JP2019095475A - Method for producing electrophotographic toner - Google Patents

Abstract

To provide a method for producing an electrophotographic toner excellent in low temperature fixability, storage property and charge stability in high temperature.SOLUTION: A method for producing an electrophotographic toner includes a step of suspension-polymerizing a polymerizable monomer composition containing a crystalline polyester resin, a composite resin (A), a polymerizable monomer and a coloring agent in an aqueous medium, in which the crystalline polyester resin is a polycondensation product of an alcohol component containing 80 mol% or more of α,ω-aliphatic diol having 2 or more and 16 or less carbon atoms and a carboxylic acid component containing an aliphatic dicarboxylic acid having 4 or more and 18 or less carbon atoms, the composite resin (A) contains a polyester resin segment, a vinyl-based resin segment that is an addition polymer of a raw material monomer containing a styrene-based compound, a constitutional unit derived from a bireactive monomer bonded with the polyester resin segment and the vinyl-based segment through a covalent bond, and a constitutional unit derived from hydrocarbon wax (II) bonded with the polyester resin segment through a covalent bond, and the hydrocarbon wax (II) has at least one group selected from a hydroxyl group and a carboxyl group and has a melting point of 60°C or higher and 130°C or lower.SELECTED DRAWING: None

Description

  The present invention relates to a method of producing a toner for electrophotography.

  In recent years, with the speeding up and energy saving of printers and copiers, toners capable of meeting these demands are increasingly required. From the viewpoint of further speeding up of the printing apparatus and energy saving, a high degree of compatibility between the low temperature fixability and the storage stability is required, and the use of a crystalline polyester resin is being studied.

  In Patent Document 1, a crystalline polyester (1-%) obtained using a raw material monomer containing a diol having 8 to 12 carbon atoms and a dicarboxylic acid compound having 10 to 12 carbon atoms, and the total content of both is 80 mol% or more 1) A raw material monomer of an amorphous condensation polymerization resin containing an alcohol component and a carboxylic acid component containing an aromatic dicarboxylic acid compound, a raw material monomer of an addition polymerization resin and a raw material monomer of the addition polymerization resin 100 weight Amorphous condensation polymerization system obtained by polymerizing a compound capable of reacting with 3 to 15 parts by weight of a raw material monomer of an amorphous condensation polymerization resin and a raw material monomer of an addition polymerization resin A toner for developing an electrostatic charge image, comprising a binder resin comprising an amorphous hybrid resin (2-1) comprising a resin component and an addition polymerization resin component, which comprises the above-described binder. Ratio of crystalline polyester (1-1) to amorphous hybrid resin (2-1) (crystalline polyester (1-1) / amorphous hybrid resin (2-1)) is 1/99 to 40/60 The toner for electrostatic image development is described. According to the toner, it is described that the low temperature fixability and the heat resistant storage stability are excellent, and furthermore, the storage stability of the printed matter and the image density are also good.

JP, 2013-109237, A

As shown in Patent Document 1, when a crystalline polyester resin is used for the toner, the low temperature fixing property is improved but the storage stability is lowered.
Even in the case of a suspension polymerization toner, when a crystalline polyester resin is used, the low temperature fixability is improved, but the storage stability tends to be lowered. Furthermore, when a crystalline polyester resin is used for the suspension polymerization toner, there is no problem immediately after the production of the toner, but under high temperature conditions, phase separation with the crystalline polyester resin is promoted with time, and as a result, the chargeability is maintained. Found that it would be difficult.
Therefore, the present invention relates to a method for producing a toner for electrophotography, which is excellent in low-temperature fixability, storage stability, and charge stability at high temperatures.

The present inventors have found that the above-mentioned problems can be solved by using a specific crystalline polyester resin and a specific composite resin (A) in combination.
The present invention provides a toner for electrophotography comprising the step of suspension polymerizing a polymerizable monomer composition containing a crystalline polyester resin, a composite resin (A), a polymerizable monomer and a colorant in an aqueous medium. Method,
The polycondensation of an alcohol component containing 80 mol% or more of an α, ω-aliphatic diol having 2 to 16 carbon atoms and a carboxylic acid component containing an aliphatic dicarboxylic acid having 4 to 18 carbon atoms in the crystalline polyester resin It is a thing,
The composite resin (A) is a vinyl resin segment, which is an addition polymer of a polyester resin segment and a raw material monomer containing a styrenic compound, and both reactions bonded via covalent bonds to the polyester resin segment and the vinyl resin segment. Hydrocarbon wax (II) is selected from a hydroxyl group and a carboxy group, comprising a structural unit derived from a cationic monomer and a structural unit derived from a hydrocarbon wax (II) bonded to the polyester resin segment via a covalent bond The present invention relates to a method for producing a toner for electrophotography having at least one type of group and having a melting point of 60 ° C. or more and 130 ° C. or less.

  According to the present invention, it is possible to provide a method for producing a toner for electrophotography which is excellent in low-temperature fixability, storage stability and charge stability under high temperature.

[Method for producing electrophotographic toner]
The process for producing the toner for electrophotography (hereinafter, also simply referred to as “toner”) of the present invention is a polymerizable monomer composition comprising a crystalline polyester resin, a composite resin (A), a polymerizable monomer and a colorant. Suspension polymerization in an aqueous medium.
The crystalline polyester resin is a polycondensate of an alcohol component containing 80 mol% or more of an α, ω-aliphatic diol having 2 to 16 carbon atoms and a carboxylic acid component containing an aliphatic dicarboxylic acid having 4 to 18 carbon atoms. It is.
The composite resin (A) is a vinyl resin segment, which is an addition polymer of a polyester resin segment and a raw material monomer containing a styrenic compound, both bonded to the polyester resin segment and the vinyl resin segment via a covalent bond. The hydrocarbon wax (II) is selected from a hydroxyl group and a carboxy group, and contains a constituent unit derived from a reactive monomer and a constituent unit derived from a hydrocarbon wax (II) bonded to the polyester resin segment via a covalent bond. The melting point is 60.degree. C. or more and 130.degree. C. or less.
According to the above manufacturing method, it is possible to provide a method for manufacturing a toner for electrophotography which is excellent in low-temperature fixability, storage stability and charge stability at high temperature.

Although the reason is not clear, it is considered as follows.
Since the composite resin (A) has a polyester resin segment, it has good affinity with the crystalline polyester resin, and since it has a vinyl-based resin segment, it has good affinity with the polymer of the polymerizable monomer. Because of this, the crystalline polyester resin is finely dispersed and exhibits high stability even after production, so it is considered that storage stability and charge stability under high temperature are improved. The low temperature fixability is improved by finely dispersing the crystalline polyester resin in the toner.

Definitions of various terms in the present specification are shown below.
Whether the resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is defined as the ratio of the softening point of the resin to the highest endothermic peak temperature (softening point (° C.) / The highest endothermic peak temperature (° C.)) in the measurement methods described in the examples described later. The crystalline resin is a resin having a crystallinity index of 0.6 or more and less than 1.4, preferably 0.7 or more, more preferably 0.9 or more, and preferably 1.2 or less. An amorphous resin is a resin having a crystallinity index of 1.4 or more, or less than 0.6, preferably 1.5 or more, or 0.5 or less, more preferably 1.6 or more, or 0.5 or less It is. The crystallinity index can be appropriately adjusted according to the type and ratio of the raw material monomers, and the production conditions such as the reaction temperature, the reaction time, and the cooling rate. The highest endothermic peak temperature refers to the temperature of the highest end of the observed endothermic peaks. The crystallinity index can be calculated from the values obtained by the methods for measuring the softening point and endothermic peak temperature of the resin described in the examples.
In the specification, the carboxylic acid component of the polyester resin includes not only the exemplified compounds but also an anhydride which is decomposed during the reaction to form an acid, and an alkyl ester of each carboxylic acid (the carbon number of the alkyl group is 1 to 3) The following is included.
In the specification, the binder resin component means a component which forms a resin component of toner particles, which contains a resin component such as crystalline polyester resin and composite resin (A) and a polymerizable monomer.

In the production method of the present invention, the polymerizable monomer composition is suspension-polymerized in an aqueous medium.
As a manufacturing method of the present invention, for example,
Obtaining a suspension of the polymerizable monomer composition in an aqueous medium (hereinafter also referred to as “step 1”);
A step of suspension polymerizing the polymerizable monomer composition in an aqueous medium by the suspension (hereinafter, also referred to as “step 2”);
And the like.
Hereinafter, the present invention will be described in detail by taking the above-mentioned manufacturing method as an example.

<Step 1>
[Water based medium]
As the aqueous medium, one containing water as a main component is preferable.
The content of water in the aqueous medium is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more, and 100% by mass or less It is more preferably 100% by mass. As water, deionized water or distilled water is preferred.
As components other than water that may be contained in the aqueous medium, for example, alkyl alcohol having 1 to 5 carbon atoms; dialkyl ketone having 3 to 5 carbon atoms such as acetone and methyl ethyl ketone; and dissolution in water such as cyclic ether such as tetrahydrofuran Organic solvents can be mentioned.

[Polymerizable Monomer Composition]
The polymerizable monomer composition contains a crystalline polyester resin, a composite resin (A), a polymerizable monomer and a colorant.
The polymerizable monomer composition includes, for example, charge control agents, mold release agents, magnetic powders, fluidity improvers, conductivity adjusters, reinforcing fillers such as fibrous substances, antioxidants, antiaging agents, cleaning It may contain a sex enhancer.

