Toner for electrostatic charge image development

Abstract

To provide a toner for electrostatic charge image development having excellent hot off-set resistance and durability.SOLUTION: A toner for electrostatic charge image development 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 azide group, and a release agent C. As an alcohol component constituting the amorphous resin A, ethylene glycol is contained.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an electrostatic charge image developing toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or the like.

Background Art

[0002] In the field of electrophotography, with the development of electrophotographic systems, there is a demand for the development of electrophotographic toners that can cope with high image quality and high speed.

[0003] In Patent Document 1, for the purpose of providing an electrostatic charge image developing toner excellent in durability and coloring power, an amorphous resin having an acidic group, a colorant, a wax, an aliphatic hydrocarbon group having 12 or more and 30 or less carbon atoms, and a compound B having 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 are contained. An electrostatic charge image developing toner is disclosed. In Patent Document 2, for the purpose of providing an electrostatic charge image developing toner excellent in low-temperature fixability and durability, an electrostatic charge image developing toner containing a binder resin (A), a wax (B), and a wax dispersant (C), wherein the melting point of the wax (B) is 70 to 105 ° C, and the heat absorption amount ΔH1 of the endothermic peak derived from the wax (B) of the toner measured by a differential scanning calorimeter is 4 to 15 J / g, and the heat absorption amount ΔH2 of the endothermic peak derived from the wax (B) of the toner measured by a differential scanning calorimeter after washing the toner with hexane satisfies the relational expression of ΔH2 / ΔH1>0.4. An electrostatic charge image developing toner is disclosed.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] When a release agent (wax) is finely dispersed using compound B in the toners of Patent Documents 1 and 2, although excellent in durability, the transfer of the release agent to the toner surface is inhibited, and further improvement in hot offset resistance has been demanded. The present invention relates to an electrostatic charge image developing toner excellent in hot offset resistance and durability.

Means for Solving the Problems

[0006] The present invention 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 azide group, and a release agent C, and relates to an electrostatic charge image developing toner containing ethylene glycol as an alcohol component constituting the amorphous resin A.

Effects of the Invention

[0007] According to the present invention, an electrostatic charge image developing toner excellent in hot offset resistance and durability is provided.

Modes for Carrying Out the Invention

[0008] [Electrostatic Charge Image Developing Toner] The electrostatic charge image developing toner (hereinafter, also simply referred to as "toner") according to the present invention contains an amorphous resin A having an acidic group (hereinafter, also simply referred to as "amorphous resin A"), a polyolefin skeleton, and a compound B having 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 (hereinafter, also simply referred to as "compound B"), and a release agent C, and contains ethylene glycol as an alcohol component constituting the amorphous resin A. According to the above configuration, a toner excellent in hot offset resistance and durability is provided.

[0009] Although the reason why the toner for electrostatic charge image development of the present invention is excellent in durability and hot offset resistance is not clear, it is considered as follows. Due to the acid-base interaction between the acidic group of the amorphous resin A and the basic nitrogen-containing group of the compound B, the compound B is finely dispersed in the amorphous resin A. Along with this, a state is formed in which the polyolefin chemically bonded to the compound B is finely dispersed in the amorphous resin A. As a result of the highly hydrophobic release agent being finely dispersed by the polyolefin, the amount of the release agent on the toner surface is reduced, which is presumably why the durability is excellent. Furthermore, surprisingly, it was found that by containing ethylene glycol as the alcohol component constituting the amorphous resin A, it is also excellent in hot offset resistance. Generally, the release agent exhibits hot offset resistance by melting during toner fixing and migrating to the toner surface. When the release agent is finely dispersed using the compound B, the migration to the toner surface is likely to be inhibited along with the dispersion stabilization of the release agent. Here, by containing ethylene glycol as the alcohol component constituting the amorphous resin A, the hydrophilicity of the resin is improved, and presumably because the compatibility with the locally hydrophobic release agent deteriorates, it quickly migrates to the toner surface during fixing and is considered to be excellent in hot offset resistance.

[0010] The definitions of various terms in this specification are shown below. Whether the resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is defined as the ratio of the softening point of the resin to the maximum peak temperature of endotherm (softening point (°C) / maximum peak temperature of endotherm (°C)) in the measurement method described in the examples below. A crystalline resin is a resin having a crystallinity index of 0.6 or more and 1.4 or less. An amorphous resin is a resin having a crystallinity index of less than 0.6 or more than 1.4. The crystallinity index can be appropriately adjusted by the type and ratio of the raw material monomers, and production conditions such as reaction temperature, reaction time, and cooling rate. In this specification, the "binder resin" means the 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 form acids, and alkyl esters (alkyl groups having 1 to 3 carbon atoms) of each carboxylic acid. "(Meth)acrylic acid alkyl" means acrylic acid alkyl or methacrylic acid alkyl. Further, for the alkyl moiety, "(iso)" means normal alkyl or isoalkyl.

[0011] <Amorphous resin A> Amorphous resin A has an acidic group from the viewpoint of obtaining a toner excellent in hot offset resistance and durability. Examples of the acidic group include a carboxy group, a sulfo group, and a phosphoric acid group. Among these, a carboxy group is preferable. Amorphous resin A is not particularly limited as long as it has an acidic group, and examples thereof include polyester resins and polystyrene resins. Among these, polyester resins are preferable. In the case of polyester resins, the carboxy group at the polymer chain end of the resin corresponds to at least the aforementioned acidic group. Examples of the polyester resin include a polyester resin and a modified polyester resin. Examples of the modified polyester resin include a urethane-modified polyester resin in which a polyester resin is modified with a urethane bond, an epoxy-modified polyester resin in which a polyester resin is modified with an epoxy bond, and a composite resin containing a polyester resin segment and a vinyl resin segment.

