JP2020034891A - Toner for electrostatic charge image development - Google Patents

Abstract

To provide a toner for electrostatic charge image development which is excellent in low temperature fixability and hot-offset resistance, and has a wide fixation width.SOLUTION: A toner for electrostatic charge image development contains a polyester-based resin L, a polyester-based resin H having a softening point higher than a softening point of the polyester-based resin L by 5°C or more, and a release agent, in which the polyester-based resin L and the polyester-based resin H each independently contains at least a polycondensate of an alcohol component and a carboxylic acid component containing a succinic acid or its anhydride substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms, and the polyester-based resin L and the polyester-based resin H each independently has a molar ratio of the succinic acid or its anhydride substituted with a linear aliphatic hydrocarbon group having 16 carbon atoms in the carboxylic acid component to the succinic acid or its anhydride substituted with a linear aliphatic hydrocarbon group having 18 carbon atoms of 30/70 or more and 70/30 or less.SELECTED DRAWING: None

Description

  The present invention relates to an electrostatic 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.

  In the field of electrophotography, with the development of electrophotographic systems, development of electrophotographic toners corresponding to high image quality and high speed has been demanded.

  Patent Document 1 discloses a toner for developing an electrostatic image containing core-shell particles as a binder resin, wherein a core portion is obtained by polycondensing a carboxylic acid component (L-ac) and an alcohol component (L-al). A polyester (H) obtained by polycondensing a carboxylic acid component (H-ac) and an alcohol component (H-ac), and the shell portion contains a polyester (L) and a wax. The acid component (L-ac) contains at least one selected from alkenyl succinic acids and alkyl succinic acids having a specific branched structure, and the alkenyl succinic acid and the alkyl succinic acid in the carboxylic acid component (L-ac) The total content of one or more acids selected from the group consisting of 3 mol% or more is selected from the group consisting of alkenyl succinic acid and alkyl succinic acid in the carboxylic acid component (H-ac). Content of more than, less than 3 mol%, the toner for developing electrostatic images is described. It is described that the toner has both low-temperature fixability and heat-resistant storage stability, and is excellent in gloss and smear of printed matter.

  Patent Document 2 discloses a toner for developing an electrostatic image containing core-shell particles as a binder resin, wherein a core portion is obtained by polycondensing a carboxylic acid component (L-ac) and an alcohol component (L-al). A polyester (L) obtained by subjecting the carboxylic acid component (H-ac) and an alcohol component (H-al) to polycondensation. The acid component (H-ac) contains at least one selected from alkenyl succinic acids and alkyl succinic acids having a specific branched structure, and the alkenyl succinic acid and the alkyl succinic acid in the carboxylic acid component (H-ac) The total content of at least one selected from acids is 3 mol% or more, and at least one selected from the alkenylsuccinic acid and the alkylsuccinic acid in the carboxylic acid component (L-ac); The total content of the above is less than 3 mol%, the toner for developing electrostatic images is described. It is described that the toner satisfies low-temperature fixability, and is excellent in heat-resistant storage stability, hot offset resistance, and smearing property of printed matter.

JP-A-2006-105139 JP 2016-197207 A

According to Patent Documents 1 and 2, a polyester resin containing succinic acid or an anhydride thereof substituted with a long-chain aliphatic hydrocarbon group as a carboxylic acid component in combination with a release agent such as wax is used. Thus, various characteristics such as low-temperature fixability can be improved.
However, it is difficult to obtain a toner for developing an electrostatic charge image exhibiting excellent hot offset resistance while exhibiting excellent low-temperature fixability, and it has been required to increase the fixing width.
Accordingly, the present invention relates to a toner for developing an electrostatic image, which is excellent in low-temperature fixing property and hot offset resistance and has a wide fixing width.

The present inventors have used two types of polyester resins having different softening points, and as a carboxylic acid component of these polyester resins, a succinic acid substituted with a linear aliphatic hydrocarbon group having 16 carbon atoms or an anhydride thereof. And a succinic acid or an anhydride thereof substituted with a straight-chain aliphatic hydrocarbon group having 18 carbon atoms are included in a predetermined molar ratio range, so that the low-temperature fixability and the hot offset resistance are excellent. It has been found that a toner for developing electrostatic images having a wide fixing width can be obtained.
The present invention contains a polyester resin L, a polyester resin H having a softening point higher than the softening point of the polyester resin L by 5 ° C. or more, and a release agent,
The polyester resin L and the polyester resin H are each independently an alcohol component and a carboxylic acid component containing a succinic acid or an anhydride thereof substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms. Including at least a polycondensate,
The polyester-based resin L and the polyester-based resin H are each independently a succinic acid or an anhydride thereof substituted with a straight-chain aliphatic hydrocarbon group having 16 carbon atoms in a carboxylic acid component and a straight-chain aliphatic chain having 18 carbon atoms. The present invention relates to a toner for developing an electrostatic image, wherein the molar ratio of succinic acid or its anhydride substituted with a hydrocarbon group is 30/70 or more and 70/30 or less.

  According to the present invention, it is possible to provide a toner for developing an electrostatic image, which is excellent in low-temperature fixing property and hot offset resistance and has a wide fixing width.

[Electrostatic image developing toner]
The toner for developing an electrostatic image of the present invention (hereinafter, also referred to as “toner”) has a polyester resin L (hereinafter, also simply referred to as “resin L”) and a softening point higher than the softening point of the resin L by 5 ° C. or more. Containing a polyester resin H (hereinafter, also simply referred to as “resin H”) and a release agent,
The resin L and the resin H each independently include at least a polycondensate of an alcohol component and a carboxylic acid component containing a succinic acid or an anhydride thereof substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms. ,
Resin L and resin H were each independently substituted with a succinic acid or an anhydride thereof substituted with a straight-chain aliphatic hydrocarbon group having 16 carbon atoms and a straight-chain aliphatic hydrocarbon group having 18 carbon atoms in a carboxylic acid component. The molar ratio of succinic acid or its anhydride (hereinafter, also simply referred to as “C16 / C18 molar ratio”) is 30/70 or more and 70/30 or less.
According to the above configuration, it is possible to obtain a toner for developing an electrostatic image, which is excellent in low-temperature fixing property and hot offset resistance and has a wide fixing width.

The reason why the toner of the present invention is excellent in low-temperature fixing property and hot offset resistance and exhibits a wide fixing width is not clear, but is considered as follows.
The toner of the present invention contains a release agent and, as a carboxylic acid component, a polyester resin containing succinic acid substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms or an anhydride thereof.
By containing a unit derived from succinic acid or its anhydride substituted with a linear aliphatic hydrocarbon group having a high affinity for the release agent in the polymer chain of the polyester resin, the dispersibility of the release agent in the toner is improved. It is considered that as a result, the low-temperature fixability is excellent.
Further, in the polyester resin, the moles of succinic acid or an anhydride thereof substituted with a linear aliphatic hydrocarbon group having 16 carbon atoms and succinic acid or anhydride thereof substituted with a linear aliphatic hydrocarbon group having 18 carbon atoms. When the ratio is 30/70 or more and 70/30 or less, the molecular weight distribution of the polyester obtained as a polyester resin having a softening point suitable for the binder resin of the toner is widened. Since the endothermic peak near the glass transition point in calorimetric analysis (DSC) becomes broad, there is an effect that a very wide fixing region is provided. Furthermore, by using two kinds of resins, a resin L and a resin H having a softening point higher than the softening point of the resin L by 5 ° C. or more, contradictory properties such as low-temperature fixing and hot offset resistance are achieved. It is thought that the fixing width can be expanded.

The definitions of various terms in this specification are shown below.
Whether the resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is defined by the ratio of the softening point of the resin to the maximum endothermic peak temperature (softening point (° C.) / Endothermic maximum peak temperature (° C.)) in the measurement method described in Examples described later. The crystalline resin has a crystallinity index of 0.6 or more and 1.4 or less. An amorphous resin is one having a crystallinity index of less than 0.6 or more than 1.4. The crystallinity index can be appropriately adjusted depending on the kind and ratio of the raw material monomers, and the production conditions such as the reaction temperature, the reaction time, and the cooling rate.

(Toner particles)
The toner includes, for example, toner particles. The toner particles preferably contain a resin L, a resin H, and a release agent described below. The toner particles contain additives such as a coloring agent, a charge control agent, a magnetic powder, a flow improver, a conductivity adjuster, a reinforcing filler such as a fibrous substance, an antioxidant, and a cleaning improver. And preferably contains a colorant and a charge control agent.

<Polyester resin L>
Resin L is excellent in low-temperature fixing property and hot offset resistance, and from the viewpoint of obtaining a toner having a wide fixing width, succinic acid substituted with an alcohol component and a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms. Or at least a polycondensate with a carboxylic acid component containing an anhydride thereof.
As the resin L, a polyester resin (LI) which is a polycondensate of an alcohol component and a carboxylic acid component containing succinic acid or an anhydride thereof substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms. And a polyester segment which is a polycondensation part of an alcohol component and a carboxylic acid component containing a succinic acid or an anhydride thereof substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms, and a monomer containing a styrene compound One or more selected from composite resins (L-II) having a vinyl-based resin segment, which is an addition-polymerized part of the component. As the resin L, a polyester resin (LI) is preferable from the viewpoint of obtaining a toner having excellent low-temperature fixing property and hot offset resistance and having a wide fixing width.
Resin L is excellent in low-temperature fixing property and hot offset resistance, and from the viewpoint of obtaining a toner having a wide fixing width, succinic acid or a succinic acid obtained by substituting a straight-chain aliphatic hydrocarbon group having 16 carbon atoms in the carboxylic acid component. The molar ratio of the anhydride to the succinic acid substituted by the straight-chain aliphatic hydrocarbon group having 18 carbon atoms or the anhydride thereof is 30/70 or more and 70/30 or less.
The resin L is preferably an amorphous resin.

