JP2022162968A - Toner and method for manufacturing toner - Google Patents

Abstract

To provide a toner that is excellent in low temperature fixability and heat-resistant storage property and is excellent in durability, scratch resistance of a fixed image, and electrification stability.SOLUTION: A toner has a toner particle having a binder resin. In differential scanning calorimetry with the toner as a sample, a peak temperature of endothermic peak derived from the binder resin during the first heating is 50°C or more and 70°C or less, and the endothermic quantity per 1 g of the toner is 30 J/g or more and 70 J/g or less. When acetonitrile is used as a poor solvent and chloroform is used as a good solvent to chloroform solubles of the binder resin, and an elution component when a mobile phase composition of 100 volume% of acetonitrile is linearly changed to a mobile phase composition of 100 volume% of chloroform is subjected to gradient LC analysis, the toner has a specific peak relationship.SELECTED DRAWING: None

Description

The present disclosure relates to a toner used in electrophotography and electrostatic recording, and a method for producing the toner.

Conventionally, energy saving has been regarded as a major technical issue in electrophotographic apparatuses as well, and considerable reduction in the amount of heat applied to fixing devices has been studied. In particular, there is an increasing need for so-called "low-temperature fixability" in which toner can be fixed with lower energy. Techniques for enabling fixing at low temperatures include lowering the glass transition temperature (Tg) of the binder resin in the toner. However, since lowering the Tg leads to lower heat-resistant storage stability of the toner, it is considered difficult to achieve both low-temperature fixability and heat-resistant storage stability of the toner in this method.

As a countermeasure, for example, Patent Documents 1 and 2 discuss a toner containing a plasticizer. The plasticizer has the effect of increasing the softening speed of the binder resin while maintaining the Tg of the toner, and can achieve both low-temperature fixability and heat-resistant storage stability. However, since the toner is softened through the step of melting the plasticizer and plasticizing the binder resin, there is a limit to the melting speed of the toner, and further improvement in low-temperature fixability is desired.

Therefore, a method of using a crystalline vinyl resin as a binder resin has been investigated in order to achieve both further low-temperature fixability and heat-resistant storage stability of the toner. Amorphous resins generally used as binder resins for toners do not show a clear endothermic peak in differential scanning calorimetry (DSC measurement). An endothermic peak appears.

A crystalline vinyl resin has a property that it hardly softens up to the melting point due to the regular arrangement of side chains in the molecule. In addition, the crystal melts abruptly at the boundary of the melting point, resulting in a rapid decrease in viscosity. For this reason, it is attracting attention as a material that has excellent sharp-melt properties and achieves both low-temperature fixability and heat-resistant storage stability. Generally, a crystalline vinyl resin has a long-chain alkyl group as a side chain in the main chain skeleton, and exhibits crystallinity by crystallization of the long-chain alkyl groups of the side chains.

Patent document 3 uses a crystalline vinyl resin obtained by copolymerizing a polymerizable monomer having a long-chain alkyl group and an amorphous polymerizable monomer having a SP value different from that of the polymerizable monomer. A toner that has Accordingly, it is possible to achieve both low-temperature fixability and heat-resistant storage stability. Further, Japanese Patent Application Laid-Open No. 2002-200002 proposes a toner that uses a crystalline vinyl resin and a resin having a smaller contact angle with water than the crystalline vinyl resin.

WO2013/047296 JP 2016-066018 A JP 2020-173414 A Japanese Patent Application Laid-Open No. 2002-108018

However, it has been found that the toners described in Patent Documents 3 and 4 are difficult to satisfy both the abrasion resistance of fixed images and the charging stability in a high-temperature and high-humidity environment while satisfying low-temperature fixability and heat-resistant storage stability. rice field. Long-chain alkyl groups are characterized by high hydrophobicity and low affinity with paper. In the configurations of the toners described in Patent Documents 3 and 4, when the content of the long-chain alkyl group is increased in order to ensure low-temperature fixability, the adhesiveness to paper is lowered, and the fixed image is inferior in abrasion resistance. Also, the durability is lowered. Further, it has been found that when the content of the long-chain alkyl group is reduced, the polarity of the binder resin is increased, causing the toner to absorb water in a high-temperature and high-humidity environment, resulting in poor charging stability.

As described above, the present disclosure provides a toner excellent in low-temperature fixability and heat-resistant storage stability, and further excellent in durability, charging stability in a high-temperature and high-humidity environment, and abrasion resistance of a fixed image, and a method for producing the toner. .

The present disclosure provides a toner having toner particles having a binder resin,
In differential scanning calorimeter measurement using the toner as a sample,
The peak temperature of the endothermic peak derived from the binder resin in the first temperature rise is 50° C. or higher and 70° C. or lower, and the heat absorption amount per 1 g of the toner is 30 J/g or higher and 70 J/g or lower;
Using acetonitrile as a poor solvent and chloroform as a good solvent for the chloroform-soluble portion of the binder resin, the mobile phase composition was linearly changed from acetonitrile 100% by volume to chloroform 100% by volume. It relates to a toner that satisfies the following formulas (1) and (2) when eluted components are analyzed by gradient LC.
0.08≦B/T≦0.30 (1)
0.40≦C/T≦0.70 (2)
T represents the peak area of the peak detected using a Corona charged particle detector when the proportion of chloroform in the mobile phase is 5.0% by volume or more and 95.0% by volume or less,
B represents the peak area of the peak detected using a Corona charged particle detector when the proportion of chloroform in the mobile phase is 30.0% by volume or more and 60.0% by volume or less,
C represents the peak area of the peak detected using the Corona charged particle detector when the proportion of chloroform in the mobile phase is 80.0% by volume or more and 95.0% by volume or less.

式（９）中、Ｒ^１は水素原子又はメチル基を表し、ｍは１５～３５の整数を表す。
４０≦Ｒ１≦６０ ・・・（１０）
６５≦Ｒ２≦８５ ・・・（１１）
Ｒ１＋５≦Ｔ１≦Ｒ１＋１５ ・・・（１２）
Ｒ２＋５≦Ｔ２≦Ｒ２＋２０ ・・・（１３） The present disclosure also provides a method for producing a toner having toner particles containing a binder resin, comprising:
A polymerizable monomer composition containing a polymerizable monomer (x) represented by the following formula (9), other polymerizable monomers other than the polymerizable monomer (x), and a polymerization initiator and a polymerization step of obtaining toner particles by polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition. ,
In the granulation step, the content of the polymerizable monomer (x) in the polymerizable monomers contained in the polymerizable monomer composition is 40.0% by mass or more and 80.0% by mass or less. and
The polymerization initiator contains a first polymerization initiator and a second polymerization initiator, the 10-hour half-life temperature of the first polymerization initiator is R1, and the 10-hour When the half-life temperature is R2, R1 and R2 satisfy the following formulas (10) and (11),
The polymerization step is
The following temperature T1 ( ° C.), and after polymerizing at the temperature T1 (° C.), polymerize at the following temperature T2 (° C.) until the polymerization conversion of the polymerizable monomer (x) reaches 95% by mass or more. The present invention relates to a method for producing a toner having a step of forming a toner.

In formula (9), R ¹ represents a hydrogen atom or a methyl group, and m represents an integer of 15-35.
40≦R1≦60 (10)
65≦R2≦85 (11)
R1+5≤T1≤R1+15 (12)
R2+5≤T2≤R2+20 (13)

The present disclosure also provides a method for producing a toner having toner particles containing a binder resin, comprising:
A polymerizable monomer composition containing a polymerizable monomer (x) represented by formula (9), other polymerizable monomers other than the polymerizable monomer (x), and a polymerization initiator a granulation step of forming particles in an aqueous medium; and a polymerization step of polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition to obtain toner particles;
In the granulation step, the content of the polymerizable monomer (x) in the polymerizable monomers contained in the polymerizable monomer composition is 40.0% by mass or more and 80.0% by mass or less. and
In the polymerization step,
After polymerizing until the polymerization conversion rate of the polymerizable monomer (x) reaches 60% by mass to 80% by mass and the polymerization conversion rate of the other polymerizable monomer reaches 90% by mass to 99% by mass. and a method for producing a toner, in which a polymerization initiator is further added and polymerized until the polymerization conversion of the polymerizable monomer (x) reaches 95% by mass or more.

The present disclosure also provides a method for producing a toner having toner particles containing a binder resin, comprising:
A polymerizable monomer composition containing a polymerizable monomer (x) represented by formula (9), other polymerizable monomers other than the polymerizable monomer (x), and a polymerization initiator a granulation step of forming particles in an aqueous medium; and a polymerization step of polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition to obtain toner particles;
In the granulation step, the content of the polymerizable monomer (x) in the polymerizable monomers contained in the polymerizable monomer composition is 30.0% by mass or more and 75.0% by mass or less. and
The polymerization step is
The step (i) of polymerizing the polymerizable monomer (x) and the other polymerizable monomer until the polymerization conversion rate reaches 90% by mass to 99% by mass, and after the step (i), further Step (ii) of adding a polymerizable monomer (x) and polymerizing until the polymerization conversion rate of the polymerizable monomer (x) is 95% by mass or more
has
The amount of the polymerizable monomer (x) added in the step (ii) is 20.0% by mass or more and 50.0% by mass with respect to the amount of the polymerizable monomer (x) added in the granulation step % or less.

According to the present disclosure, it is possible to provide a toner that is excellent in low-temperature fixability and heat-resistant storage stability, as well as excellent in durability, charge stability in a high-temperature and high-humidity environment, and abrasion resistance of a fixed image.

In the present disclosure, the descriptions of “XX or more and YY or less” or “XX to YY” representing numerical ranges mean numerical ranges including the lower and upper limits, which are endpoints, unless otherwise specified. (Meth)acrylic acid ester means acrylic acid ester and/or methacrylic acid ester. When numerical ranges are stated stepwise, the upper and lower limits of each numerical range can be combined arbitrarily. "Monomer unit" refers to the reacted form of the monomeric material in the polymer. For example, one unit is defined as one segment of carbon-carbon bond in the main chain in which the polymerizable monomer in the polymer is polymerized. A polymerizable monomer can be represented by the following formula (C).

In formula (C), R 1 _A represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group), and R 2 _B represents an arbitrary substituent. A crystalline resin is a resin that exhibits a distinct endothermic peak in differential scanning calorimetry.

The present inventors have found that the above problems can be solved by appropriately controlling the peak temperature of the endothermic peak derived from the binder resin, the amount of heat absorbed, and the polarity of the chloroform-soluble portion of the binder resin.

The present disclosure provides a toner having toner particles having a binder resin,
In differential scanning calorimetry using the toner as a sample,
The peak temperature of the endothermic peak derived from the binder resin in the first temperature rise is 50° C. or higher and 70° C. or lower, and the heat absorption amount per 1 g of the toner is 30 J/g or higher and 70 J/g or lower;
Using acetonitrile as a poor solvent and chloroform as a good solvent for the chloroform-soluble portion of the binder resin, the mobile phase composition was linearly changed from acetonitrile 100% by volume to chloroform 100% by volume. It relates to a toner that satisfies the following formulas (1) and (2) when eluted components are analyzed by gradient LC.
0.08≦B/T≦0.30 (1)
0.40≦C/T≦0.70 (2)
T represents the peak area of the peak detected using a Corona charged particle detector when the proportion of chloroform in the mobile phase is 5.0% by volume or more and 95.0% by volume or less,
B represents the peak area of the peak detected using a Corona charged particle detector when the proportion of chloroform in the mobile phase is 30.0% by volume or more and 60.0% by volume or less,
C represents the peak area of the peak detected using the Corona charged particle detector when the proportion of chloroform in the mobile phase is 80.0% by volume or more and 95.0% by volume or less.

In order to achieve both low-temperature fixability and heat-resistant storage stability, the binder resin as a whole has crystallinity, and it is necessary to secure an effective amount of crystals. For this purpose, the amount of heat absorption indicating the amount of crystalline components in the binder resin must be sufficient (the amount of heat absorption at the endothermic peak). endothermic peak temperature).

