Toner for electrostatic charge image development

Abstract

To provide a toner for electrostatic charge image development that is excellent in durability, bending resistance of printed matter and shelf life at high temperature and high humidity.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, a C4-8 aliphatic alcohol 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] Patent Document 1 discloses an electrostatic charge image developing toner containing 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, for the purpose of providing an electrostatic charge image developing toner excellent in durability and coloring power. Patent Document 2 discloses an electrostatic charge image developing toner containing a binder resin (A), a wax (B), and a wax dispersant (C), for the purpose of providing an electrostatic charge image developing toner excellent in low-temperature fixability and durability, wherein the melting point of the wax (B) is 70 to 105°C, 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 after washing the toner with hexane measured by a differential scanning calorimeter satisfies the relational expression ΔH2 / ΔH1>0.4.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] The present invention relates to an electrostatic charge image developing toner excellent in durability, fold resistance of printed matter, and storage stability under high temperature and high humidity.

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 an aliphatic alcohol having 4 to 8 carbon atoms as an alcohol component constituting the amorphous resin A.

Effects of the Invention

[0007] According to the present invention, there is provided an electrostatic charge image developing toner excellent in durability, fold resistance of printed matter, and storage stability under high temperature and high humidity.

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 an aliphatic alcohol having 4 to 8 carbon atoms as an alcohol component constituting the amorphous resin A. According to the above configuration, a toner excellent in durability, fold resistance of printed matter, and storage stability under high temperature and high humidity is provided.

[0009] The reason why the electrostatic charge image developing toner of the present invention is excellent in durability, fold resistance of printed matter, and storage stability under high temperature and high humidity is not clear, but it is considered as follows. Due to the acid-base interaction between the acidic groups of the amorphous resin A and the basic nitrogen-containing groups 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 an aliphatic alcohol having 4 to 8 carbon atoms as the alcohol component constituting the amorphous resin A, the print is also excellent in folding resistance and storage stability under high temperature and high humidity. In order to improve the folding resistance of the print, it is important to have a high affinity between the toner and the paper and to increase the fixing strength, and it is known to use an aliphatic alcohol. However, since using an aliphatic alcohol increases the ester group concentration of the resin, the hygroscopicity increases and the storage stability decreases under high temperature and high humidity. By containing an aliphatic alcohol having 4 to 8 carbon atoms as the alcohol component constituting the amorphous resin A, it was presumably possible to achieve appropriate hydrophilicity and an increase in the ester group concentration, so the print is considered to be excellent in folding resistance and storage stability under high temperature and high humidity.

[0010] The definitions of various terms in this specification are shown below. Whether a 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 in the measurement method described in the examples below (softening point (°C) / maximum peak temperature of endotherm (°C)). 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 types and ratios 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 produce acids and alkyl esters of each carboxylic acid (alkyl group having 1 to 3 carbon atoms). "(Meth)acrylic acid alkyl" means acrylic acid alkyl or methacrylic acid alkyl. Also, 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 durability, fold resistance of printed matter, and storage stability under high temperature and high humidity. 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 trivalent or higher valence. These alcohol components may be used alone or in combination of two or more.

[0013] In the amorphous resin A of the present invention, from the viewpoint of obtaining a toner excellent in durability, foldability of printed matter, and storage stability under high temperature and high humidity, it contains an aliphatic alcohol having 4 to 8 carbon atoms as an alcohol component constituting the amorphous resin A. The number of carbon atoms of the aliphatic alcohol is preferably 4 or more and 6 or less. The aliphatic alcohol may be a linear or branched aliphatic diol, an alicyclic diol, or a polyhydric alcohol having a trivalent or higher valence. Further, the aliphatic alcohol preferably has a branched structure.

[0014] Examples of the linear or branched aliphatic diol 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 referred to 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 preferable, and 2,2-dimethyl-1,3-propanediol is more preferable.

[0015] Examples of the polyhydric alcohol having a trivalent or higher valence and having 4 to 8 carbon atoms include pentaerythritol, trimethylolpropane, and sorbitol.

[0016] From the viewpoint of obtaining a toner excellent in durability, foldability of printed matter, and storage stability under high temperature and high humidity, the total content of the aliphatic alcohol having 4 to 8 carbon atoms is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 40 mol% or more, and preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 70 mol% or less, still more preferably 65 mol% or less, based on 100 mol% of all the alcohol components constituting the amorphous resin A.

