JP2016145857A - Toner and two-component developer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that has excellent low-temperature fixability and can suppress the occurrence of filming on a surface of a photoreceptor.SOLUTION: The toner comprises a binder resin containing an amorphous polyester resin and a crystalline polyester resin, and a release agent, in which the amorphous polyester resin is obtained by polymerization condensation of a dicarboxylic acid monomer essentially comprising terephthalic acid or isophthalic acid with a diol monomer essentially comprising ethylene glycol, and the crystalline polyester resin is obtained by polymerization condensation of a dicarboxylic acid monomer essentially comprising an aliphatic dicarboxylic acid having 9 to 22 carbon atoms with a diol monomer essentially comprising an aliphatic diol having 2 to 10 carbon atoms. The release agent is a synthetic ester wax having a hydroxyl value of less than 5 mgKOH/g.SELECTED DRAWING: None

Description

  The present invention relates to a toner and a two-component developer containing the toner, and more particularly to a toner used in an electrophotographic image forming apparatus.

  In order to improve the low-temperature fixability of the toner, it is known to use a binder resin in which a crystalline polyester resin is dispersed in an amorphous polyester resin, but the crystallinity of the crystalline polyester resin is lowered. In addition, the storage stability of the toner (toner aggregation resistance) is lowered, and the toner is liable to aggregate.

  In response to this drawback, in JP 2012-32639 A (Patent Document 1), as a binder resin, a polyvalent carboxylic acid containing terephthalic acid or isophthalic acid as a main component and a diol containing ethylene glycol as a main component, A non-crystalline polyester resin obtained by polycondensation of a dicarboxylic acid, a dicarboxylic acid containing a C9-22 aliphatic dicarboxylic acid as a main component, and a diol containing a C2-10 aliphatic diol as a main component. By using a crystalline polyester resin obtained by condensation polymerization, a toner is prepared by a kneading and pulverizing method, so that both storage stability of the toner (toner aggregation resistance) and low-temperature fixability are achieved.

JP 2012-32639 A

  However, when the toner described in Japanese Patent Application Laid-Open No. 2012-32639 is used, there is a problem in that filming occurs on the surface of the photoreceptor and image quality is deteriorated. In particular, when the surface layer of the photoconductor is an organic photoconductor containing a polycarbonate resin as a main component, the occurrence of filming is significant.

  Accordingly, an object of the present invention is to provide a toner that solves the above-described problems of the prior art, has excellent low-temperature fixability, and can prevent filming on the surface of the photoreceptor. Another object of the present invention is to provide a two-component developer containing such toner.

The inventor has examined the cause of filming that occurs when a toner as described in JP 2012-32639 A is used. Such a toner is produced by a kneading and pulverizing method using a binder resin containing an amorphous polyester resin and a crystalline polyester resin specified as described above. It has been found that when the toner is heated in the component developing device or in the toner cartridge, the toner tends to bleed out on the surface of the toner base particles.
In Japanese Patent Application Laid-Open No. 2012-32639, natural wax or the like is described as a mold release agent, and carnauba wax is actually used. Carnauba wax is a natural wax containing an ester compound as a main component, but is also known to contain a compound having a hydroxy group such as a hydroxy fatty acid ester or an aliphatic alcohol. For this reason, a transesterification reaction occurs between the crystalline polyester resin and the free alcohol contained in the carnauba wax, and the crystalline structure of the crystalline polyester collapses and exists in an unstable state in the toner. Therefore, it is considered that when the toner is heated in the developing tank or in the toner cartridge, the transesterified crystalline polyester resin and the wax bleed out.
Therefore, as a result of intensive studies to achieve the above object, the present inventor has found that when a synthetic ester wax having a hydroxyl value of less than 5 mgKOH / g is used as a release agent, the crystalline polyester resin is stained from toner base particles. As a result, it was found that the occurrence of filming on the surface of the photoreceptor can be prevented, and the present invention has been completed.

That is, the toner of the present invention is a toner including a binder resin containing an amorphous polyester resin and a crystalline polyester resin, and a release agent.
The amorphous polyester resin is an amorphous polyester resin obtained by polycondensing a dicarboxylic acid monomer containing terephthalic acid or isophthalic acid as a main component and a diol monomer containing ethylene glycol as a main component,
The crystalline polyester resin is obtained by polycondensing a dicarboxylic acid monomer mainly containing an aliphatic dicarboxylic acid having 9 to 22 carbon atoms and a diol monomer mainly containing an aliphatic diol having 2 to 10 carbon atoms. A crystalline polyester resin,
The release agent is a synthetic ester wax having a hydroxyl value of less than 5 mgKOH / g.

  In a preferred example of the toner of the present invention, the synthetic ester wax contains a monoester compound.

  A two-component developer according to the present invention includes the above toner and a carrier.

  According to the toner of the present invention, an amorphous polyester resin obtained by polycondensation of a dicarboxylic acid monomer containing terephthalic acid or isophthalic acid as a main component and a diol monomer containing ethylene glycol as a main component, and a carbon number of 9 to To a binder resin containing a crystalline polyester resin obtained by polycondensation of a dicarboxylic acid monomer containing 22 aliphatic dicarboxylic acid as a main component and a diol monomer containing a C 2-10 aliphatic diol as a main component, By combining a release agent that is a synthetic ester wax having a hydroxyl value of less than 5 mgKOH / g, a toner that has excellent low-temperature fixability and can prevent filming on the surface of the photoreceptor can be provided.

  Further, according to the two-component developer of the present invention, it is possible to provide a two-component developer that has excellent low-temperature fixability and can prevent filming on the surface of the photoreceptor by using such a toner. Can do.

[toner]
Hereinafter, the toner of the present invention will be described in detail. The toner of the present invention is a toner containing a binder resin containing an amorphous polyester resin and a crystalline polyester resin, and a release agent, wherein the amorphous polyester resin contains terephthalic acid or isophthalic acid as a main component. A non-crystalline polyester resin obtained by polycondensation of a dicarboxylic acid monomer and a diol monomer containing ethylene glycol as a main component, wherein the crystalline polyester resin is mainly composed of an aliphatic dicarboxylic acid having 9 to 22 carbon atoms. Is a crystalline polyester resin obtained by polycondensation of a dicarboxylic acid monomer contained as a main component with a diol monomer containing a C 2-10 aliphatic diol as a main component, and the release agent has a hydroxyl value of less than 5 mgKOH / g It is characterized by being a synthetic ester wax.

  The toner of the present invention comprises toner base particles containing a binder resin and a release agent, and external additives externally added to the surface of the toner base particles as necessary. Further, internal additives such as a colorant and a charge control agent are further included. The toner of the present invention preferably has a volume average particle diameter of 5 μm to 10 μm.

