JP2016142786A - toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner having excellent low-temperature fixability and hot offset resistance, a wide fixable temperature range and high heat-resistant storage property.SOLUTION: A toner includes: toner particles having a core-shell structure having a shell phase comprising a resin (A); and organic inorganic composite fine particles. The resin (A) has such characteristics that: (i) the resin has a siloxane bond; (ii) the resin shows in DSC measurement, a maximum endothermic peak temperature TpA of 55°C or higher and 80°C or lower in the first time of temperature elevation; and (iii) in viscoelasticity measurement, loss moduli G" (TpA) [Pa] and G"(TpA+10) [Pa] satisfy {log(G"(TpA))-log(G"(TpA+10))}≥1.0. The organic inorganic composite fine particles have such characteristics that: (iv) the particles have an embedded structure of inorganic fine particles in a surface of a resin particle comprising a resin having a siloxane bond, with a part of the inorganic fine particles exposed from the surface, and a resin component of the resin particle has a THF insoluble content of 70.0 mass% or more; and (v) the particles have a number average particle diameter of 50 nm or more and 500 nm or less.SELECTED DRAWING: None

Description

  The present invention relates to a toner used in a recording method using an electrophotographic method, an electrostatic recording method, and a toner jet recording method. Specifically, a toner used in an image forming method for forming a toner image on an electrostatic latent image carrier and then transferring the image onto a transfer material to form a toner image and fixing the image under thermal pressure to obtain a fixed image About.

  In recent years, in the field of copiers and printers, energy saving has been considered as a major technical issue, and in electrophotographic apparatuses, a great reduction in the amount of heat applied to the fixing apparatus has been cited. Therefore, there is an increasing need for low-temperature fixability that enables a toner to be sufficiently fixed with a low heat quantity.

  Conventionally, in order to enable fixing at a lower temperature, it is known as one of effective methods to impart a sharp melt property that melts a binder resin with a small temperature change. Focusing on this point, toner using crystalline polyester resin has been introduced. Crystalline polyester is not considered to exhibit a clear glass transition due to the regular arrangement of molecular chains, and is difficult to soften to the crystalline melting point. It has been broken.

  Patent Document 1 proposes a solution suspension method toner in which a block polymer in which a crystalline part containing a polyester resin and a non-crystalline part are bonded is used as a binder resin.

  In this proposal, low temperature fixability is controlled by controlling the endothermic peak temperature in the heat of fusion measurement using a differential scanning calorimeter (DSC) of the toner and the viscoelastic behavior before and after the melting start temperature in a descending flow tester. The aim is to achieve both blocking resistance.

  However, when crystalline polyester is used as the binder resin, it is possible to give the toner a sharp melt property, but the viscosity at the time of melting the toner is insufficient, and the toner adheres to the fixing member during fixing at a high temperature. (So-called hot offset) is likely to occur.

  In the toner having a core-shell structure, in order to further improve the low-temperature fixability, studies are being made to improve the low-temperature fixability by introducing a resin having crystallinity not only in the core resin but also in the shell material itself. .

  In Patent Document 2, a crystalline resin having a long chain alkyl group or a crystalline polyester chain is introduced into a shell material to impart sharp melt properties to the shell material, thereby achieving both low temperature fixability and heat resistant storage stability. A method has been proposed.

  However, it has been found that even with this method, it is difficult to maintain the viscosity when the toner is melted, and the hot offset resistance is insufficient.

  In Patent Document 3, in an aggregating toner containing a crystalline resin in a core, cross-linking between resin molecular chains is performed using metal ions in an aggregating agent used when agglomerating fine particles. As a result, the viscosity of the binder resin when the toner is melted is maintained, and the temperature range capable of fixing is expanded.

  However, in this method, it was found that the low-temperature fixability tends to decrease although the hot offset is improved by chemically bonding the molecular chains by ionic crosslinking.

  Therefore, further technical improvements have been required to improve the low-temperature fixability and the hot offset resistance.

  On the other hand, there is a demand for achieving higher image quality for toner.

  Toners made by chemical granulation methods such as dissolution suspension method, emulsion aggregation method, suspension polymerization method (so-called chemical toners) have a spherical and sharp particle size distribution, and therefore have excellent transferability and fine line reproducibility. Have. However, in these toners, when a cleaning method that uses a blade to remove the transfer residual toner on the photoconductor is used, the greater the circularity, the easier the toner slips through the blade, and the toner is removed. It tends to be difficult. As a result, the slipped toner tends to cause defects such as vertical stripes in the image on paper.

  Therefore, in order to improve the cleaning property, a device using an external additive has been devised. However, when used for a long period of time, embedding and detachment of external additives tend to occur, causing a deterioration in cleaning properties, and image defects as described above are likely to occur.

  Further, when the external additive is desorbed in the developing device, the toner adheres to the regulating blade of the developing device with the external additive as a core, and the supply of the toner is inhibited at the adhering portion, and the image on the paper is lost. Defects such as vertical stripes are likely to occur.

  In Patent Document 4, there is a means for embedding fine particles in spherical toner base particles to form irregularities on the surface, reducing the residual toner by reducing the adhesion between the photoconductor and the toner, and improving the cleaning property. Proposed. However, even in that case, it has been difficult to maintain sufficient cleaning properties for long-term use.

JP 2010-217849 A JP 2010-150535 A Japanese Patent No. 4285289 JP 2012-68325 A

  The present invention provides a toner having excellent low-temperature fixability and hot offset resistance, a wide fixable temperature range, and high heat-resistant storage stability.

  In addition, the present invention provides a toner capable of preventing toner deterioration due to embedding and desorption of an external additive and obtaining a good image over a long period of time.

The present invention relates to a toner having a core containing a binder resin, a colorant, and a wax, a core-shell toner particle having a shell phase containing a resin A, and organic-inorganic composite fine particles,
The resin A is
(I) a resin having a siloxane bond,
(Ii) In the measurement with a differential scanning calorimeter (DSC), the peak temperature TpA (° C.) of the maximum endothermic peak at the first temperature rise is 55 ° C. or more and 80 ° C. or less,
(Iii) In the viscoelasticity measurement, the loss elastic modulus at the TpA (° C.) is G ″ (TpA) [Pa], and the loss elastic modulus at a temperature TpA + 10 (° C.) 10 ° C. higher than the TpA is G ″ (TpA + 10) [Pa ]
G ″ (TpA) and G ″ (TpA + 10) satisfy the following formula (1):
{Log (G ″ (TpA)) − log (G ″ (TpA + 10))} ≧ 1.0 (1)
The organic-inorganic composite fine particles are
(Iv) Tetrahydrofuran (THF), which is a resin component that has a structure in which inorganic fine particles are embedded in a partially exposed state on the surface of a resin particle containing a resin having a siloxane bond, and which constitutes the resin particle Insoluble matter is 70.0% by mass or more,
(V) the number average particle diameter is 50 nm or more and 500 nm or less,
This invention relates to a toner.

  According to the present invention, both the sharp melt property of the toner and the maintenance of the viscosity at the time of melting the toner are achieved, and the low temperature fixing property and the hot offset resistance are more excellent than the conventional ones. It is possible to provide toner.

  Furthermore, it is possible to provide a toner that can prevent deterioration of the toner due to embedding or detaching of the external additive even in the spherical toner and can obtain a good image over a long period of time.

It is the schematic of the measurement sample and jig | tool for measuring the viscoelasticity of this invention. It is a figure which shows the viscoelasticity of the toner of this invention. 1 is a schematic view of a toner manufacturing apparatus.

  The toner of the present invention is a toner having core-shell toner particles in which a shell phase containing a resin A is formed on the surface of a core containing a binder resin, a colorant and a wax. The shell phase may cover the core as a layer having a clear interface, but may have a form in which the core is covered in a state where no clear interface exists.

  The resin A in the toner of the present invention has a maximum endothermic peak peak temperature TpA (° C.) of 55 ° C. or higher and 80 ° C. or lower, preferably 55 ° C., as measured by a differential scanning calorimeter (DSC). It is not lower than 75 ° C and not higher than 75 ° C. When TpA is less than 55 ° C., the heat-resistant storage stability deteriorates, and toner aggregation occurs depending on the temperature rise during operation in the electrophotographic apparatus. When TpA exceeds 80 ° C., control of the viscoelasticity of the toner is severe, and it becomes difficult to design a toner that exhibits sharp melt properties in a temperature range aimed at low-temperature fixing.

  The value of TpA can be adjusted to the above range by appropriately changing the type of monomer that is a raw material used for the synthesis of the resin A.

In the toner of the present invention, in the measurement of the viscoelasticity of the resin A, the loss elastic modulus at TpA (° C.) is G ″ (TpA) [Pa], and the loss elastic modulus at temperature TpA + 10 (° C.) 10 ° C. higher than TpA is G ″. When (TpA + 10) [Pa], the relationship of the following formula (1) is satisfied.
log (G ″ (TpA)) − log (G ″ (TpA + 10)) ≧ 1.0 (1)

  The value on the left side in the formula (1) represents the amount of change in viscoelasticity in the vicinity of the melting point of the resin A. When the change in the viscoelasticity of the resin A satisfies the formula (1), the sharp melt of the shell phase is sufficiently secured, and the sharp melt property of the toner can be maximized.

  Note that “log” used in the present invention is a common logarithm with a base of 10.

  When the value on the left side of the formula (1) is less than 1.0, the shell phase is not sufficiently melted in the fixing temperature region, and the elution of the binder resin is hindered to deteriorate the low temperature fixing property. Preferably, the value on the left side of the formula (1) is 2.0 or more, more preferably 3.0 or more. However, when the value is increased, the shell material is sufficiently melted, but the viscosity of the toner is remarkably lowered at a high temperature, the viscosity is severely maintained, and it is difficult to improve the hot offset resistance.

  The toner of the present invention is obtained by externally adding organic resin composite particles to the surface of the toner particles described above. The organic / inorganic composite fine particles in the present invention are particles having a structure in which the mother particles are resin particles and the inorganic fine particles are embedded in a state where a part of the mother particles is exposed. These organic / inorganic composite fine particles exhibit chargeability and fluidity equivalent to those of colloidal silica, have a lower specific gravity than colloidal silica, and have many contact points due to surface irregularities. It has the feature that it can be suppressed.

  As a result, toner deterioration can be suppressed in the toner aimed at further improvement in low-temperature fixability.

  In the temperature range where the above-described hot offset occurs, it is considered that the toner is almost melted. The inventors of the present invention have considered that the occurrence of hot offset can be suppressed if the decrease in the viscosity of the toner can be suppressed even at such a temperature that the toner melts.

  Generally, it is known that when a minute rigid body is dispersed in a fluid having a certain viscosity, the viscosity of the fluid increases (thickening effect). This is called Einstein's law of viscosity.

  With reference to this theory, the toner melted at a high temperature is regarded as a fluid, and a study of imparting a thickening effect by the organic-inorganic composite particles was conducted. As a result, it has been found that hot offset at high temperature has an improvement effect.

  First, in order for the organic / inorganic composite fine particles to exhibit a thickening effect, it is necessary that the added organic / inorganic composite particles have sufficient viscosity in a temperature region where hot offset occurs. Therefore, it is preferable that the resin component of the organic-inorganic composite fine particles is made of a material stable to heat and has a sufficient cross-linked structure. In the present invention, a resin having a siloxane structure is used as a heat-stable resin component. In addition, as an index of the crosslinked structure of the resin component, solubility in tetrahydrofuran (THF) solvent was expressed as THF insoluble matter. In order to satisfy the present invention, the THF-insoluble content of the resin component of the organic / inorganic composite fine particles needs to be 70.0% by mass or more. This is because in order for the organic-inorganic composite fine particles to exert a thickening effect in the melted toner at the time of heat fixing, it is necessary to maintain the shape even in a temperature region where high temperature offset occurs. . When the THF-insoluble content of the organic-inorganic composite fine particle resin is less than 70.0% by mass, the thickening effect cannot be sufficiently exhibited, which is not preferable. The THF-insoluble content of the resin of the organic / inorganic composite fine particles is preferably 95.0% by mass or more.