(Polyester resin (LI))
The polyester resin (LI) is a polycondensate of an alcohol component and a carboxylic acid component containing succinic acid or an anhydride thereof substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms.
Examples of the alcohol component include an aromatic diol, a linear or branched aliphatic diol, an alicyclic diol, and a trihydric or higher polyhydric alcohol. Among these, an aromatic diol or a linear or branched aliphatic diol is preferred.
The amount of the aromatic diol in the alcohol component is preferably 70 mol% or more, more preferably 90 mol% or more, further preferably 95 mol% or more, and 100 mol% or less, and further preferably 100 mol% or less. %.
The aromatic diol is preferably an alkylene oxide adduct of bisphenol A, more preferably of formula (I):

(Where OR ¹ and R ² O are an oxyalkylene group, R ¹ and R ² are each independently an ethylene group or a propylene group, x and y represent the average number of moles of alkylene oxide added, and And the sum of x and y is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, and more preferably 4 or less. It is an oxide adduct.
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. Among these, a propylene oxide adduct of bisphenol A is preferred.
The amount of the alkylene oxide adduct of bisphenol A in the alcohol component is preferably at least 70 mol%, more preferably at least 90 mol%, still more preferably at least 95 mol%, and at most 100 mol%. Preferably it is 100 mol%.

Examples of the linear or branched aliphatic diol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. , 2,3-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, , 12-dodecanediol.
Among these, a branched aliphatic diol is preferred. Examples of the branched aliphatic diol include 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, and 2,2-dimethyl-1,3-propanediol. Is mentioned. Among these, 1,2-propanediol is more preferred.
The amount of the branched aliphatic diol in the alcohol component is preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol% or less, and further preferably 100 mol% or less. 100 mol%.

Examples of the alicyclic diol include hydrogenated bisphenol A [2,2-bis (4-hydroxycyclohexyl) propane], alkylene oxide having 2 to 4 carbon atoms of hydrogenated bisphenol A (average addition number of 2 to 12). Below) adducts.
Examples of the trihydric or higher polyhydric alcohol include glycerin, pentaerythritol, trimethylolpropane, and sorbitol.
One or more of these alcohol components may be used.

The carboxylic acid component is excellent in low-temperature fixing property and hot offset resistance, and from the viewpoint of obtaining a toner having a wide fixing width, succinic acid or a succinic acid substituted with a straight-chain aliphatic hydrocarbon group having 16 to 18 carbon atoms. Contains anhydride.
The linear aliphatic hydrocarbon group may be unsaturated or saturated. Among these, a linear unsaturated aliphatic hydrocarbon group is preferable.
The number of carbon atoms of the linear aliphatic hydrocarbon group is preferably 16 or 18 from the viewpoint of availability.
Examples of the succinic acid or an anhydride thereof substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms include hexadecenyl succinic acid, octadecenyl succinic acid and an anhydride thereof.

  The C16 / C18 molar ratio in the carboxylic acid component is 30/70 or more, preferably 35/65 or more, from the viewpoint of obtaining a toner having excellent low-temperature fixing property and hot offset resistance and having a wide fixing width. It is more preferably at least 40/60, even more preferably at least 50/50, and at most 70/30, preferably at most 65/35, more preferably at most 60/40.

The proportion of succinic acid or its anhydride substituted by a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms is preferably 1 mol part or more, more preferably 3 mol parts or more, based on 100 mol parts of the alcohol component. It is more preferably at least 5 mol parts, even more preferably at least 8 mol parts, and preferably at most 50 mol parts, more preferably at most 40 mol parts, still more preferably at most 30 mol parts, even more preferably at most 20 mol parts. , More preferably 12 mol parts or less.
The amount of succinic acid or its anhydride substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms is preferably 1 mol% or more, more preferably 3 mol% or more, and still more preferably, in the carboxylic acid component. 5 mol% or more, more preferably 8 mol% or more, and preferably 50 mol% or less, more preferably 40 mol% or less, further preferably 30 mol% or less, further preferably 20 mol% or less, and still more preferably Is 12 mol% or less.

As the carboxylic acid component, for example, other dicarboxylic acids and trivalent or higher polycarboxylic acids may be contained.
Other dicarboxylic acids include, for example, aromatic dicarboxylic acids, linear or branched aliphatic dicarboxylic acids other than succinic acid substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms or anhydrides thereof (hereinafter, referred to as “dicarboxylic acid”). "Other linear or branched aliphatic dicarboxylic acids") and alicyclic dicarboxylic acids. Among these, at least one selected from aromatic dicarboxylic acids and other 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 in the carboxylic acid component is preferably at least 20 mol%, more preferably at least 30 mol%, still more preferably at least 40 mol%, and preferably at most 90 mol%, more preferably at most 90 mol%. It is at most 80 mol%, more preferably at most 75 mol%.

The carbon number of other linear or branched aliphatic dicarboxylic acids is preferably 2 or more, more preferably 3 or more, and preferably 30 or less, more preferably 20 or less.
As other linear or branched aliphatic dicarboxylic acids, for example, oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecane diacid, Azelaic acid. Among these, fumaric acid, adipic acid and sebacic acid are preferred.
The amount of other linear or branched aliphatic dicarboxylic acids in the carboxylic acid component is preferably at least 1 mol%, more preferably at least 10 mol%, and preferably at most 40 mol%, more preferably at most 30 mol%. Mol% or less.

The trivalent or more polyvalent carboxylic acid is preferably a trivalent carboxylic acid, for example, trimellitic acid or an anhydride thereof.
It is preferable that the polyester resin (LI) does not contain a trivalent or higher polyvalent carboxylic acid.
One or more of these carboxylic acid components may be used.

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

The polyester resin (LI) may be produced, for example, by a method including a step of performing a polycondensation reaction with an alcohol component and a carboxylic acid component.
In this step, if necessary, esterification of di (2-ethylhexanoic acid) tin (II), dibutyltin oxide, titanium bisisopropoxybistriethanolaminate, titaniumbishydroxybistriethanolaminate, titanium diisopropoxyterephthalate, etc. The catalyst is used in an amount of 0.01 to 5 parts by mass based on 100 parts by mass of the total of the alcohol component and the carboxylic acid component; an esterification cocatalyst such as gallic acid (the same as 3,4,5-trihydroxybenzoic acid). May be used in an amount of 0.001 to 0.5 parts by mass with respect to 100 parts by mass of the total of the alcohol component and the carboxylic acid component for polycondensation.
When a monomer having an unsaturated bond such as fumaric acid is used in the polycondensation reaction, preferably 0.001 part by mass relative to 100 parts by mass of the alcohol component and the carboxylic acid component as necessary. At least 0.5 part by mass of the radical polymerization inhibitor may be used. Examples of the radical polymerization inhibitor include 4-tert-butylcatechol.
The temperature of the polycondensation reaction is preferably 120 ° C. or higher, more preferably 160 ° C. or higher, even more preferably 180 ° C. or higher, and preferably 250 ° C. or lower, more preferably 240 ° C. or lower. The polycondensation may be performed in an inert gas atmosphere.

(Composite resin (L-II))
The composite resin (L-II) is a polyester segment that is a polycondensation part of an alcohol component and a carboxylic acid component containing a succinic acid or an anhydride thereof substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms, And a vinyl-based resin segment which is an addition-polymerized portion of a monomer component containing a styrene compound.
The polyester segment is made of polyester, and a preferable example of the polyester is the same as the polyester resin (LI) described above.

(Vinyl resin segment)
The vinyl-based resin segment is preferably an addition polymer of a monomer component containing a styrene compound.
Examples of the styrene compound include styrene and styrene derivatives such as α-methylstyrene and vinyltoluene.

  The content of the styrene compound is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and still more preferably 75% by mass in the raw material monomer of the vinyl resin from the viewpoint of hot offset resistance. % And 100% by mass or less.

  Raw material monomers for vinyl resins other than styrene compounds include (meth) acrylic acid alkyl esters; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; halovinyls such as vinyl chloride; Vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as vinyl methyl ether; vinylidene halides such as vinylidene chloride; and N-vinyl compounds such as N-vinylpyrrolidone.

  Two or more types of raw material monomers for vinyl resins other than styrene compounds can be used. In this specification, “(meth) acrylic acid” means at least one selected from acrylic acid and methacrylic acid.

  Among the raw material monomers of the vinyl resin used other than the styrene compound, alkyl (meth) acrylate is preferable from the viewpoint of improving the low-temperature fixability of the toner. The carbon number of the alkyl group in the (meth) acrylic acid alkyl ester is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably 22 or less, more preferably 18 or less from the above viewpoint. , More preferably 12 or less, more preferably 8 or less. Note that the carbon number of the alkyl ester refers to the carbon number derived from the alcohol component constituting the ester.

  As the alkyl (meth) acrylate, specifically, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (iso or tertiary) ) Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (iso) octyl (meth) acrylate, (iso) decyl (meth) acrylate, (iso) stearyl (meth) acrylate, and the like. Here, “(iso or tertiary)” and “(iso)” mean both the case where these prefixes are present and the case where they are not. Indicates normal. Further, “(meth) acrylate” means at least one or more selected from acrylate and methacrylate.

  The content of the alkyl (meth) acrylate is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less, from the viewpoint of low-temperature fixability in the raw material monomers of the vinyl resin segment. , More preferably 25% by mass or less, and preferably 0% by mass or more.