[Binder resin]
The binder resin used in the toner of the present invention includes at least the amorphous polyester resin and the crystalline polyester resin. The crystalline polyester resin and internal additives such as a release agent, a colorant, and a charge control agent are dispersed in the amorphous polyester resin.

  In general, a crystalline polyester resin can reduce the softening temperature and melt viscosity of the toner without lowering the mechanical strength of the toner as compared to the amorphous polyester resin. It is known that the low-temperature fixability of toner can be improved when used in combination with a conductive polyester resin. Further, in the binder resin used in the toner of the present invention, the amorphous polyester resin and the crystalline polyester resin are different in the main component of the dicarboxylic acid monomer and in some cases even the main component of the diol monomer. Therefore, the toner design can achieve a balance between low-temperature fixability and storage stability.

  In the present invention, the main component of the dicarboxylic acid monomer and the main component of the diol monomer refer to a monomer having the maximum molar content among the monomers constituting each, but in the case of a single monomer (that is, , Terephthalic acid, isophthalic acid, ethylene glycol, aliphatic dicarboxylic acid having 9 to 22 carbon atoms, or aliphatic diol having 2 to 10 carbon atoms is 100%).

  In the toner of the present invention, the mass ratio (A / B) of the crystalline polyester resin (A) and the amorphous polyester resin (B) in the binder resin is not particularly limited, and is appropriately determined as necessary. Although it can be adjusted, the content of the crystalline polyester resin in the toner base particles is preferably 5 to 20% by mass from the viewpoint of achieving both low-temperature fixability and storage stability.

In the present invention, the amorphous resin and the crystalline resin are distinguished by the crystallinity index. A resin having a crystallinity index in the range of 0.6 to 1.5 is defined as a crystalline resin, and the crystallinity index is 0.6. A resin that is less than or exceeds 1.5 is defined as an amorphous resin. A resin having a crystallinity index of more than 1.5 is amorphous, and a resin having a crystallinity index of less than 0.6 has low crystallinity and many amorphous portions.
The crystallinity index is a physical property that serves as an index of the degree of crystallization of the resin, and is defined by the ratio between the softening temperature and the maximum endothermic peak temperature (softening temperature / maximum endothermic peak temperature). Here, the highest endothermic peak temperature refers to the temperature of the peak on the highest temperature side among the observed endothermic peaks. In the crystalline polyester resin, the highest peak temperature is the melting point, and in the amorphous polyester resin, a straight line obtained by extending the base line on the high temperature side of the endothermic peak corresponding to the glass transition of the obtained DSC curve to the low temperature side, The glass transition temperature (Tg) is defined as the temperature at the intersection with a tangent drawn at a point where the gradient is maximum with respect to the curve from the peak rising portion to the apex. The degree of crystallization can be controlled by adjusting the type and ratio of raw material monomers, production conditions (for example, reaction temperature, reaction time, cooling rate) and the like.

[Amorphous polyester resin]
The amorphous polyester resin used in the toner of the present invention is an amorphous polyester resin obtained by polycondensation of a dicarboxylic acid monomer containing terephthalic acid or isophthalic acid as a main component and a diol monomer containing ethylene glycol as a main component. It is.

  The dicarboxylic acid monomer used for the synthesis of the amorphous polyester resin contains terephthalic acid or isophthalic acid as a main component. Here, the molar content of terephthalic acid or isophthalic acid in the dicarboxylic acid monomer is preferably 70% or more and 100% or less, and more preferably 80% or more and 100% or less.

  The dicarboxylic acid monomer may contain an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid other than terephthalic acid and isophthalic acid. Examples of the aromatic dicarboxylic acid other than terephthalic acid and isophthalic acid include fumaric acid, and examples of the aliphatic dicarboxylic acid include adipic acid, sebacic acid, and succinic acid. The dicarboxylic acid monomer may also include ester-forming derivatives of terephthalic acid or isophthalic acid, ester-forming derivatives of aromatic dicarboxylic acids other than terephthalic acid and isophthalic acid, and ester-forming derivatives of aliphatic dicarboxylic acids. In the present invention, ester-forming derivatives include carboxylic acid anhydrides and alkyl esters. In addition, when using dicarboxylic acid monomers other than terephthalic acid and isophthalic acid, this dicarboxylic acid monomer may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the synthesis of the amorphous polyester resin, a tricarboxylic or higher polycarboxylic acid monomer may be used together with the dicarboxylic acid monomer. As the trivalent or higher polycarboxylic acid monomer, trivalent or higher polycarboxylic acid such as trimellitic acid or pyromellitic acid or an ester-forming derivative thereof can be used. When using trivalent or higher polycarboxylic acid monomers, these polycarboxylic acid monomers may be used singly or in combination of two or more.

  The diol monomer used for the synthesis of the amorphous polyester resin contains ethylene glycol as a main component. Here, the molar content of ethylene glycol in the diol monomer is preferably 70% or more and 100% or less, and more preferably 80% or more and 100% or less.

  The diol monomer can include 1,3-propylene glycol, 1,4-butanediol, and the like. When using diol monomers other than ethylene glycol, these diol monomers may be used alone or in combination of two or more.

  The amorphous polyester resin used in the toner of the present invention can be produced in the same manner as in a normal polyester production method. For example, by performing a polycondensation reaction in a nitrogen gas atmosphere at a temperature of 190 to 240 ° C. using a dicarboxylic acid monomer, a diol monomer, and optionally a polycarboxylic acid monomer having a valence of 3 or more, an amorphous property A polyester resin can be synthesized.

  In the above polycondensation reaction, the reaction ratio between the diol monomer and the carboxylic acid monomer (including a dicarboxylic acid monomer and, optionally, a tricarboxylic or higher polycarboxylic acid monomer) is an equivalent ratio [OH] / hydroxyl group to carboxyl group. [COOH] is preferably 1.3 / 1 to 1 / 1.2. In the polycondensation reaction, the molar content of the dicarboxylic acid monomer in the carboxylic acid monomer is preferably 80 to 100%. Furthermore, in the polycondensation reaction, an esterification catalyst such as dibutyltin oxide or titanium alkoxide (for example, tetrabutoxy titanate) can be used as necessary.

  The glass transition temperature (Tg) of the amorphous polyester resin is preferably 60 to 70 ° C. from the viewpoint of fixability, storage stability and durability.

  The softening point (Tm) of the amorphous polyester resin is preferably 100 to 140 ° C. from the viewpoint of achieving both low-temperature fixability and hot offset resistance.

  The molecular weight of the amorphous polyester resin is determined by gel peak permeation chromatography (GPC), the peak top molecular weight (Mp) of tetrahydrofuran (THF) soluble matter, and the heat resistance, heat storage property and low temperature of the toner. From the viewpoint of coexistence of fixability, 3000 to 15000 is preferable. In GPC, tetrahydrofuran (THF) is used as a mobile phase, and polystyrene is used as a standard substance. The peak top molecular weight refers to a molecular weight showing the maximum peak height in a chromatogram obtained by GPC measurement.

