JP6448392B2 - Toner production method - Google Patents

Description

  The present invention relates to a toner used in an electrophotographic system, an electrostatic recording system, an electrostatic printing system, and a toner jet system.

  In recent years, with the widespread use of electrophotographic full-color copiers, further higher image quality and energy savings are required. In particular, in the POD market, due to the high process speed and the large number of printed sheets, there is a demand for a toner having higher stress resistance than ever and a toner having stable charging performance. When high stress is applied to the toner, the inorganic fine powder (external additive) on the toner surface is buried in the toner base and the spacer effect is weakened. Therefore, the toner is attached to the object (carrier, photosensitive drum, intermediate transfer member, etc.). Adhesion increases, leading to deterioration of developability and transferability. In particular, if a large amount of external additives having a small particle size is used, the toner is easily buried, and the spacer effect cannot be maintained, resulting in a toner having low stress resistance.

  In order to improve this, Patent Document 1 attempts to maintain a spacer function after applying stress by coating a toner base with a large particle size monodispersed spherical external additive. However, the external additive having a large particle size is easily detached from the surface of the base material, and the detached external additive adheres to the surface of the development carrier, and the triboelectric charging performance with the toner is lowered, causing the toner charge amount to be lowered. Further, it may adhere to a member such as a charging roller and cause an image defect.

  Patent Document 2 discloses a method of immobilizing a large particle size inorganic fine powder on the surface of toner particles by applying strong shearing in the gap between the rotation drive unit and the casing in the external additive mixing tank. However, this method is not always effective when the toner particles have an uneven shape like pulverized toner. There is a possibility that the inorganic fine powder rolls into the concave portions of the toner particles due to a strong shearing force in the gap between the rotation drive unit and the casing, and the function as an external additive cannot be sufficiently performed.

  In Patent Document 3, there is an example in which non-spherical amorphous silica having a large particle size is externally added in order to achieve both suppression of burying and rolling as described above. However, it is difficult to uniformly adhere such an external additive to the surface of the base material in a highly diffusible state, and it is difficult to achieve both excellent spacer effect and separation through durability.

  From the above, there is still room for improvement regarding the durability stability of the toner, in particular, the compatibility between the maintenance of the spacer effect by the external additive and the removal of the external additive.

JP 2002-318467 A JP 2008-292675 A JP 2007-279702 A

  The object of the present invention is to satisfy a stable durability throughout. In particular, (1) the external additive is buried in the toner base and the spacer function cannot be performed, and the adhesion force increases (developability and transferability deteriorates), and (2) the external additive is released from the toner surface. It is an object of the present invention to provide a toner that prevents adhesion to a carrier surface and a decrease in chargeability.

The present invention is a method for producing a toner containing toner particles containing a binder resin and organic-inorganic composite particles,
The method for producing the toner includes:
Mixing the toner base particles containing the binder resin and the organic-inorganic composite particles; and
A step of fixing the organic-inorganic composite particles to the surface of the toner base particles by surface treatment with hot air to obtain toner particles having the organic-inorganic composite particles fixed to the surface;
Have
The organic-inorganic composite particles have a number average particle size of 50 nm to 200 nm, and the organic-inorganic composite particles have a structure in which inorganic fine particles are embedded in vinyl-based resin particles. There are a plurality of convex portions derived from inorganic fine particles,
The present invention relates to a toner manufacturing method .

  According to the present invention, it is possible to provide a toner that exhibits excellent development stability and transfer stability through durability.

FIG. 3 is a cross-sectional view of the toner of the present invention using an electron beam transmission microscope. FIG. 3 is a diagram showing a major axis length and a minor axis length of a crystalline polyester in a toner cross section of the toner of the present invention by an electron beam transmission microscope. It is a 1.0 micrometer x 1.0 micrometer visual field after the binarization in the toner cross section by the electron beam transmission microscope of the toner of this invention. It is a figure of the thermal spheronization processing apparatus used for this invention.

  The toner of the present invention is a toner containing toner particles containing a binder resin and organic-inorganic composite particles. The surface of the toner particles is fixed by heat treatment of the organic-inorganic composite particles. The inorganic composite particles have a number average particle diameter of 50 nm or more and 200 nm or less, and the organic / inorganic composite particles have a structure in which inorganic fine particles are embedded in vinyl resin particles, and inorganic fine particles are formed on the surface of the organic / inorganic composite particles. There are a plurality of convex portions derived from the above.

  In order to exhibit excellent durability stability, it is necessary to maintain the spacer effect by inorganic fine particles (also referred to as external additives) throughout. If there is no spacer effect, the toner base comes in direct contact with the object (development carrier, photosensitive drum, intermediate transfer member, etc.), and the non-electrostatic adhesion force between the toner and the object becomes large. Then, the responsiveness due to the electric field is deteriorated, leading to a decrease in developability, a decrease in transfer efficiency / a generation of a transfer margin, and the like. The maintenance of the spacer effect is achieved by suppressing the embedding and liberation of the external additive on the base material surface. In order to prevent the embedding, it is advantageous to use an external additive having a large particle diameter, but the external additive having a large particle diameter is easily detached from the toner surface. In order to prevent this detachment, if an external addition device is used to strongly fix the toner base to the toner base, a phenomenon occurs in which the external additive gathers in the concave and convex portions of the base. In particular, when an irregular toner base such as a mechanically pulverized toner is used, the external additive tends not to adhere to the convex portion of the toner base and concentrates on the concave portion. In addition, this phenomenon is more likely to occur as the particle size of the external additive becomes larger and close to a spherical shape.

  The external additive can exhibit its function more effectively when it is uniformly diffused and adhered to the toner surface. When an irregular toner base is used, the external additive gathers in the concave portion, so that it is difficult to adhere the external additive to the convex portion. However, since the convex portion mainly comes into contact with the object, it is important to attach the external additive to the convex portion in a highly diffusible state. On the other hand, the external additive attached to the concave portion does not effectively exhibit the spacer function or the charge imparting function.

  In the present invention, by using organic-inorganic composite particles having a plurality of convex portions derived from inorganic fine particles, the particles can be adhered in a state where the diffusibility to the toner surface is enhanced. This is thought to be due to the fact that the fine irregularities formed by the inorganic fine particle components of the organic-inorganic composite particles used in the present invention are effective. The inventor thinks that the unevenness between the organic-inorganic composite particles prevents aggregation between the organic-inorganic composite particles and has an appropriate catch on the toner surface, so that the bias to the base recess does not occur. It is important that there are a plurality of convex portions derived from inorganic fine particles like the organic-inorganic composite particles used in the present invention. For example, it is uniform if the inorganic fine particles are completely embedded in the resin particles and there are no convex portions. Diffusivity cannot be expected. The organic-inorganic composite particles used in the present invention have a shape like so-called confetti.

  On the other hand, it is necessary to suppress the release (release) of the external additive as a condition of the toner having excellent durability stability. When the external additive is detached, it adheres to the surface of the developing carrier, and the triboelectric chargeability between the toner and the carrier is lowered, resulting in a decrease in the charge amount of the toner. In the present invention, since the external additive can be thermally fixed to the toner surface by the hot air treatment, it is possible to create a state resistant to separation. In the present invention, since the organic-inorganic composite particles having the characteristics as described above are used, the particles can be adhered to the toner base surface in a highly diffusible state. Since the position can be fixed / fixed by hot air treatment in this state, the toner of the present invention can realize an excellent spacer function and chargeability for a long period of time.

  In addition, since the organic-inorganic composite particles of the present invention have a resin component, the fixing performance by hot air treatment is higher than those composed only of inorganic particles. This is because the resin component has a higher thermal conductivity than the inorganic substance, and is thus easily fixed.

  The organic-inorganic composite particles used in the present invention can exhibit excellent durability by using particles having a number average particle diameter of 50 nm to 200 nm. When the number average particle diameter is less than 50 nm, the spacer function is weakened and the effect expected in the present invention is not achieved. On the other hand, if it exceeds 200 nm, the external additive detachment easily occurs in the hot air treatment apparatus, which is not suitable.

  In the present invention, a crystalline polyester is contained in the toner base, and a higher-performance toner can be obtained depending on the dispersion state of the crystalline polyester. Specifically, in the transmission electron microscope (TEM) cross section of the toner particles treated with ruthenium dye, the crystalline polyester forms crystals that are observed in a needle shape on the cross section of the toner particles, and the long axis of the crystals When the number average diameter (D1) of the length is 60 nm or more and 250 nm or less and the area occupied by the crystalline polyester in the toner particles in a 1.0 μm × 1.0 μm visual field in the cross section of the toner particles is determined, When a toner having a standard deviation of area of 10.0% or less is used, higher external additive diffusion performance is exhibited.

  If the crystalline polyester is finely dispersed in the above state, it can be said that the crystalline polyester is also finely dispersed on the surface of the toner base. Then, it is considered that the crystalline polyester present on the surface becomes wedges, and the organic / inorganic fine particles are fixed together with the convex portions of the organic / inorganic composite particles, and high diffusibility is obtained. If the number average diameter (D1) of the major axis length of the crystal is less than 60 nm, the expected diffusivity could not be obtained because the crystal diameter was too small. If the thickness exceeds 250 nm, the dispersion is not finely dispersed, so that the expected diffusivity cannot be obtained.

  The diffusibility can be visually grasped by SEM described later, or the external additive coverage is measured using ESCA, and in the case of the same number of added external additives, it is determined that the diffusivity is high when the coverage is high. I can do it.

  The organic-inorganic composite particles used in the present invention can be produced, for example, according to the description of Examples in WO2013 / 063291.

