JP7178313B2 - Toner for electrostatic charge image development - Google Patents

Description

The present invention relates to an electrostatic charge image developing toner used for developing latent images formed in electrophotography, electrostatic recording, electrostatic printing, and the like.

In the field of electrophotography, with the development of electrophotographic systems, there is a demand for the development of electrophotographic toners capable of achieving higher image quality and higher speed.

Patent Document 1 discloses a toner for developing an electrostatic charge image containing core-shell particles as a binder resin, wherein the core portion is obtained by polycondensation of a carboxylic acid component (L-ac) and an alcohol component (L-al). and a wax, the shell portion contains a polyester (H) obtained by polycondensation of a carboxylic acid component (H-ac) and an alcohol component (H-ac), and carboxylic The acid component (L-ac) contains one or more selected from alkenylsuccinic acid and alkylsuccinic acid having a specific branched structure, and the alkenylsuccinic acid and the alkylsuccinic acid in the carboxylic acid component (L-ac) The total content of one or more selected from acids is 3 mol% or more, and the content of one or more selected from the alkenylsuccinic acid and the alkylsuccinic acid in the carboxylic acid component (H-ac) is Electrostatic image developing toners are described which are less than 3 mol %. It is described that the toner satisfies both low-temperature fixability and heat-resistant storage stability, and is excellent in glossiness and smear resistance of printed matter.

Patent Document 2 discloses a toner for electrostatic image development containing core-shell particles as a binder resin, wherein the core portion is obtained by polycondensation of a carboxylic acid component (L-ac) and an alcohol component (L-al). and a wax, the shell portion contains a polyester (H) obtained by polycondensation of a carboxylic acid component (H-ac) and an alcohol component (H-al), and carboxylic The acid component (H-ac) contains one or more selected from alkenylsuccinic acid and alkylsuccinic acid having a specific branched structure, and the alkenylsuccinic acid and the alkylsuccinic acid in the carboxylic acid component (H-ac) The total content of one or more selected from acids is 3 mol% or more, and the total content of one or more selected from the alkenylsuccinic acid and the alkylsuccinic acid in the carboxylic acid component (L-ac) is 3. Less than mol % of electrostatic charge image developing toners are described. It is described that the toner satisfies low-temperature fixability and is excellent in heat-resistant storage stability, hot-offset resistance, and smear resistance of printed matter.

JP 2016-105139 A JP 2016-197207 A

According to Patent Documents 1 and 2, a polyester resin containing succinic acid substituted with a long-chain aliphatic hydrocarbon group or its anhydride as a carboxylic acid component is used in combination with a mold release agent such as wax. It is possible to improve various properties such as low-temperature fixability.
However, it is difficult to obtain a toner for electrostatic charge image development that exhibits excellent low-temperature fixability as well as excellent hot offset resistance.
Accordingly, the present invention relates to a toner for electrostatic charge image development, which is excellent in low-temperature fixability and hot offset resistance, and has a wide fixation width.

The present inventors used two types of polyester resins having different softening points, and used succinic acid or anhydride thereof substituted with a linear aliphatic hydrocarbon group having 16 carbon atoms as the carboxylic acid component of these polyester resins. and succinic acid or its anhydride substituted with a linear aliphatic hydrocarbon group having 18 carbon atoms are contained within a predetermined molar ratio range, so that low-temperature fixability and hot offset resistance are excellent. Furthermore, the inventors have found that a toner for developing an electrostatic charge image having a wide fixation 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 each independently contain an alcohol component and a carboxylic acid component containing succinic acid or its anhydride 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 its anhydride substituted with a straight-chain aliphatic hydrocarbon group having 16 carbon atoms in the carboxylic acid component and a straight-chain aliphatic hydrocarbon having 18 carbon atoms. The present invention relates to a toner for electrostatic image development, wherein the molar ratio of hydrocarbon-substituted succinic acid or its anhydride is 30/70 or more and 70/30 or less.

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

[Electrostatic charge image developing toner]
The toner for electrostatic charge image development of the present invention (hereinafter also referred to as "toner") comprises polyester resin L (hereinafter also simply referred to as "resin L") and a softening point higher than the softening point of resin L by 5°C or more. containing a polyester resin H (hereinafter also simply referred to as "resin H") and a release agent,
Resin L and Resin H each independently contain at least a polycondensate of an alcohol component and a carboxylic acid component containing succinic acid or its anhydride substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms. ,
Resin L and Resin H are each independently substituted with succinic acid or an anhydride thereof substituted with a linear aliphatic hydrocarbon group having 16 carbon atoms in the carboxylic acid component and a linear aliphatic hydrocarbon group having 18 carbon atoms. 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 electrostatic charge image development that is excellent in low-temperature fixability and hot offset resistance and has a wide fixation width.

Although the reason why the toner of the present invention exhibits excellent low-temperature fixability and hot offset resistance and exhibits a wide fixation width is not clear, the following is considered.
The toner of the present invention contains a release agent and a polyester resin containing succinic acid substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms or an anhydride thereof as a carboxylic acid component.
Including units derived from succinic acid or its anhydride substituted with a straight-chain aliphatic hydrocarbon group that has a high affinity for the release agent in the polymer chain of the polyester resin improves the dispersibility of the release agent in the toner. It is considered that the improvement in the low-temperature fixability results in the improvement of the
Furthermore, moles of succinic acid or anhydride substituted with a linear aliphatic hydrocarbon group having 16 carbon atoms and succinic acid or anhydride substituted with a linear aliphatic hydrocarbon group having 18 carbon atoms in the polyester resin When the ratio is 30/70 or more and 70/30 or less, the molecular weight distribution of the polyester resin obtained as a polyester resin having a softening point suitable for the binder resin of the toner is widened. Since the endothermic peak in the vicinity of the glass transition point in calorimetric analysis (DSC) is broadened, there is an effect of having a very wide fixing range. Furthermore, by using two kinds of resins, the resin L and the resin H having a softening point higher than the softening point of the resin L by 5°C or more, both of the contradictory properties of low-temperature fixing and hot offset resistance can be achieved. It is considered that the fixing width can be widened.

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

[Toner particles]
Toner includes, for example, toner particles. The toner particles preferably contain a resin L, a resin H, and a releasing agent, which will be described later. The toner particles contain additives such as colorants, charge control agents, magnetic powders, fluidity improvers, conductivity modifiers, reinforcing fillers such as fibrous substances, antioxidants, and cleaning improvers. may also contain a coloring agent and a charge control agent.

