JP6545037B2 - TONER AND METHOD FOR MANUFACTURING TONER - Google Patents

Description

  The present invention relates to a toner for developing an electrostatic charge image used for image formation of an electrophotographic system represented by a copying machine or a printer, and a method for producing the toner.

In recent years, in printers and the like, there are increasing demands for energy saving due to high-speed printing, improvement in the quality of printed images, and a decrease in fixing temperature. Therefore, it is important to reduce the particle size of the electrostatic image developing toner (hereinafter sometimes referred to as toner), control its shape, and melt it at a lower temperature, and improvement has been attempted. Further, the low temperature fixability, the heat resistant storage stability and the developability are usually in a trade-off relationship, and it is desired to achieve both.
In order to achieve high image quality by achieving a smaller particle size of the toner and a narrower particle size distribution for these problems, polymerization produced by a polymerization method such as a suspension polymerization method, an emulsion polymerization aggregation method, a dissolution suspension method, etc. Toner research and development is actively conducted. The polymerized toner is easier to reduce in particle size than a pulverized toner, and a sharp particle size distribution can be easily obtained. Furthermore, since it is possible to form a capsule structure (core / shell structure) of toner particles, there is also an advantage that a toner having low temperature fixability, heat resistant storage stability, and developability can be obtained.
As toner particles by these polymerization methods, a crystalline polyester resin having sharp melt properties advantageous for low temperature fixability is added to the inside of the toner particles, and the outside of the toner is non-crystalline excellent in heat resistance storage stability, stress resistance, etc. Toners having a so-called core / shell structure covered with a polyester resin have been proposed. (Patent Document 1, Patent Document 2)

JP, 2002-182428, A JP 2005-234046 A Japanese Patent Application Publication No. 2005-308995

In the case of toner by the suspension polymerization method, the addition of a crystalline polyester resin is effective for improving low temperature fixability, but the crystalline polyester resin is partially compatible with the amorphous polyester resin forming the shell layer. Or exposed to the toner surface. When the crystalline polyester resin is compatible with the amorphous polyester resin forming the shell layer, the glass transition temperature of the shell portion is lowered, so the developability such as heat resistance storage stability and stress resistance tends to be insufficient. . In addition, when the crystalline polyester resin is exposed on the toner surface, it may be attached to the member of the developing device, which may cause an image adverse effect. In addition, since the crystalline polyester resin has low electric resistance, the chargeability of the toner may be lowered.
It has been reported that these problems can be improved by performing the heat treatment step, but a very long time of treatment is required and the problems can not be solved sufficiently. (Patent Document 3)
From the above reasons, it is a reality that toners having sufficiently low temperature fixability, heat resistant storage stability and developability are desired.

  An object of the present invention is to provide a toner which is manufactured by a suspension polymerization method and to which a crystalline polyester resin is added, and in which the low temperature fixability, the heat resistant storage stability and the developability are sufficiently compatible. Furthermore, it is an object of the present invention to provide a toner capable of stably obtaining high definition and high image quality over a long period of time without exhibiting any adverse effect on the production stability of the toner.

The above object is solved by the following invention.
A toner having toner particles of a core-shell structure in which a shell phase containing an amorphous polyester resin A is formed on a core containing a resin containing a vinyl polymer and a crystalline polyester resin B ,
Relative to the vinyl polymer 100.0 parts by mass, the content of the non-crystalline polyester resin A is 40.0 mass parts or less than 1.0 part by weight,
The content of the crystalline polyester resin B is 1.0 parts by mass or more and 50.0 parts by mass or less with respect to 100.0 parts by mass of the vinyl polymer.
The amorphous polyester resin A contains isosorbide unit represented by the formula (1) in an amount of 0.1 mol% or more and 30.0 mol% or less based on all monomer units constituting the amorphous polyester resin A,

The crystalline polyester resin B is produced from a monomer containing an aliphatic dicarboxylic acid represented by the following formula (2) and an aliphatic diol represented by the following formula (3):
HOOC- _{(CH 2)} m -COOH Formula (2)
[Wherein, m represents an integer of 4 or more and 14 or less]
HO- (CH ₂ ) _n -OH Formula (3)
[Wherein, n represents an integer of 4 or more and 16 or less]
The present invention relates to a toner characterized in that the degree of compatibility of the crystalline polyester resin B with the amorphous polyester resin A is 60% or less.

  The toner of the present invention is produced by a suspension polymerization method, and when a crystalline polyester resin is added, a toner in which low temperature fixability, heat resistant storage stability and developability are sufficiently compatible can be obtained. Furthermore, it is possible to obtain a toner capable of stably obtaining high definition and high image quality over a long period of time without exhibiting any adverse effect on production stability of the toner.

The present invention relates to a toner which is produced by a suspension polymerization method and to which a crystalline polyester resin is added for the purpose of imparting low temperature fixability, low temperature fixability, heat resistance storage stability and developability, which are usually contradictory. We carefully studied about the coexistence of
As a result, it has been found that, in the crystalline polyester resin and the non-crystalline polyester resin forming the shell, by using the structure and physical properties described in detail below, it is possible to obtain a toner that solves the above-mentioned problems.

The toner of the present invention is a non-crystalline polyester resin in a resin containing a vinyl polymer (preferably a vinyl copolymer) and a crystalline polyester resin B, and a core optionally containing a coloring agent and a wax. A toner having toner particles of a core-shell structure in which a shell layer containing A is formed,
The toner particles are polymerizable including the amorphous polyester resin A, the crystalline polyester resin B, a polymerizable monomer for forming the vinyl polymer, and a colorant and a wax optionally added. It is produced by forming particles of the monomer composition in an aqueous medium and polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition (suspension polymerization method).
In the suspension polymerization method, a polar resin is added to the polymerizable monomer composition to produce toner particles, and a core is formed mainly from the resin and, if necessary, the colorant and the wax added. Toner particles having a core-shell structure coated with a shell layer formed of a polar resin can be obtained.

In the present invention, an amorphous polyester resin A described in detail below is added as a polar resin for forming a shell layer.
The amorphous polyester resin A of the present invention contains the isosorbide unit represented by the formula (1) in an amount of 0.1 mol% or more and 30.0 mol% or less based on all monomer units constituting the amorphous polyester resin A. Preferably, the content is 0.3 mol% or more and 20.0 mol% or less. In addition, a "monomer unit" means the form which the monomer substance in a polymer reacted.

Further, the degree of compatibility of the crystalline polyester resin B with respect to the amorphous polyester resin A is 60% or less, preferably 40% or less. The lower limit of the degree of compatibility is preferably 0% or more. The method of measuring the degree of compatibility will be described later.
The degree of compatibility can be controlled by the amount of isosorbide unit of the amorphous polyester resin A, the acid value, and the like.
When the degree of compatibility is within the above range, the crystalline polyester is not compatible with the amorphous polyester forming the shell layer or exposed to the toner surface. Therefore, even if a large amount of crystalline polyester resin is added to improve the low temperature fixability, the heat resistant storage stability and the developability are hardly deteriorated.

  The isosorbide unit has a very high polarity because it is a cyclic structure having an ether group in the molecule. Therefore, when the content of the isosorbide unit of the amorphous polyester resin A is more than 30.0 mol%, the solubility in the polymerizable monomer is reduced, the formation of the shell becomes unstable, and the heat resistant storage stability and stress resistance When the ink is used for a long time, developability such as fog and image density stability may be deteriorated.

If the amount is less than 0.1 mol%, the difference in polarity with the crystalline polyester resin will be small, and part of the crystalline polyester will be compatible with the amorphous polyester forming the shell layer, or exposed to the toner surface There are times when When the crystalline polyester is compatible with the non-crystalline polyester forming the shell layer, the glass transition temperature of the shell portion is lowered, so that the heat resistance storage stability and the developability tend to be insufficient. In addition, if the crystalline polyester is exposed, the crystalline polyester may be attached to a member of the developing device, which may cause image defects. Further, in general, crystalline polyester has a low electrical resistance, which may lower the chargeability of the toner.
If the amount of isosorbide unit and the degree of compatibility are in the above ranges, the heat resistance storage stability and the developability are less likely to decrease even if a large amount of crystalline polyester B described later is added to improve the low temperature fixability.

The content of the non-crystalline polyester resin A of the present invention is 1.0 parts by mass or more and 40.0 parts by mass or less, preferably 1.5 parts by mass with respect to 100.0 parts by mass of the vinyl polymer forming the core. More than mass part and 10.0 mass parts or less.
Within the above range, even if the crystalline polyester resin B is added for the purpose of imparting low temperature fixability, a good toner can be obtained without deterioration in heat resistance storage stability and developability.
When the amount of the amorphous polyester resin A is less than 1.0 parts by mass, the shell layer is in the range of the above-described isosorbide monomer content or even when the degree of compatibility with the crystalline polyester resin B is in the specified range. As a result, the crystalline polyester resin B is exposed on the toner surface, and the heat resistant storage stability and the developability are reduced.
When the amount of the amorphous polyester resin A is more than 40.0 parts by mass, it becomes difficult to dissolve in the polymerizable monomer, the formation of the shell becomes unstable, the heat resistance storage stability, the stress resistance and the like are deteriorated, The developability may be deteriorated, such as the occurrence of fogging at the time of image formation and the deterioration of the image density stability.

The non-crystalline polyester resin A of the present invention uses isosorbide as the alcohol component, but the following can also be used in combination as the other alcohol component.
Examples of the dihydric alcohol component include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl). ) Propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4) Alkylene oxide adducts of bisphenol A such as -hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene Glycol, 1,3-propylene glycol, 1,4-butanediol, neope Fats like chill glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol Group diols; bisphenol A such as bisphenol A and hydrogenated bisphenol A.
Examples of trihydric or higher alcohol components include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, and 1,2,4-butanetriol. 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene It can be mentioned.

