JP7716912B2 - Toner for developing electrostatic images - Google Patents

Description

The present invention relates to a toner for developing electrostatic images used to develop latent images formed in electrophotography, electrostatic recording, electrostatic printing, etc.

In the field of electrophotography, with the advancement of electrophotographic systems, there is a demand for the development of electrophotographic toner that can support higher image quality and faster speeds.

Patent Document 1 discloses a toner for developing electrostatic images that is excellent in durability and coloring power, and contains an amorphous resin having an acidic group, a colorant, a wax, and a compound B having an aliphatic hydrocarbon group having from 12 to 30 carbon atoms, and at least one basic nitrogen-containing group selected from the group consisting of an amino group, an imino group, a cyano group, an azo group, a diazo group, and an azido group.
Patent Document 2 discloses an electrostatic image developing toner containing a binder resin (A), a wax (B), and a wax dispersant (C) for the purpose of providing a toner for developing electrostatic images that is excellent in low-temperature fixing property and durability, wherein the wax (B) has a melting point of 70 to 105°C, the endothermic heat ΔH1 of the endothermic peak derived from the wax (B) measured by a differential scanning calorimeter of the toner is 4 to 15 J/g, and the endothermic heat ΔH2 of the endothermic peak derived from the wax (B) measured by a differential scanning calorimeter after the toner is washed with hexane satisfies the relational expression ΔH2/ΔH1>0.4.

Japanese Patent Application Laid-Open No. 2019-174672 Japanese Patent Application Laid-Open No. 2019-184931

The present invention relates to a toner for developing electrostatic images that has excellent durability, bending resistance of printed images, and storage stability under high-temperature and high-humidity conditions.

The present invention relates to a toner for developing electrostatic images, which contains an amorphous resin A having an acidic group, a compound B having a polyolefin skeleton and at least one basic nitrogen-containing group selected from the group consisting of an amino group, an imino group, a cyano group, an azo group, a diazo group, and an azido group, and a release agent C, and which contains an aliphatic alcohol having 4 to 8 carbon atoms as the alcohol component constituting the amorphous resin A.

The present invention provides a toner for developing electrostatic images that is excellent in durability, resistance to bending of printed images, and storage stability under high-temperature and high-humidity conditions.

[Toner for developing electrostatic images]
The toner for developing electrostatic images according to the present invention (hereinafter also simply referred to as "toner") contains an amorphous resin A having an acidic group (hereinafter also simply referred to as "amorphous resin A"), a compound B (hereinafter also simply referred to as "compound B") having a polyolefin skeleton and at least one basic nitrogen-containing group selected from the group consisting of an amino group, an imino group, a cyano group, an azo group, a diazo group, and an azide group, and a release agent C, and contains an aliphatic alcohol having from 4 to 8 carbon atoms as an alcohol component constituting the amorphous resin A.
According to the above-mentioned constitution, a toner is provided which is excellent in durability, bending resistance of printed matter, and storage stability under high temperature and high humidity conditions.

The reason why the toner for developing electrostatic images of the present invention is excellent in durability, bending resistance of printed matter, and storage stability under high temperature and high humidity conditions is not clear, but is thought to be as follows.
Due to an acid-base interaction between the acidic groups of amorphous resin A and the basic nitrogen-containing groups of compound B, compound B is finely dispersed in amorphous resin A. As a result, the polyolefin chemically bonded to compound B is finely dispersed in amorphous resin A. It is thought that the highly hydrophobic release agent is finely dispersed by the polyolefin, resulting in a reduction in the amount of release agent on the toner surface, resulting in excellent durability.
Furthermore, it was surprisingly found that the inclusion of an aliphatic alcohol having 4 to 8 carbon atoms as the alcohol component constituting the amorphous resin A resulted in excellent bending resistance of the printed matter and excellent storage stability under high temperature and high humidity. To improve the bending resistance of the printed matter, it is important to have a high affinity between the toner and paper and increase the fixing strength, and it is known that an aliphatic alcohol is used. However, the use of an aliphatic alcohol increases the ester group concentration of the resin, which increases the hygroscopicity under high temperature and high humidity, resulting in a decrease in storage stability. It is believed that the inclusion of an aliphatic alcohol having 4 to 8 carbon atoms as the alcohol component constituting the amorphous resin A enabled appropriate hydrophilization and an increase in the ester group concentration, which resulted in excellent bending resistance of the printed matter and excellent storage stability under high temperature and high humidity.

The definitions of various terms used in this specification are shown below.
Whether a resin is crystalline or amorphous is determined by its crystallinity index. The crystallinity index is defined as the ratio of the softening point of the resin to the endothermic maximum peak temperature (softening point (°C)/endothermic maximum peak temperature (°C)) in the measurement method described in the Examples below. A crystalline resin is a resin with a crystallinity index of 0.6 or more and 1.4 or less. An amorphous resin is a resin with a crystallinity index of less than 0.6 or more than 1.4. The crystallinity index can be appropriately adjusted by adjusting the types and ratios of raw material monomers, as well as production conditions such as reaction temperature, reaction time, and cooling rate.
In this specification, the term "binder resin" refers to a resin component contained in the toner containing the amorphous resin A.
In the specification, the carboxylic acid component of the polyester resin includes not only the exemplified compounds but also anhydrides that decompose during the reaction to produce an acid, and alkyl esters of each carboxylic acid (the alkyl group has 1 to 3 carbon atoms).
The term "alkyl (meth)acrylate" refers to alkyl acrylate or alkyl methacrylate. The term "(iso)" in the alkyl moiety refers to normal alkyl or isoalkyl.

<Amorphous Resin A>
The amorphous resin A has an acidic group from the viewpoint of obtaining a toner that is excellent in durability, bending resistance of printed matter, and storage stability under high temperature and high humidity conditions.
Examples of the acidic group include a carboxy group, a sulfo group, and a phosphate group, with the carboxy group being preferred.
The amorphous resin A is not particularly limited as long as it has an acidic group, but examples thereof include polyester-based resins and polystyrene-based resins. Among these, polyester-based resins are preferred. In the case of polyester-based resins, the carboxyl group at the polymer chain terminal of the resin corresponds to at least the acidic group described above.
Examples of polyester resins include polyester resins and modified polyester resins, such as urethane-modified polyester resins in which polyester resins are modified with urethane bonds, epoxy-modified polyester resins in which polyester resins are modified with epoxy bonds, and composite resins containing polyester resin segments and vinyl resin segments.

[Polyester resin]
The polyester resin is, for example, a condensation product of an alcohol component and a carboxylic acid component.
Examples of the alcohol component include linear or branched aliphatic diols, alicyclic diols, aromatic diols, and trihydric or higher polyhydric alcohols. These alcohol components may be used alone or in combination of two or more.