[0017] Examples of the linear or branched aliphatic diols other than the aliphatic alcohols having 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 the alicyclic diols include hydrogenated bisphenol A [2,2-bis(4-hydroxycyclohexyl)propane] and alkylene oxide adducts (average addition mole number: 2 or more and 12 or less) of hydrogenated bisphenol A having 2 to 4 carbon atoms.

[0018] The aromatic diol is preferably an alkylene oxide adduct of bisphenol A, more preferably represented by the formula (I):

Chemical formula

[0019] Examples of the alkylene oxide adduct 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 of two or more.

[0020] 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, still 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 the alcohol components constituting the amorphous resin A, from the viewpoint of obtaining a toner excellent in the folding resistance of the printed matter.

[0021] Examples of the polyhydric alcohol having a valency of 3 or more other than the aliphatic alcohol having 4 to 8 carbon atoms include glycerin.

[0022] When a polyhydric alcohol having a valency of 3 or more is included, the amount of the polyhydric alcohol having a valency 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 the alcohol components constituting the amorphous resin A, from the viewpoint of obtaining a toner excellent in durability, folding resistance of the printed matter, and storage stability under high temperature and high humidity.

[0023] Examples of the carboxylic acid component include dicarboxylic acids and polyvalent carboxylic acids having a valency of 3 or more. These carboxylic acid components may be used alone or in combination of two or more.

[0024] 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 the carboxylic acid components constituting the amorphous resin A.

[0025] 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 preferred. 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 the total carboxylic acid component constituting the amorphous resin A.

[0026] The polyvalent carboxylic acid having a valence of 3 or more is preferably a trivalent carboxylic acid, and examples thereof include trimellitic acid. When a polyvalent carboxylic acid having a valence of 3 or more is included, 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 the total carboxylic acid component constituting the amorphous resin A.

[0027] 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. From the viewpoint of obtaining a toner excellent in durability, fold resistance of printed matter, and storage stability under high temperature and high humidity, it is preferably a resin obtained by polycondensing with polyethylene terephthalate.

[0028] As the polyethylene terephthalate, those produced according to a conventional method by polycondensation of ethylene glycol and terephthalic acid, dimethyl terephthalate, etc. can be used.

[0029] 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 viewpoint of obtaining a toner excellent in durability. The IV value is an index of the molecular weight. The IV value of polyethylene terephthalate can be adjusted by the polycondensation time or the like. The measurement of the IV value can be carried out, 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. [Number] [In the formula, k is Huggins' constant, C is the concentration of the sample solution (g / dL), η = (t1 / t0) - 1, t0 is the dropping time in seconds of only the solvent, and t1 is the dropping time in seconds of the sample solution. k was taken as 0.33. ]

[0030] 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), etc.

[0031] The equivalent ratio of the carboxy group of the carboxylic acid component to the hydroxy 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.

[0032] [[Composite resin]] The composite resin contains a polyester resin segment and a vinyl-based resin segment. The polyester resin segment is preferably composed 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 with 3 to 22 carbon atoms.

[0033] 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.

[0034] 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.

[0035] [[Method for producing amorphous resin A]] When the amorphous resin A is a polyester resin, it can be obtained, for example, 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, or 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 of the total amount 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 of the total amount 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 preferably 250°C or lower, more preferably 240°C or lower. The polycondensation may be carried out in an inert gas atmosphere.

[0036] 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 using an alcohol component and a carboxylic acid component, and step B of performing an addition polymerization reaction using 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 a 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 both reactive monomers are further advanced. This method is preferred. The conditions of step A are the same as those of the method for producing the polyester resin described above.

[0037] 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 based on 100 parts by mass of the raw material monomer of the vinyl-based resin segment. The temperature of the additional 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.

[0038] 〔Physical properties of amorphous resin A〕 From the viewpoint of further improving the storage stability under high temperature and high humidity, 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 storage stability under high temperature and high humidity, 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.

[0039] From the viewpoints of durability, flexural resistance of the printed matter, and further improving the storage stability under high temperature and high humidity, the acid value of the amorphous resin A is preferably 2 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, and the manufacturing conditions such as reaction temperature, reaction time, and cooling rate. Also, these values are determined by the methods described in the examples. When two or more kinds of the amorphous resin A are used in combination, it is preferable that the values of the softening point, glass transition temperature, and acid value obtained as the mixture are respectively within the above-mentioned ranges.