Moreover, as an acid component used in order to form amorphous polyester resin A, the following are mentioned. For example, aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and pyromellitic acid; carbons such as fumaric acid, maleic acid, adipic acid, succinic acid, and dodecenyl succinic acid, octenyl succinic acid Aliphatic polyvalent carboxylic acids such as succinic acid substituted with alkyl groups of 1 to 20 or alkenyl groups of 2 to 20 carbons; anhydrides of those acids and alkyls of those acids (1 to 8 carbon atoms) Ester is mentioned.
Among them, preferred is non-crystalline polyester resin A obtained by condensation polymerization of a bisphenol derivative as an alcohol component and a divalent or higher carboxylic acid or its acid anhydride or its lower alkyl ester as an acid component. It can be used.

The acid value of the amorphous polyester resin A is preferably 0.5 mg KOH / g or more and 25.0 mg KOH / g or less, and more preferably 0.5 mg KOH / g or more and 15.0 mg KOH / g or less.
When the acid value of the amorphous polyester resin A is 0.5 mg KOH / g or more, the compatibility with the vinyl polymer forming the core is not too good, so that the formation of the shell layer becomes good, and the heat resistance storage stability, The developability is improved.
In addition, when the acid value of the amorphous polyester resin A is in the above range, the particle size distribution at the time of producing the toner particles by the suspension polymerization method becomes good, and the developability becomes good.
The acid value of the amorphous polyester resin A can be controlled by the monomer composition ratio at the time of polymerization.

The weight average molecular weight (Mw) of the amorphous polyester resin A is preferably 5,000 or more and 30,000 or less, and more preferably 7,000 or more and 20,000 or less.
Within the above range, both low temperature fixability, heat resistant storage stability, and developability become better.
When the weight average molecular weight (Mw) is 5,000 or more, the strength of the shell layer becomes high, and the developability becomes good.
When the weight average molecular weight (Mw) is 30,000 or less, the low temperature fixability is improved.

In the present invention, conventionally known polyester resins may be used in combination with the vinyl polymer, the amorphous polyester resin A and the crystalline polyester B.
The crystalline polyester resin B is added to the toner of the present invention. The addition of the crystalline polyester resin B is preferable from the viewpoint of low-temperature fixability.
In the present embodiment, “crystalline” means having a clear endothermic peak (having a melting point Tm (C)) in measurement of differential scanning calorimetry (DSC) described later. On the other hand, a resin in which no clear endothermic peak is observed means that it is amorphous.
The melting point Tm (C) of the crystalline polyester resin B used in the present invention is preferably 55 ° C. or more and 90 ° C. or less, and more preferably 60 ° C. or more and 85 ° C. or less. When the temperature is 55 ° C. or higher, the heat-resistant storage stability of the toner becomes good. On the other hand, when the melting point is 90 ° C. or less, the low temperature fixability is good.

The crystalline polyester resin B of the present invention is produced by the polycondensation of an aliphatic dicarboxylic acid and an aliphatic diol.
Tm (C) can be adjusted by the kind of aliphatic dicarboxylic acid and aliphatic diol to be used, the degree of polymerization, and the like.
The crystalline polyester resin B used in the present invention is produced from a monomer containing a linear aliphatic dicarboxylic acid represented by the following formula (2) and a linear aliphatic diol represented by the following formula (3) Ru.
HOOC- _{(CH 2)} m -COOH Formula (2)
[Wherein, m represents an integer of 4 or more and 14 or less (preferably 6 or more and 12 or less)]
HO- (CH ₂ ) _n -OH Formula (3)
[Wherein, n represents an integer of 4 or more and 16 or less (preferably 6 or more and 14 or less)]

The crystalline polyester resin B may have an aliphatic dicarboxylic acid other than the linear aliphatic dicarboxylic acid represented by the formula (2). Examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, glutaconic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, isophthalic acid, terephthalic acid, n-dodecyl succinic acid, n -Dodecenylsuccinic acid, cyclohexanedicarboxylic acid, anhydrides or lower alkyl esters of these acids, etc. may be mentioned.
In the present invention, trivalent or higher polyvalent carboxylic acids may be used in addition to the above components.
Examples of trivalent or higher polyvalent carboxylic acid components include trimellitic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid, 1,2,4-butanetricarboxylic acid, Examples thereof include 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, and derivatives thereof such as acid anhydrides or lower alkyl esters thereof.
These may be used alone or in combination of two or more.

The crystalline polyester resin B may have an aliphatic diol other than the linear aliphatic diol represented by the formula (3). Specific examples of aliphatic diols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, trimethylene glycol, neopentyl glycol, 4-butadiene glycol and the like.
In the present invention, the alcohol monomer as described above is used as the main component, but in addition to the above components, polyoxyethylenated bisphenol A, polyoxypropyleneated bisphenol A, 1,4-cyclohexanedimethanol, etc. Dihydric alcohols, aromatic alcohols such as 1,3,5-trihydroxymethylbenzene, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol It is also possible to use trihydric alcohols such as glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane and the like.
Examples of trihydric or higher alcohols include glycerin, trimethylol ethane, trimethylol propane, pentaerythritol and the like.
These may be used alone or in combination of two or more.

From the viewpoint of crystallinity of the crystalline polyester resin B, the content of the linear aliphatic dicarboxylic acid represented by the formula (2) in the acid component is preferably 80 mol% or more and 100 mol% or less, and 90 mol% The content is more preferably 100 mol% or less and still more preferably 100 mol%.
From the viewpoint of crystallinity of the crystalline polyester resin B, the content of the linear aliphatic diol represented by the formula (3) in the alcohol component is preferably 80 mol% or more and 100 mol% or less, and 90 mol% or more It is more preferably 100 mol% or less, and still more preferably 100 mol%.
When the linear type is used, the crystallinity of the polyester resin is excellent, and the crystalline melting point is appropriate, so that the heat-resistant storage stability and low-temperature fixability of the toner are excellent. Moreover, since melting | fusing point (Tm) is appropriate as m in said Formula (2) and n in said Formula (3) are 4 or more, it is excellent in heat-resistant storage property and low temperature fixability. In addition, when m in the formula (2) is 14 or less and n in the formula (3) is 16 or less, it is easy to obtain practical materials.
If necessary, a monovalent acid such as acetic acid or benzoic acid or a monohydric alcohol such as cyclohexanol benzyl alcohol may also be used for the purpose of adjusting the acid value or hydroxyl value.

The crystalline polyester resin B is more preferably a saturated polyester. Compared with the case where the crystalline polyester resin B has an unsaturated portion, the crosslinking reaction does not occur in the reaction with the peroxide-based polymerization initiator, which is advantageous in terms of the solubility of the crystalline polyester resin B. is there.
The crystalline polyester resin B used in the present invention can be produced by a conventional polyester synthesis method. For example, it can be obtained by esterification reaction or transesterification reaction of a dicarboxylic acid component and a diol component, followed by polycondensation reaction according to a conventional method under reduced pressure or by introducing nitrogen gas.
At the time of esterification or transesterification, conventional esterification catalysts or transesterification catalysts such as sulfuric acid, tertiary butyltitanium butoxide, dibutyltin oxide, manganese acetate, magnesium acetate and the like can be used, if necessary. With regard to polymerization, conventional polymerization catalysts, for example, known ones such as tertiary butyl titanium butoxide, dibutyl tin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide and germanium dioxide may be used. it can. The polymerization temperature and the catalyst amount are not particularly limited, and may be arbitrarily selected as necessary.

It is desirable to use a titanium catalyst as the catalyst, and it is more desirable to use a chelate type titanium catalyst. This is because the reactivity of the titanium catalyst is appropriate and a polyester having a desired molecular weight distribution can be obtained in the present invention. In addition, the crystalline polyester resin produced by using a titanium catalyst is superior in terms of the chargeability of the toner, that is, the titanium or titanium catalyst incorporated into the polyester during production.
The effect of these catalysts is large when it is a chelate type titanium catalyst, and the product of hydrolysis of the catalyst during the reaction is incorporated into the polyester, whereby the hydrogen abstraction reaction from the peroxide polymerization initiator can be appropriately made. Desirable to control. Furthermore, the durability of the toner is also improved.

  Moreover, the acid value of crystalline polyester resin can also be controlled by sealing the carboxy group of a polymer terminal. A monocarboxylic acid or monoalcohol can be used for end capping. Examples of monocarboxylic acids include benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, dodecanoic acid, Monocarboxylic acids such as stearic acid can be mentioned. Also, as monoalcohols, methanol, ethanol, propanol, isopropanol, butanol and higher alcohols can be used.

In addition, crystalline polyester resin B is a crystalline polyester resin copolymerized (modified) in the proportion of 0% by mass or more and 60% by mass or less (preferably 30% by mass or less) with respect to the crystalline polyester resin portion. (Hybrid crystalline polyester resin) may be used.
Since one of the resins forming the core of the toner of the present invention is a vinyl polymer, when the crystalline polyester resin B has a polymer moiety obtained by polymerizing other components, the polymer moiety is an amorphous vinyl polymer It is preferable that it is a combination (amorphous vinyl site).
When the polymer portion is an amorphous vinyl polymer, the compatibility of the crystalline polyester resin B with the vinyl polymer is improved, and the crystalline polyester resin B is more finely dispersed in the toner than before. It becomes possible. This makes it possible to obtain excellent low temperature fixability and stable developability over a long period of time.
Furthermore, when the crystalline polyester resin B is melted in the fixing step, it can be instantaneously compatible with the resin forming the core which is the same vinyl polymer, and the vinyl polymer can be sufficiently plasticized. . Therefore, the low temperature fixability can be further improved.