In order to obtain a toner that is excellent in durability, bending resistance of printed matter, and storage stability under high temperature and high humidity, the amorphous resin A in the present invention contains an aliphatic alcohol having 4 to 8 carbon atoms as the alcohol component that constitutes the amorphous resin A. The number of carbon atoms in the aliphatic alcohol is preferably 4 to 6. The aliphatic alcohol may be a linear or branched aliphatic diol, an alicyclic diol, or a trihydric or higher polyhydric alcohol. It is also preferable that the aliphatic alcohol has a branched structure.

Examples of linear or branched aliphatic diols having 4 to 8 carbon atoms include 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2,2-dimethyl-1,3-propanediol (also known as neopentyl glycol), 1,6-hexanediol, and 1,8-octanediol. Among these, at least one selected from the group consisting of 1,4-butanediol, 2,3-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, and 1,8-octanediol is preferred, with 2,2-dimethyl-1,3-propanediol being more preferred.

Examples of trivalent or higher polyhydric alcohols having 4 to 8 carbon atoms include pentaerythritol, trimethylolpropane, and sorbitol.

From the viewpoint of obtaining a toner that exhibits excellent durability, bending resistance of printed matter, and storage stability under high temperature and high humidity conditions, the total content of aliphatic alcohols having 4 to 8 carbon atoms is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, and even more preferably 40 mol% or more, relative to 100 mol% of all alcohol components constituting amorphous resin A, and is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and even more preferably 65 mol% or less.

Examples of linear or branched aliphatic diols other than aliphatic alcohols having from 4 to 8 carbon atoms include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol. The ethylene glycol contained as an alcohol component constituting the amorphous resin A may be derived from polyethylene terephthalate.
Examples of alicyclic diols include hydrogenated bisphenol A [2,2-bis(4-hydroxycyclohexyl)propane] and alkylene oxide adducts of hydrogenated bisphenol A having 2 to 4 carbon atoms (average number of moles added: 2 to 12).

The aromatic diol is preferably an alkylene oxide adduct of bisphenol A, more preferably represented by formula (I):

(wherein ^OR1 and ^R2O are oxyalkylene groups, ^R1 and ^R2 each independently represent an ethylene group or a propylene group, x and y each represent the average number of moles of alkylene oxide added and are positive numbers, and the sum of x and y is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, more preferably 4 or less.)
It is an alkylene oxide adduct of bisphenol A represented by the formula:

Examples of alkylene oxide adducts of bisphenol A include propylene oxide adducts of bisphenol A [2,2-bis(4-hydroxyphenyl)propane] and ethylene oxide adducts of bisphenol A. These may be used alone or in combination.

From the viewpoint of obtaining a toner that exhibits excellent folding resistance in printed images, the total content of the ethylene oxide adduct of bisphenol A or the propylene oxide adduct of bisphenol A is preferably 70 mol% or less, more preferably 60 mol% or less, even more preferably 50 mol% or less, even more preferably 40 mol% or less, and preferably 0 mol% or more, relative to 100 mol% of all alcohol components constituting amorphous resin A.

Examples of trihydric or higher polyhydric alcohols other than aliphatic alcohols having 4 to 8 carbon atoms include glycerin.

When a trihydric or higher polyhydric alcohol is contained, the amount of the trihydric or higher polyhydric alcohol is preferably 2 mol% or more, more preferably 5 mol% or more, relative to 100 mol% of all alcohol components constituting the amorphous resin A, from the viewpoint of obtaining a toner that is excellent in durability, bending resistance of printed matter, and storage stability under high temperature and high humidity conditions, and is preferably 30 mol% or less, more preferably 20 mol% or less.

Examples of carboxylic acid components include dicarboxylic acids and tricarboxylic or higher polycarboxylic acids. These carboxylic acid components may be used alone or in combination.

Examples of dicarboxylic acids include aromatic dicarboxylic acids, linear or branched aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids. Among these, at least one selected from the group consisting of aromatic dicarboxylic acids and linear or branched aliphatic dicarboxylic acids is preferred.
Examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid, and terephthalic acid. Among these, isophthalic acid and terephthalic acid are preferred, and terephthalic acid is more preferred.
The amount of aromatic dicarboxylic acid is preferably 80 mol% or more, more preferably 90 mol% or more, and even more preferably 95 mol% or more, relative to 100 mol% of all carboxylic acid components constituting the amorphous resin A, and is preferably 100 mol% or less, more preferably 100 mol%.

The linear or branched aliphatic dicarboxylic acid preferably has 2 or more carbon atoms, more preferably 3 or more carbon atoms, and preferably 30 or less, more preferably 20 or less carbon atoms.
Examples of linear or branched aliphatic dicarboxylic acids include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, azelaic acid, and succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. Examples of succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms include dodecylsuccinic acid, dodecenylsuccinic acid, and octenylsuccinic acid. Among these, succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms is preferred.
The amount of the linear or branched aliphatic dicarboxylic acid is preferably 20 mol% or less, more preferably 10 mol% or less, and even more preferably 5 mol% or less, relative to 100 mol% of all carboxylic acid components constituting the amorphous resin A, and is preferably 0 mol% or more, more preferably 0 mol%.

The trivalent or higher polyvalent carboxylic acid is preferably a trivalent carboxylic acid, such as trimellitic acid.
When a trivalent or higher polycarboxylic acid is contained, the amount of the trivalent or higher polycarboxylic acid is preferably 30 mol% or less, more preferably 20 mol% or less, relative to 100 mol% of all carboxylic acid components constituting the amorphous resin A, and is preferably 0 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more.

The polyester resin may be a resin obtained by polycondensing a polycondensable monomer containing a carboxylic acid component and an alcohol component with polyethylene terephthalate, but from the perspective of obtaining a toner that has excellent durability, bending resistance of printed images, and storage stability under high temperature and humidity conditions, it is preferable that the polyester resin be a resin obtained by polycondensing polyethylene terephthalate.

Polyethylene terephthalate can be produced in accordance with conventional methods by polycondensation of ethylene glycol with terephthalic acid, dimethyl terephthalate, etc.

From the viewpoint of obtaining a toner having excellent durability, the intrinsic viscosity (hereinafter also referred to as "IV value") of polyethylene terephthalate is preferably 0.4 or more, more preferably 0.5 or more, even more preferably 0.55 or more, and is preferably 1.0 or less, more preferably 0.9 or less, even more preferably 0.8 or less, even more preferably 0.75 or less, even more preferably 0.7 or less. The IV value is an index of molecular weight. The IV value of polyethylene terephthalate can be adjusted by the polycondensation time, etc.
The IV value can be measured, for example, by dissolving a sample in a mixed solvent of phenol/tetrachloroethane = 60/40 (mass ratio) at a concentration of 0.4 g/dL, measuring with an Ubbelohde viscometer, and calculating according to the following formula.