  Furthermore, the present inventors considered that when the organic-inorganic composite fine particles are used as an external additive, it is necessary to be instantaneously mixed in the toner melted at the time of fixing.

  Thus, as a result of paying attention to the material of the shell, the present inventors have found that a higher thickening effect is exhibited by using a resin having a siloxane bond in the shell. That is, it has been found that the resin A contained in the shell phase is a resin having a siloxane bond, and that the resin component of the organic-inorganic composite fine particles needs to contain a siloxane bond.

  Due to the affinity between the resin A of the shell phase and the resin component of the organic / inorganic composite fine particles, the so-called wettability effect, the organic / inorganic composite fine particles are easily dispersed in the toner melted at the time of fixing. As a result, it is considered that even when the viscosity of the resin A is sufficiently lowered, the thickening effect works and the effect of hot offset is exhibited without inhibiting the low-temperature fixability.

  Further, the resin A contained in the shell phase is a resin having a siloxane bond, and the organic-inorganic composite particles from the toner particles in the long-term use can be obtained by adding the siloxane bond to the resin component of the organic-inorganic composite fine particles. It has been found that detachment can be suppressed and the image defect due to toner deterioration is also improved.

  The number average particle size of the organic-inorganic composite fine particles is 50 nm or more and 500 nm or less. When the number average particle diameter is larger than 500 nm, the surface area is relatively reduced, and thus the thickening effect cannot be sufficiently exhibited, which is not preferable. When the number average particle size is smaller than 50 nm, the particle size itself is too small, and thus the thickening effect of the shell resin is not sufficiently exhibited, which is not preferable. Further, the organic-inorganic composite fine particles are not preferable because they are easily embedded in the toner particles and do not function as an external additive during long-term use.

(Organic inorganic composite fine particles)
The organic-inorganic composite fine particles of the present invention are prepared by preparing an aqueous dispersion of a composition containing inorganic fine particles and a monomer constituting a resin component, and then adding a polymerization initiator to the aqueous dispersion to polymerize the monomers. Can be produced. By this method, organic-inorganic composite fine particles having inorganic fine particles uniformly present on the surface of the resin particles can be obtained.

  Another example is a method in which a solution in which a resin component is dissolved in an organic solvent is added in a state where inorganic fine particles are dispersed in an aqueous medium to form organic-inorganic composite emulsified particles. By removing the organic solvent from the emulsified particles, organic-inorganic composite fine particles in which inorganic fine particles are uniformly present on the surface of the resin particles can be obtained.

  In addition, a manufacturing method in which inorganic fine particles are implanted into resin particles later is also included. As a method for implanting inorganic fine particles into resin particles, a hybridizer (manufactured by Nara Machinery Co., Ltd.), Nobilta (manufactured by Hosokawa Micron Co., Ltd.), mechanofusion (manufactured by Hosokawa Micron Co., Ltd.), or Hi-Flex Grall (manufactured by Earth Technica Co., Ltd.) can be used. .

In the present invention, the resin component contained in the organic / inorganic composite fine particles is preferably a resin synthesized by a silane compound represented by the following chemical formula [1].
Chemical formula [1]
X-SiH _3-n (OR) _n
Here, X represents an organic functional group, R represents a methyl or ethyl group, and n represents an integer of 1 to 3.

  In order to synthesize a resin using the silane compound represented by the chemical formula [1], the organic functional group X preferably has a polymerizable functional group such as a vinyl group, an acrylate group, or a methacrylate group. Preferred are the compounds listed below. Vinyltriacetoxysilane, (3-acryloxypropyl) trimethoxysilane, (3-acryloxypropyl) triethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxy Methyltriethoxysilane, (3-acryloxypropyl) methyldimethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropyldimethylethoxysilane, methacryloxypropyldimethylmethoxysilane, allyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxy Silane, vinyltris (2-methoxyethoxy) silane.

  The resin component contained in the organic-inorganic composite fine particles of the present invention preferably contains 50.0% by mass or more of a resin synthesized from a silane compound. Thereby, affinity with resin A which forms a shell phase becomes favorable.

  The resin component of the organic-inorganic composite fine particles of the present invention may contain the following resins in addition to the resin having a siloxane bond. Polystyrene, homopolymer of styrene of polyvinyltoluene and substituted products thereof; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-acrylic Ethyl acid copolymer, Styrene-butyl acrylate copolymer, Styrene-octyl acrylate copolymer, Styrene-dimethylaminoethyl acrylate copolymer, Styrene-methyl methacrylate copolymer, Styrene-ethyl methacrylate copolymer Polymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, Styrene-butier Copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene copolymer of styrene-maleic acid ester copolymer, polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, Polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic acid resin, polyolefin resin, polyacrylonitrile, polyvinyl acetate, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether and polyvinyl ketone, vinyl chloride-acetic acid Vinyl copolymer, straight silicone resin composed of organosiloxane bond or modified product thereof, fluorine resin, phenol resin, amino resin, benzoguanamine resin, Rear resins, polyamide resins, it is possible to use an epoxy resin, they may be used alone or in combination of plural kinds.

  The organic-inorganic composite fine particles of the present invention may have a hydrophobic surface. The hydrophobic treatment may be applied to the organic / inorganic composite fine particles, or the inorganic fine particles subjected to the hydrophobic treatment may be combined with a resin.

  As a method of chemically hydrophobizing inorganic fine particles used for organic / inorganic composite fine particles or organic / inorganic composite fine particles with an organosilicon compound, silica fine particles generated by vapor phase oxidation of a silicon halide compound are treated with an organosilicon compound. There is a way to handle it. Examples of such organosilicon compounds include the following.

  Hexamethyldisilazane, methyltrimethoxysilane, octyltrimethoxysilane, isobutyltrimethoxysilane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichloro Silane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane , Dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, 1-hexamethyl Disiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and 2 to 12 siloxane units per molecule, each bonded to a terminal Si unit Dimethylpolysiloxane containing hydroxyl groups. These are used alone or in a mixture of two or more.

  The inorganic fine particles used for the organic / inorganic composite fine particles or the organic / inorganic composite fine particles may be hydrophobized with silicone oil, or may be treated together with the hydrophobizing treatment.

As a preferable silicone oil, one having a viscosity at 25 ° C. of 30 mm ² / s or more and 1000 mm ² / s or less is used. For example, dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, and fluorine modified silicone oil are particularly preferred.

  Examples of the method for treating silicone oil include the following methods. A method in which inorganic fine particles treated with a silane coupling agent and silicone oil are directly mixed using a mixer such as a Henschel mixer. A method of spraying silicone oil onto inorganic fine particles as a base. Alternatively, after dissolving or dispersing silicone oil in an appropriate solvent, inorganic fine particles are added and mixed to remove the solvent.

  Examples of the inorganic fine particles of the organic-inorganic composite fine particles of the present invention include silica, alumina, titania, zinc oxide, strontium titanate, cerium oxide, and calcium carbonate. In particular, when the inorganic fine particles are silica, it is preferable because the chargeability is excellent and an effect on the developability is obtained. Silica may be obtained by a dry method such as fumed silica, or may be obtained by a wet method such as sol-gel silica.

  In the organic-inorganic composite fine particles of the present invention, the surface presence rate of the inorganic fine particles is preferably 20% or more and 70% or less. When the surface abundance ratio of the inorganic fine particles on the surface of the organic / inorganic composite fine particles is less than 20%, the exposed portion of the inorganic fine particles is small, so that the cleaning blade passes through and contaminates the charging member. Further, the synthesis of the organic-inorganic composite fine particles becomes insufficient, and it becomes difficult to exert a thickening effect. If it exceeds 70%, the amount of resin on the surface is reduced, and the compatibility with the shell resin is deteriorated. In addition, the electrostatic adhesion is increased and the cleaning property is lowered. More preferably, the surface presence rate of the inorganic fine powder particles is 30% or more and 60% or less.

(Resin A)
In the present invention, in order to achieve the endothermic characteristics and the viscoelastic characteristics by the differential scanning calorimeter (DSC), it is preferable to use a resin in which the resin A has a portion capable of taking a crystal structure. Furthermore, it is preferable that the site | part which can take the said crystal structure is a site | part derived from crystalline polyester. Here, the part which can take the above-mentioned crystal structure means a part which regularly arranges and expresses crystallinity when a large number of the parts are collected, and means a crystalline polymer chain. Crystalline polyester is a material that causes a sudden change in endothermic characteristics and viscoelasticity by a differential scanning calorimeter (DSC) at a melting point specific to the material composition. By introducing a portion derived from crystalline polyester into the resin A, it is possible to obtain a toner satisfying low-temperature fixability.

  The portion derived from the crystalline polyester is preferably contained in an amount of 20.0% by mass or more based on the resin A. More preferably, it is 30.0 mass% or more.

  In the present invention, the resin A is preferably a resin containing an organic polysiloxane in a molecular structure. By using a resin containing an organic polysiloxane in the molecular structure, it is possible to increase the affinity with the organic-inorganic composite fine particles having a siloxane bond as a resin component without increasing the viscosity of the resin A itself. It becomes possible to improve.

  In the present invention, the resin A may have a content of Si derived from the organic polysiloxane of 1.0% by mass or more and 10.0% by mass or less with respect to the resin A in a composition analysis with fluorescent X-rays. preferable. More preferably, the content is 2.0% by mass or more and 5.0% by mass or less.

  In the present invention, the resin A is obtained by copolymerizing a vinyl monomer a having a molecular structure with a site capable of forming a crystal structure and a vinyl monomer b having a siloxane bond site in the molecular structure. Can do.

(Vinyl monomer a)
The vinyl monomer a includes a vinyl monomer containing a linear alkyl group in the molecular structure, a vinyl monomer containing a polyester component in the molecular structure, and a vinyl monomer containing a polyether component in the molecular structure as a part capable of taking a crystal structure. Is mentioned. Among these, a vinyl monomer containing a polyester component in the molecular structure is particularly preferable.

  The polyester component is preferably a crystalline polyester component obtained by reacting an aliphatic diol having 4 to 20 carbon atoms and a polycarboxylic acid. Furthermore, the aliphatic diol is desirably a linear aliphatic diol that easily improves crystallinity.

  Examples of the linear aliphatic diol include the following, but are not limited thereto. Depending on the case, it is also possible to use a mixture. 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1 , 11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol.

  Of these, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are more preferable from the viewpoint of the melting point suitable for low-temperature fixability in the present invention.

  Next, the polyvalent carboxylic acid is preferably an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid, more preferably an aliphatic dicarboxylic acid, and particularly preferably a linear aliphatic dicarboxylic acid from the viewpoint of forming a crystal structure.

  Examples of the linear aliphatic dicarboxylic acid include, but are not limited to, the following. Depending on the case, it is also possible to use a mixture. Succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid. Or its lower alkyl ester and acid anhydride.

  Among these, in the present invention, adipic acid, sebacic acid, dodecanedicarboxylic acid and octadecanedicarboxylic acid are preferable from the viewpoint of a melting point suitable for low-temperature fixability.

  Examples of the aromatic dicarboxylic acid include the following. Terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid.

  The method for producing the crystalline polyester component is not particularly limited, and can be produced by a general polyester polymerization method in which an acid component and an alcohol component are reacted. For example, direct polycondensation or transesterification can be performed using a monomer. Produced separately for different types.

  The production of the crystalline polyester component is preferably carried out at a polymerization temperature of 180 ° C. or higher and 230 ° C. or lower. If necessary, the reaction system is reduced in pressure and reacted while removing water and alcohol generated during condensation. Is preferred. When the monomer is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point is preferably added as a solubilizer and dissolved. In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. In the case where a monomer having poor compatibility exists in the copolymerization reaction, it is preferable that the monomer having poor compatibility and the monomer and the acid or alcohol to be polycondensed are condensed in advance and then polycondensed together with the main component.