When the mass ratio of the amorphous vinyl moiety in the crystalline polyester resin B is 60% by mass or less, the compatibility between the crystalline polyester resin B and the vinyl polymer does not excessively progress, and the heat-resistant storage stability of the toner is improved. It does not cause it to decline. In addition, the degree of crystallinity of the crystalline polyester resin B is not excessively lowered, and sufficient sharp melt properties in the fixing step can be exhibited.
Moreover, in crystalline polyester resin B of this invention, in order to raise compatibility with a vinyl polymer, it is also preferable to adjust the ester group density | concentration of crystalline polyester resin B. That is, by increasing the ester group concentration of the crystalline polyester resin B, the compatibility with the vinyl polymer can be enhanced, and the same effect as the above-mentioned effect of the amorphous vinyl moiety can be obtained.
Since the Tm (C) of the crystalline polyester resin B may be lowered by increasing the ester group concentration, it is preferable to adjust the ester group concentration while considering the glass transition temperature (Tg).

The crystalline polyester resin B preferably has a weight average molecular weight (Mw) of 6000 to 80000, and more preferably 8000 to 40000. When the Mw is in the above range, it is possible to obtain the plastic effect of the crystalline polyester resin B rapidly in the fixing step while maintaining the crystallinity degree of the crystalline polyester resin B high in the toner production process. Therefore, it is possible to achieve both excellent heat resistant storage stability and excellent fixability under low temperature conditions and high speed conditions.
The weight average molecular weight (Mw) of the crystalline polyester resin B can be controlled by various production conditions of the crystalline polyester resin. The method for measuring the weight average molecular weight (Mw) of the crystalline polyester resin B will be described later.

  Moreover, when crystalline polyester resin B has an amorphous vinyl site | part, it is preferable that the weight average molecular weight (Mw) of an amorphous vinyl site | part is 2000-12000. When the weight average molecular weight (Mw) is 2,000 or more and 12,000 or less, the non-crystalline vinyl portion is more uniformly dispersed in the crystalline polyester resin. As a result, the compatibility between the crystalline polyester resin and the vinyl polymer is further improved, and the low temperature fixability is improved. The weight average molecular weight (Mw) of the non-crystalline vinyl moiety can be controlled by various production conditions of the polyester, such as the addition amount of the bireactive monomer at the time of producing the crystalline polyester resin. In addition, the measuring method of the weight average molecular weight (Mw) of an amorphous vinyl site | part is mentioned later.

The acid value of the crystalline polyester resin B used in the present invention is preferably 0.1 mg KOH / g or more and 5.0 mg KOH / g or less, and 0.2 mg KOH / g or more and 4.2 mg KOH / g or less. Is more preferred.
When the acid value of the crystalline polyester resin B used in the present invention is 5.0 mg KOH / g or less, the distribution of the crystalline polyester resin in the vinyl polymer is less likely to be biased, and the crystalline polyester resin is A moderate dispersion of is obtained. Therefore, the desired plasticizing effect on the vinyl polymer can be obtained, and excellent low temperature fixing performance can be satisfied. Moreover, the crystallinity degree of crystalline polyester resin B can be raised, and heat resistant storage stability improves.
In addition, when the toner particles are produced by the suspension polymerization method by lowering the acid value, aggregation of toner particles tends to be less likely to occur, which is desirable because charge stability and stress resistance are improved.
The acid value of the crystalline polyester resin B can be controlled by the ratio of the alcohol component to the acid component constituting the crystalline polyester resin B, the type of monomer, and the end group treatment of the crystalline polyester resin B. The method for measuring the acid value of the crystalline polyester resin B will be described later.

The content of the crystalline polyester resin B is 1.0 part by mass or more and 50.0 parts by mass or less, and 3.0 parts by mass or more and 30 parts by mass or less with respect to 100.0 parts by mass of the vinyl polymer forming the core. It is preferable that it is 0 mass part or less.
When the content of the crystalline polyester resin B is 1.0 parts by mass or more, the low-temperature fixability is more favorable and desirable. Further, since the crystalline polyester resin generally has low electric resistance, if it is added in an amount of more than 50 parts by mass with respect to the resin forming the core, the charging uniformity of the toner tends to be impaired, which may lead to an increase in fog. In addition, when the content of the crystalline polyester resin B is 50 parts by mass or less, the decrease in the melt viscosity due to the presence of the excess crystalline polyester resin does not occur, so that the offset hardly occurs.

Further, the toner particles of the present invention are preferably heated and held at a temperature T1 (° C.) represented by the following formula (4) in the polymerization step, if necessary.
T1 ≧ Tm (C) +5 Equation (4)
In the polymerization step of the toner particles, the crystalline polyester resin B is sufficiently melted by being heated and held at a temperature equal to or higher than the melting point Tm (C) of the crystalline polyester resin B, and the phase with the vinyl polymer Melting progresses. As a result, the fine dispersibility of the crystalline polyester resin B in the vinyl polymer is improved, and the low-temperature fixability is improved. More preferably, T1 is 10 ° C. or more higher than Tm (C).

Further, after passing through the polymerization step, the toner particles are preferably heat-held (annealed) for 60 minutes or more at a temperature T2 (° C.) represented by the following formula (5) as necessary.
Tm (C) -30 ≦ T2 ≦ Tm (C) -5 Formula (5)
The crystalline polyester resin B tends to be partially amorphous during the production of the toner, and the degree of crystallinity tends to be lowered. The amorphized crystalline polyester resin B may be compatible with the vinyl polymer forming the core to soften the vinyl polymer. After the polymerization step of the toner particles, the crystallinity degree of the crystalline resin is improved by heating and holding at temperature T2 represented by the above formula (5) for 60 minutes or more. That is, even when the crystalline polyester resin B is finely dispersed, the crystallinity is sufficiently maintained, and excellent fixability can be obtained while maintaining the heat resistant storage stability and the durability of the toner.

Further, the dispersion state of the crystalline polyester resin B in the toner can be controlled also by the physical properties such as the acid value and the molecular weight of the crystalline polyester resin B, and the conditions of the melting point and the polymerization temperature of the crystalline resin.
Examples of the method for producing the hybrid crystalline polyester resin B include a method in which a polymerization reaction is allowed to proceed in a pressurized environment when forming an amorphous vinyl site. Specifically, transesterification reaction between hydroxyl group contained in polyester and (meth) acrylic acid ester contained in non-crystalline vinyl site, carboxy group contained in hydroxyl group contained in polyester and non-crystalline vinyl site Generate radicals in the polyester by the esterification reaction with esterification, the esterification reaction between the carboxy group contained in the polyester and the hydroxyl group contained in the amorphous vinyl moiety, and a vinyl monomer is added And polymerization in a pressurized environment. At that time, the degree of pressurization is preferably 0.20 MPa or more and 0.45 MPa or less.

As a vinyl-type polymerizable monomer used when manufacturing the said hybrid crystalline polyester resin B, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.
Examples of monofunctional polymerizable monomers include styrene; styrene derivatives such as α-methylstyrene, o-methylstyrene, m-methylstyrene and p-methylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso -Propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, etc. Acrylic polymerizable monomers; and methacrylic polymerizable monomers in which the acrylic polymerizable monomers are changed to methacrylates.

  As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Acrylic multifunctional polymerizable monomers such as diacrylate, polypropylene glycol diacrylate, 2,2'-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate and tetramethylolmethane tetraacrylate A methacrylic polyfunctional polymerizable monomer in which the acrylic polyfunctional polymerizable monomer is changed to a methacrylate; divinylbenzene, divinyl naphthalene, divinyl Ether and the like.

As the vinyl-based polymerizable monomer, one having a carboxy group or a hydroxy group, or one containing a (meth) acrylic acid ester is preferable. This means that when a strongly polar functional group such as a carboxy group is present in the amorphous vinyl site of the hybrid resin, the amorphous vinyl site has an appropriate polarity, and the toner in an aqueous medium It is preferable in order to stabilize toner particles at the time of particle production.
Further, it is preferable that the non-crystalline vinyl moiety of the hybrid resin is a copolymer with acrylic acid, because the surface of the toner becomes strong and the durability is excellent due to the hydrogen bond due to the carboxy group possessed by acrylic acid. However, when the content of acrylic acid in the hybrid resin exceeds 3.0% by mass, the hygroscopicity tends to increase in a high temperature and high humidity environment, and the chargeability of the toner tends to decrease.

If it is a range which does not inhibit the effect of this invention as a polymerization initiator used in order to polymerize the above-mentioned polymerizable monomer at the time of manufacturing the above-mentioned hybrid resin, an oil soluble initiator and / or a water soluble initiator It is possible to use as appropriate. For example, as oil-soluble initiators, azo compounds such as 2,2'-azobisisobutyro nitrile; t-butyl peroxy neodecanoate, t-hexyl peroxy pivalate, lauroyl peroxide, t Peroxides such as -butylperoxy 2-ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxyisophthalate, di-t-butyl peroxide and the like can be mentioned.
As a water-soluble initiator, ammonium persulfate, potassium persulfate, 2,2'-azobis (N, N'-dimethylene isobutyroamidine) hydrochloride, 2,2'-azobis (2-aminodinopropane) hydrochloric acid Salt, azobis (isobutylamidine) hydrochloride, sodium 2,2'-azobisisobutyronitrile sulfonate, 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2 -Hydroxyethyl] propionamide}, 2,2'-azobis {2-methyl-N- [2- (1-hydroxybutyl)]-propionamide}, hydrochloride ferrous sulfate or hydrogen peroxide can be mentioned.
Particularly preferred is a peroxide, and when the polyester resin is vinyl-modified by hydrogen abstraction reaction, one having a 10 hour half-life temperature of 70 ° C. or more and 170 ° C. or less, preferably 75 ° C. or more and 130 ° C. or less When used, it is more preferable because it has appropriate reactivity.