  The number average particle size and shape of the organic-inorganic composite particles can be adjusted by changing the particle size of the inorganic fine particles used in the organic-inorganic composite particles or the amount ratio of the inorganic fine particles to the resin.

  These organic / inorganic composite particles are preferably 2.0 parts by mass or more and 15.0 parts by mass or less, and 3.0 parts by mass or more and 10.0 parts by mass or less with respect to 100.00 parts by mass of the toner base. More preferred. When the amount is less than 2.0 parts by mass, the spacer function expected in the present invention is not effectively expressed. If the amount is more than 15.0 parts by mass, the level of particle detachment will be poor even when it is fixed using hot air treatment.

<Inorganic particles (external additives)>
Other inorganic fine particles that can be used in the present invention include, for example, fluorine-based resin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder, titanium oxide fine powder, alumina fine powder, wet-process silica, and dry-process silica. Fine powder silica, and treated silica obtained by subjecting them to surface treatment with a silane compound, an organosilicon compound, a titanium coupling agent, silicone oil, or the like.

  As the silica that can be used in the present invention, both wet process silica and dry process silica can be used. As a wet process silica, in particular, a sol-gel method in which a solvent is removed from a silica sol suspension obtained by hydrolysis and condensation reaction with a catalyst in an organic solvent in which water is present, and then dried to form particles. There are silica particles that are produced. The silica particles produced by the sol-gel method have a sharp particle size distribution of the obtained particles, and approximately spherical particles are obtained, and particles having a desired particle size distribution can be obtained by changing the reaction time. Preferably used.

The dry process silica is a fine powder produced by vapor phase oxidation of a silicon halogen compound, which is called so-called dry process silica or fumed silica, and is manufactured by a conventionally known technique. . For example, a thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame is used, and the basic reaction formula is as follows.
SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl

  In this production process, it is also possible to obtain a composite fine powder of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride or titanium chloride together with silicon halogen compounds. .

  In the case of titanium oxide fine powder, fine particles of titanium oxide obtained by low-temperature oxidation (thermal decomposition, hydrolysis) of sulfuric acid method, chlorine method, volatile titanium compounds such as titanium alkoxide, titanium halide, titanium acetylacetonate are used. . As the crystal system, any of anatase type, rutile type, mixed crystal type thereof, and amorphous type can be used.

  And if it is alumina fine powder, buyer method, improved buyer method, ethylene chlorohydrin method, underwater spark discharge method, organoaluminum hydrolysis method, aluminum alum pyrolysis method, ammonium aluminum carbonate pyrolysis method, aluminum chloride flame Alumina fine powder obtained by a decomposition method is used. As the crystal system, α, β, γ, δ, ξ, η, θ, κ, χ, ρ type, mixed crystal type, amorphous type, α, δ, γ, θ, mixed crystal can be used. A mold or an amorphous material is preferably used.

  As a method for hydrophobizing the inorganic fine powder, it is applied by chemical or physical treatment with an organosilicon compound that reacts or physically adsorbs with the inorganic fine powder.

  As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halogen compound is treated with an organosilicon compound. Examples of such organosilicon compounds are hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane. , Bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyl Dimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane 1,3-diphenyltetramethyldisiloxane, and dimethylpolysiloxane containing 2 to 12 siloxane units per molecule and containing hydroxyl groups bonded to one Si at each terminal unit. These are used alone or in a mixture of two or more.

  As inorganic fine particles that can be used in the present invention, the above-described wet process silica or dry process silica treated with a coupling agent having an amino group or silicone oil is used as necessary to achieve the object of the present invention. It doesn't matter.

As an external additive for improving fluidity, an inorganic fine powder having a BET specific surface area of 50 m ² / g or more and 400 m ² / g or less is preferable.

  For mixing the toner particles and the external additive, a known mixer such as a Henschel mixer can be used.

<Amorphous resin A / B configuration>
The toner of the present invention contains, as a binder resin, a polyester resin A having an aromatic diol as a main component and a small weight average molecular weight, and a polyester resin B having an aromatic diol as a main component and a large weight average molecular weight.

  By using two polyesters with different weight average molecular weights as the binder resin, the low temperature fixability of the toner is improved by the polyester having a low weight average molecular weight, and the hot offset resistance of the toner is improved by the polyester having a high weight average molecular weight. Can do.

  The sum of the content of the polyester resin A and the polyester resin B with respect to 100 parts by mass of the binder resin is preferably 90 parts by mass or more.

  In the present invention, the content ratio (A / B) of the polyester resin B to the polyester resin A is preferably 80/20 or more and 60/40 or less on a mass basis. When (A / B) is within this range, the balance between low-temperature fixability and hot offset resistance is good.

  Both polyester resin A and polyester resin B have a polyhydric alcohol unit and a polycarboxylic acid unit. In the present invention, the polyhydric alcohol unit is a component derived from the polyhydric alcohol component used in the condensation polymerization of polyester. In the present invention, the polyvalent carboxylic acid unit is a component derived from the polyvalent carboxylic acid used in the polyester polycondensation or its anhydride or lower alkyl ester.

  Both the polyester resin A and the polyester resin B of the present invention have a polyhydric alcohol unit and a polycarboxylic acid unit, and 90 mol of the polyhydric alcohol unit derived from the aromatic diol with respect to the total number of moles of the polyhydric alcohol unit. % Or more. If the polyhydric alcohol unit derived from the aromatic diol is less than 90 mol% with respect to the total number of moles of the polyhydric alcohol unit, the fog is deteriorated.

  Since the polyhydric alcohol unit of the polyester resin A has a structure derived from an aromatic diol common to the polyester resin B, it is easily compatible and the dispersibility of the polyester A and the polyester B is improved.

  Examples of the component derived from the aromatic diol include bisphenol represented by the formula (1) and derivatives thereof.

（式中、Ｒはエチレンまたはプロピレン基であり、ｘ、ｙはそれぞれ０以上の整数であり、かつ、ｘ＋ｙの平均値は０〜１０である。）

(In the formula, R is an ethylene or propylene group, x and y are each an integer of 0 or more, and the average value of x + y is 0 to 10.)

  Among them, it is preferable that R in the formula (1) of the polyester resin A and the polyester resin B is the same because they are easily compatible during melt kneading. Furthermore, a propylene oxide adduct of bisphenol A in which both R are propylene groups and the average value of x + y is 2 to 4 is preferred in terms of charging stability.

  If a polyester resin is the main component, a hybrid resin containing other resin components may be used. For example, a hybrid resin of a polyester resin and a vinyl resin can be given. As a method of obtaining a reaction product of a vinyl resin or a vinyl copolymer unit and a polyester resin, such as a hybrid resin, a monomer component capable of reacting with each of the vinyl resin, the vinyl copolymer unit and the polyester resin is included. Where a polymer is present, a method of performing a polymerization reaction of one or both resins is preferable.

  For example, among the monomers constituting the polyester resin component, those capable of reacting with the vinyl copolymer include, for example, unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid and itaconic acid, or anhydrides thereof. It is done. Among the monomers constituting the vinyl copolymer component, those capable of reacting with the polyester resin component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  In the present invention, if a polyester resin is the main component of the binder resin, various resin compounds conventionally known as binder resins can be used in addition to the above vinyl resins. Examples of such resin compounds include phenol resin, natural resin-modified phenol resin, natural resin-modified male resin, acrylic resin, methacrylic resin, polyvinyl acetate resin, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy Examples include resins, xylene resins, polyvinyl butyral, terpene resins, coumaroindene resins, petroleum resins, and the like.

  The peak molecular weight of the high molecular weight binder resin is preferably from 10,000 to 20,000 from the viewpoint of hot offset resistance. The acid value of the high molecular weight binder resin is preferably 15 mgKOH / g or more and 30 mgKOH / g or less from the viewpoint of charging stability in a high temperature and high humidity environment.

  The number average molecular weight of the low molecular weight binder resin is preferably 1500 or more and 3500 or less from the viewpoint of low-temperature fixability. The acid value of the low molecular weight binder resin is preferably 10 mgKOH / g or less from the viewpoint of charging stability in a high temperature and high humidity environment.

<Amorphous resin B>
The polyester resin B of the present invention has 0.1 mol% of polyhydric alcohol units derived from oxyalkylene ethers of novolac-type phenolic resin with respect to the total number of moles of polyhydric alcohol units relative to the total number of moles of polyhydric alcohol units. It is preferable to contain 10.0 mol% or less.

  The oxyalkylene ether of the novolak type phenol resin has a trihydric or higher alcoholic hydroxyl value and reacts with the acid component to form a flexible cross-linked structure with a wide network. Therefore, when the polyester resin B is mixed with the polyester A in the melt kneading step of the toner, the steric hindrance in the vicinity of the crosslinking point of the crosslinked structure of the polyester A is reduced, and the polyester B is easily entangled. As a result, the polyester resin B is well dispersed in the polyester resin A, the dispersibility of the crystalline polyester is also improved, and the crystalline polyester crystal tends to be neatly dispersed.

  The oxyalkylene ether of the novolac type phenol resin is a reaction product of the novolac type phenol resin and a compound having one epoxy ring in the molecule.