<Polyester resin L>
Resin L is a succinic acid substituted with an alcohol component and a straight-chain aliphatic hydrocarbon group having 16 to 18 carbon atoms from the viewpoint of obtaining a toner having excellent low-temperature fixability and hot offset resistance and a wide fixation width. or at least a polycondensate with a carboxylic acid component including an anhydride thereof.
The resin L is a polyester resin (LI) which is a polycondensate of an alcohol component and a carboxylic acid component containing succinic acid or its anhydride substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms. , And a polyester segment that is a polycondensation portion of an alcohol component and a carboxylic acid component containing succinic acid or its anhydride 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 portion of the component, may be used. As the resin L, a polyester resin (LI) is preferable from the viewpoint of obtaining a toner excellent in low-temperature fixability and hot offset resistance and having a wide fixation width.
Resin L is succinic acid or its The molar ratio of the anhydride and the succinic acid substituted with a linear aliphatic hydrocarbon group having 18 carbon atoms or its anhydride is 30/70 or more and 70/30 or less.
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 its anhydride substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms.
Examples of alcohol components include aromatic diols, linear or branched aliphatic diols, alicyclic diols, and polyhydric alcohols having a valence of 3 or more. Among these, aromatic diols or linear or branched aliphatic diols are preferred.
The amount of the aromatic 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, more preferably 100 mol%. %.
The aromatic diol is preferably an alkylene oxide adduct of bisphenol A, more preferably of formula (I):

(Wherein, OR ¹ and R ² O are oxyalkylene groups, R ¹ and R ² are each independently an ethylene group or a propylene group, x and y represent the average number of added moles of alkylene oxide, each positive and the sum of x and y is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, more preferably 4 or less). It is an oxide adduct.
The alkylene oxide adducts of bisphenol A include, for example, propylene oxide adducts of bisphenol A [2,2-bis(4-hydroxyphenyl)propane] and ethylene oxide adducts of bisphenol A. These may be used alone or in combination of two or more. Among these, the propylene oxide adduct of bisphenol A is preferred.
The amount of the alkylene oxide adduct of bisphenol A 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 it is 100 mol %.

Examples of linear or branched aliphatic diols 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, 1 , 12-dodecanediol.
Among these, branched aliphatic diols are preferred. Branched aliphatic diols include, for example, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 2,2-dimethyl-1,3-propanediol is mentioned. Among these, 1,2-propanediol is more preferable.
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 is 100 mol% or less, more preferably 100 mol %.

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

The carboxylic acid component is succinic acid substituted with a straight-chain aliphatic hydrocarbon group having 16 to 18 carbon atoms or succinic acid substituted with a straight-chain aliphatic hydrocarbon group having 16 to 18 carbon atoms from the viewpoint of obtaining a toner having excellent low-temperature fixability and hot offset resistance and a wide fixation width. Contains anhydride.
A linear aliphatic hydrocarbon group may be either unsaturated or saturated. Among these, straight-chain unsaturated aliphatic hydrocarbon groups are preferred.
The number of carbon atoms in the linear aliphatic hydrocarbon group is preferably 16 or 18 from the viewpoint of availability.
Examples of the succinic acid or anhydride thereof substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms include hexadecenylsuccinic acid, octadecenylsuccinic acid and 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 fixability and hot offset resistance and a wide fixation width. More preferably 40/60 or more, still more preferably 50/50 or more, and 70/30 or less, preferably 65/35 or less, more preferably 60/40 or less.

The ratio of succinic acid or anhydride thereof substituted with 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, per 100 mol parts of the alcohol component, It is more preferably 5 mol parts or more, still more preferably 8 mol parts or more, and preferably 50 mol parts or less, more preferably 40 mol parts or less, still more preferably 30 mol parts or less, still more preferably 20 mol parts or less. , 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, still more preferably 3 mol% or more, 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, still more preferably 30 mol% or less, still more preferably 20 mol% or less, still more preferably is 12 mol % or less.

As the carboxylic acid component, for example, other dicarboxylic acids and polyvalent carboxylic acids having a valence of 3 or more may be included.
Other dicarboxylic acids include, for example, aromatic dicarboxylic acids, linear or branched aliphatic dicarboxylic acids (hereinafter referred to as Also referred to as "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 preferred.
Examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid, and terephthalic acid. Among these, isophthalic acid and terephthalic acid are preferred, and terephthalic acid is more preferred.
The amount of the aromatic dicarboxylic acid in the carboxylic acid component is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, and preferably 90 mol% or less, more preferably 80 mol % or less, more preferably 75 mol % or less.

The other linear or branched aliphatic dicarboxylic acids preferably have 2 or more carbon atoms, more preferably 3 or more carbon atoms, and preferably 30 or less carbon atoms, more preferably 20 or less carbon atoms.
Other linear or branched aliphatic dicarboxylic acids include, for example, oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, Azelaic acid is mentioned. 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 1 mol% or more, more preferably 10 mol% or more, and preferably 40 mol% or less, more preferably 30 mol% or less. mol% or less.

The trivalent or higher polyvalent carboxylic acid is preferably a trivalent carboxylic acid, such as trimellitic acid or its anhydride.
It is preferable that the polyester resin (LI) does not contain a polycarboxylic acid having a valence of 3 or more.
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, or more. It is preferably 1.2 or less.

Polyester resin (LI) may be produced, for example, by a method including a step of conducting 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 bisisopropoxybistriethanolamine, titanium bishydroxybistriethanolamine, titanium diisopropoxyterephthalate, etc. 0.01 parts by mass or more and 5 parts by mass or less of the catalyst per 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component; may be polycondensed using 0.001 parts by mass or more and 0.5 parts by mass or less per 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component.
Further, when a monomer having an unsaturated bond such as fumaric acid is used in the polycondensation reaction, it is preferably 0.001 part by mass with respect to 100 parts by mass as the total amount of the alcohol component and the carboxylic acid component, if necessary. More than 0.5 parts by mass or less of the radical polymerization inhibitor may be used. Examples of radical polymerization inhibitors include 4-tert-butylcatechol.
The temperature of the polycondensation reaction is preferably 120° C. or higher, more preferably 160° C. or higher, still more preferably 180° C. or higher, and preferably 250° C. or lower, more preferably 240° C. or lower. In addition, you may perform polycondensation in an inert gas atmosphere.

(Composite resin (L-II))
The composite resin (L-II) is a polyester segment which is a polycondensation portion of an alcohol component and a carboxylic acid component containing succinic acid or its anhydride substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms, and a vinyl resin segment that is an addition polymerization portion of a monomer component containing a styrene compound.
The polyester segment is made of polyester, and preferred examples of the polyester include those similar to the polyester resin (LI) described above.

(vinyl resin segment)
The vinyl resin segment is preferably an addition polymer of a monomer component containing a styrene compound.
Examples of styrene compounds 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, still more preferably 75% by mass, from the viewpoint of hot offset resistance in the raw material monomer of the vinyl resin. % or more and 100 mass % or less.

Raw material monomers for vinyl resins used 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 kinds of raw material monomers for vinyl-based resins other than the styrene compound can be used. In this specification, "(meth)acrylic acid" means at least one selected from acrylic acid and methacrylic acid.