Next, the toner and the method for producing the toner of the present invention will be described in detail.
The weight average particle diameter (D4) of the toner of the present invention is preferably 4.0 μm or more and 9.0 μm or less, more preferably 5.0 μm or more and 7.5 μm or less.
When the weight average particle diameter of the toner is 4.0 μm or more, it becomes difficult to cause charge up, and it becomes difficult to cause adverse effects such as fogging and scattering due to charge up and thin image density. In addition, it becomes difficult to contaminate the charging member in long-term image output, and it becomes easy to provide a stable high-quality image. Furthermore, not only cleaning of the transfer residual toner remaining on the photosensitive member is facilitated, but also fusion and the like are less likely to occur.
If the thickness is 9.0 μm or less, it is difficult to cause deterioration of thin line reproducibility such as small characters and the like and image scattering, and a high quality image desired nowadays can be provided.

In the method for producing toner particles according to the present invention, the toner particles may comprise a non-crystalline polyester resin A, a crystalline polyester resin B, a polymerizable monomer, a colorant if necessary, and a wax. It is a suspension polymerization method which is produced by forming particles of the monomer composition in an aqueous medium and polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition.
The toner produced by the suspension polymerization method of the present invention will be described in detail.
The toner particles produced by the suspension polymerization method of the present invention are produced, for example, as follows. Amorphous polyester resin A, crystalline polyester resin B, a polymerizable monomer, if necessary, a colorant, a mold release agent, a polymerization initiator and the like are mixed to prepare a polymerizable monomer composition. next,
The polymerizable monomer composition is dispersed in an aqueous medium to granulate particles of the polymerizable monomer composition. Then, the polymerizable monomer in the particles of the polymerizable monomer composition is polymerized in an aqueous medium to obtain toner particles.

As the polymerizable monomer, a vinyl-based polymerizable monomer capable of radical polymerization is used. The vinyl polymer according to the present invention is derived from the polymerizable monomer. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a multifunctional polymerizable monomer can be used.
Examples of monofunctional polymerizable monomers include the following. Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p- n-Hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, styrene derivatives such as p-phenylstyrene; methyl acrylate, Ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n- Acrylic polymerizable monomers such as nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate, etc .; methyl methacrylate, ethyl methacrylate, n -Propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl Phosphate ethyl methacrylate, dibutyl phosphate Methacrylic polymerizable monomers such as methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and vinyl formate; vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl Vinyl ethers such as ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone;

Examples of the polyfunctional polymerizable monomer include the following. Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2 '-Bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-buty Glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4- (methacryloxydiethoxy) phenyl) propane, 2,2'-bis ( 4- (methacryloxy-polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinyl naphthalene, divinyl ether and the like.
Monofunctional polymerizable monomers are used alone or in combination of two or more, or in combination with polyfunctional polymerizable monomers. Multifunctional polymerizable monomers can also be used as crosslinkers.

The polymerizable monomer composition in the above step is prepared by mixing a dispersion obtained by dispersing a coloring agent in a first polymerizable monomer with a second polymerizable monomer. Is preferred. That is, after the colorant is sufficiently dispersed in the first polymerizable monomer, the colorant is more favorably dispersed by mixing it with the other toner material and the second polymerizable monomer. It can be present in the toner particles.

An oil soluble initiator and / or a water soluble initiator is used as a polymerization initiator used in the polymerization of the polymerizable monomer. Examples of oil-soluble initiators include the following. 2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethyl valeronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4 Pigment dispersants such as -methoxy-2,4-dimethyl valeronitrile; acetyl cyclohexyl sulfonyl peroxide, diisopropyl peroxy carbonate, decanoyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide, acetyl peroxide, t- Butylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butylperoxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, t-butylhydroperoxa Peroxide initiators such as id, di-t-butyl peroxide and cumene hydroperoxide;
The water soluble initiators include the following. Ammonium persulfate, potassium persulfate, 2,2′-azobis (N, N′-dimethylene isobutyroamidine) hydrochloride, 2,2′-azobis (2-aminodinopropane) hydrochloride, azobis (isobutylamidine) Hydrochloride, sodium 2,2'-azobisisobutyronitrile sulfonate, ferrous sulfate or hydrogen peroxide.

Moreover, in order to control the polymerization degree of a polymerizable monomer, it is also possible to further add and use a chain transfer agent, a polymerization inhibitor, and the like.
The concentration of the polymerization initiator is preferably in the range of 0.1 parts by mass to 20 parts by mass, and more preferably in the range of 0.1 parts by mass to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer. It is. Although the kind of the said polymerizable initiator changes with polymerization methods somewhat, it is used individually or in mixture with reference to half temperature for 10 hours.

Further, in the present invention, a crosslinking agent can be used at the time of synthesis of the vinyl-based polymer in order to enhance the stress resistance of the toner particles and to control the molecular weight of the particle constituting molecules.
As a crosslinking agent, a compound having two or more polymerizable double bonds is used. Specifically, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate and 1,3-butanediol dimethacrylate; And divinyl compounds such as divinyl aniline, divinyl ether, divinyl sulfide, and divinyl sulfone; and compounds having three or more vinyl groups. These are used alone or as a mixture.
These crosslinking agents are preferably in the range of 0.05 to 10 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the above-mentioned polymerizable monomer in terms of the fixing property and the offset resistance of the toner. Used in the range of 5 parts by mass.

  The polymerizable monomer and the crosslinking agent may be used alone or as a mixture of monomers as appropriate, such that the theoretical glass transition temperature (Tg) exhibits a range of 40 to 75 ° C. When the theoretical glass transition temperature is 40 ° C. or higher, problems do not easily occur from the viewpoint of storage stability and stress resistance of the toner, and when 75 ° C. or lower, the transparency and low temperature fixability in full color image formation of the toner It does not decline.

The aqueous medium used in the suspension polymerization method preferably contains a dispersion stabilizer.
As the dispersion stabilizer, known inorganic and organic dispersion stabilizers can be used. As an inorganic dispersion stabilizer, for example, calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate , Barium sulfate, bentonite, silica, alumina and the like.
Examples of the organic dispersion stabilizer include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, starch and the like. In addition, nonionic, anionic and cationic surfactants can also be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium stearate, potassium stearate, calcium oleate and the like can be mentioned.

Among the above-mentioned dispersion stabilizers, in the present invention, it is preferable to use a poorly water-soluble inorganic dispersion stabilizer which is soluble in an acid. Further, in the present invention, when preparing a water-based dispersion medium using the poorly water-soluble inorganic dispersion stabilizer, these dispersion stabilizers are contained in an amount of 0.2 to 2 with respect to 100 parts by mass of the polymerizable monomer. It is preferable to use it in the ratio which becomes the range of 0 mass part. By using it in the ratio which becomes such a range, it is because the droplet stability in the aqueous medium of a polymerizable monomer composition improves. In the present invention, it is preferable to prepare an aqueous medium using water in the range of 300 to 3000 parts by mass with respect to 100 parts by mass of the polymerizable monomer composition.
In the present invention, when preparing an aqueous medium in which the poorly water-soluble inorganic dispersion stabilizer is dispersed, a commercially available dispersion stabilizer may be dispersed as it is. However, in order to obtain dispersion stabilizer particles having a fine uniform particle size, it is preferable to prepare by preparing the above-mentioned poorly water-soluble inorganic dispersion stabilizer under high-speed stirring in water. For example, when using calcium phosphate as a dispersion stabilizer, a preferable dispersion stabilizer can be obtained by mixing an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high-speed stirring to form fine particles of calcium phosphate.

In the suspension polymerization method, a polar resin is added to the polymerizable monomer composition to produce toner particles, thereby mainly forming a core-forming resin and a release agent added as needed, etc. A toner having a core-shell structure coated with a polar resin (shell) such as amorphous polyester resin A can be obtained.
Therefore, the toner by these polymerization methods has a good release agent encapsulated in the toner, so even if it contains a relatively large amount of release agent, the exposure to the toner surface is small and the toner deterioration in continuous printing Can be suppressed.

A colorant may be used in the toner of the present invention. As colorants, the following black, yellow, magenta and cyan pigments and, if necessary, dyes can be used.
A well-known black coloring agent can be used as a black coloring agent. For example, black colorants include carbon black. Moreover, what mixed the yellow / magenta / cyan coloring agent shown below and adjusted to black is mentioned.
The carbon black is not particularly limited. For example, carbon black obtained by a thermal method, an acetylene method, a channel method, a furnace method, a lamp black method or the like can be used.

The average primary particle size of the carbon black used in the present invention is not particularly limited, but the average primary particle size is preferably 14 to 80 nm, more preferably 25 to 50 nm. When the average primary particle size is 14 nm or more, the toner does not exhibit reddish color and is preferable as black for full color image formation. When the average primary particle size of carbon black is 80 nm or less, it is preferable because the pigment is well dispersed and the coloring power is not excessively lowered.
In addition, the average primary particle size of carbon black can be measured by photographing a magnified image with a scanning electron microscope.
The carbon black may be used alone or in combination of two or more. These may be crude pigments, and may be pigment compositions prepared unless they significantly impair the effect of the pigment dispersant of the present invention.

A well-known yellow coloring agent can be used as a yellow coloring agent.
As the pigment-based yellow colorant, compounds typified by fused polycyclic pigments, isoindolinone compounds, anthraquinone compounds, azo metal complex methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 3, 7, 10, 12, 13, 14, 15, 17, 23, 24, 60, 62, 74, 75, 83, 93, 94, 95, 99, 100, 101, 104, 108, 109, 110 111, 117, 123, 128, 129, 138, 139, 147, 148, 150, 155, 166, 168, 169, 177, 179, 180, 181, 183, 185, 191, 191, 192, 193 , 199.
As a dye-based yellow colorant, C.I. I. solvent Yellow 33, 56, 79, 82, 93, 112, 162, 163, C.I. I. disperse Yellow 42, 64, 201, 211 can be mentioned.