  The acid value of the amorphous polyester resin is preferably 0 to 40 mgKOH / g from the viewpoint of charging characteristics, and the hydroxyl value of the amorphous polyester resin is preferably 0 to 40 mgKOH / g from the viewpoint of hot offset resistance. preferable.

  The SP value (solubility parameter) of the amorphous polyester resin is preferably 10.5 to 12.5.

  In the toner of the present invention, the content of the amorphous polyester resin is not particularly limited, but is preferably 60 to 80% by mass in the toner base particles.

[Crystalline polyester resin]
The crystalline polyester resin used in the toner of the present invention comprises a dicarboxylic acid monomer containing an aliphatic dicarboxylic acid having 9 to 22 carbon atoms as a main component and a diol monomer containing an aliphatic diol having 2 to 10 carbon atoms as a main component. It is a crystalline polyester resin obtained by polycondensation.

  The dicarboxylic acid monomer used for the synthesis of the crystalline polyester resin contains an aliphatic dicarboxylic acid having 9 to 22 carbon atoms as a main component. Here, the molar content of the aliphatic dicarboxylic acid having 9 to 22 carbon atoms in the dicarboxylic acid monomer is preferably 80% or more and 100% or less.

  Examples of the aliphatic dicarboxylic acid having 9 to 22 carbon atoms include azelaic acid, zebacic acid, 1,10-decanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, and the like. The dicarboxylic acid monomer can also contain ester-forming derivatives of these aliphatic dicarboxylic acids. In addition, these dicarboxylic acid monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the synthesis of the crystalline polyester resin, a tricarboxylic or higher polycarboxylic acid monomer may be used together with the dicarboxylic acid monomer. As the trivalent or higher polycarboxylic acid monomer, trivalent or higher polycarboxylic acid such as trimellitic acid or pyromellitic acid or an ester-forming derivative thereof can be used. When using trivalent or higher polycarboxylic acid monomers, these polycarboxylic acid monomers may be used singly or in combination of two or more.

  The diol monomer used for the synthesis of the crystalline polyester resin contains an aliphatic diol having 2 to 10 carbon atoms as a main component. Here, the molar content of the aliphatic diol having 2 to 10 carbon atoms in the diol monomer is preferably 80% or more and 100% or less.

  Examples of the aliphatic diol having 2 to 10 carbon atoms include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like. In addition, these diol monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the synthesis of the crystalline polyester resin, a trivalent or higher valent polyol monomer may be used together with the diol monomer. As the trivalent or higher polyol monomer, glycerin, trimethylolpropane or the like can be used. When using a trivalent or higher polyol monomer, the polyol monomer may be used alone or in combination of two or more.

  The crystalline polyester resin used in the toner of the present invention can be produced in the same manner as a normal polyester production method. For example, a polycondensation reaction is performed at a temperature of 190 to 240 ° C. in a nitrogen gas atmosphere using a dicarboxylic acid monomer, a diol monomer, and optionally a tricarboxylic or higher polycarboxylic acid monomer or a trivalent or higher polyol monomer. By doing so, a crystalline polyester resin can be synthesized.

  In the polycondensation reaction, a hydroxyl group of a polyol monomer (including a diol monomer and optionally a trivalent or higher polyol monomer), a carboxylic acid monomer (a dicarboxylic acid monomer, and optionally a trivalent or higher polycarboxylic acid monomer) The equivalent ratio (including OH) to the carboxyl group (OH group / COOH group) is preferably 1.01 to 1.14 from the viewpoint of storage stability. In the polycondensation reaction, the molar content of the dicarboxylic acid monomer in the carboxylic acid monomer is preferably 90 to 100%. The smaller the molar content of the dicarboxylic acid monomer, the lower the rate and speed of crystallization and the insufficient toner aggregation resistance. Furthermore, in the polycondensation reaction, the molar content of the diol monomer in the polyol monomer is preferably 80 to 100%. In the polycondensation reaction, an esterification catalyst such as dibutyltin oxide or titanium alkoxide (for example, tetrabutoxy titanate) can be used as necessary.

  The melting point (Tmp) of the crystalline polyester resin is more preferably 60 to 90 ° C. from the viewpoints of fixability, storage stability and durability.

  The softening point (Tm) of the crystalline polyester resin is preferably 65 to 110 ° C. from the viewpoints of low temperature fixability and blocking resistance.

  The crystalline polyester resin preferably has a softening point (Tm) to melting point (Tmp) ratio (Tm / Tmp) of 1.0 to 1.4 from the viewpoint of crystallization speed and blocking resistance.

  The molecular weight of the crystalline polyester resin is such that the peak top molecular weight (Mp) of the tetrahydrofuran (THF) soluble component measured using gel permeation chromatography (GPC) is from the viewpoint of storage stability and low temperature fixability, etc. 10,000 to 90,000 are preferable. In GPC, tetrahydrofuran (THF) is used as a mobile phase, and polystyrene is used as a standard substance. The peak top molecular weight refers to a molecular weight showing the maximum peak height in a chromatogram obtained by GPC measurement.

  The acid value of the crystalline polyester resin is preferably 0 to 30 mg KOH / g from the viewpoint of charging characteristics, and the hydroxyl value of the crystalline polyester resin is preferably 0 to 40 mg KOH / g from the viewpoint of hot offset resistance.

  The SP value (solubility parameter) of the crystalline polyester resin is preferably 9.3 to 10.0. When the SP value is less than 9.3, the compatibility with the amorphous polyester resin becomes too low, and the durability may be insufficient. On the other hand, if the SP value exceeds 10.0, the Tg of the binder resin may decrease, and the blocking resistance may decrease. In addition, if the difference in SP value between the amorphous resin and the crystalline resin is close, they are too compatible. In this case, although effective for low-temperature fixing, blocking resistance may be reduced. On the other hand, if the difference in SP value is too far away, there may be no effect on the low-temperature fixability, so it is important to select an amorphous resin and a crystalline polyester resin.

  In the toner of the present invention, the content of the crystalline polyester resin is not particularly limited, but is preferably 5 to 20% by mass in the toner base particles.

[Release agent]
The release agent is added to impart releasability to the toner when the toner is fixed on the recording medium. The release agent used in the present invention is a synthetic ester wax having a hydroxyl value of less than 5 mgKOH / g, and a synthetic ester wax obtained from a carboxylic acid and an alcohol can be used.