Also, resins that generally exhibit crystallinity have sites with low polarity, such as long-chain alkyls. It was found that since long-chain alkyl and other low-polarity moieties have low affinity with paper, scratch resistance tends to decrease as the amount increases. In order to ensure scratch resistance, it is considered necessary to secure a certain amount of a highly polar component while minimizing a low polar component in the binder resin (formula (1) and (2)). For example, in crystalline vinyl resins, since long-chain alkyl groups have a low affinity for paper, scratch resistance tends to decrease as the amount of long-chain alkyl groups increases. Control is preferred.

On the other hand, when the amount of low-polarity components such as long-chain alkyl groups in the binder resin is reduced, the amount of high-polarity components increases, which increases the amount of moisture absorbed and causes fogging due to insufficient charging in high-temperature, high-humidity environments. was found to occur. In order to ensure environmental stability in a high-temperature, high-humidity environment, we believe that it is necessary to secure a certain amount of low-polarity components while minimizing the high-polarity components in the binder resin. (Formulas (1) and (2)).

The toner will be described in detail below. In differential scanning calorimetry using a toner as a sample, the peak temperature of the endothermic peak derived from the binder resin in the first temperature rise is 50° C. or higher and 70° C. or lower. When the endothermic peak temperature is within the above range, both heat-resistant storage stability and low-temperature fixability of the toner can be achieved. When the peak temperature is lower than 50° C., the low-temperature fixability is advantageous, but the heat-resistant storage stability of the toner is remarkably deteriorated. On the other hand, when the peak temperature is higher than 70° C., the low-temperature fixability is deteriorated although excellent heat-resistant storage stability is exhibited.

When the binder resin is a vinyl resin having a long-chain alkyl group, the endothermic peak temperature can be controlled by the length of the long-chain alkyl group, the proportion of the long-chain alkyl group in the binder resin, and the like. Moreover, when the binder resin is a polyester resin, it can be controlled by the number of carbon atoms in the diol component and the dicarboxylic acid component used. The endothermic peak temperature is preferably 57°C or higher and 65°C or lower.

Further, the amount of heat absorption at the endothermic peak derived from the binder resin is 30 J/g or more and 70 J/g or less per 1 g of toner. The endothermic amount of the endothermic peak reflects the ratio of the crystalline substance present in the toner while maintaining its crystallinity to the entire binder resin. That is, even when a large amount of crystalline substance is present in the toner, if the crystallinity is impaired, the endothermic amount at the endothermic peak becomes small. Accordingly, a toner having an endothermic peak endothermic amount within the above range has an appropriate proportion of a crystalline resin that maintains crystallinity in the toner, and good low-temperature fixability can be obtained.

When the endothermic peak endothermic amount per 1 g of toner is smaller than 30 J/g, it indicates that the ratio of the amorphous resin is relatively large. As a result, the influence of the glass transition temperature (Tg) derived from the amorphous resin component is greater. Therefore, it becomes difficult to exhibit good low-temperature fixability. When the endothermic peak endothermic amount per 1 g of the toner is larger than 70 J/g, the crystal component becomes too large, and cleavage at the crystal interface tends to occur, so that the resin tends to become brittle and the durability decreases.

The endothermic amount of the endothermic peak can be controlled by the type of resin exhibiting crystallinity and the proportion of the component exhibiting crystallinity in the binder resin. The lower limit of the heat absorption amount at the endothermic peak per 1 g of toner is preferably 35 J/g or more, and the upper limit is preferably 60 J/g or less, more preferably 55 J/g or less.

Acetonitrile was used as a poor solvent and chloroform was used as a good solvent for the chloroform-soluble portion of the binder resin, and the mobile phase composition was linearly changed from acetonitrile 100% by volume to chloroform 100% by volume. The following formulas (1) and (2) are satisfied when the gradient LC analysis is performed on the eluted components at the time of mixing.
0.08≦B/T≦0.30 (1)
0.40≦C/T≦0.70 (2)
T represents the peak area of the peak detected using a Corona charged particle detector when the proportion of chloroform in the mobile phase is 5.0% by volume or more and 95.0% by volume or less,
B represents the peak area of the peak detected using a Corona charged particle detector when the proportion of chloroform in the mobile phase is 30.0% by volume or more and 60.0% by volume or less,
C represents the peak area of the peak detected using the Corona charged particle detector when the proportion of chloroform in the mobile phase is 80.0% by volume or more and 95.0% by volume or less.

The above formulas (1) and (2) focus on the polarity of the chloroform-soluble component in the binder resin. The details of the gradient LC analysis will be described later, but for the chloroform-soluble portion of the binder resin, the elution component when linearly changing the mobile phase composition from acetonitrile 100% by volume to chloroform 100% by volume. is detected using a Corona charged particle detector. Acetonitrile is a highly polar solvent and elutes highly polar components. Since chloroform has low polarity, when the amount of chloroform is increased linearly, components with low polarity are gradually eluted from components with high polarity. Therefore, in this analysis, separation according to the polarity of the resin in the binder resin can be performed.

B/T represents the ratio of components with a relatively high polarity in the binder resin, and C/T represents the ratio of components with low polarity in the binder resin. That B/T and C/T are within the ranges of formulas (1) and (2) means that the binder resin contains a relatively high polar component and also contains a low polar component. indicates By satisfying the above range, it is possible to secure the charging stability and the scratch resistance of the fixed image in a high-temperature and high-humidity environment.

When B/T is less than 0.08, the amount of components having a relatively high polarity in the binder resin is too small, and the scratch resistance of the fixed image is lowered. If B/T is more than 0.30, the charging stability in a high-temperature and high-humidity environment is poor due to too many high-polarity components. B/T preferably satisfies the following formula (4).
0.10≦B/T≦0.25 (4)

On the other hand, when C/T is less than 0.40, the low polarity components are too small, resulting in deterioration of charging stability in a high-temperature and high-humidity environment. . If C/T is greater than 0.70, the amount of low-polarity components is too high, resulting in poor adhesion to paper. C/T preferably satisfies the following formula (5).
0.50≦C/T≦0.70 (5)

In order to satisfy the above formulas (1) and (2), there is a method in which the composition of the binder resin is biased so that a polymer with a relatively high polarity composition and a polymer with a low polarity composition are appropriately present. is mentioned. As a means for achieving this, when the binder resin is a vinyl-based resin, it is possible to add additional monomers or a polymerization initiator according to the reactivity of the monomers used or the transition of the conversion rate.

When the chloroform-soluble portion of the binder resin is subjected to gradient LC analysis using acetonitrile as a poor solvent and chloroform as a good solvent, the following formula (6) is preferably satisfied. More preferably, the formula (6') is satisfied.
0.00≤A/T≤0.05 (6)
0.00≤A/T≤0.03 (6')

In the formula, A represents the peak area of the peak detected using the Corona charged particle detector when the proportion of chloroform in the mobile phase is 5.0% by volume or more and less than 30.0% by volume. A/T represents a highly polar component in the chloroform-soluble portion of the binder resin. When A/T satisfies the above formula (6), the charging stability is further improved, and the standing fog in a high-temperature and high-humidity environment is easily suppressed. A/T can be controlled by the amount of the highly polar component used.

The content of the chloroform-soluble matter in the binder resin is preferably 30% by mass or more and 100% by mass or less, more preferably 60% by mass or more and 99% by mass or less, based on the mass of the binder resin. When the content of the chloroform-soluble component in the binder resin is within the above range, the amount of the gel component can be controlled to be small, making it easier to ensure low-temperature fixability. The content of the chloroform-soluble component in the binder resin can be controlled by the type and amount of the cross-linking agent used.

The binder resin will be described. Examples of the binder resin include crystalline vinyl resins, polyester resins, polyurethane resins, epoxy resins, and the like. Also, a hybrid resin in which a vinyl resin and a polyester resin are combined may be used. The binder resin preferably contains a vinyl-based resin, and is preferably a vinyl-based resin. The content of the vinyl resin in the binder resin is preferably 50% by mass to 100% by mass, more preferably 80% by mass to 100% by mass, and still more preferably 90% by mass to 100% by mass. , particularly preferably 100% by mass.

The vinyl-based resin is a polymer or copolymer of a compound containing a group having an ethylenically unsaturated bond such as a vinyl group. Examples of groups having an ethylenically unsaturated bond include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups. Also, the binder resin preferably has a monomer unit (a) represented by the following formula (3).

In formula (3), R ⁴ represents a hydrogen atom or a methyl group, and n represents an integer of 15-35. Formula (3) represents a monomer unit having a long-chain alkyl group, and when the binder resin has a long-chain alkyl group, the binder resin tends to exhibit crystallinity. When n in formula (3) is from 15 to 35, it becomes easier to control the peak temperature of the endothermic peak derived from the binder resin within the range. n is preferably an integer of 17-29.

As a method for introducing the monomer unit represented by formula (3), there is a method of polymerizing a vinyl monomer or a resin containing an ethylenically unsaturated bond with the following (meth)acrylic acid ester. . For example, stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acrylate , octacosa (meth)acrylate, myricyl (meth)acrylate, dotriaconta (meth)acrylate and 2-decyltetradecyl (meth)acrylate.

The binder resin may contain two or more monomer units represented by formula (3). The content of the monomer unit (a) represented by formula (3) in the binder resin is preferably 40.0% by mass or more and 80.0% by mass or less, and more preferably 40.0% by mass or more and 70.0% by mass. It is more preferably not more than 40.0% by mass and even more preferably 40.0% by mass or more and 60.0% by mass or less. Within the above range, the balance between the high-polarity component and the low-polarity component in the binder resin is improved, and the low-temperature fixability, adhesion to paper, charging stability and durability are further improved.

In addition to the monomer unit (a), the binder resin contains a monomer unit ( _b ) different from the monomer unit (a). is SP _b , it is preferable to satisfy the following formula (7).
3.00≦(SP _b −SP _a )≦25.00 (7)

By satisfying the above formula (7), the crystallinity of the binder resin is less likely to decrease, and the melting point is easily maintained. This makes it easier to achieve both low-temperature fixability and heat-resistant storage stability. This mechanism is inferred as follows. The monomer units (a) are incorporated into the polymer, and the monomer units (a) are aggregated to form domains, thereby exhibiting crystallinity. In general, when other monomer units are incorporated, crystallization is likely to be inhibited, making it difficult for the polymer to exhibit crystallinity. This tendency becomes remarkable when the monomer unit (a) and other monomer units are randomly combined in one molecule of the polymer.

On the other hand, when SP _b −SP _a is in the range of the formula (7), the monomer unit (a) and the monomer unit (b) are not compatible with each other in the binder resin, and a distinct phase separation state can be formed. It is considered that the melting point can be easily maintained without lowering the crystallinity. SP _b −SP _a more preferably satisfies the following formula (7′).
6.00≦(SP _b −SP _a )≦12.00 (7′)

When two or more types of monomer units (a) are contained, SP _a represents an average value calculated from the molar ratio of each monomer unit (a). For example, the monomer unit A with an SP value of SP ₁₁₁ is included in A mol% based on the total number of moles of the monomer units that satisfy the requirements for the monomer unit (a), and the monomer unit B with an SP value of SP ₁₁₂ is included in the monomer unit (a). The SP value (SP ₁₁ ) when containing (100-A) mol% based on the number of moles of the entire monomer unit that satisfies the requirements of
SP ₁₁ = (SP ₁₁₁ ×A+SP ₁₁₂ ×(100−A))/100
is.

式中、Ｒ^５は、それぞれ水素原子又はメチル基を表し、Ｒ^８は、水素原子又はメチル基を表す。 On the other hand, when there are two or more monomer units (b), SP _b represents the SP value of each monomer unit, and SP _b −SP _a is determined for each monomer unit (b). That is, the monomer unit (b) preferably has SP _b that satisfies formula (7) with respect to SP ₁₁ calculated by the above method. The monomer unit (b) is preferably at least one selected from the group consisting of monomer units represented by formulas (8a) to (8c) below, and preferably represented by formula (8) below.

^In the formula, R5 represents a hydrogen atom or a methyl group, and ^R8 represents a hydrogen atom or a methyl group.

