JP2016139063A - toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide toner that has both durable stability and fixability superior than that of the prior art.SOLUTION: Toner includes toner particles having organic-inorganic complex particles fixed on the surface, obtained by: fusing and kneading a mixture containing crystalline polyester resin, amorphous polyester resin, and wax; pulverizing the obtained kneaded product to obtain a toner particle precursor; and mixing the toner particle precursor and organic-inorganic complex particles before surface treatment by heat. The organic-inorganic complex particles and inorganic fine particles A are present on the surface of the toner particles. The organic-inorganic complex particles have a number average particle diameter of 50 nm or more and 350 or less, and have a structure where inorganic fine particles B are embedded in vinyl resin particles. A plurality of projections due to the inorganic fine particles B are present on the surface of the organic-inorganic complex particles. The inorganic fine particles A include primary particles having a number average particle diameter of 60 nm or more and 300 nm or less.SELECTED DRAWING: None

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 a 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, so that the object (development carrier, photosensitive drum, intermediate transfer member, etc.) Adhesive force increases, leading to deterioration in 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, an attempt has been made to maintain the spacer function after applying stress by coating a toner base with a large particle size monodispersed spherical external additive (see Patent Document 1). However, the external additive having a large particle size is easily detached from the surface of the base, and the detached external additive adheres to the surface of the development carrier, resulting in a problem that the triboelectric charging performance with the toner is lowered and the charge amount of the toner is reduced. Disclosed is a method for immobilizing an inorganic fine powder having a large particle size on the toner particle surface by applying strong shearing in the gap between the rotary drive unit and the casing in the external additive mixing tank in order to strongly attach the external additive to the toner base. (See Patent Document 2). 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.

  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 (Patent Document 3). 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.

  On the other hand, in order to improve transfer efficiency, a proposal has been made to increase the circularity of the toner by heat-treating the toner (see Patent Document 4). However, in the heat-treated toner, the circularity of the toner is increased and the transferability is improved, while the highly adherent wax is eluted near the toner surface. For this reason, when stress is applied to the toner and the external additive is buried, the highly adhesive wax comes into contact with the object, leading to a decrease in transferability or developability. If a wax having a relatively high melting point is used, it is possible to reduce the adhesion of the wax. However, when such a wax is used, since the viscosity is high, there may occur a problem that paper is wound around the fixing member at the time of fixing (deterioration of separability).

  Further, from the viewpoint of energy saving, it is desired to realize a toner that can be fixed quickly and at low energy by melting at a lower temperature than before.

  In order to satisfy these requirements, it is necessary to soften the toner, but this cannot be achieved simply by softening the toner from the viewpoint of heat-resistant storage stability and durability.

  Therefore, a toner has been proposed in which a low-temperature fixing performance and storage stability of a toner are improved by adding a composite resin composed of a crystalline resin having sharp melt properties and an amorphous resin (see Patent Document 5). .

  However, even when such toner is used, if image output is performed for a long time in a high temperature and high humidity environment, the temperature in the copying machine body rises, so that the wax in the vicinity of the toner surface is eluted and the transfer efficiency is increased. May be reduced.

  As described above, there is still room for improvement with regard to achieving both the durability stability and the fixing property of the toner while achieving high image quality.

JP 2002-318467 A JP 2008-292675 A JP 2007-279702 A JP 2013-15830 A JP 2011-123352 A

  An object of the present invention is to satisfy stable durability from beginning to end and to obtain excellent fixing properties. In particular, (1) prevention of an increase in adhesion (deterioration of developability and transferability) due to the external additive being embedded in the toner base and preventing the spacer function from being achieved, and (2) a wax having a relatively high melting point was used. Even in such a case, it is desirable to provide a toner that exhibits excellent separation performance, and (3) prevents the external additive from adhering to the surface of the carrier due to liberation from the surface of the toner and thus reducing the chargeability.