  Examples of the novolac type phenolic resin include hydrochloric acid, phosphoric acid, phosphoric acid, as described in the paragraph of Encyclopedia of Polymer Science and Technology (Interscience Publishers), Volume 10, page 1 Examples thereof include those produced by polycondensation from phenols and aldehydes using an inorganic acid such as sulfuric acid or an organic acid such as paratoluenesulfonic acid or oxalic acid or a metal salt such as zinc acetate as a catalyst. Examples of the phenols include phenols and substituted phenols having one or more hydrocarbon groups having 1 to 35 carbon atoms and / or halogen groups as substituents. Specific examples of the substituted phenol include cresol (ortho, meta or para), ethylphenol, nonylphenol, octylphenol, phenylphenol, styrenated phenol, isopropenylphenol, 3-chlorophenol, 3-bromophenol, 3, 5-xylenol, 2,4-xylenol, 2,6-xylenol, 3,5-dichlorophenol, 2,4-dichlorophenol, 3-chloro-5-methylphenol, dichloroxylenol, dibromoxylenol, Examples include 2,4,5-trichlorophenol and 6-phenyl-2-chlorophenol. Two or more phenols may be used in combination. In these, the substituted phenol substituted by the phenol and the hydrocarbon group is preferable, and especially phenol, cresol, t-butylphenol, and nonylphenol are preferable. Phenol and cresol are preferred in terms of imparting cost and offset resistance of the toner, and substituted phenols substituted with hydrocarbon groups typified by t-butylphenol and nonylphenol are preferred in terms of reducing the temperature dependence of the toner charge amount. preferable. Examples of aldehydes include formalin (formaldehyde solutions with various concentrations), paraformaldehyde, trioxane, hexamethylenetetramine and the like. The number average molecular weight of the novolak type phenol resin is usually 300 or more and 8000 or less, preferably 450 or more and 3000 or less, and more preferably 400 or more and 2000 or less.

  The number average number of phenolic nuclei in the novolak type phenolic resin is usually 3 or more and 60 or less, preferably 3 or more and 20 or less, and more preferably 4 or more and 15 or less. The softening point (JIS K2531; ring and ball method) is usually 40 ° C. or higher and 180 ° C. or lower, preferably 40 ° C. or higher and 150 ° C. or lower, more preferably 50 ° C. or higher and 130 ° C. or lower. If the softening point is less than 40 ° C., it will be blocked at room temperature and difficult to handle. On the other hand, when the softening point exceeds 180 ° C., gelation is caused in the production process of the polyester resin, which is not preferable.

  Specific examples of the compound having one epoxy ring in the molecule include ethylene oxide (EO), 1,2-propylene oxide (PO), 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, epichlorohydrin. Etc. Further, aliphatic monohydric alcohol having 1 to 20 carbon atoms or glycidyl ether of monohydric phenol can be used. Of these, EO and / or PO are preferred. The number of moles of the compound having one epoxy ring in the molecule relative to 1 mole of the novolak type phenol resin is usually 1 mole to 30 moles, preferably 2 moles to 15 moles, more preferably 2.5 moles to 10 moles. It is as follows. Moreover, the average addition mole number of the compound having one epoxy ring in the molecule with respect to one phenolic hydroxyl group in the novolak type phenol resin is usually 0.1 mol or more and 10 mol or less, preferably 0.1 mol or more and 4 mol or less. More preferably, it is 0.2 mol or more and 2 mol or less.

  The structure of the oxyalkylene ether of the novolak type phenol resin particularly preferably used in the present invention is illustrated.

（式中Ｒはエチレンまたはプロピレン基であり、ｘは０以上の数で、ｙ１〜ｙ３は０以上の同一又は異なった数である。）

(In the formula, R is an ethylene or propylene group, x is a number of 0 or more, and y1 to y3 are 0 or more of the same or different numbers.)

  The number average molecular weight of the oxyalkylene ether of the novolak type phenol resin is usually 300 or more and 10,000 or less, preferably 350 or more and 5,000 or less, and more preferably 450 or more and 3,000 or less. If the number average molecular weight is less than 300, sufficient hot offset resistance of the toner cannot be secured, and if it exceeds 10,000, gelation is caused in the production process of the polyester resin A, which is not preferable.

  The hydroxyl value (total of alcoholic and phenolic hydroxyl groups) of the oxyalkylene ether of the novolak type phenol resin is usually 10 mgKOH / g or more and 550 mgKOH / g or less, preferably 50 mgKOH / g or more and 500 mgKOH / g or less, more preferably 100 mgKOH / g or more. It is 450 mgKOH / g or less. Of the hydroxyl values, the phenolic hydroxyl value is usually from 0 mgKOH / g to 500 mgKOH / g, preferably from 0 mgKOH / g to 350 mgKOH / g, more preferably from 5 mgKOH / g to 250 mgKOH / g.

  An example of a method for producing an oxyalkylene ether of a novolak-type phenol resin is as follows: by adding a compound having one epoxy ring in a molecule to a novolak-type phenol resin in the presence of a catalyst (basic catalyst or acidic catalyst) as necessary. can get. The reaction temperature is usually 20 ° C. or higher and 250 ° C. or lower, preferably 70 ° C. or higher and 200 ° C. or lower. The reaction can be performed under normal pressure, increased pressure, or even reduced pressure. The reaction can also be carried out in the presence of a solvent (for example, xylene, dimethylformamide, etc.) or other dihydric alcohols and / or other trihydric or higher alcohols.

  When the polyhydric alcohol unit derived from the oxyalkylene ether of the novolak-type phenol resin of the polyester resin B is less than 0.1 mol%, the above-described flexible cross-linked structure portion having a wide network is reduced. Therefore, the dispersibility between the polyester resin A and the crystalline polyester is hardly improved. On the other hand, if it exceeds 10 mol%, the gel content of the polyester resin B is excessively increased, so that the polyester A and the crystalline polyester are hardly mixed at the time of melt-kneading, and the dispersibility of the crystalline polyester is hardly improved.

  As the component constituting the polyhydric alcohol unit of the polyester resin B, in addition to the aromatic diol and the oxyalkylene ether of the novolac type phenol resin, the following polyhydric alcohol components can be used as necessary. . Ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1, 6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbit, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol , Dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butant Ol, trimethylol ethane, trimethylol propane, 1,3,5-trihydroxy methyl benzene.

  The polyester resin B of the present invention is derived from an aliphatic dicarboxylic acid having a straight chain hydrocarbon having 4 to 16 carbon atoms as a main chain and having carboxyl groups at both ends with respect to the total number of moles of polyvalent carboxylic acid units. It is preferable to contain 15 mol% or more and 50 mol% or less of a polyvalent carboxylic acid unit because the dispersibility between the resins is improved.

  An aliphatic dicarboxylic acid having a straight chain hydrocarbon having 4 to 16 carbon atoms as a main chain and having carboxyl groups at both ends has a straight chain hydrocarbon structure in the main chain of the polyester when reacted with an alcohol component. Therefore, the main chain has a partially flexible structure. Therefore, in the toner melt-kneading step, the polyester resin A having a low softening point is mixed with the polyester resin B having a high softening point starting from this flexible structure, and entangled with the main chain of the cross-linking point polyester resin A to achieve dispersibility. And the dispersibility of the crystalline polyester is also improved.

  Aliphatic dicarboxylic acids having a straight chain hydrocarbon having 4 to 16 carbon atoms and having carboxyl groups at both ends are, for example, alkyl such as adipic acid, azelaic acid, sebacic acid, tetradecanedioic acid and octadecanedioic acid. Examples thereof include dicarboxylic acids, anhydrides thereof, and lower alkyl esters. In addition, a compound having a structure in which a part of the main chain is branched by an alkyl group such as a methyl group, an ethyl group, or an octyl group, or an alkylene group. Carbon number of this linear hydrocarbon becomes like this. Preferably it is 4-12, More preferably, it is 4-10.

  Examples of other polyvalent carboxylic acid units contained in the polyester resin B include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, or anhydrides thereof; alkyl groups or alkenyl groups having 6 to 18 carbon atoms. Substituted succinic acids or anhydrides thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof. Among these, carboxylic acid having an aromatic ring such as terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and their anhydrides or their derivatives are likely to improve hot offset resistance. Therefore, it is preferably used.

<Amorphous resin A>
The polyester resin A of the present invention has a polyhydric alcohol unit and a polycarboxylic acid unit, and contains 90 mol% or more of a polyhydric alcohol unit derived from an aromatic diol with respect to the total number of moles of the polyhydric alcohol unit. Is preferred. If the polyhydric alcohol unit derived from the aromatic diol is less than 90 mol% with respect to the total number of moles of the polyhydric alcohol unit, the fog is deteriorated. In order to ensure compatibility with the polyester B in the present invention, it is preferably 95 mol% or more, and more preferably 100 mol%.

  As components other than the aromatic diol that forms the polyhydric alcohol unit of the polyester resin B, the following polyhydric alcohol components can be used. Ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1, 6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbit, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol , Dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butant Ol, trimethylol ethane, trimethylol propane, 1,3,5-trihydroxy methyl benzene.

  The polyester resin A of the present invention preferably contains 90 mol% or more of a polyvalent carboxylic acid unit derived from an aromatic dicarboxylic acid or a derivative thereof based on the total number of moles of the polyvalent carboxylic acid unit.

  When the polyvalent carboxylic acid unit derived from the aromatic dicarboxylic acid or its derivative is in the above range, the compatibility with the polyester A is improved, and density fluctuations and fogging after long-time printing can be suppressed.

  Aromatic dicarboxylic acids or derivatives thereof include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, or anhydrides thereof.

  Further, when the polyvalent carboxylic acid unit derived from the aliphatic dicarboxylic acid or its derivative is contained in an amount of 0.1 mol% or more and 10.0 mol% or less with respect to the total number of moles of the polyvalent carboxylic acid unit, the low temperature fixability of the toner is further improved. It is preferable because it improves.

