JP2022016370A - Toner for electrostatic charge image development - Google Patents

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

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

In the field of electrophotographic, with the development of electrophotographic systems, there is a demand for the development of toners for electrophotographics that can achieve high image quality and high speed.

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

Japanese Unexamined Patent Publication No. 2019-174672 Japanese Unexamined Patent Publication No. 2019-184931

The present invention relates to a toner for static charge image development, which is excellent in durability, bending resistance of printed matter, and storage under high temperature and high humidity.

The present invention is at least one basic nitrogen selected from the group consisting of an amorphous resin A having an acidic group, a polyolefin skeleton, and an amino group, an imino group, a cyano group, an azo group, a diazo group, and an azi group. The present invention relates to a toner for static charge image development, which contains a compound B having a containing group and a mold release agent C, and contains an aliphatic alcohol having 4 or more and 8 or less carbon atoms as an alcohol component constituting the amorphous resin A.

According to the present invention, there is provided a toner for static charge image development which is excellent in durability, bending resistance of printed matter, and storage under high temperature and high humidity.

[Toner for developing static charge image]
The static charge image developing toner (hereinafter, also simply referred to as “toner”) according to the present invention includes an amorphous resin A having an acidic group (hereinafter, also simply referred to as “acrystalline resin A”), a polyolefin skeleton, and the like. In addition, 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 azi group (hereinafter, also simply referred to as “compound B”). , A mold release agent C, and an aliphatic alcohol having 4 or more and 8 or less carbon atoms as an alcohol component constituting the amorphous resin A.
According to the above configuration, a toner having excellent durability, bending resistance of printed matter, and storage under high temperature and high humidity is provided.

The reason why the toner for static charge image development of the present invention is excellent in durability, bending resistance of printed matter, and storage stability under high temperature and high humidity is not clear, but it is considered as follows.
The acid-base interaction between the acidic group of the amorphous resin A and the basic nitrogen-containing group of the compound B causes the compound B to be finely dispersed in the amorphous resin A. Along with this, a state in which the polyolefin chemically bonded to the compound B is finely dispersed in the amorphous resin A is formed. It is considered that the release agent having high hydrophobicity is finely dispersed by the polyolefin, and as a result, the amount of the release agent on the toner surface is reduced, so that the durability is excellent.
Furthermore, surprisingly, by containing an aliphatic alcohol having 4 or more and 8 or less carbon atoms as an alcohol component constituting the amorphous resin A, the printed matter has bending resistance and storage stability under high temperature and high humidity. Also turned out to be excellent. In order to improve the bending resistance of the printed matter, 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 the ester group concentration of the resin is increased by using the aliphatic alcohol, the hygroscopicity is increased and the storage stability is deteriorated under high temperature and high humidity. By containing an aliphatic alcohol having 4 or more carbon atoms and 8 or less carbon atoms as an alcohol component constituting the amorphous resin A, it was possible to appropriately hydrophilize and increase the ester group concentration, probably because the printed matter was resistant to bending. It is considered to have excellent properties and storage stability under high temperature and high humidity.

Definitions of various terms in the present specification are shown below.
Whether the resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is defined by the ratio of the softening point of the resin to the maximum endothermic peak temperature (softening point (° C.) / maximum endothermic peak temperature (° C.)) in the measurement method described in Examples described later. The crystalline resin is a resin having a crystallinity index of 0.6 or more and 1.4 or less. 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 depending on the type and ratio of the raw material monomers, and the production conditions such as reaction temperature, reaction time, and cooling rate.
As used herein, the term "binding resin" means a resin component contained in a toner containing an amorphous resin A.
In the specification, the carboxylic acid component of the polyester resin includes not only the exemplified compound but also an anhydride which decomposes during the reaction to generate an acid, and an alkyl ester of each carboxylic acid (alkyl group having 1 or more carbon atoms and 3 carbon atoms). The following) is also included.
"Alkyl (meth) acrylate" means alkyl acrylate or alkyl methacrylate. Further, with respect to the alkyl moiety, "(iso)" means normal alkyl or isoalkyl.

<Amorphous resin A>
The amorphous resin A has an acidic group from the viewpoint of obtaining a toner having excellent durability, bending resistance of printed matter, and storage under high temperature and high humidity.
Examples of the acidic group include a carboxy group, a sulfo group and a phosphoric acid group. Of these, the carboxy group is preferable.
The amorphous resin A is not particularly limited as long as it has an acidic group, and examples thereof include polyester-based resins and polystyrene-based resins. Among these, polyester resin is preferable. In the case of a polyester resin, the carboxy group at the end of the polymer chain of the resin corresponds to at least the above-mentioned acidic group.
Examples of the polyester-based resin include polyester resins and modified polyester-based resins. Examples of the modified polyester resin include a urethane modified polyester resin in which the polyester resin is modified by a urethane bond, an epoxy modified polyester resin in which the polyester resin is modified by an epoxy bond, a polyester resin segment and a vinyl resin segment. Examples thereof include composite resins containing.

[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 trihydric or higher polyhydric alcohols. These alcohol components may be used alone or in combination of two or more.