The present invention provides a toner particle precursor by melt-kneading a mixture containing a crystalline polyester resin, an amorphous polyester resin, and a wax, and pulverizing the obtained kneaded product. A toner having toner particles obtained by mixing the composite particles and then performing a surface treatment with heat, the organic / inorganic composite particles fixed on the surface,
The organic-inorganic composite particles and inorganic fine particles A are present on the surface of the toner particles,
The wax is a hydrocarbon wax, and has a melting point T (° C.) measured by a differential scanning calorimeter (DSC) of 80 ° C. or more and 120 ° C. or less,
The organic-inorganic composite particles have a number average particle size of 50 nm or more and 350 nm or less, and have a structure in which inorganic fine particles B are embedded in vinyl resin particles, and the surface of the organic-inorganic composite particles has protrusions derived from the inorganic fine particles B. There are multiple parts,
The inorganic fine particles A have a number average particle size of primary particles of 60 nm to 300 nm,
Regarding the abundance ratio of the organic-inorganic composite particles and inorganic fine particles A on the surface of the toner, determined by X-ray photoelectron spectroscopy,
i) The total existence ratio of the organic-inorganic composite particles and the inorganic fine particles A is 30% to 70%,
ii) The abundance ratio of the organic-inorganic composite particles is 10% or more and 50% or less of the abundance ratio of the inorganic fine particles A.
This invention relates to a toner.

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

It is a figure of the thermal spheronization processing apparatus used for this invention.

The present invention provides a toner particle precursor by melt-kneading a mixture containing a crystalline polyester resin, an amorphous polyester resin, and a wax, and pulverizing the obtained kneaded product. A toner having toner particles to which the organic / inorganic composite particles are fixed on the surface, obtained by mixing the composite particles and then performing a surface treatment with heat, the surface of the toner particles having the organic / inorganic composite Particles and inorganic fine particles A exist,
The wax is a hydrocarbon wax, and has a melting point T (° C.) measured by a differential scanning calorimeter (DSC) of 80 ° C. or more and 120 ° C. or less,
The organic-inorganic composite particles have a number average particle size of 50 nm or more and 350 nm or less, and have a structure in which inorganic fine particles B are embedded in vinyl resin particles, and the surface of the organic-inorganic composite particles has protrusions derived from the inorganic fine particles B. There are multiple parts,
The inorganic fine particles A have a number average particle size of primary particles of 60 nm to 300 nm,
Regarding the abundance ratio of the organic-inorganic composite particles and inorganic fine particles A on the surface of the toner, determined by X-ray photoelectron spectroscopy,
i) The total existence ratio of the organic-inorganic composite particles and the inorganic fine particles A is 30% to 70%,
ii) The abundance ratio of the organic-inorganic composite particles is 10% or more and 50% or less of the abundance ratio of the inorganic fine particles A.
It is characterized by that.

  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.

  When the organic / inorganic composite particles of the present invention are used, they 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 minute irregularities formed by the inorganic fine particle component contained in the organic-inorganic composite fine particles are effective. The authors think that the minute unevenness prevents aggregation between the organic-inorganic composite particles, and has an appropriate catch on the surface of the toner particle precursor (also referred to as toner base), so that the bias to the base recess does not occur. I guess. 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, the inorganic fine particles are completely embedded in the resin particles and there are no convex portions. Uniform 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, they can be adhered to the surface of the toner base 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 the present invention, the state in which the toner particle precursor (toner base) is subjected to hot air treatment is referred to as toner particles. Since the organic-inorganic composite particles are fixed to the toner base by hot air treatment, they are fixed in the toner particles.