[0012] 〔Polyester resin〕 The polyester resin is, for example, a condensate 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 polyhydric alcohols having a valence of 3 or more. These alcohol components may be used alone or in combination of two or more.

[0013] From the perspective of obtaining a toner excellent in hot offset resistance and durability, the amorphous resin A in the present invention contains ethylene glycol as an alcohol component constituting the amorphous resin A. The ethylene glycol contained as an alcohol component constituting the amorphous resin A may be derived from polyethylene terephthalate.

[0014] For polyethylene terephthalate, those produced according to a conventional method by polycondensation of ethylene glycol with terephthalic acid, dimethyl terephthalate, etc. can be used.

[0015] The intrinsic viscosity of polyethylene terephthalate (hereinafter also referred to as "IV value") is preferably 0.4 or more, more preferably 0.5 or more, still more preferably 0.55 or more, and preferably 1.0 or less, more preferably 0.9 or less, still more preferably 0.8 or less, still more preferably 0.75 or less, still more preferably 0.7 or less from the perspective of obtaining a toner excellent in hot offset resistance and durability. The IV value is an index of the molecular weight. The IV value of polyethylene terephthalate can be adjusted by the polycondensation time, etc. The measurement of the IV value can be carried out, for example, by dissolving a sample at a concentration of 0.4 g / dL in a mixed solvent of phenol / tetrachloroethane = 60 / 40 (mass ratio), measuring with an Ubbelohde viscometer, and calculating according to the following formula.

Equation

[0016] Examples of commercially available polyethylene terephthalates 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), "TRN-RTJC" (manufactured by Teijin Limited, IV value: 0.64), and the like.

[0017] From the viewpoint of obtaining a toner excellent in hot offset resistance and durability, the total content of ethylene glycol is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 35 mol% or more, and preferably 60 mol% or less, more preferably 50 mol% or less, still more preferably 45 mol% or less, based on 100 mol% of all the alcohol components constituting the amorphous resin A.

[0018] Examples of the linear or branched aliphatic diol other than ethylene glycol include 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol. Examples of the alicyclic diol include hydrogenated bisphenol A [2,2-bis(4-hydroxycyclohexyl)propane] and an alkylene oxide adduct of hydrogenated bisphenol A having 2 to 4 carbon atoms (average addition mole number: 2 to 12).

[0019] The aromatic diol is preferably an alkylene oxide adduct of bisphenol A, more preferably the formula (I):

Chemical formula

[0020] Examples of the alkylene oxide adduct of bisphenol A include a propylene oxide adduct of bisphenol A [2,2-bis(4-hydroxyphenyl)propane] and an ethylene oxide adduct of bisphenol A. These may be used alone or in combination of two or more.

[0021] From the viewpoint of obtaining a toner excellent in hot offset resistance and durability, the total content of the ethylene oxide adduct of bisphenol A or the propylene oxide adduct of bisphenol A is preferably 75 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less, and preferably 0 mol% or more, based on 100 mol% of all alcohol components constituting the amorphous resin A.

[0022] Examples of the polyhydric alcohol having a valence of 3 or more include glycerin, pentaerythritol, trimethylolpropane, and sorbitol.

[0023] When a polyhydric alcohol having a valence of 3 or more is included, the amount of the polyhydric alcohol having a valence of 3 or more is preferably 2 mol% or more, more preferably 5 mol% or more, and preferably 30 mol% or less, more preferably 20 mol% or less, based on 100 mol% of all alcohol components constituting the amorphous resin A, from the viewpoint of obtaining a toner excellent in hot offset resistance and durability.

[0024] Examples of the carboxylic acid component include dicarboxylic acids and polyvalent carboxylic acids having a valence of 3 or more. These carboxylic acid components may be used alone or in combination of two or more.

[0025] Examples of the dicarboxylic acid 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 preferable. Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, and terephthalic acid. Among these, isophthalic acid and terephthalic acid are preferable, and terephthalic acid is more preferable. The amount of the aromatic dicarboxylic acid is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and preferably 100 mol% or less, more preferably 100 mol%, based on 100 mol% of all carboxylic acid components constituting the amorphous resin A.

[0026] The number of carbon atoms of the linear or branched aliphatic dicarboxylic acid is preferably 2 or more, more preferably 3 or more, and preferably 30 or less, more preferably 20 or less. Examples of the linear or branched aliphatic dicarboxylic acid 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 the succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, and octenyl succinic 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 preferable. The amount of the linear or branched aliphatic dicarboxylic acid is preferably 20 mol% or less, more preferably 10 mol% or less, still more preferably 5 mol% or less, and preferably 0 mol% or more, more preferably 0 mol%, based on 100 mol% of all carboxylic acid components constituting the amorphous resin A.

[0027] As the polyvalent carboxylic acid having a valence of 3 or more, a trivalent carboxylic acid is preferable, and examples thereof include trimellitic acid. When including a polyvalent carboxylic acid having a valence of 3 or more, the amount of the polyvalent carboxylic acid having a valence of 3 or more is preferably 30 mol% or less, more preferably 20 mol% or less, and preferably 0 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, based on 100 mol% of all carboxylic acid components constituting the amorphous resin A.

[0028] The equivalent ratio of the carboxy group of the carboxylic acid component to the hydroxyl group of the alcohol component [COOH group / OH group] is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, more preferably 1.2 or less.

[0029] [Composite resin] The composite resin includes a polyester resin segment and a vinyl-based resin segment. The polyester resin segment preferably consists of the aforementioned polyester resin. The vinyl-based resin segment is preferably an addition polymer of a raw material monomer containing a styrene-based compound, and more preferably an addition polymer of a raw material monomer containing a styrene-based compound and a vinyl-based monomer having an aliphatic hydrocarbon group having 3 to 22 carbon atoms.

[0030] 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, still more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 75% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less. The amount of the vinyl-based resin segment in the composite resin is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, still more preferably 30% by mass or less.