The amorphous resin A in the present invention has 4 carbon atoms as an alcohol component constituting the amorphous resin A from the viewpoint of obtaining a toner having excellent durability, bending resistance of printed matter, and storage under high temperature and high humidity. It contains 8 or more and 8 or less aliphatic alcohols. The carbon number 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 trihydric or higher polyhydric alcohol. Moreover, it is preferable that the aliphatic alcohol has a branched structure.

Examples of the linear or branched aliphatic diol having 4 or more and 8 or less carbon atoms include 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, and 2, Examples thereof include 2-dimethyl-1,3-propanediol (also referred to as neopentyl glycol), 1,6-hexanediol, and 1,8-octanediol. Among these, it is 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. At least one is preferable, and 2,2-dimethyl-1,3-propanediol is more preferable.

Examples of the trihydric or higher polyhydric alcohol having 4 or more and 8 or less carbon atoms include pentaerythritol, trimethylolpropane, and sorbitol.

The total content of the aliphatic alcohol having 4 or more and 8 or less carbon atoms constitutes the amorphous resin A from the viewpoint of obtaining a toner having excellent durability, bending resistance of printed matter, and storage under high temperature and high humidity. 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 more, based on 100 mol% of the total alcohol component. Below, it is more preferably 80 mol% or less, still more preferably 70 mol% or less, still more preferably 65 mol% or less.

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

（式中、ＯＲ¹及びＲ²Ｏはオキシアルキレン基であり、Ｒ¹及びＲ²はそれぞれ独立にエチレン基又はプロピレン基であり、ｘ及びｙはアルキレンオキシドの平均付加モル数を示し、それぞれ正の数であり、ｘとｙの和の値は、１以上、好ましくは１．５以上であり、１６以下、好ましくは８以下、より好ましくは４以下である）
で表されるビスフェノールＡのアルキレンオキシド付加物である。 The aromatic diol is preferably an alkylene oxide adduct of bisphenol A, more preferably of the formula (I) :.

(In the formula, OR ¹ and R ² O are oxyalkylene groups, R ¹ and R ² are independently ethylene or propylene groups, and x and y indicate the average number of moles of alkylene oxide added, respectively, which are positive. The value of the sum of x and y is 1 or more, preferably 1.5 or more, 16 or less, preferably 8 or less, and more preferably 4 or less).
It is an alkylene oxide adduct of bisphenol A represented by.

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.

The total content of the ethylene oxide adduct of bisphenol A or the propylene oxide adduct of bisphenol A is 100 mol% of the total alcohol component constituting the amorphous resin A from the viewpoint of obtaining a toner having excellent bending resistance of the printed matter. On the other hand, it 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.

Examples of the trihydric or higher polyhydric alcohol other than the aliphatic alcohol having 4 or more and 8 or less carbon atoms include glycerin.

When a trihydric or higher polyhydric alcohol is contained, the amount of the trihydric or higher polyhydric alcohol is amorphous from the viewpoint of obtaining a toner having excellent durability, bending resistance of printed matter, and storage under high temperature and high humidity. It 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 the total alcohol component constituting the sex resin A. ..

Examples of the carboxylic acid component include a dicarboxylic acid and a trivalent or higher valent carboxylic acid. As these carboxylic acid components, one kind or two or more kinds may be used.

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, based on 100 mol% of the total carboxylic acid component constituting the amorphous resin A. , And preferably 100 mol% or less, more preferably 100 mol%.

The linear or branched aliphatic dicarboxylic acid has 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, dodecanedic acid, and azelaic acid. , Succinic acid substituted with an alkyl group having 1 or more and 20 or less carbon atoms or an alkenyl group having 2 or more and 20 or less 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 with respect to 100 mol% of the total carboxylic acid component constituting the amorphous resin A. It is less than or equal to mol%, and preferably more than 0 mol%, more preferably 0 mol%.

The trivalent or higher valent carboxylic acid is preferably a trivalent carboxylic acid, and examples thereof include trimellitic acid.
When a trivalent or higher polyvalent carboxylic acid is contained, the amount of the trivalent or higher polyvalent carboxylic acid is preferably 30 mol% or less, preferably 30 mol% or less, based on 100 mol% of the total carboxylic acid component constituting the amorphous resin A. It is preferably 20 mol% or less, preferably 0 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more.

The polyester resin may be a resin obtained by polycondensing a polycondensable monomer containing a carboxylic acid component and an alcohol component with polyethylene terephthalate, and has durability, bending resistance of a printed matter, and high temperature and humidity. From the viewpoint of obtaining a toner having excellent storage stability, a resin obtained by polycondensing with polyethylene terephthalate is preferable.

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

〔式中、ｋはハギンズの定数であり、Ｃは試料溶液の濃度（ｇ／ｄＬ）であり、η＝（ｔ₁／ｔ₀）－１であり、ｔ₀は溶媒のみの落下秒数であり、ｔ₁は試料溶液の落下秒数である。ｋは0.33とした。〕 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, from the viewpoint of obtaining a toner having excellent durability. Yes, and it is 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. The IV value is an index of molecular weight. The IV value of polyethylene terephthalate can be adjusted by the polycondensation time and the like.
To measure the IV value, for example, dissolve the sample in a mixed solvent of phenol / tetrachloroethane = 60/40 (mass ratio) at a concentration of 0.4 g / dL, measure with an Ubbelohde viscometer, and use the following formula. It can be calculated according to.