(Crystalline polyester resin)
The crystalline polyester resin contains 80 mol% or more of an α, ω-aliphatic diol having 2 to 16 carbon atoms from the viewpoint of obtaining a toner excellent in low-temperature fixability, storage stability, and charge stability at high temperatures. It is a polycondensate of an alcohol component and a carboxylic acid component containing an aliphatic dicarboxylic acid having 4 to 18 carbon atoms.

The carbon number of the α, ω-aliphatic diol is 2 or more, preferably 4 or more, more preferably 6 or more, still more preferably 10 or more, and 16 or less, preferably 14 or less, more preferably 12 or less. is there.
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, 1,14-tetradecanediol It can be mentioned. Among these, ethylene glycol or 1,12-dodecanediol is preferable, and 1,12-dodecanediol is more preferable.

  The amount of the α, ω-aliphatic diol is at least 80 mol%, preferably 85 mol, based on the alcohol component, from the viewpoint of obtaining a toner excellent in low-temperature fixability, storage stability and charge stability at high temperatures. %, More preferably 90 mol% or more, further preferably 95 mol% or more, and 100 mol% or less, still more preferably 100 mol%.

  The alcohol component may contain other alcohol components 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 adduct of bisphenol A; glycerin, penta Examples thereof include trihydric or higher alcohols such as erythritol and trimethylolpropane. These alcohol components can be used alone or in combination of two or more.

The aliphatic dicarboxylic acid having 4 to 18 carbon atoms is preferably a linear aliphatic dicarboxylic acid.
The carbon number of the aliphatic dicarboxylic acid is 4 or more, preferably 8 or more, more preferably 10 or more, and 18 or less, preferably 16 or less, more preferably 14 or less.
Examples of aliphatic dicarboxylic acids include fumaric acid, sebacic acid, dodecanedioic acid and tetradecanedioic acid. Among these, sebacic acid and tetradecanedioic acid are preferable, and tetradecanedioic acid is more preferable. These carboxylic acid components can be used alone or in combination of two or more.

  The amount of the aliphatic dicarboxylic acid having 4 to 18 carbon atoms 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 less than or equal to 100 mol%, and even more preferably 100 mol%.

The carboxylic acid component preferably comprises an aliphatic monocarboxylic acid, more preferably a linear aliphatic monocarboxylic acid.
The carbon number of the aliphatic monocarboxylic acid is preferably 8 or more, more preferably 10 or more, still more preferably 14 or more, and preferably 20 or less, more preferably 18 or less.
Examples of aliphatic monocarboxylic acids include octanoic acid, dodecanoic acid, lauric acid, myristic acid, palmitic acid and stearic acid. Among these, stearic acid is preferred. These carboxylic acid components can be used alone or in combination of two or more.

  The amount of aliphatic monocarboxylic acid is 20 mol% or less, more preferably 15 mol% or less, still more preferably 10 mol% or less, still more preferably 5 mol% or less in the carboxylic acid component, and preferably 1 It is preferably at least 2 mol%, more preferably at least 2 mol%.

  The carboxylic acid component may contain an aliphatic dicarboxylic acid or another carboxylic acid component different from the aliphatic monocarboxylic 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. These carboxylic acid components can be used alone or in combination of two or more.

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

[Physical Properties of Crystalline Polyester Resin]
The softening point of the crystalline polyester resin is preferably 60 ° C. or more, more preferably 70 ° C. or more, still more preferably 80 ° C. or more, from the viewpoint of further improving storage stability, and further improving low-temperature fixability. From the viewpoint, it is preferably 150 ° C. or less, more preferably 120 ° C. or less, still more preferably 100 ° C. or less.

  The melting point of the crystalline polyester resin is preferably 50 ° C. or more, more preferably 60 ° C. or more, still more preferably 70 ° C. or more, from the viewpoint of further improving storage stability, and further improving the low temperature fixability. Preferably, the temperature is 100 ° C. or less, more preferably 90 ° C. or less.

  The acid value of the crystalline polyester resin is preferably 35 mg KOH / g or less, more preferably 15 mg KOH / g or less, still more preferably 10 mg KOH / g or less, still more preferably 5 mg KOH, from the viewpoint of further improving storage stability and low temperature fixability. / G or less, more preferably 3 mg KOH / g or less, and 0 mg KOH / g or more, preferably 1 mg KOH / g or more.

  The hydroxyl value of the crystalline polyester resin is preferably 1 mg KOH / g or more, more preferably 2 mg KOH / g or more, and still more preferably 3 mg KOH / g or more from the viewpoint of further improving storage stability and low temperature fixability. It is preferably 35 mg KOH / g or less, more preferably 30 mg KOH / g or less, still more preferably 20 mg KOH / g, further preferably 10 mg KOH / g or less.

  The softening point, melting point, acid value and hydroxyl value of the crystalline polyester resin can be appropriately adjusted according to the type and ratio of the raw material monomers, and the production conditions such as the reaction temperature, the reaction time and the cooling rate. Those values can be determined by the methods described in the examples below. When two or more kinds of crystalline resins are used in combination, the values of the softening point, the melting point, the acid value and the hydroxyl value obtained as a mixture thereof are preferably in the above ranges.

The crystalline polyester resin is obtained, for example, by polycondensation of an alcohol component and a carboxylic acid component.
In the polycondensation, if necessary, an esterification catalyst such as di (2-ethylhexanoic acid) tin (II), dibutyltin oxide, titanium diisopropylate bistriethanolaminate, etc. is used as a total of 100 for the alcohol component and the carboxylic acid component. 0.01 parts by mass or more and 5 parts by mass or less with respect to parts by mass; an esterification promoter such as gallic acid (same as 3,4,5-trihydroxybenzoic acid) 100 parts in total of the alcohol component and the carboxylic acid component It may carry out polycondensation using 0.001 mass part or more and 0.5 mass part or less with respect to a part.
The temperature of polycondensation is preferably 120 ° C. or more, more preferably 160 ° C. or more, still more preferably 180 ° C. or more, and preferably 250 ° C. or less, more preferably 240 ° C. or less. The polycondensation may be carried out in an inert gas atmosphere.

  The content of the crystalline polyester resin is preferably 1% by mass or more in the polymerizable monomer composition from the viewpoint of further improving the low temperature fixability of the toner, the storage stability, and the charge stability at high temperatures. More preferably, it is 3% by mass or more, further preferably 5% by mass or more, and preferably 60% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, still more preferably 20% by mass or less More preferably, it is 15% by mass or less.

  A crystalline polyester resin, a composite resin (A) and a polymerizable monomer from the viewpoint that the content of the crystalline polyester resin further improves the low temperature fixability, storage stability, and charge stability at high temperature of the toner. Preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, still more preferably 7% by mass or more, and preferably 30% by mass or less, more preferably Is 25 mass% or less, more preferably 20 mass% or less.

(Composite resin (A))
The composite resin (A) is a vinyl, which is an addition polymer of a polyester resin segment and a raw material monomer containing a styrenic compound, from the viewpoint of obtaining a toner excellent in low temperature fixability, storage stability, and charge stability at high temperatures. Type resin segment, a constituent unit derived from a bireactive monomer bonded via a covalent bond to a polyester resin segment and a vinyl resin segment, and a hydrocarbon wax (II) derived from the polyester resin segment via a covalent bond And its constituent units.
The composite resin (A) is preferably an amorphous composite resin.

(Polyester resin segment)
The polyester resin segment is made of, for example, a polycondensate of an alcohol component and a carboxylic acid component.
As an alcohol component, an aromatic polyol and an aliphatic polyol are mentioned, for example.
The aromatic polyol is preferably an alkylene oxide adduct of bisphenol A, more preferably a compound of formula (I):

[Wherein, OR and RO each represent an oxyalkylene group, R represents at least one selected from an ethylene group and a propylene group, x and y each represent an average addition mole number of an alkylene oxide, and each is a positive number. The value of 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 alkylene oxide adduct of bisphenol A represented by these.

  As the alkylene oxide adduct of bisphenol A represented by the formula (I), for example, a propylene oxide adduct of 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane And ethylene oxide adducts of Among these, a propylene oxide adduct of 2,2-bis (4-hydroxyphenyl) propane is preferable. One or more of these may be used.

  The content of the alkylene oxide adduct of bisphenol A represented by the formula (I) is preferably 60 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, still more preferably in the alcohol component. It is 90 mol% or more, more preferably 95 mol% or more, and 100 mol% or less, and preferably 100 mol%.

Examples of aliphatic polyols include aliphatic diols having 2 to 20 carbon atoms, and trivalent or higher aliphatic alcohols such as glycerin.
As an aliphatic diol, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4- Examples include butenediol, 1,3-butanediol, neopentyl glycol, 1,10-decanediol and 1,12-dodecanediol.

  The carboxylic acid component preferably contains a dicarboxylic acid. The dicarboxylic acid may be an aromatic dicarboxylic acid or an aliphatic dicarboxylic acid.