[0031] Regarding 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.

[0032] 〔Method for Producing Amorphous Resin A〕 When the amorphous resin A is a polyester resin, for example, it can be obtained by polycondensation of an alcohol component and a carboxylic acid component. If necessary, an esterification catalyst such as tin(II) bis(2-ethylhexanoate), dibutyltin oxide, titanium diisopropoxide bis(triethanolamineate) may be used in an amount of 0.01 parts by mass or more and 5 parts by mass or less based on 100 parts by mass in total of the alcohol component and the carboxylic acid component; an esterification co-catalyst such as gallic acid (the same as 3,4,5-trihydroxybenzoic acid) may be used in an amount of 0.001 parts by mass or more and 0.5 parts by mass or less based on 100 parts by mass in total of the alcohol component and the carboxylic acid component for polycondensation. The temperature of the polycondensation reaction is preferably 120 °C or higher, more preferably 160 °C or higher, still more preferably 180 °C or higher, and is preferably 250 °C or lower, more preferably 240 °C or lower. The polycondensation may be carried out in an inert gas atmosphere.

[0033] When the amorphous resin A is a composite resin, for example, it may be produced by a method including Step A of performing a polycondensation reaction with an alcohol component and a carboxylic acid component, and Step B of performing an addition polymerization reaction with a raw material monomer of a vinyl-based resin segment and a both-reactive 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. In Step A, a part of the carboxylic acid component is subjected to the polycondensation reaction, then after Step B is carried out, the remainder of the carboxylic acid component is added to the polymerization system, and the polycondensation reaction of Step A and, if necessary, the reaction with the both-reactive monomer are further advanced. This method is preferred. The conditions of Step A are the same as those of the aforementioned method for producing a polyester resin.

[0034] Examples of the polymerization initiator 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 with respect to 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.

[0035] 〔Physical properties of amorphous resin A〕 From the viewpoint of further improving the hot offset resistance, the softening point of the amorphous resin A is preferably 70°C or higher, more preferably 90°C or higher, still more preferably 100°C or higher, and from the viewpoint of further improving the low-temperature fixing property, it is preferably 160°C or lower, more preferably 150°C or lower, still more preferably 140°C or lower. From the viewpoint of further improving the heat storage stability, the glass transition temperature of the amorphous resin A is preferably 30°C or higher, more preferably 35°C or higher, still more preferably 40°C or higher, and from the viewpoint of further improving the low-temperature fixing property, it is preferably 80°C or lower, more preferably 75°C or lower, still more preferably 70°C or lower.

[0036] From the viewpoints of further improving the hot offset resistance and durability, the acid value of the amorphous resin A is preferably 1 mgKOH / g or higher, more preferably 5 mgKOH / g or higher, still more preferably 10 mgKOH / g or higher, still more preferably 12 mgKOH / g or higher, and preferably 40 mgKOH / g or lower, more preferably 35 mgKOH / g or lower, still more preferably 30 mgKOH / g or lower. The softening point, glass transition temperature, and acid value of the amorphous resin A can be appropriately adjusted according to the types and amounts of the raw material monomers used, as well as the production conditions such as the reaction temperature, reaction time, and cooling rate. These values are determined by the method described in the examples. In addition, when two or more types of amorphous resin A are used in combination, it is preferable that the softening point, glass transition temperature, and acid value obtained as their mixture are each within the aforementioned ranges.

[0037] In the binder resin of the toner, the content of the amorphous resin A is preferably 50% by mass or more, more preferably 60% by mass or more, still 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, still more preferably 90% by mass or less, and still more preferably 88% by mass or less.

[0038] In the present invention, from the viewpoints of hot offset resistance and durability, the polyester resin may contain two or more types of polyester resins having different softening points, preferably 5°C or more, more preferably 10°C or more. Among the two or more types of polyester resins, the softening point of the polyester resin having the lowest softening point is preferably 70°C or more, more preferably 90°C or more, still more preferably 100°C or more, from the viewpoint of further improving durability, and is preferably 135°C or less, more preferably 120°C or less, still more preferably 115°C or less, from the viewpoint of further improving low-temperature fixability. Among the two or more types of polyester resins, the softening point of the polyester resin having the highest softening point is preferably 110°C or more, more preferably 120°C or more, from the viewpoint of improving the hot offset resistance of the toner, and is preferably 160°C or less, more preferably 150°C or less, still more preferably 140°C or less, from the viewpoint of further improving low-temperature fixability. When containing two or more types of polyester resins, it is preferable to use two types in combination from the viewpoint of improving the productivity of the toner. 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, still more preferably 15°C or more, from the viewpoint of hot offset resistance, and is preferably 60°C or less, more preferably 50°C or less, still more preferably 40°C or less, from the viewpoints of durability and low-temperature fixability.

[0039] When using two types of polyester resins, 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, still more preferably 30 / 70 or more, and preferably 90 / 10 or less, more preferably 80 / 20 or less, still more preferably 70 / 30 or less.

[0040] <Compound B> Compound B has a polyolefin skeleton and a basic nitrogen-containing group from the viewpoint of obtaining a toner excellent in hot offset resistance and durability. Compound B is preferably dispersed in the amorphous resin A. That is, it is preferable that Compound B is dispersed inside the toner particles.

[0041] 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 (=N2), and an azide group (-N3). The amino group may be any of a primary amino group, a secondary amino group, and a tertiary amino group. From the viewpoint of the affinity of Compound B for the binder resin A, an amino group is preferable.

[0042] Examples of the functional group contained in addition to the basic nitrogen-containing group include a hydroxy group, a formyl group, an acetal group, an oxime group, and a thiol group.