Among raw material monomers for vinyl-based resins that are used other than styrene compounds, (meth)acrylic acid alkyl esters are preferable from the viewpoint of improving the low-temperature fixability of the toner. The number of carbon atoms in 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 viewpoints. , more preferably 12 or less, more preferably 8 or less. The number of carbon atoms in the alkyl ester refers to the number of carbon atoms derived from the alcohol component that constitutes the ester.

Specific examples of (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, (isopropyl)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 when these prefixes are present and when they are not, and when these prefixes are not present indicates normal. In addition, "(meth)acrylate" means at least one selected from acrylate and methacrylate.

The content of the (meth)acrylic acid alkyl ester is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less in terms of low-temperature fixability in the raw material monomer 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 raw material monomers containing a styrene compound and a (meth)acrylic acid alkyl ester is also called a styrene-(meth)acrylic resin.

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

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

(Both reactive monomers)
From the viewpoint of improving the low-temperature fixability of the toner, the composite resin (L-II) contains a raw material monomer for the polyester segment and a raw material monomer for the vinyl resin segment in addition to a raw material monomer for the polyester segment and a raw material monomer for the vinyl resin segment. It is preferably a composite resin obtained using a bi-reactive monomer that can react with either of the monomers. Therefore, when polymerizing the starting monomer for the polyester segment and the starting monomer for the vinyl resin segment to obtain a composite resin, the polycondensation reaction and/or the addition polymerization reaction are preferably carried out in the presence of both reactive monomers. As a result, the composite resin becomes a composite resin in which the polyester segment and the vinyl resin segment are bonded via the structural unit derived from the bi-reactive monomer, and the polyester segment and the vinyl resin segment are finer and more uniform. become dispersed.

As the bi-reactive monomer, at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, a primary amino group and a secondary amino group, preferably a hydroxyl group and a carboxyl group, is contained in the molecule. At least one functional group selected from the group consisting of, more preferably a compound having a carboxyl group and an ethylenically unsaturated bond. Dispersibility can be further improved. The dual-reactive monomer is preferably at least one selected from the group consisting of acrylic acid, methacrylic acid, fumaric acid, maleic acid and maleic anhydride, from the viewpoint of reactivity in polycondensation reaction and addition polymerization reaction. Therefore, 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 a polymerization inhibitor, the polyvalent carboxylic acid having an ethylenically unsaturated bond such as fumaric acid functions as a raw material monomer for the polyester segment. In this case, fumaric acid or the like is not a bireactive monomer but a starting monomer for the polyester segment.

From the viewpoint of improving the low-temperature fixability of the toner, the amount of the bi-reactive monomer used is preferably 1 mol part or more, more preferably 2 mol parts or more, relative to the total 100 mol parts of the alcohol component of the polyester segment. The amount is preferably 3 mol parts or more, and from the viewpoint of obtaining a toner having excellent hot offset resistance and a wide fixation width, it is preferably 20 mol parts or less, more preferably 10 mol parts or less, still more preferably 7 mol parts. It is below the department.

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 60/40 or more, from the viewpoint of improving the low-temperature fixability of the toner. is 70/30 or more, more preferably 75/25 or more, 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 fixation width. Below, more preferably below 85/15. In the above calculation, the mass of the polyester segment is the amount obtained by subtracting the amount of reaction water dehydrated by the polycondensation reaction (calculated value) from the mass of the raw material monomer of the polycondensation resin used. The amount of the organic monomer is included in the amount of raw material monomers for the polyester segment. Also, the amount of the vinyl resin segment is the amount of raw material monomers for the vinyl resin segment, but the amount of the polymerization initiator is included in the amount of raw material monomers for the vinyl resin segment.

(Physical properties of polyester resin L)
The softening point of Resin L is preferably 70° C. or higher, more preferably 90° C. or higher, still more preferably 100° C. or higher, and is 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 less.
The glass transition temperature of Resin L is preferably 30°C or higher, more preferably 40°C or higher, still more preferably 50°C or higher, and is preferably 80°C or lower, more preferably 70°C or lower, and still more preferably 60°C. It is below.

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

The number average molecular weight of Resin L is preferably 1,500 or more, more preferably 2,000 or more, still more preferably 2,500 or more, still more preferably 3,000 or more, and preferably 8,000 or less, It is more preferably 6,000 or less, still more preferably 5,000 or less, still more preferably 4,000 or less.

The weight average molecular weight of Resin L is preferably 5,000 or more, more preferably 8,000 or more, still more preferably 10,000 or more, still more preferably 12,000 or more, and preferably 1,000,000. Below, more preferably 800,000 or less, still more preferably 100,000 or less, 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 type and amount of raw material monomer used, and production conditions such as reaction temperature, reaction time and cooling rate. These values can be obtained by the method described in Examples.

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

<Polyester resin H>
Resin H is an alcohol component and a succinic acid substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms from the viewpoint of obtaining a toner having excellent low-temperature fixability and hot offset resistance and having a wide fixation width. or at least a polycondensate with a carboxylic acid component including an anhydride thereof.
Resin H is a polyester resin (HI) which is a polycondensate of an alcohol component and a carboxylic acid component containing succinic acid or its anhydride substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms, And a polyester segment which is a polycondensation portion of an alcohol component and a carboxylic acid component containing succinic acid or its anhydride substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms, and a monomer component containing a styrene compound. One or more selected from composite resins (H-II) having a vinyl-based resin segment, which is an addition polymerization portion of. As the resin H, a polyester resin (HI) is preferable from the viewpoint of obtaining a toner excellent in low-temperature fixability and hot offset resistance and having a wide fixation width.
Resin H is succinic acid or its The molar ratio of the anhydride and the succinic acid substituted with a linear aliphatic hydrocarbon group having 18 carbon atoms or its anhydride is 30/70 or more and 70/30 or less.
The resin H has a softening point higher than that 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 its anhydride substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms.
Examples and amounts of the alcohol component and the carboxylic acid component in the polyester resin (HI) are the same as those given for 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 preferred, and a propylene oxide adduct of bisphenol A and an ethylene oxide adduct of bisphenol A are more preferred.
The amount of the alkylene oxide adduct of bisphenol A is preferably 60 mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, in the alcohol component, and 100 mol % or less, more preferably 100 mol %.

The polyester resin (HI) preferably contains a polyvalent carboxylic acid having a valence of 3 or more as a carboxylic acid component. The trivalent or higher polyvalent carboxylic acid is preferably a trivalent carboxylic acid, more preferably trimellitic acid or its anhydride.
The amount of 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 30 mol % or less, still more preferably 30 mol % or less.