Examples of aromatic dicarboxylic acids include phthalic acid, isophthalic acid and terephthalic acid. Among these, terephthalic acid and isophthalic acid are preferable, and terephthalic acid is more preferable. One or more of these may be used.
The content of the aromatic dicarboxylic acid is preferably 10 mol% or more, more preferably 30 mol% or more, still more preferably 50 mol% or more, and 100 mol% or less, preferably 95 mol, of the carboxylic acid component. % Or less, more preferably 90 mol% or less.

Examples of aliphatic dicarboxylic acids include carbon numbers such as oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, dodecanedioic acid, dodecenyl succinic acid, octyl succinic acid and the like Aliphatic dicarboxylic acids such as succinic acid substituted with an alkyl group of 1 or more and 20 or less or an alkenyl group of 2 or more and 20 or less carbon atoms can be mentioned. One or more of these may be used. Among these, adipic acid is preferred.
The content of the aliphatic dicarboxylic acid is preferably 5 mol% or more, more preferably 7 mol% or more, still more preferably 9 mol% or more, and preferably 90 mol% or less, more preferably in the carboxylic acid component. It is 70 mol% or less, more preferably 50 mol% or less, still more preferably 30 mol% or less, still more preferably 15 mol% or less.

Moreover, it is preferable that the carboxylic acid component contains the trivalent or more carboxylic acid from a viewpoint of productivity.
Examples of trivalent or higher carboxylic acids include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, and pyromellitic acid. Among these, trimellitic acid or its acid anhydride is preferred.

  The content of the trivalent or higher carboxylic acid in the carboxylic acid component is preferably 1 mol% or more, more preferably 3 mol% or more, still more preferably 5 mol% or more, and preferably 50 mol% or less, More preferably, it is 40 mol% or less, still more preferably 20 mol% or less, still more preferably 15 mol% or less.

  A monohydric alcohol may be suitably contained in the alcohol component, and a monobasic carboxylic acid compound may be suitably contained in the carboxylic acid component from the viewpoint of molecular weight adjustment.

  The equivalent ratio of the carboxyl 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, from the viewpoint of adjusting the terminal group Preferably, it is 1.3 or less, more preferably 1.2 or less.

(Vinyl-based resin segment)
The vinyl-based resin segment is an addition polymer of a raw material monomer containing a styrene-based compound, from the viewpoint of obtaining a toner excellent in low-temperature fixability, storage stability, and charge stability at high temperatures, preferably a styrene-based compound And an addition polymer of a raw material monomer containing 1% by mass or more and 30% by mass or less of a vinyl-based monomer having an aliphatic hydrocarbon group having 3 to 22 carbon atoms.

Examples of styrenic compounds include substituted or unsubstituted styrene. As a substituent, a C1-C5 alkyl group, a halogen atom, a C1-C5 alkoxy group, a sulfonic acid group, its salt etc. are mentioned, for example.
Examples of the styrene compounds include styrenes such as styrene, methylstyrene, α-methylstyrene, β-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrene sulfonic acid or salts thereof Be Among these, styrene is preferred.
The amount of the styrenic compound is preferably 50% by mass or more, more preferably 65% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more in the raw material monomer of the vinyl resin segment 100% by weight or less, and more preferably 100% by weight.

  The carbon number of the hydrocarbon group of the vinyl monomer having an aliphatic hydrocarbon group is preferably 3 or more, more preferably 4 or more, and preferably 22 or less, more preferably 18 or less, still more preferably 10 or less. More preferably, it is 8 or less.

As an aliphatic hydrocarbon group, an alkyl group, an alkynyl group, an alkenyl group is mentioned, for example. Among these, an alkyl group and an alkenyl group are preferable, and an alkyl group is preferable. The aliphatic hydrocarbon group may be either branched or linear.
The vinyl-based monomer having an aliphatic hydrocarbon group is preferably an alkyl ester of (meth) acrylic acid. In the case of alkyl esters of (meth) acrylic acid, the hydrocarbon group is the alcohol-side residue of the ester.
Examples of the alkyl ester of (meth) acrylic acid include (meth) acrylic acid (iso) propyl, (meth) acrylic acid (iso) butyl, (meth) acrylic acid (iso) hexyl, cyclohexyl (meth) acrylic acid, (Meth) acrylic acid (iso) octyl (hereinafter, also referred to as (meth) acrylic acid 2-ethylhexyl), (meth) acrylic acid (iso) decyl, (meth) acrylic acid (iso) dodecyl (hereinafter, (meth) acrylic) Examples include acid (iso) lauryl), (meth) acrylic acid (iso) palmityl, (meth) acrylic acid (iso) stearyl, and (meth) acrylic acid (iso) behenyl. Among these, butyl (meth) acrylate is preferable.
Here, "alkyl (meth) acrylate" indicates alkyl acrylate or alkyl methacrylate. Also, "(iso)" for the alkyl moiety means normal alkyl or isoalkyl.

  The amount of the vinyl-based monomer having an aliphatic hydrocarbon group having 3 to 22 carbon atoms is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass, based on the raw material monomers of the vinyl resin segment. % Or less, more preferably 20% by mass or less, and 0% by mass or more, and further preferably 0% by mass.

  Examples of other starting monomers include ethylenically unsaturated monoolefins such as ethylene and propylene; conjugated dienes such as butadiene; halovinyls such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; ) (Meth) acrylic acid aminoalkyl esters such as dimethylaminoethyl acrylate; vinyl ethers such as methyl vinyl ether; vinylidene halides such as vinylidene chloride; N-vinyl compounds such as N-vinyl pyrrolidone.

  The total amount of the styrene-based compound and the vinyl-based monomer having an aliphatic hydrocarbon group having 3 to 22 carbon atoms in the raw material monomers in the vinyl-based resin segment is preferably 80% by mass or more, more preferably 90% by mass or more More preferably, it is 95 mass% or more, and is 100 mass% or less, preferably 100 mass%.

(Constituent unit derived from both reactive monomers)
The composite resin (A) has a structural unit derived from a bireactive monomer bonded via a covalent bond to the polyester resin segment and the vinyl resin segment in order to connect the polyester resin segment and the vinyl resin segment.
The “structural unit derived from a bireactive monomer” means a unit in which a functional group of a bireactive monomer and a vinyl site have reacted.
Examples of the dual reactive monomer include vinyl monomers having at least one functional group selected from a hydroxyl group, a carboxy group, an epoxy group, a primary amino group and a secondary amino group in the molecule. Among these, from the viewpoint of reactivity, vinyl-based monomers having a hydroxyl group or a carboxy group are preferable, and vinyl-based monomers having a carboxy group are more preferable.
Examples of the dual reactive monomer include acrylic acid, methacrylic acid, fumaric acid, and maleic acid. Among these, acrylic acid and methacrylic acid are preferable, and acrylic acid is more preferable, from the viewpoint of the reactivity of both the polycondensation reaction and the addition polymerization reaction.
The amount of the structural unit derived from the bireactive monomer is preferably 1 mol part or more, more preferably 2 mol parts or more, still more preferably 3 parts by mol with respect to 100 mol parts of the alcohol component of the polyester resin segment of the composite resin (A). The amount is preferably at least 30 parts by mole, more preferably at most 20 parts by mole, and still more preferably at most 10 parts by mole.

(Constituent unit derived from hydrocarbon wax (II))
The composite resin (A) is derived from a hydrocarbon wax (II) bonded to the polyester resin segment via a covalent bond, from the viewpoint of obtaining a toner excellent in low-temperature fixability, storage stability, and charge stability at high temperatures. Includes building blocks. The structural unit derived from the hydrocarbon wax (II) is obtained, for example, by polycondensation of an alcohol component, a carboxylic acid component, and a hydrocarbon wax (II).
The hydrocarbon wax (II) has at least one group selected from a hydroxyl group and a carboxy group from the viewpoint of obtaining a toner excellent in low-temperature fixing ability, storage stability, and charging stability at high temperature, and has a melting point 60 ° C. or more and 130 ° C. or less.

  The hydrocarbon wax (II) preferably has a hydroxyl group and a carboxyl group, from the viewpoint of obtaining a toner excellent in low-temperature fixability, storage stability, and charge stability at high temperatures.

The melting point of the hydrocarbon wax (II) is 60 ° C. or more, preferably 65 ° C. or more, more preferably 70 or more, from the viewpoint of further improving the low temperature fixability, storage stability and charge stability at high temperature of the toner. And 130 ° C. or less, preferably 120 ° C. or less, more preferably 115 ° C. or less, still more preferably 110 ° C. or less.
The melting point can be measured by the method described in the examples.

  Hereinafter, “hydrocarbon wax having a hydroxyl group” may have a carboxy group in addition to a hydroxyl group, but means a wax having an equivalent or higher hydroxyl value based on the hydroxyl group as compared to the acid value based on a carboxy group . The “hydrocarbon wax having a carboxy group” may have a hydroxyl group in addition to a carboxy group, but includes a wax having a higher acid value based on a carboxy group as compared to the hydroxyl value based on a hydroxyl group.

The hydrocarbon wax having a hydroxyl group is obtained, for example, by modifying a hydrocarbon wax such as paraffin wax, Fischer-Tropsch wax, microcrystalline wax, polyethylene wax or the like by oxidation treatment. As a method of an oxidation treatment, the method of Unexamined-Japanese-Patent No. 62-79267, the Unexamined-Japanese-Patent No. 2010-197979, etc. are mentioned, for example.
Specifically, there is a method of liquid-phase oxidation of hydrocarbon wax with an oxygen-containing gas in the presence of boric acid. As commercially available products of hydrocarbon wax having a hydroxyl group, "Unillin 700", "Unillin 425", "Unillin 550" (above, manufactured by Baker Petrolite Co., Ltd.), "Paracor 6420", "Paracor 6470", "Paracor 6490" (These are manufactured by Nippon Seiwa Co., Ltd.) and the like.