Examples of the synthetic ester wax include ester compounds such as monoester compounds, diester compounds, triester compounds, and tetraester compounds. The carboxylic acid used for the synthesis of the ester wax is preferably a higher fatty acid having 13 to 30 carbon atoms, and the alcohol is preferably an alcohol having 2 to 30 carbon atoms.
The monoester compound is an ester compound obtained from a monovalent carboxylic acid and a monovalent alcohol.
As the monovalent carboxylic acid, for example, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melicic acid and the like can be used.
As the monovalent alcohol, for example, myristyl alcohol, cetyl alcohol, stearyl alcohol, aralkyl alcohol, behenyl alcohol, tetracosanol, hexacosanol, octacosanol, triacontanol and the like can be used.
The diester compound is an ester compound obtained from a monovalent carboxylic acid and a divalent alcohol.
Examples of the divalent alcohol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, 1,20-eicosanediol, 1,30-triacontanediol, diethylene glycol, dipropylene Glycol, 2,2,4-trimethyl-1,3-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, spiroglycol, 1,4-phenylene glycol and the like can be used.
The triester compound is an ester compound obtained from a monovalent carboxylic acid and a trivalent alcohol.
Examples of the trivalent alcohol include 1,2,4-butanetriol, 1,2,5-pentanetriol, 2-methyl-1,2,4-butanetriol, glycerin, 2-methylpropanetriol, and trimethylol. Ethane, triethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene and the like can be used.
The tetraester compound is an ester compound obtained from a monovalent carboxylic acid and a tetravalent alcohol.
As the tetravalent alcohol, for example, 1,2,3,6-hexanetetrol, pentaerythritol and the like can be used.

Synthetic ester wax is obtained from carboxylic acid and alcohol as described above. When synthetic alcohol wax contains a large amount of raw material alcohol, that is, when a large amount of free alcohol is contained, toner production process ( In the kneading step), the dispersion state of the crystalline polyester resin dispersed in the amorphous polyester resin is affected, and the crystalline polyester resin tends to bleed out. The cause of this is presumed that the crystal structure of the crystalline polyester resin has changed due to the transesterification reaction between the crystalline polyester resin and a free alcohol (particularly a primary alcohol).
According to the toner of the present invention, since the hydroxyl value of the synthetic ester wax is less than 5 mgKOH / g, the transesterification reaction with the crystalline polyester resin can be sufficiently suppressed, and the bleed-out of the crystalline polyester resin is eventually achieved. Can be suppressed.

  The ester compound constituting the synthetic ester wax preferably accounts for 99% by mass to 100% by mass of the wax. Moreover, it is preferable that an ester compound is a monoester compound which has one ester bond from a viewpoint of the improvement effect of blocking resistance.

  The synthetic ester wax used in the toner of the present invention preferably has a melting point of 70 ° C. or higher and 95 ° C. or lower.

  In the toner of the present invention, the synthetic ester wax as a release agent is dispersed in the amorphous polyester resin, and the content of the synthetic ester wax is not particularly limited, but is 1 to 5 mass in the toner base particles. % Is preferred.

  In the toner of the present invention, a release agent other than the synthetic ester wax may be used within a range not impairing the object of the present invention, and examples thereof include polypropylene wax, polyethylene wax and derivatives thereof, and microcrystalline wax. It is done.

[Colorant]
As the colorant, known pigments and dyes generally used for toners can be used. Specifically, the following colorants can be used.
As a black toner colorant, carbon black, magnetite, or the like can be used.
Examples of the colorant for yellow toner include C.I. I. Pigment Yellow 1, 3, 74, 97, 98, etc. acetoacetic acid arylamide monoazo yellow pigments, C.I. I. Pigment Yellow 12, 13, 13, 14, etc., acetoacetic acid arylamide disazo yellow pigments, C.I. I. Condensed monoazo yellow pigments such as CI Pigment Yellow 93 and 155; I. Other yellow pigments such as C.I. Pigment Yellow 180, 150 and 185, C.I. I. Solvent Yellow 19, 77, 79, C.I. I. A yellow dye such as Disperse Yellow 164 can be used.
Examples of the colorant for magenta toner include C.I. I. Pigment Red 48, 49: 1, 53: 1, 57, 57: 1, 81, 122, 5, 146, 184, 238, C.I. I. Red or red pigments such as CI Pigment Violet 19; I. Red dyes such as Solvent Red 49, 52, 58 and 8 can be used.
Examples of the colorant for cyan toner include C.I. I. Pigment Blue 15: 3, 15: 4, and the like, and blue dyes and pigments of copper phthalocyanine and derivatives thereof; C.I. I. Green pigments such as CI Pigment Green 7 and 36 (phthalocyanine green) can be used.
In the toner of the present invention, the content of the colorant is not particularly limited, but is preferably 2 to 10% by mass in the toner base particles.

[Charge control agent]
The charge control agent is added in order to impart preferable chargeability to the toner. As the charge control agent that can be used in the toner of the present invention, a charge control agent for positive charge control or negative charge control can be used. Examples of the charge control agent for controlling positive charge include nigrosine dyes and derivatives thereof, triphenylmethane derivatives, quaternary ammonium salts, quaternary phosphonium salts, quaternary pyridinium salts, guanidine salts and amidine salts. As the charge control agent for controlling negative charge, chromium azo complex dye, iron azo complex dye, cobalt azo complex dye, salicylic acid or its derivative chromium / zinc / aluminum / boron complex or salt compound, naphtholic acid or its derivative chromium / zinc -Aluminum-boron complex or salt compound, chromium-zinc-aluminum-boron complex or salt compound of benzylic acid or its derivative, long chain alkyl carboxylate, long chain alkyl sulfonate, etc. In the toner of the present invention, the content of the charge control agent is not particularly limited, but is preferably 0.5 to 5% by mass in the toner base particles.

[External additive]
The external additive that can be used in the toner of the present invention is made of silica fine particles having a primary particle diameter of 75 nm to 220 nm that have been subjected to a hydrophobization treatment, from the viewpoint of preventing the image sticking phenomenon that the toner constituents are fused to the surface of the developing roller. It is preferable to include at least. The primary particle size of the silica fine particles refers to the average primary particle size of the silica fine particles after the hydrophobization treatment.

(Large particle size silica particles)
The large particle size silica fine particles that can be used as an external additive in the toner of the present invention are not particularly limited as long as the primary particle size is 75 nm to 220 nm, but may be silica fine particles produced by a sol-gel method. preferable. Since the silica fine particles produced by the sol-gel method have a sharp particle size distribution, a high scraping effect can be obtained. Examples of the method for producing silica fine particles by the sol-gel method include a method described in JP2013-249215A.