  A resin obtained by addition polymerization of a raw material monomer containing a styrene compound and an alkyl (meth) acrylate is also referred to as a styrene- (meth) acrylic resin.

  The addition polymerization reaction of the raw material monomer of the vinyl resin can be carried out by a conventional method, for example, in the presence of a polymerization initiator such as dibutyl peroxide, a crosslinking agent, or the like, in the presence of an organic solvent or in the absence of a solvent. The conditions are preferably 110 ° C. or higher, more preferably 120 ° C. or higher, further preferably 130 ° C. or higher, and preferably 250 ° C. or lower, more preferably 200 ° C. or lower, and further preferably 170 ° C. or lower.

  When an organic solvent is used in the addition polymerization reaction, xylene, toluene, methyl ethyl ketone, acetone, or the like can be used. The amount of the organic solvent used is preferably from 10 parts by mass to 50 parts by mass with respect to 100 parts by mass of the raw material monomer of the vinyl resin.

(Bi-reactive monomer)
From the viewpoint of improving the low-temperature fixability of the toner, the composite resin (L-II) further includes a raw material monomer for the polyester segment and a raw material for the vinyl resin segment in addition to the raw material monomer for the polyester segment and the raw material monomer for the vinyl resin segment. It is preferable that the resin is a composite resin obtained by using an amphoteric monomer which can react with any of the monomers. Therefore, when polymerizing the raw material monomer of the polyester segment and the raw material monomer of the vinyl-based resin segment to obtain a composite resin, the polycondensation reaction and / or the addition polymerization reaction are preferably performed in the presence of a bi-reactive monomer. Thereby, the composite resin becomes a composite resin in which the polyester segment and the vinyl-based resin segment are bonded via the constituent unit derived from the bi-reactive monomer, and the polyester segment and the vinyl-based resin segment are more finely and uniformly. It becomes dispersed.

  The bi-reactive monomer includes at least one functional group selected from the group consisting of a hydroxyl group, a carboxy group, an epoxy group, a primary amino group and a secondary amino group in the molecule, preferably a hydroxyl group and a carboxy group. A compound having at least one functional group selected from the group consisting of, more preferably a carboxy group and an ethylenically unsaturated bond, and by using such a bi-reactive monomer, Dispersibility can be further improved. The bi-reactive monomer is preferably at least one selected from the group consisting of acrylic acid, methacrylic acid, fumaric acid, maleic acid and maleic anhydride, but from the viewpoint of the reactivity of the polycondensation reaction and the addition polymerization reaction. Thus, acrylic acid, methacrylic acid or fumaric acid is more preferred, and acrylic acid or methacrylic acid is even more preferred. However, when used together with the polymerization inhibitor, a polyvalent carboxylic acid having an ethylenically unsaturated bond such as fumaric acid functions as a raw material monomer of the polyester segment. In this case, fumaric acid or the like is not a bi-reactive monomer but a raw material monomer for the polyester segment.

  From the viewpoint of improving the low-temperature fixability of the toner, the amount of the amphoteric monomer is preferably 1 mol part or more, more preferably 2 mol parts or more, based on 100 mol parts in total of the alcohol component of the polyester segment. It is preferably at least 3 mol parts, and from the viewpoint of obtaining a toner having excellent hot offset resistance and a wide fixing width, preferably at most 20 mol parts, more preferably at most 10 mol parts, even more preferably at least 7 mol parts. Part or less.

  The mass ratio of the polyester segment to the vinyl resin segment (polyester segment / vinyl resin segment) in the composite resin (L-II) is preferably 60/40 or more, more preferably, from the viewpoint of improving the low-temperature fixability of the toner. Is not less than 70/30, more preferably not less than 75/25, and is preferably 95/5 or less, more preferably 90/10, from the viewpoint of obtaining a toner having excellent hot offset resistance and a wide fixing width. Or less, more preferably 85/15 or less. In the above calculation, the mass of the polyester segment is the mass of the raw material monomer of the polycondensation resin used, excluding the amount of the reaction water dehydrated by the polycondensation reaction (calculated value). The amount of the reactive monomer is included in the amount of the raw material monomer of the polyester segment. The amount of the vinyl-based resin segment is the amount of the raw material monomer of the vinyl-based resin segment, and the amount of the polymerization initiator is included in the amount of the raw material monomer of the vinyl-based resin segment.

(Physical properties of polyester resin L)
The softening point of the resin L is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, even more preferably 100 ° C. or higher, and preferably 140 ° C. or lower, more preferably 130 ° C. or lower, and still more preferably 120 ° C. or lower. And more preferably 111 ° C. or lower.
The glass transition temperature of the resin L is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, even more preferably 50 ° C. or higher, and preferably 80 ° C. or lower, more preferably 70 ° C. or lower, and further preferably 60 ° C. or lower. It is as follows.

  The acid value of the resin L is preferably 5 mg KOH / g or more, more preferably 8 mg KOH / g or more, further preferably 10 mg KOH / g or more, and preferably 40 mg KOH / g or less, more preferably 35 mg KOH / g or less. Preferably it is 30 mgKOH / g or less.

  The number average molecular weight of the resin L is preferably at least 1,500, more preferably at least 2,000, even more preferably at least 2,500, further preferably at least 3,000, and preferably at most 8,000, It is more preferably at most 6,000, more preferably at most 5,000, even more preferably at most 4,000.

  The weight average molecular weight of the resin L is preferably 5,000 or more, more preferably 8,000 or more, further preferably 10,000 or more, further preferably 12,000 or more, and preferably 1,000,000. Or less, more preferably 800,000 or less, further preferably 100,000 or less, and still more preferably 25,000 or less.

  The softening point, glass transition temperature, acid value, number average molecular weight and weight average molecular weight of the resin L can be appropriately adjusted depending on the kind of the raw material monomer and its use amount, and the production conditions such as reaction temperature, reaction time and cooling rate. Yes, and their values are determined by the methods described in the examples.

  The content of the resin L in the resin component of the toner particles is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 30% by mass or more, and more preferably Is 95% by mass or less, more preferably 90% by mass or less, further preferably 80% by mass or less, and further preferably 70% by mass or less.

<Polyester resin H>
Resin H is a succinic acid substituted with an alcohol component and a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms from the viewpoint of obtaining a toner having excellent low-temperature fixing property and hot offset resistance and having a wide fixing width. Or at least a polycondensate with a carboxylic acid component containing an anhydride thereof.
The resin H is a polyester resin (HI) which is a polycondensate of an alcohol component and a carboxylic acid component containing a succinic acid or an anhydride thereof substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms, A polyester segment that is a polycondensation part of an alcohol component and a carboxylic acid component containing a succinic acid or an anhydride thereof substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms, and a monomer component containing a styrene compound. And at least one selected from composite resins (H-II) having a vinyl-based resin segment which is an addition-polymerized portion of the above. As the resin H, a polyester resin (HI) is preferable from the viewpoint of obtaining a toner having excellent low-temperature fixing property and hot offset resistance and having a wide fixing width.
Resin H is excellent in low-temperature fixing property and hot offset resistance, and from the viewpoint of obtaining a toner having a wide fixing width, succinic acid or its succinic acid substituted by a straight-chain aliphatic hydrocarbon group having 16 carbon atoms in the carboxylic acid component. The molar ratio of the anhydride to the succinic acid substituted by the straight-chain aliphatic hydrocarbon group having 18 carbon atoms or the anhydride thereof is 30/70 or more and 70/30 or less.
The resin H has a softening point higher than the softening point of the resin L by 5 ° C. or more.
Resin H is preferably an amorphous resin.

(Polyester resin (HI))
The polyester resin (HI) is a polycondensate of an alcohol component and a carboxylic acid component containing succinic acid or an anhydride thereof substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms.
Examples of the alcohol component and the carboxylic acid component in the polyester resin (HI) and the amounts thereof are the same as those of the polyester resin (LI).
Preferred examples of the polyester resin (HI) are shown below.
As the alcohol component, an alkylene oxide adduct of bisphenol A is preferable, and a propylene oxide adduct of bisphenol A and an ethylene oxide adduct of bisphenol A are more preferable.
The amount of the alkylene oxide adduct of bisphenol A in the alcohol component is preferably 60 mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more. Mol% or less, and more preferably 100 mol%.

The polyester resin (HI) preferably contains a trivalent or higher polycarboxylic acid as a carboxylic acid component. The trivalent or higher polycarboxylic acid is preferably a trivalent carboxylic acid, more preferably trimellitic acid or its anhydride.
The amount of the trivalent or higher polycarboxylic acid is preferably 1 mol% or more, more preferably 5 mol% or more, still more preferably 8 mol% or more, and preferably 40 mol% or less in the carboxylic acid component. , More preferably at most 30 mol%, further preferably at most 30 mol%.

(Composite resin (H-II))
The composite resin (H-II) is a polyester segment which is a polycondensation part of an alcohol component and a carboxylic acid component containing a succinic acid or an anhydride thereof substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms, And a vinyl resin segment which is an addition polymerized portion of a monomer component containing a styrene compound.
The polyester segment is made of polyester, and a preferable example of the polyester is the same as the polyester resin (HI) described above.
The configuration of the vinyl-based resin segment is the same as that of the above-described composite resin (L-II), and the preferable range is also the same.