The monomer unit (b) represented by formula (8) tends to satisfy formula (7) above. As a method for introducing the monomer unit represented by the formula (8) into the binder resin, acrylonitrile or methacrylonitrile is combined with an ethylenically unsaturated bond in the resin, or a monomer having an ethylenically unsaturated bond and a method of polymerizing. The monomer forming the monomer unit (b) (polymerizable monomer (Y)) is at least one selected from the group consisting of (meth)acrylonitrile, (meth)acrylic acid, methyl (meth)acrylate, and vinyl acetate. is preferably

When the binder resin contains a vinyl resin, examples of the monomer forming the monomer unit (b) (polymerizable monomer (Y)) include the following in addition to the above.

Monomers having a hydroxy group; for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and the like.
A monomer having an amide group; for example, acrylamide, an amine having 1 to 30 carbon atoms and a carboxylic acid having 2 to 30 carbon atoms having an ethylenically unsaturated bond (acrylic acid, methacrylic acid, etc.) are reacted by a known method. a monomer.

Urethane group-containing monomers: for example, alcohols having 2 to 22 carbon atoms having an ethylenically unsaturated bond (2-hydroxyethyl methacrylate, vinyl alcohol, etc.) and isocyanates having 1 to 30 carbon atoms [monoisocyanate compounds (benzenesulfonyl isocyanate, tosyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, butyl isocyanate, hexyl isocyanate, t-butyl isocyanate, cyclohexyl isocyanate, octyl isocyanate, 2-ethylhexyl isocyanate, dodecyl isocyanate, adamantyl isocyanate, 2,6-dimethylphenyl isocyanate, 3,5-dimethylphenyl isocyanate and 2,6-dipropylphenyl isocyanate, etc.), aliphatic diisocyanate compounds (trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1 , 3-butylene diisocyanate, dodecamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate, etc.), alicyclic diisocyanate compounds (1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate and hydrogenated tetramethylxylylene diisocyanate, etc.), and aromatic diisocyanate compounds (phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6 -tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate and xylylene diisocyanate, etc.)] by a known method, and alcohols having 1 to 26 carbon atoms (methanol, ethanol, propanol, isopropyl alcohol, butanol, t-butyl alcohol, pentanol, Heptanol, octanol, 2-ethylhexanol, nonanol, decanol, undecy alcohol, lauryl alcohol, dodecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetanol, heptadecanol, stearyl alcohol, isostearyl alcohol, elaidyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, nonadecyl alcohol, hexyl alcohol eicosanol, behenyl alcohol, erucyl alcohol, etc.) and an isocyanate having 2 to 30 carbon atoms having an ethylenically unsaturated bond [2-isocyanatoethyl (meth)acrylate, (meth)acrylic acid 2-(0-[1 '-methylpropylideneamino]carboxyamino)ethyl, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate and 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate, etc.] is reacted by a known method, and the like.

Monomers having a urea group: For example, amines having 3 to 22 carbon atoms [primary amines (normal butylamine, t-butylamine, propylamine, isopropylamine, etc.), secondary amines (di-normal ethylamine, di-normal propylamine, di- n-butylamine, etc.), aniline and cycloxylamine, etc.] and a monomer having an ethylenically unsaturated bond and an isocyanate having 2 to 30 carbon atoms reacted by a known method.
Carboxy group-containing monomers; for example, methacrylic acid, acrylic acid, 2-carboxyethyl (meth)acrylate.

The content of the monomer unit (b) in the binder resin is preferably 5.0% by mass to 40.0% by mass, more preferably 20.0% by mass to 35.0% by mass. .

The binder resin may contain other monomer units different from the monomer units (a) and (b) in addition to the monomer units (a) and (b). For example, it may have a third monomer unit polymerized from a third polymerizable monomer and a fourth monomer unit polymerized from a fourth polymerizable monomer. Examples of monomers that form other monomer units include the following. Styrene, α-methylstyrene, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate (Meth)acrylic acid esters such as

As the third polymerizable monomer and the fourth polymerizable monomer, styrene and (meth)acrylic having 1 to 4 carbon atoms (preferably 1 to 3, more preferably 1 or 2, more preferably 2) It is preferred to use acid esters. For example, preferably, the third polymerizable monomer is styrene, and the fourth polymerizable monomer has 1 to 4 carbon atoms (preferably 1 to 3, more preferably 1 or 2, more preferably 2) is at least one selected from the group consisting of (meth)acrylic acid esters; That is, the binder resin preferably has a monomer unit in which styrene represented by the following formula (A) is polymerized and a monomer unit in which a (meth)acrylic acid ester represented by the following formula (B) is polymerized. In formula (B), R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ represents an alkyl group having 1 to 4 carbon atoms (preferably 1 to 3, more preferably 1 or 2, still more preferably 2).

The content of other monomer units in the binder resin is preferably 5.0% by mass to 30.0% by mass. The content of the monomer unit represented by formula (A) in the binder resin is preferably 5.0% by mass to 30.0% by mass, more preferably 8.0% by mass to 20.0% by mass. %. The content of the monomer unit represented by formula (B) in the binder resin is preferably 1.0% by mass to 20.0% by mass, more preferably 5.0% by mass to 10.0% by mass. %.

In addition, the weight average molecular weight (Mw) of the tetrahydrofuran (THF)-soluble portion of the binder resin measured by gel permeation chromatography (GPC) is preferably 10,000 or more and 200,000 or less, more preferably 20,000 or more and 150,000 or less. more preferably 70000 or more and 110000 or less. When Mw is within the above range, it becomes easier to maintain elasticity near room temperature.

The binder resin may contain a polyester resin. A polyester resin that can be used as a binder resin will be described.

A polyester resin can be obtained by reacting a polyhydric carboxylic acid having a valence of 2 or more and a polyhydric alcohol. Examples of polyvalent carboxylic acids include the following compounds. Dibasic acids such as succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, malonic acid, dodecenylsuccinic acid, and their anhydrides or their lower alkyl esters, as well as maleic acid, fumaric acid, Aliphatic unsaturated dicarboxylic acids such as itaconic acid and citraconic acid. 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, and their anhydrides or their lower alkyl esters. These may be used individually by 1 type, and may use 2 or more types together.

Examples of polyhydric alcohols include the following compounds. Alkylene glycol (ethylene glycol, 1,2-propylene glycol and 1,3-propylene glycol); alkylene ether glycol (polyethylene glycol and polypropylene glycol); alicyclic diol (1,4-cyclohexanedimethanol); bisphenols (bisphenol A); Alkylene oxide (ethylene oxide and propylene oxide) adducts of alicyclic diols. The alkyl portion of alkylene glycols and alkylene ether glycols may be linear or branched. Furthermore, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like. These may be used individually by 1 type, and may use 2 or more types together.

For the purpose of adjusting the acid value and hydroxyl value, monohydric acids such as acetic acid and benzoic acid, and monohydric alcohols such as cyclohexanol and benzyl alcohol can be used as necessary. The method for producing the polyester resin is not particularly limited, but for example, transesterification or direct polycondensation can be used alone or in combination.

Next, the polyurethane resin will be described. A polyurethane resin is a reaction product of a diol and a substance containing a diisocyanate group, and by adjusting the diol and diisocyanate, a resin having various functions can be obtained.

Examples of the diisocyanate component include the following. Aromatic diisocyanates having 6 to 20 carbon atoms (excluding carbon atoms in the NCO group, hereinafter the same), aliphatic diisocyanates having 2 to 18 carbon atoms, alicyclic diisocyanates having 4 to 15 carbon atoms, and these diisocyanates Modified products of (urethane group, carbodiimide group, allophanate group, urea group, biuret group, uretdione group, uretimine group, isocyanurate group or oxazolidone group-containing modified product; hereinafter also referred to as "modified diisocyanate"), and these A mixture of two or more of

Aromatic diisocyanates include the following. m- and/or p-xylylene diisocyanate (XDI) and α,α,α',α'-tetramethylxylylene diisocyanate.
Moreover, the following are mentioned as an aliphatic diisocyanate. ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI) and dodecamethylene diisocyanate.
Moreover, the following are mentioned as an alicyclic diisocyanate. isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate, cyclohexylene diisocyanate and methylcyclohexylene diisocyanate.

Among these, preferred are aromatic diisocyanates having 6 to 15 carbon atoms, aliphatic diisocyanates having 4 to 12 carbon atoms, and alicyclic diisocyanates having 4 to 15 carbon atoms, and XDI is particularly preferred. , IPDI and HDI. In addition to the diisocyanate component, a tri- or higher functional isocyanate compound can also be used. As the diol component that can be used in the polyurethane resin, the dihydric alcohol that can be used in the polyester resin described above can be used.

The toner particles may contain core particles having a binder resin and shells covering the core particles. The resin forming the shell is not particularly limited, but vinyl resins or polyester resins are preferable from the viewpoint of charging stability. Amorphous polyester resins are more preferred. The shell does not necessarily cover the entire core, and the core may be partially exposed.

<Release agent>
The toner may contain a release agent. The release agent is preferably at least one selected from the group consisting of hydrocarbon waxes and ester waxes. By using hydrocarbon wax and/or ester wax, it becomes easier to ensure effective releasability. The hydrocarbon wax is not particularly limited, and examples thereof include the following.

Aliphatic hydrocarbon waxes: low-molecular-weight polyethylene, low-molecular-weight polypropylene, low-molecular-weight olefin copolymer, Fischer-Tropsch wax, or oxidized or acid-added waxes thereof.

The ester wax may have at least one ester bond in one molecule, and either natural ester wax or synthetic ester wax may be used. The ester wax is not particularly limited, but examples thereof include the following.
esters of monohydric alcohols and monocarboxylic acids such as behenyl behenate, stearyl stearate, and palmityl palmitate;
Divalent carboxylic acid and monoalcohol esters such as dibehenyl sebacate;
Esters of dihydric alcohols and monocarboxylic acids such as ethylene glycol distearate and hexanediol dibehenate;
Esters of trihydric alcohols and monocarboxylic acids such as glycerin tribehenate;
Esters of tetrahydric alcohols and monocarboxylic acids such as pentaerythritol tetrastearate and pentaerythritol tetrapalmitate;
Esters of hexahydric alcohol and monocarboxylic acid such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate, dipentaerythritol hexabehenate;
esters of polyfunctional alcohols such as polyglycerin behenate and monocarboxylic acids; natural ester waxes such as carnauba wax and rice wax;

Among them, esters of hexahydric alcohols such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate, and dipentaerythritol hexabehenate and monocarboxylic acids are preferable.

As the release agent, a hydrocarbon wax or an ester wax may be used alone, a hydrocarbon wax and an ester wax may be used in combination, or two or more of each may be mixed and used. It is preferable to use one type of wax or two or more types of waxes. More preferably, the release agent is a hydrocarbon wax.

The content of the release agent in the toner particles is preferably 1.0% by mass or more and 30.0% by mass or less, more preferably 2.0% by mass or more and 25.0% by mass or less. When the content of the release agent in the toner particles is within the above range, it becomes easier to ensure release properties during fixing.

The melting point of the release agent is preferably 60° C. or higher and 120° C. or lower. When the melting point of the releasing agent is within the above range, it melts during fixing and easily seeps out onto the surface of the toner particles, and the releasing property is easily exhibited. More preferably, it is 70°C or higher and 100°C or lower.

<Colorant>
The toner may contain a colorant. Examples of the coloring agent include known organic pigments, organic dyes, inorganic pigments, carbon black as a black coloring agent, and magnetic particles. In addition, colorants that are conventionally used in toners may be used.

Examples of yellow colorants include the following. condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, allylamide compounds; Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74
, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, 180 are preferably used.

Colorants for magenta include the following. condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254 are preferably used.

Examples of cyan colorants include the following. Copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62 and 66 are preferably used. Colorants are selected in terms of hue angle, chroma, brightness, lightfastness, OHP transparency, and dispersibility in toner.

The content of the colorant is preferably 1.0 parts by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin. When magnetic particles are used as the colorant, the content thereof is preferably 40.0 parts by mass or more and 150.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin.