(Method for producing silica fine particles by the sol-gel method)
As a method for producing silica fine particles by a sol-gel method, for example, tetraalkoxysilane and an alkali catalyst are supplied in an alcohol solvent containing an alkali catalyst to form silica fine particles, and then a dispersion of the silica fine particles is used as a solvent. The method of removing and crushing is mentioned. As the alcohol solvent, for example, methanol, ethanol or the like can be used, and a mixed solvent to which water, ketone or the like is added can be used as necessary. The alkali catalyst is a catalyst for promoting the hydrolysis reaction and condensation reaction of tetraalkoxysilane, and for example, ammonia, urea or the like can be used. Examples of the tetraalkoxysilane include the following general formula (1) such as tetramethoxysilane and tetraethoxysilane:
Si (OR ₁ ) ₄ (1)
(Wherein, R _{1 s} are the same or different from each other and are alkyl groups having 1 to 4 carbon atoms). Examples of the solvent removal method include filtration, centrifugation, distillation, and the like, and it is preferable to dry the silica fine particles with a vacuum dryer or the like after removing the solvent. As a crushing method, for example, it can be carried out using a dry crushing apparatus such as a jet mill or a vibration mill.

(Hydrophobic treatment)
As a hydrophobizing method, a method in which a hydrophobizing agent is reacted with the surface of silica fine particles can be used. Specifically, silica fine particles are put into a four-necked flask equipped with a stirring member and a thermometer and through which an introduction pipe for introducing an inert gas such as a hydrophobizing agent and nitrogen gas is inserted, and kept at 120 to 350 ° C. The silica fine particles can be hydrophobized by introducing a hydrophobizing agent and an inert gas and reacting for a predetermined time (for example, 2 to 8 hours) while stirring. As the hydrophobizing agent, for example, silane coupling agents such as hexamethyldisilazane, methyltrimethoxysilane, dimethyldimethoxysilane, and trimethylchlorosilane, silicone oil, silicone varnish, and the like can be used, and hexamethyldisilazane is preferable. Moreover, it is preferable that the hydrophobized silica fine particles (hereinafter also referred to as hydrophobic silica fine particles) have a hydrophobicity of 95% or more and 100% or less. Silica fine particles having a hydrophobicity of 95% or more and 100% or less that have been hydrophobized with hexamethyldisilazane are less likely to be attracted to the crystalline polyester resin even if the crystalline polyester resin adheres to the developing roller. It becomes difficult to be fixed to the roller surface. Furthermore, it is preferable that the silica fine particles subjected to the hydrophobic treatment have a loss on drying of 0.8% by mass or less.

  In the toner of the present invention, the addition amount of the hydrophobized large particle size silica particles having a primary particle size of 75 nm to 220 nm is not particularly limited, but is 0.5 to 3 parts by mass with respect to 100 parts by mass of the toner base particles. Is preferred.

(Other external additives)
The external additive that can be used in the toner of the present invention may include an external additive other than the fine silica particles having a primary particle diameter of 75 nm to 220 nm that has been subjected to a hydrophobic treatment (hereinafter also referred to as other external additives). . For example, inorganic fine particles having an average particle diameter of 7 nm to 50 nm can be used for the purpose of imparting fluidity to the toner. Examples of the inorganic fine particles include inorganic fine particles such as silica, titanium oxide, and alumina, and those obtained by subjecting the inorganic fine particles to a surface treatment (hydrophobization treatment) with a silane coupling agent, a titanium coupling agent, or silicone oil. In the toner of the present invention, the amount of other external additives added is not particularly limited, but is preferably 0.8 to 2 parts by mass with respect to 100 parts by mass of toner base particles.

  The toner of the present invention can be used as a one-component developer, but as will be described later, the toner and carrier mixture of the present invention can also be used as a two-component developer.

[Toner production method]
Next, a method for producing the toner of the present invention will be described. The toner of the present invention can be produced by a known method such as a kneading and pulverizing method or an aggregating method. For example, when the toner of the present invention is produced by a kneading and pulverizing method, first, a binder resin containing an amorphous polyester resin and a crystalline polyester resin, a release agent, and a colorant appropriately selected as necessary, Internal additives such as charge control agents are mixed with an air flow mixer such as a Henschel mixer, and the resulting raw material mixture is kneaded at a temperature of about 100 to 180 ° C. with a melt kneader such as a biaxial kneader or an open roll kneader. To do. Then, the obtained melt-kneaded product is cooled and solidified, the solidified product is pulverized by an air pulverizer such as a jet mill, and the toner base particles are produced by adjusting the particle size such as classification as required. As a method for adding the external additive, a method in which the toner base particles and the external additive are mixed with an air flow mixer such as a Henschel mixer is generally used.

[Two-component developer]
The case where the toner of the present invention is used as a two-component developer will be described below. The two-component developer includes the toner of the present invention described above and a carrier. For example, the toner can be obtained using a mixer such as a Nauta mixer (trade name: VL-0, manufactured by Hosokawa Micron Corporation). And a carrier. Further, the mixing ratio of the toner and the carrier is preferably a mass ratio of 10:90 to 5:95, for example.

[Career]
As the carrier, magnetic particles having a volume average particle diameter of 20 to 45 μm can be used. If the volume average particle diameter of the carrier is less than 20 μm, white spots may occur in the resulting image due to the carrier moving from the developing roller to the photoreceptor during development. On the other hand, if it exceeds 45 μm, the dot reproducibility deteriorates and the image becomes rough. In the present invention, the volume average particle diameter of the carrier is determined by using a dry dispersion apparatus RODOS (manufactured by SYMPATEC) and a dispersion pressure of 3.0 bar using a laser diffraction particle size distribution measuring apparatus HELOS (manufactured by SYMPATEC). This is the value when measured.

  Regarding the saturation magnetization of the carrier, the lower the saturation magnetization, the softer the magnetic brush (formed on the surface of the developing roller) in contact with the photoconductor, so that an image faithful to the electrostatic latent image can be obtained, but the saturation magnetization is too low. As a result, carriers adhere to the surface of the photoreceptor, and white spots are likely to occur. On the other hand, if the saturation magnetization is too high, it becomes difficult to obtain an image faithful to the electrostatic latent image due to the stiffening of the magnetic brush. For this reason, it is preferable that the saturation magnetization of a carrier exists in the range of 30-100 emu / g.

  As such a carrier, a coated carrier in which a coating layer is provided on the surface of magnetic core particles is generally used. Known magnetic particles can be used as the core particles, but ferrite particles are preferred. When ferrite particles are used, carriers with high saturation magnetization can be obtained, and the amount of carriers attached to the photoreceptor can be reduced. Known ferrite particles can be used, such as zinc ferrite, nickel ferrite, copper ferrite, nickel-zinc ferrite, manganese-magnesium ferrite, copper-magnesium ferrite, manganese-zinc ferrite, Manganese-copper-zinc ferrite and the like can be mentioned.

These ferrite particles can be produced by a known method. For example, ferrite raw materials such as Fe ₂ O ₃ and Mg (OH) ₂ are mixed, and this mixed powder is heated in a heating furnace and calcined. After the obtained calcined product is cooled, it is pulverized with a vibration mill so as to have particles of approximately 1 μm, and a dispersant and water are added to the pulverized powder to prepare a slurry. The slurry is wet pulverized with a wet ball mill, and the resulting suspension is granulated and dried with a spray dryer to obtain ferrite particles.