(In the formula, k is Huggins' constant, C is the concentration of the sample solution (g/dL), η = (t ₁ /t ₀ ) - 1, t ₀ is the number of seconds it takes for the solvent alone to fall, and t ₁ is the number of seconds it takes for the sample solution to fall. k was set to 0.33.)

Commercially available polyethylene terephthalate products include "RAMAPET L1" (manufactured by Indorama Ventures, IV value: 0.60), "RAMAPET N2G" (manufactured by Indorama Ventures, IV value: 0.75), "TRN-NTJ" (manufactured by Teijin Limited, IV value: 0.53), and "TRN-RTJC" (manufactured by Teijin Limited, IV value: 0.64).

The equivalent ratio of the carboxyl groups of the carboxylic acid component to the hydroxyl groups of the alcohol component [COOH groups/OH groups] is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, more preferably 1.2 or less.

[Composite resin]
The composite resin contains a polyester resin segment and a vinyl resin segment, and the polyester resin segment is preferably made of the above-mentioned polyester resin.
The vinyl resin segment is preferably an addition polymer of raw material monomers containing a styrene compound, and more preferably an addition polymer of raw material monomers containing a styrene compound and a vinyl monomer having an aliphatic hydrocarbon group having from 3 to 22 carbon atoms.

The amount of the polyester resin segment in the composite resin is preferably 40% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 75% by mass or more, and is preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less.
The amount of the vinyl resin segment in the composite resin is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, even more preferably 30% by mass or less.

As for the composite resin, for example, the composite resins described in International Publication No. 2018/216336, Japanese Patent No. 6267579, Japanese Patent No. 6496970, etc. can be used.

[Method for producing amorphous resin A]
When the amorphous resin A is a polyester resin, it is obtained, for example, by polycondensation of an alcohol component and a carboxylic acid component.
If necessary, polycondensation may be carried out using an esterification catalyst such as tin(II) di(2-ethylhexanoate), dibutyltin oxide, or titanium diisopropylate bistriethanolamine in an amount of 0.01 to 5 parts by mass per 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component; or an esterification promoter such as gallic acid (equivalent to 3,4,5-trihydroxybenzoic acid) in an amount of 0.001 to 0.5 parts by mass per 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component.
The temperature of the polycondensation reaction is preferably 120° C. or higher, more preferably 160° C. or higher, and even more preferably 180° C. or higher, and is preferably 250° C. or lower, and more preferably 240° C. or lower. The polycondensation may be carried out in an inert gas atmosphere.

When the amorphous resin A is a composite resin, it may be produced by a method including, for example, step A of carrying out a polycondensation reaction of an alcohol component and a carboxylic acid component, and step B of carrying out an addition polymerization reaction of a raw material monomer of a vinyl resin segment and a bireactive monomer.
Step B may be carried out after step A, step A may be carried out after step B, or step A and step B may be carried out simultaneously.
A preferred method is to subject a part of the carboxylic acid component to a polycondensation reaction in step A, then carry out step B, and then add the remainder of the carboxylic acid component to the polymerization system, thereby further promoting the polycondensation reaction of step A and, if necessary, the reaction with the bireactive monomer.
The conditions for step A are the same as those for the above-described method for producing a polyester resin.

Examples of polymerization initiators for the addition polymerization reaction include peroxides such as dibutyl peroxide, persulfates such as sodium persulfate, and azo compounds such as 2,2'-azobis(2,4-dimethylvaleronitrile).
The amount of the polymerization initiator used is preferably 1 part by mass or more and 20 parts by mass or less based on 100 parts by mass of the raw material monomer of the vinyl resin segment.
The temperature of the addition polymerization reaction is preferably 110°C or higher, more preferably 130°C or higher, and preferably 220°C or lower, more preferably 210°C or lower.

[Physical Properties of Amorphous Resin A]
The softening point of the amorphous resin A is preferably 70°C or higher, more preferably 90°C or higher, and even more preferably 100°C or higher, from the viewpoint of further improving storage stability under high temperature and high humidity conditions, and is preferably 160°C or lower, more preferably 150°C or lower, and even more preferably 140°C or lower, from the viewpoint of further improving low-temperature fixability.
The glass transition temperature of the amorphous resin A is preferably 30°C or higher, more preferably 35°C or higher, and even more preferably 40°C or higher, from the viewpoint of further improving storage stability under high-temperature and high-humidity conditions, and is preferably 80°C or lower, more preferably 75°C or lower, and even more preferably 70°C or lower, from the viewpoint of further improving low-temperature fixability.

From the viewpoint of further improving durability, bending resistance of printed matter, and storage stability under high temperature and high humidity conditions, the acid value of the amorphous resin A is preferably 2 mgKOH/g or more, more preferably 5 mgKOH/g or more, even more preferably 10 mgKOH/g or more, and still more preferably 12 mgKOH/g or more, and is preferably 40 mgKOH/g or less, more preferably 35 mgKOH/g or less, and still more preferably 30 mgKOH/g or less.
The softening point, glass transition temperature, and acid value of the amorphous resin A can be appropriately adjusted by adjusting the types and amounts of raw material monomers used, as well as production conditions such as reaction temperature, reaction time, and cooling rate, and these values can be determined by the methods described in the examples.
When two or more kinds of amorphous resins A are used in combination, it is preferable that the softening point, glass transition temperature, and acid value of the mixture thereof are each within the above-mentioned ranges.

In the binder resin of the toner, the content of amorphous resin A is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and is 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and even more preferably 88% by mass or less.

In the present invention, the polyester resin may contain two or more polyester resins whose softening points differ from each other by preferably 5° C. or more, more preferably 10° C. or more, from the viewpoint of durability. The softening point of the polyester resin having the lowest softening point among the two or more polyester resins is preferably 70° C. or more, more preferably 90° C. or more, even more preferably 100° C. or more, from the viewpoint of further improving durability. Furthermore, the softening point of the polyester resin having the highest softening point among the two or more polyester resins is preferably 110° C. or more, more preferably 120° C. or more, and from the viewpoint of further improving low-temperature fixability, it is preferably 160° C. or less, more preferably 150° C. or less, even more preferably 140° C. or less. When two or more polyester resins are contained, it is preferable to use two or more polyester resins in combination, from the viewpoint of improving toner productivity.
The difference between the softening point of the high-softening-point polyester resin and the softening point of the low-softening-point polyester resin is preferably 5°C or more, more preferably 10°C or more, and even more preferably 15°C or more. From the viewpoints of durability and low-temperature fixability, the difference is preferably 60°C or less, more preferably 50°C or less, and even more preferably 40°C or less.

When two types of polyester resins are used, the mass ratio of the high-softening point polyester resin to the low-softening point polyester resin (high-softening point polyester resin/low-softening point polyester resin) is preferably 10/90 or more, more preferably 20/80 or more, even more preferably 30/70 or more, and is preferably 90/10 or less, more preferably 80/20 or less, even more preferably 70/30 or less.