  Examples of the aliphatic dicarboxylic acid or derivatives thereof include alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; succinic acid substituted with an alkyl group or alkenyl group having 6 to 18 carbon atoms, or Examples thereof include unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid, or anhydrides thereof. Of these, succinic acid, adipic acid, fumaric acid, acid anhydrides thereof, and lower alkyl esters are preferably used.

  Examples of other polyvalent carboxylic acid units include trivalent or tetravalent carboxylic acids such as trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, and anhydrides thereof.

<Other binder resins>
As the binder resin used in the toner of the present invention, in addition to the above polyester resin A and polyester resin B, the following resins may be used for the purpose of improving pigment dispersibility and improving toner charging stability and blocking resistance. It is also possible to add the polymer in an amount that does not impair the effects of the present invention.

  Examples of other resins used for the binder resin of the toner of the present invention include the following resins. Styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene, and homopolymers thereof; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene -Acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether Styrene copolymers such as copolymers, styrene-vinyl methyl ketone copolymers, styrene-acrylonitrile-indene copolymers; polyvinyl chloride, phenol resins, natural modified phenol resins, natural resin modified maleic resins, acrylic resins , Methacrylic tree , Polyvinyl acetate, silicone resins, polyester resins, polyurethane, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumarone - indene resins, petroleum resins, and the like.

<Release agent (WAX)>
Examples of the wax used in the toner of the present invention include the following. Low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymer, hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of hydrocarbon wax such as oxidized polyethylene wax or block copolymer thereof; Waxes mainly composed of fatty acid esters such as carnauba wax; those obtained by partially or fully deoxidizing fatty acid esters such as deoxidized carnauba wax. Furthermore, the following are mentioned. Saturated linear fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid and valinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, Saturated alcohols such as sil alcohols; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid, montanic acid, and stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, Esters with alcohols such as sil alcohols; Fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; Methylene bis stearic acid amide, ethylene biscapric acid Saturated fatty acid bisamides such as amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide; ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N 'dioleyl adipic acid amide, N, N' dioleyl Unsaturated fatty acid amides such as sebacic acid amides; aromatic bisamides such as m-xylene bis-stearic acid amide, N, N ′ distearyl isophthalic acid amide; calcium stearate, calcium laurate, zinc stearate, magnesium stearate Aliphatic metal salts such as those commonly referred to as metal soaps; waxes grafted to aliphatic hydrocarbon waxes using vinylic monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglycerides Alcohol Partial ester; methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable fats and oils.

  Among these waxes, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax or fatty acid ester waxes such as carnauba wax are preferable from the viewpoint of improving low-temperature fixability and hot offset resistance. In the present invention, a hydrocarbon wax is more preferable in that the hot offset resistance is further improved.

  In the present invention, the wax is preferably used in an amount of 1 to 20 parts by mass per 100 parts by mass of the binder resin.

  Moreover, in the endothermic curve at the time of temperature rise measured with a differential scanning calorimetry (DSC) apparatus, the peak temperature of the maximum endothermic peak of the wax is preferably 45 ° C. or higher and 140 ° C. or lower. It is preferable that the peak temperature of the maximum endothermic peak of the wax is within the above range because both the storage stability of the toner and the hot offset resistance can be achieved.

<Colorant>
Examples of the colorant that can be contained in the toner include the following.

  Examples of the black colorant include carbon black; those prepared by using a yellow colorant, a magenta colorant, and a cyan colorant and adjusting the color to black. As the colorant, a pigment may be used alone, but it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together.

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

  Examples of the magenta toner dye include the following. C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; I. Disper thread 9; I. Solvent violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. B. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

  Examples of the cyan toner pigment include the following. C. I. Pigment blue 2, 3, 15: 2, 15: 3, 15: 4, 16, 17; I. Bat Blue 6; C.I. I. Acid Blue 45, a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.

  Examples of cyan toner dyes include C.I. I. There is Solvent Blue 70.

  Examples of the yellow toner pigment include the following. C. I. 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, 185; I. Bat yellow 1, 3, 20

  Examples of the dye for yellow toner include C.I. I. There is Solvent Yellow 162.

  The amount of the colorant used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the binder resin.

<Charge control agent>
The toner may contain a charge control agent as necessary. As the charge control agent contained in the toner, known ones can be used. In particular, a metal compound of an aromatic carboxylic acid that is colorless, has a high toner charging speed, and can stably maintain a constant charge amount is preferable.

  Negative charge control agents include salicylic acid metal compounds, naphthoic acid metal compounds, dicarboxylic acid metal compounds, polymeric compounds having sulfonic acid or carboxylic acid in the side chain, sulfonates or sulfonated compounds in the side chain. Examples thereof include a polymer compound, a polymer compound having a carboxylate or a carboxylic acid ester in the side chain, a boron compound, a urea compound, a silicon compound, and calixarene. Examples of the positive charge control agent include quaternary ammonium salts, polymer compounds having the quaternary ammonium salt in the side chain, guanidine compounds, and imidazole compounds. The charge control agent may be added internally or externally to the toner particles. The addition amount of the charge control agent is preferably 0.2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin.

<Crystalline resin>
The toner of the present invention contains crystalline polyester and is present in a finely dispersed state, whereby the function as a toner can be further enhanced.

  In the toner of the present invention, the crystalline polyester contained in the toner particles is a monomer composition containing an aliphatic diol having 2 to 22 carbon atoms and an aliphatic dicarboxylic acid having 2 to 22 carbon atoms as main components. Can be obtained by polycondensation reaction.

  The aliphatic diol having 2 to 22 carbon atoms (more preferably 2 to 12 carbon atoms) is not particularly limited, but is preferably a chain (more preferably linear) aliphatic diol, , Ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,4-butadiene glycol, trimethylene glycol, tetramethylene glycol, Examples include pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, and neopentyl glycol. Of these, linear aliphatic groups such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol, and α, ω-diol are particularly preferred.

  Among the alcohol components, preferably 50% by mass or more, more preferably 70% by mass or more is an alcohol selected from aliphatic diols having 2 to 22 carbon atoms.

  In the present invention, a polyhydric alcohol monomer other than the aliphatic diol can also be used. Among the polyhydric alcohol monomers, examples of the dihydric alcohol monomer include aromatic alcohols such as polyoxyethylenated bisphenol A and polyoxypropylenated bisphenol A; 1,4-cyclohexanedimethanol and the like. Among the polyhydric alcohol monomers, trihydric or higher polyhydric alcohol monomers include aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; pentaerythritol, dipentaerythritol, tripentaerythritol. 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane and the like Group alcohol and the like.

  Furthermore, in this invention, you may use a monovalent alcohol to such an extent that the characteristic of crystalline polyester is not impaired. Examples of the monovalent alcohol include monofunctional groups such as n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, lauryl alcohol, 2-ethylhexanol, decanol, cyclohexanol, benzyl alcohol, and dodecyl alcohol. And alcohol.

  On the other hand, the aliphatic dicarboxylic acid having 2 to 22 carbon atoms (more preferably 4 to 14 carbon atoms) is not particularly limited, but is a chain (more preferably linear) aliphatic dicarboxylic acid. Is preferred. Specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, Examples include maleic acid, fumaric acid, mesaconic acid, citraconic acid, and itaconic acid, and those obtained by hydrolyzing these acid anhydrides or lower alkyl esters.

  In the present invention, among the carboxylic acid components, preferably 50% by mass or more, more preferably 70% by mass or more is a carboxylic acid selected from aliphatic dicarboxylic acids having 2 to 22 carbon atoms.

  In the present invention, a polyvalent carboxylic acid other than the aliphatic dicarboxylic acid having 2 to 22 carbon atoms may be used. Among the other polyvalent carboxylic acid monomers, divalent carboxylic acids include aromatic carboxylic acids such as isophthalic acid and terephthalic acid; n-dodecyl succinic acid, n-dodecenyl succinic aliphatic carboxylic acid; cyclohexane dicarboxylic acid Examples thereof include alicyclic carboxylic acids such as acids, and these acid anhydrides or lower alkyl esters are also included. Among the other carboxylic acid monomers, trivalent or higher polyvalent carboxylic acids include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, Aromatic carboxylic acids such as 2,4-naphthalenetricarboxylic acid and pyromellitic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2 -Aliphatic carboxylic acids such as methylenecarboxypropane, and derivatives of these acid anhydrides or lower alkyl esters are also included.

  Furthermore, in this invention, you may contain monovalent carboxylic acid to such an extent that the characteristic of crystalline polyester is not impaired. Examples of the monovalent carboxylic acid include benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, Examples thereof include monocarboxylic acids such as dodecanoic acid and stearic acid.

  The crystalline polyester in the present invention can be produced according to an ordinary polyester synthesis method. For example, the above-mentioned carboxylic acid monomer and alcohol monomer are esterified or transesterified, and then subjected to a polycondensation reaction in accordance with a conventional method under reduced pressure or by introducing nitrogen gas. Crystalline polyester can be obtained.

  The esterification or transesterification reaction can be performed using a normal esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate, and magnesium acetate, if necessary.

  The polycondensation reaction can be carried out using a conventional polymerization catalyst, for example, a known catalyst such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide. . The polymerization temperature and the catalyst amount are not particularly limited, and may be determined appropriately.

  In the esterification or transesterification reaction or polycondensation reaction, all monomers are charged together to increase the strength of the resulting crystalline polyester, or divalent monomers are first reacted to reduce low molecular weight components. Then, a method of adding a trivalent or higher monomer and reacting the monomer may be used.

<Developer>
The toner of the present invention can also be used as a one-component developer, but in order to further improve dot reproducibility, it can be mixed with a magnetic carrier and used as a two-component developer. Is preferable in that it is obtained.