(Physical properties of polyester resin H)
The softening point of the resin H is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, further preferably 100 ° C. or higher, further preferably 110 ° C. or higher, further preferably 112 ° C. or higher, and preferably 140 ° C. or lower. , More preferably 130 ° C or lower, further preferably 125 ° C or lower.
The difference [ _MH - _ML ] between the softening point of the resin H and the softening point of the resin L is preferably 5 ° C or more, more preferably 6 ° C or more, from the viewpoint of expanding the fixing width and improving the heat-resistant storage stability. It is preferably 8 ° C. or higher, and more preferably 30 ° C. or lower, more preferably 20 ° C. or lower, further preferably 15 ° C. or lower, further preferably 12 ° C. or lower, and still more preferably 10 ° C. or lower.
The glass transition temperature of the resin H is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, even more preferably 50 ° C. or higher, and preferably 80 ° C. or lower, more preferably 70 ° C. or lower, and further preferably 60 ° C. or lower. It is as follows.

  The acid value of the resin H is preferably 5 mgKOH / g or more, more preferably 8 mgKOH / g or more, further preferably 10 mgKOH / g or more, and preferably 40 mgKOH / g or less, more preferably 35 mgKOH / g or less. Preferably it is 30 mgKOH / g or less.

  The number average molecular weight of the resin H is preferably at least 3,000, more preferably at least 3,500, even more preferably at least 4,000, and preferably at most 8,000, more preferably at most 6,000, More preferably, it is 5,000 or less.

  The weight average molecular weight of the resin H is preferably 10,000 or more, more preferably 20,000 or more, still more preferably 30,000 or more, and preferably 1,000,000 or less, more preferably 800,000. Or less, more preferably 100,000 or less.

  The softening point, glass transition temperature, acid value, number average molecular weight and weight average molecular weight of the resin H can be appropriately adjusted according to the type of the raw material monomer and its use amount, and the production conditions such as the reaction temperature, reaction time and cooling rate. Yes, and their values are determined by the methods described in the examples.

  The content of the resin H in the resin component of the toner particles is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, further preferably 30% by mass or more, and preferably Is 95% by mass or less, more preferably 90% by mass or less, further preferably 80% by mass or less, and further preferably 70% by mass or less.

From the viewpoint of further improving the low-temperature fixing property and the hot offset resistance, and further expanding the fixing width, a succinic acid having a straight-chain aliphatic hydrocarbon group having 16 to 18 carbon atoms per 100 mol parts of the alcohol component of the resin H is substituted. The ratio of the acid or its anhydride (hereinafter, also simply referred to as “ _RH ”) is succinic acid substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms per 100 mol parts of the alcohol component of the resin L or its anhydride. It is preferably higher than the ratio of the substances (hereinafter, also simply referred to as “ _RL ”).
The difference [ _{RH- RL} ] between _RH and _RL is preferably -20 mol parts or more, more preferably at least -20 mol parts, from the viewpoint of further improving the low-temperature fixing property and the hot offset resistance and further expanding the fixing width. Is -15 mol parts or more, more preferably -10 mol parts or more, more preferably -5 mol parts or more, more preferably 0 mol parts or more, more preferably 3 mol parts or more, and preferably 50 mol parts or more. The amount is preferably at most 40 mol parts, more preferably at most 30 mol parts, still more preferably at most 20 mol parts, even more preferably at most 10 mol parts.

  The mass ratio of the resin H to the resin L [resin H / resin L] is preferably 5/95 or more, more preferably 10/90 or more, still more preferably 20/80 or more, and still more preferably 30/70 or more. And it is preferably 95/5 or less, more preferably 90/10 or less, preferably 80/20 or less, and preferably 70/30 or less.

<Crystalline polyester resin C>
The toner preferably contains a crystalline polyester resin C (hereinafter, also simply referred to as “resin C”) from the viewpoint of improving the fixing width.
The resin C is, for example, a polycondensate of an alcohol component and a carboxylic acid component.
The alcohol component preferably comprises an α, ω-aliphatic diol.
The carbon number of the α, ω-aliphatic diol is preferably 2 or more, more preferably 4 or more, still more preferably 6 or more, and preferably 16 or less, more preferably 14 or less, and still more preferably 12 or less. is there.
Examples of the α, ω-aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol No. Among these, 1,6-hexanediol and 1,9-nonanediol are preferred, and 1,6-hexanediol is more preferred.

  The amount of the α, ω-aliphatic diol in the alcohol component is preferably at least 80 mol%, more preferably at least 85 mol%, still more preferably at least 90 mol%, even more preferably at least 95 mol%, and It is 100 mol% or less, more preferably 100 mol%.

  The alcohol component may contain another alcohol component different from the α, ω-aliphatic diol. Other alcohol components include, for example, aliphatic diols other than α, ω-aliphatic diols such as 1,2-propylene glycol and neopentyl glycol; aromatic diols such as alkylene oxide adducts of bisphenol A; glycerin, pentane And trihydric or higher alcohols such as erythritol and trimethylolpropane. One or more of these alcohol components may be used.

The carboxylic acid component preferably comprises an aliphatic dicarboxylic acid.
The number of carbon atoms of the aliphatic dicarboxylic acid is preferably 4 or more, more preferably 8 or more, further preferably 10 or more, and preferably 14 or less, more preferably 12 or less.
Examples of the aliphatic dicarboxylic acid include fumaric acid, sebacic acid, dodecandioic acid, and tetradecandioic acid. Among these, sebacic acid, dodecandioic acid, and tetradecandioic acid are preferable, sebacic acid and dodecandioic acid are more preferable, and dodecandioic acid is still more preferable. One or more of these carboxylic acid components may be used.

  The amount of the aliphatic dicarboxylic acid in the carboxylic acid component is preferably 80 mol% or more, more preferably 85 mol% or more, further preferably 90 mol% or more, further preferably 95 mol% or more, and 100 mol% or more. % Or less, and more preferably 100 mol%.

  The carboxylic acid component may contain another carboxylic acid component different from the aliphatic dicarboxylic acid. Other carboxylic acid components include, for example, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid; and trivalent or higher polycarboxylic acids. One or more of these carboxylic acid components may be used.

  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. Preferably it is 1.2 or less.

(Physical properties of crystalline polyester resin C)
From the viewpoint of further improving the hot offset resistance, the softening point of the resin C is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, still more preferably 75 ° C. or higher, and further preferably 80 ° C. or higher. From the viewpoint of further improving the fixability, the temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 100 ° C. or lower.

  From the viewpoint of further improving the hot offset resistance, the melting point of the resin C is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, further preferably 70 ° C. or higher, and further preferably 72 ° C. or higher. From the viewpoint of further improving the properties, the temperature is preferably 100 ° C or lower, more preferably 95 ° C or lower.

  The acid value of the resin C is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, and preferably 35 mgKOH / g or less, more preferably 30 mgKOH / g or less, and further preferably 25 mgKOH / g or less. .

  The softening point, melting point, and acid value of the resin C can be appropriately adjusted depending on the types and ratios of the raw material monomers and production conditions such as a reaction temperature, a reaction time, and a cooling rate. Those values are obtained by the method described in the examples described later. When two or more resins C are used in combination, the values of the softening point, melting point, and acid value obtained as a mixture thereof are preferably within the above ranges.

  Resin C is obtained, for example, by polycondensation of an alcohol component and a carboxylic acid component. As the conditions for the polycondensation, for example, the conditions described for the polycondensation in the resin L can be applied.

  The mass ratio of the resin C to the total amount of the resin L and the resin H [resin C / (resin L + resin H)] is preferably 1/99 or more, more preferably 5/95 or more, and still more preferably 8/92 or more. And preferably 50/50 or less, more preferably 40/60 or less, even more preferably 35/65 or less.

  In the resin component of the toner, the content of the resin L, the resin H, and the resin C is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and 100% by mass or less. And preferably 100% by weight.

<Release agent>
As the release agent, wax is preferable.
Examples of the wax include a hydrocarbon wax, an ester wax, a silicone wax, and a fatty acid amide wax.
Examples of the hydrocarbon wax include mineral or petroleum hydrocarbon wax such as paraffin wax and Fischer-Tropsch wax; and synthetic hydrocarbon wax such as polyolefin wax such as polyethylene wax, polypropylene wax and polybutene wax.
Examples of the ester wax include mineral or petroleum ester waxes such as montan wax; vegetable ester waxes such as carnauba wax, rice wax and candelilla wax; and animal ester waxes such as beeswax.
Examples of the fatty acid amide wax include oleic acid amide and stearic acid amide. These may be used alone or in combination of two or more.
Of these, hydrocarbon waxes are preferred, and paraffin waxes are more preferred, from the viewpoint of increasing the fixing width and further improving the heat stability.

The melting point of the release agent is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, and is preferably 160 ° C. or lower, more preferably 150 ° C. or lower, and even more preferably 140 ° C. or lower.
The method for measuring the melting point of the release agent is based on the method described in Examples.

  The amount of the release agent is preferably at least 0.1 part by mass, more preferably at least 1 part by mass, still more preferably at least 3 parts by mass with respect to 100 parts by mass of the total amount of the resin L, the resin H and the resin C. And it is preferably at most 30 parts by mass, more preferably at most 20 parts by mass, even more preferably at most 10 parts by mass.

<Colorant>
Examples of the coloring agent include carbon black, phthalocyanine blue, permanent brown FG, brilliant fast scarlet, pigment green B, rhodamine-B base, solvent red 49, solvent red 146, solvent blue 35, quinacridone, carmine 6B, and disazo yellow. No.
The toner may be either a black toner or a color toner other than black.
From the viewpoint of improving the image density of the toner, the content of the colorant is preferably at least 1 part by mass, more preferably at least 2 parts by mass, based on 100 parts by mass of the total amount of the resin L, the resin H and the resin C. And preferably 20 parts by mass or less, more preferably 10 parts by mass or less.