<Compound B>
From the viewpoint of obtaining a toner excellent in durability, bending resistance of printed matter, and storage stability under high temperature and high humidity conditions, compound B has a polyolefin skeleton and a basic nitrogen-containing group. Compound B is preferably dispersed in amorphous resin A. In other words, compound B is preferably dispersed inside toner particles.

The basic nitrogen-containing group is at least one selected from the group consisting of an amino group, an imino group (=NH), a cyano group (-CN), an azo group (-N=N-), a diazo group (=N ₂ ), and an azide group (-N ₃ ).
The amino group may be a primary amino group, a secondary amino group, or a tertiary amino group.
From the viewpoint of the affinity of the compound B to the binder resin A, an amino group is preferred.

Functional groups other than the basic nitrogen-containing group include, for example, a hydroxy group, a formyl group, an acetal group, an oxime group, and a thiol group.

Compound B has a polyolefin skeleton from the viewpoint of obtaining a toner that is excellent in durability, bending resistance of printed matter, and storage stability under high temperature and high humidity conditions.
Examples of polyolefins that form the polyolefin skeleton include polyethylene, polypropylene, polybutylene, polymethylpentene, polytetradecene, polyhexadecene, polyoctadecene, polyeicosene, polydococene, and copolymers of these monomers.
The polyolefin skeleton is preferably a polypropylene skeleton, a polyethylene skeleton, or a propylene/ethylene copolymer skeleton, more preferably a polyethylene skeleton or a polypropylene skeleton, and even more preferably a polypropylene skeleton.

Compound B is, for example, a reaction product of a basic nitrogen-containing group source and a polyolefin backbone source.
Examples of the basic nitrogen-containing group raw material include polyamine compounds.
Examples of the polyamine compound include polyalkyleneamine, polyallylamine, and polyaminoalkyl methacrylate.
As the polyamine compound, from the viewpoint of adsorption to a binder resin having an acidic group, a polyalkyleneamine having at least one amino group selected from the group consisting of a primary amino group and a secondary amino group is preferred.
Examples of polyalkyleneamines include polyethyleneamine, polypropyleneamine, and polybutyleneamine.
Examples of polyethyleneamines include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and polyethyleneimine having a number average molecular weight of 300 to 15,000. Among these, tetraethylenepentamine, pentaethylenehexamine, and polyethyleneimine having a number average molecular weight of 300 to 3,000 are more preferred, and tetraethylenepentamine is even more preferred.

The polyethyleneimine preferably contains, for example, a primary amino group, a secondary amino group, and a tertiary amino group, and has a branched structure.
Commercially available polyethyleneimine products include, for example, "SP-003,""SP-006,""SP-012," and "SP-018" from the "Epomin" series (all manufactured by Junsei Chemical Co., Ltd.).
An example of the polyaminoalkyl methacrylate is polydimethylaminoethyl methacrylate.

The amine value of the basic nitrogen-containing group raw material is preferably 1 mmol/g or more, more preferably 3 mmol/g or more, even more preferably 5 mmol/g or more, and is preferably 50 mmol/g or less, more preferably 40 mmol/g or less, even more preferably 30 mmol/g or less, even more preferably 25 mmol/g or less.
The amine value of the basic nitrogen-containing group raw material can be measured by the method described in the Examples below.

From the viewpoint of adsorption to the resin having acidic groups, the number average molecular weight of the basic nitrogen-containing group raw material is preferably 100 or more, more preferably 140 or more, and even more preferably 180 or more, and is preferably 15,000 or less, more preferably 10,000 or less, even more preferably 5,000 or less, even more preferably 3,000 or less, and even more preferably 2,000 or less.

Examples of polyolefin backbone raw materials include polyolefins having reactive functional groups. Examples of reactive functional groups include carboxy groups, halogeno groups, epoxy groups, formyl groups, and isocyanate groups. The carboxy groups may be their anhydrides. Examples of halogeno groups include chloro groups, bromo groups, and iodo groups. Among these, from the viewpoints of safety and reactivity, carboxy groups or their anhydrides and halogeno groups are preferred, and carboxy groups or their anhydrides are more preferred.
Examples of polyolefin backbone raw materials include maleic anhydride-modified polyolefins such as maleic anhydride-modified polypropylene, maleic anhydride-modified polyethylene, maleic anhydride-modified ethylene/propylene copolymer, and maleic anhydride-modified ethylene/hexene copolymer.
The acid-modified polyolefin is preferably a polyolefin modified with an acid at one end, more preferably a polyolefin modified with maleic anhydride at one end.

The content of polyolefins having reactive functional groups in the polyolefin skeleton raw material is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and is 100% by mass or less, even more preferably 100% by mass.

The melting point of the polyolefin backbone raw material is preferably 60°C or higher, more preferably 70°C or higher, even more preferably 80°C or higher, and preferably 160°C or lower, more preferably 150°C or lower, even more preferably 140°C or lower.

The number average molecular weight of the polyolefin skeleton raw material is preferably 100 or more, more preferably 200 or more, even more preferably 300 or more, and preferably 5,000 or less, more preferably 3,000 or less, even more preferably 2,500 or less.
The number average molecular weight of the polyolefin skeleton raw material can be determined, for example, by gel permeation chromatography (GPC).

Examples of polypropylene skeleton raw materials having a polypropylene skeleton include the "Yumex" series "100Ts," "110Ts," "1001," and "1010" (all manufactured by Sanyo Chemical Industries, Ltd.), the "Hardlen" series "13-LP," "13-LLP," "14-LWP," "15-LP," "15-LLP," "16-LP," "DX-526P," "CY-9122P," "CY-9124P," "HM-21P," "M-28P," "F-2P," and "F-6P" (all manufactured by Toyobo Co., Ltd.), and the "Toyotack" series "M-100," "M-300," "M-312," and "PMA" H1000P" and "PMA-F2" (all manufactured by Toyobo Co., Ltd.), the "Superclone" series "C", "L-206", "813A", "803M", "803MW", "803LT", "1026", "803L", "814H", "390S", "814B", "360T", "370M", "2027MB", "822", "892L", "930", "842LM", and "851L" (all manufactured by Nippon Paper Industries Co., Ltd.), and "X-10065", "X-10088", "X-10082", "X-10087", "X-10053", and "X-10052" (all manufactured by Baker Hughes).

[Method for producing compound B]
Compound B is obtained by reacting a basic nitrogen-containing group source with a polyolefin backbone source.
The reaction temperature is preferably 100°C or higher, more preferably 120°C or higher, and even more preferably 150°C or higher, and is preferably 200°C or lower, more preferably 180°C or lower, and even more preferably 170°C or lower.

The ratio (A/N) of the number of moles (A) of reactive functional groups in the polyolefin backbone raw material to the number of moles (N) of basic nitrogen in the basic nitrogen-containing group raw material is preferably 0.05 or more, more preferably 0.1 or more, and is preferably 0.8 or less, more preferably 0.7 or less, and even more preferably 0.6 or less.