  A known resin material can be used as the coating material constituting the coating layer of the carrier, and examples thereof include an acrylic resin and a silicone resin. In particular, a coated carrier coated with a silicone resin, that is, a coated carrier having a silicone resin coating layer is preferable. When a coated carrier having a silicone resin coating layer is used, toner components such as a crystalline polyester resin and a release agent are less likely to adhere to the surface of the carrier, thereby suppressing carrier contamination and excellent charging stability.

  A well-known thing can be used as a silicone resin. Moreover, the silicone resin is marketed, for example with the form of a varnish, and these can be used conveniently. Specific examples include silicone varnish (manufactured by Toshiba Corporation: TSR115, TSR114, TSR102, TSR103, YR3061, TSR110, TSR116, TSR117, TSR108, TSR109, TSR180, TSR181, TSR187, TSR144, TSR165, manufactured by Shin-Etsu Chemical Co., Ltd .: KR271, KR272, KR275, KR280, KR282, KR267, KR269, KR211, KR212), alkyd-modified silicone varnish (manufactured by Toshiba Corporation: TSR184, TSR185), epoxy-modified silicone varnish (manufactured by Toshiba Corporation: TSR194, YS54), polyester Resin-modified silicone varnish (Toshiba Corporation: TSR187), acrylic-modified silicone varnish (Toshiba Corporation: TSR) 70, TSR171), urethane-modified silicone varnish (manufactured by Toshiba Corporation: TSR175), reactive silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd .: KA1008, KBE1003, KBC1003, KBM303, KBM403, KBM503, KBM602, KBM603) and the like. .

  In order to control the volume resistivity value of the carrier, a conductive material is preferably added to the covering material. Examples of the conductive material include silicon oxide, alumina, carbon black, graphite, zinc oxide, titanium black, iron oxide, titanium oxide, tin oxide, potassium titanate, calcium titanate, aluminum borate, magnesium oxide, barium sulfate, Examples thereof include calcium carbonate. Among these conductive materials, carbon black is preferable from the viewpoint of production stability, cost, and low electrical resistance. The type of carbon black is not particularly limited, but a carbon black having a DBP (dibutyl phthalate) oil absorption in the range of 90 to 170 ml / 100 g is preferable in terms of excellent production stability. In addition, particles having a primary particle size of 100 nm or less are particularly preferable because of excellent dispersibility. These conductive materials may be used alone or in combination of two or more. It is preferable that the addition amount of a electrically conductive material is 0.1-20 mass parts with respect to 100 mass parts of coating | covering materials.

  In order to coat the carrier particles with the coating material, a known method can be employed. For example, an immersion method in which carrier particles are immersed in an organic solvent solution of the coating material, a spray method in which the organic solvent solution of the coating material is sprayed on the carrier particles, an organic solvent solution of the coating material in a state where the carrier particles are suspended by flowing air And a kneader coater method in which carrier particles and an organic solvent solution of a coating material are mixed in a kneader coater to remove a solvent such as an organic solvent. Here, the organic solvent solution of the covering material preferably contains a conductive material.

[Physical property measurement method]
Below, the measuring method of each physical-property value regarding this invention is demonstrated.

{Molecular weight of resin}
In the present invention, the molecular weight [peak top molecular weight (Mp) and number average molecular weight (Mn)] of the polyester resin is measured under the following conditions using gel permeation chromatography (GPC). For the measurement of molecular weight, a polyester resin is dissolved in THF, and the insoluble matter is filtered off with a glass filter, and used as a sample solution. The peak top molecular weight refers to a molecular weight showing the maximum peak height in a chromatogram obtained by GPC measurement.
Device (example): HLC-8120 manufactured by Tosoh Corporation
Column (example): TSK GEL GMH6 2 [Tosoh Corp.]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF (tetrahydrofuran) solution Solution injection amount: 100 μl
Detection apparatus: Refractive index detector Reference material: Tosoh standard polystyrene (TSK standard POLYSYRENE) 12 points (molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)

{Acid value and hydroxyl value of resin}
In the present invention, the acid value and hydroxyl value of the polyester resin are values measured by a method defined in JIS K0070 (1992 edition). In addition, when the sample has a solvent-insoluble component accompanying crosslinking, a sample after melt kneading is used as a sample by the following method.
Kneading device: Labo plast mill MODEL4M150 manufactured by Toyo Seiki Co., Ltd.
Kneading conditions: 130 ° C., 70 rpm, 30 minutes

{SP value}
In the present invention, the SP value is calculated by the method described in “POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pp. 147 to 154)” proposed by Fedors et al. Is done.

{Melting point}
Using a differential scanning calorimeter (for example, DSC210, manufactured by Seiko Denshi Kogyo Co., Ltd.), the sample to be measured was heated to 200 ° C. and then cooled to 0 ° C. at a temperature decreasing rate of 10 ° C./min. The temperature is increased at a rate of 1 minute / minute, and the endothermic change is measured. A graph of “endothermic amount” and “temperature” is drawn, and the temperature corresponding to the maximum peak of the endothermic amount is defined as the melting point (Tmp).

{Softening point}
Using a flow tester (trade name: CFT-100C, manufactured by Shimadzu Corporation), a 1 g measurement sample was heated at a heating rate of 6 ° C./min. , Extrude from a nozzle with a length of 1 mm, draw a graph of "plunger descent amount (flow value)" and "temperature", and read the temperature corresponding to 1/2 of the maximum value of plunger descent amount from the graph This value (temperature when half of the measurement sample flows out) is defined as a softening point (Tm).

{Glass-transition temperature}
In accordance with Japanese Industrial Standard (JIS) K7121-1987, a differential scanning calorimeter (trade name: DSC220, manufactured by Seiko Denshi Kogyo Co., Ltd.) was used to heat a 10 mg sample at a heating rate of 10 ° C. per minute to obtain a DSC curve. taking measurement. Draw the endothermic peak corresponding to the glass transition of the obtained DSC curve at a point where the slope is maximum with respect to the straight line that extends the base line on the high temperature side to the low temperature side and the curve from the rising part of the peak to the vertex. The temperature at the intersection with the tangent is defined as the glass transition temperature (Tg).

{Volume average particle diameter of toner}
To 50 ml of electrolyte (trade name: ISOTON-II, manufactured by Beckman Coulter, Inc.), 20 mg of toner particles and 1 ml of sodium alkyl ether sulfate are added, and an ultrasonic disperser (trade name: UH-50, manufactured by SMT Corporation). Was used for dispersion treatment at an ultrasonic frequency of 20 kHz for 3 minutes to prepare a measurement sample. The sample for measurement is measured using a particle size distribution measuring device (trade name: Coulter Multisizer II, manufactured by Beckman Coulter, Inc.) under the conditions of an aperture diameter of 100 μm and the number of measured particles of 50000 counts. The volume average particle diameter of the toner was determined from the particle size distribution.