<Charge control agent>
The charge control agent may contain any of a positive charge control agent and a negative charge control agent.
Examples of the positively chargeable charge control agent include a nigrosine dye, a triphenylmethane dye containing a tertiary amine as a side chain, a quaternary ammonium salt compound, a polyamine resin, an imidazole derivative, and a styrene-acrylic resin.
Examples of the nigrosine dye include “Nigrosine Base EX”, “Oil Black BS”, “Oil Black SO”, “Bontron N-01”, “Bontron N-04”, “Bontron N-07”, and “Bontron N-09”. And Bontron N-11 (all manufactured by Orient Chemical Industries, Ltd.). Examples of the quaternary ammonium salt compound include "Bontron P-51" (manufactured by Orient Chemical Co., Ltd.), cetyltrimethylammonium bromide, and "COPY CHARGE PX VP435" (manufactured by Clariant). As the polyamine resin, for example, "AFP-B" (manufactured by Orient Chemical Co., Ltd.) can be mentioned. Examples of the imidazole derivative include “PLZ-2001” and “PLZ-8001” (all manufactured by Shikoku Chemical Industry Co., Ltd.). As the styrene-acrylic resin, for example, "FCA-701PT" (manufactured by Fujikura Kasei Co., Ltd.) can be mentioned.

Examples of the negatively chargeable charge control agent include metal-containing azo dyes, metal compounds of benzylic acid compounds, metal compounds of salicylic acid compounds, copper phthalocyanine dyes, quaternary ammonium salts, nitroimidazole derivatives, and organometallic compounds.
Examples of the metal-containing azo dyes include “Varifast Black 3804”, “Bontron S-31”, “Bontron S-32”, “Bontron S-34”, and “Bontron S-36” (hereinafter, Orient Chemical Co., Ltd.) Manufactured by Eizen Spiron Black TRH, and "T-77" (manufactured by Hodogaya Chemical Industry Co., Ltd.). Examples of the metal compound of the benzyl acid compound include “LR-147” and “LR-297” (all manufactured by Nippon Carlit Co., Ltd.). Examples of the metal compound of the salicylic acid compound include “Bontron E-81”, “Bontron E-84”, “Bontron E-88”, “Bontron E-304” (all manufactured by Orient Chemical Industry Co., Ltd.), “TN -105 "(manufactured by Hodogaya Chemical Industry Co., Ltd.). Examples of the quaternary ammonium salt include “COPY CHARGE NX VP434” (manufactured by Clariant). As the organometallic compound, for example, "TN105" (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be mentioned.

  The content of the charge control agent is preferably at least 0.01 part by mass, more preferably at least 0.2 part by mass, and still more preferably at least 0.2 part by mass, based on 100 parts by mass of the total amount of the resin L, the resin H and the resin C. It is at least 3 parts by mass, and preferably at most 10 parts by mass, more preferably at most 5 parts by mass, further preferably at most 2 parts by mass.

The toner may be a chemical toner obtained by an emulsion aggregation method or a pulverized toner obtained by a melt kneading method.
When a chemical toner, the toner preferably comprises a core and core-shell toner particles having a shell located on the surface of the core.
The core contains a resin L, a resin H, and a release agent, and may contain a resin C and an additive as needed.
The shell preferably contains a resin L and a resin H. Also, the shell preferably covers the surface of the core.
The total content of the resin L and the resin H contained in the shell is preferably at least 5 parts by mass, more preferably at least 100 parts by mass of the total content of the resin L, the resin H and the resin C contained in the core. The amount is at least 8 parts by mass, more preferably at least 10 parts by mass, and preferably at most 30 parts by mass, more preferably at most 25 parts by mass, still more preferably at most 20 parts by mass, even more preferably at most 15 parts by mass.

<Physical properties of toner particles>
The volume median particle diameter (D ₅₀ ) of the toner particles is preferably 2 μm or more, more preferably 3 μm or more, and still more preferably 4 μm or more, from the viewpoint of obtaining a high quality image and further improving the cleaning property of the toner. And preferably 10 μm or less, more preferably 8 μm or less, and still more preferably 6 μm or less.
The volume median particle size (D ₅₀ ) of the toner particles can be measured by the method described in Examples.

(External additives)
Although the toner particles can be used as they are, it is preferable to use a toner obtained 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. Among these, hydrophobic silica is preferred.
When the surface treatment of the toner particles is performed by using an external additive, the amount of the external additive is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and still more preferably 100 parts by mass of the toner particles. It is at least 3 parts by mass, and preferably at most 5 parts by mass, more preferably at most 4.5 parts by mass, even more preferably at most 4 parts by mass.

  The toner is used for developing an electrostatic image in electrophotographic printing. The toner can be used, for example, as a one-component developer or as a two-component developer by mixing with a carrier.

[Production method]
The toner may be a toner obtained by any method such as a melt-kneading method, an emulsification phase inversion method, a polymerization method, and an agglomeration fusion method. A chemical toner by a fusion method and a pulverized toner by a melt-kneading method are preferable, and a chemical toner by an aggregation and fusion method is more preferable.

(Agglutination fusion method)
In the case of a chemical toner by an agglomeration fusion method, a method for producing a toner includes, for example,
Step of aggregating resin particles containing resin L and resin H in the same or different particles and, if necessary, resin particles containing resin C and release agent particles W to obtain aggregated particles (1) , "Step 1"),
A process of adhering resin particles containing resin L and resin H to the aggregated particles (1) in the same or different particles to obtain aggregated particles (2) (hereinafter also referred to as “step 2”) and aggregated particles (2) Step of fusing in an aqueous medium (hereinafter, also referred to as “step 3”)
including.

As the various resin particles used in the step 1, a dispersion liquid in which resins such as resin L, resin H, and resin C are dispersed in an aqueous medium in advance is used. The dispersion method is not particularly limited, but it is preferable to disperse by, for example, a phase inversion emulsification method. Examples of the phase inversion emulsification method include a method in which an aqueous medium is added to an organic solvent solution of a resin or a molten resin to perform phase inversion emulsification. The aqueous medium is preferably one containing water as a main component, and the content of water in the aqueous medium is, for example, 80% by mass or more and 100% by mass or less. The aqueous medium may contain an organic solvent soluble in water.
As the release agent particles W used in the step 1, a dispersion in which the release agent is dispersed in advance by a known method may be used. In step 1, the various additives described above may be aggregated.
In step 1, for example, in the presence of a surfactant such as an alkylbenzene sulfonate, the dispersion liquid is mixed, and a coagulant such as ammonium sulfate is added to cause coagulation. Aggregated particles (1) are obtained by adding a terminator.

In step 2, the resin particle dispersion containing the resin L and the resin H is added to the aggregated particle (1) by adding the resin particle dispersion containing the resin L and the resin H to the system containing the aggregated particle (1). To obtain aggregated particles (2). Aggregation can be performed in the same manner as in step 1.
In step 3, the aggregated particles (2) are fused in an aqueous medium. By fusion, the particles contained in the aggregated particles are fused to obtain fused particles.
After the step 3, post-treatment may be performed. For example, toner particles can be obtained by solid-liquid separation of the fused particles present in the aqueous medium and drying. Further, the above-mentioned external additives may be added to the toner particles.

(Melting and kneading method)
In the case of the pulverized toner by the melt-kneading method, for example, materials such as a resin L, a resin H, a resin C, a release agent, a colorant, and a charge control agent are uniformly mixed by a mixer such as a Henschel mixer, and then a closed kneader. It can be produced by melt-kneading with a single-screw or twin-screw extruder, open-roll kneader, or the like, cooling, pulverizing, and classifying.
The method for producing the pulverized toner preferably includes a step of melt-kneading the mixture containing the binder resin composition at a temperature in the range of 80 ° C. or more and 160 ° C. or less. The melt-kneading temperature is preferably 85 ° C. or higher, more preferably 90 ° C. or higher, and is preferably 150 ° C. or lower, more preferably 130 ° C. or lower.
The binder resin composition of the present invention has a high affinity between the amorphous resin and the crystalline resin but is hardly compatible with each other, and the crystallinity of the crystalline resin which can be present in a finely dispersed state in the amorphous resin. Therefore, the binder resin can be crystallized by the above-described melt-kneading step.

  The method for producing a pulverized toner preferably includes a step of pulverizing and classifying the mixture obtained by melt-kneading to obtain toner particles. The pulverization and classification can be performed by a known method.

  The properties of the resin, resin particles, toner and the like were measured and evaluated by the following methods.

[Measuring method]
(Acid value of resin)
The acid value of the resin was measured based on the method of JIS K0070: 1992. However, only the measurement solvent was changed from a mixed solvent of ethanol and ether specified in JIS K 0070: 1992 to a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

[Softening point of resin, maximum temperature of endothermic peak, glass transition temperature]
(1) Softening point Using a flow tester “CFT-500D” (manufactured by Shimadzu Corporation), a 1.96 MPa load was applied by a plunger while heating 1 g of a sample at a heating rate of 6 ° C./min. It was extruded from a 1 mm, 1 mm long nozzle. The plunger depression amount of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was taken as the softening point.
(2) Maximum temperature of endothermic peak Using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), 0 ° C. at a rate of 10 ° C./min from room temperature (20 ° C.). The sample cooled to the temperature was kept still for 1 minute, and then the temperature was measured at a rate of 10 ° C./min while the temperature was raised to 180 ° C. Of the endothermic peaks observed, the temperature of the peak on the highest temperature side was taken as the maximum temperature of the endothermic peak.
(3) Glass transition temperature Using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of a sample is weighed in an aluminum pan, and the temperature is 200 ° C. The temperature was raised to 0 ° C. at a rate of 10 ° C./min. Next, the measurement was performed while the temperature was raised to 150 ° C. at a rate of 10 ° C./min. The temperature at the intersection of the extension line of the base line below the maximum temperature of the endothermic peak and the tangent line indicating the maximum slope from the peak rising portion to the peak apex was defined as the glass transition temperature.