The ratio (A/N) is calculated as follows.
Ratio (A/N) = 1000 x [number of reactive functional groups per molecule of aliphatic hydrocarbon group raw material (A) x (charged amount of aliphatic hydrocarbon group raw material/molecular weight of aliphatic hydrocarbon group raw material)] / [amine value of basic nitrogen-containing group raw material (mmol/g) x charged amount of basic nitrogen-containing group raw material]
However, in the polyolefin skeleton raw material having a maleic anhydride moiety, the number of reactive functional groups per molecule is set to one.
The amine value of the basic nitrogen-containing group source can be measured by hydrochloric acid titration or perchloric acid titration.

In the case of the reaction between a polyamine compound and a maleic anhydride-modified polyolefin, it is preferable that an imide bond is formed by the reaction, which can be confirmed by observing a peak (1700 cm ⁻¹ ) derived from the imide bond by infrared spectroscopy (hereinafter also simply referred to as “IR”).

[Physical properties of compound B]
From the viewpoint of improving durability, bending resistance of printed matter, and storage stability under high temperature and high humidity, the melting point of compound B is preferably 40°C or higher, more preferably 50°C or higher, even more preferably 65°C or higher, and even more preferably 80°C or higher, and is preferably 150°C or lower, more preferably 140°C or lower, and even more preferably 130°C or lower.
The melting point was measured by the method described in the Examples.

From the viewpoint of improving durability, the folding resistance of printed matter, and storage stability under high temperature and humidity conditions, the number average molecular weight of compound B is preferably 500 or more, more preferably 800 or more, even more preferably 1,000 or more, and is preferably 20,000 or less, more preferably 10,000 or less, even more preferably 7,000 or less.

From the viewpoint of improving durability, the folding resistance of printed matter, and storage stability under high temperature and high humidity conditions, the content of compound B is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more, relative to 100 parts by mass of binder resin, and is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less.

<Release Agent C>
Examples of the release agent C include hydrocarbon waxes or oxides thereof, ester waxes, fatty acid amides, fatty acids, fatty acid metal salts, and higher alcohols. Among these, hydrocarbon waxes or oxides thereof, or ester waxes are preferred, hydrocarbon waxes or oxides thereof are more preferred, and hydrocarbon waxes are even more preferred.
Examples of hydrocarbon waxes include polyolefin waxes such as polypropylene wax, polyethylene wax, and polypropylene-polyethylene copolymer wax; paraffin wax, microcrystalline wax, Fischer-Tropsch wax, and Sasol wax.
Examples of the ester wax include carnauba wax, montan wax or deacidified waxes thereof, fatty acid ester wax, etc. These may be used alone or in combination of two or more.

The melting point of the release agent C is preferably 60° C. or higher, more preferably 70° C. or higher, and is preferably 160° C. or lower, more preferably 130° C. or lower, and even more preferably 115° C. or lower. The melting point of the release agent C can be determined by the method described in the examples below.
The content of the release agent C is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more, relative to 100 parts by mass of the binder resin, and is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less.

<Charge control agent>
The toner may contain a charge control agent, which may be either a positively chargeable charge control agent or a negatively chargeable charge control agent.
Examples of positively chargeable charge control agents include nigrosine dyes such as "Nigrosine Base EX,""Oil Black BS,""Oil Black SO,""BontronN-01,""BontronN-04,""BontronN-07,""BontronN-09," and "Bontron N-11" (all manufactured by Orient Chemical Industries Co., Ltd.); triphenylmethane dyes containing a tertiary amine as a side chain; quaternary ammonium salt compounds such as "Bontron P-51" (manufactured by Orient Chemical Industries Co., Ltd.), cetyltrimethylammonium bromide, and "COPY CHARGE PX" (manufactured by Orient Chemical Industries Co., Ltd.). VP435 (manufactured by Clariant), etc.; polyamine resins, such as "AFP-B" (manufactured by Orient Chemical Industries Co., Ltd.), etc.; imidazole derivatives, such as "PLZ-2001" and "PLZ-8001" (both manufactured by Shikoku Chemical Industries Co., Ltd.), etc.; styrene-acrylic resins, such as "FCA-701PT" (manufactured by Fujikura Chemical Co., Ltd.), etc.

Examples of negatively chargeable charge control agents include metal-containing azo dyes such as "Balifast Black 3804," "Bontron S-31," "Bontron S-32," "Bontron S-34," and "Bontron S-36" (all manufactured by Orient Chemical Industries, Ltd.), "Eizenspiron Black TRH," and "T-77" (manufactured by Hodogaya Chemical Co., Ltd.); metal compounds of benzilic acid compounds such as "LR-147" and "LR-297" (manufactured by Nippon Carlit Co., Ltd.); metal compounds of salicylic acid compounds such as "Bontron E-81," "Bontron E-84," "Bontron E-88," and "Bontron E-304" (all manufactured by Orient Chemical Industries, Ltd.), and "TN-105" (manufactured by Hodogaya Chemical Co., Ltd.); copper phthalocyanine dyes; quaternary ammonium salts such as "COPY CHARGE NX VP434" (manufactured by Clariant), nitroimidazole derivatives, and organometallic compounds.

The content of the charge control agent is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less, per 100 parts by mass of the binder resin.

<Coloring Agent>
The toner may contain a colorant.
As the colorant, dyes, pigments, etc. used as colorants for toners can be used, and examples thereof include carbon black, phthalocyanine blue, permanent brown FG, brilliant fast scarlet, pigment green B, rhodamine-B base, solvent red 49, solvent red 146, solvent blue 35, quinacridone, carmine 6B, and disazo yellow. The toner of the present invention may be either a black toner or a color toner other than black.

From the viewpoint of improving the image density of the toner, the content of the colorant is preferably 1 part by weight or more, more preferably 2 parts by weight or more, and preferably 40 parts by weight or less, more preferably 20 parts by weight or less, and even more preferably 10 parts by weight or less, per 100 parts by weight of the binder resin.

The toner may also contain additives such as magnetic powder, flowability improvers, conductivity adjusters, reinforcing fillers such as fibrous materials, antioxidants, anti-aging agents, and cleaning improvers.

The toner includes, for example, toner particles. The toner particles preferably contain an amorphous resin A, a compound B, and a release agent C. A charge control agent, a colorant, and other additives are preferably contained in the toner particles.
Although the toner particles can be used as they are, it is preferable to use the toner after adding an external additive, which will be described later, to the surface of the toner particles.
The toner is preferably used as a dry toner.

[Toner manufacturing method]
The toner may be obtained by any known method such as a melt-kneading method, an emulsion phase inversion method, an emulsion polymerization method, or an emulsion aggregation method. However, from the viewpoint of productivity and dispersibility of the colorant, a pulverized toner obtained by a melt-kneading method is preferred.