  Examples of the catalyst that can be used during the production of the crystalline polyester component include the following. Titanium catalyst of titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide. Tin catalyst of dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide.

  Examples of a method for producing a vinyl monomer containing a polyester component in a molecular structure as a site capable of taking a crystal structure include a method in which the crystalline polyester component and a hydroxyl group-containing vinyl monomer are urethanized with a diisocyanate as a binder.

  At this time, the crystalline polyester component is preferably alcohol-terminated. Therefore, in the preparation of the crystalline polyester, the molar ratio of the acid component to the alcohol component (alcohol component / carboxylic acid component) is preferably 1.02 or more and 1.20 or less.

  Examples of the hydroxyl group-containing vinyl monomer include hydroxystyrene, N-methylolacrylamide, N-methylolmethacrylamide, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, polyethylene glycol acrylate, polyethylene glycol monomethacrylate, allyl alcohol. , Methallyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, An example is sucrose allyl ether. Of these, preferred is hydroxyethyl methacrylate.

  Examples of the diisocyanate include the following. C6-C20 aromatic diisocyanate, C2-C18 aliphatic diisocyanate, C4-C15 alicyclic diisocyanate, C8 or more (except for carbon in the NCO group) 15 or less aromatic hydrocarbon diisocyanates and modified products of these diisocyanates (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group-containing modified product) , Also called modified diisocyanate), and mixtures of two or more thereof.

  Examples of the aliphatic diisocyanate include the following. Ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate.

  Examples of the alicyclic diisocyanate include the following. Isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate.

  Examples of the aromatic hydrocarbon diisocyanate include the following. m- and / or p-xylylene diisocyanate (XDI), α, α, α ', α'-tetramethylxylylene diisocyanate.

  Among these, preferred are aromatic diisocyanates having 6 to 15 carbon atoms, aliphatic diisocyanates having 4 to 12 carbon atoms, and alicyclic diisocyanates having 4 to 15 carbon atoms, and having 8 to 15 carbon atoms. Aromatic hydrocarbon diisocyanates, particularly preferred are HDI, IPDI, and XDI.

  Moreover, the method of urethanating the said crystalline polyester component and the vinyl monomer containing isocyanate is mentioned.

  Examples of the vinyl monomer containing isocyanate include 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate.

  The crystalline polyester component of the vinyl monomer a preferably has a maximum endothermic peak temperature of 55 ° C. or higher and 80 ° C. or lower in DSC measurement. By being this range, it becomes possible to make TpA of resin A into the above-mentioned range.

  The crystalline polyester component of the vinyl monomer a has a number average molecular weight (Mn) of 1000 to 20000 and a weight average molecular weight (Mw) in gel permeation chromatography (GPC) soluble in tetrahydrofuran (THF). Is preferably 2000 or more and 40000 or less. By being in this range, it is possible to maintain good heat-resistant storage stability and to impart sharp melt properties to the toner. A more preferable range of Mn is 2000 to 15000, and a more preferable range of Mw is 3000 to 20000. Further, Mw / Mn is preferably 5 or less, and a more preferable range of Mw / Mn is 3 or less.

  The resin A preferably contains 20.0% by mass or more of the vinyl monomer a with respect to the total vinyl monomers used for preparing the resin A. When the content of the vinyl monomer a in the resin A is less than 20.0% by mass, the equation (1) is a change in the loss elastic modulus of the resin A from the temperature TpA (° C.) to TpA + 10 (° C.). It becomes difficult to satisfy the relationship 1).

(Vinyl monomer b)
As the vinyl monomer b, it is preferable to use a vinyl monomer having an organic polysiloxane represented by the following chemical formula [2] in the molecular structure. Use of the vinyl monomer having the organic polysiloxane in the molecular structure facilitates dispersion of the organic-inorganic composite fine particles in the melted toner at the time of fixing, and can exhibit a thickening effect.

  Furthermore, in the method for producing toner particles using high-pressure carbon dioxide as a dispersion medium, which will be described later, the resin fine particles containing the resin A play a role as a dispersant.

Here, R ¹ and R ² each independently represent an alkyl group, preferably each having 1 to 3 carbon atoms, and more preferably ¹ carbon atoms in R ¹ . R ³ is preferably an alkylene group, and more preferably 1 to 3 carbon atoms. R ⁴ represents hydrogen or a methyl group. Moreover, n is a polymerization degree and it is preferable that the said polymerization degree n is an integer of 2-18.

  The resin A preferably contains 5.0% by mass or more of the vinyl monomer b with respect to the total vinyl monomers used for preparing the resin A. When the content of the vinyl monomer b in the resin A is less than 5.0% by mass, sufficient affinity with the organic-inorganic composite fine particles cannot be obtained.

(Vinyl monomer c)
In the present invention, for the synthesis of the resin A, a vinyl monomer c may be used in addition to the vinyl monomer a and the vinyl monomer b. The vinyl monomer c to be used is composed of one or more kinds of vinyl monomers, and the following monomers can be used.

  Aliphatic vinyl hydrocarbons: alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, other α-olefins; alkadienes such as butadiene, isoprene, 1,4- Pentadiene, 1,6-hexadiene and 1,7-octadiene.

  Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as cyclohexene, cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene; terpenes such as pinene, limonene, indene.

  Aromatic vinyl hydrocarbons: styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substitutions such as α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butyl Styrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene, divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene; and vinylnaphthalene.

  Carboxyl group-containing vinyl monomers and metal salts thereof: unsaturated monocarboxylic acids having 3 to 30 carbon atoms, unsaturated dicarboxylic acids and anhydrides thereof and monoalkyl (1 to 27 carbon atoms) esters such as acrylic acid, Methacrylic acid, maleic acid, maleic anhydride, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl Ester, cinnamic acid carboxyl group-containing vinyl monomer.

  Vinyl esters such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl 4-vinylbenzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, vinyl Methoxy acetate, vinyl benzoate, ethyl α-ethoxy acrylate, alkyl acrylate and alkyl methacrylate having 1 to 11 carbon atoms (linear or branched) (methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, Propyl methacrylate, butyl acrylate, butyl methacrylate, 2- Tilhexyl acrylate, 2-ethylhexyl methacrylate, dialkyl fumarate (dialkyl fumarate) (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl Maleate (maleic acid dialkyl ester) (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), polyallyloxyalkanes (diallyloxyethane) , Triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane), vinyl monomers having a polyalkylene glycol chain (polyethylene glycol (molecular weight 300) monoacrylate, polyethylene glycol ( Molecular weight 300) Monomethacrylate , Polypropylene glycol (molecular weight 500) monoacrylate, polypropylene glycol (molecular weight 500) monomethacrylate, methyl alcohol ethylene oxide (ethylene oxide is hereinafter abbreviated as EO) 10 mol adduct acrylate, methyl alcohol ethylene oxide (ethylene oxide is hereinafter referred to as EO) (Abbreviated) 10 mol adduct methacrylate, lauryl alcohol EO 30 mol adduct acrylate lauryl alcohol EO 30 mol adduct methacrylate), polyacrylates and polymethacrylates (polyacrylates and polymethacrylates of polyhydric alcohols: ethylene glycol diacrylate, ethylene Glycol dimethacrylate, propylene glycol diacrylate, propylene glycol di Methacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, polyethylene glycol diacrylate. Polyethylene glycol dimethacrylate.

  The resin A has a number average molecular weight (Mn) of 8000 to 40000 and a weight average molecular weight (Mw) of 15,000 to 90,000 in gel permeation chromatography (GPC) soluble in tetrahydrofuran (THF). preferable. By being in this range, it is possible to maintain good heat-resistant storage stability and to impart sharp melt properties to the toner. A more preferable range of Mn is 8000 to 25000, and a more preferable range of Mw is 20000 to 80000. Further, Mw / Mn is preferably 7 or less.

  The resin A is preferably not dissolved in the dispersion medium when used as a fine particle dispersant in a method for producing toner particles using carbon dioxide in a high-pressure state, which will be described later, as a dispersion medium. Therefore, a crosslinked structure may be introduced into the resin A.

  Moreover, it is preferable that the ratio of the resin A in resin which forms the shell phase in this invention is 80.0 mass% or more, and it is especially preferable not to use resin other than the resin A as a shell phase.

(Binder resin)
In the toner of the present invention, as the binder resin, either a crystalline resin or an amorphous resin can be used. These may be mixed or used. Among these, the binder resin preferably contains a crystalline resin. In the present invention, it is preferable to use crystalline polyester as the crystalline resin.

  In the toner of the present invention, the content of the crystalline resin in the binder resin is 50.0% by mass or more and 85.0% by mass or less, so that both low temperature fixability and heat resistant storage stability can be achieved. It becomes easier.

  In the binder resin of the present invention, the peak temperature of the maximum endothermic peak derived from the crystalline resin in the first temperature increase is preferably 55 ° C. or higher and 80 ° C. or lower in the measurement with a differential scanning calorimeter (DSC). .

  When a crystalline polyester is used as the crystalline resin, a monomer that can be used for the synthesis of the crystalline polyester component that can be used for the resin A is preferably used for the synthesis. At this time, an aliphatic diol having a double bond can also be used as the aliphatic diol. Examples of the aliphatic diol having a double bond include the following compounds. 2-butene-1,4-diol, 3-hexene-1,6-diol, 4-octene-1,8-diol.

  Furthermore, a dicarboxylic acid having a double bond can also be used as the polyvalent carboxylic acid. Examples of such dicarboxylic acids include, but are not limited to, fumaric acid, maleic acid, 3-hexenedioic acid, and 3-octenedioic acid. Moreover, these lower alkyl esters and acid anhydrides are also included. Among these, fumaric acid and maleic acid are preferable in terms of cost.

  Next, an amorphous resin that can be used for the binder resin of the present invention will be described.

  Examples of the amorphous resin used for the binder resin include, but are not limited to, vinyl resins such as polyurethane resins, polyester resins, styrene acrylic resins, and polystyrene. These resins may be modified with urethane, urea, or epoxy. Of these, polyester resins and polyurethane resins are preferably used from the viewpoint of maintaining elasticity.

  Examples of the monomer used for the polyester resin as the amorphous resin include divalent or trivalent or higher carboxylic acids and divalent or trivalent or higher alcohols. Specific examples of these monomer components include the following compounds. Divalent carboxylic acids include succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, malonic acid, dodecenyl succinic acid dibasic acid, anhydrides thereof and lower alkyl esters thereof, maleic acid , Fumaric acid, itaconic acid, citraconic acid aliphatic unsaturated dicarboxylic acid. Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, anhydrides thereof, and lower alkyl esters thereof. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the divalent alcohol include the following compounds. Bisphenol A, hydrogenated bisphenol A, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, ethylene glycol, propylene glycol. Examples of the trivalent or higher alcohols include the following compounds. Glycerin, trimethylol ethane, trimethylol propane, pentaerythritol. These may be used individually by 1 type and may use 2 or more types together. If necessary, a monovalent acid such as acetic acid or benzoic acid, or a monovalent alcohol such as cyclohexanol or benzyl alcohol can be used for the purpose of adjusting the acid value or the hydroxyl value.

  The polyester resin can be synthesized by a conventionally known method using the monomer component.

  Next, the polyurethane resin as the amorphous resin will be described. The polyurethane resin is a reaction product of an aliphatic diol and a diisocyanate, and the functionality of the resulting resin can be changed by changing the aliphatic diol and the diisocyanate.

  Examples of the diisocyanate include diisocyanates that can be used for the resin A. Moreover, the following are mentioned as an aliphatic diol which can be used for a polyurethane resin.

  Alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol); alkylene ether glycol (polyethylene glycol, polypropylene glycol); alicyclic diol (1,4-cyclohexanedimethanol); bisphenols (bisphenol) A); alkylene oxide (ethylene oxide, propylene oxide) adduct of the alicyclic diol; the alkyl portion of the alkylene ether glycol may be linear or branched. In the present invention, an alkylene glycol having a branched structure can also be preferably used.

