, and the softening temperature (Tm) was 65°C.

[0249] <Production Example of Second Resin 4 (Amorphous Resin 4)>

[0250] (Formula of polyester resin 1)

[0251]

[0252]

[0253] A total of 90 parts of a mixture of monomers for producing polyester resin 1 was placed in a four-necked flask. A decompression device, a water separator, a nitrogen gas introduction device, a temperature measuring device, and a stirring device were then installed, and stirring was performed at 160°C in a nitrogen atmosphere. Here, 10 parts of vinyl-based polymerizable monomers (81.0 parts of styrene, 17.0 parts of n-butyl acrylate, 0.9 parts of acrylic acid, and 1.1 parts of divinylbenzene) for producing the vinyl-based resin and 1 part of benzoyl peroxide as a polymerization initiator were added dropwise from a dropping funnel over 4 hours, and the mixture was reacted at 160°C for 5 hours. The temperature was then raised to 230°C, 0.2 parts of tetrabutoxytitanium was added to the total amount of monomers for producing the polyester resin, and polymerization was performed until the softening temperature reached 115°C. After the reaction was complete, the mixture was removed from the container, cooled, and pulverized to obtain second resin 4 (amorphous resin 4).

[0254] <Production Example of Toner 1>

[0255]

[0256] A Henschel mixer (FM-75 model, manufactured by Nippon Coke Industries Co., Ltd.) was used for 20 s. -1 The above materials were mixed at a speed of 250 rpm and a rotation time of 5 minutes, and then mixed with a twin-screw mixer (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.) with a temperature setting of 130°C at a screw speed of 250 rpm and a discharge temperature of 130°C. The obtained mixed product was rolled while cooling through a drum flaker (MBD30-30, manufactured by Nippon Coke Co., Ltd.). The temperature of the cooling water was set to 15°C, and the conditions were set so that the thickness of the resin composition after rolling and cooling was 1.0 mm. The time from melting until the melting point Tp of the first resin was reached was (10 seconds), and the cooling rate from rolling until the melting point Tp of the first resin was reached was (7°C / second).

[0257] The coarsely pulverized product was obtained by coarsely pulverizing to 1 mm or less using a hammer mill. The coarsely pulverized product obtained was finely pulverized using a mechanical pulverizer (T-250, manufactured by Freund-Turbo Corporation). Then, classification was performed using Faculty F-300 (manufactured by Hosokawa Micron Corporation) to obtain toner particles 1 having a weight-average particle size of about 6.0 μm. The operating conditions were a rotation speed of the classification rotor of 130 s -1 and dispersion rotor speed 120s -1 .

[0258] A total of 0.5 parts of the precipitate surface-treated with 4% by mass of hexamethyldisilazane had a BET specific surface area of ​​25 m 2 / g of hydrophobic silica fine particles and 0.5 parts of a 10% by mass polydimethylsiloxane surface-treated particle having a BET specific surface area of ​​100 m 2 / g of hydrophobic silica fine particles are added to 100 parts of Toner Particles 1 and mixed with a Henschel mixer (FM-75 type, manufactured by Nippon Coke Industries Co., Ltd.) for 30 seconds. -1 The mixture was mixed at a rotation speed of 0.05 and a rotation time of 10 minutes to obtain Toner 1. Based on the above method, the produced Toner 1 was cross-sectionally observed, and the domain matrix structure, the average major diameter of the domain, the standard deviation of the angle in the longitudinal direction of the domain, and La / Lb were evaluated, and the results are shown in Table 3.

[0259] <Production Examples of Toners 2, 6 to 8, and 23 to 28>

[0260] Toners 2, 6 to 8, and 23 to 28 were obtained in the same manner as in the production example of Toner 1, except that the first resin and the second resin were changed to the resins shown in Table 2. Table 3 shows the evaluation results of Toners 2, 6 to 8, and 23 to 28.

[0261] <Production Examples of Toners 3 to 5>

[0262] Toners 3 to 5 were obtained in the same manner as in the production example of Toner 1, except that the cooling water temperature during rolling and cooling was changed to the conditions shown in Table 2. Table 3 shows the evaluation results of Toners 3 to 5.