As the magenta colorant, known magenta colorants can be used.
As the magenta colorant, a condensed polycyclic pigment, a diketopyrrolopyrrole compound, an anthraquinone, a quinacridone compound, a base dye lake compound, a naphthol compound, a benzimidazolone compound, a thioindigo compound and a perylene compound are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 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 Violet 19 is mentioned.
As cyan colorants, phthalocyanine compounds and derivatives thereof, anthraquinone compounds and basic dye lake compounds are used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.
The colorants can be used alone, in a mixture, or in the form of a solid solution. In the present invention, the colorant is selected in terms of hue angle, saturation, lightness, weather resistance, OHT transparency, and dispersibility in toner. It is preferable that the addition amount of a coloring agent is 1 mass part or more and 20 mass parts or less with respect to 100 mass parts of resin which forms a core.

  The toner of the present invention preferably contains one or more release agents. The total amount of the releasing agent contained in the toner is preferably 2.5 parts by mass or more and 25.0 parts by mass or less in 100 parts by mass of the toner particles. The total amount of the release agent contained in the toner is more preferably 4.0 parts by mass or more and 20 parts by mass or less, and still more preferably 6.0 parts by mass or more and 18.0 parts by mass or less.

The following are mentioned as a mold release agent. Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, Fischer-Tropsch wax, paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof Dewaxed partially or entirely of fatty acid esters such as carnauba wax and montanic acid ester wax and fatty acid esters such as deacidified carnauba wax; palmitic acid, stearic acid, montanic acid, etc. Saturated linear fatty acids; Brandic acid, eleostearic acid,
Unsaturated fatty acids such as palinaric acid; Stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnavir alcohol, ceryl alcohol, saturated alcohols such as mercyl alcohol; Polyhydric alcohols such as sorbitol; Linoleic acid amide, oleic acid amide, Fatty acid amides such as lauric acid amide; Saturated fatty acid bisamides such as methylene bis stearic acid amide, ethylene bis capric acid amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide; ethylene bis oleic acid amide, hexamethylene bis olein Unsaturated fatty acid amides such as acid amide, N, N 'dioleyl adipamide, N, N' dioleyl sebacic acid amide; m-xylene bis stearic acid amide, N, N 'distearyl Aromatic bisamides such as sophthalic acid amide; aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate etc. (generally referred to as metal soaps); aliphatic hydrocarbon waxes such as styrene Waxes grafted using a vinyl-based monomer such as acrylic acid; partial esterified product of fatty acid and polyhydric alcohol such as behenic acid monoglyceride; methyl ester compound having a hydroxy group obtained by hydrogenation of vegetable oil and the like It can be mentioned.

The toner of the present invention may use a charge control agent in order to keep the chargeability of the toner stable regardless of the environment.
Examples of the negatively chargeable charge control agent include the following. Monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, metal compounds of oxycarboxylic acids and dicarboxylic acids, aromatic oxycarboxylic acids, aromatic mono and polycarboxylic acids and metal salts thereof Examples thereof include anhydrides, esters, phenol derivatives such as bisphenol, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarenes, and resin-based charge control agents.

Examples of the positively chargeable charge control agent include the following. Nigrosine and fatty acid metal salt etc. nigrosine modified product; guanidine compound; imidazole compound; tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, quaternary ammonium salt such as tetrabutylammonium tetrafluoroborate, and analogues thereof Onium salts such as phosphonium salts and their lake pigments; triphenylmethane dyes and their lake pigments (as lakeing agents, phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic Acids, ferricyanides, ferrocyanides, etc.); metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide, etc .; DOO, dioctyl tin borate, diorgano tin borate such as dicyclohexyl tin borate; resin charge control agents.
These can be used alone or in combination of two or more.
Among them, as the charge control agent other than the resin charge control agent, a metal-containing salicylic acid type compound is preferable, and the metal is more preferably aluminum or zirconium. A further preferred control agent is an aluminum salicylate compound.

As the resin charge control agent, it is preferable to use a polymer or copolymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group, a salicylic acid site, and a benzoic acid site.
The preferable blending amount of the charge control agent is 0.01 parts by mass to 20.00 parts by mass, more preferably 0.05 parts by mass to 10.00 parts by mass with respect to 100.00 parts by mass of the polymerizable monomer. .

In the toner of the present invention, in addition to the amorphous polyester resin A, a polar resin forming a shell layer may be used. As a polar resin, although an example is given to the following, things other than these may be used.
Examples of the polar resin used in the present invention include polyester resins, polycarbonate resins, phenol resins, epoxy resins, polyamide resins, cellulose resins and the like. More preferably, polyester resins are desired because of the variety of materials. The polar resin is 20.0 parts by mass or less, more preferably 10.0 parts by mass or less, per 100 parts by mass of the resin forming the core, in order to obtain the detailed effects of the amorphous polyester resin A. Is preferred.

The toner of the present invention preferably has inorganic fine particles on the surface of toner particles. The inorganic fine particles are added to, and mixed with, toner particles in order to improve the flowability of the toner and equalize the charge, and the added inorganic fine particles are present in a state of being uniformly attached to the surface of the toner particles.
The inorganic fine particles in the present invention preferably have a number average particle diameter (D1) of primary particles of 4 nm or more and 500 nm or less.
As the inorganic fine particles used in the present invention, inorganic fine particles selected from silica, alumina, and titania, or composite oxides thereof, and the like can be used. Examples of the composite oxide include silica-alumina composite oxide, silica-titania composite oxide, and strontium titanate fine particles. These inorganic fine particles are preferably used after the surface is subjected to a hydrophobization treatment.

  Furthermore, the toner used in the present invention may further contain other additives such as lubricant powder such as Teflon (registered trademark) powder, zinc stearate powder and polyvinylidene fluoride powder, as long as the toner does not substantially adversely affect the toner. Polishing agents such as cerium oxide powder and boron carbide powder, anti-caking agents, or organic and / or inorganic fine particles of reverse polarity may be used in small amounts as a developability improver. These additives can also be used after the surface is hydrophobized.

The toner of the present invention is applicable to an image forming method using a known one-component developing method or two-component developing method.
The toner of the present invention can be used in any system, for example, toners for high-speed systems, toners for oilless fixing, toners for cleanerless systems, and carriers in a developing unit deteriorated due to long-term use are collected sequentially and fresh. The present invention can be applied to an image forming method using a known one-component developing method or a two-component developing method, such as a developing method toner for replenishing a carrier.

Hereinafter, the measuring method used in the present invention will be described.
«Measurement of average particle size and particle size distribution of toner»
The average particle size and particle size distribution of the toner can be measured by various methods such as Coulter Counter Model TA-III or Coulter Multisizer (manufactured by Coulter Co.). In the present invention, Coulter counter type TA-III (manufactured by Coulter, Inc.) is used to calculate number distribution and weight distribution. The weight average particle diameter (D4) and the number average particle diameter (D1) of the toner are calculated as follows.
As a measuring apparatus, a precise particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) having a 100 μm aperture tube and using a pore electrical resistance method is used. The setting of measurement conditions and the analysis of measurement data use the attached special software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.). The measurement is performed with 25,000 channels of effective measurement channels.
As the electrolytic aqueous solution used for the measurement, a solution in which special grade sodium chloride is dissolved in ion exchange water so that the concentration is about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.
In addition, before performing measurement and analysis, setting of dedicated software was performed as follows.
In the "Change Standard Measurement Method (SOM)" screen of the special software, set the total count number in the control mode to 50000 particles, set the number of measurements once, and the Kd value "standard particle 10.0 μm" (Beckman Coulter Inc. Make the obtained value. The threshold and noise level are automatically set by pressing the "Threshold / noise level measurement button". Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check “Aperture tube flush after measurement”.
In the dedicated software “pulse to particle size conversion setting” screen, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range from 2 μm to 60 μm.

The specific measurement method is as follows.
(1) Place about 200 ml of the electrolytic aqueous solution in a 250 ml round bottom beaker made exclusively for Multisizer 3 and set it on a sample stand, and stir the stirrer rod counterclockwise at 24 revolutions / second. Then, dirt and air bubbles in the aperture tube are removed by the "aperture flush" function of special software.
(2) About 30 ml of the electrolytic aqueous solution is placed in a 100 ml flat bottom beaker made of glass. Among them, “contaminone N” (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH 7 precision measuring instrument cleaning consisting of organic builders as a dispersing agent, Wako Pure Chemical Industries, Ltd. Add about 0.3 ml of a diluted solution obtained by diluting about 3 times by mass with deionized water.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in with 180 degrees of phase shift, and an ultrasonic dispersion device "Ultrasonic Dispensation System Tetora 150" (manufactured by Nikkaki Bios Co., Ltd.) having an electrical output of 120 W is prepared. A predetermined amount of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of the contaminone N is added to the water tank.
(4) The beaker of said (2) is set to the beaker fixing hole of the said ultrasonic dispersion device, and an ultrasonic dispersion device is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid surface of the electrolytic aqueous solution in the beaker is maximized.
(5) In the state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves,
A small amount of mg is added to the aqueous electrolytic solution and dispersed. In addition, when confirming the granulation property of the toner particles, the toner particle suspension after completion of the polymerization reaction is added little by little to the above aqueous electrolytic solution and dispersed. Then, ultrasonic dispersion processing is continued for another 60 seconds. In ultrasonic dispersion, the water temperature of the water tank is appropriately adjusted so as to be 10 ° C. or more and 40 ° C. or less.
(6) In the round bottom beaker of the above (1) placed in the sample stand, the electrolyte aqueous solution of the above (5) in which the toner is dispersed using a pipette is dropped to adjust the measurement concentration to about 5%. . Then, measurement is performed until the number of measurement particles reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the device to calculate the weight average particle diameter (D4) and the number average particle diameter (D1). The “average diameter” on the “analysis / weight statistical value (arithmetic mean)” screen when the graph / volume% is set by dedicated software is the weight average particle size (D4). The “average diameter” on the “Analysis / number statistics (arithmetic mean)” screen when the graph / number% is set by dedicated software is the number average particle diameter (D1).