[In the formula, k is the Huggins constant, C is the concentration of the sample solution (g / dL), η = (t ₁ / t ₀ ) -1, and t ₀ is the number of seconds that the solvent alone falls. Yes, t ₁ is the number of seconds the sample solution has fallen. k was set to 0.33. ]

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

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. It is preferably 1.2 or less.

[Composite resin]
The composite resin includes a polyester resin segment and a vinyl resin segment. The polyester resin segment is preferably made of the polyester resin described above.
The vinyl-based resin segment is preferably an addition polymer of a raw material monomer containing a styrene-based compound, and more preferably contains a styrene-based compound and a vinyl-based monomer having an aliphatic hydrocarbon group having 3 or more and 22 or less carbon atoms. It is an addition polymer of the raw material monomer.

The amount of the polyester resin segment 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 in the composite resin. Yes, 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 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 more in the composite resin. It is mass% or less, more preferably 40% by mass or less, still more preferably 30% by mass or less.

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

[Manufacturing method of 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, add an esterification catalyst such as di (2-ethylhexanoic acid) tin (II), dibutyl tin oxide, and titanium diisopropyrate bistriethanol aminated to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. 0.01 part by mass or more and 5 parts by mass or less; 0 parts by mass of an esterification co-catalyst such as gallic acid (same as 3,4,5-trihydroxybenzoic acid) for a total amount of 100 parts by mass of alcohol component and carboxylic acid component. It may be polycondensed by using 001 parts by mass or more and 0.5 parts by mass or less.
The temperature of the polycondensation reaction is preferably 120 ° C. or higher, more preferably 160 ° C. or higher, further 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.

When the amorphous resin A is a composite resin, for example, a step A in which a polycondensation reaction is carried out with an alcohol component and a carboxylic acid component, and a step in which an addition polymerization reaction is carried out with a raw material monomer and a bireactive monomer of a vinyl resin segment. It may be manufactured by a method including B.
The process B may be performed after the process A, the process A may be performed after the process B, or the process A and the process B may be performed at the same time.
In step A, a part of the carboxylic acid component is subjected to a polycondensation reaction, then step B is carried out, and then the rest of the carboxylic acid component is added to the polymerization system, and the polycondensation reaction of step A and, if necessary, both reactions. A method of further advancing the reaction with the sex monomer is preferable.
The conditions of step A are the same as the above-mentioned method for producing a polyester resin.

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). Can be mentioned.
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.

[Physical characteristics of amorphous resin A]
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 low temperature from the viewpoint of further improving the storage stability under high temperature and high humidity. From the viewpoint of further improving the fixability, the temperature is preferably 160 ° C. or lower, more preferably 150 ° C. or lower, still more preferably 140 ° C. or lower.
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 storage stability under high temperature and high humidity. From the viewpoint of further improving the low temperature fixability, the temperature is preferably 80 ° C. or lower, more preferably 75 ° C. or lower, and further preferably 70 ° C. or lower.

The acid value of the amorphous resin A is preferably 2 mgKOH / g or more, more preferably 5 mgKOH / g or more, from the viewpoint of further improving durability, bending resistance of the printed matter, and storage stability under high temperature and high humidity. It is more preferably 10 mgKOH / g or more, still more preferably 12 mgKOH / g or more, and preferably 40 mgKOH / g or less, more preferably 35 mgKOH / g or less, still more preferably 30 mgKOH / g or less.
The softening point, glass transition temperature, and acid value of the amorphous resin A can be appropriately adjusted depending on the type of the raw material monomer and the amount used thereof, and the production conditions such as the reaction temperature, the reaction time, and the cooling rate. Those values are determined by the method described in the examples.
When two or more kinds of amorphous resins A are used in combination, it is preferable that the softening point, the glass transition temperature, and the acid value obtained as a mixture thereof are within the above-mentioned ranges.

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 100% by mass or less. It is 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.

In the present invention, the polyester resin may contain two or more kinds of polyester resins having a softening point of preferably 5 ° C. or higher, more preferably 10 ° C. or higher, and different from each other, from the viewpoint of durability. 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 higher, more preferably 90 ° C. or higher, still more preferably, from the viewpoint of further improving durability. The temperature is 100 ° C. or higher, and from the viewpoint of further improving the low temperature fixability, the temperature is preferably 135 ° C. or lower, more preferably 120 ° C. or lower, still more preferably 115 ° C. or lower. 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 higher, more preferably 120 ° C. or higher, and the viewpoint of further improving the low temperature fixability. Therefore, it is preferably 160 ° C. or lower, more preferably 150 ° C. or lower, and further preferably 140 ° C. or lower. When two or more kinds of polyester resins are contained, 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 higher, more preferably 10 ° C. or higher, still more preferably 15 ° C. or higher, and durability. From the viewpoint of low temperature fixability, the temperature is preferably 60 ° C. or lower, more preferably 50 ° C. or lower, still more preferably 40 ° C. or lower.

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

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

Basic nitrogen-containing groups include amino group, imino group (= NH), cyano group (-CN), azo group (-N = N-), diazo group (= N ₂ ), and azi group (-N ₃ ). It is at least one species selected from the group consisting of.
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.