As a hydrocarbon wax which has a carboxy group, an acid-modified wax is mentioned, for example.
Examples of the acid modification method include the methods described in JP-A-2006-328388, JP-A-2007-84787, and the like. Specifically, a carboxy group can be introduced by adding an organic peroxide compound (reaction initiator) such as dicumyl peroxide and the like and a carboxylic acid compound to a melt of a hydrocarbon wax to cause a reaction.
As a hydrocarbon wax used as a reaction raw material, paraffin wax, Fischer-Tropsch wax, olefin, microcrystalline wax, polyethylene wax etc. are mentioned, for example. Among these, paraffin wax and Fischer-Tropsch wax are preferable.
As commercial products of paraffin wax and Fischer-Tropsch wax as reaction raw materials, for example, “HNP-11”, “HNP-9”, “HNP-10”, “FT-0070”, “HNP-51”, “FNP “-0090” (above, manufactured by Nippon Seiwa Co., Ltd.).
As a hydrocarbon wax which has a carboxy group, "HIWAX 1105A" (maleic anhydride modified | denatured ethylene propylene copolymer, Mitsui Chemicals, Inc. make) etc. are mentioned, for example.

The number average molecular weight of the hydrocarbon wax (II) is preferably 400 or more, more preferably 500 or more, and further preferably from the viewpoint of further improving the low temperature fixability of the toner, storage stability and charge stability under high temperature. Is 600 or more, and preferably 3000 or less, more preferably 2500 or less, and still more preferably 2000 or less.
The said number average molecular weight can be measured by the method as described in an Example.

The hydroxyl value of the hydrocarbon wax (II) is preferably 40 mg KOH / g or more, more preferably 55 mg KOH / g or more from the viewpoint of further improving the low temperature fixability, storage stability and charge stability at high temperature of the toner. More preferably, it is 65 mg KOH / g or more, and preferably 180 mg KOH / g or less, more preferably 150 mg KOH / g or less, more preferably 120 mg KOH / g or less, more preferably 110 mg KOH / g or less.
The acid value of the hydrocarbon wax (II) is preferably 40 mg KOH / g or more, more preferably 50 mg KOH / g or more from the viewpoint of further improving the low temperature fixability, storage stability and charge stability at high temperature of the toner. More preferably, it is 55 mg KOH / g or more, and preferably 180 mg KOH / g or less, more preferably 150 mg KOH / g or less, more preferably 120 mg KOH / g or less, more preferably 100 mg KOH / g or less.

The total value of the hydroxyl value and acid value of the hydrocarbon wax (II) is preferably 40 mg KOH from the viewpoint of enhancing the affinity of the crystalline polyester resin and the composite resin (A) and enhancing the dispersibility of the crystalline polyester resin. / G or more, more preferably 50 mg KOH / g or more, more preferably 60 mg KOH / g or more, and preferably 200 mg KOH / g or less, more preferably 180 mg KOH / g or less, more preferably 160 mg KOH / g or less, more preferably It is 140 mg KOH / g or less.
The hydroxyl value and acid value of the hydrocarbon wax are measured by the method described in the examples.

  The amount of the polyester resin segment is preferably 40% by mass or more, more preferably 50% by mass in the composite resin (A), from the viewpoint of further improving the low temperature fixability of the toner, storage stability and charge stability at high temperatures. The content is preferably not less than 55% by mass, more preferably not more than 95% by mass, more preferably not more than 90% by mass, still more preferably not more than 85% by mass, still more preferably not more than 80% by mass.

  The amount of the vinyl-based resin segment is preferably 3% by mass or more, more preferably in the composite resin (A), from the viewpoint of further improving the low-temperature fixability, storage stability, and charge stability at high temperatures of the toner. It is 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and preferably 60% by mass or less, more preferably 45% by mass or less, still more preferably 30% by mass or less, more preferably Is 20 mass% or less.

  The amount of the structural unit derived from the dual reactive monomer is preferably 0.1 mass in the composite resin (A) from the viewpoint of further improving the low temperature fixability, storage stability and charge stability at high temperature of the toner. % Or more, more preferably 0.2% by mass or more, further preferably 0.3% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less is there.

  The amount of the structural unit derived from the hydrocarbon wax (II) is preferably 0.1% by mass or more, preferably from the viewpoint of further improving the low temperature fixability of the toner, storage stability, and charge stability under high temperature. 0.5% by mass or more, more preferably 1% by mass or more, more preferably 2% by mass or more, more preferably 3% by mass or more, more preferably 4% by mass or more, and preferably 20% by mass or less More preferably, it is 10% by mass or less, more preferably 8% by mass or less, more preferably 7% by mass or less.

  The total amount of the polyester resin segment in the composite resin (A), the vinyl resin segment, the structural unit derived from the bireactive monomer, and the structural unit derived from the hydrocarbon wax (II) is preferably 80% by mass or more, more preferably Is 90% by mass or more, more preferably 93% by mass or more, still more preferably 95% by mass or more, and 100% by mass or less, preferably 99% by mass or less.

  The mass ratio of the total weight of the polyester resin segment and the constituent units derived from both reactive monomers and the vinyl resin segment is preferably 60/40 or more, more preferably 70/30 or more, more preferably 75/25 or more. And preferably not more than 95/5, more preferably not more than 90/10, still more preferably not more than 85/15 parts by mass.

  The above amount is calculated based on the ratio of the amounts of the polyester resin segment, the raw material monomer of the vinyl resin segment, the bireactive monomer, and the polymerization initiator, and the amount of dehydration due to polycondensation in the polyester resin segment and the like is not considered. In addition, when a polymerization initiator is used, the mass of a polymerization initiator is included in a vinyl-type resin segment, and is calculated.

(Physical properties of composite resin (A))
The acid value of the composite resin (A) is preferably 40 mg KOH / g or less, more preferably 30 mg KOH / g or less, still more preferably 20 mg KOH / g or less, still more preferably 10 mg KOH / g or less, and preferably 0 mg KOH / g. It is above.

  The hydroxyl value of the composite resin (A) is preferably 5 mg KOH / g or more, more preferably 15 mg KOH / g or more, still more preferably 20 mg KOH / g or more, and preferably 60 mg KOH / g or less, more preferably 50 mg KOH / g The following, more preferably 40 mg KOH / g or less.

  The softening point of the composite resin (A) is preferably 70 ° C. or more, more preferably 80 ° C. or more, still more preferably 90 ° C. or more, and preferably 140 ° C. or less, from the viewpoint of further improving low-temperature fixability. The temperature is more preferably 130 ° C. or less, still more preferably 125 ° C. or less.

  The glass transition temperature of the composite resin (A) is preferably 45 ° C. or more, more preferably 48 ° C. or more, still more preferably 50 ° C. or more, from the viewpoint of further improving the low temperature fixability of the toner. C. or less, more preferably 60 ° C. or less, still more preferably 55 ° C. or less.

  The number average molecular weight of the composite resin (A) is preferably 1,000 or more, more preferably 2,000 or more, still more preferably 2,500 or more, from the viewpoint of further improving the low-temperature fixability of the toner. Preferably it is 10,000 or less, More preferably, it is 7,000 or less, More preferably, it is 4,000 or less.

  The weight average molecular weight of the composite resin (A) is preferably 1,000 or more, more preferably 5,000 or more, and still more preferably 10,00 or more, from the viewpoint of further improving the low temperature fixability of the toner. Preferably it is 100,000 or less, More preferably, it is 50,000 or less, More preferably, it is 30,000 or less.

The acid value, hydroxyl value, softening point, glass transition temperature, number average molecular weight, and weight average molecular weight of the composite resin (A) are the types of raw material monomers and the amount thereof used, and the reaction temperature, reaction time, cooling rate, etc. The conditions can be appropriately adjusted, and their values can be determined by the methods described in the examples.
When two or more of the composite resins (A) are used in combination, the acid value, hydroxyl value, softening point, glass transition temperature, number average molecular weight and weight average molecular weight of any one of them are as described above. It is preferable to be within the range.