[0263] <Production Examples of Toners 9 to 14>

[0264] Toners 9 to 14 were obtained in the same manner as in Production Example of Toner 1, except that the ratio of the first resin to the second resin was changed to the conditions shown in Table 2. Table 3 shows the evaluation results of Toners 9 to 14.

[0265] <Production Example of Toners 15 and 16>

[0266] Toners 15 and 16 were obtained in the same manner as in the Production Example of Toner 1, except that the second resin was changed to the resin shown in Table 2 and Wax 1 was changed to the following Wax 2.

[0267] - Wax 2 5.0 parts

[0268] (Microcrystalline wax; melting point 65°C)

[0269] Table 3 shows the evaluation results of Toners 15 and 16.

[0270] <Production Examples of Toners 17 to 22>

[0271] Toners 17 to 22 were obtained in the same manner as in Production Example of Toner 1, except that the screw rotation speed and discharge temperature were changed to the conditions shown in Table 2 as the operating conditions of the twin-screw kneader (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.).

[0272] [Table 2]

[0273]

[0274] The crystalline resin and the non-crystalline resin used in the toners other than Toner 26 in Table 2 used a combination in which the crystalline resin and the non-crystalline resin were incompatible when the melt-kneaded product melt-kneaded at 150°C was observed at 150°C.

[0275] <Production Example of Toner 29>

[0276] An emulsion polymerization method was used to produce Toner 29. First, each dispersion liquid was produced by the following method.

[0277] <Production Example of Crystalline Resin 1 Fine Particle Dispersion>

[0278] -Toluene (manufactured by Wako Pure Chemical Industries, Ltd.) 300 parts

[0279] -Crystalline resin 1 100 parts

[0280] The above materials were weighed and mixed and dissolved at 100 ° C. Separately, 5.0 parts of sodium dodecylbenzenesulfonate and 10.0 parts of sodium laurate were added to 700 parts of ion exchange water and dissolved by heating at 100 ° C. Next, the toluene solution and the aqueous solution were mixed and stirred at 7000 rpm using an ultra-high-speed stirrer TK ROBOMIX (manufactured by PRIMIX Corporation). Further, high-pressure impact disperser NANOMIZER (manufactured by Yoshida Kikai Co., Ltd.) was used to emulsify under a pressure of 200 MPa. Then, toluene was removed using an evaporator, and the concentration was adjusted with ion exchange water to obtain an aqueous dispersion (crystalline resin 1 fine particle dispersion) having a concentration of 20% by mass of crystalline resin 1 fine particles. The 50% particle diameter (D50) based on volume distribution of the crystalline resin 1 was measured using a dynamic light scattering type particle size distribution meter NANOTRACK UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.40 μm.

[0281] <Production Example of Non-Crystallinity Resin 1 Fine Particle Dispersion>

[0282] -Tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) 300 parts

[0283] - Non-crystalline resin 1 100 parts

[0284] - 0.5 parts of anionic surfactant NEOGEN RK (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)

[0285] The above materials were weighed, mixed and dissolved. Next, 20.0 parts of 1 mol / L ammonia water were added and stirred at 4000 rpm using an ultra-high speed stirrer TKROBOMIX (manufactured by PRIMIX Corporation). Further, 700 parts of ion exchange water were added at a rate of 8 g / min to precipitate the fine particles of the non-crystalline resin 1. Then, tetrahydrofuran was removed using an evaporator, and the concentration was adjusted with ion exchange water to obtain an aqueous dispersion (non-crystalline resin 1 fine particle dispersion) having a concentration of 20% by mass of the fine particles of the non-crystalline resin 1. The 50% particle size (D50) of the fine particles of the non-crystalline resin 1 based on volume distribution was 0.14 μm.

[0286] <Production Example of Wax Fine Particle Dispersion>

[0287] - Wax 1 100.0 parts

[0288] (Fischer-Tropsch wax; the peak temperature of the maximum endothermic peak is 90°C)

[0289] - 5 parts of anionic surfactant NEOGEN RK (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)

[0290] - 395 parts of ion exchange water

[0291] The above materials were weighed, put into a mixing container equipped with a stirrer, heated to 90° C., circulated to CLEAREMIX W-MOTION (manufactured by M-Technique Co., Ltd.), and subjected to dispersion treatment for 60 minutes. The conditions for the dispersion treatment were as follows.