  About the granulation property in a granulation process, it investigated by D50 weight% / D50 number% measured by the Coulter counter. The term “D50 volume% / D50 number%” means 50% particle size based on weight distribution and 50% particle size based on number distribution.

«Weight-average molecular weight of amorphous polyester resin A and crystalline polyester resin B»
After dispersing and dissolving 0.03 g of crystalline polyester resin in 10 ml of o-dichlorobenzene, it is shaken with a shaker at 135 ° C. for 24 hours, filtered with a 0.2 μm filter, and the filtrate is used as a sample. Analyze under conditions.
[Analysis conditions]
Separation column: Shodex (TSK GMHHR-H HT20) × 2
Column temperature: 135 ° C
Mobile phase solvent: o-dichlorobenzene mobile phase flow rate: 1.0 ml / min.
Sample concentration: about 0.3%
Injection volume: 300 μl
Detector: Differential refractive index detector Shodex RI-71
In addition, when calculating the molecular weight of the sample, standard polystyrene resin (TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-, manufactured by Tosoh Corp.) 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500), and a molecular weight calibration curve is used.

«Weight average molecular weight of amorphous vinyl moiety in crystalline polyester resin B»
The measurement of the molecular weight of the amorphous vinyl moiety in the crystalline polyester resin is carried out by hydrogenolysis of the polyester portion of the crystalline polyester resin. Specifically, 5 ml of dioxane and 1 ml of a 10% by mass aqueous potassium hydroxide solution are added to 30 mg of crystalline polyester resin and shaken at a temperature of 70 ° C. for 6 hours to hydrolyze the polyester portion. The solution was then dried to prepare a sample for measurement of the molecular weight of the vinyl moiety.
After dispersing and dissolving 0.03 g of the sample for measurement in 10 ml of o-dichlorobenzene, shake with a shaker at 135 ° C. for 24 hours, filter with a 0.2 μm filter, and use the filtrate as a sample under the following conditions Perform the analysis.
[Analysis conditions]
Separation column: Shodex (TSK GMHHR-H HT20) × 2
Column temperature: 135 ° C
Mobile phase solvent: o-dichlorobenzene mobile phase flow rate: 1.0 ml / min.
Sample concentration: about 0.3%
Injection volume: 300 μl
Detector: Differential refractive index detector Shodex RI-71
In addition, when calculating the molecular weight of the sample, standard polystyrene resin (TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-, manufactured by Tosoh Corp.) 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500), and a molecular weight calibration curve is used.

<< Melting point of crystalline polyester resin Tm (C) >>
The melting point of the crystalline polyester resin B is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the heat of fusion uses the heat of fusion of indium.
Specifically, 1 mg of crystalline polyester resin is precisely weighed and placed in an aluminum pan, using an empty aluminum pan as a reference, in the measurement range of 20 ° C. to 140 ° C., with the following settings: Make modulation measurements.
・ The heating rate 1 ° C / min
・ Amplitude temperature range ± 0.318 ° C / min
In this temperature rising process, a specific heat change is obtained in the temperature range of 20 ° C. to 140 ° C. The melting point Tm (C) of the crystalline polyester resin B is taken as the maximum endothermic peak temperature in the specific heat change curve.

«Acid Value of Amorphous Polyester Resin A and Crystalline Polyester Resin B»
The acid value of the non-polyester resin A and the crystalline polyester resin B in the present invention can be determined by the following operation.
The acid value is the number of mg of potassium hydroxide necessary to neutralize the acid contained in 1 g of the sample. The acid value of the polar resin was measured according to JIS K 0070-1992. Specifically, it measured according to the following procedures.
(1) Preparation of Reagent 1.0 g of phenolphthalein was dissolved in 90 ml of ethyl alcohol (95 vol%), ion-exchanged water was added to make it 100 ml, and a phenolphthalein solution was obtained.
7 g of special grade potassium hydroxide was dissolved in 5 ml of water, and ethyl alcohol (95 vol%) was added to make 1 liter. The mixture was placed in an alkali resistant container and allowed to stand for 3 days so as not to touch carbon dioxide gas and the like, and then filtered to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution was stored in an alkali resistant container. The factor of the potassium hydroxide solution is as follows: 25 ml of 0.1 mol / l hydrochloric acid is taken in an Erlenmeyer flask, several drops of the phenolphthalein solution are added, titrated with the potassium hydroxide solution, and the hydroxide required for neutralization It was determined from the amount of potassium solution. The 0.1 mol / l hydrochloric acid used was prepared according to JIS K 8001-1998.
(2) Operation (A) Main Test A 2.0 g sample of crushed amorphous polyester resin A or crystalline polyester resin B was precisely weighed in a 200 ml Erlenmeyer flask, and 100 ml of a mixed solution of toluene: ethanol (2: 1) Was added and dissolved over 5 hours. Subsequently, several drops of the phenolphthalein solution were added as an indicator, and titration was performed using the potassium hydroxide solution. The end point of the titration was when the pale pink color of the indicator continued for about 30 seconds.
(B) Blank test
The same titration as in the above operation was performed except that the sample was not used (that is, only a mixed solution of toluene: ethanol (2: 1) was used).
(3) The acid value was calculated by substituting the obtained result into the following equation.
A = [(C−B) × f × 5.61] / S
Here, A: acid value (mg KOH / g), B: addition amount of potassium hydroxide solution of blank test (ml), C: addition amount of potassium hydroxide solution of this test (ml), f: potassium hydroxide Solution factor, S: sample (g).

«Compatibility of crystalline polyester resin B with amorphous polyester resin A»
(A) Preparation of measurement sample 180 mg of amorphous polyester resin A and 20 mg of crystalline polyester resin B were mixed, and then Japan Analytical Industry Co. A sample was prepared by crushing to 5 μm to about 50 μm by freeze-grinding using liquid nitrogen using Cryogenic Sample Crusher (Model JFC-300) manufactured by ltd. The obtained powder was put into a test tube, sufficiently heated in an oil bath heated to 200 ° C., and sufficiently mixed by stirring with a glass rod. After thorough mixing, the test tube was placed in liquid nitrogen and quenched.
(B) Measurement of degree of compatibility The degree of compatibility of the crystalline polyester resin B with the amorphous polyester resin A was measured by a powder X-ray diffractometer as follows.
The powder X-ray diffractometer was manufactured using a sample horizontal type strong X-ray diffractometer "RINT.TTR2" manufactured by Rigaku Corporation.
Each of the freeze-milled sample (A) and the sample heated to 200 ° C. and quenched with liquid nitrogen were each measured by X-ray diffraction as follows.
The measurement sample is placed on a nonreflective sample plate (made by RIGAKU) that does not have a diffraction peak in the measurement range while lightly pressing so as to be flat as powder. If it is strongly pressed, the crystals may be oriented and the correct area ratio may not be calculated. When flat, set the entire sample plate into the device.
"Measurement condition"
・ Tube: Cu
・ Parallel beam optical system ・ Voltage: 50kV
・ Current: 300 mA
・ Start angle: 3 °
End angle: 40 °
・ Sampling width: 0.02 °
・ Scan speed: 10.00 ° / min
・ Divergence slit: Open ・ Divergence longitudinal slit: 10 mm
-Scattering slit: Opening-Reception slit: Opening Based on the largest peak obtained by measurement, the degree of compatibility was calculated as follows using "JADE 6" of analysis software attached to the above-mentioned apparatus.
(1) The largest peak area derived from the crystal of the crystalline polyester resin B obtained by X-ray diffraction measurement was determined. (In the case of crystalline polyester resin 1 described later, a peak around 2θ = 21.5)
(2) The degree of compatibility is calculated according to the following formula.
Degree of compatibility (%) = (B-A) / B x 100
A: Peak area of sample heated to 200 ° C. and quenched with liquid nitrogen B: Peak area of sample after freeze grinding

  EXAMPLES The invention will be specifically described below with reference to Examples, but the invention is not limited in any way. All parts and percentages in the examples and comparative examples are on a mass basis unless otherwise noted. The method for producing the resin and the toner will be described below.

<Production Example of Amorphous Polyester Resin 1>
100 parts by mass of a mixture of raw material monomers mixed in amounts as shown in Table 1 and 0.52 parts by mass of tin di (2-ethylhexanoate) as a catalyst as a catalyst 6 equipped with a nitrogen introducing pipe, a dewatering pipe, a stirrer and a thermocouple The mixture was placed in a 1-liter four-necked flask and reacted under nitrogen atmosphere at 200 ° C. for 6 hours. Furthermore, trimellitic anhydride was added at 210 ° C., and the reaction was performed under a reduced pressure of 40 kPa, and the reaction was continued until the weight average molecular weight (Mw) became 12,000. The obtained polyester resin is referred to as resin 1. Table 1 shows the results of composition analysis of the resin 1. The acid value of the obtained resin 1 was as shown in Table 1.

Compositional analysis of the amorphous polyester resin A was performed by ¹ H-NMR. The specific measurement method is as follows.
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by Nippon Denshi Co., Ltd.)
Measurement frequency: 400 MHz
Pulse condition: 5.0 μs
Frequency range: 10500 Hz
Accumulated number of times: 64 times Measurement temperature: 30 ° C
A 50 mg sample is placed in a sample tube with an inner diameter of 5 mm, heavy chloroform (CDCl ₃ ) is added as a solvent, and this is dissolved in a thermostat at 40 ° C. to prepare a measurement sample. It measured on the said conditions using the said measurement sample.