In the case of pulverized toner, the toner can be produced by, for example,
The method includes: step 1: a step of melt-kneading a mixture containing an amorphous resin A, a compound B, and a release agent C; and step 2: a step of pulverizing and classifying the melt-kneaded product obtained in step 1 to obtain toner particles.

In step 1, the mixture may contain additives such as a charge control agent and a colorant. These toner raw materials are preferably mixed in advance in a mixer such as a Henschel mixer or a ball mill, and then supplied to the kneader.
The melt-kneading in step 1 can be carried out using a known kneader such as an internal kneader, a single-screw extruder, a twin-screw extruder, an open-roll kneader, etc. Among these, a twin-screw extruder is preferred because it allows the kneading temperature to be set over a wide range.
The melt-kneading temperature is preferably 80°C or higher and 160°C or lower.
The melt-kneaded product obtained in step 1 is cooled to a degree that allows it to be pulverized, and then subjected to the subsequent step 2.

The pulverization in step 2 may be carried out in multiple stages. For example, the melt-kneaded product may be coarsely pulverized to a particle size of 1 mm to 5 mm, and then finely pulverized to a desired particle size.
Examples of mills suitable for coarse pulverization include hammer mills, atomizers, and rotoplexes. Examples of mills suitable for fine pulverization include fluidized bed jet mills, impaction plate jet mills, and rotary mechanical mills. Among these, from the viewpoint of pulverization efficiency, fluidized bed jet mills and impaction plate jet mills are preferred, and impaction plate jet mills are more preferred.

Classifiers used for classification include, for example, rotor classifiers, air classifiers, inertial classifiers, and sieve classifiers. During the classification process, any pulverized material that is removed due to insufficient pulverization may be subjected to the pulverization process again, and the pulverization and classification processes may be repeated as necessary.

From the viewpoint of obtaining high-quality images, the volume median particle size (D ₅₀ ) of the toner particles is preferably 2 μm or more, more preferably 3 μm or more, and even more preferably 4 μm or more, and is preferably 10 μm or less, and more preferably 8 μm or less.

The toner is preferably treated by adding a fluidizing agent or the like as an external additive to the surface of the toner particles.
Examples of external additives include inorganic material particles such as hydrophobic silica, titanium oxide, alumina, cerium oxide, and carbon black, and polymer particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, hydrophobic silica is preferred.
When an external additive is used, the amount of the external additive added is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, even more preferably 2 parts by mass or more, and preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less, even more preferably 4 parts by mass or less, relative to 100 parts by mass of toner particles.

Toner is used to develop latent images formed in electrophotography, electrostatic recording, electrostatic printing, etc. Toner can be used as a one-component developer or mixed with a carrier to form a two-component developer.

[measurement]
[Acid value of resin]
The acid value of the resin was measured based on the method of JIS K 0070. However, the measurement solvent was changed from the mixed solvent of ethanol and ether specified in JIS K 0070 to a mixed solvent of acetone and toluene (acetone:toluene = 1:1 (volume ratio)).

[Resin softening point, glass transition temperature, etc.]
(1) Softening Point Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), 1 g of a sample was extruded from a nozzle having a diameter of 1 mm and a length of 1 mm while applying a load of 1.96 MPa with a plunger while heating at a temperature increase rate of 6°C/min. The plunger depression amount of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was taken as the softening point.
(2) Maximum Endothermic Peak Temperature Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), a sample was cooled from room temperature (20°C) to 0°C at a temperature drop rate of 10°C/min, held there for 1 minute, and then heated to 180°C at a temperature increase rate of 10°C/min, while being measured. The temperature of the highest endothermic peak observed was taken as the maximum endothermic peak temperature.
(3) Glass Transition Temperature Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of a sample was weighed into an aluminum pan, heated to 200°C, and cooled from that temperature to 0°C at a rate of 10°C/min. Next, measurement was performed while raising the temperature to 150°C at a rate of 10°C/min. The glass transition temperature was determined as the temperature at the intersection of an extension of the baseline below the maximum endothermic peak temperature and a tangent line showing the maximum slope from the rising part of the peak to the peak apex.

[Number average molecular weight and weight average molecular weight of polyester resin]
The molecular weight distribution was measured by gel permeation chromatography (GPC) according to the following method, and the number average molecular weight Mn and weight average molecular weight Mw of the resin were determined.
(1) Preparation of sample solution: The resin was dissolved in chloroform to a concentration of 0.5 g/100 mL. This solution was then filtered through a fluororesin filter (manufactured by Sumitomo Electric Industries, Ltd., product name: FP-200) with a pore size of 2 μm to remove insoluble components, thereby obtaining a sample solution.
(2) Molecular Weight Measurement Using the following equipment, chloroform was used as the eluent at a flow rate of 1 mL per minute, and the column was stabilized in a thermostatic bath at 40°C. 100 μL of sample solution was injected into the column for measurement. The molecular weight of the sample was calculated based on a calibration curve prepared in advance. For the calibration curve, several types of monodisperse polystyrene with known molecular weights (manufactured by Tosoh Corporation: 2.63 × 10 ³ , 2.06 × 10 ⁴ , 1.02 × 10 ⁵ , and manufactured by GL Sciences Inc.: 2.10 × 10 ³ , 7.00 × 10 ³ , 5.04 × 10 ⁴ ) were used as standard samples.
Measuring device: CO-8010 (product name, manufactured by Tosoh Corporation)
Analytical column: GMH _XL + G3000H _XL (both product names, manufactured by Tosoh Corporation)

[Melting points of wax and compound B]
Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of a sample was weighed into an aluminum pan, heated to 200°C, and then cooled from 200°C to 0°C at a temperature decrease rate of 10°C/min. The sample was then heated at a temperature increase rate of 10°C/min, the calorific value was measured, and the maximum endothermic peak temperature was taken as the melting point.

[Amine value of basic nitrogen-containing group raw material]
The amine value of the basic nitrogen-containing group raw material was measured based on the method of JIS K2501: 2003, except that the measurement solvent was changed from chlorobenzene specified in JIS K2501: 2003 to chloroform.

[Volume Median Particle Size (D ₅₀ ) of Toner]
The volume median particle diameter of the toner was measured as follows.
- Measuring instrument: Coulter Multisizer III (product name, manufactured by Beckman Coulter)
Aperture diameter: 50 μm
Analysis software: Multisizer III version 3.51 (product name, manufactured by Beckman Coulter)
Electrolyte: Isoton II (product name, manufactured by Beckman Coulter)
Dispersion: Polyoxyethylene lauryl ether (manufactured by Kao Corporation, trade name: Emulgen 109P, HLB: 13.6) was dissolved in the electrolytic solution to obtain a dispersion with a concentration of 5% by mass.
Dispersion conditions: 10 mg of the measurement sample was added to 5 mL of the dispersion liquid, and the mixture was dispersed for 1 minute using an ultrasonic disperser. Thereafter, 25 mL of the electrolyte solution was added, and the mixture was further dispersed for 1 minute using the ultrasonic disperser to prepare a sample dispersion liquid.
Measurement conditions: The sample dispersion was added to 100 mL of the electrolyte to adjust the concentration to a level that would allow the particle diameters of 30,000 particles to be measured in 20 seconds, and the volume median particle diameter (D ₅₀ ) was then determined from the particle size distribution.