{Hydroxyl value in wax}
The hydroxyl value is a value defined as the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated, according to JIS K 0070 (1992). Measured.
Specifically, sample Xg (about 1 g) is precisely weighed in a flask, and 20 ml of an acetylating reagent (a solution obtained by adding pyridine to 20 ml of acetic anhydride to 400 ml) is accurately added thereto. An air cooling tube is attached to the mouth of the flask and heated in a glycerin bath at 95-100 ° C. After 1 hour and 30 minutes, the mixture is cooled, 1 ml of purified water is added from an air condenser, and acetic anhydride is decomposed into acetic acid.
Next, titration is performed with a 0.5 mol / L potassium hydroxide ethanol solution using a potentiometric titrator, and the inflection point of the obtained titration curve is set as the end point.
Further, as a blank test, titration is performed without a sample, and an inflection point of the titration curve is obtained.
The hydroxyl value is calculated by the following formula.
Hydroxyl value = {(BC) × f × 28.05 / X} + D
In the formula, B is the amount (ml) of 0.5 mol / L potassium hydroxide ethanol solution used for the blank test, C is the amount (ml) of 0.5 mol / L potassium hydroxide ethanol solution used for titration, f is a factor of 0.5 mol / L potassium hydroxide ethanol solution, X is the mass (g) of the sample, D is an acid value, and 28.05 is 1/2 of 1 mol amount of potassium hydroxide 56.11 .

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

(Preparation of amorphous polyester resin PA1)
In the reaction tank, 440 g (2.7 mol) of terephthalic acid, 235 g (1.4 mol) of isophthalic acid, 7 g (0.05 mol) of adipic acid, 554 g (8.9 mol) of ethylene glycol, and tetrabutoxy as a polymerization catalyst. After adding 0.5 g of titanate and reacting for 5 hours while distilling off the water and ethylene glycol produced at 210 ° C. under a nitrogen stream, the reaction was carried out for 1 hour under reduced pressure of 5 to 20 mmHg. Next, 103 g (0.54 mol) of trimellitic anhydride was added and reacted for 1 hour under normal pressure, then reacted under reduced pressure of 20 to 40 mmHg, and the resin was taken out at a predetermined softening point. The recovered ethylene glycol was 219 g (3.5 mol). The obtained resin was cooled to room temperature and then pulverized into particles. This was designated as amorphous polyester resin PA1. Amorphous polyester resin PA1 had a Tg of 63 ° C., a Tm of 115 ° C., an Mp of 4800, an acid value of 22 mgKOH / g, and a hydroxyl value of 35 mgKOH / g.

(Preparation of amorphous polyester resin PA2)
In the reaction vessel, terephthalic acid 310 g (1.9 mol), isophthalic acid 465 g (2.8 mol), adipic acid 36 g (0.25 mol), ethylene glycol 610 g (9.8 mol), tetrabutoxy as a polymerization catalyst. After adding 0.5 g of titanate and reacting for 5 hours while distilling off the water and ethylene glycol produced at 210 ° C. under a nitrogen stream, the reaction was carried out for 1 hour under reduced pressure of 5 to 20 mmHg. Next, 52 g (0.27 mol) of trimellitic anhydride was added and reacted under normal pressure for 1 hour, and then reacted under reduced pressure of 20 to 40 mmHg to take out the resin at a predetermined softening point. The recovered ethylene glycol was 262 g (4.2 mol). The obtained resin was cooled to room temperature and then pulverized into particles. This was designated as amorphous polyester resin PA2. Amorphous polyester resin PA2 had a Tg of 60 ° C., a Tm of 140 ° C., an Mp of 10500, an acid value of 10 mgKOH / g, and a hydroxyl value of 0 mgKOH / g.

(Preparation of crystalline polyester resin PC1)
In a reaction vessel, 132 g (1.12 mol) of 1,6-hexanediol, 230 g (1.0 mol) of 1,10-decanedicarboxylic acid, and 3 g of tetrabutoxy titanate as a polymerization catalyst were added at 210 ° C. under normal pressure. The reaction was carried out for 5 hours while distilling off the water produced. Subsequently, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and the resin was taken out when the acid value became 2 mgKOH / g or less. The obtained resin was cooled to room temperature and then pulverized into particles. This was designated as crystalline polyester resin PC1. The crystalline polyester resin PC1 had a Tmp of 66 ° C., a Tm of 73 ° C. (Tm / Tmp = 1.1), and an Mp of 13500.

(Preparation of crystalline polyester resin PC2)
In a reactor, 132 g (1.12 mol) of 1,6-hexanediol, 343 g (1.0 mol) of 1,18-octadecanedicarboxylic acid, and 3 g of tetrabutoxy titanate as a polymerization catalyst were added at 210 ° C. under normal pressure. The reaction was carried out for 5 hours while distilling off the water produced. Subsequently, the reaction was continued under a reduced pressure of 5 to 20 mmHg, and the resin was taken out when the acid value became 2 mgKOH / g or less. The obtained resin was cooled to room temperature and then pulverized into particles. This was designated as crystalline polyester resin PC2. Crystalline polyester resin PC2 had Tmp of 68 ° C., Tm of 95 ° C. (Tm / Tmp = 1.4), and Mp of 20000.

[Example 1]
(Preparation of Toner T1)
Amorphous polyester resin PA1 80 parts by weight Crystalline polyester resin PC1 20 parts by weight Synthetic ester wax (WEP-5, NOF Corporation, pentaerythritol tetrabehenate (tetraester compound), hydroxyl value 1.5 mgKOH / g) 5 parts by mass Carbon black (MA-100, manufactured by Mitsubishi Chemical Co., Ltd.) 7 parts by mass Charge control agent (Bontron E84, manufactured by Orient Chemical Co., Ltd.) 1 part by mass The above toner raw material was mixed with a Henschel mixer (FM20C, manufactured by Nippon Coke) for 5 minutes. After stirring and mixing, the obtained stirring mixture was melt-kneaded with an open roll type continuous kneader (MOS320-1800, manufactured by Mitsui Mining Co., Ltd.).
The obtained melt-kneaded product is cooled by a cooling belt, then coarsely pulverized using a speed mill having a φ2 mm screen, and then using a jet type pulverizer (IDS-2, manufactured by Nippon Pneumatic Industry Co., Ltd.). Finely pulverized and further classified using an elbow jet classifier (manufactured by Nippon Steel & Mining Co., Ltd., model: EJ-LABO) to obtain toner base particles having a volume average particle diameter of 6.5 μm.
Next, to 100 parts by mass of the obtained toner base particles, 0.7 parts by mass of silica particles having an average primary particle diameter of 16 nm hydrophobized with a silane coupling agent as an external additive (R972 manufactured by Nippon Aerosil Co., Ltd.) And an air flow mixer (Mitsui Mining Co., Ltd., Henschel mixer) in which 1 part by mass of titanium oxide having an average primary particle size of 30 to 40 nm (ST550 manufactured by Titanium Industry Co., Ltd.) was set at a tip speed of a stirring blade of 15 m / sec. The toner T1 of Example 1 having a volume average particle size of 6.5 μm was prepared by stirring for 2 minutes.