[0043] Compound B has a polyolefin skeleton from the viewpoint of obtaining a toner excellent in hot offset resistance and durability. Examples of the polyolefin forming the polyolefin skeleton include polyethylene, polypropylene, polybutylene, polymethylpentene, polytetradecene, polyhexadecene, polyoctadecene, polyeicosene, polydocosene, or a copolymer of these monomers. As the polyolefin skeleton, a polypropylene skeleton, a polyethylene skeleton, or a propylene / ethylene copolymer skeleton is preferable, a polyethylene skeleton or a polypropylene skeleton is more preferable, and a polypropylene skeleton is still more preferable.

[0044] Compound B is, for example, a reaction product of a basic nitrogen-containing group raw material and a polyolefin skeleton raw material. 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 the adsorptivity to the 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 preferable. Examples of the polyalkyleneamine include polyethyleneamine, polypropyleneamine, and polybutyleneamine. Examples of the polyethyleneamine include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and polyethyleneimine having a number average molecular weight of 300 or more and 15,000 or less. Among them, tetraethylenepentamine, pentaethylenehexamine, and polyethyleneimine having a number average molecular weight of 300 or more and 3,000 or less are still more preferable, and tetraethylenepentamine is still more preferable.

[0045] The polyethyleneimine contains, for example, a primary amino group, a secondary amino group, and a tertiary amino group, and preferably has a branched structure. Examples of the commercially available product of polyethyleneimine include "SP-003", "SP-006", "SP-012", and "SP-018" of the "Epomin" series (manufactured by Junsei Chemical Co., Ltd.). Examples of the polyaminoalkyl methacrylate include polydimethylaminoethyl methacrylate.

[0046] 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, still more preferably 5 mmol / g or more, and preferably 50 mmol / g or less, more preferably 40 mmol / g or less, still more preferably 30 mmol / g or less, still 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.

[0047] From the viewpoint of the adsorptivity to the resin having an acidic group, the number average molecular weight of the basic nitrogen-containing group raw material is preferably 100 or more, more preferably 140 or more, still more preferably 180 or more, and preferably 15,000 or less, more preferably 10,000 or less, still more preferably 5,000 or less, still more preferably 3,000 or less, still more preferably 2,000 or less.

[0048] Examples of the polyolefin skeleton raw material include polyolefins having a reactive functional group. Examples of the reactive functional group include a carboxy group, a halogeno group, an epoxy group, a formyl group, and an isocyanate group. The carboxy group may be its anhydride. Examples of the halogeno group include a chloro group, a bromo group, and an iodo group. Among these, from the viewpoints of safety and reactivity, a carboxy group or its anhydride and a halogeno group are preferable, and a carboxy group or its anhydride is more preferable. Examples of the polyolefin skeleton raw material 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 mono-terminal acid-modified polyolefin, and more preferably a mono-terminal maleic anhydride-modified polyolefin.

[0049] The content of the polyolefin having a reactive functional group in the polyolefin skeletal raw material is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and is 100% by mass or less, and more preferably 100% by mass.

[0050] The melting point of the polyolefin skeletal raw material is preferably 60 °C or higher, more preferably 70 °C or higher, still more preferably 80 °C or higher, and is preferably 160 °C or lower, more preferably 150 °C or lower, still more preferably 140 °C or lower.

[0051] The number average molecular weight of the polyolefin skeletal raw material is preferably 100 or more, more preferably 200 or more, still more preferably 300 or more, and is preferably 5,000 or less, more preferably 3,000 or less, still more preferably 2,500 or less. The number average molecular weight of the polyolefin skeletal raw material can be determined, for example, by the gel permeation chromatography (GPC) method.

[0052] Examples of polypropylene skeleton raw materials having a polypropylene skeleton include "100Ts", "110Ts", "1001", "1010" (manufactured by Sanyo Chemical Industries, Ltd.), "13-LP", "13-LLP", "14-LWP", "15-LP", "15-LLP", "16-LP", "DX-526P", "CY-9122P", "CY-9124P", "HM-21P", "M-28P", "F-2P", "F-6P" (manufactured by Toyobo Co., Ltd.) in the "Umemex" series, "M-100", "M-300", "M-312", "PMA H1000P", "PMA-F2" (manufactured by Toyobo Co., Ltd.) in the "Toyotack" series, "C", "L-206", "813A", "803M", "803MW", "803LT", "1026", "803L", "814H", "390S", "814B", "360T", "370M", "2027MB", "822", "892L", "930", "842LM", "851L" (manufactured by Nippon Paper Industries Co., Ltd.) in the "Super Kron" series, and "X-10065", "X-10088", "X-10082", "X-10087", "X-10053", "X-10052" (manufactured by Baker Hughes).

[0053] 〔Method for Producing Compound B〕 Compound B is obtained by reacting a basic nitrogen-containing group raw material with a polyolefin skeleton raw material. The reaction temperature is preferably 100 °C or higher, more preferably 120 °C or higher, still more preferably 150 °C or higher, and preferably 200 °C or lower, more preferably 180 °C or lower, still more preferably 170 °C or lower.

[0054] The ratio (A / N) of the number of moles (A) of the reactive functional group of the polyolefin skeleton raw material to the number of moles (N) of the basic nitrogen of the basic nitrogen-containing group raw material is preferably 0.05 or more, more preferably 0.1 or more, and preferably 0.8 or less, more preferably 0.7 or less, still more preferably 0.6 or less.

[0055] The above ratio (A / N) is calculated as follows. Ratio (A / N) = 1000 × [number of reactive functional groups per molecule of aliphatic hydrocarbon group raw material (A) × (charge amount of aliphatic hydrocarbon group raw material / molecular weight of aliphatic hydrocarbon group raw material)] / [amine value (mmol / g) of basic nitrogen-containing group raw material × charge amount of basic nitrogen-containing group raw material] However, in the case of a polyolefin backbone raw material having a maleic anhydride moiety, the number of reactive functional groups per molecule is 1. The amine value of the basic nitrogen-containing group raw material can be measured by hydrochloric acid titration or perchloric acid titration.