  In the present invention, it is possible to maintain elasticity after the crystalline resin is sharp-melted by including the amorphous resin as long as the binder resin does not affect low-temperature fixability.

  The glass transition temperature (Tg) of the amorphous resin in the binder resin is preferably 50 ° C. or higher and 130 ° C. or lower. More preferably, it is 70 degreeC or more and 130 degrees C or less. By being in this range, the elasticity in the fixing region is easily maintained.

  Furthermore, in the toner of the present invention, it is also a preferable aspect to use, as a binder resin, a block polymer in which a portion that can take a crystal structure and a portion that cannot take a crystal structure are chemically bonded.

  The block polymer is a polymer in which polymers are linked by a covalent bond within one molecule. Here, the part which can take a crystal structure is crystalline polyester, and the part which cannot take a crystal structure is polyester or polyurethane as an amorphous resin.

  The block polymer includes an AB type diblock polymer, an ABA type triblock polymer, a BAB type triblock polymer, an ABAB type, which has a part (A) that can take a crystal structure and a part (B) that cannot take a crystal structure. Type multi-block polymers, and any form can be used in the present invention.

  In the block polymer, examples of a bonding form in which a portion that can take a crystal structure and a portion that cannot take a crystal structure are covalently bonded include an ester bond, a urea bond, and a urethane bond. Among these, a block polymer bonded with a urethane bond is more preferable. By being a block polymer bonded with a urethane bond, elasticity is easily maintained.

  In the present invention, the content of the portion capable of taking the crystal structure in the binder resin is preferably 50% by mass or more.

  As a method of preparing the block polymer, a method of preparing a component that can take a crystal structure and a component that forms a site that cannot take a crystal structure separately and combining them is used (two-step method). be able to. In addition, a method (one-step method) in which a component that forms a site capable of taking a crystal structure and a raw material of a component that forms a site that cannot take a crystal structure are simultaneously prepared and prepared at one time can be used.

  The block polymer in the present invention can be synthesized by selecting from various methods in consideration of the reactivity of each terminal functional group.

  In the case of a block polymer in which both a portion that can take a crystal structure and a portion that cannot take a crystal structure are polyester resins, each component can be prepared separately and then bonded using a binder. In particular, when the acid value of one polyester is high and the hydroxyl value of the other polyester is high, it is not necessary to use a binder, and the condensation reaction can proceed while heating and reducing pressure as it is. At this time, the reaction temperature is preferably about 200 ° C.

  When the binder is used, the following binders are exemplified. Polyvalent carboxylic acid, polyhydric alcohol, polyvalent isocyanate, polyfunctional epoxy, polyhydric acid anhydride. These binders can be used for synthesis by dehydration reaction or addition reaction.

  In addition, in the case of a block polymer in which the crystalline structure is a crystalline polyester and the crystalline structure cannot be made of polyurethane, after preparing each part separately, the crystalline polyester alcohol ends and polyurethane isocyanate It can be prepared by urethanating the end. The synthesis can also be performed by mixing a crystalline polyester having an alcohol terminal and a diol and diisocyanate constituting polyurethane and heating. In this case, at the initial stage of the reaction when the concentrations of the diol and the diisocyanate are high, these selectively react to form a polyurethane, and after the molecular weight increases to some extent, the urethane between the isocyanate terminal of the polyurethane and the alcohol terminal of the crystalline polyester. Happens.

  The number average molecular weight of the block polymer is preferably 3000 or more and 40000 or less, and more preferably 7000 or more and 25000 or less. The block polymer preferably has a weight average molecular weight of 10,000 to 60,000, more preferably 20,000 to 50,000. By being in this range, it is possible to maintain good heat-resistant storage stability and to impart sharp melt properties to the toner.

  In the present invention, when adjusting and adjusting the acid value of the block polymer, the terminal isocyanate group, hydroxyl group and carboxyl group of the block polymer are changed to polyvalent carboxylic acids, polyhydric alcohols, polyvalent isocyanates, polyfunctional epoxies. , Modification with polyanhydrides, and polyvalent amines.

(Coloring agent)
The toner of the present invention requires a colorant in order to impart coloring power. Examples of the colorant preferably used in the present invention include the following organic pigments, organic dyes, and inorganic pigments, and the colorants conventionally used in toners can be used. The colorant used in the toner of the present invention is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner.

  The following are mentioned as a coloring agent used for this invention.

  Examples of the colorant for yellow include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specific examples include the following. C. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 128, 129, 138, 147, 150, 151, 154, 155, 168, 180, 185, 213, 214. These can be used alone or in combination of two or more.

  Examples of the colorant for magenta include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specific examples include the following. C. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. Pigment Bio Red 19. These can be used alone or in combination of two or more.

  Examples of the colorant for cyan include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specific examples include the following. C. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66. These can be used alone or in combination of two or more.

  Examples of black colorants include the following. Furnace black, channel black, acetylene black, thermal black, lamp black carbon black. Further, metal oxides such as magnetite and ferrite are also used.

  In the present invention, when used as a colorant for a normal color toner, the content of the colorant is preferably 2.0% by mass or more and 15.0% by mass or less based on the toner. When the amount is less than 2.0% by mass, the coloring power tends to decrease. On the other hand, when it is more than 15.0% by mass, the color space tends to be small. More preferably, it is 2.5 mass% or more and 12.0 mass% or less. Further, a light color toner having a reduced density can be preferably used in combination with a normal color toner. In this case, the content of the colorant is preferably 0.5% by mass or more and 5.0% by mass or less with respect to the toner.

(wax)
The toner particles used in the toner of the present invention contain a wax. The wax is not particularly limited, but includes the following.

  Low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymer, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax; fat A wax mainly composed of a fatty acid ester such as an aromatic hydrocarbon ester wax; and a partially or completely deoxidized fatty acid ester such as a deoxidized carnauba wax; a partial ester of a fatty acid and a polyhydric alcohol such as behenic acid monoglyceride A methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

  The wax particularly preferably used in the present invention is an aliphatic hydrocarbon because of ease of preparation of the wax dispersion, ease of incorporation into the prepared toner, seepage from the toner during fixing, and releasability. System waxes and ester waxes are preferred. In the present invention, the ester wax only needs to have at least one ester bond in one molecule, and either natural ester wax or synthetic ester wax may be used.

Examples of the synthetic ester wax include monoester wax synthesized from a long-chain linear saturated fatty acid and a long-chain linear saturated aliphatic alcohol. The long-chain linear saturated fatty acid is represented by the general formula C _n H _{2n + 1} COOH, and those having n = 5 to 28 are preferably used. The long-chain straight-chain saturated aliphatic alcohol is represented by C _n H _{2n + 1} OH, and n = 5 to 28 is preferably used. Examples of natural ester waxes include candelilla wax, carnauba wax, rice wax, and derivatives thereof.

  Among the above, more preferable waxes are synthetic ester waxes composed of long-chain linear saturated fatty acids and long-chain linear saturated aliphatic alcohols, or natural waxes based on the above esters.

  In the present invention, the wax content in the toner is preferably 1.0% by mass or more and 20.0% by mass or less, and more preferably 2.0% by mass or more and 15.0% by mass or less. If the amount is less than 1.0% by mass, the toner releasability tends to decrease, and when the fixing member such as the fixing roller and the fixing belt becomes low temperature, the toner releasability to the fixing member is insufficient. Therefore, the transfer paper is easily wound around the fixing member. When the amount is more than 20.0% by mass, the wax tends to be exposed on the toner surface, and the heat resistant storage stability tends to be lowered.

  In the present invention, the wax preferably has a maximum endothermic peak at 60 ° C. or higher and 120 ° C. or lower as measured by a differential scanning calorimeter (DSC). More preferably, it is 60 degreeC or more and 90 degrees C or less. When the maximum endothermic peak is lower than 60 ° C., the wax tends to be exposed on the toner surface and the heat resistant storage stability tends to be lowered. On the other hand, if the maximum endothermic peak is higher than 120 ° C., it becomes difficult for the wax to melt properly at the time of fixing, and the low-temperature fixing property tends to be lowered and hot offset tends to occur.

(Charge control agent)
In the toner of the present invention, a charge control agent can be mixed with toner particles and used as necessary. Further, it may be added when the toner particles are produced. By blending the charge control agent, the charge characteristics can be stabilized and the optimum triboelectric charge amount can be controlled according to the development system.

  As the charge control agent, a known one can be used, and a charge control agent that has a high charging speed and can stably maintain a constant charge amount is particularly preferable.

  Examples of the charge control agent that control the toner to be negatively charged include the following. Organic metal compounds and chelate compounds are effective, and examples include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds. The toner of the present invention can contain these charge control agents alone or in combination of two or more.

  A preferable blending amount of the charge control agent is 0.01% by mass or more and 20% by mass or less, and more preferably 0.5% by mass or more and 10% by mass or less with respect to the toner.

(Other external additives)
In addition to the toner particles and organic / inorganic composite fine particles used in the present invention, it is preferable to further add inorganic fine powder as a fluidity improver. Examples of the inorganic fine powder to be added to the toner particles used in the present invention include fine powder such as silica fine powder, titanium oxide fine powder, alumina fine powder or double oxide fine powder thereof. Among the inorganic fine powders, silica fine powder and titanium oxide fine powder are preferable.

Examples of the silica fine powder include dry silica or fumed silica produced by vapor phase oxidation of silicon halide, and wet silica produced from water glass. As the inorganic fine powder, dry silica having less silanol groups on the surface and inside the silica fine powder and less Na ₂ O and SO ₃ ²⁻ is preferable. The dry silica may be a composite fine powder of silica and another metal oxide produced by using a metal halogen compound such as aluminum chloride or titanium chloride together with a silicon halogen compound in the production process. Specific examples of the inorganic fine particles include the following.

  Silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara , Antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride.

  The inorganic fine powder is preferably externally added to the toner particles in order to improve the fluidity of the toner and make the toner particles uniformly charged. In addition, the hydrophobic treatment of the inorganic fine powder makes it possible to adjust the charge amount of the toner, improve the environmental stability, and improve the characteristics in a high-humidity environment. More preferably, the body is used. When the inorganic fine powder added to the toner absorbs moisture, the charge amount as the toner is reduced, and the developability and transferability are easily lowered.

  Treatment agents for hydrophobizing inorganic fine powder include unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, and organic titanium. Compounds. These treatment agents may be used alone or in combination.

  Among these, inorganic fine powder treated with silicone oil is preferable. More preferably, the hydrophobicity-treated inorganic fine powder treated with silicone oil treated with silicone oil simultaneously or after the hydrophobic treatment of the inorganic fine powder with a coupling agent increases the charge amount of the toner particles even in a high humidity environment. It is good for maintaining high and reducing selective developability.

  The addition amount of the inorganic fine powder is preferably 0.1 parts by mass or more and 4.0 parts by mass or less, more preferably 0.2 parts by mass or more and 3.5 parts by mass with respect to 100 parts by mass of the toner particles. It is as follows.

(Method for producing toner of the present invention)
The toner of the present invention is a toner having a core-shell structure having a shell phase on the surface of the core. The shell phase may be formed at the same time as the core formation step or after the core is formed. From the viewpoint of simplicity, it is preferable to simultaneously perform the formation of the core and the shell phase.

  Further, the method for forming the shell phase is not limited at all. When the shell phase is provided after the core is formed, there is a method in which the core and resin fine particles are dispersed in an aqueous medium, and then the resin fine particles are aggregated and adsorbed on the surface of the core. The resin fine particles forming the shell phase are preferably 3.0 parts by mass or more and 15.0 parts by mass or less with respect to 100 parts by mass of the binder resin (resin contained in the core).