<Production Example of Amorphous Polyester Resin 2 to 12>
Amorphous polyester resins 2 to 12 were produced in the same manner as in the production example of the amorphous polyester resin 1 except that the amounts of the acid component and the alcohol component were changed as shown in Table 1. Physical properties of the amorphous polyester resins 2 to 12 are shown in Table 1.

<Production Example of Amorphous Polyester Resins 13 to 18>
A non-crystalline polyester resin 13 to 18 was produced in the same manner as in Production Example 1 of the non-crystalline polyester resin except that the reaction time was adjusted and the weight average molecular weight (Mw) was changed. Physical properties of the amorphous polyester resins 13 to 18 are shown in Table 1.

※樹脂組成の表記はアルコール成分のトータルモル数を１００とした時のモル比を示す。ＴＰＡ：テレフタル酸
ＩＰＡ：イソフタル酸
ＴＭＡ：無水トリメリット酸
ＢＰＡ（ＰＯ）：ビスフェノールＡのプロピレンオキサイド２モル付加物
ＥＧ：エチレングリコール

* The notation of the resin composition shows the molar ratio when the total number of moles of the alcohol component is 100. TPA: Terephthalic acid IPA: Isophthalic acid TMA: Trimellitic anhydride BPA (PO): Propylene oxide 2 molar adduct of bisphenol A EG: Ethylene glycol

<Production of Crystalline Polyester Resin 1>
In a reaction vessel equipped with a nitrogen introducing pipe, a dewatering pipe, a stirrer and a thermocouple, 68.4 parts by mass of 1,6-hexanediol as an alcohol monomer, 117.1 parts by mass of 1,12-dodecanediol, and a carboxylic acid As a monomer, 230.3 parts by mass of 1,12-dodecanedioic acid was charged. Then, 1 part by mass of tin dioctylate as a catalyst was added with respect to 100 parts by mass of the total amount of monomers, and heated at 140 ° C. in a nitrogen atmosphere to react for 8 hours while distilling off water under normal pressure. Next, the reaction is carried out while raising the temperature to 200 ° C. at 10 ° C./hour, and after reaching 200 ° C. for 2 hours, the reaction tank is decompressed to 5 kPa or less and reacted at 200 ° C. for 3 hours. Crystalline polyester resin 1 was obtained. Physical properties of the obtained crystalline polyester resin 1 are shown in Table 2.

<Production of Crystalline Polyester Resin 2>
100.0 parts by mass of sebacic acid and 83 parts by mass of 1,9-nonanediol are added to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introducing pipe, a dehydrating pipe, and a decompression device, and the temperature is stirred. Heated to 130 ° C. Titanium (IV) isopropoxide 0.7 as an esterification catalyst
After adding the mass part, the temperature was raised to 160 ° C. and condensation polymerization was carried out for 5 hours. Thereafter, the temperature was raised to a temperature of 180 ° C., and reaction was carried out while reducing pressure until the desired molecular weight was obtained, to obtain polyester (1). The weight average molecular weight (Mw) of the polyester (1) was 19000, and the melting point (Tm) was 83 ° C.
Next, 100.0 parts by mass of polyester (1) and 440.0 parts by mass of dehydrated chloroform were completely dissolved in a reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introducing tube. Thereafter, 5.0 parts by mass of triethylamine was added, and 15.0 parts by mass of 2-bromoisobutyryl bromide was gradually added under ice cooling. Then, it stirred at room temperature (25 degreeC) overnight.
The resin solution was gradually dropped in a container containing 550.0 parts by mass of methanol to reprecipitate the resin component, and then filtered, purified, and dried to obtain a polyester resin A.
Next, 100.0 parts by mass of the polyester resin A obtained above, 365.0 parts by mass of styrene, and 4.8 parts by mass of copper (I) bromide in a reaction vessel provided with a stirrer, a thermometer, and a nitrogen introducing pipe And 11 parts by mass of pentamethyldiethylene triamine were added. After the addition, the polymerization reaction was carried out at a temperature of 110 ° C. while stirring. When the desired molecular weight was achieved, the reaction was stopped, reprecipitated with 250.0 parts by mass of methanol, filtered and purified to remove unreacted styrene and catalyst.
Then, it dried with the vacuum dryer set to 50 degreeC, and obtained the crystalline polyester resin 2 which has a polyester site | part and a vinyl polymer site | part. Physical properties of the obtained crystalline polyester resin 2 are shown in Table 2.

<Production of crystalline polyester resins 3 to 4>
A crystalline polyester resin 3 to 4 was obtained in the same manner as in the method for producing the crystalline polyester resin 2 except that the ratio of styrene to the polyester resin A and the ratio of copper bromide and pentamethyldiethylene triamine were changed. Physical properties of the obtained crystalline polyester resins 3 to 4 are shown in Table 2.

<Production of crystalline polyester resins 5 to 7>
The same procedure as in the method for producing the crystalline polyester resin 1 was repeated except that the reaction time was shortened and the weight average molecular weight was adjusted, to obtain crystalline polyester resins 5 to 7. Physical properties of the obtained crystalline polyester resins 5 to 7 are shown in Table 2.
<Production of crystalline polyester resin 8 to 10>
A crystalline polyester resin 8 to 10 was obtained in the same manner as in the method for producing the crystalline polyester resin 1 except that the reaction time was lengthened, the amount of catalyst was increased, and the weight average molecular weight was adjusted. Physical properties of the obtained crystalline polyester resins 8 to 10 are shown in Table 2.

<Production of Crystalline Polyester Resin 11>
A crystalline polyester resin 11 was obtained in the same manner as in the method for producing the crystalline polyester resin 1 except that 1,6-hexanediol was changed to 52.2 parts by mass of 1,4-butanediol. Physical properties of the obtained crystalline polyester resin 11 are shown in Table 2.
<Production of crystalline polyester resin 12>
In the method for producing the crystalline polyester resin 1, 1,12-dodecanediol is 1, 1
A crystalline polyester resin 12 was obtained in the same manner as in 149.6 parts by mass of 6-hexadecanediol. Physical properties of the obtained crystalline polyester resin 12 are shown in Table 2.

<Production of crystalline polyester resin 13>
In the method for producing crystalline polyester resin 1, 1,6-hexanediol is eliminated, 1,12-dodecanediol is added to 234.2 parts by mass, and 1,12-dodecanediol is added to 146.14 parts by mass of hexanedioic acid A crystalline polyester resin 13 was obtained in the same manner as described above. Physical properties of the obtained crystalline polyester resin 13 are shown in Table 2.
<Production of Crystalline Polyester Resin 14>
A crystalline polyester resin 14 was obtained in the same manner as in the method for producing the crystalline polyester resin 1 except that 1,12-dodecanedioic acid was changed to 1,16-hexadecanediol 258.4. Physical properties of the obtained crystalline polyester resin 14 are shown in Table 2.

結晶性ポリエステル樹脂２及び３の分子量は、非晶性ビニル部の重量平均分子量を除いた値である

The molecular weight of the crystalline polyester resins 2 and 3 is the value excluding the weight average molecular weight of the amorphous vinyl part

(Production example of cyan toner 1)
5 parts by mass of Na ₃ PO ₄ .12H ₂ O is added to 332 parts by mass of ion-exchanged water and heated to a temperature of 60 ° C., and then 58.3 rotations per second using a stirrer (Claremix, manufactured by Emtechnics Co., Ltd.) It stirred at (3500 rpm). To this, 27 parts by mass of a 1.0 mol / liter CaCl ₂ aqueous solution was added to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .
Further, the following materials were uniformly dissolved and mixed at 100 r / min with a propeller type stirring device to prepare a resin-containing monomer.
Styrene 45 parts by mass n-butyl acrylate 25 parts by mass Crystalline polyester resin 1 (10 parts by mass)
Amorphous polyester resin 1 (4 parts by mass)
Further, the following materials were dispersed by an attritor to obtain a fine particle colorant-containing monomer.
-Styrene 30 parts by mass-C.I. I. Pigment Blue 15: 3 (6.8 parts by mass)
Charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 5.0 parts by mass Next, the finely divided colorant-containing monomer and the resin-containing monomer are uniformly mixed, and a wax (HNP-51; After adding 9.0 parts by mass of Nippon Seiwa Co., Ltd. to obtain a polymerizable monomer composition, the polymerizable monomer composition was heated to 60 ° C. Next, the polymerizable monomer composition is introduced into the above aqueous medium, and stirring is carried out for 10 minutes at 58.3 revolutions per second (3500 rpm) using a stirrer (Cleamix, manufactured by Em Technic Co., Ltd.) for polymerization. Of the polymerizable monomer composition to form particles of the polymerizable monomer composition.
Then, 10.0 parts by mass of a polymerization initiator tert-butyl peroxypivalate was added thereto, and granulation was continued for 10 minutes.
Then, it was transferred to a propeller type stirring apparatus, reacted at 70 ° C. for 5 hours while stirring at 100 r / min, heated up to 85 ° C., and reacted for 2 hours to carry out a polymerization reaction. After completion of the polymerization reaction, distillation was performed for 5 hours at 98 ° C. or higher in order to remove unreacted polymerizable monomers and the like. Thereafter, the temperature was lowered to 55 ° C. and annealing treatment was performed for 5 hours. The slurry containing the particles was cooled to room temperature (25 ° C.), and hydrochloric acid was added to the suspension to dissolve the calcium phosphate salt, followed by filtration and washing with water to obtain wet colored particles. Then, the colored particles were dried at a temperature of 40 ° C. for 12 hours to obtain toner particles 1.
100 parts by mass of Toner particles 1 and 1.6 parts by mass of hydrophobic silica fine particles having a BET value of 300 m ² / g and a primary particle diameter of 8 nm are mixed by means of a Henschel mixer (Mitsui Miike Koko Co., Ltd.) Thus, cyan toner 1 was obtained.