[0056] 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. The formation of the imide bond can be confirmed by infrared spectroscopy (hereinafter, also simply referred to as "IR") by observing a peak (1700 cm -1 ) derived from the imide bond.

[0057] [Physical properties of Compound B] From the viewpoint of improving hot offset resistance and durability, the melting point of Compound B is preferably 40°C or higher, more preferably 50°C or higher, still more preferably 65°C or higher, still more preferably 80°C or higher, and preferably 150°C or lower, more preferably 140°C or lower, still more preferably 130°C or lower. The melting point is measured by the method described in the examples.

[0058] From the viewpoint of improving hot offset resistance and durability, the number average molecular weight of Compound B is preferably 500 or higher, more preferably 800 or higher, still more preferably 1,000 or higher, and preferably 20,000 or lower, more preferably 10,000 or lower, still more preferably 7,000 or lower.

[0059] From the viewpoint of improving hot offset resistance and durability, the content of Compound B is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, still more preferably 1 part by mass or more, still more preferably 2 part by mass or more, per 100 parts by mass of the binder resin, and is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less.

[0060] <Release Agent C> Examples of Release Agent C include hydrocarbon waxes or their oxides, ester waxes, fatty acid amides, fatty acids, fatty acid metal salts, higher alcohols, etc. Among these, hydrocarbon waxes or their oxides, or ester waxes are preferred, hydrocarbon waxes or their oxides are more preferred, and hydrocarbon waxes are still 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, Sasol wax, etc. Examples of ester waxes include carnauba wax, montan wax or their deacidified waxes, fatty acid ester waxes, etc. These can be used alone or in combination of two or more.

[0061] The melting point of 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, still more preferably 115°C or lower. The melting point of Release Agent C is determined by the method described in the examples below. The content of Release Agent C is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, still more preferably 2 part by mass or more, per 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, still more preferably 10 parts by mass or less.

[0062] <Charge Control Agent> The toner may contain a charge control agent. The charge control agent may contain either a positive charge control agent or a negative charge control agent. Examples of the positive charge control agent include nigrosine dyes such as "Nigrosine Base EX", "Oil Black BS", "Oil Black SO", "Bontron N-01", "Bontron N-04", "Bontron N-07", "Bontron N-09", "Bontron N-11" (manufactured by Orient Chemical Industries Co., Ltd., etc.); triphenylmethane dyes containing a tertiary amine in the side chain, quaternary ammonium salt compounds such as "Bontron P-51" (manufactured by Orient Chemical Industries Co., Ltd.), cetyltrimethylammonium bromide, "COPY CHARGE PX 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", "PLZ-8001" (manufactured by Shikoku Kasei Kogyo Co., Ltd., etc.); styrene-acrylic resins such as "FCA-701PT" (manufactured by Fujikura Kasei Co., Ltd., etc.).

[0063] Examples of the negative charge control agent include metal-containing azo dyes such as "Vari Fast Black 3804", "Bontron S-31", "Bontron S-32", "Bontron S-34", "Bontron S-36" (manufactured by Orient Chemical Industries Co., Ltd., etc.), "Eisenspirone Black TRH", "T-77" (manufactured by Hodogaya Chemical Co., Ltd., etc.); metal compounds of benzoic acid compounds such as "LR-147", "LR-297" (manufactured by Nippon Carlit Co., Ltd., etc.); metal compounds of salicylic acid compounds such as "Bontron E-81", "Bontron E-84", "Bontron E-88", "Bontron E-304" (manufactured by Orient Chemical Industries Co., Ltd., etc.), "TN-105" (manufactured by Hodogaya Chemical Co., Ltd., etc.); copper phthalocyanine dyes; quaternary ammonium salts such as "COPY CHARGE NX VP434" (manufactured by Clariant), nitroimidazole derivatives, etc.; organometallic compounds.

[0064] The content of the charge control agent is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, based on 100 parts by mass of the binder resin.

[0065] <Colorant> The toner may contain a colorant. As the colorant, dyes, pigments, etc. used as colorants for toners can be used. For example, 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, disazo yellow can be mentioned. The toner of the present invention may be either a black toner or a color toner other than black.

[0066] From the viewpoint of improving the image density of the toner, the content of the colorant is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and preferably 40 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, based on 100 parts by mass of the binder resin.

[0067] The toner may further contain other reinforcing fillers such as magnetic powder, fluidity improvers, conductivity adjusters, fibrous substances, and additives such as antioxidants, anti - aging agents, and cleaning property improvers.

[0068] The toner contains, for example, toner particles. The toner particles preferably contain amorphous resin A, compound B, and release agent C. The charge control agent, colorant, and other additives are preferably contained in the toner particles. Although the toner particles can be used as the toner as they are, it is preferable to use those obtained by adding and treating the external additives described below on the surface of the toner particles as the toner. The toner is preferably used as a dry toner.

[0069] [Method for manufacturing toner] The toner may be a toner obtained by any known method such as a melt-kneading method, an emulsion phase inversion method, an emulsion polymerization method, an emulsion aggregation method, etc. However, from the viewpoints of productivity and dispersibility of the colorant, a pulverized toner obtained by the melt-kneading method is preferred.

[0070] In the case of a pulverized toner, the method for manufacturing the toner is, for example, 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 is included.

[0071] In Step 1, additives such as a charge control agent and a colorant may be included in the mixture. These toner raw materials are preferably mixed in advance with a mixer such as a Henschel mixer or a ball mill and then supplied to a kneader. For the melt-kneading in Step 1, known kneaders such as a closed kneader, a single-screw extruder, a twin-screw extruder, and an open roll type kneader can be used. Among these, a twin-screw extruder that can widely set the kneading temperature is preferred. The temperature for melt-kneading 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 pulverization and then subjected to the subsequent Step 2.