[0040] 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, still more preferably 88% by mass or less.

[0041] In the present invention, from the viewpoint of durability, the polyester resin may preferably contain two or more kinds of polyester resins having different softening points of preferably 5°C or more, more preferably 10°C or more. Among the two or more kinds 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 the 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 the low-temperature fixability. Among the two or more kinds 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, 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 the low-temperature fixability. When containing two or more kinds of polyester resins, it is preferable to use two kinds 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, 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.

[0042] When using two kinds 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 is preferably 90 / 10 or less, more preferably 80 / 20 or less, still more preferably 70 / 30 or less.

[0043] <Compound B> Compound B has a polyolefin skeleton and a basic nitrogen-containing group from the viewpoint of obtaining a toner excellent in durability, fold resistance of printed matter, and storage stability under high temperature and high humidity. Compound B is preferably dispersed in the amorphous resin A. That is, it is preferable that Compound B is dispersed inside the toner particles.

[0044] 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.

[0045] 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.

[0046] Compound B has a polyolefin skeleton from the viewpoint of obtaining a toner excellent in durability, fold resistance of printed matter, and storage stability under high temperature and high humidity. 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, and a propylene / ethylene copolymer skeleton are preferable, a polyethylene skeleton or a polypropylene skeleton is more preferable, and a polypropylene skeleton is still more preferable.

[0047] 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. 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 as the polyamine compound. 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 more preferable, and tetraethylenepentamine is even more preferable.

[0048] The polyethyleneimine preferably contains, for example, a primary amino group, a secondary amino group, and a tertiary amino group and has a branched structure. Examples of the commercially available products 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.

[0049] 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, and 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.

[0050] 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, from the viewpoint of the adsorptivity to the resin having an acidic group.

[0051] 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-end acid-modified polyolefin, and more preferably a mono-end maleic anhydride-modified polyolefin.

[0052] The content of the polyolefin having a reactive functional group in the polyolefin skeleton 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 100% by mass or less, and still more preferably 100% by mass.

[0053] The melting point of the polyolefin skeleton raw material is preferably 60°C or more, more preferably 70°C or more, still more preferably 80°C or more, and preferably 160°C or less, more preferably 150°C or less, still more preferably 140°C or less.

[0054] The number average molecular weight of the polyolefin backbone raw material is preferably 100 or more, more preferably 200 or more, still more preferably 300 or more, and 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 backbone raw material can be determined, for example, by the gel permeation chromatography (GPC) method.

[0055] Examples of the polypropylene backbone raw material having a polypropylene backbone include "100Ts", "110Ts", "1001", "1010" of the "Umemex" series (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" of the "Hardlen" series (manufactured by Toyobo Co., Ltd.), "M-100", "M-300", "M-312", "PMA H1000P", "PMA-F2" of the "Toyotack" series (manufactured by Toyobo Co., Ltd.), "C", "L-206", "813A", "803M", "803MW", "803LT", "1026", "803L", "814H", "390S", "814B", "360T", "370M", "2027MB", "822", "892L", "930", "842LM", "851L" of the "Super Kron" series (manufactured by Nippon Paper Industries Co., Ltd.), and "X-10065", "X-10088", "X-10082", "X-10087", "X-10053", "X-10052" (manufactured by Baker Hughes).

[0056] [Method for producing Compound B] Compound B is obtained by reacting a basic nitrogen-containing group raw material with a polyolefin backbone 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.

[0057] The ratio (A / N) of the number of moles (A) of the reactive functional groups of the polyolefin backbone 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.

[0058] 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 polyolefin backbone raw material having a maleic anhydride moiety, the number of reactive functional groups per molecule is taken as 1. The amine value of the basic nitrogen-containing group raw material can be measured by hydrochloric acid titration or perchloric acid titration.

[0059] In the case of the reaction between the polyamine compound and the 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.

[0060] [Physical properties of Compound B] 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, from the viewpoints of improving durability, fold resistance of the printed matter, and storage stability under high temperature and high humidity. The melting point is measured by the method described in the examples.

[0061] The number average molecular weight of Compound B is preferably 500 or more, more preferably 800 or more, still more preferably 1,000 or more, and preferably 20,000 or less, more preferably 10,000 or less, still more preferably 7,000 or less, from the viewpoints of improving durability, bend resistance of the printed matter, and storage stability under high temperature and high humidity conditions.