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.

Compound B has a polyolefin skeleton from the viewpoint of obtaining a toner having excellent durability, bending resistance of printed matter, and storage under high temperature and high humidity.
Examples of the polyolefin forming the polyolefin skeleton include polyethylene, polypropylene, polybutylene, polymethylpentene, polytetradecene, polyhexadecene, polyoctadecene, polyeicosene, polydococene, and copolymers 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 further preferable.

Compound B is, for example, a reaction product of a basic nitrogen-containing base raw material and a polyolefin skeleton raw material.
Examples of the basic nitrogen-containing base raw material include polyamine compounds.
Examples of the polyamine compound include polyalkyleneamine, polyallylamine, and polyaminoalkylmethacrylate.
As the polyamine compound, a polyalkylene amine having at least one amino group selected from the group consisting of a primary amino group and a secondary amino group is preferable from the viewpoint of adsorptivity to a binder resin having an acidic group.
Examples of the polyalkylene amine include polyethylene amine, polypropylene amine, and polybutylene amine.
Examples of 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 further preferable.

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 commercially available polyethyleneimine products include "SP-003", "SP-006", "SP-012", and "SP-018" (all manufactured by Junsei Chemical Co., Ltd.) of the "Epomin" series. ..
Examples of the polyaminoalkyl methacrylate include polydimethylaminoethyl methacrylate.

The amine value of the basic nitrogen-containing group raw material is preferably 1 mmol / g or more, more preferably 3 mmol / g or more, still more preferably 5 mmol / g or more, and preferably 50 mmol / g or less, more preferably 40 mmol / g. It is g or less, 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 Examples described later.

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, from the viewpoint of the adsorptivity of the acidic group to the resin. It is 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.

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 the anhydride thereof. Examples of the halogeno group include a chloro group, a bromo group and an iodine group. Among these, a carboxy group or an anhydride thereof or a halogeno group is preferable, and a carboxy group or an anhydride thereof is more preferable, from the viewpoint of safety and reactivity.
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. Be done.
As the acid-modified polyolefin, one-ended acid-modified polyolefin is preferable, and one-ended maleic anhydride-modified polyolefin is more preferable.

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, further preferably 90% by mass or more, and 100% by mass or less. , More preferably 100% by mass.

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

The number average molecular weight of the polyolefin skeleton 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,. It is 500 or less.
The number average molecular weight of the polyolefin skeleton raw material can be determined, for example, by a gel permeation chromatography (GPC) method.

Examples of the polypropylene skeleton raw material having a polypropylene skeleton include "100Ts", "110Ts", "1001", "1010" (all manufactured by Sanyo Kasei Kogyo Co., Ltd.) in the "Yumex" series, and "13" in the "Hardlen" series. -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" (all manufactured by Toyobo Co., Ltd.), "Toyo Tuck" series "M-100", "M-300" , "M-312", "PMA H1000P", "PMA-F2" (all manufactured by Toyobo Co., Ltd.), "C", "L-206", "813A", "803M" of the "Supercron" series. , "803MW", "803LT", "1026", "803L", "814H", "390S", "814B", "360T", "370M", "2027MB", "822", "892L", " 930 "," 842LM "," 851L "(all manufactured by Nippon Paper Co., Ltd.)," X-10065 "," X-10088 "," X-10082 "," X-10087 "," X-10053 ", Examples thereof include "X-10052" (all manufactured by Baker Hughes).

[Method for producing compound B]
Compound B is obtained by reacting a basic nitrogen-containing base 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.

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

The above ratio (A / N) is calculated as follows.
Ratio (A / N) = 1000 x [Number of reactive functional groups per molecule of aliphatic hydrocarbon group raw material (A) x (Amount of aliphatic hydrocarbon group raw material charged / Molecular weight of aliphatic hydrocarbon group raw material)] / [Amine value of basic nitrogen-containing group raw material (mmol / g) x amount of basic nitrogen-containing group raw material charged]
However, in the polyolefin skeleton 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 method or perchloric acid titration.

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 observing a peak (1700 cm ^-1 ) derived from the imide bond by infrared spectroscopy (hereinafter, also simply referred to as “IR”).

[Physical characteristics 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, from the viewpoint of improving durability, bending resistance of printed matter, and storage stability under high temperature and high humidity. It is 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 Examples.

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, from the viewpoint of improving durability, bending resistance of printed matter, and storage under high temperature and high humidity. And preferably 20,000 or less, more preferably 10,000 or less, still more preferably 7,000 or less.

The content of the compound B is preferably 0.1 part by mass or more with respect to 100 parts by mass of the binder resin from the viewpoint of improving durability, bending resistance of the printed matter and storage stability under high temperature and high humidity. It is more preferably 0.5 parts by mass or more, further preferably 1 part by mass or more, further 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. Hereinafter, it is more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less.