  The present invention is characterized in that inorganic fine particles A having a primary particle number average particle size of 60 nm to 300 nm are used in combination with the organic-inorganic composite particles. Normally, when only inorganic fine particles of 60 nm or more and 300 nm or less are used as external additives, it is difficult to uniformly diffuse and adhere to the toner base surface. However, in the present invention, by using the organic-inorganic composite particles in combination, it is possible to uniformly diffuse inorganic fine particles of 60 nm or more and 300 nm or less. This is presumably because the organic-inorganic composite particles are uniformly diffused and scattered, thereby preventing the inorganic fine particles from rolling on the surface of the base material and preventing the depression of the concave portions. 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 exhibit excellent durability by using particles having a number average particle diameter of 50 nm or more and 350 nm or less. 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. Further, the size is not sufficient to prevent the inorganic fine particles A from rolling. On the other hand, if it exceeds 350 nm, the external additive is easily detached in the hot air treatment apparatus, and is not suitable. On the other hand, when the number average particle diameter of the inorganic fine particles A is 60 nm or more and 300 nm or less, excellent durability can be expressed. If the thickness is less than 60 nm, the spacer function is weakened and the effect expected in the present invention cannot be obtained. On the other hand, if it exceeds 300 nm, it will be easy to detach from the toner particle surface, or it will be difficult to uniformly diffuse without being dammed by the organic-inorganic composite particles during external addition.

  Further, the total existence ratio (coverage) of the organic / inorganic composite particles and the inorganic fine particles A is suitably 30% or more and 70% or less. If it is less than 30%, the area where the toner base is exposed increases, the adhesion to the object increases, and the toner has only a conventional level of durability stability. If it exceeds 70%, the external additive inhibits heat conduction and the low-temperature fixability required in the present invention cannot be obtained.

  In the present invention, a wax having a melting point of 80 ° C. or higher and 120 ° C. or lower is used for further improving the durability. In the present invention, as described above, the shape, particle size, and coverage of the external additive are characterized by providing durability that exceeds the conventional one. However, when a strong stress is applied to the toner, the external additive is inevitably embedded in the toner base. As a result, a portion where the toner base comes into contact with the object appears. The toner base has higher adhesion than the external additive, which is considered to be caused by the softness of the toner base. When the substance is soft, the contact area with the object increases, and it is considered that the non-electrostatic adhesion force increases. An example of a substance in the toner base relating to the softness is wax. One of the purposes of including the wax in the toner is to exude the wax during the fixing process and form a release layer between the fixing member and the toner layer to prevent the paper from being fixedly wound. It is considered that the separation performance can be obtained by reducing the viscosity at the time of fixing, thereby obtaining a releasing effect. However, lowering the viscosity when the temperature increases means that it becomes softer when the temperature rises in the machine and the adhesion is increased. In particular, it is considered that the toner base produced by the melt pulverization method of the present invention is easily affected by the presence of wax on the surface.

  In the present invention, by using a wax having a melting point of 80 ° C. or higher, excellent durability can be obtained even when stress is applied in the developing device when the temperature rises in the apparatus. This is presumably because the adhesion of the toner base could be weakened as described above.

  However, when a wax having a high melting point is used, the above-described fixing separation performance tends to be inferior. In the present invention, hot air treatment is used to improve this. When heat is applied to the toner base, the wax moves to the vicinity of the surface. In the present invention, the presence of a large amount of wax in the vicinity of the surface of the toner base can promote the seepage of the wax during fixing, thereby improving the separation performance.

  Moreover, although crystalline polyester is used in this invention, it discovered that this presence also contributed to separation improvement. Although the mechanism of the release effect at this time is not completely clarified, the present inventors considered as follows. As described above, in order to express the releasing effect more effectively, it is important that the wax appears on the toner surface promptly at the time of fixing. In the present invention, since the crystalline polyester is present, the crystalline polyester is compatible with the amorphous polyester at the time of fixing, and the melted wax passes through the compatible portion to promote the expression of the wax on the toner surface. It is thought that it is done. This phenomenon is considered to be manifested specifically because the toner base produced by the melt-kneading method can exist in a state in which the crystalline polyester is finely dispersed. When crystalline polyester is present as a domain as in the polymerization method, it is considered that the leaching of wax cannot be quickly deposited on the entire surface.