[Production of alkenyl succinic anhydride]
(Production of alkylene compound A)
Propylene tetramer (manufactured by Nippon Oil Corporation, trade name: "Light Tetramer") was fractionally distilled under heating conditions of 183 to 208°C to obtain an alkylene compound (a). The obtained alkylene compound (a) had 40 peaks in gas chromatography mass spectrometry, which will be described later. The distribution of the alkylene compound was measured according to the analysis of alkylene compound A by mass spectrometry gas chromatography in JP 2014-013384 A, and was found _{to be C9H18: 0.5 mass%, C10H20: 4 mass%, C11H22: 20 mass%, C12H24 : 66 mass % , C13H26 :} 9 mass%, and _C14H28 : 0.5 mass% ₍ 6 _peaks corresponding to _alkylene compounds having 9 to 14 carbon atoms).

(Production of alkenyl succinic anhydride)
A 1 L autoclave manufactured by Nitto Koatsu Co., Ltd. was charged with 542.4 g of alkylene compound A, 157.2 g of maleic anhydride, 0.4 g of antioxidant Chelex-O (manufactured by SC Organic Chemical Co., Ltd., Triisooctyl phosphate), and 0.1 g of butylhydroquinone as a polymerization inhibitor, and pressurized and nitrogen-purged (0.2 MPaG) was repeated three times. After stirring was started at 60 ° C, the temperature was raised to 230 ° C over 1 hour and the reaction was carried out for 6 hours. The pressure when the reaction temperature was reached was 0.3 MPaG. After completion of the reaction, the mixture was cooled to 80 ° C, returned to normal pressure (101.3 kPa), and transferred to a 1 L four-neck flask. The temperature was raised to 180 ° C with stirring, and the remaining alkylene compound was distilled off at 1.3 kPa over 1 hour. The mixture was cooled to room temperature (25° C.) and then returned to atmospheric pressure (101.3 kPa), yielding 406.1 g of the target alkenyl succinic anhydride. The average molecular weight of the alkenyl succinic anhydride calculated from the acid value was 268.

[Production of Resin H and Resin L]
Production examples H1 to H7, H10 to H13, H15, H16, L1 to L7, L10 to L15
(Production of Resins H-1 to H-7, H-10 to H-13, H-15, H-16, L-1 to L-7, L-10 to L-15)
The raw material monomers for the polyester resin, the esterification catalyst, and gallic acid shown in Tables 1 and 2 were placed in a 5-liter four-neck flask equipped with a nitrogen inlet tube, a stirrer, and a thermocouple, and after maintaining the temperature at 180°C for 1 hour under a nitrogen atmosphere, the temperature was increased from 180°C to 230°C at a rate of 10°C/hr, and then polycondensation was carried out at 230°C for 5 hours. The reaction was further carried out at 230°C under a reduced pressure of 10 kPa until the softening point shown in Tables 1 and 2 was reached, thereby obtaining polyester resins.

Production examples H8, H9, L8, L9
(Resin H-8, H-9, L-8, L-9)
The raw material monomers for the polyester resins, the esterification catalyst, and gallic acid shown in Tables 1 and 2 were placed in a 5-liter four-neck flask equipped with a nitrogen inlet tube, a dehydration tube fitted with a fractionating column through which hot water at 98°C was passed, a stirrer, and a thermocouple, and the mixture was kept at 180°C for 1 hour under a nitrogen atmosphere, then the temperature was increased from 180°C to 230°C at a rate of 10°C/hr, and polycondensation was then carried out at 230°C for 5 hours. The reaction was further carried out at 230°C under a reduced pressure of 10 kPa until the softening points shown in Tables 1 and 2 were reached, yielding polyester resins.

Production example H14
(Production of Resin H-14)
The raw material monomers for polyester resins other than trimellitic anhydride, an esterification catalyst, and gallic acid shown in Table 1 were placed in a 5-liter four-neck flask equipped with a nitrogen inlet tube, a stirrer, and a thermocouple, and after maintaining the temperature at 180°C for 1 hour under a nitrogen atmosphere, the temperature was increased from 180°C to 230°C at a rate of 10°C/hr, and then polycondensation was carried out at 230°C for 5 hours. The temperature was then lowered to 210°C, and trimellitic anhydride was added. The reaction was carried out at 210°C for 1 hour, and then further reaction was carried out at 210°C under a reduced pressure of 10 kPa until the softening point shown in Table 1 was reached, thereby obtaining polyester resins.

Production example, H17, L16
(Production of Resins H-17 and L-16)
The raw material monomers for the polyester resin, the esterification catalyst, and gallic acid shown in Tables 1 and 2 were placed in a 5-liter four-neck flask equipped with a nitrogen inlet tube, a stirrer, and a thermocouple, and the temperature was raised to 235°C under a nitrogen atmosphere, followed by polycondensation at 235°C for 6 hours. The temperature was then lowered to 210°C, and the reaction was continued under a reduced pressure of 10 kPa until the softening point shown in Tables 1 and 2 was reached, yielding a polyester resin.

[Production of Compound B]
Manufacturing example B1
(Production of Compound B-1)
A 2 L four-neck flask equipped with a condenser, a nitrogen inlet tube, a stirrer, a dehydration tube, and a thermocouple was charged with 28 g of tetraethylenepentamine (amine value 23 mmol/g) as a basic nitrogen-containing group raw material, 300 g of one-terminal maleic anhydride-modified polypropylene (PPSA1000) (Baker Hughes "X-10065", melting point 108 ° C, number average molecular weight 1,000) as a wax affinity group raw material, and 328 g of xylene (Fujifilm Wako Pure Chemical Industries, Ltd.), and the atmosphere in the reaction vessel was purged with nitrogen gas. The reaction vessel was heated to 150 ° C and maintained for 1 hour, then heated to 160 ° C and maintained for 1 hour, and the pressure in the flask was reduced to 8.3 kPa to carry out the reaction while distilling off the solvent. IR analysis confirmed that the peak (1780 cm ⁻¹ ) of the acid anhydride derived from PPSA had disappeared and the peak (1700 cm ⁻¹ ) derived from the imide bond had appeared, yielding Compound B-1. The melting point is shown in Table 3.

Manufacturing example B2
(Production of Compound B-2)
Compound B-2 was obtained in the same manner as in Production Example B1, except that the wax-compatible group raw material was changed to one-terminal maleic anhydride-modified polypropylene (PPSA2500) ("X-10088" manufactured by Baker Hughes, melting point 119°C, number average molecular weight 2,500) and the amounts of basic nitrogen-containing group raw material and xylene were changed as shown in Table 3. The melting points are shown in Table 3.