<Release C>
Examples of the release agent C include hydrocarbon waxes or oxides thereof, ester waxes, fatty acid amides, fatty acids, fatty acid metal salts, higher alcohols and the like. Among these, a hydrocarbon wax or an oxide thereof or an ester wax is preferable, a hydrocarbon wax or an oxide thereof is more preferable, and a hydrocarbon wax is further preferable.
Examples of the hydrocarbon wax include polyolefin waxes such as polypropylene wax, polyethylene wax and polypropylene-polyethylene copolymer wax; paraffin wax, microcrystalline wax, Fishertropsh wax, sazole wax and the like.
Examples of the ester wax include carnauba wax, montan wax, deoxidizing wax thereof, fatty acid ester wax and the like. These can be used alone or in combination of two or more.

The melting point of the release agent C is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, and preferably 160 ° C. or lower, more preferably 130 ° C. or lower, still more preferably 115 ° C. or lower. The melting point of the release agent C is determined by the method described in Examples described later.
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 2 parts by mass or more with respect to 100 parts by mass of the binder resin. It is 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less.

<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.
Positive charge control agents include niglosin dyes such as "niglocin base EX", "oil black BS", "oil black SO", "bontron N-01", "bontron N-04", and "bontron N-07". , "Bontron N-09", "Bontron N-11" (all manufactured by Orient Chemical Industries Co., Ltd.), etc .; Triphenylmethane dyes containing a tertiary amine as a side chain, for example, a quaternary ammonium salt compound, for example, " Bontron P-51 "(manufactured by Orient Chemical Industries Co., Ltd.), cetyltrimethylammonium bromide," COPY CHARGE PX VP435 "(manufactured by Clariant), etc .; Polyamine resin, for example," AFP-B "(manufactured by Orient Chemical Industries Co., Ltd.), etc. Imidazole derivatives such as "PLZ-2001" and "PLZ-8001" (manufactured by Shikoku Kasei Kogyo Co., Ltd.); styrene-acrylic resins such as "FCA-701PT" (manufactured by Fujikura Kasei Co., Ltd.) and the like. Will be.

Examples of the negative charge control agent include metal-containing azo dyes such as "Varifast Black 3804", "Bontron S-31", "Bontron S-32", "Bontron S-34", and "Bontron S-36" ( (Manufactured by Orient Chemical Industry Co., Ltd.), "Eisenspiron Black TRH", "T-77" (manufactured by Hodoya Chemical Industry Co., Ltd.), etc .; Metal compounds of benzylic acid compounds, for example, "LR-147", " LR-297 "(above, manufactured by Nippon Carlit Co., Ltd.); metal compounds of salicylic acid compounds, for example," Bontron E-81 "," Bontron E-84 "," Bontron E-88 "," Bontron E-304 " (The above is manufactured by Orient Chemical Industry Co., Ltd.), "TN-105" (manufactured by Hodoya Chemical Industry Co., Ltd.), etc .; Copper phthalocyanine dye; Quadruple ammonium salt, for example, "COMPY CHARGE NX VP434" (manufactured by Clariant), Nitro Imidazole derivatives and the like; examples include organic metal compounds.

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, with respect to 100 parts by mass of the binder resin. Is 5 parts by mass or less, more preferably 3 parts by mass or less.

<Colorant>
The toner may contain a colorant.
As the colorant, dyes, pigments and the like used as colorants for toner can be used, for example, carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rodamine-B base, etc. Examples thereof include Solvent Red 49, Solvent Red 146, Solvent Blue 35, Quinacridone, Carmin 6B, and Disazo Yellow. The toner of the present invention may be either a black toner or a color toner other than black.

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 with respect to 100 parts by mass of the binder resin from the viewpoint of improving the image density of the toner. Parts or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less.

The toner may also contain additives such as a magnetic powder, a fluidity improver, a conductivity modifier, a reinforcing filler such as a fibrous substance, an antioxidant, an antioxidant, and a cleaning property improver.

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

[Toner manufacturing method]
The toner may be a toner obtained by any known method such as a melt-kneading method, an emulsification phase inversion method, an emulsification polymerization method, an emulsification aggregation method, etc., but from the viewpoint of productivity and dispersibility of the colorant, the toner may be obtained. Crushed toner by the melt-kneading method is preferable.

In the case of pulverized toner, the method for producing the toner is, for example,
Step 1: A step of melt-kneading a mixture containing an amorphous resin A, a compound B, and a mold release agent C, and a step 2: a step of crushing and classifying the melt-kneaded product obtained in Step 1 to obtain toner particles. including.

In step 1, additives such as a charge control agent and a colorant may be contained in the mixture. It is preferable that these toner raw materials are mixed in advance with a mixer such as a Henschel mixer or a ball mill and then supplied to the kneader.
The melt kneading in step 1 can be carried out using a known kneader such as a closed kneader, a single-screw extruder, a twin-screw extruder, or an open roll type kneader. Among these, a twin-screw extruder capable of setting a wide kneading temperature is preferable.
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 extent that it can be pulverized, and then subjected to the subsequent step 2.

The pulverization in step 2 may be performed in multiple stages. For example, the melt-kneaded product may be coarsely pulverized to 1 mm or more and 5 mm or less, and then further pulverized to a desired particle size.
Examples of the crusher preferably used for coarse crushing include a hammer mill, an atomizer, and a rotoplex. Examples of the pulverizer preferably used for fine pulverization include a fluidized bed type jet mill, a collision plate type jet mill, and a rotary mechanical type mill. Among these, a fluidized bed type jet mill and a collision plate type jet mill are preferable, and a collision plate type jet mill is more preferable, from the viewpoint of pulverization efficiency.