  As described above, the hot air treatment of the present invention is aimed at fixing the organic-inorganic composite particles to the toner base in a highly diffused state and moving the wax to the vicinity of the surface. From the viewpoint of fixing the external additive, the inorganic fine particles A may also be thermally fixed. Even when the organic-inorganic composite particles and the inorganic fine particles A are simultaneously externally added to the toner base, uniform diffusion is possible. This is due to the shape of the organic / inorganic fine particles, which is thought to prevent aggregation of external additives and prevent the inorganic fine particles from shifting (rolling). When the organic / inorganic composite particles and the inorganic fine particles A are fixed to the toner base by hot air treatment, the external additive can be prevented from being released from the toner base, and higher durability can be obtained.

<Organic inorganic composite particles (external additive)>
The organic-inorganic composite fine particles used in the present invention can be produced, for example, according to the description of the examples in WO2013 / 063291.

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

<Inorganic fine particles (external additives)>
Examples of the inorganic fine particles that can be used in the present invention include fluorine 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. There are powdered silica, treated silica obtained by subjecting them to surface treatment with a silane compound, an organosilicon compound, a titanium coupling agent, silicone oil and 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.

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

[Amorphous polyester resin]
The amorphous polyester resin used in the toner of the present invention needs to have a polyester resin as a main component. Monomers used in the polyester unit of the polyester resin include polyhydric alcohols (divalent or trivalent or higher alcohols), polyvalent carboxylic acids (divalent or trivalent or higher carboxylic acids), acid anhydrides thereof or lower ones thereof. Alkyl esters are used. Here, when preparing a branched polymer, it is effective to partially crosslink in the molecule | numerator of binder resin, and it is preferable to use the polyfunctional compound more than trivalence for that purpose. Therefore, it is preferable to include a trivalent or higher carboxylic acid, its acid anhydride or its lower alkyl ester, and / or a trivalent or higher alcohol as a raw material monomer for the polyester unit.

  As the polyhydric alcohol monomer used in the polyester unit of the polyester resin, the following polyhydric alcohol monomers can be used.

  Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and bisphenol represented by formula (A) and derivatives thereof;

（式中、Ｒはエチレンまたはプロピレン基であり、ｘ及び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以上１０以下である。）
式（Ｂ）で示されるジオール類；

(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 or more and 10 or less.)
Diols represented by formula (B);

が挙げられる。

Is mentioned.

  Examples of the trivalent or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol. 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene Can be mentioned. Of these, glycerol, trimethylolpropane, and pentaerythritol are preferably used. These dihydric alcohols and trihydric or higher alcohols can be used alone or in combination.

  As the polyvalent carboxylic acid monomer used in the polyester unit of the polyester resin, the following polyvalent carboxylic acid monomers can be used.

  Examples of the divalent carboxylic acid component include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, anhydrides of these acids and These lower alkyl esters are mentioned. Of these, maleic acid, fumaric acid, terephthalic acid, and n-dodecenyl succinic acid are preferably used.

  Examples of the trivalent or higher carboxylic acid, its acid anhydride or its lower alkyl ester include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid. 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra ( Methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empole trimer acid, acid anhydrides thereof, or lower alkyl esters thereof. Among these, in particular, 1,2,4-benzenetricarboxylic acid, that is, trimellitic acid or its derivative, is inexpensive and easy to control, so that it is preferably used. These divalent carboxylic acids and the like and trivalent or higher carboxylic acids can be used alone or in combination.

  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.

  Further, the peak molecular weight of the binder resin of the present invention is preferably 8000 or more and 13000 or less from the viewpoints of low-temperature fixability and hot offset resistance. The acid value of the binder resin of the present invention 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. Furthermore, the hydroxyl value of the binder resin of the present invention is preferably 2 mgKOH / g or more and 20 mgKOH / g or less from the viewpoint of low-temperature fixability and storage stability.

  Further, the binder resin of the present invention may be used by mixing a low molecular weight binder resin B and a high molecular weight binder resin A together. The content ratio (A / B) of the high molecular weight binder resin A and the low molecular weight binder resin B is 10/90 or more and 60/40 or less in terms of mass, from the viewpoint of low temperature fixability and hot offset resistance. To preferred.