(Number average molecular weight of polyester resin, weight average molecular weight)
The molecular weight distribution was measured by gel permeation chromatography (GPC) according to the following method, and the number average molecular weight Mn and weight average molecular weight Mw of the resin were determined.
(1) Preparation of sample solution The polyester resin was dissolved in chloroform so that the concentration became 0.5 g / 100 mL. Subsequently, this solution was filtered using a fluororesin filter “FP-200” (manufactured by Sumitomo Electric Industries, Ltd.) having a pore size of 2 μm to remove insoluble components to obtain a sample solution.
(2) Measurement of molecular weight Using the following apparatus, chloroform was flowed as an eluent at a flow rate of 1 mL / min, and the column was stabilized in a constant temperature bath at 40 ° C. 100 μL of the sample solution was injected thereinto and the measurement was performed. The molecular weight of the sample was calculated based on a previously prepared calibration curve. In the calibration curve at this time, several kinds of monodisperse polystyrenes with known molecular weights of “2.63 × 10 ³ ”, “2.06 × 10 ⁴ ”, “1.02 × 10 ⁵ ” (all manufactured by Tosoh Corporation) )
Those prepared as standard samples of “2.10 × 10 ³ ”, “7.00 × 10 ³ ”, and “5.04 × 10 ⁴ ” (all manufactured by GL Sciences Inc.) were used.
Measuring device: "CO-8010" (manufactured by Tosoh Corporation)
Analysis column: "GMH _XL " + "G3000H _XL " (all manufactured by Tosoh Corporation)

(Melting point of release agent)
Using a differential scanning calorimeter “DSC Q20” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of a sample is weighed in an aluminum pan and heated at a rate of 10 ° C./min. Then, the temperature is raised to -10 ° C at a rate of 5 ° C / min. Next, the sample is heated to 180 ° C. at a rate of 10 ° C./min and measured. The highest endothermic peak temperature observed from the obtained melting endothermic curve is defined as the melting point of the release agent.

[Agglomerated Particles (1), Toner Particles, and Volume Median Particle Diameter (D ₅₀ ) and CV Value of Toner]
The volume median particle size (D ₅₀ ) of the aggregated particles (1), the toner particles, and the toner was measured as follows.
-Measuring machine: "Coulter Multisizer III" (manufactured by Beckman Coulter, Inc.)
・ Aperture diameter: 50 μm
・ Analysis software: "Multisizer III Version 3.51" (Beckman Coulter, Inc.)
・ Electrolyte: "Isothon II" (Beckman Coulter, Inc.)
Dispersion: Polyoxyethylene lauryl ether “Emulgen 109P” (manufactured by Kao Corporation, HLB: 13.6) was dissolved in the electrolyte to obtain a dispersion having a concentration of 5% by mass.
Dispersion conditions: 10 mg of a toner measurement sample was added to 5 mL of the above dispersion, dispersed for 1 minute with an ultrasonic disperser, and then 25 mL of electrolyte solution was added, and further dispersed for 1 minute with an ultrasonic disperser. A sample dispersion was prepared.
Measurement conditions: The sample dispersion was added to 100 mL of the electrolytic solution to adjust the particle size of 30,000 particles to a concentration that can be measured in 20 seconds, and then 30,000 particles were measured, and the particle size distribution was measured. The volume median particle size (D ₅₀ ) was determined from.
The volume average particle diameter (D _v ) was determined in the same manner as the volume median particle diameter (D ₅₀ ), and the CV value (%) was calculated according to the following equation.
CV value (%) = (standard deviation of particle size distribution / volume average particle size (D _v )) × 100

[Volume median particle diameter (D ₅₀ ) of colorant particles, charge control agent particles, and release agent particles]
The volume median particle size (D ₅₀ ) of the colorant particles, charge control agent particles, and release agent particles was measured as follows.
(1) Measuring device: Laser diffraction type particle size analyzer "LA-920" (manufactured by Horiba, Ltd.)
(2) Measurement conditions: Distilled water was added to the measurement cell, and the volume median particle size (D ₅₀ ) was measured at a concentration at which the absorbance was within an appropriate range.

(Solid concentration of dispersion)
Using an infrared moisture meter “FD-230” (manufactured by Kett Science Laboratory Co., Ltd.), 5 g of the sample was dried at 150 ° C. in a measurement mode of 96 (monitoring time: 2.5 minutes / fluctuation: 0.05%). And dried, and the water content (% by mass) of the sample was measured. The solid content was calculated according to the following equation.
Solid content concentration (% by mass) = 100−moisture of sample (% by mass)

[Evaluation]
(Fixing width)
The fixing width is the difference between the minimum fixing temperature obtained from the following evaluation of low-temperature fixing property and the minimum temperature at which hot offset occurs, obtained from the following evaluation of hot offset resistance.
(Low temperature fixability)
The toner was mounted on an apparatus in which a fixing machine of a copying machine “AR-505” (manufactured by Sharp Corporation) was modified so that it could be fixed outside the apparatus, and a printed matter was obtained in an unfixed state (print area: 2 cm). × 12 cm, adhesion amount: 0.5 mg / cm ² ). Then, while using a fixing machine (fixing speed 300 mm / sec) adjusted so that the total fixing pressure becomes 40 kgf, the temperature of the fixing roll is gradually increased from 100 ° C. to 240 ° C. in 5 ° C. steps, and unfixed at each temperature. A fixing test of the printed matter in the state was performed. Cellophane adhesive tape "UNICEF Cellophane" (manufactured by Mitsubishi Pencil Co., Ltd., width: 18 mm, JIS Z1522: 2009) was attached to the image portion of the obtained printed matter, and the temperature was set to 30 ° C. different from the fixing roll of the fixing machine. After passing through the fixing roller, the tape was peeled off. The optical reflection density before and after the tape was applied was measured using a reflection densitometer “RD-915” (manufactured by Gretag Macbeth), and the ratio of both (after peeling / before application × 100) was initially 90%. The temperature of the fixing roll exceeding the minimum fixing temperature was defined as the minimum fixing temperature. The lower the minimum fixing temperature, the better the low-temperature fixability. As the fixing paper, “Copy Bond SF-70NA” (manufactured by Sharp Corporation, 75 g / m ² ) was used.
(Hot offset resistance)
During the evaluation of the above-mentioned "low-temperature fixability", occurrence of hot offset was visually observed, and the lowest temperature at which hot offset occurred was confirmed as hot offset resistance. The higher the temperature at which the hot offset occurs, the better.

[Production of alkenyl succinic anhydride]
Production Example a (Production of alkenyl succinic anhydride a)
In a 1 L autoclave (manufactured by Nitto Koatsu Co., Ltd.), α-olefin “Linearene 16” (Idemitsu Kosan Co., Ltd.) such that α-olefin having 16 carbon atoms / α-olefin having 18 carbon atoms = 52 mol% / 48 mol%. 273.5 g, α-olefin “Linearene 18” (Idemitsu Kosan Co., Ltd.) 253.9 g, maleic anhydride 157.2 g, antioxidant “Chelex-O” (SC Organic Chemical Co., Ltd.) 0.4 g of triisooctyl phosphite) and 0.1 g of butyl hydroquinone as a polymerization inhibitor were charged, and the pressure substitution with nitrogen (0.2 MPa (G)) was repeated three times. After stirring was started at 60 ° C., the temperature was raised to 230 ° C. over 1 hour, and the reaction was carried out for 6 hours. The pressure 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 the reaction product was transferred to a 1 L four-necked flask. The temperature was raised while stirring to 180 ° C., and the remaining internal olefin 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 alkenyl succinic anhydride a as a target product. The average molecular weight of alkenyl succinic anhydride a determined from the acid value was 337.

Production Examples b to g (production of alkenyl succinic anhydrides b to g)
Alkenyl succinic anhydrides b to g were obtained in the same manner as in Production Example a, except that the types and amounts of the raw materials, the antioxidant, and the polymerization inhibitor were changed as shown in Table 1. The average molecular weight of the alkenyl succinic anhydride was determined from the acid value, and is shown in Table 1.

[Production of polyester resin]
Production Examples H1, H3 to H5, H8 to H18 (Production of Amorphous Polyester Resins H-1, H-3 to H-5, H-8 to H-18)
The raw material monomer, esterification catalyst and esterification cocatalyst of the polyester resin other than trimellitic anhydride shown in Table 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. in a nitrogen atmosphere, and then polycondensation was performed at 235 ° C. for 6 hours. Thereafter, the temperature was lowered to 210 ° C., trimellitic anhydride was added, and the mixture was reacted at 210 ° C. for 1 hour. Thereafter, the reaction was carried out at 210 ° C. under a reduced pressure of 10 kPa until the softening points described in Table 2 were obtained to obtain amorphous polyester resins H-1, H-3 to H-5, and H-8 to H-18. Was. Various physical properties were measured, and the physical properties are shown in Table 2.

Production Examples H2 and H7 (Production of amorphous polyester resins H-2 and H-7)
A raw material monomer, an esterification catalyst and an esterification cocatalyst of a polyester resin other than sebacic acid and trimellitic anhydride shown in Table 2 were converted into a four-liter five-liter port equipped with a nitrogen inlet tube, a stirrer, and a thermocouple. The mixture was placed in a flask, heated to 235 ° C. in a nitrogen atmosphere, and then subjected to polycondensation at 235 ° C. for 6 hours. Thereafter, the temperature was lowered to 180 ° C., sebacic acid and trimellitic anhydride were added, and the temperature was raised to 210 ° C. at a rate of 10 ° C./hour, followed by a reaction at 210 ° C. for 1 hour. Thereafter, the reaction was carried out at 210 ° C. under a reduced pressure of 10 kPa to the softening point shown in Table 2, to obtain amorphous polyester resins H-2 and H-7. Various physical properties were measured, and the physical properties are shown in Table 2.