Examples of the classifying machine used for classifying include a rotor type classifying machine, an air flow type classifying machine, an inertial type classifying machine, and a sieve type classifying machine. In the classification step, the pulverized product removed due to insufficient pulverization may be subjected to the pulverization step again, or the pulverization step and the classification step may be repeated as necessary.

The volume median particle size (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, from the viewpoint of obtaining a high-quality image. It is preferably 8 μm or less.

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

The toner is used for developing a latent image formed by an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or the like. The toner can be used as a one-component developer or mixed with a carrier as a two-component developer.

[measurement]
[Acid value of resin]
The acid value of the resin was measured based on the method of JIS K 0070. However, only the measurement solvent was changed from the mixed solvent of ethanol and ether specified in JIS K0070 to the mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

[Resin softening point, glass transition temperature, etc.]
(1) Softening point Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), a 1 g sample is heated at a heating rate of 6 ° C./min while a load of 1.96 MPa is applied by a plunger to give a diameter of 1.96 MPa. Extruded from a 1 mm, 1 mm long nozzle. The amount of plunger drop of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was used as the softening point.
(2) Maximum peak endothermic temperature Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), the temperature was cooled from room temperature (20 ° C) to 0 ° C at a temperature lowering rate of 10 ° C / min. The sample was held as it was for 1 minute, and then the measurement was carried out while raising the temperature to 180 ° C. at a heating rate of 10 ° C./min. Of the observed endothermic peaks, the temperature of the peak on the highest temperature side was defined as the maximum endothermic temperature.
(3) Glass transition temperature Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.01 to 0.02 g of the sample into an aluminum pan and raise the temperature to 200 ° C. Then, the temperature was cooled to 0 ° C. at a temperature lowering rate of 10 ° C./min. Next, the measurement was performed while raising the temperature to 150 ° C. at a heating rate of 10 ° C./min. The temperature at the intersection of the extension of the baseline below the maximum endothermic temperature and the tangent showing the maximum slope from the rising portion of the peak to the peak of the peak was defined as the glass transition temperature.

[Number average molecular weight and weight average molecular weight of polyester resin]
The molecular weight distribution was measured by the gel permeation chromatography (GPC) method by the following method, and the number average molecular weight Mn and the 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 was 0.5 g / 100 mL. Then, this solution was filtered using a fluororesin filter having a pore size of 2 μm (manufactured by Sumitomo Electric Industries, Ltd., trade name: FP-200) to remove insoluble components, and used as a sample solution.
(2) Molecular weight measurement Using the following device, chloroform was flowed as an eluent at a flow rate of 1 mL per minute to stabilize the column in a constant temperature bath at 40 ° C. 100 μL of the sample solution was injected therein and the measurement was performed. The molecular weight of the sample was calculated based on a calibration curve prepared in advance. At this time, the calibration curve shows monodisperse polystyrene with several known molecular weights (manufactured by Tosoh Corporation; 2.63 × 10 ³ , 2.06 × ^{10 4} , 1.02 × 105, manufactured by GL Sciences Co., Ltd .; 2.10 × 10 ³ , 7.00 × 10 ³ , 5.04 × 10 ⁴ ) were used as standard samples.
Measuring device: CO-8010 (trade name, manufactured by Tosoh Corporation)
Analytical column: GMH _XL + G3000H _XL (both product names, manufactured by Tosoh Corporation)

[Melting point of wax and compound B]
Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.02 g of the sample into an aluminum pan, raise the temperature to 200 ° C, and then lower the temperature from 200 ° C to 10 ° C. It was cooled to 0 ° C. at / min. Next, the sample was heated at a heating rate of 10 ° C./min, the amount of heat was measured, and the maximum peak temperature of endotherm was taken as the melting point.

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

[Medium particle size of toner (D ₅₀ )]
The volume median particle size of the toner was measured as follows.
・ Measuring machine: 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: Polyoxyethylene lauryl ether (manufactured by Kao Corporation, trade name: Emargen 109P, HLB: 13.6) was dissolved in the electrolytic solution to obtain a dispersion having a concentration of 5% by mass.
Dispersion conditions: 10 mg of the measurement sample was added to 5 mL of the dispersion, dispersed for 1 minute with an ultrasonic disperser, then 25 mL of an electrolytic solution was added, and further dispersed with an ultrasonic disperser for 1 minute. A sample dispersion was prepared.
-Measurement conditions: By adding the sample dispersion to 100 mL of the electrolytic solution, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, and then the particle size distribution of 30,000 particles is measured. The volume median particle size (D ₅₀ ) was determined from.

[Manufacturing of alkenyl succinic anhydride]
(Production of alkylene compound A)
A alkylene compound (a) was obtained by fractional distillation under heating conditions of 183 to 208 ° C. using propylene tetramer (manufactured by Nippon Oil Co., Ltd., trade name: “light tetramer”). 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 mass analysis gas chromatography of the alkylene compound A of JP2014-103384, C ₉ H 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 (number of peaks corresponding to alkylene compounds having 9 to 14 carbon atoms) It was 6).