  The peak molecular weight of the high molecular weight binder resin A is preferably 10,000 or more and 20,000 or less 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 B 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.

[Crystalline resin]
The toner of the present invention contains a crystalline polyester.

  When a polyester resin is used as the amorphous resin, it is important to use polyester as the crystalline resin in order to sufficiently exhibit the plastic effect.

  In the toner of the present invention, the crystalline polyester contained in the toner particles is obtained by a polycondensation reaction of a monomer composition containing an aliphatic diol and an aliphatic dicarboxylic acid as main components. The aliphatic diol and the aliphatic dicarboxylic acid preferably have 6 to 12 carbon atoms.

  The aliphatic diol is not particularly limited, but is preferably a chain (more preferably linear) aliphatic diol, such as 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, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene And glycol 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 6 to 12 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 is not particularly limited, but is preferably a chain (more preferably linear) aliphatic dicarboxylic acid. 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 6 to 12 carbon atoms.

  In the present invention, polyvalent carboxylic acids other than aliphatic dicarboxylic acids can also 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 the polycondensation reaction, all monomers may be charged at once in order to increase the strength of the resulting crystalline polyester. In order to reduce the low molecular weight component, a method in which a divalent monomer is first reacted and then a trivalent or higher monomer is added and reacted may be used.

  It is important that the crystalline polyester is contained in an amount of 1.0 to 15 parts by mass with respect to 100 parts by mass of the amorphous resin. When the content of the crystalline polyester is in this range, it is possible to efficiently precipitate the wax during fixing while improving the low-temperature fixability. When the content of the crystalline polyester is less than 1.0 part by mass, the low-temperature fixability is impaired. When the content of the crystalline polyester exceeds 15 parts by mass, the amount of the crystalline polyester that is compatible with the amorphous polyester exceeds the limit, and the crystallization of the crystalline polyesters proceeds. For this reason, the wax is expected to be deposited at the time of fixing, which is expected in the present invention.

[wax]
The release agent contained in the toner used in the present invention is preferably a hydrocarbon wax. The toner used in the present invention uses a polyester resin as the binder resin. However, if the toner is too compatible with the polyester resin, the separating function from the toner as a release agent may be insufficient. It is considered that the offset of the polyester resin component tends to occur, and the component remaining on the heating roll after the offset tends to adhere to the metal roll in contact with the pressure roll. Hydrocarbon wax, which is considered to be incompatible with polyester, is easy to bleed from the toner, and even if an offset component is generated, it does not adhere to the metal roll and does not accumulate easily, so image stains are unlikely to occur. Become.

  The melting point of the hydrocarbon wax is preferably 80 ° C. or higher and 120 ° C. or lower. When the melting point of the hydrocarbon wax exceeds 120 ° C., the separation performance at the time of fixing becomes severe even in the constitution using the hot air treatment and crystalline polyester of the present invention. Moreover, durability is not satisfy | filled as above-mentioned that it is less than 80 degreeC.

  Examples of the hydrocarbon wax include paraffin wax, olefin wax, Fischer-Tropsch wax, and polyethylene wax.

  The toner used in the present invention preferably contains a hydrocarbon wax at 3% by mass or more and 15% by mass or less from the viewpoint of durability and separability.

[Colorant]
Examples of the colorant that can be contained in the toner of the present invention 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 colored 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 coloring 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.

  The following are mentioned as a cyan coloring pigment. 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 coloring dyes include C.I. I. There is Solvent Blue 70.

  The following are mentioned as a yellow coloring pigment. 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 yellow coloring dyes 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 of the present invention 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. 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.

<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 KC K ), Co-kneader (manufactured by Buss), kneedex (manufactured by Nippon Coke Industries Co., Ltd.) 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 device such as a hybrid (manufactured by Nippon Coke Industries Co., Ltd.), Nobilta (manufactured by Hosokawa Micron Co., Ltd.) or the like as an external adder.

  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.

  Discrimination between organic-inorganic composite particles and inorganic fine particles can be made easier than S-4800 due to the difference in particle shape.