  Examples of the magnetic carrier include iron powder whose surface is oxidized, non-oxidized iron powder, metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, rare earth, and the like Magnetic material dispersed resin carriers (so-called resin carriers) containing magnetic materials such as alloy particles, oxide particles, ferrite, and the like, and magnetic materials and binder resins that hold the magnetic materials in a dispersed state are generally known. Things can be used.

  When the toner of the present invention is mixed with a magnetic carrier and used as a two-component developer, the carrier mixing ratio at that time is 2% by mass or more and 15% by mass or less, preferably as a toner concentration in the two-component developer. In general, good results are obtained when the content is from 4% by mass to 13% by mass.

<Manufacturing method>
As a method for producing toner particles, since it is necessary to melt and knead the binder resin, the colorant, and the wax, the binder resin, the colorant, and the wax are melt-kneaded, and the kneaded product is cooled, A pulverization method of pulverization and classification is preferred.

  Hereinafter, a toner manufacturing procedure using the pulverization method will be described.

  In the raw material mixing step, as a material constituting the toner particles, for example, a predetermined amount of other components such as a binder resin, a wax, a colorant, and a charge control agent as necessary are mixed and mixed. Examples of the mixing apparatus include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a mechano-hybrid (manufactured by Nippon Coke Industries, Ltd.).

  Next, the mixed material is melt-kneaded to disperse wax or the like in the binder resin. In the melt-kneading process, a batch kneader such as a pressure kneader or a Banbury mixer or a continuous kneader can be used, and a single-screw or twin-screw extruder has become the mainstream because of the advantage of continuous production. ing. For example, KTK type twin screw extruder (manufactured by Kobe Steel Co., Ltd.), TEM type twin screw extruder (manufactured by Toshiba Machine Co., Ltd.), PCM kneader (manufactured by Ikekai Tekko), twin screw extruder (manufactured by Kay Sea Kay Co., Ltd.) ), Co-kneader (manufactured by Buss), kneedex (manufactured by Nippon Coke Industries Co., Ltd.), and the like. Furthermore, the resin composition obtained by melt-kneading may be rolled with two rolls or the like and cooled with water or the like in the cooling step.

  Next, the cooled product of the resin composition is pulverized to a desired particle size in the pulverization step. In the pulverization step, for example, after coarse pulverization with a pulverizer such as a crusher, a hammer mill, or a feather mill, for example, a kryptron system (manufactured by Kawasaki Heavy Industries), a super rotor (manufactured by Nisshin Engineering), a turbo mill Finely pulverize with a turbomill (made by Turbo Industries) or air jet type fine pulverizer.

  Then, if necessary, classification such as inertial class elbow jet (manufactured by Nippon Steel & Mining Co., Ltd.), centrifugal classification turboplex (manufactured by Hosokawa Micron), TSP separator (manufactured by Hosokawa Micron), Faculty (manufactured by Hosokawa Micron) Classification using a machine or sieving machine to obtain a classified product (toner particles). Among these, Faculty (manufactured by Hosokawa Micron Corporation) is preferable from the viewpoint of improving the transfer efficiency because it can perform the spheroidizing treatment of toner particles simultaneously with the classification.

  Further, an external additive is applied to the surface of the toner particles as necessary. As a method of externally adding external additives, a predetermined amount of classified toner and various known external additives are blended, and a double-con mixer, V-type mixer, drum-type mixer, super mixer, Henschel mixer, Nauta mixer, mechano Examples thereof include a method of stirring and mixing using a mixing apparatus such as a hybrid (manufactured by Nippon Coke Industries Co., Ltd.), Nobilta (manufactured by Hosokawa Micron Co., Ltd.) or the like as an external additive.

  A method for measuring various physical properties of toner and raw materials will be described below.

<Method for measuring number average particle diameter of external additive>
The average primary particle size (number average particle size) of the external additive was observed with a transmission electron microscope “H-800” (manufactured by Hitachi, Ltd.), and in the field of view enlarged up to 2 million times, 100 primary particles The major diameter is measured to determine the average primary particle size. The observation magnification is appropriately adjusted according to the size of the external additive. As a scanning electron microscope, S-4800 (manufactured by Hitachi, Ltd.) was used.

<Measurement method of weight average molecular weight of resin>
The molecular weight distribution of the THF soluble part of the resin was measured by gel permeation chromatography (GPC) as follows.

First, the toner was dissolved in tetrahydrofuran (THF) at room temperature over 24 hours. Thereafter, the obtained solution was filtered through a solvent-resistant membrane filter “Maescho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution was adjusted so that the concentration of the component soluble in THF was about 0.8% by mass. Using this sample solution, measurement was performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml

  In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F— 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 "manufactured by Tosoh Corporation) were used.

<Measurement of BET specific surface area of inorganic fine particles>
The BET specific surface area of the inorganic fine particles is measured according to JIS Z8830 (2001). A specific measurement method is as follows.

  As a measuring device, an “automatic specific surface area / pore distribution measuring device TriStar 3000 (manufactured by Shimadzu Corporation)” which employs a gas adsorption method by a constant volume method as a measuring method is used. Setting of measurement conditions and analysis of measurement data are performed using dedicated software “TriStar3000 Version 4.00” attached to the apparatus, and a vacuum pump, a nitrogen gas pipe, and a helium gas pipe are connected to the apparatus. The value calculated by the BET multipoint method using nitrogen gas as the adsorption gas is taken as the BET specific surface area of the inorganic fine particles in the present invention.

  The BET specific surface area is calculated as follows.

First, nitrogen gas is adsorbed onto the inorganic fine particles, and then the equilibrium pressure P (Pa) in the sample cell and the nitrogen adsorption amount Va (mol · g ⁻¹ ) of the external additive are measured. The relative pressure Pr, which is a value obtained by dividing the equilibrium pressure P (Pa) in the sample cell by the saturated vapor pressure Po (Pa) of nitrogen, is plotted on the horizontal axis, and the nitrogen adsorption amount Va (mol · g ⁻¹ ) is plotted on the vertical axis. The adsorption isotherm is obtained. Next, a monomolecular layer adsorption amount Vm (mol · g ⁻¹ ), which is an adsorption amount necessary for forming a monomolecular layer on the surface of the external additive, is determined by applying the following BET equation.
Pr / Va (1-Pr) = 1 / (Vm * C) + (C-1) * Pr / (Vm * C)
(Here, C is a BET parameter, which is a variable that varies depending on the measurement sample type, adsorbed gas type, and adsorption temperature.)

The BET equation is interpreted as a straight line with an inclination of (C-1) / (Vm × C) and an intercept of 1 / (Vm × C), where Pr is X axis and Pr / Va (1-Pr) is Y axis. Yes (this line is called a BET plot).
Straight line slope = (C-1) / (Vm × C)
Straight line intercept = 1 / (Vm × C)

  When the measured value of Pr and the measured value of Pr / Va (1-Pr) are plotted on a graph and a straight line is drawn by the least square method, the slope and intercept value of the straight line can be calculated. Vm and C can be calculated by solving the simultaneous equations of the slope and intercept using these values.

Furthermore, the BET specific surface area S (m ² / g) of the inorganic fine particles is calculated from the calculated Vm and the molecular occupation cross-sectional area (0.162 nm ² ) of the nitrogen molecule based on the following formula.
S = Vm × N × 0.162 × 10 ⁻¹⁸
(N is Avogadro's number (mole- ¹ ).)

  The measurement using this apparatus follows the “TriStar 3000 Instruction Manual V4.0” attached to the apparatus, and specifically, the measurement is performed according to the following procedure.

  Thoroughly weigh the tare of a dedicated glass sample cell (stem diameter 3/8 inch, volume about 5 ml) that has been thoroughly cleaned and dried. Then, about 0.1 g of an external additive is put into the sample cell using a funnel.

  The sample cell containing the inorganic fine particles is set in a “pretreatment device Bacrepprep 061 (manufactured by Shimadzu Corporation)” connected with a vacuum pump and a nitrogen gas pipe, and vacuum degassing is continued at 23 ° C. for about 10 hours. During vacuum deaeration, the inorganic fine particles are gradually deaerated while adjusting the valve so that the inorganic fine particles are not sucked into the vacuum pump. The pressure in the cell gradually decreases with deaeration and finally becomes about 0.4 Pa (about 3 mTorr). After completion of vacuum degassing, nitrogen gas is gradually injected to return the inside of the sample cell to atmospheric pressure, and the sample cell is removed from the pretreatment device. Then, the mass of the sample cell is precisely weighed, and the accurate mass of the external additive is calculated from the difference from the tare. At this time, the sample cell is covered with a rubber plug during weighing so that the external additive in the sample cell is not contaminated by moisture in the atmosphere.

  Next, a dedicated “isothermal jacket” is attached to the stem portion of the sample cell containing the inorganic fine particles. Then, a dedicated filler rod is inserted into the sample cell, and the sample cell is set in the analysis port of the apparatus. The isothermal jacket is a cylindrical member having an inner surface made of a porous material and an outer surface made of an impermeable material capable of sucking liquid nitrogen to a certain level by capillary action.

  Subsequently, the free space of the sample cell including the connection tool is measured. The free space is measured by measuring the volume of the sample cell using helium gas at 23 ° C., and then measuring the volume of the sample cell after cooling the sample cell with liquid nitrogen using helium gas. It is calculated by converting from the difference in volume. Further, the saturated vapor pressure Po (Pa) of nitrogen is automatically measured separately using a Po tube built in the apparatus.