[0062] 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 parts by mass or more, and 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, based on 100 parts by mass of the binder resin, from the viewpoints of improving durability, bend resistance of the printed matter, and storage stability under high temperature and high humidity conditions.

[0063] <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.

[0064] The melting point of Release Agent C is preferably 60°C or higher, more preferably 70°C or higher, and 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 the release agent C is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, still more preferably 2 parts by mass or more, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less, based on 100 parts by mass of the binder resin.

[0065] <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.

[0066] 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, Ltd.), "Eisen Spiron 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, Ltd.), "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.; and organometallic compounds.

[0067] 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, and still more preferably 3 parts by mass or less with respect to 100 parts by mass of the binder resin.

[0068] <Colorant> The toner may contain a colorant. Examples of the colorant that can be used include dyes, pigments, etc. used as colorants for toners, such as 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. The toner of the present invention may be either a black toner or a color toner other than black.

[0069] 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.

[0070] The toner may further contain other reinforcing fillers such as magnetic powder, fluidity improver, conductivity regulator, fibrous substances, and additives such as antioxidant, anti-aging agent, and cleaning property improver.

[0071] For example, the toner contains toner particles. The toner particles preferably contain amorphous resin A, compound B, and 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 the toner as they are, it is preferable to use the toner particles with an external additive added to the surface of the toner particles as the toner. The toner is preferably used as a dry toner.

[0072] [Manufacturing method of toner] 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 viewpoints of productivity and dispersibility of the colorant, a pulverized toner obtained by the melt-kneading method is preferable.

[0073] In the case of a pulverized toner, the manufacturing method of the toner is, for example, Step 1: A step of melt-kneading a mixture containing amorphous resin A, compound B, and 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.

[0074] In Step 1, additives such as a charge control agent and a colorant may be contained 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, an open roll kneader, etc. 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. After cooling the melt-kneaded product obtained in Step 1 to an extent that it can be pulverized, it is fed to the subsequent Step 2.

[0075] The pulverization in Step 2 may be carried out in multiple stages. For example, after roughly 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 suitably used for rough pulverization include a hammer mill, an atomizer, and a rotorplex. Examples of pulverizers suitably used for fine pulverization include a fluidized bed jet mill, a collision plate jet mill, and a rotary mechanical mill. Among these, from the viewpoint of pulverization efficiency, a fluidized bed jet mill and a collision plate jet mill are preferred, and a collision plate jet mill is more preferred.

[0076] Examples of classifiers used for classification include a rotor classifier, an air classifier, an inertial classifier, and a sieve classifier. During the classification step, the pulverized product that was not sufficiently pulverized and removed may be fed back to the pulverization step, and the pulverization step and the classification step may be repeated as necessary.

[0077] The volume median 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.

[0078] It is preferable that a fluidizing agent or the like is added as an external additive to the surface of the toner particles. Examples of the external additive include fine particles of inorganic materials such as hydrophobic silica, titanium oxide, alumina, cerium oxide, and carbon black, and polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, hydrophobic silica is preferred. 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.

[0079] The toner is used for developing a latent image formed in electrophotography, electrostatic recording, electrostatic printing, etc. The toner can be used as a one-component developer or as a two-component developer by mixing with a carrier. [Examples]

[0080] [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)).

[0081] [Softening point, glass transition temperature, etc. of 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. The plunger descent amount of the flow tester was plotted against the temperature, 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 0 °C 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 0 °C to 150 °C at a heating rate of 10 °C / min. The temperature of 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.

[0082] [Number average molecular weight and weight average molecular weight of the polyester resin] 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 by the following method. (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 flow 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 there for measurement. The molecular weight of the sample was calculated based on a calibration curve prepared in advance. The calibration curve at this time included 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 , 7.00×103 , 5.04×10 4 ) was used as a standard sample. Measuring device: CO-8010 (trade name, manufactured by Tosoh Corporation) Analysis column: GMH XL +G3000H XL (both are trade names, manufactured by Tosoh Corporation)

[0083] [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. The maximum peak temperature of the endotherm was taken as the melting point.

[0084] [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.