<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.

<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 Nikkiki 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.

<Method of measuring coverage by ESCA>
The external additive coverage in the present invention is calculated from the atomic weight of silicon derived from silica (hereinafter abbreviated as Si) present on the surface of the toner particles, as measured by ESCA (X-ray photoelectron spectroscopy). ESCA is an analysis method for detecting atoms in a region of several nm or less in the depth direction of the sample surface. Therefore, it is possible to detect atoms on the surface of the magnetic toner. As a sample holder, a 75 mm square platen (provided with a screw hole of about 1 mm diameter for fixing the sample) attached to the apparatus was used. Since the screw hole of the platen penetrates, the hole is closed with resin or the like, and a recess for measuring powder having a depth of about 0.5 mm is produced. A sample was prepared by filling the recess with a measurement sample with a spatula or the like and grinding it.

  The ESCA apparatus and measurement conditions are as follows.

Device used: PHI5000 VersaProbeII manufactured by ULVAC-PHI
Analysis method: Narrow analysis Measurement conditions:
X-ray source: Al-Kα
X-ray conditions: 100μ25W15kV
Photoelectron capture angle: 45 °
PassEnergy: 58.70eV
Measurement range: 300 μm × 200 μm

  Measurement was performed under the above conditions. The analysis method first corrects the peak derived from the C—C bond of the carbon 1s orbital to 285 eV. Then, from the peak area derived from the silicon 2p orbit where the peak top is detected at 100 eV or more and 105 eV or less, the relative sensitivity factor provided by ULVAC-PHI is used to calculate the amount of Si derived from silica relative to the total amount of constituent elements. To do. Next, the silica alone applied to the toner was measured by the same method as described above, the amount of Si derived from silica relative to the total amount of the constituent elements was calculated, and the toner relative to the amount of Si when measuring the external additive alone was measured. The ratio of the amount of Si at that time is defined as the silica coverage in the present invention.

  The method for measuring the inorganic fine particle surface abundance ratio of the organic / inorganic composite particles is performed using the above-mentioned ESCA, and the apparatus, measurement conditions, and analysis method are the same as those for measuring the silica coverage of the toner. First, organic-inorganic composite particles are measured. Moreover, the particle | grains of the inorganic component used when producing organic-inorganic composite particle | grains by the same method are measured. When the inorganic component is silica, the ratio of the amount of Si when the organic-inorganic composite particles are measured to the amount of Si when the silica particles are measured is the abundance ratio of the inorganic fine particles on the surface of the organic-inorganic composite particles in the present invention. To do. In this measurement, calculation was performed using the sol-gel silica particles (number average particle diameter 101 nm) described in the production examples as the silica particles.

  Incidentally, when the external additive is silica alone, the silica content is 100%, and when the surface treatment is not particularly performed, the silica content of the resin particles is 0%.

<Measurement of DSC endotherm (ΔH) of wax and CPES>
The peak temperature (Tp) of the maximum endothermic peak of the toner or the like (toner, crystalline polyester) in the present invention is measured using DSC Q1000 (manufactured by TA Instruments) under the following conditions.
Temperature increase rate: 10 ° C / min
Measurement start temperature: 20 ° C
Measurement end temperature: 180 ° C

  The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.

  Specifically, about 5 mg of a sample is precisely weighed, placed in a silver pan, and measured once. A silver empty pan is used as a reference.

  When using toner as a sample, if the maximum endothermic peak (maximum endothermic peak derived from the binder resin) does not overlap with the endothermic peaks of resins other than wax and crystalline resin, the endothermic amount of the maximum endothermic peak obtained Is treated as the endothermic amount of the maximum endothermic peak derived from the wax and the crystalline resin. On the other hand, when the toner is used as a sample, if the endothermic peak of the resin other than the wax and the binder resin overlaps with the maximum endothermic peak of the binder resin, the endothermic amount derived from the resin other than the wax and the binder resin is calculated. It is necessary to subtract from the endothermic amount of the maximum endothermic peak obtained.