[0072] The pulverization in Step 2 may be carried out in multiple stages. For example, after coarsely pulverizing the melt-kneaded product to 1 mm or more and 5 mm or less, it may be further finely pulverized to a desired particle size. Examples of pulverizers preferably used for coarse pulverization include a hammer mill, an atomizer, and a rotor plex. Examples of pulverizers preferably used for fine pulverization include a fluidized bed jet mill, a collision plate type jet mill, and a rotary mechanical mill. Among these, from the viewpoint of pulverization efficiency, a fluidized bed jet mill and a collision plate type jet mill are preferred, and a collision plate type jet mill is more preferred.

[0073] Examples of the classifier used for classification include, for example, a rotor classifier, an air classifier, an inertial classifier, and a screen classifier. During the classification process, the crushed material that has not been sufficiently crushed and removed may be subjected to the crushing process again, and the crushing process and the classification process may be repeated as necessary.

[0074] The volume median particle diameter (D 50 ) of the toner particles is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, from the viewpoint of obtaining a high-quality image.

[0075] It is preferable that the toner is added and treated on the surface of the toner particles using a fluidizing agent or the like as an external additive. Examples of the external additive include fine particles of inorganic materials such as hydrophobic silica, titanium oxide, alumina, cerium oxide, and carbon black, and fine particles of polymers such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, hydrophobic silica is preferable. When using an external additive, the addition amount of the external additive is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, still 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, still more preferably 4 parts by mass or less, based on 100 parts by mass of the toner particles.

[0076] The toner is used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, etc. The toner can be used as a one-component developer or as a two-component developer mixed with a carrier.

Examples

[0077] [Measurement] [Acid value of resin] The acid value of the resin was measured based on the method of JIS K 0070. However, only 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)).

[0078] [Softening point, glass transition temperature, etc. of the resin] (1) Softening point Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), while heating 1 g of the sample at a heating rate of 6 °C / min, a load of 1.96 MPa was applied by a plunger and extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. With respect to the temperature, the plunger descent amount of the flow tester was plotted, and the temperature at which half of the sample flowed out was defined 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 cooled from room temperature (20 °C) to 0 °C at a cooling rate of 10 °C / min was held as it was for 1 minute, and then measured while heating from that temperature to 180 °C at a heating rate of 10 °C / min. Among the observed endothermic peaks, the temperature of the peak on the highest temperature side was defined 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 - 0.02 g of the sample was weighed into an aluminum pan, heated to 200 °C, and cooled from that temperature to 0 °C at a cooling rate of 10 °C / min. Next, it was measured while heating from that temperature to 150 °C at a heating rate of 10 °C / min. The temperature at the intersection of the extension line of the baseline below the maximum endothermic peak temperature and the tangent line showing the maximum slope from the rising part of the peak to the apex of the peak was defined as the glass transition temperature.

[0079] [Number average molecular weight and weight average molecular weight of the polyester resin] By the following method, the molecular weight distribution was measured by gel permeation chromatography (GPC) 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 so that the concentration became 0.5 g / 100 mL. Then, this solution was filtered using a fluororesin filter with a pore size of 2 μm (manufactured by Sumitomo Electric Industries, Ltd., trade name: FP-200) to remove insoluble components, and used as the sample solution. (2) Molecular weight measurement ​Using the following apparatus, chloroform was used as the eluent and flowed at a rate of 1 mL per minute, and the column was stabilized in a constant temperature bath at 40°C. 100 μL of the sample solution was injected therein for measurement. The molecular weight of the sample was calculated based on a calibration curve prepared in advance. The calibration curve at this time used a calibration curve prepared using several monodisperse polystyrenes with known molecular weights (manufactured by Tosoh Corporation; 2.63×10 3 , 2.06×10 4 , 1.02×10 5 , manufactured by GL Sciences Inc.; 2.10×10 3 , 7.00×10 3 , 5.04×10 4 ) as standard samples. Measuring apparatus: CO-8010 (trade name, manufactured by Tosoh Corporation) Analysis column: GMH XL +G3000H XL (both are trade names, manufactured by Tosoh Corporation)

[0080] [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 the sample was weighed into an aluminum pan, heated up to 200°C, and then cooled from 200°C to 0°C at a cooling rate of 10°C / min. Next, the sample was heated up at a heating rate of 10°C / min, and the heat quantity was measured, and the maximum peak temperature of endotherm was taken as the melting point.

[0081] [Amine value of the 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. However, only the measurement solvent was changed from chlorobenzene specified in JIS K2501:2003 to chloroform.

[0082] [Volume median diameter (D 50 ) of the toner] The volume median diameter of the toner was measured as follows. · Measuring instrument: Coulter Multisizer III (trade name, manufactured by Beckman Coulter, Inc.) · Aperture diameter: 50 μm · Analysis software: Multi-Sizer III version 3.51 (product name, manufactured by Beckman Coulter) · Electrolyte: Isoton II (product name, manufactured by Beckman Coulter) · Dispersion solution: Polyoxyethylene lauryl ether (manufactured by Kao Corporation, product name: Emulgen 109P, HLB: 13.6) was dissolved in the above electrolyte to obtain a dispersion solution with a concentration of 5% by mass. · Dispersion conditions: 10 mg of the measurement sample was added to 5 mL of the above dispersion solution and dispersed with an ultrasonic disperser for 1 minute. Then, 25 mL of the electrolyte was added and further dispersed with an ultrasonic disperser for 1 minute to prepare a sample dispersion solution. · Measurement conditions: By adding the above sample dispersion solution to 100 mL of the electrolyte, the concentration was adjusted to a concentration at which the particle size of 30,000 particles could be measured in 20 seconds. Then, 30,000 particles were measured, and the volume median diameter (D 50 ) was determined from the particle size distribution.