(Composite resin (H-II))
The composite resin (H-II) is a polyester segment which is a polycondensation portion of an alcohol component and a carboxylic acid component containing succinic acid or its anhydride substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms, and a vinyl-based resin segment that is an addition polymerization portion of a monomer component containing a styrene-based compound.
The polyester segment is made of polyester, and preferred examples of the polyester include those similar to the polyester resin (HI) described above.
The structure of the vinyl-based resin segment is the same as that of the composite resin (L-II) described above, and the preferred range is also the same, so the description is omitted.

(Physical properties of polyester resin H)
The softening point of Resin H is preferably 70° C. or higher, more preferably 90° C. or higher, still more preferably 100° C. or higher, still more preferably 110° C. or higher, still more preferably 112° C. or higher, and preferably 140° C. or lower. , more preferably 130° C. or lower, still more preferably 125° C. or lower.
The difference [M _H −M _L ] 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 widening the fixing range and improving the heat-resistant storage stability. It is preferably 8° C. or higher, and preferably 30° C. or lower, more preferably 20° C. or lower, still more preferably 15° C. or lower, still more preferably 12° C. or lower, further preferably 10° C. or lower.
The glass transition temperature of Resin H is preferably 30°C or higher, more preferably 40°C or higher, still more preferably 50°C or higher, and is preferably 80°C or lower, more preferably 70°C or lower, and still more preferably 60°C. It is below.

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

The number average molecular weight of Resin H is preferably 3,000 or more, more preferably 3,500 or more, still more preferably 4,000 or more, and preferably 8,000 or less, more preferably 6,000 or less, More preferably, it is 5,000 or less.

The weight average molecular weight of 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. 100,000 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 Resin H can be appropriately adjusted depending on the type and amount of raw material monomer used, and production conditions such as reaction temperature, reaction time and cooling rate. These values can be obtained by the method described in Examples.

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

From the viewpoint of further improving low-temperature fixability and hot-offset resistance and further widening the fixation width, succinic substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms per 100 mol parts of the alcohol component of Resin H. The ratio of the acid or its anhydride (hereinafter also simply referred to as “R _H ”) is succinic acid or its anhydride substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms with respect to 100 mol parts of the alcohol component of the resin L. It is preferable that the ratio is higher than the product ratio (hereinafter also simply referred to as “R _L ”).
The difference [R _H -R _L ] between R _H and R _L is preferably -20 mol parts or more, more preferably -20 mol parts or more, from the viewpoint of further improving low-temperature fixability and hot offset resistance and further widening the fixing range. is -15 mole parts or more, more preferably -10 mole parts or more, more preferably -5 mole parts or more, more preferably 0 mole parts or more, still more preferably 3 mole parts or more, and preferably 50 mole parts Below, more preferably 40 mol parts or less, still more preferably 30 mol parts or less, still more preferably 20 mol parts or less, still more preferably 10 mol parts or less.

The mass ratio of Resin H and 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, 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, preferably 70/30 or less.

<Crystalline polyester resin C>
From the viewpoint of improving the fixing width, the toner preferably contains a crystalline polyester resin C (hereinafter also simply referred to as "resin C").
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 number of carbon atoms in 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, still more preferably 12 or less. be.
Examples of α,ω-aliphatic diols 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, and 1,14-tetradecanediol mentioned. 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 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and It is 100 mol % or less, more preferably 100 mol %.

The alcohol component may contain other alcohol components different from the α,ω-aliphatic diol. Examples of other alcohol components include 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; 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 in the aliphatic dicarboxylic acid is preferably 4 or more, more preferably 8 or more, still more preferably 10 or more, and preferably 14 or less, more preferably 12 or less.
Aliphatic dicarboxylic acids include, for example, fumaric acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid. Among these, sebacic acid, dodecanedioic acid, and tetradecanedioic acid are preferred, sebacic acid and dodecanedioic acid are more preferred, and dodecanedioic acid is even more preferred. 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, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 mol % or less, more preferably 100 mol %.

The carboxylic acid component may contain other carboxylic acid components 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 polyvalent carboxylic 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, or more. It is preferably 1.2 or less.

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

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

The acid value of 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, still more preferably 25 mgKOH/g or less. .

The softening point, melting point, and acid value of Resin C can be appropriately adjusted depending on the type and ratio of raw material monomers, and production conditions such as reaction temperature, reaction time, and cooling rate. Those values are determined by the method described in Examples below. When two or more resins C are used in combination, the softening point, melting point, and acid value of the mixture are preferably within the ranges described above.

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 shown for the polycondensation in the resin L described above can be applied.

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

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

<Release agent>
Wax is preferred as the release agent.
Waxes include, for example, hydrocarbon waxes, ester waxes, silicone waxes, and fatty acid amide waxes.
Hydrocarbon waxes include, for example, mineral or petroleum hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax; synthetic hydrocarbon waxes such as polyolefin waxes such as polyethylene wax, polypropylene wax and polybutene wax.
Examples of ester waxes 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.
Fatty acid amide waxes include, for example, oleic acid amide and stearic acid amide. These may use 1 type(s) or 2 or more types.
Among these, hydrocarbon waxes are preferred, and paraffin waxes are more preferred, from the viewpoint of widening the fixation range and further improving heat resistance stability.

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

The amount of the release agent is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 3 parts by mass or more with respect to 100 parts by mass of the total amount of Resin L, Resin H and Resin C. Yes, and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less.

<Colorant>
Examples of colorants include carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine-B base, solvent red 49, solvent red 146, solvent blue 35, quinacridone, carmine 6B, and disazo yellow. mentioned.
The toner may be black toner or color toner other than black.
From the viewpoint of improving the image density of the toner, the content of the colorant is preferably 1 part by mass or more, more preferably 2 parts by mass or more with respect to 100 parts by mass of the total amount of resin L, resin H and resin C. Yes, 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 either a positive charge control agent or a negative charge control agent.
Examples of positive charge control agents include nigrosine dyes, triphenylmethane dyes containing a tertiary amine as a side chain, quaternary ammonium salt compounds, polyamine resins, imidazole derivatives, and styrene-acrylic resins.
Examples of nigrosine dyes 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” (manufactured by Orient Chemical Industry Co., Ltd.). Examples of quaternary ammonium salt compounds include "Bontron P-51" (manufactured by Orient Chemical Industry Co., Ltd.), cetyltrimethylammonium bromide, and "COPY CHARGE PX VP435" (manufactured by Clariant). Examples of polyamine resins include "AFP-B" (manufactured by Orient Chemical Industry Co., Ltd.). Examples of imidazole derivatives include "PLZ-2001" and "PLZ-8001" (manufactured by Shikoku Kasei Co., Ltd.). Examples of the styrene-acrylic resin include "FCA-701PT" (manufactured by Fujikura Kasei Co., Ltd.).