  The toner particles used in the present invention particularly preferably contain 3.0 parts by mass or more and 15.0 parts by mass or less of the resin A contained in the shell phase with respect to 100.0 parts by mass of the core. It is an aspect. When the amount of the resin A contained in the shell phase is less than 3.0 parts by mass, the heat resistant storage stability of the toner tends to be lowered. On the other hand, when it exceeds 15.0 parts by mass, the elution of the binder resin tends to be hindered, and the low-temperature fixability tends to be lowered.

  In the present invention, a dissolution suspension method in which toner particles having a core-shell structure can be prepared in one step is preferable. In the aqueous dissolution suspension method, a resin composition obtained by dissolving a binder resin as a core in an organic medium is dispersed in an aqueous medium in which resin fine particles as a shell phase are dispersed. Then, the organic medium can be removed to obtain toner particles.

  The method for preparing the resin fine particles is not particularly limited, and may be prepared by dissolving the emulsion polymerization method or the resin in a solvent or liquefying it, and suspending it in an aqueous medium. it can. At this time, a known surfactant or dispersant can be used, or the resin constituting the fine particles can be made self-emulsifying.

  Solvents that can be used as an organic medium for dissolving the binder resin include hydrocarbon solvents such as xylene and hexane, halogenated hydrocarbon solvents such as methylene chloride, chloroform, and dichloroethane, methyl acetate, ethyl acetate, butyl acetate, Examples thereof include ester solvents such as isopropyl acetate, ether solvents such as diethyl ether, and ketone solvents such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexane.

  As an aqueous medium, water alone may be used, but a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohol (methanol, isopropanol, ethylene glycol), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve), and lower ketones (acetone, 1-butanone).

  The method for dispersing the resin composition in the dispersion medium is not particularly limited, and general-purpose devices such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be used. Preferably, any general-purpose emulsifier and disperser can be used.

  For example, Ultra Turrax (manufactured by IKA), Polytron (manufactured by Kinematica), TK Auto Homo Mixer (manufactured by Special Mechanized Industry Co., Ltd.), Ebara Milder (manufactured by Ebara Corporation), TK Homomic Line Flow (Made by Special Machine Industries Co., Ltd.), colloid mill (made by Shinko Pantech Co., Ltd.), thrasher, trigonal wet pulverizer (made by Mitsui Miike Chemical Co., Ltd.), Cavitron (made by Eurotech), fine flow mill Examples thereof include a continuous emulsifier (manufactured by Taiheiyo Kiko Co., Ltd.), a clear mix (manufactured by M Technique Co., Ltd.), a batch type of Philmix (manufactured by Tokushu Kika Kogyo Co., Ltd.), or a continuous-use emulsifier.

  When a high-speed shearing disperser is used, the number of rotations is not particularly limited, but is usually 1000 rpm to 30000 rpm, preferably 3000 rpm to 20000 rpm. In the case of a batch method, the dispersion time is usually from 0.1 minutes to 5 minutes. The temperature during dispersion is usually 10 ° C. or higher and 55 ° C. or lower, preferably 10 ° C. or higher and 40 ° C. or lower.

  In the present invention, a non-aqueous dissolution suspension method using carbon dioxide in a high-pressure state can also be used as a dispersion medium. That is, the resin composition is dispersed in carbon dioxide in a high-pressure state, granulated, the organic solvent contained in the granulated particles is extracted and removed into the carbon dioxide phase, and then the pressure is released. This is a method of separating carbon dioxide to obtain toner particles. The high pressure carbon dioxide preferably used in the present invention is liquid or supercritical carbon dioxide.

  Here, liquid carbon dioxide is a gas passing through a triple point (temperature = −57 ° C., pressure = 0.5 MPa) and a critical point (temperature = 31 ° C., pressure = 7.4 MPa) on the phase diagram of carbon dioxide. It represents carbon dioxide in the liquid boundary line, the isotherm of the critical temperature, and the temperature and pressure conditions of the portion surrounded by the solid-liquid boundary line. Moreover, the carbon dioxide in a supercritical state represents carbon dioxide under temperature and pressure conditions above the critical point of the carbon dioxide.

  In the present invention, the dispersion medium may contain an organic solvent as another component. In this case, it is preferable that carbon dioxide and the organic solvent form a homogeneous phase.

  According to this method, since granulation is performed under high pressure, when a crystalline resin is used as the binder resin, not only is the crystallinity of the crystalline resin easy to maintain, but it is also possible to increase it. And is particularly suitable.

  Hereinafter, a method for producing toner particles that uses liquid or supercritical carbon dioxide as a dispersion medium, which is suitable for obtaining toner particles used in the present invention, will be described as an example.

  First, add a binder resin, colorant, wax, and other additives as required in an organic solvent that can dissolve the binder resin, and disperse it as a homogenizer, ball mill, colloid mill, or ultrasonic disperser. Dissolve or disperse uniformly with a machine. Next, the thus obtained solution or dispersion (hereinafter simply referred to as a binder resin solution) is dispersed in liquid or supercritical carbon dioxide to form oil droplets.

  At this time, it is necessary to disperse the dispersant in the liquid or supercritical carbon dioxide as the dispersion medium. As the dispersant, a resin fine particle dispersant is used. Since the dispersant adsorbed on the surface of the oil droplet remains as it is after the toner particles are formed, toner particles whose surfaces are coated with resin fine particles can be formed.

  The resin A fine particles preferably have a number average particle size of 5 nm or more and 500 nm or less so that the toner particles form a core-shell structure. More preferably, it is 50 nm or more and 300 nm or less. If the particle size of the resin fine particles is too small, the stability of the oil droplets during granulation tends to decrease. If it is too large, it will be difficult to control the particle size of the oil droplets to a desired size.

  In the present invention, any method may be used as a method of dispersing the dispersant in a liquid or supercritical carbon dioxide. As a specific example, there is a method in which the dispersant and liquid or supercritical carbon dioxide are charged in a container and directly dispersed by stirring or ultrasonic irradiation. Another example is a method in which a dispersion liquid in which the dispersant is dispersed in an organic solvent is introduced into a container charged with liquid or supercritical carbon dioxide using a high-pressure pump.

  In the present invention, any method may be used for dispersing the binder resin solution in liquid or supercritical carbon dioxide. As a specific example, there is a method of introducing the binder resin solution into a container containing a liquid in which the dispersant is dispersed or carbon dioxide in a supercritical state using a high-pressure pump. Further, a liquid in which the dispersant is dispersed or carbon dioxide in a supercritical state may be introduced into a container charged with the binder resin solution.

  In the present invention, it is important that the liquid or supercritical carbon dioxide dispersion medium is a single phase. When granulation is performed by dispersing the binder resin solution in liquid or supercritical carbon dioxide, part of the organic solvent in the oil droplets moves into the dispersion. At this time, it is not preferable that the carbon dioxide phase and the organic solvent phase exist in a separated state, which causes the stability of the oil droplets to be impaired. Therefore, the temperature and pressure of the dispersion medium, and the amount of the binder resin solution with respect to the liquid or supercritical carbon dioxide are preferably adjusted within a range in which the carbon dioxide and the organic solvent can form a homogeneous phase. .

  In addition, regarding the temperature and pressure of the dispersion medium, attention should be paid to granulation properties (ease of oil droplet formation) and solubility of the constituent components in the binder resin solution in the dispersion medium. . The binder resin and wax in the binder resin solution may be dissolved in the dispersion medium depending on temperature conditions and pressure conditions. In general, the lower the temperature and the lower the pressure, the more the solubility of the above components in the dispersion medium is suppressed, but the formed oil droplets are likely to agglomerate and coalesce, and the granulation property is lowered. On the other hand, although the granulation property is improved as the temperature and pressure are increased, the components tend to be easily dissolved in the dispersion medium.

  Furthermore, the temperature of the dispersion medium is preferably set to a temperature lower than the melting point of the crystalline polyester component, for example, when it is not desired to impair the crystallinity of the crystalline polyester component.

  Therefore, in the production of the toner particles of the present invention, the temperature of the dispersion medium is preferably 10 ° C. or higher and 40 ° C. or lower.

  The pressure in the container forming the dispersion medium is preferably 1.0 MPa or more and 20.0 MPa or less, and more preferably 2.0 MPa or more and 15.0 MPa or less. In addition, the pressure in this invention shows the total pressure, when components other than a carbon dioxide are contained in a dispersion medium.

  After the granulation is completed in this manner, the organic solvent remaining in the oil droplets is removed through a dispersion medium of carbon dioxide in a liquid or supercritical state. Specifically, liquid or supercritical carbon dioxide is further mixed with the dispersion medium in which oil droplets are dispersed, and the remaining organic solvent is extracted into a carbon dioxide phase, and carbon dioxide containing the organic solvent is removed. Further, it is performed by substituting with carbon dioxide in a liquid or supercritical state.

  In the mixing of the dispersion medium and the liquid or supercritical carbon dioxide, a higher pressure liquid or supercritical carbon dioxide may be added to the dispersion medium. May also be added to low pressure liquid or supercritical carbon dioxide.

  And as a method of further replacing carbon dioxide containing an organic solvent with liquid or supercritical carbon dioxide, there is a method of circulating liquid or supercritical carbon dioxide while keeping the pressure in the container constant. . At this time, the toner particles to be formed are performed while being supplemented by a filter.

  When the liquid or supercritical carbon dioxide is not sufficiently substituted, and the organic solvent remains in the dispersion medium, the container is decompressed in order to recover the obtained toner particles. In some cases, the organic solvent dissolved in the toner may condense and the toner particles may be redissolved or the toner particles may coalesce. Therefore, the substitution with carbon dioxide in the liquid or supercritical state must be performed until the organic solvent is completely removed. The amount of liquid or supercritical carbon dioxide to be circulated is preferably 1 to 100 times, more preferably 1 to 50 times, most preferably 1 to 30 times the volume of the dispersion medium. It is.

  When extracting toner particles from a liquid containing toner particles dispersed or a dispersion containing carbon dioxide in a supercritical state, the container may be depressurized to room temperature and normal pressure at once, but the container is pressure controlled independently. The pressure may be reduced stepwise by providing multiple stages. The decompression speed is preferably set within a range where the toner particles do not foam. The organic solvent, liquid, or supercritical carbon dioxide used in the present invention can be recycled.

  The toner of the present invention has a number average molecular weight (Mn) of 5000 to 40000 and a weight average molecular weight (Mw) of 15000 to 60000 in gel permeation chromatography (GPC) soluble in tetrahydrofuran (THF). Is preferred. By being in this range, it is possible to maintain good heat-resistant storage stability and to impart an appropriate sharp melt property to the toner. A more preferable range of Mn is 7000 to 25000, and a more preferable range of Mw is 20000 to 50000. Further, Mw / Mn is preferably 6 or less. A more preferable range of Mw / Mn is 4 or less.

  A method for measuring various physical properties of the toner and toner material of the present invention will be described below.

<Measurement method of peak temperature of maximum endothermic peak>
The peak temperature of the maximum endothermic peak in the present invention is measured under the following conditions using DSC Q1000 (manufactured by TA Instruments).
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. In the present invention, the peak temperature of the maximum endothermic peak in the first temperature increase of the resin A is TpA (° C.).

  The “melting point” of the crystalline substance (for example, crystalline polyester) in the present invention is the peak temperature of the maximum endothermic peak at the first temperature rise of the crystalline substance in the above method.

<Measurement method of loss modulus G ''>
In the present invention, the loss modulus G ″ is measured using a viscoelasticity measuring device (rheometer) ARES (manufactured by Rheometrics Scientific). The outline of the measurement is an ARES operation manual 902-30004 issued by Rheometrics Scientific. (August 1997 version), 902-00153 (July 1993 version), as described below.
・ Measurement jig: torsion rectangular
Measurement sample: A rectangular parallelepiped sample having a width of about 12 mm, a height of about 20 mm, and a thickness of about 2.5 mm is prepared for the resin used as the shell phase (maintaining 15 kN for 1 minute at room temperature). The pressure molding machine uses a 100 kN press NT-100H manufactured by NPa Systems.