<Charge control agent>
A charge control agent may be incorporated into the toner particles, if desired. A charge control agent may also be externally added to the toner particles. By blending the charge control agent, it becomes possible to stabilize the charge characteristics and control the optimum amount of triboelectrification according to the development system. As the charge control agent, a known one can be used, and a charge control agent having a high charging speed and capable of stably maintaining a constant charge amount is particularly preferable.

Examples of charge control agents that control the toner to be negatively charged include the following. Organic metal compounds and chelate compounds are effective, including monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids and dicarboxylic acid metal compounds.

Methods for controlling the toner to be positively chargeable include the following. Nigrosine, quaternary ammonium salts, metal salts of higher fatty acids, diorganostin borates, guanidine compounds and imidazole compounds. The content of the charge control agent is preferably 0.01 parts by mass or more and 20.0 parts by mass or less, more preferably 0.5 parts by mass or more and 10.0 parts by mass or less with respect to 100.0 parts by mass of the toner particles. be.

<External Additives>
The toner particles may be used as the toner as they are, or may be mixed with an external additive or the like and adhered to the surface of the toner particles as the toner may be used. Examples of external additives include inorganic fine particles selected from the group consisting of silica fine particles, alumina fine particles, and titania fine particles, and composite oxides thereof. Examples of composite oxides include silica aluminum fine particles and strontium titanate fine particles. The content of the external additive is preferably 0.01 parts by mass or more and 8.0 parts by mass or less, and is 0.1 parts by mass or more and 4.0 parts by mass or less with respect to 100 parts by mass of the toner particles. is more preferred.

Next, a method for manufacturing toner will be described in detail. The toner particles may be produced by any conventionally known method such as a suspension polymerization method, an emulsion aggregation method, a dissolution suspension method, and a pulverization method, as long as the toner particles are within the scope of the present configuration. Among them, the suspension polymerization method is preferable because it easily satisfies the above formulas (1) and (2).

<Method for Producing Toner by Suspension Polymerization>
(Dispersion process)
A raw material dispersion is prepared by mixing various materials such as a polymerizable monomer for forming a binder resin and, if necessary, a colorant, and melting, dissolving, or dispersing them using a dispersing machine. Furthermore, waxes, charge control agents, solvents for adjusting viscosity, and other additives listed in the section on materials can be appropriately added to the raw material dispersion, if necessary. As the solvent for adjusting the viscosity, any known solvent can be used without particular limitation as long as it can dissolve and disperse the above materials well and has low solubility in water. Examples include toluene, xylene, ethyl acetate and the like. Dispersers include, for example, homogenizers, ball mills, colloid mills, and ultrasonic dispersers.

(Granulation process)
A raw material dispersion is put into an aqueous medium prepared in advance, and a suspension is prepared using a dispersing machine such as a high-speed stirrer or an ultrasonic dispersing machine. The aqueous medium preferably contains a dispersion stabilizer for particle size adjustment and aggregation suppression. As the dispersion stabilizer, conventionally known dispersion stabilizers can be used without particular limitation.

For example, as inorganic dispersion stabilizers, phosphates represented by hydroxyapatite, tricalcium phosphate, dicalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, etc.; carbonates represented by calcium carbonate, magnesium carbonate, etc. salts; metal hydroxides represented by calcium hydroxide, magnesium hydroxide, aluminum hydroxide; sulfates represented by calcium sulfate, barium sulfate, calcium metasilicate, bentonite, silica, alumina and the like.

Examples of organic dispersion stabilizers include polyvinyl alcohol, gelatin, methyl cellulose, methylhydroxypropyl cellulose, ethyl cellulose, sodium salts of carboxymethyl cellulose, polyacrylic acid and its salts, and starch.

Among them, an inorganic dispersion stabilizer is preferable because it has a large charge polarization and a strong adsorptive power to the oil phase, and therefore has a strong anti-agglomeration effect. Further, hydroxyapatite, tricalcium phosphate, and dicalcium phosphate are more preferable because they can be easily removed by pH adjustment.

(Polymerization process)
Toner particles are obtained by polymerizing the polymerizable monomer in the suspension. The polymerization initiator may be mixed with other additives when preparing the raw material dispersion, or may be mixed into the raw material dispersion immediately before suspending it in the aqueous medium. Moreover, it can be added in a state of being dissolved in a polymerizable monomer or another solvent, if necessary, during the granulation process or after the completion of the granulation process, that is, immediately before starting the polymerization process, or during the polymerization process. After polymerizing the polymerizable monomer to obtain a polymer, solvent removal treatment is performed by heating or reducing pressure as necessary to obtain an aqueous dispersion of toner particles.

As the polymerization initiator, a known polymerization initiator can be used without any particular limitation. Specific examples include the following. hydrogen peroxide, acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propionyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, lauroyl peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, pertriphenylacetic acid-tert-hydroperoxide, tert-butyl performate,
tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl permethoxyacetate, perN-(3-toluyl)palmitate-tert-butylbenzoyl peroxide, t -butyl peroxy 2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate , cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, a peroxide polymerization initiator represented by lauroyl peroxide;
2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis -azo or diazo polymerization initiators represented by 4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile and the like;

When a highly hydrophilic amorphous resin is added to the raw material dispersion, the amorphous resin migrates to the surface of the toner particles and forms a shell layer from the granulation process to the polymerization process.

(Filtration process, washing process, drying process, classification process, external addition process)
Toner particles are obtained by carrying out a filtering step of obtaining a solid content from an aqueous dispersion of toner particles by solid-liquid separation, and optionally a washing step, a drying step, and a classification step for adjusting the particle size. The toner particles may be used as toner as they are. If necessary, toner particles and an external additive such as inorganic fine powder can be mixed and adhered using a mixer to obtain a toner. In order to easily satisfy the above formulas (1) and (2) in the suspension polymerization method, the toner particles are preferably produced by any one of the following methods (I) to (III).

The manufacturing method (I) is as follows. A method for producing a toner having toner particles containing a binder resin, comprising a polymerizable monomer (x) represented by the following formula (9) and other polymerizable monomers other than the polymerizable monomer (x) A granulation step of forming particles of a polymerizable monomer composition containing a monomer and a polymerization initiator in an aqueous medium, and the polymerizable monomer composition contained in the particles of the polymerizable monomer composition a polymerization step of obtaining toner particles by polymerizing a monomer;
In the granulation step, the content of the polymerizable monomer (x) in the polymerizable monomers contained in the polymerizable monomer composition is 40.0% by mass or more and 80.0% by mass or less. (More preferably 45.0% by mass to 60.0% by mass),
The polymerization initiator contains a first polymerization initiator and a second polymerization initiator, the 10-hour half-life temperature of the first polymerization initiator is R1, and the 10-hour When the half-life temperature is R2, R1 and R2 satisfy the following formulas (10) and (11),
The polymerization step is
The polymerization conversion rate of the polymerizable monomer (x) is 60% by mass to 80% by mass (more preferably 65% by mass to 75% by mass), and the polymerization conversion rate of the other polymerizable monomer is 90% by mass. % to 99% by mass (more preferably 92% to 97% by mass), a step of polymerizing at a temperature T1 (° C.) (first stage polymerization reaction), and after polymerizing at the temperature T1 (° C.) , polymerizing at temperature T2 (° C.) until the polymerization conversion rate of the polymerizable monomer (x) reaches 95% by mass or more (preferably 99% by mass or more) (second-stage polymerization reaction). Toner manufacturing method.

In formula (9), R ¹ is the same as R ⁴ in formula (3), and m is the same as n. That is, R ¹ represents a hydrogen atom or a methyl group, and m represents an integer of 15-35 (preferably an integer of 17-29).
40≦R1≦60 (10)
65≦R2≦85 (11)
R1+5≤T1≤R1+15 (12)
R2+5≤T2≤R2+20 (13)

(10), (11), (12) and (13) are more preferably the following (10'), (11'), (12') and (13') respectively.
50≦R1≦60 (10′)
70≦R2≦80 (11′)
R1+10≤T1≤R1+15 (12')
R2+10≤T2≤R2+17 (13')

The manufacturing method (II) is as follows. A method for producing a toner having toner particles containing a binder resin, comprising:
A polymerizable monomer composition containing a polymerizable monomer (x) represented by formula (9), other polymerizable monomers other than the polymerizable monomer (x), and a polymerization initiator a granulation step of forming particles in an aqueous medium; and a polymerization step of polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition to obtain toner particles;
In the granulation step, the content of the polymerizable monomer (x) in the polymerizable monomers contained in the polymerizable monomer composition is 40.0% by mass or more and 80.0% by mass or less. (More preferably 45.0% by mass to 60.0% by mass),
In the polymerization step,
The polymerization conversion rate of the polymerizable monomer (x) is 60% by mass to 80% by mass (preferably 65% by mass to 75% by mass), and the polymerization conversion rate of the other polymerizable monomer is 90% by mass. After polymerizing until it reaches ~99% by mass (first stage polymerization reaction), a polymerization initiator is further added so that the polymerization conversion rate of the polymerizable monomer (x) is 95% by mass or more (preferably 99 mass % or more) (second-stage polymerization reaction).

The manufacturing method (III) is as follows. A method for producing a toner having toner particles containing a binder resin, comprising:
A polymerizable monomer composition containing a polymerizable monomer (x) represented by formula (9), other polymerizable monomers other than the polymerizable monomer (x), and a polymerization initiator a granulation step of forming particles in an aqueous medium; and a polymerization step of polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition to obtain toner particles;
In the granulation step, the content of the polymerizable monomer (x) in the polymerizable monomers contained in the polymerizable monomer composition is 30.0% by mass or more and 75.0% by mass or less. (More preferably 30.0% by mass to 40.0% by mass),
The polymerization step is
The step (i) of polymerizing the polymerizable monomer (x) and the other polymerizable monomer until the polymerization conversion rate reaches 90% by mass to 99% by mass, and after the step (i), further A step (ii) of adding a polymerizable monomer (x) and polymerizing until the polymerization conversion rate of the polymerizable monomer (x) is 95% by mass or more (preferably 99% by mass or more). ,
The amount of the polymerizable monomer (x) added in the step (ii) is 20.0% by mass or more and 50.0% by mass with respect to the amount of the polymerizable monomer (x) added in the granulation step % or less (more preferably 35.0 mass % or more and 45.0 mass % or less).

By adopting any one of the above production methods (I) to (III), it is possible to produce a binder resin in which the amount of the polymerizable monomer (x) is biased to some extent. and (2) can be satisfied.

A polymerizable monomer (x) represented by formula (9) forms a monomer unit (a) represented by formula (3). Other polymerizable monomers other than the polymerizable monomer (x) are the polymerizable monomer (Y) forming the monomer unit (b), the third polymerizable monomer and the fourth A polymerizable monomer is mentioned. Other polymerizable monomers other than the polymerizable monomer (x) preferably include the polymerizable monomer (Y), more preferably the polymerizable monomer (Y), the third polymerizable monomer monomer and a fourth polymerizable monomer.

Moreover, the polymerization initiator is not particularly limited, and any known one as described above may be used, and one having desired reactivity may be appropriately selected. For example, one that satisfies formulas (10) and (11) may be selected from the polymerization initiators described above. For example, 6.0 to 10.0 parts by mass of t-butyl peroxypivalate and 0.4 to 1.5 parts by mass of t-butyl peroxyisobutyrate are added to 100 parts by mass of the polymerizable monomer. can be used.

Calculation methods and measurement methods for various physical properties of the toner and toner materials are described below.
<Separation of chloroform-soluble matter in binder resin from toner and measurement of content ratio>
1.5 g of toner is precisely weighed (W1 [g]), put into a pre-precisely weighed cylindrical filter paper (trade name: No. 86R, size 28×100 mm, manufactured by Advantec Toyo Co., Ltd.), and set in a Soxhlet extractor. Extraction is performed for 18 hours using 200 mL of chloroform as a solvent, and extraction is performed at a reflux rate such that the extraction cycle of the solvent is about once every 5 minutes.
After the extraction is completed, the thimble is taken out and air-dried, then vacuum-dried at 40°C for 8 hours. The mass of the thimble containing the extraction residue is weighed, and the mass of the extraction residue is obtained by subtracting the mass of the thimble. W2[g]) is calculated. The "chloroform-soluble matter contained in the toner" is obtained by sufficiently distilling off chloroform from this chloroform extract using an evaporator.