Examples of negative charge control agents include metal-containing azo dyes, metal compounds of benzilic acid compounds, metal compounds of salicylic acid compounds, copper phthalocyanine dyes, quaternary ammonium salts, nitroimidazole derivatives, and organometallic compounds.
Examples of metal-containing azo dyes include "Varifast Black 3804", "Bontron S-31", "Bontron S-32", "Bontron S-34", and "Bontron S-36" (Orient Chemical Industry Co., Ltd. (manufactured by Hodogaya Chemical Industry Co., Ltd.), “Eizenspiron Black TRH”, and “T-77” (manufactured by Hodogaya Chemical Industry Co., Ltd.). Examples of metal compounds of benzylic acid compounds include "LR-147" and "LR-297" (manufactured by Nihon Carlit Co., Ltd.). Examples of metal compounds of salicylic acid compounds include "Bontron E-81", "Bontron E-84", "Bontron E-88", "Bontron E-304" (manufactured by Orient Chemical Industry Co., Ltd.), "TN -105” (manufactured by Hodogaya Chemical Industry Co., Ltd.). Examples of quaternary ammonium salts include "COPY CHARGE NX VP434" (manufactured by Clariant). Examples of organometallic compounds include "TN105" (manufactured by Hodogaya Chemical Industry Co., Ltd.).

The content of the charge control agent is preferably 0.01 parts by mass or more, more preferably 0.2 parts by mass or more, and still more preferably 0.2 parts by mass, based on 100 parts by mass of the total amount of Resin L, Resin H and Resin C. It is 3 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 2 parts by mass or less.

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

<Physical properties of toner particles>
The volume-median particle diameter ( _D50 ) 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 high-quality images and further improving the cleanability of the toner. Yes, and preferably 10 μm or less, more preferably 8 μm or less, and even more preferably 6 μm or less.
The volume-median particle size ( _D50 ) of toner particles can be measured by the method described in Examples.

[External additive]
Although the toner particles can be used as the toner as it is, it is preferable to use the toner after adding a fluidizing agent or the like as an external additive to the surface of the toner particles.
Examples of external additives include inorganic material 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 toner particles are surface-treated using an external additive, the amount of the external additive added 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 3 parts by mass or more, and preferably 5 parts by mass or less, more preferably 4.5 parts by mass or less, and even more preferably 4 parts by mass or less.

Toners are used for electrostatic image development in electrophotographic printing. The toner can be used, for example, as a one-component developer or mixed with a carrier as a two-component developer.

[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, or an aggregation-fusion method. A chemical toner obtained by a bonding method and a pulverized toner obtained by a melt-kneading method are preferable, and a chemical toner obtained by an aggregation fusion bonding method is more preferable.

[Aggregation and fusion method]
In the case of a chemical toner produced by the aggregation fusion method, the method for producing the toner includes, for example,
A step of aggregating resin particles containing resin L and resin H in the same or different particles, optionally resin particles containing resin C, and release agent particles W to obtain aggregated particles (1) (hereinafter referred to as , also referred to as “Step 1”),
A step of attaching resin particles containing resin L and resin H in the same or different particles to aggregated particles (1) to obtain aggregated particles (2) (hereinafter also referred to as “step 2”); A step of fusing in an aqueous medium (hereinafter also referred to as “step 3”)
including.

As the various resin particles used in step 1, a dispersion liquid in which resins such as resin L, resin H, and resin C are previously dispersed in an aqueous medium is used. Although the dispersion method is not particularly limited, it is preferable to disperse by, for example, a phase inversion emulsification method. The phase inversion emulsification method includes, for example, a method in which an aqueous medium is added to an organic solvent solution of a resin or a molten resin to effect phase inversion emulsification. The aqueous medium preferably contains 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 a water-soluble organic solvent.
As the release agent particles W used in step 1, a dispersion liquid in which the release agent is previously dispersed 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 alkylbenzenesulfonate, the dispersion is mixed, a flocculating agent such as ammonium sulfate is added to flocculate, and if necessary, flocculation of the surfactant or the like. Aggregated particles (1) are obtained by adding a terminating agent.

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

[Melt-kneading method]
In the case of pulverized toner by the melt-kneading method, raw materials such as resin L, resin H, resin C, release agent, colorant, charge control agent, etc. are uniformly mixed with a mixer such as a Henschel mixer, and then mixed with a closed kneader. , a single-screw or twin-screw extruder, an open-roll type kneader, or the like, followed by cooling, pulverization, and classification.
The method for producing a pulverized toner preferably includes a step of melt-kneading a mixture containing the binder resin composition at a temperature in the range of 80° C. or higher and 160° C. or lower. The melt-kneading temperature is preferably 85° C. or higher, more preferably 90° C. or higher, and preferably 150° C. or lower, more preferably 130° C. or lower.
In the binder resin composition of the present invention, the affinity between the amorphous resin and the crystalline resin is high, but they are difficult to be compatible with each other. Therefore, the binder resin can be crystallized by the melt-kneading step described above.

The method for producing 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 known methods.

Properties of the resin, resin particles, toner, etc. were measured and evaluated by the following methods.

[Measuring method]
[Acid value of resin]
The acid value of the resin was measured according to JIS K 0070:1992. However, only the measurement solvent was changed from the 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)).

[Resin softening point, maximum endothermic peak temperature, glass transition temperature]
(1) Softening point Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), while heating a 1 g sample at a temperature increase rate of 6 ° C./min, a load of 1.96 MPa is applied with a plunger, and the diameter It was extruded through a 1 mm, 1 mm long nozzle. The amount of plunger depression of the flow tester was plotted against the temperature, and the softening point was defined as the temperature at which half of the sample flowed out.
(2) Maximum temperature of endothermic peak Using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), the temperature was lowered from room temperature (20 ° C.) to 0 ° C. at a cooling rate of 10 ° C./min. The sample cooled to 10° C. was allowed to stand still for 1 minute, and then measured while being heated to 180° C. at a heating rate of 10° C./min. Among the observed endothermic peaks, the temperature of the peak on the highest temperature side was 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 the sample is weighed in an aluminum pan and heated to 200 ° C. and cooled to 0°C from that temperature at a cooling rate of 10°C/min. Next, the temperature was measured while the temperature was raised to 150° C. at a rate of temperature rise of 10° C./min. The glass transition temperature was defined as the temperature at the intersection of the extended line of the baseline below the maximum temperature of the endothermic peak and the tangential line showing the maximum slope from the rising portion of the peak to the apex of the peak.