(Production example of cyan toner 2 to 43)
A cyan toner 2 to 43 was obtained in the same manner as in the production example of cyan toner 1 except that the types of amorphous polyester resin and crystalline polyester resin and the composition ratio were changed as shown in Table 3.

Example 1
The following blocking test (storage test), durability test, and fixing test were performed using the cyan toner 1. The results of each evaluation are shown in Table 4.

«Blocking test»
10 g of toner was placed in a 50 ml poly cup. The condition of the toner when left to stand in a thermostat at a temperature of 55 ° C. for 72 hours was visually judged as follows. The judgment criteria are shown below.
A: No blocking at all, almost similar to the initial condition.
B: Slightly cohesive, but it is broken by the rotation of the poly cup, and does not cause any problem.
C: Cohesive, but broken by hand.
D: Strong aggregation (solidification).

"Image evaluation"
Remodeled Canon printer LBP 5300 (using a 10 μm thick SUS blade as a toner regulation member, and modifying this toner regulation member so that a blade bias of -200 V can be applied to the development bias), Image evaluation was performed under the environment. The evaluation was carried out by mounting a toner filled with 175 g of the above-mentioned cyan toner 1 as a toner to a cyan station, and mounted a dummy cartridge as the others, and carried out image evaluation.
The image evaluation was performed in an environment of 32.5 ° C./80% RH (high temperature and high humidity environment, hereinafter sometimes abbreviated as HH environment). The operation of outputting one sheet of an image having a printing rate of 1% is repeated, and each time the number of output sheets reaches 200 sheets is left for one week in the HH environment, and then the output of 200 sheets is repeated. Image output was performed and evaluated by the following method. The evaluation results are shown in Table 4. (1) Evaluation of fogging In the HH environment, it was repeated to output an image having a white background portion on the first sheet before and after leaving for one week. After that, the whiteness (reflectance Ds (%)) of the white background portion of the printout image and the white color of the transfer paper measured with “REFLECTMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku Co., Ltd.) for the image having all white background portions From the difference in degree (average reflectance Dr (%)), fog density (%) (= Dr (%)-Ds (%)) was calculated to evaluate fog. The fog was ranked as follows for what was worst in each evaluation.
The filter used was an amber light filter. Although A, B and C are levels that do not pose a problem in use, D is a level that poses a problem in use.
A: less than 0.3% B: 0.3% or more and less than 0.8% C: 0.8% or more and less than 1.3% D: 1.3% or more and less than 2.0%

[Image density stability]
Image density is measured with a color reflectance densitometer (e.g., X-RITE 404 Manufactured by X-Rite Co.). Solid images were output one by one before and after leaving in an HH environment, and the difference in density between the images was measured, and the one with the largest difference in density was shown based on the following evaluation criteria.
A: 0.2 or less B: more than 0.2 0.3 or less C: more than 0.3

(3) Stripes were evaluated by visually observing the solid image of the evaluation toner (toning amount 0.45 mg / cm 2) and the developing roller, and evaluation was made according to the following criteria.
A: No longitudinal stripes in the sheet discharge direction, which are seen as developing stripes, are not seen on the developing roller or on a solid image. There is no problem at all in practice.
B: Although there are 1 to 5 thin streaks in the circumferential direction at both ends of the developing roller, longitudinal streaks in the sheet discharge direction seen as a development streak can not be seen on a solid image. There is no problem at all in practice.
C: There are several thin streaks in the circumferential direction at both ends of the developing roller, and several fine development streaks of 1 to 5 can be seen on a solid image. However, there is no problem in practical use at the level that can be erased by image processing. D: Several thick streaks are observed on the developing roller and on the solid image, and can not be erased even by image processing. Practically problematic level.
E: A large number of development streaks are observed on the developing roller and on the solid image and can not be erased even by image processing. Significantly problematic levels in practice.

<Fixing test>
Low temperature fixability
Using the above evaluation machine, using business 4200 (manufactured by Xerox Co., Ltd.) having a basis weight of 105 g / m ² as an evaluation paper, while changing the set temperature control at intervals of 5 ° C. in the temperature range from 130 ° C. to 220 ° C. The original image was output at temperature.
The original image was an image in which a solid patch image (toner coverage of 0.90 mg / cm ² ) of 10 mm square was divided into nine parts of the paper surface and the image was arranged at the center.
Subsequently, the minimum fixable temperature was determined according to the following criteria by performing a rubbing resistance test of the fixed image output at each temperature.
The minimum fixable temperature is defined as the fixed image density and the image density after rubbing the fixed image 5 times with silbon paper loaded with a load of 50 g / cm ² in each patch, and the average of the determined density reduction rates It is defined as a fixed state in which the value satisfies 5% or less.
In addition, "Macbeth reflection densitometer RD 918" (made by Macbeth) was used for the measurement of density | concentration.
A: A stable fixed image is obtained at a minimum fixing temperature of 160 ° C. or less.
B: A stable fixed image is obtained at a minimum fixing temperature of not less than 160 ° C. and not more than 165 ° C.
C: A stable fixed image is obtained when the minimum fixing temperature is higher than 165 ° C. and not higher than 170 ° C.
D: The minimum fixing temperature is higher than 175 ° C. or has no fixable temperature.

(2) Hot offset resistance 10 mm for density measurement adjusted so that the toner mass per unit area is 0.70 mg / cm ² at the center of the tip of A4 copy paper (75 g / m ² ) for copiers A hot offset phenomenon (a part of the fixed image adheres to the surface of the member of the fixing device at the rear end of the recording material in the sheet passing direction when the fixing device passes) outputs an image having a large number of 10 mm solid images. The temperature of the surface of the fixing heating unit at the time when the phenomenon of fixing on the recording material occurred was measured, and the temperature was determined to be the temperature at which the hot offset phenomenon occurred, and was evaluated based on the following evaluation criteria. In addition, when outputting an image, the process speed was made to be 50 mm / sec by changing the gear and software of the evaluation machine main body. Moreover, the toner before leaving was used as the toner to be evaluated.
A: 225 ° C. or more B: 210 ° C. or more and less than 225 ° C. C: 195 ° C. or more and less than 210 ° C. D: less than 195 ° C.

[Examples 2 to 36, Comparative Examples 1 to 7]
The blocking test (storage stability test), the durability test, and the fixing test of Examples 2 to 36 and Comparative Examples 1 to 7 were performed in the same manner as Example 1 using cyan toners 2 to 43. The results of each evaluation are shown in Table 4.

Claims (6)

A toner having toner particles of a core-shell structure in which a shell layer containing an amorphous polyester resin A is formed on a core containing a resin containing a vinyl polymer and a crystalline polyester resin B ,
Relative to the vinyl polymer 100.0 parts by mass, the content of the non-crystalline polyester resin A is 40.0 mass parts or less than 1.0 part by weight,
The content of the crystalline polyester resin B is 1.0 parts by mass or more and 50.0 parts by mass or less with respect to 100.0 parts by mass of the vinyl polymer.
The amorphous polyester resin A contains isosorbide unit represented by the formula (1) in an amount of 0.1 mol% or more and 30.0 mol% or less based on all monomer units constituting the amorphous polyester resin A,

The crystalline polyester resin B is produced from a monomer containing an aliphatic dicarboxylic acid represented by the following formula (2) and an aliphatic diol represented by the following formula (3): HOOC- (CH ₂ ) _m -COOH Formula (2)
[Wherein, m represents an integer of 4 or more and 14 or less]
HO- (CH ₂ ) _n -OH Formula (3)
[Wherein, n represents an integer of 4 or more and 16 or less]
A toner characterized in that the degree of compatibility of the crystalline polyester resin B with the amorphous polyester resin A is 60% or less.   The toner according to claim 1, wherein the acid value of the amorphous polyester resin A is 0.5 mg KOH / g or more and 25.0 mg KOH / g or less. The toner according to claim 1, wherein an acid value of the crystalline polyester resin B is 5.0 mg KOH / g or less. The toner according to any one of claims 1 to 3, wherein the toner particles are suspension polymerized toner particles. The toner particles include particles of a polymerizable monomer composition containing the amorphous polyester resin A, the crystalline polyester resin B, and a polymerizable monomer for forming the vinyl polymer in an aqueous medium. The toner according to any one of claims 1 to 4, which is a toner particle formed by polymerizing said polymerizable monomer contained in said particles of said polymerizable monomer composition. . A method for producing a toner having toner particles of a core-shell structure in which a shell layer containing an amorphous polyester resin A is formed on a core containing a resin containing a vinyl polymer and a crystalline polyester resin B,
The production method comprises the steps of preparing a polymerizable monomer composition comprising the non-crystalline polyester resin A, the crystalline polyester resin B and a polymerizable monomer for forming the vinyl polymer,
Forming the particles of the polymerizable monomer composition in an aqueous medium, and polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition,
Have
The content of the amorphous polyester resin A is 1.0 to 40.0 parts by mass with respect to 100.0 parts by mass of the vinyl polymer.
The content of the crystalline polyester resin B is 1.0 parts by mass or more and 50.0 parts by mass or less with respect to 100.0 parts by mass of the vinyl polymer.
The amorphous polyester resin A contains isosorbide unit represented by the formula (1) in an amount of 0.1 mol% or more and 30.0 mol% or less based on all monomer units constituting the amorphous polyester resin A,

The crystalline polyester resin B is produced from a monomer containing an aliphatic dicarboxylic acid represented by the following formula (2) and an aliphatic diol represented by the following formula (3): HOOC- (CH ₂ ) _m -COOH Formula (2)
[Wherein, m represents an integer of 4 or more and 14 or less]
HO- (CH ₂ ) _n -OH Formula (3)
[Wherein, n represents an integer of 4 or more and 16 or less]
A method of producing a toner, wherein the degree of compatibility of the crystalline polyester resin B with the amorphous polyester resin A is 60% or less.