Next, the content (W3 [g]) of components other than the resin component is obtained by the following procedure. About 2 g of toner is accurately weighed (Wa [g]) into a 30 mL magnetic crucible that has been weighed in advance.
Place the magnetic crucible in an electric furnace and heat at about 900° C. for about 3 hours, allow to cool in the electric furnace, allow to cool in a desiccator at room temperature for 1 hour or more, and weigh the mass of the crucible containing the incineration residual ash, The incineration residual ash content (Wb [g]) is calculated by subtracting the mass of the crucible.
Then, the mass (W3 [g]) of the incinerated residual ash in the sample W1 [g] is calculated by the following formula (A).
W3=W1×(Wb/Wa) (A)

Further, when the toner contains a release agent, it is necessary to separate the binder resin and the release agent. Separation of the binder resin and the release agent is carried out by separating a component having a molecular weight of 2000 or less as the release agent by recycling HPLC. The separation method is shown below.
First, the molecular weight distribution of "the chloroform-soluble matter contained in the toner" obtained by the above-described method is measured. In order to measure the molecular weight distribution, the "chloroform-soluble matter contained in the toner" was dissolved in chloroform, and the resulting solution was passed through a solvent-resistant membrane filter "Myshoridisc" with a pore diameter of 0.2 µm ( Tosoh Corporation) to obtain a sample solution. The sample solution is adjusted so that the concentration of chloroform-soluble components is 1.0% by mass. Using this sample solution, the molecular weight distribution is measured under the following conditions.
・ Apparatus: LC-Sakura NEXT (manufactured by Nippon Analytical Industry Co., Ltd.)
・Column: JAIGEL2H, 4H (manufactured by Japan Analytical Industry Co., Ltd.)
・ Eluent: chloroform ・ Flow rate: 10.0 ml / min
・Oven temperature: 40.0°C
・Sample injection volume: 1.0 ml

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

Based on the molecular weight curve obtained in this manner, components having a molecular weight of 2,000 or less are repeatedly fractionated from the chloroform solution of the "chloroform-soluble matter contained in the toner." The binder resin component (Wc [g]) obtained by removing chloroform from the residue after removing the components having a molecular weight of 2000 or less is the "chloroform-soluble component of the binder resin". On the other hand, the release agent component (Wd [g]) is obtained by removing chloroform from the isolated component having a molecular weight of 2000 or less.
Then, the content (W5 [g]) of the binder resin component in the chloroform-soluble matter (W4 [g]) in the sample W1 [g] is calculated from the following formula.
W4=W1-W2
W5=W4×(Wc/(Wc+Wd))

In this case, the content ratio of the chloroform-soluble component in the binder resin in the toner is obtained by the following formula.
Content ratio of chloroform-soluble matter in binder resin in toner (% by mass)=W5/{W5+(W2−W3)}×100

<Gradient LC Analysis Method for Chloroform-Soluble Content of Binder Resin>
The above-described "chloroform-soluble portion of the binder resin" is used as a sample. The sample was adjusted to a sample concentration of 0.1% by mass with chloroform, and the resulting solution was filtered through a 0.45 μm PTFE filter and subjected to measurement. Gradient polymer LC measurement conditions are shown below.
Apparatus: Ultimate 3000 (manufactured by Thermo Fisher Scientific)
Mobile phase: A chloroform (HPLC), B acetonitrile (HPLC)
Gradient: 2 min (A/B = 0/100) → 25 min (A/B = 100/0)
(Note that the slope of the change in the mobile phase was set to be linear.)
Flow rate: 1.0 mL/min Injection: 0.1% by mass x 20 µL
Column: Tosoh TSKgel ODS (4.6 mmφ x 150 mm x 5 µm)
Column temperature: 40°C
Detector: Corona charged particle detector (Corona-CAD) (Therm
o Fisher Scientific)

Regarding the time-intensity graph obtained by the measurement, after converting the time into the ratio of chloroform, the peak area of the following ratio of chloroform is calculated. The percentage of chloroform in the mobile phase is 5.0% by volume or more and 95.0% by volume or less, and the area of the peak is T, and the percentage of chloroform in the mobile phase is 30.0% by volume or more and 60.0% by volume or less. Let B be the area of , and let C be the area of the peak when the proportion of chloroform in the mobile phase is 80.0% by volume or more and 95.0% by volume or less. Further, let A be the area of the peak when the proportion of chloroform in the mobile phase is 5.0% by volume or more and less than 30.0% by volume. The peak area is, for example, in the case of a peak at a chloroform ratio of 5.0% by volume or more and 95.0% by volume or less, the vertical axis of 5.0% by volume, the vertical axis of 95.0% by volume, the intensity curve and the horizontal axis ( It suffices to calculate the area of the range surrounded by the intensity 0).

<Measurement method of peak temperature of endothermic peak and endothermic amount of endothermic peak>
The endothermic peak temperature and endothermic amount of the binder resin in the toner are measured using DSC Q2000 (manufactured by TA Instruments) under the following conditions.
Heating rate: 10°C/min
Measurement start temperature: 20°C
Measurement end temperature: 180°C

The melting points of indium and zinc are used to correct the temperature of the device detector, and the heat of fusion of indium is used to correct the amount of heat. Specifically, 5 mg of a sample (toner) is accurately weighed, placed in an aluminum pan, and subjected to differential scanning calorimetry. An empty silver pan is used as a reference. As the temperature rising process, the temperature is raised to 180°C at a rate of 10°C/min. Then, the peak temperature and endothermic amount are calculated from each peak. When there are a plurality of peaks derived from the binder resin, the maximum peak is used for the peak temperature. As for the endothermic amount, the sum of the endothermic amounts of all peaks is calculated.

A toner is used as a sample, and if the endothermic peak derived from the binder resin does not overlap with the endothermic peak of the release agent or the like, the endothermic peak derived from the binder resin is treated as it is. On the other hand, when the endothermic peak of the release agent overlaps with the endothermic peak derived from the binder resin, it is necessary to subtract the endothermic amount derived from the release agent.

By the following method, the endothermic peak derived from the binder resin can be obtained by subtracting the endothermic amount derived from the release agent. First, a separate DSC measurement is performed on the release agent alone to determine the endothermic characteristics. Next, the release agent content in the toner is determined. The release agent content in the toner can be measured by known structural analysis. After that, the amount of heat absorption due to the release agent is calculated from the release agent content in the toner, and this amount is subtracted from the peak attributed to the binder resin.

If the release agent is easily compatible with the resin component, it is necessary to multiply the content of the release agent by the compatibility rate, calculate the amount of heat absorption due to the release agent, and subtract the result. The compatibility rate is the amount of heat absorption obtained by melting and mixing a molten mixture of resin components and a release agent at the same ratio as the content of the release agent, and the amount of heat absorption of the molten mixture obtained in advance. It is calculated from the value divided by the theoretical endothermic amount calculated from the endothermic amount of the template alone. The endothermic amount is 10.0°C from a temperature 20.0°C lower than the endothermic peak.
The amount of heat absorbed up to a temperature higher than °C is calculated using DSC analysis software (TA Universal Analysis).

<Method for Measuring Content Ratio of Various Monomer Units in Binder Resin>
The content ratio of various monomer units in the binder resin is measured by ¹ H-NMR under the following conditions.
・ Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.)
・Measurement frequency: 400MHz
・Pulse condition: 5.0 μs
・Frequency range: 10500Hz
・Number of accumulated times: 64 times ・Measurement temperature: 30℃
・Sample: 50 mg of a sample to be measured is placed in a sample tube with an inner diameter of 5 mm, deuterated chloroform (CDCl ₃ ) is added as a solvent, and this is dissolved in a constant temperature bath at 40° C. to prepare.

From the obtained ¹ H-NMR chart, from among the peaks attributed to the constituent elements of the monomer unit (a), a peak independent of the peaks attributed to the constituent elements of the other monomer units is selected, and this peak is Calculate the integrated value _S1 of Similarly, among the peaks attributed to the constituents of the monomer unit ( _b ), a peak independent of the peaks attributed to the constituents of the other monomer units is selected, and the integrated value S2 of this peak is calculated. do.

Furthermore, when the third and fourth monomer units are contained, what is the peak attributed to the other monomer unit constituents from the peaks attributed to the constituents of the third and fourth monomer units? Select an independent peak and calculate the integrals _S3 and _S4 of this peak.

The content ratio of the monomer unit (a) is determined as follows using the integral values S ₁ , S ₂ , S ₃ and S ₄ . Note that n ₁ , n ₂ , n ₃ , and n ₄ are the numbers of hydrogen atoms in the component to which the focused peaks are assigned for each site.
Content ratio (mol%) of monomer unit (a) =
{(S ₁ /n ₁ )/((S ₁ /n ₁ )+(S ₂ /n ₂ )+(S ₃ /n ₃ )+(S ₄ /n ₄ ))}×100
Similarly, the proportions of the monomer unit (b) and the third and fourth monomer units are obtained as follows.
Content ratio (mol%) of monomer unit (b) =
{(S ₂ /n ₂ )/((S ₁ /n ₁ )+(S ₂ /n ₂ )+(S ₃ /n ₃ )+(S ₄ /n ₄ ))}×100
Content ratio of the third monomer unit (mol%) =
{(S ₃ /n ₃ )/((S ₁ /n ₁ )+(S ₂ /n ₂ )+(S ₃ /n ₃ )+(S ₄ /n ₄ ))}×100
Content ratio of the fourth monomer unit (mol%) =
{(S ₄ /n ₄ )/((S ₁ /n ₁ )+(S ₂ /n ₂ )+(S ₃ /n ₃ )+(S ₄ /n ₄ ))}×100

In the case where the binder resin contains a polymerizable monomer that does not contain a hydrogen atom as a constituent element other than the vinyl group, ¹³ C-NMR is used with ¹³ C as the atomic nucleus to be measured, and the single pulse mode is used. , and similarly calculated by ¹ H-NMR. Further, when the toner is produced by suspension polymerization, the peaks of the release agent and the shell resin may overlap and independent peaks may not be observed. As a result, the content ratio of each unit in the binder resin may not be calculated. In this case, the binder resin' can be produced by carrying out similar suspension polymerization without using a release agent or other resins, and the binder resin' can be regarded as the binder resin for analysis.

<Method for calculating SP value>
SP _a and SP _b are obtained as follows according to the calculation method proposed by Fedors. From the table described in "Polym. Eng. Sci., 14(2), 147-154 (1974)", the vaporization energy (Δei) (cal/mol) is ) and molar volume (Δvi) (cm ³ /mol), and (4.184×ΣΔei/ΣΔvi) ^0.5 is defined as SP value (J/cm ³ ) ^0.5 .