[Number average molecular weight and weight average molecular weight of polyester resin]
The molecular weight distribution was measured by gel permeation chromatography (GPC) by 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 A polyester resin was dissolved in chloroform so as to have a concentration of 0.5 g/100 mL. Subsequently, this solution was filtered using a fluororesin filter "FP-200" (manufactured by Sumitomo Electric Industries, Ltd.) with a pore size of 2 μm to remove insoluble components to obtain a sample solution.
(2) Molecular weight measurement Using the following apparatus, chloroform was passed 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 measured. The molecular weight of the sample was calculated based on a previously prepared calibration curve. In the calibration curve at this time, several types of monodisperse polystyrene with known molecular weights "2.63 × 10 ³ ", "2.06 × 10 ⁴ ", "1.02 × 10 ⁵ " (manufactured by Tosoh Corporation )
Standard samples of “2.10×10 ³ ”, “7.00×10 ³ ”, and “5.04×10 ⁴ ” (manufactured by GL Sciences Inc.) were used.
Measuring device: "CO-8010" (manufactured by Tosoh Corporation)
Analysis column: "GMH _XL " + "G3000H _XL " (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 the sample was weighed into an aluminum pan, and heated to 200 at a heating rate of 10 ° C./min. °C, and then cooled to -10°C at a cooling rate of 5°C/min. Next, the sample is heated to 180° C. at a heating rate of 10° C./min and measured. The maximum endothermic peak temperature observed from the melting endothermic curve thus obtained is taken as the melting point of the release agent.

[Volume Median Particle Diameter (D ₅₀ ) and CV Value of Aggregated Particles (1), Toner Particles, and Toner]
The volume-median particle size (D ₅₀ ) of aggregated particles (1), toner particles, and 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" (manufactured by Beckman Coulter, Inc.)
・Electrolyte: “Isoton II” (manufactured by Beckman Coulter, Inc.)
- Dispersion: Polyoxyethylene lauryl ether "Emulgen 109P" (manufactured by Kao Corporation, HLB: 13.6) was dissolved in the electrolytic solution to obtain a dispersion having a concentration of 5% by mass.
Dispersion conditions: 10 mg of a toner measurement sample was added to 5 mL of the dispersion liquid, dispersed for 1 minute with an ultrasonic disperser, then 25 mL of an electrolytic solution was added, and dispersed for 1 minute with an ultrasonic disperser. , to prepare a sample dispersion.
Measurement conditions: By adding the sample dispersion to 100 mL of the electrolytic solution, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, then 30,000 particles are measured, and the particle size distribution The volume median particle size (D ₅₀ ) was obtained from
Also, the volume average particle diameter (D _v ) was obtained in the same manner as the volume median particle diameter (D ₅₀ ), and the CV value (%) was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution/volume average particle size ( _Dv )) x 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 particle size measuring machine “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 the proper range.

[Solid content concentration of dispersion]
Using an infrared moisture meter "FD-230" (manufactured by Ketsuto Kagaku Kenkyusho Co., Ltd.), 5 g of the sample is dried at a temperature of 150 ° C. and under the conditions of measurement mode 96 (monitoring time 2.5 minutes / fluctuation width 0.05%). The sample was dried with a vacuum cleaner, and the moisture content (% by mass) of the sample was measured. The solid content was calculated according to the following formula.
Solid content concentration (mass%) = 100 - water content of sample (mass%)

[evaluation]
[Fixation width]
The fixation width is the difference between the minimum fixation temperature obtained from the low-temperature fixability evaluation described below and the minimum temperature at which hot offset occurs obtained from the hot offset resistance evaluation described below.
(low temperature fixability)
Toner was mounted on a copier "AR-505" (manufactured by Sharp Corporation) in which the fixing device was improved so that it could be fixed outside the device, and printed matter was obtained in an unfixed state (printing area: 2 cm) × 12 cm, adhesion amount: 0.5 mg/cm ² ). After that, using a fixing machine (fixing speed: 300 mm/sec) adjusted so that the total fixing pressure was 40 kgf, the temperature of the fixing roll was increased from 100° C. to 240° C. by 5° C. in increments of 5° C., and unfixed at each temperature. A fixing test of the printed matter in the state was performed. A 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 resulting printed matter, and the temperature was set to 30 ° C. separately from the fixing roll of the fixing machine. After passing through the fixing roller, the tape was peeled off. The optical reflection density before the tape was applied and after it was removed was measured using a reflection densitometer "RD-915" (manufactured by Gretag Macbeth), and the ratio of the two (after peeling/before pasting x 100) was initially 90%. was taken as the lowest fixing temperature. The lower the minimum fixing temperature, the better the low-temperature fixability. As the fixing paper, "CopyBond SF-70NA" (manufactured by Sharp Corporation, 75 g/m ² ) was used.
(Hot offset resistance)
During the evaluation of the "low-temperature fixability" described above, occurrence of hot offset was visually observed, and the minimum temperature at which hot offset occurred was confirmed as hot offset resistance. The higher the temperature at which this 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 Kouatsu Co., Ltd.), α-olefin "Linearene 16" (Idemitsu Kosan Co., Ltd.), 253.9 g of α-olefin "Linearene 18" (manufactured by Idemitsu Kosan Co., Ltd.), 157.2 g of maleic anhydride, antioxidant "Chelex-O" (SC Organic Chemical Co., Ltd.) 0.4 g of triisooctyl phosphite (manufactured by Sanyo Co., Ltd.) and 0.1 g of butylhydroquinone as a polymerization inhibitor were charged, and pressure nitrogen substitution (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 when reaching the reaction temperature was 0.3 MPaG. After completion of the reaction, the reaction mixture was cooled to 80° C., returned to normal pressure (101.3 kPa), and the reactant was transferred to a 1 L four-necked flask. The temperature was raised to 180° C. with stirring, 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 the target alkenyl succinic anhydride a. 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, antioxidants, and polymerization inhibitors were changed as shown in Table 1. The average molecular weight of the alkenyl succinic anhydride was obtained from the acid value and shown in Table 1.