  The maximum endothermic peak means a peak where the endothermic amount is maximum when there are a plurality of peaks. Further, the endothermic amount (ΔH) of the maximum endothermic peak is obtained from the peak area by calculation using analysis software attached to the apparatus.

  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 organic-inorganic composite particle has a plurality of convex portions derived from silica (inorganic fine particles B) on the surface thereof.

<Production example of inorganic fine particles 1 to 3>
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, by adding 10 parts by mass of hexamethyldisilazane as a surface treatment agent to 100 parts by mass of the silica fine particles obtained, a hydrophobic treatment is performed to obtain inorganic fine particles 1. The shape exists in a mixed state from spherical to indefinite shape. The physical properties are shown in Table 2.

  The inorganic fine particles 2 and 3 were produced by changing the average gas supply rate, the hydrogen supply amount, and the oxygen ratio.

<Example of production of inorganic fine particles 4>
The inorganic fine particles 4 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 fine 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.

<Inorganic fine particles 5>
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.

<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.

<Amorphous polyester resin B production example 1>
・ 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.

<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 90 ° 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 minutes, the mixture was kneaded at a discharge temperature of 150 ° C. with a biaxial 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 .

2.5 parts by mass of the organic / inorganic composite particles 1 and 0.2 parts by mass of the inorganic fine particles 5 are added to the obtained toner base, and the number of rotations is increased with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.). The mixture was mixed for 30 s ⁻¹ for 10 minutes in rotation time to obtain an external additive mixture 1 of toner precursor. The purpose of adding the inorganic fine particles 5 is to impart fluidity to the toner base. Since the inorganic fine particle 5 has a small particle size, it does not contribute to the durability of the effect expected in the present invention, but is added for the purpose of imparting the fluidity necessary for performing uniform processing in the hot air apparatus.

The mixture was heat-treated with the surface treatment apparatus shown in FIG. The operating conditions were a feed amount = 5 kg / hr, a hot air temperature = 160 ° C., and a 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. Injection air flow rate = 1 m ³ / min. It was.

Further, with respect to 100 parts by mass of the heat-treated toner particles 1, 5.5 parts by mass of inorganic fine particles 1 as inorganic fine particles A were mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical 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. Table 4 shows the total existence ratio and the existence ratio of the organic-inorganic composite particles and the inorganic fine particles A of the toner 1.

<Toner Production Examples 2 to 26>
Toners 2 to 26 were produced in the same manner as in Toner Production Example 1 except that the amount of crystalline resin C1, the kind / amount of organic / inorganic composite particles, the kind / amount of inorganic fine particles, the melting point of wax, and hot air treatment conditions were varied. Table 3 shows the material formulation and manufacturing conditions. Table 4 shows the total existence ratio and the existence ratio of the organic-inorganic composite particles and the inorganic fine particles A of the obtained toner.

<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 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 pulverizing 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 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 magnetic carrier production>
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.

In more toner 1-26 and magnetic carrier, a toner concentration of 8.0% by mass so as to V-type mixer: with (V-10 type, Ltd. Tokuju Seisakusho) 0.5 s ^-1, at rotation time 5min Two-component developers 1 to 26 were obtained by mixing.

[Examples 1 to 20, Comparative Examples 1 to 6]
Each of the following evaluation items was examined.

<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: No occurrence (very good)
B: 1 or more and less than 5 (good)
C: 5 or more and less than 20 (Acceptable level in the present invention)
D: 20 or more (not acceptable in the present invention)

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

<Evaluation of paper separation>
A Canon full-color copier imageRUNNER ADVANCE C9075PRO was modified so that the fixing temperature and process speed could be freely set, and the fixing temperature region test was conducted. The image was adjusted so that the amount of toner applied on the paper was 1.2 mg / cm ² in a single color mode under a normal temperature and humidity environment (23 ° C./50%), and an unfixed image was created. The evaluation paper used was copy paper GFR070 (A4, basis weight 67.0 g / m ² sold by Canon Marketing Japan Inc.), and an image was formed at an image printing ratio of 25%. The tip margin was 4 mm. Thereafter, in a high-temperature and high-humidity environment (30 ° C./85%), the process speed is set to 320 mm / sec, the fixing temperature is increased in increments of 5 ° C. in order from 100 ° C., and the temperature range at which separation failure from the fixing member does not occur. Separable area. The upper limit temperature of the separable region was defined as the separable temperature. The evaluation results are shown in Table 5.