<Method for measuring molecular weight of resin>
The molecular weight (weight average molecular weight Mw, number average molecular weight Mn) of the THF-soluble portion of the resin is measured by gel permeation chromatography (GPC) as follows. First, the sample is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Myshoridisc" (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of THF-soluble components is 0.8% by mass. This sample solution is used for measurement under the following conditions.
・ Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
・Column: 7 columns of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko)
- Eluent: tetrahydrofuran (THF)
・Flow rate: 1.0 ml/min
・Oven temperature: 40.0°C
・Sample injection volume: 0.10 ml

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

<Method for measuring polymerization conversion rate of polymerizable monomer>
The polymerization conversion rate of the polymerizable monomer is measured using gas chromatography (GC) as follows. 500 mg of the toner particle dispersion is precisely weighed and placed in a sample bottle. After adding 10 g of accurately weighed acetone to this and covering it with a lid, it was mixed well and was washed in a desktop ultrasonic cleaner (trade name “B2510J-MTH”, manufactured by Branson) with an oscillation frequency of 42 kHz and an electrical output of 125 W. Ultrasound for 30 minutes. Thereafter, filtration is performed using a solvent-resistant membrane filter "Myshoridisc" (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm, and 2 μL of the filtrate is analyzed by gas chromatography.
GC: HP 6890GC
Column: HP INNOWax (200 μm × 0.40 μm × 25 m)
Carrier gas: He (constant pressure mode: 20 psi)
Oven: (1) hold at 50°C for 10 minutes, (2) heat up to 200°C at 10°C/min, (3) hold at 200°C for 5 minutes Inlet: 200°C, pulsed splitless mode (20→40 psi, until 0.5 minutes)
Split ratio: 5.0:1.0
Detector: 250°C (FID)

Then, the "remaining amount" of the remaining polymerizable monomer is calculated from a calibration curve prepared using the previously used polymerizable monomer. After that, the polymerization conversion rate (% by mass) of the polymerizable monomer is defined according to the following formula.
Polymerization conversion rate (% by mass) =
100 × (1-(remaining amount of polymerizable monomer) / (total amount of polymerizable monomer used))

In the case of polymerizable monomers (e.g., behenyl acrylate) that cannot be detected by gas chromatography, the polymerization conversion rate can be determined by gel permeation chromatography (GP
C) is used to measure as follows. First, about 500 mg of the toner particle dispersion during polymerization is precisely weighed and put into a sample bottle. This is dissolved in about 10 g of precisely weighed tetrahydrofuran (THF). Then, the obtained solution is filtered through a solvent-resistant membrane filter "Myshoridisc" (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. This sample solution is used for measurement under the following conditions.
・ Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
・Column: 7 columns of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko)
- Eluent: tetrahydrofuran (THF)
・Flow rate: 1.0 ml/min
・Oven temperature: 40.0°C
・Sample injection volume: 0.10 ml

Then, the "remaining amount" of the remaining polymerizable monomer is calculated from a calibration curve prepared using the previously used polymerizable monomer. After that, the polymerization conversion rate (% by mass) of the polymerizable monomer is defined according to the following formula. The measuring apparatus and measuring conditions are the same as those used for measuring the molecular weight of the resin.
Polymerization conversion rate (% by mass) =
100 × (1-(remaining amount of polymerizable monomer) / (total amount of polymerizable monomer used))

EXAMPLES The present invention will be specifically described below with reference to Examples, but these are not intended to limit the present invention in any way. In addition, in the following prescriptions, parts are based on mass unless otherwise specified.

<Example 1>
[Production of Toner by Suspension Polymerization]
(Production of toner particles 1)
- Methacrylonitrile (polymerizable monomer (Y)) 30.0 parts - Styrene (third polymerizable monomer) 13.0 parts - Ethyl methacrylate (fourth polymerizable monomer)7. 0 parts Aluminum di-t-butylsalicylate 1.0 parts Colorant Pigment Blue 15:3 6.5 parts A mixture of the above materials was prepared. The above mixture was put into an attritor (manufactured by Nippon Coke Co., Ltd.) and dispersed at 200 rpm for 2 hours using zirconia beads with a diameter of 5 mm to obtain a raw material dispersion. On the other hand, 735.0 parts of ion-exchanged water and 16.0 parts of trisodium phosphate (12-hydrate) were added to a container equipped with a high-speed stirring device Homomixer (manufactured by Primix) and a thermometer, and stirred at 12000 rpm. The temperature was raised to 60° C. while A calcium chloride aqueous solution prepared by dissolving 9.0 parts of calcium chloride (dihydrate) in 65.0 parts of ion-exchanged water was added thereto, and the mixture was stirred at 12000 rpm for 30 minutes while maintaining the temperature at 60°C. 10% Hydrochloric acid was added thereto to adjust the pH to 6.0 to obtain an aqueous medium in which an inorganic dispersion stabilizer containing hydroxyapatite was dispersed in water.

Subsequently, the raw material dispersion was transferred to a container equipped with a stirrer and a thermometer, and the temperature was raised to 60° C. while stirring at 100 rpm.
・ Behenyl acrylate (polymerizable monomer (X)) 50.0 parts ・ Release agent 1 10.0 parts (Release agent 1: DP18 (dipentaerythritol stearate ester wax, melting point 79 ° C., Nippon Seiro company)
There, after adding the above materials and stirring at 100 rpm for 30 minutes while maintaining 60 ° C., 7.0 parts of t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) as a polymerization initiator, and t After adding 1.0 part of -butyl peroxyisobutyrate (L80 manufactured by Arkema Yoshitomi Co., Ltd.) and stirring for 1 minute, the mixture was added to the aqueous medium being stirred at 12000 rpm with the high-speed stirring device. Stirring was continued at 12,000 rpm for 20 minutes with the high-speed stirring device while maintaining the temperature at 60° C. to obtain a granulation liquid.

The granulation liquid was transferred to a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube, heated to 70°C (temperature T1) while stirring at 150 rpm under a nitrogen atmosphere, and then heated to 70°C (temperature T1) at 150 rpm. A stepwise polymerization reaction was carried out. The holding time of the polymerization reaction in the first stage is such that the polymerization conversion rate of the polymerizable monomer (x) is 70% by mass when the polymerization conversion rate is measured while the above reaction is performed in advance, and the other polymerizable monomers are The time was defined as the time when the polymerization conversion rate of the polymer reached 95% by mass. After that, the temperature was raised to 90° C., and the second-stage polymerization reaction was carried out for 5 hours while maintaining the temperature at 90° C. (temperature T2), thereby obtaining a toner particle dispersion. The polymerization conversion rate of the polymerizable monomer (x) in the second-stage polymerization reaction was 100% by mass.

The obtained toner particle dispersion was cooled to 45° C. while being stirred at 150 rpm, and then heat-treated for 5 hours while maintaining the temperature at 45° C. Thereafter, while stirring was maintained, dilute hydrochloric acid was added until the pH reached 1.5 to dissolve the dispersion stabilizer. The solid content was separated by filtration, thoroughly washed with deionized water, and vacuum-dried at 30° C. for 24 hours to obtain toner particles 1 .

(Preparation of Toner 1)
For 1:100.0 parts of the toner particles, silica fine particles (hydrophobic treatment with hexamethyldisilazane, number average particle size of primary particles: 10 nm, BET specific surface area: 170 m ² /g) are added as an external additive. Toner 1 was obtained by adding 2.0 parts and mixing for 15 minutes at 3000 rpm using a Henschel mixer (manufactured by Nippon Coke Co., Ltd.). Table 3 shows the physical properties of the obtained Toner 1, and Table 4 shows the evaluation results.

各トナーにおいて、表１－２に記載の重合転化率になるまで温度Ｔ１で重合を行い、その後、温度Ｔ２にて第二の重合反応を行った。

For each toner, polymerization was performed at temperature T1 until the polymerization conversion rate shown in Table 1-2 was reached, and then the second polymerization reaction was performed at temperature T2.

モノマーユニット（ａ）の割合は、結着樹脂中の含有割合を示す。Ｍｗは、結着樹脂のテトラヒドロフラン可溶分の重量平均分子量を示す。

The ratio of the monomer unit (a) indicates the content ratio in the binder resin. Mw represents the weight-average molecular weight of the tetrahydrofuran-soluble portion of the binder resin.

<Examples 2 to 18>
In Example 1, the types and amounts of the polymerizable monomers used, the types and amounts of the first polymerization initiator and the second polymerization initiator, and the polymerization conditions are shown in Tables 1-1 and 1-2. Toner particles 2 to 18 were obtained in the same manner except for changing to . Furthermore, external addition was performed in the same manner as in Example 1 to obtain toners 2 to 18. Table 3 shows the physical properties of the toner, and Table 4 shows the evaluation results. In Table 1-1, HDDA described in the cross-linking agent represents 1,6-hexanedioldiacrylate.

<Example 19>
(Production of toner particles 19)
- Methacrylonitrile (polymerizable monomer (Y)) 30.0 parts - Styrene (third polymerizable monomer) 13.0 parts - Ethyl methacrylate (fourth polymerizable monomer)7. 0 parts Aluminum di-t-butylsalicylate 1.0 parts Colorant Pigment Blue 15:3 6.5 parts A mixture of the above materials was prepared. The above mixture was put into an attritor (manufactured by Nippon Coke Co., Ltd.) and dispersed at 200 rpm for 2 hours using zirconia beads with a diameter of 5 mm to obtain a raw material dispersion.

On the other hand, 735.0 parts of ion-exchanged water and 16.0 parts of trisodium phosphate (12-hydrate) were added to a container equipped with a high-speed stirring device Homomixer (manufactured by Primix) and a thermometer, and stirred at 12000 rpm. The temperature was raised to 60° C. while A calcium chloride aqueous solution prepared by dissolving 9.0 parts of calcium chloride (dihydrate) in 65.0 parts of ion-exchanged water was added thereto, and the mixture was stirred at 12000 rpm for 30 minutes while maintaining the temperature at 60°C. 10% Hydrochloric acid was added thereto to adjust the pH to 6.0 to obtain an aqueous medium in which an inorganic dispersion stabilizer containing hydroxyapatite was dispersed in water.

Subsequently, the raw material dispersion was transferred to a container equipped with a stirrer and a thermometer, and the temperature was raised to 60° C. while stirring at 100 rpm.
Behenyl acrylate (polymerizable monomer (X)) 50.0 parts Release agent 1 10.0 parts The above materials were added thereto, and the mixture was stirred at 100 rpm for 30 minutes while maintaining the temperature at 60°C. After adding 7.0 parts of t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) as a polymerization initiator and stirring for an additional 1 minute, the aqueous medium is stirred at 12000 rpm with the high-speed stirring device. was put into Stirring was continued at 12,000 rpm for 20 minutes with the high-speed stirring device while maintaining the temperature at 60° C. to obtain a granulation liquid.

The granulation solution was transferred to a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube, heated to 70° C. while stirring at 150 rpm under a nitrogen atmosphere, and stirred at 150 rpm for the first-stage polymerization reaction. did The holding time of the polymerization reaction in the first stage is such that the polymerization conversion rate of the polymerizable monomer (x) is 70% by mass when the polymerization conversion rate is measured while the above reaction is performed in advance, and the other polymerizable monomers are The time was defined as the time when the polymerization conversion rate of the polymer reached 95% by mass. After that, 2.0 parts of t-butyl peroxypivalate was added, and the second-stage polymerization reaction was carried out for 5 hours to obtain a toner particle dispersion. The polymerization conversion rate of the polymerizable monomer (x) in the second-stage polymerization reaction was 100% by mass.

The obtained toner particle dispersion was cooled to 45° C. while being stirred at 150 rpm, and then heat-treated for 5 hours while maintaining the temperature at 45° C. Thereafter, while stirring was maintained, dilute hydrochloric acid was added until the pH reached 1.5 to dissolve the dispersion stabilizer. The solid content was separated by filtration, thoroughly washed with deionized water, and vacuum-dried at 30° C. for 24 hours to obtain toner particles 19 .

(Preparation of Toner 19)
For 19:100.0 parts of the toner particles, as an external additive, silica fine particles (hydrophobization treatment with hexamethyldisilazane, number average particle diameter of primary particles: 10 nm, BET specific surface area: 170 m ² /g) Toner 19 was obtained by adding 2.0 parts and mixing for 15 minutes at 3000 rpm using a Henschel mixer (manufactured by Nippon Coke Co., Ltd.). Table 3 shows the physical properties of the obtained Toner 19, and Table 4 shows the evaluation results.

<Example 20>
(Production of toner particles 20)
- Methacrylonitrile (polymerizable monomer (Y)) 30.0 parts - Styrene (third polymerizable monomer) 13.0 parts - Ethyl methacrylate (fourth polymerizable monomer)7. 0 parts Aluminum di-t-butylsalicylate 1.0 parts Colorant Pigment Blue 15:3 6.5 parts A mixture of the above materials was prepared. The above mixture was put into an attritor (manufactured by Nippon Coke Co., Ltd.) and dispersed at 200 rpm for 2 hours using zirconia beads with a diameter of 5 mm to obtain a raw material dispersion.