  Next, after performing vacuum deaeration in the sample cell, the sample cell is cooled with liquid nitrogen while continuing the vacuum deaeration. Thereafter, nitrogen gas is gradually introduced into the sample cell to adsorb nitrogen molecules to the toner. At this time, since the adsorption isotherm is obtained by measuring the equilibrium pressure P (Pa) as needed, the adsorption isotherm is converted into a BET plot. Note that the points of the relative pressure Pr for collecting data are set to a total of 6 points of 0.05, 0.10, 0.15, 0.20, 0.25, and 0.30. A straight line is drawn from the obtained measurement data by the least square method, and Vm is calculated from the slope and intercept of the straight line. Furthermore, using the value of Vm, the BET specific surface area of the inorganic fine particles is calculated as described above.

<Method for Measuring Weight Average Particle Size (D4) of Toner Particles>
The weight average particle diameter (D4) of the toner particles is measured with a precision particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube. Measured data with 25,000 effective measurement channels using the dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) for condition setting and measurement data analysis Was analyzed and calculated.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, the dedicated software was set as follows.

  In the “Standard measurement method (SOM) change screen” of the dedicated software, set the total count in the control mode to 50000 particles, the number of measurements is 1 and the Kd value is “standard particles 10.0 μm” (Beckman Coulter The value obtained using the product was set. 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 was set to 2, the electrolyte was set to ISOTON II, and the aperture tube flash after the measurement was checked.

  In the “Pulse to Particle Size Conversion Setting Screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm or more and 60 μm or less.

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution was placed in a glass 250 ml round-bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod was stirred counterclockwise at 24 rpm. Then, dirt and bubbles in the aperture tube were previously removed by the “aperture flush” function of the analysis software.
(2) About 30 ml of the electrolytic aqueous solution is put in a glass 100 ml flat bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder pH 7 precision measurement is used as a dispersant therein. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing a vessel (made by Wako Pure Chemical Industries, Ltd.) 3 times with ion-exchanged water was added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and placed in a water tank of an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikkaki Bios Co., Ltd.) having an electrical output of 120 W A predetermined amount of ion-exchanged water was added, and about 2 ml of the above-mentioned Contaminone N was added to this water tank.
(4) The beaker of (2) was set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser was operated. Then, the height position of the beaker was adjusted so that the resonance state of the liquid surface of the electrolytic aqueous solution in the beaker was maximized.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) was irradiated with ultrasonic waves, about 10 mg of toner was added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion treatment was further continued for 60 seconds. In the ultrasonic dispersion, the water temperature in the water tank was appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte aqueous solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . The measurement was performed until the number of measured particles reached 50000.
(7) The measurement data was analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) was calculated. The “average diameter” on the analysis / volume statistics (arithmetic average) screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

<Average circularity of toner>
The average circularity of the toner was measured with a flow type particle image analyzer “FPIA-3000 type” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during calibration.

  The measurement principle of the flow-type particle image analyzer “FPIA-3000 type” (manufactured by Sysmex Corporation) is to take a flowing particle as a still image and perform image analysis. The sample added to the sample chamber is fed into the flat sheath flow cell by a sample suction syringe. The sample fed into the flat sheath flow is sandwiched between sheath liquids to form a flat flow. The sample passing through the flat sheath flow cell is irradiated with strobe light at 1/60 second intervals, and the flowing particles can be photographed as a still image. Further, since the flow is flat, the image is taken in a focused state. The particle images are picked up by a CCD camera, and the picked-up image is 512 pixels × 512 pixels in one field of view, and image processing is performed at an image processing resolution of 0.37 × 0.37 μm per pixel, and the contour of each particle image Extraction is performed, and the projected area and perimeter of the particle image are measured.

Next, the projected area S and the perimeter L of each particle image are obtained. Using the area S and the perimeter L, the equivalent circle diameter and the circularity are obtained. The circular equivalent diameter is the diameter of a circle having the same area as the projected area of the particle image, and the circularity is a value obtained by dividing the circumference of the circle obtained from the circular diameter by the circumference of the projected particle image. Defined and calculated by the following formula.
Circularity C = 2 × (π × S) ^1/2 / L

  When the particle image is a perfect circle, the circularity becomes 1.000, and the circularity becomes smaller as the degree of irregularities on the outer periphery of the particle image increases.

  After calculating the circularity of each particle, the range of the circularity of 0.2 to 1.0 is allocated to 800 divided channels, the average value is calculated using the center value of each channel as a representative value, and the average circularity is calculated.

  As a specific measurement method, 0.02 g of a surfactant as a dispersant, preferably sodium dodecylbenzenesulfonate, is added to 20 ml of ion-exchanged water, 0.02 g of a measurement sample is added, an oscillation frequency of 50 kHz, electrical Dispersion treatment was performed for 2 minutes using a desktop ultrasonic cleaner / disperser with an output of 150 W (for example, “VS-150” (manufactured by Velvo Crea Co., Ltd.)) to obtain a dispersion for measurement. Is suitably cooled so that the temperature becomes 10 ° C. or higher and 40 ° C. or lower.

  The flow type particle image analyzer equipped with a standard objective lens (10 ×) was used for the measurement, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion prepared in accordance with the above procedure is introduced into the flow type particle image analyzer, 3000 toner particles are measured in the total count mode in the HPF measurement mode, and the binarization threshold at the time of particle analysis is 85%. The analysis particle diameter was limited to a circle equivalent diameter of 2.00 μm to 200.00 μm, and the average circularity of the toner was determined.

  In the measurement, automatic focus adjustment is performed using standard latex particles (for example, Duke Scientific 5200A diluted with ion-exchanged water) before the measurement is started. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.

  In the examples of the present application, a flow type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation is used, and the analysis particle diameter is limited to a circle equivalent diameter of 2.00 μm to 200.00 μm. The measurement was performed under the measurement and analysis conditions when the calibration certificate was received.

<Evaluation of crystalline state of crystalline polyester by TEM observation>
Cross-sectional observation of the toner with a transmission electron microscope (TEM) and evaluation of the crystalline polyester domain were carried out as follows.

  By ruthenium dyeing the toner cross section, a crystalline polyester resin can be obtained as a clear contrast. The crystalline polyester resin is dyed weaker than the organic component constituting the inside of the toner. This is presumably because the infiltration of the dye material into the crystalline polyester resin is weaker than the organic component inside the toner due to a difference in density.

  Because the amount of ruthenium atoms varies depending on the intensity of staining, the strongly stained part has many of these atoms, the electron beam does not pass through, it becomes black on the observation image, and the part that is weakly stained is The electron beam is easily transmitted and becomes white on the observation image.

  Using an osmium plasma coater (filgen, OPC80T), the toner is coated with an Os film (5 nm) and a naphthalene film (20 nm) as a protective film, and embedded with a photo-curing resin D800 (JEOL). Using a sonic ultramicrotome (Leica, UC7), a toner cross section having a film thickness of 60 nm (or 70 nm) was prepared at a cutting speed of 1 mm / s.

  The obtained cross section was dyed in a RuO4 gas 500 Pa atmosphere for 15 minutes using a vacuum electron dyeing apparatus (filgen, VSC4R1H), and STEM observation was performed using TEM (JEOL, JEM2800).

  The STEM probe size was 1 nm, and the image size was 1024 × 1024 pixels.

  The obtained image was binarized (threshold 120/255 stage) with image processing software “Image-Pro Plus (Media Cybernetics)”.

  The obtained cross-sectional image before binarization is shown in FIG. As can be seen in FIG. 1, the crystalline domains of the crystalline polyester can be confirmed as black bars, and the obtained domains are binarized to extract the crystalline domains. For 20 randomly selected toners, the total length of the crystalline polyester crystal domains whose length can be measured was measured in total, and the average number of crystalline polyesters in the toner was determined from the number of measured crystal domains. The major axis length was calculated. In addition, the cross section of the toner is cut with a mesh of 1.0 μm intervals, and a 1.0 μm × 1.0 μm visual field (see FIG. 3) is extracted from the inside of the toner. The standard deviation of the area occupied by CPES in each visual field was calculated.

  Here, the long axis length of the crystalline domain of the crystalline polyester is the longest distance (a in FIG. 2) in the crystal domain of the cross-sectional image, as shown in FIG. This is the shortest distance (b in FIG. 2) at the point position.

  The needle shape in the present invention is a shape that is elongated and has a high straightness, a short axis length of 25 nm or less, an aspect ratio of 5 or more, and a short axis direction in both of the long axis directions of the crystal. When the center points were connected with a straight line, the shape of the crystal outline deviated from the straight line was defined as a shape within 100% of the crystal minor axis length. It is a representative element.

  Although the basic configuration and features of the present invention have been described above, the present invention will be specifically described below based on examples. However, this does not limit the embodiment of the present invention.

<Production example of organic-inorganic composite particles 1 to 3>
The organic-inorganic composite particles can be produced according to the description of the examples in WO2013 / 063291.

  As the organic-inorganic composite particles 1 to 3 used in Examples described later, those prepared according to Example 1 of WO2013 / 063291 using silica shown in Table 1 are prepared. Table 1 shows the particle diameter of the organic-inorganic composite particles. Each of the organic-inorganic composite particles shown in Table 1 has a plurality of convex portions derived from inorganic fine particles (silica) on the surface thereof.

<Example of production of inorganic particles 1>
The inorganic particles 1 are obtained by a general sol-gel method using a wet method.

  In a glass reactor equipped with a stirrer, a dropping funnel and a thermometer, 693.0 g of methanol, 46.0 g of water and 55.3 g of 5.4 mass% aqueous ammonia solution were added as alcohol solvents, and methanol, water and ammonia were added. Prepare a mixed solution.