[Manufacturing 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 polyester resin raw material monomers other than trimellitic anhydride, the esterification catalyst, and the esterification co-catalyst shown in Table 2 are placed in a 5-liter four-necked flask equipped with a nitrogen inlet tube, a stirrer, and a thermocouple. , under a nitrogen atmosphere, was heated to 235°C, and then polycondensed at 235°C for 6 hours. After that, 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 to the softening point shown in Table 2 to obtain amorphous polyester resins H-1, H-3 to H-5, and H-8 to H-18. rice field. 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)
Raw material monomers for polyester resins other than sebacic acid and trimellitic anhydride, esterification catalysts and esterification co-catalysts shown in Table 2 were added to a 5-liter four-neck flask equipped with a nitrogen inlet tube, a stirrer and a thermocouple. It was placed in a flask, heated to 235° C. under a nitrogen atmosphere, and then polycondensed at 235° C. for 6 hours. Then, the temperature was lowered to 180°C, sebacic acid and trimellitic anhydride 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. After that, 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)
The polyester resin starting monomers other than trimellitic anhydride, the esterification catalyst and the esterification co-catalyst shown in Table 2 were added to a dehydration tube equipped with a nitrogen introduction tube and a fractionation tube through which hot water at 98 ° C. was passed, and stirred. placed in a 5-liter four-necked flask equipped with a vessel and a thermocouple, held at 180 ° C. for 1 hour under a nitrogen atmosphere, then heated from 180 ° C. to 210 ° C. at a rate of 10 ° C./hour, and then at 210 ° C. Timed polycondensation. After that, trimellitic anhydride was added and reacted at 210° C. for 1 hour, and then further reacted at 210° C. under a reduced pressure of 10 kPa to the softening point shown in Table 2. 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)
Equipped with a dehydration tube equipped with a nitrogen introduction tube, a stirrer and a thermocouple, with the raw material monomer, esterification catalyst and esterification co-catalyst of the polyester resin (segment (B1)) other than trimellitic anhydride shown in Table 2. The mixture was placed in a 5-liter four-necked flask, heated to 235° C. under a nitrogen atmosphere, and then polycondensed at 235° C. for 6 hours. Thereafter, the temperature was lowered to 160° C., and a mixture of raw material monomers for acrylic acid (dually reactive monomer), vinyl resin (segment (B2)), and a polymerization initiator was added dropwise from a dropping funnel over 1 hour. After the dropwise addition, the addition polymerization reaction was allowed to mature for 1 hour while the temperature was kept at 160° C., then the temperature was raised to 200° C. and the pressure was reduced at 10 kPa for 1 hour. After that, 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. Furthermore, 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 polyester resin raw material monomers other than fumaric acid, the esterification catalyst and the esterification co-catalyst shown in Table 3 were placed in a 5-liter four-necked flask equipped with a nitrogen inlet tube, a stirrer and a thermocouple, and placed in a nitrogen atmosphere. Then, the temperature was raised to 235°C, and polycondensation was carried out at 235°C for 6 hours. After that, 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 to the softening point shown in Table 3 to obtain amorphous polyester resins L-1, L-3 to L-5, and L-8 to L-17. rice field. 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 polyester resin raw material monomers other than sebacic acid and fumaric acid, the esterification catalyst, and the esterification co-catalyst shown in Table 3 were placed in a 5-liter four-necked flask equipped with a nitrogen inlet tube, a stirrer, and a thermocouple. , under a nitrogen atmosphere, was heated to 235°C, and then polycondensed at 235°C for 6 hours. After that, the temperature was lowered to 180°C, sebacic acid, 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. After that, 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)
Raw material monomers for polyester resins other than fumaric acid, esterification catalysts and esterification co-catalysts shown in Table 3 were added to a dehydration tube equipped with a nitrogen introduction tube, a fractionation tube through which hot water at 98 ° C. was passed, a stirrer and a thermoelectric generator. Placed in a 5-liter four-necked flask equipped with a coupler, maintained at 180°C for 1 hour under a nitrogen atmosphere, heated from 180°C to 210°C at a rate of 10°C/hour, and then polycondensed at 210°C for 10 hours. let me After that, 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, reaction was carried out at 210° C. under a reduced pressure of 10 kPa to the softening point shown in the table to obtain 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)
Raw material monomers for polyester resin (segment (B1)) other than fumaric acid (segment (B1)) shown in Table 3, an esterification catalyst and an esterification co-catalyst were added to 5 liters equipped with a dehydration tube equipped with a nitrogen introduction tube, a stirrer and a thermocouple. The mixture was placed in a four-necked flask with a capacity of 1,000 liters, heated to 235° C. under a nitrogen atmosphere, and then polycondensed at 235° C. for 6 hours. Thereafter, the temperature was lowered to 160° C., and a mixture of raw material monomers for acrylic acid (dually reactive monomer), vinyl resin (segment (B2)), and a polymerization initiator was added dropwise from a dropping funnel over 1 hour. After the dropwise addition, the addition polymerization reaction was allowed to mature for 1 hour while the temperature was kept at 160° C., then the temperature was raised to 200° C. and the pressure was reduced at 10 kPa for 1 hour. After that, 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 a rate of 10°C/hour, and then the reaction was carried out at 210°C for 1 hour. Furthermore, 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 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 placed in a 5-liter four-necked flask equipped with a thermometer, stainless steel stirring rod, flow-down condenser and nitrogen inlet tube, and heated to 200°C in a nitrogen atmosphere in a mantle heater. The temperature was raised over time. After that, 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 (resin particle dispersion liquid XH-1)
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 above was heated to 60°C. was added and allowed to dissolve. To the resulting solution, a 20 mass% aqueous ammonia solution (pKa: 9.3) was added so that the degree of neutralization was 100 mol% with respect to the acid value of Resin H-1, and the mixture was stirred for 30 minutes. got Subsequently, 675 g of ion-exchanged water was added over 77 minutes. Next, while stirring at 250 r/min, methyl ethyl ketone is distilled off at a temperature of 50° C. or less under reduced pressure, and then an anionic surfactant “Emar E27C” (manufactured by Kao Corporation, polyoxyethylene lauryl ether sodium sulfate, 16.7 g of solid content 28% by mass) was mixed and completely dissolved. After that, the solid content concentration of the dispersion liquid was measured, and ion-exchanged water was added to adjust the solid content concentration of the dispersion liquid to 20% by mass. The resulting dispersion is referred to as XH-1.

Production Examples XH2 to XH20 (resin particle dispersions XH-2 to XH-20)
In Production Example XH1, 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. Dispersions XH-2 to XH-20 of resin particles were obtained in the same manner as in Production Example XH1. Various physical properties of the resulting dispersion were measured and shown in Table 5.

Production Examples XL1 to XL19 (resin particle dispersions XL-1 to XL-19)
In Production Example XH1, 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. Dispersions XL-1 to XL-19 of resin particles were obtained in the same manner as in Production Example XH1. Various physical properties of the resulting dispersion were measured and shown in Table 6.

Production Examples XC1 to XC2 (resin particle dispersions XC-1 to XC-2)
In Production Example XH1, the amorphous polyester resin used was changed to crystalline polyester resins C-1 and 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. Dispersions XC-1 and XC-2 of resin particles were obtained in the same manner as in Production Example XH1 except for the above. Various physical properties of the resulting dispersion were measured and shown in Table 7.

[Production of Release Agent Dispersion]
Production Example W1 (Production of Release Agent Dispersion W-1)
50 g of paraffin wax “HNP0190” (manufactured by Nippon Seiro Co., Ltd., melting point: 85° C.), 5 g of cationic surfactant “Sanizol B50” (manufactured by Kao Corporation) and 200 g of deionized water were heated to 95° C. and homogenized. was used to disperse the paraffin wax, followed by dispersion treatment with a pressure discharge homogenizer to obtain a release agent dispersion W-1 containing release agent particles having a solid concentration of 20% by mass. The volume median particle size ( _D50 ) of the release agent particles was 550 nm.