After the jig and sample are left at room temperature (23 ° C.) for 1 hour, the sample is attached to the jig (see FIG. 1). As shown in FIG. 1, the measurement unit is fixed so that the width is about 12 mm, the thickness is about 2.5 mm, and the height is 10.0 mm. The temperature is controlled over 10 minutes up to the measurement start temperature of 30 ° C., and then measured with the following settings.
Measurement frequency: 6.28 rad / s
・ Measurement strain setting: Initial value is set to 0.1% and measurement is performed in automatic measurement mode ・ Sample extension correction: Adjustment in automatic measurement mode ・ Measurement temperature: 2 from 30 ° C. to 150 ° C. per minute Increase the temperature at a rate of ℃ ・ Measurement interval: Measure viscoelasticity data every 30 seconds, that is, every 1 ℃

  Data is transferred through an interface to an RSI Orchestrator (control, data collection and analysis software) (manufactured by Rheometrics Scientific) operating on Windows (registered trademark) 2000 manufactured by Microsoft Corporation.

  Of these, the loss elastic moduli G ″ a (TpA) and G ″ a () at each temperature of TpA (° C.) and TpA + 10 (° C.) with respect to the value of TpA determined by the method for measuring the peak temperature of the maximum endothermic peak. Read the value of TpA + 10) (see FIG. 2).

<Method for measuring number average particle diameter of organic-inorganic composite fine particles>
The number average particle diameter of the primary particles of the organic / inorganic composite fine particles is measured using a scanning electron microscope “S-4800” (trade name; manufactured by Hitachi, Ltd.). The toner to which the organic / inorganic composite fine particles are externally added is observed, and the major axis of the primary particles of 100 organic / inorganic composite fine particles is randomly measured in the field of view enlarged up to 200,000 times to obtain the number average particle size. The observation magnification is appropriately adjusted according to the size of the organic-inorganic composite fine particles.

<Calculation method of the ratio (mass%) of the part which can take a crystal structure>
The ratio (mol%) of the part that can take a crystal structure in the binder resin is measured by ¹ H-NMR under the following conditions.
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Frequency range: 10500Hz
Integration count: 64 times Measurement temperature: 30 ° C
Sample: A block polymer (50 mg) is put in a sample tube having an inner diameter of 5 mm, deuterated chloroform (CDCl ₃ ) is added as a solvent, and this is dissolved in a constant temperature bath at 40 ° C. From the obtained ¹ H-NMR chart, a peak independent of the peaks attributed to other constituent elements is selected from the peaks attributed to the constituent elements of the portion capable of taking a crystal structure, and the integration of this peak is selected. to calculate the value S _1. Similarly, a peak independent of the peaks attributed to other constituent elements is selected from the peaks attributed to the constituent elements of the amorphous portion, and the integrated value S ₂ of this peak is calculated. The ratio of the part that can take the crystal structure is obtained as follows using the integral value S ₁ and the integral value S ₂ . Note that n ₁ and n ₂ are the numbers of hydrogen in the constituent elements to which the focused peak belongs.
Percentage of sites that can take a crystal structure (mol%) =
{(S ₁ / n ₁ ) / ((S ₁ / n ₁ ) + (S ₂ / n ₂ ))} × 100

  The proportion (mol%) of the portion capable of taking the crystal structure thus obtained is converted to mass% according to the molecular weight of each component.

<Method for Measuring Insoluble Content of Organic Inorganic Composite Fine Particle Resin>
The THF-insoluble content of the organic-inorganic composite fine particle resin was quantified as follows.

  About 0.1 g of organic / inorganic composite fine particles (Wc [g]) are weighed in advance, and weighed in advance (for example, trade name “Oakridge centrifuge tube 3119-0050” (size 28.8 × 106.7 mm)). , Manufactured by Nalgene). To this, 20 g of THF is added, and the mixture is allowed to stand at room temperature for 24 hours to extract a THF soluble component. Next, this centrifuge bottle is set in a centrifuge “himac CR22G” (manufactured by Hitachi Koki Co., Ltd.), set to 20 ° C., and centrifuged at 15,000 rpm for 1 hour to obtain organic. The THF-insoluble matter of the entire inorganic composite fine particles was completely precipitated. The centrifuge bottle was taken out and the THF-soluble extract was separated and removed, and the centrifuge bottle with the contents contained therein was vacuum-dried at 40 ° C. for 8 hours. The centrifuge bottle was weighed and the mass of the centrifuge bottle weighed in advance was subtracted to obtain the mass (Wr [g]) of the THF-insoluble matter of the whole organic-inorganic composite fine particles.

The THF-insoluble content [% by mass] of the resin of the organic / inorganic composite fine particle was calculated by the following formula, where the content of the inorganic fine particle in the organic / inorganic composite fine particle was Wi [% by mass].
THF-insoluble matter [mass%] of organic / inorganic composite fine particle resin
= {(Wr−Wc × Wi / 100) / Wc × (100−Wi) / 100} × 100

<Measurement method of Si amount by X-ray fluorescence analyzer (XRF)>
In the present invention, the Si content of the resin A is determined with a fluorescent X-ray analyzer. Using a wavelength dispersive X-ray fluorescence analyzer Axios advanced (manufactured by PANalytical), the elements from Na to U in the toner particles are directly measured by the FP method in a He atmosphere. The total mass of the detected elements is taken as 100%, and the content (mass%) of Si with respect to the total mass is determined by software UniQuant5 (ver. 5.49).

<Measurement method of surface presence rate of inorganic fine particles on organic / inorganic composite fine particle surface>
The surface presence rate of the inorganic fine particles on the surface of the organic / inorganic composite fine particles is measured by ESCA (X-ray photoelectron spectroscopy). When the inorganic fine particles are silica particles, it is calculated from the silica-derived silicon (hereinafter abbreviated as Si) atomic weight. 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 organic / inorganic composite fine particles.

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 sealed with resin, and a recess for measuring powder having a depth of about 0.5 mm is produced. The measurement sample was packed into the concave portion with a spatula, and the sample was prepared by grinding.
The ESCA apparatus and measurement conditions are as follows.
Equipment used: Quantum 2000 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: φ100μm

  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.

  First, organic-inorganic composite fine particles are measured. Moreover, the particle | grains of the inorganic component used when producing organic-inorganic composite fine particles by the same method are measured. When the inorganic component is silica, the ratio of “Si amount when measuring organic / inorganic composite fine particles” to “Si amount when measuring silica particles” is the presence of the inorganic fine particles on the surface of the organic / inorganic composite fine particles in the present invention. Rate. In this measurement, calculation was performed using sol-gel silica particles (number average particle diameter 110 nm) as silica particles.

  The method for separating the organic / inorganic composite fine particles from the toner can be performed, for example, by the method described in the method for quantifying organic / inorganic composite fine particles and inorganic fine particles in the toner.

  Although the case where the inorganic fine particles are silica particles has been described, when the inorganic fine particles are not silica particles, the metal species included in the inorganic fine particles are identified from the database attached to the measuring apparatus, It is only necessary to perform a focused analysis.

  The coverage of the inorganic fine particles on the surface of the organic / inorganic composite fine particles was observed with a transmission electron microscope “H-800” (manufactured by Hitachi, Ltd.). Set the observation conditions to be clear and observe. Under that condition, 100 observations were made. Using the obtained projection image, the area ratio (area%) of the portion derived from the inorganic fine particles was calculated. Image processing software Image-Pro Plus 5.1J (manufactured by Media Cybernetics) was used for the area% of the portion derived from the inorganic fine powder particles.

<Method for measuring the amount of Si derived from polysiloxane in organic-inorganic composite fine particles by solid-state NMR>
The amount of Si derived from polysiloxane in the organic / inorganic composite fine particles can be determined from the atomic peak area by ²⁹ Si-NMR. 1.0 g of organic / inorganic composite fine particles are put in a sample tube, set in “CMX-300” manufactured by Chemanetics, and measured. Among the other signals obtained, a peak near 100 ppm (having a peak at 85 ppm to 115 ppm) is attributed to a peak derived from SiO _2, and a peak near 65 ppm (having a peak at 50 ppm to 80 ppm) is poly. The amount of Si derived from polysiloxane (atomic%) was determined from the siloxane-derived peak and the area ratio.

The measurement conditions for solid-state NMR in the present invention are as follows.
Apparatus: “CMX-300” manufactured by Chemagnetics
Temperature: 25 ° C
Reference substance: HMB (external standard: 17.35 ppm)
Measurement nucleus: 13C nuclear pulse width: 4.5 μsec (90 ° pulse)
Pulse repetition time: ACQTM 34.13msec
PD = 5sec (CP / MAS)
Data points: POINT 8192, SAMPO 1024
Spectrum width: 30.03 kHz
Pulse mode: CP / MAS
Sample rotation speed: 4 kHz
Contact time: 1.5 msec.

<Measuring method of weight average particle diameter (D4) and number average particle diameter (D1)>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.

  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 is set as follows.

  On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is 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 to 60 μm.

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) having an electrical output of 120 W is prepared. About 3.3 L of ion exchange water is placed in the water tank of the ultrasonic disperser, and about 2 mL of Contaminone N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. In the beaker, the height position of the beaker is adjusted so that the resonance state of the liquid surface of the electrolytic aqueous solution is maximized.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is 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 solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. The “average diameter” on the “analysis / volume statistic (arithmetic average)” screen when the graph / volume% is set in the dedicated software is the weight average particle size (D4). When the number% is set, the “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).

<Measurement Method of Number Average Molecular Weight Mn and Weight Average Molecular Weight Mw by Gel Permeation Chromatography (GPC)>
The number average molecular weight Mn and the weight average molecular weight Mw of the resin by gel permeation chromatography (GPC) were measured by GPC using THF as a solvent for the tetrahydrofuran (THF) soluble content of the resin. The measurement conditions are as follows.

(1) Preparation of measurement sample Resin (sample) and THF were mixed at a concentration of about 0.5 to 5 mg / mL (for example, about 5 mg / mL) and left at room temperature for several hours (for example, 5 to 6 hours). After that, the mixture was sufficiently shaken, and the THF and the sample were mixed well until there was no union of the sample. Furthermore, it left still at room temperature for 12 hours or more (for example, 24 hours). At this time, the time from the start of mixing the sample and THF to the end of standing was set to 24 hours or longer.

  Thereafter, a sample processing filter (pore size 0.45 to 0.5 μm, Mysori Disc H-25-2 [manufactured by Tosoh Corp.], Excro Disc 25CR [manufactured by Gelman Science Japan Ltd.] can be preferably used) is passed. Was used as a GPC sample.

(2) Sample measurement The column is stabilized in a heat chamber at 40 ° C., and THF as a solvent is flowed through the column at this temperature at a flow rate of 1 ml / min, so that the sample concentration is 0.5 to 5 mg / mL. Measurement was made by injecting 50 to 200 μl of a THF sample solution of the prepared resin.

  In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the calibration curve prepared from several monodisperse polystyrene standard samples and the number of counts.

As a standard polystyrene sample for preparing a calibration curve, Pressure Chemical Co. Manufactured by Toyo Soda Kogyo Co., Ltd. and having molecular weights of 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3 .9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ were used. An RI (refractive index) detector was used as the detector.

As the column, in order to accurately measure a molecular weight region of 1 × 10 ^{3 to} 2 × 10 ⁶ , a plurality of commercially available polystyrene gel columns were used in combination as described below. The measurement conditions of GPC in the present invention are as follows.