(Manufacturing of alkenyl succinic anhydride)
1 L of autoclave manufactured by Nitto High Pressure Co., Ltd., alkylene compound A 542.4 g, maleic anhydride 157.2 g, antioxidant Chelex-O (SC Organic Chemical Co., Ltd., Trisooctyl phosphite) 0.4 g, butyl as a polymerization inhibitor 0.1 g of hydroquinone was charged, and pressurized nitrogen substitution (0.2 MPaG) was repeated 3 times. After starting stirring at 60 ° C., the temperature was raised to 230 ° C. over 1 hour, and the reaction was carried out for 6 hours. The pressure at the time of reaching the reaction temperature was 0.3 MPaG. After completion of the reaction, the mixture was cooled to 80 ° C., returned to normal pressure (101.3 kPa), and transferred to a 1 L four-necked flask. The temperature was raised with stirring to 180 ° C., and the residual alkylene compound was distilled off at 1.3 kPa in 1 hour. Subsequently, after cooling to room temperature (25 ° C.), the pressure was returned to normal pressure (101.3 kPa) to obtain 406.1 g of the target alkenyl succinic anhydride. The average molecular weight of alkenyl succinic anhydride determined from the acid value was 268.

[Manufacturing of resin H and resin L]
Production Examples H1 to H7, H10 to H13, H15, H16, L1 to L7, L10 to L15
(Manufacturing 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 polyester resin raw material monomers, esterification catalysts and galvanic acid shown in Tables 1 and 2 are placed in a 5-liter four-necked flask equipped with a nitrogen introduction tube, a stirrer and a thermocouple, and placed at 180 ° C. under a nitrogen atmosphere. After keeping the temperature 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 at 230 ° C. under a reduced pressure of 10 kPa to the softening points shown in Tables 1 and 2 to obtain a polyester resin.

Production example H8, H9, L8, L9
(Resin H-8, H-9, L-8, L-9)
Equipped with a nitrogen introduction tube, a dehydration tube equipped with a distilling tube through which hot water at 98 ° C was passed, a stirrer, and a thermocouple for the raw material monomers of polyester resin, esterification catalyst, and galvanic acid shown in Tables 1 and 2. It was placed in a 5-liter four-necked flask, kept warm at 180 ° C. for 1 hour under a nitrogen atmosphere, heated 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 points shown in Tables 1 and 2 to obtain a polyester resin.

Production example H14
(Manufacturing of resin H-14)
The raw material monomers of the polyester resin other than trimellitic acid anhydride, the esterification catalyst and the galvanic acid shown in Table 1 are placed in a 5-liter four-necked flask equipped with a nitrogen introduction tube, a stirrer and a thermocouple, and a nitrogen atmosphere is provided. After keeping 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. Then, the temperature was lowered to 210 ° C., anhydrous trimellitic acid was added, the reaction was carried out at 210 ° C. for 1 hour, and then the reaction was further carried out at 210 ° C. under a reduced pressure of 10 kPa to the softening point shown in Table 1 to obtain a polyester resin. Got

Production example, H17, L16
(Manufacturing of resins H-17 and L-16)
The raw material monomers of the polyester resin, esterification catalyst and galvanic acid shown in Tables 1 and 2 were placed in a 5-liter four-necked flask equipped with a nitrogen introduction tube, a stirrer and a thermocouple, and placed at 235 ° C. under a nitrogen atmosphere. The temperature was raised to 235 ° C. and then polycondensed 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 to the softening points shown in Tables 1 and 2 to obtain a polyester resin.

[Manufacturing of compound B]
Production example B1
(Manufacturing of compound B-1)
In a 2 L volume four-necked flask equipped with a cooling tube, nitrogen introduction tube, stirrer, dehydration tube and thermocouple, 28 g of tetraethylenepentamine (amine value 23 mmol / g) as a basic nitrogen-containing base raw material, wax affinity. One-ended maleic anhydride-modified polypropylene (PPSA1000) ("X-10065" manufactured by Baker Hughes, melting point 108 ° C., number average molecular weight 1,000) 300 g, and xylene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 328 g as base raw materials Was put in, and the inside of the reaction vessel was replaced with nitrogen gas. The inside of the reaction vessel was heated to 150 ° C. and held for 1 hour, then heated to 160 ° C. and held for 1 hour, the pressure inside the flask was further lowered, and the pressure was reduced to 8.3 kPa to distill off the solvent. While reacting. From IR analysis, it was confirmed that the peak of acid anhydride derived from PPSA (1780 cm ^-1 ) disappeared and the peak derived from imide bond (1700 cm ^-1 ) was generated, and compound B-1 was obtained. The melting points are shown in Table 3.