  The obtained mixed solution is adjusted to a reaction temperature of 45 ° C., stirred while maintaining the reaction temperature, and the dropwise addition time of tetramethoxysilane is dropped for 8 hours. The ammonia water is adjusted so that dropping is completed one hour earlier than tetramethoxysilane. After completion of the dropping, the mixture is stirred for 1 hour to cause a hydrolysis reaction to obtain a methanol-water dispersion of sol-gel silica fine particles.

  The dispersion is then heated to 75 ° C. to distill off 1320 g of methanol and then add 1320 g of water. Then, the dispersion is heated to 90 ° C. to distill off 532.4 g of methanol to obtain an aqueous dispersion of sol-gel silica fine particles.

  After adding 1584 g of methyl isobutyl ketone to the aqueous dispersion, methanol and water are distilled off at 100 ° C./15 hours.

After cooling the obtained methyl isobutyl ketone dispersion of sol-gel silica to 25 ° C., 322 g of hexamethyldisilazane was added as a surface treating agent (0.24 mol relative to 1 mol of SiO ₂ unit), and 110 ° C./5 Surface treatment is performed by reacting for a time.

  The inorganic particles 1 are obtained by distilling off the solvent from the dispersion at 80 ° C. under reduced pressure. The shape is spherical. The physical properties are shown in Table 2.

<Example of production of inorganic particles 2>
After supplying oxygen gas to the burner at 30 Nm ³ / h and igniting the ignition burner, hydrogen gas is supplied to the burner at 50 Nm ³ / h to form a flame. The raw material silicon tetrachloride is charged at 100 kg / h for gasification, the residence time is set to 0.010 sec, the flame hydrolysis reaction is performed, and the generated silica powder is recovered.

  Thereafter, the obtained silica powder is transferred to an electric furnace and spread in a thin layer, followed by heat treatment at 700 ° C. to sinter and agglomerate.

  Next, 10 parts by mass of hexamethyldisilazane is added as a surface treatment agent to 100 parts by mass of the silica fine particles obtained, so that a hydrophobic treatment is performed to obtain inorganic particles 2. The shape exists in a mixed state from spherical to indefinite shape. The physical properties are shown in Table 2.

<Inorganic particles 3>
As the inorganic particles 3, silica having a base BET of 200 mm ² / g and a primary particle diameter of 15 nm obtained by the fumed method is used. The shape is irregular. The physical properties are shown in Table 2.

<Inorganic particles 4>
A rutile type titanium oxide having a BET specific surface area of 100 m ² / g was used. The shape is irregular. The physical properties are shown in Table 2.

<Organic particles 1>
The organic particle 1 uses an eposter manufactured by Nippon Shokubai Co., Ltd. The physical properties are shown in Table 2.

<Production Example 1 of Amorphous Polyester Resin A>
・ 2,2-bis (4-hydroxyphenyl) propane: 64.7 parts by mass (0.18 mol; 100.0 mol% based on the total number of polyhydric alcohols)
-Terephthalic acid: 24.1 parts by mass (0.15 mol; 96.0 mol% based on the total number of polyvalent carboxylic acids)
Titanium tetrabutoxide (esterification catalyst): 0.5 part by mass The above materials were weighed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2 hours while stirring at a temperature of 200 ° C.

  Further, the pressure in the reaction vessel was lowered to 8.3 kPa, maintained for 1 hour, then cooled to 180 ° C. and returned to atmospheric pressure (first reaction step).

-Acrylic acid: 0.2 parts by mass-Styrene: 8.2 parts by mass-2-Ethylhexyl acrylate: 1.6 parts by mass-Dibutyl peroxide (polymerization initiator): 1.5 parts by mass Was added dropwise over 1 hour and held for 1 hour (StAc conversion reaction step).

・ Trimellitic anhydride:
1.2 parts by mass (0.01 mol; 4.0 mol% based on the total number of polyvalent carboxylic acids)
Tert-butylcatechol (polymerization inhibitor): 0.1 part by mass Thereafter, the above materials are added, the pressure in the reaction vessel is lowered to 8.3 kPa, and the reaction is continued for 1 hour while maintaining the temperature at 160 ° C. (second Reaction step), an amorphous resin A1 having a weight average molecular weight (Mw) of 5000 was obtained.

<Production Example 1 of Amorphous Polyester Resin B>
・ 2,2-bis (4-hydroxyphenyl) propane: 47.1 parts by mass (0.13 mol; 90.0 mol% based on the total number of moles of polyhydric alcohol)
-Novolac-type phenol resin (5 mol propylene oxide adduct having about 5 nuclei):
11.9 parts by mass (0.01 mol; 10.0 mol% based on the total number of moles of polyhydric alcohol)
·Terephthalic acid:
16.3 parts by mass (0.10 mol; 80.0 mol% with respect to the total number of polyvalent carboxylic acids)
Titanium tetrabutoxide (esterification catalyst): 0.5 part by mass The above materials were weighed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2 hours while stirring at a temperature of 200 ° C.

  Further, the pressure in the reaction vessel was lowered to 8.3 kPa, maintained for 1 hour, then cooled to 180 ° C. and returned to atmospheric pressure (first reaction step).

-Acrylic acid: 0.5 part by mass-Styrene: 16.4 parts by mass-2-ethylhexyl acrylate: 3.1 parts by mass-Dibutyl peroxide (polymerization initiator): 1.5 parts by mass Was added dropwise over 1 hour and held for 1 hour (StAc conversion reaction step).

・ Trimellitic anhydride:
6.4 parts by mass (0.03 mol; 20.0 mol% based on the total number of polyvalent carboxylic acids)
Tert-Butylcatechol (polymerization inhibitor): 0.1 part by mass Thereafter, the above materials are added, the pressure in the reaction vessel is lowered to 8.3 kPa, and the reaction is continued for 15 hours while maintaining the temperature at 160 ° C. (second Reaction step), an amorphous resin B1 having a weight average molecular weight (Mw) of 100,000 was obtained.

<Production Example 2 of Amorphous Polyester Resin B>
Weight average molecular weight (Mw) in the same manner as in Production Example 1 of Amorphous Resin B, except that 11.9 parts by mass of novolak-type phenolic resin (5 mol of propylene oxide adduct having about 5 nuclei) was changed to 0 parts by mass An amorphous resin B2 of 100,000 was obtained.

<Crystalline polyester resin C production example 1>
1,10-decanediol:
46.9 parts by mass (0.27 mol; 100.0 mol% based on the total number of moles of polyhydric alcohol)
-Sebacic acid:
53.1 parts by mass (0.26 mol; 100.0 mol% with respect to the total number of polyvalent carboxylic acids)
The above materials were weighed into a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 3 hours while stirring at a temperature of 140 ° C.

-Tin 2-ethylhexanoate: 0.5 part by mass Thereafter, the above materials were added, the pressure in the reaction vessel was lowered to 8.3 kPa, and the reaction was continued for 4 hours while maintaining the temperature at 200 ° C. Got.

<Toner Production Example 1>
Polyester resin A1 75 parts by mass Polyester resin B1 25 parts by mass Crystalline polyester resin C1 10 parts by mass Hydrocarbon wax (peak temperature of maximum endothermic peak 78 ° C) 6 parts by mass I. Pigment Blue 15: 3 6.8 parts by mass • 3,5-di-t-butylsalicylic acid aluminum compound 0.25 parts by mass Using the above materials with a Henschel mixer (FM-75 type, manufactured by Mitsui Mining Co., Ltd.), After mixing at a rotation speed of 20 s ⁻¹ and a rotation time of 5 min, the mixture was kneaded at a discharge temperature of 150 ° C. with a twin-screw kneader (PCM-30 type, manufactured by Ikegai Co., Ltd.) set at a temperature of 130 ° C. The obtained kneaded product was cooled at a cooling rate of 15 ° C./min, and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized product. The obtained coarsely crushed material was finely pulverized with a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.). Further, classification was performed using Faculty F-300 (manufactured by Hosokawa Micron Corporation) to obtain toner particles. The operating conditions were a classification rotor rotational speed of 130 s-1 and a distributed rotor rotational speed of 120 s- ¹ .

4.0 parts by mass of organic-inorganic composite particles 1 and 0.2 parts by mass of inorganic particles 4 are added to the obtained toner base, and the number of revolutions is increased with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.). The toner particles 1 were obtained by mixing for 30 s ⁻¹ and a rotation time of 10 minutes (see Table 3).

The toner particles 1 were heat-treated with the surface treatment apparatus shown in FIG. The operating conditions are feed rate = 5 kg / hr, hot air temperature = 160 ° C., hot air flow rate = 6 m ³ / min, cold air temperature = −5 ° C., cold air flow rate = 4 m ³ / min, blower air flow = 20 m ³ / min, The injection air flow rate was 1 m ³ / min.

Further, with respect to 100 parts by mass of the heat-treated toner particles 1, 0.2 parts by mass of the inorganic particles 3 and 0.2 parts by mass of the inorganic particles 4 are adjusted to a Henschel mixer (FM-75 type, for the purpose of chargeability and fluidity adjustment. (Mitsui Miike Kako Co., Ltd.). Toner 1 was obtained by mixing at a rotation speed of 30 s ⁻¹ and a rotation time of 10 min. Toner 1 had a weight average particle diameter (D4) of 6.5 μm and an average circularity of 0.965. The physical properties of the toner are shown in Table 4.

<Toner Production Examples 2 to 18>
Toners 2 to 18 shown in Table 4 were produced in the same manner as in Toner Production Example 1 except that the type of resin B, the amount of crystalline resin C1, the number of kneading revolutions, and the kneading temperature were varied. However, the hot air treatment for fixing the organic / inorganic composite particles to the toner particle surfaces was not performed on the toner particles 12, 14, and 16. Table 3 shows the material formulation and manufacturing conditions. Table 3 also shows the types and amounts of the external additives used.