[0292] -Rotor outer diameter: 3cm

[0293] - Clearance: 0.3mm

[0294] -Rotor speed: 19000r / min

[0295] -Screen speed: 19000r / min

[0296] After the dispersion treatment, cooling was performed to 40° C. under cooling conditions of a rotor speed of 1000 r / min, a mesh speed of 0 r / min, and a cooling rate of 10° C. / min to obtain an aqueous dispersion (wax fine particle dispersion) having a wax fine particle concentration of 20% by mass. The 50% particle diameter (D50) of the wax fine particles based on volume distribution was measured using a dynamic light scattering particle size distribution meter NANOTRACK UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and was found to be 0.15 μm.

[0297] <Production Example of Colorant Fine Particle Dispersion Liquid>

[0298] - Colorant 1 50.0 parts

[0299] (Cyan pigment: Pigment Blue 15:3, manufactured by Dainichiseika Color & Chem MFG Co., Ltd.)

[0300] - 7.5 parts of anionic surfactant NEOGEN RK (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)

[0301] - 442.5 parts of ion exchange water

[0302] The above materials were weighed, mixed, dissolved, and dispersed for about 1 hour using a high-pressure impact disperser NANOMIZER (manufactured by Yoshida Kikai Co., Ltd.) to obtain an aqueous dispersion (colorant fine particle dispersion) in which the colorant was dispersed and the concentration of the colorant fine particles was 10% by mass. The 50% particle diameter (D50) of the colorant fine particles based on volume distribution was measured using a dynamic light scattering particle size distribution meter NANOTRACKUPA-EX150 (manufactured by Nikkiso Co., Ltd.) and was found to be 0.20 μm.

[0303] Toner particles were produced by the following method using each dispersion produced by the above method.

[0304] <Production Example of Toner Particles>

[0305]

[0306] The materials other than the above-mentioned post-treatment crystalline resin 1 fine particle dispersion are placed in a round stainless steel flask and mixed. Subsequently, a homogenizer ULTRA-TURRAX T50 (manufactured by IKA Works Inc.) is used to disperse at 5000r / min for 10 minutes. After adding 1.0% nitric acid aqueous solution and adjusting the pH to 3.0, a stirring blade is used in a water bath for heating, and heating is performed to 58°C while appropriately adjusting the number of revolutions of the stirred mixed solution. Coulter Multisizer III is used to appropriately confirm the formed aggregated particles and maintain them until the weight-average particle size (D4) becomes about 6.4 μm. Then, a post-treatment crystalline resin 1 fine particle dispersion is added, which is then continued to be maintained for 30 minutes, and then the pH is adjusted to 9.0 using 5% sodium hydroxide aqueous solution.

[0307] Thereafter, the mixture was heated to 75°C while continuing to stir. The aggregated particles were then fused by holding the mixture at 75°C for 1 hour. The mixture was then cooled to 50°C and held for 3 hours to promote crystallization of the resin. After cooling to 25°C, the mixture was filtered, solid-liquid separated, thoroughly washed with ion-exchanged water, and dried to obtain toner particles 29. Toner particles 29 were subjected to the same external addition treatment as toner 1 to obtain toner 29. The weight-average particle size (D4) of toner 29 was approximately 6.0 μm.

[0308] Table 3 shows the evaluation results of Toner 29.

[0309] [Table 3]

[0310]

[0311] The area ratio of the matrix of the toner particles 9 is the area ratio when the matrix is ​​a non-crystalline resin. The "standard deviation of domain angles" represents the standard deviation of angles in the longitudinal direction of the domains.

[0312] <Manufacturing Example of Magnetic Carrier 1>

[0313] The magnetization intensity of magnetite with a number average particle size of 0.30 μm in a magnetic field of 1000 / 4π(kA / m) is 65 Am 2 / kg)

[0314] The magnetization intensity of magnetite 2 (1000 / 4π(kA / m) with a number average particle size of 0.50 μm) is 65 Am 2 / kg)

[0315] 4.0 parts of a silane compound (3-(2-aminoethylaminopropyl)trimethoxysilane) was added to 100 parts of each of the above materials, and mixed and stirred at a high speed at 100° C. or higher in a container to process each fine particle.