[GPC measurement conditions]
Apparatus: LC-GPC 150C (manufactured by Waters)
Column: KF801, 802, 803, 804, 805, 806, 807 (manufactured by Shodex) Column connection temperature Column temperature: 40 ° C
Mobile phase: THF (tetrahydrofuran)

<Measurement method of particle diameter of colorant particle, wax particle, resin fine particle for shell>
The particle diameter of each fine particle is measured using a Microtrac particle size distribution analyzer HRA (X-100) (manufactured by Nikkiso Co., Ltd.) with a range setting of 0.001 μm to 10 μm, and the number average particle diameter (μm or nm). Measure as In addition, acetone was selected as a dilution solvent.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

<Synthesis example of crystalline polyester 1>
-111.0 parts by weight of sebacic acid-20.5 parts by weight of adipic acid-68.5 parts by weight of 1,4-butanediol-0.1 part by weight of dibutyltin oxide In a reaction vessel equipped with a stirrer and a thermometer, nitrogen was added. The above was charged while replacing. After replacing the interior of the system with nitrogen by depressurization, the mixture was stirred at 250 ° C. for 1 hour. Crystalline polyester 1 was synthesize | combined by air-cooling when it became a viscous state and stopping reaction. Table 1 shows the physical properties of the crystalline polyester 1.

<Synthesis example of crystalline polyesters 2 to 5>
Crystalline polyesters 2 to 5 were synthesized in the same manner except that the materials and addition amounts of the acid component and alcohol component in the synthesis example of crystalline polyester 1 were changed as shown in Table 1. Table 1 shows the physical properties of the crystalline polyesters 2 to 5.

<Synthesis Example of Crystalline Polyester 6>
Sebacic acid 105.0 parts by mass Adipic acid 28.0 parts by mass 1,4-butanediol 67.0 parts by mass Dibutyltin oxide 0.1 part by mass In a reaction vessel equipped with a stirrer and a thermometer, nitrogen was added. The above was charged while replacing. After the inside of the system was purged with nitrogen by depressurization, the mixture was stirred at 180 ° C. for 6 hours. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure while continuing stirring, and the temperature was further maintained for 2 hours. Crystalline polyester 6 was synthesize | combined by air-cooling when it became a viscous state and stopping reaction. Table 1 shows the physical properties of the crystalline polyester 6.

<Synthesis example of block polymer 1>
-Crystalline polyester 6 210.0 parts by mass-Xylylene diisocyanate (XDI 56.0 parts by mass-Cyclohexanedimethanol (CHDM) 34.0 parts by mass-Tetrahydrofuran (THF) 300.0 parts by mass A stirrer and a thermometer are provided. The above was charged into the reaction vessel while substituting with nitrogen, heated to 50 ° C. and subjected to urethanization reaction for 15 hours, and then 3.0 parts by mass of salicylic acid was added to modify the isocyanate terminal. The solvent, THF, was distilled off to obtain block polymer 1.

<Synthesis example of vinyl monomer a1>
Crystalline polyester 1 100.0 parts by mass Tetrahydrofuran 100.0 parts by mass The above materials were charged into a reaction vessel equipped with a stirrer and a thermometer while being purged with nitrogen, and dissolved at 40 ° C.

  6.2 parts by mass of 2-isocyanatoethyl methacrylate (Karenz MOI manufactured by Showa Denko KK) was added dropwise and reacted at 40 ° C. for 2 hours. Subsequently, tetrahydrofuran was removed under reduced pressure at 40 ° C. for 5 hours by a rotary evaporator to obtain a vinyl monomer a1.

<Synthesis example of vinyl monomers a2 to a5>
In the synthesis example of vinyl monomer a1, by using crystalline polyesters 2 to 5 instead of crystalline polyester 1, vinyl monomers a2 to a5 were obtained.

<Preparation of vinyl monomer b1>
Commercially available vinyl-modified silicone monomer (X-22-2475: manufactured by Shin-Etsu Chemical Co., Ltd.)
Was prepared as vinyl monomer b1.

<Synthesis example of resin dispersion 1 for shell>
-Vinyl monomer b1 15.0 parts by mass-Vinyl monomer a1 50.0 parts by mass-Styrene 32.0 parts by mass-Acrylic acid 3.0 parts by mass-Azobismethoxydimethylvaleronitrile 0.3 mass Part / normal hexane 80.0 parts by mass The above materials were charged into a reaction vessel equipped with a stirrer and a thermometer while purging with nitrogen. A monomer solution was prepared by stirring and mixing at 20 ° C., and the solution was introduced into a dropping funnel previously heated and dried. Separately from this, 300 parts by mass of normal hexane was charged into a heat-dried two-necked flask. After substituting with nitrogen, a dropping funnel was attached, and the monomer solution was added dropwise over one hour at 40 ° C. in a sealed state. Stirring was continued for 3 hours from the end of dropping, and a mixture of 0.3 parts by mass of azobismethoxydimethylvaleronitrile and 20.0 parts by mass of normal hexane was added again, followed by stirring at 40 ° C. for 3 hours. Then, the resin dispersion liquid 1 for shells with a solid content of 20.0 mass% was obtained by cooling to room temperature. Table 2 shows the volume average particle diameter of the resin fine particles in the shell resin dispersion 1.

  Subsequently, a part of the shell resin dispersion 1 was removed under reduced pressure by a rotary evaporator at 40 ° C. for 5 hours to obtain a shell resin A1. DSC measurement was performed on the shell resin A1, and it was confirmed that the peak temperature of the maximum endothermic peak was 61 ° C. The viscoelasticity of the shell resin A1 was measured based on the above <Measurement Method of Loss Elastic Modulus G ″. Table 3 shows the physical properties of the loss elastic modulus of the shell resin A1.

  Further, the number average molecular weight and the weight average molecular weight of the resin A1 for the shell were also measured based on <Method of measuring the number average molecular weight Mn and the weight average molecular weight Mw by gel permeation chromatography (GPC)>. The results are also shown in Table 3.

<Synthesis Example of Shell Resin Dispersions 2 to 14>
In the synthesis example of the shell resin dispersion 1, the composition and addition amount of the vinyl monomer a, the vinyl monomer b, and the vinyl monomer c are changed to those shown in Table 2, and the shell resin dispersion is changed. Liquids 2 to 14 were obtained. Table 2 shows the volume average particle diameters of the resin fine particles of the shell resin dispersions 2 to 14.

  Subsequently, a part of the shell resin dispersions 2 to 14 was removed under reduced pressure by a rotary evaporator at 40 ° C. for 5 hours to obtain shell resins A2 to A14. The physical properties of the shell resins A2 to A14 were measured in the same manner as the shell resin A1. Table 3 shows the physical properties.

<Example of preparation of core resin solution 1>
Block polymer 1 100.0 parts by mass Acetone 100.0 parts by mass The above materials were put in a beaker and stirred at 3000 rpm for 1 minute using a disper (manufactured by Tokushu Kika Co., Ltd.) to obtain a core resin solution 1. A part of the core resin solution 1 was removed under reduced pressure by a rotary evaporator at 40 ° C. for 5 hours to obtain a core resin 1. The core resin 1 was confirmed to have 70 mass% of the portion capable of taking the crystal structure obtained based on the above <Method for calculating the ratio (mass%) of the portion capable of taking the crystal structure>. The maximum endothermic temperature in the DSC measurement of the core resin was 58 ° C.

<Preparation example of wax dispersion 1>
Paraffin wax HNP9 (melting point: 76 ° C., manufactured by Nippon Seiwa Co., Ltd.) 16.0 parts by mass Wax dispersant (in the presence of 15.0 parts by mass of polyethylene, 50.0 parts by mass of styrene, 25.0 n-butyl acrylate) A copolymer with a peak molecular weight of 8,500 obtained by graft copolymerization of 10.0 parts by mass with 10.0 parts by mass of acrylonitrile) 8.0 parts by mass, 76.0 parts by mass of a glass beaker with a stirring blade (made by IWAKI glass) And the paraffin wax was dissolved in acetone by heating the system to 70 ° C.

  Then, the system was gradually cooled while gently stirring at 50 rpm, and cooled to 25 ° C. over 3 hours to obtain a milky white liquid.

  This solution is put into a heat-resistant container together with 20 parts by weight of 1 mm glass beads and dispersed for 3 hours in a paint shaker to obtain a wax dispersion 1 having a volume average particle size of 270 nm and a wax solid content of 16% by mass. Obtained.

<Preparation Example of Colorant Dispersion 1>
・ C. I. Pigment Blue 15: 3 100.0 parts by mass, acetone 150.0 parts by mass, glass beads (1 mm) 200.0 parts by mass The above materials are put into a heat-resistant glass container, and dispersed in a paint shaker for 5 hours. The glass beads were removed with a nylon mesh to obtain a colorant dispersion 1 having a solid content of 40.0% by mass. The volume average particle diameter of the colorant particles was 100 nm.

<Production Example of Toner Particle 1>
In the apparatus shown in FIG. 3, first, the valves V1 and V2 and the pressure adjusting valve V3 are closed, and the shell resin dispersion 1 is placed in a pressure-resistant granulation tank T1 having a filter and a stirring mechanism for capturing toner particles. 35.0 parts by mass, and the internal temperature was adjusted to 25 ° C. Next, the valve V1 was opened, carbon dioxide (purity 99.99%) was introduced into the granulation tank T1 from the cylinder B1 using the pump P1, and the valve V1 was closed when the internal pressure reached 3.0 MPa.

Charge resin solution tank T2 with 175.0 parts by mass of resin solution 1 for the core, 31.3 parts by mass of wax dispersion 1, 12.5 parts by mass of colorant dispersion 1, 31.2 parts by mass of acetone, and adjust the internal temperature. Adjusted to 25 ° C.

  Next, the valve V2 is opened and the contents of the resin solution tank T2 are introduced into the granulation tank T1 using the pump P2 while stirring the inside of the granulation tank T1 at 1000 rpm. V2 was closed. After the introduction, the internal pressure of the granulation tank T1 was 5.0 MPa. The mass of the introduced carbon dioxide was measured using a mass flow meter.

  After the introduction of the contents of the resin solution tank T2 to the granulation tank T1, granulation was performed by further stirring for 10 minutes at a temperature of 25 ° C. and 2000 rpm.

  Next, the valve V1 was opened, and carbon dioxide was introduced into the granulation tank T1 from the cylinder B1 using the pump P1. At this time, the pressure regulating valve V3 was set to 10.0 MPa, and carbon dioxide was further circulated while maintaining the internal pressure of the granulation tank T1 at 10.0 MPa. By this operation, carbon dioxide containing the organic solvent (mainly acetone) extracted from the granulated droplets was discharged to the solvent recovery tank T3, and the organic solvent and carbon dioxide were separated.

  The introduction of carbon dioxide into the granulation tank T1 was stopped when it reached 15 times the mass of carbon dioxide initially introduced into the granulation tank T1. At this point, the operation of replacing carbon dioxide containing the solvent with carbon dioxide containing no solvent was completed.

  Further, the pressure regulating valve V3 was opened little by little, and the internal pressure of the granulation tank T1 was reduced to atmospheric pressure, whereby the toner particles (before treatment) 1 captured by the filter were collected.

  The obtained toner particles (before treatment) 1 were subjected to DSC measurement, and the peak temperature (Tm) of the maximum endothermic peak derived from the binder resin was determined to be 58 ° C.

(Annealing process)
The annealing treatment was performed using a constant temperature dryer (Satake Chemical 41-S5). The internal temperature of the constant temperature dryer was adjusted to 50 ° C.

  The toner particles (before treatment) 1 were spread evenly in a stainless steel vat, placed in the constant temperature dryer and allowed to stand for 2 hours, and then taken out. Thus, annealed toner particles (after treatment) 1 were obtained.

  The obtained toner 1 (after treatment) was subjected to DSC measurement, and the peak temperature (Tm) of the maximum endothermic peak derived from the binder resin was determined to be 61 ° C.

<Production Example of Toner Particles (After Treatment) 2 to Toner Particles (After Treatment) 14>
In the production example of toner particles 1, toner particles (before treatment) 2 to toner particles (before treatment) 14 were obtained in the same manner except that the type of the shell resin dispersion used was changed as shown in Table 4. .

  Subsequently, toner particles 1 (after treatment) 2 to toner particles (after treatment) 14 were obtained by performing the same treatment as the annealing treatment step for toner particles 1 (after treatment).