[0085] [Volume median diameter (D 50 )] The volume median diameter of the toner was measured as follows. · Measuring instrument: Coulter Multisizer III (trade name, manufactured by Beckman Coulter) · Aperture diameter: 50 μm · Analysis software: Multisizer III version 3.51 (trade name, manufactured by Beckman Coulter) · Electrolyte: Isoton II (trade name, manufactured by Beckman Coulter) · Dispersion liquid: Polyoxyethylene lauryl ether (manufactured by Kao Corporation, trade name: Emulgen 109P, HLB: 13.6) was dissolved in the above electrolyte to obtain a dispersion liquid with a concentration of 5 mass%. ·Dispersion conditions: 10 mg of the measurement sample was added to 5 mL of the dispersion liquid, and dispersed for 1 minute using an ultrasonic disperser. Then, 25 mL of the electrolytic solution was added, and further dispersed for 1 minute using an ultrasonic disperser to prepare a sample dispersion liquid. ·Measurement conditions: By adding the sample dispersion liquid to 100 mL of the electrolytic solution, after adjusting the concentration to a level where the particle sizes of 30,000 particles could be measured in 20 seconds, 30,000 particles were measured, and the volume median diameter (D 50 ) was determined from the particle size distribution.

[0086] [Production of alkenyl succinic anhydride] (Production of alkylene compound A) Using propylene tetramer (manufactured by Nippon Oil Corporation, trade 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 the gas chromatography-mass spectrometry described later. The distribution of the alkylene compound was measured according to the analysis by gas chromatography-mass spectrometry of alkylene compound A in JP-A-2014-013384, and C9H 18 : 0.5 mass%, C 10 H 20 : 4 mass%, C 11 H 22 : 20 mass%, C 12 H 24 : 66 mass%, C 13 H 26 : 9 mass%, C 14 H 28 : 0.5 mass% (the number of peaks corresponding to alkylene compounds with 9 to 14 carbon atoms was 6).

[0087] (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 Chemicals 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 pressure 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 completion of the reaction, 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 in 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.

[0088] [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, 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 introduction tube, stirrer, and 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.

[0089] Production Examples H8, H9, L8, L9 (Resins H-8, H-9, L-8, L-9) The raw material monomers of the polyester resin, the esterification catalyst, and gallic acid 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 fractionation tube through which hot water at 98°C passed, a stirrer, and a thermocouple. After maintaining the temperature at 180°C for 1 hour under a nitrogen atmosphere, the temperature was raised 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. Further, the reaction was carried out under a reduced pressure of 10 kPa at 230°C until the softening point described in Tables 1 and 2 was reached to obtain a polyester resin.

[0090] Production Example H14 (Production of Resin H-14) The raw material monomers of the polyester resin other than trimellitic anhydride, the esterification catalyst, and gallic acid shown in Table 1 were placed in a 5-liter four-necked flask equipped with a nitrogen inlet tube, a stirrer, and a thermocouple. After maintaining the temperature at 180°C for 1 hour under a nitrogen atmosphere, the temperature was raised 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. Then, 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 until the softening point described in Table 1 was reached to obtain a polyester resin.

[0091] Production Examples, H17, L16 (Production of Resins H-17, L-16) The raw material monomers of the polyester resin, the esterification catalyst, and gallic acid 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. The temperature was raised to 235°C under a nitrogen atmosphere, and then polycondensation was carried out at 235°C for 6 hours. Then, the temperature was lowered to 210°C, and the reaction was carried out under a reduced pressure of 10 kPa until the softening point described in Tables 1 and 2 was reached to obtain a polyester resin.

[0092]

Table 1-1

[0093]

Table 1-2

[0094]

Table 1-3

[0095]

Table 2-1

[0096]

Table 2-2

[0097]

Table 2-3

[0098] [Production of Compound B] Production Example B1 (Production of Compound B-1) Into a 2 L four-necked flask equipped with a condenser, nitrogen inlet tube, stirrer, dehydrating tube, and 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 end anhydride (PPSA1000) (manufactured by Baker Hughes, trade name "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 placed, 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 of the acid anhydride derived from PPSA (1780 cm -1 ) disappeared and the peak of the imide bond (1700 cm -1 ) appeared, and Compound B-1 was obtained. The melting point is shown in Table 3.

[0099] Production Example B2 (Production of Compound B-2) The wax affinity group raw material was changed to maleic anhydride-modified polypropylene with one end anhydride (PPSA2500) (manufactured by Baker Hughes, "X-10088", melting point 119°C, number average molecular weight 2,500), and the amounts of the basic nitrogen-containing group raw material and xylene were changed as shown in Table 3. Compound B-2 was obtained in the same manner as in Production Example B1 except for these changes. The melting point is shown in Table 3.