(Method for producing composite resin (A))
The method for producing the composite resin (A) includes, for example, polycondensation of an alcohol component and a carboxylic acid component in the presence of a hydrocarbon wax (II), and a raw material monomer of a vinyl resin segment and a bireactive monomer. The method includes addition polymerization, and examples thereof include the following methods (i) to (iii).
(i) A method of carrying out addition polymerization of a vinyl resin segment with a raw material monomer and a bireactive monomer after polycondensation with an alcohol component and a carboxylic acid component in the presence of a hydrocarbon wax (II)
(ii) Method of carrying out polycondensation with an alcohol component and a carboxylic acid component in the presence of a hydrocarbon wax (II) after addition polymerization of a vinyl resin segment with a raw material monomer and a bireactive monomer
(iii) Method in which polycondensation with an alcohol component and a carboxylic acid component and addition polymerization with a raw material monomer of a vinyl resin segment and both reactive monomers are performed in parallel in the presence of a hydrocarbon wax (II). Both polycondensation and addition polymerization in the method of (iii) are preferably carried out in the same vessel.
The composite resin (A) is preferably produced by the method (i) or (ii) from the viewpoint that the degree of freedom of the reaction temperature of the polycondensation reaction is high, and the above (i) is more preferred.
From the viewpoint of reactivity, a catalyst such as an esterification catalyst or an esterification co-catalyst may be used, and further, a polymerization initiator and a polymerization inhibitor may be used.
The conditions for the polycondensation are preferably the same as the conditions described in the above-mentioned method for producing a crystalline polyester resin.
From the viewpoint of further carrying out the polycondensation and, if necessary, the reaction with the bireactive monomer, a part of the carboxylic acid component is subjected to polycondensation, and after addition polymerization is carried out, the reaction temperature is raised again and the remainder is reacted. Preferably it is added to the system.

In addition polymerization, the raw material monomer of a vinyl resin segment and both reactive monomers are addition-polymerized.
The temperature of addition polymerization is preferably 110 ° C. or more, more preferably 130 ° C. or more, and preferably 220 ° C. or less, more preferably 200 ° C. or less. Moreover, it is preferable to accelerate the reaction by reducing the pressure of the reaction system in the latter half of the polymerization.

Examples of the polymerization initiator for addition polymerization include peroxides such as di-tert-butyl peroxide, persulfates such as sodium persulfate, and 2,2′-azobis (2,4-dimethylvaleronitrile) Known polymerization initiators such as azo compounds can be used.
The amount of the polymerization initiator used is preferably 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 5 parts by mass or more, with respect to 100 parts by mass of the raw material monomer of the vinyl resin segment Is 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less.

  The content of the composite resin (A) is preferably 1% by mass or more in the polymerizable monomer composition from the viewpoint of further improving the low temperature fixability of the toner, storage stability, and charge stability at high temperatures. More preferably, it is 3% by mass or more, further preferably 5% by mass or more, and preferably 60% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, further preferably 20% by mass The content is more preferably 15% by mass or less, still more preferably 10% by mass or less.

  From the viewpoint that the content of the composite resin (A) further improves the low temperature fixability, storage stability and charge stability at high temperature of the toner, the crystalline polyester resin, the composite resin (A) and the polymerizable unit amount It is preferably 2% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, based on the total amount of the body. Preferably it is 20 mass% or less, More preferably, it is 15 mass% or less.

(Polymerizable monomer)
The polymerizable monomer is, for example, a polymerizable monomer having an unsaturated double bond.
The polymerizable monomer composition preferably contains, for example, a styrene compound and a (meth) acrylic acid ester as the polymerizable monomer.

As a styrene compound, substituted or unsubstituted styrene is mentioned, for example. As a substituent, a C1-C5 alkyl group, a halogen atom, a C1-C5 alkoxy group, a sulfonic acid group, its salt etc. are mentioned, for example.
Examples of styrene compounds include styrenes such as styrene, methylstyrene, α-methylstyrene, β-methylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrene sulfonic acid or salts thereof . Among these, styrene is preferred.
The amount of the styrene compound in the polymerizable monomer is preferably 50% by mass or more, more preferably 65% by mass or more, still more preferably 70% by mass or more, and preferably 95% by mass or less, more preferably It is 90 mass% or less.

The (meth) acrylic acid ester is preferably a (meth) acrylic acid ester having an aliphatic hydrocarbon group.
The carbon number of the aliphatic hydrocarbon group of the (meth) acrylic acid ester having an aliphatic hydrocarbon group is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, still more preferably 4 or more, , Preferably 22 or less, more preferably 18 or less, further preferably 12 or less, further preferably 8 or less, further preferably 6 or less.

As an aliphatic hydrocarbon group, an alkyl group, an alkynyl group, an alkenyl group is mentioned, for example. Among these, an alkyl group and an alkenyl group are preferable, and an alkyl group is preferable. The aliphatic hydrocarbon group may be either branched or linear.
Examples of (meth) acrylic acid esters include (meth) acrylic acid (iso) propyl, (meth) acrylic acid (iso) butyl, (meth) acrylic acid (iso) hexyl, (meth) acrylic acid cyclohexyl, ) Acrylic acid (iso) octyl, (meth) acrylic acid (iso) decyl, (meth) acrylic acid (iso) dodecyl, (meth) acrylic acid (iso) palmityl, (meth) acrylic acid (iso) stearyl, (meth) And acrylic acid (iso) behenyl. Among these, butyl (meth) acrylate is preferable.
Here, "(meth) acrylic acid" indicates acrylic acid or methacrylic acid. Also, "(iso)" for the alkyl moiety means normal alkyl or isoalkyl.

  The amount of (meth) acrylic acid alkyl ester is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 50% by mass or less, more preferably 45% by mass in the polymerizable monomer. The content is more preferably 30% by mass or less.

  Examples of other starting monomers include ethylenically unsaturated monoolefins such as ethylene and propylene; conjugated dienes such as butadiene; halovinyls such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; ) (Meth) acrylic acid aminoalkyl esters such as dimethylaminoethyl acrylate; vinyl ethers such as methyl vinyl ether; vinylidene halides such as vinylidene chloride; N-vinyl compounds such as N-vinyl pyrrolidone.

  The total amount of the styrene compound and the (meth) acrylic acid ester in the polymerizable monomer is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and 100 It is not more than mass%, preferably 100 mass%.

  The content of the polymerizable monomer is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 75% by mass or more, still more preferably 80% by mass or more in the polymerizable monomer composition. And preferably not more than 95% by mass, more preferably not more than 90% by mass, still more preferably not more than 85% by mass.

  The content of the polymerizable monomer is a crystalline polyester resin, a composite resin (A) and a polymerizable monomer, from the viewpoint of further improving the low temperature fixability, storage stability and charge stability at high temperature of the toner. Preferably it is 40 mass% or more, more preferably 50 mass% or more, still more preferably 60 mass% or more, and preferably 96 mass% or less, more preferably 94 mass% or less, based on the total amount of the body. Preferably it is 90 mass% or less.

  The mass ratio of the crystalline polyester resin to the polymerizable monomer in the polymerizable monomer composition is preferably 3/97 or more, more preferably 5/95 or more, and still more preferably 8/92 or more. And it is preferably 30/70 or less, more preferably 25/85 or less, further preferably 20/80 or less.

(Colorant)
As the coloring agent, a pigment and a dye are used, and a pigment is preferable from the viewpoint of further improving the color forming effect. As the pigment, any of inorganic pigments and organic pigments can be used, but organic pigments are preferable.
Examples of the inorganic pigment include carbon black and inorganic complex oxides.
Examples of organic pigments include yellow pigments, magenta pigments, and cyan pigments.
Examples of the magenta organic pigment include monoazo compounds, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, base dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds. Specifically, C.I. I. Pigment red 2,3,5,6,7,23,48: 1,48: 2,48: 3,48: 4,57: 1,81: 1,122,144,146,150,166,169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. Pigment bio red 19 may be mentioned. Among these, naphthol compounds are preferable, and C.I. I. Pigment red 269 is more preferred.

  Examples of cyan organic pigments include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. More specifically, C.I. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66. Among these, copper phthalocyanine compounds are preferable, and C.I. I. Pigment Blue 15: 3 is more preferable.

Examples of yellow organic pigments include monoazo compounds, disazo compounds, condensed azo compounds, isoindolinone compounds, isoindoline compounds, benzimidazolone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and the like. , C. I. Pigment yellow 17, 74, 93, 95, 109, 111, 128, 139, 151, 154, 155, 174, 180, 185. Among these, monoazo compounds are preferable, and C.I. I. Pigment yellow 74 is more preferable.
Examples of dyes include acridine dyes, azo dyes, benzoquinone dyes, azine dyes, anthraquinone dyes, indigo dyes, phthalocyanine dyes, and aniline black dyes. One or more of these may be used.

  The amount of the colorant is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 3 parts by mass or more, and preferably 30 parts by mass or less, based on 100 parts by mass of the binder resin component. More preferably, it is 20 parts by mass or less, still more preferably 10 parts by mass or less.

(Mold release agent (I))
The polymerizable monomer preferably contains a releasing agent (I) from the viewpoint of further improving the low temperature fixability and storage stability of the toner. The releasing agent (I) means a releasing agent contained in the polymerizable monomer composition, unlike the above-mentioned hydrocarbon wax (II). By including the release agent (I) in combination with the composite resin (A), the dispersibility in the toner particles becomes good, and the low temperature fixability and the storage stability are improved.
As a mold release agent (I), a wax is mentioned, for example.
Waxes include, for example, hydrocarbon waxes, ester waxes, silicone waxes and fatty acid amide waxes.
Examples of the hydrocarbon wax include mineral or petroleum hydrocarbon waxes such as paraffin wax and Fischer Tropsch wax; and synthetic hydrocarbon waxes 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; plant based ester waxes such as carnauba wax, rice wax and candelilla wax; and animal based ester waxes such as beeswax.
Examples of fatty acid amide waxes include oleic acid amide and stearic acid amide.
Among these, from the viewpoint of toner releasability, hydrocarbon wax or ester wax is preferable, hydrocarbon wax is more preferable, paraffin wax, Fischer-Tropsch wax, and polyolefin wax are more preferable, and paraffin wax is more preferable.