Production Example H6 (Production of amorphous polyester resin H-6)
A raw material monomer, an esterification catalyst and an esterification co-catalyst of a polyester resin other than trimellitic anhydride shown in Table 2 were mixed with a nitrogen introduction tube, a dehydration tube equipped with a fractionation tube through which hot water of 98 ° C. was passed, and a stirring tube. Into a 5 liter four-necked flask equipped with a vessel and a thermocouple, kept at 180 ° C. for 1 hour in a nitrogen atmosphere, and then heated from 180 ° C. to 210 ° C. at a rate of 10 ° C./hour. Time polycondensation. Thereafter, trimellitic anhydride was added and reacted at 210 ° C. for 1 hour, and further reacted at 210 ° C. under a reduced pressure of 10 kPa to the softening point described in Table 2 to obtain an amorphous polyester resin H. -6 was obtained. Various physical properties were measured, and the physical properties are shown in Table 2.

Production Examples H19 and H20 (Production of amorphous composite resins H-19 and H-20)
The raw material monomer, esterification catalyst and esterification cocatalyst of the polyester resin (segment (B1)) other than trimellitic anhydride shown in Table 2 are equipped with a dehydration tube equipped with a nitrogen inlet tube, a stirrer, and a thermocouple. The mixture was placed in a 5-liter four-necked flask, heated to 235 ° C. in a nitrogen atmosphere, and then subjected to polycondensation at 235 ° C. for 6 hours. Thereafter, the temperature was lowered to 160 ° C., and a mixture of acrylic acid (amphoteric monomer), a raw material monomer of a vinyl-based resin (segment (B2)), and a polymerization initiator was dropped by a dropping funnel over 1 hour. After dropping, the addition polymerization reaction was aged for 1 hour while maintaining the temperature at 160 ° C., and then the temperature was raised to 200 ° C. and the pressure was reduced at 10 kPa for 1 hour. Thereafter, the pressure was released, trimellitic anhydride was added, the temperature was raised to 210 ° C. at a rate of 10 ° C./hour, and then the reaction was carried out at 210 ° C. for 1 hour. Further, the reaction was carried out at 210 ° C. under a reduced pressure of 10 kPa to the softening point shown in Table 2 to obtain amorphous composite resins H-19 and H-20. Various physical properties were measured, and the physical properties are shown in Table 2.

Production Examples L1, L3 to L5, L8 to L17 (Production of amorphous polyester resins L-1, L-3 to L-5, L-8 to L-17)
The raw material monomer of the polyester resin other than fumaric acid, the esterification catalyst and the esterification cocatalyst shown in Table 3 were put into a five-liter four-necked flask equipped with a nitrogen inlet tube, a stirrer, and a thermocouple. Then, the temperature was raised to 235 ° C., followed by polycondensation at 235 ° C. for 6 hours. Thereafter, the temperature was lowered to 180 ° C., fumaric acid and a polymerization inhibitor were added, the temperature was raised to 210 ° C. at a rate of 10 ° C./hour, and then the reaction was carried out at 210 ° C. for 1 hour. Thereafter, the reaction was carried out at 210 ° C. under a reduced pressure of 10 kPa until the softening points described in Table 3 were obtained to obtain amorphous polyester resins L-1, L-3 to L-5, and L-8 to L-17. Was. Various physical properties were measured, and the physical properties are shown in Table 3.

Production Examples L2 and L7 (Production of amorphous polyester resins L-2 and L-7)
The raw material monomer, esterification catalyst and esterification promoter of the polyester resin other than sebacic acid and fumaric acid shown in Table 3 were put into a 5-liter four-necked flask equipped with a nitrogen inlet tube, a stirrer and a thermocouple. The temperature was raised to 235 ° C. in a nitrogen atmosphere, and then polycondensation was performed at 235 ° C. for 6 hours. Thereafter, the temperature was lowered to 180 ° C., sebacic acid, fumaric acid and a polymerization inhibitor were added, and the temperature was raised to 210 ° C. at a rate of 10 ° C./hour, followed by a reaction at 210 ° C. for 1 hour. Thereafter, the reaction was carried out at 210 ° C. under a reduced pressure of 10 kPa to the softening point shown in Table 3, to obtain amorphous polyester resins L-2 and L-7. Various physical properties were measured, and the physical properties are shown in Table 3.

Production Example L6 (Production of amorphous polyester resin L-6)
The raw material monomers of the polyester resin other than fumaric acid, the esterification catalyst and the esterification cocatalyst shown in Table 3 were supplied to a nitrogen introduction pipe, a dehydration pipe equipped with a fractionating pipe through which hot water of 98 ° C. was passed, a stirrer and a thermoelectric Put in a 5 liter four-necked flask equipped with a pair, keep at 180 ° C for 1 hour in a nitrogen atmosphere, raise the temperature from 180 ° C to 210 ° C at 10 ° C / hour, and then polycondensate at 210 ° C for 10 hours I let it. Thereafter, the temperature was lowered to 180 ° C., fumaric acid and a polymerization inhibitor were added, and the temperature was raised to 210 ° C. at a rate of 10 ° C./hour, followed by a reaction at 210 ° C. for 1 hour. Thereafter, the reaction was carried out at 210 ° C. under a reduced pressure of 10 kPa to the softening point shown in the table to obtain an amorphous polyester resin L-6. Various physical properties were measured, and the physical properties are shown in Table 3.

Production Examples L18 and L19 (Production of Amorphous Composite Resins L-18 and L-19)
A raw material monomer, an esterification catalyst and an esterification cocatalyst of a polyester resin (segment (B1)) other than fumaric acid shown in Table 3 were supplied to a dehydration tube equipped with a nitrogen introduction tube, a stirrer and a thermocouple equipped with 5 liters. The mixture was placed in a four-necked flask, heated to 235 ° C. in a nitrogen atmosphere, and then subjected to polycondensation at 235 ° C. for 6 hours. Thereafter, the temperature was lowered to 160 ° C., and a mixture of acrylic acid (amphoteric monomer), a raw material monomer of a vinyl-based resin (segment (B2)), and a polymerization initiator was dropped by a dropping funnel over 1 hour. After dropping, the addition polymerization reaction was aged for 1 hour while maintaining the temperature at 160 ° C., and then the temperature was raised to 200 ° C. and the pressure was reduced at 10 kPa for 1 hour. Thereafter, the pressure was released, the temperature was lowered to 180 ° C., fumaric acid and a polymerization inhibitor were added, the temperature was raised to 210 ° C. at 10 ° C./hour, and then the reaction was carried out at 210 ° C. for 1 hour. Further, the reaction was carried out at 210 ° C. under a reduced pressure of 10 kPa until the softening points described in Table 3 were obtained to obtain amorphous composite resins L-18 and L-19. Various physical properties were measured, and the physical properties are shown in Table 3.

Production Examples C1 and C2 (Production of crystalline polyester resins C-1 and C-2)
The raw material monomers shown in Table 4 were put into a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a falling condenser, and a nitrogen inlet tube, and heated to 200 ° C. in a mantle heater under a nitrogen atmosphere. The temperature was raised over time. Thereafter, an esterification catalyst was added, and the reaction was carried out at 8.0 kPa until the softening point shown in Table 4 was reached, to obtain crystalline polyester resins C-1 and C-2. Various physical properties were measured, and the physical properties are shown in Table 4.

[Production of dispersion]
Production Example XH1 (Dispersion XH-1 of resin particles)
600 g of methyl ethyl ketone was charged into a 5 L container equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen inlet tube, and 150 g of the amorphous polyester resin H-1 produced in Production Example H1 was heated to 60 ° C. And dissolved. To the obtained solution, a 20% by mass aqueous ammonia solution (pKa: 9.3) was added so as to have a degree of neutralization of 100 mol% with respect to the acid value of the resin H-1, and the mixture was stirred for 30 minutes. I got Subsequently, 675 g of ion-exchanged water was added over 77 minutes. Subsequently, while stirring at 250 r / min, methyl ethyl ketone was distilled off under reduced pressure at a temperature of 50 ° C. or less, and then anionic surfactant “Emal E27C” (manufactured by Kao Corporation, sodium polyoxyethylene lauryl ether sulfate, (Solid content: 28% by mass) were mixed and completely dissolved. Thereafter, the solid content concentration of the dispersion was measured, and the solid content concentration of the dispersion was adjusted to 20% by mass by adding ion-exchanged water. The resulting dispersion XH-1 was used.

Production Examples XH2 to XH20 (Dispersions XH-2 to XH-20 of resin particles)
In Production Example XH1, except that the amorphous polyester resin used was changed to amorphous polyester resins H-2 to H-18 and amorphous composite resins H-19 to H-20 as shown in Table 5. In the same manner as in Production Example XH1, dispersions XH-2 to XH-20 of resin particles were obtained. Various physical properties of the obtained dispersion were measured and are shown in Table 5.

Production Examples XL1 to XL19 (Dispersions XL-1 to XL-19 of resin particles)
In Production Example XH1, except that the amorphous polyester resin used was changed to amorphous polyester resins L-1 to L-17 and amorphous composite resins L-18 to L-19 as shown in Table 6. In the same manner as in Production Example XH1, dispersions XL-1 to XL-19 of resin particles were obtained. Various physical properties of the obtained dispersion were measured and are shown in Table 6.