  Table 4 also shows the dispersion state (number average major axis length, area standard deviation) of the crystalline polyester in the TEM cross section when the crystalline resin C1 is added.

<Example of production of magnetic core particles>
Process 1 (weighing / mixing process):
Fe ₂ O ₃ 60.2 mass%
MnCO ₃ 33.9% by mass
Mg (OH) ₂ 4.8% by mass
SrCO ₃ 1.1% by mass
The ferrite raw material was weighed so that Thereafter, the mixture was pulverized and mixed for 2 hours in a dry ball mill using zirconia (φ10 mm) balls.

Step 2 (temporary firing step):
After pulverization and mixing, firing was performed at 1000 ° C. for 3 hours in the air using a burner-type firing furnace to prepare calcined ferrite. The composition of the ferrite is as follows.
(MnO) a (MgO) b (SrO) c (Fe 2 O 3) d
In the above formula, a = 0.39, b = 0.11, c = 0.01, d = 0.50

Step 3 (grinding step):
After crushing to about 0.5 mm with a crusher, 30 parts by mass of water was added to 100 parts by mass of calcined ferrite using zirconia (φ10 mm) balls, and the mixture was pulverized with a wet ball mill for 2 hours.

  The slurry was pulverized for 4 hours by a wet bead mill using zirconia beads (φ1.0 mm) to obtain a ferrite slurry.

Process 4 (granulation process):
To the ferrite slurry, 2.0 parts by mass of polyvinyl alcohol was added as a binder with respect to 100 parts by mass of calcined ferrite, and granulated into spherical particles of about 36 μm with a spray dryer (manufacturer: Okawahara Chemical).

Process 5 (main baking process):
In order to control the firing atmosphere, firing was performed at 1150 ° C. for 4 hours in an electric furnace under a nitrogen atmosphere (oxygen concentration of 1.00% by volume or less).

Process 6 (screening process):
After the aggregated particles were crushed, coarse particles were removed by sieving with a sieve having an opening of 250 μm to obtain magnetic core particles 1.

<Example of coating resin production>
Cyclohexyl methacrylate monomer 26.8 parts by mass Methyl methacrylate monomer 0.2 part by mass Methyl methacrylate macromonomer 8.4 parts by mass (macromonomer having a methacryloyl group at one end and a weight average molecular weight of 5000)
Toluene 31.3 parts by mass Methyl ethyl ketone 31.3 parts by mass The above materials were added to a four-necked separable flask equipped with a reflux condenser, thermometer, nitrogen introduction tube and stirring device, and nitrogen gas was introduced to sufficiently In a nitrogen atmosphere. Thereafter, the mixture was heated to 80 ° C., 2.0 parts by mass of azobisisobutyronitrile was added, and the mixture was refluxed for 5 hours for polymerization. Hexane was injected into the obtained reaction product to precipitate a copolymer, and the precipitate was filtered off and dried under vacuum to obtain a coat resin.

<Example of manufacturing magnetic carrier>
Coat resin 20.0% by mass
Toluene 80.0% by mass
The above materials were dispersed and mixed with a bead mill to obtain a resin liquid.

  100 parts by mass of the magnetic core particles were put into a Nauta mixer, and further, the resin liquid was put into a Nauta mixer so as to be 2.0 parts by mass as a resin component. The mixture was heated to 70 ° C. under reduced pressure, mixed at 100 rpm, and solvent removal and coating operations were performed over 4 hours. Thereafter, the obtained sample was transferred to a Julia mixer, heat-treated at 100 ° C. for 2 hours in a nitrogen atmosphere, and then classified with a sieve having an opening of 70 μm to obtain a magnetic carrier. The volume distribution standard 50% particle size (D50) of the obtained magnetic carrier was 38.2 μm.

<Manufacture of two-component developer>
With the above magnetic carrier and toners 1-18, 0.5 s ^{−1 with} a V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) and a rotation time of 5 min so that the toner concentration becomes 8.0% by mass. Two-component developers 1 to 18 were obtained by mixing.

[Example 1]
The following evaluation was performed using the two-component developer 1.

<Durability evaluation Low printing rate mode>
Image evaluation was performed after the developer of Canon full color copier imageRUNNER ADVANCE C5051 was idly rotated (no toner replenished) and the developer was stressed. This evaluation is performed for the purpose of promoting evaluation of a low printing rate, that is, durability in a state where there is almost no toner replacement. As a specific method, in an environment of high temperature and high humidity (40 ° C / 40% Rh), an image is output with the developer after being idled for 5 hours by the development idle rotation jig for imageRUNNER ADVANCE, and the occurrence of white spots is observed. Evaluating. The white spot here is a phenomenon that occurs when the developing carrier flies onto the photosensitive drum together with the toner during development, and the toner around the carrier is not transferred at the primary transfer portion. This is a phenomenon that easily occurs when the developability of the toner is remarkably lowered, and occurs because the necessary development contrast for outputting an appropriate image density increases. In general, when the non-electrostatic adhesion force between the toner and the carrier becomes large, it becomes impossible to respond to the flying force due to the electric field, and the developability deteriorates. In this idling evaluation, stress is applied to the toner to create a state in which the external additive is buried or the external additive falls into the recess of the base material. As the embedding and dropping progress, the toner base comes into direct contact with the carrier, and the non-electrostatic adhesion force between the toner and the carrier increases, resulting in white spots. The image quality was evaluated using an imageRUNNER ADVANCE C5051 in a normal temperature and normal humidity (23 ° C., 50%) environment. The image density was output using a X-Rite color reflection densitometer (500 series: manufactured by X-Rite) under the condition that the solid on paper (FFh) density was 1.4. As the evaluation paper, CS-680 (68.0 g / m ² ) (sold from Canon Marketing Japan Inc.) was used. The number of white spots was A4 size, and 17 gradations (00h to FFh, each horizontal band 10 mm × 290 mm) were output and the number of occurrences was counted.

The evaluation criteria were as follows. (Number of white spots after 5h idling)
A: Less than 3 (excellent)
B: 3 or more and less than 10 (slightly better)
C: 10 or more and less than 20 (Acceptable level in the present invention)
D: 20 or more (Unacceptable level in the present invention)

  Table 5 shows the results of evaluating the toner by the above evaluation methods and standards.

<Durability evaluation High printing rate mode>
An endurance test was conducted at a high printing rate (printing rate 40%) in a high temperature and high humidity environment (30 ° C./80% Rh) using a modified machine of Canon full color copying machine imageRUNNER ADVANCE C5051. Here, a phenomenon is observed in which the chargeability of the toner is reduced by the external additive of the toner being detached and moving to the carrier surface. Durability in the high printing mode increases the amount of toner replenished, and as a result, the total amount of the external additive to be removed increases, so it is suitable for expeditious evaluation of the carrier surface spent due to the external additive (leading to a decrease in carrier charging ability). ing. Replacement of development carrier during endurance (auto refresh mechanism) is not performed. A change in toner charge amount is not preferable because it leads to fluctuations in image density.

As the evaluation paper, CS-680 (68.0 g / m ² ) (sold from Canon Marketing Japan Inc.) was used.

  The number of durable sheets was A4 chart, continuous 20000 sheets. For the evaluation of charging property, an average toner charge amount of 3000 toners in the developer was measured using an E-spart analyzer manufactured by Hosokawa Micron.

The evaluation criteria were as follows.
A: Less than 10% (excellent)
B: 10 or more and less than 20% (Acceptable level in the present invention)
C: 20% or more (Unacceptable level in the present invention)

  Table 5 shows the results of evaluating the toner by the above evaluation methods and standards.

[Examples 2 to 11 and Comparative Examples 1 to 7]
Evaluation was performed in the same manner as in Example 1 except that the two-component developer was changed as shown in Table 5. The evaluation results are shown in Table 5.

1. 1. Raw material quantitative supply means, 2. compressed gas flow rate adjusting means; 3. Introducing tube, 4. Protruding member, 5. supply pipe, 6. processing chamber; Hot air supply means, 8. Cold air supply means, 9. Regulatory means, 10. Recovery means, 11. 11. Hot air supply means outlet, 12. distribution member; Swivel member,
14 Powder particle supply port

Claims (2)

A method for producing a toner containing toner particles containing a binder resin and organic-inorganic composite particles,
The method for producing the toner includes:
Mixing the toner base particles containing the binder resin and the organic-inorganic composite particles; and
A step of fixing the organic-inorganic composite particles to the surface of the toner base particles by surface treatment with hot air to obtain toner particles having the organic-inorganic composite particles fixed to the surface;
Have
The organic-inorganic composite particles have a number average particle size of 50 nm to 200 nm, and the organic-inorganic composite particles have a structure in which inorganic fine particles are embedded in vinyl-based resin particles. There are a plurality of convex portions derived from inorganic fine particles,
And a method for producing the toner. The binder resin contains a crystalline polyester resin and an amorphous polyester resin,
In the transmission electron microscope (TEM) cross section of the toner particles treated with ruthenium dyeing, the crystalline polyester forms crystals that are observed in a needle shape on the cross section of the toner particles, and the major axis length of the crystals is When the number average diameter (D1) is 60 nm or more and 250 nm or less and the area occupied by the crystalline polyester in the toner particle cross section in the 1.0 μm × 1.0 μm visual field in the cross section of the toner particle is obtained, the area standard The deviation is 10.0% or less,
The method for producing a toner according to claim 1, wherein:

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