The melting point of the releasing agent (I) is preferably 60 ° C. or more, more preferably 65 ° C. or more, still more preferably 70 ° C. or more from the viewpoint of toner releasability, and the low temperature fixability of the toner is improved Preferably, the temperature is 100 ° C. or less, more preferably 95 ° C. or less, still more preferably 90 ° C. or less, and still more preferably 85 ° C. or less.
The melting point of the release agent (I) is determined by the method described in the examples.

  The amount of the releasing agent (I) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 3 parts by mass with respect to 100 parts by mass of the binder resin component from the viewpoint of toner releasability. The amount is preferably at least 25 parts by mass, more preferably at most 20 parts by mass, and still more preferably at most 15 parts by mass.

(Polymerization initiator)
As a polymerization initiator, a well-known polymerization initiator can be mentioned, For example, an azo compound, an organic peroxide, an inorganic peroxide, an organometallic compound, a photoinitiator is mentioned.
As a polymerization initiator, for example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4 Azo polymerization initiators such as -dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis (isobutyrate), and aliphatic diacyl peroxides such as dilauryl peroxide Oxide peroxide-based polymerization initiator, benzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxybenzoate such as tert-butyl peroxybenzoate, etc. organic peroxide based polymerization initiation Inorganic peroxide type polymerization initiator such as potassium persulfate, ammonium persulfate, hydrogen peroxide The first iron-based, BPO-dimethyl aniline, cerium (IV) salt - and the like redox initiators alcohol or the like. Examples of the photopolymerization initiator include acetophenone type, benzoin ether type and ketal type. One or more of these may be used.
Among these, an azo-based polymerization initiator and an aliphatic diacyl peroxide-based polymerization initiator are preferable, and 2,2′-azobis (2,4-dimethylvaleronitrile) and dilauryl peroxide are more preferable.

  The amount of the polymerization initiator is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 1 part by mass or more, with respect to 100 parts by mass of the polymerizable monomer. The amount is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less.

(Charge control agent)
The polymerizable monomer composition may contain a charge control agent.
The charge control agent may contain any of a positively chargeable charge control agent and a negatively chargeable charge control agent.
As positively chargeable charge control agents, nigrosine dyes such as "Nigrosine Base EX", "Oil Black BS", "Oil Black SO", "Bontron N-01", "Bontron N-04", "Bontron N-07" “Bontron N-09”, “Bontron N-11” (all, manufactured by Orient Chemical Industries, Ltd.), etc .; Triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salt compounds, eg, “ Bontron P-51 "(Orient Chemical Industry Co., Ltd.), cetyltrimethyl ammonium bromide," COPY CHARGE PX VP 435 "(Clariant Co., Ltd.), etc .; Polyamine resin such as" AFP-B "(Orient Chemical Co., Ltd.) etc. Imidazole derivatives such as “PLZ-2001”, “PLZ-800” "(Above, manufactured by Shikoku Chemicals Corporation) and the like; styrene - acrylic resin, for example," FCA-701PT "(manufactured by Fujikura Kasei), and the like.

As a negatively chargeable charge control agent, metal-containing azo dyes such as, for example, "Varifast black 3804", "Bontron S-31", "Bontron S-32", "Bontron S-34", "Bontron S-36" ( As described above, Orient Chemical Industry Co., Ltd.), “Aisenspirone Black TRH”, “T-77” (Hodogaya Chemical Co., Ltd.), etc .; metal compounds of benzylic acid compounds, for example, “LR-147” LR-297 "(above, manufactured by Nippon Carlit Co., Ltd.) and the like; metal compounds of salicylic acid compounds, for example," Bontron E-81 "," Bontron E-84 "," Bontron E-88 "," Bontron E-304 " (The above, made by Orient Chemical Industry Co., Ltd.), "TN-105" (made by Hodogaya Chemical Industry Co., Ltd.), etc .; Copper phthalocyanine dye; Unsalted, for example, "COPY CHARGE NX VP434" (manufactured by Clariant), nitroimidazole derivatives, and the like; organic metal compounds, and the like.
One or more of these may be used.
Among charge control agents, a negatively chargeable charge control agent is preferable, and a metal compound of a benzylic acid compound or a metal compound of a salicylic acid compound is more preferable.

  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 preferably 10 parts by mass or less, with respect to 100 parts by mass of the binder resin component. The amount is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and still more preferably 2 parts by mass or less.

In the step 1, it is preferable to mix the crystalline polyester resin, the composite resin (A), the polymerizable monomer and the colorant before obtaining a suspension.
Process 1 is preferably a process including the following process 1-1 and process 1-2.
Step 1-1: A step of mixing a crystalline polyester resin, a composite resin (A), a polymerizable monomer and a colorant to obtain a polymerizable monomer composition Step 1-2: composition of the polymerizable monomer The waste into an aqueous medium to obtain a suspension

<Step 1-1>
In the step 1-1, it is preferable that the polymerizable monomer composition be mixed by heating and mixing the respective components to form a mixed solution in which the respective components are uniformly dissolved.
Here, it is preferable to mix the charge control agent and the release agent.
The mixing temperature is preferably 40 ° C. or more, more preferably 45 ° C. or more, further preferably 50 ° C. or more, and preferably 80 ° C. or less, more preferably 70 ° C. or less, still more preferably 65 ° C. or less.
After obtaining the polymerizable monomer composition in which the respective components are compatible, it is preferable to add and mix a polymerization initiator.

In step 1-2, the aqueous medium may be a mixed aqueous medium mixed with a dispersion stabilizer and a surfactant.
(Dispersion stabilizer)
Examples of dispersion stabilizers include carbonates, metal phosphates, sulfates and metal hydroxides. Examples of carbonates include barium carbonate, calcium carbonate and magnesium carbonate. Examples of metal phosphates include aluminum phosphate, magnesium phosphate, calcium phosphate, barium phosphate and zinc phosphate. Examples of the sulfate include barium sulfate and calcium sulfate. Examples of metal hydroxides include calcium hydroxide, aluminum hydroxide, magnesium hydroxide and ferric hydroxide. Among these, calcium phosphate is preferred.
The amount of the dispersion stabilizer is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass in the mixed aqueous medium. It is preferably at most 10% by mass, more preferably at most 10% by mass.

(Surfactant)
As the surfactant, various surfactants such as anionic surfactants, cationic surfactants, and nonionic surfactants can be used. Among these, anionic surfactants are preferred.
Examples of anionic surfactants include alkyl benzene sulfonates, alkyl sulfates and polyoxyalkylene alkyl ether sulfates. As a salt, an alkali metal salt is preferable, and a sodium salt is more preferable.
Examples of the alkyl benzene sulfonate include sodium dodecyl benzene sulfonate. Examples of the alkyl sulfate include sodium dodecyl sulfate. The polyoxyalkylene alkyl ether sulfate is preferably a polyoxyethylene alkyl ether sulfate. Examples of polyoxyalkylene alkyl ether sulfates include sodium polyoxyethylene lauryl ether sulfate. One or more of these may be used.
Among these, alkyl benzene sulfonates and polyoxyalkylene alkyl ether sulfates are preferable, dodecyl benzene sulfonate and polyoxyethylene lauryl ether sulfate are more preferable, and sodium dodecyl benzene sulfonate is still more preferable.
The amount of surfactant is preferably 1 mass ppm or more, more preferably 3 mass ppm or more, still more preferably 5 mass ppm or more, and preferably 30 mass ppm or less, more preferably 20 in the mixed aqueous medium. It is at most ppm by mass, more preferably at most 10 ppm by mass.

<Step 1-2>
The temperature at which the polymerizable monomer composition is introduced into the aqueous medium in step 1-2 is preferably 40 ° C. or more, more preferably 45 ° C. or more, still more preferably 50 ° C. or more, and preferably The temperature is 80 ° C. or less, more preferably 70 ° C. or less, still more preferably 65 ° C. or less.

At the time of charging, it is preferable to mix by stirring.
As an apparatus used at the said process, it can carry out by the vertical type stirring tank which installed the stirrer which has high shear force, for example. As a commercial item of a stirrer having high shear force, for example, "High share mixer" (manufactured by IKA), "TK homomixer", "TK. Company made) and CLEA MIX (made by M. Technics Co., Ltd.).
The stirring speed is preferably 1,000 r / min or more, more preferably 5,000 r / min or more, still more preferably 8,000 r / min or more, and preferably 30,000 r / min or less, more preferably 20 Or less, more preferably 15,000 r / min or less.

  The mass ratio of the polymerizable monomer composition to be introduced to the aqueous medium is preferably 3/97 or more, more preferably 5/95 or more, still more preferably 10/90 or more, and preferably 40/60. The following is more preferably 30/70 or less, more preferably 20/80 or less.

<Step 2>
In step 2, the polymerizable monomer is polymerized in suspension.
The temperature for polymerization is preferably 50 ° C. or more, more preferably 55 ° C. or more, still more preferably 60 ° C. or more, and preferably 90 ° C. or less, more preferably 80 ° C. or less, still more preferably 75 ° C. or less .
The polymerization is preferably carried out with stirring. The apparatus to be used is not particularly limited.
The stirring speed is preferably 50 r / min or more, more preferably 100 r / min or more, still more preferably 150 r / min or more, and preferably 1,000 r / min or less, more preferably 500 r / min or less, more preferably Is less than 300 r / min.