[0083] [Production of alkenyl succinic anhydride] (Production of alkylene compound A) Using propylene tetramer (manufactured by Nippon Oil Corporation, product name: "Light Tetramer"), fractional distillation was carried out 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 described later. The distribution of the alkylene compound was measured according to the analysis by gas chromatography of the alkylene compound A in JP-A-2014-013384, and C9H 18 : 0.5% by mass, C 10 H 20 : 4% by mass, C 11 H 22 : 20% by mass, C 12 H 24 : 66% by mass, C 13 H 26 : 9% by mass, C 14 H 28 : 0.5% by mass (the number of peaks corresponding to alkylene compounds having 9 to 14 carbon atoms was 6).

[0084] (Production of alkenyl succinic anhydride) 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 phosphite), and 0.1 g of butylhydroquinone as a polymerization inhibitor were charged into a 1 L autoclave manufactured by Nitto Koatsu Co., Ltd., and the pressurized nitrogen substitution (0.2 MPaG) was repeated three times. After starting stirring at 60°C, the temperature was raised to 230°C over 1 hour and reacted for 6 hours. The pressure at the time of reaching the reaction temperature was 0.3 MPaG. After the reaction was completed, it was cooled to 80°C, returned to normal pressure (101.3 kPa), and transferred to a 1 L four-necked flask. The temperature was raised to 180°C with stirring, and the residual alkylene compound was distilled off at 1.3 kPa over 1 hour. Subsequently, after cooling to room temperature (25°C) and returning to normal pressure (101.3 kPa), 406.1 g of the target alkenyl succinic anhydride was obtained. The average molecular weight of the alkenyl succinic anhydride determined from the acid value was 268.

[0085] [Production of Resin H and Resin L] Production Examples H1 to H3, H6, H10, L1 to L3, L6, L9 (Production of Resins H-1 to H-3, H-6, H-10, L-1 to L-3, L-6, L-9) The raw material monomers, esterification catalyst, and gallic acid of the polyester resin shown in Tables 1 and 2 were placed in a 5 L four-necked flask equipped with a nitrogen inlet tube, a stirrer, and a thermocouple, and kept at 180°C for 1 hour under a nitrogen atmosphere, then the temperature was raised from 180°C to 230°C at 10°C / hr, and then polycondensed at 230°C for 5 hours. Further, the reaction was carried out at 230°C under a reduced pressure of 10 kPa to the softening point described in Tables 1 and 2 to obtain a polyester resin.

[0086] Production Examples H4, H5, H12, L4, L5, L11 (Production of Resins H-4, H-5, H-12, L-4, L-5, L-11) The raw material monomers, esterification catalyst, and gallic acid of the polyester resin shown in Tables 1 and 2 were placed in a 5-liter four-necked flask equipped with a nitrogen inlet tube, a stirrer, and a thermocouple. Under a nitrogen atmosphere, the temperature was raised to 235°C, and then polycondensation was carried out at 235°C for 6 hours. Thereafter, the temperature was lowered to 210°C, and the reaction was carried out under a reduced pressure of 10 kPa to the softening point described in Tables 1 and 2 to obtain a polyester resin.

[0087] Production Examples H7, H8, H11, L7, L8, L10 (Production of Resins H-7, H-8, H-11, L-7, L-8, L-10) The raw material monomers, esterification catalyst, and gallic acid of the polyester resin shown in Tables 1 and 2 were placed in a 5-liter four-necked flask equipped with a nitrogen inlet tube, a dehydration tube equipped with a fractionating tube through which hot water at 98°C passed, a stirrer, and a thermocouple. Under a nitrogen atmosphere, after maintaining the temperature at 180°C for 1 hour, the temperature was raised from 180°C to 230°C at 10°C / hr, and then polycondensation was carried out at 230°C for 5 hours. Further, the reaction was carried out under a reduced pressure of 10 kPa at 230°C to the softening point described in Tables 1 and 2 to obtain a polyester resin.

[0088] Production Example H9 (Production of Resin H-9) The raw material monomers, esterification catalyst, and gallic acid of the polyester resin other than trimellitic anhydride shown in Table 1 were placed in a 5-liter four-necked flask equipped with a nitrogen inlet tube, a stirrer, and a thermocouple. Under a nitrogen atmosphere, after maintaining the temperature at 180°C for 1 hour, the temperature was raised from 180°C to 230°C at 10°C / hr, and then polycondensation was carried out at 230°C for 5 hours. Thereafter, the temperature was lowered to 210°C, trimellitic anhydride was added, and after reacting at 210°C for 1 hour, the reaction was further carried out under a reduced pressure of 10 kPa at 210°C to the softening point described in Table 1 to obtain a polyester resin.

[0089]

Table 1-1

[0090]

Table 1-2

[0091]

Table 2-1

[0092]

Table 2-2

[0093] [Production of Compound B] Production Example B1 (Production of Compound B-1) Into a 2 L four-necked flask equipped with a cooling tube, a nitrogen inlet tube, a stirrer, a dehydrating tube, and a thermocouple, 28 g of tetraethylenepentamine (amine value 23 mmol / g) as a basic nitrogen-containing group raw material, 300 g of maleic anhydride-modified polypropylene with one terminal anhydride group (PPSA1000) (manufactured by 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 (manufactured by Fujifilm Wako Pure Chemical Corporation) were added, and the inside of the reaction vessel was purged with nitrogen gas. After heating the inside of the reaction vessel to 150°C and holding for 1 hour, the temperature was raised to 160°C and held for 1 hour. Further, the pressure inside the flask was reduced, and the reaction was carried out while distilling off the solvent under reduced pressure to 8.3 kPa. From IR analysis, it was confirmed that the peak (1780 cm -1 ) of the acid anhydride derived from PPSA disappeared and the peak (1700 cm -1 ) derived from the imide bond appeared, and Compound B-1 was obtained. The melting point is shown in Table 3.