[0316] Phenol: 10% by mass

[0317] Formaldehyde solution: 6% by mass

[0318] (Formaldehyde 40% by mass, methanol 10% by mass, water 50% by mass)

[0319] Magnetite treated with silane compound 1: 58 mass%

[0320] Magnetite treated with a silane compound 2: 26% by mass

[0321] 100 parts of these materials, 5 parts of 28% by mass ammonia aqueous solution and 20 parts of water were put into a flask and stirred and mixed with heating to 85° C. for 30 minutes and maintained for 3 hours to perform polymerization reaction and harden the resulting phenolic resin.

[0322] The hardened phenolic resin was then cooled to 30°C, water was added, the supernatant was removed, and the precipitate was washed with water and air-dried. It was then dried at 60°C under reduced pressure (5 mmHg or less) to obtain a magnetic-dispersed spherical magnetic carrier 1. The volume-based 50% particle size (D50) of the magnetic carrier 1 was 34.2 μm.

[0323] <Production Example of Two-Component Developer 1>

[0324] A total of 8.0 parts of Toner 1 is added to 92.0 parts of Magnetic Carrier 1 and mixed with a V-type mixer (V-20, manufactured by Seishin Enterprise Co., Ltd.), whereby a two-component developer 1 is obtained.

[0325] <Production Examples of Two-Component Developers 2 to 29>

[0326] Two-component developers 2 to 29 were obtained in the same manner as in the production example of the two-component developer 1, except that the toner 1 was changed to the toners 2 to 29, respectively.

[0327] <Example 1>

[0328] Use two-component developer 1 to be evaluated. As image forming apparatus, the imageRUNNER ADVANCE C5560 of Canon printer for digital commercial printing of transformation is used, and two-component developer 1 is placed in the developing device of cyan. The transformation printer makes it possible to freely set the fixing temperature, process speed, DC voltage VDC of developer carrying member, charging voltage VD of electrostatic latent image carrying member and laser power. In image output evaluation, the FFh image (solid image) with the desired image ratio is output, VDC, VD and laser power are adjusted to obtain the desired toner carrying amount on the FFh image on paper, and the following evaluation is performed. FFh is a value showing 256 grayscales in hexadecimal, 00h is the first grayscale (white background portion) in 256 grayscales, and FFh is the 256th grayscale (solid portion) in 256 grayscales. Evaluate based on the following evaluation method, and the result is shown in Table 4.

[0329] <Low-temperature fixability>

[0330] -Paper: GFC-081(81.0g / m 2 )

[0331] (Sold by Canon Marketing Japan Inc.)

[0332] -Toner loading on paper: 0.70 mg / cm 2

[0333] (Adjusted by the DC voltage VDC of the developer carrying member, the charging voltage VD of the electrostatic latent image bearing member, and the laser power)

[0334] - Evaluation image: 2cm x 5cm image located in the center of A4 paper

[0335] -Test environment: Low temperature and low humidity environment: Temperature 15°C / Humidity 10% RH (hereinafter referred to as "L / L")

[0336] -Fixing temperature: 140℃

[0337] -Processing speed: 400mm / s

[0338] The above evaluation images were output and the low-temperature fixing properties were evaluated. The value of the image density reduction rate was used as an evaluation index for the low-temperature fixing properties. For the image density reduction rate, first, the image density of the center portion was measured using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite, Inc.). Next, at 4.9 kPa (50 g / cm 2 ) was applied to the portion where the image density was measured, the fixed image was rubbed with Sylbon paper (5 reciprocating times), and the image density was measured again. The image density reduction rate during rubbing was then calculated using the following formula. The obtained image density reduction rate was evaluated according to the following evaluation criteria.

[0339] Image density reduction rate = [(image density before rubbing) – (image density after rubbing)] / (image density before rubbing) × 100

[0340] (Evaluation Criteria)

[0341] AA: Image density reduction rate is less than 1.0%

[0342] A: Image density reduction rate is 1.0% or more and less than 3.0%

[0343] B: Image density reduction rate is 3.0% or more and less than 5.0%

[0344] C: Image density reduction rate is 5.0% or more and less than 8.0%

[0345] D: Image density reduction rate is 8.0% or more

[0346] <Fixing Separability>

[0347] -Paper: CS-052(52.0g / m 2 )

[0348] (Sold by Canon Marketing Japan Inc.)