From the viewpoint of dissolving the dispersion stabilizer after polymerization and facilitating the separation of the toner particles, it is preferable to add a mineral acid.
Examples of mineral acids include hydrochloric acid and sulfuric acid.
After polymerization, solid-liquid separation is preferable to obtain toner particles. After solid-liquid separation, it may be washed and dried. As a drying method, for example, a vacuum low temperature drying method, a vibration type fluid drying method, a spray drying method, a freeze drying method, a flash jet method may be mentioned.

The volume median particle diameter (D ₅₀ ) of the toner particles obtained is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 20 μm or less from the viewpoint of obtaining a high quality image. More preferably, it is 15 micrometers or less, More preferably, it is 10 micrometers or less.
The CV value of the toner particles is preferably 12% or more, more preferably 15% or more, still more preferably 20% or more, from the viewpoint of obtaining a high quality image, and preferably 35% or less, more preferably 30. % Or less.
Volume median particle size (D ₅₀ ) and CV values are measured by the methods described in the examples.

The glass transition temperature of the toner particles is preferably 40 ° C. or more, more preferably 45 ° C. or more, and preferably 80 ° C. or less, more preferably 75 ° C. or less, still more preferably 70 ° C. or less, still more preferably 65 ° C. It is below.
The glass transition temperature of toner particles is measured by the method described in the examples.

<Step 3>
The method for producing a toner may further include the step of mixing the obtained toner particles with an external additive.
Examples of the external additive include inorganic fine particles such as hydrophobic silica, titanium oxide, alumina, cerium oxide, carbon black and the like, and polymer fine particles such as polycarbonate, polymethyl methacrylate, silicone resin and the like. Among these, hydrophobic silica is preferred.
The average particle size of the external additive is preferably 1 nm or more, more preferably 5 nm or more, further preferably 10 nm or more, and preferably 500 nm or less, more preferably 300 nm or less, still more preferably 100 nm or less.
When surface treatment of toner particles is performed using an external additive, the amount of external additive added is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, with respect to 100 parts by mass of toner particles. More preferably, it is 1 part by mass or more, and preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and still more preferably 3 parts by mass or less.

  The toner is used to develop a latent image formed in electrophotography, electrostatic recording, electrostatic printing, and the like. Also, the toner can be used as a one-component developer or as a two-component developer mixed with a carrier.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by these examples. Each physical property value of resin etc. was measured and evaluated by the following method.

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

[Amorphous Resin, Crystalline Resin, Hydrocarbon Wax, Maximum Peak Temperature, Melting Point, and Glass Transition Temperature of Release Agent]
Using a differential scanning calorimeter “DSC Q20” (manufactured by TEA Instruments Japan Co., Ltd.), measure 0.01 to 0.02 g of a sample on an aluminum pan, raise the temperature to 200 ° C, and decrease the temperature decrease rate from that temperature Cool to 0 ° C. at 10 ° C./min. Next, the sample is heated at a temperature rising rate of 10 ° C./min to measure an endothermic peak. The temperature at the peak top of the endothermic peak is taken as the highest endothermic peak temperature. In the case of a crystalline resin, a hydrocarbon wax, and a mold release agent, the maximum peak temperature of the endotherm is taken as the melting point. In the case of an amorphous resin, the maximum peak temperature of the endotherm is taken as the glass transition temperature.

[Glass transition temperature (Tg) of toner particles]
Using a differential scanning calorimeter “DSC Q20” (manufactured by TEA Instruments Japan Co., Ltd.), measure 0.01 to 0.02 g of a sample on an aluminum pan, raise the temperature to 200 ° C, and decrease the temperature decrease rate from that temperature Cool to 0 ° C. at 10 ° C./min. Next, the sample is heated at a temperature rising rate of 10 ° C./min to measure an endothermic peak. The temperature at the intersection of the extension of the baseline below the highest endothermic peak temperature and the tangent showing the maximum slope from the rising portion of the peak to the peak of the peak is taken as the glass transition temperature.

[Softening point]
Using a flow tester “CFT-500D” (manufactured by Shimadzu Corporation), while heating a 1 g sample at a temperature elevation rate of 6 ° C./min, a load of 1.96 MPa is applied by a plunger, diameter 1 mm, length 1 mm Push out of the nozzle. The plunger drop amount of the flow tester is plotted against the temperature, and the temperature at which half of the sample flowed out is taken as the softening point.

[Weight average molecular weight of resin and wax, number average molecular weight]
The molecular weight distribution is measured by gel permeation chromatography (GPC) according to the following method to determine the weight average molecular weight and the number average molecular weight.
(1) Preparation of sample solution The sample is dissolved in tetrahydrofuran at 25 ° C. to a concentration of 0.5 g / 100 mL. Next, this solution is filtered using a fluororesin filter “DISMIC-25 JP” (manufactured by ADVANTEC) having a pore size of 0.2 μm to remove insoluble components, and used as a sample solution.
(2) Molecular weight measurement Using the following measuring device and analysis column, flow tetrahydrofuran as an eluent at a flow rate of 1 mL per minute, and stabilize the column in a 40 ° C. thermostat. Then, 100 μL of the sample solution is injected to perform measurement. The molecular weight of the sample is calculated based on a calibration curve prepared in advance. In the calibration curve at this time, several types of monodispersed polystyrene (“A-500” (5.0 × 10 ² ), “A-1000” (1.01 × 10 ³ ), “A-2500” (2. 63 × 10 ³ ), “A-5000” (5.97 × 10 ³ ), “F-1” (1.02 × 10 ⁴ ), “F-2” (1.81 × 10 ⁴ ), “F −4 ”(3.97 × 10 ⁴ ),“ F-10 ”(9.64 × 10 ⁴ ),“ F-20 ”(1.90 × 10 ⁵ ),“ F-40 ”(4.27 ×) 10 ⁵ ), “F-80” (7.06 × 10 ⁵ ), “F-128” (1.09 × 10 ⁶ ) (all manufactured by Tosoh Corporation)) are used as standard samples.
Measuring device: "HLC-8220GPC" (made by Tosoh Corporation)
Analysis column: "GMHXL" + "G3000HXL" (above, made by Tosoh Corporation)

[Volume median particle diameter (D ₅₀ ) of toner particles]
The volume median particle size (D ₅₀ ) of the toner particles was measured by the following method.
Measuring machine: Coulter Multisizer II (made by Beckman Coulter)
Aperture diameter: 50μm
Analysis software: Coulter multisizer Accucomp version 1.19 (manufactured by Beckman Coulter)
Electrolyte: Isoton II (manufactured by Beckman Coulter)
Dispersion: Emulgen 109P (Kao Co., Ltd., polyoxyethylene lauryl ether, HLB: 13.6) 5% by mass Electrolytic solution Dispersion conditions: 10 mg of the measurement sample is added to 5 mL of the dispersion, and 1 minute with an ultrasonic dispersion machine After dispersion, 25 mL of an electrolytic solution is added, and further dispersed for 1 minute with an ultrasonic dispersion machine.
Measurement conditions: 100 mL of the electrolyte and the dispersion are added to a beaker, and 30,000 particles are measured at a concentration that can measure the particle diameter of 30,000 particles in 20 seconds, and the volume median particle diameter Find D ₅₀ ).

[Number average particle size of external additive]
The average particle size of the external additive refers to the number average particle size, and the particle size (average value of the major axis and the minor axis) of 500 particles is measured from a scanning electron microscope (SEM) photograph, and their number average value I assume.

[Production Example of Composite Resin (A)]
Production Examples A1 to A3 and A52 (Resins A-1 to A-3, A-52)
The alcohol component, terephthalic acid and hydrocarbon wax (II) shown in Table 1 are placed in a 10 liter four-necked flask equipped with a dehydrating tube equipped with a nitrogen introducing tube, a stirrer and a thermocouple under a nitrogen atmosphere. The temperature was raised to 160 ° C.
Thereafter, a mixture of acrylic acid as a bireactive monomer, a raw material monomer of a vinyl resin segment and a polymerization initiator was dropped over 1 hour by a dropping funnel. After the dropwise addition, the addition polymerization reaction was aged for 1 hour while being maintained at 160 ° C. Subsequently, di (2-ethylhexanoic acid) tin and gallic acid were added, and the temperature was raised to 235 ° C. to cause a polycondensation reaction for 6 hours, and then the reaction was performed at 235 ° C. and 8.0 kPa for 1 hour. After cooling to 180 ° C., add the adipic acid and trimellitic anhydride shown in the table, raise the temperature from 180 ° C. to 210 ° C. at 10 ° C./hour, and react at 210 ° C. for 1 hour, 210 The reaction was carried out at a temperature of 10 kPa and at a softening point shown in the table to obtain resins A-1 to A-3 and A-52.