On the other hand, 735.0 parts of ion-exchanged water and 16.0 parts of trisodium phosphate (12-hydrate) were added to a container equipped with a high-speed stirring device Homomixer (manufactured by Primix) and a thermometer, and stirred at 12000 rpm. The temperature was raised to 60° C. while A calcium chloride aqueous solution prepared by dissolving 9.0 parts of calcium chloride (dihydrate) in 65.0 parts of ion-exchanged water was added thereto, and the mixture was stirred at 12000 rpm for 30 minutes while maintaining the temperature at 60°C. 10% Hydrochloric acid was added thereto to adjust the pH to 6.0 to obtain an aqueous medium in which an inorganic dispersion stabilizer containing hydroxyapatite was dispersed in water.

Subsequently, the raw material dispersion was transferred to a container equipped with a stirrer and a thermometer, and the temperature was raised to 60° C. while stirring at 100 rpm.
・Behenyl acrylate (polymerizable monomer (X)) 35.0 parts ・Release agent 1 10.0 parts The above ingredients were added thereto, and the mixture was stirred at 100 rpm for 30 minutes while maintaining the temperature at 60°C. After adding 9.0 parts of t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) as a polymerization initiator and stirring for another minute, the aqueous medium is stirred at 12000 rpm with the high-speed stirring device. was put into Stirring was continued at 12,000 rpm for 20 minutes with the high-speed stirring device while maintaining the temperature at 60° C. to obtain a granulation liquid.

The granulation solution was transferred to a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube, heated to 70° C. while stirring at 150 rpm under a nitrogen atmosphere, and stirred at 150 rpm for the first-stage polymerization reaction. did The holding time of the polymerization reaction in the first stage is such that the polymerization conversion rate of the polymerizable monomer (x) is 93% by mass when the polymerization conversion rate is measured while the above reaction is performed in advance, and the other polymerizable monomers are The time was defined as the time when the polymerization conversion rate of the polymer reached 95% by mass. After that, 15.0 parts of behenyl acrylate was added, and the second-stage polymerization reaction was carried out for 5 hours to obtain a toner particle dispersion. The polymerization conversion rate of the polymerizable monomer (x) in the second-stage polymerization reaction was 100% by mass.

The obtained toner particle dispersion was cooled to 45° C. while being stirred at 150 rpm, and then heat-treated for 5 hours while maintaining the temperature at 45° C. Thereafter, while stirring was maintained, dilute hydrochloric acid was added until the pH reached 1.5 to dissolve the dispersion stabilizer. The solid content was separated by filtration, thoroughly washed with ion-exchanged water, and vacuum-dried at 30° C. for 24 hours to obtain toner particles 20 .

(Preparation of Toner 20)
For 20:100.0 parts of the toner particles, silica fine particles (hydrophobization treatment with hexamethyldisilazane, number average particle diameter of primary particles: 10 nm, BET specific surface area: 170 m ² /g) are added as an external additive. Toner 20 was obtained by adding 2.0 parts and mixing for 15 minutes at 3000 rpm using a Henschel mixer (manufactured by Nippon Coke Co., Ltd.). Table 3 shows the physical properties of the obtained toner 20, and Table 4 shows the evaluation results.

<Comparative Example 1>
(Production of comparative toner particles 1)
・Methacrylonitrile (polymerizable monomer (Y)) 22.0 parts ・Styrene (third polymerizable monomer) 11.0 parts ・Aluminum di-t-butylsalicylate 1.0 parts ・Colorant Pigment Blue 15:3 6.5 parts A mixture of the above ingredients was prepared. The above mixture was put into an attritor (manufactured by Nippon Coke Co., Ltd.) and dispersed at 200 rpm for 2 hours using zirconia beads with a diameter of 5 mm to obtain a raw material dispersion.

On the other hand, 735.0 parts of ion-exchanged water and 16.0 parts of trisodium phosphate (12-hydrate) were added to a container equipped with a high-speed stirring device Homomixer (manufactured by Primix) and a thermometer, and stirred at 12000 rpm. The temperature was raised to 60° C. while A calcium chloride aqueous solution prepared by dissolving 9.0 parts of calcium chloride (dihydrate) in 65.0 parts of ion-exchanged water was added thereto, and the mixture was stirred at 12000 rpm for 30 minutes while maintaining the temperature at 60°C. 10% Hydrochloric acid was added thereto to adjust the pH to 6.0 to obtain an aqueous medium in which an inorganic dispersion stabilizer containing hydroxyapatite was dispersed in water.

Subsequently, the raw material dispersion was transferred to a container equipped with a stirrer and a thermometer, and the temperature was raised to 60° C. while stirring at 100 rpm.
・ Behenyl acrylate (polymerizable monomer (X)) 67.0 parts ・ Release agent 1 10.0 parts (Release agent 1: DP18 (dipentaerythritol stearate ester wax, melting point 79 ° C., Nippon Seiro company)
After adding the above materials and stirring at 100 rpm for 30 minutes while maintaining the temperature at 60° C., 8.0 parts of t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) was added as a polymerization initiator. After further stirring for 1 minute, the mixture was put into the aqueous medium being stirred at 12,000 rpm with the high-speed stirring device. Stirring was continued at 12,000 rpm for 20 minutes with the high-speed stirring device while maintaining the temperature at 60° C. to obtain a granulation liquid.

The granulation liquid was transferred to a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer and a nitrogen inlet tube, and heated to 70° C. under a nitrogen atmosphere while being stirred at 150 rpm. A polymerization reaction was carried out at 150 rpm for 10 hours while maintaining the temperature at 70° C. to obtain a toner particle dispersion.

The obtained toner particle dispersion was cooled to 45° C. while being stirred at 150 rpm, and then heat-treated for 5 hours while maintaining the temperature at 45° C. Thereafter, while stirring was maintained, dilute hydrochloric acid was added until the pH reached 1.5 to dissolve the dispersion stabilizer. The solid content was separated by filtration, thoroughly washed with deionized water, and vacuum-dried at 30° C. for 24 hours to obtain toner particles 1 for comparison.

(Preparation of Comparative Toner 1)
For 1:100.0 parts of the comparative toner particles, as an external additive, silica fine particles (hydrophobization treatment with hexamethyldisilazane, number average particle size of primary particles: 10 nm, BET specific surface area: 170 m ² / 2.0 parts of g) was added and mixed at 3000 rpm for 15 minutes using a Henschel mixer (manufactured by Nippon Coke Co., Ltd.) to obtain Comparative Toner 1. Table 3 shows the physical properties of Comparative Toner 1 obtained, and Table 4 shows the evaluation results.

<Comparative Example 2>
Comparative Toner Particle 2 was obtained in the same manner as in Comparative Example 1, except that the type and amount of the polymerizable monomer used were changed as shown in Table 1-1. Furthermore, external addition was performed in the same manner as in Example 1 to obtain Comparative Toner 2. Table 3 shows the physical properties of the toner, and Table 4 shows the evaluation results.

<Comparative Examples 3 to 6>
In Example 1, the types and amounts of the polymerizable monomers used, the types and amounts of the first polymerization initiator and the second polymerization initiator, and the polymerization conditions are shown in Tables 1-1 and 1-2. Comparative Toner Particles 3 to 6 were obtained in the same manner except for changing to . Furthermore, the same external addition as in Example 1 was performed to obtain toners 3 to 6 for comparison. Table 3 shows the physical properties of the toner, and Table 4 shows the evaluation results.

<Comparative Example 7>
(Preparation of Resin Particle Dispersion 1)
・Styrene 300.0 parts ・Stearyl acrylate 700.0 parts ・Dodecyl mercaptan 6.0 parts ・Decanediol acrylic acid ester 4.0 parts (manufactured by NOF CORPORATION) was dissolved in 1300.0 parts of deionized water, and dispersed and emulsified in a flask. While stirring for 10 minutes, 200.0 parts of ion-exchanged water dissolving 20.0 parts of ammonium persulfate was added, and after nitrogen substitution, the content was heated to 70° C., and emulsion polymerization was performed for 6 hours. rice field. Thereafter, the resin particle dispersion liquid 1 was prepared by cooling the reaction liquid to room temperature.

(Preparation of Resin Particle Dispersion Liquid 2)
・Styrene 300.0 parts ・Stearyl acrylate 700.0 parts ・Acrylic acid 20.0 parts ・Dodecyl mercaptan 12.0 parts ・Decanediol acrylate 4.0 parts 20.0 parts of the surfactant Nulex Paste H (manufactured by NOF Corporation) was dissolved in 1300.0 parts of deionized water, and dispersed and emulsified in a flask. While stirring for 10 minutes, 200.0 parts of ion-exchanged water dissolving 20.0 parts of ammonium persulfate was added, and after nitrogen substitution, the content was heated to 70° C., and emulsion polymerization was performed for 6 hours. rice field. After that, the resin particle dispersion liquid 2 was prepared by cooling the reaction liquid to room temperature.

(Preparation of colorant dispersion)
Phthalocyanine pigment 250 parts (manufactured by Dainichiseika Co., Ltd.: PV FAST BLUE)
Anionic surfactant: 20 parts (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.: Neogen RK)
Ion-exchanged water: 730 parts After mixing and dissolving the above, the mixture was dispersed using a homogenizer (Ultra Turrax manufactured by IKA) to obtain a colorant dispersion.

(Preparation of release agent particle dispersion)
Polyethylene wax 400 parts (manufactured by Toyo Petrolite Co., Ltd.: Polywax725)
Anionic surfactant: 20 parts (manufactured by NOF Corporation: Newex R)
Ion-exchanged water 580 parts or more were mixed and dissolved, dispersed using a homogenizer (manufactured by IKA: Ultra Turrax), and then dispersed using a pressure discharge homogenizer. A release agent particle dispersion was prepared by dispersing release agent particles (polyethylene wax).

(Production of Comparative Toner Particles 7)
Resin particle dispersion 1 900.0 parts Resin particle dispersion 2 225.0 parts Colorant particle dispersion 100.0 parts Release agent particle dispersion 63.0 parts Aluminum sulfate 5.0 parts (manufactured by Wako Pure Chemical Industries, Ltd.)
Ion-exchanged water 1000.0 parts or more was placed in a round stainless steel flask, adjusted to pH 2.0, dispersed using a homogenizer (manufactured by IKA: Ultra Turrax T50), and then heated in an oil bath. It was heated with stirring to 64° C. in the medium. After holding at 61° C. for 3 hours, observation with an optical microscope confirmed that aggregated particles with an average particle size of about 5.0 μm were formed. After heating and stirring at 61° C. for another 4 hours, observation with an optical microscope confirmed the formation of agglomerated particles with an average particle size of about 5.4 μm. The pH of this aggregated particle was 2.5. Therefore, an aqueous solution obtained by diluting sodium hydrogen carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) to 0.5% by weight was added to adjust the pH to 7.2, and then heated to 90 ° C. while continuing to stir and held for 6 hours. . Thereafter, the reaction product was filtered, thoroughly washed with ion-exchanged water, and dried using a vacuum dryer to obtain Comparative Toner Particles 7 . The average particle size of the obtained Comparative Toner Particles 7 was 5.5 μm. Furthermore, external addition was performed in the same manner as in Example 1, and Comparative Toner 7 was obtained. Table 3 shows the physical properties of the toner, and Table 4 shows the evaluation results.

<Toner evaluation method>
<1> Low Temperature Fixability A process cartridge filled with toner was left at 25° C. and 40% RH for 48 hours. Using LBP-712Ci modified to operate even if the fixing device is removed, an unfixed image having an image pattern in which 9-point square images of 10 mm×10 mm are evenly arranged on the transfer paper was output. The toner laying amount on the transfer paper was 0.80 mg/cm ² and the fixing start temperature was evaluated. Fox River Bond (90 g/m ² ) was used as the transfer paper.