[0349] -Toner loading on paper: 0.60 mg / cm 2

[0350] (Adjusted by the DC voltage VDC of the developer carrying member, the charging voltage VD of the electrostatic latent image bearing member, and the laser power)

[0351] - Evaluation image: A 2 cm x 20 cm image located at the long end of an A4 paper in the paper feed direction, with a margin of 1.5 mm from the leading end of the paper

[0352] -Test environment: High temperature and high humidity environment: Temperature 30°C / Humidity 80% RH (hereinafter referred to as "H / H")

[0353] - Fixing temperature: from 140℃, increase by 5℃

[0354] -Processing speed: 400mm / s

[0355] The evaluation image was output, and the wrapping resistance was evaluated according to the following criteria at the maximum fixing temperature at which wrapping did not occur.

[0356] (Evaluation Criteria)

[0357] AA: above 175℃

[0358] A: 165℃ or higher and less than 175℃

[0359] B: 155℃ or higher and less than 165℃

[0360] C: 145℃ or higher and less than 155℃

[0361] D: less than 145℃

[0362] <Examples 2 to 24 and Comparative Examples 1 to 5>

[0363] The evaluation was performed in the same manner as in Example 1, except that two-component developers 2 to 29 were used instead of two-component developer 1. The evaluation results are shown in Table 4.

[0364] [Table 4]

[0365]

[0366] While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments.The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions.

Claims

1. A toner comprising toner particles, wherein the toner particles comprise: Binder resin and release agent, characterized in that The binder resin includes a first resin and a second resin; The first resin is a crystalline resin having a melting point Tp of 50° C. to 90° C.; The second resin is a non-crystalline resin; In a cross section of the toner particle observed by a transmission electron microscope, The toner particles have a cross-section having a matrix-domain structure composed of a matrix including the first resin and domains including the second resin; an area ratio of the matrix in the total area of ​​the cross section of the toner particle of 35 to 70 area %; and When the longest direction of each of the domains is defined as the longitudinal direction, the standard deviation of angles of the domains in the longitudinal directions is 25° or less. 2 . The toner according to claim 1 , wherein the softening temperature Tm of the second resin is higher than the melting point Tp of the first resin by 10° C. or more. 3 . The toner according to claim 1 , wherein an area ratio of the matrix is ​​60 area % or less of a total area of ​​a cross section of the toner particle. 4 . The toner according to claim 1 , wherein an average length of the domains in the longitudinal direction is from 20 nm to 500 nm in observation of a cross section of the toner. 5 . The toner according to claim 1 , wherein in observation of a cross section of the toner, a ratio La / Lb of a length La of the domain in the longitudinal direction to a maximum length Lb in a direction perpendicular to the longitudinal direction is 8.0 or less.

6. The toner according to claim 1 or 2, wherein the first resin includes a first monomer unit represented by the following formula (1): In formula (1), R Z1 represents a hydrogen atom or a methyl group, and R 1 It represents an alkyl group having 18 to 36 carbon atoms.

7. The toner according to claim 1 or 2, wherein The first resin includes a vinyl resin, and The second resin includes a styrene acrylic resin. 8 . The toner according to claim 1 , wherein the releasing agent comprises a hydrocarbon wax.

9. A method for producing a toner according to any one of claims 1 to 8, characterized in that: The method comprises: a melt-kneading step of melt-kneading a composition including a binder resin comprising the first resin and the second resin and the release agent to obtain a melt-kneaded product; a cooling and solidifying step of cooling and solidifying the melt-kneaded product to obtain a cooled solidified product, and a pulverizing step of pulverizing the cooled solidified product to obtain a pulverized product, wherein The melt-kneaded product is rolled while being cooled during cooling and solidification.

10. The method for producing a toner according to claim 9, wherein the first resin and the second resin are a combination in which, when a melt-kneaded product obtained by melt-kneading a mixture of the first resin and the second resin at 150° C. is observed at 150° C., the first resin and the second resin are incompatible.

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