[0094] Production Example B2 (Production of Compound B-2) The wax affinity group raw material was changed to maleic anhydride-modified polypropylene with one terminal anhydride group (PPSA2500) (manufactured by Baker Hughes, "X-10088", melting point 119°C, number average molecular weight 2,500), and Compound B-2 was obtained in the same manner as in Production Example B1 except that the amounts of the basic nitrogen-containing group raw material and xylene were changed as shown in Table 3. The melting point is shown in Table 3.

[0095] [Table 3]

[0096] [Manufacture of Toner] Example 1 To 100 parts by mass of a polyester resin (60 parts by mass of resin H-1 and 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 a negative charge control agent "Bontron (registered trademark) S-34" (manufactured by Orient Chemical Industries, Ltd.), and 6 parts by mass of paraffin wax "HNP-9" (manufactured by Nippon Seiro Co., Ltd., melting point 77°C) as a release agent C were mixed with a Henschel mixer to obtain a mixture. The obtained mixture was melt-kneaded using a co-rotating twin-screw extruder with a total length of the kneading section 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 set temperature of 100°C to obtain a melt-kneaded product. The supply rate of the mixture was 20 kg / hr, and the average residence time was about 18 seconds. After cooling and coarsely pulverizing the obtained melt-kneaded product, it was pulverized with a jet mill and classified to obtain a powder (toner mother particles) having a volume median diameter (D 50 ) of 7.0 μm. To 100 parts by mass of the obtained powder (toner mother particles), 1.5 parts by mass of hydrophobic silica "RY50" (manufactured by Nippon Aerosil Co., Ltd., hydrophobizing agent: silicone oil, average particle diameter 40 nm) and 1.0 part by mass of hydrophobic silica "R972" (manufactured by Nippon Aerosil Co., Ltd., hydrophobizing agent: DMDS, average particle diameter 16 nm) as external additives were mixed with a Henschel mixer for 3 minutes to obtain toner. The evaluation results of the obtained toner are shown in Table 4.

[0097] Examples 2 to 13, Comparative Examples 1 to 4 In Example 1, 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 were changed to the types and amounts of the aqueous dispersion of resin particles shown in Table 4. The evaluation results of the obtained toner are shown in Table 4.

[0098] [Evaluation] [Hot offset property of toner] Toner was mounted on a device obtained by improving the fixing device of a copying machine "AR-505" (manufactured by Sharp Corporation) so that fixing outside the device was possible, and a printed matter was obtained in an unfixed state (printed surface area: 2 cm × 12 cm, adhesion amount: 0.5 mg / cm 2 ). Thereafter, using a fixing machine adjusted so that the total fixing pressure became 40 kgf (fixing speed 300 mm / sec), while sequentially raising the temperature of the fixing roll from 100°C to 200°C by 5°C each time, a fixing test of the unfixed printed matter was conducted at each temperature. The occurrence of hot offset was visually observed, and the temperature at which hot offset occurred was confirmed as the hot offset resistance. The higher the temperature at which this hot offset occurs, the more preferable it is.

[0099] [Durability of toner] Toner was mounted on a printing machine "Page Press N-4" (manufactured by Casio Computer Co., Ltd., fixing: contact fixing method, development: non-magnetic one-component development method, development roll diameter: 2.3 cm), and a diagonal stripe pattern with a blackening rate of 5.5% was continuously printed in an environment of temperature 32°C and humidity 85%. During this process, a solid black image was printed every 500 sheets, and the presence or absence of streaks on the image was confirmed. Printing was stopped when streaks occurred on the image, and up to 9000 sheets were printed. The number of printed sheets until streaks were visually observed on the image was regarded as the number of sheets in which streaks occurred due to the fusion and adhesion of toner to the development roll, and the durability was evaluated. That is, it can be judged that the higher the number of sheets without streaks, the higher the durability of the toner.

[0100]

Table 4

[0101] From the results of the examples and comparative examples above, it can be seen that a toner excellent in hot offset resistance and durability can be obtained by containing an amorphous resin A having an acidic group, a compound B, and a release agent C.

Claims

1. An electrostatic charge image developing toner containing an amorphous resin A having an acidic group, a compound B which is a reaction product of a basic nitrogen-containing group raw material and a polyolefin skeleton raw material, and a release agent C, and containing ethylene glycol as an alcohol component constituting the amorphous resin A, wherein the amorphous resin A is a polyester resin, the polyester resin is a condensate of the alcohol component and a carboxylic acid component, the content of ethylene glycol is 10 mol% or more with respect to 100 mol% of all the alcohol components constituting the polyester resin, the content of one or more selected from isophthalic acid and terephthalic acid is 80 mol% or more with respect to 100 mol% of the carboxylic acid component constituting the polyester resin, the basic nitrogen-containing group raw material is a polyalkyleneamine having at least one amino group selected from the group consisting of a primary amino group and a secondary amino group and not having a tertiary amino group, the ratio (A / N) of the number of moles (A) of the reactive functional group of the polyolefin skeleton raw material to the number of moles (N) of the basic nitrogen of the amino group of the polyalkyleneamine is 0.05 or more and 0.8 or less, the release agent C is a hydrocarbon wax, and the electrostatic charge image developing toner.

2. The electrostatic charge image developing toner according to claim 1, wherein the polyolefin skeleton is a polyethylene skeleton or a polypropylene skeleton.

3. The electrostatic charge image developing toner according to claim 1 or 2, wherein the acid value of the polyester resin is 5 mgKOH / g or more and 40 mgKOH / g or less.

4. The electrostatic charge image developing toner according to any one of claims 1 to 3, wherein the ethylene glycol contained as an alcohol component constituting the polyester resin is derived from polyethylene terephthalate.

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