As a fixing device, the fixing device of LBP-712Ci was removed to the outside, and an external fixing device was used so that it could operate outside the laser beam printer. The fixing temperature of the external fixing device was increased from 90° C. by 5° C. and the process speed was 230 mm/sec. The fixed image was visually observed, and the lowest temperature at which cold offset did not occur was defined as the fixing start temperature, and the low temperature fixability was evaluated according to the following criteria. Table 4 shows the evaluation results.
[Evaluation criteria]
A: Fixing start temperature is 100° C. or less B: Fixing start temperature is 105° C. or more and 110° C. or less C: Fixing start temperature is 115° C. or more and 120° C. or less D: Fixing start temperature is 125° C. or more

<2> Heat-resistant storage stability Evaluation of heat-resistant storage stability was performed in order to evaluate the stability during storage. 5 g of toner was placed in a 100 ml resin cup and left for 3 days in an environment of temperature 50° C. and humidity 70% RH. rice field. As a measuring device, a digital display type vibration meter "Digivibro MODEL 1332A" (manufactured by Showa Sokki Co., Ltd.) was connected to the side of the vibration table of "Powder Tester" (manufactured by Hosokawa Micron Co., Ltd.). A sieve with an opening of 38 μm (400 mesh), a sieve with an opening of 75 μm (200 mesh), and a sieve with an opening of 150 μm (100 mesh) were stacked in this order on the vibrating table of the powder tester. The measurement was performed in the following manner under the environment of 23° C. and 60% RH.

(1) The amplitude of vibration of the vibration table was previously adjusted so that the displacement value of the digital display type vibration meter was 0.60 mm (peak-to-peak).
(2) The toner left for 3 days as described above was left for 24 hours in an environment of 23° C. and 60% RH in advance. Then, 5.00 g of toner was accurately weighed and gently placed on the uppermost sieve with an opening of 150 μm.
(3) After vibrating the sieve for 15 seconds, the mass of the toner remaining on each sieve was measured, and the aggregation degree was calculated based on the following formula. Table 4 shows the evaluation results.
Aggregation degree (%) = {(Sample mass (g) on a sieve with an opening of 150 µm) / 5.00 (g)} × 100 + {(Sample mass on a sieve with an opening of 75 µm (g)) / 5.00 (g)} × 100 × 0.6 + {(Sample mass (g) on a sieve with an opening of 38 µm) / 5.00 (g)} × 100 × 0.2 [Evaluation criteria]
A: The degree of aggregation is less than 10% B: The degree of aggregation is 10% or more and less than 15%.
C: Degree of aggregation is 15% or more and less than 20%.
D: Aggregation degree is 20% or more

<3> Adhesion to paper (scratch resistance of fixed image)
A fixed image was printed in the same manner as in the evaluation of <1> above. The fixing temperature was set to be 10° C. higher than the fixing start temperature. The image area of the obtained fixed image was covered with a soft thin paper (trade name “Dasper”, manufactured by Ozu Sangyo Co., Ltd.), and the image area was rubbed back and forth five times while applying a load of 4.9 kPa on the thin paper. did. The image densities before and after rubbing were measured, and the reduction rate ΔD (%) of the image density was calculated by the following formula. This ΔD (%) was used as an index of scratch resistance. ΔD (%)={(image density before rubbing−image density after rubbing)/image density before rubbing}×100
The image density was measured with a color reflection densitometer (Color reflection densitometer X-Rite 404A: manufactured by X-Rite). Table 4 shows the evaluation results.
[Evaluation criteria]
A: Density decrease rate of less than 3.0% B: Density decrease rate of 3.0% to less than 7.0% C: Density decrease rate of 7.0% to less than 10.0% D: Density decrease rate of 10 .0% or more

<4> Charging stability Using LBP-712Ci, print out 3000 sheets of an image with a printing rate of 1% using the printer in a high temperature and high humidity environment (HH) (temperature 32.5 ° C., humidity 80% RH). did. After being left for 3 days, one sheet of an image having a white background portion was printed out. Reflectance of the obtained image was measured using a reflection densitometer (reflectometer model TC-6DS manufactured by Tokyo Denshoku Co., Ltd.). An amber filter was used for the filter used in the measurement. The fog was evaluated according to the following criteria, using the worst value Ds (%) of the white background portion reflectance and Dr-Ds when the reflectance of the transfer material before image formation was defined as Dr (%). Table 4 shows the evaluation results.
[Evaluation criteria]
A: Less than 1.0% fog B: 1.0% to less than 3.0% fog C: 3.0% to less than 5.0% fog D: 5.0% or more fog

<5> Durability Durability was evaluated using a commercially available printer LBP712Ci manufactured by Canon. The LBP-712Ci employs one-component contact development, and regulates the amount of toner on the developing carrier by means of a toner regulation member. As the evaluation cartridge, the toner contained in the commercially available cartridge was removed, the inside was cleaned by an air blow, and then 100 g of the toner to be evaluated was filled. Evaluation was carried out by installing the above cartridge in the cyan station and installing dummy cartridges in the others.

Fox River Bond (90 g/m ² ) was used in an environment of 15° C. and 10% RH, and images with a print rate of 1% were continuously printed. After outputting 11,000 sheets, a solid image with a toner lay-on amount of 0.40 mg/cm ² was output, and the presence or absence of streaks (development streaks) on the image was checked. After that, images with a coverage rate of 1% were continuously output, and every time 1000 sheets were output, a solid image was output to confirm the presence or absence of development streaks. Table 4 shows the evaluation results.
[Evaluation criteria]
A: No development streaks until 15,000 sheets B: Development streaks at 14,000 sheets C: Development streaks at 12,000 and 13,000 sheets D: Development streaks at 11,000 sheets

Claims (14)

A toner having toner particles having a binder resin,
In differential scanning calorimetry using the toner as a sample,
The peak temperature of the endothermic peak derived from the binder resin in the first temperature rise is 50° C. or higher and 70° C. or lower, and the heat absorption amount per 1 g of the toner is 30 J/g or higher and 70 J/g or lower;
Using acetonitrile as a poor solvent and chloroform as a good solvent for the chloroform-soluble portion of the binder resin, the mobile phase composition was linearly changed from acetonitrile 100% by volume to chloroform 100% by volume. A toner that satisfies the following formulas (1) and (2) when an eluted component is subjected to gradient LC analysis.
0.08≦B/T≦0.30 (1)
0.40≦C/T≦0.70 (2)
T represents the peak area of the peak detected using a Corona charged particle detector when the proportion of chloroform in the mobile phase is 5.0% by volume or more and 95.0% by volume or less,
B represents the peak area of the peak detected using a Corona charged particle detector when the proportion of chloroform in the mobile phase is 30.0% by volume or more and 60.0% by volume or less,
C represents the peak area of the peak detected using the Corona charged particle detector when the proportion of chloroform in the mobile phase is 80.0% by volume or more and 95.0% by volume or less. 2. The toner according to claim 1, wherein the binder resin has a monomer unit (a) represented by the following formula (3).

In formula (3), R ⁴ represents a hydrogen atom or a methyl group, and n represents an integer of 15-35. 3. The toner according to claim 2, wherein the content of the monomer unit (a) represented by the formula (3) in the binder resin is 40.0% by mass or more and 80.0% by mass or less. the binder resin contains, in addition to the monomer unit (a), a monomer unit (b) different from the monomer unit (a);
4. The toner according to claim 2, wherein the SP value of the monomer unit (a) is SP _a and the SP value of the monomer unit (b) is SP _b , satisfying the following formula (7).
3.00≦(SP _b −SP _a )≦25.00 (7) 5. The toner according to claim 4, wherein the monomer unit (b) is at least one selected from the group consisting of monomer units represented by formulas (8a) to (8c) below.

^In the formula, R5 represents a hydrogen atom or a methyl group, and ^R8 represents a hydrogen atom or a methyl group. 5. The toner according to claim 4, wherein the monomer unit (b) is represented by the following formula (8).

^In the formula, R5 represents a hydrogen atom or a methyl group. The toner according to any one of claims 1 to 6, wherein B/T satisfies the following formula (4).
0.10≦B/T≦0.25 (4) The toner according to any one of claims 1 to 7, wherein the C/T satisfies the following formula (5).
0.50≦C/T≦0.70 (5) 9. The method according to any one of claims 1 to 8, wherein the chloroform-soluble portion of the binder resin satisfies the following formula (6) when subjected to gradient LC analysis using acetonitrile as a poor solvent and chloroform as a good solvent. 1. The toner according to item 1.
0.00≤A/T≤0.05 (6)
In formula (6), A represents the peak area of the peak detected using the Corona charged particle detector when the proportion of chloroform in the mobile phase is 5.0% by volume or more and less than 30.0% by volume. 10. The toner according to any one of claims 1 to 9, wherein the content of chloroform-soluble matter in the binder resin is 30% by mass or more and 100% by mass or less based on the mass of the binder resin. The toner according to any one of claims 1 to 10, wherein the binder resin is a vinyl resin. A method for producing a toner having toner particles containing a binder resin, comprising:
A polymerizable monomer composition containing a polymerizable monomer (x) represented by the following formula (9), other polymerizable monomers other than the polymerizable monomer (x), and a polymerization initiator and a polymerization step of obtaining toner particles by polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition. ,
In the granulation step, the content of the polymerizable monomer (x) in the polymerizable monomers contained in the polymerizable monomer composition is 40.0% by mass or more and 80.0% by mass or less. and
The polymerization initiator contains a first polymerization initiator and a second polymerization initiator, the 10-hour half-life temperature of the first polymerization initiator is R1, and the 10-hour When the half-life temperature is R2, R1 and R2 satisfy the following formulas (10) and (11),
The polymerization step is
The following temperature T1 ( ° C.), and after polymerizing at the temperature T1 (° C.), polymerize at the following temperature T2 (° C.) until the polymerization conversion of the polymerizable monomer (x) reaches 95% by mass or more. A method for producing a toner, comprising a step of forming a toner.

In formula (9), R ¹ represents a hydrogen atom or a methyl group, and m represents an integer of 15-35.
40≦R1≦60 (10)
65≦R2≦85 (11)
R1+5≤T1≤R1+15 (12)
R2+5≤T2≤R2+20 (13) A method for producing a toner having toner particles containing a binder resin, comprising:
A polymerizable monomer composition containing a polymerizable monomer (x) represented by the following formula (9), other polymerizable monomers other than the polymerizable monomer (x), and a polymerization initiator and a polymerization step of obtaining toner particles by polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition. ,
In the granulation step, the content of the polymerizable monomer (x) in the polymerizable monomers contained in the polymerizable monomer composition is 40.0% by mass or more and 80.0% by mass or less. and
In the polymerization step,
After polymerizing until the polymerization conversion rate of the polymerizable monomer (x) reaches 60% by mass to 80% by mass and the polymerization conversion rate of the other polymerizable monomer reaches 90% by mass to 99% by mass. and a method for producing a toner, further comprising adding a polymerization initiator and polymerizing the polymerizable monomer (x) until the polymerization conversion rate reaches 95% by mass or more.

In formula (9), R ¹ represents a hydrogen atom or a methyl group, and m represents an integer of 15-35. A method for producing a toner having toner particles containing a binder resin, comprising:
A polymerizable monomer composition containing a polymerizable monomer (x) represented by the following formula (9), other polymerizable monomers other than the polymerizable monomer (x), and a polymerization initiator and a polymerization step of obtaining toner particles by polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition. ,
In the granulation step, the content of the polymerizable monomer (x) in the polymerizable monomers contained in the polymerizable monomer composition is 30.0% by mass or more and 75.0% by mass or less. and
The polymerization step is
The step (i) of polymerizing the polymerizable monomer (x) and the other polymerizable monomer until the polymerization conversion rate reaches 90% by mass to 99% by mass, and after the step (i), further Step (ii) of adding a polymerizable monomer (x) and polymerizing until the polymerization conversion rate of the polymerizable monomer (x) is 95% by mass or more
has
The amount of the polymerizable monomer (x) added in the step (ii) is 20.0% by mass or more and 50.0% by mass with respect to the amount of the polymerizable monomer (x) added in the granulation step % or less.

In formula (9), R ¹ represents a hydrogen atom or a methyl group, and m represents an integer of 15-35.