(Evaluation criteria for paper separation)
A: 150 ° C. or higher Excellent B: 140 ° C. or higher and lower than 150 ° C. Good C: 120 ° C. or higher and lower than 140 ° C. D: less than 120 ° C. which is not a problem in the present invention Unacceptable in the present invention

<Low temperature fixability>
Paper: CS-680 (68.0 g / m ² )
(Sold from Canon Marketing Japan Inc.)
Amount of toner on paper: 1.20 mg / cm ²
Evaluation image: An image of 10 cm ² is placed in the center of the above A4 paper. Fixing test environment: Low temperature and low humidity environment: Temperature 15 ° C./Humidity 10% RH (hereinafter “L / L”)

After adjusting the DC voltage V _DC of the developer carrier, the charging voltage V _D of the electrostatic latent image carrier, and the laser power so that the toner loading amount on the paper becomes the above, the process speed is set to 450 mm / sec, The fixing temperature was set to 130 ° C. and the low temperature fixing property was evaluated. The value of the image density reduction rate was used as an evaluation index for low-temperature fixability. The image density reduction rate is determined by first measuring the image density at the center using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite). Next, a load of 4.9 kPa (50 g / cm ² ) is applied to the portion where the image density has been measured, and the fixed image is rubbed (reciprocated 5 times) with sylbon paper, and the image density is measured again. Then, the reduction rate (%) of the image density before and after rubbing was measured.

(Evaluation criteria for low-temperature fixability)
A: Density reduction rate is less than 1.0% (very good)
B: Density reduction rate of 1.0% or more and less than 5.0% (good)
C: Density reduction rate of 5.0% or more and less than 10.0% (a level that is not a problem in the present invention)
D: Density reduction rate of 10.0% or more (not acceptable in the present invention)

<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% (very good)
B: 10% or more and less than 20% (good)
C: 20% or more and less than 30% (Acceptable level in the present invention)
D: 30% or more (not acceptable in the present invention)

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

  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 mixture containing a crystalline polyester resin, an amorphous polyester resin, and a wax is melt-kneaded, and the resulting kneaded product is pulverized to obtain a toner particle precursor, and the toner particle precursor and the organic-inorganic composite particles are combined. A toner having toner particles obtained by performing a surface treatment with heat after mixing and having the organic-inorganic composite particles fixed on the surface,
The organic-inorganic composite particles and inorganic fine particles A are present on the surface of the toner particles,
The wax is a hydrocarbon wax, and has a melting point T (° C.) measured by a differential scanning calorimeter (DSC) of 80 ° C. or more and 120 ° C. or less,
The organic-inorganic composite particles have a number average particle size of 50 nm or more and 350 nm or less, and have a structure in which inorganic fine particles B are embedded in vinyl resin particles, and the surface of the organic-inorganic composite particles has protrusions derived from the inorganic fine particles B. There are multiple parts,
The inorganic fine particles A have a number average particle size of primary particles of 60 nm to 300 nm,
Regarding the abundance ratio of the organic-inorganic composite particles and inorganic fine particles A on the surface of the toner, determined by X-ray photoelectron spectroscopy,
i) The total existence ratio of the organic-inorganic composite particles and the inorganic fine particles A is 30% to 70%,
ii) The abundance ratio of the organic-inorganic composite particles is 10% or more and 50% or less of the abundance ratio of the inorganic fine particles A.
Toner characterized by the above.   The toner according to claim 1, wherein the inorganic fine particles A are fixed to the surface of the toner particles by heat.

Images