[0100]

Table 3

[0101] [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 Co., 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 part 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. The obtained melt-kneaded product was cooled and coarsely pulverized, and then pulverized and classified with a jet mill to obtain a powder (toner mother particles) having a volume median diameter (D 50 ) of 7.0 μm. 100 parts by mass of the obtained powder (toner mother particles) and, as external additives, 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) were mixed with a Henschel mixer for 3 minutes to obtain a toner. The evaluation results of the obtained toner are shown in Table 4.

[0102] Examples 2 to 17, Comparative Examples 1 to 5 In Example 1, 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 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.

[0103] [Evaluation] [Heat-resistant storage stability of toner] 10 g of the toner was placed in a 50 mL poly cup and kept in an environment of 50°C and 60% RH for 24 hours. Then, three sieves of Sieve A (aperture 250 μm), Sieve B (aperture 150 μm), and Sieve C (aperture 75 μm) were stacked in order from above on a powder tester (manufactured by Hosokawa Micron Corporation), 10 g of the toner was placed on Sieve A, and vibration was applied for 60 seconds. The fluidity was evaluated based on the following evaluation criteria for the value (α) calculated from the following formula. The larger the numerical value, the more preferable. α = 100 - 〔(mass of toner remaining on Sieve A (g)) + (mass of toner remaining on Sieve B (g)) × 0.6 + (mass of toner remaining on Sieve C (g)) × 0.2〕 / 10 (g) × 100

[0104] [Flex resistance] The toner was mounted on a device in which the fixing unit of a copying machine "AR-505" (manufactured by Sharp Corporation) was improved so that fixing outside the device was possible, and a printed matter was obtained in an unfixed state (printing area: 20 cm × 20 cm, adhesion amount: 0.5 mg / cm 2 ). Then, using a fixing unit (fixing speed 300 mm / sec) adjusted so that the total fixing pressure was 40 kgf, the fixing was performed with the temperature of the fixing roll set at 160°C. The maximum value of the width of the image defect after this image was bent inward for 30 seconds at 50 g / cm 2 and then opened again and the damaged image was wiped off with a soft cloth was used as an index of the flex resistance of the printed matter. The smaller the maximum value of the width of the image defect, the better the flex resistance of the printed matter. Note that "CopyBond SF-70NA" (manufactured by Sharp Corporation, 75 g / m 2 ) was used as the fixing paper.

[0105] [Durability of Toner] Toner was mounted on a printing machine "PagePress N-4" (manufactured by Casio Computer Co., Ltd., fixing: contact fixing method, developing: non-magnetic one-component developing 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 a temperature of 32 °C and a humidity of 85%. During the 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 9,000 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 developing 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.

[0106]

Table 4

[0107] From the results of the examples and comparative examples above, it can be seen that a toner excellent in durability, folding resistance of printed matter, and storage stability under high temperature and high humidity 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 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 containing an aliphatic alcohol having 4 to 8 carbon atoms as an alcohol component constituting the amorphous resin A, wherein the content of the aliphatic alcohol having 4 to 8 carbon atoms is 10 mol% or more with respect to 100 mol% of the total alcohol components constituting the amorphous resin A, the release agent C is a hydrocarbon wax, an electrostatic charge image developing toner.

2. The electrostatic charge image developing toner according to claim 1, wherein the compound B is a reaction product of a basic nitrogen-containing group raw material and a polyolefin skeleton raw material.

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

4. The electrostatic charge image developing toner according to any one of claims 1 to 3, wherein the basic nitrogen-containing group is an amino group.

5. The electrostatic charge image developing toner according to any one of claims 1 to 4, wherein the acid value of the amorphous resin A is 5 mgKOH / g or more and 40 mgKOH / g or less.

6. The electrostatic charge image developing toner according to any one of claims 1 to 5, 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 with respect to 100 mol% of the total alcohol components constituting the amorphous resin A.

7. The electrostatic charge image developing toner according to any one of claims 1 to 6, containing an aliphatic alcohol having 4 to 6 carbon atoms as an alcohol component constituting the amorphous resin A.

8. The electrostatic charge image developing toner according to any one of claims 1 to 7, wherein the aliphatic alcohol component having 4 to 8 carbon atoms contained as an alcohol component constituting the amorphous resin A has a branched structure.

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