[Toner production]
Example 1
100 parts by mass of polyester resin (60 parts by mass of resin H-1, 40 parts by mass of resin L-1), 3 parts by mass of compound B-1, 4 parts by mass of carbon black "MOGUL (registered trademark) L" (manufactured by Cabot Corporation), 1 part by mass of negatively chargeable charge control agent "Bontron (registered trademark) S-34" (manufactured by Orient Chemical Industries Co., Ltd.), and 6 parts by mass of paraffin wax "HNP-9" (manufactured by Nippon Seiro Co., Ltd., melting point 77°C) as release agent C were mixed in a Henschel mixer to obtain a mixture.
The resulting mixture was melt-kneaded using a co-rotating twin-screw extruder having a kneading section with a total length of 1560 mm, a screw diameter of 42 mm, and a barrel inner diameter of 43 mm at a screw rotation speed of 200 r/min and a barrel temperature setting of 100° C. to obtain a melt-kneaded product. The feed rate of the mixture was 20 kg/hr, and the average residence time was about 18 seconds.
The resulting melt-kneaded product was cooled and coarsely pulverized, then pulverized in a jet mill and classified to obtain powder (toner base particles) having a volume median particle size (D ₅₀ ) of 7.0 μm.
100 parts by mass of the obtained powder (toner base particles) and 1.5 parts by mass of hydrophobic silica "RY50" (manufactured by Nippon Aerosil Co., Ltd., hydrophobic treatment agent: silicone oil, average particle size 40 nm) and 1.0 part by mass of hydrophobic silica "R972" (manufactured by Nippon Aerosil Co., Ltd., hydrophobic treatment agent: DMDS, average particle size 16 nm) as external additives were mixed in a Henschel mixer for 3 minutes to obtain a toner. The evaluation results of the obtained toner are shown in Table 4.

Examples 2 to 17, Comparative Examples 1 to 5
A toner was obtained in the same manner as in Example 1, except that the types and amounts of the polyester resin, compound B, and release agent C used in Example 1 were changed to the types and amounts of the aqueous dispersions of resin particles shown in Table 4. The evaluation results of the obtained toner are shown in Table 4.

[evaluation]
[Heat-resistant storage stability of toner]
10 g of toner was placed in a 50 mL plastic cup and kept in an environment of 50°C and 60% RH for 24 hours. Thereafter, three sieves, namely, sieve A (mesh size 250 μm), sieve B (mesh size 150 μm), and sieve C (mesh size 75 μm), were placed one on top of the other in a powder tester (manufactured by Hosokawa Micron Corporation). 10 g of toner was placed on sieve A and vibrated for 60 seconds. The value (α) calculated from the following formula was used to evaluate fluidity based on the following evaluation criteria. The larger the value, the better.
α=100−[(toner mass (g) remaining on sieve A)+(toner mass (g) remaining on sieve B)×0.6+(toner mass (g) remaining on sieve C)×0.2]/10(g)×100

[Bending resistance]
The toner was loaded into a copy machine "AR-505" (manufactured by Sharp Corporation) with a modified fuser that allowed for off-machine fusing, and a printout was obtained in an unfixed state (print area: 20 cm x 20 cm, deposition amount: 0.5 mg/ ^cm² ). The printout was then fixed using a fuser (fixing speed: 300 mm/sec) adjusted to a total fusing pressure of 40 kgf, with the fusing roll temperature set to 160°C. The image was folded inward at 50 g/ ^cm² for 30 seconds, reopened, and the damaged image was wiped off with a soft cloth. The maximum width of the image defect, after which the printout's folding resistance was measured. The smaller the maximum width of the image defect, the better the printout's folding resistance. The fixing paper used was "CopyBond SF-70NA" (manufactured by Sharp Corporation, 75 g/ ^m² ).

[Toner durability]
The toner was loaded onto a printing machine "PagePresto N-4" (manufactured by Casio Computer Co., Ltd., fixing: contact fixing method, development: non-magnetic single-component development method, developing roll diameter: 2.3 cm), and a diagonal stripe pattern with a blackening rate of 5.5% was continuously printed in an environment of 32°C temperature and 85% humidity. During the printing, a black solid image was printed every 500 sheets, and the presence or absence of streaks on the image was checked. Printing was stopped when streaks appeared on the image, and continued up to a maximum of 9,000 sheets. The number of printed sheets up to the point where streaks were visually observed on the image was taken as the number of sheets on which streaks appeared due to toner fusing and adhering to the developing roll, and durability was evaluated. In other words, the greater the number of sheets on which streaks did not appear, the higher the durability of the toner can be determined.

From the results of the above examples and comparative examples, it can be seen that by containing amorphous resin A having an acidic group, compound B, and release agent C, a toner can be obtained that is excellent in durability, bending resistance of printed matter, and storage stability under high temperature and humidity conditions.

Claims (8)

A toner for developing electrostatic images, comprising: an amorphous resin A having an acidic group; a compound B having a polyolefin skeleton and at least one basic nitrogen-containing group selected from the group consisting of an amino group, an imino group, a cyano group, an azo group, a diazo group, and an azido group; and a release agent C, wherein the alcohol component constituting the amorphous resin A is an aliphatic alcohol having from 4 to 8 carbon atoms,
the content of aliphatic alcohols having 4 to 8 carbon atoms is 10 mol % or more relative to 100 mol % of all alcohol components constituting the amorphous resin A,
The toner for developing electrostatic images, wherein the release agent C is a hydrocarbon wax. The toner for developing electrostatic images according to claim 1, wherein compound B is a reaction product of a basic nitrogen-containing group raw material and a polyolefin skeleton raw material. The toner for developing electrostatic images according to claim 1 or 2, wherein the polyolefin skeleton is a polyethylene skeleton or a polypropylene skeleton. The toner for developing electrostatic images according to any one of claims 1 to 3, wherein the basic nitrogen-containing group is an amino group. The toner for developing electrostatic images according to any one of claims 1 to 4, wherein the acid value of the amorphous resin A is 5 mg KOH/g or more and 40 mg KOH/g or less. 6. The toner for developing electrostatic images according to claim 1, wherein the total content of the ethylene oxide adduct of bisphenol A and the propylene oxide adduct of bisphenol A is 50 mol % or less relative to 100 mol % of all alcohol components constituting the amorphous resin A. 7. The toner for developing electrostatic images according to claim 1 , wherein the alcohol component constituting the amorphous resin A contains an aliphatic alcohol having 4 to 6 carbon atoms. 8. The toner for developing electrostatic images according to claim 1, wherein the aliphatic alcohol component having 4 to 8 carbon atoms contained as the alcohol component constituting the amorphous resin A has a branched structure.