[Examples 2 to 5 and Comparative Examples 1 to 2]
(Preparation of toners T2 to T7)
Examples 2 to 5 and Comparative Examples 1 to 2 having a volume average particle diameter of 6.5 μm were prepared in the same manner as in the preparation of the toner T1, except that the type of the toner raw material was changed to that shown in Table 1. Toners T2-5 and T6-7 were prepared.

WEP3: Synthetic ester wax, manufactured by NOF Corporation, behenyl behenate (monoester compound), hydroxyl value 2.5 mgKOH / g
WEP7: Synthetic ester wax, manufactured by NOF Corporation, hexaglycerin octabehenate (polymer ester compound), hydroxyl value 8.0 mgKOH / g
Carnauba wax: hydroxyl value 12.8 mgKOH / g

(Preparation of carrier)
Ferrite particles (volume average particle size 45 μm) 100 parts by mass Toluene 15 parts by mass Silicone resin (number average molecular weight: about 15000) 2 parts by mass Carbon black (primary particle size 25 nm, oil absorption 150 ml / 100 g) 0.15 parts by mass Octyl acid 0.1 parts by mass The above materials excluding ferrite particles were stirred with a stirrer for 10 minutes to prepare a dispersed coating solution, and the coating solution and ferrite particles were placed in a vacuum degassing kneader at 60 ° C. After stirring for 25 minutes, the mixture was further depressurized while being heated, degassed, and dried, so that the volume average particle size was 45 μm, the coverage of the silicone resin was 100%, the volume resistivity was 2 × 10 ¹¹ Ω · cm, A carrier having a saturation magnetization of 65 emu / g was produced.

(Preparation of two-component developer D1)
The toner T1 (A) and the carrier (B) are charged into a Nauter mixer (trade name: VL-0, manufactured by Hosokawa Micron Corporation) at a mass ratio (A: B) of 6:94 and stirred and mixed for 20 minutes. Thus, a two-component developer D1 of Example 1 was produced.

(Preparation of two-component developers D2 to D7)
The two-component developers D2 of Examples 2 to 5 and Comparative Examples 1 to 2 were prepared in the same manner as the preparation of the two-component developer D1 except that the toners T2 to T7 were used instead of the toner T1. 5 and D6-7 were prepared.

(Evaluation)
Low-temperature fixability of the produced toners T1 to T5 and T6 to 7 and two-component developers D1 to 5 and D6 to 7 of Examples 1 to 5 and Comparative Examples 1 to 2 according to the evaluation method described below. The filming phenomenon and blocking resistance were evaluated. The evaluation results are shown in Table 2.

(Evaluation method for low-temperature fixability)
The produced two-component developer and toner are filled in a developing device and a toner cartridge of a color composite machine (trade name: MX-2640, manufactured by Sharp Corporation), respectively, and the fixing roller temperature in the fixing device is 150 ° C. ± 1 ° C. And an image sample for fixing strength measurement was prepared in an environment with an air temperature of 20 ° C. and a humidity of 60%.
As an image sample for fixing strength measurement, a document including a solid image portion (image density ID = 1.5) having a side of 3 cm is copied onto a recording paper (trade name: PPC paper SF-4AM3, manufactured by Sharp Corporation). Created by.
The solid image portion of the image sample was folded inward, and in the folded state, an 850 g roller was rolled back and forth on the fold line at a constant pressure to produce a peel sample in which the toner image was peeled off at the folded portion.
The peeled sample was spread out and the peeled toner was blown off with an air brush, and the peel width (maximum white line width that can be formed in the bent portion) was measured as an index of fixing strength.
Evaluation criteria for low-temperature fixability are as follows.
○: Good. Peel width is less than 0.3 mm.
Δ: Slightly poor Peel width is 0.3 mm or more and less than 0.5 mm.
X: Defect. Peel width is 0.5mm or more.

(Filming phenomenon evaluation method)
The produced two-component developer and toner are filled in a developing device and a toner cartridge of a color composite machine (trade name: MX-2640, manufactured by Sharp Corporation), respectively, and the central portion and both end portions in the axial direction of the developing roller are filled. A continuous print test of 50000 sheets was performed so that a square solid image (ID = 1.45 to 1.50) having a side of 1 cm was formed at three positions. Thereafter, a solid image (ID 1.6 to 1.8) was output on A3 paper, and the image was visually determined.
The evaluation criteria for the filming phenomenon are as follows.
○: Good. There is no roughness in the output solid image, and there is no toner fusion on the surface of the photoreceptor.
Δ: Slightly poor Although the output solid image is not rough, there is toner fusion on the surface of the photoreceptor.
X: Defect. Roughness can be confirmed in the output solid image, and toner is fused on the surface of the photoreceptor.

(Evaluation method for blocking resistance)
The produced two-component developer and toner were filled in a commercially available copying machine (trade name: MX-5111FN, manufactured by Sharp Corporation), and adjusted so that the image was not developed on the photoconductor. Only the developing machine was continuously operated for 2 hours below, and it was confirmed whether the two-component developer was biased and aggregates were generated.
The evaluation criteria for blocking resistance are as follows.
A: Very good. There is no bias of two-component developer.
○: Good. Although there is a slight bias in the two-component developer, there is no generation of aggregates.
X: Defect. There is agglomeration.

Claims (3)

In a toner including a binder resin including an amorphous polyester resin and a crystalline polyester resin, and a release agent,
The amorphous polyester resin is an amorphous polyester resin obtained by polycondensing a dicarboxylic acid monomer containing terephthalic acid or isophthalic acid as a main component and a diol monomer containing ethylene glycol as a main component,
The crystalline polyester resin is obtained by polycondensing a dicarboxylic acid monomer mainly containing an aliphatic dicarboxylic acid having 9 to 22 carbon atoms and a diol monomer mainly containing an aliphatic diol having 2 to 10 carbon atoms. A crystalline polyester resin,
A toner, wherein the release agent is a synthetic ester wax having a hydroxyl value of less than 5 mgKOH / g.   The toner according to claim 1, wherein the synthetic ester wax contains a monoester compound.   A two-component developer comprising the toner according to claim 1 and a carrier.