<Example of production of organic-inorganic composite fine particles 1>
In a 250 mL four-necked round bottom flask equipped with a stirring motor, a condenser, and a thermocouple, 18.7 g of an aqueous dispersion of colloidal silica having a number average particle diameter of 25 nm (silica concentration: 40% by mass), 125 mL of ion-exchanged water, and 16.5 g of methacryloxypropyl-trimethoxysilane (MPS) was added. The mixture was heated to 65 ° C. with stirring at 120 rpm. Nitrogen was blown into the mixture for 30 minutes, and after 3 hours, 0.16 g of a radical initiator 2,2′-azobisisobutyronitrile (abbreviated as AIBN) dissolved in 10 mL of ethanol was added, and the temperature was set to 75 ° C. did. Radical polymerization was performed at 75 ° C. for 5 hours, and then 3 mL (2.3 g) of 1,1,1,3,3,3-hexamethyldisilazane (HMDS) was added to the mixture. The reaction was further carried out for 3 hours, and the mixture was filtered through a 170 mesh sieve to remove aggregates, transferred to a stainless steel tray, and then dried at 120 ° C. for 12 hours. A white powdery solid was collected and pulverized for 1 minute using an oster blender OB-1. The volume was set to 250 ml and the rotation was set to 15700 rpm.

<Production example of organic-inorganic composite fine particles 2 to 6>
In the production example of the organic / inorganic composite fine particles 1, as shown in Table 5, except that the addition amount of methacryloxypropyl-trimethoxysilane, the type of colloidal silica, and the addition amount were changed, the organic / inorganic composite fine particles 2 to 6 were similarly used. Got.

<Preparation of sol-gel silica particles 1>
A sol-gel silica particle 1 having a number average particle diameter of 110 nm and surface-treated with HMDS (hexamethyldisilazane) was prepared.

<Preparation of resin particle 1>
EPOSTA S manufactured by Nippon Shokubai Co., Ltd., which is a commercially available melamine-formaldehyde resin particle and has a number average particle diameter of 300 nm, was prepared as resin particle 1.

[Example 1]
(Preparation of toner 1 and two-component developer 1)
Next, the external additives listed in Table 6 were externally added to the toner particles (after treatment) 1 with Nobilta (manufactured by Hosokawa Micron Corporation) at a power of 0.5 kW for 5 minutes to obtain toner 1.

[Comparative Examples 1 to 6]
In the same manner as in Example 1, toner particles (after treatment) 1 to toner particles (after treatment) 4 were externally added using the external additives shown in Table 6 to obtain toners 2 to 7.

[Examples 2 to 18]
In the same manner as in Example 1, toner particles (after treatment) 1 and toner particles (after treatment) 5 to toner particles (after treatment) 14 were externally added using the external additives listed in Table 6, and toners 8 to 24 was obtained.

  The following evaluation test was performed using the obtained toner. The evaluation results are shown in Table 6.

<Evaluation of heat-resistant storage stability>
About 10 g of toner was put in a 100 ml polycup and allowed to stand at 53 ° C. for 3 days, and then each of the left samples was visually evaluated. In the present invention, it was judged that A rank to C rank have good heat-resistant storage stability.
(Evaluation criteria)
A: Aggregates are not seen.
B: The aggregate is slightly seen.
C: Aggregates are seen but easily collapse.
D: Almost all aggregates.

<Evaluation of low-temperature fixability>
A commercially available Canon printer LBP5300 was used to evaluate the fixability. The LBP 5300 employs one-component contact development and regulates the amount of toner on the development carrier by a toner regulating member. As the evaluation cartridge, the toner contained in a commercially available cartridge was taken out, the inside was cleaned by air blow, and a cartridge filled with 160 g of the toner was used. The cartridge was installed in the cyan station, and the other cartridges were evaluated by installing dummy cartridges.

The development contrast of the copying machine is adjusted so that the amount of toner on the paper is 0.6 / cm ² , and a “solid” unfixed image having a front margin of 5 mm, a width of 100 mm, and a length of 280 mm is obtained in the single color mode. It was created in a normal temperature and humidity environment (23 ° C./60% RH). The paper used was A4 paper (“Prober Bond paper”: 105 g / m ² , manufactured by Fox River).

Next, the fixing device of LBP5900 (manufactured by Canon Inc.) was modified so that the fixing temperature can be manually set, and the rotation speed of the fixing device was changed to 300 mm / s. Further, the pressure during fixing was set to 0.75 kgf / cm ² . Each of the above-mentioned “solid” unfixed images was increased by increasing the fixing temperature by 5 ° C. in the range of 80 ° C. to 180 ° C. in the normal temperature and humidity environment (23 ° C./60% RH) using the modified fixing device. A fixed image at temperature was obtained.

  Cover the image area of the obtained fixed image with a soft thin paper (for example, trade name “Dasper”, manufactured by Ozu Sangyo Co., Ltd.), and apply the load of 1.0 KPa on the thin paper three times, Rubbed. The image density before and after rubbing was measured, respectively, and the reduction rate ΔD (%) of the image density was calculated by the following formula. The temperature at which ΔD (%) was less than 10% was defined as the fixing start temperature, and the low temperature fixability was evaluated according to the following evaluation criteria.

The image density was measured with a color reflection densitometer (Color reflection densitometer X-Rite 404A: manufacturer X-Rite).
(Formula): ΔD (%) = (Image density before rubbing−Image density after rubbing) / Image density before rubbing × 100

In the present invention, A rank to C rank were judged as good low temperature fixability.
(Evaluation criteria)
A: Fixing start temperature is less than 100 ° C. B: Fixing start temperature is 100 ° C. or more and less than 110 ° C. C: Fixing start temperature is 110 ° C. or more and less than 120 ° C. D: Fixing start temperature is 120 ° C. or more.

<Evaluation of hot offset resistance of toner>
The fixed image obtained in the evaluation of the fixing start temperature was evaluated for occurrence of hot offset (a phenomenon in which the fixed image adheres from the paper to the fixing roller, and the fixing roller rotates once and reattaches to the paper).

  When the image density of the non-image portion showed a density of 0.05 times or more of the solid image density, an offset was generated. The image density was evaluated using a reflection densitometer (500 Series Spectrodensitometer; manufactured by X-Rite).

In the present invention, from A rank to C rank was judged as good offset resistance.
(Evaluation criteria)
A: Hot offset occurs at 170 ° C. or higher.
B: Hot offset occurred at 160 ° C or 165 ° C.
C: Hot offset occurred at 150 ° C or 155 ° C.
D: Hot offset occurs at 145 ° C. or lower, resulting in poor offset resistance.

<Evaluation of fixing temperature range>
The upper limit range in which hot offset does not occur was set as the fixable temperature, and the difference between the fixable temperature and the fixing start temperature was evaluated as the fixing temperature range. The evaluation criteria for the fixing temperature range are as follows. In the present invention, it was judged that the rank A to rank C had a good fixing temperature range.
(Evaluation criteria)
A: Fixing temperature range is 70 ° C. or more B: Fixing temperature range is 60 ° C. or more and less than 70 ° C. C: Fixing temperature range is 50 ° C. or more and less than 60 ° C. D: Fixing temperature range is less than 50 ° C.

  The toner chargeability was evaluated using the initial charge amount in an N / N (temperature 23 ° C., relative humidity 50%) environment and the rate of decrease in the triboelectric charge amount of the toner before and after leaving the environment under each environment.

<Toner cleaning property>
In a low-temperature and low-humidity environment (10 ° C / 14% Rh), a durability test was performed to continuously output 3000 ruled line images with a printing ratio of 5%, and the presence or absence of vertical streaks due to poor cleaning on the output image was visually observed. And evaluated.
A: No vertical streak is observed even after 3000 sheets are output.
B: Minor vertical stripes are observed between 2501 and 3000.
C: Vertical stripes are observed between 2001 and 2500.
D: Vertical stripes occur between 101 and 2000.
E: Vertical streaks occur with 100 sheets or less.

<Durability>
Using the above-mentioned Canon printer LBP5300, durability was evaluated. The LBP 5300 employs one-component contact development and regulates the amount of toner on the development carrier by a toner regulating member. As the evaluation cartridge, the toner contained in a commercially available cartridge was taken out, the inside was cleaned by air blow, and a cartridge filled with 160 g of the toner was used. The cartridge was installed in the cyan station, and the other cartridges were evaluated by installing dummy cartridges.

In a low-temperature and low-humidity environment at 15 ° C. and 10% RH, an image with a printing rate of 1% was continuously output. A solid image and a halftone image were output each time 1,000 sheets were output, and the presence or absence of occurrence of vertical stripes due to toner fusion to the regulating member, that is, so-called development stripes, was visually confirmed. Finally, 15,000 images were output.
A: No development streak occurred on 15,000 sheets.
B: The development streak in the halftone image occurs between 10,000 and 14,999 sheets, and the development streak cannot be confirmed in the solid image at 15,000 sheets.
C: A development streak in a halftone image occurs between 10,001 sheets and 14,999 sheets and an image at the time of 15,000 sheets can be confirmed with a solid image.
D: The development streak occurs in a halftone image at 10,000 or less.

  T1: Granulation tank, T2: Resin solution tank, T3: Solvent recovery tank, B1: Carbon dioxide cylinder, P1, P2: Pump, V1, V2: Valve, V3: Pressure adjustment valve, 1: Suction machine (measuring vessel 2 2: Metal measuring container, 3: 500 mesh screen, 4: Metal lid, 5: Vacuum gauge, 6: Air flow control valve, 7: Suction port, 8: Condenser , 9: Electrometer

Claims (7)

A toner having a core containing a binder resin, a colorant, and a wax, a core-shell structured toner particle having a shell phase containing resin A, and a toner having organic-inorganic composite fine particles,
The resin A is
(I) a resin having a siloxane bond,
(Ii) In the measurement with a differential scanning calorimeter (DSC), the peak temperature TpA (° C.) of the maximum endothermic peak at the first temperature rise is 55 ° C. or more and 80 ° C. or less,
(Iii) In the viscoelasticity measurement, the loss elastic modulus at the TpA (° C.) is G ″ (TpA) [Pa], and the loss elastic modulus at a temperature TpA + 10 (° C.) 10 ° C. higher than the TpA is G ″ (TpA + 10) [Pa ]
G ″ (TpA) and G ″ (TpA + 10) satisfy the following formula (1):
{Log (G ″ (TpA)) − log (G ″ (TpA + 10))} ≧ 1.0 (1)
The organic-inorganic composite fine particles are
(Iv) Tetrahydrofuran (THF), which is a resin component that has a structure in which inorganic fine particles are embedded in a partially exposed state on the surface of a resin particle containing a resin having a siloxane bond, and which constitutes the resin particle Insoluble matter is 70.0% by mass or more,
(V) the number average particle diameter is 50 nm or more and 500 nm or less,
Toner characterized by the above.   The toner according to claim 1, wherein the resin A is a resin having a portion having a crystal structure.   The toner according to claim 2, wherein the portion having the crystal structure is a portion derived from crystalline polyester and is contained in an amount of 20.0% by mass or more based on the resin A.   The toner according to claim 1, wherein the resin A is a resin containing an organic polysiloxane in a molecular structure.   The resin A is characterized in that the content of Si derived from the organopolysiloxane is 1.0% by mass or more and 10.0% by mass or less with respect to the resin A in compositional analysis by fluorescent X-ray. Item 5. The toner according to Item 4.   6. The toner according to claim 1, wherein the organic / inorganic composite fine particles have a surface abundance ratio of the inorganic fine particles of 20% or more and 70% or less. 7. The resin component contained in the organic-inorganic composite fine particles contains 50.0% by mass or more of a silane compound polymer represented by the following formula [1]. The toner described in 1.
X-SiH _3-n (OR) _n ... [1]
Here, X represents an organic functional group, R represents a methyl or ethyl group, and n represents an integer of 1 to 3.

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