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

[Manufacturing of toner]
Example 1
For 100 parts by mass of 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 and carbon black "MOGUL (registered trademark) L" (manufactured by Cabot) 4 1 part by mass, 1 part by mass of negative charge control agent "Bontron (registered trademark) S-34" (manufactured by Orient Chemical Industry Co., Ltd.), and paraffin wax "HNP-9" (Nippon Seiwa Co., Ltd.) as the release agent C. (M), melting point 77 ° C.) 6 parts by mass was mixed with a Henshell mixer to obtain a mixture.
The obtained mixture is melt-kneaded at a screw rotation speed of 200 r / min and a barrel set temperature of 100 ° C. using a co-rotating twin-screw extruder having a total length of 1560 mm, a screw diameter of 42 mm, and a barrel inner diameter of 43 mm. Got 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 roughly pulverized, then pulverized by a jet mill and classified to obtain a powder (toner mother particle) having a volume medium particle size (D ₅₀ ) of 7.0 μm.
100 parts by mass of the obtained powder (toner mother particles) and 1.5 mass of hydrophobic silica "RY50" (manufactured by Nippon Aerosil Co., Ltd., hydrophobizing agent: silicone oil, average particle size 40 nm) as an external additive. Parts and 1.0 part by mass of hydrophobic silica "R972" (manufactured by Nippon Aerosil Co., Ltd., hydrophobizing agent: DMDS, average particle size 16 nm) were mixed for 3 minutes with a Henshell mixer to obtain toner. .. Table 4 shows the evaluation results of the obtained toner.

Examples 2 to 17, Comparative Examples 1 to 5
Same as Example 1 except that the types and amounts of the polyester resin, compound B, and mold release agent C used in Example 1 were changed to the types and amounts of the aqueous dispersion of the resin particles shown in Table 4. And got the toner. Table 4 shows the evaluation results of the obtained toner.

[evaluation]
[Heat-resistant storage of toner]
10 g of toner was placed in a 50 mL plastic cup and kept at 50 ° C. and 60% RH for 24 hours. After that, three sieves, sieve A (opening 250 μm), sieve B (opening 150 μm), and sieve C (opening 75 μm), were placed on a powder tester (manufactured by Hosokawa Micron Co., Ltd.) in order from the top. 10 g of toner was placed on the sieve A and vibrated for 60 seconds. The liquidity of the value (α) calculated from the following formula was evaluated based on the following evaluation criteria. The larger the 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) x 100

[Bending resistance]
Toner was mounted on a device that was improved so that the fixing machine of the copying machine "AR-505" (manufactured by Sharp Corporation) could be fixed outside the device, and printed matter was obtained in an unfixed state (printed area: 20 cm). × 20 cm, adhesion amount: 0.5 mg / cm ² ). Then, using a fixing machine (fixing speed 300 mm / sec) adjusted so that the total fixing pressure was 40 kgf, the fixing roll was fixed at a temperature of 160 ° C. This image was folded inward at 50 g / cm ² for 30 seconds, reopened, and the damaged image was wiped off with a soft cloth. The maximum value of the width of the image defect was used as an index of the bending resistance of the printed matter. The smaller the maximum value of the width of the image defect, the better the bending resistance of the printed matter. As the fixing paper, "CopyBondo SF-70NA" (manufactured by Sharp Corporation, 75 g / m ² ) was used.

[Toner durability]
Toner is mounted on the printing machine "Page Presto 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), temperature 32 ° C, humidity. A pattern of diagonal stripes with a blackening ratio of 5.5% was continuously printed under an environment of 85%. On the way, 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 appeared on the image, and printing was performed up to 9000 sheets. The number of printed sheets up to the time when the streaks were visually observed on the image was defined as the number of sheets in which the streaks were generated due to the fusion and adhesion of the toner to the developing roll, and the durability was evaluated. That is, it can be determined that the durability of the toner is higher as the number of sheets without streaks increases.

From the results of Examples and Comparative Examples, the inclusion of the amorphous resin A having an acidic group, the compound B, and the release agent C provides durability, bending resistance of the printed matter, and high temperature and humidity. It can be seen that a toner having excellent storage stability can be obtained.

Claims (9)

It has an amorphous resin A having an acidic group, 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 azi group. A toner for static charge image development, which contains a compound B and a mold release agent C, and contains an aliphatic alcohol having 4 or more and 8 or less carbon atoms as an alcohol component constituting the amorphous resin A. The toner for developing an electrostatic charge image according to claim 1, wherein the compound B is a reaction product of a basic nitrogen-containing base raw material and a polyolefin skeleton raw material. The toner for developing an electrostatic charge image according to claim 1 or 2, wherein the polyolefin skeleton is a polyethylene skeleton or a polypropylene skeleton. The toner for developing an electrostatic charge image according to any one of claims 1 to 3, wherein the basic nitrogen-containing group is an amino group. The toner for static charge image development 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. Claims 1 to 5 in which the total content of the ethylene oxide adduct of bisphenol A or the propylene oxide adduct of bisphenol A is 50 mol% or less with respect to 100 mol% of the total alcohol component constituting the amorphous resin A. The toner for developing an electrostatic charge image according to any one of the above. One of claims 1 to 6, wherein the content of the aliphatic alcohol having 4 or more and 8 or less carbon atoms is 20 mol% or more with respect to 100 mol% of the total alcohol component constituting the amorphous resin A. The above-mentioned static charge image developing toner. The toner for static charge image development according to any one of claims 1 to 7, which contains an aliphatic alcohol having 4 or more and 6 or less carbon atoms as an alcohol component constituting the amorphous resin A. The static charge image development according to any one of claims 1 to 8, wherein the aliphatic alcohol component having 4 or more carbon atoms and 8 or less carbon atoms contained as the alcohol component constituting the amorphous resin A has a branched structure. toner.