Production Examples XC1 and XC2 (Dispersions XC-1 and XC-2 of resin particles)
In Production Example XH1, the amorphous polyester resin used was changed to crystalline polyester resins C-1 to C-2 as shown in Table 7, and the addition temperature and the methyl ethyl ketone distillation temperature under reduced pressure were set to 73 ° C. Other than the above, dispersions XC-1 to XC-2 of resin particles were obtained in the same manner as in Production Example XH1. Various physical properties of the obtained dispersion were measured and are shown in Table 7.

[Production of release agent dispersion]
Production Example W1 (Production of release agent dispersion liquid W-1)
50 g of paraffin wax “HNP0190” (manufactured by Nippon Seiro Co., Ltd., melting point: 85 ° C.), 5 g of cationic surfactant “Sanisol B50” (manufactured by Kao Corporation) and 200 g of ion-exchanged water are heated to 95 ° C. After dispersing the paraffin wax using, a dispersion treatment was performed with a pressure discharge type homogenizer to obtain a release agent dispersion liquid W-1 containing release agent particles having a solid content concentration of 20% by mass. The volume median particle size (D ₅₀ ) of the release agent particles was 550 nm.

[Production of colorant dispersion]
Production Example P1 (Production of Colorant Dispersion P-1)
A mixture of 50 g of copper phthalocyanine "ECB-301" (manufactured by Dainichi Seika Kogyo Co., Ltd.), 5 g of nonionic surfactant "Emulgen 150" (manufactured by Kao Corporation, polyoxyethylene lauryl ether) and 200 g of ion-exchanged water, The mixture was dispersed at 25 ° C. for 10 minutes using a homogenizer to obtain a colorant dispersion P-1 containing colorant particles. The volume median particle size (D ₅₀ ) of the colorant particles having a solid content of 20% by mass was 120 nm.

[Production of charge control agent dispersion]
Production Example CH1 (Production of charge control agent dispersion liquid CH-1)
A mixture of 50 g of a salicylic acid-based compound "Bontron E-84" (manufactured by Orient Chemical Industry Co., Ltd.), 5 g of a nonionic surfactant "Emulgen 150" (manufactured by Kao Corporation) and 200 g of ion-exchanged water as a charge control agent, The beads were dispersed using a sand grinder at 25 ° C. for 10 minutes to obtain a charge control agent dispersion CH-1 containing charge control agent particles. The volume median particle diameter (D ₅₀ ) of the charge control agent particles having a solid content of 20% by mass was 500 nm.

[Manufacture of toner for developing electrostatic image]
Example 1 (Production of Toner 1)
Dispersion XH-1 150g, Dispersion XL-1 150g, Dispersion XC-1 38g, Release Agent Dispersion W-1 15g, Colorant Dispersion P-1 8g, Charge Control Agent Dispersion CH-12g In a 3 L container, 150 g of a 0.1% by mass aqueous solution of calcium chloride was added dropwise at 30 ° C. over 30 minutes while stirring at 100 r / min (peripheral speed: 31 m / min) with an anchor type stirrer. Thereafter, the temperature was raised to 50 ° C. while stirring. After 3 hours, aggregated particles (1) having a volume median particle size (D ₅₀ ) of 5 μm were obtained. Thereafter, a mixture of 22.5 g of the dispersion XH-1 and 22.5 g of the dispersion XL-1 was added, and the mixture was stirred and dispersed to obtain aggregated particles (2). Thereafter, a diluent obtained by diluting 4.2 g of an anionic surfactant “Emal E27C” (manufactured by Kao Corporation, solid content: 28% by mass) with 37 g of deionized water in the dispersion of the aggregated particles (2) was used as a coagulation terminator. Was added. Next, the temperature was raised to 80 ° C., and after maintaining at 80 ° C. for 1 hour from the time when the temperature reached 80 ° C., the heating was terminated. After forming fused particles by this, it is gradually cooled to 20 ° C., filtered through a wire mesh of 150 mesh (aperture 150 μm), suction-filtered, sufficiently washed with ion-exchanged water, and dried. By doing so, toner particles were obtained. The volume-median particle size (D ₅₀ ) of the obtained toner particles was 5.1 μm.
To 100 parts by mass of the toner particles, 0.5 parts by mass of hydrophobic silica “Aerosil R-972” (manufactured by Nippon Aerosil Co., Ltd., number average particle size: 16 nm) was added as an external additive, and a Henschel mixer (Nippon Coke Co., Ltd.) was added. The mixture was mixed at 3600 r / min (peripheral speed: 31.7 m / sec) for 5 minutes with the use of Industrial Co., Ltd. to obtain Toner 1 having a volume median particle size (D ₅₀ ) of 5.1 μm. Various evaluations were made and the results are shown in Table 8.

Examples 2-9, 11-21 and Comparative Examples 1-9 (Production of Toners 2-9, 11-21, 81-89)
In the same manner as in Example 1, except that the type and amount of the resin particle dispersion used were changed to the type and amount of the resin particle dispersion shown in Table 8, the toners 2 to 9, 11 and 11 were used. ~ 21, 81-89. Table 8 shows the evaluation results of the obtained toner.

Example 10 (production of toner 10)
100 parts by mass of binder resin (resin H-1 / resin L-1 / resin C-1 = 45/45/10 (mass ratio)), coloring agent "ECB-301" (manufactured by Dainichi Seika Kogyo Co., Ltd.) 5 Parts by mass, 1 part by mass of a charge control agent “LR-147” (manufactured by Nippon Carlit Co., Ltd.), and 2 parts by mass of a paraffin wax “HNP0190” (manufactured by Nippon Seiro Co., Ltd., melting point: 85 ° C.) as a release agent. After thoroughly stirring with a Henschel mixer, the mixture was melt-kneaded using a co-rotating twin-screw extruder having a total length of a kneading portion of 1560 mm, a screw diameter of 42 mm and a barrel inner diameter of 43 mm. The screw rotation speed was 200 r / min, the heating set temperature in the screw was 90 ° C., the temperature of the kneaded material was 140 ° C., the supply speed of the kneaded material was 10 kg / h, and the average residence time was about 18 seconds. The obtained kneaded material was cooled from 140 ° C. to 50 ° C. in 1.5 hours, rolled and cooled at 50 ° C. with a cooling roller, left at 45 ° C. for 4 hours, pulverized and classified by a jet mill, and the volume was reduced. Toner particles having a median particle size (D ₅₀ ) of 5.5 μm were obtained.

  1.5 parts by mass of hydrophobic silica "Aerosil R-972" (manufactured by Nippon Aerosil Co., Ltd., hydrophobizing agent: DMDS, average particle diameter: 16 nm) as an external additive with respect to 100 parts by mass of the obtained toner particles. , And 1.0 part by mass of hydrophobic silica "RY-50" (manufactured by Nippon Aerosil Co., Ltd., hydrophobizing agent: silicone oil, average particle size: 40 nm), and mixed at 3600 r / min for 5 minutes with a Henschel mixer. As a result, an external addition process was performed, and a toner 10 was obtained. Various evaluations were made and the results are shown in Table 8.

  As described above, the results of Examples and Comparative Examples indicate that the toner of the present invention is excellent in low-temperature fixing property and hot offset resistance, and has a wide fixing width.

Claims (8)

A polyester resin L, a polyester resin H having a softening point higher than the softening point of the polyester resin L by 5 ° C. or more, and a release agent;
The polyester resin L and the polyester resin H are each independently an alcohol component and a carboxylic acid component containing a succinic acid or an anhydride thereof substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms. Including at least a polycondensate,
The polyester-based resin L and the polyester-based resin H are each independently a succinic acid or an anhydride thereof substituted with a straight-chain aliphatic hydrocarbon group having 16 carbon atoms in a carboxylic acid component and a straight-chain aliphatic chain having 18 carbon atoms. A toner for developing an electrostatic image, wherein the molar ratio of succinic acid or its anhydride substituted with a hydrocarbon group is 30/70 or more and 70/30 or less.   The ratio of succinic acid or an anhydride thereof substituted by a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms to 100 mol parts of the alcohol component of the polyester resin H is such that the carbon content is 100 mol parts of the alcohol component of the polyester resin L. The electrostatic image developing toner according to claim 1, wherein the ratio of the succinic acid or its anhydride substituted with the linear aliphatic hydrocarbon group of Formulas 16 to 18 is higher.   The polyester-based resin L and the polyester-based resin H are each independently a proportion of succinic acid or an anhydride thereof substituted by a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms, relative to 100 mol parts of an alcohol component. The electrostatic image developing toner according to claim 1, wherein the amount of the toner is 1 mol part or more and 30 mol parts or less.   The electrostatic image developing toner according to any one of claims 1 to 3, wherein the alcohol component of the polyester resin L contains at least 70 mol% of a propylene oxide adduct of bisphenol A in the alcohol component.   The electrostatic image developing toner according to any one of claims 1 to 4, wherein the alcohol component of the polyester resin H contains an alkylene oxide adduct of bisphenol A in an amount of 60 mol% or more of the alcohol component.   The static electricity according to any one of claims 1 to 5, wherein a mass ratio of the polyester resin H and the polyester resin L [polyester resin H / polyester resin L] is 5/95 or more and 95/5 or less. Charge image developing toner.   The electrostatic image developing toner according to claim 1, further comprising a crystalline polyester resin.   The polyester-based resin L and the polyester-based resin H are each independently composed of an alcohol component and a carboxylic acid component containing succinic acid or an anhydride thereof substituted by a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms. Polyester resin which is a polycondensate, and a polyester segment which is a polycondensation portion of an alcohol component and a carboxylic acid component containing a succinic acid or an anhydride thereof substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms. The electrostatic image developing toner according to any one of claims 1 to 7, wherein the toner is at least one selected from a composite resin having a vinyl-based resin segment that is an addition-polymerized portion of a monomer component containing a styrene compound.