Production Example A51 (Resin A-51)
The alcohol component, terephthalic acid and hydrocarbon wax (II) shown in Table 1 are placed in a 10 liter four-necked flask equipped with a dehydrating tube equipped with a nitrogen introducing tube, a stirrer and a thermocouple, and under a nitrogen atmosphere, 140 After di (2-ethylhexanoate) tin and gallic acid were added at .degree. C., the temperature was raised to 235.degree. C., a polycondensation reaction was performed for 6 hours, and a reaction was further performed at 235.degree. C. and 8.0 kPa for 1 hour. After cooling to 180 ° C., add adipic acid and trimellitic anhydride, raise the temperature from 180 ° C. to 210 ° C. at 10 ° C./hour, carry out the reaction at 210 ° C. for 1 hour, 210 ° C., 10 kPa The reaction was carried out to the softening point shown in the table to obtain a resin A-51.

[Production Example of Crystalline Resin]
Production Example C1 to C2 (Resins C-1 to C-2)
The alcohol components shown in Table 2 were placed in a 10 L four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple, and heated to 120 ° C. At 120 ° C., the carboxylic acid components shown in the table were added and further heated to 200 ° C. over 10 hours. Di (2-ethylhexanoic acid) tin (II) and gallic acid are added, reacted at 200 ° C. for 1 hour, and reacted at 8.3 kPa for 1 hour to obtain a crystalline resin (Resin C-1) ~ C-2) was obtained.

[Toner production]
Examples 1 to 6 and Comparative Examples 1 to 4 (Toners 1 to 6 and 51 to 54)
Raw material monomers and resin of styrene acrylic resin shown in Table 3, coloring agent "Pigment Blue 15: 3" (manufactured by Dainichi Seika Kogyo Co., Ltd.) 5 g, charge control agent "Bontron E-88" in a 300 mL glass beaker 1 g of Orient Chemical Industries, Ltd., aluminum salicylate, and 10 g of a mold release agent “HNP-9” (Nippon Seiwa Co., Ltd., paraffin wax, melting point: 75.5 ° C.) are added and stirred and mixed at 60 ° C. Heat up to a level and dissolve uniformly. Thereafter, 4 g of a polymerization initiator "V-65"(2,2'-azobis (2,4-dimethylvaleronitrile) manufactured by Wako Pure Chemical Industries, Ltd.) was added to prepare a resin solution. 150 g of ion-exchanged water, calcium triphosphate (chemical formula: 3 [Ca ₃ (PO ₄ ) ₂ ] · Ca (OH) ₂ ) 10 mass% slurry “TCP-10 · U” (Taipei Kagaku) in a 1-liter glass beaker An aqueous medium was prepared by adding 500 g of Sangyo Co., Ltd.) and 0.004 g of an anionic surfactant "Neoperex G-15" (Kao Co., sodium dodecylbenzene sulfonate) and stirring. The aqueous medium is heated to 60 ° C., and while maintaining the temperature at 60 ° C., the resin solution is added all at once, and stirred for 4 minutes at 12,000 r / min with a homomixer “MARK II 2.5 type” (manufactured by PRIMIX Corporation) , Obtained a suspension.
The suspension was transferred to a separable flask and polymerized for 8 hours while stirring at 70 ° C. and 200 r / min. Thereafter, the temperature was raised to 80 ° C., and the remaining monomer was distilled off under reduced pressure. It cooled to 20 degreeC, continuing stirring, and hydrochloric acid was added until the pH of system inside became 1 or less. After washing and drying, toner particles of volume median particle diameter (D ₅₀ ) shown in Table 3 were obtained.

  To 100 parts by mass of toner particles, 1.0 part by mass of hydrophobic silica "Aerosil R-972" (manufactured by Nippon Aerosil Co., Ltd., average particle size: 16 nm) is added as an external additive, and 3600 r / min. By mixing for a minute, the external additive treatment was performed to obtain toners 1 to 6 and 51 to 54.

[Evaluation]
The following evaluations were performed on the obtained toner, and the results are shown in Table 4.

Low temperature fixability
The toner is mounted on an apparatus obtained by improving the fixing device of the copying machine “AR-505” (manufactured by Sharp Corporation) so that fixing is possible outside the apparatus, and paper [CopyBond SF-70NA (75 g / m ² )] ( Printed matter was obtained in an unfixed state such that the amount of toner adhesion was 0.5 mg / cm ² on Sharp Co., Ltd.). The unfixed state at each temperature while sequentially increasing the temperature of the fixing roller from 90 ° C. to 240 ° C. by 5 ° C. using a fixing device (fixing speed 200 mm / sec) adjusted so that the total fixing pressure is 40 kgf The fixing test of the printed matter was conducted.
A sand eraser with a load of 500 g and a bottom of 15 mm x 7.5 mm rubs the image fixed through the fuser 5 times back and forth, and the optical reflection density before and after the reflection densitometer “RD-915” (Macbeth Co., Ltd.) The temperature of the fixing roller where the ratio of both (after rubbing / before rubbing) first exceeds 70% was taken as the minimum fixing temperature.

[Preservation stability]
10 g of the toner was placed in a cylindrical container with a radius of 12 mm, a 100 g weight was placed from the top, and held for 72 hours in an environment of 50 ° C. and 60% relative humidity.
Three sieves, sieve A (250 μm mesh), sieve B (150 μm mesh) and sieve C (50 μm mesh), are stacked in this order on top of a powder tester (manufactured by Hosokawa Micron Corporation). 10 g of toner was placed on top and vibrated for 60 seconds.
The toner mass W _A (g) remaining on the sieve A, the toner mass W _B (g) remaining on the sieve B, and the toner mass W _C (g) remaining on the sieve C are measured, respectively. :
_{α = 100- (W A + W} B × 0.6 + W C × 0.2) / 10 × 100
Storage stability was evaluated based on the value (α) calculated according to. The closer the value (α) is to 100, the better the storage stability, the value (α) 100-80 is A, the value (α) 80-60 is B, the value (α) 60-40 is C, the value (α) 40 or less is written as D.

[Charging stability]
The chargeability characteristics were evaluated under the condition that the toner was left to stand immediately after production and in an environment of temperature 45 ° C. and relative humidity 50% for two weeks.
Immediately after production and after standing, the toner is 0.6 g of toner and a silicone-coated ferrite carrier (manufactured by Kanto Denka Kogyo Co., Ltd.) having a volume average particle diameter of 60 μm under an environment of an arbitrary temperature and a relative humidity of 50%. 4 g was placed in a 20 mL cylindrical poly bottle, and the container was fixed in a turbula shaker and rotated at a speed of 90 r / min. The charge amount over time (the charge amount at a mixing time of 1 minute and 10 minutes) was measured with a q / m meter (manufactured by Epping), and a 10-minute value / one-minute value was calculated for each.
[Q / m meter setting]
Mesh size: 400 mesh (made of stainless steel)
Soft blow suction time (blow pressure 1050 V): 90 seconds charge amount (μC / g) = total electric amount after 90 seconds of toner suction time (μC) / sucked toner amount (g)

  As described above, according to the comparison between the examples and the comparative examples, it is understood that according to the production method of the present invention, a toner having excellent low temperature fixability, storage stability, and charge stability under high temperature conditions can be obtained.

Claims (7)

A process for producing a toner for electrophotography, comprising the step of suspension-polymerizing a polymerizable monomer composition containing a crystalline polyester resin, a composite resin (A), a polymerizable monomer and a colorant in an aqueous medium. ,
The polycondensation of an alcohol component containing 80 mol% or more of an α, ω-aliphatic diol having 2 to 16 carbon atoms and a carboxylic acid component containing an aliphatic dicarboxylic acid having 4 to 18 carbon atoms in the crystalline polyester resin It is a thing,
The composite resin (A) is a vinyl resin segment, which is an addition polymer of a polyester resin segment and a raw material monomer containing a styrenic compound, and both reactions bonded via covalent bonds to the polyester resin segment and the vinyl resin segment. A constituent unit derived from a cationic monomer and a constituent unit derived from hydrocarbon wax (II) bonded to the polyester resin segment via a covalent bond,
The method for producing an electrophotographic toner, wherein the hydrocarbon wax (II) has at least one group selected from a hydroxyl group and a carboxy group, and has a melting point of 60 ° C. or more and 130 ° C. or less.   The method for producing an electrophotographic toner according to claim 1, wherein the polymerizable composition further contains a releasing agent (I).   The method for producing a toner for electrophotography according to claim 1 or 2, wherein a total value of a hydroxyl value and an acid value of the hydrocarbon wax (II) is 40 mgKOH / g or more and 200 mgKOH / g or less.   The mass ratio of the total mass of the polyester resin segment and the constituent unit derived from the bireactive monomer in the composite resin (A) to the vinyl resin segment is 60/40 or more and 95/5 or less. The manufacturing method of the toner for electrophotography in any one of Claims 1-3.   Content of the said composite resin (A) is 2 mass% or more and 30 mass% or less with respect to the total amount of the said crystalline polyester resin, the said composite resin (A), and the said polymerizable monomer, Crystalline polyester resin The content of the said is 2 mass% or more and 30 mass% or less with respect to the total amount of the said crystalline polyester resin, the said composite resin (A), and the said polymerizable monomer. Of electrophotographic toner.   The raw material monomer of the said vinyl-type resin segment contains 1 mass% or more and 30 mass% or less of the vinyl-type monomers which have C3 or more and 22 or less aliphatic hydrocarbon group. Method of producing toner for electrophotography.   The method for producing a toner for electrophotography according to any one of claims 1 to 6, wherein a mass ratio of the crystalline polyester resin to the polymerizable monomer is 5/90 or more and 25/75 or less.