[Production of colorant dispersion]
Production Example P1 (Production of Colorant Dispersion P-1)
Copper phthalocyanine "ECB-301" (manufactured by Dainichiseika Kogyo Co., Ltd.) 50 g, nonionic surfactant "Emulgen 150" (manufactured by Kao Corporation, polyoxyethylene lauryl ether) 5 g and ion-exchanged water 200 g are mixed, Dispersed at 25° C. for 10 minutes using a homogenizer to obtain a colorant dispersion P-1 containing colorant particles. The volume median particle diameter ( _D50 ) of the colorant particles having a solid content concentration of 20% by mass was 120 nm.

[Production of charge control agent dispersion]
Production Example CH1 (Production of Charge Control Agent Dispersion CH-1)
50 g of a salicylic acid-based compound "Bontron E-84" (manufactured by Orient Chemical Industry Co., Ltd.) as a charge control agent, 5 g of a nonionic surfactant "Emulgen 150" (manufactured by Kao Corporation) and 200 g of ion-exchanged water are mixed, and a glass is prepared. The beads were dispersed at 25° C. for 10 minutes using a sand grinder to obtain a charge control agent dispersion CH-1 containing charge control agent particles. The volume-median particle diameter ( _D50 ) of the charge control agent particles having a solid content concentration of 20% by mass was 500 nm.

[Production of Toner for Developing Electrostatic Charge Image]
Example 1 (Production of Toner 1)
150 g of Dispersion XH-1, 150 g of Dispersion XL-1, 38 g of Dispersion XC-1, 15 g of Release Agent Dispersion W-1, 8 g of Colorant Dispersion P-1, and 2 g of Charge Control Agent Dispersion CH-1 were prepared. , and 150 g of a 0.1% by mass calcium chloride aqueous solution was added dropwise at 20° C. over 30 minutes while stirring at 100 r/min (peripheral speed 31 m/min) with an anchor type stirrer. After that, the temperature was raised to 50° C. while stirring. Aggregated particles (1) having a volume-median particle diameter (D ₅₀ ) of 5 μm after 3 hours were obtained. Thereafter, a mixture of 22.5 g of Dispersion XH-1 and 22.5 g of Dispersion XL-1 was added and dispersed by stirring to obtain aggregated particles (2). After that, a diluted solution obtained by diluting 4.2 g of an anionic surfactant "Emar E27C" (manufactured by Kao Corporation, solid content 28% by mass) as an aggregation terminator in the dispersion of aggregated particles (2) with 37 g of deionized water. was added. Then, the temperature was raised to 80° C., and after the temperature was maintained at 80° C. for 1 hour, the heating was terminated. After the fused particles are formed in this manner, the particles are slowly cooled to 20° C., filtered through a wire mesh of 150 mesh (opening of 150 micrometers), subjected to suction filtration, thoroughly washed with deionized water, and dried. Toner particles were obtained by The volume median particle size ( _D50 ) of the resulting toner particles was 5.1 μm.
To 100 parts by mass of toner particles, 0.5 parts by mass of hydrophobic silica "Aerosil R-972" (manufactured by Nippon Aerosil Co., Ltd., number average particle diameter: 16 nm) is added as an external additive, and a Henschel mixer (Nippon Coke Kogyo Co., Ltd.) at 3600 r/min (peripheral speed 31.7 m/sec) for 5 minutes to obtain Toner 1 having a volume median particle size (D ₅₀ ) of 5.1 μm. Various evaluations were performed and the results are shown in Table 8.

Examples 2-9, 11-21 and Comparative Examples 1-9 (manufacture of toners 2-9, 11-21, 81-89)
Toners 2 to 9 and 11 were prepared in the same manner as in Example 1, except that the type and amount of the resin particle dispersion used in Example 1 were changed to those shown in Table 8. ~21, 81-89 were obtained. 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 Dainichiseika Kogyo Co., Ltd.) Part by mass, 1 part by mass of charge control agent "LR-147" (manufactured by Nippon Carlit Co., Ltd.), and 2 parts by mass of 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 kneading part with a total length of 1560 mm, a screw diameter of 42 mm and a barrel inner diameter of 43 mm. The rotation speed of the screw was 200 r/min, the set heating temperature in the screw was 90°C, the temperature of the kneaded material was 140°C, the supply rate of the kneaded material was 10 kg/h, and the average residence time was about 18 seconds. The resulting kneaded product was cooled from 140° C. to 50° C. in 1.5 hours, rolled and cooled at 50° C. with a cooling roller, allowed to stand at 45° C. for 4 hours, pulverized with a jet mill, classified, and volumetrically Toner particles with a median particle size (D ₅₀ ) of 5.5 μm were obtained.

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

From the results of the examples and comparative examples described above, it can be seen that the toner of the present invention is excellent in low-temperature fixability and hot offset resistance, and has a wide fixation range.

Claims (8)

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 each independently contain an alcohol component and a carboxylic acid component containing succinic acid or its anhydride 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 its anhydride substituted with a straight-chain aliphatic hydrocarbon group having 16 carbon atoms in the carboxylic acid component and a straight-chain aliphatic hydrocarbon having 18 carbon atoms. A toner for electrostatic charge image development, wherein the molar ratio of succinic acid substituted with a hydrocarbon group or its anhydride is 30/70 or more and 70/30 or less. The ratio of succinic acid or its anhydride substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms with respect to 100 mol parts of the alcohol component of the polyester resin H is carbon with respect to 100 mol parts of the alcohol component of the polyester resin L. 2. The electrostatic image developing toner according to claim 1, wherein the proportion of the succinic acid or its anhydride substituted with a linear aliphatic hydrocarbon group of number 16 to 18 is higher than that of the succinic acid or its anhydride. In the polyester resin L and the polyester resin H, the proportion of succinic acid or its anhydride substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms is 3. The toner for electrostatic charge image development according to claim 1, wherein the amount is 1 mol part or more and 30 mol parts or less. 4. The toner for electrostatic charge image development according to claim 1, wherein the alcohol component of said polyester resin L contains 70 mol % or more of a propylene oxide adduct of bisphenol A in the alcohol component. 5. The toner for electrostatic charge image development according to claim 1, wherein the alcohol component of the polyester resin H contains 60 mol % or more of the alkylene oxide adduct of bisphenol A in the alcohol component. The static generator according to any one of claims 1 to 5, wherein the 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. Toner for charge image development. 7. The toner for electrostatic charge image development according to claim 1, further comprising a crystalline polyester resin. The polyester resin L and the polyester resin H are each independently composed of an alcohol component and a carboxylic acid component containing succinic acid or its anhydride substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms. A polyester resin that is a polycondensate, and a polyester segment that is a polycondensation portion of an alcohol component and a carboxylic acid component containing succinic acid or its anhydride substituted with a linear aliphatic hydrocarbon group having 16 to 18 carbon atoms. , and a composite resin having a vinyl resin segment which is an addition polymerization portion of a monomer component containing a styrene compound.